catena-Poly[[tetra­aqua­copper(II)]-μ-pyrazine-2-carboxamide-κ3N4:N1,O-[bis­(sulfato-κO)copper(II)]-μ-pyrazine-2-carboxamide-κ3N1,O:N4]

Shirvan, S.A.; Haydari Dezfuli, S.

doi:10.1107/S1600536812031844

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 8| August 2012| Pages m1082-m1083

https://doi.org/10.1107/S1600536812031844

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catena-Poly[[tetraaquacopper(II)]-μ-pyrazine-2-carboxamide-κ³N⁴:N¹,O-[bis(sulfato-κO)copper(II)]-μ-pyrazine-2-carboxamide-κ³N¹,O:N⁴]

Sadif A. Shirvan ^a ^* and Sara Haydari Dezfuli ^a

^aDepartment of Chemistry, Omidieh Branch, Islamic Azad University, Omidieh, Iran
^*Correspondence e-mail: sadif.shirvan1@gmail.com

(Received 27 June 2012; accepted 12 July 2012; online 18 July 2012)

In the crystal of the title polymeric compound, [Cu₂(SO₄)₂(C₅H₅N₃O)₂(H₂O)₄]_n, two independent Cu^II atoms are located on individual inversion centers. One Cu^II atom is coordinated by four water molecules and two pyrazine-2-carboxamide ligands in a distorted O₄N₂ octahedral geometry; the other is N,O-chelated by two pyrazine-2-carboxamide ligands and further coordinated by two sulfate anions in a distorted O₄N₂ octahedral geometry. The pyrazine-2-carboxamide ligands bridge the Cu^II atoms to form a polymeric chain running along [110]. The crystal structure features N—H⋯O, O—H⋯O and weak C—H⋯O hydrogen bonds.

Related literature

For related structures, see: Abu-Youssef et al. (2006 ); Azhdari Tehrani et al. (2010 ); Goher & Mautner (2000 ); Kristiansson (2002 ); Mir Mohammad Sadegh et al. (2010 ); Munakata et al. (1997 ); Pacigova et al. (2008 ); Shirvan & Haydari Dezfuli (2012a ,b ,c ).

Experimental

Crystal data

[Cu₂(SO₄)₂(C₅H₅N₃O)₂(H₂O)₄]
M_r = 318.77
Monoclinic, P 2₁ /c
a = 11.2699 (12) Å
b = 7.3799 (7) Å
c = 11.8669 (15) Å
β = 95.267 (9)°
V = 982.81 (19) Å³
Z = 4
Mo Kα radiation
μ = 2.47 mm⁻¹
T = 298 K
0.25 × 0.20 × 0.04 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.589, T_max = 0.926
7420 measured reflections
1928 independent reflections
1544 reflections with I > 2σ(I)
R_int = 0.090

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.103
S = 1.07
1928 reflections
173 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.83 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O1	1.961 (3)
Cu1—O6	2.447 (3)
Cu1—N1	1.979 (3)
Cu2—O2	2.363 (2)
Cu2—O3	1.968 (3)
Cu2—N2	2.034 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2B⋯O4ⁱ	0.83 (3)	2.01 (4)	2.845 (4)	177 (5)
O2—H2C⋯O7ⁱⁱ	0.83 (4)	2.03 (3)	2.815 (4)	159 (3)
O3—H3D⋯O7ⁱⁱⁱ	0.82 (3)	1.87 (3)	2.687 (3)	175 (5)
O3—H3E⋯O4ⁱⁱ	0.82 (3)	1.87 (3)	2.679 (4)	169 (3)
N3—H3B⋯O6^iv	0.86	2.01	2.820 (4)	157
N3—H3C⋯O5^v	0.86	2.03	2.862 (5)	162
C1—H1⋯O7^vi	0.93	2.24	3.108 (5)	154
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) x, y-1, z; (v) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vi) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812031844/xu5585sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812031844/xu5585Isup2.hkl

checkCIF report

Comment top

Pyrazine-2-carboxamide (pzc) is a good ligand, and a few complexes with pzc have been prepared, such as that of mercury (Azhdari Tehrani et al., 2010; Mir Mohammad Sadegh et al., 2010), vanadium (Pacigova et al., 2008), manganese (Abu-Youssef et al., 2006), copper (Kristiansson, 2002; Munakata et al., 1997; Goher & Mautner, 2000), zinc (Shirvan & Haydari Dezfuli, 2012a,b,c). Here, we report the synthesis and structure of the title compound.

