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Article

Synthesis and X-ray Structure Combined with Hirshfeld and AIM Studies on a New Trinuclear Zn(II)-Azido Complex with s-Triazine Pincer Ligand

by
Kholood A. Dahlous
1,
Saied M. Soliman
2,*,
Ayman El-Faham
2 and
Raghdaa A. Massoud
2
1
Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia
2
Department of Chemistry, Faculty of Science, Alexandria University, Ibrahimia, P.O. Box 426, Alexandria 21321, Egypt
*
Author to whom correspondence should be addressed.
Crystals 2022, 12(12), 1786; https://doi.org/10.3390/cryst12121786
Submission received: 14 November 2022 / Revised: 1 December 2022 / Accepted: 6 December 2022 / Published: 8 December 2022
Browse Figures
Versions Notes

Abstract

:
The trinuclear [Zn3(PMT)2(Cl4)(N3)2] complex of the N-pincer ligand, 2,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)-6-methoxy-1,3,5-triazine (PMT), was obtained by self-assembly of the polydentate ligand (PMT) with ZnCl2 in the presence of azide ion as an auxiliary bridging ligand. The X-ray structure analysis revealed a monoclinic crystal system and centrosymmetric space group C2/c. There are two crystallographically independent Zn(II) sites where the Zn1 and Zn2 are tetra- and penta-coordinated with ZnN2Cl2 and ZnN4Cl coordination environments, respectively. The distortion τ4 and τ5 parameters for the Zn1 and Zn2 sites are 0.93 and 0.52, respectively. Hence, the Zn(1)N2Cl2 has a distorted tetrahedral configuration, while the Zn(2)N4Cl coordination sphere is intermediate between the square pyramidal and trigonal bipyramidal configurations. In this complex, the PMT is a tridentate N-chelate, while the chloride and azide anions are terminal and μ(1,1) bridged ligands, respectively. The %H…H, N…H, Cl…H, and C…H are 40.8, 17.2, 16.0, and 10.1%, respectively, based on Hirshfeld analysis. The charges at the Zn1 (+0.996 e) and Zn2 (+1.067 e) sites are calculated to be less than the official charge of the isolated Zn(II) ion. The μ(1,1) bridged azide has two asymmetric N–N bonds with clear covalent characters. In contrast, the Zn–N and Zn–Cl bonds have predominant closed-shell characters.

1. Introduction

Organic molecules with more than one donor atoms arranged in the ligand backbone by the way that could form stable metal chelates with metal ion are called multidentate ligands. This class of ligands can easily form more stable coordination compounds than the simple monodentate ligands. The extra stability of these metal complexes is derived from the chelate effect. There is a special interest from researchers in the symmetric multidentate ligands due to their great importance for the synthesis of interesting supramolecular structures with diverse applications in different fields [1,2,3,4].
Triazine compounds have a wide range of commercial uses as resins and for the removal of pesticides [5,6]. In industry, s-triazine derivatives have many applications as pharmaceutical materials and in textile manufacturing [7,8,9]. Metal triazine complexes [10,11,12,13,14] have demonstrated interesting antimicrobial, anticancer, and antiviral activities [15,16,17]. In addition, these complexes have interesting magnetic [18,19,20] and catalytic [21,22,23,24,25,26,27,28,29,30,31,32] properties. s-Triazine is a six-membered ring with alternating nitrogen and carbon atoms in the ring backbone. Due to the high electron deficiency of this ring, different nucleophiles could be added to the carbon atoms of the s-triazine, leading to a diverse and large number of mono-, di-, and tri-substituted s-triazines. In this class of ligands, varying the substituents attached to the s-triazine core changes their steric and electronic properties, leading to great effects on the reactivity of the coordinated metal ion. Derivatives of s-triazine such as 2,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)-6-methoxy-1,3,5-triazine (Figure 1) are among the multidentate ligands that attracted the attention of our research group [33,34,35,36,37]. On the other hand, incorporation of auxiliary bridged ligand such as azide could produce a significant impact on the nuclearity of the resulting coordination compound. Azide is a powerful bridging ligand with different bonding modes and has a great ability to connect different metal centers, leading to the construction of polynuclear complexes (Scheme 1) [38,39,40,41,42,43,44]. The most common modes of bonding are the end-on (μ(1,1) or EO) and end-to-end (μ(1,3) or EE) [38,39,45].
Zinc(II) complexes have attracted the interest of researchers due to their diverse biological applications in different fields [46,47,48,49,50,51], where Zn(II) is considered as an essential trace metal in biological systems [52]. In our previous work, we presented the synthesis of Zn(II) complexes with PMT ligand in the presence of different anions (X=Cl−, Br−, NO3−, SCN−, and ClO4−) [53,54]. In all cases, the mononuclear Zn(II) complexes [Zn(3,5-dimethylpyrazole)2Cl2], [Zn(PMT)(Br)2], [Zn(PMT)(NO3)2], [Zn(PMT)(NCS)2], and [Zn(PMT)(H2O)Cl]ClO4 were obtained, respectively. In this work and in light of the interesting bridging power of azide ion as an auxiliary linker ligand and in continuation with our interest with this pincer (Figure 1), we merged ZnCl2 and PMT in the presence of sodium azide in one pot. The newly synthesized complex was characterized using FTIR spectra, elemental analysis, and single crystal X-ray structure analysis. Its molecular and supramolecular structural properties were analyzed with the aid of a single crystal X-ray structure and Hirshfeld and DFT calculations. In addition, analysis of the different coordination interactions was performed using atoms in molecules (AIM) calculations.

2. Materials and Methods

2.1. Synthesis of [Zn3(PMT)2(Cl4)(N3)2]

A mixture of the PMT (30.0 mg, 0.01 mmol) pincer ligand in 10 mL methanol and 5 mL aqueous solution of ZnCl2 (18.3 mg, 0.01 mmol) in the presence of 1 mL saturated NaN3 solution (41.0 mg, 0.63 mmol) was left at room temperature to slowly evaporate. The titled complex was obtained as colorless block crystals after 8 days. The crystals were harvested from solution by filtration.
Yield: C28H34Cl4N20O2Zn3 (83.7%). Anal. Calc.: C, 32.95; H, 3.36; N, 27.45%. Found: C, 32.80; H, 3.29; N, 27.30%. IR (KBr, cm−1): 3121, 2998, 2099, 2047, 1621, 1543; Figure S1 (Supplementary Materials).

2.2. Physicochemical Characterizations

All instrumental and chemicals details used, as well as the X-ray measurements including data collection and structure solution, are described in the Supplementary Materials [55,56,57].

2.3. Computational Details

All details regarding Hirshfeld [58] and DFT [59,60,61,62,63] calculations are described in the Supplementary Materials.

3. Results and Discussion

3.1. Chemistry

The coordination behavior of the 2,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)-6-methoxy-1,3,5-triazine (PMT) pincer ligand was found to be sensitive to the nature of the metal ion. In most cases, this ligand behaves as a tridentate N-chelate [33,34,35,36,37,53,54], while in other instances, the ligand undergoes hydrolysis prior to the complexation with the metal ion [64,65,66]. In our previous work, we reported the behavior of the PMT ligand towards different Zn(II) salts (Scheme 2). In continuation of this work, we reported here the reaction of the same ligand with ZnCl2 in the presence of azide as an auxiliary bridging ligand. Unlike the thiocyanate analogue, which afforded the monomeric [Zn(PMT)(NCS)2] complex, the self-assembly of PMT, ZnCl2, and azide afforded a new trinuclear Zn(II) complex, which was revealed using elemental analysis, FTIR spectra, and single crystal X-ray diffraction to have the formula [Zn3(PMT)2(Cl4)(N3)2]. In the FTIR spectra of this complex, a clear double split band was detected at 2099 and 2047 cm−1, which confirmed the presence of the azide ion. Additionally, ν(C=N) and ν(C=C) bands were detected at 1621 cm−1 and 1543 cm−1, respectively, instead of 1593 cm−1 and 1555 cm−1, respectively, for the free PMT. It is clear that the complexation between PMT and the Zn(II) ion shifted the ν(C=N) mode to a higher wavenumber. In contrast, the ν(C=C) mode was shifted to a lower wavenumber compared to the free ligand.

