Poly[aqua­hexa­benzimidazole­octa-μ-cyanido-octa­cyanidotricopper(II)ditungstate(V)]

Imoto, K.; Kaneko, S.; Tsunobuchi, Y.; Nakabayashi, K.; Ohkoshi, S.

doi:10.1107/S160053681000841X

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Pages m403-m404

doi:10.1107/S160053681000841X

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Poly[aquahexabenzimidazoleocta-μ-cyanido-octacyanidotricopper(II)ditungstate(V)]

Kenta Imoto,^a Souhei Kaneko,^a Yoshihide Tsunobuchi,^a Koji Nakabayashi ^a and Shin-ichi Ohkoshi ^a ^*

^aDepartment of Chemistry, School of Science, University of Tokyo, 7-3-1 Hongo, Bunkyo-Ku, Tokyo 113-0033, Japan
^*Correspondence e-mail: ohkoshi@chem.s.u-tokyo.ac.jp

(Received 5 February 2010; accepted 4 March 2010; online 13 March 2010)

In the polymeric title compound, [Cu₃W₂(CN)₁₆(C₇H₆N₂)₆(H₂O)]_n, the coordination geometry of the W(V) atom is eight-coordinate dodecahedral, where four CN groups of [W(CN)₈] are bridged to Cu^II ions, and the other four CN groups are not bridged. The coordination geometries of the Cu^II ions are five-coordinate pseudo-square-based pyramidal. There are two distinct Cu sites, which build and link the cyanido-bridged Cu—W ladder chains. Successive connections lead to the formation of a two-dimensional network. The H atoms of a coordinated water molecule and the imino groups form hydrogen bonds to the N atoms of non-bridged CN groups.

Related literature

For general background to molecule-based magnets, see: Catala et al. (2005 ); Garde et al. (1999 ); Herrera et al. (2004 , 2008 ); Kosaka et al. (2009 ); Leipoldt et al. (1994 ); Ohkoshi et al. (2006 , 2007 , 2008 ); Sieklucka et al. (2009 ); Zhong et al. (2000 ). For related structures, see: Ohkoshi et al. (2003 ); Podgajny et al. (2002 ); Kaneko et al. (2007 ).

Experimental

Crystal data

[Cu₃W₂(CN)₁₆(C₇H₆N₂)₆(H₂O)]
M_r = 1701.46
Monoclinic, C 2/c
a = 32.0103 (8) Å
b = 10.2389 (3) Å
c = 19.5533 (5) Å
β = 93.8269 (8)°
V = 6394.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 4.63 mm⁻¹
T = 296 K
0.45 × 0.12 × 0.08 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.327, T_max = 0.690
31073 measured reflections
7321 independent reflections
6376 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.085
S = 1.02
7321 reflections
421 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.85 e Å⁻³
Δρ_min = −1.08 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N6	1.05 (12)	2.20 (12)	3.178 (7)	154 (10)
N10—H10N⋯N5ⁱ	0.86	1.97	2.802 (5)	163
N12—H12N⋯N8ⁱⁱ	0.86	2.04	2.888 (5)	169
N14—H14N⋯N7ⁱⁱⁱ	0.86	2.18	2.973 (5)	154
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+2, z+{\script{1\over 2}}]$ ; (iii) $[x, -y+2, z-{\script{1\over 2}}]$ .

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2007 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and VESTA (Momma & Izumi, 2006 ); software used to prepare material for publication: CrystalStructure .

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681000841X/pk2226sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681000841X/pk2226Isup2.hkl

checkCIF report

Comment top

In molecule-based magnets, preparing compounds with a high Curie temperature (T_C) is a challenging issue. From this view point, octacyanometalate [M(CN)₈] (M = Mo, W, Nb)-based magnets have been aggressively studied due to their high T_C (Garde et al., 1999; Zhong et al., 2000; Herrera et al., 2008; Sieklucka et al., 2009; Kosaka et al., 2009) and properties such as photomagnetism (Herrera et al., 2004; Catala et al., 2005; Ohkoshi et al., 2006; Ohkoshi et al., 2008) and chemically sensitive magnetism (Ohkoshi et al., 2007). Octacyanometalates, [M(CN)₈] (M = Mo, W, Nb), a versatile class of building blocks, can adopt different spatial configurations depending on their chemical environment, e.g., square antiprism (D_4d), dodecahedron (D_2d), and bicapped trigonal prism (C_2v) (Leipoldt et al., 1994). Thus, crystal structures of their complexes have various coordination geometries. Several octacyanometalate-based magnets of Cu—W systems such as {[Cu₃[W(CN)₈]₂]3.4H₂O}_n (3-dimensional network complex, 3-D) (Garde et al., 1999), {[Cu₃[W(CN)₈]₂(pyrimidine)₂]8H₂O}_n (3-D) (Ohkoshi et al., 2007), {[(tetrenH₅)_0.8Cu₄ [W(CN)₈]₄]7.2H₂O}_n (2-D) (Sieklucka et al., 2009), {[Cu₃[W(CN)₈]₂(3-cyanopyridine)₆]4H₂O}_n (2-D), and {[Cu₃[W(CN)₈]₂(4-cyanopyridine)₆]8H₂O}_n (2-D) (Ohkoshi et al., 2003), have been reported.

The asymmetric unit of the present compound consists of a [W(CN)₈]^3- anion, a [Cu1(benzimidazole)₂]²⁺ cation and one-half of [Cu2(benzimidazole)(H₂O)]²⁺ cation (Fig. 1). The coordination geometry of W is an 8-coordinated dodecahedron, where four CN groups of [W(CN)₈] are bridged to Cu ions (three Cu1 and one Cu2), and other four CN groups are not bridged. The coordination geometries of the two types of Cu^II ions (Cu1 and Cu2) are 5-coordinated pseudo-square pyramidal. The Cu1 atom is coordinated to three nitrogen atoms of CN groups and two nitrogen atoms of benzimidazole molecules. The Cu2 atom is coordinated to two nitrogen atoms of CN groups, two nitrogen atoms of benzimidazole molecules, and an oxygen atom of an H₂O molecule. The cyano-bridged-Cu1—W ladder chains are linked by Cu2 pillar units (Fig. 2). The benzimidazole molecules coordinated to Cu1 are aligned alternately between the layers with the intermolecular shortest distance of 3.452 (7) Å.

The field-cooled magnetization (FCM) curve at 10 Oe showed that the magnetization value gradually increased below 10 K and then drastically dropped below 7.5 K with decreasing temperature. The magnetization vs. external magnetic field (M-H) curve at 2 K showed a spin-flip transition with the critical magnetic field of 900 Oe and the saturation magnetization (M_s) value of 5.2 µ_B. This M_s value is close to the expected value of 5.0 µ_B for the ferromagnetic ordering of W^V (S = 1/2) ions and Cu^II (S = 1/2) ions. These FCM and M-H curves indicate that this compound is a metamagnet.

Related literature top

For general background to molecule-based magnets, see: Catala et al. (2005); Garde et al. (1999); Herrera et al. (2004, 2008); Kosaka et al. (2009); Leipoldt et al. (1994); Ohkoshi et al. (2006, 2007, 2008); Sieklucka et al. (2009); Zhong et al. (2000). For related structures, see: Ohkoshi et al. (2003); Podgajny et al. (2002); Kaneko et al. (2007).

