Aqua­[3-carb­oxy-2-(3,5-dibromo-2-oxidobenzyl­amino-κ2N,O)propanoato-κO1](dimethyl­formamide-κO)copper(II) dimethyl­formamide solvate monohydrate

Jin, L.-X.; Zhang, S.-H.; Liu, Z.; Li, G.-Z.

doi:10.1107/S1600536807041517

Aqua[3-carboxy-2-(3,5-dibromo-2-oxidobenzylamino-κ²N,O)propanoato-κO¹](dimethylformamide-κO)copper(II) dimethylformamide solvate monohydrate

L.-X. Jin, S.-H. Zhang, Z. Liu and G.-Z. Li

In the title compound, [Cu(C₁₁H₇Br₂NO₅)(C₃H₇NO)(H₂O)]·C₃H₇NO·H₂O, the Cu^II atom is coordinated in a slightly distorted square-pyramidal geometry defined by two O atoms and one N atom from a 3-carboxy-2-(3,5-dibromo-2-oxidobenzylamino)propanoate ligand, one O atom from a dimethylformamide (DMF) molecule in the basal plane, and by one O atom from an aqua ligand in the apical position. In the crystal structure, the water molecules are linked by O—H

O hydrogen bonds into chains which resemble a pearl necklace. The molecules form a three-dimensional supramolecular network through O—H

O hydrogen bonds and C—H

Br hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041517/er2034sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041517/er2034Isup2.hkl Contains datablock I

CCDC reference: 667095

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.006 Å
R factor = 0.038
wR factor = 0.087
Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    -   O9      ..       9.50 su
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N3
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          3
            O6  -CU1 -N1  -C5   -146.70  1.20   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          7
            O6  -CU1 -N1  -C2     41.60  1.40   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          9
            O5  -CU1 -O1  -C1    -86.20  0.80   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         14
            O1  -CU1 -O5  -C7     74.90  0.90   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         18
            N1  -CU1 -O6  -C12   151.20  1.30   1.555   1.555   1.555   1.555

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C2     = ...          S
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       2.24

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   7 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

Rencently, compounds containing dimmer water (Ghosh & Bharadwaj, 2003), water ring (Moorthy et al., 2002, Ugalde et al., 2000, Ghosh & Bharadwaj, 2004), water chain (Neogi & Bharadwaj, 2005, Cheruzel et al., 2003, Ghosh et al., 2005), metal-water chain (Ye et al., 2004), water network (Zhang et al., 2005), water-methanol intermix clusters (Raghuraman et al., 2003), and water ring chain (Feng, et al., 2007) give rise to considerable interest. Because these dimmer water, water ring, water chain, metal-water chain, water network, water ring chain and intermix clusters are potentially important form of water that is poorly understood. Water chains appear to facilitate the selective permeation (Tajkhorshid et al., 2002) of water across membranes and also to be important (Zaslavsky, & Gennis, 2000) in the control of proton fluxes in a variety of biomolecules.

The title compound, (I), is a Cu^II complex containing a ligand constructed from 2-(3,5-dibromo-2-hydroxy-benzylamino)-succinic acid and 3,5-dichloro-2-hydroxy-benzaldehyde. Each Cu^II atom is coordinated by two O atoms and one N atom from L^2- and one O atom from DMF and one O atom from H₂O to furnish a slightly distorted tetragonal pyramidal(Table 1). The asymmetric unit (Fig. 1) comprises one Cu^II complexes, one water molecule and one DMF molecule. The water molecules are linked by O—H···O hydrogen bonds (Table 2), forming a 'peral necklace' water chains. In the 'pearl necklace' water chains, the O8 water act as thread and the O9 water as pearl along 101 plan(Fig. 2). The water chains lie between layers of Cu^II complexes (Fig. 3), forming O—H···O hydrogen bonds to the O2 atoms of the carboxylate groups. The complex are further constructed three-dimensional supramolecular network through O—H···O hydrogen bond and C—H···Br hydrogen bond (Fig. 3).

