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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 9| September 2015| Pages m171-m172
https://doi.org/10.1107/S2056989015015194

Crystal structure of bis­­(μ2-tetra­bromo­phthalato-κ2O1:O2)bis­[aqua(N,N,N′,N′-tetra­methyl­ethane-1,2-di­amine-κ2N,N′)copper(II)]

CROSSMARK_Color_square_no_text.svg
Luis Manuel Tobón-Trujillo,a Luis Felipe Villanueva-Sánchez,a Diego Martínez-Oteroa and Alejandro Dorazco-Gonzáleza*

aCentro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Instituto de Química, Universidad Nacional Autónoma de México, Carretera Toluca-Atlacomulco, Km 14.5 CP 50200 Toluca, Estado de México, México
*Correspondence e-mail: adg@unam.mx

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 12 August 2015; accepted 14 August 2015; online 22 August 2015)

In the title complex, [Cu2(C8Br4O4)2(C6H16N2)2(H2O)2], the CuII cation is chelated by a tetra­methyl­ethane-1,2-di­amine ligand and coordinated by a water mol­ecule as well as bridged by two tetra­bromo­phthalate anions in a distorted O3N2 trigonal–bipyramidal geometry. The two symmetry-related tetra­bromo­phthalate anions bridge the two CuII cations, forming a centrosymmetric dinuclear complex in which the Cu⋯Cu separation is 5.054 (2) Å. Intra­molecular classic O—H⋯O hydrogen bonds and weak C—H⋯O hydrogen bonds occur in the dinuclear mol­ecule. In the crystal, the mol­ecules are linked by weak C—H⋯Br and C—H⋯O inter­actions into supra­molecular chains propagating along the b-axis direction.

CCDC reference: 1418832

Similar articles

1. Related literature

For the crystal structures of related copper(II) complexes with tetramethylethylen-1,2-diamine and carboxyl­ate ligands; see: Ene et al. (2009[Ene, C. D., Madalan, A. M., Maxim, C., Jurca, B., Avarvari, N. & Andruh, M. (2009). J. Am. Chem. Soc. 131, 4586-4587.]); Dorazco-González et al. (2013[Dorazco-González, A., Martínez-Vargas, S., Hernández-Ortega, S. & Valdés-Martínez, J. (2013). CrystEngComm, 15, 5961-5968.]); Liang et al. (2004[Liang, M., Liao, D.-Z., Jiang, Z.-H., Yan, S.-P. & Cheng, P. (2004). Inorg. Chem. Commun. 7, 173-175.]). For the synthesis of coordination compounds with one-dimensional polymeric structures, see: Hong & You (2004[Hong, C. S. & You, Y. S. (2004). Polyhedron, 23, 3043-3050.]); Colacio et al. (2009[Colacio, E., Aouryaghal, H., Mota, A. J., Cano, J., Sillanpää, R. & Rodríguez-Diéguez, A. (2009). CrystEngComm, 11, 2054-2064.]); Rodpun et al. (2015[Rodpun, K., Blackman, A. G., Gardiner, M. G., Tan, E. W., Meledandri, C. J. & Lucas, N. T. (2015). CrystEngComm, 17, 2974-2988.]); Yang et al. (2002[Yang, S.-Y., Long, L.-S., Wu, Z.-Y., Zhan, M.-X., Huang, R.-B. & Zheng, L.-S. (2002). Transition Met. Chem. 27, 546-549.]). For their magnetic properties, see: Ene et al. (2009[Ene, C. D., Madalan, A. M., Maxim, C., Jurca, B., Avarvari, N. & Andruh, M. (2009). J. Am. Chem. Soc. 131, 4586-4587.]); Kozlevčar et al. (2004[Kozlevčar, B., Leban, I., Petrič, M., Petriček, S., Roubeau, O., Reedijk, J. & Šegedin, P. (2004). Inorg. Chim. Acta, 357, 4220-4230.]). For supra­molecular polymorphism, see: Dorazco-González et al. (2013[Dorazco-González, A., Martínez-Vargas, S., Hernández-Ortega, S. & Valdés-Martínez, J. (2013). CrystEngComm, 15, 5961-5968.]); Stibrany et al. (2009[Stibrany, R. T. (2009). J. Chem. Crystallogr. 39, 719-722.]); Aakeröy et al. (2003[Aakeröy, C. B., Beatty, A. M., Desper, J., O'Shea, M. & Valdés-Martínez, J. (2003). Dalton Trans. pp. 3956-3962.]); Valdés-Martínez et al. (1993[Valdés-Martínez, J., Cervantes-Lee, F. & ter Haar, L. W. (1993). J. Appl. Phys. 74, 1918-1921.]); Julve et al. (1984[Julve, M., Faus, J., Verdaguer, M. & Gleizes, A. (1984). J. Am. Chem. Soc. 106, 8306-8308.]). For mol­ecular recognition and sensing; see: Dorazco-González & Yatsimirsky (2010[Dorazco-González, A. & Yatsimirsky, A. K. (2010). Inorg. Chim. Acta, 363, 270-274.]); Mendy et al. (2010[Mendy, J. S., Saeed, M. A., Fronczek, F. R., Powell, D. R. & Hossain, A. (2010). Inorg. Chem. 49, 7223-7225.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • [Cu2(C8Br4O4)2(C6H16N2)2(H2O)2]

