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The asymmetric unit of the title compound, (C14H13N2)2[PtCl6], contains one independent protonated 2,9-dimethyl-1,10-phenanthrolinium cation and half of a centrosymmetric [PtCl6]2− anion. The Pt ion has an octa­hedral coordination. Intra­molecular N—H...Cl and N—H...N hydrogen bonds help to stabilize the structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807059594/hk2386sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807059594/hk2386Isup2.hkl
Contains datablock I

CCDC reference: 674061

Key indicators

  • Single-crystal X-ray study
  • T = 120 K
  • Mean [sigma](C-C) = 0.007 Å
  • R factor = 0.037
  • wR factor = 0.100
  • Data-to-parameter ratio = 20.9

checkCIF/PLATON results

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Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C1 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C12 PLAT432_ALERT_2_C Short Inter X...Y Contact Cl2 .. C9 .. 3.22 Ang. PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1 C14 H13 N2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

We reported the synthesis and crystal structure of [(H2DA18C6)Cl2], (II), (Yousefi et al., 2007), [H2DA18C6][PtCl6]·2H2O, (III), (Yousefi et al., 2007a) and [TBA]3[PtCl6]Cl, (IV), (Yousefi et al., 2007b) [where H2DA18C6 is 1,10-Diazonia-18-crown-6 and TBA is tribenzylammonium], recently. We have also, reported the synthesis and crystal structure of [PtCl4(pz)2], (V), (Yousefi et al., 2007c) [where pz is pyrazine]. Several proton transfer systems using 2,9-dimethyl-1,10-phenanthroline, with proton donor molecules, such as [Dmphen](ClO4), (VI), (Morsali, 2005), [Dmphen](NO3), (VII), (Yu et al., 2006), [Dmphen][Ru(CO)3Cl3], (VIII), (Moreno et al., 2006) and [Dmphen] [FeCl4], (IX), (Veidis et al., 1981) [where Dmphen is 2,9-dimethyl-1,10 -phenanthrolinium] 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, (X), and [HpyI-3]2 [PtCl6]·2H2O, (XI), (Zordan & Brammer, 2004), [BMIM]2[PtCl6], (XII), and [EMIM]2[PtCl6], (XIII), (Hasan et al., 2001), {(DABCO)H2[PtCl6]}, (XIV), (Juan et al., 1998), {p-C6H4(CH2ImMe)2[PtCl6]}, (XV), (Li & Liu, 2003), [het][PtCl6]·2H2O, (XVI), (Hu et al., 2003), [9-MeGuaH]2 [PtCl6]·2H2O, (XVII), (Terzis & Mentzafos, 1983), [H10[30]aneN10] [PtCl6]2Cl6·2H2O, (XVIII), (Bencini et al., 1992), [H2Me2ppz] [PtCl6], (XIX), (Ciccarese et al., 1998), [PA]2[PtCl6]Cl, (XX), (Delafontaine et al., 1987), [DEA]2[PtCl6], (XXI), (Bokach et al., 2003) and [HpyCl-3]3[PtCl6]Cl, (XXII), (Zordan et al., 2005) [where hpy is halopyridinium, BMIM+ is 1-n-butyl-3-methylimidazolium, EMIM+ is 1-ethyl -3-methylimidazolium, DABCO is 1,4-diazabicyclooctane, Im is imidazolium, het is 2-(α-hydroxyethyl)thiamine, 9-MeGuaH is 9-methylguaninium, [H10[30]aneN10] is [C20H60N10]10+ cation, H2Me2ppz is N,N'-dimethylpiperazinium, PA is pentane-1,5-diammonium and DEA is diethyl- ammonium] 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 independent protonated 2,9-dimethyl-1,10-phenanthroline cation and one half PtCl2-6 anion. The Pt ion has an octahedral coordination (Table 1). In cation, the bond lengths and angles are in good agreement with the corresponding values in (VI) and (VII). In PtCl2-6 anion, the Pt—Cl bond lengths and Cl—Pt—Cl bond angles (Table 1) are also within normal ranges, as in (III) and (IV).

The intramolecular N—H···Cl and N—H···N hydrogen bonds (Table 2) seem to be effective in the stabilization of the structure.

Related literature top

For related literature, see: Yousefi, Amani et al. (2007); Yousefi, Teimouri et al. (2007a,b,c); Morsali (2005); Yu et al. (2006); Moreno et al. (2006); Veidis et al. (1981); Zordan & Brammer (2004); Hasan et al. (2001); Juan et al. (1998); Li & Liu (2003); Hu et al. (2003); Terzis & Mentzafos (1983); Bencini et al. (1992); Ciccarese et al. (1998); Delafontaine et al. (1987); Bokach et al. (2003); Zordan et al. (2005).

For related literature, see: Delafontaine et al. (1987).

Experimental top

For the preparation of the title compound, (I), a solution of 2,9-dimethyl-1,10 -phenanthroline (0.31 g, 1.48 mmol) in methanol (10 ml) was added to a solution of H2PtCl6·6H2O, (0.38 g, 0.74 mmol) in methanol (10 ml) at room temperature. The suitable crystals for X-ray analysis were obtained by methanol diffusion in a solution of yellow precipitate in DMSO after one week (yield; 0.51 g, 83.4%).

Refinement top

H atom (for NH) was located in difference syntheses and refined isotropically [N—H = 0.93 (7) Å and Uiso(H) = 0.021 (14) Å2]. The remaining H atoms were positioned geometrically, with C—H = 0.93 and 0.96 Å, for aromatic and methyl H atoms and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).

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.
Bis(2,9-dimethyl-1,10-phenanthrolinium) hexachloridoplatinate(IV) top
Crystal data top
(C14H13N2)2[PtCl6]Z = 1
Mr = 826.31F(000) = 402
Triclinic, P1Dx = 1.862 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.9617 (10) ÅCell parameters from 4500 reflections
b = 9.2179 (10) Åθ = 2.3–29.2°
c = 9.9930 (11) ŵ = 5.33 mm1
α = 78.427 (9)°T = 120 K
β = 66.464 (8)°Block, orange
γ = 79.540 (9)°0.50 × 0.27 × 0.25 mm
V = 736.70 (14) Å3
Data collection top
Stoe IPDSII
diffractometer
3817 independent reflections
Radiation source: fine-focus sealed tube3813 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.073
Detector resolution: 0.15 mm pixels mm-1θmax = 29.2°, θmin = 2.3°
rotation method scansh = 1212
Absorption correction: numerical
(shape of crystal determined optically)
k = 1112
Tmin = 0.195, Tmax = 0.265l = 1313
8112 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)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.100 w = 1/[σ2(Fo2) + (0.0772P)2 + 0.2717P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.015
3817 reflectionsΔρmax = 2.93 e Å3
183 parametersΔρmin = 3.20 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.061 (6)
Crystal data top
(C14H13N2)2[PtCl6]γ = 79.540 (9)°
Mr = 826.31V = 736.70 (14) Å3
Triclinic, P1Z = 1
a = 8.9617 (10) ÅMo Kα radiation
b = 9.2179 (10) ŵ = 5.33 mm1
c = 9.9930 (11) ÅT = 120 K
α = 78.427 (9)°0.50 × 0.27 × 0.25 mm
β = 66.464 (8)°
Data collection top
Stoe IPDSII
diffractometer
3817 independent reflections
Absorption correction: numerical
(shape of crystal determined optically)
3813 reflections with I > 2σ(I)
Tmin = 0.195, Tmax = 0.265Rint = 0.073
8112 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.100H atoms treated by a mixture of independent and constrained refinement
S = 1.10Δρmax = 2.93 e Å3
3817 reflectionsΔρmin = 3.20 e Å3
183 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
Pt10.00000.50000.00000.01485 (12)
Cl10.24815 (12)0.59692 (11)0.02163 (13)0.0257 (2)
Cl20.03063 (12)0.26384 (11)0.02698 (12)0.02210 (19)
Cl30.13725 (14)0.43950 (12)0.25290 (11)0.0255 (2)
N10.2722 (5)0.1814 (4)0.5578 (4)0.0221 (6)
N20.3408 (4)0.1347 (4)0.3301 (4)0.0205 (6)
H20.349 (8)0.228 (7)0.356 (7)0.021 (14)*
C10.2682 (9)0.3619 (6)0.7008 (6)0.0383 (12)
H1A0.38210.39740.72500.046*
H1B0.20350.42450.61570.046*
H1C0.23850.36440.78250.046*
C20.2375 (6)0.2055 (5)0.6681 (5)0.0254 (8)
C30.1730 (6)0.0873 (5)0.7538 (5)0.0254 (8)
H30.14840.10820.82950.031*
C40.1473 (6)0.0565 (5)0.7255 (5)0.0243 (8)
H40.10680.13380.78190.029*
C50.1839 (5)0.0844 (5)0.6073 (4)0.0210 (7)
C60.1628 (6)0.2299 (5)0.5680 (5)0.0244 (8)
H60.11930.31090.61860.029*
C70.2057 (6)0.2517 (5)0.4571 (5)0.0238 (7)
H70.19340.34740.43470.029*
C80.2693 (5)0.1287 (5)0.3755 (4)0.0203 (7)
C90.3174 (5)0.1435 (5)0.2607 (5)0.0250 (8)
H90.31030.23730.23610.030*
C100.3751 (5)0.0186 (6)0.1850 (5)0.0257 (8)
H100.40690.02880.10980.031*
C110.3858 (5)0.1233 (5)0.2207 (5)0.0228 (7)
C120.4467 (6)0.2634 (6)0.1432 (5)0.0288 (9)
H12A0.36300.32940.10030.035*
H12B0.54250.31110.21280.035*
H12C0.47380.23950.06710.035*
C130.2848 (5)0.0152 (4)0.4093 (4)0.0178 (6)
C140.2458 (5)0.0393 (4)0.5291 (4)0.0185 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.01930 (15)0.01366 (15)0.01486 (14)0.00114 (7)0.01009 (9)0.00206 (7)
Cl10.0245 (4)0.0221 (4)0.0365 (5)0.0005 (3)0.0191 (4)0.0028 (4)
Cl20.0259 (4)0.0170 (4)0.0267 (5)0.0028 (3)0.0117 (4)0.0061 (3)
Cl30.0373 (5)0.0220 (4)0.0172 (4)0.0047 (4)0.0099 (4)0.0026 (3)
N10.0298 (17)0.0175 (15)0.0190 (15)0.0037 (12)0.0090 (13)0.0023 (12)
N20.0219 (15)0.0207 (16)0.0194 (15)0.0020 (12)0.0093 (12)0.0008 (12)
C10.072 (4)0.020 (2)0.029 (2)0.007 (2)0.025 (2)0.0055 (17)
C20.038 (2)0.0199 (18)0.0201 (18)0.0067 (15)0.0115 (17)0.0014 (14)
C30.036 (2)0.025 (2)0.0188 (17)0.0073 (16)0.0135 (16)0.0022 (15)
C40.034 (2)0.0250 (19)0.0174 (17)0.0060 (15)0.0140 (16)0.0009 (14)
C50.0282 (18)0.0202 (18)0.0165 (16)0.0053 (14)0.0102 (14)0.0004 (13)
C60.032 (2)0.0170 (17)0.0227 (18)0.0015 (14)0.0115 (16)0.0012 (14)
C70.033 (2)0.0176 (17)0.0222 (18)0.0003 (14)0.0122 (16)0.0044 (14)
C80.0226 (17)0.0197 (17)0.0192 (17)0.0024 (13)0.0076 (14)0.0050 (14)
C90.0238 (18)0.028 (2)0.0247 (19)0.0057 (15)0.0082 (16)0.0060 (16)
C100.0239 (18)0.036 (2)0.0210 (18)0.0054 (16)0.0100 (15)0.0068 (16)
C110.0170 (15)0.031 (2)0.0208 (18)0.0020 (14)0.0097 (14)0.0012 (15)
C120.0261 (19)0.034 (2)0.028 (2)0.0002 (16)0.0165 (17)0.0040 (17)
C130.0207 (16)0.0188 (17)0.0153 (15)0.0017 (12)0.0087 (13)0.0019 (12)
C140.0243 (17)0.0177 (17)0.0154 (15)0.0047 (13)0.0085 (13)0.0023 (13)
Geometric parameters (Å, º) top
Pt1—Cl12.3184 (10)C6—C71.369 (6)
Pt1—Cl1i2.3184 (10)C6—H60.9300
Pt1—Cl22.3235 (9)C7—C81.429 (6)
Pt1—Cl2i2.3235 (9)C7—H70.9300
Pt1—Cl3i2.3263 (11)C8—C131.403 (5)
Pt1—Cl32.3263 (11)C8—C91.414 (6)
N2—H20.93 (7)C9—C101.383 (7)
C1—C21.495 (6)C9—H90.9300
C1—H1A0.9600C10—C111.400 (6)
C1—H1B0.9600C10—H100.9300
C1—H1C0.9600C11—N21.336 (5)
C2—N11.325 (6)C11—C121.498 (6)
C2—C31.432 (6)C12—H12A0.9600
C3—C41.370 (6)C12—H12B0.9600
C3—H30.9300C12—H12C0.9600
C4—C51.426 (6)C13—N21.364 (5)
C4—H40.9300C13—C141.441 (5)
C5—C141.407 (6)C14—N11.355 (5)
C5—C61.431 (6)
Cl1—Pt1—Cl1i180C7—C6—H6119.5
Cl1—Pt1—Cl291.41 (4)C5—C6—H6119.5
Cl1i—Pt1—Cl288.59 (4)C6—C7—C8120.6 (4)
Cl1—Pt1—Cl2i88.59 (4)C6—C7—H7119.7
Cl1i—Pt1—Cl2i91.41 (4)C8—C7—H7119.7
Cl2—Pt1—Cl2i180C13—C8—C9117.6 (4)
Cl1—Pt1—Cl3i90.59 (4)C13—C8—C7118.9 (4)
Cl1i—Pt1—Cl3i89.41 (4)C9—C8—C7123.5 (4)
Cl2—Pt1—Cl3i91.76 (4)C10—C9—C8120.0 (4)
Cl2i—Pt1—Cl3i88.24 (4)C10—C9—H9120.0
Cl1—Pt1—Cl389.41 (4)C8—C9—H9120.0
Cl1i—Pt1—Cl390.59 (4)C9—C10—C11120.5 (4)
Cl2—Pt1—Cl388.24 (4)C9—C10—H10119.7
Cl2i—Pt1—Cl391.76 (4)C11—C10—H10119.7
Cl3i—Pt1—Cl3180N2—C11—C10118.5 (4)
C2—C1—H1A109.5N2—C11—C12118.1 (4)
C2—C1—H1B109.5C10—C11—C12123.4 (4)
H1A—C1—H1B109.5C11—C12—H12A109.5
C2—C1—H1C109.5C11—C12—H12B109.5
H1A—C1—H1C109.5H12A—C12—H12B109.5
H1B—C1—H1C109.5C11—C12—H12C109.5
N1—C2—C3121.8 (4)H12A—C12—H12C109.5
N1—C2—C1117.6 (4)H12B—C12—H12C109.5
C3—C2—C1120.5 (4)N2—C13—C8120.0 (4)
C4—C3—C2120.6 (4)N2—C13—C14118.9 (3)
C4—C3—H3119.7C8—C13—C14121.1 (4)
C2—C3—H3119.7N1—C14—C5124.9 (4)
C3—C4—C5118.3 (4)N1—C14—C13116.8 (4)
C3—C4—H4120.9C5—C14—C13118.3 (4)
C5—C4—H4120.9C2—N1—C14117.6 (4)
C14—C5—C4116.8 (4)C11—N2—C13123.4 (4)
C14—C5—C6120.0 (4)C11—N2—H2119 (4)
C4—C5—C6123.3 (4)C13—N2—H2117 (4)
C7—C6—C5121.0 (4)
N1—C2—C3—C41.0 (7)C7—C8—C13—C143.2 (6)
C1—C2—C3—C4179.0 (5)C4—C5—C14—N10.2 (6)
C2—C3—C4—C50.9 (7)C6—C5—C14—N1179.3 (4)
C3—C4—C5—C140.5 (6)C4—C5—C14—C13179.8 (4)
C3—C4—C5—C6179.6 (4)C6—C5—C14—C130.6 (6)
C14—C5—C6—C71.6 (7)N2—C13—C14—N11.8 (5)
C4—C5—C6—C7177.5 (4)C8—C13—C14—N1176.9 (4)
C5—C6—C7—C81.4 (7)N2—C13—C14—C5178.3 (4)
C6—C7—C8—C130.9 (6)C8—C13—C14—C53.1 (6)
C6—C7—C8—C9179.4 (4)C3—C2—N1—C140.6 (7)
C13—C8—C9—C100.9 (6)C1—C2—N1—C14179.4 (4)
C7—C8—C9—C10178.8 (4)C5—C14—N1—C20.2 (6)
C8—C9—C10—C110.2 (6)C13—C14—N1—C2179.8 (4)
C9—C10—C11—N20.7 (6)C10—C11—N2—C130.0 (6)
C9—C10—C11—C12179.9 (4)C12—C11—N2—C13179.4 (4)
C9—C8—C13—N21.6 (6)C8—C13—N2—C111.2 (6)
C7—C8—C13—N2178.1 (4)C14—C13—N2—C11177.5 (4)
C9—C8—C13—C14177.1 (4)
Symmetry code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···Cl30.93 (7)2.73 (7)3.418 (4)132 (5)
N2—H2···N10.93 (7)2.32 (7)2.711 (6)105 (5)

Experimental details

Crystal data
Chemical formula(C14H13N2)2[PtCl6]
Mr826.31
Crystal system, space groupTriclinic, P1
Temperature (K)120
a, b, c (Å)8.9617 (10), 9.2179 (10), 9.9930 (11)
α, β, γ (°)78.427 (9), 66.464 (8), 79.540 (9)
V3)736.70 (14)
Z1
Radiation typeMo Kα
µ (mm1)5.33
Crystal size (mm)0.50 × 0.27 × 0.25
Data collection
DiffractometerStoe IPDSII
diffractometer
Absorption correctionNumerical
(shape of crystal determined optically)
Tmin, Tmax0.195, 0.265
No. of measured, independent and
observed [I > 2σ(I)] reflections
8112, 3817, 3813
Rint0.073
(sin θ/λ)max1)0.685
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.100, 1.10
No. of reflections3817
No. of parameters183
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)2.93, 3.20

Computer programs: X-AREA (Stoe & Cie, 2005), X-RED (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
Pt1—Cl12.3184 (10)Pt1—Cl32.3263 (11)
Pt1—Cl22.3235 (9)
Cl1—Pt1—Cl291.41 (4)Cl2—Pt1—Cl3i91.76 (4)
Cl1—Pt1—Cl2i88.59 (4)Cl1—Pt1—Cl389.41 (4)
Cl1—Pt1—Cl3i90.59 (4)Cl2—Pt1—Cl388.24 (4)
Symmetry code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···Cl30.93 (7)2.73 (7)3.418 (4)132 (5)
N2—H2···N10.93 (7)2.32 (7)2.711 (6)105 (5)
 

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