Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111026011/ov3005sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111026011/ov3005Isup2.hkl |
CCDC reference: 846626
For related literature, see: Allen (2002); Bailey & Gray (1992); Field et al. (2003, 2007); Frisch et al. (2004); Hay & Dunning (1976); Hay & Wadt (1985a,b,c); Jaganyi et al. (2008); Perdew et al. (1997); Pitteri et al. (1995); Thurston (2007).
The complex, chloro(2,2':6',2"-terpyridine)platinum(II)chloride dihydrate, [Pt(terpy)C1]C1.2H2O was synthesized as described by literature methods (Pitteri et al., 1995). AgClO4 (54 mg, 0.26 mmol) was added to [Pt(terpy)C1]C1.2H2O (70 mg, 0.13 mmol) dissolved in nitromethane (4 ml) and stirred at approximately 323 K for 1 h. The solution turned pale yellow and a white precipitate, AgCl(s), formed. This precipitate was filtered off. Pyrazole (9 mg, 0.13 mmol) was added to the solution which immediately turned dark yellow in colour. Yellow crystals of [Pt(terpy)(pyz)](ClO4)2(CH3NO2) were grown via vapour diffusion of diethylether into a concentrated nitromethane solution of the platinum(II) terpyridine (yield 69%).
The positions of all hydrogen atoms were calculated using the standard riding model of SHELXL97. with C—H(aromatic) distances of 0.93 Å and Uiso = 1.2 Ueq. The only exception is the pyrazole hydrogen atom which was located in the difference Fourier map and allowed to refine isotropically. The perchorlate oxygen atoms were treated with a static disorder model with isotropic oxygen atoms. This method lead to a smaller range of Cl—O bond lengrhs and improved s.u.'s when compared to a dynamic model. Each perchlorate anion shows orientational disorder. Around Cl1 there are two sets of possible positions defined by O1A/O2A/O3A/O4A and O1B/O2B/O3B/O4B, while around Cl2 there are O5A/O6A/O7A/O8A and O5B/O6B/O7B/O8B. The Cl—O distances were restrained to 1.43 (2) Å. The occupancies for the sites A and B around Cl1 converged to 52.1 (5) and 47.9 (5)%, respectively, while around Cl2 the occupancies converged to 63.2 (5) and 36.8 (5)%, respectively.
Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis CCD (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: WinGX (Farrugia, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Pt(C15H11N3)(C3H4N2)](ClO4)2·CH3NO2 | F(000) = 1464 |
Mr = 756.38 | Dx = 2.032 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4879 reflections |
a = 16.351 (5) Å | θ = 2.9–26° |
b = 11.534 (4) Å | µ = 5.96 mm−1 |
c = 14.075 (5) Å | T = 296 K |
β = 111.311 (5)° | Needle, yellow |
V = 2472.9 (14) Å3 | 0.60 × 0.40 × 0.20 mm |
Z = 4 |
Oxford Diffraction Xcalibur2 CCD diffractometer | 4877 independent reflections |
Radiation source: fine-focus sealed tube | 3848 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
ω scans at fixed θ angles | θmax = 26.0°, θmin = 2.9° |
Absorption correction: multi-scan (Blessing, 1995) | h = −20→19 |
Tmin = 0.124, Tmax = 0.382 | k = −14→14 |
16387 measured reflections | l = −11→17 |
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)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.131 | w = 1/[σ2(Fo2) + (0.091P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.004 |
4877 reflections | Δρmax = 2.24 e Å−3 |
339 parameters | Δρmin = −1.68 e Å−3 |
49 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0028 (3) |
[Pt(C15H11N3)(C3H4N2)](ClO4)2·CH3NO2 | V = 2472.9 (14) Å3 |
Mr = 756.38 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.351 (5) Å | µ = 5.96 mm−1 |
b = 11.534 (4) Å | T = 296 K |
