Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801001416/ya6003sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801001416/ya6003Isup2.hkl |
CCDC reference: 159837
The synthesis of the title complex was effected by adding 10 ml of aqueous mixture of PdCl2 (0.025 M) and NaSCN (2 M) to 10 ml of 0.1 M solution of DB18C6 in 1,2-dichloroethane. The reaction mixture was stirred for 2 h at room temperature and then filtered. The precipitate was dissolved in acetone. M. p. 485–487 K. Found: C 47.51, H 4.25, N 4.72, S 11.23%; C44H48Na2N4O12PdS4 requires: C 47.79, H 4.38, N 5.07, S 11.58%. Selected FT—IR n/cm-1: 2920, 2850, 2111, 1695, 1595, 1504, 1251, 1213, 1125, 960, 940, 751. The single-crystal was obtained from 4:1 diethyl ether/acetone solution.
The H atoms were located in the difference map and were refined isotropically; the C—H bond lengths span the range 0.88–1.08 Å.
Data collection: CAD-4 Manual (Enraf-Nonius, 1988); cell refinement: CAD-4 Manual; data reduction: SDP-Plus (Frenz, 1985); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1996); software used to prepare material for publication: SHELXL97.
[Na(C20H24O6)]2[Pd(SCN)4] | Z = 1 |
Mr = 1105.48 | F(000) = 560 |
Triclinic, P1 | Dx = 1.487 Mg m−3 |
a = 11.5695 (10) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.568 (3) Å | Cell parameters from 25 reflections |
c = 12.976 (2) Å | θ = 10.5–13.5° |
α = 81.58 (2)° | µ = 0.63 mm−1 |
β = 104.804 (10)° | T = 293 K |
γ = 96.85 (2)° | Prism, orange |
V = 1225.7 (5) Å3 | 0.60 × 0.50 × 0.40 mm |
Enraf-Nonius CAD-4 diffractometer | 3190 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.020 |
Graphite monochromator | θmax = 25.2°, θmin = 1.6° |
θ/2θ scans | h = −13→13 |
Absorption correction: ψ scan (North et al., 1968) | k = −10→10 |
Tmin = 0.834, Tmax = 0.884 | l = 0→15 |
4622 measured reflections | 3 standard reflections every 200 reflections |
4406 independent reflections | intensity decay: 5.0% |
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)] = 0.028 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.080 | All H-atom parameters refined |
S = 1.0 | w = 1/[σ2(Fo2) + (0.0375P)2 + 0.4501P] where P = (Fo2 + 2Fc2)/3 |
4406 reflections | (Δ/σ)max < 0.001 |
