Poly[[di-aqua-deca-μ2-cyanido-κ(20) C:N-hexa-cyanido-κ(6) C-bis-(μ2-5-methyl-pyrimidine-κ(2) N:N')bis-(5-methyl-pyrimidine-κN)tricopper(II)ditungstate(V)] dihydrate].

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 mol-ecules and 5-methyl-pyrimidine mol-ecules. O-H⋯O and O-H⋯N hydrogen bonds involve the coordinating and non-coordin-ating water mol-ecules, the CN groups and the 5-methyl-pyrimidine mol-ecules.

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 = 1423.19

Triclinic,

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[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.079

S = 1.24

5666 reflections

333 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 3.02 e Å−3

Δρmin = −0.86 e Å−3

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 ▶).

Crystal structure: contains datablock(s) I, shelxl. DOI: 10.1107/S1600536814000166/tk5281sup1.cif

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

CCDC reference:

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Cu3W2(CN)16(C5H6N2)4(H2O)2]·2H2O	Z = 1
Mr = 1423.19	F(000) = 683
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.0422P)2 + 0.3667P] where P = (Fo2 + 2Fc2)/3
5666 reflections	(Δ/σ)max = 0.003
333 parameters	Δρmax = 3.02 e Å−3
6 restraints	Δρmin = −0.86 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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—N4iv	1.991 (3)	C9—H9	0.9300
Cu2—N4v	1.991 (3)	C10—C11	1.383 (5)
Cu2—N11vi	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—N3vi	2.427 (3)	C12—H12	0.9300
Cu3—O1	1.943 (3)	C13—H13A	0.9600
Cu3—O1vii	1.943 (3)	C13—H13B	0.9600
Cu3—N10vii	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—Cu1v	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)	N10vii—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—Cu1v	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
N4iv—Cu2—N4v	179.998 (1)	H13A—C13—H13C	109.5
N4iv—Cu2—N11vi	89.30 (13)	H13B—C13—H13C	109.5
N4v—Cu2—N11vi	90.70 (13)	N11—C14—N12	124.8 (5)
N4iv—Cu2—N11	90.70 (13)	N11—C14—H14	117.6
N4v—Cu2—N11	89.30 (13)	N12—C14—H14	117.6
N11vi—Cu2—N11	179.999 (1)	N12—C15—C16	123.5 (4)
N4iv—Cu2—N3	88.44 (13)	N12—C15—H15	118.3
N4v—Cu2—N3	91.56 (13)	C16—C15—H15	118.3
N11vi—Cu2—N3	90.62 (13)	C15—C16—C17	115.1 (4)
N11—Cu2—N3	89.38 (13)	C15—C16—C18	123.5 (5)
N4iv—Cu2—N3vi	91.56 (13)	C17—C16—C18	121.5 (5)
N4v—Cu2—N3vi	88.44 (13)	N11—C17—C16	122.6 (4)
N11vi—Cu2—N3vi	89.38 (13)	N11—C17—H17	118.7
N11—Cu2—N3vi	90.62 (13)	C16—C17—H17	118.7
N3—Cu2—N3vi	180.0	C16—C18—H18A	109.5
O1—Cu3—O1vii	180.00 (17)	C16—C18—H18B	109.5
O1—Cu3—N10vii	92.98 (12)	H18A—C18—H18B	109.5
O1vii—Cu3—N10vii	87.01 (12)	C16—C18—H18C	109.5
O1—Cu3—N10	87.02 (12)	H18A—C18—H18C	109.5
O1vii—Cu3—N10	92.98 (12)	H18B—C18—H18C	109.5
N4iv—Cu2—N3—C3	153.2 (18)	Cu2ii—N4—C4—W1	−113 (6)
N4v—Cu2—N3—C3	−26.8 (18)	C1—W1—C4—N4	24 (7)
N11vi—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)
N3vi—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)
O1vii—Cu3—N10—C9	71.8 (3)	C2—W1—C6—N6	−131 (62)
N10vii—Cu3—N10—C9	56 (80)	C1—W1—C7—N7	−151 (6)
O1—Cu3—N10—C10	63.1 (3)	C8—W1—C7—N7	−60 (6)
O1vii—Cu3—N10—C10	−116.9 (3)	C4—W1—C7—N7	−3 (6)
N10vii—Cu3—N10—C10	−133 (80)	C5—W1—C7—N7	55 (6)
N4iv—Cu2—N11—C14	−55.8 (4)	C3—W1—C7—N7	122 (6)
N4v—Cu2—N11—C14	124.2 (4)	C6—W1—C7—N7	134 (6)
N11vi—Cu2—N11—C14	−19 (27)	C2—W1—C7—N7	−100 (6)
N3—Cu2—N11—C14	−144.2 (4)	Cu1—N8—C8—W1	−6 (14)
N3vi—Cu2—N11—C14	35.8 (4)	C1—W1—C8—N8	44 (13)
N4iv—Cu2—N11—C17	126.5 (3)	C4—W1—C8—N8	−168 (13)
N4v—Cu2—N11—C17	−53.5 (3)	C5—W1—C8—N8	−104 (13)
N11vi—Cu2—N11—C17	164 (27)	C3—W1—C8—N8	141 (12)
N3—Cu2—N11—C17	38.1 (3)	C7—W1—C8—N8	−36 (13)
N3vi—Cu2—N11—C17	−141.9 (3)	C6—W1—C8—N8	−15 (13)
Cu1v—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)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N6viii	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···N12ix	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)

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) ; (ii) ; (iii) .