research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 6| June 2015| Pages 644-646

Crystal structure of trans-di­chlorido­(4-nitro­aniline-κN1)(piperidine-κN)platinum(II)

aChemistry Department, Hanoi National University of Education, 136 – Xuan Thuy – Cau Giay, Hanoi, Vietnam, and bChemistry 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 8 May 2015; accepted 14 May 2015; online 20 May 2015)

In the title complex, [PtCl2(C5H11N)(C6H6N2O2)], the PtII metal atom displays a slightly distorted trans-PtN2Cl2 square-planar coordination geometry. The dihedral angle between the mean plane of the benzene and piperidine rings is 89.03 (3)°. In the crystal structure, inversion dimers are formed via N—H⋯Cl hydrogen-bond inter­actions, resulting in chains parallel to the [001] direction. The benzene rings within the chains show ππ stacking inter­actions [centroid-to-centroid distances of 3.801 (3) Å] and neighbouring chains inter­act via N—H⋯O hydrogen bonds.

1. Chemical context

The title compound is one of many complexes which have been synthesized for the purpose of potential medical applications (Klein & Hambley, 2009[Klein, A. V. & Hambley, T. W. (2009). Chem. Rev. 109, 4911-4920.]; Wilson & Lippard, 2014[Wilson, J. J. & Lippard, S. J. (2014). Chem. Rev. 114, 4470-4495.]; Peng et al., 2014[Peng, Y., Zhong, H., Chen, Z.-F., Liu, Y.-C., Zhang, G.-H., Qin, Q.-P. & Liang, H. (2014). Chem. Pharm. Bull. 62, 221-228.]). It is notable that according to the procedure used for the synthesis of complexes of the type cis-[PtCl2(piperidine)(another amine)] (piperidine hereafter denoted Pip) (Dinh & Da, 2003[Dinh, N. H. & Da, T. T. (2003). J. Coord. Chem. 41, 683-689.]; Nguyen Thi Thanh et al., 2014[Nguyen Thi Thanh, C., Nguyen Bich, N. & Van Meervelt, L. (2014). Acta Cryst. C70, 297-301.]), the reaction between K[PtCl3(Pip)] and p-nitro­aniline under appropriate conditions gave no cis complex, as expected, but instead gave the trans-[PtCl2(p-nitro­aniline)(Pip)] derivative, (I).

[Scheme 1]

To explain this we suppose that p-nitro­aniline first coordinates with PtII via the N atom of the amino group to form cis-[PtCl2(p-nitro­aniline)(Pip)] based on the trans effect. Then, in the reaction solution, the cis complex converts into the trans complex and the thermodynamics of this conversion are currently under investigation by us.

The anti­cancer activity of the title compound was tested according to the method described by Skehan et al. (1990[Skehan, P., Storeng, R., Scudiero, D., Monks, A., McMahon, J., Vistica, D., Warren, J. T., Bokesch, H., Kenney, S. & Boyd, M. R. (1990). J. Natl. Cancer Inst. 82, 1107-1112.]) against four human cancer cell lines (HepG2, RD, MCF7 and Fl). The IC50 values calculated based on OD values taken on an Elisa instrument at 515–540 nm are >10, 4.86, >10 and 8.25 µg ml−1, respectively.

2. Structural commentary

The mol­ecular structure of the title compound is illustrated in Fig. 1[link] and surprisingly shows a trans arrangement of the two Cl atoms [Cl8—Pt1—Cl9 = 177.84 (4)°]. The piperidine ring adopts the usual chair conformation, with the N2—Pt1 bond in the equatorial position. The piperidine ring is oriented nearly perpendicular to the coordination plane of the PtII atom, thereby reducing the van der Waals repulsion; the dihedral angle between the least-squares mean planes through the piperdine ring and the four atoms coordinated to the Pt atom is 89.6 (2)°. One short intra­molecular contact is observed, i.e. H7B⋯Cl8 = 2.83 Å. The mean planes through the piperidine ring and the benzene ring make a dihedral angle of 89.0 (3)°. The dihedral angle between the mean planes of the nitro substituent and the benzene ring is 16.6 (3)°.

[Figure 1]
Figure 1
The mol­ecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

3. Supra­molecular features

In the crystal, inversion dimers are formed via N—H⋯Cl inter­actions between the aniline N atom and both Cl atoms, resulting in chains of mol­ecules along the [001] direction (Fig. 2[link] and Table 1[link]). Within these chains, ππ inter­actions occur between the aromatic rings [CgCgiv = 3.801 (3) Å; Cg is the centroid of the C11–C16 ring; symmetry code: (iv) −x, y, −z + [{3\over 2}]; Fig. 2[link]]. Neighbouring chains are linked via N—H⋯O hydrogen bonds between the piperidine N atom and a nitro O atom (Fig. 2[link] and Table 1[link]).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H2⋯O18i 0.93 2.27 3.182 (6) 165
N10—H10A⋯Cl8ii 0.92 2.32 3.198 (4) 158
N10—H10B⋯Cl9iii 0.92 2.37 3.255 (4) 161
Symmetry codes: (i) [x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]; (ii) -x, -y+2, -z+1; (iii) [-x, y, -z+{\script{1\over 2}}].
[Figure 2]
Figure 2
Partial packing diagram of the title compound, showing a chain of mol­ecules formed parallel to the [001] direction via N—H⋯Cl inter­actions (green dotted lines) and ππ inter­actions (grey dotted line). Neighbouring chains inter­act via N—H⋯O hydrogen bonds (red dotted line).

4. Database survey

A search of the Cambridge Structural Database (Version 5.36; last update February 2015; Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) for Pt complexes with Pt coordinated to exactly two Cl atoms and two N atoms gave 713 hits. The majority of these Pt complexes display a cis coordination of the Cl atoms (474 structures), with the remaining 239 structures showing a trans coordination. There is no difference in the Pt—Cl distances between both configurations. The average Pt—Cl distances are 2.300 (15) and 2.299 (12) Å for the cis and trans arrangements, respectively, and correspond to the observed distances of 2.3039 (11) and 2.2917 (12) Å for Pt1—Cl8 and Pt1—Cl9, respectively.

5. Synthesis and crystallization

The starting complex K[PtCl3(piperidine)] (0.425 g, 1 mmol), prepared according to the synthetic procedure of Da et al. (2001[Da, T. T., Vu, D. B. & Dinh, N. H. (2001). J. Pharm. Sci. (Vietnam), 6, 6-8.]) with slight modifications, was dissolved in water (10 ml) and filtered to afford a clear solution. To this solution, p-nitro­aniline (1 mmol) in ethanol (10 ml) was added gradually while stirring at 413–318 K. After 1 h, a brown powder appeared and the reaction mixture was then stirred further for 24 h until all the precipitate was completely dissolved. The solvent was removed in vacuo to give a brown–yellow product. The product was washed consecutively with a 0.1 M HCl solution (2 × 2 ml), warm water (2 × 2 ml) and diethyl ether (2 × 2 ml). The yield was 80%. Single crystals suitable for X-ray determination were obtained by slow evaporation within 12 h from an acetone solution at room temperature. IR (KBr, cm−1): 3199, 3113 (νNH); 3070, 2927, 2862 (νCH); 1596, 1525, 1479 (νC=C arom); 1342, 1325 (νNO); 1H NMR (CDCl3, 500 MHz): δ 8.21 (2H, d, 3J = 9.0 Hz, Ar-H), 7.47 (2H, d, 3J = 9.0 Hz, Ar-H), 5.49 (2H, br, O2NC6H4NH2), 3.66 (1H, br, C5H10NH), 3.26 (2Hαe, d, 2Jae = 13.0 Hz, C5H10NH), 2.99 (2Hαa, q, 2Jae, 3Jaa, 3Jaa(NH) = 13.0 Hz, C5H10NH), 1.69–1.43 (4Hβ, 2Hγ, ov, C5H10NH). 13C{1H} NMR (125 MHz, CDCl3): δ 149.6, 125.1, 124.2 (O2NC6H4NH2), 54.0, 27.2, 24.3 (C5H10NH).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. All H atoms were placed at idealized positions and refined in riding mode, with Uiso(H) values assigned as 1.2Ueq of the parent atoms, with C—H distances of 0.95 (aromatic) and 0.99 Å (methyl­ene), and N—H distances of 0.93 (NH) and 0.92 Å (NH2).

Table 2
Experimental details

Crystal data
Chemical formula [PtCl2(C5H11N)(C6H6N2O2)]
Mr 489.27
Crystal system, space group Monoclinic, C2/c
Temperature (K) 100
a, b, c (Å) 15.8763 (11), 18.5394 (11), 10.8707 (6)
β (°) 103.119 (7)
V3) 3116.1 (3)
Z 8
Radiation type Mo Kα
μ (mm−1) 9.35
Crystal size (mm) 0.35 × 0.15 × 0.1
 
Data collection
Diffractometer Agilent SuperNova (single source at offset, Eos detector)
Absorption correction Multi-scan (CrysAlis PRO; Agilent, 2012[Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England.])
Tmin, Tmax 0.538, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections 8156, 3109, 2713
Rint 0.044
(sin θ/λ)max−1) 0.625
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.072, 1.10
No. of reflections 3109
No. of parameters 172
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 2.75, −1.82
Computer programs: CrysAlis PRO (Agilent, 2012[Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England.]), 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

The title compound is one of many complexes which have been synthesized for the purpose of potential medical applications (Klein & Hambley, 2009; Wilson & Lippard, 2014; Peng et al., 2014). It is notable that according to the procedure used for the synthesis of complexes of the type cis-[PtCl2(piperidine)(another amine)] (piperidine hereafter denoted Pip) (Dinh & Da, 2003; Nguyen Thi Thanh et al., 2014), the reaction between K[PtCl3(Pip)] and p-nitro­aniline under appropriate conditions gave no cis complex, as expected, but instead gave the trans-[PtCl2(p-nitro­aniline)(Pip)] derivative.

To explain this we suppose that p-nitro­aniline first coordinates with PtII via the N atom of the amino group to form cis-[PtCl2(p-nitro­aniline)(Pip)] based on the trans effect. Then, in the reaction solution, the cis complex converts into the trans complex and the thermodynamics of this conversion are currently under investigation by us.

The anti­cancer activity of the title compound was tested according to the method described by Skehan et al. (1990) against four human cancer cell lines (HepG2, RD, MCF7 and Fl). The IC50 values calculated based on OD values taken on an Elisa instrument at 515–540 nm are >10, 4.86, >10 and 8.25 µg ml-1, respectively.

Structural commentary top

The molecular structure of the title compound is illustrated in Fig. 1 and surprisingly shows a trans arrangement of the two Cl atoms [Cl8—Pt1—Cl9 = 177.84 (4)°]. The piperidine ring adopts the usual chair conformation, with the N2—Pt1 bond in the equatorial position. The piperidine ring is oriented nearly perpendicular to the coordination plane of the PtII atom, thereby reducing the van der Waals repulsion; the dihedral angle between the least-squares mean planes through the piperdine ring and the four atoms coordinated to the Pt atom is 89.6 (2)°. One short intra­molecular contact is observed, i.e. H7B···Cl8 = 2.83 Å. The mean planes through the piperidine ring and the benzene ring make a dihedral angle of 89.0 (3)°. The dihedral angle between the mean planes of the nitro substituent and the benzene ring is 16.6 (3)°.

Supra­molecular features top

In the crystal, inversion dimers are formed via N—H···Cl inter­actions between the aniline N atom and both Cl atoms, resulting in chains of molecules along the [001] direction (Fig. 2 and Table 1). Within these chains, ππ inter­actions occur between the aromatic rings [Cg···Cgiv = 3.801 (3) Å; Cg is the centroid of the C11–C16 ring; symmetry code: (iv) -x, y, -z+3/2; Fig. 2]. Neighbouring chains are linked via N—H···O hydrogen bonds between the piperidine N atom and a nitro O atom (Fig. 2 and Table 1).

