Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107044009/bm3040sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107044009/bm3040Isup2.hkl |
CCDC reference: 665490
For related literature, see: Abe (2007); Abe & Shinozaki (2005); Cárdenas & Echavarren (1999); Farley et al. (2005); Krönke (1963); Te Velde et al. (2001); Ziegler (1991); Williams et al. (2003).
1,3-Di(5-methyl-2-pyridyl)benzene (5Hdpb) was synthesized from 1,3-diacetylbenzene, methacrolein and ammonium acetate by the procedure described by Krönke (1963). [Pt(5 d pb)Cl] was prepared from K2PtCl4 (200 mg) and 5Hdpb (140 mg) by refluxing in acetic acid (100 ml) for 24 h. Partial removal of solvent by evaporation gave yellow crystals. These were collected by filtration [AUTHOR: At this point you have the sample as solid crystals. Logically, before you can pass them through the column you must either (a) re-dissolve them or (b) place the solid material on top of the column and add an eluent. Please clarify what you did.] and purified by passage through a silica-gel column (1.5 cm in diameter and 30 cm in length) eluted with CHCl3 (200 ml) three times. Addition of hexane to the solution gave bright-yellow crystals (yield 50%). 1H NMR (270 MHz, CDCl3, 298 K, TMS): δ 9.06 (2H, s, CH), 7.68 (2H, d, CH), 7.51 (2H, d, CH), 7.32 (2H, d, CH), 7.13 (1H, t, CH), and 2.37 (6H, s, CH3); ESI–MS m/z = 454 [M—Cl]+, 491 [M+H]+. A single-crystal suitable for X-ray analysis was obtained by the slow evaporation of solvent from an ethanol–toluene (1:1) solution.
Methyl H atoms were located from ΔF syntheses and refined as rigid groups which were allowed to rotate but not tip or distort [C—H = 0.98 Å and Uiso(H) = 1.2Ueq(C)]. Aromatic H atoms were placed geometrically and constrained to ride on their parent atoms [C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C)].
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku, 2005); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[PtCl(C18H15N2)] | F(000) = 928 |
Mr = 489.86 | Dx = 2.097 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71075 Å |
a = 9.657 (4) Å | Cell parameters from 12459 reflections |
b = 12.969 (5) Å | θ = 3.1–27.4° |
c = 12.962 (6) Å | µ = 9.21 mm−1 |
β = 107.092 (17)° | T = 200 K |
V = 1551.7 (11) Å3 | Parallelepiped, yellow |
Z = 4 | 0.20 × 0.15 × 0.12 mm |
Rigaku R-AXIS RAPID diffractometer | 3524 independent reflections |
Radiation source: fine-focus sealed tube | 3301 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
Detector resolution: 10.00 pixels mm-1 | θmax = 27.4°, θmin = 3.1° |
