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In the structure of trans-bis­(ethanol-[kappa]O)tetra­kis­(1H-imidazole-[kappa]N3)copper(II) bis­[[mu]-N-(2-oxidobenzyl­idene)-D,L-glutamato]-[kappa]4O1,N,O2':O2';[kappa]4O2':O1,N,O2'-bis­[(1H-imidazole-[kappa]N3)cuprate(II)], [Cu(C3H4N2)4(C2H6O)2][Cu2(C15H14N3O5)2], both ions are located on centres of inversion. The cation is mononuclear, showing a distorted octa­hedral coordination, while the anion is a binuclear centrosymmetric dimer with a square-pyramidal copper(II) coordination. An extensive three-dimensional hydrogen-bonding network is formed between the ions. According to B3LYP/6-31G* calculations, the two equivalent components of the anion are in doublet states (spin density located mostly on CuII ions) and are coupled as a triplet, with only marginal preference over an open-shell singlet.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011204276X/sk3453sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827011204276X/sk3453Isup2.hkl
Contains datablock I

CCDC reference: 914645

Comment top

Recently, considerable attention has been devoted to copper(II) complexes containing Schiff bases derived from salicylaldehyde and various amino acids, and N- or O-donor neutral ligands; this is due to the interest from many fields of bioinorganic chemistry. Copper(II) complexes of tridentate Schiff bases derived from salicylaldehyde and glutamic acid containing water or diazoles as additional ligands have proved to be superoxide dismutase mimetics, the most efficient scavenger of O2-. radicals, [and to?] exhibit antimicrobial, anti-inflammatory and antipyretic activities. In our previous work (Andrezálová et al., 1998; Kohútová et al., 2000), the synthesis and properties of copper(II) complexes containing Schiff bases derived from salicylaldehyde and glutamic acid were described. The neutral ligands pyridine, pyrazole, imidazole and their derivatives were used. As stated earlier, based on IR spectra and then confirmed by single-crystal X-ray analysis (Krätsmár-Šmogrovič et al., 1991; Kožíšek et al., 1991; Sivý et al., 1994), one of the two carboxylic acid groups of glutamic acid remained uncoordinated even after complexation. From this group of substances the structures of (1-methylimidazole)(N-salicylidene-rac-glutamato)copper(II) (Langer et al., 2003), (2-methylimidazole)(N-salicylidene-rac-glutamato)copper(II) (Langer, Scholtzová et al., 2004), aqua(N-salicylidene-L-glutamato methyl ester)copper(II) monohydrate (Langer, Gyepesová et al., 2004) and dimeric (isoquinoline)(N-salicylidene-D,L-glutamato)copper(II) ethanol solvate (Langer et al., 2009) have been determined. In a continuation of these studies, a new complex trans-bis(ethanol)tetrakis(1H-imidazole)copper(II) bis[µ-N-(2-oxidobenzylidene)-D,L-glutamato]bis[(1H-imidazole)cuprate(II)], (I), is presented herein. In the structure of (I), both ions are located on centres of inversion (Fig. 1). This complex has quite spectacular structural features. The cation is mononuclear, while the anion is binuclear and compound (I) is a racemic complex. Racemic complexes are often observed even though optically active amino acids have been employed (for examples, see Kettmann et al., 1993; Sivý et al., 1994; Langer et al., 2003; Langer, Scholtzová et al., 2004).

