supplementary materials


Acta Cryst. (2007). E63, m1667    [ doi:10.1107/S1600536807022817 ]

cis-Dichlorido(N-cyclohexylpropane-1,3-diamine-[kappa]2N,N')platinum(II)

M.-J. Xie, X.-Z. Chen, W.-P. Liu, S.-Q. Hou and Q.-S. Ye

Abstract top

The reaction of N-cyclohexylpropane-1,3-diamine with potassium tetrachloroplatinate(II) produced the monomeric title complex, [PtCl2(C9H18N2)]. In the asymmetric unit there are two crystallographically independent PtII complexes, where each PtII ion is tetracoordinate in a distorted square-planar geometry. N-H...Cl hydrogen bonds between the complexes form a three-dimensional network in the crystal structure.

Comment top

Cisplatin is commonly used for the treatment of testicular and overian cancer as well as cervical, bladder, head and neck tumors. The application of cisplatin in therapy is limited by the dose-dependent nephrotoxicity and other side effects (Jakuper et al., 2003). Therefore, the search for the new potent platinum complexes possessing high antitumor activity and lack of cross-resistance is continuing. The title compound, (I), is a new soluble cisplatin analogue containing an asymmetric chelating diamine N-cyclohexylpropane-1,3-diamine and its carrier and anticancer tests are in progress.

The PtII ion has a square planar geometry formed by an N-cyclohexylpropane-1,3-diamine ligand and two Cl atoms (Fig. 1). The crystal structures of a large number of square-planar dichloroplatinum(II) complexes with amine ligands have been reported, as found in the Cambridge Structural Database, Version 5.27 (Allen 2002). Among them, several PtII complexes contain the chelating ligand 1,2-diaminoethane as well as its N-substituted derivatives, such as, N,N-dimethylethane-1,2-diamine (Melanson et al., 1987) and N-(2-hydroxyethyl)ethane-1,2-diamine (Davies et al., 2002). The chelating nature of the 1,2-diaminoethane portion of these ligands ensures a cis configuration; in the present study, the N-cyclohexylpropane-1,3-diamine ligand also ensures such a geometry. In the crystal structure, he N—H···Cl hydrogen bonds (Table 1) form a three-dimensional network.

Related literature top

For related literature, see: Allen (2002); Davies et al. (2002); Jakuper et al. (2003); Melanson et al. (1987).

Experimental top

Potassium tetrachloroplatinate (5 g, 12 mmol) was dissolved in water (50 ml) and treated with KI (12 g, 72 mmol). After standing in dark for 30 min at room temperature, an aqueous solution (50 ml) of N-cyclohexylpropane-1,3-diamine (1.8 g, 12 mmol) was added dropwise. The mixture was stirred for 4 h and the yellow precipitate was filtrated off. Then to a suspension of di(N-cyclohexylpropane-1,3-diamine)PtI2 (2.5 g, 0.044 mmol) in 100 ml water was added silver nitrate (1.26 g, 7.40 mmol), and the reaction mixture was stirred at 313 K for 8 h. After that the AgI formed was filtrated off, potassium chloride (1.1 g, 14.7 mmol) was added to the filtrate and then a yellow crystalline product precipitated. Single crystals suitable for X-ray diffraction were obtained from aqueous solution.

Refinement top

The H atoms were placed at calculated positions (C—H = 0.97 or 0.98 Å, N—H = 0.90 or 0.91 Å) and were refined as riding, with Uiso(H) = 1.2Ueq(C,N). The highest peak and deepest hole in the final difference Fourier map are located 1.91 and 0.62 Å, respectively, from atoms Cl3 and Pt2.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), shown with 30% probability displacement ellipsoids.
cis-Dichlorido(N-cyclohexylpropane-1,3-diamine-κ2N,N')platinum(II) top
Crystal data top
[PtCl2(C9H18N2)]F(000) = 1600
Mr = 422.26Dx = 2.166 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4537 reflections
a = 18.6553 (17) Åθ = 2.3–27.4°
b = 12.2229 (11) ŵ = 11.22 mm1
c = 11.7912 (10) ÅT = 293 K
β = 105.620 (1)°BLOCK, yellow
V = 2589.4 (4) Å30.27 × 0.25 × 0.18 mm
Z = 8
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer
6027 independent reflections
Radiation source: fine-focus sealed tube4679 reflections with I > 2σ(I)
graphiteRint = 0.034
φ and ω scansθmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
h = 2324
Tmin = 0.068, Tmax = 0.133k = 1415
16372 measured reflectionsl = 815
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.090 w = 1/[σ2(Fo2) + (0.0458P)2 + 1.8205P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.002
6027 reflectionsΔρmax = 2.68 e Å3
253 parametersΔρmin = 1.16 e Å3
0 restraintsExtinction correction: SHELXL97
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00297 (8)
Crystal data top
[PtCl2(C9H18N2)]V = 2589.4 (4) Å3
Mr = 422.26Z = 8
Monoclinic, P21/cMo Kα radiation
a = 18.6553 (17) ŵ = 11.22 mm1
b = 12.2229 (11) ÅT = 293 K
c = 11.7912 (10) Å0.27 × 0.25 × 0.18 mm
β = 105.620 (1)°
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer
6027 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
4679 reflections with I > 2σ(I)
Tmin = 0.068, Tmax = 0.133Rint = 0.034
16372 measured reflectionsθmax = 28.3°
Refinement top
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.090Δρmax = 2.68 e Å3
S = 1.00Δρmin = 1.16 e Å3
6027 reflectionsAbsolute structure: ?
253 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Pt10.602854 (15)0.33059 (2)0.54069 (2)0.03545 (9)
Pt20.723992 (16)0.86089 (2)0.35584 (2)0.03850 (9)
Cl10.52757 (11)0.18859 (15)0.56509 (17)0.0517 (5)
Cl20.66417 (14)0.32878 (19)0.73912 (17)0.0716 (7)
Cl30.63984 (11)0.75890 (16)0.21861 (15)0.0524 (5)
Cl40.79928 (14)0.8797 (2)0.2320 (2)0.0754 (7)
N10.5448 (3)0.3328 (4)0.3681 (5)0.0397 (13)
H1A0.57480.30910.32490.048*
H1B0.50680.28520.35760.048*
N20.6684 (3)0.4588 (4)0.5132 (5)0.0414 (14)
H2A0.69200.48400.58630.050*
N30.6554 (3)0.8520 (4)0.4639 (5)0.0370 (13)
H3A0.61290.81860.42480.044*
H3B0.67720.80980.52620.044*
