N,N'-Di-tert-butyl-N''-(2,6-difluoro-benzo-yl)phospho-ric triamide.

In the title compound, C(15)H(24)F(2)N(3)O(2)P, the phosphoryl and carbonyl groups adopt anti positions relative to each other. The P atom is in a tetra-hedral coordination environment and the environment of each N atom is essentially planar. In the crystal, adjacent mol-ecules are linked via N-H⋯O=P and N-H⋯O=C hydrogen bonds into an extended chain parallel to the a axis. The crystal studied was a non-merohedral twin with a minor twin component of 36.4 (1)%.

Related literature

Carbacyl­amido­phosphates with a C(O)NHP(O) skeleton have attracted attention because of their roles as O,O′-donor ligands for metal complexation, see: Gholivand et al. (2010 ▶). CELL_NOW (Sheldrick, 2008a ▶) was used to generate the components of the twin.

Experimental

Crystal data

C15H24F2N3O2P

M = 347.34

Triclinic,

a = 9.8142 (12) Å

b = 10.2886 (13) Å

c = 10.6091 (16) Å

α = 117.171 (4)°

β = 98.636 (4)°

γ = 97.988 (3)°

V = 915.6 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.18 mm−1

T = 200 K

0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART X2S benchtop CCD area-detector diffractometer

Absorption correction: multi-scan (TWINABS; Sheldrick, 2008a ▶) T min = 0.948, T max = 0.965

7847 measured reflections

4225 independent reflections

3525 reflections with I > 2σ(I)

R int = 0.057

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.121

S = 1.05

4225 reflections

224 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.35 e Å−3

Δρmin = −0.27 e Å−3

Data collection: GIS (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810045927/ng5051sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810045927/ng5051Isup2.hkl

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

C15H24F2N3O2P	Z = 2
Mr = 347.34	F(000) = 368
Triclinic, P1	Dx = 1.260 Mg m−3
a = 9.8142 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.2886 (13) Å	Cell parameters from 2837 reflections
c = 10.6091 (16) Å	θ = 2.2–27.9°
α = 117.171 (4)°	µ = 0.18 mm−1
β = 98.636 (4)°	T = 200 K
γ = 97.988 (3)°	Block, colorless
V = 915.6 (2) Å3	0.30 × 0.25 × 0.20 mm

Bruker SMART X2S benchtop CCD area-detector diffractometer	4225 independent reflections
Radiation source: micro focus sealed tube	3525 reflections with I > 2σ(I)
doubly curved silicon crystal	Rint = 0.057
φ and ω scans	θmax = 27.9°, θmin = 2.2°
Absorption correction: multi-scan (TWINABS; Sheldrick, 2008a)	h = −12→12
Tmin = 0.948, Tmax = 0.965	k = −13→12
7847 measured reflections	l = 0→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: inferred from neighbouring sites
wR(F2) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0548P)2 + 0.3384P] where P = (Fo2 + 2Fc2)/3
4225 reflections	(Δ/σ)max = 0.007
224 parameters	Δρmax = 0.35 e Å−3
3 restraints	Δρmin = −0.26 e Å−3

Experimental. Data refinement indicated a twin system and program Cell_Now (Sheldrick, 2008) was used to generate the two components of the twin (63.6 (1)/36.4 ratio). Data was integrated using SAINT and corrected for absorption using TWINABS (Shelrick, 2008).

