Poly[[di­aqua­deca-μ2-cyanido-κ20C:N-hexa­cyanido-κ6C-bis­(μ2-5-methyl­pyrimidine-κ2N:N′)bis­(5-methyl­pyrimidine-κN)tricopper(II)ditungstate(V)] dihydrate]

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

doi:10.1107/S1600536814000166

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 70| Part 2| February 2014| Pages m47-m48

doi:10.1107/S1600536814000166

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Poly[[diaquadeca-μ₂-cyanido-κ²⁰C:N-hexacyanido-κ⁶C-bis(μ₂-5-methylpyrimidine-κ²N:N′)bis(5-methylpyrimidine-κN)tricopper(II)ditungstate(V)] dihydrate]

Yoshihide Tsunobuchi,^a Souhei Kaneko,^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 16 December 2013; accepted 4 January 2014; online 18 January 2014)

In the title complex, {[Cu₃[W(CN)₈]₂(C₅H₆N₂)₄(H₂O)₂]·2H₂O}_n, the coordination polyhedron of the eight-coordinated W^V atom is a bicapped trigonal prism, in which five CN groups are bridged to Cu^II ions, and the other three CN groups are terminally bound. Two of the Cu^II ions lie on a centre of inversion and each of the three independent Cu^II cations is pseudo-octahedrally coordinated. In the crystal structure, cyanido-bridged-Cu—W—Cu layers are linked by pillars involving the third independent Cu^II ion, generating a three-dimensional network with non-coordinating water molecules and 5-methylpyrimidine molecules. O—H⋯O and O—H⋯N hydrogen bonds involve the coordinating and non-coordinating water molecules, the CN groups and the 5-methylpyrimidine molecules.

CCDC reference: 979660

Related literature

For background to functional three-dimensional networks, see: Catala et al. (2005 ); Garde et al. (1999 ); Herrera et al. (2004 , 2008 ); Imoto et al. (2012 ); Leipoldt et al. (1994 ); Ohkoshi & Tokoro (2012 ); Ohkoshi et al. (2011 ); Sieklucka et al. (2009 ); Zhong et al. (2000 ). For related structures, see: Ohkoshi et al. (2007 , 2012); Podgajny et al. (2002 ).

Experimental

Crystal data

[Cu₃W₂(CN)₁₆(C₅H₆N₂)₄(H₂O)₂]·2H₂O
M_r = 1423.19
Triclinic, $[P \overline 1]$
a = 7.5953 (4) Å
b = 11.8232 (7) Å
c = 14.7017 (8) Å
α = 79.614 (1)°
β = 84.824 (2)°
γ = 73.090 (1)°
V = 1241.45 (12) Å³
Z = 1
Mo Kα radiation
μ = 5.94 mm⁻¹
T = 296 K
0.16 × 0.10 × 0.05 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.452, T_max = 0.772
12240 measured reflections
5666 independent reflections
5465 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.079
S = 1.24
5666 reflections
333 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 3.02 e Å⁻³
Δρ_min = −0.86 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N6ⁱ	0.92 (2)	1.86 (2)	2.771 (5)	167 (5)
O1—H2⋯O2	0.93 (2)	1.79 (2)	2.700 (4)	165 (4)
O2—H3⋯N12ⁱⁱ	0.95 (2)	2.00 (3)	2.914 (5)	161 (4)
O2—H4⋯N2ⁱⁱⁱ	0.93 (2)	2.02 (2)	2.944 (5)	169 (6)
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) x+1, y, z+1; (iii) -x+1, -y+2, -z+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: PyMOLWin (DeLano, 2007 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 979660

Crystal structure: contains datablocks I, shelxl. DOI: 10.1107/S1600536814000166/tk5281sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814000166/tk5281Isup2.hkl

checkCIF report

Experimental top

Synthesis and crystallization 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 CuCl₂·2H₂O (1.8 × 10 ^-2 mol dm^-3), 5-methylpyrimidine (2.4 × 10 ^-2 mol dm^-3) at room temperature. The prepared compound was a green plate-type crystal. Elemental analyses: calcd for Cu₃[W(CN)₈]₂(5-methylpyrimidine)₄·4H₂O, Calculated: Cu, 13.40; W, 25.83; C, 30.38; H, 2.27; N, 23.63%. Found: Cu, 13.12; W, 25.96; C, 30.05; H, 2.35; N, 23.64%. In the Infrared (IR) spectra, cyano stretching peaks were observed at 2204, 2194, 2169, 2161, 2148, and 2142 cm^-1.

Refinement top

The H atoms of the 5-methylpyrimidine molecules were placed in calculated positions with C—H = 0.95 Å, and refined using a riding model with U_iso(H) = 1.2 U_eq(C). The H atoms of water molecules were placed by using restraints of 0.96 (2) Å for O—H distances and DANG of 1.5 (4) Å for H—H distances. The maximum and minimum residual electron density peaks were located 0.74 and 1.60 Å, respectively, from the W1 and C3 atoms.

Results and discussion top

Synthesis of various kinds of three-dimensional network complexes exhibiting long-range magnetic ordering is an important issue. From this perspective, octacyanometalate [M(CN)₈] (M = Mo, W, Nb)-based magnets have been studied because they show high T_C (Garde et al., 1999; Zhong et al., 2000; Herrera et al., 2008; Sieklucka et al., 2009; Imoto et al., 2012) and functionalities such as photomagnetism (Herrera et al., 2004; Catala et al., 2005; Ohkoshi et al., 2011, 2012) and chemically sensitive magnetism (Ohkoshi et al., 2007). In addition, octacyanometalates have an advantage to construct various crystal structures due to the versatility that they 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). Several octacyanometalate-based magnets of Cu—W systems such as {[Cu₃[W(CN)₈]₂]·3.4H₂O}_n (Garde et al., 1999), {[Cu₃[W(CN)₈]₂(pyrimidine)₂]·8H₂O}_n (Ohkoshi et al., 2007), {[Cu₃[W(CN)₈]₂(pyrimidine)₄]·4H₂O}_n (Ohkoshi et al., 2012), {[(tetrenH₅)_0.8Cu₄[W(CN)₈]₄]·7.2H₂O}_n (Podgajny et al., 2002), have been reported. Here, we present a new candidate for copper-octacyanotungstate-based magnets, {[Cu₃[W(CN)₈]₂(5-methylpyrimidine)₄(H₂O)₂]·2H₂O}_n.

The asymmetric unit of the present compound consists of a [W(CN)₈]^3- anion, a one-half of [Cu1(5-methylpyrimidine)₂]²⁺ cation, a one-half of [Cu2(5-methylpyrimidine)₂]²⁺ cation, a one-half of [Cu3(H₂O)₂]²⁺ cation, and a water molecule (Fig. 1). The coordination geometry of W is an eight-coordinated bicapped trigonal prism, where five CN groups of [W(CN)₈] are bridged to Cu²⁺ ions (two Cu1, two Cu2 and one Cu3), and the other three CN groups are free. The coordination geometries of the three types of Cu²⁺ ions (Cu1, Cu2 and Cu3) are six-coordinated pseudo-octahedron. Cu1 is coordinated to four nitrogen atoms of CN ligands, two nitrogen atoms of 5-methylpyrimidine molecules. Cu2 is coordinated to four nitrogen atoms of CN ligands, two nitrogen atoms of 5-methylpyrimidine molecules. Cu3 is coordinated to two nitrogen atoms of CN ligands, two nitrogen atoms of 5-methylpyrimidine molecules, and two oxygen atoms of H₂O molecules. The cyano-bridged-Cu1—W—Cu2 layers are linked by Cu3 pillar unit (Figs. 2 and 3) and then, involving non-coordinated water molecules, the 3-D structure is constructed. In the crystal structure, the coordinated water make hydrogen bonds with the non-coordinated water (O1—H2···O2, 2.700 (4)) and the CN groups (O1—H1···N6, 2.771 (5)). Besides, hydrogen bonds between the non-coordinated water and the CN groups (O2—H4···N2, 2.944 (5)) or the 5-methylpyrimidine molecules (O2—H3···N12, 2.914 (5)).

The magnetization versus. temperature curve at 10 Oe showed a spontaneous magnetization with a Curie temperature (T_C) of 10 K, the coercive field (H_c) of 150 Oe at 2 K, and, the saturation magnetization (M_s) value of 3.1 µ_B. This M_s value agrees with the expected value of 3.0 µ_B, indicating that this compound is a ferrimagnet in which W^V (S = 1/2) and Cu^II (S = 1/2, Cu1 and Cu2) in the layer are ferromagnetically coupled and W^V and the bridged Cu^II (S = 1/2, Cu3) are antiferromagnetically coupled.

Related literature top

For background to functional three-dimensional networks, see: Catala et al. (2005); Garde et al. (1999); Herrera et al. (2004, 2008); Leipoldt et al. (1994); Ohkoshi & Tokoro (2012); Ohkoshi et al. (2012); Sieklucka et al. (2009); Zhong et al. (2000). For related structures, see: Ohkoshi et al. (2007, 2012); Podgajny et al. (2002).

