Neutral 4-phenyl-1-[phenyl(pyridin-2-yl)methylidene]semicarbazide and its salt forms with inorganic anions

Article abstract of DOI:10.1107/S2053229618016467

Semicarbazones can exist in two tautomeric forms. In the solid state, they are found in the keto form. This work presents the synthesis, structures and spectroscopic characterization (IR and NMR spectroscopy) of four such compounds, namely the neutral mol

Full text of DOI:10.1107/S2053229618016467

research papers
Neutral 4-phenyl-1-[phenyl(pyridin-2-yl)methyl-
idene]semicarbazide and its salt forms with
inorganic anions
ISSN 2053-2296
a
b
c
´
ˆ
´
Vinicius Oliveira Araujo, Barbara Tirloni, Lıvia Streit and Vania Denise
Schwadea*
Received 10 November 2018
Accepted 19 November 2018
a
ˆ
Faculdade de Ciencias Exatas e Tecnologia, Universidade Federal da Grande Dourados, Rodovia Dourados/Itahum,
b
´
km 12, Dourados, Mato Grosso do Sul 79804-970, Brazil, Departamento de Quımica, Universidade Federal de Santa
Maria, Avenida Roraima, n. 1000, Santa Maria, Rio Grande do Sul 97105-900, Brazil, and cDepartment of Chemistry and
Biochemistry, University of North Georgia, 3820 Mundy Mill Rd, Oakwood, GA 30566, USA. *Correspondence e-mail:
vaniaschwade@gmail.com
Edited by A. L. Spek, Utrecht University, The
Netherlands
Keywords: semicarbazide; crystal structure;
Semicarbazones can exist in two tautomeric forms. In the solid state, they are
found in the keto form. This work presents the synthesis, structures and
spectroscopic characterization (IR and NMR spectroscopy) of four such com-
pounds, namely the neutral molecule 4-phenyl-1-[phenyl(pyridin-2-yl)methyl-
idene]semicarbazide, C19H16N4O, (I), abbreviated as HBzPyS, and three
different hydrated salts, namely the chloride dihydrate, C19H17N4O+ꢀClꢁꢀ2H2O,
(II), the nitrate dihydrate, C19H17N4O+ꢀNO3ꢁꢀ2H2O, (III), and the thiocyanate
2.5-hydrate, C19H17N4O+ꢀSCNꢁꢀ2.5H2O, (IV), of 2-[phenyl({[(phenylcarbamo-
yl)amino]imino})methyl]pyridinium, abbreviated as [H2BzPyS]+ꢀXꢁꢀnH2O, with
X = Clꢁ and n = 2 for (II), X = NO3ꢁ and n = 2 for (III), and X = SCNꢁ and n =
2.5 for (IV), showing the influence of the anionic form in the intermolecular
interactions. Water molecules and counter-ions (chloride or nitrate) are involved
in the formation of a two-dimensional arrangement by the establishment of
hydrogen bonds with the N—H groups of the cation, stabilizing the E isomers in
the solid state. The neutral HBzPyS molecule crystallized as the E isomer due to
the existence of weak ꢀ–ꢀ interactions between pairs of molecules. The
calculated IR spectrum of the hydrated [H2BzPyS]+ cation is in good agreement
with the experimental results.
hydrogen bond; supramolecular arrangement.
CCDC references: 1879906; 1879905;
1879904; 1879903
Supporting information: this article has
supporting information at journals.iucr.org/c
1. Introduction
Hydrazones belong to a class of organic compounds with the
structure R1R2C NNH2. These compounds possess diverse
biological and pharmacological properties, such as anti-
microbial, anti-inflammatory, analgesic, antifungal, antiviral,
anticancer, antimalarial, antitrypanosomal etc. (Verma et al.,
2014). The biological properties of this class of compounds are
often related to metal ion coordination (Beraldo & Gambino,
2004). Recently, AgI complexes with 2-benzoylpyridine-
derived hydrazones have shown cytotoxic activity (Santos et
al., 2018). There are several studies concerning the hydrazone
derived from 2-benzoylpyridine and 4-phenylsemicarbazide
based on CuII complexes (Patel, 2009, 2010a,b; Patel et al.,
2009, 2010; Kurup et al., 2011; Aiswarya et al., 2013). In these
CuII complexes, the hydrazone coordinates as a tridentate
N,N0,O-chelating ligand, mainly without deprotonation.
Semicarbazone can exist in two tautomeric forms, namely
keto and enol, or in an equilibrium mixture of the two forms
due to the amide –NH—C( O) function. In the solid state, it
is well established by IR spectroscopy that the keto form
remains (Kurup et al., 2011). The rearrangement of the elec-
tron density in the whole molecule and, consequently, signif-
# 2019 International Union of Crystallography
Acta Cryst. (2019). C75
https://doi.org/10.1107/S2053229618016467 1 of 7

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Table 1
Experimental details.
For all determinations, the temperature was 100 K, Z was 4, the radiation type was Mo Kꢃ, the diffractometer was a Bruker D8 Venture Photon 100 and the
absorption correction was multi-scan (SADABS; Bruker, 2015).
(I)
(II)
(III)
(IV)
Crystal data
Chemical formula
Mr
Crystal system, space group
C19H16N4O
316.36
Monoclinic, P21/c
5.6126 (3), 10.0683 (4),
27.2349 (12)
90.095 (2)
1539.02 (12)
0.09
0.31 ꢄ 0.13 ꢄ 0.07
C19H17N4O+ꢀClꢁꢀ2H2O
388.85
Monoclinic, P21/c
9.4452 (19), 9.5489 (19),
21.039 (4)
95.26 (3)
1889.5 (7)
0.23
0.28 ꢄ 0.23 ꢄ 0.13
C19H17N4O+ꢀNO3ꢁꢀ2H2O
415.41
Monoclinic, P21/c
9.5556 (4), 9.3050 (4),
22.2715 (10)
96.048 (2)
1969.24 (15)
0.11
0.21 ꢄ 0.10 ꢄ 0.08
C19H17N4O+ꢀNCSꢁꢀ2.5H2O
420.48
Monoclinic, P21/n
13.0053 (4), 7.7965 (2),
20.8703 (7)
107.887 (1)
2013.87 (11)
0.20
0.24 ꢄ 0.10 ꢄ 0.05
˚
a, b, c (A)
ꢄ (ꢃ)
3
˚
V (A )
ꢅ (mmꢁ1
Crystal size (mm)
)
Data collection
Tmin, Tmax
0.715, 0.746
37458, 4693, 3813
0.724, 0.745
66072, 5794, 4889
0.683, 0.746
42340, 6023, 3810
0.707, 0.746
31447, 6146, 4590
No. of measured, indepen-
dent and observed
[I > 2ꢆ(I)] reflections
Rint
0.039
0.715
0.119
0.716
0.068
0.716
0.040
0.716
ꢁ1
˚
(sin ꢇ/ꢈ)max (A
)
Refinement
R[F2 > 2ꢆ(F2)], wR(F2), S
No. of reflections
0.048, 0.130, 1.02
4693
0.041, 0.112, 1.04
5794
0.058, 0.140, 1.03
6023
0.049, 0.131, 1.02
6146
No. of parameters
No. of restraints
H-atom treatment
217
0
256
0
293
0
326
6
H-atom parameters
constrained
H atoms treated by a
mixture of independent
and constrained refine-
ment
H atoms treated by a
mixture of independent
and constrained refine-
ment
H atoms treated by a
mixture of independent
and constrained refine-
ment
ꢁ3
˚
Áꢉmax, Áꢉmin (e A
)
0.43, ꢁ0.24
Computer programs: APEX3 (Bruker, 2015), SAINT (Bruker, 2015), SHELXT2014 (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), DIAMOND (Brandenburg, 2012) and WinGX
0.42, ꢁ0.39
0.37, ꢁ0.54
0.4, ꢁ0.41
(Farrugia, 2012).
icant changes in the spectral and photophysical behaviours are
possible once tautomerism can occur by proton exchange
between two or more forms, a process of great importance for
dyes (Rauf et al., 2015).
In this article, we present the synthesis, structure and
spectroscopic characterization of four compounds, namely
yellow microcrystalline compound formed, which was filtered
off and dried (yield 98%).
2.1.2. Synthesis of [HBzPyS], (I). Hydrated salt (II)
(176 mg, 0.45 mmol) was added to ethanol (4 ml) and to the
resulting suspension, deionized water (2 ml) was added, giving
a clear yellow solution. Solid sodium acetate (62 mg,
0.75 mmol) was added. Immediately, the solution became
colourless and a white solid appeared. After 1 h of stirring at
room temperature, the solid was filtered off and dried in air,
affording (I) in 92% yield.
2.1.3. Synthesis of [H2BzPyS]XꢀnH2O [X = NO3 and n = 2
for (III); X= SCN and n = 2.5 for (IV)]. Hydrated salts (III) and
(IV) were prepared by adding sodium nitrate or potassium
thiocyanate (0.75 mmol) to a solution of (II) (176 mg,
0.45 mmol) in ethanol (4 ml) and deionized water (2 ml).
Slowly, a yellow solid appeared while the mixture was stirred
for 1 h. The solid was filtered off and dried in air, giving (III)
and (IV) in yields of 82 and 74%, respectively.
neutral
4-phenyl-1-[phenyl(pyridin-2-yl)methylidene]semi-
carbazide, (I) (see Scheme), denoted HBzPyS, and three
different salts of [H2BzPyS]+ with chloride, (II), nitrate, (III),
and thiocyanate, (IV), showing the influence of the anionic
form in the intermolecular interactions.
2. Experimental
2.1. Synthesis and crystallization
All chemicals and the solvent (ethanol) were used without
further purification. Single crystals suitable for X-ray analyses
were obtained from the mother solution of the reactions after
about one week by slow evaporation of the solvent.
2.2. Spectroscopic data
2.1.1. Synthesis of [H2BzPyS]Clꢀ2H2O, (II). Hydrated salt
(II) was obtained by the condensation reaction of 2-benzoyl-
pyridine (916 mg, 5 mmol) and 4-phenylsemicarbazide hydro-
chloride (938 mg, 5 mmol) in ethanol (15 ml). The mixture was
refluxed with stirring for 6 h. After cooling to room
temperature, the solution was set aside for a few hours until a
For (I): IR (KBr pellet, ꢁ, cmꢁ1): 3375 (m), 3341 (m), 3048
(w), 3029 (w), 1698 (s), 1600 (m), 1535 (s), 1446 (m), 1418 (m),
1310 (m), 1268 (m), 1234 (m), 1189 (m), 1132 (m), 794 (w), 756
(m), 694 (m), 614 (m), 555 (m), 508 (m). 1H NMR (600 MHz,
DMSO-d6, ppm): ꢂ 9.26 (s, 1H), 8.92 (s, 1H), 8.44 (ddd, J = 4.8,
1.7, 0.9 Hz, 1H), 8.31–8.24 (m, 1H), 7.90–7.85 (m, 1H), 7.61–
ꢂ
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1
Table 2
Selected geometric parameters (A, ) for compounds (I)–(IV).
(m), 712 (m), 694 (m), 618 (m). H NMR (600 MHz, DMSO-
d6, ppm): ꢂ 10.08 (s, 1H), 9.71 (s, 1H), 8.87 (d, J = 5.0 Hz, 1H),
8.39 (t, J = 7.6 Hz, 1H), 7.90 (t, J = 6.1 Hz, 1H), 7.77 (d, J =
7.9 Hz, 2H), 7.68–7.60 (m, 3H), 7.53 (d, J = 6.3 Hz, 1H), 7.48–
7.45 (m, 2H), 7.33–7.29 (m, 2H), 7.05 (tt, J = 7.5, 1.1 Hz, 1H).
13C NMR (150 MHz, DMSO-d6, ppm): ꢂ 151.98, 148.99,
144.14, 143.70, 140.70, 138.74, 130.42, 129.79, 129.16, 129.03,
128.45, 125.73, 125.10, 123.02, 120.50.
ꢃ
˚
Compound (I)
O1—C13
N1—C1
N1—C5
N2—C6
N2—N3
1.2173 (15)
1.3385 (16)
1.3462 (14)
1.2919 (14)
1.3615 (14)
N3—C13
N4—C13
N4—C14
C5—C6
C6—C7
1.3839 (15)
1.3610 (15)
1.4066 (14)
1.4804 (16)
1.4949 (15)
C6—N2—N3
N2—N3—C13
C13—N4—C14
N1—C5—C6
N2—C6—C5
117.67 (9)
121.17 (9)
127.66 (10)
116.36 (10)
116.03 (10)
N2—C6—C7
C5—C6—C7
O1—C13—N4
O1—C13—N3
N4—C13—N3
123.52 (10)
120.45 (9)
126.70 (11)
120.02 (10)
113.28 (10)
Compound (II)
O1—C13
N1—C1
N1—C5
N2—C6
N2—N3
1.2298 (14)
1.3384 (15)
1.3575 (15)
1.2902 (15)
1.3447 (13)
N3—C13
N4—C13
N4—C14
C5—C6
C6—C7
1.3910 (14)
1.3507 (14)
1.4081 (14)
1.4775 (15)
1.4927 (16)
C6—N2—N3
N2—N3—C13
C13—N4—C14
N1—C5—C6
N2—C6—C5
119.08 (10)
117.20 (9)
127.57 (10)
117.58 (10)
113.87 (10)
N2—C6—C7
C5—C6—C7
O1—C13—N4
O1—C13—N3
N4—C13—N3
125.44 (10)
120.68 (10)
126.05 (10)
122.53 (10)
111.42 (10)
For (III): IR (KBr pellet, ꢁ, cmꢁ1): 3394 (m), 3092 (w), 3051
(w), 3033 (w), 1704 (s), 1617 (m), 1558 (vs), 1519 (s), 1502 (s),
1446 (m), 1383 (s), 1321 (s), 1250 (m), 1199 (vs), 1135 (s), 785
(m), 759 (m), 741 (m), 710 (m), 692 (m), 510 (m).
For (IV): IR (KBr pellet, ꢁ, cmꢁ1): 3420 (m), 3327 (m), 3276
(m), 3036 (w), 2056 (s), 1699 (s), 1617 (m), 1559 (s), 1498 (s),
1445 (m), 1381 (m), 1320 (m), 1252 (m), 1204 (s), 1161 (m),
1135 (m), 782 (m), 758 (m), 740 (m), 698 (m), 506 (m).
Compound (III)
O1—C13
N1—C1
N1—C5
N2—C6
N2—N3
N3—C13
N4—C13
1.224 (2)
1.339 (2)
1.354 (2)
1.293 (2)
1.3451 (18)
1.391 (2)
1.350 (2)
N4—C14
C5—C6
C6—C7
N5—O4
N5—O3
N5—O5B
N5—O5A
1.408 (2)
1.477 (2)
1.490 (2)
1.185 (2)
1.224 (2)
1.353 (3)
1.363 (3)
C6—N2—N3
N2—N3—C13
C13—N4—C14
N1—C5—C6
N2—C6—C5
N2—C6—C7
C5—C6—C7
O1—C13—N4
118.62 (14)
117.15 (13)
128.13 (14)
117.94 (14)
114.14 (14)
125.70 (14)
120.16 (14)
126.03 (15)
O1—C13—N3
N4—C13—N3
O4—N5—O3
O4—N5—O5B
O3—N5—O5B
O4—N5—O5A
O3—N5—O5A
122.58 (14)
111.39 (14)
126.39 (16)
106.1 (2)
118.2 (2)
104.9 (2)
114.96 (19)
2.3. Refinement
Crystal data, data collection and structure refinement
details are summarized in Table 1. H atoms bonded to phenyl-
ring C atoms were placed at calculated positions, with C—H =
˚
0.98 A, and treated as riding on the parent atoms, with
Uiso(H) = 1.2Ueq(C). The highest remaining electron densities
are not attributable to any additional atom. Hydrated salts
(III) and (IV) showed positional disorder in the anion which
was handled with SHELXL (Sheldrick, 2015b) PART
instructions which ensure that geometrical calculations do not
simultaneously involve atoms from different disordered
congeners. The O5 atom in the nitrate anion and the
N5 C20—S1 thiocyanate anion were calculated in two
positions having almost 50% occupancy each. In (IV), a
disordered water molecule was also successfully handled using
PART instructions and restraints.
Compound (IV)
O1—C13
N1—C1
N1—C5
N2—C6
N2—N3
N3—C13
N4—C13
1.2232 (17)
1.3431 (17)
1.3542 (17)
1.2895 (18)
1.3492 (15)
1.3902 (18)
1.3585 (17)
N4—C14
C5—C6
C6—C7
S1A—C20A
C20A—N5A
S1B—C20B
C20B—N5B
1.4081 (18)
1.4798 (18)
1.4855 (18)
1.650 (5)
1.166 (6)
1.616 (8)
1.159 (8)
C6—N2—N3
N2—N3—C13
C13—N4—C14
N1—C5—C6
N2—C6—C5
N2—C6—C7
119.00 (12)
117.37 (11)
127.43 (12)
118.07 (12)
114.46 (12)
126.82 (12)
C5—C6—C7
118.65 (12)
125.70 (13)
122.73 (12)
111.57 (12)
177.1 (5)
O1—C13—N4
O1—C13—N3
N4—C13—N3
N5A—C20A—S1A
N5B—C20B—S1B
177.7 (5)
2.4. Computational details
7.55 (m, 2H), 7.55–7.49 (m, 3H), 7.35 (ddd, J = 7.4, 4.8, 1.1 Hz,
1H), 7.33–7.27 (m, 4H), 7.01 (t, J = 7.4 Hz, 1H). 13C NMR
(150 MHz, DMSO-d6, ppm): ꢂ 155.32, 151.94, 148.58, 148.39,
139.02, 136.58, 132.06, 129.13, 129.11, 128.88, 128.76, 123.57,
122.66, 121.39, 119.40.
For (II): IR (KBr pellet, ꢁ, cmꢁ1): 3373 (m), 3239 (m), 3197
(m), 3017 (m), 1701 (s), 1616 (s), 1599 (s), 1560 (s), 1536 (s),
1493 (s), 1446 (s), 1375 (m), 1321 (s), 1200 (vs), 1134 (s), 760
Vibrational analysis of the [H2BzPyS]+ cation was carried
out on the optimized structure using the density functional
theory (DFT) formalism at the B3LYP/6-311G** level,
including empirical dispersion corrections of Grimme at the
D3 level. The GAUSSIAN16 (Frisch et al., 2016) suite of codes
was used for all calculations. Optimization and frequency
calculations were performed using XSEDE supercomputing
resources (Towns et al., 2014). Structure and IR spectrum
ꢂ
Acta Cryst. (2019). C75
Araujo et al.
A neutral semicarbazide and its inorganic salts 3 of 7

