Bis(1,10-phenanthroline-κ2N,N′)(sulfato-O)copper(II) propane-1,3-diol monosolvate

Zhong, K.-L.

doi:10.1107/S1600536812047721

metal-organic compounds

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Volume 68| Part 12| December 2012| Page m1555

doi:10.1107/S1600536812047721

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Bis(1,10-phenanthroline-κ²N,N′)(sulfato-O)copper(II) propane-1,3-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: zklong76@163.com

(Received 12 November 2012; accepted 20 November 2012; online 28 November 2012)

In the title compound, [Cu(SO₄)(C₁₂H₈N₂)₂]·C₃H₈O₂, the Cu^II ion is bonded to two chelating 1,10-phenanthroline (phen) ligands and one O atom from a monodentate sulfate ligand in a distorted square-based pyramidal arrangement, with the O atom in a basal site. The two chelating N₂C₂ groups subtend a dihedral angle of 71.10 (15)°. In the crystal, the solvent molecule forms two O—H⋯O hydrogen bonds to its adjacent complex molecule. The chosen crystal was found to be a racemic twin; 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 and high R and wR values.

Related literature

For the ethane-1,2-diol solvate of the title complex, see: Zhong (2011a ) and for the propane-1,2-diol solvate of the title complex, see: Zhong (2011b ). For related structures of five-coordinate copper complexes and background references, see: Murphy & Hathaway (2003 ); Potočňák et al. (2008 ).

Experimental

Crystal data

[Cu(SO₄)(C₁₂H₈N₂)₂]·C₃H₈O₂
M_r = 596.10
Monoclinic, C c
a = 17.523 (4) Å
b = 12.562 (3) Å
c = 13.438 (3) Å
β = 123.44 (3)°
V = 2468.4 (13) Å³
Z = 4
Mo Kα radiation
μ = 1.02 mm⁻¹
T = 223 K
0.30 × 0.20 × 0.20 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.750, T_max = 1.000
6895 measured reflections
4049 independent reflections
3892 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.094
S = 1.07
4049 reflections
354 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.82 e Å⁻³
Absolute structure: Flack (1983 ), 1224 Friedel pairs
Flack parameter: 0.56 (1)

Table 1
Selected bond lengths (Å)

Cu1—O1	1.956 (3)
Cu1—N1	2.001 (3)
Cu1—N3	2.009 (3)
Cu1—N2	2.071 (3)
Cu1—N4	2.175 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5B⋯O3	0.82	1.99	2.788 (4)	166
O6—H6B⋯O4	0.82	2.01	2.817 (5)	166

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/S1600536812047721/hb6990sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812047721/hb6990Isup2.hkl

checkCIF report

Comment top

Understanding the shape of coordination polyhedral in the case of five-coordination in the coordination chemistry has been caused much attention in the past few years (Murphy & Hathaway, 2003; Potočňák et al., 2008). The title compound, (I), was unexpectedly obtained via a alcohol-solvothermal reaction and its crystal structure is now described.

The title complex is isostructural to the previously reported [CuSO₄(C₁₂H₈N₂)₂].C₂H₆O₂, (II), (Zhong, 2011a) and Cu-Phen complex with propane-1,2-diol monosolvate, (III), (Zhong, 2011b). In the title compound, X-ray diffraction experiment revealed that the Cu^II metal ion is five-coordinated in a distorted square-pyramidal manner 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 O1 atom site the apex of a square pyramid surrounding each metal atom. The Cu—O bond distance [1.956 (3) Å], the Cu—N bond distance [2.001 (3) - 2.175 (4) Å], and the N—Cu—N bite angle [80.09 (14) - 81.16 (14)°] are in good agreement with that observed in (II) and (III) (Table 1). The two chelating N2C2 groups are oriented at 71.10 (15)°, this is almost equal to that reported in (II) [71.1 (2)°] and smaller than that found in (III) [84.9 (4)°]. In the crystal, the neutral monomeric complex [CuSO₄(C₁₂H₈N₂)₂] and solvent propane-1,3-diol components of (I) are connected by a pair of intermolecular O—H···O hydrogen bonding with the uncoordinated O atoms of the sulfate group(Table 2 & Fig. 1).