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	0.18621 (6)	0.39181 (6)	0.41180 (6)	0.02191 (14)
F1	0.4134 (2)	0.6847 (2)	0.94162 (17)	0.0611 (5)
F2	0.23506 (19)	0.89470 (17)	0.66107 (18)	0.0523 (4)
O1	0.45094 (16)	0.62402 (19)	0.64132 (18)	0.0363 (4)
O2	0.03152 (16)	0.32970 (16)	0.36977 (17)	0.0305 (4)
N1	0.20980 (18)	0.55903 (19)	0.56848 (19)	0.0241 (4)
H1N	0.1375 (17)	0.592 (3)	0.595 (3)	0.029*
N2	0.2528 (2)	0.4227 (2)	0.29337 (19)	0.0276 (4)
H2N	0.3378 (14)	0.411 (3)	0.293 (3)	0.033*
N3	0.28600 (19)	0.2910 (2)	0.4441 (2)	0.0260 (4)
H3N	0.3739 (13)	0.318 (3)	0.449 (3)	0.031*
C1	0.3611 (3)	0.7959 (3)	0.9332 (3)	0.0404 (6)
C2	0.3480 (4)	0.9159 (4)	1.0587 (3)	0.0597 (9)
H2A	0.3767	0.9216	1.1511	0.072*
C3	0.2927 (4)	1.0271 (4)	1.0475 (4)	0.0675 (10)
H3A	0.2807	1.1087	1.1327	0.081*
C4	0.2544 (3)	1.0216 (3)	0.9142 (4)	0.0593 (9)
H4A	0.2183	1.0995	0.9069	0.071*
C5	0.2699 (3)	0.8998 (3)	0.7919 (3)	0.0386 (6)
C6	0.3228 (2)	0.7840 (2)	0.7961 (2)	0.0283 (5)
C7	0.3352 (2)	0.6488 (2)	0.6613 (2)	0.0243 (4)
C8	0.1874 (3)	0.4811 (3)	0.1991 (2)	0.0353 (5)
C9	0.1621 (4)	0.6356 (3)	0.2928 (3)	0.0580 (9)
H9A	0.2518	0.7042	0.3598	0.087*
H9B	0.0940	0.6275	0.3491	0.087*
H9C	0.1241	0.6747	0.2297	0.087*
C10	0.0477 (3)	0.3691 (4)	0.0967 (3)	0.0569 (8)
H10A	−0.0227	0.3709	0.1536	0.085*
H10B	0.0640	0.2677	0.0478	0.085*
H10C	0.0126	0.3972	0.0234	0.085*
C11	0.2913 (4)	0.4907 (4)	0.1095 (3)	0.0535 (7)
H11A	0.3809	0.5611	0.1750	0.080*
H11B	0.2515	0.5263	0.0439	0.080*
H11C	0.3084	0.3911	0.0518	0.080*
C12	0.2566 (3)	0.1929 (3)	0.5095 (3)	0.0336 (5)
C13	0.1325 (3)	0.0588 (3)	0.4049 (4)	0.0579 (8)
H13A	0.1533	0.0073	0.3088	0.087*
H13B	0.0460	0.0945	0.3956	0.087*
H13C	0.1188	−0.0112	0.4433	0.087*
C14	0.2251 (5)	0.2791 (4)	0.6581 (4)	0.0677 (10)
H14A	0.3057	0.3642	0.7232	0.102*
H14B	0.2093	0.2123	0.6997	0.102*
H14C	0.1400	0.3165	0.6470	0.102*
C15	0.3893 (3)	0.1343 (4)	0.5243 (4)	0.0525 (7)
H15A	0.4090	0.0802	0.4280	0.079*
H15B	0.3742	0.0661	0.5645	0.079*
H15C	0.4701	0.2191	0.5898	0.079*

	U11	U22	U33	U12	U13	U23
P1	0.0176 (2)	0.0218 (2)	0.0242 (3)	0.00825 (19)	0.00585 (19)	0.0082 (2)
F1	0.0786 (14)	0.0696 (11)	0.0426 (9)	0.0253 (10)	0.0115 (8)	0.0322 (9)
F2	0.0626 (11)	0.0417 (8)	0.0565 (10)	0.0198 (8)	0.0103 (8)	0.0264 (8)
O1	0.0199 (7)	0.0431 (9)	0.0381 (9)	0.0093 (7)	0.0107 (7)	0.0117 (7)
O2	0.0185 (7)	0.0288 (7)	0.0359 (8)	0.0083 (6)	0.0062 (6)	0.0083 (7)
N1	0.0179 (8)	0.0251 (8)	0.0258 (8)	0.0100 (7)	0.0080 (7)	0.0073 (7)
N2	0.0238 (9)	0.0369 (10)	0.0278 (9)	0.0147 (8)	0.0093 (8)	0.0174 (8)
N3	0.0190 (9)	0.0280 (9)	0.0367 (10)	0.0111 (7)	0.0116 (8)	0.0173 (8)
C1	0.0370 (14)	0.0419 (13)	0.0338 (12)	0.0027 (11)	0.0089 (10)	0.0131 (11)
C2	0.0572 (19)	0.067 (2)	0.0259 (13)	0.0018 (16)	0.0120 (12)	0.0022 (13)
C3	0.061 (2)	0.0446 (17)	0.0517 (18)	0.0063 (15)	0.0210 (16)	−0.0140 (14)
C4	0.0560 (19)	0.0317 (13)	0.067 (2)	0.0160 (13)	0.0164 (16)	0.0030 (14)
C5	0.0337 (13)	0.0274 (11)	0.0418 (13)	0.0036 (10)	0.0092 (11)	0.0072 (10)
C6	0.0205 (9)	0.0265 (10)	0.0276 (10)	0.0022 (8)	0.0075 (8)	0.0052 (8)
C7	0.0210 (10)	0.0264 (10)	0.0252 (10)	0.0067 (8)	0.0083 (8)	0.0112 (8)
C8	0.0437 (14)	0.0373 (12)	0.0308 (11)	0.0163 (11)	0.0077 (10)	0.0198 (10)
C9	0.087 (3)	0.0501 (16)	0.0516 (16)	0.0393 (17)	0.0195 (16)	0.0298 (14)
C10	0.0501 (18)	0.0689 (19)	0.0498 (16)	0.0046 (14)	−0.0106 (13)	0.0366 (15)
C11	0.068 (2)	0.0642 (18)	0.0426 (15)	0.0200 (16)	0.0189 (14)	0.0346 (14)
C12	0.0338 (13)	0.0360 (12)	0.0445 (13)	0.0173 (10)	0.0172 (10)	0.0259 (11)
C13	0.0462 (18)	0.0477 (16)	0.087 (2)	0.0019 (13)	0.0107 (16)	0.0424 (17)
C14	0.108 (3)	0.075 (2)	0.0601 (19)	0.055 (2)	0.052 (2)	0.0477 (18)
C15	0.0503 (17)	0.0584 (17)	0.0721 (19)	0.0294 (14)	0.0168 (15)	0.0456 (16)

