Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107046288/bg3050sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107046288/bg3050Isup2.hkl |
CCDC reference: 631934
The pmpo ligand was synthesized following a procedure reported previously (Dodd & Nishi, 1997). At room temperature, to a solution of Cd(NO3)·4H2O (0.0308 g, 0.1 mmol) in CH3OH (5 ml) was added a solution of pmpo (0.0540 g, 0.2 mmol) in CH3CN (5 ml) with vigorous stirring for 10 min, and then potassium thiocyanate (0.0194 g, 0.2 mmol) in aqueous solution (5 ml) was added slowly to the above mixed solution under reflux condition. The reaction mixture was filtered and left to stand at room temperature. Well shaped prismatic colourless single crystals suitable for X-ray analysis were obtained after several days by slow evaporation of the solvent (yield 34%).
All H atoms were positioned geometrically, with C—H distances of 0.93 (CH) and 0.97 Å (CH2), and constrained to ride on their parent atoms [Uiso(H) = 1.2Ueq(C)].
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[Cd(NCS)2(C13H10N4OS)2] | Z = 2 |
Mr = 769.18 | F(000) = 772 |
Triclinic, P1 | Dx = 1.657 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.8868 (13) Å | Cell parameters from 1434 reflections |
b = 11.1060 (18) Å | θ = 2.5–28.3° |
c = 19.050 (4) Å | µ = 1.03 mm−1 |
α = 104.686 (4)° | T = 291 K |
β = 93.920 (5)° | Prism, colourless |
γ = 105.202 (3)° | 0.50 × 0.21 × 0.12 mm |
V = 1541.2 (5) Å3 |
Siemens SMART CCD diffractometer | 5756 independent reflections |
Radiation source: fine-focus sealed tube | 4955 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
ω scans | θmax = 25.5°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.628, Tmax = 0.887 | k = −13→13 |
11469 measured reflections | l = −23→22 |
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)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.054 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0215P)2 + 0.5618P] where P = (Fo2 + 2Fc2)/3 |
5695 reflections | (Δ/σ)max = 0.001 |
406 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
[Cd(NCS)2(C13H10N4OS)2] | γ = 105.202 (3)° |
Mr = 769.18 | V = 1541.2 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.8868 (13) Å | Mo Kα radiation |
b = 11.1060 (18) Å | µ = 1.03 mm−1 |
c = 19.050 (4) Å | T = 291 K |
α = 104.686 (4)° | 0.50 × 0.21 × 0.12 mm |
β = 93.920 (5)° |
Siemens SMART CCD diffractometer | 5756 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4955 reflections with I > 2σ(I) |
Tmin = 0.628, Tmax = 0.887 | Rint = 0.015 |
11469 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.054 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.21 e Å−3 |
