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The title complex, [Pt(C10H8N2)2](ClO4)2, adopts a square-planar geometry in which all four N-atom donors are strictly coplanar as the Pt ion lies on an inversion centre. However, the 2,2′-bipyridine ligand deviates significantly from planarity, as demonstrated by the angle of 20.52 (11)° between the mean planes of the two pyridine rings.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805029089/tk6260sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805029089/tk6260Isup2.hkl
Contains datablock I

CCDC reference: 287738

Key indicators

  • Single-crystal X-ray study
  • T = 85 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.014
  • wR factor = 0.036
  • Data-to-parameter ratio = 18.8

checkCIF/PLATON results

No syntax errors found



Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.361 0.572 Tmin and Tmax expected: 0.275 0.572 RR = 1.315 Please check that your absorption correction is appropriate. PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large ....... 1.33
Alert level G REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values From the CIF: _diffrn_reflns_theta_max 33.20 From the CIF: _reflns_number_total 3010 From the CIF: _diffrn_reflns_limit_ max hkl 10. 12. 13. From the CIF: _diffrn_reflns_limit_ min hkl -7. -11. -13. TEST1: Expected hkl limits for theta max Calculated maximum hkl 12. 13. 13. Calculated minimum hkl -12. -13. -13.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 2 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 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The title complex, (I) (Fig. 1), was obtained during a study of the reactivity of [Pt(C10H8N2)2]2+ in aqueous alkaline solution (McInnes et al., 2003). Complex (I) crystallizes in the triclinic space group P1 with the Pt ion lying on an inversion centre, thus requiring it to be strictly coplanar with the four attached N atoms. The Pt—N distances [2.0227 (18) and 2.0292 (17) Å] are similar to those found in [Pt(C10H8N2)2](NO3)2·H2O (Hazell et al., 1986) and [Pt(C10H8N2)2](CF3SO3)2 (Fedotova et al., 2003), and are typical of those found in Pt complexes containing pyridine ligands (mean = 2.064 Å, SD = 0.074 Å for 997 structurally characterized complexes and 2214 individual Pt—N distances; Cambridge Structural Database, Version 5.26 of November 2004 (Allen, 2002)]. The 2,2'-bipyridine ligands display a bow distortion (Fig. 2) with a remarkably large angle of 20.52 (11)° between the mean planes of the two rings (Hazell, 2004). A similar distortion is seen in the trifluoromethanesulfonate salt of the complex (Fedotova et al., 2003) and presumably prevents the close inter-ligand approach of atoms H1 and H10. It is tempting to speculate that the strain inherent in such a distortion is responsible for the unusual behaviour of [Pt(C10H8N2)2]2+ in aqueous alkaline solution, allowing facile coordination of hydroxide ion to give a pseudo-five-coordinate complex (McInnes et al., 2003).

There are weak π-stacking interactions throughout the three-dimensional structure (Fig. 3), with centroid-to-centroid distances between the pyridine rings of 3.703 (3) (−1 − x, −y, −z) and 3.924 (3) Å (−x, −y, 1 − z). The perchlorate ions are also involved in anion–π interactions, with O1–centroid (at 1 + x, y, 1 + z) and O4–centroid (at −x, 1 − y, 1 − z) distances of 3.064 (3) and 3.356 (3) Å, respectively.

Experimental top

Complex (I) precipitated on addition of one drop of 6 M NaClO4(aq) to a solution of [Pt(C10H8N2)2](NO3)2·H2O (53 mg), prepared according to McInnes et al. (2003) in water (1 ml) to which one equivalent of 1 M NaOH(aq) (84 ml) had been added. Dilution to approximately 20 ml with hot water and subsequent slow cooling gave (I) as small pale-yellow crystals.

Refinement top

All H atoms were included in the riding-model approximation, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The highest residual peak in the difference map is 0.79 Å from atom Pt1.

