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

Vahdani Alviri, B.; Pourayoubi, M.; Farhadipour, A.; Nečas, M.; Bertolasi, V.

doi:10.1107/S2053229618014006

A combined X-ray crystallography and theoretical study of N—HOX (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

B. Vahdani Alviri, M. Pourayoubi, A. Farhadipour, M. Nečas and V. Bertolasi

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)(OC₆H₅)₂, (I), and N,N′-(1,4-phenylene)bis(O,O′-dimethylthiophosphoramide), C₁₀H₁₈N₂O₄P₂S₂ 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—H

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—H

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 σ*(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—H

O hydrogen bonds observed in the crystal packing. The details of the intermolecular interactions were studied by Hirshfeld surface maps and two-dimensional fingerprint plots.

Keywords: phosphoramide; thiophosphoramide; X-ray diffraction; N—H

O hydrogen bond; crystal structure; quantum chemical calculations; Hirshfeld surface analysis.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229618014006/cu3131sup1.cif Contains datablocks bv91, bv18, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618014006/cu3131bv91sup2.hkl Contains datablock bv91
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618014006/cu3131bv18sup3.hkl Contains datablock bv18
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229618014006/cu3131sup4.pdf Additional details of the CSD analysis, Hirshfeld surface analysis, NMR spectra, delocalization energies, and natural charge and electron configuration

CCDC references: 1405616; 1871198

Computing details top

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) top

Crystal data top

C₃₀H₃₂N₂O₆P₂	Z = 2
M_r = 578.51	F(000) = 608
Triclinic, P1	D_x = 1.338 Mg m⁻³
a = 10.2789 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.8253 (4) Å	Cell parameters from 12958 reflections
c = 15.0200 (6) Å	θ = 3.2–29.8°
α = 101.229 (4)°	µ = 0.20 mm⁻¹
β = 105.716 (4)°	T = 120 K
γ = 109.782 (4)°	Block, colourless
V = 1436.22 (12) Å³	0.20 × 0.20 × 0.10 mm

Data collection top

AFC11 (Right): Eulerian 3 circle CCD diffractometer	9009 reflections with I > 2σ(I)
Radiation source: Rotating Anode MicroMax-007HF DW 1.2 kW	R_int = 0.023
Profile data from ω–scans	θ_max = 25.4°, θ_min = 3.0°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −11→12
T_min = 0.893, T_max = 1.000	k = −13→12
15732 measured reflections	l = −17→18
9396 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.030	w = 1/[σ²(F_o²) + (0.0467P)² + 0.2585P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.078	(Δ/σ)_max = 0.014
S = 1.01	Δρ_max = 0.40 e Å⁻³
9396 reflections	Δρ_min = −0.30 e Å⁻³
733 parameters	Absolute structure: Flack x determined using 3782 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
7 restraints	Absolute structure parameter: 0.09 (3)

