metal-organic compounds
Bis[2-(1H-pyrazol-3-yl-κN2)pyridine-κN]dithiocyanato-κN,κS-cadmium(II)
aCollege of Science, Civil Aviation University of China, Tianjin 300300, People's Republic of China
*Correspondence e-mail: caihua-1109@163.com
The molecular structure of the mononuclear complex, [Cd(SCN)2(C8H7N3)2], contains a CdII atom in a distorted octahedral coordination defined by five N atoms from two bidentate chelate 2-(1H-pyrazol-3-yl)pyridine ligands and by one SCN− anion. The second SCN− anion provides its S atom for completion of the coordination sphere. The complex is linked to four others by N—H⋯N and N—H⋯S hydrogen-bonding interactions between the pyrazol N—H group and the terminal S and N atoms of neighbouring SCN− anions. This arrangement leads to the formation of sheets parallel to (100). Face-to-face π–π stacking interactions with shortest interplanar distances of 3.805 (2) and 3.696 (2) Å help to consolidate the crystal packing.
Related literature
For background to self assembly in supramolecular chemistry, see: Beatty (2003); Braga et al. (2003); Chen & Liu (2002); Zhang et al. (2004). For related structures, see: Hu et al. (2008).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2003); cell SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536810034604/wm2396sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536810034604/wm2396Isup2.hkl
Complex (I) was obtained by the reaction of Cd(NO3)2.4H2O, 3-(2-pyridyl)pyrazole (L) and NH4SCN in the molar ratio 1: 1: 1 in water (10 ml) under hydrothermal conditions at 393 K for three days. The autoclave was finally cooled down to room temperature at a rate of 5 Kh-1. The resulting solution was filtered and left to stand at room temperature. Colorless block-shaped crystals suitable for X-ray analysis were obtained in about 65% yield by slow evaporation of the solvent over a period of 1 week. Anal. calcd for C18H14CdN8S2: C,41.67; H,2.72, N, 21.59%; found: C, 41.63; H, 2.69; N, 21.54%.
Although all H atoms were visible in difference maps, they were finally placed in geometrically calculated positions, with C—H distances of 0.93Å and N—H distances of 0.86 Å, and included in the final
in the riding model approximation, with Uiso(H) = 1.2Ueq(C, N) for aromatic H atoms.Data collection: APEX2 (Bruker, 2003); cell
SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELX97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).[Cd(NCS)2(C8H7N3)2] | F(000) = 1032 |
Mr = 518.89 | Dx = 1.687 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4275 reflections |
a = 14.4612 (19) Å | θ = 2.5–27.4° |
b = 9.6043 (12) Å | µ = 1.30 mm−1 |
