Tetra­imidazolium hexa-μ4-oxido-dodeca-μ2-oxido-dodeca­oxidohexa­arsenate(III)hexa­molybdenum(VI)cuprate(II)

Liu, M.; Su, Z.; Shang, Y.

doi:10.1107/S1600536810037414

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page m1308

doi:10.1107/S1600536810037414

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Tetraimidazolium hexa-μ₄-oxido-dodeca-μ₂-oxido-dodecaoxidohexaarsenate(III)hexamolybdenum(VI)cuprate(II)

Meiduo Liu,^a,^b Zhanhua Su ^a ^* and Yongchen Shang ^a

^aCollege of Chemistry and Chemical Engineering, Harbin Normal University, Harbin, People's Republic of China, and ^bDepartment of Safety and Environmental Engineering, Jixi University, Jixi, People's Republic of China
^*Correspondence e-mail: su_zhan_hua@yahoo.com

(Received 3 September 2010; accepted 18 September 2010; online 30 September 2010)

The title compound, (C₃H₅N₂)₄[As₆CuMo₆O₃₀], is made up of a centrosymmetric anionic cluster and four imidazolium cations. In the cluster, the central Cu^II atom is six-coordinated and lies on an inversion center. Adjacent clusters are linked via N—H⋯O hydrogen bonds between the imidazole cations and polyoxidoanions into a three-dimensional supramolecular architecture.

Related literature

For general background to polyoxidometalates, see: Müller et al. (1998 ). For general background to molybdoarsenates, see: Fidalgo et al. (2002 ); Sun et al. (2007 ).

Experimental

Crystal data

(C₃H₅N₂)₄[As₆CuMo₆O₃₀]
M_r = 1845.07
Monoclinic, P 2₁ /c
a = 10.5696 (7) Å
b = 19.2842 (12) Å
c = 10.4678 (7) Å
β = 106.747 (1)°
V = 2043.1 (2) Å³
Z = 2
Mo Kα radiation
μ = 7.22 mm⁻¹
T = 298 K
0.28 × 0.25 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.237, T_max = 0.326
12666 measured reflections
4906 independent reflections
4057 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.073
S = 1.03
4906 reflections
286 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −1.94 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4ⁱ	0.86	1.81	2.664 (5)	173
N2—H2A⋯O3	0.86	1.99	2.748 (5)	146
N2—H2A⋯O9ⁱⁱ	0.86	2.42	3.020 (5)	127
N3—H3A⋯O7ⁱⁱ	0.86	2.09	2.867 (6)	150
N4—H4A⋯O2ⁱⁱⁱ	0.86	2.00	2.834 (6)	165
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x-1, y, z; (iii) x, y, z+1.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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 I, global. DOI: 10.1107/S1600536810037414/hy2352sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810037414/hy2352Isup2.hkl

checkCIF report

Comment top

Polyoxometalates have unusual structural chemistry and properties that make them attractive for applications in materials science, electrochemical, catalysis and photochemical (Müller et al., 1998). Molybdenum arsenates are an important part in this field. So far the reports on molybdenum arsenates have been mainly concentrated on several discrete molybdenum arsenate clusters (Fidalgo et al., 2002; Sun et al., 2007). Therefore, further research is necessary to enrich and develop this branch. We try to obtain new materials based on inorganic molybdenum arsenate with novel structures. Here, the synthesis and crystal structure of the title compound is reported.

The structure of the title compound is shown in Fig. 1. The asymmetric unit consists of two protonated imidazole cations and a half cluster anion. The anion is centrosymmetric with the Cu^II atom lying on an inversion center. The cluster is derived from the A-type Anderson anion, in which a central CuO₆ octahedron is coordinated with six MoO₆ octahedra hexagonally arranged by sharing their edges in a plane. Two cyclic As₃O₃ trimers are capped on the opposite faces of the Anderson-type anion plane. The four free protonated imidazole molecules act as charge compensating cations. The adjacent clusters are linked via N—H···O hydrogen bonds between the imidazole cations and polyoxoanions into a three-dimensional supramolecular architecture (Table 1).