400 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.43 e Å−3 |
[Na(C20H24O6)]2[Pd(SCN)4] | γ = 96.85 (2)° |
Mr = 1105.48 | V = 1225.7 (5) Å3 |
Triclinic, P1 | Z = 1 |
a = 11.5695 (10) Å | Mo Kα radiation |
b = 8.568 (3) Å | µ = 0.63 mm−1 |
c = 12.976 (2) Å | T = 293 K |
α = 81.58 (2)° | 0.60 × 0.50 × 0.40 mm |
β = 104.804 (10)° |
Enraf-Nonius CAD-4 diffractometer | 3190 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.020 |
Tmin = 0.834, Tmax = 0.884 | 3 standard reflections every 200 reflections |
4622 measured reflections | intensity decay: 5.0% |
4406 independent reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.080 | All H-atom parameters refined |
S = 1.0 | Δρmax = 0.41 e Å−3 |
4406 reflections | Δρmin = −0.43 e Å−3 |
400 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 | ||
Pd1 | 0.5000 | 0.5000 | 0.5000 | 0.04075 (11) | |
S1 | 0.44659 (8) | 0.43541 (12) | 0.32522 (7) | 0.0645 (2) | |
S2 | 0.68440 (7) | 0.39662 (11) | 0.52685 (6) | 0.0588 (2) | |
Na1 | 0.76645 (10) | 0.12092 (14) | 0.27043 (10) | 0.0570 (3) | |
N1 | 0.6354 (3) | 0.3245 (4) | 0.2641 (2) | 0.0748 (8) | |
N2 | 0.7893 (3) | 0.3538 (5) | 0.7474 (3) | 0.0971 (12) | |
O1 | 0.78730 (18) | 0.0540 (2) | 0.47380 (16) | 0.0538 (5) | |
O2 | 0.93244 (18) | 0.2640 (2) | 0.40380 (16) | 0.0555 (5) | |
O3 | 0.91422 (19) | 0.3214 (2) | 0.18705 (16) | 0.0590 (5) | |
O4 | 0.7735 (2) | 0.1203 (3) | 0.05228 (17) | 0.0663 (6) | |
O5 | 0.6207 (2) | −0.0745 (3) | 0.11971 (18) | 0.0660 (6) | |
O6 | 0.60868 (18) | −0.0860 (3) | 0.32723 (18) | 0.0633 (6) | |
C1 | 0.5615 (3) | 0.3706 (4) | 0.2935 (2) | 0.0559 (8) | |
C2 | 0.7444 (3) | 0.3723 (4) | 0.6585 (3) | 0.0618 (9) | |
C3 | 0.8901 (3) | 0.0918 (4) | 0.5487 (2) | 0.0516 (7) | |
C4 | 0.9705 (3) | 0.2065 (4) | 0.5094 (2) | 0.0512 (7) | |
C5 | 1.0079 (3) | 0.3870 (4) | 0.3608 (3) | 0.0597 (8) | |
C6 | 0.9386 (3) | 0.4480 (4) | 0.2522 (3) | 0.0637 (9) | |
C7 | 0.8642 (4) | 0.3736 (5) | 0.0779 (3) | 0.0795 (12) | |
C8 | 0.8562 (4) | 0.2399 (6) | 0.0159 (3) | 0.0816 (12) | |
C9 | 0.7500 (3) | −0.0184 (5) | 0.0064 (2) | 0.0648 (9) | |
C10 | 0.6663 (3) | −0.1251 (4) | 0.0440 (2) | 0.0613 (8) | |
C11 | 0.5300 (3) | −0.1745 (5) | 0.1586 (3) | 0.0732 (10) | |
C12 | 0.5021 (3) | −0.0968 (5) | 0.2421 (3) | 0.0720 (10) | |
