Bis(1,10-phenanthroline-κ2N,N′)(sulfato-O)copper(II) butane-2,3-diol monosolvate

Zhong, K.-L.; Cao, G.-Q.

doi:10.1107/S1600536812049951

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 1| January 2013| Pages m40-m41

https://doi.org/10.1107/S1600536812049951

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Bis(1,10-phenanthroline-κ²N,N′)(sulfato-O)copper(II) butane-2,3-diol monosolvate

Kai-Long Zhong ^a ^* and Guo-Qing Cao ^a

^aDepartment of Applied Chemistry, Nanjing College of Chemical Technology, Nanjing 210048, People's Republic of China
^*Correspondence e-mail: zklong76@163.com

(Received 30 November 2012; accepted 6 December 2012; online 12 December 2012)

The title compound, [Cu(SO₄)(C₁₂H₈N₂)₂]·C₄H₁₀O₂, is comprised of neutral monomeric complex and butane-2,3-diol solvent molecules. In the complex, the Cu^II ion is in a distorted square-pyramidal coordination environment defined by four N atoms from two chelating 1,10-phenanthroline ligands and one O atom from a monodentate sulfate anion; the O atom is at the apex. The two chelating N₂C₂ groups subtend a dihedral angle of 85.8 (4)°. In the crystal, the neutral monomeric complex and butane-2,3-diol solvent molecules are held together by O—H⋯O hydrogen bonding, which leads to additional stabilization of the structure. 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. The sulfate anion is disordered over two sets of sites with occupancies of 0.55 (1) and 0.45 (1).

Related literature

For the ethane-1,2-diol solvate of the title complex, see: Zhong (2011a ), for the propane-1,2-diol solvate, see: Zhong (2011b ) and for the propane-1,3-diol solvate, see: Zhong (2012 ). For related structures of transition metal complexes with a sulfate anion, see: Wang & Zhong (2011 ); Zhong & Ni (2012 ); Cui et al. (2010 ); Lu et al. (2006 ).

Experimental

Crystal data

[Cu(SO₄)(C₁₂H₈N₂)₂]·C₄H₁₀O₂
M_r = 610.13
Monoclinic, C c
a = 17.352 (4) Å
b = 13.070 (3) Å
c = 13.444 (3) Å
β = 123.84 (3)°
V = 2532.4 (13) Å³
Z = 4
Mo Kα radiation
μ = 1.00 mm⁻¹
T = 223 K
0.32 × 0.27 × 0.21 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.741, T_max = 0.818
7154 measured reflections
4178 independent reflections
3542 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.135
S = 0.99
4178 reflections
408 parameters
124 restraints
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.53 e Å⁻³
Absolute structure: Flack (1983 ), 1317 Friedel pairs
Flack parameter: 0.55 (2)

Table 1
Selected bond lengths (Å)

Cu1—O1	1.922 (11)
Cu1—O1′	1.944 (10)
Cu1—N1	2.000 (7)
Cu1—N4	2.014 (7)
Cu1—N3	2.091 (6)
Cu1—N2	2.186 (7)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5B⋯O3	0.82	1.92	2.73 (2)	172
O5—H5B⋯O4′	0.82	2.01	2.83 (2)	176
O6—H6⋯O3′	0.82	2.19	2.919 (16)	148
O6—H6⋯O4	0.82	1.95	2.720 (14)	156

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).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812049951/bq2380sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812049951/bq2380Isup2.hkl

checkCIF report

Comment top

In the past few years, we have unexpectedly obtained and characterized some transition metal complexes with bidentate-chelating sulfate auxiliary ligand via alcohol-solvothermal reaction during attempts to synthesize mixed-ligand coordination polymers, such as cobalt complex (Wang & Zhong, 2011), nickel complex (Zhong & Ni, 2012), zinc complex (Cui et al., 2010), cadmium complex (Lu et al., 2006). The title compound [CuSO₄(C₁₂H₈N₂)₂].C₄H₁₀O₂, (I), was obtained by the similar alcohol-solvothermal reaction and its crystal structure has not hitherto been reported.

The X-ray diffraction experiment found that the title complex is isotypical to the previously reported [CuSO₄(C₁₂H₈N₂)₂].C₂H₆O₂ (Zhong, 2011a), (II), [CuSO₄(C₁₂H₈N₂)₂].CH₂OHCHOHCH₃ (Zhong, 2011b), (III), and [CuSO₄(C₁₂H₈N₂)₂].CH₂OHCH₂CH₂OH (Zhong, 2012), (IV). The geometry of the phenanthroline and sulfate ligands are in good agreement with those reported in the (II), (III) and (IV). The Cu^II metal ion is five-coordinated by four N atoms from two chelating phen ligands and an O atoms from a monodentate sulfate ligand, resulting in a distorted CuN₄O square-pyramidal environment. 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 (Fig 1). The dihedral angle of the two chelating N2C2 groups is 85.8 (4)°, which is larger than those reported in (II) [71.1 (2)°], (III) [84.9 (4)°] and (IV) [71.10 (15) Å], respectively. The Cu—O bond distance [1.922 (11) Å - 1.944 (10) Å], the Cu—N bond distance [2.000 (7) - 2.186 (7) Å], and the N—Cu—N bite angle [79.8 (3) - 81.6 (3)°] are comparable to those observed in (II), (III) and (IV) (Table 1).

