catena-Poly[[[[2-(2-pyridyl-κN)-1H-benzimidazole-κN3]copper(II)]-μ-l-methio­ninato-κ3N,O:O′] perchlorate]

Lu, Y.-M.; Le, X.-Y.

doi:10.1107/S1600536811014000

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 5| May 2011| Pages m642-m643

doi:10.1107/S1600536811014000

Open

access

catena-Poly[[[[2-(2-pyridyl-κN)-1H-benzimidazole-κN³]copper(II)]-μ-L-methioninato-κ³N,O:O′] perchlorate]

Yan-Mei Lu ^a and Xue-Yi Le ^b ^*

^aDepartment of Applied Chemistry, South China Agricultural University, 510642 Guangzhou, Guangdong, People's Republic of China, and ^bInstitue of Biomaterial, South China Agricultural University, 510642 Guangzhou, Guangdong, People's Republic of China
^*Correspondence e-mail: lexyfu@163.com

(Received 18 March 2011; accepted 13 April 2011; online 29 April 2011)

The structure of the title compound, {[Cu(C₅H₁₀NO₂S)(C₁₂H₉N₃)]ClO₄}_n, has orthorhombic symmetry. The chain structure is constructed from square-pyramidally coordinated Cu^II atoms linked through L-methionate ligands. The chains propagate along the a-axis direction and are linked to perchlorate anions via N—H⋯O hydrogen bonds.

Related literature

For the biological activity of benzimidazole derivatives and their metal complexes, see: Devereux et al. (2004 , 2007 ); El-Sherif & Jeragh (2007 ). For metal complexes of L-α-amino acids, see: Lin et al. (2006 ), Yamauchi et al. (1992 ); Zhou et al. (2005 ).

Experimental

Crystal data

[Cu(C₅H₁₀NO₂S)(C₁₂H₉N₃)]ClO₄
M_r = 506.41
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.9718 (4) Å
b = 11.8902 (6) Å
c = 24.7024 (13) Å
V = 2047.73 (19) Å³
Z = 4
Mo Kα radiation
μ = 1.34 mm⁻¹
T = 293 K
0.45 × 0.35 × 0.13 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.583, T_max = 0.845
12781 measured reflections
4464 independent reflections
3557 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.111
S = 1.05
4464 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.28 e Å⁻³
Absolute structure: Flack (1983 ), 1874 Friedel pairs
Flack parameter: −0.001 (17)

Table 1
Selected bond lengths (Å)

Cu1—O2ⁱ	2.272 (3)
Cu1—O1	1.929 (3)
Cu1—N1	1.996 (2)
Cu1—N3	2.023 (3)
Cu1—N4	1.985 (3)
O2—Cu1ⁱⁱ	2.272 (3)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+2]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+2]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2a⋯O3ⁱⁱⁱ	0.86	2.06	2.904 (6)	168
N4—H4a⋯O5^iv	0.90	2.53	3.370 (7)	155
N4—H4b⋯O4	0.90	2.31	3.064 (7)	141
Symmetry codes: (iii) $[x-{\script{1\over 2}}, -y+{\script{5\over 2}}, -z+2]$ ; (iv) x-1, y, z.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT-Plus (Bruker, 2003 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811014000/ff2004sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811014000/ff2004Isup2.hkl

checkCIF report

Comment top

In recent years, structure investigations of benzimidazole derivatives and their metal complexes have attracted an interest due to their antioxidant, antimycobacterium, antiparasitic activity and cytotoxicity (Devereux et al., 2004, 2007; El-Sherif & Jeragh, 2007). Furthermore, L-α-amino acids are important biological ligands, taking flexible coordination modes with metal ions (Lin et al.., 2006, Yamauchi et al., 1992, Zhou et al., 2005). With L-α-amino acids being involved, the biological activities of complexes can be improved. We report herein the synthesis and crystal structure of the title complex.

The crystal structure of the title complex consists of [Cu(C₁₂H₉N₃)(C₅H₁₀NO₂S)]_n polymeric chains (Fig. 2). The Cu(II) atom is in a slightly distorted square–pyramidal geometry (Fig. 1). The equatorial plane is occupied by two nitrogen atoms of 2-(2-pyridyl)benzimidazole ligand and one nitrogen atom and one oxygen atom of L-methionate ligand, while the apical position is occupied by another carboxylate oxygen atom from a symmetry-related neighboring L-methioninate ligand. The chains are connected by N—H···O hydrogen bonds to the perchlorate anions.

