Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102009022/fr1373sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102009022/fr1373Isup2.hkl |
CCDC reference: 192940
Dafone was prepared according to a reported method (Henderson et al., 1984). An aqueous solution (15 ml) containing CuCl2·2H2O (0.85 g, 0.5 mmol) was mixed with an aqueous solution (15 ml) containing thiourea (0.076 g, 1 mmol) at room temperature. Thiourea reduced CuII to CuI (Perrin, 1970) and a large amount of white precipitate of a CuI compound appeared. Dafone (0.182 g, 1 mmol) was introduced in to the solution involving the precipitate. The solution was refluxed for about 2 h until the white precipitate had completely disappeared. Then the yellow solution was filtered and the filtrate kept in a thermostat with 338 K. Yellow crystals of the title compound were obtained after 2 d. Analysis (Carlo-Erba 1160 instrument) calculated for C24H22ClCuN8O3S2: C 45.50, H 3.48, N 17.60%; found: C 45.12, H 3.41, N 17.14%.
H atoms were placed on calculated positions with C—H distances of 0.93 Å, N—H distances of 0.86 Å and O—H distances of 0.85 Å (Nardelli, 1999). All H atoms were included in the final cycles of least-squares refinement; water H atoms with fixed coordinates and Uiso values of 0.08 Å2, while the other H atom were refined as riding on their parent non-H atoms with Uiso values 1.2 times the Ueq values of the parent atoms.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1985); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[CuCl(CH4N2S)2]·2C11H6N2O·H2O | Z = 2 |
Mr = 633.64 | F(000) = 648 |
Triclinic, P1 | Dx = 1.549 Mg m−3 |
a = 8.3016 (9) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 11.8473 (18) Å | Cell parameters from 25 reflections |
c = 14.3024 (9) Å | θ = 4.6–9.9° |
α = 93.896 (8)° | µ = 1.10 mm−1 |
β = 99.206 (7)° | T = 298 K |
γ = 100.562 (10)° | Prism, yellow |
V = 1358.1 (3) Å3 | 0.44 × 0.40 × 0.38 mm |
Rigaku AFC-7S diffractometer | 3411 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.031 |
Graphite monochromator | θmax = 26°, θmin = 2.2° |
ω/2θ scans | h = −10→10 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→14 |
Tmin = 0.617, Tmax = 0.659 | l = −17→17 |
5608 measured reflections | 3 standard reflections every 100 reflections |
5336 independent reflections | intensity decay: 0.5% |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0711P)2 + 0.5579P] where P = (Fo2 + 2Fc2)/3 |
5336 reflections | (Δ/σ)max < 0.001 |
352 parameters | Δρmax = 0.81 e Å−3 |
0 restraints | Δρmin = −0.57 e Å−3 |
[CuCl(CH4N2S)2]·2C11H6N2O·H2O | γ = 100.562 (10)° |
