Tetra-ammonium diaqua-diperoxidoocta-molybdate(VI) tetra-hydrate.

The title compound (NH(4))(4)[Mo(8)O(24)(O(2))(2)(H(2)O)(2)]·4H(2)O, consists of an octa-molybdate cluster with a crystallographic centre of symmetry. The clusters pack in a cubic close packing arrangement defining channels containing water mol-ecules and ammonium cations, which exhibit hydrogen bonding with neighbouring clusters. Hydrogen bonding also exists between the coordinated water mol-ecules of one cluster with one of the O atoms of the peroxido fragment in a neighbouring cluster.

Related literature

For work on polyoxidomolybdates, see: Pope (1983 ▶); Pope & Müller (2001 ▶); Hill (1998 ▶). Baerwald (1885 ▶) probably reported the first peroxidomolybdate. Stomberg et al. have prepared a range of peroxidomolybdates and obtained crystal structures of these species, see: Larking & Stomberg (1970 ▶, 1972 ▶); Olson & Stomberg (1996 ▶, 1997a ▶,b ▶); Persdotter et al. (1986a ▶,b ▶,c ▶); Stomberg (1968 ▶, 1969 ▶, 1970 ▶, 1988a ▶,b ▶, 1992 ▶, 1995 ▶); Stomberg & Trysberg (1969 ▶); Stomberg & Olson (1996 ▶); Trysberg & Stomberg (1968 ▶, 1981 ▶). The versatile MoO6 octa­hedron building block [see: Pope & Müller (1991 ▶); Chen & Zubieta (1992 ▶)] results in an exceptionally large family of polyoxidomolybdates, see: Michailovski & Patzke (2006 ▶). For a review of the structural chemistry of peroxidomolybdates, see: Dickman & Pope (1994 ▶): Sergienko (2008 ▶). The tetra­ammonium salt of the centrosymmetric [Mo8O24(O2)2(H2O)2]4− anion has been characterized with moderate precision, see: Trysberg & Stomberg (1981 ▶): Olson & Stomberg (1997a ▶). For bonds lengths in polyoxidomolybdates, see: Feng & Mao (2004 ▶); Long et al. (2003 ▶); Shi et al. (2006 ▶).

Experimental

Crystal data

(NH4)4[Mo8O24(O2)2(H2O)2]·4H2O

M = 1395.78

Monoclinic,

a = 10.405 (3) Å

b = 7.8706 (19) Å

c = 18.063 (4) Å

β = 96.991 (4)°

V = 1468.3 (6) Å3

Z = 2

Mo Kα radiation

μ = 3.43 mm−1

T = 150 K

0.32 × 0.19 × 0.08 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: gaussian (XPREP; Bruker, 1995 ▶; Coppens et al., 1965 ▶) T min = 0.398, T max = 0.773

14005 measured reflections

3542 independent reflections

3434 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.019

wR(F 2) = 0.043

S = 1.16

3542 reflections

250 parameters

14 restraints

Only H-atom coordinates refined

Δρmax = 1.02 e Å−3

Δρmin = −0.70 e Å−3

Data collection: SMART (Bruker, 1995 ▶); cell refinement: SAINT (Bruker, 1995 ▶); data reduction: SAINT and XPREP (Bruker, 1995 ▶; Coppens et al., 1965 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: TEXSAN for Windows (Molecular Structure Corporation, 1998 ▶), Xtal3.7 (Hall et al., 2000 ▶), ORTEPII (Johnson, 1976 ▶) and WinGX (Farrugia, 1999 ▶); software used to prepare material for publication: enCIFer (Allen et al., 2004 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809023460/br2108sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809023460/br2108Isup2.hkl

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

(NH4)4[Mo8O24(O2)2(H2O)2]·4H2O	F(000) = 1328
Mr = 1395.78	Dx = 3.157 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1023 reflections
a = 10.405 (3) Å	θ = 2.8–28.3°
b = 7.8706 (19) Å	µ = 3.43 mm−1
c = 18.063 (4) Å	T = 150 K
β = 96.991 (4)°	Blade, yellow
V = 1468.3 (6) Å3	0.32 × 0.19 × 0.08 mm
Z = 2

Bruker SMART 1000 CCD diffractometer	3542 independent reflections
Radiation source: sealed tube	3434 reflections with I > 2σ(I)
graphite	Rint = 0.032
ω scans	θmax = 28.3°, θmin = 2.2°
Absorption correction: gaussian (XPREP; Bruker, 1995; Coppens et al., 1965)	h = −13→13
Tmin = 0.398, Tmax = 0.773	k = −10→10
14005 measured reflections	l = −24→24

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)] = 0.019	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.043	Only H-atom coordinates refined
S = 1.16	w = 1/[σ2(Fo2) + (0.016P)2 + 2.2853P] where P = (Fo2 + 2Fc2)/3
3542 reflections	(Δ/σ)max = 0.001
250 parameters	Δρmax = 1.01 e Å−3
14 restraints	Δρmin = −0.70 e Å−3

Experimental. attached with Exxon Paratone N, to a short length of fibre supported on a thin piece of copper wire inserted in a copper mounting pin. The crystal was quenched in a cold nitrogen gas stream from an Oxford Cryosystems Cryostream.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Mo1	0.578257 (18)	0.03860 (2)	0.654717 (10)	0.00883 (5)
Mo2	0.267481 (18)	0.07806 (2)	0.612704 (10)	0.00964 (5)
Mo3	0.153081 (18)	0.16838 (2)	0.442190 (11)	0.00992 (5)
Mo4	0.473839 (18)	0.21902 (2)	0.486860 (10)	0.00802 (5)
O1	0.75337 (18)	0.1060 (2)	0.69344 (10)	0.0214 (4)
O2	0.65823 (18)	0.2109 (2)	0.72269 (10)	0.0216 (4)
O3	0.54977 (16)	−0.1215 (2)	0.71260 (9)	0.0146 (3)
O4	0.42192 (15)	0.1707 (2)	0.66940 (9)	0.0111 (3)
O5	0.59440 (16)	0.2362 (2)	0.56376 (9)	0.0117 (3)
O6	0.25417 (17)	−0.1077 (2)	0.65969 (9)	0.0153 (3)
O7	0.15724 (16)	0.2132 (2)	0.64528 (10)	0.0154 (3)
O8	0.17259 (16)	0.0052 (2)	0.51832 (9)	0.0123 (3)
O9	0.32211 (15)	0.2731 (2)	0.52672 (9)	0.0112 (3)
O10	0.06078 (16)	0.3204 (2)	0.47923 (10)	0.0154 (3)
O11	0.05378 (17)	0.0689 (2)	0.37343 (10)	0.0178 (4)
O12	0.20013 (18)	0.3722 (2)	0.36953 (10)	0.0165 (3)
O13	0.32947 (15)	0.0976 (2)	0.41274 (9)	0.0108 (3)
O14	0.50583 (16)	0.3819 (2)	0.42998 (9)	0.0133 (3)
O15	0.55751 (15)	0.02784 (19)	0.43622 (9)	0.0095 (3)
O16	0.1645 (2)	0.5543 (2)	0.69018 (11)	0.0235 (4)
O17	0.89009 (18)	0.3251 (2)	0.61140 (10)	0.0181 (4)
N1	0.7945 (2)	0.3830 (3)	0.45833 (12)	0.0163 (4)
N2	0.4450 (3)	0.5128 (3)	0.72139 (13)	0.0225 (5)
H12A	0.203 (3)	0.354 (5)	0.3179 (7)	0.034*
H12B	0.162 (3)	0.481 (2)	0.372 (2)	0.034*
H16B	0.128 (3)	0.597 (4)	0.7317 (13)	0.034*
H16A	0.135 (3)	0.441 (2)	0.691 (2)	0.034*
H17A	0.854 (3)	0.267 (4)	0.6492 (15)	0.034*
H17B	0.9770 (14)	0.290 (4)	0.615 (2)	0.034*
H1B	0.8775 (17)	0.434 (4)	0.465 (2)	0.034*
H1A	0.728 (2)	0.462 (4)	0.463 (2)	0.034*
H1C	0.797 (3)	0.361 (5)	0.4069 (7)	0.034*
H1D	0.797 (4)	0.303 (4)	0.4976 (14)	0.034*
H2A	0.3570 (14)	0.546 (5)	0.716 (2)	0.034*
H2B	0.447 (4)	0.405 (2)	0.6981 (19)	0.034*
H2C	0.468 (3)	0.505 (5)	0.7736 (7)	0.034*
H2D	0.494 (3)	0.589 (4)	0.6960 (18)	0.034*

	U11	U22	U33	U12	U13	U23
Mo1	0.00872 (9)	0.00944 (9)	0.00819 (9)	0.00024 (6)	0.00051 (7)	−0.00073 (6)
Mo2	0.00888 (9)	0.01032 (9)	0.00991 (9)	−0.00013 (7)	0.00191 (7)	−0.00078 (7)
Mo3	0.00759 (9)	0.01116 (9)	0.01077 (9)	0.00088 (7)	0.00020 (7)	−0.00090 (7)
Mo4	0.00759 (9)	0.00779 (9)	0.00865 (9)	0.00016 (6)	0.00085 (7)	−0.00025 (6)
O1	0.0209 (9)	0.0228 (9)	0.0195 (9)	−0.0036 (8)	−0.0015 (7)	−0.0021 (7)
O2	0.0199 (9)	0.0253 (10)	0.0186 (9)	−0.0046 (8)	−0.0013 (7)	−0.0022 (7)
O3	0.0155 (8)	0.0143 (8)	0.0137 (8)	0.0014 (7)	0.0009 (6)	0.0009 (6)
O4	0.0108 (7)	0.0116 (7)	0.0111 (7)	0.0002 (6)	0.0016 (6)	−0.0033 (6)
O5	0.0115 (8)	0.0109 (7)	0.0126 (8)	−0.0006 (6)	0.0012 (6)	−0.0001 (6)
O6	0.0167 (8)	0.0146 (8)	0.0148 (8)	−0.0021 (7)	0.0030 (7)	−0.0002 (6)
O7	0.0119 (8)	0.0166 (8)	0.0183 (8)	0.0013 (6)	0.0045 (7)	−0.0031 (7)
O8	0.0120 (7)	0.0119 (7)	0.0129 (8)	−0.0017 (6)	0.0010 (6)	−0.0009 (6)
O9	0.0105 (7)	0.0099 (7)	0.0132 (8)	−0.0002 (6)	0.0010 (6)	−0.0007 (6)
O10	0.0108 (8)	0.0181 (8)	0.0177 (8)	0.0022 (7)	0.0029 (6)	−0.0019 (7)
O11	0.0145 (8)	0.0201 (9)	0.0177 (8)	0.0001 (7)	−0.0019 (7)	−0.0040 (7)
O12	0.0211 (9)	0.0143 (8)	0.0144 (8)	0.0035 (7)	0.0031 (7)	0.0034 (7)
O13	0.0093 (7)	0.0116 (7)	0.0113 (7)	−0.0001 (6)	0.0001 (6)	−0.0013 (6)
O14	0.0144 (8)	0.0123 (8)	0.0129 (8)	0.0003 (6)	0.0005 (6)	0.0008 (6)
O15	0.0090 (7)	0.0100 (7)	0.0093 (7)	0.0008 (6)	0.0008 (6)	−0.0012 (6)
O16	0.0344 (11)	0.0182 (9)	0.0186 (9)	−0.0031 (8)	0.0056 (8)	−0.0005 (7)
O17	0.0171 (9)	0.0166 (8)	0.0207 (9)	0.0037 (7)	0.0023 (7)	0.0026 (7)
N1	0.0146 (10)	0.0173 (10)	0.0166 (10)	−0.0010 (8)	−0.0004 (8)	−0.0002 (8)
N2	0.0322 (13)	0.0187 (11)	0.0159 (10)	−0.0009 (10)	0.0001 (9)	0.0021 (9)

Mo1—O3	1.6864 (17)	Mo4—O15	2.0131 (16)
Mo1—O1	1.9443 (19)	Mo4—O13	2.1148 (16)
Mo1—O2	1.9468 (19)	Mo4—O15i	2.4335 (16)
Mo1—O13i	1.9599 (16)	O1—O2	1.438 (3)
Mo1—O4	1.9755 (16)	O12—H12A	0.947 (10)
Mo1—O15i	2.0983 (16)	O12—H12B	0.949 (10)
Mo1—O5	2.2836 (17)	O13—Mo1i	1.9599 (16)
Mo2—O6	1.7045 (18)	O15—Mo1i	2.0983 (16)
Mo2—O7	1.7200 (17)	O15—Mo2i	2.2768 (16)
Mo2—O4	1.9397 (16)	O15—Mo4i	2.4335 (16)
Mo2—O8	1.9496 (16)	O16—H16B	0.94 (3)
Mo2—O15i	2.2768 (16)	O16—H16A	0.943 (10)
Mo2—O9	2.3037 (17)	O17—H17A	0.94 (3)
Mo3—O11	1.7062 (18)	O17—H17B	0.939 (10)
Mo3—O10	1.7198 (17)	N1—H1B	0.948 (10)
Mo3—O8	1.8744 (17)	N1—H1A	0.94 (3)
Mo3—O13	2.0493 (17)	N1—H1C	0.948 (10)
Mo3—O12	2.1663 (18)	N1—H1D	0.95 (3)
Mo3—O9	2.3348 (16)	N2—H2A	0.946 (10)
Mo4—O14	1.7007 (17)	N2—H2B	0.945 (10)
Mo4—O5	1.7600 (16)	N2—H2C	0.946 (10)
Mo4—O9	1.8626 (17)	N2—H2D	0.94 (3)
O3—Mo1—O1	102.03 (8)	O12—Mo3—O9	85.81 (6)
O3—Mo1—O2	102.90 (8)	O14—Mo4—O5	104.22 (8)
O1—Mo1—O2	43.38 (8)	O14—Mo4—O9	107.38 (8)
O3—Mo1—O13i	96.49 (8)	O5—Mo4—O9	103.51 (8)
O1—Mo1—O13i	82.20 (8)	O14—Mo4—O15	99.30 (7)
O2—Mo1—O13i	124.68 (8)	O5—Mo4—O15	96.32 (7)
O3—Mo1—O4	95.75 (8)	O9—Mo4—O15	141.30 (7)
O1—Mo1—O4	123.99 (8)	O14—Mo4—O13	97.71 (7)
O2—Mo1—O4	81.05 (8)	O5—Mo4—O13	156.59 (7)
O13i—Mo1—O4	147.69 (7)	O9—Mo4—O13	77.16 (7)
O3—Mo1—O15i	98.44 (7)	O15—Mo4—O13	71.81 (6)
O1—Mo1—O15i	149.52 (7)	O14—Mo4—O15i	175.07 (7)
O2—Mo1—O15i	149.62 (7)	O5—Mo4—O15i	75.11 (7)
O13i—Mo1—O15i	73.21 (7)	O9—Mo4—O15i	77.47 (6)
O4—Mo1—O15i	75.48 (6)	O15—Mo4—O15i	76.00 (7)
O3—Mo1—O5	171.45 (7)	O13—Mo4—O15i	82.33 (6)
O1—Mo1—O5	85.71 (7)	O2—O1—Mo1	68.40 (11)
O2—Mo1—O5	85.18 (7)	O1—O2—Mo1	68.21 (11)
O13i—Mo1—O5	80.85 (7)	Mo2—O4—Mo1	111.97 (8)
O4—Mo1—O5	82.64 (6)	Mo4—O5—Mo1	114.05 (8)
O15i—Mo1—O5	73.02 (6)	Mo3—O8—Mo2	115.98 (8)
O6—Mo2—O7	105.20 (9)	Mo4—O9—Mo2	113.49 (7)
O6—Mo2—O4	99.89 (8)	Mo4—O9—Mo3	105.84 (7)
O7—Mo2—O4	97.53 (8)	Mo2—O9—Mo3	88.71 (6)
O6—Mo2—O8	96.89 (8)	Mo3—O12—H12A	121 (2)
O7—Mo2—O8	101.14 (8)	Mo3—O12—H12B	121 (2)
O4—Mo2—O8	150.60 (7)	H12A—O12—H12B	104 (3)
O6—Mo2—O15i	89.80 (7)	Mo1i—O13—Mo3	146.31 (9)
O7—Mo2—O15i	163.24 (7)	Mo1i—O13—Mo4	106.07 (7)
O4—Mo2—O15i	72.07 (6)	Mo3—O13—Mo4	107.61 (7)
O8—Mo2—O15i	84.07 (6)	Mo4—O15—Mo1i	104.76 (7)
O6—Mo2—O9	161.61 (7)	Mo4—O15—Mo2i	149.38 (8)
O7—Mo2—O9	92.75 (7)	Mo1i—O15—Mo2i	95.68 (6)
O4—Mo2—O9	81.31 (6)	Mo4—O15—Mo4i	104.00 (7)
O8—Mo2—O9	75.33 (6)	Mo1i—O15—Mo4i	97.11 (6)
O15i—Mo2—O9	73.00 (6)	Mo2i—O15—Mo4i	95.65 (6)
O11—Mo3—O10	106.56 (9)	H16B—O16—H16A	99 (3)
O11—Mo3—O8	102.80 (8)	H17A—O17—H17B	105 (3)
O10—Mo3—O8	101.94 (8)	H1B—N1—H1A	112 (3)
O11—Mo3—O13	99.70 (8)	H1B—N1—H1C	94 (3)
O10—Mo3—O13	148.24 (7)	H1A—N1—H1C	108 (3)
O8—Mo3—O13	89.08 (7)	H1B—N1—H1D	104 (3)
O11—Mo3—O12	93.46 (8)	H1A—N1—H1D	110 (3)
O10—Mo3—O12	84.18 (8)	H1C—N1—H1D	128 (3)
O8—Mo3—O12	159.99 (7)	H2A—N2—H2B	106 (3)
O13—Mo3—O12	76.61 (7)	H2A—N2—H2C	104 (3)
O11—Mo3—O9	168.36 (7)	H2B—N2—H2C	112 (3)
O10—Mo3—O9	84.95 (7)	H2A—N2—H2D	111 (3)
O8—Mo3—O9	75.90 (6)	H2B—N2—H2D	108 (3)
O13—Mo3—O9	68.81 (6)	H2C—N2—H2D	116 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12A···O2ii	0.95 (1)	1.80 (2)	2.715 (3)	161 (3)
O12—H12A···O1ii	0.95 (1)	2.39 (2)	3.299 (3)	161 (3)
O12—H12B···O17iii	0.95 (1)	1.66 (1)	2.599 (3)	171 (4)
O16—H16B···O4iv	0.94 (3)	2.01 (3)	2.939 (3)	170 (3)
O16—H16A···O7	0.94 (1)	2.00 (2)	2.803 (3)	142 (3)
O17—H17A···O1	0.94 (3)	1.88 (2)	2.776 (3)	159 (3)
O17—H17B···O7v	0.94 (1)	1.98 (1)	2.909 (3)	169 (3)
N1—H1B···O10v	0.95 (1)	2.09 (3)	2.795 (3)	130 (3)
N1—H1B···O10iii	0.95 (1)	2.24 (3)	2.929 (3)	129 (3)
N1—H1A···O9iii	0.94 (3)	2.16 (2)	2.992 (3)	146 (3)
N1—H1A···O14	0.94 (3)	2.40 (3)	2.985 (3)	120 (3)
N1—H1C···O16iii	0.95 (1)	1.96 (2)	2.811 (3)	148 (3)
N1—H1C···O6i	0.95 (1)	2.36 (3)	3.038 (3)	128 (3)
N1—H1D···O17	0.95 (3)	2.17 (3)	2.859 (3)	129 (3)
N1—H1D···O8i	0.95 (3)	2.47 (3)	3.097 (3)	124 (3)
N1—H1D···O5	0.95 (3)	2.60 (3)	3.203 (3)	122 (3)
N2—H2A···O16	0.95 (1)	2.00 (1)	2.923 (3)	164 (3)
N2—H2B···O4	0.95 (1)	1.93 (1)	2.852 (3)	165 (3)
N2—H2C···O11vi	0.95 (1)	2.00 (2)	2.912 (3)	162 (3)
N2—H2C···O7iv	0.95 (1)	2.65 (3)	3.169 (3)	115 (3)
N2—H2D···O3vii	0.94 (3)	2.36 (3)	3.089 (3)	134 (3)
N2—H2D···O14iii	0.94 (3)	2.29 (3)	2.961 (3)	128 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O12—H12A⋯O2i	0.947 (10)	1.802 (15)	2.715 (3)	161 (3)
O12—H12A⋯O1i	0.947 (10)	2.391 (16)	3.299 (3)	161 (3)
O12—H12B⋯O17ii	0.949 (10)	1.658 (12)	2.599 (3)	171 (4)
O16—H16B⋯O4iii	0.94 (3)	2.01 (3)	2.939 (3)	170 (3)
O16—H16A⋯O7	0.943 (10)	2.00 (2)	2.803 (3)	142 (3)
O17—H17A⋯O1	0.94 (3)	1.883 (16)	2.776 (3)	159 (3)
O17—H17B⋯O7iv	0.939 (10)	1.983 (12)	2.909 (3)	169 (3)
N1—H1B⋯O10iv	0.948 (10)	2.09 (3)	2.795 (3)	130 (3)
N1—H1B⋯O10ii	0.948 (10)	2.24 (3)	2.929 (3)	129 (3)
N1—H1A⋯O9ii	0.94 (3)	2.16 (2)	2.992 (3)	146 (3)
N1—H1A⋯O14	0.94 (3)	2.40 (3)	2.985 (3)	120 (3)
N1—H1C⋯O16ii	0.948 (10)	1.96 (2)	2.811 (3)	148 (3)
N1—H1C⋯O6v	0.948 (10)	2.36 (3)	3.038 (3)	128 (3)
N1—H1D⋯O17	0.95 (3)	2.17 (3)	2.859 (3)	129 (3)
N1—H1D⋯O8v	0.95 (3)	2.47 (3)	3.097 (3)	124 (3)
N1—H1D⋯O5	0.95 (3)	2.60 (3)	3.203 (3)	122 (3)
N2—H2A⋯O16	0.946 (10)	2.001 (14)	2.923 (3)	164 (3)
N2—H2B⋯O4	0.945 (10)	1.927 (14)	2.852 (3)	165 (3)
N2—H2C⋯O11vi	0.946 (10)	1.999 (15)	2.912 (3)	162 (3)
N2—H2C⋯O7iii	0.946 (10)	2.65 (3)	3.169 (3)	115 (3)
N2—H2D⋯O3vii	0.94 (3)	2.36 (3)	3.089 (3)	134 (3)
N2—H2D⋯O14ii	0.94 (3)	2.29 (3)	2.961 (3)	128 (3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .