N,N'-Dicyclo-hexyl-N''-(3-fluoro-benzo-yl)-N,N'-dimethyl-phospho-ric triamide.

In the title compound, C(21)H(33)FN(3)O(2)P, the P atom has a distorted tetra-hedral environment and the N atoms display geometries consistent with a model of sp(2) hybridization (with bond-angle sums for the tertiary N atoms of 357.8 and 358.7°). The phosphoryl and carbonyl groups are anti with respect to each other. In the crystal, inversion dimers linked by pairs of N-H⋯O hydrogen bonds generate R(2) (2)(8) loops.

Related literature

For the coordination properties of carbacyl­amido­phosphates, see: Pourayoubi et al. (2011b ▶); Gholivand et al. (2010 ▶); Znovjyak et al. (2009 ▶); Trush et al. (2005 ▶); Gubina et al. (2002 ▶). For related structures, see: Pourayoubi et al. (2011a ▶); Pourayoubi & Saneei (2011 ▶). For the syn orientation of the P(=O) group and NH unit in the C(O)NHP(O) skeleton for most known carbacyl­amido­phosphates, see: Toghraee et al. (2011 ▶). For a procedure to synthesise the starting phospho­rus–chlorine compound, see: Pourayoubi et al. (2011c ▶). For graph-set notation of hydrogen bonds, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C21H33FN3O2P

M = 409.47

Monoclinic,

a = 22.6634 (8) Å

b = 12.9587 (5) Å

c = 17.6627 (7) Å

β = 119.061 (1)°

V = 4534.3 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.15 mm−1

T = 296 K

0.32 × 0.28 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ▶) T min = 0.658, T max = 0.746

20958 measured reflections

4228 independent reflections

3254 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.157

S = 1.02

4228 reflections

257 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.93 e Å−3

Δρmin = −0.29 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX (Dolomanov et al., 2003 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶) and enCIFer (Allen et al., 2004 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811043017/qm2034sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811043017/qm2034Isup2.hkl

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

C21H33FN3O2P	F(000) = 1760
Mr = 409.47	Dx = 1.200 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8133 reflections
a = 22.6634 (8) Å	θ = 2.4–27.0°
b = 12.9587 (5) Å	µ = 0.15 mm−1
c = 17.6627 (7) Å	T = 296 K
β = 119.061 (1)°	Cubic, colourless
V = 4534.3 (3) Å3	0.32 × 0.28 × 0.16 mm
Z = 8

Bruker APEXII CCD diffractometer	4228 independent reflections
Radiation source: fine-focus sealed tube	3254 reflections with I > 2σ(I)
graphite	Rint = 0.031
φ and ω scans	θmax = 25.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −27→27
Tmin = 0.658, Tmax = 0.746	k = −15→15
20958 measured reflections	l = −21→21

