Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103014082/iz1033sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103014082/iz1033Isup2.hkl |
Single crystals of MnSbSe2I were obtained as a by-product of the reaction of Sm (1.20 mmol, Alfa, 40 mesh, 99.9%), Mn (0.20 mmol, Alfa, 100 mesh, 99.9%), Sb (0.20 mmol, Alfa, 325 mesh, 99.5%) and Se (2.40 mmol, Alfa, 325 mesh, 99.99%) in a fused-silica tube to which a small amount of I2 was added. The reaction tube was heated at 1223 K for 4 d before being cooled to 973 K at a rate of 3 K h−1, at which point the furnace was turned off. The final product consisted mainly of golden plate-like crystals of SmSe3 and a few black prisms of MnSbSe2I. Qualitative energy-dispersive X-ray analysis performed on several of these prisms revealed an average composition (at. %) of 19 (2)% Mn, 22 (2)% Sb, 39 (2)% Se and 21 (2)% I, in good agreement with that deduced from the single-crystal X-ray analysis. No trace of Sm could be detected.
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: ATOMS 5.1 (Dowty, 1999); software used to prepare material for publication: SHELXTL 5.1.
Fig. 1. (a) MnSbSe2I viewed along the b axis. (b) UFeS3 viewed along the a axis. Displacement ellipsoids are drawn at the 99% probability level in both cases. |
MnSbSe2I | F(000) = 788 |
Mr = 461.51 | Dx = 5.645 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2y | Cell parameters from 2097 reflections |
a = 13.319 (3) Å | θ = 3.1–28.6° |
b = 4.0359 (8) Å | µ = 26.21 mm−1 |
c = 10.105 (2) Å | T = 153 K |
β = 91.27 (3)° | Prism, black |
V = 543.08 (19) Å3 | 0.19 × 0.04 × 0.02 mm |
Z = 4 |
Bruker SMART 1000 CCD area-detector diffractometer | 737 independent reflections |
Radiation source: fine-focus sealed tube | 709 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
0.3° ω scans | θmax = 28.6°, θmin = 2.0° |
Absorption correction: numerical XP in SHELXTL (Sheldrick, 1997) | h = −17→17 |
Tmin = 0.145, Tmax = 0.656 | k = −5→5 |
2404 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)] = 0.026 | w = 1/[σ2(Fo2) + (0.04Fo2)2] |
wR(F2) = 0.071 | (Δ/σ)max < 0.001 |
S = 1.37 | Δρmax = 2.11 e Å−3 |
737 reflections | Δρmin = −1.63 e Å−3 |
34 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0022 (3) |
MnSbSe2I | V = 543.08 (19) Å3 |
Mr = 461.51 | Z = 4 |
Monoclinic, C2/m | Mo Kα radiation |
a = 13.319 (3) Å | µ = 26.21 mm−1 |
b = 4.0359 (8) Å | T = 153 K |
c = 10.105 (2) Å | 0.19 × 0.04 × 0.02 mm |
β = 91.27 (3)° |
Bruker SMART 1000 CCD area-detector diffractometer | 737 independent reflections |
Absorption correction: numerical XP in SHELXTL (Sheldrick, 1997) | 709 reflections with I > 2σ(I) |
Tmin = 0.145, Tmax = 0.656 | Rint = 0.026 |
2404 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 34 parameters |
wR(F2) = 0.071 | 0 restraints |
S = 1.37 | Δρmax = 2.11 e Å−3 |
737 reflections | Δρmin = −1.63 e Å−3 |
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 | ||
I1 | 0.36336 (3) | 0.0000 | 0.07710 (4) | 0.01207 (17) | |
Sb1 | 0.29385 (3) | 0.0000 | 0.68476 (4) | 0.01329 (18) | |
Se1 | 0.07442 (4) | 0.0000 | 0.25801 (6) | 0.01032 (18) | |
Se2 | 0.36110 (4) | 0.0000 | 0.44523 (6) | 0.00988 (19) | |
Mn1 | 0.0000 | 0.0000 | 0.5000 | 0.0115 (3) | |
Mn2 | 0.0000 | 0.0000 | 0.0000 | 0.0116 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.0109 (2) | 0.0113 (3) | 0.0140 (3) | 0.000 | 0.00066 (16) | 0.000 |
Sb1 | 0.0145 (3) | 0.0132 (3) | 0.0122 (3) | 0.000 | 0.00112 (17) | 0.000 |
Se1 | 0.0111 (3) | 0.0098 (3) | 0.0099 (3) | 0.000 | −0.0028 (2) | 0.000 |
Se2 | 0.0094 (3) | 0.0104 (3) | 0.0097 (3) | 0.000 | −0.0015 (2) | 0.000 |
Mn1 | 0.0106 (6) | 0.0113 (6) | 0.0125 (7) | 0.000 | 0.0005 (5) | 0.000 |
Mn2 | 0.0115 (6) | 0.0106 (6) | 0.0127 (6) | 0.000 | 0.0002 (5) | 0.000 |
I1—Mn2i | 2.8380 (5) | Se1—I1xii | 3.8843 (10) |
I1—Mn2ii | 2.8380 (5) | Se1—I1v | 4.0436 (9) |
I1—Se2 | 3.7208 (10) | Se1—I1vi | 4.0436 (9) |
I1—Sb1iii | 3.8041 (9) | Se2—Mn1i | 2.7849 (6) |
I1—Sb1iv | 3.8041 (9) | Se2—Mn1ii | 2.7849 (6) |
I1—Se1i | 3.8843 (10) | Se2—Sb1iv | 3.1523 (8) |
I1—Se1ii | 3.8843 (10) | Se2—Sb1iii | 3.1523 (8) |
I1—I1v | 3.9257 (10) | Se2—I1ix | 5.4894 (9) |
I1—I1vi | 3.9257 (10) | Se2—I1viii | 5.4894 (9) |
I1—I1vii | 3.9910 (12) | Mn1—Se1xiii | 2.6590 (9) |
I1—I1viii | 4.0359 (8) | Mn1—Se2xi | 2.7849 (6) |
I1—I1ix | 4.0359 (8) | Mn1—Se2iii | 2.7849 (6) |
I1—Se1v | 4.0436 (9) | Mn1—Se2xii | 2.7849 (6) |
I1—Se1vi | 4.0436 (9) | Mn1—Se2iv | 2.7849 (6) |
I1—Sb1x | 4.0514 (11) | Mn1—I1iii | 5.0301 (12) |
Sb1—Se2 | 2.5995 (9) | Mn1—I1xi | 5.0301 (12) |
