Crystal structure and Hirshfeld surface analysis of bis­(6,7,8,9-tetra­hydro-11H-pyrido[2,1-b]quinazolin-5-ium) tetra­chlorido­zincate

Tojiboev, A.; Okmanov, R.; Englert, U.; Wang, R.; Pan, F.; Turgunov, K.; Tashkhodjaev, B.

doi:10.1107/S2056989021004989

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ISSN: 2056-9890

Volume 77| Part 6| June 2021| Pages 629-633

https://doi.org/10.1107/S2056989021004989

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Crystal structure and Hirshfeld surface analysis of bis(6,7,8,9-tetrahydro-11H-pyrido[2,1-b]quinazolin-5-ium) tetrachloridozincate

Akmaljon Tojiboev,^a ^* Rasul Okmanov,^b Ulli Englert,^c Ruimin Wang,^c Fangfang Pan,^d Kambarali Turgunov ^b,^e and Bakhodir Tashkhodjaev ^b

^aLaboratory of Thermal Physics of Multiphase Systems, Arifov Institute of Ion-Plasma and Laser Technologies, Academy of Sciences of Uzbekistan, Durmon yuli str. 33, Tashkent, 100125, Uzbekistan, ^bS.Yunusov Institute of Chemistry of Plant Substances, Academy of Science of Uzbekistan, Mirzo Ulugbek Str. 77, 100170 Tashkent, Uzbekistan, ^cInstitute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056, Aachen, Germany, ^dCollege of Chemistry, Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, Hubei International Scientific and Technological Cooperation Base of Pesticide and Green Synthesis, Central China Normal University, Luoyu Road 152, Wuhan, Hubei Province 430079, People's Republic of China, and ^eTurin Polytechnic University in Tashkent, Kichik Khalka yuli str., 17, 100095 Tashkent, Uzbekistan
^*Correspondence e-mail: a_tojiboev@yahoo.com

Edited by V. Jancik, Universidad Nacional Autónoma de México, México (Received 24 March 2021; accepted 11 May 2021; online 14 May 2021)

The title compound, (C₁₂H₁₅N₂)₂[ZnCl₄], is a salt with two symmetrically independent, essentially planar heterocyclic cations and a slightly distorted tetrahedral chlorozincate dianion. N—H⋯Cl hydrogen bonds link these ionic constituents into a discrete aggregate, which comprises one formula unit. The effect of hydrogen bonding is reflected in the minor distortions of the [ZnCl₄]²⁻ moiety: distances between the cation and chlorido ligands engaged in classical hydrogen bonds are significantly longer than the others. Secondary interactions comprise C—H⋯π hydrogen bonding and weak π–π stacking. A Hirshfeld surface analysis indicates that the most abundant contacts in packing stem from H⋯H (47.8%) and Cl⋯H/H⋯Cl (29.3%) interactions.

Keywords: tricyclic quinazoline; intermolecular interactions; Hirshfeld surface; crystal structure.

CCDC reference: 2082994

1. Chemical context

Tricyclic quinazolines are counted among the most exciting quinazoline alkaloids. Specifically, the alkaloid mackinazoline was isolated from Mackinlaya sp. (Johns & Lamberton, 1965 ). Tricyclic quinazolines have several different reactive sites and can react with electrophilic and nucleophilic reagents to form various derivatives with potential biological activity (Michael, 2004 ). As quinazoline alkaloids are scarcely available from natural sources, multiple methods for their synthesis have been developed (Shakhidoyatov & Elmuradov, 2014 ). In the context of these synthetic efforts, reaction intermediates similar to the title compound have been studied (Sharma et al., 1993 ; Sargazakov et al., 1991 ; Tozhiboev et al., 2005 ). We investigated the crystal structure of bis(6,7,8,9-tetrahydro-11H-pyrido[2,1-b]quinazolin-5-ium) tetrachloridozincate, an intermediate in the synthesis of mackinazolinone, using high-resolution diffraction data and Hirshfeld surface analysis.

2. Structural commentary

The title compound crystallizes in the P2₁/n space group, with two [C₁₂H₁₅N₂]⁺ cations and a [ZnCl₄]²⁻ counter-anion in the asymmetric unit (Fig. 1). The benzene and pyrimidine rings in either cation and the attached carbon atoms of the aliphatic ring (C9A and C12A for residue A and C9B and C12B for residue B) are essentially coplanar, with r.m.s. deviations of 0.0437 and 0.0168 Å for molecules A and B, respectively. The remaining atoms of the third ring are significantly displaced above the opposite faces of these planes with deviations of 0.3877 (12) Å for C10A and 0.3831 (11) Å for C11A in residue A and 0.4705 (11) Å for C10B and 0.2495 (11) Å for C11B in residue B. Fig. 2 shows that the independent cations are almost superimposable including the conformationally soft aliphatic ring.

Figure 1
Asymmetric unit of the title compound with the atom-numbering scheme (Spek, 2020

). Displacement ellipsoids for non-hydrogen atoms are drawn at the 50% probability level.

Figure 2
Overlay (Spek, 2020

) of the independent cations in the title compound in the least-squares (top) and most-squares plane (bottom); residue A is depicted in black, residue B in red.