3.2. Crystal Structure Description

The structure of the trinuclear [Zn3(PMT)2(Cl4)(N3)2] complex was confirmed using single crystal X-ray diffraction analysis. This complex crystallized in the centrosymmetric space group C2/c in the monoclinic crystal system. The crystal parameters were a = 18.549(11) Å, b = 11.371(7) Å, c = 20.123(11) Å, and β = 97.098(11)°. Further crystal data details are depicted in Table 1, while the crystal structure of this trinuclear complex is shown in the left part of Figure 2.
In this trinuclear complex, there was a two-fold rotation axis passing through the Zn(1) site. Hence, the asymmetric formula contained one half of the [Zn3(PMT)2(Cl4)(N3)2] complex formula. As a result, the trinuclear Zn(II) complex comprised two halves of the asymmetric formula, shown in the right part of Figure 2. It is clear that there were two crystallographically independent Zn(II) sites, which differed completely in the coordination environment. The Zn(1) site was tetra-coordinated and had a complete inorganic coordination environment with two chloride and two azide ions as ligands. Due to symmetry consideration, the two Zn1–Cl1 bonds were equidistant (2.2305(12) Å). In addition, the same was true for the Zn1–N10 bonds (2.040(2) Å). The bond angles for the coordination environment around the Zn(1) site ranged from 105.46(8)° to 118.35(7)° for the N10–Zn1–Cl1# and Cl1–Zn1–Cl1#, respectively (Table 2). Since the distances between the Zn(1) site and donor atoms differed significantly in addition to the bond angles, the coordination geometry around Zn(1) could be described as a distorted tetrahedral. With the aid of the τ4 parameter, the configuration around the Zn(1) site was described. The distortion τ4 parameter was zero for a square planar configuration and one for a perfect tetrahedron [67]. In the case of Zn(1), the τ4 value was 0.93, which confirmed a more tetrahedral-like configuration around Zn(1) with some deviations from the ideal case.
On the other hand, the Zn(2) site was penta-coordinated with mixed organic and inorganic coordination environments. In this case, the Zn(2) was coordinated with one PMT pincer ligand as a tridentate chelate, one chloride ion as a terminal ligand, and one μ(1,1) bridged azide that connected the two Zn(1) and Zn(2) sites. The three Zn–N interactions with the PMT ligand were not equidistant, where the Zn2–N8 bond with the s-triazine core was shorter (2.072(2) Å) than the two Zn2–N3 (2.181(3) Å) and Zn2–N7 (2.279(2) Å) bonds with the two pyrazolyl moieties. The bite angles of the PMT tridentate ligand were 71.66(8)° and 73.53(8)° for the N8–Zn2–N7 and N8–Zn2–N3 angles, respectively. These values were in good agreement with the structurally related Zn(II) complexes with the same ligand [53,54]. The Zn2–Cl2 and Zn2–N10 bond distances were 2.1924(14) and 2.036(2) Å, respectively. Hence, the coordination environment around the Zn(2) site was a distorted penta-coordinated system. Based on τ5 parameter analysis for the penta-coordinated Zn(2) atom [68], the estimated τ5 value was 0.52. This intermediate value between the two extremes revealed an intermediate structure between the square pyramidal (τ5 = 0) and trigonal bipyramidal (τ5 = 1) configurations.
It is worth noting that the reaction of CdCl2 with the same ligand in the presence of sodium azide afforded the dinuclear [Cd(PMT)(Cl)(N3)]2 complex [69]. Similar to the present [Zn3(PMT)2(Cl4)(N3)2] complex, the PMT acted as a tridentate pincer chelate. Unlike the Zn(II) complex, the two Cd(II) centers were found connected by two azide ions in the double μ(1,1) bridging mode, leading to the [Cd(PMT)(Cl)(N3)]2 dinuclear formula. The diversity in the azide bonding mode in both complexes could be attributed to the different sizes of the central metal ion. It might be concluded that the two azide ions could not connect a small size metal ion such as Zn(II) in a stable double μ(1,1) bridging mode as a consequence of the steric preferences of the bulky PMT ligands.
In the studied trinuclear Zn(II) complex, the packing structure did not show any classical hydrogen bonds. On the other hand, the packing was controlled by significantly long non-classical C–H…N contacts between the C7–H11 group and the freely un-coordinated nitrogen atom (N11) of the azide group (Figure 3). The H…N and C…N distances were 2.62 Å and 3.421(5) Å, respectively, while the C12–H12C…N10 angle was 145°. A view of the packing for the complex units along the crystallographic a-direction is shown in Figure 4.

3.3. Analysis of Molecular Packing

The different Hirshfeld surfaces (dnorm, shape index, and curvedness) of the trinuclear [Zn3(PMT)2(Cl4)(N3)2] complex are presented in Figure 5. This complex has a highly symmetric structure due to the presence of a two-fold rotation axis passing through the Zn(1) metal center. As a result, there is a highly symmetric distribution for the intermolecular contacts, which control the molecular packing of this complex. In the upper part of Figure 5, the dnorm map indicates the presence of many red spots corresponding to the H…C, N…H, and Cl…C interactions. Although there are four red spots for each interaction, all belong to the same intermolecular contact for each interaction. All the four red spots labelled by the letter A belong to the same H…C interaction. The corresponding interaction distance is 2.716 Å (C5…H8). Similarly, the red spots B and C, which belong to the N…H and Cl…C interactions, are related to the N11…H1 (2.493 Å) and Cl2…C5 (3.109 Å).
Another important aspect of the Hirshfeld calculations is the high ability of such tools to predict the percentages of all possible interactions among neighboring atoms. A summary of all contacts noted in the crystal structure of the trinuclear [Zn3(PMT)2(Cl4)(N3)2] complex is depicted in Figure 6. The H…H, N…H, Cl…H, and C…H were the most abundant contacts. Their percentages were calculated with the aid of the fingerprint plots’ decomposition to be 40.8, 17.2, 16.0, and 10.1%, respectively.
The decomposed fingerprint plots not only gave an indication of the contribution of each intermolecular contact in the studied crystal structure but also shed light on the strength of each interaction. As is clearly seen from the decomposed fingerprint plots presented in Figure 7, the H…C, N…H, and Cl…C have the characteristic sharp spikes of strong interactions. In addition, the decomposed fingerprint plots are highly symmetric, which is in good accord with the highly symmetric structure of the trinuclear complex.

3.4. Natural Charge Distribution

Natural charges of the ligand groups and the Zn atom were calculated using the [Zn3(PMT)2(Cl4)(N3)2] molecule as obtained from the crystal structure without geometry optimization. In this trinuclear Zn(II) complex, there are two crystallographically independent Zn(II) atoms with different coordination environments. As a result of these coordination interactions, there must be a partial charge compensation for the divalent Zn(II) ion as a consequence of the interactions with the ligand donor atoms. In a chemical sense, the negatively charged donor atoms could compensate the metal ion positive charge to a higher extent than the neutrally charged donor atoms. In addition, the number of donor atoms coordinated to the Zn(II) ion increased as the charge compensation increased. Analysis of the natural charge at the two Zn(II) sites revealed a decrease in their positive charges to 0.996 and 1.067 e for the tetra- and penta-coordinated Zn(II) ions, respectively. The presence of the negatively charged chloride and azide ions coordinated to the tetra-coordinated Zn(II) compensated the positive charge to higher extent compared to the penta-coordinated Zn(II) ion, which is coordinated to one azide, one chloride, and three nitrogen atoms from the neutral tridentate pincer ligand. In case of the former, the two chloride ions have a net charge of −1.328 e. Hence, the amount of electron density transferred from the two chloride ions to the tetra-coordinated Zn(II) is 0.672 e. The net charge of the bridged azide ion is −0.625 e. As a result, the amount of electron density transferred to the two Zn(II) ions is 0.375 e. For the tridentate N-pincer chelate, the net charge is +0.359 e, which represents the amount of electron density transferred from this neutral ligand to the penta-coordinated Zn(II).

3.5. The Atoms in Molecules (AIM) Studies

The AIM calculations were performed on the [Zn3(PMT)2(Cl4)(N3)2] molecule as obtained from the crystal structure without geometry optimization. The study of the bond properties with the aid of AIM calculations was used to shed light on the nature and strength of bonds under interest [70,71,72,73,74]. The AIM parameters for the Zn–N and Zn–Cl bonds are depicted in Table 3. Bonds with electron density functions (ρ) less than 0.1 a.u. have predominant closed-shell characters. It is clear from the results collected in Table 3 that all bonds satisfied this requirement. Hence, all Zn–N (0.0277–0.0572 a.u.) and Zn–Cl (0.0431–0.0461 a.u.) bonds had mainly closed shell characters. In agreement with these results, the V(r)/G(r) values were generally slightly less than 1. In addition, the total energy density (H(r)) had either positive or very small negative values, which further revealed the predominant closed-shell character of all coordination interactions [75]. In addition, the value of this function had a direct relation to the bond strength. In this regard, we plotted the electron density function (ρ) against the Zn–N distances, and the result is shown in Figure 8. It is obvious that there was an inverse relation between the electron density function (ρ) and the Zn–N distances, which confirmed the above conclusion (R2 = 0.9666).
On the other hand, it is well known that the coordination between the azide ion and the metal ion usually affects the degree of asymmetry in the N–N bonds of the azide group. The free azide ion has two equidistant N–N bonds, while the coordinated azide usually violates this role. In the [Zn3(PMT)2(Cl4)(N3)2] complex, the N10–N1 and N1–N11 bonds of the coordinated azide differed by 0.081 Å, where the former was longer than the latter, indicating a decrease in the bond order for the N–N bond comprising the nitrogen atom coordinated to the metal ion. As clearly seen from the results shown in Table 3, the AIM topology parameters revealed these facts very well. The electron density function (ρ) was smaller for the N10–N1 bond (0.4607 a.u.) than the N1–N11 bond (0.5725 a.u.). In all cases, clear covalent characters were detected for the two N–N bonds, where V(r)/G(r) > 1 and H(r) < 0.

4. Conclusions

The X-ray structure of the trinuclear [Zn3(PMT)2(Cl4)(N3)2] complex is presented. It comprises two crystallographically independent Zn(II) sites. The Zn(1) has an inorganic coordination environment with two chloride ions as terminal ligands and two μ(1,1) bridged azide groups. On the other hand, the Zn(2) has a mixed organic and inorganic coordination environment with one PMT as a tridentate pincer chelate and one chloride ion, in addition to the bridged azide group. Hence the coordination numbers of the Zn(1) and Zn(2) sites are 4 and 5, respectively, while the coordination geometries are distorted tetrahedral and mixed square pyramidal/trigonal bipyramidal configurations, respectively. The molecular packing of this complex is controlled by short H…C (10.1%), N…H (17.2%), and Cl…C (2.0%) interactions. Due to symmetry consideration, the asymmetric formula of this complex is half [Zn3(PMT)2(Cl4)(N3)2] formula unit. The charges at the Zn(1) and Zn(2) are calculated to be +0.996 e and +1.067 e, respectively which are less than that for the isolated Zn(II) ion. While the Zn–N and Zn–Cl bonds have predominant closed shell characters, the two N–N bonds of the azide have clear covalent characters based on AIM analysis. The Zn–N bond distances were found to correlate inversely with the electron density function (ρ).

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/cryst12121786/s1, Figure S1. FTIR spectra of the trinuclear [Zn3(PMT)2(Cl4)(N3)2] complex; physicochemical characterizations; synthesis of PMT; X-ray measurements and computational details.

Author Contributions

Conceptualization, S.M.S., A.E.-F. and R.A.M.; methodology, R.A.M. and S.M.S.; software, R.A.M. and S.M.S.; validation, R.A.M., A.E.-F., K.A.D. and S.M.S.; formal analysis, R.A.M., A.E.-F., K.A.D. and S.M.S.; investigation, R.A.M. and S.M.S.; resources, R.A.M., A.E.-F., K.A.D. and S.M.S.; data curation, R.A.M., A.E.-F. and S.M.S.; writing—original draft preparation, R.A.M., A.E.-F. and S.M.S.; writing—review and editing, R.A.M., A.E.-F., K.A.D. and S.M.S.; visualization, R.A.M. and S.M.S.; supervision, R.A.M. and S.M.S.; project administration, R.A.M., A.E.-F., K.A.D. and S.M.S.; funding acquisition, A.E.-F., K.A.D. and S.M.S. All authors have read and agreed to the published version of the manuscript.

Funding

This project was funded by the Researchers Supporting Project number (RSP-2021/388), King Saud University, Riyadh, Saudi Arabia.

Data Availability Statement

Not applicable.

Acknowledgments

The authors extend their sincere appreciation to the Researchers Supporting Project (RSP-2021/388), King Saud University, Riyadh, Saudi Arabia.

Conflicts of Interest

The authors declare no conflict of interest.

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Crystals 12 01786 g001 550
Figure 1. Structure of the PMT ligand.
Figure 1. Structure of the PMT ligand.
Crystals 12 01786 g001
Crystals 12 01786 sch001 550
Scheme 1. Coordination modes for azide ion.
Scheme 1. Coordination modes for azide ion.
Crystals 12 01786 sch001
Crystals 12 01786 sch002 550
Scheme 2. Synthesis of different Zn(II) complexes with different anions.
Scheme 2. Synthesis of different Zn(II) complexes with different anions.
Crystals 12 01786 sch002
Crystals 12 01786 g002 550
Figure 2. The X-ray structure of the [Zn3(PMT)2(Cl4)(N3)2] complex. Symmetry code: # −x,y,1/2−z.
Figure 2. The X-ray structure of the [Zn3(PMT)2(Cl4)(N3)2] complex. Symmetry code: # −x,y,1/2−z.
Crystals 12 01786 g002
Crystals 12 01786 g003 550
Figure 3. The hydrogen bond contacts in the [Zn3(PMT)2(Cl4)(N3)2] complex.
Figure 3. The hydrogen bond contacts in the [Zn3(PMT)2(Cl4)(N3)2] complex.
Crystals 12 01786 g003
Crystals 12 01786 g004 550
Figure 4. The packing scheme of the [Zn3(PMT)2(Cl4)(N3)2] complex units via non-classical C–H…N interactions along the ac plane.
Figure 4. The packing scheme of the [Zn3(PMT)2(Cl4)(N3)2] complex units via non-classical C–H…N interactions along the ac plane.
Crystals 12 01786 g004
Crystals 12 01786 g005 550
Figure 5. Hirshfeld surfaces for the trinuclear Zn(II) complex. The letters A, B, and C in the dnorm map refer to the H…C, N…H, and Cl…C contacts, respectively.
Figure 5. Hirshfeld surfaces for the trinuclear Zn(II) complex. The letters A, B, and C in the dnorm map refer to the H…C, N…H, and Cl…C contacts, respectively.
Crystals 12 01786 g005
Crystals 12 01786 g006 550
Figure 6. The possible intermolecular contacts and their percentages in the trinuclear Zn(II) complex.
Figure 6. The possible intermolecular contacts and their percentages in the trinuclear Zn(II) complex.
Crystals 12 01786 g006
Crystals 12 01786 g007 550
Figure 7. Decomposed fingerprint plots for the important interactions in the Zn(II) complex.
Figure 7. Decomposed fingerprint plots for the important interactions in the Zn(II) complex.
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Crystals 12 01786 g008 550
Figure 8. Correlation between the ρ and Zn–N bond distances.
Figure 8. Correlation between the ρ and Zn–N bond distances.
Crystals 12 01786 g008
Table
Table 1. Crystallographic data for the [Zn3(PMT)2(Cl4)(N3)2] complex.
Table 1. Crystallographic data for the [Zn3(PMT)2(Cl4)(N3)2] complex.
CCDC2219487
Empirical formulaC28H34Cl4N20O2Zn3
F.Wt1020.66 g/mol
T293(2) K
λ0.71073 Å
Crystal systemMonoclinic
Space groupC2/c
Unit cell dimensionsa = 18.549(11) Åα = 90°
b = 11.371(7) Åβ = 97.098(11)°
c = 20.123(11) Åγ = 90°
V4212.0(4) Å3
Z4
D (calc.)1.610 g/cm3
Absorption coefficient2.003 mm−1
F(000)2064
θ range for data collection2.21 to 30.58°
Index ranges−23 ≤ h ≤ 26, −16 ≤ k ≤ 16, −28 ≤ l ≤ 28
Reflections collected29,481
Independent reflections6452 [R(int) = 0.0365]
Completeness to θ = 25.35°99.50%
Refinement methodFull-matrix least-squares on F2
Data/restraints/parameters6452/0/264
Goodness-of-fit on F21.04
Final R indices [I > 2sigma(I)]R1 = 0.0414, wR2 = 0.1215
R indices (all data)R1 = 0.0632, wR2 = 0.1363
Largest diff. peak and hole1.456 and −0.639
Table
Table 2. The most important bond distances (Å) and angles (°) in the [Zn3(PMT)2(Cl4)(N3)2] complex.
Table 2. The most important bond distances (Å) and angles (°) in the [Zn3(PMT)2(Cl4)(N3)2] complex.
BondDistanceBondDistance
Zn1–N102.040(2)Zn2–N32.181(3)
Zn1–Cl12.2305(12)Zn2–Cl22.1924(14)
Zn2–N102.036(2)Zn2–N72.279(2)
Zn2–N82.072(2)
BondsAngleBondsAngle
N10–Zn1–N10 #105.87(14)N10–Zn2–Cl2111.83(8)
N10–Zn1–Cl1110.55(8)N8–Zn2–Cl2142.79(7)
N10–Zn1–Cl1 #105.46(8)N3–Zn2–Cl2103.76(7)
Cl1–Zn1–Cl1 #118.35(7)N10–Zn2–N794.69(9)
N10–Zn2–N8104.77(10)N8–Zn2–N771.66(8)
N10–Zn2–N3102.91(9)N3–Zn2–N7143.96(8)
N8–Zn2–N373.53(8)Cl2–Zn2–N798.30(6)
Symmetry code: # −x,y,1/2−z.
Table
Table 3. AIM parameters (a.u.) for Zn–N and Zn–Cl bonds in the [Zn3(PMT)2(Cl4)(N3)2] complex.
Table 3. AIM parameters (a.u.) for Zn–N and Zn–Cl bonds in the [Zn3(PMT)2(Cl4)(N3)2] complex.
BondBDρG(r) aV(r) bH(r)V(r)/G(r)
Zn1–Cl12.2300.04310.0864−0.08030.00600.930
Zn1–N102.0400.05680.1138−0.11110.00270.976
Zn2–N32.1810.03350.0505−0.0507−0.00021.004
Zn2–N72.2790.02770.0537−0.04850.00520.903
Zn2–N82.0720.05200.1044−0.10120.00310.969
Zn2–N102.0360.05720.1172−0.11410.00310.974
Zn2–Cl22.1930.04610.0960−0.08890.00710.926
N10–N11.2100.46070.3902−1.0560−0.66582.706
N1–N111.1290.57250.5704−1.5492−0.97882.716
a G(r): kinetic energy density; b V(r): potential energy density.
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Dahlous, K.A.; Soliman, S.M.; El-Faham, A.; Massoud, R.A. Synthesis and X-ray Structure Combined with Hirshfeld and AIM Studies on a New Trinuclear Zn(II)-Azido Complex with s-Triazine Pincer Ligand. Crystals 2022, 12, 1786. https://doi.org/10.3390/cryst12121786

AMA Style

Dahlous KA, Soliman SM, El-Faham A, Massoud RA. Synthesis and X-ray Structure Combined with Hirshfeld and AIM Studies on a New Trinuclear Zn(II)-Azido Complex with s-Triazine Pincer Ligand. Crystals. 2022; 12(12):1786. https://doi.org/10.3390/cryst12121786

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Dahlous, Kholood A., Saied M. Soliman, Ayman El-Faham, and Raghdaa A. Massoud. 2022. "Synthesis and X-ray Structure Combined with Hirshfeld and AIM Studies on a New Trinuclear Zn(II)-Azido Complex with s-Triazine Pincer Ligand" Crystals 12, no. 12: 1786. https://doi.org/10.3390/cryst12121786

APA Style

Dahlous, K. A., Soliman, S. M., El-Faham, A., & Massoud, R. A. (2022). Synthesis and X-ray Structure Combined with Hirshfeld and AIM Studies on a New Trinuclear Zn(II)-Azido Complex with s-Triazine Pincer Ligand. Crystals, 12(12), 1786. https://doi.org/10.3390/cryst12121786

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