P1—O2	1.4761 (16)	C8—C9	1.522 (4)
P1—N3	1.6301 (18)	C8—C10	1.536 (4)
P1—N2	1.631 (2)	C9—H9A	0.9800
P1—N1	1.7142 (17)	C9—H9B	0.9800
F1—C1	1.351 (3)	C9—H9C	0.9800
F2—C5	1.353 (3)	C10—H10A	0.9800
O1—C7	1.226 (2)	C10—H10B	0.9800
N1—C7	1.352 (3)	C10—H10C	0.9800
N1—H1N	0.858 (10)	C11—H11A	0.9800
N2—C8	1.495 (3)	C11—H11B	0.9800
N2—H2N	0.860 (10)	C11—H11C	0.9800
N3—C12	1.485 (3)	C12—C14	1.520 (4)
N3—H3N	0.856 (10)	C12—C15	1.526 (3)
C1—C2	1.381 (4)	C12—C13	1.532 (4)
C1—C6	1.390 (4)	C13—H13A	0.9800
C2—C3	1.377 (5)	C13—H13B	0.9800
C2—H2A	0.9500	C13—H13C	0.9800
C3—C4	1.381 (6)	C14—H14A	0.9800
C3—H3A	0.9500	C14—H14B	0.9800
C4—C5	1.380 (4)	C14—H14C	0.9800
C4—H4A	0.9500	C15—H15A	0.9800
C5—C6	1.381 (3)	C15—H15B	0.9800
C6—C7	1.509 (3)	C15—H15C	0.9800
C8—C11	1.517 (4)
O2—P1—N3	116.57 (10)	C8—C9—H9A	109.5
O2—P1—N2	115.98 (9)	C8—C9—H9B	109.5
N3—P1—N2	102.21 (9)	H9A—C9—H9B	109.5
O2—P1—N1	103.22 (8)	C8—C9—H9C	109.5
N3—P1—N1	109.37 (9)	H9A—C9—H9C	109.5
N2—P1—N1	109.43 (10)	H9B—C9—H9C	109.5
C7—N1—P1	126.27 (14)	C8—C10—H10A	109.5
C7—N1—H1N	113.8 (16)	C8—C10—H10B	109.5
P1—N1—H1N	119.9 (16)	H10A—C10—H10B	109.5
C8—N2—P1	127.01 (16)	C8—C10—H10C	109.5
C8—N2—H2N	118.1 (19)	H10A—C10—H10C	109.5
P1—N2—H2N	114.6 (19)	H10B—C10—H10C	109.5
C12—N3—P1	128.21 (15)	C8—C11—H11A	109.5
C12—N3—H3N	114.1 (19)	C8—C11—H11B	109.5
P1—N3—H3N	114.8 (18)	H11A—C11—H11B	109.5
F1—C1—C2	119.7 (3)	C8—C11—H11C	109.5
F1—C1—C6	117.6 (2)	H11A—C11—H11C	109.5
C2—C1—C6	122.7 (3)	H11B—C11—H11C	109.5
C3—C2—C1	118.8 (3)	N3—C12—C14	111.4 (2)
C3—C2—H2A	120.6	N3—C12—C15	106.2 (2)
C1—C2—H2A	120.6	C14—C12—C15	110.4 (2)
C2—C3—C4	120.9 (3)	N3—C12—C13	109.3 (2)
C2—C3—H3A	119.5	C14—C12—C13	110.8 (3)
C4—C3—H3A	119.5	C15—C12—C13	108.5 (2)
C3—C4—C5	118.3 (3)	C12—C13—H13A	109.5
C3—C4—H4A	120.9	C12—C13—H13B	109.5
C5—C4—H4A	120.9	H13A—C13—H13B	109.5
