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Acta Cryst. (2007). E63, m1700    [ doi:10.1107/S1600536807023598 ]

catena-Poly[piperazinium di-[mu]-sulfido-gallium]

P. Vaqueiro and M. L. Romero

Abstract top

The structure of the title compound, {(C4H11N2)[GaS2]}n, which was prepared under solvothermal conditions, consists of one-dimensional [GaS2]- chains of edge-sharing GaS4 tetrahedra, separated by monoprotonated piperazinium cations. The crystal packing is consolidated by N-H...N and N-H...S hydrogen bonds.

Comment top

Solvothermal synthesis has been increasingly used for the preparation of a variety of sulfides containing the main group elements tin, germanium, arsenic, antimony and indium. By contrast, few solvothermally prepared gallium sulfides are known. Initial studies (Zheng et al., 2003) suggested that there was large degree of similarity between the structural chemistry of solvothermally prepared indium and gallium sulfides. However, while the vast majority of reported structures for indium sulfides are based on supertetrahedral clusters (Bu, Zheng & Feng, 2004), recent work on gallium sulfides has resulted in the preparation of materials containing a variety of building units, including the one-dimensional [GaS2]- chains observed in the title compound, (I).

The local coordination and the atom labelling scheme for the title compound is depicted in Figure 1. The structure of {(C4H11N2)[GaS2]}n contains GaS4 tetrahedra, linked together by sharing non-adjacent edges to form one-dimensional [GaS2]- chains, as shown in Figure 2. The [GaS2]- chains, which run parallel to the a-axis, are separated by monoprotonated piperazinium cations. As shown in Figure 3, each piperazinium cation exhibits hydrogen-bonding interactions with sulfur atoms in the [GaS2]- chains as well as with other piperazinium cations (Table 2).

The compound reported here is isostructural to piperazinium gallium selenide, {(C4H11N2)[GaSe2]}n (Bu, Zheng, Wang et al., 2004), which contains [GaSe2]- chains. A gallium selenide containing six-gallium atom fragments, [Ga6Se14]10-, of this type of one-dimensional chains has also been reported (Deiseroth & Fu-Son, 1981). Recently some solvothermally prepared gallium sulfides, [C10N4H26]0.5[GaS2] and [M(en)3]0.5[GaS2] (M = Mn, Co, Ni), which contain [GaS2]- chains separated by monoprotonated 1,4-bis(3-aminopropyl)piperazine or [M(en)3]2+ complexes respectively, have also been described (Vaqueiro, 2006ab). Furthermore, the one-dimensional [GaS2]- chains of the title compound are similar to those found in SiS2 (Peters & Krebs, 1982) and in KFeS2-type compounds (Bronger et al., 1987). While all of these compounds contain [MQ2]-chains (M= Si, Fe, Ga; Q = S, Se) formed by edge-sharing MQ4 tetrahedra, the packing of the chains differs significantly between these phases. This might be related to the presence of a hydrogen-bond network in some of these materials.

Related literature top

For related literature, see: Zheng et al. (2003); Bu, Zheng & Feng (2004); Peters & Krebs (1982); Bronger et al. (1987). The isostructural gallium selenide, {(C4H11N2)[GaSe2]}n, was described by Bu, Zheng, Wang et al. (2004). Related structures containing one-dimensional [GaS2]- chains were described by Vaqueiro (2006a,b). A fragment of a gallium selenide chain, [Ga6Se14]10-, was reported by Deiseroth & Fu-Son (1981).

For related literature, see: Bu, Zheng & Feng (2004).

Experimental top

A mixture of Ga2S3 (136.8 mg; 0.58 mmol), sulfur (148.5 mg; 4.64 mmol) and piperazine (1.290 g, 15 mmol) was loaded into a 23 ml Teflon-lined stainless steel autoclave. 3 ml of methanol were added to form a mixture with an approximate molar composition Ga2S3:S:piperazine:methanol of 0.58:4.64:15:74. After stirring the mixture, the container was closed, heated at 443 K for 10 days, and then cooled to room temperature at a cooling rate of 1 K min-1. The product, which contained a large number of colourless blocks of the title compound, was filtered, washed with methanol, deionized water and acetone and dried in air at room temperature.

