Hydrogen versus fluorine: effects on mol­ecular structure and inter­molecular inter­actions in a platinum iso­cyanate complex

At the mol­ecular level, the enantio­merically pure square-planar organo­platinum com­plex (SP-4-4)-(R)-[2-(1-amino­ethyl)-5-fluorophenyl-[kappa]²C¹,N][(R)-1-(4-fluoro­phenyl)ethyl­amine-[kappa]N](iso­cyanato-[kappa]N)platinum(II), [Pt(C₈H₉FN)(NCO)(C₈H₁₀FN)], and its congener without fluorine substituents on the aryl rings adopt the same structure within error. The similarities between the compounds extend to the most relevant inter­molecular inter­actions, i.e. N-H...O and N-H...N hydrogen bonds link neighbouring mol­ecules into chains along the shortest lattice parameter in each structure. Differences between the crystal structures of the fluoro-substituted and parent complex become obvious with respect to secondary inter­actions perpendicular to the classical hydrogen bonds; the fluorinated compound features short C-H...F contacts with an F...H distance of ca 2.6 Å. The fluorine substitution is also reflected in reduced backbonding from the metal cation to the iso­cyanate ligand.

S1. Introduction

In 1968, Cope & Friedrich (1968) discovered orthometallation of activated benzyl amines with palladium and platinum. In the following years, the reaction with palladium was successfully expanded to more general substrates (Cockburn et al., 1973; Dunina et al., 1988; Avshu et al., 1983; Fuchita & Tsuchiya, 1993; Fuchita et al., 1997; Vicente et al., 1993). Our group reported the crystal structures of inter­mediates along the reaction pathway (Calmuschi & Englert, 2002; Calmuschi, Jonas & Englert, 2004) and of the first trans-configured cyclo­palladated amine (Calmuschi-Cula et al., 2005). With respect to crystal engineering, we used the cyclo­palladated primary amines for the construction of quasiracemic solids (Calmuschi, Alesi & Englert, 2004; Calmuschi & Englert, 2005). In contrast with these achievements in the field of cyclo­palladation, only modest progress was made with respect to cyclo­platination until 2007 (Capapé et al., 2007). In 2008, our group reported the first convenient route to cyclo­platination of primary amines via a mixed-valent platinum iodide precursor (Calmuschi-Cula & Englert, 2008). The cyclo­platinated primary amines thus obtained allowed the preparation of a whole class of derivatives: the σ-donor and iodide ligands may be substituted (Calmuschi-Cula & Englert, 2008; Raven et al., 2014), a chelating ligand can be introduced (Raven et al., 2015a), and Pt^IV complexes are accessible via oxidative addition (Raven et al., 2015b).

In the context of our earlier work, we reported the synthesis and structural characterization of the Pt^II iso­cyanate complex (1) (Raven et al., 2014) (Scheme 1). Such complexes are accessible via abstraction of the iodide ligand by a silver salt of a weakly coordinating anion such as tetra­fluoro­borate or perchlorate. Subsequent addition of an equimolar qu­antity of sodium iso­cyanate yields the target compounds.

We discuss here the analogous derivative of 1-(4-fluoro­phenyl)­ethyl­amine, complex (2), with an emphasis on the effects of fluoro substitution in (2). One might expect that such an electronegative atom in the para position would significantly reduce the electron density of the aromatic rings without major steric effects.

S2. Experimental

S2.1. Synthesis and crystallization

Chemicals were used without further purification. NMR samples contained tetra­methyl­silane as the standard. The measurements were conducted at the Institute for Inorganic Chemistry with a Bruker Avance II Ultrashield Plus 400.

Complex (1) was prepared according to the procedure of Raven et al. (2014).

The cyclo­platinated aqua precursor of (2) was prepared according to Raven et al. (2014). At room temperature, this aqua complex (100 mg, 0.17 mmol) was dissolved in methanol (10 ml) and NaOCN (11 mg, 0.17 mmol) was added. After 10 min, the brown solution turned purple. Water (2 ml) was added and a light-purple solid precipitated. The solid was recovered by centrifugation and dissolved in methanol (5 ml). Complex (2) was crystallized by addition of water and isolated by filtration (yield 71 mg, 0.12 mmol, 70%). Decomposition was observed at 472 K [for comparison, the unsubstituted parent complex (1) decomposes at 451 K].

