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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 69| Part 10| October 2013| Pages m568-m569
doi:10.1107/S1600536813026093

Bis(1,10-phenanthroline-κ2N,N′)(sulfato-κO)copper(II) ethanol monosolvate

Natthaya Meundaeng,a Timothy J. Priorb and Apinpus Rujiwatraa*

aDepartment of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand, and bDepartment of Chemistry, University of Hull, Cottingham Road, Hull, HU6 7RX, England
*Correspondence e-mail: apinpus@gmail.com

(Received 2 September 2013; accepted 21 September 2013; online 28 September 2013)

The crystal structure of the title compound, [Cu(SO4)(C12H8N2)2]·C2H5OH, arises from the assembly of the neutral complex [Cu(SO4)(C12H8N2)2] and an ethanol solvent mol­ecule. The CuII ion is five-coordinate, surrounded by two pairs of N atoms from two independent N,N′-chelating 1,10-phenanthroline ligands, and one O atom of monodentate sulfate ligand, in a distorted trigonal-bipyramidal fashion. Spatial orientation of the ligands and the assembly in the solid state are stabilized by the C—H⋯O hydrogen-bonding inter­actions, established between the O atoms (from the sulfate ligand and the ethanol mol­ecule) and the neighbouring 1,10-phenanthroline mol­ecules. There is also an offset face-to-face π–π stacking between the 1,10-phenanthroline ligands. The ethanol solvent mol­ecule is disordered over two orientations in the ratio 0.663 (10):0.337 (10). The crystal examined was subject to racemic twinning and the refined twin fraction was 0.346 (19).

CCDC reference: 962540

Related literature

Zhong has published many similar compounds with different solvent systems, see, for example: Zhong (2011a[Zhong, K.-L. (2011a). Z. Kristallogr. New Cryst. Struct. 226, 286-288.],b[Zhong, K.-L. (2011b). Acta Cryst. E67, m1215-m1216.], 2012[Zhong, K.-L. (2012). Acta Cryst. E68, m1555.]); Zhong & Cao (2013[Zhong, K.-L. & Cao, G.-Q. (2013). Acta Cryst. E69, m40-m41.]). For a similar centrosymmetric compound featuring 2,2′-bi­pyridine and bidentate sulfate, see: Wojciechowska et al. (2011[Wojciechowska, A., Jezierska, J., Bieńko, A. & Daszkiewicz, M. (2011). Polyhedron, 30, 1547-1554.]). For similar compounds of different first-row transition metals, see, for example: Zhu et al. (2006[Zhu, Y.-M., Zhong, K.-L. & Lu, W.-J. (2006). Acta Cryst. E62, m2725-m2726.]); Zhong et al. (2009[Zhong, K.-L., Ni, C. & Wang, J.-M. (2009). Acta Cryst. E65, m911.]).

[Scheme 1]

Experimental

Crystal data

  • [Cu(SO4)(C12H8N2)2]·C2H6O

  • Mr = 564.06

  • Monoclinic, C c

  • a = 17.5488 (14) Å

  • b = 11.9360 (11) Å

  • c = 13.0663 (9) Å

  • β = 120.664 (5)°

  • V = 2354.2 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 1.06 mm−1

  • T = 150 K

  • 0.32 × 0.24 × 0.12 mm
Data collection

  • Stoe IPDS2 diffractometer

  • Absorption correction: numerical (X-AREA; Stoe & Cie, 2002[Stoe & Cie (2002). X-AREA. Stoe & Cie, Darmstadt, Germany.]) Tmin = 0.727, Tmax = 0.883

  • 10087 measured reflections

  • 5771 independent reflections

  • 4259 reflections with I > 2σ(I)

  • Rint = 0.070
Refinement

  • R[F2 > 2σ(F2)] = 0.058

  • wR(F2) = 0.160

  • S = 1.01

  • 5771 reflections

  • 331 parameters

  • 8 restraints

  • H-atom parameters constrained

  • Δρmax = 1.02 e Å−3

  • Δρmin = −1.09 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 2594 Friedel pairs

