A combined X-ray crystallography and theoretical study of N—H…OX (X is =P and —C) hydrogen bonds in two new structures with a (C—O)2(N)P(=Y) (Y is O and S) skeleton

Article abstract of DOI:10.1107/S2053229618014006

The crystal structures of N,N′-(cyclohexane-1,4-diyl)bis(O,O′-diphenylphosphoramide), C₃₀H₃₂N₂O₆P₂ or (C₆H₅O)₂P(O)(1-NH)(C₆H₁₀)(4-NH)P(O)(OC

Full text of DOI:10.1107/S2053229618014006

research papers
A combined X-ray crystallography and theoretical
study of N—Hꢀ ꢀ ꢀOX (X is P and —C) hydrogen
bonds in two new structures with a (C—O)2(N)-
P( Y) (Y is O and S) skeleton
ISSN 2053-2296
Banafsheh Vahdani Alviri,a Mehrdad Pourayoubi,a* Abolghasem Farhadipour,a
b,c
Marek Necas and Valerio Bertolasid
ˇ
Received 25 July 2018
Accepted 2 October 2018
aDepartment of Chemistry, Faculty of Science, Ferdowsi University of Mashhad, Mashhad, Iran, bDepartment of
Chemistry, Masaryk University, Kotlarska 2, Brno CZ-6113, Czech Republic, cCEITEC–Central European Institute of
Technology, Masaryk University, Kamenice 5, 62500 Brno, Czech Republic, and dDipartimento di Scienze Chimiche e
Edited by E. Y. Cheung, Amgen Inc., USA
`
Farmaceutiche and Centro di Strutturistica Diffrattometrica, Universita di Ferrara, 44121 Ferrara, Italy. *Correspondence
Keywords: phosphoramide; thiophospho-
ramide; X-ray diffraction; N—Hꢀ ꢀ ꢀO hydrogen
bond; crystal structure; quantum chemical
calculations; Hirshfeld surface analysis.
e-mail: pourayoubi@um.ac.ir
The crystal structures of N,N0-(cyclohexane-1,4-diyl)bis(O,O0-diphenylphosphor-
amide), C30H32N2O6P2 or (C6H5O)2P(O)(1-NH)(C6H10)(4-NH)P(O)(OC6H5)2,
(I), and N,N0-(1,4-phenylene)bis(O,O0-dimethylthiophosphoramide), C10H18-
N2O4P2S2 or (CH3O)2P(S)(1-NH)(C6H4)(4-NH)P(S)(OCH3)2, (II), have been
investigated. In the structure of (I), with an (O)2(N)P(O) skeleton, two
symmetry-independent phosphoramide molecules are linked through N—
Hꢀ ꢀ ꢀO P hydrogen bonds. In the structure of (II), with an (O)2(N)P(S)
skeleton, the ester O atoms take part in N—Hꢀ ꢀ ꢀO—C hydrogen bonds as
acceptors; the P S groups do not participate in hydrogen-bonding interactions.
The strengths of these hydrogen bonds were evaluated, using quantum chemical
calculations with the GAUSSIAN09 software package at the B3LYP/6-
311G(d,p) level of theory. For this, LP(O) to ꢀ*(NH) charge transfers were
studied, according to the second-order perturbation theory in natural bond
orbital (NBO) methodology, for a three-component cluster of hydrogen-bonded
molecules for both structures, including all of the independent N—Hꢀ ꢀ ꢀO
hydrogen bonds observed in the crystal packing. The details of the inter-
molecular interactions were studied by Hirshfeld surface maps and two-
dimensional fingerprint plots.
CCDC references: 1405616; 1871198
Supporting information: this article has
supporting information at journals.iucr.org/c
1. Introduction
The N—Hꢀ ꢀ ꢀO P hydrogen bond is the predominant feature
in different families of (NH)P O-based compounds and
usually acts as a directing interaction in supramolecular
structures (Saneei et al., 2018). In various published articles,
different aspects regarding hydrogen bonds, including their
ˇ
strengths (Hamzehee, Pourayoubi, Necas et al., 2017), patterns
(Pourayoubi, Toghraee et al., 2014) and motifs (Pourayoubi,
Tarahhomi et al., 2012) were studied through a statistical
analysis of the Cambridge Structural Database (CSD; Groom
et al., 2016). Furthermore, theoretical approaches were
applied to the evaluation of hydrogen-bond strengths in
compounds with (C)2(N)P(O), (N)3P(O) and (O)2(N)P(O)
skeletons (Hamzehee, Pourayoubi, Farhadipour et al., 2017;
Pourayoubi et al., 2013; Gholivand et al., 2013).
In the hydrogen bonds formed, the P O group has a better
acceptor capability than the other acceptor groups that usually
exist in the structures, typically C O (Vahdani Alviri et al.,
2018), S O (Pourayoubi et al., 2011) and N O/N—O
(Gholivand et al., 2009), and a much better capability than
# 2018 International Union of Crystallography
1610 https://doi.org/10.1107/S2053229618014006
Acta Cryst. (2018). C74, 1610–1621

research papers
acceptors such as P S (Cupertino et al., 1998), C S (Omrani
et al., 2015) and OAr (Ar = aryl) (Sabbaghi et al., 2016) groups.
Thus, the P O group usually dictates the hydrogen-bond
pattern as the best hydrogen-bond acceptor in the molecule.
On the other hand, if there is only one hydrogen-bond donor
in a molecule, it usually selects the P O as a partner to form a
hydrogen-bond interaction. In thiophosphoryl-based com-
pounds with a typical ester O atom (OCP in the C—OCP—P
fragment), there is competition between OCP, with a small
hydrogen-bond acceptor capability, and the P S group
(Sabbaghi et al., 2016).
(I), and thiophosphoramide (CH3O)2P(S)NH(C6H4)NHP-
(S)(OCH3)2, (II) (Scheme 1). The strengths of two kinds of
hydrogen bonds, namely N—Hꢀ ꢀ ꢀO P in (I) and N—
Hꢀ ꢀ ꢀOCP in (II), were investigated by quantum chemical
calculations. A Hirshfeld surface analysis was performed on
the newly determined structures in order to explore the
intermolecular interactions in the crystal networks.
2. Experimental
2.1. Synthesis and crystallization
2.1.1. Synthesis of (I). To a solution of diphenyl phosphoryl
chloride (2.2 mmol) in dry CH3CN (20 ml), a solution of trans-
1,4-diaminocyclohexane (1.1 mmol) and triethylamine
(2.2 mmol) in the same solvent was added and stirred at 273 K.
Stirring was continued for 4 h and then the solvent was
removed in a vacuum. The solid obtained was washed with
distilled water. Colourless single crystals suitable for X-ray
analysis were obtained at room temperature from a CH3OH/
CHCl3 (4:1 v/v) mixture.
Analytical data: colourless block-shaped crystal. IR (KBr,
cmꢁ1): 3206, 2928, 1594, 1490, 1459, 1251, 1223, 1198, 1163,
1114, 1024, 940, 770, 687. 31P{1H} NMR (121.8 MHz, DMSO-
1
d6): ꢁ ꢁ0.30 (s). H NMR (300.8 MHz, DMSO-d6): ꢁ 1.20 (m,
4H, CH2), 1.66 (m, 4H, CH2), 2.93 (m, 2H, CH), 5.78 (dd, J =
13.4 Hz, J = 9.5 Hz, 2H, NH), 7.22 (m, 12H, Ar–H), 7.40 (m,
8H, Ar–H). 13C NMR (75.6 MHz, DMSO-d6): ꢁ 33.91 (s), 50.46
(s), 120.60 (d, JP–C = 5.3 Hz, Cortho), 125.16 (s), 130.21 (s),
2
151.18 (d, JP–C = 6.8 Hz, Cipso). MS (70 eV, EI): m/z (%)
579 (4) [M + 1]+, 578 (12) [M]+, 577 (< 1) [M ꢁ 1]+, 345 (100)
[M ꢁ (C6H5O)2PO]+, 233 (5) [C12H10O3P]+, 156 (14) [C6H5-
O3P]+, 77 (30) [C6H5]+.
Typical examples for a comparison between the hydrogen-
bond-acceptor capability of P Y (Y = O and S) and an ester
O atom, studied using the CSD, are compounds with the
(C—O)2–x(O)x(NH)P(S) and (C—O)2–x(O)x(NH)P(O) skele-
tons (x = 0 and 1). In P(S)-based structures, there is compe-
tition between OCP and P S, with the latter exhibiting a
better hydrogen-bond-acceptor capability, while in P(O)-
based structures, the N—Hꢀ ꢀ ꢀO P hydrogen bond is predo-
minant (Sabbaghi et al., 2016).
Quantum chemical calculations were also applied to an
evaluation of N—Hꢀ ꢀ ꢀY P (Y = O and S) hydrogen-bond
strengths, which in a typical N—Hꢀ ꢀ ꢀS P hydrogen bond
examined is about one-half with respect to N—Hꢀ ꢀ ꢀO P, e.g.
4.00 kcal molꢁ1 (1 kcal molꢁ1 = 4.184 kJ molꢁ1) in [2,4,6-
(CH3)3C6H2NH]P(S)[OCH2CH3]2 (Torabi Farkhani et al.,
2018) and 6.99 kcal molꢁ1 in [(4-CH3O)C6H4C(O)NH]-
P(O)[NHCH2C6H4(4-CH3)]2 (Taherzadeh et al., 2017).
Furthermore, Shainyan et al. (2010) reported the calculated
hydrogen-bond energies for N—Hꢀ ꢀ ꢀS and N—Hꢀ ꢀ ꢀO within
the ranges 3.8–6.0 and 4.8–8.6 kcal molꢁ1, respectively, for
some sulfonamide derivatives. The CSD-based analysis
showed the presence of only negligible exceptions for N—
Hꢀ ꢀ ꢀOCP hydrogen bonds in compounds with a (C—
O)2(NH)P(O) skeleton versus a competition between N—
3
2.1.2. Synthesis of (II). The synthesis of compound (II) has
been reported in the literature, together with IR and NMR
(31P, 1H, 13C) spectroscopic studies, electrochemical behaviour
and interactions with DNA, and this compound was also
proposed as a potential candidate for a DNA-sensing device
(Gholivand et al., 2016). Here, we report the single-crystal
X-ray diffraction analysis and some complementary spectro-
scopic features. Compound (II) was prepared by a procedure
similar to that reported in the literature from the reaction of
dimethyl chlorothiophosphate, 1,4-phenylenediamine and tri-
ethylamine (2:1:2 molar ratio, reaction time 4 h, ice-bath
temperature) in dry CH3CN. Colourless single crystals suitable
for X-ray analysis were obtained at room temperature from a
CH3OH/CHCl3 (4:1 v/v) mixture. The IR and NMR spectra
were re-investigated and the mass spectrum was also recorded.
In the NMR spectra, there are some differences, especially in
the coupling constants of some peaks in the 1H and 13C NMR
spectra. The differences may be due to the higher scan
numbers of experiments applied by us; thus, we report the new
data here. The phosphorus signal is equal to the reported value
(69.55 ppm in the literature, solvent DMSO-d6).
Hꢀ ꢀ ꢀS
P
and N—Hꢀ ꢀ ꢀOCP hydrogen bonds in (C—
O)2(NH)P(S)-based structures. None of these structures has
thus far been used for an evaluation of N—Hꢀ ꢀ ꢀOCP
hydrogen-bond strength (by computational means).
Analytical data: colourless block-shaped crystal. IR (KBr,
cmꢁ1): 3332, 3056, 2941, 2848, 1730, 1518, 1481, 1379, 1277,
1217, 1179, 1025, 955, 831, 731, 658. 31P{1H} NMR (121.5 MHz,
With this background in mind, we present here the synth-
esis, crystal structure and spectroscopic characterization of
phosphoramide (C6H5O)2P(O)NH(C6H10)NHP(O)(OC6H5)2,
1
DMSO-d6): ꢁ 69.56 (s). H NMR (300.1 MHz, DMSO-d6): ꢁ
ꢂ
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Two structures with a (C—O)2(N)P( Y) (Y is O and S) 1611

