Bis(1,10-phenanthroline-κ2N,N′)[2-(4-sulfonato­anilino)acetato-κO]copper(II) dihydrate

Lu, Y.; Li, X.; Bing, Y.; Zha, M.-Q.; Li, Y.-X.

doi:10.1107/S160053681100746X

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Pages m402-m403

doi:10.1107/S160053681100746X

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Bis(1,10-phenanthroline-κ²N,N′)[2-(4-sulfonatoanilino)acetato-κO]copper(II) dihydrate

Yue Lu,^a Xing Li,^a ^* Yue Bing,^a Mei-Qin Zha ^a and Yin-Xin Li ^a

^aFaculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhejiang 315211, People's Republic of China
^*Correspondence e-mail: lixing@nbu.edu.cn

(Received 20 February 2011; accepted 28 February 2011; online 9 March 2011)

In the title compound, [Cu(C₈H₇NO₅S)(C₁₂H₈N₂)₂]·2H₂O, the Cu^II ion is coordinated by four N atoms from two 1,10-phenanthroline (phen) ligands and one O atom from a 2-(4-sulfonatoanilino)acetate (spia) ligand in a distorted square-pyramidal geometry. Intermolecular N—H⋯O and O—H⋯O hydrogen bonds, as well as π–π interactions between phen ligands and between phen and spia ligands [centroid–centroid distances = 3.663 (3), 3.768 (3) and 3.565 (3) Å], result in a three-dimensional supramolecular structure.

Related literature

For metal complexes with flexible or semi-rigid ligands, see: Chu et al. (2008 ); Xu et al. (2006a ,b ); Yong et al. (2004 , 2005 ).

Experimental

Crystal data

[Cu(C₈H₇NO₅S)(C₁₂H₈N₂)₂]·2H₂O
M_r = 689.19
Triclinic, $[P \overline 1]$
a = 9.3437 (19) Å
b = 13.274 (3) Å
c = 13.880 (3) Å
α = 64.61 (3)°
β = 88.77 (3)°
γ = 69.83 (3)°
V = 1443.6 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.89 mm⁻¹
T = 293 K
0.24 × 0.18 × 0.08 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.825, T_max = 0.931
14102 measured reflections
6590 independent reflections
5238 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.130
S = 1.11
6590 reflections
409 parameters
H-atom parameters constrained
Δρ_max = 0.83 e Å⁻³
Δρ_min = −1.99 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O2	1.993 (2)
Cu1—N1	1.999 (2)
Cu1—N2	2.049 (2)
Cu1—N3	2.005 (2)
Cu1—N4	2.212 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯O2ⁱ	0.86	2.35	3.173 (4)	160
O6—H6A⋯O4	0.76	2.11	2.850 (5)	166
O6—H6B⋯O1ⁱⁱ	0.86	2.15	2.963 (5)	156
O7—H7B⋯O3ⁱⁱⁱ	0.72	2.24	2.915 (4)	156
O7—H7A⋯O5^iv	0.76	2.11	2.785 (4)	148
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x+1, y-1, z; (iii) -x+1, -y+1, -z; (iv) x-1, y, z.

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: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681100746X/hy2409sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681100746X/hy2409Isup2.hkl

checkCIF report

Comment top

Flexible or semi-rigid ligands can adopt various conformations and coordination modes according to the geometric requirements of different metal ions, which have attracted more attention in the fields of supramolecular chemistry (Chu et al., 2008; Xu et al., 2006a,b; Yong et al., 2004, 2005). Here we use N-(4-sulfanilicphenyl)iminoacetic acid (H₂spia) and CuSO₄.5H₂O to prepare a copper compound with the spia ligand. The title compound is a mononuclear complex, with five-coordinated Cu^II ions. As shown in Fig. 1, the Cu^II ion is coordinated by one O atom from an spia ligand and four N atoms from two 1,10-phenanthroline ligands. There are two uncoordinated water molecules in the asymmetric unit.

Related literature top

For metal complexes with flexible or semi-rigid ligands, see: Chu et al. (2008); Xu et al. (2006a,b); Yong et al. (2004, 2005).