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analyses, as well as band assignment, were carried out using
GaussView (Dennington et al., 2016).
intermolecular hydrogen bonds between the –NHPh group
and the carbonyl O atom are not observed in (I). Furthermore,
as the orientation of the pyridine N atom also differs from that
of the hydrazone derived from 2-benzoylpyridine and semi-
carbazide, intramolecular hydrogen bonding is also not
present in (I). This may be due to the existence of weak ꢀ–ꢀ
interactions between pairs of molecules, with a centroid–
3. Results and discussion
In the solid state, the asymmetric unit of (I) consists of one
independent molecule of HBzPyS (Fig. 1). The compound
crystallizes as the E isomer (where E refers to the configura-
tion around the C N bond), thus differing from the hydra-
zone derived from 2-benzoylpyridine and semicarbazide
which crystallized as the Z isomer (Lima et al., 2008). Due to
the presence of the –NHPh group instead of an –NH2 group,
˚
˚
centroid distance of 4.0784 (7) A (slippage ꢅ1.37 A) (Fig. 2).
Aromatic ꢀ–ꢀ stacking interactions have been observed in
CuII complexes (Patel, 2010a,b; Kurup et al., 2011) and by us in
PbII complexes with hydrazone-type ligands (Schwade et al.,
2016a,b). The imine N2 C6 bond length (Table 2) is in
Figure 1
The molecular structures of (a) (I), (b) (II), (c) (III) and (d) (IV). Displacement ellipsoids are drawn at the 50% probability level. In (III) and (IV),
disordered atoms are labelled with suffixes A and B.
ꢂ
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Table 3
Hydrogen-bond geometry (A, ) for (II).
Table 4
Hydrogen-bond geometry (A, ) for (III).
ꢃ
ꢃ
˚
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
O2—H1Wꢀ ꢀ ꢀO1
N3—H3Aꢀ ꢀ ꢀCl1i
O3—H3Wꢀ ꢀ ꢀCl1ii
N1—H1Aꢀ ꢀ ꢀO2
N4—H4Aꢀ ꢀ ꢀCl1i
O3—H4Wꢀ ꢀ ꢀCl1
O2—H2Wꢀ ꢀ ꢀO3
0.79 (2)
0.86
0.92 (2)
0.86
0.86
2.01 (2)
2.52
2.25 (2)
1.82
2.31
2.7905 (13)
3.2700 (12)
3.1665 (14)
2.6533 (14)
3.1434 (13)
3.1974 (14)
2.7370 (15)
169.6 (19)
146
171.2 (19)
163
164
N1—H1Aꢀ ꢀ ꢀO2
N3—H3Aꢀ ꢀ ꢀO6i
N4—H4Aꢀ ꢀ ꢀO6i
O2—H1Wꢀ ꢀ ꢀO1
O2—H2Wꢀ ꢀ ꢀO3
O6—H3Wꢀ ꢀ ꢀO4
O6—H3Wꢀ ꢀ ꢀO5A
O6—H3Wꢀ ꢀ ꢀO5B
O6—H4Wꢀ ꢀ ꢀO3ii
O6—H4Wꢀ ꢀ ꢀO5Bii
0.88
0.88
0.88
0.86 (3)
0.84 (3)
0.91 (3)
0.91 (3)
0.91 (3)
0.99 (3)
0.99 (3)
1.81
2.08
2.03
1.92 (3)
1.96 (3)
1.95 (3)
2.55 (3)
2.28 (3)
1.87 (3)
2.51 (3)
2.6639 (19)
2.8794 (19)
2.875 (2)
2.7756 (17)
2.783 (2)
2.816 (2)
3.172 (3)
3.008 (4)
2.833 (2)
3.210 (4)
164
150
159
174 (2)
165 (2)
159 (2)
126 (2)
137 (2)
163 (2)
127.0 (19)
0.85 (2)
0.86 (2)
2.35 (2)
1.90 (2)
178 (2)
164.0 (18)
1
2
1
2
1
2
1
2
Symmetry codes: (i) x; ꢁy þ ; z þ ; (ii) ꢁx; y þ ; ꢁz þ .
3
2
1
2
1
2
1
2
Symmetry codes: (i) x; ꢁy þ ; z þ ; (ii) ꢁx þ 1; y þ ; ꢁz þ .
accordance with that reported for the hydrazone derived from
2-benzoylpyridine and semicarbazide (Lima et al., 2008),
which was obtained by the addition of an equimolar amount of
influenced by the hydrogen bonds with the solvent molecules
and the anion, and so the E isomers are observed. Figs. S1 and
S2 in the supporting information present the extended
supramolecular arrangements for (II) and (III).
The existence of hydrogen bonding involving the carbonyl
O atom causes a slight elongation of the C O bond.
˚
Compared to the distance in (I), which is 1.2173 (15) A, in
compounds (II)–(IV), the C O distances are in the range
˚
1.2232 (17)–1.2298 (14) A (Table 2). In addition, the N—N
bond length is somewhat shortened to 1.3447 (13)–
´
sodium acetate to the reaction mixture (Perez-Rebolledo et
al., 2006). In this work, (I) was obtained by the reaction of
4-phenyl-1-[phenyl(pyridin-2-yl)methylidene]semicarbazidium
chloride, (II), with sodium acetate.
The direct reaction of 2-benzoylpyridine and 4-phenyl-
semicarbazide hydrochloride gives as the product the hydro-
chloride derivative of (I) in good yield. The asymmetric unit of
(II) consists of one [H2BzPyS]+ cation, a chloride anion and
two solvent water molecules (Fig. 1). The water molecules are
involved in hydrogen bonding producing a supramolecular
two-dimensional arrangement in the crystallographic bc plane
(Fig. 3). One of the water molecules participates in hydrogen
bonding with the pyridinium H atom and the carbonyl O atom
acting as donor and acceptor, respectively (Table 3).
Hydrated salts (III) and (IV) were prepared in an ethanolic/
aqueous media of (I) and sodium nitrate or potassium thio-
cyanate. The same feature concerning hydrogen bonds with
one water molecule is observed in the crystal structures of
(III) (Fig. 3 and Table 4) and (IV) (Fig. 4 and Table 5). An
analogous supramolecular two-dimensional arrangement has
been observed for (III). Concerning the hydrazonium salts, it
can be seen that the orientation of the cation is strongly
˚
˚
1.3492 (15) A compared to the value of 1.3615 (14) A in (I).
Hydrated salts (III) and (IV) are soluble in pure ethanol.
Salt (II) initially dissolves in ethanol; however, it precipitates
again if water is not added. Compound (I) is soluble in ethanol
and other common organic solvents, but insoluble in water.
The salts were characterized by the experimental IR spectra
of the compounds (Fig. S3 in the supporting information) and
by the calculated IR spectrum of the hydrated [H2BzPyS]+
cation, as shown in Table 6. The N—H stretching vibrations of
the amide groups are found around 3330–3200 cmꢁ1. The
O—H stretching vibrations in the range 3420–3373 cmꢁ1 are
due to the solvent water molecules. The ꢁ(C O) and
ꢁ(C N) bands are found at approximately 1700 and
1617 cmꢁ1, respectively. N—H bending vibrations appear at
1558–1560 cmꢁ1. The NO and CN stretching vibration bands
of the nitrate and thiocyanate anions are found at 1383 and
2056 cmꢁ1, respectively. The calculated spectrum (Fig. S4 in
the supporting information) is in good agreement with the
experimental results, showing normal modes of vibration
Table 5
Hydrogen-bond geometry (A, ) for (IV).
ꢃ
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N1—H1Aꢀ ꢀ ꢀO2
0.88
0.88
0.88
0.88
1.79
2.40
2.04
2.00
2.6531 (17)
3.123 (5)
2.809 (5)
2.845 (4)
2.718 (4)
2.7575 (15)
3.225 (2)
3.280 (3)
3.319 (5)
3.185 (5)
166
139
146
160
N3—H3Aꢀ ꢀ ꢀO3A
N3—H3Aꢀ ꢀ ꢀO3B
N4—H4Aꢀ ꢀ ꢀO3A
N4—H4Aꢀ ꢀ ꢀO3B
O2—H1Wꢀ ꢀ ꢀO1
0.88
1.88
160
0.82 (3)
0.83 (3)
0.83 (3)
0.86 (1)
0.86 (1)
1.94 (3)
2.40 (3)
2.47 (3)
2.69 (3)
2.34 (2)
174 (2)
168 (2)
164 (2)
131 (4)
166 (5)
O2—H2Wꢀ ꢀ ꢀS1A
O2—H2Wꢀ ꢀ ꢀS1B
O3A—H3WAꢀ ꢀ ꢀS1Ai
O3B—H3WBꢀ ꢀ ꢀS1Bi
Figure 2
A view of the ꢀ-stacking interaction between two molecules in (I).
Aromatic H atoms have been omitted for clarity. [Symmetry code: (i)
ꢁx + 1, ꢁy, ꢁz + 1.]
Symmetry code: (i) ꢁx þ 1; ꢁy þ 1; ꢁz þ 1.
ꢂ
Acta Cryst. (2019). C75
Araujo et al.
A neutral semicarbazide and its inorganic salts 5 of 7