The two CuII ions are located in different coordination polyhedra, as shown in Fig. 2. The mononuclear unit of the cation is formed by four imidazole ligands [Cu2—N distances = 2.0391 (12)–2.0628 (13) Å] and by two O atoms of ethanol molecules [Cu2—O = 2.6228 (13) Å]. The anion has square-pyramidal CuII coordination defined by a tridentate N-salicylidene-rac-glutamate Schiff base dianion and a neutral monodentate imidazole ligand bound in the basal plane. The axial position is occupied by a phenolic O atom from an adjacent glutamate ligand [Cu1—O3(-x, -y+1, -z+1) = 2.5305 (11) Å], forming a centrosymmetric dimer. The molecules are arranged in dimeric units in good agreement with the result found for other dimeric compounds of this type, e.g. dimeric (imidazole-κN3)(N-salicylidene-rac-alaninato-κ3O,N,O')copper(II), with a Cu—Oapical distance of 2.500 (3) Å (Warda, 1998) and dimeric (pyrazole-κN2)(N-salicylidene-2,2-dimethylglycinato-κ3O, N,O')copper(II) pyrazole solvate (Hill & Warda,1999), in which the apex of the pyramids are [is] occupied by the phenolate O atom from an adjacent chelate molecule at a distance of 2.605 (2) Å, thus building a centrosymmetric dimer. All equatorial distances involving CuII in (I) are in normal ranges, the most variable copper distance in this class of compounds being the apical one. A rich variety of axial distortions ranging from square-planar to square-pyramidal has been found. It may be one of the reasons for the diversity of interactions of these CuII complexes with biological systems, e.g. the structure of (1-methylimidazole)(N-salicylidene-rac-glutamato)copper(II) (Langer et al., 2003) adopts a square-planar copper coordination mode. Atoms N1A and N1B, together with their respective centrosymmetrically related partners [N1Ai and N1Bi; symmetry code: (i) -x + 2, -y, -z], coordinate in a plane around the Cu2 atom, which lies on a centre of symmetry. The Cu2—N1A and Cu2—N1B bond lengths in (I) (Table 1) are slightly longer than the Cu1—N2 bond length in the anion, which indicates different bond strengths. Both ethanol O atoms (O3C and O3Ci) interact weakly in axial positions with the Cu2 atom, at a distance of 2.6228 (13) Å. The cation displays a slightly distorted octahedral coordination. The ions are associated via hydrogen bonding (Table 2), thus forming a complicated three-dimensional network.

In order to understand some interesting features of the electronic structure of the title compound, the electronic structures for two chemically relevant models A and B were calculated at the B3LYP/6–31G* level using the GAUSSIAN98 (Frisch et al., 1998) and PC GAMESS (Granovsky, 2003) programs. Model A represents the bidental anion with both CH2–COO- groups removed and dangling bonds capped with H atoms. All H atoms were re-optimized at the B3LYP/6–31G* level. The purpose of this model is twofold: (i) to estimate the bonding energy of both Cu—O bonds and (ii) to understand the spin state of both subunits and the electronic configuration of the central Cu atom. The most stable spin state is a triplet, but energetically very close is an open-shell singlet (S2 = 1.005). The interaction energy of two identical doublet subunits is approximatelly 4 kcal mol-1 (BSSE corrected). From the NBO analysis (Glendening et al., 1993) it follows that the electronic configuration of both Cu atoms in the anion (both in triplet or open-shell singlet coupling) is 4 s0.373 d9.15. Model B consists of the cation with two CH2–COO- groups (representing two different anions) as hydrogen-bond acceptors for ethanol molecules. As in the previous case, all H atoms were re-optimized. The electronic configuration of the central Cu atom from NBO analysis is 4 s0.333 d9.14, i.e. only slightly different from that of the Cu atoms in the anion. The interaction energy of ethanol in this model (i.e. 1/2 of energy for removing both ethanol molecules) is approximatelly 23 kcal mol-1 (BSSE corrected). The calculated Cu2—O3C energy is 11 kcal mol-1; the HB energy for the EtOH–CH3COO- interaction is 18 kcal mol-1. This relatively large HB energy is due to the fact that the O2 atom possesses a large negative charge (the Mulliken charge is -0.62). Thus, ethanol serves as a bridge, which binds the cation and anion by a relatively strong hydrogen bond in addition to the ionic interaction. This implies that the presence of ethanol is important for building the crystal structure.

Related literature top

For related literature, see: Andrezálová et al. (1998); Frisch (1998); Glendening et al. (1993); Granovsky (2003); Hill & Warda (1999); Kettmann et al. (1993); Kožíšek et al. (1991); Kohútová et al. (2000); Krätsmár-Šmogrovič, Pavelčík, Soldánová, Sivý, Seressová & Žemlička (1991); Langer et al. (2003, 2009); Langer, Gyepesová, Scholtzová, Mach, Kohútová, Valent & Smrčok (2004); Langer, Scholtzová, Gyepesová, Kohútová & Valent (2004); Sivý et al. (1994); Warda (1998).

Experimental top

Crystals of (I) were prepared at room temperature by the reaction of [Cu(sal-L-glu)(H2O)2].H2O [where sal-L-glu is N-salicylidene-L-glutamate(2-)], with imidazole in ethanol solution in a 1:2 molar ratio. Crystals were obtained after a few days by slow evaporation of the solvent at room temperature. The crystals were filtered off and washed with a small amount of cooled ethanol and ether and were finally air dried.