Experimental top

H₂spia was prepared following the method described by Yong et al. (2005). A solution of KOH (2.694 g, 48 mmol) in water (5 ml) was added dropwise to chloroacetic acid sodium salt (2.796 g, 24 mmol) in water (5 ml) with stirring. Sulfanilic acid (1.044 g, 6 mmol) was slowly added to the reaction mixture and KI (0.025 g) was added as catalyst. Then the mixture was refluxed at about 80°C for 30 h. The reaction solution was cooled to room temperature and acidified with HCl (6 mol/L) until the desired white acidic material precipitated (pH = 3), which was filtered, washed with water and dried in air.

The title compound was prepared by a solvent evaporation method. A mixture of CuSO₄.5H₂O (0.025 g, 0.1 mmol), H₂spia (0.029 g, 0.1 mmol), and 1,10-phenanthroline (0.040 g, 0.20 mmol) in 15 ml of water was heated for 30 min. One drop of KOH solution was added to adjust pH to 5, and then the mixture was filtered. Dark green single crystals suitable for X-ray analysis were obtained by slow evaporation of solvent at room temperature.

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: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Crystal packing of the title compound, showing π–π stacking interactions (dashed lines) between the phen ligands [centroid–centroid distances = 3.663 (3) and 3.768 (3) Å] and between the phen and spia ligands [centroid–centroid distance = 3.565 (3) Å].

Bis(1,10-phenanthroline-κ²N,N')[2-(4- sulfonatoanilino)acetato-κO]copper(II) dihydrate top

Crystal data top

[Cu(C₈H₇NO₅S)(C₁₂H₈N₂)₂]·2H₂O	Z = 2
M_r = 689.19	F(000) = 710
Triclinic, P1	D_x = 1.585 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3437 (19) Å	Cell parameters from 14102 reflections
b = 13.274 (3) Å	θ = 3.1–27.5°
c = 13.880 (3) Å	µ = 0.89 mm⁻¹
α = 64.61 (3)°	T = 293 K
β = 88.77 (3)°	Platelet, dark green
γ = 69.83 (3)°	0.24 × 0.18 × 0.08 mm
V = 1443.6 (8) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	6590 independent reflections
Radiation source: rotation anode	5238 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −11→12
T_min = 0.825, T_max = 0.931	k = −17→17
14102 measured reflections	l = −17→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0596P)² + 1.1815P] where P = (F_o² + 2F_c²)/3
6590 reflections	(Δ/σ)_max = 0.001
409 parameters	Δρ_max = 0.83 e Å⁻³
0 restraints	Δρ_min = −1.99 e Å⁻³

