RbMn₆(As₂O₇)₂(As₃O₁₀): a new manganese(II) arsenate

Single crystals of rubidium manganese arsenate, RbMn₆(As₂O₇)₂(As₃O₁₀), have been prepared by a solid-state reaction at 1173 K. The compound crystallizes in the monoclinic system, space group P2₁/m. The structure consists of a complex network of edge-sharing MnO₆ octahedra, forming folded layers that are linked together by As₂O₇ and As₃O₁₀ groups, which is highly unusual. This arrangement delimits a tunnel parallel to the a-axis direction which accommodates Rb⁺.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](Mn-O) = 0.006 Å
• R factor = 0.037
• wR factor = 0.111
• Data-to-parameter ratio = 12.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT213_ALERT_2_B Atom O6      has ADP max/min Ratio .............       4.10 oblate

Alert level C
PLAT213_ALERT_2_C Atom O13     has ADP max/min Ratio .............       3.30 oblate
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       2.85 Ratio
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ....        O13

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Diamond (Brandenburg, 1998); software used to prepare material for publication: SHELXL97.

Rubidium manganese arsenate(1;6;7)

Crystal data

As7Mn6O24Rb	F(000) = 1220
Mr = 1323.53	Dx = 4.358 Mg m^−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 25 reflections
a = 5.555 (1) Å	θ = 1.5–27.0°
b = 27.830 (9) Å	µ = 17.56 mm^−1
c = 6.842 (2) Å	T = 293 K
β = 107.56 (2)°	Prismatic, colourless
V = 1008.5 (5) Å^3	0.1 × 0.05 × 0.04 mm
Z = 2

Data collection

Enarf–Nonius CAD-4 diffractometer	1726 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.079
Graphite monochromator	θmax = 27.0°, θmin = 1.5°
ω/2θ scans	h = 0→7
Absorption correction: ψ scan (North et al., 1968)	k = 0→35
Tmin = 0.363, Tmax = 0.495	l = −8→8
2461 measured reflections	2 standard reflections every 120 min
2240 independent reflections	intensity decay: 0.4%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	w = 1/[σ^2(Fo^2) + (0.0524P)^2 + 3.8056P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.111	(Δ/σ)max < 0.001
S = 1.09	Δρmax = 1.58 e Å^−3
2240 reflections	Δρmin = −1.47 e Å^−3
179 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0007 (2)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
As1	0.27497 (14)	0.47698 (3)	0.69774 (12)	0.0063 (2)
As2	0.68483 (15)	0.38723 (3)	0.87410 (12)	0.0069 (2)
As3	0.5271 (2)	0.2500	0.56840 (17)	0.0069 (3)
As4	0.22919 (14)	0.33587 (3)	0.27565 (12)	0.0067 (2)
Rb	0.6964 (2)	0.2500	0.10323 (18)	0.0157 (3)
Mn1	−0.1836 (2)	0.54331 (5)	0.82064 (19)	0.0092 (3)
Mn2	−0.2149 (2)	0.40166 (5)	0.40127 (18)	0.0085 (3)
Mn3	0.1078 (2)	0.31554 (4)	0.74999 (18)	0.0085 (3)
O1	0.8760 (10)	0.4017 (2)	0.1078 (8)	0.0087 (11)
O2	0.1082 (11)	0.4523 (2)	0.4749 (9)	0.0106 (12)
O3	0.4178 (11)	0.52893 (19)	0.6737 (9)	0.0100 (11)
O4	0.8293 (15)	0.2500	0.7056 (13)	0.0133 (18)
O5	0.3887 (11)	0.38634 (19)	0.2693 (9)	0.0106 (12)
O6	0.8518 (11)	0.3769 (2)	0.7101 (8)	0.0122 (12)
O7	0.4942 (11)	0.2986 (2)	0.4071 (9)	0.0138 (12)
O8	0.0451 (10)	0.3365 (2)	0.4307 (8)	0.0104 (12)
O9	0.1132 (11)	0.4800 (2)	0.8687 (9)	0.0117 (12)
O10	0.1027 (11)	0.3067 (2)	0.0578 (8)	0.0116 (12)
O11	0.3127 (15)	0.2500	0.6908 (12)	0.0098 (16)
O12	0.4812 (11)	0.3433 (2)	0.8713 (10)	0.0160 (13)
O13	0.5441 (13)	0.4425 (2)	0.7970 (11)	0.0250 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
As1	0.0062 (4)	0.0067 (4)	0.0068 (4)	0.0002 (3)	0.0032 (3)	−0.0005 (3)
As2	0.0051 (4)	0.0089 (4)	0.0070 (4)	0.0005 (3)	0.0023 (3)	−0.0008 (3)
As3	0.0055 (5)	0.0079 (5)	0.0081 (5)	0.000	0.0033 (4)	0.000
As4	0.0068 (4)	0.0070 (4)	0.0075 (4)	−0.0007 (3)	0.0041 (3)	−0.0010 (3)
Rb	0.0164 (6)	0.0182 (6)	0.0150 (6)	0.000	0.0084 (5)	0.000
Mn1	0.0083 (6)	0.0112 (6)	0.0091 (6)	0.0005 (5)	0.0043 (5)	0.0019 (5)
Mn2	0.0075 (6)	0.0106 (6)	0.0086 (6)	−0.0005 (5)	0.0044 (5)	0.0006 (5)
Mn3	0.0095 (6)	0.0088 (6)	0.0083 (6)	0.0010 (5)	0.0042 (5)	−0.0003 (5)
O1	0.010 (3)	0.010 (3)	0.007 (3)	−0.001 (2)	0.003 (2)	0.002 (2)
O2	0.009 (3)	0.013 (3)	0.012 (3)	−0.003 (2)	0.005 (2)	−0.002 (2)
O3	0.012 (3)	0.004 (3)	0.018 (3)	−0.001 (2)	0.009 (2)	0.000 (2)
O4	0.004 (4)	0.022 (5)	0.013 (4)	0.000	0.001 (3)	0.000
O5	0.010 (3)	0.003 (3)	0.019 (3)	−0.002 (2)	0.004 (2)	0.000 (2)
O6	0.014 (3)	0.018 (3)	0.008 (3)	0.003 (2)	0.009 (2)	−0.002 (2)
O7	0.014 (3)	0.010 (3)	0.019 (3)	0.008 (2)	0.007 (2)	0.008 (2)
O8	0.010 (3)	0.015 (3)	0.010 (3)	0.008 (2)	0.007 (2)	0.006 (2)
O9	0.013 (3)	0.013 (3)	0.013 (3)	−0.001 (2)	0.009 (2)	−0.002 (2)
O10	0.017 (3)	0.012 (3)	0.006 (3)	−0.005 (2)	0.004 (2)	0.000 (2)
O11	0.011 (4)	0.014 (4)	0.008 (4)	0.000	0.008 (3)	0.000
O12	0.012 (3)	0.017 (3)	0.021 (3)	−0.007 (2)	0.007 (3)	0.000 (3)
O13	0.017 (3)	0.016 (3)	0.037 (4)	0.012 (3)	−0.001 (3)	0.003 (3)

Geometric parameters (Å, º)

As1—O2	1.674 (6)	Rb—O12^vi	3.090 (6)
As1—O9	1.679 (6)	Rb—O12^v	3.090 (6)
As1—O3	1.681 (5)	Rb—O8^iii	3.456 (6)
As1—O13	1.733 (6)	Rb—O8^iv	3.456 (6)
As2—O12	1.661 (6)	Mn1—O9^vii	2.143 (6)
As2—O1^i	1.680 (5)	Mn1—O3^viii	2.175 (6)
As2—O6	1.683 (5)	Mn1—O2^ix	2.189 (6)
As2—O13	1.734 (6)	Mn1—O1^x	2.235 (6)
As3—O11	1.650 (8)	Mn1—O5^ix	2.255 (6)
As3—O4	1.658 (8)	Mn1—O9	2.366 (6)
As3—O7^ii	1.721 (6)	Mn2—O6^viii	2.145 (6)
As3—O7	1.721 (6)	Mn2—O5^viii	2.156 (6)
As4—O10	1.656 (6)	Mn2—O1^viii	2.213 (5)
As4—O5	1.668 (5)	Mn2—O2	2.217 (6)
As4—O8	1.681 (5)	Mn2—O3^ix	2.217 (6)
As4—O7	1.803 (6)	Mn2—O8	2.289 (6)
Rb—O10^iii	2.846 (6)	Mn3—O10^i	2.129 (6)
Rb—O10^iv	2.846 (6)	Mn3—O12	2.134 (6)
Rb—O7	2.971 (6)	Mn3—O8	2.185 (5)
Rb—O7^ii	2.971 (6)	Mn3—O6^viii	2.186 (6)
Rb—O11^v	2.980 (8)	Mn3—O11	2.251 (5)
Rb—O4^v	3.026 (8)	Mn3—O4^viii	2.351 (5)
O2—As1—O9	113.0 (3)	O10^iv—Rb—O8^iii	98.57 (15)
O2—As1—O3	114.3 (3)	O7^ii—Rb—O8^iii	96.89 (15)
O9—As1—O3	113.1 (3)	O11^v—Rb—O8^iii	135.62 (9)
O2—As1—O13	107.7 (3)	O4^v—Rb—O8^iii	109.98 (14)
O9—As1—O13	109.6 (3)	O12^vi—Rb—O8^iii	166.54 (15)
O3—As1—O13	97.9 (3)	O10^iii—Rb—O8^iv	98.57 (15)
O12—As2—O1^i	114.9 (3)	O7—Rb—O8^iv	96.89 (15)
O12—As2—O6	112.2 (3)	O11^v—Rb—O8^iv	135.62 (9)
O1^i—As2—O6	111.0 (3)	O4^v—Rb—O8^iv	109.98 (14)
O12—As2—O13	113.9 (3)	O12^v—Rb—O8^iv	166.54 (15)
O1^i—As2—O13	100.0 (3)	O9^vii—Mn1—O3^viii	105.0 (2)
O6—As2—O13	103.7 (3)	O9^vii—Mn1—O2^ix	154.8 (2)
O11—As3—O4	118.4 (4)	O3^viii—Mn1—O2^ix	92.0 (2)
O11—As3—O7^ii	111.9 (2)	O9^vii—Mn1—O1^x	95.3 (2)
O4—As3—O7^ii	104.9 (3)	O3^viii—Mn1—O1^x	146.3 (2)
O11—As3—O7	111.9 (2)	O9^vii—Mn1—O5^ix	117.4 (2)
O4—As3—O7	104.9 (3)	O3^viii—Mn1—O9	119.8 (2)
O7^ii—As3—O7	103.7 (4)	O1^x—Mn1—O9	91.4 (2)
O10—As4—O5	118.3 (3)	O5^ix—Mn1—O9	163.2 (2)
O10—As4—O8	113.5 (3)	O6^viii—Mn2—O5^viii	101.6 (2)
O5—As4—O8	115.9 (3)	O6^viii—Mn2—O1^viii	151.0 (2)
O10—As4—O7	103.2 (3)	O5^viii—Mn2—O1^viii	96.0 (2)
O5—As4—O7	97.9 (3)	O6^viii—Mn2—O2	95.3 (2)
O8—As4—O7	104.6 (3)	O5^viii—Mn2—O2	151.1 (2)
O10^iii—Rb—O7	107.67 (17)	O6^viii—Mn2—O3^ix	115.6 (2)
O10^iv—Rb—O7	143.95 (16)	O1^viii—Mn2—O3^ix	91.6 (2)
O10^iii—Rb—O7^ii	143.95 (16)	O5^viii—Mn2—O8	114.7 (2)
O10^iv—Rb—O7^ii	107.67 (17)	O2—Mn2—O8	92.1 (2)
O10^iii—Rb—O11^v	105.12 (17)	O3^ix—Mn2—O8	166.8 (2)
O10^iv—Rb—O11^v	105.12 (17)	O10^i—Mn3—O8	166.9 (2)
O7—Rb—O11^v	110.44 (17)	O12—Mn3—O8	97.8 (2)
O7^ii—Rb—O11^v	110.44 (17)	O10^i—Mn3—O6^viii	90.7 (2)
O7—Rb—O4^v	151.10 (12)	O12—Mn3—O6^viii	106.5 (2)
O7^ii—Rb—O4^v	151.10 (12)	O10^i—Mn3—O11	104.0 (2)
O10^iii—Rb—O12^vi	127.33 (16)	O6^viii—Mn3—O11	162.9 (3)
O7—Rb—O12^vi	124.96 (17)	O12—Mn3—O4^viii	148.9 (2)
O10^iv—Rb—O12^v	127.33 (16)	O8—Mn3—O4^viii	100.2 (3)
O7^ii—Rb—O12^v	124.96 (17)	O6^viii—Mn3—O4^viii	102.3 (2)
O12^vi—Rb—O12^v	114.4 (2)

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