cis-Dichloridobis(2-phenyl­pyridine-κN)platinum(II)

In the title complex, cis-[PtCl₂(C₁₁H₉N)₂], the Pt^II ion is situated in a slightly distorted square-planar environment coordinated by two N atoms from two 2-phenyl­pyridine ligands and two Cl atoms. The two pyridyl planes are inclined with dihedral angles of 59.1 (2) and 61.84 (19)° with respect to the PtCl₂N₂ plane. In the crystal, the complex mol­ecules display inter- and intra­molecular π–π stacking inter­actions, with centroid-centroid distances of 3.806 (5)–3.845 (5) Å, which form a one-dimensional column structure along the a axis.

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.014 Å
• R factor = 0.039
• wR factor = 0.076
• Data-to-parameter ratio = 18.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT973_ALERT_2_B Large Calcd. Positive Residual Density on    Pt1       1.53 eA-3

Alert level C
PLAT213_ALERT_2_C Atom N2              has ADP max/min Ratio .....       3.90 oblat
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.31 Ratio
PLAT342_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..         14
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          4
PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       1.52 eA-3
PLAT234_ALERT_4_C Large Hirshfeld Difference C10    --  C11     ..       0.18 Ang.
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          3

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.43
           From the CIF: _reflns_number_total               4488
           Count of symmetry unique reflns         2352
           Completeness (_total/calc)            190.82%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      2136
           Fraction of Friedel pairs measured     0.908
           Are heavy atom types Z>Si present        yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2
PLAT917_ALERT_2_G The FCF is likely NOT based on a BASF/TWIN Flack          !
PLAT794_ALERT_5_G Note: Tentative Bond Valency for Pt1     .......       2.07

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

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

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S1. Comment

It has been well known that metal complexes with 2-phenylpyridinate (ppy = C₁₁H₈N) show intense photoluminescence, especially for Ir^III and Pt^II complexes (Evans et al., 2006; Chi & Chou, 2010). Recently, we found that the Ir^III complex having both ppy and D-Hpen ligands, [Ir^III(ppy)₂(D-Hpen)] (D—H₂pen = D-penicillamine), readily reacts with Ag^I ion to give a luminescent S bridged Ir^IIIAg^IIr^III trinuclear complex, [Ag{Ir(ppy)₂(D—H_0.5pen)}₂] (Saito et al., 2010). We report herein the crystal structure of a platinum(II) complex with two monodentate 2-phenylpyridine ligands, [PtCl₂(C₁₁H₉N)₂] (I), which was accidentally obtained in the course of the reaction of [PtCl(ppy-κ²N,C)]₂ with 1-thio-β-D-glucose.

The molecular structure of (I) is shown in Fig. 1. In (I), the two pyridyl planes of 2-phenylpyridine ligands are tilted to the coordination plane of Pt1; each of the dihedral angles of the pyridyl unit with respect to the Pt1/N1/N2/Cl1/Cl2 plane is 59.1 (2)° for the N1/C1–C5 plane and 61.84 (19)° for the N2/C12–C16 plane. In each 2-phenylpyridine ligand, the pyridyl and phenyl rings are inclined with angles of 40.4 (2)° for the N1/C1–C5 and C6—C11 planes and 48.1 (2)° for the N2/C12–C16 and C17—C22 planes, allowing them to form a pair of intramolecular π–π stacking interactions with the closest separations of 3.201 (9) and 3.256 (9) Å. Moreover, the complex molecule contacts to the neighboring molecules through intermolecular π–π stacking interactions with the closest separations of 3.438 (10) and 3.389 (10) Å, giving a one-dimensional columnar structure along the a axis (Fig. 2).

Related literature

For an NMR study on the title compound, see: Pazderski et al. (2009). For the crystal structures of closely related metal complexes, see: Chi & Chou (2010); Evans et al. (2006); Mdleleni et al. (1995); Okada et al. (2001); Saito et al. (2010).

S2. Experimental

The reaction of [PtCl(ppy)]₂ with 1-thio-β-D-glucose sodium salt in ethanol/water (v/v = 4/1) gave a yellow solution. The reaction solution was evaporated to dryness and was recrystallized from hot ethanol to give a small amount of yellow needle crystals of (I).

