catena-Poly[[[diaqua­copper(II)]-bis­[μ-1,5-bis­(1H-imidazol-1-yl)pentane-κ2N3:N3′]] naphthalene-1,5-disulfonate]

Zhang, L.-P.; Wen, S.-T.; Fu, X.-N.

doi:10.1107/S1600536812045679

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page m1505

doi:10.1107/S1600536812045679

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catena-Poly[[[diaquacopper(II)]-bis[μ-1,5-bis(1H-imidazol-1-yl)pentane-κ²N³:N^3′]] naphthalene-1,5-disulfonate]

Lai-Ping Zhang,^a ^* Shu-Tang Wen ^a and Xiao-Ning Fu ^a

^aDepartment of Chemistry and Chemical Engineering, Xinxiang University, Xinxiang 453000, People's Republic of China
^*Correspondence e-mail: zhanglaiping2010@yahoo.com.cn

(Received 21 October 2012; accepted 5 November 2012; online 17 November 2012)

In the title complex, {[Cu(C₁₁H₁₆N₄)₂(H₂O)₂](C₁₀H₆O₆S₂)}_n, the Cu^II atom, lying on an inversion center, is six-coordinated by two water molecules and four N atoms from four 1,5-bis(1H-imidazol-1-yl)pentane (biim-5) ligands in a distorted octahedral geometry. Adjacent Cu^II atoms are linked by two biim-5 ligands, forming a chain along [111]. Two atoms of the pentane group are disordered over two sets of sites, with an occupancy ratio of 0.554 (18):0.446 (18). Intermolecular O—H⋯O hydrogen bonds link the chains and the centrosymmetric naphthalene-1,5-disulfonate anions into a layer structure parallel to (0-11).

Related literature

For background to metal-organic coordination polymers with N-donor ligands, see: Kesanli et al. (2005 ); Wei et al. (2008 ); Zhang et al. (2010 ).

Experimental

Crystal data

[Cu(C₁₁H₁₆N₄)₂(H₂O)₂](C₁₀H₆O₆S₂)
M_r = 790.37
Triclinic, $[P \overline 1]$
a = 9.300 (5) Å
b = 9.880 (5) Å
c = 11.020 (5) Å
α = 95.490 (5)°
β = 102.930 (5)°
γ = 114.000 (5)°
V = 881.5 (8) Å³
Z = 1
Mo Kα radiation
μ = 0.80 mm⁻¹
T = 293 K
0.41 × 0.33 × 0.21 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.970, T_max = 0.980
8706 measured reflections
3995 independent reflections
2218 reflections with I > 2σ(I)
R_int = 0.076

Refinement

R[F² > 2σ(F²)] = 0.074
wR(F²) = 0.167
S = 1.03
3995 reflections
258 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O2	0.89 (6)	1.97 (6)	2.836 (6)	163 (6)
O1W—H1B⋯O1ⁱ	0.89 (4)	2.11 (4)	3.001 (6)	178 (7)
Symmetry code: (i) -x, -y+1, -z+1.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); 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 I, global. DOI: 10.1107/S1600536812045679/hy2599sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812045679/hy2599Isup2.hkl

checkCIF report

Comment top

There is currently much interest in adopting N-donor ligands as second ligands to prepare new metal-organic coordination polymers because of their special coordination character (Kesanli et al., 2005). Among the N-donor bridging ligands, bis(imidazole) ligands, as an important family of flexible N-donor ligands, have attracted great interest. The main reason is that the flexible nature of the alkyl spacer allows the backbone of the bis(imidazole) ligand to bend and rotate freely so as to conform to the coordination geometries of central metal atoms (Wei et al., 2008). As a result, the bis(imidazole) ligands, especially 1,1'-(1,4-butanediyl)bis(imidazole) (biim-4), have widely introduced into the construction of coordination polymers (Zhang et al., 2010). Compared with the biim-4 ligand, 1,1'-(1,5-pentanediyl)bis(imidazole) (biim-5) ligand, bearing a longer methylene (-CH₂-)₅ skeleton, tends to exhibit more flexible conformations. Although compounds based on carboxylate ions and biim-5 have been reported widely, the compounds consist of sulfonate ions are relatively rare.