  • Mr = 1354.97

  • Monoclinic, P 21 /n

  • a = 9.0961 (2) Å

  • b = 9.2281 (2) Å

  • c = 24.4026 (7) Å

  • β = 95.4910 (6)°

  • V = 2038.95 (9) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 8.94 mm−1

  • T = 100 K

  • 0.25 × 0.15 × 0.08 mm

2.2. Data collection

  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2012[Bruker (2012). APEX2, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA.]) Tmin = 0.442, Tmax = 0.745

  • 17394 measured reflections

  • 3739 independent reflections

  • 3547 reflections with I > 2σ(I)

  • Rint = 0.019

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.016

  • wR(F2) = 0.039

  • S = 1.07

  • 3739 reflections

  • 245 parameters

  • 2 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.80 e Å−3

  • Δρmin = −0.41 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O5—H5A⋯O2 0.81 (2) 1.87 (2) 2.649 (2) 161 (2)
O5—H5B⋯O4i 0.82 (2) 1.83 (2) 2.630 (2) 167 (3)
C10—H10A⋯Br4ii 0.99 2.84 3.729 (3) 150
C11—H11C⋯O4 0.98 2.40 3.376 (3) 179
C13—H13A⋯O4iii 0.98 2.58 3.506 (3) 158
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x-1, y-1, z; (iii) x-1, y, z.

Data collection: APEX2 (Bruker, 2012[Bruker (2012). APEX2, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2012[Bruker (2012). APEX2, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 1418832

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989015015194/xu5866sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015015194/xu5866Isup2.hkl

checkCIF report


Introduction top

The self-assembly of metal complexes with benzene-multi­carboxyl­ate ligands remains an active area in coordination chemistry especially with copper due to the very wide structural diversity and inter­esting properties in magnetism, host-guest systems, porous material (Ene et al., 2009; Dorazco-González et al., 2013; Liang et al., 2004). Dinuclear copper(II) compounds have been used in magnetism, as biomimetic active sites in bioinorganic chemistry and in the design and synthesis of metallic networks (Lu et al., 2004). Herein we present a dinuclear copper complex synthesised by self-assembly between copper perchlorate, a aliphatic di­amine (tmen) and a bulky benzendi­carboxyl­ate (tetra­bromo­phthalate). The tittle compound represents the first example of copper complex with tetra­bromo­phthalate.

Experimental top

Compound. Cu(ClO4)2.6H2O (0.1 mmol, 0.037 g) was added directly to a solution of tmen (0.1 mmol) in metanol-water solution 1:1 (8 mL). Then the dianion of tetra­bromo­phthalic acid (0.1 mmol, 0.055 g) in methanol-water solution 1:1 again (12 mL) was slowly added with stirring at room temperature, and a slight warming at 50 °C for 3 minutes.

Synthesis and crystallization top

Blue deep suitable crystals for diffraction X-ray were grown directly from solution by slow evaporation during 5 days. IR(KBr pellet), 3012 (w), 2971 (w), 2947 (w), 1741 (s), 1606 (m), 1396 (m), 1504 (w), 1459 (w), 1371 (s), 1315 (m), 1213 (m), 1096 (w), 1018 (w), 951 (w), 867 (w), 805 (w), 765 (w), 733 (w), 558 (w), 525 (w).

