Dianilinium bis­(pyridine-2,6-dicarboxyl­ato-κ3O2,N,O6)cuprate(II) hexa­hydrate

Shokooh Saljooghi, A.; Amiri Rudbari, H.; Nicolò, F.; Zahmati, M.; Delavar Mendi, F.; Eshtiagh-Hosseini, H.; Mirzaei, M.

doi:10.1107/S1600536812028590

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Pages m1020-m1021

https://doi.org/10.1107/S1600536812028590

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Dianilinium bis(pyridine-2,6-dicarboxylato-κ³O²,N,O⁶)cuprate(II) hexahydrate

Amir Shokooh Saljooghi,^a ^* Hadi Amiri Rudbari,^b Francesco Nicolò,^b Maliheh Zahmati,^a Fatemeh Delavar Mendi,^a Hossein Eshtiagh-Hosseini ^a and Masoud Mirzaei ^a

^aDepartment of Chemistry, Ferdowsi University of Mashhad, Mashhad 91779, Iran, and ^bDipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina, Salita Sperone, 31 Contrada Papardo, 98166 Messina, Italy
^*Correspondence e-mail: amir.saljooghi@yahoo.com

(Received 19 April 2012; accepted 23 June 2012; online 4 July 2012)

The asymmetric unit of the title complex, (C₆H₈N)₂[Cu(C₇H₃NO₄)₂]·6H₂O, contains half a copper(II)–dipicolinate complex located on a twofold rotation axis, one protonated aniline molecule and three solvent water molecules. The Cu^II atom is coordinated by four O atoms and two N atoms from two dipicolinate ligands in a distorted octahedral environment. In the crystal, the components are linked into a three-dimensional framework by intermolecular O—H⋯O and N—H⋯O interactions.

Related literature

For metal complexes formed by pyridinedicarboxylic acids, see: Crans (2000 ); Wang et al. (2004 ); Park et al. (2007 ); Aghabozorg et al. (2008 , 2011 ); Tabatabaee (2010 ).

Experimental

Crystal data

(C₆H₈N)₂[Cu(C₇H₃NO₄)₂]·6H₂O
M_r = 690.11
Monoclinic, C 2/c
a = 20.9117 (6) Å
b = 7.9115 (2) Å
c = 19.8842 (5) Å
β = 117.706 (2)°
V = 2912.52 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.83 mm⁻¹
T = 293 K
0.44 × 0.36 × 0.35 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.652, T_max = 0.746
48649 measured reflections
5321 independent reflections
4990 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.073
S = 1.06
5321 reflections
213 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N1	1.9232 (7)
Cu1—O1	2.2577 (7)
Cu1—O2	2.1701 (7)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O4ⁱ	0.83	1.91	2.7267 (11)	171
N2—H2B⋯O7ⁱⁱ	0.89	1.93	2.8071 (12)	168
N2—H2C⋯O3ⁱⁱⁱ	0.88	2.14	2.9842 (12)	162
O5—H5A⋯O2^iv	0.85	1.88	2.732	176
O5—H5B⋯O6ⁱⁱ	0.85	1.97	2.8026 (12)	166
O6—H6A⋯O3^v	0.85	1.97	2.8066 (11)	167
O6—H6B⋯O5^vi	0.85	1.93	2.7760 (13)	177
O7—H7A⋯O1^vii	0.85	1.92	2.750	164
O7—H7B⋯O6^viii	0.85	2.17	3.0083 (12)	170
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x+1, -y+1, -z+1; (iii) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iv) x, y-1, z; (v) $[x, -y+1, z+{\script{1\over 2}}]$ ; (vi) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vii) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (viii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XPW (Siemens, 1996 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812028590/vn2037sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812028590/vn2037Isup2.hkl

checkCIF report

Comment top

Pyridine-2,6-dicarboxylic acid (dipicolinic acid) is a versatile N—O donor capable of forming stable chelates (Park et al., 2007), with various metal ions and it can exhibit diverse coordination modes such as monodentate (Park et al., 2007), bidentate (Wang et al., 2004), tridentate (Park et al., 2007), meridian (Park et al., 2007), or bridging (Aghabozorg et al., 2008, 2011). Dipicolinic acid (H₂dipic) and its anions (Hdipic^-, dipic2^-), have been extensively used in the design of coordination compounds, due to the variety of their bonding ability and the relatively strong hydrogen bonds they form. Dipicolinic acid is a beneficial compound for the human organism and it is involved in several essential biochemical processes. It shows various biological functions and is a suitable ligand for modeling potential pharmacological compounds because of its low toxicity and amphiphilic nature (Crans, 2000). In recent years, syntheses and crystal structures of a large number of complexes with dipicolinic acid and some amino compounds have been reported (Aghabozorg et al., 2008; Tabatabaee, 2010). Here, we present the preparation and the crystal structure of the title compund, (C₆H₈N)₂ [Cu(C₇H₃NO₄)₂].6H₂O. The molecular structure of the title compound is shown in Fig. 1. The cationic portion of the asymmetric unit consists of one protonated aniline molecule (anilinium cation) and the anionic portion is the [Cu(pydc)₂]^2- complex.In the anion, the angles O1—Cu1—O1 [103.65 (5)°], O2—Cu1—O2 [102.71 (5)°] and N1—Cu1—N1 [179.46 (5)°] indicate that the coordination environment around Cu(II) ion is a distorted octahedron. There are extensive intermolecular O—H···O, N—H···O and weak C—H···O hydrogen bonds, which increases the stability of the crystal structure (Fig. 2).

Related literature top

For metal complexes formed by pyridinedicarboxylic acids, see: Crans (2000); Wang et al. (2004); Park et al. (2007); Aghabozorg et al. (2008, 2011); Tabatabaee (2010).

Experimental top

The title compound was synthesized by the reaction of copper(II) acetate, pyridine-2,6-dicarboxylic acid (pydcH₂) and aniline in aqueous solution in a 1:1:1 molar ratio. Green crystals of the title compound were obtained by slow evaporation of the solvent at room temperature.

Structure description top

For metal complexes formed by pyridinedicarboxylic acids, see: Crans (2000); Wang et al. (2004); Park et al. (2007); Aghabozorg et al. (2008, 2011); Tabatabaee (2010).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XPW (Siemens, 1996); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure and atom labeling scheme for title compound with displacement ellipsoids at the 50% probability level.
	Fig. 2. A view of H-bonded chain in crystal network of title compound, hydrogen bonds are shown as dashed lines.

Dianilinium bis(pyridine-2,6-dicarboxylato- κ³O²,N,O⁶)cuprate(II) hexahydrate top

Crystal data top

(C₆H₈N)₂[Cu(C₇H₃NO₄)₂]·6H₂O	F(000) = 1436
M_r = 690.11	D_x = 1.574 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9787 reflections
a = 20.9117 (6) Å	θ = 2.3–32.7°
b = 7.9115 (2) Å	µ = 0.83 mm⁻¹
c = 19.8842 (5) Å	T = 293 K
β = 117.706 (2)°	Irregular, green
V = 2912.52 (13) Å³	0.44 × 0.36 × 0.35 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	5321 independent reflections
Radiation source: fine-focus sealed tube	4990 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
φ and ω scans	θ_max = 32.7°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −31→31
T_min = 0.652, T_max = 0.746	k = −12→12
48649 measured reflections	l = −30→30

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0415P)² + 1.1609P] where P = (F_o² + 2F_c²)/3
5321 reflections	(Δ/σ)_max = 0.001
213 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

(C₆H₈N)₂[Cu(C₇H₃NO₄)₂]·6H₂O	V = 2912.52 (13) Å³
M_r = 690.11	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 20.9117 (6) Å	µ = 0.83 mm⁻¹
b = 7.9115 (2) Å	T = 293 K
c = 19.8842 (5) Å	0.44 × 0.36 × 0.35 mm
β = 117.706 (2)°

Data collection top

Bruker APEXII CCD diffractometer	5321 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	4990 reflections with I > 2σ(I)
T_min = 0.652, T_max = 0.746	R_int = 0.017
48649 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.06	Δρ_max = 0.39 e Å⁻³
5321 reflections	Δρ_min = −0.55 e Å⁻³
213 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2σ(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	0.5000	0.979382 (19)	0.2500	0.02257 (5)
O1	0.59158 (4)	0.80292 (10)	0.26847 (4)	0.03298 (14)
O2	0.43941 (4)	1.15066 (10)	0.28429 (4)	0.03275 (14)
O3	0.70644 (4)	0.77108 (10)	0.35839 (4)	0.03315 (14)
O4	0.43162 (4)	1.20999 (11)	0.39036 (4)	0.03787 (16)
N1	0.55834 (4)	0.98045 (9)	0.35855 (4)	0.02101 (12)
C1	0.64268 (4)	0.81793 (11)	0.33490 (5)	0.02413 (14)
C2	0.62266 (4)	0.90375 (10)	0.39060 (4)	0.02198 (13)
C3	0.66492 (5)	0.90453 (12)	0.46879 (5)	0.02786 (15)
H3	0.7102	0.8535	0.4911	0.033*
C4	0.63852 (5)	0.98284 (13)	0.51321 (5)	0.03126 (18)
H4	0.6656	0.9822	0.5658	0.038*
C5	0.57176 (5)	1.06210 (12)	0.47912 (5)	0.02811 (16)
H5	0.5534	1.1150	0.5082	0.034*
C6	0.53317 (4)	1.06049 (11)	0.40074 (4)	0.02196 (13)
C7	0.46167 (4)	1.14859 (11)	0.35519 (5)	0.02438 (14)
N2	0.65628 (5)	0.54403 (11)	0.60233 (5)	0.03183 (16)
H2A	0.6328	0.6190	0.6098	0.038*
H2B	0.6526	0.4490	0.6238	0.038*
H2C	0.7012	0.5780	0.6201	0.038*
C8	0.63075 (5)	0.51163 (11)	0.52136 (6)	0.02671 (15)
C9	0.67563 (6)	0.42455 (14)	0.50001 (6)	0.03540 (19)
H9	0.7207	0.3871	0.5364	0.042*
C10	0.65261 (7)	0.39375 (16)	0.42367 (7)	0.0440 (2)
H10	0.6826	0.3359	0.4087	0.053*
C11	0.58577 (8)	0.44806 (16)	0.36981 (7)	0.0442 (3)
H11	0.5706	0.4266	0.3186	0.053*
C12	0.54110 (7)	0.53474 (16)	0.39200 (7)	0.0418 (2)
H12	0.4959	0.5711	0.3556	0.050*
C13	0.56340 (5)	0.56767 (14)	0.46834 (6)	0.03397 (18)
H13	0.5337	0.6262	0.4834	0.041*
O5	0.29295 (4)	0.17557 (11)	0.19901 (5)	0.03988 (17)
H5A	0.3387	0.1722	0.2247	0.060*
H5B	0.2852	0.2755	0.2092	0.060*
O6	0.74953 (5)	0.49186 (10)	0.79362 (5)	0.04002 (17)
H6A	0.7296	0.4169	0.8082	0.060*
H6B	0.7635	0.4372	0.7660	0.060*
O7	0.37393 (5)	0.76400 (11)	0.34828 (4)	0.03909 (16)
H7A	0.3829	0.7562	0.3108	0.059*
H7B	0.3414	0.8380	0.3387	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01931 (7)	0.02986 (8)	0.01981 (7)	0.000	0.01017 (5)	0.000
O1	0.0284 (3)	0.0478 (4)	0.0232 (3)	0.0025 (3)	0.0124 (2)	−0.0029 (3)
O2	0.0236 (3)	0.0484 (4)	0.0236 (3)	0.0075 (3)	0.0088 (2)	0.0010 (3)
O3	0.0245 (3)	0.0373 (4)	0.0392 (3)	0.0072 (3)	0.0161 (3)	−0.0025 (3)
O4	0.0355 (3)	0.0459 (4)	0.0394 (4)	0.0126 (3)	0.0236 (3)	−0.0026 (3)
N1	0.0190 (3)	0.0251 (3)	0.0198 (3)	0.0023 (2)	0.0097 (2)	0.0004 (2)
C1	0.0232 (3)	0.0254 (3)	0.0259 (3)	0.0028 (3)	0.0133 (3)	0.0011 (3)
C2	0.0193 (3)	0.0245 (3)	0.0222 (3)	0.0025 (2)	0.0097 (2)	0.0014 (2)
C3	0.0229 (3)	0.0320 (4)	0.0237 (3)	0.0049 (3)	0.0068 (3)	0.0031 (3)
C4	0.0306 (4)	0.0393 (5)	0.0188 (3)	0.0029 (3)	0.0071 (3)	0.0008 (3)
C5	0.0293 (4)	0.0348 (4)	0.0213 (3)	0.0014 (3)	0.0127 (3)	−0.0027 (3)
C6	0.0204 (3)	0.0261 (3)	0.0209 (3)	0.0009 (3)	0.0109 (3)	−0.0012 (3)
C7	0.0212 (3)	0.0271 (4)	0.0262 (3)	0.0017 (3)	0.0122 (3)	−0.0021 (3)
N2	0.0293 (4)	0.0354 (4)	0.0315 (4)	0.0046 (3)	0.0147 (3)	−0.0007 (3)
C8	0.0267 (4)	0.0248 (3)	0.0313 (4)	−0.0010 (3)	0.0157 (3)	0.0005 (3)
C9	0.0346 (5)	0.0356 (5)	0.0415 (5)	0.0057 (4)	0.0223 (4)	0.0012 (4)
C10	0.0554 (7)	0.0432 (6)	0.0474 (6)	0.0012 (5)	0.0357 (5)	−0.0046 (5)
C11	0.0581 (7)	0.0425 (6)	0.0352 (5)	−0.0113 (5)	0.0244 (5)	−0.0043 (4)
C12	0.0367 (5)	0.0438 (6)	0.0364 (5)	−0.0043 (4)	0.0098 (4)	0.0018 (4)
C13	0.0272 (4)	0.0349 (4)	0.0386 (5)	0.0013 (3)	0.0144 (4)	−0.0004 (4)
O5	0.0276 (3)	0.0430 (4)	0.0443 (4)	0.0022 (3)	0.0128 (3)	0.0012 (3)
O6	0.0493 (5)	0.0317 (4)	0.0429 (4)	−0.0055 (3)	0.0246 (4)	−0.0021 (3)
O7	0.0470 (4)	0.0429 (4)	0.0332 (3)	0.0045 (3)	0.0235 (3)	0.0054 (3)

