Di­chlorido­(2,2′-methyl­enedipyridine)­zinc(II)

Siegfried, A.; McAbee, B.; Zotov, V.; McMillen, C.; Hanks, T.

doi:10.1107/S2414314619001317

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 1| January 2019| x190131

https://doi.org/10.1107/S2414314619001317

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Dichlorido(2,2′-methylenedipyridine)zinc(II)

Adam Siegfried,^a ^* Brett McAbee,^b Vladimir Zotov,^b Colin McMillen ^c and Timothy Hanks ^b

^aDivision of Science, Math, Health, and Computer Science, Spartanburg Methodist College, 1000 Powell Mill Rd., Spartanburg, SC 29301, 864-587-4214, USA, ^bDepartment of Chemistry, Furman University, 3300 Poinsett Highway, Greenville, SC 29613, USA, and ^cDepartment of Chemistry, Hunter Laboratories, Clemson University, Clemson, SC 29634, USA
^*Correspondence e-mail: siegfrieda@smcsc.edu

Edited by J. Simpson, University of Otago, New Zealand (Received 26 December 2018; accepted 24 January 2019; online 29 January 2019)

The title complex, [ZnCl₂(C₁₁H₁₀N₂)], crystallizes in the P2₁/c space group with di-2-pyridylmethane acting as a bidentate ligand coordinating the zinc atom in a distorted tetrahedral geometry. The asymmetric unit consists of a single molecule of the title complex. The title complex folds with an angle of 53.82 (5)° between the planes of the two pyridine rings. The crystal packing is stabilized by hydrogen bonds and π–π interactions involving both pyridine rings.

Keywords: crystal structure; zinc coordination compound.

CCDC reference: 1893123

Structure description

Polynuclear d¹⁰ metal complexes are known to possess luminescence properties and have been studied extensively (Yam & Lo, 1999 ). Mononuclear d¹⁰ metal complexes such as the title compound were first synthesized by Friedrich et al. (1962 ) in a search for new methods of producing known dyes. A few years later, Black et al. (1967 ) produced a series of bidentate chelate complexes including the title complex. Di-2-pyridylmethane can be coupled to form tetra-2-pyridylethane, which in turn can be oxidized further to form tetra-2-pyridylethylene. Both tetra-2-pyridylethane and the ethylene derivative have been used as a ligands in metal coordination chemistry (D'Alessandro et al., 2003 ). Herein we report the crystal structure of the title compound, Fig. 1, which we produced serendipitously in an attempt to prepare a tetra-2-pyridyl derivative, Fig. 2.

Figure 1
The structure of the title complex with displacement ellipsoids drawn at the 50% probability level.

Figure 2
Expected and actual reaction schemes leading to the synthesis of the title complex.

The asymmetric unit of the title compound consists of one molecule on a general position. The two pyridine rings are planar to within 0.0076 (13)Å and 0.0071 (11) Å and are inclined to one another at a dihedral angle of 53.82 (5)°, Fig. 3. The Zn^II atom coordinates in a distorted tetrahedral geometry with the 2,2′-methylenedipyridine unit acting as a bidentate chelating ligand through the N atoms of the two pyridine rings.

Figure 3
A plot showing the dihedral angle between the two pyridine rings in the title complex.

C—H⋯π and π–π interactions are observed between molecules of the title compound. Two π–π interactions involve both pyridine rings, Fig. 4, with distances of 3.8843 (5) and 3.5828 (11) Å, respectively, between the centroids of the N2/C7–C11 pyridine rings running along the b-axis direction and between the centroids of the N1/C1–C5 pyridine rings running along the [ $[\overline{13}]$ _′7_′0] direction. The H10⋯π (N1/C1–C5) interaction distance is 2.99 Å, which is just outside the H⋯Cp distance of 2.9 Å suggested for such contacts (Takahashi et al., 2001 ). C—H⋯Cl interactions are also observed (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N1/C1–C5 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯Cl1ⁱ	0.95	2.89	3.7719 (19)	154
C11—H11⋯Cl2ⁱⁱ	0.95	2.86	3.591 (2)	134
C10—H10⋯Cg1ⁱⁱⁱ	0.95	2.99	3.718 (2)	135
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+2; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 4
π–π interactions between adjacent molecules of the title complex.

A search of the CSD (Groom et al., 2016 ) found five complexes that utilize bis(2-pyridyl)methane as a ligand and nine complexes with related di-2-pyridylketone ligands. Metals reported in these structures are Zn^II, Pt^II, and Pt^IV for the di-2-pyridylketone structures [refcodes ERAPUI (Crowder et al., 2004 ), LUCBOA (Katsoulakou et al., 2002 ), SIQZEX (Lo et al., 2015 ), XARDOK, XARDUQ, XARFAY, XARFAC, XARFIG, XAVRIW (Zhang et al., 2005 )] with the majority being Pt complexes. Bis(2-pyridyl)methane complexes are found for Pt^II, Cu^I, Re^I, Hg^I, and Li cations. [refcodes CASXUQ (Elie et al., 2017 ), HEWPIL (Gornitzka & Stalke, 1994 ), MPYHGA (Marti et al., 2005 ), SAXVOD (Zhang et al., 2005), YIFJEC (Canty et al., 1980 )]. Of the previously mentioned organometallic complexes, only the Zn^II chloride complexed with di-2-pyridylketone structure (LUCBOA; Katsoulakou et al., 2002) has a tetrahedral coordination about the metal. The tetrahedron has close to ideal bond angles due to the conformation of the di-2-pyridylketone ligand.

Synthesis and crystallization

The synthesis of the title compound was performed using previously reported methods for McMurry coupling (McMurry et al., 1974 ; McMurry, 1989 ) but the reaction resulted in the formation of the title compound rather than a coupled product similar to that previously published·(Qi et al., 2016 ), Fig. 2. The synthesis of the title complex was carried out under a nitrogen atmosphere with a 250 mL three-necked round-bottomed flask charged with Zn metal (0.17g, 1.74mmol) and cooled to −78°C. Then TiCl₄ (0.11mL, 1.74mmol) and pyridine (0.14mL, 1.7mmol) were added slowly, resulting in a green solution. The catalyst mixture was allowed to warm to room temperature then refluxed for an hour then cooled to −78°C, at which point di-2-pyridylketone (0.32g, 1.74mmol) in 50mL of THF was added, producing a dark-blue solution. The reaction mixture was allowed to return to room temperature then refluxed for four h. The reaction mixture was then allowed to return to room temperature and the THF was removed under vacuum. The mixture left in the reaction flask was extracted three times with dichloromethane (DCM). The solvent was removed under vacuum to produce the title compound as an off-white powder. The title compound was recrystallized from DCM.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[ZnCl₂(C₁₁H₁₀N₂)]
M_r	306.48
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	12.1865 (8), 7.6666 (5), 14.1087 (9)
β (°)	111.467 (2)
V (Å³)	1226.72 (14)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.41
Crystal size (mm)	0.30 × 0.28 × 0.18

Data collection
Diffractometer	Bruker D8 Venture Photon 100
Absorption correction	Multi-scan (SADABS; Bruker et al., 2015 )
T_min, T_max	0.935, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	36532, 2535, 2403
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.058, 1.06
No. of reflections	2535
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.39
Computer programs: APEX3 and SAINT (Bruker, 2015), SHELXT (Sheldrick 2015a ), SHELXL2016/6 (Sheldrick 2015b ), Mercury (Macrae et al., 2006 ) and SHELXTL (Sheldrick 2008 ).

Structural data

CCDC reference: 1893123

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314619001317/sj4199sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619001317/sj4199Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick 2015a); program(s) used to refine structure: SHELXL2016/6 (Sheldrick 2015b); molecular graphics: SHELXL2016/6 (Sheldrick 2015b), Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick 2008).

Dichlorido(2,2'-methylenedipyridine)zinc(II) top

Crystal data top

[ZnCl₂(C₁₁H₁₀N₂)]	F(000) = 616
M_r = 306.48	D_x = 1.659 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.1865 (8) Å	Cell parameters from 9749 reflections
b = 7.6666 (5) Å	θ = 3.1–30.5°
c = 14.1087 (9) Å	µ = 2.41 mm⁻¹
β = 111.467 (2)°	T = 100 K
V = 1226.72 (14) Å³	Block, colourless
Z = 4	0.30 × 0.28 × 0.18 mm