In the crystal, the sulfate group is disordered over two positions with refined site occupancies of 0.55 (1) and 0.45 (1), and is hydrogen bonded to the solvent butane-2,3-diol molecule (Table 2 & Fig. 1).

Related literature top

For the ethane-1,2-diol solvate of the title complex, see: Zhong (2011a), for the propane-1,2-diol solvate, see: Zhong (2011b) and for the propane-1,3-diol solvate, see: Zhong (2012). For related structures of transition metal complexes with a sulfate anion, see: Wang & Zhong (2011); Zhong & Ni (2012); Cui et al. (2010); Lu et al. (2006).

Experimental top

The single crystals of (I) suitable to X-ray analysis were obtained by 0.2 mmol phen, 0.1 mmol CuSO₄.5H₂O, 2.0 ml propane-1,3-diol and 1.0 ml water mixed and placed in a thick Pyrex tube, which was sealed and heated to 453 K for 72 h.

Structure description top

For the ethane-1,2-diol solvate of the title complex, see: Zhong (2011a), for the propane-1,2-diol solvate, see: Zhong (2011b) and for the propane-1,3-diol solvate, see: Zhong (2012). For related structures of transition metal complexes with a sulfate anion, see: Wang & Zhong (2011); Zhong & Ni (2012); Cui et al. (2010); Lu et al. (2006).

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 35% probability level. Hydrogen bonds O—H···O are shown as dashed lines.

Bis(1,10-phenanthroline-κ²N,N')(sulfato-O)copper(II) butane-2,3-diol monosolvate top

Crystal data top

[Cu(SO₄)(C₁₂H₈N₂)₂]·C₄H₁₀O₂	F(000) = 1260
M_r = 610.13	D_x = 1.600 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 5509 reflections
a = 17.352 (4) Å	θ = 3.2–27.5°
b = 13.070 (3) Å	µ = 1.00 mm⁻¹
c = 13.444 (3) Å	T = 223 K
β = 123.84 (3)°	Block, green
V = 2532.4 (13) Å³	0.32 × 0.27 × 0.21 mm
Z = 4

Data collection top

Rigaku Mercury CCD diffractometer	4178 independent reflections
Radiation source: fine-focus sealed tube	3542 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.026
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
ω scans	h = −15→22
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −16→15
T_min = 0.741, T_max = 0.818	l = −17→16
7154 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)] = 0.046	H-atom parameters constrained
wR(F²) = 0.135	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.002
4178 reflections	Δρ_max = 0.60 e Å⁻³
408 parameters	Δρ_min = −0.53 e Å⁻³
124 restraints	Absolute structure: Flack (1983), 1317 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.55 (2)

Crystal data top

[Cu(SO₄)(C₁₂H₈N₂)₂]·C₄H₁₀O₂	V = 2532.4 (13) Å³
M_r = 610.13	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 17.352 (4) Å	µ = 1.00 mm⁻¹
b = 13.070 (3) Å	T = 223 K
c = 13.444 (3) Å	0.32 × 0.27 × 0.21 mm
β = 123.84 (3)°

Data collection top

Rigaku Mercury CCD diffractometer	4178 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	3542 reflections with I > 2σ(I)
T_min = 0.741, T_max = 0.818	R_int = 0.026
7154 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.135	Δρ_max = 0.60 e Å⁻³
S = 0.99	Δρ_min = −0.53 e Å⁻³
4178 reflections	Absolute structure: Flack (1983), 1317 Friedel pairs
408 parameters	Absolute structure parameter: 0.55 (2)
124 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	Occ. (<1)
Cu1	0.26519 (10)	0.30074 (3)	0.29387 (13)	0.02436 (16)
S1	0.2748 (3)	0.5417 (4)	0.2771 (4)	0.0265 (13)	0.547 (12)
S1'	0.2569 (3)	0.5422 (4)	0.3106 (4)	0.0170 (14)	0.453 (12)
O1	0.2897 (10)	0.4419 (8)	0.3416 (12)	0.043 (3)	0.547 (12)
O1'	0.2430 (10)	0.4435 (7)	0.2448 (11)	0.027 (3)	0.453 (12)
O2	0.2706 (8)	0.5188 (9)	0.1677 (9)	0.037 (3)	0.547 (12)
O2'	0.2653 (8)	0.5225 (8)	0.4213 (8)	0.023 (3)	0.453 (12)
O3	0.1922 (11)	0.5995 (16)	0.2536 (19)	0.041 (5)	0.547 (12)
O3'	0.3442 (10)	0.5860 (12)	0.3305 (17)	0.021 (3)	0.453 (12)
O4	0.3552 (9)	0.6066 (10)	0.3586 (11)	0.021 (3)	0.547 (12)
O4'	0.1754 (13)	0.6044 (16)	0.2259 (16)	0.027 (5)	0.453 (12)
O5	0.2174 (4)	0.7813 (3)	0.3686 (4)	0.0442 (11)
H5B	0.2079	0.7299	0.3282	0.066*
O6	0.3460 (5)	0.8062 (5)	0.2956 (8)	0.096 (3)
H6	0.3455	0.7532	0.3279	0.144*
N1	0.3506 (5)	0.2822 (5)	0.2394 (6)	0.0244 (14)
N2	0.3706 (5)	0.2068 (4)	0.4426 (6)	0.0236 (15)
N3	0.1647 (5)	0.2096 (5)	0.1528 (5)	0.0220 (14)
N4	0.1742 (5)	0.2848 (5)	0.3410 (6)	0.0232 (14)
C1	0.3444 (6)	0.3269 (7)	0.1484 (8)	0.0282 (17)
H1A	0.3000	0.3772	0.1053	0.034*
C2	0.4087 (7)	0.2967 (7)	0.1148 (9)	0.038 (2)
H2A	0.4052	0.3285	0.0505	0.046*
C3	0.4728 (6)	0.2229 (7)	0.1768 (8)	0.0375 (18)
H3A	0.5100	0.2000	0.1517	0.045*
C4	0.4826 (7)	0.1813 (8)	0.2797 (9)	0.038 (2)
C5	0.5554 (7)	0.1082 (5)	0.3559 (8)	0.032 (2)
H5A	0.5958	0.0858	0.3355	0.039*
C6	0.5640 (6)	0.0738 (6)	0.4535 (8)	0.036 (2)
H6A	0.6112	0.0273	0.5009	0.043*
C7	0.5031 (6)	0.1051 (6)	0.4909 (8)	0.0281 (18)
C8	0.5105 (7)	0.0762 (5)	0.5960 (9)	0.032 (2)
H8A	0.5567	0.0309	0.6490	0.038*
C9	0.4489 (6)	0.1151 (7)	0.6208 (8)	0.038 (2)
H9A	0.4540	0.0982	0.6915	0.046*
C10	0.3805 (6)	0.1789 (7)	0.5391 (7)	0.0277 (18)
H10A	0.3384	0.2035	0.5554	0.033*
C11	0.4289 (5)	0.1747 (6)	0.4123 (7)	0.0270 (18)
C12	0.4198 (5)	0.2096 (5)	0.3075 (7)	0.0183 (15)
C13	0.1532 (6)	0.1797 (6)	0.0470 (7)	0.0293 (19)
H13A	0.1933	0.2046	0.0273	0.035*
C14	0.0804 (6)	0.1109 (6)	−0.0329 (7)	0.032 (2)
H14A	0.0736	0.0927	−0.1043	0.039*
C15	0.0208 (6)	0.0714 (7)	−0.0069 (8)	0.033 (2)
H15A	−0.0248	0.0245	−0.0575	0.040*
C16	0.0311 (6)	0.1046 (6)	0.1007 (8)	0.0284 (18)
C17	−0.0306 (6)	0.0719 (6)	0.1307 (7)	0.035 (2)
H17A	−0.0777	0.0261	0.0808	0.042*
C18	−0.0226 (6)	0.1067 (7)	0.2327 (8)	0.037 (2)
H18A	−0.0630	0.0823	0.2521	0.045*
C19	0.0465 (5)	0.1794 (6)	0.3089 (6)	0.0215 (15)
C20	0.0547 (6)	0.2284 (8)	0.4077 (7)	0.0346 (18)
H20A	0.0129	0.2132	0.4283	0.042*
C21	0.1237 (7)	0.2981 (6)	0.4733 (9)	0.036 (2)
H21A	0.1324	0.3270	0.5420	0.043*
C22	0.1777 (6)	0.3233 (7)	0.4369 (6)	0.0324 (19)
H22A	0.2228	0.3726	0.4816	0.039*
C23	0.1077 (6)	0.2146 (6)	0.2782 (7)	0.0281 (18)
C24	0.1010 (5)	0.1709 (6)	0.1728 (6)	0.0194 (15)
C25	0.2642 (9)	0.9498 (6)	0.4054 (10)	0.059 (3)
H25A	0.2309	0.9594	0.4425	0.089*
H25B	0.2663	1.0133	0.3711	0.089*
H25C	0.3262	0.9275	0.4643	0.089*
C26	0.2142 (7)	0.8676 (6)	0.3052 (8)	0.053 (2)
H26A	0.1498	0.8877	0.2462	0.063*
C27	0.2654 (7)	0.8516 (5)	0.2453 (8)	0.058 (2)
H27A	0.2238	0.8072	0.1771	0.069*
C28	0.2703 (13)	0.9468 (10)	0.1881 (16)	0.101 (5)
H28A	0.3013	0.9326	0.1487	0.151*
H28B	0.3040	0.9982	0.2482	0.151*
H28C	0.2086	0.9709	0.1304	0.151*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0249 (3)	0.0219 (2)	0.0321 (3)	−0.0008 (5)	0.0194 (2)	−0.0011 (5)
S1	0.026 (3)	0.027 (2)	0.029 (2)	−0.0005 (17)	0.017 (2)	−0.0049 (19)
S1'	0.017 (3)	0.014 (2)	0.017 (2)	−0.0005 (17)	0.008 (2)	−0.0029 (18)
O1	0.054 (5)	0.037 (5)	0.044 (5)	−0.006 (3)	0.031 (4)	0.005 (3)
O1'	0.045 (5)	0.009 (4)	0.029 (5)	0.001 (3)	0.023 (4)	0.004 (3)
O2	0.043 (5)	0.049 (5)	0.029 (4)	−0.002 (3)	0.025 (3)	−0.002 (3)
O2'	0.022 (4)	0.024 (4)	0.015 (4)	−0.009 (3)	0.006 (3)	0.001 (3)
O3	0.034 (6)	0.042 (6)	0.047 (7)	0.000 (4)	0.022 (4)	0.005 (4)
O3'	0.017 (5)	0.016 (5)	0.028 (5)	−0.001 (3)	0.011 (4)	−0.003 (4)
O4	0.017 (4)	0.019 (5)	0.021 (5)	0.004 (3)	0.007 (3)	−0.004 (3)
O4'	0.029 (6)	0.028 (6)	0.024 (6)	0.002 (4)	0.016 (4)	0.003 (4)
O5	0.066 (3)	0.038 (2)	0.041 (2)	0.001 (2)	0.037 (2)	−0.0007 (19)
O6	0.076 (4)	0.060 (4)	0.188 (7)	0.039 (3)	0.096 (5)	0.071 (4)
N1	0.023 (3)	0.026 (3)	0.027 (3)	−0.003 (3)	0.016 (3)	−0.002 (3)
N2	0.027 (3)	0.017 (3)	0.038 (4)	−0.001 (2)	0.025 (3)	0.000 (2)
N3	0.019 (3)	0.026 (3)	0.011 (3)	0.002 (2)	0.002 (2)	−0.001 (2)
N4	0.022 (3)	0.027 (3)	0.019 (3)	−0.008 (3)	0.010 (3)	−0.007 (3)
C1	0.033 (4)	0.026 (3)	0.047 (5)	0.009 (3)	0.036 (4)	0.008 (3)
C2	0.034 (4)	0.055 (5)	0.035 (4)	0.002 (3)	0.025 (4)	−0.009 (3)
C3	0.038 (4)	0.046 (4)	0.048 (4)	0.005 (3)	0.035 (4)	−0.011 (4)
C4	0.043 (5)	0.035 (4)	0.048 (5)	0.003 (4)	0.033 (4)	−0.007 (3)
C5	0.034 (5)	0.017 (3)	0.044 (5)	0.008 (3)	0.021 (4)	−0.004 (3)
C6	0.023 (4)	0.025 (4)	0.054 (5)	0.009 (3)	0.018 (4)	−0.016 (3)
C7	0.023 (4)	0.019 (3)	0.031 (4)	0.007 (3)	0.009 (3)	0.007 (3)
C8	0.029 (5)	0.015 (3)	0.033 (5)	−0.002 (3)	0.006 (4)	0.008 (3)
C9	0.034 (5)	0.053 (5)	0.039 (5)	−0.006 (4)	0.028 (4)	0.001 (4)
C10	0.026 (4)	0.034 (4)	0.026 (4)	−0.009 (4)	0.016 (4)	−0.014 (3)
C11	0.019 (4)	0.022 (3)	0.031 (4)	−0.006 (3)	0.008 (3)	−0.004 (3)
C12	0.013 (3)	0.016 (3)	0.034 (4)	0.001 (3)	0.018 (3)	−0.002 (3)
C13	0.031 (4)	0.030 (3)	0.026 (4)	−0.001 (4)	0.015 (4)	−0.013 (3)
C14	0.039 (5)	0.020 (3)	0.020 (4)	0.001 (3)	0.005 (4)	−0.009 (3)
C15	0.021 (5)	0.043 (4)	0.028 (4)	−0.005 (4)	0.009 (4)	−0.003 (4)
C16	0.022 (4)	0.030 (4)	0.029 (4)	0.007 (3)	0.012 (3)	0.015 (4)
C17	0.026 (4)	0.036 (4)	0.030 (4)	0.002 (3)	0.007 (4)	−0.013 (3)
C18	0.022 (4)	0.060 (5)	0.034 (5)	−0.005 (4)	0.018 (4)	0.009 (4)
C19	0.009 (3)	0.033 (3)	0.020 (3)	0.005 (3)	0.007 (3)	0.007 (3)
C20	0.029 (4)	0.051 (4)	0.019 (3)	0.012 (3)	0.010 (3)	0.005 (3)
C21	0.044 (5)	0.036 (4)	0.033 (4)	0.007 (3)	0.025 (4)	−0.013 (3)
C22	0.024 (4)	0.039 (4)	0.017 (4)	−0.001 (3)	0.001 (3)	−0.006 (3)
C23	0.033 (4)	0.023 (4)	0.019 (4)	0.001 (3)	0.008 (3)	0.003 (3)
C24	0.026 (4)	0.017 (3)	0.019 (3)	0.000 (3)	0.015 (3)	0.002 (3)
C25	0.104 (6)	0.036 (4)	0.074 (5)	−0.044 (4)	0.071 (5)	−0.042 (4)
C26	0.070 (5)	0.046 (4)	0.069 (5)	0.016 (4)	0.055 (5)	0.009 (4)
C27	0.104 (7)	0.031 (3)	0.082 (6)	0.038 (4)	0.079 (6)	0.028 (4)
C28	0.149 (10)	0.089 (8)	0.110 (8)	0.024 (7)	0.100 (7)	0.021 (6)

