Dichloridobis(pyridine-2-carboxyl-ato-κN,O)platinum(IV) acetonitrile solvate.

The asymmetric unit of the title compound, [PtCl(2)(C(6)H(4)NO(2))(2)]·CH(3)CN, contains a neutral Pt(IV) complex and an acetonitrile solvent mol-ecule. In the complex, the Pt(4+) atom is six-coordinated in a distorted octa-hedral environment by two N atoms and two O atoms from two pyridine-carboxyl-ate (pic) ligands and two Cl atoms. The Cl atoms are cis with respect to each other. The compound displays inter- and intra-molecular C-H⋯O and C-H⋯Cl hydrogen bonding.

Related literature

For the synthesis and structure of the Pt(IV)-pic complex, [PtCl4(pic)]−, see: Griffith et al. (2005 ▶). For a related Pt(II)-dipicolinate complex, see: Goodgame et al. (1995 ▶).

Experimental

Crystal data

[PtCl2(C6H4NO2)2]·C2H3N

M = 551.25

Monoclinic,

a = 6.103 (3) Å

b = 27.988 (12) Å

c = 9.823 (4) Å

β = 91.076 (7)°

V = 1677.7 (12) Å3

Z = 4

Mo Kα radiation

μ = 8.71 mm−1

T = 293 K

0.20 × 0.15 × 0.15 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.203, T max = 0.271

9732 measured reflections

3437 independent reflections

3051 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.023

wR(F 2) = 0.052

S = 1.11

3437 reflections

218 parameters

H-atom parameters constrained

Δρmax = 1.04 e Å−3

Δρmin = −0.58 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: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809017966/bt2950sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809017966/bt2950Isup2.hkl

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

[PtCl2(C6H4NO2)2]·C2H3N	F(000) = 1040
Mr = 551.25	Dx = 2.182 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 979 reflections
a = 6.103 (3) Å	θ = 2.5–25.9°
b = 27.988 (12) Å	µ = 8.71 mm−1
c = 9.823 (4) Å	T = 293 K
β = 91.076 (7)°	Stick, colorless
V = 1677.7 (12) Å3	0.20 × 0.15 × 0.15 mm
Z = 4

Bruker SMART 1000 CCD diffractometer	3437 independent reflections
Radiation source: fine-focus sealed tube	3051 reflections with I > 2σ(I)
graphite	Rint = 0.025
φ and ω scans	θmax = 26.4°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −6→7
Tmin = 0.203, Tmax = 0.271	k = −35→33
9732 measured reflections	l = −12→12

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.052	H-atom parameters constrained
S = 1.11	w = 1/[σ2(Fo2) + (0.0126P)2 + 3.1343P] where P = (Fo2 + 2Fc2)/3
3437 reflections	(Δ/σ)max = 0.001
218 parameters	Δρmax = 1.04 e Å−3
0 restraints	Δρmin = −0.58 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 > 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.

	x	y	z	Uiso*/Ueq
Pt1	0.67421 (3)	0.119200 (6)	0.082756 (17)	0.03061 (6)
Cl1	0.47415 (19)	0.06563 (4)	−0.04645 (12)	0.0421 (3)
Cl2	0.9275 (2)	0.12741 (4)	−0.08481 (13)	0.0454 (3)
O1	0.5138 (5)	0.17577 (11)	0.0066 (3)	0.0444 (8)
O2	0.4983 (9)	0.25418 (14)	0.0228 (6)	0.0971 (19)
O3	0.4557 (5)	0.11261 (11)	0.2338 (3)	0.0389 (7)
O4	0.3574 (6)	0.06264 (14)	0.3949 (4)	0.0533 (10)
N1	0.8376 (6)	0.17036 (13)	0.1894 (4)	0.0336 (8)
N2	0.8101 (6)	0.06220 (12)	0.1765 (4)	0.0297 (8)
C1	1.0064 (8)	0.16447 (16)	0.2751 (5)	0.0410 (11)
H1	1.0535	0.1337	0.2961	0.049*
C2	1.1128 (9)	0.20275 (18)	0.3335 (5)	0.0504 (14)
H2	1.2320	0.1980	0.3923	0.060*
C3	1.0415 (10)	0.2478 (2)	0.3040 (6)	0.0610 (16)
H3	1.1108	0.2743	0.3428	0.073*
C4	0.8651 (11)	0.25356 (19)	0.2158 (7)	0.0680 (19)
H4	0.8137	0.2841	0.1957	0.082*
C5	0.7654 (9)	0.21476 (17)	0.1578 (5)	0.0452 (12)
C6	0.5793 (10)	0.21694 (19)	0.0564 (6)	0.0550 (15)
C7	0.9907 (8)	0.03922 (17)	0.1407 (5)	0.0380 (11)
H7	1.0735	0.0509	0.0695	0.046*
C8	1.0567 (9)	−0.00183 (17)	0.2081 (5)	0.0451 (12)
H8	1.1841	−0.0176	0.1832	0.054*
C9	0.9325 (10)	−0.01915 (18)	0.3122 (6)	0.0520 (14)
H9	0.9745	−0.0468	0.3581	0.062*
C10	0.7448 (9)	0.00483 (18)	0.3481 (5)	0.0476 (13)
H10	0.6595	−0.0064	0.4187	0.057*
C11	0.6848 (7)	0.04566 (16)	0.2781 (4)	0.0341 (10)
C12	0.4840 (8)	0.07409 (17)	0.3081 (5)	0.0386 (11)
N3	0.7810 (12)	0.1214 (2)	0.5485 (7)	0.091 (2)
C13	0.4113 (12)	0.1411 (2)	0.6554 (7)	0.0761 (19)
H13A	0.3723	0.1734	0.6331	0.114*
H13B	0.4226	0.1376	0.7525	0.114*
H13C	0.3007	0.1198	0.6201	0.114*
C14	0.6175 (14)	0.1297 (2)	0.5963 (7)	0.0677 (18)

	U11	U22	U33	U12	U13	U23
Pt1	0.02912 (10)	0.02809 (10)	0.03449 (10)	0.00214 (7)	−0.00261 (7)	0.00113 (7)
Cl1	0.0381 (6)	0.0414 (6)	0.0465 (7)	−0.0055 (5)	−0.0040 (5)	−0.0048 (5)
Cl2	0.0479 (7)	0.0448 (7)	0.0439 (7)	−0.0037 (5)	0.0083 (5)	0.0066 (5)
O1	0.044 (2)	0.0332 (18)	0.055 (2)	0.0085 (15)	−0.0173 (17)	0.0024 (15)
O2	0.122 (4)	0.035 (2)	0.131 (4)	0.026 (2)	−0.079 (4)	−0.002 (2)
O3	0.0307 (17)	0.0435 (18)	0.0428 (19)	0.0064 (14)	0.0072 (14)	−0.0001 (15)
O4	0.048 (2)	0.063 (2)	0.049 (2)	−0.0049 (18)	0.0169 (18)	−0.0001 (18)
N1	0.033 (2)	0.030 (2)	0.037 (2)	0.0027 (16)	−0.0055 (17)	−0.0021 (16)
N2	0.031 (2)	0.0259 (18)	0.0325 (19)	0.0037 (15)	−0.0014 (16)	−0.0002 (15)
C1	0.040 (3)	0.031 (2)	0.052 (3)	0.002 (2)	−0.009 (2)	0.001 (2)
C2	0.051 (3)	0.044 (3)	0.055 (3)	−0.002 (2)	−0.019 (3)	−0.006 (2)
C3	0.069 (4)	0.039 (3)	0.074 (4)	−0.005 (3)	−0.023 (3)	−0.010 (3)
C4	0.084 (5)	0.027 (3)	0.092 (5)	0.009 (3)	−0.031 (4)	−0.009 (3)
C5	0.052 (3)	0.030 (3)	0.053 (3)	0.010 (2)	−0.013 (3)	0.000 (2)
C6	0.064 (4)	0.036 (3)	0.064 (4)	0.013 (3)	−0.024 (3)	0.001 (3)
C7	0.036 (3)	0.038 (3)	0.040 (3)	0.003 (2)	0.003 (2)	−0.002 (2)
C8	0.044 (3)	0.037 (3)	0.055 (3)	0.010 (2)	−0.007 (2)	−0.004 (2)
C9	0.065 (4)	0.034 (3)	0.057 (3)	0.004 (3)	−0.011 (3)	0.006 (2)
C10	0.060 (4)	0.042 (3)	0.041 (3)	−0.002 (3)	0.002 (3)	0.012 (2)
C11	0.036 (3)	0.035 (2)	0.032 (2)	−0.005 (2)	−0.001 (2)	0.0020 (19)
C12	0.038 (3)	0.043 (3)	0.035 (3)	−0.003 (2)	0.002 (2)	−0.009 (2)
N3	0.097 (5)	0.099 (5)	0.078 (4)	0.003 (4)	−0.014 (4)	−0.009 (4)
C13	0.097 (6)	0.065 (4)	0.067 (4)	−0.004 (4)	0.001 (4)	0.012 (3)
C14	0.092 (6)	0.057 (4)	0.053 (4)	−0.002 (4)	−0.017 (4)	−0.002 (3)

