Poly[[aqua­(μ-4,4′-bipyridine-κ2N:N′)(μ3-2-nitro-5-sulfonatobenzoato-κ3O1:O1′:O5)copper(II)] 4,4′-bipyridine hemisolvate]

Zhang, Z.

doi:10.1107/S1600536809039294

metal-organic compounds

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Volume 65| Part 11| November 2009| Pages m1272-m1273

https://doi.org/10.1107/S1600536809039294

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Poly[[aqua(μ-4,4′-bipyridine-κ²N:N′)(μ₃-2-nitro-5-sulfonatobenzoato-κ³O¹:O^1′:O⁵)copper(II)] 4,4′-bipyridine hemisolvate]

Zheyu Zhang ^a ^*

^aDepartment of Chemistry, Baicheng Normal College, Baicheng 137000, People's Republic of China
^*Correspondence e-mail: chemzyzhang@yahoo.cn

(Received 14 September 2009; accepted 28 September 2009; online 3 October 2009)

In the title compound, [Cu(C₇H₃NO₇S)(C₁₀H₈N₂)(H₂O)]·0.5C₁₀H₈N₂, the Cu^II atom is six-coordinated by two N atoms from two different bipyridine (bipy) ligands, one sulfonate O atom and two carboxylate O atoms from three 2-nitro-5-sulfonatobenzoate ligands and one water O atom in a distorted octahedral geometry. The bipy solvent molecule lies on an inversion center. The Cu^II atoms are linked by the bipy ligands, forming one-dimensional chains, which are connected by the 2-nitro-5-sulfonatobenzoate ligands into a two-dimensional layer-like network. The two-dimensional structure is extended by O—H⋯O and O—H⋯N hydrogen bonds into a three-dimensional supramolecular network.

Related literature

For general background to copper(II) sulfonate complexes, see: Du et al. (2009 ); Li et al. (2009 ); Liu et al. (2009 ); Sonnauer & Stock (2008 ); Sonnauer et al. (2009 ). For related structures, see: Dong et al. (2009 ).

Experimental

Crystal data

[Cu(C₇H₃NO₇S)(C₁₀H₈N₂)(H₂O)]·0.5C₁₀H₈N₂
M_r = 561.00
Monoclinic, P 2₁ /c
a = 11.4549 (17) Å
b = 11.0447 (16) Å
c = 17.089 (3) Å
β = 92.738 (3)°
V = 2159.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.17 mm⁻¹
T = 293 K
0.23 × 0.17 × 0.14 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.767, T_max = 0.850
11892 measured reflections
4260 independent reflections
2560 reflections with I > 2σ(I)
R_int = 0.088

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.135
S = 1.00
4260 reflections
331 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.86 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N2	1.986 (4)
Cu1—N3ⁱ	2.004 (4)
Cu1—O2ⁱⁱ	2.565 (4)
Cu1—O4	1.969 (3)
Cu1—O5ⁱⁱⁱ	2.299 (4)
Cu1—O6	2.032 (4)
Symmetry codes: (i) x, y+1, z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) -x+1, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H1A⋯O1ⁱⁱ	0.83 (5)	1.94 (5)	2.758 (5)	171 (6)
O6—H1B⋯N4^iv	0.86 (5)	2.00 (5)	2.801 (6)	156 (5)
Symmetry codes: (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809039294/hy2230sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809039294/hy2230Isup2.hkl

checkCIF report

Comment top

In recent years, the design and synthesis of copper(II) sulfonates have attracted great attention because of their flexible coordination modes, interesting inorganic-organic lamellar structures, selective and reversible guest inclusion properties, and their ability to intercalate guest molecules (Du et al., 2009; Sonnauer et al., 2009). It is noteworthy that some copper(II) sulfonate complexes with nitrogen-based secondary ligands, exhibiting different bonding modes dependent on the presence of secondary ligands, have been reported (Liu et al., 2009; Sonnauer & Stock, 2008). It has also been demonstrated that the existence and changes of the secondary ligands can have a great effect on the structures of copper(II) sulfonates, often with surprising results (Li et al., 2009). In this paper, we utilized 2-nitro-5-sulfobenzoic acid (H₂nsb) as an organic sulfonate ligand and 4,4'-bipyridine (bipy) as an N-donor ligand, providing a coordination compound, [Cu(nsb)(bipy)(H₂O)].0.5bipy, which is reported here.

In the title compound, the central Cu^II ion is six-coordinated by two N atoms from two different bipy ligands, one sulfonate O atom, two carboxylate O atoms from three nsb ligand and one water molecule in a distorted octahedral coordination geometry (Table 1). There are free bipy molecules in the structure, stabilized by hydrogen bonds (Fig. 1). The Cu—O distances are comparable to those found in other crystallographically characterized Cu^II complexes (Dong et al., 2009). The Cu atoms are linked by the bipy ligands, forming an extended one-dimensional chain. These chains are further connected by the nsb ligands into a two-dimensional layer-like network. In addition, the existence of O—H···O and O—H···N hydrogen bonds (Table 2) extends the two-dimensional layer into a three-dimensional supramolecular architecture (Fig. 2).

Related literature top

For general background to copper(II) sulfonate complexes, see: Du et al. (2009); Li et al. (2009); Liu et al. (2009); Sonnauer & Stock (2008); Sonnauer et al. (2009). For related structures, see: Dong et al. (2009).

Experimental top

A mixture of Cu(CH₃CO₂)₂.2H₂O (0.040 g, 0.2 mmol), 2-nitro-5-sulfobenzoic acid (0.049 g, 0.2 mmol), 4,4'-bipyridine (0.039 g, 0.2 mmol), and H₂O (15 ml) was sealed in a 25 ml Teflon-lined stainless steel reactor, which was heated at 443 K for 72 h and then it was cooled to room temperature. Blue crystals of the title compound were collected.

Structure description top

For general background to copper(II) sulfonate complexes, see: Du et al. (2009); Li et al. (2009); Liu et al. (2009); Sonnauer & Stock (2008); Sonnauer et al. (2009). For related structures, see: Dong et al. (2009).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) x, 1+y, z; (ii) 1-x, -0.5+y, 1.5-z; (iii) 1-x, 1-y, 1-z; (iv) -x, 1-y, 2-z.]
	Fig. 2. View of the three-dimensional supramolecular network in the title compound. Dashed lines denote hydrogen bonds.

Poly[[aqua(µ-4,4'-bipyridine-κ²N:N')(µ₃-2-nitro-5- sulfonatobenzoato-κ³O¹:O^1':O⁵)copper(II)] 4,4'-bipyridine hemisolvate] top

Crystal data top

[Cu(C₇H₃NO₇S)(C₁₀H₈N₂)(H₂O)]·0.5C₁₀H₈N₂	F(000) = 1144
M_r = 561.00	D_x = 1.725 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4260 reflections
a = 11.4549 (17) Å	θ = 1.8–26.0°
b = 11.0447 (16) Å	µ = 1.17 mm⁻¹
c = 17.089 (3) Å	T = 293 K
β = 92.738 (3)°	Block, blue
V = 2159.5 (5) Å³	0.23 × 0.17 × 0.14 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	4260 independent reflections
Radiation source: fine-focus sealed tube	2560 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.088
φ and ω scans	θ_max = 26.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −14→14
T_min = 0.767, T_max = 0.850	k = −13→13
11892 measured reflections	l = −21→10

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0455P)²] where P = (F_o² + 2F_c²)/3
4260 reflections	(Δ/σ)_max = 0.001
331 parameters	Δρ_max = 0.86 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

[Cu(C₇H₃NO₇S)(C₁₀H₈N₂)(H₂O)]·0.5C₁₀H₈N₂	V = 2159.5 (5) Å³
M_r = 561.00	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.4549 (17) Å	µ = 1.17 mm⁻¹
b = 11.0447 (16) Å	T = 293 K
c = 17.089 (3) Å	0.23 × 0.17 × 0.14 mm
β = 92.738 (3)°