Structure description top

Synthesis and crystallization top

Refinement details top

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: PyMOLWin (DeLano, 2007); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Displacement ellipsoid plot (30% probability level) of the atoms comprising the asymmetric unit of {[Cu₃[W(CN)₈]₂(C₅H₆N₂)₄(H₂O)₂]·2H₂O}_n. Symmetry codes: (i) +x,+y,+z and (ii) -x,-y,-z.
	Fig. 2. Crystal structure of {[Cu₃[W(CN)₈]₂(C₅H₆N₂)₄(H₂O)₂]·2H₂O}_n along the a axis. Blue, orange, gray, light blue, and red represent W, Cu, C, N, and O atoms, respectively. Hydrogen atoms are omitted for clarity.
	Fig. 3. Crystal structure of {[Cu₃[W(CN)₈]₂(C₅H₆N₂)₄(H₂O)₂]·2H₂O}_n along the b axis. Blue, orange, gray, light blue, and red represent W, Cu, C, N, and O atoms, respectively. Hydrogen atoms are omitted for clarity.

Poly[[diaquadeca-µ₂-cyanido-κ²⁰C:N-hexacyanido-κ⁶C-bis(µ₂-5-methylpyrimidine-κ²N:N')bis(5-methylpyrimidine-κN)tricopper(II)ditungstate(V)] dihydrate] top

Crystal data top

[Cu₃W₂(CN)₁₆(C₅H₆N₂)₄(H₂O)₂]·2H₂O	Z = 1
M_r = 1423.19	F(000) = 683
Triclinic, P1	D_x = 1.904 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 7.5953 (4) Å	Cell parameters from 10947 reflections
b = 11.8232 (7) Å	θ = 3.0–27.5°
c = 14.7017 (8) Å	µ = 5.94 mm⁻¹
α = 79.614 (1)°	T = 296 K
β = 84.824 (2)°	Platelet, green
γ = 73.090 (1)°	0.16 × 0.10 × 0.05 mm
V = 1241.45 (12) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	5666 independent reflections
Radiation source: fine-focus sealed tube	5465 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −9→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −15→14
T_min = 0.452, T_max = 0.772	l = −19→19
12240 measured reflections

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.24	w = 1/[σ²(F_o²) + (0.0422P)² + 0.3667P] where P = (F_o² + 2F_c²)/3
5666 reflections	(Δ/σ)_max = 0.003
333 parameters	Δρ_max = 3.02 e Å⁻³
6 restraints	Δρ_min = −0.86 e Å⁻³

