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

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

doi:10.1107/S1600536807032175

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

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

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 Zn^II and Cu^I atoms bridged by cyanide ions, and the guest consists of Cu^II, ethylenediamine, a cyanide and a water molecule. The guest and host species are linked through five N—H

N hydrogen bonds. Zn^II and Cu^I in the host (or cation), have tetrahedral coordination. Cu^II in the guest (or anion) are penta- and hexacoordinated, leading to distorted square-pyramidal and square-bipyramidal structures, respectively

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032175/bt2425sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032175/bt2425Isup2.hkl Contains datablock I

CCDC reference: 657589

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.013 Å
R factor = 0.037
wR factor = 0.101
Data-to-parameter ratio = 15.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT110_ALERT_2_B ADDSYM Detects Potential Lattice Centering or Halving .   ?
PLAT213_ALERT_2_B Atom C18     has ADP max/min Ratio .............       4.90 prola
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       4.05 Ratio
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for        C37
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        Cu1
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        Cu3
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        N38
PLAT360_ALERT_2_B Short  C(sp3)-C(sp3) Bond  C36    -   C37    ...       1.32 Ang.

Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
            Tmin and Tmax reported:      0.929     0.983
            Tmin and Tmax expected:      0.430     0.544
            RR =      1.196
            Please check that your absorption correction is appropriate.
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large .......       1.21
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.55
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT220_ALERT_2_C Large Non-Solvent    N     Ueq(max)/Ueq(min) ...       2.66 Ratio
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.55 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        N17
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C36
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C43
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C47
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Cu2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C15
PLAT320_ALERT_2_C Check Hybridisation of  C18    in Main Residue .          ?
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         13
PLAT420_ALERT_2_C D-H Without Acceptor       N31    -   H31A   ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N31    -   H31B   ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N34    -   H34A   ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N34    -   H34B   ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N35    -   H35B   ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N38    -   H38A   ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N38    -   H38B   ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N44    -   H44A   ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N45    -   H45B   ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N48    -   H48A   ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N48    -   H48B   ...          ?
PLAT432_ALERT_2_C Short Inter X...Y Contact  N44    ..  C18     ..       3.01 Ang.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          1
            C7  -ZN1 -C1  -N2   -167.00  9.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          2
            C5  -ZN1 -C1  -N2     61.00  9.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          3
            C3  -ZN1 -C1  -N2    -43.00  9.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          4
            ZN1 -C1  -N2  -CU1   120.00  8.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          5
            N4  -CU1 -N2  -C1    127.00  7.00   2.556   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          6
            N6  -CU1 -N2  -C1     13.00  7.00   4.576   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          7
            N17 -CU1 -N2  -C1   -110.00  7.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          8
            C7  -ZN1 -C3  -N4   -161.00  3.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          9
            C1  -ZN1 -C3  -N4     75.00  3.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         10
            C5  -ZN1 -C3  -N4    -36.00  3.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         11
            ZN1 -C3  -N4  -CU1   -35.00  8.00   1.555   1.555   1.555   2.546
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         15
            ZN1 -C5  -N6  -CU1    28.00 10.00   1.555   1.555   1.555   4.575
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         16
            C1  -ZN1 -C7  -N8     53.00 11.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         17
            C5  -ZN1 -C7  -N8     18.00  0.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         18
            C3  -ZN1 -C7  -N8    -67.00 11.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         19
            ZN1 -C7  -N8  -CU2  -178.00  5.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         20
            N13 -CU2 -N8  -C7    -52.00 10.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         21
            N9  -CU2 -N8  -C7     18.00  0.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         22
            N11 -CU2 -N8  -C7     67.00 10.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         26
            CU2 -N9  -C10 -ZN2   134.00 17.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         27
            C15 -ZN2 -C10 -N9    117.00 18.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         28
            C14 -ZN2 -C10 -N9     -9.00 18.00   4.576   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         29
            C12 -ZN2 -C10 -N9   -127.00 18.00   3.677   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         33
            CU2 -N11 -C12 -ZN2     7.00  0.00   1.555   1.555   1.555   3.677
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         34
            N8  -CU2 -N13 -C14  -157.00  5.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         35
            N9  -CU2 -N13 -C14   -28.00  5.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         36
            N11 -CU2 -N13 -C14    83.00  5.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         37
            CU2 -N13 -C14 -ZN2   154.00  4.00   1.555   1.555   1.555   4.575
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         38
            C10 -ZN2 -C15 -N16    60.00  4.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         39
            C14 -ZN2 -C15 -N16    18.00  0.00   4.576   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         40
            C12 -ZN2 -C15 -N16   -59.00  4.00   3.677   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         41
            N2  -CU1 -N17 -C18    18.00  0.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         42
            N4  -CU1 -N17 -C18   -57.00  6.00   2.556   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         43
            N6  -CU1 -N17 -C18    58.00  6.00   4.576   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         86
            N34 -CU3 -N3  -C4   -150.00 20.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         87
            N35 -CU3 -N3  -C4    112.00 20.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         88
            N31 -CU3 -N3  -C4    -66.00 20.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         89
            N38 -CU3 -N3  -C4     30.00 20.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         92
            CU3 -N3  -C4  -CU4     3.00  0.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         93
            N45 -CU4 -C4  -N3   -114.00 16.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         94
            N44 -CU4 -C4  -N3     63.00 16.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         95
            N41 -CU4 -C4  -N3    147.00 16.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         96
            N48 -CU4 -C4  -N3    -31.00 16.00   1.555   1.555   1.555   1.555

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.553
            Tmax scaled      0.544 Tmin scaled      0.514
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       2.10
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu2         (1)       1.18
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu3         (2)       1.92
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu4         (1)       0.99

   0 ALERT level A = In general: serious problem
   8 ALERT level B = Potentially serious problem
  71 ALERT level C = Check and explain
   7 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  29 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
  45 ALERT type 4 Improvement, methodology, query or suggestion
   4 ALERT type 5 Informative message, check

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 Zn^II and two Cu^I atoms linked through nine cyanido ions and two Cu^II-en₂ bridged through a CN group and a lattice water molecule as guest (Fig. 1). All the metal atoms in the host, Zn^II and Cu^I, are observed to be tetra-coordinated whereas Cu^II 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.

Structure description top

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

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

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

	Fig. 1. The asymmetric unit of the title compound, with the atom-numbering scheme and 50% probability displacement ellipsoids.
	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
M_r = 901.52	D_x = 1.726 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.1816 (9) Å	Cell parameters from 25 reflections
b = 12.4844 (7) Å	θ = 10.3–13.6°
c = 16.1923 (8) Å	µ = 3.81 mm⁻¹
β = 109.246 (11)°	T = 293 K
V = 3470.0 (3) Å³	Needle, blue
Z = 4	0.26 × 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 tube	R_int = 0.029
Graphite monochromator	θ_max = 25.0°, θ_min = 2.0°
ω–2θ scans	h = −21→20
Absorption correction: ψ scan (North et al., 1968)	k = −1→14
T_min = 0.929, T_max = 0.983	l = 0→19
6961 measured reflections	3 standard reflections every 60 min
6089 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0329P)² + 8.1818P] where P = (F_o² + 2F_c²)/3
6089 reflections	(Δ/σ)_max = 0.001
382 parameters	Δρ_max = 0.75 e Å⁻³
0 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

{[Cu₂(CN)(C₂H₈N₂)₄(H₂O)][Cu₂Zn₂(CN)₉]}	V = 3470.0 (3) Å³
M_r = 901.52	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.1816 (9) Å	µ = 3.81 mm⁻¹
b = 12.4844 (7) Å	T = 293 K
c = 16.1923 (8) Å	0.26 × 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)	R_int = 0.029
T_min = 0.929, T_max = 0.983	3 standard reflections every 60 min
6961 measured reflections	intensity decay: none
6089 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.04	Δρ_max = 0.75 e Å⁻³
6089 reflections	Δρ_min = −0.56 e Å⁻³
382 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

	x	y	z	U_iso*/U_eq
Zn1	0.11314 (4)	0.68154 (6)	0.68142 (4)	0.03848 (18)
Zn2	0.55735 (4)	0.79273 (5)	1.12894 (4)	0.03891 (18)
Cu1	−0.05596 (4)	0.78446 (5)	0.86348 (4)	0.03212 (17)
Cu2	0.39149 (3)	0.81159 (5)	0.81452 (4)	0.02642 (15)
C1	0.0475 (3)	0.7268 (5)	0.7513 (3)	0.0402 (14)
N2	0.0068 (3)	0.7495 (4)	0.7895 (3)	0.0476 (13)
C3	0.1056 (3)	0.5226 (5)	0.6729 (4)	0.0353 (13)
N4	0.0915 (3)	0.4338 (4)	0.6600 (3)	0.0468 (13)
C5	0.0553 (3)	0.7155 (5)	0.5575 (4)	0.0409 (14)
N6	0.0167 (3)	0.7182 (4)	0.4860 (3)	0.0515 (14)
C7	0.2213 (3)	0.7327 (5)	0.7319 (4)	0.0396 (14)
N8	0.2837 (3)	0.7603 (4)	0.7642 (3)	0.0443 (12)
N9	0.4488 (3)	0.7682 (4)	0.9355 (3)	0.0455 (12)
C10	0.4898 (3)	0.7781 (5)	1.0063 (4)	0.0408 (14)
N11	0.3914 (3)	0.9700 (4)	0.8244 (3)	0.0404 (12)
C12	0.4097 (3)	1.0570 (5)	0.8421 (4)	0.0339 (13)
N13	0.4524 (3)	0.7726 (4)	0.7388 (3)	0.0445 (12)
C14	0.4932 (3)	0.7508 (5)	0.7007 (3)	0.0377 (13)
C15	0.6530 (4)	0.7099 (5)	1.1432 (4)	0.0510 (16)
N16	0.7093 (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)
Cu4	0.25758 (5)	0.92268 (6)	0.49821 (6)	0.0483 (2)
N41	0.3639 (3)	0.9584 (5)	0.4690 (4)	0.0615 (16)
H41A	0.3808	0.8993	0.4491	0.074*
H41B	0.3544	1.0093	0.4274	0.074*
C42	0.4230 (4)	0.9960 (7)	0.5493 (5)	0.082 (2)
H42A	0.4503	0.9350	0.5827	0.098*
H42B	0.4608	1.0402	0.5345	0.098*
C43	0.3869 (5)	1.0576 (8)	0.6019 (6)	0.094 (3)
H43A	0.3675	1.1249	0.5729	0.112*
H43B	0.4252	1.0736	0.6584	0.112*
N44	0.3220 (3)	0.9955 (5)	0.6141 (3)	0.0709 (18)
H44A	0.2911	1.0394	0.6321	0.085*
H44B	0.3412	0.9453	0.6555	0.085*
N45	0.1873 (3)	0.9957 (5)	0.3858 (3)	0.0560 (15)
H45A	0.2144	1.0475	0.3699	0.067*
H45B	0.1726	0.9472	0.3423	0.067*
C46	0.1189 (4)	1.0420 (7)	0.3983 (5)	0.080 (2)
H46A	0.0794	1.0549	0.3420	0.096*
H46B	0.1321	1.1100	0.4285	0.096*
C47	0.0879 (5)	0.9660 (8)	0.4513 (5)	0.090 (3)
H47A	0.0453	0.9994	0.4652	0.108*
H47B	0.0683	0.9017	0.4176	0.108*
N48	0.1501 (4)	0.9382 (5)	0.5316 (4)	0.0691 (17)
H48A	0.1391	0.8760	0.5532	0.083*
H48B	0.1555	0.9897	0.5721	0.083*
Cu3	0.25415 (4)	0.49772 (6)	0.50091 (5)	0.04579 (18)
N31	0.2732 (3)	0.4842 (5)	0.6358 (3)	0.0608 (15)
H31A	0.2465	0.5351	0.6531	0.073*
H31B	0.2574	0.4196	0.6480	0.073*
N38	0.1321 (3)	0.4859 (5)	0.4631 (4)	0.0679 (17)
H38A	0.1187	0.4332	0.4932	0.082*
H38B	0.1119	0.5478	0.4743	0.082*
N34	0.3741 (3)	0.4748 (5)	0.5404 (4)	0.0677 (17)
H34A	0.3858	0.4238	0.5074	0.081*
H34B	0.3979	0.5360	0.5339	0.081*
N35	0.2314 (3)	0.4734 (7)	0.3669 (4)	0.096 (3)
H35A	0.2573	0.5219	0.3458	0.116*
H35B	0.2467	0.4074	0.3572	0.116*
C33	0.4008 (4)	0.4424 (8)	0.6318 (5)	0.083 (3)
H33A	0.4556	0.4596	0.6581	0.100*
H33B	0.3949	0.3655	0.6357	0.100*
C32	0.3559 (4)	0.4971 (8)	0.6801 (5)	0.084 (3)
H32A	0.3696	0.4677	0.7386	0.101*
H32B	0.3688	0.5727	0.6850	0.101*
C37	0.1033 (5)	0.4634 (13)	0.3725 (6)	0.153 (4)
H37A	0.0909	0.3876	0.3658	0.184*
H37B	0.0547	0.5021	0.3480	0.184*
N3	0.2591 (4)	0.6693 (4)	0.4970 (5)	0.0652 (15)
C36	0.1473 (5)	0.4855 (13)	0.3244 (6)	0.153 (4)
H36A	0.1370	0.5588	0.3040	0.184*
H36B	0.1314	0.4395	0.2732	0.184*
C4	0.2595 (4)	0.7598 (5)	0.4957 (5)	0.0597 (17)
O1W	0.2468 (5)	0.2864 (6)	0.4956 (6)	0.161 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0349 (3)	0.0439 (4)	0.0356 (4)	−0.0074 (3)	0.0101 (3)	−0.0064 (3)
Zn2	0.0438 (4)	0.0372 (4)	0.0365 (4)	−0.0040 (3)	0.0143 (3)	−0.0010 (3)
Cu1	0.0380 (4)	0.0311 (4)	0.0274 (3)	0.0056 (3)	0.0109 (3)	0.0005 (3)
Cu2	0.0245 (3)	0.0282 (3)	0.0249 (3)	−0.0051 (3)	0.0059 (3)	−0.0044 (3)
C1	0.044 (3)	0.043 (4)	0.030 (3)	−0.004 (3)	0.007 (3)	−0.006 (3)
N2	0.056 (3)	0.053 (3)	0.038 (3)	0.011 (3)	0.021 (3)	−0.006 (2)
C3	0.031 (3)	0.041 (4)	0.038 (3)	−0.007 (3)	0.017 (3)	−0.004 (3)
N4	0.050 (3)	0.042 (3)	0.048 (3)	−0.009 (3)	0.017 (3)	−0.003 (3)
C5	0.042 (3)	0.040 (3)	0.040 (3)	−0.006 (3)	0.012 (3)	0.003 (3)
N6	0.059 (3)	0.055 (4)	0.033 (3)	−0.015 (3)	0.006 (2)	0.000 (3)
C7	0.040 (3)	0.040 (3)	0.039 (3)	−0.011 (3)	0.014 (3)	−0.010 (3)
N8	0.033 (3)	0.054 (3)	0.043 (3)	−0.013 (2)	0.009 (2)	−0.014 (3)
N9	0.049 (3)	0.050 (3)	0.034 (3)	−0.004 (3)	0.010 (2)	0.002 (2)
C10	0.044 (3)	0.041 (4)	0.036 (3)	−0.004 (3)	0.011 (3)	0.003 (3)
N11	0.040 (3)	0.033 (3)	0.047 (3)	−0.002 (2)	0.012 (2)	−0.008 (2)
C12	0.034 (3)	0.035 (4)	0.031 (3)	−0.002 (3)	0.009 (2)	−0.003 (3)
N13	0.045 (3)	0.048 (3)	0.045 (3)	−0.002 (3)	0.020 (2)	−0.011 (3)
C14	0.041 (3)	0.039 (3)	0.032 (3)	−0.003 (3)	0.010 (3)	−0.005 (3)
C15	0.052 (4)	0.045 (4)	0.056 (4)	0.004 (3)	0.017 (3)	−0.014 (3)
N16	0.063 (4)	0.111 (6)	0.140 (7)	0.027 (4)	0.019 (4)	−0.059 (5)
N17	0.117 (6)	0.096 (6)	0.088 (5)	0.006 (5)	0.005 (5)	0.038 (5)
C18	0.071 (6)	0.148 (10)	0.158 (10)	−0.068 (6)	−0.010 (6)	0.104 (8)
Cu4	0.0679 (5)	0.0376 (4)	0.0450 (4)	−0.0025 (4)	0.0263 (4)	0.0003 (4)
N41	0.080 (4)	0.047 (3)	0.068 (4)	0.004 (3)	0.039 (3)	0.008 (3)
C42	0.066 (5)	0.097 (7)	0.091 (6)	0.000 (5)	0.037 (5)	−0.016 (5)
C43	0.062 (5)	0.123 (8)	0.088 (6)	−0.011 (5)	0.015 (5)	−0.031 (6)
N44	0.064 (4)	0.105 (5)	0.041 (3)	0.004 (4)	0.014 (3)	−0.004 (4)
N45	0.053 (3)	0.071 (4)	0.042 (3)	−0.010 (3)	0.014 (3)	0.003 (3)
C46	0.063 (5)	0.106 (7)	0.067 (5)	−0.001 (5)	0.015 (4)	0.013 (5)
C47	0.065 (5)	0.137 (8)	0.074 (6)	−0.038 (5)	0.029 (5)	−0.024 (6)
N48	0.090 (4)	0.063 (4)	0.070 (4)	−0.023 (3)	0.046 (4)	−0.003 (3)
Cu3	0.0310 (3)	0.0597 (4)	0.0480 (4)	0.0039 (4)	0.0149 (3)	−0.0018 (5)
N31	0.052 (3)	0.073 (4)	0.063 (4)	0.002 (3)	0.026 (3)	0.001 (3)
N38	0.045 (3)	0.088 (5)	0.078 (4)	0.001 (3)	0.030 (3)	−0.010 (4)
N34	0.046 (3)	0.088 (5)	0.076 (4)	0.024 (3)	0.029 (3)	0.016 (4)
N35	0.053 (4)	0.159 (7)	0.088 (5)	−0.027 (4)	0.037 (4)	−0.049 (5)
C33	0.040 (4)	0.125 (8)	0.079 (6)	0.021 (4)	0.012 (4)	0.039 (5)
C32	0.065 (5)	0.129 (8)	0.049 (4)	−0.017 (5)	0.005 (4)	−0.002 (5)
C37	0.047 (4)	0.319 (13)	0.088 (5)	−0.012 (6)	0.014 (3)	−0.032 (7)
N3	0.066 (4)	0.040 (3)	0.088 (4)	0.003 (3)	0.023 (3)	0.000 (4)
C36	0.047 (4)	0.319 (13)	0.088 (5)	−0.012 (6)	0.014 (3)	−0.032 (7)
C4	0.072 (5)	0.042 (4)	0.072 (4)	0.006 (4)	0.033 (4)	0.004 (4)
O1W	0.178 (8)	0.106 (6)	0.189 (9)	0.019 (6)	0.048 (7)	−0.001 (7)

Geometric parameters (Å, º) top

Zn1—C7	1.971 (6)	C43—H43B	0.9700
Zn1—C1	1.979 (6)	N44—H44A	0.9000
Zn1—C5	1.980 (6)	N44—H44B	0.9000
Zn1—C3	1.991 (6)	N45—C46	1.445 (9)
Zn2—C10	1.969 (6)	N45—H45A	0.9000
Zn2—C15	1.970 (6)	N45—H45B	0.9000
Zn2—C14ⁱ	1.974 (6)	C46—C47	1.508 (11)
Zn2—C12ⁱⁱ	1.978 (6)	C46—H46A	0.9700
Cu1—N2	1.957 (5)	C46—H46B	0.9700
Cu1—N4ⁱⁱⁱ	1.968 (5)	C47—N48	1.456 (9)
Cu1—N6ⁱ	1.989 (5)	C47—H47A	0.9700
Cu1—N17	2.053 (9)	C47—H47B	0.9700
Cu2—N13	1.966 (5)	N48—H48A	0.9000
Cu2—N8	1.966 (5)	N48—H48B	0.9000
Cu2—N9	1.968 (5)	Cu3—N34	2.081 (5)
Cu2—N11	1.984 (5)	Cu3—N35	2.092 (6)
C1—N2	1.144 (7)	Cu3—N31	2.102 (5)
C3—N4	1.142 (7)	Cu3—N38	2.103 (5)
N4—Cu1^iv	1.968 (5)	Cu3—N3	2.145 (5)
C5—N6	1.139 (7)	N31—C32	1.445 (8)
N6—Cu1^v	1.989 (5)	N31—H31A	0.9000
C7—N8	1.134 (6)	N31—H31B	0.9000
N9—C10	1.149 (7)	N38—C37	1.413 (10)
N11—C12	1.145 (7)	N38—H38A	0.9000
C12—Zn2ⁱⁱ	1.978 (6)	N38—H38B	0.9000
N13—C14	1.142 (6)	N34—C33	1.455 (9)
C14—Zn2^v	1.974 (5)	N34—H34A	0.9000
C15—N16	1.132 (8)	N34—H34B	0.9000
N17—C18	1.122 (9)	N35—C36	1.464 (10)
Cu4—C4	2.034 (7)	N35—H35A	0.9000
Cu4—N45	2.060 (5)	N35—H35B	0.9000
Cu4—N44	2.066 (5)	C33—C32	1.471 (10)
Cu4—N41	2.182 (5)	C33—H33A	0.9700
Cu4—N48	2.202 (6)	C33—H33B	0.9700
N41—C42	1.465 (9)	C32—H32A	0.9700
N41—H41A	0.9000	C32—H32B	0.9700
N41—H41B	0.9000	C37—C36	1.317 (12)
C42—C43	1.455 (10)	C37—H37A	0.9700
C42—H42A	0.9700	C37—H37B	0.9700
C42—H42B	0.9700	N3—C4	1.131 (8)
C43—N44	1.479 (10)	C36—H36A	0.9700
C43—H43A	0.9700	C36—H36B	0.9700

C7—Zn1—C1	112.2 (2)	H45A—N45—H45B	108.0
C7—Zn1—C5	118.4 (2)	N45—C46—C47	109.1 (7)
C1—Zn1—C5	107.4 (2)	N45—C46—H46A	109.9
C7—Zn1—C3	112.9 (2)	C47—C46—H46A	109.9
C1—Zn1—C3	106.5 (2)	N45—C46—H46B	109.9
C5—Zn1—C3	98.1 (2)	C47—C46—H46B	109.9
C10—Zn2—C15	107.6 (2)	H46A—C46—H46B	108.3
C10—Zn2—C14ⁱ	105.9 (2)	N48—C47—C46	109.5 (6)
C15—Zn2—C14ⁱ	117.2 (3)	N48—C47—H47A	109.8
C10—Zn2—C12ⁱⁱ	111.5 (2)	C46—C47—H47A	109.8
C15—Zn2—C12ⁱⁱ	106.5 (2)	N48—C47—H47B	109.8
C14ⁱ—Zn2—C12ⁱⁱ	108.2 (2)	C46—C47—H47B	109.8
N2—Cu1—N4ⁱⁱⁱ	108.3 (2)	H47A—C47—H47B	108.2
N2—Cu1—N6ⁱ	106.1 (2)	C47—N48—Cu4	107.0 (4)
N4ⁱⁱⁱ—Cu1—N6ⁱ	106.0 (2)	C47—N48—H48A	110.3
N2—Cu1—N17	118.7 (3)	Cu4—N48—H48A	110.3
N4ⁱⁱⁱ—Cu1—N17	108.0 (3)	C47—N48—H48B	110.3
N6ⁱ—Cu1—N17	109.1 (3)	Cu4—N48—H48B	110.3
N13—Cu2—N8	110.53 (19)	H48A—N48—H48B	108.6
N13—Cu2—N9	109.3 (2)	N34—Cu3—N35	97.3 (2)
N8—Cu2—N9	116.8 (2)	N34—Cu3—N31	82.7 (2)
N13—Cu2—N11	108.2 (2)	N35—Cu3—N31	166.9 (3)
N8—Cu2—N11	109.3 (2)	N34—Cu3—N38	168.0 (2)
N9—Cu2—N11	102.0 (2)	N35—Cu3—N38	81.9 (2)
N2—C1—Zn1	176.6 (5)	N31—Cu3—N38	95.4 (2)
C1—N2—Cu1	175.3 (5)	N34—Cu3—N3	95.5 (2)
N4—C3—Zn1	170.7 (5)	N35—Cu3—N3	96.3 (3)
C3—N4—Cu1^iv	174.0 (5)	N31—Cu3—N3	96.7 (3)
N6—C5—Zn1	168.4 (5)	N38—Cu3—N3	96.4 (2)
C5—N6—Cu1^v	175.8 (5)	C32—N31—Cu3	107.2 (4)
N8—C7—Zn1	177.2 (5)	C32—N31—H31A	110.3
C7—N8—Cu2	177.1 (5)	Cu3—N31—H31A	110.3
C10—N9—Cu2	156.9 (5)	C32—N31—H31B	110.3
N9—C10—Zn2	178.1 (5)	Cu3—N31—H31B	110.3
C12—N11—Cu2	163.4 (5)	H31A—N31—H31B	108.5
N11—C12—Zn2ⁱⁱ	178.8 (5)	C37—N38—Cu3	108.2 (5)
C14—N13—Cu2	174.4 (5)	C37—N38—H38A	110.1
N13—C14—Zn2^v	175.9 (5)	Cu3—N38—H38A	110.1
N16—C15—Zn2	171.4 (8)	C37—N38—H38B	110.1
C18—N17—Cu1	173.3 (11)	Cu3—N38—H38B	110.1
C4—Cu4—N45	115.8 (3)	H38A—N38—H38B	108.4
C4—Cu4—N44	116.7 (3)	C33—N34—Cu3	108.3 (4)
N45—Cu4—N44	127.5 (2)	C33—N34—H34A	110.0
C4—Cu4—N41	100.2 (2)	Cu3—N34—H34A	110.0
N45—Cu4—N41	93.1 (2)	C33—N34—H34B	110.0
N44—Cu4—N41	80.2 (2)	Cu3—N34—H34B	110.0
C4—Cu4—N48	96.6 (2)	H34A—N34—H34B	108.4
N45—Cu4—N48	80.5 (2)	C36—N35—Cu3	107.0 (5)
N44—Cu4—N48	91.3 (2)	C36—N35—H35A	110.3
N41—Cu4—N48	163.1 (2)	Cu3—N35—H35A	110.3
C42—N41—Cu4	108.5 (4)	C36—N35—H35B	110.3
C42—N41—H41A	110.0	Cu3—N35—H35B	110.3
Cu4—N41—H41A	110.0	H35A—N35—H35B	108.6
C42—N41—H41B	110.0	N34—C33—C32	110.8 (6)
Cu4—N41—H41B	110.0	N34—C33—H33A	109.5
H41A—N41—H41B	108.4	C32—C33—H33A	109.5
C43—C42—N41	110.4 (6)	N34—C33—H33B	109.5
C43—C42—H42A	109.6	C32—C33—H33B	109.5
N41—C42—H42A	109.6	H33A—C33—H33B	108.1
C43—C42—H42B	109.6	N31—C32—C33	110.7 (6)
N41—C42—H42B	109.6	N31—C32—H32A	109.5
H42A—C42—H42B	108.1	C33—C32—H32A	109.5
C42—C43—N44	109.5 (8)	N31—C32—H32B	109.5
C42—C43—H43A	109.8	C33—C32—H32B	109.5
N44—C43—H43A	109.8	H32A—C32—H32B	108.1
C42—C43—H43B	109.8	C36—C37—N38	118.8 (9)
N44—C43—H43B	109.8	C36—C37—H37A	107.6
H43A—C43—H43B	108.2	N38—C37—H37A	107.6
C43—N44—Cu4	110.4 (5)	C36—C37—H37B	107.6
C43—N44—H44A	109.6	N38—C37—H37B	107.6
Cu4—N44—H44A	109.6	H37A—C37—H37B	107.0
C43—N44—H44B	109.6	C4—N3—Cu3	177.7 (6)
Cu4—N44—H44B	109.6	C37—C36—N35	116.4 (9)
H44A—N44—H44B	108.1	C37—C36—H36A	108.2
C46—N45—Cu4	111.4 (4)	N35—C36—H36A	108.2
C46—N45—H45A	109.3	C37—C36—H36B	108.2
Cu4—N45—H45A	109.3	N35—C36—H36B	108.2
C46—N45—H45B	109.3	H36A—C36—H36B	107.3
Cu4—N45—H45B	109.3	N3—C4—Cu4	177.0 (7)

C7—Zn1—C1—N2	−167 (9)	N41—C42—C43—N44	51.5 (10)
C5—Zn1—C1—N2	61 (9)	C42—C43—N44—Cu4	−42.6 (8)
C3—Zn1—C1—N2	−43 (9)	C4—Cu4—N44—C43	114.3 (6)
Zn1—C1—N2—Cu1	120 (8)	N45—Cu4—N44—C43	−68.5 (6)
N4ⁱⁱⁱ—Cu1—N2—C1	127 (7)	N41—Cu4—N44—C43	17.8 (5)
N6ⁱ—Cu1—N2—C1	13 (7)	N48—Cu4—N44—C43	−147.6 (5)
N17—Cu1—N2—C1	−110 (7)	C4—Cu4—N45—C46	108.5 (5)
C7—Zn1—C3—N4	−161 (3)	N44—Cu4—N45—C46	−68.7 (6)
C1—Zn1—C3—N4	75 (3)	N41—Cu4—N45—C46	−148.6 (5)
C5—Zn1—C3—N4	−36 (3)	N48—Cu4—N45—C46	15.6 (5)
Zn1—C3—N4—Cu1^iv	−35 (8)	Cu4—N45—C46—C47	−41.1 (7)
C7—Zn1—C5—N6	144 (3)	N45—C46—C47—N48	53.5 (9)
C1—Zn1—C5—N6	−88 (3)	C46—C47—N48—Cu4	−38.1 (8)
C3—Zn1—C5—N6	22 (3)	C4—Cu4—N48—C47	−102.2 (6)
Zn1—C5—N6—Cu1^v	28 (10)	N45—Cu4—N48—C47	12.9 (5)
C1—Zn1—C7—N8	53 (11)	N44—Cu4—N48—C47	140.8 (5)
C5—Zn1—C7—N8	179 (100)	N41—Cu4—N48—C47	81.7 (10)
C3—Zn1—C7—N8	−67 (11)	N34—Cu3—N31—C32	15.6 (5)
Zn1—C7—N8—Cu2	−178 (5)	N35—Cu3—N31—C32	106.4 (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—C7	67 (10)	N34—Cu3—N38—C37	−84.1 (14)
N13—Cu2—N9—C10	94.8 (12)	N35—Cu3—N38—C37	2.9 (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—C37	98.4 (8)
Cu2—N9—C10—Zn2	134 (17)	N35—Cu3—N34—C33	−156.0 (6)
C15—Zn2—C10—N9	117 (18)	N31—Cu3—N34—C33	10.8 (6)
C14ⁱ—Zn2—C10—N9	−9 (18)	N38—Cu3—N34—C33	−70.6 (13)
C12ⁱⁱ—Zn2—C10—N9	−127 (18)	N3—Cu3—N34—C33	106.9 (6)
N13—Cu2—N11—C12	−71.8 (17)	N34—Cu3—N35—C36	179.7 (8)
N8—Cu2—N11—C12	167.8 (16)	N31—Cu3—N35—C36	90.5 (13)
N9—Cu2—N11—C12	43.4 (17)	N38—Cu3—N35—C36	11.8 (8)
Cu2—N11—C12—Zn2ⁱⁱ	73 (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—C14	83 (5)	N34—C33—C32—N31	51.8 (10)
Cu2—N13—C14—Zn2^v	154 (4)	Cu3—N38—C37—C36	−20.3 (16)
C10—Zn2—C15—N16	60 (4)	N34—Cu3—N3—C4	−150 (20)
C14ⁱ—Zn2—C15—N16	179 (100)	N35—Cu3—N3—C4	112 (20)
C12ⁱⁱ—Zn2—C15—N16	−59 (4)	N31—Cu3—N3—C4	−66 (20)
N2—Cu1—N17—C18	180 (100)	N38—Cu3—N3—C4	30 (20)
N4ⁱⁱⁱ—Cu1—N17—C18	−57 (6)	N38—C37—C36—N35	33 (2)
N6ⁱ—Cu1—N17—C18	58 (6)	Cu3—N35—C36—C37	−27.3 (15)
C4—Cu4—N41—C42	−106.7 (5)	Cu3—N3—C4—Cu4	31 (34)
N45—Cu4—N41—C42	136.4 (5)	N45—Cu4—C4—N3	−114 (16)
N44—Cu4—N41—C42	8.9 (5)	N44—Cu4—C4—N3	63 (16)
N48—Cu4—N41—C42	69.3 (10)	N41—Cu4—C4—N3	147 (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, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N41—H41A···N9^v	0.90	2.48	3.352 (7)	165
N41—H41B···N16^vi	0.90	2.42	3.242 (9)	153
N44—H44B···N11	0.90	2.60	3.234 (7)	128
N45—H45A···N16^vi	0.90	2.13	3.020 (8)	170
N35—H35A···N11^v	0.90	2.58	3.280 (7)	136

Symmetry codes: (v) x, −y+3/2, z−1/2; (vi) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	{[Cu₂(CN)(C₂H₈N₂)₄(H₂O)][Cu₂Zn₂(CN)₉]}
M_r	901.52
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	18.1816 (9), 12.4844 (7), 16.1923 (8)
β (°)	109.246 (11)
V (Å³)	3470.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.81
Crystal size (mm)	0.26 × 0.19 × 0.16

Data collection
Diffractometer	Enraf-Nonius MACH3 sealed tube
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.929, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	6961, 6089, 3637
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.101, 1.04
No. of reflections	6089
No. of parameters	382
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.75, −0.56

Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003), SHELXL97.

Selected torsion angles (º) top

Zn1—C7—N8—Cu2

−178 (5)