Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106054047/sq3054sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106054047/sq3054Isup2.hkl |
CCDC reference: 638304
CuCl (1 mmol) was added to a solution of 1,4-oxathiane (1 mmol) in benzene (2 ml) at 5°. The resulting product was mainly composed of light-brown crystals of complex (I). Detailed examination of some batches revealed also some dark-brown plate-like crystals of complex (III) (Salivon et al., 2006).
H atoms were treated using a riding model (C—H = 0.97 Å), with isotropic displacement parameters 1.2 times Ueq of the neighbouring non-H atom.
Data collection: EXPOSE in IPDS Software (Stoe & Cie, 1999); cell refinement: CELL in IPDS Software; data reduction: TWIN in IPDS Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.
[CuCl(C4H8OS)] | F(000) = 408 |
Mr = 203.17 | Dx = 1.974 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ybc | Cell parameters from 1892 reflections |
a = 9.5068 (12) Å | θ = 7.3–55.7° |
b = 6.5035 (10) Å | µ = 3.79 mm−1 |
c = 11.4259 (16) Å | T = 293 K |
β = 104.572 (15)° | Prism, light brown |
V = 683.71 (17) Å3 | 0.17 × 0.09 × 0.07 mm |
Z = 4 |
Stoe IPDS diffractometer | 1658 independent reflections |
Radiation source: fine-focus sealed tube | 892 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
ϕ oscillation scans | θmax = 28.1°, θmin = 3.6° |
Absorption correction: numerical (X-RED; Stoe & Cie, 1999) | h = −12→10 |
Tmin = 0.739, Tmax = 0.859 | k = −8→8 |
4497 measured reflections | l = −13→15 |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.070 | H-atom parameters constrained |
S = 0.77 | w = 1/[σ2(Fo2) + (0.0294P)2] where P = (Fo2 + 2Fc2)/3 |
1600 reflections | (Δ/σ)max = 0.044 |
43 parameters | Δρmax = 0.53 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
[CuCl(C4H8OS)] | V = 683.71 (17) Å3 |
Mr = 203.17 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.5068 (12) Å | µ = 3.79 mm−1 |
b = 6.5035 (10) Å | T = 293 K |
c = 11.4259 (16) Å | 0.17 × 0.09 × 0.07 mm |
β = 104.572 (15)° |
Stoe IPDS diffractometer | 1658 independent reflections |
Absorption correction: numerical (X-RED; Stoe & Cie, 1999) | 892 reflections with I > 2σ(I) |
Tmin = 0.739, Tmax = 0.859 | Rint = 0.061 |
4497 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.070 | H-atom parameters constrained |
S = 0.77 | Δρmax = 0.53 e Å−3 |
1600 reflections | Δρmin = −0.37 e Å−3 |
43 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 | −0.01359 (7) | 0.55929 (8) | 0.86419 (5) | 0.03878 (17) | |
Cl1 | 0.15683 (12) | 0.65605 (14) | 1.04318 (9) | 0.0371 (3) | |
S1 | 0.11153 (12) | 0.29782 (13) | 0.77934 (9) | 0.0291 (2) | |
O1 | 0.4328 (4) | 0.1343 (5) | 0.8666 (3) | 0.0499 (8) | |
C1 | 0.1952 (5) | 0.1440 (6) | 0.9110 (4) | 0.0367 (10) | |
H1A | 0.2330 | 0.2339 | 0.9794 | 0.044* | |
H1B | 0.1224 | 0.0557 | 0.9310 | 0.044* | |
C2 | 0.3166 (5) | 0.0141 (6) | 0.8882 (4) | 0.0410 (11) | |
H2A | 0.3538 | −0.0738 | 0.9577 | 0.049* | |
H2B | 0.2786 | −0.0737 | 0.8189 | 0.049* | |
C3 | 0.3919 (5) | 0.2477 (7) | 0.7570 (5) | 0.0478 (11) | |
H4A | 0.3526 | 0.1541 | 0.6908 | 0.057* | |
H4B | 0.4775 | 0.3121 | 0.7417 | 0.057* | |
C4 | 0.2809 (5) | 0.4105 (6) | 0.7604 (4) | 0.0440 (11) | |
H5A | 0.2610 | 0.4889 | 0.6858 | 0.053* | |
H5B | 0.3197 | 0.5041 | 0.8268 | 0.053* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0447 (3) | 0.0384 (3) | 0.0310 (3) | 0.0011 (3) | 0.0053 (2) | 0.0052 (2) |
Cl1 | 0.0455 (7) | 0.0340 (4) | 0.0292 (5) | −0.0120 (4) | 0.0048 (5) | 0.0000 (4) |
S1 | 0.0350 (6) | 0.0256 (4) | 0.0252 (5) | 0.0025 (4) | 0.0046 (4) | −0.0011 (4) |
O1 | 0.043 (2) | 0.0495 (16) | 0.0529 (19) | 0.0014 (14) | 0.0047 (17) | 0.0142 (15) |
C1 | 0.046 (3) | 0.0343 (18) | 0.026 (2) | 0.0011 (19) | 0.002 (2) | 0.0047 (16) |
C2 | 0.042 (3) | 0.035 (2) | 0.041 (2) | 0.0046 (18) | 0.001 (2) | 0.0091 (17) |
C3 | 0.040 (3) | 0.047 (2) | 0.058 (3) | −0.008 (2) | 0.016 (2) | 0.008 (2) |
C4 | 0.053 (3) | 0.035 (2) | 0.042 (2) | −0.0043 (19) | 0.009 (2) | 0.0075 (18) |
Cu1—S1i | 2.2792 (10) | C1—H1A | 0.9700 |
Cu1—Cl1 | 2.3529 (12) | C1—H1B | 0.9700 |
Cu1—Cl1ii | 2.3793 (12) | C2—H2A | 0.9700 |
Cu1—S1 | 2.4139 (12) | C2—H2B | 0.9700 |
S1—C1 | 1.815 (4) | C3—C4 | 1.502 (6) |
S1—C4 | 1.831 (5) | C3—H4A | 0.9700 |
O1—C3 | 1.420 (6) | C3—H4B | 0.9700 |
O1—C2 | 1.425 (5) | C4—H5A | 0.9700 |
C1—C2 | 1.505 (6) | C4—H5B | 0.9700 |
S1i—Cu1—Cl1 | 120.71 (4) | H1A—C1—H1B | 108.0 |
S1i—Cu1—Cl1ii | 123.01 (5) | O1—C2—C1 | 112.6 (3) |
Cl1—Cu1—Cl1ii | 96.71 (4) | O1—C2—H2A | 109.1 |
S1i—Cu1—S1 | 110.11 (3) | C1—C2—H2A | 109.1 |
Cl1—Cu1—S1 | 103.67 (4) | O1—C2—H2B | 109.1 |
Cl1ii—Cu1—S1 | 99.15 (4) | C1—C2—H2B | 109.1 |
Cu1—Cl1—Cu1ii | 83.29 (4) | H2A—C2—H2B | 107.8 |
C1—S1—C4 | 95.9 (2) | O1—C3—C4 | 112.5 (4) |
C1—S1—Cu1iii | 103.63 (14) | O1—C3—H4A | 109.1 |
C4—S1—Cu1iii | 113.55 (15) | C4—C3—H4A | 109.1 |
C1—S1—Cu1 | 102.29 (14) | O1—C3—H4B | 109.1 |
C4—S1—Cu1 | 107.61 (14) | C4—C3—H4B | 109.1 |
Cu1iii—S1—Cu1 | 127.96 (5) | H4A—C3—H4B | 107.8 |
C3—O1—C2 | 112.7 (4) | C3—C4—S1 | 111.4 (3) |
C2—C1—S1 | 111.2 (3) | C3—C4—H5A | 109.3 |
C2—C1—H1A | 109.4 | S1—C4—H5A | 109.3 |
S1—C1—H1A | 109.4 | C3—C4—H5B | 109.3 |
C2—C1—H1B | 109.4 | S1—C4—H5B | 109.3 |
S1—C1—H1B | 109.4 | H5A—C4—H5B | 108.0 |
S1i—Cu1—Cl1—Cu1ii | 135.07 (5) | Cl1ii—Cu1—S1—Cu1iii | 62.93 (6) |
Cl1ii—Cu1—Cl1—Cu1ii | 0.0 | C4—S1—C1—C2 | −52.2 (3) |
S1—Cu1—Cl1—Cu1ii | −101.15 (4) | Cu1iii—S1—C1—C2 | 63.9 (3) |
S1i—Cu1—S1—C1 | 174.22 (16) | Cu1—S1—C1—C2 | −161.7 (3) |
Cl1—Cu1—S1—C1 | 43.77 (16) | C3—O1—C2—C1 | −66.5 (5) |
Cl1ii—Cu1—S1—C1 | −55.49 (16) | S1—C1—C2—O1 | 63.2 (4) |
S1i—Cu1—S1—C4 | 73.83 (15) | C2—O1—C3—C4 | 66.1 (5) |
Cl1—Cu1—S1—C4 | −56.62 (15) | O1—C3—C4—S1 | −62.5 (5) |
Cl1ii—Cu1—S1—C4 | −155.88 (15) | C1—S1—C4—C3 | 52.1 (4) |
S1i—Cu1—S1—Cu1iii | −67.36 (7) | Cu1iii—S1—C4—C3 | −55.6 (4) |
Cl1—Cu1—S1—Cu1iii | 162.19 (5) | Cu1—S1—C4—C3 | 157.0 (3) |
Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x, −y+1, −z+2; (iii) −x, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [CuCl(C4H8OS)] |
Mr | 203.17 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 9.5068 (12), 6.5035 (10), 11.4259 (16) |
β (°) | 104.572 (15) |
V (Å3) | 683.71 (17) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.79 |
Crystal size (mm) | 0.17 × 0.09 × 0.07 |
Data collection | |
Diffractometer | Stoe IPDS diffractometer |
Absorption correction | Numerical (X-RED; Stoe & Cie, 1999) |
Tmin, Tmax | 0.739, 0.859 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4497, 1658, 892 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.662 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.070, 0.77 |
No. of reflections | 1600 |
No. of parameters | 43 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.53, −0.37 |
Computer programs: EXPOSE in IPDS Software (Stoe & Cie, 1999), CELL in IPDS Software, TWIN in IPDS Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.
Cu1—S1i | 2.2792 (10) | Cu1—S1 | 2.4139 (12) |
Cu1—Cl1 | 2.3529 (12) | S1—C1 | 1.815 (4) |
Cu1—Cl1ii | 2.3793 (12) | S1—C4 | 1.831 (5) |
S1i—Cu1—Cl1 | 120.71 (4) | Cl1—Cu1—S1 | 103.67 (4) |
S1i—Cu1—Cl1ii | 123.01 (5) | Cl1ii—Cu1—S1 | 99.15 (4) |
Cl1—Cu1—Cl1ii | 96.71 (4) | C1—S1—C4 | 95.9 (2) |
S1i—Cu1—S1 | 110.11 (3) | Cu1iii—S1—Cu1 | 127.96 (5) |
Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x, −y+1, −z+2; (iii) −x, y−1/2, −z+3/2. |
1,4-Oxathiane (xt) behaves either as a monodentate ligand in mononuclear transition metal complexes (McEwen & Sim, 1967; Barnes et al., 1977; Olmstead et al., 1982) or as a bridging ligand in polymeric complexes (Barnes & Paton, 1982, 1984; Barnes et al., 1983; Boorman et al., 1998; Salivon et al., 2006). In the latter case it may coordinate to metal atoms via both S and O atoms. The copper(I)–halide complexes [CuX(xt)], where X is Cl, (I), or Br, (II), are known to be not isomorphous (Barnes et al., 1983). However, the structure was determined only for the bromine-containing compound (II) (Barnes & Paton, 1982), while no suitable crystals were obtained for the chorine-containing analogue (Barnes et al., 1983). We have succeeded in obtaining complex (I) in the form of good quality single crystals and we report here its crystal structure.
A major factor governing structure formation in complexes (I) and (II) is the competition between the halide (X = Cl and Br) and S atoms for the coordination to CuI. Both structures contain polynuclear (CuS)n fragments. In (I), the infinite spiral-like (—Cu—S—Cu'—S'—)n chains (Fig. 1) are similar to the Zn–S chains running along [100] in the sphalerite structure; the torsion angles Cu—S—Cu'—S' = [-72.8 (2)°] and S—Cu'—S'—Cu [-67.3 (2)°] in (I) are close to the corresponding angles Zn—S—Zn'—S' and S—Zn'—S'—Zn (both -60°) in sphalerite. The Cl atoms do not form polymeric fragments with CuI on their own. Instead, they form isolated centrosymmetric Cu2Cl2 fragments (Fig. 2a). Hence, at the S:Cl ratio 1:1, the softer base (the S atom) appears to be more competitive in the formation of polymeric structures with a soft acid (CuI atom) than the harder base (the O atom). The Cl atoms are merely bridging the (CuS)n chains into layers in the (100) plane (Fig. 1). Polymeric (CuCl)n fragments appear only when the S:Cl ratio is changed in favour of the Cl atoms. For example polymeric (Cu2Cl2)n strips appear in the structure of the [(CuCl)3(xt)2] complex (III) (Salivon et al., 2006). These strips are linked via the bridging S atoms into layers in the (010) plane (Fig. 2c). The bromine-containing compound (II) is built in a slightly different manner. The (CuS)n fragments are represented by isolated eight-membered Cu4S4 rings, which are linked via Br atoms into infinite chains running along [001] (Fig. 2b).
A significant difference between the two Cu—S bond lengths in complex (I) [Cu1—S1' = 2.279 (1) Å and Cu1—S1 = 2.414 (1) Å] indicates a pyramidal deformation of the nearly tetrahedral coordination of the CuI atom. A similar difference between the two Cu—S distances is observed for one of the three Cu atoms in complex (III); in all other cases this asymmetry is even less noticeable (Olmstead et al., 1982; Barnes & Paton, 1982). The 1,4-oxathiane molecule has a chair conformation in all the known transition metal complexes (Fowler & Griffiths, 1978; Olmstead et al., 1982; Barnes et al., 1983; Buchholz et al., 1996; Boorman et al., 1998).
The O atoms do not realise their coordination abilities in any of the complexes mentioned here. This falls into a pattern of the preferred interaction weak acid (CuI atom)–weak base (S atom). On the other hand, the harder base (O atom) may form a hydrogen bond; in (I), a bond with an O···C2 distance of 3.33 (3) Å links the layers into a three-dimensional structure. However, the O atom of the 1,4-oxathiane molecule can also be involved in an interaction with a transition metal. This can be achieved either by an increase of the acid's hardness, as in the CuII complexes [(CuCl2)3(xt)2] and [CuCl2(xt)2] (Barnes et al., 1983), where oxathiane becomes a bidentate ligand (coordination via the S and O atoms), or by an increase of the metal-to-ligand ratio, as in the AgI complex [(AgNO3)6(xt)] (Barnes & Paton, 1984), where oxathiane behaves as a tetradentate ligand (µ2-S and µ2-O).