C13 | 0.5856 (3) | −0.0474 (5) | 0.4219 (3) | 0.0644 (9) | |
C14 | 0.6979 (3) | −0.0548 (4) | 0.5094 (3) | 0.0616 (8) | |
C112 | 0.9188 (4) | 0.0279 (5) | 0.6542 (3) | 0.0659 (9) | |
C113 | 1.0262 (4) | 0.0779 (6) | 0.7219 (3) | 0.0797 (12) | |
C114 | 1.1050 (4) | 0.1858 (5) | 0.6840 (3) | 0.0758 (11) | |
C115 | 1.0785 (3) | 0.2522 (5) | 0.5776 (3) | 0.0640 (9) | |
C121 | 0.8011 (5) | −0.0554 (7) | −0.0702 (3) | 0.0870 (13) | |
C122 | 0.7706 (5) | −0.2001 (8) | −0.1086 (4) | 0.1013 (16) | |
C123 | 0.6900 (6) | −0.3057 (7) | −0.0710 (3) | 0.0957 (16) | |
C124 | 0.6355 (4) | −0.2698 (5) | 0.0046 (3) | 0.0807 (12) | |
H1 | 1.026 (3) | 0.485 (4) | 0.405 (2) | 0.063 (9)* | |
H2 | 1.083 (3) | 0.337 (4) | 0.353 (3) | 0.071 (10)* | |
H3 | 0.863 (4) | 0.486 (4) | 0.254 (3) | 0.088 (12)* | |
H4 | 0.983 (3) | 0.534 (4) | 0.219 (3) | 0.061 (9)* | |
H5 | 0.782 (4) | 0.413 (5) | 0.069 (3) | 0.097 (14)* | |
H6 | 0.911 (3) | 0.459 (4) | 0.053 (3) | 0.065 (10)* | |
H7 | 0.823 (3) | 0.268 (5) | −0.058 (3) | 0.089 (12)* | |
H8 | 0.938 (4) | 0.181 (4) | 0.031 (3) | 0.086 (12)* | |
H9 | 0.461 (3) | −0.193 (4) | 0.102 (3) | 0.071 (10)* | |
H10 | 0.470 (3) | 0.019 (4) | 0.214 (3) | 0.064 (10)* | |
H11 | 0.561 (3) | −0.282 (4) | 0.191 (3) | 0.068 (10)* | |
H12 | 0.445 (3) | −0.166 (4) | 0.276 (3) | 0.074 (10)* | |
H13 | 0.559 (3) | 0.066 (4) | 0.400 (3) | 0.065 (9)* | |
H14 | 0.523 (3) | −0.126 (4) | 0.441 (2) | 0.059 (9)* | |
H15 | 0.681 (3) | −0.017 (4) | 0.573 (3) | 0.076 (11)* | |
H16 | 0.725 (3) | −0.162 (4) | 0.523 (3) | 0.070 (10)* | |
H112 | 0.870 (3) | −0.053 (4) | 0.674 (2) | 0.050 (9)* | |
H113 | 1.047 (3) | 0.035 (4) | 0.795 (3) | 0.084 (12)* | |
H114 | 1.179 (4) | 0.214 (5) | 0.727 (3) | 0.087 (12)* | |
H115 | 1.128 (3) | 0.326 (4) | 0.547 (2) | 0.052 (9)* | |
H121 | 0.857 (4) | 0.012 (5) | −0.092 (3) | 0.093 (15)* | |
H122 | 0.810 (4) | −0.237 (6) | −0.162 (4) | 0.132 (18)* | |
H123 | 0.667 (4) | −0.403 (6) | −0.087 (4) | 0.120 (19)* | |
H124 | 0.578 (3) | −0.334 (5) | 0.035 (3) | 0.081 (13)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.03754 (17) | 0.04263 (19) | 0.04051 (18) | −0.00244 (12) | 0.00870 (13) | −0.00607 (13) |
S1 | 0.0550 (5) | 0.0935 (7) | 0.0476 (5) | 0.0151 (4) | 0.0045 (4) | −0.0237 (4) |
S2 | 0.0434 (4) | 0.0789 (6) | 0.0549 (5) | 0.0117 (4) | 0.0079 (3) | −0.0125 (4) |
Na1 | 0.0530 (7) | 0.0594 (7) | 0.0609 (7) | 0.0007 (6) | 0.0214 (6) | −0.0049 (6) |
N1 | 0.073 (2) | 0.095 (2) | 0.0640 (19) | 0.0219 (17) | 0.0190 (16) | −0.0170 (16) |
N2 | 0.0637 (19) | 0.156 (4) | 0.058 (2) | 0.016 (2) | 0.0078 (16) | 0.023 (2) |
O1 | 0.0520 (12) | 0.0596 (12) | 0.0502 (12) | −0.0016 (10) | 0.0177 (10) | −0.0037 (10) |
O2 | 0.0507 (11) | 0.0590 (13) | 0.0549 (13) | −0.0069 (10) | 0.0130 (10) | −0.0095 (10) |
O3 | 0.0681 (14) | 0.0531 (12) | 0.0517 (12) | −0.0008 (10) | 0.0140 (10) | 0.0012 (10) |
O4 | 0.0652 (14) | 0.0805 (16) | 0.0532 (13) | −0.0068 (12) | 0.0191 (11) | −0.0099 (12) |
O5 | 0.0658 (14) | 0.0654 (14) | 0.0666 (14) | −0.0078 (11) | 0.0198 (12) | −0.0109 (11) |
O6 | 0.0478 (12) | 0.0802 (15) | 0.0658 (14) | −0.0072 (11) | 0.0242 (11) | −0.0133 (12) |
C1 | 0.063 (2) | 0.0587 (19) | 0.0423 (16) | 0.0036 (15) | 0.0064 (15) | −0.0067 (14) |
C2 | 0.0376 (16) | 0.076 (2) | 0.067 (2) | 0.0036 (15) | 0.0131 (15) | 0.0077 (17) |
C3 | 0.0582 (18) | 0.0510 (17) | 0.0503 (17) | 0.0180 (14) | 0.0127 (14) | −0.0109 (14) |
C4 | 0.0507 (16) | 0.0554 (18) | 0.0525 (17) | 0.0143 (14) | 0.0111 (14) | −0.0171 (14) |
C5 | 0.0540 (19) | 0.0524 (18) | 0.073 (2) | −0.0080 (15) | 0.0187 (16) | −0.0138 (16) |
C6 | 0.066 (2) | 0.0453 (18) | 0.077 (2) | −0.0071 (16) | 0.0199 (19) | −0.0033 (17) |
C7 | 0.097 (3) | 0.071 (3) | 0.058 (2) | −0.013 (2) | 0.018 (2) | 0.0178 (19) |
C8 | 0.091 (3) | 0.104 (3) | 0.044 (2) | −0.012 (2) | 0.023 (2) | 0.008 (2) |
C9 | 0.065 (2) | 0.086 (3) | 0.0388 (17) | 0.0132 (18) | 0.0014 (15) | −0.0082 (16) |
C10 | 0.065 (2) | 0.069 (2) | 0.0451 (17) | 0.0145 (17) | −0.0036 (15) | −0.0134 (15) |
C11 | 0.058 (2) | 0.074 (3) | 0.079 (3) | −0.0173 (19) | 0.0087 (19) | −0.013 (2) |
C12 | 0.0433 (18) | 0.089 (3) | 0.080 (3) | −0.0150 (18) | 0.0181 (17) | −0.009 (2) |
C13 | 0.0566 (19) | 0.071 (2) | 0.072 (2) | −0.0082 (18) | 0.0353 (18) | −0.0046 (18) |
C14 | 0.065 (2) | 0.063 (2) | 0.064 (2) | 0.0025 (17) | 0.0347 (18) | 0.0028 (17) |
C112 | 0.080 (3) | 0.064 (2) | 0.057 (2) | 0.023 (2) | 0.0179 (19) | −0.0030 (17) |
C113 | 0.094 (3) | 0.092 (3) | 0.051 (2) | 0.045 (3) | −0.001 (2) | −0.009 (2) |
C114 | 0.069 (2) | 0.086 (3) | 0.071 (3) | 0.030 (2) | −0.007 (2) | −0.031 (2) |
C115 | 0.056 (2) | 0.067 (2) | 0.070 (2) | 0.0102 (17) | 0.0066 (18) | −0.0246 (18) |
C121 | 0.091 (3) | 0.121 (4) | 0.051 (2) | 0.012 (3) | 0.015 (2) | −0.021 (2) |
C122 | 0.123 (4) | 0.136 (5) | 0.052 (2) | 0.040 (4) | 0.013 (3) | −0.025 (3) |
C123 | 0.140 (5) | 0.090 (3) | 0.050 (2) | 0.035 (3) | −0.009 (3) | −0.019 (2) |
C124 | 0.103 (3) | 0.077 (3) | 0.053 (2) | 0.012 (2) | −0.001 (2) | −0.013 (2) |
Pd1—S1i | 2.3241 (9) | C6—H4 | 0.96 (3) |
Pd1—S1 | 2.3241 (9) | C7—C8 | 1.474 (6) |
Pd1—S2 | 2.3319 (8) | C7—H5 | 1.02 (4) |
Pd1—S2i | 2.3319 (8) | C7—H6 | 0.93 (4) |
S1—C1 | 1.663 (4) | C8—H7 | 0.95 (4) |
S2—C2 | 1.664 (4) | C8—H8 | 1.08 (4) |
Na1—N1 | 2.423 (3) | C9—C121 | 1.368 (5) |
Na1—O1 | 2.572 (2) | C9—C10 | 1.383 (5) |
Na1—O2 | 2.559 (2) | C10—C124 | 1.383 (5) |
Na1—O3 | 2.597 (2) | C11—C12 | 1.471 (6) |
Na1—O4 | 2.853 (2) | C11—H9 | 0.95 (3) |
Na1—O5 | 2.841 (3) | C11—H11 | 1.02 (3) |
Na1—O6 | 2.559 (2) | C12—H10 | 1.08 (3) |
Na1—C113ii | 3.077 (4) | C12—H12 | 0.98 (4) |
Na1—C114ii | 3.082 (4) | C13—C14 | 1.492 (5) |
N1—C1 | 1.151 (4) | C13—H13 | 1.03 (3) |
N2—C2 | 1.133 (4) | C13—H14 | 0.98 (3) |
O1—C3 | 1.368 (4) | C14—H15 | 1.00 (4) |
O1—C14 | 1.428 (4) | C14—H16 | 0.99 (4) |
O2—C4 | 1.364 (4) | C112—C113 | 1.388 (6) |
O2—C5 | 1.428 (4) | C112—H112 | 0.89 (3) |
O3—C7 | 1.413 (4) | C113—C114 | 1.350 (6) |
O3—C6 | 1.430 (4) | C113—Na1ii | 3.077 (4) |
O4—C9 | 1.374 (4) | C113—H113 | 0.94 (4) |
O4—C8 | 1.430 (4) | C114—C115 | 1.385 (6) |
O5—C10 | 1.370 (4) | C114—Na1ii | 3.082 (4) |
O5—C11 | 1.420 (4) | C114—H114 | 0.92 (4) |
O6—C13 | 1.413 (4) | C115—H115 | 0.91 (3) |
O6—C12 | 1.434 (4) | C121—C122 | 1.378 (7) |
C3—C112 | 1.370 (5) | C121—H121 | 0.89 (4) |
C3—C4 | 1.403 (4) | C122—C123 | 1.352 (8) |
C4—C115 | 1.384 (4) | C122—H122 | 1.02 (5) |
C5—C6 | 1.486 (5) | C123—C124 | 1.381 (7) |
C5—H1 | 1.06 (3) | C123—H123 | 0.88 (5) |
C5—H2 | 1.05 (4) | C124—H124 | 0.94 (4) |
C6—H3 | 0.98 (4) | ||
S1i—Pd1—S1 | 180.0 | O3—C6—H3 | 109 (2) |
S1i—Pd1—S2 | 90.15 (3) | C5—C6—H3 | 112 (2) |
S1—Pd1—S2 | 89.85 (3) | O3—C6—H4 | 108.5 (19) |
S2—Pd1—S2i | 180.0 | C5—C6—H4 | 111.7 (19) |
O2—Na1—O3 | 64.23 (7) | H3—C6—H4 | 107 (3) |
