N-(2,6-Difluoro-benzo-yl)-P,P-bis-(pyrrolidin-1-yl)phosphinic amide.

The phosphoryl and carbonyl groups in the title compound, C(15)H(20)F(2)N(3)O(2)P, are anti with respect to each other (but the P- and C-groups are separated by another atom) and the P atom is in a tetra-hedral coordination environment. Two C atoms in one of the pyrrolidinyl fragments are disordered over two sets of sites with occupancies of 0.746 (8) and 0.254 (8). The environments of the pyrrolidinyl N atoms show a slight deviation from planarity and none of the three N atoms is involved in any hydrogen bond as an acceptor. In the crystal, pairs of inter-molecular N-H⋯O hydrogen bonds form inversion dimers.

Related literature

For hydrogen-bond patterns in compounds containing a C(O)NHP(O) skeleton, see: Toghraee et al. (2011 ▶); Pourayoubi et al. (2011 ▶). For hydrogen-bond strength, see: Pourayoubi et al. (2011 ▶). For a related structure, see: Pourayoubi et al. (2010 ▶). For bond lengths, angles and torsion angles, see: Tarahhomi et al. (2011 ▶). For graph-set motifs, see Bernstein et al. (1995 ▶). For a related phospho­ric triamide, see: Sabbaghi et al. (2010 ▶).

Experimental

Crystal data

C15H20F2N3O2P

M = 343.31

Monoclinic,

a = 10.286 (3) Å

b = 14.873 (4) Å

c = 10.917 (3) Å

β = 99.296 (3)°

V = 1648.3 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.20 mm−1

T = 100 K

0.40 × 0.30 × 0.25 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.925, T max = 0.952

13279 measured reflections

3776 independent reflections

2953 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.119

S = 1.05

3776 reflections

230 parameters

7 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.39 e Å−3

Δρmin = −0.41 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; 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/S1600536811033216/jj2098sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811033216/jj2098Isup2.hkl

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

C15H20F2N3O2P	F(000) = 720
Mr = 343.31	Dx = 1.383 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7152 reflections
a = 10.286 (3) Å	θ = 2.5–27.9°
b = 14.873 (4) Å	µ = 0.20 mm−1
c = 10.917 (3) Å	T = 100 K
β = 99.296 (3)°	Block, colourless
V = 1648.3 (7) Å3	0.40 × 0.30 × 0.25 mm
Z = 4

Bruker APEXII CCD diffractometer	3776 independent reflections
Radiation source: fine-focus sealed tube	2953 reflections with I > 2σ(I)
graphite	Rint = 0.043
φ and ω scans	θmax = 27.9°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −13→13
Tmin = 0.925, Tmax = 0.952	k = −19→14
13279 measured reflections	l = −14→14

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0419P)2 + 1.0825P] where P = (Fo2 + 2Fc2)/3
3776 reflections	(Δ/σ)max < 0.001
230 parameters	Δρmax = 0.39 e Å−3
7 restraints	Δρmin = −0.41 e Å−3

Experimental. IR (KBr, ν, cm-1): 3062 (NH), 2846, 1684, 1622, 1465, 1442, 1284, 1218, 1181, 1092, 1008, 876, 800, 768, 708, 586.

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	0.58132 (4)	0.60634 (4)	0.14444 (5)	0.02623 (15)
F1	0.06841 (11)	0.66217 (8)	0.14052 (12)	0.0357 (3)
F2	0.33806 (10)	0.40553 (8)	0.20332 (11)	0.0333 (3)
O1	0.34013 (13)	0.65942 (10)	0.26101 (14)	0.0340 (4)
O2	0.65277 (12)	0.54022 (11)	0.07877 (12)	0.0322 (4)
N1	0.42250 (14)	0.57290 (13)	0.12010 (15)	0.0283 (4)
H1A	0.402 (2)	0.5349 (12)	0.0604 (16)	0.034*
N2	0.64224 (15)	0.60885 (11)	0.29142 (15)	0.0260 (4)
N3	0.57871 (16)	0.71092 (14)	0.10109 (18)	0.0396 (5)
C1	0.08224 (17)	0.57212 (14)	0.15613 (17)	0.0249 (4)
C2	−0.02954 (17)	0.52080 (14)	0.15101 (18)	0.0282 (4)
H2A	−0.1144	0.5478	0.1386	0.034*
C3	−0.01492 (18)	0.42859 (15)	0.16440 (19)	0.0304 (5)
H3A	−0.0908	0.3919	0.1621	0.036*
C4	0.10900 (19)	0.38887 (14)	0.18117 (18)	0.0284 (4)
H4A	0.1190	0.3256	0.1904	0.034*
C5	0.21675 (17)	0.44419 (14)	0.18402 (17)	0.0260 (4)
C6	0.20909 (16)	0.53694 (13)	0.17294 (16)	0.0225 (4)
C7	0.32904 (17)	0.59659 (14)	0.18895 (17)	0.0249 (4)
C8	0.6309 (2)	0.68401 (14)	0.3773 (2)	0.0328 (5)
H8A	0.5548	0.7229	0.3452	0.039*
H8B	0.7120	0.7209	0.3900	0.039*
C9	0.6109 (3)	0.63821 (17)	0.4964 (2)	0.0440 (6)
H9A	0.5167	0.6244	0.4962	0.053*
H9B	0.6438	0.6761	0.5695	0.053*
C10	0.6916 (3)	0.55236 (17)	0.4966 (2)	0.0450 (6)
H10A	0.6603	0.5057	0.5497	0.054*
H10B	0.7862	0.5641	0.5265	0.054*
C11	0.6688 (2)	0.52362 (14)	0.36086 (18)	0.0334 (5)
H11A	0.7477	0.4934	0.3391	0.040*
H11B	0.5926	0.4823	0.3431	0.040*
C12	0.7037 (2)	0.75855 (18)	0.0940 (3)	0.0512 (7)
H12A	0.7311	0.7953	0.1693	0.061*	0.746 (8)
H12B	0.7748	0.7152	0.0857	0.061*	0.746 (8)
H12C	0.7680	0.7205	0.0597	0.061*	0.254 (8)
H12D	0.7447	0.7840	0.1748	0.061*	0.254 (8)
C13	0.6757 (6)	0.8164 (5)	−0.0173 (6)	0.0601 (19)	0.746 (8)
H13A	0.6871	0.7829	−0.0933	0.072*	0.746 (8)
H13B	0.7335	0.8700	−0.0094	0.072*	0.746 (8)
C14	0.5338 (4)	0.8424 (3)	−0.0195 (4)	0.0520 (13)	0.746 (8)
H14A	0.4933	0.8646	−0.1024	0.062*	0.746 (8)
H14B	0.5252	0.8890	0.0434	0.062*	0.746 (8)
C13A	0.6387 (15)	0.8325 (12)	0.0017 (13)	0.043 (4)	0.254 (8)
H13C	0.6062	0.8819	0.0495	0.051*	0.254 (8)
H13D	0.7061	0.8577	−0.0438	0.051*	0.254 (8)
C14A	0.5278 (10)	0.7968 (8)	−0.0887 (9)	0.048 (3)	0.254 (8)
H14C	0.5559	0.7543	−0.1492	0.057*	0.254 (8)
H14D	0.4704	0.8443	−0.1318	0.057*	0.254 (8)
C15	0.4701 (2)	0.7512 (2)	0.0127 (3)	0.0557 (8)
H15A	0.3910	0.7613	0.0518	0.067*	0.746 (8)
H15B	0.4462	0.7131	−0.0620	0.067*	0.746 (8)
H15C	0.4195	0.7936	0.0565	0.067*	0.254 (8)
H15D	0.4095	0.7034	−0.0250	0.067*	0.254 (8)