Related literature top

For the ethane-1,2-diol solvate of the title complex, see: Zhong (2011a) and for the propane-1,2-diol solvate of the title complex, see: Zhong (2011b). For related structures of five-coordinate copper complexes and background references, see: Murphy & Hathaway (2003); Potočňák et al. (2008).

Experimental top

0.2 mmol phen, 0.1 mmol melamine, 0.1 mmol CuSO₄.5H₂O, 2.0 ml propane-1,3-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.

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 displacement ellipsoids drawn at the 35% probability level. Hydrogen bonds O—H···O are shown as dashed lines.

Bis(1,10-phenanthroline-κ²N,N')(sulfato-O)copper(II) propane-1,3-diol monosolvate top

Crystal data top

[Cu(SO₄)(C₁₂H₈N₂)₂]·C₃H₈O₂	F(000) = 1228
M_r = 596.10	D_x = 1.604 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 6081 reflections
a = 17.523 (4) Å	θ = 3.1–27.5°
b = 12.562 (3) Å	µ = 1.02 mm⁻¹
c = 13.438 (3) Å	T = 223 K
β = 123.44 (3)°	Block, blue
V = 2468.4 (13) Å³	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection top

Rigaku Mercury CCD diffractometer	4049 independent reflections
Radiation source: fine-focus sealed tube	3892 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scan	h = −22→20
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −15→15
T_min = 0.750, T_max = 1.000	l = −17→15
6895 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.036	w = 1/[σ²(F_o²) + (0.0678P)² + 0.9364P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.094	(Δ/σ)_max = 0.002
S = 1.07	Δρ_max = 0.70 e Å⁻³
4049 reflections	Δρ_min = −0.82 e Å⁻³
354 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.0074 (6)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1224 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.56 (1)

Crystal data top

[Cu(SO₄)(C₁₂H₈N₂)₂]·C₃H₈O₂	V = 2468.4 (13) Å³
M_r = 596.10	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 17.523 (4) Å	µ = 1.02 mm⁻¹
b = 12.562 (3) Å	T = 223 K
c = 13.438 (3) Å	0.30 × 0.20 × 0.20 mm
β = 123.44 (3)°