Special details top

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) top

	x	y	z	U_iso*/U_eq
P1	−0.01942 (7)	−0.09038 (7)	0.06356 (5)	0.01710 (15)
P2	0.09162 (7)	0.54319 (7)	0.53492 (5)	0.01731 (16)
O1	0.1377 (2)	−0.0603 (2)	0.10889 (15)	0.0237 (4)
O2	−0.0577 (2)	0.5311 (2)	0.48320 (15)	0.0229 (4)
O3	−0.0683 (2)	−0.07426 (19)	−0.04192 (14)	0.0224 (4)
O4	−0.1284 (2)	−0.25020 (19)	0.02886 (14)	0.0215 (4)
O5	0.2148 (2)	0.69728 (19)	0.58839 (14)	0.0198 (4)
O6	0.1030 (2)	0.4849 (2)	0.62401 (15)	0.0228 (4)
N1	−0.0773 (3)	−0.0049 (2)	0.13168 (18)	0.0188 (5)
H1N	−0.161 (3)	−0.003 (3)	0.107 (2)	0.023*
N2	0.1578 (3)	0.4690 (2)	0.46732 (17)	0.0196 (5)
H2N	0.248 (3)	0.481 (3)	0.492 (2)	0.024*
C1	−0.0099 (3)	0.0619 (3)	−0.0466 (2)	0.0200 (6)
C2	−0.0984 (3)	0.1332 (3)	−0.0525 (2)	0.0235 (6)
H2C	−0.196901	0.091346	−0.054063	0.028*
C3	−0.0418 (4)	0.2671 (3)	−0.0560 (2)	0.0296 (7)
H3A	−0.101658	0.317639	−0.060358	0.036*
C4	0.1026 (4)	0.3275 (3)	−0.0533 (2)	0.0332 (7)
H4A	0.141577	0.419496	−0.055456	0.040*
C5	0.1892 (4)	0.2539 (4)	−0.0473 (3)	0.0342 (8)
H5A	0.288179	0.295787	−0.044900	0.041*
C6	0.1330 (3)	0.1192 (3)	−0.0449 (2)	0.0278 (7)
H6A	0.191672	0.067546	−0.042118	0.033*
C7	−0.1320 (3)	−0.3334 (3)	0.0902 (2)	0.0213 (6)
C8	−0.2232 (3)	−0.4726 (3)	0.0431 (2)	0.0278 (7)
H8A	−0.277701	−0.505712	−0.025122	0.033*
C9	−0.2331 (4)	−0.5628 (3)	0.0981 (3)	0.0367 (8)
H9A	−0.293877	−0.658855	0.066975	0.044*
C10	−0.1556 (4)	−0.5141 (4)	0.1971 (3)	0.0343 (8)
H10A	−0.163778	−0.576278	0.234062	0.041*
C11	−0.0659 (4)	−0.3747 (3)	0.2428 (2)	0.0317 (7)
H11A	−0.013364	−0.341187	0.311247	0.038*
C12	−0.0524 (3)	−0.2832 (3)	0.1889 (2)	0.0268 (6)
H12A	0.010852	−0.187684	0.219774	0.032*
C13	0.2305 (3)	0.7902 (3)	0.5343 (2)	0.0205 (6)
C14	0.1535 (3)	0.8727 (3)	0.5368 (2)	0.0272 (6)
H14A	0.088763	0.864500	0.572182	0.033*
C15	0.1729 (4)	0.9676 (3)	0.4865 (3)	0.0352 (8)
H15A	0.121914	1.026139	0.487907	0.042*
C16	0.2659 (4)	0.9782 (3)	0.4340 (3)	0.0374 (8)
H16A	0.277387	1.042676	0.398768	0.045*
C17	0.3423 (4)	0.8942 (3)	0.4331 (3)	0.0350 (8)
H17A	0.407097	0.902204	0.397734	0.042*
C18	0.3249 (3)	0.7991 (3)	0.4832 (2)	0.0272 (7)
H18A	0.376589	0.741153	0.482568	0.033*
C19	0.0515 (3)	0.5245 (3)	0.6981 (2)	0.0204 (6)
C20	−0.0663 (3)	0.4232 (3)	0.7061 (2)	0.0268 (6)
H20A	−0.114556	0.332794	0.660240	0.032*
C21	−0.1122 (4)	0.4568 (4)	0.7824 (2)	0.0330 (7)
H21A	−0.192378	0.388376	0.789429	0.040*
C22	−0.0432 (4)	0.5879 (4)	0.8481 (2)	0.0334 (7)
H22A	−0.075535	0.609828	0.900281	0.040*
C23	0.0739 (4)	0.6883 (4)	0.8382 (2)	0.0334 (8)
H23A	0.120862	0.779304	0.883214	0.040*
C24	0.1223 (3)	0.6565 (3)	0.7631 (2)	0.0285 (7)
H24A	0.203124	0.724589	0.756441	0.034*
C26	−0.0522 (3)	0.0945 (3)	0.2995 (2)	0.0220 (6)
H26A	−0.152266	0.093273	0.273895	0.026*
H26B	−0.063867	0.005809	0.312337	0.026*
C27	0.0411 (3)	0.2137 (3)	0.3943 (2)	0.0232 (6)
H27A	−0.010222	0.204182	0.441290	0.028*
H27B	0.137874	0.209769	0.423043	0.028*
C28	0.0674 (3)	0.3527 (3)	0.3772 (2)	0.0181 (6)
H28A	−0.031368	0.356025	0.350978	0.022*
C29	0.1403 (3)	0.3683 (3)	0.3022 (2)	0.0204 (6)
H29A	0.241239	0.371807	0.328686	0.024*
H29B	0.150183	0.456595	0.289110	0.024*
C30	0.0505 (3)	0.2489 (3)	0.2069 (2)	0.0192 (6)
H30A	0.105590	0.258315	0.162067	0.023*
H30B	−0.045086	0.253496	0.175647	0.023*
C32	0.0198 (3)	0.1084 (3)	0.2235 (2)	0.0190 (6)
H32A	0.116408	0.100391	0.247602	0.023*
P51	0.59715 (8)	0.51364 (7)	0.56468 (5)	0.02132 (17)
P52	0.49858 (7)	−0.01130 (7)	0.03851 (5)	0.02157 (17)
O51	0.4625 (2)	0.5299 (2)	0.51600 (15)	0.0280 (5)
O52	0.6611 (2)	0.0448 (2)	0.07061 (15)	0.0260 (5)
O53	0.7353 (2)	0.6527 (2)	0.63427 (15)	0.0254 (5)
O54	0.5762 (2)	0.4288 (2)	0.63893 (15)	0.0253 (5)
O55	0.4222 (2)	0.0145 (2)	−0.05940 (16)	0.0318 (5)
O56	0.4173 (2)	−0.1749 (2)	0.00698 (16)	0.0302 (5)
N51	0.6598 (3)	0.4376 (3)	0.49526 (19)	0.0265 (6)
H51N	0.754 (3)	0.479 (3)	0.508 (3)	0.032*
N52	0.4371 (3)	0.0499 (2)	0.11513 (19)	0.0219 (5)
H52N	0.346 (3)	0.017 (3)	0.105 (3)	0.026*
C51	0.7833 (3)	0.7776 (3)	0.6141 (2)	0.0250 (6)
C52	0.7386 (4)	0.7885 (4)	0.5217 (3)	0.0360 (8)
H52C	0.672085	0.708835	0.467307	0.043*
C53	0.7925 (5)	0.9180 (4)	0.5098 (3)	0.0439 (9)
H53A	0.762647	0.927119	0.446643	0.053*
C54	0.8891 (5)	1.0332 (4)	0.5889 (3)	0.0459 (9)
H54A	0.925727	1.121561	0.580353	0.055*
C55	0.9324 (5)	1.0198 (4)	0.6804 (3)	0.0479 (10)
H55A	0.999018	1.099197	0.734969	0.057*
C56	0.8793 (4)	0.8910 (3)	0.6933 (3)	0.0354 (8)
H56A	0.909342	0.881647	0.756331	0.043*
C57	0.5117 (3)	0.4587 (3)	0.7070 (2)	0.0226 (6)
C58	0.5908 (3)	0.5738 (3)	0.7887 (2)	0.0273 (7)
H58A	0.687327	0.637050	0.797858	0.033*
C59	0.5276 (4)	0.5959 (3)	0.8571 (2)	0.0298 (7)
H59A	0.581000	0.675047	0.913608	0.036*
C60	0.3865 (4)	0.5034 (3)	0.8440 (2)	0.0312 (7)
H60A	0.343089	0.519239	0.890988	0.037*
C61	0.3105 (4)	0.3885 (3)	0.7623 (3)	0.0341 (7)
H61A	0.214524	0.324495	0.753476	0.041*
C62	0.3717 (3)	0.3649 (3)	0.6929 (2)	0.0292 (7)
H62A	0.318441	0.285618	0.636443	0.035*
C63	0.4746 (3)	0.0130 (3)	−0.1361 (2)	0.0223 (6)
C64	0.5044 (4)	−0.0946 (3)	−0.1764 (3)	0.0311 (7)
H64A	0.489926	−0.170591	−0.151648	0.037*
C65	0.5556 (4)	−0.0936 (4)	−0.2529 (3)	0.0393 (8)
H65A	0.578412	−0.166997	−0.279690	0.047*
C66	0.5725 (4)	0.0155 (4)	−0.2890 (3)	0.0416 (9)
H66A	0.606502	0.016385	−0.341821	0.050*
C67	0.5414 (4)	0.1240 (4)	−0.2507 (3)	0.0396 (8)
H67A	0.553488	0.198339	−0.277099	0.048*
C68	0.4919 (4)	0.1234 (4)	−0.1726 (3)	0.0366 (8)
H68A	0.470542	0.197440	−0.145023	0.044*
C69	0.4200 (4)	−0.2400 (3)	0.0792 (3)	0.0303 (7)
C70	0.5416 (4)	−0.2626 (4)	0.1231 (3)	0.0459 (10)
H70A	0.626665	−0.232796	0.105712	0.055*
C71	0.5393 (5)	−0.3287 (5)	0.1924 (4)	0.0706 (16)
H71A	0.622447	−0.345967	0.222593	0.085*
C72	0.4148 (5)	−0.3702 (6)	0.2184 (5)	0.0759 (17)
H72A	0.414384	−0.413225	0.267800	0.091*
C73	0.2929 (5)	−0.3492 (4)	0.1727 (4)	0.0550 (12)
H73A	0.207170	−0.379974	0.189258	0.066*
C74	0.2945 (4)	−0.2836 (3)	0.1030 (3)	0.0365 (8)
H74A	0.210461	−0.268358	0.071514	0.044*
C75	0.5652 (3)	0.3272 (3)	0.4023 (2)	0.0217 (6)
H75A	0.461588	0.287969	0.401526	0.026*
C76	0.6184 (3)	0.2118 (3)	0.3918 (2)	0.0250 (6)
H76A	0.609956	0.169972	0.444124	0.030*
H76B	0.724407	0.251145	0.399439	0.030*
C77	0.5282 (3)	0.0996 (3)	0.2927 (2)	0.0236 (6)
H77A	0.570326	0.029933	0.286882	0.028*
H77B	0.424610	0.052260	0.288412	0.028*
C78	0.5282 (3)	0.1592 (3)	0.2092 (2)	0.0208 (6)
H78A	0.632622	0.199943	0.211595	0.025*
C79	0.4734 (4)	0.2731 (3)	0.2185 (2)	0.0253 (6)
H79A	0.367420	0.233105	0.210725	0.030*
H79B	0.481747	0.314594	0.166012	0.030*
C80	0.5637 (4)	0.3857 (3)	0.3178 (2)	0.0262 (7)
H80A	0.666999	0.433605	0.321884	0.031*
H80B	0.520889	0.454931	0.323514	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0177 (3)	0.0172 (3)	0.0191 (4)	0.0079 (3)	0.0094 (3)	0.0065 (3)
P2	0.0171 (3)	0.0172 (3)	0.0191 (4)	0.0075 (3)	0.0086 (3)	0.0052 (3)
O1	0.0211 (10)	0.0248 (10)	0.0307 (12)	0.0116 (8)	0.0137 (9)	0.0102 (9)
O2	0.0166 (10)	0.0260 (10)	0.0271 (11)	0.0094 (8)	0.0100 (9)	0.0066 (8)
O3	0.0296 (11)	0.0169 (9)	0.0204 (10)	0.0075 (8)	0.0106 (9)	0.0069 (8)
O4	0.0264 (10)	0.0177 (9)	0.0216 (10)	0.0080 (8)	0.0112 (9)	0.0075 (8)
O5	0.0203 (10)	0.0184 (10)	0.0185 (10)	0.0059 (8)	0.0072 (8)	0.0052 (8)
O6	0.0294 (11)	0.0246 (10)	0.0250 (11)	0.0153 (9)	0.0177 (9)	0.0116 (9)
N1	0.0147 (11)	0.0212 (12)	0.0198 (12)	0.0086 (9)	0.0051 (10)	0.0047 (9)
N2	0.0152 (11)	0.0238 (12)	0.0183 (13)	0.0090 (10)	0.0061 (10)	0.0018 (10)
C1	0.0250 (14)	0.0176 (13)	0.0173 (14)	0.0077 (11)	0.0084 (12)	0.0067 (11)
C2	0.0204 (14)	0.0300 (15)	0.0221 (15)	0.0094 (12)	0.0103 (12)	0.0106 (12)
C3	0.0387 (17)	0.0293 (16)	0.0355 (17)	0.0225 (14)	0.0185 (15)	0.0183 (13)
C4	0.0380 (18)	0.0260 (15)	0.0398 (19)	0.0109 (14)	0.0183 (16)	0.0178 (14)
C5	0.0276 (16)	0.0381 (18)	0.045 (2)	0.0118 (14)	0.0199 (15)	0.0244 (15)
C6	0.0280 (16)	0.0335 (17)	0.0328 (17)	0.0169 (13)	0.0170 (14)	0.0171 (14)
C7	0.0230 (14)	0.0226 (14)	0.0295 (16)	0.0138 (11)	0.0162 (13)	0.0140 (12)
C8	0.0305 (15)	0.0221 (14)	0.0324 (17)	0.0103 (12)	0.0136 (14)	0.0102 (13)
C9	0.0376 (18)	0.0250 (16)	0.054 (2)	0.0129 (14)	0.0212 (17)	0.0211 (15)
C10	0.0331 (17)	0.0364 (18)	0.052 (2)	0.0198 (14)	0.0238 (16)	0.0307 (16)
C11	0.0286 (16)	0.0454 (19)	0.0320 (17)	0.0209 (14)	0.0134 (14)	0.0214 (15)
C12	0.0274 (16)	0.0265 (15)	0.0296 (17)	0.0129 (12)	0.0105 (13)	0.0122 (12)
C13	0.0193 (13)	0.0171 (13)	0.0184 (14)	0.0026 (11)	0.0050 (11)	0.0034 (11)
C14	0.0273 (15)	0.0268 (15)	0.0316 (16)	0.0114 (12)	0.0149 (13)	0.0119 (12)