c = 14.075 (5) Å | 0.60 × 0.40 × 0.20 mm |
β = 111.311 (5)° |
Oxford Diffraction Xcalibur2 CCD diffractometer | 4877 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 3848 reflections with I > 2σ(I) |
Tmin = 0.124, Tmax = 0.382 | Rint = 0.057 |
16387 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 49 restraints |
wR(F2) = 0.131 | H-atom parameters constrained |
S = 1.02 | Δρmax = 2.24 e Å−3 |
4877 reflections | Δρmin = −1.68 e Å−3 |
339 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 | Occ. (<1) | |
Pt1 | 0.771959 (17) | 0.29071 (2) | 0.081761 (19) | 0.04125 (15) | |
C1 | 0.6910 (5) | 0.1477 (8) | 0.2054 (7) | 0.061 (2) | |
H1 | 0.6725 | 0.2169 | 0.2248 | 0.073* | |
C2 | 0.6705 (6) | 0.0482 (9) | 0.2401 (7) | 0.073 (3) | |
H2 | 0.6385 | 0.0498 | 0.2829 | 0.088* | |
C3 | 0.6957 (6) | −0.0543 (9) | 0.2140 (8) | 0.077 (3) | |
H3 | 0.6805 | −0.1236 | 0.2369 | 0.092* | |
C4 | 0.7438 (6) | −0.0538 (8) | 0.1534 (7) | 0.071 (3) | |
H4 | 0.7631 | −0.1232 | 0.1353 | 0.085* | |
C5 | 0.7637 (5) | 0.0490 (6) | 0.1191 (6) | 0.0480 (16) | |
C6 | 0.8144 (5) | 0.0607 (7) | 0.0508 (6) | 0.0512 (18) | |
C7 | 0.8485 (5) | −0.0262 (7) | 0.0087 (7) | 0.062 (2) | |
H7 | 0.8425 | −0.1034 | 0.0240 | 0.074* | |
C8 | 0.8902 (6) | 0.0013 (9) | −0.0541 (8) | 0.074 (3) | |
H8 | 0.9122 | −0.0573 | −0.0834 | 0.089* | |
C9 | 0.9013 (5) | 0.1188 (8) | −0.0766 (6) | 0.058 (2) | |
H9 | 0.9309 | 0.1385 | −0.1196 | 0.070* | |
C11 | 0.8689 (5) | 0.3284 (7) | −0.0477 (6) | 0.0513 (18) | |
C12 | 0.9104 (5) | 0.3813 (7) | −0.1045 (6) | 0.059 (2) | |
H12 | 0.9396 | 0.3374 | −0.1377 | 0.071* | |
C13 | 0.9087 (6) | 0.4989 (8) | −0.1119 (7) | 0.068 (2) | |
H13 | 0.9366 | 0.5360 | −0.1504 | 0.082* | |
C14 | 0.8650 (6) | 0.5631 (8) | −0.0615 (7) | 0.064 (2) | |
H14 | 0.8636 | 0.6436 | −0.0655 | 0.076* | |
C15 | 0.8238 (6) | 0.5059 (7) | −0.0059 (6) | 0.0547 (19) | |
H15 | 0.7933 | 0.5488 | 0.0265 | 0.066* | |
C16 | 0.5985 (7) | 0.5049 (9) | 0.1483 (8) | 0.077 (3) | |
H16 | 0.5411 | 0.5218 | 0.1419 | 0.093* | |
C17 | 0.6674 (9) | 0.5637 (9) | 0.2017 (8) | 0.090 (4) | |
H17 | 0.6693 | 0.6312 | 0.2386 | 0.107* | |
C10 | 0.8673 (5) | 0.2010 (6) | −0.0333 (6) | 0.0480 (18) | |
C18 | 0.7394 (7) | 0.5028 (7) | 0.1920 (7) | 0.069 (3) | |
H18 | 0.7982 | 0.5227 | 0.2237 | 0.083* | |
N1 | 0.7359 (4) | 0.1519 (6) | 0.1452 (5) | 0.0483 (15) | |
N2 | 0.8252 (4) | 0.1701 (5) | 0.0295 (5) | 0.0434 (13) | |
N3 | 0.8260 (4) | 0.3913 (5) | 0.0030 (4) | 0.0464 (14) | |
N4 | 0.7095 (4) | 0.4136 (6) | 0.1309 (5) | 0.0512 (15) | |
N5 | 0.6227 (4) | 0.4176 (6) | 0.1043 (5) | 0.0633 (17) | |
H5 | 0.5870 | 0.3691 | 0.0635 | 0.076* | |
Cl1 | 0.55827 (15) | 0.30650 (19) | 0.37359 (16) | 0.0602 (5) | |
O1A | 0.4833 (8) | 0.3207 (17) | 0.2852 (10) | 0.127 (8)* | 0.52 (2) |
O2A | 0.5643 (12) | 0.1910 (9) | 0.4103 (15) | 0.122 (8)* | 0.52 (2) |
O3A | 0.6361 (7) | 0.3313 (14) | 0.3532 (11) | 0.083 (5)* | 0.52 (2) |
O4A | 0.5575 (10) | 0.3835 (14) | 0.4524 (10) | 0.122 (8)* | 0.52 (2) |
O1B | 0.4887 (9) | 0.3697 (17) | 0.3023 (15) | 0.138 (9)* | 0.48 (2) |
O2B | 0.5630 (17) | 0.1906 (11) | 0.343 (2) | 0.150 (10)* | 0.48 (2) |
O3B | 0.6372 (8) | 0.3682 (17) | 0.3837 (16) | 0.113 (7)* | 0.48 (2) |
O4B | 0.5511 (14) | 0.2894 (16) | 0.4654 (16) | 0.107 (8)* | 0.48 (2) |
Cl2 | 0.94052 (15) | 0.71134 (14) | 0.24900 (17) | 0.0531 (5) | |
O5A | 1.0162 (16) | 0.7872 (15) | 0.2902 (19) | 0.142 (8)* | 0.632 (18) |
O6A | 0.8914 (9) | 0.7249 (10) | 0.1425 (10) | 0.093 (5)* | 0.632 (18) |
O7A | 0.9620 (11) | 0.5924 (12) | 0.2502 (11) | 0.089 (4)* | 0.632 (18) |
O8A | 0.8889 (10) | 0.7330 (10) | 0.3095 (11) | 0.080 (4)* | 0.632 (18) |
O5B | 0.992 (2) | 0.803 (2) | 0.232 (3) | 0.109 (10)* | 0.368 (18) |
O6B | 0.8541 (17) | 0.7254 (17) | 0.261 (2) | 0.080 (7)* | 0.368 (18) |
O7B | 0.9970 (14) | 0.6104 (16) | 0.2836 (15) | 0.066 (5)* | 0.368 (18) |
O8B | 0.9714 (19) | 0.736 (2) | 0.356 (2) | 0.111 (9)* | 0.368 (18) |
C1S | 0.4259 (8) | 0.1564 (13) | 0.0890 (9) | 0.107 (4) | |
H1S1 | 0.3858 | 0.0922 | 0.0733 | 0.160* | |
H1S2 | 0.4646 | 0.1518 | 0.1591 | 0.160* | |
H1S3 | 0.4598 | 0.1539 | 0.0458 | 0.160* | |
N1S | 0.3770 (7) | 0.2641 (9) | 0.0722 (7) | 0.081 (2) | |
O1S | 0.3053 (8) | 0.2563 (10) | 0.0784 (9) | 0.126 (3) | |
O2S | 0.4083 (8) | 0.3523 (10) | 0.0574 (8) | 0.156 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.0349 (2) | 0.0406 (2) | 0.0461 (2) | 0.00298 (10) | 0.01213 (13) | −0.00055 (11) |
C1 | 0.052 (5) | 0.068 (6) | 0.069 (5) | 0.017 (4) | 0.030 (4) | 0.021 (4) |
C2 | 0.050 (5) | 0.089 (7) | 0.081 (6) | −0.004 (5) | 0.025 (5) | 0.031 (5) |
C3 | 0.073 (6) | 0.065 (6) | 0.095 (7) | 0.000 (5) | 0.034 (5) | 0.032 (5) |
C4 | 0.056 (5) | 0.049 (5) | 0.094 (7) | 0.001 (4) | 0.011 (5) | 0.014 (5) |
C5 | 0.040 (4) | 0.042 (4) | 0.054 (4) | 0.003 (3) | 0.008 (3) | 0.005 (3) |
C6 | 0.044 (4) | 0.050 (4) | 0.052 (4) | 0.008 (3) | 0.008 (3) | −0.002 (3) |
C7 | 0.062 (5) | 0.043 (4) | 0.075 (5) | 0.007 (4) | 0.019 (4) | −0.011 (4) |
C8 | 0.061 (6) | 0.074 (6) | 0.080 (6) | 0.018 (5) | 0.018 (5) | −0.021 (5) |
C9 | 0.049 (5) | 0.064 (5) | 0.065 (5) | 0.013 (4) | 0.024 (4) | 0.002 (4) |
C11 | 0.035 (4) | 0.061 (4) | 0.050 (4) | −0.005 (3) | 0.006 (3) | −0.001 (4) |
C12 | 0.048 (5) | 0.063 (5) | 0.067 (5) | 0.015 (4) | 0.022 (4) | 0.009 (4) |
C13 | 0.057 (5) | 0.077 (6) | 0.069 (5) | −0.008 (4) | 0.021 (4) | 0.012 (5) |
C14 | 0.064 (5) | 0.057 (5) | 0.072 (5) | 0.005 (4) | 0.027 (4) | 0.012 (4) |
C15 | 0.061 (5) | 0.045 (4) | 0.059 (5) | 0.002 (3) | 0.022 (4) | 0.003 (3) |
C16 | 0.078 (7) | 0.077 (6) | 0.089 (7) | 0.024 (5) | 0.045 (6) | 0.000 (5) |
C17 | 0.156 (12) | 0.059 (6) | 0.083 (7) | 0.020 (7) | 0.080 (8) | −0.003 (5) |
C10 | 0.030 (4) | 0.055 (5) | 0.050 (4) | 0.006 (3) | 0.004 (3) | 0.002 (3) |
C18 | 0.100 (8) | 0.048 (5) | 0.067 (5) | −0.014 (5) | 0.040 (5) | −0.013 (4) |
N1 | 0.028 (3) | 0.052 (4) | 0.058 (4) | −0.001 (3) | 0.008 (3) | 0.006 (3) |
N2 | 0.031 (3) | 0.044 (3) | 0.051 (3) | 0.007 (2) | 0.010 (3) | −0.003 (3) |
N3 | 0.045 (3) | 0.044 (3) | 0.051 (3) | 0.002 (3) | 0.019 (3) | −0.002 (3) |
N4 | 0.054 (4) | 0.048 (4) | 0.056 (4) | 0.005 (3) | 0.024 (3) | 0.002 (3) |
N5 | 0.050 (4) | 0.067 (4) | 0.075 (4) | 0.018 (3) | 0.025 (3) | 0.005 (3) |
Cl1 | 0.0514 (12) | 0.0708 (13) | 0.0538 (11) | 0.0038 (9) | 0.0137 (9) | 0.0015 (9) |
Cl2 | 0.0609 (13) | 0.0431 (10) | 0.0621 (12) | 0.0059 (8) | 0.0304 (10) | 0.0033 (8) |
C1S | 0.087 (8) | 0.138 (12) | 0.090 (8) | 0.014 (8) | 0.027 (7) | −0.010 (8) |
N1S | 0.077 (7) | 0.090 (7) | 0.070 (6) | −0.002 (5) | 0.021 (5) | 0.001 (5) |
O1S | 0.092 (7) | 0.119 (6) | 0.161 (10) | 0.027 (7) | 0.040 (6) | 0.009 (7) |
O2S | 0.197 (11) | 0.130 (9) | 0.121 (8) | −0.041 (9) | 0.035 (7) | 0.030 (7) |
Pt1—N2 | 1.922 (6) | C17—H17 | 0.9300 |
Pt1—N4 | 2.011 (6) | C10—N2 | 1.352 (10) |
Pt1—N3 | 2.018 (6) | C18—N4 | 1.315 (10) |
Pt1—N1 | 2.022 (6) | C18—H18 | 0.9300 |
C1—N1 | 1.308 (10) | N4—N5 | 1.331 (8) |
C1—C2 | 1.337 (12) | N5—H5 | 0.8600 |
C1—H1 | 0.9300 | Cl1—O4B | 1.35 (2) |
C2—C3 | 1.346 (14) | Cl1—O1A | 1.403 (8) |
C2—H2 | 0.9300 | Cl1—O1B | 1.415 (8) |
C3—C4 | 1.353 (13) | Cl1—O2B | 1.415 (9) |
