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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 70| Part 2| February 2014| Pages m54-m55
doi:10.1107/S1600536814000798

Tetra­kis(μ3-2-{[1,1-bis­­(hy­dr­oxy­meth­yl)-2-oxidoeth­yl]imino­meth­yl}-6-nitro­pheno­lato)tetra­copper(II)

Eduard N. Chygorin,a Yuri O. Smal,a Vladimir N. Kokozaya* and Irina V. Omelchenkob

aDepartment of Inorganic Chemistry, Taras Shevchenko National University of Kyiv, 64\13 Volodymyrska St, Kyiv 01601, Ukraine, and bSTC `Institute for Single Crystals', National Academy of Sciences of Ukraine, 60 Lenina Avenue, Kharkiv 61001, Ukraine
*Correspondence e-mail: kokozay@univ.kiev.ua

(Received 11 December 2013; accepted 13 January 2014; online 18 January 2014)

The title cluster, [Cu4(C11H12N2O6)4], was obtained from the Cu0–FeCl2·4H2O–H4L–Et3N–DMF reaction system (in air), where H4L is 2-hy­droxy­methyl-2{[(2-hy­droxy-3-nitro­phen­yl)methyl­idene]amino}­propane-1,3-diol and DMF is di­methyl­formamide. The asymmetric unit consists of one Cu2+ ion and one dianionic ligand; a -4 symmetry element generates the cluster, which contains a {Cu4O4} cubane-like core. The metal ion has an elongated square-based pyramidal CuNO4 coordination geometry with the N atom in a basal site. An intra­molecular O—H⋯O hydrogen bond is observed. The solvent mol­ecules were found to be highly disordered and their contribution to the scattering was removed with the SQUEEZE procedure in PLATON [Spek (2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]). Acta Cryst. D65, 148–155], which indicated a solvent cavity of volume 3131 Å3 containing approximately 749 electrons. These solvent molecules are not considered in the given chemical formula.

CCDC reference: 981257

Related literature

For general background to direct synthesis (DS), see: Kokozay & Shevchenko (2005[Kokozay, V. N. & Shevchenko, D. V. (2005). Mater. Sci. Pol. 23, 287-312.]). For related structures, see: Dey et al. (2002[Dey, M., Rao, C. P., Saarenketo, P. K. & Rissanen, K. (2002). Inorg. Chem. Commun. 5, 380-383.]); Dong et al. (2007[Dong, J.-F., Li, L.-Z., Xu, H.-Y. & Wang, D.-Q. (2007). Acta Cryst. E63, m2300.]); Guo et al. (2008[Guo, Y., Li, L., Liu, Y., Dong, J. & Wang, D. (2008). Acta Cryst. E64, m675-m676.]). For successful realisation of DS, see: Chygorin et al. (2012[Chygorin, E. N., Nesterova, O. V., Rusanova, J. A., Kokozay, V. N., Bon, V. V., Boca, R. & Ozarowski, A. (2012). Inorg. Chem. 51, 386-396.]); Nesterov et al. (2012[Nesterov, D. S., Chygorin, E. N., Kokozay, V. N., Bon, V. V., Boca, R., Kozlov, Y. N., Shul'pina, L. S., Jezierska, J., Ozarowski, A., Pombeiro, A. J. L. & Shul'pin, G. B. (2012). Inorg. Chem. 51, 9110-9122.]).

[Scheme 1]

Experimental

Crystal data

  • [Cu4(C11H12N2O6)4]

  • Mr = 1327.06

  • Tetragonal, I 41 /a

  • a = 20.5587 (14) Å

  • c = 18.010 (2) Å

  • V = 7612.0 (11) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 1.17 mm−1

  • T = 173 K

  • 0.40 × 0.40 × 0.30 mm
Data collection

  • Agilent Xcalibur Sapphire3 diffractometer

  • Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)[Agilent (2012). CrysAlis PRO, CrysAlis CCD and CrysAlis RED. Agilent Technologies Ltd, Yarnton, England.] Tmin = 0.653, Tmax = 0.721

  • 3349 measured reflections

  • 3349 independent reflections

  • 1395 reflections with I > 2σ(I)
Refinement

  • R[F2 > 2σ(F2)] = 0.075

  • wR(F2) = 0.184

  • S = 0.80

  • 3349 reflections

  • 182 parameters

  • H-atom parameters constrained

  • Δρmax = 0.94 e Å−3

  • Δρmin = −0.57 e Å−3

Table 1
Selected bond lengths (Å)

Cu1—O1 1.892 (5)
Cu1—O6i 1.940 (5)
Cu1—N1 1.952 (6)
Cu1—O6 1.954 (4)
Cu1—O6ii 2.524 (5)
Symmetry codes: (i) [-y+{\script{5\over 4}}, x+{\script{1\over 4}}, -z+{\script{1\over 4}}]; (ii) [-x+1, -y+{\script{3\over 2}}, z].

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O4—H4A⋯O4ii 0.78 1.96 2.729 (9) 171
Symmetry code: (ii) [-x+1, -y+{\script{3\over 2}}, z].

Data collection: CrysAlis CCD (Agilent, 2012[Agilent (2012). CrysAlis PRO, CrysAlis CCD and CrysAlis RED. Agilent Technologies Ltd, Yarnton, England.]); cell refinement: CrysAlis RED (Agilent, 2012[Agilent (2012). CrysAlis PRO, CrysAlis CCD and CrysAlis RED. Agilent Technologies Ltd, Yarnton, England.]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]); molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information

CCDC reference: 981257

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814000798/hb7174sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814000798/hb7174Isup2.hkl

checkCIF report


Comment top

In last few decades polynuclear complexes have been in focus of intense interest due to their relevance to the active sites of metaloenzimes, and their potential applications as magnetic materials. Thus development of synthetic approaches that could lead to new polynuclear compounds or improve their yields is quite important. Our research group is interested in employment of so-called "direct synthesis" (DS), a serendipitous self-assembling approach based on utilization of metal powders as starting materials to construct coordination compounds both homo- and heterometallic ones. Recently we have shown its ability to produce Co/Fe complexes with Schiff base ligand (Chygorin et al., 2012; Nesterov et al., 2012). It should be noted that outcome of DS is not highly predictable and sometimes we can isolated homometallic or mononuclear complexes only. Such a case was observed in the investigated system: Cu0–FeCl2.4H2O–H4L–Et3N–dmf, where H4L is 2-hydroxymethyl-2{[(2-hydroxy-3-nitrophenyl)methylene]amino}propane-1,3-diol (Fig. 1). The Schiff base ligand, that is obtained by condencation of the salicylaldehyde derivative and tris(hydroxymethyl)aminomethane is typical hydroxy-rich ligand, which can coordinate to several metal centers and accepts various coordination modes, and thus it is an attractive ligand system for serendipitous self-assembling. Despite of this fact this Schiff base ligand has recived little attention to date [only 35 hits were found by searching via CSD (http://www.ccdc.cam.ac.uk/cgi-bin/catreq.cgi?)]. Herein we report the synthesis of a new tetranuclear cubane complex starting from potentially polydentate hydroxyl-rich ligand.

The reaction of copper powder with iron(II) chloride in dmf solution of the tetrapodal Schiff base ligand, formed in situ, in basic medium with free access of air leads to the isolation of the homometallic cuban complex [Cu4(C11H12O6N2)4]. The Schiff base ligand H4L was obtained by condensation of 3-nitro-salicylaldehyde and tris(hydroxymethyl)aminomethane (Fig. 1). The molar ratio of starting materials (Cu0: FeCl2: Schiff base ligand) was taken 1:1:2. The reaction was carried out in air with heating and stirring till total dissolution of metal powder was observed.

Tetranuclear molecular complex (Fig. 2) consists of the discrete [Cu4(H2L)4] moiety with a {Cu4O4} cubane-like core. Eight alternately arranged netal centers and oxygen atoms from methoxy groups form a distorted {Cu4O4} cube with local S4-symmetry. Each of four ligands coordinates in a tridentate mode as an (H2L)2- dianion, with the phenoxyl and one of the alkoxyl groups deprotonated. The NO2 donor set from one ligand molecule together with O-atom from methoxy arm of another ligand forms distorted square coordination polyhedra around each metal center (with RMS deviation of atoms from square plane of 0.135 Å). Coordination lengths vary in the range of 1.892 - 1.955 Å, and X—Cu—Y angles vary in the range of 84.8 - 94.9° that is comparable with the known literature data. The oxygen atom of the methoxy group of the third ligand molecule coordinates on this metal atom with Cu—O length of 2.524 Å, so that can be threated as additional coordination. In crystal, weak C4—H4B···O2' hydrogen bonds (1.25 - y,x - 0.25,z - 0.25; H···O' 2.51 Å, C—H···O' 153°) form three-dimensional-connected network with channels along (111) crystallographic direction. Minimal channel dimension is about 6.74 Å (O5···O5' distance). The crystal packing diagram is shown in Fig. 3.

