Syn- and anti-rotamers of the ortho-stereoisomer [Pt{(o-BrC6F4)N(CH2)2NEt2}Cl(py)]

Ojha, R.; Bond, A.M.; Junk, P.C.; Deacon, G.B.

doi:10.1107/S2053229625006837

research papers

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 81| Part 9| September 2025| Pages 513-518

https://doi.org/10.1107/S2053229625006837

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Syn- and anti-rotamers of the ortho-stereoisomer [Pt{(o-BrC₆F₄)N(CH₂)₂NEt₂}Cl(py)]

Ruchika Ojha,^a,^b Alan M. Bond,^a ^* Peter C. Junk ^c ^* and Glen B. Deacon ^a ^*

^aSchool of Chemistry, Monash University, VIC 3800, Australia, ^bSchool of Science, STEM College, RMIT University, Melbourne, VIC 3000, Australia, and ^cCollege of Science & Engineering, James Cook University, Townsville, Qld 4811, Australia
^*Correspondence e-mail: [email protected], [email protected], [email protected]

Edited by M. Yousufuddin, University of North Texas at Dallas, USA (Received 23 July 2025; accepted 30 July 2025; online 21 August 2025)

The crystal structure of the ortho-isomer trans-[N-(2-bromo-3,4,5,6-tetrafluorophenyl)-N′,N′-diethylethane-1,2-diaminato(1−)]chloridopyridineplatinum(II), [PtBr_0.1(C₁₂H₁₄BrF₄N₂)Cl_0.9(C₅H₅N)][PtBr_0.4(C₁₂H₁₄BrF₄N₂)Cl_0.6(C₅H₅N)] or [Pt{(o-BrC₆F₄)N(CH₂)₂NEt₂}Cl(py)], 1o, revealed syn and anti rotamers in a 1:1 ratio in the solid state. 1o crystallizes in the centrosymmetric space group P1. The Pt-coordinated Cl ligand exhibits partial occupancy with Br, predominantly in the syn-rotamer. Notably, agostic interactions are observed between the Pt centre and a H atom of one of the ethyl groups. The ortho-isomer 1o was successfully isolated as a side product from the reaction of [Pt{H₂N(CH₂)₂NEt₂}Cl₂], Tl₂CO₃ and C₆F₅Br. While the para-isomer [Pt{(p-BrC₆F₄)N(CH₂)₂NEt₂}Cl(py)], 1p, is the main product, the higher solubility of 1o facilitates its isolation.

Keywords: crystal structure; platinum anticancer agent; syn and anti rotamers; agostic interactions; synchrotron.

CCDC references: 2481234; 2477306

1. Introduction

Polyfluoroaryl-substituted organoamidoplatinum(II) complexes [Pt{RN(CH₂)₂NR′₂}X(py)] [R = p-YC₆F₄ (Y = F, Cl, Br or I), CH₃, etc.; R′ = Me or Et; X = Cl, Br or I; py = pyridine] have been shown to have good in vitro and modest in vivo activity (Talarico et al., 1999 ; Ojha et al., 2021 ) against a number of tumour cells. They are conveniently prepared by reaction of [PtX₂(NH₂CH₂CH₂NR′₂)] with thallium(I) carbonate (or K₂CO₃ in some cases) and a polyfluoroarene, RF, in boiling pyridine (Fig. 1) (Battle et al., 2010 ; Ojha et al., 2015 ). The CO₂ generated from Tl₂CO₃ during the reaction was trapped as BaCO₃ by a Ba(OH)₂ solution, and the yield of CO₂ was measured gravimetrically.

Figure 1
General synthesis of [Pt{RN(CH₂)₂NR′₂}X(py)].

One step in the complex CO₂ elimination reaction paths is nucleophilic substitution of F on the polyfluorobenzene, RF, by the –NH₂ group, plausibly partially deprotonated by the carbonate group. The substitution pattern of the major products (Battle et al., 2010; Buxton et al., 1988 ; Deacon et al., 1991 ) corresponds to that (para to substituent Y), as observed in the nucleophilic substitution of polyfluoroarenes (Chambers et al., 1974 , 1977 ; Chambers, 2004 ). Although the ¹⁹F NMR spectra of crude reaction products sometimes suggested that the reactions were not entirely regiospecific, simple recrystallization usually gave isomerically pure products (Battle et al., 2010; Buxton et al., 1988; Deacon et al., 1991). However, the reaction of [PtCl₂(en)] (en is ethylenediamine), Tl₂CO₃ and 2-bromo-1,3,4,5-tetrafluorobenzene in pyridine gave isomers with the N atom para to both H and Br. Only the former was isolated, the latter being identified spectroscopically in the reaction mixture (Battle et al., 2010).

We have recently reported anticancer activity (Ojha et al., 2021), chemical oxidation (Ojha et al., 2023 ) and the synthesis of [Pt{(p-BrC₆F₄)N(CH₂)₂NEt₂}Cl(py)], 1p (with X = Cl, R′ = Et and R = p-BrC₆F₄), in 64% yield by reaction between [PtCl₂{H₂N(CH₂)₂NEt₂}], Tl₂CO₃ and C₆F₅Br in pyridine (Fig. 2) (Ojha et al., 2015). During this study, it was noticed that the hexane washings of the crude product (to remove adherent pyridine) had a yellow colour. We have now investigated the source of the colour and have isolated and crystallized the ortho-isomer, [Pt{(o-BrC₆F₄)N(CH₂)₂NEt₂}Cl(py)], 1o. This has been identified by X-ray crystallography, employing synchrotron radiation, and found to crystallize as a 1:1 mixture of the syn (1ox) and anti (1oy) rotamers (with respect to the o-Br and Pt—Cl positions) in the asymmetric unit.

Figure 2
Carbon dioxide elimination reaction for the synthesis of 1p and 1ox/1oy.

2. Experimental

2.1. General

NMR spectra were recorded in deuterated acetone with a Bruker DPX 400 spectrometer supported by Top Spin NMR software on a Windows NT workstation. CFCl₃ and tetramethylsilane (TMS) were used for the internal calibration of the ¹⁹F NMR and ¹H NMR spectra, respectively. IR spectra were recorded on a Perkin–Elmer 1600 FT–IR spectrophotometer as Nujol and hexachlorobutadiene (HCB) mulls between NaCl plates or recorded with an Agilent Cary 630 attenuated total reflectance (ATR) spectrometer in the range 4000–600 cm⁻¹.

2.2. X-ray crystallography

Crystal data, data collection and structure refinement details are summarized in Table 1. X-ray diffraction data obtained from single crystals of 1ox/1oy were collected at a wavelength of λ = 0.712 Å using the MX1 beamline at the Australian Synchrotron, Victoria, Australia, with a Blue Ice (McPhillips et al., 2002 ) GUI, using the same method as mentioned in the Experimental section of Ojha et al. (2015). Data were processed with the XDS (Kabsch, 1993 ) software package. Single crystals were loaded onto a fine glass fiber or cryoloop using hydrocarbon oil, with the collection kept at 123 K using an Oxford Cryosystems open-flow N₂ Cryostream. The program OLEX2 (Dolomanov et al., 2009 ) was used as the graphical interface. H atoms attached to C atoms were placed in calculated positions and allowed to ride on the atom to which they were attached.

Table 1
Crystallographic data for the molecular structures of 1ox/1oy and comparison with 1p

	ortho-1ox/1oy	1p (Ojha et al., 2015)
Empirical formula	C₃₄H₃₈Br_2.5Cl_1.5F₈N₆Pt₂	C₁₇H₁₉BrClF₄N₃Pt
Formula weight	1321.39	651.78
Crystal system	Triclinic	Monoclinic
Space group	P $[\overline{1}]$	P2₁/c
a (Å)	9.4810 (19)	10.960 (2)
b (Å)	14.656 (3)	11.961 (2)
c (Å)	15.094 (3)	15.224 (3)
α (°)	75.02 (3)	90
β (°)	74.62 (3)	98.46 (3)
γ (°)	86.28 (3)	90
V (Å³)	1953.5 (8)	1974.0 (7)
Z	2	4
ρ (calcd) (Mg m⁻³)	2.246	2.193
μ (mm⁻¹)	9.790	9.311
F(000)	1246.0	1232
Reflections collected/unique	24773/8572	22718/3354
R_int	0.0553	0.0267
2θ_max (°)	55.8	50.0
Goodness-of-fit on F²	1.052	1.126
R1 indices [I > 2σ(I)]	0.0626	0.0217
wR2 indices	0.1743	0.0518
Computer programs: Blue Ice (McPhillips et al., 2002), XDS (Kabsch, 1993), SHELXT2014 (Sheldrick, 2015a ) and SHELXL2018 (Sheldrick, 2015b ).

2.3. Isolation of ortho-isomers [Pt{(o-BrC₆F₄)NCH₂CH₂NEt₂}Cl(py)], 1ox/1oy

After completion of the typical synthesis of 1p by a CO₂ elimination reaction (Ojha et al., 2015), pyridine was removed under vacuum until dryness. Hexane was added to remove traces of residual pyridine and decanted. The major product 1p was extracted with acetone from the remaining solid, as reported earlier. The decanted hexane was yellow–orange, rather than colourless, indicating that it had not just removed the remaining pyridine, but possibly an isomer.

To isolate and crystallize the isomers, some acetone was added to the decanted solution. Crystals of 1ox/1oy suitable for structure determination were obtained by slow evaporation of the solvent. 1ox and 1oy are present in a 1:1 ratio. Apart from the X-ray data, the integrations for ¹H resonances measured in (CD₃)₂CO show 1ox/1oy in a 1:1 ratio.

Metallic yellow–orange blocks (yield: 0.130 g, 20%). ¹⁹F NMR [(CD₃)₂CO]: δ −140.6 (d, 2F, F3), −151.2 (d, 2F, F6), −160.9 (t, 2F, F5), −171.1 (m, 2F, F4). ¹H NMR [(CD₃)₂CO]: δ 1.53 (t, ³J_H,H = 7.15 Hz, 12H, NCH₂CH₃), 2.48 (t, with ¹⁹⁵Pt–H satellites, ³J_H,H = 6, ³J_H,Pt = 30 Hz, 4H, CH₂NEt₂), 2.80 (m, 4H, NCHAHBCH₃), 3.34 [m, 8H, made up of 4H CH₂N(p-BrC₆F₄) and 4H NCHBHACH₃], 7.09 [t, ³J_H,H = 7 Hz, 2H, H3,5(py)], 7.15 [t, 2H, ³J_H,H = 7 Hz, H3,5(py)], 7.65 [tt, ³J_H,H = 7, ⁴J_H,H = 1 Hz, 1H, H4 (py)], 7.70 [tt, ³J_H,H = 7, ⁴J_H,H = 1 Hz, 1H, H4 (py)], 8.50 [d with ¹⁹⁵Pt–H satellites, ³J_H,H = 5, ³J_H,Pt = 36 Hz, 2H, H2,6(py)], 8.54 [d with ¹⁹⁵Pt–H satellites, ³J_H,H = 5, ³J_H,Pt = 36 Hz, 2H, H2,6(py)]. IR (cm⁻¹): 2960 (w), 2922 (w), 2853 (w), 1654 (w), 1618 (w), 1607 (b), 1458 (s), 1450 (s), 1375 (m), 1345 (w), 1258 (s), 1208 (m), 1133 (s), 1073 (s), 1014 (s), 962 (s), 898 (m), 875 (m), 794 (s), 765 (s), 691 (s).

3. Results and discussion

The ortho-isomer 1o was preferentially isolated due to its markedly greater solubility in hexane compared to the para-isomer 1p. The synthesis predominantly afforded 1p (Ojha et al., 2015) by a CO₂ elimination reaction (Fig. 2). A subsequent hexane washing, intended to remove residual pyridine, unexpectedly exhibited a yellow–orange coloration. This observation suggested the presence of an additional platinum-containing species, which could be a different isomer, rather than merely solvent. Therefore, it was investigated further, and slow evaporation of the hexane washing enabled the isolation of the ortho-isomer [Pt{(o-BrC₆F₄)NCH₂CH₂NEt₂}Cl(py)], 1o, which was considerably more soluble in the low-polarity solvent hexane (with a trace of pyridine) than 1p. The ortho-isomer 1o crystallized as a 1:1 mixture of the anti (1ox) and syn (1oy) rotamers in the asymmetric unit. This procedure facilitates isolation of the pure para-isomer (1p) as the major product from the reaction mixture.

3.1. Characterization of 1o

The initial identification of 1o was via ¹H and ¹⁹F NMR spectroscopy in (CD₃)₂CO. The coordination of pyridine and the amide ligand to platinum was evident from the observation of ³J(¹⁹⁵Pt,H) satellites (¹⁹⁵Pt isotope, nuclear spin I = 1/2, natural abundance = 33.8%) on the signals of the H2,6(pyridine) and CH₂(N-ethyl) protons, with the coupling constants ³J(Pt,H2,6-py) and ³J(Pt,CH₂-N) having values (36 and 30 Hz, respectively) similar to those (35 and 28 Hz) observed for 1p (Ojha et al., 2015). Other ¹H chemical shifts and integrations, which are similar to those of 1p, are consistent with the composition of 1o.

Evidence for the proposed polyfluorophenyl substitution pattern comes from ¹⁹F NMR spectroscopy. Four equal-intensity ¹⁹F resonances indicate either a m-BrC₆F₄ or an o-BrC₆F₄ group compared with two for 1p (Fig. S1 for the F-atom numbering system). Chemical shift calculations {based on substituent chemical shifts for Br (Bruce, 1968 ; Ando & Matsuura, 1995 ), for o- and m-[N(–CH₂)Pt] groups derived from 1p (Ojha et al., 2015), and for p-[N(CH₂–)Pt] derived from several [Pt{C₆F₅NCH₂CH₂NEt₂}X(py)] complexes (Deacon et al., 1991)] clearly support the presence of an o-BrC₆F₄ substituent in 1o, and compares well with the observed chemical shift (Table 2). The ¹⁹F NMR spectrum is provided in the supporting information (Fig. S2) and shows the same chemical shifts for 1ox and 1oy. In the ¹H NMR spectrum, the pyridine resonances in 1ox and 1oy appear 0.1 ppm apart, as shown in Fig. S3, and show 1ox and 1oy in a 1:1 ratio.

Table 2
Observed and calculated chemical shifts (ppm) for 1o and their comparison with calculated m-BrC₆F₄ organoamidoplatinum(II) compounds

F	Observed	Calculated for o-BrC₆F₄	F	Calculated for m-BrC₆F₄
F3	−140.6	−140.6	F2	−122.5
F6	−151.2	−151.1	F6	−145.1
F5	−160.9	−163.2	F4	−145.2
F4	−171.1	−174.8	F5	−169.2

The unequivocal identification of 1o was provided by X-ray crystallography. The crystallographic data differ considerably from those of 1p (Table 1). 1o crystallizes in the triclinic space group P $[\overline{1}]$ with the rotamers 1ox and 1oy (Fig. 2) in the asymmetric unit (Table 1). In 1ox, Br and Cl are anti with a Br—Pt—Cl angle of 156.86 (6)°, whereas in 1oy, they are in a syn disposition with a Br—Pt—Cl angle of 113.61 (8)°.

In the proposed mechanism, initially, both chloride ligands on Pt are replaced by pyridine. Due to the hydrogen bonding between –NH₂ and CO₃²⁻, a lone-pair character is generated on the N atom and initiates nucleophilic substitution in the polyfluoroaryl ring (Deacon et al., 1998 ), as shown in Scheme S1 in the supporting information.

The Meisenheimer intermediates involved in the formation of 1p and 1o are depicted in Fig. 3. In the case of 1p, the negative charge generated during the nucleophilic substitution of the polyfluoroaryl ring is stabilized by two ortho- and two meta-fluorines, relative to the site of substitution (see Scheme S2 in the supporting information). Similarly, the formation of the ortho-Br isomers is also feasible because the negative charge in the Meisenheimer intermediate (Fig. 3) is located para and ortho to the site of substitution. This causes the positions ortho and para to Br to be electron deficient and thus susceptible to nucleophilic attack (Scheme S2). The negative charge in the Meisenheimer intermediate is stabilized by two o-F and two m-F atoms in 1p, and by two o-F and one m-F atom in 1o.

Figure 3
The Meisenheimer intermediates formed during the formation of 1p (left) and 1o (right).

The displacement of the pyridine ligand trans to the amide group by the chloride ion gives the target compound (see Scheme S1 in the supporting information). This regiospecificity is obtained as the trans effect of the –N(p-BrC₆F₄) N atom is greater than that of the –NEt₂ N atom, in line with the trans-influence values from platinum–H coupling constants (Buxton et al., 1988).

In 1ox, the Cl ligand coordinated to the Pt atom has a shared occupancy with Br, cf. 0.59 (1):0.41 (1), yielding 0.59 Cl and 0.41 Br, while for 1oy, the Cl remains the major occupant, with 0.91 (1) Cl and a slight sharing 0.09 (1) with Br. The Br atom is derived from C₆F₅Br. It has previously been shown that some elimination of Br occurs during the oxidation of 1p by hydrogen peroxide (Ojha et al., 2021), and replacement of chloride coordinated to Pt by bromide is consistent with the stability constants for soft metals (Ault et al., 1977 ).

The molecular structure of 1o shows that the Pt atom is coordinated in a square-planar array by a chelating {(o-BrC₆F₄)NCH₂CH₂NEt₂}⁻, pyridine and chloride ligands, with the chloride ligand being trans to the amide N atom and pyridine being trans to the amine group (Fig. 4). Thus, it is a trans-isomer in terms of the positions of the like-charged donor atoms. Selected bond lengths and angles for 1ox/1oy are given in Table 3 and compared with those of 1p. In general, the values for 1ox/1oy and 1p agree within or near the 3 e.s.d. level. However, the Pt—Cl bond of 1ox is longer than that of 1oy or 1p, owing to the shared Cl/Br occupancy. This is not a steric effect as the bond does not appear crowded. Supramolecular effects need to be considered. The Pt—N bond lengths follow the sequence Pt—N(amide) < Pt—N(py) < Pt—N(Et₂) (Table 3), as was also observed for 1p. Most bond angles around the Pt centre are 90°, with the smallest being the bite angles of 84.1° for 1ox and 83.5° for 1oy. The –NCH₂—CH₂N– sawhorse backbone is crooked, as seen in 1p and other compounds of this class (Deacon et al., 1991; Ojha et al., 2016 ).

Table 3
Selected bond lengths (Å) and bond angles (°) for 1ox/1oy and comparison with 1p

Bond	1ox	1oy	1p	Angle	1ox	1oy	1p
Pt—Cl	2.35 (3)	2.323 (7)	2.344 (10)	Cl—Pt—N(amide)	177.5 (9)	175.8 (4)	176.17 (9)
Pt—Br	2.534 (16)	2.62 (3)	–	N(amide)—Pt—N(Et₂)	84.2 (4)	83.5 (4)	82.65 (12)
Pt—N(amide)	1.993 (11)	2.006 (11)	2.006 (3)	N(amide)—Pt—N(py)	91.6 (4)	93.2 (4)	93.27 (12)
Pt—N(Et₂)	2.087 (10)	2.076 (9)	2.074 (3)	Cl—Pt—N(Et₂)	93.3 (8)	92.3 (4)	93.98 (9)
Pt—N(py)	2.034 (9)	2.026 (9)	2.013 (3)	Cl—Pt—N(py)	90.9 (8)	90.9 (4)	90.25 (8)
N(amide)—C(C₆F₄)	1.383 (19)	1.362 (19)	1.354 (4)	N(Et₂)—Pt—N(py)	174.8 (4)	173.8 (4)	173.53 (12)

Figure 4
The molecular crystal structures of rotamers 1ox (anti) and 1oy (syn) cocrystallized in a single unit cell, showing 50% probability displacement ellipsoids.

Intramolecular hydrogen bonding in 1ox is observed as (NEt₂)H⋯Br, with an H⋯Br distance of 2.91 (2) Å, while 1oy displayed an (NEt₂)H⋯Br interaction of 2.91 (4) Å and an (NEt₂)H⋯Cl interaction of 2.754 (9) Å (Fig. 4). Intermolecular hydrogen bonding between the 1ox Cl/Br atoms and the H(NEt₂) atom of 1oy, with an (NEt₂)H⋯Br distance of 3.093 (19) Å and an (NEt₂)H⋯Cl distance of 2.97 (3) Å, was also observed. A π–π interaction between the two polyfluoroaryl rings is present (but not between py rings) and, in this arrangement, the polyfluoroaryl rings are not parallel but have an interplanar angle of 6.703 (3)°, as shown in Fig. 5. The ortho-Br atoms of both molecules are on the same side (as shown in the inset of Fig. 5), resulting in significant steric hindrance on one side. Consequently, the polyfluoroaryl rings are tilted at an angle of 6.703 (3)° to reduce the steric hindrance. The inter-centroid distance is 3.7969 (10) Å and the rings are offset by 1.7513 (15) Å, as was also observed for other similar compounds (Ojha et al., 2018 ). On the other hand, in 1p, a π–π interaction was observed between two pyridine rings, and not between polyfluoroaryl rings.

Figure 5
The π–π interaction between the two polyfluoroaryl rings of two molecules with an angle of 6.703 (3)°, where the mirror image is rotated by 180° and the symmetry code is (−x + 1, −y, −z + 1). The inset shows the ortho-Br atoms.

The π–π interaction is further anchored by strong intermolecular hydrogen bonding between the para-F atom of 1ox with a methylene H of the ligand backbone of 1oy, and vice versa, as shown in Fig. 6, with H⋯F distances of 2.352 (7) and 2.424 (10) Å. Additionally, comparatively weak interactions, such as between the para-F atom of 1ox with a methyl H atom of the NEt₂ group, with an H⋯F distance of 3.012 (8) Å, and a very weak interaction between the ortho-F atom of 1ox and a methylene H atom of the ligand backbone of 1oy, with a H⋯F distance of 3.353 (11) Å, further stabilize the π–π interaction.

Figure 6
The crystal packing in 1ox/1oy, showing the π–π interactions between the two polyfluoroaryl rings of 1ox and 1oy, and inter- and intramolecular hydrogen bonding.

In the 1ox/1oy isomers, one Et group makes an agostic interaction with Pt; the Pt⋯H(CH₃) distance is 2.8043 (11) Å and the bond angles are 118.8 (3)° for H—Pt—N(py), 103.8 (3)° for H—Pt—N(C₆F₅) and 65.3 (3)° for H—Pt—N(Et)₂ in 1ox, and the Pt⋯H(CH₃) distance is 3.0032 (11) Å and the bond angles are 120.0 (3)° for H—Pt—N(py), 106.7 (3)° for H—Pt—N(C₆F₅) and 66.1 (3)° for H—Pt—N(Et)₂ in 1oy. The ortho-F atom of 1ox makes an intramolecular hydrogen-bonding contact with a methyl H atom of –N(Et₂), which exhibits an agostic interaction with Pt, with an H⋯F distance of 2.994 (7) Å (Fig. 7). These rotamers display the entire network of supramolecular interactions, as illustrated in Fig. 7. The p-H(py) atom of 1ox is anchored by intermolecular hydrogen bonding with the Cl/Br atom of the two adjacent 1ox molecules, with H⋯Br distances of 3.050 (16) and 3.26 (2) Å, and H⋯Cl distances of 3.15 (2) and 3.41 (3) Å (see Fig. 7). Similarly, the m-H(py) atom is involved in hydrogen bonding with the Cl/Br atom of another 1ox molecule, with a H⋯Br distance of 2.78 (4) Å and a H⋯Cl distance of 2.578 (8) Å.

Figure 7
The crystal packing in 1ox/1oy, showing H⋯Cl interactions for 1ox and C⋯H interactions for 1oy as intermolecular hydrogen bonding.

Intermolecular F⋯H hydrogen bonding of two adjacent 1ox molecules, with an F⋯H distance of 2.915 (9) Å, was observed between the m-F atom of the polyfluoroaryl ring and a methyl H of the Et group (–NEt₂), the one not showing the agostic interactions with Pt (Fig. 7). These supramolecular interactions may facilitate the docking of the drug and reinforce the nucleobase–Pt interactions.

4. Conclusion

Further examination of the products of the reaction between [PtCl₂{H₂N(CH₂)₂NEt₂}], Tl₂CO₃ and bromopentafluorobenzene in refluxing pyridine has revealed that, in addition to the major product, [Pt{(p-BrC₆F₄)N(CH₂)₂NEt₂}Cl(py)], i.e. 1p, a significant amount of the ortho-stereoisomer, [Pt{(o-BrC₆F₄)N(CH₂)₂NEt₂}Cl(py)], i.e. 1o, can also be isolated, taking advantage of the much higher solubility of 1o. The new regioisomer, which was characterized by synchrotron X-ray crystallography, crystallizes as a 1:1 mixture of two rotameric isomers, i.e. 1ox and 1oy, according to whether the Br substituent and the Cl ligand are in an anti (in 1ox) or syn (in 1oy) disposition. The ¹H and ¹⁹F NMR spectra in (CD₃)₂CO are consistent with the structural assignment.

Supporting information

CCDC references: 2481234; 2477306

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2053229625006837/yd3064sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2053229625006837/yd3064Isup2.hkl

Numbering schemes, reation pathway, resonance structures and ¹⁹F and ¹H NMR spectra. DOI: https://doi.org/10.1107/S2053229625006837/yd3064sup3.pdf

Computing details top

trans-[N-(2-Bromo-3,4,5,6-tetrafluorophenyl)-N',N'-diethylethane-1,2-diaminato(1-)]chloridopyridineplatinum(II) top

Crystal data top

[PtBr_0.1(C₁₂H₁₄BrF₄N₂)(C₅H₅N)Cl_0.9] [PtBr_0.4(C₁₂H₁₄BrF₄N₂)(C₅H₅N)Cl_0.6]	Z = 2
M_r = 1321.39	F(000) = 1246
Triclinic, P1	D_x = 2.246 Mg m⁻³
a = 9.4810 (19) Å	Synchrotron radiation, λ = 0.7108 Å
b = 14.656 (3) Å	Cell parameters from 8572 reflections
c = 15.094 (3) Å	θ = 1.4–27.9°
α = 75.02 (3)°	µ = 9.79 mm⁻¹
β = 74.62 (3)°	T = 100 K
γ = 86.28 (3)°	Prism, yellow
V = 1953.5 (8) Å³	0.02 × 0.02 × 0.01 mm

Data collection top

ADSC Quantum 210r diffractometer	θ_max = 27.9°, θ_min = 1.4°
Radiation source: Australian Synchrotron MX1	h = −12→12
phi scans	k = −19→19
24773 measured reflections	l = −19→19
8572 independent reflections	8572 standard reflections every 0 reflections
6722 reflections with I > 2σ(I)	intensity decay: none
R_int = 0.055

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.063	w = 1/[σ²(F_o²) + (0.0879P)² + 22.6555P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.174	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 2.78 e Å⁻³
8572 reflections	Δρ_min = −2.37 e Å⁻³
506 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
38 restraints	Extinction coefficient: 0.0085 (5)
Primary atom site location: dual

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	U_iso*/U_eq	Occ. (<1)
Pt1	0.68588 (5)	0.26255 (3)	0.69629 (3)	0.03652 (16)
Pt2	0.84692 (4)	0.40034 (3)	0.21031 (3)	0.03580 (16)
Br1	0.29324 (18)	0.10436 (12)	0.96603 (11)	0.0617 (4)
Br2	0.76261 (16)	0.27209 (12)	0.07351 (11)	0.0582 (4)
Br1A	0.844 (2)	0.4020 (10)	0.5902 (13)	0.036 (2)	0.414 (11)
Br2A	1.011 (5)	0.549 (2)	0.112 (3)	0.0371 (12)	0.091 (10)
F1	0.1118 (10)	−0.0192 (6)	0.9139 (9)	0.083 (3)
F2	0.1215 (11)	−0.0589 (5)	0.7548 (8)	0.085 (3)
F3	0.3670 (13)	0.0166 (6)	0.5945 (8)	0.078 (3)
F4	0.5838 (7)	0.1069 (5)	0.6057 (5)	0.0454 (17)
F5	0.5008 (10)	0.1702 (7)	0.0865 (6)	0.065 (2)
F6	0.2804 (7)	0.0882 (4)	0.2309 (6)	0.0478 (18)
F7	0.2840 (9)	0.1086 (6)	0.4125 (6)	0.062 (2)
F8	0.4821 (8)	0.2093 (5)	0.4402 (5)	0.0447 (16)
N1	0.5650 (12)	0.1575 (8)	0.7918 (8)	0.048 (3)
N2	0.8564 (11)	0.1972 (7)	0.7524 (7)	0.040 (2)
N3	0.5077 (10)	0.3228 (7)	0.6537 (7)	0.036 (2)
N4	0.7279 (12)	0.2856 (8)	0.2896 (8)	0.048 (3)
N5	1.0108 (10)	0.3299 (7)	0.2689 (8)	0.041 (2)
N6	0.6742 (10)	0.4682 (7)	0.1676 (7)	0.0348 (19)
C1	0.3369 (12)	0.0695 (9)	0.8536 (10)	0.049 (3)
C2	0.2294 (14)	0.0143 (8)	0.8452 (10)	0.058 (4)
C3	0.2381 (17)	−0.0042 (10)	0.7587 (10)	0.072 (5)
C4	0.3514 (14)	0.0330 (10)	0.6810 (12)	0.072 (5)
C5	0.4619 (16)	0.0853 (9)	0.6918 (10)	0.052 (3)
C6	0.4588 (12)	0.1060 (8)	0.7783 (8)	0.041 (3)
C7	0.6381 (14)	0.1128 (10)	0.8651 (9)	0.048 (3)
H7A	0.593910	0.050255	0.900527	0.057*
H7B	0.629319	0.152434	0.910403	0.057*
C8	0.7960 (14)	0.1022 (9)	0.8160 (10)	0.047 (3)
H8A	0.804889	0.055707	0.777419	0.056*
H8B	0.852798	0.078673	0.863654	0.056*
C9	0.8925 (15)	0.2589 (10)	0.8095 (10)	0.047 (3)
H9A	0.801059	0.270905	0.854930	0.056*
H9B	0.928483	0.320540	0.765718	0.056*
C10	1.0060 (16)	0.2195 (10)	0.8650 (11)	0.054 (3)
H10A	1.095621	0.203945	0.821542	0.082*
H10B	0.967023	0.162426	0.914066	0.082*
H10C	1.028032	0.266938	0.894813	0.082*
C11	0.9930 (14)	0.1841 (10)	0.6768 (10)	0.048 (3)
H11A	1.037998	0.246810	0.643044	0.058*
H11B	1.064064	0.145908	0.708542	0.058*
C12	0.9669 (17)	0.1370 (11)	0.6047 (10)	0.056 (3)
H12A	1.057406	0.138283	0.554506	0.084*
H12B	0.889970	0.170742	0.576982	0.084*
H12C	0.936461	0.071332	0.635813	0.084*
C13	0.3853 (12)	0.3349 (8)	0.7196 (8)	0.037 (2)
H13	0.383238	0.312461	0.784832	0.044*
C14	0.2652 (13)	0.3781 (9)	0.6955 (9)	0.043 (3)
H14	0.180904	0.386731	0.743289	0.051*
C15	0.2668 (14)	0.4097 (9)	0.5995 (9)	0.045 (3)
H15	0.183628	0.439585	0.580795	0.054*
C16	0.3898 (13)	0.3966 (10)	0.5339 (10)	0.046 (3)
H16	0.393144	0.417337	0.468304	0.055*
C17	0.5108 (13)	0.3533 (9)	0.5618 (8)	0.039 (2)
H17	0.596855	0.345227	0.515042	0.047*
C18	0.5011 (11)	0.1986 (8)	0.3484 (9)	0.041 (3)
C19	0.3930 (14)	0.1453 (10)	0.3386 (9)	0.052 (3)
C20	0.3927 (14)	0.1386 (9)	0.2490 (9)	0.056 (4)
C21	0.5055 (12)	0.1814 (9)	0.1724 (9)	0.049 (3)
C22	0.6140 (14)	0.2328 (10)	0.1837 (9)	0.048 (3)
C23	0.6197 (12)	0.2407 (9)	0.2731 (7)	0.040 (3)
C24	0.7917 (13)	0.2382 (9)	0.3686 (9)	0.042 (3)
H24A	0.750692	0.173742	0.398470	0.050*
H24B	0.771736	0.274514	0.417514	0.050*
C25	0.9527 (13)	0.2342 (9)	0.3248 (9)	0.044 (3)
H25A	1.004040	0.209574	0.375300	0.053*
H25B	0.971497	0.190623	0.282661	0.053*
C26	1.0383 (14)	0.3876 (9)	0.3331 (9)	0.044 (3)
H26A	0.944977	0.392396	0.380404	0.053*
H26B	1.066652	0.452355	0.294031	0.053*
C27	1.1553 (16)	0.3502 (11)	0.3865 (11)	0.056 (4)
H27A	1.251437	0.354006	0.340966	0.084*
H27B	1.133435	0.284230	0.421567	0.084*
H27C	1.155826	0.388277	0.431002	0.084*
C28	1.1543 (13)	0.3234 (10)	0.1954 (10)	0.044 (3)
H28A	1.222347	0.281796	0.227181	0.053*
H28B	1.199440	0.386960	0.168609	0.053*
C29	1.1344 (14)	0.2848 (10)	0.1138 (10)	0.050 (3)
H29A	1.093553	0.334224	0.070248	0.075*
H29B	1.067544	0.230496	0.139831	0.075*
H29C	1.229399	0.264957	0.079482	0.075*
C30	0.5450 (12)	0.4683 (9)	0.2321 (8)	0.039 (2)
H30	0.536734	0.433241	0.295741	0.047*
C31	0.4239 (13)	0.5171 (8)	0.2102 (9)	0.041 (3)
H31	0.334751	0.515894	0.257648	0.050*
C32	0.4356 (13)	0.5677 (9)	0.1176 (10)	0.045 (3)
H32	0.354726	0.602666	0.100600	0.055*
C33	0.5671 (13)	0.5669 (9)	0.0493 (9)	0.043 (3)
H33	0.575966	0.599672	−0.015072	0.051*
C34	0.6869 (14)	0.5168 (9)	0.0768 (9)	0.044 (3)
H34	0.777604	0.517330	0.030862	0.053*
Cl1	0.837 (3)	0.3837 (16)	0.586 (2)	0.030 (3)	0.586 (11)
Cl2	0.9986 (9)	0.5287 (5)	0.1236 (6)	0.0371 (12)	0.909 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pt1	0.0295 (2)	0.0424 (3)	0.0387 (3)	0.00454 (19)	−0.01210 (17)	−0.00950 (18)
Pt2	0.0266 (2)	0.0453 (3)	0.0386 (3)	0.00293 (19)	−0.01070 (16)	−0.01434 (19)
Br1	0.0605 (9)	0.0669 (9)	0.0567 (8)	−0.0041 (7)	−0.0199 (7)	−0.0080 (7)
Br2	0.0504 (8)	0.0756 (10)	0.0541 (8)	0.0061 (7)	−0.0173 (6)	−0.0233 (7)
Br1A	0.041 (3)	0.030 (6)	0.044 (2)	0.006 (4)	−0.0188 (18)	−0.014 (3)
Br2A	0.031 (2)	0.037 (3)	0.042 (3)	−0.002 (2)	−0.0059 (18)	−0.010 (3)
F1	0.050 (5)	0.052 (5)	0.127 (9)	−0.010 (4)	−0.006 (5)	0.000 (5)
F3	0.115 (9)	0.053 (5)	0.092 (7)	0.015 (5)	−0.056 (7)	−0.036 (5)
F5	0.072 (6)	0.079 (6)	0.068 (6)	0.017 (5)	−0.039 (5)	−0.041 (5)
F6	0.029 (3)	0.026 (3)	0.093 (6)	−0.001 (3)	−0.026 (3)	−0.013 (3)
F7	0.052 (5)	0.056 (5)	0.070 (6)	−0.007 (4)	−0.017 (4)	0.000 (4)
F8	0.051 (4)	0.044 (4)	0.043 (4)	0.003 (3)	−0.017 (3)	−0.014 (3)
N1	0.040 (6)	0.057 (6)	0.046 (6)	0.002 (5)	−0.019 (5)	−0.003 (5)
N2	0.035 (5)	0.038 (5)	0.049 (6)	0.009 (4)	−0.018 (4)	−0.009 (4)
N3	0.029 (5)	0.035 (5)	0.046 (5)	0.008 (4)	−0.013 (4)	−0.013 (4)
N4	0.038 (6)	0.060 (7)	0.049 (6)	−0.001 (5)	−0.022 (5)	−0.008 (5)
N5	0.026 (5)	0.048 (6)	0.055 (6)	0.014 (4)	−0.021 (4)	−0.018 (5)
N6	0.025 (4)	0.039 (5)	0.042 (5)	0.005 (4)	−0.007 (4)	−0.015 (4)
C1	0.038 (7)	0.040 (6)	0.065 (9)	0.010 (6)	−0.004 (6)	−0.019 (6)
C2	0.032 (7)	0.026 (6)	0.109 (13)	0.000 (5)	−0.019 (7)	−0.002 (7)
C3	0.068 (11)	0.040 (7)	0.128 (17)	0.004 (8)	−0.057 (11)	−0.024 (9)
C4	0.065 (11)	0.054 (9)	0.116 (15)	0.020 (8)	−0.063 (11)	−0.018 (10)
C5	0.058 (9)	0.042 (7)	0.066 (9)	0.010 (6)	−0.035 (7)	−0.015 (6)
C6	0.034 (6)	0.033 (5)	0.056 (7)	−0.002 (5)	−0.017 (5)	−0.004 (5)
C7	0.037 (6)	0.060 (8)	0.043 (7)	−0.007 (6)	−0.013 (5)	−0.004 (6)
C8	0.044 (7)	0.043 (6)	0.051 (7)	−0.006 (6)	−0.018 (6)	0.001 (5)
C9	0.044 (7)	0.052 (7)	0.050 (7)	0.005 (6)	−0.028 (6)	−0.008 (6)
C10	0.050 (8)	0.055 (8)	0.071 (9)	0.017 (7)	−0.037 (7)	−0.020 (7)
C11	0.037 (7)	0.045 (7)	0.064 (8)	0.011 (6)	−0.015 (6)	−0.016 (6)
C12	0.054 (8)	0.057 (8)	0.054 (8)	0.030 (7)	−0.015 (6)	−0.016 (6)
C13	0.029 (5)	0.040 (6)	0.042 (6)	0.006 (5)	−0.010 (4)	−0.012 (5)
C14	0.026 (5)	0.058 (7)	0.051 (7)	0.007 (5)	−0.014 (5)	−0.024 (6)
C15	0.042 (7)	0.046 (7)	0.054 (7)	0.003 (6)	−0.023 (6)	−0.013 (6)
C16	0.030 (6)	0.064 (8)	0.052 (7)	0.012 (6)	−0.019 (5)	−0.023 (6)
C17	0.032 (6)	0.054 (7)	0.033 (6)	0.011 (5)	−0.011 (4)	−0.014 (5)
C18	0.029 (6)	0.038 (6)	0.058 (7)	0.003 (5)	−0.011 (5)	−0.015 (5)
C19	0.037 (7)	0.053 (8)	0.066 (9)	−0.004 (6)	−0.018 (6)	−0.008 (6)
C20	0.050 (8)	0.040 (7)	0.097 (12)	0.011 (6)	−0.042 (8)	−0.031 (7)
C21	0.057 (8)	0.054 (7)	0.057 (8)	0.026 (7)	−0.036 (7)	−0.033 (7)
C22	0.042 (7)	0.058 (8)	0.055 (8)	0.007 (6)	−0.020 (6)	−0.027 (6)
C23	0.025 (5)	0.047 (6)	0.051 (7)	0.012 (5)	−0.012 (5)	−0.016 (5)
C24	0.030 (6)	0.052 (7)	0.042 (6)	0.006 (5)	−0.008 (5)	−0.015 (5)
C25	0.039 (6)	0.050 (7)	0.049 (7)	0.002 (6)	−0.022 (5)	−0.011 (6)
C26	0.041 (7)	0.053 (7)	0.049 (7)	0.003 (6)	−0.022 (5)	−0.021 (6)
C27	0.057 (8)	0.058 (8)	0.058 (8)	−0.010 (7)	−0.032 (7)	−0.004 (7)
C28	0.026 (5)	0.050 (7)	0.060 (8)	0.018 (5)	−0.010 (5)	−0.023 (6)
C29	0.036 (6)	0.058 (8)	0.055 (8)	−0.003 (6)	−0.007 (5)	−0.018 (6)
C30	0.026 (5)	0.053 (7)	0.039 (6)	0.005 (5)	−0.005 (4)	−0.018 (5)
C31	0.028 (6)	0.041 (6)	0.058 (7)	0.009 (5)	−0.012 (5)	−0.018 (5)
C32	0.031 (6)	0.050 (7)	0.065 (8)	0.009 (6)	−0.024 (5)	−0.020 (6)
C33	0.039 (6)	0.043 (6)	0.049 (7)	0.003 (5)	−0.021 (5)	−0.007 (5)
C34	0.033 (6)	0.054 (7)	0.043 (6)	0.005 (6)	−0.017 (5)	−0.002 (5)
Cl1	0.034 (4)	0.020 (6)	0.042 (4)	0.001 (4)	−0.012 (3)	−0.014 (4)
F4	0.028 (3)	0.043 (4)	0.052 (4)	−0.001 (3)	−0.015 (3)	0.017 (3)
F2	0.092 (7)	0.032 (4)	0.177 (10)	0.015 (4)	−0.103 (7)	−0.042 (5)
Cl2	0.031 (2)	0.037 (3)	0.042 (3)	−0.002 (2)	−0.0059 (18)	−0.010 (3)

Geometric parameters (Å, º) top

Pt1—N1	1.993 (11)	C10—H10B	0.9800
Pt1—N3	2.034 (9)	C10—H10C	0.9800
Pt1—N2	2.087 (10)	C11—C12	1.508 (19)
Pt1—Cl1	2.35 (3)	C11—H11A	0.9900
Pt1—Br1A	2.534 (16)	C11—H11B	0.9900
Pt2—N4	2.006 (11)	C12—H12A	0.9800
Pt2—N6	2.026 (9)	C12—H12B	0.9800
Pt2—N5	2.076 (9)	C12—H12C	0.9800
Pt2—Cl2	2.323 (7)	C13—C14	1.355 (16)
Pt2—Br2A	2.62 (3)	C13—H13	0.9500
Br1—C1	1.833 (13)	C14—C15	1.399 (18)
Br2—C22	1.858 (14)	C14—H14	0.9500
F1—C2	1.324 (16)	C15—C16	1.354 (18)
F3—C4	1.36 (2)	C15—H15	0.9500
F5—C21	1.360 (13)	C16—C17	1.386 (16)
F6—C20	1.454 (13)	C16—H16	0.9500
F7—C19	1.324 (15)	C17—H17	0.9500
F8—C18	1.396 (14)	C18—C19	1.388 (11)
N1—C6	1.382 (15)	C18—C23	1.409 (11)
N1—C7	1.452 (15)	C19—C20	1.381 (12)
N2—C9	1.510 (16)	C20—C21	1.390 (12)
N2—C8	1.519 (15)	C21—C22	1.383 (11)
N2—C11	1.521 (17)	C22—C23	1.400 (12)
N3—C17	1.336 (14)	C24—C25	1.498 (17)
N3—C13	1.349 (14)	C24—H24A	0.9900
N4—C23	1.361 (15)	C24—H24B	0.9900
N4—C24	1.474 (15)	C25—H25A	0.9900
N5—C25	1.491 (16)	C25—H25B	0.9900
N5—C26	1.518 (14)	C26—C27	1.532 (17)
N5—C28	1.526 (15)	C26—H26A	0.9900
N6—C34	1.348 (15)	C26—H26B	0.9900
N6—C30	1.349 (14)	C27—H27A	0.9800
C1—C2	1.392 (12)	C27—H27B	0.9800
C1—C6	1.408 (12)	C27—H27C	0.9800
C2—C3	1.381 (13)	C28—C29	1.539 (18)
C3—C4	1.380 (14)	C28—H28A	0.9900
C3—F2	1.430 (15)	C28—H28B	0.9900
C4—C5	1.403 (12)	C29—H29A	0.9800
C5—C6	1.408 (12)	C29—H29B	0.9800
C5—F4	1.471 (16)	C29—H29C	0.9800
C7—C8	1.502 (18)	C30—C31	1.382 (16)
C7—H7A	0.9900	C30—H30	0.9500
C7—H7B	0.9900	C31—C32	1.381 (19)
C8—H8A	0.9900	C31—H31	0.9500
C8—H8B	0.9900	C32—C33	1.393 (18)
C9—C10	1.530 (16)	C32—H32	0.9500
C9—H9A	0.9900	C33—C34	1.408 (16)
C9—H9B	0.9900	C33—H33	0.9500
C10—H10A	0.9800	C34—H34	0.9500

