research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 3| March 2015| Pages 272-274

Crystal structure and luminescent properties of [1-(bi­phenyl-4-yl)-1H-imidazole-κN3]di­chloridozinc

CROSSMARK_Color_square_no_text.svg

aChangchun University of Science & Technology, School of Chemistry and Environmental Engineering, Changchun 130022, People's Republic of China
*Correspondence e-mail: ywt1982@163.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 19 January 2015; accepted 9 February 2015; online 13 February 2015)

The mononuclear title compound, [ZnCl2(C15H12N2)2], was synthesized by reaction of zinc chloride and 1-(biphenyl-4-yl)-1H-imidazole (bpi) under hydro­thermal conditions. The ZnII atom is tetra­hedrally coordinated by the free imidazole N atoms of two bpi ligands and by two Cl atoms. The bpi ligands are not planar, with dihedral angles of 37.52 (14) and 42.45 (14)° between the phenyl rings and 37.13 (14) and 40.05 (14)° between the phenyl rings and the attached imidazole rings, respectively. Mutual ππ inter­actions, with a centroid-to-centroid distance of 3.751 (2) Å between the phenyl and imidazole rings of neighbouring ligands, are present, leading to dimers that are arranged in rows parallel to [-211].

1. Chemical context

Metal coordination polymers constructed from organic ligands and metal cations have received attention because of their structural diversity and inter­esting physical and chemical properties, including adsorption, mol­ecular separation, heterogeneous catalysis and non-linear optics (Sumida et al., 2012[Sumida, K., Rogow, D. L., Mason, J. A., McDonald, T. M., Bloch, E. D., Herm, Z. R., Bae, T. H. & Long, J. R. (2012). Chem. Rev. 112, 724-781.]; Colombo et al., 2012[Colombo, V., Montoro, C., Maspero, A., Palmisano, G., Masciocchi, N., Galli, S., Barea, E. & Navarro, J. A. R. (2012). J. Am. Chem. Soc. 134, 12830-12843.]; Henke et al., 2012[Henke, S., Schneemann, A., Wütscher, A. & Fischer, R. A. (2012). J. Am. Chem. Soc. 134, 9464-9474.]). The development of such materials for various applications is reliant on the functionalities and modulations of the inorganic central atoms and the organic linkers. Materials constructed from d10 metal ions can be promising photoactive candidates (Lan et al., 2009[Lan, A., Li, K., Wu, H., Olson, D. H., Emge, T. J., Ki, W., Hong, M. & Li, J. (2009). Angew. Chem. Int. Ed. 48, 2334-2338.]; Qin et al., 2014[Qin, J. S., Zhang, S. R., Du, D. Y., Shen, P., Bao, S. J., Lan, Y. Q. & Su, Z. M. (2014). Chem. Eur. J. 20, 5625-5630.]). For example, a series of zinc- and cadmium-based coordination polymers were reported to be luminescent sensors for the detection of small organic mol­ecules (Yi et al., 2012[Yi, F. Y., Yang, W. T. & Sun, Z. M. (2012). J. Mater. Chem. 22, 23201-23209.]; Wang et al., 2013[Wang, H., Yang, W. T. & Sun, Z. M. (2013). Chem. Asian J. 8, 982-989.]). On the other hand, the choice of the organic ligands or linkers is important for the supra­molecular arrangement.

[Scheme 1]