Refinement top

Water H atoms were placed in a difference Fourier map and positional parameters were refined, Uiso(H) = 1.2Ueq(O). Other H atoms were placed in calculated positions with C—H = 0.98–0.99 Å and refined in riding mode, Uiso(H) = 1.2Ueq(C) for methyl­ene H atoms and 1.5Ueq(C) for methyl H atoms.

Results and discussion top

The reaction between the aqua-complex [Cu(tmen)(H2O)x](ClO4)2 and potassium salt of tetra­bromo­phthalate in mixture ethanol gives the title compound in good yield (>94 %) as blue suitable crystals for X ray diffraction. The single-crystal X-ray analysis reveals that the compound is a neutral dinuclear centro-symmetric copper (II) complex which crystallizes in monoclinic crystal system, space group P21/n (Figure 1). The asymmetric unit contains a five-coordinate copper atom [Cu(N2O3)] with two sites occupied by di­amine and three sites by oxygen atoms from two carboxyl­ate groups and one molecule of water. The Addison tau-parameter has been used to describe the distortion around coordination geometry, τ = (difference between two largest angles/60 for five-coordinated metal centers allows the distinction between trigonal-bipyramidal (ideally τ = 1) and square-pyramidal (ideally τ = 0). In this context, the coordination geometry of complex is distorted trigonal-bypiramide, τ = 0.68. The distance Cu ··· Cu is 5.054 (2) Å and a macrocycle is formed by 14 atoms containing two TBr-phthalate-bridge ligands. The combination of copper(II) with multi-carb­oxy­lic acids has formed one of the largest subgroups in metal-organic compounds and despite this there are few examples of coordination complex with 1,2,3,4,-tetra­halogenated benzenes among these only with tetra­chloro­phthalate have been reported (Hong & You, 2004; Yang et al., 2002). The present compound represents the first example with tetra­bromo­phthalate.

Related literature top

For the crystal structures of related copper(II) complexes with tetramethylethylene and carboxylate ligands; see: Ene et al. (2009); Dorazco-González et al. (2013); Liang et al. (2004). For the synthesis of one-dimensional coordination polymers, see: Hong & You (2004); Colacio et al. (2009); Rodpun et al. (2015); Yang et al. (2002). For their magnetic properties, see: Ene et al. (2009); Kozlevčar et al. (2004). For supramolecular polymorphism, see: Dorazco-González et al. (2013); Stibrany et al. (2009); Aakeröy et al. (2003); Valdés-Martínez et al. (1993); Julve et al. (1984). For molecular recognition and sensing; see: Dorazco-González & Yatsimirsky (2010); Mendy et al. (2010).

Structure description top

The self-assembly of metal complexes with benzene-multi­carboxyl­ate ligands remains an active area in coordination chemistry especially with copper due to the very wide structural diversity and inter­esting properties in magnetism, host-guest systems, porous material (Ene et al., 2009; Dorazco-González et al., 2013; Liang et al., 2004). Dinuclear copper(II) compounds have been used in magnetism, as biomimetic active sites in bioinorganic chemistry and in the design and synthesis of metallic networks (Lu et al., 2004). Herein we present a dinuclear copper complex synthesised by self-assembly between copper perchlorate, a aliphatic di­amine (tmen) and a bulky benzendi­carboxyl­ate (tetra­bromo­phthalate). The tittle compound represents the first example of copper complex with tetra­bromo­phthalate.

Compound. Cu(ClO4)2.6H2O (0.1 mmol, 0.037 g) was added directly to a solution of tmen (0.1 mmol) in metanol-water solution 1:1 (8 mL). Then the dianion of tetra­bromo­phthalic acid (0.1 mmol, 0.055 g) in methanol-water solution 1:1 again (12 mL) was slowly added with stirring at room temperature, and a slight warming at 50 °C for 3 minutes.

The reaction between the aqua-complex [Cu(tmen)(H2O)x](ClO4)2 and potassium salt of tetra­bromo­phthalate in mixture ethanol gives the title compound in good yield (>94 %) as blue suitable crystals for X ray diffraction. The single-crystal X-ray analysis reveals that the compound is a neutral dinuclear centro-symmetric copper (II) complex which crystallizes in monoclinic crystal system, space group P21/n (Figure 1). The asymmetric unit contains a five-coordinate copper atom [Cu(N2O3)] with two sites occupied by di­amine and three sites by oxygen atoms from two carboxyl­ate groups and one molecule of water. The Addison tau-parameter has been used to describe the distortion around coordination geometry, τ = (difference between two largest angles/60 for five-coordinated metal centers allows the distinction between trigonal-bipyramidal (ideally τ = 1) and square-pyramidal (ideally τ = 0). In this context, the coordination geometry of complex is distorted trigonal-bypiramide, τ = 0.68. The distance Cu ··· Cu is 5.054 (2) Å and a macrocycle is formed by 14 atoms containing two TBr-phthalate-bridge ligands. The combination of copper(II) with multi-carb­oxy­lic acids has formed one of the largest subgroups in metal-organic compounds and despite this there are few examples of coordination complex with 1,2,3,4,-tetra­halogenated benzenes among these only with tetra­chloro­phthalate have been reported (Hong & You, 2004; Yang et al., 2002). The present compound represents the first example with tetra­bromo­phthalate.

For the crystal structures of related copper(II) complexes with tetramethylethylene and carboxylate ligands; see: Ene et al. (2009); Dorazco-González et al. (2013); Liang et al. (2004). For the synthesis of one-dimensional coordination polymers, see: Hong & You (2004); Colacio et al. (2009); Rodpun et al. (2015); Yang et al. (2002). For their magnetic properties, see: Ene et al. (2009); Kozlevčar et al. (2004). For supramolecular polymorphism, see: Dorazco-González et al. (2013); Stibrany et al. (2009); Aakeröy et al. (2003); Valdés-Martínez et al. (1993); Julve et al. (1984). For molecular recognition and sensing; see: Dorazco-González & Yatsimirsky (2010); Mendy et al. (2010).

Synthesis and crystallization top

Blue deep suitable crystals for diffraction X-ray were grown directly from solution by slow evaporation during 5 days. IR(KBr pellet), 3012 (w), 2971 (w), 2947 (w), 1741 (s), 1606 (m), 1396 (m), 1504 (w), 1459 (w), 1371 (s), 1315 (m), 1213 (m), 1096 (w), 1018 (w), 951 (w), 867 (w), 805 (w), 765 (w), 733 (w), 558 (w), 525 (w).

Refinement details top

Water H atoms were placed in a difference Fourier map and positional parameters were refined, Uiso(H) = 1.2Ueq(O). Other H atoms were placed in calculated positions with C—H = 0.98–0.99 Å and refined in riding mode, Uiso(H) = 1.2Ueq(C) for methyl­ene H atoms and 1.5Ueq(C) for methyl H atoms.

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure with displacement ellipsoids drawn at the 30% probability level and H atoms shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. View of interactions in the crystal.
Bis(µ2-tetrabromophthalato-κ2O1:O2)bis[aqua(N,N,N',N'-tetramethylethane-1,2-diamine-κ2N,N')copper(II)] top
Crystal data top
[Cu2(C8Br4O4)2(C6H16N2)2(H2O)2]F(000) = 1300
Mr = 1354.97Dx = 2.207 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 9.0961 (2) ÅCell parameters from 9880 reflections
b = 9.2281 (2) Åθ = 2.4–25.7°
c = 24.4026 (7) ŵ = 8.94 mm−1
β = 95.4910 (6)°T = 100 K
V = 2038.95 (9) Å3Prism, blue
Z = 20.25 × 0.15 × 0.08 mm
Data collection top
Bruker APEXII CCD
diffractometer		3739 independent reflections
Radiation source: Incoatec ImuS3547 reflections with I > 2σ(I)
Mirrors monochromatorRint = 0.019
ω scansθmax = 25.4°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2012)		h = −10→10
Tmin = 0.442, Tmax = 0.745k = −11→11
17394 measured reflectionsl = −29→29
Refinement top
Refinement on F22 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.016H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.039 w = 1/[σ2(Fo2) + (0.0162P)2 + 2.4857P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.002
3739 reflectionsΔρmax = 0.80 e Å−3
245 parametersΔρmin = −0.41 e Å−3
Crystal data top
[Cu2(C8Br4O4)2(C6H16N2)2(H2O)2]V = 2038.95 (9) Å3
Mr = 1354.97Z = 2
Monoclinic, P21/nMo Kα radiation
a = 9.0961 (2) ŵ = 8.94 mm−1
b = 9.2281 (2) ÅT = 100 K
c = 24.4026 (7) Å0.25 × 0.15 × 0.08 mm
β = 95.4910 (6)°
Data collection top
Bruker APEXII CCD
diffractometer		3739 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2012)		3547 reflections with I > 2σ(I)
Tmin = 0.442, Tmax = 0.745Rint = 0.019
17394 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0162 restraints
wR(F2) = 0.039H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.80 e Å−3
3739 reflectionsΔρmin = −0.41 e Å−3
245 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.34950 (2)0.30336 (3)0.71377 (2)0.01607 (6)
Br20.62992 (3)0.47283 (3)0.78249 (2)0.02118 (6)
Br30.95418 (3)0.47738 (3)0.73268 (2)0.01934 (6)
Br41.00627 (2)0.27574 (3)0.62483 (2)0.01671 (6)
Cu10.32727 (3)−0.12890 (3)0.55897 (2)0.01122 (6)
O10.45257 (16)0.02014 (16)0.59851 (6)0.0143 (3)
O20.32220 (16)0.22748 (16)0.58559 (6)0.0135 (3)
O30.65378 (16)0.19336 (16)0.52428 (6)0.0132 (3)
O40.79787 (17)0.02815 (16)0.57131 (6)0.0144 (3)
O50.17319 (17)0.01324 (17)0.53376 (6)0.0133 (3)
H5A0.205 (3)0.091 (2)0.5454 (10)0.016*
H5B0.179 (3)0.014 (3)0.5006 (7)0.016*
N10.4780 (2)−0.2831 (2)0.58485 (7)0.0153 (4)
N20.1667 (2)−0.2787 (2)0.57861 (8)0.0180 (4)
C10.5567 (2)0.2309 (2)0.63834 (8)0.0102 (4)
C20.5382 (2)0.3046 (2)0.68693 (8)0.0108 (4)
C30.6563 (2)0.3755 (2)0.71631 (8)0.0119 (4)
C40.7951 (2)0.3723 (2)0.69622 (8)0.0123 (4)
C50.8155 (2)0.2926 (2)0.64905 (8)0.0114 (4)
C60.6979 (2)0.2221 (2)0.62005 (8)0.0101 (4)
C70.4303 (2)0.1547 (2)0.60456 (8)0.0104 (4)
C80.7190 (2)0.1388 (2)0.56745 (8)0.0112 (4)
C90.3941 (3)−0.4200 (2)0.57551 (10)0.0206 (5)
H9A0.4525−0.50170.59250.025*
H9B0.3757−0.43880.53550.025*
C100.2483 (3)−0.4091 (3)0.60056 (11)0.0267 (6)
H10A0.1885−0.49700.59150.032*
H10B0.2665−0.40220.64110.032*
C110.6075 (3)−0.2849 (3)0.55284 (11)0.0221 (5)
H11A0.5747−0.29790.51370.033*
H11B0.6728−0.36510.56550.033*
H11C0.6611−0.19310.55810.033*
C120.5316 (3)−0.2652 (3)0.64386 (10)0.0295 (6)
H12A0.5925−0.17760.64850.044*
H12B0.5908−0.34970.65640.044*
H12C0.4470−0.25640.66570.044*
C130.0750 (3)−0.2171 (3)0.61946 (10)0.0270 (6)
H13A0.0211−0.13270.60360.040*
H13B0.1384−0.18740.65230.040*
H13C0.0045−0.29030.62970.040*
C140.0693 (3)−0.3163 (3)0.52836 (10)0.0244 (5)
H14A0.0251−0.22770.51190.037*
H14B−0.0091−0.38150.53810.037*
H14C0.1275−0.36440.50190.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.01284 (11)0.02352 (12)0.01199 (11)0.00231 (9)0.00185 (8)−0.00263 (9)
Br20.02459 (13)0.02531 (13)0.01399 (11)−0.00390 (10)0.00359 (9)−0.01160 (9)
Br30.02013 (12)0.02323 (13)0.01411 (11)−0.01075 (9)−0.00115 (8)−0.00597 (9)
Br40.01220 (11)0.02355 (13)0.01461 (11)−0.00571 (9)0.00253 (8)−0.00292 (9)
Cu10.01308 (13)0.00842 (13)0.01167 (13)−0.00056 (10)−0.00133 (10)−0.00121 (10)
O10.0144 (8)0.0097 (8)0.0178 (8)−0.0008 (6)−0.0039 (6)−0.0018 (6)
O20.0123 (8)0.0125 (8)0.0151 (8)0.0011 (6)−0.0019 (6)−0.0023 (6)
O30.0172 (8)0.0142 (8)0.0080 (7)0.0012 (6)0.0002 (6)−0.0017 (6)
O40.0168 (8)0.0129 (8)0.0130 (7)0.0032 (6)−0.0005 (6)−0.0012 (6)
O50.0160 (8)0.0127 (8)0.0109 (7)−0.0013 (6)−0.0006 (6)−0.0043 (6)
N10.0210 (10)0.0108 (9)0.0136 (9)−0.0004 (8)−0.0011 (7)0.0003 (7)
N20.0196 (10)0.0167 (10)0.0185 (10)−0.0029 (8)0.0052 (8)0.0036 (8)
C10.0138 (10)0.0060 (10)0.0103 (10)0.0006 (8)−0.0015 (8)0.0030 (8)
C20.0125 (10)0.0084 (10)0.0116 (10)0.0017 (8)0.0023 (8)0.0020 (8)
C30.0190 (11)0.0095 (10)0.0070 (10)0.0005 (9)0.0003 (8)−0.0012 (8)
C40.0160 (11)0.0100 (10)0.0100 (10)−0.0037 (9)−0.0040 (8)0.0007 (8)
C50.0131 (10)0.0115 (10)0.0100 (10)−0.0017 (8)0.0032 (8)0.0027 (8)
C60.0148 (11)0.0084 (10)0.0069 (10)0.0001 (8)−0.0003 (8)0.0031 (8)
C70.0122 (10)0.0117 (11)0.0074 (9)−0.0017 (8)0.0022 (8)−0.0004 (8)
C80.0104 (10)0.0117 (11)0.0116 (10)−0.0047 (9)0.0025 (8)−0.0009 (8)
C90.0255 (13)0.0097 (11)0.0260 (13)−0.0008 (10)0.0003 (10)0.0021 (9)
C100.0288 (14)0.0165 (12)0.0357 (15)−0.0019 (11)0.0077 (11)0.0117 (11)
C110.0169 (12)0.0180 (12)0.0311 (14)0.0039 (10)0.0009 (10)0.0069 (10)
C120.0426 (16)0.0238 (14)0.0194 (13)0.0077 (12)−0.0113 (11)0.0013 (10)
C130.0276 (14)0.0328 (15)0.0228 (13)0.0022 (12)0.0140 (11)0.0060 (11)
C140.0196 (12)0.0228 (13)0.0307 (14)−0.0104 (10)0.0010 (10)−0.0042 (11)
Geometric parameters (Å, º) top
Br1—C21.895 (2)N1—C91.482 (3)
Br2—C31.883 (2)N1—C121.485 (3)
Br3—C41.892 (2)N2—C131.473 (3)
Br4—C51.893 (2)N2—C141.484 (3)
Cu1—O51.9744 (16)N2—C101.487 (3)
Cu1—O11.9776 (15)C1—C21.391 (3)
Cu1—N12.0340 (19)C1—C61.402 (3)
Cu1—N22.0995 (19)C1—C71.521 (3)
Cu1—O3i2.1396 (14)C2—C31.396 (3)
O1—C71.269 (3)C3—C41.398 (3)
O2—C71.243 (3)C4—C51.393 (3)
O3—C81.263 (3)C5—C61.387 (3)
O3—Cu1i2.1396 (14)C6—C81.524 (3)
O4—C81.246 (3)C9—C101.516 (3)
