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The photophysical properties of transition metal complexes of the 5,6-dimethyl-2-(pyridin-2-yl)-1-(pyridin-2-ylmethyl)-1
H-benzimidazole ligand are of interest. Dichlorido[5,6-dimethyl-2-(pyridin-2-yl)-1-(pyridin-2-ylmethyl)-1
H-benzimidazole-κ
2N2,
N3]platinum(II), [PtCl
2(C
20H
18N
4)], is luminescent in the solid state at room temperature. The compound displays a distorted square-planar coordination geometry. The Pt—N(imidazole) bond length is shorter than the Pt—N(pyridine) bond length. The extended structure reveals that symmetry-related molecules display weak C—H
N, C—H
Cl, and C—H
Pt hydrogen-bonding interactions that are clearly discernable in the Hirshfeld surface and fingerprint plots. The intermolecular C—H
Pt and C—H
N interactions have been explored using density functional theory. The result of an analysis of the distance dependence of C—H
Pt yields a value consistent with that observed in the solid-state structure. The energy of interaction for the C—H
Pt interaction is found to be about −11 kJ mol
−1.
Supporting information
CCDC reference: 1567122
Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).
Dichlorido{5,6-dimethyl-2-(pyridin-2-yl)-1-(pyridin-2-ylmethyl)-1
H-benzimidazole-
κ2N2,
N3}platinum(II)
top
Crystal data top
[PtCl2(C20H18N4)] | F(000) = 1112 |
Mr = 580.37 | Dx = 1.978 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.6134 (14) Å | Cell parameters from 4378 reflections |
b = 15.7166 (16) Å | θ = 2.3–25.7° |
c = 11.8754 (17) Å | µ = 7.49 mm−1 |
β = 100.376 (5)° | T = 200 K |
V = 1948.5 (4) Å3 | Parallelepiped, clear orange |
Z = 4 | 0.30 × 0.30 × 0.10 mm |
Data collection top
Bruker SMART X2S benchtop diffractometer | 4257 independent reflections |
Radiation source: sealed microfocus tube | 3302 reflections with I > 2σ(I) |
Doubly curved silicon crystal monochromator | Rint = 0.059 |
Detector resolution: 8.3330 pixels mm-1 | θmax = 27.1°, θmin = 2.3° |
ω scans | h = −13→7 |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | k = −18→19 |
Tmin = 0.38, Tmax = 0.52 | l = −15→15 |
17697 measured reflections | |
Refinement top
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.069 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0239P)2] where P = (Fo2 + 2Fc2)/3 |
4257 reflections | (Δ/σ)max = 0.001 |
246 parameters | Δρmax = 2.30 e Å−3 |
0 restraints | Δρmin = −0.89 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pt1 | 0.68067 (2) | 0.59249 (2) | 0.61444 (2) | 0.02459 (8) | |
Cl1 | 0.77201 (12) | 0.52216 (9) | 0.77871 (13) | 0.0402 (4) | |
Cl2 | 0.88400 (13) | 0.62712 (11) | 0.58952 (15) | 0.0500 (4) | |
N1 | 0.4961 (4) | 0.5684 (2) | 0.6216 (4) | 0.0246 (10) | |
N2 | 0.2894 (4) | 0.5832 (2) | 0.5472 (4) | 0.0258 (10) | |
N3 | 0.5929 (4) | 0.6543 (2) | 0.4708 (4) | 0.0262 (10) | |
N4 | 0.2100 (5) | 0.7468 (3) | 0.5602 (4) | 0.0424 (13) | |
C1 | 0.4263 (4) | 0.5256 (3) | 0.6944 (5) | 0.0243 (11) | |
C2 | 0.2964 (5) | 0.5357 (3) | 0.6464 (5) | 0.0273 (12) | |
C3 | 0.2013 (5) | 0.5002 (3) | 0.6993 (5) | 0.0326 (13) | |
H3 | 0.1133 | 0.5088 | 0.6684 | 0.039* | |
C4 | 0.2376 (6) | 0.4525 (3) | 0.7971 (5) | 0.0373 (14) | |
C5 | 0.3714 (5) | 0.4417 (3) | 0.8451 (5) | 0.0341 (13) | |
C6 | 0.4666 (5) | 0.4793 (3) | 0.7922 (5) | 0.0323 (13) | |
H6 | 0.555 | 0.4728 | 0.8231 | 0.039* | |
C7 | 0.4107 (4) | 0.6021 (3) | 0.5360 (4) | 0.0226 (11) | |
C8 | 0.4618 (5) | 0.6507 (3) | 0.4494 (5) | 0.0259 (12) | |
C9 | 0.3925 (5) | 0.6914 (3) | 0.3537 (5) | 0.0344 (14) | |
H9 | 0.3017 | 0.6871 | 0.3369 | 0.041* | |
C10 | 0.4565 (6) | 0.7375 (3) | 0.2843 (5) | 0.0411 (15) | |
H10 | 0.4101 | 0.7671 | 0.2201 | 0.049* | |
C11 | 0.5889 (6) | 0.7412 (3) | 0.3076 (5) | 0.0400 (15) | |
H11 | 0.6342 | 0.7731 | 0.26 | 0.048* | |
C12 | 0.6536 (5) | 0.6980 (3) | 0.4007 (5) | 0.0330 (13) | |
H12 | 0.7446 | 0.6992 | 0.4155 | 0.04* | |
C13 | 0.1693 (5) | 0.6084 (3) | 0.4725 (5) | 0.0316 (13) | |
H13A | 0.0972 | 0.5778 | 0.4967 | 0.038* | |
H13B | 0.1727 | 0.591 | 0.393 | 0.038* | |
C14 | 0.1443 (5) | 0.7031 (3) | 0.4747 (5) | 0.0294 (13) | |
C15 | 0.0569 (6) | 0.7390 (4) | 0.3881 (6) | 0.0488 (17) | |
H15 | 0.0117 | 0.7052 | 0.3278 | 0.059* | |
C16 | 0.0367 (7) | 0.8262 (4) | 0.3915 (7) | 0.065 (2) | |
H16 | −0.0214 | 0.8536 | 0.3324 | 0.078* | |
C17 | 0.1012 (7) | 0.8714 (4) | 0.4803 (7) | 0.060 (2) | |
H17 | 0.0873 | 0.9309 | 0.4858 | 0.072* | |
C18 | 0.1865 (7) | 0.8303 (4) | 0.5617 (6) | 0.059 (2) | |
H18 | 0.232 | 0.863 | 0.6232 | 0.071* | |
C41 | 0.1378 (6) | 0.4107 (4) | 0.8548 (6) | 0.0523 (18) | |
H41A | 0.0524 | 0.4298 | 0.8181 | 0.078* | |
H41B | 0.1528 | 0.4265 | 0.936 | 0.078* | |
H41C | 0.1436 | 0.3488 | 0.8478 | 0.078* | |
C51 | 0.4093 (7) | 0.3882 (4) | 0.9496 (6) | 0.0550 (19) | |
H51A | 0.5027 | 0.3896 | 0.9732 | 0.083* | |
H51B | 0.3813 | 0.3295 | 0.9326 | 0.083* | |
H51C | 0.369 | 0.4105 | 1.0115 | 0.083* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pt1 | 0.02383 (11) | 0.02320 (13) | 0.02634 (13) | 0.00094 (8) | 0.00340 (8) | −0.00134 (10) |
Cl1 | 0.0326 (7) | 0.0456 (9) | 0.0396 (9) | −0.0005 (6) | −0.0012 (6) | 0.0088 (7) |
Cl2 | 0.0287 (7) | 0.0699 (11) | 0.0518 (11) | −0.0063 (7) | 0.0082 (7) | 0.0102 (9) |
N1 | 0.024 (2) | 0.021 (2) | 0.026 (3) | 0.0047 (17) | −0.0011 (18) | −0.0039 (19) |
N2 | 0.024 (2) | 0.021 (2) | 0.032 (3) | 0.0038 (17) | 0.0053 (18) | −0.002 (2) |
N3 | 0.033 (2) | 0.019 (2) | 0.026 (3) | 0.0031 (18) | 0.0048 (19) | −0.001 (2) |
N4 | 0.053 (3) | 0.025 (3) | 0.045 (4) | 0.007 (2) | −0.005 (3) | −0.008 (2) |
C1 | 0.028 (3) | 0.018 (3) | 0.029 (3) | 0.001 (2) | 0.009 (2) | −0.003 (2) |
C2 | 0.029 (3) | 0.022 (3) | 0.031 (3) | −0.001 (2) | 0.006 (2) | −0.006 (2) |
C3 | 0.033 (3) | 0.028 (3) | 0.036 (4) | −0.002 (2) | 0.006 (2) | −0.006 (3) |
C4 | 0.051 (4) | 0.026 (3) | 0.039 (4) | −0.010 (3) | 0.021 (3) | −0.007 (3) |
C5 | 0.047 (4) | 0.026 (3) | 0.032 (4) | −0.002 (3) | 0.014 (3) | −0.004 (3) |
C6 | 0.054 (4) | 0.020 (3) | 0.022 (3) | 0.000 (2) | 0.004 (3) | 0.002 (2) |
C7 | 0.026 (3) | 0.020 (3) | 0.022 (3) | 0.002 (2) | 0.005 (2) | −0.006 (2) |
C8 | 0.031 (3) | 0.023 (3) | 0.024 (3) | 0.006 (2) | 0.005 (2) | −0.003 (2) |
C9 | 0.032 (3) | 0.037 (3) | 0.032 (4) | 0.003 (2) | 0.001 (2) | 0.005 (3) |
C10 | 0.052 (4) | 0.038 (3) | 0.032 (4) | 0.008 (3) | 0.002 (3) | 0.009 (3) |
C11 | 0.068 (4) | 0.026 (3) | 0.030 (4) | −0.004 (3) | 0.017 (3) | 0.008 (3) |
C12 | 0.042 (3) | 0.029 (3) | 0.029 (3) | −0.005 (2) | 0.009 (3) | −0.001 (3) |
C13 | 0.020 (3) | 0.031 (3) | 0.040 (4) | 0.005 (2) | −0.004 (2) | −0.002 (3) |
C14 | 0.026 (3) | 0.032 (3) | 0.030 (3) | 0.006 (2) | 0.005 (2) | −0.001 (3) |
C15 | 0.051 (4) | 0.050 (4) | 0.040 (4) | 0.013 (3) | −0.006 (3) | −0.002 (3) |
C16 | 0.083 (5) | 0.058 (5) | 0.051 (5) | 0.039 (4) | 0.005 (4) | 0.026 (4) |
C17 | 0.080 (5) | 0.042 (4) | 0.063 (6) | 0.023 (4) | 0.029 (4) | 0.005 (4) |
C18 | 0.077 (5) | 0.037 (4) | 0.058 (5) | 0.011 (3) | −0.003 (4) | −0.014 (4) |
C41 | 0.056 (4) | 0.051 (4) | 0.056 (5) | −0.013 (3) | 0.026 (4) | 0.001 (4) |
C51 | 0.072 (5) | 0.052 (4) | 0.043 (5) | −0.014 (3) | 0.017 (4) | 0.011 (3) |
Geometric parameters (Å, º) top
Pt1—N1 | 2.012 (4) | C9—C10 | 1.368 (8) |
Pt1—N3 | 2.037 (4) | C9—H9 | 0.95 |
Pt1—Cl2 | 2.2959 (14) | C10—C11 | 1.384 (8) |
Pt1—Cl1 | 2.2992 (14) | C10—H10 | 0.95 |
N1—C7 | 1.343 (6) | C11—C12 | 1.372 (7) |
N1—C1 | 1.406 (6) | C11—H11 | 0.95 |
