N-(4-Nitro­benz­yl)quinolinium bis­(2-thioxo-1,3-dithiole-4,5-dithiol­ato)palladium(III) acetone solvate

In the title ion-pair compound, (C₁₆H₁₃N₂O₂)[Pd(C₃S₅)₂]·C₃H₆O, the Pd^III atom exhibits square-planar coordination geometry involving four S atoms of two 2-thioxo-1,3-dithiole-4,5-dithiol­ate (dmit) ligands. Some weak S...S inter­actions and hydrogen bonds are found, resulting in a three-dimensional supra­molecular network structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.044
• wR factor = 0.086
• Data-to-parameter ratio = 16.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    S7     -   C4      ..       7.54 su

Alert level C
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N1     -   C15     ..       6.12 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N1     -   C16     ..       5.10 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S5     -   C1      ..       6.88 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S6     -   C4      ..       5.52 su
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.15
PLAT362_ALERT_2_C Short  C(sp3)-C(sp2) Bond  C24    -   C25    ...       1.41 Ang.

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   7 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

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Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXL97.

N-(4-Nitrobenzyl)quinolinium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)palladium(III) acetone solvate

Crystal data

(C16H13N2O2)[Pd(C3S5)2]·C3H6O	F(000) = 1652
Mr = 822.54	Dx = 1.734 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 700 reflections
a = 12.224 (2) Å	θ = 2.7–19.6°
b = 8.0880 (16) Å	µ = 1.28 mm^−1
c = 32.711 (6) Å	T = 293 K
β = 103.015 (6)°	Block, black
V = 3151.0 (10) Å^3	0.3 × 0.2 × 0.2 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	6128 independent reflections
Radiation source: fine-focus sealed tube	4753 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
φ and ω scans	θmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −14→11
Tmin = 0.745, Tmax = 0.778	k = −9→9
16294 measured reflections	l = −40→40

