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Acta Cryst. (2007). E63, m2160    [ doi:10.1107/S1600536807032175 ]

Poly[[aqua-[mu]-cyanido-tetrakis(ethylenediamine)dicopper(II)] [nona-[mu]-cyanido-dizincate(II)dicuprate(I)]]

G. Indramahalakshmi, A. Thamaraichelvan, R. Gandhidasan, S. Athimoolam and S. Natarajan

Abstract top

The title compound, {[Cu2(CN)(C2H8N2)4(H2O)][Cu2Zn2(CN)9]}n, is a host-guest structure in which the host is constituted by the ZnII and CuI atoms bridged by cyanide ions, and the guest consists of CuII, ethylenediamine, a cyanide and a water molecule. The guest and host species are linked through five N-H...N hydrogen bonds. ZnII and CuI in the host (or cation), have tetrahedral coordination. CuII in the guest (or anion) are penta- and hexacoordinated, leading to distorted square-pyramidal and square-bipyramidal structures, respectively

Comment top

Cyanide–metal complexes which form host frameworks, is one of the archetypal host–guest materials and its discovery has spawned a very rich structural chemistry. Hofmann type clathrates of the general formula MLNi(CN)4.g (M=bivalent metal ion, L-Ligand, g-guest) have been studied extensively (Akyuz et al., 1974). However, studies on clathrates with Men2Ni(CN)4 and MenM'(CN)4 (M'=Cd, Zn, Hg, Ni; en=ethylenediamine) as hosts are limited in literature (Iwamoto & Shriver, 1972). During the process of synthesizing Men2M'(CN)4 (M'=Cd, Zn, Hg), the single crystals of the title compound were obtained.

The asymmetric unit contains two ZnII and two CuI atoms linked through nine cyanido ions and two CuII-en2 bridged through a CN group and a lattice water molecule as guest (Fig. 1). All the metal atoms in the host, ZnII and CuI, are observed to be tetra-coordinated whereas CuII atoms are penta- and hexa coordinated in the guest. The en molecules in guest are in the gauche conformation. The angle between the planes N35—Cu3—N38 and N31—Cu3—N34 is 16.6 (1)° while this value is 53.3 (2)° for planes N45—Cu4—N48 and N41—Cu4—N44. These values replicate the angle of orientation between the en2 molecules.

There are five intermolecular N—H···N hydrogen bonds in the structure through which guest and host molecules are linked (Table 2; Fig. 2).

Related literature top

For related literature, see: Akyuz et al. (1974); Iwamoto & Shriver (1972); Macrae et al. (2006).

Experimental top

5 mmol of ethylenediamine was added to 2.5 mmol of CuCl2 in 10 ml of water. This solution was mixed up with the 10 ml of water containing 2.5 mmol of K2Zn(CN)4. Tiny needle-shaped crystals were found within a week, at room temperature by slow evaporation.

Refinement top

All the H atoms were positioned geometrically and refined using a riding model, with C—H = 0.9 Å and N—H= 0.97 Å with Uiso(H) = 1.2Ueq (C or N). Attempts to locate the H atoms of the water oxygen present in the lattice were not successfull, due to the presence of heavy atoms in the structure.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound, with the atom-numbering scheme and 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. Packing diagram of the molecules viewed down the b-axis. H-bonds are shown as dashed lines.
Poly[[aqua-µ-cyanido-tetrakis(ethylenediamine)dicopper(II)] [nona-µ-cyanido-dizincate(II)dicuprate(I)]] top
Crystal data top
{[Cu2(CN)(C2H8N2)4(H2O)][Cu2Zn2(CN)9]}F(000) = 1800
Mr = 901.52Dx = 1.726 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 18.1816 (9) ÅCell parameters from 25 reflections
b = 12.4844 (7) Åθ = 10.3–13.6°
c = 16.1923 (8) ŵ = 3.81 mm−1
β = 109.246 (11)°T = 293 K
V = 3470.0 (3) Å3Needle, blue
Z = 40.26 × 0.19 × 0.16 mm
Data collection top
Enraf-Nonius MACH3 sealed tube
diffractometer		3637 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.029
graphiteθmax = 25.0°, θmin = 2.0°
ω–2θ scansh = −21→20
Absorption correction: ψ scan
(North et al., 1968)		k = −1→14
Tmin = 0.929, Tmax = 0.983l = 0→19
6961 measured reflections3 standard reflections every 60 min
6089 independent reflections intensity decay: none
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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0329P)2 + 8.1818P]
where P = (Fo2 + 2Fc2)/3
6089 reflections(Δ/σ)max = 0.001
382 parametersΔρmax = 0.75 e Å−3
0 restraintsΔρmin = −0.56 e Å−3
Crystal data top
{[Cu2(CN)(C2H8N2)4(H2O)][Cu2Zn2(CN)9]}V = 3470.0 (3) Å3
Mr = 901.52Z = 4
Monoclinic, P21/cMo Kα radiation
a = 18.1816 (9) ŵ = 3.81 mm−1
b = 12.4844 (7) ÅT = 293 K
c = 16.1923 (8) Å0.26 × 0.19 × 0.16 mm
β = 109.246 (11)°
Data collection top
Enraf-Nonius MACH3 sealed tube
diffractometer		3637 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.029
Tmin = 0.929, Tmax = 0.983θmax = 25.0°
6961 measured reflections3 standard reflections every 60 min
6089 independent reflections intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.101Δρmax = 0.75 e Å−3
S = 1.04Δρmin = −0.56 e Å−3
6089 reflectionsAbsolute structure: ?
382 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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*/Ueq
Zn10.11314 (4)0.68154 (6)0.68142 (4)0.03848 (18)
Zn20.55735 (4)0.79273 (5)1.12894 (4)0.03891 (18)
Cu1−0.05596 (4)0.78446 (5)0.86348 (4)0.03212 (17)
Cu20.39149 (3)0.81159 (5)0.81452 (4)0.02642 (15)
C10.0475 (3)0.7268 (5)0.7513 (3)0.0402 (14)
N20.0068 (3)0.7495 (4)0.7895 (3)0.0476 (13)
C30.1056 (3)0.5226 (5)0.6729 (4)0.0353 (13)
N40.0915 (3)0.4338 (4)0.6600 (3)0.0468 (13)
C50.0553 (3)0.7155 (5)0.5575 (4)0.0409 (14)
N60.0167 (3)0.7182 (4)0.4860 (3)0.0515 (14)
C70.2213 (3)0.7327 (5)0.7319 (4)0.0396 (14)
N80.2837 (3)0.7603 (4)0.7642 (3)0.0443 (12)
N90.4488 (3)0.7682 (4)0.9355 (3)0.0455 (12)
C100.4898 (3)0.7781 (5)1.0063 (4)0.0408 (14)
N110.3914 (3)0.9700 (4)0.8244 (3)0.0404 (12)
C120.4097 (3)1.0570 (5)0.8421 (4)0.0339 (13)
N130.4524 (3)0.7726 (4)0.7388 (3)0.0445 (12)
C140.4932 (3)0.7508 (5)0.7007 (3)0.0377 (13)
C150.6530 (4)0.7099 (5)1.1432 (4)0.0510 (16)
N160.7093 (4)0.6706 (6)1.1437 (5)0.108 (3)
N17−0.1511 (5)0.6910 (7)0.8548 (5)0.108 (3)
C18−0.2042 (5)0.6461 (9)0.8560 (7)0.137 (5)
Cu40.25758 (5)0.92268 (6)0.49821 (6)0.0483 (2)
N410.3639 (3)0.9584 (5)0.4690 (4)0.0615 (16)
H41A0.38080.89930.44910.074*
H41B0.35441.00930.42740.074*
C420.4230 (4)0.9960 (7)0.5493 (5)0.082 (2)
H42A0.45030.93500.58270.098*
H42B0.46081.04020.53450.098*
C430.3869 (5)1.0576 (8)0.6019 (6)0.094 (3)
H43A0.36751.12490.57290.112*
H43B0.42521.07360.65840.112*
N440.3220 (3)0.9955 (5)0.6141 (3)0.0709 (18)
H44A0.29111.03940.63210.085*
H44B0.34120.94530.65550.085*
N450.1873 (3)0.9957 (5)0.3858 (3)0.0560 (15)
H45A0.21441.04750.36990.067*
H45B0.17260.94720.34230.067*
C460.1189 (4)1.0420 (7)0.3983 (5)0.080 (2)
H46A0.07941.05490.34200.096*
H46B0.13211.11000.42850.096*
C470.0879 (5)0.9660 (8)0.4513 (5)0.090 (3)
H47A0.04530.99940.46520.108*
H47B0.06830.90170.41760.108*
N480.1501 (4)0.9382 (5)0.5316 (4)0.0691 (17)
H48A0.13910.87600.55320.083*
H48B0.15550.98970.57210.083*
Cu30.25415 (4)0.49772 (6)0.50091 (5)0.04579 (18)
N310.2732 (3)0.4842 (5)0.6358 (3)0.0608 (15)
H31A0.24650.53510.65310.073*
H31B0.25740.41960.64800.073*
N380.1321 (3)0.4859 (5)0.4631 (4)0.0679 (17)
H38A0.11870.43320.49320.082*
H38B0.11190.54780.47430.082*
N340.3741 (3)0.4748 (5)0.5404 (4)0.0677 (17)
H34A0.38580.42380.50740.081*
H34B0.39790.53600.53390.081*
N350.2314 (3)0.4734 (7)0.3669 (4)0.096 (3)
H35A0.25730.52190.34580.116*
H35B0.24670.40740.35720.116*
C330.4008 (4)0.4424 (8)0.6318 (5)0.083 (3)
H33A0.45560.45960.65810.100*
H33B0.39490.36550.63570.100*
C320.3559 (4)0.4971 (8)0.6801 (5)0.084 (3)
H32A0.36960.46770.73860.101*
H32B0.36880.57270.68500.101*
C370.1033 (5)0.4634 (13)0.3725 (6)0.153 (4)
H37A0.09090.38760.36580.184*
H37B0.05470.50210.34800.184*
N30.2591 (4)0.6693 (4)0.4970 (5)0.0652 (15)
C360.1473 (5)0.4855 (13)0.3244 (6)0.153 (4)
H36A0.13700.55880.30400.184*
H36B0.13140.43950.27320.184*
C40.2595 (4)0.7598 (5)0.4957 (5)0.0597 (17)
O1W0.2468 (5)0.2864 (6)0.4956 (6)0.161 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0349 (3)0.0439 (4)0.0356 (4)−0.0074 (3)0.0101 (3)−0.0064 (3)
Zn20.0438 (4)0.0372 (4)0.0365 (4)−0.0040 (3)0.0143 (3)−0.0010 (3)
Cu10.0380 (4)0.0311 (4)0.0274 (3)0.0056 (3)0.0109 (3)0.0005 (3)
Cu20.0245 (3)0.0282 (3)0.0249 (3)−0.0051 (3)0.0059 (3)−0.0044 (3)
C10.044 (3)0.043 (4)0.030 (3)−0.004 (3)0.007 (3)−0.006 (3)
N20.056 (3)0.053 (3)0.038 (3)0.011 (3)0.021 (3)−0.006 (2)
C30.031 (3)0.041 (4)0.038 (3)−0.007 (3)0.017 (3)−0.004 (3)
N40.050 (3)0.042 (3)0.048 (3)−0.009 (3)0.017 (3)−0.003 (3)
C50.042 (3)0.040 (3)0.040 (3)−0.006 (3)0.012 (3)0.003 (3)
N60.059 (3)0.055 (4)0.033 (3)−0.015 (3)0.006 (2)0.000 (3)
C70.040 (3)0.040 (3)0.039 (3)−0.011 (3)0.014 (3)−0.010 (3)
N80.033 (3)0.054 (3)0.043 (3)−0.013 (2)0.009 (2)−0.014 (3)
N90.049 (3)0.050 (3)0.034 (3)−0.004 (3)0.010 (2)0.002 (2)
C100.044 (3)0.041 (4)0.036 (3)−0.004 (3)0.011 (3)0.003 (3)
N110.040 (3)0.033 (3)0.047 (3)−0.002 (2)0.012 (2)−0.008 (2)
C120.034 (3)0.035 (4)0.031 (3)−0.002 (3)0.009 (2)−0.003 (3)
N130.045 (3)0.048 (3)0.045 (3)−0.002 (3)0.020 (2)−0.011 (3)
C140.041 (3)0.039 (3)0.032 (3)−0.003 (3)0.010 (3)−0.005 (3)
C150.052 (4)0.045 (4)0.056 (4)0.004 (3)0.017 (3)−0.014 (3)
N160.063 (4)0.111 (6)0.140 (7)0.027 (4)0.019 (4)−0.059 (5)
N170.117 (6)0.096 (6)0.088 (5)0.006 (5)0.005 (5)0.038 (5)
C180.071 (6)0.148 (10)0.158 (10)−0.068 (6)−0.010 (6)0.104 (8)
Cu40.0679 (5)0.0376 (4)0.0450 (4)−0.0025 (4)0.0263 (4)0.0003 (4)
N410.080 (4)0.047 (3)0.068 (4)0.004 (3)0.039 (3)0.008 (3)
C420.066 (5)0.097 (7)0.091 (6)0.000 (5)0.037 (5)−0.016 (5)
C430.062 (5)0.123 (8)0.088 (6)−0.011 (5)0.015 (5)−0.031 (6)
N440.064 (4)0.105 (5)0.041 (3)0.004 (4)0.014 (3)−0.004 (4)
N450.053 (3)0.071 (4)0.042 (3)−0.010 (3)0.014 (3)0.003 (3)
C460.063 (5)0.106 (7)0.067 (5)−0.001 (5)0.015 (4)0.013 (5)
C470.065 (5)0.137 (8)0.074 (6)−0.038 (5)0.029 (5)−0.024 (6)
N480.090 (4)0.063 (4)0.070 (4)−0.023 (3)0.046 (4)−0.003 (3)
Cu30.0310 (3)0.0597 (4)0.0480 (4)0.0039 (4)0.0149 (3)−0.0018 (5)
N310.052 (3)0.073 (4)0.063 (4)0.002 (3)0.026 (3)0.001 (3)
N380.045 (3)0.088 (5)0.078 (4)0.001 (3)0.030 (3)−0.010 (4)
N340.046 (3)0.088 (5)0.076 (4)0.024 (3)0.029 (3)0.016 (4)
N350.053 (4)0.159 (7)0.088 (5)−0.027 (4)0.037 (4)−0.049 (5)
C330.040 (4)0.125 (8)0.079 (6)0.021 (4)0.012 (4)0.039 (5)
C320.065 (5)0.129 (8)0.049 (4)−0.017 (5)0.005 (4)−0.002 (5)
C370.047 (4)0.319 (13)0.088 (5)−0.012 (6)0.014 (3)−0.032 (7)
N30.066 (4)0.040 (3)0.088 (4)0.003 (3)0.023 (3)0.000 (4)
C360.047 (4)0.319 (13)0.088 (5)−0.012 (6)0.014 (3)−0.032 (7)
C40.072 (5)0.042 (4)0.072 (4)0.006 (4)0.033 (4)0.004 (4)
O1W0.178 (8)0.106 (6)0.189 (9)0.019 (6)0.048 (7)−0.001 (7)
Geometric parameters (Å, °) top
Zn1—C71.971 (6)C43—H43B0.9700
Zn1—C11.979 (6)N44—H44A0.9000
Zn1—C51.980 (6)N44—H44B0.9000
Zn1—C31.991 (6)N45—C461.445 (9)
Zn2—C101.969 (6)N45—H45A0.9000
Zn2—C151.970 (6)N45—H45B0.9000
Zn2—C14i1.974 (6)C46—C471.508 (11)
Zn2—C12ii1.978 (6)C46—H46A0.9700
Cu1—N21.957 (5)C46—H46B0.9700
Cu1—N4iii1.968 (5)C47—N481.456 (9)
Cu1—N6i1.989 (5)C47—H47A0.9700
Cu1—N172.053 (9)C47—H47B0.9700
Cu2—N131.966 (5)N48—H48A0.9000
Cu2—N81.966 (5)N48—H48B0.9000
Cu2—N91.968 (5)Cu3—N342.081 (5)
Cu2—N111.984 (5)Cu3—N352.092 (6)
C1—N21.144 (7)Cu3—N312.102 (5)
C3—N41.142 (7)Cu3—N382.103 (5)
N4—Cu1iv1.968 (5)Cu3—N32.145 (5)
C5—N61.139 (7)N31—C321.445 (8)
N6—Cu1v1.989 (5)N31—H31A0.9000
C7—N81.134 (6)N31—H31B0.9000
N9—C101.149 (7)N38—C371.413 (10)
N11—C121.145 (7)N38—H38A0.9000
C12—Zn2ii1.978 (6)N38—H38B0.9000
N13—C141.142 (6)N34—C331.455 (9)
C14—Zn2v1.974 (5)N34—H34A0.9000
C15—N161.132 (8)N34—H34B0.9000
N17—C181.122 (9)N35—C361.464 (10)
Cu4—C42.034 (7)N35—H35A0.9000
Cu4—N452.060 (5)N35—H35B0.9000
Cu4—N442.066 (5)C33—C321.471 (10)
Cu4—N412.182 (5)C33—H33A0.9700
Cu4—N482.202 (6)C33—H33B0.9700
N41—C421.465 (9)C32—H32A0.9700
N41—H41A0.9000C32—H32B0.9700
N41—H41B0.9000C37—C361.317 (12)
C42—C431.455 (10)C37—H37A0.9700
C42—H42A0.9700C37—H37B0.9700
C42—H42B0.9700N3—C41.131 (8)
C43—N441.479 (10)C36—H36A0.9700
C43—H43A0.9700C36—H36B0.9700
C7—Zn1—C1112.2 (2)H45A—N45—H45B108.0
C7—Zn1—C5118.4 (2)N45—C46—C47109.1 (7)
C1—Zn1—C5107.4 (2)N45—C46—H46A109.9
C7—Zn1—C3112.9 (2)C47—C46—H46A109.9
C1—Zn1—C3106.5 (2)N45—C46—H46B109.9
C5—Zn1—C398.1 (2)C47—C46—H46B109.9
C10—Zn2—C15107.6 (2)H46A—C46—H46B108.3
C10—Zn2—C14i105.9 (2)N48—C47—C46109.5 (6)
C15—Zn2—C14i117.2 (3)N48—C47—H47A109.8
C10—Zn2—C12ii111.5 (2)C46—C47—H47A109.8
C15—Zn2—C12ii106.5 (2)N48—C47—H47B109.8
C14i—Zn2—C12ii108.2 (2)C46—C47—H47B109.8
N2—Cu1—N4iii108.3 (2)H47A—C47—H47B108.2
N2—Cu1—N6i106.1 (2)C47—N48—Cu4107.0 (4)
N4iii—Cu1—N6i106.0 (2)C47—N48—H48A110.3
N2—Cu1—N17118.7 (3)Cu4—N48—H48A110.3
N4iii—Cu1—N17108.0 (3)C47—N48—H48B110.3
N6i—Cu1—N17109.1 (3)Cu4—N48—H48B110.3
N13—Cu2—N8110.53 (19)H48A—N48—H48B108.6
N13—Cu2—N9109.3 (2)N34—Cu3—N3597.3 (2)
N8—Cu2—N9116.8 (2)N34—Cu3—N3182.7 (2)
N13—Cu2—N11108.2 (2)N35—Cu3—N31166.9 (3)
N8—Cu2—N11109.3 (2)N34—Cu3—N38168.0 (2)
N9—Cu2—N11102.0 (2)N35—Cu3—N3881.9 (2)
N2—C1—Zn1176.6 (5)N31—Cu3—N3895.4 (2)
C1—N2—Cu1175.3 (5)N34—Cu3—N395.5 (2)
N4—C3—Zn1170.7 (5)N35—Cu3—N396.3 (3)
C3—N4—Cu1iv174.0 (5)N31—Cu3—N396.7 (3)
N6—C5—Zn1168.4 (5)N38—Cu3—N396.4 (2)
C5—N6—Cu1v175.8 (5)C32—N31—Cu3107.2 (4)