C15	0.0395 (18)	0.0286 (16)	0.049 (2)	0.0194 (14)	0.0214 (17)	0.0197 (15)
C16	0.044 (2)	0.0348 (18)	0.045 (2)	0.0165 (15)	0.0231 (17)	0.0269 (16)
C17	0.0380 (18)	0.0365 (18)	0.0378 (19)	0.0131 (15)	0.0241 (16)	0.0162 (14)
C18	0.0263 (15)	0.0258 (15)	0.0312 (17)	0.0102 (12)	0.0136 (13)	0.0095 (12)
C19	0.0228 (14)	0.0264 (15)	0.0176 (14)	0.0127 (12)	0.0106 (12)	0.0098 (11)
C20	0.0279 (15)	0.0261 (15)	0.0278 (16)	0.0089 (12)	0.0122 (13)	0.0125 (12)
C21	0.0281 (16)	0.0450 (19)	0.0334 (18)	0.0153 (14)	0.0162 (14)	0.0205 (15)
C22	0.0337 (17)	0.054 (2)	0.0248 (16)	0.0254 (16)	0.0171 (14)	0.0153 (15)
C23	0.0305 (17)	0.0387 (18)	0.0246 (16)	0.0137 (14)	0.0081 (14)	0.0000 (13)
C24	0.0248 (15)	0.0274 (16)	0.0282 (17)	0.0067 (13)	0.0102 (13)	0.0047 (13)
C26	0.0266 (15)	0.0182 (13)	0.0229 (15)	0.0085 (12)	0.0119 (13)	0.0072 (11)
C27	0.0287 (16)	0.0240 (14)	0.0191 (15)	0.0101 (12)	0.0114 (13)	0.0092 (12)
C28	0.0176 (13)	0.0207 (13)	0.0158 (14)	0.0097 (11)	0.0050 (12)	0.0038 (11)
C29	0.0225 (15)	0.0192 (13)	0.0217 (15)	0.0080 (11)	0.0121 (12)	0.0066 (11)
C30	0.0227 (14)	0.0206 (13)	0.0175 (14)	0.0092 (11)	0.0110 (12)	0.0073 (11)
C32	0.0180 (13)	0.0208 (14)	0.0178 (14)	0.0085 (11)	0.0065 (12)	0.0043 (11)
P51	0.0151 (3)	0.0249 (4)	0.0223 (4)	0.0076 (3)	0.0072 (3)	0.0044 (3)
P52	0.0166 (3)	0.0305 (4)	0.0196 (4)	0.0104 (3)	0.0086 (3)	0.0082 (3)
O51	0.0185 (10)	0.0399 (12)	0.0267 (11)	0.0142 (9)	0.0084 (9)	0.0086 (9)
O52	0.0192 (10)	0.0353 (12)	0.0271 (11)	0.0128 (9)	0.0115 (9)	0.0103 (9)
O53	0.0225 (10)	0.0226 (10)	0.0258 (11)	0.0058 (8)	0.0069 (9)	0.0060 (8)
O54	0.0252 (10)	0.0254 (11)	0.0304 (12)	0.0123 (9)	0.0150 (9)	0.0094 (9)
O55	0.0282 (11)	0.0504 (14)	0.0277 (12)	0.0224 (10)	0.0146 (10)	0.0183 (10)
O56	0.0323 (12)	0.0275 (11)	0.0274 (12)	0.0096 (9)	0.0138 (10)	0.0025 (9)
N51	0.0135 (12)	0.0325 (14)	0.0257 (14)	0.0059 (10)	0.0067 (11)	0.0001 (11)
N52	0.0141 (11)	0.0234 (12)	0.0265 (14)	0.0043 (10)	0.0105 (11)	0.0058 (10)
C51	0.0236 (15)	0.0243 (14)	0.0310 (17)	0.0095 (12)	0.0155 (13)	0.0100 (12)
C52	0.0368 (18)	0.0361 (18)	0.0299 (18)	0.0116 (15)	0.0099 (15)	0.0091 (14)
C53	0.060 (2)	0.046 (2)	0.045 (2)	0.0275 (18)	0.030 (2)	0.0273 (18)
C54	0.063 (2)	0.0303 (18)	0.062 (3)	0.0204 (17)	0.043 (2)	0.0210 (17)
C55	0.062 (2)	0.0265 (17)	0.048 (2)	0.0072 (16)	0.029 (2)	0.0058 (16)
C56	0.0403 (19)	0.0308 (17)	0.0317 (18)	0.0086 (14)	0.0180 (15)	0.0065 (14)
C57	0.0224 (14)	0.0263 (14)	0.0272 (16)	0.0140 (12)	0.0122 (12)	0.0133 (12)
C58	0.0227 (15)	0.0268 (15)	0.0316 (18)	0.0101 (12)	0.0101 (14)	0.0078 (13)
C59	0.0321 (17)	0.0324 (16)	0.0294 (17)	0.0168 (14)	0.0123 (14)	0.0118 (13)
C60	0.0333 (17)	0.0410 (18)	0.0344 (18)	0.0214 (14)	0.0203 (15)	0.0214 (14)
C61	0.0269 (16)	0.0405 (18)	0.041 (2)	0.0119 (14)	0.0179 (15)	0.0226 (15)
C62	0.0252 (15)	0.0265 (15)	0.0305 (17)	0.0056 (13)	0.0081 (13)	0.0097 (13)
C63	0.0168 (13)	0.0283 (15)	0.0190 (14)	0.0073 (11)	0.0051 (11)	0.0074 (11)
C64	0.0277 (17)	0.0321 (17)	0.0323 (18)	0.0105 (13)	0.0136 (14)	0.0071 (14)
C65	0.0346 (19)	0.046 (2)	0.0300 (18)	0.0130 (16)	0.0116 (15)	0.0036 (15)
C66	0.0322 (18)	0.054 (2)	0.0297 (18)	0.0084 (16)	0.0102 (15)	0.0137 (16)
C67	0.0351 (18)	0.049 (2)	0.0334 (19)	0.0102 (16)	0.0113 (15)	0.0250 (16)
C68	0.0338 (18)	0.0356 (18)	0.0394 (19)	0.0145 (15)	0.0092 (15)	0.0156 (15)
C69	0.0331 (17)	0.0197 (15)	0.0433 (19)	0.0135 (13)	0.0195 (15)	0.0084 (13)
C70	0.039 (2)	0.047 (2)	0.077 (3)	0.0283 (17)	0.037 (2)	0.033 (2)
C71	0.055 (3)	0.094 (4)	0.125 (5)	0.057 (3)	0.056 (3)	0.083 (4)
C72	0.068 (3)	0.100 (4)	0.133 (5)	0.061 (3)	0.068 (3)	0.100 (4)
C73	0.052 (2)	0.058 (2)	0.099 (4)	0.038 (2)	0.052 (3)	0.054 (3)
C74	0.0324 (17)	0.0338 (17)	0.059 (2)	0.0204 (14)	0.0250 (17)	0.0248 (16)
C75	0.0161 (14)	0.0244 (14)	0.0230 (16)	0.0074 (11)	0.0093 (12)	0.0033 (12)
C76	0.0249 (15)	0.0255 (14)	0.0259 (16)	0.0102 (12)	0.0088 (13)	0.0119 (12)
C77	0.0248 (15)	0.0192 (14)	0.0288 (16)	0.0088 (12)	0.0110 (13)	0.0105 (12)
C78	0.0156 (13)	0.0232 (14)	0.0232 (16)	0.0066 (11)	0.0082 (12)	0.0077 (12)
C79	0.0292 (16)	0.0234 (14)	0.0274 (16)	0.0142 (12)	0.0097 (13)	0.0114 (12)
C80	0.0305 (17)	0.0239 (15)	0.0292 (17)	0.0161 (13)	0.0114 (14)	0.0094 (13)

Geometric parameters (Å, º) top

P1—O1	1.463 (2)	P51—O51	1.466 (2)
P1—O3	1.590 (2)	P51—O53	1.585 (2)
P1—O4	1.5937 (19)	P51—O54	1.590 (2)
P1—N1	1.609 (2)	P51—N51	1.603 (3)
P2—O2	1.468 (2)	P52—O52	1.468 (2)
P2—O6	1.580 (2)	P52—O56	1.586 (2)
P2—O5	1.5900 (19)	P52—O55	1.593 (2)
P2—N2	1.602 (2)	P52—N52	1.595 (3)
O3—C1	1.415 (3)	O53—C51	1.398 (3)
O4—C7	1.407 (3)	O54—C57	1.405 (4)
O5—C13	1.406 (3)	O55—C63	1.397 (4)
O6—C19	1.411 (3)	O56—C69	1.404 (4)
N1—C32	1.473 (4)	N51—C75	1.467 (4)
N1—H1N	0.85 (2)	N51—H51N	0.87 (2)
N2—C28	1.464 (3)	N52—C78	1.468 (4)
N2—H2N	0.85 (2)	N52—H52N	0.84 (2)
C1—C2	1.375 (4)	C51—C56	1.368 (4)
C1—C6	1.378 (4)	C51—C52	1.380 (5)
C2—C3	1.385 (4)	C52—C53	1.390 (5)
C2—H2C	0.9500	C52—H52C	0.9500
C3—C4	1.390 (5)	C53—C54	1.378 (6)
C3—H3A	0.9500	C53—H53A	0.9500
C4—C5	1.379 (5)	C54—C55	1.378 (6)
C4—H4A	0.9500	C54—H54A	0.9500
C5—C6	1.387 (4)	C55—C56	1.389 (5)
C5—H5A	0.9500	C55—H55A	0.9500
C6—H6A	0.9500	C56—H56A	0.9500
C7—C12	1.375 (4)	C57—C58	1.378 (4)
C7—C8	1.385 (4)	C57—C62	1.381 (4)
C8—C9	1.393 (4)	C58—C59	1.380 (5)
C8—H8A	0.9500	C58—H58A	0.9500
C9—C10	1.375 (5)	C59—C60	1.389 (5)
C9—H9A	0.9500	C59—H59A	0.9500
C10—C11	1.382 (5)	C60—C61	1.375 (5)
C10—H10A	0.9500	C60—H60A	0.9500
C11—C12	1.390 (4)	C61—C62	1.381 (5)
C11—H11A	0.9500	C61—H61A	0.9500
C12—H12A	0.9500	C62—H62A	0.9500
C13—C14	1.381 (4)	C63—C64	1.373 (5)
C13—C18	1.382 (4)	C63—C68	1.388 (5)
C14—C15	1.382 (4)	C64—C65	1.387 (5)
C14—H14A	0.9500	C64—H64A	0.9500
C15—C16	1.385 (5)	C65—C66	1.372 (6)
C15—H15A	0.9500	C65—H65A	0.9500
C16—C17	1.389 (5)	C66—C67	1.379 (6)
C16—H16A	0.9500	C66—H66A	0.9500
C17—C18	1.382 (5)	C67—C68	1.400 (5)
C17—H17A	0.9500	C67—H67A	0.9500
C18—H18A	0.9500	C68—H68A	0.9500
C19—C24	1.375 (4)	C69—C70	1.371 (5)
C19—C20	1.383 (4)	C69—C74	1.384 (5)
C20—C21	1.385 (4)	C70—C71	1.375 (6)
C20—H20A	0.9500	C70—H70A	0.9500
C21—C22	1.373 (5)	C71—C72	1.393 (6)
C21—H21A	0.9500	C71—H71A	0.9500
C22—C23	1.389 (5)	C72—C73	1.372 (6)
C22—H22A	0.9500	C72—H72A	0.9500
C23—C24	1.381 (5)	C73—C74	1.375 (5)
C23—H23A	0.9500	C73—H73A	0.9500
C24—H24A	0.9500	C74—H74A	0.9500
C26—C27	1.523 (4)	C75—C76	1.523 (4)
C26—C32	1.524 (4)	C75—C80	1.523 (4)
C26—H26A	0.9900	C75—H75A	1.0000
C26—H26B	0.9900	C76—C77	1.528 (4)
C27—C28	1.522 (4)	C76—H76A	0.9900
C27—H27A	0.9900	C76—H76B	0.9900
C27—H27B	0.9900	C77—C78	1.518 (4)
C28—C29	1.520 (4)	C77—H77A	0.9900
C28—H28A	1.0000	C77—H77B	0.9900
C29—C30	1.525 (4)	C78—C79	1.518 (4)
C29—H29A	0.9900	C78—H78A	1.0000
C29—H29B	0.9900	C79—C80	1.533 (4)
C30—C32	1.529 (4)	C79—H79A	0.9900
C30—H30A	0.9900	C79—H79B	0.9900
C30—H30B	0.9900	C80—H80A	0.9900
C32—H32A	1.0000	C80—H80B	0.9900

O1—P1—O3	115.74 (12)	O51—P51—O53	115.32 (12)
O1—P1—O4	114.34 (12)	O51—P51—O54	112.46 (12)
O3—P1—O4	94.73 (10)	O53—P51—O54	100.97 (11)
O1—P1—N1	113.23 (12)	O51—P51—N51	116.36 (14)
O3—P1—N1	109.01 (12)	O53—P51—N51	104.92 (12)
O4—P1—N1	108.18 (12)	O54—P51—N51	105.21 (13)
O2—P2—O6	113.89 (12)	O52—P52—O56	114.91 (13)
O2—P2—O5	115.07 (12)	O52—P52—O55	113.48 (12)
O6—P2—O5	100.23 (11)	O56—P52—O55	100.21 (13)
O2—P2—N2	114.21 (13)	O52—P52—N52	114.76 (12)
O6—P2—N2	106.65 (12)	O56—P52—N52	107.10 (12)
O5—P2—N2	105.44 (11)	O55—P52—N52	104.95 (13)
C1—O3—P1	116.03 (17)	C51—O53—P51	126.20 (19)
C7—O4—P1	123.86 (18)	C57—O54—P51	121.73 (19)
C13—O5—P2	118.23 (17)	C63—O55—P52	123.82 (19)
C19—O6—P2	122.84 (18)	C69—O56—P52	119.24 (19)
C32—N1—P1	124.40 (19)	C75—N51—P51	123.7 (2)
C32—N1—H1N	113 (2)	C75—N51—H51N	119 (2)
P1—N1—H1N	119 (2)	P51—N51—H51N	116 (2)
C28—N2—P2	124.3 (2)	C78—N52—P52	125.6 (2)
C28—N2—H2N	115 (2)	C78—N52—H52N	114 (2)
P2—N2—H2N	118 (2)	P52—N52—H52N	120 (2)
C2—C1—C6	122.0 (3)	C56—C51—C52	121.5 (3)
C2—C1—O3	118.5 (2)	C56—C51—O53	115.1 (3)
C6—C1—O3	119.5 (3)	C52—C51—O53	123.5 (3)
C1—C2—C3	119.0 (3)	C51—C52—C53	118.8 (3)
C1—C2—H2C	120.5	C51—C52—H52C	120.6
C3—C2—H2C	120.5	C53—C52—H52C	120.6
C2—C3—C4	120.0 (3)	C54—C53—C52	120.4 (4)
C2—C3—H3A	120.0	C54—C53—H53A	119.8
C4—C3—H3A	120.0	C52—C53—H53A	119.8
C5—C4—C3	119.9 (3)	C55—C54—C53	119.7 (3)
C5—C4—H4A	120.0	C55—C54—H54A	120.1
C3—C4—H4A	120.0	C53—C54—H54A	120.1
C4—C5—C6	120.5 (3)	C54—C55—C56	120.4 (3)
C4—C5—H5A	119.8	C54—C55—H55A	119.8
C6—C5—H5A	119.8	C56—C55—H55A	119.8
C1—C6—C5	118.6 (3)	C51—C56—C55	119.2 (3)
C1—C6—H6A	120.7	C51—C56—H56A	120.4
C5—C6—H6A	120.7	C55—C56—H56A	120.4
C12—C7—C8	121.7 (3)	C58—C57—C62	121.3 (3)
C12—C7—O4	123.8 (3)	C58—C57—O54	120.4 (3)
C8—C7—O4	114.5 (3)	C62—C57—O54	118.1 (3)
C7—C8—C9	118.5 (3)	C57—C58—C59	119.0 (3)
C7—C8—H8A	120.8	C57—C58—H58A	120.5
C9—C8—H8A	120.8	C59—C58—H58A	120.5
C10—C9—C8	120.5 (3)	C58—C59—C60	120.6 (3)
C10—C9—H9A	119.7	C58—C59—H59A	119.7
C8—C9—H9A	119.7	C60—C59—H59A	119.7
C9—C10—C11	120.1 (3)	C61—C60—C59	119.3 (3)
C9—C10—H10A	119.9	C61—C60—H60A	120.4
C11—C10—H10A	119.9	C59—C60—H60A	120.4
C10—C11—C12	120.2 (3)	C60—C61—C62	121.0 (3)
C10—C11—H11A	119.9	C60—C61—H61A	119.5
C12—C11—H11A	119.9	C62—C61—H61A	119.5
C7—C12—C11	118.9 (3)	C57—C62—C61	118.8 (3)
C7—C12—H12A	120.5	C57—C62—H62A	120.6
C11—C12—H12A	120.5	C61—C62—H62A	120.6
C14—C13—C18	122.3 (3)	C64—C63—C68	120.6 (3)
C14—C13—O5	118.3 (3)	C64—C63—O55	122.0 (3)
C18—C13—O5	119.4 (3)	C68—C63—O55	117.4 (3)
C13—C14—C15	118.3 (3)	C63—C64—C65	120.7 (3)
C13—C14—H14A	120.8	C63—C64—H64A	119.7
C15—C14—H14A	120.8	C65—C64—H64A	119.7
C14—C15—C16	120.7 (3)	C66—C65—C64	118.7 (4)
C14—C15—H15A	119.6	C66—C65—H65A	120.6
C16—C15—H15A	119.6	C64—C65—H65A	120.6
C15—C16—C17	119.7 (3)	C65—C66—C67	121.8 (3)
C15—C16—H16A	120.1	C65—C66—H66A	119.1
C17—C16—H16A	120.1	C67—C66—H66A	119.1
C18—C17—C16	120.5 (3)	C66—C67—C68	119.2 (3)
C18—C17—H17A	119.8	C66—C67—H67A	120.4
C16—C17—H17A	119.8	C68—C67—H67A	120.4
C13—C18—C17	118.5 (3)	C63—C68—C67	119.0 (3)
C13—C18—H18A	120.8	C63—C68—H68A	120.5
C17—C18—H18A	120.8	C67—C68—H68A	120.5
C24—C19—C20	121.9 (3)	C70—C69—C74	121.1 (3)
C24—C19—O6	120.8 (2)	C70—C69—O56	121.0 (3)
C20—C19—O6	117.2 (2)	C74—C69—O56	117.8 (3)
C19—C20—C21	118.4 (3)	C69—C70—C71	119.4 (3)
C19—C20—H20A	120.8	C69—C70—H70A	120.3
C21—C20—H20A	120.8	C71—C70—H70A	120.3
C22—C21—C20	120.7 (3)	C70—C71—C72	119.9 (4)
C22—C21—H21A	119.6	C70—C71—H71A	120.1
C20—C21—H21A	119.6	C72—C71—H71A	120.1
C21—C22—C23	119.9 (3)	C73—C72—C71	120.1 (4)
C21—C22—H22A	120.1	C73—C72—H72A	120.0
C23—C22—H22A	120.1	C71—C72—H72A	120.0
C24—C23—C22	120.3 (3)	C72—C73—C74	120.2 (4)
C24—C23—H23A	119.9	C72—C73—H73A	119.9
C22—C23—H23A	119.9	C74—C73—H73A	119.9
C19—C24—C23	118.8 (3)	C73—C74—C69	119.2 (3)
C19—C24—H24A	120.6	C73—C74—H74A	120.4
C23—C24—H24A	120.6	C69—C74—H74A	120.4
C27—C26—C32	111.1 (2)	N51—C75—C76	110.4 (2)
C27—C26—H26A	109.4	N51—C75—C80	110.1 (2)
C32—C26—H26A	109.4	C76—C75—C80	110.9 (2)
C27—C26—H26B	109.4	N51—C75—H75A	108.4
C32—C26—H26B	109.4	C76—C75—H75A	108.4
H26A—C26—H26B	108.0	C80—C75—H75A	108.4
C28—C27—C26	111.2 (2)	C75—C76—C77	111.7 (2)
C28—C27—H27A	109.4	C75—C76—H76A	109.3
C26—C27—H27A	109.4	C77—C76—H76A	109.3
C28—C27—H27B	109.4	C75—C76—H76B	109.3
C26—C27—H27B	109.4	C77—C76—H76B	109.3
H27A—C27—H27B	108.0	H76A—C76—H76B	108.0
N2—C28—C29	109.6 (2)	C78—C77—C76	111.8 (2)
N2—C28—C27	112.2 (2)	C78—C77—H77A	109.3
C29—C28—C27	110.8 (2)	C76—C77—H77A	109.3
N2—C28—H28A	108.0	C78—C77—H77B	109.3
C29—C28—H28A	108.0	C76—C77—H77B	109.3
C27—C28—H28A	108.0	H77A—C77—H77B	107.9
C28—C29—C30	111.6 (2)	N52—C78—C79	110.2 (2)
C28—C29—H29A	109.3	N52—C78—C77	110.6 (2)
C30—C29—H29A	109.3	C79—C78—C77	111.2 (3)
C28—C29—H29B	109.3	N52—C78—H78A	108.2
C30—C29—H29B	109.3	C79—C78—H78A	108.2
H29A—C29—H29B	108.0	C77—C78—H78A	108.2
C29—C30—C32	111.8 (2)	C78—C79—C80	111.1 (3)
C29—C30—H30A	109.3	C78—C79—H79A	109.4
C32—C30—H30A	109.3	C80—C79—H79A	109.4
C29—C30—H30B	109.3	C78—C79—H79B	109.4
C32—C30—H30B	109.3	C80—C79—H79B	109.4
H30A—C30—H30B	107.9	H79A—C79—H79B	108.0
N1—C32—C26	109.4 (2)	C75—C80—C79	112.2 (2)
N1—C32—C30	110.6 (2)	C75—C80—H80A	109.2
C26—C32—C30	111.2 (2)	C79—C80—H80A	109.2
N1—C32—H32A	108.5	C75—C80—H80B	109.2
C26—C32—H32A	108.5	C79—C80—H80B	109.2
C30—C32—H32A	108.5	H80A—C80—H80B	107.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O52ⁱ	0.85 (2)	2.03 (2)	2.863 (3)	167 (3)
N2—H2N···O51	0.85 (2)	2.00 (2)	2.820 (3)	162 (3)
N51—H51N···O2ⁱⁱ	0.87 (2)	1.98 (3)	2.802 (3)	158 (3)
N52—H52N···O1	0.84 (2)	2.04 (2)	2.866 (3)	168 (3)
C22—H22A···O4ⁱⁱⁱ	0.95	2.51	3.418 (4)	160
C6—H6A···O55	0.95	2.69	3.565 (4)	154
C74—H74A···O1	0.95	2.61	3.329 (4)	133
C2—H2C···O52ⁱ	0.95	2.69	3.465 (3)	139
C2—H2C···CG1ⁱ	0.95	2.92	3.593 (8)	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) top

Crystal data top

C₁₀H₁₈N₂O₄P₂S₂	F(000) = 744
M_r = 356.32	D_x = 1.388 Mg m⁻³
Monoclinic, P2₁/a	Mo Kα radiation, λ = 0.71073 Å
a = 13.2517 (3) Å	Cell parameters from 6840 reflections
b = 10.0091 (2) Å	θ = 3.1–28.0°
c = 13.9580 (3) Å	µ = 0.51 mm⁻¹
β = 112.9309 (12)°	T = 295 K
V = 1705.05 (6) Å³	Block, colourless
Z = 4	0.43 × 0.36 × 0.31 mm

Data collection top

Nonius KappaCCD diffractometer	3267 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.019
φ scans and ω scans	θ_max = 28.0°, θ_min = 3.1°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −17→17
T_min = 0.790, T_max = 0.845	k = −12→13
6840 measured reflections	l = −18→18
4091 independent reflections

Refinement top

Refinement on F²	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.115	w = 1/[σ²(F_o²) + (0.0488P)² + 0.9571P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
4091 reflections	Δρ_max = 0.70 e Å⁻³
191 parameters	Δρ_min = −0.48 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	−0.10510 (16)	0.22673 (18)	0.16416 (14)	0.0383 (4)
C2	−0.05330 (16)	0.33804 (19)	0.22145 (15)	0.0406 (4)
H2	−0.080489	0.422741	0.197783	0.049*
C3	0.03820 (16)	0.3252 (2)	0.31329 (15)	0.0432 (5)
H3	0.071866	0.400946	0.350764	0.052*
C4	0.07964 (16)	0.19929 (19)	0.34936 (15)	0.0401 (4)
C5	0.03004 (16)	0.0882 (2)	0.29087 (15)	0.0442 (5)
H5	0.058510	0.003716	0.313678	0.053*
C6	−0.06154 (17)	0.10094 (19)	0.19870 (15)	0.0441 (5)
H6	−0.093740	0.025412	0.160088	0.053*
N1	−0.19948 (15)	0.24601 (16)	0.07154 (14)	0.0491 (5)
H1N	−0.218 (2)	0.3233 (18)	0.060 (2)	0.059*
P1	−0.27879 (4)	0.13688 (5)	−0.00992 (4)	0.03875 (14)
S1	−0.39878 (5)	0.22087 (6)	−0.11912 (5)	0.05876 (19)
O1	−0.20470 (13)	0.04058 (16)	−0.04448 (12)	0.0535 (4)
C7	−0.1410 (3)	0.0939 (5)	−0.0986 (3)	0.1061 (13)
H7A	−0.185412	0.153669	−0.152217	0.159*
H7B	−0.115829	0.022073	−0.129260	0.159*
H7C	−0.079075	0.141495	−0.050487	0.159*
O2	−0.30821 (13)	0.02609 (16)	0.05507 (12)	0.0553 (4)
C8	−0.3725 (3)	0.0616 (4)	0.1146 (3)	0.0930 (11)
H8A	−0.335379	0.130267	0.163726	0.140*
H8B	−0.381900	−0.015587	0.151065	0.140*
H8C	−0.442969	0.093827	0.068415	0.140*
N2	0.17100 (16)	0.18068 (18)	0.44518 (14)	0.0541 (5)
H2N	0.188 (2)	0.0995 (18)	0.460 (2)	0.065*
P2	0.24331 (4)	0.28916 (5)	0.53117 (4)	0.04238 (15)
S2	0.35199 (5)	0.20676 (7)	0.65024 (5)	0.0634 (2)
O3	0.28520 (14)	0.39623 (18)	0.47204 (13)	0.0635 (4)
C9	0.3563 (4)	0.3603 (6)	0.4224 (3)	0.1276 (17)
H9A	0.427943	0.341952	0.474035	0.191*
H9B	0.360601	0.432479	0.378888	0.191*
H9C	0.328474	0.282030	0.380640	0.191*
O4	0.16411 (17)	0.3914 (2)	0.55171 (14)	0.0803 (6)
C10	0.1129 (4)	0.3727 (6)	0.6169 (4)	0.152 (2)
H10A	0.147202	0.300551	0.663516	0.228*
H10B	0.037320	0.351315	0.577502	0.228*
H10C	0.117510	0.452852	0.656121	0.228*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0372 (10)	0.0324 (9)	0.0343 (9)	−0.0009 (7)	0.0021 (8)	−0.0010 (7)
C2	0.0435 (10)	0.0282 (8)	0.0395 (10)	0.0019 (8)	0.0046 (8)	0.0011 (8)
C3	0.0459 (11)	0.0317 (9)	0.0397 (10)	−0.0028 (8)	0.0033 (8)	−0.0040 (8)
C4	0.0369 (10)	0.0365 (9)	0.0345 (9)	0.0010 (8)	0.0005 (8)	0.0003 (8)
C5	0.0461 (11)	0.0307 (9)	0.0426 (10)	0.0051 (8)	0.0027 (8)	0.0010 (8)
C6	0.0472 (11)	0.0305 (9)	0.0401 (10)	0.0007 (8)	0.0012 (8)	−0.0040 (8)
N1	0.0479 (10)	0.0277 (8)	0.0458 (9)	0.0019 (7)	−0.0100 (8)	−0.0005 (7)
P1	0.0376 (3)	0.0323 (3)	0.0363 (3)	−0.00116 (19)	0.0034 (2)	−0.0027 (2)
S1	0.0486 (3)	0.0500 (3)	0.0506 (3)	0.0034 (2)	−0.0103 (2)	−0.0014 (3)
O1	0.0531 (9)	0.0547 (9)	0.0502 (8)	0.0068 (7)	0.0172 (7)	−0.0068 (7)
C7	0.094 (2)	0.145 (3)	0.104 (3)	0.021 (2)	0.065 (2)	0.021 (3)
O2	0.0567 (9)	0.0503 (9)	0.0557 (9)	−0.0091 (7)	0.0183 (7)	0.0048 (7)
C8	0.092 (2)	0.125 (3)	0.0770 (19)	−0.020 (2)	0.0494 (18)	0.000 (2)
N2	0.0529 (11)	0.0343 (9)	0.0469 (10)	0.0037 (8)	−0.0114 (8)	−0.0006 (8)
P2	0.0421 (3)	0.0426 (3)	0.0335 (3)	0.0027 (2)	0.0050 (2)	−0.0046 (2)
S2	0.0600 (4)	0.0617 (4)	0.0421 (3)	0.0054 (3)	−0.0089 (3)	−0.0022 (3)
O3	0.0650 (10)	0.0615 (10)	0.0548 (9)	−0.0133 (9)	0.0134 (8)	0.0006 (8)
C9	0.111 (3)	0.191 (5)	0.108 (3)	−0.007 (3)	0.073 (3)	0.016 (3)
O4	0.0843 (13)	0.0981 (15)	0.0541 (10)	0.0405 (12)	0.0220 (9)	−0.0052 (10)
C10	0.128 (4)	0.238 (6)	0.122 (3)	0.063 (4)	0.085 (3)	0.007 (4)

Geometric parameters (Å, º) top

C1—C2	1.387 (3)	C7—H7B	0.9600
C1—C6	1.391 (3)	C7—H7C	0.9600
C1—N1	1.419 (2)	O2—C8	1.447 (3)
C2—C3	1.385 (3)	C8—H8A	0.9600
C2—H2	0.9300	C8—H8B	0.9600
C3—C4	1.389 (3)	C8—H8C	0.9600
C3—H3	0.9300	N2—P2	1.6253 (18)
C4—C5	1.385 (3)	N2—H2N	0.847 (17)
C4—N2	1.424 (2)	P2—O4	1.5702 (18)
C5—C6	1.388 (3)	P2—O3	1.5794 (18)
C5—H5	0.9300	P2—S2	1.9109 (8)
C6—H6	0.9300	O3—C9	1.416 (4)
N1—P1	1.6307 (17)	C9—H9A	0.9600
N1—H1N	0.807 (16)	C9—H9B	0.9600
P1—O2	1.5749 (16)	C9—H9C	0.9600
P1—O1	1.5795 (16)	O4—C10	1.343 (4)
P1—S1	1.9156 (7)	C10—H10A	0.9600
O1—C7	1.437 (3)	C10—H10B	0.9600
C7—H7A	0.9600	C10—H10C	0.9600

