A three-dimensional Cu^II–W^IV bimetallic porous assembly containing a zigzag ladder structure

The asymmetric unit of the three-dimensional Cu^II–W^IV polymeric assembly {[Cu(en)₂][Cu(en)][W(CN)₈]·4H₂O}_n (en is ethyl­enedi­amine, C₂H₈N₂) or {[Cu₂W(CN)₈(C₂H₈N₂)₃]·4H₂O}_n, which can be named as polymeric bis­(ethyl­enedi­amine)copper(II) (ethyl­enedi­amine)copper(II) octa­cyano­tungstate(IV) tetrahydrate or penta-μ-cyano-tri­cyano­tris­(ethyl­enedi­amine)­dicopper(II)­tungsten(IV) tetra­hydrate, consists of two half [Cu(en)₂]²⁺ cations (Cu²⁺ on inversion centres), a [Cu(en)]²⁺ cation and a [W(CN)₈]⁴⁻ ion, together with four water mol­ecules. The latter Cu^II site is coordinated by five N atoms from an en ligand and by three cyanides in a distorted square-pyramidal geometry. The Cu^II atoms of the two [Cu(en)₂]²⁺ cations reside in an elongated octahedral coordination environment, and one of them is localized at a centre of inversion. The W atom is coordinated by eight cyano groups in an irregular square antiprism. Five of these act as bridging units connecting the W and the three Cu atoms, to form an infinite three-dimensional porous network containing a zigzag ladder structure.

S1. Comment

Recently, there has been a growing interest in the design and construction of engineered supramolecular frameworks with specific topologies by utilizing molecular precursors containing the cyano group, which is used for its distinct advantage in connecting transition metal ions (Berseth et al., 2000; Ohba et al., 1999; Sokol et al., 2001; Sra et al., 2000; Zhang et al., 2000). These cyano-containing synthons are mainly cyanometallate anions, which show various geometries, e.g. linear, as in [Ag(CN)₂]^-, trigonal, as in [Cu(CN)₃]^2-, tetrahedral, as in [Cd(CN)₄]^2-, square planar, as in [Ni(CN)₄]^2-, and octahedral, as in [Fe(CN)₆]^3- (Yuan et al., 2000). This geometric diversity of the cyanometallates makes it possible for chemists to construct desired structures in an effective manner.

Currently, hexacyanometallate ions, [M(CN)₆]^n- (M is Fe, Cr, Mn, etc.), acting as good building blocks, have been employed successfully to obtain bimetallic assemblies with one-dimensional (one-dimensional) chain, one-dimensional rope-ladder, two-dimensional (two-dimensional) honeycomb, two-dimensional square and three-dimensional (three-dimensional) cubane network structures (Ohba et al., 1999). Octacyanometallates, [M(CN)₈]^n- (M is Mo or W), as one of these potential connecting moieties, may show various geometrical structures, e.g. square antiprism, dodecahedron, or bicapped trigonal prism (Zhong et al., 2000). These flexible species may be used as versatile synthons to construct a variety of supramolecular architectures or networks with novel topological structures. However, structurally characterized complexes based on [M(CN)₈]^4- are still very rare (Sieklucka et al., 2000). Here, we present the structure of a novel three-dimensional Cu^II—W^IV porous coordination polymer, {[Cu(en)₂][Cu(en)][W(CN)₈]}_n.4nH₂O, (I). \sch

The asymmetric unit of (I) consists of a [W(CN)₈]^4- ion, a [Cu(en)]²⁺ ion, two half [Cu(en)₂]²⁺ ions and four water molecules. The W atom is coordinated by eight CN groups in an irregular square antiprism, with W—C distances ranging from 2.156 (5) to 2.172 (5) Å (Fig. 1). Atoms Cu2 and Cu3 are located at the special equivalent positions (0,0,1/2) and (0,0,0), respectively, and both are in an elongated octahedral coordination environment, in which four N atoms from two en ligands occupy the equatorial positions, with Cu—N_eq bond distances in the range 2.011 (6)–2.024 (4) Å.

The axial sites are occupied by two N atoms from the bridging cyanide groups on different [W(CN)₈]^4- anions. Owing to Jahn-Teller effects, the two Cu—N_cyanide distances are much longer than those of the equatorial positions, with Cu2—N7 = 2.644 (5) Å and Cu3—N8 = 2.500 (4) Å.

