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ISSN: 2056-9890

Crystal structure of chlorido­{4,5-dimeth­­oxy-2-[(2,3-η)-2-prop-2-en-1-yl]phenyl-κC1}(piperidine-κN)platinum(II) ethanol monosolvate

aChemistry Department, University of Kinshasa, Kinshasa XI BP 190, D.R. Congo, bChemistry Department, Hanoi National University of Education, 136 – Xuan Thuy – Cau Giay, Hanoi, Vietnam, and cChemistry Department, KU Leuven, Celestijnenlaan 200F, B-3001, Leuven (Heverlee), Belgium
*Correspondence e-mail: luc.vanmeervelt@chem.kuleuven.be

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 30 September 2014; accepted 27 October 2014; online 31 October 2014)

In the title compound, [Pt(C11H13O2)Cl(C5H11N)]·C2H5OH, the PtII cation is penta­coordinated in a distorted square-planar geometry. In the crystal, inversion dimers showing C—H⋯Cl and C—H⋯π inter­actions are further stacked in columns along the a axis via C—H⋯π inter­actions. The ethanol solvate mol­ecule inter­acts with neighbouring meth­oxy groups of methyl­eugenol through O—H⋯O hydrogen bonds.

1. Chemical context

Methyl­eugenol or 4-allyl-1,2-di­meth­oxy­benzene (Meug, C11H14O2) is a natural product occurring in a number of plants such as fennel, pimento, lemongrass and nutmeg, and frequently used in perfumery and as flavouring agent (Ford et al., 2000[Ford, R. A., Domeyer, B., Easterday, O., Maier, K. & Middleton, J. (2000). Regul. Toxicol. Pharmacol. 31, 166-181.]). Methyl­eugenol is used as a fruit-fly attractant in agriculture (Todd et al., 2008[Todd, E. S., James, E., Elaine, P., Suk, L. W. & Ritsuo, N. (2008). Entomol. Exp. Appl. 128, 380-388.]) and in the formulation of UV absorbers, analgesics, and psychotropic drugs in medicine (Darshan & Doreswamy, 2004[Darshan, S. & Doreswamy, R. (2004). Phytother. Res. 18, 343-357.]; Freeman & Alder, 2002[Freeman, S. & Alder, J. F. (2002). Eur. J. Med. Chem. 37, 527-539.]). Platinum(II) complexes containing methyl­eugenol of formula [PtCl2(Meug)(Amine)] and deprotonated methyl­eugenol of formula [PtCl(Meug-1H)(Amine)] have been described in very few works (Da et al., 2007[Da, T. T., Minh, N. T. T., Chi, N. T. T. & Dinh, N. H. (2007). Polyhedron, 26, 3271-3276.], 2010[Da, T. T., Kim, Y., Mai, T. T. C., Cuong, N. C. & Dinh, N. H. (2010). J. Coord. Chem. 63, 473-483.], 2015[Da, T. T., Chi, N. T. T., Van Meervelt, L., Mangwala Kimpende, P. & Dinh, N. H. (2015). Polyhedron, 85, 104-109.]). It is inter­esting that some of these complexes exhibit strong activities on human cancer cells KB with IC50 = 3.2–3.7 µg/mL (Da et al., 2015[Da, T. T., Chi, N. T. T., Van Meervelt, L., Mangwala Kimpende, P. & Dinh, N. H. (2015). Polyhedron, 85, 104-109.]). Based on these observations and prompted by the fact that one of our research areas focuses on the design and synthesis of compounds with high biological activity starting from inexpensive natural products, we have prepared the title compound [PtCl(Meug-1H)(Piperidine)] and determined its crystal structure.

[Scheme 1]

2. Structural commentary

In [PtCl(Meug-1H)(piperidine)], the PtII cation is penta­coordinated with PtII at the centre of a distorted square-planar geometry. The methyl­eugenol is bound with the PtII cation both at the ethyl­enic double bond and at a deprotonated benzene carbon atom (Fig. 1[link]). The two meth­oxy groups of the methyl­eugenol part are almost in the phenyl plane, as illustrated by the torsion angles C2—C3—O1—C7 [−7.9 (6)°] and C5—C4—O2—C8 [−4.0 (6)°]. The piperidine is in the cis position with respect to the ethyl­enic double bond. The piperidine ring occurs in the usual chair conformation with the N1—Pt1 bond in the equatorial position. The best planes through the two six-membered rings make a dihedral angle of 24.6 (2)°. In order to avoid steric hindrance between Cl1 and the two ring systems, especially atoms C2 and C12, both rings rotate along their bond with Pt1. This is easier for the piperidine ring [resulting in a C12—N1—Pt1—Cl1 torsion angle of 70.7 (2)°] than for the phenyl ring [C2—C1—Pt1—Cl1 torsion angle of only −25.0 (4)°]. As a consequence the H12B⋯Cl1 distance (2.831 Å) is larger than the H2⋯Cl1 distance (2.789 Å).

[Figure 1]
Figure 1
Mol­ecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level and the O—H⋯O inter­actions shown as dashed lines.

3. Supra­molecular features

In the crystal packing (Fig. 2[link]), the complex forms inversion dimers by pairs of C—H⋯Cl and C—H⋯π inter­actions (C10—H10⋯Cl1 and C15—H15ACg1 inter­actions, Cg1 is the centroid of the C1–C6 aromatic ring, see Table 1[link]). These dimers are stacked in columns along [100] by C12—H12ACg1 inter­actions. The ethanol mol­ecule inter­acts by bifurcated O—H⋯O hydrogen bonds with both meth­oxy groups of methyl­eugenol and further on by C—H⋯O inter­actions to a neighboring meth­oxy group. No voids are present in the crystal packing.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A D—H H⋯A DA D—H⋯A
O3—H3⋯O1 0.84 2.10 2.869 (4) 152
O3—H3⋯O2 0.84 2.47 3.158 (4) 140
C10—H10⋯Cl1i 0.95 2.74 3.466 (4) 134
C7—H7A⋯O3ii 0.98 2.59 3.276 (6) 127
C15—H15ACg1i 0.99 2.68 3.572 (5) 149
C12—H12ACg1iii 0.99 2.61 3.529 (5) 154
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+1, -y+1, -z; (iii) -x+1, -y+1, -z+1.
[Figure 2]
Figure 2
View of the crystal packing for the title compound, with O—H⋯O, C—H⋯Cl and C—H⋯π hydrogen bonds shown as red, green and blue dashed lines, respectively. Cg1 is the centroid of the C1–C6 ring. [Symmetry codes: (i) −x, −y + 1, −z + 1; (ii) −x + 1, −y + 1, −z; (iii) −x + 1, −y + 1, −z + 1.]

4. Database survey

The Cambridge Structural Database (CSD, Version 5.35, May 2014; Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) contains 52 1,2-di­meth­oxy­phenyl fragments in which the meth­oxy oxygen atoms inter­act simultaneously with a third oxygen atom (O⋯O distance less than the sum of the van der Waals radii). The third oxygen atom belongs in descending order to a water, alcohol, oxime or carb­oxy­lic acid, and the mean O⋯O distance is 2.916 Å. In the 690 4-substituted 1,2-di­meth­oxy­phenyl fragments present in the CSD, the majority of the C—C—O—CH3 torsion angles vary between −28 and +32° (only 11 torsion angles are outside this region).

5. Synthesis and crystallization

The dinuclear complex [Pt2Cl2(Meug-1H)2] was prepared from K[PtCl3(Meug)] in high yield (85%) according to Da et al. (2010[Da, T. T., Kim, Y., Mai, T. T. C., Cuong, N. C. & Dinh, N. H. (2010). J. Coord. Chem. 63, 473-483.]).

The title compound was synthesized by adding a solution of 1 mmol of piperidine in 3 ml of acetone to a mixture of 408 mg (0.5 mmol) of [Pt2Cl2(Meug-1H)2] and 6ml of acetone. The reaction mixture was stirred at room temperature for 30 min. The obtained solution was cooled to 255 K after which the precipitate was collected and washed with Et2O. The yield was 320 mg (65%). The powder was dissolved in an acetone–ethanol mixture. Colourless plate-like crystals were harvested after slow evaporation of acetone at room temperature.

IR (cm−1): 3512 (νOH from ethanol solvate); 3247 (νNH); 3060, 2946, 2838 (νCH); 1581, 1557 (νC=C). 1H NMR (δ p.p.m.; d6-acetone, Bruker Avance 500 MHz): 7.00 (1H, s, 3J PtH = 38 Hz, H2), 6.57 (1H, s, H5), 4.71 (1H, m, 2J PtH = 74 Hz, H10), 3.86 (1H, d, 3J = 7 Hz, 2J PtH = 76 Hz, H11A), 3.71 (3H, s, methyl C7), 3.66 (3H, s, methyl C8), 3.61 (1H, dd, 2J = 17 Hz, 3J = 6 Hz, H9B), 3.57 (1H, d, 3J = 13 Hz, 2J PtH = 70 Hz, H11B), 3.19 (1H, t, 3Jaa = 12 Hz, H1), 3.10 (1H, d, 2Jae = 13 Hz, H16A), 3.08 (1H, d, 2Jae = 13 Hz, H12B), 2.95 (1H, qd, 2Jae = 13 Hz, 3Jaa = 12 Hz, 3Jae = 3 Hz, H12A), 2.93 (1H, qd, 2Jae = 13 Hz, 3Jaa = 12 Hz, 3Jae = 3 Hz, H16B), 2.53 (1H, d, 2J = 17 Hz, H9A), 1.68 (3H, d, 2Jae = 12 Hz, H13A, H14B, H15B), 1.59 (2H, m, H13B, H15A), 1.48 (1H, m, H14A). Calculated for [PtCl(Meug-1H)(Piperidine)]: C16H24ClNO2Pt, M = 491–495 au; found (by ESI MS, m/z): 490–494 ([M−H]+).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. All hydrogen atoms were placed in idealized positions and refined in riding mode with Uiso assigned the values to be 1.2 times those of their parent atoms (1.5 times for methyl and hydroxyl groups) with C—H distances of 0.95 (aromatic), 0.98 (meth­yl) and 0.99 Å (methyl­ene), N—H distance of 0.93 (NH) and O—H distance of 0.84 Å.

Table 2
Experimental details

Crystal data
Chemical formula [Pt(C11H13O2)Cl(C5H11N)]·C2H6O
Mr 538.97
Crystal system, space group Triclinic, P[\overline{1}]
Temperature (K) 100
a, b, c (Å) 8.5280 (2), 8.7520 (2), 13.3309 (3)
α, β, γ (°) 97.905 (1), 97.684 (1), 99.880 (1)
V3) 958.21 (4)
Z 2
Radiation type Cu Kα
μ (mm−1) 15.10
Crystal size (mm) 0.60 × 0.15 × 0.07
 
Data collection
Diffractometer Bruker SMART 6000
Absorption correction Multi-scan (SADABS; Bruker, 2003[Bruker (2003). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.107, 0.347
No. of measured, independent and observed [I > 2σ(I)] reflections 13448, 3533, 3410
Rint 0.050
(sin θ/λ)max−1) 0.612
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.069, 1.08
No. of reflections 3533
No. of parameters 220
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 1.57, −2.16
Computer programs: SMART and SAINT (Bruker, 2003[Bruker (2003). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 and SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]).

Supporting information


Chemical context top

Methyl­eugenol or 4-allyl-1,2-di­meth­oxy­benzene (Meug, C11H14O2) is a natural product occurring in a number of plants such as fennel, pimento, lemongrass and nutmeg, and frequently used in perfumery and as flavouring agent (Ford et al., 2000). Methyl­eugenol is used as a fruit-fly attra­ctant in agriculture (Todd et al., 2008) and in the formulation of UV absorbers, analgesics, and psychotropic drugs in medicine (Darshan & Doreswamy, 2004; Freeman & Alder, 2002). Platinum(II) complexes containing methyl­eugenol of formula [PtCl2(Meug)(Amine)] and deprotonated methyl­eugenol of formula [PtCl(Meug-1H)(Amine)] have been described in very few works (Da et al., 2007, 2010, 2015). It is inter­esting that some of these complexes exhibit strong activities on human cancer cells KB with IC50 = 3.2–3.7 µg/mL (Da et al., 2015). Based on these observations and prompted by the fact that one of our research areas focuses on the design and synthesis of compounds with high biological activity starting from inexpensive natural products, we have prepared the title compound [PtCl(Meug-1H)(Piperidine)] and determined its crystal structure.

Structural commentary top

In [PtCl(Meug-1H)(piperidine)], the PtII cation is penta­coordinated with PtII at the centre of a distorted trigonal bipyramid. The methyl­eugenol is bound with PtII both at the ethyl­enic double bond and a deprotonated benzene carbon atom (Fig. 1). The two meth­oxy groups of the methyl­eugenol part are almost in the phenyl plane, as illustrated by the torsion angles C2—C3—O1—C7 [-7.9 (6)°] and C5—C4—O2—C8 [-4.0 (6)°]. The piperidine is in the cis position with respect to the ethyl­enic double bond. The piperidine ring occurs in the usual chair conformation with the N1—Pt1 bond in the equatorial position. The best planes through the two six-membered rings make a dihedral angle of 24.6 (2)°. In order to avoid steric hindrance between Cl1 and the two ring systems, especially atoms C2 and C12, both rings rotate along their bond with Pt1. This is easier for the piperidine ring [resulting in a C12—N1—Pt1—Cl1 torsion angle of 70.7 (2)°] than for the phenyl ring [C2—C1—Pt1—Cl1 torsion angle of only -25.0 (4)°]. As a consequence the H12B···Cl1 distance (2.831 Å) is larger than the H2···Cl1 distance (2.789 Å).[Pt(C11H13O2)Cl(C5H11N)].C2H5OH

Supra­molecular features top

In the crystal packing (Fig. 2), the complex forms inversion dimers by pairs of C—H···Cl and C—H···π inter­actions (C10—H10···Cl1 and C15—H15A···Cg1 inter­actions, Cg1 is the centroid of the C1–C6 aromatic ring, see Table 1). These dimers are stacked in columns along [100] by C12—H12A···Cg1 inter­actions. The ethanol molecule inter­acts by O—H···O hydrogen bonds with both meth­oxy groups of methyl­eugenol and further on by C—H···O inter­actions to a neighboring meth­oxy group. No voids are present in the crystal packing.

Database survey top

The Cambridge Structural Database (CSD, Version 5.35, May 2014; Groom & Allen, 2014) contains 52 1,2-di­meth­oxy­phenyl fragments in which the meth­oxy oxygen atoms inter­act simultaneously with a third oxygen atom (O···O distance less than the sum of the van der Waals radii). The third oxygen atom belongs in descending order to a water, alcohol, oxime or carb­oxy­lic acid, and the mean O···O distance is 2.916 Å. In the 690 4-substituted 1,2-di­meth­oxy­phenyl fragments present in the CSD, the majority of the C—C—O—CH3 torsion angles vary between -28 and +32° (only 11 torsion angles are outside this region).

Synthesis and crystallization top

The dinuclear complex [Pt2Cl2(Meug-1H)2] was prepared from K[PtCl3(Meug)] in high yield (85%) according to Da et al. (2010).

The title compound was synthesized by adding a solution of 1 mmol of piperidine in 3 mL of acetone to a mixture of 408 mg (0.5mmol) of [Pt2Cl2(Meug-1H)2] and 6mL of acetone. The reaction mixture was stirred at room temperature for 30 min. The obtained solution was cooled to 255 K after which the precipitate was collected and washed with Et2O. The yield was 320 mg (65%). The powder was dissolved in an acetone–ethanol mixture. Colourless plate-like crystals were harvested after slow evaporation of acetone at room temperature.

IR (cm-1): 3512 (νOH from ethanol solvate); 3247 (νNH); 3060, 2946, 2838 (νCH); 1581, 1557 (νC=C). 1H NMR (δ p.p.m.; d6-acetone, Bruker Avance 500 MHz): 7.00 (1H, s, 3J PtH = 38 Hz, H2), 6.57 (1H, s, H5), 4.71 (1H, m, 2J PtH = 74 Hz, H10), 3.86 (1H, d, 3J = 7 Hz, 2J PtH = 76 Hz, H11A), 3.71 (3H, s, methyl C7), 3.66 (3H, s, methyl C8), 3.61 (1H, dd, 2J = 17 Hz, 3J = 6 Hz, H9B), 3.57 (1H, d, 3J = 13 Hz, 2J PtH = 70 Hz, H11B), 3.19 (1H, t, 3Jaa = 12 Hz, H1), 3.10 (1H, d, 2Jae = 13 Hz, H16A), 3.08 (1H, d, 2Jae = 13 Hz, H12B), 2.95 (1H, qd, 2Jae = 13 Hz, 3Jaa = 12 Hz, 3Jae = 3 Hz, H12A), 2.93 (1H, qd, 2Jae = 13 Hz, 3Jaa = 12 Hz, 3Jae = 3 Hz, H16B), 2.53 (1H, d, 2J = 17 Hz, H9A), 1.68 (3H, d, 2Jae = 12 Hz, H13A, H14B, H15B), 1.59 (2H, m, H13B, H15A), 1.48 (1H, m, H14A). Calculated for [PtCl(Meug-1H)(Piperidine)]: C16H24ClNO2Pt, M = 491--495 au; found (by ESI MS, m/z): 490–494 ([M-H]-).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. All hydrogen atoms were placed in idealized positions and refined in riding mode with Uiso assigned the values to be 1.2 times those of their parent atoms (1.5 times for methyl and hydroxyl groups) with C—H distances of 0.95 (aromatic), 0.98 (methyl) and 0.99 Å (methyl­ene), N—H distance of 0.93 (NH) and O—H distance of 0.84 Å.

Related literature top

For related literature, see: Allen (2002); Da et al. (2007, 2010, 2015); Darshan & Doreswamy (2004); Ford et al. (2000); Freeman & Alder (2002); Todd et al. (2008).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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).

Figures top
Molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level and the O—H···O interactions drawn as dashed lines.

View of the crystal packing for the title compound, with O—H···O, C—H···Cl and C—H···π hydrogen bonds drawn as red, green and blue dashed lines, respectively. Cg1 is the centroid of the C1–C6 ring. [Symmetry codes: (i) -x, -y + 1, -z + 1; (ii) -x + 1, -y + 1, -z; (iii) -x + 1, -y + 1, -z + 1.]
Chlorido{4,5-dimethoxy-2-[(2,3-η)-2-prop-2-en-1-yl]phenyl-κC1}(piperidine-κN)platinum(II) ethanol monosolvate top
Crystal data top
[Pt(C11H13O2)Cl(C5H11N)]·C2H6OZ = 2
Mr = 538.97F(000) = 528
Triclinic, P1Dx = 1.868 Mg m3
Hall symbol: -P 1Cu Kα radiation, λ = 1.54178 Å
a = 8.5280 (2) ÅCell parameters from 5133 reflections
b = 8.7520 (2) Åθ = 3.4–70.6°
c = 13.3309 (3) ŵ = 15.10 mm1
α = 97.905 (1)°T = 100 K
β = 97.684 (1)°Plate, colourless
γ = 99.880 (1)°0.6 × 0.15 × 0.07 mm
V = 958.21 (4) Å3
Data collection top
Bruker SMART 6000
diffractometer
3533 independent reflections
Radiation source: fine-focus sealed tube3410 reflections with I > 2σ(I)
Crossed Globel mirrors monochromatorRint = 0.050
ω and ϕ scanθmax = 70.6°, θmin = 3.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
h = 109
Tmin = 0.107, Tmax = 0.347k = 1010
13448 measured reflectionsl = 1616
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)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0436P)2]
where P = (Fo2 + 2Fc2)/3
3533 reflections(Δ/σ)max = 0.002
220 parametersΔρmax = 1.57 e Å3
0 restraintsΔρmin = 2.16 e Å3
Crystal data top
[Pt(C11H13O2)Cl(C5H11N)]·C2H6Oγ = 99.880 (1)°
Mr = 538.97V = 958.21 (4) Å3
Triclinic, P1Z = 2
a = 8.5280 (2) ÅCu Kα radiation
b = 8.7520 (2) ŵ = 15.10 mm1
c = 13.3309 (3) ÅT = 100 K
α = 97.905 (1)°0.6 × 0.15 × 0.07 mm
β = 97.684 (1)°
Data collection top
Bruker SMART 6000
diffractometer
3533 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
3410 reflections with I > 2σ(I)
Tmin = 0.107, Tmax = 0.347Rint = 0.050
13448 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.069H-atom parameters constrained
S = 1.08Δρmax = 1.57 e Å3
3533 reflectionsΔρmin = 2.16 e Å3
220 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
C10.2696 (5)0.6176 (4)0.3785 (3)0.0129 (7)
C20.2869 (5)0.5527 (4)0.2787 (3)0.0139 (7)
H20.27720.44220.26090.017*
C30.3180 (5)0.6489 (5)0.2064 (3)0.0143 (8)
C40.3316 (5)0.8132 (4)0.2317 (3)0.0148 (8)
C50.3171 (5)0.8779 (4)0.3304 (3)0.0158 (8)
H50.32710.98840.34830.019*
C60.2877 (5)0.7806 (4)0.4034 (3)0.0140 (7)
C70.3414 (6)0.4356 (4)0.0807 (3)0.0204 (8)
H7A0.42840.40940.12710.031*
H7B0.36150.41500.00990.031*
H7C0.23830.37100.08680.031*
C80.3631 (6)1.0615 (4)0.1765 (3)0.0251 (9)
H8A0.26081.07920.19710.038*
H8B0.37941.10910.11540.038*
H8C0.45191.10940.23250.038*
C90.2713 (5)0.8472 (4)0.5106 (3)0.0155 (7)
H9A0.16420.87650.51060.019*
H9B0.35480.94330.53590.019*
C100.2902 (5)0.7269 (4)0.5813 (3)0.0149 (8)
H100.21090.70200.62330.018*
C110.4226 (5)0.6527 (4)0.5851 (3)0.0168 (8)
H11A0.50230.67710.54330.020*
H11B0.43310.57770.62960.020*
C120.2720 (6)0.2472 (4)0.6279 (3)0.0167 (8)
H12A0.38560.30120.65120.020*
H12B0.26550.18240.56000.020*
C130.2216 (6)0.1398 (5)0.7040 (3)0.0198 (9)
H13A0.29730.06660.71160.024*
H13B0.11240.07660.67730.024*
C140.2212 (6)0.2365 (5)0.8087 (3)0.0183 (8)
H14A0.33250.29080.83920.022*
H14B0.18060.16610.85560.022*
C150.1132 (5)0.3579 (5)0.7960 (3)0.0175 (8)
H15A0.00000.30280.77270.021*
H15B0.11870.42470.86310.021*
C160.1647 (6)0.4609 (5)0.7188 (3)0.0166 (8)
H16A0.08880.53360.70960.020*
H16B0.27320.52510.74630.020*
C170.0871 (8)0.8141 (7)0.0783 (4)0.0431 (13)
H17A0.03140.71510.12200.065*
H17B0.03050.89870.09370.065*
H17C0.08830.80320.00610.065*
C180.2570 (7)0.8527 (5)0.0987 (3)0.0289 (10)
H18A0.25510.86230.17200.035*
H18B0.31090.95540.05720.035*
N10.1688 (4)0.3676 (4)0.6172 (2)0.0129 (6)
H10.06450.31050.59530.016*
O10.3355 (4)0.5974 (3)0.10741 (19)0.0179 (6)
O20.3593 (4)0.8968 (3)0.1539 (2)0.0199 (6)
O30.3470 (4)0.7364 (4)0.0749 (2)0.0259 (6)
H30.35040.72920.01240.039*
Cl10.10276 (11)0.26360 (9)0.38151 (6)0.01464 (19)
Pt10.224748 (17)0.495406 (13)0.492434 (9)0.01051 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.014 (2)0.0130 (17)0.0109 (18)0.0030 (13)0.0011 (13)0.0001 (13)
C20.016 (2)0.0157 (17)0.0102 (17)0.0041 (13)0.0001 (14)0.0019 (13)
C30.017 (2)0.0165 (18)0.0079 (17)0.0031 (14)0.0011 (14)0.0007 (13)
C40.017 (2)0.0154 (17)0.0109 (18)0.0013 (14)0.0008 (14)0.0035 (14)
C50.021 (2)0.0137 (17)0.0130 (18)0.0057 (14)0.0019 (15)0.0020 (14)
C60.018 (2)0.0138 (17)0.0101 (18)0.0037 (14)0.0016 (14)0.0003 (13)
C70.032 (2)0.0185 (18)0.0117 (17)0.0053 (15)0.0067 (15)0.0010 (13)
C80.043 (3)0.0166 (18)0.0144 (19)0.0030 (17)0.0038 (16)0.0037 (14)
C90.022 (2)0.0131 (16)0.0122 (17)0.0061 (14)0.0033 (14)0.0006 (13)
C100.019 (2)0.0155 (16)0.0079 (17)0.0007 (14)0.0002 (13)0.0004 (13)
C110.013 (2)0.0238 (18)0.0117 (17)0.0022 (14)0.0050 (13)0.0040 (14)
C120.026 (2)0.0146 (17)0.0105 (17)0.0056 (15)0.0028 (15)0.0024 (13)
C130.033 (3)0.0168 (18)0.0119 (19)0.0080 (16)0.0059 (16)0.0031 (14)
C140.027 (2)0.0189 (18)0.0108 (18)0.0088 (15)0.0041 (15)0.0036 (14)
C150.023 (2)0.0224 (19)0.0087 (17)0.0091 (15)0.0037 (14)0.0022 (14)
C160.027 (2)0.0171 (18)0.0078 (17)0.0080 (15)0.0052 (14)0.0008 (14)
C170.043 (3)0.053 (3)0.033 (3)0.019 (3)0.001 (2)0.002 (2)
C180.044 (3)0.025 (2)0.020 (2)0.0132 (19)0.0033 (18)0.0073 (16)
N10.0166 (18)0.0134 (14)0.0081 (15)0.0034 (12)0.0001 (12)0.0007 (11)
O10.0315 (17)0.0161 (12)0.0057 (12)0.0041 (11)0.0029 (10)0.0011 (9)
O20.0338 (18)0.0150 (12)0.0115 (12)0.0043 (11)0.0038 (11)0.0051 (10)
O30.0371 (19)0.0297 (15)0.0174 (14)0.0148 (13)0.0097 (12)0.0104 (11)
Cl10.0205 (5)0.0124 (4)0.0082 (4)0.0003 (3)0.0003 (3)0.0018 (3)
Pt10.01549 (13)0.01067 (11)0.00481 (11)0.00278 (6)0.00084 (7)0.00016 (6)
Geometric parameters (Å, º) top
C1—C21.410 (6)C11—Pt12.109 (4)
C1—C61.396 (5)C12—H12A0.9900
C1—Pt12.014 (4)C12—H12B0.9900
C2—H20.9500C12—C131.528 (5)
C2—C31.387 (6)C12—N11.493 (5)
C3—C41.412 (6)C13—H13A0.9900
C3—O11.371 (5)C13—H13B0.9900
C4—C51.388 (6)C13—C141.531 (5)
C4—O21.372 (5)C14—H14A0.9900
C5—H50.9500C14—H14B0.9900
C5—C61.400 (5)C14—C151.533 (6)
C6—C91.501 (5)C15—H15A0.9900
C7—H7A0.9800C15—H15B0.9900
C7—H7B0.9800C15—C161.517 (5)
C7—H7C0.9800C16—H16A0.9900
C7—O11.423 (5)C16—H16B0.9900
C8—H8A0.9800C16—N11.491 (5)
C8—H8B0.9800C17—H17A0.9800
C8—H8C0.9800C17—H17B0.9800
C8—O21.425 (5)C17—H17C0.9800
C9—H9A0.9900C17—C181.500 (9)
C9—H9B0.9900C18—H18A0.9900
C9—C101.521 (5)C18—H18B0.9900
C10—H100.9500C18—O31.420 (6)
C10—C111.395 (6)N1—H10.9300
C10—Pt12.143 (4)N1—Pt12.188 (3)
C11—H11A0.9500O3—H30.8400
C11—H11B0.9500Cl1—Pt12.3289 (8)
C2—C1—Pt1125.6 (3)C12—C13—H13B109.5
C6—C1—C2118.6 (3)C12—C13—C14110.7 (3)
C6—C1—Pt1115.7 (3)H13A—C13—H13B108.1
C1—C2—H2119.8C14—C13—H13A109.5
C3—C2—C1120.5 (4)C14—C13—H13B109.5
C3—C2—H2119.8C13—C14—H14A109.8
C2—C3—C4120.4 (4)C13—C14—H14B109.8
O1—C3—C2125.0 (3)C13—C14—C15109.6 (3)
O1—C3—C4114.7 (3)H14A—C14—H14B108.2
C5—C4—C3119.4 (3)C15—C14—H14A109.8
O2—C4—C3115.5 (3)C15—C14—H14B109.8
O2—C4—C5125.1 (3)C14—C15—H15A109.4
C4—C5—H5120.0C14—C15—H15B109.4
C4—C5—C6120.1 (4)H15A—C15—H15B108.0
C6—C5—H5120.0C16—C15—C14111.3 (4)
C1—C6—C5121.1 (4)C16—C15—H15A109.4
C1—C6—C9117.7 (3)C16—C15—H15B109.4
C5—C6—C9121.2 (3)C15—C16—H16A109.1
H7A—C7—H7B109.5C15—C16—H16B109.1
H7A—C7—H7C109.5H16A—C16—H16B107.8
H7B—C7—H7C109.5N1—C16—C15112.5 (3)
O1—C7—H7A109.5N1—C16—H16A109.1
O1—C7—H7B109.5N1—C16—H16B109.1
O1—C7—H7C109.5H17A—C17—H17B109.5
H8A—C8—H8B109.5H17A—C17—H17C109.5
H8A—C8—H8C109.5H17B—C17—H17C109.5
H8B—C8—H8C109.5C18—C17—H17A109.5
O2—C8—H8A109.5C18—C17—H17B109.5
O2—C8—H8B109.5C18—C17—H17C109.5
O2—C8—H8C109.5C17—C18—H18A109.2
C6—C9—H9A109.6C17—C18—H18B109.2
C6—C9—H9B109.6H18A—C18—H18B107.9
C6—C9—C10110.2 (3)O3—C18—C17112.2 (4)
H9A—C9—H9B108.1O3—C18—H18A109.2
C10—C9—H9A109.6O3—C18—H18B109.2
C10—C9—H9B109.6C12—N1—H1105.2
C9—C10—H10119.6C12—N1—Pt1110.7 (2)
C9—C10—Pt1109.1 (2)C16—N1—C12111.2 (3)
C11—C10—C9120.7 (4)C16—N1—H1105.2
C11—C10—H10119.6C16—N1—Pt1118.0 (2)
C11—C10—Pt169.5 (2)Pt1—N1—H1105.2
Pt1—C10—H1091.3C3—O1—C7117.2 (3)
C10—C11—H11A120.0C4—O2—C8116.0 (3)
C10—C11—H11B120.0C18—O3—H3109.5
C10—C11—Pt172.2 (2)C1—Pt1—C1081.39 (15)
H11A—C11—H11B120.0C1—Pt1—C1186.96 (15)
Pt1—C11—H11A107.8C1—Pt1—N1177.85 (13)
Pt1—C11—H11B90.0C1—Pt1—Cl194.15 (11)
H12A—C12—H12B107.8C10—Pt1—N197.56 (13)
C13—C12—H12A109.1C10—Pt1—Cl1167.26 (12)
C13—C12—H12B109.1C11—Pt1—C1038.29 (16)
N1—C12—H12A109.1C11—Pt1—N193.39 (13)
N1—C12—H12B109.1C11—Pt1—Cl1153.95 (12)
N1—C12—C13112.6 (4)N1—Pt1—Cl186.47 (8)
C12—C13—H13A109.5
C1—C2—C3—C40.4 (6)C9—C10—Pt1—Cl149.7 (6)
C1—C2—C3—O1179.5 (4)C10—C11—Pt1—C179.9 (2)
C1—C6—C9—C1018.0 (5)C10—C11—Pt1—N197.9 (2)
C2—C1—C6—C52.1 (6)C10—C11—Pt1—Cl1173.18 (18)
C2—C1—C6—C9179.1 (4)C11—C10—Pt1—C196.0 (2)
C2—C1—Pt1—C10167.0 (4)C11—C10—Pt1—N185.9 (2)
C2—C1—Pt1—C11128.9 (4)C11—C10—Pt1—Cl1166.3 (4)
C2—C1—Pt1—Cl125.0 (4)C12—C13—C14—C1555.2 (5)
C2—C3—C4—C51.4 (6)C12—N1—Pt1—C10121.5 (3)
C2—C3—C4—O2178.8 (4)C12—N1—Pt1—C1183.2 (3)
C2—C3—O1—C77.9 (6)C12—N1—Pt1—Cl170.7 (2)
C3—C4—C5—C60.6 (6)C13—C12—N1—C1654.6 (4)
C3—C4—O2—C8176.2 (4)C13—C12—N1—Pt1172.1 (3)
C4—C3—O1—C7173.0 (4)C13—C14—C15—C1655.4 (5)
C4—C5—C6—C11.2 (6)C14—C15—C16—N155.6 (5)
C4—C5—C6—C9180.0 (4)C15—C16—N1—C1254.4 (5)
C5—C4—O2—C84.0 (6)C15—C16—N1—Pt1176.0 (3)
C5—C6—C9—C10163.2 (4)C16—N1—Pt1—C108.4 (3)
C6—C1—C2—C31.3 (6)C16—N1—Pt1—C1146.6 (3)
C6—C1—Pt1—C1011.7 (3)C16—N1—Pt1—Cl1159.5 (3)
C6—C1—Pt1—C1149.8 (3)N1—C12—C13—C1455.7 (5)
C6—C1—Pt1—Cl1156.3 (3)O1—C3—C4—C5179.5 (4)
C6—C9—C10—C1151.5 (5)O1—C3—C4—O20.4 (5)
C6—C9—C10—Pt125.5 (4)O2—C4—C5—C6179.6 (4)
C9—C10—C11—Pt1100.7 (3)Pt1—C1—C2—C3179.9 (3)
C9—C10—Pt1—C120.5 (3)Pt1—C1—C6—C5179.1 (3)
C9—C10—Pt1—C11116.6 (4)Pt1—C1—C6—C90.3 (5)
C9—C10—Pt1—N1157.6 (3)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C1–C6 ring.
D—H···AD—HH···AD···AD—H···A
O3—H3···O10.842.102.869 (4)152
O3—H3···O20.842.473.158 (4)140
C10—H10···Cl1i0.952.743.466 (4)134
C7—H7A···O3ii0.982.593.276 (6)127
C15—H15A···Cg1i0.992.683.572 (5)149
C12—H12A···Cg1iii0.992.613.529 (5)154
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y+1, z; (iii) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C1–C6 ring.
D—H···AD—HH···AD···AD—H···A
O3—H3···O10.842.102.869 (4)152
O3—H3···O20.842.473.158 (4)140
C10—H10···Cl1i0.952.743.466 (4)134
C7—H7A···O3ii0.982.593.276 (6)127
C15—H15A···Cg1i0.992.683.572 (5)149
C12—H12A···Cg1iii0.992.613.529 (5)154
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y+1, z; (iii) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Pt(C11H13O2)Cl(C5H11N)]·C2H6O
Mr538.97
Crystal system, space groupTriclinic, P1
Temperature (K)100
a, b, c (Å)8.5280 (2), 8.7520 (2), 13.3309 (3)
α, β, γ (°)97.905 (1), 97.684 (1), 99.880 (1)
V3)958.21 (4)
Z2
Radiation typeCu Kα
µ (mm1)15.10
Crystal size (mm)0.6 × 0.15 × 0.07
Data collection
DiffractometerBruker SMART 6000
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2003)
Tmin, Tmax0.107, 0.347
No. of measured, independent and
observed [I > 2σ(I)] reflections
13448, 3533, 3410
Rint0.050
(sin θ/λ)max1)0.612
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.069, 1.08
No. of reflections3533
No. of parameters220
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.57, 2.16

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

 

Acknowledgements

This research was funded by the Vietnam National Foundation for Science and Technology Development (NAFOSTED) under grant No. 104.02–2012.66. We thank VLIR–UOS and the Chemistry Department of KU Leuven for support of this work.

References

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