Tetra-methyl N,N'-(2,2,3,3,4,4-hexa-fluoro-1,5-dioxopentane-1,5-di-yl)bis-(phospho-ramidate).

The mol-ecule of the title compound, C(9)H(14)F(6)N(2)O(8)P(2), lies on a twofold rotation axis that passes through the middle C atom of the three-atom fluoro-methyl-ene unit. The carbonyl and phosphoryl groups are in an antiperiplanar conformation. In the crystal, N-H⋯O=P hydrogen bonds link the mol-ecules into polymeric chains parallel to the c axis.

Related literature

For background to the chemistry of phospho­rus–organic compounds, see: Ly & Woollins (1998 ▶). For the biological and pharmacological properties of carbacyl­amido­phosphate der­iv­atives, see: Adams et al. (2002 ▶). For details of the synthesis and properties of phospho­ramide derivatives, see: Kirsanov & Levchenko (1957 ▶); For structural analogues of phospho­rylated carbacyl­amides and their properties, see: Trush et al. (2005 ▶); Gubina et al. (2000 ▶). For the synthesis and properties of fluorinated compounds, see: Leontieva et al. (2002 ▶).

Experimental

Crystal data

C9H14F6N2O8P2

M = 454.16

Monoclinic,

a = 19.7862 (13) Å

b = 5.2801 (4) Å

c = 16.9943 (11) Å

β = 100.427 (6)°

V = 1746.1 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.35 mm−1

T = 293 K

0.40 × 0.20 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur3 diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T min = 0.872, T max = 0.966

7084 measured reflections

2504 independent reflections

1669 reflections with I > 2σ(I)

R int = 0.023

2 standard reflections every 50 reflections intensity decay: 0.3%

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.106

S = 0.93

2504 reflections

125 parameters

H-atom parameters constrained

Δρmax = 0.29 e Å−3

Δρmin = −0.24 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2006 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812011191/fj2523sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812011191/fj2523Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812011191/fj2523Isup3.cml

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

C9H14F6N2O8P2	F(000) = 920
Mr = 454.16	Dx = 1.728 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2504 reflections
a = 19.7862 (13) Å	θ = 2.9–30°
b = 5.2801 (4) Å	µ = 0.35 mm−1
c = 16.9943 (11) Å	T = 293 K
β = 100.427 (6)°	Block, colourless
V = 1746.1 (2) Å3	0.40 × 0.20 × 0.10 mm
Z = 4

Oxford Diffraction Xcalibur3 diffractometer	1669 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.023
Graphite monochromator	θmax = 30.0°, θmin = 2.9°
ω scans	h = −27→27
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −7→7
Tmin = 0.872, Tmax = 0.966	l = −23→22
7084 measured reflections	2 standard reflections every 50 reflections
2504 independent reflections	intensity decay: 0.3%

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106	H-atom parameters constrained
S = 0.93	w = 1/[σ2(Fo2) + (0.0667P)2] where P = (Fo2 + 2Fc2)/3
2504 reflections	(Δ/σ)max = 0.001
125 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

Experimental. Analysis found: IR (KBr pellet, cm-1): 3095(s, NH), 2925(ns, CH), 1190(s), 1746(s, C=O), 1478(s CN); 1291 (as, CF), 1212 (s, PO), 1141 (s, CF). NMR - 1H (DMSO-d6): C—H 3.74 (d) 12H, 3JPH = 11.6 Hz; NH 11.38 (d) 2H; 31P (DMSO-d6): -0.28 (hept) 3JHP = 11.6 Hz; 13C (DMSO-d6): C(O) 159.68, CF 108.6 - 105.9, CH3 54.74.

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
F1	0.54045 (6)	−0.1156 (2)	0.30276 (6)	0.0559 (3)
F2	0.58399 (6)	−0.5823 (2)	0.25478 (7)	0.0568 (3)
F3	0.50776 (6)	−0.5503 (2)	0.14516 (6)	0.0495 (3)
P1	0.61282 (2)	0.06932 (8)	0.04812 (2)	0.03549 (13)
N1	0.57021 (7)	−0.1298 (3)	0.09836 (8)	0.0368 (3)
H1NA	0.5280	−0.1619	0.0784	0.044*
O1	0.65572 (7)	−0.2202 (3)	0.20427 (8)	0.0509 (3)
O2	0.67108 (6)	−0.0844 (2)	0.01929 (7)	0.0470 (3)
O3	0.65216 (6)	0.2593 (2)	0.10883 (7)	0.0458 (3)
O4	0.56309 (6)	0.1876 (3)	−0.01514 (7)	0.0463 (3)
C1	0.5000	−0.2656 (4)	0.2500	0.0349 (5)
C2	0.54710 (9)	−0.4170 (3)	0.20389 (9)	0.0368 (3)
C3	0.59784 (8)	−0.2443 (3)	0.16861 (9)	0.0359 (3)
C4	0.65304 (12)	−0.2569 (4)	−0.04796 (13)	0.0609 (6)
H4C	0.6191	−0.3749	−0.0369	0.091*
H4B	0.6933	−0.3475	−0.0561	0.091*
H4A	0.6349	−0.1621	−0.0953	0.091*
C5	0.72440 (10)	0.2612 (5)	0.14340 (16)	0.0672 (6)
H5C	0.7340	0.4008	0.1799	0.101*
H5B	0.7509	0.2787	0.1017	0.101*
H5A	0.7363	0.1054	0.1716	0.101*

