catena-Poly[μ(2)-iodido-diiodidobis(μ(3)-pyridine-2-thione-κ(3)S:S:S)(μ(2)-pyridine-2-thione-κ(2)S:S)tricopper(I)].

In the title compound, [Cu(3)I(3)(C(5)H(5)NS)(3)](n), a polymeric structure is formed along [100] through bridging iodide and pyridine-2-thione ligands. The metal atoms are engaged in [Cu(3)S(3)] and [Cu(2)S(2)] rings sharing Cu-S edges, with the [Cu(2)S(2)] rings located about inversion centers. Cu(I) atoms bridged by iodide ions exhibit the shortest Cu⋯Cu separation in the polymer [2.8590 (14) Å]. The three independent Cu(I) atoms all display distorted tetra-hedral coordination geometries.

Related literature

For applications of CuI complexes and coordination compounds based on 1H-pyridine-2-thione, see: Kitagawa et al. (1990 ▶); Raper (1996 ▶, 1997 ▶); García-Vázquez et al. (1999 ▶); Akrivos (2001 ▶); Lobana & Castineiras (2002 ▶). For the structure of a polymer isoformular to the title compound, see: Lobana et al. (2003 ▶).

Experimental

Crystal data

[Cu3I3(C5H5NS)3]

M = 904.80

Triclinic,

a = 10.035 (1) Å

b = 10.9220 (11) Å

c = 12.2500 (15) Å

α = 105.956 (2)°

β = 100.088 (3)°

γ = 109.377 (3)°

V = 1164.1 (2) Å3

Z = 2

Mo Kα radiation

μ = 6.97 mm−1

T = 298 K

0.40 × 0.23 × 0.15 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.167, T max = 0.421

6013 measured reflections

4009 independent reflections

3215 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.115

S = 1.06

4009 reflections

244 parameters

H-atom parameters constrained

Δρmax = 1.33 e Å−3

Δρmin = −1.45 e Å−3

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812052051/bh2469sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812052051/bh2469Isup2.hkl

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

[Cu3I3(C5H5NS)3]	Z = 2
Mr = 904.80	F(000) = 840
Triclinic, P1	Dx = 2.581 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.035 (1) Å	Cell parameters from 3445 reflections
b = 10.9220 (11) Å	θ = 2.2–26.0°
c = 12.2500 (15) Å	µ = 6.97 mm−1
α = 105.956 (2)°	T = 298 K
β = 100.088 (3)°	Block, yellow
γ = 109.377 (3)°	0.40 × 0.23 × 0.15 mm
V = 1164.1 (2) Å3

Bruker SMART CCD diffractometer	4009 independent reflections
Radiation source: fine-focus sealed tube	3215 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
φ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.167, Tmax = 0.421	k = −12→12
6013 measured reflections	l = −14→10

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0556P)2 + 2.5913P] where P = (Fo2 + 2Fc2)/3
4009 reflections	(Δ/σ)max < 0.001
244 parameters	Δρmax = 1.33 e Å−3
0 restraints	Δρmin = −1.45 e Å−3
0 constraints

	x	y	z	Uiso*/Ueq
Cu1	0.48634 (11)	0.50567 (10)	0.61815 (8)	0.0417 (3)
Cu2	0.79614 (11)	0.58824 (10)	0.71789 (8)	0.0432 (3)
Cu3	0.14805 (12)	0.65287 (11)	0.57965 (8)	0.0495 (3)
I1	0.58333 (6)	0.39571 (5)	0.75952 (5)	0.04314 (17)
I2	0.95579 (7)	0.79131 (6)	0.91260 (5)	0.0568 (2)
I3	0.16049 (6)	0.90228 (5)	0.63917 (5)	0.04906 (18)
N1	0.1790 (7)	0.0857 (6)	0.3003 (6)	0.0479 (17)
H1	0.1089	0.1095	0.2766	0.057*
N2	1.0746 (7)	0.3244 (7)	0.6514 (6)	0.0422 (15)
H2	1.0476	0.2886	0.5751	0.051*
N3	0.3203 (7)	0.7738 (6)	0.8801 (5)	0.0410 (15)
H3	0.2341	0.7575	0.8377	0.049*
S1	0.3069 (2)	0.35003 (18)	0.43695 (15)	0.0328 (4)
S2	0.9240 (2)	0.4776 (2)	0.61847 (16)	0.0403 (5)
S3	0.3492 (2)	0.6317 (2)	0.67672 (16)	0.0422 (5)
C1	0.3003 (8)	0.1836 (7)	0.3837 (6)	0.0325 (16)
C2	0.4146 (10)	0.1418 (8)	0.4198 (7)	0.047 (2)
H2A	0.5022	0.2054	0.4778	0.057*
C3	0.3937 (11)	0.0047 (9)	0.3675 (8)	0.055 (2)
H3A	0.4690	−0.0231	0.3900	0.066*
C4	0.2641 (11)	−0.0914 (8)	0.2828 (8)	0.053 (2)
H4	0.2506	−0.1836	0.2491	0.063*
C5	0.1579 (11)	−0.0491 (8)	0.2500 (9)	0.058 (2)
H5	0.0695	−0.1122	0.1926	0.069*
C6	1.0204 (8)	0.4156 (8)	0.7040 (6)	0.0360 (16)
C7	1.0588 (9)	0.4641 (8)	0.8276 (7)	0.0438 (19)
H7	1.0206	0.5237	0.8674	0.053*
C8	1.1536 (11)	0.4235 (10)	0.8911 (8)	0.061 (3)
H8	1.1787	0.4547	0.9736	0.073*
C9	1.2119 (11)	0.3342 (11)	0.8293 (9)	0.063 (3)
H9	1.2795	0.3095	0.8705	0.075*
C10	1.1695 (10)	0.2871 (9)	0.7138 (9)	0.055 (2)
H10	1.2054	0.2260	0.6729	0.066*
C11	0.4100 (8)	0.7287 (7)	0.8249 (6)	0.0334 (16)
C12	0.5518 (9)	0.7651 (8)	0.8966 (7)	0.045 (2)
H12	0.6184	0.7385	0.8625	0.053*
C13	0.5946 (11)	0.8381 (9)	1.0143 (8)	0.061 (3)
H13	0.6904	0.8635	1.0603	0.074*
C14	0.4937 (11)	0.8752 (9)	1.0667 (7)	0.056 (2)
H14	0.5207	0.9219	1.1482	0.067*
C15	0.3594 (11)	0.8436 (9)	0.9995 (7)	0.053 (2)
H15	0.2922	0.8689	1.0337	0.064*

	U11	U22	U33	U12	U13	U23
Cu1	0.0459 (6)	0.0397 (5)	0.0395 (5)	0.0245 (5)	0.0052 (4)	0.0097 (4)
Cu2	0.0466 (6)	0.0423 (6)	0.0382 (5)	0.0235 (5)	0.0080 (4)	0.0064 (4)
Cu3	0.0618 (7)	0.0513 (6)	0.0355 (5)	0.0371 (5)	0.0002 (4)	0.0065 (4)
I1	0.0422 (3)	0.0431 (3)	0.0480 (3)	0.0177 (2)	0.0081 (2)	0.0245 (2)
I2	0.0619 (4)	0.0487 (4)	0.0412 (3)	0.0151 (3)	0.0040 (3)	0.0043 (3)
I3	0.0481 (3)	0.0371 (3)	0.0573 (4)	0.0208 (3)	0.0090 (3)	0.0095 (2)
N1	0.034 (4)	0.029 (3)	0.063 (4)	0.009 (3)	0.004 (3)	0.004 (3)
N2	0.051 (4)	0.043 (4)	0.047 (4)	0.030 (3)	0.016 (3)	0.024 (3)
N3	0.039 (4)	0.037 (3)	0.039 (3)	0.015 (3)	0.009 (3)	0.005 (3)
S1	0.0351 (9)	0.0281 (9)	0.0313 (9)	0.0152 (8)	0.0038 (7)	0.0058 (7)
S2	0.0494 (11)	0.0546 (12)	0.0292 (9)	0.0364 (10)	0.0111 (8)	0.0142 (8)
S3	0.0396 (11)	0.0502 (12)	0.0335 (10)	0.0285 (9)	0.0024 (8)	0.0026 (8)
C1	0.040 (4)	0.032 (4)	0.032 (4)	0.021 (3)	0.013 (3)	0.011 (3)
C2	0.058 (5)	0.038 (4)	0.042 (4)	0.023 (4)	0.005 (4)	0.012 (4)
C3	0.077 (6)	0.048 (5)	0.055 (5)	0.043 (5)	0.018 (5)	0.020 (4)
C4	0.075 (6)	0.029 (4)	0.058 (5)	0.026 (4)	0.023 (5)	0.013 (4)
C5	0.060 (6)	0.026 (4)	0.068 (6)	0.009 (4)	0.012 (5)	0.002 (4)
C6	0.037 (4)	0.040 (4)	0.040 (4)	0.019 (3)	0.014 (3)	0.021 (3)
C7	0.054 (5)	0.046 (5)	0.032 (4)	0.021 (4)	0.009 (3)	0.017 (3)
C8	0.066 (6)	0.066 (6)	0.037 (5)	0.010 (5)	−0.002 (4)	0.030 (4)
C9	0.056 (6)	0.072 (7)	0.076 (7)	0.032 (5)	0.006 (5)	0.049 (6)
C10	0.060 (6)	0.057 (6)	0.084 (7)	0.044 (5)	0.032 (5)	0.046 (5)
C11	0.041 (4)	0.023 (3)	0.032 (4)	0.012 (3)	0.007 (3)	0.007 (3)
C12	0.039 (4)	0.044 (5)	0.048 (5)	0.027 (4)	0.000 (3)	0.009 (4)
C13	0.063 (6)	0.049 (5)	0.060 (6)	0.029 (5)	−0.017 (5)	0.013 (4)
C14	0.079 (7)	0.045 (5)	0.026 (4)	0.012 (5)	0.005 (4)	0.007 (4)
C15	0.067 (6)	0.044 (5)	0.045 (5)	0.015 (4)	0.029 (5)	0.012 (4)

Cu1—S3	2.315 (2)	S2—Cu3i	2.290 (2)
Cu1—S1	2.356 (2)	S2—Cu3iii	2.639 (3)
Cu1—S1i	2.480 (2)	S3—C11	1.708 (7)
Cu1—I1	2.5917 (11)	C1—C2	1.414 (10)
Cu1—Cu2	2.8590 (14)	C2—C3	1.384 (11)
Cu1—Cu1i	2.928 (2)	C2—H2A	0.9300
Cu2—S2	2.315 (2)	C3—C4	1.376 (13)
Cu2—S1i	2.367 (2)	C3—H3A	0.9300
Cu2—I2	2.5632 (11)	C4—C5	1.337 (13)
Cu2—I1	2.6896 (12)	C4—H4	0.9300
Cu3—S3	2.273 (2)	C5—H5	0.9300
Cu3—S2i	2.290 (2)	C6—C7	1.393 (10)
Cu3—I3	2.5726 (11)	C7—C8	1.385 (12)
Cu3—S2ii	2.639 (3)	C7—H7	0.9300
N1—C1	1.330 (9)	C8—C9	1.412 (14)
N1—C5	1.357 (10)	C8—H8	0.9300
N1—H1	0.8600	C9—C10	1.300 (13)
N2—C10	1.353 (10)	C9—H9	0.9300
N2—C6	1.354 (9)	C10—H10	0.9300
N2—H2	0.8600	C11—C12	1.396 (10)
N3—C11	1.355 (9)	C12—C13	1.351 (12)
N3—C15	1.365 (10)	C12—H12	0.9300
N3—H3	0.8600	C13—C14	1.399 (13)
S1—C1	1.728 (7)	C13—H13	0.9300
S1—Cu2i	2.367 (2)	C14—C15	1.326 (13)
S1—Cu1i	2.480 (2)	C14—H14	0.9300
S2—C6	1.721 (7)	C15—H15	0.9300
S3—Cu1—S1	95.70 (7)	Cu3i—S2—Cu3iii	87.07 (8)
S3—Cu1—S1i	109.08 (8)	Cu2—S2—Cu3iii	112.17 (9)
S1—Cu1—S1i	105.53 (6)	C11—S3—Cu3	112.4 (3)
S3—Cu1—I1	118.52 (7)	C11—S3—Cu1	113.8 (3)
S1—Cu1—I1	116.47 (6)	Cu3—S3—Cu1	133.81 (9)
S1i—Cu1—I1	110.13 (5)	N1—C1—C2	116.4 (6)
S3—Cu1—Cu2	126.14 (6)	N1—C1—S1	118.1 (5)
S1—Cu1—Cu2	135.86 (6)	C2—C1—S1	125.6 (6)
S1i—Cu1—Cu2	52.03 (5)	C3—C2—C1	118.9 (8)
I1—Cu1—Cu2	58.89 (3)	C3—C2—H2A	120.6
S3—Cu1—Cu1i	110.90 (7)	C1—C2—H2A	120.6
S1—Cu1—Cu1i	54.69 (6)	C4—C3—C2	121.5 (8)
S1i—Cu1—Cu1i	50.84 (5)	C4—C3—H3A	119.3
I1—Cu1—Cu1i	130.56 (5)	C2—C3—H3A	119.3
Cu2—Cu1—Cu1i	93.24 (5)	C5—C4—C3	118.5 (7)
S2—Cu2—S1i	97.69 (7)	C5—C4—H4	120.8
S2—Cu2—I2	114.82 (7)	C3—C4—H4	120.8
S1i—Cu2—I2	115.43 (6)	C4—C5—N1	120.0 (8)
S2—Cu2—I1	107.63 (7)	C4—C5—H5	120.0
S1i—Cu2—I1	110.49 (6)	N1—C5—H5	120.0
I2—Cu2—I1	110.04 (4)	N2—C6—C7	117.0 (7)
S2—Cu2—Cu1	120.62 (6)	N2—C6—S2	119.4 (5)
S1i—Cu2—Cu1	55.70 (5)	C7—C6—S2	123.3 (6)
I2—Cu2—Cu1	124.49 (4)	C8—C7—C6	120.0 (8)
I1—Cu2—Cu1	55.59 (3)	C8—C7—H7	120.0
S3—Cu3—S2i	110.21 (7)	C6—C7—H7	120.0
S3—Cu3—I3	114.83 (7)	C7—C8—C9	119.3 (8)
S2i—Cu3—I3	118.15 (7)	C7—C8—H8	120.4
S3—Cu3—S2ii	104.12 (8)	C9—C8—H8	120.4
S2i—Cu3—S2ii	92.93 (8)	C10—C9—C8	119.0 (8)
I3—Cu3—S2ii	113.75 (6)	C10—C9—H9	120.5
Cu1—I1—Cu2	65.52 (3)	C8—C9—H9	120.5
C1—N1—C5	124.8 (7)	C9—C10—N2	121.9 (8)
C1—N1—H1	117.6	C9—C10—H10	119.1
C5—N1—H1	117.6	N2—C10—H10	119.1
C10—N2—C6	122.8 (7)	N3—C11—C12	116.0 (7)
C10—N2—H2	118.6	N3—C11—S3	120.9 (6)
C6—N2—H2	118.6	C12—C11—S3	123.1 (6)
C11—N3—C15	123.5 (7)	C13—C12—C11	121.5 (8)
C11—N3—H3	118.3	C13—C12—H12	119.2
C15—N3—H3	118.3	C11—C12—H12	119.2
C1—S1—Cu1	117.6 (3)	C12—C13—C14	119.5 (8)
C1—S1—Cu2i	111.4 (2)	C12—C13—H13	120.3
Cu1—S1—Cu2i	125.91 (8)	C14—C13—H13	120.3
C1—S1—Cu1i	104.9 (3)	C15—C14—C13	119.7 (8)
Cu1—S1—Cu1i	74.47 (6)	C15—C14—H14	120.1
Cu2i—S1—Cu1i	72.26 (6)	C13—C14—H14	120.1
C6—S2—Cu3i	112.1 (3)	C14—C15—N3	119.7 (8)
C6—S2—Cu2	112.9 (3)	C14—C15—H15	120.1
Cu3i—S2—Cu2	126.77 (9)	N3—C15—H15	120.1
C6—S2—Cu3iii	98.9 (3)
S3—Cu1—Cu2—S2	−164.32 (10)	S2i—Cu3—S3—Cu1	−1.65 (19)
S1—Cu1—Cu2—S2	−6.01 (13)	I3—Cu3—S3—Cu1	−138.06 (12)
S1i—Cu1—Cu2—S2	−77.56 (9)	S2ii—Cu3—S3—Cu1	96.91 (15)
I1—Cu1—Cu2—S2	91.21 (8)	S1—Cu1—S3—C11	162.0 (3)
Cu1i—Cu1—Cu2—S2	−45.38 (9)	S1i—Cu1—S3—C11	−89.3 (3)
S3—Cu1—Cu2—S1i	−86.77 (10)	I1—Cu1—S3—C11	37.7 (3)
S1—Cu1—Cu2—S1i	71.55 (11)	Cu2—Cu1—S3—C11	−32.9 (3)
I1—Cu1—Cu2—S1i	168.77 (6)	Cu1i—Cu1—S3—C11	−143.7 (3)
Cu1i—Cu1—Cu2—S1i	32.17 (6)	S1—Cu1—S3—Cu3	−17.16 (16)
S3—Cu1—Cu2—I2	12.56 (11)	S1i—Cu1—S3—Cu3	91.46 (15)
S1—Cu1—Cu2—I2	170.87 (8)	I1—Cu1—S3—Cu3	−141.50 (12)
S1i—Cu1—Cu2—I2	99.32 (7)	Cu2—Cu1—S3—Cu3	147.85 (12)
I1—Cu1—Cu2—I2	−91.91 (5)	Cu1i—Cu1—S3—Cu3	37.13 (17)
Cu1i—Cu1—Cu2—I2	131.49 (6)	C5—N1—C1—C2	0.8 (12)
S3—Cu1—Cu2—I1	104.47 (9)	C5—N1—C1—S1	179.9 (7)
S1—Cu1—Cu2—I1	−97.22 (9)	Cu1—S1—C1—N1	162.9 (5)
S1i—Cu1—Cu2—I1	−168.77 (6)	Cu2i—S1—C1—N1	−40.6 (7)
Cu1i—Cu1—Cu2—I1	−136.59 (5)	Cu1i—S1—C1—N1	−117.0 (6)
S3—Cu1—I1—Cu2	−117.13 (8)	Cu1—S1—C1—C2	−18.1 (8)
S1—Cu1—I1—Cu2	129.49 (7)	Cu2i—S1—C1—C2	138.4 (6)
S1i—Cu1—I1—Cu2	9.41 (5)	Cu1i—S1—C1—C2	61.9 (7)
Cu1i—Cu1—I1—Cu2	64.56 (7)	N1—C1—C2—C3	0.0 (12)
S2—Cu2—I1—Cu1	−115.48 (6)	S1—C1—C2—C3	−179.0 (7)
S1i—Cu2—I1—Cu1	−9.89 (5)	C1—C2—C3—C4	−0.9 (14)
I2—Cu2—I1—Cu1	118.74 (4)	C2—C3—C4—C5	1.1 (15)
S3—Cu1—S1—C1	−149.4 (3)	C3—C4—C5—N1	−0.3 (15)
S1i—Cu1—S1—C1	99.0 (3)	C1—N1—C5—C4	−0.7 (15)
I1—Cu1—S1—C1	−23.6 (3)	C10—N2—C6—C7	−4.2 (12)
Cu2—Cu1—S1—C1	48.0 (3)	C10—N2—C6—S2	169.9 (7)
Cu1i—Cu1—S1—C1	99.0 (3)	Cu3i—S2—C6—N2	15.5 (7)
S3—Cu1—S1—Cu2i	57.90 (12)	Cu2—S2—C6—N2	166.3 (5)
S1i—Cu1—S1—Cu2i	−53.73 (9)	Cu3iii—S2—C6—N2	−75.0 (6)
I1—Cu1—S1—Cu2i	−176.24 (7)	Cu3i—S2—C6—C7	−170.8 (6)
Cu2—Cu1—S1—Cu2i	−104.64 (10)	Cu2—S2—C6—C7	−20.0 (8)
Cu1i—Cu1—S1—Cu2i	−53.73 (9)	Cu3iii—S2—C6—C7	98.7 (7)
S3—Cu1—S1—Cu1i	111.63 (8)	N2—C6—C7—C8	2.8 (12)
S1i—Cu1—S1—Cu1i	0.0	S2—C6—C7—C8	−171.0 (7)
I1—Cu1—S1—Cu1i	−122.51 (6)	C6—C7—C8—C9	0.7 (14)
Cu2—Cu1—S1—Cu1i	−50.91 (9)	C7—C8—C9—C10	−3.2 (15)
S1i—Cu2—S2—C6	179.4 (3)	C8—C9—C10—N2	2.0 (15)
I2—Cu2—S2—C6	56.7 (3)	C6—N2—C10—C9	1.8 (14)
I1—Cu2—S2—C6	−66.2 (3)	C15—N3—C11—C12	−3.8 (11)
Cu1—Cu2—S2—C6	−126.1 (3)	C15—N3—C11—S3	175.5 (6)
S1i—Cu2—S2—Cu3i	−34.96 (14)	Cu3—S3—C11—N3	19.6 (7)
I2—Cu2—S2—Cu3i	−157.63 (10)	Cu1—S3—C11—N3	−159.8 (5)
I1—Cu2—S2—Cu3i	79.47 (13)	Cu3—S3—C11—C12	−161.2 (6)
Cu1—Cu2—S2—Cu3i	19.54 (16)	Cu1—S3—C11—C12	19.4 (8)
S1i—Cu2—S2—Cu3iii	68.67 (9)	N3—C11—C12—C13	1.5 (12)
I2—Cu2—S2—Cu3iii	−54.00 (9)	S3—C11—C12—C13	−177.8 (7)
I1—Cu2—S2—Cu3iii	−176.90 (5)	C11—C12—C13—C14	1.7 (14)
Cu1—Cu2—S2—Cu3iii	123.16 (7)	C12—C13—C14—C15	−2.8 (14)
S2i—Cu3—S3—C11	179.1 (3)	C13—C14—C15—N3	0.7 (14)
I3—Cu3—S3—C11	42.7 (3)	C11—N3—C15—C14	2.7 (13)
S2ii—Cu3—S3—C11	−82.3 (3)

Table 1

Selected bond lengths (Å)

Cu1—S3	2.315 (2)
Cu1—S1	2.356 (2)
Cu1—S1i	2.480 (2)
Cu1—I1	2.5917 (11)
Cu1—Cu2	2.8590 (14)
Cu1—Cu1i	2.928 (2)
Cu2—S2	2.315 (2)
Cu2—S1i	2.367 (2)
Cu2—I2	2.5632 (11)
Cu2—I1	2.6896 (12)
Cu3—S3	2.273 (2)
Cu3—S2i	2.290 (2)
Cu3—I3	2.5726 (11)
Cu3—S2ii	2.639 (3)

Symmetry codes: (i) ; (ii) .