Experimental top

The title compound was prepared by reacting an aqueous solution of Cs₃[W(CN)₈]2H₂O (1.2 × 10 ^-2 mol dm^-3) with a mixed aqueous solution of CuCl₂2H₂O (1.8 × 10 ^-2 mol dm^-3) and benzimidazole (2.0 × 10 ^-2 mol dm^-3) at room temperature. The prepared compound was a deep blue rod-shaped crystal. Elemental analyses: calculated for Cu₃[W(CN)₈]₂(benzimidazole)₆(H₂O), Calculated: Cu, 11.20; W, 21.61; C, 40.94; H, 2.25; N, 23.05. Found: Cu, 11.32; W, 21.78; C, 40.65; H, 2.42; N, 23.15.

In the Infrared (IR) spectra, cyano stretching peaks were observed at 2206, 2201, 2186, 2183, and 2165 cm^-1.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and VESTA (Momma & Izumi, 2006); software used to prepare material for publication: CrystalStructure (Rigaku, 2007).

Figures top

	Fig. 1. Thermal ellipsoid plots (50% probability level) of Cu₃[W(CN)₈]₂(C₇H₆N₂)₆(H₂O). Magenta, Green, gray, light blue, red, and white circle represent W, Cu, C, N, O, and H atoms, respectively. The asterisks indicate the atoms generated by symmetry operations.
	Fig. 2. A structure diagram of Cu₃[W(CN)₈]₂(C₇H₆N₂)₆(H₂O). Magenta, Green, gray, light blue, and red represent W, Cu, C, N, and O atoms, respectively. Hydrogen atoms are omitted for clarity.

Poly[aquahexabenzimidazoleocta-µ-cyanido- octacyanidotricopper(II)ditungstate(V)] top

Crystal data top

[Cu₃W₂(CN)₁₆(C₇H₆N₂)₆(H₂O)]	F(000) = 3300.00
M_r = 1701.46	D_x = 1.767 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -C 2yc	Cell parameters from 24759 reflections
a = 32.0103 (8) Å	θ = 3.0–27.5°
b = 10.2389 (3) Å	µ = 4.63 mm⁻¹
c = 19.5533 (5) Å	T = 296 K
β = 93.8269 (8)°	Stick, blue
V = 6394.3 (3) Å³	0.45 × 0.12 × 0.08 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	6376 reflections with F² > 2σ(F²)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.059
ω scans	θ_max = 27.5°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −39→41
T_min = 0.327, T_max = 0.690	k = −13→13
31073 measured reflections	l = −25→24
7321 independent reflections

Refinement top

Refinement on F²	0 restraints
R[F² > 2σ(F²)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.085	w = 1/[σ²(F_o²) + (0.043P)² + 13.526P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.002
7321 reflections	Δρ_max = 1.85 e Å⁻³
421 parameters	Δρ_min = −1.08 e Å⁻³

Crystal data top

[Cu₃W₂(CN)₁₆(C₇H₆N₂)₆(H₂O)]	V = 6394.3 (3) Å³
M_r = 1701.46	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 32.0103 (8) Å	µ = 4.63 mm⁻¹
b = 10.2389 (3) Å	T = 296 K
c = 19.5533 (5) Å	0.45 × 0.12 × 0.08 mm
β = 93.8269 (8)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	7321 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	6376 reflections with F² > 2σ(F²)
T_min = 0.327, T_max = 0.690	R_int = 0.059
31073 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.043P)² + 13.526P] where P = (F_o² + 2F_c²)/3
7321 reflections	Δρ_max = 1.85 e Å⁻³
421 parameters	Δρ_min = −1.08 e Å⁻³