5695 reflections | Δρmin = −0.30 e Å−3 |
406 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 | ||
Cd1 | 0.28131 (2) | 0.238922 (14) | 0.494519 (8) | 0.03671 (6) | |
S1 | 0.63962 (8) | −0.16775 (6) | 0.02115 (3) | 0.04457 (14) | |
S2 | 0.14998 (8) | 0.69266 (6) | 1.00176 (3) | 0.04411 (14) | |
S3 | 0.05369 (8) | −0.16342 (6) | 0.57902 (3) | 0.04660 (15) | |
S4 | 0.36063 (8) | 0.66414 (6) | 0.43973 (4) | 0.04900 (15) | |
O1 | 0.5671 (2) | −0.07891 (14) | 0.15504 (8) | 0.0401 (4) | |
O2 | 0.1917 (2) | 0.60210 (14) | 0.86397 (8) | 0.0396 (3) | |
N1 | 0.3880 (2) | 0.10997 (17) | 0.39976 (9) | 0.0385 (4) | |
N2 | 0.5591 (3) | −0.23645 (18) | 0.20743 (10) | 0.0457 (5) | |
N3 | 0.6006 (3) | −0.27639 (18) | 0.13600 (10) | 0.0460 (5) | |
N4 | 0.6614 (3) | −0.2659 (2) | −0.12716 (11) | 0.0547 (5) | |
N5 | 0.2303 (2) | 0.37982 (17) | 0.60142 (9) | 0.0391 (4) | |
N6 | 0.1883 (3) | 0.75943 (18) | 0.81254 (10) | 0.0467 (5) | |
N7 | 0.1723 (3) | 0.80373 (18) | 0.88757 (10) | 0.0476 (5) | |
N8 | 0.1027 (3) | 0.77607 (19) | 1.14823 (11) | 0.0482 (5) | |
N9 | 0.2141 (3) | 0.07060 (18) | 0.54816 (10) | 0.0463 (5) | |
N10 | 0.3172 (3) | 0.40427 (18) | 0.43687 (10) | 0.0473 (5) | |
C1 | 0.4569 (3) | 0.1603 (2) | 0.34775 (13) | 0.0496 (6) | |
H1 | 0.4687 | 0.2476 | 0.3524 | 0.059* | |
C2 | 0.5112 (3) | 0.0899 (2) | 0.28772 (13) | 0.0479 (6) | |
H2 | 0.5584 | 0.1292 | 0.2528 | 0.057* | |
C3 | 0.4947 (3) | −0.0399 (2) | 0.28003 (11) | 0.0357 (5) | |
C4 | 0.4280 (3) | −0.0923 (2) | 0.33454 (12) | 0.0427 (5) | |
H4 | 0.4178 | −0.1788 | 0.3318 | 0.051* | |
C5 | 0.3770 (3) | −0.0150 (2) | 0.39294 (12) | 0.0424 (5) | |
H5 | 0.3328 | −0.0512 | 0.4293 | 0.051* | |
C6 | 0.5414 (3) | −0.1218 (2) | 0.21601 (11) | 0.0368 (5) | |
C7 | 0.6034 (3) | −0.1814 (2) | 0.10807 (12) | 0.0384 (5) | |
C8 | 0.6399 (3) | −0.3348 (2) | −0.01680 (13) | 0.0493 (6) | |
H8A | 0.7298 | −0.3538 | 0.0124 | 0.059* | |
H8B | 0.5254 | −0.3932 | −0.0155 | 0.059* | |
C9 | 0.6775 (3) | −0.3560 (2) | −0.09465 (12) | 0.0414 (5) | |
C10 | 0.7233 (3) | −0.4657 (2) | −0.12957 (14) | 0.0536 (6) | |
H10 | 0.7364 | −0.5256 | −0.1048 | 0.064* | |
C11 | 0.7489 (4) | −0.4846 (3) | −0.20202 (15) | 0.0667 (8) | |
H11 | 0.7769 | −0.5587 | −0.2272 | 0.080* | |
C12 | 0.7329 (4) | −0.3936 (3) | −0.23641 (15) | 0.0669 (8) | |
H12 | 0.7501 | −0.4041 | −0.2852 | 0.080* | |
C13 | 0.6909 (4) | −0.2863 (3) | −0.19721 (14) | 0.0662 (8) | |
H13 | 0.6823 | −0.2236 | −0.2206 | 0.079* | |
C14 | 0.1740 (3) | 0.4841 (2) | 0.60249 (12) | 0.0463 (6) | |
H14 | 0.1413 | 0.4978 | 0.5580 | 0.056* | |
C15 | 0.1623 (3) | 0.5719 (2) | 0.66606 (12) | 0.0459 (6) | |
