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At the mol­ecular level, the enantio­merically pure square-planar organo­platinum com­plex (SP-4-4)-(R)-[2-(1-amino­ethyl)-5-fluorophenyl-κ2C1,N][(R)-1-(4-fluoro­phenyl)ethyl­amine-κN](iso­cyanato-κN)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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616002382/yf3099sup1.cif
Contains datablocks 2, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229616002382/yf30992sup2.hkl
Contains datablock 2

CCDC reference: 1452182

Introduction top

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 PtIV 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 PtII 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.

Experimental top

Synthesis and crystallization top

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, CHarom), 6.61 (m,1H, CHarom), 6.85 (m, 1H, CHarom), 7.10 (m, 2H, CHarom), 7.36 (m, 2H, CHarom); 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 top

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 Uiso(H) = 1.2Ueq(C) for aliphatic CH groups, C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C) for CH3 groups, and C—H = 0.95 Å and Uiso(H) = 1.2Ueq(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 Uiso(H) = 1.2Ueq(N). The enanti­opol parameter (Parsons & Flack, 2004) confirmed the central chirality of the coordinated phenyl­ethyl­amine ligands.

Results and discussion top

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 PtII 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.

Conclusion top

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 top

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 PtIV 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 PtII 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 PtII 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 top

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, CHarom), 6.61 (m,1H, CHarom), 6.85 (m, 1H, CHarom), 7.10 (m, 2H, CHarom), 7.36 (m, 2H, CHarom); 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 top

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 Uiso(H) = 1.2Ueq(C) for aliphatic CH groups, C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C) for CH3 groups, and C—H = 0.95 Å and Uiso(H) = 1.2Ueq(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 Uiso(H) = 1.2Ueq(N). The enanti­opol parameter (Parsons & Flack, 2004) confirmed the central chirality of the coordinated phenyl­ethyl­amine ligands.