Computing details top

Data collection: APEX-II (Bruker, 2004); cell refinement: APEX-II and SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 and SHELXTL (Bruker, 2001); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The structure of the cation of (I), with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. View of the cation of (I), emphasizing the bow distortion of the 2,2'-bipyridine ligands.
[Figure 3] Fig. 3. Packing, viewed down the a axis. Close interactions are indicated as dashed lines.
bis(2,2'-bipyridine-κ2N,N')platinum(II) bis(perchlorate) top
Crystal data top
[Pt(C10H8N2)2](ClO4)2Z = 1
Mr = 706.35F(000) = 340
Triclinic, P1Dx = 2.227 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71069 Å
a = 7.811 (5) ÅCell parameters from 5644 reflections
b = 8.621 (5) Åθ = 2.4–33.0°
c = 9.054 (5) ŵ = 6.97 mm1
α = 72.972 (5)°T = 85 K
β = 86.553 (5)°Plate, pale-yellow
γ = 64.960 (5)°0.32 × 0.16 × 0.08 mm
V = 526.7 (5) Å3
Data collection top
Bruker Kappa-APEX-II area-detector
diffractometer
3010 independent reflections
Radiation source: fine-focus sealed tube3010 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
ϕ and ω scansθmax = 33.2°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 710
Tmin = 0.361, Tmax = 0.572k = 1112
11349 measured reflectionsl = 1313
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.014Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.036H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0182P)2 + 0.2101P]
where P = (Fo2 + 2Fc2)/3
3010 reflections(Δ/σ)max < 0.001
160 parametersΔρmax = 1.19 e Å3
0 restraintsΔρmin = 1.34 e Å3
Crystal data top
[Pt(C10H8N2)2](ClO4)2γ = 64.960 (5)°
Mr = 706.35V = 526.7 (5) Å3
Triclinic, P1Z = 1
a = 7.811 (5) ÅMo Kα radiation
b = 8.621 (5) ŵ = 6.97 mm1
c = 9.054 (5) ÅT = 85 K
α = 72.972 (5)°0.32 × 0.16 × 0.08 mm
β = 86.553 (5)°
Data collection top
Bruker Kappa-APEX-II area-detector
diffractometer
3010 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
3010 reflections with I > 2σ(I)
Tmin = 0.361, Tmax = 0.572Rint = 0.028
11349 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0140 restraints
wR(F2) = 0.036H-atom parameters constrained
S = 1.08Δρmax = 1.19 e Å3
3010 reflectionsΔρmin = 1.34 e Å3
160 parameters
Special details top

