Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807059855/bt2621sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807059855/bt2621Isup2.hkl |
CCDC reference: 672747
CuBr and 4,4'-bipyridyldisulfide was obtained from Alfa Aesar and ethanole was obtained from Fluka. 0.125 mmol (17.0 mg) copper(I) bromide, 0.125 mmol (27.5 mg) 4,4'-bipyridyldisulfide and 1.0 ml of ethanol were transfered in test-tube, which were closed and heated to 120 °C for three days. On cooling red block-shaped single crystals of (I) are obtained.
All H atoms were located in difference map but were positioned with idealized geometry and were refined isotropic with Ueq = 1.2 Ueq of the parent atom using a riding model with C—H = 0.95 Å and N—H = 0.88 Å. Cu1 is disordered in two positions and was refined using a split model. Cu2 is also disordered around a 2-fold-axis. Therefore, structure refinement was also be performed in space groups I41 and I2/a but the disordering remains constant. From the inspection of the reciprocal space there are no hints for super structure reflections or satellites.
Data collection: IPDS (Stoe & Cie, 1998b); cell refinement: IPDS (Stoe & Cie, 1998b); data reduction: IPDS (Stoe & Cie, 1998b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 1998); software used to prepare material for publication: CIFTAB in SHELXTL (Bruker, 1998).
[Cu6Br6(C5H5NS)4] | Dx = 2.787 Mg m−3 |
Mr = 1305.34 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | Cell parameters from 8000 reflections |
a = 15.3161 (9) Å | θ = 10.2–27.4° |
c = 13.2602 (8) Å | µ = 12.03 mm−1 |
V = 3110.6 (3) Å3 | T = 170 K |
Z = 4 | Block, red |
F(000) = 2464 | 0.11 × 0.10 × 0.09 mm |
Stoe IPDS-1 diffractometer | 1853 independent reflections |
Radiation source: fine-focus sealed tube | 1566 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
ϕ scans | θmax = 28.0°, θmin = 2.7° |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998a) | h = −20→20 |
Tmin = 0.231, Tmax = 0.349 | k = −20→20 |
13166 measured reflections | l = −16→16 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.076 | w = 1/[σ2(Fo2) + (0.040P)2 + 16.8187P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
1853 reflections | Δρmax = 0.76 e Å−3 |
106 parameters | Δρmin = −1.01 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00071 (9) |
[Cu6Br6(C5H5NS)4] | Z = 4 |
Mr = 1305.34 | Mo Kα radiation |
Tetragonal, I41/a | µ = 12.03 mm−1 |
a = 15.3161 (9) Å | T = 170 K |
c = 13.2602 (8) Å | 0.11 × 0.10 × 0.09 mm |
V = 3110.6 (3) Å3 |
Stoe IPDS-1 diffractometer | 1853 independent reflections |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998a) | 1566 reflections with I > 2σ(I) |
Tmin = 0.231, Tmax = 0.349 | Rint = 0.048 |
13166 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.040P)2 + 16.8187P] where P = (Fo2 + 2Fc2)/3 |
1853 reflections | Δρmax = 0.76 e Å−3 |
106 parameters | Δρmin = −1.01 e Å−3 |
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 | Occ. (<1) | |
Cu1 | 0.4617 (3) | 0.5805 (3) | 0.5937 (3) | 0.0423 (8) | 0.60 |
Cu1' | 0.4786 (3) | 0.5808 (4) | 0.5715 (4) | 0.0194 (6) | 0.40 |
Cu2 | 0.48859 (13) | 0.77650 (11) | 0.45951 (9) | 0.0490 (7) | 0.50 |
Br1 | 0.39720 (3) | 0.44117 (3) | 0.56699 (3) | 0.02079 (14) | |
Br2 | 0.5000 | 0.7500 | 0.28378 (4) | 0.01889 (15) | |
S1 | 0.38433 (6) | 0.69606 (6) | 0.53945 (7) | 0.0143 (2) | |
C1 | 0.3113 (2) | 0.6747 (2) | 0.4421 (3) | 0.0142 (7) | |
C2 | 0.3238 (3) | 0.6077 (3) | 0.3712 (3) | 0.0217 (8) | |
H2 | 0.3740 | 0.5714 | 0.3750 | 0.026* | |
N1 | 0.1928 (2) | 0.6479 (3) | 0.2893 (3) | 0.0310 (9) | |
H1 | 0.1554 | 0.6397 | 0.2399 | 0.037* | |
C3 | 0.2632 (3) | 0.5951 (3) | 0.2966 (3) | 0.0265 (9) | |
H3 | 0.2706 | 0.5488 | 0.2497 | 0.032* | |
C4 | 0.1787 (3) | 0.7131 (4) | 0.3560 (4) | 0.0377 (12) | |
H4 | 0.1286 | 0.7492 | 0.3494 | 0.045* | |
C5 | 0.2365 (3) | 0.7272 (3) | 0.4331 (4) | 0.0291 (10) | |
H5 | 0.2260 | 0.7725 | 0.4805 | 0.035* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.061 (2) | 0.0210 (8) | 0.045 (2) | −0.0072 (12) | −0.0381 (13) | 0.0073 (12) |
Cu1' | 0.0236 (11) | 0.0183 (10) | 0.0164 (14) | 0.0035 (7) | −0.0060 (7) | −0.0003 (9) |
Cu2 | 0.0315 (11) | 0.1027 (19) | 0.0126 (5) | −0.0408 (12) | 0.0046 (5) | −0.0101 (6) |
Br1 | 0.0270 (2) | 0.0170 (2) | 0.0184 (2) | −0.00091 (14) | 0.00016 (15) | −0.00071 (14) |
Br2 | 0.0169 (3) | 0.0285 (3) | 0.0112 (3) | 0.0030 (2) | 0.000 | 0.000 |
S1 | 0.0128 (4) | 0.0197 (4) | 0.0102 (4) | 0.0017 (3) | −0.0010 (3) | −0.0028 (3) |
C1 | 0.0132 (16) | 0.0196 (18) | 0.0098 (18) | −0.0018 (14) | 0.0028 (13) | 0.0014 (13) |
C2 | 0.026 (2) | 0.024 (2) | 0.015 (2) | 0.0031 (16) | −0.0010 (15) | −0.0053 (15) |
N1 | 0.0221 (19) | 0.054 (3) | 0.017 (2) | −0.0103 (17) | −0.0069 (14) | −0.0011 (17) |
C3 | 0.033 (2) | 0.032 (2) | 0.015 (2) | −0.0063 (18) | −0.0014 (17) | −0.0063 (17) |
C4 | 0.025 (2) | 0.061 (3) | 0.026 (3) | 0.012 (2) | −0.0053 (19) | −0.011 (2) |
C5 | 0.022 (2) | 0.045 (3) | 0.020 (2) | 0.0159 (19) | −0.0050 (16) | −0.0080 (19) |
Cu1—S1 | 2.249 (5) | Br1—Cu2v | 2.9058 (18) |
Cu1—S1i | 2.253 (5) | Br2—Cu2ii | 2.3718 (13) |
Cu1—Br1 | 2.377 (4) | S1—C1 | 1.739 (4) |
Cu1—Cu2ii | 2.924 (4) | S1—Cu1vi | 2.253 (5) |
Cu1'—S1 | 2.319 (6) | S1—Cu2ii | 2.256 (2) |
Cu1'—S1i | 2.324 (7) | S1—Cu1'vi | 2.324 (7) |
Cu1'—Br1 | 2.477 (6) | C1—C2 | 1.405 (5) |
Cu1'—Br1iii | 2.666 (3) | C1—C5 | 1.405 (6) |
Cu1'—Cu2ii | 2.689 (6) | C2—C3 | 1.370 (6) |
Cu2—Cu2ii | 0.884 (3) | C2—H2 | 0.9500 |
Cu2—S1ii | 2.256 (2) | N1—C3 | 1.351 (7) |
Cu2—S1 | 2.278 (2) | N1—C4 | 1.351 (7) |
Cu2—Br2 | 2.3718 (13) | N1—H1 | 0.8800 |
Cu2—Cu1'ii | 2.689 (6) | C3—H3 | 0.9500 |
Cu2—Br1iv | 2.9058 (18) | C4—C5 | 1.369 (7) |
Cu2—Cu1ii | 2.924 (4) | C4—H4 | 0.9500 |
Br1—Cu1'iii | 2.666 (3) | C5—H5 | 0.9500 |
S1—Cu1—S1i | 105.20 (17) | Cu1'iii—Br1—Cu2v | 57.53 (13) |
S1—Cu1—Br1 | 116.11 (19) | Cu2—Br2—Cu2ii | 21.47 (8) |
S1i—Cu1—Br1 | 133.8 (2) | C1—S1—Cu1 | 115.35 (17) |
S1—Cu1—Cu2ii | 49.64 (9) | C1—S1—Cu1vi | 113.14 (17) |
S1i—Cu1—Cu2ii | 88.90 (13) | Cu1—S1—Cu1vi | 117.82 (10) |
Br1—Cu1—Cu2ii | 133.62 (17) | C1—S1—Cu2ii | 103.96 (13) |
S1—Cu1'—S1i | 100.7 (2) | Cu1—S1—Cu2ii | 80.94 (10) |
S1—Cu1'—Br1 | 109.9 (2) | Cu1vi—S1—Cu2ii | 121.47 (12) |
S1i—Cu1'—Br1 | 125.0 (2) | C1—S1—Cu2 | 101.96 (13) |
S1—Cu1'—Br1iii | 114.5 (2) | Cu1—S1—Cu2 | 101.85 (10) |
S1i—Cu1'—Br1iii | 103.7 (2) | Cu1vi—S1—Cu2 | 103.73 (11) |
Br1—Cu1'—Br1iii | 103.49 (18) | Cu2ii—S1—Cu2 | 22.47 (8) |
S1—Cu1'—Cu2ii | 52.91 (13) | C1—S1—Cu1' | 113.1 (2) |
S1i—Cu1'—Cu2ii | 93.4 (2) | Cu1—S1—Cu1' | 9.69 (15) |
Br1—Cu1'—Cu2ii | 141.5 (3) | Cu1vi—S1—Cu1' | 125.38 (18) |
Br1iii—Cu1'—Cu2ii | 65.72 (11) | Cu2ii—S1—Cu1' | 71.99 (12) |
Cu2ii—Cu2—S1ii | 80.2 (2) | Cu2—S1—Cu1' | 93.47 (13) |
Cu2ii—Cu2—S1 | 77.3 (2) | C1—S1—Cu1'vi | 117.1 (2) |
S1ii—Cu2—S1 | 119.14 (7) | Cu1—S1—Cu1'vi | 108.83 (14) |
Cu2ii—Cu2—Br2 | 79.26 (4) | Cu1vi—S1—Cu1'vi | 9.67 (14) |
S1ii—Cu2—Br2 | 115.46 (8) | Cu2ii—S1—Cu1'vi | 125.75 (15) |
S1—Cu2—Br2 | 114.60 (8) | Cu2—S1—Cu1'vi | 110.33 (13) |
Cu2ii—Cu2—Cu1'ii | 132.2 (2) | Cu1'—S1—Cu1'vi | 116.86 (16) |
S1ii—Cu2—Cu1'ii | 55.10 (11) | C2—C1—C5 | 118.2 (4) |
S1—Cu2—Cu1'ii | 108.27 (15) | C2—C1—S1 | 123.2 (3) |
Br2—Cu2—Cu1'ii | 131.90 (15) | C5—C1—S1 | 118.7 (3) |
Cu2ii—Cu2—Br1iv | 171.01 (19) | C3—C2—C1 | 119.6 (4) |
S1ii—Cu2—Br1iv | 108.10 (7) | C3—C2—H2 | 120.2 |
S1—Cu2—Br1iv | 100.83 (7) | C1—C2—H2 | 120.2 |
Br2—Cu2—Br1iv | 93.74 (5) | C3—N1—C4 | 121.5 (4) |
Cu1'ii—Cu2—Br1iv | 56.75 (9) | C3—N1—H1 | 119.2 |
Cu2ii—Cu2—Cu1ii | 125.8 (2) | C4—N1—H1 | 119.2 |
S1ii—Cu2—Cu1ii | 49.42 (9) | N1—C3—C2 | 120.5 (4) |
S1—Cu2—Cu1ii | 107.74 (10) | N1—C3—H3 | 119.7 |
Br2—Cu2—Cu1ii | 135.00 (11) | C2—C3—H3 | 119.7 |
Cu1'ii—Cu2—Cu1ii | 6.43 (14) | N1—C4—C5 | 120.1 (4) |
Br1iv—Cu2—Cu1ii | 63.17 (8) | N1—C4—H4 | 119.9 |
Cu1—Br1—Cu1' | 8.97 (13) | C5—C4—H4 | 119.9 |
Cu1—Br1—Cu1'iii | 85.40 (14) | C4—C5—C1 | 120.0 (4) |
Cu1'—Br1—Cu1'iii | 76.51 (18) | C4—C5—H5 | 120.0 |
Cu1—Br1—Cu2v | 126.65 (10) | C1—C5—H5 | 120.0 |
Cu1'—Br1—Cu2v | 120.68 (12) |
Symmetry codes: (i) −y+5/4, x+1/4, −z+5/4; (ii) −x+1, −y+3/2, z; (iii) −x+1, −y+1, −z+1; (iv) x, y+1/2, −z+1; (v) x, y−1/2, −z+1; (vi) y−1/4, −x+5/4, −z+5/4. |
Experimental details
Crystal data | |
Chemical formula | [Cu6Br6(C5H5NS)4] |
Mr | 1305.34 |
Crystal system, space group | Tetragonal, I41/a |
Temperature (K) | 170 |
a, c (Å) | 15.3161 (9), 13.2602 (8) |
V (Å3) | 3110.6 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 12.03 |
Crystal size (mm) | 0.11 × 0.10 × 0.09 |
Data collection | |
Diffractometer | Stoe IPDS1 diffractometer |
Absorption correction | Numerical (X-SHAPE; Stoe & Cie, 1998a) |
Tmin, Tmax | 0.231, 0.349 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13166, 1853, 1566 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.076, 1.03 |
No. of reflections | 1853 |
No. of parameters | 106 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.040P)2 + 16.8187P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.76, −1.01 |
Computer programs: IPDS (Stoe & Cie, 1998b), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL (Bruker, 1998), CIFTAB in SHELXTL (Bruker, 1998).
Cu1—S1 | 2.249 (5) | Cu2—S1 | 2.278 (2) |
Cu1—S1i | 2.253 (5) | Cu2—Br2 | 2.3718 (13) |
Cu1—Br1 | 2.377 (4) | Cu2—Cu1'ii | 2.689 (6) |
Cu1—Cu2ii | 2.924 (4) | Cu2—Br1iv | 2.9058 (18) |
Cu1'—S1 | 2.319 (6) | Cu2—Cu1ii | 2.924 (4) |
Cu1'—S1i | 2.324 (7) | Br1—Cu1'iii | 2.666 (3) |
Cu1'—Br1 | 2.477 (6) | Br1—Cu2v | 2.9058 (18) |
Cu1'—Br1iii | 2.666 (3) | Br2—Cu2ii | 2.3718 (13) |
Cu1'—Cu2ii | 2.689 (6) | S1—Cu1vi | 2.253 (5) |
Cu2—Cu2ii | 0.884 (3) | S1—Cu2ii | 2.256 (2) |
Cu2—S1ii | 2.256 (2) | S1—Cu1'vi | 2.324 (7) |
Symmetry codes: (i) −y+5/4, x+1/4, −z+5/4; (ii) −x+1, −y+3/2, z; (iii) −x+1, −y+1, −z+1; (iv) x, y+1/2, −z+1; (v) x, y−1/2, −z+1; (vi) y−1/4, −x+5/4, −z+5/4. |
Recently, we are interested in the synthesis, structures and thermal properties of coordination polymers based on copper(I) halides and N-donor ligands (Je\&s et al., 2007; Näther & Je\&s, 2006 and Näther et al., 2003). We have found for example that most of the ligand rich compounds can be transformed into ligand deficient compounds on heating. Starting from these findings we have initiated systematic investigations on this topic. In these investigations we have reacted copper(I) bromide with 4,4'-bipyridyldisulfide. In this reaction, a cleavage of the S—S bond takes place leading to the formation of the title compound (I). To identify this product in further reaction by X-ray powder diffraction, a structure determination was performed.
The title compound is isotypic to that of the corresponding chlorine compound reported by Cheng et al. (2004). In this compound unusual large anisotropic displacement parameters were found, which are indicative for disordering. In the present structure determination similar observations were made but in contrast to the previous work a reasonable split model was used in the structure refinement.
The asymmetric unit of the title compound consists of two copper atoms, one bromine atom and one 4-pyridiniumthiolate ligand in general positions as well as one bromine atom which is located on a 2-fold axis. One copper atom is located near the 2-fold axis and therefore, disordered due to symmetry (see experimental part). The second copper atom shows also disorder and was refined using a split model, with both split positions located in general positions.
The crystal structure consists of a hexanuclear Cu6Cl6S4 cluster, which are located on 4-fold rotoinversion axis (Fig. 1). The copper atoms forms strongly distorted octahedra (Fig. 2). Each of the copper atoms is connected to one bromine atom. Two of these bromine atoms act as terminal ligands, whereas the others bridge the clusters via µ2 coordination. The Cu2Br2 units are located on centres of inversion. The sulfur atoms are each connected to three copper atoms via µ3 coordination. The CuBr distances are in the range of 2.377 (4)–2.9058 (18) Å, and the CuS distances are in the range of 2.249 (5)–2.324 (7) Å. These values are comparable to the corresponding chlorine compound reported by Cheng et al. (2004).