Among the various organic ligands used for the construction of coordination polymers, nitro­gen-donor species are dominant due to their strong affinities for binding metal atoms (Yang et al., 2013[Yang, W. T., Yi, F. Y., Li, X. D., Wang, L., Dang, S. & Sun, Z. M. (2013). RSC Adv. 3, 25065-25070.], 2014[Yang, W., Yi, F. Y., Tian, T., Tian, W. G. & Sun, Z. M. (2014). Cryst. Growth Des. 14, 1366-1374.]). In particular, imidazoles are of great inter­est for the construction of zeolite imidazolate frameworks, which exhibit high stability and practical applications (Phan et al., 2010[Phan, A., Doonan, C. J., Uribe-Romo, F. J., Knobler, C. B., O'Keeffe, M. & Yaghi, O. M. (2010). Acc. Chem. Res. 43, 58-67.]). By further modification of imidazole ligands, various compounds with different structural set-ups have been reported, including one-dimensional, two-dimensional and three-dimensional architectures (Kan et al., 2012[Kan, W. Q., Yang, J., Liu, Y. Y. & Ma, J. F. (2012). CrystEngComm, 14, 6934-6945.]). Recently, two one-dimensional imidazole-based zinc complexes were synthesized by using 1,4-di(1H-imidazol-1-yl)benzene (dib), and 1,3,5-tri(1H-imidazol-1-yl)benzene (tib) as ligands (Wang et al., 2014[Wang, H., Yang, X. Y., Ma, Y. Q., Cui, W. B., Li, Y. H., Tian, W. G., Yao, S., Gao, Y., Dang, S. & Zhu, W. (2014). Inorg. Chim. Acta, 416, 63-68.]). To obtain further effects on the final structure by modification of the substituent of the imidazoles, 1-(biphenyl-4-yl)-1H-imidazole (bpi) was chosen as ligand and reacted with Zn2+ ions in this work, yielding the title compound ZnCl2(C15H12N2)2, (I)[link]. Apart from the structure determination, its photoluminescent property is also reported.

2. Structural commentary

As shown in Fig. 1[link], the asymmetric unit of (I)[link] consists of one zinc(II) cation, two bpi ligands and two chlorine ligands. The cation has a distorted tetra­hedral coordination sphere defined by the free imidazole N atoms and two Cl atoms. The Zn—N and Zn—Cl bond lengths (Table 1[link]) are typical for tetra­hedrally coordinated ZnII. The dihedral angles between the two phenyl rings in the two bpi ligands are 37.52 (14) and 42.45 (14)°, respectively, while the dihedral angles between the phenyl rings and the attached imidazole rings are 37.13 (14) and 40.05 (14)°.

Table 1
Selected bond lengths (Å)

Zn1—N1 2.021 (2) Zn1—Cl1 2.2258 (7)
Zn1—N3 2.028 (2) Zn1—Cl2 2.2447 (8)
[Figure 1]
Figure 1
The mol­ecular structure of compound (I)[link]. Displacement ellipsoids were drawn at the 30% probability level.

ZnII-based compounds with metal-organic framework structures are well-known for their luminescence properties. The photoluminescence spectrum of compound (I)[link] in the solid state is shown in Fig. 2[link]. On excitation at 278 nm, the emission band is centred at 350 nm. Compared to the free bpi ligand, which exhibits one main fluorescent emission band around 400 nm when excited at 271 nm, the emission band of complex (I)[link] is about 50 nm hypochromatically shifted. Considering metal atoms with a d10 electron configuration and the bonding inter­actions with the ligand, such broad emission bands may be assigned to a ligand-to-ligand charge transfer (LLCT), admixing with metal-to-ligand (MLCT) and ligand-to-metal (LMCT) charge transfers (Gong et al., 2011[Gong, Y., Li, J., Qin, J.-B., Wu, T., Cao, R. & Li, J.-H. (2011). Cryst. Growth Des. 11, 1662-1674.]).

[Figure 2]
Figure 2
Excitation and emission spectra of compound (I)[link] in the solid state.

3. Supra­molecular features

As mentioned before, the imidazole-based ligands dib and tib, featuring two and three imidazole rings, respectively, can adopt different structural dimensionalities. The bpi ligand used in this study, however, has only one available N-donor, thus preventing the formation of a polymeric structure. Nevertheless, there are weak inter­molecular ππ stacking inter­actions between single mol­ecules in the crystal packing. The terminal phenyl ring and the imidazole ring of a neighbouring ligand are tilted to each other by 11.72 (17)°, with a centroid-to-centroid distance of 3.751 (2) Å (Fig. 3[link]).

[Figure 3]
Figure 3
View of the crystal structure along [010] emphasizing ππ inter­actions (dotted lines and inset).

