Tetra-imidazolium hexa-μ(4)-oxido-dodeca-μ(2)-oxido-dodeca-oxidohexa-arsenate(III)hexa-molybdenum(VI)cuprate(II).

The title compound, (C(3)H(5)N(2))(4)[As(6)CuMo(6)O(30)], 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 supra-molecular 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 = 1845.07

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.073

S = 1.03

4906 reflections

286 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.56 e Å−3

Δρmin = −1.94 e Å−3

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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810037414/hy2352sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C3H5N2)4[As6CuMo6O30]	F(000) = 1734
Mr = 1845.07	Dx = 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

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

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(Fo2) + (0.0338P)2 + 2.1525P] where P = (Fo2 + 2Fc2)/3
4906 reflections	(Δ/σ)max = 0.001
286 parameters	Δρmax = 0.56 e Å−3
1 restraint	Δρmin = −1.94 e Å−3

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···O2iv	0.86	2.00	2.834 (6)	165

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) ; (ii) ; (iii) .