Crystal structure, spectroscopic studies and theoretical studies of thiobarbituric acid derivatives: understanding the hydrogen-bonding patterns

research paper s

Crystal structure, spectroscopic studies and theo-

retical studies of thiobarbituric acid derivatives:

understanding the hydrogen-bonding patterns

ISSN 2053-2296

a

b

c

Anamika Sharma, ‡ Sizwe J. Zamisa, ‡ Sikabwe Noki, Zainab Almarhoon, Ayman

c,d

e

b,c,f,g

El-Faham, * Beatriz G. de la Torre * and Fernando Albericio

*

Received 24 July 2018

a

School of Health Sciences, University of KwaZulu Natal, University Road, Westville, Durban, 4000, South Africa,

Accepted 2 November 2018

b

School of Chemistry and Physics, University of KwaZulu Natal, Private bag X54001, Westville campus, Durban, 4000,

c

South Africa, Department of Chemistry, College of Science, King Saud University, 2455 Riyadh, 11451, Saudi Arabia,

d

Edited by F. A. Almeida Paz, University of

Aveiro, Portugal

e

Department of Chemistry, Faculty of Science, Alexandria University, 426 Alexandria, 21321, Egypt, KRISP, College of

f

Health Sciences, University of KwaZulu Natal, Durban, 4001, South Africa, Department of Organic Chemistry,

g

University of Barcelona, Mart ´ı i Franqu e´ s 1-11, Barcelona 08028, Spain, and CIBER–BBN, Networking Centre on

‡

These authors contributed equally to the work

Bioengineering, Biomaterials and Nanomedicine, Barcelona Science Park, Baldiri Reixac 10, Barcelona 08028, Spain.

*Correspondence e-mail: aymanel_faham@hotmail.com, garciadelatorreb@ukzn.ac.za, albericio@ukzn.ac.za

Keywords: thiobarbituric acid; X-ray crystal-

lography; UV spectroscopy; crystal structure; IR

spectroscopy; DFT calculations; transition state.

In addition to their wide-ranging applications in the pharmaceutical industry,

thiobarbituric acid (TBA) derivatives are also known to possess applications in

engineering and materials science. 20 TBA derivatives, with diversity at the N

and C-5 positions through acylation, Schiff base formation, Knoevenagel

condensation, thioamide and enamine formation, were studied. The absolute

conﬁgurations for six derivatives, namely 5-acetyl-1,3-diethyl-2-thioxodihydro-

pyrimidine-4,6(1H,5H)-dione, C H N O S, A01, 1,3-diethyl-5-propionyl-2-

CCDC references: 1822987; 1822988;

1822985; 1822984; 1822986; 1822983

Supporting information: this article has

supporting information at journals.iucr.org/c

10

14

2

3

thioxodihydropyrimidine-4,6(1H,5H)-dione, C H N O S, A02, tert-butyl

3

11

16

2

[1-(1,3-diethyl-4,6-dioxo-2-thioxohexahydropyrimidin-5-yl)-3-methyl-1-oxobutan-2-

yl]carbamate, C H N O S, A06, 1,3-diethyl-4,6-dioxo-2-thioxo-N-(p-tolyl)-

18

29

3

5

hexahydropyrimidine-5-carbothioamide, C H N O S , A13, 5-(1-aminoethyl-

19

16

3

2 2

idene)-1,3-diethyl-2-thioxodihydropyrimidine-4,6(1H,5H)-dione, C H N O S,

15

10

3

2

A17, and 5-(1-aminopropylidene)-1,3-diethyl-2-thioxodihydropyrimidine-

,6(1H,5H)-dione, C H N O S, A18, were conﬁrmed by single-crystal X-ray

4

11

17

3

2

crystallography, which indicates the formation of intramolecular hydrogen bonding

in all six cases and intermolecular hydrogen bonding for A17. In A13, the presence

of two intramolecular hydrogen bonds was observed. The stabilization of the enol

form over the keto form was conﬁrmed by computation. In order to convert the

ꢀ1

keto form to the enol form, an energy barrier of 55.05 kcal mol needs to be

overcome, as conﬁrmed by transition-state calculations.

1

. Introduction

A prerequisite for rational drug design and structure-based

functional studies is an accurate knowledge of the molecular

structure, which is derived solely by X-ray crystallography

(Aitipamula & Vangala, 2017; Deschamps, 2008; Zheng et al.,

2014). It is the most reliable technique available for deter-

mining a three-dimensional (3D) structure with the correct

conﬁguration of the molecule at the atomic level. As structure

and function are related, conﬁguration plays a critical role in

biological systems, as changes in this may alter the response of

the biologic system (Mason, 1983). Compounds containing the

barbituric acid/thiobarbituric acid (BA/TBA) moiety (Fig. 1)

play a vital role as anti-anxiety agents in the central nervous

system by binding to the ꢀ-aminobutyric acid (GABA)

receptor (Kapoor et al., 2016; Ahluwalia & Aggarwal, 1996).

Thiobarbituric acid (TBA) derivatives are privileged

structures which display a broad range of biological activities,

#

2018 International Union of Crystallography

Acta Cryst. (2018). C74, 1703–1714

https://doi.org/10.1107/S2053229618015516 1703

research papers

tion software was used for data processing over a 5–95%

gradient of CH CN (0.1% triﬂuoroacetic acid)/H O (0.1%

3

2

triﬂuoroacetic acid) over a period of 15 min, with a ﬂow rate of

1.0 ml min and detection at 220 nm. High resolution mass

ꢀ1

spectrometry (HRMS) was performed using a Bruker ESI–

QTOF mass spectrometer in positive-ion mode.

Figure 1

General structure of BA and TBA. The atom-labelling scheme is shown in

Fig. 4.

2

.2. Synthesis of derivatives

Derivatives A01–A20 were synthesized as reported

previously by our group (Sharma et al., 2018). Further char-

acterizations are given in the following sections.

including antiepileptic, anticancer, antioxidant, anticon-

vulsant, immuno-modulatory, gelatinase inhibiting, HIV inte-

grase inhibiting, antifungal, antiviral, tyrosinase inhibiting,

anti-inﬂammatory and antidiabetic effects (Agarwal et al.,

2.2.1. 5-Acetyl-1,3-diethyl-2-thioxodihydropyrimidine-4,6-

(1H,5H)-dione (A01). Pale-white solid; 82% yield; m.p. 40–

42 C; HPLC t = 11.9 min; ꢁ

ꢂ

ꢀ1

= 316 nm; IR (cm ): 1231

R

max

1

2

006; Singh et al., 2009; Khan et al., 2008; Jursic & Neumann,

001; Jursic et al., 2003; Wang et al., 2011; Rajamaki et al., 2009;

(C S), 1685 (C O); H NMR (400 MHz, DMSO-d ): ꢂ 1.18

6

1

3

(t, J = 7 Hz, –CH ), 2.65 (s, –CH ), 4.40 (q, J = 7 Hz, –CH ); C

3

2

Lee et al., 2011; Chen et al., 2014; Penthala et al., 2013). The

bioactivity, however, differs from molecule to molecule

depending on the tautomerization and the nature of the

substituents (Chierotti et al., 2010; Demeunynck et al., 2006).

Apart from their importance in the pharmaceutical industry,

TBA derivatives are also known to possess nonlinear optical

properties (NLO), corrosion inhibition properties, applica-

tions in analytical chemistry and they are suitable for crystal

engineering materials possessing speciﬁc programmed prop-

erties due to their possessing both hydrogen-bond donors and

NMR (100 MHz, DMSO-d ): ꢂ 11.8, 24.5, 42.5, 78.9, 97.4,

6

177.1, 197.3. HRMS (m/z): calculated for C H N O S:

3

1

0

14

2

+

243.0798 [M + H] ; found: 243.0811.

2.2.2. 1,3-Diethyl-5-propionyl-2-thioxodihydropyrimidine-

4,6(1H,5H)-dione (A02). Pale-white solid; 56% yield; m.p. 74–

ꢂ

ꢀ1

75 C; HPLC t = 12.9 min; IR (cm ): 1227 (C S), 1680

R

1

(C O); H NMR (400 MHz, DMSO-d ): ꢂ 1.14 (t, J = 7.4 Hz,

6

–CH ), 1.19 (t, J = 7.0 Hz, –CH ), 3.11 (q, J = 7.4 Hz, –CH ),

3

2

1

3

4.41 (q, J = 7.0 Hz, –CH₂); C NMR (100 MHz, DMSO-d ): ꢂ

6

8.9, 11.8, 30.7, 42.6, 96.6, 171.6, 177.0, 201.4. HRMS (m/z):

+

calculated for C H N O S: 257.0954 [M + H] ; found:

257.0966.

¨

acceptors (Ivanova & Spiteller, 2010; Ozcan et al., 2008; Roux

et al., 2012).

11

16

2

3

Protons at the C-5 position in TBA are highly acidic and

hence undergo various reactions, including acylation and

Knoevenagel condensation, among others (Faidallah & Khan,

2.2.3. 5-Benzoyl-1,3-diethyl-2-thioxodihydropyrimidine-

4,6(1H,5H)-dione (A03). Pale-white solid; 36% yield; m.p.

ꢂ

ꢀ1

92–93 C; HPLC t = 13.1 min; IR (cm ): 1287 (C S), 1675

R

1

2012). Substitution at C-5 increases lipophilicity and hence

(C O); H NMR (400 MHz, DMSO-d ): ꢂ 1.18 (t, J = 7.0 Hz,

6

1

3

facilitates the transport of BA and TBA analogs towards their

enzyme targets (Ahluwalia & Aggarwal, 1996). In view of the

signiﬁcance of TBA derivatives, we became interested in

synthesizing new TBA derivatives with several C-5 substitu-

tions, including amino acid–TBA conjugates, followed by

density functional theory (DFT) calculations to understand

the keto–enol conformation of the TBA derivatives.

–CH ), 4.39 (q, J = 7.0 Hz, –CH ), 7.4–7.6 (m, ArH); C NMR

3 2

(100 MHz, DMSO-d ): ꢂ 12.1, 42.3, 96.3, 127.6, 128.4, 131.4,

6

137.1, 161.6, 167.3, 177.0, 192.3. HRMS (m/z): calculated for

+

C H N O S: 305.0954 [M + H] ; found: 305.0957.

15

16

2

3

2.2.4. tert-Butyl [1-(1,3-diethyl-4,6-dioxo-2-thioxohexa-

hydropyrimidin-5-yl)-1-oxo-3-phenylpropan-2-yl]carbamate

ꢂ

(A04). Pale-pink solid; 94% yield; m.p. 130–131 C; HPLC t =

R

ꢀ

1

4.4 min; ꢁ_m_a_x= 322 nm; IR (cm ): 1164 (C S), 1682

O), 3359 (N—H); H NMR (400 MHz, DMSO-d ): ꢂ 1.18

t, J = 7.2 Hz, –CH ), 1.28 (s, –CH ), 3.09–3.12 (m, –CH ), 4.44

3

1

(

C

6

2

. Experimental

3

2

2.1. General

q, J = 7.2 Hz, –CH ), 5.52 (t, J = 7.8, –CH), 7.16 (d, J = 7.3 Hz,

2

13

All reagents and solvents were purchased from commercial

–NH), 7.21–7.33 (m, Ar-H); C NMR (100 MHz, DMSO-d₆):

ꢂ 12.4, 18.8, 28.1, 45.7, 60.2, 69.9, 71.9, 125.7, 127.7, 129.3, 138.9,

155.1, 177.1, 183.8, 216.1. HRMS (m/z): calculated for

suppliers and were used without further puriﬁcation, unless

otherwise stated. Fourier transform infrared (FT–IR) spectra

were recorded on a Bruker-ALPHA Spectrophotometer in

+

C H N O S: 448.1900 [M + H] ; found: 448.1901.

29

22

3

5

ꢀ

1

the spectral range 400–4000 cm . The electronic spectra of

the studied compounds (1 mg in 50 ml solvent) were measured

using a 3600 Series UV-Spectrophotometer in different

solvents, such as acetonitrile, ethanol and dichloromethane.

2.2.5. 1,3-Diethyl-5-phenylalanyl-2-thioxodihydropyrimi-

dine-4,6(1H,5H)-dione (A05). Pale-pink gum; 98% yield;

1

HPLC t_R= 7.6 min; ꢁ_m_a_x= 308 nm; H NMR (400 MHz,

DMSO-d ): ꢂ 1.15 (t, J = 6.8 Hz, –CH ), 3.08–3.12 (m, –CH ),

6

3

2

1

13

NMR spectra ( H NMR and C NMR) were recorded on a

Bruker AVANCE III 400 MHz spectrometer. Chemical shift

values are expressed in parts per million (ppm). Analytical

HPLC was performed on an Agilent 1100 system using a

Phenomenax C₁₈column (3 mm, 4.6 ꢁ 50 mm) and Chemsta-

4.20 (t, J = 5.5 Hz, –CH), 4.40 (q, J = 6.8 Hz, –CH ), 7.23–7.30

2

1

3

(m, Ar-H), 7.72 (bs, –NH ); C NMR (100 MHz, DMSO-d ): ꢂ

2

6

12.5, 41.5, 53.1, 58.5, 95.0, 128.4, 128.6, 129.4, 136.5, 160.2,

176.7, 189.6. HRMS (m/z): calculated for C H N O S:

1

7

21

3

+

348.1376 [M + H] ; found: 348.1388.

ꢃ

1

704 Sharma et al. Thiobarbituric acid derivatives

Acta Cryst. (2018). C74, 1703–1714

research papers

ꢂ

solid; 76% yield; m.p. 163–165 C; HPLC t = 12.2 min;

R

2

.2.6. tert-Butyl [1-(1,3-diethyl-4,6-dioxo-2-thioxohexa-

ꢀ

1

hydropyrimidin-5-yl)-3-methyl-1-oxobutan-2-yl)carbamate

ꢁ_m_a_x= 289 nm; IR (cm ): 1108 (C S), 1611 (C O); H

NMR (400 MHz, DMSO-d ): ꢂ 1.14 (t, J = 6.7 Hz, –CH ), 4.40

ꢂ

(

A06). Dark-pink solid; 92% yield; m.p. 100–101 C; HPLC

ꢀ

6

3

1

13

t_R= 14.1 min; ꢁ_m_a_x= 320 nm; IR (cm ): 1105 (C S), 1623

(q, J = 6.7 Hz, –CH ), 6.42 (s, –CH), 7.51–8.41 (m, Ar-H); C

2

1

(

C

O) 3369 (N—H); H NMR (400 MHz, DMSO-d ): ꢂ 0.81

NMR (100 MHz, DMSO-d ): ꢂ 12.1, 32.3, 42.8, 94.2, 118.9,

6

(

3

5

d, J = 6.8 Hz, –CH ), 1.18 (t, J = 6.6 Hz, –CH ), 1.37 (s, –CH ),

3

125.6, 130.9, 143.4, 145.5, 149.3, 160.7, 174.4. HRMS (m/z):

+

calculated for C H N O S : 579.1326 [M + H] ; found:

3

.06–3.11 (m, –CH), 3.80 (s, –CH), 4.41 (q, J = 6.8 Hz, –CH ),

2

23 26

6

8 2

13

.52 (d, J = 7.3 Hz, –CH), 6.87 (s, NH); C NMR (100 MHz,

579.1322.

2.2.13. 1,3-Diethyl-4,6-dioxo-2-thioxo–(p-tolyl)hexahydro-

pyrimidine-5-carbothioamide (A13). Pale-yellow solid; 90%

DMSO-d ): ꢂ 11.9, 28.1, 30.1, 42.6, 52.1, 58.9, 78.1, 139.1, 155.6,

1

4

6

68.7, 176.8, 199.5. HRMS (m/z): calculated for C H N O S:

18 29 3 5

+

ꢂ

00.1901 [M + H] ; found: 400.1884.

.2.7. 1,3-Diethyl-2-thioxo-5-valyldihydropyrimidine-

,6(1H,5H)-dione (A07). Dark-pink gum; 97% yield;

yield; m.p. 132–133 C; HPLC t = 15.6 min; ꢁ = 333 nm; IR

R

max

ꢀ1

1

(cm ): 1105 (C S), 1645 (C O); H NMR (400 MHz,

2

4

DMSO-d ): ꢂ 1.31 (t, J = 7.0 Hz, –CH ), 2.39 (s, –CH ), 4.58 (q,

6

3

1

13

J = 7.0, –CH ), 7.31–7.39 (m, Ar-H), 13.9 (s, –NH); C NMR

HPLC t = 6.6 min; H NMR (400 MHz, DMSO-d ): ꢂ 0.76 (d,

R

6

2

J = 7 Hz, –CH ), 1.2 (t, J = 7 Hz, –CH ), 2.16 (m, –CH), 3.10

3

(100 MHz, DMSO-d ): ꢂ 11.6, 20.7, 43.8, 91.7, 125.2, 129.5,

3

6

(

7

m, –CH), 4.37 (q, J = 7 Hz, –CH ), 4.96 (d, J = 8.5 Hz, –CH),

2

134.5, 137.0, 174.3, 184.9, 202.9. HRMS (m/z): calculated for

+

C H N O S : 350.0991 [M + H] ; found: 350.0962.

1

3

.66 (bs, NH₂); C NMR (100 MHz, DMSO-d ): ꢂ 12.5, 15.8,

6

16 19

3

2 2

19.6, 29.1, 41.5, 61.5, 160.1, 176.7, 190.5. HRMS (m/z): calcu-

lated for C H N O S: 300.1376 [M + H] ; found: 300.1377.

2.2.14. 2-Thioxo-1,3-di-p-tolyldihydropyrimidine-4,6(1H,5H)-

+

ꢂ

1

3

21

3

dione (A14). Yellow solid; 92% yield; m.p. 218–220 C; HPLC

ꢀ

1

2.2.8. (E)-1,3-Diethyl-5-{1-[(pyridin-2-ylmethyl)imino]eth-

t_R= 10.2 min; ꢁ = 241 nm, 286 nm; IR (cm ): 1339 (C S),

max

1

yl}-2-thioxodihydropyrimidine-4,6(1H,5H)-dione (A08). Pale-

yellow solid (gummy at room temperature); 86% yield; HPLC

1700 (C O); H NMR (400 MHz, DMSO-d ): ꢂ 2.27 (s,

6

–CH ), 7.12 (d, J = 8.1 Hz, Ar-H), 7.33 (d, J = 8.1 Hz, Ar-H),

3

1

13

9.58 (s, –CH ,); C NMR (100 MHz, DMSO-d ): ꢂ 21.1, 40.6,

128.4, 129.5, 136.6, 137.9, 169.3, 174.2. HRMS (m/z):

t = 8.8 min; H NMR (400 MHz, CDCl ): ꢂ 1.22 (t, J = 7.0 Hz,

R

3

2

6

–

CH ), 2.69 (s, –CH ), 4.49 (q, J = 7.0 Hz, –CH ), 4.75 (d, J =

3

2

13

+

calculated for C H N O S: 325.1005 [M + H] ; found:

5.6 Hz, –CH ), 7.2–8.6 (m, Ar-H), 13.3 (s, –CH); C NMR

2

18 16

2

(

100 MHz, CDCl ): ꢂ 11.4, 17.9, 41.8, 42.2, 48.2, 92.3, 120.4,

325.1025.

2.2.15. 5-Acetyl-2-thioxo-1,3-di-p-tolyldihydropyrimidine-

4,6(1H,5H)-dione (A15). Yellow solid; 45% yield; m.p. 185–

3

122.1, 136.3, 148.9, 153.3, 174.3, 176.6. HRMS (m/z): calculated

for C H N O S: 333.1380 [M + H] ; found: 333.1387.

+

1

6

20

4

2

ꢂ

186 C; HPLC t = 12.0 min; H NMR (400 MHz, DMSO-d ):

R 6

1

2.2.9. (E)-1,3-Diethyl-5-{1-[(4-methoxybenzyl)imino]eth-

yl}-2-thioxodihydropyrimidine-4,6(1H,5H)-dione (A09). White

ꢂ 2.34 (s, –CH ), 2.65 (s, –CH ), 7.15 (d, J = 8.2 Hz, Ar-H), 7.26

3

ꢂ

1

13

solid; 69% yield; m.p. 98–100 C; HPLC t_R= 12.6 min; H

NMR (400 MHz, CDCl ): ꢂ 1.21 (t, J = 6.9 Hz, –CH ), 2.10 (s,

(d, J = 8.2 Hz, Ar-H); C NMR (100 MHz, DMSO-d ): ꢂ 20.7,

6

3

24.5, 98.2, 128.5, 129.5, 136.7, 137.6, 179.6, 196.3, 206.9. HRMS

+

(m/z): calculated for C H N O S: 366.1077 [M + H] ; found:

–

OCH ), 2.66 (s, –CH ), 3.75 (s, –CH ), 4.47 (q, J = 7.0 Hz,

3

2

3

20 18

2

3

13

–CH ), 6.84–7.15 (m, Ar-H), 12.96 (s, –CH); C NMR

2

366.1100.

2.2.16. 5-Propionyl-2-thioxo-1,3-di-p-tolyldihydropyrimi-

dine-4,6(1H,5H)-dione (A16). Yellow solid; 57% yield; m.p.

(

100 MHz, CDCl ): ꢂ 11.4, 17.2, 41.8, 42.6, 46.8, 54.9, 113.7,

3

127.4, 130.1, 152.1, 154.4, 167.4, 173.6 HRMS (m/z): calculated

for C H N O S: 362.1533 [M + H] ; found: 362.1535.

+

ꢂ

1

8

23

3

140–141 C; HPLC t = 12.7 min; ꢁ

R

= 318 nm; H NMR

max

2.2.10. 1,3-Diethyl-5-(4-fluorobenzylidene)-2-thioxodi-

(400 MHz, DMSO-d ): ꢂ 1.14 (t, J = 7.4 Hz, –CH ), 2.33 (s,

6 3

hydropyrimidine-4,6(1H,5H)-dione (A10). Yellow solid;

–CH ), 2.91 (q, J = 7.4 Hz, –CH ), 7.08 (d, J = 8.2 Hz, Ar-H),

3 2

ꢂ

13

7

2

0% yield; m.p. 180–182 C; HPLC t = 11.9 min; ꢁ_m_a_x

=

87 nm, 361 nm; IR (cm ): 1108 (C S), 1614 (C O); H

7.20 (d, J = 8.2 Hz, Ar-H); C NMR (100 MHz, DMSO-d ): ꢂ

R

6

ꢀ

1

10.1, 20.7, 30.1, 63.4, 128.5, 129.5, 137.6, 166.2, 170.6, 179.5,

187.6. HRMS (m/z): calculated for C H N O S: 381.1290

NMR (400 MHz, CDCl ): ꢂ 1.30 (t, J = 7.0 Hz, –CH ), 4.59 (q,

3

21 20

2

3

13

+

[M + H] ; found: 381.1267.

J = 7.0 Hz, –CH ), 7.00–7.04 (m, Ar-H), 13.86 (s, –CH);

2

C

NMR (100 MHz, CDCl ): ꢂ 12.1, 45.2, 97.4, 115.2, 115.4, 127.9,

2.2.17. 5-(1-Aminoethylidene)-1,3-diethyl-2-thioxodihydro-

3

128.0, 162.2, 163.7, 174.6. HRMS (m/z): calculated for

C H N O S: 307.0911 [M + H] ; found: 307.0908.

pyrimidine-4,6(1H,5H)-dione (A17). Yellow solid; m.p. 190–

+

ꢂ

ꢀ1

1

5

15

2

191 C; HPLC t = 9.2 min; ꢁ

R

max

= 320 nm; IR (cm ): 1357

0

1

(C S), 1613 (C O) 3295 (N—H); H NMR (400 MHz,

2.2.11. 5,5 -[(3,5-Dimethoxyphenyl)methylene]bis[1,3-di-

ethyl-2-thioxodihydropyrimidine-4,6(1H,5H)-dione] (A11).

DMSO-d ): ꢂ 1.14 (t, J = 7 Hz, –CH ), 2.53 (s, –CH ), 4.37 (q,

J = 7 Hz, –CH ), 9.7 (s, –NH ), 11.1 (s, –NH ); C NMR

2 2 2

6

3

13

ꢂ

Yellow solid; 74% yield; m.p. 150–151 C; HPLC t = 13.2 min;

R

1

ꢁ_m_a_x= 284 nm, 366 nm; H NMR (400 MHz, DMSO-d ): ꢂ 1.16

(100 MHz, DMSO-d ): ꢂ 12.1, 24.3, 42.0, 91.2, 175.8, 176.9,

6

(

J = 7.0 Hz, –CH ), 6.10–6.26 (m, Ar-H), 8.10 (d, J = 6.6, –CH);

t, J = 7.0 Hz, –CH ), 3.44 (m, –CH), 3.62 (s, –OCH ), 4.45 (q,

197.3. HRMS (m/z): calculated for C H N O S: 242.0958

2

3

10 15

3

+

2

[M + H] ; found: 242.0966.

2.2.18. 5-(1-Aminopropylidene)-1,3-diethyl-2-thioxodi-

hydropyrimidine-4,6(1H,5H)-dione (A18). Yellow solid; m.p.

1

3

C NMR (100 MHz, DMSO-d ): ꢂ 12.3, 18.5, 33.6, 42.8, 54.8,

6

96.3, 104.9, 145.2, 160.1, 161.1, 174.0. HRMS (m/z): calculated

for C H N O S : 549.1836 [M + H] ; found: 549.1821.

+

ꢂ

1

2

5

32

4

6

2

101–102 C; HPLC t = 10.1 min; H NMR (400 MHz, DMSO-

R

0

2

.2.12. 5,5 -[(2,4-Dinitrophenyl)methylene]bis[1,3-diethyl-

d ): ꢂ 1.15 (t, J = 7.3 Hz, –CH ), 1.16 (t, J = 6.9 Hz, –CH ), 2.53

6

3

2-thioxodihydropyrimidine-4,6(1H,5H)-dione] (A12). Buff

(q, J= 7.3 Hz, –CH ), 4.40 (q, J= 6.9 Hz, –CH ), 9.68 (s, –NH ),

2

3

2

ꢃ

Acta Cryst. (2018). C74, 1703–1714

Sharma et al.

Thiobarbituric acid derivatives 1705

research papers

Table 1

Experimental details.

All determinations used a temperature of 100 K, a Bruker APEXII CCD diffractometer and a multi-scan (SADABS; Bruker, 2012) absorption correction.

A01

A02

A06

Crystal data

Chemical formula

C

10

H N

14 2

3

O S

C

H

11 16

N O

2 3

S

18 29 3 5

C H N O S

M

r

242.29

Monoclinic, P2

4.6212 (1), 12.5742 (4), 19.3936 (6)

90, 92.869 (1), 90

1125.51 (6)

256.32

Monoclinic, P2

4.9140 (1), 12.9450 (3), 9.7630 (3)

90, 103.474 (1), 90

603.95 (3)

399.50

1 1 1

Orthorhombic, P2 2 2

8.3816 (12), 9.6258 (14), 24.297 (3)

90, 90, 90

1960.3 (5)

4

Mo Kꢃ

0.20

Crystal system, space group

˚

1

/n

1

a, b, c (A)

ꢂ

ꢃ, ꢄ, ꢀ ( )

˚

3

V (A )

Z

Radiation type

ꢅ (mm

Crystal size (mm)

4

2

Mo Kꢃ

0.28

0.29 ꢁ 0.23 ꢁ 0.12

Mo Kꢃ

0.27

0.19 ꢁ 0.14 ꢁ 0.07

ꢀ

1

)

0.33 ꢁ 0.25 ꢁ 0.21

Data collection

T

min, Tmax

0.911, 0.978

14896, 2704, 2309

0.940, 0.991

8623, 8623, 8469

0.925, 0.968

15360, 15360, 14556

No. of measured, independent and

observed [I > 2ꢆ(I)] reﬂections

R

int

0.016

0.667

0.000

0.650

0.000

0.654

˚

ꢀ1

)

(sin ꢇ/ꢁ)max (A

Reﬁnement

2

R[F > 2ꢆ(F )], wR(F ), S

No. of reﬂections

0.030, 0.085, 1.05

2704

146

0

H-atom parameters constrained

0.027, 0.070, 1.09

8623

158

1

H-atom parameters constrained

0.028, 0.070, 1.04

15360

264

5

H atoms treated by a mixture of

independent and constrained

reﬁnement

No. of parameters

No. of restraints

H-atom treatment

˚

ꢀ3

)

Áꢈmax, Áꢈmin (e A

Absolute structure

⁰–^.⁴⁰^,^ꢀ⁰^.¹⁹

0.21, ꢀ0.26

0.47, ꢀ0.30

Flack x determined using 1252

+

Flack x determined using 1707

+

ꢀ

quotients [(I ) ꢀ (I )]/

+

(I ) + (I )] (Parsons et al., 2013)

ꢀ

+

ꢀ

[

0.034 (16)

[(I ) + (I )] (Parsons et al., 2013)

0.001 (2)

Absolute structure parameter

–

A13

A17

A18

Crystal data

Chemical formula

C

H

16 19

N O

3 2

S

2

C

10

H N

15 3

2

O S

11 17 3 2

C H N O S

M

r

349.46

Monoclinic, P2

4.8156 (2), 21.7395 (7), 15.1912 (5)

241.31

Monoclinic, P2

12.8983 (4), 9.8458 (3), 18.2217 (6)

255.33

Orthorhombic, P2

4.9625 (3), 10.6358 (7),

3.2402 (15)

90, 90, 90

1226.62 (14)

4

Mo Kꢃ

0.26

0.25 ꢁ 0.11 ꢁ 0.09

Crystal system, space group

˚

a, b, c (A)

1

/c

1

/c

1 1 1

2 2

2

ꢂ

ꢃ, ꢄ, ꢀ ( )

90, 95.656 (1), 90

1582.61 (10)

4

Mo Kꢃ

0.35

90, 98.250 (2), 90

2290.10 (13)

8

Mo Kꢃ

0.27

˚

3

V (A )

Z

Radiation type

ꢅ (mm

Crystal size (mm)

ꢀ

1

)

0.19 ꢁ 0.12 ꢁ 0.11

0.19 ꢁ 0.13 ꢁ 0.09

Data collection

T

min, Tmax

0.925, 0.976

25387, 4036, 3430

0.941, 0.985

14727, 5036, 4323

0.924, 0.988

10534, 10534, 9991

No. of measured, independent and

observed [I > 2ꢆ(I)] reﬂections

R

int

0.027

0.675

0.024

0.642

0.000

0.649

˚

ꢀ1

)

(sin ꢇ/ꢁ)max (A

Reﬁnement

2

R[F > 2ꢆ(F )], wR(F ), S

No. of reﬂections

0.031, 0.078, 1.04

4036

212

0

H-atom parameters constrained

0.033, 0.088, 1.03

5036

291

3

H-atom parameters constrained

0.032, 0.076, 1.04

10534

154

0

No. of parameters

No. of restraints

H-atom treatment

Áꢈmax, Áꢈmin (e A

Absolute structure

H-atom parameters constrained

0.28, ꢀ0.22

˚

ꢀ3

)

⁰–^.³⁸^,^ꢀ⁰^.²⁵

⁰–^.²⁸^,^ꢀ⁰^.²⁷

Flack x determined using 1038

+

ꢀ

quotients [(I ) ꢀ (I )]/

+

(I ) + (I )] (Parsons et al., 2013)

ꢀ

[

Absolute structure parameter

–

ꢀ0.02 (3)

Computer programs: APEX2 (Bruker, 2008), SAINT-Plus (Bruker, 2008), XPREP (Bruker, 2008), SHELXT (Sheldrick, 2015a), SHELXL2016 (Sheldrick, 2015b), ORTEP-3 (Farrugia,

2012) and WinGX (Farrugia, 2012).