Database survey top

A search of the Cambridge Structural Database (Version 5.36; last update February 2015; Groom & Allen, 2014) for Pt complexes with Pt coordinated to exactly two Cl atoms and two N atoms gave 713 hits. The majority of these Pt complexes display a cis coordination of the Cl atoms (474 compounds), with the remaining 239 compounds showing a trans coordination. There is no difference in the Pt—Cl distances between both configurations. The average Pt—Cl distances are 2.300 (15) and 2.299 (12) Å for the cis and trans arrangements, respectively, and correspond to the observed distances of 2.3039 (11) and 2.2917 (12) Å for Pt1—Cl8 and Pt1—Cl9, respectively.

Synthesis and crystallization top

The starting complex K[PtCl3(piperidine)] (0.425 g, 1 mmol), prepared according to the synthetic procedure of Da et al. (2001) with slight modifications, was dissolved in water (10 ml) and filtered to afford a clear solution. To this solution, p-nitro­aniline (1 mmol) in ethanol (10 ml) was added gradually while stirring at 413–318 K. After 1 h, a brown powder appeared and the reaction mixture was then stirred further for 24 h until all the precipitate was completely dissolved. The solvent was removed in vacuo to give a brown–yellow product. The product was washed consecutively with a 0.1 M HCl solution (2 × 2 ml), warm water (2 × 2 ml) and di­ethyl ether (2 × 2 ml). The yield was 80%. Single crystals suitable for X-ray determination were obtained by slow evaporation within 12 h from an acetone solution at room temperature. IR (KBr, cm-1): 3199, 3113 (νNH); 3070, 2927, 2862 (νCH); 1596, 1525, 1479 (νCC arom); 1342, 1325 (νNO); 1H NMR (CDCl3, 500 MHz): δ 8.21 (2H, d, 3J = 9.0 Hz, Ar-H), 7.47 (2H, d, 3J = 9.0 Hz, Ar-H), 5.49 (2H, br, O2NC6H4NH2), 3.66 (1H, br, C5H10NH), 3.26 (2Hαe, d, 2Jae = 13.0 Hz, C5H10NH), 2.99 (2Hαa , q, 2Jae, 3Jaa, 3Jaa(NH) = 13.0 Hz, C5H10NH), 1.69–1.43 (4Hβ, 2Hγ, ov, C5H10NH). 13C{1H} NMR (125 MHz, CDCl3): δ 149.6, 125.1, 124.2 (O2NC6H4NH2), 54.0, 27.2, 24.3 (C5H10NH).

