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Acta Crystallogr Sect E Struct Rep Online. 2009 February 1; 65(Pt 2): m230.
Published online 2009 January 28. doi:  10.1107/S1600536809002694
PMCID: PMC2968294

Tetra­chlorido(1,10-phenanthroline-κ2 N,N′)platinum(IV) monohydrate

Abstract

In the title complex, [PtCl4(C12H8N2)]·H2O, the Pt4+ ion is six-coordinated in a distorted octa­hedral environment by two N atoms of a 1,10-phenanthroline ligand and by four Cl atoms. As a result of the different trans effects of the N and Cl atoms, the Pt—Cl bonds trans to the N atom are slightly shorter than those trans to the Cl atom. The compound displays inter­molecular π–π inter­actions between the six-membered rings, with a centroid–centroid distance of 3.834 Å. There are also weak intra­molecular C—H(...)Cl hydrogen bonds. According to the IR spectrum, solvent water was present in the crystal, but owing to the high thermal motion of the uncoordinated O atom, the H atoms could not be detected.

Related literature

For details of some other Pt–phenanthroline complexes, see: Buse et al. (1977 [triangle]); Fanizzi et al. (1996 [triangle]). For related Pt–bipyridine complexes, see: Hambley (1986 [triangle]); Hojjat Kashani et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0m230-scheme1.jpg

Experimental

Crystal data

  • [PtCl4(C12H8N2)]·H2O
  • M r = 535.11
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m230-efi1.jpg
  • a = 14.8481 (19) Å
  • b = 12.4079 (16) Å
  • c = 17.379 (2) Å
  • V = 3201.8 (7) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 9.43 mm−1
  • T = 293 (2) K
  • 0.25 × 0.08 × 0.06 mm

Data collection

  • Bruker SMART 1000 CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.418, T max = 0.568
  • 18465 measured reflections
  • 3521 independent reflections
  • 2414 reflections with I > 2σ(I)
  • R int = 0.047

Refinement

  • R[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.141
  • S = 1.02
  • 3521 reflections
  • 181 parameters
  • H-atom parameters constrained
  • Δρmax = 1.41 e Å−3
  • Δρmin = −0.56 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809002694/fj2191sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809002694/fj2191Isup2.hkl

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

Acknowledgments

This work was supported by a Korea Research Foundation grant funded by the Korean Government (MOEHRD) (grant No. KRF-2007-412-J02001).

supplementary crystallographic information

Comment

The asymmetric unit of the title compound, [PtCl4(C12H8N2)].H2O, contains a neutral PtIV complex and a water molecule (Fig. 1 and 2). In the complex, the Pt4+ ion is six-coordinated in a distorted octahedral environment by two N atoms of the 1,10-phenanthroline ligand and four Cl atoms. The main contribution to the distortion is the tight N1—Pt1—N2 chelate angle (80.1 (2)°), which result in non-linear trans axes (<Cl1—Pt1—N1 = 174.0 (2)°, <Cl2—Pt1—N2 = 173.9 (2)° and <Cl3—Pt1—Cl4 = 176.84 (10)°). As a result of the different trans effects of the N and Cl atoms, the Pt—Cl bonds trans to the N atom (lengths: 2.317 (3) and 2.320 (2) Å) are slightly shorter than bond lengths to mutually trans Cl atoms (lengths: 2.343 (3) and 2.335 (3) Å). The compound displays intermolecular π-π interactions between six-membered rings, with a shortest centroid-centroid distance of 3.834 Å and with a dihedral angle between the ring planes of 1.48°. There are also weak intramolecular C—H···Cl hydrogen bonds (Table 1). According to the IR spectrum, water was present in the crystal.

Experimental

To a solution of K2PtCl6 (0.3002 g, 0.618 mmol) in H2O (20 ml) was added 1,10-phenanthroline (0.1108 g, 0.615 mmol) in MeOH (10 ml), and stirred for 3 h at room temperature. The formed precipitate was separated by filtration and washed with water and MeOH and dried under vacuum, to give a yellow powder (0.1655 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH2Cl2 solution. IR (KBr): 3424 cm-1 (broad).

