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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 63| Part 1| January 2007| Pages m27-m29
doi:10.1107/S010827010605044X

1,4,8,11-Tetra­aza­cyclo­tetra­decane anti­mony(III) sulfide

CROSSMARK_Color_square_no_text.svg
Rachel J. E. Lees,a Anthony V. Powell,a* David J. Watkinb and Ann M. Chippindalec

aDepartment of Chemistry, Heriot–Watt University, Edinburgh EH14 4AS, Scotland, bChemical Crystallography Laboratory, Chemistry Research Laboratory, University of Oxford, Oxford OX1 3TA, England, and cSchool of Chemistry, The University of Reading, Whiteknights, Reading RG6 6AD, England
*Correspondence e-mail: a.v.powell@hw.ac.uk

(Received 24 October 2006; accepted 22 November 2006; online 23 December 2006)

Poly[1,4,8,11-tetra­azacyclo­tetra­decane(2+) [hepta-μ-sulfido-tris­ulfidohexa­anti­mony(III)]], {(C10H26N4)[Sb6S10]}n, consists of novel [Sb6S10]2− layers containing Sb2S2, Sb4S4 and Sb7S7 hetero-rings, which are separated by macrocyclic amine mol­ecules. The macrocyclic amine mol­ecules are disordered over two crystallographically distinct positions and are diprotonated in order to balance the charge of the anionic layers.

Comment

Template-directed synthesis of antimony(III) sulfides under solvothermal conditions has produced a wide variety of novel structures. The structural diversity arises from the stereochemical effect of the lone pair of electrons associated with SbIII, together with the potential for antimony to exhibit coordination numbers that range from 3 to 6. The primary building units in solvothermally synthesized antimony sulfides are [SbS3]3− trigonal pyramids. These may be connected through corner- or edge-sharing to create larger secondary building units, including a variety of SbxSx hetero-rings and [Sb3S6]3− semicubes. Condensation of these building units can form chain, layered and three-dimensional antimony–sulfide structures, such as [Fe(C2H8N2)3]2[Sb4S8] (Lees et al., 2005[Lees, R. J. E., Powell, A. V. & Chippindale, A. M. (2005). Polyhedron, 24, 1941-1948.]), [Fe(C4H13N3)2][Sb6S10]·0.5H2O (Stahler et al., 2001[Stahler, R., Nather, C. & Bensch, W. (2001). Eur. J. Inorg. Chem. 7, 1835-1840.]) and [Co(C2H8N2)3]2[Sb12S19] (Vaqueiro, Chippindale et al., 2004[Vaqueiro, P., Chippindale, A. M. & Powell, A. V. (2004). Inorg. Chem. 43, 7963-7965.]), respectively. The synthesis of these materials is generally performed using organic amines as structure-directing agents. The amines used to date have been principally linear and branched long-chain aliphatic amines and polyamines and alicyclic amines, such as ethyl­ene­diamine (Tan et al., 1994[Tan, K., Ko, Y. & Parise, J. B. (1994). Acta Cryst. C50, 1439-1442.]), tris­(2-amino­ethyl)amine (Vaqueiro, Darlow et al., 2004[Vaqueiro, P., Darlow, D. P., Powell, A. V. & Chippindale, A. M. (2004). Solid State Ionics, 172, 601-605.]) and piperazine (Parise & Ko, 1992[Parise, J. B. & Ko, Y. (1992). Chem. Mater. 4, 1446-1450.]). The organic species is generally protonated in order to balance the negative charge of the anionic antimony–sulfide framework. Recently, we demonstrated that the macrocyclic amine cyclam can act as a structure-directing agent for solvothermally synthesized anti­mony sulfides (Powell et al., 2006[Powell, A. V., Lees, R. J. E. & Chippindale, A. M. (2006). Inorg. Chem. 45, 4261-4267.]). We prepared (C10H26N4)[Sb4S7], which represents a rare example of a truly three-dimensional antimony–sulfide framework and contains diprotonated cyclam mol­ecules in the framework pores. We report here the structure of (C10H26N4)[Sb6S10], a layered antimony sulfide containing diprotonated cyclam, which was obtained as a minor product during the synthesis of (C10H26N4)[Sb4S7].