C2—C1—C6	118.81 (17)	H7A—C7—H7C	109.5
C2—C1—N1	118.59 (17)	H7B—C7—H7C	109.5
C6—C1—N1	122.59 (17)	C8—O2—P1	119.39 (19)
C3—C2—C1	121.15 (18)	O2—C8—H8A	109.5
C3—C2—H2	119.4	O2—C8—H8B	109.5
C1—C2—H2	119.4	H8A—C8—H8B	109.5
C2—C3—C4	119.95 (18)	O2—C8—H8C	109.5
C2—C3—H3	120.0	H8A—C8—H8C	109.5
C4—C3—H3	120.0	H8B—C8—H8C	109.5
C5—C4—C3	119.05 (17)	C4—N2—P2	130.33 (15)
C5—C4—N2	118.90 (17)	C4—N2—H2N	113.7 (19)
C3—C4—N2	122.05 (17)	P2—N2—H2N	115.9 (18)
C4—C5—C6	121.01 (18)	O4—P2—O3	92.82 (12)
C4—C5—H5	119.5	O4—P2—N2	109.06 (11)
C6—C5—H5	119.5	O3—P2—N2	107.07 (10)
C5—C6—C1	119.96 (18)	O4—P2—S2	116.96 (8)
C5—C6—H6	120.0	O3—P2—S2	116.63 (7)
C1—C6—H6	120.0	N2—P2—S2	112.43 (7)
C1—N1—P1	130.09 (14)	C9—O3—P2	121.3 (3)
C1—N1—H1N	113.4 (19)	O3—C9—H9A	109.5
P1—N1—H1N	116.4 (19)	O3—C9—H9B	109.5
O2—P1—O1	93.96 (9)	H9A—C9—H9B	109.5
O2—P1—N1	107.88 (10)	O3—C9—H9C	109.5
O1—P1—N1	108.26 (10)	H9A—C9—H9C	109.5
O2—P1—S1	116.89 (7)	H9B—C9—H9C	109.5
O1—P1—S1	116.54 (7)	C10—O4—P2	125.7 (3)
N1—P1—S1	111.75 (7)	O4—C10—H10A	109.5
C7—O1—P1	119.8 (2)	O4—C10—H10B	109.5
O1—C7—H7A	109.5	H10A—C10—H10B	109.5
O1—C7—H7B	109.5	O4—C10—H10C	109.5
H7A—C7—H7B	109.5	H10A—C10—H10C	109.5
O1—C7—H7C	109.5	H10B—C10—H10C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O3	0.93	2.67	3.237 (2)	120
C3—H3···O4	0.93	2.59	3.158 (3)	120
N1—H1N···O1ⁱ	0.81 (2)	2.38 (2)	3.174 (2)	169 (2)
N2—H2N···O3ⁱⁱ	0.85 (2)	2.22 (2)	3.042 (3)	165 (2)

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

All the POC bond angles and the contribution portions of s and p orbitals of BD(P-O) and BD(C-O) in both (I) and (II) top

Compound (I)
Segment	Bond angles (°)	BD(P-O)	Contribution portions (%)	BD(C-O)	Contribution portions (%)
P1O3C1	125.0815	BD(P1-O3)	s (26.17), p (73.79)	BD(O3-C1)	s (37.13), p (62.81)
P1O4C7	124.7019	BD(P1-O4	s (27.14), p (72.82)	BD(O4-C7)	s (37.20), p (62.75)
P2O5C13	125.0868	BD(P2-O5)	s (28.18), p (71.78)	BD(O5-C13)	s (37.94), p (62.01)
P2O6C19	122.9743	BD(P2-O6)	s (27.10), p (72.85)	BD(O6-C19)	s (37.33), p (62.62)
P51O53C51	125.6914	BD(P51-O53)	s (27.28), p (72.67)	BD(O53-C51)	s (37.88), p (62.07)
P51O54C57	124.4525	BD(P51-O54)	s (25.76), p (74.19)	BD(O54-C57)	s (36.49), p (63.45)
P52O55C63	124.3808	BD(P52-O56)	s (26.58), p (73.38)	BD(O55-C63)	s (36.89), p (63.0 6)
P52O56C69	124.7025	BD(P52-O55)	s (26.48), p (73.47)	BD(O56-C69)	s (37.31), p (62.63)

Compound (II)
Segment	Bond angles (?)	BD(P-O)	Contribution portions (%)	BD(C-O)	Contribution portions (%)
P1O1C7	120.6189	BDP1-O1	s (28.60), p (71.35)	BD(O1-C7)	s (30.69), p (69.25)
P1O2C8	120.5541	BDP1-O2	s (28.58), p (71.37)	BD(O2-C8)	s (30.67), p (69.28)
P2O3C9	120.5650	BDP2-O3	s (28.58), p (71.37)	BD(O3-C9)	s (30.67), p (69.27)
P2O4C10	120.6046	BDP2-O4	s (28.59), p (71.36)	BD(O4-C10)	s (30.69), p (69.26)

The contribution portions of s and p orbitals of two lone pair at O atoms top

(I)
LP O	Contribution portions (%)	π O	Contribution portions (%)
LP O3	s (32.03), p (67.94)	π O3	s (4.65), p (95.32)
LP O4	s (32.68), p (67.29)	π O4	s (2.97), p (96.99)
LP O5	s (32.33), p (67.64)	π O5	s (1.54), p (98.42)
LP O6	s (31.53), p (68.43)	π O6	s (4.01), p (95.95)
LP O53	s (32.53), p (67.44)	π O53	s (2.30), p (97.67)
LP O54	s (32.98), p (66.99)	π O54	s (4.75), p (95.22)
LP O55	s (32.98), p (66.98)	π O55	s (3.53), p (96.43)
LP O56	s (32.23), p (67.74)	π O56	s (3.95), p (96.01)

(II)
LP O1	s (40.54), p (59.43)	π O1	s (0.15), p (99.81)
LP O2	s (40.56), p (59.41)	π O2	s (0.18), p (99.78)
LP O3	s (40.55), p (59.41)	π O3	s (0.17), p (99.79)
LP O4	s (40.54), p (59.42)	π O4	s (0.16), p (99.80)

NBO analysis results of (I) at the B3LYP/6-311g(d,p) method top

Donor	Occu. No	E (a.u.)	Acceptor	Occu. No	E (a.u.)	E⁽²⁾ (kcal mol^-1)
LP O52	1.9660	-0.7549	BD*(1) N1—H1N	0.0287	0.4623	7.09
LP O51	1.9662	-0.7572	BD*(1) N2—H2N	0.0287	0.4642	7.03
LP O1	1.9638	-0.7389	BD*(1) N52—H52N	0.0325	0.4729	8.60
LP O2	1.9656	-0.7430	BD*(1) N51—H51N	0.0303	0.4676	7.33

NBO analysis results of (II) at the B3LYP/6-311g(d,p) method top

Donor	Occu. No	E (a.u.)	Acceptor	Occu. No	E (a.u.)	E⁽²⁾ (kcal mol^-1)
LP O1	1.94905	-0.65940	BD*(1) N1—H1N	0.02426	0.42790	4.88
LP O3	1.94410	-0.65654	BD*(1) N2—H2N	0.03007	0.42825	8.16

NBO analysis results of (I) at the B3LYP/6-311g(d,p) method (optimization is with restriction) top

Donor	Occu. No	E (a.u.)	Acceptor	Occu. No	E (a.u.)	E⁽²⁾ (kcal mol^-1)
LP O51	1.9556	-0.8519	BD*(1) N1—H1N	0.0422	0.4557	12.86
LP O52	1.9544	-0.8285	BD*(1) N2—H2N	0.0455	0.4672	13.87
LP O1	1.9567	-0.8287	BD*(1) N52—H52N	0.0427	0.4672	13.41
LP O2	1.9536	-0.8534	BD*(1) N51—H51N	0.0486	0.4517	14.21

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A combined X-ray crystallography and theoretical study of N—HOX (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

Supporting information

A combined X-ray crystallography and theoretical study of N—HOX (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