c = 14.9089 (19) Å | T = 296 K |
β = 99.290 (2)° | Block, colourless |
V = 2043.5 (5) Å3 | 0.32 × 0.26 × 0.22 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 3602 independent reflections |
Radiation source: fine-focus sealed tube | 3119 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
phi and ω scans | θmax = 25.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −17→9 |
Tmin = 0.682, Tmax = 0.764 | k = −11→11 |
10166 measured reflections | l = −17→17 |
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) = 0.053 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0226P)2 + 0.5639P] where P = (Fo2 + 2Fc2)/3 |
3602 reflections | (Δ/σ)max = 0.001 |
262 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
[Cd(NCS)2(C8H7N3)2] | V = 2043.5 (5) Å3 |
Mr = 518.89 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.4612 (19) Å | µ = 1.30 mm−1 |
b = 9.6043 (12) Å | T = 296 K |
c = 14.9089 (19) Å | 0.32 × 0.26 × 0.22 mm |
β = 99.290 (2)° |
Bruker APEXII CCD area-detector diffractometer | 3602 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 3119 reflections with I > 2σ(I) |
Tmin = 0.682, Tmax = 0.764 | Rint = 0.022 |
10166 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.053 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.33 e Å−3 |
3602 reflections | Δρmin = −0.24 e Å−3 |
262 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 | 0.229952 (12) | 0.555357 (17) | 0.337364 (11) | 0.03567 (7) | |
S1 | 0.32477 (5) | 1.02032 (7) | 0.45051 (5) | 0.05433 (19) | |
S2 | 0.12657 (5) | 0.57892 (7) | 0.46990 (5) | 0.04796 (17) | |
N1 | 0.10594 (14) | 0.5820 (2) | 0.21453 (13) | 0.0402 (5) | |
N2 | 0.18138 (14) | 0.3329 (2) | 0.27202 (13) | 0.0413 (5) | |
N3 | 0.21610 (16) | 0.2024 (2) | 0.27632 (15) | 0.0510 (6) | |
H3 | 0.2600 | 0.1737 | 0.3182 | 0.061* | |
N4 | 0.34659 (14) | 0.42207 (19) | 0.43362 (13) | 0.0359 (5) | |
N5 | 0.36346 (15) | 0.5293 (2) | 0.26918 (14) | 0.0419 (5) | |
N6 | 0.38935 (16) | 0.5695 (2) | 0.19073 (14) | 0.0481 (5) | |
H6 | 0.3551 | 0.6189 | 0.1501 | 0.058* | |
N7 | 0.25827 (17) | 0.7890 (2) | 0.34656 (15) | 0.0552 (6) | |
N8 | 0.26347 (18) | 0.7180 (3) | 0.59283 (16) | 0.0653 (7) | |
C1 | 0.06579 (19) | 0.7044 (3) | 0.19052 (18) | 0.0494 (7) | |
H1 | 0.0925 | 0.7850 | 0.2179 | 0.059* | |
C2 | −0.0137 (2) | 0.7152 (3) | 0.12667 (19) | 0.0589 (8) | |
H2 | −0.0390 | 0.8020 | 0.1095 | 0.071* | |
C3 | −0.0551 (2) | 0.5966 (4) | 0.0887 (2) | 0.0681 (9) | |
H3A | −0.1102 | 0.6021 | 0.0470 | 0.082* | |
C4 | −0.0156 (2) | 0.4704 (4) | 0.11192 (18) | 0.0590 (8) | |
H4 | −0.0435 | 0.3890 | 0.0868 | 0.071* | |
C5 | 0.06664 (17) | 0.4655 (3) | 0.17354 (16) | 0.0421 (6) | |
