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The cation of the title complex salt, chlorido{2,2-dimethyl-N-[(E)-1-(pyridin-2-yl)ethyl­idene]propane-1,3-diamine}­pla­ti­n­um(II) tetra­fluoridoborate, [PtCl(C12H19N3)]BF4, exhibits a nominally square-planar PtII ion coordinated to a chloride ion [Pt—Cl = 2.3046 (9) Å] and three unique N-atom types, viz. pyridine, imine and amine, of the tridentate Schiff base ligand formed by the 1:1 condensation of 1-(pyridin-2-yl)ethanone and 2,2-dimethyl­propane-1,3-diamine. The cations are π-stacked in inversion-related pairs (dimers), with a mean plane separation of 3.426 Å, an intra­dimer Pt...Pt separation of 5.0785 (6) Å and a lateral shift of 3.676 Å. The centroid (Cg) of the pyridine ring is positioned approximately over the PtII ion of the neighbouring cation (Pt...Cg = 3.503 Å).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112023748/fn3105sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112023748/fn3105Isup2.hkl
Contains datablock I

CCDC reference: 893483

Comment top

Mono(cationic) polypyridine complexes of PtII are well known for their ability to form π-stacks in the crystalline solid state (Abel et al., 1994; Bardwell et al., 1994; Consorti et al., 2004). In the simplest type of stacking, discrete dimers are formed and the cations typically stack in a head-to-head fashion (Rotondo et al., 2003; Shafaatian et al., 2007; Kui et al., 2006). The PtII ions within these stacks span a range of Pt···Pt separations from ca 3.32 Å to beyond 7 Å, giving rise to several classes of stacked species based upon the lateral shift (LS) of one cation relative to the other (as derived by consideration of the metal ion coordinates). A recent systematic geometric and trigonometric analysis of π-stacked centrosymmetric dimers in terpyridine complexes of PtII (Field et al., 2011) showed that there are three categories of dimer based on the metrics of their interactions. Type-I dimers have short lateral shifts typically ranging from 0 to 1.6 Å, exhibit head-to-head overlap, and are governed by stabilizing Pt···Pt 5dz2···5dz2 orbital interactions as well as ππ interactions between stacked pyridine rings. The Pt···Pt orbital overlaps in type-I dimers lead to characteristic and potentially exploitable long-lived 3MmlCT emissive states (MmlCT, metal-to-metal-ligand charge-transfer) in the crystalline solids (Field et al., 2008; Field & Grimmer et al., 2010; Mathew & Sun, 2010). Type-II dimers exhibit head-to-head overlap and have longer lateral shifts (1.8–3.5 Å), consequently lacking Pt···Pt orbital overlaps, and are stabilized by ππ interactions and cation···π interactions. These dimers have normal 3mlCT emission in the solid state (Wen et al., 2011; Field & Gertenbach et al., 2010). The third category of dimers (type III) have long-range head-to-tail overlap, LS values in the range 5.5–7.5 Å, and are stabilized mainly by ππ interactions. In each class of dimeric species, ππ interactions are prevalent between the pyridine rings of the stacked cations. Furthermore, the interplanar spacings, or mean plane separation (MPS) values, span the range 3.2–3.5 Å (Field et al., 2011) and are similar in magnitude to that of graphite (3.35 Å; Bacon, 1951), the archetypal π-stacked aromatic system.

Our initial objective in this study was to synthesize and structurally characterize dicationic tetradentate bis(pyridyl–imine) chelates of PtII in an effort to determine whether or not the charge on the cation impacts on the π-stacking, the photophysics of this class of compounds, and the ability of such species to bind to DNA, particularly in view of a significant body of recent literature highlighting the DNA-targeting behaviour of cytotoxic PtII complexes bearing pyridine-based ligands (Rubino et al., 2011; Shi et al., 2010; Ruiz et al., 2010). The tetradentate ligand chosen for our study, 2,2-dimethyl-N,N'-bis[(pyridin-2-yl)ethylene]propane-1,3-diamine, was synthesized by the condensation of two molar equivalents of 1-(pyridin-2-yl)ethanone with one molar equivalent of 2,2-dimethylpropane-1,3-diamine and fully characterized prior to use in reaction with K2[PtCl4]. However, hydrolysis of one of the Schiff base imine units occurred during metalation and resulted in the isolation of the novel tridentate bis(chelate) of PtII, chlorido{2,2-dimethyl-N-[(E)-1-(pyridin-2-yl)ethylidene]propane-1,3-diamine}platinum(II) tetrafluoridoborate, hereafter (I). This mono(pyridyl–imine) complex of PtII has a net cationic charge and is still sufficiently planar and aromatic to assemble into π-stacked dimers in the crystalline solid state. Interestingly, two other mono(pyridyl–imine) complexes of PtII have been analysed by single-crystal X-ray diffraction (Mandal et al., 2010; Hinman et al., 2000), and show similar π-stacking behaviour to (I), suggesting that the presence of a single pyridine moiety as part of a chelating ligand for PtII might be a sufficient structural motif for π-stacking.

The cation of (I) is predominantly planar with the exception of the central C atom (C9) of the substituted propyl bridge linking the imine (N2) and amine (N3) N atoms, which is canted above the plane of the metal ion and four coordinated ligand atoms. The six-membered chelate ring based on these two N-atom donors adopts a typical half-chair conformation. The nominally square-planar PtII ion is coordinated to three chemically distinct N-atom types: pyridine (N1), imine (N2) and amine (N3), as shown in Fig. 1. The Pt—Npyridine and Pt—Nimine distances are equivalent at 2.007 (3) and 2.003 (3) Å, respectively, consistent with the fact that both of these N-atom types exhibit sp2-hybridization and are donors within a five-membered chelate ring (Table 1). The Pt—Npyridine bond distance is consistent with those observed between pyridine and PtII in a variety of polypyridine complexes of the metal, including terpyridine derivatives (Field et al., 2011). This suggests that the five-membered chelate ring incorporating the pyridine and imine groups in (I) is not substantially different from the five-membered chelate rings in polypyridine chelates of the metal. The Pt—Namine distance, being part of a six-membered chelate ring and sp3-hybridized, is commensurately longer at 2.038 (3) Å. The fourth coordination site of the metal ion is occupied by a chloride ligand consistent with similar coordination interactions for PtII derivatives in the literature (Che et al., 2011; Panda et al., 2005). The Pt1—Cl1 bond measures 2.3046 (9) Å .

Because the pyridyl–imine ligand of (I) comprises adjacent five- and six-membered chelate rings, the bond angles subtended at the PtII ion deviate significantly from the ideal 90° angles expected for a truly square-planar geometry. From Table 1, it is evident that the N1—Pt1—N2 bond angle within the five-membered chelate ring is particularly acute at 80.25 (12)°, while the N2—Pt1—N3 bond angle of the six-membered chelate ring is correspondingly quite obtuse, measuring 97.62 (12)°. This significant difference in the cis-N—Pt—N bond angles is in fact large enough to be clearly evident upon visual inspection of Fig. 1. The distortion of the coordination sphere of the metal ion away from an idealized square-planar geometry is further reflected by the cis-N—Pt—Cl bond angles, which measure 96.48 (9) and 85.68 (8)° for the N1—Pt1—Cl1 and N3—Pt1—Cl1 angles, respectively. The four bond angles subtended at the metal centre by the coordinated ligands sum to 360.03°. The perpendicular displacements of the four ligand donor atoms from their mean plane are -0.022 (2), 0.023 (1), -0.021 (1) and 0.019 (1) Å for N1, N2, N3 and Cl1, respectively. These out-of-plane displacements of the ligand donor atoms from the plane containing the metal ion are small and confirm the fundamentally square-planar 5d8 geometry and electron configuration for the PtII ion. Moreover, if we define the nine-atom mean plane of the cation by all sp2-hybridized C and N atoms plus the metal ion, the perpendicular displacements of the individual atoms from this mean plane are not inconsistent with a generally planar chelate system: N1 0.034 (3) Å; C1 0.039 (3) Å; C2 -0.002 (3) Å; C3 -0.053 (3) Å; C4 -0.014 (3) Å; C5 0.024 (3) Å; C6 0.061 (3) Å; N2 -0.050 (2) Å; Pt1 -0.039 (2) Å. (For this set of atomic displacements, negative values indicate a displacement perpendicular to the nine-atom mean plane in the same direction as the out-of-plane C atom of the six-membered chelate ring, C9, in Fig. 1.)

