Bis(4-nitro­phenyl) N,N-di­methyl­phosphoramidate

The P-N bond in the title compound, C₁₄H₁₄N₃O₇P, exhibits double-bond character that is attributed to the presence of the nitro substituents. Contrary to what is expected, the P-N bond in such a compound is not weak.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.046
• wR factor = 0.134
• Data-to-parameter ratio = 17.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

The title compound, (I), which acts as an inhibitor of blood coagulation (De Lange & Hemker, 1972), has been characterized by mass spectrometry (Meyer et al., 1978). It possesses a nitro substituent in the para position of the aromatic ring; the presence of two nitrophenyl entities considerably shortens the P—N bond [1.6032 (17) Å], which is significantly shorter than the corresponding distance (1.77 Å) found in NaHPO₃(NH₂), but is much longer than that (1.57 Å) found in (C₆H₅)₃PN (Corbridge, 1995). On the basis of the P—N distance, the P—N bond in (I) is expected to display double-bond character. The double-bond character is also shown by the sum of the angles at the N atom of almost 360°.

S2. Experimental

The title compound was synthesized from the reaction of sodium p-nitrophenoxide and N,N-dimethylaminophosphoryl dichloride. Crystals were obtained by recrystallization from chloroform–ethanol (1/1).

Computing details

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1989); cell refinement: CAD-4 EXPRESS; data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. ORTEPII (Johnson, 1976) plot of the title compound at the 50% probability level. H atoms are drawn as spheres of arbitrary radii.

N,N-dimethylphosphoramidic acid bis(4-nitrophenyl) ester

Crystal data

C14H14N3O7P	Dx = 1.475 Mg m^−3
Mr = 367.25	Melting point = 143–144 K
Monoclinic, P21/a	Mo Kα radiation, λ = 0.71073 Å
a = 9.139 (2) Å	Cell parameters from 25 reflections
b = 11.083 (2) Å	θ = 12–18°
c = 16.411 (3) Å	µ = 0.21 mm^−1
β = 95.838 (2)°	T = 298 K
V = 1653.5 (5) Å^3	Irregular block, colorless
Z = 4	0.65 × 0.18 × 0.18 mm
F(000) = 760

