Sodium 3,5-di­nitro­benzoate

Jones, H.P.; Gillon, A.L.; Davey, R.J.

doi:10.1107/S1600536805014893

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 61| Part 6| June 2005| Pages m1131-m1132

https://doi.org/10.1107/S1600536805014893

Sodium 3,5-dinitrobenzoate

Helen P. Jones,^a ^* Amy L. Gillon ^a ‡ and Roger J. Davey ^a

^aColloids, Crystals and Interfaces Group, School of Chemical Engineering and Analytical Sciences, The University of Manchester, PO Box 88, Manchester M60 1QD, England
^*Correspondence e-mail: h.jones-2@postgrad.manchester.ac.uk

(Received 5 April 2005; accepted 10 May 2005; online 14 May 2005)

Sodium 3,5-dinitrobenzoate, Na⁺·C₇H₃N₂O₆⁻, was obtained by evaporation at room temperature of an aqueous solution of ethylenediammonium 3,5-dinitrobenzoate in sodium hydroxide. The structure is trigonal and the benzoate ion has twofold crystallographic symmetry.

Comment

During work on crystallization of the salt ethylenediammonium 3,5-dinitrobenzoate, an aqueous solution of the salt at pH 12 was prepared and allowed to evaporate at room temperature, giving red prisms of sodium 3,5-dinitrobenzoate (NaDNB), (I). The crystal structure was not found in the Cambridge Structural Database (CSD, Version 5.25; Allen, 2002 ) and hence its structure was determined by single-crystal X-ray diffraction at 150 K.

The benzoate ion is on a twofold axis of symmetry, passing through the carboxylate group (Fig. 1).

Figure 1
View of NaDNB, showing the whole benzoate anion. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) x − y, −y, −z + $[2\over3]$ .]

Figure 2
The packing of sodium 3,5-dinitrobenzoate, viewed along the c axis, showing the threefold symmetry.

Figure 3
The twofold axis of symmetry perpendicular to the c axis.

Experimental

3,5-Dinitrobenzoic acid (Aldrich, 99%) was dissolved in sodium hydroxide solution and a solution of ethylenediamine (Aldrich, 99%) was added. The solution was filtered and the pH recorded as 12.14. The solution pH was measured using an Accumet Basic AB15 pH meter with an Accumet glass calomel pH electrode. The solution was allowed to evaporate to dryness in air at room temperature. Crystals of ethylenediammonium 3,5-dinitrobenzoate, sodium hydroxide and red prisms of sodium 3,5-dinitrobenzoate formed.

Crystal data

Na⁺·C₇H₃N₂O₆⁻
M_r = 234.1
Trigonal, P3₁21
a = 10.7701 (5) Å
c = 6.3526 (2) Å
V = 638.15 (5) Å³
Z = 3
D_x = 1.828 Mg m⁻³
Mo Kα radiation
Cell parameters from 2522 reflections
θ = 1.0–27.5°
μ = 0.20 mm⁻¹
T = 150 K
Prism, red
0.25 × 0.25 × 0.25 mm

Data collection

Nonius KappaCCD diffractometer
Thick-slice φ and ω scans
Absorption correction: multi-scan (Blessing, 1995 ) T_min = 0.796, T_max = 0.951
3498 measured reflections
554 independent reflections
537 reflections with I > 2σ(I)
R_int = 0.027
θ_max = 27.5°
h = −12 → 13
k = −8 → 13
l = −8 → 8

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.066
S = 1.09
554 reflections
76 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0336P)² + 0.1582P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.18 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.14 (2)

In the absence of significant anomalous dispersion effects, Friedel pairs were merged. The choice of space group P3₁21 rather than P3₂21 is arbitrary. All H atoms were positioned geometrically and refined as riding, with C—H = 0.93–0.98 Å and U_iso(H) = 1.2U_eq(C).

Data collection: COLLECT (Nonius, 2000 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SORTAV (Blessing, 1987 ,1989 , SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536805014893/ww6381sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805014893/ww6381Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Sodium 3,5-dinitrobenzoate top

Crystal data top

Na⁺·C₇H₃N₂O₆⁻	D_x = 1.828 Mg m⁻³
M_r = 234.1	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3₁21	Cell parameters from 2522 reflections
Hall symbol: P 31 2"	θ = 1.0–27.5°
a = 10.7701 (5) Å	µ = 0.20 mm⁻¹
c = 6.3526 (2) Å	T = 150 K
V = 638.15 (5) Å³	Prism, red
Z = 3	0.25 × 0.25 × 0.25 mm
F(000) = 354

Data collection top

Nonius KappaCCD diffractometer	554 independent reflections
Radiation source: Enraf Nonius FR590	537 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
CCD rotation images, thick slices scans	θ_max = 27.5°, θ_min = 3.8°
Absorption correction: multi-scan (Blessing, 1995)	h = −12→13
T_min = 0.796, T_max = 0.951	k = −8→13
3498 measured reflections	l = −8→8

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.026	H-atom parameters constrained
wR(F²) = 0.066	w = 1/[σ²(F_o²) + (0.0336P)² + 0.1582P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
554 reflections	Δρ_max = 0.24 e Å⁻³
76 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.14 (2)

Special details top

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.

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

	x	y	z	U_iso*/U_eq
C1	0.2002 (2)	1	−0.1667	0.0113 (5)
C2	0.3418 (2)	1	−0.1667	0.0122 (5)
C3	0.3701 (2)	0.92732 (19)	−0.0104 (2)	0.0131 (4)
H3	0.3033	0.8786	0.0952	0.016*
O3	0.11648 (14)	0.93745 (13)	−0.01613 (17)	0.0138 (3)
C4	0.4994 (2)	0.9287 (2)	−0.0143 (2)	0.0151 (4)
C5	0.6034 (2)	1	−0.1667	0.0155 (5)
H5	0.6897	1	−0.1667	0.019*
N2	0.52972 (17)	0.85204 (18)	0.1513 (2)	0.0186 (4)
Na1	0.87486 (9)	0.87486 (9)	0	0.0131 (3)
O1	0.63430 (15)	0.83610 (16)	0.1274 (2)	0.0242 (4)
O2	0.45083 (19)	0.8090 (2)	0.3043 (2)	0.0329 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0111 (8)	0.0108 (11)	0.0118 (10)	0.0054 (5)	−0.0016 (4)	−0.0031 (8)
C2	0.0115 (9)	0.0135 (11)	0.0122 (10)	0.0067 (6)	−0.0012 (4)	−0.0024 (9)
C3	0.0136 (9)	0.0142 (9)	0.0121 (8)	0.0073 (7)	0.0010 (6)	0.0001 (6)
O3	0.0118 (6)	0.0162 (7)	0.0133 (6)	0.0069 (5)	0.0013 (4)	0.0010 (5)
C4	0.0170 (8)	0.0185 (9)	0.0132 (8)	0.0115 (7)	−0.0009 (6)	0.0006 (7)
C5	0.0130 (9)	0.0179 (13)	0.0173 (11)	0.0089 (6)	0.0002 (5)	0.0005 (9)
N2	0.0179 (8)	0.0226 (9)	0.0183 (7)	0.0125 (7)	0.0007 (6)	0.0056 (6)
Na1	0.0131 (4)	0.0131 (4)	0.0128 (4)	0.0064 (4)	−0.00068 (18)	0.00068 (18)
O1	0.0170 (7)	0.0323 (9)	0.0300 (7)	0.0174 (7)	0.0027 (6)	0.0104 (6)
O2	0.0356 (9)	0.0548 (11)	0.0228 (7)	0.0335 (9)	0.0132 (6)	0.0209 (7)

Geometric parameters (Å, º) top

C1—O3	1.2547 (16)	O3—Na1ⁱⁱ	2.3416 (14)
C1—C2	1.525 (3)	C4—C5	1.386 (2)
C2—C3	1.389 (2)	C4—N2	1.471 (2)
C3—C4	1.386 (2)	C5—H5	0.93
C3—H3	0.93	N2—O2	1.220 (2)
O3—Na1ⁱ	2.3083 (11)	N2—O1	1.231 (2)

O3ⁱⁱⁱ—C1—O3	126.5 (2)	O3^iv—Na1—O3^v	167.89 (8)
O3—C1—C2	116.77 (11)	O3^v—Na1—O3^vi	86.31 (5)
C3ⁱⁱⁱ—C2—C3	119.9 (2)	O3^v—Na1—O3^vii	102.24 (5)
C3—C2—C1	120.06 (11)	O3^vi—Na1—O3^vii	91.20 (7)
C4—C3—C2	118.90 (16)	O3^iv—Na1—O1	79.55 (5)
C4—C3—H3	120.5	O3^v—Na1—O1	93.24 (5)
C2—C3—H3	120.5	O3^vi—Na1—O1	82.64 (5)
C1—O3—Na1ⁱ	131.53 (9)	O3^vii—Na1—O1	162.96 (5)
C1—O3—Na1ⁱⁱ	125.81 (12)	O1^viii—Na1—O1	107.43 (8)
Na1ⁱ—O3—Na1ⁱⁱ	85.34 (5)	O3^iv—Na1—Na1^ix	47.77 (3)
C3—C4—C5	123.23 (16)	O3^v—Na1—Na1^ix	143.85 (5)
C3—C4—N2	119.02 (15)	O3^vi—Na1—Na1^ix	77.64 (3)
C5—C4—N2	117.74 (16)	O3^vii—Na1—Na1^ix	46.88 (4)
C4ⁱⁱⁱ—C5—C4	115.8 (2)	O1^viii—Na1—Na1^ix	108.62 (3)
C4—C5—H5	122.1	O1—Na1—Na1^ix	116.10 (3)
O2—N2—O1	123.91 (16)	Na1^ix—Na1—Na1^x	100.20 (3)
O2—N2—C4	118.34 (14)	N2—O1—Na1	160.96 (12)
O1—N2—C4	117.74 (15)

Symmetry codes: (i) −y+1, x−y+1, z+1/3; (ii) x−1, y, z; (iii) x−y+1, −y+2, −z−1/3; (iv) −x+1, −x+y, −z+1/3; (v) −x+y, −x+1, z−1/3; (vi) y, x+1, −z; (vii) x+1, y, z; (viii) y, x, −z; (ix) −y+2, x−y+1, z+1/3; (x) −x+y+1, −x+2, z−1/3.

Footnotes

‡Current address: Pharmaceutical R&D, Pfizer Global R&D (IPC 435), Ramsgate Road, Sandwich, Kent CT13 9NJ, England

Acknowledgements

The authors thank Sanofī–Aventis Ltd for funding.

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