Data collection top

Rigaku Mercury CCD diffractometer	4049 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	3892 reflections with I > 2σ(I)
T_min = 0.750, T_max = 1.000	R_int = 0.017
6895 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.094	Δρ_max = 0.70 e Å⁻³
S = 1.07	Δρ_min = −0.82 e Å⁻³
4049 reflections	Absolute structure: Flack (1983), 1224 Friedel pairs
354 parameters	Absolute structure parameter: 0.56 (1)
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	0.27326 (3)	0.20114 (3)	0.12409 (3)	0.01905 (12)
S1	0.26222 (7)	−0.04682 (6)	0.13203 (9)	0.0231 (2)
O1	0.24083 (19)	0.0554 (2)	0.0634 (2)	0.0302 (6)
O2	0.27343 (19)	−0.0240 (2)	0.2470 (2)	0.0320 (6)
O3	0.1834 (2)	−0.1175 (2)	0.0615 (3)	0.0289 (6)
O4	0.3462 (2)	−0.0955 (3)	0.1531 (3)	0.0384 (8)
O5	0.2035 (3)	−0.3097 (2)	0.1774 (3)	0.0356 (8)
H5B	0.1993	−0.2483	0.1543	0.053*
O6	0.3321 (3)	−0.2976 (2)	0.0534 (3)	0.0402 (9)
H6B	0.3338	−0.2348	0.0713	0.060*
N1	0.3609 (2)	0.2146 (2)	0.0734 (3)	0.0182 (7)
N2	0.3697 (2)	0.2982 (2)	0.2604 (3)	0.0187 (7)
N3	0.1833 (2)	0.2196 (2)	0.1711 (3)	0.0211 (7)
N4	0.1724 (3)	0.3012 (2)	−0.0218 (3)	0.0200 (7)
C1	0.3546 (3)	0.1723 (3)	−0.0219 (3)	0.0231 (8)
H1A	0.3088	0.1225	−0.0664	0.028*
C2	0.4122 (3)	0.1985 (3)	−0.0580 (4)	0.0238 (9)
H2A	0.4048	0.1674	−0.1256	0.029*
C3	0.4815 (3)	0.2722 (3)	0.0085 (4)	0.0246 (8)
H3A	0.5207	0.2913	−0.0148	0.030*
C4	0.4922 (3)	0.3180 (3)	0.1117 (4)	0.0220 (8)
C5	0.5640 (3)	0.3893 (3)	0.1891 (4)	0.0246 (8)
H5A	0.6067	0.4091	0.1719	0.030*
C6	0.5707 (3)	0.4287 (3)	0.2877 (4)	0.0242 (9)
H6A	0.6178	0.4755	0.3372	0.029*
C7	0.5067 (3)	0.3993 (3)	0.3165 (3)	0.0213 (7)
C8	0.5099 (3)	0.4370 (3)	0.4191 (4)	0.0239 (8)
H8A	0.5559	0.4833	0.4722	0.029*
C9	0.4455 (3)	0.4046 (4)	0.4383 (4)	0.0292 (9)
H9A	0.4473	0.4287	0.5050	0.035*
C10	0.3765 (3)	0.3353 (3)	0.3588 (3)	0.0232 (8)
H10A	0.3333	0.3138	0.3745	0.028*
C11	0.4352 (3)	0.3301 (3)	0.2419 (3)	0.0180 (7)
C12	0.4292 (3)	0.2867 (3)	0.1391 (4)	0.0172 (8)
C13	0.1905 (3)	0.1780 (4)	0.2671 (4)	0.0253 (8)
H13A	0.2369	0.1293	0.3136	0.030*
C14	0.1285 (4)	0.2067 (3)	0.2998 (5)	0.0282 (10)
H14A	0.1355	0.1784	0.3684	0.034*
C15	0.0597 (3)	0.2749 (3)	0.2311 (4)	0.0265 (9)
H15A	0.0187	0.2932	0.2517	0.032*
C16	0.0500 (3)	0.3184 (3)	0.1289 (4)	0.0221 (8)
C17	−0.0231 (3)	0.3899 (3)	0.0491 (4)	0.0273 (9)
H17A	−0.0653	0.4110	0.0664	0.033*
C18	−0.0307 (3)	0.4266 (3)	−0.0513 (4)	0.0275 (9)
H18A	−0.0796	0.4705	−0.1030	0.033*
C19	0.0350 (3)	0.3991 (3)	−0.0794 (4)	0.0217 (7)
C20	0.0297 (3)	0.4362 (3)	−0.1815 (4)	0.0295 (9)
H20A	−0.0173	0.4816	−0.2346	0.035*
C21	0.0948 (3)	0.4043 (3)	−0.2017 (4)	0.0274 (9)
H21A	0.0918	0.4270	−0.2697	0.033*
C22	0.1665 (3)	0.3369 (3)	−0.1190 (4)	0.0250 (8)
H22A	0.2110	0.3169	−0.1328	0.030*
C23	0.1081 (3)	0.3307 (3)	−0.0015 (3)	0.0194 (7)
C24	0.1152 (3)	0.2895 (3)	0.1030 (4)	0.0197 (8)
C25	0.1907 (4)	−0.3797 (4)	0.0891 (5)	0.0443 (12)
H25A	0.1684	−0.3402	0.0160	0.053*
H25B	0.1443	−0.4314	0.0739	0.053*
C26	0.2772 (4)	−0.4380 (3)	0.1223 (6)	0.0428 (10)
H26A	0.2953	−0.4846	0.1894	0.051*
H26B	0.2648	−0.4822	0.0557	0.051*
C27	0.3551 (4)	−0.3643 (4)	0.1545 (5)	0.0478 (13)
H27A	0.3683	−0.3199	0.2212	0.057*
H27B	0.4095	−0.4055	0.1784	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01945 (19)	0.01898 (19)	0.02378 (19)	−0.00159 (19)	0.01512 (15)	−0.0013 (2)
S1	0.0213 (5)	0.0179 (3)	0.0240 (4)	−0.0008 (4)	0.0087 (3)	−0.0011 (4)
O1	0.0415 (16)	0.0209 (12)	0.0289 (13)	−0.0051 (11)	0.0199 (12)	0.0000 (10)
O2	0.0374 (15)	0.0364 (15)	0.0205 (12)	0.0032 (12)	0.0149 (12)	0.0005 (11)
O3	0.0291 (15)	0.0270 (14)	0.0299 (14)	−0.0041 (11)	0.0158 (13)	0.0025 (11)
O4	0.0218 (15)	0.0423 (16)	0.056 (2)	−0.0006 (12)	0.0247 (15)	−0.0109 (15)
O5	0.051 (2)	0.0288 (15)	0.0388 (18)	−0.0008 (13)	0.0325 (17)	0.0025 (13)
O6	0.062 (2)	0.0354 (19)	0.043 (2)	0.0029 (14)	0.0413 (19)	0.0006 (13)
N1	0.0179 (17)	0.0201 (16)	0.0172 (16)	−0.0027 (12)	0.0100 (15)	−0.0017 (12)
N2	0.0177 (17)	0.0196 (17)	0.0179 (16)	0.0009 (11)	0.0093 (15)	0.0022 (11)
N3	0.0235 (19)	0.0175 (15)	0.0267 (19)	−0.0016 (13)	0.0167 (17)	−0.0002 (13)
N4	0.0241 (19)	0.0194 (18)	0.0202 (17)	0.0009 (12)	0.0145 (16)	0.0022 (12)
C1	0.023 (2)	0.0238 (18)	0.0231 (19)	−0.0027 (17)	0.0132 (17)	−0.0066 (17)
C2	0.026 (2)	0.024 (2)	0.026 (2)	−0.0010 (14)	0.017 (2)	−0.0043 (15)
C3	0.025 (2)	0.031 (2)	0.024 (2)	0.0026 (17)	0.0172 (18)	0.0021 (17)
C4	0.0194 (19)	0.0232 (18)	0.0225 (19)	0.0006 (16)	0.0110 (17)	0.0036 (16)
C5	0.020 (2)	0.028 (2)	0.0269 (19)	0.0011 (15)	0.0138 (17)	0.0037 (17)
C6	0.021 (2)	0.022 (2)	0.0263 (19)	−0.0022 (14)	0.0110 (17)	0.0021 (15)
C7	0.0219 (19)	0.0216 (18)	0.0185 (17)	0.0003 (15)	0.0099 (16)	0.0002 (15)
C8	0.025 (2)	0.021 (2)	0.0211 (17)	−0.0031 (15)	0.0095 (17)	−0.0036 (15)
C9	0.033 (2)	0.033 (2)	0.0174 (18)	−0.0021 (18)	0.0112 (19)	−0.0055 (16)
C10	0.027 (2)	0.026 (2)	0.0230 (19)	−0.0014 (16)	0.0177 (18)	−0.0017 (16)
C11	0.0199 (18)	0.0166 (16)	0.0190 (17)	0.0003 (14)	0.0116 (16)	0.0001 (15)
C12	0.0178 (19)	0.0170 (18)	0.0169 (18)	0.0017 (13)	0.0096 (16)	0.0014 (13)
C13	0.030 (2)	0.0236 (18)	0.029 (2)	−0.0012 (17)	0.021 (2)	−0.0020 (18)
C14	0.035 (3)	0.032 (2)	0.029 (2)	−0.0057 (16)	0.025 (2)	−0.0029 (15)
C15	0.029 (2)	0.028 (2)	0.033 (2)	−0.0009 (17)	0.024 (2)	−0.0052 (18)
C16	0.025 (2)	0.0209 (17)	0.028 (2)	−0.0048 (16)	0.0192 (18)	−0.0066 (17)
C17	0.022 (2)	0.026 (2)	0.037 (2)	0.0046 (16)	0.0182 (19)	−0.0045 (18)
C18	0.021 (2)	0.025 (2)	0.027 (2)	0.0065 (14)	0.0081 (18)	−0.0025 (16)
C19	0.0194 (19)	0.0185 (18)	0.0235 (18)	−0.0019 (15)	0.0094 (16)	−0.0047 (15)
C20	0.027 (2)	0.028 (2)	0.023 (2)	0.0028 (16)	0.0075 (18)	0.0029 (17)
C21	0.034 (2)	0.026 (2)	0.0211 (19)	0.0008 (17)	0.0148 (19)	0.0039 (16)
C22	0.031 (2)	0.024 (2)	0.0231 (19)	0.0028 (17)	0.0175 (18)	0.0023 (16)
C23	0.0188 (18)	0.0181 (17)	0.0190 (17)	−0.0019 (15)	0.0090 (16)	−0.0049 (15)
C24	0.018 (2)	0.0178 (18)	0.024 (2)	−0.0015 (13)	0.0115 (18)	−0.0029 (14)
C25	0.052 (3)	0.037 (3)	0.049 (3)	−0.014 (2)	0.031 (3)	−0.002 (2)
C26	0.059 (3)	0.0205 (15)	0.053 (2)	0.014 (2)	0.034 (2)	0.009 (3)
C27	0.043 (3)	0.052 (3)	0.046 (3)	0.011 (2)	0.022 (3)	0.006 (2)

Geometric parameters (Å, º) top

Cu1—O1	1.956 (3)	C8—C9	1.350 (6)
Cu1—N1	2.001 (3)	C8—H8A	0.9300
Cu1—N3	2.009 (3)	C9—C10	1.392 (6)
Cu1—N2	2.071 (3)	C9—H9A	0.9300
Cu1—N4	2.175 (4)	C10—H10A	0.9300
S1—O3	1.466 (3)	C11—C12	1.433 (6)
S1—O4	1.469 (3)	C13—C14	1.425 (6)
S1—O2	1.475 (3)	C13—H13A	0.9300
S1—O1	1.503 (3)	C14—C15	1.347 (7)
O5—C25	1.392 (6)	C14—H14A	0.9300
O5—H5B	0.8200	C15—C16	1.399 (6)
O6—C27	1.451 (6)	C15—H15A	0.9300
O6—H6B	0.8200	C16—C24	1.413 (6)
N1—C1	1.333 (5)	C16—C17	1.443 (6)
N1—C12	1.367 (5)	C17—C18	1.360 (6)
N2—C10	1.343 (5)	C17—H17A	0.9300
N2—C11	1.363 (5)	C18—C19	1.438 (6)
N3—C13	1.331 (6)	C18—H18A	0.9300
N3—C24	1.352 (6)	C19—C20	1.403 (6)
N4—C22	1.331 (5)	C19—C23	1.413 (6)
N4—C23	1.349 (5)	C20—C21	1.371 (6)
C1—C2	1.380 (6)	C20—H20A	0.9300
C1—H1A	0.9300	C21—C22	1.411 (6)
C2—C3	1.390 (6)	C21—H21A	0.9300
C2—H2A	0.9300	C22—H22A	0.9300
C3—C4	1.416 (6)	C23—C24	1.436 (6)
C3—H3A	0.9300	C25—C26	1.513 (7)
C4—C12	1.398 (6)	C25—H25A	0.9700
C4—C5	1.423 (6)	C25—H25B	0.9700
C5—C6	1.358 (6)	C26—C27	1.503 (8)
C5—H5A	0.9300	C26—H26A	0.9700
C6—C7	1.422 (6)	C26—H26B	0.9700
C6—H6A	0.9300	C27—H27A	0.9700
C7—C11	1.395 (6)	C27—H27B	0.9700
C7—C8	1.429 (5)