Mr = 633.64 | V = 1358.1 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.3016 (9) Å | Mo Kα radiation |
b = 11.8473 (18) Å | µ = 1.10 mm−1 |
c = 14.3024 (9) Å | T = 298 K |
α = 93.896 (8)° | 0.44 × 0.40 × 0.38 mm |
β = 99.206 (7)° |
Rigaku AFC-7S diffractometer | 3411 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.031 |
Tmin = 0.617, Tmax = 0.659 | 3 standard reflections every 100 reflections |
5608 measured reflections | intensity decay: 0.5% |
5336 independent reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.81 e Å−3 |
5336 reflections | Δρmin = −0.57 e Å−3 |
352 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cu | 0.80725 (6) | 0.64355 (4) | 0.73924 (3) | 0.05318 (16) | |
Cl | 0.71265 (16) | 0.80875 (9) | 0.74969 (8) | 0.0766 (4) | |
S1 | 0.81548 (14) | 0.52762 (8) | 0.85440 (6) | 0.0580 (3) | |
S2 | 0.91653 (15) | 0.58813 (8) | 0.61706 (7) | 0.0638 (3) | |
O1 | 0.4098 (4) | 0.8012 (3) | 1.41964 (19) | 0.0775 (9) | |
O2 | 0.8428 (4) | 1.0801 (2) | 0.09320 (17) | 0.0645 (7) | |
O3 | 0.8123 (5) | 0.3155 (3) | 1.0905 (3) | 0.1016 (12) | |
N1 | 0.7090 (4) | 0.5148 (3) | 1.0171 (2) | 0.0632 (9) | |
H1 | 0.6616 | 0.5372 | 1.0622 | 0.076* | |
H2 | 0.7488 | 0.4528 | 1.0197 | 0.076* | |
N2 | 0.6598 (4) | 0.6695 (2) | 0.9410 (2) | 0.0536 (8) | |
H3 | 0.6126 | 0.6910 | 0.9866 | 0.064* | |
H4 | 0.6668 | 0.7098 | 0.8936 | 0.064* | |
N3 | 0.9863 (4) | 0.6710 (3) | 0.4602 (2) | 0.0585 (8) | |
H5 | 0.9877 | 0.7199 | 0.4184 | 0.070* | |
H6 | 1.0306 | 0.6115 | 0.4530 | 0.070* | |
N4 | 0.8496 (4) | 0.7787 (2) | 0.5446 (2) | 0.0530 (7) | |
H7 | 0.8518 | 0.8270 | 0.5023 | 0.064* | |
H8 | 0.8035 | 0.7904 | 0.5932 | 0.064* | |
N5 | 0.6202 (4) | 0.5686 (2) | 1.2035 (2) | 0.0522 (7) | |
N6 | 0.5164 (4) | 0.7722 (2) | 1.10323 (19) | 0.0489 (7) | |
N7 | 0.9693 (4) | 0.7860 (2) | 0.2849 (2) | 0.0487 (7) | |
N8 | 0.8257 (4) | 0.9575 (2) | 0.40162 (18) | 0.0467 (7) | |
C1 | 0.7209 (4) | 0.5755 (3) | 0.9439 (2) | 0.0463 (8) | |
C2 | 0.9165 (4) | 0.6872 (3) | 0.5350 (2) | 0.0458 (8) | |
C3 | 0.6497 (5) | 0.4873 (3) | 1.2611 (3) | 0.0636 (10) | |
H9 | 0.6947 | 0.4271 | 1.2378 | 0.076* | |
C4 | 0.6174 (6) | 0.4874 (4) | 1.3535 (3) | 0.0693 (11) | |
H10 | 0.6383 | 0.4276 | 1.3897 | 0.083* | |
C5 | 0.5542 (5) | 0.5766 (3) | 1.3909 (3) | 0.0598 (10) | |
H11 | 0.5332 | 0.5798 | 1.4529 | 0.072* | |
C6 | 0.5234 (4) | 0.6606 (3) | 1.3330 (2) | 0.0467 (8) | |
C7 | 0.4534 (5) | 0.7664 (3) | 1.3487 (2) | 0.0502 (8) | |
C8 | 0.4481 (4) | 0.8204 (3) | 1.2574 (2) | 0.0443 (7) | |
C9 | 0.3956 (5) | 0.9174 (3) | 1.2298 (3) | 0.0537 (9) | |
H12 | 0.3561 | 0.9652 | 1.2713 | 0.064* | |