Related literature top

For general background to direct synthesis (DS), see: Kokozay & Shevchenko (2005). For related structures, see: Dey et al. (2002); Dong et al. (2007); Guo et al. (2008). For successful realisation of DS, see: Chygorin et al. (2012); Nesterov et al. (2012).

Experimental top

Tris(hydroxymethyl)aminomethane (0.303 g, 2.5 mmol), 3-Nitrosalicylaldehyde (0.418 g, 2.5 mmol), and triethylamine (0.35 ml, 2.5 mmol) were dissolved in dmf (25 ml) in this order, forming an orange solution and magnetically stirred at 60–70°C (15 min). Then, copper powder (0.079 g, 1.25 mmol) and FeCl2.4H2O (0.248 g, 1.25 mmol) were successfully added to the hot orange solution with stirring about 3 h. Brown blocks were isolated by adding diethylether to the dark orange-brown solution after 2 days. Yield: 0.4 g, 48%. The compound is sparingly soluble in dmso and dmf, and it is stable in air.

Refinement top

All H atoms were placed in idealized positions (C–H = 0.95 – 0.99 Å, O–H = 0.84 Å) and constrained to ride on their parent atoms, with Uiso = 1.2Ueq (except Uiso = 1.5Ueq for hydroxyl groups). Hydrogen atom of the hydroxyl group O4–H4 was disordered over two sites with equal occupancy factors of 0.50 in order to fit the intramolecular hydrogen bond O4–H4A···O4'. Several isolated electron density peaks were located during the refinement, whose were believe to be a solvent molecules. Large displacement parameters were observed modeling the disordered oxygen, carbon, and sulfur atoms. SQUEEZE procedure of PLATON indicated a solvent cavity of volume 3131 Å3 centered at (0,0,0), containing approximately 749 electrons. In the final refinement, this contribution was removed from the intensity data that produced better refinement results. The hydroxyl group O5—H5A located near the void was believed to be H-bonded with one of the removed solvent molecules. Several reflections with great differences between calculated and observed F2 were omitted during the refinement. These reflections were believed to arise because of little impurities of the crystal under study.

Structure description top

In last few decades polynuclear complexes have been in focus of intense interest due to their relevance to the active sites of metaloenzimes, and their potential applications as magnetic materials. Thus development of synthetic approaches that could lead to new polynuclear compounds or improve their yields is quite important. Our research group is interested in employment of so-called "direct synthesis" (DS), a serendipitous self-assembling approach based on utilization of metal powders as starting materials to construct coordination compounds both homo- and heterometallic ones. Recently we have shown its ability to produce Co/Fe complexes with Schiff base ligand (Chygorin et al., 2012; Nesterov et al., 2012). It should be noted that outcome of DS is not highly predictable and sometimes we can isolated homometallic or mononuclear complexes only. Such a case was observed in the investigated system: Cu0–FeCl2.4H2O–H4L–Et3N–dmf, where H4L is 2-hydroxymethyl-2{[(2-hydroxy-3-nitrophenyl)methylene]amino}propane-1,3-diol (Fig. 1). The Schiff base ligand, that is obtained by condencation of the salicylaldehyde derivative and tris(hydroxymethyl)aminomethane is typical hydroxy-rich ligand, which can coordinate to several metal centers and accepts various coordination modes, and thus it is an attractive ligand system for serendipitous self-assembling. Despite of this fact this Schiff base ligand has recived little attention to date [only 35 hits were found by searching via CSD (http://www.ccdc.cam.ac.uk/cgi-bin/catreq.cgi?)]. Herein we report the synthesis of a new tetranuclear cubane complex starting from potentially polydentate hydroxyl-rich ligand.

The reaction of copper powder with iron(II) chloride in dmf solution of the tetrapodal Schiff base ligand, formed in situ, in basic medium with free access of air leads to the isolation of the homometallic cuban complex [Cu4(C11H12O6N2)4]. The Schiff base ligand H4L was obtained by condensation of 3-nitro-salicylaldehyde and tris(hydroxymethyl)aminomethane (Fig. 1). The molar ratio of starting materials (Cu0: FeCl2: Schiff base ligand) was taken 1:1:2. The reaction was carried out in air with heating and stirring till total dissolution of metal powder was observed.

Tetranuclear molecular complex (Fig. 2) consists of the discrete [Cu4(H2L)4] moiety with a {Cu4O4} cubane-like core. Eight alternately arranged netal centers and oxygen atoms from methoxy groups form a distorted {Cu4O4} cube with local S4-symmetry. Each of four ligands coordinates in a tridentate mode as an (H2L)2- dianion, with the phenoxyl and one of the alkoxyl groups deprotonated. The NO2 donor set from one ligand molecule together with O-atom from methoxy arm of another ligand forms distorted square coordination polyhedra around each metal center (with RMS deviation of atoms from square plane of 0.135 Å). Coordination lengths vary in the range of 1.892 - 1.955 Å, and X—Cu—Y angles vary in the range of 84.8 - 94.9° that is comparable with the known literature data. The oxygen atom of the methoxy group of the third ligand molecule coordinates on this metal atom with Cu—O length of 2.524 Å, so that can be threated as additional coordination. In crystal, weak C4—H4B···O2' hydrogen bonds (1.25 - y,x - 0.25,z - 0.25; H···O' 2.51 Å, C—H···O' 153°) form three-dimensional-connected network with channels along (111) crystallographic direction. Minimal channel dimension is about 6.74 Å (O5···O5' distance). The crystal packing diagram is shown in Fig. 3.

For general background to direct synthesis (DS), see: Kokozay & Shevchenko (2005). For related structures, see: Dey et al. (2002); Dong et al. (2007); Guo et al. (2008). For successful realisation of DS, see: Chygorin et al. (2012); Nesterov et al. (2012).

Computing details top

Data collection: CrysAlis CCD (Agilent, 2012); cell refinement: CrysAlis RED (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: OLEX2 (Dolomanov et al., 2009); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Schiff base ligand: the product of condensation of 3-nitro-salicylaldehyde and tris(hydroxymethyl)aminomethane.
[Figure 2] Fig. 2. View of cubane tetranuclear complex [Cu4(C11H12O6N2)4] (H atoms are omitted for clarity, the non-hydrogen atoms are shown as 30% thermal ellipsoids). Symmetry transformation used to generate equivalent atoms: a 1 - x, 1.5 - y, z; b x + 0.25, 1.25 - y, 0.25 - z; c 1.25 - x, y - 0.25,0.25 - z.
[Figure 3] Fig. 3. The crystal-packing diagram along the (001) direction.
Tetrakis(µ3-2-{[1,1-bis(hydroxymethyl)-2-oxidoethyl]iminomethyl}-6-nitrophenolato)tetracopper(II) top
Crystal data top
[Cu4(C11H12N2O6)4]Dx = 1.158 Mg m−3
Mr = 1327.06Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/aCell parameters from 462 reflections
Hall symbol: -I 4adθ = 3.0–25.0°
a = 20.5587 (14) ŵ = 1.17 mm−1
c = 18.010 (2) ÅT = 173 K
V = 7612.0 (11) Å3Block, brown
Z = 40.40 × 0.40 × 0.30 mm
F(000) = 2704
Data collection top
Agilent Xcalibur Sapphire3
diffractometer		3349 independent reflections
Radiation source: Enhance (Mo) X-ray Source1395 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.000
Detector resolution: 16.1827 pixels mm-1θmax = 25.0°, θmin = 3.2°
ω scansh = −16→17
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)		k = 0→24
Tmin = 0.653, Tmax = 0.721l = 0→21
3349 measured reflections
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)] = 0.075Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.184H-atom parameters constrained
S = 0.80 w = 1/[σ2(Fo2) + (0.060P)2]
where P = (Fo2 + 2Fc2)/3
3349 reflections(Δ/σ)max = 0.001
182 parametersΔρmax = 0.94 e Å−3
0 restraintsΔρmin = −0.57 e Å−3
Crystal data top
[Cu4(C11H12N2O6)4]Z = 4
Mr = 1327.06Mo Kα radiation
Tetragonal, I41/aµ = 1.17 mm−1
a = 20.5587 (14) ÅT = 173 K
c = 18.010 (2) Å0.40 × 0.40 × 0.30 mm
V = 7612.0 (11) Å3
Data collection top
Agilent Xcalibur Sapphire3
diffractometer		3349 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)		1395 reflections with I > 2σ(I)
Tmin = 0.653, Tmax = 0.721Rint = 0.000
3349 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0750 restraints
wR(F2) = 0.184H-atom parameters constrained
S = 0.80Δρmax = 0.94 e Å−3
3349 reflectionsΔρmin = −0.57 e Å−3
182 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
xyzUiso*/UeqOcc. (<1)
Cu10.48941 (4)0.66864 (4)0.06731 (4)0.0396 (3)
O10.5536 (2)0.6041 (2)0.0524 (3)0.0451 (13)
N10.4460 (3)0.6539 (3)−0.0276 (3)0.0406 (16)
C10.5204 (4)0.5693 (4)−0.0716 (4)0.047 (2)
N20.6541 (4)0.5153 (3)0.0538 (4)0.0542 (19)
O20.6303 (3)0.5101 (3)0.1159 (3)0.0611 (17)
C20.5608 (4)0.5690 (4)−0.0063 (5)0.047 (2)
O30.7144 (3)0.5100 (3)0.0436 (3)0.0751 (19)
C30.6141 (4)0.5230 (4)−0.0096 (5)0.050 (2)
O40.4358 (3)0.7332 (3)−0.1606 (3)0.0761 (19)
H4A0.47280.7401−0.16460.114*0.50
H4C0.41450.7014−0.17690.114*0.50
C40.6276 (4)0.4875 (4)−0.0723 (5)0.061 (2)
H4B0.66440.4596−0.07280.073*
O50.2776 (3)0.7029 (3)−0.0736 (4)0.0732 (18)
H5A0.24300.6816−0.07840.110*
C50.5890 (4)0.4913 (4)−0.1342 (5)0.061 (3)
H5B0.59910.4672−0.17770.073*
O60.4282 (2)0.7408 (2)0.0779 (2)0.0369 (12)
C60.5353 (4)0.5310 (4)−0.1317 (4)0.052 (2)
H6A0.50710.5320−0.17350.063*
C70.4659 (4)0.6122 (4)−0.0773 (4)0.048 (2)
H7A0.44160.6101−0.12200.057*
C80.3906 (4)0.6972 (4)−0.0412 (4)0.047 (2)
C90.4121 (4)0.7530 (4)−0.0911 (4)0.057 (2)
H9A0.37470.7826−0.09890.069*
H9B0.44650.7780−0.06530.069*
C100.3319 (4)0.6594 (4)−0.0737 (5)0.058 (2)
H10A0.34150.6448−0.12490.069*
H10B0.32230.6206−0.04300.069*
C110.3712 (4)0.7262 (4)0.0359 (4)0.0436 (19)
H11A0.34540.76630.02850.052*
H11B0.34400.69450.06330.052*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0337 (6)0.0344 (6)0.0509 (5)0.0009 (5)−0.0021 (5)−0.0018 (4)
O10.044 (3)0.029 (3)0.062 (3)−0.005 (3)−0.002 (3)−0.015 (3)
N10.039 (4)0.037 (4)0.046 (3)−0.005 (3)−0.001 (3)−0.006 (3)
C10.032 (5)0.046 (5)0.064 (5)0.001 (4)0.007 (4)−0.004 (5)
N20.053 (5)0.038 (4)0.071 (5)0.012 (4)−0.004 (4)−0.017 (4)
O20.059 (4)0.040 (4)0.084 (4)0.008 (3)−0.019 (4)−0.004 (3)
C20.034 (5)0.022 (4)0.084 (6)−0.001 (4)0.003 (5)−0.009 (4)
O30.032 (4)0.077 (5)0.116 (5)0.013 (3)−0.001 (3)−0.026 (4)
C30.039 (5)0.041 (5)0.071 (5)−0.023 (4)−0.002 (5)−0.018 (5)
O40.082 (5)0.088 (5)0.059 (3)−0.014 (4)0.006 (3)0.006 (3)
C40.039 (5)0.045 (6)0.098 (6)−0.004 (5)0.005 (5)−0.024 (5)
O50.038 (4)0.065 (4)0.116 (5)0.001 (3)−0.020 (4)0.000 (4)
C50.037 (5)0.051 (6)0.094 (6)−0.004 (5)0.020 (5)−0.033 (5)
O60.019 (3)0.029 (3)0.063 (3)0.002 (2)−0.007 (2)0.004 (2)
C60.040 (5)0.054 (6)0.062 (5)−0.012 (5)0.005 (4)−0.016 (5)
C70.044 (5)0.048 (5)0.051 (5)−0.013 (4)−0.001 (4)0.010 (4)
C80.032 (5)0.043 (5)0.067 (5)0.005 (4)−0.013 (4)0.004 (4)
C90.048 (6)0.063 (6)0.062 (5)−0.010 (5)−0.017 (4)0.010 (5)
C100.041 (5)0.061 (6)0.071 (5)0.005 (5)0.000 (5)−0.007 (5)
C110.030 (5)0.041 (5)0.059 (4)0.000 (4)0.003 (4)−0.002 (4)
Geometric parameters (Å, º) top
Cu1—O11.892 (5)C4—C51.371 (11)
Cu1—O6i1.940 (5)C4—H4B0.9500
Cu1—N11.952 (6)O5—C101.430 (9)
Cu1—O61.954 (4)O5—H5A0.8400
Cu1—O6ii2.524 (5)C5—C61.374 (11)
O1—C21.288 (8)C5—H5B0.9500
N1—C71.304 (9)O6—C111.428 (8)
N1—C81.467 (9)O6—Cu1iii1.940 (5)
C1—C61.373 (10)C6—H6A0.9500
C1—C71.428 (10)C7—H7A0.9500
C1—C21.440 (10)C8—C91.524 (10)
N2—O21.224 (8)C8—C101.551 (10)
N2—O31.259 (8)C8—C111.562 (10)
N2—C31.417 (10)C9—H9A0.9900
C2—C31.449 (10)C9—H9B0.9900
C3—C41.373 (10)C10—H10A0.9900
O4—C91.403 (9)C10—H10B0.9900
O4—H4A0.7773C11—H11A0.9900
O4—H4C0.8400C11—H11B0.9900
O1—Cu1—O6i93.6 (2)C6—C5—H5B120.9
O1—Cu1—N194.9 (2)C11—O6—Cu1iii118.5 (4)
O6i—Cu1—N1164.4 (2)C11—O6—Cu1108.5 (4)
O1—Cu1—O6174.8 (2)Cu1iii—O6—Cu1108.6 (2)
O6i—Cu1—O687.9 (2)C1—C6—C5123.1 (8)
O1—Cu1—O6ii93.45 (18)C1—C6—H6A118.5
O6i—Cu1—O6ii73.19 (17)C5—C6—H6A118.5
N1—Cu1—O6ii119.2 (2)N1—C7—C1127.0 (7)
O6—Cu1—O6ii82.22 (17)N1—C7—H7A116.5