Special details top

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
W(1)	0.145909 (4)	0.677683 (13)	0.197487 (7)	0.01965 (5)
Cu(2)	0.0000	0.49203 (8)	0.2500	0.03412 (16)
Cu(1)	0.188606 (15)	1.17685 (4)	0.21356 (2)	0.02394 (11)
O(1)	0.0000	0.7293 (9)	0.2500	0.122 (3)
N(2)	0.05975 (11)	0.5193 (3)	0.23372 (18)	0.0370 (8)
N(1)	0.17619 (12)	0.9853 (3)	0.21299 (18)	0.0346 (7)
N(3)	0.17679 (12)	0.3708 (3)	0.21001 (18)	0.0342 (7)
N(4)	0.24430 (12)	0.6811 (3)	0.26064 (19)	0.0339 (8)
N(5)	0.10782 (14)	0.5221 (4)	0.0592 (2)	0.0526 (11)
N(6)	0.06447 (17)	0.8632 (4)	0.1550 (3)	0.0742 (16)
N(7)	0.13445 (14)	0.7107 (5)	0.36327 (19)	0.0533 (11)
N(8)	0.19927 (14)	0.7590 (4)	0.06671 (18)	0.0495 (10)
N(9)	0.01423 (12)	0.4524 (4)	0.34652 (19)	0.0422 (9)
N(10)	0.04890 (15)	0.4583 (5)	0.4471 (2)	0.0610 (12)
N(11)	0.17406 (12)	1.1776 (3)	0.31062 (18)	0.0334 (8)
N(12)	0.17738 (19)	1.1969 (4)	0.4229 (2)	0.0611 (13)
N(13)	0.18846 (12)	1.1756 (3)	0.11163 (18)	0.0306 (7)
N(14)	0.16506 (13)	1.2126 (4)	0.00448 (19)	0.0410 (8)
C(2)	0.09067 (13)	0.5704 (4)	0.22258 (19)	0.0295 (8)
C(1)	0.16532 (12)	0.8801 (3)	0.21138 (19)	0.0276 (8)
C(3)	0.16736 (12)	0.4779 (3)	0.20814 (18)	0.0253 (7)
C(4)	0.21022 (13)	0.6805 (3)	0.2396 (2)	0.0276 (8)
C(5)	0.12014 (14)	0.5790 (4)	0.1062 (2)	0.0339 (9)
C(6)	0.09391 (15)	0.8020 (4)	0.1676 (2)	0.0399 (10)
C(7)	0.13846 (14)	0.7019 (4)	0.3060 (2)	0.0334 (9)
C(8)	0.18115 (14)	0.7292 (4)	0.11189 (19)	0.0329 (8)
C(9)	0.04547 (15)	0.5048 (5)	0.3837 (2)	0.0499 (12)
C(10)	−0.00421 (16)	0.3619 (5)	0.3883 (2)	0.0478 (11)
C(11)	−0.03601 (18)	0.2733 (6)	0.3741 (3)	0.0692 (16)
C(12)	−0.0462 (2)	0.1936 (7)	0.4281 (5)	0.097 (2)
C(13)	−0.0237 (3)	0.2026 (9)	0.4940 (5)	0.111 (3)
C(14)	0.0073 (3)	0.2874 (8)	0.5065 (3)	0.086 (2)
C(15)	0.01723 (19)	0.3657 (6)	0.4523 (2)	0.0585 (14)
C(16)	0.19871 (18)	1.2102 (5)	0.3653 (2)	0.0452 (11)
C(17)	0.13574 (16)	1.1428 (4)	0.3341 (2)	0.0422 (10)
C(18)	0.09927 (18)	1.1010 (6)	0.2988 (3)	0.0673 (16)
C(19)	0.0650 (2)	1.0730 (8)	0.3375 (6)	0.111 (3)
C(20)	0.0680 (3)	1.0858 (9)	0.4067 (6)	0.117 (3)
C(21)	0.1033 (3)	1.1243 (8)	0.4433 (4)	0.104 (3)
C(22)	0.1385 (2)	1.1537 (5)	0.4053 (3)	0.0569 (14)
C(23)	0.15930 (14)	1.2307 (4)	0.0704 (2)	0.0365 (9)
C(24)	0.21615 (14)	1.1184 (4)	0.0683 (2)	0.0328 (8)
C(25)	0.25409 (15)	1.0524 (4)	0.0820 (2)	0.0426 (10)
C(26)	0.27512 (18)	1.0159 (5)	0.0266 (3)	0.0545 (13)
C(27)	0.2601 (2)	1.0414 (5)	−0.0407 (2)	0.0577 (14)
C(28)	0.2242 (2)	1.1052 (5)	−0.0553 (2)	0.0526 (13)
C(29)	0.20135 (17)	1.1435 (4)	0.0004 (2)	0.0394 (10)
H(1)	0.025 (3)	0.784 (12)	0.233 (6)	0.20 (5)*
H(9)	0.0633	0.5677	0.3674	0.060*
H(10N)	0.0672	0.4809	0.4791	0.073*
H(11)	−0.0499	0.2671	0.3309	0.083*
H(12)	−0.0679	0.1336	0.4215	0.116*
H(12N)	0.1873	1.2136	0.4639	0.073*
H(13)	−0.0311	0.1475	0.5291	0.133*
H(14)	0.0215	0.2937	0.5494	0.103*
H(14N)	0.1489	1.2395	−0.0295	0.049*
H(16)	0.2264	1.2378	0.3643	0.054*
H(18)	0.0975	1.0918	0.2514	0.081*
H(19)	0.0399	1.0454	0.3155	0.133*
H(20)	0.0445	1.0671	0.4304	0.140*
H(21)	0.1045	1.1312	0.4908	0.124*
H(23)	0.1369	1.2775	0.0860	0.044*
H(25)	0.2644	1.0343	0.1265	0.051*
H(26)	0.3005	0.9722	0.0341	0.065*
H(27)	0.2756	1.0132	−0.0765	0.069*
H(28)	0.2147	1.1234	−0.1002	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
W(1)	0.02408 (10)	0.01523 (9)	0.01913 (9)	0.00006 (5)	−0.00245 (6)	−0.00061 (5)
Cu(2)	0.0216 (3)	0.0477 (4)	0.0322 (3)	0.0000	−0.0040 (2)	0.0000
Cu(1)	0.0300 (2)	0.0160 (2)	0.0255 (2)	0.00025 (17)	−0.0012 (2)	−0.00081 (16)
O(1)	0.105 (6)	0.069 (5)	0.200 (10)	0.0000	0.080 (6)	0.0000
N(2)	0.0287 (18)	0.044 (2)	0.0377 (19)	−0.0043 (15)	−0.0018 (15)	−0.0010 (15)
N(1)	0.048 (2)	0.0204 (17)	0.0353 (18)	−0.0029 (15)	0.0027 (16)	−0.0029 (13)
N(3)	0.045 (2)	0.0225 (18)	0.0347 (18)	0.0024 (15)	−0.0027 (15)	0.0004 (14)
N(4)	0.0310 (19)	0.033 (2)	0.037 (2)	−0.0025 (13)	−0.0035 (16)	0.0025 (13)
N(5)	0.070 (2)	0.050 (2)	0.035 (2)	−0.006 (2)	−0.017 (2)	−0.0103 (18)
N(6)	0.068 (3)	0.042 (2)	0.107 (4)	0.020 (2)	−0.031 (3)	−0.001 (2)
N(7)	0.055 (2)	0.079 (3)	0.0264 (19)	−0.017 (2)	0.0053 (18)	−0.0072 (18)
N(8)	0.069 (2)	0.052 (2)	0.0286 (18)	−0.014 (2)	0.0124 (19)	−0.0029 (17)
N(9)	0.0318 (19)	0.058 (2)	0.0361 (19)	−0.0047 (17)	−0.0057 (16)	0.0074 (17)
N(10)	0.058 (2)	0.083 (3)	0.040 (2)	0.004 (2)	−0.015 (2)	0.004 (2)
N(11)	0.042 (2)	0.0267 (18)	0.0315 (18)	0.0020 (14)	0.0016 (16)	−0.0003 (12)
N(12)	0.097 (4)	0.059 (3)	0.028 (2)	0.015 (2)	0.009 (2)	−0.0020 (18)
N(13)	0.0363 (19)	0.0273 (18)	0.0283 (17)	0.0036 (13)	0.0021 (15)	0.0009 (12)
N(14)	0.046 (2)	0.046 (2)	0.0304 (18)	0.0035 (18)	−0.0019 (16)	0.0012 (16)
C(2)	0.030 (2)	0.032 (2)	0.0264 (18)	−0.0022 (16)	−0.0030 (16)	−0.0040 (15)
C(1)	0.034 (2)	0.0203 (19)	0.0285 (18)	−0.0010 (15)	0.0013 (16)	−0.0035 (14)
C(3)	0.0311 (19)	0.0179 (18)	0.0262 (17)	0.0002 (14)	−0.0043 (15)	0.0004 (13)
C(4)	0.032 (2)	0.023 (2)	0.0271 (19)	−0.0037 (14)	−0.0003 (17)	0.0012 (14)
C(5)	0.041 (2)	0.030 (2)	0.030 (2)	−0.0001 (17)	−0.0059 (18)	0.0013 (16)
C(6)	0.036 (2)	0.028 (2)	0.054 (2)	0.0076 (17)	−0.010 (2)	−0.0015 (18)
C(7)	0.030 (2)	0.038 (2)	0.033 (2)	−0.0081 (17)	0.0011 (17)	−0.0037 (17)
C(8)	0.042 (2)	0.033 (2)	0.0233 (18)	−0.0021 (18)	0.0009 (17)	−0.0063 (16)
C(9)	0.037 (2)	0.073 (3)	0.038 (2)	−0.007 (2)	−0.010 (2)	0.000 (2)
C(10)	0.039 (2)	0.054 (3)	0.051 (2)	0.009 (2)	0.007 (2)	0.013 (2)
C(11)	0.046 (3)	0.060 (3)	0.102 (4)	0.002 (2)	0.009 (3)	0.013 (3)
C(12)	0.075 (5)	0.057 (4)	0.163 (9)	0.003 (3)	0.038 (5)	0.037 (4)
C(13)	0.132 (8)	0.083 (6)	0.123 (7)	0.032 (5)	0.053 (6)	0.063 (5)
C(14)	0.112 (6)	0.084 (5)	0.065 (4)	0.031 (4)	0.033 (4)	0.035 (3)
C(15)	0.062 (3)	0.067 (3)	0.047 (2)	0.024 (3)	0.006 (2)	0.011 (2)
C(16)	0.059 (3)	0.044 (2)	0.032 (2)	0.003 (2)	−0.002 (2)	−0.0059 (19)
C(17)	0.051 (2)	0.026 (2)	0.052 (2)	0.0041 (19)	0.015 (2)	−0.0012 (19)
C(18)	0.050 (3)	0.056 (3)	0.096 (4)	−0.002 (2)	0.014 (3)	−0.016 (3)
C(19)	0.058 (4)	0.086 (6)	0.197 (10)	−0.015 (3)	0.059 (5)	−0.046 (6)
C(20)	0.099 (6)	0.081 (6)	0.181 (10)	−0.019 (5)	0.093 (7)	−0.022 (6)
C(21)	0.163 (9)	0.063 (4)	0.096 (5)	0.017 (5)	0.086 (6)	0.011 (4)
C(22)	0.076 (4)	0.042 (3)	0.056 (3)	0.005 (2)	0.031 (3)	0.003 (2)
C(23)	0.043 (2)	0.035 (2)	0.031 (2)	0.0034 (19)	0.0008 (18)	−0.0015 (17)
C(24)	0.043 (2)	0.021 (2)	0.034 (2)	−0.0031 (17)	0.0031 (18)	−0.0004 (15)
C(25)	0.049 (2)	0.032 (2)	0.046 (2)	0.005 (2)	0.003 (2)	−0.0017 (19)
C(26)	0.058 (3)	0.036 (2)	0.071 (3)	0.010 (2)	0.019 (2)	−0.005 (2)
C(27)	0.081 (4)	0.042 (3)	0.055 (3)	0.000 (2)	0.032 (2)	−0.009 (2)
C(28)	0.084 (4)	0.039 (2)	0.036 (2)	−0.002 (2)	0.015 (2)	−0.004 (2)
C(29)	0.060 (3)	0.027 (2)	0.032 (2)	−0.004 (2)	0.003 (2)	0.0008 (16)