O1—Cu1—N1	92.19 (12)	N2—C11—C7	124.4 (3)
O1—Cu1—N3	98.11 (12)	N2—C11—C12	116.3 (3)
N1—Cu1—N3	168.47 (9)	C7—C11—C12	119.3 (3)
O1—Cu1—N2	145.89 (12)	N1—C12—C4	123.6 (4)
N1—Cu1—N2	81.16 (14)	N1—C12—C11	116.6 (4)
N3—Cu1—N2	93.02 (14)	C4—C12—C11	119.8 (4)
O1—Cu1—N4	105.07 (12)	N3—C13—C14	121.2 (4)
N1—Cu1—N4	92.28 (13)	N3—C13—H13A	119.4
N3—Cu1—N4	80.09 (14)	C14—C13—H13A	119.4
N2—Cu1—N4	108.58 (9)	C15—C14—C13	119.7 (4)
O3—S1—O4	110.99 (16)	C15—C14—H14A	120.1
O3—S1—O2	109.25 (16)	C13—C14—H14A	120.1
O4—S1—O2	109.75 (19)	C14—C15—C16	120.0 (4)
O3—S1—O1	107.05 (16)	C14—C15—H15A	120.0
O4—S1—O1	111.03 (18)	C16—C15—H15A	120.0
O2—S1—O1	108.70 (15)	C15—C16—C24	117.7 (4)
S1—O1—Cu1	128.81 (16)	C15—C16—C17	123.4 (4)
C25—O5—H5B	109.5	C24—C16—C17	118.9 (4)
C27—O6—H6B	109.5	C18—C17—C16	120.7 (4)
C1—N1—C12	117.7 (4)	C18—C17—H17A	119.6
C1—N1—Cu1	128.3 (3)	C16—C17—H17A	119.6
C12—N1—Cu1	113.5 (3)	C17—C18—C19	121.5 (4)
C10—N2—C11	116.8 (3)	C17—C18—H18A	119.2
C10—N2—Cu1	131.4 (3)	C19—C18—H18A	119.2
C11—N2—Cu1	111.7 (3)	C20—C19—C23	118.1 (4)
C13—N3—C24	119.2 (4)	C20—C19—C18	123.1 (4)
C13—N3—Cu1	126.0 (3)	C23—C19—C18	118.8 (4)
C24—N3—Cu1	114.5 (3)	C21—C20—C19	118.8 (4)
C22—N4—C23	119.0 (4)	C21—C20—H20A	120.6
C22—N4—Cu1	131.6 (3)	C19—C20—H20A	120.6
C23—N4—Cu1	109.3 (3)	C20—C21—C22	119.8 (4)
N1—C1—C2	123.6 (4)	C20—C21—H21A	120.1
N1—C1—H1A	118.2	C22—C21—H21A	120.1
C2—C1—H1A	118.2	N4—C22—C21	121.9 (4)
C1—C2—C3	118.8 (4)	N4—C22—H22A	119.1
C1—C2—H2A	120.6	C21—C22—H22A	119.1
C3—C2—H2A	120.6	N4—C23—C19	122.2 (3)
C2—C3—C4	119.8 (4)	N4—C23—C24	117.8 (3)
C2—C3—H3A	120.1	C19—C23—C24	119.9 (3)
C4—C3—H3A	120.1	N3—C24—C16	122.1 (4)
C12—C4—C3	116.5 (4)	N3—C24—C23	117.7 (4)
C12—C4—C5	119.6 (4)	C16—C24—C23	120.1 (4)
C3—C4—C5	123.9 (4)	O5—C25—C26	113.0 (5)
C6—C5—C4	120.5 (4)	O5—C25—H25A	109.0
C6—C5—H5A	119.7	C26—C25—H25A	109.0
C4—C5—H5A	119.7	O5—C25—H25B	109.0
C5—C6—C7	121.0 (4)	C26—C25—H25B	109.0
C5—C6—H6A	119.5	H25A—C25—H25B	107.8
C7—C6—H6A	119.5	C27—C26—C25	112.9 (3)
C11—C7—C6	119.7 (3)	C27—C26—H26A	109.0
C11—C7—C8	116.3 (4)	C25—C26—H26A	109.0
C6—C7—C8	124.0 (4)	C27—C26—H26B	109.0
C9—C8—C7	119.4 (4)	C25—C26—H26B	109.0
C9—C8—H8A	120.3	H26A—C26—H26B	107.8
C7—C8—H8A	120.3	O6—C27—C26	110.3 (5)
C8—C9—C10	120.4 (4)	O6—C27—H27A	109.6
C8—C9—H9A	119.8	C26—C27—H27A	109.6
C10—C9—H9A	119.8	O6—C27—H27B	109.6
N2—C10—C9	122.7 (4)	C26—C27—H27B	109.6
N2—C10—H10A	118.7	H27A—C27—H27B	108.1
C9—C10—H10A	118.7

O3—S1—O1—Cu1	144.4 (2)	C10—N2—C11—C12	177.6 (3)
O4—S1—O1—Cu1	−94.3 (2)	Cu1—N2—C11—C12	−3.8 (4)
O2—S1—O1—Cu1	26.5 (3)	C6—C7—C11—N2	−179.0 (3)
N1—Cu1—O1—S1	110.9 (2)	C8—C7—C11—N2	0.7 (6)
N3—Cu1—O1—S1	−74.3 (2)	C6—C7—C11—C12	2.1 (6)
N2—Cu1—O1—S1	33.5 (4)	C8—C7—C11—C12	−178.2 (4)
N4—Cu1—O1—S1	−156.1 (2)	C1—N1—C12—C4	−0.1 (6)
O1—Cu1—N1—C1	34.3 (3)	Cu1—N1—C12—C4	−172.7 (3)
N3—Cu1—N1—C1	−119.1 (8)	C1—N1—C12—C11	−179.3 (4)
N2—Cu1—N1—C1	−179.4 (4)	Cu1—N1—C12—C11	8.1 (4)
N4—Cu1—N1—C1	−70.9 (3)	C3—C4—C12—N1	1.2 (6)
O1—Cu1—N1—C12	−154.1 (3)	C5—C4—C12—N1	−176.6 (4)
N3—Cu1—N1—C12	52.5 (11)	C3—C4—C12—C11	−179.6 (4)
N2—Cu1—N1—C12	−7.7 (3)	C5—C4—C12—C11	2.6 (6)
N4—Cu1—N1—C12	100.7 (3)	N2—C11—C12—N1	−2.7 (5)
O1—Cu1—N2—C10	−94.7 (4)	C7—C11—C12—N1	176.2 (4)
N1—Cu1—N2—C10	−175.5 (4)	N2—C11—C12—C4	178.0 (4)
N3—Cu1—N2—C10	14.5 (4)	C7—C11—C12—C4	−3.0 (6)
N4—Cu1—N2—C10	95.1 (3)	C24—N3—C13—C14	−0.7 (6)
O1—Cu1—N2—C11	87.0 (3)	Cu1—N3—C13—C14	172.2 (3)
N1—Cu1—N2—C11	6.2 (2)	N3—C13—C14—C15	1.8 (6)
N3—Cu1—N2—C11	−163.8 (3)	C13—C14—C15—C16	−0.8 (6)
N4—Cu1—N2—C11	−83.2 (3)	C14—C15—C16—C24	−1.1 (6)
O1—Cu1—N3—C13	75.9 (3)	C14—C15—C16—C17	178.4 (4)
N1—Cu1—N3—C13	−131.1 (8)	C15—C16—C17—C18	−177.6 (4)
N2—Cu1—N3—C13	−71.8 (3)	C24—C16—C17—C18	1.8 (6)
N4—Cu1—N3—C13	179.8 (4)	C16—C17—C18—C19	−2.3 (6)
O1—Cu1—N3—C24	−110.9 (3)	C17—C18—C19—C20	−179.4 (4)
N1—Cu1—N3—C24	42.2 (11)	C17—C18—C19—C23	1.2 (6)
N2—Cu1—N3—C24	101.4 (3)	C23—C19—C20—C21	0.4 (6)
N4—Cu1—N3—C24	−6.9 (3)	C18—C19—C20—C21	−179.0 (4)
O1—Cu1—N4—C22	−80.9 (4)	C19—C20—C21—C22	−1.2 (7)
N1—Cu1—N4—C22	12.0 (4)	C23—N4—C22—C21	−0.3 (6)
N3—Cu1—N4—C22	−176.7 (4)	Cu1—N4—C22—C21	−178.4 (3)
N2—Cu1—N4—C22	93.4 (4)	C20—C21—C22—N4	1.2 (7)
O1—Cu1—N4—C23	100.9 (2)	C22—N4—C23—C19	−0.6 (6)
N1—Cu1—N4—C23	−166.2 (2)	Cu1—N4—C23—C19	177.9 (3)
N3—Cu1—N4—C23	5.1 (2)	C22—N4—C23—C24	178.9 (3)
N2—Cu1—N4—C23	−84.8 (3)	Cu1—N4—C23—C24	−2.6 (4)
C12—N1—C1—C2	−0.8 (6)	C20—C19—C23—N4	0.5 (6)
Cu1—N1—C1—C2	170.5 (3)	C18—C19—C23—N4	180.0 (3)
N1—C1—C2—C3	0.6 (6)	C20—C19—C23—C24	−179.0 (4)
C1—C2—C3—C4	0.6 (6)	C18—C19—C23—C24	0.5 (6)
C2—C3—C4—C12	−1.4 (6)	C13—N3—C24—C16	−1.3 (6)
C2—C3—C4—C5	176.3 (4)	Cu1—N3—C24—C16	−175.0 (3)
C12—C4—C5—C6	−1.3 (6)	C13—N3—C24—C23	−178.4 (4)
C3—C4—C5—C6	−178.9 (4)	Cu1—N3—C24—C23	7.8 (4)
C4—C5—C6—C7	0.4 (6)	C15—C16—C24—N3	2.2 (6)
C5—C6—C7—C11	−0.8 (6)	C17—C16—C24—N3	−177.3 (4)
C5—C6—C7—C8	179.5 (4)	C15—C16—C24—C23	179.3 (4)
C11—C7—C8—C9	0.0 (6)	C17—C16—C24—C23	−0.2 (6)
C6—C7—C8—C9	179.7 (4)	N4—C23—C24—N3	−3.2 (5)
C7—C8—C9—C10	−0.1 (6)	C19—C23—C24—N3	176.3 (4)
C11—N2—C10—C9	1.2 (6)	N4—C23—C24—C16	179.6 (4)
Cu1—N2—C10—C9	−177.1 (3)	C19—C23—C24—C16	−0.9 (6)
C8—C9—C10—N2	−0.5 (7)	O5—C25—C26—C27	−55.4 (6)
C10—N2—C11—C7	−1.3 (6)	C25—C26—C27—O6	−61.9 (6)
Cu1—N2—C11—C7	177.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···O3	0.82	1.99	2.788 (4)	166
O6—H6B···O4	0.82	2.01	2.817 (5)	166

