Poly[(μ5-2-methyl-3,5-dinitro­benzoato)sodium]

Danish, M.; Saleem, I.; Ahmad, N.; Raza, A.R.; Starosta, W.; Leciejewicz, J.

doi:10.1107/S1600536810000498

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page m137

https://doi.org/10.1107/S1600536810000498

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Poly[(μ₅-2-methyl-3,5-dinitrobenzoato)sodium]

Muhammad Danish,^a ^* Iram Saleem,^a Nazir Ahmad,^a Abdul Rauf Raza,^a Wojciech Starosta ^b and Janusz Leciejewicz ^b

^aDepartment of Chemistry, University of Sargodha, Sargodha 40100, Pakistan, and ^bInstitute of Nuclear Chemistry and Technology, ul.Dorodna 16, 03-195 Warszawa, Poland
^*Correspondence e-mail: drdanish62@gmail.com

(Received 11 December 2009; accepted 5 January 2010; online 9 January 2010)

In the crystal of the title coordination polymer, [Na(C₈H₅N₂O₆)]_n, the Na(I) ion is linked to five nearby anions. Their bonding modes are three monodentate carboxylate O atoms, one O,O′-bidentate carboxylate group and one O,O′-bidentate nitro group. This results in an irregular NaO₇ coordination geometry for the metal ion. This connectivity leads to a layered network propagating in (100).

Related literature

For the structure of a trimethyl-tin complex with the ortho-toluate ligand, see: Danish et al. (2010 ).

Experimental

Crystal data

[Na(C₈H₅N₂O₆)]
M_r = 248.13
Orthorhombic, P b c n
a = 27.8428 (13) Å
b = 10.452 (2) Å
c = 6.642 (6) Å
V = 1932.8 (17) Å³
Z = 8
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 293 K
0.42 × 0.14 × 0.08 mm

Data collection

Kuma KM-4 four-circle diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England]$ ) T_min = 0.975, T_max = 0.984
2659 measured reflections
2406 independent reflections
1273 reflections with I > 2σ(I)
R_int = 0.047
3 standard reflections every 200 reflections intensity decay: 0.01%

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.132
S = 1.00
2406 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Selected bond lengths (Å)

Na1—O1	2.4567 (19)
Na1—O2	2.780 (2)
Na1—O2ⁱ	2.3571 (17)
Na1—O1ⁱⁱ	2.364 (3)
Na1—O2ⁱⁱⁱ	2.383 (3)
Na1—O22^iv	2.6102 (19)
Na1—O21^iv	2.635 (2)
Symmetry codes: (i) -x+2, -y, -z+2; (ii) $[x, -y, z+{\script{1\over 2}}]$ ; (iii) $[x, -y, z-{\script{1\over 2}}]$ ; (iv) x, y-1, z.

Data collection: KM-4 Software (Kuma, 1996 $[Kuma (1996). KM-4 Software. Kuma Diffraction Ltd, Wrocław, Poland.]$ ); cell refinement: KM-4 Software; data reduction: DATAPROC (Kuma, 2001 $[Kuma (2001). DATAPROC. Kuma Diffraction Ltd, Wrocław, Poland.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810000498/hb5280sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810000498/hb5280Isup2.hkl

checkCIF report

Comment top

The structure of compound (1) is composed of molecular sheets in which Na(I) ions are bridged by ligand carboxylate and nitro-group O atoms. The carboxylate O1 atom acts as bidentate and chelates Na1 and Na1(IV) ions, the O2 atom is bonded to Na1(II) and Na1(V) ions and to the Na1 ion at a longer distance of 2.780 (2) Å. The O1, O2, Na and Na^(II) ions form a distorted plane [r.m.s. 0.0261 (2) Å], the O1 atom chelates the Na^(IV) ion below this plane, the O2 atom - the Na^(V)ion above, giving rise to a molecular column. However, when distances between atoms from a nitro-group of an adjacent ligand to the Na ion are accounted for, the columns form molecular sheets. The coordination geometry of the Na1 ion is represented by a strongly distorted eight-faced polyhedron with an equatorial plane formed by carboxylate O1 and O2(II), nitro O21(VI) and O22(VI) atoms and Na1 [r.m.s. 0.1217 (2)Å]. Carboxylate O2(IV) is at an apex on one side, O2 and O1(V) form two apices on the other side of the equatorial plane. The toluene ring is planar [r.m.s. 0.0070 (2) Å], the carboxylate group makes with it a dihedral angle of 78.0 (2)^o, the nitro-groups - dihedral angles of 42.0 (2)^o (N1/O11/O12) and 9.5 (2)^o (N2/O21/O22). The sheets are held together via weak interactions of the van der Waals type since the closest approach between two atoms from adjacent sheets is 3.54 (4) Å.