Data collection

Enraf-Nonius CAD-4 diffractometer	2557 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.016
Graphite monochromator	θmax = 30.0°, θmin = 2.5°
ω–2θ scans	h = 0→12
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968)	k = −15→0
Tmin = 0.898, Tmax = 0.953	l = −23→22
5105 measured reflections	3 standard reflections every 60 min
4823 independent reflections	intensity decay: <1%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.134	All H-atom parameters refined
S = 0.92	w = 1/[σ^2(Fo^2) + (0.0759P)^2] where P = (Fo^2 + 2Fc^2)/3
4823 reflections	(Δ/σ)max < 0.001
282 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
P1	0.52277 (5)	0.46416 (4)	0.27788 (3)	0.04861 (15)
O1	0.65806 (15)	0.52294 (11)	0.33169 (8)	0.0580 (4)
O2	0.9657 (2)	0.36753 (18)	0.67212 (10)	0.0899 (5)
O3	1.0619 (2)	0.23912 (18)	0.59589 (11)	0.0969 (6)
O4	0.61086 (14)	0.36642 (12)	0.23028 (8)	0.0583 (4)
O5	0.3742 (2)	−0.10725 (16)	0.05943 (12)	0.0947 (6)
O6	0.2380 (3)	0.02187 (19)	−0.00993 (12)	0.1161 (8)
O7	0.40922 (15)	0.41214 (12)	0.32308 (9)	0.0612 (4)
N1	0.9786 (2)	0.32234 (17)	0.60607 (11)	0.0634 (4)
N2	0.3342 (2)	−0.0039 (2)	0.04428 (12)	0.0728 (5)
N3	0.46889 (17)	0.56651 (15)	0.21257 (10)	0.0554 (4)
C1	0.73351 (19)	0.46569 (16)	0.39975 (11)	0.0488 (4)
C2	0.8331 (2)	0.37487 (19)	0.38961 (13)	0.0579 (5)
C3	0.9124 (2)	0.32727 (19)	0.45735 (13)	0.0577 (5)
C4	0.8912 (2)	0.37177 (16)	0.53312 (11)	0.0490 (4)
C5	0.7908 (2)	0.46074 (18)	0.54392 (13)	0.0575 (5)
C6	0.7107 (2)	0.50799 (19)	0.47591 (13)	0.0575 (5)
C7	0.53685 (19)	0.27564 (17)	0.18405 (11)	0.0490 (4)
C8	0.5683 (2)	0.15850 (19)	0.20631 (13)	0.0612 (5)
C9	0.5008 (2)	0.0665 (2)	0.16059 (14)	0.0636 (5)
C10	0.4038 (2)	0.09416 (18)	0.09400 (11)	0.0531 (5)
C11	0.3700 (3)	0.2107 (2)	0.07197 (13)	0.0657 (6)
C12	0.4380 (3)	0.3028 (2)	0.11770 (13)	0.0656 (6)
C13	0.3291 (3)	0.6297 (2)	0.21513 (17)	0.0696 (6)
C14	0.5698 (4)	0.6232 (3)	0.1607 (2)	0.0929 (9)
H3	0.979 (3)	0.269 (2)	0.4549 (14)	0.072 (7)*
H2	0.849 (2)	0.3467 (19)	0.3405 (14)	0.067 (6)*
H5	0.771 (2)	0.4874 (18)	0.5960 (14)	0.066 (6)*
H6	0.645 (2)	0.573 (2)	0.4775 (14)	0.075 (7)*
H8	0.635 (3)	0.141 (2)	0.2532 (15)	0.082 (7)*
H9	0.526 (3)	−0.011 (2)	0.1710 (14)	0.075 (7)*
H11	0.302 (3)	0.228 (2)	0.0270 (17)	0.098 (8)*