H15 | 0.1233 | 0.6434 | 0.6644 | 0.055* | |
C16 | 0.2097 (3) | 0.5517 (2) | 0.73299 (11) | 0.0357 (5) | |
C17 | 0.2673 (3) | 0.4439 (2) | 0.73271 (12) | 0.0399 (5) | |
H17 | 0.2996 | 0.4275 | 0.7765 | 0.048* | |
C18 | 0.2756 (3) | 0.3614 (2) | 0.66618 (12) | 0.0418 (5) | |
H18 | 0.3146 | 0.2894 | 0.6663 | 0.050* | |
C19 | 0.1975 (3) | 0.6422 (2) | 0.80140 (11) | 0.0372 (5) | |
C20 | 0.1738 (3) | 0.7084 (2) | 0.91447 (11) | 0.0389 (5) | |
C21 | 0.1475 (4) | 0.8584 (2) | 1.04240 (12) | 0.0491 (6) | |
H21A | 0.2644 | 0.9178 | 1.0457 | 0.059* | |
H21B | 0.0638 | 0.8807 | 1.0119 | 0.059* | |
C22 | 0.0945 (3) | 0.8708 (2) | 1.11793 (12) | 0.0412 (5) | |
C23 | 0.0405 (3) | 0.9770 (2) | 1.15250 (13) | 0.0498 (6) | |
H23 | 0.0338 | 1.0400 | 1.1291 | 0.060* | |
C24 | −0.0031 (3) | 0.9878 (3) | 1.22224 (13) | 0.0546 (7) | |
H24 | −0.0372 | 1.0592 | 1.2471 | 0.066* | |
C25 | 0.0047 (3) | 0.8915 (3) | 1.25428 (13) | 0.0542 (7) | |
H25 | −0.0245 | 0.8961 | 1.3012 | 0.065* | |
C26 | 0.0566 (3) | 0.7878 (3) | 1.21532 (14) | 0.0552 (7) | |
H26 | 0.0597 | 0.7221 | 1.2370 | 0.066* | |
C27 | 0.1457 (3) | −0.0266 (2) | 0.55996 (11) | 0.0337 (5) | |
C28 | 0.3365 (3) | 0.5119 (2) | 0.43828 (11) | 0.0359 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.04687 (10) | 0.02825 (9) | 0.03274 (9) | 0.00628 (7) | 0.00983 (7) | 0.00831 (6) |
S1 | 0.0550 (4) | 0.0423 (3) | 0.0390 (3) | 0.0150 (3) | 0.0140 (3) | 0.0130 (3) |
S2 | 0.0556 (4) | 0.0455 (3) | 0.0360 (3) | 0.0197 (3) | 0.0120 (3) | 0.0132 (3) |
S3 | 0.0468 (3) | 0.0389 (3) | 0.0555 (4) | 0.0063 (3) | 0.0001 (3) | 0.0238 (3) |
S4 | 0.0499 (4) | 0.0337 (3) | 0.0625 (4) | 0.0110 (3) | 0.0040 (3) | 0.0143 (3) |
O1 | 0.0466 (9) | 0.0400 (8) | 0.0388 (8) | 0.0171 (7) | 0.0130 (7) | 0.0135 (7) |
O2 | 0.0500 (9) | 0.0383 (8) | 0.0346 (8) | 0.0180 (7) | 0.0119 (7) | 0.0107 (7) |
N1 | 0.0411 (11) | 0.0363 (10) | 0.0363 (10) | 0.0092 (8) | 0.0075 (8) | 0.0086 (8) |
N2 | 0.0592 (13) | 0.0458 (11) | 0.0394 (11) | 0.0232 (10) | 0.0135 (9) | 0.0148 (9) |
N3 | 0.0586 (13) | 0.0443 (11) | 0.0410 (11) | 0.0227 (10) | 0.0148 (9) | 0.0123 (9) |
N4 | 0.0714 (15) | 0.0547 (13) | 0.0437 (12) | 0.0235 (11) | 0.0118 (10) | 0.0174 (10) |
N5 | 0.0452 (11) | 0.0391 (10) | 0.0350 (10) | 0.0131 (9) | 0.0092 (8) | 0.0120 (8) |
N6 | 0.0681 (14) | 0.0397 (11) | 0.0382 (11) | 0.0214 (10) | 0.0161 (10) | 0.0132 (9) |
N7 | 0.0688 (14) | 0.0428 (11) | 0.0371 (10) | 0.0245 (10) | 0.0157 (10) | 0.0111 (9) |
N8 | 0.0525 (12) | 0.0531 (12) | 0.0460 (12) | 0.0224 (10) | 0.0147 (10) | 0.0169 (10) |
N9 | 0.0463 (12) | 0.0417 (11) | 0.0474 (11) | 0.0025 (9) | 0.0008 (9) | 0.0186 (9) |