Crystal data top

[Cu₃W₂(CN)₁₆(C₅H₆N₂)₄(H₂O)₂]·2H₂O	γ = 73.090 (1)°
M_r = 1423.19	V = 1241.45 (12) Å³
Triclinic, P1	Z = 1
a = 7.5953 (4) Å	Mo Kα radiation
b = 11.8232 (7) Å	µ = 5.94 mm⁻¹
c = 14.7017 (8) Å	T = 296 K
α = 79.614 (1)°	0.16 × 0.10 × 0.05 mm
β = 84.824 (2)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	5666 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	5465 reflections with I > 2σ(I)
T_min = 0.452, T_max = 0.772	R_int = 0.033
12240 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	6 restraints
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.24	Δρ_max = 3.02 e Å⁻³
5666 reflections	Δρ_min = −0.86 e Å⁻³
333 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
W1	0.548569 (15)	0.875339 (10)	0.768726 (8)	0.01497 (6)
Cu1	1.0000	1.0000	1.0000	0.01979 (14)
Cu2	0.0000	1.0000	0.5000	0.02293 (14)
Cu3	1.0000	0.5000	1.0000	0.02754 (15)
O1	0.9257 (4)	0.4659 (3)	1.12961 (19)	0.0325 (6)
O2	0.8939 (5)	0.6502 (3)	1.2207 (3)	0.0446 (8)
N1	0.2221 (4)	0.9864 (3)	0.9186 (2)	0.0253 (6)
N2	0.4282 (6)	1.1699 (3)	0.7155 (3)	0.0439 (10)
N3	0.2648 (5)	0.9438 (3)	0.5964 (3)	0.0352 (8)
N4	0.8430 (4)	0.9479 (3)	0.6057 (2)	0.0274 (7)
N5	0.7737 (7)	0.6301 (4)	0.6849 (4)	0.0615 (13)
N6	0.2689 (5)	0.7008 (4)	0.8104 (3)	0.0437 (9)
N7	0.6975 (5)	0.6771 (3)	0.9555 (3)	0.0376 (9)
N8	0.8384 (5)	0.9585 (3)	0.8789 (2)	0.0309 (7)
N9	1.1037 (4)	0.8172 (3)	1.0463 (2)	0.0222 (6)
N10	1.1143 (4)	0.6182 (3)	1.0366 (2)	0.0240 (6)
N11	0.0743 (4)	0.8306 (3)	0.4682 (2)	0.0271 (7)
N12	0.0945 (6)	0.6994 (4)	0.3619 (3)	0.0550 (12)
C1	0.3400 (5)	0.9497 (3)	0.8680 (2)	0.0219 (7)
C2	0.4714 (5)	1.0702 (4)	0.7326 (3)	0.0262 (8)
C3	0.3692 (5)	0.9207 (4)	0.6532 (3)	0.0272 (8)
C4	0.7413 (5)	0.9202 (3)	0.6609 (2)	0.0219 (7)
C5	0.6973 (6)	0.7146 (3)	0.7133 (3)	0.0323 (9)
C6	0.3645 (5)	0.7610 (3)	0.7957 (3)	0.0269 (8)
C7	0.6405 (5)	0.7462 (3)	0.8920 (3)	0.0260 (8)
C8	0.7391 (5)	0.9303 (3)	0.8395 (3)	0.0231 (7)
C9	1.0448 (5)	0.7368 (3)	1.0154 (3)	0.0227 (7)
H9	0.9472	0.7651	0.9758	0.027*
C10	1.2529 (5)	0.5779 (3)	1.0949 (3)	0.0281 (8)
H10	1.3036	0.4958	1.1111	0.034*
C11	1.3227 (5)	0.6550 (3)	1.1315 (3)	0.0286 (8)
C12	1.2427 (5)	0.7751 (4)	1.1046 (3)	0.0292 (8)
H12	1.2865	0.8296	1.1276	0.035*
C13	1.4754 (7)	0.6078 (4)	1.1980 (4)	0.0532 (14)
H13A	1.5110	0.5219	1.2077	0.064*
H13B	1.4340	0.6354	1.2558	0.064*
H13C	1.5790	0.6360	1.1730	0.064*
C14	0.0516 (6)	0.8084 (4)	0.3854 (3)	0.0413 (10)
H14	0.0022	0.8735	0.3403	0.050*
C15	0.1642 (7)	0.6077 (4)	0.4271 (4)	0.0501 (12)
H15	0.1950	0.5309	0.4125	0.060*
C16	0.1936 (7)	0.6203 (4)	0.5156 (4)	0.0423 (11)
C17	0.1426 (6)	0.7371 (4)	0.5327 (3)	0.0332 (9)
H17	0.1568	0.7507	0.5916	0.040*
C18	0.2772 (12)	0.5161 (6)	0.5890 (5)	0.083 (2)
H18A	0.2844	0.5452	0.6451	0.099*
H18B	0.3987	0.4749	0.5684	0.099*
H18C	0.2019	0.4620	0.6003	0.099*
H1	0.868 (7)	0.410 (3)	1.159 (3)	0.052 (15)*
