N,N'-Dibenzyl-N''-(2-chloro-2,2-difluoro-acet-yl)phospho-ric triamide.

In the title mol-ecule, C(16)H(17)ClF(2)N(3)O(2)P, the N-H unit of the C(=O)NHP(=O) fragment adopts a syn orientation with respect to the P=O group. The two F atoms and the Cl atom of the ClF(2)C group are disordered over two sets of sites with refined occupancies of 0.605 (6) and 0.395 (6). In the crystal, mol-ecules are linked via N-H⋯O=C hydrogen bonds the and the (N-H⋯)(N-H⋯)O=P group into chains along [010].

Related literature

For related structures with a P(=O)[NHC(=O)CClF2] fragment, and for reference values of P=O, C=O and P—N bond lengths and P—N—C bond angles, see: Pourayoubi et al. (2011 ▶); Raissi Shabari et al. (2011 ▶); Pourayoubi & Saneei (2011 ▶). For the double hydrogen-bond acceptor capability of the phosphoryl O atom in phospho­ramidates, see: Pourayoubi et al. (2012 ▶). For the synthesis of the starting material, CClF2C(=O)NHP(=O)Cl2, see: Iriarte et al. (2008 ▶).

Experimental

Crystal data

C16H17ClF2N3O2P

M = 387.75

Monoclinic,

a = 12.9734 (5) Å

b = 4.9900 (2) Å

c = 13.7750 (4) Å

β = 96.482 (3)°

V = 886.06 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.34 mm−1

T = 173 K

0.35 × 0.22 × 0.12 mm

Data collection

Oxford Xcalibur (Eos, Gemini) diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T min = 0.890, T max = 0.960

9633 measured reflections

5460 independent reflections

4909 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.122

S = 1.09

5460 reflections

263 parameters

18 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.55 e Å−3

Δρmin = −0.71 e Å−3

Absolute structure: Flack (1983 ▶), with 2216 Friedel pairs

Flack parameter: 0.06 (11)

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and enCIFer (Allen et al., 2004 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812039712/lh5506sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812039712/lh5506Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H17ClF2N3O2P	F(000) = 400
Mr = 387.75	Dx = 1.453 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3176 reflections
a = 12.9734 (5) Å	θ = 3.3–32.2°
b = 4.9900 (2) Å	µ = 0.34 mm−1
c = 13.7750 (4) Å	T = 173 K
β = 96.482 (3)°	Block, colourless
V = 886.06 (6) Å3	0.35 × 0.22 × 0.12 mm
Z = 2

Oxford Xcalibur (Eos, Gemini) diffractometer	5460 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4909 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 16.1500 pixels mm-1	θmax = 32.2°, θmin = 3.3°
ω scans	h = −18→19
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	k = −7→6
Tmin = 0.890, Tmax = 0.960	l = −9→20
9633 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.122	w = 1/[σ2(Fo2) + (0.048P)2 + 0.3968P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max = 0.001
5460 reflections	Δρmax = 0.55 e Å−3
263 parameters	Δρmin = −0.71 e Å−3
18 restraints	Absolute structure: Flack (1983), with 2216 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.06 (11)