Geometric parameters (Å, º) top

Cu1—N1	1.9232 (7)	N2—C8	1.4641 (13)
Cu1—N1ⁱ	1.9232 (7)	N2—H2A	0.8262
Cu1—O2ⁱ	2.1701 (7)	N2—H2B	0.8855
Cu1—O1	2.2577 (7)	N2—H2C	0.8779
Cu1—O2	2.1701 (7)	C8—C9	1.3807 (13)
Cu1—O1ⁱ	2.2577 (7)	C8—C13	1.3823 (14)
O1—C1	1.2603 (10)	C9—C10	1.3841 (16)
O2—C7	1.2628 (10)	C9—H9	0.9300
O3—C1	1.2467 (10)	C10—C11	1.376 (2)
O4—C7	1.2364 (10)	C10—H10	0.9300
N1—C2	1.3365 (10)	C11—C12	1.3859 (19)
N1—C6	1.3389 (10)	C11—H11	0.9300
C1—C2	1.5146 (11)	C12—C13	1.3897 (16)
C2—C3	1.3858 (11)	C12—H12	0.9300
C3—C4	1.3865 (13)	C13—H13	0.9300
C3—H3	0.9300	O5—H5A	0.8500
C4—C5	1.3863 (13)	O5—H5B	0.8500
C4—H4	0.9300	O6—H6A	0.8502
C5—C6	1.3823 (11)	O6—H6B	0.8500
C5—H5	0.9300	O7—H7A	0.8499
C6—C7	1.5109 (11)	O7—H7B	0.8500

N1—Cu1—N1ⁱ	179.49 (4)	C4—C5—H5	120.8
N1—Cu1—O2ⁱ	101.04 (3)	N1—C6—C5	121.15 (8)
N1ⁱ—Cu1—O2ⁱ	78.64 (3)	N1—C6—C7	114.23 (7)
N1—Cu1—O2	78.64 (3)	C5—C6—C7	124.61 (7)
N1ⁱ—Cu1—O2	101.04 (3)	O4—C7—O2	127.31 (8)
O2ⁱ—Cu1—O2	102.72 (4)	O4—C7—C6	117.63 (8)
N1—Cu1—O1ⁱ	103.46 (3)	O2—C7—C6	115.06 (7)
N1ⁱ—Cu1—O1ⁱ	76.86 (3)	C8—N2—H2A	112.3
O2ⁱ—Cu1—O1ⁱ	155.50 (2)	C8—N2—H2B	108.2
O2—Cu1—O1ⁱ	82.08 (3)	H2A—N2—H2B	109.3
N1—Cu1—O1	76.86 (3)	C8—N2—H2C	105.7
N1ⁱ—Cu1—O1	103.46 (3)	H2A—N2—H2C	108.8
O2ⁱ—Cu1—O1	82.08 (3)	H2B—N2—H2C	112.5
O2—Cu1—O1	155.50 (2)	C9—C8—C13	121.51 (10)
O1ⁱ—Cu1—O1	103.61 (4)	C9—C8—N2	118.23 (9)
C1—O1—Cu1	110.73 (6)	C13—C8—N2	120.26 (8)
C7—O2—Cu1	112.14 (5)	C8—C9—C10	119.05 (10)
C2—N1—C6	121.17 (7)	C8—C9—H9	120.5
C2—N1—Cu1	120.39 (5)	C10—C9—H9	120.5
C6—N1—Cu1	118.44 (5)	C11—C10—C9	120.53 (11)
O3—C1—O1	127.06 (8)	C11—C10—H10	119.7
O3—C1—C2	118.06 (7)	C9—C10—H10	119.7
O1—C1—C2	114.87 (7)	C10—C11—C12	119.86 (11)
N1—C2—C3	120.56 (7)	C10—C11—H11	120.1
N1—C2—C1	114.45 (7)	C12—C11—H11	120.1
C3—C2—C1	124.99 (7)	C11—C12—C13	120.45 (11)
C2—C3—C4	118.79 (8)	C11—C12—H12	119.8
C2—C3—H3	120.6	C13—C12—H12	119.8
C4—C3—H3	120.6	C8—C13—C12	118.59 (10)
C5—C4—C3	119.95 (8)	C8—C13—H13	120.7
C5—C4—H4	120.0	C12—C13—H13	120.7
C3—C4—H4	120.0	H5A—O5—H5B	99.9
C6—C5—C4	118.33 (8)	H6A—O6—H6B	103.6
C6—C5—H5	120.8	H7A—O7—H7B	109.5

N1—Cu1—O1—C1	−14.29 (6)	O3—C1—C2—C3	−13.90 (13)
N1ⁱ—Cu1—O1—C1	165.31 (6)	O1—C1—C2—C3	166.50 (9)
O2ⁱ—Cu1—O1—C1	89.06 (6)	N1—C2—C3—C4	1.50 (13)
O2—Cu1—O1—C1	−14.29 (11)	C1—C2—C3—C4	−177.53 (9)
O1ⁱ—Cu1—O1—C1	−115.21 (7)	C2—C3—C4—C5	−1.60 (15)
N1—Cu1—O2—C7	−11.16 (6)	C3—C4—C5—C6	−0.05 (15)
N1ⁱ—Cu1—O2—C7	169.24 (6)	C2—N1—C6—C5	−2.07 (13)
O2ⁱ—Cu1—O2—C7	−110.06 (7)	Cu1—N1—C6—C5	178.37 (7)
O1ⁱ—Cu1—O2—C7	94.37 (6)	C2—N1—C6—C7	176.68 (7)
O1—Cu1—O2—C7	−11.16 (11)	Cu1—N1—C6—C7	−2.87 (9)
O2ⁱ—Cu1—N1—C2	−71.51 (7)	C4—C5—C6—N1	1.91 (14)
O2—Cu1—N1—C2	−172.44 (7)	C4—C5—C6—C7	−176.72 (9)
O1ⁱ—Cu1—N1—C2	108.66 (6)	Cu1—O2—C7—O4	−167.46 (8)
O1—Cu1—N1—C2	7.56 (6)	Cu1—O2—C7—C6	12.58 (9)
O2ⁱ—Cu1—N1—C6	108.06 (6)	N1—C6—C7—O4	172.64 (8)
O2—Cu1—N1—C6	7.12 (6)	C5—C6—C7—O4	−8.65 (13)
O1ⁱ—Cu1—N1—C6	−71.77 (7)	N1—C6—C7—O2	−7.39 (11)
O1—Cu1—N1—C6	−172.88 (7)	C5—C6—C7—O2	171.32 (9)
Cu1—O1—C1—O3	−162.04 (8)	C13—C8—C9—C10	0.37 (16)
Cu1—O1—C1—C2	17.52 (9)	N2—C8—C9—C10	−179.56 (10)
C6—N1—C2—C3	0.33 (12)	C8—C9—C10—C11	−0.45 (18)
Cu1—N1—C2—C3	179.88 (6)	C9—C10—C11—C12	0.19 (19)
C6—N1—C2—C1	179.46 (7)	C10—C11—C12—C13	0.16 (18)
Cu1—N1—C2—C1	−0.99 (10)	C9—C8—C13—C12	−0.03 (15)
O3—C1—C2—N1	167.02 (8)	N2—C8—C13—C12	179.90 (9)
O1—C1—C2—N1	−12.58 (11)	C11—C12—C13—C8	−0.24 (17)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O4ⁱⁱ	0.83	1.91	2.7267 (11)	171
N2—H2B···O7ⁱⁱⁱ	0.89	1.93	2.8071 (12)	168
N2—H2C···O3^iv	0.88	2.14	2.9842 (12)	162
O5—H5A···O2^v	0.85	1.88	2.732	176
O5—H5B···O6ⁱⁱⁱ	0.85	1.97	2.8026 (12)	166
O6—H6A···O3^vi	0.85	1.97	2.8066 (11)	167
O6—H6B···O5^vii	0.85	1.93	2.7760 (13)	177
O7—H7A···O1ⁱ	0.85	1.92	2.750	164
O7—H7B···O6^viii	0.85	2.17	3.0083 (12)	170

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

Experimental details

Crystal data
Chemical formula	(C₆H₈N)₂[Cu(C₇H₃NO₄)₂]·6H₂O
M_r	690.11
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	20.9117 (6), 7.9115 (2), 19.8842 (5)
β (°)	117.706 (2)
V (Å³)	2912.52 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.83
Crystal size (mm)	0.44 × 0.36 × 0.35

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.652, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	48649, 5321, 4990
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.760

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.073, 1.06
No. of reflections	5321
No. of parameters	213
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.55

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XPW (Siemens, 1996), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—N1	1.9232 (7)	Cu1—O2	2.1701 (7)
Cu1—O1	2.2577 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O4ⁱ	0.83	1.91	2.7267 (11)	170.6
N2—H2B···O7ⁱⁱ	0.89	1.93	2.8071 (12)	168.2
N2—H2C···O3ⁱⁱⁱ	0.88	2.14	2.9842 (12)	161.7
O5—H5A···O2^iv	0.85	1.88	2.732	176.2
O5—H5B···O6ⁱⁱ	0.85	1.97	2.8026 (12)	166.1
O6—H6A···O3^v	0.85	1.97	2.8066 (11)	166.7
O6—H6B···O5^vi	0.85	1.93	2.7760 (13)	176.5
O7—H7A···O1^vii	0.85	1.92	2.750	164.4
O7—H7B···O6^viii	0.85	2.17	3.0083 (12)	169.5

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

Acknowledgements

Support for this study by Ferdowsi University of Mashhad is gratefully acknowledged.

References

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