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

In the title mol-ecule, C(18)H(21)ClF(2)N(3)O(2)P, the P=O and N-H groups are syn to each other. The P atom adopts a slightly distorted tetra-hedral environment and the N atoms of the tertiary amine groups are bonded in an essentially planar geometry. In the crystal, pairs of inter-molecular N-H⋯O(P) hydrogen bonds form centrosymmetric dimers.

Related literature

For metal complexes with phosphoryl donor ligands, see: Gholivand et al. (2010 ▶). For a polyoxometalate-based inorganic–organic compound containing a phosphoryl ligand, see: Niu et al. (1996 ▶). For phospho­ric triamide compounds having a C(=O)NHP(=O) skeleton, see: Pourayoubi & Sabbaghi (2009 ▶) and references cited therein. For bond lengths in related structures, see: Sabbaghi et al. (2010 ▶). For hydrogen-bond motifs, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶). For the synthesis of the starting material, CClF2C(O)NHP(O)Cl2, see: Iriarte et al. (2008 ▶).

Experimental

Crystal data

C18H21ClF2N3O2P

M = 415.80

Triclinic,

a = 10.3059 (9) Å

b = 10.5030 (9) Å

c = 10.9473 (9) Å

α = 71.743 (2)°

β = 67.294 (2)°

γ = 63.265 (2)°

V = 962.15 (14) Å3

Z = 2

Mo Kα radiation

μ = 0.32 mm−1

T = 120 K

0.28 × 0.22 × 0.15 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ▶) T min = 0.916, T max = 0.954

9258 measured reflections

4148 independent reflections

3359 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.111

S = 1.00

4148 reflections

247 parameters

H-atom parameters constrained

Δρmax = 0.39 e Å−3

Δρmin = −0.37 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 1998 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005423/lh5205sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005423/lh5205Isup2.hkl

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

C18H21ClF2N3O2P	Z = 2
Mr = 415.80	F(000) = 432
Triclinic, P1	Dx = 1.435 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.3059 (9) Å	Cell parameters from 3946 reflections
b = 10.5030 (9) Å	θ = 2.3–29.1°
c = 10.9473 (9) Å	µ = 0.32 mm−1
α = 71.743 (2)°	T = 120 K
β = 67.294 (2)°	Prism, colourless
γ = 63.265 (2)°	0.28 × 0.22 × 0.15 mm
V = 962.15 (14) Å3

Bruker SMART 1000 CCD area-detector diffractometer	4148 independent reflections
Radiation source: fine-focus sealed tube	3359 reflections with I > 2σ(I)
graphite	Rint = 0.025
φ and ω scans	θmax = 27.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −13→13
Tmin = 0.916, Tmax = 0.954	k = −13→13
9258 measured reflections	l = −13→13

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049	Hydrogen site location: mixed
wR(F2) = 0.111	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0309P)2 + 1.6759P] where P = (Fo2 + 2Fc2)/3
4148 reflections	(Δ/σ)max < 0.001
247 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.37 e Å−3