N40.7996 (3)0.9567 (5)0.4747 (5)0.0456 (15)
H4B0.82510.99090.42910.055*
C10.5145 (4)0.4410 (6)0.3228 (7)0.0481 (18)
H1D0.48190.46700.36870.058*
H1C0.48500.43320.24190.058*
C20.5749 (4)0.5249 (6)0.3282 (6)0.0457 (18)
H2B0.55210.59160.29050.055*
H2C0.60800.49780.28370.055*
C30.6210 (4)0.5524 (5)0.4530 (6)0.0450 (17)
H3C0.65290.61440.44960.054*
H3D0.58770.57400.49960.054*
C40.7300 (4)0.4255 (6)0.4594 (6)0.0404 (16)
H4A0.70750.38530.38660.049*
C50.7835 (5)0.3490 (6)0.5422 (8)0.059 (2)
H5A0.75690.28380.55450.071*
H5B0.80250.38470.61780.071*
C60.8496 (5)0.3153 (8)0.4940 (10)0.083 (3)
H6A0.88380.26990.55130.099*
H6B0.83150.27310.42230.099*
C70.8893 (5)0.4154 (9)0.4688 (9)0.076 (3)
H7A0.92990.39380.43670.091*
H7B0.91020.45510.54140.091*
C80.8363 (5)0.4884 (8)0.3822 (8)0.069 (2)
H8A0.81740.44940.30850.083*
H8B0.86280.55250.36670.083*
C90.7717 (4)0.5242 (6)0.4281 (7)0.0497 (18)
H9A0.73760.56800.36870.060*
H9B0.79010.56930.49750.060*
C100.6367 (4)0.9577 (6)0.5071 (6)0.0434 (17)
H10A0.60070.94690.55200.052*
H10B0.61441.00470.44080.052*
C110.7055 (4)1.0122 (6)0.5841 (6)0.0490 (18)
H11A0.73000.96130.64540.059*
H11B0.69011.07500.62210.059*
C120.7617 (4)1.0502 (6)0.5198 (7)0.0522 (19)
H12A0.73641.09590.45390.063*
H12B0.79921.09460.57290.063*
C130.8599 (4)0.9035 (7)0.5691 (7)0.057 (2)
H13A0.83910.88610.63490.068*
C140.8847 (5)0.7984 (8)0.5265 (9)0.079 (3)
H14A0.90170.81260.45700.095*
H14B0.84290.74840.50440.095*
C150.9478 (5)0.7448 (10)0.6214 (11)0.103 (4)
H15A0.92940.72420.68790.124*
H15B0.96400.67890.58980.124*
C161.0129 (6)0.8215 (10)0.6624 (11)0.100 (4)
H16A1.03430.83710.59770.119*
H16B1.05090.78730.72500.119*
C170.9875 (6)0.9275 (11)0.7069 (11)0.117 (5)
H17A0.97120.91240.77680.140*
H17B1.02910.97790.72860.140*
C180.9242 (5)0.9807 (8)0.6145 (9)0.085 (3)
H18A0.90701.04450.64830.102*
H18B0.94261.00510.54920.102*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.04393 (17)0.03630 (14)0.02848 (15)0.00389 (11)0.01381 (11)0.00052 (10)
Pt20.04833 (18)0.04223 (16)0.02812 (15)0.00332 (12)0.01576 (12)0.00176 (11)
Cl10.0504 (11)0.0522 (11)0.0551 (12)0.0103 (8)0.0186 (9)0.0089 (9)
Cl20.0905 (17)0.0851 (16)0.0325 (10)0.0331 (13)0.0052 (10)0.0066 (10)
Cl30.0640 (12)0.0575 (11)0.0339 (9)0.0017 (9)0.0103 (9)0.0100 (8)
Cl40.0845 (17)0.1035 (18)0.0551 (13)0.0096 (14)0.0477 (13)0.0110 (12)
N10.040 (3)0.046 (3)0.035 (3)0.006 (3)0.014 (3)0.007 (3)
N20.056 (4)0.036 (3)0.033 (3)0.009 (3)0.014 (3)0.003 (2)
N30.041 (3)0.043 (3)0.028 (3)0.002 (2)0.012 (2)0.003 (2)
N40.042 (3)0.056 (4)0.041 (3)0.014 (3)0.015 (3)0.005 (3)
C10.041 (4)0.055 (5)0.048 (5)0.008 (3)0.013 (3)0.009 (4)
C20.053 (5)0.041 (4)0.047 (4)0.005 (3)0.020 (4)0.014 (3)
C30.056 (5)0.037 (4)0.051 (5)0.001 (3)0.029 (4)0.003 (3)
C40.038 (4)0.049 (4)0.035 (4)0.003 (3)0.011 (3)0.005 (3)
C50.061 (5)0.050 (5)0.071 (6)0.005 (4)0.027 (5)0.009 (4)
C60.064 (6)0.073 (7)0.111 (9)0.021 (5)0.025 (6)0.013 (6)
C70.046 (5)0.095 (7)0.088 (7)0.008 (5)0.022 (5)0.013 (6)
C80.051 (5)0.091 (7)0.069 (6)0.007 (5)0.022 (4)0.011 (5)
C90.055 (5)0.056 (5)0.041 (4)0.007 (4)0.019 (4)0.000 (3)
C100.047 (4)0.046 (4)0.039 (4)0.009 (3)0.014 (3)0.012 (3)
C110.049 (5)0.052 (4)0.043 (4)0.000 (4)0.007 (3)0.008 (3)
C120.056 (5)0.044 (4)0.051 (5)0.005 (4)0.006 (4)0.000 (4)
C130.039 (4)0.076 (6)0.060 (5)0.001 (4)0.021 (4)0.001 (4)
C140.061 (6)0.073 (6)0.098 (8)0.005 (5)0.014 (5)0.003 (6)
C150.049 (6)0.107 (9)0.144 (11)0.013 (6)0.009 (7)0.033 (8)
C160.043 (6)0.142 (11)0.112 (10)0.021 (6)0.017 (6)0.006 (8)
C170.053 (7)0.145 (12)0.130 (11)0.005 (7)0.012 (7)0.034 (9)
C180.055 (6)0.090 (7)0.100 (8)0.002 (5)0.004 (5)0.037 (6)
Geometric parameters (Å, °) top
Pt1—N12.031 (5)C6—H6A0.9700
Pt1—N22.067 (5)C6—H6B0.9700
Pt1—Cl12.2990 (18)C7—C81.509 (12)
Pt1—Cl22.311 (2)C7—H7A0.9700
Pt2—N32.038 (5)C7—H7B0.9700
Pt2—N42.064 (6)C8—C91.513 (11)
Pt2—Cl42.294 (2)C8—H8A0.9700
Pt2—Cl32.2954 (19)C8—H8B0.9700
N1—C11.481 (8)C9—H9A0.9700
N1—H1A0.9000C9—H9B0.9700
N1—H1B0.9000C10—C111.512 (9)
N2—C31.503 (8)C10—H10A0.9700
N2—C41.509 (9)C10—H10B0.9700
N2—H2A0.9100C11—C121.521 (10)
N3—C101.465 (8)C11—H11A0.9700
N3—H3A0.9000C11—H11B0.9700
N3—H3B0.9000C12—H12A0.9700
N4—C131.501 (9)C12—H12B0.9700
N4—C121.514 (9)C13—C141.498 (12)
N4—H4B0.9100C13—C181.507 (11)
C1—C21.512 (10)C13—H13A0.9800
C1—H1D0.9700C14—C151.535 (13)
C1—H1C0.9700C14—H14A0.9700
C2—C31.528 (10)C14—H14B0.9700
C2—H2B0.9700C15—C161.507 (15)
C2—H2C0.9700C15—H15A0.9700
C3—H3C0.9700C15—H15B0.9700
C3—H3D0.9700C16—C171.520 (15)
C4—C51.516 (10)C16—H16A0.9700
C4—C91.534 (9)C16—H16B0.9700
C4—H4A0.9800C17—C181.520 (14)
C5—C61.546 (12)C17—H17A0.9700
C5—H5A0.9700C17—H17B0.9700
C5—H5B0.9700C18—H18A0.9700
C6—C71.500 (13)C18—H18B0.9700
N1—Pt1—N290.6 (2)C6—C7—C8110.3 (7)
N1—Pt1—Cl187.50 (16)C6—C7—H7A109.6
N2—Pt1—Cl1178.14 (16)C8—C7—H7A109.6
N1—Pt1—Cl2177.55 (17)C6—C7—H7B109.6
N2—Pt1—Cl290.78 (16)C8—C7—H7B109.6
Cl1—Pt1—Cl291.06 (7)H7A—C7—H7B108.1
N3—Pt2—N492.0 (2)C7—C8—C9111.7 (7)
N3—Pt2—Cl4177.16 (16)C7—C8—H8A109.3
N4—Pt2—Cl487.25 (17)C9—C8—H8A109.3
N3—Pt2—Cl389.21 (16)C7—C8—H8B109.3
N4—Pt2—Cl3177.96 (17)C9—C8—H8B109.3
Cl4—Pt2—Cl391.46 (9)H8A—C8—H8B107.9
C1—N1—Pt1115.0 (4)C8—C9—C4111.3 (7)
C1—N1—H1A108.5C8—C9—H9A109.4
Pt1—N1—H1A108.5C4—C9—H9A109.4
C1—N1—H1B108.5C8—C9—H9B109.4
Pt1—N1—H1B108.5C4—C9—H9B109.4
H1A—N1—H1B107.5H9A—C9—H9B108.0
C3—N2—C4115.2 (5)N3—C10—C11110.8 (6)
C3—N2—Pt1110.7 (4)N3—C10—H10A109.5
C4—N2—Pt1114.2 (4)C11—C10—H10A109.5
