Bis(benzene-1,2-diamine-κ2N,N′)(sulfato-κO)copper(II) monohydrate

Djebli, Y.; Boufas, S.; Bencharif, L.; Roisnel, T.; Bencharif, M.

doi:10.1107/S1600536812041967

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Pages m1411-m1412

doi:10.1107/S1600536812041967

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Bis(benzene-1,2-diamine-κ²N,N′)(sulfato-κO)copper(II) monohydrate

Yacine Djebli,^a Sihem Boufas,^b ^* Leila Bencharif,^a Thierry Roisnel ^c and Mustafa Bencharif ^a

^aUniversité Mentouri de Constantine, 25000 Constantine, Algeria, ^bUniversité 20 Aout 1955, 21000 Skikda, Algeria, and ^cSciences Chimiques de Rennes (UMR CNRS 6226), Université de Rennes 1, Avenue du Général Leclerc, 35042 Rennes Cedex, France
^*Correspondence e-mail: boufas_sihem@yahoo.fr

(Received 8 September 2012; accepted 7 October 2012; online 27 October 2012)

The title complex, [Cu(SO₄)(C₆H₈N₂)₂]·H₂O, was obtained under hydrothermal conditions. The Cu^II ion is five-coordinated in a distorted square-pyramidal manner by four N atoms from two benzene-1,2-diamine ligands at the base and one O atom from a monodentate sulfate anion at the apex of the coordination polyhedron. N—H⋯O hydrogen bonding between the amino functions and the sulfate groups leads to the formation of layers parallel to (001). C—H⋯O hydrogen bonding interactions between the layers consolidate the three-dimensional set-up. There are voids in the structure filled with lattice water molecules that are disordered over three sites in a 0.430 (6):0.270 (6):0.300 (6) ratio.

Related literature

For bio-inorganic chemistry and the coordination chemistry of copper(II), see: Datta et al. (2008 ); Diallo et al. (2008 ); Khalaji et al. (2009 ). For graph-set notation, see: Bernstein et al. (1995 ); Etter et al. (1990 ).

Experimental

Crystal data

[Cu(SO₄)(C₆H₈N₂)₂]·H₂O
M_r = 393.90
Orthorhombic, P b c a
a = 18.6794 (4) Å
b = 7.5317 (2) Å
c = 21.9757 (5) Å
V = 3091.71 (13) Å³
Z = 8
Mo Kα radiation
μ = 1.58 mm⁻¹
T = 120 K
0.38 × 0.15 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ) T_min = 0.543, T_max = 0.924
42067 measured reflections
3555 independent reflections
2957 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.097
S = 1.08
3555 reflections
212 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.29 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N2	2.014 (2)
Cu1—N4	2.020 (2)
Cu1—N1	2.022 (2)
Cu1—N3	2.023 (2)
Cu1—O1	2.2433 (18)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4ⁱ	0.90	2.03	2.904 (3)	164
N1—H1B⋯O2	0.90	2.06	2.873 (4)	149
N2—H2A⋯O3ⁱⁱ	0.90	2.16	3.059 (4)	174
N2—H2B⋯O3ⁱⁱⁱ	0.90	2.02	2.890 (4)	161
N3—H3A⋯O3ⁱⁱⁱ	0.90	2.45	3.188 (4)	139
N3—H3A⋯O4ⁱⁱⁱ	0.90	2.24	3.068 (4)	153
N4—H4A⋯O4	0.90	2.37	3.202 (4)	153
N4—H4B⋯O2ⁱ	0.90	1.96	2.825 (4)	160
C4—H4⋯O4^iv	0.93	2.59	3.512 (4)	172
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) x, y+1, z; (iv) -x, -y+1, -z.

Data collection: COLLECT (Nonius, 2002 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ); data reduction: EVALCCD (Duisenberg et al., 2003 ); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEPIII (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PARST (Nardelli, 1995 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812041967/wm2682sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812041967/wm2682Isup2.hkl

checkCIF report

Comment top

Copper(II) complexes have been widely investigated in both bioinorganic chemistry and coordination chemistry (Datta et al., 2008; Diallo et al., 2008; Khalaji et al., 2009) due to the important role of copper in living organisms and its peculiar coordination chemistry, i.e. the Jahn-Teller distortion. We report here the structure of the title mononuclear copper(II) complex, [Cu(SO₄)(C₆H₈N₂)₂]^.H₂O.

As shown in Fig. 1, the complex molecule exhibits copper(II) in a distorted [4 + 1] square-pyramidal coordination environment. The basal plane is defined by the amino nitrogen donors of the benzene-1,2-diamine ligand, while the apical position is occupied by one oxygen atom of the SO₄^2- anion. As expected, the organic moieties are approximately planar. In the organic moiety bonded to the copper atom with N1 and N2, the r.m.s. deviation for the non-H atoms is 0.0103 Å, with the maximum deviation of N1 from the mean plane being -0.018 (2) Å. The 1,2 benzene-1,2-diamine molecule linked to Cu(II) with N3 and N4 has a r.m.s deviation for non-H atoms of 0.0173 Å with a maximum deviation from the mean plane being -0.027 (2) Å (for N4). In the crystal structure, π···π stacking interactions occur between adjacent rings, with centroid-centroid separations of 3.583 (2) Å for Cg1···Cg2ⁱ (Cg1 and Cg2 are the centroids of the C1—C6 and C7—C12 rings, respectively; symmetry code: (i) (-x, -y, -z)).

In the title compound, the individual molecules are linked by N—H···O hydrogen bonds into a two-dimensional network parallel to (001). In the layers alternating R²₂(8), R²₁(4), R¹₂(6) and dual R³₃(9) (Bernstein et al., 1995) hydrogen-bonded motifs are formed. These layers are linked by means of C15—H15···O22 hydrogen bonds. In terms of graph-set analysis (Etter et al., 1990; Bernstein et al., 1995), the descriptor for this pattern is R²₄(16).

In the structure voids with an approximate volume of 62 Å³ are present. These voids are filled with a water molecule disordered over three positions with an occupancy ratio of 0.4320 (6):0.270 (6):0.300 (6). Although the H positions of the disordered water molecule could not be located, O···O and O···N interactions suggest likewise an involvement in hydrogen bonding, e.g. N3···O1WC = 2.98 (4) Å, O1···O1WA = 2.73 (3) Å.

Related literature top

For bio-inorganic chemistry and the coordination chemistry of copper(II), see: Datta et al. (2008); Diallo et al. (2008); Khalaji et al. (2009). For graph-set notation, see: Bernstein et al. (1995); Etter et al. (1990).

Experimental top

Benzene-1,2-diamine (0.2 mmol) and CuSO₄.5H₂O (0.1 mmol) were dissolved in H₂O (5 ml). The mixture was stirred for 16 h at room temperature to give a violet solution. After allowing the resulting solution to stand in air, violet plate-shaped crystals of the compound were formed on slow evaporation of the solvent.

Computing details top

Data collection: COLLECT (Nonius, 2002); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PARST (Nardelli, 1995).

Figures top

	Fig. 1. The molecular structure of the title compound drawn with displacement parameters at the 50% probability level.
	Fig. 2. Part of the crystal structure of (I), showing the formation of R²₂(8), R²₁(4),hy2596 R¹₂(6) and R³₃(9) rings. Hydrogen bonds are shown as dashed lines. Hydrogen atoms not involved in the motif have been omitted for clarity.

Bis(benzene-1,2-diamine-κ²N,N')(sulfato-κO)copper(II) monohydrate top

Crystal data top

[Cu(SO₄)(C₆H₈N₂)₂]·H₂O	F(000) = 1624
M_r = 393.90	D_x = 1.693 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 102968 reflections
a = 18.6794 (4) Å	θ = 2.9–27.5°
b = 7.5317 (2) Å	µ = 1.58 mm⁻¹
c = 21.9757 (5) Å	T = 120 K
V = 3091.71 (13) Å³	Plate, violet
Z = 8	0.38 × 0.15 × 0.05 mm

Data collection top

Nonius KappaCCD diffractometer	3555 independent reflections
Radiation source: Enraf Nonius FR590	2957 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
Detector resolution: 9 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
CCD rotation images, thin slices scans	h = −24→24
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −9→9
T_min = 0.543, T_max = 0.924	l = −28→28
42067 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) = 0.097	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0455P)² + 5.6842P] where P = (F_o² + 2F_c²)/3
3555 reflections	(Δ/σ)_max = 0.005
212 parameters	Δρ_max = 1.29 e Å⁻³
1 restraint	Δρ_min = −0.64 e Å⁻³