Crystal data top

[Cu(C₈H₇NO₅S)(C₁₂H₈N₂)₂]·2H₂O	γ = 69.83 (3)°
M_r = 689.19	V = 1443.6 (8) Å³
Triclinic, P1	Z = 2
a = 9.3437 (19) Å	Mo Kα radiation
b = 13.274 (3) Å	µ = 0.89 mm⁻¹
c = 13.880 (3) Å	T = 293 K
α = 64.61 (3)°	0.24 × 0.18 × 0.08 mm
β = 88.77 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	6590 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	5238 reflections with I > 2σ(I)
T_min = 0.825, T_max = 0.931	R_int = 0.042
14102 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 1.11	Δρ_max = 0.83 e Å⁻³
6590 reflections	Δρ_min = −1.99 e Å⁻³
409 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.50512 (4)	0.83070 (3)	0.27467 (2)	0.02821 (11)
S1	0.82946 (9)	0.30436 (7)	0.13978 (6)	0.03859 (18)
O1	0.2037 (3)	0.7912 (2)	0.2589 (2)	0.0650 (7)
O2	0.4453 (2)	0.68782 (18)	0.34176 (16)	0.0363 (5)
O3	0.7572 (3)	0.3723 (2)	0.02907 (19)	0.0601 (7)
O4	0.8555 (2)	0.17807 (19)	0.18310 (17)	0.03859 (18)
O5	0.9698 (3)	0.3209 (3)	0.1589 (3)	0.0700 (8)
O6	0.8946 (4)	−0.0692 (3)	0.2861 (3)	0.0805 (9)
H6B	0.9681	−0.1096	0.2628	0.097*
H6A	0.8849	−0.0049	0.2496	0.097*
O7	0.2154 (3)	0.3957 (3)	0.0958 (3)	0.0848 (10)
H7B	0.2070	0.4536	0.0521	0.102*
H7A	0.1317	0.4014	0.0956	0.102*
N1	0.6589 (3)	0.7539 (2)	0.20033 (18)	0.0299 (5)
N2	0.5263 (3)	0.9827 (2)	0.15768 (17)	0.0286 (5)
N3	0.3742 (3)	0.9116 (2)	0.35647 (17)	0.0280 (5)
N4	0.6770 (3)	0.7688 (2)	0.41483 (18)	0.0307 (5)
N5	0.4049 (3)	0.4718 (2)	0.4122 (2)	0.0372 (6)
H5A	0.4238	0.4250	0.4803	0.045*
C1	0.3090 (4)	0.6979 (3)	0.3178 (2)	0.0355 (6)
C2	0.2737 (3)	0.5822 (3)	0.3707 (3)	0.0379 (7)
H2A	0.2164	0.5843	0.4294	0.046*
H2B	0.2073	0.5823	0.3179	0.046*
C3	0.5021 (3)	0.4384 (2)	0.3459 (2)	0.0322 (6)
C4	0.6514 (3)	0.3536 (2)	0.3900 (2)	0.0339 (6)
H4	0.6851	0.3226	0.4631	0.041*
C5	0.7493 (3)	0.3154 (3)	0.3265 (2)	0.0342 (6)
H6	0.8485	0.2593	0.3573	0.041*
C6	0.7018 (3)	0.3596 (2)	0.2172 (2)	0.0321 (6)
C7	0.5545 (3)	0.4453 (3)	0.1722 (2)	0.0367 (6)
H7	0.5219	0.4765	0.0989	0.044*
C8	0.4560 (4)	0.4848 (3)	0.2347 (2)	0.0372 (6)
H5	0.3581	0.5428	0.2031	0.045*
C9	0.7205 (3)	0.6388 (3)	0.2225 (2)	0.0363 (6)
H9	0.6801	0.5856	0.2715	0.044*
C10	0.8439 (4)	0.5948 (3)	0.1746 (3)	0.0442 (7)
H10	0.8843	0.5136	0.1916	0.053*
C11	0.9054 (4)	0.6718 (3)	0.1025 (3)	0.0447 (7)
H11	0.9889	0.6429	0.0713	0.054*
C12	0.8420 (3)	0.7936 (3)	0.0762 (2)	0.0361 (6)
C13	0.8923 (4)	0.8835 (3)	−0.0014 (3)	0.0457 (8)
H13	0.9745	0.8606	−0.0362	0.055*
