Bis(2,2′-bipyrid­yl)-1κ2N,N′;3κ2N,N′-bis­(4-bromo-2-formyl­phenolato)-1κ2O,O′;3κ2O,O′-bis­[μ-2-(5-bromo-2-oxidobenzylidene­amino)­ethane­sul­fon­ato]-1:2κ3O:N,O2;2:3κ3N,O2:O-tricopper(II) monohydrate

Zhang, L.

doi:10.1107/S1600536809014263

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page m552

doi:10.1107/S1600536809014263

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Bis(2,2′-bipyridyl)-1κ²N,N′;3κ²N,N′-bis(4-bromo-2-formylphenolato)-1κ²O,O′;3κ²O,O′-bis[μ-2-(5-bromo-2-oxidobenzylideneamino)ethanesulfonato]-1:2κ³O:N,O²;2:3κ³N,O²:O-tricopper(II) monohydrate

Ling Zhang ^a ^*

^aDepartment of Chemistry, Lishui University, 323000 Lishui, Zhejiang, People's Republic of China
^*Correspondence e-mail: zhangling2005@126.com

(Received 11 April 2009; accepted 16 April 2009; online 22 April 2009)

The title complex, [Cu₃(C₉H₈BrNO₄S)₂(C₇H₄BrO₂)₂(C₁₀H₈N₂)₂]·H₂O, lies on an inversion center located on the central Cu atom, which is four-coordinated in a square-planar geometry, whereas the outer Cu atoms related by symmetry are five-coordinated in a square-pyramidal geometry. The trinuclear molecules, with an intramolecular Cu⋯Cu separation of 6.313 (3) Å, are linked to each other, forming a chain through O—H⋯O and O—H⋯Br hydrogen bonds involving the half-occupied water molecule. Futhermore, weak C—H⋯O interactions link the chains to form a supramolecular network.

Related literature

For general background on coordination polymers and open framework materials, see: Kim et al. (2003 ); Iglesias et al. (2003 ); Moulton & Zaworotko (2001 ). For background on 2,2′-bipyridyl and 5-bromo-2-hydroxybenzaldehyde, see: Sun & Gao (2005 ); Murphy et al. (2004 ).

Experimental

Crystal data

[Cu₃(C₉H₈BrNO₄S)₂(C₇H₄BrO₂)₂(C₁₀H₈N₂)₂]·H₂O
M_r = 1533.30
Triclinic, $[P \overline 1]$
a = 10.031 (2) Å
b = 11.480 (2) Å
c = 12.913 (3) Å
α = 73.13 (3)°
β = 78.58 (3)°
γ = 75.24 (3)°
V = 1363.6 (6) Å³
Z = 1
Mo Kα radiation
μ = 4.24 mm⁻¹
T = 293 K
0.23 × 0.16 × 0.10 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.442, T_max = 0.677
12051 measured reflections
4888 independent reflections
1651 reflections with I > 2σ(I)
R_int = 0.077

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.099
S = 0.76
4888 reflections
367 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WB⋯O2	0.84	2.40	3.197 (11)	159
O1W—H1WA⋯Br2ⁱ	0.83	2.55	3.145 (9)	130
C4—H4⋯O1ⁱⁱ	0.93	2.42	3.316 (9)	163
C23—H23⋯O2ⁱⁱⁱ	0.93	2.54	3.324 (9)	142
Symmetry codes: (i) -x, -y+1, -z+2; (ii) -x, -y+2, -z; (iii) x+1, y, z.

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809014263/dn2446sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809014263/dn2446Isup2.hkl

checkCIF report

Comment top

Molecular self-assembly of supramolecular architectures has received much attention during recent decades (Kim et al., 2003; Iglesias et al., 2003; Moulton & Zaworotko, 2001). The structures and properties of such systems depend on the coordination and geometric preferences of both the central metals ions and bridging building blocks as well as the influence of weaker non-covalent interactions, such as hydrogen bonds and π-π stacking interactions. 2,2'-bipyridyl, 5-bromo-2-hydroxybenzaldehyde are excellent candidates for the construction of supramolecula complexes, since they not only have multiple coordination modes but also can form regular hydrogen bonds by functioning as both hydrogen-bond donor and acceptor (Sun & Gao, 2005; Murphy et al., 2004). 2-(5-bromo-2-hydroxybenzylamino)ethanesulfonic has a versatile binding ability, whose structure of complexes have not been reported to date. Recently, we obtained the title novel trinuclear copper complex (I) by the reaction of copper nitryl, 2,2'-bipyridyl, 5-bromo-2-hydroxybenzaldehyde and 2-(5-bromo-2-hydroxybenzylamino)ethanesulfonic in an aqueous solution, and its crystal is reported here.

