Di­chlorido­(4,4′-dimethyl-2,2′-bi­pyridine-κ2N,N′)zinc(II) aceto­nitrile monosolvate

Adrian, R.A.; Rios, J.J.; Arman, H.D.

doi:10.1107/S241431462201149X

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 7| Part 12| December 2022| x221149

https://doi.org/10.1107/S241431462201149X

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Dichlorido(4,4′-dimethyl-2,2′-bipyridine-κ²N,N′)zinc(II) acetonitrile monosolvate

Rafael A. Adrian,^a ^* Jadan J. Rios ^a and Hadi D. Arman ^b

^aDepartment of Chemistry and Biochemistry, University of the Incarnate Word, San Antonio, Texas 78209, USA, and ^bDepartment of Chemistry, The University of Texas at San Antonio, San Antonio, Texas 78249, USA
^*Correspondence e-mail: adrian@uiwtx.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 17 November 2022; accepted 30 November 2022; online 6 December 2022)

In the title complex, [ZnCl₂(C₁₂H₁₂N₂)]·CH₃CN, the zinc(II) atom is fourfold coordinated by two chloride ligands and a bidentate 4,4′-dimethyl-2,2′-bipyridine ligand in a distorted tetrahedral shape with a molecule of acetonitrile sitting in the outer coordination sphere of the complex. π–π stacking interactions between the pyridyl rings in adjacent molecules contribute to the alignment of the complexes in columns parallel to the a axis.

Keywords: zinc; crystal structure; 4,4′-dimethyl-2,2′-bipyridine; 2,2′-bi-4-picoline; dmb; coordinating chloride; tetrahedral coordination sphere.

CCDC reference: 2223395

Structure description

Over the last decade, metal complexes of 4,4′-dimethyl-2,2′-bipyridine have garnered significant attention due to their photophysical properties (Tamer et al., 2020 ; Queiroz et al., 2022 ), electrocatalytic activity (Ogihara et al., 2018 ; Taylor et al., 2018 ), and potential as antitumor agents (Amani et al., 2014 ). Recently, platinum complexes incorporating 4,4′-dimethyl-2,2′-bipyridine were found to be effective against several cancer cell lines, including L1210 murine leukemia, HT29 human colon carcinoma, and U87 human glioblastoma (Pages et al., 2015 ). Our research group interest currently lies in synthesizing metal complexes with applications in biological systems; as part of our research in this area, herein, we describe the synthesis and structure of the title complex, which promises to be a useful starting material in the synthesis of novel zinc(II) complexes.

The asymmetric unit contains one molecule of the title compound and one solvent molecule of acetonitrile. The zinc(II) atom exhibits a distorted tetrahedral cooordination environment defined by two pyridine nitrogen atoms from the 4,4′-dimethyl-2,2′-bipyridine ligand and two chlorido ligands (Fig. 1). The Zn—N bond lengths are in good agreement with the comparable bromide analog complex currently available in the CSD (version 5.43 with update June 2022; Alizadeh et al., 2010 , refcode DURYAR) and with other 2,2′-bipyridine-based zinc(II) complexes (Khan & Tuck, 1984 , refcode CEFFOI; Hossienifard et al., 2011 , refcode DAKMUZ; Nauha et al., 2016 , refcode EMERAR; Khalighi et al., 2008 , refcode POFKOL). Similar behavior is observed for the Zn—Cl bond lengths. The small bite angle N2—Zn1—N1 of 80.19 (7)° reflects the distortion from the ideal tetrahedral coordination. Numerical data of relevant bonds and angles are presented in Table 1.

Table 1
Selected geometric parameters (Å, °)

Zn1—Cl1	2.2065 (6)	Zn1—N1	2.0570 (17)
Zn1—Cl2	2.2005 (6)	Zn1—N2	2.0562 (17)

Cl2—Zn1—Cl1	116.82 (2)	N2—Zn1—Cl1	110.49 (5)
N1—Zn1—Cl1	117.12 (5)	N2—Zn1—Cl2	117.59 (5)
N1—Zn1—Cl2	109.48 (5)	N2—Zn1—N1	80.19 (7)

Figure 1
The structures of the molecular entities of the title compound with displacement ellipsoids drawn at the 50% probability level; H atoms are omitted for clarity.

The title complex packs into layers extending parallel to the bc plane that are packed along the a-axis direction (Fig. 2). Contiguous pyridine rings show π–π stacking interactions, with centroid-to-centroid distances (Cg⋯Cg) alternating between 3.718 (1) Å and 3.725 (1) Å, and offset distances of 1.166 and 1.191 Å, respectively (Fig. 3). No other significant supramolecular interaction is present in the crystal packing of the title compound.

Figure 2
Perspective view of the crystal packing of the title complex approximately along the b axis; H atoms are omitted for clarity.

Figure 3
Capped sticks representation of the title molecule showing π–π stacking interactions (red). H atoms and acetonitrile molecule are omitted for clarity.

Synthesis and crystallization

Zinc(II) chloride (0.370 g, 2.71 mmol) was added to a methanol solution (40 ml) of 4,4′-dimethyl-2,2′-bipyridine (0.500 g, 2.71 mmol). After stirring for 30 min, the resulting suspension was filtrated to obtain a white precipitate of the title compound (0.470 g, 54%). Crystals suitable for X-ray diffraction were obtained by vapor diffusion of diethyl ether over a saturated acetonitrile solution of the title compound at 277 K.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	[ZnCl₂(C₁₂H₁₂N₂)]·C₂H₃N
M_r	361.56
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.2893 (1), 13.3443 (2), 16.1667 (3)
β (°)	92.486 (2)
V (Å³)	1571.06 (4)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	5.23
Crystal size (mm)	0.26 × 0.10 × 0.05

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.467, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15078, 3137, 2851
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.630

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.089, 1.07
No. of reflections	3137
No. of parameters	184
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.75
Computer programs: CrysAlis PRO (Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2223395

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S241431462201149X/wm4177sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431462201149X/wm4177Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431462201149X/wm4177Isup3.mol

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2020); cell refinement: CrysAlis PRO (Rigaku OD, 2020); data reduction: CrysAlis PRO (Rigaku OD, 2020); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

Dichlorido(4,4'-dimethyl-2,2'-bipyridine-κ²N,N')zinc(II) acetonitrile monosolvate top

Crystal data top

[ZnCl₂(C₁₂H₁₂N₂)]·C₂H₃N	F(000) = 736
M_r = 361.56	D_x = 1.529 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 7.2893 (1) Å	Cell parameters from 7600 reflections
b = 13.3443 (2) Å	θ = 4.3–75.6°
c = 16.1667 (3) Å	µ = 5.23 mm⁻¹
β = 92.486 (2)°	T = 100 K
V = 1571.06 (4) Å³	Plank, clear colourless
Z = 4	0.26 × 0.10 × 0.05 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	3137 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2851 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.040
Detector resolution: 10.0000 pixels mm^-1	θ_max = 76.3°, θ_min = 4.3°
ω scans	h = −9→8
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2020)	k = −16→11
T_min = 0.467, T_max = 1.000	l = −20→18
15078 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.0506P)² + 0.740P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.002
3137 reflections	Δρ_max = 0.47 e Å⁻³
184 parameters	Δρ_min = −0.75 e Å⁻³
0 restraints

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	0.26341 (4)	0.28826 (2)	0.57710 (2)	0.02312 (11)
Cl1	0.52433 (7)	0.21775 (4)	0.61998 (3)	0.03091 (14)
Cl2	0.01137 (8)	0.20050 (4)	0.59191 (4)	0.03469 (15)
N1	0.2201 (2)	0.43399 (12)	0.61281 (10)	0.0234 (3)
N2	0.2934 (2)	0.35984 (12)	0.46587 (10)	0.0238 (3)
C6	0.2711 (3)	0.46056 (15)	0.46862 (12)	0.0229 (4)
C5	0.2270 (3)	0.50205 (15)	0.55085 (12)	0.0224 (4)
N3	0.2294 (3)	0.42938 (15)	0.88678 (12)	0.0386 (5)
C4	0.1954 (3)	0.60303 (15)	0.56446 (13)	0.0257 (4)
H4	0.199479	0.649436	0.520011	0.031*
C7	0.2912 (3)	0.51951 (15)	0.39878 (13)	0.0258 (4)
H7	0.275570	0.590064	0.401893	0.031*
C1	0.1812 (3)	0.46558 (16)	0.68887 (13)	0.0271 (4)
H1	0.174326	0.417554	0.731999	0.032*
C8	0.3344 (3)	0.47496 (16)	0.32421 (13)	0.0271 (4)
C2	0.1508 (3)	0.56532 (16)	0.70690 (13)	0.0287 (4)
H2	0.125591	0.585262	0.761657	0.034*
C10	0.3363 (3)	0.31691 (16)	0.39416 (13)	0.0277 (4)
H10	0.352298	0.246295	0.392476	0.033*
C3	0.1576 (3)	0.63621 (15)	0.64396 (13)	0.0279 (4)
C9	0.3580 (3)	0.37158 (16)	0.32278 (13)	0.0287 (4)
H9	0.388748	0.338853	0.273078	0.034*
C13	0.2438 (3)	0.47359 (16)	0.94688 (14)	0.0296 (4)
C12	0.3516 (3)	0.53683 (18)	0.24735 (14)	0.0350 (5)
H12A	0.232760	0.539310	0.216670	0.053*
H12B	0.443377	0.506603	0.212485	0.053*
H12C	0.389982	0.604955	0.262723	0.053*
C14	0.2648 (3)	0.52852 (18)	1.02426 (14)	0.0334 (5)
H14A	0.321179	0.593786	1.014092	0.050*
H14B	0.343360	0.490338	1.063596	0.050*
H14C	0.143993	0.538499	1.047313	0.050*
C11	0.1310 (3)	0.74589 (17)	0.66062 (16)	0.0360 (5)
H11A	0.248128	0.781058	0.656074	0.054*
H11B	0.086842	0.754766	0.716555	0.054*
H11C	0.040579	0.773390	0.620108	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02849 (17)	0.01792 (16)	0.02321 (17)	0.00069 (9)	0.00410 (11)	0.00276 (9)
Cl1	0.0305 (3)	0.0271 (3)	0.0353 (3)	0.00510 (18)	0.0030 (2)	0.00574 (19)
Cl2	0.0334 (3)	0.0319 (3)	0.0392 (3)	−0.0078 (2)	0.0068 (2)	0.0031 (2)
N1	0.0274 (8)	0.0205 (8)	0.0223 (8)	0.0008 (6)	0.0021 (6)	0.0005 (6)
N2	0.0300 (8)	0.0187 (8)	0.0227 (8)	0.0000 (6)	0.0028 (6)	0.0006 (6)
C6	0.0253 (9)	0.0213 (9)	0.0221 (9)	−0.0014 (7)	0.0002 (7)	0.0011 (7)
C5	0.0235 (9)	0.0209 (9)	0.0225 (9)	0.0001 (7)	−0.0017 (7)	0.0013 (8)
N3	0.0588 (13)	0.0285 (10)	0.0286 (10)	−0.0025 (9)	0.0040 (9)	−0.0004 (8)
C4	0.0292 (10)	0.0215 (10)	0.0260 (10)	0.0001 (8)	−0.0014 (8)	0.0013 (8)
C7	0.0300 (10)	0.0226 (9)	0.0245 (10)	−0.0007 (8)	−0.0015 (8)	0.0028 (8)
C1	0.0322 (10)	0.0261 (10)	0.0229 (10)	0.0009 (8)	0.0013 (8)	0.0023 (8)
C8	0.0286 (10)	0.0297 (10)	0.0229 (10)	−0.0003 (8)	−0.0004 (8)	0.0038 (8)
C2	0.0318 (10)	0.0292 (11)	0.0253 (10)	0.0011 (8)	0.0021 (8)	−0.0046 (8)
C10	0.0336 (10)	0.0235 (10)	0.0262 (10)	−0.0001 (8)	0.0027 (8)	−0.0028 (8)
C3	0.0285 (10)	0.0233 (10)	0.0317 (11)	0.0003 (8)	−0.0012 (8)	−0.0033 (8)
C9	0.0329 (10)	0.0309 (11)	0.0224 (9)	−0.0009 (8)	0.0018 (8)	−0.0025 (8)
C13	0.0344 (11)	0.0267 (10)	0.0280 (11)	0.0008 (8)	0.0023 (8)	0.0025 (9)
C12	0.0434 (13)	0.0386 (12)	0.0229 (10)	0.0005 (10)	0.0010 (9)	0.0083 (9)
C14	0.0374 (12)	0.0341 (12)	0.0288 (11)	0.0012 (9)	0.0009 (9)	−0.0042 (9)
C11	0.0435 (13)	0.0233 (11)	0.0414 (13)	−0.0009 (9)	0.0024 (10)	−0.0075 (9)

Geometric parameters (Å, º) top

Zn1—Cl1	2.2065 (6)	C8—C9	1.390 (3)
Zn1—Cl2	2.2005 (6)	C8—C12	1.502 (3)
Zn1—N1	2.0570 (17)	C2—H2	0.9500
Zn1—N2	2.0562 (17)	C2—C3	1.392 (3)
N1—C5	1.355 (3)	C10—H10	0.9500
N1—C1	1.342 (3)	C10—C9	1.380 (3)
N2—C6	1.355 (3)	C3—C11	1.502 (3)
N2—C10	1.342 (3)	C9—H9	0.9500
C6—C5	1.488 (3)	C13—C14	1.452 (3)
C6—C7	1.389 (3)	C12—H12A	0.9800
C5—C4	1.386 (3)	C12—H12B	0.9800
N3—C13	1.138 (3)	C12—H12C	0.9800
C4—H4	0.9500	C14—H14A	0.9800
C4—C3	1.398 (3)	C14—H14B	0.9800
C7—H7	0.9500	C14—H14C	0.9800
C7—C8	1.392 (3)	C11—H11A	0.9800
C1—H1	0.9500	C11—H11B	0.9800
C1—C2	1.382 (3)	C11—H11C	0.9800