Refinement top

Aromatic, primary and secondary H atoms were refined isotropically, with Uiso(H) = 1.2Ueq(C), and their positions were constrained to an ideal geometry using an appropriate riding model (C—H = 0.95 Å for aromatic, 1.00 Å for primary and 0.99 Å for secondary H atoms). For methyl groups, the C—C—H angles were kept fixed (109.5°), while the torsion angles were allowed to refine with the starting positions based on the circular Fourier synthesis averaged using the local threefold axis, with Uiso(H) = 1.5Ueq(C) and the C—H distances constrained to 0.98 Å. For the hydroxy group, the C—O—H angle was kept fixed (109.5°), while the torsion angle was allowed to refine with the starting positions based on the circular Fourier synthesis, with Uiso(H) = 1.5Ueq(O) and the O—H distance constrained to 0.84 Å.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003) and SADABS (Sheldrick, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A perspective drawing of the title compound, showing the atom-numbering scheme (a) for the cation [symmetry code: (i) -x+2, -y, -z] and (b) for the anion [unlabelled atoms are produced by symmetry code (-x, -y+1, -z+1)]. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The coordination polyhedra of the Cu atoms in (I). H atoms are shown as small spheres of arbitrary radii.
trans-bis(ethanol-κO)tetrakis(1H-imidazole- κN3)copper(II) bis[µ-N-(2-oxidobenzylidene)-D,L-glutamato]- κ4O1,N,O2':O2';κ4O2':O1,N,O2'-bis[(1H-imidazole- κN3)cuprate(II)] top
Crystal data top
[Cu(C3H4N2)4(C2H6O)2][Cu2(C15H14N3O5)2]Z = 1
Mr = 1187.67F(000) = 613
Triclinic, P1Dx = 1.494 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.0275 (1) ÅCell parameters from 8192 reflections
b = 9.9401 (1) Åθ = 2.1–30.5°
c = 16.8444 (1) ŵ = 1.27 mm1
α = 96.607 (1)°T = 173 K
β = 95.134 (1)°Needle, blue
γ = 96.394 (1)°0.60 × 0.12 × 0.09 mm
V = 1319.71 (2) Å3
Data collection top
Siemens SMART CCD area-detector
diffractometer
7695 independent reflections
Radiation source: fine-focus sealed tube6910 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
ω scansθmax = 30.5°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 1111
Tmin = 0.516, Tmax = 0.894k = 1413
19560 measured reflectionsl = 2323
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0487P)2 + 0.7014P]
where P = (Fo2 + 2Fc2)/3
7695 reflections(Δ/σ)max = 0.001
342 parametersΔρmax = 0.65 e Å3
0 restraintsΔρmin = 0.51 e Å3
Crystal data top
[Cu(C3H4N2)4(C2H6O)2][Cu2(C15H14N3O5)2]γ = 96.394 (1)°
Mr = 1187.67V = 1319.71 (2) Å3
Triclinic, P1Z = 1
a = 8.0275 (1) ÅMo Kα radiation
b = 9.9401 (1) ŵ = 1.27 mm1
c = 16.8444 (1) ÅT = 173 K
α = 96.607 (1)°0.60 × 0.12 × 0.09 mm
β = 95.134 (1)°
Data collection top
Siemens SMART CCD area-detector
diffractometer
7695 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
6910 reflections with I > 2σ(I)
Tmin = 0.516, Tmax = 0.894Rint = 0.026
19560 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.087H-atom parameters constrained
S = 1.00Δρmax = 0.65 e Å3
7695 reflectionsΔρmin = 0.51 e Å3
342 parameters
Special details top

Experimental. Data were collected at 173 K using a Siemens SMART CCD diffractometer equipped with LT-2 A cooling device. A full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal–to–detector distance of 3.97 cm, 30 s per frame. Preliminary orientation matrix was obtained from the first 100 frames using SMART (Bruker, 2003). The collected frames were integrated using the preliminary orientation matrix which was updated every 100 frames. Final cell parameters were obtained by refinement on the position of 8192 reflections with I>10σ(I) after integration of all the frames data using SAINT (Bruker, 2003).