Geometric parameters (Å, º) top

W(1)—C(2)	2.165 (4)	C(10)—C(15)	1.388 (7)
W(1)—C(1)	2.176 (3)	C(11)—C(12)	1.390 (12)
W(1)—C(3)	2.163 (3)	C(12)—C(13)	1.436 (14)
W(1)—C(4)	2.166 (4)	C(13)—C(14)	1.329 (13)
W(1)—C(5)	2.166 (3)	C(14)—C(15)	1.383 (10)
W(1)—C(6)	2.145 (4)	C(17)—C(18)	1.384 (7)
W(1)—C(7)	2.165 (4)	C(17)—C(22)	1.394 (7)
W(1)—C(8)	2.146 (4)	C(18)—C(19)	1.403 (11)
Cu(2)—N(2)	1.980 (3)	C(19)—C(20)	1.356 (17)
Cu(2)—N(2)ⁱ	1.980 (3)	C(20)—C(21)	1.355 (14)
Cu(2)—N(9)	1.954 (3)	C(21)—C(22)	1.421 (12)
Cu(2)—N(9)ⁱ	1.954 (3)	C(24)—C(25)	1.400 (6)
Cu(1)—N(1)	2.001 (3)	C(24)—C(29)	1.403 (5)
Cu(1)—N(3)ⁱⁱ	2.022 (3)	C(25)—C(26)	1.364 (7)
Cu(1)—N(4)ⁱⁱⁱ	2.174 (3)	C(26)—C(27)	1.396 (7)
Cu(1)—N(11)	1.984 (3)	C(27)—C(28)	1.335 (8)
Cu(1)—N(13)	1.993 (3)	C(28)—C(29)	1.408 (7)
N(2)—C(2)	1.153 (5)	O(1)—H(1)	1.05 (12)
N(1)—C(1)	1.131 (5)	O(1)—H(1)ⁱ	1.05 (12)
N(3)—C(3)	1.137 (5)	N(10)—H(10N)	0.860
N(4)—C(4)	1.140 (5)	N(12)—H(12N)	0.860
N(5)—C(5)	1.136 (5)	N(14)—H(14N)	0.860
N(6)—C(6)	1.145 (6)	C(9)—H(9)	0.930
N(7)—C(7)	1.139 (5)	C(11)—H(11)	0.930
N(8)—C(8)	1.131 (5)	C(12)—H(12)	0.930
N(9)—C(9)	1.312 (6)	C(13)—H(13)	0.930
N(9)—C(10)	1.392 (6)	C(14)—H(14)	0.930
N(10)—C(9)	1.326 (6)	C(16)—H(16)	0.930
N(10)—C(15)	1.396 (8)	C(18)—H(18)	0.930
N(11)—C(16)	1.327 (5)	C(19)—H(19)	0.930
N(11)—C(17)	1.385 (6)	C(20)—H(20)	0.930
N(12)—C(16)	1.362 (7)	C(21)—H(21)	0.930
N(12)—C(22)	1.345 (8)	C(23)—H(23)	0.930
N(13)—C(23)	1.318 (5)	C(25)—H(25)	0.930
N(13)—C(24)	1.394 (5)	C(26)—H(26)	0.930
N(14)—C(23)	1.328 (5)	C(27)—H(27)	0.930
N(14)—C(29)	1.367 (6)	C(28)—H(28)	0.930
C(10)—C(11)	1.378 (8)