N8—C7—Zn1177.2 (5)C32—N31—H31A110.3
C7—N8—Cu2177.1 (5)Cu3—N31—H31A110.3
C10—N9—Cu2156.9 (5)C32—N31—H31B110.3
N9—C10—Zn2178.1 (5)Cu3—N31—H31B110.3
C12—N11—Cu2163.4 (5)H31A—N31—H31B108.5
N11—C12—Zn2ii178.8 (5)C37—N38—Cu3108.2 (5)
C14—N13—Cu2174.4 (5)C37—N38—H38A110.1
N13—C14—Zn2v175.9 (5)Cu3—N38—H38A110.1
N16—C15—Zn2171.4 (8)C37—N38—H38B110.1
C18—N17—Cu1173.3 (11)Cu3—N38—H38B110.1
C4—Cu4—N45115.8 (3)H38A—N38—H38B108.4
C4—Cu4—N44116.7 (3)C33—N34—Cu3108.3 (4)
N45—Cu4—N44127.5 (2)C33—N34—H34A110.0
C4—Cu4—N41100.2 (2)Cu3—N34—H34A110.0
N45—Cu4—N4193.1 (2)C33—N34—H34B110.0
N44—Cu4—N4180.2 (2)Cu3—N34—H34B110.0
C4—Cu4—N4896.6 (2)H34A—N34—H34B108.4
N45—Cu4—N4880.5 (2)C36—N35—Cu3107.0 (5)
N44—Cu4—N4891.3 (2)C36—N35—H35A110.3
N41—Cu4—N48163.1 (2)Cu3—N35—H35A110.3
C42—N41—Cu4108.5 (4)C36—N35—H35B110.3
C42—N41—H41A110.0Cu3—N35—H35B110.3
Cu4—N41—H41A110.0H35A—N35—H35B108.6
C42—N41—H41B110.0N34—C33—C32110.8 (6)
Cu4—N41—H41B110.0N34—C33—H33A109.5
H41A—N41—H41B108.4C32—C33—H33A109.5
C43—C42—N41110.4 (6)N34—C33—H33B109.5
C43—C42—H42A109.6C32—C33—H33B109.5
N41—C42—H42A109.6H33A—C33—H33B108.1
C43—C42—H42B109.6N31—C32—C33110.7 (6)
N41—C42—H42B109.6N31—C32—H32A109.5
H42A—C42—H42B108.1C33—C32—H32A109.5
C42—C43—N44109.5 (8)N31—C32—H32B109.5
C42—C43—H43A109.8C33—C32—H32B109.5
N44—C43—H43A109.8H32A—C32—H32B108.1
C42—C43—H43B109.8C36—C37—N38118.8 (9)
N44—C43—H43B109.8C36—C37—H37A107.6
H43A—C43—H43B108.2N38—C37—H37A107.6
C43—N44—Cu4110.4 (5)C36—C37—H37B107.6
C43—N44—H44A109.6N38—C37—H37B107.6
Cu4—N44—H44A109.6H37A—C37—H37B107.0
C43—N44—H44B109.6C4—N3—Cu3177.7 (6)
Cu4—N44—H44B109.6C37—C36—N35116.4 (9)
H44A—N44—H44B108.1C37—C36—H36A108.2
C46—N45—Cu4111.4 (4)N35—C36—H36A108.2
C46—N45—H45A109.3C37—C36—H36B108.2
Cu4—N45—H45A109.3N35—C36—H36B108.2
C46—N45—H45B109.3H36A—C36—H36B107.3
Cu4—N45—H45B109.3N3—C4—Cu4177.0 (7)
C7—Zn1—C1—N2−167 (9)N41—C42—C43—N4451.5 (10)
C5—Zn1—C1—N261 (9)C42—C43—N44—Cu4−42.6 (8)
C3—Zn1—C1—N2−43 (9)C4—Cu4—N44—C43114.3 (6)
Zn1—C1—N2—Cu1120 (8)N45—Cu4—N44—C43−68.5 (6)
N4iii—Cu1—N2—C1127 (7)N41—Cu4—N44—C4317.8 (5)
N6i—Cu1—N2—C113 (7)N48—Cu4—N44—C43−147.6 (5)
N17—Cu1—N2—C1−110 (7)C4—Cu4—N45—C46108.5 (5)
C7—Zn1—C3—N4−161 (3)N44—Cu4—N45—C46−68.7 (6)
C1—Zn1—C3—N475 (3)N41—Cu4—N45—C46−148.6 (5)
C5—Zn1—C3—N4−36 (3)N48—Cu4—N45—C4615.6 (5)
Zn1—C3—N4—Cu1iv−35 (8)Cu4—N45—C46—C47−41.1 (7)
C7—Zn1—C5—N6144 (3)N45—C46—C47—N4853.5 (9)
C1—Zn1—C5—N6−88 (3)C46—C47—N48—Cu4−38.1 (8)
C3—Zn1—C5—N622 (3)C4—Cu4—N48—C47−102.2 (6)
Zn1—C5—N6—Cu1v28 (10)N45—Cu4—N48—C4712.9 (5)
C1—Zn1—C7—N853 (11)N44—Cu4—N48—C47140.8 (5)
C5—Zn1—C7—N8179 (100)N41—Cu4—N48—C4781.7 (10)
C3—Zn1—C7—N8−67 (11)N34—Cu3—N31—C3215.6 (5)
Zn1—C7—N8—Cu2−178 (5)N35—Cu3—N31—C32106.4 (11)
N13—Cu2—N8—C7−52 (10)N38—Cu3—N31—C32−176.3 (5)
N9—Cu2—N8—C7−178 (100)N3—Cu3—N31—C32−79.2 (5)
N11—Cu2—N8—C767 (10)N34—Cu3—N38—C37−84.1 (14)
N13—Cu2—N9—C1094.8 (12)N35—Cu3—N38—C372.9 (8)
N8—Cu2—N9—C10−138.7 (12)N31—Cu3—N38—C37−164.2 (8)
N11—Cu2—N9—C10−19.6 (12)N3—Cu3—N38—C3798.4 (8)
Cu2—N9—C10—Zn2134 (17)N35—Cu3—N34—C33−156.0 (6)
C15—Zn2—C10—N9117 (18)N31—Cu3—N34—C3310.8 (6)
C14i—Zn2—C10—N9−9(18)N38—Cu3—N34—C33−70.6 (13)
C12ii—Zn2—C10—N9−127 (18)N3—Cu3—N34—C33106.9 (6)
N13—Cu2—N11—C12−71.8 (17)N34—Cu3—N35—C36179.7 (8)
N8—Cu2—N11—C12167.8 (16)N31—Cu3—N35—C3690.5 (13)
N9—Cu2—N11—C1243.4 (17)N38—Cu3—N35—C3611.8 (8)
Cu2—N11—C12—Zn2ii73 (30)N3—Cu3—N35—C36−83.9 (8)
N8—Cu2—N13—C14−157 (5)Cu3—N34—C33—C32−35.7 (8)
N9—Cu2—N13—C14−28 (5)Cu3—N31—C32—C33−39.7 (8)
N11—Cu2—N13—C1483 (5)N34—C33—C32—N3151.8 (10)
Cu2—N13—C14—Zn2v154 (4)Cu3—N38—C37—C36−20.3 (16)
C10—Zn2—C15—N1660 (4)N34—Cu3—N3—C4−150 (20)
C14i—Zn2—C15—N16179 (100)N35—Cu3—N3—C4112 (20)
C12ii—Zn2—C15—N16−59 (4)N31—Cu3—N3—C4−66 (20)
N2—Cu1—N17—C18180 (100)N38—Cu3—N3—C430 (20)
N4iii—Cu1—N17—C18−57 (6)N38—C37—C36—N3533 (2)
N6i—Cu1—N17—C1858 (6)Cu3—N35—C36—C37−27.3 (15)
C4—Cu4—N41—C42−106.7 (5)Cu3—N3—C4—Cu431 (34)
N45—Cu4—N41—C42136.4 (5)N45—Cu4—C4—N3−114 (16)
N44—Cu4—N41—C428.9 (5)N44—Cu4—C4—N363 (16)
N48—Cu4—N41—C4269.3 (10)N41—Cu4—C4—N3147 (16)
Cu4—N41—C42—C43−34.7 (9)N48—Cu4—C4—N3−31 (16)
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+1, −y+2, −z+2; (iii) −x, y+1/2, −z+3/2; (iv) −x, y−1/2, −z+3/2; (v) x, −y+3/2, z−1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N41—H41A···N9v0.902.483.352 (7)165
N41—H41B···N16vi0.902.423.242 (9)153
N44—H44B···N110.902.603.234 (7)128
N45—H45A···N16vi0.902.133.020 (8)170
N35—H35A···N11v0.902.583.280 (7)136
Symmetry codes: (v) x, −y+3/2, z−1/2; (vi) −x+1, y+1/2, −z+3/2.
Table 1
Selected geometric parameters (°) top
Zn1—C7—N8—Cu2−178 (5)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N41—H41A···N9i0.902.483.352 (7)165
N41—H41B···N16ii0.902.423.242 (9)153
N44—H44B···N110.902.603.234 (7)128
N45—H45A···N16ii0.902.133.020 (8)170
N35—H35A···N11i0.902.583.280 (7)136
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, y+1/2, −z+3/2.
Acknowledgements top

GI thanks the University Grants Commission (UGC), Government of India and the management of Cardamom Planters Association College, Bodinayakanur for providing a teacher fellowship. GI and AT thank the management of Thiagarajar College, Madurai.

references
References top

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