The trinuclear complex lyies on a crystallographic inversion center located on the central Cu1 atom which is four-coordinated in a square planar geometry, whereas the other Cu2 atoms related by symmetry are five-coordinated in a square pyramidal geometry (Fig. 1). The compound forms trinuclear structure via the flexible 2-(5-bromo-2-hydroxybenzylamino)ethanesulfonic ligand, with a Cu···Cu separation of 6.313 (3) Å. These trinuclear units are linked to each other to form a chain through O-H···O and O-H···Br hydrogen bonds involving the water molecule (table 1, Fig. 2). Futhermore, weak C-H···O interactions link the chain to form a supramolecular network.

Related literature top

For general background on coordination polymers and open framework materials, see: Kim et al. (2003); Iglesias et al. (2003); Moulton & Zaworotko (2001). For background on 2,2'-bipyridyl and 5-bromo-2-hydroxybenzaldehyde, see: Sun & Gao (2005); Murphy et al. (2004).

Experimental top

A mixture of copper chloride(1 mmol), 5-bromo-2-hydroxybenzaldehyde (1 mmol), 2,2'-bipyridyl(1 mmol), 2-(5-bromo-2-hydroxybenzylamino)ethanesulfonic (1 mmol) and H₂O (12 ml) was placed in a 23 ml Teflon reactor, which was heated to 433 K for three days and then cooled to room temperature at a rate of 10 K h^-1. The crystals obtained were washed with water and dryed in air.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: APEX2 (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the trinuclear complex with the atom labeling scheme, Displacement ellipsoids are shown at the 30% probability level. H atom and water molecule have been omitted for clarity. [Symmetry code: (i) -x+1, -y+1, -z+1]
	Fig. 2. Partial packing view showing the H bond interactions linking the trinuclear unit through the water molecule. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.[Symmetry codes: (ii) -x, -y+1, -z+2]

Bis(2,2'-bipyridyl)-1κ²N,N';3κ²N,N'- bis(4-bromo-2-formylphenolato)- 1κ²O,O';3κ²O,O'- bis[µ-2-(5-bromo-2-oxidobenzylideneamino)ethanesulfonato]- 1:2κ³O:N,O²;2:3κ³N,O²:O- tricopper(II) monohydrate top

Crystal data top

[Cu₃(C₉H₈BrNO₄S)₂(C₇H₄BrO₂)₂(C₁₀H₈N₂)₂]·H₂O	Z = 1
M_r = 1533.30	F(000) = 759
Triclinic, P1	D_x = 1.867 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.031 (2) Å	Cell parameters from 2895 reflections
b = 11.480 (2) Å	θ = 2.4–27.9°
c = 12.913 (3) Å	µ = 4.24 mm⁻¹
α = 73.13 (3)°	T = 293 K
β = 78.58 (3)°	Block, colorless
γ = 75.24 (3)°	0.23 × 0.16 × 0.10 mm
V = 1363.6 (6) Å³

Data collection top

Bruker APEXII area-detector diffractometer	4888 independent reflections
Radiation source: fine-focus sealed tube	1651 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.077
ϕ and ω scans	θ_max = 25.2°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −12→12
T_min = 0.442, T_max = 0.677	k = −13→13
12051 measured reflections	l = −15→15

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H-atom parameters constrained
S = 0.76	w = 1/[σ²(F_o²) + (0.0382P)²] where P = (F_o² + 2F_c²)/3
4888 reflections	(Δ/σ)_max = 0.001
367 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

