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

The title complex, [Cu(SO(4))(C(6)H(8)N(2))(2)]·H(2)O, was obtained under hydro-thermal 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 inter-actions between the layers consolidate the three-dimensional set-up. There are voids in the structure filled with lattice water mol-ecules 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 = 393.90

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.097

S = 1.08

3555 reflections

212 parameters

1 restraint

H-atom parameters constrained

Δρmax = 1.29 e Å−3

Δρmin = −0.64 e Å−3

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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812041967/wm2682sup1.cif

Click here for additional data file.

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(SO4)(C6H8N2)2]·H2O	F(000) = 1624
Mr = 393.90	Dx = 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

Nonius KappaCCD diffractometer	3555 independent reflections
Radiation source: Enraf Nonius FR590	2957 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
Detector resolution: 9 pixels mm-1	θmax = 27.5°, θmin = 3.1°
CCD rotation images, thin slices scans	h = −24→24
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −9→9
Tmin = 0.543, Tmax = 0.924	l = −28→28
42067 measured reflections

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(Fo2) + (0.0455P)2 + 5.6842P] where P = (Fo2 + 2Fc2)/3
3555 reflections	(Δ/σ)max = 0.005
212 parameters	Δρmax = 1.29 e Å−3
1 restraint	Δρmin = −0.64 e Å−3

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.

	x	y	z	Uiso*/Ueq	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)

	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)

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)

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···O4iv	0.93	2.59	3.512 (4)	172

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⋯O4iv	0.93	2.59	3.512 (4)	172

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .