Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680703913X/sj2325sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680703913X/sj2325Isup2.hkl |
CCDC reference: 660084
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.041
- wR factor = 0.101
- Data-to-parameter ratio = 15.7
checkCIF/PLATON results
No syntax errors found 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
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%).
All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.93 Å, Uiso=1.2Ueq (C) for aromatic and 0.97 Å, Uiso = 1.2Ueq (C) for CH2 atoms.
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 CuI 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 CuI centers forming a Cu2Cl2 core. Within these cores the CuI 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).
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).
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.
[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) Å3 | 0.20 × 0.18 × 0.15 mm |
Z = 4 |
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 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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0493P)2 + 1.7815P] where P = (Fo2 + 2Fc2)/3 |
2422 reflections | (Δ/σ)max = 0.001 |
154 parameters | Δρmax = 0.53 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
[Cu2Cl2(C9H8N4S2)2] | V = 2508.8 (5) Å3 |
Mr = 670.61 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 12.3432 (13) Å | µ = 2.27 mm−1 |
b = 13.2611 (14) Å | T = 293 K |
c = 15.5179 (17) Å | 0.20 × 0.18 × 0.15 mm |
β = 98.992 (2)° |
Bruker APEX area-detector diffractometer | 2422 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2032 reflections with I > 2σ(I) |
Tmin = 0.660, Tmax = 0.727 | Rint = 0.029 |
6900 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.53 e Å−3 |
2422 reflections | Δρmin = −0.32 e Å−3 |
154 parameters |
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 | ||
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Cu1—N4i | 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—Cl1ii | 2.3704 (10) | N3—C6 | 1.331 (4) |
Cu1—Cu1ii | 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—Cu1ii | 2.3704 (10) | N4—Cu1i | 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 | ||
N4i—Cu1—N1 | 115.34 (10) | C6—N3—C9 | 115.9 (3) |
N4i—Cu1—Cl1 | 110.69 (7) | C7—N4—C6 | 115.8 (3) |
N1—Cu1—Cl1 | 105.24 (7) | C7—N4—Cu1i | 121.6 (2) |
N4i—Cu1—Cl1ii | 113.04 (7) | C6—N4—Cu1i | 122.6 (2) |
N1—Cu1—Cl1ii | 109.65 (7) | N2—C1—N1 | 126.9 (3) |
Cl1—Cu1—Cl1ii | 101.76 (3) | N2—C1—S1 | 120.0 (2) |
N4i—Cu1—Cu1ii | 126.16 (7) | N1—C1—S1 | 113.1 (2) |
N1—Cu1—Cu1ii | 118.34 (7) | S1—C5—S2 | 116.02 (18) |
Cl1—Cu1—Cu1ii | 50.89 (2) | S1—C5—H5B | 108.3 |
Cl1ii—Cu1—Cu1ii | 50.87 (2) | S2—C5—H5B | 108.3 |
C1—S1—C5 | 101.88 (15) | S1—C5—H5A | 108.3 |
Cu1—Cl1—Cu1ii | 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 | ||
N4i—Cu1—Cl1—Cu1ii | 120.39 (8) | C4—N1—C1—S1 | −178.0 (2) |
N1—Cu1—Cl1—Cu1ii | −114.37 (8) | Cu1—N1—C1—S1 | −7.5 (3) |
Cl1ii—Cu1—Cl1—Cu1ii | 0.0 | C5—S1—C1—N2 | −5.1 (3) |
N4i—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) |
Cl1ii—Cu1—N1—C1 | 76.1 (2) | C6—S2—C5—S1 | −72.9 (2) |
Cu1ii—Cu1—N1—C1 | 131.5 (2) | C9—N3—C6—N4 | −1.3 (5) |
N4i—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) |
Cl1ii—Cu1—N1—C4 | −113.9 (2) | Cu1i—N4—C6—N3 | 179.4 (3) |
Cu1ii—Cu1—N1—C4 | −58.5 (2) | C7—N4—C6—S2 | −178.4 (2) |
C1—N1—C4—C3 | −0.2 (4) | Cu1i—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) | Cu1i—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. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···Cl1iii | 0.93 | 2.67 | 3.537 (4) | 155 |
Symmetry code: (iii) x, −y, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu2Cl2(C9H8N4S2)2] |
Mr | 670.61 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 12.3432 (13), 13.2611 (14), 15.5179 (17) |
β (°) | 98.992 (2) |
V (Å3) | 2508.8 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.27 |
Crystal size (mm) | 0.20 × 0.18 × 0.15 |
Data collection | |
Diffractometer | Bruker APEX area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.660, 0.727 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6900, 2422, 2032 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.101, 1.06 |
No. of reflections | 2422 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.53, −0.32 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2002), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···Cl1i | 0.93 | 2.67 | 3.537 (4) | 155.3 |
Symmetry code: (i) x, −y, z+1/2. |
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 CuI 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 CuI centers forming a Cu2Cl2 core. Within these cores the CuI 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).