The protonation of the ring occurs at the basic heteroatoms of the pyrimidine rings, N1A and N1B, respectively, and the acquired positive charge is delocalized within the –N–C–N– moiety in the ring, where the N1A—C2A and N1B—C2B bonds are only slightly longer than C2A—N3A and C2B—N3B (Table 1). Similar differences were observed in related reported complexes (Sharma et al., 1993; Turgunov et al., 2003 ; Tozhiboev et al., 2005).

Table 1
Selected geometric parameters (Å, °)

Zn1—Cl4	2.2484 (3)	N1A—C2A	1.3373 (11)
Zn1—Cl3	2.2664 (4)	N1B—C2B	1.3317 (10)
Zn1—Cl2	2.2868 (4)	C2A—N3A	1.3102 (10)
Zn1—Cl1	2.3019 (3)	C2B—N3B	1.3114 (9)

Cl4—Zn1—Cl3	111.219 (10)	Cl4—Zn1—Cl1	109.994 (13)
Cl4—Zn1—Cl2	115.057 (11)	Cl3—Zn1—Cl1	110.340 (12)
Cl3—Zn1—Cl2	106.573 (10)	Cl2—Zn1—Cl1	103.331 (11)

However, these C—N bond lengths are shorter than those in the related tricyclic protonated (PYQAZP: Reck et al., 1974 ) and non-protonated (GUCZUZ: Le Gall et al., 1999 ; LIZMOX: Zhang et al., 2008 ) quinazoline derivatives. In these three compounds, the sp³ character of the carbon atom between the two nitrogen atoms and the lack of the C=N double bond within the –N–C–N– moiety hampers the delocalization of the positive charge within this unit. It is instead delocalized over the –N=CH—C(phenylene) fragment (see Table S1 in the supporting information).

Analysis of the residual electron density (Spek, 2020 ) reveals that the covalent bonds in the heterocyclic cations clearly show up as local density maxima (Fig. 3).

Figure 3
Residual electron density in the planes through C2A, C4A and C8AA (top) and C2B, C4B and C4AB (bottom); contour lines are drawn at 0.2 e Å⁻³. Covalent bonds in the heterocyclic cations clearly show up as local density maxima.

The Zn^II centre in the dianion adopts a slightly distorted geometry, with τ⁴ = 0.95 (Yang et al., 2007 ). The high resolution (θ_max = 109.6°, sin θ/λ = 1.150 Å⁻¹, d = 0.43 Å) and the very favourable ratio between observations and variables (100:1) in our diffraction data result in small standard uncertainties for atomic coordinates and derived geometric parameters and allow to discuss more subtle details. The most acute angle of 103.33 (11)° within the tetrachloridozincate dianion (Table 1) is subtended by Cl1 and Cl2. These atoms are associated with the longest Zn—Cl distances, which, in turn, are correlated with the most relevant intermolecular interactions in the structure: Cl1 is involved in the shortest and most linear N—H⋯Cl hydrogen bond (see Table 2) and represents the most distant ligand in the anion. Cl2 is significantly closer to Zn1 and is engaged in a longer and presumably weaker hydrogen bond. The remaining chlorido ligands are not associated with any classical short contacts. Similar features have been reported for structurally related compounds (Sharma et al., 1993; Sargazakov et al., 1991; Tozhiboev et al., 2005; Wang et al., 2017 ).

Table 2
Hydrogen-bond geometry (Å, °)

Cg3 and Cg9 are the centroids of the C5A–C8A/C4AA/C8AA and C5B–C8B/C4AB/C8AB rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1A⋯Cl2	0.89 (2)	2.44 (2)	3.2659 (8)	155.9 (19)
N1B—H1B⋯Cl1ⁱ	0.83 (2)	2.352 (19)	3.1661 (7)	166.6 (18)
C11A—H11A⋯Cg9ⁱⁱ	0.99	2.67	3.5718 (10)	151
C12B—H12D⋯Cg3ⁱⁱⁱ	0.99	2.57	3.4002 (10)	142
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

3. Supramolecular features

In the crystal structure, the protonated N1A and N1B nitrogen atoms in the cations interact with the chlorido ligands Cl2 and Cl1, respectively, via relatively short N—H⋯Cl bonds and generate a D₂²(5) graph-set motif (Bernstein et al., 1995 ) (Table 2 and Fig. 4).

Figure 4
Crystal packing and short contacts in the title compound. Colour code: N—H⋯Cl interactions light-blue dashed lines, intermolecular C—H⋯π contacts red dashed lines, Zn—Cl⋯π contacts green dashed lines, π-π stacking interactions dark-blue dashed lines. Centroid for the pyrimidine (Cg1, Cg7) and benzene rings (Cg3, Cg9) are shown as blue and red spheres, respectively.

The crystal packing is further stabilized by intermolecular C—H⋯π interactions (Table 2) and additional short contacts between Cl3 and the N–C–N segment of the pyrimidine rings. The shortest contact distance occurs between Cl3 and C2B [3.5273 (9) Å] and involves an interaction between the electron-rich equatorial region of the halogen atom and the ring atom attached to two N-atom neighbours, most probably the most electron-deficient atom in the heterocycle. These contacts link anions and cations into a three-dimensional network. Weak π–π stacking interactions occur between pyrimidine (Cg1, Cg7) and benzene (Cg3, Cg9) rings of antiparallel pairs of cations and involve contact distances of Cg1⋯Cg3 (−x, −y, −z) = 3.6225 (5) Å (slippage 0.857 Å) and of Cg7⋯Cg9 (1 − x, −y, 1 − z) = 3.6246 (7) Å (slippage 0.994 Å).

4. Hirshfeld surface analysis

A Hirshfeld surface (HS) analysis (Spackman & Jayatilaka, 2009 ) was carried out using CrystalExplorer17.5 (Turner et al., 2017 ) to visualize interactions between the constituents of the title compound. The HS mapped with d_norm is represented in Fig. 5. The white surface indicates contacts with distances equal to the sum of van der Waals radii, and the red and blue colours indicate distances shorter or longer than the van der Waals radii, respectively. The bright-red spot near Cl1 indicates its role as a hydrogen-bond donor towards N1.

Figure 5
Three-dimensional Hirshfeld surface of the title compound mapped with d_norm.

The classical N—H⋯Cl hydrogen bonds correspond to Cl⋯H/H⋯Cl contacts (29.3% contribution) in Fig. 6c and show up as a pair of spikes. The most abundant contributions to the Hirshfeld surface arise from H⋯H contacts at 47.8%. Cl⋯H/H⋯Cl and C⋯H/H⋯C interactions follow with contributions of 29.3% and 15.9%, respectively (Fig. 6). Minor contributors are due to C⋯N/N⋯C (2.2%), N⋯H/H⋯N (2.0%), C⋯C (1.9%), C⋯Cl/Cl⋯C (0.4%), N⋯Cl/Cl⋯N (0.3%) and Zn⋯H/H⋯Zn (0.3%) contacts.

Figure 6
Two-dimensional fingerprint plots for the title compound, showing (a) all interactions, and decomposed into (b) H⋯H, (c) Cl⋯H/H⋯Cl, (d) C⋯H/H⋯C interactions. Values for d_i and d_e represent the closest internal and external distances (in Å) from given points on the Hirshfeld surface.

5. Database survey

A search in the Cambridge Structural Database (CSD, version 5.41, including the update of January 2020; Groom et al., 2016 ) confirmed that four related compounds had been structurally characterized in which similar cations interact with [ZnCl₄]²⁻ anions. They are associated with refcodes PODLUP (Sharma et al., 1993), PODLUP01 (Sargazakov et al., 1991) and SECFAI and SECFAI01 (Tozhiboev et al., 2005). An additional match for a similar cation interacting with a Cl⁻ anion was identified: EYUHEL (Turgunov et al., 2003) and PYQAZP (Reck et al., 1974).

6. Synthesis and crystallization

3 g (0.015 mol) of 2,3-tetramethylenquinazoline-4-one (Fig. 7) were placed in a 300 mL flat-bottom flask equipped with a magnetic stirrer and a reflux condenser. 72 mL of hydrochloric acid (15%) were added under stirring. 12 g of Zn powder were added in small portions over a period of 1 h, and the mixture was heated in a water bath for 4 h. The hot reaction mixture was filtered and the filtrate was left to precipitate overnight. The precipitate corresponding to 2,3-tetramethylenquinazoline hydrochloride was removed by filtration (Fig. 7). Colourless single crystals of the title compound were obtained by slow evaporation of the resulting filtrate at room temperature.

Figure 7
Synthesis scheme for 2,3-tetramethylene-3,4-dihydroquinazoline hydrochloride.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms attached to C were positioned geometrically, with C—H = 0.95 Å (for aromatic) or C—H = 0.99 Å (for methylene H atoms), and were refined with U_iso(H) = 1.2U_eq(C). H atoms bonded to nitrogen were located in a difference-Fourier map, and their positional and isotropic displacement parameters were freely refined.

Table 3
Experimental details

Crystal data
Chemical formula	(C₁₂H₁₅N₂)₂[ZnCl₄]
M_r	581.69
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	9.2910 (13), 15.682 (2), 17.275 (2)
β (°)	95.642 (2)
V (Å³)	2504.7 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.43
Crystal size (mm)	0.30 × 0.25 × 0.23

Data collection
Diffractometer	Bruker D8 gonimeter with APEX CCD detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
T_min, T_max	0.634, 0.751
No. of measured, independent and observed [I > 2σ(I)] reflections	170944, 31478, 21664
R_int	0.071
(sin θ/λ)_max (Å⁻¹)	1.150

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.124, 1.04
No. of reflections	31478
No. of parameters	306
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.29, −0.54
Computer programs: APEX2 (Bruker, 2008), and SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ), PLATON (Spek, 2020), publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2082994

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021004989/jq2006sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021004989/jq2006Isup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021004989/jq2006sup4.docx

checkCIF report

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: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis(6,7,8,9-tetrahydro-11H-pyrido[2,1-b]quinazolin-5-ium) tetrachloridozincate top

Crystal data top

(C₁₂H₁₅N₂)₂[ZnCl₄]	F(000) = 1200
M_r = 581.69	D_x = 1.543 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.2910 (13) Å	Cell parameters from 9853 reflections
b = 15.682 (2) Å	θ = 2.4–53.5°
c = 17.275 (2) Å	µ = 1.43 mm⁻¹
β = 95.642 (2)°	T = 100 K
V = 2504.7 (6) Å³	Block, colourless
Z = 4	0.30 × 0.25 × 0.23 mm