research papers
mostly due to the N—H stretching of 3329 cmꢁ1 for the
pyridinium group, and 3474 and 3552 cmꢁ1 for the amide
groups. The normal modes found in the range from 3892 to
3530 cmꢁ1 can be assigned to the O—H stretching of solvent
water molecules. The normal mode at 1733 cmꢁ1 is due to the
For the neutral compound, (I), the N—H stretching vibra-
tions are observed as sharp bands at 3375 and 3341 cmꢁ1
,
while the ꢁ(C O) and ꢁ(C N) bands are found at 1698 and
1600 cmꢁ1, respectively, as has been observed previously
(Kurup et al., 2011). A band found at 1132 cmꢁ1 is assigned to
the ꢁ(N—N) band of semicarbazide. The N—H bending
vibration appears at 1535 cmꢁ1, which differs from that found
in the salts since the main difference is the absence of
C
O stretching, and the normal modes found at 1585 and
N
1581 cmꢁ1 correspond to the asymmetric and symmetric C
stretching vibrations, respectively.
Figure 3
Aview of the hydrogen bonds in (a) (II) and (b) (III), showing the formation of a two-dimensional supramolecular arrangement. Aromatic H atoms have
been omitted for clarity. [Symmetry codes for (II): (i) x, ꢁy + 12, z + 21; (ii) ꢁx, y + 21, ꢁz + 12; symmetry codes for (III): (i) x, ꢁy + 23, z + 21; (ii) ꢁx + 1, y + 12,
1
ꢁz + .]
2
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Table 6
Selected normal modes of vibration calculated for the hydrated
[H2BzPyS]+ cation.
Normal vibrations Frequency (cmꢁ1) Normal vibrations Frequency (cmꢁ1
)
ꢁ2(O2—H)
ꢁ1(O2—H)
ꢁ2(O3—H)
ꢁ1(O3—H)
ꢁ1(N4—H)
3892.64
3530.41
3883.54
3763.48
3552.76
ꢁ1(N3—H)
ꢁ1(N1—H)
ꢁ1(C13—O1)
ꢁ2(C13—N4)
ꢁ1(C13—N4)
3474.86
3329.39
1733.86
1585.25
1581.30
hydrogen bonds (Fig. S3 in the supporting information). In the
solid state, all compounds are in the keto form, which has been
proven by the crystal structures.
The NMR spectra of compounds (I) and (II) were recorded
in the same deuterated solvent (DMSO-d6). The signals for
the amide-group H atoms appear as singlets at 9.26 and
8.92 ppm for (I), and at 10.08 and 9.71 ppm for (II). These
differences in chemical shifts can be rationalized by differ-
ences in the strengths of the hydrogen bonds involving the
N3—H and N4—H amidic H atoms, since (II) could interact
preferentially with water molecules or chloride ions present in
the sample, leading to stronger interactions. Also, it is worthy
of note that the signals in the 1H and 13C NMR spectra are not
duplicated, indicating the presence of only one configurational
isomeric form for each compound in DMSO-d6 solution.
Figure 4
A view of the hydrogen bonds (dashed lines) in (IV). Only hydrogen
bonds involving molecules with full occupancy were considered.
Aromatic H atoms have been omitted for clarity. [Symmetry code: (i)
ꢁx + 1, ꢁy + 1, ꢁz + 1.]
Funding information
Funding for this research was provided by: the Brazilian
agency CAPES (Coordenac¸a˜o de Aperfeic¸oamento de
´
Pessoal de Nıvel Superior) and the Extreme Science and
Patel, R. N., Shukla, K. K., Singh, A., Choudhary, M., Chauhan, U. K.
& Dwivedi, S. (2009). Inorg. Chim. Acta, 362, 4891–4898.
Patel, R. N., Shukla, K. K., Singh, A., Choudhary, M. & Patel, D. K.
(2010). J. Coord. Chem. 63, 586–599.
Engineering Discovery Environment (XSEDE), which is
supported by the National Science Foundation (grant No.
MCB-170108).
´
Perez-Rebolledo, A., Piro, O. E., Castellano, E., Teixeira, L. R.,
Batista, A. & Beraldo, H. (2006). J. Mol. Struct. 794, 18–23.
Rauf, M. A., Hisaindee, S. & Saleh, N. (2015). RSC Adv. 5, 18097–
18110.
References
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Beraldo, H. (2018). ACS Omega, 3, 7027–7035.
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Aiswarya, N., Sithambaresan, M., Kurup, M. R. P. & Ng, S. W. (2013).
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Beraldo, H. & Gambino, D. (2004). Mini Rev. Med. Chem. 4, 31–39.
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Germany.
Schwade, V. D., Faoro, E. & Schulz Lang, E. (2016b). Acta Cryst. C72,
525–529.
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Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8.
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8.
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A., Hazlewood, V., Lathrop, S., Lifka, D., Peterson, G. D., Roskies,
R., Scott, J. R. & Wilkens-Diehr, N. (2014). Comput. Sci. Eng. 16,
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& Alam, M. M. (2014). J. Pharm. Bioallied Sci. 6, 69–80.
Xu, Y., Chen, C.-L., Zhou, J. & Li, M.-X. (2008). Acta Cryst. E64,
m177.
Dennington, R., Keith, T. A. & Millam, J. M. (2016). GaussView.
Version 6. Semichem, Inc., Shawnee Mission, KS, USA.
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ꢂ
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A neutral semicarbazide and its inorganic salts 7 of 7