  • Absolute structure parameter: 0.346 (19)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C3—H3⋯O2i 0.95 2.48 3.389 (9) 161
C5—H5⋯O1i 0.95 2.34 3.263 (9) 165
C6—H6⋯O2ii 0.95 2.35 3.252 (11) 158
C9—H9⋯O4iii 0.95 2.28 3.188 (9) 161
C10—H10⋯O1 0.95 2.41 2.973 (8) 118
C21—H21⋯O1iv 0.95 2.44 3.175 (8) 134
C25—H25⋯O1v 0.95 2.44 3.285 (11) 149
C25—H25⋯O4v 0.95 2.39 3.255 (11) 151
C26—H26⋯O3vi 0.95 2.50 3.200 (8) 130
C28—H28⋯O4vi 0.95 2.46 3.367 (10) 159
C30—H30⋯O41iii 0.95 2.45 3.165 (12) 132
Symmetry codes: (i) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]; (ii) [x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]; (iii) [x, -y+1, z+{\script{1\over 2}}]; (iv) [x, -y+1, z-{\script{1\over 2}}]; (v) [x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]; (vi) [x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}].

Data collection: X-AREA (Stoe & Cie, 2002[Stoe & Cie (2002). X-AREA. Stoe & Cie, Darmstadt, Germany.]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS86 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information

CCDC reference: 962540

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536813026093/gg2128sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813026093/gg2128Isup2.hkl

checkCIF report


Comment top

The crystal structure of the title complex, [Cu(SO4)(C12H8N2)2]·C2H6O (I), is isostructural with the propane-1,2-diol and ethane-1,2-diol solvates, Cu(C12H8N2)2(SO4)·C3H8O2 (Zhong, 2011a) and [CuSO4(C12H8N2)2]·C2H6O2 (Zhong, 2011b). The neutral complex [Cu(SO4)(C12H8N2)2] in I is composed of a central CuII ion, coordinated by a single oxygen atom (O3) of the monodentate sulfato ligand, and two pairs of nitrogen atoms (N1, N2, N3 and N4) of two independent N,N'–chelating o–phen (see Fig. 1). Rather than the square pyramidal geometry described for some related complexes (Zhong, 2011a; Zhong, 2011b), the coordination about the CuII ion in I is better described as a trigonal bipyramid. In some previous reports, disorder of the sulfato ligand has introduced problems in the refinement. (e.g a Cu–O bond of length 1.4 Å (Zhong, 2011a)) We see no evidence for disorder in the sulfato ligand. The coordinating atoms N1, N4 and O3 are located in the trigonal bipyramidal plane with a summation of the three angles about the metal center close to 360°: O3—Cu1—N1 103.76 (18)°, O3—Cu1—N4 146.72 (19)° and N1—Cu1—N4 109.17 (14)°. The apical positions of the trigonal bipyramid are occupied by atoms N2 and N3 with the N2—Cu1—N3 angle of 170.74 (16)°. The Cu—O (1.947 (4) Å) and Cu—N (1.995 (5)–2.191 (6) Å) bond lengths in complex I are nontheless in good agreement with those reported for the relevant structures (Zhong, 2011a; Zhong, 2011b). The two independent chelating o–phen ligands anchored onto the same metal ion are oriented in a different planes with a slanting angle of 70.8 (1)° between the two molecular planes.

The spatial arrangement of each structural building motifs and the three–dimensional supramolecular assembly in I are regulated by the weak C—H···O hydrogen-bonding interactions (Fig. 2) in synergy with the π-π interactions (Fig. 3). Every oxygen atom, including those of the sulfato ligand, and the solvent molecule display C—H···O interactions with the chelating o–phen ligands, calculated by using the program PLATON (Spek, 2009). A close proximity between the sulfato oxygen atoms and the hydroxyl group of the solvent molecule suggests the possibility for the hydrogen bonding interactions between the two: O41···O2 2.8757 (89) Å and O42···O4 2.719 (16) Å. In addition to the hydrogen bonding interactions, the two adjacent o-phens exhibit the offset face-to-face π-π stacking with the inter–plane distance of 3.529 Å, centroid–to–centroid distance of 4.455 Å, and a displacement angle of 32.72°.

