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

Starynowicz, P.; Lis, T.

doi:10.1107/S2052520614010439

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

P. Starynowicz and T. Lis

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.

Keywords: charge-density distribution; density-functional calculations; polarization effects.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520614010439/pi5018sup1.cif Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520614010439/pi5018Isup2.hkl Contains datablock I
	Portable Document Format (PDF) file https://doi.org/10.1107/S2052520614010439/pi5018sup3.pdf Intensity statistics, bond lengths and Hessian matrix decomposition

CCDC reference: 1001668

Experimental top

Refinement top

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

Results and discussion top

Computing details top

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 top

sodium bis(4-nitrophenyl)phosphate top

Crystal data top

C₁₂H₈N₂NaO₈P	Z = 2
M_r = 362.16	D_x = 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) Å³

Data collection top

Xcalibur, Ruby diffractometer	27119 independent reflections
Radiation source: Enhance (Mo) X-ray Source	23369 reflections with > 3σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 10.3456 pixels mm^-1	θ_max = 73.6°, θ_min = 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
T_min = 0.893, T_max = 0.938	l = −28→30
118238 measured reflections

Refinement top

Refinement on F	0 restraints
Least-squares matrix: full	w1 = [F_o*sqrt(w2) + sqrt(F_o²w2² + sqrt(w2²))]² where w2 = q/[s²(F_o²) + (0.00 P)² + 0.00 P + 0.00 + 0.00 sin(th)] where P = (0.3333 F_o² + 0.6667 F_c²) q = 1.0
R[F² > 2σ(F²)] = 0.013	(Δ/σ)_max = 0.00001
wR(F²) = 0.013	Δρ_max = 0.25 e Å⁻³
S = 1.46	Δρ_min = −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)

Crystal data top

C₁₂H₈N₂NaO₈P	γ = 106.35 (3)°
M_r = 362.16	V = 666.0 (4) Å³
Triclinic, P1	Z = 2
a = 6.9661 (16) Å	Mo Kα radiation
b = 9.843 (3) Å	µ = 0.29 mm⁻¹
c = 11.215 (3) Å	T = 80 K
α = 103.93 (3)°	0.63 × 0.36 × 0.33 mm
β = 105.94 (3)°

Data collection top

Xcalibur, Ruby diffractometer	27119 independent reflections
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)	23369 reflections with > 3σ(I)
T_min = 0.893, T_max = 0.938	R_int = 0.020
118238 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.013	635 parameters
wR(F²) = 0.013	0 restraints
S = 1.46	Δρ_max = 0.25 e Å⁻³
16041 reflections	Δρ_min = −0.23 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

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.

Experimental details

Crystal data
Chemical formula	C₁₂H₈N₂NaO₈P
M_r	362.16
Crystal system, space group	Triclinic, P1
Temperature (K)	80
a, b, c (Å)	6.9661 (16), 9.843 (3), 11.215 (3)
α, β, γ (°)	103.93 (3), 105.94 (3), 106.35 (3)
V (Å³)	666.0 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.63 × 0.36 × 0.33

Data collection
Diffractometer	Xcalibur, Ruby diffractometer
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)
T_min, T_max	0.893, 0.938
No. of measured, independent and observed [ > 3σ(I)] reflections	118238, 27119, 23369
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	1.350

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.013, 0.013, 1.46
No. of reflections	16041
No. of parameters	635
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.23

Computer programs: CrysAlis PRO, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET) (compiled Oct 27 2011,15:02:11), Volkov et al., (2006).

Selected geometric parameters (Å, º) top

P—O(11)	1.6293 (1)	C(5)—C(6)	1.3891 (2)
P—O(21)	1.6301 (1)	C(11)—C(21)	1.4009 (2)
P—O(31)	1.4748 (1)	C(11)—C(61)	1.4011 (1)
P—O(41)	1.4845 (1)	C(21)—C(31)	1.3887 (2)
O(1)—N(1)	1.2254 (2)	C(21)—H(21)	1.0900 (1)
O(2)—N(1)	1.2353 (2)	C(31)—C(41)	1.3917 (2)
O(3)—N(2)	1.2244 (2)	C(31)—H(31)	1.0900 (1)
O(4)—N(2)	1.2324 (2)	C(41)—C(51)	1.3903 (2)
O(11)—C(1)	1.3627 (1)	C(51)—C(61)	1.3890 (2)
O(21)—C(11)	1.3619 (1)	C(51)—H(51)	1.0900 (1)
N(1)—C(4)	1.4550 (1)	C(61)—H(61)	1.0900 (1)
N(2)—C(41)	1.4547 (1)	NA—O(2)	2.4617 (1)
C(1)—C(2)	1.4011 (1)	NA—O(4)ⁱ	2.3880 (2)
C(1)—C(6)	1.4000 (2)	NA—O(31)ⁱⁱ	2.2403 (1)
C(2)—C(3)	1.3866 (2)	NA—O(41)ⁱⁱⁱ	2.3141 (1)
C(3)—C(4)	1.3926 (2)	NA—O(41)^iv	2.4055 (1)
C(4)—C(5)	1.3918 (1)

O(11)—P—O(21)	92.413 (5)	O(21)—P—O(41)	110.157 (7)
O(11)—P—O(31)	110.884 (7)	O(31)—P—O(41)	119.668 (7)
O(11)—P—O(41)	110.005 (6)	P—O(11)—C(1)	123.757 (9)
O(21)—P—O(31)	110.355 (7)	P—O(21)—C(11)	123.765 (8)

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.

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