Sb1—Se1iii | 2.7277 (6) | Mn1—I1iv | 5.0301 (11) |
Sb1—Se1iv | 2.7277 (6) | Mn1—I1xii | 5.0301 (11) |
Sb1—Se2iv | 3.1523 (8) | Mn2—Se1xiv | 2.7687 (9) |
Sb1—Se2iii | 3.1523 (8) | Mn2—I1xi | 2.8380 (5) |
Se1—Mn1 | 2.6590 (9) | Mn2—I1vi | 2.8380 (5) |
Se1—Sb1iii | 2.7277 (6) | Mn2—I1xii | 2.8380 (5) |
Se1—Sb1iv | 2.7277 (6) | Mn2—I1v | 2.8380 (5) |
Se1—Mn2 | 2.7687 (9) | Mn2—I1xiv | 4.8850 (11) |
Se1—I1xi | 3.8843 (10) | ||
Mn2i—I1—Mn2ii | 90.64 (2) | Sb1iii—Se1—I1xii | 99.84 (2) |
Mn2i—I1—Se2 | 107.09 (2) | Sb1iv—Se1—I1xii | 159.973 (19) |
Mn2ii—I1—Se2 | 107.09 (2) | Mn2—Se1—I1xii | 46.889 (19) |
Mn2i—I1—Sb1iii | 99.31 (2) | I1xi—Se1—I1xii | 62.60 (2) |
Mn2ii—I1—Sb1iii | 156.376 (14) | Mn1—Se1—I1v | 149.060 (10) |
Se2—I1—Sb1iii | 49.516 (17) | Sb1iii—Se1—I1v | 113.83 (3) |
Mn2i—I1—Sb1iv | 156.376 (14) | Sb1iv—Se1—I1v | 70.46 (2) |
Mn2ii—I1—Sb1iv | 99.31 (2) | Mn2—Se1—I1v | 44.529 (12) |
Se2—I1—Sb1iv | 49.516 (17) | I1xi—Se1—I1v | 60.41 (2) |
Sb1iii—I1—Sb1iv | 64.07 (2) | I1xii—Se1—I1v | 91.42 (2) |
Mn2i—I1—Se1i | 45.414 (13) | Mn1—Se1—I1vi | 149.060 (10) |
Mn2ii—I1—Se1i | 92.110 (18) | Sb1iii—Se1—I1vi | 70.46 (2) |
Se2—I1—Se1i | 63.34 (2) | Sb1iv—Se1—I1vi | 113.82 (3) |
Sb1iii—I1—Se1i | 80.181 (18) | Mn2—Se1—I1vi | 44.529 (12) |
Sb1iv—I1—Se1i | 112.37 (2) | I1xi—Se1—I1vi | 91.42 (2) |
Mn2i—I1—Se1ii | 92.110 (18) | I1xii—Se1—I1vi | 60.41 (2) |
Mn2ii—I1—Se1ii | 45.414 (13) | I1v—Se1—I1vi | 59.873 (18) |
Se2—I1—Se1ii | 63.34 (2) | Mn1—Se1—I1 | 138.32 (3) |
Sb1iii—I1—Se1ii | 112.37 (2) | Sb1iii—Se1—I1 | 60.806 (16) |
Sb1iv—I1—Se1ii | 80.181 (18) | Sb1iv—Se1—I1 | 60.806 (16) |
Se1i—I1—Se1ii | 62.60 (2) | Mn2—Se1—I1 | 84.53 (3) |
Mn2i—I1—I1v | 138.491 (18) | I1xi—Se1—I1 | 116.450 (19) |
Mn2ii—I1—I1v | 91.023 (16) | I1xii—Se1—I1 | 116.450 (19) |
Se2—I1—I1v | 111.94 (3) | I1v—Se1—I1 | 56.06 (2) |
Sb1iii—I1—I1v | 95.42 (2) | I1vi—Se1—I1 | 56.06 (2) |
Sb1iv—I1—I1v | 63.195 (17) | Sb1—Se2—Mn1i | 93.21 (2) |
Se1i—I1—I1v | 174.976 (18) | Sb1—Se2—Mn1ii | 93.21 (2) |
Se1ii—I1—I1v | 117.521 (18) | Mn1i—Se2—Mn1ii | 92.87 (2) |
Mn2i—I1—I1vi | 91.023 (16) | Sb1—Se2—Sb1iv | 98.75 (2) |
Mn2ii—I1—I1vi | 138.491 (18) | Mn1i—Se2—Sb1iv | 166.55 (2) |
Se2—I1—I1vi | 111.94 (3) | Mn1ii—Se2—Sb1iv | 92.57 (2) |
Sb1iii—I1—I1vi | 63.195 (17) | Sb1—Se2—Sb1iii | 98.75 (2) |
Sb1iv—I1—I1vi | 95.42 (2) | Mn1i—Se2—Sb1iii | 92.57 (2) |
Se1i—I1—I1vi | 117.521 (18) | Mn1ii—Se2—Sb1iii | 166.55 (2) |
Se1ii—I1—I1vi | 174.976 (18) | Sb1iv—Se2—Sb1iii | 79.61 (3) |
I1v—I1—I1vi | 61.87 (2) | Sb1—Se2—I1 | 160.31 (2) |
Mn2i—I1—I1vii | 45.321 (10) | Mn1i—Se2—I1 | 100.29 (2) |
Mn2ii—I1—I1vii | 45.321 (10) | Mn1ii—Se2—I1 | 100.29 (2) |
Se2—I1—I1vii | 114.71 (3) | Sb1iv—Se2—I1 | 66.62 (2) |
Sb1iii—I1—I1vii | 140.047 (16) | Sb1iii—Se2—I1 | 66.62 (2) |
Sb1iv—I1—I1vii | 140.047 (16) | Sb1—Se2—I1ix | 129.658 (11) |
Se1i—I1—I1vii | 61.771 (17) | Mn1i—Se2—I1ix | 130.83 (2) |
Se1ii—I1—I1vii | 61.771 (17) | Mn1ii—Se2—I1ix | 65.69 (2) |
I1v—I1—I1vii | 123.038 (19) | Sb1iv—Se2—I1ix | 42.296 (16) |
I1vi—I1—I1vii | 123.038 (19) | Sb1iii—Se2—I1ix | 101.63 (2) |
Mn2i—I1—I1viii | 44.679 (10) | I1—Se2—I1ix | 47.326 (10) |
Mn2ii—I1—I1viii | 135.321 (10) | Sb1—Se2—I1viii | 129.658 (11) |
Se2—I1—I1viii | 90.0 | Mn1i—Se2—I1viii | 65.69 (2) |
Sb1iii—I1—I1viii | 57.963 (10) | Mn1ii—Se2—I1viii | 130.83 (2) |
Sb1iv—I1—I1viii | 122.037 (10) | Sb1iv—Se2—I1viii | 101.63 (2) |
Se1i—I1—I1viii | 58.701 (10) | Sb1iii—Se2—I1viii | 42.296 (16) |
Se1ii—I1—I1viii | 121.299 (10) | I1—Se2—I1viii | 47.326 (10) |
I1v—I1—I1viii | 120.933 (10) | I1ix—Se2—I1viii | 94.652 (19) |
I1vi—I1—I1viii | 59.067 (10) | Se1xiii—Mn1—Se1 | 180.0 |
I1vii—I1—I1viii | 90.0 | Se1xiii—Mn1—Se2xi | 85.60 (2) |
Mn2i—I1—I1ix | 135.321 (10) | Se1—Mn1—Se2xi | 94.40 (2) |
Mn2ii—I1—I1ix | 44.679 (11) | Se1xiii—Mn1—Se2iii | 94.40 (2) |
Se2—I1—I1ix | 90.0 | Se1—Mn1—Se2iii | 85.60 (2) |
Sb1iii—I1—I1ix | 122.037 (10) | Se2xi—Mn1—Se2iii | 180.00 (3) |
Sb1iv—I1—I1ix | 57.963 (10) | Se1xiii—Mn1—Se2xii | 85.60 (2) |
Se1i—I1—I1ix | 121.299 (10) | Se1—Mn1—Se2xii | 94.40 (2) |
Se1ii—I1—I1ix | 58.701 (10) | Se2xi—Mn1—Se2xii | 92.87 (2) |
I1v—I1—I1ix | 59.067 (10) | Se2iii—Mn1—Se2xii | 87.13 (2) |
I1vi—I1—I1ix | 120.933 (10) | Se1xiii—Mn1—Se2iv | 94.40 (2) |
I1vii—I1—I1ix | 90.0 | Se1—Mn1—Se2iv | 85.60 (2) |
I1viii—I1—I1ix | 180.000 (10) | Se2xi—Mn1—Se2iv | 87.13 (2) |
Mn2i—I1—Se1v | 88.87 (2) | Se2iii—Mn1—Se2iv | 92.87 (2) |
Mn2ii—I1—Se1v | 43.168 (17) | Se2xii—Mn1—Se2iv | 180.0 |
Se2—I1—Se1v | 147.526 (11) | Se1xiii—Mn1—I1iii | 49.749 (16) |
Sb1iii—I1—Se1v | 156.985 (17) | Se1—Mn1—I1iii | 130.251 (16) |
Sb1iv—I1—Se1v | 113.014 (19) | Se2xi—Mn1—I1iii | 133.296 (19) |
Se1i—I1—Se1v | 119.59 (2) | Se2iii—Mn1—I1iii | 46.704 (19) |
Se1ii—I1—Se1v | 88.58 (2) | Se2xii—Mn1—I1iii | 95.99 (2) |
I1v—I1—Se1v | 65.24 (2) | Se2iv—Mn1—I1iii | 84.01 (2) |
I1vi—I1—Se1v | 95.41 (2) | Se1xiii—Mn1—I1xi | 130.251 (16) |
I1vii—I1—Se1v | 57.82 (2) | Se1—Mn1—I1xi | 49.749 (16) |
I1viii—I1—Se1v | 119.937 (9) | Se2xi—Mn1—I1xi | 46.704 (19) |
I1ix—I1—Se1v | 60.063 (9) | Se2iii—Mn1—I1xi | 133.296 (19) |
Mn2i—I1—Se1vi | 43.168 (18) | Se2xii—Mn1—I1xi | 84.01 (2) |
Mn2ii—I1—Se1vi | 88.87 (2) | Se2iv—Mn1—I1xi | 95.99 (2) |
Se2—I1—Se1vi | 147.526 (11) | I1iii—Mn1—I1xi | 180.0 |
Sb1iii—I1—Se1vi | 113.014 (19) | Se1xiii—Mn1—I1iv | 49.749 (16) |
Sb1iv—I1—Se1vi | 156.985 (17) | Se1—Mn1—I1iv | 130.251 (16) |
Se1i—I1—Se1vi | 88.58 (2) | Se2xi—Mn1—I1iv | 95.99 (2) |
Se1ii—I1—Se1vi | 119.59 (2) | Se2iii—Mn1—I1iv | 84.01 (2) |
I1v—I1—Se1vi | 95.41 (2) | Se2xii—Mn1—I1iv | 133.296 (19) |
I1vi—I1—Se1vi | 65.24 (2) | Se2iv—Mn1—I1iv | 46.704 (19) |
I1vii—I1—Se1vi | 57.82 (2) | I1iii—Mn1—I1iv | 47.303 (14) |
I1viii—I1—Se1vi | 60.063 (9) | I1xi—Mn1—I1iv | 132.697 (14) |
I1ix—I1—Se1vi | 119.937 (9) | Se1xiii—Mn1—I1xii | 130.251 (16) |
Se1v—I1—Se1vi | 59.873 (18) | Se1—Mn1—I1xii | 49.749 (16) |
Mn2i—I1—Sb1x | 82.26 (2) | Se2xi—Mn1—I1xii | 84.01 (2) |
Mn2ii—I1—Sb1x | 82.26 (2) | Se2iii—Mn1—I1xii | 95.99 (2) |
Se2—I1—Sb1x | 166.328 (15) | Se2xii—Mn1—I1xii | 46.704 (19) |
Sb1iii—I1—Sb1x | 120.132 (18) | Se2iv—Mn1—I1xii | 133.296 (19) |
Sb1iv—I1—Sb1x | 120.132 (18) | I1iii—Mn1—I1xii | 132.697 (14) |
Se1i—I1—Sb1x | 127.44 (2) | I1xi—Mn1—I1xii | 47.303 (14) |
Se1ii—I1—Sb1x | 127.44 (2) | I1iv—Mn1—I1xii | 180.0 |
I1v—I1—Sb1x | 56.94 (2) | Se1—Mn2—Se1xiv | 180.0 |
I1vi—I1—Sb1x | 56.94 (2) | Se1—Mn2—I1xi | 87.70 (2) |
I1vii—I1—Sb1x | 78.96 (3) | Se1xiv—Mn2—I1xi | 92.30 (2) |
I1viii—I1—Sb1x | 90.0 | Se1—Mn2—I1vi | 92.30 (2) |
I1ix—I1—Sb1x | 90.0 | Se1xiv—Mn2—I1vi | 87.70 (2) |
Se1v—I1—Sb1x | 39.383 (12) | I1xi—Mn2—I1vi | 180.000 (11) |
Se1vi—I1—Sb1x | 39.383 (12) | Se1—Mn2—I1xii | 87.70 (2) |
Se2—Sb1—Se1iii | 87.94 (2) | Se1xiv—Mn2—I1xii | 92.30 (2) |
Se2—Sb1—Se1iv | 87.94 (2) | I1xi—Mn2—I1xii | 90.64 (2) |
Se1iii—Sb1—Se1iv | 95.43 (3) | I1vi—Mn2—I1xii | 89.36 (2) |
Se2—Sb1—Se2iv | 81.25 (2) | Se1—Mn2—I1v | 92.30 (2) |
Se1iii—Sb1—Se2iv | 166.92 (2) | Se1xiv—Mn2—I1v | 87.70 (2) |
Se1iv—Sb1—Se2iv | 91.54 (2) | I1xi—Mn2—I1v | 89.36 (2) |
Se2—Sb1—Se2iii | 81.25 (2) | I1vi—Mn2—I1v | 90.64 (2) |
Se1iii—Sb1—Se2iii | 91.54 (2) | I1xii—Mn2—I1v | 180.000 (11) |
Se1iv—Sb1—Se2iii | 166.92 (2) | Se1—Mn2—I1xiv | 118.88 (3) |
Se2iv—Sb1—Se2iii | 79.61 (3) | Se1xiv—Mn2—I1xiv | 61.12 (3) |
Mn1—Se1—Sb1iii | 93.22 (2) | I1xi—Mn2—I1xiv | 53.466 (12) |
Mn1—Se1—Sb1iv | 93.22 (2) | I1vi—Mn2—I1xiv | 126.534 (12) |
Sb1iii—Se1—Sb1iv | 95.43 (3) | I1xii—Mn2—I1xiv | 53.466 (12) |
Mn1—Se1—Mn2 | 137.15 (3) | I1v—Mn2—I1xiv | 126.534 (12) |
Sb1iii—Se1—Mn2 | 114.51 (2) | Se1—Mn2—I1 | 61.12 (3) |
Sb1iv—Se1—Mn2 | 114.51 (2) | Se1xiv—Mn2—I1 | 118.88 (3) |
Mn1—Se1—I1xi | 98.75 (2) | I1xi—Mn2—I1 | 126.534 (12) |
Sb1iii—Se1—I1xi | 159.973 (19) | I1vi—Mn2—I1 | 53.466 (12) |
Sb1iv—Se1—I1xi | 99.84 (2) | I1xii—Mn2—I1 | 126.534 (12) |
Mn2—Se1—I1xi | 46.889 (19) | I1v—Mn2—I1 | 53.466 (12) |
Mn1—Se1—I1xii | 98.75 (2) | I1xiv—Mn2—I1 | 180.0 |
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x+1/2, y−1/2, z; (iii) −x+1/2, −y+1/2, −z+1; (iv) −x+1/2, −y−1/2, −z+1; (v) −x+1/2, −y−1/2, −z; (vi) −x+1/2, −y+1/2, −z; (vii) −x+1, −y, −z; (viii) x, y+1, z; (ix) x, y−1, z; (x) x, y, z−1; (xi) x−1/2, y−1/2, z; (xii) x−1/2, y+1/2, z; (xiii) −x, −y, −z+1; (xiv) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | MnSbSe2I |
Mr | 461.51 |
Crystal system, space group | Monoclinic, C2/m |
Temperature (K) | 153 |
a, b, c (Å) | 13.319 (3), 4.0359 (8), 10.105 (2) |
β (°) | 91.27 (3) |
V (Å3) | 543.08 (19) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 26.21 |
Crystal size (mm) | 0.19 × 0.04 × 0.02 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD area-detector diffractometer |
Absorption correction | Numerical XP in SHELXTL (Sheldrick, 1997) |
Tmin, Tmax | 0.145, 0.656 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2404, 737, 709 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.674 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.071, 1.37 |
No. of reflections | 737 |
No. of parameters | 34 |
Δρmax, Δρmin (e Å−3) | 2.11, −1.63 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXTL (Sheldrick, 1997), ATOMS 5.1 (Dowty, 1999), SHELXTL 5.1.
Sb1—Se2 | 2.5995 (9) | Mn1—Se2iii | 2.7849 (6) |
Sb1—Se1i | 2.7277 (6) | Mn2—Se1iv | 2.7687 (9) |
Mn1—Se1ii | 2.6590 (9) | Mn2—I1iii | 2.8380 (5) |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x, −y, −z+1; (iii) x−1/2, y−1/2, z; (iv) −x, −y, −z. |
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Quaternary phases consisting of a transition metal and several types of p-block elements in an ordered arrangement are relatively scarce. In the TM—Pn—Q—X systems (where TM is a transition metal, Pn = P, As, Sb and Bi, Q = S, Se and Te, and X = F, Cl, Br and I), the most prevalent examples contain Cu, for example, Cu6PS5Br (Haznar et al., 1999), (CuBr)3P4Se4 (Reiser et al., 2003), (CuI)P4Se4 (Pfitzner et al., 1999), (CuI)3P4Se4 (Pfitzner & Reiser, 1999), (CuI)2P8Se3 (Pfitzner et al., 2000), (CuI)2Cu3SbS3 (Pfitzner, 1997), Cu3Bi2S4Cl (Lewis & Kupcik, 1974) and Cu3Bi2S4Br (Mariolacos & Kupcik, 1975), or another late d-block element, for example, CdSb6S8I4 (Sirota et al., 1976) and Hg3AsQ4X (Q = S and Se, and X = Cl, Br and I; Beck et al., 2000). In most cases, the metal adopts a tetrahedral coordination, as expected for these late d-block elements; an interesting exception is CdSb6S8I4, in which Cd adopts an octahedral coordination. There appear to be no examples of compounds of formula TM1Pn1Q2X.
MnSbSe2I represents a new layered structure type, as shown in Fig. 1(a). The layers are parallel to the bc plane and contain two kinds of Mn-centered octahedra; atom Mn1 is surrounded by four Se2 and two Se1 atoms, whereas atom Mn2 is surrounded by four I1 and two Se1 atoms. The octahedra share their corners along the c direction and share their edges along the b direction. The Mn—Se distances of 2.6590 (9), 2.7849 (6) and 2.7687 (9) Å and the Mn—I distances of 2.8380 (5) Å are comparable to those found in olivine-type Mn2SiSe4 [2.671 (4)—2.756 (3) Å; Jobic et al., 1995] and in CsMnI3 [2.920 (2) Å; Zandbergen, 1980], respectively, where octahedrally coordinated Mn is present. Between the layers lie the Sb1 atoms, which are coordinated to three Se atoms to form a trigonal pyramid at distances of 2.5995 (9) and 2.7277 (6) Å, similar to those in Sb2Se3 [2.589 (1)–2.803 (1) Å; Voutsas et al., 1985]. The closest distance between an Sb1 atom in one layer and an Se atom in the adjacent layer is 3.1523 (8) Å, which is too long to be considered as a covalent bond.
The structure of monoclinic MnSbSe2I (C2/m) is a distorted variant of that of orthorhombic UFeS3 (Cmcm; Fig. 1 b and Noël & Padiou, 1976). In the latter structure, layers of Fe-centered octahedra are also evident, but the intervening U atoms are arranged more symmetrically, residing in tricapped trigonal-prismatic sites. The lower monoclinic symmetry (β = 91.27°) of MnSbSe2I arises from the absence of mirror and glide planes associated with the displacement of the Sb atoms as well as the chemical inequivalence of the two types of Mn-centered octahedra. The irregular position of the Sb atom is indicative of Sb3+, implying the presence of a lone pair. This assignment is consistent with the charge-balanced formulation (Mn2+)(Sb3+)(Se2−)2(I−). Comparison with the analogous formulation (U3+)(Fe3+)(S2−)3 shows that replacement of one of the chalcogen atoms in UFeS3 by a halogen atom in MnSbSe2I is compensated by substitution with a lower-charged transition-metal ion.