RbCu₂VS₄

The reaction of Cu and V in a Rb₂S₅ melt yields black crystals of rubidium dicopper vanadium tetra­sulfide, RbCu₂VS₄. The structure is comprised of [Cu₂VS₄]^- layers within the (010) plane which are separated by Rb⁺ cations. The layers consist of a network of edge- and corner-sharing [VS₄] and [CuS₄] tetrahedra parallel to (010). The optical band gap was determined as 1.45 eV.

Computing details

Data collection: DIF4 (Stoe & Cie, 1991); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1991); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: CIFTAB in SHELXL93.

Rubidiumdicoppervanadiumtetrasulfide

Crystal data

RbCu2VS4	F(000) = 728
Mr = 391.73	Dx = 3.580 Mg m^−3
Orthorhombic, Ama2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: A 2 -2a	Cell parameters from 10 reflections
a = 7.382 (3) Å	θ = 13–24°
b = 18.187 (11) Å	µ = 14.74 mm^−1
c = 5.413 (2) Å	T = 293 K
V = 726.7 (6) Å^3	Needle, black
Z = 4	0.08 × 0.08 × 0.07 mm

Data collection

STOE AED-II four-circle diffractometer	483 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.055
Graphite monochromator	θmax = 25.0°, θmin = 2.2°
ω–θ scans	h = 0→8
Absorption correction: empirical (using intensity measurements) (XEMP in SHELXTL/PC; Siemens, 1990)	k = −21→21
Tmin = 0.290, Tmax = 0.345	l = −6→4
1230 measured reflections	4 standard reflections every every 2 h min
628 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	w = 1/[σ^2(Fo^2) + (0.0374P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.078	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.95 e Å^−3
628 reflections	Δρmin = −0.66 e Å^−3
46 parameters	Absolute structure: Flack (1983)
1 restraint	Absolute structure parameter: −0.01 (3)

Special details

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 on F² for ALL reflections except for 0 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating _R_factor_obs 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 (Ų)

	x	y	z	Uiso*/Ueq
V	0.2500	0.10888 (13)	0.6036 (7)	0.0143 (6)
Cu1	0.0000	0.0000	0.6253 (4)	0.0214 (5)
Cu2	0.2500	0.10573 (10)	0.1029 (4)	0.0204 (6)
S1	0.2500	0.2040 (2)	0.3668 (17)	0.0248 (9)
S2	0.0076 (3)	0.10917 (14)	0.8357 (7)	0.0194 (5)
S3	0.2500	0.0076 (2)	0.3709 (8)	0.0157 (7)
Rb	0.7500	0.18224 (8)	0.3550 (6)	0.0294 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V	0.0132 (12)	0.0164 (12)	0.013 (2)	0.000	0.000	0.000 (2)
Cu1	0.0150 (7)	0.0242 (9)	0.0249 (10)	−0.0039 (8)	0.000	0.000
Cu2	0.0224 (10)	0.0252 (11)	0.0136 (12)	0.000	0.000	0.0029 (14)
S1	0.041 (2)	0.016 (2)	0.017 (2)	0.000	0.000	0.004 (3)
S2	0.0152 (10)	0.0265 (11)	0.0164 (13)	0.0031 (9)	−0.001 (3)	−0.0014 (13)
S3	0.0162 (14)	0.0157 (15)	0.015 (2)	0.000	0.000	−0.001 (3)
Rb	0.0336 (8)	0.0271 (7)	0.0274 (8)	0.000	0.000	0.0048 (13)

Geometric parameters (Å, º)

