Cu(2)ZnSiS(4).

Single crystals of Cu(2)ZnSiS(4), dicopper(I) zinc silicon tetrasulfide, have been prepared via high-temperature solid-state synthesis. Cu(2)ZnSiS(4) was found to have the wurtz-stannite structure type, like that of Li(2)CdGeS(4), Li(2)CdSnS(4), and Cu(2)CdSiS(4). Each sulfur anion is tetra-hedrally 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 = 348.78

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.020

wR(F 2) = 0.051

S = 1.14

1078 reflections

44 parameters

1 restraint

Δρmax = 0.72 e Å−3

Δρmin = −1.01 e Å−3

Absolute structure: Flack (1983 ▶), 449 Friedel pairs

Flack parameter: 0.02 (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 ▶).

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Cu2ZnSiS4	F(000) = 332
Mr = 348.78	Dx = 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

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

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0067P)2 + 0.2702P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.020	(Δ/σ)max < 0.001
wR(F2) = 0.051	Δρmax = 0.72 e Å−3
S = 1.14	Δρmin = −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	Flack parameter: 0.02 (1)

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
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)

	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)

Cu1—S2i	2.3170 (7)	Si1—S3vi	2.136 (1)
Cu1—S3	2.325 (1)	Si1—S2vii	2.143 (3)
Cu1—S1	2.3270 (6)	S1—Cu1viii	2.3270 (6)
Cu1—S3ii	2.3426 (7)	S2—Si1iv	2.143 (3)
Zn1—S2	2.322 (1)	S2—Cu1vi	2.3170 (7)
Zn1—S1	2.322 (1)	S2—Cu1v	2.3170 (7)
Zn1—S3iii	2.3650 (7)	S3—Si1i	2.136 (1)
Zn1—S3iv	2.3650 (7)	S3—Cu1ix	2.3426 (7)
Si1—S1	2.131 (1)	S3—Zn1vii	2.3650 (7)
Si1—S3v	2.136 (1)
S2i—Cu1—S3	112.51 (4)	Si1—S1—Zn1	112.05 (8)
S2i—Cu1—S1	106.98 (3)	Si1—S1—Cu1viii	111.72 (5)
S3—Cu1—S1	111.92 (4)	Zn1—S1—Cu1viii	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)	Cu1viii—S1—Cu1	104.51 (4)
S2—Zn1—S1	112.01 (5)	Si1iv—S2—Cu1vi	115.21 (4)
S2—Zn1—S3iii	107.88 (4)	Si1iv—S2—Cu1v	115.21 (4)
S1—Zn1—S3iii	108.84 (4)	Cu1vi—S2—Cu1v	108.34 (5)
S2—Zn1—S3iv	107.88 (4)	Si1iv—S2—Zn1	113.46 (6)
S1—Zn1—S3iv	108.84 (4)	Cu1vi—S2—Zn1	101.47 (4)
S3iii—Zn1—S3iv	111.40 (5)	Cu1v—S2—Zn1	101.47 (4)
S1—Si1—S3v	108.68 (7)	Si1i—S3—Cu1	111.38 (7)
S1—Si1—S3vi	108.68 (7)	Si1i—S3—Cu1ix	110.92 (5)
S3v—Si1—S3vi	111.40 (7)	Cu1—S3—Cu1ix	108.76 (3)
S1—Si1—S2vii	110.60 (9)	Si1i—S3—Zn1vii	111.42 (5)
S3v—Si1—S2vii	108.74 (7)	Cu1—S3—Zn1vii	105.21 (4)
S3vi—Si1—S2vii	108.74 (7)	Cu1ix—S3—Zn1vii	108.95 (3)

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—S3iv	2.3650 (7)
Si1—S1	2.131 (1)
Si1—S3v	2.136 (1)
Si1—S3vi	2.136 (1)
Si1—S2vii	2.143 (3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .