Dichloridobis(2-phenyl­pyridine-κN)zinc(II)

Dharmalingam, S.; Lee, H.-J.; Yoon, S.

doi:10.1107/S1600536812010616

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Pages m431-m432

doi:10.1107/S1600536812010616

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Dichloridobis(2-phenylpyridine-κN)zinc(II)

Sivanesan Dharmalingam,^a Ha-Jin Lee ^b and Sungho Yoon ^a ^*

^aDepartment of Bio & Nano Chemistry, College of Natural Sciences, Kookmin University, 861-1 Jeongneung-dong, Seongbuk-gu, Seoul 136-702, Republic of Korea, and ^bJeonju Center, Korea Basic Science Institute (KBSI), 664-14 Dukjin dong 1-ga, Dukjin-gu, Jeonju 561-756, Republic of Korea
^*Correspondence e-mail: yoona@kookmin.ac.kr

(Received 3 March 2012; accepted 10 March 2012; online 17 March 2012)

In the title compound, [ZnCl₂(C₁₁H₉N)₂], the Zn²⁺ cation lies on a twofold axis and is coordinated by two Cl⁻ anions and the N atoms of two 2-phenylpyridine ligands, forming a ZnN₂Cl₂ polyhedron with a slightly distorted tetrahedral coordination geometry. The dihedral angle between the phenyl ring and the metal-bound pyridine ring is 50.3 (4)° for each 2-phenylpyridine ligand. This arranges the phenyl ring from one ligand in the complex above the pyridine ring of the other resulting in an intramolecular π–π interaction, with a centroid–centroid distance of 3.6796 (17) Å. Weak C—H⋯Cl hydrogen bonds stabilize the crystal packing, linking molecules into chains along the c axis.

Related literature

For background to metal complexes with 2-phenylpyridine ligands, see: Samha et al. (1993 ); Yoshinari et al. (2010 ); Zhao et al. (2008 ). For those involving substituted 2-phenylpyridine ligands, see: Santoro et al. (2011 ).

Experimental

Crystal data

[ZnCl₂(C₁₁H₉N)₂]
M_r = 446.67
Tetragonal, I 4₁ c d
a = 15.2803 (3) Å
c = 16.4339 (7) Å
V = 3837.1 (2) Å³
Z = 8
Mo Kα radiation
μ = 1.57 mm⁻¹
T = 200 K
0.31 × 0.29 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.814, T_max = 1.00
13165 measured reflections
2231 independent reflections
1754 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.074
S = 1.09
2231 reflections
123 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.36 e Å⁻³
Absolute structure: Flack (1983 ), 997 Friedel pairs
Flack parameter: 0.02 (2)

Table 1
Selected bond lengths (Å)

Zn1—N1	2.097 (2)
Zn1—Cl1	2.2432 (11)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯Cl1ⁱ	0.95	2.90	3.666 (3)	138
Symmetry code: (i) $[-x, y, z-{\script{1\over 2}}]$ .

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812010616/sj5207sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812010616/sj5207Isup2.hkl

checkCIF report

Comment top

2-Phenylpyridine coordinated metal complexes of Ir^III and Pt^II are well known for their intense photoluminescence (Samha et al., 1993; Yoshinari et al., 2010; Zhao et al., 2008). A four coordinate Pt^II square planar metal complex has also been reported with two 2-phenylpyridine and two Cl^- ligands (Yoshinari et al. 2010). Complexes with substituted 2-phenylpyridine ligands have also been reported (Santoro et al., 2011). Here, we report the structure of a tetrahedrally coordinated Zn²⁺ complex which crystallizes in the tetragonal space group I4₁cd with one half molecule in the asymmetric unit. Bond distances to the metal are given in Table 1 with the structure of the molecule shown in Fig 1 and its crystal packing involving weak intermolecular C—H···Cl interactions detailed in Fig 2 and Table 2.

Related literature top

For background to metal complexes with 2-phenylpyridine ligands, see: Samha et al. (1993); Yoshinari et al. (2010); Zhao et al. (2008). For those involving substituted 2-phenylpyridine ligands, see: Santoro et al. (2011).

Experimental top

To a solution of 2-phenylpyridine (1.56 ml, 11.0 mmol) in 30 mL of acetonitrile, ZnCl₂ (0.50 g, 3.6 mmol) was added at room temperature. After three hours, acetonitrile was removed under reduced pressure and crystals were collected from a dichloromethane and pentane layering system. Colorless block-like crystals. Yield = 90%, (1.45 g).

Structure description top

For background to metal complexes with 2-phenylpyridine ligands, see: Samha et al. (1993); Yoshinari et al. (2010); Zhao et al. (2008). For those involving substituted 2-phenylpyridine ligands, see: Santoro et al. (2011).

Computing details top

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom-numbering and with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A crystal packing diagram of the title compound, viewed along the a axis.

Dichloridobis(2-phenylpyridine-κN)zinc(II) top

Crystal data top

[ZnCl₂(C₁₁H₉N)₂]	D_x = 1.546 Mg m⁻³
M_r = 446.67	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁cd	Cell parameters from 4803 reflections
Hall symbol: I 4bw -2c	θ = 2.7–28.1°
a = 15.2803 (3) Å	µ = 1.57 mm⁻¹
c = 16.4339 (7) Å	T = 200 K
V = 3837.1 (2) Å³	Block, colorless
Z = 8	0.31 × 0.29 × 0.14 mm
F(000) = 1824

Data collection top

Bruker SMART CCD area-detector diffractometer	2231 independent reflections
Radiation source: fine-focus sealed tube	1754 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
φ and ω scans	θ_max = 28.3°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −18→20
T_min = 0.814, T_max = 1.00	k = −20→20
13165 measured reflections	l = −21→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.074	w = 1/[σ²(F_o²) + (0.0275P)² + 1.0418P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
2231 reflections	Δρ_max = 0.37 e Å⁻³
123 parameters	Δρ_min = −0.36 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 997 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (2)

Crystal data top

[ZnCl₂(C₁₁H₉N)₂]	Z = 8
M_r = 446.67	Mo Kα radiation
Tetragonal, I4₁cd	µ = 1.57 mm⁻¹
a = 15.2803 (3) Å	T = 200 K
c = 16.4339 (7) Å	0.31 × 0.29 × 0.14 mm
V = 3837.1 (2) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2231 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1754 reflections with I > 2σ(I)
T_min = 0.814, T_max = 1.00	R_int = 0.047
13165 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.074	Δρ_max = 0.37 e Å⁻³
S = 1.09	Δρ_min = −0.36 e Å⁻³
2231 reflections	Absolute structure: Flack (1983), 997 Friedel pairs
123 parameters	Absolute structure parameter: 0.02 (2)
1 restraint

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

	x	y	z	U_iso*/U_eq
Zn1	0.0000	0.0000	0.48912 (7)	0.02540 (12)
N1	0.08480 (15)	−0.05713 (15)	0.40397 (14)	0.0207 (5)
C1	0.08984 (19)	−0.14499 (19)	0.40824 (18)	0.0265 (6)
H1	0.0670	−0.1733	0.4551	0.032*
C2	0.12652 (19)	−0.19583 (19)	0.34786 (19)	0.0298 (7)
H2	0.1299	−0.2576	0.3536	0.036*
C3	0.1581 (2)	−0.1554 (2)	0.27923 (19)	0.0329 (7)
H3	0.1834	−0.1888	0.2365	0.039*
C4	0.1525 (2)	−0.0650 (2)	0.27340 (18)	0.0291 (7)
H4	0.1735	−0.0361	0.2261	0.035*
C5	0.11645 (16)	−0.01706 (17)	0.33602 (17)	0.0222 (6)
C6	0.11275 (18)	0.07988 (17)	0.33127 (17)	0.0226 (6)
C7	0.1446 (2)	0.13120 (19)	0.39417 (19)	0.0298 (7)
H7	0.1688	0.1040	0.4411	0.036*
C8	0.1416 (2)	0.2216 (2)	0.3894 (2)	0.0373 (8)
H8	0.1634	0.2564	0.4328	0.045*
C9	0.1067 (2)	0.2607 (2)	0.3209 (2)	0.0389 (8)
H9	0.1040	0.3227	0.3174	0.047*
C10	0.0756 (2)	0.2102 (2)	0.2572 (2)	0.0353 (8)
H10	0.0520	0.2376	0.2102	0.042*
C11	0.0787 (2)	0.1198 (2)	0.26203 (17)	0.0285 (7)
H11	0.0577	0.0851	0.2182	0.034*
Cl1	0.04582 (6)	0.10755 (6)	0.57169 (5)	0.0421 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0278 (3)	0.0310 (3)	0.0174 (2)	0.0033 (2)	0.000	0.000
N1	0.0218 (12)	0.0206 (12)	0.0196 (12)	0.0022 (10)	−0.0029 (10)	0.0004 (10)
C1	0.0260 (17)	0.0283 (16)	0.0253 (15)	0.0001 (13)	−0.0036 (13)	0.0026 (13)
C2	0.0321 (17)	0.0206 (15)	0.0368 (18)	0.0012 (12)	−0.0012 (13)	−0.0022 (13)
C3	0.0350 (18)	0.0287 (18)	0.0350 (18)	0.0024 (14)	0.0066 (15)	−0.0096 (15)
C4	0.0316 (17)	0.0297 (17)	0.0260 (15)	−0.0030 (13)	0.0089 (13)	0.0005 (13)
C5	0.0164 (13)	0.0272 (15)	0.0229 (16)	−0.0006 (11)	−0.0030 (11)	0.0014 (12)
C6	0.0216 (14)	0.0202 (13)	0.0262 (16)	0.0004 (12)	0.0049 (12)	0.0025 (12)
C7	0.0288 (17)	0.0308 (17)	0.0297 (17)	0.0000 (13)	−0.0015 (13)	0.0027 (13)
C8	0.0353 (19)	0.0274 (17)	0.049 (2)	−0.0038 (15)	0.0000 (16)	−0.0047 (15)
C9	0.0400 (18)	0.0252 (15)	0.051 (2)	0.0026 (15)	0.0091 (17)	0.0056 (17)
C10	0.0346 (17)	0.0371 (18)	0.0344 (19)	0.0056 (14)	0.0054 (14)	0.0184 (14)
C11	0.0266 (16)	0.0325 (17)	0.0264 (18)	0.0005 (13)	0.0038 (12)	0.0050 (13)
Cl1	0.0487 (5)	0.0513 (5)	0.0262 (4)	−0.0041 (4)	−0.0028 (4)	−0.0125 (4)

Geometric parameters (Å, º) top

Zn1—N1	2.097 (2)	C4—H4	0.9500
Zn1—N1ⁱ	2.097 (2)	C5—C6	1.484 (4)
Zn1—Cl1ⁱ	2.2432 (11)	C6—C7	1.386 (4)
Zn1—Cl1	2.2432 (11)	C6—C11	1.392 (4)
N1—C1	1.347 (4)	C7—C8	1.384 (4)
N1—C5	1.362 (3)	C7—H7	0.9500
C1—C2	1.379 (4)	C8—C9	1.382 (5)
C1—H1	0.9500	C8—H8	0.9500
C2—C3	1.374 (4)	C9—C10	1.384 (5)
C2—H2	0.9500	C9—H9	0.9500
C3—C4	1.388 (4)	C10—C11	1.384 (4)
C3—H3	0.9500	C10—H10	0.9500
C4—C5	1.378 (4)	C11—H11	0.9500

N1—Zn1—N1ⁱ	96.30 (13)	N1—C5—C4	121.0 (2)
N1—Zn1—Cl1ⁱ	106.95 (7)	N1—C5—C6	118.6 (2)
N1ⁱ—Zn1—Cl1ⁱ	121.04 (6)	C4—C5—C6	120.4 (2)
N1—Zn1—Cl1	121.04 (6)	C7—C6—C11	119.6 (3)
N1ⁱ—Zn1—Cl1	106.95 (7)	C7—C6—C5	120.8 (2)
Cl1ⁱ—Zn1—Cl1	105.55 (7)	C11—C6—C5	119.6 (3)
C1—N1—C5	118.1 (2)	C8—C7—C6	120.7 (3)
C1—N1—Zn1	114.56 (19)	C8—C7—H7	119.6
C5—N1—Zn1	125.39 (18)	C6—C7—H7	119.6
N1—C1—C2	123.2 (3)	C9—C8—C7	119.3 (3)
N1—C1—H1	118.4	C9—C8—H8	120.3
C2—C1—H1	118.4	C7—C8—H8	120.3
C3—C2—C1	118.7 (3)	C8—C9—C10	120.5 (3)
C3—C2—H2	120.6	C8—C9—H9	119.7
C1—C2—H2	120.6	C10—C9—H9	119.7
C2—C3—C4	118.8 (3)	C9—C10—C11	120.1 (3)
C2—C3—H3	120.6	C9—C10—H10	120.0
C4—C3—H3	120.6	C11—C10—H10	120.0
C5—C4—C3	120.2 (3)	C10—C11—C6	119.8 (3)
C5—C4—H4	119.9	C10—C11—H11	120.1
C3—C4—H4	119.9	C6—C11—H11	120.1

Symmetry code: (i) −x, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···Cl1ⁱⁱ	0.95	2.90	3.666 (3)	138

Symmetry code: (ii) −x, y, z−1/2.

Experimental details

Crystal data
Chemical formula	[ZnCl₂(C₁₁H₉N)₂]
M_r	446.67
Crystal system, space group	Tetragonal, I4₁cd
Temperature (K)	200
a, c (Å)	15.2803 (3), 16.4339 (7)
V (Å³)	3837.1 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.57
Crystal size (mm)	0.31 × 0.29 × 0.14

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.814, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	13165, 2231, 1754
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.074, 1.09
No. of reflections	2231
No. of parameters	123
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.36
Absolute structure	Flack (1983), 997 Friedel pairs
Absolute structure parameter	0.02 (2)

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Zn1—N1

2.097 (2)

Zn1—Cl1

2.2432 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···Cl1ⁱ	0.95	2.90	3.666 (3)	138.4

Symmetry code: (i) −x, y, z−1/2.

Acknowledgements

This research was supported by the Basic Science Research program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (MEST) (KRF-2008-C00146).

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