Refinement

H atoms were positioned geometrically and allowed to ride on their respective parent atoms [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C)]. Due to the high thermal motion of the oxygen atom of the solvent H2O molecule, the H atoms could neither be located from Fourier difference maps, nor added geometrically.

Figures

Fig. 1.
The structure of the title compound, with displacement ellipsoids drawn at the 30% probability level for non-H atoms.
Fig. 2.
View of the unit-cell contents of the title compound.

Crystal data

[PtCl4(C12H8N2)]·H2OF(000) = 2000
Mr = 535.11Dx = 2.220 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 943 reflections
a = 14.8481 (19) Åθ = 3.2–23.2°
b = 12.4079 (16) ŵ = 9.43 mm1
c = 17.379 (2) ÅT = 293 K
V = 3201.8 (7) Å3Stick, yellow
Z = 80.25 × 0.08 × 0.06 mm

Data collection

Bruker SMART 1000 CCD diffractometer3521 independent reflections
Radiation source: fine-focus sealed tube2414 reflections with I > 2σ(I)
graphiteRint = 0.047
[var phi] and ω scansθmax = 27.1°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)h = −18→18
Tmin = 0.418, Tmax = 0.568k = −11→15
18465 measured reflectionsl = −22→21

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.0738P)2 + 11.9979P] where P = (Fo2 + 2Fc2)/3
3521 reflections(Δ/σ)max < 0.001
181 parametersΔρmax = 1.41 e Å3
0 restraintsΔρmin = −0.56 e Å3

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 (Å2)

xyzUiso*/Ueq
Pt1−0.12471 (3)0.29079 (3)0.18568 (2)0.04495 (16)
Cl1−0.27151 (18)0.3484 (2)0.20445 (16)0.0580 (7)
Cl2−0.15722 (18)0.12006 (19)0.23250 (16)0.0549 (6)
Cl3−0.16047 (19)0.23631 (19)0.06024 (15)0.0537 (6)
Cl4−0.0833 (2)0.3517 (2)0.30779 (14)0.0568 (6)
N10.0092 (5)0.2536 (6)0.1619 (4)0.0364 (16)
N2−0.0815 (5)0.4383 (5)0.1425 (4)0.0368 (16)
C10.0512 (7)0.1599 (7)0.1735 (5)0.045 (2)
H10.01930.10160.19320.054*
C20.1400 (7)0.1490 (8)0.1567 (7)0.051 (2)
H20.16900.08450.16790.062*
C30.1871 (7)0.2308 (8)0.1239 (6)0.052 (3)
H30.24710.22040.11050.062*
C40.1462 (6)0.3308 (7)0.1100 (6)0.041 (2)
C50.1870 (6)0.4213 (8)0.0779 (6)0.048 (2)
H50.24720.41770.06330.058*
C60.1405 (6)0.5157 (8)0.0675 (5)0.048 (2)
H60.16970.57380.04480.058*
C70.0491 (6)0.5276 (7)0.0901 (5)0.039 (2)
C8−0.0011 (6)0.6212 (7)0.0837 (6)0.047 (2)
H80.02490.68320.06340.057*
C9−0.0879 (8)0.6221 (7)0.1068 (6)0.056 (3)
H9−0.12130.68530.10280.067*
C10−0.1284 (6)0.5293 (7)0.1368 (6)0.047 (2)
H10−0.18820.53110.15260.057*
C110.0064 (6)0.4363 (6)0.1212 (5)0.0369 (19)
C120.0537 (6)0.3380 (7)0.1308 (5)0.0361 (19)
O10.0973 (14)0.4296 (19)0.4629 (12)0.258 (11)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Pt10.0506 (3)0.0368 (2)0.0475 (3)0.00031 (15)−0.00128 (17)0.00387 (15)
Cl10.0537 (14)0.0544 (15)0.0658 (17)0.0055 (11)0.0089 (12)0.0134 (12)
Cl20.0589 (14)0.0404 (12)0.0653 (17)−0.0065 (11)0.0036 (12)0.0105 (11)
Cl30.0648 (15)0.0489 (13)0.0475 (15)−0.0084 (11)−0.0064 (12)0.0002 (11)
Cl40.0744 (17)0.0486 (14)0.0473 (15)0.0025 (12)−0.0074 (12)−0.0021 (11)
N10.036 (4)0.036 (4)0.037 (4)−0.001 (3)0.002 (3)−0.006 (3)
N20.043 (4)0.024 (3)0.044 (4)−0.001 (3)0.000 (3)0.004 (3)
C10.053 (6)0.030 (5)0.053 (6)0.002 (4)0.003 (5)−0.002 (4)
C20.056 (6)0.037 (5)0.062 (7)0.008 (4)−0.008 (5)−0.001 (5)
C30.041 (5)0.058 (6)0.056 (6)0.012 (4)−0.006 (5)−0.017 (5)
C40.041 (5)0.042 (5)0.040 (5)−0.007 (4)0.002 (4)−0.011 (4)
C50.040 (5)0.056 (6)0.048 (6)−0.010 (4)0.003 (4)−0.008 (5)
C60.058 (6)0.050 (6)0.037 (5)−0.017 (4)0.001 (4)0.001 (4)
C70.054 (5)0.036 (5)0.027 (4)−0.010 (4)−0.006 (4)−0.004 (3)
C80.062 (6)0.032 (5)0.048 (6)−0.013 (4)−0.002 (5)−0.003 (4)
C90.084 (7)0.025 (4)0.059 (7)0.003 (5)−0.010 (6)0.000 (4)
C100.053 (5)0.039 (5)0.050 (6)0.002 (4)−0.002 (5)0.002 (4)
C110.048 (5)0.032 (4)0.030 (5)−0.002 (4)−0.007 (4)−0.006 (4)
C120.044 (5)0.032 (4)0.032 (5)−0.006 (4)−0.006 (4)−0.005 (3)
O10.33 (3)0.29 (3)0.151 (17)0.06 (2)0.028 (17)0.043 (17)