Related literature top

For the biological activity of benzimidazole derivatives and their metal complexes, see: Devereux et al. (2004, 2007); El-Sherif & Jeragh (2007). For metal complexes of L-α-amino acids, see Lin et al. (2006), Yamauchi et al. (1992); Zhou et al. (2005).

Experimental top

To a stirred ethanol solution (20 ml) containing 2-(2-pyridyl) benzimidazole (HPB) (0.098 g, 0.5 mmol) was added an aqueous solution(1 ml) of Cu(ClO₄)₂ 6H₂O (0.188 g,0.5 mmol). An aqueous solution of L-Met(0.075 g, 0.5 mmol) and NaOH (0.020 g, 0.5 mmol) was then added to the mixture. After stirring continuously at 333 K for 1 h, the resulting green solution was filtered. The single crystals were obtained from the filtrate after two weeks (yield 67% based on Cu).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, drawn with 30% probability displacement ellipsoids. Symmetry codes: (i) -0.5+x, 1.5-y, 2-z.
	Fig. 2. The crystal packing viewed along the b axis. Hydrogen bonds are drawn as dashed lines. Hydrogen atoms not involved in hydrogen bonding are omitted for clarity.

catena-Poly[[[[2-(2-pyridyl-κN)-1H-benzimidazole- κN³]copper(II)]-µ-L-methioninato-κ³N,O:O'] perchlorate] top

Crystal data top

[Cu(C₅H₁₀NO₂S)(C₁₂H₉N₃)]ClO₄	F(000) = 1036
M_r = 506.41	D_x = 1.643 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5099 reflections
a = 6.9718 (4) Å	θ = 2.4–26.5°
b = 11.8902 (6) Å	µ = 1.34 mm⁻¹
c = 24.7024 (13) Å	T = 293 K
V = 2047.73 (19) Å³	Block, blue
Z = 4	0.45 × 0.35 × 0.13 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	4464 independent reflections
Radiation source: fine-focus sealed tube	3557 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω scans	θ_max = 27.1°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→8
T_min = 0.583, T_max = 0.845	k = −15→14
12781 measured reflections	l = −30→31

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)] = 0.042	H-atom parameters constrained
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0626P)²] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
4464 reflections	Δρ_max = 0.45 e Å⁻³
272 parameters	Δρ_min = −0.28 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1874 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.001 (17)

Crystal data top

[Cu(C₅H₁₀NO₂S)(C₁₂H₉N₃)]ClO₄	V = 2047.73 (19) Å³
M_r = 506.41	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.9718 (4) Å	µ = 1.34 mm⁻¹
b = 11.8902 (6) Å	T = 293 K
c = 24.7024 (13) Å	0.45 × 0.35 × 0.13 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	4464 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3557 reflections with I > 2σ(I)
T_min = 0.583, T_max = 0.845	R_int = 0.035
12781 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.111	Δρ_max = 0.45 e Å⁻³
S = 1.05	Δρ_min = −0.28 e Å⁻³
4464 reflections	Absolute structure: Flack (1983), 1874 Friedel pairs
272 parameters	Absolute structure parameter: −0.001 (17)
0 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	0.03097 (7)	0.92990 (4)	1.007152 (16)	0.03414 (14)
S1	0.1487 (2)	0.72711 (14)	0.75829 (5)	0.0695 (4)
C1	0.0206 (6)	1.1839 (3)	0.96479 (14)	0.0319 (8)
C2	0.0198 (7)	1.1840 (3)	0.90774 (15)	0.0422 (10)
H2	0.0161	1.1176	0.8879	0.051*
C3	0.0246 (7)	1.2888 (4)	0.88271 (16)	0.0517 (11)
H3	0.0244	1.2923	0.8451	0.062*
C4	0.0297 (7)	1.3874 (4)	0.91190 (17)	0.0496 (11)
H4	0.0311	1.4552	0.8932	0.060*
C5	0.0329 (7)	1.3900 (3)	0.96696 (16)	0.0444 (10)
H5	0.0390	1.4573	0.9861	0.053*
C6	0.0265 (5)	1.2874 (3)	0.99268 (14)	0.0348 (8)
C7	0.0303 (6)	1.1451 (3)	1.04985 (14)	0.0324 (8)
C8	0.0452 (6)	1.0774 (3)	1.09845 (13)	0.0334 (8)
C9	0.0441 (7)	1.1167 (4)	1.15117 (15)	0.0463 (10)
H9	0.0334	1.1933	1.1584	0.056*
C10	0.0590 (8)	1.0405 (4)	1.19261 (16)	0.0557 (13)
H10	0.0574	1.0646	1.2284	0.067*
C11	0.0767 (6)	0.9258 (4)	1.18046 (17)	0.0496 (11)
H11	0.0878	0.8729	1.2080	0.059*
C12	0.0774 (6)	0.8931 (4)	1.12754 (16)	0.0416 (10)
H12	0.0885	0.8169	1.1196	0.050*
C14	0.1548 (5)	0.7221 (3)	0.97297 (14)	0.0312 (8)
C15	0.0420 (6)	0.7667 (3)	0.92357 (13)	0.0318 (8)
H15	−0.0844	0.7307	0.9240	0.038*
C16	0.1402 (6)	0.7342 (3)	0.87040 (15)	0.0374 (9)
H16A	0.2677	0.7667	0.8697	0.045*
H16B	0.1543	0.6530	0.8692	0.045*
C17	0.0311 (7)	0.7726 (4)	0.81999 (15)	0.0542 (11)
H17A	0.0217	0.8540	0.8201	0.065*
H17B	−0.0980	0.7423	0.8210	0.065*
C18	0.0818 (9)	0.5877 (5)	0.7533 (2)	0.088 (2)
H18A	0.0984	0.5516	0.7878	0.132*
H18B	0.1602	0.5508	0.7268	0.132*
H18C	−0.0504	0.5831	0.7427	0.132*
N1	0.0205 (4)	1.0973 (2)	1.00175 (11)	0.0331 (7)
N2	0.0307 (5)	1.2578 (2)	1.04683 (12)	0.0381 (8)
H2A	0.0330	1.3035	1.0738	0.046*
N3	0.0626 (5)	0.9665 (3)	1.08662 (12)	0.0359 (8)
N4	0.0118 (5)	0.8879 (2)	0.92955 (11)	0.0348 (7)
H4A	−0.1048	0.9066	0.9167	0.042*
H4B	0.1005	0.9257	0.9103	0.042*
O1	0.1548 (4)	0.7856 (2)	1.01441 (10)	0.0413 (6)