Experimental details

Crystal data
Chemical formula	[Cu(SO₄)(C₁₂H₈N₂)₂]·C₃H₈O₂
M_r	596.10
Crystal system, space group	Monoclinic, Cc
Temperature (K)	223
a, b, c (Å)	17.523 (4), 12.562 (3), 13.438 (3)
β (°)	123.44 (3)
V (Å³)	2468.4 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.02
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (REQAB; Jacobson, 1998)
T_min, T_max	0.750, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6895, 4049, 3892
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.094, 1.07
No. of reflections	4049
No. of parameters	354
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.82
Absolute structure	Flack (1983), 1224 Friedel pairs
Absolute structure parameter	0.56 (1)

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

Selected bond lengths (Å) top

Cu1—O1	1.956 (3)	Cu1—N2	2.071 (3)
Cu1—N1	2.001 (3)	Cu1—N4	2.175 (4)
Cu1—N3	2.009 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···O3	0.82	1.99	2.788 (4)	166
O6—H6B···O4	0.82	2.01	2.817 (5)	166

Acknowledgements

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

References

Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Jacobson, R. (1998). REQAB. Molecular Structure Corporation, The Woodlands, Texas, USA. Google Scholar
Murphy, B. & Hathaway, B. (2003). Coord. Chem. Rev. 243, 237-262. Web of Science CrossRef CAS Google Scholar
Potočňák, I., Špilovský, M. & Trávníček, Z. (2008). Acta Cryst. C64, m161–m163. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2007). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhong, K.-L. (2011a). Acta Cryst. E67, m1215–m1216. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhong, K.-L. (2011b). Z. Kristallogr. New Cryst. Struct. 226, 286–288. CAS Google Scholar

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