

Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808037616/pk2131sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536808037616/pk2131Isup2.hkl |
CCDC reference: 712314
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean
(C-C) = 0.003 Å
- R factor = 0.024
- wR factor = 0.063
- Data-to-parameter ratio = 17.5
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for C2 -- C4 .. 7.01 su PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Pd1 -- S1 .. 11.93 su
Alert level C Value of measurement temperature given = 173.000 Value of melting point given = 0.000 PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Pd1 -- S2 .. 9.61 su PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C2 - C3 ... 1.42 Ang. PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C2 - C4 ... 1.43 Ang.
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound (C16H36N)2[Pd(S2C4N2)2] was prepared using a procedure similar to that described by Fackler and Coucouvanis (1966) substituting the use of tetra-n-propylammonium iodide with tetra-n-butylammonium bromide. The title compound has been previously characterized by Werden et al. (1966). Spectroscopic analysis of the title compound obtained by this procedure was consistent with the data previously reported. Crystals were obtained by diffusion of diethyl ether into a concentrated solution of the title compound dissolved in acetone.
The H atoms were geometrically placed (C—H = 0.98–0.99 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![]() | Fig. 1. The molecular structure of (C16H36N)2[Pd(S2C4N2)2] showing 50% displacement ellipsoids for the non-hydrogen atoms. Only the crystallographically independent atoms are labelled. |
(C16H36N)2[Pd(C4N2S2)2] | F(000) = 928 |
Mr = 871.68 | Dx = 1.246 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3632 reflections |
a = 13.9468 (13) Å | θ = 2.2–25.0° |
b = 8.6267 (8) Å | µ = 0.61 mm−1 |
c = 20.3231 (19) Å | T = 173 K |
β = 108.218 (2)° | Block, orange |
V = 2322.6 (4) Å3 | 0.50 × 0.40 × 0.33 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 4124 independent reflections |
Radiation source: normal-focus sealed tube | 3613 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
ϕ scans | θmax = 25.1°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker 2003) | h = −16→16 |
Tmin = 0.749, Tmax = 0.824 | k = −10→10 |
22206 measured reflections | l = −24→24 |
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)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.063 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0322P)2 + 0.8279P] where P = (Fo2 + 2Fc2)/3 |
4124 reflections | (Δ/σ)max = 0.001 |
236 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
(C16H36N)2[Pd(C4N2S2)2] | V = 2322.6 (4) Å3 |
Mr = 871.68 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.9468 (13) Å | µ = 0.61 mm−1 |
b = 8.6267 (8) Å | T = 173 K |
c = 20.3231 (19) Å | 0.50 × 0.40 × 0.33 mm |
β = 108.218 (2)° |
Bruker SMART CCD area-detector diffractometer | 4124 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker 2003) | 3613 reflections with I > 2σ(I) |
Tmin = 0.749, Tmax = 0.824 | Rint = 0.027 |
22206 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.063 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.25 e Å−3 |
4124 reflections | Δρmin = −0.28 e Å−3 |
236 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 | 0.0000 | 1.0000 | 1.0000 | 0.03612 (8) | |
S1 | 0.15463 (4) | 1.09186 (5) | 0.99538 (2) | 0.04065 (12) | |
C1 | 0.19356 (14) | 1.09487 (19) | 1.08491 (9) | 0.0367 (4) | |
N1 | 0.40960 (13) | 1.2828 (2) | 1.07224 (9) | 0.0542 (5) | |
S2 | 0.10006 (4) | 1.02365 (5) | 1.11567 (3) | 0.04049 (12) | |
N2 | 0.33826 (14) | 1.1436 (2) | 1.25846 (10) | 0.0597 (5) | |
C2 | 0.28567 (14) | 1.1511 (2) | 1.12541 (9) | 0.0375 (4) | |
N3 | 0.25990 (9) | 0.61333 (15) | 0.92368 (7) | 0.0254 (3) | |
C3 | 0.35433 (15) | 1.2222 (2) | 1.09551 (10) | 0.0415 (5) | |
C4 | 0.31446 (15) | 1.1474 (2) | 1.19936 (11) | 0.0438 (5) | |
C5 | 0.17965 (12) | 0.64663 (19) | 0.95836 (8) | 0.0280 (4) | |
H5A | 0.1898 | 0.7533 | 0.9772 | 0.034* | |
H5B | 0.1125 | 0.6430 | 0.9226 | 0.034* | |
C6 | 0.17926 (13) | 0.53612 (19) | 1.01639 (9) | 0.0312 (4) | |
H6A | 0.2494 | 0.5187 | 1.0465 | 0.037* | |
H6B | 0.1510 | 0.4350 | 0.9965 | 0.037* | |
C7 | 0.11676 (13) | 0.6011 (2) | 1.05940 (9) | 0.0338 (4) | |
H7A | 0.1484 | 0.6980 | 1.0823 | 0.041* | |
H7B | 0.0484 | 0.6270 | 1.0285 | 0.041* | |
C8 | 0.10805 (15) | 0.4871 (2) | 1.11407 (10) | 0.0402 (4) | |
H8A | 0.0707 | 0.5352 | 1.1423 | 0.060* | |
H8B | 0.1757 | 0.4583 | 1.1437 | 0.060* | |
H8C | 0.0721 | 0.3942 | 1.0915 | 0.060* | |
C9 | 0.25005 (12) | 0.44804 (19) | 0.89542 (8) | 0.0278 (4) | |
H9A | 0.3061 | 0.4288 | 0.8763 | 0.033* | |
H9B | 0.2585 | 0.3754 | 0.9345 | 0.033* | |
C10 | 0.15178 (13) | 0.4104 (2) | 0.84001 (10) | 0.0379 (4) | |
H10A | 0.1458 | 0.4731 | 0.7981 | 0.045* | |
H10B | 0.0944 | 0.4367 | 0.8568 | 0.045* | |
C11 | 0.14795 (15) | 0.2387 (2) | 0.82185 (10) | 0.0413 (4) | |
H11A | 0.2031 | 0.2147 | 0.8025 | 0.050* | |
H11B | 0.1592 | 0.1769 | 0.8646 | 0.050* | |
C12 | 0.04792 (16) | 0.1920 (3) | 0.76986 (12) | 0.0587 (6) | |
H12A | 0.0489 | 0.0809 | 0.7600 | 0.088* | |
H12B | 0.0372 | 0.2510 | 0.7269 | 0.088* | |
H12C | −0.0069 | 0.2140 | 0.7891 | 0.088* | |
C13 | 0.24560 (12) | 0.7323 (2) | 0.86637 (8) | 0.0302 (4) | |
H13A | 0.1768 | 0.7201 | 0.8333 | 0.036* | |
H13B | 0.2496 | 0.8370 | 0.8870 | 0.036* | |
C14 | 0.32053 (13) | 0.7239 (2) | 0.82619 (9) | 0.0364 (4) | |
H14A | 0.3276 | 0.6150 | 0.8131 | 0.044* | |
H14B | 0.3874 | 0.7602 | 0.8559 | 0.044* | |
C15 | 0.28591 (14) | 0.8236 (2) | 0.76111 (9) | 0.0434 (5) | |