C6 | 0.11593 (17) | 0.3351 (3) | 0.19786 (16) | 0.0410 (6) | |
C7 | 0.1093 (2) | 0.2035 (3) | 0.15527 (19) | 0.0589 (8) | |
H7 | 0.0693 | 0.1775 | 0.1027 | 0.071* | |
C8 | 0.1745 (2) | 0.1224 (3) | 0.2080 (2) | 0.0586 (8) | |
H8 | 0.1874 | 0.0293 | 0.1981 | 0.070* | |
C9 | 0.33719 (18) | 0.3731 (2) | 0.51578 (16) | 0.0415 (6) | |
H9 | 0.2809 | 0.3882 | 0.5368 | 0.050* | |
C10 | 0.40707 (19) | 0.3014 (3) | 0.57064 (17) | 0.0454 (6) | |
H10 | 0.3983 | 0.2685 | 0.6273 | 0.054* | |
C11 | 0.4903 (2) | 0.2798 (3) | 0.53915 (18) | 0.0485 (7) | |
H11 | 0.5389 | 0.2325 | 0.5749 | 0.058* | |
C12 | 0.50132 (17) | 0.3284 (2) | 0.45472 (17) | 0.0413 (6) | |
H12 | 0.5573 | 0.3141 | 0.4329 | 0.050* | |
C13 | 0.42789 (16) | 0.3990 (2) | 0.40266 (16) | 0.0354 (5) | |
C14 | 0.43478 (17) | 0.4553 (2) | 0.31247 (16) | 0.0371 (6) | |
C15 | 0.5074 (2) | 0.4489 (3) | 0.26009 (18) | 0.0475 (6) | |
H15 | 0.5648 | 0.4038 | 0.2746 | 0.057* | |
C16 | 0.4754 (2) | 0.5230 (3) | 0.18351 (18) | 0.0510 (7) | |
H16 | 0.5072 | 0.5385 | 0.1350 | 0.061* | |
C17 | 0.28474 (18) | 0.8847 (3) | 0.39008 (17) | 0.0411 (6) | |
C18 | 0.20761 (19) | 0.6625 (3) | 0.54154 (17) | 0.0435 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.03330 (11) | 0.03163 (10) | 0.03974 (11) | 0.00163 (8) | −0.00116 (7) | −0.00255 (8) |
S1 | 0.0605 (5) | 0.0379 (4) | 0.0599 (4) | −0.0038 (3) | −0.0042 (4) | −0.0060 (3) |
S2 | 0.0363 (4) | 0.0557 (4) | 0.0517 (4) | −0.0017 (3) | 0.0065 (3) | −0.0062 (3) |
N1 | 0.0355 (11) | 0.0463 (13) | 0.0389 (11) | 0.0059 (10) | 0.0061 (9) | 0.0059 (9) |
N2 | 0.0411 (12) | 0.0385 (12) | 0.0425 (12) | −0.0033 (10) | 0.0012 (9) | −0.0049 (9) |
N3 | 0.0541 (14) | 0.0407 (13) | 0.0558 (14) | 0.0018 (11) | 0.0014 (11) | 0.0011 (11) |
N4 | 0.0348 (11) | 0.0334 (11) | 0.0375 (11) | 0.0022 (9) | −0.0002 (9) | 0.0004 (8) |
N5 | 0.0401 (12) | 0.0405 (12) | 0.0449 (12) | −0.0012 (10) | 0.0063 (10) | 0.0034 (9) |
N6 | 0.0533 (14) | 0.0481 (13) | 0.0425 (12) | −0.0007 (11) | 0.0067 (10) | 0.0090 (10) |
N7 | 0.0670 (16) | 0.0360 (13) | 0.0611 (15) | −0.0061 (12) | 0.0062 (12) | −0.0068 (11) |
N8 | 0.0662 (17) | 0.0773 (18) | 0.0530 (15) | −0.0144 (15) | 0.0116 (13) | −0.0167 (13) |
C1 | 0.0483 (16) | 0.0484 (16) | 0.0530 (16) | 0.0079 (14) | 0.0130 (13) | 0.0077 (13) |
C2 | 0.0558 (18) | 0.070 (2) | 0.0540 (17) | 0.0284 (17) | 0.0177 (14) | 0.0211 (16) |
C3 | 0.0472 (18) | 0.105 (3) | 0.0520 (18) | 0.0130 (19) | 0.0083 (14) | 0.0102 (18) |
C4 | 0.0439 (17) | 0.086 (2) | 0.0451 (16) | −0.0041 (16) | 0.0013 (13) | 0.0025 (15) |
C5 | 0.0360 (14) | 0.0607 (18) | 0.0296 (12) | −0.0066 (13) | 0.0052 (11) | 0.0008 (12) |
C6 | 0.0412 (15) | 0.0465 (15) | 0.0350 (13) | −0.0099 (12) | 0.0050 (11) | −0.0022 (11) |
C7 | 0.068 (2) | 0.0604 (19) | 0.0467 (16) | −0.0134 (17) | 0.0038 (14) | −0.0142 (14) |
C8 | 0.079 (2) | 0.0358 (15) | 0.0612 (18) | −0.0050 (16) | 0.0124 (16) | −0.0120 (14) |
C9 | 0.0458 (15) | 0.0356 (13) | 0.0418 (14) | −0.0009 (12) | 0.0029 (11) | −0.0029 (11) |
C10 | 0.0586 (18) | 0.0360 (14) | 0.0386 (14) | 0.0024 (13) | −0.0011 (12) | 0.0011 (11) |
C11 | 0.0530 (17) | 0.0361 (14) | 0.0494 (16) | 0.0057 (13) | −0.0131 (13) | −0.0012 (12) |
C12 | 0.0359 (14) | 0.0327 (13) | 0.0529 (15) | 0.0021 (11) | −0.0007 (11) | −0.0064 (11) |
C13 | 0.0351 (13) | 0.0251 (11) | 0.0427 (13) | 0.0004 (10) | −0.0037 (11) | −0.0081 (10) |
C14 | 0.0370 (13) | 0.0307 (13) | 0.0423 (13) | −0.0029 (11) | 0.0027 (11) | −0.0069 (11) |
C15 | 0.0436 (15) | 0.0455 (15) | 0.0545 (16) | 0.0038 (13) | 0.0115 (13) | −0.0060 (13) |
C16 | 0.0557 (18) | 0.0499 (17) | 0.0517 (17) | −0.0015 (14) | 0.0213 (14) | −0.0015 (13) |
C17 | 0.0398 (14) | 0.0332 (13) | 0.0495 (15) | 0.0054 (12) | 0.0052 (11) | 0.0072 (12) |
C18 | 0.0445 (15) | 0.0479 (15) | 0.0404 (14) | 0.0025 (13) | 0.0142 (12) | −0.0024 (12) |
Cd1—N7 | 2.281 (2) | C2—C3 | 1.367 (4) |
Cd1—N5 | 2.336 (2) | C2—H2 | 0.9300 |
Cd1—N1 | 2.361 (2) | C3—C4 | 1.360 (4) |
Cd1—N4 | 2.4004 (18) | C3—H3A | 0.9300 |
Cd1—N2 | 2.406 (2) | C4—C5 | 1.381 (4) |
Cd1—S2 | 2.6730 (8) | C4—H4 | 0.9300 |
S1—C17 | 1.636 (3) | C5—C6 | 1.458 (4) |
S2—C18 | 1.660 (3) | C6—C7 | 1.410 (4) |
N1—C1 | 1.335 (3) | C7—C8 | 1.368 (4) |
N1—C5 | 1.355 (3) | C7—H7 | 0.9300 |
N2—C6 | 1.335 (3) | C8—H8 | 0.9300 |
N2—N3 | 1.348 (3) | C9—C10 | 1.378 (3) |
N3—C8 | 1.339 (3) | C9—H9 | 0.9300 |
N3—H3 | 0.8600 | C10—C11 | 1.376 (4) |
N4—C9 | 1.339 (3) | C10—H10 | 0.9300 |
N4—C13 | 1.349 (3) | C11—C12 | 1.376 (4) |
N5—C14 | 1.331 (3) | C11—H11 | 0.9300 |
N5—N6 | 1.341 (3) | C12—C13 | 1.387 (3) |
N6—C16 | 1.342 (3) | C12—H12 | 0.9300 |
N6—H6 | 0.8600 | C13—C14 | 1.468 (3) |
N7—C17 | 1.154 (3) | C14—C15 | 1.408 (4) |
N8—C18 | 1.150 (3) | C15—C16 | 1.362 (4) |
C1—C2 | 1.372 (4) | C15—H15 | 0.9300 |
C1—H1 | 0.9300 | C16—H16 | 0.9300 |
N7—Cd1—N5 | 88.76 (8) | C2—C3—H3A | 120.0 |
N7—Cd1—N1 | 92.68 (8) | C3—C4—C5 | 118.7 (3) |
N5—Cd1—N1 | 104.58 (7) | C3—C4—H4 | 120.6 |
N7—Cd1—N4 | 112.75 (7) | C5—C4—H4 | 120.6 |
N5—Cd1—N4 | 69.68 (7) | N1—C5—C4 | 121.7 (3) |
N1—Cd1—N4 | 153.36 (7) | N1—C5—C6 | 116.4 (2) |
N7—Cd1—N2 | 159.38 (7) | C4—C5—C6 | 121.9 (3) |
N5—Cd1—N2 | 86.36 (7) | N2—C6—C7 | 110.3 (2) |
N1—Cd1—N2 | 69.29 (7) | N2—C6—C5 | 118.2 (2) |
N4—Cd1—N2 | 84.23 (6) | C7—C6—C5 | 131.5 (2) |
N7—Cd1—S2 | 89.35 (6) | C8—C7—C6 | 105.1 (2) |
N5—Cd1—S2 | 158.58 (5) | C8—C7—H7 | 127.4 |