H2	0.913 (6)	0.520 (3)	1.170 (3)	0.047 (14)*
H3	0.981 (5)	0.653 (5)	1.262 (3)	0.044 (14)*
H4	0.785 (4)	0.699 (5)	1.244 (4)	0.08 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
W1	0.01514 (9)	0.01469 (9)	0.01571 (9)	−0.00529 (6)	0.00316 (6)	−0.00411 (6)
Cu1	0.0179 (3)	0.0139 (3)	0.0246 (3)	−0.0026 (2)	0.0084 (2)	−0.0033 (2)
Cu2	0.0273 (3)	0.0226 (3)	0.0205 (3)	−0.0112 (3)	0.0107 (3)	−0.0063 (3)
Cu3	0.0403 (4)	0.0269 (3)	0.0249 (3)	−0.0228 (3)	0.0015 (3)	−0.0074 (3)
O1	0.0436 (16)	0.0348 (16)	0.0273 (14)	−0.0244 (14)	0.0064 (12)	−0.0076 (12)
O2	0.0377 (17)	0.056 (2)	0.0461 (19)	−0.0118 (16)	0.0010 (15)	−0.0275 (17)
N1	0.0222 (14)	0.0207 (15)	0.0297 (16)	−0.0032 (12)	0.0065 (13)	−0.0039 (13)
N2	0.052 (2)	0.0182 (18)	0.057 (3)	−0.0024 (17)	−0.003 (2)	−0.0084 (17)
N3	0.0321 (18)	0.042 (2)	0.0337 (19)	−0.0125 (16)	−0.0125 (15)	−0.0027 (16)
N4	0.0259 (15)	0.0313 (17)	0.0242 (15)	−0.0099 (14)	0.0073 (13)	−0.0038 (13)
N5	0.076 (3)	0.035 (2)	0.068 (3)	−0.006 (2)	0.019 (3)	−0.024 (2)
N6	0.048 (2)	0.043 (2)	0.052 (2)	−0.0315 (19)	0.0051 (18)	−0.0095 (18)
N7	0.050 (2)	0.0295 (19)	0.0361 (19)	−0.0172 (17)	−0.0145 (17)	0.0056 (16)
N8	0.0343 (17)	0.0225 (16)	0.0375 (18)	−0.0093 (14)	−0.0094 (15)	−0.0026 (14)
N9	0.0204 (14)	0.0214 (15)	0.0237 (15)	−0.0041 (12)	0.0020 (12)	−0.0058 (13)
N10	0.0310 (16)	0.0206 (15)	0.0244 (15)	−0.0138 (13)	0.0000 (13)	−0.0033 (12)
N11	0.0303 (16)	0.0279 (16)	0.0260 (16)	−0.0092 (14)	0.0038 (13)	−0.0122 (14)
N12	0.064 (3)	0.051 (3)	0.053 (3)	−0.003 (2)	−0.012 (2)	−0.031 (2)
C1	0.0194 (16)	0.0170 (16)	0.0269 (17)	−0.0041 (13)	0.0024 (14)	−0.0012 (14)
C2	0.0224 (18)	0.026 (2)	0.0273 (19)	−0.0029 (15)	0.0001 (15)	−0.0046 (16)
C3	0.0276 (18)	0.0292 (19)	0.0279 (18)	−0.0138 (16)	0.0020 (16)	−0.0045 (16)
C4	0.0210 (16)	0.0225 (17)	0.0212 (17)	−0.0045 (14)	0.0014 (14)	−0.0051 (14)
C5	0.040 (2)	0.0203 (18)	0.034 (2)	−0.0060 (17)	0.0104 (18)	−0.0099 (16)
C6	0.0270 (18)	0.0239 (18)	0.0299 (19)	−0.0087 (15)	0.0015 (15)	−0.0032 (15)
C7	0.0311 (19)	0.0220 (18)	0.0274 (19)	−0.0125 (16)	−0.0013 (16)	−0.0020 (16)
C8	0.0279 (17)	0.0190 (16)	0.0233 (17)	−0.0085 (14)	0.0001 (15)	−0.0030 (14)
C9	0.0266 (18)	0.0149 (16)	0.0270 (18)	−0.0075 (14)	−0.0051 (15)	0.0008 (14)
C10	0.0301 (18)	0.0183 (17)	0.037 (2)	−0.0066 (15)	−0.0039 (16)	−0.0065 (15)
C11	0.0229 (17)	0.0195 (17)	0.042 (2)	−0.0009 (15)	−0.0094 (16)	−0.0066 (16)
C12	0.0270 (18)	0.0244 (19)	0.041 (2)	−0.0109 (15)	−0.0042 (17)	−0.0110 (17)
C13	0.047 (3)	0.030 (2)	0.085 (4)	−0.001 (2)	−0.038 (3)	−0.014 (3)
C14	0.049 (3)	0.040 (2)	0.032 (2)	0.000 (2)	−0.008 (2)	−0.0137 (19)
C15	0.054 (3)	0.030 (2)	0.065 (3)	0.002 (2)	−0.006 (3)	−0.023 (2)
C16	0.047 (3)	0.027 (2)	0.050 (3)	−0.004 (2)	−0.001 (2)	−0.009 (2)
C17	0.042 (2)	0.033 (2)	0.028 (2)	−0.0157 (19)	0.0000 (18)	−0.0070 (18)
C18	0.120 (6)	0.043 (3)	0.070 (4)	−0.007 (4)	−0.010 (4)	0.006 (3)