Related literature top

For the structure of a trimethyl-tin complex with the ortho-toluate ligand, see: Danish et al. (2010).

Experimental top

0.0119 mol of 3,5-dinitro-ortho toluic acid was suspended in 15 ml of distilled water contained in a round-bottom flask. Then, 0.0119 mol of an aqueous solution of sodium bicarbonate was added drop-wise with stirring. The mixture was refluxed for 3 h and concentrated to half of its volume, then left at room temperature. Crude crystals appeared within a week. Yellow needles of (I) crystals were obtained by recrystallization from a water/ethanol 3:1 mixture at room temperature.

Structure description top

For the structure of a trimethyl-tin complex with the ortho-toluate ligand, see: Danish et al. (2010).

Computing details top

Data collection: KM-4 Software (Kuma, 1996); cell refinement: KM-4 Software (Kuma, 1996); data reduction: DATAPROC (Kuma, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A structural unit of (1) with 50% probability displacement ellipsoids. Symmetry code: ^(I) x,y + 1,z; ^(II) -x + 2,-y,-z + 2; ^(III) -x + 2,y,-z + 3/2; ^(IV) x,-y,z - 1/2; ^(V) x,-y,z + 1/2; ^(VI) x,y - 1,z.
	Fig. 2. Packing diagram of the structure.

Poly[(µ₅-2-methyl-3,5-dinitrobenzoato)sodium] top

Crystal data top

[Na(C₈H₅N₂O₆)]	D_x = 1.705 Mg m⁻³
M_r = 248.13	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 25 reflections
a = 27.8428 (13) Å	θ = 6–15°
b = 10.452 (2) Å	µ = 0.18 mm⁻¹
c = 6.642 (6) Å	T = 293 K
V = 1932.8 (17) Å³	Needle, yellow
Z = 8	0.42 × 0.14 × 0.08 mm
F(000) = 1008

Data collection top

Kuma KM-4 four-circle diffractometer	1273 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.047
Graphite monochromator	θ_max = 29.1°, θ_min = 1.5°
profile data from ω/2θ scans	h = 0→36
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	k = −14→1
T_min = 0.975, T_max = 0.984	l = 0→9
2659 measured reflections	3 standard reflections every 200 reflections
2406 independent reflections	intensity decay: 0.01%

Refinement top

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) = 0.132	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0681P)² + 0.6169P] where P = (F_o² + 2F_c²)/3
2406 reflections	(Δ/σ)_max = 0.001
155 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Na(C₈H₅N₂O₆)]	V = 1932.8 (17) Å³
M_r = 248.13	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 27.8428 (13) Å	µ = 0.18 mm⁻¹
b = 10.452 (2) Å	T = 293 K
c = 6.642 (6) Å	0.42 × 0.14 × 0.08 mm

Data collection top

Kuma KM-4 four-circle diffractometer	1273 reflections with I > 2σ(I)
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	R_int = 0.047
T_min = 0.975, T_max = 0.984	3 standard reflections every 200 reflections
2659 measured reflections	intensity decay: 0.01%
2406 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.132	H-atom parameters constrained
S = 1.00	Δρ_max = 0.33 e Å⁻³
2406 reflections	Δρ_min = −0.30 e Å⁻³
155 parameters