C3—H3 | 0.9300 | Cl1—O2A | 1.420 (9) |
C4—C5 | 1.364 (11) | Cl1—O4A | 1.425 (9) |
C4—H4 | 0.9300 | Cl1—O3A | 1.432 (8) |
C5—N1 | 1.368 (10) | Cl1—O3B | 1.434 (8) |
C5—C6 | 1.486 (11) | O1A—O1B | 0.61 (3) |
C6—N2 | 1.324 (10) | O2A—O2B | 0.94 (3) |
C6—C7 | 1.381 (10) | O2A—O4B | 1.43 (2) |
C7—C8 | 1.336 (13) | O3A—O3B | 0.60 (2) |
C7—H7 | 0.9300 | O4A—O4B | 1.112 (18) |
C8—C9 | 1.418 (13) | Cl2—O7A | 1.414 (13) |
C8—H8 | 0.9300 | Cl2—O5B | 1.42 (3) |
C9—C10 | 1.351 (11) | Cl2—O8A | 1.422 (13) |
C9—H9 | 0.9300 | Cl2—O6A | 1.428 (13) |
C11—C12 | 1.366 (11) | Cl2—O8B | 1.43 (3) |
C11—N3 | 1.375 (10) | Cl2—O5A | 1.45 (2) |
C11—C10 | 1.485 (11) | Cl2—O7B | 1.455 (18) |
C12—C13 | 1.360 (12) | Cl2—O6B | 1.49 (2) |
C12—H12 | 0.9300 | O5A—O5B | 0.79 (3) |
C13—C14 | 1.389 (12) | O5A—O8B | 1.49 (3) |
C13—H13 | 0.9300 | O7A—O7B | 0.63 (2) |
C14—C15 | 1.373 (11) | O8A—O6B | 0.72 (2) |
C14—H14 | 0.9300 | O8A—O8B | 1.27 (3) |
C15—N3 | 1.326 (9) | C1S—N1S | 1.449 (16) |
C15—H15 | 0.9300 | C1S—H1S1 | 0.9600 |
C16—C17 | 1.295 (15) | C1S—H1S2 | 0.9600 |
C16—N5 | 1.316 (10) | C1S—H1S3 | 0.9600 |
C16—H16 | 0.9300 | N1S—O2S | 1.191 (13) |
C17—C18 | 1.420 (14) | N1S—O1S | 1.210 (14) |
N2—Pt1—N4 | 176.7 (2) | O1B—Cl1—O2A | 132.3 (11) |
N2—Pt1—N3 | 81.7 (3) | O2B—Cl1—O2A | 38.8 (11) |
N4—Pt1—N3 | 99.3 (3) | O4B—Cl1—O4A | 47.1 (8) |
N2—Pt1—N1 | 80.9 (3) | O1A—Cl1—O4A | 111.4 (8) |
N4—Pt1—N1 | 98.1 (3) | O1B—Cl1—O4A | 89.9 (11) |
N3—Pt1—N1 | 162.6 (3) | O2B—Cl1—O4A | 147.5 (12) |
N1—C1—C2 | 122.9 (9) | O2A—Cl1—O4A | 108.7 (8) |
N1—C1—H1 | 118.6 | O4B—Cl1—O3A | 127.8 (11) |
C2—C1—H1 | 118.6 | O1A—Cl1—O3A | 110.7 (8) |
C1—C2—C3 | 120.7 (9) | O1B—Cl1—O3A | 107.4 (12) |
C1—C2—H2 | 119.6 | O2B—Cl1—O3A | 88.6 (13) |
C3—C2—H2 | 119.6 | O2A—Cl1—O3A | 108.1 (8) |
C2—C3—C4 | 118.3 (8) | O4A—Cl1—O3A | 106.9 (7) |
C2—C3—H3 | 120.8 | O4B—Cl1—O3B | 111.4 (12) |
C4—C3—H3 | 120.8 | O1A—Cl1—O3B | 119.6 (11) |
C3—C4—C5 | 119.7 (9) | O1B—Cl1—O3B | 106.1 (9) |
C3—C4—H4 | 120.2 | O2B—Cl1—O3B | 110.6 (14) |
C5—C4—H4 | 120.2 | O2A—Cl1—O3B | 119.2 (11) |
C4—C5—N1 | 120.9 (8) | O4A—Cl1—O3B | 82.9 (10) |
C4—C5—C6 | 124.7 (7) | O3A—Cl1—O3B | 24.2 (9) |
N1—C5—C6 | 114.4 (6) | O1B—O1A—Cl1 | 78.6 (11) |
N2—C6—C7 | 119.1 (7) | O2B—O2A—Cl1 | 70.3 (7) |
N2—C6—C5 | 112.6 (6) | O2B—O2A—O4B | 126.5 (12) |
C7—C6—C5 | 128.3 (7) | Cl1—O2A—O4B | 56.6 (9) |
C8—C7—C6 | 119.6 (8) | O3B—O3A—Cl1 | 78.2 (10) |
C8—C7—H7 | 120.2 | O4B—O4A—Cl1 | 63.1 (12) |
C6—C7—H7 | 120.2 | O1A—O1B—Cl1 | 76.4 (10) |
C7—C8—C9 | 120.8 (8) | O2A—O2B—Cl1 | 70.9 (8) |
C7—C8—H8 | 119.6 | O3A—O3B—Cl1 | 77.7 (10) |
C9—C8—H8 | 119.6 | O4A—O4B—Cl1 | 69.8 (12) |
C10—C9—C8 | 117.5 (8) | O4A—O4B—O2A | 129.9 (19) |
C10—C9—H9 | 121.2 | Cl1—O4B—O2A | 61.1 (10) |
C8—C9—H9 | 121.2 | O7A—Cl2—O5B | 124.3 (13) |
C12—C11—N3 | 121.5 (8) | O7A—Cl2—O8A | 111.2 (7) |
C12—C11—C10 | 124.0 (8) | O5B—Cl2—O8A | 119.0 (13) |
N3—C11—C10 | 114.5 (7) | O7A—Cl2—O6A | 99.3 (8) |
C13—C12—C11 | 119.3 (9) | O5B—Cl2—O6A | 83.3 (15) |
C13—C12—H12 | 120.3 | O8A—Cl2—O6A | 112.3 (8) |
C11—C12—H12 | 120.3 | O7A—Cl2—O8B | 101.0 (12) |
C12—C13—C14 | 119.5 (8) | O5B—Cl2—O8B | 91.3 (17) |
C12—C13—H13 | 120.2 | O8A—Cl2—O8B | 52.8 (11) |
C14—C13—H13 | 120.2 | O6A—Cl2—O8B | 158.4 (12) |
C15—C14—C13 | 119.0 (8) | O7A—Cl2—O5A | 114.1 (10) |
C15—C14—H14 | 120.5 | O5B—Cl2—O5A | 31.9 (13) |
C13—C14—H14 | 120.5 | O8A—Cl2—O5A | 105.1 (11) |
N3—C15—C14 | 122.0 (8) | O6A—Cl2—O5A | 115.2 (11) |
N3—C15—H15 | 119.0 | O8B—Cl2—O5A | 62.3 (13) |
C14—C15—H15 | 119.0 | O7A—Cl2—O7B | 25.3 (8) |
C17—C16—N5 | 109.1 (9) | O5B—Cl2—O7B | 107.9 (15) |