O2—Na1—O1 | 59.40 (7) | O3—C7—C8 | 107.9 (3) |
O3—Na1—O4 | 59.83 (7) | O3—C7—H5 | 110 (2) |
O5—Na1—O4 | 52.46 (7) | C8—C7—H5 | 112 (2) |
O6—Na1—O1 | 64.00 (7) | O3—C7—H6 | 111 (2) |
O6—Na1—O5 | 60.17 (7) | C8—C7—H6 | 110 (2) |
C113ii—Na1—C114ii | 25.32 (11) | H5—C7—H6 | 106 (3) |
S1i—Pd1—S2i | 89.85 (3) | O4—C8—C7 | 106.4 (3) |
S1—Pd1—S2i | 90.15 (3) | O4—C8—H7 | 106 (2) |
C1—S1—Pd1 | 111.05 (11) | C7—C8—H7 | 112 (2) |
C2—S2—Pd1 | 107.44 (12) | O4—C8—H8 | 104 (2) |
N1—Na1—O2 | 89.57 (10) | C7—C8—H8 | 115 (2) |
N1—Na1—O6 | 88.79 (10) | H7—C8—H8 | 113 (3) |
O2—Na1—O6 | 123.36 (8) | C121—C9—O4 | 125.9 (4) |
N1—Na1—O1 | 90.25 (9) | C121—C9—C10 | 120.1 (4) |
N1—Na1—O3 | 92.12 (10) | O4—C9—C10 | 114.0 (3) |
O6—Na1—O3 | 172.38 (9) | O5—C10—C9 | 114.8 (3) |
O1—Na1—O3 | 123.55 (8) | O5—C10—C124 | 125.5 (4) |
N1—Na1—O5 | 101.98 (10) | C9—C10—C124 | 119.6 (4) |
O2—Na1—O5 | 168.18 (8) | O5—C11—C12 | 107.0 (3) |
O1—Na1—O5 | 122.25 (8) | O5—C11—H9 | 112 (2) |
O3—Na1—O5 | 112.27 (8) | C12—C11—H9 | 112 (2) |
N1—Na1—O4 | 104.56 (10) | O5—C11—H11 | 110.0 (19) |
O2—Na1—O4 | 122.44 (8) | C12—C11—H11 | 110 (2) |
O6—Na1—O4 | 112.63 (8) | H9—C11—H11 | 107 (3) |
O1—Na1—O4 | 164.91 (8) | O6—C12—C11 | 107.6 (3) |
N1—Na1—C113ii | 167.78 (14) | O6—C12—H10 | 110.3 (18) |
O2—Na1—C113ii | 81.18 (10) | C11—C12—H10 | 114.0 (18) |
O6—Na1—C113ii | 102.95 (12) | O6—C12—H12 | 104 (2) |
O1—Na1—C113ii | 91.88 (10) | C11—C12—H12 | 110 (2) |
O3—Na1—C113ii | 76.70 (12) | H10—C12—H12 | 111 (3) |
O5—Na1—C113ii | 87.03 (10) | O6—C13—C14 | 109.0 (3) |
O4—Na1—C113ii | 74.27 (9) | O6—C13—H13 | 103.6 (18) |
N1—Na1—C114ii | 165.47 (13) | C14—C13—H13 | 112.1 (18) |
O2—Na1—C114ii | 93.38 (10) | O6—C13—H14 | 107.3 (18) |
O6—Na1—C114ii | 77.70 (12) | C14—C13—H14 | 110.4 (18) |
O1—Na1—C114ii | 79.10 (10) | H13—C13—H14 | 114 (3) |
O3—Na1—C114ii | 101.98 (12) | O1—C14—C13 | 107.4 (3) |
O5—Na1—C114ii | 76.06 (10) | O1—C14—H15 | 108 (2) |
O4—Na1—C114ii | 85.82 (10) | C13—C14—H15 | 107 (2) |
C1—N1—Na1 | 150.4 (3) | O1—C14—H16 | 109 (2) |
C3—O1—C14 | 117.6 (2) | C13—C14—H16 | 110 (2) |
C3—O1—Na1 | 123.03 (17) | H15—C14—H16 | 115 (3) |
C14—O1—Na1 | 118.08 (19) | C3—C112—C113 | 120.1 (4) |
C4—O2—C5 | 117.3 (2) | C3—C112—H112 | 117 (2) |
C4—O2—Na1 | 123.30 (18) | C113—C112—H112 | 122 (2) |