Data collection top

Bruker SMART APEX CCD diffractometer	4260 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2560 reflections with I > 2σ(I)
T_min = 0.767, T_max = 0.850	R_int = 0.088
11892 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.86 e Å⁻³
4260 reflections	Δρ_min = −0.46 e Å⁻³
331 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.2223 (4)	0.7923 (4)	0.6944 (3)	0.0215 (13)
C2	0.2994 (4)	0.7254 (4)	0.6511 (3)	0.0198 (12)
H2	0.3565	0.7656	0.6243	0.024*
C3	0.2929 (4)	0.5989 (5)	0.6472 (3)	0.0195 (12)
C4	0.2051 (5)	0.5449 (4)	0.6866 (3)	0.0224 (13)
C5	0.1244 (5)	0.6090 (5)	0.7293 (4)	0.0321 (15)
H5	0.0649	0.5692	0.7542	0.039*
C6	0.1356 (5)	0.7338 (5)	0.7335 (4)	0.0313 (15)
H6	0.0846	0.7786	0.7627	0.038*
C7	0.3842 (5)	0.5338 (4)	0.6006 (3)	0.0177 (12)
C8	0.5609 (4)	0.2511 (4)	0.6504 (3)	0.0229 (13)
H8	0.5129	0.2936	0.6831	0.027*
C9	0.5560 (4)	0.1262 (4)	0.6501 (3)	0.0237 (13)
H9	0.5067	0.0860	0.6831	0.028*
C10	0.6248 (5)	0.0607 (4)	0.6005 (3)	0.0183 (13)
C11	0.6982 (4)	0.1266 (4)	0.5532 (3)	0.0205 (13)
H11	0.7454	0.0869	0.5186	0.025*
C12	0.6997 (4)	0.2501 (4)	0.5582 (3)	0.0208 (13)
H12	0.7504	0.2924	0.5273	0.025*
C13	0.6233 (4)	−0.0732 (4)	0.5994 (3)	0.0191 (13)
C14	0.6096 (4)	−0.1390 (4)	0.6673 (3)	0.0207 (13)
H14	0.5960	−0.0992	0.7140	0.025*
C15	0.6162 (5)	−0.2632 (4)	0.6656 (3)	0.0241 (13)
H15	0.6098	−0.3057	0.7122	0.029*
C16	0.6431 (5)	−0.2628 (4)	0.5338 (3)	0.0248 (13)
H16	0.6541	−0.3054	0.4878	0.030*
C17	0.6397 (5)	−0.1375 (4)	0.5304 (3)	0.0236 (13)
H17	0.6482	−0.0971	0.4833	0.028*
C18	0.0395 (6)	0.2255 (6)	1.0226 (4)	0.052 (2)
H18	0.0316	0.1641	1.0593	0.063*
C19	0.0134 (6)	0.3431 (6)	1.0445 (4)	0.0483 (19)
H19	−0.0057	0.3597	1.0957	0.058*
C20	0.0160 (5)	0.4360 (5)	0.9900 (4)	0.0353 (16)
C21	0.0488 (5)	0.4042 (6)	0.9165 (4)	0.0408 (17)
H21	0.0509	0.4629	0.8776	0.049*
C22	0.0790 (5)	0.2855 (6)	0.8995 (4)	0.0421 (17)
H22	0.1028	0.2677	0.8495	0.051*
N1	0.1916 (4)	0.4121 (4)	0.6833 (3)	0.0327 (13)
N2	0.6323 (4)	0.3136 (3)	0.6052 (3)	0.0212 (11)
N3	0.6313 (4)	−0.3253 (4)	0.5997 (3)	0.0194 (10)
N4	0.0754 (4)	0.1954 (5)	0.9520 (3)	0.0406 (14)
O1	0.1331 (3)	0.9957 (3)	0.7351 (2)	0.0321 (9)
O2	0.3416 (3)	0.9755 (3)	0.7461 (2)	0.0283 (10)
O3	0.2451 (4)	0.9910 (3)	0.6178 (2)	0.0373 (10)
O4	0.4740 (3)	0.5046 (3)	0.6409 (2)	0.0223 (8)
O5	0.3643 (3)	0.5231 (3)	0.5297 (2)	0.0277 (9)
O6	0.8116 (3)	0.4917 (4)	0.6061 (2)	0.0259 (9)
O7	0.2618 (3)	0.3519 (3)	0.6486 (3)	0.0376 (11)
O8	0.1112 (4)	0.3662 (4)	0.7165 (3)	0.0676 (17)
S1	0.23675 (13)	0.95326 (12)	0.69752 (9)	0.0243 (4)
Cu1	0.63413 (5)	0.49342 (5)	0.60435 (4)	0.0195 (2)
H1A	0.833 (5)	0.486 (5)	0.653 (3)	0.029*
H1B	0.843 (5)	0.543 (5)	0.576 (3)	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.025 (3)	0.019 (3)	0.021 (3)	0.002 (2)	−0.001 (3)	−0.003 (3)
C2	0.024 (3)	0.018 (3)	0.019 (3)	−0.002 (2)	0.004 (2)	0.001 (2)
C3	0.020 (3)	0.018 (3)	0.021 (3)	0.003 (2)	0.001 (3)	−0.002 (3)
C4	0.027 (3)	0.013 (3)	0.027 (4)	0.001 (2)	0.005 (3)	0.005 (2)
C5	0.027 (3)	0.029 (3)	0.042 (4)	−0.001 (3)	0.018 (3)	0.007 (3)
C6	0.032 (3)	0.026 (3)	0.037 (4)	0.009 (3)	0.013 (3)	0.001 (3)
C7	0.030 (3)	0.007 (3)	0.016 (3)	−0.005 (2)	0.006 (3)	0.001 (2)
C8	0.029 (3)	0.015 (3)	0.027 (3)	0.000 (2)	0.014 (3)	0.001 (3)
C9	0.030 (3)	0.014 (3)	0.028 (4)	−0.004 (2)	0.007 (3)	0.002 (3)
C10	0.029 (3)	0.005 (2)	0.020 (3)	0.002 (2)	−0.007 (3)	0.001 (2)
C11	0.028 (3)	0.011 (3)	0.024 (3)	−0.001 (2)	0.010 (3)	−0.004 (2)
C12	0.026 (3)	0.011 (3)	0.027 (3)	−0.001 (2)	0.007 (3)	0.004 (2)
C13	0.024 (3)	0.009 (3)	0.025 (4)	0.000 (2)	0.005 (3)	−0.002 (3)
C14	0.030 (3)	0.013 (3)	0.021 (3)	0.002 (2)	0.010 (3)	0.000 (2)
C15	0.032 (3)	0.016 (3)	0.025 (4)	−0.001 (2)	0.008 (3)	0.005 (3)
C16	0.040 (3)	0.014 (3)	0.022 (3)	0.003 (3)	0.011 (3)	−0.006 (3)
C17	0.035 (3)	0.015 (3)	0.021 (3)	−0.001 (3)	0.006 (3)	0.006 (3)
C18	0.068 (5)	0.043 (4)	0.048 (5)	0.014 (4)	0.020 (4)	0.011 (4)
C19	0.066 (5)	0.034 (4)	0.045 (5)	0.019 (4)	0.013 (4)	−0.004 (4)
C20	0.030 (4)	0.039 (4)	0.038 (4)	0.007 (3)	0.004 (3)	−0.004 (3)
C21	0.049 (4)	0.037 (4)	0.037 (4)	0.010 (3)	0.003 (4)	0.000 (3)
C22	0.047 (4)	0.043 (4)	0.037 (4)	0.007 (3)	0.004 (3)	−0.013 (4)
N1	0.033 (3)	0.025 (3)	0.041 (4)	−0.006 (2)	0.006 (3)	0.001 (3)
N2	0.029 (3)	0.011 (2)	0.024 (3)	0.002 (2)	0.005 (2)	−0.003 (2)
N3	0.022 (2)	0.011 (2)	0.026 (3)	−0.0013 (19)	0.005 (2)	0.001 (2)
N4	0.038 (3)	0.036 (3)	0.048 (4)	0.002 (2)	0.000 (3)	−0.003 (3)
O1	0.031 (2)	0.026 (2)	0.039 (2)	0.0052 (19)	0.0013 (19)	−0.006 (2)
O2	0.029 (2)	0.020 (2)	0.036 (3)	−0.0042 (16)	0.0006 (19)	−0.0048 (19)
O3	0.065 (3)	0.023 (2)	0.025 (2)	0.002 (2)	0.002 (2)	0.001 (2)
O4	0.0249 (19)	0.0142 (18)	0.028 (2)	0.0021 (17)	0.0053 (17)	0.0024 (19)
O5	0.045 (2)	0.017 (2)	0.021 (2)	0.0056 (17)	0.0079 (19)	−0.0030 (18)
O6	0.030 (2)	0.021 (2)	0.027 (2)	−0.0013 (18)	0.0064 (19)	0.006 (2)
O7	0.046 (3)	0.019 (2)	0.049 (3)	−0.005 (2)	0.019 (2)	−0.007 (2)
O8	0.066 (3)	0.035 (3)	0.106 (5)	−0.012 (2)	0.056 (3)	0.005 (3)
S1	0.0298 (8)	0.0166 (7)	0.0269 (9)	0.0041 (6)	0.0063 (7)	−0.0020 (6)
Cu1	0.0252 (3)	0.0066 (3)	0.0273 (4)	0.0008 (3)	0.0082 (3)	−0.0005 (3)

Geometric parameters (Å, º) top

C1—C6	1.382 (7)	C15—H15	0.9300
C1—C2	1.391 (7)	C16—N3	1.334 (6)
C1—S1	1.787 (5)	C16—C17	1.385 (7)
C2—C3	1.401 (6)	C16—H16	0.9300
C2—H2	0.9300	C17—H17	0.9300
C3—C4	1.373 (7)	C18—N4	1.335 (8)
C3—C7	1.525 (7)	C18—C19	1.389 (9)
C4—C5	1.398 (7)	C18—H18	0.9300
C4—N1	1.475 (7)	C19—C20	1.386 (9)
C5—C6	1.386 (7)	C19—H19	0.9300
C5—H5	0.9300	C20—C21	1.375 (8)
C6—H6	0.9300	C20—C20ⁱ	1.505 (11)
C7—O5	1.227 (6)	C21—C22	1.390 (8)
C7—O4	1.254 (6)	C21—H21	0.9300
C8—N2	1.341 (6)	C22—N4	1.342 (8)
C8—C9	1.381 (7)	C22—H22	0.9300
C8—H8	0.9300	N1—O8	1.216 (6)
C9—C10	1.388 (7)	N1—O7	1.219 (6)
C9—H9	0.9300	O1—S1	1.454 (4)
C10—C11	1.398 (7)	O2—S1	1.448 (4)
C10—C13	1.479 (6)	O3—S1	1.432 (4)
C11—C12	1.366 (6)	O6—H1A	0.83 (5)
C11—H11	0.9300	O6—H1B	0.86 (5)
C12—N2	1.339 (6)	Cu1—N2	1.986 (4)
C12—H12	0.9300	Cu1—N3ⁱⁱ	2.004 (4)
C13—C14	1.384 (7)	Cu1—O2ⁱⁱⁱ	2.565 (4)
C13—C17	1.397 (7)	Cu1—O4	1.969 (3)
C14—C15	1.374 (6)	Cu1—O5^iv	2.299 (4)
C14—H14	0.9300	Cu1—O6	2.032 (4)
C15—N3	1.337 (6)

