Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102000458/jz1489sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102000458/jz1489Isup2.hkl |
CCDC reference: 182972
The electrochemical oxidation of a copper anode in an acetonitrile solution (50 ml) containing p-toluenesulfonic acid monohydrate (76.1 mg, 0.40 mmol), 1,10-phenanthroline monohydrate (70.5 mg, 0.40 mmol) and tetramethylammonium perchlorate (ca 10 mg) for 1 h at 8 V and 10 mA, resulted in a loss of 21.5 mg of copper from the anode and the formation of a green solution, which after concentration by slow evaporation at room temperature gave a crystalline solid.
Aryl and rigid rotating-group methyl H atoms were placed in calculated positions and refined with a riding model, with C—H distances of 0.93 and 0.96 Å, and Uiso values of 1.2Ueq and 1.5Ueq, respectively, of the C atoms to which they are attached. H atoms of the coordinated water molecule were located in a difference map and were refined isotropically with O—H distances restrained to 0.82 Å.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1998); software used to prepare material for publication: SHELXL97.
[CuCl(C7H7O3S)(C12H8N2)(H2O)] | Z = 2 |
Mr = 468.40 | F(000) = 478 |
Triclinic, P1 | Dx = 1.601 Mg m−3 |
a = 7.0887 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.9723 (9) Å | Cell parameters from 3380 reflections |
c = 14.4170 (13) Å | θ = 2.5–27.8° |
α = 83.773 (2)° | µ = 1.40 mm−1 |
β = 78.629 (2)° | T = 293 K |
γ = 77.153 (2)° | Prism, blue |
V = 971.90 (16) Å3 | 0.55 × 0.36 × 0.18 mm |
Bruker SMART CCD area-detector diffractometer | 3249 independent reflections |
Radiation source: fine-focus sealed tube | 2858 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Siemens, 1996) | h = −8→7 |
Tmin = 0.506, Tmax = 0.778 | k = −11→11 |
5013 measured reflections | l = −17→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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.126 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0943P)2] where P = (Fo2 + 2Fc2)/3 |
3249 reflections | (Δ/σ)max < 0.001 |
262 parameters | Δρmax = 1.09 e Å−3 |
0 restraints | Δρmin = −0.80 e Å−3 |
[CuCl(C7H7O3S)(C12H8N2)(H2O)] | γ = 77.153 (2)° |
Mr = 468.40 | V = 971.90 (16) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.0887 (7) Å | Mo Kα radiation |
b = 9.9723 (9) Å | µ = 1.40 mm−1 |
c = 14.4170 (13) Å | T = 293 K |
α = 83.773 (2)° | 0.55 × 0.36 × 0.18 mm |
β = 78.629 (2)° |
Bruker SMART CCD area-detector diffractometer | 3249 independent reflections |
Absorption correction: multi-scan (SADABS; Siemens, 1996) | 2858 reflections with I > 2σ(I) |
Tmin = 0.506, Tmax = 0.778 | Rint = 0.036 |
