Bis(1,10-phenanthroline-κ2N,N′)(sulfato-O)copper(II) ethane-1,2-diol monosolvate

Zhong, K.-L.

doi:10.1107/S1600536811031175

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Pages m1215-m1216

doi:10.1107/S1600536811031175

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Bis(1,10-phenanthroline-κ²N,N′)(sulfato-O)copper(II) ethane-1,2-diol monosolvate

Kai-Long Zhong ^a ^*

^aDepartment of Applied Chemistry, Nanjing College of Chemical Technology, Nanjing, 210048, People's Republic of China
^*Correspondence e-mail: zklong@tom.com

(Received 28 July 2011; accepted 2 August 2011; online 11 August 2011)

In the title compound, [Cu(SO₄)(C₁₂H₈N₂)₂]·C₂H₆O₂, the Cu^II ion is five-coordinated in a distorted square-pyramidal manner by four N atoms from two chelating 1,10-phenanthroline (phen) ligands and one O atom from a monodentate sulfate anion. The four N atoms comprise a square and the one O atom the apex of a square pyramid. The two chelating N₂C₂ groups are oriented at 71.1 (2)°. In the crystal, the components are connected by intermolecular O—H⋯O hydrogen bonding. The presence of pseudosymmetry in the structure suggests the higher symmetry space group C2/c, but attempts to refine the structure in this space group resulted in an unsatisfactory model.

Related literature

For the propane-1,2-diol solvate of the title complex, see: Zhong (2011 ). For related structures of transition metal complexes of phen and for background references, see: Zhong et al. (2006 ; 2009 ); Zhong & Cui (2010 ); Ni et al. (2010 ); Zhong (2010 ); Cui et al. (2010 ).

Experimental

Crystal data

[Cu(SO₄)(C₁₂H₈N₂)₂]·C₂H₆O₂
M_r = 582.08
Monoclinic, C c
a = 17.666 (4) Å
b = 11.992 (2) Å
c = 13.122 (3) Å
β = 120.96 (3)°
V = 2383.8 (11) Å³
Z = 4
Mo Kα radiation
μ = 1.06 mm⁻¹
T = 223 K
0.40 × 0.35 × 0.25 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.776, T_max = 1.000
6663 measured reflections
4089 independent reflections
3835 reflections with I > 2/s(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.102
S = 1.06
4089 reflections
344 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 1.07 e Å⁻³
Δρ_min = −0.81 e Å⁻³
Absolute structure: Flack (1983 ), 1396 Friedel pairs
Flack parameter: 0.254 (14)

Table 1
Selected geometric parameters (Å, °)

Cu1—O1	1.957 (3)
Cu1—N2	1.990 (4)
Cu1—N3	2.006 (4)
Cu1—N4	2.073 (4)
Cu1—N1	2.162 (4)
S1—O4	1.469 (3)
S1—O2	1.470 (3)
S1—O3	1.475 (3)
S1—O1	1.504 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6B⋯O4	0.82	1.93	2.751 (5)	176
O5—H5B⋯O3	0.82	1.98	2.798 (5)	171

Data collection: CrystalClear (Rigaku, 2007 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811031175/bt5595sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811031175/bt5595Isup2.hkl

checkCIF report

Comment top

In the past few years, we have reported many metal-Phen complexes with bidentate-chelating sulfate auxiliary ligand via a alcohlol-solvothermal reaction, such as [CoSO₄(C₁₂H₈N₂)₂].C₂H₆O₂ (Zhong et al., 2006), [NiSO₄(C₁₂H₈N₂)₂].C₂H₆O₂ (Zhong et al., 2009), [CoSO₄(C₁₂H₈N₂)₂].C₃H₈O₂ (Zhong, 2010), [ZnSO₄(C₁₂H₈N₂)₂].C₃H₈O₂ (Cui et al., 2010), [NiSO₄(C₁₂H₈N₂)₂].C₃H₈O₂ (Ni et al., 2010 and [CdSO₄(C₁₂H₈N₂)₂].C₃H₈O₂ (Zhong & Cui, 2010). The title compound was obtained during an attempt to synthesize a complex of Cu-complex with bidentate-chelating sulfate ligand by the similar route. The crystal structure of the title complex [CuSO₄(C₁₂H₈N₂)₂].C₂H₆O₂, (I) has not hitherto been reported.