Computing details top

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 top
[Figure 1] 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.
[Figure 2] Fig. 2. Superposition of the complex molecule of (1) (dark grey) and that of (2) (light grey). H and F atoms have been omitted.
[Figure 3] Fig. 3. A histogram of the C—N distances in transition metal isocyanates; the search criteria are given in the text.
[Figure 4] Fig. 4. The arrangements of the helical chains built by hydrogen bonds in (top) (1) and (bottom) (2).
[Figure 5] 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.
[Figure 6] 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 CN 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) top
Crystal data top
[Pt(C8H9FN)(NCO)(C8H10FN)]Dx = 2.079 Mg m3
Mr = 514.44Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 4450 reflections
a = 4.5317 (4) Åθ = 2.8–26.9°
b = 12.6474 (11) ŵ = 8.57 mm1
c = 28.675 (3) ÅT = 100 K
V = 1643.5 (2) Å3Needle, colourless
Z = 40.38 × 0.06 × 0.06 mm
F(000) = 984
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
4634 reflections with I > 2σ(I)
Radiation source: Incoatec microsourceRint = 0.063
/w scansθmax = 30.9°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 66
Tmin = 0.444, Tmax = 0.746k = 1817
24890 measured reflectionsl = 3940
4902 independent reflections
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.031 w = 1/[σ2(Fo2) + (0.0283P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.065(Δ/σ)max = 0.001
S = 1.07Δρmax = 1.49 e Å3
4902 reflectionsΔρmin = 1.63 e Å3
231 parametersAbsolute structure: Flack x parameter determined using 1800 quotients [(I+) - (I-)]/[(I+) + (I-)] (Parsons & Flack, 2004)
1 restraintAbsolute structure parameter: 0.017 (8)
Crystal data top
[Pt(C8H9FN)(NCO)(C8H10FN)]V = 1643.5 (2) Å3
Mr = 514.44Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 4.5317 (4) ŵ = 8.57 mm1
b = 12.6474 (11) ÅT = 100 K
c = 28.675 (3) Å0.38 × 0.06 × 0.06 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
4902 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
4634 reflections with I > 2σ(I)
Tmin = 0.444, Tmax = 0.746Rint = 0.063
24890 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.031H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.065Δρmax = 1.49 e Å3
S = 1.07Δρmin = 1.63 e Å3
4902 reflectionsAbsolute structure: Flack x parameter determined using 1800 quotients [(I+) - (I-)]/[(I+) + (I-)] (Parsons & Flack, 2004)
231 parametersAbsolute structure parameter: 0.017 (8)
1 restraint
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
xyzUiso*/Ueq
Pt10.69301 (6)0.90613 (2)0.08788 (2)0.01164 (7)
F11.2278 (10)1.2205 (3)0.18502 (14)0.0239 (10)
F21.6691 (11)0.4306 (3)0.21189 (16)0.0271 (10)
O10.6356 (14)0.5815 (4)0.04159 (18)0.0303 (14)
N10.3905 (14)0.9848 (5)0.0488 (2)0.0141 (12)
H1A0.355 (19)0.953 (6)0.021 (3)0.021*
H1B0.218 (10)0.975 (6)0.063 (3)0.021*
N21.0033 (13)0.8247 (5)0.1267 (2)0.0142 (12)
H2A1.107 (18)0.784 (6)0.107 (3)0.021*
H2B1.142 (19)0.871 (6)0.131 (3)0.021*
N30.5517 (15)0.7584 (4)0.0643 (2)0.0199 (13)
C10.7981 (17)1.0527 (5)0.1073 (2)0.0136 (12)
C20.6578 (15)1.1325 (5)0.0811 (2)0.0136 (13)
C30.7053 (16)1.2393 (5)0.0911 (3)0.0171 (12)
H30.60471.29170.07350.021*
C40.8948 (17)1.2698 (5)0.1260 (3)0.0202 (15)
H40.92851.34240.13280.024*
C51.0344 (17)1.1908 (6)0.1510 (2)0.0187 (15)
C60.9913 (15)1.0851 (6)0.1432 (2)0.0145 (13)
H61.09071.03400.16170.017*
C70.4690 (15)1.0984 (6)0.0409 (2)0.0141 (12)