N1—C111.475 (3)
O5—Cu1—O192.80 (6)C2—C1—C7122.73 (19)
O5—Cu1—N1177.14 (7)C6—C1—C7117.98 (18)
O1—Cu1—N189.71 (7)C1—C2—C3121.13 (19)
O5—Cu1—N291.13 (7)C1—C2—Br1118.64 (16)
O1—Cu1—N2136.68 (7)C3—C2—Br1120.21 (16)
N1—Cu1—N286.10 (8)C2—C3—C4119.12 (19)
O5—Cu1—O3i90.46 (6)C2—C3—Br2120.61 (16)
O1—Cu1—O3i124.17 (6)C4—C3—Br2120.27 (15)
N1—Cu1—O3i89.26 (7)C5—C4—C3119.80 (19)
N2—Cu1—O3i98.90 (7)C5—C4—Br3120.18 (16)
C7—O1—Cu1130.25 (14)C3—C4—Br3120.02 (15)
C8—O3—Cu1i127.37 (14)C6—C5—C4120.80 (19)
C11—N1—C9109.53 (18)C6—C5—Br4119.17 (16)
C11—N1—C12108.07 (19)C4—C5—Br4120.01 (16)
C9—N1—C12111.12 (19)C5—C6—C1119.73 (19)
C11—N1—Cu1113.14 (14)C5—C6—C8120.89 (19)
C9—N1—Cu1103.09 (14)C1—C6—C8119.35 (18)
C12—N1—Cu1111.86 (15)O2—C7—O1127.93 (19)
C13—N2—C14108.52 (19)O2—C7—C1118.85 (18)
C13—N2—C10111.32 (19)O1—C7—C1113.20 (18)
C14—N2—C10110.3 (2)O4—C8—O3127.65 (19)
C13—N2—Cu1110.61 (15)O4—C8—C6117.88 (18)
C14—N2—Cu1109.81 (14)O3—C8—C6114.47 (18)
C10—N2—Cu1106.31 (14)N1—C9—C10109.8 (2)
C2—C1—C6119.26 (19)N2—C10—C9109.52 (19)
C6—C1—C2—C33.0 (3)C2—C1—C6—C8178.75 (18)
C7—C1—C2—C3−178.78 (19)C7—C1—C6—C80.5 (3)
C6—C1—C2—Br1−175.50 (15)Cu1—O1—C7—O2−1.5 (3)
C7—C1—C2—Br12.7 (3)Cu1—O1—C7—C1−179.92 (13)
C1—C2—C3—C40.2 (3)C2—C1—C7—O260.4 (3)
Br1—C2—C3—C4178.71 (15)C6—C1—C7—O2−121.4 (2)
C1—C2—C3—Br2−179.24 (15)C2—C1—C7—O1−121.0 (2)
Br1—C2—C3—Br2−0.7 (2)C6—C1—C7—O157.2 (2)
C2—C3—C4—C5−3.3 (3)Cu1i—O3—C8—O4−6.9 (3)
Br2—C3—C4—C5176.09 (16)Cu1i—O3—C8—C6172.16 (13)
C2—C3—C4—Br3176.10 (15)C5—C6—C8—O466.3 (3)
Br2—C3—C4—Br3−4.5 (2)C1—C6—C8—O4−115.6 (2)
C3—C4—C5—C63.3 (3)C5—C6—C8—O3−112.8 (2)
Br3—C4—C5—C6−176.16 (16)C1—C6—C8—O365.3 (3)
C3—C4—C5—Br4−175.18 (16)C11—N1—C9—C10−170.79 (19)
Br3—C4—C5—Br45.4 (2)C12—N1—C9—C1069.9 (2)
C4—C5—C6—C10.0 (3)Cu1—N1—C9—C10−50.1 (2)
Br4—C5—C6—C1178.46 (15)C13—N2—C10—C9−148.7 (2)
C4—C5—C6—C8178.09 (19)C14—N2—C10—C990.8 (2)
Br4—C5—C6—C8−3.4 (3)Cu1—N2—C10—C9−28.2 (2)
C2—C1—C6—C5−3.1 (3)N1—C9—C10—N254.4 (3)
C7—C1—C6—C5178.62 (18)
Symmetry code: (i) −x+1, −y, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O20.81 (2)1.87 (2)2.649 (2)161 (2)
O5—H5B···O4i0.82 (2)1.83 (2)2.630 (2)167 (3)
C10—H10A···Br4ii0.992.843.729 (3)150
C11—H11C···O40.982.403.376 (3)179
C13—H13A···O4iii0.982.583.506 (3)158
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y−1, z; (iii) x−1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O20.81 (2)1.87 (2)2.649 (2)161 (2)
O5—H5B···O4i0.816 (18)1.829 (18)2.630 (2)167 (3)
C10—H10A···Br4ii0.992.843.729 (3)150
C11—H11C···O40.982.403.376 (3)179
C13—H13A···O4iii0.982.583.506 (3)158
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y−1, z; (iii) x−1, y, z.
 

Acknowledgements

We thank MSc Lizbeth Triana Cruz for technical assistence. The financial support of this research by CONACyT (CB239648) is gratefully acknowledged.

References

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ISSN: 2056-9890
Volume 71| Part 9| September 2015| Pages m171-m172
https://doi.org/10.1107/S2056989015015194
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