Geometric parameters (Å, º) top

Cu1—O1	1.922 (11)	C7—C11	1.445 (11)
Cu1—O1'	1.944 (10)	C8—C9	1.382 (14)
Cu1—N1	2.000 (7)	C8—H8A	0.9300
Cu1—N4	2.014 (7)	C9—C10	1.364 (12)
Cu1—N3	2.091 (6)	C9—H9A	0.9300
Cu1—N2	2.186 (7)	C10—H10A	0.9300
S1—O2	1.463 (10)	C11—C12	1.404 (12)
S1—O4	1.471 (12)	C13—C14	1.430 (11)
S1—O3	1.490 (15)	C13—H13A	0.9300
S1—O1	1.506 (11)	C14—C15	1.365 (14)
S1'—O2'	1.435 (10)	C14—H14A	0.9300
S1'—O4'	1.470 (15)	C15—C16	1.423 (14)
S1'—O3'	1.498 (14)	C15—H15A	0.9300
S1'—O1'	1.507 (10)	C16—C24	1.361 (12)
O5—C26	1.396 (9)	C16—C17	1.405 (12)
O5—H5B	0.8200	C17—C18	1.377 (12)
O6—C27	1.307 (9)	C17—H17A	0.9300
O6—H6	0.8200	C18—C19	1.423 (12)
N1—C1	1.306 (10)	C18—H18A	0.9300
N1—C12	1.399 (10)	C19—C20	1.408 (11)
N2—C10	1.265 (11)	C19—C23	1.412 (11)
N2—C11	1.350 (11)	C20—C21	1.366 (13)
N3—C24	1.372 (10)	C20—H20A	0.9300
N3—C13	1.379 (10)	C21—C22	1.318 (14)
N4—C23	1.341 (10)	C21—H21A	0.9300
N4—C22	1.352 (11)	C22—H22A	0.9300
C1—C2	1.472 (12)	C23—C24	1.472 (11)
C1—H1A	0.9300	C25—C26	1.555 (13)
C2—C3	1.352 (13)	C25—H25A	0.9600
C2—H2A	0.9300	C25—H25B	0.9600
C3—C4	1.406 (13)	C25—H25C	0.9600
C3—H3A	0.9300	C26—C27	1.510 (9)
C4—C12	1.384 (11)	C26—H26A	0.9800
C4—C5	1.455 (13)	C27—C28	1.490 (14)
C5—C6	1.314 (13)	C27—H27A	0.9800
C5—H5A	0.9300	C28—H28A	0.9600
C6—C7	1.460 (12)	C28—H28B	0.9600
C6—H6A	0.9300	C28—H28C	0.9600
C7—C8	1.398 (14)

O1—Cu1—O1'	32.6 (2)	N2—C10—C9	124.3 (8)
O1—Cu1—N1	99.6 (4)	N2—C10—H10A	117.9
O1'—Cu1—N1	92.2 (4)	C9—C10—H10A	117.9
O1—Cu1—N4	93.5 (4)	N2—C11—C12	121.1 (7)
O1'—Cu1—N4	99.5 (4)	N2—C11—C7	119.1 (8)
N1—Cu1—N4	166.8 (3)	C12—C11—C7	119.7 (8)
O1—Cu1—N3	140.1 (4)	C4—C12—N1	121.5 (7)
O1'—Cu1—N3	109.3 (4)	C4—C12—C11	121.2 (7)
N1—Cu1—N3	90.7 (3)	N1—C12—C11	116.9 (7)
N4—Cu1—N3	79.8 (3)	N3—C13—C14	120.9 (8)
O1—Cu1—N2	108.5 (4)	N3—C13—H13A	119.6
O1'—Cu1—N2	139.1 (4)	C14—C13—H13A	119.6
N1—Cu1—N2	81.6 (3)	C15—C14—C13	121.6 (8)
N4—Cu1—N2	93.3 (3)	C15—C14—H14A	119.2
N3—Cu1—N2	111.08 (12)	C13—C14—H14A	119.2
O2—S1—O4	111.2 (9)	C14—C15—C16	117.5 (7)
O2—S1—O3	112.8 (11)	C14—C15—H15A	121.3
O4—S1—O3	105.5 (12)	C16—C15—H15A	121.3
O2—S1—O1	107.4 (7)	C24—C16—C17	120.5 (8)
O4—S1—O1	106.5 (8)	C24—C16—C15	118.5 (8)
O3—S1—O1	113.4 (12)	C17—C16—C15	121.0 (8)
O2'—S1'—O4'	113.7 (11)	C18—C17—C16	121.0 (8)
O2'—S1'—O3'	112.0 (9)	C18—C17—H17A	119.5
O4'—S1'—O3'	111.5 (12)	C16—C17—H17A	119.5
O2'—S1'—O1'	110.2 (7)	C17—C18—C19	121.0 (8)
O4'—S1'—O1'	104.4 (10)	C17—C18—H18A	119.5
O3'—S1'—O1'	104.3 (10)	C19—C18—H18A	119.5
S1—O1—Cu1	134.8 (9)	C20—C19—C23	115.4 (7)
S1'—O1'—Cu1	133.3 (8)	C20—C19—C18	125.8 (8)
C26—O5—H5B	109.5	C23—C19—C18	118.5 (7)
C27—O6—H6	109.5	C21—C20—C19	120.3 (8)
C1—N1—C12	120.6 (7)	C21—C20—H20A	119.9
C1—N1—Cu1	126.8 (6)	C19—C20—H20A	119.9
C12—N1—Cu1	112.6 (5)	C22—C21—C20	118.4 (8)
C10—N2—C11	121.6 (7)	C22—C21—H21A	120.8
C10—N2—Cu1	131.8 (6)	C20—C21—H21A	120.8
C11—N2—Cu1	106.6 (5)	C21—C22—N4	126.6 (8)
C24—N3—C13	115.4 (6)	C21—C22—H22A	116.7
C24—N3—Cu1	112.8 (5)	N4—C22—H22A	116.7
C13—N3—Cu1	131.8 (6)	N4—C23—C19	124.2 (8)
C23—N4—C22	114.9 (8)	N4—C23—C24	116.8 (8)
C23—N4—Cu1	115.1 (6)	C19—C23—C24	119.0 (7)
C22—N4—Cu1	129.3 (6)	C16—C24—N3	126.2 (7)
N1—C1—C2	119.2 (8)	C16—C24—C23	119.7 (7)
N1—C1—H1A	120.4	N3—C24—C23	113.9 (7)
C2—C1—H1A	120.4	C26—C25—H25A	109.5
C3—C2—C1	120.4 (9)	C26—C25—H25B	109.5
C3—C2—H2A	119.8	H25A—C25—H25B	109.5
C1—C2—H2A	119.8	C26—C25—H25C	109.5
C2—C3—C4	119.4 (8)	H25A—C25—H25C	109.5
C2—C3—H3A	120.3	H25B—C25—H25C	109.5
C4—C3—H3A	120.3	O5—C26—C27	112.2 (6)
C12—C4—C3	118.7 (8)	O5—C26—C25	102.5 (7)
C12—C4—C5	119.4 (9)	C27—C26—C25	110.4 (9)
C3—C4—C5	121.9 (9)	O5—C26—H26A	110.5
C6—C5—C4	119.9 (9)	C27—C26—H26A	110.5
C6—C5—H5A	120.1	C25—C26—H26A	110.5
C4—C5—H5A	120.1	O6—C27—C28	107.1 (9)
C5—C6—C7	123.2 (8)	O6—C27—C26	124.3 (7)
C5—C6—H6A	118.4	C28—C27—C26	112.2 (8)
C7—C6—H6A	118.4	O6—C27—H27A	103.6
C8—C7—C11	116.9 (8)	C28—C27—H27A	103.6
C8—C7—C6	126.6 (8)	C26—C27—H27A	103.6
C11—C7—C6	116.4 (8)	C27—C28—H28A	109.5
C9—C8—C7	119.8 (8)	C27—C28—H28B	109.5
C9—C8—H8A	120.1	H28A—C28—H28B	109.5
C7—C8—H8A	120.1	C27—C28—H28C	109.5
C10—C9—C8	118.3 (8)	H28A—C28—H28C	109.5
C10—C9—H9A	120.9	H28B—C28—H28C	109.5
C8—C9—H9A	120.9

