Non-centrosymmetric Rb2Mn2(MoO4)3.

The title compound, dirubidium dimanganese(II) tris-(tetra-oxo-molyb-date), Rb2Mn2(MoO4)3, was prepared by solid-state reactions. The structure can be described as being composed of MnO6 octa-hedra sharing corners with MoO4 tetra-hedra. The three-dimensional framework contains cavities in which the rubidium ions are located. The Rb(+) cations are within distorted nine- and 12-vertex polyhedra. The pairs of different Mn(2+) and Rb(+) cations are each located on threefold rotation axes.. Rb2Mn2(MoO4)3 is isotypic with compounds of the Cs2 M 2Mo3O12 (M = Ni, Fe) family. A comparative structural description is provided between the structure of the title compound and those of related phases. Differences with structures such as alluaudite are discussed.

Related literature

For isotypic structures, see: Zolotova et al. (2011 ▶); Namsara­eva et al. (2011 ▶). For background to the physico-chemical properties of related compounds, see: Chaalia et al. (2012 ▶); Prabaharan et al. (1997 ▶); Ouerfelli et al. (2007 ▶); Hansen et al. (1988 ▶); Masquelier et al. (1995 ▶). For details of of the preparation and for structurally related compounds, see: Solodovnikov et al. (1986 ▶, 1998 ▶); Solodovnikov & Solodovnikova (1997 ▶); Tsyrenova et al. (2004 ▶); Bouzidi et al. (2014 ▶). For details of structurally different compounds, see: Brahim & Amor (2003 ▶); Warner et al. (1993 ▶); Korzenski et al. (1998 ▶); Chouaibi et al. (2001 ▶); Pertlik (1987 ▶); Antenucci et al. (1995 ▶); Zid et al. (2005 ▶); Hatert et al. (2004 ▶); Lii & Shih (1994 ▶). For bond lengths, see: Souilem et al. (2014 ▶); Frigui et al. (2012 ▶); Leclaire & Raveau (1988 ▶); Sebastian et al. (2003 ▶) and for bond-valence sums, see: Brown & Altermatt (1985 ▶).

Experimental

Crystal data

Rb2Mn2(MoO4)3

M = 760.64

Cubic,

a = 10.9002 (9) Å

V = 1295.10 (19) Å3

Z = 4

Mo Kα radiation

μ = 12.24 mm−1

T = 298 K

0.25 × 0.15 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.071, T max = 0.210

2949 measured reflections

916 independent reflections

838 reflections with I > 2σ(I)

R int = 0.044

2 standard reflections every 120 min intensity decay: 1.3%

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.079

S = 1.10

916 reflections

59 parameters

Δρmax = 1.03 e Å−3

Δρmin = −0.96 e Å−3

Absolute structure: Flack (1983 ▶), 264 Friedel pairs

Absolute structure parameter: 0.04 (2)

Data collection: CAD-4 EXPRESS (Duisenberg, 1992 ▶; Macíček & Yordanov, 1992 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2001 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814013099/ru2059sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814013099/ru2059Isup2.hkl

CCDC reference: 1006923

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

Rb2Mn2(MoO4)3	Dx = 3.901 Mg m−3
Mr = 760.64	Mo Kα radiation, λ = 0.71073 Å
Cubic, P213	Cell parameters from 25 reflections
Hall symbol: P 2ac 2ab 3	θ = 11–15°
a = 10.9002 (9) Å	µ = 12.24 mm−1
V = 1295.10 (19) Å3	T = 298 K
Z = 4	Prism, yellow
F(000) = 1384	0.25 × 0.15 × 0.10 mm

Enraf–Nonius CAD-4 diffractometer	838 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.044
Graphite monochromator	θmax = 26.9°, θmin = 2.6°
ω/2θ scans	h = −13→1
Absorption correction: ψ scan (North et al., 1968)	k = −1→13
Tmin = 0.071, Tmax = 0.210	l = −13→6
2949 measured reflections	2 standard reflections every 120 min
916 independent reflections	intensity decay: 1.3%

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0187P)2 + 14.7659P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.035	(Δ/σ)max < 0.001
wR(F2) = 0.079	Δρmax = 1.03 e Å−3
S = 1.10	Δρmin = −0.96 e Å−3
916 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
59 parameters	Extinction coefficient: 0.0049 (4)
0 restraints	Absolute structure: Flack (1983), 264 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (2)

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
Mo1	0.37706 (7)	0.52435 (7)	0.79714 (7)	0.0157 (2)
Mn1	0.38791 (13)	0.61209 (13)	1.11209 (13)	0.0197 (5)
Mn2	0.33762 (13)	0.83762 (13)	0.66238 (13)	0.0227 (6)
Rb1	0.04628 (12)	0.54628 (12)	0.95372 (12)	0.0487 (6)
Rb2	0.31889 (10)	0.18111 (10)	0.81889 (10)	0.0371 (5)
O1	0.3993 (13)	0.6707 (9)	0.7457 (11)	0.083 (4)
O2	0.2720 (11)	0.4448 (11)	0.7079 (10)	0.083 (4)
O3	0.3323 (11)	0.5164 (12)	0.9489 (8)	0.084 (4)
O4	0.5171 (12)	0.4546 (14)	0.7765 (13)	0.109 (5)

	U11	U22	U33	U12	U13	U23
Mo1	0.0163 (4)	0.0156 (4)	0.0152 (4)	0.0025 (3)	−0.0033 (3)	−0.0012 (3)
Mn1	0.0197 (5)	0.0197 (5)	0.0197 (5)	0.0016 (6)	0.0016 (6)	−0.0016 (6)
Mn2	0.0227 (6)	0.0227 (6)	0.0227 (6)	−0.0053 (6)	0.0053 (6)	0.0053 (6)
Rb1	0.0487 (6)	0.0487 (6)	0.0487 (6)	−0.0082 (6)	0.0082 (6)	0.0082 (6)
Rb2	0.0371 (5)	0.0371 (5)	0.0371 (5)	0.0042 (5)	−0.0042 (5)	0.0042 (5)
O1	0.113 (10)	0.041 (5)	0.096 (9)	−0.022 (7)	−0.024 (8)	0.029 (6)
O2	0.099 (9)	0.098 (9)	0.051 (6)	−0.054 (7)	−0.058 (6)	0.026 (6)
O3	0.102 (9)	0.128 (10)	0.021 (4)	−0.055 (8)	0.022 (5)	−0.033 (6)
O4	0.084 (9)	0.129 (11)	0.113 (11)	0.089 (9)	−0.019 (8)	0.004 (9)

Mo1—O1	1.708 (10)	Rb1—O3iii	3.135 (12)
Mo1—O4	1.721 (11)	Rb1—O3ix	3.135 (12)
Mo1—O3	1.726 (8)	Rb1—O2ii	3.407 (13)
Mo1—O2	1.734 (10)	Rb1—O2x	3.407 (13)
Mn1—O2i	2.125 (10)	Rb1—O2xi	3.407 (13)
Mn1—O2ii	2.125 (10)	Rb1—O4x	3.586 (13)
Mn1—O2iii	2.125 (10)	Rb1—O4ii	3.586 (13)
Mn1—O3	2.150 (9)	Rb1—O4xi	3.586 (13)
Mn1—O3iv	2.150 (9)	Rb2—O1xii	3.153 (15)
Mn1—O3v	2.150 (9)	Rb2—O1xiii	3.153 (15)
Mn2—O4vi	2.139 (10)	Rb2—O1iv	3.153 (15)
Mn2—O4vii	2.139 (10)	Rb2—O2xiv	3.160 (12)
Mn2—O4viii	2.139 (10)	Rb2—O2	3.160 (12)
Mn2—O1ix	2.142 (10)	Rb2—O2x	3.160 (12)
Mn2—O1iii	2.142 (10)	Rb2—O4xii	3.221 (17)
Mn2—O1	2.142 (10)	Rb2—O4iv	3.221 (17)
Rb1—O3	3.135 (12)	Rb2—O4xiii	3.221 (17)
O1—Mo1—O4	104.1 (7)	O2iii—Mn1—O3v	91.9 (4)
O1—Mo1—O3	113.7 (6)	O3—Mn1—O3v	88.2 (5)
O4—Mo1—O3	110.7 (6)	O3iv—Mn1—O3v	88.2 (5)
O1—Mo1—O2	112.1 (5)	O4vi—Mn2—O4vii	88.6 (5)
O4—Mo1—O2	107.0 (7)	O4vi—Mn2—O4viii	88.6 (5)
O3—Mo1—O2	109.0 (6)	O4vii—Mn2—O4viii	88.6 (5)
O2i—Mn1—O2ii	88.8 (5)	O4vi—Mn2—O1ix	168.3 (6)
O2i—Mn1—O2iii	88.8 (5)	O4vii—Mn2—O1ix	98.2 (5)
O2ii—Mn1—O2iii	88.8 (5)	O4viii—Mn2—O1ix	82.1 (6)
O2i—Mn1—O3	179.2 (5)	O4vi—Mn2—O1iii	82.1 (6)
O2ii—Mn1—O3	91.9 (4)	O4vii—Mn2—O1iii	168.3 (6)
O2iii—Mn1—O3	91.0 (6)	O4viii—Mn2—O1iii	98.2 (5)
O2i—Mn1—O3iv	91.9 (4)	O1ix—Mn2—O1iii	92.3 (6)
O2ii—Mn1—O3iv	91.0 (6)	O4vi—Mn2—O1	98.2 (5)
O2iii—Mn1—O3iv	179.2 (5)	O4vii—Mn2—O1	82.1 (6)
O3—Mn1—O3iv	88.2 (5)	O4viii—Mn2—O1	168.3 (6)
O2i—Mn1—O3v	91.0 (6)	O1ix—Mn2—O1	92.3 (6)
O2ii—Mn1—O3v	179.2 (5)	O1iii—Mn2—O1	92.3 (6)