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: inferred from neighbouring sites
wR(F2) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0936P)2 + 3.0653P] where P = (Fo2 + 2Fc2)/3
4228 reflections	(Δ/σ)max < 0.001
257 parameters	Δρmax = 0.93 e Å−3
1 restraint	Δρmin = −0.29 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.19691 (2)	0.87686 (4)	0.02588 (3)	0.03552 (19)
O2	0.30019 (9)	0.98806 (14)	0.18782 (12)	0.0637 (5)
F1	0.46037 (14)	0.6077 (2)	0.31270 (17)	0.1416 (10)
O1	0.16844 (7)	0.78142 (11)	−0.02507 (9)	0.0426 (4)
N1	0.27588 (8)	0.84697 (15)	0.10211 (11)	0.0370 (4)
C1	0.31644 (10)	0.90341 (18)	0.17448 (13)	0.0417 (5)
C3	0.15054 (14)	1.02308 (19)	0.0955 (2)	0.0618 (7)
H3A	0.1710	1.0669	0.0709	0.093*
H3B	0.1751	1.0282	0.1575	0.093*
H3C	0.1047	1.0443	0.0749	0.093*
N2	0.20318 (9)	0.97566 (15)	−0.02662 (12)	0.0479 (5)
C19	0.0611 (3)	0.7585 (4)	0.2030 (4)	0.135 (2)
H19A	0.0582	0.8200	0.2323	0.162*
H19B	0.0428	0.7012	0.2204	0.162*
C20	0.0200 (2)	0.7734 (4)	0.1057 (4)	0.1268 (18)
H20A	−0.0261	0.7903	0.0905	0.152*
H20B	0.0193	0.7094	0.0769	0.152*
C21	0.04874 (15)	0.8595 (3)	0.0735 (2)	0.0828 (10)
H21A	0.0231	0.8637	0.0108	0.099*
H21B	0.0450	0.9252	0.0971	0.099*
C16	0.12210 (11)	0.83718 (19)	0.10158 (15)	0.0477 (5)
H16	0.1235	0.7713	0.0752	0.057*
N3	0.15171 (9)	0.91587 (14)	0.06955 (12)	0.0429 (4)
C4	0.38187 (11)	0.8550 (2)	0.23687 (13)	0.0458 (6)
C5	0.39071 (12)	0.7492 (2)	0.24479 (15)	0.0563 (6)
H5	0.3560	0.7044	0.2099	0.068*
C6	0.45265 (15)	0.7122 (3)	0.30609 (18)	0.0740 (9)
C7	0.50556 (14)	0.7743 (4)	0.35762 (17)	0.0865 (12)
H7	0.5470	0.7466	0.3975	0.104*
C18	0.1330 (3)	0.7373 (3)	0.2291 (3)	0.1109 (15)
H18A	0.1362	0.6723	0.2041	0.133*
H18B	0.1588	0.7311	0.2917	0.133*
C17	0.16264 (17)	0.8231 (3)	0.19916 (18)	0.0774 (9)
H17A	0.1626	0.8871	0.2277	0.093*
H17B	0.2090	0.8064	0.2154	0.093*
C10	0.26677 (11)	1.00986 (18)	−0.02259 (15)	0.0462 (5)
H10	0.3035	0.9781	0.0293	0.055*
C15	0.27532 (14)	0.9741 (2)	−0.09852 (16)	0.0599 (7)
H15A	0.2726	0.8994	−0.1022	0.072*
H15B	0.2390	1.0019	−0.1518	0.072*
C14	0.34258 (17)	1.0089 (3)	−0.0885 (2)	0.0776 (9)
H14A	0.3454	0.9893	−0.1397	0.093*
H14B	0.3788	0.9743	−0.0391	0.093*
C13	0.35163 (19)	1.1247 (3)	−0.0759 (2)	0.0881 (10)
H13A	0.3961	1.1439	−0.0664	0.106*
H13B	0.3183	1.1595	−0.1277	0.106*
C12	0.34381 (19)	1.1582 (3)	0.0008 (3)	0.0898 (10)
H12A	0.3480	1.2326	0.0066	0.108*
H12B	0.3796	1.1278	0.0532	0.108*
C11	0.27582 (17)	1.1256 (2)	−0.0098 (2)	0.0723 (8)
H11A	0.2729	1.1454	0.0412	0.087*
H11B	0.2400	1.1606	−0.0594	0.087*
C2	0.13971 (13)	1.0138 (2)	−0.09931 (19)	0.0692 (8)
H2A	0.1022	0.9864	−0.0948	0.104*
H2B	0.1367	0.9921	−0.1530	0.104*
H2C	0.1389	1.0878	−0.0975	0.104*
C9	0.43442 (12)	0.9204 (3)	0.28957 (16)	0.0652 (7)
H9	0.4284	0.9915	0.2851	0.078*
C8	0.49597 (15)	0.8784 (4)	0.34893 (19)	0.0887 (12)
H8	0.5315	0.9221	0.3836	0.106*
H1	0.2925 (11)	0.8035 (17)	0.0877 (14)	0.038 (6)*

	U11	U22	U33	U12	U13	U23
P1	0.0267 (3)	0.0428 (3)	0.0322 (3)	0.0018 (2)	0.0104 (2)	−0.0015 (2)
O2	0.0569 (11)	0.0588 (11)	0.0590 (11)	0.0018 (8)	0.0153 (9)	−0.0221 (8)
F1	0.117 (2)	0.160 (2)	0.1197 (19)	0.0660 (17)	0.0356 (16)	0.0554 (17)
O1	0.0301 (7)	0.0530 (9)	0.0395 (8)	−0.0025 (6)	0.0128 (6)	−0.0097 (7)
N1	0.0297 (9)	0.0432 (10)	0.0319 (9)	0.0053 (7)	0.0100 (7)	−0.0046 (7)
C1	0.0344 (11)	0.0534 (14)	0.0345 (11)	−0.0035 (9)	0.0145 (9)	−0.0065 (9)
C3	0.0623 (16)	0.0495 (15)	0.0805 (19)	0.0079 (12)	0.0401 (15)	−0.0068 (13)
N2	0.0341 (10)	0.0566 (12)	0.0448 (10)	0.0024 (8)	0.0127 (8)	0.0117 (9)
C19	0.197 (6)	0.116 (3)	0.183 (5)	−0.055 (3)	0.164 (5)	−0.036 (3)
C20	0.098 (3)	0.134 (4)	0.195 (5)	−0.058 (3)	0.108 (4)	−0.058 (4)
C21	0.0469 (15)	0.108 (2)	0.099 (2)	−0.0154 (15)	0.0406 (16)	−0.0275 (19)
C16	0.0438 (12)	0.0544 (14)	0.0504 (13)	−0.0089 (10)	0.0272 (11)	−0.0132 (11)
N3	0.0382 (10)	0.0433 (10)	0.0495 (10)	0.0031 (8)	0.0231 (8)	−0.0041 (8)
C4	0.0318 (11)	0.0755 (17)	0.0283 (10)	−0.0034 (10)	0.0133 (9)	−0.0064 (10)
C5	0.0392 (13)	0.0812 (19)	0.0388 (12)	0.0100 (12)	0.0113 (10)	0.0077 (12)
C6	0.0586 (17)	0.106 (2)	0.0518 (15)	0.0363 (17)	0.0225 (14)	0.0271 (16)
C7	0.0364 (15)	0.173 (4)	0.0375 (14)	0.0246 (19)	0.0079 (12)	0.0137 (19)
C18	0.168 (5)	0.103 (3)	0.096 (3)	−0.021 (3)	0.090 (3)	0.008 (2)
C17	0.080 (2)	0.096 (2)	0.0561 (17)	−0.0145 (17)	0.0327 (16)	0.0047 (16)
C10	0.0408 (12)	0.0554 (14)	0.0414 (12)	−0.0026 (10)	0.0192 (10)	0.0040 (10)
C15	0.0671 (17)	0.0661 (17)	0.0508 (14)	−0.0006 (13)	0.0321 (13)	−0.0005 (12)
C14	0.081 (2)	0.104 (2)	0.0696 (19)	−0.0008 (18)	0.0532 (18)	0.0014 (17)
C13	0.081 (2)	0.109 (3)	0.092 (2)	−0.0239 (19)	0.055 (2)	0.0053 (19)
C12	0.087 (2)	0.085 (2)	0.116 (3)	−0.0347 (19)	0.064 (2)	−0.021 (2)
C11	0.077 (2)	0.0608 (17)	0.095 (2)	−0.0165 (14)	0.0536 (18)	−0.0173 (15)
C2	0.0450 (14)	0.0756 (19)	0.0676 (17)	0.0094 (13)	0.0120 (13)	0.0298 (14)
C9	0.0389 (13)	0.104 (2)	0.0453 (14)	−0.0153 (13)	0.0144 (11)	−0.0201 (14)
C8	0.0348 (14)	0.173 (4)	0.0450 (16)	−0.0165 (19)	0.0090 (12)	−0.020 (2)

P1—O1	1.4803 (15)	C6—C7	1.362 (5)
P1—N2	1.6271 (19)	C7—C8	1.362 (5)
P1—N3	1.6333 (17)	C7—H7	0.9300
P1—N1	1.6808 (17)	C18—C17	1.521 (4)
O2—C1	1.216 (3)	C18—H18A	0.9700
F1—C6	1.363 (4)	C18—H18B	0.9700
N1—C1	1.368 (3)	C17—H17A	0.9700
N1—H1	0.78 (2)	C17—H17B	0.9700
C1—C4	1.490 (3)	C10—C11	1.515 (3)
C3—N3	1.467 (3)	C10—C15	1.518 (3)
C3—H3A	0.9600	C10—H10	0.9800
C3—H3B	0.9600	C15—C14	1.515 (4)
C3—H3C	0.9600	C15—H15A	0.9700
N2—C2	1.472 (3)	C15—H15B	0.9700
N2—C10	1.476 (3)	C14—C13	1.516 (4)
C19—C18	1.487 (6)	C14—H14A	0.9700
C19—C20	1.518 (7)	C14—H14B	0.9700
C19—H19A	0.9700	C13—C12	1.513 (5)
C19—H19B	0.9700	C13—H13A	0.9700
C20—C21	1.533 (5)	C13—H13B	0.9700
C20—H20A	0.9700	C12—C11	1.519 (4)
C20—H20B	0.9700	C12—H12A	0.9700
C21—C16	1.514 (4)	C12—H12B	0.9700
C21—H21A	0.9700	C11—H11A	0.9700
C21—H21B	0.9700	C11—H11B	0.9700
C16—N3	1.476 (3)	C2—H2A	0.9600
C16—C17	1.520 (4)	C2—H2B	0.9600
C16—H16	0.9800	C2—H2C	0.9600
C4—C5	1.383 (4)	C9—C8	1.386 (4)
C4—C9	1.388 (3)	C9—H9	0.9300
C5—C6	1.377 (3)	C8—H8	0.9300
C5—H5	0.9300
O1—P1—N2	116.35 (10)	C19—C18—C17	111.1 (4)
O1—P1—N3	110.95 (9)	C19—C18—H18A	109.4
N2—P1—N3	105.90 (10)	C17—C18—H18A	109.4
O1—P1—N1	105.93 (9)	C19—C18—H18B	109.4
N2—P1—N1	106.50 (9)	C17—C18—H18B	109.4
N3—P1—N1	111.17 (9)	H18A—C18—H18B	108.0
C1—N1—P1	126.58 (16)	C16—C17—C18	110.9 (3)
C1—N1—H1	118.4 (17)	C16—C17—H17A	109.5
P1—N1—H1	113.4 (16)	C18—C17—H17A	109.5
O2—C1—N1	122.3 (2)	C16—C17—H17B	109.5
O2—C1—C4	121.5 (2)	C18—C17—H17B	109.5
N1—C1—C4	116.18 (19)	H17A—C17—H17B	108.0
N3—C3—H3A	109.5	N2—C10—C11	111.3 (2)
N3—C3—H3B	109.5	N2—C10—C15	114.0 (2)
H3A—C3—H3B	109.5	C11—C10—C15	111.6 (2)
N3—C3—H3C	109.5	N2—C10—H10	106.5
H3A—C3—H3C	109.5	C11—C10—H10	106.5
H3B—C3—H3C	109.5	C15—C10—H10	106.5
C2—N2—C10	117.30 (19)	C14—C15—C10	111.0 (2)
C2—N2—P1	116.26 (16)	C14—C15—H15A	109.4
C10—N2—P1	124.22 (15)	C10—C15—H15A	109.4
C18—C19—C20	110.6 (3)	C14—C15—H15B	109.4
C18—C19—H19A	109.5	C10—C15—H15B	109.4
C20—C19—H19A	109.5	H15A—C15—H15B	108.0
C18—C19—H19B	109.5	C15—C14—C13	111.6 (3)
C20—C19—H19B	109.5	C15—C14—H14A	109.3
H19A—C19—H19B	108.1	C13—C14—H14A	109.3
C19—C20—C21	112.0 (3)	C15—C14—H14B	109.3
C19—C20—H20A	109.2	C13—C14—H14B	109.3
C21—C20—H20A	109.2	H14A—C14—H14B	108.0
C19—C20—H20B	109.2	C12—C13—C14	110.4 (3)
C21—C20—H20B	109.2	C12—C13—H13A	109.6
H20A—C20—H20B	107.9	C14—C13—H13A	109.6
C16—C21—C20	109.7 (3)	C12—C13—H13B	109.6
C16—C21—H21A	109.7	C14—C13—H13B	109.6