Related literature top

For general background to polyoxometalates, see: Müller et al. (1998). For general background to molybdenum arsenates, see: Fidalgo et al. (2002); Sun et al. (2007).

Experimental top

A mixture of hexaammonium heptamolybdate tetrahydrate (1.11 g, 0.89 mmol), sodium arsenite (0.41 g, 3.03 mmol), cupric chloride (0.20 g, 1.17 mmol), imidazole (0.27 g, 4.01 mmol) and water (20 ml) was placed in a 30 ml Teflon-lined Parr bomb. The bomb was heated to 413 K for 5 d. Blue block shaped crystals were isolated from the cooled solution in a 72% yield based on Mo. Analysis, calculated for C₁₂H₂₀As₆CuMo₆N₈O₃₀: C 7.81, H 1.09, N 6.07%; found: C 7.83, H 1.13, N 6.04%.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted. [Symmetry code: (i) 2-x, -y, -z.]

Tetraimidazolium hexa-µ₄-oxido-dodeca-µ₂-oxido- dodecaoxidohexaarsenate(III)hexamolybdenum(VI)cuprate(II) top

Crystal data top

(C₃H₅N₂)₄[As₆CuMo₆O₃₀]	F(000) = 1734
M_r = 1845.07	D_x = 2.999 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4555 reflections
a = 10.5696 (7) Å	θ = 2.3–28.1°
b = 19.2842 (12) Å	µ = 7.22 mm⁻¹
c = 10.4678 (7) Å	T = 298 K
β = 106.747 (1)°	Block, blue
V = 2043.1 (2) Å³	0.28 × 0.25 × 0.20 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	4906 independent reflections
Radiation source: fine-focus sealed tube	4057 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −13→14
T_min = 0.237, T_max = 0.326	k = −25→19
12666 measured reflections	l = −13→13

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0338P)² + 2.1525P] where P = (F_o² + 2F_c²)/3
4906 reflections	(Δ/σ)_max = 0.001
286 parameters	Δρ_max = 0.56 e Å⁻³
1 restraint	Δρ_min = −1.94 e Å⁻³

Crystal data top

(C₃H₅N₂)₄[As₆CuMo₆O₃₀]	V = 2043.1 (2) Å³
M_r = 1845.07	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.5696 (7) Å	µ = 7.22 mm⁻¹
b = 19.2842 (12) Å	T = 298 K
c = 10.4678 (7) Å	0.28 × 0.25 × 0.20 mm
β = 106.747 (1)°

Data collection top

Bruker APEXII CCD diffractometer	4906 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	4057 reflections with I > 2σ(I)
T_min = 0.237, T_max = 0.326	R_int = 0.029
12666 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	1 restraint
wR(F²) = 0.073	H-atom parameters constrained
S = 1.03	Δρ_max = 0.56 e Å⁻³
4906 reflections	Δρ_min = −1.94 e Å⁻³
286 parameters