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
Na1	0.95606 (3)	−0.10192 (7)	0.92650 (12)	0.0318 (2)
O2	0.96094 (6)	0.14635 (16)	1.0752 (2)	0.0389 (4)
O11	0.75046 (8)	0.2906 (2)	0.8738 (4)	0.0747 (7)
O1	0.93442 (7)	0.10334 (16)	0.7707 (3)	0.0482 (5)
N1	0.77183 (7)	0.3679 (2)	0.9765 (4)	0.0427 (5)
C1	0.90187 (7)	0.28318 (18)	0.9385 (3)	0.0246 (4)
C7	0.93555 (7)	0.16846 (18)	0.9265 (3)	0.0268 (4)
C5	0.89172 (7)	0.50978 (19)	0.9440 (3)	0.0273 (4)
C3	0.82465 (7)	0.3756 (2)	0.9576 (3)	0.0294 (5)
C2	0.85223 (7)	0.26469 (19)	0.9491 (3)	0.0283 (5)
C4	0.84279 (7)	0.4982 (2)	0.9550 (3)	0.0287 (4)
H4	0.8228	0.5695	0.9604	0.034*
C6	0.92178 (8)	0.40496 (18)	0.9386 (3)	0.0273 (4)
H6	0.9549	0.4157	0.9350	0.033*
C8	0.83187 (9)	0.1325 (2)	0.9644 (5)	0.0479 (7)
H8A	0.8039	0.1339	1.0489	0.072*
H8B	0.8555	0.0762	1.0214	0.072*
H8C	0.8232	0.1027	0.8326	0.072*
O12	0.75280 (7)	0.4416 (2)	1.0929 (3)	0.0605 (6)
N2	0.91229 (7)	0.63855 (17)	0.9404 (3)	0.0328 (4)
O21	0.88557 (7)	0.72989 (15)	0.9215 (3)	0.0461 (5)
O22	0.95584 (7)	0.64912 (16)	0.9575 (3)	0.0537 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Na1	0.0349 (5)	0.0263 (4)	0.0341 (5)	−0.0013 (3)	0.0000 (4)	0.0016 (3)
O2	0.0341 (9)	0.0433 (9)	0.0392 (9)	0.0091 (7)	−0.0041 (7)	0.0086 (7)
O11	0.0389 (9)	0.0753 (15)	0.1098 (19)	−0.0043 (11)	−0.0178 (13)	−0.0198 (15)
O1	0.0640 (12)	0.0410 (9)	0.0396 (10)	0.0191 (9)	0.0004 (9)	−0.0092 (8)
N1	0.0259 (9)	0.0409 (10)	0.0614 (14)	0.0058 (8)	−0.0002 (10)	0.0064 (11)
C1	0.0269 (9)	0.0237 (8)	0.0233 (10)	0.0025 (7)	−0.0026 (9)	0.0012 (8)
C7	0.0245 (9)	0.0250 (9)	0.0309 (11)	0.0025 (8)	0.0038 (9)	0.0057 (9)
C5	0.0373 (11)	0.0244 (9)	0.0204 (9)	−0.0007 (8)	−0.0007 (9)	0.0008 (8)
C3	0.0257 (10)	0.0349 (11)	0.0276 (10)	0.0022 (8)	−0.0011 (8)	−0.0009 (9)
C2	0.0275 (10)	0.0283 (10)	0.0292 (11)	−0.0004 (8)	−0.0018 (9)	0.0014 (9)
C4	0.0332 (9)	0.0294 (9)	0.0235 (10)	0.0085 (9)	0.0002 (9)	0.0016 (8)
C6	0.0291 (10)	0.0279 (9)	0.0247 (10)	−0.0015 (8)	−0.0004 (8)	0.0018 (9)
C8	0.0372 (12)	0.0314 (11)	0.0751 (19)	−0.0062 (10)	0.0010 (14)	0.0028 (12)
O12	0.0391 (9)	0.0542 (11)	0.0881 (15)	0.0131 (9)	0.0199 (11)	0.0039 (12)
N2	0.0467 (11)	0.0250 (8)	0.0266 (9)	−0.0013 (8)	0.0019 (9)	0.0017 (7)
O21	0.0611 (12)	0.0252 (7)	0.0518 (11)	0.0044 (7)	−0.0022 (10)	0.0003 (7)
O22	0.0440 (10)	0.0352 (9)	0.0819 (14)	−0.0116 (8)	0.0011 (10)	0.0017 (9)

Geometric parameters (Å, º) top

Na1—O1	2.4567 (19)	C1—C2	1.397 (3)
Na1—O2	2.780 (2)	C1—C7	1.524 (3)
Na1—O2ⁱ	2.3571 (17)	C5—C4	1.370 (3)
Na1—O1ⁱⁱ	2.364 (3)	C5—C6	1.379 (3)
Na1—O2ⁱⁱⁱ	2.383 (3)	C5—N2	1.463 (3)
Na1—O22^iv	2.6102 (19)	C3—C4	1.377 (3)
Na1—O21^iv	2.635 (2)	C3—C2	1.392 (3)
Na1—Na1ⁱ	3.3881 (17)	C2—C8	1.497 (3)
Na1—Na1^v	3.389 (2)	C4—H4	0.9300
Na1—Na1ⁱⁱⁱ	3.946 (3)	C6—H6	0.9300
O2—C7	1.237 (3)	C8—H8A	0.9600
O2—Na1ⁱ	2.3571 (17)	C8—H8B	0.9600
O2—Na1ⁱⁱ	2.383 (3)	C8—H8C	0.9600
O11—N1	1.213 (3)	N2—O21	1.217 (2)
O1—C7	1.239 (3)	N2—O22	1.223 (2)
O1—Na1ⁱⁱⁱ	2.364 (3)	N2—Na1^vi	2.975 (2)
N1—O12	1.212 (3)	O21—Na1^vi	2.635 (2)
N1—C3	1.478 (3)	O22—Na1^vi	2.6102 (19)
C1—C6	1.388 (3)