N(5)···N(10)^iv	2.802 (5)	C(27)···H(12N)^vi	3.506
N(7)···N(14)^v	2.973 (5)	C(27)···H(16)^vi	3.538
N(8)···N(12)^vi	2.889 (5)	C(28)···H(12N)^vi	3.500
N(8)···C(26)^vii	3.482 (6)	H(9)···H(14)^ix	3.551
N(8)···C(27)^vii	3.391 (7)	H(10N)···N(5)^viii	1.968
N(10)···N(5)^viii	2.802 (5)	H(10N)···C(5)^viii	2.976
N(10)···C(14)^ix	3.324 (10)	H(10N)···C(13)^ix	3.580
N(10)···C(15)^ix	3.485 (7)	H(10N)···C(14)^ix	3.389
N(12)···N(8)^v	2.889 (5)	H(10N)···C(15)^ix	3.472
N(12)···C(28)^v	3.451 (7)	H(11)···C(18)^xii	3.360
N(14)···N(7)^vi	2.973 (5)	H(11)···H(18)^xii	2.795
N(14)···C(26)^x	3.453 (6)	H(11)···H(23)^xii	3.320
N(14)···C(27)^x	3.515 (7)	H(12)···N(6)^xii	3.152
C(9)···C(14)^ix	3.531 (10)	H(12)···C(23)^xii	3.104
C(14)···N(10)^ix	3.324 (10)	H(12)···H(18)^xii	3.476
C(14)···C(9)^ix	3.531 (10)	H(12)···H(20)^ix	3.589
C(15)···N(10)^ix	3.485 (7)	H(12)···H(21)^ix	3.453
C(15)···C(15)^ix	3.539 (8)	H(12)···H(23)^xii	2.652
C(23)···C(27)^x	3.555 (7)	H(12N)···N(8)^v	2.040
C(24)···C(28)^x	3.433 (7)	H(12N)···C(8)^v	2.971
C(26)···N(8)^vii	3.482 (6)	H(12N)···C(27)^v	3.506
C(26)···N(14)^x	3.453 (6)	H(12N)···C(28)^v	3.500
C(27)···N(8)^vii	3.391 (7)	H(13)···C(20)^ix	2.980
C(27)···N(14)^x	3.515 (7)	H(13)···H(20)^ix	2.384
C(27)···C(23)^x	3.555 (7)	H(14)···N(5)^viii	3.340
C(27)···C(29)^x	3.524 (7)	H(14)···N(6)^viii	2.890
C(28)···N(12)^vi	3.451 (7)	H(14)···N(9)^ix	3.538
C(28)···C(24)^x	3.433 (7)	H(14)···N(10)^ix	3.399
C(29)···C(27)^x	3.524 (7)	H(14)···C(5)^viii	3.525
N(3)···H(27)^vii	3.329	H(14)···C(6)^viii	3.310
N(4)···H(28)^v	3.556	H(14)···C(9)^ix	3.307
N(5)···H(10N)^iv	1.968	H(14)···H(9)^ix	3.551
N(5)···H(14)^iv	3.340	H(14N)···N(7)^vi	2.177
N(5)···H(26)^vii	3.558	H(14N)···C(7)^vi	3.267
N(6)···H(12)^xi	3.152	H(14N)···C(26)^x	3.489
N(6)···H(14)^iv	2.890	H(14N)···H(26)^x	3.371
N(6)···H(21)^vi	3.534	H(16)···C(27)^v	3.538
N(7)···H(14N)^v	2.177	H(16)···H(27)^v	3.190
N(7)···H(28)^v	3.123	H(18)···C(11)^xi	3.566
N(8)···H(12N)^vi	2.040	H(18)···H(11)^xi	2.795
N(8)···H(21)^vi	3.475	H(18)···H(12)^xi	3.476
N(8)···H(26)^vii	3.080	H(20)···C(13)^ix	3.222
N(8)···H(27)^vii	2.904	H(20)···H(12)^ix	3.589
N(9)···H(14)^ix	3.538	H(20)···H(13)^ix	2.384
N(10)···H(14)^ix	3.399	H(21)···N(6)^v	3.534
N(12)···H(28)^v	3.531	H(21)···N(8)^v	3.475
N(13)···H(27)^x	3.472	H(21)···C(6)^v	3.561
N(14)···H(26)^x	3.508	H(21)···C(8)^v	3.591
C(3)···H(27)^vii	3.255	H(21)···H(12)^ix	3.453
C(5)···H(10N)^iv	2.976	H(23)···C(11)^xi	3.374
C(5)···H(14)^iv	3.525	H(23)···C(12)^xi	3.024
C(5)···H(27)^vii	3.555	H(23)···H(11)^xi	3.320
C(6)···H(14)^iv	3.310	H(23)···H(12)^xi	2.652
C(6)···H(21)^vi	3.561	H(23)···H(27)^x	3.542
C(7)···H(14N)^v	3.267	H(26)···N(5)^vii	3.558
C(7)···H(28)^v	3.453	H(26)···N(8)^vii	3.080
C(8)···H(12N)^vi	2.971	H(26)···N(14)^x	3.508
C(8)···H(21)^vi	3.591	H(26)···H(14N)^x	3.371
C(8)···H(27)^vii	2.947	H(27)···N(3)^vii	3.329
C(9)···H(14)^ix	3.307	H(27)···N(8)^vii	2.904
C(11)···H(18)^xii	3.566	H(27)···N(13)^x	3.472
C(11)···H(23)^xii	3.374	H(27)···C(3)^vii	3.255
C(12)···H(23)^xii	3.024	H(27)···C(5)^vii	3.555
C(13)···H(10N)^ix	3.580	H(27)···C(8)^vii	2.947
C(13)···H(20)^ix	3.222	H(27)···C(16)^vi	3.493
C(14)···H(10N)^ix	3.389	H(27)···C(23)^x	3.348
C(15)···H(10N)^ix	3.472	H(27)···H(16)^vi	3.190
C(16)···H(27)^v	3.493	H(27)···H(23)^x	3.542
C(16)···H(28)^v	3.513	H(28)···N(4)^vi	3.556
C(18)···H(11)^xi	3.360	H(28)···N(7)^vi	3.123
C(20)···H(13)^ix	2.980	H(28)···N(12)^vi	3.531
C(23)···H(12)^xi	3.104	H(28)···C(7)^vi	3.453
C(23)···H(27)^x	3.348	H(28)···C(16)^vi	3.513
C(24)···H(28)^x	3.476	H(28)···C(24)^x	3.476
C(25)···H(28)^x	3.477	H(28)···C(25)^x	3.477
C(26)···H(14N)^x	3.489

C(2)—W(1)—C(1)	133.28 (14)	N(9)—C(10)—C(11)	131.1 (5)
C(2)—W(1)—C(3)	75.96 (14)	N(9)—C(10)—C(15)	107.9 (4)
C(2)—W(1)—C(4)	133.67 (14)	C(11)—C(10)—C(15)	120.9 (5)
C(2)—W(1)—C(5)	71.25 (15)	C(10)—C(11)—C(12)	116.2 (6)
C(2)—W(1)—C(6)	74.47 (16)	C(11)—C(12)—C(13)	121.0 (7)
C(2)—W(1)—C(7)	72.00 (15)	C(12)—C(13)—C(14)	122.0 (8)
C(2)—W(1)—C(8)	141.36 (14)	C(13)—C(14)—C(15)	116.5 (7)
C(1)—W(1)—C(3)	143.38 (14)	N(10)—C(15)—C(10)	105.7 (4)
C(1)—W(1)—C(4)	71.55 (13)	N(10)—C(15)—C(14)	130.9 (5)
C(1)—W(1)—C(5)	129.57 (14)	C(10)—C(15)—C(14)	123.3 (6)
C(1)—W(1)—C(6)	71.26 (15)	N(11)—C(16)—N(12)	109.7 (4)
C(1)—W(1)—C(7)	79.50 (15)	N(11)—C(17)—C(18)	130.5 (4)
C(1)—W(1)—C(8)	72.70 (15)	N(11)—C(17)—C(22)	108.2 (4)
C(3)—W(1)—C(4)	71.85 (13)	C(18)—C(17)—C(22)	121.2 (5)
C(3)—W(1)—C(5)	74.89 (14)	C(17)—C(18)—C(19)	117.2 (6)
C(3)—W(1)—C(6)	145.36 (15)	C(18)—C(19)—C(20)	120.8 (7)
C(3)—W(1)—C(7)	93.95 (14)	C(19)—C(20)—C(21)	123.8 (9)
C(3)—W(1)—C(8)	97.32 (15)	C(20)—C(21)—C(22)	116.5 (8)
C(4)—W(1)—C(5)	128.28 (15)	N(12)—C(22)—C(17)	106.0 (5)
C(4)—W(1)—C(6)	142.77 (15)	N(12)—C(22)—C(21)	133.6 (6)
C(4)—W(1)—C(7)	77.88 (15)	C(17)—C(22)—C(21)	120.4 (6)
C(4)—W(1)—C(8)	75.95 (15)	N(13)—C(23)—N(14)	113.3 (4)
C(5)—W(1)—C(6)	78.82 (17)	N(13)—C(24)—C(25)	131.7 (3)
C(5)—W(1)—C(7)	143.17 (16)	N(13)—C(24)—C(29)	108.0 (3)
C(5)—W(1)—C(8)	70.29 (15)	C(25)—C(24)—C(29)	120.1 (4)
C(6)—W(1)—C(7)	93.73 (17)	C(24)—C(25)—C(26)	116.7 (4)
C(6)—W(1)—C(8)	94.60 (17)	C(25)—C(26)—C(27)	122.7 (5)
C(7)—W(1)—C(8)	146.55 (16)	C(26)—C(27)—C(28)	122.0 (5)
N(2)—Cu(2)—N(2)ⁱ	163.78 (16)	C(27)—C(28)—C(29)	117.1 (4)
N(2)—Cu(2)—N(9)	91.10 (15)	N(14)—C(29)—C(24)	105.9 (3)
N(2)—Cu(2)—N(9)ⁱ	92.26 (15)	N(14)—C(29)—C(28)	132.6 (4)
N(2)ⁱ—Cu(2)—N(9)	92.26 (15)	C(24)—C(29)—C(28)	121.4 (4)
N(2)ⁱ—Cu(2)—N(9)ⁱ	91.10 (15)	H(1)—O(1)—H(1)ⁱ	116 (9)
N(9)—Cu(2)—N(9)ⁱ	156.03 (18)	C(9)—N(10)—H(10N)	126.4
N(1)—Cu(1)—N(3)ⁱⁱ	157.80 (15)	C(15)—N(10)—H(10N)	126.4
N(1)—Cu(1)—N(4)ⁱⁱⁱ	102.33 (14)	C(16)—N(12)—H(12N)	125.4
N(1)—Cu(1)—N(11)	87.14 (14)	C(22)—N(12)—H(12N)	125.4
N(1)—Cu(1)—N(13)	90.06 (13)	C(23)—N(14)—H(14N)	126.2
N(3)ⁱⁱ—Cu(1)—N(4)ⁱⁱⁱ	99.67 (14)	C(29)—N(14)—H(14N)	126.2
N(3)ⁱⁱ—Cu(1)—N(11)	88.48 (14)	N(9)—C(9)—H(9)	123.7
N(3)ⁱⁱ—Cu(1)—N(13)	89.08 (13)	N(10)—C(9)—H(9)	123.7
N(4)ⁱⁱⁱ—Cu(1)—N(11)	93.97 (14)	C(10)—C(11)—H(11)	121.9
N(4)ⁱⁱⁱ—Cu(1)—N(13)	99.71 (14)	C(12)—C(11)—H(11)	121.9
N(11)—Cu(1)—N(13)	166.32 (15)	C(11)—C(12)—H(12)	119.5
Cu(2)—N(2)—C(2)	160.9 (3)	C(13)—C(12)—H(12)	119.5
Cu(1)—N(1)—C(1)	173.5 (3)	C(12)—C(13)—H(13)	119.0
Cu(1)^xiii—N(3)—C(3)	175.4 (3)	C(14)—C(13)—H(13)	119.0
Cu(1)^xiv—N(4)—C(4)	172.1 (3)	C(13)—C(14)—H(14)	121.7
Cu(2)—N(9)—C(9)	124.8 (3)	C(15)—C(14)—H(14)	121.8
Cu(2)—N(9)—C(10)	128.6 (3)	N(11)—C(16)—H(16)	125.2
C(9)—N(9)—C(10)	106.5 (3)	N(12)—C(16)—H(16)	125.2
C(9)—N(10)—C(15)	107.3 (4)	C(17)—C(18)—H(18)	121.4
Cu(1)—N(11)—C(16)	127.3 (3)	C(19)—C(18)—H(18)	121.4
Cu(1)—N(11)—C(17)	125.9 (2)	C(18)—C(19)—H(19)	119.6
C(16)—N(11)—C(17)	106.8 (3)	C(20)—C(19)—H(19)	119.6
C(16)—N(12)—C(22)	109.2 (4)	C(19)—C(20)—H(20)	118.1
Cu(1)—N(13)—C(23)	124.3 (3)	C(21)—C(20)—H(20)	118.1
Cu(1)—N(13)—C(24)	130.6 (2)	C(20)—C(21)—H(21)	121.7
C(23)—N(13)—C(24)	105.1 (3)	C(22)—C(21)—H(21)	121.7
C(23)—N(14)—C(29)	107.6 (3)	N(13)—C(23)—H(23)	123.3
W(1)—C(2)—N(2)	175.6 (3)	N(14)—C(23)—H(23)	123.4
W(1)—C(1)—N(1)	174.2 (3)	C(24)—C(25)—H(25)	121.7
W(1)—C(3)—N(3)	175.3 (3)	C(26)—C(25)—H(25)	121.7
W(1)—C(4)—N(4)	178.7 (3)	C(25)—C(26)—H(26)	118.7
W(1)—C(5)—N(5)	176.6 (3)	C(27)—C(26)—H(26)	118.7
W(1)—C(6)—N(6)	174.9 (4)	C(26)—C(27)—H(27)	119.0
W(1)—C(7)—N(7)	177.9 (4)	C(28)—C(27)—H(27)	119.0
W(1)—C(8)—N(8)	178.4 (4)	C(27)—C(28)—H(28)	121.4
N(9)—C(9)—N(10)	112.6 (4)	C(29)—C(28)—H(28)	121.4