C17—C16—H16 | 125.5 | O8A—Cl2—O7B | 112.5 (9) |
N5—C16—H16 | 125.5 | O6A—Cl2—O7B | 119.0 (9) |
C16—C17—C18 | 105.2 (9) | O8B—Cl2—O7B | 82.6 (13) |
C16—C17—H17 | 127.4 | O5A—Cl2—O7B | 90.2 (12) |
C18—C17—H17 | 127.4 | O7A—Cl2—O6B | 110.2 (10) |
C9—C10—N2 | 120.1 (7) | O5B—Cl2—O6B | 125.4 (14) |
C9—C10—C11 | 127.0 (8) | O8A—Cl2—O6B | 28.4 (9) |
N2—C10—C11 | 112.8 (7) | O6A—Cl2—O6B | 84.9 (12) |
N4—C18—C17 | 109.0 (10) | O8B—Cl2—O6B | 81.2 (14) |
N4—C18—H18 | 125.5 | O5A—Cl2—O6B | 126.4 (12) |
C17—C18—H18 | 125.5 | O7B—Cl2—O6B | 124.2 (11) |
C1—N1—C5 | 117.5 (7) | O5B—O5A—Cl2 | 72 (3) |
C1—N1—Pt1 | 129.6 (6) | O5B—O5A—O8B | 124 (4) |
C5—N1—Pt1 | 112.9 (5) | Cl2—O5A—O8B | 58.1 (13) |
C6—N2—C10 | 122.7 (6) | O7B—O7A—Cl2 | 81 (2) |
C6—N2—Pt1 | 119.1 (5) | O6B—O8A—O8B | 145 (3) |
C10—N2—Pt1 | 118.0 (5) | O6B—O8A—Cl2 | 81 (2) |
C15—N3—C11 | 118.6 (7) | O8B—O8A—Cl2 | 63.9 (13) |
C15—N3—Pt1 | 128.5 (6) | O5A—O5B—Cl2 | 76 (3) |
C11—N3—Pt1 | 112.9 (5) | O8A—O6B—Cl2 | 70 (2) |
C18—N4—N5 | 105.2 (7) | O7A—O7B—Cl2 | 74 (2) |
C18—N4—Pt1 | 131.4 (7) | O8A—O8B—Cl2 | 63.3 (13) |
N5—N4—Pt1 | 123.4 (5) | O8A—O8B—O5A | 111 (2) |
C16—N5—N4 | 111.5 (8) | Cl2—O8B—O5A | 59.6 (14) |
C16—N5—H5 | 124.3 | N1S—C1S—H1S1 | 109.5 |
N4—N5—H5 | 124.3 | N1S—C1S—H1S2 | 109.5 |
O4B—Cl1—O1A | 120.8 (12) | H1S1—C1S—H1S2 | 109.5 |
O4B—Cl1—O1B | 115.2 (13) | N1S—C1S—H1S3 | 109.5 |
O1A—Cl1—O1B | 24.9 (11) | H1S1—C1S—H1S3 | 109.5 |
O4B—Cl1—O2B | 100.8 (13) | H1S2—C1S—H1S3 | 109.5 |
O1A—Cl1—O2B | 88.1 (12) | O2S—N1S—O1S | 124.4 (13) |
O1B—Cl1—O2B | 112.9 (10) | O2S—N1S—C1S | 121.0 (13) |
O4B—Cl1—O2A | 62.3 (9) | O1S—N1S—C1S | 114.6 (11) |
O1A—Cl1—O2A | 110.8 (8) | ||
N1—C1—C2—C3 | −0.1 (14) | O2B—Cl1—O1B—O1A | 6 (4) |
C1—C2—C3—C4 | 1.4 (15) | O2A—Cl1—O1B—O1A | −35 (4) |
C2—C3—C4—C5 | −1.4 (14) | O4A—Cl1—O1B—O1A | −150 (3) |
C3—C4—C5—N1 | 0.1 (12) | O3A—Cl1—O1B—O1A | 102 (3) |
C3—C4—C5—C6 | −178.8 (8) | O3B—Cl1—O1B—O1A | 127 (3) |
C4—C5—C6—N2 | −179.5 (7) | O4B—O2A—O2B—Cl1 | 7 (3) |
N1—C5—C6—N2 | 1.6 (10) | O4B—Cl1—O2B—O2A | −6 (2) |
C4—C5—C6—C7 | 1.3 (13) | O1A—Cl1—O2B—O2A | −127.5 (19) |
N1—C5—C6—C7 | −177.7 (7) | O1B—Cl1—O2B—O2A | −130 (2) |
N2—C6—C7—C8 | −1.3 (12) | O4A—Cl1—O2B—O2A | 2 (3) |
C5—C6—C7—C8 | 177.9 (8) | O3A—Cl1—O2B—O2A | 121.8 (19) |
C6—C7—C8—C9 | 1.2 (14) | O3B—Cl1—O2B—O2A | 111 (2) |
C7—C8—C9—C10 | −0.8 (14) | O4B—Cl1—O3B—O3A | 137 (2) |
N3—C11—C12—C13 | −0.6 (12) | O1A—Cl1—O3B—O3A | −74 (3) |
C10—C11—C12—C13 | −179.3 (8) | O1B—Cl1—O3B—O3A | −97 (3) |
C11—C12—C13—C14 | 0.1 (13) | O2B—Cl1—O3B—O3A | 26 (3) |
C12—C13—C14—C15 | −0.5 (13) | O2A—Cl1—O3B—O3A | 68 (3) |
C13—C14—C15—N3 | 1.5 (13) | O4A—Cl1—O3B—O3A | 175 (3) |
N5—C16—C17—C18 | −2.6 (11) | Cl1—O4A—O4B—O2A | 12 (2) |
C8—C9—C10—N2 | 0.5 (12) | O1A—Cl1—O4B—O4A | −91.5 (15) |
C8—C9—C10—C11 | −178.3 (8) | O1B—Cl1—O4B—O4A | −64.0 (17) |
C12—C11—C10—C9 | −3.7 (13) | O2B—Cl1—O4B—O4A | 174.2 (16) |
N3—C11—C10—C9 | 177.6 (7) | O2A—Cl1—O4B—O4A | 169.6 (19) |
C12—C11—C10—N2 | 177.4 (7) | O3A—Cl1—O4B—O4A | 77.5 (16) |
N3—C11—C10—N2 | −1.4 (9) | O3B—Cl1—O4B—O4A | 56.9 (17) |
C16—C17—C18—N4 | 2.0 (11) | O1A—Cl1—O4B—O2A | 98.8 (12) |
C2—C1—N1—C5 | −1.1 (12) | O1B—Cl1—O4B—O2A | 126.4 (13) |
C2—C1—N1—Pt1 | 178.7 (6) | O2B—Cl1—O4B—O2A | 4.6 (15) |
C4—C5—N1—C1 | 1.1 (11) | O4A—Cl1—O4B—O2A | −169.6 (19) |
C6—C5—N1—C1 | −179.9 (7) | O3A—Cl1—O4B—O2A | −92.1 (12) |
C4—C5—N1—Pt1 | −178.7 (6) | O3B—Cl1—O4B—O2A | −112.7 (13) |
C6—C5—N1—Pt1 | 0.3 (8) | O2B—O2A—O4B—O4A | −21 (5) |
N2—Pt1—N1—C1 | 178.9 (7) | Cl1—O2A—O4B—O4A | −13 (2) |
N4—Pt1—N1—C1 | −4.3 (7) | O2B—O2A—O4B—Cl1 | −8 (3) |
N3—Pt1—N1—C1 | 177.0 (7) | O7A—Cl2—O5A—O5B | 117 (3) |
N2—Pt1—N1—C5 | −1.3 (5) | O8A—Cl2—O5A—O5B | −121 (3) |
N4—Pt1—N1—C5 | 175.5 (5) | O6A—Cl2—O5A—O5B | 3 (3) |
N3—Pt1—N1—C5 | −3.2 (11) | O8B—Cl2—O5A—O5B | −153 (3) |
C7—C6—N2—C10 | 1.0 (11) | O7B—Cl2—O5A—O5B | 125 (3) |
C5—C6—N2—C10 | −178.3 (6) | O6B—Cl2—O5A—O5B | −100 (3) |
C7—C6—N2—Pt1 | 176.5 (6) | O7A—Cl2—O5A—O8B | −90.1 (15) |
C5—C6—N2—Pt1 | −2.8 (9) | O5B—Cl2—O5A—O8B | 153 (3) |
C9—C10—N2—C6 | −0.7 (12) | O8A—Cl2—O5A—O8B | 31.9 (14) |
C11—C10—N2—C6 | 178.3 (6) | O6A—Cl2—O5A—O8B | 156.0 (14) |
C9—C10—N2—Pt1 | −176.2 (6) | O7B—Cl2—O5A—O8B | −81.5 (15) |
C11—C10—N2—Pt1 | 2.9 (8) | O6B—Cl2—O5A—O8B | 53.0 (19) |
N3—Pt1—N2—C6 | −178.2 (6) | O5B—Cl2—O7A—O7B | 55 (3) |
N1—Pt1—N2—C6 | 2.4 (5) | O8A—Cl2—O7A—O7B | −98 (2) |
N3—Pt1—N2—C10 | −2.5 (6) | O6A—Cl2—O7A—O7B | 144 (2) |
N1—Pt1—N2—C10 | 178.0 (6) | O8B—Cl2—O7A—O7B | −44 (3) |
C14—C15—N3—C11 | −2.0 (12) | O5A—Cl2—O7A—O7B | 21 (3) |
C14—C15—N3—Pt1 | 179.1 (6) | O6B—Cl2—O7A—O7B | −128 (3) |
C12—C11—N3—C15 | 1.6 (11) | O7A—Cl2—O8A—O6B | −93 (2) |
C10—C11—N3—C15 | −179.7 (7) | O5B—Cl2—O8A—O6B | 112 (3) |
C12—C11—N3—Pt1 | −179.4 (6) | O6A—Cl2—O8A—O6B | 17 (2) |
C10—C11—N3—Pt1 | −0.6 (8) | O8B—Cl2—O8A—O6B | 179 (3) |
N2—Pt1—N3—C15 | −179.4 (7) | O5A—Cl2—O8A—O6B | 143 (2) |
N4—Pt1—N3—C15 | 3.8 (7) | O7B—Cl2—O8A—O6B | −121 (2) |
N1—Pt1—N3—C15 | −177.5 (7) | O7A—Cl2—O8A—O8B | 87.9 (16) |
N2—Pt1—N3—C11 | 1.6 (5) | O5B—Cl2—O8A—O8B | −67 (2) |
N4—Pt1—N3—C11 | −175.2 (5) | O6A—Cl2—O8A—O8B | −161.9 (14) |
N1—Pt1—N3—C11 | 3.5 (11) | O5A—Cl2—O8A—O8B | −36.0 (16) |
C17—C18—N4—N5 | −0.7 (9) | O7B—Cl2—O8A—O8B | 60.6 (17) |
C17—C18—N4—Pt1 | 179.7 (6) | O6B—Cl2—O8A—O8B | −179 (3) |
N3—Pt1—N4—C18 | −63.5 (7) | O8B—O5A—O5B—Cl2 | −27 (3) |
N1—Pt1—N4—C18 | 116.9 (7) | O7A—Cl2—O5B—O5A | −81 (3) |
N3—Pt1—N4—N5 | 116.9 (6) | O8A—Cl2—O5B—O5A | 71 (3) |
N1—Pt1—N4—N5 | −62.7 (6) | O6A—Cl2—O5B—O5A | −177 (3) |
C17—C16—N5—N4 | 2.4 (11) | O8B—Cl2—O5B—O5A | 24 (3) |
C18—N4—N5—C16 | −1.0 (9) | O7B—Cl2—O5B—O5A | −59 (3) |
Pt1—N4—N5—C16 | 178.7 (6) | O6B—Cl2—O5B—O5A | 104 (3) |
O4B—Cl1—O1A—O1B | 84 (3) | O8B—O8A—O6B—Cl2 | 2 (4) |
O2B—Cl1—O1A—O1B | −175 (3) | O7A—Cl2—O6B—O8A | 97 (2) |
O2A—Cl1—O1A—O1B | 153 (3) | O5B—Cl2—O6B—O8A | −86 (3) |
O4A—Cl1—O1A—O1B | 32 (3) | O6A—Cl2—O6B—O8A | −164 (2) |
O3A—Cl1—O1A—O1B | −87 (3) | O8B—Cl2—O6B—O8A | −1 (2) |
O3B—Cl1—O1A—O1B | −62 (3) | O5A—Cl2—O6B—O8A | −47 (3) |
O4B—Cl1—O2A—O2B | 173 (2) | O7B—Cl2—O6B—O8A | 74 (2) |
O1A—Cl1—O2A—O2B | 58 (2) | O5B—Cl2—O7B—O7A | −134 (3) |
O1B—Cl1—O2A—O2B | 73 (2) | O8A—Cl2—O7B—O7A | 92 (2) |
O4A—Cl1—O2A—O2B | −179 (2) | O6A—Cl2—O7B—O7A | −42 (3) |
O3A—Cl1—O2A—O2B | −63 (2) | O8B—Cl2—O7B—O7A | 137 (3) |
O3B—Cl1—O2A—O2B | −87 (2) | O5A—Cl2—O7B—O7A | −161 (2) |
O1A—Cl1—O2A—O4B | −114.8 (14) | O6B—Cl2—O7B—O7A | 63 (3) |
O1B—Cl1—O2A—O4B | −99.9 (17) | O6B—O8A—O8B—Cl2 | −2 (5) |
O2B—Cl1—O2A—O4B | −173 (2) | O6B—O8A—O8B—O5A | 34 (6) |
O4A—Cl1—O2A—O4B | 8.0 (15) | Cl2—O8A—O8B—O5A | 36.4 (15) |
O3A—Cl1—O2A—O4B | 123.8 (13) | O7A—Cl2—O8B—O8A | −108.4 (12) |
O3B—Cl1—O2A—O4B | 100.2 (15) | O5B—Cl2—O8B—O8A | 126.3 (15) |
O4B—Cl1—O3A—O3B | −53 (3) | O6A—Cl2—O8B—O8A | 51 (4) |
O1A—Cl1—O3A—O3B | 117 (3) | O5A—Cl2—O8B—O8A | 140.1 (17) |
O1B—Cl1—O3A—O3B | 91 (3) | O7B—Cl2—O8B—O8A | −125.7 (14) |
O2B—Cl1—O3A—O3B | −156 (3) | O6B—Cl2—O8B—O8A | 0.6 (13) |
O2A—Cl1—O3A—O3B | −122 (3) | O7A—Cl2—O8B—O5A | 111.5 (12) |
O4A—Cl1—O3A—O3B | −5 (3) | O5B—Cl2—O8B—O5A | −13.8 (17) |
O1A—Cl1—O4A—O4B | 112.7 (16) | O8A—Cl2—O8B—O5A | −140.1 (17) |
O1B—Cl1—O4A—O4B | 125.6 (16) | O6A—Cl2—O8B—O5A | −89 (4) |
O2B—Cl1—O4A—O4B | −11 (3) | O7B—Cl2—O8B—O5A | 94.2 (14) |
O2A—Cl1—O4A—O4B | −9.7 (18) | O6B—Cl2—O8B—O5A | −139.5 (14) |
O3A—Cl1—O4A—O4B | −126.2 (15) | O5B—O5A—O8B—O8A | −7 (5) |
O3B—Cl1—O4A—O4B | −128.2 (17) | Cl2—O5A—O8B—O8A | −38.0 (15) |
O4B—Cl1—O1B—O1A | −109 (3) | O5B—O5A—O8B—Cl2 | 31 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···O2Ai | 0.86 | 2.16 | 2.85 (2) | 134 (1) |
C1—H1···O3A | 0.93 | 2.47 | 3.31 (2) | 149 (1) |
C1S—H1S2···O1A | 0.96 | 2.58 | 3.20 (2) | 123 (1) |
C1S—H1S3···O4Ai | 0.96 | 2.46 | 3.40 (2) | 170 (1) |
C7—H7···O6Aii | 0.93 | 2.52 | 3.36 (2) | 150 (1) |
C8—H8···O8Ai | 0.93 | 2.47 | 3.31 (2) | 150 (1) |
C14—H14···O8Aiii | 0.93 | 2.41 | 3.08 (2) | 128 (1) |
C16—H16···O2Aiv | 0.93 | 2.52 | 3.28 (2) | 139 (1) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, y−1, z; (iii) x, −y+3/2, z−1/2; (iv) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Pt(C15H11N3)(C3H4N2)](ClO4)2·CH3NO2 |
Mr | 756.38 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 16.351 (5), 11.534 (4), 14.075 (5) |
β (°) | 111.311 (5) |
V (Å3) | 2472.9 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.96 |
Crystal size (mm) | 0.60 × 0.40 × 0.20 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur2 CCD diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.124, 0.382 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16387, 4877, 3848 |
Rint | 0.057 |
(sin θ/λ)max (Å−1) | 0.618 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.131, 1.02 |
No. of reflections | 4877 |
No. of parameters | 339 |
No. of restraints | 49 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.24, −1.68 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···O2Ai | 0.86 | 2.16 | 2.85 (2) | 134 (1) |
C1—H1···O3A | 0.93 | 2.47 | 3.31 (2) | 149 (1) |
C1S—H1S2···O1A | 0.96 | 2.58 | 3.20 (2) | 123 (1) |
C1S—H1S3···O4Ai | 0.96 | 2.46 | 3.40 (2) | 170 (1) |
C7—H7···O6Aii | 0.93 | 2.52 | 3.36 (2) | 150 (1) |
C8—H8···O8Ai | 0.93 | 2.47 | 3.31 (2) | 150 (1) |
C14—H14···O8Aiii | 0.93 | 2.41 | 3.08 (2) | 128 (1) |
C16—H16···O2Aiv | 0.93 | 2.52 | 3.28 (2) | 139 (1) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, y−1, z; (iii) x, −y+3/2, z−1/2; (iv) −x+1, y+1/2, −z+1/2. |
Bond/angle | Exp. length/angle | Calc. length/angle |
Pt—N1 | 2.025 (7) | 2.037 |
Pt—N2 | 1.924 (7) | 1.954 |
Pt—N3 | 2.016 (7) | 2.037 |
Pt—N4 | 2.012 (7) | 2.035 |
N1—Pt—N2 | 80.9 (3) | 81.1 |
N2—Pt—N3 | 81.5 (3) | 81.1 |
N3—Pt—N4 | 99.4 (3) | 98.89 |
N4—Pt—N1 | 98.2 (3) | 98.89 |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
Platinum(II) chelates have been extensively studied since their application as anti-tumour agents was discovered in the 1960s (Jaganyi et al., 2008). Although cis-diaminedichloroplatinum(II) (cisplatin) has been effective in the treatment of particular tumour cell lines, cisplatin resistance in certain cancer cell lines has sparked much research into developing new-generation platinum-based drugs (Thurston, 2007). The substitution kinetics of the title metal chelate have been studied to further develop the understanding of the interactions between the platinum(II) ion and various nucleophiles. This research is critical to the development of new drugs (Jaganyi et al., 2008). The structure of the pyrazole-substituted platinum(II)terpyridine, [Pt(terpy)(pyz)](ClO4)2.(CH3NO2) (where terpy = 2,2':6',2''-terpyridine and pyz = pyrazole), was elucidated to further develop the understanding of the binding mode of the ancillary ligand, i.e. whether the pyrazole ligand was deprotonated or not.
A search of the Cambridge Structural Database (CSD; Allen, 2002) showed that the title compound is a novel structure. There is, however, a reported µ2-pyrazolyl structure (Bailey & Gray, 1992). The reported metal chelate was synthesized under basic conditions and, as a result, the pyrazole ligand is deprotonated and a platinum(II)terpyridine cation is bound to each nitrogen atom of the ancillary ligand. The pyrazolyl ligand thus bridges the two chelates.
The title metal chelate crystallized in the monoclinic space group P21/c with Z = 4. The cation in the asymmetric unit was associated with two perchlorate anions and a nitromethane solvent molecule in the lattice. In the title compound the pyrazole ligand has bound in a more conventional manner than the previously reported µ2-pyrazolyl structure, with the nucleophilic ligand displacing the chloride ligand and covalently bonding to the metal centre. The pyrazole ligand occupies the fourth site of the platinum(II) centre, while the terpyridine ligand occupies the other three binding sites, giving a nominally square-planar metal chelate. The Pt1—N1, Pt1—N3 and Pt1—N4 bond lengths are approximately equal at 2.022 (6), 2.018 (6) and 2.011 (6) Å, respectively. The Pt1—N2 bond distance is noticeably shorter at 1.922 (6) Å (refer to Fig. 1 for the numbering scheme). The PtII ion is displaced from the least-squares plane defined by the four coordinating N atoms by 0.027 (1) Å. As expected, the N1—Pt1—N4 and N3—Pt1—N4 angles are approximately equal at 98.1 (3) and 99.3 (3)°, respectively. Similarly, the N1—Pt1—N2 and N2—Pt1—N3 angles are similar in magnitude at 80.9 (3) and 81.7 (3)°, respectively. These bond lengths show no noteworthy deviation from those previously reported for similar platinum(II) chelates (Field et al., 2007). It would appear that in the absence of a strong base the pyrazole ligand will preferentially bind through the N atom of the ancillary ligand as opposed to through the deprotonated NH atom.
Insofar as the packing of the metal cation is concerned the metal chelate reported in this work is devoid of any Pt···Pt or π···π interactions as the chelates are not arranged parallel to one another. This is likely due to electrostatic repulsion between the highly charged chelates (dicationic as compared to monocationic species with this ligand architecture) (Field et al., 2003). This repulsion overrides any attractive force from Pt···Pt or π···π interactions.
The structure exhibits a number of hydrogen bonds. The perchlorate anions are hydrogen bonded to both the nitromethane solvent in the lattice and the pyrazole NH group. In addition to this there are numerous aromatic–perchlorate C—H···O interactions. In all cases, the perchlorate O atoms act as hydrogen-bond acceptors and the pyrazole N—H and aromatic C—H hydrogens act as donors. There are additional hydrogen bonds in the lattice between the aromatic C—H groups and the perchlorate anions; however, these intereactions are longer than the sum of the van der Waals radii minus 0.1 Å and are therefore likely to be weak hydrogen bonds and are not discussed. Each methyl group of the nitromethane molecule bridges two perchlorate anions through hydrogen bonding. These perchlorate anions are in turn hydrogen bonded to two adjacent platinum(II) chelates. This combination of hydrogen bonds allows for the formation of an extended three-dimensional supramolecular structure. The hydrogen-bond lengths and angles are summarized in Table 1.
These hydrogen-bond lengths are all shorter than the sum of the van der Waals radii minus 0.2 Å. Although hydrogen-bond length does not necessarily correlate linearly with bond strength because of packing constraints in the lattice, it is probable that these bonds are moderate in strength as the bond lengths are considerably shorter than the van der Waals radii of the atoms. The strongly electron-withdrawing nitro group of the solvent will result in a more polar C—H bond than usual and as such could increase the strength of this hydrogen bond, based on simple electrostatic arguments.
The pyrazole ligand is neither coplanar nor perpendicular to the terpyridine ligand; the N1—Pt—N4—N5 torsion angle is 62.4 (6)°. The structure of the metal chelate in vacuo was calculated using density functional theory (DFT) methods at the PBE1PBE/LANL2DZ level of theory. PBE1PBE (Perdew et al., 1997) is a gradient-corrected functional. The LANL2DZ (Hay & Dunning, 1976; Hay & Wadt, 1985a,b,c) basis set makes use of effective core potentials to deal with atoms in the second row of the periodic table and beyond. The DFT calculations were all performed with GAUSSIAN03W (Frisch et al., 2004) with no symmetry constraints imposed on any of the calculations. The X-ray structure coordinates were used for the input structure for a full geometry optimization.
The geometry-optimized cation shows that in vacuo the pyrazole ligand in the lowest-energy conformation is perpendicular to the terpyridine ligand (i.e. 90°). This conformation would lead to minimal non-bonded repulsion between the pyridine hydrogen atoms and the pyrazole ligand and as such is a low-energy structure. This orientation would also allow for π-interaction between the pyrazole ligand and the dxy orbital of the PtII, which is non-bonding with respect to the terpyridine ligand. In the solid-state structure the pyrazole ligand is orientated at an angle of 62.4 (6)° relative to the terpyridine ligand. This deviation from the lowest-energy conformation is seemingly due to hydrogen bonding between the pyrazole NH and the perchlorate anion in the lattice. It would appear that the stability gained through the hydrogen bonding is sufficient for the molecule to adopt a higher-energy conformation.
Aside from the torsion angle of the pyrazole ligand the calculated and experimental structures are very similar, with minimal differences in geometry about the platinum(II) centre and the terpyridine ligand. The Pt—N bond lengths of the calculated and experimental structures are essentially equivalent (within 3σ). These bond lengths are summarized in Table 2. An overlay of the two structures has been calculated using Mercury 2.3 (Fig. 2) and shows that the solid-state structure deviates only slightly from the calculated, lowest energy conformation. This minimal deviation is indicated by the relatively small r.m.s. deviation value of 0.202 Å.