ꢃ

1

706 Sharma et al. Thiobarbituric acid derivatives

Acta Cryst. (2018). C74, 1703–1714

research papers

1

3

13

Ar-H), 9.62 (s, –NH ), 10.97 (s, –NH ); C NMR (100 MHz,

1

1.18 (s, –NH₂); C NMR (100 MHz, DMSO-d ): ꢂ 12.2, 12.7,

6

2

29.2, 42.1, 90.3, 161.2, 176.9, 180.6. HRMS (m/z): calculated for

C H N O S: 256.1080 [M + H] ; found: 256.1096.

DMSO-d ): ꢂ 9.8, 20.7, 24.5, 98.2, 128.5, 129.5, 136.7, 137.6,

6

+

162.4, 179.6, 196.3. HRMS (m/z): calculated for C H N O S:

3

1

17

3

2

21 21

2

+

380.1436 [M + H] ; found: 380.1427.

2

.2.19. 5-(1-Aminoethylidene)-2-thioxo-1,3-di-p-tolyldi-

hydropyrimidine-4,6(1H,5H)-dione (A19). Yellow solid;

ꢂ

1

m.p. 198–200 C; HPLC t = 9.9 min; H NMR (400 MHz,

R

2.3. Structure determination

DMSO-d ): ꢂ 1.23 (s, –CH ), 2.33 (s, –CH ), 7.07 (d, J =

6

3

8

.2 Hz, Ar-H), 7.20 (d, J = 8.2 Hz, Ar-H), 9.69 (s, –NH ), 10.9

2

Crystal data, data collection and structure reﬁnement

details are summarized in Table 1. All non-H atoms were ﬁrst

reﬁned isotropically and then anisotropically with full-matrix

1

3

(

s, –NH₂); C NMR (100 MHz, DMSO-d ): ꢂ 20.8, 23.4,

6

1

01.2, 129.8, 132.4, 136.2, 137.3, 162.8, 167.3, 172.5. HRMS

+

m/z): calculated for C H N O S: 366.1282 [M + H] ;

2

least-squares based on F using SHELXL (Sheldrick, 2015b).

(

found: 366.1271.

2

0

19

3

2

All H atoms were positioned geometrically, allowed to ride on

their parent atoms and reﬁned isotropically. In A06, the H

atom of the enol unit was found to be disordered over two

positions between the enol and one of the carbonyl groups of

the thiobarbituric ring. Equal occupancies were used for the

two components.

2.2.20. 5-(1-Aminopropylidene)-2-thioxo-1,3-di-p-tolyldi-

hydropyrimidine-4,6(1H,5H)-dione (A20). Yellow solid; m.p.

1

d ): ꢂ 1.14 (t, J = 7.4 Hz, CH ), 2.33 (s, –CH ), 2.91 (q, J =

7

ꢂ

59–160 C; HPLC t = 10.6 min; H NMR (400 MHz, DMSO-

R

1

6

3

.4 Hz, CH ), 7.08 (d, J = 8.2 Hz, Ar-H), 7.20 (d, J = 8.2 Hz,

2

Figure 2

Conditions: (a) anhydride/NaHCO

3

/H

2

O, overnight; (b) tert-butyloxycarbonyl-protected amino acids (Boc–amino acid), 1-ethyl-3-(3-dimethylamino-

4

propyl)carbodiimide (EDC), 1-hydroxybenzotriazole (HOBt), 4-dimethylaminopyridine (DMAP), dichloromethane (DCM), 16 h; (c) NH Cl/EtOH,

overnight; (d) amine/conc. HCl/EtOH, overnight; (e) aldehyde/EtOH, 10 min; (f) 1-isothiocyanato-4-methylbenzene, N,N-diisopropylethylamine

ꢂ

(DIEA), DCM, overnight; (g) triﬂuoroacetic acid (TFA), 1 h; (h) malonic acid and acetyl chloride, 40 C, 12 h; (i) acetic acid/propionic acid, few drops

2 4

conc. H SO , reﬂux 1 h.

ꢃ

Acta Cryst. (2018). C74, 1703–1714

Sharma et al.

Thiobarbituric acid derivatives 1707

research papers

ꢀ

1

around 1541 cm indicates the enol ‘–OH’ group. A distinct

2

.4. Theoretical calculations

ꢀ

1

signal at 3295 cm in A17 further indicates the presence of

primary amine, clearly supporting the enamine formation.

In A01, the C-5 proton in acetylated 1,3-diethyl-2-thio-

barbituric acid (DETBA) showed a signal at 17.72 ppm

The above crystal structures were used as the starting points

for the calculations which were performed using the DFT-

B3LYP/6-311++(d,p) method implemented in GAUSSIAN09

(Frisch et al., 2009) without solvent correction. Vibration

analysis showed that the optimized structure indeed repre-

sents a minimum on the potential energy surface (no negative

eigenvalues). A four-membered ring transition state was

calculated (Gonzalez & Schlegel, 1989, 1990).

(

singlet), which reﬂects the presence of OH, hence indicating

that the enol form is more stable than the keto form. The

enolization of the carbonyl group was also in excellent

agreement with the observed signal at 96.7 ppm for C-5 in the

13

C NMR spectrum. Furthermore, the NMR spectra for A17,

A18, A19 and A20 revealed a shift of the peaks during the

conversion from enol to enamine. Of note, we detected an

interesting feature in all the enamine derivatives where the

3

. Results and discussion

All the derivatives (Fig. 2) were synthesized earlier by our

group (Sharma et al., 2018) and well characterized by a variety

of spectroscopic techniques which will be discussed in the

subsequent sections.

‘NH ’ proton showed two distinct peaks, one around 9.7 ppm

2

and another at 11 ppm, clearly indicating different chemical

environments of the two protons in ‘–NH₂’.

Given the non-aromaticity of TBA, they absorb UV on the

thin-layer chromatography (TLC) plate and during the HPLC,

UV absorption of a few derivatives was also studied using

acetonitrile (ACN), ethanol and dichloromethane (DCM) as

solvent. 1,3-Diethyl-2-thiobarbituric acid (DETBA) showed a

ꢁ_m_a_xabsorption at 285 nm. A01 showed absorption at a

maximum (ꢁ_m_a_x) of 316 nm, whereas A04 and A12 showed

absorptions at 322 and 289 nm, respectively. However, similar

results were obtained for A12 in the case of ethanol as solvent,

but in case of DCM as solvent, ꢁ_m_a_xwas observed at 305 nm.

Also the derivative with an aryl substitution on ‘N’, i.e. A14,

absorbed at 286 nm. However, with further substitution at C-5 in

A14 affording A16, ꢁ_m_a_xshifts to 318 nm. A comparison of A01

and A17 revealed UVabsorption changes from 316 to 320 nm as

the conversion from the keto to the enamine form occurred.

In the case of A04, the ꢁ_m_a_xabsorption was at 322 nm and

absorption shifted slightly to 308 nm after Boc removal in

3

.1. Synthesis and characterization

All the derivatives were synthesized earlier by our group

Sharma et al., 2018) and were characterized by NMR and UV

(

spectrometry (Fig. 3) in a variety solvents. Some of the deri-

vatives (A01, A02, A03, A04, A06, A10, A12, A13, A14 and

A17) were evaluated using IR spectroscopy and different

absorption stretching frequencies were compared to the

reported literature (Larkin, 2017). The stretching frequencies

of C S in all spectra were found in the range 1108–

ꢀ

1

1357 cm , which is in agreement with a C S group attached

to a tertiary nitrogen (Pretsch et al., 2000). In A12, the

1

stretching frequency at 1377 cm indicated the presence of a

ꢀ

nitro group (NO ). The presence of stretching frequencies at

2

ꢀ

1

680/825 and 1613/838 cm in A01 and A17, respectively,

1

indicates the presence of ‘substituted alkene’. A broad signal

Figure 3

UV spectra of some TBA derivatives.

ꢃ

1

708 Sharma et al. Thiobarbituric acid derivatives

Acta Cryst. (2018). C74, 1703–1714

research papers

Table 2

RMSD (r.m.s. deviation) values of ﬁtted atoms of PDETBA and dihedral

angles ( ) PDETBA–PENOL, PDETBA–PENAMINE and PDETBA–PTHIOAMIDE

observed in A01, A02, A06, A13, A17 and A18.

Table 4

Selected hydrogen bonds observed in A01, A02, A06, A13, A17 and A18.

ꢂ

D—Hꢄ ꢄ ꢄA

D—H

Hꢄ ꢄ ꢄA

Dꢄ ꢄ ꢄA

D—Hꢄ ꢄ ꢄA

A01

RMSD of ﬁtted

Compound atoms of PDETBA

Dihedral angle

b

i

a

c

d

C10—H10Aꢄ ꢄ ꢄS1

0.98

0.84

2.88

1.71

3.8316 (14)

2.4756 (13)

163

150

[PDETBA–PENOL /PENAMINE /PTHIOAMIDE ]

O3—H3ꢄ ꢄ ꢄO2

A01

A02

A06

A13

A17

A18

0.0187

0.0270

0.0117

0.0171

0.0544, 0.0465

0.0245

6.3 (1)

7.3 (2)

8.7 (2)

0.2 (2)

7.9 (2), 5.3 (2)

5.6 (2)

A02

i

C2—H2Aꢄ ꢄ ꢄO2

0.99

0.84

2.56

2.57

2.56

1.67

3.384 (2)

3.440 (2)

3.539 (2)

2.4395 (17)

140

146

170

151

ii

C6—H6Aꢄ ꢄ ꢄO1

iii

C11—H11Bꢄ ꢄ ꢄO2

O3—H3ꢄ ꢄ ꢄO2

Notes: (a) Atoms used to deﬁne PDETBA: (A01) C3–C6–C7–C8–N1–N2; (A02) C4–C5–

C9–N2–C8–N1; (A06) C8–C3–C6–N2–N1–C7; (A13) C3–C4–C11–C14–N1–N3; (A17)

C3–C9–C10–C8–N3–N2; (A18) C3–C9–C10–C11–N1–N2. (b) Atoms used to deﬁne

A06

i

C11—H11ꢄ ꢄ ꢄN2

1.00

0.98

0.83 (1)

0.86 (1)

2.63

2.85

2.87 (1)

1.59 (1)

1.56 (1)

3.613 (3)

3.760 (2)

3.6957 (17)

2.3723 (19)

166

154

172 (2)

150 (1)

155 (1)

ii

C18—H18Aꢄ ꢄ ꢄS1

P

ENOL: (A01) C9–C10–O3; (A02) C1–C2–C3–O3; (A06) C9–C10–O3. (c) Atoms used to

deﬁne PENAMINE: (A17) C6–C7–C8–N1; (A18) C6–C7–C8–N3. (d) Atoms used to deﬁne

THIOAMIDE: (A13) C5–N2–S2.

i

N3—H3ꢄ ꢄ ꢄS1

P

O2—H2Hꢄ ꢄ ꢄO3

O3—H1Hꢄ ꢄ ꢄO2

A13

N2—H2Aꢄ ꢄ ꢄO1

A05. A06 showed the ꢁ_m_a_xabsorption at 320 nm, a value that

did not differ greatly from that of A04. UV–Vis absorption

was also studied for the Knoevenagel reaction (A10 and A11).

Two ꢁ_m_a_xabsorption peaks – one caused by DETBA and the

other by the respective aldehyde – were detected. For A10, the

ꢁ_m_a_xabsorption peaks were at 287 and 361 nm, whereas for

A11, they were at 284 and 366 nm. The reaction of DETBA

with p-tolyl isothiocyanate resulted in A13, which has a thio-

amide bond, which showed a shift from 285 (in case of

DETBA) to 333 nm. Furthermore, A14 showed two UV–Vis

absorption peaks at 241 and 286 nm, which were caused by the

presence of ‘tolyl’, as well as a ‘thiobarbituric ring’.

0.88

0.84

1.79

1.99

2.5671 (15)

2.7802 (10)

147

157

O2—H2ꢄ ꢄ ꢄS2

A17

i

C6—H6Aꢄ ꢄ ꢄO3

0.98

0.88

2.43

1.99

2.07

3.3103 (17)

2.8540 (15)

2.9473 (15)

149

168

172

i

N1—H1Eꢄ ꢄ ꢄO3

N4—H4Dꢄ ꢄ ꢄO1

A18

C1—H1Aꢄ ꢄ ꢄS1

i

0.98

0.99

0.88

2.80

2.54

2.24

3.661 (2)

3.505 (2)

2.999 (2)

147

166

145

ii

C7—H7Aꢄ ꢄ ꢄO1

iii

N3—H3Bꢄ ꢄ ꢄO2

1

2

3

2

1

2

1

Symmetry codes for A01: (i) x ꢀ , ꢀy + , z ꢀ ; for A02: (i) ꢀx, y + , ꢀz + 1; (ii) ꢀx + 1,

2

1

2

1

3

2

y ꢀ , ꢀz + 1; (iii) ꢀx + 1, y + , ꢀz + 1; for A06: (i) ꢀx + 1, y ꢀ , ꢀz + ; (ii) ꢀx + , ꢀy + 2,

2

1

2

1

2

3

1

2

z ꢀ ; for A17: (i) ꢀx + 1, y ꢀ , ꢀz + ; for A18: (i) x ꢀ , ꢀy + , ꢀz + 2; (ii) ꢀx + 1, y + ,

2

3

2

3

1

2

ꢀ

z + ; (iii) ꢀx, y ꢀ , ꢀz + .

2

3.2. Crystal structure descriptions of A01, A02, A06, A13,

A17 and A18

P_E_N_A_M_I_N_Eor P_D_E_T_B_A–P_T_H_I_O_A_M_I_D_E. R.m.s. deviations (RMSDs,

˚

usually measured in Angstr o¨ m) of the ﬁtted atoms of DETBA,

Colourless X-ray-quality crystals of A01, A02, A06, A13,

A17 and A18 were obtained by hot recrystallization from

ethanol.

along with the dihedral angles between the various planes, are

listed in Table 2. The six-membered DETBA ring did not

appear to be completely planar in any of the compounds, since

the RMSD values of the ﬁtted atoms of the DETBA rings

were all greater than zero. The RMSD of PDETBA increased as

the carbon chain on the enol in A01 (0.0187) extended to A02

(0.0270). Interestingly, the presence of a bulky Boc–Val group

on the enol in A06 signiﬁcantly improved the planarity of

Molecules in the asymmetric unit of these derivatives are

shown in Fig. 4. Each molecule consists of a DETBA ring with

either an enol (in A01, A02 and A06), enamine (in A17 and

A18) or thioamide (in A13) moiety. The DETBA ring, toge-

ther with the various moieties, were identiﬁed as approxi-

mately planar, which best describes the molecular

conformations of A01, A02, A06, A13, A17 and A18. In

Table 2, the DETBA, enol, enamine and thioamide planes are

P

DETBA over that observed in A01. However, the PDETBA

ENOL dihedral angle appeared to increase with the carbon

–

denoted as P_D_E_T_B_A, P_E_N_O_L, P_E_N_A_M_I_N_Eand P_T_H_I_O_A_M_I_D_E

respectively, whilst the dihedral angles between the corre-

,

chain length and steric demand of the enol moiety. Compound

A17 is an enamine form of A01 and showed RMSD values

(0.0465–0.544) higher than those of all the enol counterparts,

sponding planes are designated as P_D_E_T_B_A–P_E_N_O_L, P_D_E_T_B_A

–

Table 3

Selected bond lengths (A) observed in A01, A02, A06, A17 and A18.

˚

Bond parameter

A01

A02

A06

A17

A18

a

C

carbonyl—Ocarbonyl

1.247 (2)

1.435 (2)

1.398 (2)

1.309 (2)

1.257 (2)

1.430 (3)

1.406 (3)

1.301 (2)

1.250 (2)

1.404 (2)

1.394 (2)

1.260 (2)

1.239 (2) 1.237 (2)

1.434 (2) 1.437 (2)

1.425 (2) 1.425 (2)

1.308 (2) 1.312 (2)

1.242 (2)

1.436 (3)

1.430 (3)

1.314 (2)

b

carbonyl—Cethylene

ethylene—Cenol/enamine

enol/enamine—Oenol/Nenamine

c

d

Notes: (a) A01 = C6—O2; A02 = C4—O2; A06 = C2—O6; A17 = C10—O2 and C19—O4; A18 = C10—O1; (b) A01 = C6—C7; A02 = C4—C5; A06 = C6—C7; A17 = C10—C8 and

C19—C18; A18 = C10—C9; (c) A01 = C7—C8; A02 = C5—C3; A06 = C7—C9; A17 = C8—C7 and C18—C17; A18 = C9—C8; (d) A01 = C9—O3; A02 = C3—O3; A06 = C9—O3; A17 =

C7—N1 and C17—N4; A18 = C8—N3.

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Acta Cryst. (2018). C74, 1703–1714

Sharma et al.

Thiobarbituric acid derivatives 1709

research papers

with P_D_E_T_B_A–P_E_N_A_M_I_N_Edihedral angles ranging between

ꢂ

vation reveals electron delocalization between a carbonyl

group of the DETBA ring and the enol moiety, which is

unique to A06.

Hydrogen-bonding patterns in the crystal packing of A01,

A02, A06, A13, A17 and A18 are shown in Fig. 5, while the

hydrogen-bond parameters are listed in Table 4. Intra-

5.2 (2) and 7.9 (2) . In contrast to enol derivatives A01 and

A02, extending the carbon chain of the enamine forms of A01

and A02 led to a decrease in the RMSD of the DETBA ring

from 0.0465–0.0544 (in A17) to 0.0245 (in A18). Exchanging

the enamine for a thioamide moiety in A13 resulted in the

ꢂ

smallest dihedral angle [P_D_E_T_B_A–P_T_H_I_O_A_M_I_D_E= 0.2 (2) ]

molecular O—Hꢄ ꢄ ꢄO hydrogen bonds with graph-set notation

2

observed in this series, with a P_D_E_T_B_ARMSD that was inter-

mediate between that of the enol derivatives (Table 2).

The bond lengths and angles are comparable to those of

related compounds (Coe et al., 1999; Asiri et al., 2009; Gal a´ n et

al., 2012; Bourhill et al., 1994); the bond parameters of interest

in compounds A01, A02, A06, A17 and A18 are summarized

in Table 3. Compounds A01 and A02 displayed enolic prop-

R (6) were observed in enol derivatives A01, A02 and A06.

Nonclassical intermolecular C—Hꢄ ꢄ ꢄS hydrogen bonds link

neighbouring molecules to form chains of a one-dimensional

supramolecular structure that extend along the crystal-

lographic c axis. In A02, intermolecular C—Hꢄ ꢄ ꢄO hydrogen

bonds join adjacent molecules to form a two-dimensional

honeycomb-like supramolecular network extending along the

crystallographic ab axis. The N—Hꢄ ꢄ ꢄS hydrogen bonds link

neighbouring molecules of A06 to form chains that extend

along the crystallographic b axis. These chains were further

joined via C—Hꢄ ꢄ ꢄO hydrogen bonds along the crystal-

lographic a axis, forming a two-dimensional corrugated sheet-

like supramolecular structure. A combination of inter-

erties, evidenced by a shorter C_c_a_r_b_o_n_y_l—O_c_a_r_b_o_n_y_l[1.247 (2)—

˚

1

.257 (2) A] bond length than C_e_n_o_l—O_e_n_o_l[1.309 (2)—

˚

.301 (2) A], which were comparable with that of enamine

1

forms A17 and A18. Furthermore, C_e_t_h_y_l_e_n_e—C_e_n_o_l[1.398 (2)—

˚

.406 (3) A] appeared to be shorter than C_c_a_r_b_o_n_y_l—C_e_t_h_y_l_e_n_e

1

˚

1.435 (2)—1.430 (3) A]. In compound A06, the C_c_a_r_b_o_n_y_l—

[

C_e_t_h_y_l_e_n_e[1.404 (2) A] and C_e_n_o_l—O_e_n_o_l[1.260 (2) A] bonds

were signiﬁcantly shorter than in A01 and A02. This obser-

˚

molecular N—Hꢄ ꢄ ꢄO and C—Hꢄ ꢄ ꢄO hydrogen bonds (in A17)

1

2

forms six-membered rings with graph-set notation R (6) and

Figure 4

The molecular structures of compounds A01, A02, A06, A13, A17 and A18, drawn with displacement ellipsoids at the 50% probability level. One of the

two molecules of compound A17 has been omitted for clarity.

ꢃ

1

710 Sharma et al. Thiobarbituric acid derivatives

Acta Cryst. (2018). C74, 1703–1714

research papers

result in a single-stranded helical supramolecular structure

that elongates along the crystallographic b axis. On the other

hand, N—Hꢄ ꢄ ꢄO hydrogen bonds link neighbouring molecules

to form chains that extend along the crystallographic b axis.

Then C—Hꢄ ꢄ ꢄO hydrogen bonds join the chains along the

crystallographic a axis to form a two-dimensional sheet-like

supramolecular architecture.

3.3. Theoretical calculations

A density functional theory (DFT) geometry optimization

with the GAUSSIAN09 program package (Frisch et al., 2009),

employing the B3LYP [Becke three parameters Lee–Yang–

Parr exchange correlation functional, which combines the

hybrid exchange functional of Becke (1988) with the gradient-

correlation functional of Lee, Yang and Parr (Lee et al., 1988)]

Figure 5

Hydrogen-bonding patterns observed in the crystal packing of compounds A01, A02, A06, A13, A17 and A18. Intramolecular O—Hꢄ ꢄ ꢄO, N—Hꢄ ꢄ ꢄO and

O—Hꢄ ꢄ ꢄS hydrogen bonds are represented as dashed blue, purple and light-blue bonds, respectively. Intermolecular C—Hꢄ ꢄ ꢄO, C—Hꢄ ꢄ ꢄS, N—Hꢄ ꢄ ꢄO

and N—Hꢄ ꢄ ꢄS hydrogen bonds are shown as dashed orange, light-green, magenta and pink bonds, respectively.

ꢃ

Acta Cryst. (2018). C74, 1703–1714

Sharma et al.

Thiobarbituric acid derivatives 1711

research papers

Table 5

Total energy and frontier orbital energy [B3LYP/6-311++G(d,p)] for A01

in Hartrees.

molecular orbital and LUMO is the lowest unoccupied mol-

ecular orbital) that was greater than that of enol form. HOMO

and LUMO are important factors that affect bioactivity,

chemical reactivity, and electron afﬁnity and ionization

potential (Clare, 1994, 1995; Zhang & Musgrave, 2007). Thus,

a study of the frontier orbital energy can provide useful

information about the biological and chemical reaction

mechanism.

DFT (keto form)

DFT (enol form)

a

total

E

ꢀ1123.12965976

ꢀ0.24121

ꢀ1123.15077113

ꢀ0.23291

HOMO

LUMO

ꢀ0.09332

ꢀ0.09290

b

ÁE

0.14789

0.14001

Notes: (a) 1 Hartree = 4.35974417 ꢁ 10–18 J = 27.2113845 eV; (b) ÁE = ELUMO

ꢀ

E

HOMO

.

3

.4. Transition state calculations

Table 6

Calculated reaction proﬁle using DFT [B3LYP/6-311++G(d,p)].

A transition state is broadly considered as the ﬁrst order

ꢀ

1

)

saddle point on the Potential Energy Surface (PES) of a

molecular system. The vibrational spectrum of a transition

state is characterized by one imaginary frequency (implying a

negative force constant), which means that in one direction in

the nuclear conﬁguration space the energy has a maximum,

Relative Energies (kcal mol

Keto form

Transition state

Enol form

0

43.51

ꢀ11.54

using the 6-311G++(d,p) basis set was performed in the gas

phase. No solvent corrections were made with these calcula-

tions, as gas-phase calculations frequently correspond quite

well with crystal structures (Honarparvar et al., 2013). The

starting geometries for A01, A04, A13, A17 and A18 were

taken from the X-ray-reﬁned data. The optimized-geometry

results in the free molecule state were compared to those in

the crystalline state. No negative vibrational modes were

obtained. The DFT calculated structure and geometric para-

meters (bond lengths and angles) were in agreement with each

other. All optimized structures had a C1 point group.

The optimized geometry of A01 indicates electron deloca-

lization between atoms C16—C17—C19—O28. The C19—

˚

O28 bond length was 1.31 A, which is slightly longer than that

˚

of the carbonyl (C O, usually 1.22 A), and the H3—O3

group formed a strong intramolecular hydrogen bond with

atom O2. However, A04, with a similar structure, showed

delocalization of electrons in the TBA ring, unlike that found

in A01, but also the presence of strong intramolecular

hydrogen bonding. A13 showed the presence of two intra-

molecular hydrogen bonds caused by the presence of a thio-

amide bond. A17 and A18 showed the presence of

intermolecular hydrogen bonding, in addition to intra-

molecular hydrogen bonding.

Figure 6

Frontier molecular orbitals of A01 [B3LYP/6-311++G(d,p)].

3.3.1. Frontier orbital energy analysis and molecular total

energies. Molecular total energy and frontier orbital energy

levels were calculated using DFT (Table 5), as discussed

previously by our group (Sharma et al., 2017).

The crystal structure of A01 (enol form) was used for DFT

calculations. The energy gap between the HOMO and LUMO

was calculated by the B3LYP method using the 6-311G++(d,p)

basis set. The title compound (in enol form) showed an energy

gap (ÁE = 0.14001 Hartree = 3.78 eV) for HOMO – LUMO

(Fig. 6). This energy gap affords the theoretical absorption at

ꢁ_m_a_x= 326 nm. The keto form was optimized using Gauss-

View05 (Dennington et al., 2009), and the results were

compared with those of the enol form (Table 5). The keto form

showed an energy gap (ÁE = 0.14789 Hartree = 3.99 eV; ꢁ_m_a_x

3

=

08 nm) for HOMO – LUMO (HOMO is the highest occupied

Figure 7

Transition state for the keto–enol form of A01.

ꢃ

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712 Sharma et al. Thiobarbituric acid derivatives

Acta Cryst. (2018). C74, 1703–1714

research papers

while in all other orthogonal directions the energy is a

minimum (Lewars, 2003). In order to verify this, A01 (keto

form) was optimized using GAUSSIAN09, followed by

frequency calculations at the same computational level as that

used for the enol form (A01). The energies calculated are

listed in Table 6 and shown schematically in Fig. 7.

The calculated energy conﬁrms that the reaction (Fig. 7) is

more favourable in a forward direction, i.e. the enol form. In

order to convert the keto form to the enol, an energy barrier

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ꢀ

1

ꢀ1

of 55.05 kcal mol (1 kcal mol = 4.184 kJ mol ) needs to

be overcome (Table 6); this value is much higher than the

ꢀ

1

inherent energy limit of 15–20 kcal mol at room temperature

(Kruger, 2002; Singh et al., 2012).

The theoretical results thus suggest that if the product

enol) forms, it will not interconvert at room temperature. This

(

notion was also conﬁrmed by the NMR spectra (only the enol

form was observed). A similar observation was made for all

similar derivatives.

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4

. Conclusion

We have demonstrated the successful characterization of

synthesized TBA derivatives by various spectroscopic tech-

niques. UV spectroscopy explained the absorptivity for the

TBA derivatives at different wavelengths depending on the

structure. The ꢁ_m_a_xfor the TBA derivatives did not reveal any

signiﬁcant shift with change of solvent. Intramolecular

hydrogen bonding is observed in all cases (A01, A02, A06,

A13, A17 and A18) and intermolecular hydrogen bonding is

also observed for A17. In A13, the presence of two intra-

molecular hydrogen bonds was observed. Acylation with

simple carboxylic acid derivatives afforded the enamine, as

104.

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1

shown by H NMR spectroscopy and X-ray crystallography.

The preference of the enol over the keto form was conﬁrmed

using the GAUSSIAN09 program package. To convert the

keto form to the enol form, an energy barrier of 55.05 kcal

mol needs to be overcome, as conﬁrmed by transition-state

calculations. These studies provide an insight into the ﬁeld of

materials science, since TBA derivatives possess good NLO

properties and corrosion inhibition properties. These results

also support the application of TBA derivatives in the design

of engineering materials due to their possessing both

hydrogen-bond donors and acceptors.

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Funding information

Lee, J.-H., Lee, S., Park, M. Y. & Myung, H. (2011). Virol. J. 8 , article

No. 18.

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Funding for this research was provided by: National Research

Foundation (NRF) (Blue Sky’s Research Programme) and the

University of KwaZulu-Natal (South Africa) (award No.

110960); International Scientiﬁc Partnership Program ISPP at

King Saud University (Saudi Arabia) (award No. ISPP 0061);

Spanish Ministry of Economy, Industry and Competitiveness

(MINECO) (award No. CTQ2015-67870-P); Generalitat de

Catalunya (Spain) (award No. 2014 SGR 137).

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714 Sharma et al. Thiobarbituric acid derivatives

Acta Cryst. (2018). C74, 1703–1714

supporting information

Acta Cryst. (2018). C74, 1703-1714 [https://doi.org/10.1107/S2053229618015516]

Crystal structure, spectroscopic studies and theoretical studies of thiobarbituric

acid derivatives: understanding the hydrogen-bonding patterns

Anamika Sharma, Sizwe J. Zamisa, Sikabwe Noki, Zainab Almarhoon, Ayman El-Faham, Beatriz

G. de la Torre and Fernando Albericio

Computing details

For all structures, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT-Plus (Bruker, 2008); data reduction:

SAINT-Plus and XPREP (Bruker, 2008); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s)

used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: ORTEP-3 (Farrugia, 2012); software used

to prepare material for publication: WinGX (Farrugia, 2012).

5-Acetyl-1,3-diethyl-2-thioxodihydropyrimidine-4,6(1H,5H)-dione (A01)

Crystal data

C

M

10

H

14

N

2

O

3

S

F(000) = 512

= 1.430 Mg m

−3

r

= 242.29

D

x

Monoclinic, P2

1

/n

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 8036 reflections

θ = 2.7–28.3°

µ = 0.28 mm

T = 100 K

a = 4.6212 (1) Å

b = 12.5742 (4) Å

c = 19.3936 (6) Å

β = 92.869 (1)°

V = 1125.51 (6) Å

Z = 4

−1

3

Rod, colourless

0.29 × 0.23 × 0.12 mm

Data collection

Bruker APEXII CCD

diffractometer

Radiation source: sealed tube

Graphite monochromator

φ and ω scans

14896 measured reflections

2704 independent reflections

2309 reflections with I > 2σ(I)

R

int = 0.016

θ

max = 28.3°, θmin = 1.9°

Absorption correction: multi-scan

h = −5→6

(

SADABS; Bruker, 2012)

k = −16→15

l = −25→24

T

min = 0.911, Tmax = 0.978

Refinement

2

Refinement on F

Hydrogen site location: inferred from

neighbouring sites

Least-squares matrix: full

R[F > 2σ(F )] = 0.030

2

H-atom parameters constrained

2

wR(F ) = 0.085

w = 1/[σ (F

o

) + (0.041P) + 0.5533P]

2

S = 1.05

where P = (F

o

+ 2F )/3

c

2

1

0

704 reflections

46 parameters

restraints

(Δ/σ)max = 0.002

Δρmax = 0.40 e Å

Δρmin = −0.19 e Å

−

3

−

3

Acta Cryst. (2018). C74, 1703-1714

sup-1

supporting information

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance

matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;

correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate

(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. School of Chemsitry and Physics University of KwaZulu-Natal Private Bag X 54001 Durban 4000

2

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )

x

y

z

Uiso*/Ueq

C1

0.7202 (3)

0.8478

0.5607

0.6415

0.8914 (3)

0.9735

0.48420 (11)

0.4238

0.4853

0.4771

0.58714 (10)

0.5935

0.60194 (7)

0.6134

0.6334

0.5543

0.60935 (7)

0.6573

0.0266 (3)

0.040*

0.0210 (3)

0.025*

H1A

H1B

H1C

C2

H2A

H2B

C3

1.0545

0.5853

0.5781

0.025*

0.5442 (3)

0.2000 (3)

0.1216

0.0344

0.3853 (4)

0.2676

0.72435 (9)

0.86382 (11)

0.8095

0.9021

0.94198 (11)

0.9758

0.64289 (6)

0.67718 (7)

0.7082

0.6543

0.71960 (8)

0.7541

0.0160 (2)

0.0221 (3)

0.027*

0.0302 (3)

0.045*

C4

H4A

H4B

C5

H5A

H5B

H5C

C6

C7

C8

C9

C10

H10A

H10B

H10C

N1

N2

O1

O2

O3

0.5475

0.4603

0.9041

0.9965

0.7430

0.6891

0.045*

0.3421 (3)

0.5078 (3)

0.7076 (3)

0.4614 (3)

0.6033 (3)

0.4933

0.85049 (10)

0.80209 (9)

0.71693 (10)

0.83582 (10)

0.79100 (11)

0.8115

0.55737 (6)

0.50516 (6)

0.52324 (6)

0.43682 (7)

0.37626 (7)

0.3338

0.0174 (2)

0.0170 (2)

0.0183 (2)

0.0191 (2)

0.0251 (3)

0.038*

0.6090

0.8013

0.7133

0.8186

0.3799

0.3751

0.038*

0.7069 (2)

0.3693 (2)

0.8729 (2)

0.1740 (2)

0.2780 (2)

0.2035

0.68092 (8)

0.81041 (8)

0.67545 (8)

0.92637 (7)

0.91243 (8)

0.9341

0.59257 (5)

0.62405 (5)

0.48428 (5)

0.54481 (5)

0.42115 (5)

0.4572

0.0165 (2)

0.0167 (2)

0.0281 (2)

0.0236 (2)

0.0240 (2)

0.036*

H3

S1

0.55504 (7)

0.67705 (2)

0.72282 (2)

0.02091 (10)

2

Atomic displacement parameters (Å )

11

22

33

12

13

23

U

C1

C2

C3

C4

0.0310 (7)

0.0181 (6)

0.0139 (5)

0.0217 (6)

0.0206 (6)

0.0226 (6)

0.0162 (5)

0.0239 (6)

0.0278 (7)

0.0059 (5)

0.0061 (5)

−0.0027 (4)

0.0049 (5)

−0.0021 (5)

−0.0008 (4)

0.0070 (5)

−0.0034 (5)

0.0006 (5)

−0.0016 (4)

−0.0015 (5)

0.0219 (6)

0.0179 (6)

0.0213 (6)

Acta Cryst. (2018). C74, 1703-1714

sup-2

supporting information

C5

C6

C7

C8

C9

C10

N1

N2

O1

O2

O3

S1

0.0407 (9)

0.0152 (6)

0.0153 (6)

0.0165 (6)

0.0162 (6)

0.0277 (7)

0.0150 (5)

0.0162 (5)

0.0285 (5)

0.0239 (5)

0.0247 (5)

0.02501 (18)

0.0231 (7)

0.0182 (5)

0.0188 (6)

0.0204 (6)

0.0214 (6)

0.0304 (7)

0.0175 (5)

0.0351 (6)

0.0232 (5)

0.0271 (5)

0.02170 (17)

0.0272 (7)

0.0188 (6)

0.0167 (6)

0.0178 (6)

0.0194 (6)

0.0170 (6)

0.0170 (5)

0.0164 (5)

0.0214 (5)

0.0235 (5)

0.0200 (5)

0.01597 (16)

0.0010 (6)

−0.0015 (4)

−0.0007 (4)

−0.0033 (4)

0.0007 (5)

0.0019 (4)

0.0014 (4)

0.0119 (4)

0.0076 (4)

0.0036 (4)

−0.00059 (11)

0.0064 (6)

−0.0010 (4)

0.0000 (4)

0.0004 (4)

−0.0008 (4)

0.0007 (5)

−0.0004 (4)

0.0017 (4)

0.0075 (4)

−0.0008 (4)

0.00046 (11)

−0.0074 (5)

−0.0007 (4)

−0.0001 (4)

−0.0002 (5)

0.0009 (5)

0.0005 (5)

0.0003 (4)

−0.0009 (4)

0.0014 (4)

0.0018 (4)

0.0028 (4)

0.00196 (11)

Geometric parameters (Å, º)

C1—C2

1.5202 (19)

C5—H5B

0.9800

C1—H1A

C1—H1B

C1—H1C

C2—N1

C2—H2A

C2—H2B

C3—N1

C3—N2

C3—S1

C4—N2

C4—C5

0.9800

1.4818 (15)

0.9900

C5—H5C

C6—O2

C6—N2

C6—C7

C7—C9

C7—C8

C8—O1

C8—N1

C9—O3

C9—C10

C10—H10A

C10—H10B

C10—H10C

O3—H3

0.9800

1.2469 (15)

1.3877 (16)

1.4350 (17)

1.3979 (17)

1.4457 (17)

1.2184 (16)

1.4188 (16)

1.3089 (15)

1.4847 (18)

0.9800

0.9900

1.3746 (16)

1.3887 (15)

1.6588 (12)

1.4849 (15)

1.518 (2)

0.9900

C4—H4A

C4—H4B

C5—H5A

0.9800

0.8400

0.9900

0.9800

C2—C1—H1A

C2—C1—H1B

H1A—C1—H1B

C2—C1—H1C

H1A—C1—H1C

H1B—C1—H1C

N1—C2—C1

N1—C2—H2A

C1—C2—H2A

N1—C2—H2B

C1—C2—H2B

H2A—C2—H2B

N1—C3—N2

109.5

111.45 (10)

109.3

108.0

117.05 (10)

121.94 (9)

121.01 (9)

111.49 (11)

109.3

H5B—C5—H5C

O2—C6—N2

O2—C6—C7

N2—C6—C7

C9—C7—C6

C9—C7—C8

C6—C7—C8

O1—C8—N1

O1—C8—C7

N1—C8—C7

109.5

119.10 (11)

122.41 (11)

118.49 (11)

118.59 (11)

121.36 (11)

119.99 (11)

118.83 (11)

125.41 (12)

115.75 (11)

120.68 (12)

113.72 (11)

125.59 (12)

109.5

O3—C9—C7

O3—C9—C10

C7—C9—C10

C9—C10—H10A

C9—C10—H10B

H10A—C10—H10B

C9—C10—H10C

N1—C3—S1

N2—C3—S1

N2—C4—C5

N2—C4—H4A

109.5

Acta Cryst. (2018). C74, 1703-1714

sup-3

supporting information

C5—C4—H4A

N2—C4—H4B

C5—C4—H4B

H4A—C4—H4B

C4—C5—H5A

C4—C5—H5B

H5A—C5—H5B

C4—C5—H5C

H5A—C5—H5C

109.3

108.0

109.5

H10A—C10—H10C

H10B—C10—H10C

C3—N1—C8

C3—N1—C2

C8—N1—C2

C6—N2—C3

C6—N2—C4

C3—N2—C4

C9—O3—H3

109.5

124.98 (10)

119.30 (10)

115.70 (10)

123.53 (10)

117.14 (10)

119.33 (10)

109.5

O2—C6—C7—C9

N2—C6—C7—C9

O2—C6—C7—C8

N2—C6—C7—C8

C9—C7—C8—O1

C6—C7—C8—O1

C9—C7—C8—N1

C6—C7—C8—N1

C6—C7—C9—O3

C8—C7—C9—O3

C6—C7—C9—C10

C8—C7—C9—C10

N2—C3—N1—C8

S1—C3—N1—C8

N2—C3—N1—C2

S1—C3—N1—C2

−5.16 (18)

174.28 (11)

177.67 (11)

−2.89 (17)

8.3 (2)

−174.57 (12)

−172.03 (11)

5.06 (17)

O1—C8—N1—C3

C7—C8—N1—C3

O1—C8—N1—C2

C7—C8—N1—C2

C1—C2—N1—C3

C1—C2—N1—C8

O2—C6—N2—C3

C7—C6—N2—C3

O2—C6—N2—C4

C7—C6—N2—C4

N1—C3—N2—C6

S1—C3—N2—C6

N1—C3—N2—C4

S1—C3—N2—C4

C5—C4—N2—C6

C5—C4—N2—C3

176.16 (12)

−3.50 (17)

−5.83 (17)

174.51 (10)

84.75 (14)

−93.38 (13)

178.14 (11)

−1.32 (17)

−1.88 (17)

178.66 (11)

2.99 (17)

−177.18 (9)

−176.99 (10)

2.84 (15)

−98.68 (13)

81.30 (14)

2.29 (18)

179.42 (11)

−177.00 (12)

0.13 (19)

−0.42 (17)

179.74 (9)

−178.36 (10)

1.80 (15)

Hydrogen-bond geometry (Å, º)

D—H···A

D—H

H···A

D···A

D—H···A

C5—H5B···S1

C10—H10A···S1

0.98

0.84

2.88

1.71

2.47

3.4223 (15)

3.8316 (14)

2.4756 (13)

3.0073 (13)

116

163

150

122

i

O3—H3···O2

ii

Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) −x, −y+2, −z+1.

1,3-Diethyl-5-propionyl-2-thioxodihydropyrimidine-4,6(1H,5H)-dione (A02)

Crystal data

C

M

11

H

16

N

2

O

3

S

F(000) = 272

= 1.409 Mg m

−3

r

= 256.32

D

x

Monoclinic, P2

1

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 7194 reflections

θ = 2.7–27.5°

µ = 0.27 mm

T = 100 K

a = 4.9140 (1) Å

b = 12.9450 (3) Å

c = 9.7630 (3) Å

β = 103.474 (1)°

−1

3

V = 603.95 (3) Å

Block, colourless

Z = 2

0.19 × 0.14 × 0.07 mm

Acta Cryst. (2018). C74, 1703-1714

sup-4

supporting information

Data collection

Bruker APEXII CCD

diffractometer

8623 measured reflections

8623 independent reflections

Radiation source: sealed tube

Graphite monochromator

φ and ω scans

8469 reflections with I > 2σ(I)

R

int = 0.000

θ

max = 27.5°, θmin = 2.2°

Absorption correction: multi-scan

h = −6→6

(

SADABS; Bruker, 2012)

k = −16→16

l = −12→12

T

min = 0.940, Tmax = 0.991

Refinement

2

Refinement on F

H-atom parameters constrained

2

Least-squares matrix: full

R[F > 2σ(F )] = 0.027

w = 1/[σ (F

where P = (F

o

) + (0.0441P) + 0.0526P]

2

o

+ 2F )/3

c

2

wR(F ) = 0.070

(Δ/σ)max < 0.001

Δρmax = 0.21 e Å

Δρmin = −0.26 e Å

−

3

S = 1.09

−

3

8623 reflections

158 parameters

1 restraint

Absolute structure: Flack x determined using

1252 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et

al., 2013)

Hydrogen site location: inferred from

neighbouring sites

Absolute structure parameter: 0.034 (16)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance

matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;

correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate

(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

2

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )

x

y

z

Uiso*/Ueq

O1

O2

C5

N2

0.3177 (3)

0.1016 (3)

0.1988 (4)

0.4821 (4)

−0.1348 (5)

−0.030796

−0.324936

−0.143850

0.0123 (4)

−0.093981

0.200516

0.0435 (4)

0.2242 (4)

0.3909 (3)

0.4312 (4)

0.434322

0.614315

0.72567 (12)

0.37732 (11)

0.54922 (16)

0.64360 (14)

0.58442 (19)

0.526690

0.561794

0.641443

0.62058 (18)

0.679108

0.646446

0.53884 (15)

0.46125 (17)

0.46756 (14)

0.37043 (16)

0.311261

0.372912

0.35365 (19)

0.347983

0.49804 (17)

0.38393 (16)

0.4577 (2)

0.32802 (19)

0.7760 (3)

0.828470

0.730933

0.840824

0.6641 (2)

0.612254

0.711133

0.5607 (2)

0.3735 (2)

0.27790 (19)

0.2038 (2)

0.268416

0.178006

0.0718 (2)

0.097378

0.0214 (4)

0.0186 (3)

0.0146 (4)

0.0155 (4)

0.0281 (6)

0.042*

0.0191 (5)

0.023*

0.0159 (4)

0.0155 (4)

0.0157 (4)

0.0176 (5)

0.021*

0.0234 (5)

0.035*

C1

H1A

H1B

H1C

C2

H2A

H2B

C3

C4

N1

C6

H6A

H6B

C7

H7A

H7B

0.2017 (4)

0.020823

0.238772

0.289922

0.025153

0.035*

Acta Cryst. (2018). C74, 1703-1714

sup-5

supporting information

H7C

C8

C9

O3

H3

C11

H11A

H11B

C12

H12A

H12B

H12C

S1

0.197113

0.412224

0.007745

0.2455 (2)

0.4348 (2)

0.57302 (17)

0.513011

0.2997 (2)

0.263124

0.388804

0.1941 (3)

0.106781

0.174372

0.232739

0.11383 (6)

0.035*

0.5062 (4)

0.3308 (4)

−0.0832 (3)

−0.053435

0.6030 (4)

0.771894

0.660559

0.3955 (5)

0.334132

0.484358

0.233420

0.66844 (10)

0.55963 (19)

0.64530 (17)

0.45221 (11)

0.409823

0.74399 (18)

0.731567

0.783241

0.80712 (19)

0.767587

0.0160 (4)

0.0158 (4)

0.0198 (3)

0.030*

0.0198 (5)

0.024*

0.0261 (5)

0.039*

0.871449

0.823310

0.56606 (5)

0.039*

0.02182 (15)

2

Atomic displacement parameters (Å )

11

22

33

12

13

23

U

O1

O2

C5

N2

C1

C2

C3

C4

N1

C6

C7

C8

C9

O3

C11

C12

S1

0.0278 (8)

0.0214 (7)

0.0156 (8)

0.0164 (8)

0.0436 (13)

0.0241 (10)

0.0150 (9)

0.0133 (9)

0.0180 (9)

0.0198 (10)

0.0252 (11)

0.0135 (8)

0.0150 (9)

0.0249 (8)

0.0228 (10)

0.0334 (12)

0.0268 (3)

0.0164 (8)

0.0139 (7)

0.0131 (12)

0.0136 (9)

0.0212 (14)

0.0177 (11)

0.0154 (11)

0.0162 (10)

0.0138 (9)

0.0127 (11)

0.0235 (13)

0.0163 (10)

0.0166 (11)

0.0143 (8)

0.0165 (11)

0.0172 (12)

0.0199 (3)

0.0221 (8)

−0.0033 (6)

−0.0018 (6)

0.0000 (8)

−0.0022 (7)

0.0035 (10)

0.0017 (9)

0.0025 (8)

0.0020 (7)

0.0033 (8)

0.0033 (9)

0.0018 (9)

0.0012 (8)

−0.0015 (6)

−0.0057 (8)

0.0044 (10)

0.0010 (2)

0.0104 (7)

0.0085 (6)

0.0036 (7)

0.0053 (7)

0.0193 (11)

0.0090 (9)

0.0022 (8)

0.0020 (8)

0.0056 (7)

0.0080 (9)

0.0056 (9)

0.0027 (8)

0.0021 (8)

0.0122 (7)

0.0089 (9)

0.0163 (11)

0.0151 (2)

−0.0031 (6)

0.0006 (6)

0.0004 (8)

−0.0004 (7)

0.0023 (9)

−0.0006 (8)

0.0027 (8)

0.0035 (8)

−0.0005 (7)

−0.0015 (8)

−0.0043 (10)

0.0007 (9)

0.0015 (9)

−0.0008 (6)

0.0003 (9)

0.0074 (10)

0.0016 (2)

0.0221 (8)

0.0152 (9)

0.0172 (10)

0.0252 (12)

0.0176 (11)

0.0166 (10)

0.0164 (10)

0.0161 (9)

0.0217 (11)

0.0217 (12)

0.0178 (10)

0.0152 (11)

0.0234 (9)

0.0218 (12)

0.0320 (14)

0.0233 (3)

Geometric parameters (Å, º)

O1—C9

O2—C4

C5—C3

C5—C4

C5—C9

N2—C8

N2—C9

N2—C11

C1—C2

C1—H1A

C1—H1B

1.219 (3)

N1—C8

N1—C6

C6—C7

C6—H6A

C6—H6B

C7—H7A

C7—H7B

C7—H7C

C8—S1

1.388 (3)

1.258 (3)

1.403 (3)

1.427 (3)

1.444 (3)

1.375 (3)

1.415 (3)

1.481 (3)

1.518 (3)

0.9800

1.487 (3)

1.517 (3)

0.9900

0.9800

1.665 (2)

0.8400

1.510 (3)

O3—H3

C11—C12

0.9800

Acta Cryst. (2018). C74, 1703-1714

sup-6

supporting information

C1—H1C

C2—C3

C2—H2A

C2—H2B

C3—O3

C4—N1

0.9800

1.495 (3)

0.9900

1.302 (2)

1.380 (3)

C11—H11A

C11—H11B

C12—H12A

C12—H12B

C12—H12C

0.9900

0.9800

C3—C5—C4

C3—C5—C9

C4—C5—C9

C8—N2—C9

C8—N2—C11

C9—N2—C11

C2—C1—H1A

C2—C1—H1B

H1A—C1—H1B

C2—C1—H1C

H1A—C1—H1C

H1B—C1—H1C

C3—C2—C1

C3—C2—H2A

C1—C2—H2A

C3—C2—H2B

C1—C2—H2B

H2A—C2—H2B

O3—C3—C5

O3—C3—C2

C5—C3—C2

O2—C4—N1

O2—C4—C5

N1—C4—C5

C4—N1—C8

C4—N1—C6

C8—N1—C6

N1—C6—C7

N1—C6—H6A

118.13 (18)

122.15 (18)

119.72 (18)

125.18 (18)

119.42 (17)

115.24 (18)

109.5

114.14 (19)

108.7

C7—C6—H6A

N1—C6—H6B

C7—C6—H6B

H6A—C6—H6B

C6—C7—H7A

C6—C7—H7B

H7A—C7—H7B

C6—C7—H7C

H7A—C7—H7C

H7B—C7—H7C

N2—C8—N1

N2—C8—S1

N1—C8—S1

O1—C9—N2

O1—C9—C5

N2—C9—C5

C3—O3—H3

N2—C11—C12

N2—C11—H11A

C12—C11—H11A

N2—C11—H11B

C12—C11—H11B

H11A—C11—H11B

C11—C12—H12A

C11—C12—H12B

H12A—C12—H12B

C11—C12—H12C

H12A—C12—H12C

H12B—C12—H12C

109.2

107.9

109.5

116.74 (17)

122.36 (17)

120.90 (17)

119.02 (19)

125.34 (19)

115.63 (18)

109.5

111.45 (17)

109.3

108.0

109.5

108.7

107.6

120.04 (19)

114.87 (18)

125.08 (18)

118.5 (2)

122.33 (19)

119.19 (18)

122.91 (18)

116.51 (17)

120.51 (17)

112.16 (17)

109.2

109.5

C4—C5—C3—O3

C9—C5—C3—O3

C4—C5—C3—C2

C9—C5—C3—C2

C1—C2—C3—O3

C1—C2—C3—C5

C3—C5—C4—O2

C9—C5—C4—O2

C3—C5—C4—N1

C9—C5—C4—N1

O2—C4—N1—C8

−3.1 (3)

C11—N2—C8—N1

C9—N2—C8—S1

C11—N2—C8—S1

C4—N1—C8—N2

C6—N1—C8—N2

C4—N1—C8—S1

C6—N1—C8—S1

C8—N2—C9—O1

C11—N2—C9—O1

C8—N2—C9—C5

C11—N2—C9—C5

179.47 (16)

175.37 (14)

0.2 (3)

176.66 (18)

175.57 (18)

−4.6 (3)

6.4 (3)

−172.34 (19)

3.6 (3)

−176.22 (18)

−175.80 (18)

4.4 (3)

9.3 (3)

−173.90 (16)

−171.45 (15)

5.3 (3)

−177.70 (19)

−2.4 (3)

1.3 (3)

176.63 (16)

171.61 (18)

Acta Cryst. (2018). C74, 1703-1714

sup-7

supporting information

C5—C4—N1—C8

O2—C4—N1—C6

C5—C4—N1—C6

C4—N1—C6—C7

C8—N1—C6—C7

C9—N2—C8—N1

−9.0 (3)

−5.3 (3)

174.09 (16)

87.0 (2)

−90.0 (2)

−5.4 (3)

C3—C5—C9—O1

C4—C5—C9—O1

C3—C5—C9—N2

C4—C5—C9—N2

C8—N2—C11—C12

C9—N2—C11—C12

−1.6 (3)

178.24 (19)

179.51 (18)

−0.7 (3)

88.9 (2)

−86.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A

D—H

H···A

D···A

D—H···A

i

C2—H2A···O2

C6—H6A···O1

0.99

0.84

2.57

2.56

1.67

3.385 (3)

3.440 (3)

3.541 (3)

2.440 (2)

140

146

170

151

ii

iii

C11—H11B···O2

O3—H3···O2

Symmetry codes: (i) −x, y+1/2, −z+1; (ii) −x+1, y−1/2, −z+1; (iii) −x+1, y+1/2, −z+1.

tert-Butyl [1-(1,3-diethyl-4,6-dioxo-2-thioxohexahydropyrimidin-5-yl)-3-methyl-1-oxobutan-2-yl)carbamate

A06)

(

Crystal data

−3

C

18

H N O

29 3 5

S

x

D = 1.354 Mg m

M

r

= 399.50

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 9709 reflections

θ = 2.3–27.6°

µ = 0.20 mm

T = 100 K

Orthorhombic, P2

a = 8.3816 (12) Å

b = 9.6258 (14) Å

c = 24.297 (3) Å

1

2

1 1

−1

3

V = 1960.3 (5) Å

Block, colourless

Z = 4

0.33 × 0.25 × 0.21 mm

F(000) = 856

Data collection

Bruker APEXII CCD

diffractometer

Radiation source: sealed tube

Graphite monochromator

φ and ω scans

15360 measured reflections

15360 independent reflections

14556 reflections with I > 2σ(I)

R

int = 0.000

θ

max = 27.7°, θmin = 2.3°

Absorption correction: multi-scan

h = −10→8

k = −12→12

l = −31→28

(

SADABS; Bruker, 2012)

T

min = 0.925, Tmax = 0.968

Refinement

2

Refinement on F

H atoms treated by a mixture of independent

and constrained refinement

Least-squares matrix: full

R[F > 2σ(F )] = 0.028

2

w = 1/[σ (F

o

) + (0.0272P) + 0.5031P]

2

wR(F ) = 0.070

where P = (F

o

+ 2F )/3

c

S = 1.04

(Δ/σ)max = 0.001

Δρmax = 0.47 e Å

Δρmin = −0.30 e Å

Absolute structure: Flack x determined using

1707 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et

al., 2013)

−

3

15360 reflections

264 parameters

5 restraints

−

3

Hydrogen site location: mixed

Absolute structure parameter: 0.001 (2)

Acta Cryst. (2018). C74, 1703-1714

sup-8

supporting information

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance

matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;

correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate

(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

2

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )

x

y

z

Uiso*/Ueq

Occ. (<1)

C1

0.2383 (3)

0.176111

0.165661

0.306906

0.3395 (3)

0.269559

0.405263

0.3789 (3)

0.4471 (3)

0.2971 (2)

0.244444

0.6228 (3)

0.4478 (3)

0.6270 (3)

0.528464

0.636686

0.718745

0.5935 (3)

0.6383 (3)

0.6884 (2)

0.8554 (3)

0.894512

0.922293

0.8721 (3)

0.839680

0.804131

0.983622

0.1811 (3)

0.228993

0.1553 (3)

0.079967

0.111986

0.257240

0.0255 (3)

0.045063

−0.024473

−0.045504

0.5949 (3)

0.676742

0.8543 (3)

0.780871

0.921401

0.813187

0.9267 (2)

0.974270

0.998194

0.7723 (2)

0.6340 (2)

0.6640 (2)

0.748873

0.8459 (2)

0.7825 (2)

0.7970 (3)

0.824740

0.695525

0.838476

0.8077 (2)

0.6611 (2)

0.72189 (19)

0.6961 (3)

0.774890

0.690459

0.5651 (3)

0.486213

0.569445

0.553283

0.5412 (2)

0.463815

0.4880 (3)

0.410248

0.562602

0.456467

0.5789 (3)

0.607953

0.655239

0.498008

0.9999 (2)

1.048385

0.93914 (10)

0.921212

0.956221

0.967456

0.89713 (9)

0.870259

0.0272 (6)

0.041*

0.0179 (5)

0.021*

H1A

H1B

H1C

C2

H2A

H2B

C8

0.915642

0.021*

0.81999 (9)

0.73724 (9)

0.70544 (9)

0.720766

0.56077 (10)

0.63569 (9)

0.50255 (10)

0.483854

0.0147 (5)

0.0157 (5)

0.0154 (5)

0.018*

0.0204 (5)

0.0170 (5)

0.0302 (6)

0.045*

C9

C10

H10

C15

C14

C17

H17A

H17B

H17C

C3

0.501853

0.483697

0.045*

0.88664 (9)

0.80864 (9)

0.85597 (8)

0.87195 (10)

0.894399

0.838428

0.90395 (12)

0.881032

0.936715

0.915187

0.70810 (10)

0.686188

0.76531 (10)

0.764402

0.788342

0.780629

0.68128 (11)

0.643222

0.701633

0.681496

0.56391 (12)

0.542446

0.0172 (5)

0.0170 (5)

0.0165 (4)

0.0249 (6)

0.030*

0.0366 (7)

0.055*

0.0190 (5)

0.023*

0.0252 (6)

0.038*

0.0294 (6)

0.044*

0.0336 (7)

0.050*

C6

N2

C4

H4A

H4B

C5

H5A

H5B

H5C

C11

H11

C12

H12A

H12B

H12C

C13

H13A

H13B

H13C

C18

H18A

Acta Cryst. (2018). C74, 1703-1714

sup-9

supporting information

H18B

H18C

C16

H16A

H16B

H16C

N1

C7

N3

O1

O2

O3

O4

O5

S1

H3

H2

H3A

0.600427

0.489215

0.7711 (3)

0.782223

0.764416

1.030111

1.021770

0.8032 (3)

0.701934

0.832903

0.602386

0.548949

0.59051 (11)

0.588917

0.629021

0.050*

0.0279 (6)

0.042*

0.863932

0.846781

0.573080

0.042*

0.4442 (2)

0.4840 (3)

0.3372 (2)

0.24103 (17)

0.73574 (18)

0.54486 (19)

0.50057 (18)

0.48618 (18)

0.66106 (8)

0.327 (3)

0.83019 (18)

0.6877 (2)

0.6871 (2)

0.79625 (16)

0.58447 (17)

0.55537 (17)

0.86552 (17)

0.77041 (17)

0.88046 (6)

0.624 (2)

0.86787 (7)

0.78880 (9)

0.64868 (8)

0.80922 (6)

0.78407 (7)

0.71284 (7)

0.66745 (6)

0.58289 (6)

0.94304 (3)

0.6266 (9)

0.7528 (9)

0.7338 (10)

0.0140 (4)

0.0139 (5)

0.0170 (4)

0.0184 (4)

0.0210 (4)

0.0203 (4)

0.0223 (4)

0.0192 (4)

0.02442 (16)

0.027 (7)*

0.695 (3)

0.627 (3)

0.563 (5)

0.549 (5)

0.03 (2)*

0.50 (7)

2

Atomic displacement parameters (Å )

11

22

33

12

13

23

U

C1

C2

C8

C9

C10

C15

C14

C17

C3

C6

N2

C4

C5

C11

C12

C13

C18

C16

N1

0.0309 (14)

0.0224 (12)

0.0179 (12)

0.0157 (12)

0.0150 (12)

0.0230 (12)

0.0179 (12)

0.0366 (16)

0.0217 (13)

0.0191 (12)

0.0139 (10)

0.0152 (12)

0.0322 (15)

0.0184 (12)

0.0254 (13)