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
xyzUiso*/Ueq
Cu10.13452 (2)0.630052 (16)0.479545 (10)0.01747 (5)
Cu21.00000.00000.00000.01931 (6)
O10.40911 (19)0.57001 (14)0.15490 (9)0.0419 (3)
O20.40280 (18)0.34096 (14)0.13837 (10)0.0425 (3)
O30.16929 (14)0.47814 (10)0.54060 (6)0.0206 (2)
O50.10670 (14)0.78228 (10)0.41445 (6)0.0221 (2)
O60.17486 (17)0.86298 (11)0.30070 (7)0.0297 (3)
N10.23993 (16)0.55297 (12)0.38624 (7)0.0178 (2)
N20.08240 (16)0.74564 (12)0.57708 (7)0.0192 (2)
N30.01714 (18)0.91090 (13)0.65249 (8)0.0235 (3)
H30.06410.98490.66620.028*
C10.34089 (18)0.45884 (14)0.38862 (9)0.0190 (3)
H10.40840.44620.34550.023*
C20.35872 (17)0.37114 (13)0.45233 (9)0.0182 (2)
C30.46818 (19)0.26835 (14)0.44106 (10)0.0224 (3)
H3A0.52500.26110.39390.027*
C40.4940 (2)0.17786 (15)0.49765 (11)0.0258 (3)
H40.56740.11010.48920.031*
C50.4085 (2)0.18953 (15)0.56764 (10)0.0261 (3)
H50.42320.12780.60600.031*
C60.3025 (2)0.29101 (15)0.58099 (9)0.0233 (3)
H60.24840.29780.62900.028*
C70.27345 (17)0.38493 (13)0.52395 (9)0.0182 (2)
C80.23665 (19)0.63546 (14)0.31764 (8)0.0191 (3)
H80.35370.65550.30250.023*
C90.11962 (19)0.56409 (15)0.24275 (9)0.0223 (3)
H9A0.00570.54080.25920.027*
H9B0.11030.62980.20320.027*
C100.17714 (19)0.43306 (15)0.20089 (9)0.0217 (3)
H10A0.08690.39040.15870.026*
H10B0.18890.36840.24100.026*
C110.34439 (19)0.45190 (15)0.16194 (9)0.0221 (3)
C120.1081 (2)0.72372 (15)0.65720 (9)0.0236 (3)
H120.15980.65050.67620.028*
C130.0463 (2)0.82577 (16)0.70441 (9)0.0270 (3)
H130.04710.83580.76120.032*
C140.0062 (2)0.85949 (15)0.57691 (9)0.0221 (3)
H140.02690.89860.53000.027*
C150.16902 (19)0.77178 (14)0.34626 (8)0.0189 (3)
N1A0.85635 (16)0.10789 (13)0.07061 (7)0.0205 (2)
N3A0.66783 (19)0.25775 (15)0.11300 (9)0.0304 (3)
H3A10.57750.31660.11320.036*
C2A0.7109 (2)0.19082 (17)0.05029 (10)0.0262 (3)
H2A0.64700.20130.00080.031*
C4A0.7912 (2)0.21658 (19)0.17611 (11)0.0318 (4)
H4A0.79500.24650.22770.038*
C5A0.9082 (2)0.12371 (17)0.14998 (9)0.0250 (3)
H5A1.00750.07810.18080.030*
N1B0.88269 (16)0.17106 (13)0.02825 (8)0.0209 (2)
N3B0.69987 (18)0.30377 (15)0.07838 (9)0.0290 (3)
H3B0.62030.33130.10680.035*
C2B0.7615 (2)0.18189 (17)0.07787 (10)0.0263 (3)
H2B0.72360.11270.10890.032*
C4B0.7850 (2)0.37652 (18)0.02618 (11)0.0327 (4)
H4B0.76870.46530.01370.039*
C5B0.8982 (2)0.29490 (17)0.00431 (11)0.0300 (3)
H5B0.97500.31890.04160.036*
O3C0.77625 (16)0.07884 (13)0.12461 (8)0.0313 (3)
H3C0.73790.16200.13210.047*
C1C0.5324 (3)0.0495 (3)0.22109 (13)0.0452 (5)
H1C10.60210.04520.26580.068*
H1C20.44110.00720.22820.068*
H1C30.48430.14420.21990.068*
C2C0.6408 (2)0.0028 (2)0.14211 (12)0.0348 (4)
H2C10.69040.09790.14420.042*
H2C20.56790.00390.09770.042*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02400 (9)0.01273 (8)0.01862 (9)0.00762 (6)0.00815 (6)0.00463 (6)
Cu20.02176 (12)0.01692 (11)0.02207 (12)0.00350 (9)0.01122 (9)0.00634 (9)
O10.0463 (8)0.0278 (6)0.0554 (9)0.0020 (6)0.0281 (7)0.0097 (6)
O20.0348 (7)0.0274 (6)0.0667 (10)0.0042 (5)0.0272 (7)0.0052 (6)
O30.0262 (5)0.0160 (4)0.0231 (5)0.0089 (4)0.0081 (4)0.0064 (4)
O50.0315 (6)0.0166 (5)0.0225 (5)0.0110 (4)0.0115 (4)0.0072 (4)
O60.0518 (7)0.0194 (5)0.0239 (5)0.0158 (5)0.0147 (5)0.0091 (4)
N10.0236 (6)0.0130 (5)0.0182 (5)0.0055 (4)0.0055 (4)0.0026 (4)
N20.0243 (6)0.0150 (5)0.0202 (5)0.0054 (4)0.0070 (4)0.0040 (4)
N30.0328 (7)0.0162 (5)0.0234 (6)0.0076 (5)0.0089 (5)0.0007 (4)
C10.0223 (6)0.0153 (6)0.0208 (6)0.0059 (5)0.0063 (5)0.0017 (5)
C20.0192 (6)0.0123 (5)0.0238 (6)0.0038 (5)0.0025 (5)0.0030 (5)
C30.0224 (7)0.0149 (6)0.0311 (7)0.0065 (5)0.0049 (6)0.0026 (5)
C40.0240 (7)0.0139 (6)0.0408 (9)0.0076 (5)0.0020 (6)0.0051 (6)
C50.0267 (7)0.0173 (6)0.0356 (8)0.0050 (5)0.0010 (6)0.0102 (6)
C60.0261 (7)0.0200 (6)0.0259 (7)0.0057 (5)0.0029 (5)0.0087 (5)
C70.0189 (6)0.0127 (5)0.0240 (6)0.0035 (5)0.0024 (5)0.0048 (5)
C80.0261 (7)0.0154 (6)0.0178 (6)0.0073 (5)0.0056 (5)0.0033 (5)
C90.0228 (7)0.0226 (7)0.0225 (7)0.0067 (5)0.0044 (5)0.0018 (5)
C100.0228 (7)0.0199 (6)0.0223 (6)0.0022 (5)0.0061 (5)0.0008 (5)
C110.0239 (7)0.0211 (6)0.0211 (6)0.0004 (5)0.0049 (5)0.0024 (5)
C120.0319 (8)0.0181 (6)0.0223 (7)0.0062 (6)0.0037 (6)0.0051 (5)
C130.0414 (9)0.0204 (7)0.0201 (7)0.0049 (6)0.0071 (6)0.0026 (5)
C140.0313 (7)0.0166 (6)0.0205 (6)0.0078 (5)0.0062 (5)0.0032 (5)
C150.0249 (7)0.0139 (6)0.0192 (6)0.0063 (5)0.0043 (5)0.0022 (5)
N1A0.0222 (6)0.0194 (5)0.0218 (6)0.0023 (4)0.0089 (4)0.0061 (4)
N3A0.0298 (7)0.0246 (6)0.0388 (8)0.0027 (5)0.0148 (6)0.0098 (6)
C2A0.0245 (7)0.0263 (7)0.0284 (7)0.0010 (6)0.0082 (6)0.0061 (6)
C4A0.0382 (9)0.0341 (9)0.0285 (8)0.0072 (7)0.0151 (7)0.0148 (7)
C5A0.0279 (7)0.0266 (7)0.0222 (7)0.0046 (6)0.0080 (6)0.0053 (5)
N1B0.0224 (6)0.0200 (6)0.0216 (6)0.0029 (4)0.0071 (4)0.0035 (4)
N3B0.0256 (6)0.0272 (7)0.0356 (7)0.0085 (5)0.0101 (5)0.0006 (6)
C2B0.0241 (7)0.0251 (7)0.0322 (8)0.0052 (6)0.0117 (6)0.0044 (6)
C4B0.0416 (10)0.0242 (7)0.0358 (9)0.0123 (7)0.0108 (7)0.0051 (6)
C5B0.0412 (9)0.0222 (7)0.0307 (8)0.0087 (6)0.0149 (7)0.0077 (6)
O3C0.0282 (6)0.0246 (6)0.0413 (7)0.0017 (5)0.0059 (5)0.0051 (5)
C1C0.0386 (10)0.0560 (13)0.0396 (10)0.0023 (9)0.0003 (8)0.0113 (9)
C2C0.0288 (8)0.0340 (9)0.0420 (10)0.0044 (7)0.0058 (7)0.0044 (7)
Geometric parameters (Å, º) top
Cu1—O31.9533 (10)C9—H9A0.9900
Cu1—N11.9694 (12)C9—H9B0.9900
Cu1—O51.9887 (10)C10—C111.549 (2)
Cu1—N21.9974 (12)C10—H10A0.9900
Cu2—N1A2.0391 (12)C10—H10B0.9900
Cu2—N1Ai2.0391 (12)C12—C131.380 (2)
Cu2—N1Bi2.0628 (13)C12—H120.9500
Cu2—N1B2.0628 (13)C13—H130.9500
O1—C111.2528 (19)C14—H140.9500
O2—C111.281 (2)N1A—C2A1.345 (2)
O3—C71.3383 (16)N1A—C5A1.396 (2)
O5—C151.2911 (17)N3A—C2A1.362 (2)
O6—C151.2531 (17)N3A—C4A1.378 (2)
N1—C11.3061 (18)N3A—H3A10.8800
N1—C81.4918 (17)C2A—H2A0.9500
N2—C141.3452 (18)C4A—C5A1.379 (2)
N2—C121.3926 (19)C4A—H4A0.9500
N3—C141.3533 (19)C5A—H5A0.9500
N3—C131.388 (2)N1B—C2B1.3432 (19)
N3—H30.8800N1B—C5B1.402 (2)
C1—C21.4653 (19)N3B—C2B1.358 (2)
C1—H10.9500N3B—C4B1.381 (2)
C2—C31.4274 (19)N3B—H3B0.8800
C2—C71.440 (2)C2B—H2B0.9500
C3—C41.401 (2)C4B—C5B1.379 (2)
C3—H3A0.9500C4B—H4B0.9500
C4—C51.416 (2)C5B—H5B0.9500
C4—H40.9500O3C—C2C1.456 (2)
C5—C61.402 (2)O3C—H3C0.8400
C5—H50.9500C1C—C2C1.527 (3)
C6—C71.4366 (19)C1C—H1C10.9800
C6—H60.9500C1C—H1C20.9800
C8—C91.553 (2)C1C—H1C30.9800
C8—C151.5569 (19)C2C—H2C10.9900
C8—H81.0000C2C—H2C20.9900
C9—C101.545 (2)
O3—Cu1—N194.15 (5)C11—C10—H10B108.3
O3—Cu1—O5177.53 (4)H10A—C10—H10B107.4
N1—Cu1—O583.52 (4)O1—C11—O2125.82 (15)
O3—Cu1—N291.78 (5)O1—C11—C10119.14 (14)
N1—Cu1—N2164.51 (5)O2—C11—C10115.03 (13)
O5—Cu1—N290.28 (5)C13—C12—N2108.89 (13)
N1A—Cu2—N1Ai180.0C13—C12—H12125.6
N1A—Cu2—N1Bi88.77 (5)N2—C12—H12125.6
N1Ai—Cu2—N1Bi91.23 (5)N3—C13—C12106.43 (13)
N1A—Cu2—N1B91.23 (5)N3—C13—H13126.8
N1Ai—Cu2—N1B88.77 (5)C12—C13—H13126.8
N1Bi—Cu2—N1B180.0N2—C14—N3110.98 (13)
C7—O3—Cu1125.14 (9)N2—C14—H14124.5
C15—O5—Cu1115.76 (9)N3—C14—H14124.5
C1—N1—C8119.38 (12)O6—C15—O5124.23 (13)
C1—N1—Cu1124.10 (10)O6—C15—C8117.82 (12)
C8—N1—Cu1114.46 (8)O5—C15—C8117.92 (12)
C14—N2—C12106.09 (12)C2A—N1A—C5A106.18 (13)
C14—N2—Cu1125.46 (10)C2A—N1A—Cu2129.31 (11)
C12—N2—Cu1128.38 (10)C5A—N1A—Cu2123.92 (10)
C14—N3—C13107.60 (12)C2A—N3A—C4A107.62 (14)
C14—N3—H3126.2C2A—N3A—H3A1126.2
C13—N3—H3126.2C4A—N3A—H3A1126.2
N1—C1—C2125.43 (13)N1A—C2A—N3A110.66 (15)
N1—C1—H1117.3N1A—C2A—H2A124.7
C2—C1—H1117.3N3A—C2A—H2A124.7
C3—C2—C7119.86 (13)C5A—C4A—N3A106.91 (14)
C3—C2—C1116.69 (13)C5A—C4A—H4A126.5
C7—C2—C1123.44 (12)N3A—C4A—H4A126.5
C4—C3—C2121.76 (14)C4A—C5A—N1A108.63 (15)