Pt1—O1	1.999 (3)	C3—H3	0.9300
Pt1—N2	2.013 (3)	C4—C5	1.364 (7)
Pt1—O3	2.022 (3)	C4—H4	0.9300
Pt1—N1	2.025 (4)	C5—C6	1.498 (7)
Pt1—Cl2	2.2910 (14)	C7—C8	1.382 (6)
Pt1—Cl1	2.3003 (13)	C7—H7	0.9300
O1—C6	1.311 (6)	C8—C9	1.373 (7)
O2—C6	1.197 (6)	C8—H8	0.9300
O3—C12	1.312 (6)	C9—C10	1.379 (7)
O4—C12	1.205 (6)	C9—H9	0.9300
N1—C1	1.328 (6)	C10—C11	1.379 (6)
N1—C5	1.352 (6)	C10—H10	0.9300
N2—C7	1.329 (6)	C11—C12	1.495 (6)
N2—C11	1.350 (5)	N3—C14	1.134 (10)
C1—C2	1.373 (6)	C13—C14	1.432 (10)
C1—H1	0.9300	C13—H13A	0.9600
C2—C3	1.364 (7)	C13—H13B	0.9600
C2—H2	0.9300	C13—H13C	0.9600
C3—C4	1.379 (8)
O1—Pt1—N2	173.39 (14)	C5—C4—H4	119.8
O1—Pt1—O3	91.24 (14)	C3—C4—H4	119.8
N2—Pt1—O3	82.16 (13)	N1—C5—C4	119.7 (5)
O1—Pt1—N1	82.32 (14)	N1—C5—C6	115.4 (4)
N2—Pt1—N1	97.41 (15)	C4—C5—C6	124.9 (5)
O3—Pt1—N1	90.57 (14)	O2—C6—O1	122.7 (5)
O1—Pt1—Cl2	89.09 (11)	O2—C6—C5	121.5 (5)
N2—Pt1—Cl2	97.51 (11)	O1—C6—C5	115.7 (4)
O3—Pt1—Cl2	178.67 (10)	N2—C7—C8	120.7 (5)
N1—Pt1—Cl2	88.19 (11)	N2—C7—H7	119.6
O1—Pt1—Cl1	93.37 (10)	C8—C7—H7	119.6
N2—Pt1—Cl1	86.89 (11)	C9—C8—C7	119.4 (5)
O3—Pt1—Cl1	89.70 (10)	C9—C8—H8	120.3
N1—Pt1—Cl1	175.68 (10)	C7—C8—H8	120.3
Cl2—Pt1—Cl1	91.57 (5)	C8—C9—C10	119.4 (5)
C6—O1—Pt1	114.4 (3)	C8—C9—H9	120.3
C12—O3—Pt1	113.7 (3)	C10—C9—H9	120.3
C1—N1—C5	120.3 (4)	C9—C10—C11	119.3 (5)
C1—N1—Pt1	127.5 (3)	C9—C10—H10	120.3
C5—N1—Pt1	112.1 (3)	C11—C10—H10	120.3
C7—N2—C11	120.9 (4)	N2—C11—C10	120.2 (4)
C7—N2—Pt1	126.8 (3)	N2—C11—C12	116.2 (4)
C11—N2—Pt1	112.1 (3)	C10—C11—C12	123.6 (4)
N1—C1—C2	121.5 (4)	O4—C12—O3	122.2 (5)
N1—C1—H1	119.2	O4—C12—C11	122.5 (5)
C2—C1—H1	119.2	O3—C12—C11	115.3 (4)
C3—C2—C1	119.2 (5)	C14—C13—H13A	109.5
C3—C2—H2	120.4	C14—C13—H13B	109.5
C1—C2—H2	120.4	H13A—C13—H13B	109.5
C2—C3—C4	118.9 (5)	C14—C13—H13C	109.5
C2—C3—H3	120.6	H13A—C13—H13C	109.5
C4—C3—H3	120.6	H13B—C13—H13C	109.5
C5—C4—C3	120.5 (5)	N3—C14—C13	178.8 (8)
O3—Pt1—O1—C6	89.9 (4)	C1—N1—C5—C4	−0.8 (8)
N1—Pt1—O1—C6	−0.5 (4)	Pt1—N1—C5—C4	−176.9 (5)
