Charge-density distribution in sodium bis(4-nitrophenyl)phosphate

The electron-density distribution in sodium bis(4-nitro­phenyl)phosphate has been analyzed using the multipole refinement of X-ray diffraction data and of theoretical density-functional theory (DFT) calculations. The ester P-O bonds are particularly long and their topological parameters (density at the bond critical point, Laplacian) are lower than for other P-O bonds. Some disagreement between the experimental and theoretical charges of atoms constituting the nitro groups has been observed and the possible reasons are discussed. Weak polarization effects produced by sodium cations may be observed within the phosphate fragment; they are more manifest in the case of the nitro groups.

S1. Experimental

S1.1. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

S2. Results and discussion

Computing details

Data collection: CrysAlis PRO, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET) (compiled Oct 27 2011,15:02:11); cell refinement: CrysAlis PRO, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET) (compiled Oct 27 2011,15:02:11); data reduction: CrysAlis PRO, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET) (compiled Oct 27 2011,15:02:11); program(s) used to refine structure: Volkov et al., (2006); molecular graphics: Volkov et al., (2006); software used to prepare material for publication: Volkov et al., (2006).

Figures

sodium bis(4-nitrophenyl)phosphate

Crystal data

C12H8N2NaO8P	Z = 2
Mr = 362.16	Dx = 1.806 Mg m^−3
Triclinic, P1	Mo Kα radiation, λ = 0.7107 Å
a = 6.9661 (16) Å	Cell parameters from 64250 reflections
b = 9.843 (3) Å	θ = 3.2–73.6°
c = 11.215 (3) Å	µ = 0.29 mm^−1
α = 103.93 (3)°	T = 80 K
β = 105.94 (3)°	Irregular, yellow
γ = 106.35 (3)°	0.63 × 0.36 × 0.33 mm
V = 666.0 (4) Å^3

Data collection

Xcalibur, Ruby diffractometer	27119 independent reflections
Radiation source: Enhance (Mo) X-ray Source	23369 reflections with > 3σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 10.3456 pixels mm^-1	θmax = 73.6°, θmin = 3.2°
ω scans	h = −18→17
Absorption correction: analytical CrysAlis PRO, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET) (compiled Oct 27 2011,15:02:11) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)	k = −24→26
Tmin = 0.893, Tmax = 0.938	l = −28→30
118238 measured reflections

Refinement

Refinement on F	0 restraints
Least-squares matrix: full	w1 = [Fo*sqrt(w2) + sqrt(Fo^2w2^2 + sqrt(w2^2))]^2 where w2 = q/[s^2(Fo^2) + (0.00 P)^2 + 0.00 P + 0.00 + 0.00 sin(th)] where P = (0.3333 Fo^2 + 0.6667 Fc^2) q = 1.0
R[F^2 > 2σ(F^2)] = 0.013	(Δ/σ)max = 0.00001
wR(F^2) = 0.013	Δρmax = 0.25 e Å^−3
S = 1.46	Δρmin = −0.23 e Å^−3
16041 reflections	Extinction correction: Becker-Coppens type 1 Gaussian isotropic, Becker, P.J. & Coppens, P. (1974) Acta Cryst., A30, 129-153.
635 parameters	Extinction coefficient: 0.184 (5)