H15A | 0.2205 | 0.7840 | 0.7306 | 0.052* | |
H15B | 0.2754 | 0.9312 | 0.7743 | 0.052* | |
C16 | 0.36177 (18) | 0.8238 (3) | 0.72159 (12) | 0.0618 (6) | |
H16A | 0.3374 | 0.8910 | 0.6809 | 0.093* | |
H16B | 0.3702 | 0.7180 | 0.7067 | 0.093* | |
H16C | 0.4268 | 0.8625 | 0.7516 | 0.093* | |
C17 | 0.36558 (11) | 0.62498 (19) | 0.97581 (8) | 0.0271 (3) | |
H17A | 0.3757 | 0.5354 | 1.0077 | 0.033* | |
H17B | 0.4152 | 0.6155 | 0.9503 | 0.033* | |
C18 | 0.38904 (12) | 0.7716 (2) | 1.01894 (9) | 0.0323 (4) | |
H18A | 0.3397 | 0.7849 | 1.0445 | 0.039* | |
H18B | 0.3843 | 0.8627 | 0.9885 | 0.039* | |
C19 | 0.49551 (13) | 0.7591 (2) | 1.06987 (9) | 0.0375 (4) | |
H19A | 0.4987 | 0.6693 | 1.1008 | 0.045* | |
H19B | 0.5435 | 0.7399 | 1.0438 | 0.045* | |
C20 | 0.52758 (15) | 0.9040 (2) | 1.11359 (11) | 0.0516 (5) | |
H20A | 0.5969 | 0.8913 | 1.1444 | 0.077* | |
H20B | 0.4823 | 0.9207 | 1.1413 | 0.077* | |
H20C | 0.5242 | 0.9935 | 1.0833 | 0.077* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.05110 (14) | 0.02259 (11) | 0.03883 (13) | 0.00135 (8) | 0.02006 (10) | −0.00010 (8) |
S1 | 0.0562 (3) | 0.0330 (2) | 0.0383 (3) | 0.0008 (2) | 0.0228 (2) | 0.00116 (19) |
C1 | 0.0513 (11) | 0.0244 (9) | 0.0408 (10) | 0.0087 (8) | 0.0236 (9) | 0.0046 (7) |
N1 | 0.0447 (10) | 0.0646 (12) | 0.0576 (11) | 0.0134 (9) | 0.0224 (9) | 0.0267 (9) |
S2 | 0.0536 (3) | 0.0341 (3) | 0.0400 (3) | −0.0036 (2) | 0.0237 (2) | 0.00052 (19) |
N2 | 0.0626 (12) | 0.0758 (14) | 0.0422 (11) | −0.0116 (10) | 0.0185 (9) | 0.0066 (9) |
C2 | 0.0451 (11) | 0.0344 (10) | 0.0376 (10) | 0.0092 (8) | 0.0197 (9) | 0.0077 (8) |
N3 | 0.0217 (7) | 0.0270 (7) | 0.0260 (7) | 0.0027 (5) | 0.0054 (6) | −0.0010 (6) |
C3 | 0.0414 (11) | 0.0426 (11) | 0.0419 (11) | 0.0145 (9) | 0.0149 (9) | 0.0148 (9) |
C4 | 0.0453 (11) | 0.0418 (11) | 0.0486 (13) | 0.0000 (9) | 0.0209 (10) | 0.0068 (9) |
C5 | 0.0226 (8) | 0.0282 (8) | 0.0331 (9) | 0.0038 (7) | 0.0085 (7) | −0.0034 (7) |
C6 | 0.0307 (9) | 0.0273 (9) | 0.0378 (10) | 0.0033 (7) | 0.0138 (8) | −0.0023 (7) |
C7 | 0.0299 (9) | 0.0350 (10) | 0.0376 (10) | 0.0043 (7) | 0.0120 (8) | −0.0073 (8) |
C8 | 0.0382 (10) | 0.0494 (12) | 0.0377 (10) | 0.0005 (9) | 0.0188 (8) | −0.0042 (8) |
C9 | 0.0269 (8) | 0.0267 (8) | 0.0294 (9) | 0.0027 (7) | 0.0083 (7) | −0.0022 (7) |
C10 | 0.0293 (9) | 0.0410 (11) | 0.0402 (10) | 0.0017 (8) | 0.0062 (8) | −0.0107 (8) |
C11 | 0.0508 (12) | 0.0384 (10) | 0.0344 (10) | −0.0087 (9) | 0.0126 (9) | −0.0071 (8) |
C12 | 0.0543 (13) | 0.0669 (15) | 0.0559 (13) | −0.0249 (12) | 0.0187 (11) | −0.0259 (12) |
C13 | 0.0278 (9) | 0.0300 (9) | 0.0289 (9) | 0.0024 (7) | 0.0034 (7) | 0.0033 (7) |
C14 | 0.0345 (10) | 0.0385 (10) | 0.0363 (10) | 0.0008 (8) | 0.0112 (8) | 0.0038 (8) |
C15 | 0.0409 (11) | 0.0538 (12) | 0.0330 (10) | −0.0038 (9) | 0.0078 (8) | 0.0069 (9) |