supporting information
supporting information
Acta Cryst. (2019). C75 [https://doi.org/10.1107/S2053229618016467]
Neutral 4-phenyl-1-[phenyl(pyridin-2-yl)methylidene]semicarbazide and its salt
forms with inorganic anions
Vinicius Oliveira Araujo, Bárbara Tirloni, Lívia Streit and Vânia Denise Schwade
Computing details
For all structures, data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT
(Bruker, 2015); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine
structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2012); software used to
prepare material for publication: WinGX (Farrugia, 2012).
4-Phenyl-1-[phenyl(pyridin-2-yl)methylidene]semicarbazide (I)
Crystal data
C19H16N4O
Mr = 316.36
F(000) = 664
Dx = 1.365 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 9971 reflections
θ = 2.5–30.5°
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 5.6126 (3) Å
b = 10.0683 (4) Å
c = 27.2349 (12) Å
β = 90.095 (2)°
V = 1539.02 (12) Å3
Z = 4
µ = 0.09 mm−1
T = 100 K
Block, colourless
0.31 × 0.13 × 0.07 mm
Data collection
Bruker D8 Venture Photon 100
diffractometer
Radiation source: microfocus X ray tube
φ and ω scans
4693 independent reflections
3813 reflections with I > 2σ(I)
Rint = 0.039
θ
max = 30.5°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2015)
h = −8→8
k = −14→14
l = −38→38
T
min = 0.715, Tmax = 0.746
37458 measured reflections
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.048
wR(F2) = 0.130
S = 1.02
4693 reflections
217 parameters
0 restraints
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0685P)2 + 0.7078P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.43 e Å−3
Δρmin = −0.24 e Å−3
0 constraints
Acta Cryst. (2019). C75
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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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
O1
N1
N2
N3
H3A
N4
H4A
C1
1.05213 (17)
0.09296 (18)
0.58312 (18)
0.73938 (19)
0.7275
0.91577 (18)
0.7922
−0.0760 (2)
−0.1889
0.05900 (9)
0.44896 (10)
0.28384 (10)
0.18385 (10)
0.14
0.22644 (10)
0.2792
0.53746 (13)
0.5609
0.62708 (3)
0.55743 (4)
0.61287 (3)
0.60314 (4)
0.5753
0.67747 (4)
0.6812
0.56891 (4)
0.5444
0.0231 (2)
0.0173 (2)
0.0152 (2)
0.0182 (2)
0.022*
0.0173 (2)
0.021*
0.0199 (2)
0.024*
H1
C2
H2
−0.0950 (2)
−0.2206
0.59682 (12)
0.6573
0.61466 (4)
0.6216
0.0196 (2)
0.023*
C3
H3
0.0740 (2)
0.0673
0.56568 (12)
0.6056
0.65015 (4)
0.6817
0.0200 (2)
0.024*
C4
H4
0.2517 (2)
0.3705
0.47617 (12)
0.4545
0.63895 (4)
0.6625
0.0181 (2)
0.022*
C5
C6
C7
C8
0.2540 (2)
0.4318 (2)
0.4285 (2)
0.2388 (2)
0.1083
0.41762 (11)
0.31515 (11)
0.25270 (11)
0.17334 (12)
0.1594
0.59223 (4)
0.57900 (4)
0.52920 (4)
0.51455 (4)
0.5361
0.0135 (2)
0.0136 (2)
0.0135 (2)
0.0185 (2)
0.022*
H8
C9
H9
0.2392 (2)
0.1087
0.11422 (12)
0.0605
0.46839 (5)
0.4585
0.0204 (2)
0.024*
C10
H10
C11
H11
C12
H12
C13
C14
C15
H15
C16
H16
C17
H17
C18
H18
C19
0.4293 (2)
0.4298
0.6184 (2)
0.7484
0.6188 (2)
0.749
0.9165 (2)
1.0893 (2)
1.2864 (2)
1.3078
1.4520 (2)
1.5862
1.4241 (2)
1.5396
1.2252 (2)
1.2029
1.0589 (2)
0.13349 (12)
0.0923
0.21273 (14)
0.2264
0.27252 (13)
0.3269
0.15002 (11)
0.23100 (12)
0.14683 (13)
0.0797
0.16245 (13)
0.1051
0.26024 (14)
0.271
0.34212 (13)
0.4082
0.32794 (12)
0.43688 (4)
0.4055
0.45113 (4)
0.4294
0.49728 (4)
0.507
0.63625 (4)
0.71477 (4)
0.71683 (4)
0.6927
0.75474 (4)
0.7563
0.79021 (4)
0.8154
0.78834 (4)
0.8128
0.75103 (4)
0.0191 (2)
0.023*
0.0215 (3)
0.026*
0.0189 (2)
0.023*
0.0158 (2)
0.0154 (2)
0.0183 (2)
0.022*
0.0213 (3)
0.026*
0.0227 (3)
0.027*
0.0218 (3)
0.026*
0.0188 (2)
Acta Cryst. (2019). C75
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supporting information
H19
0.9234
0.3844
0.7501
0.023*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
O1
N1
N2
N3
N4
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
0.0272 (5)
0.0197 (5)
0.0171 (5)
0.0223 (5)
0.0169 (5)
0.0205 (6)
0.0211 (6)
0.0257 (6)
0.0214 (6)
0.0155 (5)
0.0157 (5)
0.0158 (5)
0.0172 (5)
0.0207 (6)
0.0254 (6)
0.0211 (6)
0.0163 (5)
0.0197 (5)
0.0161 (5)
0.0175 (5)
0.0169 (5)
0.0220 (6)
0.0272 (6)
0.0211 (6)
0.0230 (4)
0.0177 (5)
0.0149 (4)
0.0183 (5)
0.0201 (5)
0.0214 (6)
0.0176 (5)
0.0208 (6)
0.0209 (5)
0.0133 (5)
0.0133 (5)
0.0129 (5)
0.0197 (5)
0.0191 (5)
0.0178 (5)
0.0284 (6)
0.0243 (6)
0.0155 (5)
0.0176 (5)
0.0221 (6)
0.0286 (6)
0.0304 (7)
0.0224 (6)
0.0189 (5)
0.0191 (4)
0.0144 (4)
0.0137 (4)
0.0138 (4)
0.0149 (4)
0.0180 (5)
0.0199 (5)
0.0135 (5)
0.0120 (5)
0.0118 (4)
0.0120 (4)
0.0118 (4)
0.0186 (5)
0.0213 (5)
0.0142 (5)
0.0150 (5)
0.0160 (5)
0.0124 (5)
0.0124 (5)
0.0154 (5)
0.0182 (5)
0.0157 (5)
0.0159 (5)
0.0164 (5)
0.0077 (4)
−0.0005 (4)
−0.0004 (4)
0.0031 (4)
0.0040 (4)
0.0009 (5)
0.0009 (4)
−0.0007 (5)
−0.0014 (5)
−0.0034 (4)
−0.0038 (4)
−0.0003 (4)
−0.0055 (4)
−0.0056 (5)
−0.0014 (5)
−0.0046 (5)
−0.0061 (5)
−0.0016 (4)
−0.0008 (4)
0.0023 (4)
0.0035 (5)
−0.0030 (5)
−0.0020 (5)
0.0017 (4)
−0.0042 (3)
−0.0046 (4)
−0.0020 (3)
−0.0044 (4)
−0.0028 (4)
−0.0049 (4)
0.0003 (4)
−0.0006 (4)
−0.0036 (4)
−0.0018 (4)
−0.0010 (4)
−0.0021 (4)
0.0019 (4)
−0.0028 (3)
−0.0013 (4)
0.0009 (3)
−0.0035 (4)
−0.0023 (4)
−0.0012 (4)
−0.0016 (4)
−0.0028 (4)
−0.0003 (4)
0.0012 (4)
0.0009 (4)
0.0003 (4)
−0.0029 (4)
−0.0048 (4)
−0.0023 (4)
−0.0013 (5)
−0.0010 (4)
0.0016 (4)
0.0027 (4)
0.0014 (4)
0.0033 (5)
0.0012 (5)
−0.0019 (4)
0.0005 (4)
−0.0016 (4)
−0.0015 (4)
0.0026 (4)
−0.0011 (4)
−0.0003 (4)
−0.0013 (4)
−0.0001 (4)
−0.0014 (4)
−0.0036 (4)
−0.0018 (4)
−0.0016 (4)
Geometric parameters (Å, º)
O1—C13
N1—C1
N1—C5
N2—C6
N2—N3
N3—C13
N3—H3A
N4—C13
N4—C14
N4—H4A
C1—C2
C1—H1
C2—C3
C2—H2
C3—C4
C3—H3
1.2173 (15)
C7—C12
C8—C9
C8—H8
C9—C10
C9—H9
C10—C11
C10—H10
C11—C12
C11—H11
C12—H12
C14—C15
C14—C19
C15—C16
C15—H15
C16—C17
C16—H16
1.3926 (16)
1.3911 (16)
0.95
1.3839 (18)
0.95
1.3829 (18)
0.95
1.3936 (16)
0.95
0.95
1.3949 (16)
1.3990 (16)
1.3968 (16)
0.95
1.3883 (18)
0.95
1.3385 (16)
1.3462 (14)
1.2919 (14)
1.3615 (14)
1.3839 (15)
0.88
1.3610 (15)
1.4066 (14)
0.88
1.3864 (17)
0.95
1.3891 (17)
0.95
1.3785 (18)
0.95
Acta Cryst. (2019). C75
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supporting information
C4—C5
C4—H4
C5—C6
C6—C7
C7—C8
1.4024 (15)
0.95
1.4804 (16)
1.4949 (15)
1.3894 (16)
C17—C18
C17—H17
C18—C19
C18—H18
C19—H19
1.3888 (19)
0.95
1.3858 (16)
0.95
0.95
C1—N1—C5
C6—N2—N3
N2—N3—C13
N2—N3—H3A
C13—N3—H3A
C13—N4—C14
C13—N4—H4A
C14—N4—H4A
N1—C1—C2
N1—C1—H1
C2—C1—H1
C1—C2—C3
C1—C2—H2
C3—C2—H2
C4—C3—C2
C4—C3—H3
C2—C3—H3
C3—C4—C5
C3—C4—H4
C5—C4—H4
N1—C5—C4
N1—C5—C6
C4—C5—C6
N2—C6—C5
N2—C6—C7
C5—C6—C7
C8—C7—C12
C8—C7—C6
C12—C7—C6
C7—C8—C9
C7—C8—H8
C9—C8—H8
C10—C9—C8
117.81 (10)
117.67 (9)
121.17 (9)
119.4
119.4
127.66 (10)
116.2
116.2
123.55 (11)
118.2
118.2
118.32 (11)
120.8
120.8
119.15 (11)
120.4
120.4
118.90 (10)
120.5
C10—C9—H9
C8—C9—H9
119.9
119.9
119.92 (11)
120
120
120.16 (11)
119.9
119.9
120.07 (11)
120
120
126.70 (11)
120.02 (10)
113.28 (10)
119.53 (11)
123.87 (10)
116.59 (10)
119.22 (11)
120.4
120.4
121.23 (12)
119.4
119.4
119.14 (11)
120.4
C11—C10—C9
C11—C10—H10
C9—C10—H10
C10—C11—C12
C10—C11—H11
C12—C11—H11
C7—C12—C11
C7—C12—H12
C11—C12—H12
O1—C13—N4
O1—C13—N3
N4—C13—N3
C15—C14—C19
C15—C14—N4
C19—C14—N4
C14—C15—C16
C14—C15—H15
C16—C15—H15
C17—C16—C15
C17—C16—H16
C15—C16—H16
C16—C17—C18
C16—C17—H17
C18—C17—H17
C19—C18—C17
C19—C18—H18
C17—C18—H18
C18—C19—C14
C18—C19—H19
C14—C19—H19
120.5
122.21 (11)
116.36 (10)
121.41 (10)
116.03 (10)
123.52 (10)
120.45 (9)
119.43 (10)
120.71 (10)
119.86 (10)
120.21 (11)
119.9
120.4
120.40 (12)
119.8
119.8
120.45 (11)
119.8
119.9
120.20 (11)
119.8
C6—N2—N3—C13
C5—N1—C1—C2
N1—C1—C2—C3
C1—C2—C3—C4
C2—C3—C4—C5
C1—N1—C5—C4
C1—N1—C5—C6
C3—C4—C5—N1
175.88 (11)
−0.80 (19)
1.8 (2)
−0.86 (19)
−0.99 (18)
−1.21 (17)
177.43 (10)
2.11 (18)
C7—C8—C9—C10
C8—C9—C10—C11
0.36 (19)
−0.59 (19)
0.42 (19)
−0.19 (18)
178.94 (11)
−0.03 (19)
10.2 (2)
C9—C10—C11—C12
C8—C7—C12—C11
C6—C7—C12—C11
C10—C11—C12—C7
C14—N4—C13—O1
C14—N4—C13—N3
−170.32 (11)
Acta Cryst. (2019). C75
sup-4