C6—C1—C2	119.9 (5)	N4—C18—C19	123.8 (7)
C6—C1—S1	121.2 (4)	N4—C18—H18	118.1
C2—C1—S1	118.9 (4)	C19—C18—H18	118.1
C1—C2—C3	121.4 (5)	C20—C19—C18	119.9 (7)
C1—C2—H2	119.3	C20—C19—H19	120.0
C3—C2—H2	119.3	C18—C19—H19	120.0
C4—C3—C2	116.7 (5)	C21—C20—C19	116.2 (6)
C4—C3—C7	126.0 (5)	C21—C20—C20ⁱ	121.8 (8)
C2—C3—C7	117.3 (5)	C19—C20—C20ⁱ	122.0 (8)
C3—C4—C5	123.6 (5)	C20—C21—C22	120.9 (6)
C3—C4—N1	119.4 (5)	C20—C21—H21	119.5
C5—C4—N1	116.9 (5)	C22—C21—H21	119.5
C6—C5—C4	117.9 (5)	N4—C22—C21	122.9 (6)
C6—C5—H5	121.0	N4—C22—H22	118.6
C4—C5—H5	121.0	C21—C22—H22	118.6
C1—C6—C5	120.5 (5)	O8—N1—O7	122.2 (5)
C1—C6—H6	119.8	O8—N1—C4	118.4 (5)
C5—C6—H6	119.8	O7—N1—C4	119.4 (5)
O5—C7—O4	128.8 (5)	C12—N2—C8	117.4 (4)
O5—C7—C3	117.5 (5)	C12—N2—Cu1	120.8 (4)
O4—C7—C3	113.6 (5)	C8—N2—Cu1	121.7 (4)
N2—C8—C9	122.5 (5)	C16—N3—C15	117.9 (4)
N2—C8—H8	118.7	C16—N3—Cu1^v	123.2 (4)
C9—C8—H8	118.7	C15—N3—Cu1^v	118.8 (4)
C8—C9—C10	119.9 (5)	C18—N4—C22	116.2 (6)
C8—C9—H9	120.0	C7—O4—Cu1	126.4 (3)
C10—C9—H9	120.0	C7—O5—Cu1^iv	168.9 (4)
C9—C10—C11	117.2 (4)	Cu1—O6—H1A	105 (4)
C9—C10—C13	121.5 (5)	Cu1—O6—H1B	115 (4)
C11—C10—C13	121.4 (5)	H1A—O6—H1B	122 (5)
C12—C11—C10	119.3 (5)	O3—S1—O2	113.9 (2)
C12—C11—H11	120.4	O3—S1—O1	114.8 (2)
C10—C11—H11	120.4	O2—S1—O1	111.4 (2)
N2—C12—C11	123.7 (5)	O3—S1—C1	105.8 (3)
N2—C12—H12	118.1	O2—S1—C1	105.0 (2)
C11—C12—H12	118.1	O1—S1—C1	104.9 (2)
C14—C13—C17	117.7 (5)	O4—Cu1—N2	92.84 (16)
C14—C13—C10	121.1 (5)	O4—Cu1—N3ⁱⁱ	86.36 (16)
C17—C13—C10	121.1 (5)	N2—Cu1—N3ⁱⁱ	177.66 (18)
C15—C14—C13	119.9 (5)	O4—Cu1—O6	160.42 (16)
C15—C14—H14	120.1	N2—Cu1—O6	90.09 (17)
C13—C14—H14	120.1	N3ⁱⁱ—Cu1—O6	91.39 (17)
N3—C15—C14	122.6 (5)	O4—Cu1—O5^iv	111.89 (14)
N3—C15—H15	118.7	N2—Cu1—O5^iv	85.92 (16)
C14—C15—H15	118.7	N3ⁱⁱ—Cu1—O5^iv	92.34 (16)
N3—C16—C17	123.2 (5)	O6—Cu1—O5^iv	87.62 (15)
N3—C16—H16	118.4	O2ⁱⁱⁱ—Cu1—N2	85.20 (17)
C17—C16—H16	118.4	O2ⁱⁱⁱ—Cu1—N3ⁱⁱ	96.74 (17)
C16—C17—C13	118.5 (5)	O2ⁱⁱⁱ—Cu1—O4	75.35 (13)
C16—C17—H17	120.7	O2ⁱⁱⁱ—Cu1—O5^iv	168.81 (12)
C13—C17—H17	120.7	O2ⁱⁱⁱ—Cu1—O6	85.63 (13)