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) top
xyzUiso*/Ueq
Pt10.00000.00000.00000.00959 (3)
Cl10.72870 (7)0.55282 (6)0.74243 (5)0.01562 (9)
O30.6723 (2)0.74430 (19)0.68472 (17)0.0190 (3)
O40.5894 (3)0.5191 (3)0.8406 (2)0.0298 (4)
O10.9085 (2)0.4714 (2)0.8310 (2)0.0302 (4)
N10.1963 (2)0.0954 (2)0.07318 (17)0.0107 (3)
O20.7429 (4)0.4830 (3)0.6145 (2)0.0413 (5)
C20.3843 (3)0.2526 (3)0.0693 (2)0.0148 (3)
H20.43580.30070.01470.018*
C40.3484 (3)0.1824 (3)0.2993 (2)0.0142 (3)
H40.37300.18580.40170.017*
N20.1036 (2)0.1103 (2)0.17412 (17)0.0113 (3)
C80.2114 (3)0.1948 (3)0.4482 (2)0.0152 (4)
H80.24070.21890.54250.018*
C90.1373 (3)0.2933 (3)0.3368 (2)0.0145 (3)
H90.12170.38810.35340.017*
C10.2730 (3)0.1673 (2)0.0017 (2)0.0128 (3)
H10.25020.15920.10510.015*
C100.0865 (3)0.2491 (2)0.2004 (2)0.0135 (3)
H100.03920.31710.12490.016*
C30.4180 (3)0.2651 (3)0.2239 (2)0.0154 (4)
H30.48610.32810.27610.018*
C70.2414 (3)0.0596 (3)0.4169 (2)0.0137 (3)
H70.29560.00500.48840.016*
C60.1895 (3)0.0221 (2)0.2780 (2)0.0115 (3)
C50.2424 (3)0.0950 (2)0.2205 (2)0.0119 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.01102 (5)0.00998 (5)0.00989 (5)0.00593 (4)0.00202 (3)0.00391 (3)
Cl10.0217 (2)0.0170 (2)0.01378 (18)0.01234 (18)0.00363 (16)0.00656 (15)
O30.0224 (7)0.0149 (6)0.0192 (6)0.0078 (6)0.0016 (6)0.0038 (5)
O40.0348 (10)0.0429 (10)0.0297 (8)0.0320 (8)0.0123 (7)0.0143 (7)
O10.0205 (8)0.0213 (8)0.0394 (9)0.0071 (7)0.0057 (7)0.0029 (7)
N10.0113 (7)0.0108 (6)0.0121 (6)0.0065 (6)0.0020 (5)0.0036 (5)
O20.0820 (16)0.0377 (10)0.0229 (8)0.0363 (11)0.0158 (9)0.0208 (8)
C20.0136 (8)0.0154 (8)0.0181 (8)0.0070 (7)0.0011 (7)0.0076 (7)
C40.0150 (8)0.0151 (8)0.0143 (8)0.0079 (7)0.0033 (7)0.0049 (6)
N20.0116 (7)0.0121 (7)0.0125 (6)0.0066 (6)0.0017 (5)0.0045 (5)
C80.0139 (8)0.0185 (9)0.0156 (8)0.0064 (7)0.0026 (7)0.0094 (7)
C90.0138 (9)0.0133 (8)0.0191 (8)0.0058 (7)0.0015 (7)0.0087 (6)
C10.0120 (8)0.0135 (8)0.0139 (7)0.0048 (7)0.0008 (6)0.0064 (6)
C100.0127 (8)0.0123 (8)0.0168 (8)0.0062 (7)0.0019 (7)0.0051 (6)
C30.0151 (9)0.0154 (8)0.0195 (9)0.0094 (7)0.0042 (7)0.0067 (7)
C70.0128 (8)0.0161 (8)0.0134 (8)0.0067 (7)0.0024 (6)0.0055 (6)
C60.0101 (8)0.0116 (7)0.0132 (7)0.0048 (6)0.0011 (6)0.0041 (6)
C50.0109 (8)0.0125 (8)0.0123 (7)0.0047 (7)0.0010 (6)0.0042 (6)
Geometric parameters (Å, º) top
Pt1—N1i2.0227 (18)C4—H40.9300
Pt1—N12.0227 (18)N2—C101.346 (2)
Pt1—N22.0292 (17)N2—C61.360 (2)
Pt1—N2i2.0292 (17)C8—C91.385 (3)
Cl1—O21.4328 (18)C8—C71.387 (3)
Cl1—O41.4350 (18)C8—H80.9300
Cl1—O11.4420 (19)C9—C101.384 (3)
Cl1—O31.4488 (17)C9—H90.9300
N1—C11.346 (2)C1—H10.9300
N1—C51.362 (2)C10—H100.9300
C2—C11.381 (3)C3—H30.9300
C2—C31.389 (3)C7—C61.385 (3)
C2—H20.9300C7—H70.9300
C4—C51.380 (3)C6—C51.465 (3)
C4—C31.388 (3)
N1i—Pt1—N1180.00 (8)C9—C8—C7118.97 (17)
N1i—Pt1—N2101.17 (7)C9—C8—H8120.5
N1—Pt1—N278.83 (7)C7—C8—H8120.5
N1i—Pt1—N2i78.83 (7)C10—C9—C8119.34 (18)
N1—Pt1—N2i101.17 (7)C10—C9—H9120.3
N2—Pt1—N2i180.00 (10)C8—C9—H9120.3
O2—Cl1—O4109.56 (12)N1—C1—C2122.41 (17)
O2—Cl1—O1110.92 (13)N1—C1—H1118.8
O4—Cl1—O1109.44 (12)C2—C1—H1118.8
O2—Cl1—O3109.35 (11)N2—C10—C9121.75 (18)
O4—Cl1—O3109.29 (11)N2—C10—H10119.1
O1—Cl1—O3108.25 (10)C9—C10—H10119.1
C1—N1—C5118.46 (16)C4—C3—C2119.06 (18)
C1—N1—Pt1127.86 (13)C4—C3—H3120.5
C5—N1—Pt1113.52 (12)C2—C3—H3120.5
C1—C2—C3118.82 (18)C6—C7—C8119.21 (18)
C1—C2—H2120.6C6—C7—H7120.4
C3—C2—H2120.6C8—C7—H7120.4
C5—C4—C3119.23 (17)N2—C6—C7121.46 (17)
C5—C4—H4120.4N2—C6—C5114.00 (16)
C3—C4—H4120.4C7—C6—C5124.07 (17)
C10—N2—C6118.88 (16)N1—C5—C4121.63 (17)
C10—N2—Pt1127.63 (13)N1—C5—C6114.01 (16)
C6—N2—Pt1113.36 (12)C4—C5—C6123.97 (16)
Symmetry code: (i) x, y, z.

Experimental details

Crystal data
Chemical formula[Pt(C10H8N2)2](ClO4)2
Mr706.35
Crystal system, space groupTriclinic, P1
Temperature (K)85
a, b, c (Å)7.811 (5), 8.621 (5), 9.054 (5)
α, β, γ (°)72.972 (5), 86.553 (5), 64.960 (5)
V3)526.7 (5)
Z1
Radiation typeMo Kα
µ (mm1)6.97
Crystal size (mm)0.32 × 0.16 × 0.08
Data collection
DiffractometerBruker Kappa-APEX-II area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.361, 0.572
No. of measured, independent and
observed [I > 2σ(I)] reflections
11349, 3010, 3010
Rint0.028
(sin θ/λ)max1)0.770
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.014, 0.036, 1.08
No. of reflections3010
No. of parameters160
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.19, 1.34

Computer programs: APEX-II (Bruker, 2004), APEX-II and SAINT (Bruker, 2001), SAINT, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997 and SHELXTL (Bruker, 2001), WinGX (Farrugia, 1999).

 

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