4. Synthesis and crystallization

All chemicals were purchased commercially and used without further purification. A mixture of ZnCl2 (81.6 mg, 5 mmol), bpi (130 mg, 0.6 mmol), and de-ionized water (9 ml) was loaded into a 20 ml Teflon-lined stainless steel autoclave. The autoclave was sealed and heated at 423 K for 5 d, and then cooled to room temperature by switching off the furnace. Colourless block-shaped crystals were isolated, which were filtered off and washed with de-ionized water. The final product was dried at ambient temperature (yield 75% based on zinc). Analysis calculated (wt%) for ZnCl2(C15H12N2)2: C, 62.47; H, 4.19; N, 9.71. Found: C, 62.45; H, 4.15; N, 9.79.

Elemental analyses of C, H, and N were conducted on a Perkin–Elmer 2400 elemental analyser. The photoluminescence (PL) excitation and emission spectra were recorded with an F-7000 luminescence spectrometer equipped with a xenon lamp of 450 W as an excitation light source. The photomultiplier tube voltage was 400 V, the scan speed was 1200 nm min−1, both the excitation and the emission slit widths were 5.0 nm.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. All hydrogen atoms were positioned geometrically with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).

Table 2
Experimental details

Crystal data
Chemical formula [ZnCl2(C15H12N2)2]
Mr 576.80
Crystal system, space group Triclinic, P[\overline{1}]
Temperature (K) 296
a, b, c (Å) 9.2410 (6), 9.2595 (5), 16.4106 (10)
α, β, γ (°) 87.770 (1), 88.819 (1), 72.823 (1)
V3) 1340.50 (14)
Z 2
Radiation type Mo Kα
μ (mm−1) 1.14
Crystal size (mm) 0.40 × 0.30 × 0.30
 
Data collection
Diffractometer Bruker APEXII CCD area detector
Absorption correction Multi-scan (SADABS; Bruker, 2008[Bruker, (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.658, 0.726
No. of measured, independent and observed [I > 2σ(I)] reflections 8564, 5308, 4067
Rint 0.025
(sin θ/λ)max−1) 0.619
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.091, 1.00
No. of reflections 5308
No. of parameters 334
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.31, −0.35
Computer programs: APEX2 and SAINT (Bruker, 2008[Bruker, (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 and SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), DIAMOND (Brandenburg, 2006[Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Chemical context top

Metal coordination polymers constructed from organic ligands and metal cations have received attention because of their structural diversity and inter­esting physical and chemical properties, including adsorption, molecular separation, heterogeneous catalysis and non-linear optics (Sumida et al., 2012; Colombo et al., 2012; Henke et al., 2012). The development of such materials for various applications is reliant on the functionalities and modulations of the inorganic central atom and the organic linker. Materials constructed from d10 metal ions can be promising photoactive candidates (Lan et al., 2009; Qin et al., 2014). For example, a series of zinc- and cadmium-based coordination polymers were reported to be luminescent sensors for the detection of small organic molecules (Yi et al., 2012; Wang et al., 2013). On the other hand, the choice of the organic ligand or linkers is important for the supra­molecular arrangement.

Among the various organic ligands used for the construction of coordination polymers, nitro­gen-donor species are dominant due to their strong affinities for binding metal atoms (Yang et al., 2013, 2014). In particular, imidazoles are of great inter­est for the construction of zeolite imidazolate frameworks, which exhibit high stability and practical applications (Phan et al., 2010). By further modification of imidazole ligands, various compounds with different structural set-ups have been reported, including one-dimensional, two-dimensional and three-dimensional architectures (Kan et al., 2012). Recently, two one-dimensional imidazole-based zinc complexes were synthesized by using 1,4-di(1H-imidazol-1-yl)benzene (dib), and 1,3,5-tri(1H-imidazol-1-yl)benzene (tib) as ligands (Wang et al., 2014). To obtain further effects on the final structure by modification of the substituent of the imidazoles, 1-(bi­phenyl-4-yl)-1H-imidazole (bpi) was chosen as ligand and reacted with Zn2+ ions in this work, yielding the title compound ZnCl2(C15H12N2)2, (I). Apart from the structure determination, its photoluminescent properties are also reported.

Structural commentary top

As shown in Fig. 1, the asymmetric unit of (I) consists of one zinc(II) cation, two bpi ligands and two chlorine ligands. The cation has a distorted tetra­hedral coordination sphere defined by the free imidazole N atoms and two Cl atoms. The Zn—N and Zn—Cl bond lengths (Table 1) are typical for tetra­hedrally coordinated ZnII. The dihedral angles between the two phenyl rings in the two bpi ligands are 37.52 (14) and 42.45 (14)°, respectively, while the dihedral angles between the phenyl rings and the attached imidazole rings are 37.13 (14) and 40.05 (14)°.

ZnII-based compounds with metal-organic framework structures are well-known for their luminescence properties. The photoluminescence spectrum of compound (I) in the solid state is shown in Fig. 2. On excitation at 278 nm, the emission band is centred at 350 nm. Compared to the free bpi ligand, which exhibits one main fluorescent emission band around 400 nm when excited at 271 nm, the emission band of complex (I) is about 50 nm hypochromatically shifted. Considering metal atoms with a d10 electron configuration and the bonding inter­actions with the ligand, such broad emission bands may be assigned to a ligand-to-ligand charge transfer (LLCT), admixing with metal-to-ligand (MLCT) and ligand-to-metal (LMCT) charge transfers (Gong et al., 2011).

Supra­molecular features top

As mentioned before, the imidazole-based ligands dib and tib, featuring two and three imidazole rings, respectively, can adopt different structural dimensionalities. The bpi ligand used in this study, however, has only one available N-donor, thus preventing the formation of a polymeric structure. Nevertheless, there are weak inter­molecular ππ stacking inter­actions between single molecules in the crystal packing. The terminal phenyl ring and the imidazole ring of a neighbouring ligand are tilted to each other by 11.72 (17)°, with a centroid-to-centroid distance of 3.751 Å (Fig. 3).

Synthesis and crystallization top

All chemicals were purchased commercially and used without further purification. A mixture of ZnCl2 (81.6 mg, 5 mmol), bpi (130 mg, 0.6 mmol), and de-ionized water (9 ml) was loaded into a 20 ml Teflon-lined stainless steel autoclave. The autoclave was sealed and heated at 423 K for 5 d, and then cooled to room temperature by switching off the furnace. Colourless block-shaped crystals were isolated, which were filtered off and washed with de-ionized water. The final product was dried at ambient temperature (yield 75% based on zinc). Analysis calculated (wt%) for ZnCl2(C15H12N2)2: C, 62.47; H, 4.19; N, 9.71. Found: C, 62.45; H, 4.15; N, 9.79.

Elemental analyses of C, H, and N were conducted on a Perkin–Elmer 2400 elemental analyser. The photoluminescence (PL) excitation and emission spectra were recorded with an F-7000 luminescence spectrometer equipped with a xenon lamp of 450 W as an excitation light source. The photomultiplier tube voltage was 400 V, the scan speed was 1200 nm min-1, both the excitation and the emission slit widths were 5.0 nm.

Refinement top

All hydrogen atoms were positioned geometrically with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).

Related literature top

For related literature, see: Colombo et al. (2012); Gong et al. (2011); Henke et al. (2012); Kan et al. (2012); Lan et al. (2009); Phan et al. (2010); Qin et al. (2014); Sumida et al. (2012); Wang et al. (2013, 2014); Yang et al. (2013, 2014); Yi et al. (2012).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of compound (I). Displacement ellipsoids were drawn at the 30% probability level.
[Figure 2] Fig. 2. Excitation and emission spectra of compound (I) in the solid state.
[Figure 3] Fig. 3. View of the crystal structure along [010] emphasizing ππ interactions (dotted lines and inset).
[1-(Biphenyl-4-yl)-1H-imidazole-κN3]dichloridozinc top
Crystal data top
[ZnCl2(C15H12N2)2]Z = 2
Mr = 576.80F(000) = 592
Triclinic, P1#Added by publCIF
_symmetry_space_group_name_hall '-P 1' #Added by publCIF
_audit_update_record
Hall symbol: -P 1Dx = 1.429 Mg m3
a = 9.2410 (6) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.2595 (5) ÅCell parameters from 2594 reflections
c = 16.4106 (10) Åθ = 2.3–24.3°
α = 87.770 (1)°µ = 1.14 mm1
β = 88.819 (1)°T = 296 K
γ = 72.823 (1)°Block, colourless
V = 1340.50 (14) Å30.40 × 0.30 × 0.30 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
5308 independent reflections
Radiation source: fine-focus sealed tube4067 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
phi and ω scansθmax = 26.1°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 1111
Tmin = 0.658, Tmax = 0.726k = 1111
8564 measured reflectionsl = 2017
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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0389P)2 + 0.3283P]
where P = (Fo2 + 2Fc2)/3
5308 reflections(Δ/σ)max = 0.014
334 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.35 e Å3
Crystal data top
[ZnCl2(C15H12N2)2]γ = 72.823 (1)°
Mr = 576.80V = 1340.50 (14) Å3
Triclinic, P1Z = 2
a = 9.2410 (6) ÅMo Kα radiation
b = 9.2595 (5) ŵ = 1.14 mm1
c = 16.4106 (10) ÅT = 296 K
α = 87.770 (1)°0.40 × 0.30 × 0.30 mm
β = 88.819 (1)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
5308 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
4067 reflections with I > 2σ(I)
Tmin = 0.658, Tmax = 0.726Rint = 0.025
8564 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.091H-atom parameters constrained
S = 1.00Δρmax = 0.31 e Å3
5308 reflectionsΔρmin = 0.35 e Å3
334 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
Zn10.49124 (3)1.09677 (3)0.333749 (18)0.04334 (11)
N30.5776 (2)0.8683 (2)0.33926 (13)0.0451 (5)
N10.2746 (2)1.1586 (2)0.37469 (13)0.0472 (5)
N20.0780 (2)1.2196 (2)0.45740 (13)0.0452 (5)
N40.6993 (2)0.6477 (2)0.28944 (12)0.0418 (5)
C280.6686 (3)0.7984 (3)0.28125 (16)0.0466 (6)
H28A0.70720.84750.23950.056*
C250.7889 (3)0.5422 (3)0.23310 (15)0.0414 (6)
C100.0104 (3)1.2386 (3)0.53170 (16)0.0456 (6)
C70.1776 (3)1.2747 (3)0.67615 (16)0.0452 (6)
