Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805030849/cv6579sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805030849/cv6579Isup2.hkl |
CCDC reference: 287544
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.021 Å
- R factor = 0.059
- wR factor = 0.138
- Data-to-parameter ratio = 17.3
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT241_ALERT_2_B Check High Ueq as Compared to Neighbors for C14 PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for C18 PLAT342_ALERT_3_B Low Bond Precision on C-C bonds (x 1000) Ang ... 21
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 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C10 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N5 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C15 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C8 PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C3 - C4 ... 1.42 Ang. PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C7 - C8 ... 1.42 Ang.
0 ALERT level A = In general: serious problem 3 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 8 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion
Disodium maleonitriledithiolate (Na2mnt) was prepared following the known procedure of Davison & Holm (1967). 1-(4-Bromobenzyl)pyridinium chloride was prepared by reacting 4-bromobenzylchlorine with 1.5 equivalents of pyridine in refluxing acetone for 4 h. The obtained product, containing white microcrystals, was filtered and washed with acetone and diethyl ether in turn, and then dried in vacuo, with a yield ca 80%. K2PtCl4, Na2mnt and 1-(4'-bromobenzyl)pyridinium chloride (equivalent molar ratio 1:2:2) were mixed in water. The red product which precipitated was separated, washed with water and then dissolved in a MeCN. Iodine (1.5 molar equivalents) was added to the boiling solution with stirring. Five times the resulting volume of MeOH was then added and the mixture allowed to stand for 24 h. The microcrystals which formed were separated, washed with MeOH and dried in vacuo, with a yield ca 55%. The saturated MeCN solution of (I) at room temperature was placed in a refrigerator at 277 K for one week, and single crystals of (I) suitable for X-ray crystal structure analysis were obtained.
All H atoms were placed in geometrically calculated positions and refined as riding, with C—H = 0.93–0.97 Å and Uiso(H) = 1.2Ueq(C). The residual electron density of 1.86 e Å−3 and the deepest hole of −1.58 e Å−3 are situated at 1.04 and 1.74 Å from Pt1, respectively.
Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97.
(C12H11BrN)[Pt(C4N2S2)2] | F(000) = 1372 |
Mr = 724.58 | Dx = 2.046 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 851 reflections |
a = 7.3814 (8) Å | θ = 2.9–23.8° |
b = 26.180 (3) Å | µ = 8.04 mm−1 |
c = 12.6488 (14) Å | T = 293 K |
β = 105.739 (2)° | Needle, black |
V = 2352.7 (5) Å3 | 0.20 × 0.15 × 0.10 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 4851 independent reflections |
Radiation source: fine-focus sealed tube | 2886 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.097 |
ϕ and ω scans | θmax = 26.5°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.24, Tmax = 0.45 | k = −32→28 |
13418 measured reflections | l = −13→15 |
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 0.92 | w = 1/[σ2(Fo2) + (0.0566P)2] where P = (Fo2 + 2Fc2)/3 |
4851 reflections | (Δ/σ)max = 0.001 |
280 parameters | Δρmax = 1.86 e Å−3 |
0 restraints | Δρmin = −1.58 e Å−3 |
(C12H11BrN)[Pt(C4N2S2)2] | V = 2352.7 (5) Å3 |
Mr = 724.58 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.3814 (8) Å | µ = 8.04 mm−1 |
b = 26.180 (3) Å | T = 293 K |
c = 12.6488 (14) Å | 0.20 × 0.15 × 0.10 mm |
β = 105.739 (2)° |
Bruker SMART CCD area-detector diffractometer | 4851 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2886 reflections with I > 2σ(I) |
Tmin = 0.24, Tmax = 0.45 | Rint = 0.097 |
13418 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 0.92 | Δρmax = 1.86 e Å−3 |
4851 reflections | Δρmin = −1.58 e Å−3 |
280 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 | ||
Pt1 | 0.71258 (6) | 0.977887 (18) | 0.48253 (3) | 0.04922 (17) | |
Br1 | 0.8054 (3) | 1.07958 (7) | 0.0098 (3) | 0.1851 (14) | |
S1 | 0.8524 (4) | 1.02629 (12) | 0.6303 (2) | 0.0566 (7) | |
S2 | 0.7040 (4) | 1.04611 (12) | 0.3725 (2) | 0.0606 (8) | |
S3 | 0.7259 (4) | 0.90745 (11) | 0.5886 (2) | 0.0577 (7) | |
S4 | 0.5705 (4) | 0.93170 (13) | 0.3331 (2) | 0.0622 (8) | |
N1 | 1.0213 (17) | 1.1546 (4) | 0.7077 (9) | 0.085 (3) | |
N2 | 0.829 (2) | 1.1787 (5) | 0.3721 (11) | 0.116 (5) | |
N3 | 0.6142 (19) | 0.7689 (5) | 0.5580 (11) | 0.103 (4) | |
N4 | 0.424 (2) | 0.8005 (6) | 0.2463 (12) | 0.131 (5) | |
N5 | 0.7887 (17) | 0.8212 (4) | −0.0571 (11) | 0.075 (3) | |
C1 | 0.9528 (18) | 1.1241 (5) | 0.6459 (10) | 0.065 (3) | |
C2 | 0.8713 (14) | 1.0842 (4) | 0.5749 (9) | 0.051 (3) | |
C3 | 0.8034 (16) | 1.0935 (5) | 0.4631 (10) | 0.060 (3) | |
C4 | 0.818 (2) | 1.1418 (5) | 0.4154 (12) | 0.079 (4) | |
C5 | 0.6219 (18) | 0.8114 (6) | 0.5307 (10) | 0.074 (4) | |
C6 | 0.6339 (15) | 0.8620 (5) | 0.4944 (8) | 0.056 (3) | |
C7 | 0.5614 (15) | 0.8723 (5) | 0.3828 (9) | 0.059 (3) | |
C8 | 0.4851 (19) | 0.8322 (5) | 0.3087 (11) | 0.073 (4) | |
C9 | 0.776 (2) | 0.8045 (6) | −0.1567 (13) | 0.104 (5) | |
H9A | 0.6660 | 0.8108 | −0.2119 | 0.125* | |
C10 | 0.917 (3) | 0.7786 (6) | −0.1818 (13) | 0.118 (6) | |
H10A | 0.9023 | 0.7658 | −0.2522 | 0.142* | |
C11 | 1.080 (2) | 0.7714 (6) | −0.1025 (16) | 0.100 (5) | |
H11A | 1.1815 | 0.7557 | −0.1198 | 0.120* | |
C12 | 1.097 (2) | 0.7869 (5) | 0.0013 (14) | 0.093 (5) | |
H12A | 1.2052 | 0.7802 | 0.0571 | 0.111* | |
C13 | 0.947 (3) | 0.8132 (5) | 0.0226 (12) | 0.086 (4) | |
H13A | 0.9575 | 0.8253 | 0.0931 | 0.103* | |
C14 | 0.637 (2) | 0.8527 (6) | −0.0313 (15) | 0.120 (6) | |
H14A | 0.5214 | 0.8479 | −0.0891 | 0.144* | |
H14B | 0.6157 | 0.8404 | 0.0367 | 0.144* | |
C15 | 0.6801 (17) | 0.9062 (5) | −0.0204 (11) | 0.065 (3) | |
C16 | 0.6734 (19) | 0.9332 (6) | −0.1101 (11) | 0.082 (4) | |
H16A | 0.6432 | 0.9167 | −0.1778 | 0.098* | |
C17 | 0.709 (2) | 0.9838 (7) | −0.1060 (12) | 0.094 (6) | |
H17A | 0.7029 | 1.0019 | −0.1701 | 0.113* | |