C14	0.8231 (4)	0.9996 (3)	−0.0246 (3)	0.0455 (8)
H14	0.8580	1.0555	−0.0757	0.055*
C15	0.6969 (3)	1.0401 (3)	0.0272 (2)	0.0356 (6)
C16	0.6218 (4)	1.1597 (3)	0.0083 (3)	0.0451 (8)
H16	0.6543	1.2192	−0.0397	0.054*
C17	0.5005 (4)	1.1882 (3)	0.0611 (3)	0.0453 (8)
H17	0.4483	1.2676	0.0479	0.054*
C18	0.4555 (4)	1.0975 (3)	0.1349 (2)	0.0375 (6)
H18	0.3722	1.1184	0.1696	0.045*
C19	0.6454 (3)	0.9541 (2)	0.1040 (2)	0.0287 (5)
C20	0.7174 (3)	0.8311 (2)	0.1275 (2)	0.0289 (5)
C21	0.2280 (3)	0.9850 (3)	0.3261 (2)	0.0347 (6)
H21	0.1803	1.0065	0.2583	0.042*
C22	0.1422 (4)	1.0315 (3)	0.3907 (3)	0.0403 (7)
H22	0.0398	1.0836	0.3660	0.048*
C23	0.2101 (3)	0.9997 (3)	0.4914 (2)	0.0371 (6)
H23	0.1542	1.0301	0.5356	0.044*
C24	0.3645 (3)	0.9212 (2)	0.5271 (2)	0.0295 (6)
C25	0.4415 (4)	0.8779 (3)	0.6331 (2)	0.0368 (6)
H25	0.3886	0.9037	0.6808	0.044*
C26	0.5888 (4)	0.8008 (3)	0.6650 (2)	0.0383 (7)
H26	0.6350	0.7717	0.7352	0.046*
C27	0.6758 (3)	0.7627 (2)	0.5921 (2)	0.0322 (6)
C28	0.8313 (4)	0.6867 (3)	0.6195 (3)	0.0432 (7)
H28	0.8838	0.6579	0.6878	0.052*
C29	0.9051 (4)	0.6555 (3)	0.5448 (3)	0.0481 (8)
H29	1.0088	0.6059	0.5617	0.058*
C30	0.8241 (3)	0.6985 (3)	0.4431 (3)	0.0399 (7)
H30	0.8762	0.6766	0.3930	0.048*
C31	0.6037 (3)	0.8018 (2)	0.4881 (2)	0.0269 (5)
C32	0.4447 (3)	0.8800 (2)	0.4561 (2)	0.0262 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.03390 (19)	0.02680 (19)	0.02459 (18)	−0.01173 (14)	0.00970 (12)	−0.01201 (13)
S1	0.0437 (4)	0.0380 (4)	0.0373 (4)	−0.0160 (3)	0.0141 (3)	−0.0195 (3)
O1	0.0678 (17)	0.0393 (14)	0.0659 (18)	−0.0111 (13)	−0.0156 (14)	−0.0099 (13)
O2	0.0408 (11)	0.0305 (10)	0.0413 (12)	−0.0188 (9)	0.0159 (9)	−0.0157 (9)
O3	0.0700 (17)	0.0599 (16)	0.0314 (12)	−0.0063 (14)	0.0115 (11)	−0.0178 (11)
O4	0.0437 (4)	0.0380 (4)	0.0373 (4)	−0.0160 (3)	0.0141 (3)	−0.0195 (3)
O5	0.0512 (15)	0.106 (2)	0.092 (2)	−0.0452 (17)	0.0369 (15)	−0.068 (2)
O6	0.073 (2)	0.0683 (19)	0.094 (2)	−0.0366 (17)	0.0195 (17)	−0.0232 (17)
O7	0.0587 (17)	0.072 (2)	0.078 (2)	−0.0235 (16)	−0.0072 (15)	0.0056 (16)
N1	0.0365 (12)	0.0315 (12)	0.0264 (11)	−0.0165 (10)	0.0094 (9)	−0.0144 (9)
N2	0.0342 (12)	0.0281 (11)	0.0240 (11)	−0.0109 (10)	0.0028 (9)	−0.0125 (9)
N3	0.0318 (11)	0.0278 (11)	0.0242 (11)	−0.0112 (10)	0.0050 (9)	−0.0115 (9)
N4	0.0305 (11)	0.0330 (12)	0.0303 (12)	−0.0130 (10)	0.0078 (9)	−0.0148 (10)
N5	0.0506 (15)	0.0279 (12)	0.0327 (13)	−0.0158 (11)	0.0167 (11)	−0.0128 (10)
C1	0.0452 (17)	0.0315 (15)	0.0304 (15)	−0.0134 (14)	0.0094 (12)	−0.0153 (12)
C2	0.0390 (16)	0.0378 (16)	0.0457 (17)	−0.0195 (14)	0.0189 (13)	−0.0229 (14)
C3	0.0439 (16)	0.0270 (13)	0.0319 (14)	−0.0212 (13)	0.0141 (12)	−0.0129 (11)
C4	0.0467 (16)	0.0285 (14)	0.0247 (13)	−0.0155 (13)	0.0052 (11)	−0.0092 (11)
C5	0.0384 (15)	0.0269 (13)	0.0328 (15)	−0.0101 (12)	0.0034 (11)	−0.0108 (11)
C6	0.0391 (15)	0.0299 (14)	0.0318 (14)	−0.0174 (13)	0.0113 (11)	−0.0146 (11)
C7	0.0421 (16)	0.0373 (16)	0.0266 (14)	−0.0131 (14)	0.0049 (11)	−0.0121 (12)
C8	0.0374 (15)	0.0352 (15)	0.0340 (15)	−0.0094 (13)	0.0032 (12)	−0.0140 (12)
C9	0.0401 (16)	0.0310 (15)	0.0410 (16)	−0.0146 (13)	0.0129 (12)	−0.0182 (13)
C10	0.0457 (18)	0.0367 (16)	0.053 (2)	−0.0115 (15)	0.0120 (15)	−0.0261 (15)
C11	0.0402 (17)	0.055 (2)	0.0489 (19)	−0.0174 (16)	0.0181 (14)	−0.0335 (16)
C12	0.0354 (15)	0.0477 (17)	0.0345 (15)	−0.0204 (14)	0.0121 (12)	−0.0230 (13)
C13	0.0421 (17)	0.061 (2)	0.0409 (18)	−0.0271 (17)	0.0189 (14)	−0.0233 (16)
C14	0.0472 (18)	0.056 (2)	0.0363 (17)	−0.0332 (17)	0.0127 (13)	−0.0129 (15)
C15	0.0400 (15)	0.0404 (16)	0.0290 (14)	−0.0238 (14)	0.0016 (11)	−0.0107 (12)
C16	0.0546 (19)	0.0388 (17)	0.0385 (17)	−0.0269 (16)	0.0012 (14)	−0.0068 (13)
C17	0.056 (2)	0.0293 (15)	0.0463 (19)	−0.0153 (15)	−0.0018 (15)	−0.0135 (14)
C18	0.0459 (17)	0.0331 (15)	0.0347 (15)	−0.0128 (13)	0.0038 (12)	−0.0177 (12)
C19	0.0315 (13)	0.0345 (14)	0.0227 (12)	−0.0160 (12)	0.0020 (10)	−0.0121 (11)
C20	0.0319 (13)	0.0354 (14)	0.0252 (13)	−0.0167 (12)	0.0067 (10)	−0.0156 (11)
C21	0.0315 (14)	0.0349 (15)	0.0342 (15)	−0.0074 (12)	0.0024 (11)	−0.0162 (12)
C22	0.0326 (15)	0.0379 (16)	0.0456 (18)	−0.0082 (13)	0.0066 (12)	−0.0185 (14)
C23	0.0405 (16)	0.0360 (15)	0.0405 (16)	−0.0148 (13)	0.0165 (12)	−0.0224 (13)
C24	0.0356 (14)	0.0277 (13)	0.0301 (14)	−0.0161 (12)	0.0112 (11)	−0.0142 (11)
C25	0.0509 (18)	0.0376 (16)	0.0277 (14)	−0.0181 (14)	0.0120 (12)	−0.0186 (12)
C26	0.0523 (18)	0.0357 (15)	0.0265 (14)	−0.0156 (14)	0.0022 (12)	−0.0140 (12)
C27	0.0388 (15)	0.0278 (13)	0.0290 (14)	−0.0135 (12)	0.0012 (11)	−0.0110 (11)
C28	0.0409 (17)	0.0435 (18)	0.0381 (17)	−0.0108 (15)	−0.0076 (13)	−0.0154 (14)
C29	0.0316 (15)	0.051 (2)	0.052 (2)	−0.0060 (15)	−0.0022 (13)	−0.0211 (16)
C30	0.0315 (14)	0.0434 (17)	0.0430 (17)	−0.0100 (13)	0.0089 (12)	−0.0210 (14)
C31	0.0324 (13)	0.0236 (12)	0.0261 (13)	−0.0130 (11)	0.0059 (10)	−0.0105 (10)
C32	0.0321 (13)	0.0235 (12)	0.0245 (12)	−0.0130 (11)	0.0074 (10)	−0.0101 (10)