N2—C7 | 1.352 (6) | C12—H12 | 0.95 |
N2—C2 | 1.385 (7) | C13—C14 | 1.513 (6) |
N2—C13 | 1.470 (6) | C13—H13A | 0.99 |
N3—C12 | 1.332 (7) | C13—H13B | 0.99 |
N3—C8 | 1.370 (6) | C14—C15 | 1.375 (7) |
N4—C14 | 1.317 (7) | C15—C16 | 1.389 (8) |
N4—C18 | 1.337 (7) | C15—H15 | 0.95 |
C1—C6 | 1.372 (7) | C16—C17 | 1.351 (9) |
C1—C2 | 1.403 (6) | C16—H16 | 0.95 |
C2—C3 | 1.398 (7) | C17—C18 | 1.363 (9) |
C3—C4 | 1.378 (8) | C17—H17 | 0.95 |
C3—H3 | 0.95 | C18—H18 | 0.95 |
C4—C5 | 1.441 (8) | C41—H41A | 0.98 |
C4—C41 | 1.512 (8) | C41—H41B | 0.98 |
C5—C6 | 1.412 (7) | C41—H41C | 0.98 |
C5—C51 | 1.493 (8) | C51—H51A | 0.98 |
C6—H6 | 0.95 | C51—H51B | 0.98 |
C7—C8 | 1.461 (7) | C51—H51C | 0.98 |
C8—C9 | 1.393 (7) | | |
| | | |
N1—Pt1—N3 | 79.81 (17) | C9—C10—C11 | 119.9 (5) |
N1—Pt1—Cl2 | 174.27 (13) | C9—C10—H10 | 120.1 |
N3—Pt1—Cl2 | 94.46 (12) | C11—C10—H10 | 120.1 |
N1—Pt1—Cl1 | 97.97 (13) | C12—C11—C10 | 119.0 (5) |
N3—Pt1—Cl1 | 177.73 (12) | C12—C11—H11 | 120.5 |
Cl2—Pt1—Cl1 | 87.76 (5) | C10—C11—H11 | 120.5 |
C7—N1—C1 | 107.2 (4) | N3—C12—C11 | 122.0 (5) |
C7—N1—Pt1 | 115.0 (3) | N3—C12—H12 | 119.0 |
C1—N1—Pt1 | 137.7 (3) | C11—C12—H12 | 119.0 |
C7—N2—C2 | 107.2 (4) | N2—C13—C14 | 113.0 (4) |
C7—N2—C13 | 128.2 (5) | N2—C13—H13A | 109.0 |
C2—N2—C13 | 124.6 (4) | C14—C13—H13A | 109.0 |
C12—N3—C8 | 119.7 (5) | N2—C13—H13B | 109.0 |
C12—N3—Pt1 | 124.7 (4) | C14—C13—H13B | 109.0 |
C8—N3—Pt1 | 115.6 (3) | H13A—C13—H13B | 107.8 |
C14—N4—C18 | 116.6 (5) | N4—C14—C15 | 123.7 (5) |
C6—C1—C2 | 122.5 (5) | N4—C14—C13 | 117.1 (5) |
C6—C1—N1 | 131.0 (5) | C15—C14—C13 | 119.2 (5) |
C2—C1—N1 | 106.5 (4) | C14—C15—C16 | 118.0 (6) |
N2—C2—C3 | 131.6 (5) | C14—C15—H15 | 121.0 |
N2—C2—C1 | 107.8 (4) | C16—C15—H15 | 121.0 |
C3—C2—C1 | 120.6 (5) | C17—C16—C15 | 118.9 (6) |
C4—C3—C2 | 118.8 (5) | C17—C16—H16 | 120.6 |
C4—C3—H3 | 120.6 | C15—C16—H16 | 120.6 |
C2—C3—H3 | 120.6 | C16—C17—C18 | 118.9 (6) |
C3—C4—C5 | 120.2 (5) | C16—C17—H17 | 120.6 |
C3—C4—C41 | 120.4 (6) | C18—C17—H17 | 120.6 |
C5—C4—C41 | 119.4 (6) | N4—C18—C17 | 123.9 (6) |
C6—C5—C4 | 120.5 (5) | N4—C18—H18 | 118.1 |
C6—C5—C51 | 119.9 (5) | C17—C18—H18 | 118.1 |
C4—C5—C51 | 119.6 (5) | C4—C41—H41A | 109.5 |
C1—C6—C5 | 117.4 (5) | C4—C41—H41B | 109.5 |
C1—C6—H6 | 121.3 | H41A—C41—H41B | 109.5 |
C5—C6—H6 | 121.3 | C4—C41—H41C | 109.5 |
N1—C7—N2 | 111.3 (4) | H41A—C41—H41C | 109.5 |
N1—C7—C8 | 117.0 (4) | H41B—C41—H41C | 109.5 |
N2—C7—C8 | 131.7 (5) | C5—C51—H51A | 109.5 |
N3—C8—C9 | 120.1 (5) | C5—C51—H51B | 109.5 |
N3—C8—C7 | 112.6 (4) | H51A—C51—H51B | 109.5 |
C9—C8—C7 | 127.3 (5) | C5—C51—H51C | 109.5 |
C10—C9—C8 | 119.3 (5) | H51A—C51—H51C | 109.5 |
C10—C9—H9 | 120.4 | H51B—C51—H51C | 109.5 |
C8—C9—H9 | 120.4 | | |
| | | |
C7—N1—C1—C6 | 178.4 (5) | C2—N2—C7—C8 | −179.5 (5) |
Pt1—N1—C1—C6 | −2.8 (9) | C13—N2—C7—C8 | −0.7 (8) |
C7—N1—C1—C2 | 0.4 (5) | C12—N3—C8—C9 | 1.0 (7) |
Pt1—N1—C1—C2 | 179.2 (4) | Pt1—N3—C8—C9 | 179.6 (4) |
C7—N2—C2—C3 | 179.4 (5) | C12—N3—C8—C7 | −178.6 (4) |
C13—N2—C2—C3 | 0.6 (8) | Pt1—N3—C8—C7 | 0.0 (5) |
C7—N2—C2—C1 | −0.5 (5) | N1—C7—C8—N3 | −0.2 (6) |
C13—N2—C2—C1 | −179.3 (4) | N2—C7—C8—N3 | −180.0 (5) |
C6—C1—C2—N2 | −178.2 (4) | N1—C7—C8—C9 | −179.8 (5) |
N1—C1—C2—N2 | 0.1 (5) | N2—C7—C8—C9 | 0.5 (9) |
C6—C1—C2—C3 | 1.9 (8) | N3—C8—C9—C10 | −2.6 (8) |
N1—C1—C2—C3 | −179.9 (4) | C7—C8—C9—C10 | 177.0 (5) |
N2—C2—C3—C4 | 177.6 (5) | C8—C9—C10—C11 | 2.0 (9) |
C1—C2—C3—C4 | −2.4 (8) | C9—C10—C11—C12 | 0.1 (9) |
C2—C3—C4—C5 | 1.7 (8) | C8—N3—C12—C11 | 1.2 (8) |
C2—C3—C4—C41 | −178.1 (5) | Pt1—N3—C12—C11 | −177.3 (4) |
C3—C4—C5—C6 | −0.5 (8) | C10—C11—C12—N3 | −1.7 (8) |
C41—C4—C5—C6 | 179.3 (5) | C7—N2—C13—C14 | −67.0 (7) |
C3—C4—C5—C51 | −178.6 (5) | C2—N2—C13—C14 | 111.5 (5) |
C41—C4—C5—C51 | 1.2 (8) | C18—N4—C14—C15 | 1.2 (9) |
C2—C1—C6—C5 | −0.6 (7) | C18—N4—C14—C13 | −179.6 (6) |
N1—C1—C6—C5 | −178.4 (5) | N2—C13—C14—N4 | −16.9 (7) |
C4—C5—C6—C1 | −0.1 (8) | N2—C13—C14—C15 | 162.4 (5) |
C51—C5—C6—C1 | 178.0 (5) | N4—C14—C15—C16 | −0.2 (10) |
C1—N1—C7—N2 | −0.7 (5) | C13—C14—C15—C16 | −179.3 (6) |
Pt1—N1—C7—N2 | −179.8 (3) | C14—C15—C16—C17 | −1.4 (11) |
C1—N1—C7—C8 | 179.5 (4) | C15—C16—C17—C18 | 1.8 (11) |
Pt1—N1—C7—C8 | 0.4 (5) | C14—N4—C18—C17 | −0.8 (11) |
C2—N2—C7—N1 | 0.8 (5) | C16—C17—C18—N4 | −0.8 (12) |
C13—N2—C7—N1 | 179.5 (4) | | |
Hydrogen-bond geometry (Å, º) topCg refers to the centroid of the five-membered platinum diimine ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···Cl2 | 0.95 | 2.58 | 3.205 (6) | 124 |
C10—H10···N4i | 0.95 | 2.59 | 3.388 (8) | 142 |
C18—H18···Cl1ii | 0.95 | 2.76 | 3.546 (7) | 140 |
C11—H11···Pt1i | 0.95 | 2.83 | 3.722 (6) | 157 |
C11—H11···Cgi | 0.95 | 3.21 | 3.885 (6) | 130 |
C13—H13A···Cl2iii | 0.99 | 2.80 | 3.564 (6) | 135 |
C13—H13B···Cl1iv | 0.99 | 2.84 | 3.764 (6) | 155 |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, y+1/2, −z+3/2; (iii) x−1, y, z; (iv) −x+1, −y+1, −z+1. |
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