Cu2ZnSiS4

Rosmus, K.A.; Aitken, J.A.

doi:10.1107/S1600536811008889

inorganic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page i28

doi:10.1107/S1600536811008889

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Cu₂ZnSiS₄

Kimberly A. Rosmus ^a and Jennifer A. Aitken ^a ^*

^aDepartment of Chemistry and Biochemistry, Duquesne University, 600 Forbes Avenue, Pittsburgh, PA 15282, USA
^*Correspondence e-mail: aitkenj@duq.edu

(Received 12 February 2011; accepted 8 March 2011; online 15 March 2011)

Single crystals of Cu₂ZnSiS₄, dicopper(I) zinc silicon tetrasulfide, have been prepared via high-temperature solid-state synthesis. Cu₂ZnSiS₄ was found to have the wurtz-stannite structure type, like that of Li₂CdGeS₄, Li₂CdSnS₄, and Cu₂CdSiS₄. Each sulfur anion is tetrahedrally coordinated by two Cu cations, one Si cation, and one Zn cation, forming a three-dimensional honeycomb structure. When viewed along the c axis, the atoms are aligned in rows in which each cation alternates with the sulfur anions.

Related literature

For synthetic procedures, see: Himmrich & Haeuseler (1991 ); Nitsche et al. (1967 ); Yao et al. (1987 ). For related structures, see: Chapuis & Niggli (1972 ); Lekse et al. (2008 , 2009 ); Schäfer & Nitsche (1974 ). For optical properties, see: Levcenco et al. (2010 ).

Experimental

Crystal data

Cu₂ZnSiS₄
M_r = 348.78
Orthorhombic, P m n 2₁
a = 7.4374 (1) Å
b = 6.4001 (1) Å
c = 6.1394 (1) Å
V = 292.24 (1) Å³
Z = 2
Mo Kα radiation
μ = 12.77 mm⁻¹
T = 296 K
0.13 × 0.07 × 0.06 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ) T_min = 0.290, T_max = 0.500
5153 measured reflections
1078 independent reflections
1023 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.020
wR(F²) = 0.051
S = 1.14
1078 reflections
44 parameters
1 restraint
Δρ_max = 0.72 e Å⁻³
Δρ_min = −1.01 e Å⁻³
Absolute structure: Flack (1983 ), 449 Friedel pairs
Flack parameter: 0.02 (1)

Table 1
Selected bond lengths (Å)

Cu1—S2ⁱ	2.3170 (7)
Cu1—S3	2.325 (1)
Cu1—S1	2.3270 (6)
Cu1—S3ⁱⁱ	2.3426 (7)
Zn1—S2	2.322 (1)
Zn1—S1	2.322 (1)
Zn1—S3ⁱⁱⁱ	2.3650 (7)
Zn1—S3^iv	2.3650 (7)
Si1—S1	2.131 (1)
Si1—S3^v	2.136 (1)
Si1—S3^vi	2.136 (1)
Si1—S2^vii	2.143 (3)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y, z+{\script{1\over 2}}]$ ; (iii) -x, y, z+1; (iv) x, y, z+1; (v) $[-x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (vi) $[x-{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (vii) x, y, z-1.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2010 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811008889/si2337sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811008889/si2337Isup2.hkl

checkCIF report

Comment top

Cu₂ZnSiS₄ was prepared as crystals via iodine vapor transport reactions as early as 1967 (Nitsche et al., 1967); however, only lattice parameters were reported. Using the same synthetic method to prepare Cu₂ZnSiS₄, Yao et al. reported the infrared spectrum of this compound (Yao et al., 1987). Alternatively Cu₂ZnSiS₄ can be synthesized by grinding stoichiometric amounts of the elements and reacting them in a vibrational mill multiple times during the heating process (Himmrich & Haeuseler, 1991). More recently, the band gap of the title compound has been reported (Levcenco et al., 2010). In this paper, Cu₂ZnSiS₄ was prepared as relatively small single crystals using a simple high-temperature solid-state synthesis.

Cu₂ZnSiS₄ possesses the wurtz-stannite structure type (Schäfer, & Nitsche, 1974) like that of Li₂CdGeS₄, Li₂CdSnS₄ (Lekse et al., 2009), and Cu₂CdSiS₄ (Chapuis & Niggli, 1972). The asymmetric unit can be observed in Figure 1. Cu₂ZnSiS₄ has a diamond-like structure, where every cation is tetrahedrally coordinated with sulfur anions. The bond lengths for M—S range from 2.3170 (7)–2.3426 (7)Å for M=Cu, 2.322 (1)–2.3650 (7)Å for M=Zn, and 2.131 (1)–2.143 (3)Å for M=Si (Table 1). Every MS₄ tetrahedron points in the same direction along the crystallographic b axis rendering the structure noncentrosymmetric (Fig.2). When viewed down the c axis, the ions are aligned in rows where each cation alternates with the sulfur anions (Fig.3).

Recently second harmonic generation for a couple of compounds of this structure type, Li₂CdGeS₄ and Li₂CdSnS₄, have been reported on powder samples (Lekse et al., 2009). Therefore it is of interest to further study Cu₂ZnSiS₄.

Related literature top

For synthetic procedures, see: Himmrich & Haeuseler (1991); Nitsche et al. (1967); Yao et al. (1987). For related structures, see: Chapuis & Niggli (1972); Lekse et al. (2008); Lekse et al. (2009); Schäfer & Nitsche (1974). For optical properties, see: Levcenco et al. (2010).

Experimental top

Cu₂ZnSiS₄ was prepared via high-temperature solid-state synthesis. Stoichiometric ratios of the elements were weighed and then ground for 30 min in an argon-filled glovebox using an agate mortar and pestle. The sample was placed into a graphite crucible, which was then inserted in a 12 mm outer diameter fused-silica tube. The tube was flame sealed under a vacuum of 10^-3 mbar and transported to a computer-controlled furnace. The sample was heated to 1000°C in 12hrs, held at 1000°C for 168hrs and then cooled at 7.5°C/hr to room temperature. When removed from the furnace, blue rod-like crystals of approximate size 0.13 x 0.07 x 0.6 mm were found under a light microscope.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2010); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Asymetric unit of Cu₂ZnSiS₄ using 95% probability thermal ellipsoids.
	Fig. 2. Polyhedral view down the b axis of Cu₂ZnSiS₄ with sulfur anions as the corners of each tetrahedron.
	Fig. 3. Cu₂ZnSiS₄ viewed along the c axis showing a three-dimensional honeycomb structure where the atoms are aligned in rows with each cation alternating with sulfur anions. Color code: Cu - green, Zn - blue, Si - red, and S - yellow.

dicopper(I) zinc silicon tetrasulfide top

Crystal data top

Cu₂ZnSiS₄	F(000) = 332
M_r = 348.78	D_x = 3.964 Mg m⁻³
Orthorhombic, Pmn2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac -2	Cell parameters from 3127 reflections
a = 7.4374 (1) Å	θ = 3.2–32.2°
b = 6.4001 (1) Å	µ = 12.77 mm⁻¹
c = 6.1394 (1) Å	T = 296 K
V = 292.24 (1) Å³	Rod, blue
Z = 2	0.13 × 0.07 × 0.06 mm

Data collection top

Bruker SMART APEX diffractometer	1078 independent reflections
Radiation source: fine-focus sealed tube	1023 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 32.9°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −11→11
T_min = 0.290, T_max = 0.500	k = −9→9
5153 measured reflections	l = −9→9

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0067P)² + 0.2702P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.020	(Δ/σ)_max < 0.001
wR(F²) = 0.051	Δρ_max = 0.72 e Å⁻³
S = 1.14	Δρ_min = −1.01 e Å⁻³
1078 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
44 parameters	Extinction coefficient: 0.025 (1)
1 restraint	Absolute structure: Flack (1983), 449 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (1)

Crystal data top

Cu₂ZnSiS₄	V = 292.24 (1) Å³
M_r = 348.78	Z = 2
Orthorhombic, Pmn2₁	Mo Kα radiation
a = 7.4374 (1) Å	µ = 12.77 mm⁻¹
b = 6.4001 (1) Å	T = 296 K
c = 6.1394 (1) Å	0.13 × 0.07 × 0.06 mm

Data collection top

Bruker SMART APEX diffractometer	1078 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	1023 reflections with I > 2σ(I)
T_min = 0.290, T_max = 0.500	R_int = 0.021
5153 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	1 restraint
wR(F²) = 0.051	Δρ_max = 0.72 e Å⁻³
S = 1.14	Δρ_min = −1.01 e Å⁻³
1078 reflections	Absolute structure: Flack (1983), 449 Friedel pairs
44 parameters	Absolute structure parameter: 0.02 (1)

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.24741 (3)	0.17426 (4)	0.33723 (8)	0.0133 (1)
Zn1	0.0000	0.34747 (7)	0.84124 (15)	0.0211 (1)
Si1	0.0000	0.6743 (1)	0.3451 (4)	0.0071 (1)
S1	0.0000	0.3611 (1)	0.4632 (1)	0.0094 (1)
S2	0.0000	0.6784 (1)	0.9961 (2)	0.0089 (2)
S3	0.26269 (8)	0.1724 (1)	−0.0411 (1)	0.0100 (1)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0141 (1)	0.0135 (1)	0.0125 (2)	−0.0007 (1)	−0.0008 (1)	0.0000 (2)
Zn1	0.0235 (2)	0.0210 (2)	0.0191 (3)	0.000	0.000	−0.0016 (3)
Si1	0.0078 (3)	0.0077 (3)	0.0058 (5)	0.000	0.000	0.0007 (4)
S1	0.0126 (3)	0.0072 (3)	0.0085 (5)	0.000	0.000	0.0011 (4)
S2	0.0099 (3)	0.0104 (3)	0.0064 (6)	0.000	0.000	−0.0001 (3)
S3	0.0089 (2)	0.0101 (3)	0.0110 (5)	−0.0012 (1)	0.0006 (3)	0.0000 (3)

Geometric parameters (Å, º) top

Cu1—S2ⁱ	2.3170 (7)	Si1—S3^vi	2.136 (1)
Cu1—S3	2.325 (1)	Si1—S2^vii	2.143 (3)
Cu1—S1	2.3270 (6)	S1—Cu1^viii	2.3270 (6)
Cu1—S3ⁱⁱ	2.3426 (7)	S2—Si1^iv	2.143 (3)
Zn1—S2	2.322 (1)	S2—Cu1^vi	2.3170 (7)
Zn1—S1	2.322 (1)	S2—Cu1^v	2.3170 (7)
Zn1—S3ⁱⁱⁱ	2.3650 (7)	S3—Si1ⁱ	2.136 (1)
Zn1—S3^iv	2.3650 (7)	S3—Cu1^ix	2.3426 (7)
Si1—S1	2.131 (1)	S3—Zn1^vii	2.3650 (7)
Si1—S3^v	2.136 (1)

S2ⁱ—Cu1—S3	112.51 (4)	Si1—S1—Zn1	112.05 (8)
S2ⁱ—Cu1—S1	106.98 (3)	Si1—S1—Cu1^viii	111.72 (5)
S3—Cu1—S1	111.92 (4)	Zn1—S1—Cu1^viii	108.24 (4)
S2ⁱ—Cu1—S3ⁱⁱ	106.09 (4)	Si1—S1—Cu1	111.72 (5)
S3—Cu1—S3ⁱⁱ	108.38 (3)	Zn1—S1—Cu1	108.24 (4)
S1—Cu1—S3ⁱⁱ	110.82 (4)	Cu1^viii—S1—Cu1	104.51 (4)
S2—Zn1—S1	112.01 (5)	Si1^iv—S2—Cu1^vi	115.21 (4)
S2—Zn1—S3ⁱⁱⁱ	107.88 (4)	Si1^iv—S2—Cu1^v	115.21 (4)
S1—Zn1—S3ⁱⁱⁱ	108.84 (4)	Cu1^vi—S2—Cu1^v	108.34 (5)
S2—Zn1—S3^iv	107.88 (4)	Si1^iv—S2—Zn1	113.46 (6)
S1—Zn1—S3^iv	108.84 (4)	Cu1^vi—S2—Zn1	101.47 (4)
S3ⁱⁱⁱ—Zn1—S3^iv	111.40 (5)	Cu1^v—S2—Zn1	101.47 (4)
S1—Si1—S3^v	108.68 (7)	Si1ⁱ—S3—Cu1	111.38 (7)
S1—Si1—S3^vi	108.68 (7)	Si1ⁱ—S3—Cu1^ix	110.92 (5)
S3^v—Si1—S3^vi	111.40 (7)	Cu1—S3—Cu1^ix	108.76 (3)
S1—Si1—S2^vii	110.60 (9)	Si1ⁱ—S3—Zn1^vii	111.42 (5)
S3^v—Si1—S2^vii	108.74 (7)	Cu1—S3—Zn1^vii	105.21 (4)
S3^vi—Si1—S2^vii	108.74 (7)	Cu1^ix—S3—Zn1^vii	108.95 (3)

Symmetry codes: (i) −x+1/2, −y+1, z−1/2; (ii) −x+1/2, −y, z+1/2; (iii) −x, y, z+1; (iv) x, y, z+1; (v) −x+1/2, −y+1, z+1/2; (vi) x−1/2, −y+1, z+1/2; (vii) x, y, z−1; (viii) −x, y, z; (ix) −x+1/2, −y, z−1/2.

Experimental details

Crystal data
Chemical formula	Cu₂ZnSiS₄
M_r	348.78
Crystal system, space group	Orthorhombic, Pmn2₁
Temperature (K)	296
a, b, c (Å)	7.4374 (1), 6.4001 (1), 6.1394 (1)
V (Å³)	292.24 (1)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	12.77
Crystal size (mm)	0.13 × 0.07 × 0.06

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2002)
T_min, T_max	0.290, 0.500
No. of measured, independent and observed [I > 2σ(I)] reflections	5153, 1078, 1023
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.763

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.051, 1.14
No. of reflections	1078
No. of parameters	44
No. of restraints	1
Δρ_max, Δρ_min (e Å⁻³)	0.72, −1.01
Absolute structure	Flack (1983), 449 Friedel pairs
Absolute structure parameter	0.02 (1)

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalMaker (Palmer, 2010), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Cu1—S2ⁱ	2.3170 (7)	Zn1—S3ⁱⁱⁱ	2.3650 (7)
Cu1—S3	2.325 (1)	Zn1—S3^iv	2.3650 (7)
Cu1—S1	2.3270 (6)	Si1—S1	2.131 (1)
Cu1—S3ⁱⁱ	2.3426 (7)	Si1—S3^v	2.136 (1)
Zn1—S2	2.322 (1)	Si1—S3^vi	2.136 (1)
Zn1—S1	2.322 (1)	Si1—S2^vii	2.143 (3)

Symmetry codes: (i) −x+1/2, −y+1, z−1/2; (ii) −x+1/2, −y, z+1/2; (iii) −x, y, z+1; (iv) x, y, z+1; (v) −x+1/2, −y+1, z+1/2; (vi) x−1/2, −y+1, z+1/2; (vii) x, y, z−1.

Acknowledgements

Special thanks are extended to Dr Tomislav Pintauer and Dr William T. Eckenhoff. The project was funded by the National Science Foundation (CRIF-0234872) and a CAREER Award (DMR-0645304).

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