Cl2—Zn1—Cl1	116.82 (2)	C1—C2—C3	119.29 (19)
N1—Zn1—Cl1	117.12 (5)	C3—C2—H2	120.4
N1—Zn1—Cl2	109.48 (5)	N2—C10—H10	118.8
N2—Zn1—Cl1	110.49 (5)	N2—C10—C9	122.41 (19)
N2—Zn1—Cl2	117.59 (5)	C9—C10—H10	118.8
N2—Zn1—N1	80.19 (7)	C4—C3—C11	120.37 (19)
C5—N1—Zn1	114.53 (13)	C2—C3—C4	118.13 (19)
C1—N1—Zn1	126.54 (14)	C2—C3—C11	121.5 (2)
C1—N1—C5	118.89 (17)	C8—C9—H9	120.3
C6—N2—Zn1	114.51 (13)	C10—C9—C8	119.47 (19)
C10—N2—Zn1	126.48 (14)	C10—C9—H9	120.3
C10—N2—C6	118.99 (17)	N3—C13—C14	178.8 (3)
N2—C6—C5	115.42 (17)	C8—C12—H12A	109.5
N2—C6—C7	121.21 (18)	C8—C12—H12B	109.5
C7—C6—C5	123.36 (18)	C8—C12—H12C	109.5
N1—C5—C6	115.31 (17)	H12A—C12—H12B	109.5
N1—C5—C4	121.51 (18)	H12A—C12—H12C	109.5
C4—C5—C6	123.18 (18)	H12B—C12—H12C	109.5
C5—C4—H4	120.2	C13—C14—H14A	109.5
C5—C4—C3	119.63 (19)	C13—C14—H14B	109.5
C3—C4—H4	120.2	C13—C14—H14C	109.5
C6—C7—H7	120.1	H14A—C14—H14B	109.5
C6—C7—C8	119.85 (19)	H14A—C14—H14C	109.5
C8—C7—H7	120.1	H14B—C14—H14C	109.5
N1—C1—H1	118.7	C3—C11—H11A	109.5
N1—C1—C2	122.54 (19)	C3—C11—H11B	109.5
C2—C1—H1	118.7	C3—C11—H11C	109.5
C7—C8—C12	120.8 (2)	H11A—C11—H11B	109.5
C9—C8—C7	118.07 (19)	H11A—C11—H11C	109.5
C9—C8—C12	121.12 (19)	H11B—C11—H11C	109.5
C1—C2—H2	120.4

Zn1—N1—C5—C6	−2.1 (2)	C6—C7—C8—C12	178.3 (2)
Zn1—N1—C5—C4	178.15 (15)	C5—N1—C1—C2	−1.1 (3)
Zn1—N1—C1—C2	−178.79 (15)	C5—C6—C7—C8	179.38 (19)
Zn1—N2—C6—C5	−0.7 (2)	C5—C4—C3—C2	−0.8 (3)
Zn1—N2—C6—C7	178.55 (15)	C5—C4—C3—C11	177.39 (19)
Zn1—N2—C10—C9	−178.35 (16)	C7—C6—C5—N1	−177.36 (19)
N1—C5—C4—C3	0.8 (3)	C7—C6—C5—C4	2.4 (3)
N1—C1—C2—C3	1.0 (3)	C7—C8—C9—C10	0.7 (3)
N2—C6—C5—N1	1.8 (3)	C1—N1—C5—C6	179.95 (18)
N2—C6—C5—C4	−178.40 (18)	C1—N1—C5—C4	0.2 (3)
N2—C6—C7—C8	0.2 (3)	C1—C2—C3—C4	−0.1 (3)
N2—C10—C9—C8	−0.2 (3)	C1—C2—C3—C11	−178.2 (2)
C6—N2—C10—C9	−0.3 (3)	C10—N2—C6—C5	−178.96 (18)
C6—C5—C4—C3	−179.00 (18)	C10—N2—C6—C7	0.2 (3)
C6—C7—C8—C9	−0.7 (3)	C12—C8—C9—C10	−178.3 (2)

Acknowledgements

We are thankful for the support of the Department of Chemistry and Biochemistry at the University of the Incarnate Word and the X-ray Diffraction Laboratory at the University of Texas at San Antonio.

Funding information

Funding for this research was provided by: National Science Foundation (award No. 1920059); Welch Foundation (award No. BN0032).

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