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

	x	y	z	U_iso*/U_eq
Mo1	0.73132 (3)	0.054936 (18)	0.07751 (3)	0.01939 (9)
Mo2	1.01930 (3)	0.143475 (18)	0.18894 (3)	0.02087 (9)
Mo3	1.29116 (3)	0.084229 (18)	0.11868 (4)	0.02065 (9)
Cu1	1.0000	0.0000	0.0000	0.02300 (16)
As1	1.03800 (5)	0.16004 (2)	−0.13845 (4)	0.02655 (11)
As2	0.75566 (4)	0.08081 (2)	−0.24782 (4)	0.02711 (11)
As3	0.98689 (4)	−0.02215 (2)	0.32318 (4)	0.02600 (11)
O1	0.7044 (3)	−0.04164 (14)	0.0461 (3)	0.0222 (6)
O2	0.5905 (3)	0.09037 (16)	−0.0244 (3)	0.0324 (7)
O3	0.7135 (3)	0.05775 (16)	0.2348 (3)	0.0301 (7)
O4	0.8381 (3)	0.13750 (14)	0.0796 (3)	0.0222 (6)
O5	0.9982 (3)	0.14957 (17)	0.3446 (3)	0.0335 (7)
O6	1.0471 (3)	0.22633 (16)	0.1453 (3)	0.0347 (7)
O7	1.1939 (3)	0.10410 (15)	0.2460 (3)	0.0240 (6)
O8	1.3348 (3)	0.16566 (16)	0.0847 (3)	0.0355 (8)
O9	1.4277 (3)	0.05057 (17)	0.2328 (3)	0.0330 (7)
O10	1.0708 (3)	0.10168 (14)	0.0027 (3)	0.0194 (6)
O11	0.8615 (3)	0.15371 (15)	−0.1931 (3)	0.0311 (7)
O12	0.8071 (3)	0.02681 (14)	−0.1035 (3)	0.0190 (6)
O13	0.9515 (3)	0.02733 (14)	0.1712 (3)	0.0193 (6)
O14	0.9234 (3)	−0.10364 (16)	0.2570 (3)	0.0294 (7)
O15	1.1601 (3)	−0.03719 (17)	0.3501 (3)	0.0306 (7)
C1	0.7300 (6)	0.1970 (3)	0.4181 (6)	0.0547 (16)
H1	0.8100	0.1911	0.3989	0.066*
C2	0.5755 (5)	0.2391 (3)	0.4939 (5)	0.0402 (12)
H2	0.5301	0.2679	0.5369	0.048*
C3	0.5305 (6)	0.1807 (3)	0.4292 (6)	0.0481 (14)
H3	0.4477	0.1610	0.4181	0.058*
C4	0.2581 (6)	0.1681 (3)	0.5787 (6)	0.0498 (14)
H4	0.2056	0.2032	0.5297	0.060*
C5	0.3261 (7)	0.1725 (4)	0.7012 (7)	0.072 (2)
H5	0.3326	0.2109	0.7565	0.087*
C6	0.3535 (7)	0.0703 (4)	0.6296 (9)	0.072 (2)
H6	0.3815	0.0249	0.6254	0.086*
N1	0.6994 (4)	0.2487 (2)	0.4856 (5)	0.0422 (11)
H1A	0.7501	0.2831	0.5190	0.051*
N2	0.6282 (5)	0.1554 (2)	0.3826 (5)	0.0511 (13)
H2A	0.6240	0.1179	0.3369	0.061*
N3	0.2742 (4)	0.1053 (3)	0.5320 (5)	0.0493 (12)
H3A	0.2388	0.0906	0.4521	0.059*
N4	0.3864 (5)	0.1108 (5)	0.7346 (6)	0.091 (3)
H4A	0.4378	0.0998	0.8118	0.109*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.01533 (17)	0.02100 (17)	0.02186 (18)	0.00083 (13)	0.00538 (13)	−0.00261 (13)
Mo2	0.01802 (18)	0.02131 (18)	0.02259 (18)	−0.00029 (14)	0.00474 (14)	−0.00575 (13)
Mo3	0.01496 (17)	0.02128 (18)	0.02509 (19)	−0.00293 (13)	0.00477 (14)	−0.00520 (13)
Cu1	0.0210 (4)	0.0247 (4)	0.0227 (4)	−0.0005 (3)	0.0052 (3)	−0.0014 (3)
As1	0.0304 (3)	0.0220 (2)	0.0268 (2)	−0.00166 (18)	0.00755 (19)	0.00428 (17)
As2	0.0213 (2)	0.0327 (2)	0.0245 (2)	0.00458 (18)	0.00205 (18)	0.00643 (18)
As3	0.0291 (2)	0.0318 (2)	0.0175 (2)	0.00211 (19)	0.00728 (18)	0.00140 (17)
O1	0.0210 (15)	0.0219 (14)	0.0254 (15)	−0.0049 (12)	0.0095 (12)	−0.0016 (11)
O2	0.0228 (16)	0.0330 (18)	0.0384 (18)	0.0045 (13)	0.0038 (14)	−0.0019 (14)
O3	0.0300 (17)	0.0327 (17)	0.0309 (17)	−0.0025 (14)	0.0142 (14)	−0.0056 (13)
O4	0.0188 (14)	0.0185 (14)	0.0270 (15)	0.0012 (11)	0.0029 (12)	−0.0012 (11)
O5	0.0263 (17)	0.046 (2)	0.0284 (17)	0.0003 (14)	0.0087 (14)	−0.0085 (14)
O6	0.0355 (18)	0.0233 (16)	0.045 (2)	−0.0010 (14)	0.0103 (15)	−0.0075 (14)
O7	0.0185 (14)	0.0308 (16)	0.0209 (14)	−0.0014 (12)	0.0028 (11)	−0.0075 (12)
O8	0.0338 (18)	0.0262 (16)	0.050 (2)	−0.0092 (14)	0.0182 (16)	−0.0082 (15)
O9	0.0175 (15)	0.0403 (19)	0.0362 (18)	0.0017 (14)	−0.0005 (13)	−0.0076 (14)
O10	0.0177 (14)	0.0203 (14)	0.0196 (14)	−0.0009 (11)	0.0046 (11)	−0.0005 (11)
O11	0.0302 (17)	0.0274 (16)	0.0338 (18)	0.0048 (13)	0.0063 (14)	0.0065 (13)
O12	0.0150 (13)	0.0215 (14)	0.0190 (14)	−0.0002 (11)	0.0028 (11)	0.0025 (11)
O13	0.0185 (14)	0.0213 (14)	0.0178 (13)	0.0018 (11)	0.0049 (11)	0.0000 (11)
O14	0.0324 (17)	0.0286 (16)	0.0296 (17)	−0.0015 (13)	0.0126 (14)	0.0037 (13)
O15	0.0294 (17)	0.0382 (18)	0.0213 (15)	0.0017 (14)	0.0028 (13)	0.0038 (13)
C1	0.052 (4)	0.047 (3)	0.076 (4)	−0.002 (3)	0.036 (3)	−0.008 (3)
C2	0.038 (3)	0.036 (3)	0.050 (3)	0.000 (2)	0.017 (2)	−0.010 (2)
C3	0.048 (3)	0.048 (3)	0.053 (3)	−0.021 (3)	0.021 (3)	−0.017 (3)
C4	0.052 (4)	0.044 (3)	0.048 (3)	0.011 (3)	0.005 (3)	0.010 (3)
C5	0.073 (5)	0.084 (5)	0.059 (4)	−0.036 (4)	0.018 (4)	−0.023 (4)
C6	0.062 (5)	0.054 (4)	0.112 (7)	0.019 (3)	0.045 (5)	0.049 (4)
N1	0.037 (2)	0.028 (2)	0.061 (3)	−0.0103 (18)	0.014 (2)	−0.0152 (19)
N2	0.074 (4)	0.032 (2)	0.057 (3)	−0.012 (2)	0.034 (3)	−0.019 (2)
N3	0.038 (3)	0.055 (3)	0.048 (3)	−0.009 (2)	0.000 (2)	−0.004 (2)
N4	0.034 (3)	0.190 (8)	0.041 (3)	0.001 (4)	0.000 (3)	0.060 (4)

Geometric parameters (Å, º) top

Mo1—O2	1.704 (3)	As2—O11	1.785 (3)
Mo1—O3	1.711 (3)	As2—O12	1.786 (3)
Mo1—O1	1.898 (3)	As2—O15ⁱ	1.788 (3)
Mo1—O4	1.948 (3)	As3—O14	1.770 (3)
Mo1—O13	2.312 (3)	As3—O15	1.793 (3)
Mo1—O12	2.324 (3)	As3—O13	1.800 (3)
Mo2—O6	1.710 (3)	C1—N2	1.308 (7)
Mo2—O5	1.711 (3)	C1—N1	1.316 (7)
Mo2—O7	1.925 (3)	C1—H1	0.9300
Mo2—O4	1.931 (3)	C2—C3	1.329 (7)
Mo2—O10	2.315 (3)	C2—N1	1.351 (6)
Mo2—O13	2.343 (3)	C2—H2	0.9300
Mo3—O8	1.703 (3)	C3—N2	1.354 (7)
Mo3—O9	1.714 (3)	C3—H3	0.9300
Mo3—O1ⁱ	1.923 (3)	C4—C5	1.280 (9)
Mo3—O7	1.941 (3)	C4—N3	1.334 (7)
Mo3—O10	2.320 (3)	C4—H4	0.9300
Mo3—O12ⁱ	2.365 (3)	C5—N4	1.349 (10)
Cu1—O13	2.069 (3)	C5—H5	0.9300
Cu1—O13ⁱ	2.069 (3)	C6—N3	1.308 (8)
Cu1—O12	2.080 (3)	C6—N4	1.310 (10)
Cu1—O12ⁱ	2.080 (3)	C6—H6	0.9300
Cu1—O10ⁱ	2.096 (3)	N1—H1A	0.8600
Cu1—O10	2.096 (3)	N2—H2A	0.8600
As1—O14ⁱ	1.783 (3)	N3—H3A	0.8600
As1—O11	1.791 (3)	N4—H4A	0.8600
As1—O10	1.810 (3)

O2—Mo1—O3	105.76 (15)	O11—As1—O10	98.94 (13)
O2—Mo1—O1	102.98 (14)	O11—As2—O12	100.25 (13)
O3—Mo1—O1	98.34 (13)	O11—As2—O15ⁱ	100.87 (15)
O2—Mo1—O4	94.47 (13)	O12—As2—O15ⁱ	98.60 (13)
O3—Mo1—O4	100.78 (13)	O14—As3—O15	99.93 (14)
O1—Mo1—O4	149.46 (12)	O14—As3—O13	99.56 (13)
O2—Mo1—O13	161.51 (13)	O15—As3—O13	99.65 (13)
O3—Mo1—O13	88.59 (12)	Mo1—O1—Mo3ⁱ	122.20 (14)
O1—Mo1—O13	85.98 (11)	Mo2—O4—Mo1	121.87 (14)
O4—Mo1—O13	70.99 (10)	Mo2—O7—Mo3	121.00 (14)
O2—Mo1—O12	91.53 (13)	As1—O10—Cu1	125.93 (14)
O3—Mo1—O12	162.04 (13)	As1—O10—Mo2	115.77 (13)
O1—Mo1—O12	72.51 (10)	Cu1—O10—Mo2	99.64 (10)
O4—Mo1—O12	82.27 (10)	As1—O10—Mo3	116.41 (13)
O13—Mo1—O12	75.58 (9)	Cu1—O10—Mo3	99.92 (11)
O6—Mo2—O5	105.65 (16)	Mo2—O10—Mo3	93.11 (9)
O6—Mo2—O7	103.19 (14)	As2—O11—As1	130.91 (17)
O5—Mo2—O7	96.23 (14)	As2—O12—Cu1	126.82 (14)
O6—Mo2—O4	96.59 (13)	As2—O12—Mo1	117.47 (13)
O5—Mo2—O4	100.89 (13)	Cu1—O12—Mo1	98.60 (10)
O7—Mo2—O4	149.22 (11)	As2—O12—Mo3ⁱ	116.78 (13)
O6—Mo2—O10	90.01 (13)	Cu1—O12—Mo3ⁱ	98.95 (10)
O5—Mo2—O10	162.31 (13)	Mo1—O12—Mo3ⁱ	91.05 (9)
O7—Mo2—O10	71.73 (10)	As3—O13—Cu1	126.18 (14)
O4—Mo2—O10	85.07 (11)	As3—O13—Mo1	115.12 (13)
O6—Mo2—O13	160.76 (13)	Cu1—O13—Mo1	99.30 (10)
O5—Mo2—O13	91.16 (13)	As3—O13—Mo2	117.13 (13)
O7—Mo2—O13	83.77 (11)	Cu1—O13—Mo2	99.54 (11)
O4—Mo2—O13	70.57 (10)	Mo1—O13—Mo2	93.50 (10)
O10—Mo2—O13	75.00 (9)	As3—O14—As1ⁱ	132.63 (17)
O8—Mo3—O9	105.69 (16)	As2ⁱ—O15—As3	130.07 (17)
O8—Mo3—O1ⁱ	97.38 (14)	N2—C1—N1	108.0 (5)
O9—Mo3—O1ⁱ	103.31 (14)	N2—C1—H1	126.0
O8—Mo3—O7	100.96 (14)	N1—C1—H1	126.0
O9—Mo3—O7	95.87 (13)	C3—C2—N1	107.2 (5)
O1ⁱ—Mo3—O7	148.71 (11)	C3—C2—H2	126.4
O8—Mo3—O10	92.78 (13)	N1—C2—H2	126.4
O9—Mo3—O10	159.45 (13)	C2—C3—N2	107.0 (5)
O1ⁱ—Mo3—O10	82.70 (11)	C2—C3—H3	126.5
O7—Mo3—O10	71.35 (10)	N2—C3—H3	126.5
O8—Mo3—O12ⁱ	163.96 (13)	C5—C4—N3	109.5 (6)
O9—Mo3—O12ⁱ	88.23 (13)	C5—C4—H4	125.2
O1ⁱ—Mo3—O12ⁱ	71.15 (10)	N3—C4—H4	125.2
O7—Mo3—O12ⁱ	85.17 (11)	C4—C5—N4	106.7 (7)
O10—Mo3—O12ⁱ	74.99 (9)	C4—C5—H5	126.7
O13—Cu1—O13ⁱ	180.0	N4—C5—H5	126.7
O13—Cu1—O12	86.42 (10)	N3—C6—N4	107.7 (6)
O13ⁱ—Cu1—O12	93.58 (10)	N3—C6—H6	126.2
O13—Cu1—O12ⁱ	93.58 (10)	N4—C6—H6	126.2
O13ⁱ—Cu1—O12ⁱ	86.42 (10)	C1—N1—C2	108.8 (4)
O12—Cu1—O12ⁱ	180.0	C1—N1—H1A	125.6
O13—Cu1—O10ⁱ	94.21 (10)	C2—N1—H1A	125.6
O13ⁱ—Cu1—O10ⁱ	85.79 (10)	C1—N2—C3	109.1 (5)
O12—Cu1—O10ⁱ	86.14 (10)	C1—N2—H2A	125.5
O12ⁱ—Cu1—O10ⁱ	93.86 (10)	C3—N2—H2A	125.5
O13—Cu1—O10	85.79 (10)	C6—N3—C4	107.6 (6)
O13ⁱ—Cu1—O10	94.21 (10)	C6—N3—H3A	126.2
O12—Cu1—O10	93.86 (10)	C4—N3—H3A	126.2
O12ⁱ—Cu1—O10	86.14 (10)	C6—N4—C5	108.5 (5)
O10ⁱ—Cu1—O10	180.0	C6—N4—H4A	125.8
O14ⁱ—As1—O11	99.33 (14)	C5—N4—H4A	125.8
O14ⁱ—As1—O10	99.24 (13)

Symmetry code: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱⁱ	0.86	1.81	2.664 (5)	173
N2—H2A···O3	0.86	1.99	2.748 (5)	146
N2—H2A···O9ⁱⁱⁱ	0.86	2.42	3.020 (5)	127
N3—H3A···O7ⁱⁱⁱ	0.86	2.09	2.867 (6)	150
N4—H4A···O2^iv	0.86	2.00	2.834 (6)	165

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

Experimental details

Crystal data
Chemical formula	(C₃H₅N₂)₄[As₆CuMo₆O₃₀]
M_r	1845.07
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	10.5696 (7), 19.2842 (12), 10.4678 (7)
β (°)	106.747 (1)
V (Å³)	2043.1 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	7.22
Crystal size (mm)	0.28 × 0.25 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.237, 0.326
No. of measured, independent and observed [I > 2σ(I)] reflections	12666, 4906, 4057
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.073, 1.03
No. of reflections	4906
No. of parameters	286
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −1.94

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.86	1.81	2.664 (5)	173
N2—H2A···O3	0.86	1.99	2.748 (5)	146
N2—H2A···O9ⁱⁱ	0.86	2.42	3.020 (5)	127
N3—H3A···O7ⁱⁱ	0.86	2.09	2.867 (6)	150
N4—H4A···O2ⁱⁱⁱ	0.86	2.00	2.834 (6)	165

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

Acknowledgements

This work was supported by the Science and Technology Project of the Education Office of Heilongjiang Province (11531249), the Scientific Research Foundation for Doctors of Harbin Normal University (09XBKQ11) and the Research Project of Harbin Normal University (KM2007–09).

References

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