C4—C3—H3A119.1C4A—C5A—H5A125.7
C2—C3—H3A119.1N1A—C5A—H5A125.7
C3—C4—C5118.65 (13)C2B—N1B—C5B104.89 (13)
C3—C4—H4120.7C2B—N1B—Cu2126.15 (11)
C5—C4—H4120.7C5B—N1B—Cu2128.71 (10)
C6—C5—C4120.85 (14)C2B—N3B—C4B107.39 (14)
C6—C5—H5119.6C2B—N3B—H3B126.3
C4—C5—H5119.6C4B—N3B—H3B126.3
C5—C6—C7121.67 (14)N1B—C2B—N3B111.79 (14)
C5—C6—H6119.2N1B—C2B—H2B124.1
C7—C6—H6119.2N3B—C2B—H2B124.1
O3—C7—C6118.17 (13)C5B—C4B—N3B106.42 (15)
O3—C7—C2124.64 (12)C5B—C4B—H4B126.8
C6—C7—C2117.19 (12)N3B—C4B—H4B126.8
N1—C8—C9113.10 (12)C4B—C5B—N1B109.50 (15)
N1—C8—C15107.57 (11)C4B—C5B—H5B125.3
C9—C8—C15107.96 (11)N1B—C5B—H5B125.3
N1—C8—H8109.4C2C—O3C—H3C109.5
C9—C8—H8109.4C2C—C1C—H1C1109.5
C15—C8—H8109.4C2C—C1C—H1C2109.5
C10—C9—C8115.32 (12)H1C1—C1C—H1C2109.5
C10—C9—H9A108.4C2C—C1C—H1C3109.5
C8—C9—H9A108.4H1C1—C1C—H1C3109.5
C10—C9—H9B108.4H1C2—C1C—H1C3109.5
C8—C9—H9B108.4O3C—C2C—C1C113.49 (17)
H9A—C9—H9B107.5O3C—C2C—H2C1108.9
C9—C10—C11116.10 (12)C1C—C2C—H2C1108.9
C9—C10—H10A108.3O3C—C2C—H2C2108.9
C11—C10—H10A108.3C1C—C2C—H2C2108.9
C9—C10—H10B108.3H2C1—C2C—H2C2107.7
N1—Cu1—O3—C715.35 (12)C8—C9—C10—C1165.05 (17)
N2—Cu1—O3—C7150.33 (12)C9—C10—C11—O111.1 (2)
N1—Cu1—O5—C152.52 (11)C9—C10—C11—O2169.94 (15)
N2—Cu1—O5—C15163.26 (11)C14—N2—C12—C130.00 (18)
O3—Cu1—N1—C119.06 (12)Cu1—N2—C12—C13177.12 (11)
O5—Cu1—N1—C1160.14 (12)C14—N3—C13—C120.30 (19)
N2—Cu1—N1—C193.2 (2)N2—C12—C13—N30.18 (19)
O3—Cu1—N1—C8177.42 (10)C12—N2—C14—N30.20 (18)
O5—Cu1—N1—C83.39 (10)Cu1—N2—C14—N3177.42 (10)
N2—Cu1—N1—C870.4 (2)C13—N3—C14—N20.31 (19)
O3—Cu1—N2—C14163.51 (13)Cu1—O5—C15—O6174.04 (12)
N1—Cu1—N2—C1484.0 (2)Cu1—O5—C15—C87.78 (17)
O5—Cu1—N2—C1417.84 (13)N1—C8—C15—O6171.77 (13)
O3—Cu1—N2—C1213.09 (13)C9—C8—C15—O665.87 (17)
N1—Cu1—N2—C1299.4 (2)N1—C8—C15—O59.93 (18)
O5—Cu1—N2—C12165.56 (13)C9—C8—C15—O5112.43 (14)
C8—N1—C1—C2179.41 (13)N1Bi—Cu2—N1A—C2A85.74 (14)
Cu1—N1—C1—C216.6 (2)N1B—Cu2—N1A—C2A94.27 (14)
N1—C1—C2—C3176.04 (14)N1Bi—Cu2—N1A—C5A84.19 (12)
N1—C1—C2—C74.4 (2)N1B—Cu2—N1A—C5A95.81 (12)
C7—C2—C3—C40.9 (2)C5A—N1A—C2A—N3A0.30 (18)
C1—C2—C3—C4179.50 (14)Cu2—N1A—C2A—N3A171.61 (11)
C2—C3—C4—C50.1 (2)C4A—N3A—C2A—N1A0.3 (2)
C3—C4—C5—C61.2 (2)C2A—N3A—C4A—C5A0.2 (2)
C4—C5—C6—C71.3 (2)N3A—C4A—C5A—N1A0.01 (19)
Cu1—O3—C7—C6171.46 (10)C2A—N1A—C5A—C4A0.19 (18)
Cu1—O3—C7—C28.9 (2)Cu2—N1A—C5A—C4A172.09 (11)
C5—C6—C7—O3179.37 (14)N1A—Cu2—N1B—C2B1.01 (14)
C5—C6—C7—C20.3 (2)N1Ai—Cu2—N1B—C2B178.99 (14)
C3—C2—C7—O3179.57 (13)N1A—Cu2—N1B—C5B172.51 (14)
C1—C2—C7—O30.0 (2)N1Ai—Cu2—N1B—C5B7.49 (14)