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Table 1
Experimental details.
(I)
(II)
Crystal data
Chemical formula
Mr
C30H32N2O6P2
578.51
C10H18N2O4P2S2
356.32
Crystal system, space group
Temperature (K)
Triclinic, P1
120
10.2789 (5), 10.8253 (4), 15.0200 (6)
101.229 (4), 105.716 (4), 109.782 (4)
1436.22 (12)
2
Mo Kꢂ
0.20
Monoclinic, P21/a
295
13.2517 (3), 10.0091 (2), 13.9580 (3)
90, 112.9309 (12), 90
1705.05 (6)
4
Mo Kꢂ
0.51
˚
a, b, c (A)
ꢂ, ꢃ, ꢄ (ꢃ)
3
˚
V (A )
Z
Radiation type
ꢅ (mmꢁ1
Crystal size (mm)
)
0.20 ꢄ 0.20 ꢄ 0.10
0.43 ꢄ 0.36 ꢄ 0.31
Data collection
Diffractometer
Absorption correction
Tmin, Tmax
AFC11 (Right): Eulerian 3 circle CCD
Multi-scan (CrysAlis PRO; Rigaku OD, 2015)
0.893, 1.000
Nonius KappaCCD
Multi-scan (SORTAV; Blessing, 1995)
0.790, 0.845
No. of measured, independent and observed
[I > 2ꢀ(I)] reflections
Rint
15732, 9396, 9009
6840, 4091, 3267
0.023
0.602
0.019
0.661
ꢁ1
˚
(sin ꢆ/ꢇ)max (A
)
Refinement
R[F2 > 2ꢀ(F2)], wR(F2), S
No. of reflections
No. of parameters
No. of restraints
H-atom treatment
0.030, 0.078, 1.01
9396
733
7
0.042, 0.115, 1.02
4091
191
2
H atoms treated by a mixture of independent
H atoms treated by a mixture of independent
and constrained refinement
0.40, ꢁ0.30
and constrained refinement
0.70, ꢁ0.48
ꢁ3
˚
Áꢈmax, Áꢈmin (e A
Absolute structure
)
Flack x determined using 3782 quotients
[(I+) ꢁ (Iꢁ)]/[(I+) + (Iꢁ)] (Parsons et al., 2013)
0.09 (3)
–
Absolute structure parameter
–
Computer programs: CrystalClear-SM Expert (Rigaku, 2014), COLLECT (Nonius, 1998), CrysAlis PRO (Rigaku OD, 2015), DENZO SMN (Otwinowski & Minor, 1997), SHELXT2014
(Sheldrick, 2015a), SIR97 (Altomare et al., 1999), SHELXL2018 (Sheldrick, 2015b), SHELXL2015 (Sheldrick, 2015b), Mercury (Macrae et al., 2008), enCIFer (Allen et al., 2004),
PLATON (Spek, 2009) and ORTEPIII (Burnett & Johnson, 1996).
3.60 (d, 3JP–H = 13.9 Hz, 12H, CH3), 6.92 (s, 4H, Ar–H), 8.19 (d,
2JP–H = 15.3 Hz, 2H, NH). 13C NMR (75.5 MHz, DMSO-d6): ꢁ
phoramide molecules [denoted (IA) and (IB)], i.e. Z0 = 2
(Fig. 1). The asymmetric unit of (CH3O)2P(S)(1-NH)-
(C6H4)(4-NH)P(S)(OCH3)2, (II), consists of one complete
molecule (Fig. 2) and the compound crystallizes in the
centrosymmetric space group P21/a. Selected bond lengths,
angles and hydrogen-bond geometries are presented in Tables
2–5. In both structures, the P atoms are within a distorted
tetrahedral environment, with bond angles ranging from
94.73 (10) (O3—P1—O4) to 115.74 (12)ꢃ (O1—P1—O3) for
(IA), 100.21 (13) (O56—P52—O55) to 116.36 (14)ꢃ (O51—
P51—N51) for (IB) and 92.82 (12) (O4—P2—O3) to
116.96 (8)ꢃ (O4—P2—S2) for (II). For both structures, the
bond-angle sums at the N atoms (C—N—H + H—N—P + C—
N—P) show small deviations (by about less than 4ꢃ) from the
ideal sp2 value of 360ꢃ.
3
52.90 (s), 119.18 (d, JP–C = 7.2 Hz, Cortho), 134.41 (d,
2JP–C = 2.9 Hz, Cipso). MS (70 eV, EI): m/z (%) 357 (2) [M + 1]+,
356 (10) [M]+, 355 (73) [M ꢁ 1]+, 354 (71) [M ꢁ 2]+, 353 (100)
[M ꢁ 3]+, 231 (18) [M ꢁ (CH3O)2PS]+, 125 (36) [C2H6O2PS]+.
2.2. Refinement
Crystal data, data collection and structure refinement
details are summarized in Table 1. For (I) and (II), all carbon-
bound H atoms were placed in calculated positions and were
refined as riding, with their Uiso values set at 1.2Ueq or
1.5Ueq(methyl) of the respective carrier atoms; in addition, the
methyl H atoms were allowed to rotate about the C—C bond.
Nitrogen-bound H atoms were located in a difference Fourier
map and refined isotropically, with their Uiso values set at
1.2Ueq of the carrier N atoms; the N—H bond lengths were
In the structure (I), the P O bond lengths [1.463 (2) and
˚
1.468 (2) A for (IA), and 1.466 (2) and 1.468 (2) A for (IB)]
˚
are within the standard ranges for analogous compounds
˚
˚
restrained to be 0.86 A, with an s.u. value of 0.01 A.
ˇ
(Pourayoubi, Necas & Negari, 2012) and are higher than the
normal phosphorus–oxygen double-bond length (1.45 A;
˚
3. Results and discussion
Corbridge, 1995). The P—N bond lengths [1.609 (2) and
3.1. X-ray structure description
˚
˚
1.602 (2) A for (IA), and 1.603 (3) and 1.595 (3) A for (IB)]
are standard for structures with an (O)2(N)P(O) skeleton
(Sabbaghi et al., 2016) and smaller than a typical P—N single-
bond length (Corbridge, 1995).
Achiral (C6H5O)2P(O)(1-NH)(C6H10)(4-NH)P(O)(OC6H5)2,
(I), crystallizes in the chiral space group P1, with the asym-
metric unit composed of two-symmetry-independent phos-
ꢂ
1612 Vahdani Alviri et al.
Two structures with a (C—O)2(N)P( Y) (Y is O and S)
Acta Cryst. (2018). C74, 1610–1621

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Figure 1
Displacement ellipsoid plot (50% probability level) of the components of the asymmetric unit of (I), showing the atom-numbering schemes. H atoms are
drawn as circles of arbitrary radii.
˚
The P S bond lengths [1.9156 (7) and 1.9109 (8) A] in
Table 3
Hydrogen-bond geometry (A, ) for (I).
ꢃ
˚
compound (II) are within the expected range for compounds
with an (O)2(N)P(S) skeleton. A recently published paper,
based on a CSD analysis, shows that the maximum populations
of P S bond lengths in this family of compounds are in the
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N1—H1Nꢀ ꢀ ꢀO52i
N2—H2Nꢀ ꢀ ꢀO51
N51—H51Nꢀ ꢀ ꢀO2ii
N52—H52Nꢀ ꢀ ꢀO1
C22—H22Aꢀ ꢀ ꢀO4iii
C6—H6Aꢀ ꢀ ꢀO55
C74—H74Aꢀ ꢀ ꢀO1
C2—H2Cꢀ ꢀ ꢀO52i
C2—H2Cꢀ ꢀ ꢀCG1i
0.85 (2)
0.85 (2)
0.87 (2)
0.84 (2)
0.95
0.95
0.95
0.95
0.95
2.03 (2)
2.00 (2)
1.98 (3)
2.04 (2)
2.51
2.69
2.61
2.69
2.92
2.863 (3)
2.820 (3)
2.802 (3)
2.866 (3)
3.418 (4)
3.565 (4)
3.329 (4)
3.465 (3)
3.593 (8)
167 (3)
162 (3)
158 (3)
168 (3)
160
154
133
139
129
˚
range 1.90–1.92 A (Pourayoubi, Abrishami et al., 2014). The
˚
P—N bond lengths [1.6307 (17) and 1.6253 (18) A for (II)] are
within the expected range for (O)2(N)P(S)-based structures
and are smaller than the maximum population of P—N bond
lengths found for (N)3P(S)-based structures (Alamdar et al.,
2015; Raissi Shabari et al., 2015). The P—N bonds in
phosphoramide (I) are slightly shorter than the P—N bonds in
thiophosphoramide (II). A CSD analysis of P—N bond
Symmetry codes: (i) x ꢁ 1; y; z; (ii) x þ 1; y; z; (iii) x; y þ 1; z þ 1.
lengths in structures with the (O)2(N)P(O) and (O)2(N)P(S)
skeletons also shows a trend to a few longer P—N bonds in the
thiophosphoryl compounds relative to the phosphoryl ones,
where the maximum populations of P—N bond lengths are in
Table 2
Selected geometric parameters (A, ) for (I).
ꢃ
˚
P1—O1
P1—O3
P1—O4
P1—N1
P2—O2
P2—O6
P2—O5
P2—N2
N1—C32
N2—C28
1.463 (2)
1.590 (2)
1.5937 (19)
1.609 (2)
1.468 (2)
1.580 (2)
1.5900 (19)
1.602 (2)
1.473 (4)
1.464 (3)
P51—O51
P51—O53
P51—O54
P51—N51
P52—O52
P52—O56
P52—O55
P52—N52
N51—C75
N52—C78
1.466 (2)
1.585 (2)
1.590 (2)
1.603 (3)
1.468 (2)
1.586 (2)
1.593 (2)
1.595 (3)
1.467 (4)
1.468 (4)
˚
the ranges 1.62–1.64 and 1.60–1.62 A, respectively. The details
of the CSD analysis are given in the supporting information
and the related histogram is shown in Fig. S1. In phospho-
ramides, it was postulated that in addition to the resonance
interaction between the nonbonding electrons of the N atom
and the P O ꢉ system, there might be another type of
O1—P1—O3
O1—P1—O4
O3—P1—O4
O1—P1—N1
O3—P1—N1
O4—P1—N1
O2—P2—O6
O2—P2—O5
O6—P2—O5
O2—P2—N2
O6—P2—N2
O5—P2—N2
C1—O3—P1
C7—O4—P1
C13—O5—P2
C19—O6—P2
C32—N1—P1
C28—N2—P2
115.74 (12)
114.34 (12)
94.73 (10)
113.23 (12)
109.01 (12)
108.18 (12)
113.89 (12)
115.07 (12)
100.23 (11)
114.21 (13)
106.65 (12)
105.44 (11)
116.03 (17)
123.86 (18)
118.23 (17)
122.84 (18)
124.40 (19)
124.3 (2)
O51—P51—O53
O51—P51—O54
O53—P51—O54
O51—P51—N51
O53—P51—N51
O54—P51—N51
O52—P52—O56
O52—P52—O55
O56—P52—O55
O52—P52—N52
O56—P52—N52
O55—P52—N52
C51—O53—P51
C57—O54—P51
C63—O55—P52
C69—O56—P52
C75—N51—P51
C78—N52—P52
115.32 (12)
112.46 (12)
100.97 (11)
116.36 (14)
104.92 (12)
105.21 (13)
114.91 (13)
113.48 (12)
100.21 (13)
114.76 (12)
107.10 (12)
104.95 (13)
126.20 (19)
121.73 (19)
123.82 (19)
119.24 (19)
123.7 (2)
Figure 2
Displacement ellipsoid plot (50% probability level) for (II), showing the
atom-numbering scheme.
125.6 (2)
ꢂ
Acta Cryst. (2018). C74, 1610–1621
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Two structures with a (C—O)2(N)P( Y) (Y is O and S) 1613

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Figure 3
Overlay for the molecule pairs P1/P2 and P51/P52 of (I), showing the greatest (left side) and least (right side) similarities.
Table 5
Hydrogen-bond geometry (A, ) for (II).
Table 4
Selected geometric parameters (A, ) for (II).
ꢃ
˚
ꢃ
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
C1—N1
C4—N2
N1—P1
P1—O2
P1—O1
1.419 (2)
1.424 (2)
1.6307 (17)
1.5749 (16)
1.5795 (16)
P1—S1
N2—P2
P2—O4
P2—O3
P2—S2
1.9156 (7)
1.6253 (18)
1.5702 (18)
1.5794 (18)
1.9109 (8)
C3—H3ꢀ ꢀ ꢀO3
C3—H3ꢀ ꢀ ꢀO4
N1—H1Nꢀ ꢀ ꢀO1i
N2—H2Nꢀ ꢀ ꢀO3ii
0.93
0.93
0.81 (2)
0.85 (2)
2.67
2.59
2.38 (2)
2.22 (2)
3.237 (2)
3.158 (3)
3.174 (2)
3.042 (3)
120
120
169 (2)
165 (2)
C1—N1—P1
O2—P1—O1
O2—P1—N1
O1—P1—N1
O2—P1—S1
O1—P1—S1
N1—P1—S1
C7—O1—P1
C8—O2—P1
130.09 (14)
93.96 (9)
C4—N2—P2
O4—P2—O3
O4—P2—N2
O3—P2—N2
O4—P2—S2
O3—P2—S2
N2—P2—S2
C9—O3—P2
130.33 (15)
92.82 (12)
109.06 (11)
107.07 (10)
116.96 (8)
116.63 (7)
112.43 (7)
121.3 (3)
1
1
1
2
1
2
Symmetry codes: (i) ꢁx ꢁ ; y þ ; ꢁz; (ii) ꢁx þ ; y ꢁ ; ꢁz þ 1.
2
2
107.88 (10)
108.26 (10)
116.89 (7)
116.54 (7)
111.75 (7)
119.8 (2)
˚
molecules after fitting is 1.5464 A, with a maximum deviation
˚
of 3.4446 A, or 1.5694 A, with a maximum deviation of
˚
3.2956 A. The relatively high RMSD indicates that there are
large torsional liberties (Collins et al., 2006) in different
segments of the molecules, typically for the PhO segments, as
can be seen in Fig. 3.
˚
119.39 (19)
resonance interaction along the P—N bond which is proposed
as N!P back-donation effect (Xue et al., 1989). These factors
should be more effective in P( O)N-based structures with
respect to the P( S)N-based ones.
The P—O—C bond angles in both structures are close to
120ꢃ, typically 122.84 (18)ꢃ (P2—O6–C19) in (IA),
121.73 (19)ꢃ (P51—O54—C57) in (IB) and 121.3 (3)ꢃ (P2—
O3—C9) in (II), which indicate an sp2-hybridization state for
the O atoms noted. This hybridization state is in accordance
with a recently published CSD analysis of structures with
P(Y)(O—C)2(N) (Y = O and S) skeletons (Sabbaghi et al.,
2016).
In the crystal structure of (I), two symmetry-independent
molecules are assembled into a one-dimensional arrangement,
along the a axis, through four different types of N—Hꢀ ꢀ ꢀO
P
hydrogen bonds. This pattern includes a noncentrosymmetric
R22(18) ring motif combined with a C22(8) chain motif (Fig. 4);
for graph-set notation details, see Bernstein et al. (1995). The
other possible acceptor groups, i.e. the N atom bonded to P(O)
and also the ester O atoms, are much weaker hydrogen-bond
acceptors with regard to P O, as supported by a previously
reported CSD analysis (Sabbaghi et al., 2016).
Fig. 5 shows the hydrogen-bond pattern made by the
synergistic co-operation of N—Hꢀ ꢀ ꢀO [labelled (a)], C—
Hꢀ ꢀ ꢀO [labelled (b)] and C—Hꢀ ꢀ ꢀꢉ [labelled (c)] interactions.
There are four weak C—Hꢀ ꢀ ꢀO interactions in the structure,
and one of them is responsible for extending the dimension-
ality made by N—Hꢀ ꢀ ꢀO hydrogen bonds to a two-dimen-
sional (2D) architecture along the (011) plane. The three other
C—Hꢀ ꢀ ꢀO interactions may be considered as auxiliary
hydrogen bonds and do not extend the dimensionality of the
hydrogen-bond pattern, as two of them take part in an (N—
Hꢀ ꢀ ꢀ)(C—Hꢀ ꢀ ꢀ)O grouping in the a direction and the
remaining one occurs as an independent interaction in the a
direction, similar to the direction of the N—Hꢀ ꢀ ꢀO hydrogen
bonds. In this assembly, the noncentrosymmetric graph-set
motifs C22(12), R21(8), R22(10), R22(12) and R22(22) are distin-
guishable. The C—Hꢀ ꢀ ꢀꢉ interaction does not extend the
dimensionality.
Fig. 3 shows the overlay for two symmetry-independent
molecules of (I). The r.m.s. deviation (RMSD) between these
Figure 4
A crystal packing diagram for (I), showing the 1D network along the a
axis formed by N—Hꢀ ꢀ ꢀO P hydrogen bonds.
The structure of (II) shows a different hydrogen-bond
pattern with regard to the motifs formed, where N—Hꢀ ꢀ ꢀO
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Figure 5
The two-dimensional array of (I) along the (011) plane formed by N—
Hꢀ ꢀ ꢀO and C—Hꢀ ꢀ ꢀO hydrogen bonds. Symmetry-independent mol-
ecules are shown with green and blue colours, and N—Hꢀ ꢀ ꢀO, C—Hꢀ ꢀ ꢀO
and C—Hꢀ ꢀ ꢀꢉ interactions are shown as dashed black, red and light-blue
lines, respectively, which are also indicated with the labels (a), (b) and (c)
for some representative interactions. The black-coloured labels are
auxiliary hydrogen bonds and the red-coloured labels show the hydrogen
bonds responsible for the dimensionality observed.
Figure 6
A crystal packing diagram for (II), showing the 2D network along the
(101) plane formed by N—Hꢀ ꢀ ꢀOCP hydrogen bonds.
hydrogen bonds take part in the formation of ring motifs (see
Fig. 6), while the P S groups do not take part in the
hydrogen-bonding pattern (the acceptor O atoms are the ester
ones). These interactions build a 2D arrangement along the
(101) plane (Fig. 6).
(including at least one O—C bond), a competition between
the S atom and the ester O atom was found to act as an
acceptor group with regards to N—H, where, respectively,
about 40 and 14% participations of N—Hꢀ ꢀ ꢀS P and N—
Hꢀ ꢀ ꢀOCP were found (Sabbaghi et al., 2016).
The structure with the CSD refcode NOHTAG,
i.e. (CH3CH2O)2P(S)(1-NH)(C6H4)(4-NH)P(S)(OCH2CH3)2
(Ren et al., 2007), is similar to the structure of (II), the only
difference being in the alkoxy groups attached to phosphorus.
The overlay of these two structures shows the similarity,
especially in the directions of possible donor and acceptor
sites, but with a few differences in the directions of the Et and
Me groups in the two structures (Fig. 7, top). The basic
hydrogen-bond graph-set motif formed in NOHTAG is similar
to the structure of (II), i.e. R44(26), and the hydrogen-bond
patterns are also similar, i.e. a two-dimensional architecture,
but conjunctions in these assemblies are different due to the
involvement of N—Hꢀ ꢀ ꢀOCP hydrogen bonds in the structure
of (II) and N—Hꢀ ꢀ ꢀS hydrogen bonds in NOHTAG (Fig. 7,
bottom). It is noted again that none of the N—Hꢀ ꢀ ꢀOCP and
N—Hꢀ ꢀ ꢀS hydrogen bonds are directing, as both of them are
weak.
3.2. Hirshfeld surface analysis
The intermolecular interactions of structures (I) and (II)
were quantified by Hirshfeld surface (HS) analysis, using
three-dimensional (3D) surface functions, and 2D fingerprint
(FP) plots (Spackman & McKinnon, 2002; McKinnon et al.,
2007). The Hirshfeld surfaces mapped with dnorm and corre-
sponding shape index associated 2D FP plots were generated
using the CrystalExplorer software (Version 3.1; Wolff et al.,
2013), using the CIFs of structures (I) and (II) as the input
files. The details of the 3D surface functions are given in the
supporting information and the related visualizations are
shown in Figs. S2 and S3 for structures (I) and (II), respec-
tively. Figs. 8, 9 and 10 show the 2D FP plots for the two
symmetry-independent molecules (IA) and (IB) of (I) and for
(II), respectively.
The decomposed FP plots show that the percentages of the
interactions in (IA) and (IB) are very close to each other. For
both molecules, the Hꢀ ꢀ ꢀH contacts represent the largest
relative contribution [55.6% for (IA) (Fig. 8b) and 56.8% for
(IB) (Fig. 9b)], with one spike for both molecules which is
slightly sharper for molecule (IB). The other major inter-
actions are Hꢀ ꢀ ꢀC/Cꢀ ꢀ ꢀH [23.4% for both (IA) and (IB)
(Figs. 8c and 9c)] and Hꢀ ꢀ ꢀO/Oꢀ ꢀ ꢀH [17.7% for (IA) (Fig. 8d)
and 16.3% for (IB) (Fig. 9d)]. The minor contacts in the crystal
In the structure of (II), no important intermolecular C—
Hꢀ ꢀ ꢀO hydrogen bonds are distinguishable in the hydrogen-
˚
bond pattern and the nearest Cꢀ ꢀ ꢀO separation is about 3.8 A.
There are two intramolecular C—Hꢀ ꢀ ꢀO hydrogen bonds in
the structure of (II), with the geometries as given in Table 5.
As was noted in the Introduction, a CSD analysis for
(O)2(N)P(O)-based structures (including at least one O—C
bond) showed only four exceptions (about 2%) with partici-
pation of the OCP atom (versus P O) as a hydrogen-bond
acceptor. Moreover, for (O)2(N)P(S)-based structures
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3.3.2. IR. The lower N—H stretching frequency of (I)
relative to (II) (3206 and 3332 cmꢁ1, respectively) reflects the
stronger hydrogen bonds of (I), as was discussed in x3.1
(strength of N—Hꢀ ꢀ ꢀO P > N—Hꢀ ꢀ ꢀOCP).
are Oꢀ ꢀ ꢀC/Cꢀ ꢀ ꢀO [2.1% for both (IA) and (IB) (Figs. 8e and
9e)] and Cꢀ ꢀ ꢀC [1.2% for both (IA) and (IB) (Figs. 8f and 9f)].
For (II), similar to (I), the most important interactions are
the Hꢀ ꢀ ꢀH contacts (51.3%; Fig. 10b). The other interactions
are Hꢀ ꢀ ꢀS/Sꢀ ꢀ ꢀH (21.9%; Fig. 10c), Hꢀ ꢀ ꢀO/Oꢀ ꢀ ꢀH (14.3%;
Fig. 10d), Cꢀ ꢀ ꢀH/Hꢀ ꢀ ꢀC (9.9%; Fig. 10e) and Sꢀ ꢀ ꢀS (1.8%;
Fig. 10f). The presence of Sꢀ ꢀ ꢀS contacts is a result of the ring
motif illustrated in Fig. 7 (right), in which the two S atoms in
adjacent molecules are directed towards each other, with an
3.3.3. MS. The mass spectra of both compounds reveal the
presence of the molecular ion peaks in a 70 eV experiment, at
m/z = 578 for (I) and 356 for (II). The base peaks are revealed
at m/z 345 for (I) and at 353 for (II) belonging to [M ꢁ
P(O)(OPh)2]+ and [M ꢁ 3]+, respectively. The other important
signals appear at 233 ([C12H10O3P]+) and 156 ([C6H5O3P]+)
for (I), and at 231 ([M ꢁ P(S)(OMe)2]+) and 125 ([C2H6O2-
PS]+) for (II).
˚
Sꢀ ꢀ ꢀS separation of about 3.6 A. Furthermore, the S atom
involves some neighbouring H atoms in intermolecular Hꢀ ꢀ ꢀS
interactions which causes a reduction of the Hꢀ ꢀ ꢀH contacts in
(II) with respect to (I). The Cꢀ ꢀ ꢀH contacts are less prominent
in (II), which has a lesser number of unsaturated C atoms.
3.4. Computational details
The quantum chemical calculations were performed using
the GAUSSIAN09 software package at the B3LYP/6-
311G(d,p) level of theory and the GaussView 5.0.8 program
was applied for visualizing the structure and verification of the
molecular-orbital contour diagrams (Frisch et al., 2009). A
natural bond orbital (NBO) analysis was carried out to obtain
natural atomic charges, natural electron configurations,
hybridization states and intermolecular interactions, using the
NBO 3.1 version in GAUSSIAN09 (Glendening et al., 2003).
3.4.1. Optimized structures and hybridization states of O
atoms. The optimized structures of compounds (I) and (II) are
shown in Figs. S8 and S9, respectively (see supporting infor-
mation). As the ester O atom may be a potential hydrogen-
bond acceptor, we decided to examine its hybridization state
in the phosphoramide and thiophosphoramide studied here.
So, for the P—O—C segment, the percent contributions of the
3.3. Spectroscopic study
3.3.1. NMR. The phosphorus signals of phosphoramide (I)
and thiophosphoramide (II) appear at ꢁ0.30 and 69.56 ppm,
respectively; in comparison with the signals of typical ana-
logous compounds, e.g. P(O)(OC6H5)2(NHNHC6H5) at
ꢁ1.49 ppm (Sabbaghi et al., 2016) and P(S)(OCH2CH3)2(NH-
NHC6H5) at 71.08 ppm (Pourayoubi, Abrishami et al., 2014).
2
3
1
The J and J couplings of phosphorus with H and 13C
nuclei demonstrate the bond formation between phosphorus
and organic moieties. These couplings cause the ‘dd’ signal of
the NH proton in (I), the doublet signals for the methyl and
NH protons in (II), and the doublet signals for the ortho and
ipso C atoms of the C6H5O group in (I) and the NHC6H4NH
group in (II); see Figs. S4–S7 in the supporting information.
Figure 7
An overlay of the structures of NOHTAG (purple) and (II) (green) (top), and the hydrogen-bond motifs of NOHTAG (bottom left) and (II) (bottom
right). The hydrogen-bond motif of NOHTAG was regenerated from the CSD data.
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Table 6
All the P—O—C bond angles (ꢃ) and the contributions (%) of the s and p orbitals of BD(P—O) and BD(C—O) in both (I) and (II).
Segment
Bond angles
BD(P—O)
Percent contributions
BD(C—O)
Percent contributions
Compound (I)
P1—O3—C1
P1—O4—C7
125.0815
124.7019
125.0868
122.9743
125.6914
124.4525
124.3808
124.7025
BD(P1—O3)
BD(P1—O4)
BD(P2—O5)
BD(P2—O6)
BD(P51—O53)
BD(P51—O54)
BD(P52—O55)
BD(P52—O56)
s (26.17), p (73.79)
s (27.14), p (72.82)
s (28.18), p (71.78)
s (27.10), p (72.85)
s (27.28), p (72.67)
s (25.76), p (74.19)
s (26.58), p (73.38)
s (26.48), p (73.47)
BD(O3—C1)
BD(O4—C7)
s (37.13), p (62.81)
s (37.20), p (62.75)
s (37.94), p (62.01)
s (37.33), p (62.62)
s (37.88), p (62.07)
s (36.49), p (63.45)
s (36.89), p (63.06)
s (37.31), p (62.63)
P2—O5—C13
P2—O6—C19
P51—O53—C51
P51—O54—C57
P52—O55—C63
P52—O56—C69
BD(O5—C13)
BD(O6—C19)
BD(O53—C51)
BD(O54—C57)
BD(O55—C63)
BD(O56—C69)
Compound (II)
P1—O1—C7
P1—O2—C8
P2—O3—C9
P2—O4—C10
120.6189
120.5541
120.5650
120.6046
BD(P1—O1)
BD(P1—O2)
BD(P2—O3)
BD(P2—O4)
s (28.60), p (71.35)
s (28.58), p (71.37)
s (28.58), p (71.37)
s (28.59), p (71.36)
BD(O1—C7)
BD(O2—C8)
BD(O3—C9)
BD(O4—C10)
s (30.69), p (69.25)
s (30.67), p (69.28)
s (30.67), p (69.27)
s (30.69), p (69.26)
Table 7
The contributions (%) of the s and p orbitals of the two remaining
orbitals associated with O atoms.
involvement of ꢉ in resonance interactions with phosphorus
(see Tables S1 and S2 in the supporting information), and as
will be discussed later, the LP takes part in the hydrogen-
bonding interaction.
Lp O
Percent contributions
ꢉ O
Percent contributions
Similar results were obtained for compound (II) and, as an
example, the data for P1—O1—C7 are discussed below. The
contributions of the s and p orbitals for P1—O1 are 28.60 and
71.35%, and for C7—O1 are 30.69 and 69.25%, indicating
hybridization states of sp2.5 and sp2.3, respectively. For the LP
of O1, the contributions of the s and p orbitals (40.54 and
59.43%) indicate an sp1.5 state. The remaining orbital asso-
ciated with the O atom has contributions of mainly p character
(99.81%) and very little s character (0.15%).
Compound (I)
Lp O3
Lp O4
Lp O5
Lp O6
Lp O53
Lp O54
Lp O55
Lp O56
s (32.03), p (67.94)
s (32.68), p (67.29)
s (32.33), p (67.64)
s (31.53), p (68.43)
s (32.53), p (67.44)
s (32.98), p (66.99)
s (32.98), p (66.98)
s (32.23), p (67.74)
ꢉ O3
ꢉ O4
ꢉ O5
ꢉ O6
ꢉ O53
ꢉ O54
ꢉ O55
ꢉ O56
s (4.65), p (95.32)
s (2.97), p (96.99)
s (1.54), p (98.42)
s (4.01), p (95.95)
s (2.30), p (97.67)
s (4.75), p (95.22)
s (3.53), p (96.43)
s (3.95), p (96.01)
Compound (II)
In a recently published paper (Sabbaghi et al., 2016), a CSD
survey of compounds with a (C—O)2–x(O)x(N)P(Y) fragment
(Y = O and S; x = 0 and 1) shows that the P—O—C bond
angles conform to a hybridization state close to sp2. Moreover,
for (C—O)2–x(O)x(NH)P(O)-based structures, the CSD
analysis shows effectively only the presence of N—Hꢀ ꢀ ꢀOP
hydrogen bonds and not N—Hꢀ ꢀ ꢀOC, demonstrating the
greater hydrogen-bond-acceptor capability of the phosphoryl
O atom with respect to the ester one. For compounds with the
(C—O)2–x(O)x(NH)P(S) segment, there is competition
between the S atom and the ester O atom as hydrogen-bond
acceptors. In the next section, the calculated natural charges
and electron configurations of possible acceptor atoms O and
S will be inspected, together with the values related to the N
atom (bonded to H) and also H.
3.4.2. Natural charge and electron configuration of H, N,
O and S. The natural electronic configurations of the atoms
and the related charges were obtained by a natural population
analysis performed on the optimized structures and the results
for atoms O, N, S and H are given in Table S3. In compound
(I), the most concentrations of negative charges occur on the
terminal O atoms, i.e. O1 (ꢁ1.08013) and O2 (ꢁ1.1136), which
are more than the negative charges on the ester O atoms, i.e.
O3 (ꢁ0.80896), O4 (ꢁ0.80242), O5 (ꢁ0.81111) and O6
(ꢁ0.81538). These differences are reflected in the better
hydrogen-bond-acceptor capability of the terminal O atoms,
Lp O1
Lp O2
Lp O3
Lp O4
s (40.54), p (59.43)
s (40.56), p (59.41)
s (40.55), p (59.41)
s (40.54), p (59.42)
ꢉ O1
ꢉ O2
ꢉ O3
ꢉ O4
s (0.15), p (99.81)
s (0.18), p (99.78)
s (0.17), p (99.79)
s (0.16), p (99.80)
s and p orbitals to the bonding and nonbonding molecular
orbitals were evaluated and the results, together with the
calculated P—O—C bond angles, are gathered in Tables 6
and 7.
For both (I) and (II), the P—O—C bond angles are some-
what larger than the ideal sp2 angle (by about 6ꢃ), indicating
the hybridization state of the bonding orbitals to be near sp2.
Furthermore, the contributions of the s and p orbitals of
BD(P—O) and BD(C—O) (Table 6) indicate a near sp2-
hybridization state for the orbitals constructing the bonds in
the POC segment. The two other orbitals associated with the
O atom (LP and ꢉ) (Table 7) have considerably different s and
p characters, indicating a near sp2-hybridized state for LP and
a mainly p character for ꢉ. Typically for the P1—O3—C1
segment of (I), the contributions of the s and p orbitals of P1—
O3 are 26.17 and 73.79%, and for C1—O3 are 37.13 and
62.81%, in agreement with hybridization states of sp2.8 and
sp1.7, respectively. For the two orbitals at O3, the contributions
of the s and p orbitals were obtained as 32.03 and 67.94% for
LP (sp2.1 state), and as 4.65 and 95.32% for ꢉ. The delocali-
zation energies of LP and ꢉ in both (I) and (II) support the
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(ꢁ1.01154), N51 (ꢁ1.03795) and N52 (ꢁ1.01595), and the
positive character of the H atoms, i.e. H1N (0.4478), H2N
(0.4031), H51N (0.4495) and H52N (0.4047), can also be
considered as a driving force for intermolecular hydrogen-
bond formation.
It should be noted that the N atom is not usually a potential
hydrogen-bond-acceptor group in phosphoramide com-
pounds, as it is usually involved in a resonance interaction with
the P atom and shows sp2 character. This is supported by the
recently published CSD analysis of bond-angle sums at the N
atoms bonded to P O and P S examined for (N)3P(Y)-
based structures (Y = O and S) (Pourayoubi, Jasinski et al.,
2012; Raissi Shabari et al., 2015), where a value near 360ꢃ was
obtained, and also such an N atom shows a very weak Lewis
base characteristic and is not capable as a hydrogen-bond
acceptor (Sabbaghi et al., 2017).
For compound (II), atoms O1, O2, O3 and O4 all have a
charge value of ꢁ0.81819, and the S atoms have a lesser
negative charge of ꢁ0.60476. Also, a positive charge of 0.4154
was observed for the H1N and H2N atoms.
3.4.3. Donor–acceptor interactions. For considering the
donor–acceptor interaction energies in both (I) and (II), a
hydrogen-bonded cluster of three molecules was constructed
and used as the input file for the computational calculations.
This cluster allows all the independent hydrogen-bond inter-
actions in the crystal to be considered. It is important to note
that the input file of cluster (II) is a chain assembly including
weak intermolecular interactions and in order to retain a
geometry similar to what was observed in the X-ray crystal
structure, the ModRedundant option was used and some
geometry parameters were fixed. This option deletes the
Figure 8
Two-dimensional fingerprint plots of molecule (IA), showing (a) full, (b)
Hꢀ ꢀ ꢀH, (c) Hꢀ ꢀ ꢀC/Cꢀ ꢀ ꢀH, (d) Hꢀ ꢀ ꢀO/Oꢀ ꢀ ꢀH, (e) Oꢀ ꢀ ꢀC/Cꢀ ꢀ ꢀO and (f)
Cꢀ ꢀ ꢀC.
as was discussed in the description of the crystal structure. The
negative character of the N atoms, i.e. N1 (ꢁ1.04297), N2
Figure 9
Figure 10
Two-dimensional fingerprint plots of molecule (IB), showing (a) full, (b)
Hꢀ ꢀ ꢀH, (c) Hꢀ ꢀ ꢀC/Cꢀ ꢀ ꢀH, (d) Hꢀ ꢀ ꢀO/Oꢀ ꢀ ꢀH, (e) Oꢀ ꢀ ꢀC/Cꢀ ꢀ ꢀO and (f)
Cꢀ ꢀ ꢀC.
Two-dimensional fingerprint plots of molecule (II), showing (a) full, (b)
Hꢀ ꢀ ꢀH, (c) Hꢀ ꢀ ꢀS/Sꢀ ꢀ ꢀH, (d) Hꢀ ꢀ ꢀO/Oꢀ ꢀ ꢀH, (e) Cꢀ ꢀ ꢀH/Hꢀ ꢀ ꢀC and (f)
Sꢀ ꢀ ꢀS.
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Table 8
NBO analysis results of (I) by the B3LYP/6-311g(d,p) method.
Donor Occu.
No.
E
(a.u.)
Acceptor
Occu.
No.
E
E(2)
(a.u.) (kcal molꢁ1
)
Lp O52 1.9660 ꢁ0.7549 BD* N1—H1N
Lp O51 1.9662 ꢁ0.7572 BD* N2—H2N
0.0287 0.4623 7.09
0.0287 0.4642 7.03
Lp O1 1.9638 ꢁ0.7389 BD* N52—H52N 0.0325 0.4729 8.60
Lp O2 1.9656 ꢁ0.7430 BD* N51—H51N 0.0303 0.4676 7.33
Table 9
NBO analysis results of (II) by the B3LYP/6-311g(d,p) method.
Donor Occu.
No.
E
(a.u.)
Acceptor
Occu.
No.
E
(a.u.)
E(2)
(kcal molꢁ1
)
Lp O1 1.94905 ꢁ0.65940 BD* N1—H1N 0.02426 0.42790 4.88
Lp O3 1.94410 ꢁ0.65654 BD* N2—H2N 0.03007 0.42825 8.16
Figure 11
The optimized structure of the three-molecule cluster of (I) at the
B3LYP/6-311g(d,p) level.
The overlap between the lone pair of the O atom and
ꢀ*(N—H) leads to an intermolecular charge transfer. The
energies of the interactions were estimated by second-order
perturbation theory [E(2)] using NBO 3.1 (Glendening et al.,
2003). In this approach, a large stabilization energy [E(2)]
shows a strong interaction between an electron donor and an
electron acceptor.
The cluster of (I) includes four independent N—Hꢀ ꢀ ꢀO
hydrogen bonds (Figs. 11 and 13) and the NBO details of the
N—Hꢀ ꢀ ꢀO hydrogen bonds are listed in Table 8, which
includes the electron occupancy number and the energies of
redundant short interactions before performing the calcula-
tion and maintains similarity with the intermolecular geometry
found in the crystal. During the calculation, these redundant
interactions may cause the positions of the molecules to
change in the hydrogen-bonded cluster, only including weak
interactions. The structures were optimized by the B3LYP/6-
311g(d,p) method and are shown in Figs. 11 and 12 for clusters
(I) and (II), respectively.
Figure 12
The optimized structure of the three-molecule cluster of (II) at the B3LYP/6-311g(d,p) level.
Figure 13
Contour diagrams of the LP O atoms (left), the ꢀ* N—H bonds (middle) and the resulting hydrogen bonds (right) in (I) by the B3LYP/6-311g(d,p)
method.
ꢂ
Acta Cryst. (2018). C74, 1610–1621
Vahdani Alviri et al.
Two structures with a (C—O)2(N)P( Y) (Y is O and S) 1619