supporting information
C3—C4—C5—C6
N3—N2—C6—C5
N3—N2—C6—C7
N1—C5—C6—N2
C4—C5—C6—N2
N1—C5—C6—C7
C4—C5—C6—C7
N2—C6—C7—C8
C5—C6—C7—C8
N2—C6—C7—C12
C5—C6—C7—C12
C12—C7—C8—C9
C6—C7—C8—C9
−176.45 (11)
175.80 (10)
−3.42 (16)
−178.80 (10)
−0.15 (16)
0.45 (15)
179.09 (10)
113.46 (13)
−65.72 (15)
−65.65 (15)
115.16 (12)
0.03 (18)
N2—N3—C13—O1
N2—N3—C13—N4
178.95 (11)
−0.52 (16)
C13—N4—C14—C15
C13—N4—C14—C19
C19—C14—C15—C16
N4—C14—C15—C16
C14—C15—C16—C17
C15—C16—C17—C18
C16—C17—C18—C19
C17—C18—C19—C14
C15—C14—C19—C18
N4—C14—C19—C18
−5.38 (19)
173.74 (11)
−0.99 (18)
178.09 (11)
−0.18 (19)
1.3 (2)
−1.2 (2)
0.00 (19)
1.09 (18)
−178.07 (11)
−179.09 (11)
2-[Phenyl({[(phenylcarbamoyl)amino]imino})methyl]pyridinium chloride dihydrate (II)
Crystal data
C19H17N4O+·Cl−·2H2O
Mr = 388.85
F(000) = 816
Dx = 1.367 Mg m−3
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 9.4452 (19) Å
b = 9.5489 (19) Å
c = 21.039 (4) Å
β = 95.26 (3)°
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 9932 reflections
θ = 2.9–30.5°
µ = 0.23 mm−1
T = 100 K
Block, yellow
V = 1889.5 (7) Å3
Z = 4
0.28 × 0.23 × 0.13 mm
Data collection
Bruker D8 Venture Photon 100
diffractometer
Radiation source: microfocus X ray tube
φ and ω scans
5794 independent reflections
4889 reflections with I > 2σ(I)
Rint = 0.119
θ
max = 30.6°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2015)
h = −13→13
k = −13→13
l = −30→30
T
min = 0.724, Tmax = 0.745
66072 measured reflections
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.041
wR(F2) = 0.112
S = 1.04
5794 reflections
Secondary atom site location: structure-
invariant direct methods
Hydrogen site location: mixed
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0553P)2 + 0.9098P]
where P = (Fo2 + 2Fc2)/3
256 parameters
0 restraints
0 constraints
Primary atom site location: structure-invariant
direct methods
(Δ/σ)max = 0.001
Δρmax = 0.42 e Å−3
Δρmin = −0.39 e Å−3
Acta Cryst. (2019). C75
sup-5

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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Cl1
O1
N1
H1A
N2
N3
H3A
N4
H4A
C1
0.06783 (3)
−0.17520 (9)
0.10125 (10)
0.0284
0.05449 (10)
0.01723 (10)
0.0691
−0.13882 (10)
−0.081
0.11352 (13)
0.0446
0.09797 (4)
0.40910 (9)
0.07050 (10)
0.1283
0.24698 (10)
0.33890 (10)
0.3502
0.49480 (11)
0.4876
−0.01729 (13)
−0.0152
0.22145 (2)
0.50096 (4)
0.43270 (4)
0.4307
0.52436 (4)
0.56830 (4)
0.6049
0.60335 (5)
0.6384
0.38390 (5)
0.3481
0.02280 (9)
0.01606 (18)
0.01254 (18)
0.015*
0.01189 (18)
0.01274 (19)
0.015*
0.01421 (19)
0.017*
0.0155 (2)
0.019*
H1
C2
H2
0.22502 (13)
0.2337
−0.11075 (13)
−0.1734
0.38504 (6)
0.3505
0.0164 (2)
0.02*
C3
H3
0.32428 (13)
0.4021
−0.11085 (13)
−0.1742
0.43795 (6)
0.44
0.0169 (2)
0.02*
C4
H4
0.30990 (12)
0.378
−0.01824 (13)
−0.0184
0.48798 (5)
0.5241
0.0153 (2)
0.018*
C5
C6
C7
C8
0.19622 (12)
0.17085 (12)
0.27603 (12)
0.30414 (13)
0.2542
0.07440 (12)
0.17684 (12)
0.19470 (12)
0.08615 (13)
0
0.48516 (5)
0.53552 (5)
0.59235 (5)
0.63600 (6)
0.6305
0.0116 (2)
0.0116 (2)
0.0125 (2)
0.0165 (2)
0.02*
H8
C9
H9
0.40567 (14)
0.4248
0.10438 (14)
0.0305
0.68769 (6)
0.7175
0.0204 (3)
0.024*
C10
H10
C11
H11
C12
H12
C13
C14
C15
H15
C16
H16
C17
H17
C18
0.47906 (13)
0.5501
0.44861 (13)
0.4973
0.34667 (12)
0.3253
−0.10673 (12)
−0.25407 (12)
−0.24406 (12)
−0.161
0.22994 (15)
0.2408
0.33944 (14)
0.4261
0.32249 (13)
0.3979
0.41545 (12)
0.58765 (12)
0.68459 (12)
0.6875
0.69591 (6)
0.7305
0.65360 (6)
0.6598
0.60189 (5)
0.5732
0.55349 (5)
0.60569 (5)
0.65562 (5)
0.6847
0.0201 (3)
0.024*
0.0191 (2)
0.023*
0.0153 (2)
0.018*
0.0118 (2)
0.0115 (2)
0.0139 (2)
0.017*
−0.35501 (13)
−0.3471
−0.47787 (13)
−0.5545
0.77650 (12)
0.8433
0.77128 (13)
0.8333
0.66282 (5)
0.6964
0.62103 (6)
0.6264
0.0154 (2)
0.018*
0.0169 (2)
0.02*
−0.48763 (13)
0.67484 (13)
0.57150 (6)
0.0168 (2)
Acta Cryst. (2019). C75
sup-6

supporting information
H18
C19
H19
O2
H1W
H2W
O3
−0.5714
−0.37619 (12)
−0.3834
−0.13582 (10)
−0.144 (2)
−0.154 (2)
−0.17336 (12)
−0.152 (2)
−0.110 (2)
0.6714
0.58294 (12)
0.5178
0.21563 (10)
0.278 (2)
0.2521 (19)
0.28318 (13)
0.377 (2)
0.5429
0.56314 (5)
0.5289
0.40474 (4)
0.4289 (9)
0.3676 (10)
0.27789 (5)
0.2752 (10)
0.2630 (11)
0.02*
0.0140 (2)
0.017*
0.01835 (18)
0.028*
0.028*
0.0287 (2)
0.043*
0.043*
H3W
H4W
0.232 (2)
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
Cl1
O1
N1
N2
N3
N4
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
O2
0.02539 (17)
0.0156 (4)
0.0126 (4)
0.0118 (4)
0.0120 (4)
0.0124 (4)
0.0179 (5)
0.0186 (6)
0.0158 (5)
0.0133 (5)
0.0115 (5)
0.0112 (5)
0.0093 (5)
0.0183 (5)
0.0235 (6)
0.0149 (5)
0.0144 (5)
0.0136 (5)
0.0110 (5)
0.0112 (5)
0.0128 (5)
0.0175 (5)
0.0162 (5)
0.0145 (5)
0.0141 (5)
0.0207 (4)
0.0287 (5)
0.02989 (17)
0.0207 (4)
0.0153 (4)
0.0132 (4)
0.0165 (5)
0.0190 (5)
0.0188 (5)
0.0188 (6)
0.0192 (6)
0.0201 (6)
0.0143 (5)
0.0137 (5)
0.0175 (5)
0.0169 (5)
0.0235 (6)
0.0319 (7)
0.0277 (6)
0.0202 (6)
0.0127 (5)
0.0132 (5)
0.0177 (5)
0.0160 (5)
0.0166 (5)
0.0190 (6)
0.0154 (5)
0.0202 (4)
0.0355 (6)
0.01209 (14)
−0.00797 (12)
0.0054 (3)
0.0016 (3)
0.0017 (3)
0.0041 (3)
0.0058 (4)
−0.0007 (4)
0.0001 (4)
0.0041 (4)
0.0030 (4)
−0.0004 (4)
0.0013 (4)
0.0034 (4)
0.0052 (4)
0.0101 (5)
0.0060 (5)
−0.0027 (5)
−0.0001 (4)
0.0015 (4)
0.0022 (4)
−0.0002 (4)
0.0010 (4)
0.0057 (4)
0.0049 (4)
0.0029 (4)
0.0053 (3)
0.0013 (5)
−0.00386 (11)
−0.0033 (3)
0.0009 (3)
0.0013 (3)
−0.0016 (3)
−0.0033 (3)
0.0007 (4)
0.0036 (4)
0.0032 (4)
0.0005 (4)
0.0015 (4)
0.0008 (4)
0.0005 (4)
−0.0005 (4)
−0.0029 (4)
−0.0024 (4)
0.0017 (4)
0.0015 (4)
0.0007 (4)
0.0009 (4)
−0.0003 (4)
0.0032 (4)
0.0015 (4)
−0.0035 (4)
−0.0023 (4)
−0.0034 (3)
−0.0020 (4)
−0.00191 (11)
−0.0029 (3)
0.0000 (3)
0.0110 (4)
0.0097 (4)
0.0107 (4)
0.0093 (4)
0.0104 (4)
0.0098 (5)
0.0123 (5)
0.0161 (5)
0.0125 (5)
0.0092 (4)
0.0097 (4)
0.0106 (5)
0.0139 (5)
0.0133 (5)
0.0127 (5)
0.0153 (5)
0.0123 (5)
0.0118 (5)
0.0100 (4)
0.0109 (5)
0.0130 (5)
0.0178 (5)
0.0160 (5)
0.0119 (5)
0.0132 (4)
0.0213 (5)
−0.0013 (3)
−0.0029 (3)
−0.0034 (3)
−0.0010 (4)
−0.0028 (4)
−0.0026 (4)
−0.0027 (4)
−0.0003 (4)
−0.0003 (4)
−0.0027 (4)
−0.0020 (4)
−0.0015 (4)
−0.0074 (5)
−0.0068 (5)
−0.0015 (4)
−0.0002 (4)
0.0001 (4)
−0.0025 (4)
−0.0042 (4)
−0.0019 (4)
−0.0020 (4)
−0.0026 (4)
−0.0023 (3)
0.0026 (4)
O3
Geometric parameters (Å, º)
O1—C13
N1—C1
N1—C5
N1—H1A
N2—C6
1.2298 (14)
C8—H8
C9—C10
C9—H9
C10—C11
C10—H10
0.95
1.388 (2)
0.95
1.3863 (19)
0.95
1.3387 (15)
1.3575 (15)
0.88
1.2901 (14)
Acta Cryst. (2019). C75
sup-7

supporting information
N2—N3
N3—C13
N3—H3A
N4—C13
N4—C14
N4—H4A
C1—C2
C1—H1
C2—C3
C2—H2
C3—C4
C3—H3
C4—C5
C4—H4
C5—C6
C6—C7
C7—C8
C7—C12
C8—C9
1.3448 (13)
1.3912 (14)
0.88
1.3507 (14)
1.4083 (14)
0.88
1.3790 (17)
0.95
1.3881 (17)
0.95
1.3910 (16)
0.95
1.3883 (16)
0.95
1.4777 (15)
1.4926 (16)
1.3942 (16)
1.3963 (17)
1.3935 (17)
C11—C12
C11—H11
C12—H12
C14—C19
C14—C15
C15—C16
C15—H15
C16—C17
C16—H16
C17—C18
C17—H17
C18—C19
C18—H18
C19—H19
O2—H1W
O2—H2W
O3—H3W
O3—H4W
1.3946 (17)
0.95
0.95
1.3946 (16)
1.3968 (15)
1.3858 (16)
0.95
1.3911 (17)
0.95
1.3874 (17)
0.95
1.3939 (16)
0.95
0.95
0.79 (2)
0.86 (2)
0.92 (2)
0.85 (2)
C1—N1—C5
C1—N1—H1A
C5—N1—H1A
C6—N2—N3
N2—N3—C13
N2—N3—H3A
C13—N3—H3A
C13—N4—C14
C13—N4—H4A
C14—N4—H4A
N1—C1—C2
N1—C1—H1
C2—C1—H1
C1—C2—C3
C1—C2—H2
C3—C2—H2
C2—C3—C4
C2—C3—H3
C4—C3—H3
C5—C4—C3
C5—C4—H4
C3—C4—H4
N1—C5—C4
N1—C5—C6
C4—C5—C6
N2—C6—C5
N2—C6—C7
C5—C6—C7
122.92 (10)
118.5
118.5
119.08 (10)
117.18 (9)
121.4
121.4
127.56 (10)
116.2
116.2
120.77 (11)
119.6
119.6
118.23 (11)
120.9
120.9
120.06 (11)
120
120
120.10 (11)
120
C10—C9—H9
C8—C9—H9
119.8
119.8
119.99 (11)
120
120
120.08 (12)
120
120
120.02 (11)
120
120
126.06 (10)
122.54 (10)
111.40 (10)
119.95 (10)
123.62 (10)
116.38 (10)
120.14 (11)
119.9
119.9
120.24 (11)
119.9
119.9
119.52 (11)
120.2
C11—C10—C9
C11—C10—H10
C9—C10—H10
C10—C11—C12
C10—C11—H11
C12—C11—H11
C11—C12—C7
C11—C12—H12
C7—C12—H12
O1—C13—N4
O1—C13—N3
N4—C13—N3
C19—C14—C15
C19—C14—N4
C15—C14—N4
C16—C15—C14
C16—C15—H15
C14—C15—H15
C15—C16—C17
C15—C16—H16
C17—C16—H16
C18—C17—C16
C18—C17—H17
C16—C17—H17
C17—C18—C19
C17—C18—H18
120
117.92 (10)
117.56 (10)
124.52 (10)
113.87 (10)
125.44 (10)
120.68 (10)
120.2
120.91 (11)
119.5
Acta Cryst. (2019). C75
sup-8

supporting information
C8—C7—C12
C8—C7—C6
C12—C7—C6
C9—C8—C7
C9—C8—H8
C7—C8—H8
C10—C9—C8
119.69 (11)
121.02 (11)
119.29 (10)
119.81 (12)
120.1
C19—C18—H18
C18—C19—C14
C18—C19—H19
C14—C19—H19
H1W—O2—H2W
H3W—O3—H4W
119.5
119.24 (10)
120.4
120.4
104.9 (18)
111 (2)
120.1
120.35 (12)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
O2—H1W···O1
N3—H3A···Cl1i
O3—H3W···Cl1ii
N1—H1A···O2
N4—H4A···Cl1i
O3—H4W···Cl1
O2—H2W···O3
0.79 (2)
0.88
0.92 (2)
0.88
0.88
0.85 (2)
0.86 (2)
2.01 (2)
2.5
2.25 (2)
1.8
2.29
2.35 (2)
1.90 (2)
2.7906 (13)
3.2698 (12)
3.1665 (14)
2.6531 (14)
3.1432 (13)
3.1973 (14)
2.7370 (15)
169.6 (19)
146
171.1 (19)
162
163
178 (2)
163.8 (18)
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x, y+1/2, −z+1/2.
2-[Phenyl({[(phenylcarbamoyl)amino]imino})methyl]pyridinium nitrate dihydrate (III)
Crystal data
C19H17N4O+·NO3−·2H2O
Mr = 415.41
F(000) = 872
Dx = 1.401 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 8565 reflections
θ = 2.7–27.9°
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 9.5556 (4) Å
b = 9.3050 (4) Å
c = 22.2715 (10) Å
β = 96.048 (2)°
µ = 0.11 mm−1
T = 100 K
Block, colourless
0.21 × 0.10 × 0.08 mm
V = 1969.24 (15) Å3
Z = 4
Data collection
Bruker D8 Venture Photon 100
diffractometer
Radiation source: microfocus X ray tube
φ and ω scans
6023 independent reflections
3810 reflections with I > 2σ(I)
Rint = 0.068
θ
max = 30.6°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2015)
h = −10→13
k = −11→13
l = −31→31
T
min = 0.683, Tmax = 0.746
42340 measured reflections
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.058
wR(F2) = 0.140
S = 1.02
6023 reflections
293 parameters
0 restraints
0 constraints
Hydrogen site location: mixed
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.055P)2 + 0.9729P]
where P = (Fo2 + 2Fc2)/3
Acta Cryst. (2019). C75
sup-9

supporting information
(Δ/σ)max = 0.001
Δρmax = 0.37 e Å−3
Δρmin = −0.54 e Å−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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Occ. (<1)
O1
N1
H1A
N2
N3
H3A
N4
H4A
C1
0.32424 (12)
0.61087 (14)
0.538
0.55957 (14)
0.52299 (14)
0.5761
0.36940 (14)
0.434
0.62604 (18)
0.5586
0.59204 (13)
0.92847 (15)
0.8701
0.74698 (14)
0.65225 (15)
0.6381
0.49149 (15)
0.4888
1.01918 (19)
1.0192
0.50656 (5)
0.44107 (6)
0.438
0.52725 (6)
0.56847 (6)
0.6027
0.60069 (6)
0.6319
0.39554 (8)
0.361
0.0272 (3)
0.0235 (3)
0.028*
0.0222 (3)
0.0231 (3)
0.028*
0.0257 (3)
0.031*
0.0276 (4)
0.033*
H1
C2
H2
0.73808 (19)
0.7494
1.11222 (19)
1.1762
0.39826 (8)
0.3659
0.0287 (4)
0.034*
C3
H3
0.83374 (18)
0.9118
1.11048 (19)
1.1742
0.44915 (8)
0.4522
0.0298 (4)
0.036*
C4
H4
0.81631 (17)
0.8822
1.01591 (19)
1.0152
0.49601 (8)
0.5311
0.0278 (4)
0.033*
C5
C6
C7
C8
0.70294 (16)
0.67558 (16)
0.77787 (16)
0.79217 (19)
0.7356
0.92278 (17)
0.81803 (17)
0.80131 (18)
0.90835 (19)
0.9924
0.49155 (7)
0.53874 (7)
0.59359 (7)
0.63769 (8)
0.6332
0.0220 (3)
0.0222 (3)
0.0232 (3)
0.0283 (4)
0.034*
H8
C9
H9
0.8892 (2)
0.898
0.8918 (2)
0.9643
0.68806 (8)
0.7183
0.0341 (4)
0.041*
C10
H10
C11
H11
C12
H12
C13
C14
C15
H15
C16
H16
C17
H17
0.97306 (19)
1.0416
0.95692 (18)
1.013
0.85883 (18)
0.8471
0.39750 (17)
0.24971 (17)
0.25362 (19)
0.3352
0.7707 (2)
0.7615
0.6625 (2)
0.5782
0.6771 (2)
0.6023
0.57767 (17)
0.40541 (17)
0.31422 (19)
0.311
0.69468 (8)
0.7286
0.65172 (8)
0.6567
0.60138 (8)
0.5723
0.55469 (7)
0.60497 (7)
0.65482 (8)
0.6831
0.0323 (4)
0.039*
0.0313 (4)
0.038*
0.0281 (4)
0.034*
0.0228 (3)
0.0240 (3)
0.0304 (4)
0.036*
0.1394 (2)
0.1436
0.0190 (2)
−0.0598
0.2286 (2)
0.1656
0.2338 (2)
0.1755
0.66323 (9)
0.6969
0.62299 (9)
0.6292
0.0344 (4)
0.041*
0.0353 (4)
0.042*
Acta Cryst. (2019). C75
sup-10

supporting information
C18
H18
C19
H19
N5
0.0146 (2)
−0.068
0.12930 (18)
0.1254
0.35984 (18)
0.27741 (16)
0.4492 (2)
0.3005 (3)
0.4115 (4)
0.36998 (14)
0.359 (2)
0.32443 (19)
0.3281
0.41061 (18)
0.4721
0.7937 (2)
0.73306 (18)
0.8758 (3)
0.8518 (4)
0.7187 (4)
0.78603 (15)
0.721 (3)
0.57376 (8)
0.5461
0.56400 (8)
0.5298
0.0337 (4)
0.04*
0.0277 (4)
0.033*
0.0420 (4)
0.0475 (4)
0.0799 (7)
0.0435 (11)
0.0774 (15)
0.0318 (3)
0.048*
0.26526 (7)
0.29534 (6)
0.28338 (8)
0.21244 (13)
0.22044 (14)
0.41599 (6)
0.4424 (11)
0.3815 (12)
0.18834 (6)
0.2169 (12)
0.2014 (12)
O3
O4
O5A
O5B
O2
H1W
H2W
O6
0.448 (4)
0.552 (4)
0.342 (2)
0.60636 (15)
0.563 (3)
0.755 (3)
0.95394 (19)
0.907 (3)
0.048*
0.0431 (4)
0.065*
H3W
H4W
0.656 (3)
1.044 (3)
0.065*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
O1
N1
N2
N3
N4
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
N5
0.0320 (6)
0.0258 (7)
0.0244 (7)
0.0235 (7)
0.0228 (7)
0.0330 (9)
0.0355 (9)
0.0290 (9)
0.0247 (8)
0.0235 (8)
0.0223 (8)
0.0211 (7)
0.0330 (9)
0.0424 (11)
0.0272 (9)
0.0272 (8)
0.0277 (8)
0.0261 (8)
0.0283 (8)
0.0315 (9)
0.0429 (11)
0.0423 (11)
0.0398 (10)
0.0360 (9)
0.0413 (9)
0.0451 (8)
0.0730 (12)
0.0423 (19)
0.109 (3)
0.0274 (6)
0.0223 (7)
0.0218 (7)
0.0262 (7)
0.0290 (7)
0.0281 (9)
0.0257 (8)
0.0285 (9)
0.0320 (9)
0.0231 (8)
0.0241 (8)
0.0272 (8)
0.0245 (8)
0.0338 (10)
0.0462 (11)
0.0415 (10)
0.0340 (9)
0.0200 (8)
0.0191 (7)
0.0308 (9)
0.0273 (9)
0.0262 (9)
0.0280 (9)
0.0221 (8)
0.0690 (12)
0.0632 (10)
0.1290 (18)
0.060 (2)
0.0225 (6)
0.0234 (7)
0.0217 (6)
0.0201 (6)
0.0259 (7)
0.0230 (8)
0.0278 (8)
0.0341 (9)
0.0276 (8)
0.0209 (7)
0.0214 (7)
0.0227 (8)
0.0279 (8)
0.0261 (9)
0.0239 (8)
0.0265 (9)
0.0238 (8)
0.0237 (8)
0.0267 (8)
0.0308 (9)
0.0367 (10)
0.0399 (10)
0.0336 (10)
0.0259 (8)
0.0153 (7)
0.0341 (7)
0.0398 (9)
0.0261 (16)
0.0463 (19)
−0.0074 (5)
0.0041 (5)
0.0079 (5)
0.0084 (5)
0.0047 (5)
0.0055 (5)
0.0091 (7)
0.0162 (7)
0.0136 (7)
0.0075 (7)
0.0086 (6)
0.0079 (6)
0.0084 (6)
0.0055 (7)
0.0026 (8)
0.0044 (7)
0.0087 (7)
0.0082 (7)
0.0084 (6)
0.0134 (7)
0.0126 (7)
0.0208 (8)
0.0166 (9)
0.0056 (8)
0.0073 (7)
0.0002 (6)
0.0034 (6)
0.0160 (8)
−0.0057 (13)
0.0351 (19)
0.0012 (5)
−0.0009 (5)
0.0006 (5)
0.0039 (5)
0.0053 (6)
0.0030 (7)
0.0043 (7)
0.0009 (7)
0.0005 (7)
−0.0016 (6)
−0.0007 (6)
0.0020 (6)
0.0019 (7)
−0.0011 (7)
0.0073 (8)
0.0058 (8)
−0.0011 (7)
−0.0015 (6)
−0.0015 (6)
0.0065 (7)
0.0051 (8)
−0.0042 (8)
−0.0054 (7)
−0.0038 (7)
−0.0117 (7)
0.0024 (7)
−0.0220 (11)
0.0111 (14)
−0.0313 (17)
−0.0013 (6)
0.0005 (6)
−0.0013 (6)
−0.0008 (6)
0.0029 (7)
0.0033 (7)
−0.0042 (7)
−0.0027 (7)
0.0018 (6)
0.0024 (6)
−0.0025 (7)
−0.0027 (7)
−0.0081 (8)
−0.0064 (8)
0.0067 (8)
0.0035 (7)
0.0010 (6)
0.0006 (6)
0.0049 (8)
0.0009 (8)
−0.0122 (8)
−0.0127 (8)
−0.0072 (7)
−0.0250 (9)
−0.0108 (7)
−0.0472 (13)
−0.0135 (16)
−0.036 (2)
O3
O4
O5A
O5B
0.082 (3)
Acta Cryst. (2019). C75
sup-11

supporting information
O2
O6
0.0369 (7)
0.0371 (8)
0.0350 (7)
0.0598 (10)
0.0232 (6)
0.0333 (8)
−0.0070 (6)
−0.0059 (7)
0.0023 (5)
0.0082 (6)
0.0055 (5)
−0.0129 (7)
Geometric parameters (Å, º)
O1—C13
N1—C1
N1—C5
N1—H1A
N2—C6
N2—N3
N3—C13
N3—H3A
N4—C13
N4—C14
N4—H4A
C1—C2
C1—H1
C2—C3
C2—H2
C3—C4
C3—H3
C4—C5
C4—H4
C5—C6
C6—C7
C7—C12
C7—C8
C8—C9
C8—H8
C9—C10
1.224 (2)
C9—H9
0.95
1.386 (3)
0.95
1.390 (2)
0.95
0.95
1.392 (2)
1.395 (2)
1.380 (3)
0.95
1.383 (3)
0.95
1.381 (3)
0.95
1.393 (2)
0.95
1.339 (2)
1.354 (2)
0.88
C10—C11
C10—H10
C11—C12
C11—H11
C12—H12
C14—C19
C14—C15
C15—C16
C15—H15
C16—C17
C16—H16
C17—C18
C17—H17
C18—C19
C18—H18
C19—H19
N5—O4
1.293 (2)
1.3451 (18)
1.391 (2)
0.88
1.350 (2)
1.408 (2)
0.88
1.373 (2)
0.95
1.379 (3)
0.95
1.389 (2)
0.95
1.383 (2)
0.95
1.477 (2)
1.490 (2)
1.391 (2)
1.395 (2)
1.386 (2)
0.95
0.95
1.185 (2)
1.224 (2)
1.353 (3)
1.363 (3)
0.86 (3)
0.84 (3)
0.91 (3)
0.99 (3)
N5—O3
N5—O5B
N5—O5A
O2—H1W
O2—H2W
O6—H3W
O6—H4W
1.382 (3)
C1—N1—C5
C1—N1—H1A
C5—N1—H1A
C6—N2—N3
N2—N3—C13
N2—N3—H3A
C13—N3—H3A
C13—N4—C14
C13—N4—H4A
C14—N4—H4A
N1—C1—C2
N1—C1—H1
C2—C1—H1
C1—C2—C3
C1—C2—H2
C3—C2—H2
122.74 (15)
118.6
118.6
118.62 (14)
117.15 (13)
121.4
121.4
128.13 (14)
115.9
115.9
120.68 (16)
119.7
C9—C10—C11
C9—C10—H10
C11—C10—H10
C10—C11—C12
C10—C11—H11
C12—C11—H11
C11—C12—C7
C11—C12—H12
C7—C12—H12
O1—C13—N4
O1—C13—N3
N4—C13—N3
C19—C14—C15
C19—C14—N4
C15—C14—N4
C16—C15—C14
119.83 (17)
120.1
120.1
120.15 (17)
119.9
119.9
120.04 (17)
120
120
126.03 (15)
122.58 (14)
111.39 (14)
119.60 (16)
123.86 (15)
116.51 (15)
120.28 (17)
119.7
118.35 (16)
120.8
120.8
Acta Cryst. (2019). C75
sup-12

supporting information
C2—C3—C4
C2—C3—H3
C4—C3—H3
C5—C4—C3
C5—C4—H4
C3—C4—H4
N1—C5—C4
N1—C5—C6
C4—C5—C6
N2—C6—C5
N2—C6—C7
C5—C6—C7
C12—C7—C8
C12—C7—C6
C8—C7—C6
C9—C8—C7
C9—C8—H8
C7—C8—H8
C10—C9—C8
C10—C9—H9
C8—C9—H9
120.23 (16)
119.9
119.9
119.88 (16)
120.1
120.1
118.10 (15)
117.94 (14)
123.96 (15)
114.14 (14)
125.70 (14)
120.16 (14)
119.55 (16)
119.81 (15)
120.64 (15)
119.86 (17)
120.1
C16—C15—H15
C14—C15—H15
C15—C16—C17
C15—C16—H16
C17—C16—H16
C18—C17—C16
C18—C17—H17
C16—C17—H17
C17—C18—C19
C17—C18—H18
C19—C18—H18
C14—C19—C18
C14—C19—H19
C18—C19—H19
O4—N5—O3
119.9
119.9
120.53 (17)
119.7
119.7
119.32 (17)
120.3
120.3
121.13 (18)
119.4
119.4
119.15 (16)
120.4
120.4
126.39 (16)
106.1 (2)
118.2 (2)
104.9 (2)
114.96 (19)
109 (2)
116 (2)
O4—N5—O5B
O3—N5—O5B
O4—N5—O5A
O3—N5—O5A
H1W—O2—H2W
H3W—O6—H4W
120.1
120.50 (17)
119.7
119.7
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
N1—H1A···O2
N3—H3A···O6i
N4—H4A···O6i
O2—H1W···O1
O2—H2W···O3
O6—H3W···O4
O6—H3W···O5A
O6—H3W···O5B
O6—H4W···O3ii
O6—H4W···O5Bii
0.88
0.88
0.88
0.86 (3)
0.84 (3)
0.91 (3)
0.91 (3)
0.91 (3)
0.99 (3)
0.99 (3)
1.81
2.08
2.03
1.92 (3)
1.96 (3)
1.95 (3)
2.55 (3)
2.28 (3)
1.87 (3)
2.51 (3)
2.6639 (19)
2.8794 (19)
2.875 (2)
2.7756 (17)
2.783 (2)
2.816 (2)
3.172 (3)
3.008 (4)
2.833 (2)
3.210 (4)
164
150
159
174 (2)
165 (2)
159 (2)
126 (2)
137 (2)
163 (2)
127.0 (19)
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+1, y+1/2, −z+1/2.
2-[Phenyl({[(phenylcarbamoyl)amino]imino})methyl]pyridinium thiocyanate 2.5-hydrate (IV)
Crystal data
C19H17N4O+·NCS−·2.5H2O
Mr = 420.48
V = 2013.87 (11) Å3
Z = 4
Monoclinic, P21/n
Hall symbol: -P 2yn
a = 13.0053 (4) Å
b = 7.7965 (2) Å
c = 20.8703 (7) Å
β = 107.887 (1)°
F(000) = 884
Dx = 1.387 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 9596 reflections
θ = 2.8–30.4°
µ = 0.20 mm−1
Acta Cryst. (2019). C75
sup-13

supporting information
T = 100 K
0.24 × 0.10 × 0.05 mm
Block, colourless
Data collection
Bruker D8 Venture Photon 100
diffractometer
Radiation source: microfocus X ray tube
φ and ω scans
6146 independent reflections
4590 reflections with I > 2σ(I)
Rint = 0.040
θ
max = 30.6°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2015)
h = −18→18
k = −9→11
l = −29→29
T
min = 0.707, Tmax = 0.746
31447 measured reflections
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.049
wR(F2) = 0.131
S = 1.02
Hydrogen site location: mixed
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0561P)2 + 1.2977P]
where P = (Fo2 + 2Fc2)/3
6146 reflections
326 parameters
6 restraints
(Δ/σ)max < 0.001
Δρmax = 0.4 e Å−3
Δρmin = −0.41 e Å−3
0 constraints
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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Occ. (<1)
O1
N1
H1A
N2
N3
H3A
N4
H4A
C1
H1
C2
H2
C3
H3
C4
H4
C5
C6
C7
0.47184 (8)
0.61991 (9)
0.6215
0.44095 (9)
0.35678 (9)
0.29
0.28807 (9)
0.2267
0.71372 (11)
0.7798
0.71496 (11)
0.7811
0.61693 (12)
0.6155
0.52099 (11)
0.454
0.52304 (10)
0.42486 (10)
0.32143 (10)
0.41475 (14)
0.14483 (15)
0.203
0.23927 (15)
0.30584 (16)
0.2947
0.44702 (15)
0.42
0.09103 (18)
0.1174
−0.00216 (19)
−0.0414
−0.03710 (19)
−0.1005
0.02051 (18)
−0.0039
0.11323 (17)
0.17971 (17)
0.17993 (17)
0.59764 (5)
0.45619 (6)
0.4926
0.48298 (6)
0.49958 (6)
0.4729
0.57257 (6)
0.5421
0.44878 (7)
0.4824
0.39290 (7)
0.3877
0.34444 (8)
0.3053
0.35314 (7)
0.32
0.40989 (7)
0.42306 (7)
0.36716 (7)
0.0210 (2)
0.0149 (2)
0.018*
0.0152 (2)
0.0177 (2)
0.021*
0.0174 (2)
0.021*
0.0180 (3)
0.022*
0.0197 (3)
0.024*
0.0209 (3)
0.025*
0.0182 (3)
0.022*
0.0141 (3)
0.0143 (2)
0.0149 (3)
Acta Cryst. (2019). C75
sup-14

supporting information
C8
H8
0.31493 (11)
0.376
0.27020 (19)
0.3318
0.30834 (7)
0.3048
0.0197 (3)
0.024*
C9
H9
0.21989 (12)
0.2161
0.2705 (2)
0.3321
0.25502 (8)
0.2151
0.0219 (3)
0.026*
C10
H10
C11
0.13050 (12)
0.0656
0.13570 (11)
0.0741
0.23077 (11)
0.2343
0.37967 (11)
0.28004 (11)
0.17552 (12)
0.1152
0.18130 (19)
0.1813
0.09185 (19)
0.0316
0.09030 (18)
0.0282
0.39275 (17)
0.54163 (17)
0.5914 (2)
0.5589
0.25987 (8)
0.2232
0.31826 (8)
0.3216
0.37174 (7)
0.4115
0.56052 (7)
0.62831 (7)
0.62653 (8)
0.5896
0.0209 (3)
0.025*
0.0209 (3)
0.025*
0.0179 (3)
0.022*
0.0162 (3)
0.0163 (3)
0.0218 (3)
0.026*
H11
C12
H12
C13
C14
C15
H15
C16
0.16016 (13)
0.0892
0.6876 (2)
0.7209
0.67847 (8)
0.677
0.0252 (3)
0.03*
H16
C17
H17
C18
H18
C19
H19
S1A
C20A
N5A
O3A
H3WA
H4WA
S1B
C20B
N5B
O3B
H3WB
H4WB
O2
0.24754 (13)
0.2369
0.35041 (13)
0.4103
0.36737 (11)
0.4384
0.7358 (2)
0.8039
0.68370 (19)
0.7143
0.58715 (18)
0.5526
0.73280 (8)
0.768
0.73511 (8)
0.7727
0.68315 (7)
0.6852
0.0243 (3)
0.029*
0.0231 (3)
0.028*
0.0188 (3)
0.023*
0.0352 (6)
0.0380 (13)
0.0572 (18)
0.0432 (12)
0.065*
0.89347 (17)
0.9293 (4)
0.9541 (3)
0.1094 (3)
0.068 (3)
0.077 (3)
0.9023 (2)
0.9362 (5)
0.9595 (5)
0.1309 (4)
0.110 (4)
0.098 (5)
0.65756 (10)
0.604 (2)
0.714 (2)
−0.0067 (3)
−0.0156
0.4590 (5)
0.3324 (9)
0.2489 (9)
0.2788 (8)
0.319 (6)
0.204 (5)
0.4113 (5)
0.2778 (9)
0.1776 (7)
0.3389 (7)
0.407 (5)
0.243 (4)
0.29775 (19)
0.340 (3)
0.346 (3)
0.0865 (5)
0.0898
0.6458 (2)
0.5930 (3)
0.5538 (3)
0.4800 (2)
0.4430 (14)
0.496 (2)
0.6645 (2)
0.6152 (4)
0.5811 (3)
0.4610 (3)
0.4269 (17)
0.453 (3)
0.57474 (6)
0.5815 (12)
0.5973 (13)
0.46176 (17)
0.5085
0.571 (10)
0.571 (10)
0.571 (10)
0.571 (10)
0.571 (10)
0.571 (10)
0.429 (10)
0.429 (10)
0.429 (10)
0.429 (10)
0.429 (10)
0.429 (10)
0.065*
0.0313 (5)
0.0328 (13)
0.0436 (13)
0.0346 (11)
0.052*
0.052*
0.0339 (3)
0.051*
H1W
H2W
O4
H5W
H6W
0.051*
0.0568 (8)
0.085*
0.5
0.5
0.5
0.0065
−0.036
0.4523
0.085*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
O1
N1
N2
N3
0.0158 (5)
0.0160 (5)
0.0157 (5)
0.0139 (5)
0.0269 (5)
0.0168 (5)
0.0156 (5)
0.0215 (6)
0.0219 (5)
0.0135 (5)
0.0172 (6)
0.0195 (6)
0.0016 (4)
0.0018 (4)
0.0024 (4)
0.0027 (4)
0.0084 (4)
0.0068 (4)
0.0092 (4)
0.0080 (4)
−0.0045 (4)
0.0022 (4)
0.0026 (4)
−0.0014 (5)
Acta Cryst. (2019). C75
sup-15

supporting information
N4
C1
C2
C3
C4
C5
C6
C7
0.0146 (5)
0.0149 (6)
0.0191 (6)
0.0252 (7)
0.0185 (6)
0.0150 (6)
0.0138 (6)
0.0145 (6)
0.0163 (6)
0.0220 (7)
0.0186 (6)
0.0178 (6)
0.0193 (6)
0.0185 (6)
0.0201 (6)
0.0185 (6)
0.0242 (7)
0.0327 (8)
0.0274 (7)
0.0202 (6)
0.0246 (5)
0.0224 (16)
0.0403 (19)
0.0255 (14)
0.0217 (6)
0.036 (3)
0.0208 (6)
0.0207 (7)
0.0208 (7)
0.0202 (7)
0.0187 (6)
0.0131 (6)
0.0140 (6)
0.0148 (6)
0.0220 (7)
0.0238 (7)
0.0199 (7)
0.0194 (7)
0.0177 (6)
0.0153 (6)
0.0144 (6)
0.0259 (7)
0.0273 (8)
0.0204 (7)
0.0204 (7)
0.0166 (6)
0.0454 (12)
0.054 (3)
0.0185 (6)
0.0195 (7)
0.0229 (7)
0.0219 (7)
0.0189 (7)
0.0158 (6)
0.0167 (6)
0.0163 (6)
0.0219 (7)
0.0192 (7)
0.0211 (7)
0.0260 (8)
0.0183 (7)
0.0179 (7)
0.0184 (7)
0.0243 (8)
0.0314 (8)
0.0279 (8)
0.0249 (8)
0.0228 (7)
0.0383 (11)
0.039 (3)
0.0025 (4)
0.0034 (5)
0.0054 (5)
0.0026 (5)
0.0002 (5)
0.0012 (5)
0.0006 (5)
0.0014 (5)
0.0007 (5)
0.0037 (6)
0.0024 (5)
−0.0030 (5)
−0.0006 (5)
0.0018 (5)
0.0022 (5)
0.0026 (6)
0.0043 (6)
−0.0004 (6)
−0.0022 (6)
0.0014 (5)
−0.0050 (6)
−0.0089 (19)
−0.007 (2)
0.0072 (15)
−0.0032 (6)
−0.009 (2)
−0.004 (2)
0.0023 (16)
0.0060 (5)
−0.0040 (17)
0.0078 (4)
0.0071 (5)
0.0122 (6)
0.0139 (6)
0.0080 (5)
0.0069 (5)
0.0068 (5)
0.0063 (5)
0.0073 (5)
0.0052 (6)
0.0017 (5)
0.0076 (6)
0.0080 (5)
0.0102 (5)
0.0119 (5)
0.0114 (6)
0.0195 (6)
0.0214 (7)
0.0132 (6)
0.0111 (6)
0.0136 (6)
0.0109 (18)
0.0193 (19)
−0.0012 (12)
0.0068 (7)
0.012 (2)
−0.0007 (5)
0.0073 (5)
0.0063 (6)
−0.0008 (6)
−0.0005 (5)
0.0036 (5)
0.0031 (5)
−0.0002 (5)
0.0053 (6)
0.0065 (6)
−0.0004 (5)
−0.0019 (6)
0.0012 (5)
0.0020 (5)
0.0032 (5)
0.0020 (6)
0.0019 (6)
−0.0014 (6)
−0.0019 (6)
0.0015 (5)
−0.0152 (8)
−0.016 (2)
−0.033 (3)
−0.0149 (17)
−0.0009 (8)
0.006 (2)
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
S1A
C20A
N5A
O3A
S1B
C20B
N5B
O3B
O2
0.076 (4)
0.064 (3)
0.0371 (11)
0.032 (3)
0.036 (3)
0.044 (3)
0.0557 (8)
0.055 (2)
0.058 (3)
0.033 (2)
0.0338 (11)
0.031 (3)
0.038 (3)
0.031 (2)
0.0280 (6)
0.055 (2)
0.063 (3)
0.025 (2)
0.009 (2)
0.0267 (19)
0.0160 (5)
0.066 (2)
0.0051 (15)
0.0041 (5)
0.0280 (17)
−0.0012 (17)
−0.0176 (6)
−0.0048 (16)
O4
Geometric parameters (Å, º)
O1—C13
N1—C1
N1—C5
N1—H1A
N2—C6
N2—N3
N3—C13
N3—H3A
N4—C13
N4—C14
N4—H4A
C1—C2
1.2232 (17)
C10—H10
0.95
1.388 (2)
0.95
1.3431 (17)
1.3542 (17)
0.88
1.2895 (18)
1.3492 (15)
1.3902 (18)
0.88
1.3585 (17)
1.4081 (18)
0.88
1.378 (2)
0.95
C11—C12
C11—H11
C12—H12
C14—C19
C14—C15
C15—C16
C15—H15
C16—C17
C16—H16
C17—C18
C17—H17
C18—C19
C18—H18
C19—H19
0.95
1.388 (2)
1.4030 (19)
1.382 (2)
0.95
1.388 (2)
0.95
1.385 (2)
0.95
1.392 (2)
0.95
C1—H1
C2—C3
C2—H2
1.389 (2)
0.95
0.95
Acta Cryst. (2019). C75
sup-16

supporting information
C3—C4
C3—H3
C4—C5
C4—H4
C5—C6
C6—C7
C7—C8
C7—C12
C8—C9
C8—H8
C9—C10
C9—H9
C10—C11
1.3894 (19)
0.95
1.3809 (19)
0.95
1.4798 (18)
1.4855 (18)
1.3950 (19)
1.3988 (19)
1.386 (2)
0.95
S1A—C20A
C20A—N5A
O3A—H3WA
O3A—H4WA
S1B—C20B
C20B—N5B
O3B—H3WB
O3B—H4WB
O2—H1W
1.650 (5)
1.166 (6)
0.855 (10)
0.850 (10)
1.616 (8)
1.159 (8)
0.863 (10)
0.856 (10)
0.82 (3)
O2—H2W
O4—H5W
O4—H6W
0.83 (3)
1.016
1.0012
1.385 (2)
0.95
1.388 (2)
C1—N1—C5
C1—N1—H1A
C5—N1—H1A
C6—N2—N3
N2—N3—C13
N2—N3—H3A
C13—N3—H3A
C13—N4—C14
C13—N4—H4A
C14—N4—H4A
N1—C1—C2
N1—C1—H1
C2—C1—H1
C1—C2—C3
C1—C2—H2
C3—C2—H2
C2—C3—C4
C2—C3—H3
C4—C3—H3
C5—C4—C3
C5—C4—H4
C3—C4—H4
N1—C5—C4
N1—C5—C6
C4—C5—C6
N2—C6—C5
N2—C6—C7
C5—C6—C7
C8—C7—C12
C8—C7—C6
C12—C7—C6
C9—C8—C7
C9—C8—H8
C7—C8—H8
122.68 (12)
118.7
118.7
119.00 (12)
117.37 (11)
121.3
121.3
127.43 (12)
116.3
116.3
120.60 (13)
119.7
119.7
118.20 (13)
120.9
120.9
120.11 (13)
119.9
119.9
119.98 (13)
120
C9—C10—C11
C9—C10—H10
C11—C10—H10
C10—C11—C12
C10—C11—H11
C12—C11—H11
C11—C12—C7
C11—C12—H12
C7—C12—H12
O1—C13—N4
120.07 (13)
120
120
120.10 (13)
119.9
119.9
120.14 (13)
119.9
119.9
125.70 (13)
122.73 (12)
111.57 (12)
119.45 (13)
124.44 (12)
116.10 (13)
120.10 (14)
119.9
119.9
120.55 (14)
119.7
119.7
119.26 (14)
120.4
120.4
120.93 (15)
119.5
119.5
119.68 (13)
120.2
120.2
177.1 (5)
111 (3)
177.7 (5)
111 (3)
O1—C13—N3
N4—C13—N3
C19—C14—C15
C19—C14—N4
C15—C14—N4
C16—C15—C14
C16—C15—H15
C14—C15—H15
C15—C16—C17
C15—C16—H16
C17—C16—H16
C18—C17—C16
C18—C17—H17
C16—C17—H17
C17—C18—C19
C17—C18—H18
C19—C18—H18
C14—C19—C18
C14—C19—H19
C18—C19—H19
N5A—C20A—S1A
120
118.41 (12)
118.07 (12)
123.52 (12)
114.46 (12)
126.82 (12)
118.65 (12)
119.19 (13)
119.16 (12)
121.65 (12)
120.36 (13)
119.8
H3WA—O3A—H4WA
N5B—C20B—S1B
H3WB—O3B—H4WB
119.8
Acta Cryst. (2019). C75
sup-17

supporting information
C10—C9—C8
C10—C9—H9
C8—C9—H9
120.14 (14)
119.9
119.9
H1W—O2—H2W
H5W—O4—H6W
112 (2)
106.9
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
N1—H1A···O2
0.88
0.88
0.88
0.88
1.79
2.4
2.04
2
2.6531 (17)
3.123 (5)
2.809 (5)
2.845 (4)
2.718 (4)
2.7575 (15)
3.225 (2)
3.280 (3)
3.319 (5)
3.185 (5)
166
139
146
160
N3—H3A···O3A
N3—H3A···O3B
N4—H4A···O3A
N4—H4A···O3B
O2—H1W···O1
O2—H2W···S1A
O2—H2W···S1B
O3A—H3WA···S1Ai
O3B—H3WB···S1Bi
0.88
1.88
160
0.82 (3)
0.83 (3)
0.83 (3)
0.86 (1)
0.86 (1)
1.94 (3)
2.40 (3)
2.47 (3)
2.69 (3)
2.34 (2)
174 (2)
168 (2)
164 (2)
131 (4)
166 (5)
Symmetry code: (i) −x+1, −y+1, −z+1.
Acta Cryst. (2019). C75
sup-18