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
P1	0.24133 (6)	0.55399 (6)	0.07097 (5)	0.01766 (13)
Cl1	0.40224 (7)	0.93801 (7)	−0.06620 (6)	0.03255 (16)
F1	0.45008 (15)	0.79512 (15)	0.15810 (14)	0.0304 (3)
F2	0.25207 (16)	0.99322 (15)	0.16926 (15)	0.0346 (3)
O1	0.37544 (16)	0.44767 (15)	−0.00684 (15)	0.0207 (3)
O2	0.09472 (17)	0.85802 (17)	0.16326 (17)	0.0290 (4)
N1	0.11179 (19)	0.66717 (19)	−0.00324 (17)	0.0194 (4)
N2	0.1560 (2)	0.47741 (19)	0.21311 (17)	0.0205 (4)
N3	0.3102 (2)	0.66075 (19)	0.09736 (18)	0.0197 (4)
H3N	0.4088	0.6297	0.0731	0.039 (8)*
C1	−0.0432 (3)	0.6755 (3)	0.0358 (2)	0.0300 (5)
H1A	−0.0678	0.6791	−0.0435	0.045*
H1B	−0.1129	0.7630	0.0751	0.045*
H1C	−0.0534	0.5902	0.1021	0.045*
C2	0.1497 (3)	0.7723 (2)	−0.1223 (2)	0.0232 (4)
H2A	0.2436	0.7795	−0.1257	0.028*
H2B	0.0671	0.8685	−0.1125	0.028*
C3	0.1726 (2)	0.7347 (2)	−0.2540 (2)	0.0215 (4)
C4	0.1249 (2)	0.8454 (2)	−0.3561 (2)	0.0241 (5)
H4A	0.0693	0.9420	−0.3396	0.029*
C5	0.1583 (3)	0.8152 (3)	−0.4825 (2)	0.0281 (5)
H5A	0.1265	0.8912	−0.5521	0.034*
C6	0.2378 (3)	0.6744 (3)	−0.5067 (2)	0.0299 (5)
H6A	0.2612	0.6537	−0.5929	0.036*
C7	0.2835 (3)	0.5633 (3)	−0.4041 (2)	0.0293 (5)
H7A	0.3371	0.4666	−0.4204	0.035*
C8	0.2511 (3)	0.5929 (2)	−0.2784 (2)	0.0254 (5)
H8A	0.2825	0.5165	−0.2088	0.030*
C9	0.0398 (3)	0.5614 (2)	0.3182 (2)	0.0254 (5)
H9A	−0.0450	0.5282	0.3573	0.038*
H9B	0.0031	0.6641	0.2790	0.038*
H9C	0.0839	0.5478	0.3885	0.038*
C10	0.2044 (3)	0.3195 (2)	0.2526 (2)	0.0235 (4)
H10A	0.2779	0.2738	0.1736	0.028*
H10B	0.1151	0.2927	0.2808	0.028*
C11	0.2766 (2)	0.2604 (2)	0.3657 (2)	0.0217 (4)
C12	0.4040 (3)	0.2854 (2)	0.3528 (2)	0.0249 (5)
H12A	0.4465	0.3391	0.2720	0.030*
C13	0.4683 (3)	0.2321 (2)	0.4577 (2)	0.0263 (5)
H13A	0.5547	0.2497	0.4485	0.032*
C14	0.4077 (3)	0.1535 (2)	0.5757 (2)	0.0267 (5)
H14A	0.4521	0.1177	0.6473	0.032*
C15	0.2827 (3)	0.1271 (2)	0.5896 (2)	0.0279 (5)
H15A	0.2415	0.0723	0.6702	0.034*
C16	0.2175 (3)	0.1812 (2)	0.4847 (2)	0.0250 (5)
H16A	0.1309	0.1635	0.4948	0.030*
C17	0.2317 (2)	0.7958 (2)	0.1275 (2)	0.0213 (4)