Single crystal X-ray diffraction experiment indicated that the title compound is isostructual to the recently reported Cu(C₁₂H₈N₂)₂(SO₄).C₃H₈O₂, (II) (Zhong, 2011), the Cu^II metal ion is five-coordinated in a distorted square-pyramidal coordination environment formed by four N atoms(N1, N2, N3 and N4) from two chelating phen ligands and an O atoms(O1) from a monodentate sulfate ligand, the N1, N2, N3 and N4 atoms comprise a square, and the O3 atom the apex of a square pyramid surrounding each metal atom. The geometry of the phen and sulfate ligands is in good agreement with those reported in the isomorphs complex(II). The dihedral angle between the two chelating N2C2 groups is 71.1 (2)°, this is smaller than that found in (II) [84.9 (4)°]. The Cu—O bond distance [1.957 (3) Å], the Cu—N bond distance [1.990 (4) - 2.162 (4) Å], and the N—Cu—N bite angle [80.4 (2) - 81.4 (2)°] are in good agreement with observed in (II), [1.901 (1) Å, 1.991 (7) - 2.154 (8)Å and 80.4 (3) - 80.7 (3)°, respectively](see Table 1). The metal complex and solvent entities of (I) are held together by a pair of intermolecular O—H···O hydrogen bonds with the uncoordinated O atoms of the sulfate group(see Table 2 & Fig. 1).

Related literature top

For the propane-1,2-diol solvate of the title complex, see: Zhong (2011). For related structures of transition metal complexes of phen and for background references, see: Zhong et al. (2006; 2009); Zhong & Cui (2010); Ni et al. (2010); Zhong (2010); Cui et al. (2010).

Experimental top

0.2 mmol phen, 0.1 mmol CuSO₄.5H₂O, 2.0 ml e thane-1,2-diol and 1.0 ml water were mixed and placed in a thick Pyrex tube, which was sealed and heated to 453 K for 96 h, whereupon Blue block-shaped crystals of (I) were obtained. The presence of pseudo-symmetry in the structure suggests a higher symmetry space group C2/c. But attempts to refine the structure in the space group C2/c resulted in a disorder model with high R and wR values. Hence the requirement to solve in Cc. The reported Flack parameter was refined as s full least-squares and obtained by TWIN/BASF procedure in SHELXL (Sheldrick, 2008).

Computing details top

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure showing the atom-numbering scheme and with displacement ellipsoids drawn at the 50% probability level. The dashed lines represent O—H···O interactions.

Bis(1,10-phenanthroline-κ²N,N')(sulfato- κ²O,O')copper(II) ethane-1,2-diol monosolvate top

Crystal data top

[Cu(SO₄)(C₁₂H₈N₂)₂]·C₂H₆O₂	F(000) = 1196
M_r = 582.08	D_x = 1.622 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 5713 reflections
a = 17.666 (4) Å	θ = 3.2–27.5°
b = 11.992 (2) Å	µ = 1.06 mm⁻¹
c = 13.122 (3) Å	T = 223 K
β = 120.96 (3)°	Block, green
V = 2383.8 (11) Å³	0.40 × 0.35 × 0.25 mm
Z = 4

Data collection top

Rigaku Mercury CCD diffractometer	4089 independent reflections
Radiation source: fine-focus sealed tube	3835 reflections with I > 2/s(I)
Graphite Monochromator monochromator	R_int = 0.018
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ω scans	h = −21→22
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −13→15
T_min = 0.776, T_max = 1.000	l = −15→17
6663 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.064P)² + 1.9064P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
4089 reflections	Δρ_max = 1.07 e Å⁻³
344 parameters	Δρ_min = −0.81 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 1396 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.254 (14)

Crystal data top

[Cu(SO₄)(C₁₂H₈N₂)₂]·C₂H₆O₂	V = 2383.8 (11) Å³
M_r = 582.08	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 17.666 (4) Å	µ = 1.06 mm⁻¹
b = 11.992 (2) Å	T = 223 K
c = 13.122 (3) Å	0.40 × 0.35 × 0.25 mm
β = 120.96 (3)°

Data collection top

Rigaku Mercury CCD diffractometer	4089 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	3835 reflections with I > 2/s(I)
T_min = 0.776, T_max = 1.000	R_int = 0.018
6663 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.102	Δρ_max = 1.07 e Å⁻³
S = 1.06	Δρ_min = −0.81 e Å⁻³
4089 reflections	Absolute structure: Flack (1983), 1396 Friedel pairs
344 parameters	Absolute structure parameter: 0.254 (14)
2 restraints

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
Cu1	0.17114 (3)	0.28325 (3)	0.03203 (4)	0.02354 (12)
S1	0.16061 (6)	0.54366 (7)	0.04366 (9)	0.0262 (2)
N3	0.2587 (3)	0.2724 (3)	−0.0216 (4)	0.0220 (8)
N2	0.0827 (3)	0.2673 (3)	0.0820 (4)	0.0253 (8)
C24	0.3290 (3)	0.2059 (3)	0.0478 (4)	0.0215 (9)
N1	0.0735 (2)	0.1831 (3)	−0.1135 (3)	0.0246 (8)
N4	0.2650 (2)	0.1851 (3)	0.1690 (3)	0.0223 (7)
C11	0.0105 (3)	0.2038 (3)	0.0078 (4)	0.0235 (9)
C8	−0.0484 (3)	0.2248 (4)	0.1356 (5)	0.0298 (11)
H8A	−0.0915	0.2107	0.1546	0.036*
C15	0.3855 (4)	0.2311 (4)	−0.0817 (5)	0.0335 (11)
H15A	0.4279	0.2186	−0.1023	0.040*
O4	0.0858 (2)	0.6189 (3)	−0.0263 (3)	0.0336 (7)
C14	0.2517 (3)	0.3163 (4)	−0.1194 (4)	0.0268 (9)
H14A	0.2038	0.3622	−0.1669	0.032*
C10	0.0876 (3)	0.3084 (4)	0.1789 (5)	0.0313 (10)
H10A	0.1356	0.3532	0.2291	0.038*
C12	0.0056 (3)	0.1594 (4)	−0.0968 (4)	0.0218 (8)
C19	0.4077 (3)	0.0962 (3)	0.2325 (4)	0.0255 (10)
C4	−0.0682 (3)	0.0986 (4)	−0.1775 (4)	0.0264 (10)
O3	0.2432 (2)	0.5960 (3)	0.0654 (3)	0.0365 (8)
C13	0.3122 (4)	0.2966 (4)	−0.1525 (5)	0.0320 (11)
H13A	0.3042	0.3272	−0.2225	0.038*
C9	0.0224 (4)	0.2870 (3)	0.2096 (5)	0.0298 (11)
H9A	0.0287	0.3154	0.2795	0.036*
C18	0.4738 (3)	0.0761 (4)	0.2050 (5)	0.0302 (11)
H18A	0.5224	0.0334	0.2573	0.036*
C5	−0.1378 (3)	0.0776 (4)	−0.1545 (4)	0.0316 (11)
H5A	−0.1872	0.0370	−0.2087	0.038*
C7	−0.0582 (3)	0.1810 (4)	0.0300 (4)	0.0251 (9)
C16	0.3945 (3)	0.1835 (4)	0.0227 (4)	0.0260 (9)
C17	0.4695 (3)	0.1164 (4)	0.1054 (4)	0.0315 (10)
H17A	0.5145	0.1010	0.0904	0.038*
C3	−0.0707 (3)	0.0591 (4)	−0.2814 (4)	0.0310 (10)
H3A	−0.1183	0.0171	−0.3374	0.037*
C23	0.3340 (3)	0.1616 (4)	0.1529 (4)	0.0218 (8)
C6	−0.1316 (3)	0.1171 (4)	−0.0534 (4)	0.0318 (10)
H6A	−0.1766	0.1018	−0.0385	0.038*
C20	0.4089 (3)	0.0575 (4)	0.3340 (4)	0.0318 (10)
H20A	0.4558	0.0141	0.3892	0.038*
C2	−0.0025 (4)	0.0838 (4)	−0.2974 (5)	0.0350 (12)
H2A	−0.0038	0.0601	−0.3658	0.042*
C22	0.2710 (3)	0.1466 (4)	0.2686 (4)	0.0294 (10)
H22A	0.2257	0.1632	0.2826	0.035*
C21	0.3416 (4)	0.0832 (4)	0.3522 (4)	0.0348 (12)
H21A	0.3430	0.0584	0.4203	0.042*
C1	0.0701 (3)	0.1451 (4)	−0.2109 (4)	0.0300 (9)
H1A	0.1171	0.1593	−0.2220	0.036*
O1	0.1418 (2)	0.4369 (2)	−0.0255 (3)	0.0357 (7)
O6	0.1139 (3)	0.8222 (3)	0.0846 (4)	0.0541 (11)
H6B	0.1059	0.7631	0.0492	0.081*
O5	0.2232 (3)	0.8087 (3)	−0.0330 (4)	0.0503 (10)
H5B	0.2288	0.7496	0.0017	0.075*
C26	0.1316 (6)	0.9055 (4)	0.0264 (7)	0.058 (2)
H26A	0.1279	0.9770	0.0584	0.070*
H26B	0.0857	0.9042	−0.0569	0.070*
C25	0.2177 (4)	0.8984 (5)	0.0348 (6)	0.0586 (18)
H25A	0.2289	0.9681	0.0072	0.070*
H25B	0.2635	0.8890	0.1175	0.070*
O2	0.1672 (2)	0.5194 (2)	0.1578 (2)	0.0332 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0233 (2)	0.0247 (2)	0.0272 (2)	0.0012 (2)	0.01621 (16)	0.0011 (3)
S1	0.0221 (5)	0.0222 (4)	0.0277 (5)	0.0012 (4)	0.0079 (4)	−0.0003 (4)
N3	0.022 (2)	0.0252 (19)	0.0229 (19)	0.0066 (14)	0.0142 (17)	0.0048 (15)
N2	0.025 (2)	0.0251 (19)	0.027 (2)	0.0026 (15)	0.0137 (19)	−0.0009 (16)
C24	0.024 (2)	0.021 (2)	0.019 (2)	0.0000 (16)	0.0106 (18)	−0.0046 (16)
N1	0.0242 (19)	0.0254 (19)	0.0228 (18)	−0.0047 (15)	0.0110 (16)	−0.0030 (15)
N4	0.0291 (19)	0.0201 (17)	0.0215 (17)	−0.0015 (15)	0.0158 (16)	−0.0010 (15)
C11	0.020 (2)	0.022 (2)	0.028 (2)	0.0029 (16)	0.012 (2)	0.0011 (18)
C8	0.027 (3)	0.033 (3)	0.038 (3)	−0.0001 (19)	0.023 (2)	0.005 (2)
C15	0.040 (3)	0.037 (3)	0.034 (3)	−0.003 (2)	0.026 (2)	−0.001 (2)
O4	0.0286 (16)	0.0358 (16)	0.0351 (16)	0.0043 (13)	0.0155 (14)	0.0010 (14)
C14	0.025 (2)	0.035 (2)	0.023 (2)	0.0033 (19)	0.015 (2)	0.005 (2)
C10	0.035 (3)	0.028 (2)	0.034 (3)	−0.002 (2)	0.019 (2)	−0.003 (2)
C12	0.024 (2)	0.0184 (18)	0.0227 (19)	0.0034 (17)	0.0119 (18)	0.0053 (17)
C19	0.025 (2)	0.018 (2)	0.023 (2)	−0.0011 (17)	0.0053 (19)	−0.0057 (18)
C4	0.024 (2)	0.028 (2)	0.025 (2)	0.0002 (18)	0.010 (2)	0.0010 (19)
O3	0.0219 (16)	0.0410 (19)	0.049 (2)	0.0042 (13)	0.0197 (15)	0.0121 (15)
C13	0.034 (3)	0.038 (3)	0.029 (3)	0.004 (2)	0.019 (2)	0.005 (2)
C9	0.037 (3)	0.031 (3)	0.033 (3)	0.0004 (19)	0.026 (2)	0.0018 (19)
C18	0.022 (2)	0.032 (3)	0.032 (2)	0.0006 (18)	0.010 (2)	−0.002 (2)
C5	0.025 (3)	0.028 (2)	0.030 (2)	−0.0058 (18)	0.005 (2)	−0.0016 (19)
C7	0.027 (2)	0.024 (2)	0.028 (2)	0.0057 (18)	0.016 (2)	0.0078 (19)
C16	0.020 (2)	0.027 (2)	0.031 (2)	−0.0002 (18)	0.013 (2)	−0.001 (2)
C17	0.023 (2)	0.032 (2)	0.035 (2)	−0.0005 (19)	0.012 (2)	−0.006 (2)
C3	0.033 (3)	0.029 (2)	0.025 (2)	−0.001 (2)	0.010 (2)	−0.004 (2)
C23	0.021 (2)	0.022 (2)	0.0214 (19)	0.0024 (17)	0.0105 (18)	0.0008 (17)
C6	0.025 (2)	0.037 (3)	0.038 (3)	−0.006 (2)	0.019 (2)	0.001 (2)
C20	0.031 (3)	0.030 (3)	0.025 (2)	0.006 (2)	0.007 (2)	0.002 (2)
C2	0.046 (3)	0.032 (3)	0.028 (2)	−0.007 (2)	0.020 (2)	−0.006 (2)
C22	0.033 (3)	0.035 (2)	0.027 (2)	0.008 (2)	0.021 (2)	0.006 (2)
C21	0.040 (3)	0.035 (3)	0.025 (2)	0.004 (2)	0.014 (2)	0.009 (2)
C1	0.035 (3)	0.030 (2)	0.026 (2)	−0.001 (2)	0.017 (2)	−0.002 (2)
O1	0.0474 (18)	0.0267 (13)	0.0325 (15)	0.0058 (13)	0.0201 (14)	−0.0012 (12)
O6	0.084 (3)	0.037 (2)	0.069 (3)	−0.003 (2)	0.059 (3)	−0.008 (2)
O5	0.068 (3)	0.047 (2)	0.057 (2)	−0.006 (2)	0.048 (2)	0.0026 (19)
C26	0.111 (6)	0.020 (2)	0.068 (4)	−0.002 (3)	0.065 (5)	−0.006 (3)
C25	0.053 (4)	0.059 (4)	0.058 (4)	−0.029 (3)	0.025 (3)	−0.014 (3)
O2	0.0381 (17)	0.0364 (15)	0.0265 (13)	−0.0035 (13)	0.0176 (13)	0.0002 (13)

Geometric parameters (Å, º) top

Cu1—O1	1.957 (3)	C19—C18	1.409 (7)
Cu1—N2	1.990 (4)	C19—C23	1.415 (6)
Cu1—N3	2.006 (4)	C4—C3	1.422 (7)
Cu1—N4	2.073 (4)	C4—C5	1.432 (7)
Cu1—N1	2.162 (4)	C13—H13A	0.9300
S1—O4	1.469 (3)	C9—H9A	0.9300
S1—O2	1.470 (3)	C18—C17	1.358 (7)
S1—O3	1.475 (3)	C18—H18A	0.9300
S1—O1	1.504 (3)	C5—C6	1.359 (7)
N3—C14	1.333 (6)	C5—H5A	0.9300
N3—C24	1.358 (6)	C7—C6	1.416 (7)
N2—C10	1.324 (7)	C16—C17	1.451 (7)
N2—C11	1.371 (6)	C17—H17A	0.9300
C24—C16	1.382 (6)	C3—C2	1.358 (7)
C24—C23	1.437 (6)	C3—H3A	0.9300
N1—C1	1.330 (6)	C6—H6A	0.9300
N1—C12	1.354 (5)	C20—C21	1.363 (7)
N4—C22	1.338 (6)	C20—H20A	0.9300
N4—C23	1.369 (5)	C2—C1	1.406 (7)
C11—C7	1.412 (6)	C2—H2A	0.9300
C11—C12	1.433 (6)	C22—C21	1.389 (7)
C8—C9	1.347 (8)	C22—H22A	0.9300
C8—C7	1.408 (7)	C21—H21A	0.9300
C8—H8A	0.9300	C1—H1A	0.9300
C15—C13	1.386 (8)	O6—C26	1.386 (7)
C15—C16	1.415 (7)	O6—H6B	0.8200
C15—H15A	0.9300	O5—C25	1.430 (7)
C14—C13	1.365 (7)	O5—H5B	0.8200
C14—H14A	0.9300	C26—C25	1.472 (8)
C10—C9	1.426 (7)	C26—H26A	0.9700
C10—H10A	0.9300	C26—H26B	0.9700
C12—C4	1.390 (6)	C25—H25A	0.9700
C19—C20	1.401 (7)	C25—H25B	0.9700

O1—Cu1—N2	96.90 (14)	C8—C9—C10	118.8 (5)
O1—Cu1—N3	91.43 (13)	C8—C9—H9A	120.6
N2—Cu1—N3	170.72 (10)	C10—C9—H9A	120.6
O1—Cu1—N4	143.49 (13)	C17—C18—C19	122.8 (5)
N2—Cu1—N4	94.19 (15)	C17—C18—H18A	118.6
N3—Cu1—N4	81.39 (15)	C19—C18—H18A	118.6
O1—Cu1—N1	104.46 (13)	C6—C5—C4	119.8 (4)
N2—Cu1—N1	80.37 (15)	C6—C5—H5A	120.1
N3—Cu1—N1	93.63 (15)	C4—C5—H5A	120.1
N4—Cu1—N1	111.67 (10)	C8—C7—C11	116.6 (4)
O4—S1—O2	109.46 (18)	C8—C7—C6	124.2 (4)
O4—S1—O3	110.01 (16)	C11—C7—C6	119.2 (4)
O2—S1—O3	109.6 (2)	C24—C16—C15	117.5 (4)
O4—S1—O1	107.30 (19)	C24—C16—C17	119.0 (4)
O2—S1—O1	108.83 (17)	C15—C16—C17	123.5 (4)
O3—S1—O1	111.61 (19)	C18—C17—C16	119.6 (5)
C14—N3—C24	118.5 (4)	C18—C17—H17A	120.2
C14—N3—Cu1	127.3 (3)	C16—C17—H17A	120.2
C24—N3—Cu1	114.0 (3)	C2—C3—C4	118.9 (4)
C10—N2—C11	117.8 (4)	C2—C3—H3A	120.6
C10—N2—Cu1	127.3 (4)	C4—C3—H3A	120.6
C11—N2—Cu1	114.9 (3)	N4—C23—C19	123.7 (4)
N3—C24—C16	122.9 (4)	N4—C23—C24	116.9 (4)
N3—C24—C23	116.3 (4)	C19—C23—C24	119.4 (4)
C16—C24—C23	120.7 (4)	C5—C6—C7	121.7 (4)
C1—N1—C12	118.5 (4)	C5—C6—H6A	119.2
C1—N1—Cu1	131.3 (3)	C7—C6—H6A	119.2
C12—N1—Cu1	110.2 (3)	C21—C20—C19	120.3 (4)
C22—N4—C23	116.7 (4)	C21—C20—H20A	119.9
C22—N4—Cu1	132.0 (3)	C19—C20—H20A	119.9
C23—N4—Cu1	111.2 (3)	C3—C2—C1	120.1 (5)
N2—C11—C7	123.1 (4)	C3—C2—H2A	119.9
N2—C11—C12	117.5 (4)	C1—C2—H2A	119.9
C7—C11—C12	119.4 (4)	N4—C22—C21	123.3 (4)
C9—C8—C7	121.0 (5)	N4—C22—H22A	118.4
C9—C8—H8A	119.5	C21—C22—H22A	118.4
C7—C8—H8A	119.5	C20—C21—C22	119.6 (4)
C13—C15—C16	118.6 (5)	C20—C21—H21A	120.2
C13—C15—H15A	120.7	C22—C21—H21A	120.2
C16—C15—H15A	120.7	N1—C1—C2	121.8 (4)
N3—C14—C13	122.6 (4)	N1—C1—H1A	119.1
N3—C14—H14A	118.7	C2—C1—H1A	119.1
C13—C14—H14A	118.7	S1—O1—Cu1	129.51 (18)
N2—C10—C9	122.7 (5)	C26—O6—H6B	109.5
N2—C10—H10A	118.6	C25—O5—H5B	109.5
C9—C10—H10A	118.6	O6—C26—C25	115.7 (6)
N1—C12—C4	123.3 (4)	O6—C26—H26A	108.3
N1—C12—C11	117.1 (4)	C25—C26—H26A	108.3
C4—C12—C11	119.7 (4)	O6—C26—H26B	108.3
C20—C19—C18	125.2 (4)	C25—C26—H26B	108.3
C20—C19—C23	116.4 (4)	H26A—C26—H26B	107.4
C18—C19—C23	118.4 (4)	O5—C25—C26	113.3 (5)
C12—C4—C3	117.4 (4)	O5—C25—H25A	108.9
C12—C4—C5	120.2 (4)	C26—C25—H25A	108.9
C3—C4—C5	122.4 (4)	O5—C25—H25B	108.9
C14—C13—C15	119.9 (5)	C26—C25—H25B	108.9
C14—C13—H13A	120.0	H25A—C25—H25B	107.7
C15—C13—H13A	120.0

O1—Cu1—N3—C14	−37.2 (4)	N2—C10—C9—C8	−1.8 (7)
N4—Cu1—N3—C14	178.8 (4)	C20—C19—C18—C17	−179.6 (5)
N1—Cu1—N3—C14	67.4 (4)	C23—C19—C18—C17	−0.2 (7)
O1—Cu1—N3—C24	147.5 (3)	C12—C4—C5—C6	−0.1 (7)
N4—Cu1—N3—C24	3.5 (3)	C3—C4—C5—C6	179.7 (5)
N1—Cu1—N3—C24	−107.9 (3)	C9—C8—C7—C11	1.2 (7)
O1—Cu1—N2—C10	−76.9 (4)	C9—C8—C7—C6	−178.6 (4)
N4—Cu1—N2—C10	68.3 (4)	N2—C11—C7—C8	−1.6 (6)
N1—Cu1—N2—C10	179.6 (4)	C12—C11—C7—C8	178.5 (4)
O1—Cu1—N2—C11	105.0 (3)	N2—C11—C7—C6	178.2 (4)
N4—Cu1—N2—C11	−109.8 (3)	C12—C11—C7—C6	−1.6 (6)
N1—Cu1—N2—C11	1.5 (3)	N3—C24—C16—C15	−1.2 (7)
C14—N3—C24—C16	1.2 (7)	C23—C24—C16—C15	−179.3 (4)
Cu1—N3—C24—C16	176.9 (3)	N3—C24—C16—C17	176.7 (4)
C14—N3—C24—C23	179.4 (4)	C23—C24—C16—C17	−1.4 (7)
Cu1—N3—C24—C23	−4.9 (5)	C13—C15—C16—C24	−0.2 (7)
O1—Cu1—N1—C1	83.4 (4)	C13—C15—C16—C17	−178.1 (5)
N2—Cu1—N1—C1	178.1 (4)	C19—C18—C17—C16	0.2 (7)
N3—Cu1—N1—C1	−9.1 (4)	C24—C16—C17—C18	0.6 (7)
N4—Cu1—N1—C1	−91.2 (4)	C15—C16—C17—C18	178.4 (5)
O1—Cu1—N1—C12	−95.9 (3)	C12—C4—C3—C2	−1.0 (7)
N2—Cu1—N1—C12	−1.1 (3)	C5—C4—C3—C2	179.2 (5)
N3—Cu1—N1—C12	171.7 (3)	C22—N4—C23—C19	2.7 (6)
N4—Cu1—N1—C12	89.6 (3)	Cu1—N4—C23—C19	180.0 (3)
O1—Cu1—N4—C22	94.6 (4)	C22—N4—C23—C24	−178.0 (4)
N2—Cu1—N4—C22	−12.9 (4)	Cu1—N4—C23—C24	−0.7 (5)
N3—Cu1—N4—C22	175.3 (4)	C20—C19—C23—N4	−1.8 (6)
N1—Cu1—N4—C22	−94.2 (4)	C18—C19—C23—N4	178.8 (4)
O1—Cu1—N4—C23	−82.1 (3)	C20—C19—C23—C24	178.9 (4)
N2—Cu1—N4—C23	170.3 (3)	C18—C19—C23—C24	−0.5 (6)
N3—Cu1—N4—C23	−1.5 (3)	N3—C24—C23—N4	3.7 (6)
N1—Cu1—N4—C23	89.0 (3)	C16—C24—C23—N4	−178.0 (4)
C10—N2—C11—C7	0.2 (7)	N3—C24—C23—C19	−176.9 (4)
Cu1—N2—C11—C7	178.5 (3)	C16—C24—C23—C19	1.3 (6)
C10—N2—C11—C12	−179.9 (4)	C4—C5—C6—C7	1.2 (8)
Cu1—N2—C11—C12	−1.6 (5)	C8—C7—C6—C5	179.5 (5)
C24—N3—C14—C13	0.4 (7)	C11—C7—C6—C5	−0.3 (7)
Cu1—N3—C14—C13	−174.7 (4)	C18—C19—C20—C21	179.3 (4)
C11—N2—C10—C9	1.5 (7)	C23—C19—C20—C21	−0.1 (7)
Cu1—N2—C10—C9	−176.5 (3)	C4—C3—C2—C1	1.5 (7)
C1—N1—C12—C4	−1.0 (6)	C23—N4—C22—C21	−1.7 (7)
Cu1—N1—C12—C4	178.3 (3)	Cu1—N4—C22—C21	−178.3 (4)
C1—N1—C12—C11	−178.7 (4)	C19—C20—C21—C22	1.0 (7)
Cu1—N1—C12—C11	0.7 (5)	N4—C22—C21—C20	−0.1 (8)
N2—C11—C12—N1	0.6 (6)	C12—N1—C1—C2	1.6 (6)
C7—C11—C12—N1	−179.6 (4)	Cu1—N1—C1—C2	−177.6 (3)
N2—C11—C12—C4	−177.2 (4)	C3—C2—C1—N1	−1.9 (7)
C7—C11—C12—C4	2.7 (6)	O4—S1—O1—Cu1	−145.3 (2)
N1—C12—C4—C3	0.7 (7)	O2—S1—O1—Cu1	−26.9 (3)
C11—C12—C4—C3	178.3 (4)	O3—S1—O1—Cu1	94.2 (3)
N1—C12—C4—C5	−179.4 (4)	N2—Cu1—O1—S1	72.8 (3)
C11—C12—C4—C5	−1.8 (6)	N3—Cu1—O1—S1	−111.3 (3)
N3—C14—C13—C15	−1.8 (8)	N4—Cu1—O1—S1	−33.9 (4)
C16—C15—C13—C14	1.6 (8)	N1—Cu1—O1—S1	154.6 (2)
C7—C8—C9—C10	0.3 (7)	O6—C26—C25—O5	71.3 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6B···O4	0.82	1.93	2.751 (5)	176
O5—H5B···O3	0.82	1.98	2.798 (5)	171

Experimental details

Crystal data
Chemical formula	[Cu(SO₄)(C₁₂H₈N₂)₂]·C₂H₆O₂
M_r	582.08
Crystal system, space group	Monoclinic, Cc
Temperature (K)	223
a, b, c (Å)	17.666 (4), 11.992 (2), 13.122 (3)
β (°)	120.96 (3)
V (Å³)	2383.8 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.06
Crystal size (mm)	0.40 × 0.35 × 0.25

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (REQAB; Jacobson, 1998)
T_min, T_max	0.776, 1.000
No. of measured, independent and observed [I > 2/s(I)] reflections	6663, 4089, 3835
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.102, 1.06
No. of reflections	4089
No. of parameters	344
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.07, −0.81
Absolute structure	Flack (1983), 1396 Friedel pairs
Absolute structure parameter	0.254 (14)

Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Cu1—O1	1.957 (3)	S1—O4	1.469 (3)
Cu1—N2	1.990 (4)	S1—O2	1.470 (3)
Cu1—N3	2.006 (4)	S1—O3	1.475 (3)
Cu1—N4	2.073 (4)	S1—O1	1.504 (3)
Cu1—N1	2.162 (4)	C26—C25	1.472 (8)

O1—Cu1—N2	96.90 (14)	O4—S1—O2	109.46 (18)
O1—Cu1—N3	91.43 (13)	O4—S1—O3	110.01 (16)
O1—Cu1—N4	143.49 (13)	O2—S1—O3	109.6 (2)
N3—Cu1—N4	81.39 (15)	O4—S1—O1	107.30 (19)
O1—Cu1—N1	104.46 (13)	O2—S1—O1	108.83 (17)
N2—Cu1—N1	80.37 (15)	O3—S1—O1	111.61 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6B···O4	0.82	1.93	2.751 (5)	176.1
O5—H5B···O3	0.82	1.98	2.798 (5)	171.3

Acknowledgements

This work was supported by the Scientific Research Foundation of Nanjing College of Chemical Technology (grant No. NHKY-2010–17).

References

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