C220.9495 (3)0.3553 (3)0.11331 (15)0.0420 (6)
C300.6209 (3)0.6192 (3)0.35697 (16)0.0475 (6)
H30A0.61900.52490.37780.057*
C260.7462 (3)0.4182 (3)0.21310 (17)0.0476 (6)
H26A0.66410.39700.23910.057*
C120.0612 (3)1.1433 (3)0.66213 (17)0.0506 (7)
H12A0.03851.06620.70210.061*
C270.8274 (3)0.3254 (3)0.15356 (17)0.0487 (7)
H27A0.79940.24070.14010.058*
C161.0323 (3)0.2598 (3)0.04652 (16)0.0453 (6)
C240.9140 (3)0.5714 (3)0.19650 (16)0.0483 (7)
H24A0.94490.65300.21220.058*
C230.9918 (3)0.4791 (3)0.13708 (17)0.0477 (6)
H23A1.07500.49990.11200.057*
C60.3160 (3)1.4297 (3)0.79101 (18)0.0519 (7)
H6A0.29351.51350.76740.062*
C290.5470 (3)0.7554 (3)0.38738 (16)0.0492 (6)
H29A0.48510.77040.43360.059*
C110.0216 (3)1.1242 (3)0.59019 (17)0.0523 (7)
H11A0.09831.03490.58160.063*
C10.2672 (3)1.2918 (3)0.75330 (16)0.0447 (6)
C140.1475 (3)1.2263 (3)0.33028 (18)0.0524 (7)
H14A0.14551.24340.27400.063*
C80.2076 (3)1.3875 (3)0.61520 (17)0.0517 (7)
H8A0.28611.47590.62260.062*
C90.1236 (3)1.3713 (3)0.54385 (17)0.0509 (7)
H9A0.14321.44930.50440.061*
C20.3043 (3)1.1702 (3)0.78962 (17)0.0549 (7)
H2A0.27251.07670.76550.066*
C170.9543 (4)0.2104 (3)0.01281 (18)0.0578 (7)
H17A0.84900.23770.01080.069*
C150.2278 (3)1.1556 (3)0.45106 (17)0.0511 (7)
H15A0.29071.11440.49480.061*
C50.3974 (3)1.4436 (3)0.86282 (19)0.0605 (8)
H5A0.42821.53650.88760.073*
C40.4337 (4)1.3225 (4)0.89823 (19)0.0631 (8)
H4A0.48871.33270.94680.076*
C211.1894 (3)0.2188 (3)0.0417 (2)0.0629 (8)
H21A1.24410.25160.08020.075*
C130.0260 (3)1.2647 (3)0.38006 (17)0.0550 (7)
H13A0.07371.31230.36500.066*
C30.3876 (4)1.1852 (3)0.86102 (19)0.0648 (8)
H3A0.41271.10250.88420.078*
C191.1853 (5)0.0807 (4)0.0781 (2)0.0785 (11)
H19A1.23690.02030.11970.094*
C181.0313 (5)0.1212 (4)0.07452 (19)0.0727 (10)
H18A0.97800.08870.11380.087*
C201.2645 (4)0.1285 (4)0.0208 (2)0.0775 (11)
H20A1.36970.10020.02370.093*
Cl20.62413 (8)1.20582 (8)0.41117 (4)0.05347 (18)
Cl10.49053 (9)1.16111 (8)0.20162 (4)0.05715 (19)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.04203 (18)0.03878 (17)0.04857 (19)0.01084 (13)0.00502 (13)0.00512 (13)
N30.0478 (13)0.0386 (11)0.0492 (13)0.0136 (10)0.0045 (10)0.0034 (10)
N10.0405 (12)0.0491 (13)0.0514 (14)0.0122 (10)0.0002 (10)0.0024 (10)
N20.0361 (12)0.0470 (12)0.0510 (13)0.0098 (10)0.0007 (10)0.0006 (10)
N40.0441 (12)0.0333 (11)0.0476 (12)0.0112 (9)0.0013 (10)0.0004 (9)
C280.0508 (16)0.0366 (13)0.0524 (16)0.0137 (12)0.0069 (13)0.0018 (12)
C250.0402 (14)0.0333 (13)0.0488 (15)0.0083 (11)0.0012 (11)0.0006 (11)
C100.0345 (14)0.0473 (15)0.0549 (16)0.0118 (12)0.0042 (12)0.0041 (12)
C70.0384 (14)0.0457 (15)0.0540 (16)0.0163 (12)0.0006 (12)0.0039 (12)
C220.0388 (14)0.0367 (13)0.0499 (15)0.0105 (11)0.0033 (12)0.0017 (11)
C300.0550 (16)0.0392 (14)0.0508 (16)0.0186 (13)0.0026 (13)0.0049 (12)
C260.0426 (15)0.0400 (14)0.0636 (18)0.0178 (12)0.0088 (13)0.0035 (12)
C120.0483 (16)0.0429 (15)0.0568 (17)0.0083 (13)0.0007 (13)0.0026 (12)
C270.0476 (16)0.0387 (14)0.0646 (18)0.0195 (12)0.0011 (13)0.0077 (12)
C160.0488 (16)0.0374 (13)0.0482 (15)0.0112 (12)0.0033 (12)0.0020 (11)
C240.0478 (16)0.0431 (14)0.0598 (17)0.0223 (13)0.0003 (13)0.0035 (13)
C230.0400 (14)0.0460 (15)0.0603 (17)0.0182 (12)0.0048 (13)0.0004 (13)
C60.0478 (16)0.0455 (15)0.0633 (18)0.0151 (13)0.0034 (14)0.0039 (13)
C290.0498 (16)0.0513 (16)0.0484 (16)0.0184 (13)0.0058 (12)0.0016 (12)
C110.0436 (16)0.0441 (15)0.0628 (18)0.0031 (13)0.0034 (13)0.0052 (13)
C10.0380 (14)0.0466 (15)0.0510 (16)0.0146 (12)0.0003 (12)0.0032 (12)
C140.0519 (17)0.0507 (16)0.0526 (16)0.0129 (14)0.0004 (14)0.0039 (13)
C80.0433 (15)0.0426 (15)0.0662 (18)0.0085 (12)0.0074 (14)0.0018 (13)
C90.0437 (15)0.0459 (15)0.0603 (18)0.0102 (13)0.0029 (13)0.0061 (13)
C20.0579 (18)0.0512 (16)0.0600 (18)0.0225 (14)0.0058 (14)0.0088 (14)
C170.0657 (19)0.0519 (17)0.0575 (18)0.0206 (15)0.0001 (15)0.0018 (14)
C150.0357 (14)0.0621 (17)0.0521 (17)0.0091 (13)0.0019 (12)0.0029 (13)
C50.0566 (18)0.0575 (18)0.067 (2)0.0145 (15)0.0041 (15)0.0157 (15)
C40.065 (2)0.072 (2)0.0553 (18)0.0240 (17)0.0111 (15)0.0064 (16)
C210.0498 (18)0.0642 (19)0.070 (2)0.0103 (15)0.0076 (15)0.0011 (16)
C130.0379 (15)0.0604 (18)0.0594 (18)0.0042 (13)0.0067 (13)0.0069 (14)
C30.072 (2)0.0609 (19)0.066 (2)0.0288 (17)0.0101 (17)0.0021 (15)
C190.116 (3)0.0500 (19)0.064 (2)0.019 (2)0.038 (2)0.0033 (16)
C180.112 (3)0.0595 (19)0.0515 (19)0.033 (2)0.0074 (19)0.0057 (15)
C200.066 (2)0.061 (2)0.092 (3)0.0024 (18)0.033 (2)0.0075 (19)
Cl20.0559 (4)0.0533 (4)0.0553 (4)0.0217 (3)0.0010 (3)0.0073 (3)
Cl10.0716 (5)0.0505 (4)0.0496 (4)0.0188 (4)0.0034 (3)0.0002 (3)
Geometric parameters (Å, º) top
Zn1—N12.021 (2)C16—C171.391 (4)
Zn1—N32.028 (2)C24—C231.368 (3)
Zn1—Cl12.2258 (7)C24—H24A0.9300
Zn1—Cl22.2447 (8)C23—H23A0.9300
N3—C281.314 (3)C6—C51.374 (4)
N3—C291.377 (3)C6—C11.388 (4)
N1—C151.319 (3)C6—H6A0.9300
N1—C141.367 (3)C29—H29A0.9300
N2—C151.339 (3)C11—H11A0.9300
N2—C131.372 (3)C1—C21.381 (4)
N2—C101.441 (3)C14—C131.343 (4)
N4—C281.341 (3)C14—H14A0.9300
N4—C301.371 (3)C8—C91.380 (4)
N4—C251.434 (3)C8—H8A0.9300
C28—H28A0.9300C9—H9A0.9300
C25—C261.373 (3)C2—C31.377 (4)
C25—C241.384 (3)C2—H2A0.9300
C10—C111.370 (4)C17—C181.379 (4)
C10—C91.376 (3)C17—H17A0.9300
C7—C121.389 (3)C15—H15A0.9300
C7—C81.388 (4)C5—C41.367 (4)
C7—C11.486 (3)C5—H5A0.9300
C22—C271.388 (3)C4—C31.379 (4)
C22—C231.388 (3)C4—H4A0.9300
C22—C161.486 (3)C21—C201.388 (4)
C30—C291.353 (4)C21—H21A0.9300
C30—H30A0.9300C13—H13A0.9300
C26—C271.382 (3)C3—H3A0.9300
C26—H26A0.9300C19—C181.361 (5)
C12—C111.382 (4)C19—C201.366 (5)
C12—H12A0.9300C19—H19A0.9300
C27—H27A0.9300C18—H18A0.9300
C16—C211.390 (4)C20—H20A0.9300
N1—Zn1—N3110.09 (9)C5—C6—C1120.7 (3)
N1—Zn1—Cl1108.12 (7)C5—C6—H6A119.7
N3—Zn1—Cl1105.05 (6)C1—C6—H6A119.7
N1—Zn1—Cl2107.94 (7)C30—C29—N3109.4 (2)