	U11	U22	U33	U12	U13	U23
P1	0.0153 (2)	0.0358 (3)	0.0272 (3)	−0.00273 (19)	0.00216 (18)	0.0048 (2)
F1	0.0267 (6)	0.0268 (7)	0.0548 (8)	0.0024 (5)	0.0109 (5)	−0.0006 (6)
F2	0.0230 (5)	0.0356 (7)	0.0407 (7)	0.0057 (5)	0.0034 (5)	0.0040 (5)
O1	0.0278 (7)	0.0339 (9)	0.0410 (8)	−0.0075 (6)	0.0079 (6)	−0.0103 (7)
O2	0.0182 (6)	0.0502 (10)	0.0279 (7)	−0.0018 (6)	0.0030 (5)	−0.0034 (7)
N1	0.0187 (7)	0.0436 (11)	0.0230 (8)	−0.0054 (7)	0.0046 (6)	−0.0037 (8)
N2	0.0261 (8)	0.0215 (9)	0.0284 (8)	−0.0003 (6)	−0.0019 (6)	0.0007 (7)
N3	0.0218 (8)	0.0465 (12)	0.0508 (12)	0.0006 (8)	0.0067 (7)	0.0229 (10)
C1	0.0244 (8)	0.0237 (10)	0.0277 (9)	0.0011 (7)	0.0079 (7)	−0.0022 (8)
C2	0.0179 (8)	0.0351 (12)	0.0325 (10)	−0.0003 (8)	0.0067 (7)	−0.0042 (9)
C3	0.0251 (9)	0.0355 (12)	0.0318 (10)	−0.0099 (8)	0.0083 (8)	−0.0042 (9)
C4	0.0305 (9)	0.0264 (11)	0.0291 (10)	−0.0035 (8)	0.0074 (8)	0.0001 (8)
C5	0.0215 (8)	0.0323 (11)	0.0242 (9)	0.0032 (8)	0.0035 (7)	0.0001 (8)
C6	0.0180 (8)	0.0289 (11)	0.0213 (9)	−0.0024 (7)	0.0055 (7)	−0.0018 (8)
C7	0.0189 (8)	0.0306 (11)	0.0250 (9)	−0.0026 (7)	0.0027 (7)	0.0014 (8)
C8	0.0306 (10)	0.0233 (11)	0.0408 (12)	0.0019 (8)	−0.0047 (8)	−0.0049 (9)
C9	0.0621 (15)	0.0340 (13)	0.0371 (12)	0.0038 (11)	0.0115 (11)	−0.0074 (10)
C10	0.0674 (16)	0.0360 (14)	0.0287 (11)	0.0082 (12)	−0.0009 (11)	−0.0024 (10)
C11	0.0458 (12)	0.0254 (11)	0.0272 (10)	0.0066 (9)	0.0004 (9)	−0.0005 (9)
C12	0.0343 (11)	0.0389 (15)	0.085 (2)	−0.0063 (10)	0.0237 (12)	0.0122 (14)
C13	0.091 (4)	0.038 (3)	0.064 (3)	−0.025 (3)	0.052 (3)	−0.008 (2)
C14	0.081 (3)	0.040 (2)	0.036 (2)	−0.0016 (19)	0.0119 (19)	0.0143 (18)
C13A	0.048 (8)	0.046 (9)	0.035 (7)	−0.004 (6)	0.010 (6)	0.013 (6)
C14A	0.072 (7)	0.037 (6)	0.032 (6)	0.001 (5)	0.004 (5)	0.007 (5)
C15	0.0462 (13)	0.068 (2)	0.0523 (16)	0.0092 (13)	0.0052 (12)	0.0353 (14)

P1—O2	1.4803 (16)	C9—H9B	0.9900
P1—N3	1.625 (2)	C10—C11	1.524 (3)
P1—N2	1.6261 (17)	C10—H10A	0.9900
P1—N1	1.6872 (16)	C10—H10B	0.9900
F1—C1	1.355 (2)	C11—H11A	0.9900
F2—C5	1.359 (2)	C11—H11B	0.9900
O1—C7	1.215 (2)	C12—C13	1.479 (7)
N1—C7	1.359 (2)	C12—C13A	1.566 (14)
N1—H1A	0.863 (9)	C12—H12A	0.9900
N2—C8	1.476 (3)	C12—H12B	0.9900
N2—C11	1.480 (3)	C12—H12C	0.9891
N3—C15	1.480 (3)	C12—H12D	0.9903
N3—C12	1.481 (3)	C13—C14	1.507 (7)
C1—C2	1.374 (3)	C13—H13A	0.9900
C1—C6	1.390 (2)	C13—H13B	0.9900
C2—C3	1.385 (3)	C14—C15	1.571 (4)
C2—H2A	0.9500	C14—H14A	0.9900
C3—C4	1.390 (3)	C14—H14B	0.9900
C3—H3A	0.9500	C13A—C14A	1.481 (15)
C4—C5	1.377 (3)	C13A—H13C	0.9900
C4—H4A	0.9500	C13A—H13D	0.9900
C5—C6	1.386 (3)	C14A—C15	1.500 (9)
C6—C7	1.507 (2)	C14A—H14C	0.9900
C8—C9	1.512 (3)	C14A—H14D	0.9900
C8—H8A	0.9900	C15—H15A	0.9900
C8—H8B	0.9900	C15—H15B	0.9900
C9—C10	1.523 (3)	C15—H15C	0.9892
C9—H9A	0.9900	C15—H15D	0.9898
O2—P1—N3	118.75 (10)	C13—C12—N3	105.4 (3)
O2—P1—N2	110.54 (8)	N3—C12—C13A	94.9 (6)
N3—P1—N2	104.53 (10)	C13—C12—H12A	110.7
O2—P1—N1	105.77 (9)	N3—C12—H12A	110.7
N3—P1—N1	105.44 (9)	C13A—C12—H12A	100.4
N2—P1—N1	111.79 (8)	C13—C12—H12B	110.7
C7—N1—P1	126.16 (14)	N3—C12—H12B	110.7
C7—N1—H1A	118.4 (15)	C13A—C12—H12B	130.1
P1—N1—H1A	115.3 (15)	H12A—C12—H12B	108.8
C8—N2—C11	110.53 (16)	C13—C12—H12C	94.3
C8—N2—P1	125.92 (13)	N3—C12—H12C	112.7
C11—N2—P1	119.72 (13)	C13A—C12—H12C	113.6
C15—N3—C12	110.05 (19)	H12A—C12—H12C	120.9
C15—N3—P1	123.53 (17)	C13—C12—H12D	120.5
C12—N3—P1	119.96 (15)	N3—C12—H12D	112.6
F1—C1—C2	118.29 (16)	C13A—C12—H12D	112.4
F1—C1—C6	117.78 (16)	H12B—C12—H12D	96.8
C2—C1—C6	123.90 (19)	H12C—C12—H12D	110.0
C1—C2—C3	118.04 (17)	C12—C13—C14	102.8 (4)
C1—C2—H2A	121.0	C12—C13—H13A	111.2
C3—C2—H2A	121.0	C14—C13—H13A	111.2
C2—C3—C4	121.09 (18)	C12—C13—H13B	111.2
C2—C3—H3A	119.5	C14—C13—H13B	111.2
C4—C3—H3A	119.5	H13A—C13—H13B	109.1
C5—C4—C3	117.83 (19)	C13—C14—C15	102.3 (4)
C5—C4—H4A	121.1	C13—C14—H14A	111.3
C3—C4—H4A	121.1	C15—C14—H14A	111.3
F2—C5—C4	117.79 (18)	C13—C14—H14B	111.3
F2—C5—C6	118.20 (16)	C15—C14—H14B	111.3
C4—C5—C6	123.97 (17)	H14A—C14—H14B	109.2
C5—C6—C1	115.16 (16)	C14A—C13A—C12	112.3 (12)
C5—C6—C7	122.82 (16)	C14A—C13A—H13C	109.1
C1—C6—C7	121.82 (18)	C12—C13A—H13C	109.1
O1—C7—N1	123.83 (17)	C14A—C13A—H13D	109.1
O1—C7—C6	121.16 (17)	C12—C13A—H13D	109.1
N1—C7—C6	114.99 (17)	H13C—C13A—H13D	107.9
N2—C8—C9	103.94 (17)	C13A—C14A—C15	91.4 (9)
N2—C8—H8A	111.0	C13A—C14A—H14C	113.4