The Cu1 sphere can be described as a distorted square-pyramidal geometry, with N1 as the axial atom and N2ⁱ, N3ⁱⁱ, N9 and N10 as the equatorial coordinated atoms, where atoms N2ⁱ and N3ⁱⁱ are from the cyanides of another two adjacent [W(CN)₈] moieties [symmetry codes: (i) -1 - x, -1 - y, 1 - z; (ii) x - 1, y, z]. Please check symmetry codes. Consequently, for each [W(CN)₈] unit, there are five cyano groups acting as bridging units and another three as terminal groups.

Through the bridging cyano groups (C1≡N1, C2≡N2 and C3≡N3), atoms W1 and Cu1 are linked to form a one-dimensional infinite zigzag ladder structure along the a axis (Fig. 1 b). The ladder is made up of two different collateral Cu₂W₂(CN)₄ 12-atom macrocyclic units [(Cu1—N1≡ C1—W1—C2≡N2-)₂ and (Cu1—N3≡C3—W1—C2≡N2-)₂], with a dihedral angle of 120.6° based on the two Cu₂W₂ planes. Along the b axis, the zigzag ladders are connected together by W1—C7≡ N7—Cu2 linkages to form two-dimensional sheets. Meanwhile, another kind of linkage, of the form W1—C8≡N8—Cu3, connects the two-dimensional sheets to construct a three-dimensional porous network structure, as depicted in Fig. 2.

It is worthy to note that the displacement ellipsoids of the atoms of the Cu2 cation system are smaller than those of the Cu3 cation system. This may be interpreted from the unique coordination environment about the Cu2 system. Between every two adjacent zigzag ladders, boxes are formed by two pairs of the above mentioned collateral Cu₂W₂(CN)₄ 12-atom macrocyclic units joined by four N11—H11C···N6ⁱⁱⁱ hydrogen bonds [symmetry code: (iii) 1 + x, y, z]. Please check symmetry code. In each cavity, a [Cu(en)₂]²⁺ cation system (Cu2) is encapsulated, as shown in Fig. 3. The four N atoms (N11, N12, N11ⁱ, N12ⁱ Please check symmetry code) of two en ligands are fixed by four N_en—H···N_cyanide hydrogen bonds (Fig. 3, Table 2) and the two C7≡N7 groups act like pincers to clamp the Cu2 atom, through two weak Cu1—N7 interactions. Thus, the Cu2 cation system is stabilized steadily in the void.

S2. Experimental

An aqueous solution (20 ml) of Cu(ClO₄)₂·6H₂O (74.1 mg, 0.20 mmol), ethylenediamine (0.001 ml, 0.40 mmol) and K₄[W(CN)₈]·2H₂O (58.4 mg, 0.10 mmol) was stirred at 313 K for 30 min. The resulting solution was left for several days at room temperature in the absence of light, and dark-blue crystals of (I) were obtained in ca 70% yield.

S3. Refinement

H atoms on C and N atoms were treated as riding atoms. Please provide brief details of constraints. Please also provide bond distances and angles involving H atoms, in CIF-format, for inclusion in the archived CIF. The water molecules were disordered over two sets of sites. Only a few partial H atoms of the water molecules could be found from the difference maps, so the water H atoms were not included in the refinement.

Computing details

Data collection: TEXSAN (Molecular Structure Corporation, 2000); cell refinement: TEXSAN; data reduction: TEXSAN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1998); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I). a) A drawing of the asymmetric unit, with displacement ellipsoids at the ? probability level. Please provide missing information. b) A perspective view of the zigzag ladder portion. H atoms and non-bridging cyano groups have been omitted for clarity [symmetry codes: (i) -1 - x, -1 - y, 1 - z; (ii) x - 1, y, z]. Please check symmetry codes.
	Fig. 2. A perspective view of (I) onto the bc plane, showing the three-dimensional porous structure. The dashed curve encircles the position of the zigzag ladder along the a axis. The en ligands, water molecules and non-bridged cyano groups have been omitted for clarity.
	Fig. 3. A perspective view of a cavity which capsulates a [Cu2(en)2]^2+ cation. Atoms unrelated to this box have been omitted for clarity. Symmetry codes? Please provide four missing symops.

penta-µ-cyano-tricyanotris(ethylenediamine)dicopper(II)tungsten(IV) tetrahydrate

Crystal data

[Cu2W(CN)8(C2H8N2)3]·4H2O	Z = 2
Mr = 771.48	F(000) = 756
Triclinic, P1	Dx = 1.961 Mg m^−3
Hall symbol: -p 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.0072 (7) Å	Cell parameters from 8762 reflections
b = 9.7391 (6) Å	θ = 2.6–27.5°
c = 15.5818 (11) Å	µ = 6.06 mm^−1
α = 75.407 (3)°	T = 150 K
β = 85.574 (3)°	Platelet, dark blue
γ = 81.367 (4)°	0.25 × 0.20 × 0.10 mm
V = 1306.68 (16) Å^3

Data collection

Rigaku RAXIS-RAPID imaging-plate diffractometer	4533 independent reflections
Radiation source: fine-focus sealed tube	4194 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 10.00 pixels mm^-1	θmax = 25.0°, θmin = 2.2°
ω scans	h = −10→10
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −11→11
Tmin = 0.250, Tmax = 0.548	l = −18→18
7452 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.061	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0293P)^2 + 5.1937P] where P = (Fo^2 + 2Fc^2)/3
4533 reflections	(Δ/σ)max < 0.001
359 parameters	Δρmax = 0.83 e Å^−3
0 restraints	Δρmin = −1.48 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
W1	−0.263486 (19)	−0.253509 (17)	0.308533 (11)	0.01522 (7)
Cu1	−0.73106 (6)	−0.54370 (5)	0.34559 (3)	0.01567 (12)
Cu2	0.0000	0.0000	0.5000	0.02014 (17)
Cu3	0.0000	0.0000	0.0000	0.0546 (3)
C1	−0.4764 (5)	−0.3370 (5)	0.3430 (3)	0.0212 (10)
C2	−0.2763 (5)	−0.3161 (4)	0.4517 (3)	0.0165 (9)
C3	−0.0528 (5)	−0.3845 (4)	0.3509 (3)	0.0196 (9)
C4	−0.2534 (5)	−0.4436 (5)	0.2602 (3)	0.0263 (11)
C5	−0.3927 (6)	−0.1556 (6)	0.1920 (4)	0.0330 (12)
C6	−0.4156 (5)	−0.0768 (5)	0.3409 (3)	0.0231 (10)
C7	−0.1267 (5)	−0.0993 (5)	0.3281 (3)	0.0254 (11)
C8	−0.1095 (6)	−0.2174 (5)	0.1942 (3)	0.0324 (12)
C9	−0.6225 (8)	−0.5070 (7)	0.1642 (4)	0.0548 (19)
H9A	−0.5482	−0.4421	0.1650	0.066*
H9B	−0.6441	−0.4993	0.1017	0.066*
C10	−0.5623 (6)	−0.6587 (6)	0.2087 (3)	0.0370 (13)
H10A	−0.6299	−0.7251	0.2002	0.044*
H10B	−0.4615	−0.6857	0.1829	0.044*
C11	0.2867 (6)	−0.1700 (5)	0.5308 (4)	0.0388 (13)
H11A	0.3904	−0.1948	0.5081	0.047*
H11B	0.2892	−0.1791	0.5954	0.047*
C12	0.1884 (6)	−0.2679 (5)	0.5138 (4)	0.0373 (13)
H12A	0.2178	−0.3661	0.5503	0.045*
H12B	0.1985	−0.2706	0.4505	0.045*
C13	0.2516 (10)	−0.1985 (7)	−0.0292 (4)	0.073 (3)