F2—C5—C4	118.7 (3)	C12—C13—H13C	109.5
F2—C5—C6	117.9 (2)	H13A—C13—H13C	109.5
C4—C5—C6	123.4 (3)	H13B—C13—H13C	109.5
C5—C6—C1	116.0 (2)	C12—C14—H14A	109.5
C5—C6—C7	123.1 (2)	C12—C14—H14B	109.5
C1—C6—C7	120.9 (2)	H14A—C14—H14B	109.5
O1—C7—N1	124.00 (18)	C12—C14—H14C	109.5
O1—C7—C6	121.48 (18)	H14A—C14—H14C	109.5
N1—C7—C6	114.52 (17)	H14B—C14—H14C	109.5
N2—C8—C11	106.6 (2)	C12—C15—H15A	109.5
N2—C8—C9	110.46 (19)	C12—C15—H15B	109.5
C11—C8—C9	110.4 (2)	H15A—C15—H15B	109.5
N2—C8—C10	109.0 (2)	C12—C15—H15C	109.5
C11—C8—C10	109.5 (2)	H15A—C15—H15C	109.5
C9—C8—C10	110.8 (2)	H15B—C15—H15C	109.5
O2—P1—N1—C7	169.82 (18)	C4—C5—C6—C7	178.0 (2)
N3—P1—N1—C7	45.1 (2)	F1—C1—C6—C5	−180.0 (2)
N2—P1—N1—C7	−66.1 (2)	C2—C1—C6—C5	−0.3 (4)
O2—P1—N2—C8	38.0 (2)	F1—C1—C6—C7	2.0 (3)
N3—P1—N2—C8	165.93 (18)	C2—C1—C6—C7	−178.3 (2)
N1—P1—N2—C8	−78.2 (2)	P1—N1—C7—O1	3.1 (3)
O2—P1—N3—C12	−33.9 (2)	P1—N1—C7—C6	−175.92 (16)
N2—P1—N3—C12	−161.48 (19)	C5—C6—C7—O1	114.8 (3)
N1—P1—N3—C12	82.6 (2)	C1—C6—C7—O1	−67.3 (3)
F1—C1—C2—C3	−179.2 (3)	C5—C6—C7—N1	−66.1 (3)
C6—C1—C2—C3	1.1 (5)	C1—C6—C7—N1	111.8 (2)
C1—C2—C3—C4	−1.8 (5)	P1—N2—C8—C11	179.62 (18)
C2—C3—C4—C5	1.5 (5)	P1—N2—C8—C9	59.7 (3)
C3—C4—C5—F2	−178.8 (3)	P1—N2—C8—C10	−62.3 (3)
C3—C4—C5—C6	−0.6 (4)	P1—N3—C12—C14	−55.9 (3)
F2—C5—C6—C1	178.2 (2)	P1—N3—C12—C15	−176.14 (19)
C4—C5—C6—C1	0.0 (4)	P1—N3—C12—C13	67.0 (3)
F2—C5—C6—C7	−3.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2i	0.86 (1)	1.96 (1)	2.808 (2)	172 (2)
N2—H2N···O1ii	0.86 (1)	2.22 (1)	3.042 (2)	160 (2)
N3—H3N···O1ii	0.86 (1)	2.22 (2)	3.008 (2)	152 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2i	0.86 (1)	1.96 (1)	2.808 (2)	172 (2)
N2—H2N⋯O1ii	0.86 (1)	2.22 (1)	3.042 (2)	160 (2)
N3—H3N⋯O1ii	0.86 (1)	2.22 (2)	3.008 (2)	152 (2)

Symmetry codes: (i) ; (ii) .