C5—O2—Na1 | 117.51 (18) | C114—C113—C112 | 120.6 (4) |
C7—O3—C6 | 112.0 (3) | C114—C113—Na1ii | 77.5 (2) |
C7—O3—Na1 | 111.9 (2) | C112—C113—Na1ii | 113.3 (2) |
C6—O3—Na1 | 104.05 (19) | C114—C113—H113 | 119 (2) |
C9—O4—C8 | 118.0 (3) | C112—C113—H113 | 121 (2) |
C9—O4—Na1 | 120.53 (19) | Na1ii—C113—H113 | 78 (2) |
C8—O4—Na1 | 114.3 (2) | C113—C114—C115 | 120.6 (4) |
C10—O5—C11 | 118.2 (3) | C113—C114—Na1ii | 77.1 (2) |
C10—O5—Na1 | 120.59 (19) | C115—C114—Na1ii | 115.1 (2) |
C11—O5—Na1 | 114.1 (2) | C113—C114—H114 | 121 (3) |
C13—O6—C12 | 112.4 (3) | C115—C114—H114 | 118 (3) |
C13—O6—Na1 | 108.73 (19) | Na1ii—C114—H114 | 77 (2) |
C12—O6—Na1 | 110.9 (2) | C4—C115—C114 | 119.6 (4) |
N1—C1—S1 | 174.9 (3) | C4—C115—H115 | 116 (2) |
N2—C2—S2 | 177.3 (3) | C114—C115—H115 | 125 (2) |
O1—C3—C112 | 126.0 (3) | C9—C121—C122 | 120.0 (5) |
O1—C3—C4 | 114.5 (3) | C9—C121—H121 | 119 (3) |
C112—C3—C4 | 119.6 (3) | C122—C121—H121 | 120 (3) |
O2—C4—C115 | 125.6 (3) | C123—C122—C121 | 120.1 (5) |
O2—C4—C3 | 114.8 (3) | C123—C122—H122 | 117 (3) |
C115—C4—C3 | 119.5 (3) | C121—C122—H122 | 123 (3) |
O2—C5—C6 | 107.1 (3) | C122—C123—C124 | 120.9 (5) |
O2—C5—H1 | 111.6 (17) | C122—C123—H123 | 128 (4) |
C6—C5—H1 | 105.0 (17) | C124—C123—H123 | 111 (4) |
O2—C5—H2 | 108.1 (18) | C123—C124—C10 | 119.2 (5) |
C6—C5—H2 | 108.7 (19) | C123—C124—H124 | 128 (2) |
H1—C5—H2 | 116 (2) | C10—C124—H124 | 113 (2) |
O3—C6—C5 | 107.8 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Na(C20H24O6)]2[Pd(SCN)4] |
Mr | 1105.48 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 11.5695 (10), 8.568 (3), 12.976 (2) |
α, β, γ (°) | 81.58 (2), 104.804 (10), 96.85 (2) |
V (Å3) | 1225.7 (5) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.63 |
Crystal size (mm) | 0.60 × 0.50 × 0.40 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.834, 0.884 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4622, 4406, 3190 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.080, 1.0 |
No. of reflections | 4406 |
No. of parameters | 400 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.41, −0.43 |
Computer programs: CAD-4 Manual (Enraf-Nonius, 1988), CAD-4 Manual, SDP-Plus (Frenz, 1985), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1996), SHELXL97.
Pd1—S1 | 2.3241 (9) | Na1—O4 | 2.853 (2) |
Pd1—S2 | 2.3319 (8) | Na1—O5 | 2.841 (3) |
S1—C1 | 1.663 (4) | Na1—O6 | 2.559 (2) |
S2—C2 | 1.664 (4) | Na1—C113i | 3.077 (4) |
Na1—N1 | 2.423 (3) | Na1—C114i | 3.082 (4) |
Na1—O1 | 2.572 (2) | N1—C1 | 1.151 (4) |
Na1—O2 | 2.559 (2) | N2—C2 | 1.133 (4) |
Na1—O3 | 2.597 (2) | ||
S1ii—Pd1—S2 | 90.15 (3) | O5—Na1—O4 | 52.46 (7) |
O2—Na1—O3 | 64.23 (7) | O6—Na1—O1 | 64.00 (7) |
O2—Na1—O1 | 59.40 (7) | O6—Na1—O5 | 60.17 (7) |
O3—Na1—O4 | 59.83 (7) | C113i—Na1—C114i | 25.32 (11) |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y+1, −z+1. |
Cation–π interactions have attracted considerable attention as an important non-covalent binding force. Studies in the gas phase (Sunner et al., 1981), aqueous media (Petti et al., 1988; Forman et al., 1995), solid state (Clark et al., 1992; Beer et al., 1994; Werner et al., 1996), biological systems (Ma & Dougherty, 1997; Dougherty & Stauffer, 1990), as well as theoretical calculations (Mecozzi et al., 1996; Jiang et al., 1998, 1999) established the broad scope and significance of these interactions. We have reported the first examples of crown ether complexes, [K(DB18C6)]2[Pd(SCN)4] (DB18C6 is dibenzo-18-crown-6) (Dou et al., 2000) and [K(DB18C6)]2[Pt(SCN)4] (Li et al., 2000), which exhibit cation–π interactions responsible for the formation of infinite chains in crystals. However, in spite of the growing interest, the X-ray evidence for the existence of the analogous Na+···π interaction is still limited. Bock and co-workers synthesized two compounds containing interactions of this kind, namely [(C6H5)2C═ CHC(C6H5)2]-[Na+O(C2H5)2] (Bock et al., 1990) and [(C6H5)2C═C(C6H5)2]2-2[Na+O(C2H5)2] (Bock et al., 1989). In the present paper, we report the synthesis and crystal structure of the complex of DB18C6 with Na2[Pd(SCN)4], (I), which provides a new example of Na+···π interaction.
The structure of the title complex (Fig. 1) features an ion-pair-type species consisting of two [Na(DB18C6)]+ cations and a [Pd(SCN)4]2- dianion. The Pd atom occupies a special position in the inversion center and has a square-planar coordination environment formed by four S atoms [Pd1—S1 2.3241 (9) and Pd1—S2 2.3319 (8) Å, S1—Pd1—S2 90.15 (3)°]. The average Pd—S, S—C and C—N bond lengths (2.3270, 1.671 and 1.133 Å, respectively) are consistent with the corresponding values in [K(DB18C6)]2[Pd(SCN)4] (Dou et al., 2000) and [K(DB18C6)]2[Pd(SCN)4]·H2O (Wu et al., 1991).
In the [Na(DB18C6)]+ cation, the Na—O bond lengths span the range 2.559–2.853 Å. The Na+ ion is also coordinated by the N atom of one of the SCN groups at a distance of 2.423 (3) Å, which is consistent with the Na—N distance [2.472 (8) Å] in [Na(B15C5)]2[Pd(SCN)4] (B15C5 is benzo-15-crown-5) (Zhu et al., 2000). The remainder of its coordination sphere is made up of the Na—C113i 3.077 (4) Å and Na—C114i 3.082 (4) Å [symmetry code: (i) 2 - x, -y, 1 - z] close contacts involving one of the phenylene rings of the DB18C6 ligand of the neighbouring [Na(DB18C6)]2[Pd(SCN)4] ion pair. These interactions give rise to the formation of infinite chains stretching along the [110] direction in the crystal (Fig. 2). Similar infinite chains formed due to Na···π interactions with even shorter Na···C distances were observed in the abovementioned complexes reported by Bock et al. (1989, 1990) (the average Na···C distances are 2.86 and 2.88 Å respectively).