O2—S1—O1—Cu1	−23.9 (15)	C11—C7—C8—C9	−0.8 (12)
O4—S1—O1—Cu1	−143.0 (11)	C6—C7—C8—C9	177.9 (8)
O3—S1—O1—Cu1	101.4 (15)	C7—C8—C9—C10	1.9 (12)
O1'—Cu1—O1—S1	−14.2 (12)	C11—N2—C10—C9	−0.1 (13)
N1—Cu1—O1—S1	64.7 (12)	Cu1—N2—C10—C9	176.6 (6)
N4—Cu1—O1—S1	−116.4 (12)	C8—C9—C10—N2	−1.5 (13)
N3—Cu1—O1—S1	−38.2 (16)	C10—N2—C11—C12	−177.2 (7)
N2—Cu1—O1—S1	149.0 (11)	Cu1—N2—C11—C12	5.4 (8)
O2'—S1'—O1'—Cu1	−18.3 (14)	C10—N2—C11—C7	1.3 (11)
O4'—S1'—O1'—Cu1	−140.8 (13)	Cu1—N2—C11—C7	−176.1 (6)
O3'—S1'—O1'—Cu1	102.1 (13)	C8—C7—C11—N2	−0.8 (11)
O1—Cu1—O1'—S1'	−17.4 (12)	C6—C7—C11—N2	−179.6 (7)
N1—Cu1—O1'—S1'	−121.9 (12)	C8—C7—C11—C12	177.7 (7)
N4—Cu1—O1'—S1'	64.2 (12)	C6—C7—C11—C12	−1.1 (11)
N3—Cu1—O1'—S1'	146.6 (11)	C3—C4—C12—N1	−3.4 (13)
N2—Cu1—O1'—S1'	−42.2 (15)	C5—C4—C12—N1	177.7 (7)
O1—Cu1—N1—C1	−65.3 (8)	C3—C4—C12—C11	−176.6 (8)
O1'—Cu1—N1—C1	−33.4 (8)	C5—C4—C12—C11	4.5 (12)
N4—Cu1—N1—C1	119.4 (13)	C1—N1—C12—C4	−1.3 (12)
N3—Cu1—N1—C1	76.0 (7)	Cu1—N1—C12—C4	176.2 (6)
N2—Cu1—N1—C1	−172.8 (8)	C1—N1—C12—C11	172.3 (8)
O1—Cu1—N1—C12	117.4 (6)	Cu1—N1—C12—C11	−10.3 (8)
O1'—Cu1—N1—C12	149.3 (6)	N2—C11—C12—C4	176.3 (8)
N4—Cu1—N1—C12	−57.9 (17)	C7—C11—C12—C4	−2.2 (11)
N3—Cu1—N1—C12	−101.3 (5)	N2—C11—C12—N1	2.8 (10)
N2—Cu1—N1—C12	10.0 (5)	C7—C11—C12—N1	−175.7 (7)
O1—Cu1—N2—C10	77.2 (8)	C24—N3—C13—C14	−1.5 (10)
O1'—Cu1—N2—C10	91.0 (9)	Cu1—N3—C13—C14	176.2 (5)
N1—Cu1—N2—C10	174.6 (8)	N3—C13—C14—C15	−0.9 (12)
N4—Cu1—N2—C10	−17.6 (8)	C13—C14—C15—C16	2.7 (12)
N3—Cu1—N2—C10	−97.9 (7)	C14—C15—C16—C24	−2.0 (12)
O1—Cu1—N2—C11	−105.6 (6)	C14—C15—C16—C17	176.5 (8)
O1'—Cu1—N2—C11	−91.8 (7)	C24—C16—C17—C18	0.6 (13)
N1—Cu1—N2—C11	−8.2 (5)	C15—C16—C17—C18	−177.8 (8)
N4—Cu1—N2—C11	159.6 (5)	C16—C17—C18—C19	2.1 (13)
N3—Cu1—N2—C11	79.2 (6)	C17—C18—C19—C20	172.6 (9)
O1—Cu1—N3—C24	−94.2 (8)	C17—C18—C19—C23	−0.5 (12)
O1'—Cu1—N3—C24	−107.6 (6)	C23—C19—C20—C21	−5.8 (12)
N1—Cu1—N3—C24	159.8 (5)	C18—C19—C20—C21	−179.1 (8)
N4—Cu1—N3—C24	−11.0 (5)	C19—C20—C21—C22	4.8 (13)
N2—Cu1—N3—C24	78.6 (6)	C20—C21—C22—N4	−2.1 (14)
O1—Cu1—N3—C13	88.0 (9)	C23—N4—C22—C21	0.6 (13)
O1'—Cu1—N3—C13	74.6 (8)	Cu1—N4—C22—C21	−168.9 (7)
N1—Cu1—N3—C13	−18.0 (7)	C22—N4—C23—C19	−1.9 (12)
N4—Cu1—N3—C13	171.2 (7)	Cu1—N4—C23—C19	169.2 (6)
N2—Cu1—N3—C13	−99.2 (7)	C22—N4—C23—C24	179.7 (7)
O1—Cu1—N4—C23	151.3 (7)	Cu1—N4—C23—C24	−9.2 (9)
O1'—Cu1—N4—C23	119.0 (7)	C20—C19—C23—N4	4.5 (12)
N1—Cu1—N4—C23	−33.4 (18)	C18—C19—C23—N4	178.3 (8)
N3—Cu1—N4—C23	10.9 (5)	C20—C19—C23—C24	−177.2 (7)
N2—Cu1—N4—C23	−99.9 (6)	C18—C19—C23—C24	−3.4 (11)
O1—Cu1—N4—C22	−39.2 (8)	C17—C16—C24—N3	−179.0 (7)
O1'—Cu1—N4—C22	−71.4 (8)	C15—C16—C24—N3	−0.6 (12)
N1—Cu1—N4—C22	136.2 (13)	C17—C16—C24—C23	−4.6 (12)
N3—Cu1—N4—C22	−179.6 (8)	C15—C16—C24—C23	173.9 (8)
N2—Cu1—N4—C22	69.6 (8)	C13—N3—C24—C16	2.3 (11)
C12—N1—C1—C2	2.7 (12)	Cu1—N3—C24—C16	−175.9 (6)
Cu1—N1—C1—C2	−174.3 (6)	C13—N3—C24—C23	−172.4 (7)
N1—C1—C2—C3	0.6 (13)	Cu1—N3—C24—C23	9.4 (8)
C1—C2—C3—C4	−5.2 (13)	N4—C23—C24—C16	−175.6 (7)
C2—C3—C4—C12	6.5 (14)	C19—C23—C24—C16	6.0 (11)
C2—C3—C4—C5	−174.7 (8)	N4—C23—C24—N3	−0.5 (10)
C12—C4—C5—C6	−3.6 (13)	C19—C23—C24—N3	−178.9 (7)
C3—C4—C5—C6	177.6 (9)	O5—C26—C27—O6	−42.6 (15)
C4—C5—C6—C7	0.2 (13)	C25—C26—C27—O6	71.1 (12)
C5—C6—C7—C8	−176.6 (9)	O5—C26—C27—C28	−174.2 (10)
C5—C6—C7—C11	2.0 (12)	C25—C26—C27—C28	−60.6 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···O3	0.82	1.92	2.73 (2)	172
O5—H5B···O4′	0.82	2.01	2.83 (2)	176
O6—H6···O3′	0.82	2.19	2.919 (16)	148
O6—H6···O4	0.82	1.95	2.720 (14)	156

Experimental details

Crystal data
Chemical formula	[Cu(SO₄)(C₁₂H₈N₂)₂]·C₄H₁₀O₂
M_r	610.13
Crystal system, space group	Monoclinic, Cc
Temperature (K)	223
a, b, c (Å)	17.352 (4), 13.070 (3), 13.444 (3)
β (°)	123.84 (3)
V (Å³)	2532.4 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.00
Crystal size (mm)	0.32 × 0.27 × 0.21

Data collection
Diffractometer	Rigaku Mercury CCD
Absorption correction	Multi-scan (REQAB; Jacobson, 1998)
T_min, T_max	0.741, 0.818
No. of measured, independent and observed [I > 2σ(I)] reflections	7154, 4178, 3542
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.135, 0.99
No. of reflections	4178
No. of parameters	408
No. of restraints	124
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.60, −0.53
Absolute structure	Flack (1983), 1317 Friedel pairs
Absolute structure parameter	0.55 (2)

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	1.922 (11)	Cu1—N4	2.014 (7)
Cu1—O1'	1.944 (10)	Cu1—N3	2.091 (6)
Cu1—N1	2.000 (7)	Cu1—N2	2.186 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···O3	0.82	1.92	2.73 (2)	172
O5—H5B···O4'	0.82	2.01	2.83 (2)	176
O6—H6···O3'	0.82	2.19	2.919 (16)	148
O6—H6···O4	0.82	1.95	2.720 (14)	156

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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