Hexabromidotetra­kis(μ₃-4-pyri­din­ium­thiol­ato-κ³S:S:S)hexa­copper(I)

The crystal structure of the title compound, [Cu₆Br₆(C₅H₅NS)₄], consists of a hexa­nuclear Cu₆Br₆S₄ cluster in which each copper atom is connected to one bromine atom. The sulfur atoms are each connected to three copper atoms via μ₃ coordination. Two of the bromine atoms are located on a twofold axis and the clusters are located on a fourfold rotoinversion axis. One unique Cu atom is disordered over two positions; site occupancy factors are 0.6 and 0.4. The other Cu atom is disordered about a twofold rotation axis.

Key indicators

• Single-crystal X-ray study
• T = 170 K
• Mean [sigma](C-C) = 0.006 Å
• Disorder in main residue
• R factor = 0.032
• wR factor = 0.076
• Data-to-parameter ratio = 17.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Br1    -   Cu1_d   ..      43.77 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Br1    -   Cu2_n   ..      84.75 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu1    -   Cu1'    ..      31.98 su
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for        Cu2

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       2.00 Ratio
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT215_ALERT_3_C Disordered Cu2     has ADP max/min Ratio .......       3.30
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.63 Ratio
PLAT220_ALERT_2_C Large Non-Solvent   Cu     Ueq(max)/Ueq(min) ...       2.52 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        Cu1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         S1
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.48
PLAT301_ALERT_3_C Main Residue  Disorder .........................      13.00 Perc.
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.45 Ratio
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       8.97 Deg.
              CU1  -BR1  -CU1'    1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      21.47 Deg.
              CU2  -BR2  -CU2     1.555   1.555   6.564
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      22.47 Deg.
              CU2  -S1   -CU2     6.564   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       9.69 Deg.
              CU1  -S1   -CU1'    1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       9.67 Deg.
              CU1  -S1   -CU1'   15.566   1.555  15.566

Alert level G
ABSTM02_ALERT_3_G  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.231     0.349
            Tmin(prime) and Tmax expected:      0.253     0.339
            RR(prime) =      0.888
            Please check that your absorption correction is appropriate.

   0 ALERT level A = In general: serious problem
   4 ALERT level B = Potentially serious problem
  18 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  14 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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).

Related literature

For the isotypic chloro compound, see Cheng et al. (2004).

For related literature, see: Je\&s, Taborsky, Pospisil & Näther (2007); Näther & Je\&s (2006); Näther et al. (2003).

S2. Experimental

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.

S3. Refinement

All H atoms were located in difference map but were positioned with idealized geometry and were refined isotropic with U_eq = 1.2 U_eq 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.

Computing details

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).

Figures

	Fig. 1. Crystal structure of compound I with labelling and displacement ellipsoids drawn at the 50% probability level. Symmetry codes: i = 1 - x, 1,5-y z; ii = 1.25 - y, 1/4 + x, 1.25 - z; iii = -1/4 + y, 1.25 - x, 1,25 - z.
	Fig. 2. View of the Cu6Br6S4 cluster. The strongly distorted Cu6 octahedra are indicated by black lines. The Cu—S bonds are shown as dashed lines.

#di-bromo-tetrakis(µ₂-bromo)-tetrakis(µ₃-4-pyridiniumthiolato-S)- #hexa-copper(I) Hexabromido-tetrakis(µ₃-4-pyridiniumthiolato-κ³S)hexacopper(I)

Crystal data

[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) Å^3	T = 170 K
Z = 4	Block, red
F(000) = 2464	0.11 × 0.10 × 0.09 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.076	w = 1/[σ^2(Fo^2) + (0.040P)^2 + 16.8187P] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00071 (9)

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 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 (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Cu1—S1	2.249 (5)	Br1—Cu2^v	2.9058 (18)
Cu1—S1^i	2.253 (5)	Br2—Cu2^ii	2.3718 (13)
Cu1—Br1	2.377 (4)	S1—C1	1.739 (4)
Cu1—Cu2^ii	2.924 (4)	S1—Cu1^vi	2.253 (5)
Cu1'—S1	2.319 (6)	S1—Cu2^ii	2.256 (2)
Cu1'—S1^i	2.324 (7)	S1—Cu1'^vi	2.324 (7)
Cu1'—Br1	2.477 (6)	C1—C2	1.405 (5)
Cu1'—Br1^iii	2.666 (3)	C1—C5	1.405 (6)
Cu1'—Cu2^ii	2.689 (6)	C2—C3	1.370 (6)
Cu2—Cu2^ii	0.884 (3)	C2—H2	0.9500
Cu2—S1^ii	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—Br1^iv	2.9058 (18)	C4—C5	1.369 (7)
Cu2—Cu1^ii	2.924 (4)	C4—H4	0.9500
Br1—Cu1'^iii	2.666 (3)	C5—H5	0.9500
S1—Cu1—S1^i	105.20 (17)	Cu1'^iii—Br1—Cu2^v	57.53 (13)
S1—Cu1—Br1	116.11 (19)	Cu2—Br2—Cu2^ii	21.47 (8)
S1^i—Cu1—Br1	133.8 (2)	C1—S1—Cu1	115.35 (17)
S1—Cu1—Cu2^ii	49.64 (9)	C1—S1—Cu1^vi	113.14 (17)
S1^i—Cu1—Cu2^ii	88.90 (13)	Cu1—S1—Cu1^vi	117.82 (10)
Br1—Cu1—Cu2^ii	133.62 (17)	C1—S1—Cu2^ii	103.96 (13)
S1—Cu1'—S1^i	100.7 (2)	Cu1—S1—Cu2^ii	80.94 (10)
S1—Cu1'—Br1	109.9 (2)	Cu1^vi—S1—Cu2^ii	121.47 (12)
S1^i—Cu1'—Br1	125.0 (2)	C1—S1—Cu2	101.96 (13)
S1—Cu1'—Br1^iii	114.5 (2)	Cu1—S1—Cu2	101.85 (10)
S1^i—Cu1'—Br1^iii	103.7 (2)	Cu1^vi—S1—Cu2	103.73 (11)
Br1—Cu1'—Br1^iii	103.49 (18)	Cu2^ii—S1—Cu2	22.47 (8)
S1—Cu1'—Cu2^ii	52.91 (13)	C1—S1—Cu1'	113.1 (2)
S1^i—Cu1'—Cu2^ii	93.4 (2)	Cu1—S1—Cu1'	9.69 (15)
Br1—Cu1'—Cu2^ii	141.5 (3)	Cu1^vi—S1—Cu1'	125.38 (18)
Br1^iii—Cu1'—Cu2^ii	65.72 (11)	Cu2^ii—S1—Cu1'	71.99 (12)
Cu2^ii—Cu2—S1^ii	80.2 (2)	Cu2—S1—Cu1'	93.47 (13)
Cu2^ii—Cu2—S1	77.3 (2)	C1—S1—Cu1'^vi	117.1 (2)
S1^ii—Cu2—S1	119.14 (7)	Cu1—S1—Cu1'^vi	108.83 (14)
Cu2^ii—Cu2—Br2	79.26 (4)	Cu1^vi—S1—Cu1'^vi	9.67 (14)
S1^ii—Cu2—Br2	115.46 (8)	Cu2^ii—S1—Cu1'^vi	125.75 (15)
S1—Cu2—Br2	114.60 (8)	Cu2—S1—Cu1'^vi	110.33 (13)
Cu2^ii—Cu2—Cu1'^ii	132.2 (2)	Cu1'—S1—Cu1'^vi	116.86 (16)
S1^ii—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)
Cu2^ii—Cu2—Br1^iv	171.01 (19)	C3—C2—C1	119.6 (4)
S1^ii—Cu2—Br1^iv	108.10 (7)	C3—C2—H2	120.2
S1—Cu2—Br1^iv	100.83 (7)	C1—C2—H2	120.2
Br2—Cu2—Br1^iv	93.74 (5)	C3—N1—C4	121.5 (4)
Cu1'^ii—Cu2—Br1^iv	56.75 (9)	C3—N1—H1	119.2
Cu2^ii—Cu2—Cu1^ii	125.8 (2)	C4—N1—H1	119.2
S1^ii—Cu2—Cu1^ii	49.42 (9)	N1—C3—C2	120.5 (4)
S1—Cu2—Cu1^ii	107.74 (10)	N1—C3—H3	119.7
Br2—Cu2—Cu1^ii	135.00 (11)	C2—C3—H3	119.7
Cu1'^ii—Cu2—Cu1^ii	6.43 (14)	N1—C4—C5	120.1 (4)
Br1^iv—Cu2—Cu1^ii	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—Cu2^v	126.65 (10)	C1—C5—H5	120.0
Cu1'—Br1—Cu2^v	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.