Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802002118/bt6107sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802002118/bt6107Isup2.hkl |
CCDC reference: 182580
The title compound, (I), was obtained as a green lath-shaped crystal in the midst of a crop of green acicular crystals. Both had been produced by vapour phase diffusion of diethyl ether into a methanol solution of the product of the reaction between a methanol solution (10 ml) of copper(II) chloride dihydrate (0.199 g, 0.704 mmol) and a methanol solution (20 ml) of 2-(3,5-dimethylpyrazol-1-yl)-6-(mercaptopyridin-2-yl)pyridine (0.198 g, 0.701 mmol). This last ligand had been previously prepared by treatment of 2-chloro-6-(mercaptopyridin-2-yl)pyridine with 3,5-dimethylpyrazole in the presence of sodium hydride. Mass spectrometric (electrospray), IR and analytical studies of the bulk product suggested that it comprised dichloro[2-(3,5-dimethylpyrazol-1-yl)-6-(mercaptopyridin-2-yl)pyridine]- copper(II) (yield: 0.123 g, 0.290 mmol, 42%). It is assumed that the lath-shaped crystal was a rogue crystal resulting from the presence of a small amount of unreacted 2-chloro-6-(mercaptopyridin-2-yl)pyridine in the sample of 2-(3,5-dimethylpyrazol-1-yl)-6-(mercaptopyridin-2-yl)pyridine.
After location from ΔF syntheses, the aromatic H atoms were placed geometrically and refined with a riding model in which the C—H distance was constrained to be 0.93 Å and Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT and SHELXTL/PC (Bruker, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2001).
C10H7Cl3CuN2S | Dx = 1.816 Mg m−3 |
Mr = 357.13 | Melting point: unknown K |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.1739 (12) Å | Cell parameters from 3638 reflections |
b = 9.6928 (9) Å | θ = 2.7–26.8° |
c = 21.137 (2) Å | µ = 2.42 mm−1 |
β = 104.510 (2)° | T = 150 K |
V = 2612.9 (4) Å3 | Lath, green |
Z = 8 | 0.36 × 0.11 × 0.06 mm |
F(000) = 1416 |
Bruker SMART APEX area-detector diffractometer | 3191 independent reflections |
Radiation source: normal-focus sealed tube | 2709 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω scans | θmax = 28.2°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −16→17 |
Tmin = 0.782, Tmax = 0.870 | k = −12→12 |
12577 measured reflections | l = −25→26 |
Refinement on F2 | Primary atom site location: direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier methods |
R[F2 > 2σ(F2)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.035P)2 + 3.807P] where P = (Fo2 + 2Fc2)/3 |
3019 reflections | (Δ/σ)max = 0.001 |
154 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C10H7Cl3CuN2S | V = 2612.9 (4) Å3 |
Mr = 357.13 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 13.1739 (12) Å | µ = 2.42 mm−1 |
b = 9.6928 (9) Å | T = 150 K |
c = 21.137 (2) Å | 0.36 × 0.11 × 0.06 mm |
β = 104.510 (2)° |
Bruker SMART APEX area-detector diffractometer | 3191 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2709 reflections with I > 2σ(I) |
Tmin = 0.782, Tmax = 0.870 | Rint = 0.026 |
12577 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.42 e Å−3 |
3019 reflections | Δρmin = −0.25 e Å−3 |
154 parameters |
Geometry. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 4.3612(0.0109)x + 4.7200(0.0074)y + 14.7860(0.0133)z = 14.4719(0.0042) * 0.0000 (0.0000) Cu1 * 0.0000 (0.0000) N1 * 0.0000 (0.0000) N11 Rms deviation of fitted atoms = 0.0000 -0.6243(0.0039)x + 0.1821(0.0032)y + 20.6872(0.0023)z = 12.3931(0.0025) Angle to previous plane (with approximate e.s.d.) = 36.81 (0.06) * 0.0000 (0.0000) Cu1 * 0.0000 (0.0000) Cl1A * 0.0000 (0.0000) Cl1B Rms deviation of fitted atoms = 0.0000 |
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 | 0.81283 (2) | 0.37177 (2) | 0.620326 (12) | 0.02032 (9) | |
Cl1A | 0.64623 (4) | 0.31835 (6) | 0.61577 (3) | 0.02691 (13) | |
Cl1B | 0.79542 (5) | 0.59810 (6) | 0.61781 (3) | 0.03713 (16) | |
N1 | 0.86147 (14) | 0.18898 (18) | 0.66433 (9) | 0.0213 (4) | |
C2 | 0.86340 (17) | 0.1660 (2) | 0.72696 (11) | 0.0254 (5) | |
Cl2 | 0.86089 (5) | 0.31151 (7) | 0.77305 (3) | 0.03394 (15) | |
C3 | 0.86670 (18) | 0.0364 (3) | 0.75435 (12) | 0.0311 (5) | |
H3 | 0.8646 | 0.0244 | 0.7977 | 0.037* | |
C4 | 0.87322 (18) | −0.0746 (3) | 0.71472 (13) | 0.0347 (6) | |
H4 | 0.8737 | −0.1638 | 0.7310 | 0.042* | |
C5 | 0.87900 (17) | −0.0546 (2) | 0.65108 (13) | 0.0296 (5) | |
H5 | 0.8870 | −0.1287 | 0.6248 | 0.036* | |
C6 | 0.87249 (16) | 0.0794 (2) | 0.62739 (11) | 0.0226 (4) | |
S6 | 0.87047 (4) | 0.11187 (5) | 0.54457 (3) | 0.02462 (13) | |
N11 | 0.94027 (14) | 0.36732 (17) | 0.58416 (9) | 0.0203 (4) | |
C12 | 0.96231 (16) | 0.2509 (2) | 0.55553 (10) | 0.0208 (4) | |
C13 | 1.05055 (18) | 0.2358 (2) | 0.53281 (11) | 0.0266 (5) | |
H13 | 1.0634 | 0.1539 | 0.5133 | 0.032* | |
C14 | 1.12019 (18) | 0.3455 (2) | 0.53959 (12) | 0.0296 (5) | |
H14 | 1.1801 | 0.3387 | 0.5241 | 0.036* | |
C15 | 1.09924 (17) | 0.4644 (2) | 0.56957 (11) | 0.0271 (5) | |
H15 | 1.1452 | 0.5388 | 0.5749 | 0.033* | |
C16 | 1.00967 (17) | 0.4720 (2) | 0.59152 (11) | 0.0235 (4) | |
H16 | 0.9964 | 0.5522 | 0.6122 | 0.028* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.02286 (14) | 0.01603 (13) | 0.02317 (15) | 0.00149 (9) | 0.00783 (11) | −0.00009 (9) |
Cl1A | 0.0236 (3) | 0.0286 (3) | 0.0287 (3) | −0.0013 (2) | 0.0068 (2) | −0.0071 (2) |
Cl1B | 0.0392 (3) | 0.0172 (3) | 0.0612 (4) | 0.0050 (2) | 0.0241 (3) | 0.0020 (2) |
N1 | 0.0208 (9) | 0.0219 (9) | 0.0219 (9) | −0.0008 (7) | 0.0062 (7) | 0.0020 (7) |
C2 | 0.0190 (10) | 0.0312 (11) | 0.0262 (12) | 0.0016 (8) | 0.0062 (9) | 0.0029 (9) |
Cl2 | 0.0352 (3) | 0.0433 (3) | 0.0241 (3) | 0.0036 (2) | 0.0087 (2) | −0.0041 (2) |
C3 | 0.0230 (11) | 0.0404 (13) | 0.0311 (13) | 0.0001 (10) | 0.0092 (10) | 0.0141 (10) |
C4 | 0.0254 (11) | 0.0273 (12) | 0.0508 (16) | −0.0014 (9) | 0.0083 (11) | 0.0173 (11) |
C5 | 0.0238 (11) | 0.0209 (11) | 0.0423 (14) | −0.0009 (8) | 0.0048 (10) | 0.0025 (10) |
C6 | 0.0184 (9) | 0.0214 (10) | 0.0279 (11) | −0.0014 (8) | 0.0055 (8) | 0.0016 (8) |
S6 | 0.0291 (3) | 0.0194 (3) | 0.0253 (3) | −0.0028 (2) | 0.0068 (2) | −0.0055 (2) |
N11 | 0.0233 (9) | 0.0181 (8) | 0.0197 (9) | 0.0013 (7) | 0.0057 (7) | 0.0019 (7) |
C12 | 0.0254 (10) | 0.0178 (9) | 0.0179 (10) | −0.0009 (8) | 0.0031 (8) | 0.0013 (7) |
C13 | 0.0288 (11) | 0.0269 (11) | 0.0250 (11) | 0.0030 (9) | 0.0080 (9) | −0.0024 (9) |
C14 | 0.0241 (11) | 0.0357 (12) | 0.0306 (12) | 0.0028 (9) | 0.0098 (9) | 0.0039 (10) |
C15 | 0.0231 (11) | 0.0255 (11) | 0.0311 (12) | −0.0032 (8) | 0.0036 (9) | 0.0062 (9) |
C16 | 0.0271 (11) | 0.0178 (10) | 0.0245 (11) | 0.0010 (8) | 0.0045 (9) | 0.0019 (8) |
Cu1—Cl1A | 2.2335 (6) | N11—C12 | 1.346 (3) |
Cu1—Cl1B | 2.2049 (6) | N11—C16 | 1.348 (3) |
Cu1—N1 | 2.029 (2) | C12—C13 | 1.372 (3) |
Cu1—N11 | 2.012 (2) | C13—C14 | 1.388 (3) |
N1—C2 | 1.336 (3) | C14—C15 | 1.376 (3) |
N1—C6 | 1.348 (3) | C15—C16 | 1.374 (3) |
C2—C3 | 1.379 (3) | C3—H3 | 0.93 |
C2—Cl2 | 1.719 (2) | C4—H4 | 0.93 |
C3—C4 | 1.380 (4) | C5—H5 | 0.93 |
C4—C5 | 1.380 (4) | C13—H13 | 0.93 |
C5—C6 | 1.386 (3) | C14—H14 | 0.93 |
C6—S6 | 1.772 (2) | C15—H15 | 0.93 |
S6—C12 | 1.787 (2) | C16—H16 | 0.93 |
Cl1A—Cu1—Cl1B | 97.73 (2) | N11—C12—C13 | 123.0 (2) |
Cl1A—Cu1—N1 | 90.65 (5) | N11—C12—S6 | 118.38 (16) |
Cl1A—Cu1—N11 | 152.02 (5) | C13—C12—S6 | 118.64 (16) |
Cl1B—Cu1—N11 | 95.96 (5) | C12—C13—C14 | 118.6 (2) |
Cl1B—Cu1—N1 | 154.01 (5) | C15—C14—C13 | 119.0 (2) |
N1—Cu1—N11 | 87.58 (7) | C16—C15—C14 | 119.2 (2) |
C2—N1—C6 | 117.68 (19) | N11—C16—C15 | 122.4 (2) |
C2—N1—Cu1 | 121.67 (15) | C2—C3—H3 | 121.4 |
C6—N1—Cu1 | 119.37 (14) | C4—C3—H3 | 121.4 |
N1—C2—C3 | 123.9 (2) | C3—C4—H4 | 119.7 |
N1—C2—Cl2 | 115.25 (17) | C5—C4—H4 | 119.7 |
C3—C2—Cl2 | 120.81 (19) | C4—C5—H5 | 121.0 |
C2—C3—C4 | 117.1 (2) | C6—C5—H5 | 121.0 |
C3—C4—C5 | 120.6 (2) | C12—C13—H13 | 120.7 |
C4—C5—C6 | 118.1 (2) | C14—C13—H13 | 120.7 |
N1—C6—C5 | 122.3 (2) | C15—C14—H14 | 120.5 |
N1—C6—S6 | 117.06 (16) | C13—C14—H14 | 120.5 |
C5—C6—S6 | 120.49 (18) | C16—C15—H15 | 120.4 |
C6—S6—C12 | 99.43 (10) | C14—C15—H15 | 120.4 |
C12—N11—C16 | 117.78 (19) | N11—C16—H16 | 118.8 |
C12—N11—Cu1 | 118.91 (14) | C15—C16—H16 | 118.8 |
C16—N11—Cu1 | 123.11 (15) |
Experimental details
Crystal data | |
Chemical formula | C10H7Cl3CuN2S |
Mr | 357.13 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 13.1739 (12), 9.6928 (9), 21.137 (2) |
β (°) | 104.510 (2) |
V (Å3) | 2612.9 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.42 |
Crystal size (mm) | 0.36 × 0.11 × 0.06 |
Data collection | |
Diffractometer | Bruker SMART APEX area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.782, 0.870 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12577, 3191, 2709 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.665 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.071, 1.04 |
No. of reflections | 3019 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.42, −0.25 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2000), SAINT and SHELXTL/PC (Bruker, 1997), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), CAMERON (Watkin et al., 1996), SHELXL97 and PLATON (Spek, 2001).
Cu1—Cl1A | 2.2335 (6) | Cu1—N1 | 2.029 (2) |
Cu1—Cl1B | 2.2049 (6) | Cu1—N11 | 2.012 (2) |
Cl1A—Cu1—Cl1B | 97.73 (2) | N1—Cu1—N11 | 87.58 (7) |
Cl1A—Cu1—N1 | 90.65 (5) | C2—N1—Cu1 | 121.67 (15) |
Cl1A—Cu1—N11 | 152.02 (5) | C6—N1—Cu1 | 119.37 (14) |
Cl1B—Cu1—N11 | 95.96 (5) | C12—N11—Cu1 | 118.91 (14) |
Cl1B—Cu1—N1 | 154.01 (5) | C16—N11—Cu1 | 123.11 (15) |
The structure of CuCl2L [L = 2-chloro-6-(mercaptopyridin-2-yl)pyridine], (I), is that of a neutral molecular complex (Fig. 1) in which the copper(II) centre has a distorted four-coordinate geometry comprising the two N atoms of the bidentate chelating ligand L [Cu—N 2.012 (2) and 2.029 (2) Å] and the two chloride anions [Cu—Cl 2.2049 (6) and 2.2335 (6) Å]. The coordination geometry lies between square planar and tetrahedral, with a dihedral angle (δ) between the CuN2 and CuCl2 planes of 36.81 (6)°. Distortion from planarity is unusual for copper(II) complexes. It is attributed to steric repulsion between a coordinated chloride anion and the Cl atom at the 2-position of the pyridine ring [Cl···Cl 3.787 (1) Å].
There is considerable evidence for dimer formation through Cl···S interactions (Fig. 2). Not only is the Cu···Cl distance to the chloride anion involved in dimer formation [2.2335 (6) Å] significantly longer than that to the other chloride anion [2.2049 (6) Å], but also the Ueq value for the former [0.02691 (13) Å2] is considerably smaller than that for the latter [0.03713 (16) Å2]. A search of the Cambridge Structural Database (Allen & Kennard, 1993) revealed that the intradimer Cl···S separation [3.4085 (9) Å] is typical for the distance separating the chloride anion of a CuCl2 fragment and the S atom of either an aromatic or an aliphatic thioether.