Cl2—Pt1—O1—C6	−88.8 (4)	C1—N1—C5—C6	177.9 (5)
Cl1—Pt1—O1—C6	179.7 (4)	Pt1—N1—C5—C6	1.8 (6)
O1—Pt1—O3—C12	173.1 (3)	C3—C4—C5—N1	1.3 (10)
N2—Pt1—O3—C12	−7.2 (3)	C3—C4—C5—C6	−177.3 (6)
N1—Pt1—O3—C12	−104.6 (3)	Pt1—O1—C6—O2	−179.1 (6)
Cl1—Pt1—O3—C12	79.7 (3)	Pt1—O1—C6—C5	1.6 (7)
O1—Pt1—N1—C1	−176.5 (4)	N1—C5—C6—O2	178.3 (6)
N2—Pt1—N1—C1	10.1 (4)	C4—C5—C6—O2	−3.0 (11)
O3—Pt1—N1—C1	92.3 (4)	N1—C5—C6—O1	−2.4 (8)
Cl2—Pt1—N1—C1	−87.2 (4)	C4—C5—C6—O1	176.3 (6)
O1—Pt1—N1—C5	−0.8 (3)	C11—N2—C7—C8	−1.0 (7)
N2—Pt1—N1—C5	−174.1 (3)	Pt1—N2—C7—C8	−174.9 (3)
O3—Pt1—N1—C5	−92.0 (4)	N2—C7—C8—C9	0.7 (7)
Cl2—Pt1—N1—C5	88.5 (3)	C7—C8—C9—C10	−0.3 (8)
O3—Pt1—N2—C7	−179.5 (4)	C8—C9—C10—C11	0.3 (8)
N1—Pt1—N2—C7	−89.9 (4)	C7—N2—C11—C10	1.0 (7)
Cl2—Pt1—N2—C7	−0.8 (4)	Pt1—N2—C11—C10	175.7 (4)
Cl1—Pt1—N2—C7	90.4 (4)	C7—N2—C11—C12	−179.2 (4)
O3—Pt1—N2—C11	6.2 (3)	Pt1—N2—C11—C12	−4.5 (5)
N1—Pt1—N2—C11	95.7 (3)	C9—C10—C11—N2	−0.7 (7)
Cl2—Pt1—N2—C11	−175.1 (3)	C9—C10—C11—C12	179.6 (5)
Cl1—Pt1—N2—C11	−84.0 (3)	Pt1—O3—C12—O4	−173.6 (4)
C5—N1—C1—C2	−0.3 (8)	Pt1—O3—C12—C11	6.7 (5)
Pt1—N1—C1—C2	175.1 (4)	N2—C11—C12—O4	178.8 (4)
N1—C1—C2—C3	0.9 (8)	C10—C11—C12—O4	−1.4 (7)
C1—C2—C3—C4	−0.3 (9)	N2—C11—C12—O3	−1.5 (6)
C2—C3—C4—C5	−0.8 (10)	C10—C11—C12—O3	178.3 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2i	0.93	2.45	3.207 (7)	139
C7—H7···Cl1ii	0.93	2.75	3.583 (5)	150
C7—H7···Cl2	0.93	2.76	3.334 (5)	121
C10—H10···O4iii	0.93	2.42	3.223 (6)	145
C13—H13A···O2iv	0.96	2.43	3.256 (8)	144
C13—H13B···Cl1v	0.96	2.84	3.625 (7)	140

Table 1

Selected bond lengths (Å)

Pt1—O1	1.999 (3)
Pt1—N2	2.013 (3)
Pt1—O3	2.022 (3)
Pt1—N1	2.025 (4)
Pt1—Cl2	2.2910 (14)
Pt1—Cl1	2.3003 (13)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2i	0.93	2.45	3.207 (7)	139
C7—H7⋯Cl1ii	0.93	2.75	3.583 (5)	150
C7—H7⋯Cl2	0.93	2.76	3.334 (5)	121
C10—H10⋯O4iii	0.93	2.42	3.223 (6)	145
C13—H13A⋯O2iv	0.96	2.43	3.256 (8)	144
C13—H13B⋯Cl1v	0.96	2.84	3.625 (7)	140

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .