Bis(2,9-dimethyl-1,10-phenanthrolinium) hexa­chloridoplatinate(IV)

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.

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

No syntax errors found



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

---

S1. Comment

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 PtCl^2-₆ 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 PtCl^2-₆ 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

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).

S2. Experimental

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%).

S3. Refinement

H atom (for NH) was located in difference syntheses and refined isotropically [N—H = 0.93 (7) Å and U_iso(H) = 0.021 (14) Ų]. 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 U_iso(H) = 1.2U_eq(C).

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.

Bis(2,9-dimethyl-1,10-phenanthrolinium) hexachloridoplatinate(IV)

Crystal data

(C14H13N2)2[PtCl6]	Z = 1
Mr = 826.31	F(000) = 402
Triclinic, P1	Dx = 1.862 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9617 (10) Å	Cell parameters from 4500 reflections
b = 9.2179 (10) Å	θ = 2.3–29.2°
c = 9.9930 (11) Å	µ = 5.33 mm^−1
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) Å^3

Data collection

Stoe IPDSII diffractometer	3817 independent reflections
Radiation source: fine-focus sealed tube	3813 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.073
Detector resolution: 0.15 mm pixels mm^-1	θmax = 29.2°, θmin = 2.3°
rotation method scans	h = −12→12
Absorption correction: numerical (shape of crystal determined optically)	k = −11→12
Tmin = 0.195, Tmax = 0.265	l = −13→13
8112 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.100	w = 1/[σ^2(Fo^2) + (0.0772P)^2 + 0.2717P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max = 0.015
3817 reflections	Δρmax = 2.93 e Å^−3
183 parameters	Δρmin = −3.20 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.061 (6)