S3. Refinement

H atoms bonded to C atoms were placed at calculated positions and refined as riding, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. A view of molecular structure of (I), showing the atom-numbering scheme and 50% probability displacement ellipsoids.
	Fig. 2. A view of the one-dimensional columnar structure formed along the a axis in (I).

cis-Dichloridobis(2-phenylpyridine-κN)platinum(II)

Crystal data

[PtCl2(C11H9N)2]	F(000) = 1104
Mr = 576.37	Dx = 1.859 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: C -2yc	Cell parameters from 7887 reflections
a = 7.6457 (8) Å	θ = 3.1–27.4°
b = 18.0712 (19) Å	µ = 7.08 mm^−1
c = 14.9876 (12) Å	T = 200 K
β = 96.014 (7)°	Needle, yellow
V = 2059.4 (3) Å^3	0.30 × 0.05 × 0.03 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	3862 reflections with I > 2σ(I)
Detector resolution: 10.000 pixels mm^-1	Rint = 0.046
ω scans	θmax = 27.4°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→9
Tmin = 0.329, Tmax = 0.494	k = −23→23
9783 measured reflections	l = −17→19
4488 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.076	w = 1/[σ^2(Fo^2) + (0.0331P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
4488 reflections	Δρmax = 1.71 e Å^−3
244 parameters	Δρmin = −1.44 e Å^−3
2 restraints	Absolute structure: Flack (1983), 2143 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.010 (10)

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 (Ų)