Inspection of the extended structure of (I) in Figs. 1 and 2 reveals that the tetrafluoridoborate anion is hydrogen bonded to the coordinated amino group H atoms (H3A and H3B) of two adjacent non-interacting cations (related by an inversion centre). From Table 2, the inequivalent N···F distances are 2.963 (4) and 3.005 (4) Å. The two inversion-related ion pairs therefore make up an asymmetric tetrad comprising two cations and their charge-balancing anions. Several other less conventional hydrogen bonds with longer donor···acceptor distances are also present (Table 2) and primarily involve C—H donors and acceptors such as the F atoms from nearby BF4- ions, as well as the coordinated chloride ligand of a nearby cation. Collectively, the data suggest that ion pairing in (I) mediated mainly by the shorter conventional N—H···F interactions is probably one of the more significant contributors to the stability of the salt in the solid state.

As noted earlier, pyridine complexes of PtII are well known for their ability to π-stack principally in the solid state, but also in solution depending on the solvent used (Tam et al., 2008). In the crystal structure of (I), pairs of cations are π-stacked in a head-to-head orientation (Figs. 3a and 3b) to form inversion pairs or dimers (we use the Pt—Cl bond vectors of the interacting cations to define the relative orientations of the stacked cations). The MPS between the nine-atom mean planes of the interacting cations is 3.426 Å. This is slightly larger than the graphite interlayer spacing of 3.35 Å (Bacon, 1951), but consistent with the normal range (3.33–3.48 Å) observed for terpyridine complexes of PtII (Field et al., 2011) and that for π-stacked ring systems in general (Hunter & Sanders, 1990; Janiak, 2000). Since the PtII cation has a perpendicular displacement of 0.039 (2) Å above the nine-atom mean plane in a direction away from the intradimer space, the metal-to-metal perpendicular displacement (MMPD) for the cations within the dimer is 3.504 Å. Together with the Pt···Pt separation of 5.0785 (6) Å, these values can be used to calculate the LS for the stacked cations (3.676 Å) based on the metal ion coordinates (Fig. 3b). The LS value for (I) is larger than that for many considerably more aromatic terpyridine complexes of PtII, for which LS values are typically < 3 Å (Field et al., 2011, Buchner et al., 1999). This presumably reflects two factors unique to (I): (a) the geometry of the ligand, which obviously lacks the central pyridine ring of terpyridine-based dimers (stacking of the central pyridine rings of two interacting terpyridine ligands favours modestly offset cation–cation interactions) and (b) the likely existence of a significantly stabilizing metal···π interaction (Mecozzi et al., 1996) involving the PtII ion of one cation and the pyridine ring of the second chelate of the dimer. The distance for this interaction is Pt1···Cg1v = 3.503 Å, where Cg1v is the centre of gravity of the pyridine ring of the second ligand in the dimer [symmetry code: (v) -x+1, -y, -z+2], and may be thought of as being predominantly electrostatic in origin (an electron-rich π-system donating electron density to an electron-deficient metal cation). Fig. 3(a) illustrates the slightly offset Pt···π interaction more clearly when the dimer is viewed perpendicular to the nine-atom mean plane of the upper cation. The π-stacking in (I) is similar as far as the overall arrangement of the cations is concerned to that observed for centrosymmetric dimers of mer-methyl{2-{[2-(dimethylamino)ethyl]iminomethyl}pyridine-κ3N,N',N''}platinum(II) trifluoromethanesulfonate (Hinman et al., 2000) [Cambridge Structural Database (Allen, 2002) refcode KERQAZ]. Interestingly, the latter complex has larger MPS, LS and Pt···Pt distances [3.60, 4.99 and 6.1501 (3) Å, respectively] than those observed for dimers of (I). These structural differences can be traced principally to the steric repulsion between one of the two N—CH3 groups of one ligand pointing into the space between the stacked cations and hence directly at the pyridine ring of the second ligand within the dimer. This effect is clearly absent in (I) because the bulky methyl groups appended to the six-membered chelate ring are positioned above the nine-atom mean plane of the chelate and away from the intradimer space, enabling a tighter interaction for the stacked cation pairs.

Related literature top

For related literature, see: Abel et al. (1994); Allen (2002); Bacon (1951); Bardwell et al. (1994); Buchner et al. (1999); Che et al. (2011); Consorti et al. (2004); Field et al. (2008, 2011); Field, Gertenbach, Jaganyi, McMillin, Shaira & Stewart (2010); Field, Grimmer, Munro & Waldron (2010); Hinman et al. (2000); Hunter & Sanders (1990); Janiak (2000); Kui et al. (2006); Mandal et al. (2010); Mathew & Sun (2010); Mecozzi et al. (1996); Panda et al. (2005); Rotondo et al. (2003); Rubino et al. (2011); Ruiz et al. (2010); Shafaatian et al. (2007); Shi et al. (2010); Tam et al. (2008); Wen et al. (2011).