C18 | 0.7574 (17) | 1.0093 (6) | −0.0018 (16) | 0.086 (5) | |
C19 | 0.759 (2) | 0.9788 (7) | 0.0909 (13) | 0.094 (5) | |
H19A | 0.7856 | 0.9934 | 0.1605 | 0.113* | |
C20 | 0.723 (2) | 0.9293 (6) | 0.0777 (11) | 0.082 (4) | |
H20A | 0.7272 | 0.9096 | 0.1395 | 0.098* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.0389 (2) | 0.0672 (3) | 0.0432 (2) | 0.0059 (2) | 0.01388 (17) | −0.0015 (2) |
Br1 | 0.0758 (12) | 0.0711 (12) | 0.427 (5) | 0.0013 (9) | 0.100 (2) | 0.0005 (17) |
S1 | 0.0483 (16) | 0.074 (2) | 0.0460 (16) | −0.0005 (15) | 0.0103 (13) | −0.0040 (15) |
S2 | 0.0565 (18) | 0.078 (2) | 0.0474 (17) | 0.0068 (16) | 0.0147 (14) | 0.0069 (15) |
S3 | 0.0550 (18) | 0.0653 (19) | 0.0495 (17) | 0.0065 (15) | 0.0089 (14) | −0.0002 (14) |
S4 | 0.064 (2) | 0.082 (2) | 0.0414 (16) | 0.0014 (17) | 0.0160 (14) | −0.0048 (15) |
N1 | 0.103 (9) | 0.078 (8) | 0.072 (8) | 0.001 (7) | 0.020 (7) | 0.000 (6) |
N2 | 0.170 (14) | 0.083 (10) | 0.113 (11) | 0.032 (10) | 0.068 (10) | 0.025 (8) |
N3 | 0.109 (10) | 0.085 (10) | 0.113 (10) | 0.014 (8) | 0.030 (8) | 0.004 (8) |
N4 | 0.119 (12) | 0.150 (14) | 0.116 (12) | −0.017 (10) | 0.022 (9) | −0.060 (10) |
N5 | 0.073 (8) | 0.072 (8) | 0.088 (9) | −0.015 (6) | 0.033 (7) | −0.025 (7) |
C1 | 0.073 (9) | 0.065 (9) | 0.057 (8) | 0.002 (7) | 0.019 (7) | −0.010 (7) |
C2 | 0.044 (6) | 0.064 (8) | 0.052 (7) | 0.014 (6) | 0.025 (6) | 0.005 (6) |
C3 | 0.056 (7) | 0.070 (9) | 0.061 (8) | 0.007 (6) | 0.026 (6) | 0.002 (6) |
C4 | 0.102 (11) | 0.062 (10) | 0.089 (10) | 0.020 (8) | 0.052 (9) | 0.006 (8) |
C5 | 0.065 (9) | 0.092 (12) | 0.062 (9) | 0.010 (9) | 0.012 (7) | −0.010 (8) |
C6 | 0.054 (7) | 0.071 (9) | 0.044 (7) | 0.017 (6) | 0.014 (5) | −0.001 (6) |
C7 | 0.051 (7) | 0.078 (9) | 0.052 (7) | −0.001 (6) | 0.020 (6) | −0.019 (6) |
C8 | 0.075 (9) | 0.081 (10) | 0.063 (9) | 0.007 (8) | 0.020 (7) | −0.010 (7) |
C9 | 0.105 (13) | 0.111 (14) | 0.084 (12) | 0.026 (10) | 0.005 (10) | −0.014 (10) |
C10 | 0.19 (2) | 0.099 (13) | 0.067 (11) | 0.034 (13) | 0.039 (13) | −0.003 (9) |
C11 | 0.099 (13) | 0.082 (11) | 0.117 (14) | 0.021 (10) | 0.025 (11) | −0.001 (11) |
C12 | 0.098 (13) | 0.059 (10) | 0.103 (13) | −0.008 (9) | −0.003 (10) | 0.002 (9) |
C13 | 0.113 (13) | 0.081 (11) | 0.067 (10) | −0.022 (10) | 0.029 (10) | −0.012 (8) |
C14 | 0.084 (11) | 0.110 (15) | 0.189 (19) | −0.015 (10) | 0.076 (12) | −0.026 (12) |
C15 | 0.066 (9) | 0.071 (9) | 0.065 (8) | −0.008 (7) | 0.031 (7) | 0.000 (7) |
C16 | 0.088 (11) | 0.089 (11) | 0.065 (9) | 0.022 (9) | 0.015 (8) | 0.014 (8) |
C17 | 0.075 (10) | 0.154 (17) | 0.063 (9) | 0.052 (11) | 0.037 (8) | 0.059 (11) |
C18 | 0.040 (8) | 0.087 (12) | 0.139 (16) | 0.015 (7) | 0.037 (9) | 0.018 (10) |
C19 | 0.070 (10) | 0.127 (15) | 0.078 (11) | 0.042 (11) | 0.008 (8) | −0.013 (11) |
C20 | 0.098 (11) | 0.092 (12) | 0.070 (10) | 0.019 (9) | 0.049 (9) | 0.010 (8) |
Pt1—S4 | 2.249 (3) | C9—C10 | 1.35 (2) |
Pt1—S2 | 2.255 (3) | C9—H9A | 0.9300 |
Pt1—S1 | 2.262 (3) | C10—C11 | 1.36 (2) |
Pt1—S3 | 2.267 (3) | C10—H10A | 0.9300 |
Br1—C18 | 1.871 (16) | C11—C12 | 1.348 (19) |
S1—C2 | 1.691 (11) | C11—H11A | 0.9300 |
S2—C3 | 1.713 (12) | C12—C13 | 1.385 (19) |
S3—C6 | 1.691 (12) | C12—H12A | 0.9300 |
S4—C7 | 1.687 (12) | C13—H13A | 0.9300 |
N1—C1 | 1.137 (14) | C14—C15 | 1.436 (18) |
N2—C4 | 1.124 (15) | C14—H14A | 0.9700 |
N3—C5 | 1.169 (16) | C14—H14B | 0.9700 |
N4—C8 | 1.149 (16) | C15—C16 | 1.325 (16) |
N5—C9 | 1.312 (17) | C15—C20 | 1.339 (17) |
N5—C13 | 1.339 (18) | C16—C17 | 1.349 (19) |
N5—C14 | 1.496 (17) | C16—H16A | 0.9300 |
C1—C2 | 1.403 (16) | C17—C18 | 1.43 (2) |
C2—C3 | 1.387 (15) | C17—H17A | 0.9300 |
C3—C4 | 1.417 (17) | C18—C19 | 1.42 (2) |
C5—C6 | 1.413 (18) | C19—C20 | 1.325 (18) |
C6—C7 | 1.393 (14) | C19—H19A | 0.9300 |
C7—C8 | 1.418 (16) | C20—H20A | 0.9300 |
S4—Pt1—S2 | 88.78 (11) | C11—C10—H10A | 120.6 |
S4—Pt1—S1 | 178.45 (11) | C12—C11—C10 | 120.4 (16) |
S2—Pt1—S1 | 89.79 (11) | C12—C11—H11A | 119.8 |
S4—Pt1—S3 | 89.75 (11) | C10—C11—H11A | 119.8 |
S2—Pt1—S3 | 177.76 (10) | C11—C12—C13 | 118.3 (15) |
S1—Pt1—S3 | 91.70 (11) | C11—C12—H12A | 120.9 |
C2—S1—Pt1 | 103.3 (4) | C13—C12—H12A | 120.9 |
C3—S2—Pt1 | 103.1 (4) | N5—C13—C12 | 120.7 (13) |
C6—S3—Pt1 | 102.2 (4) | N5—C13—H13A | 119.7 |
C7—S4—Pt1 | 103.8 (4) | C12—C13—H13A | 119.7 |
C9—N5—C13 | 119.5 (13) | C15—C14—N5 | 113.6 (11) |
C9—N5—C14 | 122.0 (15) | C15—C14—H14A | 108.9 |
C13—N5—C14 | 118.4 (13) | N5—C14—H14A | 108.9 |
N1—C1—C2 | 176.5 (14) | C15—C14—H14B | 108.9 |
C3—C2—C1 | 119.6 (11) | N5—C14—H14B | 108.9 |
C3—C2—S1 | 122.2 (9) | H14A—C14—H14B | 107.7 |
C1—C2—S1 | 118.1 (9) | C16—C15—C20 | 119.9 (14) |
C2—C3—C4 | 122.9 (12) | C16—C15—C14 | 118.9 (14) |
C2—C3—S2 | 121.6 (9) | C20—C15—C14 | 121.3 (14) |
C4—C3—S2 | 115.4 (10) | C15—C16—C17 | 121.9 (14) |
N2—C4—C3 | 175.9 (15) | C15—C16—H16A | 119.0 |
N3—C5—C6 | 177.8 (15) | C17—C16—H16A | 119.0 |
C7—C6—C5 | 118.0 (11) | C16—C17—C18 | 119.4 (13) |
C7—C6—S3 | 123.2 (10) | C16—C17—H17A | 120.3 |
C5—C6—S3 | 118.7 (9) | C18—C17—H17A | 120.3 |
C6—C7—C8 | 120.1 (12) | C19—C18—C17 | 116.2 (15) |
C6—C7—S4 | 120.9 (9) | C19—C18—Br1 | 122.0 (15) |
C8—C7—S4 | 119.0 (9) | C17—C18—Br1 | 121.7 (14) |
N4—C8—C7 | 178.1 (16) | C20—C19—C18 | 119.4 (14) |
N5—C9—C10 | 122.2 (16) | C20—C19—H19A | 120.3 |
N5—C9—H9A | 118.9 | C18—C19—H19A | 120.3 |
C10—C9—H9A | 118.9 | C19—C20—C15 | 123.2 (14) |
C9—C10—C11 | 118.9 (15) | C19—C20—H20A | 118.4 |
C9—C10—H10A | 120.6 | C15—C20—H20A | 118.4 |
Experimental details
Crystal data | |
Chemical formula | (C12H11BrN)[Pt(C4N2S2)2] |
Mr | 724.58 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 7.3814 (8), 26.180 (3), 12.6488 (14) |
β (°) | 105.739 (2) |
V (Å3) | 2352.7 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 8.04 |
Crystal size (mm) | 0.20 × 0.15 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.24, 0.45 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13418, 4851, 2886 |
Rint | 0.097 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.138, 0.92 |
No. of reflections | 4851 |
No. of parameters | 280 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.86, −1.58 |
Computer programs: SMART (Siemens, 1996), SMART, SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXL97.
Pt1—S4 | 2.249 (3) | Pt1—S1 | 2.262 (3) |
Pt1—S2 | 2.255 (3) | Pt1—S3 | 2.267 (3) |
S4—Pt1—S2 | 88.78 (11) | S4—Pt1—S3 | 89.75 (11) |
S4—Pt1—S1 | 178.45 (11) | S2—Pt1—S3 | 177.76 (10) |
S2—Pt1—S1 | 89.79 (11) | S1—Pt1—S3 | 91.70 (11) |
Organic charge-transfer salts with segregated stacks are the subject of intensive study, due to their unusual properties in magnetism and conductivity (Coomber et al., 1996; Kawamura et al., 1997; Xie, Ren, Song, Zou & Meng, 2002; Xie, Ren, Song, Zhang et al., 2002; Xie et al., 2003). Recently, we reported the crystal structure of an ion-pair compound, 1-(4'-bromobenzyl)pyridinium bis(maleonitriledithiolato)platinate(III), which possesses segregated and regular stacks of cations and anions. Such an anionic stack behaves as a one-dimensional magnet with S = 1/2 and undergoes a magnetostructural transition at ca 260 K, which results from the instability of the one-dimensional electron gas (Ren et al., 2004). Here, we present the crystal structure of a new polymorph of the title compound, (I) (Fig. 1), which we have called the β-phase. The α-phase corresponds to the crystal form reported earlier (Ren et al., 2004).
The β-phase crystallizes in a monoclinic space group, with one cation and one anion in the asymmetric unit. The anionic moiety, [Pt(mnt)2]−, shows a square-planar geometry (mnt is maleonitriledithiolate). The Pt—S bond lengths (Table 1) range from 2.249 (3) to 2.267 (3) Å. The S—Pt—S angles in the two chelate rings [89.79 (11) and 89.75 (11)°] are in a good agreement with the values observed in the α-phase. In the cation, the plane formed by atoms N5/C14/C15 makes dihedral angles with the benzene and pyridine rings of 72.6 (15) and 104.6 (10)°, respectively, while in the α-phase, the corresponding dihedral angles are 98.5 (6) and 93.1 (5)°, respectively. The dihedral angles between the benzene and pyridine rings in the β- and α-phases are 75.9 (4) and 114.1 (2)°, respectively. In the crystal structure of (I), the anions and cations stack into segregated columns along the a axis (Fig. 2).
There are remarkable differences in the crystal structures of the two polymorphs. The anionic stacks in the α- and β-phases are regular (Fig. 3a) and irregular (Fig. 3b), respectively. In the β-phase, two stacking patterns exist between adjacent anions, namely face-to-face overlap, and longitudinal and transverse offset. The face-to-face overlap involves an anionic pair containing atoms Pt1 and Pt1i [symmetry code: (i) 1 − x, 2 − y, 1 − z], in which the distance between the PtIII ions [3.4838 (8) Å] is comparable with that between the corresponding mean planes defined by the four coordinating S atoms [3.489 (3) Å]. The longitudinal and transverse offset involves an anionic pair containing atoms Pt1 and Pt1ii [symmetry code: (ii) 2 − x, 2 − y, 1 − z], in which the distances between the PtIII ions and between the corresponding mean planes are 4.3038 (9) and 3.6235 (4) Å, respectively. Within a cationic stack, neighbouring cations in the α- and β-phases are stacked in chair-conformation-like (Fig. 4a) and boat-conformation-like (Fig. 4b) fashions, respectively. In the β-phase, the anionic molecular planes in neighbouring stacks are inclined to each other with a dihedral angle of 27.73 (5)° [1.32 (5)° in the α-phase]. The dihedral angle between benzene rings in neighbouring cationic stacks is 21.94 (25)° [3.58 (18)° in the α-phase].
With respect to the [M(mnt)2]−-based compounds (M = Ni, Pd or Pt), their physical properties, such as conductivity and magnetism, are sensitive to the anionic stacking pattern. Therefore, the two polymorphs of (I) probably possess distinct conducting and magnetic behaviours, and such measurements are in progress.