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

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.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.013 Å
• R factor = 0.030
• wR factor = 0.085
• Data-to-parameter ratio = 24.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         O2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N1
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Pt1
PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         13
PLAT354_ALERT_3_C Short   O-H Bond (0.82A)   O3     -   H3D    ...       0.69 Ang.
PLAT360_ALERT_2_C Short  C(sp3)-C(sp3) Bond  C5     -   C6     ...       1.40 Ang.
PLAT417_ALERT_2_C Short Inter D-H..H-D       H1C    ..  H3D     ..       2.13 Ang.
PLAT482_ALERT_4_C Small D-H..A Angle Rep for N1     ..  O2      ..      97.00 Deg.
PLAT482_ALERT_4_C Small D-H..A Angle Rep for N1     ..  O1      ..      99.00 Deg.

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Pt1         (4)       3.94

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  11 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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).

S3. Refinement

H3C and H3D (for OH₂) were located in difference syntheses and refined isotropically [O—H = 0.69 (10) and 0.79 (7) Å and U_iso(H) = 0.062 (19) and 0.08 (3) Ų]. 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 U_iso(H) = 1.2U_eq(C,N).

Computing details

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

	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].
	Fig. 2. A partial packing diagram of (I). Hydrogen bonds are shown as dashed lines.

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

Crystal data

(C12H28N2O4)[PtCl6]·2H2O	F(000) = 692
Mr = 708.18	Dx = 1.972 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2000 reflections
a = 9.3668 (12) Å	θ = 2.4–29.3°
b = 12.5688 (11) Å	µ = 6.59 mm^−1
c = 10.9546 (15) Å	T = 298 K
β = 112.384 (9)°	Prism, yellow
V = 1192.5 (3) Å^3	0.25 × 0.18 × 0.10 mm
Z = 2

Data collection

Stoe IPDS II diffractometer	3168 independent reflections
Radiation source: fine-focus sealed tube	2493 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
Detector resolution: 0.15 mm pixels mm^-1	θmax = 29.3°, θmin = 2.4°
rotation method scans	h = −12→12
Absorption correction: numerical (X-RED; Stoe & Cie, 2005)	k = −17→13
Tmin = 0.250, Tmax = 0.510	l = −10→15
8277 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.22	w = 1/[σ^2(Fo^2) + (0.0394P)^2 + 0.839P] where P = (Fo^2 + 2Fc^2)/3
3168 reflections	(Δ/σ)max = 0.011
132 parameters	Δρmax = 1.27 e Å^−3
0 restraints	Δρmin = −0.66 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3080 (7)	0.8830 (6)	−0.0359 (7)	0.074 (2)
H1A	0.3526	0.9281	0.0412	0.089*
H1B	0.3907	0.8576	−0.0611	0.089*
C2	0.2280 (7)	0.7913 (5)	−0.0044 (7)	0.0660 (17)
H2A	0.1829	0.7470	−0.0822	0.079*
H2B	0.3025	0.7486	0.0643	0.079*
C3	0.0327 (10)	0.7382 (5)	0.0851 (8)	0.086 (2)
H3A	0.1064	0.7091	0.1667	0.103*
H3B	0.0038	0.6822	0.0192	0.103*
C4	−0.1087 (10)	0.7764 (6)	0.1067 (9)	0.088 (2)
H4A	−0.1832	0.8060	0.0257	0.105*
H4B	−0.1569	0.7178	0.1342	0.105*
C5	−0.1737 (10)	0.8963 (8)	0.2511 (10)	0.097 (3)
H5B	−0.2307	0.8373	0.2676	0.116*
H5A	−0.1197	0.9316	0.3348	0.116*
C6	−0.2797 (11)	0.9680 (9)	0.1662 (12)	0.108 (3)
H6A	−0.3505	0.9919	0.2061	0.130*
H6B	−0.3393	0.9326	0.0838	0.130*
N1	0.1050 (5)	0.8269 (3)	0.0404 (5)	0.0515 (10)
H1C	0.1456	0.8735	0.1072	0.062*
H1D	0.0317	0.8612	−0.0264	0.062*
O1	0.2010 (5)	0.9412 (4)	−0.1400 (5)	0.0696 (12)
O2	−0.0603 (5)	0.8538 (4)	0.2044 (5)	0.0697 (11)
O3	0.1170 (5)	1.0429 (4)	0.1461 (4)	0.0531 (9)
H3C	0.199 (8)	1.060 (6)	0.197 (7)	0.062 (19)*
H3D	0.076 (12)	1.015 (6)	0.176 (11)	0.08 (3)*
Pt1	0.5000	1.0000	0.5000	0.03249 (8)
Cl1	0.54112 (16)	1.13900 (10)	0.64977 (13)	0.0528 (3)
Cl2	0.45210 (13)	1.12134 (10)	0.32866 (12)	0.0489 (3)
Cl3	0.23954 (13)	0.99812 (10)	0.46689 (13)	0.0476 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.051 (3)	0.095 (5)	0.075 (4)	0.013 (3)	0.023 (3)	−0.023 (4)
C2	0.067 (4)	0.061 (3)	0.060 (4)	0.030 (3)	0.013 (3)	0.000 (3)
C3	0.165 (8)	0.035 (3)	0.073 (4)	−0.007 (4)	0.064 (5)	−0.004 (3)
C4	0.113 (6)	0.075 (5)	0.080 (5)	−0.045 (4)	0.043 (5)	−0.011 (4)
C5	0.103 (6)	0.115 (7)	0.103 (6)	−0.013 (5)	0.074 (6)	0.014 (6)
C6	0.072 (5)	0.143 (8)	0.131 (9)	0.000 (5)	0.063 (6)	0.036 (7)
N1	0.065 (3)	0.038 (2)	0.050 (2)	0.0104 (18)	0.019 (2)	−0.0004 (18)
O1	0.061 (2)	0.071 (3)	0.092 (3)	0.012 (2)	0.044 (2)	0.007 (3)
O2	0.082 (3)	0.053 (2)	0.090 (3)	−0.005 (2)	0.051 (3)	0.000 (2)
O3	0.044 (2)	0.063 (2)	0.046 (2)	−0.0040 (18)	0.0101 (17)	−0.002 (2)
Pt1	0.03113 (11)	0.03264 (11)	0.03280 (11)	−0.00666 (8)	0.01116 (8)	−0.00084 (10)
Cl1	0.0654 (7)	0.0460 (6)	0.0518 (7)	−0.0157 (5)	0.0276 (6)	−0.0151 (5)
Cl2	0.0440 (6)	0.0511 (7)	0.0459 (6)	−0.0080 (5)	0.0106 (5)	0.0102 (5)
Cl3	0.0354 (5)	0.0533 (6)	0.0552 (6)	−0.0044 (4)	0.0183 (4)	0.0045 (6)

Geometric parameters (Å, º)

Pt1—Cl2^i	2.3257 (12)	C2—H2A	0.9700
Pt1—Cl2	2.3257 (12)	C2—H2B	0.9700
Pt1—Cl3	2.3259 (12)	C3—N1	1.482 (8)
Pt1—Cl3^i	2.3259 (12)	C3—C4	1.509 (12)
Pt1—Cl1^i	2.3262 (12)	C3—H3A	0.9700
Pt1—Cl1	2.3262 (12)	C3—H3B	0.9700
O1—C6^ii	1.444 (11)	C4—O2	1.389 (9)
O3—H3C	0.79 (7)	C4—H4A	0.9700
O3—H3D	0.69 (10)	C4—H4B	0.9700
N1—H1C	0.9000	C5—C6	1.400 (13)
N1—H1D	0.9000	C5—O2	1.446 (9)
C1—O1	1.404 (8)	C5—H5B	0.9700
C1—C2	1.485 (10)	C5—H5A	0.9700
C1—H1A	0.9700	C6—O1^ii	1.444 (11)
C1—H1B	0.9700	C6—H6A	0.9700
C2—N1	1.483 (8)	C6—H6B	0.9700
Cl2^i—Pt1—Cl2	180	N1—C2—C1	111.5 (5)
Cl2^i—Pt1—Cl3	89.30 (4)	N1—C2—H2A	109.3
Cl2—Pt1—Cl3	90.70 (4)	C1—C2—H2A	109.3
Cl2^i—Pt1—Cl3^i	90.70 (4)	N1—C2—H2B	109.3
Cl2—Pt1—Cl3^i	89.30 (4)	C1—C2—H2B	109.3
Cl3—Pt1—Cl3^i	180	H2A—C2—H2B	108.0
Cl2^i—Pt1—Cl1^i	90.34 (5)	N1—C3—C4	110.6 (5)
Cl2—Pt1—Cl1^i	89.66 (5)	N1—C3—H3A	109.5
Cl3—Pt1—Cl1^i	90.02 (5)	C4—C3—H3A	109.5
Cl3^i—Pt1—Cl1^i	89.98 (5)	N1—C3—H3B	109.5
Cl2^i—Pt1—Cl1	89.66 (5)	C4—C3—H3B	109.5
Cl2—Pt1—Cl1	90.34 (5)	H3A—C3—H3B	108.1
Cl3—Pt1—Cl1	89.98 (5)	O2—C4—C3	107.2 (6)
Cl3^i—Pt1—Cl1	90.02 (5)	O2—C4—H4A	110.3
Cl1^i—Pt1—Cl1	180	C3—C4—H4A	110.3
C1—O1—C6^ii	108.3 (6)	O2—C4—H4B	110.3
C4—O2—C5	117.6 (6)	C3—C4—H4B	110.3
H3C—O3—H3D	112 (10)	H4A—C4—H4B	108.5
C3—N1—C2	113.1 (5)	C6—C5—O2	115.7 (7)
C3—N1—H1C	109.0	C6—C5—H5B	108.4
C2—N1—H1C	109.0	O2—C5—H5B	108.4
C3—N1—H1D	109.0	C6—C5—H5A	108.4
C2—N1—H1D	109.0	O2—C5—H5A	108.4
H1C—N1—H1D	107.8	H5B—C5—H5A	107.4
O1—C1—C2	109.1 (5)	C5—C6—O1^ii	110.8 (7)
O1—C1—H1A	109.9	C5—C6—H6A	109.5
C2—C1—H1A	109.9	O1^ii—C6—H6A	109.5
O1—C1—H1B	109.9	C5—C6—H6B	109.5
C2—C1—H1B	109.9	O1^ii—C6—H6B	109.5
H1A—C1—H1B	108.3	H6A—C6—H6B	108.1
O1—C1—C2—N1	−62.0 (7)	C1—C2—N1—C3	−174.4 (6)
N1—C3—C4—O2	−61.1 (8)	C2—C1—O1—C6^ii	178.1 (7)
O2—C5—C6—O1^ii	−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, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O2	0.90	2.55	2.803 (9)	97
N1—H1C···O3	0.90	2.21	2.936 (7)	138
N1—H1D···O1	0.90	2.57	2.852 (8)	99
O3—H3C···Cl2	0.79 (6)	2.39 (6)	3.169 (4)	173 (7)
O3—H3D···O2	0.69 (13)	2.48 (10)	3.103 (7)	152 (10)
N1—H1D···O3^ii	0.90	1.93	2.817 (6)	169
O3—H3D···O1^ii	0.69 (13)	2.53 (12)	2.961 (7)	123 (12)

Symmetry code: (ii) −x, −y+2, −z.