Experimental. IR (KBr, ν, cm-1): 3253, 1718, 1457, 1419, 1282, 1215, 1139, 1073, 977, 873, 735 and 688.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq	Occ. (<1)
P1	0.51645 (5)	0.70594 (13)	0.19236 (4)	0.01939 (13)
Cl1	0.2161 (2)	0.5360 (8)	0.3959 (2)	0.0795 (10)	0.605 (6)
F1	0.3784 (5)	0.5030 (15)	0.4995 (4)	0.086 (2)	0.605 (6)
F2	0.3555 (5)	0.8763 (7)	0.4479 (3)	0.073 (2)	0.605 (6)
Cl1A	0.3973 (4)	0.6102 (13)	0.5203 (3)	0.0829 (18)	0.395 (6)
F1A	0.2518 (6)	0.4471 (17)	0.4089 (7)	0.066 (3)	0.395 (6)
F2A	0.2775 (5)	0.8461 (12)	0.3861 (5)	0.058 (2)	0.395 (6)
O1	0.54403 (15)	0.9827 (4)	0.16821 (14)	0.0261 (4)
O2	0.4173 (2)	0.3092 (5)	0.3189 (2)	0.0528 (8)
N1	0.45241 (18)	0.5364 (5)	0.10546 (18)	0.0266 (5)
H1N	0.460 (3)	0.362 (5)	0.106 (3)	0.032*
N2	0.61194 (18)	0.5089 (5)	0.22963 (16)	0.0241 (4)
H2N	0.601 (3)	0.340 (5)	0.226 (2)	0.029*
N3	0.4401 (2)	0.7487 (5)	0.28612 (18)	0.0288 (5)
H3N	0.428 (3)	0.909 (5)	0.305 (2)	0.035*
C1	0.3635 (2)	0.6492 (6)	0.0436 (2)	0.0294 (6)
H1B	0.3792	0.6516	−0.0251	0.035*
H1A	0.3527	0.8367	0.0637	0.035*
C2	0.2652 (2)	0.4925 (6)	0.04980 (19)	0.0270 (5)
C3	0.2351 (2)	0.2941 (6)	−0.0179 (2)	0.0309 (6)
H3A	0.2759	0.2598	−0.0696	0.037*
C4	0.1463 (3)	0.1456 (7)	−0.0111 (3)	0.0391 (7)
H4A	0.1267	0.0093	−0.0577	0.047*
C5	0.0860 (2)	0.1951 (9)	0.0635 (2)	0.0432 (7)
H5A	0.0247	0.0937	0.0679	0.052*
C6	0.1150 (3)	0.3920 (9)	0.1315 (3)	0.0457 (9)
H6A	0.0742	0.4238	0.1835	0.055*
C7	0.2035 (2)	0.5440 (8)	0.1241 (2)	0.0364 (7)
H7A	0.2219	0.6832	0.1698	0.044*
C8	0.6884 (2)	0.5876 (6)	0.3112 (2)	0.0286 (6)
H8A	0.6577	0.5637	0.3733	0.034*
H8B	0.7050	0.7800	0.3048	0.034*
C9	0.7871 (2)	0.4274 (6)	0.31541 (19)	0.0263 (5)
C10	0.8070 (2)	0.2410 (7)	0.2450 (2)	0.0303 (6)
H10A	0.7574	0.2120	0.1899	0.036*
C11	0.8993 (3)	0.0966 (8)	0.2550 (3)	0.0401 (7)
H11A	0.9121	−0.0311	0.2067	0.048*
C12	0.9720 (3)	0.1367 (8)	0.3341 (3)	0.0453 (9)
H12A	1.0345	0.0358	0.3409	0.054*
C13	0.9537 (3)	0.3244 (9)	0.4035 (3)	0.0505 (10)
H13A	1.0045	0.3561	0.4575	0.061*
C14	0.8624 (3)	0.4658 (8)	0.3949 (2)	0.0403 (7)
H14A	0.8502	0.5920	0.4439	0.048*
C15	0.4032 (3)	0.5428 (6)	0.3344 (3)	0.0405 (8)
C16	0.3359 (2)	0.6241 (6)	0.4143 (2)	0.0490 (8)