C(2)—W(1)—C(1)—N(1)	−131 (3)	N(13)—Cu(1)—N(1)—C(1)	−82 (3)
C(1)—W(1)—C(2)—N(2)	53 (4)	N(3)ⁱⁱ—Cu(1)—N(4)ⁱⁱⁱ—C(4)ⁱⁱⁱ	100 (2)
C(2)—W(1)—C(3)—N(3)	64 (4)	N(4)ⁱⁱⁱ—Cu(1)—N(3)ⁱⁱ—C(3)ⁱⁱ	−165 (4)
C(3)—W(1)—C(2)—N(2)	−153 (4)	N(3)ⁱⁱ—Cu(1)—N(11)—C(16)	−82.6 (3)
C(2)—W(1)—C(4)—N(4)	115 (14)	N(3)ⁱⁱ—Cu(1)—N(11)—C(17)	98.0 (3)
C(4)—W(1)—C(2)—N(2)	160 (4)	N(11)—Cu(1)—N(3)ⁱⁱ—C(3)ⁱⁱ	−72 (4)
C(2)—W(1)—C(5)—N(5)	−89 (6)	N(3)ⁱⁱ—Cu(1)—N(13)—C(23)	−47.8 (3)
C(5)—W(1)—C(2)—N(2)	−74 (4)	N(3)ⁱⁱ—Cu(1)—N(13)—C(24)	133.9 (3)
C(2)—W(1)—C(6)—N(6)	22 (5)	N(13)—Cu(1)—N(3)ⁱⁱ—C(3)ⁱⁱ	95 (4)
C(6)—W(1)—C(2)—N(2)	9 (4)	N(4)ⁱⁱⁱ—Cu(1)—N(11)—C(16)	17.0 (3)
C(2)—W(1)—C(7)—N(7)	51 (11)	N(4)ⁱⁱⁱ—Cu(1)—N(11)—C(17)	−162.4 (3)
C(7)—W(1)—C(2)—N(2)	108 (4)	N(11)—Cu(1)—N(4)ⁱⁱⁱ—C(4)ⁱⁱⁱ	11 (2)
C(2)—W(1)—C(8)—N(8)	98 (13)	N(4)ⁱⁱⁱ—Cu(1)—N(13)—C(23)	−147.5 (3)
C(8)—W(1)—C(2)—N(2)	−68 (4)	N(4)ⁱⁱⁱ—Cu(1)—N(13)—C(24)	34.3 (3)
C(1)—W(1)—C(3)—N(3)	−148 (4)	N(13)—Cu(1)—N(4)ⁱⁱⁱ—C(4)ⁱⁱⁱ	−169 (2)
C(3)—W(1)—C(1)—N(1)	93 (3)	N(11)—Cu(1)—N(13)—C(23)	32.0 (7)
C(1)—W(1)—C(4)—N(4)	−112 (14)	N(11)—Cu(1)—N(13)—C(24)	−146.3 (5)
C(4)—W(1)—C(1)—N(1)	95 (3)	N(13)—Cu(1)—N(11)—C(16)	−162.4 (5)
C(1)—W(1)—C(5)—N(5)	140 (6)	N(13)—Cu(1)—N(11)—C(17)	18.1 (7)
C(5)—W(1)—C(1)—N(1)	−30 (3)	Cu(2)—N(2)—C(2)—W(1)	−28 (5)
C(1)—W(1)—C(6)—N(6)	−126 (5)	Cu(1)—N(1)—C(1)—W(1)	95 (4)
C(6)—W(1)—C(1)—N(1)	−87 (3)	Cu(1)^xiii—N(3)—C(3)—W(1)	−53 (7)
C(1)—W(1)—C(7)—N(7)	−166 (11)	Cu(1)^xiv—N(4)—C(4)—W(1)	11 (16)
C(7)—W(1)—C(1)—N(1)	176 (3)	Cu(2)—N(9)—C(9)—N(10)	−178.3 (3)
C(1)—W(1)—C(8)—N(8)	−42 (13)	Cu(2)—N(9)—C(10)—C(11)	2.3 (8)
C(8)—W(1)—C(1)—N(1)	15 (3)	Cu(2)—N(9)—C(10)—C(15)	178.3 (3)
C(3)—W(1)—C(4)—N(4)	66 (14)	C(9)—N(9)—C(10)—C(11)	−174.8 (6)
C(4)—W(1)—C(3)—N(3)	−150 (4)	C(9)—N(9)—C(10)—C(15)	1.2 (6)
C(3)—W(1)—C(5)—N(5)	−9 (6)	C(10)—N(9)—C(9)—N(10)	−1.1 (6)
C(5)—W(1)—C(3)—N(3)	−10 (4)	C(9)—N(10)—C(15)—C(10)	0.3 (6)
C(3)—W(1)—C(6)—N(6)	54 (5)	C(9)—N(10)—C(15)—C(14)	178.9 (7)
C(6)—W(1)—C(3)—N(3)	31 (4)	C(15)—N(10)—C(9)—N(9)	0.5 (6)
C(3)—W(1)—C(7)—N(7)	−22 (11)	Cu(1)—N(11)—C(16)—N(12)	−179.4 (3)
C(7)—W(1)—C(3)—N(3)	134 (4)	Cu(1)—N(11)—C(17)—C(18)	−0.3 (5)
C(3)—W(1)—C(8)—N(8)	174 (13)	Cu(1)—N(11)—C(17)—C(22)	178.7 (3)
C(8)—W(1)—C(3)—N(3)	−78 (4)	C(16)—N(11)—C(17)—C(18)	−179.8 (3)
C(4)—W(1)—C(5)—N(5)	42 (7)	C(16)—N(11)—C(17)—C(22)	−0.9 (5)
C(5)—W(1)—C(4)—N(4)	14 (14)	C(17)—N(11)—C(16)—N(12)	0.1 (4)
C(4)—W(1)—C(6)—N(6)	−123 (5)	C(16)—N(12)—C(22)—C(17)	−1.3 (6)
C(6)—W(1)—C(4)—N(4)	−115 (14)	C(16)—N(12)—C(22)—C(21)	−179.3 (7)
C(4)—W(1)—C(7)—N(7)	−93 (11)	C(22)—N(12)—C(16)—N(11)	0.7 (6)
C(7)—W(1)—C(4)—N(4)	165 (14)	Cu(1)—N(13)—C(23)—N(14)	−177.5 (3)
C(4)—W(1)—C(8)—N(8)	−117 (13)	Cu(1)—N(13)—C(24)—C(25)	−5.3 (6)
C(8)—W(1)—C(4)—N(4)	−36 (14)	Cu(1)—N(13)—C(24)—C(29)	178.5 (3)
C(5)—W(1)—C(6)—N(6)	95 (5)	C(23)—N(13)—C(24)—C(25)	176.2 (4)
C(6)—W(1)—C(5)—N(5)	−166 (6)	C(23)—N(13)—C(24)—C(29)	−0.0 (3)
C(5)—W(1)—C(7)—N(7)	48 (11)	C(24)—N(13)—C(23)—N(14)	1.1 (5)
C(7)—W(1)—C(5)—N(5)	−85 (6)	C(23)—N(14)—C(29)—C(24)	1.6 (5)
C(5)—W(1)—C(8)—N(8)	103 (13)	C(23)—N(14)—C(29)—C(28)	−174.7 (5)
C(8)—W(1)—C(5)—N(5)	95 (6)	C(29)—N(14)—C(23)—N(13)	−1.8 (5)
C(6)—W(1)—C(7)—N(7)	124 (11)	N(9)—C(10)—C(11)—C(12)	178.2 (6)
C(7)—W(1)—C(6)—N(6)	−48 (5)	N(9)—C(10)—C(15)—N(10)	−0.9 (6)
C(6)—W(1)—C(8)—N(8)	27 (13)	N(9)—C(10)—C(15)—C(14)	−179.6 (6)
C(8)—W(1)—C(6)—N(6)	164 (5)	C(11)—C(10)—C(15)—N(10)	175.5 (5)
C(7)—W(1)—C(8)—N(8)	−77 (13)	C(11)—C(10)—C(15)—C(14)	−3.2 (10)
C(8)—W(1)—C(7)—N(7)	−132 (11)	C(15)—C(10)—C(11)—C(12)	2.7 (9)
N(2)—Cu(2)—N(2)ⁱ—C(2)ⁱ	−7.9 (13)	C(10)—C(11)—C(12)—C(13)	−1.5 (11)
N(2)ⁱ—Cu(2)—N(2)—C(2)	−7.9 (13)	C(11)—C(12)—C(13)—C(14)	0.6 (13)
N(2)—Cu(2)—N(9)—C(9)	33.0 (4)	C(12)—C(13)—C(14)—C(15)	−0.8 (14)
N(2)—Cu(2)—N(9)—C(10)	−143.5 (4)	C(13)—C(14)—C(15)—N(10)	−176.3 (7)
N(9)—Cu(2)—N(2)—C(2)	−109.8 (10)	C(13)—C(14)—C(15)—C(10)	2.1 (12)
N(2)—Cu(2)—N(9)ⁱ—C(9)ⁱ	−131.1 (4)	N(11)—C(17)—C(18)—C(19)	−179.7 (5)
N(2)—Cu(2)—N(9)ⁱ—C(10)ⁱ	52.3 (4)	N(11)—C(17)—C(22)—N(12)	1.3 (5)
N(9)ⁱ—Cu(2)—N(2)—C(2)	93.9 (10)	N(11)—C(17)—C(22)—C(21)	179.7 (5)
N(2)ⁱ—Cu(2)—N(9)—C(9)	−131.1 (4)	C(18)—C(17)—C(22)—N(12)	−179.6 (4)
N(2)ⁱ—Cu(2)—N(9)—C(10)	52.3 (4)	C(18)—C(17)—C(22)—C(21)	−1.3 (8)
N(9)—Cu(2)—N(2)ⁱ—C(2)ⁱ	93.9 (10)	C(22)—C(17)—C(18)—C(19)	1.4 (8)
N(2)ⁱ—Cu(2)—N(9)ⁱ—C(9)ⁱ	33.0 (4)	C(17)—C(18)—C(19)—C(20)	−0.5 (10)
N(2)ⁱ—Cu(2)—N(9)ⁱ—C(10)ⁱ	−143.5 (4)	C(18)—C(19)—C(20)—C(21)	−0.6 (11)
N(9)ⁱ—Cu(2)—N(2)ⁱ—C(2)ⁱ	−109.8 (10)	C(19)—C(20)—C(21)—C(22)	0.8 (13)
N(9)—Cu(2)—N(9)ⁱ—C(9)ⁱ	131.1 (4)	C(20)—C(21)—C(22)—N(12)	178.0 (7)
N(9)—Cu(2)—N(9)ⁱ—C(10)ⁱ	−45.5 (6)	C(20)—C(21)—C(22)—C(17)	0.1 (8)
N(9)ⁱ—Cu(2)—N(9)—C(9)	131.1 (4)	N(13)—C(24)—C(25)—C(26)	−175.5 (4)
N(9)ⁱ—Cu(2)—N(9)—C(10)	−45.5 (6)	N(13)—C(24)—C(29)—N(14)	−1.0 (4)
N(1)—Cu(1)—N(3)ⁱⁱ—C(3)ⁱⁱ	7 (4)	N(13)—C(24)—C(29)—C(28)	175.8 (4)
N(3)ⁱⁱ—Cu(1)—N(1)—C(1)	5 (3)	C(25)—C(24)—C(29)—N(14)	−177.8 (4)
N(1)—Cu(1)—N(4)ⁱⁱⁱ—C(4)ⁱⁱⁱ	−77 (2)	C(25)—C(24)—C(29)—C(28)	−0.9 (6)
N(4)ⁱⁱⁱ—Cu(1)—N(1)—C(1)	178 (2)	C(29)—C(24)—C(25)—C(26)	0.3 (6)
N(1)—Cu(1)—N(11)—C(16)	119.2 (3)	C(24)—C(25)—C(26)—C(27)	−0.3 (6)
N(1)—Cu(1)—N(11)—C(17)	−60.3 (3)	C(25)—C(26)—C(27)—C(28)	0.9 (8)
N(11)—Cu(1)—N(1)—C(1)	84 (2)	C(26)—C(27)—C(28)—C(29)	−1.4 (8)
N(1)—Cu(1)—N(13)—C(23)	110.0 (3)	C(27)—C(28)—C(29)—N(14)	177.3 (5)
N(1)—Cu(1)—N(13)—C(24)	−68.3 (3)	C(27)—C(28)—C(29)—C(24)	1.5 (7)

Symmetry codes: (i) −x, y, −z+1/2; (ii) x, y+1, z; (iii) −x+1/2, y+1/2, −z+1/2; (iv) x, −y+1, z−1/2; (v) x, −y+2, z+1/2; (vi) x, −y+2, z−1/2; (vii) −x+1/2, −y+3/2, −z; (viii) x, −y+1, z+1/2; (ix) −x, −y+1, −z+1; (x) −x+1/2, −y+5/2, −z; (xi) −x, y+1, −z+1/2; (xii) −x, y−1, −z+1/2; (xiii) x, y−1, z; (xiv) −x+1/2, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O(1)—H(1)···N(6)	1.05 (12)	2.20 (12)	3.178 (7)	154 (10)
N(10)—H(10N)···N(5)^viii	0.86	1.97	2.802 (5)	163
N(12)—H(12N)···N(8)^v	0.86	2.04	2.888 (5)	169
N(14)—H(14N)···N(7)^vi	0.86	2.18	2.973 (5)	154

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

Experimental details

Crystal data
Chemical formula	[Cu₃W₂(CN)₁₆(C₇H₆N₂)₆(H₂O)]
M_r	1701.46
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	32.0103 (8), 10.2389 (3), 19.5533 (5)
β (°)	93.8269 (8)
V (Å³)	6394.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.63
Crystal size (mm)	0.45 × 0.12 × 0.08

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.327, 0.690
No. of measured, independent and observed [F² > 2σ(F²)] reflections	31073, 7321, 6376
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.085, 1.02
No. of reflections	7321
No. of parameters	421
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ²(F_o²) + (0.043P)² + 13.526P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.85, −1.08

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and VESTA (Momma & Izumi, 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O(1)—H(1)···N(6)	1.05 (12)	2.20 (12)	3.178 (7)	154 (10)
N(10)—H(10N)···N(5)ⁱ	0.860	1.968	2.802 (5)	163.1
N(12)—H(12N)···N(8)ⁱⁱ	0.860	2.040	2.888 (5)	168.6
N(14)—H(14N)···N(7)ⁱⁱⁱ	0.860	2.177	2.973 (5)	153.8

Symmetry codes: (i) x, −y+1, z+1/2; (ii) x, −y+2, z+1/2; (iii) x, −y+2, z−1/2.

Acknowledgements

The present research was supported in part by a Grant-in-Aid for Young Scientists (S) from JSPS, a grant from the Global COE Program "Chemistry Innovation through Cooperation of Science and Engineering" and the Photon Frontier Network Program from MEXT, Japan, the Izumi Science and Technology Foundation. YT is grateful to the JSPS Research Fellowships for Young Scientists.

References

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Volume 66| Part 4| April 2010| Pages m403-m404

doi:10.1107/S160053681000841X

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Poly[aqua­hexa­benzimidazole­octa-μ-cyanido-octa­cyanidotricopper(II)ditungstate(V)]

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Poly[aquahexabenzimidazoleocta-μ-cyanido-octacyanidotricopper(II)ditungstate(V)]