Tris{aqua­bis[3-(2-pyrid­yl)-1H-pyrazole]copper(II)} di-μ9-arsenato-hexa­triaconta-μ2-oxido-octa­deca­oxidoocta­deca­molybdate(VI)

Zhang, X.; Wei, P.; Shi, C.; Li, B.; Hu, B.

doi:10.1107/S160053681000156X

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Pages m174-m175

https://doi.org/10.1107/S160053681000156X

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Tris{aquabis[3-(2-pyridyl)-1H-pyrazole]copper(II)} di-μ₉-arsenato-hexatriaconta-μ₂-oxido-octadecaoxidooctadecamolybdate(VI)

Xiutang Zhang,^a,^b ^* Peihai Wei,^a Congwen Shi,^a Bin Li ^a and Bo Hu ^a

^aAdvanced Material Institute of Research, Department of Chemistry and Chemical Engineering, ShanDong Institute of Education, Jinan 250013, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, People's Republic of China
^*Correspondence e-mail: xiutangzhang@yahoo.com.cn

(Received 9 December 2009; accepted 13 January 2010; online 16 January 2010)

The title compound, [Cu(C₈H₇N₃)₂(H₂O)]₃[As₂Mo₁₈O₆₂], consists of two subunits, viz. an α-Dawson-type [As₂Mo₁₈O₆₂]⁶⁻ anion and a complex [Cu(C₈H₇N₃)₂(H₂O)]²⁺ cation. The copper(II) ion (site symmetry .2) is pentacoordinated in a distorted square-pyramidal manner by four N atoms from two chelating 3-(2-pyridyl)pyrazole ligands in equatorial positions and one water molecule in the apical position. In the heteropolyanion, two O atoms of the AsO₄ group (3. symmetry) are equally disordered about the threefold rotation axis. N—H⋯O and O—H⋯O hydrogen bonding between the neutral molecules and the water molecules leads to a consolidation of the structure.

Related literature

For background to polyoxometalates, see: Pope & Müller (1991 ). For polyoxometalates modified with amines, see: Zhang, Dou et al. (2009 ); Zhang, Wei, Shi et al. (2010 ); Zhang, Wei et al. (2009 ); Zhang, Yuan et al. (2010 ). Zhang, Wei, Zhu et al. (2010 ). For another α-Dawson-type anion, see: Li et al. (2007 ).

Experimental

Crystal data

[Cu(C₈H₇N₃)₂(H₂O)]₃[As₂Mo₁₈O₆₂]
M_r = 3984.45
Hexagonal, $[R \overline 3c ]$
a = 21.967 (3) Å
c = 34.411 (7) Å
V = 14380 (4) Å³
Z = 6
Mo Kα radiation
μ = 3.72 mm⁻¹
T = 293 K
0.12 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.664, T_max = 0.755
25458 measured reflections
2750 independent reflections
2053 reflections with I > 2σ(I)
R_int = 0.085

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.123
S = 1.00
2750 reflections
254 parameters
14 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 2.25 e Å⁻³
Δρ_min = −1.15 e Å⁻³

Table 1
Selected bond lengths (Å)

As1—O10A	1.653 (10)
As1—O10B	1.677 (10)
As1—O1	1.728 (9)
Cu1—N3	1.984 (7)
Cu1—N1	1.985 (8)
Cu1—O11	2.29 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O6ⁱ	0.86	2.27	3.097 (13)	162
O11—H1W⋯O3ⁱⁱ	0.84 (8)	2.69 (11)	2.860 (10)	94 (8)
Symmetry codes: (i) $[x+{\script{1\over 3}}, x-y+{\script{2\over 3}}, z+{\script{1\over 6}}]$ ; (ii) $[y, x, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053681000156X/wm2290sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681000156X/wm2290Isup2.hkl

checkCIF report

Comment top

The design and synthesis of polyoxometalates has attracted continuous research interest not only because of their appealing structural and topological novelties, but also due to their interesting optical, electronic, magnetic, and catalytic properties, as well as their potential medical applications (Pope et al., 1991). In our group, organic amines, such as 3-(2-pyridyl)pyrazole and pyrazine, are used to effectively modify polyoxomolybdates under hydrothermal condictions (Zhang, Dou et al., 2009; Zhang, Wei et al., 2009). Here, we describe the synthesis and structural characterization of the title compound.

As shown in Figure 1, the title compound consists of two subunits, viz. of an α-Dawson-type [As₂Mo₁₈O₆₂]^6- anion (Li et al., 2007) and a complex [Cu(H₂O)(C₈H₇N₃)₂]²⁺ cation. The copper ion is penta-coordinated in a distorted square-pyramidal geometry by four N atoms from two 3-(2-pyridyl)pyrazole ligands and by one water molecule. The Cu—N bond lengths are in the range of 1.984 (7)—1.985 (8) Å and the Cu—O bond length is 2.29 (2) Å. In the heteropolyanion, there are four kinds of oxygen atoms according to their coordination manner: (i) 18 terminal O atoms bonded to one Mo atom with their Mo—O distances in the range of 1.651 (6)—1.690 (6) Å; (ii) 36 µ₂ O atoms, the Mo—O distances in the range of 1.797 (5)—2.117 (5) Å; (iii) six µ₃ O atoms shared by one As and two Mo atoms, the Mo—O distances varying from 1.653 (8) to 2.359 (1) Å; (iv) two µ₄ O atoms which are coordinated to one As atom and three Mo atoms, Mo—O distances are between 1.728 (7) and 2.341 (7) Å, respectively. The resulting MoO₆ octahedra are considerably distorted. The AsO₄ group is disordered about a threefold rotation axis and exhibuts two sets of short As—O bond lenghts to the disordered O atoms (50% occupation) and one longer As—O bond. N—H···O and O—H···O hydrogen bonding between the neutral molecules and the water molecules leads to a consolidation of the structure (Fig. 2; Table 2) which also contains accessible voids of ca. 136 Å³.

Related literature top

For background to polyoxometalates, see: Pope & Müller (1991). For polyoxometalates modified with amines, see: Zhang, Dou et al. (2009); Zhang, Wei, Shi et al. (2010); Zhang, Wei et al. (2009); Zhang, Yuan et al. (2010). Zhang, Wei, Zhu et al. (2010). For another α-Dawson-type anion, see: Li et al. (2007).

Experimental top

A mixture of 3-(2-pyridyl)pyrazole (1 mmoL 0.14 g), sodium molybdate (2 mmoL, 0.48 g), sodium arsenate (0.2 mmoL, 0.08 g) and copper dichloride dihydrate (1 mmoL, 0.28 g) in 14 ml distilled water was sealed in a 25 ml Teflon-lined stainless steel autoclave and was kept at 433 K for three days. Blue crystals suitable for the X-ray experiment were obtained. Anal. Calc. for C₄₈H₄₈As₂Cu₃Mo₁₈N₁₈O₆₅: C 14.46, H 1.20, N 6.32%; Found: C 14.24, H 1.01, N 6.23%.

Structure description top

For background to polyoxometalates, see: Pope & Müller (1991). For polyoxometalates modified with amines, see: Zhang, Dou et al. (2009); Zhang, Wei, Shi et al. (2010); Zhang, Wei et al. (2009); Zhang, Yuan et al. (2010). Zhang, Wei, Zhu et al. (2010). For another α-Dawson-type anion, see: Li et al. (2007).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The cation and anion of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level; H atoms are given as spheres of arbitrary radius.
	Fig. 2. The crystal packing of the title compound, displayed with hydrogen bonds as dashed lines.

Tris{aquabis[3-(2-pyridyl)-1H-pyrazole]copper(II)} di-µ₉-arsenato-hexatriaconta-µ₂-oxido-octadecaoxidooctadecamolybdate(VI) top

Crystal data top

[Cu(C₈H₇N₃)₂(H₂O)]₃[As₂Mo₁₈O₆₂]	D_x = 2.761 Mg m⁻³
M_r = 3984.45	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, R3c	Cell parameters from 2750 reflections
Hall symbol: -R 3 2"c	θ = 1.6–25.0°
a = 21.967 (3) Å	µ = 3.72 mm⁻¹
c = 34.411 (7) Å	T = 293 K
V = 14380 (4) Å³	Block, blue
Z = 6	0.12 × 0.10 × 0.08 mm
F(000) = 11346

Data collection top

Bruker APEXII CCD diffractometer	2750 independent reflections
Radiation source: fine-focus sealed tube	2053 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.085
phi and ω scans	θ_max = 25.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −25→26
T_min = 0.664, T_max = 0.755	k = −26→26
25458 measured reflections	l = −40→39

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.063P)² + 278.6957P] where P = (F_o² + 2F_c²)/3
2750 reflections	(Δ/σ)_max = 0.001
254 parameters	Δρ_max = 2.25 e Å⁻³
14 restraints	Δρ_min = −1.15 e Å⁻³

Crystal data top

[Cu(C₈H₇N₃)₂(H₂O)]₃[As₂Mo₁₈O₆₂]	Z = 6
M_r = 3984.45	Mo Kα radiation
Hexagonal, R3c	µ = 3.72 mm⁻¹
a = 21.967 (3) Å	T = 293 K
c = 34.411 (7) Å	0.12 × 0.10 × 0.08 mm
V = 14380 (4) Å³

Data collection top

Bruker APEXII CCD diffractometer	2750 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2053 reflections with I > 2σ(I)
T_min = 0.664, T_max = 0.755	R_int = 0.085
25458 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	14 restraints
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.063P)² + 278.6957P] where P = (F_o² + 2F_c²)/3
2750 reflections	Δρ_max = 2.25 e Å⁻³
254 parameters	Δρ_min = −1.15 e Å⁻³

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	Occ. (<1)
As1	0.0000	0.0000	0.05884 (4)	0.0161 (3)
C1	0.2641 (5)	0.2974 (5)	0.1696 (3)	0.039 (2)
C2	0.1872 (5)	0.3163 (5)	0.2056 (3)	0.042 (2)
H2	0.1698	0.3199	0.2296	0.050*
C3	0.1552 (7)	0.3216 (5)	0.1730 (3)	0.055 (3)
H3	0.1192	0.3321	0.1747	0.066*
C4	0.1768 (7)	0.3112 (5)	0.1380 (3)	0.055 (3)
H4	0.1534	0.3113	0.1155	0.065*
C5	0.2326 (6)	0.3008 (5)	0.1359 (3)	0.042 (3)
H5	0.2493	0.2960	0.1119	0.050*
C6	0.2831 (5)	0.3216 (5)	0.3283 (2)	0.037 (2)
C7	0.2761 (7)	0.3645 (7)	0.3554 (4)	0.066 (3)
H7	0.2809	0.3636	0.3822	0.079*
C8	0.2605 (7)	0.4092 (6)	0.3343 (3)	0.067 (4)
H8	0.2523	0.4438	0.3442	0.080*
Cu1	0.28491 (9)	0.28491 (9)	0.2500	0.0444 (5)
Mo1	0.06070 (4)	0.10373 (4)	0.14523 (2)	0.0293 (2)
Mo2	0.03113 (4)	0.17477 (4)	0.05152 (2)	0.0270 (2)
Mo3	0.17292 (4)	0.14366 (4)	0.05871 (2)	0.0298 (2)
N1	0.2731 (5)	0.3393 (5)	0.2924 (2)	0.045 (2)
N2	0.2599 (5)	0.3921 (5)	0.2969 (3)	0.057 (3)
H2A	0.2518	0.4126	0.2779	0.068*
N3	0.2426 (4)	0.3063 (4)	0.2048 (2)	0.0381 (19)
O1	0.0000	0.0000	0.1090 (3)	0.023 (2)
O2	−0.0297 (3)	0.0513 (3)	0.16857 (15)	0.0250 (12)
O3	0.1016 (3)	0.1636 (3)	0.18082 (17)	0.0336 (15)
O4	0.0331 (3)	0.1452 (3)	0.10985 (16)	0.0261 (13)
O5	0.1395 (3)	0.1213 (3)	0.11134 (16)	0.0271 (13)
O6	−0.0665 (5)	0.1212 (5)	0.0577 (3)	0.075 (2)
O7	0.0438 (3)	0.2531 (3)	0.06422 (17)	0.0344 (15)
O8	0.2534 (3)	0.2085 (3)	0.06733 (18)	0.0412 (17)
O9	0.0315 (4)	0.1816 (3)	−0.00079 (17)	0.0445 (18)
O10A	−0.0288 (5)	0.0530 (5)	0.0445 (3)	0.019 (2)	0.50
O10B	−0.0832 (5)	−0.0297 (5)	0.0446 (3)	0.016 (2)	0.50
O11	0.1808 (10)	0.1808 (10)	0.2500	0.142 (2)
O12A	0.1344 (7)	0.2076 (7)	0.0591 (4)	0.030 (3)	0.50
O12B	0.1111 (7)	0.1708 (8)	0.0481 (4)	0.027 (3)	0.50
H1W	0.1487 (19)	0.179 (2)	0.264 (3)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
As1	0.0173 (4)	0.0173 (4)	0.0136 (7)	0.0086 (2)	0.000	0.000
C1	0.043 (6)	0.025 (5)	0.034 (6)	0.005 (4)	−0.004 (4)	0.000 (4)
C2	0.058 (7)	0.042 (6)	0.032 (6)	0.030 (5)	−0.006 (5)	−0.003 (4)
C3	0.081 (9)	0.041 (6)	0.051 (7)	0.038 (6)	−0.015 (6)	−0.005 (5)
C4	0.082 (9)	0.030 (6)	0.055 (8)	0.031 (6)	−0.018 (6)	−0.004 (5)
C5	0.063 (7)	0.032 (5)	0.020 (5)	0.016 (5)	−0.011 (4)	−0.002 (4)
C6	0.045 (6)	0.044 (6)	0.018 (5)	0.019 (5)	0.004 (4)	0.000 (4)
C7	0.076 (9)	0.065 (8)	0.042 (7)	0.025 (7)	0.010 (6)	0.006 (6)
C8	0.099 (10)	0.058 (8)	0.040 (7)	0.036 (7)	0.021 (7)	−0.002 (6)
Cu1	0.0590 (9)	0.0590 (9)	0.0215 (9)	0.0344 (10)	−0.0019 (4)	0.0019 (4)
Mo1	0.0391 (5)	0.0246 (4)	0.0214 (4)	0.0139 (4)	−0.0087 (3)	−0.0058 (3)
Mo2	0.0362 (5)	0.0200 (4)	0.0270 (4)	0.0156 (3)	0.0013 (3)	0.0008 (3)
Mo3	0.0201 (4)	0.0244 (4)	0.0388 (5)	0.0067 (3)	−0.0063 (3)	−0.0045 (3)
N1	0.065 (6)	0.048 (5)	0.022 (4)	0.028 (5)	0.000 (4)	−0.001 (4)
N2	0.086 (7)	0.041 (5)	0.044 (6)	0.033 (5)	0.007 (5)	0.016 (4)
N3	0.048 (5)	0.028 (4)	0.025 (4)	0.009 (4)	−0.007 (4)	0.003 (3)
O1	0.027 (3)	0.027 (3)	0.016 (5)	0.0133 (16)	0.000	0.000
O2	0.028 (3)	0.029 (3)	0.016 (3)	0.013 (3)	0.003 (2)	−0.001 (2)
O3	0.044 (4)	0.028 (3)	0.023 (3)	0.013 (3)	−0.008 (3)	−0.006 (3)
O4	0.028 (3)	0.027 (3)	0.025 (3)	0.015 (3)	0.006 (2)	0.005 (2)
O5	0.030 (3)	0.030 (3)	0.024 (3)	0.017 (3)	0.001 (2)	0.001 (2)
O6	0.074 (3)	0.075 (3)	0.073 (3)	0.0349 (15)	−0.0029 (10)	0.0033 (10)
O7	0.048 (4)	0.025 (3)	0.030 (3)	0.018 (3)	0.001 (3)	−0.001 (3)
O8	0.024 (3)	0.048 (4)	0.035 (4)	0.005 (3)	−0.002 (3)	−0.014 (3)
O9	0.087 (5)	0.030 (4)	0.022 (3)	0.034 (4)	0.001 (3)	0.002 (3)
O10A	0.015 (5)	0.022 (6)	0.020 (6)	0.009 (5)	0.003 (4)	0.001 (4)
O10B	0.017 (5)	0.012 (5)	0.020 (6)	0.009 (4)	0.009 (4)	0.001 (4)
O11	0.142 (2)	0.142 (2)	0.142 (2)	0.0707 (13)	−0.0005 (7)	0.0005 (7)
O12A	0.029 (8)	0.023 (8)	0.037 (9)	0.012 (7)	0.001 (6)	0.001 (6)
O12B	0.028 (8)	0.029 (8)	0.022 (7)	0.012 (7)	0.004 (6)	−0.005 (6)

Geometric parameters (Å, º) top

As1—O10Aⁱ	1.653 (10)	Mo1—O1	2.341 (5)
As1—O10A	1.653 (10)	Mo2—O7	1.658 (6)
As1—O10Aⁱⁱ	1.653 (10)	Mo2—O12B	1.806 (13)
As1—O10B	1.677 (10)	Mo2—O9	1.806 (6)
As1—O10Bⁱ	1.677 (10)	Mo2—O6	1.872 (9)
As1—O10Bⁱⁱ	1.677 (10)	Mo2—O12A	2.024 (13)
As1—O1	1.728 (9)	Mo2—O4	2.117 (5)
C1—N3	1.350 (12)	Mo2—O10Bⁱⁱ	2.309 (9)
C1—C5	1.371 (13)	Mo2—O10A	2.330 (10)
C1—C6ⁱⁱⁱ	1.447 (14)	Mo3—O8	1.651 (6)
C2—N3	1.342 (12)	Mo3—O12B	1.772 (13)
C2—C3	1.359 (14)	Mo3—O6ⁱⁱ	1.878 (9)
C2—H2	0.9300	Mo3—O5	1.923 (6)
C3—C4	1.355 (16)	Mo3—O12A	1.970 (13)
C3—H3	0.9300	Mo3—O9^iv	2.000 (6)
C4—C5	1.358 (15)	Mo3—O10Bⁱⁱ	2.325 (9)
C4—H4	0.9300	Mo3—O10Aⁱⁱ	2.359 (10)
C5—H5	0.9300	N1—N2	1.337 (12)
C6—N1	1.345 (11)	N2—H2A	0.8600
C6—C7	1.389 (15)	O1—Mo1ⁱ	2.341 (5)
C6—C1ⁱⁱⁱ	1.447 (14)	O1—Mo1ⁱⁱ	2.341 (5)
C7—C8	1.395 (17)	O2—Mo1ⁱ	2.053 (5)
C7—H7	0.9300	O6—Mo3ⁱ	1.878 (9)
C8—N2	1.339 (13)	O9—Mo3^v	2.000 (6)
C8—H8	0.9300	O10A—O10Bⁱⁱ	1.582 (13)
Cu1—N3ⁱⁱⁱ	1.984 (7)	O10A—O10B	1.599 (13)
Cu1—N3	1.984 (7)	O10A—Mo3ⁱ	2.359 (10)
Cu1—N1	1.985 (8)	O10B—O10Aⁱ	1.582 (13)
Cu1—N1ⁱⁱⁱ	1.985 (8)	O10B—O12Bⁱ	1.698 (17)
Cu1—O11	2.29 (2)	O10B—Mo2ⁱ	2.309 (9)
Mo1—O3	1.690 (6)	O10B—Mo3ⁱ	2.325 (9)
Mo1—O4	1.797 (5)	O11—H1W	0.84 (8)
Mo1—O2	1.904 (5)	O12A—O12B	0.804 (14)
Mo1—O5	1.959 (6)	O12B—O10Bⁱⁱ	1.698 (17)
Mo1—O2ⁱⁱ	2.053 (5)

O10Aⁱ—As1—O10A	111.5 (3)	O7—Mo2—O10A	157.6 (3)
O10Aⁱ—As1—O10Aⁱⁱ	111.5 (3)	O12B—Mo2—O10A	86.7 (5)
O10A—As1—O10Aⁱⁱ	111.5 (3)	O9—Mo2—O10A	88.2 (3)
O10Aⁱ—As1—O10B	56.7 (4)	O6—Mo2—O10A	58.5 (4)
O10A—As1—O10B	57.4 (4)	O12A—Mo2—O10A	108.2 (5)
O10Aⁱⁱ—As1—O10B	145.7 (5)	O4—Mo2—O10A	80.3 (3)
O10Aⁱ—As1—O10Bⁱ	57.4 (4)	O10Bⁱⁱ—Mo2—O10A	39.9 (3)
O10A—As1—O10Bⁱ	145.7 (5)	O8—Mo3—O12B	114.7 (5)
O10Aⁱⁱ—As1—O10Bⁱ	56.7 (4)	O8—Mo3—O6ⁱⁱ	100.9 (4)
O10B—As1—O10Bⁱ	111.8 (3)	O12B—Mo3—O6ⁱⁱ	143.7 (6)
O10Aⁱ—As1—O10Bⁱⁱ	145.7 (5)	O8—Mo3—O5	99.1 (3)
O10A—As1—O10Bⁱⁱ	56.7 (4)	O12B—Mo3—O5	91.2 (4)
O10Aⁱⁱ—As1—O10Bⁱⁱ	57.4 (4)	O6ⁱⁱ—Mo3—O5	90.1 (3)
O10B—As1—O10Bⁱⁱ	111.8 (3)	O8—Mo3—O12A	92.3 (5)
O10Bⁱ—As1—O10Bⁱⁱ	111.8 (3)	O12B—Mo3—O12A	24.1 (4)
O10Aⁱ—As1—O1	107.4 (4)	O6ⁱⁱ—Mo3—O12A	166.7 (5)
O10A—As1—O1	107.4 (4)	O5—Mo3—O12A	86.0 (4)
O10Aⁱⁱ—As1—O1	107.4 (4)	O8—Mo3—O9^iv	95.5 (3)
O10B—As1—O1	107.0 (3)	O12B—Mo3—O9^iv	80.4 (5)
O10Bⁱ—As1—O1	107.0 (3)	O6ⁱⁱ—Mo3—O9^iv	89.6 (4)
O10Bⁱⁱ—As1—O1	107.0 (3)	O5—Mo3—O9^iv	165.2 (2)
N3—C1—C5	122.0 (10)	O12A—Mo3—O9^iv	90.9 (5)
N3—C1—C6ⁱⁱⁱ	113.1 (8)	O8—Mo3—O10Bⁱⁱ	161.3 (3)
C5—C1—C6ⁱⁱⁱ	124.9 (9)	O12B—Mo3—O10Bⁱⁱ	46.6 (5)
N3—C2—C3	123.3 (10)	O6ⁱⁱ—Mo3—O10Bⁱⁱ	97.8 (4)
N3—C2—H2	118.4	O5—Mo3—O10Bⁱⁱ	82.7 (3)
C3—C2—H2	118.4	O12A—Mo3—O10Bⁱⁱ	69.1 (5)
C4—C3—C2	118.6 (11)	O9^iv—Mo3—O10Bⁱⁱ	82.7 (3)
C4—C3—H3	120.7	O8—Mo3—O10Aⁱⁱ	158.5 (3)
C2—C3—H3	120.7	O12B—Mo3—O10Aⁱⁱ	86.2 (5)
C3—C4—C5	119.9 (11)	O6ⁱⁱ—Mo3—O10Aⁱⁱ	57.9 (4)
C3—C4—H4	120.1	O5—Mo3—O10Aⁱⁱ	84.9 (3)
C5—C4—H4	120.1	O12A—Mo3—O10Aⁱⁱ	109.0 (5)
C4—C5—C1	119.1 (10)	O9^iv—Mo3—O10Aⁱⁱ	82.5 (3)
C4—C5—H5	120.4	O10Bⁱⁱ—Mo3—O10Aⁱⁱ	39.9 (3)
C1—C5—H5	120.4	N2—N1—C6	106.6 (8)
N1—C6—C7	109.3 (10)	N2—N1—Cu1	139.1 (7)
N1—C6—C1ⁱⁱⁱ	115.9 (8)	C6—N1—Cu1	114.2 (7)
C7—C6—C1ⁱⁱⁱ	134.8 (9)	N1—N2—C8	112.1 (9)
C6—C7—C8	106.0 (10)	N1—N2—H2A	124.0
C6—C7—H7	127.0	C8—N2—H2A	124.0
C8—C7—H7	127.0	C2—N3—C1	116.9 (8)
N2—C8—C7	106.1 (11)	C2—N3—Cu1	126.5 (7)
N2—C8—H8	127.0	C1—N3—Cu1	115.5 (7)
C7—C8—H8	127.0	As1—O1—Mo1ⁱ	122.13 (18)
N3ⁱⁱⁱ—Cu1—N3	166.7 (4)	As1—O1—Mo1	122.13 (18)
N3ⁱⁱⁱ—Cu1—N1	80.7 (3)	Mo1ⁱ—O1—Mo1	94.3 (2)
N3—Cu1—N1	102.5 (3)	As1—O1—Mo1ⁱⁱ	122.13 (18)
N3ⁱⁱⁱ—Cu1—N1ⁱⁱⁱ	102.5 (3)	Mo1ⁱ—O1—Mo1ⁱⁱ	94.3 (2)
N3—Cu1—N1ⁱⁱⁱ	80.7 (3)	Mo1—O1—Mo1ⁱⁱ	94.3 (2)
N1—Cu1—N1ⁱⁱⁱ	152.7 (5)	Mo1—O2—Mo1ⁱ	120.4 (3)
N3ⁱⁱⁱ—Cu1—O11	83.4 (2)	Mo1—O4—Mo2	149.5 (3)
N3—Cu1—O11	83.4 (2)	Mo3—O5—Mo1	142.9 (3)
N1—Cu1—O11	103.6 (3)	Mo2—O6—Mo3ⁱ	144.3 (5)
N1ⁱⁱⁱ—Cu1—O11	103.6 (3)	Mo2—O9—Mo3^v	170.5 (4)
O3—Mo1—O4	106.2 (3)	O10Bⁱⁱ—O10A—O10B	121.6 (9)
O3—Mo1—O2	98.8 (3)	O10Bⁱⁱ—O10A—As1	62.4 (5)
O4—Mo1—O2	94.5 (2)	O10B—O10A—As1	62.0 (5)
O3—Mo1—O5	101.8 (3)	O10Bⁱⁱ—O10A—Mo2	69.3 (5)
O4—Mo1—O5	89.2 (2)	O10B—O10A—Mo2	167.6 (7)
O2—Mo1—O5	157.1 (2)	As1—O10A—Mo2	125.6 (5)
O3—Mo1—O2ⁱⁱ	95.3 (2)	O10Bⁱⁱ—O10A—Mo3ⁱ	164.3 (7)
O4—Mo1—O2ⁱⁱ	158.1 (2)	O10B—O10A—Mo3ⁱ	68.9 (5)
O2—Mo1—O2ⁱⁱ	85.9 (3)	As1—O10A—Mo3ⁱ	121.8 (5)
O5—Mo1—O2ⁱⁱ	82.5 (2)	Mo2—O10A—Mo3ⁱ	99.2 (4)
O3—Mo1—O1	164.9 (3)	O10Aⁱ—O10B—O10A	118.4 (9)
O4—Mo1—O1	87.7 (2)	O10Aⁱ—O10B—As1	60.9 (5)
O2—Mo1—O1	73.8 (2)	O10A—O10B—As1	60.5 (5)
O5—Mo1—O1	83.8 (2)	O10Aⁱ—O10B—O12Bⁱ	121.6 (8)
O2ⁱⁱ—Mo1—O1	71.36 (19)	O10A—O10B—O12Bⁱ	119.9 (8)
O7—Mo2—O12B	113.9 (5)	As1—O10B—O12Bⁱ	159.0 (8)
O7—Mo2—O9	100.7 (3)	O10Aⁱ—O10B—Mo2ⁱ	70.8 (5)
O12B—Mo2—O9	88.5 (5)	O10A—O10B—Mo2ⁱ	169.3 (7)
O7—Mo2—O6	99.7 (4)	As1—O10B—Mo2ⁱ	125.6 (5)
O12B—Mo2—O6	144.4 (5)	O12Bⁱ—O10B—Mo2ⁱ	50.8 (5)
O9—Mo2—O6	97.0 (4)	O10Aⁱ—O10B—Mo3ⁱ	165.0 (7)
O7—Mo2—O12A	91.1 (5)	O10A—O10B—Mo3ⁱ	71.2 (5)
O12B—Mo2—O12A	23.4 (4)	As1—O10B—Mo3ⁱ	122.5 (5)
O9—Mo2—O12A	98.1 (5)	O12Bⁱ—O10B—Mo3ⁱ	49.3 (5)
O6—Mo2—O12A	159.5 (5)	Mo2ⁱ—O10B—Mo3ⁱ	98.7 (3)
O7—Mo2—O4	92.9 (3)	Cu1—O11—H1W	117 (2)
O12B—Mo2—O4	83.0 (4)	O12B—O12A—Mo3	64.0 (14)
O9—Mo2—O4	166.0 (2)	O12B—O12A—Mo2	63.0 (14)
O6—Mo2—O4	83.8 (3)	Mo3—O12A—Mo2	123.3 (7)
O12A—Mo2—O4	78.2 (4)	O12A—O12B—O10Bⁱⁱ	155.9 (19)
O7—Mo2—O10Bⁱⁱ	158.9 (3)	O12A—O12B—Mo3	91.9 (16)
O12B—Mo2—O10Bⁱⁱ	46.8 (5)	O10Bⁱⁱ—O12B—Mo3	84.1 (7)
O9—Mo2—O10Bⁱⁱ	88.6 (3)	O12A—O12B—Mo2	93.7 (16)
O6—Mo2—O10Bⁱⁱ	98.0 (4)	O10Bⁱⁱ—O12B—Mo2	82.4 (7)
O12A—Mo2—O10Bⁱⁱ	68.6 (5)	Mo3—O12B—Mo2	158.4 (8)
O4—Mo2—O10Bⁱⁱ	77.5 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O6^vi	0.86	2.27	3.097 (13)	162
O11—H1W···O3ⁱⁱⁱ	0.84 (8)	2.69 (11)	2.860 (10)	94 (8)

Symmetry codes: (iii) y, x, −z+1/2; (vi) x+1/3, x−y+2/3, z+1/6.

Experimental details

Crystal data
Chemical formula	[Cu(C₈H₇N₃)₂(H₂O)]₃[As₂Mo₁₈O₆₂]
M_r	3984.45
Crystal system, space group	Hexagonal, R3c
Temperature (K)	293
a, c (Å)	21.967 (3), 34.411 (7)
V (Å³)	14380 (4)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	3.72
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.664, 0.755
No. of measured, independent and observed [I > 2σ(I)] reflections	25458, 2750, 2053
R_int	0.085
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.123, 1.00
No. of reflections	2750
No. of parameters	254
No. of restraints	14
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ²(F_o²) + (0.063P)² + 278.6957P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	2.25, −1.15

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

As1—O10A	1.653 (10)	Cu1—N3	1.984 (7)
As1—O10B	1.677 (10)	Cu1—N1	1.985 (8)
As1—O1	1.728 (9)	Cu1—O11	2.29 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O6ⁱ	0.86	2.27	3.097 (13)	162.0
O11—H1W···O3ⁱⁱ	0.84 (8)	2.69 (11)	2.860 (10)	94 (8)

Symmetry codes: (i) x+1/3, x−y+2/3, z+1/6; (ii) y, x, −z+1/2.

Acknowledgements

Financial support from the Chinese Academy of Sciences (`Hundred Talents Program') and the Ministry of Science and Technology of China (grant No. 2007CB607608), Shandong Provincial Education Department and Shandong Institute of Education are gratefully acknowledged.

References

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