Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104026332/fa1093sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104026332/fa1093Isup2.hkl |
CCDC reference: 259013
A mixture of CuCl2·2H2O (0.170 g, 1 mmol) and pyridine-4-thiol (0.111 g, 1 mmol) was dissolved in a CH3CN–tetrahydrofuran mixture (1:1 v/v, 20 ml), stirred at room temperature (298 K) for 1 h and then filtered. The filtrate was allowed to stand at room temperature for two weeks, yielding blue crystals of (I).
H atoms bonded to C atoms were positioned geometrically and refined using a riding model [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C)]. H atoms bonded to N atoms were located from difference maps and refined with the N—H distances restrained to 0.86 (s.u.?) Å [Uiso(H) = 1.2Ueq(N)].
Data collection: SMART (Siemens, 1996); cell refinement: SMART and SAINT (Siemens,1994); data reduction: XPREP in SHELXTL (Siemens, 1994) and SAINT?; program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
(C10H10N2S)[CuCl4] | Z = 2 |
Mr = 395.62 | F(000) = 394 |
Triclinic, P1 | Dx = 1.805 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.2442 (14) Å | Cell parameters from 1200 reflections |
b = 9.4534 (16) Å | θ = 2.1–25.1° |
c = 9.5475 (15) Å | µ = 2.36 mm−1 |
α = 92.594 (3)° | T = 293 K |
β = 94.243 (3)° | Prism, blue |
γ = 100.571 (3)° | 0.38 × 0.34 × 0.20 mm |
V = 728.1 (2) Å3 |
Siemens SMART CCD area-detector diffractometer | 2598 independent reflections |
Radiation source: fine-focus sealed tube | 1667 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
ϕ and ω scans | θmax = 25.1°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.425, Tmax = 0.624 | k = −11→6 |
3836 measured reflections | l = −10→11 |
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)] = 0.074 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.178 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0678P)2 + 3.8146P] where P = (Fo2 + 2Fc2)/3 |
2598 reflections | (Δ/σ)max < 0.001 |
169 parameters | Δρmax = 0.63 e Å−3 |
2 restraints | Δρmin = −0.60 e Å−3 |
(C10H10N2S)[CuCl4] | γ = 100.571 (3)° |
Mr = 395.62 | V = 728.1 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.2442 (14) Å | Mo Kα radiation |
b = 9.4534 (16) Å | µ = 2.36 mm−1 |
c = 9.5475 (15) Å | T = 293 K |
α = 92.594 (3)° | 0.38 × 0.34 × 0.20 mm |
β = 94.243 (3)° |
Siemens SMART CCD area-detector diffractometer | 2598 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1667 reflections with I > 2σ(I) |
Tmin = 0.425, Tmax = 0.624 | Rint = 0.042 |
3836 measured reflections |
R[F2 > 2σ(F2)] = 0.074 | 2 restraints |
wR(F2) = 0.178 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.63 e Å−3 |
2598 reflections | Δρmin = −0.60 e Å−3 |
169 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 | ||
Cu | 0.42591 (13) | 0.70731 (12) | 0.69051 (11) | 0.0387 (4) | |
Cl1 | 0.3877 (3) | 0.7173 (3) | 0.9190 (2) | 0.0592 (8) | |
Cl2 | 0.3229 (4) | 0.4735 (3) | 0.6477 (3) | 0.0671 (8) | |
Cl3 | 0.6520 (3) | 0.8836 (2) | 0.7100 (2) | 0.0443 (6) | |
Cl4 | 0.3133 (3) | 0.7773 (2) | 0.4852 (2) | 0.0462 (6) | |
S | −0.0561 (3) | 0.1884 (3) | −0.0609 (3) | 0.0512 (7) | |
N1 | 0.2046 (11) | 0.4688 (9) | 0.3077 (9) | 0.057 (2) | |
H3A | 0.260 (11) | 0.516 (10) | 0.381 (7) | 0.069* | |
N2 | 0.3326 (12) | 0.0960 (9) | −0.3359 (10) | 0.061 (3) | |
H8A | 0.402 (10) | 0.088 (12) | −0.398 (9) | 0.073* | |
C1 | 0.0765 (13) | 0.3676 (12) | 0.3252 (10) | 0.052 (3) | |
H1A | 0.0393 | 0.3558 | 0.4143 | 0.062* | |
C2 | −0.0020 (11) | 0.2801 (11) | 0.2143 (10) | 0.047 (2) | |
H2A | −0.0928 | 0.2087 | 0.2268 | 0.056* | |
C3 | 0.0551 (11) | 0.2989 (10) | 0.0832 (9) | 0.042 (2) | |
C4 | 0.1893 (12) | 0.4082 (10) | 0.0653 (10) | 0.048 (2) | |
H4A | 0.2269 | 0.4252 | −0.0230 | 0.057* | |
C5 | 0.2632 (13) | 0.4893 (11) | 0.1830 (11) | 0.055 (3) | |
H5A | 0.3562 | 0.5601 | 0.1754 | 0.067* | |
C6 | 0.1830 (14) | 0.1075 (11) | −0.3930 (11) | 0.055 (3) | |
H6A | 0.1596 | 0.0964 | −0.4901 | 0.066* | |
C7 | 0.0650 (11) | 0.1356 (9) | −0.3089 (9) | 0.046 (2) | |
H7A | −0.0400 | 0.1429 | −0.3475 | 0.055* | |
C8 | 0.1043 (10) | 0.1532 (8) | −0.1649 (9) | 0.035 (2) | |
C9 | 0.2564 (11) | 0.1364 (10) | −0.1081 (10) | 0.047 (2) | |
H9A | 0.2821 | 0.1436 | −0.0112 | 0.056* | |
C10 | 0.3699 (12) | 0.1086 (10) | −0.1991 (12) | 0.058 (3) | |
H10A | 0.4749 | 0.0985 | −0.1633 | 0.069* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0370 (6) | 0.0417 (6) | 0.0354 (6) | 0.0023 (5) | 0.0027 (5) | 0.0036 (5) |
Cl1 | 0.0433 (14) | 0.093 (2) | 0.0347 (13) | −0.0056 (13) | 0.0050 (10) | 0.0040 (12) |
Cl2 | 0.090 (2) | 0.0406 (14) | 0.0609 (17) | −0.0050 (13) | −0.0150 (15) | 0.0050 (12) |
Cl3 | 0.0390 (13) | 0.0461 (13) | 0.0457 (13) | 0.0007 (10) | 0.0083 (10) | 0.0027 (10) |
Cl4 | 0.0523 (14) | 0.0446 (13) | 0.0414 (13) | 0.0109 (11) | −0.0044 (10) | 0.0043 (10) |
S | 0.0331 (13) | 0.0705 (17) | 0.0453 (14) | 0.0022 (12) | 0.0040 (10) | −0.0182 (12) |
N1 | 0.061 (6) | 0.060 (6) | 0.048 (6) | 0.017 (5) | −0.016 (5) | −0.019 (4) |
N2 | 0.062 (6) | 0.050 (5) | 0.064 (6) | −0.007 (5) | 0.028 (5) | −0.023 (4) |
C1 | 0.052 (6) | 0.066 (7) | 0.040 (6) | 0.017 (6) | 0.007 (5) | 0.000 (5) |
C2 | 0.035 (5) | 0.056 (6) | 0.050 (6) | 0.011 (5) | 0.007 (4) | 0.003 (5) |
C3 | 0.042 (5) | 0.053 (6) | 0.034 (5) | 0.020 (5) | 0.000 (4) | −0.002 (4) |
C4 | 0.054 (6) | 0.041 (5) | 0.044 (6) | 0.000 (5) | 0.001 (5) | −0.005 (4) |
C5 | 0.053 (6) | 0.045 (6) | 0.059 (7) | −0.006 (5) | −0.004 (5) | −0.009 (5) |
C6 | 0.062 (7) | 0.060 (7) | 0.042 (6) | 0.007 (6) | 0.012 (5) | −0.009 (5) |
C7 | 0.040 (5) | 0.045 (5) | 0.047 (6) | −0.002 (4) | −0.009 (4) | −0.006 (4) |
C8 | 0.034 (5) | 0.031 (4) | 0.040 (5) | 0.001 (4) | 0.007 (4) | −0.003 (4) |
C9 | 0.042 (6) | 0.060 (6) | 0.041 (5) | 0.016 (5) | 0.005 (4) | −0.005 (5) |
C10 | 0.036 (6) | 0.051 (6) | 0.083 (8) | 0.009 (5) | −0.002 (5) | −0.022 (6) |
Cu—Cl2 | 2.226 (3) | C2—C3 | 1.378 (12) |
Cu—Cl1 | 2.228 (2) | C2—H2A | 0.9300 |
Cu—Cl3 | 2.251 (2) | C3—C4 | 1.395 (12) |
Cu—Cl4 | 2.284 (2) | C4—C5 | 1.368 (12) |
S—C3 | 1.776 (9) | C4—H4A | 0.9300 |
S—C8 | 1.781 (8) | C5—H5A | 0.9300 |
N1—C1 | 1.315 (13) | C6—C7 | 1.361 (13) |
N1—C5 | 1.327 (13) | C6—H6A | 0.9300 |
N1—H3A | 0.86 (8) | C7—C8 | 1.384 (12) |
N2—C10 | 1.315 (13) | C7—H7A | 0.9300 |
N2—C6 | 1.336 (14) | C8—C9 | 1.369 (12) |
N2—H8A | 0.86 (9) | C9—C10 | 1.375 (13) |
C1—C2 | 1.359 (13) | C9—H9A | 0.9300 |
C1—H1A | 0.9300 | C10—H10A | 0.9300 |
Cl2—Cu—Cl1 | 96.91 (11) | C5—C4—C3 | 117.2 (9) |
Cl2—Cu—Cl3 | 147.18 (12) | C5—C4—H4A | 121.4 |
Cl1—Cu—Cl3 | 94.84 (9) | C3—C4—H4A | 121.4 |
Cl2—Cu—Cl4 | 95.44 (10) | N1—C5—C4 | 121.2 (9) |
Cl1—Cu—Cl4 | 138.68 (11) | N1—C5—H5A | 119.4 |
Cl3—Cu—Cl4 | 95.67 (9) | C4—C5—H5A | 119.4 |
C3—S—C8 | 102.8 (4) | N2—C6—C7 | 120.0 (9) |
C1—N1—C5 | 122.0 (8) | N2—C6—H6A | 120.0 |
C1—N1—H3A | 119 (7) | C7—C6—H6A | 120.0 |
C5—N1—H3A | 119 (7) | C6—C7—C8 | 118.6 (9) |
C10—N2—C6 | 122.0 (9) | C6—C7—H7A | 120.7 |
C10—N2—H8A | 125 (8) | C8—C7—H7A | 120.7 |
C6—N2—H8A | 113 (8) | C9—C8—C7 | 120.5 (8) |
N1—C1—C2 | 120.6 (9) | C9—C8—S | 123.0 (7) |
N1—C1—H1A | 119.7 | C7—C8—S | 116.4 (7) |
C2—C1—H1A | 119.7 | C8—C9—C10 | 117.7 (9) |
C1—C2—C3 | 118.9 (9) | C8—C9—H9A | 121.2 |
C1—C2—H2A | 120.5 | C10—C9—H9A | 121.2 |
C3—C2—H2A | 120.5 | N2—C10—C9 | 121.1 (10) |
C2—C3—C4 | 120.0 (8) | N2—C10—H10A | 119.4 |
C2—C3—S | 117.8 (7) | C9—C10—H10A | 119.4 |
C4—C3—S | 122.1 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H8A···Cl4i | 0.86 (9) | 2.67 (7) | 3.388 (9) | 142 |
N1—H3A···Cl4 | 0.86 (8) | 2.57 (7) | 3.248 (8) | 136 |
N1—H3A···Cl2 | 0.86 (8) | 2.63 (7) | 3.316 (9) | 138 |
Symmetry code: (i) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | (C10H10N2S)[CuCl4] |
Mr | 395.62 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.2442 (14), 9.4534 (16), 9.5475 (15) |
α, β, γ (°) | 92.594 (3), 94.243 (3), 100.571 (3) |
V (Å3) | 728.1 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.36 |
Crystal size (mm) | 0.38 × 0.34 × 0.20 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.425, 0.624 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3836, 2598, 1667 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.074, 0.178, 1.04 |
No. of reflections | 2598 |
No. of parameters | 169 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.63, −0.60 |
Computer programs: SMART (Siemens, 1996), SMART and SAINT (Siemens,1994), XPREP in SHELXTL (Siemens, 1994) and SAINT?, SHELXTL.
Cu—Cl2 | 2.226 (3) | Cu—Cl4 | 2.284 (2) |
Cu—Cl1 | 2.228 (2) | S—C3 | 1.776 (9) |
Cu—Cl3 | 2.251 (2) | S—C8 | 1.781 (8) |
Cl2—Cu—Cl1 | 96.91 (11) | Cl1—Cu—Cl4 | 138.68 (11) |
Cl2—Cu—Cl3 | 147.18 (12) | Cl3—Cu—Cl4 | 95.67 (9) |
Cl1—Cu—Cl3 | 94.84 (9) | C3—S—C8 | 102.8 (4) |
Cl2—Cu—Cl4 | 95.44 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H8A···Cl4i | 0.86 (9) | 2.67 (7) | 3.388 (9) | 142 |
N1—H3A···Cl4 | 0.86 (8) | 2.57 (7) | 3.248 (8) | 136 |
N1—H3A···Cl2 | 0.86 (8) | 2.63 (7) | 3.316 (9) | 138 |
Symmetry code: (i) −x+1, −y+1, −z. |
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Thiopyridines, as N,S-donor-containing ligands, have been extensively investigated in coordination chemistry because of their varied coordination modes and interesting reactivity. A large number of one-, two- and three-dimensional coordination polymers containing pyridine-2-thiol have been synthesized (Hong et al., 1999; Kato et al., 2002; Wen et al., 2004). However, only a small number of analogues containing pyridine-4-thiol have been reported (Nunokawa et al., 2003; Anjali et al., 2003). We are interested in investigating the thiopyridine–copper halide system because of its potentially interesting reaction chemistry (Cheng et al., 2004). We report here the synthesis and crystal structure of the title compound, (I), containing the 4,4'-bipyridyliumsulfide cation (H2bps2+) and the tetrachlorocuprate(II) anion.
As illustrated in Fig. 1, the asymmetric unit of the crystal structure of (I) contains one [H2bps]2+ cation and one [CuCl4]2− anion. The anion exhibits a flattened tetrahedral geometry with approximate D2 d symmetry, and the CuII ion is surrounded by four Cl atoms, with Cu—Cl distances ranging from 2.226 (3) to 2.284 (2) Å and Cl—Cu—Cl angles ranging from 94.84 (9) to 147.18 (12)°. The mean Cu—Cl bond length [2.247 (2) Å] is close to those observed in similar complexes, e. g. (C10H16N2)[CuCl4] [2.24659 (18) Å; Choi et al., 2002]. The cation is formed via the desulfurization and coupling of pyridine-4-thiol ligands and concomitant release of hydrogen sulfide (see scheme below). The cation is protonated at atoms N1 and N2. To the best of our knowledge, although complexes containing the 4,4'-bipyridyl sulfide ligand have been reported (Su et al., 2002), no structurally characterized example of a 4,4'-bipyridyliumsulfide perhalometallate complex obtained via the desulfurization and coupling of pyridine-4-thiol has been documented to date.
There are N—H···Cl hydrogen-bonding interactions between cations and anions (Fig. 2). Protonated atom N1 forms a three-center interaction with two cis-Cl atoms of one [CuCl4]2− unit, with N1—H3A···Cl2 and N1—H3A···Cl4 distances of 3.316 (9) and 3.248 (8) Å, respectively. Protonated atom N2 forms a two-center hydrogen bond with one Cl atom of another [CuCl4]2− unit, with an distance N2···Cl4i [symmetry code: (i) −x + 1, −y + 1, −z] of 3.388 (9) Å. As a result, two [H2bps]2+ cations and two [CuCl4]2− anions are held together by hydrogen-bonding interactions to form a closed `chair' configuration. The molecules of (I) are arranged regularly, as depicted in Fig. 3, to form channels parallel to the c axis, with dimensions of about 5.330 × 8.680 Å.