N3—Zn1—Cl2111.23 (7)C30—C29—H29A125.3
Cl1—Zn1—Cl2114.33 (3)N3—C29—H29A125.3
C28—N3—C29105.4 (2)C10—C11—C12119.2 (2)
C28—N3—Zn1120.15 (17)C10—C11—H11A120.4
C29—N3—Zn1133.74 (17)C12—C11—H11A120.4
C15—N1—C14105.6 (2)C2—C1—C6118.0 (2)
C15—N1—Zn1127.00 (18)C2—C1—C7120.7 (2)
C14—N1—Zn1127.06 (19)C6—C1—C7121.3 (2)
C15—N2—C13106.9 (2)C13—C14—N1109.8 (2)
C15—N2—C10126.2 (2)C13—C14—H14A125.1
C13—N2—C10126.9 (2)N1—C14—H14A125.1
C28—N4—C30106.8 (2)C9—C8—C7121.5 (2)
C28—N4—C25124.6 (2)C9—C8—H8A119.3
C30—N4—C25128.4 (2)C7—C8—H8A119.3
N3—C28—N4111.9 (2)C10—C9—C8119.3 (3)
N3—C28—H28A124.0C10—C9—H9A120.3
N4—C28—H28A124.0C8—C9—H9A120.3
C26—C25—C24120.8 (2)C3—C2—C1121.1 (3)
C26—C25—N4120.1 (2)C3—C2—H2A119.5
C24—C25—N4119.0 (2)C1—C2—H2A119.5
C11—C10—C9120.8 (2)C18—C17—C16120.7 (3)
C11—C10—N2119.1 (2)C18—C17—H17A119.6
C9—C10—N2120.0 (2)C16—C17—H17A119.6
C12—C7—C8117.5 (2)N1—C15—N2111.3 (2)
C12—C7—C1120.8 (2)N1—C15—H15A124.4
C8—C7—C1121.7 (2)N2—C15—H15A124.4
C27—C22—C23117.6 (2)C4—C5—C6120.8 (3)
C27—C22—C16121.7 (2)C4—C5—H5A119.6
C23—C22—C16120.6 (2)C6—C5—H5A119.6
C29—C30—N4106.4 (2)C5—C4—C3119.2 (3)
C29—C30—H30A126.8C5—C4—H4A120.4
N4—C30—H30A126.8C3—C4—H4A120.4
C25—C26—C27118.8 (2)C16—C21—C20119.7 (3)
C25—C26—H26A120.6C16—C21—H21A120.2
C27—C26—H26A120.6C20—C21—H21A120.2
C11—C12—C7121.6 (3)C14—C13—N2106.4 (2)
C11—C12—H12A119.2C14—C13—H13A126.8
C7—C12—H12A119.2N2—C13—H13A126.8
C26—C27—C22121.7 (2)C2—C3—C4120.2 (3)
C26—C27—H27A119.1C2—C3—H3A119.9
C22—C27—H27A119.1C4—C3—H3A119.9
C21—C16—C17118.5 (3)C18—C19—C20120.3 (3)
C21—C16—C22120.6 (3)C18—C19—H19A119.9
C17—C16—C22120.8 (2)C20—C19—H19A119.9
C23—C24—C25119.4 (2)C19—C18—C17120.1 (3)
C23—C24—H24A120.3C19—C18—H18A119.9
C25—C24—H24A120.3C17—C18—H18A119.9
C24—C23—C22121.5 (2)C19—C20—C21120.7 (3)
C24—C23—H23A119.2C19—C20—H20A119.7
C22—C23—H23A119.2C21—C20—H20A119.7
Selected bond lengths (Å) top
Zn1—N12.021 (2)Zn1—Cl12.2258 (7)
Zn1—N32.028 (2)Zn1—Cl22.2447 (8)

Experimental details

Crystal data
Chemical formula[ZnCl2(C15H12N2)2]
Mr576.80
Crystal system, space groupTriclinic, P1
Temperature (K)296
a, b, c (Å)9.2410 (6), 9.2595 (5), 16.4106 (10)
α, β, γ (°)87.770 (1), 88.819 (1), 72.823 (1)
V3)1340.50 (14)
Z2
Radiation typeMo Kα
µ (mm1)1.14
Crystal size (mm)0.40 × 0.30 × 0.30
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2008)
Tmin, Tmax0.658, 0.726
No. of measured, independent and
observed [I > 2σ(I)] reflections
8564, 5308, 4067
Rint0.025
(sin θ/λ)max1)0.619
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.091, 1.00
No. of reflections5308
No. of parameters334
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.31, 0.35

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

 

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ISSN: 2056-9890
Volume 71| Part 3| March 2015| Pages 272-274
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