N10 | 0.0596 (13) | 0.0342 (11) | 0.0425 (11) | 0.0013 (9) | 0.0056 (9) | 0.0138 (9) |
C1 | 0.0627 (16) | 0.0336 (12) | 0.0535 (15) | 0.0112 (11) | 0.0234 (12) | 0.0132 (11) |
C2 | 0.0576 (15) | 0.0408 (13) | 0.0498 (14) | 0.0123 (11) | 0.0248 (12) | 0.0182 (11) |
C3 | 0.0311 (11) | 0.0398 (12) | 0.0368 (11) | 0.0116 (9) | 0.0056 (9) | 0.0105 (10) |
C4 | 0.0558 (15) | 0.0383 (12) | 0.0404 (13) | 0.0193 (11) | 0.0093 (11) | 0.0156 (10) |
C5 | 0.0550 (15) | 0.0405 (13) | 0.0358 (12) | 0.0161 (11) | 0.0097 (11) | 0.0146 (10) |
C6 | 0.0353 (12) | 0.0407 (12) | 0.0369 (12) | 0.0123 (10) | 0.0055 (9) | 0.0140 (10) |
C7 | 0.0369 (12) | 0.0391 (12) | 0.0381 (12) | 0.0120 (10) | 0.0081 (10) | 0.0072 (10) |
C8 | 0.0620 (16) | 0.0429 (13) | 0.0476 (14) | 0.0180 (12) | 0.0159 (12) | 0.0158 (11) |
C9 | 0.0381 (13) | 0.0395 (12) | 0.0420 (13) | 0.0081 (10) | 0.0063 (10) | 0.0068 (10) |
C10 | 0.0562 (16) | 0.0428 (14) | 0.0556 (16) | 0.0130 (12) | 0.0062 (12) | 0.0052 (12) |
C11 | 0.0673 (19) | 0.0601 (18) | 0.0564 (17) | 0.0156 (15) | 0.0129 (14) | −0.0100 (14) |
C12 | 0.0611 (18) | 0.080 (2) | 0.0378 (14) | 0.0021 (15) | 0.0067 (13) | −0.0032 (14) |
C13 | 0.080 (2) | 0.074 (2) | 0.0424 (15) | 0.0130 (16) | 0.0065 (14) | 0.0222 (14) |
C14 | 0.0586 (16) | 0.0521 (14) | 0.0367 (12) | 0.0241 (12) | 0.0099 (11) | 0.0180 (11) |
C15 | 0.0602 (16) | 0.0480 (14) | 0.0404 (13) | 0.0284 (12) | 0.0124 (11) | 0.0168 (11) |
C16 | 0.0365 (12) | 0.0356 (11) | 0.0379 (12) | 0.0122 (9) | 0.0124 (9) | 0.0117 (9) |
C17 | 0.0490 (14) | 0.0425 (13) | 0.0333 (11) | 0.0177 (11) | 0.0074 (10) | 0.0146 (10) |
C18 | 0.0536 (14) | 0.0387 (12) | 0.0398 (13) | 0.0197 (11) | 0.0123 (11) | 0.0147 (10) |
C19 | 0.0403 (12) | 0.0394 (12) | 0.0357 (12) | 0.0132 (10) | 0.0105 (9) | 0.0142 (10) |
C20 | 0.0433 (13) | 0.0389 (12) | 0.0360 (12) | 0.0159 (10) | 0.0096 (10) | 0.0082 (10) |
C21 | 0.0648 (17) | 0.0458 (14) | 0.0427 (13) | 0.0234 (12) | 0.0146 (12) | 0.0136 (11) |
C22 | 0.0393 (13) | 0.0456 (13) | 0.0368 (12) | 0.0120 (10) | 0.0052 (10) | 0.0088 (10) |
C23 | 0.0575 (16) | 0.0459 (14) | 0.0443 (14) | 0.0185 (12) | 0.0040 (12) | 0.0068 (11) |
C24 | 0.0533 (16) | 0.0557 (16) | 0.0459 (14) | 0.0174 (13) | 0.0078 (12) | −0.0032 (12) |
C25 | 0.0468 (15) | 0.0722 (18) | 0.0390 (13) | 0.0136 (13) | 0.0107 (11) | 0.0100 (13) |
C26 | 0.0578 (16) | 0.0673 (17) | 0.0498 (15) | 0.0212 (14) | 0.0150 (13) | 0.0278 (13) |
C27 | 0.0329 (11) | 0.0389 (12) | 0.0289 (11) | 0.0115 (10) | 0.0031 (9) | 0.0079 (9) |
C28 | 0.0364 (12) | 0.0399 (13) | 0.0279 (11) | 0.0038 (10) | 0.0063 (9) | 0.0106 (9) |
Cd1—N9 | 2.3115 (19) | C2—H2 | 0.9300 |
Cd1—N10 | 2.3348 (19) | C3—C4 | 1.383 (3) |