0.0205 (13)

0.0482 (17)

0.0215 (13)

0.0149 (10)

0.0128 (11)

0.0203 (10)

0.0139 (8)

0.0167 (8)

0.0172 (9)

0.0264 (9)

0.0211 (9)

0.0277 (13)

0.0172 (11)

0.0122 (10)

0.0134 (11)

0.0169 (12)

0.0185 (11)

0.0176 (11)

0.0328 (15)

0.0130 (11)

0.0148 (11)

0.0171 (9)

0.0308 (14)

0.0345 (15)

0.0192 (12)

0.0251 (13)

0.0364 (15)

0.0222 (13)

0.0319 (15)

0.0143 (9)

0.0143 (11)

0.0178 (10)

0.0234 (9)

0.0258 (10)

0.0247 (9)

0.0207 (8)

0.0230 (9)

0.0229 (13)

0.0141 (12)

0.0141 (11)

0.0179 (12)

0.0142 (11)

0.0196 (12)

0.0155 (12)

0.0211 (13)

0.0168 (12)

0.0172 (12)

0.0186 (10)

0.0286 (14)

0.0430 (18)

0.0192 (13)

0.0251 (14)

0.0314 (15)

0.0304 (16)

0.0303 (15)

0.0128 (9)

0.0145 (11)

0.0129 (10)

0.0180 (9)

0.0205 (10)

0.0190 (9)

0.0199 (9)

0.0134 (8)

0.0047 (12)

0.0080 (12)

0.0003 (10)

0.0012 (10)

0.0042 (9)

−0.0008 (12)

−0.0028 (9)

0.0018 (9)

0.0013 (10)

−0.0017 (10)

0.0014 (10)

0.0002 (10)

−0.0023 (12)

0.0031 (10)

0.0014 (9)

−0.0002 (9)

−0.0051 (12)

−0.0005 (14)

−0.0004 (10)

0.0050 (11)

0.0080 (13)

0.0046 (12)

−0.0049 (13)

−0.0001 (8)

0.0017 (9)

−0.0026 (9)

−0.0028 (7)

−0.0050 (8)

−0.0065 (7)

−0.0045 (8)

−0.0002 (7)

0.0049 (11)

−0.0019 (10)

−0.0023 (11)

−0.0007 (9)

−0.0056 (10)

0.0025 (11)

−0.0102 (13)

−0.0013 (10)

−0.0009 (10)

0.0012 (8)

0.0040 (12)

0.0137 (13)

−0.0032 (10)

−0.0051 (12)

−0.0089 (12)

−0.0015 (13)

−0.0054 (12)

0.0016 (8)

−0.0004 (9)

0.0075 (11)

−0.0008 (10)

0.0074 (12)

−0.0012 (10)

0.0021 (10)

−0.0026 (8)

−0.0070 (11)

−0.0141 (14)

0.0012 (10)

0.0032 (11)

−0.0048 (11)

0.0112 (14)

0.0054 (11)

−0.0001 (8)

0.0008 (9)

C7

N3

O1

O2

O3

O4

O5

−0.0008 (9)

−0.0044 (9)

0.0036 (7)

0.0058 (7)

0.0048 (8)

−0.0010 (9)

−0.0011 (7)

0.0008 (8)

−0.0003 (8)

0.0019 (7)

−0.0064 (8)

−0.0070 (7)

0.0028 (7)

Acta Cryst. (2018). C74, 1703-1714

sup-10

supporting information

S1

0.0295 (3)

0.0236 (3)

0.0201 (3)

0.0030 (3)

−0.0098 (3)

−0.0048 (3)

Geometric parameters (Å, º)

C1—C2

1.499 (3)

C6—O2

1.252 (3)

C1—H1A

C1—H1B

C1—H1C

C2—N1

C2—H2A

C2—H2B

C8—O1

C8—N1

C8—C7

C9—O3

C9—C7

C9—C10

C10—N3

C10—C11

C10—H10

C15—O5

C15—C17

C15—C16

C15—C18

C14—O4

C14—O5

C14—N3

C17—H17A

C17—H17B

C17—H17C

C3—N1

0.9800

1.462 (3)

0.9900

C6—N2

C6—C7

N2—C4

C4—C5

1.357 (3)

1.404 (3)

1.474 (3)

1.488 (3)

0.9900

0.9800

1.497 (3)

1.502 (3)

1.0000

0.9800

0.816 (18)

0.860 (3)

C4—H4A

C4—H4B

C5—H5A

C5—H5B

C5—H5C

C11—C12

C11—C13

C11—H11

C12—H12A

C12—H12B

C12—H12C

C13—H13A

C13—H13B

C13—H13C

C18—H18A

C18—H18B

C18—H18C

C16—H16A

C16—H16B

C16—H16C

N3—H3

0.9900

1.207 (3)

1.401 (3)

1.419 (3)

1.263 (3)

1.390 (3)

1.504 (3)

1.437 (3)

1.532 (3)

1.0000

1.459 (3)

1.491 (3)

1.496 (3)

1.503 (3)

1.196 (3)

1.328 (3)

1.343 (3)

0.9800

1.349 (3)

1.368 (3)

1.640 (2)

O2—H2

O3—H3A

C3—N2

C3—S1

C2—C1—H1A

C2—C1—H1B

H1A—C1—H1B

C2—C1—H1C

H1A—C1—H1C

H1B—C1—H1C

N1—C2—C1

N1—C2—H2A

C1—C2—H2A

N1—C2—H2B

C1—C2—H2B

H2A—C2—H2B

O1—C8—N1

109.5

112.05 (19)

109.2

107.9

118.5 (2)

126.0 (2)

N2—C4—H4B

C5—C4—H4B

H4A—C4—H4B

C4—C5—H5A

C4—C5—H5B

H5A—C5—H5B

C4—C5—H5C

H5A—C5—H5C

H5B—C5—H5C

C12—C11—C13

C12—C11—C10

C13—C11—C10

C12—C11—H11

C13—C11—H11

109.3

107.9

109.5

111.1 (2)

113.2 (2)

110.26 (19)

107.3

O1—C8—C7

107.3

Acta Cryst. (2018). C74, 1703-1714

sup-11

supporting information

N1—C8—C7

O3—C9—C7

115.43 (19)

120.1 (2)

114.61 (19)

125.3 (2)

109.09 (18)

107.94 (19)

111.15 (18)

109.5

C10—C11—H11

C11—C12—H12A

C11—C12—H12B

H12A—C12—H12B

C11—C12—H12C

H12A—C12—H12C

H12B—C12—H12C

C11—C13—H13A

C11—C13—H13B

H13A—C13—H13B

C11—C13—H13C

H13A—C13—H13C

H13B—C13—H13C

C15—C18—H18A

C15—C18—H18B

H18A—C18—H18B

C15—C18—H18C

H18A—C18—H18C

H18B—C18—H18C

C15—C16—H16A

C15—C16—H16B

H16A—C16—H16B

C15—C16—H16C

H16A—C16—H16C

H16B—C16—H16C

C3—N1—C8

107.3

109.5

O3—C9—C10

C7—C9—C10

N3—C10—C9

N3—C10—C11

C9—C10—C11

N3—C10—H10

C9—C10—H10

C11—C10—H10

O5—C15—C17

O5—C15—C16

C17—C15—C16

O5—C15—C18

C17—C15—C18

C16—C15—C18

O4—C14—O5

O4—C14—N3

O5—C14—N3

C15—C17—H17A

C15—C17—H17B

H17A—C17—H17B

C15—C17—H17C

H17A—C17—H17C

H17B—C17—H17C

N1—C3—N2

109.5

102.17 (18)

109.71 (18)

110.6 (2)

110.53 (19)

111.3 (2)

112.1 (2)

126.3 (2)

124.1 (2)

109.6 (2)

109.5

116.87 (19)

122.31 (17)

120.81 (17)

117.1 (2)

123.0 (2)

119.8 (2)

122.84 (19)

116.39 (19)

120.72 (19)

111.7 (2)

109.3

125.37 (18)

119.59 (19)

114.98 (17)

116.5 (2)

123.8 (2)

119.6 (2)

119.53 (19)

115.5 (18)

119.3 (18)

107.6 (4)

106.6 (4)

120.17 (18)

N1—C3—S1

N2—C3—S1

O2—C6—N2

O2—C6—C7

N2—C6—C7

C6—N2—C3

C6—N2—C4

C3—N2—C4

C3—N1—C2

C8—N1—C2

C9—C7—C6

C9—C7—C8

C6—C7—C8

C14—N3—C10

C14—N3—H3

C10—N3—H3

N2—C4—C5

N2—C4—H4A

C5—C4—H4A

C6—O2—H2

C9—O3—H3A

C14—O5—C15

109.3

O3—C9—C10—N3

C7—C9—C10—N3

O3—C9—C10—C11

C7—C9—C10—C11

O2—C6—N2—C3

C7—C6—N2—C3

O2—C6—N2—C4

C7—C6—N2—C4

N1—C3—N2—C6

S1—C3—N2—C6

−41.3 (3)

137.3 (2)

77.6 (2)

−103.8 (3)

−180.0 (2)

1.2 (3)

2.8 (3)

−176.0 (2)

0.2 (3)

C7—C8—N1—C2

C1—C2—N1—C3

C1—C2—N1—C8

O3—C9—C7—C6

C10—C9—C7—C6

O3—C9—C7—C8

C10—C9—C7—C8

O2—C6—C7—C9

N2—C6—C7—C9

O2—C6—C7—C8

174.93 (18)

−92.5 (2)

90.1 (2)

6.1 (3)

−172.4 (2)

−177.47 (19)

4.0 (3)

−5.4 (3)

173.3 (2)

178.0 (2)

−179.03 (17)

Acta Cryst. (2018). C74, 1703-1714

sup-12

supporting information

N1—C3—N2—C4

S1—C3—N2—C4

C6—N2—C4—C5

C3—N2—C4—C5

N3—C10—C11—C12

C9—C10—C11—C12

N3—C10—C11—C13

C9—C10—C11—C13

N2—C3—N1—C8

S1—C3—N1—C8

N2—C3—N1—C2

S1—C3—N1—C2

O1—C8—N1—C3

C7—C8—N1—C3

O1—C8—N1—C2

177.34 (19)

−1.9 (3)

−86.0 (3)

96.7 (3)

168.4 (2)

48.8 (3)

−66.4 (2)

174.0 (2)

0.4 (3)

179.63 (17)

−176.76 (18)

2.5 (3)

176.7 (2)

−2.3 (3)

N2—C6—C7—C8

O1—C8—C7—C9

N1—C8—C7—C9

O1—C8—C7—C6

N1—C8—C7—C6

O4—C14—N3—C10

O5—C14—N3—C10

C9—C10—N3—C14

C11—C10—N3—C14

O4—C14—O5—C15

N3—C14—O5—C15

C17—C15—O5—C14

C16—C15—O5—C14

C18—C15—O5—C14

−3.3 (3)

8.4 (4)

−172.6 (2)

−175.3 (2)

3.7 (3)

−11.4 (3)

169.31 (19)

−53.7 (3)

−174.61 (19)

11.1 (3)

−169.58 (18)

177.0 (2)

59.7 (3)

−64.4 (3)

−6.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A

D—H

H···A

D···A

D—H···A

C10—H10···O1

C11—H11···N2

C18—H18A···S1

1.00

0.98

2.20

2.64

2.86

2.39

2.863 (3)

3.615 (3)

3.760 (3)

2.937 (3)

3.000 (3)

3.698 (2)

2.374 (2)

123

166

154

115

i

ii

C18—H18B···O4

C16—H16B···O4

0.98

2.42

117

i

N3—H3···S1

0.82 (2)

0.86 (1)

2.89 (2)

1.59 (1)

1.56 (1)

170 (2)

150 (1)

156 (1)

O2—H2···O3

O3—H3A···O2

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+3/2, −y+2, z−1/2.

1,3-Diethyl-4,6-dioxo-2-thioxo-<i.N-(p-tolyl)hexahydropyrimidine-5-carbothioamide (A13)

Crystal data

C

M

16

H

19

N

3

O

2

S

2

F(000) = 736

= 1.467 Mg m

−3

r

= 349.46

D

x

Monoclinic, P2

1

/c

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 9954 reflections

θ = 2.3–28.6°

µ = 0.35 mm

T = 100 K

a = 4.8156 (2) Å

b = 21.7395 (7) Å

c = 15.1912 (5) Å

β = 95.656 (1)°

V = 1582.61 (10) Å

Z = 4

−1

3

Rod, yellow

0.19 × 0.12 × 0.11 mm

Data collection

Bruker APEXII CCD

diffractometer

Radiation source: sealed tube

Graphite monochromator

φ and ω scans

25387 measured reflections

4036 independent reflections

3430 reflections with I > 2σ(I)

R

int = 0.027

θ

max = 28.7°, θmin = 1.9°

Absorption correction: multi-scan

h = −6→6

(

SADABS; Bruker, 2012)

k = −28→29

l = −16→20

T

min = 0.925, Tmax = 0.976

Acta Cryst. (2018). C74, 1703-1714

sup-13

supporting information

Refinement

2

Refinement on F

Hydrogen site location: inferred from

Least-squares matrix: full

neighbouring sites

2

R[F > 2σ(F )] = 0.031

H-atom parameters constrained

2

wR(F ) = 0.078

w = 1/[σ (F

o

) + (0.0319P) + 0.9919P]

2

S = 1.04

where P = (F

o

+ 2F )/3

c

4

2

0

036 reflections

12 parameters

restraints

(Δ/σ)max = 0.003

Δρmax = 0.38 e Å

Δρmin = −0.25 e Å

−

3

−

3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance

matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;

correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate

(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

2

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )

x

y

z

Uiso*/Ueq

C1

0.6364 (3)

0.444617

0.738110

0.633537

0.7801 (3)

0.802275

0.05024 (7)

0.059313

0.031661

0.021547

0.10933 (6)

0.136248

1.11011 (9)

1.122381

1.162536

1.060273

1.08713 (9)

1.139925

0.0200 (3)

0.030*

0.0165 (3)

0.020*

H1A

H1B

H1C

C2

H2B

H2C

C3

C4

C5

C6

C7

0.968596

0.099599

1.070263

0.020*

0.4240 (3)

0.2647 (3)

0.0575 (3)

−0.2913 (3)

−0.4266 (3)

−0.379058

−0.6294 (3)

−0.719285

−0.7045 (3)

−0.9212 (3)

−1.107692

−0.891626

−0.904996

0.6700 (3)

0.5668 (3)

0.767628

0.18473 (6)

0.21854 (6)

0.26444 (6)

0.33867 (6)

0.34618 (6)

0.320332

0.39103 (6)

0.395317

0.43003 (6)

0.47956 (7)

0.461102

0.499911

0.509862

0.12958 (6)

0.15332 (6)

0.145225

1.03472 (8)

0.96914 (8)

0.99080 (8)

0.91476 (8)

0.82949 (9)

0.782841

0.81270 (9)

0.754494

0.87935 (9)

0.86014 (10)

0.855538

0.804258

0.908134

0.92701 (9)

0.76841 (8)

0.764691

0.0130 (2)

0.0122 (2)

0.0124 (2)

0.0132 (3)

0.0153 (3)

0.018*

0.0166 (3)

0.020*

0.0159 (3)

0.0200 (3)

0.030*

0.0132 (2)

0.0148 (3)