H12	0.421 (2)	0.383 (2)	0.1011 (14)	0.078 (7)*
H13A	0.280 (2)	0.625 (2)	0.1605 (16)	0.076 (7)*
H13B	0.268 (3)	0.591 (3)	0.2550 (19)	0.109 (10)*
H13C	0.352 (3)	0.711 (3)	0.2305 (18)	0.104 (9)*
H14A	0.530 (3)	0.632 (3)	0.104 (2)	0.112 (10)*
H14B	0.586 (4)	0.718 (3)	0.176 (2)	0.134 (12)*
H14C	0.669 (4)	0.585 (3)	0.170 (2)	0.125 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0462 (3)	0.0482 (3)	0.0501 (3)	−0.0012 (2)	−0.00152 (19)	−0.0030 (2)
O1	0.0579 (8)	0.0510 (7)	0.0613 (8)	−0.0060 (6)	−0.0128 (6)	−0.0024 (6)
O2	0.1024 (13)	0.1145 (14)	0.0507 (9)	0.0183 (11)	−0.0025 (9)	−0.0023 (9)
O3	0.1104 (14)	0.0940 (12)	0.0824 (11)	0.0446 (11)	−0.0093 (11)	0.0054 (10)
O4	0.0481 (7)	0.0620 (8)	0.0628 (8)	0.0056 (6)	−0.0046 (6)	−0.0133 (7)
O5	0.1088 (14)	0.0669 (11)	0.1068 (14)	−0.0050 (10)	0.0034 (11)	−0.0271 (10)
O6	0.1411 (18)	0.1054 (15)	0.0894 (13)	−0.0263 (13)	−0.0487 (14)	−0.0128 (11)
O7	0.0599 (8)	0.0631 (8)	0.0618 (8)	−0.0059 (7)	0.0114 (7)	0.0018 (7)
N1	0.0630 (10)	0.0672 (11)	0.0587 (11)	0.0002 (9)	−0.0003 (8)	0.0062 (9)
N2	0.0791 (13)	0.0771 (13)	0.0622 (11)	−0.0129 (11)	0.0077 (10)	−0.0152 (10)
N3	0.0491 (8)	0.0545 (9)	0.0616 (9)	0.0023 (7)	0.0010 (7)	0.0064 (7)
C1	0.0460 (9)	0.0463 (9)	0.0522 (10)	−0.0056 (8)	−0.0047 (8)	−0.0057 (8)
C2	0.0597 (12)	0.0656 (12)	0.0476 (11)	0.0055 (10)	0.0022 (9)	−0.0112 (9)
C3	0.0554 (12)	0.0552 (11)	0.0618 (12)	0.0094 (10)	0.0029 (9)	−0.0059 (10)
C4	0.0486 (10)	0.0468 (9)	0.0507 (10)	−0.0043 (8)	0.0002 (8)	0.0005 (8)
C5	0.0616 (12)	0.0606 (12)	0.0501 (11)	0.0023 (10)	0.0048 (9)	−0.0099 (9)
C6	0.0565 (12)	0.0537 (11)	0.0615 (12)	0.0089 (9)	0.0018 (9)	−0.0094 (9)
C7	0.0449 (9)	0.0527 (10)	0.0482 (10)	0.0054 (8)	−0.0002 (8)	−0.0061 (8)
C8	0.0597 (11)	0.0617 (12)	0.0582 (12)	0.0113 (10)	−0.0136 (10)	−0.0001 (10)
C9	0.0697 (13)	0.0496 (12)	0.0690 (13)	0.0098 (10)	−0.0051 (11)	−0.0018 (10)
C10	0.0537 (10)	0.0596 (11)	0.0458 (10)	−0.0019 (9)	0.0041 (8)	−0.0088 (9)
C11	0.0748 (14)	0.0700 (14)	0.0478 (11)	0.0025 (11)	−0.0151 (10)	−0.0012 (10)
C12	0.0786 (14)	0.0554 (12)	0.0582 (12)	0.0067 (11)	−0.0153 (11)	0.0032 (10)
C13	0.0621 (13)	0.0686 (15)	0.0733 (16)	0.0121 (12)	−0.0161 (12)	−0.0067 (12)
C14	0.0800 (19)	0.095 (2)	0.104 (2)	−0.0102 (16)	0.0121 (17)	0.0388 (18)