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.087	H-atom parameters constrained
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0376P)^2 + 0.1449P] where P = (Fo^2 + 2Fc^2)/3
6128 reflections	(Δ/σ)max = 0.002
372 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.64 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Pd1	0.03584 (2)	0.34882 (4)	0.048986 (8)	0.04705 (10)
S4	0.01433 (8)	0.50565 (12)	0.10417 (3)	0.0497 (2)
C1	−0.2638 (3)	0.3498 (6)	0.15394 (12)	0.0621 (11)
C2	−0.1564 (3)	0.2864 (5)	0.09482 (11)	0.0469 (8)
C3	−0.1018 (3)	0.4190 (5)	0.11631 (10)	0.0480 (9)
C4	0.3445 (3)	0.3579 (5)	−0.05150 (12)	0.0549 (9)
C5	0.1802 (3)	0.2832 (5)	−0.01678 (10)	0.0480 (9)
C6	0.2312 (3)	0.4218 (4)	0.00321 (10)	0.0445 (8)
C7	0.2084 (3)	0.1703 (5)	0.15219 (10)	0.0454 (8)
H7	0.1580	0.1620	0.1696	0.054*
C8	0.2784 (3)	0.3061 (5)	0.15580 (11)	0.0496 (9)
H8	0.2732	0.3884	0.1751	0.060*
C9	0.3520 (3)	0.3207 (5)	0.13239 (11)	0.0501 (9)
H9	0.4015	0.4097	0.1358	0.060*
C10	0.3544 (2)	0.1969 (4)	0.10163 (9)	0.0308 (6)
C11	0.4342 (3)	0.2056 (4)	0.07464 (10)	0.0427 (8)
H11	0.4854	0.2921	0.0775	0.051*
C12	0.4333 (3)	0.0884 (5)	0.04568 (12)	0.0557 (10)
H12	0.4818	0.0960	0.0275	0.067*
C13	0.3626 (3)	−0.0398 (5)	0.04284 (11)	0.0553 (10)
H13	0.3653	−0.1221	0.0232	0.066*
C14	0.2857 (3)	−0.0549 (4)	0.06775 (10)	0.0439 (8)
H14	0.2356	−0.1430	0.0643	0.053*
C15	0.2853 (2)	0.0639 (4)	0.09781 (9)	0.0381 (7)
C16	0.1393 (3)	−0.0977 (4)	0.12161 (10)	0.0429 (8)
H16A	0.1855	−0.1947	0.1210	0.052*
H16B	0.0831	−0.0939	0.0954	0.052*
C17	0.0807 (3)	−0.1133 (4)	0.15811 (10)	0.0414 (8)
C18	−0.0289 (3)	−0.0655 (5)	0.15212 (11)	0.0511 (9)
H18	−0.0654	−0.0191	0.1267	0.061*
C19	−0.0854 (3)	−0.0860 (5)	0.18379 (11)	0.0484 (9)
H19	−0.1601	−0.0536	0.1799	0.058*
C20	−0.0327 (3)	−0.1521 (5)	0.21977 (10)	0.0489 (9)
C21	0.0784 (3)	−0.2019 (6)	0.22708 (11)	0.0587 (11)
H21	0.1135	−0.2487	0.2526	0.070*
C22	0.1355 (3)	−0.1812 (6)	0.19611 (11)	0.0577 (10)
H22	0.2105	−0.2123	0.2005	0.069*
N1	0.2113 (2)	0.0537 (3)	0.12505 (7)	0.0340 (6)
N2	−0.0945 (3)	−0.1755 (4)	0.25361 (9)	0.0461 (7)
O1	−0.0469 (2)	−0.2470 (3)	0.28494 (7)	0.0467 (6)
O2	−0.1845 (2)	−0.1139 (3)	0.25001 (7)	0.0505 (6)
S1	−0.34864 (9)	0.34368 (15)	0.18577 (3)	0.0598 (3)
S2	−0.27175 (8)	0.21276 (14)	0.11235 (3)	0.0568 (3)
S3	−0.11606 (8)	0.19310 (11)	0.05336 (3)	0.0486 (2)
S5	−0.15760 (10)	0.49045 (14)	0.15703 (3)	0.0623 (3)
S6	0.43602 (9)	0.35801 (14)	−0.08128 (3)	0.0570 (3)
S7	0.24008 (9)	0.20985 (13)	−0.05625 (3)	0.0585 (3)
S8	0.06385 (8)	0.19247 (12)	−0.00556 (3)	0.0488 (2)
S9	0.18434 (8)	0.51175 (12)	0.04435 (3)	0.0493 (2)
S10	0.34512 (8)	0.49759 (12)	−0.01232 (3)	0.0531 (2)
O3	0.38982 (19)	0.7369 (3)	0.17417 (7)	0.0477 (6)
C23	0.5234 (3)	0.7026 (5)	0.23489 (12)	0.0594 (10)
H23A	0.4704	0.6230	0.2406	0.089*
H23B	0.5350	0.7870	0.2561	0.089*
H23C	0.5934	0.6487	0.2350	0.089*
C24	0.4787 (3)	0.7791 (5)	0.19299 (10)	0.0462 (8)
C25	0.5523 (4)	0.8809 (5)	0.17648 (11)	0.0549 (10)
H25A	0.6108	0.8144	0.1697	0.082*
H25B	0.5848	0.9625	0.1969	0.082*
H25C	0.5113	0.9349	0.1516	0.082*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.05106 (17)	0.04236 (16)	0.04415 (15)	−0.00147 (13)	0.00319 (11)	0.00124 (12)
S4	0.0532 (5)	0.0446 (5)	0.0484 (5)	−0.0021 (4)	0.0052 (4)	−0.0006 (4)
C1	0.048 (2)	0.086 (3)	0.058 (2)	0.016 (2)	0.0241 (18)	0.001 (2)
C2	0.0424 (19)	0.043 (2)	0.0507 (19)	−0.0107 (16)	0.0010 (16)	−0.0077 (16)
C3	0.056 (2)	0.050 (2)	0.0357 (17)	−0.0097 (17)	0.0065 (15)	−0.0060 (15)
C4	0.051 (2)	0.050 (2)	0.068 (2)	−0.0209 (18)	0.0209 (19)	−0.0033 (19)
C5	0.054 (2)	0.048 (2)	0.0352 (16)	−0.0183 (17)	−0.0034 (15)	−0.0122 (15)
C6	0.052 (2)	0.0402 (19)	0.0346 (16)	−0.0172 (16)	−0.0047 (14)	0.0048 (14)
C7	0.0464 (19)	0.052 (2)	0.0444 (18)	−0.0014 (16)	0.0248 (15)	−0.0179 (16)
C8	0.052 (2)	0.048 (2)	0.055 (2)	−0.0122 (17)	0.0259 (18)	−0.0184 (17)
C9	0.0378 (18)	0.060 (2)	0.054 (2)	−0.0204 (17)	0.0136 (16)	−0.0214 (18)
C10	0.0233 (14)	0.0327 (17)	0.0353 (15)	0.0007 (12)	0.0043 (12)	−0.0014 (12)
C11	0.056 (2)	0.0367 (18)	0.0435 (17)	−0.0121 (16)	0.0281 (16)	0.0071 (15)
C12	0.056 (2)	0.069 (3)	0.056 (2)	−0.008 (2)	0.0403 (19)	−0.0079 (19)
C13	0.071 (3)	0.055 (2)	0.050 (2)	−0.007 (2)	0.0348 (19)	−0.0154 (18)
C14	0.055 (2)	0.0397 (19)	0.0378 (17)	−0.0095 (16)	0.0126 (15)	−0.0043 (15)
C15	0.0272 (15)	0.054 (2)	0.0310 (15)	−0.0088 (14)	0.0021 (12)	0.0001 (14)
C16	0.048 (2)	0.049 (2)	0.0372 (16)	−0.0256 (16)	0.0207 (15)	0.0034 (15)
C17	0.0336 (17)	0.050 (2)	0.0470 (18)	−0.0226 (15)	0.0226 (15)	0.0006 (15)
C18	0.0390 (19)	0.068 (3)	0.0473 (19)	−0.0112 (18)	0.0118 (16)	−0.0125 (18)
C19	0.0273 (16)	0.060 (2)	0.061 (2)	−0.0074 (16)	0.0149 (16)	−0.0147 (18)
C20	0.052 (2)	0.061 (2)	0.0367 (17)	−0.0242 (19)	0.0160 (16)	−0.0112 (17)
C21	0.060 (2)	0.082 (3)	0.0411 (19)	−0.006 (2)	0.0245 (18)	0.0054 (19)
C22	0.050 (2)	0.085 (3)	0.0428 (19)	−0.003 (2)	0.0200 (17)	0.0014 (19)
N1	0.0339 (13)	0.0394 (15)	0.0333 (13)	−0.0021 (11)	0.0175 (11)	0.0006 (11)
N2	0.0500 (18)	0.0490 (18)	0.0422 (16)	−0.0298 (15)	0.0166 (14)	−0.0033 (14)
O1	0.0513 (14)	0.0525 (15)	0.0393 (12)	−0.0266 (12)	0.0165 (11)	0.0053 (11)
O2	0.0514 (15)	0.0654 (18)	0.0412 (13)	−0.0217 (13)	0.0241 (12)	−0.0072 (12)
S1	0.0578 (6)	0.0690 (7)	0.0632 (6)	−0.0001 (5)	0.0359 (5)	0.0059 (5)
S2	0.0513 (5)	0.0638 (6)	0.0607 (5)	−0.0038 (5)	0.0240 (5)	−0.0040 (5)
S3	0.0524 (5)	0.0430 (5)	0.0469 (5)	−0.0039 (4)	0.0039 (4)	0.0001 (4)
S5	0.0660 (6)	0.0651 (7)	0.0605 (6)	−0.0041 (5)	0.0244 (5)	−0.0164 (5)
S6	0.0591 (6)	0.0605 (6)	0.0596 (5)	−0.0081 (5)	0.0305 (5)	0.0003 (5)
S7	0.0707 (7)	0.0527 (6)	0.0548 (5)	−0.0180 (5)	0.0201 (5)	−0.0117 (5)
S8	0.0529 (5)	0.0445 (5)	0.0456 (5)	−0.0024 (4)	0.0036 (4)	0.0002 (4)
S9	0.0552 (6)	0.0438 (5)	0.0452 (5)	−0.0029 (4)	0.0038 (4)	−0.0004 (4)
S10	0.0577 (6)	0.0432 (5)	0.0595 (5)	−0.0142 (4)	0.0153 (5)	−0.0020 (4)
O3	0.0389 (13)	0.0567 (16)	0.0467 (13)	−0.0008 (12)	0.0078 (11)	−0.0022 (12)
C23	0.057 (2)	0.061 (3)	0.060 (2)	−0.022 (2)	0.0116 (19)	−0.0175 (19)
C24	0.0332 (18)	0.060 (2)	0.0428 (18)	−0.0020 (16)	0.0029 (15)	−0.0054 (16)
C25	0.079 (3)	0.044 (2)	0.051 (2)	−0.0144 (19)	0.033 (2)	0.0034 (17)

Geometric parameters (Å, º)

Pd1—S4	2.2693 (10)	C12—H12	0.9300
Pd1—S3	2.2747 (10)	C13—C14	1.381 (5)
Pd1—S8	2.2749 (10)	C13—H13	0.9300
Pd1—S9	2.2757 (11)	C14—C15	1.376 (5)
S4—C3	1.708 (4)	C14—H14	0.9300
C1—S1	1.628 (4)	C15—N1	1.407 (4)
C1—S5	1.712 (5)	C16—N1	1.498 (4)
C1—S2	1.741 (4)	C16—C17	1.530 (4)
C2—C3	1.371 (5)	C16—H16A	0.9700
C2—S3	1.718 (4)	C16—H16B	0.9700
C2—S2	1.743 (4)	C17—C18	1.365 (5)
C3—S5	1.727 (4)	C17—C22	1.386 (5)
C4—S6	1.640 (4)	C18—C19	1.379 (5)
C4—S10	1.708 (4)	C18—H18	0.9300
C4—S7	1.732 (4)	C19—C20	1.321 (5)
C5—C6	1.375 (5)	C19—H19	0.9300
C5—S8	1.712 (4)	C20—C21	1.385 (5)
C5—S7	1.726 (4)	C20—N2	1.486 (4)
C6—S10	1.700 (4)	C21—C22	1.364 (5)
C6—S9	1.737 (4)	C21—H21	0.9300
C7—N1	1.301 (4)	C22—H22	0.9300
C7—C8	1.380 (5)	N2—O2	1.189 (4)
C7—H7	0.9300	N2—O1	1.206 (4)
C8—C9	1.312 (5)	O3—C24	1.173 (4)
C8—H8	0.9300	C23—C24	1.490 (5)
C9—C10	1.425 (4)	C23—H23A	0.9600
C9—H9	0.9300	C23—H23B	0.9600
C10—C15	1.356 (4)	C23—H23C	0.9600
C10—C11	1.457 (4)	C24—C25	1.414 (5)
C11—C12	1.338 (5)	C25—H25A	0.9600
C11—H11	0.9300	C25—H25B	0.9600
C12—C13	1.340 (5)	C25—H25C	0.9600
S4—Pd1—S3	90.97 (4)	N1—C16—C17	112.3 (3)
S4—Pd1—S8	178.05 (4)	N1—C16—H16A	109.1
S3—Pd1—S8	90.62 (4)	C17—C16—H16A	109.1
S4—Pd1—S9	88.07 (4)	N1—C16—H16B	109.1
S3—Pd1—S9	178.21 (4)	C17—C16—H16B	109.1
S8—Pd1—S9	90.37 (4)	H16A—C16—H16B	107.9
C3—S4—Pd1	101.94 (13)	C18—C17—C22	120.1 (3)
S1—C1—S5	124.5 (3)	C18—C17—C16	118.8 (3)
S1—C1—S2	123.3 (3)	C22—C17—C16	121.1 (3)
S5—C1—S2	112.2 (2)	C17—C18—C19	120.0 (4)
C3—C2—S3	123.7 (3)	C17—C18—H18	120.0
C3—C2—S2	115.8 (3)	C19—C18—H18	120.0
S3—C2—S2	120.5 (2)	C20—C19—C18	119.4 (3)
C2—C3—S4	122.4 (3)	C20—C19—H19	120.3
C2—C3—S5	115.2 (3)	C18—C19—H19	120.3
S4—C3—S5	122.4 (2)	C19—C20—C21	122.3 (3)
S6—C4—S10	123.9 (2)	C19—C20—N2	119.1 (3)
S6—C4—S7	122.3 (2)	C21—C20—N2	118.5 (3)
S10—C4—S7	113.8 (2)	C22—C21—C20	118.8 (4)
C6—C5—S8	123.9 (3)	C22—C21—H21	120.6
C6—C5—S7	114.4 (3)	C20—C21—H21	120.6
S8—C5—S7	121.7 (2)	C21—C22—C17	119.3 (4)
C5—C6—S10	117.8 (3)	C21—C22—H22	120.3
C5—C6—S9	121.1 (3)	C17—C22—H22	120.3
S10—C6—S9	121.0 (2)	C7—N1—C15	120.7 (3)
N1—C7—C8	121.5 (3)	C7—N1—C16	122.5 (3)
N1—C7—H7	119.2	C15—N1—C16	116.8 (3)
C8—C7—H7	119.2	O2—N2—O1	122.9 (3)
C9—C8—C7	121.0 (3)	O2—N2—C20	119.1 (3)
C9—C8—H8	119.5	O1—N2—C20	117.7 (3)
C7—C8—H8	119.5	C1—S2—C2	97.62 (19)
C8—C9—C10	118.3 (3)	C2—S3—Pd1	100.94 (12)
C8—C9—H9	120.8	C1—S5—C3	99.10 (19)
C10—C9—H9	120.8	C5—S7—C4	97.10 (18)
C15—C10—C9	120.8 (3)	C5—S8—Pd1	102.05 (12)
C15—C10—C11	118.1 (3)	C6—S9—Pd1	102.50 (12)
C9—C10—C11	121.1 (3)	C6—S10—C4	96.92 (17)
C12—C11—C10	119.7 (3)	C24—C23—H23A	109.5
C12—C11—H11	120.1	C24—C23—H23B	109.5
C10—C11—H11	120.1	H23A—C23—H23B	109.5
C11—C12—C13	119.9 (3)	C24—C23—H23C	109.5
C11—C12—H12	120.0	H23A—C23—H23C	109.5
C13—C12—H12	120.0	H23B—C23—H23C	109.5
C12—C13—C14	122.8 (3)	O3—C24—C25	124.3 (3)
C12—C13—H13	118.6	O3—C24—C23	117.8 (3)
C14—C13—H13	118.6	C25—C24—C23	117.4 (3)
C15—C14—C13	118.2 (3)	C24—C25—H25A	109.5
C15—C14—H14	120.9	C24—C25—H25B	109.5
C13—C14—H14	120.9	H25A—C25—H25B	109.5
C10—C15—C14	121.2 (3)	C24—C25—H25C	109.5
C10—C15—N1	117.6 (3)	H25A—C25—H25C	109.5
C14—C15—N1	121.2 (3)	H25B—C25—H25C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C22—H22···O3^i	0.93	2.56	3.409 (5)	152
C7—H7···O1^ii	0.93	2.35	3.226 (4)	157

Symmetry codes: (i) x, y−1, z; (ii) −x, y+1/2, −z+1/2.