catena-Poly[[dichloridocopper(II)]-μ-1,4-bis­(pyrimidin-2-ylsulfanylmeth­yl)­benzene-κ²N:N′]

In the title complex, [CuCl₂(C₁₆H₁₄N₄S₂)]_n, the Cu atom lies on a center of inversion and is bridged by two adjacent pyrimidine N atoms and two chloride counter-ions to give a square-planar coordination geometry. The bidentate thio­ether ligands link adjacent Cu atoms into an infinite chain.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.047
• wR factor = 0.111
• Data-to-parameter ratio = 17.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       2.08

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

   0 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
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

The coordination chemistry of flexible thioether ligands has attracted considerable attention recently (Caradoc-Davies & Hanton, 2003; Hanton & Lee, 2000; Hong et al., 2000). We are currently involved in the synthesis and study of Cu(I) complexes of a series of N-containing heterocyclic thioether ligands. We have found that the ligand geometry and counteranions play an essential role in the framework formation of the Cu(I) complexes (Peng et al., 2005; Peng et al., 2006). The title compound is obtained from the solvothermal reaction of copper(I) chloride and bis(2-pyrimidinesulfanylmethyl)benzene in the presence of chloroform and acetonitrile solvents. X-ray structure analysis of the crystals shows that atom Cu1 lies on a center of inversion and is coordinated by two chloride anions and two N atoms from two adjacent thioether ligands. The bond angles about the copper atom [exactly 180° for Cl–Cu–Cl and N–Cu–N, and 89.80 (7) and 90.20 (7)° for N–Cu–Cl] confirm that it is in a regular square-planar CuCl₂N₂ geometry. The necessity to balance charges and the geometrical preferences of metal ions indicate the divalent state of the copper ions, which result from Cu(I) being oxidized in air. The thioether ligands, acting as bidentate connectors, link adjacent Cu(II) ions into a zigzag one-dimensional chain.

Related literature

For related literature, see Peng et al. (2005); Caradoc-Davies & Hanton (2003); Hanton & Lee (2000); Hong et al. (2000). For the synthesis of the ligand, see Peng et al. (2006).

S2. Experimental

Bis(2-pyrimidinesulfanylmethyl)benzene was synthesized using a reported procedure (Peng et al., 2006). A mixture of CuCl (0.01 g, 0.1 mmol), bis(2-pyrimidinesulfanylmethyl)benzene (0.033 g, 0.1 mmol), CHCl₃ (2.0 ml) and acetonitrile (4.0 ml) was stirred for 15 min in air and then transferred to a 13 ml Teflon-lined reactor and sealed, then heated in an oven to 393 K for 48 h, and cooled to room temperature at a rate of 3 K 0.5 h^-1. The reaction mixture was filtered to give a yellow-red solution. Black block-shaped crystals of (I) were obtained by slow diffusion of diethyl ether into the solution after one week (yield 36%, based on Cu). Analysis calculated for C₁₆H₁₄Cl₂CuN₄S₂: C 41.66, H 3.04, N 12.15%; found: C 41.81, H 3.13, N 11.97%.

S3. Refinement

The H atoms were placed at calculated positions [aromatic C–H = 0.93 Å and methylene C–H = 0.97 Å; U_iso(H) = 1.2 times U_eq(C)].

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures

Fig. 1. View of a fragment of the chain motif in (I) showing the atom numbering scheme of the asymmetric unit and 30% displacement ellipsoids for the non-hydrogen atoms.

catena-Poly[[dichloridocopper(II)]-µ-1,4-bis(pyrimidin-2-ψlsulfanylmethyl)benzene-κ²N:N']

Crystal data

[CuCl2(C16H14N4S2)]	F(000) = 466
Mr = 460.87	Dx = 1.670 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1784 reflections
a = 8.9243 (9) Å	θ = 2.8–25.7°
b = 9.9867 (9) Å	µ = 1.72 mm^−1
c = 10.4339 (10) Å	T = 295 K
β = 99.667 (2)°	Block, black
V = 916.71 (15) Å^3	0.29 × 0.11 × 0.09 mm
Z = 2

Data collection

Bruker APEX CCD diffractometer	2034 independent reflections
Radiation source: fine-focus sealed tube	1517 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
φ and ω scans	θmax = 27.5°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→11
Tmin = 0.636, Tmax = 0.861	k = −12→12
4908 measured reflections	l = −13→13

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0589P)^2] where P = (Fo^2 + 2Fc^2)/3
2034 reflections	(Δ/σ)max < 0.001
115 parameters	Δρmax = 0.60 e Å^−3
0 restraints	Δρmin = −0.43 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	0.5000	0.5000	0.5000	0.0398 (2)
Cl1	0.57709 (10)	0.70107 (9)	0.44428 (9)	0.0612 (3)
S1	0.20657 (10)	0.64387 (9)	0.57216 (8)	0.0565 (3)
N1	0.3033 (3)	0.5254 (2)	0.3782 (3)	0.0411 (6)
N2	0.0592 (3)	0.6232 (3)	0.3285 (2)	0.0518 (7)
C1	0.2880 (4)	0.4759 (3)	0.2575 (3)	0.0504 (8)
H1	0.3661	0.4249	0.2338	0.060*
C2	0.1601 (4)	0.4987 (4)	0.1686 (3)	0.0633 (11)
H2	0.1487	0.4636	0.0849	0.076*
C3	0.0499 (4)	0.5753 (4)	0.2079 (3)	0.0625 (10)
H3	−0.0363	0.5953	0.1477	0.075*
C4	0.1860 (3)	0.5945 (3)	0.4089 (3)	0.0391 (7)
C5	0.0246 (4)	0.7224 (3)	0.5817 (3)	0.0485 (8)
H5B	−0.0553	0.6716	0.5286	0.058*
H5A	0.0072	0.7180	0.6709	0.058*
C6	0.0134 (3)	0.8652 (3)	0.5382 (3)	0.0404 (7)
C7	−0.0903 (3)	0.9039 (3)	0.4302 (3)	0.0439 (7)
H7	−0.1515	0.8397	0.3826	0.053*
C8	−0.1037 (3)	1.0371 (3)	0.3923 (3)	0.0445 (8)
H8	−0.1739	1.0612	0.3197	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0352 (3)	0.0342 (3)	0.0486 (3)	−0.0014 (2)	0.0032 (2)	−0.0005 (2)
Cl1	0.0574 (5)	0.0444 (6)	0.0783 (6)	−0.0115 (4)	0.0015 (4)	0.0115 (4)
S1	0.0658 (6)	0.0556 (6)	0.0436 (5)	0.0203 (4)	−0.0035 (4)	−0.0068 (4)
N1	0.0394 (13)	0.0373 (15)	0.0459 (14)	−0.0035 (11)	0.0052 (11)	0.0001 (11)
N2	0.0468 (15)	0.0571 (18)	0.0479 (15)	0.0075 (13)	−0.0025 (12)	−0.0003 (13)
C1	0.0462 (18)	0.057 (2)	0.0504 (19)	−0.0045 (15)	0.0162 (15)	−0.0070 (16)
C2	0.060 (2)	0.092 (3)	0.0366 (17)	−0.011 (2)	0.0051 (16)	−0.0100 (17)
C3	0.054 (2)	0.083 (3)	0.0458 (19)	−0.0016 (19)	−0.0043 (15)	0.0035 (19)
C4	0.0429 (15)	0.0329 (17)	0.0398 (15)	−0.0017 (13)	0.0018 (12)	0.0014 (13)
C5	0.058 (2)	0.038 (2)	0.0535 (19)	0.0023 (15)	0.0204 (15)	−0.0011 (15)
C6	0.0402 (16)	0.0373 (18)	0.0482 (16)	0.0029 (13)	0.0205 (13)	−0.0008 (14)
C7	0.0395 (15)	0.041 (2)	0.0527 (18)	−0.0059 (13)	0.0105 (13)	−0.0082 (15)
C8	0.0414 (17)	0.044 (2)	0.0485 (17)	0.0021 (14)	0.0082 (13)	−0.0012 (15)

Geometric parameters (Å, º)

Cu1—N1	2.003 (2)	C2—C3	1.363 (5)
Cu1—N1^i	2.003 (2)	C2—H2	0.9300
Cu1—Cl1^i	2.2311 (8)	C3—H3	0.9300
Cu1—Cl1	2.2311 (8)	C5—C6	1.495 (4)
S1—C4	1.754 (3)	C5—H5B	0.9700
S1—C5	1.821 (3)	C5—H5A	0.9700
N1—C4	1.336 (4)	C6—C7	1.387 (4)
N1—C1	1.339 (4)	C6—C8^ii	1.390 (4)
N2—C4	1.322 (4)	C7—C8	1.387 (4)
N2—C3	1.335 (4)	C7—H7	0.9300
C1—C2	1.364 (5)	C8—C6^ii	1.390 (4)
C1—H1	0.9300	C8—H8	0.9300
N1—Cu1—N1^i	180.0	C2—C3—H3	118.3
N1—Cu1—Cl1^i	90.20 (7)	N2—C4—N1	125.6 (3)
N1^i—Cu1—Cl1^i	89.80 (7)	N2—C4—S1	119.6 (2)
N1—Cu1—Cl1	89.80 (7)	N1—C4—S1	114.8 (2)
N1^i—Cu1—Cl1	90.20 (7)	C6—C5—S1	114.2 (2)
Cl1^i—Cu1—Cl1	180.0	C6—C5—H5B	108.7
C4—S1—C5	103.02 (14)	S1—C5—H5B	108.7
C4—N1—C1	117.1 (3)	C6—C5—H5A	108.7
C4—N1—Cu1	123.5 (2)	S1—C5—H5A	108.7
C1—N1—Cu1	119.4 (2)	H5B—C5—H5A	107.6
C4—N2—C3	115.5 (3)	C7—C6—C8^ii	118.5 (3)
N1—C1—C2	121.4 (3)	C7—C6—C5	120.9 (3)
N1—C1—H1	119.3	C8^ii—C6—C5	120.5 (3)
C2—C1—H1	119.3	C8—C7—C6	120.8 (3)
C3—C2—C1	116.9 (3)	C8—C7—H7	119.6
C3—C2—H2	121.6	C6—C7—H7	119.6
C1—C2—H2	121.6	C7—C8—C6^ii	120.6 (3)
N2—C3—C2	123.4 (3)	C7—C8—H8	119.7
N2—C3—H3	118.3	C6^ii—C8—H8	119.7
Cl1^i—Cu1—N1—C4	97.7 (2)	Cu1—N1—C4—N2	174.1 (2)
Cl1—Cu1—N1—C4	−82.3 (2)	C1—N1—C4—S1	174.6 (2)
Cl1^i—Cu1—N1—C1	−85.0 (2)	Cu1—N1—C4—S1	−8.0 (3)
Cl1—Cu1—N1—C1	95.0 (2)	C5—S1—C4—N2	2.1 (3)
C4—N1—C1—C2	2.0 (5)	C5—S1—C4—N1	−175.9 (2)
Cu1—N1—C1—C2	−175.4 (2)	C4—S1—C5—C6	−82.9 (3)
N1—C1—C2—C3	0.7 (5)	S1—C5—C6—C7	116.1 (3)
C4—N2—C3—C2	1.7 (6)	S1—C5—C6—C8^ii	−65.9 (3)
C1—C2—C3—N2	−2.7 (6)	C8^ii—C6—C7—C8	0.0 (5)
C3—N2—C4—N1	1.4 (5)	C5—C6—C7—C8	178.0 (3)
C3—N2—C4—S1	−176.4 (2)	C6—C7—C8—C6^ii	0.0 (5)
C1—N1—C4—N2	−3.3 (4)

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