Cd1—N1 | 2.3550 (17) | C3—C6 | 1.458 (3) |
Cd1—N5 | 2.3630 (18) | C4—C5 | 1.377 (3) |
Cd1—S3i | 2.7172 (7) | C4—H4 | 0.9300 |
Cd1—S4ii | 2.8180 (8) | C5—H5 | 0.9300 |
S1—C7 | 1.736 (2) | C8—C9 | 1.504 (3) |
S1—C8 | 1.813 (2) | C8—H8A | 0.9700 |
S2—C20 | 1.733 (2) | C8—H8B | 0.9700 |
S2—C21 | 1.813 (2) | C9—C10 | 1.382 (3) |
S3—C27 | 1.644 (2) | C10—C11 | 1.380 (4) |
S3—Cd1i | 2.7172 (7) | C10—H10 | 0.9300 |
S4—C28 | 1.644 (2) | C11—C12 | 1.363 (4) |
S4—Cd1ii | 2.8180 (8) | C11—H11 | 0.9300 |
O1—C7 | 1.366 (2) | C12—C13 | 1.370 (4) |
O1—C6 | 1.371 (2) | C12—H12 | 0.9300 |
O2—C20 | 1.367 (2) | C13—H13 | 0.9300 |
O2—C19 | 1.373 (2) | C14—C15 | 1.375 (3) |
N1—C1 | 1.336 (3) | C14—H14 | 0.9300 |
N1—C5 | 1.340 (3) | C15—C16 | 1.393 (3) |
N2—C6 | 1.287 (3) | C15—H15 | 0.9300 |
N2—N3 | 1.409 (2) | C16—C17 | 1.386 (3) |
N3—C7 | 1.293 (3) | C16—C19 | 1.457 (3) |
N4—C9 | 1.330 (3) | C17—C18 | 1.380 (3) |
N4—C13 | 1.343 (3) | C17—H17 | 0.9300 |
N5—C18 | 1.341 (3) | C18—H18 | 0.9300 |
N5—C14 | 1.341 (3) | C21—C22 | 1.509 (3) |
N6—C19 | 1.287 (3) | C21—H21A | 0.9700 |
N6—N7 | 1.415 (2) | C21—H21B | 0.9700 |
N7—C20 | 1.290 (3) | C22—C23 | 1.383 (3) |
N8—C22 | 1.335 (3) | C23—C24 | 1.379 (3) |
N8—C26 | 1.337 (3) | C23—H23 | 0.9300 |
N9—C27 | 1.158 (3) | C24—C25 | 1.371 (4) |
N10—C28 | 1.158 (3) | C24—H24 | 0.9300 |
C1—C2 | 1.375 (3) | C25—C26 | 1.379 (3) |
C1—H1 | 0.9300 | C25—H25 | 0.9300 |
C2—C3 | 1.382 (3) | C26—H26 | 0.9300 |
N9—Cd1—N10 | 173.99 (7) | H8A—C8—H8B | 108.2 |
N9—Cd1—N1 | 90.09 (7) | N4—C9—C10 | 123.0 (2) |
N10—Cd1—N1 | 91.76 (7) | N4—C9—C8 | 116.7 (2) |
N9—Cd1—N5 | 89.47 (7) | C10—C9—C8 | 120.3 (2) |
N10—Cd1—N5 | 89.80 (7) | C11—C10—C9 | 118.5 (3) |
N1—Cd1—N5 | 169.02 (6) | C11—C10—H10 | 120.7 |
N9—Cd1—S3i | 91.71 (5) | C9—C10—H10 | 120.7 |
N10—Cd1—S3i | 82.45 (5) | C12—C11—C10 | 119.4 (3) |
N1—Cd1—S3i | 93.93 (5) | C12—C11—H11 | 120.3 |
N5—Cd1—S3i | 97.05 (5) | C10—C11—H11 | 120.3 |
N9—Cd1—S4ii | 94.70 (5) | C11—C12—C13 | 118.2 (3) |
N10—Cd1—S4ii | 91.17 (5) | C11—C12—H12 | 120.9 |
N1—Cd1—S4ii | 84.64 (5) | C13—C12—H12 | 120.9 |
N5—Cd1—S4ii | 84.46 (5) | N4—C13—C12 | 124.1 (3) |
S3i—Cd1—S4ii | 173.430 (18) | N4—C13—H13 | 118.0 |
C7—S1—C8 | 95.82 (10) | C12—C13—H13 | 118.0 |
C20—S2—C21 | 96.03 (10) | N5—C14—C15 | 123.3 (2) |
C27—S3—Cd1i | 102.98 (8) | N5—C14—H14 | 118.3 |
C28—S4—Cd1ii | 96.46 (8) | C15—C14—H14 | 118.3 |
C7—O1—C6 | 101.94 (16) | C14—C15—C16 | 118.7 (2) |
C20—O2—C19 | 102.03 (16) | C14—C15—H15 | 120.6 |
C1—N1—C5 | 117.10 (19) | C16—C15—H15 | 120.6 |
C1—N1—Cd1 | 119.43 (15) | C17—C16—C15 | 118.56 (19) |
C5—N1—Cd1 | 123.41 (14) | C17—C16—C19 | 121.25 (19) |
C6—N2—N3 | 106.57 (17) | C15—C16—C19 | 120.19 (19) |
C7—N3—N2 | 105.71 (17) | C18—C17—C16 | 118.6 (2) |
C9—N4—C13 | 116.8 (2) | C18—C17—H17 | 120.7 |
C18—N5—C14 | 117.37 (19) | C16—C17—H17 | 120.7 |
C18—N5—Cd1 | 117.87 (14) | N5—C18—C17 | 123.4 (2) |
C14—N5—Cd1 | 124.47 (14) | N5—C18—H18 | 118.3 |
C19—N6—N7 | 106.45 (17) | C17—C18—H18 | 118.3 |
C20—N7—N6 | 105.78 (17) | N6—C19—O2 | 112.60 (18) |
C22—N8—C26 | 116.8 (2) | N6—C19—C16 | 128.50 (19) |
C27—N9—Cd1 | 162.39 (17) | O2—C19—C16 | 118.88 (18) |
C28—N10—Cd1 | 151.60 (17) | N7—C20—O2 | 113.12 (18) |
N1—C1—C2 | 123.5 (2) | N7—C20—S2 | 130.68 (17) |
N1—C1—H1 | 118.2 | O2—C20—S2 | 116.17 (15) |
C2—C1—H1 | 118.2 | C22—C21—S2 | 109.31 (16) |
C1—C2—C3 | 119.0 (2) | C22—C21—H21A | 109.8 |
C1—C2—H2 | 120.5 | S2—C21—H21A | 109.8 |
C3—C2—H2 | 120.5 | C22—C21—H21B | 109.8 |
C2—C3—C4 | 118.0 (2) | S2—C21—H21B | 109.8 |
C2—C3—C6 | 121.88 (19) | H21A—C21—H21B | 108.3 |
C4—C3—C6 | 120.07 (19) | N8—C22—C23 | 123.1 (2) |
C5—C4—C3 | 119.3 (2) | N8—C22—C21 | 117.0 (2) |
C5—C4—H4 | 120.4 | C23—C22—C21 | 119.9 (2) |
C3—C4—H4 | 120.4 | C24—C23—C22 | 118.8 (2) |
N1—C5—C4 | 123.0 (2) | C24—C23—H23 | 120.6 |
N1—C5—H5 | 118.5 | C22—C23—H23 | 120.6 |
C4—C5—H5 | 118.5 | C25—C24—C23 | 118.9 (2) |
N2—C6—O1 | 112.66 (18) | C25—C24—H24 | 120.5 |
N2—C6—C3 | 127.78 (19) | C23—C24—H24 | 120.5 |
O1—C6—C3 | 119.53 (18) | C24—C25—C26 | 118.4 (2) |
N3—C7—O1 | 113.12 (19) | C24—C25—H25 | 120.8 |
N3—C7—S1 | 130.00 (17) | C26—C25—H25 | 120.8 |
O1—C7—S1 | 116.85 (16) | N8—C26—C25 | 123.9 (2) |
C9—C8—S1 | 109.86 (16) | N8—C26—H26 | 118.1 |
C9—C8—H8A | 109.7 | C25—C26—H26 | 118.1 |
S1—C8—H8A | 109.7 | N9—C27—S3 | 178.1 (2) |
C9—C8—H8B | 109.7 | N10—C28—S4 | 179.1 (2) |
S1—C8—H8B | 109.7 | ||
N9—Cd1—N1—C1 | −177.81 (18) | C6—O1—C7—N3 | 0.1 (2) |
N10—Cd1—N1—C1 | 7.92 (18) | C6—O1—C7—S1 | 178.42 (15) |
N5—Cd1—N1—C1 | −90.1 (4) | C8—S1—C7—N3 | 7.3 (2) |
S3i—Cd1—N1—C1 | 90.47 (17) | C8—S1—C7—O1 | −170.74 (17) |
S4ii—Cd1—N1—C1 | −83.10 (17) | C7—S1—C8—C9 | −177.55 (18) |
N9—Cd1—N1—C5 | 5.12 (18) | C13—N4—C9—C10 | 0.4 (4) |
N10—Cd1—N1—C5 | −169.16 (18) | C13—N4—C9—C8 | −178.5 (2) |
N5—Cd1—N1—C5 | 92.8 (3) | S1—C8—C9—N4 | −15.5 (3) |
S3i—Cd1—N1—C5 | −86.60 (17) | S1—C8—C9—C10 | 165.63 (19) |
S4ii—Cd1—N1—C5 | 99.83 (17) | N4—C9—C10—C11 | −1.7 (4) |
C6—N2—N3—C7 | −0.2 (2) | C8—C9—C10—C11 | 177.1 (2) |
N9—Cd1—N5—C18 | 34.99 (17) | C9—C10—C11—C12 | 1.6 (4) |
N10—Cd1—N5—C18 | −150.97 (17) | C10—C11—C12—C13 | −0.2 (4) |
N1—Cd1—N5—C18 | −52.8 (4) | C9—N4—C13—C12 | 1.1 (4) |
S3i—Cd1—N5—C18 | 126.66 (16) | C11—C12—C13—N4 | −1.2 (5) |
S4ii—Cd1—N5—C18 | −59.77 (16) | C18—N5—C14—C15 | 0.5 (3) |
N9—Cd1—N5—C14 | −151.28 (19) | Cd1—N5—C14—C15 | −173.29 (18) |
N10—Cd1—N5—C14 | 22.75 (19) | N5—C14—C15—C16 | −0.5 (4) |
N1—Cd1—N5—C14 | 121.0 (3) | C14—C15—C16—C17 | 0.1 (3) |
S3i—Cd1—N5—C14 | −59.62 (18) | C14—C15—C16—C19 | −179.5 (2) |
S4ii—Cd1—N5—C14 | 113.95 (18) | C15—C16—C17—C18 | 0.2 (3) |
C19—N6—N7—C20 | 0.1 (3) | C19—C16—C17—C18 | 179.8 (2) |
N1—Cd1—N9—C27 | −73.5 (6) | C14—N5—C18—C17 | −0.1 (3) |
N5—Cd1—N9—C27 | 117.5 (6) | Cd1—N5—C18—C17 | 174.04 (18) |
S3i—Cd1—N9—C27 | 20.4 (6) | C16—C17—C18—N5 | −0.2 (4) |
S4ii—Cd1—N9—C27 | −158.1 (6) | N7—N6—C19—O2 | −1.0 (3) |
N1—Cd1—N10—C28 | −156.8 (4) | N7—N6—C19—C16 | 178.0 (2) |
N5—Cd1—N10—C28 | 12.3 (4) | C20—O2—C19—N6 | 1.3 (2) |
S3i—Cd1—N10—C28 | 109.4 (4) | C20—O2—C19—C16 | −177.73 (19) |
S4ii—Cd1—N10—C28 | −72.2 (4) | C17—C16—C19—N6 | 161.9 (2) |
C5—N1—C1—C2 | 1.8 (4) | C15—C16—C19—N6 | −18.5 (4) |
Cd1—N1—C1—C2 | −175.4 (2) | C17—C16—C19—O2 | −19.2 (3) |
N1—C1—C2—C3 | 0.0 (4) | C15—C16—C19—O2 | 160.4 (2) |
C1—C2—C3—C4 | −1.7 (4) | N6—N7—C20—O2 | 0.8 (3) |
C1—C2—C3—C6 | 176.9 (2) | N6—N7—C20—S2 | −176.95 (18) |
C2—C3—C4—C5 | 1.6 (3) | C19—O2—C20—N7 | −1.3 (2) |
C6—C3—C4—C5 | −177.0 (2) | C19—O2—C20—S2 | 176.79 (15) |
C1—N1—C5—C4 | −1.9 (3) | C21—S2—C20—N7 | −5.8 (3) |
Cd1—N1—C5—C4 | 175.20 (17) | C21—S2—C20—O2 | 176.55 (17) |
C3—C4—C5—N1 | 0.3 (4) | C20—S2—C21—C22 | 169.84 (17) |
N3—N2—C6—O1 | 0.2 (3) | C26—N8—C22—C23 | −0.3 (4) |
N3—N2—C6—C3 | 178.5 (2) | C26—N8—C22—C21 | 179.6 (2) |
C7—O1—C6—N2 | −0.2 (2) | S2—C21—C22—N8 | 16.0 (3) |
C7—O1—C6—C3 | −178.63 (19) | S2—C21—C22—C23 | −163.99 (19) |
C2—C3—C6—N2 | 168.0 (2) | N8—C22—C23—C24 | 1.5 (4) |
C4—C3—C6—N2 | −13.4 (4) | C21—C22—C23—C24 | −178.4 (2) |
C2—C3—C6—O1 | −13.8 (3) | C22—C23—C24—C25 | −1.4 (4) |
C4—C3—C6—O1 | 164.8 (2) | C23—C24—C25—C26 | 0.2 (4) |
N2—N3—C7—O1 | 0.1 (3) | C22—N8—C26—C25 | −1.0 (4) |
N2—N3—C7—S1 | −178.03 (17) | C24—C25—C26—N8 | 1.0 (4) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cd(NCS)2(C13H10N4OS)2] |
Mr | 769.18 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 291 |
a, b, c (Å) | 7.8868 (13), 11.1060 (18), 19.050 (4) |
α, β, γ (°) | 104.686 (4), 93.920 (5), 105.202 (3) |
V (Å3) | 1541.2 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.03 |
Crystal size (mm) | 0.50 × 0.21 × 0.12 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.628, 0.887 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11469, 5756, 4955 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.054, 1.02 |
No. of reflections | 5695 |
No. of parameters | 406 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.30 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1994).
Cd1—N9 | 2.3115 (19) | Cd1—N5 | 2.3630 (18) |
Cd1—N10 | 2.3348 (19) | Cd1—S3i | 2.7172 (7) |
Cd1—N1 | 2.3550 (17) | Cd1—S4ii | 2.8180 (8) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y+1, −z+1. |
The formation of coordination polymers has attracted great attention in recent years for their potential applications in separation and selective inclusion, and their ion exchange, catalysis, magnetism and nonlinear optical properties (Moulton & Zaworotko, 2001). 1,3,4-Oxadiazole exhibits the corresponding biological properties, such as antiphlogosis and antisepsis, which has given rise to an extensive variety of applications in both medicine and agriculture. Although many compounds containing symmetrical organic ligands bearing oxadiazole rings have been prepared (Du et al., 2006), as far as is known coordination compounds relative to asymmetrical ligands with oxadiazole groups are uncommon. We purposely synthesized the pyridyl-containing asymmetrical oxadiazole ligand 5-(4-pyridyl-κN)-2-(2-pyridylmethylsulfanyl)-1,3,4-oxadiazole (pmpo). The asymmetrical configuration, coordination variety and flexibility of pmpo are expected to meet metal coordination requirements (Du & Zhao, 2004). The heterocyclic groups in the ligand usually favor packing arrangements via π–π stacking interactions in the solid state (Atoub et al., 2007). Furthermore, thiocyanate, well known for its versatile coordination modes such as monodentate, end bridge and end-to-end bridge, was used in this research. We present here a new CdII thiocyanate complex of the asymmetrical pmpo ligand, [Cd(pmpo)2(SCN)2]n, (I).
The main structural feature of (I) is that the SCN− anions act as end-to-end bridging spacers, linking CdII centers into a double chain structure, with the pmpo ligands bound edgeways; this structure is very similar to those of several reported cadmium(II) thiocyanate complexes with pyridyl-containing oxadiazole ligands (Marsh et al., 2002). The CdII atom in (I) adopts an octahedral coordination geometry, with two S-bonded and two N-bonded thiocyanate ligands in the equatorial plane and two N-bonded 4-pyridyl rings of different pmpo ligands at the axial sites (Fig. 1).
The average Cd—N and Cd—S bond lengths in the equatorial plane are 2.323 (11) and 2.77 (5) Å, respectively, and the average Cd—Npyridyl distance at the axial sites is 2.359 (4) Å, slightly longer than that of Cd—NNCS in the equatorial plane. The average Cd—Npyridyl length is almost the same as that of {is there a value missing here?} {[Cd(bpo)(SCN)2]·(CH3CN)}n [bpo is 2,5-bis(4-pyridyl)-1,3,4-oxodiazole; Du et al. 2002] and slightly shorter than that of 2.463 (2) Å in [Cd(bpo)2(SCN)2] (Du et al., 2006). Furthermore, it is longer than that of 2.2749 (16) Å in [Cd(imH)2(NCS)(SCN)]n (imH is imidazole; Bose et al. 2004). The N—Cd—N bond angles around each CdII center are very close to 90° [mean 90.3 (15)°]; the N—Cd—S angles range from 82.45 (5) to 97.05 (5)°. The multidentate pmpo ligand behaves as a terminal ligand, with the 4-pyridyl group binding the metal center, and its two pyridyl rings subtending to each other a dihedral angle of 20.7°, deviating from the central oxadiazole plane by 14.3 and 6.7°.
Neighboring Cd···Cd distances in a chain are 5.863 (1)–6.019 (1) Å, slightly shorter than previously reported values [e.g. 6.067 (1) Å; Second et al., 2000]. There are two types of eight-membered rings formed by the SCN− anions bridging CdII centers in the same chain. As clearly portrayed in Fig. 1, the ring formed by the two SCN− anions bridging atoms Cd1 and Cd1i is nearly planar, with a mean deviation from the least-square plane of 0.045 Å, while the other ring, constructed by the SCN− anions binding atoms Cd1 and Cd1ii, displays a chair conformation with the corresponding value of 0.222 Å.
Adjacent one-dimensional polymeric chains are linked via two types of interchain π–π stacking interactions (Fig. 2). Type 1 takes place between the oxadiazole and 2-pyridyl rings, with homologous centroid-to-centroid separations of 3.603 (2) and 3.616 (2) Å, while type 2 occurs between two contiguous 4-pyridyl and 2-pyridyl rings, with a similar separation of 3.834 (2) Å. Through these interchain interactions, the one-dimensional polymeric chains stack to form a two-dimensional array.