C10 | 0.4037 (5) | 0.9415 (3) | 1.1371 (3) | 0.0566 (9) | |
H13 | 0.3698 | 1.0070 | 1.1150 | 0.068* | |
C11 | 0.4622 (5) | 0.8681 (3) | 1.0778 (3) | 0.0547 (9) | |
H14 | 0.4644 | 0.8860 | 1.0156 | 0.066* | |
C12 | 0.5072 (4) | 0.7514 (3) | 1.1928 (2) | 0.0410 (7) | |
C13 | 0.5567 (4) | 0.6525 (3) | 1.2409 (2) | 0.0432 (7) | |
C14 | 1.0171 (5) | 0.7214 (3) | 0.2175 (3) | 0.0548 (9) | |
H15 | 1.0484 | 0.6529 | 0.2339 | 0.066* | |
C15 | 1.0234 (5) | 0.7489 (3) | 0.1261 (3) | 0.0571 (9) | |
H16 | 1.0580 | 0.7001 | 0.0831 | 0.069* | |
C16 | 0.9776 (4) | 0.8499 (3) | 0.0988 (2) | 0.0521 (9) | |
H17 | 0.9805 | 0.8711 | 0.0375 | 0.063* | |
C17 | 0.9275 (4) | 0.9177 (3) | 0.1661 (2) | 0.0429 (7) | |
C18 | 0.8631 (4) | 1.0265 (3) | 0.1619 (2) | 0.0478 (8) | |
C19 | 0.8199 (4) | 1.0528 (3) | 0.2574 (2) | 0.0441 (7) | |
C20 | 0.7457 (5) | 1.1368 (3) | 0.2923 (3) | 0.0545 (9) | |
H18 | 0.7193 | 1.1955 | 0.2564 | 0.065* | |
C21 | 0.7116 (5) | 1.1302 (3) | 0.3841 (3) | 0.0572 (9) | |
H19 | 0.6608 | 1.1848 | 0.4112 | 0.069* | |
C22 | 0.7543 (5) | 1.0412 (3) | 0.4347 (2) | 0.0560 (9) | |
H20 | 0.7318 | 1.0394 | 0.4963 | 0.067* | |
C23 | 0.8561 (4) | 0.9658 (3) | 0.3138 (2) | 0.0408 (7) | |
C24 | 0.9245 (4) | 0.8819 (3) | 0.2571 (2) | 0.0410 (7) | |
H21 | 0.8933 | 0.3540 | 1.1329 | 0.080* | |
H22 | 0.8257 | 0.2447 | 1.0899 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0782 (3) | 0.0516 (3) | 0.0424 (2) | 0.0280 (2) | 0.0261 (2) | 0.01513 (18) |
Cl | 0.1269 (10) | 0.0612 (6) | 0.0689 (6) | 0.0554 (6) | 0.0474 (6) | 0.0265 (5) |
S1 | 0.0924 (7) | 0.0542 (5) | 0.0473 (5) | 0.0400 (5) | 0.0363 (5) | 0.0194 (4) |
S2 | 0.1115 (8) | 0.0570 (5) | 0.0471 (5) | 0.0482 (6) | 0.0408 (5) | 0.0252 (4) |
O1 | 0.114 (2) | 0.086 (2) | 0.0517 (16) | 0.0437 (18) | 0.0439 (16) | 0.0072 (14) |
O2 | 0.091 (2) | 0.0713 (17) | 0.0437 (13) | 0.0325 (15) | 0.0192 (13) | 0.0277 (12) |
O3 | 0.106 (3) | 0.078 (2) | 0.118 (3) | 0.033 (2) | −0.009 (2) | 0.014 (2) |
N1 | 0.104 (3) | 0.0583 (18) | 0.0461 (16) | 0.0377 (18) | 0.0370 (17) | 0.0196 (14) |
N2 | 0.086 (2) | 0.0499 (16) | 0.0397 (15) | 0.0324 (16) | 0.0295 (14) | 0.0106 (12) |
N3 | 0.094 (2) | 0.0521 (17) | 0.0433 (15) | 0.0298 (17) | 0.0299 (15) | 0.0177 (13) |
N4 | 0.080 (2) | 0.0488 (16) | 0.0430 (15) | 0.0275 (15) | 0.0242 (14) | 0.0193 (13) |
N5 | 0.072 (2) | 0.0485 (16) | 0.0445 (16) | 0.0235 (15) | 0.0192 (14) | 0.0077 (13) |
N6 | 0.0641 (19) | 0.0489 (16) | 0.0375 (14) | 0.0147 (14) | 0.0146 (13) | 0.0086 (12) |
N7 | 0.0649 (19) | 0.0439 (15) | 0.0449 (15) | 0.0192 (14) | 0.0199 (13) | 0.0106 (12) |
N8 | 0.0664 (19) | 0.0458 (15) | 0.0351 (14) | 0.0190 (14) | 0.0181 (13) | 0.0107 (12) |
C1 | 0.064 (2) | 0.0449 (18) | 0.0354 (16) | 0.0181 (16) | 0.0157 (15) | 0.0067 (13) |
C2 | 0.063 (2) | 0.0462 (18) | 0.0346 (16) | 0.0191 (16) | 0.0153 (15) | 0.0097 (14) |
C3 | 0.088 (3) | 0.055 (2) | 0.058 (2) | 0.033 (2) | 0.019 (2) | 0.0121 (18) |
C4 | 0.098 (3) | 0.061 (2) | 0.056 (2) | 0.029 (2) | 0.015 (2) | 0.0237 (19) |
C5 | 0.083 (3) | 0.062 (2) | 0.0393 (18) | 0.016 (2) | 0.0186 (18) | 0.0152 (16) |
C6 | 0.056 (2) | 0.0507 (19) | 0.0354 (16) | 0.0089 (16) | 0.0146 (15) | 0.0047 (14) |
C7 | 0.059 (2) | 0.053 (2) | 0.0427 (18) | 0.0131 (17) | 0.0186 (16) | 0.0041 (15) |
C8 | 0.0477 (19) | 0.0480 (18) | 0.0380 (16) | 0.0097 (15) | 0.0124 (14) | −0.0023 (14) |
C9 | 0.059 (2) | 0.0462 (19) | 0.061 (2) | 0.0181 (17) | 0.0181 (18) | −0.0004 (17) |
C10 | 0.065 (2) | 0.0461 (19) | 0.063 (2) | 0.0166 (18) | 0.0121 (19) | 0.0144 (17) |
C11 | 0.069 (2) | 0.051 (2) | 0.0474 (19) | 0.0136 (18) | 0.0151 (17) | 0.0144 (16) |
C12 | 0.0461 (18) | 0.0418 (17) | 0.0370 (15) | 0.0102 (14) | 0.0123 (13) | 0.0011 (13) |
C13 | 0.052 (2) | 0.0445 (17) | 0.0359 (16) | 0.0119 (15) | 0.0134 (14) | 0.0061 (13) |
C14 | 0.071 (2) | 0.0466 (19) | 0.056 (2) | 0.0219 (18) | 0.0252 (18) | 0.0086 (16) |
C15 | 0.068 (2) | 0.057 (2) | 0.053 (2) | 0.0187 (19) | 0.0251 (18) | −0.0025 (17) |
C16 | 0.060 (2) | 0.065 (2) | 0.0349 (16) | 0.0125 (18) | 0.0183 (15) | 0.0040 (15) |
C17 | 0.0491 (19) | 0.0470 (18) | 0.0352 (15) | 0.0122 (15) | 0.0106 (13) | 0.0072 (13) |
C18 | 0.057 (2) | 0.0517 (19) | 0.0383 (17) | 0.0130 (16) | 0.0137 (15) | 0.0121 (15) |
C19 | 0.056 (2) | 0.0448 (17) | 0.0360 (16) | 0.0147 (15) | 0.0138 (14) | 0.0092 (14) |
C20 | 0.070 (2) | 0.050 (2) | 0.052 (2) | 0.0265 (18) | 0.0145 (17) | 0.0134 (16) |
C21 | 0.076 (3) | 0.054 (2) | 0.051 (2) | 0.0280 (19) | 0.0222 (18) | 0.0012 (17) |
C22 | 0.081 (3) | 0.055 (2) | 0.0406 (18) | 0.0209 (19) | 0.0262 (18) | 0.0080 (16) |
C23 | 0.0504 (19) | 0.0401 (16) | 0.0350 (15) | 0.0109 (14) | 0.0121 (14) | 0.0083 (13) |
C24 | 0.0478 (19) | 0.0429 (17) | 0.0343 (15) | 0.0091 (15) | 0.0120 (14) | 0.0058 (13) |
Cu—S2 | 2.2084 (10) | C4—H10 | 0.9300 |
Cu—S1 | 2.2158 (10) | C5—C6 | 1.370 (5) |
Cu—Cl | 2.2429 (10) | C5—H11 | 0.9300 |
S1—C1 | 1.722 (3) | C6—C13 | 1.389 (4) |
S2—C2 | 1.715 (3) | C6—C7 | 1.493 (5) |
O1—C7 | 1.203 (4) | C7—C8 | 1.491 (5) |
O2—C18 | 1.212 (4) | C8—C9 | 1.363 (5) |
O3—H21 | 0.864 | C8—C12 | 1.397 (4) |
O3—H22 | 0.865 | C9—C10 | 1.384 (5) |
N1—C1 | 1.316 (4) | C9—H12 | 0.9300 |
N1—H1 | 0.8600 | C10—C11 | 1.379 (5) |
N1—H2 | 0.8600 | C10—H13 | 0.9300 |
N2—C1 | 1.306 (4) | C11—H14 | 0.9300 |
N2—H3 | 0.8600 | C12—C13 | 1.488 (4) |
N2—H4 | 0.8600 | C14—C15 | 1.374 (5) |
N3—C2 | 1.315 (4) | C14—H15 | 0.9300 |
N3—H5 | 0.8600 | C15—C16 | 1.383 (5) |
N3—H6 | 0.8600 | C15—H16 | 0.9300 |
N4—C2 | 1.315 (4) | C16—C17 | 1.374 (5) |
N4—H7 | 0.8600 | C16—H17 | 0.9300 |
N4—H8 | 0.8600 | C17—C24 | 1.399 (4) |
N5—C13 | 1.327 (4) | C17—C18 | 1.484 (5) |
N5—C3 | 1.340 (5) | C18—C19 | 1.494 (4) |
N6—C12 | 1.332 (4) | C19—C20 | 1.369 (5) |
N6—C11 | 1.347 (5) | C19—C23 | 1.398 (4) |
N7—C24 | 1.325 (4) | C20—C21 | 1.391 (5) |
N7—C14 | 1.344 (4) | C20—H18 | 0.9300 |
N8—C23 | 1.326 (4) | C21—C22 | 1.385 (5) |
N8—C22 | 1.342 (4) | C21—H19 | 0.9300 |
C3—C4 | 1.389 (5) | C22—H20 | 0.9300 |
C3—H9 | 0.9300 | C23—C24 | 1.487 (4) |
C4—C5 | 1.377 (6) | ||
S2—Cu—S1 | 113.96 (4) | C8—C9—H12 | 121.5 |
S2—Cu—Cl | 122.77 (4) | C10—C9—H12 | 121.5 |
S1—Cu—Cl | 123.15 (4) | C11—C10—C9 | 119.7 (3) |
C1—S1—Cu | 110.24 (11) | C11—C10—H13 | 120.2 |
C2—S2—Cu | 110.75 (11) | C9—C10—H13 | 120.2 |
H21—O3—H22 | 105.1 | N6—C11—C10 | 124.8 (3) |
C1—N1—H1 | 120.0 | N6—C11—H14 | 117.6 |
C1—N1—H2 | 120.0 | C10—C11—H14 | 117.6 |
H1—N1—H2 | 120.0 | N6—C12—C8 | 124.9 (3) |
C1—N2—H3 | 120.0 | N6—C12—C13 | 126.6 (3) |
C1—N2—H4 | 120.0 | C8—C12—C13 | 108.6 (3) |
H3—N2—H4 | 120.0 | N5—C13—C6 | 124.7 (3) |
C2—N3—H5 | 120.0 | N5—C13—C12 | 126.8 (3) |
C2—N3—H6 | 120.0 | C6—C13—C12 | 108.6 (3) |
H5—N3—H6 | 120.0 | N7—C14—C15 | 124.9 (3) |
C2—N4—H7 | 120.0 | N7—C14—H15 | 117.5 |
C2—N4—H8 | 120.0 | C15—C14—H15 | 117.5 |
H7—N4—H8 | 120.0 | C14—C15—C16 | 119.4 (3) |
C13—N5—C3 | 115.1 (3) | C14—C15—H16 | 120.3 |
C12—N6—C11 | 114.1 (3) | C16—C15—H16 | 120.3 |
C24—N7—C14 | 114.8 (3) | C17—C16—C15 | 117.0 (3) |
C23—N8—C22 | 114.5 (3) | C17—C16—H17 | 121.5 |
N2—C1—N1 | 119.2 (3) | C15—C16—H17 | 121.5 |
N2—C1—S1 | 122.1 (2) | C16—C17—C24 | 119.3 (3) |
N1—C1—S1 | 118.8 (3) | C16—C17—C18 | 132.3 (3) |
N4—C2—N3 | 119.0 (3) | C24—C17—C18 | 108.3 (3) |
N4—C2—S2 | 122.2 (2) | O2—C18—C17 | 126.6 (3) |
N3—C2—S2 | 118.8 (3) | O2—C18—C19 | 127.0 (3) |
N5—C3—C4 | 124.2 (4) | C17—C18—C19 | 106.3 (3) |
N5—C3—H9 | 117.9 | C20—C19—C23 | 119.5 (3) |
C4—C3—H9 | 117.9 | C20—C19—C18 | 132.2 (3) |
C5—C4—C3 | 119.4 (4) | C23—C19—C18 | 108.0 (3) |
C5—C4—H10 | 120.3 | C19—C20—C21 | 116.9 (3) |
C3—C4—H10 | 120.3 | C19—C20—H18 | 121.6 |
C6—C5—C4 | 117.2 (3) | C21—C20—H18 | 121.6 |
C6—C5—H11 | 121.4 | C22—C21—C20 | 119.2 (3) |
C4—C5—H11 | 121.4 | C22—C21—H19 | 120.4 |
C5—C6—C13 | 119.5 (3) | C20—C21—H19 | 120.4 |
C5—C6—C7 | 131.7 (3) | N8—C22—C21 | 125.0 (3) |
C13—C6—C7 | 108.8 (3) | N8—C22—H20 | 117.5 |
O1—C7—C8 | 126.8 (3) | C21—C22—H20 | 117.5 |
O1—C7—C6 | 127.7 (3) | N8—C23—C19 | 124.9 (3) |
C8—C7—C6 | 105.5 (3) | N8—C23—C24 | 126.3 (3) |
C9—C8—C12 | 119.6 (3) | C19—C23—C24 | 108.7 (3) |
C9—C8—C7 | 131.9 (3) | N7—C24—C17 | 124.4 (3) |
C12—C8—C7 | 108.5 (3) | N7—C24—C23 | 126.8 (3) |
C8—C9—C10 | 116.9 (3) | C17—C24—C23 | 108.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N5 | 0.86 | 2.12 | 2.937 (4) | 158 |
N1—H2···O3 | 0.86 | 2.08 | 2.864 (5) | 152 |
N2—H3···N6 | 0.86 | 2.20 | 3.052 (4) | 171 |
N2—H4···Cl | 0.86 | 2.48 | 3.337 (3) | 172 |
N3—H5···N7 | 0.86 | 2.11 | 2.930 (4) | 160 |
N3—H6···S2i | 0.86 | 2.64 | 3.468 (4) | 161 |
N4—H7···N8 | 0.86 | 2.20 | 3.053 (4) | 172 |
N4—H8···Cl | 0.86 | 2.48 | 3.331 (3) | 169 |
O3—H21···S1ii | 0.86 | 2.54 | 3.247 (4) | 140 |
O3—H22···O2iii | 0.86 | 1.98 | 2.848 (4) | 176 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y+1, −z+2; (iii) x, y−1, z+1. |
Experimental details
Crystal data | |
Chemical formula | [CuCl(CH4N2S)2]·2C11H6N2O·H2O |
Mr | 633.64 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 8.3016 (9), 11.8473 (18), 14.3024 (9) |
α, β, γ (°) | 93.896 (8), 99.206 (7), 100.562 (10) |
V (Å3) | 1358.1 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.10 |
Crystal size (mm) | 0.44 × 0.40 × 0.38 |
Data collection | |
Diffractometer | Rigaku AFC-7S diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.617, 0.659 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5608, 5336, 3411 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.132, 1.02 |
No. of reflections | 5336 |
No. of parameters | 352 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.81, −0.57 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1985), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N5 | 0.86 | 2.12 | 2.937 (4) | 158 |
N1—H2···O3 | 0.86 | 2.08 | 2.864 (5) | 152 |
N2—H3···N6 | 0.86 | 2.20 | 3.052 (4) | 171 |
N2—H4···Cl | 0.86 | 2.48 | 3.337 (3) | 172 |
N3—H5···N7 | 0.86 | 2.11 | 2.930 (4) | 160 |
N3—H6···S2i | 0.86 | 2.64 | 3.468 (4) | 161 |
N4—H7···N8 | 0.86 | 2.20 | 3.053 (4) | 172 |
N4—H8···Cl | 0.86 | 2.48 | 3.331 (3) | 169 |
O3—H21···S1ii | 0.86 | 2.54 | 3.247 (4) | 140 |
O3—H22···O2iii | 0.86 | 1.98 | 2.848 (4) | 176 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y+1, −z+2; (iii) x, y−1, z+1. |
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The structural study of transition metal complexes containing sulfur coordination is helpful for catalysis (Stiefel & Matsumoto, 1996) and medicinal chemistry (Jurisson et al., 1993). As a ligand containing an S atom, thiourea is an interesting reagent, having several possible modes of bonding to a metal ion.
A thiourea–CuI complex has been reported previously (Spofford & Amma, 1970) in which the thiourea acted as a bridging ligand, the S atoms bonding to neighbouring CuI atoms forming a spiral structure. Recently, during an investigation of the coordination ability of 4,5-diazafluoren-9-one (dafone), a new thiourea–CuI complex, (I), in which thiourea displays a different coordination mode from that reported, was obtained in our laboratory.
The molecular structure of (I) is illustrated in Fig. 1. Selected geometric parameters and hydrogen-bonding geometry are listed in Tables 1 and 2, respectively. The asymmetric unit consists of molecules of the CuI complex, free dafone and crystalline water. The CuI atom lies in a planar trigonal coordination environment, with a deviation of 0.0456 (9) Å from the plane formed by atoms Cl, S1 and S2. Two monodentate thiourea molecules coordinate to the CuI atom through their S atoms, with normal Cu—S distances of 2.2084 (10) and 2.2158 (10) Å. A Cl atom coordinates to the CuI atom with a distance of 2.2429 (10) Å, which is much shorter than the distances of 2.828 (5) and 3.164 (4) Å found in the CuI complex cited above (Spofford & Amma, 1970). Intramolecular hydrogen bonding between the chlorine and amine groups stabilizes the planar structure of the CuI complex.
The dafone and water molecules link the CuI complex through hydrogen bonds, as shown in Fig. 1. Both dafone and the water O atom are approximately coplanar with the CuI complex, the maximum atomic deviation from the mean plane of the complex being 0.858 (6) Å for O1. The planar dafone molecule is structurally similar to phenanthroline (phen), but the carbonyl bridge in dafone distorts the bipyridine portion. The average bond angle of 126.7 (3)° for N6—C12—C13 and N5—C13—C12 resulted in a longer N5···N6 separation of 3.075 (4) Å, while the average bond angle of 126.6 (3)° for N8—C23—C24 and N7—C24—C23 resulted in a similar N7···N8 separation of 3.066 (4) Å. The N···N separations in the present structure are in agreement with the values of 3.055 and 3.064 Å found in the reported structures containing free dafone (Fun et al., 1995; Luo et al., 2002), but much longer than N···N distance of 2.724 Å in free phen (Nishigaki et al., 1978). The longer N···N separation in dafone reduces overlap of the nitrogen–metal orbitals (Henderson et al., 1984) and results in a weaker chelating ability of dafone than phen. In fact, several complex structures with uncoordinated dafone (Menon et al., 1994; Chen, 1998; Kulkarni et al., 2001), dafone coordinated as a monodentate ligand (Lu et al., 1996) or dafone as an asymmetric chelate (i.e. one normal bond and another much longer bond) (Menon & Rajasekharan, 1998; Balagopalakrishna et al., 1992) have been reported previously. Structures with dafone symmetrically chelating to a metal ion have also been reported. It is interesting that significantly shorter N···N distances of 2.850 and 2.806 Å were found in the symmetrically chelating structures (Xiong et al., 1996; Menon & Rajasekharan, 1997). These facts imply that the structure of dafone is rather flexible and the distortion of the bipyridine portion in dafone may be self-adjusting when dafone chelates a metal ion.
With the aid of hydrogen bonds between dafone, water and thiourea, the asymmetric units link to each other to form planar chains. The chains self-assemble to form a two-dimensional sheet structure, as shown in Fig. 2. The centrosymmetric N—H···S hydrogen-bonded dimer observed in the present structure has also been found in both a free thiourea structure (Truter, 1967) and a thiourea complex (Johnson & Steed, 1998).
Between the neighboring sheets, the dafone rings are approximately parallel [dihedral angle 1.13 (10)°] and partially overlap each other, as shown in Fig. 3. Atoms of the N6A-pyridine ring deviate from the mean plane of the N7-dafone molecule with relatively shorter distances ranging from 3.354 (4) Å (C8A) to 3.455 (4) Å (C11A), which suggests the existence of aromatic π–π-stacking interactions between neighbouring dafone molecules.