metal-organic compounds
trans-Bis[2-(aminomethyl)pyridine-κ2N,N′]platinum(II)] bis(hexafluoridophosphate)
aDepartment of Chemistry, Graduate School of Arts and Sciences, The University of Tokyo, Komaba 3-8-1, Meguro-ku, Tokyo, 153-8902, Japan, and bDepartment of Chemistry & Research Center for Smart Molecules, Rikkyo University, Nishi-Ikebukuro 3-34-1, Toshima-ku, Tokyo, 171-8501, Japan
*Correspondence e-mail: cnmatsu@rikkyo.ac.jp
The title compound, [Pt(amp)2](PF6)2 [amp = 2-(aminomethyl)pyridine, C6H8N2], crystallizes in the P with a half of one [Pt(amp)2]2+ cation and one hexafluoridophosphate ion in the The PtII atom lies on an inversion centre and has a square-planar coordination sphere defined by two amino groups and two pyridine moieties of two 2-(aminomethyl)pyridine chelate ligands. The of the title salt is composed of alternating rows of [Pt(amp)2]2+ cations and PF6− anions. The crystal packing is stabilized by N—H⋯F hydrogen bonds between the amino groups and the hexafluoridophosphate anions. The PF6 anion is disordered over two sets of sites with an occupancy ratio of 0.744 (6):0.256 (6).
Keywords: crystal structure; platinum(II) complex; 2-(aminomethyl)pyridine; hexafluoridophosphate; hydrogen bonding.
CCDC reference: 1864971
Structure description
trans-Bis[(2-(aminomethyl)pyridine-κ2N,N′)platinum(II)] bis(hexafluoridophosphate), [Pt(amp)2](PF6)2 (amp = 2-(aminomethyl)pyridine), was prepared in order to elucidate the single-crystalline of [Pt(amp)2] salts. One of them, [Pt(amp)2]Cl2·H2O, has been reported as the first single-crystalline photochromic metal-complex salt (Nishimura & Matsushita, 2002). The title salt is the hexafluoridophosphate of trans-bis(2-(aminomethyl)pyridine-κ2N,N′)platinum(II) complex and does not display single-crystalline photochromic behavior under the same photo-irradiation conditions as [Pt(amp)2]Cl2·H2O, i.e. under the visible light of a tungsten lamp.
The molecular components of the title salt are displayed in Fig. 1. The comprises half of one [Pt(amp)2]2+ cation and one hexafluoridophosphate anion. The PtII atom of [Pt(amp)2]2+ cation lies on an inversion centre and is coordinated by four N atoms of two amino groups and two pyridine moieties of the two 2-(aminomethyl)pyridine chelate ligands in a trans configuration. The methylpyridine part of the 2-(aminomethyl)pyridine ligand forms a planar configuration with the r.m.s. deviation of the least-squares plane formed by atoms C1–C6 and N2 being 0.0066 Å. The dihedral angle between the methylpyridine plane and the [PtN4] coordination plane is 10.4 (2)°. The [Pt(amp)2]2+ cation does not adapt a co-planar configuration and is slightly distorted.
The Pt—Namine [2.044 (3) Å] and Pt—Npyridine [2.013 (3) Å] bond lengths, and N—Pt—N [80.67 (12)°] bond angle in the chelate ring are consistent with those values reported for [Pt(amp)2]Cl2·H2O [Pt—Namine = 2.043 (5), 2.048 (4) Å, Pt—Npyridine = 2.011 (4), 2.018 (4) Å, N—Pt—N = 81.06 (17), 81.33 (18)°; Nishimura & Matsushita, 2002].
The 2]2+ cations and PF6− anions (Fig. 2). The arrangement of the cations and anions in the crystal packing of the title salt is very similar to that of the chloride monohydrate, [Pt(amp)2]Cl2·H2O (Nishimura & Matsushita, 2002). The N—H⋯F hydrogen bonds between the amino groups of [Pt(amp)2]2+ cations and the fluorine atoms of the PF6− anions stabilize the crystal packing of the title salt (Fig. 3 and Table 1).
of the title salt is composed of alternating rows of [Pt(amp)Synthesis and crystallization
To a solution of [Pt(amp)2]Cl2·H2O (216 mg) dissolved in water (60 ml) was slowly added a solution of NH4PF6 (150 mg) dissolved in water (40 ml). A short time later, slightly yellowish colourless needle-like crystals precipitated. The crystals were collected by filtration and air-dried. Yield: 158 mg (52%). Elemental analysis: found: C, 20.51; H, 2.28; N, 7.99%, calculated for C12H16F12N4P2Pt: C, 20.55; H, 2.30; N, 7.99%. The elemental analysis was carried out by the Laboratory of Organic Elemental Analysis, Department of Chemistry, Graduate School of Science, The University of Tokyo. A single-crystal suitable for X-ray crystallography was chosen from the crystals collected.
Refinement
Crystal data, data collection and structure . The structure was refined as a two-component disordered structure of the PF6 anion, the minor fluorine atoms of which were based on the positions of residual peaks. The occupancy ratio of 0.744 (6):0.256 (6) for the two orientations was obtained by with a free variable. The maximum and minimum electron density peaks are located 0.76 and 0.68 Å, respectively, from the Pt atom.
details are summarized in Table 2Structural data
CCDC reference: 1864971
https://doi.org/10.1107/S2414314618012361/zq4030sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618012361/zq4030Isup2.hkl
Data collection: PROCESS-AUTO (Rigaku, 1998); cell
RAPID-AUTO (Rigaku, 2015); data reduction: RAPID-AUTO (Rigaku, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2018); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b) and publCIF (Westrip, 2010).[Pt(C6H8N2)2](PF6)2 | Z = 1 |
Mr = 701.32 | F(000) = 332 |
Triclinic, P1 | Dx = 2.377 Mg m−3 |
a = 7.3011 (3) Å | Mo Kα radiation, λ = 0.71075 Å |
b = 8.3055 (3) Å | Cell parameters from 13361 reflections |
c = 9.2821 (3) Å | θ = 2.5–32.6° |
α = 64.226 (4)° | µ = 7.44 mm−1 |
β = 75.212 (5)° | T = 296 K |
γ = 84.540 (6)° | Needle, colourless |
V = 489.99 (4) Å3 | 0.41 × 0.29 × 0.12 mm |
Rigaku R-AXIS RAPID imaging-plate diffractometer | 3484 independent reflections |
Radiation source: X-ray sealed tube | 3484 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
Detector resolution: 10.00 pixels mm-1 | θmax = 32.6°, θmin = 2.5° |
ω scans | h = −11→10 |
Absorption correction: integration (NUMABS; Rigaku, 1999) | k = −12→12 |
Tmin = 0.206, Tmax = 0.508 | l = −14→14 |
12933 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)] = 0.028 | H-atom parameters constrained |
wR(F2) = 0.067 | w = 1/[σ2(Fo2) + (0.0395P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
3484 reflections | Δρmax = 1.92 e Å−3 |
180 parameters | Δρmin = −1.55 e Å−3 |
48 restraints | Extinction correction: (SHELXL2014; Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: heavy-atom method | Extinction coefficient: 0.038 (3) |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Pt | 0.0000 | 0.5000 | 0.5000 | 0.03263 (7) | |
N1 | 0.1202 (5) | 0.6204 (5) | 0.2528 (4) | 0.0488 (7) | |
H1A | 0.0691 | 0.5740 | 0.2015 | 0.059* | |
H1B | 0.0954 | 0.7367 | 0.2141 | 0.059* | |
N2 | 0.2490 (4) | 0.3730 (4) | 0.4965 (3) | 0.0375 (5) | |
C1 | 0.3271 (6) | 0.5969 (6) | 0.2169 (5) | 0.0525 (8) | |
H1C | 0.3901 | 0.7028 | 0.2015 | 0.063* | |
H1D | 0.3682 | 0.5818 | 0.1155 | 0.063* | |
C2 | 0.3812 (5) | 0.4376 (5) | 0.3542 (4) | 0.0416 (6) | |
C3 | 0.5584 (6) | 0.3611 (7) | 0.3380 (6) | 0.0555 (9) | |
H3 | 0.6484 | 0.4074 | 0.2382 | 0.067* | |
C4 | 0.5998 (6) | 0.2157 (7) | 0.4716 (7) | 0.0608 (10) | |
H4 | 0.7185 | 0.1640 | 0.4638 | 0.073* | |
C5 | 0.4624 (7) | 0.1487 (6) | 0.6161 (7) | 0.0582 (10) | |
H5 | 0.4870 | 0.0500 | 0.7072 | 0.070* | |
C6 | 0.2876 (6) | 0.2284 (5) | 0.6259 (5) | 0.0489 (7) | |
H6 | 0.1946 | 0.1814 | 0.7237 | 0.059* | |
P | 0.13393 (16) | 0.17834 (14) | 0.13320 (13) | 0.04854 (19) | |
F1 | 0.3338 (7) | 0.2085 (8) | 0.1472 (8) | 0.1137 (18) | |
F3 | −0.0705 (8) | 0.1541 (9) | 0.1136 (8) | 0.132 (3) | |
F2 | 0.1733 (10) | 0.3286 (9) | −0.0505 (7) | 0.096 (2) | 0.744 (6) |
F4 | 0.0336 (12) | 0.3072 (11) | 0.2050 (11) | 0.115 (2) | 0.744 (6) |
F5 | 0.0933 (13) | 0.0057 (10) | 0.2996 (9) | 0.118 (3) | 0.744 (6) |
F6 | 0.2280 (17) | 0.0422 (11) | 0.0581 (12) | 0.135 (3) | 0.744 (6) |
F2B | 0.131 (3) | 0.399 (3) | 0.070 (3) | 0.107 (4) | 0.256 (6) |
F4B | 0.076 (4) | 0.167 (4) | 0.313 (3) | 0.115 (4) | 0.256 (6) |
F5B | 0.161 (4) | −0.014 (3) | 0.182 (4) | 0.114 (4) | 0.256 (6) |
F6B | 0.199 (4) | 0.222 (4) | −0.047 (3) | 0.110 (4) | 0.256 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt | 0.03905 (9) | 0.02788 (9) | 0.02934 (8) | 0.00042 (5) | −0.00823 (5) | −0.01065 (5) |
N1 | 0.0496 (14) | 0.0518 (17) | 0.0335 (12) | 0.0053 (13) | −0.0089 (11) | −0.0093 (11) |
N2 | 0.0410 (11) | 0.0324 (11) | 0.0383 (12) | 0.0031 (9) | −0.0117 (10) | −0.0137 (9) |
C1 | 0.0476 (16) | 0.053 (2) | 0.0392 (16) | −0.0015 (15) | −0.0034 (13) | −0.0073 (14) |
C2 | 0.0415 (13) | 0.0400 (15) | 0.0424 (15) | −0.0001 (11) | −0.0075 (12) | −0.0178 (12) |
C3 | 0.0430 (16) | 0.060 (2) | 0.061 (2) | 0.0034 (16) | −0.0062 (16) | −0.028 (2) |
C4 | 0.0504 (18) | 0.059 (2) | 0.077 (3) | 0.0162 (17) | −0.019 (2) | −0.033 (2) |
C5 | 0.058 (2) | 0.046 (2) | 0.066 (3) | 0.0142 (17) | −0.0238 (19) | −0.0179 (18) |
C6 | 0.0517 (16) | 0.0405 (16) | 0.0461 (17) | 0.0085 (14) | −0.0153 (14) | −0.0104 (13) |
P | 0.0556 (5) | 0.0396 (4) | 0.0434 (4) | 0.0051 (4) | −0.0151 (4) | −0.0104 (3) |
F1 | 0.081 (2) | 0.114 (4) | 0.137 (5) | −0.003 (2) | −0.057 (3) | −0.028 (3) |
F3 | 0.102 (3) | 0.126 (5) | 0.136 (5) | −0.032 (3) | −0.067 (3) | 0.001 (3) |
F2 | 0.103 (4) | 0.078 (3) | 0.063 (3) | −0.004 (3) | −0.022 (3) | 0.011 (3) |
F4 | 0.131 (5) | 0.106 (4) | 0.117 (5) | 0.030 (4) | −0.012 (4) | −0.072 (4) |
F5 | 0.143 (5) | 0.090 (4) | 0.071 (3) | −0.021 (4) | −0.043 (3) | 0.024 (3) |
F6 | 0.197 (7) | 0.089 (4) | 0.118 (5) | 0.038 (4) | −0.019 (5) | −0.060 (4) |
F2B | 0.125 (7) | 0.072 (6) | 0.108 (7) | 0.012 (6) | −0.025 (6) | −0.027 (6) |
F4B | 0.146 (7) | 0.117 (7) | 0.074 (6) | 0.001 (7) | −0.018 (6) | −0.038 (6) |
F5B | 0.165 (8) | 0.067 (6) | 0.099 (7) | 0.009 (6) | −0.038 (7) | −0.022 (6) |
F6B | 0.154 (8) | 0.099 (7) | 0.071 (6) | 0.005 (7) | −0.027 (6) | −0.032 (6) |
Pt—N2i | 2.013 (3) | C4—C5 | 1.373 (8) |
Pt—N2 | 2.013 (3) | C4—H4 | 0.9300 |