O2	0.2326 (4)	0.6305 (2)	0.96999 (10)	0.0381 (6)
Cl1	0.50122 (15)	0.99416 (8)	0.86259 (4)	0.0468 (3)
O3	0.5967 (8)	1.0975 (4)	0.8603 (2)	0.122 (2)
O4	0.4179 (8)	0.9815 (5)	0.91477 (17)	0.1137 (18)
O5	0.6217 (8)	0.9044 (4)	0.8494 (3)	0.129 (2)
O6	0.3501 (8)	0.9903 (5)	0.8275 (2)	0.131 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0428 (3)	0.0279 (2)	0.0317 (2)	0.0028 (2)	−0.00370 (19)	−0.00388 (17)
S1	0.0851 (10)	0.0913 (10)	0.0322 (6)	−0.0032 (8)	0.0089 (6)	0.0012 (6)
C1	0.027 (2)	0.0314 (18)	0.0379 (19)	−0.0007 (17)	−0.0005 (16)	0.0032 (14)
C2	0.054 (3)	0.039 (2)	0.0336 (18)	0.000 (2)	−0.003 (2)	−0.0036 (15)
C3	0.059 (3)	0.059 (3)	0.038 (2)	0.001 (3)	0.000 (2)	0.0104 (19)
C4	0.058 (3)	0.037 (2)	0.054 (2)	−0.005 (2)	−0.005 (2)	0.0116 (18)
C5	0.051 (3)	0.034 (2)	0.049 (2)	0.000 (2)	−0.003 (2)	0.0010 (17)
C6	0.0326 (19)	0.0346 (18)	0.0371 (18)	−0.0026 (16)	−0.0004 (18)	−0.0024 (15)
C7	0.036 (2)	0.0275 (18)	0.0336 (17)	−0.0022 (17)	−0.0004 (17)	−0.0055 (14)
C8	0.038 (2)	0.0324 (19)	0.0299 (17)	−0.0007 (19)	−0.0018 (15)	0.0003 (15)
C9	0.063 (3)	0.043 (2)	0.033 (2)	−0.006 (2)	−0.001 (2)	−0.0032 (16)
C10	0.070 (3)	0.071 (3)	0.0260 (19)	−0.005 (3)	−0.004 (2)	−0.0060 (19)
C11	0.052 (3)	0.061 (3)	0.036 (2)	−0.005 (2)	−0.0026 (18)	0.012 (2)
C12	0.046 (3)	0.037 (2)	0.042 (2)	−0.0045 (18)	−0.0055 (18)	0.0031 (17)
C14	0.029 (2)	0.033 (2)	0.0317 (18)	−0.0037 (17)	−0.0008 (15)	−0.0006 (16)
C15	0.030 (2)	0.0342 (19)	0.0311 (17)	0.0000 (17)	0.0007 (16)	−0.0035 (14)
C16	0.044 (2)	0.035 (2)	0.0331 (19)	0.0027 (18)	0.0022 (18)	−0.0028 (16)
C17	0.058 (3)	0.069 (3)	0.035 (2)	0.009 (3)	0.003 (2)	−0.003 (2)
C18	0.085 (4)	0.101 (5)	0.079 (4)	−0.011 (4)	0.012 (3)	−0.048 (4)
N1	0.0377 (17)	0.0278 (14)	0.0338 (15)	−0.0007 (12)	−0.0022 (15)	−0.0062 (11)
N2	0.047 (2)	0.0325 (17)	0.0349 (15)	−0.0035 (16)	0.0007 (16)	−0.0084 (12)
N3	0.0364 (19)	0.0374 (18)	0.0337 (16)	−0.0019 (14)	−0.0039 (14)	0.0003 (13)
N4	0.041 (2)	0.0294 (15)	0.0340 (15)	0.0083 (15)	−0.0022 (15)	−0.0002 (12)
O1	0.0508 (17)	0.0385 (15)	0.0347 (14)	0.0131 (13)	−0.0099 (13)	−0.0016 (12)
O2	0.0432 (16)	0.0257 (14)	0.0453 (16)	0.0071 (12)	−0.0008 (12)	−0.0022 (12)
Cl1	0.0479 (6)	0.0444 (5)	0.0481 (5)	−0.0055 (5)	0.0044 (5)	−0.0133 (4)
O3	0.154 (5)	0.079 (3)	0.132 (4)	−0.063 (3)	0.073 (3)	−0.055 (3)
O4	0.129 (4)	0.148 (4)	0.064 (3)	−0.044 (4)	0.026 (3)	−0.013 (3)
O5	0.120 (4)	0.074 (3)	0.192 (6)	0.029 (3)	0.052 (4)	−0.022 (3)
O6	0.104 (4)	0.176 (5)	0.114 (4)	0.002 (4)	−0.042 (3)	−0.016 (4)

Geometric parameters (Å, º) top

Cu1—O2ⁱ	2.272 (3)	C10—H10	0.9300
Cu1—O1	1.929 (3)	C11—C12	1.364 (6)
Cu1—N1	1.996 (2)	C11—H11	0.9300
Cu1—N3	2.023 (3)	C12—N3	1.339 (5)
Cu1—N4	1.985 (3)	C12—H12	0.9300
S1—C18	1.727 (6)	C14—O2	1.220 (4)
S1—C17	1.813 (4)	C14—O1	1.272 (4)
C1—N1	1.377 (4)	C14—C15	1.546 (5)
C1—C2	1.409 (5)	C15—N4	1.464 (4)
C1—C6	1.410 (5)	C15—C16	1.531 (5)
C2—C3	1.391 (6)	C15—H15	0.9800
C2—H2	0.9300	C16—C17	1.529 (6)
C3—C4	1.377 (6)	C16—H16A	0.9700
C3—H3	0.9300	C16—H16B	0.9700
C4—C5	1.360 (6)	C17—H17A	0.9700
C4—H4	0.9300	C17—H17B	0.9700
C5—C6	1.377 (5)	C18—H18A	0.9600
C5—H5	0.9300	C18—H18B	0.9600
C6—N2	1.383 (4)	C18—H18C	0.9600
C7—N1	1.319 (4)	N2—H2A	0.8600
C7—N2	1.341 (4)	N4—H4A	0.9000
C7—C8	1.449 (5)	N4—H4B	0.9000
C8—N3	1.356 (5)	O2—Cu1ⁱⁱ	2.272 (3)
C8—C9	1.384 (5)	Cl1—O6	1.365 (5)
C9—C10	1.372 (6)	Cl1—O5	1.397 (4)
C9—H9	0.9300	Cl1—O3	1.399 (4)
C10—C11	1.401 (6)	Cl1—O4	1.422 (4)

O1—Cu1—N4	84.05 (11)	O1—C14—C15	115.6 (3)
O1—Cu1—N1	155.45 (13)	N4—C15—C16	113.6 (3)
N4—Cu1—N1	100.58 (11)	N4—C15—C14	109.4 (3)
O1—Cu1—N3	92.99 (12)	C16—C15—C14	111.3 (3)
N4—Cu1—N3	176.82 (14)	N4—C15—H15	107.4
N1—Cu1—N3	81.63 (12)	C16—C15—H15	107.4
O1—Cu1—O2ⁱ	96.06 (11)	C14—C15—H15	107.4
N4—Cu1—O2ⁱ	95.67 (12)	C17—C16—C15	113.6 (4)
N1—Cu1—O2ⁱ	107.33 (11)	C17—C16—H16A	108.8
N3—Cu1—O2ⁱ	85.79 (11)	C15—C16—H16A	108.8
C18—S1—C17	102.9 (3)	C17—C16—H16B	108.8
N1—C1—C2	131.6 (3)	C15—C16—H16B	108.8
N1—C1—C6	109.2 (3)	H16A—C16—H16B	107.7
C2—C1—C6	119.2 (3)	C16—C17—S1	111.8 (3)
C3—C2—C1	116.4 (4)	C16—C17—H17A	109.3
C3—C2—H2	121.8	S1—C17—H17A	109.3
C1—C2—H2	121.8	C16—C17—H17B	109.3
C4—C3—C2	122.0 (4)	S1—C17—H17B	109.3
C4—C3—H3	119.0	H17A—C17—H17B	107.9
C2—C3—H3	119.0	S1—C18—H18A	109.5
C5—C4—C3	122.9 (4)	S1—C18—H18B	109.5
C5—C4—H4	118.5	H18A—C18—H18B	109.5
C3—C4—H4	118.5	S1—C18—H18C	109.5
C4—C5—C6	116.1 (4)	H18A—C18—H18C	109.5
C4—C5—H5	121.9	H18B—C18—H18C	109.5
C6—C5—H5	121.9	C7—N1—C1	105.9 (3)
C5—C6—N2	132.1 (3)	C7—N1—Cu1	111.6 (2)
C5—C6—C1	123.3 (3)	C1—N1—Cu1	142.2 (2)
N2—C6—C1	104.6 (3)	C7—N2—C6	107.9 (3)
N1—C7—N2	112.4 (3)	C7—N2—H2A	126.0
N1—C7—C8	120.7 (3)	C6—N2—H2A	126.0
N2—C7—C8	126.9 (3)	C12—N3—C8	118.5 (3)
N3—C8—C9	122.1 (3)	C12—N3—Cu1	126.9 (3)
N3—C8—C7	111.6 (3)	C8—N3—Cu1	114.1 (2)
C9—C8—C7	126.3 (3)	C15—N4—Cu1	109.6 (2)
C10—C9—C8	118.6 (4)	C15—N4—H4A	109.8
C10—C9—H9	120.7	Cu1—N4—H4A	109.8
C8—C9—H9	120.7	C15—N4—H4B	109.8
C9—C10—C11	119.3 (4)	Cu1—N4—H4B	109.8
C9—C10—H10	120.3	H4A—N4—H4B	108.2
C11—C10—H10	120.3	C14—O1—Cu1	116.9 (2)
C12—C11—C10	118.9 (4)	C14—O2—Cu1ⁱⁱ	132.4 (2)
C12—C11—H11	120.6	O6—Cl1—O5	106.9 (4)
C10—C11—H11	120.6	O6—Cl1—O3	111.8 (4)
N3—C12—C11	122.5 (4)	O5—Cl1—O3	112.1 (3)
N3—C12—H12	118.8	O6—Cl1—O4	104.9 (3)
C11—C12—H12	118.8	O5—Cl1—O4	112.1 (4)
O2—C14—O1	125.4 (3)	O3—Cl1—O4	108.9 (3)
O2—C14—C15	119.0 (3)

N1—C1—C2—C3	−178.6 (4)	N4—Cu1—N1—C7	179.7 (3)
C6—C1—C2—C3	−0.1 (6)	N3—Cu1—N1—C7	−2.6 (3)
C1—C2—C3—C4	−0.1 (7)	O2ⁱ—Cu1—N1—C7	80.3 (3)
C2—C3—C4—C5	0.9 (8)	O1—Cu1—N1—C1	91.8 (5)
C3—C4—C5—C6	−1.4 (8)	N4—Cu1—N1—C1	−7.1 (5)
C4—C5—C6—N2	178.6 (5)	N3—Cu1—N1—C1	170.6 (4)
C4—C5—C6—C1	1.2 (6)	O2ⁱ—Cu1—N1—C1	−106.6 (4)
N1—C1—C6—C5	178.3 (4)	N1—C7—N2—C6	−1.9 (5)
C2—C1—C6—C5	−0.5 (6)	C8—C7—N2—C6	176.1 (4)
N1—C1—C6—N2	0.3 (4)	C5—C6—N2—C7	−176.9 (5)
C2—C1—C6—N2	−178.5 (4)	C1—C6—N2—C7	0.9 (5)
N1—C7—C8—N3	4.9 (6)	C11—C12—N3—C8	−0.4 (6)
N2—C7—C8—N3	−172.9 (4)	C11—C12—N3—Cu1	−172.4 (3)
N1—C7—C8—C9	−175.5 (4)	C9—C8—N3—C12	0.6 (6)
N2—C7—C8—C9	6.7 (7)	C7—C8—N3—C12	−179.8 (4)
N3—C8—C9—C10	−0.7 (7)	C9—C8—N3—Cu1	173.6 (3)
C7—C8—C9—C10	179.8 (4)	C7—C8—N3—Cu1	−6.8 (4)
C8—C9—C10—C11	0.6 (7)	O1—Cu1—N3—C12	−26.3 (4)
C9—C10—C11—C12	−0.4 (7)	N1—Cu1—N3—C12	177.7 (4)
C10—C11—C12—N3	0.3 (7)	O2ⁱ—Cu1—N3—C12	69.5 (3)
O2—C14—C15—N4	−163.0 (3)	O1—Cu1—N3—C8	161.3 (3)
O1—C14—C15—N4	18.2 (5)	N1—Cu1—N3—C8	5.4 (3)
O2—C14—C15—C16	−36.7 (5)	O2ⁱ—Cu1—N3—C8	−102.8 (3)
O1—C14—C15—C16	144.5 (3)	C16—C15—N4—Cu1	−147.4 (3)
N4—C15—C16—C17	−58.1 (5)	C14—C15—N4—Cu1	−22.4 (4)
C14—C15—C16—C17	178.0 (3)	O1—Cu1—N4—C15	17.0 (3)
C15—C16—C17—S1	−177.8 (3)	N1—Cu1—N4—C15	172.6 (3)
C18—S1—C17—C16	78.7 (4)	O2ⁱ—Cu1—N4—C15	−78.5 (3)
N2—C7—N1—C1	2.0 (5)	O2—C14—O1—Cu1	177.1 (3)
C8—C7—N1—C1	−176.1 (4)	C15—C14—O1—Cu1	−4.2 (4)
N2—C7—N1—Cu1	177.7 (3)	N4—Cu1—O1—C14	−7.3 (3)
C8—C7—N1—Cu1	−0.5 (5)	N1—Cu1—O1—C14	−109.8 (3)
C2—C1—N1—C7	177.2 (5)	N3—Cu1—O1—C14	173.8 (3)
C6—C1—N1—C7	−1.4 (4)	O2ⁱ—Cu1—O1—C14	87.8 (3)
C2—C1—N1—Cu1	3.9 (8)	O1—C14—O2—Cu1ⁱⁱ	−48.0 (5)
C6—C1—N1—Cu1	−174.8 (3)	C15—C14—O2—Cu1ⁱⁱ	133.4 (3)
O1—Cu1—N1—C7	−81.3 (4)