C16 | 0.0645 (15) | 0.0790 (17) | 0.0487 (13) | 0.0003 (13) | 0.0276 (12) | 0.0143 (12) |
C17 | 0.0211 (8) | 0.0311 (9) | 0.0269 (8) | 0.0029 (7) | 0.0042 (7) | 0.0007 (7) |
C18 | 0.0269 (9) | 0.0317 (9) | 0.0343 (10) | 0.0012 (7) | 0.0036 (7) | −0.0024 (7) |
C19 | 0.0297 (9) | 0.0397 (10) | 0.0376 (10) | 0.0024 (8) | 0.0024 (8) | −0.0049 (8) |
C20 | 0.0426 (11) | 0.0459 (12) | 0.0541 (13) | −0.0044 (9) | −0.0025 (10) | −0.0090 (10) |
Pd1—S1i | 2.3269 (5) | C10—H10B | 0.9900 |
Pd1—S1 | 2.3269 (5) | C11—C12 | 1.518 (3) |
Pd1—S2i | 2.3375 (5) | C11—H11A | 0.9900 |
Pd1—S2 | 2.3375 (5) | C11—H11B | 0.9900 |
S1—C1 | 1.7288 (19) | C12—H12A | 0.9800 |
C1—C2 | 1.379 (3) | C12—H12B | 0.9800 |
C1—S2 | 1.7258 (19) | C12—H12C | 0.9800 |
N1—C3 | 1.148 (2) | C13—C14 | 1.516 (2) |
N2—C4 | 1.142 (2) | C13—H13A | 0.9900 |
C2—C3 | 1.424 (3) | C13—H13B | 0.9900 |
C2—C4 | 1.429 (3) | C14—C15 | 1.524 (2) |
N3—C13 | 1.518 (2) | C14—H14A | 0.9900 |
N3—C5 | 1.525 (2) | C14—H14B | 0.9900 |
N3—C17 | 1.5260 (19) | C15—C16 | 1.515 (3) |
N3—C9 | 1.527 (2) | C15—H15A | 0.9900 |
C5—C6 | 1.518 (2) | C15—H15B | 0.9900 |
C5—H5A | 0.9900 | C16—H16A | 0.9800 |
C5—H5B | 0.9900 | C16—H16B | 0.9800 |
C6—C7 | 1.521 (2) | C16—H16C | 0.9800 |
C6—H6A | 0.9900 | C17—C18 | 1.515 (2) |
C6—H6B | 0.9900 | C17—H17A | 0.9900 |
C7—C8 | 1.517 (3) | C17—H17B | 0.9900 |
C7—H7A | 0.9900 | C18—C19 | 1.525 (2) |
C7—H7B | 0.9900 | C18—H18A | 0.9900 |
C8—H8A | 0.9800 | C18—H18B | 0.9900 |
C8—H8B | 0.9800 | C19—C20 | 1.517 (3) |
C8—H8C | 0.9800 | C19—H19A | 0.9900 |
C9—C10 | 1.512 (2) | C19—H19B | 0.9900 |
C9—H9A | 0.9900 | C20—H20A | 0.9800 |
C9—H9B | 0.9900 | C20—H20B | 0.9800 |
C10—C11 | 1.523 (3) | C20—H20C | 0.9800 |
C10—H10A | 0.9900 | ||
S1i—Pd1—S1 | 180.0 | C12—C11—H11A | 109.1 |
S1i—Pd1—S2i | 75.015 (17) | C10—C11—H11A | 109.1 |
S1—Pd1—S2i | 104.985 (17) | C12—C11—H11B | 109.1 |
S1i—Pd1—S2 | 104.985 (17) | C10—C11—H11B | 109.1 |
S1—Pd1—S2 | 75.015 (17) | H11A—C11—H11B | 107.8 |
S2i—Pd1—S2 | 180.0 | C11—C12—H12A | 109.5 |
C1—S1—Pd1 | 87.29 (7) | C11—C12—H12B | 109.5 |
C2—C1—S2 | 125.26 (14) | H12A—C12—H12B | 109.5 |
C2—C1—S1 | 124.12 (14) | C11—C12—H12C | 109.5 |
S2—C1—S1 | 110.59 (11) | H12A—C12—H12C | 109.5 |
C1—S2—Pd1 | 87.02 (7) | H12B—C12—H12C | 109.5 |
C1—C2—C3 | 121.47 (17) | C14—C13—N3 | 115.69 (13) |
C1—C2—C4 | 121.52 (17) | C14—C13—H13A | 108.4 |
C3—C2—C4 | 116.93 (18) | N3—C13—H13A | 108.4 |
C13—N3—C5 | 106.73 (12) | C14—C13—H13B | 108.4 |
C13—N3—C17 | 110.78 (12) | N3—C13—H13B | 108.4 |
C5—N3—C17 | 110.85 (12) | H13A—C13—H13B | 107.4 |
C13—N3—C9 | 111.59 (12) | C13—C14—C15 | 110.84 (15) |
C5—N3—C9 | 110.92 (12) | C13—C14—H14A | 109.5 |
C17—N3—C9 | 106.04 (11) | C15—C14—H14A | 109.5 |
N1—C3—C2 | 178.4 (2) | C13—C14—H14B | 109.5 |
N2—C4—C2 | 179.3 (2) | C15—C14—H14B | 109.5 |
C6—C5—N3 | 114.98 (13) | H14A—C14—H14B | 108.1 |
C6—C5—H5A | 108.5 | C16—C15—C14 | 112.12 (17) |
N3—C5—H5A | 108.5 | C16—C15—H15A | 109.2 |
C6—C5—H5B | 108.5 | C14—C15—H15A | 109.2 |
N3—C5—H5B | 108.5 | C16—C15—H15B | 109.2 |
H5A—C5—H5B | 107.5 | C14—C15—H15B | 109.2 |
C5—C6—C7 | 110.90 (14) | H15A—C15—H15B | 107.9 |
C5—C6—H6A | 109.5 | C15—C16—H16A | 109.5 |
C7—C6—H6A | 109.5 | C15—C16—H16B | 109.5 |
C5—C6—H6B | 109.5 | H16A—C16—H16B | 109.5 |
C7—C6—H6B | 109.5 | C15—C16—H16C | 109.5 |
H6A—C6—H6B | 108.0 | H16A—C16—H16C | 109.5 |
C8—C7—C6 | 111.91 (14) | H16B—C16—H16C | 109.5 |
C8—C7—H7A | 109.2 | C18—C17—N3 | 116.33 (13) |
C6—C7—H7A | 109.2 | C18—C17—H17A | 108.2 |
C8—C7—H7B | 109.2 | N3—C17—H17A | 108.2 |
C6—C7—H7B | 109.2 | C18—C17—H17B | 108.2 |
H7A—C7—H7B | 107.9 | N3—C17—H17B | 108.2 |
C7—C8—H8A | 109.5 | H17A—C17—H17B | 107.4 |
C7—C8—H8B | 109.5 | C17—C18—C19 | 108.79 (14) |
H8A—C8—H8B | 109.5 | C17—C18—H18A | 109.9 |
C7—C8—H8C | 109.5 | C19—C18—H18A | 109.9 |
H8A—C8—H8C | 109.5 | C17—C18—H18B | 109.9 |
H8B—C8—H8C | 109.5 | C19—C18—H18B | 109.9 |
C10—C9—N3 | 115.76 (13) | H18A—C18—H18B | 108.3 |
C10—C9—H9A | 108.3 | C20—C19—C18 | 112.68 (15) |
N3—C9—H9A | 108.3 | C20—C19—H19A | 109.1 |
C10—C9—H9B | 108.3 | C18—C19—H19A | 109.1 |
N3—C9—H9B | 108.3 | C20—C19—H19B | 109.1 |
H9A—C9—H9B | 107.4 | C18—C19—H19B | 109.1 |
C9—C10—C11 | 110.14 (15) | H19A—C19—H19B | 107.8 |
C9—C10—H10A | 109.6 | C19—C20—H20A | 109.5 |
C11—C10—H10A | 109.6 | C19—C20—H20B | 109.5 |
C9—C10—H10B | 109.6 | H20A—C20—H20B | 109.5 |
C11—C10—H10B | 109.6 | C19—C20—H20C | 109.5 |
H10A—C10—H10B | 108.1 | H20A—C20—H20C | 109.5 |
C12—C11—C10 | 112.46 (17) | H20B—C20—H20C | 109.5 |
S2i—Pd1—S1—C1 | 178.05 (6) | C5—C6—C7—C8 | 175.31 (15) |
S2—Pd1—S1—C1 | −1.95 (6) | C13—N3—C9—C10 | −56.92 (18) |
Pd1—S1—C1—C2 | −175.49 (15) | C5—N3—C9—C10 | 61.94 (18) |
Pd1—S1—C1—S2 | 2.72 (8) | C17—N3—C9—C10 | −177.64 (15) |
C2—C1—S2—Pd1 | 175.47 (16) | N3—C9—C10—C11 | −174.36 (14) |
S1—C1—S2—Pd1 | −2.71 (8) | C9—C10—C11—C12 | 176.18 (16) |
S1i—Pd1—S2—C1 | −178.05 (6) | C5—N3—C13—C14 | 178.03 (14) |
S1—Pd1—S2—C1 | 1.95 (6) | C17—N3—C13—C14 | 57.26 (18) |
S2—C1—C2—C3 | −173.49 (14) | C9—N3—C13—C14 | −60.64 (18) |
S1—C1—C2—C3 | 4.5 (3) | N3—C13—C14—C15 | 167.77 (15) |
S2—C1—C2—C4 | 3.4 (3) | C13—C14—C15—C16 | 177.23 (17) |
S1—C1—C2—C4 | −178.64 (14) | C13—N3—C17—C18 | 67.16 (18) |
C13—N3—C5—C6 | 178.31 (14) | C5—N3—C17—C18 | −51.13 (18) |
C17—N3—C5—C6 | −60.97 (17) | C9—N3—C17—C18 | −171.60 (14) |
C9—N3—C5—C6 | 56.56 (17) | N3—C17—C18—C19 | 177.49 (14) |
N3—C5—C6—C7 | 165.40 (13) | C17—C18—C19—C20 | 177.67 (17) |
Symmetry code: (i) −x, −y+2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | (C16H36N)2[Pd(C4N2S2)2] |
Mr | 871.68 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 13.9468 (13), 8.6267 (8), 20.3231 (19) |
β (°) | 108.218 (2) |
V (Å3) | 2322.6 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.61 |
Crystal size (mm) | 0.50 × 0.40 × 0.33 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker 2003) |
Tmin, Tmax | 0.749, 0.824 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22206, 4124, 3613 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.063, 1.02 |
No. of reflections | 4124 |
No. of parameters | 236 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.28 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2006), SHELXTL (Sheldrick, 2008).
Salts of metal complexes of [Pd(i-mnt)2]2- (i-mnt = 2,2-dicyanoethylene-1,1-dithiolate) have been studied for their interesting electronic properties including their use in conducting charge-transfer salts (Mori et al., 1995; Zhu et al., 1991) and their redox behavior especially in relation to the analagous isomeric ligand 1,2-dicyanoethylene-1,2-dithiolate (mnt2-) complexes (Fackler & Coucouvanis, 1966; Werden et al., 1966). In sharp contrast to mnt complexes of the form [M(mnt)2]2- (M= NiII, PdII, PtII) which do exhibit reversible oxidation behavior, analagous i-mnt complexes of the form [M(i-mnt)2]2- do not. This effect is attributed to better π-delocalization of the five-membered rings formed by complexation of mnt compared with four-membered chelate rings of i-mnt complexes. Salts of [Pd(i-mnt)2]2- have also been studied as supramolecular linker groups in organic-inorganic hybrid coordination polymers (Cao et al., 1999; Dong et al., 2005; Gao et al., 2005; Long et al., 1997,1998; Sun et al., 2006). While several x-ray structures of [Pd(i-mnt)2]2- with alkali metal-complexed crown ether salts and one simple potassium salt have been reported, only one other simple non-coordinating cation salt (tetraethylammonium, Long et al. 1996) has been structurally characterized.
The structure of the anion in (C16H36N)2[Pd(S2C4N2)2] shows significant distortions from a square planar environment as forced by the four-membered chelate rings of the i-mnt ligands, with the i-mnt bite angle of S(2)—Pd(1)—S(1) 75.0159 (17)°. As the Pd sits on the inversion centre at (0,0,0) in the space group P21/c, Z'=0.5, the anion is quite planar, with a calculated r.m.s. deviation from a least-squares plane formed by all atoms of the complex anion of 0.0806 (13) Å. The bond lengths within the coordinated i-mnt ligand, in particular the bonds C(1)—C(2) 1.379 (3) Å, C(2)—C(3) 1.424 (3) Å, and C(2)—C(4) 1.429 (3)Å are very similar to those observed in the tetraethylammonium salt, showing significant π-delocalization. No columnar stacking is observed amongst the complex anions. As expected, upon comparison of this structure with that of the tetraethylammonium salt, little effect was observed on the intramolecular features of the complex anion.