C3—N2—H2A105.2N3—C10—H10B109.5
C4—N2—H2A105.2C11—C10—H10B109.5
Pt1—N2—H2A105.2H10A—C10—H10B108.1
C10—N3—Pt2114.7 (4)C10—C11—C12115.0 (6)
C10—N3—H3A108.6C10—C11—H11A108.5
Pt2—N3—H3A108.6C12—C11—H11A108.5
C10—N3—H3B108.6C10—C11—H11B108.5
Pt2—N3—H3B108.6C12—C11—H11B108.5
H3A—N3—H3B107.6H11A—C11—H11B107.5
C13—N4—C12113.2 (6)N4—C12—C11113.2 (6)
C13—N4—Pt2119.8 (5)N4—C12—H12A108.9
C12—N4—Pt2111.6 (4)C11—C12—H12A108.9
C13—N4—H4B103.3N4—C12—H12B108.9
C12—N4—H4B103.3C11—C12—H12B108.9
Pt2—N4—H4B103.3H12A—C12—H12B107.7
N1—C1—C2112.5 (6)C14—C13—N4111.1 (7)
N1—C1—H1D109.1C14—C13—C18111.6 (7)
C2—C1—H1D109.1N4—C13—C18111.0 (7)
N1—C1—H1C109.1C14—C13—H13A107.6
C2—C1—H1C109.1N4—C13—H13A107.6
H1D—C1—H1C107.8C18—C13—H13A107.6
C1—C2—C3114.2 (6)C13—C14—C15111.5 (9)
C1—C2—H2B108.7C13—C14—H14A109.3
C3—C2—H2B108.7C15—C14—H14A109.3
C1—C2—H2C108.7C13—C14—H14B109.3
C3—C2—H2C108.7C15—C14—H14B109.3
H2B—C2—H2C107.6H14A—C14—H14B108.0
N2—C3—C2113.2 (5)C16—C15—C14111.2 (9)
N2—C3—H3C108.9C16—C15—H15A109.4
C2—C3—H3C108.9C14—C15—H15A109.4
N2—C3—H3D108.9C16—C15—H15B109.4
C2—C3—H3D108.9C14—C15—H15B109.4
H3C—C3—H3D107.7H15A—C15—H15B108.0
N2—C4—C5109.9 (6)C15—C16—C17110.0 (9)
N2—C4—C9112.4 (6)C15—C16—H16A109.7
C5—C4—C9110.6 (6)C17—C16—H16A109.7
N2—C4—H4A107.9C15—C16—H16B109.7
C5—C4—H4A107.9C17—C16—H16B109.7
C9—C4—H4A107.9H16A—C16—H16B108.2
C4—C5—C6112.3 (7)C18—C17—C16111.8 (9)
C4—C5—H5A109.1C18—C17—H17A109.3
C6—C5—H5A109.1C16—C17—H17A109.3
C4—C5—H5B109.1C18—C17—H17B109.3
C6—C5—H5B109.1C16—C17—H17B109.3
H5A—C5—H5B107.9H17A—C17—H17B107.9
C7—C6—C5110.0 (8)C13—C18—C17112.2 (9)
C7—C6—H6A109.7C13—C18—H18A109.2
C5—C6—H6A109.7C17—C18—H18A109.2
C7—C6—H6B109.7C13—C18—H18B109.2
C5—C6—H6B109.7C17—C18—H18B109.2
H6A—C6—H6B108.2H18A—C18—H18B107.9
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···Cl3i0.902.683.377 (6)135
N3—H3A···Cl1ii0.902.663.374 (6)137
N2—H2A···Cl4i0.912.813.622 (6)150
N1—H1B···Cl3iii0.902.663.439 (6)146
N1—H1A···Cl2iv0.902.753.605 (6)160
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+1, y−1/2, −z+1/2; (iv) x, −y+1/2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °)
top
D—H···AD—HH···AD···AD—H···A
N3—H3B···Cl3i0.902.683.377 (6)135
N3—H3A···Cl1ii0.902.663.374 (6)137
N2—H2A···Cl4i0.912.813.622 (6)150
N1—H1B···Cl3iii0.902.663.439 (6)146
N1—H1A···Cl2iv0.902.753.605 (6)160
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+1, y−1/2, −z+1/2; (iv) x, −y+1/2, z−1/2.
Acknowledgements top

This work was financially supported by Yunnan Natural Science Foundation (Nos. 20032 C06 and 2006 C0070M) and the National Science Foundation of Yunnan University (No. 2005Q002A).

references
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