Geometric parameters (Å, º)

P1—O7	1.4547 (14)	C4—C5	1.370 (3)
P1—O1	1.5845 (13)	C5—C6	1.375 (3)
P1—O4	1.5999 (14)	C5—H5	0.94 (2)
P1—N3	1.6032 (17)	C6—H6	0.94 (2)
O1—C1	1.403 (2)	C7—C8	1.371 (3)
O2—N1	1.211 (2)	C7—C12	1.376 (3)
O3—N1	1.218 (2)	C8—C9	1.374 (3)
O4—C7	1.393 (2)	C8—H8	0.95 (3)
O5—N2	1.220 (3)	C9—C10	1.370 (3)
O6—N2	1.220 (3)	C9—H9	0.90 (2)
N1—C4	1.475 (2)	C10—C11	1.368 (3)
N2—C10	1.465 (3)	C11—C12	1.377 (3)
N3—C14	1.460 (3)	C11—H11	0.94 (3)
N3—C13	1.461 (3)	C12—H12	0.93 (2)
C1—C6	1.370 (3)	C13—H13A	0.96 (2)
C1—C2	1.379 (3)	C13—H13B	1.00 (3)
C2—C3	1.369 (3)	C13—H13C	0.95 (3)
C2—H2	0.89 (2)	C14—H14A	0.97 (3)
C3—C4	1.370 (3)	C14—H14B	1.08 (3)
C3—H3	0.90 (2)	C14—H14C	1.00 (3)
O7—P1—O1	115.81 (8)	C1—C6—H6	116.4 (14)
O7—P1—O4	113.65 (8)	C5—C6—H6	123.9 (14)
O1—P1—O4	98.49 (7)	C8—C7—C12	121.39 (19)
O7—P1—N3	115.77 (8)	C8—C7—O4	117.51 (16)
O1—P1—N3	104.53 (8)	C12—C7—O4	121.09 (17)
O4—P1—N3	106.75 (9)	C7—C8—C9	119.13 (19)
C1—O1—P1	123.38 (11)	C7—C8—H8	120.7 (14)
C7—O4—P1	120.95 (11)	C9—C8—H8	120.2 (14)
O2—N1—O3	123.73 (19)	C10—C9—C8	119.2 (2)
O2—N1—C4	118.60 (18)	C10—C9—H9	119.8 (15)
O3—N1—C4	117.66 (18)	C8—C9—H9	120.8 (15)
O6—N2—O5	123.2 (2)	C11—C10—C9	122.15 (19)
O6—N2—C10	118.2 (2)	C11—C10—N2	118.66 (18)
O5—N2—C10	118.6 (2)	C9—C10—N2	119.19 (19)
C14—N3—C13	114.6 (2)	C10—C11—C12	118.58 (19)
C14—N3—P1	121.70 (17)	C10—C11—H11	121.1 (16)
C13—N3—P1	121.99 (17)	C12—C11—H11	120.3 (16)
C6—C1—C2	121.57 (18)	C7—C12—C11	119.5 (2)
C6—C1—O1	117.60 (16)	C7—C12—H12	120.8 (14)
C2—C1—O1	120.73 (17)	C11—C12—H12	119.5 (14)
C3—C2—C1	118.98 (19)	N3—C13—H13A	105.7 (14)
C3—C2—H2	118.7 (14)	N3—C13—H13B	111.1 (16)
C1—C2—H2	122.3 (14)	H13A—C13—H13B	110 (2)
C2—C3—C4	119.10 (19)	N3—C13—H13C	106.8 (17)
C2—C3—H3	123.4 (15)	H13A—C13—H13C	112 (2)
C4—C3—H3	117.5 (15)	H13B—C13—H13C	111 (2)
C3—C4—C5	122.33 (18)	N3—C14—H14A	114.2 (18)
C3—C4—N1	119.22 (18)	N3—C14—H14B	111.4 (19)
C5—C4—N1	118.45 (18)	H14A—C14—H14B	99 (3)
C4—C5—C6	118.51 (19)	N3—C14—H14C	109.9 (18)
C4—C5—H5	122.4 (13)	H14A—C14—H14C	116 (3)
C6—C5—H5	119.0 (13)	H14B—C14—H14C	106 (3)
C1—C6—C5	119.48 (19)
O7—P1—O1—C1	47.65 (16)	O3—N1—C4—C5	176.33 (19)
O4—P1—O1—C1	−73.86 (15)	C3—C4—C5—C6	−1.1 (3)
N3—P1—O1—C1	176.28 (14)	N1—C4—C5—C6	179.16 (17)
O7—P1—O4—C7	45.88 (16)	C2—C1—C6—C5	1.3 (3)
O1—P1—O4—C7	168.97 (13)	O1—C1—C6—C5	−175.02 (17)
N3—P1—O4—C7	−82.98 (15)	C4—C5—C6—C1	−0.3 (3)
O7—P1—N3—C14	−177.6 (2)	P1—O4—C7—C8	−119.59 (18)
O1—P1—N3—C14	53.7 (2)	P1—O4—C7—C12	61.6 (2)
O4—P1—N3—C14	−50.0 (2)	C12—C7—C8—C9	0.9 (3)
O7—P1—N3—C13	18.0 (2)	O4—C7—C8—C9	−177.98 (18)
O1—P1—N3—C13	−110.61 (17)	C7—C8—C9—C10	−0.1 (3)
O4—P1—N3—C13	145.67 (17)	C8—C9—C10—C11	−0.9 (3)
P1—O1—C1—C6	−106.60 (18)	C8—C9—C10—N2	178.77 (19)
P1—O1—C1—C2	77.0 (2)	O6—N2—C10—C11	−7.1 (3)
C6—C1—C2—C3	−1.0 (3)	O5—N2—C10—C11	173.5 (2)
O1—C1—C2—C3	175.28 (17)	O6—N2—C10—C9	173.2 (2)
C1—C2—C3—C4	−0.4 (3)	O5—N2—C10—C9	−6.2 (3)
C2—C3—C4—C5	1.5 (3)	C9—C10—C11—C12	1.1 (3)
C2—C3—C4—N1	−178.79 (18)	N2—C10—C11—C12	−178.6 (2)
O2—N1—C4—C3	175.4 (2)	C8—C7—C12—C11	−0.7 (3)
O3—N1—C4—C3	−3.4 (3)	O4—C7—C12—C11	178.14 (19)
O2—N1—C4—C5	−4.9 (3)	C10—C11—C12—C7	−0.3 (3)