	x	y	z	Uiso*/Ueq
Pt1	0.74923 (3)	0.137846 (14)	0.68733 (3)	0.01865 (8)
Cl1	0.6380 (6)	0.14739 (18)	0.8241 (2)	0.0380 (9)
Cl2	0.9250 (3)	0.03890 (12)	0.73490 (14)	0.0347 (5)
N1	0.6118 (9)	0.2302 (4)	0.6440 (4)	0.0241 (16)
C1	0.6562 (11)	0.2917 (5)	0.6883 (6)	0.027 (2)
H1	0.7275	0.2878	0.7440	0.033*
C2	0.6038 (13)	0.3623 (5)	0.6577 (7)	0.036 (2)
H2	0.6377	0.4053	0.6916	0.044*
C3	0.5000 (13)	0.3672 (6)	0.5756 (8)	0.040 (3)
H3	0.4642	0.4140	0.5513	0.049*
C4	0.4511 (12)	0.3037 (5)	0.5310 (6)	0.033 (2)
H4	0.3808	0.3061	0.4749	0.039*
C5	0.5031 (11)	0.2352 (5)	0.5670 (5)	0.0252 (19)
C6	0.4362 (13)	0.1654 (5)	0.5187 (6)	0.032 (2)
C7	0.4466 (13)	0.1573 (6)	0.4288 (6)	0.040 (3)
H7	0.4962	0.1954	0.3957	0.047*
C8	0.3829 (14)	0.0917 (7)	0.3855 (7)	0.049 (3)
H8	0.3868	0.0860	0.3228	0.059*
C9	0.3158 (14)	0.0368 (6)	0.4340 (8)	0.053 (3)
H9	0.2755	−0.0074	0.4042	0.064*
C10	0.3043 (13)	0.0433 (6)	0.5251 (8)	0.046 (3)
H10	0.2548	0.0052	0.5582	0.055*
C11	0.3698 (12)	0.1092 (5)	0.5664 (6)	0.032 (2)
H11	0.3677	0.1148	0.6293	0.039*
N2	0.8432 (15)	0.1270 (4)	0.5656 (7)	0.017 (2)
C12	0.7948 (10)	0.0630 (4)	0.5202 (5)	0.0176 (17)
H12	0.7352	0.0254	0.5493	0.021*
C13	0.8316 (11)	0.0526 (5)	0.4328 (5)	0.025 (2)
H13	0.7997	0.0076	0.4025	0.030*
C14	0.9150 (11)	0.1079 (5)	0.3899 (5)	0.025 (2)
H14	0.9378	0.1022	0.3292	0.030*
C15	0.9638 (11)	0.1707 (5)	0.4360 (5)	0.0244 (19)
H15	1.0212	0.2091	0.4069	0.029*
C16	0.9313 (10)	0.1798 (5)	0.5246 (5)	0.0161 (17)
C17	0.9946 (11)	0.2464 (5)	0.5768 (5)	0.0215 (18)
C18	0.9717 (11)	0.3163 (5)	0.5396 (6)	0.030 (2)
H18	0.9115	0.3221	0.4812	0.036*
C19	1.0357 (14)	0.3774 (6)	0.5868 (9)	0.050 (3)
H19	1.0216	0.4253	0.5607	0.060*
C20	1.1213 (15)	0.3692 (6)	0.6731 (9)	0.052 (3)
H20	1.1631	0.4116	0.7063	0.063*
C21	1.1455 (12)	0.2999 (6)	0.7105 (6)	0.040 (3)
H21	1.2048	0.2947	0.7691	0.048*
C22	1.0845 (11)	0.2382 (5)	0.6636 (5)	0.0249 (19)
H22	1.1025	0.1903	0.6892	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.02321 (15)	0.01661 (13)	0.01658 (13)	0.0010 (4)	0.00416 (8)	0.0011 (3)
Cl1	0.054 (2)	0.044 (2)	0.0187 (15)	0.0007 (18)	0.0153 (13)	0.0000 (13)
Cl2	0.0444 (15)	0.0290 (13)	0.0301 (12)	0.0094 (11)	0.0017 (9)	0.0108 (9)
N1	0.018 (4)	0.029 (4)	0.026 (4)	0.006 (3)	0.004 (3)	0.000 (3)
C1	0.021 (5)	0.026 (5)	0.037 (5)	0.003 (4)	0.011 (4)	−0.004 (4)
C2	0.033 (6)	0.026 (5)	0.052 (6)	0.008 (5)	0.014 (4)	0.000 (4)
C3	0.028 (6)	0.025 (6)	0.070 (7)	0.015 (5)	0.016 (5)	0.004 (5)
C4	0.023 (5)	0.039 (6)	0.036 (5)	0.005 (5)	0.006 (4)	0.014 (4)
C5	0.021 (5)	0.026 (5)	0.031 (5)	−0.001 (4)	0.013 (3)	0.006 (4)
C6	0.040 (6)	0.027 (5)	0.027 (5)	0.011 (4)	0.000 (4)	0.003 (4)
C7	0.026 (5)	0.063 (8)	0.029 (5)	0.014 (5)	0.000 (4)	−0.001 (4)
C8	0.041 (7)	0.050 (7)	0.052 (6)	0.022 (6)	−0.019 (5)	−0.015 (6)
C9	0.031 (6)	0.037 (7)	0.085 (9)	0.011 (5)	−0.021 (6)	−0.019 (6)
C10	0.028 (6)	0.041 (7)	0.067 (8)	0.012 (5)	−0.007 (5)	0.004 (5)
C11	0.035 (6)	0.021 (5)	0.042 (6)	0.002 (4)	0.006 (4)	−0.015 (4)
N2	0.021 (5)	0.004 (4)	0.026 (6)	0.006 (3)	−0.001 (4)	0.002 (3)
C12	0.018 (4)	0.007 (4)	0.028 (4)	0.000 (3)	0.002 (3)	−0.005 (3)
C13	0.024 (5)	0.024 (5)	0.028 (5)	0.009 (4)	0.003 (3)	−0.008 (3)
C14	0.027 (5)	0.036 (5)	0.013 (4)	0.008 (4)	0.001 (3)	−0.002 (3)
C15	0.024 (5)	0.025 (5)	0.024 (5)	0.009 (4)	0.002 (3)	0.007 (4)
C16	0.014 (4)	0.018 (5)	0.017 (4)	−0.001 (4)	0.005 (3)	0.006 (3)
C17	0.020 (5)	0.020 (5)	0.026 (4)	−0.002 (4)	0.008 (3)	0.002 (3)
C18	0.024 (5)	0.021 (5)	0.045 (5)	0.001 (4)	0.007 (4)	0.004 (4)
C19	0.029 (6)	0.025 (6)	0.098 (10)	−0.004 (5)	0.018 (6)	0.007 (5)
C20	0.035 (6)	0.038 (7)	0.086 (9)	−0.020 (6)	0.019 (6)	−0.031 (6)
C21	0.032 (6)	0.058 (8)	0.032 (5)	−0.012 (5)	0.013 (4)	−0.022 (5)
C22	0.031 (5)	0.018 (5)	0.026 (5)	−0.001 (4)	0.009 (3)	−0.010 (3)

