catena-Poly[copper(I)-di-μ-chlorido-copper(I)-bis­[μ-bis­(pyrimidin-2-ylsulfan­yl)methane-κ²N:N′]]

The flexible heterocyclic thio­ether ligand bis­(pyrimidin-2-yl­sulfan­yl)methane in the centrosymmetric title compound, [Cu₂Cl₂(C₉H₈N₄S₂)₂]_n, links Cu₂Cl₂ dimers into a chain. The chains are linked into a three-dimensional network through C—H...Cl hydrogen bonds. The Cu^I atom is in a slightly distorted tetra­hedral coordination environment.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.041
• wR factor = 0.101
• Data-to-parameter ratio = 15.7

checkCIF/PLATON results

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Datablock: I


Alert level C
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
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.15 Ratio

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (1)       1.00

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

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

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S1. Comment

Heterocyclic flexible thioethers containing nitrogen and sulfur donors have attracted much attention because of the flexibility and conformational freedoms. Previously, a series of flexible thioethers were designed, and the investigations on the formation of Ag(I) complexes with these ligands have been reported (Bu et al., 2003; Hong et al., 2000; Zheng et al., 2003; Zheng et al., 2005), while those on the Cu^I complexes with heterocyclic flexible thioether ligands were much more sporadic (Peng et al., 2006; Song et al., 2005).

In the title compound, 1, Fig. 1, two chloride ions are each bound to two symmetry related Cu^I centers forming a Cu₂Cl₂ core. Within these cores the Cu^I centres are separated by a distance of 2.991 (3) Å. The dihedral angle between the two pyrimidyl rings is 83.9 (2) °, with interplanar angles between the S1—C1—S2 plane and the N1 and N3 pyrimidyl rings of the ligand 106.5 (2) ° and 73 (1) °, respectively.

There are weak intermolecular C—H···Cl interactions in the adjacent chain, furnishing a three-dimensional supramolecular array (Fig. 2).

Related literature

For details of metal complexes of bis(pyrimidin-2-ylsulfanyl)methane, see: Hou et al. (2005); Zheng et al. (2003). For complexes of other flexible thioether ligands, see: Bu et al. (2003); Hong et al. (2000); Zheng et al. (2005). For those with heterocyclic components, see: Peng et al. (2006); Song et al. (2005).

For synthesis, see: Xu et al. (1997).

S2. Experimental

The ligand bis(pyrimidin-2-ylsulfanyl)methane was synthesized according to the reported procedure (Xu et al., 1997). Equimolar quantities (0.05 mmol) of solid CuCl (5.0 mg) was added to MeCN solution (7 ml) of the ligand (12.0 mg), the mixture was stirred until a small amount of precipitate was formed. The precipitate was filtered off, and the filtrate was allowed to stand at room temperature for two weeks, well shaped yellow crystals were obtained. Yield: 5.0 mg (30%).

S3. Refinement

All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.93 Å, U_iso=1.2U_eq (C) for aromatic and 0.97 Å, U_iso = 1.2U_eq (C) for CH₂ atoms.

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level, Only the asymmetric unit and one of the symmetry related copper atoms are labelled. [symmetry code: (I) 3/2 - x, 1/2 - y, 1 - z].
	Fig. 2. A view of title compound, showing the extended three-dimensional structure linked by C—H···.Cl hydrogen interactions (dashed lines). H atoms not involved in hydrogen bonding have been omitted for clarity. Displacement ellipsoids are drawn at the 30% probability level, and H atoms are drawn as spheres of arbitrary radii.

catena-Poly[copper(I)-di-µ-chlorido-copper(I)- bis[µ-bis(pyrimidin-2-ylsulfanyl)methane-κ²N:N']]

Crystal data

[Cu2Cl2(C9H8N4S2)2]	F(000) = 1344
Mr = 670.61	Dx = 1.775 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1888 reflections
a = 12.3432 (13) Å	θ = 2.5–23.6°
b = 13.2611 (14) Å	µ = 2.27 mm^−1
c = 15.5179 (17) Å	T = 293 K
β = 98.992 (2)°	Block, yellow
V = 2508.8 (5) Å^3	0.20 × 0.18 × 0.15 mm
Z = 4

Data collection

Bruker APEX area-detector diffractometer	2422 independent reflections
Radiation source: fine-focus sealed tube	2032 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
φ and ω scans	θmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→13
Tmin = 0.660, Tmax = 0.727	k = −16→16
6900 measured reflections	l = −19→16

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0493P)^2 + 1.7815P] where P = (Fo^2 + 2Fc^2)/3
2422 reflections	(Δ/σ)max = 0.001
154 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−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 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
Cu1	0.67661 (3)	0.25183 (3)	0.56808 (3)	0.04173 (17)
S1	0.71478 (8)	0.24875 (6)	0.77139 (6)	0.0457 (2)
Cl1	0.63766 (7)	0.19728 (7)	0.42107 (5)	0.0492 (3)
N1	0.6667 (2)	0.12565 (17)	0.64085 (16)	0.0339 (6)
C4	0.6342 (3)	0.0371 (2)	0.6037 (2)	0.0403 (8)
H4	0.6262	0.0313	0.5433	0.048*
S2	0.57245 (7)	0.22466 (6)	0.91426 (6)	0.0427 (2)
C3	0.6125 (3)	−0.0448 (2)	0.6519 (2)	0.0462 (9)
H3	0.5881	−0.1055	0.6256	0.055*
N2	0.6603 (2)	0.0539 (2)	0.78057 (18)	0.0431 (7)
C2	0.6283 (3)	−0.0331 (2)	0.7404 (2)	0.0487 (9)
H2	0.6163	−0.0883	0.7747	0.058*
N3	0.6021 (2)	0.4215 (2)	0.8873 (2)	0.0495 (7)
N4	0.4249 (2)	0.36602 (19)	0.90977 (16)	0.0347 (6)
C1	0.6763 (2)	0.1290 (2)	0.7280 (2)	0.0335 (7)
C5	0.7080 (3)	0.2308 (3)	0.8853 (2)	0.0419 (8)
H5B	0.7473	0.2857	0.9177	0.050*
H5A	0.7463	0.1688	0.9042	0.050*
C6	0.5306 (3)	0.3511 (2)	0.9025 (2)	0.0372 (7)
C7	0.3891 (3)	0.4610 (2)	0.8990 (2)	0.0440 (8)
H7	0.3165	0.4750	0.9040	0.053*
C8	0.4552 (3)	0.5384 (3)	0.8808 (3)	0.0555 (10)
H8	0.4286	0.6037	0.8716	0.067*
C9	0.5628 (3)	0.5152 (3)	0.8768 (3)	0.0580 (10)
H9	0.6101	0.5668	0.8665	0.070*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0473 (3)	0.0431 (3)	0.0374 (3)	−0.00333 (17)	0.0148 (2)	0.00048 (16)
S1	0.0600 (6)	0.0452 (5)	0.0334 (5)	−0.0081 (4)	0.0119 (4)	−0.0025 (3)
Cl1	0.0425 (5)	0.0745 (6)	0.0324 (4)	−0.0175 (4)	0.0111 (4)	−0.0133 (4)
N1	0.0332 (14)	0.0363 (13)	0.0333 (14)	−0.0018 (10)	0.0089 (11)	0.0012 (11)
C4	0.0369 (18)	0.0428 (18)	0.0419 (19)	0.0027 (14)	0.0082 (15)	−0.0042 (14)
S2	0.0347 (5)	0.0452 (5)	0.0500 (5)	0.0051 (3)	0.0119 (4)	0.0040 (4)
C3	0.048 (2)	0.0329 (17)	0.058 (2)	−0.0022 (14)	0.0113 (18)	−0.0005 (15)
N2	0.0436 (16)	0.0449 (15)	0.0419 (16)	0.0064 (12)	0.0099 (13)	0.0107 (12)
C2	0.049 (2)	0.0370 (18)	0.062 (3)	0.0052 (15)	0.0137 (18)	0.0173 (16)
N3	0.0385 (16)	0.0484 (17)	0.065 (2)	−0.0026 (13)	0.0179 (15)	−0.0011 (14)
N4	0.0308 (14)	0.0413 (14)	0.0326 (14)	0.0009 (11)	0.0064 (11)	−0.0012 (11)
C1	0.0253 (15)	0.0404 (16)	0.0357 (18)	0.0039 (12)	0.0077 (13)	0.0033 (13)
C5	0.0334 (18)	0.057 (2)	0.0353 (18)	0.0070 (14)	0.0064 (14)	−0.0054 (15)
C6	0.0362 (18)	0.0459 (18)	0.0303 (16)	−0.0006 (14)	0.0074 (14)	−0.0042 (13)
C7	0.0339 (18)	0.051 (2)	0.049 (2)	0.0063 (15)	0.0096 (16)	0.0011 (16)
C8	0.054 (2)	0.0432 (19)	0.070 (3)	0.0049 (17)	0.0126 (19)	0.0068 (18)
C9	0.051 (2)	0.051 (2)	0.075 (3)	−0.0079 (17)	0.020 (2)	0.0051 (19)

Geometric parameters (Å, º)

Cu1—N4^i	2.029 (3)	N2—C1	1.322 (4)
Cu1—N1	2.033 (2)	N2—C2	1.341 (4)
Cu1—Cl1	2.3698 (9)	C2—H2	0.9300
Cu1—Cl1^ii	2.3704 (10)	N3—C6	1.331 (4)
Cu1—Cu1^ii	2.9909 (9)	N3—C9	1.334 (4)
S1—C1	1.760 (3)	N4—C7	1.337 (4)
S1—C5	1.799 (3)	N4—C6	1.343 (4)
Cl1—Cu1^ii	2.3704 (10)	N4—Cu1^i	2.029 (3)
N1—C1	1.339 (4)	C5—H5B	0.9700
N1—C4	1.341 (4)	C5—H5A	0.9700
C4—C3	1.369 (4)	C7—C8	1.368 (5)
C4—H4	0.9300	C7—H7	0.9300
S2—C6	1.755 (3)	C8—C9	1.373 (5)
S2—C5	1.801 (3)	C8—H8	0.9300
C3—C2	1.367 (5)	C9—H9	0.9300
C3—H3	0.9300
N4^i—Cu1—N1	115.34 (10)	C6—N3—C9	115.9 (3)
N4^i—Cu1—Cl1	110.69 (7)	C7—N4—C6	115.8 (3)
N1—Cu1—Cl1	105.24 (7)	C7—N4—Cu1^i	121.6 (2)
N4^i—Cu1—Cl1^ii	113.04 (7)	C6—N4—Cu1^i	122.6 (2)
N1—Cu1—Cl1^ii	109.65 (7)	N2—C1—N1	126.9 (3)
Cl1—Cu1—Cl1^ii	101.76 (3)	N2—C1—S1	120.0 (2)
N4^i—Cu1—Cu1^ii	126.16 (7)	N1—C1—S1	113.1 (2)
N1—Cu1—Cu1^ii	118.34 (7)	S1—C5—S2	116.02 (18)
Cl1—Cu1—Cu1^ii	50.89 (2)	S1—C5—H5B	108.3
Cl1^ii—Cu1—Cu1^ii	50.87 (2)	S2—C5—H5B	108.3
C1—S1—C5	101.88 (15)	S1—C5—H5A	108.3
Cu1—Cl1—Cu1^ii	78.24 (3)	S2—C5—H5A	108.3
C1—N1—C4	115.9 (3)	H5B—C5—H5A	107.4
C1—N1—Cu1	121.97 (19)	N3—C6—N4	126.3 (3)
C4—N1—Cu1	121.4 (2)	N3—C6—S2	119.8 (2)
N1—C4—C3	122.1 (3)	N4—C6—S2	114.0 (2)
N1—C4—H4	118.9	N4—C7—C8	122.5 (3)
C3—C4—H4	118.9	N4—C7—H7	118.8
C6—S2—C5	101.55 (15)	C8—C7—H7	118.8
C2—C3—C4	116.6 (3)	C7—C8—C9	117.0 (3)
C2—C3—H3	121.7	C7—C8—H8	121.5
C4—C3—H3	121.7	C9—C8—H8	121.5
C1—N2—C2	115.0 (3)	N3—C9—C8	122.6 (3)
N2—C2—C3	123.4 (3)	N3—C9—H9	118.7
N2—C2—H2	118.3	C8—C9—H9	118.7
C3—C2—H2	118.3
N4^i—Cu1—Cl1—Cu1^ii	120.39 (8)	C4—N1—C1—S1	−178.0 (2)
N1—Cu1—Cl1—Cu1^ii	−114.37 (8)	Cu1—N1—C1—S1	−7.5 (3)
Cl1^ii—Cu1—Cl1—Cu1^ii	0.0	C5—S1—C1—N2	−5.1 (3)
N4^i—Cu1—N1—C1	−52.8 (2)	C5—S1—C1—N1	175.0 (2)
Cl1—Cu1—N1—C1	−175.1 (2)	C1—S1—C5—S2	−74.1 (2)
Cl1^ii—Cu1—N1—C1	76.1 (2)	C6—S2—C5—S1	−72.9 (2)
Cu1^ii—Cu1—N1—C1	131.5 (2)	C9—N3—C6—N4	−1.3 (5)
N4^i—Cu1—N1—C4	117.2 (2)	C9—N3—C6—S2	178.2 (3)
Cl1—Cu1—N1—C4	−5.1 (2)	C7—N4—C6—N3	1.2 (5)
Cl1^ii—Cu1—N1—C4	−113.9 (2)	Cu1^i—N4—C6—N3	179.4 (3)
Cu1^ii—Cu1—N1—C4	−58.5 (2)	C7—N4—C6—S2	−178.4 (2)
C1—N1—C4—C3	−0.2 (4)	Cu1^i—N4—C6—S2	−0.2 (3)
Cu1—N1—C4—C3	−170.7 (2)	C5—S2—C6—N3	−7.6 (3)
N1—C4—C3—C2	−1.7 (5)	C5—S2—C6—N4	172.0 (2)
C1—N2—C2—C3	−0.3 (5)	C6—N4—C7—C8	0.6 (5)
C4—C3—C2—N2	2.0 (5)	Cu1^i—N4—C7—C8	−177.5 (3)
C2—N2—C1—N1	−1.9 (5)	N4—C7—C8—C9	−2.2 (6)
C2—N2—C1—S1	178.2 (2)	C6—N3—C9—C8	−0.4 (6)
C4—N1—C1—N2	2.1 (4)	C7—C8—C9—N3	2.1 (6)
Cu1—N1—C1—N2	172.6 (2)

Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+3/2, −y+1/2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cl1^iii	0.93	2.67	3.537 (4)	155

Symmetry code: (iii) x, −y, z+1/2.