Refinement top

All H atoms were placed at idealized positions and refined in riding mode, with Uiso(H) values assigned as 1.2Ueq of the parent atoms, with C—H distances of 0.95 (aromatic) and 0.99 Å (methyl­ene), and N—H distances of 0.93 (NH) and 0.92 Å (NH2).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); 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
[Figure 1] Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. Partial packing diagram of the title compound, showing a chain of molecules formed parallel to the [001] direction via N—H···Cl interactions (green dotted lines) and ππ interactions (grey dotted line). Neighbouring chains interact via N—H···O hydrogen bonds (red dotted line).
trans-Dichlorido(4-nitroaniline-κN1)(piperidine-\ κN)platinum(II) top
Crystal data top
[PtCl2(C5H11N)(C6H6N2O2)]F(000) = 1856
Mr = 489.27Dx = 2.086 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 15.8763 (11) ÅCell parameters from 3549 reflections
b = 18.5394 (11) Åθ = 3.4–28.8°
c = 10.8707 (6) ŵ = 9.35 mm1
β = 103.119 (7)°T = 100 K
V = 3116.1 (3) Å3, brown
Z = 80.35 × 0.15 × 0.1 mm
Data collection top
Agilent SuperNova (single source at offset, Eos detector)
diffractometer
3109 independent reflections
Radiation source: SuperNova (Mo) X-ray Source2713 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.044
Detector resolution: 15.9631 pixels mm-1θmax = 26.4°, θmin = 2.8°
ω scansh = 1915
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
k = 1723
Tmin = 0.538, Tmax = 1.000l = 1313
8156 measured reflections
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)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0296P)2 + 0.5839P]
where P = (Fo2 + 2Fc2)/3
3109 reflections(Δ/σ)max = 0.003
172 parametersΔρmax = 2.75 e Å3
0 restraintsΔρmin = 1.82 e Å3
Crystal data top
[PtCl2(C5H11N)(C6H6N2O2)]V = 3116.1 (3) Å3
Mr = 489.27Z = 8
Monoclinic, C2/cMo Kα radiation
a = 15.8763 (11) ŵ = 9.35 mm1
b = 18.5394 (11) ÅT = 100 K
c = 10.8707 (6) Å0.35 × 0.15 × 0.1 mm
β = 103.119 (7)°
Data collection top
Agilent SuperNova (single source at offset, Eos detector)
diffractometer
3109 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
2713 reflections with I > 2σ(I)
Tmin = 0.538, Tmax = 1.000Rint = 0.044
8156 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.072H-atom parameters constrained
S = 1.10Δρmax = 2.75 e Å3
3109 reflectionsΔρmin = 1.82 e Å3
172 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
C30.2646 (4)0.9772 (3)0.4633 (5)0.0233 (13)
H3A0.24391.01300.51730.028*
H3B0.23350.98590.37480.028*
C40.3620 (4)0.9877 (3)0.4750 (5)0.0243 (13)
H4A0.38150.95620.41320.029*
H4B0.37341.03830.45510.029*
C50.4128 (4)0.9694 (3)0.6083 (5)0.0267 (13)
H5A0.47550.97270.61220.032*
H5B0.39851.00450.66910.032*
C60.3905 (4)0.8933 (3)0.6443 (6)0.0255 (14)
H6A0.41090.85800.58920.031*
H6B0.42100.88330.73260.031*
C70.2938 (4)0.8839 (3)0.6313 (5)0.0220 (13)
H7A0.28160.83320.65010.026*
H7B0.27460.91510.69370.026*
C110.0526 (3)0.8256 (3)0.5180 (4)0.0175 (11)
C120.0838 (4)0.8538 (3)0.6181 (5)0.0193 (11)