C3—C2—C7—C60.8 (2)C5B—N1B—C2B—N3B0.21 (19)
C1—C2—C7—C6179.67 (13)Cu2—N1B—C2B—N3B174.57 (11)
C1—N1—C8—C983.97 (16)C4B—N3B—C2B—N1B0.1 (2)
Cu1—N1—C8—C9111.66 (11)C2B—N3B—C4B—C5B0.4 (2)
C1—N1—C8—C15156.90 (13)N3B—C4B—C5B—N1B0.5 (2)
Cu1—N1—C8—C157.47 (14)C2B—N1B—C5B—C4B0.5 (2)
N1—C8—C9—C1066.68 (16)Cu2—N1B—C5B—C4B174.13 (12)
C15—C8—C9—C10174.41 (12)
Symmetry code: (i) x+2, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3C—H3C···O2ii0.841.992.8064 (18)166
N3B—H3B···O20.881.882.7178 (19)158
N3—H3···O6iii0.881.892.7716 (16)176
N3A—H3A1···O1iv0.881.902.7370 (19)159
C2A—H2A···O2ii0.952.543.353 (2)144
C2B—H2B···N1A0.952.583.052 (2)111
C5A—H5A···O3Ci0.952.533.148 (2)123
C5A—H5A···O6v0.952.493.196 (2)131
C1C—H1C1···O6vi0.982.563.306 (3)133
C14—H14···O50.952.532.9629 (18)108
Symmetry codes: (i) x+2, y, z; (ii) x+1, y, z; (iii) x, y+2, z+1; (iv) x, y1, z; (v) x+1, y1, z; (vi) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula[Cu(C3H4N2)4(C2H6O)2][Cu2(C15H14N3O5)2]
Mr1187.67
Crystal system, space groupTriclinic, P1
Temperature (K)173
a, b, c (Å)8.0275 (1), 9.9401 (1), 16.8444 (1)
α, β, γ (°)96.607 (1), 95.134 (1), 96.394 (1)
V3)1319.71 (2)
Z1
Radiation typeMo Kα
µ (mm1)1.27
Crystal size (mm)0.60 × 0.12 × 0.09
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.516, 0.894
No. of measured, independent and
observed [I > 2σ(I)] reflections
19560, 7695, 6910
Rint0.026
(sin θ/λ)max1)0.714
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.087, 1.00
No. of reflections7695
No. of parameters342
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.65, 0.51

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003) and SADABS (Sheldrick, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2010), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top
Cu1—O31.9533 (10)Cu1—N21.9974 (12)
Cu1—N11.9694 (12)Cu2—N1A2.0391 (12)
Cu1—O51.9887 (10)Cu2—N1B2.0628 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3C—H3C···O2i0.841.992.8064 (18)166
N3B—H3B···O20.881.882.7178 (19)158
N3—H3···O6ii0.881.892.7716 (16)176
N3A—H3A1···O1iii0.881.902.7370 (19)159
C2A—H2A···O2i0.952.543.353 (2)144
C2B—H2B···N1A0.952.583.052 (2)111
C5A—H5A···O3Civ0.952.533.148 (2)123
C5A—H5A···O6v0.952.493.196 (2)131
C1C—H1C1···O6vi0.982.563.306 (3)133
C14—H14···O50.952.532.9629 (18)108
Symmetry codes: (i) x+1, y, z; (ii) x, y+2, z+1; (iii) x, y1, z; (iv) x+2, y, z; (v) x+1, y1, z; (vi) x+1, y+1, z.
 

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