[Cu₃(C₉H₈BrNO₄S)₂(C₇H₄BrO₂)₂(C₁₀H₈N₂)₂]·H₂O	γ = 75.24 (3)°
M_r = 1533.30	V = 1363.6 (6) Å³
Triclinic, P1	Z = 1
a = 10.031 (2) Å	Mo Kα radiation
b = 11.480 (2) Å	µ = 4.24 mm⁻¹
c = 12.913 (3) Å	T = 293 K
α = 73.13 (3)°	0.23 × 0.16 × 0.10 mm
β = 78.58 (3)°

Data collection top

Bruker APEXII area-detector diffractometer	4888 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1651 reflections with I > 2σ(I)
T_min = 0.442, T_max = 0.677	R_int = 0.077
12051 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 0.76	Δρ_max = 0.43 e Å⁻³
4888 reflections	Δρ_min = −0.39 e Å⁻³
367 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.5000	0.5000	0.5000	0.0567 (4)
Cu2	0.16643 (9)	1.01005 (8)	0.23932 (7)	0.0545 (3)
Br1	0.56422 (9)	0.78255 (8)	0.70805 (6)	0.0780 (3)
Br2	0.20594 (10)	0.35954 (9)	1.08489 (7)	0.0900 (4)
S1	0.0325 (2)	0.7374 (2)	0.34555 (18)	0.0589 (6)
N1	0.2317 (7)	0.9972 (6)	0.0858 (5)	0.0490 (16)
N2	0.0114 (6)	1.1303 (5)	0.1664 (6)	0.0499 (17)
N3	0.3009 (6)	0.5065 (5)	0.5526 (5)	0.0539 (18)
O1	0.0575 (6)	0.6616 (5)	0.2703 (4)	0.100 (2)
O2	−0.0917 (5)	0.7223 (5)	0.4217 (4)	0.0901 (18)
O3	0.0319 (5)	0.8680 (4)	0.2953 (4)	0.0853 (18)
O4	0.5413 (5)	0.4760 (5)	0.6422 (4)	0.0695 (16)
O5	0.1069 (5)	1.0634 (4)	0.3756 (4)	0.0677 (16)
O6	0.3395 (4)	0.9154 (4)	0.2812 (3)	0.0529 (13)
C1	−0.0981 (10)	1.1957 (8)	0.2182 (6)	0.066 (2)
H1	−0.1040	1.1861	0.2929	0.079*
C2	−0.2050 (8)	1.2792 (7)	0.1604 (8)	0.070 (2)
H2	−0.2822	1.3230	0.1965	0.084*
C3	−0.1923 (10)	1.2938 (8)	0.0521 (8)	0.078 (3)
H3	−0.2616	1.3488	0.0131	0.094*
C4	−0.0822 (9)	1.2309 (8)	−0.0011 (7)	0.066 (3)
H4	−0.0750	1.2429	−0.0762	0.080*
C5	0.0231 (9)	1.1459 (7)	0.0577 (8)	0.056 (2)
C6	0.1483 (9)	1.0735 (7)	0.0102 (7)	0.054 (2)
C7	0.1860 (10)	1.0791 (7)	−0.0994 (7)	0.070 (3)
H7	0.1294	1.1312	−0.1507	0.083*
C8	0.3088 (11)	1.0058 (9)	−0.1304 (7)	0.074 (3)
H8	0.3363	1.0089	−0.2041	0.089*
C9	0.3919 (9)	0.9284 (7)	−0.0566 (8)	0.074 (3)
H9	0.4750	0.8777	−0.0781	0.089*
C10	0.3483 (9)	0.9282 (7)	0.0509 (7)	0.059 (2)
H10	0.4047	0.8760	0.1023	0.071*