ω scans | h = −12→12 |
Absorption correction: numerical (SHAPE; Higashi, 1999) | k = −16→16 |
Tmin = 0.260, Tmax = 0.459 | l = −16→16 |
14606 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.018 | H-atom parameters constrained |
wR(F2) = 0.039 | w = 1/[σ2(Fo2) + (0.012P)2 + 1.691P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.002 |
3524 reflections | Δρmax = 0.92 e Å−3 |
203 parameters | Δρmin = −0.71 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00142 (12) |
[PtCl(C18H15N2)] | V = 1551.7 (11) Å3 |
Mr = 489.86 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.657 (4) Å | µ = 9.21 mm−1 |
b = 12.969 (5) Å | T = 200 K |
c = 12.962 (6) Å | 0.20 × 0.15 × 0.12 mm |
β = 107.092 (17)° |
Rigaku R-AXIS RAPID diffractometer | 3524 independent reflections |
Absorption correction: numerical (SHAPE; Higashi, 1999) | 3301 reflections with I > 2σ(I) |
Tmin = 0.260, Tmax = 0.459 | Rint = 0.028 |
14606 measured reflections |
R[F2 > 2σ(F2)] = 0.018 | 0 restraints |
wR(F2) = 0.039 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.92 e Å−3 |
3524 reflections | Δρmin = −0.71 e Å−3 |
203 parameters |
x | y | z | Uiso*/Ueq | ||
Pt1 | 0.847333 (11) | 0.139609 (7) | 0.909274 (8) | 0.02194 (5) | |
Cl1 | 0.75862 (8) | 0.23422 (6) | 1.03678 (6) | 0.03561 (17) | |
N1 | 0.9244 (2) | 0.26150 (17) | 0.84517 (17) | 0.0240 (5) | |
N2 | 0.7979 (2) | −0.00789 (17) | 0.94057 (18) | 0.0250 (5) | |
C1 | 0.9255 (3) | 0.0675 (2) | 0.8102 (2) | 0.0261 (6) | |
C2 | 0.9951 (3) | 0.1242 (2) | 0.7486 (2) | 0.0292 (6) | |
C3 | 1.0501 (3) | 0.0717 (3) | 0.6747 (3) | 0.0369 (7) | |
H3 | 1.0960 | 0.1084 | 0.6304 | 0.044* | |
C4 | 1.0364 (4) | −0.0350 (3) | 0.6675 (3) | 0.0430 (8) | |
H4 | 1.0728 | −0.0707 | 0.6169 | 0.052* | |
C5 | 0.9708 (4) | −0.0916 (2) | 0.7320 (3) | 0.0375 (7) | |
H5 | 0.9644 | −0.1645 | 0.7261 | 0.045* | |
C6 | 0.9149 (3) | −0.0397 (2) | 0.8050 (2) | 0.0292 (6) | |
C7 | 0.9979 (3) | 0.2353 (2) | 0.7720 (2) | 0.0265 (6) | |
C8 | 1.0659 (3) | 0.3109 (2) | 0.7291 (2) | 0.0345 (7) | |
H8 | 1.1195 | 0.2928 | 0.6809 | 0.041* | |
C9 | 1.0553 (3) | 0.4130 (2) | 0.7567 (2) | 0.0356 (7) | |
H9 | 1.1034 | 0.4647 | 0.7282 | 0.043* | |
C10 | 0.9752 (3) | 0.4412 (2) | 0.8256 (2) | 0.0302 (6) | |
C11 | 0.9132 (3) | 0.3615 (2) | 0.8690 (2) | 0.0267 (6) | |
H11 | 0.8602 | 0.3787 | 0.9178 | 0.032* | |
C12 | 0.8434 (3) | −0.0819 (2) | 0.8812 (2) | 0.0281 (6) | |
C13 | 0.8192 (3) | −0.1855 (2) | 0.8979 (2) | 0.0333 (6) | |
H13 | 0.8520 | −0.2370 | 0.8585 | 0.040* | |
C14 | 0.7477 (3) | −0.2137 (2) | 0.9714 (3) | 0.0346 (7) | |
H14 | 0.7309 | −0.2845 | 0.9820 | 0.041* | |
C15 | 0.7003 (3) | −0.1392 (2) | 1.0297 (3) | 0.0318 (6) | |
C16 | 0.7295 (3) | −0.0366 (2) | 1.0124 (2) | 0.0299 (6) | |
H16 | 0.6999 | 0.0152 | 1.0532 | 0.036* | |
C17 | 0.9544 (4) | 0.5519 (2) | 0.8512 (3) | 0.0381 (7) | |
H17A | 1.0486 | 0.5867 | 0.8737 | 0.046* | |
H17B | 0.9093 | 0.5554 | 0.9096 | 0.046* | |
H17C | 0.8917 | 0.5860 | 0.7868 | 0.046* | |
C18 | 0.6186 (4) | −0.1671 (3) | 1.1096 (3) | 0.0422 (8) | |
H18A | 0.5279 | −0.1280 | 1.0927 | 0.051* | |
H18B | 0.6782 | −0.1503 | 1.1829 | 0.051* | |
H18C | 0.5970 | −0.2411 | 1.1047 | 0.051* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.02406 (7) | 0.02172 (7) | 0.02167 (6) | −0.00088 (4) | 0.00927 (4) | −0.00136 (4) |
Cl1 | 0.0458 (4) | 0.0314 (4) | 0.0402 (4) | −0.0051 (3) | 0.0290 (4) | −0.0067 (3) |
N1 | 0.0243 (11) | 0.0263 (12) | 0.0222 (11) | −0.0010 (9) | 0.0078 (9) | 0.0009 (9) |
N2 | 0.0261 (12) | 0.0235 (11) | 0.0260 (11) | −0.0011 (9) | 0.0084 (10) | 0.0001 (9) |
C1 | 0.0248 (13) | 0.0287 (14) | 0.0248 (13) | 0.0032 (11) | 0.0072 (11) | −0.0039 (11) |
C2 | 0.0294 (15) | 0.0324 (15) | 0.0273 (14) | 0.0026 (12) | 0.0104 (12) | 0.0012 (11) |
C3 | 0.0408 (17) | 0.0403 (18) | 0.0366 (16) | 0.0016 (14) | 0.0219 (15) | 0.0008 (14) |
C4 | 0.051 (2) | 0.0403 (18) | 0.0454 (19) | 0.0056 (15) | 0.0266 (17) | −0.0115 (15) |
C5 | 0.0453 (18) | 0.0295 (16) | 0.0417 (17) | 0.0044 (14) | 0.0192 (15) | −0.0078 (13) |
C6 | 0.0294 (15) | 0.0283 (14) | 0.0291 (14) | 0.0021 (11) | 0.0074 (12) | −0.0027 (11) |
C7 | 0.0277 (14) | 0.0322 (15) | 0.0214 (12) | 0.0038 (11) | 0.0101 (11) | 0.0007 (11) |
C8 | 0.0348 (16) | 0.0414 (17) | 0.0318 (15) | 0.0004 (14) | 0.0168 (13) | 0.0029 (13) |
C9 | 0.0412 (17) | 0.0337 (16) | 0.0342 (16) | −0.0061 (14) | 0.0146 (14) | 0.0067 (13) |
C10 | 0.0338 (15) | 0.0298 (15) | 0.0252 (14) | −0.0049 (12) | 0.0058 (12) | 0.0033 (11) |
C11 | 0.0288 (14) | 0.0282 (14) | 0.0221 (13) | −0.0007 (11) | 0.0059 (11) | −0.0016 (10) |
C12 | 0.0270 (14) | 0.0272 (14) | 0.0272 (14) | −0.0001 (11) | 0.0034 (11) | −0.0029 (11) |
C13 | 0.0356 (16) | 0.0239 (14) | 0.0373 (16) | 0.0011 (12) | 0.0060 (13) | −0.0045 (12) |
C14 | 0.0367 (16) | 0.0236 (14) | 0.0392 (17) | −0.0055 (12) | 0.0046 (14) | 0.0023 (12) |
C15 | 0.0312 (16) | 0.0293 (15) | 0.0328 (16) | −0.0046 (12) | 0.0063 (13) | 0.0015 (12) |
C16 | 0.0292 (15) | 0.0293 (15) | 0.0306 (15) | −0.0043 (12) | 0.0079 (12) | −0.0017 (12) |
C17 | 0.0494 (19) | 0.0264 (15) | 0.0368 (17) | −0.0054 (13) | 0.0098 (15) | 0.0001 (12) |
C18 | 0.048 (2) | 0.0347 (17) | 0.049 (2) | −0.0085 (15) | 0.0222 (17) | 0.0058 (15) |
Pt1—C1 | 1.915 (3) | C8—H8 | 0.9500 |
Pt1—N1 | 2.027 (2) | C9—C10 | 1.391 (4) |
Pt1—N2 | 2.041 (2) | C9—H9 | 0.9500 |
Pt1—Cl1 | 2.4091 (10) | C10—C11 | 1.393 (4) |
N1—C11 | 1.345 (3) | C10—C17 | 1.501 (4) |
N1—C7 | 1.384 (3) | C11—H11 | 0.9500 |
N2—C16 | 1.343 (4) | C12—C13 | 1.391 (4) |
N2—C12 | 1.380 (4) | C13—C14 | 1.380 (4) |
C1—C6 | 1.394 (4) | C13—H13 | 0.9500 |
C1—C2 | 1.394 (4) | C14—C15 | 1.384 (4) |
C2—C3 | 1.400 (4) | C14—H14 | 0.9500 |
C2—C7 | 1.471 (4) | C15—C16 | 1.392 (4) |
C3—C4 | 1.392 (5) | C15—C18 | 1.519 (4) |
C3—H3 | 0.9500 | C16—H16 | 0.9500 |
C4—C5 | 1.396 (5) | C17—H17A | 0.9800 |
C4—H4 | 0.9500 | C17—H17B | 0.9800 |
C5—C6 | 1.393 (4) | C17—H17C | 0.9800 |
C5—H5 | 0.9500 | C18—H18A | 0.9800 |
C6—C12 | 1.469 (4) | C18—H18B | 0.9800 |
C7—C8 | 1.385 (4) | C18—H18C | 0.9800 |
C8—C9 | 1.383 (5) | ||
C1—Pt1—N1 | 80.87 (11) | C8—C9—C10 | 121.0 (3) |
C1—Pt1—N2 | 80.61 (11) | C8—C9—H9 | 119.5 |
N1—Pt1—N2 | 161.47 (9) | C10—C9—H9 | 119.5 |
C1—Pt1—Cl1 | 177.56 (9) | C9—C10—C11 | 116.8 (3) |
N1—Pt1—Cl1 | 97.56 (7) | C9—C10—C17 | 121.9 (3) |
N2—Pt1—Cl1 | 100.94 (7) | C11—C10—C17 | 121.3 (3) |
C11—N1—C7 | 119.1 (2) | N1—C11—C10 | 123.4 (3) |
C11—N1—Pt1 | 126.45 (19) | N1—C11—H11 | 118.3 |
C7—N1—Pt1 | 114.43 (18) | C10—C11—H11 | 118.3 |
C16—N2—C12 | 119.7 (2) | N2—C12—C13 | 119.3 (3) |
C16—N2—Pt1 | 126.13 (19) | N2—C12—C6 | 113.9 (3) |
C12—N2—Pt1 | 114.19 (18) | C13—C12—C6 | 126.7 (3) |
C6—C1—C2 | 122.6 (3) | C14—C13—C12 | 120.2 (3) |
C6—C1—Pt1 | 118.8 (2) | C14—C13—H13 | 119.9 |
C2—C1—Pt1 | 118.5 (2) | C12—C13—H13 | 119.9 |
C1—C2—C3 | 118.6 (3) | C13—C14—C15 | 120.4 (3) |
C1—C2—C7 | 112.5 (2) | C13—C14—H14 | 119.8 |
C3—C2—C7 | 129.0 (3) | C15—C14—H14 | 119.8 |
C4—C3—C2 | 118.8 (3) | C14—C15—C16 | 117.6 (3) |
C4—C3—H3 | 120.6 | C14—C15—C18 | 121.8 (3) |
C2—C3—H3 | 120.6 | C16—C15—C18 | 120.6 (3) |
C3—C4—C5 | 122.2 (3) | N2—C16—C15 | 122.8 (3) |
C3—C4—H4 | 118.9 | N2—C16—H16 | 118.6 |
C5—C4—H4 | 118.9 | C15—C16—H16 | 118.6 |
C6—C5—C4 | 119.2 (3) | C10—C17—H17A | 109.5 |
C6—C5—H5 | 120.4 | C10—C17—H17B | 109.5 |
C4—C5—H5 | 120.4 | H17A—C17—H17B | 109.5 |
C5—C6—C1 | 118.5 (3) | C10—C17—H17C | 109.5 |
C5—C6—C12 | 129.1 (3) | H17A—C17—H17C | 109.5 |
C1—C6—C12 | 112.4 (2) | H17B—C17—H17C | 109.5 |
N1—C7—C8 | 120.0 (3) | C15—C18—H18A | 109.5 |
N1—C7—C2 | 113.6 (2) | C15—C18—H18B | 109.5 |
C8—C7—C2 | 126.4 (3) | H18A—C18—H18B | 109.5 |
C9—C8—C7 | 119.6 (3) | C15—C18—H18C | 109.5 |
C9—C8—H8 | 120.2 | H18A—C18—H18C | 109.5 |
C7—C8—H8 | 120.2 | H18B—C18—H18C | 109.5 |
C1—Pt1—N1—C11 | 178.0 (2) | C11—N1—C7—C2 | −176.7 (3) |
N2—Pt1—N1—C11 | 179.2 (3) | Pt1—N1—C7—C2 | 4.7 (3) |
Cl1—Pt1—N1—C11 | −3.9 (2) | C1—C2—C7—N1 | −3.5 (4) |
C1—Pt1—N1—C7 | −3.53 (19) | C3—C2—C7—N1 | 175.9 (3) |
N2—Pt1—N1—C7 | −2.3 (4) | C1—C2—C7—C8 | 176.0 (3) |
Cl1—Pt1—N1—C7 | 174.58 (18) | C3—C2—C7—C8 | −4.6 (5) |
C1—Pt1—N2—C16 | 180.0 (3) | N1—C7—C8—C9 | −2.4 (4) |
N1—Pt1—N2—C16 | 178.7 (3) | C2—C7—C8—C9 | 178.1 (3) |
Cl1—Pt1—N2—C16 | 1.9 (2) | C7—C8—C9—C10 | −1.1 (5) |
C1—Pt1—N2—C12 | 1.0 (2) | C8—C9—C10—C11 | 3.1 (4) |
N1—Pt1—N2—C12 | −0.2 (4) | C8—C9—C10—C17 | −176.1 (3) |
Cl1—Pt1—N2—C12 | −177.10 (18) | C7—N1—C11—C10 | −1.7 (4) |
N1—Pt1—C1—C6 | 179.5 (2) | Pt1—N1—C11—C10 | 176.7 (2) |
N2—Pt1—C1—C6 | −0.1 (2) | C9—C10—C11—N1 | −1.7 (4) |
N1—Pt1—C1—C2 | 1.6 (2) | C17—C10—C11—N1 | 177.4 (3) |
N2—Pt1—C1—C2 | −178.0 (2) | C16—N2—C12—C13 | −0.8 (4) |
C6—C1—C2—C3 | 3.2 (4) | Pt1—N2—C12—C13 | 178.3 (2) |
Pt1—C1—C2—C3 | −178.9 (2) | C16—N2—C12—C6 | 179.3 (2) |
C6—C1—C2—C7 | −177.3 (3) | Pt1—N2—C12—C6 | −1.6 (3) |
Pt1—C1—C2—C7 | 0.5 (3) | C5—C6—C12—N2 | −178.6 (3) |
C1—C2—C3—C4 | −1.5 (5) | C1—C6—C12—N2 | 1.5 (4) |
C7—C2—C3—C4 | 179.2 (3) | C5—C6—C12—C13 | 1.5 (5) |
C2—C3—C4—C5 | −0.6 (5) | C1—C6—C12—C13 | −178.3 (3) |
C3—C4—C5—C6 | 1.1 (5) | N2—C12—C13—C14 | 1.3 (4) |
C4—C5—C6—C1 | 0.6 (5) | C6—C12—C13—C14 | −178.8 (3) |
C4—C5—C6—C12 | −179.3 (3) | C12—C13—C14—C15 | −0.4 (5) |
C2—C1—C6—C5 | −2.7 (4) | C13—C14—C15—C16 | −1.0 (5) |
Pt1—C1—C6—C5 | 179.4 (2) | C13—C14—C15—C18 | 178.7 (3) |
C2—C1—C6—C12 | 177.1 (3) | C12—N2—C16—C15 | −0.7 (4) |
Pt1—C1—C6—C12 | −0.8 (3) | Pt1—N2—C16—C15 | −179.6 (2) |
C11—N1—C7—C8 | 3.8 (4) | C14—C15—C16—N2 | 1.6 (5) |
Pt1—N1—C7—C8 | −174.8 (2) | C18—C15—C16—N2 | −178.1 (3) |
Experimental details
Crystal data | |
Chemical formula | [PtCl(C18H15N2)] |
Mr | 489.86 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 200 |
a, b, c (Å) | 9.657 (4), 12.969 (5), 12.962 (6) |
β (°) | 107.092 (17) |
V (Å3) | 1551.7 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 9.21 |
Crystal size (mm) | 0.20 × 0.15 × 0.12 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Numerical (SHAPE; Higashi, 1999) |
Tmin, Tmax | 0.260, 0.459 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14606, 3524, 3301 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.018, 0.039, 1.07 |
No. of reflections | 3524 |
No. of parameters | 203 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.92, −0.71 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku, 2005), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997).
Pt1—C1 | 1.915 (3) | Pt1—N2 | 2.041 (2) |
Pt1—N1 | 2.027 (2) | Pt1—Cl1 | 2.4091 (10) |
C1—Pt1—N1 | 80.87 (11) | C11—N1—Pt1 | 126.45 (19) |
C1—Pt1—N2 | 80.61 (11) | C7—N1—Pt1 | 114.43 (18) |
N1—Pt1—N2 | 161.47 (9) | C16—N2—Pt1 | 126.13 (19) |
C1—Pt1—Cl1 | 177.56 (9) | C12—N2—Pt1 | 114.19 (18) |
N1—Pt1—Cl1 | 97.56 (7) | C6—C1—Pt1 | 118.8 (2) |
N2—Pt1—Cl1 | 100.94 (7) | C2—C1—Pt1 | 118.5 (2) |
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We have been investigating the luminescence color tuning of transition-metal complex crystals due to vapochromism. For example, [Ru(dbb)2(CN)2] (dbb is di-tert-butyl-2,2'-bipyridine) shows a reversible color change from dark red to bright orange in the presence of moisture (Abe & Shinozaki, 2005). We have demonstrated the luminescence vapochromism to organic solvent vapors using a Pt compound with a pincer-type tridentate monoanionic N—C—N ligand 1,3-di(2-pyridyl)phenyl-κ3N,N',C2. Moreover, luminescence mechanochromism, which is the luminescence color change observed upon grinding crystals of the complex, was found for the title compound, (I) (Abe, 2007). However, mechanochromism has not been reported for chlorido{1,3-di(2-pyridyl-κN)phenyl-κC2}platinum(II), which has no methyl groups in the N—C—N ligand (Cárdenas & Echavarren, 1999). We report here a single-crystal X-ray structure analysis of (I).
The molecular structure of the title PtII complex is illustrated in Fig. 1, and selected geometric parameters are given in Table 1. The coordination bond lengths and the bite angles of the N—C—N ligand are typical, as compared with those of the analogous platinum(II) N—C—N tridentate complexes [PtCl{1-R-3,5-(2-py-κN)2C6H2-κC4}] [R = H, (II) (Cárdenas & Echavarren, 1999), COOMe, (III) (Williams et al., 2003), Me, (IV), and 4-PhC6H4, (V) (Farley et al., 2005)] [Pt—C = 1.903 (4)–1.912 (3) Å, Pt—N = 2.033 (6)–2.045 (2) Å, Pt—Cl = 2.405 (1)–2.4221 (8) Å, C—Pt—N = 80.1 (3)–80.9 (2)° and N—Pt—N 161.1 (2)–161.4 (2)°]. Unlike in complexes (II)–(V), the two N—Pt—Cl angles in (I) differ slightly from one another, which is indicative of the distortion of the Cl− coordination from the ideal molecular C2v symmetry. The PtII coordination plane is almost coplanar with that of the phenyl ring and with the plane of the pyridyl ring consisting of atoms N2 and C12–C16, the dihedral angles being 1.54 (8) and 3.02 (8)°, respectively. The other pyridyl ring comprising atoms N1 and C7–C11 is, however, slightly twisted from the PtII coordination plane; the dihedral angle is 6.57 (8)°. This twisting would also be related to the packing structure of compound (I) (see below).
The crystal packing of (I) (Figs. 2 and 3) contrasts with those of the related 1-R-3,5-(2-py)2C6H2 complexes (II)–(V), where one-dimensional stacking columns are constructed by the intermolecular π–π interactions (Fig. 4). In the crystal structure of (I), all the molecules are aligned with their coordination planes parallel to the crystallographic (101) plane (Fig. 2), and the aligned molecules compose a two-dimensional sheet parallel to the (101) plane. In the sheet (Fig. 3, middle), two molecules are paired by a π–π interaction in an antiparallel fashion (stack A at the bottom of Fig. 3); the distances of the closest contacts between the PtII complex molecules are 3.477 (2) Å for Pt1···C12i and 3.412 (3) Å for N1···C14i [symmetry code: (i) −x + 2, −y, −z + 2]. The antiparallel arrangement of molecules results primarily from the electrostatic interaction due to the large dipole moment of the PtII complex, which we have estimated as µ = 4.5 D by a density functional theory calculation using the Amsterdam Density Functional package (ADF 2004.01: Te Velde et al., 2001; Ziegler, 1991). On the other side of the molecular plane, however, two neighboring molecules participate in π–π stacking interactions (stack B at the top of Fig. 3) [C8···C14ii = 3.376 (3) Å and C7···C13ii = 3.364 (3) Å; symmetry code: (ii) −x + 3/2, y + 1/2, −z + 3/2]. Thus, a molecule in the crystal structure of (I) interacts in total with three neighbors. This unit expands over the crystallographic (101) plane, forming a two-dimensional sheet (Fig. 3, middle). The difference between the packing of (I) and that in (II)–(V) can be traced to the introduction of methyl substituents at the 5-positions of both pyridyl rings of the N—C—N ligand. The Me groups seem to impede sterically the formation of one-dimensional stacking columns, affording a different packing structure for (I) from those of (II)–(V) and thereby providing a structural rationalization for the novel luminescence properties of (I).