Data collection top

Bruker D8 gonimeter with APEX CCD detector diffractometer	31478 independent reflections
Radiation source: Incoatec microsource	21664 reflections with I > 2σ(I)
Multilayer optics monochromator	R_int = 0.071
ω scans	θ_max = 54.8°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −21→20
T_min = 0.634, T_max = 0.751	k = −35→35
170944 measured reflections	l = −39→37

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.124	w = 1/[σ²(F_o²) + (0.0465P)² + 0.1208P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
31478 reflections	Δρ_max = 1.29 e Å⁻³
306 parameters	Δρ_min = −0.54 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	0.40341 (2)	0.23046 (2)	0.17943 (2)	0.01331 (2)
Cl1	0.22695 (2)	0.31275 (2)	0.22716 (2)	0.01745 (3)
N1A	0.16789 (8)	0.13353 (5)	−0.01919 (5)	0.01731 (11)
H1A	0.233 (2)	0.1607 (14)	0.0126 (12)	0.033 (5)*
N1B	0.38700 (8)	−0.02546 (4)	0.36997 (4)	0.01498 (9)
H1B	0.344 (2)	−0.0665 (13)	0.3479 (11)	0.027 (5)*
Cl2	0.40142 (3)	0.27504 (2)	0.05329 (2)	0.01999 (4)
C2A	0.20841 (8)	0.09703 (5)	−0.08356 (5)	0.01372 (9)
C2B	0.31376 (8)	0.04719 (5)	0.37362 (4)	0.01304 (9)
Cl3	0.33617 (3)	0.09149 (2)	0.17498 (2)	0.01962 (4)
N3A	0.11462 (7)	0.05870 (4)	−0.13348 (4)	0.01329 (8)
N3B	0.37680 (8)	0.11694 (4)	0.40176 (4)	0.01312 (8)
Cl4	0.61489 (3)	0.24837 (2)	0.25278 (2)	0.02103 (4)
C4A	−0.04199 (9)	0.06077 (6)	−0.12794 (5)	0.01591 (11)
H4AA	−0.081466	0.002500	−0.136382	0.019*
H4AB	−0.088035	0.097703	−0.169781	0.019*
C4B	0.53321 (9)	0.12358 (5)	0.42526 (5)	0.01502 (10)
H4BA	0.548031	0.145493	0.479203	0.018*
H4BB	0.576081	0.165215	0.391071	0.018*
C4AA	−0.08071 (8)	0.09313 (5)	−0.05096 (4)	0.01320 (9)
C4AB	0.61022 (8)	0.04003 (5)	0.42109 (4)	0.01289 (9)
C5A	−0.22295 (9)	0.09044 (5)	−0.03207 (5)	0.01629 (11)
H5AA	−0.295685	0.064510	−0.066819	0.020*
C5B	0.75850 (9)	0.03353 (5)	0.44269 (5)	0.01662 (11)
H5BA	0.811468	0.082125	0.462049	0.020*
C6A	−0.25917 (10)	0.12560 (6)	0.03755 (6)	0.01813 (12)
H6AA	−0.356791	0.124795	0.049536	0.022*
C6B	0.82907 (10)	−0.04420 (6)	0.43590 (5)	0.01798 (12)
H6BA	0.929998	−0.048320	0.450822	0.022*
C7A	−0.15242 (10)	0.16192 (6)	0.08958 (5)	0.01727 (11)
H7AA	−0.177180	0.185134	0.137308	0.021*
C7B	0.75264 (10)	−0.11583 (5)	0.40740 (5)	0.01668 (11)
H7BA	0.801428	−0.168535	0.402655	0.020*
C8A	−0.00940 (10)	0.16428 (5)	0.07178 (5)	0.01643 (11)
H8AA	0.063845	0.188750	0.107176	0.020*
C8B	0.60526 (9)	−0.11006 (5)	0.38597 (5)	0.01506 (10)
H8BA	0.552357	−0.158681	0.366592	0.018*
C8AA	0.02476 (8)	0.13018 (5)	0.00118 (5)	0.01397 (10)
C8AB	0.53532 (8)	−0.03207 (5)	0.39314 (4)	0.01263 (9)
C9A	0.36640 (9)	0.09994 (6)	−0.09460 (6)	0.01879 (13)
H9AA	0.417435	0.055347	−0.061905	0.023*
H9AB	0.406030	0.155936	−0.076687	0.023*
C9B	0.15598 (9)	0.04381 (6)	0.34654 (5)	0.01737 (11)
H9BA	0.104080	0.016581	0.387400	0.021*
H9BB	0.141921	0.007614	0.299452	0.021*
C10A	0.39598 (10)	0.08639 (6)	−0.17905 (6)	0.01922 (13)
H10A	0.364050	0.136876	−0.210599	0.023*
H10B	0.500890	0.078255	−0.182272	0.023*
C10B	0.08950 (10)	0.13131 (6)	0.32782 (5)	0.01831 (12)
H10C	0.120478	0.152492	0.278085	0.022*
H10D	−0.017322	0.126944	0.322279	0.022*
C11A	0.31331 (10)	0.00783 (6)	−0.20972 (5)	0.01870 (12)
H11A	0.334131	−0.003545	−0.263874	0.022*
H11B	0.344925	−0.042305	−0.177597	0.022*
C11B	0.13845 (11)	0.19299 (6)	0.39317 (6)	0.01927 (13)
H11C	0.096932	0.250072	0.380703	0.023*
H11D	0.101903	0.173279	0.442051	0.023*
C12A	0.15251 (10)	0.02154 (6)	−0.20731 (5)	0.01692 (11)
H12A	0.116845	0.059773	−0.250607	0.020*
H12B	0.102340	−0.033882	−0.215627	0.020*
C12B	0.30183 (10)	0.19950 (5)	0.40475 (5)	0.01622 (11)
H12C	0.334665	0.237291	0.364075	0.019*
H12D	0.330136	0.226467	0.455799	0.019*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01365 (3)	0.01277 (3)	0.01329 (3)	−0.00112 (2)	0.00014 (2)	−0.00022 (2)
Cl1	0.02079 (8)	0.01451 (6)	0.01701 (7)	0.00525 (6)	0.00166 (5)	0.00210 (5)
N1A	0.0117 (2)	0.0220 (3)	0.0181 (3)	−0.00204 (19)	0.00103 (18)	−0.0070 (2)
N1B	0.0141 (2)	0.01106 (19)	0.0192 (3)	−0.00093 (16)	−0.00121 (18)	−0.00287 (17)
Cl2	0.02268 (9)	0.02343 (9)	0.01374 (7)	−0.00702 (7)	0.00123 (6)	0.00172 (6)
C2A	0.0117 (2)	0.0145 (2)	0.0149 (2)	−0.00067 (18)	0.00108 (17)	−0.00124 (18)
C2B	0.0142 (2)	0.0115 (2)	0.0135 (2)	−0.00064 (17)	0.00143 (17)	−0.00060 (16)
Cl3	0.01743 (8)	0.01217 (6)	0.02897 (10)	−0.00094 (5)	0.00082 (6)	−0.00157 (6)
N3A	0.0132 (2)	0.0139 (2)	0.0127 (2)	−0.00007 (16)	0.00030 (15)	−0.00098 (15)
N3B	0.0150 (2)	0.01093 (18)	0.0134 (2)	−0.00029 (16)	0.00118 (16)	−0.00126 (15)
Cl4	0.01708 (8)	0.02447 (9)	0.02043 (8)	−0.00490 (7)	−0.00384 (6)	0.00143 (6)
C4A	0.0116 (2)	0.0189 (3)	0.0168 (3)	−0.0002 (2)	−0.00079 (19)	−0.0033 (2)
C4B	0.0157 (3)	0.0120 (2)	0.0171 (3)	−0.00189 (19)	0.0005 (2)	−0.00154 (18)
C4AA	0.0116 (2)	0.0128 (2)	0.0150 (2)	0.00039 (17)	0.00005 (17)	−0.00033 (17)
C4AB	0.0142 (2)	0.0118 (2)	0.0128 (2)	−0.00191 (18)	0.00138 (17)	−0.00057 (16)
C5A	0.0123 (2)	0.0165 (3)	0.0201 (3)	−0.0004 (2)	0.0017 (2)	0.0008 (2)
C5B	0.0146 (3)	0.0158 (3)	0.0192 (3)	−0.0023 (2)	0.0005 (2)	−0.0004 (2)
C6A	0.0158 (3)	0.0180 (3)	0.0212 (3)	0.0010 (2)	0.0052 (2)	0.0023 (2)
C6B	0.0142 (3)	0.0190 (3)	0.0206 (3)	0.0000 (2)	0.0011 (2)	0.0011 (2)
C7A	0.0192 (3)	0.0164 (3)	0.0169 (3)	0.0027 (2)	0.0048 (2)	0.0008 (2)
C7B	0.0165 (3)	0.0154 (3)	0.0182 (3)	0.0022 (2)	0.0023 (2)	0.0003 (2)
C8A	0.0177 (3)	0.0159 (3)	0.0156 (3)	0.0021 (2)	0.0011 (2)	−0.0019 (2)
C8B	0.0161 (3)	0.0125 (2)	0.0165 (3)	0.00052 (19)	0.0011 (2)	−0.00113 (18)
C8AA	0.0123 (2)	0.0140 (2)	0.0154 (2)	0.00074 (18)	0.00041 (18)	−0.00140 (18)
C8AB	0.0134 (2)	0.0115 (2)	0.0130 (2)	−0.00062 (17)	0.00100 (17)	−0.00091 (16)
C9A	0.0123 (3)	0.0234 (3)	0.0208 (3)	−0.0012 (2)	0.0024 (2)	−0.0026 (3)
C9B	0.0138 (3)	0.0171 (3)	0.0209 (3)	−0.0010 (2)	0.0007 (2)	−0.0004 (2)
C10A	0.0168 (3)	0.0210 (3)	0.0207 (3)	−0.0002 (2)	0.0060 (2)	0.0014 (2)
C10B	0.0165 (3)	0.0192 (3)	0.0190 (3)	0.0028 (2)	0.0008 (2)	−0.0008 (2)
C11A	0.0203 (3)	0.0198 (3)	0.0167 (3)	0.0020 (2)	0.0057 (2)	0.0001 (2)
C11B	0.0195 (3)	0.0196 (3)	0.0190 (3)	0.0047 (2)	0.0032 (2)	−0.0025 (2)
C12A	0.0190 (3)	0.0186 (3)	0.0130 (2)	−0.0003 (2)	0.0012 (2)	−0.0017 (2)
C12B	0.0206 (3)	0.0122 (2)	0.0158 (3)	0.0021 (2)	0.0009 (2)	−0.00163 (19)

Geometric parameters (Å, º) top

Zn1—Cl4	2.2484 (3)	C6A—H6AA	0.9500
Zn1—Cl3	2.2664 (4)	C6B—C7B	1.3928 (13)
Zn1—Cl2	2.2868 (4)	C6B—H6BA	0.9500
Zn1—Cl1	2.3019 (3)	C7A—C8A	1.3936 (13)
N1A—C2A	1.3373 (11)	C7A—H7AA	0.9500
N1A—C8AA	1.4096 (11)	C7B—C8B	1.3858 (12)
N1A—H1A	0.89 (2)	C7B—H7BA	0.9500
N1B—C2B	1.3317 (10)	C8A—C8AA	1.3965 (11)
N1B—C8AB	1.4005 (10)	C8A—H8AA	0.9500
N1B—H1B	0.83 (2)	C8B—C8AB	1.3962 (11)
C2A—N3A	1.3102 (10)	C8B—H8BA	0.9500
C2A—C9A	1.4994 (12)	C9A—C10A	1.5257 (14)
C2B—N3B	1.3114 (9)	C9A—H9AA	0.9900
C2B—C9B	1.4952 (12)	C9A—H9AB	0.9900
N3A—C4A	1.4680 (11)	C9B—C10B	1.5262 (13)
N3A—C12A	1.4759 (11)	C9B—H9BA	0.9900
N3B—C12B	1.4735 (10)	C9B—H9BB	0.9900
N3B—C4B	1.4735 (11)	C10A—C11A	1.5193 (14)
C4A—C4AA	1.4998 (11)	C10A—H10A	0.9900
C4A—H4AA	0.9900	C10A—H10B	0.9900
C4A—H4AB	0.9900	C10B—C11B	1.5218 (13)
C4B—C4AB	1.4981 (11)	C10B—H10C	0.9900
C4B—H4BA	0.9900	C10B—H10D	0.9900
C4B—H4BB	0.9900	C11A—C12A	1.5140 (13)
C4AA—C8AA	1.3912 (11)	C11A—H11A	0.9900
C4AA—C5A	1.3927 (11)	C11A—H11B	0.9900
C4AB—C8AB	1.3891 (10)	C11B—C12B	1.5149 (14)
C4AB—C5B	1.3951 (12)	C11B—H11C	0.9900
C5A—C6A	1.3941 (13)	C11B—H11D	0.9900
C5A—H5AA	0.9500	C12A—H12A	0.9900
C5B—C6B	1.3944 (13)	C12A—H12B	0.9900
C5B—H5BA	0.9500	C12B—H12C	0.9900
C6A—C7A	1.3930 (14)	C12B—H12D	0.9900

Cl4—Zn1—Cl3	111.219 (10)	C7A—C8A—C8AA	119.08 (8)
Cl4—Zn1—Cl2	115.057 (11)	C7A—C8A—H8AA	120.5
Cl3—Zn1—Cl2	106.573 (10)	C8AA—C8A—H8AA	120.5
Cl4—Zn1—Cl1	109.994 (13)	C7B—C8B—C8AB	119.32 (7)
Cl3—Zn1—Cl1	110.340 (12)	C7B—C8B—H8BA	120.3
Cl2—Zn1—Cl1	103.331 (11)	C8AB—C8B—H8BA	120.3
C2A—N1A—C8AA	122.76 (7)	C4AA—C8AA—C8A	121.28 (7)
C2A—N1A—H1A	119.3 (14)	C4AA—C8AA—N1A	118.41 (7)
C8AA—N1A—H1A	117.9 (14)	C8A—C8AA—N1A	120.31 (7)
C2B—N1B—C8AB	122.87 (6)	C4AB—C8AB—C8B	121.48 (7)
C2B—N1B—H1B	117.3 (14)	C4AB—C8AB—N1B	118.97 (7)
C8AB—N1B—H1B	119.4 (14)	C8B—C8AB—N1B	119.53 (7)
N3A—C2A—N1A	121.36 (7)	C2A—C9A—C10A	112.83 (7)
N3A—C2A—C9A	121.75 (7)	C2A—C9A—H9AA	109.0
N1A—C2A—C9A	116.87 (7)	C10A—C9A—H9AA	109.0
N3B—C2B—N1B	121.29 (7)	C2A—C9A—H9AB	109.0
N3B—C2B—C9B	122.27 (7)	C10A—C9A—H9AB	109.0
N1B—C2B—C9B	116.41 (7)	H9AA—C9A—H9AB	107.8
C2A—N3A—C4A	123.12 (7)	C2B—C9B—C10B	113.48 (7)
C2A—N3A—C12A	123.38 (7)	C2B—C9B—H9BA	108.9
C4A—N3A—C12A	112.78 (6)	C10B—C9B—H9BA	108.9
C2B—N3B—C12B	123.39 (7)	C2B—C9B—H9BB	108.9
C2B—N3B—C4B	123.61 (7)	C10B—C9B—H9BB	108.9
C12B—N3B—C4B	112.65 (6)	H9BA—C9B—H9BB	107.7
N3A—C4A—C4AA	113.01 (6)	C11A—C10A—C9A	108.29 (7)
N3A—C4A—H4AA	109.0	C11A—C10A—H10A	110.0
C4AA—C4A—H4AA	109.0	C9A—C10A—H10A	110.0
N3A—C4A—H4AB	109.0	C11A—C10A—H10B	110.0
C4AA—C4A—H4AB	109.0	C9A—C10A—H10B	110.0
H4AA—C4A—H4AB	107.8	H10A—C10A—H10B	108.4
N3B—C4B—C4AB	112.81 (6)	C11B—C10B—C9B	109.21 (7)
N3B—C4B—H4BA	109.0	C11B—C10B—H10C	109.8
C4AB—C4B—H4BA	109.0	C9B—C10B—H10C	109.8
N3B—C4B—H4BB	109.0	C11B—C10B—H10D	109.8
C4AB—C4B—H4BB	109.0	C9B—C10B—H10D	109.8
H4BA—C4B—H4BB	107.8	H10C—C10B—H10D	108.3
C8AA—C4AA—C5A	119.02 (7)	C12A—C11A—C10A	109.98 (7)
C8AA—C4AA—C4A	120.02 (7)	C12A—C11A—H11A	109.7
C5A—C4AA—C4A	120.88 (7)	C10A—C11A—H11A	109.7
C8AB—C4AB—C5B	118.77 (7)	C12A—C11A—H11B	109.7
C8AB—C4AB—C4B	120.22 (7)	C10A—C11A—H11B	109.7
C5B—C4AB—C4B	120.99 (7)	H11A—C11A—H11B	108.2
C4AA—C5A—C6A	120.35 (8)	C12B—C11B—C10B	111.30 (7)
C4AA—C5A—H5AA	119.8	C12B—C11B—H11C	109.4
C6A—C5A—H5AA	119.8	C10B—C11B—H11C	109.4
C6B—C5B—C4AB	120.10 (8)	C12B—C11B—H11D	109.4
C6B—C5B—H5BA	120.0	C10B—C11B—H11D	109.4
C4AB—C5B—H5BA	120.0	H11C—C11B—H11D	108.0
C7A—C6A—C5A	120.09 (8)	N3A—C12A—C11A	113.56 (7)
C7A—C6A—H6AA	120.0	N3A—C12A—H12A	108.9
C5A—C6A—H6AA	120.0	C11A—C12A—H12A	108.9
C7B—C6B—C5B	120.48 (8)	N3A—C12A—H12B	108.9
C7B—C6B—H6BA	119.8	C11A—C12A—H12B	108.9
C5B—C6B—H6BA	119.8	H12A—C12A—H12B	107.7
C6A—C7A—C8A	120.15 (8)	N3B—C12B—C11B	114.03 (7)
C6A—C7A—H7AA	119.9	N3B—C12B—H12C	108.7
C8A—C7A—H7AA	119.9	C11B—C12B—H12C	108.7
C8B—C7B—C6B	119.85 (8)	N3B—C12B—H12D	108.7
C8B—C7B—H7BA	120.1	C11B—C12B—H12D	108.7
C6B—C7B—H7BA	120.1	H12C—C12B—H12D	107.6

C8AA—N1A—C2A—N3A	2.92 (13)	C5A—C4AA—C8AA—C8A	0.18 (12)
C8AA—N1A—C2A—C9A	−175.40 (8)	C4A—C4AA—C8AA—C8A	177.12 (8)
C8AB—N1B—C2B—N3B	−2.13 (12)	C5A—C4AA—C8AA—N1A	−179.12 (8)
C8AB—N1B—C2B—C9B	179.87 (7)	C4A—C4AA—C8AA—N1A	−2.18 (11)
N1A—C2A—N3A—C4A	7.04 (12)	C7A—C8A—C8AA—C4AA	−0.81 (12)
C9A—C2A—N3A—C4A	−174.72 (8)	C7A—C8A—C8AA—N1A	178.47 (8)
N1A—C2A—N3A—C12A	176.62 (8)	C2A—N1A—C8AA—C4AA	−5.18 (13)
C9A—C2A—N3A—C12A	−5.15 (12)	C2A—N1A—C8AA—C8A	175.52 (8)
N1B—C2B—N3B—C12B	177.97 (7)	C5B—C4AB—C8AB—C8B	−0.34 (12)
C9B—C2B—N3B—C12B	−4.15 (12)	C4B—C4AB—C8AB—C8B	177.67 (7)
N1B—C2B—N3B—C4B	5.30 (12)	C5B—C4AB—C8AB—N1B	−178.78 (7)
C9B—C2B—N3B—C4B	−176.82 (7)	C4B—C4AB—C8AB—N1B	−0.77 (11)
C2A—N3A—C4A—C4AA	−13.21 (11)	C7B—C8B—C8AB—C4AB	0.19 (12)
C12A—N3A—C4A—C4AA	176.22 (7)	C7B—C8B—C8AB—N1B	178.62 (8)
C2B—N3B—C4B—C4AB	−5.72 (11)	C2B—N1B—C8AB—C4AB	−0.11 (12)
C12B—N3B—C4B—C4AB	−179.08 (7)	C2B—N1B—C8AB—C8B	−178.59 (8)
N3A—C4A—C4AA—C8AA	10.43 (11)	N3A—C2A—C9A—C10A	21.96 (12)
N3A—C4A—C4AA—C5A	−172.68 (7)	N1A—C2A—C9A—C10A	−159.73 (8)
N3B—C4B—C4AB—C8AB	3.35 (10)	N3B—C2B—C9B—C10B	20.32 (12)
N3B—C4B—C4AB—C5B	−178.68 (7)	N1B—C2B—C9B—C10B	−161.70 (8)
C8AA—C4AA—C5A—C6A	0.99 (12)	C2A—C9A—C10A—C11A	−49.37 (10)
C4A—C4AA—C5A—C6A	−175.93 (8)	C2B—C9B—C10B—C11B	−46.34 (10)
C8AB—C4AB—C5B—C6B	0.16 (12)	C9A—C10A—C11A—C12A	61.61 (10)
C4B—C4AB—C5B—C6B	−177.84 (8)	C9B—C10B—C11B—C12B	57.99 (10)
C4AA—C5A—C6A—C7A	−1.52 (13)	C2A—N3A—C12A—C11A	17.27 (11)
C4AB—C5B—C6B—C7B	0.17 (14)	C4A—N3A—C12A—C11A	−172.19 (7)
C5A—C6A—C7A—C8A	0.87 (13)	C10A—C11A—C12A—N3A	−45.61 (10)
C5B—C6B—C7B—C8B	−0.33 (14)	C2B—N3B—C12B—C11B	15.61 (11)
C6A—C7A—C8A—C8AA	0.29 (13)	C4B—N3B—C12B—C11B	−171.01 (7)
C6B—C7B—C8B—C8AB	0.15 (13)	C10B—C11B—C12B—N3B	−42.79 (10)

Hydrogen-bond geometry (Å, º) top

Cg3 and Cg9 are the centroids of the C5A–C8A/C4AA/C8AA and C5B–C8B/C4AB/C8AB rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···Cl2	0.89 (2)	2.44 (2)	3.2659 (8)	155.9 (19)
N1B—H1B···Cl1ⁱ	0.83 (2)	2.352 (19)	3.1661 (7)	166.6 (18)
C11A—H11A···Cg9ⁱⁱ	0.99	2.67	3.5718 (10)	151
C12B—H12D···Cg3ⁱⁱⁱ	0.99	2.57	3.4002 (10)	142

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

Acknowledgements

The authors are grateful to the Institute of Inorganic Chemistry, RWTH Aachen University for providing laboratory facilities.

Funding information

Funding for this research was provided by: the German Academic Exchange Service (DAAD), Germany.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Johns, S. R. & Lamberton, J. A. (1965). J. Chem. Soc. Chem. Commun. p. 267a. Google Scholar
Le Gall, E., Malassene, R., Toupet, L., Hurvois, J.-P. & Moinet, C. (1999). Synlett, pp. 1383–1386. CSD CrossRef Google Scholar
Michael, J. P. (2004). Nat. Prod. Rep. 21, 650–668. Web of Science CrossRef PubMed CAS Google Scholar
Reck, G., Höhne, E. & Adam, G. (1974). J. Prakt. Chem. 316, 496–502. CSD CrossRef CAS Web of Science Google Scholar
Sargazakov, K. D., Molchanov, L. V., Tashkhodzhaev, B. & Aripova, Kh. N. (1991). Khim. Prir. Soedin. 6, 862–864. Google Scholar
Shakhidoyatov, Kh. M. & Elmuradov, B. Zh. (2014). Chem. Nat. Compd. 50, 781–800. Web of Science CrossRef CAS Google Scholar
Sharma, S. D., Gupta, V. K., Goswami, K. N. & Padmanabhan, V. M. (1993). Cryst. Res. Technol. 28, 1115–1121. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Tozhiboev, A. G., Turgunov, K. K., Tashkhodzhaev, B. & Musaeva, G. V. (2005). J. Struct. Chem. 46, 950–954. Web of Science CrossRef CAS Google Scholar
Turgunov, K. K., Tashkhodzhaev, B., Molchanov, L. V. & Shakhidoyatov, Kh. M. (2003). Chem. Nat. Compd. 39, 379–382. Web of Science CrossRef CAS Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. University of Western Australia. https://hirshfeldsurface.net. Google Scholar
Wang, A., Wang, R., Kalf, I., Dreier, A., Lehmann, C. W. & Englert, U. (2017). Cryst. Growth Des. 17, 2357–2364. Web of Science CSD CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, L., Powell, D. R. & Houser, R. P. (2007). Dalton Trans. pp. 955–964. Web of Science CSD CrossRef PubMed CAS Google Scholar
Zhang, C., De, C. K., Mal, R. & Seidel, D. (2008). J. Am. Chem. Soc. 130, 416–417. Web of Science CSD CrossRef PubMed CAS Google Scholar

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