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Acta Cryst. (2007). E63, m2460-m2461    [ doi:10.1107/S1600536807042341 ]

1,10-Diazonia-18-crown-6 hexachloridoplatinate(IV) dihydrate

M. Yousefi, S. Teimouri, V. Amani and H. R. Khavasi

Abstract top

The asymmetric unit of the title compound, (C12H28N2O4)[PtCl6]·2H2O, contains one half-cation, one half-anion and one water molecule, both ions lying on inversion centres. The Pt ion has an octahedral coordination. In the crystal structure, intermolecular O-H...Cl, N-H...O and O-H...O hydrogen bonds result in the formation of a supramolecular structure.

Comment top

Recently, we reported the synthesis and crystal structure of [(H2DA18C6)Cl2], (II), (Yousefi et al., 2007) [where H2DA18C6 is 1,10 –Diazonia-18-crown-6]. Several proton transfer systems using 1,10-diaza-18 -crown-6, with proton donor molecules,such as [(H2DA18C6)I2·2H2O], (III), (Chekhlov, 2005), [(H2DA18C6)(C2HO4)2], (IV), and [(H2DA18C6)2(C2O4)2·2H2O], (V), (Chekhlov, 2000), [(H2DA18C6)(picrate)2], (VI), (Chekhlov, 2001), [(H2DA18C6)(HPTD)2], (VII), (Simonov et al., 2003), [(H2DA18C6)(PD)2·(H2O)4], (VIII), and [(H2DA18C6)(PS)2·(H2O)2], (IX), (Fonari et al., 2004), [(H2DA18C6)(CCl3COO)2(CCl3COOH)2], (X), (Chekhlov et al., 1994), [(H2DA18C6)(CCl3COO)2], (XI), (Chekhlov & Martynov, 1998), and {[H2DA18C6][(ArSO2)2N]2}, (XII), (Moers et al., 2000) [where H2DA18C6 is 1,10-Diazonia-18-crown-6, C2O4 is oxalate, HPTD is (4Z,5E)-pyrimidine-2,4,5,6(1H,3H)-tetraone 4,5-dioxime anion, PD is 2-(2-methylphenyl)-2H-[1,2,3]triazolo[4,5-d] pyrimidine-5,7(4H,6H)-dione 3-oxide anion, PS is 6-amino-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-5-yl- sulfamate and (ArSO2)2N is bis(4-chlorobenzenesulfonyl)imide] have been synthesized and characterized by single-crystal X-ray diffraction methods.

There are also several proton transfer systems using H2[PtCl6] with proton acceptor molecules, such as [HpyBr-3]2[PtCl6]·2H2O, (XIII), and [HpyI-3]2[PtCl6]·2H2O, (XIV), (Zordan & Brammer, 2004), [BMIM]2[PtCl6], (XV), and [EMIM]2[PtCl6], (XVI), (Hasan et al., 2001), {(DABCO)H2[PtCl6]}, (XVI), (Juan et al., 1998), {p-C6H4 (CH2ImMe)2[PtCl6]}, (XVIII), (Li & Liu, 2003), [het][PtCl6]·2H2O, (XIX), (Hu et al., 2003), [9-MeGuaH]2[PtCl6]·2H2O, (XX), (Terzis & Mentzafos, 1983) and [H10[30]aneN10][PtCl6]2Cl6·2H2O, (XXI), (Bencini et al., 1992) [Where BMIM+ is 1-n-butyl-3-methylimidazolium, EMIM+ is 1-ethyl-3-methyl- imidazolium, DABCO is 1,4-diazabicyclooctane, het is 2-(?-hydroxyethyl) thiamine and 9-MeGuaH is 9-methylguaninium] have been synthesized and characterized by single-crystal X-ray diffraction methods. We report herein the synthesis and crystal structure of the title compound, (I).

The asymmetric unit of (I), (Fig. 1), contains one half-cation, one half-anion and one water molecule. The Pt ion has an octahedral coordination. The bond lengths and angles, in cation, are in good agreement with the corresponding values in (II) and (III). Also, the Pt—Cl bond lengths and angles (Table 1) are within normal ranges, as in [H10[30]ane][PtCl6]2Cl6·2H2O, (XXII), (Bencini et al., 1992).

In the crystal structure, the intermolecular O—H···Cl, N—H···O and O—H···O hydrogen bonds (Table 2) seem to be effective in the stabilization of the crystal structure, resulting in the formation of a supramolecular structure (Fig. 2).

Related literature top

For related literature, see: Bencini et al. (1992); Chekhlov (2000, 2001, 2005); Chekhlov & Martynov (1998); Chekhlov et al. (1994); Fonari et al. (2004); Hasan et al. (2001); Hu et al. (2003); Juan et al. (1998); Li & Liu (2003); Moers et al. (2000); Simonov et al. (2003); Terzis & Mentzafos (1983); Yousefi et al. (2007); Zordan & Brammer (2004).

Experimental top

For the preparation of the title compound, (I), a solution of 1,10-diaza-18 -crown-6 (0.10 g, 0.37 mmol) in water (50 ml) was added to a solution of H2PtCl6·2H2O (0.20 g, 0.37 mmol) in water (30 ml) and the resulting yellow solution was stirred for 30 min at 333 K. Then, it was left to evaporate slowly at room temperature. After 24 h, yellow prismatic crystals of (I) were isolated (yield; 0.22 g, 84%, m.p. 470–472 K).

Refinement top

H3C and H3D (for OH2) were located in difference syntheses and refined isotropically [O—H = 0.69 (10) and 0.79 (7) Å and Uiso(H) = 0.062 (19) and 0.08 (3) Å2]. The remaining H atoms were positioned geometrically, with N—H = 0.90 Å and C—H = 0.97 Å for methylene H, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,N).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-RED (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [symmetry codes: (a) 1 − x, 2 − y, 1 − z; (b) −x, 2 − y, −z].
[Figure 2] Fig. 2. A partial packing diagram of (I). Hydrogen bonds are shown as dashed lines.
1,10-Diazonia-18-crown-6 hexachloridoplatinate(IV) dihydrate top
Crystal data top
(C12H28N2O4)[PtCl6]·2H2OF000 = 692
Mr = 708.18Dx = 1.972 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2000 reflections
a = 9.3668 (12) Åθ = 2.4–29.3º
b = 12.5688 (11) ŵ = 6.59 mm−1
c = 10.9546 (15) ÅT = 298 (2) K
β = 112.384 (9)ºPrism, yellow
V = 1192.5 (3) Å30.25 × 0.18 × 0.10 mm
Z = 2
Data collection top
Stoe IPDS II
diffractometer		3168 independent reflections
Radiation source: fine-focus sealed tube2493 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.036
Detector resolution: 0.15 mm pixels mm-1θmax = 29.3º
T = 298(2) Kθmin = 2.4º
rotation method scansh = −12→12
Absorption correction: numerical
(X-RED; Stoe & Cie, 2005)		k = −17→13
Tmin = 0.250, Tmax = 0.510l = −10→15
8277 measured reflections
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)] = 0.030H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.085  w = 1/[σ2(Fo2) + (0.0394P)2 + 0.839P]
where P = (Fo2 + 2Fc2)/3
S = 1.22(Δ/σ)max = 0.011
3168 reflectionsΔρmax = 1.27 e Å−3
132 parametersΔρmin = −0.66 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
(C12H28N2O4)[PtCl6]·2H2OV = 1192.5 (3) Å3
Mr = 708.18Z = 2
Monoclinic, P21/cMo Kα
a = 9.3668 (12) ŵ = 6.59 mm−1
b = 12.5688 (11) ÅT = 298 (2) K
c = 10.9546 (15) Å0.25 × 0.18 × 0.10 mm
β = 112.384 (9)º
Data collection top
Stoe IPDS II
diffractometer		3168 independent reflections
Absorption correction: numerical
(X-RED; Stoe & Cie, 2005)		2493 reflections with I > 2σ(I)
Tmin = 0.250, Tmax = 0.510Rint = 0.036
8277 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.030132 parameters
wR(F2) = 0.085H atoms treated by a mixture of
independent and constrained refinement
S = 1.22Δρmax = 1.27 e Å−3
3168 reflectionsΔρmin = −0.66 e Å−3
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 > 2sigma(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
C10.3080 (7)0.8830 (6)−0.0359 (7)0.074 (2)
H1A0.35260.92810.04120.089*
H1B0.39070.8576−0.06110.089*
C20.2280 (7)0.7913 (5)−0.0044 (7)0.0660 (17)
H2A0.18290.7470−0.08220.079*
H2B0.30250.74860.06430.079*
C30.0327 (10)0.7382 (5)0.0851 (8)0.086 (2)
H3A0.10640.70910.16670.103*
H3B0.00380.68220.01920.103*
C4−0.1087 (10)0.7764 (6)0.1067 (9)0.088 (2)
H4A−0.18320.80600.02570.105*
H4B−0.15690.71780.13420.105*
C5−0.1737 (10)0.8963 (8)0.2511 (10)0.097 (3)
H5B−0.23070.83730.26760.116*
H5A−0.11970.93160.33480.116*
C6−0.2797 (11)0.9680 (9)0.1662 (12)0.108 (3)
H6A−0.35050.99190.20610.130*
H6B−0.33930.93260.08380.130*
N10.1050 (5)0.8269 (3)0.0404 (5)0.0515 (10)
H1C0.14560.87350.10720.062*
H1D0.03170.8612−0.02640.062*
O10.2010 (5)0.9412 (4)−0.1400 (5)0.0696 (12)
O2−0.0603 (5)0.8538 (4)0.2044 (5)0.0697 (11)
O30.1170 (5)1.0429 (4)0.1461 (4)0.0531 (9)
H3C0.199 (8)1.060 (6)0.197 (7)0.062 (19)*
H3D0.076 (12)1.015 (6)0.176 (11)0.08 (3)*
Pt10.50001.00000.50000.03249 (8)
Cl10.54112 (16)1.13900 (10)0.64977 (13)0.0528 (3)
Cl20.45210 (13)1.12134 (10)0.32866 (12)0.0489 (3)
Cl30.23954 (13)0.99812 (10)0.46689 (13)0.0476 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.051 (3)0.095 (5)0.075 (4)0.013 (3)0.023 (3)−0.023 (4)
C20.067 (4)0.061 (3)0.060 (4)0.030 (3)0.013 (3)0.000 (3)
C30.165 (8)0.035 (3)0.073 (4)−0.007 (4)0.064 (5)−0.004 (3)
C40.113 (6)0.075 (5)0.080 (5)−0.045 (4)0.043 (5)−0.011 (4)
C50.103 (6)0.115 (7)0.103 (6)−0.013 (5)0.074 (6)0.014 (6)
C60.072 (5)0.143 (8)0.131 (9)0.000 (5)0.063 (6)0.036 (7)
N10.065 (3)0.038 (2)0.050 (2)0.0104 (18)0.019 (2)−0.0004 (18)
O10.061 (2)0.071 (3)0.092 (3)0.012 (2)0.044 (2)0.007 (3)
O20.082 (3)0.053 (2)0.090 (3)−0.005 (2)0.051 (3)0.000 (2)
O30.044 (2)0.063 (2)0.046 (2)−0.0040 (18)0.0101 (17)−0.002 (2)
Pt10.03113 (11)0.03264 (11)0.03280 (11)−0.00666 (8)0.01116 (8)−0.00084 (10)
Cl10.0654 (7)0.0460 (6)0.0518 (7)−0.0157 (5)0.0276 (6)−0.0151 (5)
Cl20.0440 (6)0.0511 (7)0.0459 (6)−0.0080 (5)0.0106 (5)0.0102 (5)
Cl30.0354 (5)0.0533 (6)0.0552 (6)−0.0044 (4)0.0183 (4)0.0045 (6)
Geometric parameters (Å, °) top
Pt1—Cl2i2.3257 (12)C2—H2A0.9700
Pt1—Cl22.3257 (12)C2—H2B0.9700
Pt1—Cl32.3259 (12)C3—N11.482 (8)
Pt1—Cl3i2.3259 (12)C3—C41.509 (12)
Pt1—Cl1i2.3262 (12)C3—H3A0.9700
Pt1—Cl12.3262 (12)C3—H3B0.9700
O1—C6ii1.444 (11)C4—O21.389 (9)
O3—H3C0.79 (7)C4—H4A0.9700
O3—H3D0.69 (10)C4—H4B0.9700
N1—H1C0.9000C5—C61.400 (13)
N1—H1D0.9000C5—O21.446 (9)
C1—O11.404 (8)C5—H5B0.9700
C1—C21.485 (10)C5—H5A0.9700
C1—H1A0.9700C6—O1ii1.444 (11)
C1—H1B0.9700C6—H6A0.9700
C2—N11.483 (8)C6—H6B0.9700
Cl2i—Pt1—Cl2180N1—C2—C1111.5 (5)
Cl2i—Pt1—Cl389.30 (4)N1—C2—H2A109.3
Cl2—Pt1—Cl390.70 (4)C1—C2—H2A109.3
Cl2i—Pt1—Cl3i90.70 (4)N1—C2—H2B109.3
Cl2—Pt1—Cl3i89.30 (4)C1—C2—H2B109.3
Cl3—Pt1—Cl3i180H2A—C2—H2B108.0
Cl2i—Pt1—Cl1i90.34 (5)N1—C3—C4110.6 (5)
Cl2—Pt1—Cl1i89.66 (5)N1—C3—H3A109.5
Cl3—Pt1—Cl1i90.02 (5)C4—C3—H3A109.5
Cl3i—Pt1—Cl1i89.98 (5)N1—C3—H3B109.5
Cl2i—Pt1—Cl189.66 (5)C4—C3—H3B109.5
Cl2—Pt1—Cl190.34 (5)H3A—C3—H3B108.1
Cl3—Pt1—Cl189.98 (5)O2—C4—C3107.2 (6)
Cl3i—Pt1—Cl190.02 (5)O2—C4—H4A110.3
Cl1i—Pt1—Cl1180C3—C4—H4A110.3
C1—O1—C6ii108.3 (6)O2—C4—H4B110.3
C4—O2—C5117.6 (6)C3—C4—H4B110.3
H3C—O3—H3D112 (10)H4A—C4—H4B108.5
C3—N1—C2113.1 (5)C6—C5—O2115.7 (7)
C3—N1—H1C109.0C6—C5—H5B108.4
C2—N1—H1C109.0O2—C5—H5B108.4
C3—N1—H1D109.0C6—C5—H5A108.4
C2—N1—H1D109.0O2—C5—H5A108.4
H1C—N1—H1D107.8H5B—C5—H5A107.4
O1—C1—C2109.1 (5)C5—C6—O1ii110.8 (7)
O1—C1—H1A109.9C5—C6—H6A109.5
C2—C1—H1A109.9O1ii—C6—H6A109.5
O1—C1—H1B109.9C5—C6—H6B109.5
C2—C1—H1B109.9O1ii—C6—H6B109.5
H1A—C1—H1B108.3H6A—C6—H6B108.1
O1—C1—C2—N1−62.0 (7)C1—C2—N1—C3−174.4 (6)
N1—C3—C4—O2−61.1 (8)C2—C1—O1—C6ii178.1 (7)
O2—C5—C6—O1ii−59.2 (13)C3—C4—O2—C5−174.7 (6)
C4—C3—N1—C2−170.2 (6)C6—C5—O2—C4−75.3 (10)
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x, −y+2, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O20.902.552.803 (9)97
N1—H1C···O30.902.212.936 (7)138
N1—H1D···O10.902.572.852 (8)99
O3—H3C···Cl20.79 (6)2.39 (6)3.169 (4)173 (7)
O3—H3D···O20.69 (13)2.48 (10)3.103 (7)152 (10)
N1—H1D···O3ii0.901.932.817 (6)169
O3—H3D···O1ii0.69 (13)2.53 (12)2.961 (7)123 (12)
Symmetry codes: (ii) −x, −y+2, −z.
Selected geometric parameters (Å, °) top
Pt1—Cl2i2.3257 (12)Pt1—Cl3i2.3259 (12)
Pt1—Cl22.3257 (12)Pt1—Cl1i2.3262 (12)
Pt1—Cl32.3259 (12)Pt1—Cl12.3262 (12)
Cl2i—Pt1—Cl2180Cl3—Pt1—Cl1i90.02 (5)
Cl2i—Pt1—Cl389.30 (4)Cl3i—Pt1—Cl1i89.98 (5)
Cl2i—Pt1—Cl3i90.70 (4)Cl2i—Pt1—Cl189.66 (5)
Cl2—Pt1—Cl3i89.30 (4)Cl2—Pt1—Cl190.34 (5)
Cl3—Pt1—Cl3i180Cl3—Pt1—Cl189.98 (5)
Cl2i—Pt1—Cl1i90.34 (5)Cl3i—Pt1—Cl190.02 (5)
Cl2—Pt1—Cl1i89.66 (5)Cl1i—Pt1—Cl1180
Symmetry codes: (i) −x+1, −y+2, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O20.902.552.803 (9)97
N1—H1C···O30.902.212.936 (7)138
N1—H1D···O10.902.572.852 (8)99
O3—H3C···Cl20.79 (6)2.39 (6)3.169 (4)173 (7)
O3—H3D···O20.69 (13)2.48 (10)3.103 (7)152 (10)
N1—H1D···O3ii0.901.932.817 (6)169
O3—H3D···O1ii0.69 (13)2.53 (12)2.961 (7)123 (12)
Symmetry codes: (ii) −x, −y+2, −z.
Acknowledgements top

We are grateful to the Islamic Azad University, Shahr-e-Rey Branch, the Research Institute in Education and Shahid Beheshti University for financial support.

references
References top

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