Pt—N1 | 2.044 (3) | C5—C6 | 1.382 (6) |
Pt—N1i | 2.044 (3) | C5—H5 | 0.9300 |
N1—C1 | 1.475 (5) | C6—H6 | 0.9300 |
N1—H1A | 0.8900 | P—F5B | 1.46 (2) |
N1—H1B | 0.8900 | P—F6B | 1.50 (2) |
N2—C2 | 1.340 (4) | P—F4 | 1.532 (6) |
N2—C6 | 1.349 (4) | P—F1 | 1.551 (4) |
C1—C2 | 1.491 (5) | P—F5 | 1.565 (5) |
C1—H1C | 0.9700 | P—F4B | 1.58 (2) |
C1—H1D | 0.9700 | P—F2 | 1.586 (5) |
C2—C3 | 1.388 (5) | P—F3 | 1.590 (5) |
C3—C4 | 1.381 (7) | P—F6 | 1.590 (7) |
C3—H3 | 0.9300 | P—F2B | 1.66 (2) |
N2i—Pt—N2 | 180.0 | N2—C6—C5 | 121.3 (4) |
N2i—Pt—N1 | 99.33 (12) | N2—C6—H6 | 119.3 |
N2—Pt—N1 | 80.67 (12) | C5—C6—H6 | 119.3 |
N2i—Pt—N1i | 80.67 (12) | F5B—P—F6B | 92.5 (15) |
N2—Pt—N1i | 99.33 (12) | F5B—P—F1 | 93.4 (12) |
N1—Pt—N1i | 180.0 | F6B—P—F1 | 93.6 (11) |
C1—N1—Pt | 111.7 (2) | F4—P—F1 | 95.5 (5) |
C1—N1—H1A | 109.3 | F4—P—F5 | 96.1 (5) |
Pt—N1—H1A | 109.3 | F1—P—F5 | 93.4 (4) |
C1—N1—H1B | 109.3 | F5B—P—F4B | 96.4 (15) |
Pt—N1—H1B | 109.3 | F6B—P—F4B | 170.4 (15) |
H1A—N1—H1B | 107.9 | F1—P—F4B | 82.2 (10) |
C2—N2—C6 | 119.3 (3) | F4—P—F2 | 93.1 (5) |
C2—N2—Pt | 116.6 (2) | F1—P—F2 | 91.2 (3) |
C6—N2—Pt | 124.2 (2) | F5—P—F2 | 169.3 (5) |
N1—C1—C2 | 110.6 (3) | F5B—P—F3 | 88.2 (12) |
N1—C1—H1C | 109.5 | F6B—P—F3 | 85.2 (11) |
C2—C1—H1C | 109.5 | F4—P—F3 | 84.0 (5) |
N1—C1—H1D | 109.5 | F1—P—F3 | 178.0 (3) |
C2—C1—H1D | 109.5 | F5—P—F3 | 88.5 (4) |
H1C—C1—H1D | 108.1 | F4B—P—F3 | 98.8 (11) |
N2—C2—C3 | 121.5 (4) | F2—P—F3 | 87.0 (3) |
N2—C2—C1 | 116.0 (3) | F4—P—F6 | 177.1 (6) |
C3—C2—C1 | 122.5 (4) | F1—P—F6 | 87.4 (5) |
C4—C3—C2 | 119.3 (4) | F5—P—F6 | 83.6 (5) |
C4—C3—H3 | 120.3 | F2—P—F6 | 86.9 (5) |
C2—C3—H3 | 120.3 | F3—P—F6 | 93.2 (6) |
C5—C4—C3 | 118.8 (4) | F5B—P—F2B | 173.1 (15) |
C5—C4—H4 | 120.6 | F6B—P—F2B | 84.9 (13) |
C3—C4—H4 | 120.6 | F1—P—F2B | 80.5 (9) |
C4—C5—C6 | 119.8 (4) | F4B—P—F2B | 85.9 (13) |
C4—C5—H5 | 120.1 | F3—P—F2B | 97.8 (9) |
C6—C5—H5 | 120.1 | ||
Pt—N1—C1—C2 | 22.8 (5) | N2—C2—C3—C4 | −0.3 (7) |
C6—N2—C2—C3 | −1.3 (5) | C1—C2—C3—C4 | 178.8 (4) |
Pt—N2—C2—C3 | 179.6 (3) | C2—C3—C4—C5 | 1.2 (7) |
C6—N2—C2—C1 | 179.6 (4) | C3—C4—C5—C6 | −0.7 (8) |
Pt—N2—C2—C1 | 0.5 (4) | C2—N2—C6—C5 | 1.9 (6) |
N1—C1—C2—N2 | −15.6 (5) | Pt—N2—C6—C5 | −179.1 (3) |
N1—C1—C2—C3 | 165.3 (4) | C4—C5—C6—N2 | −0.9 (7) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···F2ii | 0.89 | 2.40 | 3.080 (8) | 133 |
N1—H1A···F4 | 0.89 | 2.24 | 2.971 (9) | 139 |
N1—H1B···F6iii | 0.89 | 2.46 | 3.233 (10) | 146 |
N1—H1A···F2B | 0.89 | 2.22 | 2.98 (2) | 143 |
N1—H1B···F5Biii | 0.89 | 2.05 | 2.84 (2) | 148 |
Symmetry codes: (ii) −x, −y+1, −z; (iii) x, y+1, z. |
Funding information
Funding for this research was provided by: JSPS KAKENHI (Coordination Asymmetry) (grant No. JP16H06509).
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