Bis(acetonitrile-κN)(1,10-phenanthroline-κ²N,N′)platinum(II) bis­(perchlorate)

The asymmetric unit of the title compound, [Pt(CH₃CN)₂(C₁₂H₈N₂)](ClO₄)₂, contains one half of a cationic Pt^II complex and pair of half perchlorate anions, one of which is disordered over two sites in a 0.53 (3):0.47 (3) ratio. The complex and anions are disposed about a crystallographic mirror plane parallel to the ac plane passing through the Pt and Cl atoms. In the complex, the Pt^II ion lies in a distorted square-planar environment defined by four N atoms of the chelating 1,10-phenanthroline ligand and two distinct acetonitrile mol­ecules. The component ions inter­act by means of inter­molecular C—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.012 Å
• Disorder in solvent or counterion
• R factor = 0.042
• wR factor = 0.100
• Data-to-parameter ratio = 11.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT342_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..         12
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          5

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         18
PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ...................      33.00 Perc.
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          !

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

The asymmetric unit of the title compound, [Pt(phen)(CH₃CN)₂](ClO₄)₂ (where phen is 1,10-phenanthroline, C₁₂H₈N₂), contains one half of a cationic Pt^II complex and half a perchlorate anion (Fig. 1). The complex and anions are disposed about a crystallographic mirror plane parallel to the ac plane passing through the Pt and Cl atoms (Fig. 2). In the complex, the Pt^II ion lies in a distorted square-planar environment defined by four N atoms of the chelating 1,10-phenanthroline ligand and two distinct acetonitrile molecules. The main contribution to the distortion is the tight N1—Pt1—N1ⁱ [symmetry code: (i) x,-y+1/2,z] chelate angle [81.9 (3)°], which results in non-linear trans arrangement [<N1—Pt1—N2ⁱ = 177.0 (2)°]. The Pt—N bond lengths are almost equal [Pt1—N(phen): 2.001 (6) Å; Pt1—N(CH₃CN): 1.994 (7) Å] (Table 1). The component ions interact by means of intermolecular C—H···O hydrogen bonds (Fig. 2 and Table 2).

Related literature

For the synthesis of [PtCl₂(phen)] (phen = 1,10-phenanthroline), see: Hodges & Rund (1975). For the crystal structure of [Pd(phen)(CH₃CN)₂]²⁺, see: Adrian et al. (2008).

S2. Experimental

To a solution of AgClO₄.H₂O (0.1006 g, 0.446 mmol) in CH₃CN (70 ml) was added [PtCl₂(phen)] (0.0996 g, 0.223 mmol) and refluxed for 7 h. The mixture was filtered to remove AgCl and then the resulting solution was dried under vacuum. The residue was washed with CH₂Cl₂ and dried at 50 °C, to give a pale gray powder (0.1401 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH₃CN solution.

S3. Refinement

H atoms were positioned geometrically and allowed to ride on their respective parent atoms [C—H = 0.95 (aromatic) or 0.98 Å (CH₃) and U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C)]. The highest peak (2.23 e Å^-3) and the deepest hole (-1.82 e Å^-3) in the difference Fourier map are located 0.86 and 0.96 Å, respectively, from the atom Pt1. The O atoms (O4, O5 and O6) of the ClO₄ anion displayed relatively large displacement factors so that the anion appears to be partially disordered. The anion was modelled as disordered over two sites with a major site occupancy factor of 0.53 (3). A total of 18 restraints were used in the refinement using the following SHELXL97 (Sheldrick, 2008) commands: SAME 0.020 Cl2' > O6' and DELU 0.010 Cl2 > O6'. In addition, the displacement parameters of the major and minor component atoms Cl2 Cl2' were constrained using the EADP command.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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 (Sheldrick, 2008).

Figures

	Fig. 1. The structure of the title compound with displacement ellipsoids drawn at the 50% probability level for non-H atoms. Unlabelled atoms are related to labelled atoms by the symmetry operation and the bonds of the minor components of the disordered ClO4 anion are shown with dashed lines.
	Fig. 2. View of the unit-cell contents of the title compound. Hydrogen-bond interactions are drawn with dashed lines.

Bis(acetonitrile-κN)(1,10-phenanthroline- κ²N,N')platinum(II) bis(perchlorate)

Crystal data

[Pt(C2H3N)2(C12H8N2)](ClO4)2	F(000) = 1256
Mr = 656.30	Dx = 2.209 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 3403 reflections
a = 9.1407 (5) Å	θ = 2.2–25.0°
b = 11.7822 (7) Å	µ = 7.44 mm^−1
c = 18.3215 (11) Å	T = 200 K
V = 1973.2 (2) Å^3	Rod, colorless
Z = 4	0.28 × 0.12 × 0.04 mm

Data collection

Bruker SMART 1000 CCD diffractometer	2043 independent reflections
Radiation source: fine-focus sealed tube	1540 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.087
ϕ and ω scans	θmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→7
Tmin = 0.763, Tmax = 1.000	k = −14→14
11860 measured reflections	l = −22→21

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0514P)^2] where P = (Fo^2 + 2Fc^2)/3
2043 reflections	(Δ/σ)max < 0.001
176 parameters	Δρmax = 2.23 e Å^−3
18 restraints	Δρmin = −1.82 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	Occ. (<1)
Pt1	0.96551 (5)	0.2500	0.10603 (2)	0.02158 (17)
N1	0.8473 (6)	0.1387 (5)	0.0483 (3)	0.0219 (14)
N2	1.0774 (7)	0.1326 (5)	0.1611 (4)	0.0278 (16)
C1	0.8490 (8)	0.0253 (6)	0.0516 (4)	0.0264 (18)
H1	0.9141	−0.0111	0.0845	0.032*
C2	0.7580 (9)	−0.0405 (7)	0.0081 (5)	0.034 (2)
H2	0.7628	−0.1209	0.0110	0.041*
C3	0.6622 (9)	0.0097 (7)	−0.0387 (5)	0.031 (2)
H3	0.5999	−0.0355	−0.0682	0.038*
C4	0.6557 (8)	0.1302 (7)	−0.0431 (5)	0.0304 (19)
C5	0.7512 (7)	0.1902 (6)	0.0018 (4)	0.0229 (17)
C6	0.5587 (9)	0.1932 (8)	−0.0901 (4)	0.034 (2)
H6	0.4937	0.1535	−0.1215	0.041*
C7	1.2397 (10)	0.0000 (8)	0.2375 (5)	0.040 (2)
H7A	1.2170	−0.0791	0.2254	0.061*
H7B	1.2217	0.0129	0.2896	0.061*
H7C	1.3427	0.0154	0.2264	0.061*
C8	1.1474 (8)	0.0750 (6)	0.1947 (4)	0.0255 (18)
Cl1	0.4808 (3)	0.2500	0.14861 (16)	0.0273 (6)
O1	0.3890 (9)	0.2500	0.2122 (5)	0.040 (2)
O2	0.3939 (10)	0.2500	0.0837 (4)	0.040 (2)
O3	0.5699 (7)	0.1506 (6)	0.1490 (4)	0.0515 (19)
Cl2	0.430 (2)	0.7500	0.341 (4)	0.033 (2)	0.53 (3)
O4	0.272 (2)	0.7500	0.340 (2)	0.080 (10)	0.53 (3)
O5	0.468 (3)	0.7500	0.4176 (11)	0.088 (10)	0.53 (3)
O6	0.4825 (19)	0.6495 (12)	0.3106 (12)	0.077 (8)	0.53 (3)
Cl2'	0.461 (3)	0.7500	0.340 (4)	0.033 (2)	0.47 (3)
O4'	0.312 (3)	0.7500	0.365 (2)	0.068 (10)	0.47 (3)
O5'	0.453 (3)	0.7500	0.2625 (11)	0.111 (15)	0.47 (3)
O6'	0.5367 (19)	0.6564 (15)	0.3651 (15)	0.073 (8)	0.47 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.0226 (3)	0.0172 (2)	0.0250 (3)	0.000	−0.00007 (19)	0.000
N1	0.027 (4)	0.014 (3)	0.025 (4)	−0.002 (2)	0.003 (3)	−0.003 (3)
N2	0.032 (4)	0.020 (3)	0.031 (4)	−0.005 (3)	−0.005 (3)	−0.003 (3)
C1	0.026 (4)	0.022 (4)	0.031 (5)	0.004 (3)	0.001 (3)	−0.005 (3)
C2	0.038 (5)	0.020 (4)	0.044 (6)	−0.006 (4)	0.006 (4)	−0.006 (4)
C3	0.031 (5)	0.030 (5)	0.034 (5)	−0.012 (4)	0.003 (4)	−0.010 (4)
C4	0.028 (5)	0.033 (5)	0.030 (5)	0.001 (3)	−0.004 (4)	−0.006 (4)
C5	0.019 (4)	0.027 (4)	0.022 (4)	0.000 (3)	0.003 (3)	0.002 (3)
C6	0.037 (5)	0.057 (6)	0.008 (4)	−0.011 (4)	0.000 (3)	−0.005 (3)
C7	0.047 (6)	0.038 (5)	0.036 (6)	0.012 (4)	−0.012 (4)	0.002 (4)
C8	0.025 (4)	0.020 (4)	0.032 (5)	−0.001 (3)	−0.002 (4)	0.000 (4)
Cl1	0.0272 (14)	0.0256 (14)	0.0292 (17)	0.000	−0.0033 (12)	0.000
O1	0.038 (5)	0.039 (5)	0.042 (6)	0.000	0.004 (4)	0.000
O2	0.055 (6)	0.031 (5)	0.035 (5)	0.000	−0.014 (4)	0.000
O3	0.058 (4)	0.055 (4)	0.041 (4)	0.033 (3)	−0.003 (3)	−0.003 (3)
Cl2	0.030 (7)	0.0226 (15)	0.047 (3)	0.000	−0.003 (11)	0.000
O4	0.031 (9)	0.077 (18)	0.13 (3)	0.000	−0.017 (11)	0.000
O5	0.11 (2)	0.09 (2)	0.063 (10)	0.000	−0.040 (13)	0.000
O6	0.072 (11)	0.034 (8)	0.124 (19)	0.002 (8)	0.025 (12)	−0.031 (10)
Cl2'	0.030 (7)	0.0226 (15)	0.047 (3)	0.000	−0.003 (11)	0.000
O4'	0.023 (11)	0.09 (2)	0.09 (2)	0.000	0.005 (13)	0.000
O5'	0.09 (2)	0.21 (4)	0.034 (9)	0.000	−0.016 (11)	0.000
O6'	0.057 (11)	0.037 (10)	0.12 (2)	0.013 (8)	0.007 (11)	0.028 (12)

Geometric parameters (Å, º)

Pt1—N2^i	1.994 (7)	C6—H6	0.9500
Pt1—N2	1.994 (7)	C7—C8	1.452 (11)
Pt1—N1	2.001 (6)	C7—H7A	0.9800
Pt1—N1^i	2.001 (6)	C7—H7B	0.9800
N1—C1	1.337 (9)	C7—H7C	0.9800
N1—C5	1.366 (9)	Cl1—O3^i	1.427 (6)
N2—C8	1.118 (9)	Cl1—O3	1.427 (6)
C1—C2	1.388 (11)	Cl1—O2	1.430 (9)
C1—H1	0.9500	Cl1—O1	1.436 (9)
C2—C3	1.360 (12)	Cl2—O6^ii	1.40 (3)
C2—H2	0.9500	Cl2—O6	1.40 (3)
C3—C4	1.424 (11)	Cl2—O5	1.44 (7)
C3—H3	0.9500	Cl2—O4	1.44 (2)
C4—C5	1.392 (10)	Cl2'—O6'^ii	1.38 (3)
C4—C6	1.442 (11)	Cl2'—O6'	1.38 (3)
C5—C5^i	1.410 (14)	Cl2'—O5'	1.42 (8)
C6—C6^i	1.338 (19)	Cl2'—O4'	1.44 (2)
N2^i—Pt1—N2	87.9 (3)	C4—C6—H6	119.5
N2^i—Pt1—N1	177.0 (2)	C8—C7—H7A	109.5
N2—Pt1—N1	95.1 (2)	C8—C7—H7B	109.5
N2^i—Pt1—N1^i	95.1 (2)	H7A—C7—H7B	109.5
N2—Pt1—N1^i	177.0 (2)	C8—C7—H7C	109.5
N1—Pt1—N1^i	81.9 (3)	H7A—C7—H7C	109.5
C1—N1—C5	118.6 (6)	H7B—C7—H7C	109.5
C1—N1—Pt1	128.7 (5)	N2—C8—C7	179.2 (9)
C5—N1—Pt1	112.7 (5)	O3^i—Cl1—O3	110.4 (6)
C8—N2—Pt1	173.4 (6)	O3^i—Cl1—O2	108.7 (3)
N1—C1—C2	121.7 (7)	O3—Cl1—O2	108.7 (3)
N1—C1—H1	119.1	O3^i—Cl1—O1	109.3 (3)
C2—C1—H1	119.1	O3—Cl1—O1	109.3 (3)
C3—C2—C1	120.3 (8)	O2—Cl1—O1	110.5 (6)
C3—C2—H2	119.9	O6^ii—Cl2—O6	116 (4)
C1—C2—H2	119.9	O6^ii—Cl2—O5	108 (3)
C2—C3—C4	119.7 (7)	O6—Cl2—O5	108 (3)
C2—C3—H3	120.1	O6^ii—Cl2—O4	110 (2)
C4—C3—H3	120.1	O6—Cl2—O4	110 (2)
C5—C4—C3	116.5 (7)	O5—Cl2—O4	105 (3)
C5—C4—C6	118.5 (7)	O6'^ii—Cl2'—O6'	106 (4)
C3—C4—C6	125.0 (8)	O6'^ii—Cl2'—O5'	111 (3)
N1—C5—C4	123.1 (7)	O6'—Cl2'—O5'	111 (3)
N1—C5—C5^i	116.3 (4)	O6'^ii—Cl2'—O4'	111 (3)
C4—C5—C5^i	120.5 (5)	O6'—Cl2'—O4'	111 (3)
C6^i—C6—C4	121.0 (5)	O5'—Cl2'—O4'	106 (4)
C6^i—C6—H6	119.5
N2—Pt1—N1—C1	1.5 (7)	C1—N1—C5—C4	−0.7 (11)
N1^i—Pt1—N1—C1	−178.3 (5)	Pt1—N1—C5—C4	−179.0 (6)
N2—Pt1—N1—C5	179.6 (5)	C1—N1—C5—C5^i	178.5 (5)
N1^i—Pt1—N1—C5	−0.2 (6)	Pt1—N1—C5—C5^i	0.2 (5)
C5—N1—C1—C2	1.2 (11)	C3—C4—C5—N1	−0.1 (11)
Pt1—N1—C1—C2	179.2 (6)	C6—C4—C5—N1	179.9 (7)
N1—C1—C2—C3	−1.0 (12)	C3—C4—C5—C5^i	−179.2 (5)
C1—C2—C3—C4	0.2 (12)	C6—C4—C5—C5^i	0.8 (9)
C2—C3—C4—C5	0.3 (12)	C5—C4—C6—C6^i	−0.8 (9)
C2—C3—C4—C6	−179.7 (8)	C3—C4—C6—C6^i	179.2 (6)

Symmetry codes: (i) x, −y+1/2, z; (ii) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O6^iii	0.95	2.60	3.48 (2)	155
C3—H3···O2^iv	0.95	2.54	3.210 (8)	127
C3—H3···O3^v	0.95	2.54	3.486 (11)	178
C7—H7A···O6^iii	0.98	2.39	3.066 (18)	126
C7—H7B···O3^vi	0.98	2.41	3.143 (11)	131

Symmetry codes: (iii) x+1/2, −y+1/2, −z+1/2; (iv) −x+1, y−1/2, −z; (v) −x+1, −y, −z; (vi) x+1/2, y, −z+1/2.