Geometric parameters (Å, º) top

Cu1—O2	1.993 (2)	C9—H9	0.9300
Cu1—N1	1.999 (2)	C10—C11	1.371 (5)
Cu1—N2	2.049 (2)	C10—H10	0.9300
Cu1—N3	2.005 (2)	C11—C12	1.394 (5)
Cu1—N4	2.212 (3)	C11—H11	0.9300
S1—O3	1.438 (3)	C12—C20	1.406 (4)
S1—O4	1.446 (2)	C12—C13	1.438 (4)
S1—O5	1.450 (3)	C13—C14	1.338 (5)
S1—C6	1.769 (3)	C13—H13	0.9300
O1—C1	1.223 (4)	C14—C15	1.434 (4)
O2—C1	1.270 (4)	C14—H14	0.9300
O6—H6B	0.86	C15—C16	1.401 (5)
O6—H6A	0.76	C15—C19	1.409 (4)
O7—H7B	0.72	C16—C17	1.369 (5)
O7—H7A	0.76	C16—H16	0.9300
N1—C9	1.326 (4)	C17—C18	1.396 (4)
N1—C20	1.359 (3)	C17—H17	0.9300
N2—C18	1.326 (4)	C18—H18	0.9300
N2—C19	1.362 (3)	C19—C20	1.421 (4)
N3—C21	1.322 (4)	C21—C22	1.389 (4)
N3—C32	1.369 (3)	C21—H21	0.9300
N4—C30	1.319 (4)	C22—C23	1.372 (4)
N4—C31	1.356 (3)	C22—H22	0.9300
N5—C3	1.380 (4)	C23—C24	1.401 (4)
N5—C2	1.432 (4)	C23—H23	0.9300
N5—H5A	0.8600	C24—C32	1.407 (4)
C1—C2	1.543 (4)	C24—C25	1.431 (4)
C2—H2A	0.9700	C25—C26	1.343 (4)
C2—H2B	0.9700	C25—H25	0.9300
C3—C4	1.397 (4)	C26—C27	1.435 (4)
C3—C8	1.405 (4)	C26—H26	0.9300
C4—C5	1.377 (4)	C27—C28	1.399 (4)
C4—H4	0.9300	C27—C31	1.402 (4)
C5—C6	1.390 (4)	C28—C29	1.365 (5)
C5—H6	0.9300	C28—H28	0.9300
C6—C7	1.388 (4)	C29—C30	1.397 (5)
C7—C8	1.378 (4)	C29—H29	0.9300
C7—H7	0.9300	C30—H30	0.9300
C8—H5	0.9300	C31—C32	1.432 (4)
C9—C10	1.395 (4)

O2—Cu1—N1	91.43 (9)	C10—C11—C12	119.6 (3)
O2—Cu1—N3	93.36 (9)	C10—C11—H11	120.2
N1—Cu1—N3	172.29 (9)	C12—C11—H11	120.2
O2—Cu1—N2	159.24 (9)	C11—C12—C20	117.3 (3)
N1—Cu1—N2	81.66 (9)	C11—C12—C13	124.6 (3)
N3—Cu1—N2	95.79 (9)	C20—C12—C13	118.0 (3)
O2—Cu1—N4	94.19 (9)	C14—C13—C12	121.3 (3)
N1—Cu1—N4	93.85 (9)	C14—C13—H13	119.3
N3—Cu1—N4	79.78 (9)	C12—C13—H13	119.3
N2—Cu1—N4	105.74 (9)	C13—C14—C15	121.8 (3)
O3—S1—O4	113.06 (15)	C13—C14—H14	119.1
O3—S1—O5	113.39 (18)	C15—C14—H14	119.1
O4—S1—O5	110.79 (17)	C16—C15—C19	117.2 (3)
O3—S1—C6	107.61 (15)	C16—C15—C14	124.6 (3)
O4—S1—C6	106.23 (13)	C19—C15—C14	118.2 (3)
O5—S1—C6	105.13 (15)	C17—C16—C15	119.5 (3)
C1—O2—Cu1	119.80 (19)	C17—C16—H16	120.3
H6B—O6—H6A	102.9	C15—C16—H16	120.3
H7B—O7—H7A	100.4	C16—C17—C18	119.6 (3)
C9—N1—C20	118.4 (2)	C16—C17—H17	120.2
C9—N1—Cu1	128.42 (19)	C18—C17—H17	120.2
C20—N1—Cu1	112.63 (18)	N2—C18—C17	122.9 (3)
C18—N2—C19	117.8 (2)	N2—C18—H18	118.5
C18—N2—Cu1	131.1 (2)	C17—C18—H18	118.5
C19—N2—Cu1	110.75 (18)	N2—C19—C15	123.0 (3)
C21—N3—C32	118.6 (2)	N2—C19—C20	117.0 (2)
C21—N3—Cu1	126.62 (19)	C15—C19—C20	120.0 (3)
C32—N3—Cu1	114.69 (18)	N1—C20—C12	122.8 (3)
C30—N4—C31	117.8 (2)	N1—C20—C19	116.6 (2)
C30—N4—Cu1	132.9 (2)	C12—C20—C19	120.6 (2)
C31—N4—Cu1	108.84 (17)	N3—C21—C22	123.1 (3)
C3—N5—C2	121.9 (2)	N3—C21—H21	118.4
C3—N5—H5A	119.1	C22—C21—H21	118.4
C2—N5—H5A	119.1	C23—C22—C21	119.2 (3)
O1—C1—O2	125.7 (3)	C23—C22—H22	120.4
O1—C1—C2	117.8 (3)	C21—C22—H22	120.4
O2—C1—C2	116.4 (3)	C22—C23—C24	119.5 (3)
N5—C2—C1	115.8 (2)	C22—C23—H23	120.3
N5—C2—H2A	108.3	C24—C23—H23	120.3
C1—C2—H2A	108.3	C23—C24—C32	118.0 (3)
N5—C2—H2B	108.3	C23—C24—C25	123.1 (3)
C1—C2—H2B	108.3	C32—C24—C25	118.9 (3)
H2A—C2—H2B	107.4	C26—C25—C24	121.3 (3)
N5—C3—C4	119.5 (3)	C26—C25—H25	119.3
N5—C3—C8	122.5 (3)	C24—C25—H25	119.3
C4—C3—C8	118.0 (3)	C25—C26—C27	120.8 (3)
C5—C4—C3	120.9 (3)	C25—C26—H26	119.6
C5—C4—H4	119.6	C27—C26—H26	119.6
C3—C4—H4	119.6	C28—C27—C31	117.3 (3)
C4—C5—C6	120.9 (3)	C28—C27—C26	123.2 (3)
C4—C5—H6	119.6	C31—C27—C26	119.5 (3)
C6—C5—H6	119.6	C29—C28—C27	119.2 (3)
C7—C6—C5	118.7 (3)	C29—C28—H28	120.4
C7—C6—S1	122.0 (2)	C27—C28—H28	120.4
C5—C6—S1	119.3 (2)	C28—C29—C30	119.7 (3)
C8—C7—C6	120.9 (3)	C28—C29—H29	120.2
C8—C7—H7	119.6	C30—C29—H29	120.2
C6—C7—H7	119.6	N4—C30—C29	122.8 (3)
C7—C8—C3	120.7 (3)	N4—C30—H30	118.6
C7—C8—H5	119.7	C29—C30—H30	118.6
C3—C8—H5	119.7	N4—C31—C27	123.2 (3)
N1—C9—C10	122.2 (3)	N4—C31—C32	117.4 (2)
N1—C9—H9	118.9	C27—C31—C32	119.4 (2)
C10—C9—H9	118.9	N3—C32—C24	121.6 (2)
C11—C10—C9	119.7 (3)	N3—C32—C31	118.4 (2)
C11—C10—H10	120.1	C24—C32—C31	120.0 (2)
C9—C10—H10	120.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O2ⁱ	0.86	2.35	3.173 (4)	160
O6—H6A···O4	0.76	2.11	2.850 (5)	166
O6—H6B···O1ⁱⁱ	0.86	2.15	2.963 (5)	156
O7—H7B···O3ⁱⁱⁱ	0.72	2.24	2.915 (4)	156
O7—H7A···O5^iv	0.76	2.11	2.785 (4)	148