0.018*

H7

C8

H8

C9

C10

H10A

H10B

H10C

C11

C12

H12A

H12B

C13

H13A

H13B

H13C

C14

C15

0.516924

0.3974 (3)

0.453484

0.431028

0.198559

0.191291

0.09994 (7)

0.061833

0.096098

0.107472

0.734493

0.72690 (9)

0.758223

0.664552

0.731147

0.018*

0.0184 (3)

0.028*

0.3072 (3)

−0.5709 (3)

0.20499 (6)

0.42136 (6)

0.87829 (8)

0.96368 (9)

0.0124 (2)

0.0187 (3)

Acta Cryst. (2018). C74, 1703-1714

sup-14

supporting information

H15

C16

H16

N1

N2

H2A

N3

O1

O2

H2

−0.621330

−0.3657 (3)

−0.277263

0.6200 (2)

−0.0813 (2)

−0.032193

0.5180 (2)

0.1706 (2)

0.4004 (2)

0.282227

0.446804

0.37673 (6)

0.372309

0.14275 (5)

0.29283 (5)

0.280534

0.16309 (5)

0.22802 (4)

0.18827 (4)

0.215350

1.010404

0.98239 (9)

1.040768

1.01321 (7)

0.92183 (7)

0.870382

0.86255 (7)

0.81289 (6)

1.11873 (6)

1.127983

0.022*

0.0183 (3)

0.022*

0.0132 (2)

0.0134 (2)

0.016*

0.0125 (2)

0.0156 (2)

0.0158 (2)

0.024*

S1

S2

0.90026 (7)

−0.00427 (8)

0.07630 (2)

0.27972 (2)

0.90407 (2)

1.09736 (2)

0.01698 (9)

0.01633 (9)

2

Atomic displacement parameters (Å )

11

22

33

12

13

23

U

C1

C2

C3

C4

C5

C6

C7

C8

0.0230 (8)

0.0157 (7)

0.0126 (6)

0.0134 (6)

0.0133 (6)

0.0134 (6)

0.0170 (7)

0.0167 (7)

0.0133 (6)

0.0165 (7)

0.0120 (6)

0.0162 (7)

0.0204 (7)

0.0123 (6)

0.0227 (7)

0.0235 (7)

0.0132 (6)

0.0161 (6)

0.0130 (6)

0.0188 (5)

0.0181 (5)

0.01535 (17)

0.02104 (18)

0.0181 (7)

0.0187 (7)

0.0126 (6)

0.0123 (6)

0.0116 (6)

0.0121 (6)

0.0159 (6)

0.0172 (6)

0.0145 (6)

0.0179 (7)

0.0121 (6)

0.0174 (6)

0.0205 (7)

0.0113 (6)

0.0169 (7)

0.0183 (7)

0.0134 (5)

0.0138 (5)

0.0133 (5)

0.0169 (5)

0.0188 (5)

0.01646 (17)

0.01790 (17)

0.0185 (7)

0.0025 (6)

0.0026 (5)

−0.0027 (5)

−0.0010 (5)

−0.0027 (5)

0.0003 (5)

−0.0007 (5)

−0.0008 (5)

−0.0016 (5)

0.0027 (5)

−0.0027 (5)

0.0011 (5)

−0.0005 (5)

−0.0024 (5)

0.0048 (6)

0.0042 (6)

0.0002 (4)

0.0025 (4)

−0.0003 (4)

0.0030 (4)

0.0032 (4)

0.00346 (12)

0.00360 (13)

0.0010 (6)

−0.0029 (5)

0.0009 (5)

0.0011 (5)

0.0015 (5)

0.0023 (5)

0.0016 (5)

−0.0015 (5)

0.0027 (5)

0.0008 (6)

0.0018 (5)

0.0053 (5)

0.0034 (5)

0.0011 (5)

0.0046 (5)

0.0005 (5)

−0.0004 (4)

0.0019 (4)

0.0023 (4)

0.0004 (4)

0.0011 (4)

0.00381 (13)

0.00249 (12)

0.0038 (5)

0.0022 (5)

0.0000 (5)

−0.0007 (4)

−0.0009 (4)

0.0002 (5)

−0.0012 (5)

0.0009 (5)

0.0025 (5)

0.0020 (5)

0.0005 (5)

−0.0003 (5)

−0.0048 (5)

−0.0009 (4)

−0.0014 (5)

−0.0007 (5)

0.0009 (4)

−0.0006 (4)

−0.0005 (4)

0.0003 (3)

0.0006 (4)

0.00027 (12)

−0.00065 (12)

0.0143 (6)

0.0137 (6)

0.0108 (5)

0.0125 (6)

0.0143 (6)

0.0129 (6)

0.0151 (6)

0.0201 (6)

0.0252 (7)

0.0155 (6)

0.0116 (6)

0.0146 (6)

0.0134 (6)

0.0171 (6)

0.0130 (6)

0.0128 (5)

0.0105 (5)

0.0115 (5)

0.0109 (4)

0.0105 (4)

0.01953 (17)

0.01023 (15)

C9

C10

C11

C12

C13

C14

C15

C16

N1

N2

N3

O1

O2

S1

S2

Geometric parameters (Å, º)

C1—C2

1.516 (2)

C9—C10

1.5078 (19)

C1—H1A

C1—H1B

C1—H1C

C2—N1

0.9800

1.4876 (16)

0.9900

C10—H10A

C10—H10B

C10—H10C

C11—N3

0.9800

1.3726 (16)

1.3846 (17)

C2—H2B

C11—N1

Acta Cryst. (2018). C74, 1703-1714

sup-15

supporting information

C2—H2C

C3—O2

C3—N1

C3—C4

C4—C14

C4—C5

C5—N2

C5—S2

C6—C16

C6—C7

C6—N2

C7—C8

C7—H7

C8—C9

C8—H8

C9—C15

0.9900

C11—S1

C12—N3

1.6639 (14)

1.4874 (16)

1.5192 (19)

0.9900

0.9800

1.2415 (16)

1.4019 (17)

1.3942 (19)

0.9500

1.2947 (16)

1.3752 (17)

1.4038 (17)

1.4453 (17)

1.4711 (18)

1.3370 (16)

1.7071 (13)

1.3931 (18)

1.4011 (18)

1.4164 (17)

1.3855 (19)

0.9500

C12—C13

C12—H12A

C12—H12B

C13—H13A

C13—H13B

C13—H13C

C14—O1

C14—N3

C15—C16

C15—H15

C16—H16

N2—H2A

O2—H2

0.9500

0.8800

0.8400

1.395 (2)

0.9500

1.3885 (19)

C2—C1—H1A

C2—C1—H1B

H1A—C1—H1B

C2—C1—H1C

H1A—C1—H1C

H1B—C1—H1C

N1—C2—C1

N1—C2—H2B

C1—C2—H2B

N1—C2—H2C

C1—C2—H2C

H2B—C2—H2C

O2—C3—N1

O2—C3—C4

N1—C3—C4

C3—C4—C14

C3—C4—C5

C14—C4—C5

N2—C5—C4

N2—C5—S2

C4—C5—S2

C16—C6—C7

C16—C6—N2

C7—C6—N2

C8—C7—C6

C8—C7—H7

C6—C7—H7

C7—C8—C9

C7—C8—H8

C9—C8—H8

C15—C9—C8

109.5

111.91 (11)

109.2

H10A—C10—H10C

H10B—C10—H10C

N3—C11—N1

N3—C11—S1

N1—C11—S1

109.5

115.75 (11)

122.66 (10)

121.58 (10)

112.27 (11)

109.2

107.9

109.5

117.45 (11)

124.63 (12)

117.92 (11)

122.49 (13)

118.8

119.45 (12)

120.3

N3—C12—C13

N3—C12—H12A

C13—C12—H12A

N3—C12—H12B

C13—C12—H12B

H12A—C12—H12B

C12—C13—H13A

C12—C13—H13B

H13A—C13—H13B

C12—C13—H13C

H13A—C13—H13C

H13B—C13—H13C

O1—C14—N3

109.2

107.9

113.75 (11)

124.99 (12)

121.24 (12)

116.88 (12)

122.11 (12)

120.98 (11)

115.81 (11)

122.21 (10)

121.98 (9)

118.85 (12)

126.56 (12)

114.56 (11)

120.49 (12)

119.8

O1—C14—C4

N3—C14—C4

C9—C15—C16

C9—C15—H15

C16—C15—H15

C6—C16—C15

C6—C16—H16

C15—C16—H16

C3—N1—C11

C3—N1—C2

C11—N1—C2

C5—N2—C6

C5—N2—H2A

120.3

119.8

121.49 (12)

119.3

117.22 (13)

123.34 (11)

117.49 (11)

119.16 (11)

133.01 (11)

113.5

Acta Cryst. (2018). C74, 1703-1714

sup-16

supporting information

C15—C9—C10

C8—C9—C10

C9—C10—H10A

C9—C10—H10B

H10A—C10—H10B

C9—C10—H10C

121.62 (13)

121.16 (12)

109.5

C6—N2—H2A

C11—N3—C14

C11—N3—C12

C14—N3—C12

C3—O2—H2

113.5

124.58 (11)

119.10 (11)

116.26 (10)

109.5

O2—C3—C4—C14

N1—C3—C4—C14

O2—C3—C4—C5

N1—C3—C4—C5

C3—C4—C5—N2

C14—C4—C5—N2

C3—C4—C5—S2

C14—C4—C5—S2

C16—C6—C7—C8

N2—C6—C7—C8

C6—C7—C8—C9

C7—C8—C9—C15

C7—C8—C9—C10

C3—C4—C14—O1

C5—C4—C14—O1

C3—C4—C14—N3

C5—C4—C14—N3

C8—C9—C15—C16

C10—C9—C15—C16

C7—C6—C16—C15

N2—C6—C16—C15

C9—C15—C16—C6

O2—C3—N1—C11

−175.61 (12)

2.86 (19)

2.6 (2)

−178.90 (12)

−179.38 (12)

−1.21 (18)

−0.13 (18)

178.04 (10)

0.5 (2)

−177.64 (12)

0.2 (2)

−1.1 (2)

178.74 (13)

175.27 (12)

−3.0 (2)

−4.98 (18)

176.76 (11)

1.3 (2)

C4—C3—N1—C11

O2—C3—N1—C2

C4—C3—N1—C2

N3—C11—N1—C3

S1—C11—N1—C3

N3—C11—N1—C2

S1—C11—N1—C2

C1—C2—N1—C3

C1—C2—N1—C11

C4—C5—N2—C6

S2—C5—N2—C6

C16—C6—N2—C5

C7—C6—N2—C5

N1—C11—N3—C14

S1—C11—N3—C14

N1—C11—N3—C12

S1—C11—N3—C12

O1—C14—N3—C11

C4—C14—N3—C11

O1—C14—N3—C12

C4—C14—N3—C12

−1.66 (19)

−1.73 (17)

179.63 (12)

2.49 (18)

−177.43 (10)

−178.82 (11)

1.26 (17)

89.70 (14)

−89.06 (15)

−179.88 (13)

0.9 (2)

15.8 (2)

−166.23 (14)

−5.00 (18)

174.92 (10)

177.82 (11)

−2.26 (17)

−173.84 (12)

6.40 (18)

3.41 (17)

−176.35 (11)

85.26 (15)

−92.15 (14)

−178.54 (14)

−0.3 (2)

177.58 (13)

−0.6 (2)

C13—C12—N3—C11

C13—C12—N3—C14

176.97 (12)

Hydrogen-bond geometry (Å, º)

D—H···A

D—H

H···A

D···A

D—H···A

i

C7—H7···O2

0.95

0.98

0.95

0.88

0.84

2.62

2.95

2.51

1.79

1.99

3.3136 (16)

3.4766 (15)

3.1509 (14)

2.5671 (15)

2.7802 (10)

130

115

125

147

157

C13—H13A···S1

C16—H16···S2

N2—H2A···O1

O2—H2···S2

Symmetry code: (i) x−1, −y+1/2, z−1/2.

5-(1-Aminoethylidene)-1,3-diethyl-2-thioxodihydropyrimidine-4,6(1H,5H)-dione (A17)

Crystal data

C

M

10

H

15

N

3

O

2

S

b = 9.8458 (3) Å

c = 18.2217 (6) Å

β = 98.250 (2)°

r

= 241.31

Monoclinic, P2

1

/c

3

a = 12.8983 (4) Å

V = 2290.10 (13) Å

Acta Cryst. (2018). C74, 1703-1714

sup-17

supporting information

Z = 8

F(000) = 1024

θ = 1.7–28.4°

µ = 0.27 mm

T = 100 K

−1

−3

D

x

= 1.400 Mg m

Mo Kα radiation, λ = 0.71073 Å

Block, colourless

Cell parameters from 9096 reflections

0.19 × 0.13 × 0.09 mm

Data collection

Bruker APEXII CCD

diffractometer

Radiation source: sealed tube

Graphite monochromator

φ and ω scans

14727 measured reflections

5036 independent reflections

4323 reflections with I > 2σ(I)

R

int = 0.024

θ

max = 27.2°, θmin = 2.3°

Absorption correction: multi-scan

h = −16→16

k = −12→12

l = −23→22

(

SADABS; Bruker, 2012)

T

min = 0.941, Tmax = 0.985

Refinement

2

Refinement on F

Hydrogen site location: inferred from

neighbouring sites

Least-squares matrix: full

R[F > 2σ(F )] = 0.033

2

H-atom parameters constrained

2

wR(F ) = 0.088

w = 1/[σ (F

o

) + (0.0456P) + 0.8588P]

2

S = 1.03

where P = (F

o

+ 2F )/3

c

5

2

3

036 reflections

91 parameters

restraints

(Δ/σ)max = 0.004

Δρmax = 0.28 e Å

Δρmin = −0.27 e Å

−

3

−

3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance

matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;

correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate

(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

2

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )

x

y

z

Uiso*/Ueq

C6

0.61243 (11)

0.6519

0.6093

0.27480 (14)

0.2775

0.3662

0.36078 (8)

0.3187

0.3816

0.0203 (3)

0.030*

H6A

H6B

H6C

C7

C10

C4

H4A

H4B

C5

H5A

H5B

H5C

C3

0.5412

0.2422

0.3440

0.030*

0.66566 (10)

0.68959 (10)

0.72421 (11)

0.7107

0.7971

0.71329 (12)

0.7629

0.6417

0.7282

0.55336 (10)

0.53259 (10)

0.38748 (10)

0.18105 (13)

0.07191 (13)

−0.01292 (14)

0.0230

0.0108

−0.16651 (15)

−0.2047

−0.1909

−0.2031

0.09224 (13)

0.21474 (13)

0.20954 (14)

0.41878 (7)

0.54211 (7)

0.66991 (8)

0.7184

0.6640

0.67012 (9)

0.7106

0.6772

0.6227

0.62285 (7)

0.50361 (7)

0.57743 (8)

0.0150 (3)

0.0149 (3)

0.0191 (3)

0.023*

0.0248 (3)

0.037*

0.0156 (3)

0.0155 (3)

0.0178 (3)

C9

C2

Acta Cryst. (2018). C74, 1703-1714

sup-18

Article Doi

Crystal structure, spectroscopic studies and theoretical studies of thiobarbituric acid derivatives: understanding the hydrogen-bonding patterns

DOI: 10.1107/S2053229618015516

Source and publish data:

Authors:

Article abstract of DOI:10.1107/S2053229618015516

Full text of DOI:10.1107/S2053229618015516

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