Geometric parameters (Å, º) top

W1—C1	2.156 (3)	N4—C4	1.141 (5)
W1—C8	2.160 (4)	N4—Cu2ⁱⁱ	1.991 (3)
W1—C4	2.160 (4)	N5—C5	1.131 (5)
W1—C5	2.167 (4)	N6—C6	1.139 (5)
W1—C3	2.167 (4)	N7—C7	1.148 (5)
W1—C7	2.171 (4)	N8—C8	1.144 (5)
W1—C6	2.178 (4)	N9—C9	1.323 (5)
W1—C2	2.182 (4)	N9—C12	1.341 (5)
Cu1—N1ⁱ	1.962 (3)	N10—C9	1.335 (5)
Cu1—N1ⁱⁱ	1.962 (3)	N10—C10	1.338 (5)
Cu1—N9	2.081 (3)	N11—C14	1.328 (5)
Cu1—N9ⁱⁱⁱ	2.081 (3)	N11—C17	1.329 (6)
Cu1—N8ⁱⁱⁱ	2.444 (3)	N12—C15	1.326 (7)
Cu1—N8	2.444 (3)	N12—C14	1.334 (6)
Cu2—N4^iv	1.991 (3)	C9—H9	0.9300
Cu2—N4^v	1.991 (3)	C10—C11	1.383 (5)
Cu2—N11^vi	2.044 (3)	C10—H10	0.9300
Cu2—N11	2.044 (3)	C11—C12	1.372 (5)
Cu2—N3	2.427 (3)	C11—C13	1.497 (6)
Cu2—N3^vi	2.427 (3)	C12—H12	0.9300
Cu3—O1	1.943 (3)	C13—H13A	0.9600
Cu3—O1^vii	1.943 (3)	C13—H13B	0.9600
Cu3—N10^vii	2.015 (3)	C13—H13C	0.9600
Cu3—N10	2.015 (3)	C14—H14	0.9300
O1—H1	0.924 (19)	C15—C16	1.380 (7)
O1—H2	0.931 (19)	C15—H15	0.9300
O2—H3	0.950 (19)	C16—C17	1.385 (6)
O2—H4	0.933 (19)	C16—C18	1.508 (8)
N1—C1	1.146 (5)	C17—H17	0.9300
N1—Cu1^v	1.962 (3)	C18—H18A	0.9600
N2—C2	1.115 (6)	C18—H18B	0.9600
N3—C3	1.145 (5)	C18—H18C	0.9600

C1—W1—C8	86.95 (13)	N10^vii—Cu3—N10	179.999 (1)
C1—W1—C4	143.19 (14)	Cu3—O1—H1	129 (3)
C8—W1—C4	75.63 (14)	Cu3—O1—H2	122 (3)
C1—W1—C5	145.49 (14)	H1—O1—H2	106 (3)
C8—W1—C5	108.53 (15)	H3—O2—H4	102 (3)
C4—W1—C5	71.32 (15)	C1—N1—Cu1^v	160.6 (3)
C1—W1—C3	96.29 (14)	C3—N3—Cu2	169.1 (3)
C8—W1—C3	145.84 (14)	C4—N4—Cu2ⁱⁱ	174.1 (3)
C4—W1—C3	81.95 (14)	C8—N8—Cu1	164.1 (3)
C5—W1—C3	87.73 (16)	C9—N9—C12	116.7 (3)
C1—W1—C7	80.17 (14)	C9—N9—Cu1	121.9 (3)
C8—W1—C7	69.75 (14)	C12—N9—Cu1	121.2 (3)
C4—W1—C7	121.55 (14)	C9—N10—C10	117.1 (3)
C5—W1—C7	76.96 (15)	C9—N10—Cu3	123.4 (2)
C3—W1—C7	144.35 (14)	C10—N10—Cu3	118.9 (2)
C1—W1—C6	73.46 (14)	C14—N11—C17	117.4 (4)
C8—W1—C6	140.10 (14)	C14—N11—Cu2	122.6 (3)
C4—W1—C6	138.18 (14)	C17—N11—Cu2	120.0 (3)
C5—W1—C6	75.27 (15)	C15—N12—C14	116.6 (4)
C3—W1—C6	72.22 (14)	N1—C1—W1	175.9 (3)
C7—W1—C6	72.80 (14)	N2—C2—W1	178.3 (5)
C1—W1—C2	71.57 (14)	N3—C3—W1	175.3 (3)
C8—W1—C2	75.22 (14)	N4—C4—W1	177.1 (4)
C4—W1—C2	72.72 (14)	N5—C5—W1	179.3 (4)
C5—W1—C2	141.37 (15)	N6—C6—W1	179.6 (4)
C3—W1—C2	73.68 (15)	N7—C7—W1	176.8 (4)
C7—W1—C2	135.68 (15)	N8—C8—W1	178.4 (3)
C6—W1—C2	127.18 (14)	N9—C9—N10	125.2 (3)
N1ⁱ—Cu1—N1ⁱⁱ	179.999 (1)	N9—C9—H9	117.4
N1ⁱ—Cu1—N9	93.24 (12)	N10—C9—H9	117.4
N1ⁱⁱ—Cu1—N9	86.76 (12)	N10—C10—C11	121.9 (3)
N1ⁱ—Cu1—N9ⁱⁱⁱ	86.76 (12)	N10—C10—H10	119.1
N1ⁱⁱ—Cu1—N9ⁱⁱⁱ	93.24 (12)	C11—C10—H10	119.1
N9—Cu1—N9ⁱⁱⁱ	179.998 (1)	C12—C11—C10	116.3 (3)
N1ⁱ—Cu1—N8ⁱⁱⁱ	90.31 (13)	C12—C11—C13	122.8 (4)
N1ⁱⁱ—Cu1—N8ⁱⁱⁱ	89.69 (13)	C10—C11—C13	120.9 (4)
N9—Cu1—N8ⁱⁱⁱ	89.69 (12)	N9—C12—C11	122.7 (3)
N9ⁱⁱⁱ—Cu1—N8ⁱⁱⁱ	90.31 (12)	N9—C12—H12	118.6
N1ⁱ—Cu1—N8	89.69 (13)	C11—C12—H12	118.6
N1ⁱⁱ—Cu1—N8	90.31 (13)	C11—C13—H13A	109.5
N9—Cu1—N8	90.31 (12)	C11—C13—H13B	109.5
N9ⁱⁱⁱ—Cu1—N8	89.69 (12)	H13A—C13—H13B	109.5
N8ⁱⁱⁱ—Cu1—N8	180.000 (1)	C11—C13—H13C	109.5
N4^iv—Cu2—N4^v	179.998 (1)	H13A—C13—H13C	109.5
N4^iv—Cu2—N11^vi	89.30 (13)	H13B—C13—H13C	109.5
N4^v—Cu2—N11^vi	90.70 (13)	N11—C14—N12	124.8 (5)
N4^iv—Cu2—N11	90.70 (13)	N11—C14—H14	117.6
N4^v—Cu2—N11	89.30 (13)	N12—C14—H14	117.6
N11^vi—Cu2—N11	179.999 (1)	N12—C15—C16	123.5 (4)
N4^iv—Cu2—N3	88.44 (13)	N12—C15—H15	118.3
N4^v—Cu2—N3	91.56 (13)	C16—C15—H15	118.3
N11^vi—Cu2—N3	90.62 (13)	C15—C16—C17	115.1 (4)
N11—Cu2—N3	89.38 (13)	C15—C16—C18	123.5 (5)
N4^iv—Cu2—N3^vi	91.56 (13)	C17—C16—C18	121.5 (5)
N4^v—Cu2—N3^vi	88.44 (13)	N11—C17—C16	122.6 (4)
N11^vi—Cu2—N3^vi	89.38 (13)	N11—C17—H17	118.7
N11—Cu2—N3^vi	90.62 (13)	C16—C17—H17	118.7
N3—Cu2—N3^vi	180.0	C16—C18—H18A	109.5
O1—Cu3—O1^vii	180.00 (17)	C16—C18—H18B	109.5
O1—Cu3—N10^vii	92.98 (12)	H18A—C18—H18B	109.5
O1^vii—Cu3—N10^vii	87.01 (12)	C16—C18—H18C	109.5
O1—Cu3—N10	87.02 (12)	H18A—C18—H18C	109.5
O1^vii—Cu3—N10	92.98 (12)	H18B—C18—H18C	109.5

N4^iv—Cu2—N3—C3	153.2 (18)	Cu2ⁱⁱ—N4—C4—W1	−113 (6)
N4^v—Cu2—N3—C3	−26.8 (18)	C1—W1—C4—N4	24 (7)
N11^vi—Cu2—N3—C3	63.9 (18)	C8—W1—C4—N4	−40 (7)
N11—Cu2—N3—C3	−116.1 (18)	C5—W1—C4—N4	−156 (7)
N3^vi—Cu2—N3—C3	−35 (58)	C3—W1—C4—N4	114 (7)
N1ⁱ—Cu1—N8—C8	−24.6 (11)	C7—W1—C4—N4	−95 (7)
N1ⁱⁱ—Cu1—N8—C8	155.4 (11)	C6—W1—C4—N4	165 (7)
N9—Cu1—N8—C8	68.6 (11)	C2—W1—C4—N4	38 (7)
N9ⁱⁱⁱ—Cu1—N8—C8	−111.4 (11)	C1—W1—C5—N5	13 (39)
N8ⁱⁱⁱ—Cu1—N8—C8	−67 (100)	C8—W1—C5—N5	126 (39)
N1ⁱ—Cu1—N9—C9	79.9 (3)	C4—W1—C5—N5	−167 (100)
N1ⁱⁱ—Cu1—N9—C9	−100.1 (3)	C3—W1—C5—N5	−84 (39)
N9ⁱⁱⁱ—Cu1—N9—C9	178 (28)	C7—W1—C5—N5	63 (39)
N8ⁱⁱⁱ—Cu1—N9—C9	170.2 (3)	C6—W1—C5—N5	−12 (39)
N8—Cu1—N9—C9	−9.8 (3)	C2—W1—C5—N5	−144 (39)
N1ⁱ—Cu1—N9—C12	−104.5 (3)	C1—W1—C6—N6	−81 (62)
N1ⁱⁱ—Cu1—N9—C12	75.5 (3)	C8—W1—C6—N6	−17 (62)
N9ⁱⁱⁱ—Cu1—N9—C12	−7 (28)	C4—W1—C6—N6	122 (62)
N8ⁱⁱⁱ—Cu1—N9—C12	−14.2 (3)	C5—W1—C6—N6	85 (62)
N8—Cu1—N9—C12	165.8 (3)	C3—W1—C6—N6	177 (100)
O1—Cu3—N10—C9	−108.2 (3)	C7—W1—C6—N6	4 (62)
O1^vii—Cu3—N10—C9	71.8 (3)	C2—W1—C6—N6	−131 (62)
N10^vii—Cu3—N10—C9	56 (80)	C1—W1—C7—N7	−151 (6)
O1—Cu3—N10—C10	63.1 (3)	C8—W1—C7—N7	−60 (6)
O1^vii—Cu3—N10—C10	−116.9 (3)	C4—W1—C7—N7	−3 (6)
N10^vii—Cu3—N10—C10	−133 (80)	C5—W1—C7—N7	55 (6)
N4^iv—Cu2—N11—C14	−55.8 (4)	C3—W1—C7—N7	122 (6)
N4^v—Cu2—N11—C14	124.2 (4)	C6—W1—C7—N7	134 (6)
N11^vi—Cu2—N11—C14	−19 (27)	C2—W1—C7—N7	−100 (6)
N3—Cu2—N11—C14	−144.2 (4)	Cu1—N8—C8—W1	−6 (14)
N3^vi—Cu2—N11—C14	35.8 (4)	C1—W1—C8—N8	44 (13)
N4^iv—Cu2—N11—C17	126.5 (3)	C4—W1—C8—N8	−168 (13)
N4^v—Cu2—N11—C17	−53.5 (3)	C5—W1—C8—N8	−104 (13)
N11^vi—Cu2—N11—C17	164 (27)	C3—W1—C8—N8	141 (12)
N3—Cu2—N11—C17	38.1 (3)	C7—W1—C8—N8	−36 (13)
N3^vi—Cu2—N11—C17	−141.9 (3)	C6—W1—C8—N8	−15 (13)
Cu1^v—N1—C1—W1	31 (5)	C2—W1—C8—N8	116 (13)
C8—W1—C1—N1	−173 (4)	C12—N9—C9—N10	−1.0 (6)
C4—W1—C1—N1	126 (4)	Cu1—N9—C9—N10	174.7 (3)
C5—W1—C1—N1	−54 (4)	C10—N10—C9—N9	1.0 (6)
C3—W1—C1—N1	41 (4)	Cu3—N10—C9—N9	172.4 (3)
C7—W1—C1—N1	−103 (4)	C9—N10—C10—C11	−0.3 (6)
C6—W1—C1—N1	−28 (4)	Cu3—N10—C10—C11	−172.1 (3)
C2—W1—C1—N1	112 (4)	N10—C10—C11—C12	−0.3 (6)
C1—W1—C2—N2	−17 (16)	N10—C10—C11—C13	178.8 (4)
C8—W1—C2—N2	−109 (16)	C9—N9—C12—C11	0.3 (6)
C4—W1—C2—N2	172 (16)	Cu1—N9—C12—C11	−175.4 (3)
C5—W1—C2—N2	150 (16)	C10—C11—C12—N9	0.3 (6)
C3—W1—C2—N2	85 (16)	C13—C11—C12—N9	−178.8 (4)
C7—W1—C2—N2	−70 (16)	C17—N11—C14—N12	−0.9 (7)
C6—W1—C2—N2	34 (16)	Cu2—N11—C14—N12	−178.6 (4)
Cu2—N3—C3—W1	17 (6)	C15—N12—C14—N11	0.2 (8)
C1—W1—C3—N3	−30 (4)	C14—N12—C15—C16	−0.1 (8)
C8—W1—C3—N3	−124 (4)	N12—C15—C16—C17	0.7 (8)
C4—W1—C3—N3	−173 (4)	N12—C15—C16—C18	−178.4 (6)
C5—W1—C3—N3	116 (4)	C14—N11—C17—C16	1.5 (7)
C7—W1—C3—N3	52 (5)	Cu2—N11—C17—C16	179.3 (4)
C6—W1—C3—N3	40 (4)	C15—C16—C17—N11	−1.4 (7)
C2—W1—C3—N3	−99 (4)	C18—C16—C17—N11	177.7 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N6^viii	0.92 (2)	1.86 (2)	2.771 (5)	167 (5)
O1—H2···O2	0.93 (2)	1.79 (2)	2.700 (4)	165 (4)
O2—H3···N12^ix	0.95 (2)	2.00 (3)	2.914 (5)	161 (4)
O2—H4···N2ⁱ	0.93 (2)	2.02 (2)	2.944 (5)	169 (6)

Symmetry codes: (i) −x+1, −y+2, −z+2; (viii) −x+1, −y+1, −z+2; (ix) x+1, y, z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N6ⁱ	0.924 (19)	1.86 (2)	2.771 (5)	167 (5)
O1—H2···O2	0.931 (19)	1.79 (2)	2.700 (4)	165 (4)
O2—H3···N12ⁱⁱ	0.950 (19)	2.00 (3)	2.914 (5)	161 (4)
O2—H4···N2ⁱⁱⁱ	0.933 (19)	2.02 (2)	2.944 (5)	169 (6)

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

Acknowledgements

The present research was supported partly by the Core Research for Evolutional Science and Technology (CREST) program of the Japan Science and Technology Agency (JST), the Asahi Glass Foundation, the Advanced Photon Science Alliance (APSA) from the Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT), the Cryogenic Research Center, The University of Tokyo, and the Center for Nano Lithography & Analysis, The University of Tokyo, supported by MEXT. YT is grateful for a JSPS Research Fellowship for Young Scientists.

References

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Volume 70| Part 2| February 2014| Pages m47-m48

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