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

	x	y	z	Uiso*/Ueq
P	0.191460 (5)	0.368711 (4)	0.291180 (3)	0.006
NA	0.755796 (10)	1.411597 (7)	0.392625 (7)	0.009
O(1)	0.53047 (3)	1.112735 (17)	0.186336 (17)	0.013
O(2)	0.66604 (3)	1.152126 (15)	0.395136 (15)	0.012
O(3)	−0.28467 (4)	−0.464995 (19)	0.15570 (2)	0.018
O(4)	−0.14141 (3)	−0.347644 (19)	0.366755 (18)	0.015
O(11)	0.18913 (2)	0.451162 (12)	0.181326 (10)	0.01
O(21)	0.025099 (19)	0.206321 (11)	0.179933 (10)	0.009
O(31)	0.404652 (19)	0.362255 (14)	0.349140 (13)	0.011
O(41)	0.086597 (18)	0.427658 (13)	0.379199 (11)	0.009
N(1)	0.556985 (18)	1.067436 (12)	0.279996 (11)	0.009
N(2)	−0.18547 (2)	−0.349160 (13)	0.252113 (13)	0.01
C(1)	0.28339 (2)	0.602920 (12)	0.212025 (11)	0.008
C(2)	0.24913 (2)	0.655591 (14)	0.105538 (12)	0.009
C(3)	0.33688 (2)	0.808379 (14)	0.126683 (12)	0.009
C(4)	0.45927 (2)	0.906969 (13)	0.255540 (11)	0.008
C(5)	0.49672 (2)	0.856008 (13)	0.362038 (11)	0.009
C(6)	0.40926 (2)	0.702930 (13)	0.340909 (11)	0.009
C(11)	−0.014377 (19)	0.073253 (12)	0.202811 (11)	0.008
C(21)	−0.14113 (2)	−0.057336 (13)	0.092193 (11)	0.009
C(31)	−0.19464 (2)	−0.198110 (14)	0.106107 (12)	0.01
C(41)	−0.12017 (2)	−0.204945 (13)	0.232229 (12)	0.009
C(51)	0.00768 (2)	−0.076736 (14)	0.342940 (12)	0.01
C(61)	0.06147 (2)	0.063937 (13)	0.328780 (12)	0.009
H(2)	0.158632	0.576755	0.004751	0.015
H(3)	0.312482	0.852672	0.045853	0.014
H(5)	0.598352	0.932411	0.462366	0.009
H(6)	0.438228	0.661117	0.423149	0.008
H(21)	−0.196138	−0.042567	−0.002954	0.014
H(31)	−0.29389	−0.297427	0.018088	0.014
H(51)	0.059425	−0.091934	0.438141	0.012
H(61)	0.153966	0.166122	0.415132	0.009

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P	0.005799 (10)	0.005201 (9)	0.007097 (9)	0.001783 (7)	0.002514 (7)	0.002159 (7)
NA	0.007193 (18)	0.007551 (18)	0.011703 (19)	0.002480 (14)	0.003734 (14)	0.003636 (15)
O(1)	0.01700 (5)	0.00912 (4)	0.01390 (4)	0.00364 (4)	0.00478 (4)	0.00659 (4)
O(2)	0.01417 (5)	0.00653 (4)	0.01224 (4)	0.00187 (3)	0.00303 (4)	0.00233 (3)
O(3)	0.02700 (8)	0.00658 (4)	0.01910 (6)	0.00273 (5)	0.01113 (6)	0.00316 (4)
O(4)	0.01925 (6)	0.01092 (5)	0.01669 (5)	0.00539 (4)	0.00723 (5)	0.00895 (4)
O(11)	0.01386 (4)	0.00570 (3)	0.00824 (3)	0.00109 (2)	0.00385 (2)	0.00270 (2)
O(21)	0.01062 (3)	0.00524 (3)	0.00849 (3)	0.00108 (2)	0.00154 (2)	0.00251 (2)
O(31)	0.00667 (3)	0.01143 (3)	0.01444 (3)	0.00401 (3)	0.00290 (3)	0.00366 (3)
O(41)	0.00878 (3)	0.01018 (3)	0.00989 (3)	0.00405 (2)	0.00499 (2)	0.00280 (2)
N(1)	0.00903 (3)	0.00613 (3)	0.01107 (3)	0.00264 (2)	0.00378 (2)	0.00352 (2)
N(2)	0.01251 (4)	0.00682 (3)	0.01480 (4)	0.00417 (3)	0.00760 (3)	0.00516 (3)
C(1)	0.00912 (3)	0.00595 (3)	0.00778 (3)	0.00185 (2)	0.00314 (2)	0.00256 (2)
C(2)	0.01121 (4)	0.00699 (3)	0.00783 (3)	0.00141 (3)	0.00251 (3)	0.00275 (2)
C(3)	0.01085 (4)	0.00737 (3)	0.00885 (3)	0.00217 (3)	0.00269 (3)	0.00369 (3)
C(4)	0.00865 (3)	0.00609 (3)	0.00915 (3)	0.00237 (2)	0.00306 (2)	0.00302 (2)
C(5)	0.01011 (4)	0.00626 (3)	0.00842 (3)	0.00206 (3)	0.00254 (3)	0.00238 (2)
C(6)	0.01072 (4)	0.00635 (3)	0.00793 (3)	0.00203 (3)	0.00270 (3)	0.00269 (2)
C(11)	0.00850 (3)	0.00566 (3)	0.00767 (3)	0.00189 (2)	0.00255 (2)	0.00231 (2)
C(21)	0.01124 (4)	0.00652 (3)	0.00787 (3)	0.00165 (3)	0.00271 (3)	0.00216 (2)
C(31)	0.01225 (4)	0.00610 (3)	0.00953 (3)	0.00179 (3)	0.00402 (3)	0.00193 (3)
C(41)	0.01021 (4)	0.00622 (3)	0.01059 (3)	0.00300 (3)	0.00482 (3)	0.00352 (3)
C(51)	0.01161 (4)	0.00751 (3)	0.00939 (3)	0.00285 (3)	0.00312 (3)	0.00400 (3)
C(61)	0.01166 (4)	0.00666 (3)	0.00812 (3)	0.00200 (3)	0.00206 (3)	0.00281 (2)
H(2)	0.0233	0.0073	0.0073	0.0003	0.0023	0.0028
H(3)	0.0215	0.0076	0.0086	0.0008	0.0025	0.0037
H(5)	0.0085	0.0064	0.0087	0.0015	0.001	0.0024
H(6)	0.0078	0.0065	0.0077	0.0018	0.0012	0.0025
H(21)	0.0202	0.0066	0.0089	0	0.0024	0.002
H(31)	0.0195	0.0063	0.0114	0.0008	0.0049	0.0022
H(51)	0.016	0.0078	0.0118	0.0027	0.003	0.0051
H(61)	0.0115	0.007	0.0088	0.0024	0.0025	0.0035

Geometric parameters (Å, º)

P—O(11)	1.6293 (1)	C(5)—C(6)	1.3891 (2)
P—O(21)	1.6301 (1)	C(5)—H(5)	1.0900 (1)
P—O(31)	1.4748 (1)	C(6)—H(6)	1.0900 (1)
P—O(41)	1.4845 (1)	C(11)—C(21)	1.4009 (2)
O(1)—N(1)	1.2254 (2)	C(11)—C(61)	1.4011 (1)
O(2)—N(1)	1.2353 (2)	C(21)—C(31)	1.3887 (2)
O(3)—N(2)	1.2244 (2)	C(21)—H(21)	1.0900 (1)
O(4)—N(2)	1.2324 (2)	C(31)—C(41)	1.3917 (2)
O(11)—C(1)	1.3627 (1)	C(31)—H(31)	1.0900 (1)
O(21)—C(11)	1.3619 (1)	C(41)—C(51)	1.3903 (2)
N(1)—C(4)	1.4550 (1)	C(51)—C(61)	1.3890 (2)
N(2)—C(41)	1.4547 (1)	C(51)—H(51)	1.0900 (1)
C(1)—C(2)	1.4011 (1)	C(61)—H(61)	1.0900 (1)
C(1)—C(6)	1.4000 (2)	NA—O(2)	2.4617 (1)
C(2)—C(3)	1.3866 (2)	NA—O(4)^i	2.3880 (2)
C(2)—H(2)	1.0900 (1)	NA—O(31)^ii	2.2403 (1)
C(3)—C(4)	1.3926 (2)	NA—O(41)^iii	2.3141 (1)
C(3)—H(3)	1.0900 (1)	NA—O(41)^iv	2.4055 (1)
C(4)—C(5)	1.3918 (1)
O(11)—P—O(21)	92.413 (5)	C(1)—C(6)—H(6)	120.438 (10)
O(11)—P—O(31)	110.884 (7)	C(5)—C(6)—H(6)	120.662 (11)
O(11)—P—O(41)	110.005 (6)	O(21)—C(11)—C(21)	116.115 (10)
O(21)—P—O(31)	110.355 (7)	O(21)—C(11)—C(61)	123.227 (10)
O(21)—P—O(41)	110.157 (7)	C(21)—C(11)—C(61)	120.647 (10)
O(31)—P—O(41)	119.668 (7)	C(11)—C(21)—C(31)	120.338 (10)
P—O(11)—C(1)	123.757 (9)	C(11)—C(21)—H(21)	117.145 (10)
P—O(21)—C(11)	123.765 (8)	C(31)—C(21)—H(21)	122.510 (11)
O(1)—N(1)—O(2)	122.810 (13)	C(21)—C(31)—C(41)	118.183 (11)
O(1)—N(1)—C(4)	119.110 (12)	C(21)—C(31)—H(31)	118.488 (11)
O(2)—N(1)—C(4)	118.073 (11)	C(41)—C(31)—H(31)	123.326 (11)
O(3)—N(2)—O(4)	123.188 (15)	N(2)—C(41)—C(31)	119.781 (11)
O(3)—N(2)—C(41)	119.183 (14)	N(2)—C(41)—C(51)	117.857 (11)
O(4)—N(2)—C(41)	117.608 (13)	C(31)—C(41)—C(51)	122.286 (10)
O(11)—C(1)—C(2)	115.949 (10)	C(41)—C(51)—C(61)	119.438 (10)
O(11)—C(1)—C(6)	123.330 (10)	C(41)—C(51)—H(51)	117.667 (10)
C(2)—C(1)—C(6)	120.718 (10)	C(61)—C(51)—H(51)	122.888 (12)
C(1)—C(2)—C(3)	120.334 (11)	C(11)—C(61)—C(51)	119.097 (11)
C(1)—C(2)—H(2)	120.496 (11)	C(11)—C(61)—H(61)	120.373 (10)
C(3)—C(2)—H(2)	119.126 (10)	C(51)—C(61)—H(61)	120.445 (10)
C(2)—C(3)—C(4)	118.407 (10)	O(2)—NA—O(4)^i	172.350 (7)
C(2)—C(3)—H(3)	121.971 (11)	O(2)—NA—O(31)^ii	84.270 (5)
C(4)—C(3)—H(3)	119.621 (11)	O(2)—NA—O(41)^iii	93.034 (5)
N(1)—C(4)—C(3)	119.460 (10)	O(2)—NA—O(41)^iv	105.615 (5)
N(1)—C(4)—C(5)	118.651 (10)	O(4)^i—NA—O(31)^ii	99.533 (6)
C(3)—C(4)—C(5)	121.860 (10)	O(4)^i—NA—O(41)^iii	81.577 (6)
C(4)—C(5)—C(6)	119.768 (11)	O(4)^i—NA—O(41)^iv	80.210 (6)
C(4)—C(5)—H(5)	121.954 (10)	O(31)^ii—NA—O(41)^iii	165.010 (5)
C(6)—C(5)—H(5)	118.241 (10)	O(31)^ii—NA—O(41)^iv	101.901 (5)
C(1)—C(6)—C(5)	118.900 (10)	O(41)^iii—NA—O(41)^iv	93.033 (4)

Symmetry codes: (i) x+1, y+2, z; (ii) x, y+1, z; (iii) x+1, y+1, z; (iv) −x+1, −y+2, −z+1.