C18	0.3323 (3)	0.8782 (2)	0.1073 (2)	0.0242 (5)

	U11	U22	U33	U12	U13	U23
P1	0.0166 (3)	0.0174 (3)	0.0179 (3)	−0.0063 (2)	−0.0047 (2)	−0.0021 (2)
Cl1	0.0383 (3)	0.0335 (3)	0.0279 (3)	−0.0217 (3)	−0.0053 (2)	−0.0007 (2)
F1	0.0315 (7)	0.0306 (7)	0.0366 (8)	−0.0135 (6)	−0.0154 (6)	−0.0052 (6)
F2	0.0362 (8)	0.0289 (7)	0.0408 (8)	−0.0132 (6)	−0.0024 (6)	−0.0182 (6)
O1	0.0184 (7)	0.0203 (7)	0.0230 (8)	−0.0061 (6)	−0.0055 (6)	−0.0059 (6)
O2	0.0209 (8)	0.0242 (8)	0.0371 (9)	−0.0052 (7)	−0.0030 (7)	−0.0108 (7)
N1	0.0179 (8)	0.0201 (9)	0.0189 (9)	−0.0076 (7)	−0.0057 (7)	−0.0004 (7)
N2	0.0197 (9)	0.0193 (9)	0.0186 (8)	−0.0077 (7)	−0.0038 (7)	0.0002 (7)
N3	0.0167 (8)	0.0188 (9)	0.0237 (9)	−0.0056 (7)	−0.0065 (7)	−0.0044 (7)
C1	0.0195 (11)	0.0406 (14)	0.0272 (12)	−0.0104 (10)	−0.0092 (9)	−0.0002 (10)
C2	0.0294 (11)	0.0194 (10)	0.0213 (11)	−0.0098 (9)	−0.0103 (9)	0.0008 (8)
C3	0.0211 (10)	0.0259 (11)	0.0195 (10)	−0.0124 (9)	−0.0057 (8)	−0.0013 (8)
C4	0.0208 (10)	0.0270 (11)	0.0239 (11)	−0.0105 (9)	−0.0070 (9)	−0.0005 (9)
C5	0.0277 (12)	0.0373 (13)	0.0210 (11)	−0.0146 (10)	−0.0114 (9)	0.0023 (9)
C6	0.0314 (12)	0.0449 (14)	0.0208 (11)	−0.0212 (11)	−0.0062 (9)	−0.0060 (10)
C7	0.0321 (12)	0.0300 (12)	0.0285 (12)	−0.0155 (10)	−0.0046 (10)	−0.0079 (10)
C8	0.0282 (11)	0.0242 (11)	0.0246 (11)	−0.0125 (9)	−0.0084 (9)	0.0001 (9)
C9	0.0250 (11)	0.0295 (12)	0.0173 (10)	−0.0114 (9)	−0.0016 (9)	−0.0023 (9)
C10	0.0275 (11)	0.0203 (10)	0.0243 (11)	−0.0116 (9)	−0.0102 (9)	0.0016 (8)
C11	0.0236 (10)	0.0171 (10)	0.0237 (11)	−0.0063 (8)	−0.0084 (9)	−0.0025 (8)
C12	0.0253 (11)	0.0253 (11)	0.0236 (11)	−0.0119 (9)	−0.0055 (9)	−0.0020 (9)
C13	0.0222 (11)	0.0258 (11)	0.0317 (12)	−0.0078 (9)	−0.0096 (9)	−0.0054 (9)
C14	0.0273 (11)	0.0249 (11)	0.0264 (11)	−0.0042 (9)	−0.0125 (9)	−0.0051 (9)
C15	0.0308 (12)	0.0236 (11)	0.0241 (11)	−0.0102 (10)	−0.0080 (9)	0.0026 (9)
C16	0.0242 (11)	0.0245 (11)	0.0268 (11)	−0.0116 (9)	−0.0092 (9)	0.0013 (9)
C17	0.0235 (11)	0.0205 (10)	0.0192 (10)	−0.0088 (9)	−0.0054 (8)	−0.0025 (8)
C18	0.0249 (11)	0.0205 (10)	0.0261 (11)	−0.0072 (9)	−0.0055 (9)	−0.0068 (9)

