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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 61| Part 12| December 2005| Pages m516-m518
doi:10.1107/S0108270105032361

Methyl­ammonium antimony sulfide

CROSSMARK_Color_square_no_text.svg
Rachel J. E. Lees,a Anthony V. Powella* and Ann M. Chippindaleb

aDepartment of Chemistry, Heriot–Watt University, Edinburgh EH14 4AS, Scotland, and bSchool of Chemistry, The University of Reading, Whiteknights, Reading RG6 6AD, England
*Correspondence e-mail: a.v.powell@hw.ac.uk

(Received 5 September 2005; accepted 10 October 2005; online 11 November 2005)

Bis(methyl­ammonium) octa­antimony(III) dodeca­sulfide per­sul­fide, (CH3NH3)2[Sb8S12(S2)], contains pairs of [Sb4S7]2− chains joined through an unusual persulfide bond to create infinite double [Sb8S14]2− chains. The double chains are ­inter­locked by longer Sb⋯S inter­actions to form sheets approximately parallel to the (101) crystallographic plane. Methylammonium cations, formed by decomposition of 2-methyl­propane-1,2-diamine during the synthesis, are located in large (Sb8S10) hetero-ring apertures created within the double chains.

Comment

Organic template-directed solvothermal synthesis of open-framework antimony(III) sulfides yields a wide variety of structural motifs. Hence, novel materials can be synthesized with potentially inter­esting electrical, optical and magnetic properties. The variety of structures is a result of the stereochemical effect of the lone pair of electrons on SbIII, together with the possibility of SbIII having coordination numbers ranging from 3 to 6. The primary building units are typically [SbS3]3− trigonal pyramids, which are connected via corner- or edge-sharing to form isolated, chain, layered or three-dimensional structures (Sheldrick & Wachhold, 1998[Sheldrick, W. & Wachhold, M. (1998). Coord. Chem. Rev. 176, 211-322.]). The [Sb4S7]2− chain is a common structural motif and is frequently present as single isolated chains (Parise & Ko, 1992[Parise, J. B. & Ko, Y. (1992). Chem. Mater. 4, 1446-1450.]). In rare examples, the chains can be linked to form infinite double chains, such as in [C2N2H10]Sb8S13 (Tan et al., 1994[Tan, K., Ko, Y. & Parise, J. B. (1994). Acta Cryst. C50, 1439-1442.]) and [C3N2H12]Sb10S16 (Wang, 1995[Wang, X. (1995). Eur. J. Solid State Inorg. Chem. 32, 303-312.]). As part of our ongoing studies of antimony–sulfide materials, we report here the structure of the title compound, [CH3NH3]2Sb8S12(S2), (I), synthesized under solvothermal conditions, using 2-methyl­propane-1,2-diamine. During the reaction, the amine decomposes and the methyl­ammonium fragment formed directs the crystallization of the antimony–sulfide structure. The structure contains the unusual feature of a persulfide linkage between antimony–sulfide chains, and represents, after [(CH3)2NH2]2Sb8S12(S2) (Tan et al., 1996[Tan, K., Ko, Y., Parise, J. B., Hark, J. H. & Darovsky, A. (1996). Chem. Mater. 8, 2510-2515.]), only the second reported example of its occurrence.

In the asymmetric unit of (I), there are four Sb atoms and seven S atoms, all of which occupy general positions (Fig. 1[link]). All of the Sb atoms show their expected pyramidal coordination (Table 1[link]). The bond-valence sums (BVS) for atoms Sb1–Sb4, calculated using the procedure of Brese & O'Keeffe (1991[Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192-197.]), are 2.73, 2.92, 2.72 and 2.91, respectively. These are in satisfactory agreement with the expected value of 3.00 for SbIII. Three [SbS3]3− pyramidal units are corner-linked to form [Sb3S6]3− semi-cubes, which are linked by [SbS3]3− trigonal pyramids to form infinite [Sb4S7]2− chains, in which semi-cubes and pyramids alternate (Fig. 2[link]). Atoms S7 and S7(−x, 1 − y, 1 − z) serve to link pairs of [Sb4S7]2− chains into double chains through a persulfide bond. The S—S bond length of 2.101 (2) Å is slightly longer than that of 2.085 (7) Å for the persulfide bond found in (Me2NH2)2Sb8S14, the only other example of such a bond in these materials (Tan et al., 1996[Tan, K., Ko, Y., Parise, J. B., Hark, J. H. & Darovsky, A. (1996). Chem. Mater. 8, 2510-2515.]).