Crystal data top

[Cu(SO₄)(C₆H₈N₂)₂]·H₂O	V = 3091.71 (13) Å³
M_r = 393.90	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 18.6794 (4) Å	µ = 1.58 mm⁻¹
b = 7.5317 (2) Å	T = 120 K
c = 21.9757 (5) Å	0.38 × 0.15 × 0.05 mm

Data collection top

Nonius KappaCCD diffractometer	3555 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	2957 reflections with I > 2σ(I)
T_min = 0.543, T_max = 0.924	R_int = 0.057
42067 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	1 restraint
wR(F²) = 0.097	H-atom parameters constrained
S = 1.08	Δρ_max = 1.29 e Å⁻³
3555 reflections	Δρ_min = −0.64 e Å⁻³
212 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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.088690 (15)	0.58928 (4)	0.199850 (13)	0.01191 (11)
S2	0.12634 (3)	0.15921 (8)	0.18987 (3)	0.01166 (14)
O4	0.06308 (9)	0.1072 (3)	0.15332 (8)	0.0193 (4)
O1	0.14861 (9)	0.3423 (2)	0.17409 (8)	0.0174 (4)
O2	0.10796 (10)	0.1495 (3)	0.25522 (8)	0.0192 (4)
O3	0.18635 (9)	0.0364 (2)	0.17653 (9)	0.0186 (4)
N3	0.09519 (11)	0.7199 (3)	0.11963 (10)	0.0155 (4)
H3A	0.1012	0.8368	0.1265	0.019*
H3B	0.1332	0.6804	0.0985	0.019*
N4	−0.00490 (11)	0.4952 (3)	0.16695 (9)	0.0145 (4)
H4A	−0.0018	0.3769	0.1618	0.017*
H4B	−0.0403	0.5171	0.1937	0.017*
N1	0.06897 (11)	0.5075 (3)	0.28588 (9)	0.0135 (4)
H1A	0.0255	0.5456	0.2977	0.016*
H1B	0.0692	0.3881	0.2874	0.016*
N2	0.17909 (11)	0.6930 (3)	0.23489 (9)	0.0141 (4)
H2A	0.2174	0.6385	0.2185	0.017*
H2B	0.1817	0.8093	0.2257	0.017*
C7	0.12327 (12)	0.5774 (3)	0.32658 (11)	0.0134 (5)
C8	0.17991 (13)	0.6705 (3)	0.30072 (11)	0.0134 (5)
C3	0.01846 (14)	0.7716 (4)	0.02813 (12)	0.0194 (5)
H3	0.0529	0.8467	0.0116	0.023*
C11	0.17574 (14)	0.6137 (4)	0.42584 (12)	0.0189 (5)
H11	0.1747	0.5948	0.4676	0.023*
C9	0.23454 (13)	0.7353 (4)	0.33737 (12)	0.0188 (5)
H9	0.2725	0.7972	0.3201	0.023*
C1	−0.02133 (13)	0.5799 (3)	0.10905 (11)	0.0149 (5)
C2	0.03023 (13)	0.6913 (3)	0.08463 (11)	0.0152 (5)
C10	0.23241 (13)	0.7075 (4)	0.39984 (12)	0.0193 (5)
H10	0.2689	0.7515	0.4244	0.023*
C6	−0.08541 (14)	0.5499 (4)	0.07848 (12)	0.0197 (6)
H6	−0.1204	0.4778	0.0957	0.024*
C4	−0.04457 (15)	0.7389 (4)	−0.00323 (12)	0.0228 (6)
H4	−0.0521	0.7903	−0.0412	0.027*
C12	0.12084 (14)	0.5486 (4)	0.38939 (11)	0.0170 (5)
H12	0.0829	0.4865	0.4066	0.02*
C5	−0.09680 (14)	0.6283 (4)	0.02224 (13)	0.0222 (6)
H5	−0.1393	0.6074	0.0014	0.027*
O1WA	0.2247 (3)	0.4801 (9)	0.0775 (2)	0.0328 (9)*	0.430 (6)
O1WB	0.2410 (5)	0.6775 (15)	0.0687 (4)	0.0328 (9)*	0.270 (6)
O1WC	0.2338 (4)	0.5778 (17)	0.0693 (4)	0.0328 (9)*	0.300 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.00820 (16)	0.01169 (17)	0.01585 (16)	−0.00014 (12)	0.00131 (10)	0.00052 (11)
S2	0.0078 (3)	0.0102 (3)	0.0170 (3)	0.0003 (2)	0.0020 (2)	0.0010 (2)
O4	0.0113 (8)	0.0240 (10)	0.0228 (9)	−0.0026 (8)	−0.0024 (7)	0.0009 (8)
O1	0.0139 (8)	0.0089 (9)	0.0295 (10)	0.0013 (7)	0.0074 (7)	0.0019 (7)
O2	0.0205 (9)	0.0205 (10)	0.0168 (9)	−0.0019 (8)	0.0026 (7)	0.0015 (7)
O3	0.0125 (8)	0.0124 (9)	0.0310 (10)	0.0038 (7)	0.0045 (7)	0.0017 (8)
N3	0.0118 (10)	0.0151 (11)	0.0197 (10)	−0.0023 (8)	0.0023 (8)	0.0007 (9)
N4	0.0114 (9)	0.0130 (10)	0.0190 (10)	−0.0008 (8)	0.0025 (8)	0.0012 (8)
N1	0.0086 (9)	0.0133 (11)	0.0186 (10)	−0.0013 (9)	0.0013 (8)	−0.0021 (8)
N2	0.0104 (9)	0.0119 (10)	0.0201 (10)	−0.0004 (8)	0.0019 (8)	0.0027 (8)
C7	0.0089 (11)	0.0118 (12)	0.0195 (12)	0.0014 (10)	−0.0001 (9)	−0.0015 (9)
C8	0.0115 (11)	0.0106 (12)	0.0182 (12)	0.0032 (10)	0.0015 (9)	0.0009 (9)
C3	0.0212 (13)	0.0186 (13)	0.0183 (12)	0.0041 (11)	0.0046 (10)	0.0007 (10)
C11	0.0182 (12)	0.0205 (14)	0.0180 (12)	0.0031 (11)	−0.0023 (10)	−0.0017 (10)
C9	0.0119 (11)	0.0155 (13)	0.0292 (13)	−0.0022 (11)	−0.0005 (10)	0.0025 (11)
C1	0.0149 (11)	0.0119 (12)	0.0178 (11)	0.0036 (10)	0.0013 (9)	−0.0032 (10)
C2	0.0135 (11)	0.0152 (13)	0.0168 (11)	0.0030 (10)	0.0030 (9)	−0.0038 (10)
C10	0.0139 (12)	0.0181 (13)	0.0260 (13)	0.0015 (10)	−0.0064 (10)	−0.0025 (11)
C6	0.0150 (12)	0.0190 (14)	0.0250 (13)	0.0008 (10)	−0.0010 (10)	−0.0034 (11)
C4	0.0273 (14)	0.0247 (14)	0.0163 (12)	0.0099 (12)	−0.0010 (10)	−0.0035 (11)
C12	0.0143 (12)	0.0189 (13)	0.0177 (12)	−0.0005 (10)	0.0020 (9)	0.0003 (10)
C5	0.0175 (12)	0.0269 (15)	0.0221 (13)	0.0065 (11)	−0.0060 (10)	−0.0064 (11)

Geometric parameters (Å, º) top

Cu1—N2	2.014 (2)	C7—C12	1.398 (3)
Cu1—N4	2.020 (2)	C8—C9	1.389 (4)
Cu1—N1	2.022 (2)	C3—C4	1.386 (4)
Cu1—N3	2.023 (2)	C3—C2	1.398 (4)
Cu1—O1	2.2433 (18)	C3—H3	0.93
S2—O2	1.4783 (18)	C11—C12	1.391 (4)
S2—O4	1.4817 (18)	C11—C10	1.395 (4)
S2—O1	1.4818 (19)	C11—H11	0.93
S2—O3	1.4827 (18)	C9—C10	1.389 (4)
N3—C2	1.453 (3)	C9—H9	0.93
N3—H3A	0.9	C1—C2	1.386 (4)
N3—H3B	0.9	C1—C6	1.391 (4)
N4—C1	1.456 (3)	C10—H10	0.93
N4—H4A	0.9	C6—C5	1.386 (4)
N4—H4B	0.9	C6—H6	0.93
N1—C7	1.451 (3)	C4—C5	1.399 (4)
N1—H1A	0.9	C4—H4	0.93
N1—H1B	0.9	C12—H12	0.93
N2—C8	1.457 (3)	C5—H5	0.93
N2—H2A	0.9	O1WA—O1WC	0.777 (10)
N2—H2B	0.9	O1WA—O1WB	1.530 (11)
C7—C8	1.391 (3)	O1WB—O1WC	0.763 (11)

N2—Cu1—N4	177.02 (9)	Cu1—N2—H2B	109.6
N2—Cu1—N1	85.04 (8)	H2A—N2—H2B	108.2
N4—Cu1—N1	94.02 (8)	C8—C7—C12	120.4 (2)
N2—Cu1—N3	95.41 (8)	C8—C7—N1	117.6 (2)
N4—Cu1—N3	84.88 (8)	C12—C7—N1	122.0 (2)
N1—Cu1—N3	166.90 (9)	C9—C8—C7	120.0 (2)
N2—Cu1—O1	89.99 (8)	C9—C8—N2	122.9 (2)
N4—Cu1—O1	92.89 (8)	C7—C8—N2	117.2 (2)
N1—Cu1—O1	94.26 (8)	C4—C3—C2	119.9 (3)
N3—Cu1—O1	98.82 (8)	C4—C3—H3	120.1
O2—S2—O4	109.16 (10)	C2—C3—H3	120.1
O2—S2—O1	109.79 (11)	C12—C11—C10	120.1 (2)
O4—S2—O1	110.08 (11)	C12—C11—H11	119.9
O2—S2—O3	109.68 (11)	C10—C11—H11	119.9
O4—S2—O3	109.30 (11)	C8—C9—C10	119.9 (2)
O1—S2—O3	108.81 (10)	C8—C9—H9	120
S2—O1—Cu1	124.94 (10)	C10—C9—H9	120
C2—N3—Cu1	109.83 (15)	C2—C1—C6	120.6 (2)
C2—N3—H3A	109.7	C2—C1—N4	117.2 (2)
Cu1—N3—H3A	109.7	C6—C1—N4	122.2 (2)
C2—N3—H3B	109.7	C1—C2—C3	119.8 (2)
Cu1—N3—H3B	109.7	C1—C2—N3	117.7 (2)
H3A—N3—H3B	108.2	C3—C2—N3	122.5 (2)
C1—N4—Cu1	109.96 (15)	C9—C10—C11	120.2 (2)
C1—N4—H4A	109.7	C9—C10—H10	119.9
Cu1—N4—H4A	109.7	C11—C10—H10	119.9
C1—N4—H4B	109.7	C5—C6—C1	119.6 (3)
Cu1—N4—H4B	109.7	C5—C6—H6	120.2
H4A—N4—H4B	108.2	C1—C6—H6	120.2
C7—N1—Cu1	109.78 (15)	C3—C4—C5	119.9 (3)
C7—N1—H1A	109.7	C3—C4—H4	120
Cu1—N1—H1A	109.7	C5—C4—H4	120
C7—N1—H1B	109.7	C11—C12—C7	119.3 (2)
Cu1—N1—H1B	109.7	C11—C12—H12	120.3
H1A—N1—H1B	108.2	C7—C12—H12	120.3
C8—N2—Cu1	110.08 (15)	C6—C5—C4	120.2 (2)
C8—N2—H2A	109.6	C6—C5—H5	119.9
Cu1—N2—H2A	109.6	C4—C5—H5	119.9
C8—N2—H2B	109.6

O2—S2—O1—Cu1	−48.22 (16)	N1—C7—C8—N2	1.2 (3)
O4—S2—O1—Cu1	71.97 (15)	Cu1—N2—C8—C9	−177.5 (2)
O3—S2—O1—Cu1	−168.27 (12)	Cu1—N2—C8—C7	3.4 (3)
N2—Cu1—O1—S2	128.22 (14)	C7—C8—C9—C10	−0.2 (4)
N4—Cu1—O1—S2	−51.05 (14)	N2—C8—C9—C10	−179.3 (2)
N1—Cu1—O1—S2	43.19 (14)	Cu1—N4—C1—C2	5.9 (3)
N3—Cu1—O1—S2	−136.31 (13)	Cu1—N4—C1—C6	−175.0 (2)
N2—Cu1—N3—C2	−172.48 (16)	C6—C1—C2—C3	−1.4 (4)
N4—Cu1—N3—C2	4.55 (16)	N4—C1—C2—C3	177.8 (2)
N1—Cu1—N3—C2	−81.2 (4)	C6—C1—C2—N3	178.6 (2)
O1—Cu1—N3—C2	96.69 (16)	N4—C1—C2—N3	−2.2 (3)
N1—Cu1—N4—C1	161.29 (16)	C4—C3—C2—C1	−0.2 (4)
N3—Cu1—N4—C1	−5.62 (16)	C4—C3—C2—N3	179.8 (2)
O1—Cu1—N4—C1	−104.23 (16)	Cu1—N3—C2—C1	−2.6 (3)
N2—Cu1—N1—C7	5.41 (16)	Cu1—N3—C2—C3	177.4 (2)
N4—Cu1—N1—C7	−171.75 (16)	C8—C9—C10—C11	0.4 (4)
N3—Cu1—N1—C7	−87.1 (4)	C12—C11—C10—C9	−0.4 (4)
O1—Cu1—N1—C7	95.04 (16)	C2—C1—C6—C5	1.9 (4)
N1—Cu1—N2—C8	−4.83 (16)	N4—C1—C6—C5	−177.2 (2)
N3—Cu1—N2—C8	162.02 (16)	C2—C3—C4—C5	1.2 (4)
O1—Cu1—N2—C8	−99.11 (16)	C10—C11—C12—C7	0.3 (4)
Cu1—N1—C7—C8	−5.1 (3)	C8—C7—C12—C11	−0.1 (4)
Cu1—N1—C7—C12	176.9 (2)	N1—C7—C12—C11	177.8 (2)
C12—C7—C8—C9	0.1 (4)	C1—C6—C5—C4	−0.9 (4)
N1—C7—C8—C9	−177.9 (2)	C3—C4—C5—C6	−0.7 (4)
C12—C7—C8—N2	179.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.90	2.03	2.904 (3)	164
N1—H1B···O2	0.90	2.06	2.873 (4)	149
N2—H2A···O3ⁱⁱ	0.90	2.16	3.059 (4)	174
N2—H2B···O3ⁱⁱⁱ	0.90	2.02	2.890 (4)	161
N3—H3A···O3ⁱⁱⁱ	0.90	2.45	3.188 (4)	139
N3—H3A···O4ⁱⁱⁱ	0.90	2.24	3.068 (4)	153
N4—H4A···O4	0.90	2.37	3.202 (4)	153
N4—H4B···O2ⁱ	0.90	1.96	2.825 (4)	160
C4—H4···O4^iv	0.93	2.59	3.512 (4)	172

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

Experimental details

Crystal data
Chemical formula	[Cu(SO₄)(C₆H₈N₂)₂]·H₂O
M_r	393.90
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	120
a, b, c (Å)	18.6794 (4), 7.5317 (2), 21.9757 (5)
V (Å³)	3091.71 (13)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.58
Crystal size (mm)	0.38 × 0.15 × 0.05

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1995)
T_min, T_max	0.543, 0.924
No. of measured, independent and observed [I > 2σ(I)] reflections	42067, 3555, 2957
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.097, 1.08
No. of reflections	3555
No. of parameters	212
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.29, −0.64

Computer programs: COLLECT (Nonius, 2002), DENZO-SMN (Otwinowski & Minor, 1997), EVALCCD (Duisenberg et al., 2003), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEPIII (Farrugia, 1997), WinGX (Farrugia, 1999) and PARST (Nardelli, 1995).

Selected bond lengths (Å) top

Cu1—N2	2.014 (2)	Cu1—N3	2.023 (2)
Cu1—N4	2.020 (2)	Cu1—O1	2.2433 (18)
Cu1—N1	2.022 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.9000	2.0300	2.904 (3)	164.00
N1—H1B···O2	0.9000	2.0600	2.873 (4)	149.00
N2—H2A···O3ⁱⁱ	0.9000	2.1600	3.059 (4)	174.00
N2—H2B···O3ⁱⁱⁱ	0.9000	2.0200	2.890 (4)	161.00
N3—H3A···O3ⁱⁱⁱ	0.9000	2.4500	3.188 (4)	139.00
N3—H3A···O4ⁱⁱⁱ	0.9000	2.2400	3.068 (4)	153.00
N4—H4A···O4	0.9000	2.3700	3.202 (4)	153.00
N4—H4B···O2ⁱ	0.9000	1.9600	2.825 (4)	160.00
C4—H4···O4^iv	0.9300	2.5900	3.512 (4)	172.00

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

Acknowledgements

This work was supported by the Laboratoire de Chimie des Materiaux, Faculté des Sciences, Université Mentouri. We would like to thank J.-Y. Saillard of Rennes 1 University for providing the diffraction facilities.

References

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