Experimental top

All reagents were purchased from Aldrich and were used as received. Standard solvent purification and instrumental analysis methods for compound characterization were used.

For the synthesis of 2,2-dimethyl-N,N'-bis[(pyridin-2-yl)ethylene]propane-1,3-diamine, 2,2-dimethylpropane-1,3-diamine (10 mmol) was stirred in methanol (20 ml). 2-Acetylpyridine (20 mmol) was added, the temperature increased and the reaction mixture was refluxed for 8 h. The solvent was reduced in volume. MgSO4 was added and then filtered off, washing with dichloromethane (~10 ml). An orange oil was obtained (yield: 2.723 g, 89%). UV–vis (CH3OH; λmax, nm): 259.0 (sh), 266.0, 280.0 (sh), 299.0. 1H NMR (500 MHz, CDCl3): δ 8.56 (d, J = 4.5 Hz, 2H, NpyCHCH), 7.73 (d, J = 7.90 Hz, 2H, NpyCHCHCHCHC), 7.65 (t of d, J = 7.5, 1.8 Hz, 2H, NpyCHCHCHCH), 7.14 (t of d, J = 6.1, 1.3 Hz, 2H, NpyCHCHCH), 2.52 (d, J = 13.1 Hz, 2H, N—CHHC–), 2.38 (d, J = 13.0 Hz, 2H, N—CHHC—), 1.38 (s, 6H, –C(CH3)N–), 1.11 [s, 6H, C(CH3)2]. 13C NMR (125 MHz, CDCl3): δ 163.6 (NC), 155.7 [NpyC—C(CH3)N], 148.9 (NpyCHCH), 136.6 (NpyCHCHCHCH), 127.0 (NpyCHCHCH), 121.6 (NpyCHCHCHCH), 71.0 [C(CH3)2], 53.2 (–CH2–), 31.6 [C(CH3)N], 23.5 [C(CH3)2]. IR ν(cm–1): 3323, 3315, 3052, 3004, 2950, 2924, 2902, 2864, 1699, 1641, 1587, 1567, 1465, 1429, 1384, 1365, 1297, 1283, 1239, 1201, 1150, 1097, 1045, 993, 953, 909, 865, 834, 781, 743, 719, 645, 621, 574, 509, 491, 420, 404. HR–ESI–MS: m/z 309.2076 [M]+; calculated for C19H25N4: 309.2079.

For the synthesis of (I), N,N'-bis[(pyridin-2-yl)ethylene]-2,2-dimethylpropane-1,3-diamine (0.3 mmol) was dissolved in acetonitrile (1 ml). The metal salt, potassium tetrachloroplatinate (0.3 mmol), was added dropwise dissolved in distilled water (1.5 ml). Silver hexafluorophosphate(V) (1.2 mmol) was added to the solution dropwise as a suspension in acetonitrile (5 ml). The mixture was refluxed for more than 30 h. After cooling to room temperature overnight, the solution was filtered. Aliquots of the filtrate were placed in test tubes and layered with ethanol; the remainder of the solution was left to evaporate slowly. Amorphous solid formed after slow evaporation of the solvent was dissolved in 2-methoxyethanol (or distilled H2O) and layered in test tubes with diethyl ether (or ethanol). Spectroscopic analysis (1H NMR) of the bulk powder precipitates from these tubes unfortunately revealed a mixture of products. However, an X-ray-quality crystal was isolated from a generally amorphous precipitate in one of these crystallization attempts. The X-ray structure revealed the presence of the tetrafluoridoborate salt of an unintended reaction product, specifically salt (I). Analysis of the commercial source of AgPF6 used in our laboratory by LC–MS and 11B NMR identified the presence of the BF4- ion as a minor impurity (< 1.5%).

Salt (I) is evidently an unintended reaction product from the above method and reflects partial hydrolysis of the bis(pyridyl–imine) ligand as well crystallization of the cation with a minor impurity anion. Clearly the synthetic method described here is not optimal for a general synthesis of (I). Given the paucity of structures such as (I) in the literature and studies on this class of compounds in general, a higheryielding and more direct method for preparing (I) as well as a range of derivatives with different diamine precursors is currently being developed in our laboratory and will be reported on elsewhere.

Refinement top

All H atoms, except those of the amino group, were constrained during refinement. H atoms attached to amino atom N3 were allowed to refine freely. The remaining H atoms were positioned geometrically and refined using a riding model, with C—H = 0.99 Å and Uiso(H) = 1.2Ueq(C) for methylene H atoms, C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms, and C—H = 0.98 Å and Uiso(H) = 1.2Ueq(C) for methyl H atoms. For methyl H atoms, the torsion angle was optimized to fit the electron density.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as spheres of an arbitrary radius. The hydrogen bond between amine atom H3A and atom F1 of the anion is shown as a broken cylinder.
[Figure 2] Fig. 2. A view of the unit-cell packing of (I). Pairs of cations and hydrogen-bonded anions are related by centres of inversion at [0, 0, 1/2] and [1, 1, 1/2]. Atoms are rendered as spheres of arbitrary radii and bonds as cylinders. Only H atoms involved in hydrogen bonding are shown for clarity.
[Figure 3] Fig. 3. (a) Selectively labelled view of an inversion-related cation pair (i.e. dimer) perpendicular to the nine-atom mean plane of the upper cation defined by the pyridine ring, the imine N and C atoms, and the PtII ion. Using the Pt—Cl bond vectors to define the relative orientations of the cations, the geometry of the dimer is best described as an offset head-to-head π-stacked pair. (b) An edge-on view of the dimer down the Cl—Pt bond vector of the upper cation. The Pt···Pt distance and MPS are indicated. The trigonometric relationships involving the PtII ions are shown on the triangle below the dimer. The MMPD is the metal-to-metal perpendicular distance. Because the PtII ions are displaced above and below the nine-atom mean plane of the top and bottom cations by 0.039 Å, respectively, the MMPD is not equivalent to the MPS. The LS is calculated using Pythagoras' theorem from the MMPD and Pt···Pt ion separation. [Symmetry code: (i) x+1, -y, -z+2.]
chlorido{2,2-dimethyl-N-[(E)-1-(pyridin-2-yl)ethylidene]propane- 1,3-diamine}platinum(II) tetrafluoridoborate top
Crystal data top
[PtCl(C12H19N3)]BF4F(000) = 992
Mr = 522.65Dx = 2.124 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 6382 reflections
a = 11.0907 (16) Åθ = 2.4–28.5°
b = 11.1644 (16) ŵ = 8.79 mm1
c = 13.480 (2) ÅT = 100 K
β = 101.664 (2)°Shard, orange
V = 1634.6 (4) Å30.25 × 0.25 × 0.20 × 0.20 (radius) mm
Z = 4
Data collection top
Bruker APEXII CCD
diffractometer
3829 independent reflections
Radiation source: fine-focus sealed tube3594 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
ϕ and ω scansθmax = 28.6°, θmin = 2.4°
Absorption correction: for a cylinder mounted on the ϕ axis
[the interpolation procedure of Dwiggins (1975) was used with some modification]
h = 1414
Tmin = 0.062, Tmax = 0.088k = 1414
9381 measured reflectionsl = 1017
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.0462P)2 + 1.2692P]
where P = (Fo2 + 2Fc2)/3
3829 reflections(Δ/σ)max = 0.003
203 parametersΔρmax = 2.72 e Å3
0 restraintsΔρmin = 2.98 e Å3
Crystal data top
[PtCl(C12H19N3)]BF4V = 1634.6 (4) Å3
Mr = 522.65Z = 4
Monoclinic, P21/nMo Kα radiation
a = 11.0907 (16) ŵ = 8.79 mm1
b = 11.1644 (16) ÅT = 100 K
c = 13.480 (2) Å0.25 × 0.25 × 0.20 × 0.20 (radius) mm
β = 101.664 (2)°
Data collection top
Bruker APEXII CCD
diffractometer
3829 independent reflections
Absorption correction: for a cylinder mounted on the ϕ axis
[the interpolation procedure of Dwiggins (1975) was used with some modification]
3594 reflections with I > 2σ(I)
Tmin = 0.062, Tmax = 0.088Rint = 0.029
9381 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.075H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 2.72 e Å3
3829 reflectionsΔρmin = 2.98 e Å3
203 parameters
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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
B10.5240 (4)0.5256 (4)0.7531 (3)0.0194 (8)
C10.3827 (3)0.0259 (3)0.8316 (3)0.0176 (7)
H10.31810.08160.83230.021*
C20.3561 (4)0.0820 (3)0.7805 (3)0.0209 (7)
H20.27440.10000.74680.025*
C30.4511 (4)0.1632 (3)0.7794 (3)0.0223 (8)
H30.43510.23610.74290.027*
C40.5700 (4)0.1371 (3)0.8324 (3)0.0203 (7)
H40.63520.19280.83450.024*
C50.5904 (3)0.0270 (3)0.8819 (3)0.0161 (7)
C60.7108 (3)0.0131 (3)0.9402 (3)0.0156 (7)
C70.8161 (3)0.0727 (3)0.9612 (3)0.0195 (7)
H7A0.87740.04421.01920.029*
H7B0.85380.07840.90160.029*
H7C0.78620.15180.97650.029*
C80.8301 (3)0.1743 (3)1.0277 (3)0.0187 (7)
H8A0.89860.14140.99900.022*
H8B0.84250.14751.09910.022*
C90.8375 (4)0.3122 (3)1.0262 (3)0.0181 (7)
C100.7406 (3)0.3701 (3)1.0777 (3)0.0184 (7)
H10A0.74110.32831.14260.022*
H10B0.76400.45461.09370.022*
C110.9646 (3)0.3436 (4)1.0906 (4)0.0249 (8)
H11A1.02910.30671.06070.037*
H11B0.97020.31341.15970.037*
H11C0.97520.43081.09250.037*
C120.8278 (4)0.3583 (3)0.9183 (3)0.0230 (8)
H12A0.74920.33280.87650.034*
H12B0.89570.32570.89010.034*
H12C0.83230.44600.91910.034*
Cl10.35981 (8)0.29778 (7)0.91997 (8)0.01894 (19)
F10.5637 (2)0.5531 (2)0.85623 (17)0.0252 (5)
F20.5498 (2)0.4068 (2)0.73558 (18)0.0266 (5)
F30.5834 (3)0.6008 (2)0.6958 (2)0.0325 (6)
F40.3974 (2)0.5459 (2)0.7264 (2)0.0328 (6)
N10.4970 (3)0.0535 (3)0.8798 (2)0.0156 (6)
N20.7131 (3)0.1232 (3)0.9713 (2)0.0155 (6)
N30.6142 (3)0.3671 (3)1.0160 (2)0.0159 (6)
H3A0.6094 (3)0.423 (2)0.9675 (17)0.019*
H3B0.5625 (19)0.3892 (9)1.0558 (14)0.019*
Pt10.551556 (11)0.209525 (11)0.948209 (9)0.01263 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
B10.0221 (19)0.0183 (19)0.0177 (19)0.0017 (15)0.0034 (15)0.0015 (16)
C10.0204 (16)0.0185 (16)0.0128 (16)0.0001 (13)0.0007 (13)0.0021 (14)
C20.0263 (18)0.0204 (17)0.0147 (17)0.0052 (14)0.0010 (14)0.0024 (15)
C30.033 (2)0.0157 (17)0.0179 (18)0.0043 (15)0.0034 (15)0.0008 (15)
C40.0290 (19)0.0145 (16)0.0182 (18)0.0004 (14)0.0069 (15)0.0010 (14)
C50.0202 (16)0.0146 (15)0.0148 (16)0.0005 (13)0.0063 (13)0.0034 (14)
C60.0177 (15)0.0145 (15)0.0163 (16)0.0004 (12)0.0077 (13)0.0026 (13)
C70.0200 (17)0.0154 (16)0.0241 (19)0.0038 (13)0.0066 (14)0.0012 (14)
C80.0191 (17)0.0153 (16)0.0210 (19)0.0010 (14)0.0027 (14)0.0005 (15)
C90.0195 (17)0.0116 (14)0.023 (2)0.0026 (13)0.0033 (15)0.0029 (15)
C100.0173 (16)0.0175 (16)0.0192 (18)0.0002 (13)0.0011 (13)0.0029 (14)
C110.0177 (17)0.0189 (18)0.036 (2)0.0000 (14)0.0013 (16)0.0029 (17)
C120.0251 (18)0.0201 (17)0.027 (2)0.0013 (14)0.0119 (15)0.0023 (16)
Cl10.0153 (4)0.0180 (4)0.0222 (5)0.0033 (3)0.0006 (3)0.0017 (3)
F10.0319 (12)0.0229 (11)0.0198 (11)0.0021 (10)0.0031 (9)0.0016 (10)
F20.0381 (13)0.0167 (10)0.0266 (12)0.0019 (9)0.0100 (10)0.0013 (9)
F30.0471 (15)0.0235 (12)0.0320 (14)0.0039 (11)0.0205 (12)0.0025 (10)
F40.0245 (11)0.0295 (12)0.0400 (15)0.0024 (10)0.0040 (10)0.0003 (12)
N10.0197 (14)0.0153 (14)0.0121 (13)0.0000 (11)0.0041 (11)0.0000 (12)
N20.0170 (13)0.0162 (14)0.0135 (14)0.0008 (11)0.0035 (11)0.0025 (12)
N30.0150 (13)0.0154 (13)0.0179 (15)0.0011 (11)0.0047 (11)0.0010 (12)
Pt10.01325 (10)0.01154 (10)0.01271 (10)0.00077 (4)0.00168 (6)0.00079 (4)
Geometric parameters (Å, º) top
B1—F21.387 (5)C8—C91.542 (5)
B1—F31.393 (5)C8—H8A0.9900
B1—F41.395 (5)C8—H8B0.9900
B1—F11.405 (5)C9—C121.526 (6)
C1—N11.338 (4)C9—C101.536 (5)
C1—C21.389 (5)C9—C111.539 (5)
C1—H10.9500C10—N31.478 (4)
C2—C31.392 (6)C10—H10A0.9900
C2—H20.9500C10—H10B0.9900
C3—C41.398 (5)C11—H11A0.9800
C3—H30.9500C11—H11B0.9800
C4—C51.394 (5)C11—H11C0.9800
C4—H40.9500C12—H12A0.9800
C5—N11.367 (4)C12—H12B0.9800
C5—C61.475 (5)C12—H12C0.9800
C6—N21.297 (4)Cl1—Pt12.3046 (9)
C6—C71.492 (5)N1—Pt12.007 (3)
C7—H7A0.9800N2—Pt12.003 (3)
C7—H7B0.9800N3—Pt12.038 (3)
C7—H7C0.9800N3—H3A0.8953
C8—N21.479 (4)N3—H3B0.8953
F2—B1—F3110.2 (3)C12—C9—C8110.9 (3)
F2—B1—F4110.1 (3)C10—C9—C8111.7 (3)
F3—B1—F4108.8 (3)C11—C9—C8105.4 (3)
F2—B1—F1110.1 (3)N3—C10—C9113.9 (3)
F3—B1—F1109.1 (3)N3—C10—H10A108.8
F4—B1—F1108.5 (3)C9—C10—H10A108.8
N1—C1—C2121.7 (3)N3—C10—H10B108.8
N1—C1—H1119.1C9—C10—H10B108.8
C2—C1—H1119.1H10A—C10—H10B107.7
C1—C2—C3119.0 (3)C9—C11—H11A109.5
C1—C2—H2120.5C9—C11—H11B109.5
C3—C2—H2120.5H11A—C11—H11B109.5
C2—C3—C4119.8 (4)C9—C11—H11C109.5
C2—C3—H3120.1H11A—C11—H11C109.5
C4—C3—H3120.1H11B—C11—H11C109.5
C5—C4—C3118.2 (3)C9—C12—H12A109.5
C5—C4—H4120.9C9—C12—H12B109.5
C3—C4—H4120.9H12A—C12—H12B109.5
N1—C5—C4121.3 (3)C9—C12—H12C109.5
N1—C5—C6114.3 (3)H12A—C12—H12C109.5
C4—C5—C6124.3 (3)H12B—C12—H12C109.5
N2—C6—C5114.6 (3)C1—N1—C5119.9 (3)
N2—C6—C7125.6 (3)C1—N1—Pt1126.2 (2)
C5—C6—C7119.7 (3)C5—N1—Pt1113.9 (2)
C6—C7—H7A109.5C6—N2—C8119.3 (3)
C6—C7—H7B109.5C6—N2—Pt1116.6 (2)
H7A—C7—H7B109.5C8—N2—Pt1123.9 (2)
C6—C7—H7C109.5C10—N3—Pt1118.1 (2)
H7A—C7—H7C109.5C10—N3—H3A107.8
H7B—C7—H7C109.5Pt1—N3—H3A107.8
N2—C8—C9114.9 (3)C10—N3—H3B107.8
N2—C8—H8A108.5Pt1—N3—H3B107.8
C9—C8—H8A108.5H3A—N3—H3B107.1
N2—C8—H8B108.5N2—Pt1—N180.25 (12)
C9—C8—H8B108.5N2—Pt1—N397.62 (12)
H8A—C8—H8B107.5N1—Pt1—N3177.51 (11)
C12—C9—C10111.6 (3)N2—Pt1—Cl1176.53 (9)
C12—C9—C11109.9 (3)N1—Pt1—Cl196.48 (9)
C10—C9—C11107.0 (3)N3—Pt1—Cl185.68 (8)
N1—C1—C2—C30.1 (5)C4—C5—N1—Pt1175.9 (3)
C1—C2—C3—C42.2 (6)C6—C5—N1—Pt14.2 (4)
C2—C3—C4—C52.4 (6)C5—C6—N2—C8178.1 (3)
C3—C4—C5—N10.5 (5)C7—C6—N2—C83.8 (5)
C3—C4—C5—C6179.7 (4)C5—C6—N2—Pt16.6 (4)
N1—C5—C6—N27.1 (5)C7—C6—N2—Pt1171.5 (3)
C4—C5—C6—N2173.0 (3)C9—C8—N2—C6157.9 (3)
N1—C5—C6—C7171.1 (3)C9—C8—N2—Pt127.1 (4)
C4—C5—C6—C78.7 (5)C9—C10—N3—Pt146.9 (4)
N2—C8—C9—C1262.2 (4)C6—N2—Pt1—N13.5 (3)
N2—C8—C9—C1063.0 (4)C8—N2—Pt1—N1178.5 (3)
N2—C8—C9—C11178.9 (3)C6—N2—Pt1—N3177.8 (3)
C12—C9—C10—N349.3 (4)C8—N2—Pt1—N32.8 (3)
C11—C9—C10—N3169.6 (3)C1—N1—Pt1—N2178.1 (3)
C8—C9—C10—N375.5 (4)C5—N1—Pt1—N20.7 (2)
C2—C1—N1—C51.8 (5)C1—N1—Pt1—Cl13.1 (3)
C2—C1—N1—Pt1175.4 (3)C5—N1—Pt1—Cl1179.5 (2)
C4—C5—N1—C11.7 (5)C10—N3—Pt1—N212.1 (3)
C6—C5—N1—C1178.2 (3)C10—N3—Pt1—Cl1166.8 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···F10.902.082.963 (4)169
N3—H3B···F1i0.902.113.005 (4)177
C1—H1···F4ii0.952.403.055 (4)126
C2—H2···Cl1ii0.952.693.496 (4)144
C3—H3···F4iii0.952.473.353 (4)154
C7—H7B···F2iv0.982.323.301 (5)178
Symmetry codes: (i) x+1, y+1, z+2; (ii) x+1/2, y1/2, z+3/2; (iii) x, y1, z; (iv) x+3/2, y1/2, z+3/2.