H70.28471.14180.04030.017*
C80.6274 (16)1.1094 (5)0.0055 (2)0.0193 (15)
H8A0.67941.18370.01060.029*
H8B0.49771.08520.03070.029*
H8C0.80741.06650.00510.029*
C91.0954 (16)0.6742 (5)0.1803 (2)0.0147 (13)
C101.2236 (16)0.6662 (5)0.2245 (2)0.0161 (14)
H101.18030.71830.24730.019*
C111.4112 (16)0.5844 (6)0.2356 (2)0.0194 (14)
H111.49280.57890.26600.023*
C121.4787 (16)0.5104 (6)0.2016 (3)0.0189 (15)
C131.3570 (15)0.5146 (5)0.1575 (2)0.0175 (15)
H131.40540.46320.13450.021*
C141.1612 (15)0.5965 (6)0.1476 (2)0.0173 (13)
H141.07030.59940.11780.021*
C150.8826 (15)0.7616 (5)0.1671 (2)0.0138 (13)
H150.69440.72780.15660.017*
C160.808 (2)0.8389 (5)0.2060 (2)0.0191 (13)
H16A0.73240.79990.23300.029*
H16B0.65850.88890.19510.029*
H16C0.98680.87770.21510.029*
C170.5954 (17)0.6717 (6)0.0531 (2)0.0168 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.01143 (11)0.01269 (10)0.01080 (10)0.00039 (11)0.00045 (10)0.00051 (10)
F10.029 (3)0.026 (2)0.0168 (19)0.007 (2)0.0039 (18)0.0037 (17)
F20.025 (2)0.024 (2)0.032 (2)0.010 (2)0.004 (2)0.0052 (17)
O10.046 (4)0.019 (3)0.026 (3)0.001 (3)0.008 (3)0.004 (2)
N10.018 (3)0.013 (3)0.012 (3)0.003 (2)0.002 (2)0.002 (2)
N20.014 (3)0.015 (3)0.014 (3)0.000 (2)0.001 (2)0.000 (2)
N30.019 (3)0.018 (3)0.023 (3)0.002 (2)0.000 (3)0.001 (2)
C10.011 (3)0.016 (3)0.013 (3)0.001 (3)0.007 (3)0.000 (2)
C20.011 (3)0.014 (3)0.016 (3)0.002 (2)0.005 (3)0.001 (2)
C30.014 (3)0.012 (3)0.026 (3)0.006 (3)0.005 (4)0.004 (3)
C40.019 (4)0.013 (3)0.029 (4)0.006 (3)0.005 (3)0.003 (3)
C50.016 (4)0.025 (4)0.014 (3)0.007 (3)0.001 (3)0.005 (3)
C60.014 (3)0.017 (3)0.012 (3)0.001 (3)0.001 (2)0.002 (3)
C70.012 (3)0.012 (3)0.018 (3)0.000 (3)0.000 (2)0.001 (3)
C80.024 (4)0.020 (3)0.014 (3)0.005 (3)0.000 (3)0.003 (3)
C90.013 (3)0.016 (3)0.015 (3)0.005 (3)0.001 (3)0.002 (2)
C100.017 (4)0.019 (3)0.012 (3)0.003 (3)0.001 (3)0.001 (2)
C110.025 (3)0.022 (3)0.011 (3)0.002 (3)0.004 (3)0.003 (3)
C120.015 (4)0.020 (3)0.021 (4)0.001 (3)0.003 (3)0.006 (3)
C130.017 (4)0.017 (3)0.019 (3)0.001 (3)0.002 (3)0.002 (3)
C140.019 (4)0.017 (3)0.015 (3)0.004 (4)0.005 (3)0.002 (3)
C150.014 (4)0.015 (3)0.012 (3)0.004 (2)0.002 (2)0.000 (2)
C160.026 (4)0.016 (3)0.015 (3)0.002 (3)0.003 (3)0.001 (2)
C170.020 (4)0.021 (3)0.010 (3)0.005 (3)0.000 (3)0.001 (3)
Geometric parameters (Å, º) top
Pt1—C11.994 (6)C6—H60.9500
Pt1—N12.031 (6)C7—C81.518 (9)
Pt1—N22.069 (6)C7—H71.0000
Pt1—N32.088 (6)C8—H8A0.9800
F1—C51.364 (8)C8—H8B0.9800
F2—C121.360 (8)C8—H8C0.9800
O1—C171.201 (8)C9—C141.391 (9)
N1—C71.498 (9)C9—C101.396 (9)
N1—H1A0.89 (8)C9—C151.516 (9)
N1—H1B0.89 (3)C10—C111.376 (10)
N2—C151.508 (8)C10—H100.9500
N2—H2A0.89 (8)C11—C121.387 (10)
N2—H2B0.87 (9)C11—H110.9500
N3—C171.160 (9)C12—C131.382 (9)
C1—C21.411 (9)C13—C141.393 (10)
C1—C61.411 (9)C13—H130.9500
C2—C31.398 (8)C14—H140.9500
C2—C71.498 (9)C15—C161.522 (9)
C3—C41.374 (10)C15—H151.0000
C3—H30.9500C16—H16A0.9800
C4—C51.383 (10)C16—H16B0.9800
C4—H40.9500C16—H16C0.9800
C5—C61.370 (10)
C1—Pt1—N182.0 (3)N1—C7—H7109.3
C1—Pt1—N298.6 (3)C2—C7—H7109.3
N1—Pt1—N2179.0 (2)C8—C7—H7109.3
C1—Pt1—N3174.9 (3)C7—C8—H8A109.5
N1—Pt1—N393.0 (2)C7—C8—H8B109.5
N2—Pt1—N386.4 (2)H8A—C8—H8B109.5
C7—N1—Pt1113.1 (4)C7—C8—H8C109.5
C7—N1—H1A110 (5)H8A—C8—H8C109.5
Pt1—N1—H1A113 (5)H8B—C8—H8C109.5
C7—N1—H1B114 (5)C14—C9—C10118.1 (6)
Pt1—N1—H1B106 (5)C14—C9—C15118.8 (6)
H1A—N1—H1B100 (7)C10—C9—C15123.0 (6)
C15—N2—Pt1115.5 (4)C11—C10—C9121.5 (6)
C15—N2—H2A111 (5)C11—C10—H10119.3
Pt1—N2—H2A108 (5)C9—C10—H10119.3
C15—N2—H2B121 (5)C10—C11—C12118.7 (6)
Pt1—N2—H2B103 (5)C10—C11—H11120.6
H2A—N2—H2B95 (7)C12—C11—H11120.6
C17—N3—Pt1152.1 (6)F2—C12—C13118.7 (6)
C2—C1—C6117.5 (6)F2—C12—C11119.2 (6)
C2—C1—Pt1114.1 (5)C13—C12—C11122.0 (7)
C6—C1—Pt1128.5 (5)C12—C13—C14118.0 (6)
C3—C2—C1120.7 (6)C12—C13—H13121.0
C3—C2—C7121.7 (6)C14—C13—H13121.0
C1—C2—C7117.5 (6)C9—C14—C13121.6 (6)
C4—C3—C2121.2 (6)C9—C14—H14119.2
C4—C3—H3119.4C13—C14—H14119.2
C2—C3—H3119.4N2—C15—C9110.3 (5)
C3—C4—C5117.4 (6)N2—C15—C16107.7 (5)
C3—C4—H4121.3C9—C15—C16115.1 (6)
C5—C4—H4121.3N2—C15—H15107.8
F1—C5—C6118.5 (6)C9—C15—H15107.8
F1—C5—C4117.7 (6)C16—C15—H15107.8
C6—C5—C4123.7 (7)C15—C16—H16A109.5
C5—C6—C1119.4 (6)C15—C16—H16B109.5
C5—C6—H6120.3H16A—C16—H16B109.5
C1—C6—H6120.3C15—C16—H16C109.5
N1—C7—C2107.2 (5)H16A—C16—H16C109.5
N1—C7—C8109.4 (5)H16B—C16—H16C109.5
C2—C7—C8112.2 (6)N3—C17—O1178.9 (9)
C6—C1—C2—C31.4 (10)C1—C2—C7—C8100.3 (7)
Pt1—C1—C2—C3178.8 (5)C14—C9—C10—C110.3 (10)
C6—C1—C2—C7175.8 (6)C15—C9—C10—C11178.6 (6)
Pt1—C1—C2—C74.0 (8)C9—C10—C11—C121.7 (11)
C1—C2—C3—C41.6 (11)C10—C11—C12—F2178.5 (6)
C7—C2—C3—C4175.5 (6)C10—C11—C12—C131.9 (11)
C2—C3—C4—C50.5 (11)F2—C12—C13—C14179.6 (6)
C3—C4—C5—F1178.6 (6)C11—C12—C13—C140.0 (11)
C3—C4—C5—C60.8 (11)C10—C9—C14—C132.2 (10)
F1—C5—C6—C1178.3 (6)C15—C9—C14—C13179.4 (6)
C4—C5—C6—C11.0 (11)C12—C13—C14—C92.1 (10)
C2—C1—C6—C50.1 (10)Pt1—N2—C15—C9157.4 (4)
Pt1—C1—C6—C5179.9 (5)Pt1—N2—C15—C1676.2 (6)
Pt1—N1—C7—C226.7 (6)C14—C9—C15—N261.7 (8)
Pt1—N1—C7—C895.2 (5)C10—C9—C15—N2120.0 (7)
C3—C2—C7—N1162.9 (6)C14—C9—C15—C16176.2 (6)
C1—C2—C7—N119.9 (8)C10—C9—C15—C162.1 (10)
C3—C2—C7—C876.9 (8)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.91 (8)2.10 (9)2.959 (8)158 (7)
N2—H2A···N3ii0.90 (8)2.38 (8)3.175 (9)148 (6)
C11—H11···F1iii0.952.603.289 (8)129
C16—H16A···F1iv0.982.563.469 (7)154
Symmetry codes: (i) x1/2, y+3/2, z; (ii) x+1, y, z; (iii) x+3, y1/2, z+1/2; (iv) x+2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Pt(C8H9FN)(NCO)(C8H10FN)]
Mr514.44
Crystal system, space groupOrthorhombic, P212121
Temperature (K)100
a, b, c (Å)4.5317 (4), 12.6474 (11), 28.675 (3)
V3)1643.5 (2)
Z4
Radiation typeMo Kα
µ (mm1)8.57
Crystal size (mm)0.38 × 0.06 × 0.06
Data collection
DiffractometerBruker SMART APEX CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2008)
Tmin, Tmax0.444, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
24890, 4902, 4634
Rint0.063
(sin θ/λ)max1)0.722
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.065, 1.07
No. of reflections4902
No. of parameters231
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)1.49, 1.63
Absolute structureFlack x parameter determined using 1800 quotients [(I+) - (I-)]/[(I+) + (I-)] (Parsons & Flack, 2004)
Absolute structure parameter0.017 (8)

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008).

Selected interatomic distances (Å) and angles (°) in (1) and (2) top
Parameter(1)(2)
Pt—N12.026 (9)2.031 (6)
Pt—N22.070 (9)2.069 (6)
Pt—N32.083 (10)2.088 (6)
Pt—C11.991 (11)1.994 (6)
N3—C171.161 (15)1.160 (9)
C17—O11.217 (14)1.201 (8)
N3—C17—O1179.6 (14)178.9 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.91 (8)2.10 (9)2.959 (8)158 (7)
N2—H2A···N3ii0.90 (8)2.38 (8)3.175 (9)148 (6)
C11—H11···F1iii0.952.6043.289 (8)129
C16—H16A···F1iv0.982.5633.469 (7)154
Symmetry codes: (i) x1/2, y+3/2, z; (ii) x+1, y, z; (iii) x+3, y1/2, z+1/2; (iv) x+2, y1/2, z+1/2.
 

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