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The title compound, (C10H10N2S)[CuCl4], was obtained by the reaction of cupric chloride with pyridine-4-thiol in a mixture of aceto­nitrile and tetra­hydro­furan, suggesting that the desulfurization and coupling reactions of pyridine-4-thiol occurred in the presence of the Cu2+ ion. X-ray diffraction analysis reveals the presence of one 4,4′-thio­dipyridinium cation, H2bps2+, and one [CuCl4]2− anion. The cations interact with the anions via N—H...Cl hydrogen-bonding interactions to form a closed `chair' conformation.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104026332/fa1093sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104026332/fa1093Isup2.hkl
Contains datablock I

CCDC reference: 259013

Comment top

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.

Experimental top

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).

Refinement top

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)].

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A view of (I), with 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. The closed `chair' configuration of (I). Hydrogen bonds are depicted as dashed lines.
[Figure 3] Fig. 3. A packing diagram of the title compound, showing channels parallel to the c axis.
4,4'-Thiodipyridinium tetrachlorocopper(II) top
Crystal data top
(C10H10N2S)[CuCl4]Z = 2
Mr = 395.62F(000) = 394
Triclinic, P1Dx = 1.805 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.2442 (14) ÅCell parameters from 1200 reflections
b = 9.4534 (16) Åθ = 2.1–25.1°
c = 9.5475 (15) ŵ = 2.36 mm1
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
Data collection top
Siemens SMART CCD area-detector
diffractometer
2598 independent reflections
Radiation source: fine-focus sealed tube1667 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
ϕ and ω scansθmax = 25.1°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 99
Tmin = 0.425, Tmax = 0.624k = 116
3836 measured reflectionsl = 1011
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.074Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.178H 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 parametersΔρmax = 0.63 e Å3
2 restraintsΔρmin = 0.60 e Å3
Crystal data top
(C10H10N2S)[CuCl4]γ = 100.571 (3)°
Mr = 395.62V = 728.1 (2) Å3
Triclinic, P1Z = 2
a = 8.2442 (14) ÅMo Kα radiation
b = 9.4534 (16) ŵ = 2.36 mm1
c = 9.5475 (15) ÅT = 293 K
α = 92.594 (3)°0.38 × 0.34 × 0.20 mm
β = 94.243 (3)°
Data collection top
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 = 0.624Rint = 0.042
3836 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0742 restraints
wR(F2) = 0.178H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.63 e Å3
2598 reflectionsΔρmin = 0.60 e Å3
169 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
Cu0.42591 (13)0.70731 (12)0.69051 (11)0.0387 (4)
Cl10.3877 (3)0.7173 (3)0.9190 (2)0.0592 (8)
Cl20.3229 (4)0.4735 (3)0.6477 (3)0.0671 (8)
Cl30.6520 (3)0.8836 (2)0.7100 (2)0.0443 (6)
Cl40.3133 (3)0.7773 (2)0.4852 (2)0.0462 (6)
S0.0561 (3)0.1884 (3)0.0609 (3)0.0512 (7)
N10.2046 (11)0.4688 (9)0.3077 (9)0.057 (2)
H3A0.260 (11)0.516 (10)0.381 (7)0.069*
N20.3326 (12)0.0960 (9)0.3359 (10)0.061 (3)
H8A0.402 (10)0.088 (12)0.398 (9)0.073*
C10.0765 (13)0.3676 (12)0.3252 (10)0.052 (3)
H1A0.03930.35580.41430.062*
C20.0020 (11)0.2801 (11)0.2143 (10)0.047 (2)
H2A0.09280.20870.22680.056*
C30.0551 (11)0.2989 (10)0.0832 (9)0.042 (2)
C40.1893 (12)0.4082 (10)0.0653 (10)0.048 (2)
H4A0.22690.42520.02300.057*
C50.2632 (13)0.4893 (11)0.1830 (11)0.055 (3)
H5A0.35620.56010.17540.067*
C60.1830 (14)0.1075 (11)0.3930 (11)0.055 (3)
H6A0.15960.09640.49010.066*
C70.0650 (11)0.1356 (9)0.3089 (9)0.046 (2)
H7A0.04000.14290.34750.055*
C80.1043 (10)0.1532 (8)0.1649 (9)0.035 (2)
C90.2564 (11)0.1364 (10)0.1081 (10)0.047 (2)
H9A0.28210.14360.01120.056*
C100.3699 (12)0.1086 (10)0.1991 (12)0.058 (3)
H10A0.47490.09850.16330.069*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu0.0370 (6)0.0417 (6)0.0354 (6)0.0023 (5)0.0027 (5)0.0036 (5)
Cl10.0433 (14)0.093 (2)0.0347 (13)0.0056 (13)0.0050 (10)0.0040 (12)
Cl20.090 (2)0.0406 (14)0.0609 (17)0.0050 (13)0.0150 (15)0.0050 (12)
Cl30.0390 (13)0.0461 (13)0.0457 (13)0.0007 (10)0.0083 (10)0.0027 (10)
Cl40.0523 (14)0.0446 (13)0.0414 (13)0.0109 (11)0.0044 (10)0.0043 (10)
S0.0331 (13)0.0705 (17)0.0453 (14)0.0022 (12)0.0040 (10)0.0182 (12)
N10.061 (6)0.060 (6)0.048 (6)0.017 (5)0.016 (5)0.019 (4)
N20.062 (6)0.050 (5)0.064 (6)0.007 (5)0.028 (5)0.023 (4)
C10.052 (6)0.066 (7)0.040 (6)0.017 (6)0.007 (5)0.000 (5)
C20.035 (5)0.056 (6)0.050 (6)0.011 (5)0.007 (4)0.003 (5)
C30.042 (5)0.053 (6)0.034 (5)0.020 (5)0.000 (4)0.002 (4)
C40.054 (6)0.041 (5)0.044 (6)0.000 (5)0.001 (5)0.005 (4)
C50.053 (6)0.045 (6)0.059 (7)0.006 (5)0.004 (5)0.009 (5)
C60.062 (7)0.060 (7)0.042 (6)0.007 (6)0.012 (5)0.009 (5)
C70.040 (5)0.045 (5)0.047 (6)0.002 (4)0.009 (4)0.006 (4)
C80.034 (5)0.031 (4)0.040 (5)0.001 (4)0.007 (4)0.003 (4)
C90.042 (6)0.060 (6)0.041 (5)0.016 (5)0.005 (4)0.005 (5)
C100.036 (6)0.051 (6)0.083 (8)0.009 (5)0.002 (5)0.022 (6)
Geometric parameters (Å, º) top
Cu—Cl22.226 (3)C2—C31.378 (12)
Cu—Cl12.228 (2)C2—H2A0.9300
Cu—Cl32.251 (2)C3—C41.395 (12)
Cu—Cl42.284 (2)C4—C51.368 (12)
S—C31.776 (9)C4—H4A0.9300
S—C81.781 (8)C5—H5A0.9300
N1—C11.315 (13)C6—C71.361 (13)
N1—C51.327 (13)C6—H6A0.9300
N1—H3A0.86 (8)C7—C81.384 (12)
N2—C101.315 (13)C7—H7A0.9300
N2—C61.336 (14)C8—C91.369 (12)
N2—H8A0.86 (9)C9—C101.375 (13)
C1—C21.359 (13)C9—H9A0.9300
C1—H1A0.9300C10—H10A0.9300
Cl2—Cu—Cl196.91 (11)C5—C4—C3117.2 (9)
Cl2—Cu—Cl3147.18 (12)C5—C4—H4A121.4
Cl1—Cu—Cl394.84 (9)C3—C4—H4A121.4
Cl2—Cu—Cl495.44 (10)N1—C5—C4121.2 (9)
Cl1—Cu—Cl4138.68 (11)N1—C5—H5A119.4
Cl3—Cu—Cl495.67 (9)C4—C5—H5A119.4
C3—S—C8102.8 (4)N2—C6—C7120.0 (9)
C1—N1—C5122.0 (8)N2—C6—H6A120.0
C1—N1—H3A119 (7)C7—C6—H6A120.0
C5—N1—H3A119 (7)C6—C7—C8118.6 (9)
C10—N2—C6122.0 (9)C6—C7—H7A120.7
C10—N2—H8A125 (8)C8—C7—H7A120.7
C6—N2—H8A113 (8)C9—C8—C7120.5 (8)
N1—C1—C2120.6 (9)C9—C8—S123.0 (7)
N1—C1—H1A119.7C7—C8—S116.4 (7)
C2—C1—H1A119.7C8—C9—C10117.7 (9)
C1—C2—C3118.9 (9)C8—C9—H9A121.2
C1—C2—H2A120.5C10—C9—H9A121.2
C3—C2—H2A120.5N2—C10—C9121.1 (10)
C2—C3—C4120.0 (8)N2—C10—H10A119.4
C2—C3—S117.8 (7)C9—C10—H10A119.4
C4—C3—S122.1 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H8A···Cl4i0.86 (9)2.67 (7)3.388 (9)142
N1—H3A···Cl40.86 (8)2.57 (7)3.248 (8)136
N1—H3A···Cl20.86 (8)2.63 (7)3.316 (9)138
Symmetry code: (i) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula(C10H10N2S)[CuCl4]
Mr395.62
Crystal system, space groupTriclinic, 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)
V3)728.1 (2)
Z2
Radiation typeMo Kα
µ (mm1)2.36
Crystal size (mm)0.38 × 0.34 × 0.20
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.425, 0.624
No. of measured, independent and
observed [I > 2σ(I)] reflections
3836, 2598, 1667
Rint0.042
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.074, 0.178, 1.04
No. of reflections2598
No. of parameters169
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.63, 0.60

Computer programs: SMART (Siemens, 1996), SMART and SAINT (Siemens,1994), XPREP in SHELXTL (Siemens, 1994) and SAINT?, SHELXTL.

Selected geometric parameters (Å, º) top
Cu—Cl22.226 (3)Cu—Cl42.284 (2)
Cu—Cl12.228 (2)S—C31.776 (9)
Cu—Cl32.251 (2)S—C81.781 (8)
Cl2—Cu—Cl196.91 (11)Cl1—Cu—Cl4138.68 (11)
Cl2—Cu—Cl3147.18 (12)Cl3—Cu—Cl495.67 (9)
Cl1—Cu—Cl394.84 (9)C3—S—C8102.8 (4)
Cl2—Cu—Cl495.44 (10)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H8A···Cl4i0.86 (9)2.67 (7)3.388 (9)142
N1—H3A···Cl40.86 (8)2.57 (7)3.248 (8)136
N1—H3A···Cl20.86 (8)2.63 (7)3.316 (9)138
Symmetry code: (i) x+1, y+1, z.
 

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