P1—O1	1.4769 (15)	C5—H5A	0.9500
P1—N2	1.6241 (18)	C6—C7	1.391 (3)
P1—N1	1.6308 (18)	C6—H6A	0.9500
P1—N3	1.7093 (18)	C7—C8	1.387 (3)
Cl1—C18	1.768 (2)	C7—H7A	0.9500
F1—C18	1.345 (3)	C8—H8A	0.9500
F2—C18	1.336 (2)	C9—H9A	0.9800
O2—C17	1.215 (3)	C9—H9B	0.9800
N1—C1	1.453 (3)	C9—H9C	0.9800
N1—C2	1.471 (3)	C10—C11	1.512 (3)
N2—C9	1.469 (3)	C10—H10A	0.9900
N2—C10	1.469 (3)	C10—H10B	0.9900
N3—C17	1.353 (3)	C11—C16	1.387 (3)
N3—H3N	0.8700	C11—C12	1.399 (3)
C1—H1A	0.9800	C12—C13	1.387 (3)
C1—H1B	0.9800	C12—H12A	0.9500
C1—H1C	0.9800	C13—C14	1.383 (3)
C2—C3	1.517 (3)	C13—H13A	0.9500
C2—H2A	0.9900	C14—C15	1.379 (3)
C2—H2B	0.9900	C14—H14A	0.9500
C3—C4	1.393 (3)	C15—C16	1.391 (3)
C3—C8	1.394 (3)	C15—H15A	0.9500
C4—C5	1.394 (3)	C16—H16A	0.9500
C4—H4A	0.9500	C17—C18	1.543 (3)
C5—C6	1.384 (4)
O1—P1—N2	112.34 (9)	C7—C8—C3	120.0 (2)
O1—P1—N1	117.13 (9)	C7—C8—H8A	120.0
N2—P1—N1	107.02 (9)	C3—C8—H8A	120.0
O1—P1—N3	105.06 (9)	N2—C9—H9A	109.5
N2—P1—N3	110.57 (9)	N2—C9—H9B	109.5
N1—P1—N3	104.38 (9)	H9A—C9—H9B	109.5
C1—N1—C2	114.36 (17)	N2—C9—H9C	109.5
C1—N1—P1	126.21 (15)	H9A—C9—H9C	109.5
C2—N1—P1	119.42 (14)	H9B—C9—H9C	109.5
C9—N2—C10	115.45 (17)	N2—C10—C11	113.28 (18)
C9—N2—P1	121.56 (14)	N2—C10—H10A	108.9
C10—N2—P1	122.42 (15)	C11—C10—H10A	108.9
C17—N3—P1	127.29 (15)	N2—C10—H10B	108.9
C17—N3—H3N	117.5	C11—C10—H10B	108.9
P1—N3—H3N	114.0	H10A—C10—H10B	107.7
N1—C1—H1A	109.5	C16—C11—C12	118.6 (2)
N1—C1—H1B	109.5	C16—C11—C10	120.9 (2)
H1A—C1—H1B	109.5	C12—C11—C10	120.59 (19)
N1—C1—H1C	109.5	C13—C12—C11	120.2 (2)
H1A—C1—H1C	109.5	C13—C12—H12A	119.9
H1B—C1—H1C	109.5	C11—C12—H12A	119.9
N1—C2—C3	114.05 (17)	C14—C13—C12	120.4 (2)
N1—C2—H2A	108.7	C14—C13—H13A	119.8
C3—C2—H2A	108.7	C12—C13—H13A	119.8
N1—C2—H2B	108.7	C15—C14—C13	120.1 (2)
C3—C2—H2B	108.7	C15—C14—H14A	120.0
H2A—C2—H2B	107.6	C13—C14—H14A	120.0
C4—C3—C8	119.4 (2)	C14—C15—C16	119.6 (2)
C4—C3—C2	119.3 (2)	C14—C15—H15A	120.2
C8—C3—C2	121.15 (19)	C16—C15—H15A	120.2
C3—C4—C5	120.3 (2)	C11—C16—C15	121.2 (2)
C3—C4—H4A	119.8	C11—C16—H16A	119.4
C5—C4—H4A	119.8	C15—C16—H16A	119.4
C6—C5—C4	120.1 (2)	O2—C17—N3	127.4 (2)
C6—C5—H5A	120.0	O2—C17—C18	118.39 (19)
C4—C5—H5A	120.0	N3—C17—C18	114.16 (18)
C5—C6—C7	119.7 (2)	F2—C18—F1	107.18 (18)
C5—C6—H6A	120.1	F2—C18—C17	110.49 (18)
C7—C6—H6A	120.1	F1—C18—C17	111.98 (17)
C8—C7—C6	120.5 (2)	F2—C18—Cl1	108.70 (15)
C8—C7—H7A	119.8	F1—C18—Cl1	109.06 (15)
C6—C7—H7A	119.8	C17—C18—Cl1	109.35 (15)
O1—P1—N1—C1	115.12 (19)	C6—C7—C8—C3	−0.1 (3)
N2—P1—N1—C1	−12.0 (2)	C4—C3—C8—C7	1.2 (3)
N3—P1—N1—C1	−129.24 (19)	C2—C3—C8—C7	−173.7 (2)
O1—P1—N1—C2	−64.27 (18)	C9—N2—C10—C11	−61.8 (2)
N2—P1—N1—C2	168.61 (15)	P1—N2—C10—C11	109.64 (19)
N3—P1—N1—C2	51.38 (17)	N2—C10—C11—C16	122.1 (2)
O1—P1—N2—C9	167.42 (16)	N2—C10—C11—C12	−57.4 (3)
N1—P1—N2—C9	−62.69 (18)	C16—C11—C12—C13	−0.2 (3)
N3—P1—N2—C9	50.40 (19)	C10—C11—C12—C13	179.2 (2)
O1—P1—N2—C10	−3.55 (19)	C11—C12—C13—C14	0.2 (3)
N1—P1—N2—C10	126.34 (17)	C12—C13—C14—C15	0.3 (3)
N3—P1—N2—C10	−120.57 (16)	C13—C14—C15—C16	−0.6 (3)
O1—P1—N3—C17	158.89 (18)	C12—C11—C16—C15	−0.1 (3)
N2—P1—N3—C17	−79.68 (19)	C10—C11—C16—C15	−179.6 (2)
N1—P1—N3—C17	35.1 (2)	C14—C15—C16—C11	0.6 (4)
C1—N1—C2—C3	−75.1 (2)	P1—N3—C17—O2	13.3 (3)
P1—N1—C2—C3	104.32 (19)	P1—N3—C17—C18	−164.20 (15)
N1—C2—C3—C4	143.87 (19)	O2—C17—C18—F2	17.7 (3)
N1—C2—C3—C8	−41.2 (3)	N3—C17—C18—F2	−164.59 (18)
C8—C3—C4—C5	−1.5 (3)	O2—C17—C18—F1	137.1 (2)
C2—C3—C4—C5	173.5 (2)	N3—C17—C18—F1	−45.2 (2)
C3—C4—C5—C6	0.7 (3)	O2—C17—C18—Cl1	−101.9 (2)
C4—C5—C6—C7	0.4 (3)	N3—C17—C18—Cl1	75.8 (2)
C5—C6—C7—C8	−0.6 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O1i	0.87	1.91	2.772 (3)	174

Table 1

Selected bond angles (°)

O1—P1—N2	112.34 (9)
O1—P1—N1	117.13 (9)
N2—P1—N1	107.02 (9)
O1—P1—N3	105.06 (9)
N2—P1—N3	110.57 (9)
N1—P1—N3	104.38 (9)
C1—N1—C2	114.36 (17)
C1—N1—P1	126.21 (15)
C2—N1—P1	119.42 (14)
C9—N2—C10	115.45 (17)
C9—N2—P1	121.56 (14)
C10—N2—P1	122.42 (15)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯O1i	0.87	1.91	2.772 (3)	174

Symmetry code: (i) .