C11	0.3250 (10)	0.4410 (6)	0.7469 (6)	0.059 (2)
C12	0.2482 (8)	0.4121 (6)	0.8509 (6)	0.059 (2)
H12	0.1554	0.4079	0.8578	0.071*
C13	0.3108 (9)	0.3899 (6)	0.9436 (5)	0.058 (2)
C14	0.4491 (9)	0.3968 (7)	0.9313 (7)	0.069 (2)
H14	0.4903	0.3812	0.9939	0.083*
C15	0.5277 (8)	0.4253 (6)	0.8325 (7)	0.061 (2)
H15	0.6201	0.4296	0.8276	0.073*
C16	0.4641 (9)	0.4487 (7)	0.7348 (7)	0.056 (2)
C17	0.2491 (7)	0.4750 (5)	0.6544 (6)	0.048 (2)
H17	0.1547	0.4741	0.6694	0.057*
C18	0.1956 (7)	0.5436 (6)	0.4753 (5)	0.056 (2)
H18A	0.1090	0.5212	0.5143	0.067*
H18B	0.2284	0.4991	0.4186	0.067*
C19	0.1708 (7)	0.6813 (6)	0.4242 (5)	0.058 (2)
H19A	0.2551	0.7010	0.3781	0.070*
H19B	0.1517	0.7245	0.4816	0.070*
C20	0.3051 (8)	0.9405 (7)	0.4636 (6)	0.0427 (19)
C21	0.3588 (8)	0.9097 (6)	0.5629 (6)	0.052 (2)
H21	0.3079	0.9415	0.6208	0.062*
C22	0.4862 (9)	0.8328 (7)	0.5734 (6)	0.053 (2)
C23	0.5646 (8)	0.7859 (6)	0.4863 (7)	0.058 (2)
H23	0.6518	0.7343	0.4951	0.069*
C24	0.5151 (8)	0.8146 (6)	0.3881 (5)	0.051 (2)
H24	0.5683	0.7829	0.3309	0.061*
C25	0.3833 (8)	0.8923 (6)	0.3751 (7)	0.0455 (19)
C26	0.1759 (9)	1.0241 (7)	0.4569 (6)	0.067 (2)
H26	0.1361	1.0541	0.5181	0.080*
O1W	−0.0713 (9)	0.6212 (10)	0.6775 (8)	0.101 (4)	0.50
H1WA	−0.1452	0.6481	0.7125	0.152*	0.50
H1WB	−0.0587	0.6569	0.6109	0.152*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0656 (10)	0.0561 (9)	0.0502 (9)	−0.0107 (8)	−0.0282 (8)	−0.0044 (7)
Cu2	0.0598 (7)	0.0578 (7)	0.0444 (6)	−0.0086 (5)	−0.0168 (5)	−0.0072 (5)
Br1	0.0910 (7)	0.0913 (7)	0.0530 (6)	−0.0181 (6)	−0.0290 (5)	−0.0083 (5)
Br2	0.1119 (8)	0.1085 (8)	0.0554 (6)	−0.0490 (7)	−0.0213 (6)	−0.0006 (5)
S1	0.0574 (16)	0.0591 (17)	0.0571 (15)	−0.0124 (13)	−0.0245 (13)	0.0013 (13)
N1	0.057 (5)	0.045 (4)	0.049 (4)	−0.012 (4)	−0.015 (4)	−0.012 (4)
N2	0.045 (5)	0.050 (5)	0.057 (5)	−0.010 (4)	−0.012 (4)	−0.014 (4)
N3	0.074 (5)	0.052 (4)	0.037 (4)	−0.019 (4)	−0.028 (4)	0.005 (3)
O1	0.132 (5)	0.107 (5)	0.067 (4)	0.007 (4)	−0.059 (4)	−0.029 (4)
O2	0.059 (4)	0.080 (4)	0.116 (5)	−0.014 (3)	−0.006 (4)	−0.005 (4)
O3	0.083 (4)	0.060 (4)	0.102 (4)	−0.023 (3)	−0.058 (3)	0.033 (3)
O4	0.061 (4)	0.094 (4)	0.055 (4)	−0.011 (3)	−0.022 (3)	−0.018 (3)
O5	0.068 (4)	0.086 (4)	0.045 (3)	0.003 (3)	−0.016 (3)	−0.021 (3)
O6	0.061 (3)	0.059 (3)	0.044 (3)	−0.011 (3)	−0.019 (3)	−0.013 (3)
C1	0.077 (7)	0.069 (7)	0.054 (6)	−0.028 (6)	−0.016 (6)	−0.004 (5)
C2	0.063 (6)	0.057 (6)	0.090 (7)	−0.014 (5)	−0.024 (6)	−0.010 (6)
C3	0.070 (7)	0.075 (7)	0.085 (8)	0.008 (6)	−0.041 (6)	−0.013 (6)
C4	0.060 (6)	0.089 (7)	0.058 (6)	−0.016 (6)	−0.026 (6)	−0.016 (6)
C5	0.060 (7)	0.048 (6)	0.064 (7)	−0.020 (5)	−0.025 (6)	−0.004 (5)
C6	0.064 (7)	0.043 (6)	0.057 (6)	−0.015 (5)	−0.017 (6)	−0.006 (5)
C7	0.103 (8)	0.062 (7)	0.040 (6)	−0.016 (6)	−0.017 (6)	−0.003 (5)
C8	0.109 (9)	0.076 (7)	0.043 (6)	−0.032 (6)	0.007 (6)	−0.025 (6)
C9	0.083 (7)	0.068 (7)	0.067 (7)	−0.007 (5)	−0.013 (6)	−0.016 (6)
C10	0.052 (6)	0.066 (6)	0.054 (6)	−0.004 (5)	−0.013 (5)	−0.009 (5)
C11	0.085 (7)	0.058 (6)	0.035 (5)	−0.014 (5)	−0.022 (5)	−0.005 (4)
C12	0.075 (6)	0.047 (5)	0.061 (6)	−0.014 (5)	−0.022 (5)	−0.013 (5)
C13	0.093 (7)	0.048 (5)	0.032 (5)	−0.021 (5)	−0.015 (5)	0.001 (4)
C14	0.061 (6)	0.086 (7)	0.064 (6)	−0.016 (5)	−0.024 (5)	−0.014 (5)
C15	0.062 (6)	0.063 (6)	0.063 (6)	−0.013 (5)	−0.025 (5)	−0.012 (5)
C16	0.063 (7)	0.047 (6)	0.060 (7)	−0.001 (5)	−0.027 (6)	−0.011 (5)
C17	0.051 (5)	0.027 (5)	0.068 (6)	−0.002 (4)	−0.033 (5)	−0.004 (4)
C18	0.065 (5)	0.048 (5)	0.062 (5)	−0.018 (4)	−0.040 (4)	0.001 (4)
C19	0.061 (6)	0.051 (5)	0.056 (5)	−0.007 (4)	−0.031 (4)	0.008 (4)
C20	0.037 (5)	0.041 (5)	0.052 (6)	0.002 (4)	−0.011 (5)	−0.021 (4)
C21	0.052 (6)	0.051 (6)	0.054 (6)	−0.016 (5)	0.001 (5)	−0.019 (4)
C22	0.057 (6)	0.059 (6)	0.047 (5)	−0.013 (5)	−0.019 (5)	−0.011 (4)
C23	0.049 (6)	0.047 (5)	0.074 (6)	0.004 (4)	−0.017 (5)	−0.017 (5)
C24	0.062 (6)	0.050 (5)	0.044 (5)	−0.010 (5)	−0.018 (5)	−0.014 (4)
C25	0.046 (6)	0.035 (5)	0.055 (6)	−0.004 (4)	−0.014 (5)	−0.009 (4)
C26	0.085 (7)	0.069 (6)	0.046 (6)	−0.014 (6)	0.003 (5)	−0.025 (5)
O1W	0.071 (8)	0.148 (11)	0.085 (8)	0.006 (7)	0.019 (7)	−0.076 (8)