The asymmetric unit of the title compound, (Fig. 1), contains two half of Cu^II atom, two half of pyrazine-2-carboxamide ligands, two water molecules and one sulfate anion. The octahedral Cu^II ions form a polymeric chain, being bridged by two pyrazine-2-carboxamide ligands. There are two crystallographically independent Cu^II centers with center adopts a {CuO₄N₂} coordination geometry, both of which reside on centers of symmetry. The first Cu(1) center defined by two oxygen and two nitrogen from two pyrazine-2-carboxamide ligands and by two oxygen from two sulfate anions. The second Cu(2) center is also found in a octahedral coordination environment by two pyrazine nitrogen donors from two pyrazine-2-carboxamide ligands and by four aquo oxygen donors. The Cu—O and Cu—N bond lengths and angles are collected in Table 1.

In the crystal structure, Intermolecular N—H···O, O—H···O and C—H···O hydrogen bonds may stabilize the structure (Table 2 & Fig. 2).

Related literature top

For related structures, see: Abu-Youssef et al. (2006); Azhdari Tehrani et al. (2010); Goher & Mautner (2000); Kristiansson (2002); Mir Mohammad Sadegh et al. (2010); Munakata et al. (1997); Pacigova et al. (2008); Shirvan & Haydari Dezfuli (2012a,b,c).

Experimental top

A solution of pyrazine-2-carboxamide (0.25 g, 2.0 mmol) in methanol (10 ml) was added to a solution of CuSO₄.5H₂O (0.25 g, 1.0 mmol) in water (5 ml) and the resulting blue solution was stirred for 15 min at room temperature. This solution was left to evaporate slowly at room temperature. After one week, blue block crystals of the title compound were isolated (yield 0.23 g, 72.2%).

Structure description top

In the crystal structure, Intermolecular N—H···O, O—H···O and C—H···O hydrogen bonds may stabilize the structure (Table 2 & Fig. 2).

For related structures, see: Abu-Youssef et al. (2006); Azhdari Tehrani et al. (2010); Goher & Mautner (2000); Kristiansson (2002); Mir Mohammad Sadegh et al. (2010); Munakata et al. (1997); Pacigova et al. (2008); Shirvan & Haydari Dezfuli (2012a,b,c).

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (a) -x,1 - y,1 - z; (b) 1 - x,-y,1 - z].
	Fig. 2. Unit-cell packing diagram for title molecule. Hydrogen bonds are shown as dashed lines.

catena-Poly[[tetraaquacopper(II)]-µ-pyrazine-2-carboxamide- κ³N⁴:N¹,O-[bis(sulfato-κO)copper(II)]- µ-pyrazine-2-carboxamide-κ³N¹,O:N⁴] top

Crystal data top

[Cu₂(SO₄)₂(C₅H₅N₃O)₂(H₂O)₄]	F(000) = 644
M_r = 318.77	D_x = 2.154 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7420 reflections
a = 11.2699 (12) Å	θ = 1.8–26.0°
b = 7.3799 (7) Å	µ = 2.47 mm⁻¹
c = 11.8669 (15) Å	T = 298 K
β = 95.267 (9)°	Plate, blue
V = 982.81 (19) Å³	0.25 × 0.20 × 0.04 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	1928 independent reflections
Radiation source: fine-focus sealed tube	1544 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.090
ω scans	θ_max = 26.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −13→13
T_min = 0.589, T_max = 0.926	k = −8→9
7420 measured reflections	l = −14→14

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.057P)²] where P = (F_o² + 2F_c²)/3
1928 reflections	(Δ/σ)_max = 0.006
173 parameters	Δρ_max = 0.83 e Å⁻³
6 restraints	Δρ_min = −0.69 e Å⁻³

Crystal data top

[Cu₂(SO₄)₂(C₅H₅N₃O)₂(H₂O)₄]	V = 982.81 (19) Å³
M_r = 318.77	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.2699 (12) Å	µ = 2.47 mm⁻¹
b = 7.3799 (7) Å	T = 298 K
c = 11.8669 (15) Å	0.25 × 0.20 × 0.04 mm
β = 95.267 (9)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1928 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1544 reflections with I > 2σ(I)
T_min = 0.589, T_max = 0.926	R_int = 0.090
7420 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	6 restraints
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.83 e Å⁻³
1928 reflections	Δρ_min = −0.69 e Å⁻³
173 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
C1	0.2270 (3)	0.3902 (5)	0.4101 (3)	0.0263 (7)
H1	0.2189	0.4879	0.3605	0.032*
C2	0.3319 (3)	0.2877 (5)	0.4182 (3)	0.0272 (8)
H2	0.3936	0.3209	0.3756	0.033*
C3	0.2541 (3)	0.1005 (5)	0.5473 (3)	0.0262 (8)
H3	0.2609	0.0001	0.5948	0.031*
C4	0.1517 (3)	0.2024 (5)	0.5411 (3)	0.0230 (7)
C5	0.0473 (3)	0.1773 (5)	0.6079 (3)	0.0261 (7)
N1	0.1397 (2)	0.3496 (4)	0.4721 (2)	0.0230 (6)
N2	0.3451 (2)	0.1431 (4)	0.4860 (2)	0.0229 (6)
N3	0.0314 (3)	0.0226 (4)	0.6589 (3)	0.0333 (8)
H3C	−0.0296	0.0077	0.6965	0.040*
H3B	0.0820	−0.0639	0.6547	0.040*
O1	−0.0233 (2)	0.3090 (4)	0.6107 (2)	0.0281 (6)
O2	0.5178 (3)	0.0396 (4)	0.3047 (2)	0.0364 (7)
H2B	0.465 (3)	0.007 (6)	0.255 (3)	0.040 (13)*
H2C	0.562 (3)	0.107 (5)	0.272 (3)	0.045 (14)*
O3	0.5887 (2)	0.2275 (4)	0.5292 (2)	0.0280 (6)
H3D	0.627 (4)	0.248 (7)	0.5901 (17)	0.069 (18)*
H3E	0.620 (3)	0.286 (5)	0.481 (2)	0.033 (12)*
O4	0.3372 (2)	0.5564 (4)	0.6316 (2)	0.0313 (6)
O5	0.2000 (3)	0.4720 (4)	0.7649 (2)	0.0364 (7)
O6	0.1397 (2)	0.6869 (4)	0.6196 (2)	0.0330 (6)
O7	0.2862 (2)	0.7724 (4)	0.7689 (2)	0.0340 (6)
Cu1	0.0000	0.5000	0.5000	0.0258 (2)
Cu2	0.5000	0.0000	0.5000	0.02044 (18)
S1	0.23960 (7)	0.61972 (11)	0.69724 (6)	0.0199 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0328 (19)	0.0213 (18)	0.0248 (16)	−0.0008 (15)	0.0027 (14)	0.0046 (14)
C2	0.0224 (17)	0.028 (2)	0.0322 (18)	0.0006 (15)	0.0065 (14)	0.0026 (15)
C3	0.0231 (17)	0.026 (2)	0.0297 (16)	0.0046 (15)	0.0026 (13)	0.0052 (15)
C4	0.0208 (17)	0.0205 (18)	0.0272 (16)	0.0014 (13)	−0.0011 (13)	−0.0019 (14)
C5	0.0228 (17)	0.0268 (19)	0.0282 (16)	0.0018 (14)	0.0000 (14)	−0.0001 (15)
N1	0.0220 (14)	0.0189 (15)	0.0275 (14)	0.0025 (11)	−0.0019 (12)	0.0008 (11)
N2	0.0162 (13)	0.0230 (16)	0.0294 (14)	0.0010 (11)	0.0021 (11)	0.0023 (12)
N3	0.0307 (17)	0.0274 (18)	0.0445 (18)	0.0118 (13)	0.0175 (15)	0.0125 (15)
O1	0.0254 (12)	0.0270 (14)	0.0325 (12)	0.0096 (10)	0.0050 (10)	0.0026 (11)
O2	0.0283 (14)	0.0500 (19)	0.0305 (13)	−0.0121 (13)	0.0003 (12)	0.0030 (13)
O3	0.0292 (14)	0.0275 (15)	0.0263 (12)	−0.0081 (11)	−0.0023 (11)	0.0035 (11)
O4	0.0297 (13)	0.0359 (15)	0.0290 (12)	0.0042 (11)	0.0068 (11)	0.0007 (11)
O5	0.0350 (15)	0.0319 (16)	0.0429 (15)	0.0014 (12)	0.0080 (12)	0.0126 (12)
O6	0.0321 (14)	0.0281 (15)	0.0358 (13)	0.0082 (11)	−0.0135 (11)	−0.0032 (11)
O7	0.0360 (14)	0.0310 (16)	0.0336 (13)	−0.0032 (12)	−0.0044 (11)	−0.0098 (12)
Cu1	0.0225 (3)	0.0205 (4)	0.0344 (3)	0.0111 (2)	0.0028 (2)	0.0033 (2)
Cu2	0.0126 (3)	0.0198 (3)	0.0290 (3)	0.0020 (2)	0.0018 (2)	0.0008 (2)
S1	0.0176 (4)	0.0204 (4)	0.0212 (4)	0.0009 (3)	−0.0011 (3)	0.0001 (3)

Geometric parameters (Å, º) top

Cu1—O1	1.961 (3)	O2—H2B	0.83 (3)
Cu1—O6	2.447 (3)	O2—H2C	0.83 (4)
Cu1—N1	1.979 (3)	O3—H3D	0.82 (3)
Cu1—O1ⁱ	1.961 (3)	O3—H3E	0.82 (3)
Cu1—O6ⁱ	2.447 (3)	N1—C1	1.316 (4)
Cu1—N1ⁱ	1.979 (3)	N1—C4	1.360 (5)
Cu2—O2	2.363 (2)	N2—C2	1.337 (5)
Cu2—O3	1.968 (3)	N2—C3	1.348 (4)
Cu2—N2	2.034 (2)	N3—C5	1.312 (5)
Cu2—O2ⁱⁱ	2.363 (2)	N3—H3C	0.8600
Cu2—O3ⁱⁱ	1.968 (3)	N3—H3B	0.8600
Cu2—N2ⁱⁱ	2.034 (2)	C1—C2	1.399 (5)
S1—O4	1.481 (2)	C3—C4	1.374 (5)
S1—O5	1.449 (3)	C4—C5	1.489 (5)
S1—O6	1.474 (3)	C1—H1	0.9300
S1—O7	1.479 (3)	C2—H2	0.9300
O1—C5	1.258 (4)	C3—H3	0.9300

S1···C4	3.683 (4)	O7···H2C^vi	2.03 (3)
S1···O2ⁱⁱⁱ	3.479 (3)	O7···H3D^vii	1.87 (3)
S1···H3B^iv	2.9500	O7···H1^x	2.2400
S1···H3C^v	2.9000	O7···H2Bⁱⁱⁱ	2.90 (4)
S1···H3^iv	3.0800	N1···S1	3.439 (3)
S1···H2C^vi	3.01 (4)	N1···O1	2.593 (3)
S1···H3E^vi	2.84 (3)	N1···O4	3.177 (4)
S1···H3D^vii	2.97 (3)	N1···O6	3.043 (4)
S1···H2Bⁱⁱⁱ	2.74 (4)	N1···N2	2.764 (4)
O1···O5	3.207 (4)	N1···C5	2.368 (4)
O1···N1	2.593 (3)	N1···O1ⁱ	2.966 (4)
O1···C4	2.343 (4)	N1···O6ⁱ	3.247 (3)
O1···N3^v	3.165 (4)	N2···O2	3.126 (4)
O1···C1ⁱ	3.187 (4)	N2···O3	2.816 (3)
O1···O6ⁱ	2.921 (3)	N2···N1	2.764 (4)
O1···N1ⁱ	2.966 (4)	N2···O2ⁱⁱ	3.110 (4)
O2···O4^viii	2.845 (4)	N2···O3ⁱⁱ	2.845 (4)
O2···N2ⁱⁱ	3.110 (4)	N2···O5^viii	3.081 (4)
O2···O3	3.044 (4)	N3···O6^xi	2.820 (4)
O2···N2	3.126 (4)	N3···C4^xii	3.428 (5)
O2···C2	3.174 (5)	N3···O1^xiii	3.165 (4)
O2···S1^viii	3.479 (3)	N3···O5^xiii	2.862 (5)
O2···O3ⁱⁱ	3.106 (4)	N3···H3	2.7700
O2···O7^vi	2.815 (4)	C1···O4	3.059 (4)
O2···C3ⁱⁱ	3.152 (5)	C1···O5^viii	3.180 (5)
O3···N2ⁱⁱ	2.845 (4)	C1···O7^xiv	3.108 (5)
O3···O7^ix	2.687 (3)	C2···O4	3.213 (4)
O3···C2	3.100 (4)	C2···O5^viii	2.949 (5)
O3···O4^vi	2.679 (4)	C3···O5^viii	3.393 (4)
O3···O2	3.044 (4)	C4···O5	3.323 (4)
O3···N2	2.816 (3)	C4···S1	3.683 (4)
O3···O2ⁱⁱ	3.106 (4)	C4···N3^xii	3.428 (5)
O3···C3ⁱⁱ	3.181 (4)	C5···O5	3.252 (5)
O4···N1	3.177 (4)	C3···H3B	2.7000
O4···C2	3.213 (4)	H1···O1ⁱ	2.7100
O4···O2ⁱⁱⁱ	2.845 (4)	H1···O7^xiv	2.2400
O4···O3^vi	2.679 (4)	H2···O2	2.6800
O4···C1	3.059 (4)	H2···O3	2.8100
O5···C2ⁱⁱⁱ	2.949 (5)	H2B···S1^viii	2.74 (4)
O5···C1ⁱⁱⁱ	3.180 (5)	H2B···O4^viii	2.01 (4)
O5···C5	3.252 (5)	H2B···O7^viii	2.90 (4)
O5···N2ⁱⁱⁱ	3.081 (4)	H2C···S1^vi	3.01 (4)
O5···C4	3.323 (4)	H2C···O7^vi	2.03 (3)
O5···O1	3.207 (4)	H2C···H3ⁱⁱ	2.5500
O5···C3ⁱⁱⁱ	3.393 (4)	H2C···H3D^viii	2.58 (5)
O5···N3^v	2.862 (5)	H3···S1^xi	3.0800
O6···N1ⁱ	3.247 (3)	H3···O6^xi	2.7100
O6···N3^iv	2.820 (4)	H3···O7^xi	2.6600
O6···N1	3.043 (4)	H3···N3	2.7700
O6···O1ⁱ	2.921 (3)	H3···H3B	2.2500
O6···C5ⁱ	3.419 (4)	H3···O2ⁱⁱ	2.6800
O7···O3^vii	2.687 (3)	H3···O3ⁱⁱ	2.8800
O7···C1^x	3.108 (5)	H3···H2Cⁱⁱ	2.5500
O7···O2^vi	2.815 (4)	H3B···S1^xi	2.9500
O1···H3C^v	2.7400	H3B···O6^xi	2.0100
O1···H1ⁱ	2.7100	H3B···O7^xi	2.8300
O2···H3ⁱⁱ	2.6800	H3B···C3	2.7000
O2···H2	2.6800	H3B···H3	2.2500
O3···H2	2.8100	H3C···S1^xiii	2.9000
O3···H3ⁱⁱ	2.8800	H3C···O1^xiii	2.7400
O4···H2Bⁱⁱⁱ	2.01 (4)	H3C···O5^xiii	2.0300
O4···H3E^vi	1.87 (3)	H3D···S1^ix	2.97 (3)
O5···H3C^v	2.0300	H3D···O7^ix	1.87 (3)
O6···H3B^iv	2.0100	H3D···H2Cⁱⁱⁱ	2.58 (5)
O6···H3^iv	2.7100	H3E···S1^vi	2.84 (3)
O7···H3^iv	2.6600	H3E···O4^vi	1.87 (3)
O7···H3B^iv	2.8300

O1—Cu1—O6	97.77 (10)	O5—S1—O7	111.47 (15)
O1—Cu1—N1	82.32 (10)	O6—S1—O7	108.29 (16)
O1—Cu1—O1ⁱ	180.00	Cu1—O1—C5	114.4 (2)
O1—Cu1—O6ⁱ	82.23 (10)	Cu1—O6—S1	125.95 (17)
O1—Cu1—N1ⁱ	97.68 (10)	Cu2—O2—H2B	123 (3)
O6—Cu1—N1	86.20 (10)	Cu2—O2—H2C	130 (3)
O1ⁱ—Cu1—O6	82.23 (10)	H2B—O2—H2C	105 (4)
O6—Cu1—O6ⁱ	180.00	Cu2—O3—H3D	122 (3)
O6—Cu1—N1ⁱ	93.80 (10)	Cu2—O3—H3E	125 (2)
O1ⁱ—Cu1—N1	97.68 (10)	H3D—O3—H3E	107 (4)
O6ⁱ—Cu1—N1	93.80 (10)	Cu1—N1—C4	112.6 (2)
N1—Cu1—N1ⁱ	180.00	C1—N1—C4	118.7 (3)
O1ⁱ—Cu1—O6ⁱ	97.77 (10)	Cu1—N1—C1	127.8 (2)
O1ⁱ—Cu1—N1ⁱ	82.32 (10)	C2—N2—C3	117.6 (3)
O6ⁱ—Cu1—N1ⁱ	86.20 (10)	Cu2—N2—C2	120.7 (2)
O2—Cu2—O3	88.84 (10)	Cu2—N2—C3	121.7 (2)
O2—Cu2—N2	90.30 (10)	C5—N3—H3C	120.00
O2—Cu2—O2ⁱⁱ	180.00	C5—N3—H3B	120.00
O2—Cu2—O3ⁱⁱ	91.16 (10)	H3B—N3—H3C	120.00
O2—Cu2—N2ⁱⁱ	89.70 (10)	N1—C1—C2	120.6 (3)
O3—Cu2—N2	89.41 (11)	N2—C2—C1	121.3 (3)
O2ⁱⁱ—Cu2—O3	91.16 (10)	N2—C3—C4	121.4 (3)
O3—Cu2—O3ⁱⁱ	180.00	N1—C4—C5	112.3 (3)
O3—Cu2—N2ⁱⁱ	90.59 (11)	C3—C4—C5	127.2 (3)
O2ⁱⁱ—Cu2—N2	89.70 (10)	N1—C4—C3	120.4 (3)
O3ⁱⁱ—Cu2—N2	90.59 (11)	N3—C5—C4	120.1 (3)
N2—Cu2—N2ⁱⁱ	180.00	O1—C5—N3	123.1 (3)
O2ⁱⁱ—Cu2—O3ⁱⁱ	88.84 (10)	O1—C5—C4	116.8 (3)
O2ⁱⁱ—Cu2—N2ⁱⁱ	90.30 (10)	N1—C1—H1	120.00
O3ⁱⁱ—Cu2—N2ⁱⁱ	89.41 (11)	C2—C1—H1	120.00
O4—S1—O5	109.61 (17)	N2—C2—H2	119.00
O4—S1—O6	109.82 (14)	C1—C2—H2	119.00
O4—S1—O7	107.53 (14)	N2—C3—H3	119.00
O5—S1—O6	110.07 (17)	C4—C3—H3	119.00

O6—Cu1—O1—C5	−91.3 (2)	O3ⁱⁱ—Cu2—N2—C3	53.3 (3)
N1—Cu1—O1—C5	−6.2 (2)	O5—S1—O6—Cu1	−47.0 (2)
O6ⁱ—Cu1—O1—C5	88.7 (2)	O7—S1—O6—Cu1	−169.06 (14)
N1ⁱ—Cu1—O1—C5	173.8 (2)	O4—S1—O6—Cu1	73.8 (2)
O1—Cu1—O6—S1	41.74 (18)	Cu1—O1—C5—C4	12.7 (4)
N1—Cu1—O6—S1	−39.97 (17)	Cu1—O1—C5—N3	−166.3 (3)
O1ⁱ—Cu1—O6—S1	−138.26 (18)	C4—N1—C1—C2	−2.3 (5)
N1ⁱ—Cu1—O6—S1	140.03 (17)	Cu1—N1—C1—C2	166.0 (3)
O1—Cu1—N1—C4	−1.9 (2)	Cu1—N1—C4—C5	8.4 (4)
O6—Cu1—N1—C4	96.4 (2)	C1—N1—C4—C5	178.4 (3)
O1ⁱ—Cu1—N1—C4	178.1 (2)	Cu1—N1—C4—C3	−168.8 (3)
O1—Cu1—N1—C1	−170.8 (3)	C1—N1—C4—C3	1.2 (5)
O6—Cu1—N1—C1	−72.5 (3)	C3—N2—C2—C1	−0.7 (5)
O1ⁱ—Cu1—N1—C1	9.2 (3)	C2—N2—C3—C4	−0.4 (5)
O6ⁱ—Cu1—N1—C1	107.6 (3)	Cu2—N2—C3—C4	177.2 (3)
O6ⁱ—Cu1—N1—C4	−83.6 (2)	Cu2—N2—C2—C1	−178.3 (3)
O3—Cu2—N2—C3	−126.7 (3)	N1—C1—C2—N2	2.1 (5)
O2ⁱⁱ—Cu2—N2—C3	−35.5 (3)	N2—C3—C4—N1	0.2 (5)
O2—Cu2—N2—C3	144.5 (3)	N2—C3—C4—C5	−176.6 (3)
O2—Cu2—N2—C2	−38.0 (3)	N1—C4—C5—O1	−14.2 (5)
O3—Cu2—N2—C2	50.8 (3)	C3—C4—C5—N3	−18.3 (6)
O2ⁱⁱ—Cu2—N2—C2	142.0 (3)	N1—C4—C5—N3	164.8 (3)
O3ⁱⁱ—Cu2—N2—C2	−129.2 (3)	C3—C4—C5—O1	162.7 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···O4^viii	0.83 (3)	2.01 (4)	2.845 (4)	177 (5)
O2—H2C···O7^vi	0.83 (4)	2.03 (3)	2.815 (4)	159 (3)
O3—H3D···O7^ix	0.82 (3)	1.87 (3)	2.687 (3)	175 (5)
O3—H3E···O4^vi	0.82 (3)	1.87 (3)	2.679 (4)	169 (3)
N3—H3B···O6^xi	0.86	2.01	2.820 (4)	157
N3—H3C···O5^xiii	0.86	2.03	2.862 (5)	162
C1—H1···O7^xiv	0.93	2.24	3.108 (5)	154

Symmetry codes: (vi) −x+1, −y+1, −z+1; (viii) x, −y+1/2, z−1/2; (ix) −x+1, y−1/2, −z+3/2; (xi) x, y−1, z; (xiii) −x, y−1/2, −z+3/2; (xiv) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[Cu₂(SO₄)₂(C₅H₅N₃O)₂(H₂O)₄]
M_r	318.77
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	11.2699 (12), 7.3799 (7), 11.8669 (15)
β (°)	95.267 (9)
V (Å³)	982.81 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.47
Crystal size (mm)	0.25 × 0.20 × 0.04

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.589, 0.926
No. of measured, independent and observed [I > 2σ(I)] reflections	7420, 1928, 1544
R_int	0.090
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.103, 1.07
No. of reflections	1928
No. of parameters	173
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)	0.83, −0.69

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

Selected bond lengths (Å) top

Cu1—O1	1.961 (3)	Cu2—O2	2.363 (2)
Cu1—O6	2.447 (3)	Cu2—O3	1.968 (3)
Cu1—N1	1.979 (3)	Cu2—N2	2.034 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···O4ⁱ	0.83 (3)	2.01 (4)	2.845 (4)	177 (5)
O2—H2C···O7ⁱⁱ	0.83 (4)	2.03 (3)	2.815 (4)	159 (3)
O3—H3D···O7ⁱⁱⁱ	0.82 (3)	1.87 (3)	2.687 (3)	175 (5)
O3—H3E···O4ⁱⁱ	0.82 (3)	1.87 (3)	2.679 (4)	169 (3)
N3—H3B···O6^iv	0.8600	2.0100	2.820 (4)	157.00
N3—H3C···O5^v	0.8600	2.0300	2.862 (5)	162.00
C1—H1···O7^vi	0.9300	2.2400	3.108 (5)	154.00

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

Acknowledgements

We are grateful to the Islamic Azad University, Omidieh Branch, for financial support.

References

Abu-Youssef, M. A. M., Escuer, A. & Langer, V. (2006). Eur. J. Inorg. Chem. pp. 3177–3184. Google Scholar
Azhdari Tehrani, A., Mir Mohammad Sadegh, B. & Khavasi, H. R. (2010). Acta Cryst. E66, m261. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Goher, M. A. S. & Mautner, F. A. (2000). Polyhedron, 19, 601–606. Web of Science CSD CrossRef CAS Google Scholar
Kristiansson, O. (2002). Acta Cryst. E58, m130–m132. Web of Science CSD CrossRef IUCr Journals Google Scholar
Mir Mohammad Sadegh, B., Azhdari Tehrani, A. & Khavasi, H. R. (2010). Acta Cryst. E66, m158. Web of Science CSD CrossRef IUCr Journals Google Scholar
Munakata, M., Wu, L. P., Sowa, T. K., Maekawa, M., Moriwaki, K. & Kitagawa, S. (1997). Inorg. Chem. 36, 5416–5418. CSD CrossRef CAS Web of Science Google Scholar
Pacigova, S., Gyepes, R., Tatiersky, J. & Sivak, M. (2008). Dalton Trans. pp. 121–130. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shirvan, S. A. & Haydari Dezfuli, S. (2012a). Acta Cryst. E68, m527. CSD CrossRef IUCr Journals Google Scholar
Shirvan, S. A. & Haydari Dezfuli, S. (2012b). Acta Cryst. E68, m627–m628. CSD CrossRef IUCr Journals Google Scholar
Shirvan, S. A. & Haydari Dezfuli, S. (2012c). Acta Cryst. E68, m546. CSD CrossRef IUCr Journals Google Scholar

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