Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101018017/br1335sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101018017/br1335Isup2.hkl |
Rb2S6 powder was prepared by reaction of stoichiometric amounts of rubidium metal (Strem, 99.9+%) and sulfur powder (Aldrich, 99.99%) in liquid ammonia (Fehér, 1975). Crystals of Rb2MnP2S6 were synthesized from a mixture of 0.1107 g (0.3044 mmol) of Rb2S6 powder, 0.0265 g (0.3046 mmol) of MnS powder (Strem, 99.9%), and 0.3127 g (1.4209 mmol) of P4S3 powder (Fluka, 98%), with 0.0503 g (0.3042 mmol) of RbBr (GFS, 99.9%) acting as a halide flux-growth solvent. The powders were ground together in an agate mortar inside a nitrogen-filled glove box, and were then loaded into fused-quartz tubing. The reaction tube was subsequently sealed under vacuum. After heating at 973 K for five days, the reaction vessel was allowed to cool to room temperature over seven days. Transparent yellow plate crystals of Rb2MnP2S6 were present throughout the reaction product, which also included MnS crystals, unreacted P4S3 powder, and RbBr.
Data collection: CrystalClear (Rigaku Corporation, 1999); cell refinement: CrystalClear (Rigaku Corporation, 1999); data reduction: CrystalClear (Rigaku Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: Molecular Structure Corporation, 1997-1999).
MnP2Rb2S6 | F(000) = 450 |
Mr = 480.18 | Dx = 2.809 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 6.1570 (12) Å | Cell parameters from 6144 reflections |
b = 12.308 (3) Å | θ = 1.7–26.1° |
c = 7.5610 (15) Å | µ = 11.00 mm−1 |
β = 97.74 (3)° | T = 293 K |
V = 567.8 (2) Å3 | Plate, yellow |
Z = 2 | 0.15 × 0.05 × 0.05 mm |
Rigaku APC8 diffractometer | 1110 independent reflections |
Radiation source: fine-focus sealed tube | 1034 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
Detector resolution: 0 pixels mm-1 | θmax = 26.1°, θmin = 3.2° |
ω scans | h = −7→7 |
Absorption correction: multi-scan REQABA Empirical Absorption Correction using REQABA (Jacobson, 1999) | k = −15→14 |
Tmin = 0.258, Tmax = 0.577 | l = −9→9 |
5210 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.055 | Secondary atom site location: difference Fourier map |
wR(F2) = 0.137 | w = 1/[σ2(Fo2) + (0.0001P)2 + 12.3434P] where P = (Fo2 + 2Fc2)/3 |
S = 1.32 | (Δ/σ)max < 0.001 |
1110 reflections | Δρmax = 1.06 e Å−3 |
52 parameters | Δρmin = −0.73 e Å−3 |
MnP2Rb2S6 | V = 567.8 (2) Å3 |
Mr = 480.18 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.1570 (12) Å | µ = 11.00 mm−1 |
b = 12.308 (3) Å | T = 293 K |
c = 7.5610 (15) Å | 0.15 × 0.05 × 0.05 mm |
β = 97.74 (3)° |
Rigaku APC8 diffractometer | 1110 independent reflections |
Absorption correction: multi-scan REQABA Empirical Absorption Correction using REQABA (Jacobson, 1999) | 1034 reflections with I > 2σ(I) |
Tmin = 0.258, Tmax = 0.577 | Rint = 0.055 |
5210 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.137 | w = 1/[σ2(Fo2) + (0.0001P)2 + 12.3434P] where P = (Fo2 + 2Fc2)/3 |
S = 1.32 | Δρmax = 1.06 e Å−3 |
1110 reflections | Δρmin = −0.73 e Å−3 |
52 parameters |
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 | ||
Rb1 | 0.22904 (19) | 0.17337 (9) | 0.02473 (16) | 0.0383 (4) | |
Mn1 | 0.0000 | 0.0000 | 0.5000 | 0.0233 (5) | |
P1 | 0.4702 (4) | 0.04003 (19) | 0.6252 (3) | 0.0166 (5) | |
S1 | 0.2286 (4) | −0.0774 (2) | 0.2535 (3) | 0.0251 (6) | |
S2 | 0.3017 (4) | −0.0697 (2) | 0.7518 (3) | 0.0235 (5) | |
S3 | 0.2731 (4) | 0.1673 (2) | 0.5466 (4) | 0.0263 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rb1 | 0.0377 (6) | 0.0316 (6) | 0.0425 (7) | 0.0101 (5) | −0.0056 (5) | −0.0046 (5) |
Mn1 | 0.0109 (9) | 0.0270 (11) | 0.0320 (12) | −0.0009 (8) | 0.0030 (8) | 0.0000 (9) |
P1 | 0.0119 (10) | 0.0161 (11) | 0.0220 (12) | −0.0011 (8) | 0.0032 (9) | −0.0010 (9) |
S1 | 0.0159 (11) | 0.0325 (13) | 0.0262 (13) | −0.0047 (10) | −0.0003 (9) | −0.0068 (10) |
S2 | 0.0166 (11) | 0.0275 (13) | 0.0273 (13) | −0.0005 (9) | 0.0061 (9) | 0.0093 (10) |
S3 | 0.0194 (11) | 0.0159 (11) | 0.0445 (16) | 0.0038 (9) | 0.0071 (11) | 0.0005 (10) |
Rb1—S2i | 3.393 (3) | Mn1—P1 | 2.964 (2) |
Rb1—S3ii | 3.446 (3) | Mn1—P1vii | 2.964 (2) |
Rb1—S1iii | 3.488 (3) | P1—S1i | 2.008 (3) |
Rb1—S1iv | 3.489 (3) | P1—S2 | 2.021 (3) |
Rb1—S1 | 3.538 (3) | P1—S3 | 2.022 (3) |
Rb1—S3v | 3.663 (3) | P1—P1i | 2.208 (5) |
Rb1—S2v | 3.695 (3) | P1—Rb1viii | 3.903 (3) |
Rb1—S2iv | 3.782 (3) | P1—Rb1ix | 3.986 (3) |
Rb1—S3vi | 3.866 (3) | P1—Rb1i | 4.002 (3) |
Rb1—P1v | 3.903 (3) | S1—P1i | 2.008 (3) |
Rb1—S3 | 3.919 (3) | S1—Rb1iii | 3.488 (3) |
Rb1—P1ii | 3.986 (3) | S1—Rb1x | 3.489 (3) |
Mn1—S2 | 2.619 (3) | S2—Rb1i | 3.393 (3) |
Mn1—S2vii | 2.619 (3) | S2—Rb1viii | 3.695 (3) |
Mn1—S3vii | 2.652 (3) | S2—Rb1x | 3.782 (3) |
Mn1—S3 | 2.652 (3) | S3—Rb1ix | 3.446 (3) |
Mn1—S1vii | 2.659 (3) | S3—Rb1viii | 3.663 (3) |
Mn1—S1 | 2.659 (3) | S3—Rb1xi | 3.866 (3) |
S2i—Rb1—S3ii | 146.56 (8) | S3—Mn1—S1 | 89.15 (8) |
S2i—Rb1—S1iii | 137.51 (7) | S1vii—Mn1—S1 | 180.00 (7) |
S3ii—Rb1—S1iii | 67.94 (7) | S2—Mn1—P1 | 41.88 (7) |
S2i—Rb1—S1iv | 95.04 (7) | S2vii—Mn1—P1 | 138.12 (7) |
S3ii—Rb1—S1iv | 59.03 (6) | S3vii—Mn1—P1 | 138.26 (7) |
S1iii—Rb1—S1iv | 126.14 (7) | S3—Mn1—P1 | 41.74 (7) |
S2i—Rb1—S1 | 59.02 (6) | S1vii—Mn1—P1 | 107.65 (7) |
S3ii—Rb1—S1 | 114.75 (7) | S1—Mn1—P1 | 72.35 (7) |
S1iii—Rb1—S1 | 86.88 (7) | S2—Mn1—P1vii | 138.12 (7) |
S1iv—Rb1—S1 | 122.48 (4) | S2vii—Mn1—P1vii | 41.88 (7) |
S2i—Rb1—S3v | 108.21 (7) | S3vii—Mn1—P1vii | 41.74 (7) |
S3ii—Rb1—S3v | 103.17 (7) | S3—Mn1—P1vii | 138.26 (7) |
S1iii—Rb1—S3v | 63.83 (6) | S1vii—Mn1—P1vii | 72.35 (7) |
S1iv—Rb1—S3v | 118.79 (7) | S1—Mn1—P1vii | 107.65 (7) |
S1—Rb1—S3v | 118.02 (6) | P1—Mn1—P1vii | 180.0 |
S2i—Rb1—S2v | 79.31 (7) | S1i—P1—S2 | 115.95 (15) |
S3ii—Rb1—S2v | 130.39 (7) | S1i—P1—S3 | 115.97 (16) |
S1iii—Rb1—S2v | 62.47 (6) | S2—P1—S3 | 109.32 (14) |
S1iv—Rb1—S2v | 166.73 (7) | S1i—P1—P1i | 104.14 (16) |
S1—Rb1—S2v | 64.84 (6) | S2—P1—P1i | 105.25 (17) |
S3v—Rb1—S2v | 53.25 (6) | S3—P1—P1i | 104.85 (18) |
S2i—Rb1—S2iv | 124.45 (7) | S1i—P1—Mn1 | 170.44 (13) |
S3ii—Rb1—S2iv | 64.55 (6) | S2—P1—Mn1 | 59.90 (9) |
S1iii—Rb1—S2iv | 88.49 (6) | S3—P1—Mn1 | 60.85 (9) |
S1iv—Rb1—S2iv | 61.67 (6) | P1i—P1—Mn1 | 85.41 (12) |
S1—Rb1—S2iv | 175.16 (6) | S1i—P1—Rb1viii | 88.52 (11) |
S3v—Rb1—S2iv | 58.40 (6) | S2—P1—Rb1viii | 68.96 (10) |
S2v—Rb1—S2iv | 111.66 (4) | S3—P1—Rb1viii | 68.02 (10) |
S2i—Rb1—S3vi | 59.65 (6) | P1i—P1—Rb1viii | 167.32 (15) |
S3ii—Rb1—S3vi | 114.59 (7) | Mn1—P1—Rb1viii | 81.95 (6) |
S1iii—Rb1—S3vi | 145.35 (7) | S1i—P1—Rb1ix | 61.07 (10) |
S1iv—Rb1—S3vi | 61.66 (6) | S2—P1—Rb1ix | 157.75 (12) |
S1—Rb1—S3vi | 118.64 (6) | S3—P1—Rb1ix | 59.85 (9) |
S3v—Rb1—S3vi | 82.73 (7) | P1i—P1—Rb1ix | 96.60 (13) |
S2v—Rb1—S3vi | 105.37 (6) | Mn1—P1—Rb1ix | 119.00 (7) |
S2iv—Rb1—S3vi | 65.04 (6) | Rb1viii—P1—Rb1ix | 88.79 (5) |
S2i—Rb1—P1v | 80.80 (6) | S1i—P1—Rb1i | 62.06 (10) |
S3ii—Rb1—P1v | 132.34 (7) | S2—P1—Rb1i | 57.95 (9) |
S1iii—Rb1—P1v | 75.61 (6) | S3—P1—Rb1i | 155.38 (13) |
S1iv—Rb1—P1v | 136.90 (7) | P1i—P1—Rb1i | 99.13 (13) |
S1—Rb1—P1v | 92.12 (6) | Mn1—P1—Rb1i | 116.56 (7) |
S3v—Rb1—P1v | 30.79 (5) | Rb1viii—P1—Rb1i | 87.38 (6) |
S2v—Rb1—P1v | 30.69 (5) | Rb1ix—P1—Rb1i | 123.07 (6) |
S2iv—Rb1—P1v | 85.39 (6) | P1i—S1—Mn1 | 98.10 (12) |
S3vi—Rb1—P1v | 80.12 (6) | P1i—S1—Rb1iii | 167.00 (13) |
S2i—Rb1—S3 | 63.43 (6) | Mn1—S1—Rb1iii | 94.77 (7) |
S3ii—Rb1—S3 | 84.78 (7) | P1i—S1—Rb1x | 88.68 (11) |
S1iii—Rb1—S3 | 122.79 (7) | Mn1—S1—Rb1x | 89.44 (8) |
S1iv—Rb1—S3 | 62.75 (6) | Rb1iii—S1—Rb1x | 89.66 (6) |
S1—Rb1—S3 | 59.72 (6) | P1i—S1—Rb1 | 87.84 (11) |
S3v—Rb1—S3 | 171.55 (8) | Mn1—S1—Rb1 | 93.76 (8) |
S2v—Rb1—S3 | 123.34 (6) | Rb1iii—S1—Rb1 | 93.12 (7) |
S2iv—Rb1—S3 | 124.33 (6) | Rb1x—S1—Rb1 | 175.57 (8) |
S3vi—Rb1—S3 | 91.41 (7) | P1—S2—Mn1 | 78.22 (10) |
P1v—Rb1—S3 | 142.13 (6) | P1—S2—Rb1i | 91.74 (10) |
S2i—Rb1—P1ii | 124.99 (6) | Mn1—S2—Rb1i | 163.36 (10) |
S3ii—Rb1—P1ii | 30.48 (5) | P1—S2—Rb1viii | 80.34 (11) |
S1iii—Rb1—P1ii | 95.94 (6) | Mn1—S2—Rb1viii | 90.77 (7) |
S1iv—Rb1—P1ii | 30.25 (5) | Rb1i—S2—Rb1viii | 100.69 (7) |
S1—Rb1—P1ii | 130.71 (7) | P1—S2—Rb1x | 106.70 (11) |
S3v—Rb1—P1ii | 106.90 (6) | Mn1—S2—Rb1x | 83.92 (7) |
S2v—Rb1—P1ii | 154.75 (6) | Rb1i—S2—Rb1x | 86.37 (6) |
S2iv—Rb1—P1ii | 51.22 (5) | Rb1viii—S2—Rb1x | 170.01 (7) |
S3vi—Rb1—P1ii | 84.80 (6) | P1—S3—Mn1 | 77.41 (10) |
P1v—Rb1—P1ii | 136.32 (6) | P1—S3—Rb1ix | 89.67 (10) |
S3—Rb1—P1ii | 78.48 (6) | Mn1—S3—Rb1ix | 160.30 (10) |
S2—Mn1—S2vii | 180.0 | P1—S3—Rb1viii | 81.19 (11) |
S2—Mn1—S3vii | 102.54 (8) | Mn1—S3—Rb1viii | 90.97 (8) |
S2vii—Mn1—S3vii | 77.46 (8) | Rb1ix—S3—Rb1viii | 101.82 (8) |
S2—Mn1—S3 | 77.46 (8) | P1—S3—Rb1xi | 152.64 (12) |
S2vii—Mn1—S3 | 102.54 (8) | Mn1—S3—Rb1xi | 81.83 (6) |
S3vii—Mn1—S3 | 180.00 (10) | Rb1ix—S3—Rb1xi | 114.59 (7) |
S2—Mn1—S1vii | 89.90 (8) | Rb1viii—S3—Rb1xi | 81.54 (6) |
S2vii—Mn1—S1vii | 90.10 (8) | P1—S3—Rb1 | 105.55 (12) |
S3vii—Mn1—S1vii | 89.15 (8) | Mn1—S3—Rb1 | 85.67 (7) |
S3—Mn1—S1vii | 90.85 (8) | Rb1ix—S3—Rb1 | 83.53 (7) |
S2—Mn1—S1 | 90.10 (8) | Rb1viii—S3—Rb1 | 171.55 (8) |
S2vii—Mn1—S1 | 89.90 (8) | Rb1xi—S3—Rb1 | 90.30 (6) |
S3vii—Mn1—S1 | 90.85 (8) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x, −y, −z; (iv) −x+1/2, y+1/2, −z+1/2; (v) x, y, z−1; (vi) x+1/2, −y+1/2, z−1/2; (vii) −x, −y, −z+1; (viii) x, y, z+1; (ix) x+1/2, −y+1/2, z+1/2; (x) −x+1/2, y−1/2, −z+1/2; (xi) x−1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | MnP2Rb2S6 |
Mr | 480.18 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 6.1570 (12), 12.308 (3), 7.5610 (15) |
β (°) | 97.74 (3) |
V (Å3) | 567.8 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 11.00 |
Crystal size (mm) | 0.15 × 0.05 × 0.05 |
Data collection | |
Diffractometer | Rigaku APC8 diffractometer |
Absorption correction | Multi-scan REQABA Empirical Absorption Correction using REQABA (Jacobson, 1999) |
Tmin, Tmax | 0.258, 0.577 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5210, 1110, 1034 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.619 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.137, 1.32 |
No. of reflections | 1110 |
No. of parameters | 52 |
w = 1/[σ2(Fo2) + (0.0001P)2 + 12.3434P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.06, −0.73 |
Computer programs: CrystalClear (Rigaku Corporation, 1999), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), Molecular Structure Corporation, 1997-1999).
Mn1—S2 | 2.619 (3) | P1—S1i | 2.008 (3) |
Mn1—S3 | 2.652 (3) | P1—S2 | 2.021 (3) |
Mn1—S1 | 2.659 (3) | P1—S3 | 2.022 (3) |
Mn1—P1 | 2.964 (2) | P1—P1i | 2.208 (5) |
S2—Mn1—S3ii | 102.54 (8) | S1i—P1—S2 | 115.95 (15) |
S2—Mn1—S3 | 77.46 (8) | S1i—P1—S3 | 115.97 (16) |
S2—Mn1—S1ii | 89.90 (8) | S2—P1—S3 | 109.32 (14) |
S3—Mn1—S1ii | 90.85 (8) | S1i—P1—P1i | 104.14 (16) |
S2—Mn1—S1 | 90.10 (8) | S2—P1—P1i | 105.25 (17) |
S3—Mn1—S1 | 89.15 (8) | S3—P1—P1i | 104.85 (18) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y, −z+1. |
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There are seven known compounds of the type A2MP2Q6 (A = K, Rb, Cs; M = Mn, Fe; and Q = S, Se), including K2FeP2S6 (Carrillo-Cabrera, et al., 1992, 1994); K2MnP2S6 (Menzel et al., 1994);
K2MnP2Se6, Rb2MnP2Se6, Cs2MnP2Se6, K2FeP2Se6, and Cs2FeP2Se6 (McCarthy & Kanatzidis, 1995). The title compound is typical of this class of compounds. The first two compounds listed above were synthesized from the elements, while the final five were synthesized in polychalcophosphate flux. We were able to prepare rubidium manganese hexathiodiphosphate using molten rubidium bromide as a flux-growth solvent, similar to the synthesis of KNb2PS10 (Do & Yun, 1996), which was performed in an eutectic mixture of LiCl and KCl. As in the other members of this class, the structure is related to that of CdCl2 (Brec, 1986, and references therein; see Fig. 1).