C6—C1—C2—C3	−1.2 (8)	C20ⁱ—C20—C21—C22	179.5 (7)
S1—C1—C2—C3	179.4 (4)	C20—C21—C22—N4	1.7 (10)
C1—C2—C3—C4	1.4 (8)	C3—C4—N1—O8	−177.7 (6)
C1—C2—C3—C7	−177.9 (5)	C5—C4—N1—O8	0.9 (8)
C2—C3—C4—C5	0.1 (9)	C3—C4—N1—O7	3.5 (8)
C7—C3—C4—C5	179.2 (5)	C5—C4—N1—O7	−178.0 (5)
C2—C3—C4—N1	178.5 (5)	C11—C12—N2—C8	1.0 (8)
C7—C3—C4—N1	−2.3 (9)	C11—C12—N2—Cu1	−176.6 (4)
C3—C4—C5—C6	−1.7 (9)	C9—C8—N2—C12	0.5 (8)
N1—C4—C5—C6	179.8 (5)	C9—C8—N2—Cu1	178.1 (4)
C2—C1—C6—C5	−0.5 (9)	C17—C16—N3—C15	−0.4 (8)
S1—C1—C6—C5	178.9 (5)	C17—C16—N3—Cu1^v	179.2 (4)
C4—C5—C6—C1	1.9 (9)	C14—C15—N3—C16	1.6 (8)
C4—C3—C7—O5	95.3 (7)	C14—C15—N3—Cu1^v	−178.0 (4)
C2—C3—C7—O5	−85.6 (6)	C19—C18—N4—C22	−3.8 (10)
C4—C3—C7—O4	−88.7 (7)	C21—C22—N4—C18	0.7 (9)
C2—C3—C7—O4	90.4 (6)	O5—C7—O4—Cu1	26.7 (7)
N2—C8—C9—C10	−1.5 (9)	C3—C7—O4—Cu1	−148.7 (3)
C8—C9—C10—C11	0.9 (8)	O4—C7—O5—Cu1^iv	−29 (2)
C8—C9—C10—C13	179.0 (5)	C3—C7—O5—Cu1^iv	146.5 (15)
C9—C10—C11—C12	0.6 (8)	C6—C1—S1—O3	−130.7 (5)
C13—C10—C11—C12	−177.6 (5)	C2—C1—S1—O3	48.7 (5)
C10—C11—C12—N2	−1.6 (8)	C6—C1—S1—O2	108.6 (5)
C9—C10—C13—C14	−35.0 (8)	C2—C1—S1—O2	−72.0 (5)
C11—C10—C13—C14	143.0 (5)	C6—C1—S1—O1	−9.0 (5)
C9—C10—C13—C17	147.2 (5)	C2—C1—S1—O1	170.5 (4)
C11—C10—C13—C17	−34.7 (8)	C7—O4—Cu1—N2	−106.1 (4)
C17—C13—C14—C15	2.0 (8)	C7—O4—Cu1—N3ⁱⁱ	71.7 (4)
C10—C13—C14—C15	−175.8 (5)	C7—O4—Cu1—O6	155.6 (5)
C13—C14—C15—N3	−2.5 (8)	C7—O4—Cu1—O5^iv	−19.4 (4)
N3—C16—C17—C13	0.1 (8)	C12—N2—Cu1—O4	153.9 (4)
C14—C13—C17—C16	−0.9 (8)	C8—N2—Cu1—O4	−23.6 (4)
C10—C13—C17—C16	176.9 (5)	C12—N2—Cu1—O6	−45.4 (4)
N4—C18—C19—C20	4.6 (11)	C8—N2—Cu1—O6	137.1 (4)
C18—C19—C20—C21	−2.0 (10)	C12—N2—Cu1—O5^iv	42.2 (4)
C18—C19—C20—C20ⁱ	177.6 (7)	C8—N2—Cu1—O5^iv	−135.3 (4)
C19—C20—C21—C22	−0.9 (10)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H1A···O1ⁱⁱⁱ	0.83 (5)	1.94 (5)	2.758 (5)	171 (6)
O6—H1B···N4^vi	0.86 (5)	2.00 (5)	2.801 (6)	156 (5)

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

Experimental details

Crystal data
Chemical formula	[Cu(C₇H₃NO₇S)(C₁₀H₈N₂)(H₂O)]·0.5C₁₀H₈N₂
M_r	561.00
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.4549 (17), 11.0447 (16), 17.089 (3)
β (°)	92.738 (3)
V (Å³)	2159.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.17
Crystal size (mm)	0.23 × 0.17 × 0.14

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.767, 0.850
No. of measured, independent and observed [I > 2σ(I)] reflections	11892, 4260, 2560
R_int	0.088
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.135, 1.00
No. of reflections	4260
No. of parameters	331
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.86, −0.46

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—N2	1.986 (4)	Cu1—O4	1.969 (3)
Cu1—N3ⁱ	2.004 (4)	Cu1—O5ⁱⁱⁱ	2.299 (4)
Cu1—O2ⁱⁱ	2.565 (4)	Cu1—O6	2.032 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H1A···O1ⁱⁱ	0.83 (5)	1.94 (5)	2.758 (5)	171 (6)
O6—H1B···N4^iv	0.86 (5)	2.00 (5)	2.801 (6)	156 (5)

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

Acknowledgements

Baicheng Normal College is thanked for supporting this work.

References

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