research papers
Table 10
NBO analysis results of (I) by the B3LYP/6-311g(d,p) method
(optimization is with restriction).
option for the optimization of (I) and the results of these
calculations are given in Table 10. As can be seen in Table 10,
the electron densities of the antibonding molecular orbitals
and the E(2) energies of all the interactions are larger than the
values without geometrical restriction, as given in Table 8. In
the case of optimization without restriction, the optimized
donor–acceptor distances are more than the experimental
values, and consequently the hydrogen-bond energies are
estimated to be smaller. With this additional calculation, we
may have a better comparison of the hydrogen-bond energies
of the two structures via a similar method, and the hydrogen-
bond energies of (I) are considerably stronger than those in
(II).
Donor Occu.
No.
E
(a.u.)
Acceptor
Occu.
No.
E
E(2)
(a.u.) (kcal molꢁ1
)
Lp O52 1.9556 ꢁ0.8519 BD* N1—H1N
Lp O51 1.9544 ꢁ0.8285 BD* N2—H2N
0.0422 0.4557 12.86
0.0455 0.4672 13.87
Lp O1 1.9567 ꢁ0.8287 BD* N52—H52N 0.0427 0.4672 13.41
Lp O2 1.9536 ꢁ0.8534 BD* N51—H51N 0.0486 0.4517 14.21
the molecular orbitals involved in a donor–acceptor inter-
action, together with the calculated E(2) value. In this struc-
ture, the stabilization energies were calculated to range from
7.03 to 8.60 kcal molꢁ1. Regarding Table 8, the highest stabi-
lization energy of E(2) is attributed to the N52—H52Nꢀ ꢀ ꢀO1
hydrogen bond, in which, however, the electron density of LP
(O1) is lower with respect to the other donor sites. The highest
energy value is related to the highest electron density of the
N52—H52N antibonding orbital (0.4729 a.u.).
4. Conclusion
The crystal packing of phosphoramide (I) is driven by N—
Hꢀ ꢀ ꢀO P hydrogen bonds, while in thiophosphoramide (II),
the ester O atoms take part in the N—Hꢀ ꢀ ꢀO—C hydrogen
bonds and the P S groups do not participate in hydrogen-
bonding interactions. The NBO methodology was used to
evaluate the strengths of these interactions, showing moderate
N—Hꢀ ꢀ ꢀO hydrogen bonds with relatively similar strengths in
(I) and weaker hydrogen bonds in (II). The NBO analysis
shows a near sp2-hybridization state for the two bonding
orbitals and one nonbonding orbital of the ester O atom,
together with one other orbital exhibiting mainly p character.
The input three-molecule cluster of (II) consists of N2—
H2Nꢀ ꢀ ꢀO3 and N1—H1Nꢀ ꢀ ꢀO1 hydrogen bonds, with the
orbital overlap between the LP for O3 or O1 with the corre-
sponding ꢀ* N—H (Figs. 12 and 14), and with E(2) values of
8.16 and 4.88 kcal molꢁ1, respectively (Table 9). As can be
seen in Table 9, the electron density of the ꢀ* N2—H2N
orbital is higher than the ꢀ* N1—H1N one, supporting the
stronger hydrogen-bond property of N2—H2Nꢀ ꢀ ꢀO3.
Finally, in order to avoid any ambiguity with respect to the
donor–acceptor interaction, we also used the ModRedundant
Acknowledgements
Support of this investigation by the Ferdowsi University of
Mashhad (project No. 39847/3) is gratefully acknowledged.
The authors appreciatively acknowledge the Cambridge
Crystallographic Data Centre for access to the CSD Enter-
prise.
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Acta Cryst. (2018). C74, 1610–1621
Vahdani Alviri et al.
Two structures with a (C—O)2(N)P( Y) (Y is O and S) 1621

supporting information
supporting information
Acta Cryst. (2018). C74, 1610-1621 [https://doi.org/10.1107/S2053229618014006]
A combined X-ray crystallography and theoretical study of N—H···OX (X is &z-
dbnd;P and —C) hydrogen bonds in two new structures with a (C—O)2(N)P(&z-
dbnd;Y) (Y is O and S) skeleton
Banafsheh Vahdani Alviri, Mehrdad Pourayoubi, Abolghasem Farhadipour, Marek Nečas and
Valerio Bertolasi
Computing details
Data collection: CrystalClear-SM Expert (Rigaku, 2014) for bv91; COLLECT (Nonius, 1998) for bv18. Cell refinement:
CrysAlis PRO (Rigaku OD, 2015) for bv91; DENZO SMN (Otwinowski & Minor, 1997) for bv18. Data reduction:
CrysAlis PRO (Rigaku OD, 2015) for bv91; DENZO SMN (Otwinowski & Minor, 1997) for bv18. Program(s) used to
solve structure: SHELXT2014 (Sheldrick, 2015a) for bv91; SIR97 (Altomare et al., 1999) for bv18. Program(s) used to
refine structure: SHELXL2018 (Sheldrick, 2015b) for bv91; SHELXL2015 (Sheldrick, 2015b) for bv18. Molecular
graphics: ORTEPIII (Burnett & Johnson, 1996) for bv18. Software used to prepare material for publication:
SHELXL2015 (Sheldrick, 2015b) for bv18.
N,N′-(Cyclohexane-1,4-diyl)bis(O,O′-diphenylphosphoramide) (bv91)
Crystal data
C30H32N2O6P2
Z = 2
Mr = 578.51
Triclinic, P1
F(000) = 608
Dx = 1.338 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 12958 reflections
θ = 3.2–29.8°
a = 10.2789 (5) Å
b = 10.8253 (4) Å
c = 15.0200 (6) Å
α = 101.229 (4)°
β = 105.716 (4)°
γ = 109.782 (4)°
V = 1436.22 (12) Å3
µ = 0.20 mm−1
T = 120 K
Block, colourless
0.20 × 0.20 × 0.10 mm
Data collection
AFC11 (Right): Eulerian 3 circle CCD
diffractometer
Radiation source: Rotating Anode
MicroMax-007HF DW 1.2 kW
Profile data from ω–scans
15732 measured reflections
9396 independent reflections
9009 reflections with I > 2σ(I)
Rint = 0.023
θ
max = 25.4°, θmin = 3.0°
Absorption correction: multi-scan
(CrysAlis PRO; Rigaku OD, 2015)
h = −11→12
k = −13→12
l = −17→18
T
min = 0.893, Tmax = 1.000
Acta Cryst. (2018). C74, 1610-1621
sup-1

supporting information
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.030
wR(F2) = 0.078
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0467P)2 + 0.2585P]
where P = (Fo2 + 2Fc2)/3
S = 1.01
9396 reflections
733 parameters
(Δ/σ)max = 0.014
Δρmax = 0.40 e Å−3
Δρmin = −0.30 e Å−3
7 restraints
Hydrogen site location: mixed
Absolute structure: Flack x determined using
3782 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et
al., 2013)
Absolute structure parameter: 0.09 (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
P1
P2
O1
O2
O3
O4
O5
O6
N1
H1N
N2
H2N
C1
C2
H2C
C3
H3A
C4
H4A
C5
H5A
C6
−0.01942 (7)
0.09162 (7)
0.1377 (2)
−0.0577 (2)
−0.0683 (2)
−0.1284 (2)
0.2148 (2)
0.1030 (2)
−0.0773 (3)
−0.161 (3)
0.1578 (3)
0.248 (3)
−0.0099 (3)
−0.0984 (3)
−0.196901
−0.0418 (4)
−0.101658
0.1026 (4)
0.141577
0.1892 (4)
0.288179
0.1330 (3)
0.191672
−0.1320 (3)
−0.2232 (3)
−0.277701
−0.2331 (4)
−0.293877
−0.09038 (7)
0.54319 (7)
−0.0603 (2)
0.5311 (2)
−0.07426 (19)
−0.25020 (19)
0.69728 (19)
0.4849 (2)
−0.0049 (2)
−0.003 (3)
0.4690 (2)
0.481 (3)
0.0619 (3)
0.1332 (3)
0.091346
0.2671 (3)
0.317639
0.3275 (3)
0.419496
0.2539 (4)
0.295787
0.1192 (3)
0.067546
−0.3334 (3)
−0.4726 (3)
−0.505712
−0.5628 (3)
−0.658855
0.06356 (5)
0.53492 (5)
0.10889 (15)
0.48320 (15)
−0.04192 (14)
0.02886 (14)
0.58839 (14)
0.62401 (15)
0.13168 (18)
0.107 (2)
0.01710 (15)
0.01731 (16)
0.0237 (4)
0.0229 (4)
0.0224 (4)
0.0215 (4)
0.0198 (4)
0.0228 (4)
0.0188 (5)
0.023*
0.0196 (5)
0.024*
0.0200 (6)
0.0235 (6)
0.028*
0.0296 (7)
0.036*
0.0332 (7)
0.040*
0.0342 (8)
0.041*
0.0278 (7)
0.033*
0.46732 (17)
0.492 (2)
−0.0466 (2)
−0.0525 (2)
−0.054063
−0.0560 (2)
−0.060358
−0.0533 (2)
−0.055456
−0.0473 (3)
−0.044900
−0.0449 (2)
−0.042118
0.0902 (2)
H6A
C7
C8
H8A
C9
H9A
0.0213 (6)
0.0278 (7)
0.033*
0.0367 (8)
0.044*
0.0431 (2)
−0.025122
0.0981 (3)
0.066975
Acta Cryst. (2018). C74, 1610-1621
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supporting information
C10
H10A
C11
H11A
C12
H12A
C13
C14
H14A
C15
H15A
C16
H16A
C17
H17A
C18
H18A
C19
C20
H20A
C21
H21A
C22
H22A
C23
H23A
C24
H24A
C26
H26A
H26B
C27
H27A
H27B
C28
H28A
C29
H29A
H29B
C30
H30A
H30B
C32
H32A
P51
−0.1556 (4)
−0.163778
−0.0659 (4)
−0.013364
−0.0524 (3)
0.010852
0.2305 (3)
0.1535 (3)
0.088763
0.1729 (4)
0.121914
0.2659 (4)
0.277387
0.3423 (4)
0.407097
0.3249 (3)
0.376589
0.0515 (3)
−0.0663 (3)
−0.114556
−0.1122 (4)
−0.192378
−0.0432 (4)
−0.075535
0.0739 (4)
0.120862
−0.5141 (4)
−0.576278
−0.3747 (3)
−0.341187
−0.2832 (3)
−0.187684
0.7902 (3)
0.8727 (3)
0.864500
0.9676 (3)
1.026139
0.9782 (3)
1.042676
0.8942 (3)
0.902204
0.7991 (3)
0.741153
0.5245 (3)
0.4232 (3)
0.332794
0.4568 (4)
0.388376
0.5879 (4)
0.609828
0.6883 (4)
0.779304
0.6565 (3)
0.724589
0.0945 (3)
0.093273
0.005809
0.2137 (3)
0.204182
0.209769
0.3527 (3)
0.356025
0.3683 (3)
0.371807
0.456595
0.2489 (3)
0.258315
0.253496
0.1084 (3)
0.100391
0.51364 (7)
−0.01130 (7)
0.5299 (2)
0.0448 (2)
0.1971 (3)
0.234062
0.2428 (2)
0.311247
0.1889 (2)
0.219774
0.5343 (2)
0.5368 (2)
0.572182
0.4865 (3)
0.487907
0.4340 (3)
0.398768
0.4331 (3)
0.397734
0.4832 (2)
0.482568
0.6981 (2)
0.7061 (2)
0.660240
0.7824 (2)
0.789429
0.8481 (2)
0.900281
0.8382 (2)
0.883214
0.7631 (2)
0.756441
0.2995 (2)
0.273895
0.312337
0.3943 (2)
0.441290
0.423043
0.3772 (2)
0.350978
0.3022 (2)
0.328686
0.289110
0.2069 (2)
0.162067
0.175647
0.2235 (2)
0.247602
0.56468 (5)
0.03851 (5)
0.51600 (15)
0.07061 (15)
0.0343 (8)
0.041*
0.0317 (7)
0.038*
0.0268 (6)
0.032*
0.0205 (6)
0.0272 (6)
0.033*
0.0352 (8)
0.042*
0.0374 (8)
0.045*
0.0350 (8)
0.042*
0.0272 (7)
0.033*
0.0204 (6)
0.0268 (6)
0.032*
0.0330 (7)
0.040*
0.0334 (7)
0.040*
0.0334 (8)
0.040*
0.0285 (7)
0.034*
0.0220 (6)
0.026*
0.026*
0.0232 (6)
0.028*
0.028*
0.0181 (6)
0.022*
0.0204 (6)
0.024*
0.024*
0.0192 (6)
0.023*
0.023*
0.0190 (6)
0.023*
0.02132 (17)
0.02157 (17)
0.0280 (5)
0.0260 (5)
0.1223 (3)
0.203124
−0.0522 (3)
−0.152266
−0.063867
0.0411 (3)
−0.010222
0.137874
0.0674 (3)
−0.031368
0.1403 (3)
0.241239
0.150183
0.0505 (3)
0.105590
−0.045086
0.0198 (3)
0.116408
0.59715 (8)
0.49858 (7)
0.4625 (2)
0.6611 (2)
P52
O51
O52
Acta Cryst. (2018). C74, 1610-1621
sup-3

supporting information
O53
O54
O55
O56
N51
H51N
N52
H52N
C51
C52
H52C
C53
H53A
C54
H54A
C55
H55A
C56
H56A
C57
C58
H58A
C59
H59A
C60
H60A
C61
H61A
C62
H62A
C63
C64
H64A
C65
H65A
C66
H66A
C67
H67A
C68
H68A
C69
C70
H70A
C71
H71A
C72
0.7353 (2)
0.5762 (2)
0.4222 (2)
0.4173 (2)
0.6598 (3)
0.754 (3)
0.4371 (3)
0.346 (3)
0.7833 (3)
0.7386 (4)
0.672085
0.7925 (5)
0.762647
0.8891 (5)
0.925727
0.9324 (5)
0.999018
0.8793 (4)
0.909342
0.5117 (3)
0.5908 (3)
0.687327
0.5276 (4)
0.581000
0.3865 (4)
0.343089
0.3105 (4)
0.214524
0.3717 (3)
0.318441
0.4746 (3)
0.5044 (4)
0.489926
0.5556 (4)
0.578412
0.5725 (4)
0.606502
0.5414 (4)
0.553488
0.4919 (4)
0.470542
0.4200 (4)
0.5416 (4)
0.626665
0.5393 (5)
0.622447
0.4148 (5)
0.414384
0.6527 (2)
0.4288 (2)
0.0145 (2)
−0.1749 (2)
0.4376 (3)
0.479 (3)
0.0499 (2)
0.017 (3)
0.7776 (3)
0.7885 (4)
0.708835
0.9180 (4)
0.927119
1.0332 (4)
1.121561
1.0198 (4)
1.099197
0.8910 (3)
0.881647
0.4587 (3)
0.5738 (3)
0.637050
0.5959 (3)
0.675047
0.5034 (3)
0.519239
0.3885 (3)
0.324495
0.63427 (15)
0.63893 (15)
−0.05940 (16)
0.00698 (16)
0.49526 (19)
0.508 (3)
0.11513 (19)
0.105 (3)
0.6141 (2)
0.5217 (3)
0.467307
0.5098 (3)
0.446643
0.5889 (3)
0.580353
0.6804 (3)
0.734969
0.6933 (3)
0.756331
0.7070 (2)
0.7887 (2)
0.797858
0.8571 (2)
0.913608
0.8440 (2)
0.890988
0.7623 (3)
0.753476
0.0254 (5)
0.0253 (5)
0.0318 (5)
0.0302 (5)
0.0265 (6)
0.032*
0.0219 (5)
0.026*
0.0250 (6)
0.0360 (8)
0.043*
0.0439 (9)
0.053*
0.0459 (9)
0.055*
0.0479 (10)
0.057*
0.0354 (8)
0.043*
0.0226 (6)
0.0273 (7)
0.033*
0.0298 (7)
0.036*
0.0312 (7)
0.037*
0.0341 (7)
0.041*
0.0292 (7)
0.035*
0.0223 (6)
0.0311 (7)
0.037*
0.0393 (8)
0.047*
0.0416 (9)
0.050*
0.3649 (3)
0.285618
0.6929 (2)
0.636443
0.0130 (3)
−0.0946 (3)
−0.170591
−0.0936 (4)
−0.166997
0.0155 (4)
0.016385
0.1240 (4)
0.198339
0.1234 (4)
0.197440
−0.2400 (3)
−0.2626 (4)
−0.232796
−0.3287 (5)
−0.345967
−0.3702 (6)
−0.413225
−0.1361 (2)
−0.1764 (3)
−0.151648
−0.2529 (3)
−0.279690
−0.2890 (3)
−0.341821
−0.2507 (3)
−0.277099
−0.1726 (3)
−0.145023
0.0792 (3)
0.1231 (3)
0.105712
0.0396 (8)
0.048*
0.0366 (8)
0.044*
0.0303 (7)
0.0459 (10)
0.055*
0.0706 (16)
0.085*
0.1924 (4)
0.222593
0.2184 (5)
0.267800
0.0759 (17)
0.091*
H72A
Acta Cryst. (2018). C74, 1610-1621
sup-4

supporting information
C73
H73A
C74
H74A
C75
H75A
C76
H76A
H76B
C77
H77A
H77B
C78
H78A
C79
H79A
H79B
C80
0.2929 (5)
0.207170
0.2945 (4)
0.210461
0.5652 (3)
0.461588
0.6184 (3)
0.609956
0.724407
0.5282 (3)
0.570326
0.424610
0.5282 (3)
0.632622
0.4734 (4)
0.367420
0.481747
0.5637 (4)
0.666999
0.520889
−0.3492 (4)
−0.379974
−0.2836 (3)
−0.268358
0.3272 (3)
0.287969
0.2118 (3)
0.169972
0.251145
0.0996 (3)
0.029933
0.052260
0.1592 (3)
0.199943
0.2731 (3)
0.233105
0.314594
0.3857 (3)
0.433605
0.454931
0.1727 (4)
0.189258
0.1030 (3)
0.071514
0.4023 (2)
0.401526
0.3918 (2)
0.444124
0.399439
0.2927 (2)
0.286882
0.288412
0.2092 (2)
0.211595
0.2185 (2)
0.210725
0.166012
0.3178 (2)
0.321884
0.323514
0.0550 (12)
0.066*
0.0365 (8)
0.044*
0.0217 (6)
0.026*
0.0250 (6)
0.030*
0.030*
0.0236 (6)
0.028*
0.028*
0.0208 (6)
0.025*
0.0253 (6)
0.030*
0.030*
0.0262 (7)
0.031*
0.031*
H80A
H80B
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
P1
P2
0.0177 (3)
0.0171 (3)
0.0172 (3)
0.0172 (3)
0.0248 (10)
0.0260 (10)
0.0169 (9)
0.0191 (4)
0.0079 (3)
0.0075 (3)
0.0116 (8)
0.0094 (8)
0.0075 (8)
0.0080 (8)
0.0059 (8)
0.0153 (9)
0.0086 (9)
0.0090 (10)
0.0077 (11)
0.0094 (12)
0.0225 (14)
0.0109 (14)
0.0118 (14)
0.0169 (13)
0.0138 (11)
0.0103 (12)
0.0129 (14)
0.0198 (14)
0.0209 (14)
0.0129 (12)
0.0026 (11)
0.0114 (12)
0.0094 (3)
0.0086 (3)
0.0137 (9)
0.0100 (9)
0.0106 (9)
0.0112 (9)
0.0072 (8)
0.0177 (9)
0.0051 (10)
0.0061 (10)
0.0084 (12)
0.0103 (12)
0.0185 (15)
0.0183 (16)
0.0199 (15)
0.0170 (14)
0.0162 (13)
0.0136 (14)
0.0212 (17)
0.0238 (16)
0.0134 (14)
0.0105 (13)
0.0050 (11)
0.0149 (13)
0.0065 (3)
0.0052 (3)
0.0102 (9)
0.0066 (8)
0.0069 (8)
0.0075 (8)
0.0052 (8)
0.0116 (9)
0.0047 (9)
0.0018 (10)
0.0067 (11)
0.0106 (12)
0.0183 (13)
0.0178 (14)
0.0244 (15)
0.0171 (14)
0.0140 (12)
0.0102 (13)
0.0211 (15)
0.0307 (16)
0.0214 (15)
0.0122 (12)
0.0034 (11)
0.0119 (12)
0.0191 (4)
0.0307 (12)
0.0271 (11)
0.0204 (10)
0.0216 (10)
0.0185 (10)
0.0250 (11)
0.0198 (12)
0.0183 (13)
0.0173 (14)
0.0221 (15)
0.0355 (17)
0.0398 (19)
0.045 (2)
O1
O2
O3
O4
O5
O6
N1
N2
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
0.0211 (10)
0.0166 (10)
0.0296 (11)
0.0264 (10)
0.0203 (10)
0.0294 (11)
0.0147 (11)
0.0152 (11)
0.0250 (14)
0.0204 (14)
0.0387 (17)
0.0380 (18)
0.0276 (16)
0.0280 (16)
0.0230 (14)
0.0305 (15)
0.0376 (18)
0.0331 (17)
0.0286 (16)
0.0274 (16)
0.0193 (13)
0.0273 (15)
0.0177 (9)
0.0184 (10)
0.0246 (10)
0.0212 (12)
0.0238 (12)
0.0176 (13)
0.0300 (15)
0.0293 (16)
0.0260 (15)
0.0381 (18)
0.0335 (17)
0.0226 (14)
0.0221 (14)
0.0250 (16)
0.0364 (18)
0.0454 (19)
0.0265 (15)
0.0171 (13)
0.0268 (15)
0.0328 (17)
0.0295 (16)
0.0324 (17)
0.054 (2)
0.052 (2)
0.0320 (17)
0.0296 (17)
0.0184 (14)
0.0316 (16)
Acta Cryst. (2018). C74, 1610-1621
sup-5

supporting information
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
C26
C27
C28
C29
C30
C32
P51
P52
O51
O52
O53
O54
O55
O56
N51
N52
C51
C52
C53
C54
C55
C56
C57
C58
C59
C60
C61
C62
C63
C64
C65
C66
C67
C68
C69
C70
C71
C72
0.0395 (18)
0.044 (2)
0.0286 (16)
0.0348 (18)
0.0365 (18)
0.0258 (15)
0.0264 (15)
0.0261 (15)
0.0450 (19)
0.054 (2)
0.049 (2)
0.045 (2)
0.0194 (14)
0.0165 (15)
0.0131 (15)
0.0102 (12)
0.0127 (12)
0.0089 (12)
0.0153 (14)
0.0254 (16)
0.0137 (14)
0.0067 (13)
0.0085 (12)
0.0101 (12)
0.0097 (11)
0.0080 (11)
0.0092 (11)
0.0085 (11)
0.0076 (3)
0.0104 (3)
0.0142 (9)
0.0128 (9)
0.0058 (8)
0.0123 (9)
0.0224 (10)
0.0096 (9)
0.0059 (10)
0.0043 (10)
0.0095 (12)
0.0116 (15)
0.0275 (18)
0.0204 (17)
0.0072 (16)
0.0086 (14)
0.0140 (12)
0.0101 (12)
0.0168 (14)
0.0214 (14)
0.0119 (14)
0.0056 (13)
0.0073 (11)
0.0105 (13)
0.0130 (16)
0.0084 (16)
0.0102 (16)
0.0145 (15)
0.0135 (13)
0.0283 (17)
0.057 (3)
0.0214 (17)
0.0231 (17)
0.0241 (16)
0.0136 (13)
0.0106 (12)
0.0122 (13)
0.0162 (14)
0.0171 (14)
0.0081 (14)
0.0102 (13)
0.0119 (13)
0.0114 (13)
0.0050 (12)
0.0121 (12)
0.0110 (12)
0.0065 (12)
0.0072 (3)
0.0086 (3)
0.0084 (9)
0.0115 (9)
0.0069 (9)
0.0150 (9)
0.0146 (10)
0.0138 (10)
0.0067 (11)
0.0105 (11)
0.0155 (13)
0.0099 (15)
0.030 (2)
0.0197 (15)
0.0269 (16)
0.0162 (14)
0.0095 (12)
0.0098 (11)
0.0125 (12)
0.0205 (15)
0.0153 (15)
0.0000 (13)
0.0047 (13)
0.0072 (11)
0.0092 (12)
0.0038 (11)
0.0066 (11)
0.0073 (11)
0.0043 (11)
0.0044 (3)
0.0082 (3)
0.0086 (9)
0.0103 (9)
0.0060 (8)
0.0094 (9)
0.0183 (10)
0.0025 (9)
0.0001 (11)
0.0058 (10)
0.0100 (12)
0.0091 (14)
0.0273 (18)
0.0210 (17)
0.0058 (16)
0.0065 (14)
0.0133 (12)
0.0078 (13)
0.0118 (13)
0.0214 (14)
0.0226 (15)
0.0097 (13)
0.0074 (11)
0.0071 (14)
0.0036 (15)
0.0137 (16)
0.0250 (16)
0.0156 (15)
0.0084 (13)
0.033 (2)
0.0380 (18)
0.0263 (15)
0.0228 (14)
0.0279 (15)
0.0281 (16)
0.0337 (17)
0.0305 (17)
0.0248 (15)
0.0266 (15)
0.0287 (16)
0.0176 (13)
0.0225 (15)
0.0227 (14)
0.0180 (13)
0.0151 (3)
0.0166 (3)
0.0185 (10)
0.0192 (10)
0.0225 (10)
0.0252 (10)
0.0282 (11)
0.0323 (12)
0.0135 (12)
0.0141 (11)
0.0236 (15)
0.0368 (18)
0.060 (2)
0.0378 (19)
0.0312 (17)
0.0176 (14)
0.0278 (16)
0.0334 (18)
0.0248 (16)
0.0246 (16)
0.0282 (17)
0.0229 (15)
0.0191 (15)
0.0158 (14)
0.0217 (15)
0.0175 (14)
0.0178 (14)
0.0223 (4)
0.0196 (4)
0.0267 (11)
0.0271 (11)
0.0258 (11)
0.0304 (12)
0.0277 (12)
0.0274 (12)
0.0257 (14)
0.0265 (14)
0.0310 (17)
0.0299 (18)
0.045 (2)
0.0387 (18)
0.0274 (16)
0.0182 (13)
0.0240 (14)
0.0207 (13)
0.0192 (13)
0.0206 (13)
0.0208 (14)
0.0249 (4)
0.0305 (4)
0.0399 (12)
0.0353 (12)
0.0226 (10)
0.0254 (11)
0.0504 (14)
0.0275 (11)
0.0325 (14)
0.0234 (12)
0.0243 (14)
0.0361 (18)
0.046 (2)
0.0303 (18)
0.0265 (17)
0.0308 (17)
0.0263 (14)
0.0268 (15)
0.0324 (16)
0.0410 (18)
0.0405 (18)
0.0265 (15)
0.0283 (15)
0.0321 (17)
0.046 (2)
0.063 (2)
0.062 (2)
0.062 (3)
0.048 (2)
0.043 (2)
0.029 (2)
0.0403 (19)
0.0224 (14)
0.0227 (15)
0.0321 (17)
0.0333 (17)
0.0269 (16)
0.0252 (15)
0.0168 (13)
0.0277 (17)
0.0346 (19)
0.0322 (18)
0.0351 (18)
0.0338 (18)
0.0331 (17)
0.039 (2)
0.0317 (18)
0.0272 (16)
0.0316 (18)
0.0294 (17)
0.0344 (18)
0.041 (2)
0.0305 (17)
0.0190 (14)
0.0323 (18)
0.0300 (18)
0.0297 (18)
0.0334 (19)
0.0394 (19)
0.0433 (19)
0.077 (3)
0.0180 (15)
0.0122 (12)
0.0101 (14)
0.0123 (14)
0.0203 (15)
0.0179 (15)
0.0081 (13)
0.0051 (11)
0.0136 (14)
0.0116 (15)
0.0102 (15)
0.0113 (15)
0.0092 (15)
0.0195 (15)
0.037 (2)
0.054 (2)
0.049 (2)
0.0356 (18)
0.0197 (15)
0.047 (2)
0.055 (3)
0.068 (3)
0.094 (4)
0.100 (4)
0.125 (5)
0.133 (5)
0.056 (3)
0.068 (3)
0.083 (4)
0.100 (4)
0.061 (3)
Acta Cryst. (2018). C74, 1610-1621
sup-6

supporting information
C73
C74
C75
C76
C77
C78
C79
C80
0.052 (2)
0.058 (2)
0.099 (4)
0.059 (2)
0.038 (2)
0.052 (3)
0.054 (3)
0.0324 (17)
0.0161 (14)
0.0249 (15)
0.0248 (15)
0.0156 (13)
0.0292 (16)
0.0305 (17)
0.0338 (17)
0.0244 (14)
0.0255 (14)
0.0192 (14)
0.0232 (14)
0.0234 (14)
0.0239 (15)
0.0204 (14)
0.0074 (11)
0.0102 (12)
0.0088 (12)
0.0066 (11)
0.0142 (12)
0.0161 (13)
0.0250 (17)
0.0093 (12)
0.0088 (13)
0.0110 (13)
0.0082 (12)
0.0097 (13)
0.0114 (14)
0.0248 (16)
0.0033 (12)
0.0119 (12)
0.0105 (12)
0.0077 (12)
0.0114 (12)
0.0094 (13)
0.0230 (16)
0.0259 (16)
0.0288 (16)
0.0232 (16)
0.0274 (16)
0.0292 (17)
Geometric parameters (Å, º)
P1—O1
1.463 (2)
P51—O51
1.466 (2)
P1—O3
P1—O4
P1—N1
P2—O2
P2—O6
P2—O5
P2—N2
O3—C1
1.590 (2)
1.5937 (19)
1.609 (2)
1.468 (2)
1.580 (2)
1.5900 (19)
1.602 (2)
1.415 (3)
1.407 (3)
1.406 (3)
1.411 (3)
1.473 (4)
0.85 (2)
1.464 (3)
0.85 (2)
1.375 (4)
1.378 (4)
1.385 (4)
0.9500
1.390 (5)
0.9500
1.379 (5)
0.9500
1.387 (4)
0.9500
0.9500
1.375 (4)
1.385 (4)
1.393 (4)
0.9500
1.375 (5)
0.9500
1.382 (5)
0.9500
1.390 (4)
0.9500
P51—O53
P51—O54
P51—N51
P52—O52
P52—O56
P52—O55
P52—N52
O53—C51
O54—C57
O55—C63
O56—C69
N51—C75
N51—H51N
N52—C78
N52—H52N
C51—C56
C51—C52
C52—C53
C52—H52C
C53—C54
C53—H53A
C54—C55
C54—H54A
C55—C56
C55—H55A
C56—H56A
C57—C58
C57—C62
C58—C59
C58—H58A
C59—C60
C59—H59A
C60—C61
C60—H60A
C61—C62
C61—H61A
1.585 (2)
1.590 (2)
1.603 (3)
1.468 (2)
1.586 (2)
1.593 (2)
1.595 (3)
1.398 (3)
1.405 (4)
1.397 (4)
1.404 (4)
1.467 (4)
0.87 (2)
1.468 (4)
0.84 (2)
1.368 (4)
1.380 (5)
1.390 (5)
0.9500
1.378 (6)
0.9500
1.378 (6)
0.9500
1.389 (5)
0.9500
0.9500
1.378 (4)
1.381 (4)
1.380 (5)
0.9500
1.389 (5)
0.9500
1.375 (5)
0.9500
1.381 (5)
0.9500
O4—C7
O5—C13
O6—C19
N1—C32
N1—H1N
N2—C28
N2—H2N
C1—C2
C1—C6
C2—C3
C2—H2C
C3—C4
C3—H3A
C4—C5
C4—H4A
C5—C6
C5—H5A
C6—H6A
C7—C12
C7—C8
C8—C9
C8—H8A
C9—C10
C9—H9A
C10—C11
C10—H10A
C11—C12
C11—H11A
Acta Cryst. (2018). C74, 1610-1621
sup-7

supporting information
C12—H12A
C13—C14
C13—C18
C14—C15
C14—H14A
C15—C16
C15—H15A
C16—C17
C16—H16A
C17—C18
C17—H17A
C18—H18A
C19—C24
C19—C20
C20—C21
C20—H20A
C21—C22
C21—H21A
C22—C23
C22—H22A
C23—C24
C23—H23A
C24—H24A
C26—C27
C26—C32
C26—H26A
C26—H26B
C27—C28
C27—H27A
C27—H27B
C28—C29
C28—H28A
C29—C30
C29—H29A
C29—H29B
C30—C32
C30—H30A
C30—H30B
C32—H32A
0.9500
C62—H62A
C63—C64
C63—C68
C64—C65
C64—H64A
C65—C66
C65—H65A
C66—C67
C66—H66A
C67—C68
C67—H67A
C68—H68A
C69—C70
C69—C74
C70—C71
C70—H70A
C71—C72
C71—H71A
C72—C73
C72—H72A
C73—C74
C73—H73A
C74—H74A
C75—C76
C75—C80
C75—H75A
C76—C77
C76—H76A
C76—H76B
C77—C78
C77—H77A
C77—H77B
C78—C79
C78—H78A
C79—C80
C79—H79A
C79—H79B
C80—H80A
C80—H80B
0.9500
1.381 (4)
1.382 (4)
1.382 (4)
0.9500
1.385 (5)
0.9500
1.389 (5)
0.9500
1.382 (5)
0.9500
1.373 (5)
1.388 (5)
1.387 (5)
0.9500
1.372 (6)
0.9500
1.379 (6)
0.9500
1.400 (5)
0.9500
0.9500
0.9500
1.375 (4)
1.383 (4)
1.385 (4)
0.9500
1.373 (5)
0.9500
1.389 (5)
0.9500
1.381 (5)
0.9500
1.371 (5)
1.384 (5)
1.375 (6)
0.9500
1.393 (6)
0.9500
1.372 (6)
0.9500
1.375 (5)
0.9500
0.9500
0.9500
1.523 (4)
1.524 (4)
0.9900
0.9900
1.522 (4)
0.9900
0.9900
1.520 (4)
1.0000
1.525 (4)
0.9900
0.9900
1.523 (4)
1.523 (4)
1.0000
1.528 (4)
0.9900
0.9900
1.518 (4)
0.9900
0.9900
1.518 (4)
1.0000
1.533 (4)
0.9900
0.9900
1.529 (4)
0.9900
0.9900
0.9900
0.9900
1.0000
O1—P1—O3
O1—P1—O4
O3—P1—O4
O1—P1—N1
O3—P1—N1
O4—P1—N1
O2—P2—O6
O2—P2—O5
115.74 (12)
114.34 (12)
94.73 (10)
113.23 (12)
109.01 (12)
108.18 (12)
113.89 (12)
115.07 (12)
O51—P51—O53
O51—P51—O54
O53—P51—O54
O51—P51—N51
O53—P51—N51
O54—P51—N51
O52—P52—O56
O52—P52—O55
115.32 (12)
112.46 (12)
100.97 (11)
116.36 (14)
104.92 (12)
105.21 (13)
114.91 (13)
113.48 (12)
Acta Cryst. (2018). C74, 1610-1621
sup-8

supporting information
O6—P2—O5
O2—P2—N2
O6—P2—N2
O5—P2—N2
C1—O3—P1
C7—O4—P1
C13—O5—P2
C19—O6—P2
C32—N1—P1
C32—N1—H1N
P1—N1—H1N
C28—N2—P2
C28—N2—H2N
P2—N2—H2N
C2—C1—C6
100.23 (11)
114.21 (13)
106.65 (12)
105.44 (11)
116.03 (17)
123.86 (18)
118.23 (17)
122.84 (18)
124.40 (19)
113 (2)
O56—P52—O55
O52—P52—N52
O56—P52—N52
O55—P52—N52
C51—O53—P51
C57—O54—P51
C63—O55—P52
C69—O56—P52
C75—N51—P51
C75—N51—H51N
P51—N51—H51N
C78—N52—P52
C78—N52—H52N
P52—N52—H52N
C56—C51—C52
C56—C51—O53
C52—C51—O53
C51—C52—C53
C51—C52—H52C
C53—C52—H52C
C54—C53—C52
C54—C53—H53A
C52—C53—H53A
C55—C54—C53
C55—C54—H54A
C53—C54—H54A
C54—C55—C56
C54—C55—H55A
C56—C55—H55A
C51—C56—C55
C51—C56—H56A
C55—C56—H56A
C58—C57—C62
C58—C57—O54
C62—C57—O54
C57—C58—C59
C57—C58—H58A
C59—C58—H58A
C58—C59—C60
C58—C59—H59A
C60—C59—H59A
C61—C60—C59
C61—C60—H60A
C59—C60—H60A
C60—C61—C62
C60—C61—H61A
C62—C61—H61A
C57—C62—C61
100.21 (13)
114.76 (12)
107.10 (12)
104.95 (13)
126.20 (19)
121.73 (19)
123.82 (19)
119.24 (19)
123.7 (2)
119 (2)
119 (2)
124.3 (2)
115 (2)
116 (2)
125.6 (2)
114 (2)
118 (2)
120 (2)
122.0 (3)
118.5 (2)
119.5 (3)
119.0 (3)
120.5
120.5
120.0 (3)
120.0
120.0
119.9 (3)
120.0
120.0
120.5 (3)
119.8
121.5 (3)
115.1 (3)
123.5 (3)
118.8 (3)
120.6
120.6
120.4 (4)
119.8
119.8
119.7 (3)
120.1
120.1
120.4 (3)
119.8
C2—C1—O3
C6—C1—O3
C1—C2—C3
C1—C2—H2C
C3—C2—H2C
C2—C3—C4
C2—C3—H3A
C4—C3—H3A
C5—C4—C3
C5—C4—H4A
C3—C4—H4A
C4—C5—C6
C4—C5—H5A
C6—C5—H5A
C1—C6—C5
C1—C6—H6A
C5—C6—H6A
C12—C7—C8
C12—C7—O4
C8—C7—O4
119.8
118.6 (3)
120.7
119.8
119.2 (3)
120.4
120.7
120.4
121.7 (3)
123.8 (3)
114.5 (3)
118.5 (3)
120.8
120.8
120.5 (3)
119.7
119.7
120.1 (3)
119.9
119.9
120.2 (3)
119.9
121.3 (3)
120.4 (3)
118.1 (3)
119.0 (3)
120.5
120.5
120.6 (3)
119.7
119.7
119.3 (3)
120.4
120.4
121.0 (3)
119.5
C7—C8—C9
C7—C8—H8A
C9—C8—H8A
C10—C9—C8
C10—C9—H9A
C8—C9—H9A
C9—C10—C11
C9—C10—H10A
C11—C10—H10A
C10—C11—C12
C10—C11—H11A
C12—C11—H11A
C7—C12—C11
119.9
118.9 (3)
119.5
118.8 (3)
Acta Cryst. (2018). C74, 1610-1621
sup-9

supporting information
C7—C12—H12A
C11—C12—H12A
C14—C13—C18
C14—C13—O5
120.5
120.5
C57—C62—H62A
C61—C62—H62A
C64—C63—C68
C64—C63—O55
C68—C63—O55
C63—C64—C65
C63—C64—H64A
C65—C64—H64A
C66—C65—C64
C66—C65—H65A
C64—C65—H65A
C65—C66—C67
C65—C66—H66A
C67—C66—H66A
C66—C67—C68
C66—C67—H67A
C68—C67—H67A
C63—C68—C67
C63—C68—H68A
C67—C68—H68A
C70—C69—C74
C70—C69—O56
C74—C69—O56
C69—C70—C71
C69—C70—H70A
C71—C70—H70A
C70—C71—C72
C70—C71—H71A
C72—C71—H71A
C73—C72—C71
C73—C72—H72A
C71—C72—H72A
C72—C73—C74
C72—C73—H73A
C74—C73—H73A
C73—C74—C69
C73—C74—H74A
C69—C74—H74A
N51—C75—C76
N51—C75—C80
C76—C75—C80
N51—C75—H75A
C76—C75—H75A
C80—C75—H75A
C75—C76—C77
C75—C76—H76A
C77—C76—H76A
C75—C76—H76B
120.6
120.6
122.3 (3)
118.3 (3)
119.4 (3)
118.3 (3)
120.8
120.8
120.7 (3)
119.6
119.6
119.7 (3)
120.1
120.1
120.5 (3)
119.8
120.6 (3)
122.0 (3)
117.4 (3)
120.7 (3)
119.7
119.7
118.7 (4)
120.6
120.6
121.8 (3)
119.1
119.1
119.2 (3)
120.4
C18—C13—O5
C13—C14—C15
C13—C14—H14A
C15—C14—H14A
C14—C15—C16
C14—C15—H15A
C16—C15—H15A
C15—C16—C17
C15—C16—H16A
C17—C16—H16A
C18—C17—C16
C18—C17—H17A
C16—C17—H17A
C13—C18—C17
C13—C18—H18A
C17—C18—H18A
C24—C19—C20
C24—C19—O6
119.8
118.5 (3)
120.8
120.4
119.0 (3)
120.5
120.8
120.5
121.9 (3)
120.8 (2)
117.2 (2)
118.4 (3)
120.8
120.8
120.7 (3)
119.6
119.6
119.9 (3)
120.1
120.1
120.3 (3)
119.9
119.9
118.8 (3)
120.6
120.6
111.1 (2)
109.4
109.4
109.4
109.4
108.0
121.1 (3)
121.0 (3)
117.8 (3)
119.4 (3)
120.3
120.3
119.9 (4)
120.1
120.1
120.1 (4)
120.0
120.0
120.2 (4)
119.9
C20—C19—O6
C19—C20—C21
C19—C20—H20A
C21—C20—H20A
C22—C21—C20
C22—C21—H21A
C20—C21—H21A
C21—C22—C23
C21—C22—H22A
C23—C22—H22A
C24—C23—C22
C24—C23—H23A
C22—C23—H23A
C19—C24—C23
C19—C24—H24A
C23—C24—H24A
C27—C26—C32
C27—C26—H26A
C32—C26—H26A
C27—C26—H26B
C32—C26—H26B
H26A—C26—H26B
C28—C27—C26
C28—C27—H27A
C26—C27—H27A
C28—C27—H27B
119.9
119.2 (3)
120.4
120.4
110.4 (2)
110.1 (2)
110.9 (2)
108.4
108.4
108.4
111.7 (2)
109.3
109.3
111.2 (2)
109.4
109.4
109.4
109.3
Acta Cryst. (2018). C74, 1610-1621
sup-10

supporting information
C26—C27—H27B
H27A—C27—H27B
N2—C28—C29
109.4
108.0
109.6 (2)
112.2 (2)
110.8 (2)
108.0
108.0
108.0
111.6 (2)
109.3
109.3
109.3
109.3
108.0
111.8 (2)
109.3
109.3
109.3
109.3
107.9
C77—C76—H76B
H76A—C76—H76B
C78—C77—C76
C78—C77—H77A
C76—C77—H77A
C78—C77—H77B
C76—C77—H77B
H77A—C77—H77B
N52—C78—C79
N52—C78—C77
C79—C78—C77
N52—C78—H78A
C79—C78—H78A
C77—C78—H78A
C78—C79—C80
C78—C79—H79A
C80—C79—H79A
C78—C79—H79B
C80—C79—H79B
H79A—C79—H79B
C75—C80—C79
C75—C80—H80A
C79—C80—H80A
C75—C80—H80B
C79—C80—H80B
H80A—C80—H80B
109.3
108.0
111.8 (2)
109.3
109.3
109.3
109.3
107.9
110.2 (2)
110.6 (2)
111.2 (3)
108.2
108.2
108.2
111.1 (3)
109.4
109.4
109.4
109.4
N2—C28—C27
C29—C28—C27
N2—C28—H28A
C29—C28—H28A
C27—C28—H28A
C28—C29—C30
C28—C29—H29A
C30—C29—H29A
C28—C29—H29B
C30—C29—H29B
H29A—C29—H29B
C29—C30—C32
C29—C30—H30A
C32—C30—H30A
C29—C30—H30B
C32—C30—H30B
H30A—C30—H30B
N1—C32—C26
108.0
112.2 (2)
109.2
109.2
109.2
109.4 (2)
110.6 (2)
111.2 (2)
108.5
108.5
108.5
N1—C32—C30
C26—C32—C30
N1—C32—H32A
C26—C32—H32A
C30—C32—H32A
109.2
107.9
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
N1—H1N···O52i
N2—H2N···O51
N51—H51N···O2ii
N52—H52N···O1
C22—H22A···O4iii
C6—H6A···O55
C74—H74A···O1
C2—H2C···O52i
C2—H2C···CG1i
0.85 (2)
0.85 (2)
0.87 (2)
0.84 (2)
0.95
0.95
0.95
0.95
0.95
2.03 (2)
2.00 (2)
1.98 (3)
2.04 (2)
2.51
2.69
2.61
2.69
2.92
2.863 (3)
2.820 (3)
2.802 (3)
2.866 (3)
3.418 (4)
3.565 (4)
3.329 (4)
3.465 (3)
3.593 (8)
167 (3)
162 (3)
158 (3)
168 (3)
160
154
133
139
129
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) x, y+1, z+1.
N,N′-(1,4-Phenylene)bis(O,O′-dimethylthiophosphoramidate) (bv18)
Crystal data
C10H18N2O4P2S2
Mr = 356.32
Monoclinic, P21/a
a = 13.2517 (3) Å
b = 10.0091 (2) Å
c = 13.9580 (3) Å
β = 112.9309 (12)°
V = 1705.05 (6) Å3
Acta Cryst. (2018). C74, 1610-1621
sup-11

supporting information
Z = 4
F(000) = 744
Dx = 1.388 Mg m−3
θ = 3.1–28.0°
µ = 0.51 mm−1
T = 295 K
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 6840 reflections
Block, colourless
0.43 × 0.36 × 0.31 mm
Data collection
Nonius KappaCCD
diffractometer
Radiation source: fine-focus sealed tube
φ scans and ω scans
4091 independent reflections
3267 reflections with I > 2σ(I)
Rint = 0.019
θ
max = 28.0°, θmin = 3.1°
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
h = −17→17
k = −12→13
l = −18→18
T
min = 0.790, Tmax = 0.845
6840 measured reflections
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.042
wR(F2) = 0.115
S = 1.02
Hydrogen site location: mixed
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0488P)2 + 0.9571P]
where P = (Fo2 + 2Fc2)/3
4091 reflections
191 parameters
2 restraints
(Δ/σ)max = 0.001
Δρmax = 0.70 e Å−3
Δρmin = −0.48 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
C1
C2
H2
C3
H3
C4
C5
H5
C6
H6
N1
H1N
P1
−0.10510 (16)
−0.05330 (16)
−0.080489
0.03820 (16)
0.071866
0.07964 (16)
0.03004 (16)
0.058510
−0.06154 (17)
−0.093740
0.22673 (18)
0.33804 (19)
0.422741
0.3252 (2)
0.400946
0.19929 (19)
0.0882 (2)
0.003716
0.10094 (19)
0.025412
0.24601 (16)
0.3233 (18)
0.13688 (5)
0.22087 (6)
0.04058 (16)
0.0939 (5)
0.153669
0.16416 (14)
0.22145 (15)
0.197783
0.31329 (15)
0.350764
0.34936 (15)
0.29087 (15)
0.313678
0.19870 (15)
0.160088
0.0383 (4)
0.0406 (4)
0.049*
0.0432 (5)
0.052*
0.0401 (4)
0.0442 (5)
0.053*
0.0441 (5)
0.053*
−0.19948 (15)
−0.218 (2)
0.07154 (14)
0.060 (2)
0.0491 (5)
0.059*
−0.27879 (4)
−0.39878 (5)
−0.20470 (13)
−0.1410 (3)
−0.185412
−0.00992 (4)
−0.11912 (5)
−0.04448 (12)
−0.0986 (3)
−0.152217
0.03875 (14)
0.05876 (19)
0.0535 (4)
0.1061 (13)
0.159*
S1
O1
C7
H7A
Acta Cryst. (2018). C74, 1610-1621
sup-12

supporting information
H7B
H7C
O2
−0.115829
−0.079075
−0.30821 (13)
−0.3725 (3)
−0.335379
−0.381900
−0.442969
0.17100 (16)
0.188 (2)
0.24331 (4)
0.35199 (5)
0.28520 (14)
0.3563 (4)
0.427943
0.022073
0.141495
−0.129260
−0.050487
0.05507 (12)
0.1146 (3)
0.163726
0.151065
0.068415
0.44518 (14)
0.460 (2)
0.53117 (4)
0.65024 (5)
0.47204 (13)
0.4224 (3)
0.474035
0.378888
0.380640
0.55171 (14)
0.6169 (4)
0.663516
0.159*
0.159*
0.0553 (4)
0.0930 (11)
0.140*
0.140*
0.140*
0.0541 (5)
0.065*
0.04238 (15)
0.0634 (2)
0.0635 (4)
0.1276 (17)
0.191*
0.191*
0.191*
0.0803 (6)
0.152 (2)
0.228*
0.02609 (16)
0.0616 (4)
0.130267
−0.015587
0.093827
0.18068 (18)
0.0995 (18)
0.28916 (5)
0.20676 (7)
0.39623 (18)
0.3603 (6)
0.341952
0.432479
0.282030
0.3914 (2)
0.3727 (6)
0.300551
C8
H8A
H8B
H8C
N2
H2N
P2
S2
O3
C9
H9A
H9B
H9C
O4
C10
H10A
H10B
H10C
0.360601
0.328474
0.16411 (17)
0.1129 (4)
0.147202
0.037320
0.117510
0.351315
0.452852
0.577502
0.656121
0.228*
0.228*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
C1
C2
C3
C4
C5
C6
N1
P1
0.0372 (10)
0.0435 (10)
0.0459 (11)
0.0369 (10)
0.0461 (11)
0.0472 (11)
0.0479 (10)
0.0376 (3)
0.0486 (3)
0.0531 (9)
0.094 (2)
0.0324 (9)
0.0282 (8)
0.0317 (9)
0.0365 (9)
0.0307 (9)
0.0305 (9)
0.0277 (8)
0.0323 (3)
0.0500 (3)
0.0547 (9)
0.145 (3)
0.0343 (9)
−0.0009 (7)
0.0019 (8)
−0.0028 (8)
0.0010 (8)
0.0051 (8)
0.0007 (8)
0.0019 (7)
−0.00116 (19)
0.0034 (2)
0.0068 (7)
0.021 (2)
−0.0091 (7)
−0.020 (2)
0.0037 (8)
0.0027 (2)
0.0054 (3)
−0.0133 (9)
−0.007 (3)
0.0405 (12)
0.063 (4)
0.0021 (8)
0.0046 (8)
0.0033 (8)
0.0005 (8)
0.0027 (8)
0.0012 (8)
−0.0100 (8)
0.0034 (2)
−0.0103 (2)
0.0172 (7)
0.065 (2)
0.0183 (7)
0.0494 (18)
−0.0114 (8)
0.0050 (2)
−0.0089 (3)
0.0134 (8)
0.073 (3)
−0.0010 (7)
0.0011 (8)
−0.0040 (8)
0.0003 (8)
0.0010 (8)
−0.0040 (8)
−0.0005 (7)
−0.0027 (2)
−0.0014 (3)
−0.0068 (7)
0.021 (3)
0.0395 (10)
0.0397 (10)
0.0345 (9)
0.0426 (10)
0.0401 (10)
0.0458 (9)
0.0363 (3)
0.0506 (3)
0.0502 (8)
0.104 (3)
0.0557 (9)
0.0770 (19)
0.0469 (10)
0.0335 (3)
0.0421 (3)
0.0548 (9)
0.108 (3)
S1
O1
C7
O2
C8
N2
P2
0.0567 (9)
0.092 (2)
0.0503 (9)
0.125 (3)
0.0048 (7)
0.000 (2)
0.0529 (11)
0.0421 (3)
0.0600 (4)
0.0650 (10)
0.111 (3)
0.0343 (9)
0.0426 (3)
0.0617 (4)
0.0615 (10)
0.191 (5)
−0.0006 (8)
−0.0046 (2)
−0.0022 (3)
0.0006 (8)
0.016 (3)
S2
O3
C9
O4
C10
0.0843 (13)
0.128 (4)
0.0981 (15)
0.238 (6)
0.0541 (10)
0.122 (3)
0.0220 (9)
0.085 (3)
−0.0052 (10)
0.007 (4)
Acta Cryst. (2018). C74, 1610-1621
sup-13

supporting information
Geometric parameters (Å, º)
C1—C2
C1—C6
C1—N1
C2—C3
C2—H2
C3—C4
C3—H3
C4—C5
C4—N2
C5—C6
C5—H5
C6—H6
N1—P1
N1—H1N
P1—O2
P1—O1
P1—S1
1.387 (3)
1.391 (3)
1.419 (2)
1.385 (3)
0.9300
1.389 (3)
0.9300
1.385 (3)
1.424 (2)
1.388 (3)
0.9300
C7—H7B
C7—H7C
O2—C8
C8—H8A
C8—H8B
C8—H8C
N2—P2
N2—H2N
P2—O4
P2—O3
0.9600
0.9600
1.447 (3)
0.9600
0.9600
0.9600
1.6253 (18)
0.847 (17)
1.5702 (18)
1.5794 (18)
1.9109 (8)
1.416 (4)
0.9600
0.9600
0.9600
1.343 (4)
0.9600
0.9600
P2—S2
O3—C9
0.9300
1.6307 (17)
0.807 (16)
1.5749 (16)
1.5795 (16)
1.9156 (7)
1.437 (3)
0.9600
C9—H9A
C9—H9B
C9—H9C
O4—C10
C10—H10A
C10—H10B
C10—H10C
O1—C7
C7—H7A
0.9600
C2—C1—C6
C2—C1—N1
C6—C1—N1
C3—C2—C1
C3—C2—H2
C1—C2—H2
C2—C3—C4
C2—C3—H3
C4—C3—H3
C5—C4—C3
C5—C4—N2
C3—C4—N2
C4—C5—C6
C4—C5—H5
C6—C5—H5
C5—C6—C1
C5—C6—H6
C1—C6—H6
C1—N1—P1
C1—N1—H1N
P1—N1—H1N
O2—P1—O1
O2—P1—N1
O1—P1—N1
O2—P1—S1
O1—P1—S1
118.81 (17)
118.59 (17)
122.59 (17)
121.15 (18)
119.4
119.4
119.95 (18)
120.0
H7A—C7—H7C
H7B—C7—H7C
C8—O2—P1
O2—C8—H8A
O2—C8—H8B
H8A—C8—H8B
O2—C8—H8C
H8A—C8—H8C
H8B—C8—H8C
C4—N2—P2
C4—N2—H2N
P2—N2—H2N
O4—P2—O3
O4—P2—N2
O3—P2—N2
O4—P2—S2
O3—P2—S2
N2—P2—S2
C9—O3—P2
O3—C9—H9A
O3—C9—H9B
H9A—C9—H9B
O3—C9—H9C
H9A—C9—H9C
H9B—C9—H9C
C10—O4—P2
109.5
109.5
119.39 (19)
109.5
109.5
109.5
109.5
109.5
109.5
130.33 (15)
113.7 (19)
115.9 (18)
92.82 (12)
109.06 (11)
107.07 (10)
116.96 (8)
116.63 (7)
112.43 (7)
121.3 (3)
109.5
120.0
119.05 (17)
118.90 (17)
122.05 (17)
121.01 (18)
119.5
119.5
119.96 (18)
120.0
120.0
130.09 (14)
113.4 (19)
116.4 (19)
93.96 (9)
107.88 (10)
108.26 (10)
116.89 (7)
116.54 (7)
109.5
109.5
109.5
109.5
109.5
125.7 (3)
Acta Cryst. (2018). C74, 1610-1621
sup-14

supporting information
N1—P1—S1
C7—O1—P1
O1—C7—H7A
O1—C7—H7B
H7A—C7—H7B
O1—C7—H7C
111.75 (7)
119.8 (2)
109.5
109.5
109.5
O4—C10—H10A
O4—C10—H10B
H10A—C10—H10B
O4—C10—H10C
H10A—C10—H10C
H10B—C10—H10C
109.5
109.5
109.5
109.5
109.5
109.5
109.5
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
C3—H3···O3
C3—H3···O4
N1—H1N···O1i
N2—H2N···O3ii
0.93
0.93
0.81 (2)
0.85 (2)
2.67
2.59
2.38 (2)
2.22 (2)
3.237 (2)
3.158 (3)
3.174 (2)
3.042 (3)
120
120
169 (2)
165 (2)
Symmetry codes: (i) −x−1/2, y+1/2, −z; (ii) −x+1/2, y−1/2, −z+1.
Acta Cryst. (2018). C74, 1610-1621
sup-15