	U11	U22	U33	U12	U13	U23
P1	0.0211 (3)	0.0136 (2)	0.0242 (3)	−0.0009 (3)	0.00582 (19)	−0.0014 (2)
Cl1	0.0438 (12)	0.139 (3)	0.0597 (12)	0.0070 (14)	0.0255 (10)	−0.0081 (14)
F1	0.076 (4)	0.169 (7)	0.0121 (19)	−0.017 (4)	0.0062 (19)	−0.016 (3)
F2	0.139 (5)	0.036 (2)	0.056 (3)	−0.013 (3)	0.066 (3)	−0.0126 (18)
Cl1A	0.076 (3)	0.148 (5)	0.0257 (15)	0.005 (3)	0.0091 (13)	−0.0213 (17)
F1A	0.028 (3)	0.079 (6)	0.098 (6)	−0.017 (4)	0.036 (4)	0.007 (5)
F2A	0.081 (5)	0.043 (3)	0.060 (4)	0.032 (3)	0.047 (4)	0.012 (3)
O1	0.0319 (10)	0.0160 (9)	0.0322 (9)	−0.0018 (7)	0.0107 (7)	0.0004 (7)
O2	0.0767 (19)	0.0144 (10)	0.0769 (18)	0.0017 (12)	0.0504 (16)	0.0025 (11)
N1	0.0229 (10)	0.0199 (11)	0.0361 (11)	0.0025 (9)	−0.0006 (8)	−0.0079 (9)
N2	0.0240 (10)	0.0158 (10)	0.0316 (11)	−0.0011 (8)	−0.0008 (8)	−0.0015 (9)
N3	0.0405 (13)	0.0129 (12)	0.0366 (11)	0.0009 (9)	0.0198 (10)	−0.0012 (8)
C1	0.0263 (12)	0.0335 (18)	0.0281 (12)	−0.0024 (10)	0.0009 (9)	0.0050 (10)
C2	0.0218 (12)	0.0308 (14)	0.0281 (12)	0.0024 (10)	0.0014 (9)	0.0067 (10)
C3	0.0275 (13)	0.0332 (16)	0.0321 (13)	0.0026 (11)	0.0033 (11)	0.0008 (11)
C4	0.0366 (16)	0.0320 (19)	0.0477 (17)	−0.0011 (12)	0.0000 (13)	−0.0013 (12)
C5	0.0271 (13)	0.0458 (19)	0.0568 (18)	−0.0050 (17)	0.0047 (12)	0.008 (2)
C6	0.0327 (17)	0.064 (3)	0.0427 (17)	−0.0004 (17)	0.0129 (13)	0.0049 (17)
C7	0.0287 (14)	0.049 (2)	0.0314 (13)	−0.0020 (14)	0.0042 (11)	−0.0040 (13)
C8	0.0296 (13)	0.0269 (14)	0.0284 (12)	0.0019 (11)	−0.0006 (10)	−0.0036 (10)
C9	0.0252 (12)	0.0265 (13)	0.0270 (12)	−0.0032 (10)	0.0025 (9)	0.0035 (10)
C10	0.0260 (12)	0.0340 (17)	0.0309 (12)	−0.0004 (12)	0.0030 (9)	−0.0017 (11)
C11	0.0298 (15)	0.0427 (19)	0.0494 (18)	0.0062 (14)	0.0113 (13)	−0.0021 (15)
C12	0.0297 (15)	0.052 (2)	0.0533 (19)	0.0088 (14)	0.0011 (13)	0.0121 (16)
C13	0.0378 (19)	0.062 (3)	0.0474 (19)	0.0040 (17)	−0.0156 (15)	0.0013 (18)
C14	0.0393 (17)	0.0429 (19)	0.0356 (15)	0.0020 (15)	−0.0096 (12)	−0.0027 (14)
C15	0.060 (2)	0.0165 (13)	0.0516 (18)	0.0013 (13)	0.0366 (16)	0.0015 (12)
C16	0.0641 (16)	0.0245 (15)	0.066 (2)	−0.0012 (15)	0.0394 (15)	0.0048 (15)

P1—O1	1.474 (2)	C3—H3A	0.9500
P1—N1	1.617 (2)	C4—C5	1.382 (5)
P1—N2	1.619 (2)	C4—H4A	0.9500
P1—N3	1.728 (2)	C5—C6	1.381 (6)
Cl1—C16	1.607 (3)	C5—H5A	0.9500
F1—C16	1.379 (5)	C6—C7	1.390 (5)
F2—C16	1.355 (4)	C6—H6A	0.9500
Cl1A—C16	1.585 (4)	C7—H7A	0.9500
F1A—C16	1.399 (5)	C8—C9	1.505 (4)
F2A—C16	1.373 (4)	C8—H8A	0.9900
O2—C15	1.203 (4)	C8—H8B	0.9900
N1—C1	1.467 (4)	C9—C10	1.388 (4)
N1—H1N	0.88 (2)	C9—C14	1.396 (4)
N2—C8	1.466 (3)	C10—C11	1.391 (4)
N2—H2N	0.86 (2)	C10—H10A	0.9500
N3—C15	1.341 (4)	C11—C12	1.373 (5)
N3—H3N	0.86 (2)	C11—H11A	0.9500
C1—C2	1.507 (4)	C12—C13	1.378 (6)
C1—H1B	0.9900	C12—H12A	0.9500
C1—H1A	0.9900	C13—C14	1.373 (5)
C2—C3	1.386 (4)	C13—H13A	0.9500
C2—C7	1.393 (4)	C14—H14A	0.9500
C3—C4	1.382 (4)	C15—C16	1.534 (4)
O1—P1—N1	116.13 (13)	C9—C8—H8B	109.0
O1—P1—N2	116.36 (12)	H8A—C8—H8B	107.8
N1—P1—N2	103.17 (12)	C10—C9—C14	118.1 (3)
O1—P1—N3	103.15 (11)	C10—C9—C8	123.6 (2)
N1—P1—N3	109.14 (13)	C14—C9—C8	118.3 (3)
N2—P1—N3	108.72 (12)	C9—C10—C11	120.2 (3)
C1—N1—P1	122.3 (2)	C9—C10—H10A	119.9
C1—N1—H1N	118 (2)	C11—C10—H10A	119.9
P1—N1—H1N	117 (2)	C12—C11—C10	120.7 (3)
C8—N2—P1	120.50 (19)	C12—C11—H11A	119.7
C8—N2—H2N	114 (2)	C10—C11—H11A	119.7
P1—N2—H2N	118 (2)	C11—C12—C13	119.5 (3)
C15—N3—P1	122.91 (19)	C11—C12—H12A	120.2
C15—N3—H3N	119 (2)	C13—C12—H12A	120.2
P1—N3—H3N	118 (2)	C14—C13—C12	120.3 (3)
N1—C1—C2	112.5 (2)	C14—C13—H13A	119.9
N1—C1—H1B	109.1	C12—C13—H13A	119.9
C2—C1—H1B	109.1	C13—C14—C9	121.2 (3)
N1—C1—H1A	109.1	C13—C14—H14A	119.4
C2—C1—H1A	109.1	C9—C14—H14A	119.4
H1B—C1—H1A	107.8	O2—C15—N3	125.7 (3)
C3—C2—C7	118.9 (3)	O2—C15—C16	119.6 (3)
C3—C2—C1	120.6 (2)	N3—C15—C16	114.6 (2)
C7—C2—C1	120.5 (3)	F2—C16—F2A	54.8 (4)
C4—C3—C2	120.8 (3)	F2—C16—F1	94.3 (4)
C4—C3—H3A	119.6	F2A—C16—F1	138.5 (4)
C2—C3—H3A	119.6	F2—C16—F1A	136.0 (5)
C5—C4—C3	120.1 (3)	F2A—C16—F1A	95.3 (5)
C5—C4—H4A	120.0	F1—C16—F1A	90.2 (5)
C3—C4—H4A	120.0	F2—C16—C15	113.0 (3)
C6—C5—C4	119.9 (3)	F2A—C16—C15	110.6 (3)
C6—C5—H5A	120.1	F1—C16—C15	106.8 (4)
C4—C5—H5A	120.1	F1A—C16—C15	107.3 (5)
C5—C6—C7	120.2 (3)	F2—C16—Cl1A	70.7 (4)
C5—C6—H6A	119.9	F2A—C16—Cl1A	120.0 (4)
C7—C6—H6A	119.9	F1A—C16—Cl1A	109.2 (5)
C6—C7—C2	120.1 (3)	C15—C16—Cl1A	112.5 (3)
C6—C7—H7A	119.9	F2—C16—Cl1	116.7 (4)
C2—C7—H7A	119.9	F2A—C16—Cl1	71.6 (4)
N2—C8—C9	112.7 (2)	F1—C16—Cl1	107.5 (4)
N2—C8—H8A	109.0	C15—C16—Cl1	115.7 (3)
C9—C8—H8A	109.0	Cl1A—C16—Cl1	120.6 (3)
N2—C8—H8B	109.0
O1—P1—N1—C1	−45.6 (3)	C14—C9—C10—C11	0.6 (5)
N2—P1—N1—C1	−174.1 (2)	C8—C9—C10—C11	−178.7 (3)
N3—P1—N1—C1	70.4 (2)	C9—C10—C11—C12	−0.3 (5)
O1—P1—N2—C8	53.1 (2)	C10—C11—C12—C13	−0.8 (6)
N1—P1—N2—C8	−178.5 (2)	C11—C12—C13—C14	1.5 (6)
N3—P1—N2—C8	−62.8 (2)	C12—C13—C14—C9	−1.2 (6)
O1—P1—N3—C15	−175.7 (3)	C10—C9—C14—C13	0.2 (5)
N1—P1—N3—C15	60.2 (3)	C8—C9—C14—C13	179.5 (3)
N2—P1—N3—C15	−51.6 (3)	P1—N3—C15—O2	−0.6 (6)
P1—N1—C1—C2	−120.2 (2)	P1—N3—C15—C16	−179.3 (2)
N1—C1—C2—C3	−94.8 (3)	O2—C15—C16—F2	157.9 (5)
N1—C1—C2—C7	84.9 (3)	N3—C15—C16—F2	−23.3 (5)
C7—C2—C3—C4	−1.2 (4)	O2—C15—C16—F2A	−142.8 (5)
C1—C2—C3—C4	178.4 (3)	N3—C15—C16—F2A	36.0 (6)
C2—C3—C4—C5	0.4 (5)	O2—C15—C16—F1	55.6 (6)
C3—C4—C5—C6	−0.4 (5)	N3—C15—C16—F1	−125.6 (4)
C4—C5—C6—C7	1.2 (6)	O2—C15—C16—F1A	−40.0 (6)
C5—C6—C7—C2	−2.0 (6)	N3—C15—C16—F1A	138.8 (5)
C3—C2—C7—C6	2.0 (5)	O2—C15—C16—Cl1A	80.1 (5)
C1—C2—C7—C6	−177.6 (3)	N3—C15—C16—Cl1A	−101.1 (4)
P1—N2—C8—C9	−162.00 (19)	O2—C15—C16—Cl1	−64.0 (5)
N2—C8—C9—C10	5.0 (4)	N3—C15—C16—Cl1	114.8 (4)
N2—C8—C9—C14	−174.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1i	0.88 (2)	2.30 (3)	3.092 (3)	151 (3)
N2—H2N···O1i	0.86 (2)	2.05 (2)	2.867 (3)	158 (3)
N3—H3N···O2ii	0.86 (2)	2.01 (2)	2.854 (3)	166 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1i	0.88 (2)	2.30 (3)	3.092 (3)	151 (3)
N2—H2N⋯O1i	0.86 (2)	2.05 (2)	2.867 (3)	158 (3)
N3—H3N⋯O2ii	0.86 (2)	2.01 (2)	2.854 (3)	166 (3)

Symmetry codes: (i) ; (ii) .