Tetra(chlorido/iodido)(1,10-phenanthroline)platinum(IV) hemi[di(chlorine/iodine)].

The asymmetric unit of the title compound, [PtCl(3.66)I(0.34)(C(12)H(8)N(2))]·0.5(Cl(0.13)I(1.87)), contains a neutral Pt(IV) complex and one half of a halogen molecule. The Pt(IV) ion is six-coordinated in a distorted octa-hedral environment by two N atoms of the 1,10-phenanthroline ligand and Cl or I atoms. The refinement of the structure and the EDX analysis indicate that the compound is a solid solution in which there is some substitution of Cl for I and vice versa. The chemical formula of the pure state of the compound would have been [PtCl(4)(C(12)H(8)N(2))]·0.5I(2). In the analysed crystal, two Cl atoms are partially (ca 25% and 9%) replaced by I atoms, and the I(2) mol-ecule has a minor component modelled as ICl. As a result of the disorder, the different trans effects of the N and Cl/I atoms are not distinct. The complex displays inter-molecular π-π inter-actions between the six-membered rings, with a centroid-centroid distance of 3.771 (4) Å. There are also weak intra-molecular C-H⋯Cl hydrogen bonds.

Related literature

For details of some other Pt–phenanthroline complexes, see: Buse et al. (1977 ▶); Fanizzi et al. (1996 ▶); Kim et al. (2009a ▶,b ▶). For related Pt–bipyridine complexes, see: Hambley (1986 ▶); Hojjat Kashani et al. (2008 ▶). For bond-length data, see: Orpen et al. (1989 ▶).

Experimental

Crystal data

[PtCl3.66I0.34(C12H8N2)]·0.5(Cl0.13I1.87)

M = 669.26

Orthorhombic,

a = 14.215 (5) Å

b = 12.733 (5) Å

c = 17.575 (6) Å

V = 3180.8 (19) Å3

Z = 8

Mo Kα radiation

μ = 11.92 mm−1

T = 293 K

0.25 × 0.17 × 0.15 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.111, T max = 0.168

17485 measured reflections

3246 independent reflections

2169 reflections with I > 2σ(I)

R int = 0.049

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.062

S = 0.86

3246 reflections

194 parameters

8 restraints

H-atom parameters constrained

Δρmax = 1.29 e Å−3

Δρmin = −0.50 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809007703/pk2156sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809007703/pk2156Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[PtCl3.66I0.34(C12H8N2)]·0.5(Cl0.13I1.87)	F(000) = 2424
Mr = 669.26	Dx = 2.795 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 973 reflections
a = 14.215 (5) Å	θ = 2.4–24.5°
b = 12.733 (5) Å	µ = 11.92 mm−1
c = 17.575 (6) Å	T = 293 K
V = 3180.8 (19) Å3	Plate, black
Z = 8	0.25 × 0.17 × 0.15 mm

Bruker SMART 1000 CCD diffractometer	3246 independent reflections
Radiation source: fine-focus sealed tube	2169 reflections with I > 2σ(I)
graphite	Rint = 0.049
φ and ω scans	θmax = 26.4°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −15→17
Tmin = 0.111, Tmax = 0.168	k = −10→15
17485 measured reflections	l = −17→21

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.062	H-atom parameters constrained
S = 0.86	w = 1/[σ2(Fo2) + (0.0244P)2] where P = (Fo2 + 2Fc2)/3
3246 reflections	(Δ/σ)max = 0.001
194 parameters	Δρmax = 1.29 e Å−3
8 restraints	Δρmin = −0.50 e Å−3

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 > 2σ(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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pt1	−0.134096 (18)	0.30394 (2)	0.177609 (15)	0.03991 (10)
Cl1	−0.17047 (13)	0.14177 (15)	0.22685 (10)	0.0521 (5)
Cl2	−0.28869 (12)	0.36077 (15)	0.19550 (10)	0.0512 (5)
Cl3	−0.0903 (14)	0.3607 (17)	0.2949 (8)	0.0494 (13)	0.746 (3)
I3	−0.0759 (11)	0.3695 (13)	0.3094 (6)	0.0494 (13)	0.254 (3)
Cl4	−0.1730 (7)	0.2478 (8)	0.0572 (3)	0.0518 (8)	0.913 (3)
I4	−0.177 (2)	0.238 (2)	0.0398 (9)	0.0518 (8)	0.087 (3)
N1	−0.0875 (4)	0.4446 (4)	0.1355 (3)	0.0393 (14)
N2	0.0029 (4)	0.2642 (4)	0.1585 (3)	0.0388 (13)
C1	−0.1341 (5)	0.5328 (6)	0.1283 (4)	0.0517 (19)
H1	−0.1978	0.5341	0.1403	0.062*
C2	−0.0911 (6)	0.6243 (6)	0.1031 (4)	0.058 (2)
H2	−0.1256	0.6863	0.0999	0.070*
C3	0.0015 (6)	0.6235 (6)	0.0831 (4)	0.055 (2)
H3	0.0305	0.6846	0.0660	0.066*
C4	0.0535 (5)	0.5285 (6)	0.0887 (4)	0.0438 (18)
C5	0.1496 (5)	0.5174 (6)	0.0688 (4)	0.0484 (19)
H5	0.1820	0.5741	0.0481	0.058*
C6	0.1946 (5)	0.4255 (6)	0.0796 (4)	0.050 (2)
H6	0.2581	0.4210	0.0672	0.061*
C7	0.1485 (5)	0.3347 (5)	0.1093 (4)	0.0403 (17)
C8	0.1899 (5)	0.2382 (6)	0.1246 (4)	0.052 (2)
H8	0.2534	0.2282	0.1141	0.062*
C9	0.1393 (5)	0.1590 (6)	0.1546 (4)	0.0494 (19)
H9	0.1678	0.0947	0.1647	0.059*
C10	0.0446 (5)	0.1735 (5)	0.1703 (4)	0.0447 (18)
H10	0.0098	0.1177	0.1897	0.054*
C11	0.0538 (5)	0.3460 (6)	0.1273 (4)	0.0384 (17)
C12	0.0055 (5)	0.4415 (5)	0.1167 (3)	0.0368 (16)
I1	0.56522 (7)	0.45323 (7)	0.04476 (5)	0.0912 (4)	0.936 (3)
Cl5	0.558 (3)	0.496 (4)	0.021 (2)	0.062 (9)*	0.064 (3)

	U11	U22	U33	U12	U13	U23
Pt1	0.04138 (16)	0.03167 (16)	0.04668 (17)	−0.00138 (13)	0.00129 (14)	0.00057 (14)
Cl1	0.0561 (11)	0.0392 (11)	0.0608 (12)	−0.0060 (9)	0.0047 (9)	0.0072 (9)
Cl2	0.0490 (11)	0.0431 (12)	0.0616 (12)	0.0050 (9)	0.0083 (9)	0.0040 (9)
Cl3	0.064 (4)	0.045 (3)	0.039 (4)	−0.005 (2)	−0.007 (2)	−0.014 (3)
I3	0.064 (4)	0.045 (3)	0.039 (4)	−0.005 (2)	−0.007 (2)	−0.014 (3)
Cl4	0.0649 (15)	0.052 (2)	0.038 (3)	−0.0073 (14)	−0.006 (3)	−0.004 (2)
I4	0.0649 (15)	0.052 (2)	0.038 (3)	−0.0073 (14)	−0.006 (3)	−0.004 (2)
N1	0.044 (4)	0.029 (4)	0.045 (3)	−0.001 (3)	−0.001 (3)	−0.002 (3)
N2	0.037 (3)	0.032 (3)	0.046 (3)	0.000 (3)	−0.005 (3)	−0.001 (3)
C1	0.053 (5)	0.048 (5)	0.055 (5)	0.001 (4)	−0.002 (4)	−0.007 (4)
C2	0.057 (5)	0.031 (5)	0.086 (6)	0.006 (4)	−0.009 (5)	−0.004 (4)
C3	0.071 (6)	0.034 (5)	0.060 (5)	−0.011 (4)	−0.003 (4)	0.003 (4)
C4	0.052 (5)	0.036 (5)	0.043 (4)	−0.006 (4)	−0.007 (4)	−0.003 (3)
C5	0.050 (5)	0.044 (5)	0.051 (5)	−0.017 (4)	−0.006 (4)	0.007 (4)
C6	0.045 (5)	0.052 (6)	0.054 (5)	−0.012 (4)	0.006 (4)	−0.011 (4)
C7	0.044 (5)	0.036 (4)	0.041 (4)	−0.001 (3)	−0.002 (3)	−0.006 (3)
C8	0.046 (5)	0.053 (5)	0.056 (5)	0.007 (4)	0.006 (4)	−0.004 (4)
C9	0.047 (5)	0.046 (5)	0.055 (5)	0.009 (4)	−0.007 (4)	−0.010 (4)
C10	0.050 (5)	0.032 (5)	0.052 (5)	−0.006 (3)	0.002 (4)	−0.002 (3)
C11	0.040 (4)	0.037 (4)	0.038 (4)	−0.007 (3)	−0.008 (3)	−0.001 (3)
C12	0.042 (4)	0.034 (4)	0.034 (4)	−0.002 (3)	−0.004 (3)	0.002 (3)
I1	0.1295 (7)	0.0635 (6)	0.0805 (6)	−0.0192 (5)	0.0312 (5)	−0.0058 (4)

Pt1—N2	2.040 (5)	C4—C12	1.391 (9)
Pt1—N1	2.048 (5)	C4—C5	1.417 (9)
Pt1—Cl3	2.272 (9)	C5—C6	1.346 (9)
Pt1—Cl1	2.2977 (19)	C5—H5	0.9300
Pt1—Cl4	2.301 (4)	C6—C7	1.428 (9)
Pt1—Cl2	2.3347 (19)	C6—H6	0.9300
Pt1—I3	2.598 (7)	C7—C8	1.389 (9)
Pt1—I4	2.635 (9)	C7—C11	1.391 (8)
N1—C1	1.309 (8)	C8—C9	1.346 (10)
N1—C12	1.364 (8)	C8—H8	0.9300
N2—C10	1.316 (8)	C9—C10	1.387 (9)
N2—C11	1.381 (8)	C9—H9	0.9300
C1—C2	1.388 (10)	C10—H10	0.9300
C1—H1	0.9300	C11—C12	1.408 (9)
C2—C3	1.364 (10)	I1—Cl5i	2.19 (4)
C2—H2	0.9300	I1—I1i	2.708 (2)
C3—C4	1.421 (10)	Cl5—I1i	2.19 (4)
C3—H3	0.9300
N2—Pt1—N1	81.3 (2)	N1—C1—H1	119.0
N2—Pt1—Cl3	88.1 (6)	C2—C1—H1	119.0
N1—Pt1—Cl3	87.8 (6)	C3—C2—C1	120.0 (7)
N2—Pt1—Cl1	93.11 (17)	C3—C2—H2	120.0
N1—Pt1—Cl1	174.14 (16)	C1—C2—H2	120.0
Cl3—Pt1—Cl1	90.3 (6)	C2—C3—C4	119.4 (7)
N2—Pt1—Cl4	90.0 (3)	C2—C3—H3	120.3
N1—Pt1—Cl4	91.0 (3)	C4—C3—H3	120.3
Cl3—Pt1—Cl4	177.9 (6)	C12—C4—C5	118.7 (7)
Cl1—Pt1—Cl4	90.8 (3)	C12—C4—C3	116.6 (7)
N2—Pt1—Cl2	175.97 (17)	C5—C4—C3	124.7 (7)
N1—Pt1—Cl2	94.69 (16)	C6—C5—C4	120.7 (7)
Cl3—Pt1—Cl2	92.1 (5)	C6—C5—H5	119.7
Cl1—Pt1—Cl2	90.91 (7)	C4—C5—H5	119.7
Cl4—Pt1—Cl2	89.7 (3)	C5—C6—C7	122.5 (7)
N2—Pt1—I3	85.6 (4)	C5—C6—H6	118.8
N1—Pt1—I3	86.5 (4)	C7—C6—H6	118.8
Cl3—Pt1—I3	2.7 (9)	C8—C7—C11	117.2 (7)
Cl1—Pt1—I3	91.4 (4)	C8—C7—C6	126.4 (7)
Cl4—Pt1—I3	175.2 (4)	C11—C7—C6	116.3 (6)
Cl2—Pt1—I3	94.6 (4)	C9—C8—C7	120.8 (7)
N2—Pt1—I4	89.4 (8)	C9—C8—H8	119.6
N1—Pt1—I4	91.3 (7)	C7—C8—H8	119.6
Cl3—Pt1—I4	177.5 (9)	C8—C9—C10	119.8 (7)
Cl1—Pt1—I4	90.4 (7)	C8—C9—H9	120.1
Cl4—Pt1—I4	0.7 (10)	C10—C9—H9	120.1
Cl2—Pt1—I4	90.3 (7)	N2—C10—C9	121.5 (7)
I3—Pt1—I4	174.8 (8)	N2—C10—H10	119.2
C1—N1—C12	119.5 (6)	C9—C10—H10	119.2
C1—N1—Pt1	128.4 (5)	N2—C11—C7	121.3 (6)
C12—N1—Pt1	112.1 (4)	N2—C11—C12	116.6 (6)
C10—N2—C11	119.3 (6)	C7—C11—C12	122.0 (6)
C10—N2—Pt1	128.5 (5)	N1—C12—C4	122.5 (6)
C11—N2—Pt1	112.2 (4)	N1—C12—C11	117.7 (6)
N1—C1—C2	121.9 (7)	C4—C12—C11	119.7 (6)
N2—Pt1—N1—C1	−176.8 (6)	C3—C4—C5—C6	176.6 (7)
Cl3—Pt1—N1—C1	−88.4 (8)	C4—C5—C6—C7	1.6 (11)
Cl4—Pt1—N1—C1	93.3 (6)	C5—C6—C7—C8	−177.6 (7)
Cl2—Pt1—N1—C1	3.6 (6)	C5—C6—C7—C11	−0.4 (10)
I3—Pt1—N1—C1	−90.8 (7)	C11—C7—C8—C9	1.1 (10)
I4—Pt1—N1—C1	93.9 (9)	C6—C7—C8—C9	178.3 (7)
N2—Pt1—N1—C12	0.2 (4)	C7—C8—C9—C10	0.1 (11)
Cl3—Pt1—N1—C12	88.7 (7)	C11—N2—C10—C9	2.1 (9)
Cl4—Pt1—N1—C12	−89.7 (5)	Pt1—N2—C10—C9	−179.7 (5)
Cl2—Pt1—N1—C12	−179.4 (4)	C8—C9—C10—N2	−1.7 (10)
I3—Pt1—N1—C12	86.3 (5)	C10—N2—C11—C7	−0.9 (9)
I4—Pt1—N1—C12	−89.0 (8)	Pt1—N2—C11—C7	−179.4 (5)
N1—Pt1—N2—C10	−179.6 (6)	C10—N2—C11—C12	−179.4 (6)
Cl3—Pt1—N2—C10	92.4 (8)	Pt1—N2—C11—C12	2.1 (7)
Cl1—Pt1—N2—C10	2.2 (5)	C8—C7—C11—N2	−0.7 (9)
Cl4—Pt1—N2—C10	−88.6 (6)	C6—C7—C11—N2	−178.2 (6)
I3—Pt1—N2—C10	93.4 (7)	C8—C7—C11—C12	177.7 (6)
I4—Pt1—N2—C10	−88.2 (9)	C6—C7—C11—C12	0.3 (9)
N1—Pt1—N2—C11	−1.3 (4)	C1—N1—C12—C4	−1.0 (9)
Cl3—Pt1—N2—C11	−89.3 (7)	Pt1—N1—C12—C4	−178.3 (5)
Cl1—Pt1—N2—C11	−179.5 (4)	C1—N1—C12—C11	178.2 (6)
Cl4—Pt1—N2—C11	89.7 (5)	Pt1—N1—C12—C11	0.9 (7)
I3—Pt1—N2—C11	−88.3 (6)	C5—C4—C12—N1	−178.4 (6)
I4—Pt1—N2—C11	90.1 (8)	C3—C4—C12—N1	2.3 (9)
C12—N1—C1—C2	−1.2 (10)	C5—C4—C12—C11	2.4 (9)
Pt1—N1—C1—C2	175.7 (5)	C3—C4—C12—C11	−176.9 (6)
N1—C1—C2—C3	1.8 (11)	N2—C11—C12—N1	−2.0 (9)
C1—C2—C3—C4	−0.4 (11)	C7—C11—C12—N1	179.5 (6)
C2—C3—C4—C12	−1.6 (10)	N2—C11—C12—C4	177.2 (6)
C2—C3—C4—C5	179.2 (7)	C7—C11—C12—C4	−1.3 (10)
C12—C4—C5—C6	−2.6 (10)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cl2	0.93	2.73	3.320 (8)	122
C10—H10···Cl1	0.93	2.66	3.240 (7)	121

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Cl2	0.93	2.73	3.320 (8)	122
C10—H10⋯Cl1	0.93	2.66	3.240 (7)	121