The asymmetric unit of the title compound contains a half of Cu^II ion, a half of naphthalene-1,5-disulfonate (1,5-nds) anion, one biim-5 ligand and one water molecule. As illustrated in Fig. 1, the Cu^II ion is six-coordinated by four N atoms from four biim-5 ligands and two water O atoms, furnishing a distorted octahedral geometry. The adjacent Cu^II atoms are linked by two biim-5 ligands, forming a chain along [1 1 1]. Intermolecular O—H···O hydrogen bonds link the chains and the 1,5-nds anions into a layer structure parallel to (0 -1 1).

Related literature top

For background to metal-organic coordination polymers with N-donor ligands, see: Kesanli et al. (2005); Wei et al. (2008); Zhang et al. (2010).

Experimental top

A mixture of Cu(CH₃COO)₂.H₂O (39.9 mg, 0.2 mmol), naphthalene-1,5-disulfonic acid (57.7 mg, 0.2 mmol) and biim-5 (41.2 mg, 0.2 mmol) was added to water (7 ml). After stirring for 15 min, the precipitate was dissolved by dropwise addition of an aqueous solution of NH₃ (14M, 3 ml). Blue crystals were obtained after allowing the solution to stand at room temperature for several days.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); 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 asymmetric unit of the title compound, with displacement ellipsoids drawn at the 30% probability level. H atoms and minor disordered sites have been omitted for clarity. [Symmetry codes: (i) 1-x, 2-y, 2-z; (ii) 1+x, 1+y, 1+z; (iii) -x, -y, -z; (iv) 1-x, 1-y, 1-z.]

catena-Poly[[[diaquacopper(II)]-bis[µ-1,5-bis(1H-imidazol-1- yl)pentane-κ²N³:N^3']] naphthalene-1,5-disulfonate] top

Crystal data top

[Cu(C₁₁H₁₆N₄)₂(H₂O)₂](C₁₀H₆O₆S₂)	Z = 1
M_r = 790.37	F(000) = 411
Triclinic, P1	D_x = 1.489 Mg m⁻³
Hall symbol: -P 1	Melting point: not measured K
a = 9.300 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.880 (5) Å	Cell parameters from 3995 reflections
c = 11.020 (5) Å	θ = 3.0–27.5°
α = 95.490 (5)°	µ = 0.80 mm⁻¹
β = 102.930 (5)°	T = 293 K
γ = 114.000 (5)°	Block, blue
V = 881.5 (8) Å³	0.41 × 0.33 × 0.21 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	3995 independent reflections
Radiation source: fine-focus sealed tube	2218 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.076
Detector resolution: 10 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −12→12
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −12→12
T_min = 0.970, T_max = 0.980	l = −13→14
8706 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)] = 0.074	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.167	w = 1/[σ²(F_o²) + (0.0505P)² + 1.4149P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3995 reflections	Δρ_max = 0.52 e Å⁻³
258 parameters	Δρ_min = −0.62 e Å⁻³
4 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.015 (3)