N1—Pt1—N3	91.6 (4)	H11A—C11—H11B	107.6
N1—Pt1—N2	84.2 (4)	C11—C12—H12A	109.5
N3—Pt1—N2	174.8 (4)	C11—C12—H12B	109.5
N1—Pt1—Cl1	177.5 (9)	H12A—C12—H12B	109.5
N3—Pt1—Cl1	90.9 (8)	C11—C12—H12C	109.5
N2—Pt1—Cl1	93.3 (8)	H12A—C12—H12C	109.5
N1—Pt1—Br1A	173.7 (5)	H12B—C12—H12C	109.5
N3—Pt1—Br1A	90.8 (5)	N3—C13—C14	122.0 (11)
N2—Pt1—Br1A	93.0 (5)	N3—C13—H13	119.0
Cl1—Pt1—Br1A	5.7 (9)	C14—C13—H13	119.0
N4—Pt2—N6	93.2 (4)	C13—C14—C15	119.2 (12)
N4—Pt2—N5	83.5 (4)	C13—C14—H14	120.4
N6—Pt2—N5	173.9 (4)	C15—C14—H14	120.4
N4—Pt2—Cl2	175.8 (4)	C16—C15—C14	118.4 (12)
N6—Pt2—Cl2	90.9 (4)	C16—C15—H15	120.8
N5—Pt2—Cl2	92.3 (4)	C14—C15—H15	120.8
N4—Pt2—Br2A	177.2 (11)	C15—C16—C17	120.5 (12)
N6—Pt2—Br2A	89.3 (10)	C15—C16—H16	119.8
N5—Pt2—Br2A	93.9 (10)	C17—C16—H16	119.8
Cl2—Pt2—Br2A	1.8 (12)	N3—C17—C16	120.7 (11)
C6—N1—C7	117.8 (11)	N3—C17—H17	119.7
C6—N1—Pt1	126.9 (8)	C16—C17—H17	119.7
C7—N1—Pt1	110.9 (8)	C19—C18—F8	114.3 (9)
C9—N2—C8	111.0 (10)	C19—C18—C23	124.0 (11)
C9—N2—C11	109.3 (10)	F8—C18—C23	121.7 (9)
C8—N2—C11	110.6 (10)	F7—C19—C20	120.1 (9)
C9—N2—Pt1	107.0 (7)	F7—C19—C18	120.6 (10)
C8—N2—Pt1	105.6 (7)	C20—C19—C18	119.0 (12)
C11—N2—Pt1	113.3 (8)	C19—C20—C21	118.6 (11)
C17—N3—C13	119.3 (10)	C19—C20—F6	123.1 (10)
C17—N3—Pt1	121.4 (8)	C21—C20—F6	118.2 (9)
C13—N3—Pt1	119.3 (8)	F5—C21—C22	122.8 (11)
C23—N4—C24	118.6 (11)	F5—C21—C20	115.7 (9)
C23—N4—Pt2	130.7 (8)	C22—C21—C20	121.5 (11)
C24—N4—Pt2	109.7 (7)	C21—C22—C23	121.8 (12)
C25—N5—C26	111.1 (10)	C21—C22—Br2	113.4 (8)
C25—N5—C28	111.2 (10)	C23—C22—Br2	124.1 (8)
C26—N5—C28	108.2 (9)	N4—C23—C22	124.7 (10)
C25—N5—Pt2	107.0 (7)	N4—C23—C18	120.6 (10)
C26—N5—Pt2	105.7 (7)	C22—C23—C18	114.7 (10)
C28—N5—Pt2	113.5 (8)	N4—C24—C25	105.2 (10)
C34—N6—C30	119.0 (10)	N4—C24—H24A	110.7
C34—N6—Pt2	121.6 (8)	C25—C24—H24A	110.7
C30—N6—Pt2	119.3 (8)	N4—C24—H24B	110.7
C2—C1—C6	123.3 (12)	C25—C24—H24B	110.7
C2—C1—Br1	113.9 (9)	H24A—C24—H24B	108.8
C6—C1—Br1	122.3 (8)	N5—C25—C24	110.7 (10)
F1—C2—C3	115.7 (11)	N5—C25—H25A	109.5
F1—C2—C1	124.7 (12)	C24—C25—H25A	109.5
C3—C2—C1	119.4 (13)	N5—C25—H25B	109.5
C4—C3—C2	120.2 (13)	C24—C25—H25B	109.5
C4—C3—F2	123.5 (11)	H25A—C25—H25B	108.1
C2—C3—F2	116.3 (11)	N5—C26—C27	116.4 (11)
F3—C4—C3	123.0 (11)	N5—C26—H26A	108.2
F3—C4—C5	117.4 (13)	C27—C26—H26A	108.2
C3—C4—C5	119.5 (15)	N5—C26—H26B	108.2
C4—C5—C6	122.7 (13)	C27—C26—H26B	108.2
C4—C5—F4	111.8 (11)	H26A—C26—H26B	107.3
C6—C5—F4	125.3 (10)	C26—C27—H27A	109.5
N1—C6—C5	124.5 (10)	C26—C27—H27B	109.5
N1—C6—C1	120.6 (10)	H27A—C27—H27B	109.5
C5—C6—C1	114.8 (11)	C26—C27—H27C	109.5
N1—C7—C8	106.9 (11)	H27A—C27—H27C	109.5
N1—C7—H7A	110.3	H27B—C27—H27C	109.5
C8—C7—H7A	110.3	N5—C28—C29	113.1 (10)
N1—C7—H7B	110.3	N5—C28—H28A	109.0
C8—C7—H7B	110.3	C29—C28—H28A	109.0
H7A—C7—H7B	108.6	N5—C28—H28B	109.0
C7—C8—N2	109.4 (11)	C29—C28—H28B	109.0
C7—C8—H8A	109.8	H28A—C28—H28B	107.8
N2—C8—H8A	109.8	C28—C29—H29A	109.5
C7—C8—H8B	109.8	C28—C29—H29B	109.5
N2—C8—H8B	109.8	H29A—C29—H29B	109.5
H8A—C8—H8B	108.2	C28—C29—H29C	109.5
N2—C9—C10	115.8 (11)	H29A—C29—H29C	109.5
N2—C9—H9A	108.3	H29B—C29—H29C	109.5
C10—C9—H9A	108.3	N6—C30—C31	123.1 (11)
N2—C9—H9B	108.3	N6—C30—H30	118.4
C10—C9—H9B	108.3	C31—C30—H30	118.4
H9A—C9—H9B	107.4	C32—C31—C30	118.4 (12)
C9—C10—H10A	109.5	C32—C31—H31	120.8
C9—C10—H10B	109.5	C30—C31—H31	120.8
H10A—C10—H10B	109.5	C31—C32—C33	119.4 (11)
C9—C10—H10C	109.5	C31—C32—H32	120.3
H10A—C10—H10C	109.5	C33—C32—H32	120.3
H10B—C10—H10C	109.5	C32—C33—C34	119.2 (12)
C12—C11—N2	114.6 (11)	C32—C33—H33	120.4
C12—C11—H11A	108.6	C34—C33—H33	120.4
N2—C11—H11A	108.6	N6—C34—C33	120.8 (12)
C12—C11—H11B	108.6	N6—C34—H34	119.6
N2—C11—H11B	108.6	C33—C34—H34	119.6

C6—C1—C2—F1	−178.4 (13)	F8—C18—C19—F7	−0.5 (19)
Br1—C1—C2—F1	−6.4 (18)	C23—C18—C19—F7	−179.5 (12)
C6—C1—C2—C3	−2 (2)	F8—C18—C19—C20	173.3 (11)
Br1—C1—C2—C3	169.9 (11)	C23—C18—C19—C20	−6 (2)
F1—C2—C3—C4	175.8 (14)	F7—C19—C20—C21	177.3 (13)
C1—C2—C3—C4	−1 (2)	C18—C19—C20—C21	3 (2)
F1—C2—C3—F2	−1.5 (19)	F7—C19—C20—F6	−3 (2)
C1—C2—C3—F2	−178.1 (12)	C18—C19—C20—F6	−177.0 (12)
C2—C3—C4—F3	179.2 (13)	C19—C20—C21—F5	178.4 (11)
F2—C3—C4—F3	−4 (2)	F6—C20—C21—F5	−1.1 (17)
C2—C3—C4—C5	3 (2)	C19—C20—C21—C22	−2 (2)
F2—C3—C4—C5	−179.5 (13)	F6—C20—C21—C22	178.2 (11)
F3—C4—C5—C6	−179.3 (12)	F5—C21—C22—C23	−177.7 (12)
C3—C4—C5—C6	−3 (2)	C20—C21—C22—C23	3 (2)
F3—C4—C5—F4	−4.5 (18)	F5—C21—C22—Br2	−6.9 (17)
C3—C4—C5—F4	171.5 (13)	C20—C21—C22—Br2	173.8 (11)
C7—N1—C6—C5	−122.4 (14)	C24—N4—C23—C22	−133.8 (13)
Pt1—N1—C6—C5	31.8 (18)	Pt2—N4—C23—C22	34.1 (19)
C7—N1—C6—C1	57.3 (17)	C24—N4—C23—C18	47.0 (17)
Pt1—N1—C6—C1	−148.4 (11)	Pt2—N4—C23—C18	−145.1 (11)
C4—C5—C6—N1	−179.7 (13)	C21—C22—C23—N4	176.1 (13)
F4—C5—C6—N1	6 (2)	Br2—C22—C23—N4	6.3 (19)
C4—C5—C6—C1	0.5 (19)	C21—C22—C23—C18	−4.7 (19)
F4—C5—C6—C1	−173.6 (12)	Br2—C22—C23—C18	−174.4 (10)
C2—C1—C6—N1	−177.5 (12)	C19—C18—C23—N4	−174.7 (13)
Br1—C1—C6—N1	11.1 (18)	F8—C18—C23—N4	6.4 (19)
C2—C1—C6—C5	2.2 (19)	C19—C18—C23—C22	6.1 (19)
Br1—C1—C6—C5	−169.2 (10)	F8—C18—C23—C22	−172.8 (11)
C6—N1—C7—C8	115.2 (12)	C23—N4—C24—C25	124.3 (12)
Pt1—N1—C7—C8	−43.0 (13)	Pt2—N4—C24—C25	−46.0 (11)
N1—C7—C8—N2	53.0 (14)	C26—N5—C25—C24	81.0 (11)
C9—N2—C8—C7	78.8 (12)	C28—N5—C25—C24	−158.4 (9)
C11—N2—C8—C7	−159.7 (10)	Pt2—N5—C25—C24	−33.9 (11)
Pt1—N2—C8—C7	−36.8 (11)	N4—C24—C25—N5	52.8 (13)
C8—N2—C9—C10	59.8 (15)	C25—N5—C26—C27	63.8 (14)
C11—N2—C9—C10	−62.5 (14)	C28—N5—C26—C27	−58.5 (14)
Pt1—N2—C9—C10	174.5 (10)	Pt2—N5—C26—C27	179.5 (10)
C9—N2—C11—C12	−170.6 (11)	C25—N5—C28—C29	69.7 (13)
C8—N2—C11—C12	66.9 (13)	C26—N5—C28—C29	−168.0 (11)
Pt1—N2—C11—C12	−51.4 (13)	Pt2—N5—C28—C29	−51.0 (13)
C17—N3—C13—C14	−0.7 (17)	C34—N6—C30—C31	−0.8 (17)
Pt1—N3—C13—C14	177.2 (9)	Pt2—N6—C30—C31	176.3 (9)
N3—C13—C14—C15	1.1 (18)	N6—C30—C31—C32	0.4 (18)
C13—C14—C15—C16	−0.6 (19)	C30—C31—C32—C33	1.0 (18)
C14—C15—C16—C17	−0.3 (19)	C31—C32—C33—C34	−2.0 (18)
C13—N3—C17—C16	−0.3 (17)	C30—N6—C34—C33	−0.2 (18)
Pt1—N3—C17—C16	−178.1 (9)	Pt2—N6—C34—C33	−177.3 (9)
C15—C16—C17—N3	1 (2)	C32—C33—C34—N6	1.6 (19)

Observed and calculated chemical shifts for 1o and their comparison with calculated M-BrC₆F₄ organoamidoplatinum(II) compounds top

F	Observed (ppm)	Calculated for o-BrC₆F₄	F	Calculated for m-BrC₆F₄
F3	-140.6	-140.6	F2	-122.5
F6	-151.2	-151.1	F6	-145.1
F5	-160.9	-163.2	F4	-145.2
F4	-171.1	-174.8	F5	-169.2

Crystallographic data for the molecular structures of 1ox/1oy and comparison with 1p top

	ortho-1ox/1oy	1p (Ojha et al., 2015)
Empirical formula	C₃₄H₃₈Br_2.5Cl_1.5F₈N₆Pt₂	C₁₇H₁₉BrClF₄N₃Pt
Formula weight	1321.39	651.78
Crystal system	Triclinic	Monoclinic
Space group	P1	P2₁/c
a (Å)	9.4810 (19)	10.960 (2)
b (Å)	14.656 (3)	11.961 (2)
c (Å)	15.094 (3)	15.224 (3)
α (°)	75.02 (3)	90
β (°)	74.62 (3)	98.46 (3)
γ (°)	86.28 (3)	90
V (Å³)	1953.5 (8)	1974.0 (7)
Z	2	4
ρ (calcd) (Mg m^-3)	2.246	2.193
µ (mm^-1)	9.790	9.311
F(000)	1246.0	1232
Reflections collected/unique	24773/8572	22718/3354
R_int	0.0553	0.0267
2θ_max (°)	55.8	50.0
Goodness-of-fit on F²	1.052	1.126
R1 indices [I > 2σ(I)]	0.0626	0.0217
wR2 indices	0.1743	0.0518

Selected bond lengths (Å) and bond angles (°) for 1ox/1oy and comparison with 1p top

Bond	1ox	1oy	1p	Angle	1ox	1oy	1p
Pt—Cl	2.35 (3)	2.323 (7)	2.344 (10)	Cl—Pt—N(amide)	177.5 (9)	175.8 (4)	176.17 (9)
Pt—Br	2.534 (16)	2.62 (3)	–	N(amide)—Pt—N(Et₂)	84.2 (4)	83.5 (4)	82.65 (12)
Pt—N(amide)	1.993 (11)	2.006 (11)	2.006 (3)	N(amide)—Pt—N(py)	91.6 (4)	93.2 (4)	93.27 (12)
Pt—N(Et₂)	2.087 (10)	2.076 (9)	2.074 (3)	Cl—Pt—N(Et₂)	93.3 (8)	92.3 (4)	93.98 (9)
Pt—N(py)	2.034 (9)	2.026 (9)	2.013 (3)	Cl—Pt—N(py)	90.9 (8)	90.9 (4)	90.25 (8)
N(amide)—C(C₆F₄)	1.383 (19)	1.362 (19)	1.354 (4)	N(Et₂)—Pt—N(py)	174.8 (4)	173.8 (4)	173.53 (12)

Acknowledgements

AMB gratefully acknowledges financial support from the Australian Research Council. RO thanks the Australian Government for the provision of an Australian Postgraduate Award. All the authors thank Dr Craig M. Forsyth for his help in the refinement of the crystal data. X-ray crystallography data collection in this research was undertaken on the MX1 beamline at the Australian Synchrotron, which is a part of ANSTO (Cowieson et al., 2015 ). Open access publishing facilitated by Monash University, as part of the Wiley–Monash University agreement via the Council of Australian University Librarians.

Funding information

Funding for this research was provided by: Australian Research Council (grant No. DP120101470).

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