Related literature top

For related literature, see: Cheruzel et al. (2003); Feng et al. (2007); Ghosh & Bharadwaj (2003); Ghosh & Bharadwaj (2004); Ghosh et al. (2005); Moorthy et al. (2002); Neogi & Bharadwaj (2005); Raghuraman et al. (2003); Tajkhorshid et al. (2002); Ugalde et al. (2000); Ye et al. (2004); Zaslavsky & Gennis (2000); Zhang et al. (2005).

Experimental top

A solution of aspartic acid (0.059 g, 0.5 mmol) and pottasium hydroxide (0.028 g, 0.5 mmol) in distilled water (10 ml) was added slowly to a solution of 3,5-dibromo-2-hydroxybenzaldehyde (0.5 mmol, 0.140 g) in ethanol (10 ml). The mixture was stirred for 1 h at 323 K, then added slowly to a solution of copper(II) nitrate (0.121 g, 0.5 mmol) in distilled water (10 ml). This mixture was stirred and refluxed for 2 h at 323 K; The precipitate was separated by filtration. Dregs were dissolved in DMF. The solution was filtered and the filtrate was left to stand at room temperature. Blue strips suitable for X-ray diffraction were obtained in a yield of 65% (based on copper nitrate).

Structure description top

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. The asymmetric unit of (I), showing displacement ellipsoids drawn at the 30% probability level for non-H atoms. The dashed lines indicate hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted.
	Fig. 2. Water molecules linked by O—H···O hydrogen bonds (dashed lines) that form chains. Displacement ellipsoids are shown at the 30% probability level for O atoms.
	Fig. 3. Projection of (I) along b, showing layers of Cu^II complexes with the water molecules lying between them. Dashed lines denote hydrogen bonds and H atoms not involved in hydrogen bonding have been omitted.

Aqua[3-carboxy-2-(3,5-dibromo-2-oxidobenzylamino-κ²N,O)propanoato-\ κO¹](dimethylformamide-κO)copper(II) dimethylformamide solvate monohydrate top

Crystal data top

[Cu(C₁₁H₇Br₂NO₅)(C₃H₇NO)(H₂O)]·C₃H₇NO·H₂O	F(000) = 2552
M_r = 638.76	D_x = 1.820 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4147 reflections
a = 46.176 (3) Å	θ = 2.7–25.7°
b = 5.1633 (19) Å	µ = 4.42 mm⁻¹
c = 21.793 (2) Å	T = 298 K
β = 116.186 (4)°	Strip, blue
V = 4662.6 (18) Å³	0.56 × 0.10 × 0.07 mm
Z = 8

Data collection top

Bruker SMART 1K CCD diffractometer	4091 independent reflections
Radiation source: fine-focus sealed tube	3197 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
Detector resolution: 10 pixels mm^-1	θ_max = 25.0°, θ_min = 1.9°
φ and ω scans	h = −54→33
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	k = −6→6
T_min = 0.191, T_max = 0.747	l = −25→25
11320 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0358P)² + 6.521P] where P = (F_o² + 2F_c²)/3
4091 reflections	(Δ/σ)_max = 0.002
290 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Cu(C₁₁H₇Br₂NO₅)(C₃H₇NO)(H₂O)]·C₃H₇NO·H₂O	V = 4662.6 (18) Å³
M_r = 638.76	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 46.176 (3) Å	µ = 4.42 mm⁻¹
b = 5.1633 (19) Å	T = 298 K
c = 21.793 (2) Å	0.56 × 0.10 × 0.07 mm
β = 116.186 (4)°

Data collection top

Bruker SMART 1K CCD diffractometer	4091 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	3197 reflections with I > 2σ(I)
T_min = 0.191, T_max = 0.747	R_int = 0.044
11320 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.04	Δρ_max = 0.47 e Å⁻³
4091 reflections	Δρ_min = −0.34 e Å⁻³
290 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
Cu1	0.667762 (11)	0.45742 (9)	0.32640 (2)	0.03304 (14)
Br1	0.631916 (12)	0.16100 (10)	0.48947 (2)	0.05071 (15)
Br2	0.550915 (11)	−0.56975 (9)	0.29641 (3)	0.05290 (15)
N1	0.64487 (7)	0.2519 (6)	0.24615 (15)	0.0299 (7)
N2	0.70705 (8)	0.8065 (7)	0.51375 (15)	0.0370 (8)
N3	0.49942 (10)	0.0691 (9)	0.3994 (2)	0.0650 (12)
O1	0.68006 (6)	0.6679 (5)	0.26737 (13)	0.0379 (7)
O2	0.67757 (7)	0.6785 (6)	0.16312 (13)	0.0459 (7)
O3	0.59772 (7)	0.6053 (6)	0.12787 (15)	0.0564 (9)
O4	0.58105 (8)	0.3707 (7)	0.03307 (14)	0.0592 (9)
H4	0.5656	0.4695	0.0201	0.089*
O5	0.64999 (6)	0.2798 (5)	0.37752 (12)	0.0377 (7)
O6	0.69090 (6)	0.6953 (5)	0.40330 (12)	0.0380 (7)
O7	0.52932 (10)	0.3581 (10)	0.4777 (2)	0.1011 (15)
O8	0.74314 (7)	0.2116 (6)	0.71684 (16)	0.0562 (8)
H18	0.7230	0.2380	0.7012	0.084*
H19	0.7466	0.0605	0.7341	0.084*
O9	0.71561 (7)	0.1607 (6)	0.34796 (14)	0.0518 (8)
H20	0.7256	0.1984	0.3244	0.078*
H21	0.7051	0.0219	0.3315	0.078*
C1	0.67179 (9)	0.5756 (8)	0.20757 (19)	0.0325 (9)
C2	0.65577 (9)	0.3065 (8)	0.19336 (18)	0.0338 (9)
H2	0.6732	0.1827	0.2015	0.041*
C3	0.63146 (9)	0.2660 (8)	0.11995 (18)	0.0366 (10)
H3A	0.6421	0.2968	0.0909	0.044*
H3B	0.6247	0.0861	0.1142	0.044*
C4	0.60197 (10)	0.4333 (8)	0.0956 (2)	0.0386 (10)
C5	0.62537 (9)	0.0658 (8)	0.23949 (19)	0.0322 (9)
H5	0.6167	−0.0235	0.1982	0.039*
C6	0.61567 (9)	−0.0170 (8)	0.29146 (19)	0.0314 (9)
C7	0.62860 (9)	0.0981 (7)	0.35723 (18)	0.0304 (9)
C8	0.61662 (9)	0.0012 (7)	0.40234 (19)	0.0323 (9)
C9	0.59465 (9)	−0.1957 (8)	0.3859 (2)	0.0371 (10)
H9	0.5880	−0.2573	0.4177	0.044*
C10	0.58250 (9)	−0.3019 (7)	0.3207 (2)	0.0353 (9)
C11	0.59296 (9)	−0.2178 (8)	0.2745 (2)	0.0345 (9)
H11	0.5850	−0.2942	0.2315	0.041*
C12	0.69048 (9)	0.6671 (8)	0.4600 (2)	0.0359 (9)
H12	0.6774	0.5373	0.4638	0.043*
C13	0.72672 (11)	1.0211 (9)	0.5119 (2)	0.0540 (12)
H13A	0.7238	1.0466	0.4659	0.081*
H13B	0.7490	0.9842	0.5410	0.081*
H13C	0.7204	1.1752	0.5276	0.081*
C14	0.70679 (12)	0.7506 (10)	0.5795 (2)	0.0557 (13)
H14A	0.6934	0.6023	0.5748	0.084*
H14B	0.6984	0.8973	0.5935	0.084*
H14C	0.7284	0.7156	0.6133	0.084*
C15	0.52653 (13)	0.1844 (12)	0.4396 (3)	0.0691 (15)
H15	0.5452	0.1250	0.4382	0.083*
C16	0.49831 (18)	−0.1326 (14)	0.3523 (4)	0.122 (3)
H16A	0.5198	−0.1692	0.3584	0.183*
H16B	0.4853	−0.0760	0.3062	0.183*
H16C	0.4891	−0.2863	0.3611	0.183*
C17	0.46963 (14)	0.1399 (15)	0.3995 (3)	0.097 (2)
H17A	0.4737	0.2536	0.4373	0.145*
H17B	0.4588	−0.0129	0.4038	0.145*
H17C	0.4563	0.2266	0.3574	0.145*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0410 (3)	0.0322 (3)	0.0282 (3)	−0.0060 (2)	0.0174 (2)	−0.0026 (2)
Br1	0.0727 (3)	0.0537 (3)	0.0363 (2)	−0.0067 (3)	0.0336 (2)	−0.0012 (2)
Br2	0.0474 (3)	0.0431 (3)	0.0706 (3)	−0.0103 (2)	0.0282 (2)	0.0033 (2)
N1	0.0345 (17)	0.0314 (18)	0.0297 (16)	0.0006 (16)	0.0197 (14)	−0.0012 (14)
N2	0.0403 (19)	0.040 (2)	0.0302 (17)	−0.0008 (17)	0.0149 (15)	−0.0066 (16)
N3	0.060 (3)	0.066 (3)	0.060 (3)	−0.004 (2)	0.018 (2)	−0.012 (2)
O1	0.0504 (16)	0.0331 (16)	0.0333 (15)	−0.0083 (14)	0.0213 (13)	−0.0022 (13)
O2	0.0609 (19)	0.0492 (19)	0.0368 (16)	−0.0100 (16)	0.0300 (15)	0.0027 (14)
O3	0.060 (2)	0.052 (2)	0.0504 (19)	0.0087 (17)	0.0179 (16)	−0.0108 (16)
O4	0.056 (2)	0.076 (3)	0.0342 (17)	0.0043 (18)	0.0098 (15)	−0.0064 (17)
O5	0.0487 (17)	0.0384 (17)	0.0305 (14)	−0.0143 (14)	0.0214 (12)	−0.0066 (13)
O6	0.0495 (17)	0.0360 (17)	0.0305 (15)	−0.0091 (14)	0.0194 (13)	−0.0041 (12)
O7	0.072 (3)	0.130 (4)	0.086 (3)	−0.023 (3)	0.021 (2)	−0.053 (3)
O8	0.0523 (19)	0.049 (2)	0.072 (2)	−0.0015 (16)	0.0317 (16)	0.0006 (17)
O9	0.0545 (18)	0.0473 (19)	0.0528 (19)	−0.0079 (16)	0.0228 (15)	0.0021 (16)
C1	0.031 (2)	0.034 (2)	0.032 (2)	0.0023 (18)	0.0140 (17)	−0.0036 (18)
C2	0.041 (2)	0.033 (2)	0.034 (2)	−0.0002 (19)	0.0231 (18)	−0.0036 (18)
C3	0.045 (2)	0.037 (2)	0.033 (2)	−0.005 (2)	0.0217 (18)	−0.0082 (19)
C4	0.049 (3)	0.037 (3)	0.033 (2)	−0.008 (2)	0.021 (2)	−0.0044 (19)
C5	0.035 (2)	0.034 (2)	0.027 (2)	0.0017 (19)	0.0142 (17)	−0.0027 (18)
C6	0.031 (2)	0.029 (2)	0.037 (2)	0.0018 (18)	0.0175 (17)	−0.0007 (17)
C7	0.036 (2)	0.029 (2)	0.030 (2)	0.0060 (19)	0.0171 (17)	0.0046 (17)
C8	0.038 (2)	0.028 (2)	0.033 (2)	0.0050 (18)	0.0171 (17)	0.0029 (17)
C9	0.041 (2)	0.035 (2)	0.042 (2)	0.005 (2)	0.0245 (19)	0.009 (2)
C10	0.033 (2)	0.028 (2)	0.044 (2)	−0.0021 (18)	0.0168 (19)	0.0005 (19)
C11	0.035 (2)	0.033 (2)	0.035 (2)	0.0025 (19)	0.0155 (18)	−0.0018 (18)
C12	0.036 (2)	0.034 (2)	0.038 (2)	−0.0040 (19)	0.0173 (18)	−0.0038 (19)
C13	0.065 (3)	0.044 (3)	0.053 (3)	−0.021 (3)	0.026 (2)	−0.013 (2)
C14	0.068 (3)	0.067 (3)	0.038 (2)	−0.005 (3)	0.028 (2)	−0.005 (2)
C15	0.058 (3)	0.077 (4)	0.062 (3)	0.003 (3)	0.017 (3)	−0.001 (3)
C16	0.110 (6)	0.089 (5)	0.135 (6)	0.014 (5)	0.024 (5)	−0.047 (5)
C17	0.069 (4)	0.134 (6)	0.090 (5)	−0.019 (4)	0.038 (4)	−0.025 (5)

Geometric parameters (Å, º) top

Cu1—O5	1.887 (3)	C2—H2	0.9800
Cu1—N1	1.916 (3)	C3—C4	1.498 (6)
Cu1—O1	1.950 (3)	C3—H3A	0.9700
Cu1—O6	1.969 (3)	C3—H3B	0.9700
Cu1—O9	2.556 (3)	C5—C6	1.454 (5)
Br1—C8	1.898 (4)	C5—H5	0.9300
Br2—C10	1.907 (4)	C6—C11	1.403 (5)
N1—C5	1.281 (5)	C6—C7	1.417 (5)
N1—C2	1.472 (5)	C7—C8	1.415 (5)
N2—C12	1.299 (5)	C8—C9	1.368 (5)
N2—C13	1.444 (5)	C9—C10	1.390 (5)
N2—C14	1.467 (5)	C9—H9	0.9300
N3—C15	1.312 (6)	C10—C11	1.366 (5)
N3—C17	1.424 (7)	C11—H11	0.9300
N3—C16	1.447 (7)	C12—H12	0.9300
O1—C1	1.277 (4)	C13—H13A	0.9600
O2—C1	1.233 (4)	C13—H13B	0.9600
O3—C4	1.202 (5)	C13—H13C	0.9600
O4—C4	1.316 (5)	C14—H14A	0.9600
O4—H4	0.8200	C14—H14B	0.9600
O5—C7	1.291 (4)	C14—H14C	0.9600
O6—C12	1.252 (4)	C15—H15	0.9300
O7—C15	1.190 (7)	C16—H16A	0.9600
O8—H18	0.8502	C16—H16B	0.9600
O8—H19	0.8500	C16—H16C	0.9600
O9—H20	0.8501	C17—H17A	0.9600
O9—H21	0.8500	C17—H17B	0.9600
C1—C2	1.540 (6)	C17—H17C	0.9600
C2—C3	1.509 (5)

O5—Cu1—N1	93.51 (12)	C11—C6—C7	120.6 (3)
O5—Cu1—O1	171.55 (12)	C11—C6—C5	117.6 (3)
N1—Cu1—O1	84.86 (12)	C7—C6—C5	121.8 (3)
O5—Cu1—O6	90.85 (11)	O5—C7—C8	119.6 (3)
N1—Cu1—O6	174.78 (12)	O5—C7—C6	124.6 (3)
O1—Cu1—O6	90.42 (11)	C8—C7—C6	115.8 (4)
O5—Cu1—O9	99.55 (11)	C9—C8—C7	123.6 (4)
N1—Cu1—O9	85.39 (11)	C9—C8—Br1	119.4 (3)
O1—Cu1—O9	88.60 (11)	C7—C8—Br1	117.0 (3)
O6—Cu1—O9	96.73 (11)	C8—C9—C10	118.6 (4)
C5—N1—C2	121.4 (3)	C8—C9—H9	120.7
C5—N1—Cu1	126.6 (3)	C10—C9—H9	120.7
C2—N1—Cu1	111.5 (2)	C11—C10—C9	120.9 (4)
C12—N2—C13	121.9 (4)	C11—C10—Br2	120.1 (3)
C12—N2—C14	121.1 (4)	C9—C10—Br2	118.9 (3)
C13—N2—C14	117.0 (3)	C10—C11—C6	120.4 (4)
C15—N3—C17	121.4 (5)	C10—C11—H11	119.8
C15—N3—C16	121.7 (5)	C6—C11—H11	119.8
C17—N3—C16	117.0 (5)	O6—C12—N2	124.5 (4)
C1—O1—Cu1	115.0 (3)	O6—C12—H12	117.8
C4—O4—H4	109.5	N2—C12—H12	117.8
C7—O5—Cu1	128.1 (2)	N2—C13—H13A	109.5
C12—O6—Cu1	121.9 (3)	N2—C13—H13B	109.5
H18—O8—H19	106.6	H13A—C13—H13B	109.5
Cu1—O9—H20	114.0	N2—C13—H13C	109.5
Cu1—O9—H21	98.3	H13A—C13—H13C	109.5
H20—O9—H21	107.2	H13B—C13—H13C	109.5
O2—C1—O1	124.7 (4)	N2—C14—H14A	109.5
O2—C1—C2	118.8 (3)	N2—C14—H14B	109.5
O1—C1—C2	116.2 (3)	H14A—C14—H14B	109.5
N1—C2—C3	116.8 (3)	N2—C14—H14C	109.5
N1—C2—C1	108.4 (3)	H14A—C14—H14C	109.5
C3—C2—C1	113.9 (3)	H14B—C14—H14C	109.5
N1—C2—H2	105.6	O7—C15—N3	125.9 (6)
C3—C2—H2	105.6	O7—C15—H15	117.1
C1—C2—H2	105.6	N3—C15—H15	117.1
C4—C3—C2	115.5 (3)	N3—C16—H16A	109.5
C4—C3—H3A	108.4	N3—C16—H16B	109.5
C2—C3—H3A	108.4	H16A—C16—H16B	109.5
C4—C3—H3B	108.4	N3—C16—H16C	109.5
C2—C3—H3B	108.4	H16A—C16—H16C	109.5
H3A—C3—H3B	107.5	H16B—C16—H16C	109.5
O3—C4—O4	123.6 (4)	N3—C17—H17A	109.5
O3—C4—C3	125.2 (4)	N3—C17—H17B	109.5
O4—C4—C3	111.3 (4)	H17A—C17—H17B	109.5
N1—C5—C6	125.1 (3)	N3—C17—H17C	109.5
N1—C5—H5	117.4	H17A—C17—H17C	109.5
C6—C5—H5	117.4	H17B—C17—H17C	109.5

O5—Cu1—N1—C5	−0.2 (3)	C1—C2—C3—C4	−65.5 (4)
O1—Cu1—N1—C5	−171.9 (3)	C2—C3—C4—O3	5.9 (6)
O6—Cu1—N1—C5	−146.7 (12)	C2—C3—C4—O4	−175.0 (4)
O9—Cu1—N1—C5	99.1 (3)	C2—N1—C5—C6	174.1 (3)
O5—Cu1—N1—C2	−171.9 (2)	Cu1—N1—C5—C6	3.2 (5)
O1—Cu1—N1—C2	16.4 (2)	N1—C5—C6—C11	177.3 (4)
O6—Cu1—N1—C2	41.6 (14)	N1—C5—C6—C7	−3.0 (6)
O9—Cu1—N1—C2	−72.6 (2)	Cu1—O5—C7—C8	−175.5 (3)
O5—Cu1—O1—C1	−86.2 (8)	Cu1—O5—C7—C6	4.6 (5)
N1—Cu1—O1—C1	−7.0 (3)	C11—C6—C7—O5	178.6 (3)
O6—Cu1—O1—C1	175.2 (3)	C5—C6—C7—O5	−1.0 (6)
O9—Cu1—O1—C1	78.5 (3)	C11—C6—C7—C8	−1.3 (5)
N1—Cu1—O5—C7	−3.6 (3)	C5—C6—C7—C8	179.1 (3)
O1—Cu1—O5—C7	74.9 (9)	O5—C7—C8—C9	−178.1 (4)
O6—Cu1—O5—C7	173.5 (3)	C6—C7—C8—C9	1.8 (5)
O9—Cu1—O5—C7	−89.5 (3)	O5—C7—C8—Br1	2.8 (5)
O5—Cu1—O6—C12	4.6 (3)	C6—C7—C8—Br1	−177.3 (3)
N1—Cu1—O6—C12	151.2 (13)	C7—C8—C9—C10	−2.2 (6)
O1—Cu1—O6—C12	176.2 (3)	Br1—C8—C9—C10	176.9 (3)
O9—Cu1—O6—C12	−95.1 (3)	C8—C9—C10—C11	2.1 (6)
Cu1—O1—C1—O2	−179.4 (3)	C8—C9—C10—Br2	−178.2 (3)
Cu1—O1—C1—C2	−4.2 (4)	C9—C10—C11—C6	−1.7 (6)
C5—N1—C2—C3	36.1 (5)	Br2—C10—C11—C6	178.6 (3)
Cu1—N1—C2—C3	−151.8 (3)	C7—C6—C11—C10	1.3 (6)
C5—N1—C2—C1	166.3 (3)	C5—C6—C11—C10	−179.1 (4)
Cu1—N1—C2—C1	−21.6 (3)	Cu1—O6—C12—N2	175.0 (3)
O2—C1—C2—N1	−167.5 (3)	C13—N2—C12—O6	3.3 (6)
O1—C1—C2—N1	17.0 (4)	C14—N2—C12—O6	−176.1 (4)
O2—C1—C2—C3	−35.7 (5)	C17—N3—C15—O7	−2.2 (10)
O1—C1—C2—C3	148.8 (3)	C16—N3—C15—O7	176.9 (6)
N1—C2—C3—C4	62.1 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O7ⁱ	0.82	1.76	2.565 (5)	169
O8—H18···O2ⁱⁱ	0.85	1.93	2.780 (4)	176
O8—H19···O8ⁱⁱⁱ	0.85	2.04	2.889 (3)	175
O9—H20···O8^iv	0.85	2.06	2.904 (4)	170
O9—H21···O1^v	0.85	2.28	3.116 (4)	167
C3—H3A···Br1^vi	0.97	3.13	3.605 (2)	112

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

Experimental details

Crystal data
Chemical formula	[Cu(C₁₁H₇Br₂NO₅)(C₃H₇NO)(H₂O)]·C₃H₇NO·H₂O
M_r	638.76
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	46.176 (3), 5.1633 (19), 21.793 (2)
β (°)	116.186 (4)
V (Å³)	4662.6 (18)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	4.42
Crystal size (mm)	0.56 × 0.10 × 0.07

Data collection
Diffractometer	Bruker SMART 1K CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2002)
T_min, T_max	0.191, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	11320, 4091, 3197
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.087, 1.04
No. of reflections	4091
No. of parameters	290
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.34

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.

Selected geometric parameters (Å, º) top

Cu1—O5	1.887 (3)	Cu1—O6	1.969 (3)
Cu1—N1	1.916 (3)	Cu1—O9	2.556 (3)
Cu1—O1	1.950 (3)

O5—Cu1—N1	93.51 (12)	O1—Cu1—O6	90.42 (11)
O5—Cu1—O1	171.55 (12)	O5—Cu1—O9	99.55 (11)
N1—Cu1—O1	84.86 (12)	N1—Cu1—O9	85.39 (11)
O5—Cu1—O6	90.85 (11)	O1—Cu1—O9	88.60 (11)
N1—Cu1—O6	174.78 (12)	O6—Cu1—O9	96.73 (11)