Refinement top

The hydrogen atoms were placed geometrically after each cycle of refinement (C—H = 1.00 Å, N—H = 1.00 Å) and Uiso(H) = 1.2Ueq(carrier), but not refined.

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 diagram for (I) showing the atom labelling scheme and displacement ellipsoids at 50% probability (arbitrary spheres for the H atoms).
[Figure 2] Fig. 2. View of the {(C4H11N2)[GaS2]}n structure along the [001] direction. Hydrogen atoms have been omitted for clarity.
[Figure 3] Fig. 3. View of the {(C4H11N2)[GaS2]}n structure showing the hydrogen-bond network (dashed lines).
catena-Poly[piperazinium di-µ-sulfido-gallium] top
Crystal data top
(C4H11N2)[GaS2]F(000) = 448
Mr = 221.00Dx = 1.836 Mg m−3
Monoclinic, P21/cMelting point: not measured K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 6.0798 (5) ÅCell parameters from 2182 reflections
b = 16.2655 (13) Åθ = 2.8–31.5°
c = 8.3611 (8) ŵ = 3.88 mm−1
β = 104.827 (5)°T = 298 K
V = 799.31 (12) Å3Block, colourless
Z = 40.20 × 0.12 × 0.08 mm
Data collection top
Bruker-Nonius APEX-2 CCD area-detector
diffractometer		1772 reflections with I > 3.00u(I)
graphiteRint = 0.025
ω/2θ scansθmax = 31.5°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→7
Tmin = 0.554, Tmax = 0.733k = −23→23
11588 measured reflectionsl = −12→12
2644 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)] = 0.022H-atom parameters not refined
wR(F2) = 0.026 Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)]
where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)2]2 Ai are: 1.32 -1.15 1.10 -0.477
[Prince, E. (1982). Mathematical Techniques in Crystallography and Materials Science. New York: Springer-Verlag. Watkin, D. (1994). Acta Cryst. A50, 411–437.]
S = 1.04(Δ/σ)max = 0.001
1772 reflectionsΔρmax = 0.55 e Å−3
82 parametersΔρmin = −0.61 e Å−3
0 restraints
Crystal data top
(C4H11N2)[GaS2]V = 799.31 (12) Å3
Mr = 221.00Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.0798 (5) ŵ = 3.88 mm−1
b = 16.2655 (13) ÅT = 298 K
c = 8.3611 (8) Å0.20 × 0.12 × 0.08 mm
β = 104.827 (5)°
Data collection top
Bruker-Nonius APEX-2 CCD area-detector
diffractometer		2644 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1772 reflections with I > 3.00u(I)
Tmin = 0.554, Tmax = 0.733Rint = 0.025
11588 measured reflectionsθmax = 31.5°
Refinement top
R[F2 > 2σ(F2)] = 0.022H-atom parameters not refined
wR(F2) = 0.026Δρmax = 0.55 e Å−3
S = 1.04Δρmin = −0.61 e Å−3
1772 reflectionsAbsolute structure: ?
82 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ga10.25176 (3)0.497823 (12)0.99690 (2)0.0164
S2−0.06988 (7)0.53947 (3)0.80332 (6)0.0200
S30.47634 (7)0.40352 (3)0.91380 (6)0.0230
N40.2400 (3)0.71296 (11)0.7036 (2)0.0272
C50.0475 (4)0.72761 (15)0.5606 (3)0.0312
C60.0018 (4)0.65667 (16)0.4372 (3)0.0322
N70.2128 (3)0.63714 (11)0.3850 (2)0.0276
C80.4055 (4)0.61672 (13)0.5316 (3)0.0295
C90.4449 (4)0.68875 (13)0.6515 (3)0.0277
H410.27300.76450.77080.0330*
H420.19940.66800.77250.0330*
H510.07980.77810.50230.0382*
H52−0.09180.73660.60110.0382*
H61−0.12170.67270.33800.0385*
H62−0.04680.60720.49030.0385*
H720.18300.58900.30810.0333*
H810.54650.60620.49410.0354*
H820.36650.56660.58780.0354*
H910.49690.73700.59660.0320*
H920.56630.67310.75210.0320*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ga10.01204 (8)0.01849 (9)0.01931 (9)0.00000 (6)0.00510 (6)−0.00066 (7)
S20.01562 (16)0.0259 (2)0.01824 (18)0.00077 (16)0.00391 (13)0.00456 (16)
S30.01648 (17)0.01957 (19)0.0337 (2)−0.00186 (16)0.00780 (16)−0.00880 (17)
N40.0356 (9)0.0248 (8)0.0221 (8)−0.0025 (7)0.0091 (7)−0.0007 (6)
C50.0234 (9)0.0401 (11)0.0320 (10)0.0026 (8)0.0103 (8)−0.0023 (9)
C60.0259 (9)0.0430 (12)0.0274 (10)−0.0110 (8)0.0063 (7)−0.0027 (9)
N70.0353 (9)0.0274 (8)0.0207 (7)−0.0051 (7)0.0083 (7)−0.0036 (6)
C80.0344 (10)0.0239 (9)0.0301 (10)0.0049 (7)0.0079 (9)−0.0008 (7)
C90.0272 (9)0.0237 (9)0.0290 (9)0.0012 (7)0.0015 (7)−0.0025 (7)
Geometric parameters (Å, °) top
Ga1—S2i2.3078 (5)C6—N71.491 (3)
Ga1—S3ii2.2877 (5)C6—H611.000
Ga1—S22.2984 (5)C6—H621.000
Ga1—S32.2771 (5)N7—C81.500 (3)
N4—C51.463 (3)N7—H721.000
N4—C91.475 (3)C8—C91.521 (3)
N4—H411.000C8—H811.000
N4—H421.000C8—H821.000
C5—C61.525 (3)C9—H911.000
C5—H511.000C9—H921.000
C5—H521.000
S2i—Ga1—S3ii112.84 (2)C5—C6—H61109.402
S2i—Ga1—S296.215 (17)N7—C6—H61109.413
S3ii—Ga1—S2115.89 (2)C5—C6—H62109.402
S2i—Ga1—S3118.656 (19)N7—C6—H62109.406
S3ii—Ga1—S397.608 (17)H61—C6—H62109.466
S2—Ga1—S3116.89 (2)C6—N7—C8111.02 (17)
Ga1i—S2—Ga183.785 (17)C6—N7—H72109.088
Ga1ii—S3—Ga182.392 (17)C8—N7—H72109.088
C5—N4—C9111.17 (16)N7—C8—C9109.05 (16)
C5—N4—H41109.046N7—C8—H81109.583
C9—N4—H41109.042C9—C8—H81109.582
C5—N4—H42109.048N7—C8—H82109.574
C9—N4—H42109.048C9—C8—H82109.580
H41—N4—H42109.470H81—C8—H82109.462
N4—C5—C6113.51 (19)C8—C9—N4113.48 (17)
N4—C5—H51108.449C8—C9—H91108.461
C6—C5—H51108.456N4—C9—H91108.464
N4—C5—H52108.445C8—C9—H92108.461
C6—C5—H52108.458N4—C9—H92108.458
H51—C5—H52109.469H91—C9—H92109.470
C5—C6—N7109.74 (16)
Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x+1, −y+1, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H41···N7iii1.001.952.898 (2)158
N4—H42···S21.002.713.6072 (19)150
N7—H72···S2iv1.002.323.2842 (18)162
Symmetry codes: (iii) x, −y+3/2, z+1/2; (iv) −x, −y+1, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Ga1—S2i2.3078 (5)Ga1—S22.2984 (5)
Ga1—S3ii2.2877 (5)Ga1—S32.2771 (5)
S2i—Ga1—S3ii112.84 (2)S2i—Ga1—S3118.656 (19)
S2i—Ga1—S296.215 (17)S3ii—Ga1—S397.608 (17)
S3ii—Ga1—S2115.89 (2)S2—Ga1—S3116.89 (2)
Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x+1, −y+1, −z+2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H41···N7iii1.001.952.898 (2)158
N4—H42···S21.002.713.6072 (19)150
N7—H72···S2iv1.002.323.2842 (18)162
Symmetry codes: (iii) x, −y+3/2, z+1/2; (iv) −x, −y+1, −z+1.
Acknowledgements top

The authors thank the UK EPSRC for grants in support of a project studentship (MLR) and an Advanced Research Fellowship for PV.

references
References top

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