H120.08320.90440.63280.023*
C130.1159 (3)0.8069 (3)0.6957 (5)0.0205 (12)
H130.13700.82480.76490.025*
C140.1167 (4)0.7338 (3)0.6710 (5)0.0225 (12)
C150.0857 (4)0.7057 (3)0.5722 (5)0.0266 (14)
H150.08700.65520.55710.032*
C160.0528 (4)0.7522 (3)0.4957 (5)0.0218 (12)
H160.03030.73390.42800.026*
Cl80.10439 (9)0.97037 (6)0.62798 (11)0.0190 (3)
Cl90.12310 (9)0.80109 (7)0.32660 (11)0.0212 (3)
N20.2441 (3)0.9028 (2)0.5016 (4)0.0160 (9)
H20.26290.87130.44690.019*
N100.0192 (3)0.8739 (2)0.4368 (4)0.0157 (9)
H10A0.04390.91850.44090.019*
H10B0.03730.85760.35520.019*
N170.1522 (3)0.6855 (3)0.7523 (4)0.0294 (12)
O180.1616 (3)0.7083 (2)0.8546 (3)0.0316 (10)
O190.1721 (4)0.6237 (2)0.7150 (4)0.0464 (14)
Pt10.113556 (13)0.887195 (10)0.474086 (16)0.01473 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C30.021 (3)0.032 (3)0.019 (3)0.008 (2)0.007 (2)0.001 (2)
C40.024 (4)0.030 (3)0.022 (3)0.003 (2)0.010 (2)0.000 (2)
C50.021 (3)0.031 (3)0.029 (3)0.001 (3)0.007 (3)0.003 (3)
C60.022 (4)0.026 (3)0.028 (3)0.000 (2)0.005 (3)0.000 (2)
C70.018 (3)0.026 (3)0.022 (3)0.001 (2)0.003 (2)0.003 (2)
C110.013 (3)0.022 (3)0.016 (2)0.002 (2)0.000 (2)0.000 (2)
C120.019 (3)0.019 (3)0.020 (3)0.001 (2)0.006 (2)0.004 (2)
C130.013 (3)0.034 (3)0.014 (2)0.003 (2)0.004 (2)0.002 (2)
C140.025 (3)0.024 (3)0.021 (3)0.004 (2)0.010 (2)0.005 (2)
C150.040 (4)0.017 (3)0.021 (3)0.001 (3)0.004 (3)0.002 (2)
C160.025 (3)0.021 (3)0.020 (3)0.001 (2)0.008 (2)0.001 (2)
Cl80.0217 (8)0.0195 (6)0.0164 (6)0.0017 (5)0.0054 (5)0.0009 (5)
Cl90.0220 (8)0.0239 (6)0.0174 (6)0.0023 (6)0.0039 (5)0.0042 (5)
N20.012 (3)0.020 (2)0.016 (2)0.0003 (18)0.0033 (18)0.0026 (18)
N100.013 (3)0.019 (2)0.015 (2)0.0011 (18)0.0022 (19)0.0009 (18)
N170.031 (3)0.030 (3)0.028 (3)0.003 (2)0.009 (2)0.006 (2)
O180.035 (3)0.044 (2)0.021 (2)0.007 (2)0.0163 (18)0.0022 (19)
O190.077 (4)0.026 (2)0.046 (3)0.006 (2)0.034 (3)0.003 (2)
Pt10.01469 (15)0.01670 (13)0.01350 (12)0.00081 (7)0.00464 (9)0.00004 (7)
Geometric parameters (Å, º) top
C3—H3A0.9900C12—H120.9500
C3—H3B0.9900C12—C131.387 (7)
C3—C41.535 (8)C13—H130.9500
C3—N21.497 (6)C13—C141.381 (7)
C4—H4A0.9900C14—C151.382 (7)
C4—H4B0.9900C14—N171.458 (7)
C4—C51.528 (8)C15—H150.9500
C5—H5A0.9900C15—C161.380 (7)
C5—H5B0.9900C16—H160.9500
C5—C61.526 (7)Cl8—Pt12.3039 (11)
C6—H6A0.9900Cl9—Pt12.2917 (12)
C6—H6B0.9900N2—H20.9300
C6—C71.520 (8)N2—Pt12.046 (4)
C7—H7A0.9900N10—H10A0.9200
C7—H7B0.9900N10—H10B0.9200
C7—N21.492 (7)N10—Pt12.068 (4)
C11—C121.396 (7)N17—O181.231 (5)
C11—C161.382 (7)N17—O191.232 (6)
C11—N101.440 (6)
H3A—C3—H3B107.9C13—C12—H12120.5
C4—C3—H3A109.3C12—C13—H13120.5
C4—C3—H3B109.3C14—C13—C12119.0 (5)
N2—C3—H3A109.3C14—C13—H13120.5
N2—C3—H3B109.3C13—C14—C15122.2 (5)
N2—C3—C4111.8 (4)C13—C14—N17118.2 (5)
C3—C4—H4A109.5C15—C14—N17119.6 (5)
C3—C4—H4B109.5C14—C15—H15120.6
H4A—C4—H4B108.1C16—C15—C14118.9 (5)
C5—C4—C3110.8 (4)C16—C15—H15120.6
C5—C4—H4A109.5C11—C16—H16120.1
C5—C4—H4B109.5C15—C16—C11119.7 (5)
C4—C5—H5A109.6C15—C16—H16120.1
C4—C5—H5B109.6C3—N2—H2106.2
H5A—C5—H5B108.1C3—N2—Pt1111.5 (3)
C6—C5—C4110.2 (5)C7—N2—C3112.2 (4)
C6—C5—H5A109.6C7—N2—H2106.2
C6—C5—H5B109.6C7—N2—Pt1113.9 (3)
C5—C6—H6A109.3Pt1—N2—H2106.2
C5—C6—H6B109.3C11—N10—H10A108.0
H6A—C6—H6B107.9C11—N10—H10B108.0
C7—C6—C5111.7 (5)C11—N10—Pt1117.0 (3)
C7—C6—H6A109.3H10A—N10—H10B107.3
C7—C6—H6B109.3Pt1—N10—H10A108.0
C6—C7—H7A109.3Pt1—N10—H10B108.0
C6—C7—H7B109.3O18—N17—C14118.7 (4)
H7A—C7—H7B108.0O18—N17—O19122.8 (5)
N2—C7—C6111.5 (4)O19—N17—C14118.5 (5)
N2—C7—H7A109.3Cl9—Pt1—Cl8177.84 (4)
N2—C7—H7B109.3N2—Pt1—Cl891.59 (12)
C12—C11—N10119.4 (4)N2—Pt1—Cl988.59 (12)
C16—C11—C12121.2 (5)N2—Pt1—N10176.94 (15)
C16—C11—N10119.4 (4)N10—Pt1—Cl889.56 (12)
C11—C12—H12120.5N10—Pt1—Cl990.37 (12)
C13—C12—C11119.0 (5)
C3—C4—C5—C654.8 (6)C12—C11—N10—Pt197.9 (5)
C3—N2—Pt1—Cl866.5 (3)C12—C13—C14—C150.7 (9)
C3—N2—Pt1—Cl9115.7 (3)C12—C13—C14—N17178.9 (5)
C4—C3—N2—C754.8 (6)C13—C14—C15—C160.0 (9)
C4—C3—N2—Pt1176.0 (3)C13—C14—N17—O1816.4 (8)
C4—C5—C6—C755.5 (6)C13—C14—N17—O19163.1 (6)
C5—C6—C7—N255.4 (6)C14—C15—C16—C110.9 (8)
C6—C7—N2—C354.8 (6)C15—C14—N17—O18164.0 (5)
C6—C7—N2—Pt1177.4 (3)C15—C14—N17—O1916.5 (8)
C7—N2—Pt1—Cl861.7 (3)C16—C11—C12—C130.3 (8)
C7—N2—Pt1—Cl9116.1 (3)C16—C11—N10—Pt181.8 (5)
C11—C12—C13—C140.6 (8)N2—C3—C4—C554.9 (6)
C11—N10—Pt1—Cl882.4 (3)N10—C11—C12—C13180.0 (5)
C11—N10—Pt1—Cl995.5 (3)N10—C11—C16—C15179.2 (5)
C12—C11—C16—C151.1 (8)N17—C14—C15—C16179.6 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O18i0.932.273.182 (6)165
N10—H10A···Cl8ii0.922.323.198 (4)158
N10—H10B···Cl9iii0.922.373.255 (4)161
Symmetry codes: (i) x+1/2, y+3/2, z1/2; (ii) x, y+2, z+1; (iii) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O18i0.932.273.182 (6)165
N10—H10A···Cl8ii0.922.323.198 (4)158
N10—H10B···Cl9iii0.922.373.255 (4)161
Symmetry codes: (i) x+1/2, y+3/2, z1/2; (ii) x, y+2, z+1; (iii) x, y, z+1/2.

Experimental details

Crystal data
Chemical formula[PtCl2(C5H11N)(C6H6N2O2)]
Mr489.27
Crystal system, space groupMonoclinic, C2/c
Temperature (K)100
a, b, c (Å)15.8763 (11), 18.5394 (11), 10.8707 (6)
β (°) 103.119 (7)
V3)3116.1 (3)
Z8
Radiation typeMo Kα
µ (mm1)9.35
Crystal size (mm)0.35 × 0.15 × 0.1
Data collection
DiffractometerAgilent SuperNova (single source at offset, Eos detector)
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2012)
Tmin, Tmax0.538, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
8156, 3109, 2713
Rint0.044
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.072, 1.10
No. of reflections3109
No. of parameters172
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)2.75, 1.82

Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

 

Acknowledgements

The authors thank the Vietnamese Ministry of Education (project B2013-17-39) and VLIR–UOS (project ZEIN­2014Z182) for financial support and the Hercules Foundation for supporting the purchase of the diffractometer through project AKUL/09/0035.

References

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Volume 71| Part 6| June 2015| Pages 644-646
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