H13A	0.2244	−0.2815	0.0176	0.088*
H13B	0.3595	−0.2178	−0.0462	0.088*
C14	0.1590 (9)	−0.1759 (7)	−0.1075 (4)	0.065 (2)
H14A	0.1670	−0.2655	−0.1276	0.078*
H14B	0.1944	−0.1006	−0.1570	0.078*
N1	−0.5884 (4)	−0.3819 (4)	0.3564 (3)	0.0250 (9)
N2	−0.2802 (4)	−0.3474 (4)	0.5278 (3)	0.0193 (8)
N3	0.0622 (4)	−0.4495 (4)	0.3667 (3)	0.0219 (8)
N4	−0.2440 (6)	−0.5449 (5)	0.2331 (3)	0.0443 (12)
N5	−0.4646 (7)	−0.1025 (7)	0.1321 (3)	0.0611 (17)
N6	−0.4976 (5)	0.0144 (4)	0.3585 (3)	0.0362 (11)
N7	−0.0487 (5)	−0.0229 (5)	0.3393 (4)	0.0383 (11)
N8	−0.0273 (6)	−0.2016 (5)	0.1334 (3)	0.0584 (17)
N9	−0.7624 (6)	−0.4682 (6)	0.2146 (3)	0.0479 (14)
H9C	−0.8403	−0.5068	0.1987	0.057*
H9D	−0.7871	−0.3702	0.2015	0.057*
N10	−0.5533 (4)	−0.6671 (4)	0.3038 (2)	0.0206 (8)
H10C	−0.4656	−0.6365	0.3133	0.025*
H10D	−0.5523	−0.7606	0.3357	0.025*
N11	0.2269 (4)	−0.0204 (4)	0.4852 (3)	0.0264 (9)
H11C	0.2557	−0.0020	0.4259	0.032*
H11D	0.2635	0.0435	0.5098	0.032*
N12	0.0312 (4)	−0.2161 (4)	0.5368 (3)	0.0264 (9)
H12C	0.0120	−0.2468	0.5969	0.032*
H12D	−0.0336	−0.2518	0.5078	0.032*
N13	0.2223 (8)	−0.0669 (6)	0.0038 (3)	0.0647 (19)
H13C	0.2742	0.0027	−0.0313	0.078*
H13D	0.2532	−0.0857	0.0610	0.078*
N14	0.0008 (8)	−0.1317 (6)	−0.0810 (4)	0.0692 (19)
H14C	−0.0434	−0.2109	−0.0521	0.083*
H14D	−0.0527	−0.0853	−0.1304	0.083*
O1A	−1.051 (3)	−1.2703 (14)	0.7317 (5)	0.061 (4)	0.81 (5)
O1B	−1.124 (4)	−1.217 (5)	0.7264 (13)	0.025 (11)	0.19 (5)
O2A	−1.1425 (18)	−1.4289 (11)	0.0200 (6)	0.069 (5)	0.65 (3)
O2B	−1.259 (5)	−1.449 (2)	0.0336 (13)	0.100 (13)	0.35 (3)
O3A	−1.3779 (10)	−1.1912 (9)	0.9672 (6)	0.077 (3)	0.680 (11)
O3B	−1.0642 (18)	−1.4384 (16)	0.8913 (11)	0.066 (6)	0.320 (11)
O4A	−1.2286 (10)	−0.8958 (15)	0.7896 (6)	0.057 (4)	0.494 (18)
O4B	−1.2208 (11)	−1.0034 (14)	0.7678 (9)	0.077 (5)	0.506 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
W1	0.01613 (10)	0.01103 (9)	0.01585 (10)	0.00081 (6)	0.00200 (6)	−0.00078 (6)
Cu1	0.0150 (3)	0.0148 (2)	0.0161 (3)	0.0016 (2)	0.0007 (2)	−0.0041 (2)
Cu2	0.0137 (4)	0.0165 (4)	0.0306 (4)	−0.0011 (3)	0.0018 (3)	−0.0078 (3)
Cu3	0.0976 (9)	0.0244 (5)	0.0262 (5)	0.0167 (5)	0.0277 (5)	−0.0008 (4)
C1	0.027 (3)	0.015 (2)	0.021 (2)	0.0027 (19)	0.0013 (19)	−0.0060 (17)
C2	0.013 (2)	0.0091 (19)	0.026 (3)	−0.0001 (16)	0.0030 (17)	−0.0032 (17)
C3	0.025 (2)	0.012 (2)	0.022 (2)	−0.0048 (19)	0.0061 (19)	−0.0033 (17)
C4	0.026 (3)	0.030 (3)	0.023 (2)	−0.001 (2)	0.002 (2)	−0.009 (2)
C5	0.034 (3)	0.033 (3)	0.031 (3)	−0.008 (2)	−0.001 (2)	−0.003 (2)
C6	0.022 (2)	0.013 (2)	0.033 (3)	−0.0017 (19)	−0.001 (2)	−0.0045 (19)
C7	0.014 (2)	0.026 (2)	0.031 (3)	0.004 (2)	0.0022 (19)	−0.001 (2)
C8	0.035 (3)	0.025 (2)	0.027 (3)	0.009 (2)	0.005 (2)	0.004 (2)
C9	0.064 (4)	0.066 (4)	0.015 (3)	0.035 (3)	0.007 (3)	−0.002 (3)
C10	0.040 (3)	0.047 (3)	0.023 (3)	0.012 (3)	0.001 (2)	−0.020 (2)
C11	0.026 (3)	0.027 (3)	0.062 (4)	0.002 (2)	0.000 (3)	−0.013 (3)
C12	0.030 (3)	0.022 (2)	0.055 (4)	0.003 (2)	0.007 (3)	−0.008 (2)
C13	0.120 (7)	0.043 (4)	0.031 (3)	0.045 (4)	0.014 (4)	−0.001 (3)
C14	0.113 (6)	0.038 (3)	0.031 (3)	0.021 (4)	0.022 (4)	−0.009 (3)
N1	0.022 (2)	0.025 (2)	0.031 (2)	−0.0063 (17)	0.0083 (17)	−0.0123 (17)
N2	0.0170 (18)	0.0171 (18)	0.021 (2)	0.0017 (15)	0.0010 (15)	−0.0030 (15)
N3	0.018 (2)	0.0185 (18)	0.027 (2)	0.0020 (16)	0.0018 (16)	−0.0050 (16)
N4	0.047 (3)	0.037 (3)	0.057 (3)	−0.006 (2)	0.011 (2)	−0.029 (2)
N5	0.057 (4)	0.084 (4)	0.031 (3)	−0.012 (3)	−0.023 (3)	0.015 (3)
N6	0.026 (2)	0.017 (2)	0.062 (3)	0.0026 (18)	0.007 (2)	−0.009 (2)
N7	0.022 (2)	0.023 (2)	0.071 (3)	−0.0082 (19)	−0.001 (2)	−0.012 (2)
N8	0.057 (3)	0.043 (3)	0.045 (3)	0.020 (3)	0.033 (3)	0.017 (2)
N9	0.046 (3)	0.066 (3)	0.020 (2)	0.034 (3)	−0.003 (2)	−0.012 (2)
N10	0.022 (2)	0.0153 (18)	0.023 (2)	0.0011 (15)	0.0029 (16)	−0.0060 (15)
N11	0.019 (2)	0.023 (2)	0.041 (2)	−0.0039 (16)	0.0044 (17)	−0.0141 (18)
N12	0.021 (2)	0.020 (2)	0.039 (2)	−0.0023 (16)	−0.0009 (18)	−0.0106 (17)
N13	0.105 (5)	0.048 (3)	0.023 (3)	0.029 (3)	0.012 (3)	−0.004 (2)
N14	0.107 (5)	0.042 (3)	0.051 (3)	0.013 (3)	0.025 (3)	−0.019 (3)
O1A	0.080 (11)	0.035 (5)	0.063 (4)	−0.008 (7)	0.019 (4)	−0.007 (3)
O1B	0.015 (16)	0.029 (18)	0.025 (11)	0.004 (13)	0.002 (8)	−0.004 (8)
O2A	0.078 (10)	0.068 (6)	0.053 (5)	0.003 (5)	0.008 (5)	−0.014 (4)
O2B	0.15 (4)	0.083 (13)	0.068 (12)	−0.023 (14)	0.028 (14)	−0.024 (10)
O3A	0.088 (6)	0.071 (5)	0.075 (6)	−0.004 (4)	−0.027 (5)	−0.020 (4)
O3B	0.063 (10)	0.056 (9)	0.078 (12)	−0.019 (8)	−0.035 (9)	0.004 (8)
O4A	0.036 (5)	0.089 (11)	0.050 (6)	−0.004 (5)	0.008 (4)	−0.028 (5)
O4B	0.042 (6)	0.066 (9)	0.115 (10)	−0.006 (5)	−0.001 (6)	−0.010 (7)

Geometric parameters (Å, º)

W1—C1	2.172 (5)	C11—N11	1.490 (6)
W1—C2	2.158 (5)	C12—N12	1.479 (6)
W1—C3	2.169 (5)	C13—N13	1.479 (8)
W1—C4	2.156 (5)	C13—C14	1.483 (11)
W1—C5	2.164 (5)	C14—N14	1.484 (9)
W1—C6	2.172 (4)	N2—Cu1^i	1.992 (4)
W1—C7	2.171 (5)	N3—Cu1^iii	1.990 (4)
W1—C8	2.161 (5)	C9—H9A	0.9900
Cu1—N1	2.222 (4)	C9—H9B	0.9900
Cu1—N2^i	1.992 (4)	C10—H10A	0.9900
Cu1—N3^ii	1.990 (4)	C10—H10B	0.9900
Cu1—N9	2.014 (4)	C11—H11A	0.9900
Cu1—N10	2.022 (4)	C11—H11B	0.9900
Cu2—N7	2.644 (5)	C12—H12A	0.9900
Cu2—N11	2.024 (4)	C12—H12B	0.9900
Cu2—N12	2.019 (4)	C13—H13A	0.9900
Cu3—N8	2.500 (4)	C13—H13B	0.9900
Cu3—N13	2.011 (6)	C14—H14A	0.9900
Cu3—N14	2.012 (6)	C14—H14B	0.9900
C1—N1	1.142 (6)	N9—H9C	0.9200
C2—N2	1.147 (6)	N9—H9D	0.9200
C3—N3	1.140 (6)	N10—H10C	0.9200
C4—N4	1.156 (6)	N10—H10D	0.9200
C5—N5	1.143 (7)	N11—H11C	0.9200
C6—N6	1.142 (6)	N11—H11D	0.9200
C7—N7	1.148 (6)	N12—H12C	0.9200
C8—N8	1.150 (7)	N12—H12D	0.9200
C9—N9	1.484 (7)	N13—H13C	0.9200
C9—C10	1.504 (8)	N13—H13D	0.9200
C10—N10	1.471 (6)	N14—H14C	0.9200
C11—C12	1.476 (8)	N14—H14D	0.9200
C4—W1—C2	108.06 (17)	C8—N8—Cu3	133.9 (4)
C4—W1—C8	76.24 (19)	C9—N9—Cu1	109.4 (3)
C2—W1—C8	143.63 (18)	C10—N10—Cu1	110.2 (3)
C4—W1—C5	83.17 (19)	C11—N11—Cu2	107.7 (3)
C2—W1—C5	143.99 (18)	C12—N12—Cu2	108.7 (3)
C8—W1—C5	71.7 (2)	C13—N13—Cu3	107.8 (5)
C4—W1—C3	73.61 (17)	C14—N14—Cu3	108.4 (5)
C2—W1—C3	72.81 (15)	N9—C9—H9A	110.4
C8—W1—C3	74.13 (17)	C10—C9—H9A	110.4
C5—W1—C3	142.28 (19)	N9—C9—H9B	110.4
C4—W1—C7	142.61 (18)	C10—C9—H9B	110.4
C2—W1—C7	84.00 (17)	H9A—C9—H9B	108.6
C8—W1—C7	74.1 (2)	N10—C10—H10A	110.2
C5—W1—C7	108.05 (19)	C9—C10—H10A	110.2
C3—W1—C7	76.80 (16)	N10—C10—H10B	110.2
C4—W1—C6	143.55 (18)	C9—C10—H10B	110.2
C2—W1—C6	77.95 (16)	H10A—C10—H10B	108.5
C8—W1—C6	120.65 (18)	C12—C11—H11A	109.9
C5—W1—C6	73.89 (19)	N11—C11—H11A	109.9
C3—W1—C6	139.47 (17)	C12—C11—H11B	109.9
C7—W1—C6	72.74 (17)	N11—C11—H11B	109.9
C4—W1—C1	71.71 (17)	H11A—C11—H11B	108.3
C2—W1—C1	74.79 (16)	C11—C12—H12A	110.0
C8—W1—C1	137.1 (2)	N12—C12—H12A	110.0
C5—W1—C1	76.83 (18)	C11—C12—H12B	110.0
C3—W1—C1	121.17 (16)	N12—C12—H12B	110.0
C7—W1—C1	144.91 (16)	H12A—C12—H12B	108.3
C6—W1—C1	75.67 (16)	N13—C13—H13A	110.2
N3^ii—Cu1—N2^i	91.68 (15)	C14—C13—H13A	110.2
N3^ii—Cu1—N9	87.71 (17)	N13—C13—H13B	110.2
N2^i—Cu1—N9	168.1 (2)	C14—C13—H13B	110.2
N3^ii—Cu1—N10	163.46 (16)	H13A—C13—H13B	108.5
N2^i—Cu1—N10	94.35 (15)	C13—C14—H14A	110.1
N9—Cu1—N10	83.21 (16)	N14—C14—H14A	110.1
N3^ii—Cu1—N1	102.76 (15)	C13—C14—H14B	110.1
N2^i—Cu1—N1	95.89 (15)	N14—C14—H14B	110.1
N9—Cu1—N1	95.9 (2)	H14A—C14—H14B	108.4
N10—Cu1—N1	91.94 (15)	C9—N9—H9C	109.8
N12^iv—Cu2—N12	180.0	Cu1—N9—H9C	109.8
N12^iv—Cu2—N11	95.41 (16)	C9—N9—H9D	109.8
N12—Cu2—N11	84.59 (16)	Cu1—N9—H9D	109.8
N12^iv—Cu2—N11^iv	84.59 (16)	H9C—N9—H9D	108.2
N12—Cu2—N11^iv	95.41 (16)	C10—N10—H10C	109.6
N11—Cu2—N11^iv	180.0	Cu1—N10—H10C	109.6
N13—Cu3—N13^v	180.0	C10—N10—H10D	109.6
N13—Cu3—N14	84.6 (3)	Cu1—N10—H10D	109.6
N13^v—Cu3—N14	95.4 (3)	H10C—N10—H10D	108.1
N13—Cu3—N14^v	95.4 (3)	C11—N11—H11C	110.2
N13^v—Cu3—N14^v	84.6 (3)	Cu2—N11—H11C	110.2
N14—Cu3—N14^v	180.0 (2)	C11—N11—H11D	110.2
N1—C1—W1	176.2 (4)	Cu2—N11—H11D	110.2
N2—C2—W1	178.3 (4)	H11C—N11—H11D	108.5
N3—C3—W1	174.7 (4)	C12—N12—H12C	109.9
N4—C4—W1	178.0 (5)	Cu2—N12—H12C	109.9
N5—C5—W1	177.9 (5)	C12—N12—H12D	109.9
N6—C6—W1	178.7 (4)	Cu2—N12—H12D	109.9
N7—C7—W1	176.7 (4)	H12C—N12—H12D	108.3
N8—C8—W1	178.4 (5)	C13—N13—H13C	110.1
N9—C9—C10	106.8 (5)	Cu3—N13—H13C	110.1
N10—C10—C9	107.6 (4)	C13—N13—H13D	110.1
C12—C11—N11	108.8 (4)	Cu3—N13—H13D	110.1
C11—C12—N12	108.6 (4)	H13C—N13—H13D	108.5
N13—C13—C14	107.7 (5)	C14—N14—H14C	110.0
C13—C14—N14	107.9 (5)	Cu3—N14—H14C	110.0
C1—N1—Cu1	150.1 (3)	C14—N14—H14D	110.0
C2—N2—Cu1^i	163.9 (3)	Cu3—N14—H14D	110.0
C3—N3—Cu1^iii	158.8 (4)	H14C—N14—H14D	108.4
C7—N7—Cu2	122.0 (4)

Symmetry codes: (i) −x−1, −y−1, −z+1; (ii) x−1, y, z; (iii) x+1, y, z; (iv) −x, −y, −z+1; (v) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9C···O1A^vi	0.92	2.48	3.16 (2)	132
N9—H9D···N8^ii	0.92	2.63	3.315 (8)	132
N10—H10C···N4	0.92	2.44	3.202 (6)	141
N10—H10D···N6^vii	0.92	2.12	2.978 (6)	155
N11—H11C···N6^iii	0.92	2.39	3.054 (6)	129
N12—H12C···O1A^viii	0.92	2.10	3.002 (10)	168
N12—H12D···N2	0.92	2.50	3.279 (5)	142
N13—H13C···N5^v	0.92	2.38	3.252 (8)	158
N14—H14C···O2A^viii	0.92	2.40	3.322 (14)	176
N14—H14D···O4B^ix	0.92	2.19	3.097 (14)	167

Symmetry codes: (ii) x−1, y, z; (iii) x+1, y, z; (v) −x, −y, −z; (vi) −x−2, −y−2, −z+1; (vii) x, y−1, z; (viii) x+1, y+1, z; (ix) x+1, y+1, z−1.