Systematic absences indicated a choice of space groups: Cc or C2/c and statistics of normalized structure factors suggested the structure was non-centric. The |Z-1| value of 0.773 for all data is close to the expected value for a non-centrosymmetric structure of 0.736. Similarly the N(Z) distribution provides a further indication suggests the structure is non-centric. Detailed E-statistics are contained within Figure 4.

Refinements in the two possible space group choices were perfomed and these clearly indicated that C2/c was incorrect. In particular, the wR2 was substantially better in the non-centric case. (wR2 = 0.1595 for all data in Cc and 0.2498 for all data in C2/c.) The C—C bond precision was better in the non-centric case (0.0115 compared with 0.0130 Å). This would not be the case if a strict centre of symmetry was present. Cc was therefore retained as the space group.

The comparison to other structure mentioned previously is important. Those similar structures reported in Cc (eg Zhong, 2011b and Zhong & Cai, 2013) have an ordered monodentate sulfate ligand. Those in C2/c (eg Wojciechowska et al., 2011; Zhu et al., 2006, and Zhong et al., 2009) have an orderd bidentate sulfate ligand. Here the stable model in Cc has a mondentate sulfate with no ligand disorder, but the model in C2/c displays a disordered monodentate sulfate in contrast to the other reports. The refinement in C2/c is contained within the CIF for completeness but the crystal data and refinements indicate this is not the correct space group.

The crystal examined displayed racemic twinning. The refined twin fraction of the second component was 0.346 (19). This value is significantly different from 1/2, the value that would be expected if the compound was truly centrosymmetric and incorrectly refined in the space group Cc.

The ethanol solvent molecule is disordered over two positions, related by a rotation of approximately 180° about the C—C bond. The atoms of each orientation were identified in difference Fourier maps. The presence of ethanol is clear from these and the existence of two molecules in different orientations is apparent. Figure 5 shows the relationship between two orientations of the ethanol. Figures 6 and 7 show Fobs Fourier maps calculated using all observed data. From these the molecule can clearly be identified as ethanol, precluding any inclusion of dimethylsulfoxide or thiourea from the reaction mixture. The two orientations are present in the ratio 66.3:33.7 (10) %. For the major orientation, O41 forms a hydrogen bond to O2 while for the minor orientation, O42 forms a hydrogen bond to O4.

Related literature top

Zhong has published many similar compounds with different solvent systems, see, for example: Zhong (2011a,b, 2012); Zhong & Cao (2013). For a similar centrosymmetric compound featuring 2,2'-bipyridine and bidentate sulfate, see: Wojciechowska et al. (2011). For similar compounds of different first-row transition metals, see, for example: Zhu et al. (2006); Zhong et al. (2009).

Experimental top

The crystals of [Cu(SO4)(C12H8N2)2]·C2H4O (I) were unexpectedly obtained as a by-product during an attempt to synthesize copper complexes using mixing ligands of 1,10–phenanthroline (o–phen) and thiourea by a bilayer-diffusion method. In a typical experiment, two immiscible solutions A and B were first prepared. Solution A: CuSO4·5H2O (0.0499 g, 0.2 mmol; Fisher Scientific 99.55%) was dissolved in 4.0 ml dimethylsulfoxide (Riedel-de Haën 99.5%) in a small test tube (diameter of ca 13 mm). Solution B: 1,10-phenanthroline (o–phen; 0.0793 g, 0.4 mmol; QRëC 99.5%) and thiourea (0.0305 g, 0.4 mmol; Merck 99.0%) were dissolved in 4.0 ml e thanol (Merck 99.9%). Solution B was then gently added onto the surface of solution A. After 24 h, blue block shaped crystals were crystallized and isolated for single-crystal X-ray diffraction experiment.

Refinement top

Hydrogen atoms were fitted using a riding model. The isotropic displacement factor for each hydrogen atom is 1.2 times that of the atom on which it rides.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-AREA (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010) and PLATON (Spek, 2009).

Figures top
The asymmetric unit of I drawn with 50% probability for displacement ellipsoids. Hydrogen atoms are omitted for clarity.

View of the hydrogen bonding interactions (dash lines). [Symmetry codes: (i) x - 1/2, -y + 1/2, z - 1/2; (ii) x - 1/2, y - 1/2, z; (iii) x, -y + 1, z + 1/2; (iv)x, -y + 1, z - 1/2; (v) x + 1/2, y - 1/2, z; (vi) x + 1/2, -y + 1/2, z + 1/2]

View of the π– π interactions between the adjacent o–phen molecules.

Normalized structure factor statistics. The inset graph shows the N(Z) distribution.

Arrangement of the two orientations of the disordered ethanol molecule. The major orientation (66%) is O41 C41a C42b. The minor orientation (34%) is O42 C42b C41b.

Fobs map calculated in the plane defined by O41 C41a C42a using all observed data. The x and y axes are labelled in Å and the scale is in eÅ-3.

Fobs map calculated in the plane defined by O42 C42b C41b using all observed data. The x and y axes are labelled in Å and the scale is in eÅ-3.
Bis(1,10-phenanthroline-κ2N,N')(sulfato-κO)copper(II) ethanol monosolvate top
Crystal data top
[Cu(SO4)(C12H8N2)2]·C2H6OF(000) = 1156
Mr = 564.06Dx = 1.591 Mg m−3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2ycCell parameters from 11381 reflections
a = 17.5488 (14) Åθ = 1.8–29.5°
b = 11.9360 (11) ŵ = 1.06 mm−1
c = 13.0663 (9) ÅT = 150 K
β = 120.664 (5)°Block, blue
V = 2354.2 (3) Å30.32 × 0.24 × 0.12 mm
Z = 4
Data collection top
Stoe IPDS2
diffractometer		5771 independent reflections
Radiation source: fine-focus sealed tube4259 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.070
Detector resolution: 6.67 pixels mm-1θmax = 29.2°, θmin = 2.2°
ω scansh = −24→23
Absorption correction: numerical
(X-AREA; Stoe & Cie, 2002)		k = −15→16
Tmin = 0.727, Tmax = 0.883l = −17→17
10087 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.058H-atom parameters constrained
wR(F2) = 0.160 w = 1/[σ2(Fo2) + (0.0966P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
5771 reflectionsΔρmax = 1.02 e Å−3
331 parametersΔρmin = −1.09 e Å−3
8 restraintsAbsolute structure: Flack (1983), 2594 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.346 (19)
Crystal data top
[Cu(SO4)(C12H8N2)2]·C2H6OV = 2354.2 (3) Å3
Mr = 564.06Z = 4
Monoclinic, CcMo Kα radiation
a = 17.5488 (14) ŵ = 1.06 mm−1
b = 11.9360 (11) ÅT = 150 K
c = 13.0663 (9) Å0.32 × 0.24 × 0.12 mm
β = 120.664 (5)°
Data collection top
Stoe IPDS2
diffractometer		5771 independent reflections
Absorption correction: numerical
(X-AREA; Stoe & Cie, 2002)		4259 reflections with I > 2σ(I)
Tmin = 0.727, Tmax = 0.883Rint = 0.070
10087 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.058H-atom parameters constrained
wR(F2) = 0.160Δρmax = 1.02 e Å−3
S = 1.01Δρmin = −1.09 e Å−3
5771 reflectionsAbsolute structure: Flack (1983), 2594 Friedel pairs
331 parametersAbsolute structure parameter: 0.346 (19)
8 restraints
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)
N10.9825 (4)0.1792 (4)0.0032 (4)0.0321 (12)
C110.9177 (5)0.2042 (4)0.1237 (6)0.0314 (14)
C90.9264 (5)0.2899 (5)0.3232 (7)0.0358 (16)
H90.93170.31890.39420.043*
C80.8537 (6)0.2293 (5)0.2455 (7)0.0388 (16)
H80.80730.21790.26160.047*
C120.9124 (4)0.1580 (5)0.0166 (5)0.0270 (12)
C70.8467 (5)0.1836 (5)0.1419 (6)0.0322 (13)
C10.9812 (5)0.1396 (6)−0.0927 (6)0.0398 (15)
H11.03030.1539−0.10280.048*
C40.8389 (5)0.0977 (5)−0.0645 (6)0.0341 (14)
C60.7713 (5)0.1197 (6)0.0568 (6)0.0363 (14)
H60.72400.10530.07050.044*
C50.7675 (5)0.0797 (5)−0.0437 (6)0.0369 (15)
H50.71660.0394−0.10040.044*
C20.9085 (6)0.0763 (5)−0.1810 (6)0.0437 (19)
H20.90910.0477−0.24840.052*
C100.9946 (5)0.3089 (5)0.2959 (6)0.0346 (14)
H101.04480.35260.34830.042*
C30.8385 (5)0.0578 (5)−0.1665 (5)0.0358 (14)
H30.78860.0176−0.22540.043*
N41.1718 (4)0.1823 (4)0.2833 (4)0.0291 (11)
N31.1675 (4)0.2753 (4)0.0952 (5)0.0289 (11)
C281.3163 (5)0.0529 (6)0.4483 (6)0.0386 (14)
H281.36360.00720.50430.046*
C271.3163 (5)0.0950 (5)0.3475 (6)0.0324 (14)
C221.2237 (6)0.3009 (6)−0.0345 (6)0.0389 (16)
H221.21570.3323−0.10610.047*
C211.1627 (5)0.3212 (6)−0.0013 (6)0.0382 (15)
H211.11470.3701−0.04890.046*
C301.1765 (5)0.1415 (5)0.3818 (6)0.0351 (14)
H301.12910.15670.39510.042*
C241.3057 (4)0.1865 (5)0.1399 (6)0.0313 (13)
C291.2464 (5)0.0790 (6)0.4645 (6)0.0386 (16)
H291.24690.05330.53360.046*
C231.2969 (6)0.2347 (6)0.0355 (6)0.0367 (15)
H231.34040.22190.01400.044*
O31.0467 (3)0.4360 (3)0.0884 (3)0.0413 (10)
O40.9925 (3)0.6192 (4)0.0848 (4)0.0398 (10)
C321.2395 (5)0.2082 (5)0.1656 (6)0.0298 (13)
C311.2409 (4)0.1608 (5)0.2672 (5)0.0278 (12)
C261.3840 (5)0.0775 (6)0.3205 (6)0.0377 (15)
H261.43380.03370.37370.045*
C251.3812 (5)0.1204 (6)0.2219 (6)0.0383 (14)
H251.42820.10690.20750.046*
Cu11.07989 (4)0.28399 (4)0.14929 (5)0.03031 (16)
S21.06669 (9)0.54426 (10)0.15762 (10)0.0283 (3)
N20.9884 (4)0.2662 (4)0.1978 (5)0.0306 (12)
O11.0717 (3)0.5217 (3)0.2709 (3)0.0329 (8)
O21.1491 (3)0.5917 (4)0.1765 (4)0.0494 (13)
C41A1.0959 (9)0.8927 (10)0.1088 (12)0.059 (3)*0.695 (15)
H41A1.07570.94780.04340.071*0.695 (15)
H41B1.14970.92560.17680.071*0.695 (15)
C42A1.0326 (8)0.8986 (9)0.1425 (11)0.050 (2)*0.695 (15)
H42A1.04910.96410.19620.060*0.695 (15)
H42B0.97630.91860.06960.060*0.695 (15)
C41B1.132 (2)0.890 (2)0.158 (3)0.059 (3)*0.305 (15)
H41C1.11780.96320.11640.071*0.305 (15)
H41D1.19540.89230.21920.071*0.305 (15)
C42B1.0858 (15)0.8890 (19)0.221 (2)0.050 (2)*0.305 (15)
H42C1.13050.87180.30440.060*0.305 (15)
H42D1.06630.96710.21970.060*0.305 (15)
O411.1240 (5)0.8127 (6)0.0766 (7)0.0523 (15)*0.663 (10)
O421.0135 (10)0.8216 (12)0.1916 (14)0.0523 (15)*0.337 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.044 (3)0.028 (3)0.030 (3)0.001 (2)0.023 (3)0.001 (2)
C110.048 (4)0.017 (3)0.027 (3)0.001 (3)0.018 (3)−0.002 (2)
C90.049 (4)0.031 (3)0.035 (4)−0.004 (3)0.027 (4)−0.003 (2)
C80.052 (4)0.032 (3)0.048 (4)0.006 (3)0.037 (4)0.007 (3)
C120.034 (3)0.023 (3)0.020 (2)0.002 (2)0.011 (3)0.001 (2)
C70.042 (4)0.024 (3)0.032 (3)0.008 (3)0.021 (3)0.008 (2)
C10.055 (4)0.037 (4)0.030 (3)0.003 (3)0.024 (3)−0.001 (3)
C40.044 (4)0.029 (3)0.027 (3)−0.001 (3)0.017 (3)0.003 (2)
C60.038 (4)0.036 (3)0.036 (3)−0.002 (3)0.020 (3)0.004 (3)
C50.043 (4)0.030 (3)0.028 (3)−0.003 (3)0.011 (3)0.000 (2)
C20.073 (6)0.031 (3)0.028 (3)−0.008 (3)0.027 (4)−0.009 (3)
C100.048 (4)0.027 (3)0.027 (3)−0.004 (3)0.017 (3)−0.007 (2)
C30.047 (4)0.027 (3)0.021 (3)−0.001 (3)0.008 (3)−0.003 (2)
N40.039 (3)0.024 (2)0.017 (2)0.001 (2)0.009 (2)0.0012 (18)
N30.031 (3)0.029 (3)0.027 (3)0.009 (2)0.015 (3)0.0079 (19)
C280.045 (4)0.034 (3)0.024 (3)0.002 (3)0.007 (3)0.000 (2)
C270.037 (4)0.024 (3)0.024 (3)−0.004 (2)0.006 (3)−0.006 (2)
C220.053 (4)0.042 (4)0.027 (3)0.001 (3)0.024 (4)0.006 (3)
C210.050 (4)0.037 (3)0.038 (4)0.006 (3)0.029 (4)0.009 (3)
C300.048 (4)0.031 (3)0.031 (3)0.008 (3)0.023 (3)0.009 (2)
C240.031 (3)0.031 (3)0.028 (3)0.002 (2)0.012 (3)−0.001 (2)
C290.049 (4)0.039 (4)0.021 (3)0.004 (3)0.013 (3)0.008 (3)
C230.046 (4)0.037 (3)0.030 (3)0.001 (3)0.021 (3)0.000 (3)
O30.069 (3)0.0277 (18)0.030 (2)0.0063 (19)0.027 (2)−0.0005 (15)
O40.041 (3)0.036 (2)0.027 (2)0.0091 (19)0.007 (2)0.0044 (18)
C320.031 (3)0.030 (3)0.023 (3)−0.003 (2)0.010 (3)−0.006 (2)
C310.033 (3)0.023 (3)0.020 (2)0.000 (2)0.008 (3)−0.002 (2)
C260.034 (4)0.040 (4)0.028 (3)0.004 (3)0.008 (3)0.000 (3)
C250.035 (4)0.035 (3)0.037 (3)0.001 (3)0.012 (3)−0.004 (3)
Cu10.0389 (3)0.0257 (2)0.0295 (3)0.0021 (4)0.0197 (3)0.0019 (3)
S20.0318 (8)0.0280 (5)0.0221 (6)−0.0002 (6)0.0116 (6)0.0000 (5)
N20.040 (3)0.029 (3)0.027 (3)−0.001 (2)0.020 (3)−0.0030 (19)
O10.038 (2)0.0352 (18)0.0220 (17)0.0030 (17)0.0128 (18)0.0037 (15)
O20.034 (3)0.075 (4)0.040 (3)−0.013 (2)0.020 (2)0.002 (2)
Geometric parameters (Å, º) top
N1—C11.329 (7)C22—C211.366 (10)
N1—C121.352 (8)C22—C231.383 (11)
N1—Cu12.191 (6)C22—H220.9500
C11—N21.342 (9)C21—H210.9500
C11—C71.405 (10)C30—C291.370 (10)
C11—C121.462 (8)C30—H300.9500
C9—C81.364 (11)C24—C321.389 (9)
C9—C101.431 (10)C24—C231.415 (9)
C9—H90.9500C24—C251.441 (10)
C8—C71.406 (9)C29—H290.9500
C8—H80.9500C23—H230.9500
C12—C41.382 (10)O3—S21.513 (4)
C7—C61.437 (10)O3—Cu11.947 (4)
C1—C21.424 (11)O4—S21.462 (5)
C1—H10.9500C32—C311.431 (8)
C4—C31.412 (9)C26—C251.363 (10)
C4—C51.429 (10)C26—H260.9500
C6—C51.366 (9)C25—H250.9500
C6—H60.9500Cu1—N22.015 (5)
C5—H50.9500S2—O21.453 (5)
C2—C31.354 (11)S2—O11.463 (3)
C2—H20.9500C41A—O411.242 (11)
C10—N21.331 (8)C41A—C42A1.391 (12)
C10—H100.9500C41A—H41A0.9900
C3—H30.9500C41A—H41B0.9900
N4—C301.340 (7)C42A—O421.260 (13)
N4—C311.356 (8)C42A—H42A0.9900
N4—Cu12.064 (5)C42A—H42B0.9900
N3—C211.337 (8)C41B—O411.360 (17)
N3—C321.378 (9)C41B—C42B1.411 (18)
N3—Cu11.995 (5)C41B—H41C0.9900
C28—C291.382 (10)C41B—H41D0.9900
C28—C271.410 (9)C42B—O421.384 (17)
C28—H280.9500C42B—H42C0.9900
C27—C261.416 (10)C42B—H42D0.9900
C27—C311.433 (9)
C1—N1—C12118.4 (6)C30—C29—C28120.7 (6)
C1—N1—Cu1131.0 (5)C30—C29—H29119.7
C12—N1—Cu1110.5 (4)C28—C29—H29119.7
N2—C11—C7123.2 (6)C22—C23—C24118.5 (6)
N2—C11—C12118.9 (6)C22—C23—H23120.7
C7—C11—C12117.9 (6)C24—C23—H23120.7
C8—C9—C10118.9 (6)S2—O3—Cu1128.5 (2)
C8—C9—H9120.6N3—C32—C24122.9 (6)
C10—C9—H9120.6N3—C32—C31115.2 (5)
C9—C8—C7120.8 (7)C24—C32—C31121.9 (6)
C9—C8—H8119.6N4—C31—C32118.3 (6)
C7—C8—H8119.6N4—C31—C27123.7 (5)
N1—C12—C4123.6 (5)C32—C31—C27118.0 (6)
N1—C12—C11115.8 (6)C25—C26—C27123.4 (7)
C4—C12—C11120.6 (6)C25—C26—H26118.3
C11—C7—C8116.5 (6)C27—C26—H26118.3
C11—C7—C6120.5 (6)C26—C25—C24119.0 (7)
C8—C7—C6123.0 (6)C26—C25—H25120.5
N1—C1—C2122.0 (7)C24—C25—H25120.5
N1—C1—H1119.0O3—Cu1—N391.59 (18)
C2—C1—H1119.0O3—Cu1—N296.1 (2)
C12—C4—C3116.9 (6)N3—Cu1—N2170.74 (16)
C12—C4—C5119.9 (6)O3—Cu1—N4146.72 (19)
C3—C4—C5123.1 (7)N3—Cu1—N481.9 (2)
C5—C6—C7120.3 (6)N2—Cu1—N494.3 (2)
C5—C6—H6119.9O3—Cu1—N1103.76 (18)
C7—C6—H6119.9N3—Cu1—N193.5 (2)
C6—C5—C4120.8 (7)N2—Cu1—N179.7 (2)
C6—C5—H5119.6N4—Cu1—N1109.17 (14)
C4—C5—H5119.6O2—S2—O4110.5 (3)
C3—C2—C1118.4 (6)O2—S2—O1111.1 (3)
C3—C2—H2120.8O4—S2—O1110.2 (2)
C1—C2—H2120.8O2—S2—O3110.0 (3)
N2—C10—C9120.8 (6)O4—S2—O3106.0 (3)
N2—C10—H10119.6O1—S2—O3108.9 (2)
C9—C10—H10119.6C10—N2—C11119.8 (6)
C2—C3—C4120.6 (7)C10—N2—Cu1125.1 (5)
C2—C3—H3119.7C11—N2—Cu1115.0 (4)
C4—C3—H3119.7O41—C41A—C42A131.8 (11)
C30—N4—C31117.3 (6)O41—C41A—H41A104.3
C30—N4—Cu1131.8 (4)C42A—C41A—H41A104.3
C31—N4—Cu1110.7 (4)O41—C41A—H41B104.3
C21—N3—C32117.6 (5)C42A—C41A—H41B104.3
C21—N3—Cu1128.5 (5)H41A—C41A—H41B105.6
C32—N3—Cu1113.8 (4)O42—C42A—C41A126.0 (13)
C29—C28—C27119.0 (6)O42—C42A—H42A105.8
C29—C28—H28120.5C41A—C42A—H42A105.8
C27—C28—H28120.5O42—C42A—H42B105.8
C28—C27—C26125.5 (7)C41A—C42A—H42B105.8
C28—C27—C31116.1 (6)H42A—C42A—H42B106.2
C26—C27—C31118.4 (6)O41—C41B—C42B126 (2)
C21—C22—C23120.4 (6)O41—C41B—H41C105.8
C21—C22—H22119.8C42B—C41B—H41C105.8
C23—C22—H22119.8O41—C41B—H41D105.8
N3—C21—C22122.9 (7)C42B—C41B—H41D105.8
N3—C21—H21118.5H41C—C41B—H41D106.2
C22—C21—H21118.5O42—C42B—C41B124 (2)
N4—C30—C29123.1 (6)O42—C42B—H42C106.3
N4—C30—H30118.4C41B—C42B—H42C106.3
C29—C30—H30118.4O42—C42B—H42D106.3
C32—C24—C23117.6 (6)C41B—C42B—H42D106.3
C32—C24—C25119.2 (6)H42C—C42B—H42D106.4
C23—C24—C25123.1 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O2i0.952.483.389 (9)161
C5—H5···O1i0.952.343.263 (9)165
C6—H6···O2ii0.952.353.252 (11)158
C9—H9···O4iii0.952.283.188 (9)161
C10—H10···O10.952.412.973 (8)118
C21—H21···O1iv0.952.443.175 (8)134
C25—H25···O1v0.952.443.285 (11)149
C25—H25···O4v0.952.393.255 (11)151
C26—H26···O3vi0.952.503.200 (8)130
C28—H28···O4vi0.952.463.367 (10)159
C30—H30···O41iii0.952.453.165 (12)132
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x−1/2, y−1/2, z; (iii) x, −y+1, z+1/2; (iv) x, −y+1, z−1/2; (v) x+1/2, y−1/2, z; (vi) x+1/2, −y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O2i0.952.483.389 (9)161
C5—H5···O1i0.952.343.263 (9)165
C6—H6···O2ii0.952.353.252 (11)158
C9—H9···O4iii0.952.283.188 (9)161
C10—H10···O10.952.412.973 (8)118
C21—H21···O1iv0.952.443.175 (8)134
C25—H25···O1v0.952.443.285 (11)149
C25—H25···O4v0.952.393.255 (11)151
C26—H26···O3vi0.952.503.200 (8)130
C28—H28···O4vi0.952.463.367 (10)159
C30—H30···O41iii0.952.453.165 (12)132
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x−1/2, y−1/2, z; (iii) x, −y+1, z+1/2; (iv) x, −y+1, z−1/2; (v) x+1/2, y−1/2, z; (vi) x+1/2, −y+1/2, z+1/2.
 

Acknowledgements

The Thailand Research Fund is acknowledged for funding. NM thanks the Science Achievement Scholarship of Thailand and the Graduate School, Chiang Mai University for schol­arships.

References

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Journal logoCRYSTALLOGRAPHIC
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ISSN: 2056-9890
Volume 69| Part 10| October 2013| Pages m568-m569
doi:10.1107/S1600536813026093
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