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

Experimental details

Crystal data
Chemical formula	[Cu(C₈H₇NO₅S)(C₁₂H₈N₂)₂]·2H₂O
M_r	689.19
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.3437 (19), 13.274 (3), 13.880 (3)
α, β, γ (°)	64.61 (3), 88.77 (3), 69.83 (3)
V (Å³)	1443.6 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.89
Crystal size (mm)	0.24 × 0.18 × 0.08

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.825, 0.931
No. of measured, independent and observed [I > 2σ(I)] reflections	14102, 6590, 5238
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.130, 1.11
No. of reflections	6590
No. of parameters	409
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.83, −1.99

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—O2	1.993 (2)	Cu1—N3	2.005 (2)
Cu1—N1	1.999 (2)	Cu1—N4	2.212 (3)
Cu1—N2	2.049 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O2ⁱ	0.86	2.35	3.173 (4)	160
O6—H6A···O4	0.76	2.11	2.850 (5)	166
O6—H6B···O1ⁱⁱ	0.86	2.15	2.963 (5)	156
O7—H7B···O3ⁱⁱⁱ	0.72	2.24	2.915 (4)	156
O7—H7A···O5^iv	0.76	2.11	2.785 (4)	148

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

Acknowledgements

This work was supported by the Ningbo Natural Science Foundation of China (2010A610060), the 'Qianjiang Talent' Projects of Zhejiang Province (2009R10032), the Ningbo University Foundation (XK1066) and the K. C. Wong Magna Fund in Ningbo University.

References

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