Geometric parameters (Å, º)

Pt1—N2	2.039 (10)	C10—H10	0.9500
Pt1—N1	2.041 (7)	C11—H11	0.9500
Pt1—Cl2	2.304 (2)	N2—C16	1.352 (11)
Pt1—Cl1	2.306 (4)	N2—C12	1.373 (11)
N1—C1	1.321 (11)	C12—C13	1.381 (11)
N1—C5	1.353 (10)	C12—H12	0.9500
C1—C2	1.400 (12)	C13—C14	1.381 (12)
C1—H1	0.9500	C13—H13	0.9500
C2—C3	1.396 (15)	C14—C15	1.361 (12)
C2—H2	0.9500	C14—H14	0.9500
C3—C4	1.360 (14)	C15—C16	1.386 (11)
C3—H3	0.9500	C15—H15	0.9500
C4—C5	1.392 (12)	C16—C17	1.489 (11)
C4—H4	0.9500	C17—C18	1.385 (12)
C5—C6	1.515 (12)	C17—C22	1.414 (11)
C6—C7	1.366 (13)	C18—C19	1.374 (14)
C6—C11	1.370 (13)	C18—H18	0.9500
C7—C8	1.413 (15)	C19—C20	1.396 (16)
C7—H7	0.9500	C19—H19	0.9500
C8—C9	1.361 (16)	C20—C21	1.376 (15)
C8—H8	0.9500	C20—H20	0.9500
C9—C10	1.383 (15)	C21—C22	1.374 (12)
C9—H9	0.9500	C21—H21	0.9500
C10—C11	1.409 (13)	C22—H22	0.9500
N2—Pt1—N1	90.7 (3)	C6—C11—C10	122.1 (9)
N2—Pt1—Cl2	87.3 (3)	C6—C11—H11	118.9
N1—Pt1—Cl2	175.3 (2)	C10—C11—H11	118.9
N2—Pt1—Cl1	178.4 (3)	C16—N2—C12	119.4 (9)
N1—Pt1—Cl1	89.8 (2)	C16—N2—Pt1	125.3 (7)
Cl2—Pt1—Cl1	92.32 (11)	C12—N2—Pt1	115.0 (7)
C1—N1—C5	118.4 (8)	N2—C12—C13	120.9 (8)
C1—N1—Pt1	115.5 (6)	N2—C12—H12	119.5
C5—N1—Pt1	125.2 (6)	C13—C12—H12	119.5
N1—C1—C2	123.5 (9)	C12—C13—C14	119.5 (8)
N1—C1—H1	118.3	C12—C13—H13	120.2
C2—C1—H1	118.3	C14—C13—H13	120.2
C3—C2—C1	117.6 (10)	C15—C14—C13	118.9 (8)
C3—C2—H2	121.2	C15—C14—H14	120.5
C1—C2—H2	121.2	C13—C14—H14	120.5
C4—C3—C2	118.8 (9)	C14—C15—C16	121.2 (8)
C4—C3—H3	120.6	C14—C15—H15	119.4
C2—C3—H3	120.6	C16—C15—H15	119.4
C3—C4—C5	120.5 (9)	N2—C16—C15	120.0 (9)
C3—C4—H4	119.8	N2—C16—C17	118.8 (8)
C5—C4—H4	119.8	C15—C16—C17	121.2 (8)
N1—C5—C4	121.0 (8)	C18—C17—C22	119.7 (8)
N1—C5—C6	119.9 (8)	C18—C17—C16	120.4 (7)
C4—C5—C6	119.1 (8)	C22—C17—C16	119.8 (7)
C7—C6—C11	119.9 (9)	C19—C18—C17	120.2 (9)
C7—C6—C5	120.6 (9)	C19—C18—H18	119.9
C11—C6—C5	119.6 (8)	C17—C18—H18	119.9
C6—C7—C8	119.3 (10)	C18—C19—C20	119.9 (10)
C6—C7—H7	120.3	C18—C19—H19	120.0
C8—C7—H7	120.3	C20—C19—H19	120.0
C9—C8—C7	119.9 (10)	C21—C20—C19	120.3 (10)
C9—C8—H8	120.1	C21—C20—H20	119.8
C7—C8—H8	120.1	C19—C20—H20	119.8
C8—C9—C10	122.1 (10)	C22—C21—C20	120.4 (9)
C8—C9—H9	118.9	C22—C21—H21	119.8
C10—C9—H9	118.9	C20—C21—H21	119.8
C9—C10—C11	116.7 (11)	C21—C22—C17	119.5 (9)
C9—C10—H10	121.7	C21—C22—H22	120.3
C11—C10—H10	121.7	C17—C22—H22	120.3
N2—Pt1—N1—C1	−118.5 (6)	N1—Pt1—N2—C16	55.4 (9)
Cl1—Pt1—N1—C1	63.0 (6)	Cl2—Pt1—N2—C16	−120.4 (9)
N2—Pt1—N1—C5	50.4 (7)	N1—Pt1—N2—C12	−117.8 (7)
Cl1—Pt1—N1—C5	−128.1 (7)	Cl2—Pt1—N2—C12	66.4 (7)
C5—N1—C1—C2	−3.3 (12)	C16—N2—C12—C13	−1.4 (14)
Pt1—N1—C1—C2	166.4 (7)	Pt1—N2—C12—C13	172.2 (6)
N1—C1—C2—C3	−0.3 (13)	N2—C12—C13—C14	−1.3 (13)
C1—C2—C3—C4	1.8 (14)	C12—C13—C14—C15	2.0 (12)
C2—C3—C4—C5	0.3 (14)	C13—C14—C15—C16	0.0 (12)
C1—N1—C5—C4	5.5 (12)	C12—N2—C16—C15	3.4 (14)
Pt1—N1—C5—C4	−163.1 (6)	Pt1—N2—C16—C15	−169.5 (7)
C1—N1—C5—C6	−174.5 (8)	C12—N2—C16—C17	−175.5 (8)
Pt1—N1—C5—C6	16.9 (11)	Pt1—N2—C16—C17	11.5 (13)
C3—C4—C5—N1	−4.0 (13)	C14—C15—C16—N2	−2.8 (13)
C3—C4—C5—C6	175.9 (8)	C14—C15—C16—C17	176.2 (8)
N1—C5—C6—C7	−130.7 (9)	N2—C16—C17—C18	−135.0 (9)
C4—C5—C6—C7	49.3 (12)	C15—C16—C17—C18	46.0 (11)
N1—C5—C6—C11	47.3 (12)	N2—C16—C17—C22	47.4 (12)
C4—C5—C6—C11	−132.7 (9)	C15—C16—C17—C22	−131.6 (8)
C11—C6—C7—C8	2.1 (14)	C22—C17—C18—C19	−0.1 (13)
C5—C6—C7—C8	−179.9 (8)	C16—C17—C18—C19	−177.7 (8)
C6—C7—C8—C9	−1.5 (14)	C17—C18—C19—C20	−1.1 (14)
C7—C8—C9—C10	1.2 (16)	C18—C19—C20—C21	1.5 (16)
C8—C9—C10—C11	−1.5 (15)	C19—C20—C21—C22	−0.5 (15)
C7—C6—C11—C10	−2.5 (15)	C20—C21—C22—C17	−0.7 (13)
C5—C6—C11—C10	179.5 (8)	C18—C17—C22—C21	1.1 (12)
C9—C10—C11—C6	2.1 (14)	C16—C17—C22—C21	178.7 (8)