V—S1	2.153 (7)	Cu2—Rb^x	4.083 (4)
V—S2^i	2.186 (4)	Cu2—Rb	4.174 (2)
V—S2	2.186 (4)	Cu2—Rb^v	4.174 (2)
V—S3	2.232 (5)	S1—Rb^iv	3.356 (9)
V—Cu2^ii	2.703 (4)	S1—Rb^x	3.458 (10)
V—Cu1	2.709 (2)	S1—Rb^v	3.713 (2)
V—Cu1^iii	2.709 (2)	S1—Rb	3.713 (2)
V—Cu2	2.711 (4)	S2—Cu2^ii	2.302 (3)
V—Rb^iv	4.035 (4)	S2—Rb^v	3.486 (4)
V—Rb^v	4.149 (2)	S2—Rb^xi	3.645 (4)
V—Rb	4.149 (2)	S3—Cu1^iii	2.307 (3)
Cu1—S2	2.290 (3)	S3—Rb^vii	3.453 (4)
Cu1—S2^vi	2.290 (3)	Rb—S1^x	3.356 (9)
Cu1—S3^vi	2.307 (3)	Rb—S3^vii	3.453 (4)
Cu1—S3	2.307 (3)	Rb—S1^iv	3.458 (10)
Cu1—V^vi	2.709 (2)	Rb—S2^xii	3.486 (4)
Cu1—Rb^vii	4.066 (2)	Rb—S2^i	3.486 (4)
Cu1—Rb^v	4.066 (2)	Rb—S2^ix	3.645 (4)
Cu2—S1	2.288 (6)	Rb—S2^xiii	3.645 (4)
Cu2—S3	2.300 (4)	Rb—S1^xii	3.713 (2)
Cu2—S2^viii	2.302 (3)	Rb—V^x	4.035 (4)
Cu2—S2^ix	2.302 (3)	Rb—Cu1^iii	4.066 (2)
Cu2—V^viii	2.703 (4)	Rb—Cu1^xii	4.066 (2)
S1—V—S2^i	109.88 (14)	Rb^x—Cu2—Rb	78.03 (3)
S1—V—S2	109.88 (14)	S1—Cu2—Rb^v	62.32 (4)
S2^i—V—S2	109.9 (3)	S3—Cu2—Rb^v	93.02 (7)
S1—V—S3	109.1 (2)	S2^viii—Cu2—Rb^v	60.59 (10)
S2^i—V—S3	109.05 (12)	S2^ix—Cu2—Rb^v	152.10 (13)
S2—V—S3	109.05 (12)	V^viii—Cu2—Rb^v	108.65 (6)
S1—V—Cu2^ii	127.7 (2)	V—Cu2—Rb^v	70.50 (6)
S2^i—V—Cu2^ii	54.94 (14)	Rb^x—Cu2—Rb^v	78.03 (3)
S2—V—Cu2^ii	54.94 (14)	Rb—Cu2—Rb^v	124.34 (8)
S3—V—Cu2^ii	123.2 (2)	V—S1—Cu2	75.16 (14)
S1—V—Cu1	127.81 (14)	V—S1—Rb^iv	91.5 (3)
S2^i—V—Cu1	122.3 (2)	Cu2—S1—Rb^iv	166.7 (3)
S2—V—Cu1	54.51 (8)	V—S1—Rb^x	163.3 (3)
S3—V—Cu1	54.63 (9)	Cu2—S1—Rb^x	88.1 (3)
Cu2^ii—V—Cu1	86.63 (10)	Rb^iv—S1—Rb^x	105.20 (11)
S1—V—Cu1^iii	127.81 (13)	V—S1—Rb^v	85.67 (11)
S2^i—V—Cu1^iii	54.51 (8)	Cu2—S1—Rb^v	84.60 (11)
S2—V—Cu1^iii	122.3 (2)	Rb^iv—S1—Rb^v	94.55 (15)
S3—V—Cu1^iii	54.63 (9)	Rb^x—S1—Rb^v	92.9 (2)
Cu2^ii—V—Cu1^iii	86.63 (10)	V—S1—Rb	85.67 (11)
Cu1—V—Cu1^iii	85.87 (8)	Cu2—S1—Rb	84.60 (11)
S1—V—Cu2	54.7 (2)	Rb^iv—S1—Rb	94.5 (2)
S2^i—V—Cu2	125.07 (14)	Rb^x—S1—Rb	92.9 (2)
S2—V—Cu2	125.07 (14)	Rb^v—S1—Rb	167.60 (11)
S3—V—Cu2	54.43 (12)	V—S2—Cu1	74.47 (13)
Cu2^ii—V—Cu2	177.58 (14)	V—S2—Cu2^ii	74.03 (11)
Cu1—V—Cu2	91.60 (11)	Cu1—S2—Cu2^ii	107.95 (11)
Cu1^iii—V—Cu2	91.60 (11)	V—S2—Rb^v	91.1 (2)
S1—V—Rb^iv	56.2 (2)	Cu1—S2—Rb^v	86.90 (10)
S2^i—V—Rb^iv	78.70 (11)	Cu2^ii—S2—Rb^v	154.63 (13)
S2—V—Rb^iv	78.70 (11)	V—S2—Rb^xi	150.59 (14)
S3—V—Rb^iv	165.3 (2)	Cu1—S2—Rb^xi	133.39 (10)
Cu2^ii—V—Rb^iv	71.51 (10)	Cu2^ii—S2—Rb^xi	86.03 (13)
Cu1—V—Rb^iv	132.33 (8)	Rb^v—S2—Rb^xi	98.74 (7)
Cu1^iii—V—Rb^iv	132.33 (8)	V—S3—Cu2	73.45 (14)
Cu2—V—Rb^iv	110.91 (11)	V—S3—Cu1^iii	73.28 (12)
S1—V—Rb^v	63.16 (5)	Cu2—S3—Cu1^iii	115.01 (10)
S2^i—V—Rb^v	156.0 (2)	V—S3—Cu1	73.28 (12)
S2—V—Rb^v	57.15 (10)	Cu2—S3—Cu1	115.01 (10)
S3—V—Rb^v	94.72 (9)	Cu1^iii—S3—Cu1	106.3 (2)
Cu2^ii—V—Rb^v	109.34 (8)	V—S3—Rb^vii	147.1 (2)
Cu1—V—Rb^v	69.09 (5)	Cu2—S3—Rb^vii	139.5 (2)
Cu1^iii—V—Rb^v	148.76 (10)	Cu1^iii—S3—Rb^vii	87.44 (9)
Cu2—V—Rb^v	71.49 (7)	Cu1—S3—Rb^vii	87.44 (9)
Rb^iv—V—Rb^v	78.85 (4)	S1^x—Rb—S3^vii	129.5 (2)
S1—V—Rb	63.16 (5)	S1^x—Rb—S1^iv	105.20 (11)
S2^i—V—Rb	57.15 (10)	S3^vii—Rb—S1^iv	125.3 (2)
S2—V—Rb	156.0 (2)	S1^x—Rb—S2^xii	145.35 (5)
S3—V—Rb	94.72 (9)	S3^vii—Rb—S2^xii	66.44 (8)
Cu2^ii—V—Rb	109.34 (8)	S1^iv—Rb—S2^xii	68.29 (14)
Cu1—V—Rb	148.76 (10)	S1^x—Rb—S2^i	145.35 (5)
Cu1^iii—V—Rb	69.09 (5)	S3^vii—Rb—S2^i	66.44 (8)
Cu2—V—Rb	71.49 (7)	S1^iv—Rb—S2^i	68.29 (13)
Rb^iv—V—Rb	78.85 (4)	S2^xii—Rb—S2^i	66.12 (11)
Rb^v—V—Rb	125.64 (11)	S1^x—Rb—S2^ix	67.51 (15)
S2—Cu1—S2^vi	120.4 (2)	S3^vii—Rb—S2^ix	69.80 (9)
S2—Cu1—S3^vi	111.61 (10)	S1^iv—Rb—S2^ix	146.73 (5)
S2^vi—Cu1—S3^vi	103.03 (11)	S2^xii—Rb—S2^ix	136.16 (9)
S2—Cu1—S3	103.03 (11)	S2^i—Rb—S2^ix	98.74 (7)
S2^vi—Cu1—S3	111.61 (10)	S1^x—Rb—S2^xiii	67.51 (15)
S3^vi—Cu1—S3	106.7 (2)	S3^vii—Rb—S2^xiii	69.80 (9)
S2—Cu1—V	51.02 (11)	S1^iv—Rb—S2^xiii	146.73 (5)
S2^vi—Cu1—V	132.23 (9)	S2^xii—Rb—S2^xiii	98.74 (7)
S3^vi—Cu1—V	124.24 (14)	S2^i—Rb—S2^xiii	136.16 (9)
S3—Cu1—V	52.09 (10)	S2^ix—Rb—S2^xiii	62.91 (9)
S2—Cu1—V^vi	132.23 (9)	S1^x—Rb—S1^xii	87.01 (13)
S2^vi—Cu1—V^vi	51.02 (11)	S3^vii—Rb—S1^xii	96.09 (5)
S3^vi—Cu1—V^vi	52.09 (10)	S1^iv—Rb—S1^xii	85.55 (14)
S3—Cu1—V^vi	124.24 (14)	S2^xii—Rb—S1^xii	59.03 (14)
V—Cu1—V^vi	175.0 (2)	S2^i—Rb—S1^xii	124.8 (2)
S2—Cu1—Rb^vii	151.01 (6)	S2^ix—Rb—S1^xii	124.8 (2)
S2^vi—Cu1—Rb^vii	58.89 (9)	S2^xiii—Rb—S1^xii	62.19 (14)
S3^vi—Cu1—Rb^vii	95.72 (10)	S1^x—Rb—S1	87.01 (14)
S3—Cu1—Rb^vii	58.04 (9)	S3^vii—Rb—S1	96.09 (5)
V—Cu1—Rb^vii	105.72 (6)	S1^iv—Rb—S1	85.55 (14)
V^vi—Cu1—Rb^vii	72.41 (6)	S2^xii—Rb—S1	124.8 (2)
S2—Cu1—Rb^v	58.89 (9)	S2^i—Rb—S1	59.03 (14)
S2^vi—Cu1—Rb^v	151.01 (6)	S2^ix—Rb—S1	62.19 (14)
S3^vi—Cu1—Rb^v	58.04 (9)	S2^xiii—Rb—S1	124.8 (2)
S3—Cu1—Rb^v	95.72 (10)	S1^xii—Rb—S1	167.60 (11)
V—Cu1—Rb^v	72.41 (6)	S1^x—Rb—V^x	32.24 (11)
V^vi—Cu1—Rb^v	105.72 (6)	S3^vii—Rb—V^x	161.7 (2)
Rb^vii—Cu1—Rb^v	137.81 (11)	S1^iv—Rb—V^x	72.95 (10)
S1—Cu2—S3	102.3 (2)	S2^xii—Rb—V^x	127.63 (7)
S1—Cu2—S2^viii	111.79 (13)	S2^i—Rb—V^x	127.63 (7)
S3—Cu2—S2^viii	114.67 (12)	S2^ix—Rb—V^x	94.78 (9)
S1—Cu2—S2^ix	111.79 (13)	S2^xiii—Rb—V^x	94.78 (9)
S3—Cu2—S2^ix	114.67 (12)	S1^xii—Rb—V^x	84.57 (8)
S2^viii—Cu2—S2^ix	102.0 (2)	S1—Rb—V^x	84.57 (8)
S1—Cu2—V^viii	127.4 (2)	S1^x—Rb—Cu1^iii	141.80 (13)
S3—Cu2—V^viii	130.30 (15)	S3^vii—Rb—Cu1^iii	34.53 (6)
S2^viii—Cu2—V^viii	51.02 (11)	S1^iv—Rb—Cu1^iii	101.50 (15)
S2^ix—Cu2—V^viii	51.02 (10)	S2^xii—Rb—Cu1^iii	70.62 (7)
S1—Cu2—V	50.2 (2)	S2^i—Rb—Cu1^iii	34.21 (5)
S3—Cu2—V	52.12 (12)	S2^ix—Rb—Cu1^iii	75.14 (6)
S2^viii—Cu2—V	128.89 (10)	S2^xiii—Rb—Cu1^iii	102.54 (6)
S2^ix—Cu2—V	128.89 (10)	S1^xii—Rb—Cu1^iii	122.14 (11)
V^viii—Cu2—V	177.58 (14)	S1—Rb—Cu1^iii	68.25 (8)
S1—Cu2—Rb^x	57.8 (2)	V^x—Rb—Cu1^iii	152.72 (2)
S3—Cu2—Rb^x	160.11 (13)	S1^x—Rb—Cu1^xii	141.80 (13)
S2^viii—Cu2—Rb^x	76.57 (10)	S3^vii—Rb—Cu1^xii	34.53 (6)
S2^ix—Cu2—Rb^x	76.57 (10)	S1^iv—Rb—Cu1^xii	101.50 (15)
V^viii—Cu2—Rb^x	69.60 (9)	S2^xii—Rb—Cu1^xii	34.21 (5)
V—Cu2—Rb^x	107.99 (9)	S2^i—Rb—Cu1^xii	70.62 (7)
S1—Cu2—Rb	62.32 (4)	S2^ix—Rb—Cu1^xii	102.54 (6)
S3—Cu2—Rb	93.02 (7)	S2^xiii—Rb—Cu1^xii	75.14 (6)
S2^viii—Cu2—Rb	152.10 (13)	S1^xii—Rb—Cu1^xii	68.25 (8)
S2^ix—Cu2—Rb	60.59 (10)	S1—Rb—Cu1^xii	122.14 (11)
V^viii—Cu2—Rb	108.65 (6)	V^x—Rb—Cu1^xii	152.72 (2)
V—Cu2—Rb	70.50 (6)	Cu1^iii—Rb—Cu1^xii	53.99 (4)

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