Experimental details

Crystal data
Chemical formula[PtCl(C12H19N3)]BF4
Mr522.65
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)11.0907 (16), 11.1644 (16), 13.480 (2)
β (°) 101.664 (2)
V3)1634.6 (4)
Z4
Radiation typeMo Kα
µ (mm1)8.79
Crystal size (mm)0.25 × 0.25 × 0.20 × 0.20 (radius)
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionFor a cylinder mounted on the ϕ axis
[the interpolation procedure of Dwiggins (1975) was used with some modification]
Tmin, Tmax0.062, 0.088
No. of measured, independent and
observed [I > 2σ(I)] reflections
9381, 3829, 3594
Rint0.029
(sin θ/λ)max1)0.674
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.075, 1.08
No. of reflections3829
No. of parameters203
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)2.72, 2.98

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008).

Selected geometric parameters (Å, º) top
C1—N11.338 (4)N1—Pt12.007 (3)
C10—N31.478 (4)N2—Pt12.003 (3)
Cl1—Pt12.3046 (9)N3—Pt12.038 (3)
C1—N1—Pt1126.2 (2)N2—Pt1—N397.62 (12)
C5—N1—Pt1113.9 (2)N1—Pt1—N3177.51 (11)
C6—N2—Pt1116.6 (2)N2—Pt1—Cl1176.53 (9)
C8—N2—Pt1123.9 (2)N1—Pt1—Cl196.48 (9)
C10—N3—Pt1118.1 (2)N3—Pt1—Cl185.68 (8)
N2—Pt1—N180.25 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···F10.902.082.963 (4)169
N3—H3B···F1i0.902.113.005 (4)177
C1—H1···F4ii0.952.403.055 (4)126
C2—H2···Cl1ii0.952.693.496 (4)144
C3—H3···F4iii0.952.473.353 (4)154
C7—H7B···F2iv0.982.323.301 (5)178
Symmetry codes: (i) x+1, y+1, z+2; (ii) x+1/2, y1/2, z+3/2; (iii) x, y1, z; (iv) x+3/2, y1/2, z+3/2.
 

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