N1—Cd1—S2 | 96.82 (5) | C6—C7—H7 | 127.4 |
N4—Cd1—S2 | 91.50 (5) | N3—C8—C7 | 107.1 (2) |
N2—Cd1—S2 | 102.30 (5) | N3—C8—H8 | 126.5 |
C18—S2—Cd1 | 95.48 (9) | C7—C8—H8 | 126.5 |
C1—N1—C5 | 118.3 (2) | N4—C9—C10 | 123.1 (2) |
C1—N1—Cd1 | 123.13 (17) | N4—C9—H9 | 118.5 |
C5—N1—Cd1 | 118.12 (15) | C10—C9—H9 | 118.5 |
C6—N2—N3 | 105.2 (2) | C11—C10—C9 | 118.1 (2) |
C6—N2—Cd1 | 116.32 (16) | C11—C10—H10 | 121.0 |
N3—N2—Cd1 | 136.43 (16) | C9—C10—H10 | 121.0 |
C8—N3—N2 | 112.3 (2) | C12—C11—C10 | 119.9 (2) |
C8—N3—H3 | 123.9 | C12—C11—H11 | 120.1 |
N2—N3—H3 | 123.9 | C10—C11—H11 | 120.1 |
C9—N4—C13 | 118.5 (2) | C11—C12—C13 | 119.1 (2) |
C9—N4—Cd1 | 124.66 (16) | C11—C12—H12 | 120.5 |
C13—N4—Cd1 | 116.77 (15) | C13—C12—H12 | 120.5 |
C14—N5—N6 | 105.9 (2) | N4—C13—C12 | 121.3 (2) |
C14—N5—Cd1 | 118.45 (16) | N4—C13—C14 | 116.4 (2) |
N6—N5—Cd1 | 135.67 (16) | C12—C13—C14 | 122.3 (2) |
N5—N6—C16 | 111.5 (2) | N5—C14—C15 | 110.1 (2) |
N5—N6—H6 | 124.2 | N5—C14—C13 | 118.7 (2) |
C16—N6—H6 | 124.2 | C15—C14—C13 | 131.2 (2) |
C17—N7—Cd1 | 149.0 (2) | C16—C15—C14 | 105.0 (2) |
N1—C1—C2 | 122.1 (3) | C16—C15—H15 | 127.5 |
N1—C1—H1 | 118.9 | C14—C15—H15 | 127.5 |
C2—C1—H1 | 118.9 | N6—C16—C15 | 107.5 (2) |
C3—C2—C1 | 119.1 (3) | N6—C16—H16 | 126.2 |
C3—C2—H2 | 120.5 | C15—C16—H16 | 126.2 |
C1—C2—H2 | 120.5 | N7—C17—S1 | 178.5 (3) |
C4—C3—C2 | 120.0 (3) | N8—C18—S2 | 178.3 (3) |
C4—C3—H3A | 120.0 | ||
N7—Cd1—S2—C18 | −51.87 (11) | N4—Cd1—N7—C17 | −36.8 (5) |
N5—Cd1—S2—C18 | 33.09 (17) | N2—Cd1—N7—C17 | 179.6 (3) |
N1—Cd1—S2—C18 | −144.49 (11) | S2—Cd1—N7—C17 | 54.5 (4) |
N4—Cd1—S2—C18 | 60.87 (10) | C5—N1—C1—C2 | 0.5 (4) |
N2—Cd1—S2—C18 | 145.29 (10) | Cd1—N1—C1—C2 | −171.50 (19) |
N7—Cd1—N1—C1 | −14.5 (2) | N1—C1—C2—C3 | 2.4 (4) |
N5—Cd1—N1—C1 | −103.9 (2) | C1—C2—C3—C4 | −2.4 (4) |
N4—Cd1—N1—C1 | −177.50 (17) | C2—C3—C4—C5 | −0.4 (4) |
N2—Cd1—N1—C1 | 175.8 (2) | C1—N1—C5—C4 | −3.4 (4) |
S2—Cd1—N1—C1 | 75.21 (19) | Cd1—N1—C5—C4 | 168.96 (19) |
N7—Cd1—N1—C5 | 173.55 (18) | C1—N1—C5—C6 | 176.5 (2) |
N5—Cd1—N1—C5 | 84.13 (18) | Cd1—N1—C5—C6 | −11.2 (3) |
N4—Cd1—N1—C5 | 10.5 (3) | C3—C4—C5—N1 | 3.4 (4) |
N2—Cd1—N1—C5 | 3.83 (16) | C3—C4—C5—C6 | −176.5 (3) |
S2—Cd1—N1—C5 | −96.78 (17) | N3—N2—C6—C7 | 0.3 (3) |
N7—Cd1—N2—C6 | −25.9 (3) | Cd1—N2—C6—C7 | 166.79 (17) |
N5—Cd1—N2—C6 | −102.57 (18) | N3—N2—C6—C5 | −178.5 (2) |
N1—Cd1—N2—C6 | 4.50 (16) | Cd1—N2—C6—C5 | −12.0 (3) |
N4—Cd1—N2—C6 | −172.49 (18) | N1—C5—C6—N2 | 15.5 (3) |
S2—Cd1—N2—C6 | 97.23 (17) | C4—C5—C6—N2 | −164.6 (2) |
N7—Cd1—N2—N3 | 135.1 (3) | N1—C5—C6—C7 | −162.9 (3) |
N5—Cd1—N2—N3 | 58.4 (2) | C4—C5—C6—C7 | 17.0 (4) |
N1—Cd1—N2—N3 | 165.5 (2) | N2—C6—C7—C8 | −0.1 (3) |
N4—Cd1—N2—N3 | −11.5 (2) | C5—C6—C7—C8 | 178.5 (3) |
S2—Cd1—N2—N3 | −101.8 (2) | N2—N3—C8—C7 | 0.4 (3) |
C6—N2—N3—C8 | −0.4 (3) | C6—C7—C8—N3 | −0.2 (3) |
Cd1—N2—N3—C8 | −162.8 (2) | C13—N4—C9—C10 | 0.7 (3) |
N7—Cd1—N4—C9 | 98.66 (19) | Cd1—N4—C9—C10 | −177.48 (18) |
N5—Cd1—N4—C9 | 178.3 (2) | N4—C9—C10—C11 | 0.2 (4) |
N1—Cd1—N4—C9 | −99.8 (2) | C9—C10—C11—C12 | −0.6 (4) |
N2—Cd1—N4—C9 | −93.47 (18) | C10—C11—C12—C13 | 0.1 (4) |
S2—Cd1—N4—C9 | 8.74 (18) | C9—N4—C13—C12 | −1.1 (3) |
N7—Cd1—N4—C13 | −79.53 (17) | Cd1—N4—C13—C12 | 177.16 (16) |
N5—Cd1—N4—C13 | 0.09 (15) | C9—N4—C13—C14 | −179.73 (19) |
N1—Cd1—N4—C13 | 82.1 (2) | Cd1—N4—C13—C14 | −1.4 (2) |
N2—Cd1—N4—C13 | 88.34 (16) | C11—C12—C13—N4 | 0.8 (3) |
S2—Cd1—N4—C13 | −169.45 (15) | C11—C12—C13—C14 | 179.3 (2) |
N7—Cd1—N5—C14 | 116.27 (17) | N6—N5—C14—C15 | 0.1 (3) |
N1—Cd1—N5—C14 | −151.29 (16) | Cd1—N5—C14—C15 | 178.69 (15) |
N4—Cd1—N5—C14 | 1.41 (16) | N6—N5—C14—C13 | 178.68 (19) |
N2—Cd1—N5—C14 | −83.78 (17) | Cd1—N5—C14—C13 | −2.7 (3) |
S2—Cd1—N5—C14 | 31.2 (3) | N4—C13—C14—N5 | 2.8 (3) |
N7—Cd1—N5—N6 | −65.6 (2) | C12—C13—C14—N5 | −175.8 (2) |
N1—Cd1—N5—N6 | 26.8 (2) | N4—C13—C14—C15 | −179.0 (2) |
N4—Cd1—N5—N6 | 179.5 (2) | C12—C13—C14—C15 | 2.4 (4) |
N2—Cd1—N5—N6 | 94.3 (2) | N5—C14—C15—C16 | 0.0 (3) |
S2—Cd1—N5—N6 | −150.72 (17) | C13—C14—C15—C16 | −178.4 (2) |
C14—N5—N6—C16 | −0.1 (3) | N5—N6—C16—C15 | 0.1 (3) |
Cd1—N5—N6—C16 | −178.39 (18) | C14—C15—C16—N6 | −0.1 (3) |
N5—Cd1—N7—C17 | −104.2 (4) | Cd1—N7—C17—S1 | 107 (9) |
N1—Cd1—N7—C17 | 151.3 (4) | Cd1—S2—C18—N8 | −129 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···S1i | 0.86 | 2.52 | 3.310 (2) | 153 |
N6—H6···N8ii | 0.86 | 2.14 | 2.958 (3) | 159 |
Symmetry codes: (i) x, y−1, z; (ii) x, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cd(NCS)2(C8H7N3)2] |
Mr | 518.89 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 14.4612 (19), 9.6043 (12), 14.9089 (19) |
β (°) | 99.290 (2) |
V (Å3) | 2043.5 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.30 |
Crystal size (mm) | 0.32 × 0.26 × 0.22 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.682, 0.764 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10166, 3602, 3119 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.053, 1.05 |
No. of reflections | 3602 |
No. of parameters | 262 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.24 |
Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2003), SHELX97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2006), SHELXTL (Sheldrick, 2008).
Cd1—N7 | 2.281 (2) | Cd1—N4 | 2.4004 (18) |
Cd1—N5 | 2.336 (2) | Cd1—N2 | 2.406 (2) |
Cd1—N1 | 2.361 (2) | Cd1—S2 | 2.6730 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···S1i | 0.86 | 2.52 | 3.310 (2) | 153.2 |
N6—H6···N8ii | 0.86 | 2.14 | 2.958 (3) | 159.1 |
Symmetry codes: (i) x, y−1, z; (ii) x, −y+3/2, z−1/2. |
Acknowledgements
We acknowledge financial support by the Special Fund for Central Universities (ZXH2009D011).
References
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Self-assembly processes directed by either hydrogen-bonding interactions or metal coordination have been extensively utilized in crystal engineering to construct supramolecular systems with novel structures and properties due to their inherent strength and reliability (Braga et al., 2003; Chen & Liu, 2002; Zhang et al., 2004). Proper selection of metal ions and ligands with suitable functionalized groups is the key issue in designing and self-assembling of molecules (Beatty, 2003). Very recently, we have initiated to utilize a multifunctional organic ligand, namely 3-(2-pyridyl)pyrazole (L), which acts as a simple bidentate chelate ligand, similar to 2,2'-bipyridine or 1,10-phenanthroline, to create a series of interesting metal-organic frameworks (Hu et al., 2008). In the present paper, we report the crystal structure of the title compound (I), a new CdII complex based on the ligand L with additional SCN- anions present.
In the molecular structure of the mononuclear complex (Fig. 1), the CdII atom is six-coordinated in a distorted octahedral geometry by five N atoms from one monodentate SCN- anion and two bidentate chelating ligands L, and by one S atom from another SCN- anion. The equatorial plane is defined by the SCN- N atom, and three N atoms of the L ligands. The axial positions are occupied by one pyrazole N atom of a L ligand and the S atom the second SCN- anion. The L ligand deviates slightly from planarity; the pyridyl and pyrazole rings make dihedral angles of 16.6 (2) and 3.3 (2)°, respectively. The L molecule adopts a bidentate chelate mode, in order to favor hydrogen bonding between the uncoordinated pyrazole N atoms and thiocyanate groups ligand. Each uncoordinated pyrazole N atom generates a hydrogen bond with two N and S atoms of the thiocyanate group. Furthermore, each complex is linked to four others, forming a (100) sheet, by N—H···N and N—H···S hydrogen bonding (Fig. 2). Face-to-face π-π stacking interactions between pyridyl-pyrazole and pyridyl-pyridyl rings link each sheet to two adjacent sheets, hence forming a three dimensional array (Fig. 3). The centroid-to-centroid distances between two neighboring almost parallel pyridyl-pyrazole rings are 3.805 (2) and 3.696 (2) Å, respectively.