C9—C8—H8A	111.0	C15—C14A—H14C	113.4
N2—C8—H8B	111.0	C13A—C14A—H14D	113.4
C9—C8—H8B	111.0	C15—C14A—H14D	113.4
H8A—C8—H8B	109.0	H14C—C14A—H14D	110.7
C8—C9—C10	103.24 (19)	N3—C15—C14A	108.5 (4)
C8—C9—H9A	111.1	N3—C15—C14	101.4 (2)
C10—C9—H9A	111.1	N3—C15—H15A	111.5
C8—C9—H9B	111.1	C14A—C15—H15A	134.5
C10—C9—H9B	111.1	C14—C15—H15A	111.5
H9A—C9—H9B	109.1	N3—C15—H15B	111.5
C9—C10—C11	103.61 (18)	C14A—C15—H15B	74.1
C9—C10—H10A	111.0	C14—C15—H15B	111.5
C11—C10—H10A	111.0	H15A—C15—H15B	109.3
C9—C10—H10B	111.0	N3—C15—H15C	110.1
C11—C10—H10B	111.0	C14A—C15—H15C	111.7
H10A—C10—H10B	109.0	C14—C15—H15C	80.1
N2—C11—C10	104.16 (17)	H15B—C15—H15C	133.1
N2—C11—H11A	110.9	N3—C15—H15D	109.8
C10—C11—H11A	110.9	C14A—C15—H15D	108.4
N2—C11—H11B	110.9	C14—C15—H15D	141.7
C10—C11—H11B	110.9	H15A—C15—H15D	77.4
H11A—C11—H11B	108.9	H15C—C15—H15D	108.3
O2—P1—N1—C7	160.11 (17)	P1—N1—C7—C6	−162.13 (14)
N3—P1—N1—C7	−73.26 (19)	C5—C6—C7—O1	−126.8 (2)
N2—P1—N1—C7	39.7 (2)	C1—C6—C7—O1	47.8 (3)
O2—P1—N2—C8	157.70 (16)	C5—C6—C7—N1	51.5 (2)
N3—P1—N2—C8	28.81 (18)	C1—C6—C7—N1	−133.96 (19)
N1—P1—N2—C8	−84.76 (18)	C11—N2—C8—C9	−16.4 (2)
O2—P1—N2—C11	−46.49 (17)	P1—N2—C8—C9	141.28 (16)
N3—P1—N2—C11	−175.38 (15)	N2—C8—C9—C10	33.4 (2)
N1—P1—N2—C11	71.05 (17)	C8—C9—C10—C11	−38.2 (2)
O2—P1—N3—C15	95.4 (2)	C8—N2—C11—C10	−7.4 (2)
N2—P1—N3—C15	−140.9 (2)	P1—N2—C11—C10	−166.62 (15)
N1—P1—N3—C15	−22.9 (2)	C9—C10—C11—N2	28.0 (2)
O2—P1—N3—C12	−53.6 (2)	C15—N3—C12—C13	−11.0 (4)
N2—P1—N3—C12	70.2 (2)	P1—N3—C12—C13	141.7 (3)
N1—P1—N3—C12	−171.80 (19)	C15—N3—C12—C13A	5.5 (7)
F1—C1—C2—C3	178.66 (18)	P1—N3—C12—C13A	158.3 (6)
C6—C1—C2—C3	0.5 (3)	N3—C12—C13—C14	33.6 (5)
C1—C2—C3—C4	−0.7 (3)	C13A—C12—C13—C14	−25 (2)
C2—C3—C4—C5	0.0 (3)	C12—C13—C14—C15	−42.7 (5)
C3—C4—C5—F2	178.50 (17)	C13—C12—C13A—C14A	89 (3)
C3—C4—C5—C6	0.9 (3)	N3—C12—C13A—C14A	−35.5 (12)
F2—C5—C6—C1	−178.62 (16)	C12—C13A—C14A—C15	47.7 (13)
C4—C5—C6—C1	−1.1 (3)	C12—N3—C15—C14A	23.9 (6)
F2—C5—C6—C7	−3.8 (3)	P1—N3—C15—C14A	−127.7 (5)
C4—C5—C6—C7	173.80 (18)	C12—N3—C15—C14	−15.1 (3)
F1—C1—C6—C5	−177.82 (17)	P1—N3—C15—C14	−166.7 (2)
C2—C1—C6—C5	0.3 (3)	C13A—C14A—C15—N3	−40.9 (10)
F1—C1—C6—C7	7.3 (3)	C13A—C14A—C15—C14	44.1 (8)
C2—C1—C6—C7	−174.62 (18)	C13—C14—C15—N3	35.1 (4)
P1—N1—C7—O1	16.1 (3)	C13—C14—C15—C14A	−70.4 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2i	0.86 (1)	1.90 (1)	2.757 (2)	175 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2i	0.86 (1)	1.90 (1)	2.757 (2)	175 (2)

Symmetry code: (i) .