5013 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.126 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 1.09 e Å−3 |
3249 reflections | Δρmin = −0.80 e Å−3 |
262 parameters |
Experimental. We have measured to theta(max) = 28.02 °. with 89.9% completeness, but the data are virtually 95% complete to 25 °. Data were 95% complete to 2θ = 50°. |
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 | 0.20979 (6) | 0.77450 (4) | 0.84191 (3) | 0.03153 (17) | |
Cl | 0.10985 (17) | 0.57819 (9) | 0.84060 (8) | 0.0571 (3) | |
O1W | 0.1351 (4) | 0.8465 (3) | 0.71753 (18) | 0.0388 (6) | |
H1 | 0.238 (5) | 0.829 (5) | 0.682 (3) | 0.082 (18)* | |
H2 | 0.044 (5) | 0.819 (5) | 0.709 (3) | 0.075 (16)* | |
O2 | 0.5005 (4) | 0.8066 (3) | 0.61529 (17) | 0.0446 (6) | |
O3 | 0.5350 (3) | 0.7226 (2) | 0.77580 (16) | 0.0390 (6) | |
O1 | 0.8077 (4) | 0.7975 (3) | 0.6680 (2) | 0.0516 (7) | |
S1 | 0.63699 (12) | 0.73579 (8) | 0.67733 (6) | 0.0343 (2) | |
C11 | 0.7225 (5) | 0.5667 (4) | 0.6395 (2) | 0.0402 (8) | |
C12 | 0.9144 (6) | 0.5009 (4) | 0.6355 (3) | 0.0554 (10) | |
H12 | 1.0045 | 0.5454 | 0.6515 | 0.066* | |
C13 | 0.9736 (8) | 0.3667 (5) | 0.6071 (3) | 0.0698 (14) | |
H13 | 1.1042 | 0.3218 | 0.6046 | 0.084* | |
C14 | 0.8424 (9) | 0.2990 (5) | 0.5827 (3) | 0.0677 (14) | |
C15 | 0.6507 (8) | 0.3672 (5) | 0.5867 (3) | 0.0702 (13) | |
H15 | 0.5612 | 0.3232 | 0.5696 | 0.084* | |
C16 | 0.5878 (7) | 0.4992 (4) | 0.6155 (3) | 0.0566 (11) | |
H16 | 0.4566 | 0.5433 | 0.6190 | 0.068* | |
C17 | 0.9096 (11) | 0.1523 (5) | 0.5542 (4) | 0.102 (2) | |
H17A | 0.8252 | 0.1341 | 0.5146 | 0.153* | |
H17B | 0.9042 | 0.0901 | 0.6099 | 0.153* | |
H17C | 1.0422 | 0.1393 | 0.5198 | 0.153* | |
N21 | 0.2159 (4) | 0.9688 (3) | 0.86886 (19) | 0.0310 (6) | |
N22 | 0.2595 (4) | 0.7371 (3) | 0.97547 (19) | 0.0310 (6) | |
C21 | 0.1970 (5) | 1.0840 (3) | 0.8123 (3) | 0.0403 (8) | |
H21 | 0.1836 | 1.0791 | 0.7499 | 0.048* | |
C22 | 0.1964 (5) | 1.2117 (3) | 0.8433 (3) | 0.0447 (9) | |
H22 | 0.1840 | 1.2900 | 0.8018 | 0.054* | |
C23 | 0.2143 (5) | 1.2217 (3) | 0.9352 (3) | 0.0445 (9) | |
H23 | 0.2097 | 1.3072 | 0.9567 | 0.053* | |
C24 | 0.2393 (5) | 1.1029 (3) | 0.9965 (3) | 0.0373 (8) | |
C25 | 0.2396 (5) | 0.9785 (3) | 0.9583 (2) | 0.0308 (7) | |
C26 | 0.2646 (4) | 0.8516 (3) | 1.0169 (2) | 0.0309 (7) | |
C27 | 0.2920 (5) | 0.8527 (4) | 1.1103 (2) | 0.0378 (8) | |
C28 | 0.3201 (5) | 0.7218 (4) | 1.1615 (2) | 0.0491 (10) | |
H28 | 0.3407 | 0.7149 | 1.2237 | 0.059* | |
C29 | 0.3169 (6) | 0.6069 (4) | 1.1197 (3) | 0.0496 (9) | |
H29 | 0.3373 | 0.5211 | 1.1529 | 0.060* | |
C210 | 0.2833 (5) | 0.6179 (4) | 1.0276 (3) | 0.0407 (8) | |
H210 | 0.2769 | 0.5386 | 1.0009 | 0.049* | |
C211 | 0.2912 (5) | 0.9792 (4) | 1.1465 (3) | 0.0453 (9) | |
H211 | 0.3076 | 0.9800 | 1.2088 | 0.054* | |
C212 | 0.2672 (5) | 1.0995 (4) | 1.0921 (3) | 0.0465 (9) | |
H212 | 0.2689 | 1.1809 | 1.1175 | 0.056* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0400 (3) | 0.0215 (2) | 0.0344 (3) | −0.00610 (17) | −0.00978 (18) | −0.00269 (16) |
Cl | 0.0880 (8) | 0.0293 (5) | 0.0664 (7) | −0.0232 (5) | −0.0324 (6) | 0.0002 (4) |
O1W | 0.0387 (15) | 0.0390 (14) | 0.0415 (14) | −0.0102 (12) | −0.0122 (12) | −0.0012 (11) |
O2 | 0.0453 (15) | 0.0458 (15) | 0.0419 (14) | −0.0059 (11) | −0.0149 (11) | 0.0067 (11) |
O3 | 0.0424 (14) | 0.0379 (13) | 0.0341 (12) | −0.0002 (10) | −0.0092 (10) | −0.0031 (10) |
O1 | 0.0428 (15) | 0.0539 (17) | 0.0638 (17) | −0.0178 (13) | −0.0141 (13) | −0.0036 (13) |
S1 | 0.0343 (5) | 0.0346 (5) | 0.0348 (5) | −0.0058 (3) | −0.0096 (3) | −0.0019 (3) |
C11 | 0.050 (2) | 0.0381 (19) | 0.0295 (17) | −0.0002 (16) | −0.0082 (15) | −0.0051 (14) |
C12 | 0.056 (2) | 0.055 (2) | 0.049 (2) | 0.0030 (19) | −0.0069 (19) | −0.0103 (19) |
C13 | 0.076 (3) | 0.062 (3) | 0.052 (3) | 0.019 (2) | 0.001 (2) | −0.009 (2) |
C14 | 0.112 (4) | 0.047 (2) | 0.034 (2) | 0.000 (3) | −0.005 (2) | −0.0076 (18) |
C15 | 0.103 (4) | 0.054 (3) | 0.061 (3) | −0.016 (3) | −0.026 (3) | −0.013 (2) |
C16 | 0.071 (3) | 0.045 (2) | 0.061 (3) | −0.009 (2) | −0.029 (2) | −0.0078 (19) |
C17 | 0.181 (7) | 0.050 (3) | 0.056 (3) | 0.005 (3) | 0.000 (4) | −0.013 (2) |
N21 | 0.0337 (14) | 0.0222 (13) | 0.0364 (15) | −0.0041 (11) | −0.0064 (11) | −0.0021 (11) |
N22 | 0.0316 (14) | 0.0244 (13) | 0.0349 (14) | −0.0039 (11) | −0.0035 (11) | −0.0017 (11) |
C21 | 0.042 (2) | 0.0310 (18) | 0.048 (2) | −0.0090 (15) | −0.0082 (16) | 0.0021 (15) |
C22 | 0.046 (2) | 0.0242 (17) | 0.062 (2) | −0.0061 (15) | −0.0098 (18) | 0.0035 (15) |
C23 | 0.0340 (19) | 0.0253 (17) | 0.075 (3) | −0.0082 (14) | −0.0054 (17) | −0.0127 (17) |
C24 | 0.0267 (17) | 0.0345 (18) | 0.052 (2) | −0.0091 (14) | −0.0011 (15) | −0.0144 (15) |
C25 | 0.0288 (17) | 0.0231 (15) | 0.0398 (18) | −0.0045 (12) | −0.0021 (13) | −0.0074 (13) |
C26 | 0.0258 (16) | 0.0320 (16) | 0.0327 (17) | −0.0030 (13) | −0.0034 (13) | −0.0025 (13) |
C27 | 0.0282 (17) | 0.047 (2) | 0.0374 (18) | −0.0059 (14) | −0.0041 (14) | −0.0083 (15) |
C28 | 0.047 (2) | 0.067 (3) | 0.0316 (19) | −0.0100 (19) | −0.0084 (16) | 0.0049 (18) |
C29 | 0.054 (2) | 0.045 (2) | 0.043 (2) | −0.0037 (18) | −0.0094 (17) | 0.0127 (17) |
C210 | 0.045 (2) | 0.0305 (17) | 0.043 (2) | −0.0060 (15) | −0.0051 (16) | 0.0024 (14) |
C211 | 0.040 (2) | 0.066 (3) | 0.0343 (18) | −0.0146 (18) | −0.0050 (15) | −0.0169 (17) |
C212 | 0.037 (2) | 0.052 (2) | 0.055 (2) | −0.0136 (17) | −0.0003 (17) | −0.0282 (19) |
Cu—O1W | 1.984 (3) | N21—C21 | 1.332 (4) |
Cu—N22 | 2.006 (3) | N21—C25 | 1.349 (4) |
Cu—N21 | 2.028 (3) | N22—C210 | 1.331 (4) |
Cu—Cl | 2.2282 (9) | N22—C26 | 1.355 (4) |
Cu—O3 | 2.281 (2) | C21—C22 | 1.393 (5) |
O1W—H1 | 0.80 (2) | C21—H21 | 0.9300 |
O1W—H2 | 0.792 (19) | C22—C23 | 1.371 (5) |
O2—S1 | 1.461 (3) | C22—H22 | 0.9300 |
O3—S1 | 1.467 (2) | C23—C24 | 1.399 (5) |
O1—S1 | 1.453 (3) | C23—H23 | 0.9300 |
S1—C11 | 1.767 (4) | C24—C25 | 1.410 (4) |
C11—C12 | 1.365 (5) | C24—C212 | 1.426 (5) |
C11—C16 | 1.396 (5) | C25—C26 | 1.440 (4) |
C12—C13 | 1.391 (6) | C26—C27 | 1.399 (5) |
C12—H12 | 0.9300 | C27—C211 | 1.415 (5) |
C13—C14 | 1.381 (8) | C27—C28 | 1.421 (5) |
C13—H13 | 0.9300 | C28—C29 | 1.358 (5) |
C14—C15 | 1.371 (7) | C28—H28 | 0.9300 |
C14—C17 | 1.510 (6) | C29—C210 | 1.384 (5) |
C15—C16 | 1.374 (6) | C29—H29 | 0.9300 |
C15—H15 | 0.9300 | C210—H210 | 0.9300 |
C16—H16 | 0.9300 | C211—C212 | 1.356 (6) |
C17—H17A | 0.9600 | C211—H211 | 0.9300 |
C17—H17B | 0.9600 | C212—H212 | 0.9300 |
C17—H17C | 0.9600 | ||
O1W—Cu—N22 | 169.20 (11) | H17B—C17—H17C | 109.5 |
O1W—Cu—N21 | 89.30 (11) | C21—N21—C25 | 117.5 (3) |
N22—Cu—N21 | 81.22 (10) | C21—N21—Cu | 129.5 (2) |
O1W—Cu—Cl | 93.22 (8) | C25—N21—Cu | 113.0 (2) |
N22—Cu—Cl | 94.22 (8) | C210—N22—C26 | 117.3 (3) |
N21—Cu—Cl | 161.91 (8) | C210—N22—Cu | 129.0 (2) |
O1W—Cu—O3 | 91.81 (10) | C26—N22—Cu | 113.7 (2) |
N22—Cu—O3 | 94.03 (9) | N21—C21—C22 | 122.3 (3) |
N21—Cu—O3 | 94.19 (10) | N21—C21—H21 | 118.9 |
Cl—Cu—O3 | 103.62 (7) | C22—C21—H21 | 118.9 |
Cu—O1W—H1 | 102 (4) | C23—C22—C21 | 119.9 (3) |
Cu—O1W—H2 | 111 (4) | C23—C22—H22 | 120.0 |
H1—O1W—H2 | 120 (5) | C21—C22—H22 | 120.0 |
S1—O3—Cu | 131.59 (14) | C22—C23—C24 | 119.8 (3) |
O1—S1—O2 | 112.62 (15) | C22—C23—H23 | 120.1 |
O1—S1—O3 | 112.78 (16) | C24—C23—H23 | 120.1 |
O2—S1—O3 | 111.06 (15) | C23—C24—C25 | 116.1 (3) |
O1—S1—C11 | 107.22 (17) | C23—C24—C212 | 124.9 (3) |
O2—S1—C11 | 106.01 (16) | C25—C24—C212 | 119.0 (3) |
O3—S1—C11 | 106.66 (15) | N21—C25—C24 | 124.4 (3) |
C12—C11—C16 | 120.0 (4) | N21—C25—C26 | 116.2 (3) |
C12—C11—S1 | 121.5 (3) | C24—C25—C26 | 119.5 (3) |
C16—C11—S1 | 118.5 (3) | N22—C26—C27 | 124.5 (3) |
C11—C12—C13 | 119.3 (4) | N22—C26—C25 | 115.8 (3) |
C11—C12—H12 | 120.3 | C27—C26—C25 | 119.7 (3) |
C13—C12—H12 | 120.3 | C26—C27—C211 | 119.4 (3) |
C14—C13—C12 | 121.3 (5) | C26—C27—C28 | 115.4 (3) |
C14—C13—H13 | 119.4 | C211—C27—C28 | 125.2 (3) |
C12—C13—H13 | 119.4 | C29—C28—C27 | 120.1 (3) |
C15—C14—C13 | 118.4 (4) | C29—C28—H28 | 119.9 |
C15—C14—C17 | 121.3 (5) | C27—C28—H28 | 119.9 |
C13—C14—C17 | 120.2 (5) | C28—C29—C210 | 119.8 (3) |
C14—C15—C16 | 121.4 (5) | C28—C29—H29 | 120.1 |
C14—C15—H15 | 119.3 | C210—C29—H29 | 120.1 |
C16—C15—H15 | 119.3 | N22—C210—C29 | 122.9 (3) |
C15—C16—C11 | 119.5 (4) | N22—C210—H210 | 118.6 |
C15—C16—H16 | 120.3 | C29—C210—H210 | 118.6 |
C11—C16—H16 | 120.3 | C212—C211—C27 | 121.4 (3) |
C14—C17—H17A | 109.5 | C212—C211—H211 | 119.3 |
C14—C17—H17B | 109.5 | C27—C211—H211 | 119.3 |
H17A—C17—H17B | 109.5 | C211—C212—C24 | 121.0 (3) |
C14—C17—H17C | 109.5 | C211—C212—H212 | 119.5 |
H17A—C17—H17C | 109.5 | C24—C212—H212 | 119.5 |
O1W—Cu—O3—S1 | −2.1 (2) | O3—Cu—N22—C26 | 96.0 (2) |
N22—Cu—O3—S1 | −173.00 (19) | C25—N21—C21—C22 | −1.5 (5) |
N21—Cu—O3—S1 | −91.5 (2) | Cu—N21—C21—C22 | 177.2 (2) |
Cl—Cu—O3—S1 | 91.66 (18) | N21—C21—C22—C23 | −0.5 (5) |
Cu—O3—S1—O1 | 133.74 (19) | C21—C22—C23—C24 | 2.1 (5) |
Cu—O3—S1—O2 | 6.2 (2) | C22—C23—C24—C25 | −1.5 (5) |
Cu—O3—S1—C11 | −108.8 (2) | C22—C23—C24—C212 | 177.4 (3) |
O1—S1—C11—C12 | 19.6 (4) | C21—N21—C25—C24 | 2.1 (5) |
O2—S1—C11—C12 | 140.1 (3) | Cu—N21—C25—C24 | −176.8 (2) |
O3—S1—C11—C12 | −101.5 (3) | C21—N21—C25—C26 | −178.5 (3) |
O1—S1—C11—C16 | −161.9 (3) | Cu—N21—C25—C26 | 2.6 (4) |
O2—S1—C11—C16 | −41.4 (3) | C23—C24—C25—N21 | −0.6 (5) |
O3—S1—C11—C16 | 77.0 (3) | C212—C24—C25—N21 | −179.6 (3) |
C16—C11—C12—C13 | 0.2 (6) | C23—C24—C25—C26 | 180.0 (3) |
S1—C11—C12—C13 | 178.6 (3) | C212—C24—C25—C26 | 1.0 (5) |
C11—C12—C13—C14 | 0.2 (7) | C210—N22—C26—C27 | −0.3 (5) |
C12—C13—C14—C15 | 0.1 (7) | Cu—N22—C26—C27 | 178.3 (2) |
C12—C13—C14—C17 | −178.7 (4) | C210—N22—C26—C25 | 179.7 (3) |
C13—C14—C15—C16 | −0.9 (7) | Cu—N22—C26—C25 | −1.7 (3) |
C17—C14—C15—C16 | 177.9 (4) | N21—C25—C26—N22 | −0.6 (4) |
C14—C15—C16—C11 | 1.3 (7) | C24—C25—C26—N22 | 178.8 (3) |
C12—C11—C16—C15 | −0.9 (6) | N21—C25—C26—C27 | 179.4 (3) |
S1—C11—C16—C15 | −179.4 (3) | C24—C25—C26—C27 | −1.2 (5) |
O1W—Cu—N21—C21 | −6.7 (3) | N22—C26—C27—C211 | −178.9 (3) |
N22—Cu—N21—C21 | 178.5 (3) | C25—C26—C27—C211 | 1.1 (5) |
Cl—Cu—N21—C21 | −104.9 (3) | N22—C26—C27—C28 | 1.5 (5) |
O3—Cu—N21—C21 | 85.1 (3) | C25—C26—C27—C28 | −178.5 (3) |
O1W—Cu—N21—C25 | 172.1 (2) | C26—C27—C28—C29 | −0.8 (5) |
N22—Cu—N21—C25 | −2.7 (2) | C211—C27—C28—C29 | 179.6 (3) |
Cl—Cu—N21—C25 | 73.8 (4) | C27—C28—C29—C210 | −1.0 (6) |
O3—Cu—N21—C25 | −96.1 (2) | C26—N22—C210—C29 | −1.6 (5) |
O1W—Cu—N22—C210 | 151.9 (5) | Cu—N22—C210—C29 | −180.0 (3) |
N21—Cu—N22—C210 | −179.2 (3) | C28—C29—C210—N22 | 2.3 (6) |
Cl—Cu—N22—C210 | 18.5 (3) | C26—C27—C211—C212 | −0.9 (5) |
O3—Cu—N22—C210 | −85.5 (3) | C28—C27—C211—C212 | 178.7 (3) |
O1W—Cu—N22—C26 | −26.6 (7) | C27—C211—C212—C24 | 0.8 (5) |
N21—Cu—N22—C26 | 2.4 (2) | C23—C24—C212—C211 | −179.7 (3) |
Cl—Cu—N22—C26 | −160.0 (2) | C25—C24—C212—C211 | −0.8 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1···O2 | 0.80 (2) | 1.90 (2) | 2.684 (4) | 168 (5) |
O1W—H2···O1i | 0.79 (2) | 1.94 (2) | 2.714 (4) | 164 (5) |
C21—H21···O1W | 0.93 | 2.52 | 3.011 (4) | 113 |
C210—H210···Cl | 0.93 | 2.75 | 3.269 (4) | 116 |
C29—H29···O3ii | 0.93 | 2.58 | 3.491 (4) | 168 |
C28—H28···Cg1ii | 0.93 | 2.76 | 3.481 (4) | 136 |
C29—H29···Cg1ii | 0.93 | 3.40 | 3.798 (4) | 109 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [CuCl(C7H7O3S)(C12H8N2)(H2O)] |
Mr | 468.40 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.0887 (7), 9.9723 (9), 14.4170 (13) |
α, β, γ (°) | 83.773 (2), 78.629 (2), 77.153 (2) |
V (Å3) | 971.90 (16) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.40 |
Crystal size (mm) | 0.55 × 0.36 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Siemens, 1996) |
Tmin, Tmax | 0.506, 0.778 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5013, 3249, 2858 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.126, 1.03 |
No. of reflections | 3249 |
No. of parameters | 262 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.09, −0.80 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1998), SHELXL97.
Cu—O1W | 1.984 (3) | Cu—O3 | 2.281 (2) |
Cu—N22 | 2.006 (3) | O2—S1 | 1.461 (3) |
Cu—N21 | 2.028 (3) | O3—S1 | 1.467 (2) |
Cu—Cl | 2.2282 (9) | O1—S1 | 1.453 (3) |
O1W—Cu—N22 | 169.20 (11) | N21—Cu—O3 | 94.19 (10) |
O1W—Cu—N21 | 89.30 (11) | Cl—Cu—O3 | 103.62 (7) |
N22—Cu—N21 | 81.22 (10) | O1—S1—O2 | 112.62 (15) |
O1W—Cu—Cl | 93.22 (8) | O1—S1—O3 | 112.78 (16) |
N22—Cu—Cl | 94.22 (8) | O2—S1—O3 | 111.06 (15) |
N21—Cu—Cl | 161.91 (8) | O1—S1—C11 | 107.22 (17) |
O1W—Cu—O3 | 91.81 (10) | O2—S1—C11 | 106.01 (16) |
N22—Cu—O3 | 94.03 (9) | O3—S1—C11 | 106.66 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1···O2 | 0.80 (2) | 1.90 (2) | 2.684 (4) | 168 (5) |
O1W—H2···O1i | 0.79 (2) | 1.94 (2) | 2.714 (4) | 164 (5) |
C21—H21···O1W | 0.93 | 2.52 | 3.011 (4) | 113.0 |
C210—H210···Cl | 0.93 | 2.75 | 3.269 (4) | 116.1 |
C29—H29···O3ii | 0.93 | 2.58 | 3.491 (4) | 168.2 |
C28—H28···Cg1ii | 0.93 | 2.76 | 3.481 (4) | 135.5 |
C29—H29···Cg1ii | 0.93 | 3.40 | 3.798 (4) | 108.7 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+2. |
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In recent years, an important research topic of our group has been the electrochemical synthesis of neutral metal sulfonamide complexes. Neutral complexes can be easily obtained when a sacrificial anode is oxidized in a cell containing an appropriate proligand with a weak acidic character (García-Vázquez et al. 1999), e.g. sulfonamides (Cabaleiro et al., 2000). The title compound, (I), was obtained using this general method (see Experimental for details).
The electrochemical efficiency, defined as the molar amount of metal dissolved per Faraday, was close to 1.0. This fact, together with the formation of H2 gas at the cathode, is compatible with a reaction mechanism involving anodic oxidation to copper(I) and deprotonation of the ligand at the cathode.
Anode: Cu → Cu+ + e-.
Cathode: HL + e- → L- + 1/2H2,
where HL and L- are p-toluenesulfonic acid and its anion, respectively.
The Cu+ compound initially formed in the electrochemical process is further oxidized in solution to give the Cu2+ product. The presence of the chloride ligand is probably attributable to the perchlorate used as the background electrolyte, through a process which is far from clear. Such behaviour has, however, been observed in the synthesis of other compounds by electrochemical procedures (Pérez-Lourido et al., 1998).
The isolated compound consists of discrete [CuCl(CH3C6H4SO3)(C12H8N2)(H2O)] molecules, where the Cu atom is coordinated by one water molecule, one chloride ion, one p-toluenesulfonate ion and one N,N'-bidentate 1,10-phenanthroline ligand. The Cu atom is in a square-pyramidal environment. Bond distances in the basal positions are slightly shorter than the sum of covalent radii [Cu—O1W 1.984 (3) Å, Cu—N21 2.028 (3) Å, Cu—N22 2.006 (3) Å and Cu—Cl 2.2282 (9) Å], but the length of the bond in the apical position is longer [Cu—O3 2.281 (2) Å]. This is, in part, because the fifth coordination position in square-pyramidal arrangements is usually longer (Murase et al., 1991, Bailey et al., 1980) and is also probably associated with the low coordination capability of the benzenesulfonate and toluenesulfonate anions, for which only eight entries are found in the Cambridge Structural Database (Version 5.22, October 2001; Allen & Kennard, 1993), coordinating to CuII atoms (deviations: mean 2.443 Å, maximum 2.594 Å, minimum 2.153 Å). For comparison, a similar search for the trifluoromethanesulfonate ligand gave 44 hits (deviations: mean 2.359 Å, maximum 2.800 Å, minimum 1.948 Å).
The basal plane O1W/N21/N22/Cl is slightly distorted (r.m.s. deviation 0.105 Å), with a maximum deviation of 0.117 (1) Å for N21. The Cu atom lies 0.219 (1) Å out of the best plane formed by the four donor atoms, which subtends a small dihedral angle with the 1,10-phenanthroline best plane (r.m.s. deviation 0.020 Å) of 12.59 (8)°.
Some distortion is found around the tetrahedral S atom, with bond angles in the range 106.01 (16)–112.78 (16)°. In part, this distortion is probably associated with the hydrogen bond between the O2 atom of this SO3 group and the coordinated water molecule (see Table 2); furthermore, the O1 atom interacts with another water molecule of a neighbouring complex. This hydrogen bond plays an important role in the maintenance of the supramolecular structure, as do some π–π-stacking interactions and non-classical (Taylor & Kennard, 1982) hydrogen bonds between C29 and O3. In addition, the theoretical sixth coordination position of the Cu-atom environment is occupied by a π-cloud of the central benzene ring of 1,10-phenanthroline, with the centroid at 3.9648 (5) Å from the metal atom. Neverthless, this distance is longer than the sum of the van der Waals radii, 3.10 Å, considering the phenyl group in a perpendicular fashion (Huheey et al., 1993), so that this disposition could be due to geometrical constraints (see below).
π–π stacking (Janiak, 2001) is observed between the pyridine moieties of different 1,10-phenanthroline groups, so alternating layers of 1,10-phenanthroline are found. Thus, the N21/C21–C25 ring is above the N22/C26–C211 ring, with inter-centroid distances of 3.590 (2) and 4.343 (2) Å, and symmetry operators (2 - x, 1 - y, 1 - z) and (1 - x, 1 - y, 1 - z), respectively.