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
Pt1	0.0000	0.5000	0.0000	0.01485 (12)
Cl1	−0.24815 (12)	0.59692 (11)	−0.02163 (13)	0.0257 (2)
Cl2	−0.03063 (12)	0.26384 (11)	−0.02698 (12)	0.02210 (19)
Cl3	−0.13725 (14)	0.43950 (12)	0.25290 (11)	0.0255 (2)
N1	−0.2722 (5)	0.1814 (4)	0.5578 (4)	0.0221 (6)
N2	−0.3408 (4)	0.1347 (4)	0.3301 (4)	0.0205 (6)
H2	−0.349 (8)	0.228 (7)	0.356 (7)	0.021 (14)*
C1	−0.2682 (9)	0.3619 (6)	0.7008 (6)	0.0383 (12)
H1A	−0.3821	0.3974	0.7250	0.046*
H1B	−0.2035	0.4245	0.6157	0.046*
H1C	−0.2385	0.3644	0.7825	0.046*
C2	−0.2375 (6)	0.2055 (5)	0.6681 (5)	0.0254 (8)
C3	−0.1730 (6)	0.0873 (5)	0.7538 (5)	0.0254 (8)
H3	−0.1484	0.1082	0.8295	0.031*
C4	−0.1473 (6)	−0.0565 (5)	0.7255 (5)	0.0243 (8)
H4	−0.1068	−0.1338	0.7819	0.029*
C5	−0.1839 (5)	−0.0844 (5)	0.6073 (4)	0.0210 (7)
C6	−0.1628 (6)	−0.2299 (5)	0.5680 (5)	0.0244 (8)
H6	−0.1193	−0.3109	0.6186	0.029*
C7	−0.2057 (6)	−0.2517 (5)	0.4571 (5)	0.0238 (7)
H7	−0.1934	−0.3474	0.4347	0.029*
C8	−0.2693 (5)	−0.1287 (5)	0.3755 (4)	0.0203 (7)
C9	−0.3174 (5)	−0.1435 (5)	0.2607 (5)	0.0250 (8)
H9	−0.3103	−0.2373	0.2361	0.030*
C10	−0.3751 (5)	−0.0186 (6)	0.1850 (5)	0.0257 (8)
H10	−0.4069	−0.0288	0.1098	0.031*
C11	−0.3858 (5)	0.1233 (5)	0.2207 (5)	0.0228 (7)
C12	−0.4467 (6)	0.2634 (6)	0.1432 (5)	0.0288 (9)
H12A	−0.3630	0.3294	0.1003	0.035*
H12B	−0.5425	0.3111	0.2128	0.035*
H12C	−0.4738	0.2395	0.0671	0.035*
C13	−0.2848 (5)	0.0152 (4)	0.4093 (4)	0.0178 (6)
C14	−0.2458 (5)	0.0393 (4)	0.5291 (4)	0.0185 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.01930 (15)	0.01366 (15)	0.01486 (14)	−0.00114 (7)	−0.01009 (9)	−0.00206 (7)
Cl1	0.0245 (4)	0.0221 (4)	0.0365 (5)	−0.0005 (3)	−0.0191 (4)	−0.0028 (4)
Cl2	0.0259 (4)	0.0170 (4)	0.0267 (5)	−0.0028 (3)	−0.0117 (4)	−0.0061 (3)
Cl3	0.0373 (5)	0.0220 (4)	0.0172 (4)	−0.0047 (4)	−0.0099 (4)	−0.0026 (3)
N1	0.0298 (17)	0.0175 (15)	0.0190 (15)	−0.0037 (12)	−0.0090 (13)	−0.0023 (12)
N2	0.0219 (15)	0.0207 (16)	0.0194 (15)	−0.0020 (12)	−0.0093 (12)	−0.0008 (12)
C1	0.072 (4)	0.020 (2)	0.029 (2)	−0.007 (2)	−0.025 (2)	−0.0055 (17)
C2	0.038 (2)	0.0199 (18)	0.0201 (18)	−0.0067 (15)	−0.0115 (17)	−0.0014 (14)
C3	0.036 (2)	0.025 (2)	0.0188 (17)	−0.0073 (16)	−0.0135 (16)	−0.0022 (15)
C4	0.034 (2)	0.0250 (19)	0.0174 (17)	−0.0060 (15)	−0.0140 (16)	0.0009 (14)
C5	0.0282 (18)	0.0202 (18)	0.0165 (16)	−0.0053 (14)	−0.0102 (14)	−0.0004 (13)
C6	0.032 (2)	0.0170 (17)	0.0227 (18)	−0.0015 (14)	−0.0115 (16)	0.0012 (14)
C7	0.033 (2)	0.0176 (17)	0.0222 (18)	−0.0003 (14)	−0.0122 (16)	−0.0044 (14)
C8	0.0226 (17)	0.0197 (17)	0.0192 (17)	−0.0024 (13)	−0.0076 (14)	−0.0050 (14)
C9	0.0238 (18)	0.028 (2)	0.0247 (19)	−0.0057 (15)	−0.0082 (16)	−0.0060 (16)
C10	0.0239 (18)	0.036 (2)	0.0210 (18)	−0.0054 (16)	−0.0100 (15)	−0.0068 (16)
C11	0.0170 (15)	0.031 (2)	0.0208 (18)	−0.0020 (14)	−0.0097 (14)	−0.0012 (15)
C12	0.0261 (19)	0.034 (2)	0.028 (2)	0.0002 (16)	−0.0165 (17)	0.0040 (17)
C13	0.0207 (16)	0.0188 (17)	0.0153 (15)	−0.0017 (12)	−0.0087 (13)	−0.0019 (12)
C14	0.0243 (17)	0.0177 (17)	0.0154 (15)	−0.0047 (13)	−0.0085 (13)	−0.0023 (13)

Geometric parameters (Å, º)

Pt1—Cl1	2.3184 (10)	C6—C7	1.369 (6)
Pt1—Cl1^i	2.3184 (10)	C6—H6	0.9300
Pt1—Cl2	2.3235 (9)	C7—C8	1.429 (6)
Pt1—Cl2^i	2.3235 (9)	C7—H7	0.9300
Pt1—Cl3^i	2.3263 (11)	C8—C13	1.403 (5)
Pt1—Cl3	2.3263 (11)	C8—C9	1.414 (6)
N2—H2	0.93 (7)	C9—C10	1.383 (7)
C1—C2	1.495 (6)	C9—H9	0.9300
C1—H1A	0.9600	C10—C11	1.400 (6)
C1—H1B	0.9600	C10—H10	0.9300
C1—H1C	0.9600	C11—N2	1.336 (5)
C2—N1	1.325 (6)	C11—C12	1.498 (6)
C2—C3	1.432 (6)	C12—H12A	0.9600
C3—C4	1.370 (6)	C12—H12B	0.9600
C3—H3	0.9300	C12—H12C	0.9600
C4—C5	1.426 (6)	C13—N2	1.364 (5)
C4—H4	0.9300	C13—C14	1.441 (5)
C5—C14	1.407 (6)	C14—N1	1.355 (5)
C5—C6	1.431 (6)
Cl1—Pt1—Cl1^i	180	C7—C6—H6	119.5
Cl1—Pt1—Cl2	91.41 (4)	C5—C6—H6	119.5
Cl1^i—Pt1—Cl2	88.59 (4)	C6—C7—C8	120.6 (4)
Cl1—Pt1—Cl2^i	88.59 (4)	C6—C7—H7	119.7
Cl1^i—Pt1—Cl2^i	91.41 (4)	C8—C7—H7	119.7
Cl2—Pt1—Cl2^i	180	C13—C8—C9	117.6 (4)
Cl1—Pt1—Cl3^i	90.59 (4)	C13—C8—C7	118.9 (4)
Cl1^i—Pt1—Cl3^i	89.41 (4)	C9—C8—C7	123.5 (4)
Cl2—Pt1—Cl3^i	91.76 (4)	C10—C9—C8	120.0 (4)
Cl2^i—Pt1—Cl3^i	88.24 (4)	C10—C9—H9	120.0
Cl1—Pt1—Cl3	89.41 (4)	C8—C9—H9	120.0
Cl1^i—Pt1—Cl3	90.59 (4)	C9—C10—C11	120.5 (4)
Cl2—Pt1—Cl3	88.24 (4)	C9—C10—H10	119.7
Cl2^i—Pt1—Cl3	91.76 (4)	C11—C10—H10	119.7
Cl3^i—Pt1—Cl3	180	N2—C11—C10	118.5 (4)
C2—C1—H1A	109.5	N2—C11—C12	118.1 (4)
C2—C1—H1B	109.5	C10—C11—C12	123.4 (4)
H1A—C1—H1B	109.5	C11—C12—H12A	109.5
C2—C1—H1C	109.5	C11—C12—H12B	109.5
H1A—C1—H1C	109.5	H12A—C12—H12B	109.5
H1B—C1—H1C	109.5	C11—C12—H12C	109.5
N1—C2—C3	121.8 (4)	H12A—C12—H12C	109.5
N1—C2—C1	117.6 (4)	H12B—C12—H12C	109.5
C3—C2—C1	120.5 (4)	N2—C13—C8	120.0 (4)
C4—C3—C2	120.6 (4)	N2—C13—C14	118.9 (3)
C4—C3—H3	119.7	C8—C13—C14	121.1 (4)
C2—C3—H3	119.7	N1—C14—C5	124.9 (4)
C3—C4—C5	118.3 (4)	N1—C14—C13	116.8 (4)
C3—C4—H4	120.9	C5—C14—C13	118.3 (4)
C5—C4—H4	120.9	C2—N1—C14	117.6 (4)
C14—C5—C4	116.8 (4)	C11—N2—C13	123.4 (4)
C14—C5—C6	120.0 (4)	C11—N2—H2	119 (4)
C4—C5—C6	123.3 (4)	C13—N2—H2	117 (4)
C7—C6—C5	121.0 (4)
N1—C2—C3—C4	−1.0 (7)	C7—C8—C13—C14	−3.2 (6)
C1—C2—C3—C4	179.0 (5)	C4—C5—C14—N1	0.2 (6)
C2—C3—C4—C5	0.9 (7)	C6—C5—C14—N1	179.3 (4)
C3—C4—C5—C14	−0.5 (6)	C4—C5—C14—C13	−179.8 (4)
C3—C4—C5—C6	−179.6 (4)	C6—C5—C14—C13	−0.6 (6)
C14—C5—C6—C7	−1.6 (7)	N2—C13—C14—N1	1.8 (5)
C4—C5—C6—C7	177.5 (4)	C8—C13—C14—N1	−176.9 (4)
C5—C6—C7—C8	1.4 (7)	N2—C13—C14—C5	−178.3 (4)
C6—C7—C8—C13	0.9 (6)	C8—C13—C14—C5	3.1 (6)
C6—C7—C8—C9	−179.4 (4)	C3—C2—N1—C14	0.6 (7)
C13—C8—C9—C10	0.9 (6)	C1—C2—N1—C14	−179.4 (4)
C7—C8—C9—C10	−178.8 (4)	C5—C14—N1—C2	−0.2 (6)
C8—C9—C10—C11	0.2 (6)	C13—C14—N1—C2	179.8 (4)
C9—C10—C11—N2	−0.7 (6)	C10—C11—N2—C13	0.0 (6)
C9—C10—C11—C12	179.9 (4)	C12—C11—N2—C13	179.4 (4)
C9—C8—C13—N2	−1.6 (6)	C8—C13—N2—C11	1.2 (6)
C7—C8—C13—N2	178.1 (4)	C14—C13—N2—C11	−177.5 (4)
C9—C8—C13—C14	177.1 (4)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl3	0.93 (7)	2.73 (7)	3.418 (4)	132 (5)
N2—H2···N1	0.93 (7)	2.32 (7)	2.711 (6)	105 (5)