Symmetry codes: (i) x−1/2, −y+3/2, −z+2; (ii) x+1/2, −y+3/2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2a···O3ⁱⁱⁱ	0.86	2.06	2.904 (6)	168
N4—H4a···O5^iv	0.90	2.53	3.370 (7)	155
N4—H4b···O4	0.90	2.31	3.064 (7)	141

Symmetry codes: (iii) x−1/2, −y+5/2, −z+2; (iv) x−1, y, z.

Experimental details

Crystal data
Chemical formula	[Cu(C₅H₁₀NO₂S)(C₁₂H₉N₃)]ClO₄
M_r	506.41
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	6.9718 (4), 11.8902 (6), 24.7024 (13)
V (Å³)	2047.73 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.34
Crystal size (mm)	0.45 × 0.35 × 0.13

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.583, 0.845
No. of measured, independent and observed [I > 2σ(I)] reflections	12781, 4464, 3557
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.640

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.111, 1.05
No. of reflections	4464
No. of parameters	272
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.28
Absolute structure	Flack (1983), 1874 Friedel pairs
Absolute structure parameter	−0.001 (17)

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2003), SHELXTL (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Selected bond lengths (Å) top

Cu1—O2ⁱ	2.272 (3)	Cu1—N3	2.023 (3)
Cu1—O1	1.929 (3)	Cu1—N4	1.985 (3)
Cu1—N1	1.996 (2)	O2—Cu1ⁱⁱ	2.272 (3)

Symmetry codes: (i) x−1/2, −y+3/2, −z+2; (ii) x+1/2, −y+3/2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2a···O3ⁱⁱⁱ	0.86	2.06	2.904 (6)	168
N4—H4a···O5^iv	0.90	2.53	3.370 (7)	155
N4—H4b···O4	0.90	2.31	3.064 (7)	141

Symmetry codes: (iii) x−1/2, −y+5/2, −z+2; (iv) x−1, y, z.

Acknowledgements

This work was supported by the Science and Technology Plan Project of Guangdong (No. 2009B020312010), the Natural Science Foundation of Guangdong (No. 10151064201000016) and the 211 Project Program Foundation of South China Agricultural University (No. 2009B010100001).

References

Bruker (2001). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2003). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Devereux, M., McCann, M. O., Shea, D., Kelly, R., Egan, D., Deegan, C., Kavanagh, K., McKee, V. & Finn, G. (2004). J. Inorg. Biochem. 98, 1023–1031. Web of Science CSD CrossRef PubMed CAS Google Scholar
Devereux, M. O., Shea, D., Kellett, A., McCann, M., Walsh, M., Egan, D., Deegan, C., Kedziora, K., Rosair, G. & Mueller-Bunz, H. (2007). J. Inorg. Biochem. 101, 881–892. Web of Science CrossRef PubMed CAS Google Scholar
El-Sherif, A. A. & Jeragh, B. J. A. (2007). Spectrochim. Acta Part A, 68, 877–882. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Lin, Q. B., Le, X. Y., Xiong, Y. H. & Feng, X. L. (2006). Chin. J. Inorg. Chem. 22, 2080–2084. CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yamauchi, O., Odani, A. & Masuda, H. (1992). Inorg. Chim. Acta, 198–200, 749–761. CrossRef CAS Google Scholar
Zhou, X. H., Le, X. Y. & Chen, S. (2005). J. Coord. Chem. 58, 993–1001. CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.