Tetra­kis(μ2-2-methyl-3,5-dinitro­benzoato-κ2O1:O1′)bis­[aqua­copper(II)] tetra­hydrate

Danish, M.; Ghafoor, S.; Tahir, M.N.; Ahmad, N.; Nisa, M.

doi:10.1107/S1600536811000547

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 2| February 2011| Pages m168-m169

doi:10.1107/S1600536811000547

Open

access

Tetrakis(μ₂-2-methyl-3,5-dinitrobenzoato-κ²O¹:O^1′)bis[aquacopper(II)] tetrahydrate

Muhammad Danish,^a Sabiha Ghafoor,^a M. Nawaz Tahir,^b ^* Nazir Ahmad ^a and Mehwish Nisa ^a

^aDepartment of Chemistry, University of Sargodha, Sargodha, Pakistan, and ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 4 January 2011; accepted 5 January 2011; online 15 January 2011)

The title compound, [Cu₂(C₈H₅N₂O₆)₄(H₂O)₂]·4H₂O, forms a centrosymmetric paddle-wheel-type dimer with an intramolecular Cu⋯Cu distance of 2.6540 (4) Å. The Cu^II atom is in a square-pyramidal coordination environment formed by four O atoms of four carboxylate groups and one water molecule, which is located in the apical position. The carboxylate groups are twisted relative to the benzene rings by 11.09 (16) and 45.55 (19)°. The nitro groups are not coplanar with the parent aromatic rings [dihedral angles = 16.2 (3)–51.45 (14)°]. O—H⋯O hydrogen bonds between the coordinated water molecules and one of the nitro groups, as well as π–π stacking interactions [centroid–centroid distance = 3.5764 (12) Å] between the benzene rings, assemble the complex molecules into a one-dimensional polymeric structure which is further extended into a three-dimensional polymeric network via O—H⋯O hydrogen bonds involving the water molecules of crystallization.

Related literature

For related crystal structures, see: Chen et al. (2007 ); Danish et al. (2010 ); Moncol et al. (2006 ); Stachova et al. (2004 ); Viossat et al. (2005 ).

Experimental

Crystal data

[Cu₂(C₈H₅N₂O₆)₄(H₂O)₂]·4H₂O
M_r = 1135.76
Monoclinic, P 2₁ /n
a = 8.9757 (3) Å
b = 22.5582 (8) Å
c = 11.2698 (3) Å
β = 104.443 (1)°
V = 2209.75 (12) Å³
Z = 2
Mo Kα radiation
μ = 1.08 mm⁻¹
T = 296 K
0.30 × 0.24 × 0.22 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.743, T_max = 0.782
21133 measured reflections
5449 independent reflections
4344 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.088
S = 1.02
5449 reflections
345 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O1	1.9616 (16)
Cu1—O7	1.9749 (16)
Cu1—O8	1.9637 (15)
Cu1—O13	2.0914 (19)
Cu1—O2ⁱ	1.9595 (16)
Symmetry code: (i) -x, -y, -z+2.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13—H13A⋯O14ⁱⁱ	0.80 (3)	1.84 (3)	2.641 (3)	175 (3)
O13—H13B⋯O10ⁱⁱⁱ	0.77 (2)	2.22 (2)	2.838 (2)	138 (3)
O14—H14A⋯O15^iv	0.81 (3)	1.95 (3)	2.758 (4)	172 (3)
O14—H14B⋯O7	0.80 (3)	2.51 (4)	3.182 (3)	143 (4)
O15—H15A⋯O12^v	0.83 (4)	2.16 (4)	2.953 (4)	161 (4)
O15—H15B⋯O5^vi	0.84 (3)	2.17 (2)	2.996 (4)	168 (4)
O15—H15B⋯O6^vi	0.84 (3)	2.60 (4)	3.273 (4)	138 (4)
Symmetry codes: (ii) -x+1, -y, -z+2; (iii) x, y, z+1; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (v) x+1, y, z; (vi) x, y, z-1.

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811000547/gk2339sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811000547/gk2339Isup2.hkl

checkCIF report

Comment top

Recently we have reported the synthesis and crystal structure of tetrakis(µ-2-methylbenzoato-κ²O:O^')bis[(methanol-O)copper(II)]. In continuation to our interest with the metal carboxylate chemistry, the title compound (I), (Fig. 1) is being reported here.

The crystal structure of (II) i.e., diaqua-tetrakis(µ₂-2,3,5-tri-iodobenzoato-k²O:O^')-di-copper(ii) bis(methanol-κO)-tetrakis(µ₂-2,3,5-tri-iodobenzoato- κ₂O:O^')-di-copper(ii) methanol solvate (Chen et al., 2007), (III) i.e., tetrakis(µ₂-2-nitrobenzoato-O,O^')-bis(aqua-copper(ii)) ethanol solvate (Moncol et al., 2006), (IV) i.e., tetrakis(µ₂-2-(3-trifluoromethylphenyl)aminonicotinato)-diaqua-di-copper(ii) N,N-dimethylformamide solvate (Viossat et al., 2005) and (V) i.e., diaqua-tetrakis(2-nitrobenzoato-O,O^')-di-copper(ii) dihydrate (Stachova et al., 2004) have been published which are related to the title compound (I) due to the coordination around copper.

The structure of (I) is centrosymmetric with a square pyramidal coordination around the Cu-atoms. Four oxygen atoms (O1/O2ⁱ/O7/O8; i = -x, -y, -z + 2) from four carboxylate groups are in plane [r. m.s deviation of 0.0014 Å] and coordinated to copper(II) with bond distance of 1.9593 (15) – 1.9749 (15) Å. The Cu—O [2.0909 (17) Å] bond of water molecule is longer as compared to Cu—O bonds of carboxylate groups. The Cu atom is at a distance of 0.2189 (8) Å from the mean square plane of carboxylate O-atoms. The separation of Cu—Cu is 2.6540 (4) Å. These values are in agreement with the reported structures [Table 1]. The toluene groups A (C2—C8) and B (C10—C16) are almost planar with r. m.s deviation of 0.0524 Å and 0.0363 Å and are nearly perpendicular to each other. The dihedral angle between A/B is 89.33 (6)°. The carboxylate moiety C (O1/C1/O2), nitro groups D (O3/N1/O4) and E (O5/N2/O6) are oriented at dihedral angles of 11.09 (16), 51.45 (14) and 45.30 (33)°, respectively with the parent toluene (A) moiety. In the other ligand, the carboxylate moiety F (O7/C9/O8ⁱ), nitro groups G (O9/N3/O10) and H (O11/N4/O12) are oriented at dihedral angles of 45.55 (19), 40.43 (23) and 16.20 (34)°, respectively with the parent toluene (B) moiety. The molecules are stabilized in the form of three-dimensional polymeric network due to strong H-bonding (Table 2, Fig. 2, Fig. 3). There also exists a π···π interaction between the benzene rings (C10—C15) with centroid-to- centroid distance of 3.5764 (12) Å.

Related literature top

For related and crystal structures, see: Chen et al. (2007); Danish et al. (2010); Moncol et al. (2006); Stachova et al. (2004); Viossat et al. (2005).

Experimental top

Aqueous solutions of sodium salt of 3,5-dinitro- o-toluic acid (0.496 g, 2.0 mol) and copper chloride dihydrate (0.170 g, 1.0 mmol) were prepared separately. Both solutions were mixed in 100 ml round-bottom flask at room temperature. On mixing dirty green precipitate was formed at the begining and it disappeared on continuous stirring of the reaction mixture for 4 h. The reaction mixture was filtered and the filtrate was concentrated by heating for few minutes. The concentrated solution was kept at room temperature for 72 h to afford greenish blue prisms of of the title compound.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title compound with the atom numbering scheme. The displacement ellipsoids are drawn at the 50% probability level. H-atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The partial packing (PLATON; Spek, 2009) which shows the H-bonding mode with neighbouring molecules through dotted lines except which are present in coordination sphere.
	Fig. 3. The partial packing (PLATON; Spek, 2009) which shows that molecules form three-dimensional polymeric network due to strong intermolecular H-bondings.

Tetrakis(µ₂-2-methyl-3,5-dinitrobenzoato- κ²O¹:O^1')bis[aquacopper(II)] tetrahydrate top

Crystal data top

[Cu₂(C₈H₅N₂O₆)₄(H₂O)₂]·4H₂O	F(000) = 1156
M_r = 1135.76	D_x = 1.707 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4344 reflections
a = 8.9757 (3) Å	θ = 2.1–28.3°
b = 22.5582 (8) Å	µ = 1.08 mm⁻¹
c = 11.2698 (3) Å	T = 296 K
β = 104.443 (1)°	Prism, blue
V = 2209.75 (12) Å³	0.30 × 0.24 × 0.22 mm
Z = 2

Data collection top

Bruker Kappa APEXII CCD diffractometer	5449 independent reflections
Radiation source: fine-focus sealed tube	4344 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Detector resolution: 7.50 pixels mm^-1	θ_max = 28.3°, θ_min = 2.1°
ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −30→30
T_min = 0.743, T_max = 0.782	l = −15→9
21133 measured reflections

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0398P)² + 0.8547P] where P = (F_o² + 2F_c²)/3
5449 reflections	(Δ/σ)_max = 0.001
345 parameters	Δρ_max = 0.33 e Å⁻³
6 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[Cu₂(C₈H₅N₂O₆)₄(H₂O)₂]·4H₂O	V = 2209.75 (12) Å³
M_r = 1135.76	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.9757 (3) Å	µ = 1.08 mm⁻¹
b = 22.5582 (8) Å	T = 296 K
c = 11.2698 (3) Å	0.30 × 0.24 × 0.22 mm
β = 104.443 (1)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	5449 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	4344 reflections with I > 2σ(I)
T_min = 0.743, T_max = 0.782	R_int = 0.035
21133 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	6 restraints
wR(F²) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.33 e Å⁻³
5449 reflections	Δρ_min = −0.28 e Å⁻³
345 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
Cu1	0.14133 (3)	−0.01627 (1)	1.05844 (2)	0.0264 (1)
O1	0.17167 (19)	0.06719 (7)	1.10736 (17)	0.0528 (6)
O2	−0.06417 (19)	0.09368 (7)	1.00866 (15)	0.0474 (5)
O3	−0.1238 (3)	0.32675 (9)	0.9849 (2)	0.0826 (9)
O4	−0.0417 (3)	0.36016 (8)	1.1678 (2)	0.0701 (8)
O5	0.5065 (2)	0.29719 (9)	1.30010 (18)	0.0624 (7)
O6	0.5609 (2)	0.20680 (10)	1.2665 (3)	0.0901 (9)
O7	0.19256 (18)	0.00393 (8)	0.90275 (14)	0.0461 (5)
O8	0.04616 (18)	−0.02830 (8)	1.19572 (13)	0.0445 (5)
O9	0.2910 (2)	−0.08610 (9)	0.45982 (19)	0.0680 (8)
O10	0.3870 (2)	−0.01075 (10)	0.38692 (16)	0.0623 (7)
O11	0.0204 (3)	0.15433 (11)	0.34615 (17)	0.0807 (9)
O12	−0.0072 (3)	0.18886 (9)	0.51609 (19)	0.0792 (9)
O13	0.3664 (2)	−0.04335 (10)	1.14010 (15)	0.0592 (7)
N1	−0.0457 (3)	0.32313 (9)	1.0898 (2)	0.0496 (7)
N2	0.4706 (2)	0.24745 (10)	1.2591 (2)	0.0518 (7)
N3	0.3119 (2)	−0.03328 (11)	0.45226 (17)	0.0472 (7)
N4	0.0329 (3)	0.15041 (10)	0.45558 (18)	0.0510 (7)
C1	0.0668 (2)	0.10469 (9)	1.07283 (18)	0.0321 (6)
C2	0.1073 (2)	0.16812 (8)	1.10974 (17)	0.0309 (6)
C3	−0.0028 (3)	0.21412 (9)	1.08940 (18)	0.0347 (6)
C4	0.0571 (3)	0.27102 (9)	1.1212 (2)	0.0373 (6)
C5	0.2074 (3)	0.28347 (10)	1.1774 (2)	0.0400 (7)
C6	0.3078 (3)	0.23623 (10)	1.19871 (19)	0.0377 (7)
C7	0.2606 (3)	0.17952 (9)	1.16425 (18)	0.0350 (6)
C8	−0.1731 (3)	0.20411 (11)	1.0466 (3)	0.0523 (8)
C9	0.0935 (2)	0.02030 (8)	0.81066 (18)	0.0308 (6)
C10	0.1378 (2)	0.03256 (9)	0.69218 (17)	0.0303 (6)
C11	0.2268 (2)	−0.00702 (9)	0.64135 (18)	0.0333 (6)
C12	0.2367 (2)	0.00750 (10)	0.52214 (19)	0.0353 (6)
C13	0.1764 (2)	0.05764 (10)	0.45945 (18)	0.0379 (7)
C14	0.0982 (2)	0.09566 (10)	0.51708 (18)	0.0355 (6)
C15	0.0760 (2)	0.08360 (9)	0.63150 (18)	0.0341 (6)
C16	0.3062 (3)	−0.05950 (12)	0.7111 (2)	0.0517 (8)
O14	0.4622 (3)	0.09823 (11)	0.9851 (3)	0.0827 (10)
O15	0.8508 (3)	0.29497 (14)	0.3805 (4)	0.1215 (14)
H5	0.24001	0.32188	1.20013	0.0480*
H7	0.33171	0.14872	1.17755	0.0421*
H8A	−0.20137	0.19949	0.95920	0.0784*
H8B	−0.22654	0.23750	1.06903	0.0784*
H8C	−0.20028	0.16893	1.08435	0.0784*
H13	0.18803	0.06549	0.38126	0.0455*
H13A	0.419 (3)	−0.0616 (13)	1.105 (2)	0.0711*
H13B	0.389 (4)	−0.0520 (14)	1.2082 (17)	0.0711*
H15	0.01980	0.10960	0.66751	0.0409*
H16A	0.34251	−0.04933	0.79617	0.0776*
H16B	0.39179	−0.07080	0.67924	0.0776*
H16C	0.23523	−0.09198	0.70265	0.0776*
H14A	0.428 (5)	0.1281 (12)	0.948 (3)	0.0993*
H14B	0.410 (4)	0.0722 (14)	1.000 (4)	0.0993*
H15A	0.910 (5)	0.2681 (17)	0.414 (4)	0.1457*
H15B	0.755 (2)	0.291 (2)	0.352 (4)	0.1457*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0288 (1)	0.0251 (1)	0.0263 (1)	0.0023 (1)	0.0088 (1)	0.0015 (1)
O1	0.0498 (9)	0.0261 (8)	0.0741 (12)	0.0047 (7)	−0.0001 (8)	−0.0090 (8)
O2	0.0451 (9)	0.0282 (8)	0.0629 (10)	0.0005 (7)	0.0023 (8)	−0.0085 (7)
O3	0.0964 (17)	0.0585 (13)	0.0761 (14)	0.0322 (12)	−0.0102 (12)	0.0002 (11)
O4	0.0857 (15)	0.0430 (11)	0.0871 (14)	0.0112 (10)	0.0318 (12)	−0.0168 (10)
O5	0.0623 (12)	0.0517 (11)	0.0660 (12)	−0.0168 (9)	0.0024 (9)	−0.0118 (9)
O6	0.0472 (12)	0.0617 (14)	0.147 (2)	0.0052 (10)	−0.0027 (13)	−0.0153 (14)
O7	0.0371 (8)	0.0709 (11)	0.0326 (8)	0.0032 (8)	0.0129 (7)	0.0138 (8)
O8	0.0399 (9)	0.0664 (11)	0.0310 (8)	0.0109 (8)	0.0160 (6)	0.0103 (7)
O9	0.0780 (14)	0.0575 (13)	0.0740 (13)	0.0053 (11)	0.0294 (11)	−0.0234 (10)
O10	0.0497 (10)	0.1042 (16)	0.0394 (9)	−0.0029 (10)	0.0233 (8)	−0.0130 (10)
O11	0.1012 (17)	0.1012 (18)	0.0450 (10)	0.0273 (14)	0.0284 (11)	0.0341 (11)
O12	0.126 (2)	0.0554 (12)	0.0644 (13)	0.0282 (13)	0.0394 (13)	0.0195 (10)
O13	0.0469 (10)	0.0925 (15)	0.0348 (9)	0.0330 (10)	0.0037 (8)	−0.0047 (10)
N1	0.0556 (13)	0.0312 (10)	0.0638 (14)	0.0042 (9)	0.0181 (11)	−0.0027 (10)
N2	0.0475 (12)	0.0485 (12)	0.0554 (13)	−0.0071 (10)	0.0054 (10)	−0.0010 (10)
N3	0.0392 (10)	0.0671 (15)	0.0365 (10)	0.0007 (10)	0.0116 (8)	−0.0167 (10)
N4	0.0581 (13)	0.0568 (13)	0.0418 (11)	0.0040 (10)	0.0192 (10)	0.0180 (10)
C1	0.0438 (12)	0.0261 (10)	0.0300 (10)	−0.0011 (8)	0.0162 (9)	−0.0007 (8)
C2	0.0423 (11)	0.0244 (9)	0.0288 (9)	−0.0011 (8)	0.0144 (8)	−0.0003 (8)
C3	0.0439 (12)	0.0298 (10)	0.0324 (10)	0.0012 (9)	0.0134 (9)	−0.0002 (8)
C4	0.0473 (12)	0.0274 (10)	0.0387 (11)	0.0048 (9)	0.0133 (10)	0.0005 (9)
C5	0.0531 (13)	0.0263 (10)	0.0408 (12)	−0.0050 (9)	0.0123 (10)	−0.0014 (9)
C6	0.0409 (12)	0.0357 (11)	0.0357 (11)	−0.0043 (9)	0.0081 (9)	−0.0010 (9)
C7	0.0417 (12)	0.0291 (10)	0.0361 (11)	0.0041 (9)	0.0131 (9)	0.0011 (9)
C8	0.0424 (13)	0.0396 (13)	0.0738 (17)	0.0033 (10)	0.0125 (12)	−0.0054 (12)
C9	0.0393 (11)	0.0265 (10)	0.0292 (10)	−0.0038 (8)	0.0137 (8)	−0.0023 (8)
C10	0.0339 (10)	0.0323 (10)	0.0264 (9)	−0.0059 (8)	0.0109 (8)	−0.0009 (8)
C11	0.0328 (10)	0.0353 (11)	0.0337 (10)	−0.0048 (8)	0.0121 (8)	−0.0043 (9)
C12	0.0330 (10)	0.0435 (12)	0.0319 (10)	−0.0068 (9)	0.0130 (8)	−0.0106 (9)
C13	0.0374 (11)	0.0503 (13)	0.0278 (10)	−0.0104 (10)	0.0115 (8)	−0.0022 (9)
C14	0.0378 (11)	0.0396 (12)	0.0297 (10)	−0.0058 (9)	0.0096 (8)	0.0041 (9)
C15	0.0378 (11)	0.0350 (11)	0.0318 (10)	−0.0043 (9)	0.0130 (9)	−0.0016 (9)
C16	0.0622 (16)	0.0480 (14)	0.0484 (14)	0.0116 (12)	0.0202 (12)	0.0036 (12)
O14	0.0699 (16)	0.0818 (18)	0.111 (2)	0.0008 (13)	0.0501 (14)	−0.0127 (15)
O15	0.0781 (19)	0.086 (2)	0.186 (3)	−0.0088 (16)	0.006 (2)	0.035 (2)

Geometric parameters (Å, º) top

Cu1—O1	1.9616 (16)	C1—C2	1.509 (3)
Cu1—O7	1.9749 (16)	C2—C3	1.412 (3)
Cu1—O8	1.9637 (15)	C2—C7	1.384 (3)
Cu1—O13	2.0914 (19)	C3—C4	1.403 (3)
Cu1—O2ⁱ	1.9595 (16)	C3—C8	1.501 (4)
O1—C1	1.253 (3)	C4—C5	1.369 (4)
O2—C1	1.242 (3)	C5—C6	1.378 (3)
O3—N1	1.218 (3)	C6—C7	1.373 (3)
O4—N1	1.207 (3)	C9—C10	1.511 (3)
O5—N2	1.226 (3)	C10—C15	1.383 (3)
O6—N2	1.213 (3)	C10—C11	1.411 (3)
O7—C9	1.243 (2)	C11—C12	1.407 (3)
O8—C9ⁱ	1.251 (2)	C11—C16	1.499 (3)
O9—N3	1.213 (3)	C12—C13	1.371 (3)
O10—N3	1.226 (3)	C13—C14	1.370 (3)
O11—N4	1.213 (3)	C14—C15	1.380 (3)
O12—N4	1.212 (3)	C5—H5	0.9300
O13—H13B	0.77 (2)	C7—H7	0.9300
O13—H13A	0.80 (3)	C8—H8A	0.9600
O14—H14A	0.81 (3)	C8—H8B	0.9600
O14—H14B	0.80 (3)	C8—H8C	0.9600
O15—H15A	0.83 (4)	C13—H13	0.9300
O15—H15B	0.84 (3)	C15—H15	0.9300
N1—C4	1.482 (3)	C16—H16B	0.9600
N2—C6	1.472 (3)	C16—H16C	0.9600
N3—C12	1.479 (3)	C16—H16A	0.9600
N4—C14	1.465 (3)

O1—Cu1—O7	88.94 (7)	C4—C5—C6	116.6 (2)
O1—Cu1—O8	88.19 (7)	C5—C6—C7	122.0 (2)
O1—Cu1—O13	96.06 (8)	N2—C6—C7	119.5 (2)
O1—Cu1—O2ⁱ	167.09 (7)	N2—C6—C5	118.6 (2)
O7—Cu1—O8	167.24 (7)	C2—C7—C6	120.1 (2)
O7—Cu1—O13	92.58 (7)	O8ⁱ—C9—C10	113.81 (17)
O2ⁱ—Cu1—O7	90.06 (7)	O7—C9—C10	120.09 (17)
O8—Cu1—O13	100.09 (7)	O7—C9—O8ⁱ	126.09 (19)
O2ⁱ—Cu1—O8	89.98 (7)	C11—C10—C15	121.60 (18)
O2ⁱ—Cu1—O13	96.84 (8)	C9—C10—C15	115.34 (17)
Cu1—O1—C1	121.32 (15)	C9—C10—C11	122.91 (17)
Cu1ⁱ—O2—C1	126.52 (14)	C10—C11—C16	122.00 (18)
Cu1—O7—C9	122.28 (14)	C10—C11—C12	114.66 (18)
Cu1—O8—C9ⁱ	124.16 (13)	C12—C11—C16	123.33 (19)
Cu1—O13—H13A	123.8 (17)	N3—C12—C13	114.37 (18)
Cu1—O13—H13B	120 (3)	C11—C12—C13	124.97 (19)
H13A—O13—H13B	109 (3)	N3—C12—C11	120.64 (19)
H14A—O14—H14B	124 (4)	C12—C13—C14	117.07 (19)
H15A—O15—H15B	125 (4)	C13—C14—C15	122.0 (2)
O3—N1—O4	124.5 (2)	N4—C14—C13	119.68 (19)
O4—N1—C4	118.1 (2)	N4—C14—C15	118.31 (19)
O3—N1—C4	117.3 (2)	C10—C15—C14	119.52 (18)
O5—N2—C6	118.0 (2)	C6—C5—H5	122.00
O6—N2—C6	118.1 (2)	C4—C5—H5	122.00
O5—N2—O6	123.9 (2)	C2—C7—H7	120.00
O9—N3—O10	124.6 (2)	C6—C7—H7	120.00
O10—N3—C12	117.0 (2)	C3—C8—H8A	109.00
O9—N3—C12	118.34 (19)	H8A—C8—H8B	110.00
O12—N4—C14	118.49 (19)	H8A—C8—H8C	109.00
O11—N4—O12	123.7 (2)	H8B—C8—H8C	109.00
O11—N4—C14	117.8 (2)	C3—C8—H8B	109.00
O1—C1—C2	116.35 (17)	C3—C8—H8C	109.00
O1—C1—O2	125.1 (2)	C12—C13—H13	121.00
O2—C1—C2	118.56 (18)	C14—C13—H13	121.00
C1—C2—C7	116.30 (17)	C10—C15—H15	120.00
C3—C2—C7	120.91 (18)	C14—C15—H15	120.00
C1—C2—C3	122.78 (17)	C11—C16—H16B	109.00
C4—C3—C8	121.0 (2)	C11—C16—H16C	109.00
C2—C3—C8	123.86 (19)	H16A—C16—H16C	109.00
C2—C3—C4	115.0 (2)	H16B—C16—H16C	109.00
N1—C4—C3	119.3 (2)	H16A—C16—H16B	109.00
N1—C4—C5	115.5 (2)	C11—C16—H16A	109.00
C3—C4—C5	125.2 (2)

O7—Cu1—O1—C1	83.36 (17)	O2—C1—C2—C3	9.2 (3)
O8—Cu1—O1—C1	−84.20 (17)	O2—C1—C2—C7	−170.12 (19)
O13—Cu1—O1—C1	175.84 (17)	C1—C2—C3—C4	−175.44 (18)
O1—Cu1—O7—C9	−88.62 (17)	C1—C2—C3—C8	9.3 (3)
O13—Cu1—O7—C9	175.36 (17)	C7—C2—C3—C4	3.8 (3)
O2ⁱ—Cu1—O7—C9	78.51 (17)	C7—C2—C3—C8	−171.5 (2)
O1—Cu1—O8—C9ⁱ	87.39 (18)	C1—C2—C7—C6	178.87 (19)
O13—Cu1—O8—C9ⁱ	−176.78 (17)	C3—C2—C7—C6	−0.4 (3)
O2ⁱ—Cu1—O8—C9ⁱ	−79.83 (17)	C2—C3—C4—N1	172.73 (19)
O7—Cu1—O2ⁱ—C1ⁱ	−84.61 (18)	C2—C3—C4—C5	−5.4 (3)
O8—Cu1—O2ⁱ—C1ⁱ	82.62 (18)	C8—C3—C4—N1	−11.8 (3)
O13—Cu1—O2ⁱ—C1ⁱ	−177.22 (17)	C8—C3—C4—C5	170.1 (2)
Cu1—O1—C1—O2	1.7 (3)	N1—C4—C5—C6	−175.0 (2)
Cu1—O1—C1—C2	−176.21 (13)	C3—C4—C5—C6	3.2 (4)
Cu1ⁱ—O2—C1—O1	−1.3 (3)	C4—C5—C6—N2	−179.9 (2)
Cu1ⁱ—O2—C1—C2	176.49 (13)	C4—C5—C6—C7	0.8 (3)
Cu1—O7—C9—C10	−177.24 (13)	N2—C6—C7—C2	178.63 (19)
Cu1—O7—C9—O8ⁱ	2.8 (3)	C5—C6—C7—C2	−2.0 (3)
Cu1—O8—C9ⁱ—O7ⁱ	0.1 (3)	O7—C9—C10—C11	48.5 (3)
Cu1—O8—C9ⁱ—C10ⁱ	−179.93 (13)	O7—C9—C10—C15	−135.9 (2)
O3—N1—C4—C3	−49.7 (3)	O8ⁱ—C9—C10—C11	−131.5 (2)
O3—N1—C4—C5	128.6 (3)	O8ⁱ—C9—C10—C15	44.1 (2)
O4—N1—C4—C3	133.4 (3)	C9—C10—C11—C12	170.77 (18)
O4—N1—C4—C5	−48.3 (3)	C9—C10—C11—C16	−10.4 (3)
O5—N2—C6—C5	8.0 (3)	C15—C10—C11—C12	−4.6 (3)
O5—N2—C6—C7	−172.6 (2)	C15—C10—C11—C16	174.3 (2)
O6—N2—C6—C5	−172.8 (3)	C9—C10—C15—C14	−174.02 (17)
O6—N2—C6—C7	6.6 (3)	C11—C10—C15—C14	1.7 (3)
O9—N3—C12—C11	39.4 (3)	C10—C11—C12—N3	−173.40 (18)
O9—N3—C12—C13	−138.8 (2)	C10—C11—C12—C13	4.5 (3)
O10—N3—C12—C11	−143.2 (2)	C16—C11—C12—N3	7.7 (3)
O10—N3—C12—C13	38.7 (3)	C16—C11—C12—C13	−174.4 (2)
O11—N4—C14—C13	15.9 (4)	N3—C12—C13—C14	176.69 (18)
O11—N4—C14—C15	−162.9 (2)	C11—C12—C13—C14	−1.3 (3)
O12—N4—C14—C13	−165.0 (2)	C12—C13—C14—N4	179.2 (2)
O12—N4—C14—C15	16.2 (3)	C12—C13—C14—C15	−2.1 (3)
O1—C1—C2—C3	−172.83 (19)	N4—C14—C15—C10	−179.30 (19)
O1—C1—C2—C7	7.9 (3)	C13—C14—C15—C10	1.9 (3)

Symmetry code: (i) −x, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13A···O14ⁱⁱ	0.80 (3)	1.84 (3)	2.641 (3)	175 (3)
O13—H13B···O10ⁱⁱⁱ	0.77 (2)	2.22 (2)	2.838 (2)	138 (3)
O14—H14A···O15^iv	0.81 (3)	1.95 (3)	2.758 (4)	172 (3)
O14—H14B···O7	0.80 (3)	2.51 (4)	3.182 (3)	143 (4)
O15—H15A···O12^v	0.83 (4)	2.16 (4)	2.953 (4)	161 (4)
O15—H15B···O5^vi	0.84 (3)	2.17 (2)	2.996 (4)	168 (4)
O15—H15B···O6^vi	0.84 (3)	2.60 (4)	3.273 (4)	138 (4)
C15—H15···O5^vii	0.93	2.60	3.438 (3)	150

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

Experimental details

Crystal data
Chemical formula	[Cu₂(C₈H₅N₂O₆)₄(H₂O)₂]·4H₂O
M_r	1135.76
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	8.9757 (3), 22.5582 (8), 11.2698 (3)
β (°)	104.443 (1)
V (Å³)	2209.75 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.08
Crystal size (mm)	0.30 × 0.24 × 0.22

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.743, 0.782
No. of measured, independent and observed [I > 2σ(I)] reflections	21133, 5449, 4344
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.088, 1.02
No. of reflections	5449
No. of parameters	345
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.28

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Selected bond lengths (Å) top

Cu1—O1	1.9616 (16)	Cu1—O13	2.0914 (19)
Cu1—O7	1.9749 (16)	Cu1—O2ⁱ	1.9595 (16)
Cu1—O8	1.9637 (15)

Symmetry code: (i) −x, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13A···O14ⁱⁱ	0.80 (3)	1.84 (3)	2.641 (3)	175 (3)
O13—H13B···O10ⁱⁱⁱ	0.77 (2)	2.22 (2)	2.838 (2)	138 (3)
O14—H14A···O15^iv	0.81 (3)	1.95 (3)	2.758 (4)	172 (3)
O14—H14B···O7	0.80 (3)	2.51 (4)	3.182 (3)	143 (4)
O15—H15A···O12^v	0.83 (4)	2.16 (4)	2.953 (4)	161 (4)
O15—H15B···O5^vi	0.84 (3)	2.17 (2)	2.996 (4)	168 (4)
O15—H15B···O6^vi	0.84 (3)	2.60 (4)	3.273 (4)	138 (4)

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

Acknowledgements

The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan.

References

Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, P.-G., Gao, S. & Ng, S. W. (2007). Acta Cryst. E63, m2617. Web of Science CSD CrossRef IUCr Journals Google Scholar
Danish, M., Saleem, I., Tahir, M. N., Ahmad, N. & Raza, A. R. (2010). Acta Cryst. E66, m528. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Moncol, J., Kavalírová, J., Lis, T. & Valigura, D. (2006). Acta Cryst. E62, m3217–m3219. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stachova, P., Valigura, D., Koman, M., Melnik, M., Korabik, M., Mrozinski, J. & Glowiak, T. (2004). Polyhedron, 23, 1303–1308. CAS Google Scholar
Viossat, B., Greenaway, F. T., Morgant, G., Daran, J.-C., Dung, N.-H. & Sorenson, J. R. J. (2005). J. Inorg. Biochem. 99, 355–367. Web of Science CSD CrossRef PubMed CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.