Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110041090/ga3158sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110041090/ga3158Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110041090/ga3158IIsup3.hkl |
CCDC references: 804114; 804115
For the synthesis of complex (I), an aqueous solution (20 ml) of copper(II) chloride dihydrate (0.429 mmol, 75 mg) and 2,2':6'2''-terpyridine (0.429 mmol, 100 mg) was heated at 353 K for 1 h. After hot filtration, the green solution was cooled to room temperature and sodium sulfite (1.717 mmol, 216 mg) was added. The resulting solution was left in the fridge for two months and emerald-green block-like crystals of (I) were obtained (yield 38 mg; 20%).
Pale-green crystals of (II) were obtained after thermogravimetric analysis of compound (I); see Comment. A sample of (I) (ca 20 mg) was heated to 433 K in a closed aluminium oxide crucible at a rate of 2 K min-1 (gas flow 150 ml min-1) at atmospheric pressure.
A small quantity of blue-green crystals were obtained as a by-product during the synthesis of (I). They were identified by X-ray crystallographic analysis to be the mononuclear complex aquachlorido(2,2':6',6''-terpyridyl)copper(II) chloride monohydrate (Schmitt et al., 2010), i.e. compound (III) mentioned above.
The analytical and spectroscopic data for (I) and (II) are available in the archived CIF.
In a difference Fourier map for compound (II) a peak of 2.0 e Å-3 was observed near an inversion centre. It was refined as a partially occupied solvent water molecule (O1W) with an occupancy of 0.5. For compound (I), the water H atoms were located in a difference electron-density map and refined isotropically, with O—H distance restraints of 0.84 (2) Å. For compound (II), the water H atoms could also be located in a difference electron-density map and they were refined with O—H distance restraints of 0.84 (2) Å and Uiso(H) = 1.5Ueq(O). For both (I) and (II), C-bound H atoms were included in calculated positions and treated as riding, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C). For compound (I), a certain number of reflections were excluded from the structure factor file. This was due to the fact that the crystal exposure time was too long and this caused overloads on the image plate. The individual intensities of these reflections could not be measured acurately and they were omitted from the final structure factor file. A comparison of similar bond lengths in the two crystal structures shows that this has little effect on the final structure analysis.
For both compounds, data collection: X-AREA (Stoe & Cie, 2006); cell refinement: X-AREA (Stoe & Cie, 2006); data reduction: X-RED32 (Stoe & Cie, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).
[Cu(C15H11N3)Cl(H2O)][Cu(C15H11N3)(S2O6)Cl]·2H2O | Z = 2 |
Mr = 878.68 | F(000) = 892 |
Triclinic, P1 | Dx = 1.763 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0705 (10) Å | Cell parameters from 33786 reflections |
b = 8.589 (1) Å | θ = 1.6–29.7° |
c = 25.177 (3) Å | µ = 1.64 mm−1 |
α = 83.096 (10)° | T = 173 K |
β = 82.870 (11)° | Plate, emerald-green |
γ = 73.675 (11)° | 0.50 × 0.37 × 0.20 mm |
V = 1655.2 (3) Å3 |
Stoe IPDS II diffractometer | 8888 independent reflections |
Radiation source: fine-focus sealed tube | 8053 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
ϕ and ω scans | θmax = 29.3°, θmin = 1.6° |
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2009) | h = −11→10 |
Tmin = 0.254, Tmax = 1.00 | k = −11→11 |
25099 measured reflections | l = −34→34 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.116 | w = 1/[σ2(Fo2) + (0.0646P)2 + 0.8251P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
8888 reflections | Δρmax = 0.95 e Å−3 |
485 parameters | Δρmin = −1.47 e Å−3 |
6 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0042 (11) |
[Cu(C15H11N3)Cl(H2O)][Cu(C15H11N3)(S2O6)Cl]·2H2O | γ = 73.675 (11)° |
Mr = 878.68 | V = 1655.2 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.0705 (10) Å | Mo Kα radiation |
b = 8.589 (1) Å | µ = 1.64 mm−1 |
c = 25.177 (3) Å | T = 173 K |
α = 83.096 (10)° | 0.50 × 0.37 × 0.20 mm |
β = 82.870 (11)° |
Stoe IPDS II diffractometer | 8888 independent reflections |
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2009) | 8053 reflections with I > 2σ(I) |
Tmin = 0.254, Tmax = 1.00 | Rint = 0.073 |
25099 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 6 restraints |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.95 e Å−3 |
8888 reflections | Δρmin = −1.47 e Å−3 |
485 parameters |
Experimental. All reagents were purchased from commercial sources and used as received. IR spectra were recorded as KBr pellets on a Perkin–Elmer 1720X FT–IR spectrometer. The TG curves were recorded using a Mettler 4000 thermogravimetric module. IR (ν, cm-1): 3430 (m), 3130 (m), 3028 (m), 3012 (m), 1638 (w), 1598 (m), 1575 (m), 1563 (m), 1498 (w), 1474 (m), 1448 (s), 1402 (m), 1326 (m), 1303 (m), 1292 (w), 1253 (m), 1192 (w), 1165 (m), 1141 (w), 1095 (w), 1049 (w), 1035 (m), 971 (w), 897 (w), 828 (w), 792 (w), 773 (s), 747 (w), 730 (w), 670 (w), 649 (m), 631 (w), 514 (w), 499 (w). |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | 0.92648 (3) | 1.03098 (3) | 0.07310 (1) | 0.0186 (1) | |
Cl1 | 0.77228 (6) | 1.18102 (6) | 0.00877 (2) | 0.0259 (1) | |
S1 | 0.74212 (6) | 1.06445 (6) | 0.20771 (2) | 0.0203 (1) | |
S2 | 0.55085 (6) | 1.25443 (6) | 0.24565 (2) | 0.0198 (1) | |
O1 | 0.7458 (2) | 1.1294 (2) | 0.15131 (6) | 0.0318 (4) | |
O2 | 0.6775 (2) | 0.9207 (2) | 0.21878 (8) | 0.0335 (5) | |
O3 | 0.89971 (19) | 1.05022 (19) | 0.23207 (7) | 0.0287 (4) | |
O4 | 0.3932 (2) | 1.2666 (2) | 0.22174 (7) | 0.0378 (5) | |
O5 | 0.6178 (2) | 1.39478 (18) | 0.23308 (7) | 0.0309 (4) | |
O6 | 0.5436 (2) | 1.19897 (18) | 0.30252 (6) | 0.0270 (4) | |
N1 | 0.8251 (2) | 0.8362 (2) | 0.08322 (7) | 0.0202 (4) | |
N2 | 1.0847 (2) | 0.8855 (2) | 0.12054 (6) | 0.0185 (4) | |
N3 | 1.0936 (2) | 1.1670 (2) | 0.07649 (7) | 0.0198 (4) | |
C1 | 0.6874 (3) | 0.8218 (3) | 0.06187 (8) | 0.0248 (5) | |
C2 | 0.6238 (3) | 0.6863 (3) | 0.07431 (9) | 0.0294 (6) | |
C3 | 0.7037 (3) | 0.5625 (3) | 0.11062 (9) | 0.0297 (6) | |
C4 | 0.8468 (3) | 0.5767 (3) | 0.13336 (9) | 0.0262 (6) | |
C5 | 0.9051 (2) | 0.7141 (2) | 0.11851 (8) | 0.0207 (5) | |
C6 | 1.0574 (2) | 0.7422 (2) | 0.13905 (8) | 0.0202 (5) | |
C7 | 1.1672 (3) | 0.6353 (3) | 0.17359 (9) | 0.0258 (5) | |
C8 | 1.3035 (3) | 0.6844 (3) | 0.18884 (9) | 0.0282 (6) | |
C9 | 1.3289 (3) | 0.8354 (3) | 0.16963 (8) | 0.0257 (5) | |
C10 | 1.2155 (2) | 0.9332 (2) | 0.13432 (8) | 0.0202 (5) | |
C11 | 1.2244 (2) | 1.0939 (2) | 0.10766 (8) | 0.0202 (5) | |
C12 | 1.3561 (3) | 1.1635 (3) | 0.11229 (9) | 0.0266 (6) | |
C13 | 1.3520 (3) | 1.3150 (3) | 0.08534 (10) | 0.0306 (6) | |
C14 | 1.2170 (3) | 1.3911 (3) | 0.05444 (9) | 0.0297 (6) | |
C15 | 1.0907 (3) | 1.3131 (3) | 0.05071 (9) | 0.0252 (5) | |
Cu2 | 0.56952 (3) | 0.45330 (3) | 0.42605 (1) | 0.0178 (1) | |
Cl2 | 0.69844 (7) | 0.28510 (6) | 0.49239 (2) | 0.0275 (1) | |
O1W | 0.7420 (2) | 0.3435 (2) | 0.35353 (6) | 0.0269 (4) | |
N4 | 0.3838 (2) | 0.3445 (2) | 0.41731 (7) | 0.0193 (4) | |
N5 | 0.4290 (2) | 0.6189 (2) | 0.37818 (6) | 0.0178 (4) | |
N6 | 0.6930 (2) | 0.6301 (2) | 0.42210 (7) | 0.0198 (4) | |
C16 | 0.3703 (3) | 0.1981 (2) | 0.43978 (9) | 0.0251 (5) | |
C17 | 0.2415 (3) | 0.1320 (3) | 0.42913 (10) | 0.0308 (6) | |
C18 | 0.1232 (3) | 0.2192 (3) | 0.39412 (11) | 0.0330 (7) | |
C19 | 0.1356 (3) | 0.3703 (3) | 0.37046 (9) | 0.0270 (6) | |
C20 | 0.2672 (2) | 0.4292 (2) | 0.38300 (8) | 0.0192 (5) | |
C21 | 0.2933 (2) | 0.5885 (2) | 0.36047 (8) | 0.0190 (5) | |
C22 | 0.1912 (3) | 0.7027 (3) | 0.32537 (8) | 0.0241 (5) | |
C23 | 0.2368 (3) | 0.8470 (3) | 0.30947 (9) | 0.0268 (6) | |
C24 | 0.3794 (3) | 0.8757 (2) | 0.32802 (8) | 0.0245 (5) | |
C25 | 0.4735 (2) | 0.7562 (2) | 0.36341 (8) | 0.0197 (5) | |
C26 | 0.6259 (3) | 0.7641 (2) | 0.38918 (8) | 0.0210 (5) | |
C27 | 0.6953 (3) | 0.8955 (3) | 0.38208 (10) | 0.0301 (6) | |
C28 | 0.8350 (3) | 0.8912 (3) | 0.40989 (11) | 0.0348 (7) | |
C29 | 0.9041 (3) | 0.7533 (3) | 0.44297 (10) | 0.0310 (6) | |
C30 | 0.8297 (3) | 0.6257 (3) | 0.44801 (9) | 0.0247 (5) | |
O2W | 0.0346 (2) | 0.3188 (2) | 0.23615 (9) | 0.0413 (6) | |
O3W | 0.8449 (2) | 0.6037 (2) | 0.28363 (7) | 0.0347 (5) | |
H1A | 0.63100 | 0.90730 | 0.03730 | 0.0300* | |
H2A | 0.52650 | 0.67880 | 0.05810 | 0.0350* | |
H3A | 0.66160 | 0.46910 | 0.11990 | 0.0360* | |
H4A | 0.90340 | 0.49360 | 0.15860 | 0.0310* | |
H7A | 1.14980 | 0.53190 | 0.18640 | 0.0310* | |
H8A | 1.38000 | 0.61380 | 0.21260 | 0.0340* | |
H9A | 1.42060 | 0.87030 | 0.18030 | 0.0310* | |
H12A | 1.44800 | 1.10860 | 0.13360 | 0.0320* | |
H13A | 1.44080 | 1.36560 | 0.08810 | 0.0370* | |
H14A | 1.21080 | 1.49550 | 0.03600 | 0.0360* | |
H15A | 0.99880 | 1.36530 | 0.02910 | 0.0300* | |
H1WA | 0.682 (4) | 0.304 (4) | 0.3370 (12) | 0.044 (9)* | |
H1WB | 0.766 (5) | 0.413 (4) | 0.3268 (13) | 0.079 (14)* | |
H16A | 0.45220 | 0.13780 | 0.46380 | 0.0300* | |
H17A | 0.23470 | 0.02830 | 0.44570 | 0.0370* | |
H18A | 0.03370 | 0.17600 | 0.38620 | 0.0400* | |
H19A | 0.05530 | 0.43200 | 0.34620 | 0.0320* | |
H22A | 0.09370 | 0.68260 | 0.31270 | 0.0290* | |
H23A | 0.16940 | 0.92710 | 0.28560 | 0.0320* | |
H24A | 0.41170 | 0.97370 | 0.31690 | 0.0290* | |
H27A | 0.64820 | 0.98790 | 0.35840 | 0.0360* | |
H28A | 0.88250 | 0.98170 | 0.40620 | 0.0420* | |
H29A | 1.00100 | 0.74680 | 0.46190 | 0.0370* | |
H30A | 0.87710 | 0.53100 | 0.47070 | 0.0300* | |
H2WA | −0.023 (3) | 0.245 (3) | 0.2448 (12) | 0.035 (8)* | |
H2WB | 0.144 (2) | 0.295 (5) | 0.2357 (15) | 0.061 (11)* | |
H3WA | 0.903 (4) | 0.530 (3) | 0.2650 (12) | 0.054 (10)* | |
H3WB | 0.791 (4) | 0.681 (3) | 0.2644 (12) | 0.048 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0194 (1) | 0.0195 (1) | 0.0178 (1) | −0.0058 (1) | −0.0067 (1) | 0.0005 (1) |
Cl1 | 0.0275 (2) | 0.0291 (2) | 0.0215 (2) | −0.0075 (2) | −0.0104 (2) | 0.0043 (2) |
S1 | 0.0185 (2) | 0.0207 (2) | 0.0227 (2) | −0.0046 (2) | −0.0032 (2) | −0.0061 (2) |
S2 | 0.0190 (2) | 0.0209 (2) | 0.0192 (2) | −0.0036 (2) | −0.0037 (2) | −0.0031 (2) |
O1 | 0.0266 (7) | 0.0424 (9) | 0.0222 (7) | −0.0019 (7) | −0.0001 (6) | −0.0065 (6) |
O2 | 0.0341 (8) | 0.0248 (7) | 0.0468 (10) | −0.0136 (6) | −0.0021 (7) | −0.0124 (7) |
O3 | 0.0221 (7) | 0.0257 (7) | 0.0389 (9) | −0.0028 (6) | −0.0117 (6) | −0.0056 (6) |
O4 | 0.0209 (7) | 0.0544 (11) | 0.0386 (9) | −0.0028 (7) | −0.0089 (6) | −0.0178 (8) |
O5 | 0.0374 (8) | 0.0181 (6) | 0.0355 (9) | −0.0068 (6) | −0.0018 (7) | 0.0014 (6) |
O6 | 0.0363 (8) | 0.0254 (7) | 0.0207 (7) | −0.0113 (6) | 0.0004 (6) | −0.0033 (5) |
N1 | 0.0222 (7) | 0.0211 (7) | 0.0185 (7) | −0.0071 (6) | −0.0029 (6) | −0.0020 (6) |
N2 | 0.0182 (7) | 0.0202 (7) | 0.0165 (7) | −0.0023 (6) | −0.0038 (5) | −0.0040 (6) |
N3 | 0.0199 (7) | 0.0209 (7) | 0.0196 (7) | −0.0059 (6) | −0.0036 (6) | −0.0034 (6) |
C1 | 0.0252 (9) | 0.0298 (10) | 0.0220 (9) | −0.0097 (8) | −0.0038 (7) | −0.0055 (7) |
C2 | 0.0279 (9) | 0.0386 (11) | 0.0271 (10) | −0.0164 (9) | −0.0016 (8) | −0.0072 (9) |
C3 | 0.0346 (10) | 0.0298 (10) | 0.0295 (11) | −0.0171 (9) | 0.0018 (8) | −0.0060 (8) |
C4 | 0.0312 (10) | 0.0232 (9) | 0.0251 (10) | −0.0093 (8) | −0.0019 (8) | −0.0021 (7) |
C5 | 0.0231 (8) | 0.0201 (8) | 0.0186 (8) | −0.0050 (7) | −0.0011 (6) | −0.0041 (7) |
C6 | 0.0211 (8) | 0.0193 (8) | 0.0185 (8) | −0.0026 (7) | −0.0020 (6) | −0.0024 (6) |
C7 | 0.0282 (9) | 0.0213 (8) | 0.0242 (9) | −0.0011 (7) | −0.0046 (7) | 0.0007 (7) |
C8 | 0.0272 (9) | 0.0277 (10) | 0.0258 (10) | 0.0003 (8) | −0.0083 (8) | 0.0002 (8) |
C9 | 0.0219 (8) | 0.0295 (10) | 0.0245 (10) | −0.0023 (8) | −0.0083 (7) | −0.0031 (8) |
C10 | 0.0191 (8) | 0.0226 (8) | 0.0184 (8) | −0.0027 (7) | −0.0038 (6) | −0.0049 (7) |
C11 | 0.0202 (8) | 0.0234 (8) | 0.0176 (8) | −0.0044 (7) | −0.0035 (6) | −0.0066 (7) |
C12 | 0.0246 (9) | 0.0300 (10) | 0.0292 (10) | −0.0093 (8) | −0.0071 (8) | −0.0089 (8) |
C13 | 0.0296 (10) | 0.0325 (11) | 0.0368 (12) | −0.0166 (9) | −0.0018 (8) | −0.0122 (9) |
C14 | 0.0368 (11) | 0.0243 (9) | 0.0305 (11) | −0.0127 (8) | −0.0004 (9) | −0.0050 (8) |
C15 | 0.0276 (9) | 0.0236 (9) | 0.0249 (10) | −0.0074 (7) | −0.0035 (7) | −0.0014 (7) |
Cu2 | 0.0202 (1) | 0.0178 (1) | 0.0175 (1) | −0.0075 (1) | −0.0067 (1) | 0.0012 (1) |
Cl2 | 0.0306 (2) | 0.0293 (2) | 0.0234 (2) | −0.0095 (2) | −0.0117 (2) | 0.0071 (2) |
O1W | 0.0262 (7) | 0.0347 (8) | 0.0229 (7) | −0.0122 (6) | −0.0028 (6) | −0.0053 (6) |
N4 | 0.0217 (7) | 0.0186 (7) | 0.0188 (7) | −0.0075 (6) | −0.0025 (6) | −0.0014 (6) |
N5 | 0.0189 (7) | 0.0183 (7) | 0.0175 (7) | −0.0060 (6) | −0.0049 (5) | −0.0012 (5) |
N6 | 0.0220 (7) | 0.0201 (7) | 0.0202 (7) | −0.0088 (6) | −0.0050 (6) | −0.0024 (6) |
C16 | 0.0296 (9) | 0.0200 (8) | 0.0269 (10) | −0.0094 (7) | −0.0031 (8) | 0.0001 (7) |
C17 | 0.0340 (11) | 0.0208 (9) | 0.0402 (12) | −0.0132 (8) | −0.0016 (9) | −0.0004 (8) |
C18 | 0.0303 (10) | 0.0260 (10) | 0.0494 (14) | −0.0162 (8) | −0.0075 (9) | −0.0054 (9) |
C19 | 0.0241 (9) | 0.0241 (9) | 0.0365 (11) | −0.0097 (7) | −0.0086 (8) | −0.0033 (8) |
C20 | 0.0196 (8) | 0.0189 (8) | 0.0214 (9) | −0.0073 (6) | −0.0022 (6) | −0.0050 (6) |
C21 | 0.0200 (8) | 0.0190 (8) | 0.0193 (8) | −0.0056 (7) | −0.0049 (6) | −0.0032 (6) |
C22 | 0.0235 (9) | 0.0252 (9) | 0.0251 (10) | −0.0070 (7) | −0.0095 (7) | −0.0001 (7) |
C23 | 0.0308 (10) | 0.0237 (9) | 0.0249 (10) | −0.0048 (8) | −0.0103 (8) | 0.0034 (7) |
C24 | 0.0302 (9) | 0.0196 (8) | 0.0233 (9) | −0.0067 (7) | −0.0061 (7) | 0.0035 (7) |
C25 | 0.0231 (8) | 0.0182 (8) | 0.0195 (8) | −0.0079 (7) | −0.0039 (7) | −0.0009 (6) |
C26 | 0.0222 (8) | 0.0194 (8) | 0.0231 (9) | −0.0082 (7) | −0.0024 (7) | −0.0023 (7) |
C27 | 0.0318 (10) | 0.0232 (9) | 0.0391 (12) | −0.0140 (8) | −0.0057 (9) | 0.0000 (8) |
C28 | 0.0333 (11) | 0.0309 (11) | 0.0479 (14) | −0.0193 (9) | −0.0051 (10) | −0.0065 (10) |
C29 | 0.0256 (9) | 0.0367 (11) | 0.0368 (12) | −0.0149 (9) | −0.0075 (8) | −0.0072 (9) |
C30 | 0.0239 (9) | 0.0279 (9) | 0.0254 (10) | −0.0092 (8) | −0.0064 (7) | −0.0051 (8) |
O2W | 0.0239 (7) | 0.0272 (8) | 0.0736 (14) | −0.0103 (6) | −0.0045 (8) | 0.0003 (8) |
O3W | 0.0388 (9) | 0.0384 (9) | 0.0293 (9) | −0.0127 (8) | −0.0049 (7) | −0.0051 (7) |
Cu1—Cl1 | 2.2203 (6) | C9—C10 | 1.387 (3) |
Cu1—O1 | 2.3901 (16) | C10—C11 | 1.477 (2) |
Cu1—N1 | 2.0368 (17) | C11—C12 | 1.380 (3) |
Cu1—N2 | 1.9342 (16) | C12—C13 | 1.387 (3) |
Cu1—N3 | 2.0322 (17) | C13—C14 | 1.381 (4) |
Cu2—Cl2 | 2.2284 (6) | C14—C15 | 1.385 (4) |
Cu2—O1W | 2.2816 (16) | C1—H1A | 0.9500 |
Cu2—N4 | 2.0216 (17) | C2—H2A | 0.9500 |
Cu2—N5 | 1.9447 (16) | C3—H3A | 0.9500 |
Cu2—N6 | 2.0245 (17) | C4—H4A | 0.9500 |
S1—O1 | 1.4618 (16) | C7—H7A | 0.9500 |
S1—O2 | 1.4551 (18) | C8—H8A | 0.9500 |
S1—S2 | 2.1332 (7) | C9—H9A | 0.9500 |
S1—O3 | 1.4481 (17) | C12—H12A | 0.9500 |
S2—O5 | 1.4413 (17) | C13—H13A | 0.9500 |
S2—O6 | 1.4532 (16) | C14—H14A | 0.9500 |
S2—O4 | 1.4464 (18) | C15—H15A | 0.9500 |
O1W—H1WB | 0.89 (3) | C16—C17 | 1.383 (3) |
O1W—H1WA | 0.84 (3) | C17—C18 | 1.378 (4) |
O2W—H2WA | 0.88 (3) | C18—C19 | 1.386 (4) |
O2W—H2WB | 0.85 (2) | C19—C20 | 1.381 (3) |
O3W—H3WA | 0.83 (3) | C20—C21 | 1.478 (2) |
O3W—H3WB | 0.82 (3) | C21—C22 | 1.393 (3) |
N1—C5 | 1.358 (2) | C22—C23 | 1.390 (3) |
N1—C1 | 1.335 (3) | C23—C24 | 1.387 (3) |
N2—C6 | 1.330 (2) | C24—C25 | 1.391 (3) |
N2—C10 | 1.331 (2) | C25—C26 | 1.481 (3) |
N3—C15 | 1.337 (3) | C26—C27 | 1.379 (3) |
N3—C11 | 1.356 (2) | C27—C28 | 1.389 (4) |
N4—C16 | 1.343 (3) | C28—C29 | 1.384 (4) |
N4—C20 | 1.352 (2) | C29—C30 | 1.377 (4) |
N5—C21 | 1.333 (2) | C16—H16A | 0.9500 |
N5—C25 | 1.326 (2) | C17—H17A | 0.9500 |
N6—C26 | 1.355 (3) | C18—H18A | 0.9500 |
N6—C30 | 1.339 (3) | C19—H19A | 0.9500 |
C1—C2 | 1.387 (4) | C22—H22A | 0.9500 |
C2—C3 | 1.382 (3) | C23—H23A | 0.9500 |
C3—C4 | 1.392 (4) | C24—H24A | 0.9500 |
C4—C5 | 1.384 (3) | C27—H27A | 0.9500 |
C5—C6 | 1.480 (2) | C28—H28A | 0.9500 |
C6—C7 | 1.388 (3) | C29—H29A | 0.9500 |
C7—C8 | 1.393 (4) | C30—H30A | 0.9500 |
C8—C9 | 1.390 (3) | ||
Cu1···Cl1i | 3.2626 (7) | Cu2···Cl2ii | 3.3492 (7) |
Cl1—Cu1—O1 | 100.64 (4) | C10—C11—C12 | 123.70 (18) |
Cl1—Cu1—N1 | 99.82 (5) | N3—C11—C10 | 114.19 (15) |
Cl1—Cu1—N2 | 171.48 (5) | C11—C12—C13 | 118.9 (2) |
Cl1—Cu1—N3 | 99.31 (5) | C12—C13—C14 | 119.0 (2) |
O1—Cu1—N1 | 88.17 (6) | C13—C14—C15 | 119.1 (2) |
O1—Cu1—N2 | 87.88 (6) | N3—C15—C14 | 122.3 (2) |
O1—Cu1—N3 | 94.37 (6) | C2—C1—H1A | 119.00 |
N1—Cu1—N2 | 80.10 (7) | N1—C1—H1A | 119.00 |
N1—Cu1—N3 | 159.89 (7) | C1—C2—H2A | 120.00 |
N2—Cu1—N3 | 80.06 (7) | C3—C2—H2A | 120.00 |
Cl2—Cu2—O1W | 100.19 (4) | C4—C3—H3A | 121.00 |
Cl2—Cu2—N4 | 99.33 (5) | C2—C3—H3A | 120.00 |
Cl2—Cu2—N5 | 169.95 (5) | C5—C4—H4A | 121.00 |
Cl2—Cu2—N6 | 99.80 (5) | C3—C4—H4A | 121.00 |
O1W—Cu2—N4 | 92.98 (7) | C8—C7—H7A | 121.00 |
O1W—Cu2—N5 | 89.86 (6) | C6—C7—H7A | 121.00 |
O1W—Cu2—N6 | 91.22 (7) | C9—C8—H8A | 120.00 |
N4—Cu2—N5 | 79.93 (7) | C7—C8—H8A | 120.00 |
N4—Cu2—N6 | 159.36 (7) | C8—C9—H9A | 121.00 |
N5—Cu2—N6 | 79.88 (7) | C10—C9—H9A | 121.00 |
S2—S1—O1 | 102.20 (7) | C11—C12—H12A | 121.00 |
S2—S1—O2 | 105.88 (8) | C13—C12—H12A | 121.00 |
S2—S1—O3 | 105.03 (7) | C14—C13—H13A | 121.00 |
O1—S1—O2 | 114.14 (11) | C12—C13—H13A | 120.00 |
O1—S1—O3 | 114.06 (10) | C15—C14—H14A | 120.00 |
O2—S1—O3 | 113.96 (10) | C13—C14—H14A | 120.00 |
S1—S2—O4 | 104.82 (7) | N3—C15—H15A | 119.00 |
S1—S2—O5 | 104.25 (7) | C14—C15—H15A | 119.00 |
S1—S2—O6 | 105.06 (7) | N4—C16—C17 | 122.3 (2) |
O4—S2—O5 | 114.60 (10) | C16—C17—C18 | 118.8 (2) |
O4—S2—O6 | 113.49 (10) | C17—C18—C19 | 119.6 (2) |
O5—S2—O6 | 113.26 (10) | C18—C19—C20 | 118.6 (2) |
Cu1—O1—S1 | 131.99 (10) | C19—C20—C21 | 123.49 (18) |
Cu2—O1W—H1WB | 117 (2) | N4—C20—C21 | 114.25 (15) |
H1WA—O1W—H1WB | 97 (3) | N4—C20—C19 | 122.26 (18) |
Cu2—O1W—H1WA | 107 (2) | N5—C21—C20 | 112.75 (16) |
H2WA—O2W—H2WB | 122 (3) | C20—C21—C22 | 126.82 (18) |
H3WA—O3W—H3WB | 110 (3) | N5—C21—C22 | 120.41 (18) |
Cu1—N1—C1 | 127.48 (15) | C21—C22—C23 | 117.8 (2) |
C1—N1—C5 | 118.74 (17) | C22—C23—C24 | 120.9 (2) |
Cu1—N1—C5 | 113.65 (12) | C23—C24—C25 | 117.74 (18) |
C6—N2—C10 | 122.17 (16) | N5—C25—C26 | 112.65 (16) |
Cu1—N2—C10 | 118.93 (13) | N5—C25—C24 | 120.80 (17) |
Cu1—N2—C6 | 118.90 (13) | C24—C25—C26 | 126.55 (17) |
Cu1—N3—C15 | 127.65 (15) | N6—C26—C25 | 114.28 (17) |
C11—N3—C15 | 118.51 (18) | C25—C26—C27 | 124.43 (18) |
Cu1—N3—C11 | 113.80 (12) | N6—C26—C27 | 121.3 (2) |
C16—N4—C20 | 118.46 (18) | C26—C27—C28 | 119.3 (2) |
Cu2—N4—C20 | 114.33 (12) | C27—C28—C29 | 119.2 (2) |
Cu2—N4—C16 | 127.15 (15) | C28—C29—C30 | 118.7 (2) |
Cu2—N5—C25 | 119.00 (13) | N6—C30—C29 | 122.5 (2) |
C21—N5—C25 | 122.36 (16) | C17—C16—H16A | 119.00 |
Cu2—N5—C21 | 118.62 (13) | N4—C16—H16A | 119.00 |
Cu2—N6—C30 | 126.80 (15) | C18—C17—H17A | 121.00 |
Cu2—N6—C26 | 114.11 (14) | C16—C17—H17A | 121.00 |
C26—N6—C30 | 119.09 (19) | C17—C18—H18A | 120.00 |
N1—C1—C2 | 122.3 (2) | C19—C18—H18A | 120.00 |
C1—C2—C3 | 119.2 (2) | C18—C19—H19A | 121.00 |
C2—C3—C4 | 119.0 (2) | C20—C19—H19A | 121.00 |
C3—C4—C5 | 118.8 (2) | C21—C22—H22A | 121.00 |
N1—C5—C6 | 114.05 (15) | C23—C22—H22A | 121.00 |
N1—C5—C4 | 121.98 (18) | C24—C23—H23A | 120.00 |
C4—C5—C6 | 123.98 (18) | C22—C23—H23A | 120.00 |
N2—C6—C7 | 120.52 (18) | C23—C24—H24A | 121.00 |
C5—C6—C7 | 126.36 (17) | C25—C24—H24A | 121.00 |
N2—C6—C5 | 113.12 (16) | C26—C27—H27A | 120.00 |
C6—C7—C8 | 117.9 (2) | C28—C27—H27A | 120.00 |
C7—C8—C9 | 120.8 (2) | C29—C28—H28A | 120.00 |
C8—C9—C10 | 117.5 (2) | C27—C28—H28A | 120.00 |
N2—C10—C11 | 112.93 (16) | C28—C29—H29A | 121.00 |
C9—C10—C11 | 126.04 (17) | C30—C29—H29A | 121.00 |
N2—C10—C9 | 121.02 (18) | C29—C30—H30A | 119.00 |
N3—C11—C12 | 122.09 (18) | N6—C30—H30A | 119.00 |
Cl1—Cu1—O1—S1 | 164.21 (12) | C11—N3—C15—C14 | 0.5 (3) |
N1—Cu1—O1—S1 | 64.56 (14) | Cu1—N3—C11—C12 | 176.13 (16) |
N2—Cu1—O1—S1 | −15.60 (14) | Cu1—N3—C11—C10 | −2.1 (2) |
N3—Cu1—O1—S1 | −95.46 (14) | Cu1—N3—C15—C14 | −177.08 (17) |
Cl1—Cu1—N1—C1 | −8.76 (18) | C15—N3—C11—C10 | 180.00 (18) |
Cl1—Cu1—N1—C5 | 175.36 (13) | C15—N3—C11—C12 | −1.8 (3) |
O1—Cu1—N1—C1 | 91.73 (18) | C20—N4—C16—C17 | −0.2 (3) |
O1—Cu1—N1—C5 | −84.16 (14) | Cu2—N4—C16—C17 | −177.08 (17) |
N2—Cu1—N1—C1 | 179.9 (2) | Cu2—N4—C20—C19 | 177.29 (16) |
N2—Cu1—N1—C5 | 4.01 (13) | Cu2—N4—C20—C21 | −2.7 (2) |
N3—Cu1—N1—C1 | −170.56 (19) | C16—N4—C20—C19 | 0.0 (3) |
N3—Cu1—N1—C5 | 13.6 (3) | C16—N4—C20—C21 | −179.97 (18) |
O1—Cu1—N2—C6 | 85.64 (14) | Cu2—N5—C21—C20 | 2.4 (2) |
O1—Cu1—N2—C10 | −93.22 (14) | Cu2—N5—C21—C22 | −178.85 (15) |
N1—Cu1—N2—C6 | −2.87 (14) | C25—N5—C21—C20 | −179.08 (17) |
N1—Cu1—N2—C10 | 178.27 (15) | Cu2—N5—C25—C24 | 178.14 (14) |
N3—Cu1—N2—C6 | −179.55 (15) | Cu2—N5—C25—C26 | −2.8 (2) |
N3—Cu1—N2—C10 | 1.59 (14) | C25—N5—C21—C22 | −0.3 (3) |
Cl1—Cu1—N3—C11 | −170.98 (13) | C21—N5—C25—C26 | 178.68 (17) |
Cl1—Cu1—N3—C15 | 6.74 (19) | C21—N5—C25—C24 | −0.4 (3) |
O1—Cu1—N3—C11 | 87.48 (14) | Cu2—N6—C30—C29 | −179.51 (18) |
O1—Cu1—N3—C15 | −94.81 (19) | C30—N6—C26—C27 | −0.2 (3) |
N1—Cu1—N3—C11 | −9.2 (3) | Cu2—N6—C26—C25 | 1.1 (2) |
N1—Cu1—N3—C15 | 168.57 (19) | Cu2—N6—C26—C27 | 180.00 (17) |
N2—Cu1—N3—C11 | 0.40 (14) | C26—N6—C30—C29 | 0.7 (3) |
N2—Cu1—N3—C15 | 178.11 (19) | C30—N6—C26—C25 | −179.08 (18) |
N6—Cu2—N4—C20 | 15.2 (3) | N1—C1—C2—C3 | 0.9 (3) |
O1W—Cu2—N5—C21 | 90.01 (14) | C1—C2—C3—C4 | −0.5 (3) |
O1W—Cu2—N5—C25 | −88.55 (15) | C2—C3—C4—C5 | −0.5 (3) |
N4—Cu2—N5—C21 | −3.04 (14) | C3—C4—C5—N1 | 1.2 (3) |
N4—Cu2—N5—C25 | 178.40 (15) | C3—C4—C5—C6 | −178.9 (2) |
N6—Cu2—N5—C21 | −178.72 (15) | N1—C5—C6—C7 | −177.1 (2) |
N6—Cu2—N5—C25 | 2.72 (14) | C4—C5—C6—N2 | −177.71 (19) |
Cl2—Cu2—N6—C26 | −171.79 (13) | C4—C5—C6—C7 | 3.0 (3) |
Cl2—Cu2—N6—C30 | 8.43 (19) | N1—C5—C6—N2 | 2.3 (2) |
O1W—Cu2—N6—C26 | 87.65 (14) | N2—C6—C7—C8 | 1.2 (3) |
O1W—Cu2—N6—C30 | −92.13 (18) | C5—C6—C7—C8 | −179.5 (2) |
N4—Cu2—N6—C26 | −14.1 (3) | C6—C7—C8—C9 | −0.5 (3) |
N4—Cu2—N6—C30 | 166.08 (19) | C7—C8—C9—C10 | −1.0 (3) |
N5—Cu2—N6—C26 | −1.99 (14) | C8—C9—C10—N2 | 1.7 (3) |
N5—Cu2—N6—C30 | 178.23 (19) | C8—C9—C10—C11 | −177.3 (2) |
N5—Cu2—N4—C20 | 3.08 (14) | N2—C10—C11—N3 | 3.3 (2) |
N6—Cu2—N4—C16 | −167.79 (18) | C9—C10—C11—C12 | 4.2 (3) |
O1W—Cu2—N4—C16 | 90.73 (18) | N2—C10—C11—C12 | −174.86 (19) |
Cl2—Cu2—N4—C16 | −10.11 (18) | C9—C10—C11—N3 | −177.69 (19) |
Cl2—Cu2—N4—C20 | 172.91 (13) | C10—C11—C12—C13 | 179.8 (2) |
O1W—Cu2—N4—C20 | −86.25 (14) | N3—C11—C12—C13 | 1.8 (3) |
N5—Cu2—N4—C16 | −179.93 (19) | C11—C12—C13—C14 | −0.4 (3) |
O1—S1—S2—O4 | 61.46 (10) | C12—C13—C14—C15 | −0.8 (4) |
O3—S1—S2—O4 | −179.21 (10) | C13—C14—C15—N3 | 0.7 (4) |
O3—S1—S2—O5 | 60.03 (10) | N4—C16—C17—C18 | 0.2 (4) |
O1—S1—S2—O5 | −59.31 (10) | C16—C17—C18—C19 | 0.0 (4) |
O1—S1—S2—O6 | −178.66 (10) | C17—C18—C19—C20 | −0.2 (4) |
O2—S1—S2—O4 | −58.31 (11) | C18—C19—C20—N4 | 0.2 (3) |
O2—S1—S2—O5 | −179.08 (11) | C18—C19—C20—C21 | −179.8 (2) |
O2—S1—S2—O6 | 61.57 (11) | N4—C20—C21—N5 | 0.3 (2) |
O3—S1—S2—O6 | −59.33 (10) | N4—C20—C21—C22 | −178.32 (19) |
S2—S1—O1—Cu1 | 174.62 (10) | C19—C20—C21—N5 | −179.68 (19) |
O2—S1—O1—Cu1 | −71.58 (15) | C19—C20—C21—C22 | 1.7 (3) |
O3—S1—O1—Cu1 | 61.85 (15) | N5—C21—C22—C23 | 0.5 (3) |
C1—N1—C5—C4 | −0.8 (3) | C20—C21—C22—C23 | 179.0 (2) |
C1—N1—C5—C6 | 179.26 (18) | C21—C22—C23—C24 | 0.1 (3) |
Cu1—N1—C5—C6 | −4.5 (2) | C22—C23—C24—C25 | −0.7 (3) |
Cu1—N1—C1—C2 | −175.98 (17) | C23—C24—C25—N5 | 0.9 (3) |
C5—N1—C1—C2 | −0.3 (3) | C23—C24—C25—C26 | −178.0 (2) |
Cu1—N1—C5—C4 | 175.50 (16) | N5—C25—C26—N6 | 1.0 (2) |
Cu1—N2—C6—C5 | 1.3 (2) | N5—C25—C26—C27 | −177.9 (2) |
Cu1—N2—C6—C7 | −179.37 (15) | C24—C25—C26—N6 | 180.0 (2) |
C10—N2—C6—C5 | −179.93 (17) | C24—C25—C26—C27 | 1.1 (3) |
C10—N2—C6—C7 | −0.6 (3) | N6—C26—C27—C28 | −1.0 (3) |
Cu1—N2—C10—C9 | 177.85 (15) | C25—C26—C27—C28 | 177.8 (2) |
Cu1—N2—C10—C11 | −3.1 (2) | C26—C27—C28—C29 | 1.7 (4) |
C6—N2—C10—C9 | −1.0 (3) | C27—C28—C29—C30 | −1.2 (4) |
C6—N2—C10—C11 | 178.10 (17) | C28—C29—C30—N6 | 0.0 (4) |
Symmetry codes: (i) −x+2, −y+2, −z; (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O6iii | 0.84 (3) | 1.95 (3) | 2.787 (2) | 176 (3) |
O1W—H1WB···O3W | 0.89 (3) | 2.06 (3) | 2.918 (2) | 162 (3) |
O2W—H2WA···O3iv | 0.88 (3) | 2.01 (3) | 2.831 (2) | 154 (3) |
O2W—H2WB···O4iii | 0.85 (2) | 1.95 (2) | 2.785 (2) | 169 (4) |
O3W—H3WA···O2Wv | 0.83 (3) | 2.00 (3) | 2.811 (2) | 166 (3) |
O3W—H3WB···O2 | 0.82 (3) | 2.24 (3) | 3.052 (2) | 168 (3) |
C4—H4A···O2Wv | 0.95 | 2.47 | 3.407 (3) | 169 |
C7—H7A···O2Wv | 0.95 | 2.43 | 3.347 (3) | 162 |
C8—H8A···O5vi | 0.95 | 2.34 | 3.217 (3) | 154 |
C9—H9A···O2v | 0.95 | 2.56 | 3.496 (3) | 171 |
C12—H12A···O1v | 0.95 | 2.56 | 3.335 (3) | 139 |
C18—H18A···O1Wvii | 0.95 | 2.57 | 3.213 (3) | 126 |
C19—H19A···O3Wvii | 0.95 | 2.50 | 3.446 (3) | 178 |
C22—H22A···O3Wvii | 0.95 | 2.51 | 3.452 (3) | 175 |
C24—H24A···O6 | 0.95 | 2.43 | 3.363 (3) | 167 |
C27—H27A···O6 | 0.95 | 2.19 | 3.141 (3) | 179 |
C29—H29A···Cl2viii | 0.95 | 2.74 | 3.690 (3) | 174 |
Symmetry codes: (iii) x, y−1, z; (iv) x−1, y−1, z; (v) x+1, y, z; (vi) x+1, y−1, z; (vii) x−1, y, z; (viii) −x+2, −y+1, −z+1. |
[Cu2(C15H11N3)2(Cl)2(S2O6)]·H2O | Z = 1 |
Mr = 842.65 | F(000) = 426 |
Triclinic, P1 | Dx = 1.828 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.1961 (13) Å | Cell parameters from 6211 reflections |
b = 8.6029 (15) Å | θ = 1.8–25.5° |
c = 12.2566 (19) Å | µ = 1.76 mm−1 |
α = 107.927 (13)° | T = 173 K |
β = 99.171 (13)° | Plate, pale-green |
γ = 105.244 (13)° | 0.21 × 0.13 × 0.11 mm |
V = 765.7 (2) Å3 |
Stoe IPDS II diffractometer | 2724 independent reflections |
Radiation source: fine-focus sealed tube | 2001 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
ϕ and ω scans | θmax = 25.2°, θmin = 1.8° |
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2009) | h = −9→9 |
Tmin = 0.846, Tmax = 1.00 | k = −10→10 |
8262 measured reflections | l = −14→14 |
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) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.89 | w = 1/[σ2(Fo2) + (0.0451P)2] where P = (Fo2 + 2Fc2)/3 |
2724 reflections | (Δ/σ)max = 0.003 |
232 parameters | Δρmax = 0.28 e Å−3 |
2 restraints | Δρmin = −0.48 e Å−3 |
[Cu2(C15H11N3)2(Cl)2(S2O6)]·H2O | γ = 105.244 (13)° |
Mr = 842.65 | V = 765.7 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.1961 (13) Å | Mo Kα radiation |
b = 8.6029 (15) Å | µ = 1.76 mm−1 |
c = 12.2566 (19) Å | T = 173 K |
α = 107.927 (13)° | 0.21 × 0.13 × 0.11 mm |
β = 99.171 (13)° |
Stoe IPDS II diffractometer | 2724 independent reflections |
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2009) | 2001 reflections with I > 2σ(I) |
Tmin = 0.846, Tmax = 1.00 | Rint = 0.055 |
8262 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 2 restraints |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.89 | Δρmax = 0.28 e Å−3 |
2724 reflections | Δρmin = −0.48 e Å−3 |
232 parameters |
Experimental. IR (ν, cm-1): 3435 (m), 3012 (m), 1598 (m), 1575 (m), 1498 (w), 1474 (m), 1448 (s), 1326 (m), 1303 (m), 1253 (m), 1192 (w), 1165 (w), 1141 (w), 1049 (w), 1035 (w), 1019 (m), 828 (w), 792 (w), 773 (s), 730 (w), 649 (w), 514 (w). |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | Occ. (<1) | |
Cu1 | 0.62148 (6) | 0.64301 (5) | 0.16282 (4) | 0.0323 (2) | |
Cl1 | 0.73281 (12) | 0.69647 (12) | 0.01910 (8) | 0.0389 (3) | |
S1 | 0.89632 (11) | 0.87944 (11) | 0.44994 (7) | 0.0329 (3) | |
O1 | 0.8512 (3) | 0.8817 (3) | 0.33023 (19) | 0.0366 (8) | |
O2 | 0.7588 (3) | 0.8854 (3) | 0.5098 (2) | 0.0404 (8) | |
O3 | 0.9735 (3) | 0.7477 (3) | 0.4565 (2) | 0.0411 (9) | |
N1 | 0.4520 (4) | 0.7782 (3) | 0.1677 (2) | 0.0330 (9) | |
N2 | 0.4891 (4) | 0.5609 (3) | 0.2630 (2) | 0.0301 (9) | |
N3 | 0.7276 (4) | 0.4603 (3) | 0.1821 (2) | 0.0330 (9) | |
C1 | 0.4386 (5) | 0.8893 (4) | 0.1132 (3) | 0.0370 (11) | |
C2 | 0.3136 (5) | 0.9691 (5) | 0.1192 (3) | 0.0389 (12) | |
C3 | 0.1949 (5) | 0.9339 (4) | 0.1827 (3) | 0.0416 (12) | |
C4 | 0.2074 (5) | 0.8198 (4) | 0.2414 (3) | 0.0366 (11) | |
C5 | 0.3368 (4) | 0.7473 (4) | 0.2330 (3) | 0.0322 (10) | |
C6 | 0.3602 (4) | 0.6214 (4) | 0.2890 (3) | 0.0326 (11) | |
C7 | 0.2589 (5) | 0.5621 (5) | 0.3576 (3) | 0.0384 (11) | |
C8 | 0.2891 (5) | 0.4308 (5) | 0.3924 (3) | 0.0364 (11) | |
C9 | 0.4191 (5) | 0.3654 (5) | 0.3618 (3) | 0.0370 (12) | |
C10 | 0.5217 (4) | 0.4362 (4) | 0.2975 (3) | 0.0330 (11) | |
C11 | 0.6644 (4) | 0.3830 (4) | 0.2556 (3) | 0.0339 (11) | |
C12 | 0.7306 (5) | 0.2649 (4) | 0.2849 (3) | 0.0379 (11) | |
C13 | 0.8586 (5) | 0.2186 (5) | 0.2354 (3) | 0.0429 (12) | |
C14 | 0.9197 (5) | 0.2937 (5) | 0.1585 (3) | 0.0412 (12) | |
C15 | 0.8518 (5) | 0.4142 (4) | 0.1351 (3) | 0.0369 (12) | |
O1W | 0.5551 (7) | 0.0699 (7) | 0.4479 (5) | 0.051 (2) | 0.500 |
H1 | 0.51940 | 0.91410 | 0.06820 | 0.0440* | |
H2 | 0.30960 | 1.04780 | 0.07960 | 0.0470* | |
H3 | 0.10600 | 0.98590 | 0.18680 | 0.0500* | |
H4 | 0.12720 | 0.79320 | 0.28640 | 0.0440* | |
H7 | 0.17170 | 0.60960 | 0.38010 | 0.0460* | |
H8 | 0.21950 | 0.38550 | 0.43770 | 0.0440* | |
H9 | 0.43810 | 0.27390 | 0.38420 | 0.0440* | |
H12 | 0.68820 | 0.21590 | 0.33880 | 0.0460* | |
H13 | 0.90410 | 0.13620 | 0.25380 | 0.0520* | |
H14 | 1.00690 | 0.26300 | 0.12250 | 0.0500* | |
H15 | 0.89540 | 0.46680 | 0.08320 | 0.0440* | |
H1WA | 0.472 (9) | 0.065 (13) | 0.486 (8) | 0.0750* | 0.500 |
H1WB | 0.638 (9) | 0.044 (13) | 0.487 (8) | 0.0750* | 0.500 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0352 (3) | 0.0323 (3) | 0.0326 (3) | 0.0135 (2) | 0.0136 (2) | 0.0119 (2) |
Cl1 | 0.0429 (5) | 0.0445 (5) | 0.0346 (5) | 0.0173 (4) | 0.0170 (4) | 0.0160 (4) |
S1 | 0.0332 (5) | 0.0314 (5) | 0.0317 (5) | 0.0096 (4) | 0.0109 (4) | 0.0082 (4) |
O1 | 0.0394 (14) | 0.0360 (13) | 0.0269 (13) | 0.0071 (11) | 0.0044 (11) | 0.0084 (11) |
O2 | 0.0351 (14) | 0.0419 (15) | 0.0431 (15) | 0.0103 (12) | 0.0186 (12) | 0.0122 (12) |
O3 | 0.0478 (16) | 0.0321 (14) | 0.0481 (15) | 0.0170 (12) | 0.0188 (13) | 0.0147 (12) |
N1 | 0.0348 (16) | 0.0294 (15) | 0.0344 (16) | 0.0103 (13) | 0.0132 (13) | 0.0095 (13) |
N2 | 0.0317 (16) | 0.0265 (15) | 0.0279 (15) | 0.0095 (12) | 0.0052 (12) | 0.0058 (12) |
N3 | 0.0331 (16) | 0.0294 (15) | 0.0312 (16) | 0.0081 (13) | 0.0071 (13) | 0.0065 (12) |
C1 | 0.042 (2) | 0.0287 (19) | 0.039 (2) | 0.0114 (16) | 0.0126 (17) | 0.0101 (16) |
C2 | 0.043 (2) | 0.034 (2) | 0.041 (2) | 0.0160 (17) | 0.0095 (18) | 0.0135 (17) |
C3 | 0.041 (2) | 0.031 (2) | 0.048 (2) | 0.0156 (17) | 0.0097 (18) | 0.0061 (17) |
C4 | 0.035 (2) | 0.0319 (19) | 0.042 (2) | 0.0129 (16) | 0.0160 (17) | 0.0079 (16) |
C5 | 0.0351 (19) | 0.0247 (17) | 0.0301 (18) | 0.0072 (15) | 0.0090 (16) | 0.0031 (14) |
C6 | 0.0355 (19) | 0.0272 (18) | 0.0293 (18) | 0.0078 (15) | 0.0072 (15) | 0.0054 (14) |
C7 | 0.037 (2) | 0.041 (2) | 0.0315 (19) | 0.0088 (17) | 0.0123 (16) | 0.0076 (16) |
C8 | 0.036 (2) | 0.039 (2) | 0.0292 (18) | 0.0050 (16) | 0.0095 (16) | 0.0116 (16) |
C9 | 0.040 (2) | 0.037 (2) | 0.032 (2) | 0.0073 (17) | 0.0084 (17) | 0.0153 (16) |
C10 | 0.0348 (19) | 0.0303 (19) | 0.0273 (18) | 0.0072 (15) | 0.0055 (15) | 0.0060 (14) |
C11 | 0.0309 (19) | 0.0295 (18) | 0.0306 (18) | 0.0037 (15) | 0.0036 (15) | 0.0043 (15) |
C12 | 0.037 (2) | 0.0318 (19) | 0.041 (2) | 0.0102 (16) | 0.0033 (17) | 0.0127 (16) |
C13 | 0.040 (2) | 0.035 (2) | 0.049 (2) | 0.0135 (17) | 0.0055 (19) | 0.0114 (18) |
C14 | 0.036 (2) | 0.040 (2) | 0.043 (2) | 0.0164 (17) | 0.0076 (17) | 0.0073 (17) |
C15 | 0.035 (2) | 0.035 (2) | 0.034 (2) | 0.0097 (16) | 0.0096 (16) | 0.0052 (16) |
O1W | 0.048 (4) | 0.047 (3) | 0.057 (4) | 0.016 (3) | 0.015 (3) | 0.019 (3) |
Cu1—Cl1 | 2.2220 (11) | C5—C6 | 1.485 (5) |
Cu1—O1 | 2.473 (2) | C6—C7 | 1.386 (5) |
Cu1—N1 | 2.030 (3) | C7—C8 | 1.389 (6) |
Cu1—N2 | 1.934 (3) | C8—C9 | 1.380 (6) |
Cu1—N3 | 2.041 (3) | C9—C10 | 1.392 (5) |
S1—O1 | 1.462 (2) | C10—C11 | 1.473 (5) |
S1—O2 | 1.443 (3) | C11—C12 | 1.381 (5) |
S1—O3 | 1.452 (3) | C12—C13 | 1.379 (6) |
S1—S1i | 2.1474 (13) | C13—C14 | 1.383 (6) |
O1W—H1WA | 0.88 (8) | C14—C15 | 1.379 (6) |
O1W—H1WB | 0.89 (9) | C1—H1 | 0.9500 |
N1—C5 | 1.357 (5) | C2—H2 | 0.9500 |
N1—C1 | 1.340 (4) | C3—H3 | 0.9500 |
N2—C6 | 1.335 (5) | C4—H4 | 0.9500 |
N2—C10 | 1.340 (4) | C7—H7 | 0.9500 |
N3—C15 | 1.336 (5) | C8—H8 | 0.9500 |
N3—C11 | 1.363 (4) | C9—H9 | 0.9500 |
C1—C2 | 1.375 (6) | C12—H12 | 0.9500 |
C2—C3 | 1.370 (6) | C13—H13 | 0.9500 |
C3—C4 | 1.399 (5) | C14—H14 | 0.9500 |
C4—C5 | 1.367 (5) | C15—H15 | 0.9500 |
Cu1···Cl1ii | 3.3765 (12) | ||
Cl1—Cu1—O1 | 96.47 (7) | N2—C6—C5 | 112.9 (3) |
Cl1—Cu1—N1 | 99.26 (8) | C6—C7—C8 | 117.8 (4) |
Cl1—Cu1—N2 | 168.94 (8) | C7—C8—C9 | 120.7 (4) |
Cl1—Cu1—N3 | 99.51 (9) | C8—C9—C10 | 118.6 (4) |
O1—Cu1—N1 | 93.04 (10) | N2—C10—C9 | 119.9 (3) |
O1—Cu1—N2 | 94.58 (10) | C9—C10—C11 | 126.7 (3) |
O1—Cu1—N3 | 93.51 (10) | N2—C10—C11 | 113.3 (3) |
N1—Cu1—N2 | 79.90 (12) | N3—C11—C12 | 121.4 (3) |
N1—Cu1—N3 | 159.27 (12) | C10—C11—C12 | 124.8 (3) |
N2—Cu1—N3 | 79.99 (12) | N3—C11—C10 | 113.8 (3) |
O1—S1—O2 | 113.74 (15) | C11—C12—C13 | 119.6 (3) |
O1—S1—O3 | 113.51 (15) | C12—C13—C14 | 119.0 (4) |
S1i—S1—O1 | 104.69 (12) | C13—C14—C15 | 118.7 (4) |
O2—S1—O3 | 114.28 (16) | N3—C15—C14 | 123.0 (3) |
S1i—S1—O2 | 104.64 (11) | C2—C1—H1 | 118.00 |
S1i—S1—O3 | 104.57 (11) | N1—C1—H1 | 118.00 |
Cu1—O1—S1 | 123.60 (15) | C1—C2—H2 | 120.00 |
H1WA—O1W—H1WB | 107 (8) | C3—C2—H2 | 120.00 |
Cu1—N1—C1 | 128.2 (3) | C4—C3—H3 | 121.00 |
C1—N1—C5 | 117.2 (3) | C2—C3—H3 | 121.00 |
Cu1—N1—C5 | 114.6 (2) | C3—C4—H4 | 120.00 |
Cu1—N2—C6 | 119.1 (2) | C5—C4—H4 | 121.00 |
Cu1—N2—C10 | 118.8 (3) | C8—C7—H7 | 121.00 |
C6—N2—C10 | 121.9 (3) | C6—C7—H7 | 121.00 |
Cu1—N3—C11 | 113.8 (2) | C7—C8—H8 | 120.00 |
Cu1—N3—C15 | 127.9 (2) | C9—C8—H8 | 120.00 |
C11—N3—C15 | 118.2 (3) | C10—C9—H9 | 121.00 |
N1—C1—C2 | 123.2 (4) | C8—C9—H9 | 121.00 |
C1—C2—C3 | 119.3 (4) | C11—C12—H12 | 120.00 |
C2—C3—C4 | 118.6 (4) | C13—C12—H12 | 120.00 |
C3—C4—C5 | 118.9 (4) | C14—C13—H13 | 120.00 |
N1—C5—C6 | 113.5 (3) | C12—C13—H13 | 120.00 |
C4—C5—C6 | 123.7 (3) | C13—C14—H14 | 121.00 |
N1—C5—C4 | 122.8 (3) | C15—C14—H14 | 121.00 |
N2—C6—C7 | 120.9 (3) | N3—C15—H15 | 119.00 |
C5—C6—C7 | 126.1 (3) | C14—C15—H15 | 118.00 |
Cl1—Cu1—O1—S1 | −154.20 (16) | Cu1—N1—C5—C6 | 0.7 (4) |
N1—Cu1—O1—S1 | 106.12 (18) | C1—N1—C5—C4 | 2.2 (5) |
N2—Cu1—O1—S1 | 26.02 (19) | C1—N1—C5—C6 | 179.4 (3) |
N3—Cu1—O1—S1 | −54.21 (19) | Cu1—N2—C6—C5 | 0.6 (4) |
Cl1—Cu1—N1—C1 | −10.0 (3) | Cu1—N2—C6—C7 | 178.1 (3) |
Cl1—Cu1—N1—C5 | 168.5 (2) | C10—N2—C6—C5 | −174.8 (3) |
O1—Cu1—N1—C1 | 87.0 (3) | C10—N2—C6—C7 | 2.8 (5) |
O1—Cu1—N1—C5 | −94.4 (2) | Cu1—N2—C10—C9 | −175.0 (3) |
N2—Cu1—N1—C1 | −178.9 (3) | Cu1—N2—C10—C11 | 2.3 (4) |
N2—Cu1—N1—C5 | −0.3 (2) | C6—N2—C10—C9 | 0.4 (5) |
N3—Cu1—N1—C1 | −164.7 (3) | C6—N2—C10—C11 | 177.6 (3) |
N3—Cu1—N1—C5 | 13.8 (4) | Cu1—N3—C11—C10 | 5.1 (4) |
O1—Cu1—N2—C6 | 92.1 (2) | Cu1—N3—C11—C12 | −175.6 (3) |
O1—Cu1—N2—C10 | −92.4 (2) | C15—N3—C11—C10 | −177.0 (3) |
N1—Cu1—N2—C6 | −0.2 (2) | C15—N3—C11—C12 | 2.4 (5) |
N1—Cu1—N2—C10 | 175.3 (3) | Cu1—N3—C15—C14 | 177.0 (3) |
N3—Cu1—N2—C6 | −175.1 (3) | C11—N3—C15—C14 | −0.7 (5) |
N3—Cu1—N2—C10 | 0.4 (2) | N1—C1—C2—C3 | −0.6 (6) |
Cl1—Cu1—N3—C11 | −171.9 (2) | C1—C2—C3—C4 | 1.2 (5) |
Cl1—Cu1—N3—C15 | 10.4 (3) | C2—C3—C4—C5 | −0.2 (5) |
O1—Cu1—N3—C11 | 90.9 (2) | C3—C4—C5—N1 | −1.5 (5) |
O1—Cu1—N3—C15 | −86.8 (3) | C3—C4—C5—C6 | −178.5 (3) |
N1—Cu1—N3—C11 | −17.3 (4) | N1—C5—C6—N2 | −0.8 (4) |
N1—Cu1—N3—C15 | 165.0 (3) | N1—C5—C6—C7 | −178.2 (3) |
N2—Cu1—N3—C11 | −3.1 (2) | C4—C5—C6—N2 | 176.4 (3) |
N2—Cu1—N3—C15 | 179.2 (3) | C4—C5—C6—C7 | −1.0 (6) |
O2—S1—O1—Cu1 | −66.8 (2) | N2—C6—C7—C8 | −3.7 (5) |
O3—S1—O1—Cu1 | 66.1 (2) | C5—C6—C7—C8 | 173.5 (3) |
S1i—S1—O1—Cu1 | 179.55 (12) | C6—C7—C8—C9 | 1.6 (5) |
O1—S1—S1i—O1i | −180.00 (15) | C7—C8—C9—C10 | 1.3 (5) |
O1—S1—S1i—O2i | −60.09 (16) | C8—C9—C10—N2 | −2.4 (5) |
O1—S1—S1i—O3i | 60.38 (16) | C8—C9—C10—C11 | −179.2 (3) |
O2—S1—S1i—O1i | 60.09 (16) | N2—C10—C11—N3 | −4.8 (4) |
O2—S1—S1i—O2i | 180.00 (16) | N2—C10—C11—C12 | 175.8 (3) |
O2—S1—S1i—O3i | −59.54 (16) | C9—C10—C11—N3 | 172.2 (3) |
O3—S1—S1i—O1i | −60.38 (16) | C9—C10—C11—C12 | −7.1 (6) |
O3—S1—S1i—O2i | 59.54 (16) | N3—C11—C12—C13 | −2.6 (5) |
O3—S1—S1i—O3i | −180.00 (15) | C10—C11—C12—C13 | 176.7 (3) |
Cu1—N1—C1—C2 | 177.4 (3) | C11—C12—C13—C14 | 0.9 (5) |
C5—N1—C1—C2 | −1.1 (5) | C12—C13—C14—C15 | 0.8 (6) |
Cu1—N1—C5—C4 | −176.6 (3) | C13—C14—C15—N3 | −0.9 (6) |
Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O2iii | 0.88 (8) | 2.05 (8) | 2.803 (7) | 142 (8) |
O1W—H1WB···O2iv | 0.89 (9) | 1.94 (10) | 2.759 (7) | 153 (10) |
C7—H7···O3v | 0.95 | 2.40 | 3.342 (5) | 174 |
C8—H8···O3iii | 0.95 | 2.47 | 3.421 (5) | 176 |
C9—H9···O1W | 0.95 | 2.47 | 3.404 (7) | 168 |
C12—H12···O1W | 0.95 | 2.31 | 3.253 (7) | 172 |
C13—H13···O1iv | 0.95 | 2.60 | 3.429 (5) | 146 |
Symmetry codes: (iii) −x+1, −y+1, −z+1; (iv) x, y−1, z; (v) x−1, y, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Cu(C15H11N3)Cl(H2O)][Cu(C15H11N3)(S2O6)Cl]·2H2O | [Cu2(C15H11N3)2(Cl)2(S2O6)]·H2O |
Mr | 878.68 | 842.65 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 173 | 173 |
a, b, c (Å) | 8.0705 (10), 8.589 (1), 25.177 (3) | 8.1961 (13), 8.6029 (15), 12.2566 (19) |
α, β, γ (°) | 83.096 (10), 82.870 (11), 73.675 (11) | 107.927 (13), 99.171 (13), 105.244 (13) |
V (Å3) | 1655.2 (3) | 765.7 (2) |
Z | 2 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.64 | 1.76 |
Crystal size (mm) | 0.50 × 0.37 × 0.20 | 0.21 × 0.13 × 0.11 |
Data collection | ||
Diffractometer | Stoe IPDS II diffractometer | Stoe IPDS II diffractometer |
Absorption correction | Multi-scan (MULABS in PLATON; Spek, 2009) | Multi-scan (MULABS in PLATON; Spek, 2009) |
Tmin, Tmax | 0.254, 1.00 | 0.846, 1.00 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25099, 8888, 8053 | 8262, 2724, 2001 |
Rint | 0.073 | 0.055 |
(sin θ/λ)max (Å−1) | 0.688 | 0.598 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.116, 1.06 | 0.034, 0.079, 0.89 |
No. of reflections | 8888 | 2724 |
No. of parameters | 485 | 232 |
No. of restraints | 6 | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.95, −1.47 | 0.28, −0.48 |
Computer programs: X-AREA (Stoe & Cie, 2006), X-RED32 (Stoe & Cie, 2006), SHELXS97 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).
Cu1—Cl1 | 2.2203 (6) | Cu2—Cl2 | 2.2284 (6) |
Cu1—O1 | 2.3901 (16) | Cu2—O1W | 2.2816 (16) |
Cu1—N1 | 2.0368 (17) | Cu2—N4 | 2.0216 (17) |
Cu1—N2 | 1.9342 (16) | Cu2—N5 | 1.9447 (16) |
Cu1—N3 | 2.0322 (17) | Cu2—N6 | 2.0245 (17) |
Cu1···Cl1i | 3.2626 (7) | Cu2···Cl2ii | 3.3492 (7) |
Symmetry codes: (i) −x+2, −y+2, −z; (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O6iii | 0.84 (3) | 1.95 (3) | 2.787 (2) | 176 (3) |
O1W—H1WB···O3W | 0.89 (3) | 2.06 (3) | 2.918 (2) | 162 (3) |
O2W—H2WA···O3iv | 0.88 (3) | 2.01 (3) | 2.831 (2) | 154 (3) |
O2W—H2WB···O4iii | 0.85 (2) | 1.95 (2) | 2.785 (2) | 169 (4) |
O3W—H3WA···O2Wv | 0.83 (3) | 2.00 (3) | 2.811 (2) | 166 (3) |
O3W—H3WB···O2 | 0.82 (3) | 2.24 (3) | 3.052 (2) | 168 (3) |
C4—H4A···O2Wv | 0.95 | 2.47 | 3.407 (3) | 169 |
C7—H7A···O2Wv | 0.95 | 2.43 | 3.347 (3) | 162 |
C8—H8A···O5vi | 0.95 | 2.34 | 3.217 (3) | 154 |
C9—H9A···O2v | 0.95 | 2.56 | 3.496 (3) | 171 |
C12—H12A···O1v | 0.95 | 2.56 | 3.335 (3) | 139 |
C18—H18A···O1Wvii | 0.95 | 2.57 | 3.213 (3) | 126 |
C19—H19A···O3Wvii | 0.95 | 2.50 | 3.446 (3) | 178 |
C22—H22A···O3Wvii | 0.95 | 2.51 | 3.452 (3) | 175 |
C24—H24A···O6 | 0.95 | 2.43 | 3.363 (3) | 167 |
C27—H27A···O6 | 0.95 | 2.19 | 3.141 (3) | 179 |
C29—H29A···Cl2viii | 0.95 | 2.74 | 3.690 (3) | 174 |
Symmetry codes: (iii) x, y−1, z; (iv) x−1, y−1, z; (v) x+1, y, z; (vi) x+1, y−1, z; (vii) x−1, y, z; (viii) −x+2, −y+1, −z+1. |
Cu1—Cl1 | 2.2220 (11) | Cu1—N2 | 1.934 (3) |
Cu1—O1 | 2.473 (2) | Cu1—N3 | 2.041 (3) |
Cu1—N1 | 2.030 (3) | ||
Cu1···Cl1i | 3.3765 (12) |
Symmetry code: (i) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O2ii | 0.88 (8) | 2.05 (8) | 2.803 (7) | 142 (8) |
O1W—H1WB···O2iii | 0.89 (9) | 1.94 (10) | 2.759 (7) | 153 (10) |
C7—H7···O3iv | 0.95 | 2.40 | 3.342 (5) | 174 |
C8—H8···O3ii | 0.95 | 2.47 | 3.421 (5) | 176 |
C9—H9···O1W | 0.95 | 2.47 | 3.404 (7) | 168 |
C12—H12···O1W | 0.95 | 2.31 | 3.253 (7) | 172 |
C13—H13···O1iii | 0.95 | 2.60 | 3.429 (5) | 146 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z; (iv) x−1, y, z. |
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Crystal-to-crystal structural transformations are not uncommon and many of these transformations are the result of dehydration of transition metal complexes or polymers (Habib et al., 2008; Lin et al., 2008; Mahmoudi & Morsali, 2008; Mobin et al., 2009). Some of these structural transformations have been shown by in situ powder X-ray diffraction to be reversible on rehydration (Wang et al., 2007; Aslani et al., 2008; Sereda et al., 2009). The ligand 2,2':6',2''-terpyridine (terpy) was first synthesized by Morgan & Burstall (1932). Since then, a very large number of transition metal complexes containing terpy have been synthesized and studied for their optical and electrochemical properties: metal-to-ligand charge transfer (MLCT) in the visible-light region, reversible reduction and oxidation, and fairly intense luminescence. A search of the Cambridge Structural Database (CSD, Version 5.1, last update May 2010; Allen, 2002) revealed the presence of more than 1100 structures involving terpy, the majority being coordination complexes.
The dithionate anion is a potentially useful component for the synthesis of multidimensional coordination polymers (Rusanov et al., 2003; Neels, et al., 2003). A search of the CSD revealed the presence of 119 transition metal complexes containing this anion. However, in the majority of cases it is not coordinated to the metal atom. Three coordination modes were found in this CSD search (A, B and C; see scheme). Coordination mode A was observed for six compounds, of which four are copper(II) complexes (Bernhardt et al., 2004; Ishii, 2001a; Donlevy et al., 1990). Coordination mode B was observed for only two compounds, both of which are copper(II) complexes (Turba et al., 2008; Ishii, 2001a); one of them, catena-poly[(µ2-dithionato-O,O')aqua[2,6-bis(2-pyridyl)pyridine]copper(II)], also involves a terpyridine ligand (Ishii, 2001a). Bridging mode C was observed in seven compounds, of which three involve a copper(II) atom (Degtyarenko et al., 2008; Kim et al., 2003; Ishii, 2001b).
Here, we report the synthesis and crystal structure of a copper(II) terpy ionic complex, (I), with the in situ synthesis of the dithionate anion which coordinates in mode A. On heating, (I) undergoes a crystal-to-crystal transformation to form a binuclear copper(II) terpy dithionate-bridged complex, (II), with the anion coordinating in bridging mode C.
Complex (I) was synthesized by adding sodium sulfite to an aqueous solution of terpy and CuCl2.2H2O. It consists of a [ClCu(terpy)(H2O)]+ cation, a [Cu(terpy)(S2O6)]- anion and two solvent water molecules (Fig. 1). In the cation, atom Cu1 is coordinated to three N atoms of the terpy ligand and a Cl- ion in the basal plane, and to a water molecule in the apical position. The coordination environment can be described as distorted square-pyramidal with a τ value for Cu1 of 0.19 (where τ = 0 for square pyramidal and 1 for trigonal pyramidal; Addison et al., 1984; Spek, 2009). This cation has pseudo-mirror symmetry and is very similar to the same cation in aquachlorido(2,2':6',6''-terpyridyl)copper(II) chloride monohydrate, (III) (Schmitt et al., 2010). The latter possesses crystallographic mirror symmetry and was produced as a by-product of the synthesis of (I). In the anion of (I), atom Cu2 is coordinated by the three N atoms of the terpy ligand and a Cl- ion in the basal plane. The coordination geometry is completed by an O atom of the dithionate anion in the apical position. The coordination environment is also distorted square-pyramidal, with a τ value for Cu2 of 0.18. The majority of the bond distances and angles in the cation and anion (Table 1) are similar to those found in (III). The main difference concerns the apical Cu—O distances: that involving an O atom of the dithionate anion, Cu1—O1, is 2.3901 (16) Å, while that involving the coordinated water molecule, Cu2—O1W, is 2.2816 (16) Å. Interestingly, in complex (III) the Cu—O(water) distance is significantly longer, at 2.3348 (19) Å.
In the crystal structure of (I) the ions are linked by O—H···O hydrogen bonds involving the coordinated and solvent water molecules and O atoms of the dithionate unit (Table 2), to form ribbon-like polymer chains propagating in [100]. These chains are linked by Cu···Cl interactions [3.2626 (7) Å in the cation and 3.3492 (7) Å in the anion, Table 1] centred about inversion centres, to form two-dimensional networks lying in and parallel to (011), as shown in Fig. 2. The overall arrangement has pseudo I centring (Spek, 2009). In the crystal structure there is one signifiant S═O···π interaction, involving the S2═O6 bond and the N4/C16–C20 pyridine ring of a neighbouring molecule at (x, 1 + y, z), with an O···centroid distance of 3.275 (2) Å and an S═O···π angle of 134.8 (1)°. There is also a large number of C—H···O interactions involving both the water and the S═O O atoms, as well as a C—H···Cl interaction (Table 2), and these lead finally to the formation of a three-dimensional network.
Previous work on silmilar complexes has shown that, by careful heating, the solvent and coordinated water molecules can be eliminated. This will leave free coordination sites on the metal atom that can be filled by suitably positioned O or N atoms (Sereda et al., 2008; Xue et al., 2008; Zhang et al., 2009). The emerald-green crystals of (I) were heated to 433 K by thermogravimetry, which indicated the loss of two water molecules at ca 363 K (weight loss of 3.94%, theoretical value 4.1%). The total weight loss at 433 K was 6.01% (equivalent to ca 2.5H2O), whereas the theoretical value for the loss of three water molecules is 6.15%. The resulting material was found to be crystalline; the original crystals had retained their shape but were now pale-green in colour. X-ray diffraction analysis revealed that complex (I) had lost the coordinated water molecule in the cation and apparently only 1.5 solvent water molecules. Dehydration led to the formation of a centrosymmetric binuclear complex, (II), which is composed of two [ClCu(terpy)]+ cations bridged by a dithionate dianion and a partially occupied water molecule (Fig. 3). The crystal-to-crystal transformation resulted in a contraction of the unit-cell volume by more than 50%, and a reduction in the length of the longest cell axis in (I) (i.e. the c axis) of more than 12 Å.
In (II), atom Cu1 is coordinated to the three N atoms of the terpy ligand and a Cl- ion in the basal plane, and to an O atom of the dithionate anion in the axial position. Again, the coordination environment can be described as distorted square-pyramidal, with a τ value of 0.16. The Cu—Cl and Cu—N bond distances are similar to those in complexes (I) and (III) (Table 3). The main difference concerns the Cu—O(dithionate) bond distance, which is longer than in (I) by 0.083 (2) Å. These distances are comparable with values observed in the copper(II) dithionate-bridged complex described by Ishii (2001b).
In the crystal structure of complex (II), molecules related by an inversion centre are linked by O—H···O hydrogen bonds involving the disordered water molecule and an O atom of the bridging thiosulfite anion, so forming a ribbon-like polymer chain propagating in [100] (Table 4, Fig. 4). These chains are linked by weak Cu···Cli interactions [3.3765 (12) Å; see Table 3 for symmetry code] to form two-dimensional networks lying parallel to and in (022), as shown in Fig. 4. As in (I), there are a number of C—H···O interactions involving both the water and the S═O O atoms (Table 4), which lead finally to the formation of a three-dimensional network.
In conclusion, we have shown that by careful drying the water molecule coordinated to the cation in the ionic complex, (I), can be removed and the vacant coordination site is then taken by an O atom of the thiosulfite ligand of the anion. This results in the transformation of the ionic complex (I) into a centrosymmetric binuclear complex, (II), as demonstrated in Fig. 5.