C20—C21—H21A	109.7	H13A—C13—H13B	108.1
C16—C21—H21B	109.7	C13—C12—C11	111.3 (3)
C20—C21—H21B	109.7	C13—C12—H12A	109.4
H21A—C21—H21B	108.2	C11—C12—H12A	109.4
N3—C16—C21	112.0 (2)	C13—C12—H12B	109.4
N3—C16—C17	112.4 (2)	C11—C12—H12B	109.4
C21—C16—C17	110.9 (2)	H12A—C12—H12B	108.0
N3—C16—H16	107.1	C10—C11—C12	110.4 (3)
C21—C16—H16	107.1	C10—C11—H11A	109.6
C17—C16—H16	107.1	C12—C11—H11A	109.6
C3—N3—C16	117.01 (18)	C10—C11—H11B	109.6
C3—N3—P1	123.44 (16)	C12—C11—H11B	109.6
C16—N3—P1	118.25 (15)	H11A—C11—H11B	108.1
C5—C4—C9	120.2 (2)	N2—C2—H2A	109.5
C5—C4—C1	122.4 (2)	N2—C2—H2B	109.5
C9—C4—C1	117.4 (2)	H2A—C2—H2B	109.5
C6—C5—C4	117.8 (3)	N2—C2—H2C	109.5
C6—C5—H5	121.1	H2A—C2—H2C	109.5
C4—C5—H5	121.1	H2B—C2—H2C	109.5
C7—C6—F1	119.7 (3)	C8—C9—C4	119.2 (3)
C7—C6—C5	123.4 (3)	C8—C9—H9	120.4
F1—C6—C5	116.9 (3)	C4—C9—H9	120.4
C6—C7—C8	118.0 (3)	C7—C8—C9	121.4 (3)
C6—C7—H7	121.0	C7—C8—H8	119.3
C8—C7—H7	121.0	C9—C8—H8	119.3
O1—P1—N1—C1	−165.46 (18)	N1—C1—C4—C9	154.3 (2)
N2—P1—N1—C1	70.1 (2)	C9—C4—C5—C6	0.1 (3)
N3—P1—N1—C1	−44.8 (2)	C1—C4—C5—C6	−178.2 (2)
P1—N1—C1—O2	−5.7 (3)	C4—C5—C6—C7	−1.4 (4)
P1—N1—C1—C4	173.91 (15)	C4—C5—C6—F1	−179.8 (2)
O1—P1—N2—C2	60.3 (2)	F1—C6—C7—C8	179.8 (3)
N3—P1—N2—C2	−63.5 (2)	C5—C6—C7—C8	1.4 (5)
N1—P1—N2—C2	178.06 (19)	C20—C19—C18—C17	56.5 (5)
O1—P1—N2—C10	−102.28 (19)	N3—C16—C17—C18	−176.7 (3)
N3—P1—N2—C10	133.94 (18)	C21—C16—C17—C18	57.1 (4)
N1—P1—N2—C10	15.5 (2)	C19—C18—C17—C16	−57.4 (4)
C18—C19—C20—C21	−56.3 (5)	C2—N2—C10—C11	63.9 (3)
C19—C20—C21—C16	55.5 (4)	P1—N2—C10—C11	−133.7 (2)
C20—C21—C16—N3	178.0 (3)	C2—N2—C10—C15	−63.3 (3)
C20—C21—C16—C17	−55.6 (4)	P1—N2—C10—C15	99.0 (2)
C21—C16—N3—C3	58.5 (3)	N2—C10—C15—C14	−178.1 (2)
C17—C16—N3—C3	−67.1 (3)	C11—C10—C15—C14	54.8 (3)
C21—C16—N3—P1	−134.1 (2)	C10—C15—C14—C13	−55.0 (3)
C17—C16—N3—P1	100.3 (2)	C15—C14—C13—C12	56.0 (4)
O1—P1—N3—C3	−156.59 (19)	C14—C13—C12—C11	−56.9 (4)
N2—P1—N3—C3	−29.5 (2)	N2—C10—C11—C12	175.9 (3)
N1—P1—N3—C3	85.8 (2)	C15—C10—C11—C12	−55.6 (4)
O1—P1—N3—C16	36.84 (18)	C13—C12—C11—C10	56.8 (4)
N2—P1—N3—C16	163.94 (15)	C5—C4—C9—C8	1.1 (4)
N1—P1—N3—C16	−80.77 (17)	C1—C4—C9—C8	179.5 (2)
O2—C1—C4—C5	152.3 (2)	C6—C7—C8—C9	−0.1 (5)
N1—C1—C4—C5	−27.3 (3)	C4—C9—C8—C7	−1.1 (4)
O2—C1—C4—C9	−26.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.78 (2)	2.04 (2)	2.807 (2)	165 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.78 (2)	2.04 (2)	2.807 (2)	165 (2)

Symmetry code: (i) .