N1—Cu1—O684.8 (2)C1—C7—H7A116.5
C2—O1—Cu1126.0 (5)N1—C8—C9109.3 (6)
C7—N1—C8121.9 (6)N1—C8—C10111.3 (6)
C7—N1—Cu1124.0 (5)C9—C8—C10112.3 (6)
C8—N1—Cu1114.0 (5)N1—C8—C11106.4 (6)
C6—C1—C7118.2 (8)C9—C8—C11108.1 (7)
C6—C1—C2120.9 (8)C10—C8—C11109.2 (6)
C7—C1—C2120.8 (7)O4—C9—C8114.1 (7)
O2—N2—O3121.3 (7)O4—C9—H9A108.7
O2—N2—C3120.9 (7)C8—C9—H9A108.7
O3—N2—C3117.6 (7)O4—C9—H9B108.7
O1—C2—C1127.1 (7)C8—C9—H9B108.7
O1—C2—C3119.0 (7)H9A—C9—H9B107.6
C1—C2—C3113.9 (7)O5—C10—C8107.0 (6)
C4—C3—N2119.1 (8)O5—C10—H10A110.3
C4—C3—C2122.3 (8)C8—C10—H10A110.3
N2—C3—C2118.6 (7)O5—C10—H10B110.3
C9—O4—H4A111.7C8—C10—H10B110.3
C9—O4—H4C110.9H10A—C10—H10B108.6
H4A—O4—H4C128.4O6—C11—C8110.0 (6)
C5—C4—C3121.4 (8)O6—C11—H11A109.7
C5—C4—H4B119.3C8—C11—H11A109.7
C3—C4—H4B119.3O6—C11—H11B109.7
C10—O5—H5A109.5C8—C11—H11B109.7
C4—C5—C6118.2 (8)H11A—C11—H11B108.2
C4—C5—H5B120.9
O6i—Cu1—O1—C2170.0 (6)O6i—Cu1—O6—C11−139.6 (4)
N1—Cu1—O1—C23.0 (6)N1—Cu1—O6—C1126.7 (4)
O6—Cu1—O1—C2−84 (2)O1—Cu1—O6—Cu1iii−116 (2)
O6ii—Cu1—O1—C2−116.7 (6)O6i—Cu1—O6—Cu1iii−9.5 (2)
O1—Cu1—N1—C7−2.5 (6)N1—Cu1—O6—Cu1iii156.7 (3)
O6i—Cu1—N1—C7−125.4 (8)C7—C1—C6—C5175.5 (7)
O6—Cu1—N1—C7172.3 (6)C2—C1—C6—C5−0.9 (12)
O6ii—Cu1—N1—C794.2 (6)C4—C5—C6—C13.4 (13)
O1—Cu1—N1—C8−178.6 (5)C8—N1—C7—C1177.6 (7)
O6i—Cu1—N1—C858.5 (11)Cu1—N1—C7—C11.8 (11)
O6—Cu1—N1—C8−3.8 (5)C6—C1—C7—N1−177.0 (7)
O6ii—Cu1—N1—C8−81.9 (5)C2—C1—C7—N1−0.6 (12)
Cu1—O1—C2—C1−2.8 (11)C7—N1—C8—C9−77.3 (8)
Cu1—O1—C2—C3178.0 (5)Cu1—N1—C8—C998.9 (6)
C6—C1—C2—O1177.4 (7)C7—N1—C8—C1047.3 (9)
C7—C1—C2—O11.0 (12)Cu1—N1—C8—C10−136.5 (5)
C6—C1—C2—C3−3.4 (11)C7—N1—C8—C11166.2 (6)
C7—C1—C2—C3−179.7 (7)Cu1—N1—C8—C11−17.6 (7)
O2—N2—C3—C4−135.5 (8)N1—C8—C9—O459.8 (8)
O3—N2—C3—C440.2 (11)C10—C8—C9—O4−64.2 (9)
O2—N2—C3—C245.5 (10)C11—C8—C9—O4175.3 (6)
O3—N2—C3—C2−138.8 (8)N1—C8—C10—O5170.8 (6)
O1—C2—C3—C4−175.1 (7)C9—C8—C10—O5−66.3 (8)
C1—C2—C3—C45.5 (11)C11—C8—C10—O553.6 (8)
O1—C2—C3—N23.8 (11)Cu1iii—O6—C11—C8−167.6 (4)
C1—C2—C3—N2−175.5 (7)Cu1—O6—C11—C8−43.2 (6)
N2—C3—C4—C5177.6 (8)N1—C8—C11—O639.5 (8)
C2—C3—C4—C5−3.5 (13)C9—C8—C11—O6−77.8 (7)
C3—C4—C5—C6−1.2 (13)C10—C8—C11—O6159.8 (6)
O1—Cu1—O6—C11114 (2)
Symmetry codes: (i) −y+5/4, x+1/4, −z+1/4; (ii) −x+1, −y+3/2, z; (iii) y−1/4, −x+5/4, −z+1/4.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···O4ii0.781.962.729 (9)171
Symmetry code: (ii) −x+1, −y+3/2, z.
Selected bond lengths (Å) top
Cu1—O11.892 (5)Cu1—O61.954 (4)
Cu1—O6i1.940 (5)Cu1—O6ii2.524 (5)
Cu1—N11.952 (6)
Symmetry codes: (i) −y+5/4, x+1/4, −z+1/4; (ii) −x+1, −y+3/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···O4ii0.781.962.729 (9)171
Symmetry code: (ii) −x+1, −y+3/2, z.
 

Acknowledgements

This work was partly supported by the State Fund for Fundamental Research of Ukraine (project 54.3/005).

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ISSN: 2056-9890
Volume 70| Part 2| February 2014| Pages m54-m55
doi:10.1107/S1600536814000798
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