Geometric parameters (Å, º) top

Cu1—O4	1.889 (5)	C7—H7	0.9300
Cu1—O4ⁱ	1.889 (5)	C8—C9	1.356 (9)
Cu1—N3	1.967 (6)	C8—H8	0.9300
Cu1—N3ⁱ	1.967 (6)	C9—C10	1.370 (9)
Cu2—O6	1.886 (4)	C9—H9	0.9300
Cu2—O5	1.963 (5)	C10—H10	0.9300
Cu2—N2	1.986 (6)	C11—C16	1.395 (10)
Cu2—N1	1.996 (6)	C11—C12	1.403 (9)
Cu2—O3	2.249 (5)	C11—C17	1.449 (8)
Br1—C22	1.922 (7)	C12—C13	1.389 (8)
Br2—C13	1.901 (7)	C12—H12	0.9300
S1—O1	1.431 (5)	C13—C14	1.385 (9)
S1—O2	1.441 (5)	C14—C15	1.359 (9)
S1—O3	1.449 (4)	C14—H14	0.9300
S1—C19	1.758 (6)	C15—C16	1.450 (9)
N1—C10	1.314 (8)	C15—H15	0.9300
N1—C6	1.369 (8)	C17—H17	0.9300
N2—C1	1.341 (8)	C18—C19	1.502 (7)
N2—C5	1.348 (8)	C18—H18A	0.9700
N3—C17	1.296 (7)	C18—H18B	0.9700
N3—C18	1.495 (7)	C19—H19A	0.9700
O4—C16	1.292 (8)	C19—H19B	0.9700
O5—C26	1.280 (7)	C20—C26	1.404 (9)
O6—C25	1.303 (7)	C20—C21	1.404 (8)
C1—C2	1.415 (9)	C20—C25	1.421 (9)
C1—H1	0.9300	C21—C22	1.362 (8)
C2—C3	1.343 (9)	C21—H21	0.9300
C2—H2	0.9300	C22—C23	1.400 (9)
C3—C4	1.339 (9)	C23—C24	1.373 (8)
C3—H3	0.9300	C23—H23	0.9300
C4—C5	1.416 (9)	C24—C25	1.405 (8)
C4—H4	0.9300	C24—H24	0.9300
C5—C6	1.449 (10)	C26—H26	0.9300
C6—C7	1.379 (9)	O1W—H1WA	0.8251
C7—C8	1.363 (9)	O1W—H1WB	0.8381

O4—Cu1—O4ⁱ	180.000 (1)	C8—C9—H9	121.4
O4—Cu1—N3	92.1 (2)	C10—C9—H9	121.4
O4ⁱ—Cu1—N3	87.9 (2)	N1—C10—C9	124.0 (8)
O4—Cu1—N3ⁱ	87.9 (2)	N1—C10—H10	118.0
O4ⁱ—Cu1—N3ⁱ	92.1 (2)	C9—C10—H10	118.0
N3—Cu1—N3ⁱ	180.0 (3)	C16—C11—C12	120.9 (7)
O6—Cu2—O5	93.61 (19)	C16—C11—C17	122.1 (7)
O6—Cu2—N2	166.7 (2)	C12—C11—C17	116.7 (8)
O5—Cu2—N2	93.4 (3)	C13—C12—C11	120.0 (7)
O6—Cu2—N1	90.5 (2)	C13—C12—H12	120.0
O5—Cu2—N1	166.5 (2)	C11—C12—H12	120.0
N2—Cu2—N1	80.3 (3)	C14—C13—C12	119.0 (7)
O6—Cu2—O3	102.37 (17)	C14—C13—Br2	120.3 (6)
O5—Cu2—O3	91.9 (2)	C12—C13—Br2	120.7 (7)
N2—Cu2—O3	88.68 (19)	C15—C14—C13	123.3 (7)
N1—Cu2—O3	99.8 (2)	C15—C14—H14	118.4
O1—S1—O2	111.7 (4)	C13—C14—H14	118.4
O1—S1—O3	114.7 (3)	C14—C15—C16	118.5 (7)
O2—S1—O3	110.9 (3)	C14—C15—H15	120.7
O1—S1—C19	106.6 (3)	C16—C15—H15	120.7
O2—S1—C19	105.8 (3)	O4—C16—C11	124.6 (7)
O3—S1—C19	106.4 (3)	O4—C16—C15	117.0 (8)
C10—N1—C6	118.0 (7)	C11—C16—C15	118.3 (8)
C10—N1—Cu2	126.4 (6)	N3—C17—C11	125.8 (7)
C6—N1—Cu2	115.5 (6)	N3—C17—H17	117.1
C1—N2—C5	120.3 (7)	C11—C17—H17	117.1
C1—N2—Cu2	124.1 (6)	N3—C18—C19	110.6 (5)
C5—N2—Cu2	115.6 (6)	N3—C18—H18A	109.5
C17—N3—C18	113.8 (6)	C19—C18—H18A	109.5
C17—N3—Cu1	124.5 (5)	N3—C18—H18B	109.5
C18—N3—Cu1	121.6 (4)	C19—C18—H18B	109.5
S1—O3—Cu2	143.6 (3)	H18A—C18—H18B	108.1
C16—O4—Cu1	129.1 (5)	C18—C19—S1	114.0 (4)
C26—O5—Cu2	124.1 (5)	C18—C19—H19A	108.7
C25—O6—Cu2	127.8 (5)	S1—C19—H19A	108.7
N2—C1—C2	120.6 (8)	C18—C19—H19B	108.7
N2—C1—H1	119.7	S1—C19—H19B	108.7
C2—C1—H1	119.7	H19A—C19—H19B	107.6
C3—C2—C1	118.5 (9)	C26—C20—C21	116.3 (8)
C3—C2—H2	120.7	C26—C20—C25	123.4 (7)
C1—C2—H2	120.7	C21—C20—C25	120.3 (7)
C4—C3—C2	121.5 (9)	C22—C21—C20	119.2 (7)
C4—C3—H3	119.3	C22—C21—H21	120.4
C2—C3—H3	119.3	C20—C21—H21	120.4
C3—C4—C5	119.7 (8)	C21—C22—C23	120.9 (7)
C3—C4—H4	120.1	C21—C22—Br1	121.7 (6)
C5—C4—H4	120.1	C23—C22—Br1	117.4 (7)
N2—C5—C4	119.3 (8)	C24—C23—C22	121.2 (7)
N2—C5—C6	115.3 (8)	C24—C23—H23	119.4
C4—C5—C6	125.3 (9)	C22—C23—H23	119.4
N1—C6—C7	121.1 (8)	C23—C24—C25	119.3 (7)
N1—C6—C5	113.3 (8)	C23—C24—H24	120.3
C7—C6—C5	125.6 (9)	C25—C24—H24	120.3
C8—C7—C6	117.9 (8)	O6—C25—C24	117.2 (7)
C8—C7—H7	121.0	O6—C25—C20	123.7 (7)
C6—C7—H7	121.0	C24—C25—C20	119.1 (7)
C9—C8—C7	121.8 (9)	O5—C26—C20	127.0 (7)
C9—C8—H8	119.1	O5—C26—H26	116.5
C7—C8—H8	119.1	C20—C26—H26	116.5
C8—C9—C10	117.1 (8)	H1WA—O1W—H1WB	116.5

Symmetry code: (i) −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—H1WB···O2	0.84	2.40	3.197 (11)	159
O1W—H1WA···Br2ⁱⁱ	0.83	2.55	3.145 (9)	130
C4—H4···O1ⁱⁱⁱ	0.93	2.42	3.316 (9)	163
C23—H23···O2^iv	0.93	2.54	3.324 (9)	142

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

Experimental details

Crystal data
Chemical formula	[Cu₃(C₉H₈BrNO₄S)₂(C₇H₄BrO₂)₂(C₁₀H₈N₂)₂]·H₂O
M_r	1533.30
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	10.031 (2), 11.480 (2), 12.913 (3)
α, β, γ (°)	73.13 (3), 78.58 (3), 75.24 (3)
V (Å³)	1363.6 (6)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	4.24
Crystal size (mm)	0.23 × 0.16 × 0.10

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.442, 0.677
No. of measured, independent and observed [I > 2σ(I)] reflections	12051, 4888, 1651
R_int	0.077
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.099, 0.76
No. of reflections	4888
No. of parameters	367
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.39

Computer programs: APEX2 (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O2	0.84	2.40	3.197 (11)	158.5
O1W—H1WA···Br2ⁱ	0.83	2.55	3.145 (9)	130.3
C4—H4···O1ⁱⁱ	0.93	2.42	3.316 (9)	162.5
C23—H23···O2ⁱⁱⁱ	0.93	2.54	3.324 (9)	141.8

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

Acknowledgements

The author acknowledges financial support by the Youth Foundation of Lishui University, China (No. QN05002).

References

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