Crystal data top

[Cu(C₁₁H₁₆N₄)₂(H₂O)₂](C₁₀H₆O₆S₂)	γ = 114.000 (5)°
M_r = 790.37	V = 881.5 (8) Å³
Triclinic, P1	Z = 1
a = 9.300 (5) Å	Mo Kα radiation
b = 9.880 (5) Å	µ = 0.80 mm⁻¹
c = 11.020 (5) Å	T = 293 K
α = 95.490 (5)°	0.41 × 0.33 × 0.21 mm
β = 102.930 (5)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3995 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2218 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.980	R_int = 0.076
8706 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.074	4 restraints
wR(F²) = 0.167	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.52 e Å⁻³
3995 reflections	Δρ_min = −0.62 e Å⁻³
258 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	Occ. (<1)
Cu	0.5000	0.5000	0.5000	0.0421 (3)
C1	0.2899 (6)	0.3794 (7)	0.2360 (5)	0.0641 (17)
H1	0.1991	0.3656	0.2646	0.077*
C2	0.5349 (6)	0.4438 (6)	0.2291 (5)	0.0485 (13)
H2	0.6490	0.4841	0.2538	0.058*
C3	0.4368 (7)	0.3741 (8)	0.1108 (5)	0.0675 (18)
H3	0.4693	0.3573	0.0391	0.081*
C4	0.1318 (13)	0.1980 (15)	0.0189 (10)	0.053 (4)	0.554 (18)
H4A	0.1603	0.1171	−0.0048	0.063*	0.554 (18)
H4B	0.0399	0.1584	0.0543	0.063*	0.554 (18)
C5	0.0905 (13)	0.2632 (15)	−0.0932 (11)	0.058 (4)	0.554 (18)
H5A	0.1793	0.2974	−0.1322	0.069*	0.554 (18)
H5B	0.0664	0.3470	−0.0694	0.069*	0.554 (18)
C4'	0.1284 (16)	0.305 (2)	0.0057 (13)	0.056 (5)	0.446 (18)
H4'1	0.0332	0.2855	0.0362	0.068*	0.446 (18)
H4'2	0.1494	0.3908	−0.0355	0.068*	0.446 (18)
C5'	0.1049 (18)	0.1697 (19)	−0.0814 (16)	0.065 (5)	0.446 (18)
H5'1	0.1007	0.0890	−0.0365	0.078*	0.446 (18)
H5'2	0.1929	0.1935	−0.1212	0.078*	0.446 (18)
C6	−0.0690 (7)	0.1223 (9)	−0.1858 (6)	0.082 (2)
C7	−0.1086 (8)	0.2045 (7)	−0.2907 (6)	0.078 (2)
H7A	−0.1019	0.3000	−0.2517	0.094*
H7B	−0.0273	0.2267	−0.3370	0.094*
C8	−0.2770 (7)	0.1114 (6)	−0.3822 (5)	0.0565 (15)
H8A	−0.3585	0.0944	−0.3364	0.068*
H8B	−0.2967	0.1679	−0.4461	0.068*
C9	−0.2189 (6)	−0.0582 (6)	−0.5301 (5)	0.0482 (13)
H9	−0.1436	0.0150	−0.5605	0.058*
C11	−0.3937 (6)	−0.1703 (6)	−0.4280 (5)	0.0445 (12)
H11	−0.4599	−0.1853	−0.3738	0.053*
C10	−0.2722 (6)	−0.2088 (6)	−0.5604 (5)	0.0511 (13)
H10	−0.2386	−0.2577	−0.6164	0.061*
C12	0.4074 (6)	0.7806 (6)	1.1100 (5)	0.0474 (13)
H12	0.3943	0.7151	1.1664	0.057*
C13	0.2935 (6)	0.7343 (5)	0.9885 (5)	0.0432 (12)
H13	0.2051	0.6385	0.9657	0.052*
C14	0.3102 (5)	0.8269 (5)	0.9041 (4)	0.0349 (11)
C15	0.4423 (5)	0.9768 (5)	0.9385 (4)	0.0366 (11)
C16	0.4633 (6)	1.0791 (6)	0.8548 (4)	0.0422 (12)
H16	0.3876	1.0500	0.7748	0.051*
N2	0.2814 (6)	0.3331 (7)	0.1160 (4)	0.0786 (18)
N1	0.4413 (5)	0.4466 (4)	0.3081 (4)	0.0413 (10)
N3	−0.2978 (5)	−0.0341 (4)	−0.4455 (4)	0.0411 (10)
N4	−0.3829 (5)	−0.2802 (5)	−0.4970 (4)	0.0426 (10)
O1	0.0560 (4)	0.6024 (4)	0.7469 (4)	0.0597 (10)
O2	0.2596 (4)	0.7717 (4)	0.6604 (3)	0.0529 (10)
O3	0.0816 (4)	0.8556 (4)	0.7419 (3)	0.0544 (10)
S1	0.16398 (15)	0.75847 (15)	0.75061 (12)	0.0442 (4)
O1W	0.2295 (5)	0.5212 (5)	0.4900 (4)	0.0657 (12)
H1A	0.217 (7)	0.588 (6)	0.542 (5)	0.099*
H1B	0.144 (5)	0.486 (7)	0.420 (3)	0.099*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.0430 (5)	0.0387 (5)	0.0300 (5)	0.0065 (4)	0.0085 (4)	−0.0002 (3)
C1	0.035 (3)	0.098 (5)	0.038 (3)	0.015 (3)	0.009 (3)	−0.007 (3)
C2	0.036 (3)	0.062 (4)	0.037 (3)	0.016 (2)	0.007 (2)	0.000 (2)
C3	0.055 (3)	0.102 (5)	0.032 (3)	0.025 (3)	0.015 (3)	−0.006 (3)
C4	0.054 (6)	0.051 (8)	0.035 (7)	0.012 (5)	0.002 (5)	0.004 (5)
C5	0.057 (7)	0.049 (8)	0.047 (8)	0.017 (6)	−0.007 (6)	0.004 (5)
C4'	0.046 (7)	0.068 (12)	0.039 (9)	0.023 (7)	−0.006 (6)	−0.007 (7)
C5'	0.074 (10)	0.046 (9)	0.061 (11)	0.034 (8)	−0.011 (8)	−0.009 (7)
C6	0.054 (4)	0.104 (6)	0.046 (4)	0.018 (4)	−0.020 (3)	−0.015 (3)
C7	0.070 (4)	0.050 (4)	0.074 (4)	−0.004 (3)	0.019 (4)	−0.027 (3)
C8	0.072 (4)	0.045 (3)	0.053 (3)	0.027 (3)	0.016 (3)	0.010 (3)
C9	0.049 (3)	0.046 (3)	0.045 (3)	0.012 (2)	0.021 (3)	0.009 (2)
C11	0.041 (3)	0.044 (3)	0.040 (3)	0.012 (2)	0.009 (2)	0.005 (2)
C10	0.054 (3)	0.050 (3)	0.048 (3)	0.017 (3)	0.027 (3)	0.005 (2)
C12	0.057 (3)	0.042 (3)	0.044 (3)	0.018 (3)	0.022 (3)	0.013 (2)
C13	0.042 (3)	0.032 (3)	0.048 (3)	0.010 (2)	0.016 (2)	0.002 (2)
C14	0.027 (2)	0.038 (3)	0.035 (2)	0.012 (2)	0.008 (2)	−0.001 (2)
C15	0.033 (2)	0.038 (3)	0.037 (2)	0.016 (2)	0.0092 (19)	0.003 (2)
C16	0.045 (3)	0.043 (3)	0.036 (3)	0.019 (2)	0.008 (2)	0.007 (2)
N2	0.038 (2)	0.133 (5)	0.030 (2)	0.016 (3)	0.001 (2)	−0.015 (3)
N1	0.038 (2)	0.042 (2)	0.036 (2)	0.0116 (18)	0.0102 (19)	0.0011 (17)
N3	0.040 (2)	0.038 (2)	0.035 (2)	0.0113 (19)	0.0035 (18)	0.0040 (17)
N4	0.046 (2)	0.040 (2)	0.036 (2)	0.0132 (19)	0.0129 (19)	0.0054 (18)
O1	0.048 (2)	0.045 (2)	0.059 (2)	0.0027 (17)	0.0022 (18)	0.0011 (17)
O2	0.052 (2)	0.059 (2)	0.042 (2)	0.0200 (18)	0.0161 (17)	−0.0015 (16)
O3	0.044 (2)	0.062 (2)	0.057 (2)	0.0268 (19)	0.0090 (18)	0.0094 (18)
S1	0.0364 (7)	0.0429 (8)	0.0408 (7)	0.0108 (6)	0.0052 (6)	−0.0013 (5)
O1W	0.055 (2)	0.068 (3)	0.059 (3)	0.028 (2)	−0.001 (2)	−0.015 (2)

Geometric parameters (Å, º) top

Cu—N4ⁱ	1.988 (4)	C8—N3	1.453 (6)
Cu—N1	2.021 (4)	C8—H8A	0.9700
Cu—O1W	2.587 (5)	C8—H8B	0.9700
C1—N1	1.302 (6)	C9—C10	1.343 (7)
C1—N2	1.331 (7)	C9—N3	1.367 (6)
C1—H1	0.9300	C9—H9	0.9300
C2—C3	1.339 (7)	C11—N4	1.316 (6)
C2—N1	1.368 (6)	C11—N3	1.339 (6)
C2—H2	0.9300	C11—H11	0.9300
C3—N2	1.350 (7)	C10—N4	1.368 (6)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.49 (2)	C12—C16ⁱⁱ	1.360 (7)
C4—N2	1.553 (11)	C12—C13	1.406 (7)
C4—H4A	0.9700	C12—H12	0.9300
C4—H4B	0.9700	C13—C14	1.355 (6)
C5—C6	1.597 (12)	C13—H13	0.9300
C5—H5A	0.9700	C14—C15	1.432 (6)
C5—H5B	0.9700	C14—S1	1.781 (4)
C4'—C5'	1.48 (3)	C15—C16	1.417 (6)
C4'—N2	1.555 (14)	C15—C15ⁱⁱ	1.425 (9)
C4'—H4'1	0.9700	C16—C12ⁱⁱ	1.360 (7)
C4'—H4'2	0.9700	C16—H16	0.9300
C5'—C6	1.615 (15)	N4—Cuⁱⁱⁱ	1.988 (4)
C5'—H5'1	0.9700	O1—S1	1.448 (4)
C5'—H5'2	0.9700	O2—S1	1.457 (4)
C6—C7	1.537 (10)	O3—S1	1.449 (4)
C7—C8	1.504 (7)	O1W—H1A	0.89 (6)
C7—H7A	0.9700	O1W—H1B	0.89 (4)
C7—H7B	0.9700

N4ⁱ—Cu—N4^iv	180.000 (1)	N3—C8—C7	112.9 (5)
N4ⁱ—Cu—N1^v	91.92 (16)	N3—C8—H8A	109.0
N4^iv—Cu—N1^v	88.08 (16)	C7—C8—H8A	109.0
N4ⁱ—Cu—N1	88.08 (16)	N3—C8—H8B	109.0
N4^iv—Cu—N1	91.92 (16)	C7—C8—H8B	109.0
N1^v—Cu—N1	180.000 (1)	H8A—C8—H8B	107.8
O1W—Cu—N1	91.80 (17)	C10—C9—N3	106.1 (5)
O1W—Cu—N4^iv	91.02 (18)	C10—C9—H9	127.0
O1W—Cu—N4ⁱ	88.98 (18)	N3—C9—H9	127.0
O1W—Cu—O1W^v	180.00	N4—C11—N3	111.7 (5)
O1W—Cu—N1^v	88.20 (17)	N4—C11—H11	124.2
N1—C1—N2	111.5 (5)	N3—C11—H11	124.2
N1—C1—H1	124.3	C9—C10—N4	110.3 (5)
N2—C1—H1	124.3	C9—C10—H10	124.8
C3—C2—N1	109.5 (5)	N4—C10—H10	124.8
C3—C2—H2	125.3	C16ⁱⁱ—C12—C13	120.1 (5)
N1—C2—H2	125.3	C16ⁱⁱ—C12—H12	120.0
C2—C3—N2	106.4 (5)	C13—C12—H12	120.0
C2—C3—H3	126.8	C14—C13—C12	121.2 (4)
N2—C3—H3	126.8	C14—C13—H13	119.4
C5—C4—N2	104.6 (10)	C12—C13—H13	119.4
C5—C4—H4A	110.8	C13—C14—C15	120.5 (4)
N2—C4—H4A	110.8	C13—C14—S1	118.6 (4)
C5—C4—H4B	110.8	C15—C14—S1	120.9 (4)
N2—C4—H4B	110.8	C16—C15—C15ⁱⁱ	119.2 (5)
H4A—C4—H4B	108.9	C16—C15—C14	122.7 (4)
C4—C5—C6	102.3 (10)	C15ⁱⁱ—C15—C14	118.1 (5)
C4—C5—H5A	111.3	C12ⁱⁱ—C16—C15	120.9 (5)
C6—C5—H5A	111.3	C12ⁱⁱ—C16—H16	119.5
C4—C5—H5B	111.3	C15—C16—H16	119.5
C6—C5—H5B	111.3	C1—N2—C3	107.3 (4)
H5A—C5—H5B	109.2	C1—N2—C4	125.1 (6)
C5'—C4'—N2	102.7 (13)	C3—N2—C4	122.1 (6)
C5'—C4'—H4'1	111.2	C1—N2—C4'	120.2 (7)
N2—C4'—H4'1	111.2	C3—N2—C4'	127.6 (7)
C5'—C4'—H4'2	111.2	C1—N1—C2	105.4 (4)
N2—C4'—H4'2	111.2	C1—N1—Cu	122.5 (4)
H4'1—C4'—H4'2	109.1	C2—N1—Cu	131.1 (3)
C4'—C5'—C6	103.8 (12)	C11—N3—C9	106.9 (4)
C4'—C5'—H5'1	111.0	C11—N3—C8	126.2 (5)
C6—C5'—H5'1	111.0	C9—N3—C8	126.8 (5)
C4'—C5'—H5'2	111.0	C11—N4—C10	105.0 (4)
C6—C5'—H5'2	111.0	C11—N4—Cuⁱⁱⁱ	126.0 (4)
H5'1—C5'—H5'2	109.0	C10—N4—Cuⁱⁱⁱ	129.0 (4)
C7—C6—C5	97.8 (7)	O1—S1—O3	113.4 (2)
C7—C6—C5'	128.2 (9)	O1—S1—O2	112.4 (2)
C8—C7—C6	112.0 (5)	O3—S1—O2	113.0 (2)
C8—C7—H7A	109.2	O1—S1—C14	105.8 (2)
C6—C7—H7A	109.2	O3—S1—C14	105.9 (2)
C8—C7—H7B	109.2	O2—S1—C14	105.5 (2)
C6—C7—H7B	109.2	H1A—O1W—H1B	107 (5)
H7A—C7—H7B	107.9

N1—C2—C3—N2	−0.1 (7)	C5—C4—N2—C4'	28.3 (11)
N2—C4—C5—C6	−177.0 (7)	C5'—C4'—N2—C1	−142.0 (11)
N2—C4'—C5'—C6	171.5 (9)	C5'—C4'—N2—C3	66.1 (17)
C4—C5—C6—C7	175.4 (10)	C5'—C4'—N2—C4	−31.9 (11)
C4—C5—C6—C5'	−34.7 (13)	N2—C1—N1—C2	0.5 (7)
C4'—C5'—C6—C7	70.9 (16)	N2—C1—N1—Cu	−169.3 (4)
C4'—C5'—C6—C5	31.7 (12)	C3—C2—N1—C1	−0.2 (7)
C5—C6—C7—C8	−167.3 (7)	C3—C2—N1—Cu	168.3 (4)
C5'—C6—C7—C8	170.4 (9)	N4ⁱ—Cu—N1—C1	61.3 (5)
C6—C7—C8—N3	−59.1 (7)	N4^iv—Cu—N1—C1	−118.7 (5)
N3—C9—C10—N4	0.1 (6)	N4ⁱ—Cu—N1—C2	−105.5 (5)
C16ⁱⁱ—C12—C13—C14	0.5 (8)	N4^iv—Cu—N1—C2	74.5 (5)
C12—C13—C14—C15	−2.0 (7)	N4—C11—N3—C9	−0.7 (5)
C12—C13—C14—S1	178.4 (4)	N4—C11—N3—C8	−178.5 (4)
C13—C14—C15—C16	−178.6 (5)	C10—C9—N3—C11	0.3 (5)
S1—C14—C15—C16	0.9 (6)	C10—C9—N3—C8	178.1 (5)
C13—C14—C15—C15ⁱⁱ	2.1 (8)	C7—C8—N3—C11	111.1 (6)
S1—C14—C15—C15ⁱⁱ	−178.3 (4)	C7—C8—N3—C9	−66.2 (7)
C15ⁱⁱ—C15—C16—C12ⁱⁱ	0.8 (8)	N3—C11—N4—C10	0.7 (5)
C14—C15—C16—C12ⁱⁱ	−178.5 (5)	N3—C11—N4—Cuⁱⁱⁱ	179.0 (3)
N1—C1—N2—C3	−0.5 (8)	C9—C10—N4—C11	−0.5 (6)
N1—C1—N2—C4	153.4 (8)	C9—C10—N4—Cuⁱⁱⁱ	−178.7 (3)
N1—C1—N2—C4'	−157.5 (9)	C13—C14—S1—O1	−3.7 (5)
C2—C3—N2—C1	0.3 (8)	C15—C14—S1—O1	176.8 (4)
C2—C3—N2—C4	−154.5 (8)	C13—C14—S1—O3	117.0 (4)
C2—C3—N2—C4'	155.1 (10)	C15—C14—S1—O3	−62.6 (4)
C5—C4—N2—C1	125.9 (9)	C13—C14—S1—O2	−123.0 (4)
C5—C4—N2—C3	−83.8 (12)	C15—C14—S1—O2	57.4 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O2	0.89 (6)	1.97 (6)	2.836 (6)	163 (6)
O1W—H1B···O1^vi	0.89 (4)	2.11 (4)	3.001 (6)	178 (7)

Symmetry code: (vi) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu(C₁₁H₁₆N₄)₂(H₂O)₂](C₁₀H₆O₆S₂)
M_r	790.37
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.300 (5), 9.880 (5), 11.020 (5)
α, β, γ (°)	95.490 (5), 102.930 (5), 114.000 (5)
V (Å³)	881.5 (8)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.80
Crystal size (mm)	0.41 × 0.33 × 0.21

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.970, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	8706, 3995, 2218
R_int	0.076
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.074, 0.167, 1.03
No. of reflections	3995
No. of parameters	258
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.62

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O2	0.89 (6)	1.97 (6)	2.836 (6)	163 (6)
O1W—H1B···O1ⁱ	0.89 (4)	2.11 (4)	3.001 (6)	178 (7)

Symmetry code: (i) −x, −y+1, −z+1.

Acknowledgements

We thank the Science and Technology Key Projects for Technological Research on Preparation and Application of TiO₂, Henan Province (grant No. 0624270006), for support.

References

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
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Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
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Wei, G.-H., Yang, J., Ma, J.-F., Liu, Y.-Y. & Li, S.-L. (2008). Acta Cryst. C64, m267–m270. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhang, L.-P., Ma, J.-F., Pang, Y.-Y., Ma, J.-C. & Yang, J. (2010). CrystEngComm, 12, 4433–4442. Web of Science CSD CrossRef CAS Google Scholar

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