18-membered (Sb8S10) hetero-rings are generated within the double chains, containing one methyl­amine mol­ecule disordered over two crystallographically independent sites. The double negative charge of the antimony–sulfide framework requires the amine group to be monoprotonated. The shortest distance between the methyl­ammonium ions and the surrounding framework atoms is the S5⋯N2 inter­atomic distance of 3.288 (7) Å, suggesting possible hydrogen bonding between the template and the antimony–sulfide framework. The [Sb8S12(S2)]2− double chains are directed along [101]. Longer secondary Sb⋯S inter­actions in the range 3.22–3.37 Å serve to crosslink double chains in a zipper-like arrangement, forming layers approximately parallel to the (101) plane (Fig. 3[link]) and linking individual layers into a three-dimensional structure.

The structure of (I) described in the space group P21/n is closely related to that of [(CH3)2NH2]2Sb8S12(S2) reported by Tan et al. (1996[Tan, K., Ko, Y., Parise, J. B., Hark, J. H. & Darovsky, A. (1996). Chem. Mater. 8, 2510-2515.]), which crystallizes in the space group Cmca. However, there is a slight variation in the crystal packing, depending on the structure-directing amine used. In [(CH3)2NH2]2Sb8S12(S2), the antimony–sulfide layers are essentially planar, whereas in (I), the layers undulate along the [010] direction.

[Figure 1]
Figure 1
The [Sb4S7]2− repeating unit and one of the two positions of the disordered methyl­ammonium cation in (I). Displacement ellipsoids are drawn at the 50% probability level. Symmetry codes are as given in Table 1[link].
[Figure 2]
Figure 2
A view of (I) along the [[\overline 1]01] direction (the a axis is eclipsed), showing the methyl­ammonium cations within the (Sb8S10) hetero-rings. Both orientations of the disordered methylammonium cation are shown. Key: antimony, large solid circles; sulfur, large open circles; carbon, small solid circles; nitro­gen, small open circles.
[Figure 3]
Figure 3
A view along the [101] direction, showing the undulating antimony sulfide layers. Methyl­ammonium cations have been omitted for clarity. The key is as for Fig. 2[link].

Experimental

Compound (I) was synthesized by the reaction of 2-methyl­propane-1,2-diamine (2 mmol), Sb2S3 (2 mmol) and sulfur (5 mmol) in distilled water (3 ml). The mixture was heated in a Teflon-lined steel autoclave with an inner volume of 23 ml for 4 d at 438 K, and then cooled to room temperature over a period of 6 h. The product, consisting of red blocks of (I) and a small amount of unreacted Sb2S3, was filtered off, washed with water and acetone, and dried in air. CHN analysis of a handpicked sample of (I) found: C 1.64, H 0.60, N 1.79%; calculated: C 1.62, H 0.81, N 1.88%. Thermogravimetric analysis under flowing N2 of handpicked ground crystals (7.29 mg) revealed a single weight loss of 8.20% over the range 541–559 K, which is consistent with the loss of the organic amine together with two moles of H2S (8.61%). Powder X-ray diffraction of the decomposition product indicates that thermal decomposition produces poorly crystalline Sb2S3.

Crystal data

  • (CH6N)2[Sb8S12(S2)]

  • Mr = 743.60

  • Monoclinic, P 21 /n

  • a = 7.0984 (9) Å

  • b = 25.139 (3) Å

  • c = 7.937 (1) Å

  • β = 97.034 (6)°

  • V = 1405.6 (3) Å3

  • Z = 4

  • Dx = 3.513 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 4140 reflections

  • θ = 1.6–30.1°

  • μ = 8.61 mm−1

  • T = 100 K

  • Plate, red

  • 0.24 × 0.06 × 0.01 mm
Data collection

  • Bruker–Nonius APEX-2 CCD area-detector diffractometer

  • ω/2θ scans

  • Absorption correction: multi-scan(SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.])Tmin = 0.547, Tmax = 0.918

  • 47592 measured reflections

  • 4143 independent reflections

  • 3187 reflections with I > 3σ(I)

  • Rint = 0.032

  • θmax = 30.2°

  • h = −10 → 9

  • k = −35 → 35

  • l = −11 → 11
Refinement

  • Refinement on F

  • R[F > 2σ(F)] = 0.024

  • wR(F) = 0.027

  • S = 1.08

  • 3187 reflections

  • 137 parameters

  • H-atom parameters constrained

  • Weighting scheme: Chebychev polynomial (Watkin, 1994[Watkin, D. J. (1994). Acta Cryst. A50, 411-437.]), w = 1/[0.562T0(x) + 0.144T1(x) + 0.274T3(x)], where x = F/Fmax; W = w[1 − (ΔF/6σF)2]2

  • (Δ/σ)max = 0.002

  • Δρmax = 1.24 e Å−3

  • Δρmin = −1.25 e Å−3

Table 1
Selected geometric parameters (Å, °)

Sb1—S1 2.4983 (12)
Sb1—S2 2.4731 (11)
Sb1—S3 2.4819 (11)
Sb2—S2 2.4944 (12)
Sb2—S4 2.4074 (11)
Sb2—S5 2.4833 (12)
Sb3—S3 2.4745 (11)
Sb3—S5 2.4771 (11)
Sb3—S6i 2.5079 (12)
Sb4—S1 2.4477 (11)
Sb4—S6 2.4467 (12)
Sb4—S7 2.4884 (11)
S7—S7ii 2.101 (2)
N1—C1 1.464 (8)
N2—C2 1.463 (8)
S1—Sb1—S2 91.41 (4) 
S1—Sb1—S3 85.14 (4)
S2—Sb1—S3 96.37 (4)
S2—Sb2—S4 96.17 (4)
S2—Sb2—S5 95.24 (4)
S4—Sb2—S5 95.83 (4)
S3—Sb3—S5 98.44 (4)
S3—Sb3—S6i 83.26 (4)
S5—Sb3—S6i 89.67 (4)
S1—Sb4—S6 92.65 (4)
S1—Sb4—S7 95.40 (4)
S6—Sb4—S7 95.36 (4)
Sb1—S1—Sb4 99.91 (4)
Sb1—S2—Sb2 97.99 (4)
Sb1—S3—Sb3 105.35 (4)
Sb2—S5—Sb3 97.85 (4)
Sb3iii—S6—Sb4 99.69 (4)
Sb4—S7—S7ii 101.09 (7)
Symmetry codes: (i) x+1, y, z+1; (ii) -x, -y+1, -z+1; (iii) x-1, y, z-1.

The methyl­ammonium cations were modelled as disordered over two independent sites, each with an occupancy of 0.5. The C—N distances were restrained to be 1.45 (1) Å in each case. The six 0.5-occupancy H atoms of each 0.5-occupancy methylammonium cation were placed geometrically in a fully staggered orientation, as they could not be located from difference Fourier maps. H atoms were positioned geometrically and allowed to ride on their respective carrier atoms [C—H = N—H = 1.00 Å and Uiso(H) = 1.2Ueq(C,N)]. Large residuals in the difference Fourier map revealed the presence of a minor twin component. The twin law was identified using the ROTAX procedure (Cooper et al., 2002[Cooper, R. I., Gould, R. O., Parsons, S. & Watkin, D. J. (2002). J. Appl. Cryst. 35, 168-174.]), implemented as a routine in CRYSTALS (Watkin et al., 1996[Watkin, D. J., Prout, C. K., Carruthers, J. R. & Betteridge, P. W. (1996). CRYSTALS. Issue 10. Chemical Crystallography Laboratory, Oxford, England.]). The model was refined as a two-component twin, (100, 010, 001) and (0.124 0 [\overline {0}.874], 0[\overline 1]0, [\overline 1.127] 0 [\overline 0.124]), with twin element scale factors 0.84 and 0.16.

Data collection: APEX2 (Bruker, 2005[Bruker (2005). APEX2. Version 1.27. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, G., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]); program(s) used to refine structure: CRYSTALS (Watkin et al., 1996[Watkin, D. J., Prout, C. K., Carruthers, J. R. & Betteridge, P. W. (1996). CRYSTALS. Issue 10. Chemical Crystallography Laboratory, Oxford, England.]); molecular graphics: ATOMS (Dowty, 2000[Dowty, E. (2000). ATOMS. Version 6.1. Shape Software, Hidden Valley Road, Kingsport, TN, USA.]); software used to prepare material for publication: CRYSTALS (Watkin et al., 1996[Watkin, D. J., Prout, C. K., Carruthers, J. R. & Betteridge, P. W. (1996). CRYSTALS. Issue 10. Chemical Crystallography Laboratory, Oxford, England.]).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S0108270105032361/bg1018sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270105032361/bg1018Isup2.hkl


Comment top

Organic template-directed solvothermal synthesis of open-framework antimony(III) sulfides yields a wide variety of structural motifs. Hence, novel materials can be synthesized with potentially interesting electrical, optical and magnetic properties. The variety of structures is a result of the stereochemical effect of the lone pair of electrons on Sb(III), together with the possibility of Sb(III) having coordination numbers ranging from 3 to 6. The primary building units are typically [SbS3]3− trigonal pyramids, which are connected via corner- or edge-sharing to form isolated, chain, layered or three-dimensional structures (Sheldrick & Wachhold, 1998). The [Sb4S7]2− chain is a common structural motif and is frequently present as single isolated chains (Parize & Ko, 1992). In rare examples, the chains can be linked to form infinite double chains such as in [C2N2H10]Sb8S13 (Tan et al., 1994) and [C3N2H12]Sb10S16 (Wang, 1995). As part of our ongoing studies of antimony sulfide materials, we report here the structure of the title compound, [CH3NH3]2Sb8S12(S2), (I), synthesized under solvothermal conditions, using 1,2-diamino-2-methylpropane. During the reaction, the amine decomposes and the methylammonium fragment formed directs the crystallization of the antimony sulfide structure. The structure contains the unusual feature of a persulfide linkage between antimony sulfide chains, and represents, after [(CH3)2NH2]2Sb8S12(S2) (Tan et al., 1996), only the second reported example of its occurrence.

In the asymmetric unit of (I), there are four Sb atoms and seven S atoms, all of which occupy general positions (Fig. 1). All of the Sb atoms show their expected pyramidal coordination (Table 1). The Sb—S bond lengths range from 2.4074 (11) to 2.5079 (12) Å. The bond-valence sums (BVS) for Sb1–Sb4, calculated using the procedure of Brese & O'Keeffe (1991), are 2.73, 2.92, 2.72 and 2.91, respectively. These are in satisfactory agreement with the expected value of 3.00 for SbIII. Three [SbS3]3− pyramidal units are corner linked to form [Sb3S6]3− semi-cubes, which are linked by [SbS3]3− trigonal pyramids to form infinite [Sb4S7]2− chains in which semi-cubes and pyramids alternate (Fig. 2). Atoms S7 and S7(−x, 1 − y, 1 − z) serve to link pairs of [Sb4S7]2− chains into double chains through a persulfide bond. The S—S bond length of 2.101 (2) Å is slightly longer than that of 2.085 (7) Å for the persulfide bond found in [Me2NH2]2Sb8S14, the only other example of such a bond in these materials. (Tan et al., 1996).

18-membered Sb8S10 heterorings are generated within the double chains, containing one methylamine molecule disordered over two crystallographically independent sites. The double negative charge of the antimony sulfide framework requires the amine group to be monoprotonated. The shortest distance between the methylammonium ions and the surrounding framework atoms is the S5···N2 interatomic distance of 3.288 (7) Å, suggesting possible hydrogen bonding between the template and the antimony sulfide framework. The [Sb8S12(S2)]2− double chains are directed along [101]. Longer secondary Sb···S interactions in the range 3.22–3.37 Å serve to cross-link double chains in a zipper-like arrangement, to form layers approximately parallel to the (101) plane (Fig. 3), and to link individual layers into a three-dimensional structure.

The structure of (I) described in space group P21/n is closely related to that of [(CH3)2NH2]2Sb8S12(S2) reported by Tan et al. (1996), which crystallizes in space group Cmca. However, there is a slight variation in the crystal packing, depending on the structure-directing amine used. In [(CH3)2NH2]2Sb8S12(S2), the antimony sulfide layers are essentially planar, whereas in (1), the layers undulate along the [010] direction.

Experimental top

Compound (I) was synthesized by the reaction of 1,2-diamino-2-methylpropane (2 mmol), Sb2S3 (6 mmol) and S (5 mmol) in distilled water (3 ml). The mixture was heated in a Teflon-lined steel autoclave with an inner volume of 23 ml for 4 d at 438, and then cooled to room temperature over a period of 6 h. The product was filtered off, washed with water and acetone and dried in air. It consisted of red blocks of (I) and a small amount of unreacted Sb2S3. CHN analysis of a handpicked sample of (I) found: C 1.64, H 0.60, N 1.79%; calculated: C 1.62, H 0.81, N 1.88%. Thermogravimetric analysis under flowing N2 of 7.29 mg of handpicked ground crystals revealed a single weight loss of 8.20% over the range 541–559 K, which is consistent with the loss of the organic amine together with two moles of H2S (8.61%). Powder X-ray diffraction of the decomposition product indicates that thermal decomposition produces poorly crystalline Sb2S3.

Refinement top

The methylammonium cations were modelled as disordered over two independent sites each with occupancy of 0.5. The C—N distances were restrained to be 1.45 (1) Å in each case. H atoms were positioned geometrically and allowed to ride on their respective carrier atoms [C—H = N—H = 1.00 Å and Uiso(H) = 1.2Ueq(C,N)]. Large residuals in the difference Fourier map revealed the presence of a minor twin component. The twin law was identified using the ROTAX procedure (Cooper et al., 2002), implemented as a routine in CRYSTALS. The model was refined as a two-component twin, (1 0 0, 0 1 0, 0 0 1) and (0.124 0 − 0.874, 0 − 1 0, −1.127 0 − 0.124), with twin element scale factors 0.84 and 0.16.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Watkin et al., 1996); molecular graphics: ATOMS (Dowty, 2000); software used to prepare material for publication: CRYSTALS (Watkin et al., 1996).

Figures top
[Figure 1] Fig. 1. The [Sb4S7]2− repeating unit and one of the two methylammonium cations in (I). Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A view of (I) along the [−101] direction (labelled a axis eclipsed in the figure), showing the methylammonium cations within the Sb8S10 heterorings. Key: antimony, large solid circles; sulfur, large open circles; carbon, small solid circles; nitrogen, small open circles.
[Figure 3] Fig. 3. A view along the [101] direction, showing the undulating antimony sulfide layers. Methylammonium cations have been omitted for clarity. Key as for Fig. 2
Bis(methylammonium) octaantimony(III) dodecasulfide persulfide top
Crystal data top
[CH3NH3]2Sb8S12(S2)F(000) = 1340.000
Mr = 743.60Dx = 3.513 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4140 reflections
a = 7.0984 (9) Åθ = 1.6–30.1°
b = 25.139 (3) ŵ = 8.61 mm−1
c = 7.937 (1) ÅT = 100 K
β = 97.034 (6)°Plate, red
V = 1405.6 (3) Å30.24 × 0.06 × 0.01 mm
Z = 4
Data collection top
Bruker–Nonius Apex-2 CCD area-detector
diffractometer		3187 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.032
ω/2θ scansθmax = 30.2°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→9
Tmin = 0.547, Tmax = 0.918k = −35→35
47592 measured reflectionsl = −11→11
4143 independent reflections
Refinement top
Refinement on FSecondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.027 Weighting scheme: Chebychev polynomial (Watkin, 1994), [weight] = 1/[0.562T0(x) + 0.144T1(x) + 0.274T3(x)],
where x = F/Fmax; W = [weight][1-(ΔF/6σF)2]2
S = 1.08(Δ/σ)max = 0.002
3187 reflectionsΔρmax = 1.24 e Å−3
137 parametersΔρmin = −1.25 e Å−3
Primary atom site location: structure-invariant direct methods
Crystal data top
[CH3NH3]2Sb8S12(S2)V = 1405.6 (3) Å3
Mr = 743.60Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.0984 (9) ŵ = 8.61 mm−1
b = 25.139 (3) ÅT = 100 K
c = 7.937 (1) Å0.24 × 0.06 × 0.01 mm
β = 97.034 (6)°
Data collection top
Bruker–Nonius Apex-2 CCD area-detector
diffractometer		4143 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3187 reflections with I > 3σ(I)
Tmin = 0.547, Tmax = 0.918Rint = 0.032
47592 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.024137 parameters
wR(F2) = 0.027H-atom parameters constrained
S = 1.08Δρmax = 1.24 e Å−3
3187 reflectionsΔρmin = −1.25 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Sb10.50977 (4)0.67525 (1)0.62802 (4)0.0093
Sb20.43274 (4)0.74430 (1)1.03262 (4)0.0103
Sb30.89702 (4)0.67429 (1)1.02881 (4)0.0093
Sb40.03673 (4)0.61340 (1)0.46256 (4)0.0093
S10.37450 (16)0.59059 (5)0.50018 (15)0.0130
S20.27312 (16)0.67716 (5)0.83217 (14)0.0127
S30.74168 (16)0.61691 (4)0.79927 (14)0.0108
S40.67106 (16)0.76983 (4)0.85695 (14)0.0111
S50.63383 (16)0.67883 (5)1.20645 (14)0.0123
S6−0.00178 (16)0.58698 (4)0.16361 (14)0.0126
S7−0.07195 (17)0.52709 (4)0.57009 (15)0.0124
N10.4330 (14)0.5592 (4)1.0473 (14)0.01900.5000
N20.4839 (16)0.5575 (4)1.1114 (14)0.02100.5000
C10.3239 (14)0.5246 (4)0.9228 (14)0.02250.5000
C20.5551 (16)0.5071 (4)1.1862 (13)0.02040.5000
H100.3579 (14)0.5254 (4)0.8076 (14)0.0261*0.5000
H110.1908 (14)0.5369 (4)0.9283 (14)0.0261*0.5000
H120.3420 (14)0.4887 (4)0.9764 (14)0.0261*0.5000
H130.5708 (14)0.5501 (4)1.0521 (14)0.0228*0.5000
H140.4128 (14)0.5971 (4)1.0122 (14)0.0228*0.5000
H150.3911 (14)0.5538 (4)1.1619 (14)0.0228*0.5000
H200.6869 (16)0.4980 (4)1.1639 (13)0.0235*0.5000
H210.5408 (16)0.5126 (4)1.3088 (13)0.0235*0.5000
H220.4554 (16)0.4818 (4)1.1348 (13)0.0235*0.5000
H230.5728 (16)0.5868 (4)1.1536 (14)0.0233*0.5000
H240.3554 (16)0.5648 (4)1.1455 (14)0.0233*0.5000
H250.4750 (16)0.5555 (4)0.9848 (14)0.0233*0.5000
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sb10.00847 (12)0.01018 (13)0.00916 (13)−0.00105 (9)0.00041 (9)−0.0004 (1)
Sb20.01087 (12)0.00959 (13)0.01100 (13)0.0009 (1)0.0032 (1)−0.0001 (1)
Sb30.00875 (12)0.01017 (13)0.00870 (12)−0.00058 (9)−0.00015 (9)−0.0004 (1)
Sb40.01034 (12)0.00761 (12)0.00954 (13)−0.00003 (9)0.00010 (9)0.0000 (1)
S10.0101 (4)0.0112 (5)0.0168 (5)−0.0002 (4)−0.0017 (4)−0.0016 (4)
S20.0101 (4)0.0154 (5)0.0130 (5)−0.0023 (4)0.0023 (4)−0.0013 (4)
S30.0108 (4)0.0105 (4)0.0106 (5)0.0003 (4)−0.0012 (3)−0.0018 (4)
S40.0111 (4)0.0113 (5)0.0110 (5)0.0000 (4)0.0013 (3)−0.0000 (4)
S50.0128 (5)0.0147 (5)0.0099 (4)0.0013 (4)0.0028 (4)0.0016 (4)
S60.0160 (5)0.0104 (5)0.0107 (5)0.0010 (4)−0.0014 (4)−0.0004 (4)
S70.0149 (5)0.0082 (4)0.0146 (5)−0.0011 (4)0.0042 (4)0.0008 (4)
N10.020 (4)0.014 (4)0.025 (5)−0.001 (3)0.008 (3)−0.002 (3)
N20.024 (4)0.018 (4)0.022 (4)−0.006 (3)0.010 (3)−0.003 (4)
C10.018 (4)0.013 (4)0.038 (5)0.002 (3)0.005 (4)0.001 (4)
C20.025 (4)0.021 (4)0.015 (4)−0.006 (3)0.004 (3)−0.003 (3)
Geometric parameters (Å, º) top
Sb1—S12.4983 (12)N1—H131.000
Sb1—S22.4731 (11)N1—H141.000
Sb1—S32.4819 (11)N1—H151.000
Sb2—S22.4944 (12)N2—C21.463 (8)
Sb2—S42.4074 (11)N2—H231.000
Sb2—S52.4833 (12)N2—H241.000
Sb3—S32.4745 (11)N2—H251.000
Sb3—S52.4771 (11)C1—H100.97 (2)
Sb3—S6i2.5079 (12)C1—H111.000
Sb4—S12.4477 (11)C1—H121.000
Sb4—S62.4467 (12)C2—H201.000
Sb4—S72.4884 (11)C2—H211.000
S7—S7ii2.101 (2)C2—H221.000
N1—C11.464 (8)
S1—Sb1—S291.41 (4)C1—N1—H15110.0 (6)
S1—Sb1—S385.14 (4)H13—N1—H15109.476
S2—Sb1—S396.37 (4)H14—N1—H15109.474
S2—Sb2—S496.17 (4)C2—N2—H23109.2 (6)
S2—Sb2—S595.24 (4)C2—N2—H24109.3 (6)
S4—Sb2—S595.83 (4)H23—N2—H24109.475
S3—Sb3—S598.44 (4)C2—N2—H25109.9 (6)
S3—Sb3—S6i83.26 (4)H23—N2—H25109.476
S5—Sb3—S6i89.67 (4)H24—N2—H25109.476
S1—Sb4—S692.65 (4)N1—C1—H10116.8 (14)
S1—Sb4—S795.40 (4)N1—C1—H11102.3 (6)
S6—Sb4—S795.36 (4)H10—C1—H11112.3 (12)
Sb1—S1—Sb499.91 (4)N1—C1—H12102.6 (6)
Sb1—S2—Sb297.99 (4)H10—C1—H12112.6 (12)
Sb1—S3—Sb3105.35 (4)H11—C1—H12109.466
Sb2—S5—Sb397.85 (4)N2—C2—H20114.2 (6)
Sb3iii—S6—Sb499.69 (4)N2—C2—H21101.8 (6)
Sb4—S7—S7ii101.09 (7)H20—C2—H21114.387
C1—N1—H13109.0 (6)N2—C2—H22101.1 (6)
N2—N1—H14111.1 (16)H20—C2—H22114.386
C1—N1—H14109.4 (6)H21—C2—H22109.467
H13—N1—H14109.475
Symmetry codes: (i) x+1, y, z+1; (ii) −x, −y+1, −z+1; (iii) x−1, y, z−1.

Experimental details

Crystal data
Chemical formula[CH3NH3]2Sb8S12(S2)
Mr743.60
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)7.0984 (9), 25.139 (3), 7.937 (1)
β (°) 97.034 (6)
V (Å3)1405.6 (3)
Z4
Radiation typeMo Kα
µ (mm−1)8.61
Crystal size (mm)0.24 × 0.06 × 0.01
Data collection
DiffractometerBruker–Nonius Apex-2 CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.547, 0.918
No. of measured, independent and
observed [I > 3σ(I)] reflections		47592, 4143, 3187
Rint0.032
(sin θ/λ)max (Å−1)0.708
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.027, 1.08
No. of reflections3187
No. of parameters137
No. of restraints?
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)1.24, −1.25

Computer programs: APEX2 (Bruker, 2005), APEX2, SIR92 (Altomare et al., 1994), CRYSTALS (Watkin et al., 1996), ATOMS (Dowty, 2000).

Selected geometric parameters (Å, º) top
Sb1—S12.4983 (12)Sb3—S6i2.5079 (12)
Sb1—S22.4731 (11)Sb4—S12.4477 (11)
Sb1—S32.4819 (11)Sb4—S62.4467 (12)
Sb2—S22.4944 (12)Sb4—S72.4884 (11)
Sb2—S42.4074 (11)S7—S7ii2.101 (2)
Sb2—S52.4833 (12)N1—C11.464 (8)
Sb3—S32.4745 (11)N2—C21.463 (8)
Sb3—S52.4771 (11)
S1—Sb1—S291.41 (4)S1—Sb4—S692.65 (4)
S1—Sb1—S385.14 (4)S1—Sb4—S795.40 (4)
S2—Sb1—S396.37 (4)S6—Sb4—S795.36 (4)
S2—Sb2—S496.17 (4)Sb1—S1—Sb499.91 (4)
S2—Sb2—S595.24 (4)Sb1—S2—Sb297.99 (4)
S4—Sb2—S595.83 (4)Sb1—S3—Sb3105.35 (4)
S3—Sb3—S598.44 (4)Sb2—S5—Sb397.85 (4)
S3—Sb3—S6i83.26 (4)Sb3iii—S6—Sb499.69 (4)
S5—Sb3—S6i89.67 (4)Sb4—S7—S7ii101.09 (7)
Symmetry codes: (i) x+1, y, z+1; (ii) −x, −y+1, −z+1; (iii) x−1, y, z−1.
 

Acknowledgements

The authors thank the UK EPSRC for grants in support of a single-crystal CCD diffractometer and a studentship for RJEL. AMC thanks The Leverhulme Trust for a Research Fellowship.

References

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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 61| Part 12| December 2005| Pages m516-m518
doi:10.1107/S0108270105032361
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