Spectroscopic analysis: ¹H NMR (400 MHz, CD₂Cl₂, δ, p.p.m.): 1.48 (d, 3H, CH₃, non-cyclo­platinated amine), 1.70 (d, 3H, CH₃, cyclo­platinated amine), 3.51 (br, 2H, NH₂), 3.71 (br, 1H, NH₂), 4.26 (m, 2H, CH, cyclo­platinated + non-cyclo­platinated amine), 4.61 (br, 1H, NH₂), 6.38 (m, 1H, CH_arom), 6.61 (m,1H, CH_arom), 6.85 (m, 1H, CH_arom), 7.10 (m, 2H, CH_arom), 7.36 (m, 2H, CH_arom); ¹³C NMR (100.61 MHz, CD₂Cl₂, δ, p.p.m.): 23.79 (s, 1 C, CH₃, non-cyclo­platinated amine), 25.17 (s, 1 C, CH₃, cyclo­platinated amine), 58.19 (s, 1 C, CH, non-cyclo­platinated amine), 62.20 (s, 1 C, cyclo­platinated amine), 110.77 (d, 1 C, sp²-C), 117.24 (d, 2 C, sp²-C), 117.51 (s, 1 C, sp²-C), 123.94 (d, 1 C, sp²-C), 129.47 (d, 2 C, sp²-C), 139.56 (d, 1 C, sp²-C), 152.43 (s, 1 C, sp²-C), 160.02 (s, 1 C, sp²-C), 162.47 (s, 1 C, sp²-C), 162.71 (s, 1 C, sp²-C), 165.16 (s, 1 C, sp-C); ¹⁹F NMR (376.48 MHz, CD₂Cl₂, δ, p.p.m.): −117.21 (s, 1 F, non-cyclo­platinated amine), −113.99 (s, 1 F, cyclo­platinated amine); ¹⁹⁵Pt NMR (85.71 MHz, CD₂Cl₂, δ, p.p.m.): −3129.61.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms attached to C atoms were introduced in their idealized positions and treated as riding, with C—H = 1.00 Å and U_iso(H) = 1.2U_eq(C) for aliphatic CH groups, C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for CH₃ groups, and C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for aromatic CH groups. H atoms attached to N atoms were located from a difference Fourier map. Their coordinates were refined; a distance restraint with a target distance of 0.90 Å was used for N1—H1B, with U_iso(H) = 1.2U_eq(N). The enanti­opol parameter (Parsons & Flack, 2004) confirmed the central chirality of the coordinated phenyl­ethyl­amine ligands.

S3. Results and discussion

Complex (2) crystallizes in the chiral space group P2₁2₁2₁ with one molecule of the complex in the asymmetric unit; Fig. 1 shows a displacement ellipsoid plot of the molecule.

We will first compare compounds (1) and (2) at the molecular level and then discuss inter­molecular inter­actions. An overlay of the molecules (Fig. 2; the two F atoms in the para positions of the aryl rings have been omitted) shows that both iso­cyanate complexes adopt the same conformation in their crystalline solids; the r.m.s. displacement between equivalent atoms in the molecules amounts to only 0.1 Å. Despite the apparent agreement between (1) and (2) with respect to their overall shape, the compounds might exhibit small but relevant differences in terms of intra­molecular distances and angles. Table 2 shows that this is not the case: the coordinative bonds in the two complexes do not differ significantly.

Metal coordination apart, equal inter­atomic distances within error are also encountered for the iso­cyanate ligand in (1) and (2). We recall a relevant observation by Cotton & Wing (1965): C—O distances in metal carbonyl complexes show only little variation and do not reflect bond orders in a sensitive way. We can confirm the same behaviour for transition metal iso­cyanate complexes. In our search for transition metal iso­cyanates in the Cambridge Structural Database (Version 5.36, including updates to May 2015; Groom & Allen, 2014), we only considered low-temperature results (T < 200 K) and excluded disordered structures, results obtained on powder and entries with unresolved errors. For 131 observations fulfilling these conditions, the C—N distance in the iso­cyanate ligand shows a sharp maximum at 1.153 (3) Å; the corresponding histogram is given in Fig. 3. The C—N bond lengths in (1) [1.161 (15) Å] and (2) [1.160 (9) Å] match this value within error.

The similarity between (1) and (2) extends to the shortest inter­molecular contacts. In each structure, neighbouring molecules inter­act via classical N—H···O and N—H···N hydrogen bonds; for the new structure of (2), their geometry has been compiled in Table 3.

In both structures, the hydrogen bonds result in helices around the twofold screw axis associated with the shortest lattice parameter of ca 4.5 Å. Fig. 4 allows a comparison of these helices in (1) and (2). Adjacent helices in the [001] direction are generated by translation along c and are therefore parallel in (1). In contrast, they are related by a twofold screw axis along c in the case of (2) and thus adopt an anti­parallel orientation.

Despite the similarities between (1) and (2) in terms of molecular geometry and hydrogen bonding, crystal chemistry is not entirely blind with respect to substitution of a para H atom by F, and the inter­molecular inter­actions perpendicular to the hydrogen-bonded chains reflect the differences. In Fig. 5, the packing features common to both compounds have been marked in pink. The essentially nonpolar periphery of (1) results in the inter­molecular contact region emphasized as a blue ellipse in Fig. 5; in structural biology, it might have been addressed as a hydro­phobic bond. In contrast with this situation, the F-substituted aryl rings in (2) favour C—H···F contacts of ca 2.6 Å. This region, dominated by long and presumably weak nonclassical hydrogen bonds, has been marked in yellow in Fig. 5.

Although the diffraction experiments do not allow the deduction of significant differences in the intra­molecular geometries of (1) and (2), the electronic effect of fluorine substitution can easily be detected. In an IR spectrum, the band associated with the C—N bond in the iso­cyanate ligand is detected at a frequency of ca 2200 cm⁻¹ (Norbury & Sinha, 1968). π backbonding according to the Dewar–Chatt–Duncanson model (Dewar, 1951; Chatt & Duncanson, 1953) leads to a reduced bond order for the C—N bond in the NCO group. In the case of (1), the higher electron density at the central Pt^II atom leads to more pronounced backbonding and hence a lower wavenumber for the band associated with the C—N bond in the iso­cyanate ligand than in complex (2), where fluoro substitution reduces the electron density at the metal. The IR spectra for the two compounds in the relevant frequency range are depicted in Fig. 6.

S4. Conclusion

Substitution of hydrogen by fluorine in the periphery of an organoplatinum complex reduces the electron density at the central metal. The principal effect may readily be detected in the IR spectrum by reduced backbonding towards the π-acceptor iso­cyanate ligand. Searching for the effects of substitution at the level of covalent or coordinative bonds means asking the wrong question, because the lengths of these strong bonds are rather insensitive to bond order. Rather, one has to read between the lines and rely on the much weaker secondary inter­actions. These occur between peripheral groups and reflect the nature and polarity of the groups involved.

Structure description

In 1968, Cope & Friedrich (1968) discovered orthometallation of activated benzyl amines with palladium and platinum. In the following years, the reaction with palladium was successfully expanded to more general substrates (Cockburn et al., 1973; Dunina et al., 1988; Avshu et al., 1983; Fuchita & Tsuchiya, 1993; Fuchita et al., 1997; Vicente et al., 1993). Our group reported the crystal structures of inter­mediates along the reaction pathway (Calmuschi & Englert, 2002; Calmuschi, Jonas & Englert, 2004) and of the first trans-configured cyclo­palladated amine (Calmuschi-Cula et al., 2005). With respect to crystal engineering, we used the cyclo­palladated primary amines for the construction of quasiracemic solids (Calmuschi, Alesi & Englert, 2004; Calmuschi & Englert, 2005). In contrast with these achievements in the field of cyclo­palladation, only modest progress was made with respect to cyclo­platination until 2007 (Capapé et al., 2007). In 2008, our group reported the first convenient route to cyclo­platination of primary amines via a mixed-valent platinum iodide precursor (Calmuschi-Cula & Englert, 2008). The cyclo­platinated primary amines thus obtained allowed the preparation of a whole class of derivatives: the σ-donor and iodide ligands may be substituted (Calmuschi-Cula & Englert, 2008; Raven et al., 2014), a chelating ligand can be introduced (Raven et al., 2015a), and Pt^IV complexes are accessible via oxidative addition (Raven et al., 2015b).

In the context of our earlier work, we reported the synthesis and structural characterization of the Pt^II iso­cyanate complex (1) (Raven et al., 2014) (Scheme 1). Such complexes are accessible via abstraction of the iodide ligand by a silver salt of a weakly coordinating anion such as tetra­fluoro­borate or perchlorate. Subsequent addition of an equimolar qu­antity of sodium iso­cyanate yields the target compounds.

We discuss here the analogous derivative of 1-(4-fluoro­phenyl)­ethyl­amine, complex (2), with an emphasis on the effects of fluoro substitution in (2). One might expect that such an electronegative atom in the para position would significantly reduce the electron density of the aromatic rings without major steric effects.

Complex (2) crystallizes in the chiral space group P2₁2₁2₁ with one molecule of the complex in the asymmetric unit; Fig. 1 shows a displacement ellipsoid plot of the molecule.

We will first compare compounds (1) and (2) at the molecular level and then discuss inter­molecular inter­actions. An overlay of the molecules (Fig. 2; the two F atoms in the para positions of the aryl rings have been omitted) shows that both iso­cyanate complexes adopt the same conformation in their crystalline solids; the r.m.s. displacement between equivalent atoms in the molecules amounts to only 0.1 Å. Despite the apparent agreement between (1) and (2) with respect to their overall shape, the compounds might exhibit small but relevant differences in terms of intra­molecular distances and angles. Table 2 shows that this is not the case: the coordinative bonds in the two complexes do not differ significantly.

Metal coordination apart, equal inter­atomic distances within error are also encountered for the iso­cyanate ligand in (1) and (2). We recall a relevant observation by Cotton & Wing (1965): C—O distances in metal carbonyl complexes show only little variation and do not reflect bond orders in a sensitive way. We can confirm the same behaviour for transition metal iso­cyanate complexes. In our search for transition metal iso­cyanates in the Cambridge Structural Database (Version 5.36, including updates to May 2015; Groom & Allen, 2014), we only considered low-temperature results (T < 200 K) and excluded disordered structures, results obtained on powder and entries with unresolved errors. For 131 observations fulfilling these conditions, the C—N distance in the iso­cyanate ligand shows a sharp maximum at 1.153 (3) Å; the corresponding histogram is given in Fig. 3. The C—N bond lengths in (1) [1.161 (15) Å] and (2) [1.160 (9) Å] match this value within error.

The similarity between (1) and (2) extends to the shortest inter­molecular contacts. In each structure, neighbouring molecules inter­act via classical N—H···O and N—H···N hydrogen bonds; for the new structure of (2), their geometry has been compiled in Table 3.

In both structures, the hydrogen bonds result in helices around the twofold screw axis associated with the shortest lattice parameter of ca 4.5 Å. Fig. 4 allows a comparison of these helices in (1) and (2). Adjacent helices in the [001] direction are generated by translation along c and are therefore parallel in (1). In contrast, they are related by a twofold screw axis along c in the case of (2) and thus adopt an anti­parallel orientation.

Despite the similarities between (1) and (2) in terms of molecular geometry and hydrogen bonding, crystal chemistry is not entirely blind with respect to substitution of a para H atom by F, and the inter­molecular inter­actions perpendicular to the hydrogen-bonded chains reflect the differences. In Fig. 5, the packing features common to both compounds have been marked in pink. The essentially nonpolar periphery of (1) results in the inter­molecular contact region emphasized as a blue ellipse in Fig. 5; in structural biology, it might have been addressed as a hydro­phobic bond. In contrast with this situation, the F-substituted aryl rings in (2) favour C—H···F contacts of ca 2.6 Å. This region, dominated by long and presumably weak nonclassical hydrogen bonds, has been marked in yellow in Fig. 5.

Although the diffraction experiments do not allow the deduction of significant differences in the intra­molecular geometries of (1) and (2), the electronic effect of fluorine substitution can easily be detected. In an IR spectrum, the band associated with the C—N bond in the iso­cyanate ligand is detected at a frequency of ca 2200 cm⁻¹ (Norbury & Sinha, 1968). π backbonding according to the Dewar–Chatt–Duncanson model (Dewar, 1951; Chatt & Duncanson, 1953) leads to a reduced bond order for the C—N bond in the NCO group. In the case of (1), the higher electron density at the central Pt^II atom leads to more pronounced backbonding and hence a lower wavenumber for the band associated with the C—N bond in the iso­cyanate ligand than in complex (2), where fluoro substitution reduces the electron density at the metal. The IR spectra for the two compounds in the relevant frequency range are depicted in Fig. 6.

Substitution of hydrogen by fluorine in the periphery of an organoplatinum complex reduces the electron density at the central metal. The principal effect may readily be detected in the IR spectrum by reduced backbonding towards the π-acceptor iso­cyanate ligand. Searching for the effects of substitution at the level of covalent or coordinative bonds means asking the wrong question, because the lengths of these strong bonds are rather insensitive to bond order. Rather, one has to read between the lines and rely on the much weaker secondary inter­actions. These occur between peripheral groups and reflect the nature and polarity of the groups involved.

Synthesis and crystallization

Chemicals were used without further purification. NMR samples contained tetra­methyl­silane as the standard. The measurements were conducted at the Institute for Inorganic Chemistry with a Bruker Avance II Ultrashield Plus 400.

Complex (1) was prepared according to the procedure of Raven et al. (2014).

The cyclo­platinated aqua precursor of (2) was prepared according to Raven et al. (2014). At room temperature, this aqua complex (100 mg, 0.17 mmol) was dissolved in methanol (10 ml) and NaOCN (11 mg, 0.17 mmol) was added. After 10 min, the brown solution turned purple. Water (2 ml) was added and a light-purple solid precipitated. The solid was recovered by centrifugation and dissolved in methanol (5 ml). Complex (2) was crystallized by addition of water and isolated by filtration (yield 71 mg, 0.12 mmol, 70%). Decomposition was observed at 472 K [for comparison, the unsubstituted parent complex (1) decomposes at 451 K].

Spectroscopic analysis: ¹H NMR (400 MHz, CD₂Cl₂, δ, p.p.m.): 1.48 (d, 3H, CH₃, non-cyclo­platinated amine), 1.70 (d, 3H, CH₃, cyclo­platinated amine), 3.51 (br, 2H, NH₂), 3.71 (br, 1H, NH₂), 4.26 (m, 2H, CH, cyclo­platinated + non-cyclo­platinated amine), 4.61 (br, 1H, NH₂), 6.38 (m, 1H, CH_arom), 6.61 (m,1H, CH_arom), 6.85 (m, 1H, CH_arom), 7.10 (m, 2H, CH_arom), 7.36 (m, 2H, CH_arom); ¹³C NMR (100.61 MHz, CD₂Cl₂, δ, p.p.m.): 23.79 (s, 1 C, CH₃, non-cyclo­platinated amine), 25.17 (s, 1 C, CH₃, cyclo­platinated amine), 58.19 (s, 1 C, CH, non-cyclo­platinated amine), 62.20 (s, 1 C, cyclo­platinated amine), 110.77 (d, 1 C, sp²-C), 117.24 (d, 2 C, sp²-C), 117.51 (s, 1 C, sp²-C), 123.94 (d, 1 C, sp²-C), 129.47 (d, 2 C, sp²-C), 139.56 (d, 1 C, sp²-C), 152.43 (s, 1 C, sp²-C), 160.02 (s, 1 C, sp²-C), 162.47 (s, 1 C, sp²-C), 162.71 (s, 1 C, sp²-C), 165.16 (s, 1 C, sp-C); ¹⁹F NMR (376.48 MHz, CD₂Cl₂, δ, p.p.m.): −117.21 (s, 1 F, non-cyclo­platinated amine), −113.99 (s, 1 F, cyclo­platinated amine); ¹⁹⁵Pt NMR (85.71 MHz, CD₂Cl₂, δ, p.p.m.): −3129.61.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1. Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms attached to C atoms were introduced in their idealized positions and treated as riding, with C—H = 1.00 Å and U_iso(H) = 1.2U_eq(C) for aliphatic CH groups, C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for CH₃ groups, and C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for aromatic CH groups. H atoms attached to N atoms were located from a difference Fourier map. Their coordinates were refined; a distance restraint with a target distance of 0.90 Å was used for N1—H1B, with U_iso(H) = 1.2U_eq(N). The enanti­opol parameter (Parsons & Flack, 2004) confirmed the central chirality of the coordinated phenyl­ethyl­amine ligands.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Figures

	Fig. 1. The asymmetric unit of (2), showing the atomic numbering scheme. H atoms have been omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Superposition of the complex molecule of (1) (dark grey) and that of (2) (light grey). H and F atoms have been omitted.
	Fig. 3. A histogram of the C—N distances in transition metal isocyanates; the search criteria are given in the text.
	Fig. 4. The arrangements of the helical chains built by hydrogen bonds in (top) (1) and (bottom) (2).
	Fig. 5. The packing of adjacent chains in (top) (1) and (bottom) (2). The view direction is the shortest lattice parameter. The regions shaded pink, blue and yellow are discussed in the text.
	Fig. 6. The IR spectra of (1) (black) and (2) (red). Only the wavenumber range between 1800 and 2600 cm^−1 is depicted, showing the characteristic bands of the C═N vibration in the isocyanate ligand.

(SP-4–4)-(R)-[2-(1-Aminoethyl)-5-fluorophenyl-κ²C¹,N][(R)-1-(4-fluorophenyl)ethylamine-κN](isocyanato-κN)platinum(II)

Crystal data

[Pt(C8H9FN)(NCO)(C8H10FN)]	Dx = 2.079 Mg m^−3
Mr = 514.44	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 4450 reflections
a = 4.5317 (4) Å	θ = 2.8–26.9°
b = 12.6474 (11) Å	µ = 8.57 mm^−1
c = 28.675 (3) Å	T = 100 K
V = 1643.5 (2) Å^3	Needle, colourless
Z = 4	0.38 × 0.06 × 0.06 mm
F(000) = 984

Data collection

Bruker SMART APEX CCD area-detector diffractometer	4634 reflections with I > 2σ(I)
Radiation source: Incoatec microsource	Rint = 0.063
/w scans	θmax = 30.9°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −6→6
Tmin = 0.444, Tmax = 0.746	k = −18→17
24890 measured reflections	l = −39→40
4902 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.031	w = 1/[σ^2(Fo^2) + (0.0283P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.065	(Δ/σ)max = 0.001
S = 1.07	Δρmax = 1.49 e Å^−3
4902 reflections	Δρmin = −1.63 e Å^−3
231 parameters	Absolute structure: Flack x parameter determined using 1800 quotients [(I^+) - (I^-)]/[(I^+) + (I^-)] (Parsons & Flack, 2004)
1 restraint	Absolute structure parameter: −0.017 (8)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Pt1	0.69301 (6)	0.90613 (2)	0.08788 (2)	0.01164 (7)
F1	1.2278 (10)	1.2205 (3)	0.18502 (14)	0.0239 (10)
F2	1.6691 (11)	0.4306 (3)	0.21189 (16)	0.0271 (10)
O1	0.6356 (14)	0.5815 (4)	0.04159 (18)	0.0303 (14)
N1	0.3905 (14)	0.9848 (5)	0.0488 (2)	0.0141 (12)
H1A	0.355 (19)	0.953 (6)	0.021 (3)	0.021*
H1B	0.218 (10)	0.975 (6)	0.063 (3)	0.021*
N2	1.0033 (13)	0.8247 (5)	0.1267 (2)	0.0142 (12)
H2A	1.107 (18)	0.784 (6)	0.107 (3)	0.021*
H2B	1.142 (19)	0.871 (6)	0.131 (3)	0.021*
N3	0.5517 (15)	0.7584 (4)	0.0643 (2)	0.0199 (13)
C1	0.7981 (17)	1.0527 (5)	0.1073 (2)	0.0136 (12)
C2	0.6578 (15)	1.1325 (5)	0.0811 (2)	0.0136 (13)
C3	0.7053 (16)	1.2393 (5)	0.0911 (3)	0.0171 (12)
H3	0.6047	1.2917	0.0735	0.021*
C4	0.8948 (17)	1.2698 (5)	0.1260 (3)	0.0202 (15)
H4	0.9285	1.3424	0.1328	0.024*
C5	1.0344 (17)	1.1908 (6)	0.1510 (2)	0.0187 (15)
C6	0.9913 (15)	1.0851 (6)	0.1432 (2)	0.0145 (13)
H6	1.0907	1.0340	0.1617	0.017*
C7	0.4690 (15)	1.0984 (6)	0.0409 (2)	0.0141 (12)
H7	0.2847	1.1418	0.0403	0.017*
C8	0.6274 (16)	1.1094 (5)	−0.0055 (2)	0.0193 (15)
H8A	0.6794	1.1837	−0.0106	0.029*
H8B	0.4977	1.0852	−0.0307	0.029*
H8C	0.8074	1.0665	−0.0051	0.029*
C9	1.0954 (16)	0.6742 (5)	0.1803 (2)	0.0147 (13)
C10	1.2236 (16)	0.6662 (5)	0.2245 (2)	0.0161 (14)
H10	1.1803	0.7183	0.2473	0.019*
C11	1.4112 (16)	0.5844 (6)	0.2356 (2)	0.0194 (14)
H11	1.4928	0.5789	0.2660	0.023*
C12	1.4787 (16)	0.5104 (6)	0.2016 (3)	0.0189 (15)
C13	1.3570 (15)	0.5146 (5)	0.1575 (2)	0.0175 (15)
H13	1.4054	0.4632	0.1345	0.021*
C14	1.1612 (15)	0.5965 (6)	0.1476 (2)	0.0173 (13)
H14	1.0703	0.5994	0.1178	0.021*
C15	0.8826 (15)	0.7616 (5)	0.1671 (2)	0.0138 (13)
H15	0.6944	0.7278	0.1566	0.017*
C16	0.808 (2)	0.8389 (5)	0.2060 (2)	0.0191 (13)
H16A	0.7324	0.7999	0.2330	0.029*
H16B	0.6585	0.8889	0.1951	0.029*
H16C	0.9868	0.8777	0.2151	0.029*
C17	0.5954 (17)	0.6717 (6)	0.0531 (2)	0.0168 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.01143 (11)	0.01269 (10)	0.01080 (10)	−0.00039 (11)	0.00045 (10)	0.00051 (10)
F1	0.029 (3)	0.026 (2)	0.0168 (19)	−0.007 (2)	−0.0039 (18)	−0.0037 (17)
F2	0.025 (2)	0.024 (2)	0.032 (2)	0.010 (2)	−0.004 (2)	0.0052 (17)
O1	0.046 (4)	0.019 (3)	0.026 (3)	−0.001 (3)	0.008 (3)	−0.004 (2)
N1	0.018 (3)	0.013 (3)	0.012 (3)	−0.003 (2)	−0.002 (2)	0.002 (2)
N2	0.014 (3)	0.015 (3)	0.014 (3)	0.000 (2)	−0.001 (2)	0.000 (2)
N3	0.019 (3)	0.018 (3)	0.023 (3)	−0.002 (2)	0.000 (3)	0.001 (2)
C1	0.011 (3)	0.016 (3)	0.013 (3)	−0.001 (3)	0.007 (3)	0.000 (2)
C2	0.011 (3)	0.014 (3)	0.016 (3)	0.002 (2)	0.005 (3)	−0.001 (2)
C3	0.014 (3)	0.012 (3)	0.026 (3)	0.006 (3)	0.005 (4)	0.004 (3)
C4	0.019 (4)	0.013 (3)	0.029 (4)	−0.006 (3)	0.005 (3)	−0.003 (3)
C5	0.016 (4)	0.025 (4)	0.014 (3)	−0.007 (3)	0.001 (3)	−0.005 (3)
C6	0.014 (3)	0.017 (3)	0.012 (3)	−0.001 (3)	−0.001 (2)	0.002 (3)
C7	0.012 (3)	0.012 (3)	0.018 (3)	0.000 (3)	0.000 (2)	−0.001 (3)
C8	0.024 (4)	0.020 (3)	0.014 (3)	−0.005 (3)	0.000 (3)	0.003 (3)
C9	0.013 (3)	0.016 (3)	0.015 (3)	−0.005 (3)	−0.001 (3)	0.002 (2)
C10	0.017 (4)	0.019 (3)	0.012 (3)	−0.003 (3)	0.001 (3)	−0.001 (2)
C11	0.025 (3)	0.022 (3)	0.011 (3)	−0.002 (3)	−0.004 (3)	0.003 (3)
C12	0.015 (4)	0.020 (3)	0.021 (4)	−0.001 (3)	−0.003 (3)	0.006 (3)
C13	0.017 (4)	0.017 (3)	0.019 (3)	0.001 (3)	0.002 (3)	−0.002 (3)
C14	0.019 (4)	0.017 (3)	0.015 (3)	−0.004 (4)	−0.005 (3)	0.002 (3)
C15	0.014 (4)	0.015 (3)	0.012 (3)	−0.004 (2)	0.002 (2)	0.000 (2)
C16	0.026 (4)	0.016 (3)	0.015 (3)	0.002 (3)	−0.003 (3)	−0.001 (2)
C17	0.020 (4)	0.021 (3)	0.010 (3)	−0.005 (3)	0.000 (3)	−0.001 (3)

Geometric parameters (Å, º)

Pt1—C1	1.994 (6)	C6—H6	0.9500
Pt1—N1	2.031 (6)	C7—C8	1.518 (9)
Pt1—N2	2.069 (6)	C7—H7	1.0000
Pt1—N3	2.088 (6)	C8—H8A	0.9800
F1—C5	1.364 (8)	C8—H8B	0.9800
F2—C12	1.360 (8)	C8—H8C	0.9800
O1—C17	1.201 (8)	C9—C14	1.391 (9)
N1—C7	1.498 (9)	C9—C10	1.396 (9)
N1—H1A	0.89 (8)	C9—C15	1.516 (9)
N1—H1B	0.89 (3)	C10—C11	1.376 (10)
N2—C15	1.508 (8)	C10—H10	0.9500
N2—H2A	0.89 (8)	C11—C12	1.387 (10)
N2—H2B	0.87 (9)	C11—H11	0.9500
N3—C17	1.160 (9)	C12—C13	1.382 (9)
C1—C2	1.411 (9)	C13—C14	1.393 (10)
C1—C6	1.411 (9)	C13—H13	0.9500
C2—C3	1.398 (8)	C14—H14	0.9500
C2—C7	1.498 (9)	C15—C16	1.522 (9)
C3—C4	1.374 (10)	C15—H15	1.0000
C3—H3	0.9500	C16—H16A	0.9800
C4—C5	1.383 (10)	C16—H16B	0.9800
C4—H4	0.9500	C16—H16C	0.9800
C5—C6	1.370 (10)
C1—Pt1—N1	82.0 (3)	N1—C7—H7	109.3
C1—Pt1—N2	98.6 (3)	C2—C7—H7	109.3
N1—Pt1—N2	179.0 (2)	C8—C7—H7	109.3
C1—Pt1—N3	174.9 (3)	C7—C8—H8A	109.5
N1—Pt1—N3	93.0 (2)	C7—C8—H8B	109.5
N2—Pt1—N3	86.4 (2)	H8A—C8—H8B	109.5
C7—N1—Pt1	113.1 (4)	C7—C8—H8C	109.5
C7—N1—H1A	110 (5)	H8A—C8—H8C	109.5
Pt1—N1—H1A	113 (5)	H8B—C8—H8C	109.5
C7—N1—H1B	114 (5)	C14—C9—C10	118.1 (6)
Pt1—N1—H1B	106 (5)	C14—C9—C15	118.8 (6)
H1A—N1—H1B	100 (7)	C10—C9—C15	123.0 (6)
C15—N2—Pt1	115.5 (4)	C11—C10—C9	121.5 (6)
C15—N2—H2A	111 (5)	C11—C10—H10	119.3
Pt1—N2—H2A	108 (5)	C9—C10—H10	119.3
C15—N2—H2B	121 (5)	C10—C11—C12	118.7 (6)
Pt1—N2—H2B	103 (5)	C10—C11—H11	120.6
H2A—N2—H2B	95 (7)	C12—C11—H11	120.6
C17—N3—Pt1	152.1 (6)	F2—C12—C13	118.7 (6)
C2—C1—C6	117.5 (6)	F2—C12—C11	119.2 (6)
C2—C1—Pt1	114.1 (5)	C13—C12—C11	122.0 (7)
C6—C1—Pt1	128.5 (5)	C12—C13—C14	118.0 (6)
C3—C2—C1	120.7 (6)	C12—C13—H13	121.0
C3—C2—C7	121.7 (6)	C14—C13—H13	121.0
C1—C2—C7	117.5 (6)	C9—C14—C13	121.6 (6)
C4—C3—C2	121.2 (6)	C9—C14—H14	119.2
C4—C3—H3	119.4	C13—C14—H14	119.2
C2—C3—H3	119.4	N2—C15—C9	110.3 (5)
C3—C4—C5	117.4 (6)	N2—C15—C16	107.7 (5)
C3—C4—H4	121.3	C9—C15—C16	115.1 (6)
C5—C4—H4	121.3	N2—C15—H15	107.8
F1—C5—C6	118.5 (6)	C9—C15—H15	107.8
F1—C5—C4	117.7 (6)	C16—C15—H15	107.8
C6—C5—C4	123.7 (7)	C15—C16—H16A	109.5
C5—C6—C1	119.4 (6)	C15—C16—H16B	109.5
C5—C6—H6	120.3	H16A—C16—H16B	109.5
C1—C6—H6	120.3	C15—C16—H16C	109.5
N1—C7—C2	107.2 (5)	H16A—C16—H16C	109.5
N1—C7—C8	109.4 (5)	H16B—C16—H16C	109.5
C2—C7—C8	112.2 (6)	N3—C17—O1	178.9 (9)
C6—C1—C2—C3	−1.4 (10)	C1—C2—C7—C8	−100.3 (7)
Pt1—C1—C2—C3	178.8 (5)	C14—C9—C10—C11	0.3 (10)
C6—C1—C2—C7	175.8 (6)	C15—C9—C10—C11	178.6 (6)
Pt1—C1—C2—C7	−4.0 (8)	C9—C10—C11—C12	1.7 (11)
C1—C2—C3—C4	1.6 (11)	C10—C11—C12—F2	178.5 (6)
C7—C2—C3—C4	−175.5 (6)	C10—C11—C12—C13	−1.9 (11)
C2—C3—C4—C5	−0.5 (11)	F2—C12—C13—C14	179.6 (6)
C3—C4—C5—F1	178.6 (6)	C11—C12—C13—C14	0.0 (11)
C3—C4—C5—C6	−0.8 (11)	C10—C9—C14—C13	−2.2 (10)
F1—C5—C6—C1	−178.3 (6)	C15—C9—C14—C13	179.4 (6)
C4—C5—C6—C1	1.0 (11)	C12—C13—C14—C9	2.1 (10)
C2—C1—C6—C5	0.1 (10)	Pt1—N2—C15—C9	157.4 (4)
Pt1—C1—C6—C5	179.9 (5)	Pt1—N2—C15—C16	−76.2 (6)
Pt1—N1—C7—C2	−26.7 (6)	C14—C9—C15—N2	−61.7 (8)
Pt1—N1—C7—C8	95.2 (5)	C10—C9—C15—N2	120.0 (7)
C3—C2—C7—N1	−162.9 (6)	C14—C9—C15—C16	176.2 (6)
C1—C2—C7—N1	19.9 (8)	C10—C9—C15—C16	−2.1 (10)
C3—C2—C7—C8	76.9 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1^i	0.91 (8)	2.10 (9)	2.959 (8)	158 (7)
N2—H2A···N3^ii	0.90 (8)	2.38 (8)	3.175 (9)	148 (6)
C11—H11···F1^iii	0.95	2.60	3.289 (8)	129
C16—H16A···F1^iv	0.98	2.56	3.469 (7)	154

Symmetry codes: (i) x−1/2, −y+3/2, −z; (ii) x+1, y, z; (iii) −x+3, y−1/2, −z+1/2; (iv) −x+2, y−1/2, −z+1/2.