The asymmetric unit of the title compound contains three Sb and five S atoms, all of which occupy general positions. Atoms Sb1 and Sb3 show trigonal–pyramidal coordination, with Sb—S bond distances ranging from 2.4072 (16) to 2.4855 (15) Å and S—Sb—S angles ranging from 84.00 (5) to 100.8 (2)° (Table 1[link]). Atom Sb2 is coordinated by four S atoms, with two shorter bonds and two longer bonds. The distances range from 2.4059 (15) to 2.8920 (15) Å, which is less than the sum of the van der Waals radii of antimony and sulfur (3.8 Å; Bondi, 1964[Bondi, A. (1964). J. Phys. Chem. 68, 441-451.]), and the S—Sb—S angles lie in the range 87.44 (5)–96.27 (5)°. The bond lengths and angles are consistent with those found in other solvothermally synthesized anti­mony–sulfide materials containing [SbS3]3− and [SbS4]5− units (Stahler et al., 2001[Stahler, R., Nather, C. & Bensch, W. (2001). Eur. J. Inorg. Chem. 7, 1835-1840.]; Spetzler et al., 2004[Spetzler, V., Kiebach, R., Näther, C. & Bensch, W. (2004). Z. Anorg. Allg. Chem. 630, 2398-2404.]). The bond-valence sums (Brese & O'Keeffe, 1991[Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192-197.]) for atoms Sb1, Sb2 and Sb3 are 2.83, 2.98 and 2.98, respectively. These values are consistent with the presence of SbIII in the framework. Vertex-linking of four [SbS3]3− trigonal–pyramidal units generates an Sb4S4 hetero-ring, in which atoms Sb1 and Sb3 alternate around the ring. Each of the four terminal S atoms of the Sb4S4 hetero-ring is shared with an [SbS4]5− unit (Fig. 1[link]). These serve to link the rings into [Sb6S10]2− layers. Edge-sharing of two adjacent [SbS4]5− units generates Sb2S2 hetero-rings within the layers (Fig. 2[link]). The anionic antimony–sulfide layers lie parallel to the bc crystallographic plane and are stacked directly above one another along [100], separated by charge-balancing diprotonated macrocyclic cations (Fig. 3[link]). Diproton­ated cyclam mol­ecules have been observed previously, examples being (C10H26N4)[Sb4S7] (Powell et al., 2006[Powell, A. V., Lees, R. J. E. & Chippindale, A. M. (2006). Inorg. Chem. 45, 4261-4267.]) and (C10H26N4)[ClO4]2 (Nave & Truter, 1974[Nave, C. & Truter, M. R. (1974). J. Chem. Soc. Dalton Trans. 21, 2351-2354.]). The distance across the cyclam ring is 3.785 (6) Å for N1⋯N1iv and 4.161 (6) Å for N2⋯N2iv (Fig. 1[link]). The shortest distance between the macrocyclic cation and the antimony–sulfide framework is 3.351 (4) Å (N2i⋯S2), which is short enough to allow hydrogen bonding between the macrocycle and the anti­mony–sulfide framework.

The structure of the [Sb6S10]2− layers of the title compound represents a new antimony–sulfide structural motif in which Sb2S2, Sb4S4 and Sb7S7 hetero-rings form the anionic layers. The structure of the layers is significantly different from those of previously reported examples of antimony–sulfide layers with the same antimony–sulfur ratio. For example, the layers within [Fe(C4H13N3)2][Sb6S10]·0.5H2O (Stahler et al., 2001[Stahler, R., Nather, C. & Bensch, W. (2001). Eur. J. Inorg. Chem. 7, 1835-1840.]) are composed of Sb2S2, Sb4S4 and Sb5S5 hetero-rings which surround Sb16S16 rings, whilst in (trans-1,4-C6H15N2)[Sb3S5] and (trans-1,2-C6H15N2)[Sb3S5] (Engelke et al., 2002[Engelke, L., Näther, C. & Bensch, W. (2002). Eur. J. Inorg. Chem. 11, 2936-2941.]), Sb2S2, Sb4S4 and Sb10S10 hetero-rings are arranged to form the anionic layers.

[Figure 1]
Figure 1
Local coordination of Sb and S atoms showing the Sb4S4 hetero-ring and an [SbS4]5− unit connected through a shared S3 atom (bottom), and one of the two disordered and diprotonated cyclam mol­ecules (top), showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) −x + 2, y + [{1\over 2}], −z + [{3\over 2}]; (ii) −x + 2, −y + 2, −z + 1; (iii) −x + 2, −y + 1, −z + 1; (iv) −x + 1, −y + 2, −z; (v) x, −y + [{3\over 2}], z − [{1\over 2}].]
[Figure 2]
Figure 2
The [Sb6S10]2− layers viewed along [100], with the unit cell outlined. Key: Sb atoms are large solid circles and S atoms are large open circles.
[Figure 3]
Figure 3
The [Sb6S10]2− layers separated by diprotonated cyclam mol­ecules, with the unit cell outlined. H atoms have been omitted. Key: Sb atoms are large solid circles, S atoms are large open circles, C atoms are small solid circles and N atoms are small open circles.

Experimental

(C10H26N4)[Sb6S10] was synthesized by the reaction of cyclam (1.5 mmol), Sb2S3 (2 mmol) and sulfur (5 mmol) in deionized water (3 ml). The mixture was heated in a 23 ml Teflon-lined stainless steel autoclave at 438 K for 4 d before cooling to room temperature at a rate of 20 K h−1. The solid product was filtered off, washed with deionized water and acetone, and dried at room temperature. The product consisted of orange blocks of the title compound as a minor phase, as well as a larger proportion of yellow blocks of (C10H26N4)[Sb4S7] (Powell et al., 2006[Powell, A. V., Lees, R. J. E. & Chippindale, A. M. (2006). Inorg. Chem. 45, 4261-4267.]) and red blocks of (C2H8N2)[Sb8S13] (Tan et al., 1994[Tan, K., Ko, Y. & Parise, J. B. (1994). Acta Cryst. C50, 1439-1442.]), identified by single-crystal X-ray diffraction and present in approximately equal amounts, together with a small amount of unreacted Sb2S3, as identified by powder X-ray diffraction.

Crystal data

  • (C10H26N4)[Sb6S10]

  • Mr = 1253.46

  • Monoclinic, P 21 /c

  • a = 9.4872 (9) Å

  • b = 15.4477 (14) Å

  • c = 10.7567 (9) Å

  • β = 105.878 (4)°

  • V = 1516.3 (2) Å3

  • Z = 2

  • Dx = 2.732 Mg m−3

  • Mo Kα radiation

  • μ = 5.97 mm−1

  • T = 100 K

  • Block, orange

  • 0.16 × 0.12 × 0.06 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 = 0.44, Tmax = 0.70

  • 49836 measured reflections

  • 4612 independent reflections

  • 4008 reflections with I > 3.0σ(I)

  • Rint = 0.083

  • θmax = 30.6°
Refinement

  • Refinement on F

  • R[F2 > 2σ(F2)] = 0.049

  • wR(F2) = 0.038

  • S = 1.08

  • 4008 reflections

  • 150 parameters

  • H-atom parameters constrained

  • Modified Chebychev polynomial (Watkin, 1994[Watkin, D. (1994). Acta Cryst. A50, 411-437.]) with coefficients 1.00, −1.11, 0.479 and −0.402

  • (Δ/σ)max = 0.007

  • Δρmax = 3.16 e Å−3

  • Δρmin = −2.81 e Å−3

Table 1
Selected geometric parameters (Å, °)

Sb1—S1i 2.4855 (15)
Sb1—S5ii 2.469 (9)
Sb1—S4 2.4621 (14)
Sb2—S2iii 2.8920 (15)
Sb2—S1 2.4723 (15)
Sb2—S2 2.4059 (15)
Sb2—S3 2.6319 (16)
Sb3—S3 2.4072 (16)
Sb3—S4 2.4826 (15)
Sb3—S5 2.4730 (15)
S1i—Sb1—S5ii 84.00 (5) 
S1i—Sb1—S4 93.80 (5)
S5ii—Sb1—S4 92.05 (5)
S2iii—Sb2—S1 88.66 (5)
S2iii—Sb2—S2 87.44 (5)
S1—Sb2—S2 96.27 (5)
S1—Sb2—S3 87.09 (5)
S2—Sb2—S3 91.97 (5)
S3—Sb3—S4 88.13 (5)
S3—Sb3—S5 100.8 (2)
S4—Sb3—S5 97.4 (3)
Symmetry codes: (i) [-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) -x+2, -y+2, -z+1; (iii) -x+2, -y+1, -z+1.

During refinement, inspection of the anisotropic displacement parameters indicated that the macrocyclic ring atoms were disordered. The C atoms were modelled as split over two positions, with both site occupancies fixed at 0.5. One set of Uij values was refined for each pair of related C atoms. Bond length and angle similarity restraints were applied between the two disordered threads and Hirshfield restraints applied to the Uij values along the bonds. C-bound H atoms were positioned geometrically [C—H = 0.97 (1) Å and Uiso(H) = 1.2Ueq(C)] and allowed to ride on the carrier atoms. The three H atoms attached to N1 and N2, which are required for charge balancing the antimony–sulfide framework, were not included in the refinement. The largest residual peak in the final Fourier map was located 0.506 Å from C31 and the largest electron density trough was located 0.883 Å from Sb2. The position of the beam stop precluded proper measurement of the omitted reflections.

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 (Betteridge et al., 2003[Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487.]); molecular graphics: ATOMS (Dowty, 2000[Dowty, E. (2000). ATOMS. Version 6.1. Shape Software, Hidden Valley Road, Kingsport, Tennessee, USA.]); software used to prepare material for publication: CRYSTALS.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S010827010605044X/ga3032sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S010827010605044X/ga3032Isup2.hkl


Comment top

Template-directed synthesis of antimony (III) sulfides under solvothermal conditions has produced a wide variety of novel structures. The structural diversity arises from the stereochemical effect of the lone pair of electrons associated with SbIII, together with the potential for antimony to exhibit coordination numbers that range from 3 to 6. The primary building units in solvothermally synthesized antimony sulfides are [SbS3]3− trigonal pyramids. These may be connected through corner or edge sharing to create larger secondary building units, including a variety of SbxSx heterorings and [Sb3S6]3− semicubes. Condensation of these building units can form chain, layered and three-dimensional antimony–sulfide structures such as [Fe(C2H8N2)3]2[Sb4S8] (Lees et al., 2005), [Fe(C4H13N3)2][Sb6S10]·0.5H2O (Stahler et al., 2001) and [Co(C2H8N2)3]2[Sb12S19] (Vaqueiro, Chippindale et al., 2004), respectively. The synthesis of these materials is generally performed using organic amines as structure-directing agents. The amines used to date have been principally linear and branched long-chain aliphatic amines and polyamines and alicyclic amines, such as ethylenediamine (Tan et al., 1994), tris(2-aminoethyl)amine (Vaqueiro, Darlow et al., 2004) and piperazine (Parize & Ko, 1992). The organic species is generally protonated in order to balance the negative charge of the anionic antimony–sulfide framework. Recently we demonstrated that the macrocyclic amine cyclam can act as a structure-directing agent for solvothermally synthesized antimony sulfides (Powell et al., 2006). We prepared (C10H26N4)[Sb4S7], which represents a rare example of a truly three-dimensional antimony–sulfide framework and contains diprotonated cyclam molecules in the framework pores. We report here the structure of (C10H26N4)[Sb6S10], a layered antimony sulfide containing diprotonated cyclam, which was obtained as a minor product during the synthesis of (C10H26N4)[Sb4S7].

The asymmetric unit of the title compound contains three Sb and five S atoms, all of which occupy general positions. Atoms Sb1 and Sb3 show trigonal–pyramidal coordination with Sb—S bond distances ranging from 2.4072 (16) to 2.4855 (15) Å, and S—Sb—S angles ranging from 84.00 (5) to 100.8 (2)°. Atom Sb2 is coordinated by four S atoms, with two shorter bonds and two longer bonds. The distances range from 2.4059 (15) to 2.8920 (15) Å, which is less than the sum of the van der Waals radii of antimony and sulfur (3.8 Å; Bondi, 1964), and S—Sb—S angles lie in the range 87.44 (5)–96.27 (5)°. The bond lengths and angles are consistent with those found in other solvothermally synthesized antimony–sulfide materials containing [SbS3]3− and [SbS4]5− units (Stahler et al., 2001, Spetzler et al., 2004). The bond-valence sums (Brese & O'Keeffe, 1991) for atoms Sb1, Sb2 and Sb3 are 2.83, 2.98 and 2.98, respectively. These values are consistent with the presence of SbIII in the framework. Vertex-linking of four [SbS3]3− trigonal–pyramidal units generates an Sb4S4 heteroring, in which atoms Sb1 and Sb3 alternate around the ring. Each of the four terminal S atoms of the Sb4S4 heteroring is shared with a [SbS4]5− unit (Fig. 1). These serve to link the rings into [Sb6S10]2− layers. Edge-sharing of two adjacent [SbS4]5− units generates Sb2S2 heterorings within the layers (Fig. 2). The anionic antimony–sulfide layers lie parallel to the bc crystallographic plane and are stacked directly above one another along [100], separated by charge-balancing diprotonated macrocyclic cations (Fig. 3). Diprotonated cyclam molecules have been observed previously in compounds including (C10H26N4)[Sb4S7] (Powell et al., 2006) and (C10H26N4)[ClO4]2 (Nave & Truter, 1974). The distance across the cyclam ring is 3.785 (6) Å for N1···N1iv and 4.161 (6) Å for N2···N2iv (Fig. 1). The shortest distance between the macrocyclic cation and the antimony–sulfide framework is 3.351 (4) Å (N2i···S2), which is short enough to allow hydrogen bonding between the macrocycle and the antimony–sulfide framework.

The structure of the [Sb6S10]2− layers of the title compound represents a new antimony–sulfide structural motif in which Sb2S2, Sb4S4 and Sb7S7 heterorings form the anionic layers. The structure of the layers is significantly different from those of previously reported examples of antimony–sulfide layers with the same antimony–sulfur ratio. For example the layers within [Fe(C4H13N3)2][Sb6S10]·0.5H2O (Stahler et al., 2001) are composed of Sb2S2, Sb4S4 and Sb5S5 heterorings which surround Sb16S16 rings, whilst in (trans-1,4-C6H15N2)[Sb3S5] and (trans-1,2-C6H15N2)[Sb3S5] (Engelke et al., 2002), Sb2S2, Sb4S4 and Sb10S10 heterorings are arranged to form the anionic layers.

Experimental top

(C10H26N4)[Sb6S10] was synthesized by the reaction of cyclam (1.5 mmol), Sb2S3 (2 mmol) and sulfur (5 mmol) in deionized water (3 ml). The mixture was heated in a 23 ml Teflon-lined stainless-steel autoclave at 438 K for 4 d before cooling to room temperature at 20 K h−1. The solid product was filtered off, washed with deionized water and acetone, and dried at room temperature. The product consisted of orange blocks of the title compound as a minor phase, as well as a larger proportion of yellow blocks of (C10H26N4)[Sb4S7] (Powell et al., 2006) and red blocks of (C2H8N2)[Sb8S13] (Tan et al., 1994), identified by single-crystal X-ray diffraction and present in approximately equal amounts, together with a small amount of unreacted Sb2S3 as identified by powder X-ray diffraction.

Refinement top

During refinement, inspection of the anisotropic displacement parameters (adps) indicated that the macrocycle ring atoms were disordered. The C atoms were modelled as split over two positions, with both site occupancies fixed at 0.5. One set of Uij values was refined for each pair of related C atoms. Bond length and bond angle similarity restraints were applied between the two disordered threads and Hirshfield restraints applied to the Uij values along the bonds. C-bound H atoms were positioned geometrically [C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C)] and allowed to ride on the carrier atoms. The three H atoms attached to N1 and N2, which are required for charge balancing the antimony–sulfide framework, were not included in the refinement. The largest residual peak in the final Fourier map was located 0.506 Å from C31, and the largest electron density trough was located 0.883 Å from Sb2. The position of the beam stop precluded proper measurement of the omitted reflections.

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 (Betteridge et al., 2003); molecular graphics: ATOMS (Dowty, 2000); software used to prepare material for publication: CRYSTALS.

Figures top
[Figure 1] Fig. 1. Local coordination of (bottom) Sb and S atoms showing the Sb4S4 heteroring and an [SbS4]5−unit connected through a shared S3 atom and (top) one of the two disordered and diprotonated cyclam molecules, showing the atom labeling scheme and displacement ellipsoids at 50% probability. (H atoms have been omitted for clarity.) [Symmetry codes: (i) −x + 2, y + 1/2, −z + 3/2; (ii) −x + 2, −y + 2, −z + 1; (iii) −x + 2, −y + 1, −z + 1; (iv) −x + 1, −y + 2, −z; (v) x, −y + 3/2, z − 1/2.]
[Figure 2] Fig. 2. The [Sb6S10]2− layers viewed along [100], with unit cell outlined. (Key: antimony, large solid circles; sulfur, large open circles).
[Figure 3] Fig. 3. The [Sb6S10]2− layers separated by diprotonated cyclam molecules, with unit cell outlined. H atoms have been omitted. (Key: antimony, large solid circles; sulfur, large open circles; carbon, small solid circles; nitrogen, small open circles).
Poly[1,4,8,11-tetraazacyclotetradecane(2+) [hepta-µ-sulfido-trisulfidohexaantimony(III)]] top
Crystal data top
(C10H20N4)[Sb6S10]F(000) = 1148
Mr = 1247.46Dx = 2.732 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4160 reflections
a = 9.4872 (9) Åθ = 2.2–30.5°
b = 15.4477 (14) ŵ = 5.97 mm−1
c = 10.7567 (9) ÅT = 100 K
β = 105.878 (4)°Block, orange
V = 1516.3 (2) Å30.16 × 0.12 × 0.06 mm
Z = 2
Data collection top
Bruker–Nonius Apex-2 CCD area-detector
diffractometer		4008 reflections with I > 3.0σ(I)
Graphite monochromatorRint = 0.083
ω/2θ scansθmax = 30.6°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −13→13
Tmin = 0.44, Tmax = 0.70k = 0→22
49836 measured reflectionsl = 0→15
4612 independent reflections
Refinement top
Refinement on FPrimary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.038 Modified Chebychev polynomial, (Watkin, 1994) with coefficients 1.00, -1.11, 0.479 and -0.402
S = 1.08(Δ/σ)max = 0.007
4008 reflectionsΔρmax = 3.16 e Å−3
150 parametersΔρmin = −2.81 e Å−3
72 restraints
Crystal data top
(C10H20N4)[Sb6S10]V = 1516.3 (2) Å3
Mr = 1247.46Z = 2
Monoclinic, P21/cMo Kα radiation
a = 9.4872 (9) ŵ = 5.97 mm−1
b = 15.4477 (14) ÅT = 100 K
c = 10.7567 (9) Å0.16 × 0.12 × 0.06 mm
β = 105.878 (4)°
Data collection top
Bruker–Nonius Apex-2 CCD area-detector
diffractometer		4612 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		4008 reflections with I > 3.0σ(I)
Tmin = 0.44, Tmax = 0.70Rint = 0.083
49836 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04972 restraints
wR(F2) = 0.038H-atom parameters constrained
S = 1.08Δρmax = 3.16 e Å−3
4008 reflectionsΔρmin = −2.81 e Å−3
150 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Sb11.00384 (4)1.08793 (2)0.65826 (4)0.0091
Sb20.97163 (4)0.62304 (2)0.50401 (4)0.0103
Sb31.01909 (4)0.8336 (2)0.68011 (4)0.0102
S11.16052 (15)0.63947 (9)0.71266 (14)0.0109
S20.84366 (15)0.50475 (9)0.56996 (15)0.0115
S30.81632 (17)0.73823 (10)0.58957 (19)0.0187
S40.85825 (15)0.95669 (9)0.58297 (14)0.0115
S51.15565 (16)0.8234 (10)0.51501 (15)0.0134
N10.4837 (6)1.1163 (3)0.0497 (6)0.0337
N20.4565 (6)0.9642 (4)0.1723 (5)0.0291
C10.515 (2)1.1615 (8)0.1700 (12)0.04980.5
C20.4566 (17)1.1105 (8)0.2678 (11)0.05150.5
C30.5160 (2)1.0191 (8)0.2928 (10)0.05330.5
C40.5149 (17)0.8740 (6)0.1742 (9)0.04530.5
C50.4599 (17)0.8345 (7)0.0411 (10)0.04960.5
C110.542 (2)1.1501 (10)0.1799 (11)0.04980.5
C210.4665 (16)1.1067 (8)0.2728 (10)0.05150.5
C310.502 (2)1.0129 (7)0.2972 (8)0.05330.5
C410.5109 (16)0.8729 (6)0.1723 (9)0.04530.5
C510.4557 (17)0.8354 (7)0.0384 (9)0.04960.5
H210.48261.14170.34940.0611*0.5
H220.35061.10740.23520.0611*0.5
H310.48620.99380.36430.064*0.5
H320.62231.02050.31390.064*0.5
H410.4820.83960.23640.057*0.5
H420.62130.87570.19860.057*0.5
H510.35350.83630.01420.063*0.5
H520.49320.7750.04330.0631*0.5
H1110.5251.2120.17910.0591*0.5
H1120.64661.13870.20910.059*0.5
H2110.49581.1370.35520.0611*0.5
H2120.36131.11220.23620.0611*0.5
H3110.45150.98980.35690.064*0.5
H3120.60731.00630.3340.064*0.5
H4110.47590.83850.23320.057*0.5
H4120.61730.87310.19740.057*0.5
H5110.34940.83930.01050.063*0.5
H5120.48570.77520.03950.0632*0.5
H110.46911.21830.15640.0591*0.5
H120.62021.1680.20390.059*0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sb10.00918 (14)0.00665 (14)0.01075 (15)0.00060 (12)0.00176 (12)−0.00020 (12)
Sb20.01056 (15)0.00842 (14)0.01083 (16)0.00027 (13)0.00106 (12)0.00012 (13)
Sb30.01191 (16)0.00749 (14)0.01076 (15)0.00031 (13)0.00243 (12)−0.00037 (13)
S10.0103 (6)0.0105 (6)0.0119 (6)−0.0018 (5)0.0030 (5)−0.0005 (5)
S20.0098 (6)0.0080 (5)0.0153 (6)−0.0011 (5)0.0009 (5)−0.0017 (5)
S30.0115 (6)0.0090 (6)0.0368 (9)−0.0013 (5)0.0086 (6)−0.0052 (6)
S40.0120 (6)0.0066 (5)0.0156 (6)0.0001 (5)0.0033 (5)−0.0010 (5)
S50.0117 (6)0.0128 (6)0.0167 (6)0.0050 (5)0.0054 (5)0.0049 (5)
N10.011 (2)0.015 (3)0.075 (6)−0.003 (2)0.012 (3)−0.011 (3)
N20.012 (2)0.045 (4)0.031 (3)0.005 (3)0.007 (2)0.017 (3)
C10.038 (5)0.049 (4)0.061 (4)0.003 (3)0.009 (5)−0.024 (4)
C20.042 (4)0.066 (4)0.043 (4)0.000 (3)0.006 (4)−0.034 (3)
C30.040 (4)0.078 (4)0.044 (4)0.003 (3)0.013 (5)−0.004 (4)
C40.032 (3)0.049 (4)0.063 (4)0.012 (3)0.027 (4)0.031 (3)
C50.0512 (10)0.0508 (10)0.0540 (10)0.0071 (7)0.026 (4)0.0005 (10)
C110.038 (5)0.049 (4)0.061 (4)0.003 (3)0.009 (5)−0.024 (4)
C210.042 (4)0.066 (4)0.043 (4)0.000 (3)0.006 (4)−0.034 (3)
C310.040 (4)0.078 (4)0.044 (4)0.003 (3)0.013 (5)−0.004 (4)
C410.032 (3)0.049 (4)0.063 (4)0.012 (3)0.027 (4)0.031 (3)
C510.0512 (10)0.0508 (10)0.0540 (10)0.0071 (7)0.026 (4)0.0005 (10)
Geometric parameters (Å, º) top
Sb1—S1i2.4855 (15)C1—C21.534 (10)
Sb1—S5ii2.469 (9)C1—H110.971
Sb1—S42.4621 (14)C1—H120.972
Sb2—S2iii2.8920 (15)C2—C31.517 (9)
Sb2—S12.4723 (15)C2—H210.973
Sb2—S22.4059 (15)C2—H220.971
Sb2—S32.6319 (16)C3—H310.972
Sb3—S32.4072 (16)C3—H320.971
Sb3—S42.4826 (15)C4—C51.512 (9)
Sb3—S52.4730 (15)C4—H410.971
N1—C5iv1.450 (9)C4—H420.971
N1—C11.429 (9)C5—H510.972
N2—C31.522 (9)C5—H520.971
N2—C41.497 (9)
S1i—Sb1—S5ii84.00 (5)C1—C2—H22108.0
S1i—Sb1—S493.80 (5)C3—C2—H22108.4
S5ii—Sb1—S492.05 (5)H21—C2—H22109.4
S2iii—Sb2—S188.66 (5)N2—C3—C2109.57 (10)
S2iii—Sb2—S287.44 (5)N2—C3—H31109.3
S1—Sb2—S296.27 (5)C2—C3—H31109.8
S1—Sb2—S387.09 (5)N2—C3—H32109.4
S2—Sb2—S391.97 (5)C2—C3—H32109.5
S3—Sb3—S488.13 (5)H31—C3—H32109.3
S3—Sb3—S5100.8 (2)N2—C4—C5109.39 (10)
S4—Sb3—S597.4 (3)N2—C4—H41109.3
C5iv—N1—C1109.35 (10)C5—C4—H41109.8
C3—N2—C4117.22 (10)N2—C4—H42109.4
N1—C1—C2110.25 (10)C5—C4—H42109.3
N1—C1—H11109.4H41—C4—H42109.6
C2—C1—H11109.8C4—C5—N1iv109.35 (10)
N1—C1—H12109.0C4—C5—H51109.4
C2—C1—H12108.8N1iv—C5—H51109.2
H11—C1—H12109.6C4—C5—H52109.5
C1—C2—C3114.44 (10)N1iv—C5—H52109.6
C1—C2—H21108.3H51—C5—H52109.9
C3—C2—H21108.2
Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+2, −y+2, −z+1; (iii) −x+2, −y+1, −z+1; (iv) −x+1, −y+2, −z.

Experimental details

Crystal data
Chemical formula(C10H20N4)[Sb6S10]
Mr1247.46
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)9.4872 (9), 15.4477 (14), 10.7567 (9)
β (°) 105.878 (4)
V (Å3)1516.3 (2)
Z2
Radiation typeMo Kα
µ (mm−1)5.97
Crystal size (mm)0.16 × 0.12 × 0.06
Data collection
DiffractometerBruker–Nonius Apex-2 CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.44, 0.70
No. of measured, independent and
observed [I > 3.0σ(I)] reflections		49836, 4612, 4008
Rint0.083
(sin θ/λ)max (Å−1)0.716
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.038, 1.08
No. of reflections4008
No. of parameters150
No. of restraints72
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)3.16, −2.81

Computer programs: APEX2 (Bruker, 2005), APEX2, SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), ATOMS (Dowty, 2000), CRYSTALS.

Selected geometric parameters (Å, º) top
Sb1—S1i2.4855 (15)Sb2—S22.4059 (15)
Sb1—S5ii2.469 (9)Sb2—S32.6319 (16)
Sb1—S42.4621 (14)Sb3—S32.4072 (16)
Sb2—S2iii2.8920 (15)Sb3—S42.4826 (15)
Sb2—S12.4723 (15)Sb3—S52.4730 (15)
S1i—Sb1—S5ii84.00 (5)S1—Sb2—S387.09 (5)
S1i—Sb1—S493.80 (5)S2—Sb2—S391.97 (5)
S5ii—Sb1—S492.05 (5)S3—Sb3—S488.13 (5)
S2iii—Sb2—S188.66 (5)S3—Sb3—S5100.8 (2)
S2iii—Sb2—S287.44 (5)S4—Sb3—S597.4 (3)
S1—Sb2—S296.27 (5)
Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+2, −y+2, −z+1; (iii) −x+2, −y+1, −z+1.
 

Acknowledgements

We 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 63| Part 1| January 2007| Pages m27-m29
doi:10.1107/S010827010605044X
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