Geometric parameters (Å, °)

Pt1—N22.080 (7)C3—H30.9300
Pt1—N12.083 (7)C4—C51.393 (13)
Pt1—Cl12.317 (3)C4—C121.424 (12)
Pt1—Cl22.320 (2)C5—C61.372 (13)
Pt1—Cl42.335 (3)C5—H50.9300
Pt1—Cl32.343 (3)C6—C71.421 (13)
N1—C11.335 (11)C6—H60.9300
N1—C121.351 (11)C7—C81.384 (13)
N2—C101.330 (11)C7—C111.405 (11)
N2—C111.357 (11)C8—C91.351 (14)
C1—C21.357 (13)C8—H80.9300
C1—H10.9300C9—C101.400 (14)
C2—C31.358 (14)C9—H90.9300
C2—H20.9300C10—H100.9300
C3—C41.402 (13)C11—C121.417 (12)
N2—Pt1—N180.1 (3)C4—C3—H3119.7
N2—Pt1—Cl194.0 (2)C5—C4—C3126.5 (8)
N1—Pt1—Cl1174.0 (2)C5—C4—C12118.0 (8)
N2—Pt1—Cl2173.9 (2)C3—C4—C12115.5 (8)
N1—Pt1—Cl293.8 (2)C6—C5—C4121.5 (9)
Cl1—Pt1—Cl292.10 (9)C6—C5—H5119.2
N2—Pt1—Cl487.8 (2)C4—C5—H5119.2
N1—Pt1—Cl490.0 (2)C5—C6—C7122.2 (8)
Cl1—Pt1—Cl491.14 (10)C5—C6—H6118.9
Cl2—Pt1—Cl491.81 (10)C7—C6—H6118.9
N2—Pt1—Cl389.3 (2)C8—C7—C11117.7 (8)
N1—Pt1—Cl388.2 (2)C8—C7—C6125.4 (8)
Cl1—Pt1—Cl390.39 (10)C11—C7—C6117.0 (8)
Cl2—Pt1—Cl390.90 (9)C9—C8—C7119.8 (9)
Cl4—Pt1—Cl3176.84 (10)C9—C8—H8120.1
C1—N1—C12120.5 (8)C7—C8—H8120.1
C1—N1—Pt1127.5 (6)C8—C9—C10120.9 (9)
C12—N1—Pt1112.0 (6)C8—C9—H9119.5
C10—N2—C11120.0 (7)C10—C9—H9119.5
C10—N2—Pt1127.7 (6)N2—C10—C9120.0 (9)
C11—N2—Pt1112.3 (5)N2—C10—H10120.0
N1—C1—C2120.5 (9)C9—C10—H10120.0
N1—C1—H1119.7N2—C11—C7121.6 (8)
C2—C1—H1119.7N2—C11—C12117.4 (7)
C1—C2—C3121.1 (9)C7—C11—C12121.0 (8)
C1—C2—H2119.5N1—C12—C11118.2 (8)
C3—C2—H2119.5N1—C12—C4121.6 (8)
C2—C3—C4120.7 (9)C11—C12—C4120.2 (8)
C2—C3—H3119.7
N2—Pt1—N1—C1179.4 (8)C11—C7—C8—C9−0.1 (13)
Cl2—Pt1—N1—C1−0.2 (8)C6—C7—C8—C9179.5 (9)
Cl4—Pt1—N1—C191.6 (7)C7—C8—C9—C10−0.6 (15)
Cl3—Pt1—N1—C1−91.0 (7)C11—N2—C10—C91.7 (14)
N2—Pt1—N1—C12−1.2 (6)Pt1—N2—C10—C9179.3 (7)
Cl2—Pt1—N1—C12179.2 (5)C8—C9—C10—N2−0.2 (15)
Cl4—Pt1—N1—C12−89.0 (5)C10—N2—C11—C7−2.5 (13)
Cl3—Pt1—N1—C1288.4 (5)Pt1—N2—C11—C7179.6 (6)
N1—Pt1—N2—C10−177.2 (8)C10—N2—C11—C12178.2 (8)
Cl1—Pt1—N2—C104.2 (8)Pt1—N2—C11—C120.3 (9)
Cl4—Pt1—N2—C10−86.8 (8)C8—C7—C11—N21.7 (12)
Cl3—Pt1—N2—C1094.6 (8)C6—C7—C11—N2−178.0 (8)
N1—Pt1—N2—C110.5 (6)C8—C7—C11—C12−179.0 (8)
Cl1—Pt1—N2—C11−178.1 (6)C6—C7—C11—C121.3 (12)
Cl4—Pt1—N2—C1190.9 (6)C1—N1—C12—C11−178.7 (8)
Cl3—Pt1—N2—C11−87.7 (6)Pt1—N1—C12—C111.8 (9)
C12—N1—C1—C22.3 (13)C1—N1—C12—C4−0.6 (12)
Pt1—N1—C1—C2−178.3 (7)Pt1—N1—C12—C4180.0 (6)
N1—C1—C2—C3−3.7 (16)N2—C11—C12—N1−1.4 (12)
C1—C2—C3—C43.2 (16)C7—C11—C12—N1179.2 (7)
C2—C3—C4—C5179.0 (10)N2—C11—C12—C4−179.6 (8)
C2—C3—C4—C12−1.4 (14)C7—C11—C12—C41.0 (12)
C3—C4—C5—C6−179.5 (9)C5—C4—C12—N1179.7 (8)
C12—C4—C5—C61.0 (14)C3—C4—C12—N10.1 (12)
C4—C5—C6—C71.4 (15)C5—C4—C12—C11−2.2 (13)
C5—C6—C7—C8177.8 (9)C3—C4—C12—C11178.2 (8)
C5—C6—C7—C11−2.6 (13)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C1—H1···Cl20.932.723.298 (10)121
C10—H10···Cl10.932.743.306 (10)121

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FJ2191).

References

  • Bruker (2000). SADABS, SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Buse, K. D., Keller, H. J. & Pritzkow, H. (1977). Inorg. Chem.16, 1072–1076.
  • Fanizzi, F. P., Natile, G., Lanfranchi, M., Tiripicchio, A., Laschi, F. & Zanello, P. (1996). Inorg. Chem.35, 3173–3182. [PubMed]
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Hambley, T. W. (1986). Acta Cryst. C42, 49–51.
  • Hojjat Kashani, L., Amani, V., Yousefi, M. & Khavasi, H. R. (2008). Acta Cryst. E64, m905–m906. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.

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