	U11	U22	U33	U12	U13	U23
F1	0.0650 (7)	0.0573 (7)	0.0483 (6)	−0.0249 (6)	0.0182 (6)	−0.0188 (5)
F2	0.0620 (7)	0.0545 (7)	0.0567 (7)	0.0208 (6)	0.0179 (6)	0.0233 (5)
F3	0.0586 (7)	0.0482 (6)	0.0447 (6)	−0.0125 (5)	0.0172 (5)	−0.0133 (5)
P1	0.0276 (2)	0.0451 (2)	0.0324 (2)	−0.00321 (17)	0.00186 (15)	0.00114 (16)
N1	0.0276 (7)	0.0485 (8)	0.0325 (6)	−0.0032 (6)	0.0008 (5)	0.0049 (6)
O1	0.0375 (7)	0.0623 (8)	0.0471 (7)	−0.0022 (6)	−0.0077 (6)	0.0082 (6)
O2	0.0322 (6)	0.0634 (8)	0.0463 (7)	−0.0026 (6)	0.0093 (5)	−0.0114 (6)
O3	0.0347 (6)	0.0518 (7)	0.0479 (7)	−0.0046 (5)	−0.0009 (5)	−0.0094 (5)
O4	0.0367 (6)	0.0573 (7)	0.0413 (7)	−0.0064 (6)	−0.0026 (5)	0.0145 (5)
C1	0.0389 (12)	0.0357 (11)	0.0296 (10)	0.000	0.0045 (9)	0.000
C2	0.0420 (9)	0.0365 (8)	0.0311 (7)	0.0032 (7)	0.0042 (6)	0.0042 (6)
C3	0.0337 (8)	0.0413 (8)	0.0317 (7)	0.0025 (7)	0.0032 (6)	0.0009 (6)
C4	0.0603 (13)	0.0614 (13)	0.0622 (13)	−0.0049 (11)	0.0143 (11)	−0.0208 (10)
C5	0.0381 (10)	0.0707 (14)	0.0843 (15)	−0.0082 (10)	−0.0121 (10)	−0.0189 (12)

F1—C1	1.3461 (16)	O3—C5	1.444 (2)
F2—C2	1.3469 (18)	C1—F1i	1.3461 (16)
F3—C2	1.3475 (18)	C1—C2i	1.545 (2)
P1—O4	1.4598 (12)	C1—C2	1.545 (2)
P1—O3	1.5444 (12)	C2—C3	1.555 (2)
P1—O2	1.5595 (13)	C4—H4C	0.9600
P1—N1	1.6751 (14)	C4—H4B	0.9600
N1—C3	1.361 (2)	C4—H4A	0.9600
N1—H1NA	0.8600	C5—H5C	0.9600
O1—C3	1.202 (2)	C5—H5B	0.9600
O2—C4	1.454 (2)	C5—H5A	0.9600
O4—P1—O3	113.89 (8)	F3—C2—C1	108.98 (12)
O4—P1—O2	115.43 (8)	F2—C2—C3	108.38 (13)
O3—P1—O2	103.65 (7)	F3—C2—C3	110.33 (12)
O4—P1—N1	108.04 (7)	C1—C2—C3	112.52 (14)
O3—P1—N1	107.84 (7)	O1—C3—N1	126.17 (16)
O2—P1—N1	107.59 (7)	O1—C3—C2	119.38 (14)
C3—N1—P1	124.51 (11)	N1—C3—C2	114.45 (13)
C3—N1—H1NA	117.7	O2—C4—H4C	109.5
P1—N1—H1NA	117.7	O2—C4—H4B	109.5
C4—O2—P1	118.85 (13)	H4C—C4—H4B	109.5
C5—O3—P1	128.21 (14)	O2—C4—H4A	109.5
F1—C1—F1i	107.92 (19)	H4C—C4—H4A	109.5
F1—C1—C2i	107.89 (7)	H4B—C4—H4A	109.5
F1i—C1—C2i	107.56 (8)	O3—C5—H5C	109.5
F1—C1—C2	107.56 (8)	O3—C5—H5B	109.5
F1i—C1—C2	107.89 (7)	H5C—C5—H5B	109.5
C2i—C1—C2	117.67 (19)	O3—C5—H5A	109.5
F2—C2—F3	108.08 (13)	H5C—C5—H5A	109.5
F2—C2—C1	108.44 (12)	H5B—C5—H5A	109.5
O4—P1—N1—C3	−169.53 (14)	F1i—C1—C2—F3	−57.75 (17)
O3—P1—N1—C3	−46.00 (15)	C2i—C1—C2—F3	64.07 (10)
O2—P1—N1—C3	65.23 (15)	F1—C1—C2—C3	−51.23 (15)
O4—P1—O2—C4	−45.46 (17)	F1i—C1—C2—C3	64.95 (15)
O3—P1—O2—C4	−170.70 (14)	C2i—C1—C2—C3	−173.22 (13)
N1—P1—O2—C4	75.24 (15)	P1—N1—C3—O1	−0.1 (3)
O4—P1—O3—C5	−137.75 (19)	P1—N1—C3—C2	178.97 (11)
O2—P1—O3—C5	−11.5 (2)	F2—C2—C3—O1	−22.1 (2)
N1—P1—O3—C5	102.4 (2)	F3—C2—C3—O1	−140.28 (16)
F1—C1—C2—F2	68.63 (17)	C1—C2—C3—O1	97.78 (17)
F1i—C1—C2—F2	−175.18 (13)	F2—C2—C3—N1	158.77 (14)
C2i—C1—C2—F2	−53.36 (10)	F3—C2—C3—N1	40.62 (19)
F1—C1—C2—F3	−173.94 (12)	C1—C2—C3—N1	−81.33 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1NA···O4ii	0.86	1.93	2.7750 (17)	168

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1NA⋯O4i	0.86	1.93	2.7750 (17)	168

Symmetry code: (i) .