Data collection top

Bruker D8 Venture Photon 100 diffractometer	2403 reflections with I > 2σ(I)
Radiation source: Incoatec IµS	R_int = 0.037
φ and ω scans	θ_max = 26.5°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker et al., 2015)	h = −15→15
T_min = 0.935, T_max = 1.000	k = −9→9
36532 measured reflections	l = −17→17
2535 independent reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.058	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.033P)² + 0.6222P] where P = (F_o² + 2F_c²)/3
2535 reflections	(Δ/σ)_max = 0.002
145 parameters	Δρ_max = 0.61 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.25054 (2)	0.61335 (2)	0.78613 (2)	0.02155 (8)
Cl1	0.15845 (4)	0.86959 (5)	0.76835 (3)	0.02930 (11)
Cl2	0.28554 (4)	0.47187 (6)	0.93074 (3)	0.03149 (11)
N1	0.16497 (11)	0.45954 (17)	0.66353 (10)	0.0204 (3)
N2	0.39694 (12)	0.62986 (17)	0.74807 (11)	0.0232 (3)
C1	0.09591 (14)	0.3254 (2)	0.66831 (13)	0.0244 (3)
H1	0.085816	0.302370	0.730777	0.029*
C2	0.03931 (15)	0.2204 (2)	0.58533 (14)	0.0296 (4)
H2	−0.010838	0.128510	0.589795	0.036*
C3	0.05713 (16)	0.2519 (2)	0.49547 (14)	0.0315 (4)
H3	0.019904	0.180510	0.437488	0.038*
C4	0.12949 (16)	0.3878 (2)	0.49059 (13)	0.0274 (4)
H4	0.143354	0.409786	0.429657	0.033*
C5	0.18135 (14)	0.4911 (2)	0.57555 (12)	0.0221 (3)
C6	0.25566 (16)	0.6490 (2)	0.57328 (13)	0.0274 (4)
H6A	0.256931	0.661095	0.503825	0.033*
H6B	0.217720	0.754678	0.587617	0.033*
C7	0.38120 (15)	0.6402 (2)	0.64853 (14)	0.0254 (4)
C8	0.47631 (18)	0.6456 (3)	0.61739 (16)	0.0339 (4)
H8	0.464084	0.654296	0.547079	0.041*
C9	0.58986 (18)	0.6380 (3)	0.68982 (18)	0.0390 (5)
H9	0.656123	0.643384	0.669675	0.047*
C10	0.60542 (17)	0.6227 (2)	0.79139 (17)	0.0359 (4)
H10	0.682304	0.614734	0.842075	0.043*
C11	0.50713 (16)	0.6192 (2)	0.81785 (15)	0.0295 (4)
H11	0.517557	0.609015	0.887723	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02095 (11)	0.02503 (12)	0.02011 (11)	−0.00055 (7)	0.00920 (8)	−0.00067 (7)
Cl1	0.0301 (2)	0.0269 (2)	0.0332 (2)	0.00416 (16)	0.01431 (18)	0.00072 (16)
Cl2	0.0407 (2)	0.0332 (2)	0.0219 (2)	0.00119 (18)	0.01292 (18)	0.00326 (16)
N1	0.0189 (6)	0.0213 (7)	0.0206 (6)	0.0017 (5)	0.0068 (5)	0.0028 (5)
N2	0.0215 (7)	0.0233 (7)	0.0261 (7)	−0.0007 (5)	0.0101 (6)	0.0005 (5)
C1	0.0201 (8)	0.0236 (8)	0.0283 (9)	0.0024 (6)	0.0076 (6)	0.0067 (7)
C2	0.0250 (8)	0.0191 (8)	0.0387 (10)	−0.0006 (6)	0.0046 (7)	0.0028 (7)
C3	0.0309 (9)	0.0245 (9)	0.0313 (9)	0.0050 (7)	0.0021 (7)	−0.0064 (7)
C4	0.0305 (9)	0.0299 (9)	0.0209 (8)	0.0076 (7)	0.0083 (7)	0.0008 (7)
C5	0.0214 (7)	0.0238 (8)	0.0207 (8)	0.0037 (6)	0.0072 (6)	0.0037 (6)
C6	0.0299 (9)	0.0299 (9)	0.0231 (8)	−0.0026 (7)	0.0106 (7)	0.0061 (7)
C7	0.0280 (9)	0.0216 (8)	0.0299 (9)	−0.0013 (6)	0.0143 (7)	0.0029 (7)
C8	0.0369 (10)	0.0336 (10)	0.0402 (11)	−0.0010 (8)	0.0249 (9)	0.0048 (8)
C9	0.0311 (10)	0.0353 (10)	0.0608 (14)	0.0021 (8)	0.0287 (10)	0.0098 (9)
C10	0.0211 (9)	0.0334 (10)	0.0509 (12)	−0.0002 (7)	0.0105 (8)	0.0069 (8)
C11	0.0238 (9)	0.0300 (9)	0.0324 (9)	−0.0018 (7)	0.0075 (7)	0.0012 (7)

Geometric parameters (Å, º) top

Zn1—N1	2.0372 (14)	C4—C5	1.382 (2)
Zn1—N2	2.0466 (14)	C4—H4	0.9500
Zn1—Cl2	2.2101 (5)	C5—C6	1.519 (2)
Zn1—Cl1	2.2306 (5)	C6—C7	1.511 (2)
N1—C1	1.346 (2)	C6—H6A	0.9900
N1—C5	1.349 (2)	C6—H6B	0.9900
N2—C11	1.346 (2)	C7—C8	1.382 (2)
N2—C7	1.348 (2)	C8—C9	1.388 (3)
C1—C2	1.380 (3)	C8—H8	0.9500
C1—H1	0.9500	C9—C10	1.380 (3)
C2—C3	1.383 (3)	C9—H9	0.9500
C2—H2	0.9500	C10—C11	1.379 (3)
C3—C4	1.383 (3)	C10—H10	0.9500
C3—H3	0.9500	C11—H11	0.9500

N1—Zn1—N2	92.15 (6)	N1—C5—C4	121.35 (16)
N1—Zn1—Cl2	111.45 (4)	N1—C5—C6	116.91 (14)
N2—Zn1—Cl2	112.35 (4)	C4—C5—C6	121.70 (15)
N1—Zn1—Cl1	109.52 (4)	C7—C6—C5	114.08 (14)
N2—Zn1—Cl1	111.53 (4)	C7—C6—H6A	108.7
Cl2—Zn1—Cl1	117.084 (18)	C5—C6—H6A	108.7
C1—N1—C5	119.28 (14)	C7—C6—H6B	108.7
C1—N1—Zn1	122.33 (11)	C5—C6—H6B	108.7
C5—N1—Zn1	118.37 (11)	H6A—C6—H6B	107.6
C11—N2—C7	119.28 (15)	N2—C7—C8	121.10 (17)
C11—N2—Zn1	122.44 (12)	N2—C7—C6	117.13 (15)
C7—N2—Zn1	118.13 (11)	C8—C7—C6	121.76 (17)
N1—C1—C2	122.05 (16)	C7—C8—C9	119.38 (19)
N1—C1—H1	119.0	C7—C8—H8	120.3
C2—C1—H1	119.0	C9—C8—H8	120.3
C1—C2—C3	118.60 (16)	C10—C9—C8	119.28 (18)
C1—C2—H2	120.7	C10—C9—H9	120.4
C3—C2—H2	120.7	C8—C9—H9	120.4
C4—C3—C2	119.57 (16)	C11—C10—C9	118.67 (18)
C4—C3—H3	120.2	C11—C10—H10	120.7
C2—C3—H3	120.2	C9—C10—H10	120.7
C5—C4—C3	119.11 (17)	N2—C11—C10	122.26 (19)
C5—C4—H4	120.4	N2—C11—H11	118.9
C3—C4—H4	120.4	C10—C11—H11	118.9

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N1/C1–C5 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Cl1ⁱ	0.95	2.89	3.7719 (19)	154
C11—H11···Cl2ⁱⁱ	0.95	2.86	3.591 (2)	134
C10—H10···Cg1ⁱⁱⁱ	0.95	2.99	3.718 (2)	135

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, −y+1, −z+2; (iii) −x+1, y+1/2, −z+3/2.

Acknowledgements

We would like to thank Furman University for hosting the NSF–REU program which allowed us to perform this work.

Funding information

Funding for this research was provided by: National Science Foundation, Division of Chemistry (grant No. CHE-1460806 to Department of Chemistry at Furman University).

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