O2ⁱ—Na1—O1ⁱⁱ	104.67 (7)	C6—C1—C2	121.45 (18)
O2ⁱ—Na1—O2ⁱⁱⁱ	84.31 (7)	C6—C1—C7	118.39 (18)
O1ⁱⁱ—Na1—O2ⁱⁱⁱ	163.77 (7)	C2—C1—C7	120.16 (17)
O2ⁱ—Na1—O1	114.23 (7)	O2—C7—O1	125.38 (19)
O1ⁱⁱ—Na1—O1	110.50 (7)	O2—C7—C1	117.19 (18)
O2ⁱⁱⁱ—Na1—O1	76.81 (7)	O1—C7—C1	117.40 (18)
O2ⁱ—Na1—O22^iv	78.83 (6)	C4—C5—C6	122.34 (19)
O1ⁱⁱ—Na1—O22^iv	85.23 (7)	C4—C5—N2	118.12 (18)
O2ⁱⁱⁱ—Na1—O22^iv	83.28 (7)	C6—C5—N2	119.53 (19)
O1—Na1—O22^iv	154.57 (7)	C4—C3—C2	124.91 (19)
O2ⁱ—Na1—O21^iv	126.78 (6)	C4—C3—N1	114.59 (18)
O1ⁱⁱ—Na1—O21^iv	79.53 (6)	C2—C3—N1	120.47 (19)
O2ⁱⁱⁱ—Na1—O21^iv	84.27 (6)	C3—C2—C1	115.62 (18)
O1—Na1—O21^iv	113.24 (7)	C3—C2—C8	123.86 (19)
O22^iv—Na1—O21^iv	48.26 (6)	C1—C2—C8	120.38 (18)
O2ⁱ—Na1—O2	97.91 (6)	C5—C4—C3	116.57 (19)
O1ⁱⁱ—Na1—O2	71.01 (6)	C5—C4—H4	121.7
O2ⁱⁱⁱ—Na1—O2	121.81 (6)	C3—C4—H4	121.7
O1—Na1—O2	49.20 (6)	C5—C6—C1	119.07 (19)
O22^iv—Na1—O2	154.51 (7)	C5—C6—H6	120.5
O21^iv—Na1—O2	131.58 (6)	C1—C6—H6	120.5
C7—O2—Na1ⁱ	126.39 (14)	C2—C8—H8A	109.5
C7—O2—Na1ⁱⁱ	141.83 (14)	C2—C8—H8B	109.5
Na1ⁱ—O2—Na1ⁱⁱ	91.28 (6)	H8A—C8—H8B	109.5
C7—O2—Na1	82.10 (12)	C2—C8—H8C	109.5
Na1ⁱ—O2—Na1	82.09 (6)	H8A—C8—H8C	109.5
Na1ⁱⁱ—O2—Na1	99.40 (6)	H8B—C8—H8C	109.5
C7—O1—Na1ⁱⁱⁱ	143.56 (16)	O21—N2—O22	123.02 (18)
C7—O1—Na1	97.00 (14)	O21—N2—C5	118.96 (19)
Na1ⁱⁱⁱ—O1—Na1	109.83 (7)	O22—N2—C5	118.02 (17)
O12—N1—O11	124.5 (2)	N2—O21—Na1^vi	93.83 (13)
O12—N1—C3	117.0 (2)	N2—O22—Na1^vi	94.88 (13)
O11—N1—C3	118.5 (2)

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

Experimental details

Crystal data
Chemical formula	[Na(C₈H₅N₂O₆)]
M_r	248.13
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	27.8428 (13), 10.452 (2), 6.642 (6)
V (Å³)	1932.8 (17)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.42 × 0.14 × 0.08

Data collection
Diffractometer	Kuma KM-4 four-circle diffractometer
Absorption correction	Analytical (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.975, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	2659, 2406, 1273
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.683

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.132, 1.00
No. of reflections	2406
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.30

Computer programs: KM-4 Software (Kuma, 1996), DATAPROC (Kuma, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Na1—O1	2.4567 (19)	Na1—O2ⁱⁱⁱ	2.383 (3)
Na1—O2	2.780 (2)	Na1—O22^iv	2.6102 (19)
Na1—O2ⁱ	2.3571 (17)	Na1—O21^iv	2.635 (2)
Na1—O1ⁱⁱ	2.364 (3)

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

Acknowledgements

MD is grateful to the Australian Government for the award of Endeavour Post Doctoral Fellowships for the year 2009–2010

References

Danish, M., Saleem, I., Ahmad, N., Starosta, W. & Leciejewicz, J. (2010). Acta Cryst. E66, m4. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kuma (1996). KM-4 Software. Kuma Diffraction Ltd, Wrocław, Poland. Google Scholar
Kuma (2001). DATAPROC. Kuma Diffraction Ltd, Wrocław, Poland. Google Scholar
Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar