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Article

X-ray Structures and Hirshfeld Studies of Two Dinuclear Cd(II) Complexes with a s-Triazine/Pyrazolo Ligand and Pesudohalides as a Linker

by
Saied M. Soliman
1,*,
Hessa H. Al-Rasheed
2,*,
Sarah A. AL-khamis
2,
Matti Haukka
3 and
Ayman El-Faham
1
1
Department of Chemistry, Faculty of Science, Alexandria University, P.O. Box 426, Ibrahimia, Alexandria 21321, Egypt
2
Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia
3
Department of Chemistry, University of Jyväskylä, P.O. Box 35, FI-40014 Jyväskylä, Finland
*
Authors to whom correspondence should be addressed.
Crystals 2023, 13(8), 1198; https://doi.org/10.3390/cryst13081198
Submission received: 20 July 2023 / Revised: 29 July 2023 / Accepted: 31 July 2023 / Published: 2 August 2023
(This article belongs to the Section Organic Crystalline Materials)
Browse Figures
Versions Notes

Abstract

:
The two dinuclear Cd(II) complexes [Cd(BPMST)(SCN)]2 (1) and [Cd(BPMST)(N3)Cl]2 (2) of a s-triazine/pyrazolo ligand (BPMST) were synthesized. The preparation of both complexes was performed in a water–ethanol solvent mixture and involved the mixing of the functional ligand BPMST with CdCl2 in the presence of thiocyanate or azide as linkers, respectively. The dinuclear formula of both complexes and the involvement of the pesudohalide as a linker between the Cd(II) centers were approved by single crystal X-ray structures. The Cd(II) was hexa-coordinated and the CdN5S (1) and CdN5Cl (2) coordination environments had distorted octahedral geometry. In the [Cd(BPMST)(SCN)]2 and [Cd(BPMST)(N3)Cl]2, the BPMST acted as a pincer tridentate N-chelate. In the case of 1, the SCN¯ acted as a μ(1,3) bridging ligand between the Cd(II) centers, while the N3¯ had a μ(1,1) bridging mode in 2. As a result, the Cd…Cd distance was significantly longer in 1 (5.8033(5) Å) than in 2 (3.796(2) Å). In both complexes, the Cd(II) had distorted octahedral coordination geometry. Hirshfeld surface analysis was performed to inspect the supramolecular aspects of the two Cd(II) complexes. The C…H, N…H and S…H contacts were important in the case of [Cd(BPMST)(SCN)]2 (1). Their percentages were calculated to be 14.7, 17.0 and 13.4%, respectively. In the case of [Cd(BPMST)(N3)Cl]2 (2), the most significant contacts were the Cl…H, C…H and N…H contacts. Their contributions in the molecular packing were 16.5, 9.7 and 25.3%, respectively. The propensity of atom pairs of elements to form contacts in the crystal structure was analyzed using enrichment ratio (EXY).

1. Introduction

Cadmium is an extremely poisonous heavy metal [1,2,3,4]. Despite this well-known fact, Cd and its compounds are of great importance. Cd serves as a catalytic center in carbonic anhydrase [5]. Also, it has interesting DNA binding abilities [6,7,8], antibacterial activities [9,10] and antitumor properties [11,12] and is a known catalyst for organic transformations [13,14,15,16,17,18]. Also, Cd(II) compounds have many applications in photoluminescence and non-linear optics [19,20,21,22]. Cd(II) coordination compounds with N-donor ligands have successful applications in ligand exchange chromatography [23,24,25]. Also, Cd(II) complexes have interesting and versatile applications in nanoscience [26,27]. From an electronics point of view, Cd(II) has high flexibility to form complexes with diverse coordination numbers ranging from four to eight. In this regard, the self-assembly method is a very simple technique used for the synthesis of coordination compounds with fascinating molecular and supramolecular structures [28,29,30,31,32,33,34,35,36,37].
s-triazines are attractive ligands for researchers interested in building interesting coordination compounds due to their flexible coordination behavior [38,39,40,41,42,43] and brilliant ability to construct metal complexes with fascinating supramolecular structures [44,45,46]. s-triazine coordination compounds are stable compounds with fascinating properties [47,48,49,50,51,52,53,54,55]. In addition, the highly symmetric structure of s-triazine (s-Trz) moiety is an important requirement in crystal engineering for the construction of interesting supramolecular structures [56,57,58,59,60,61,62,63,64,65,66]. s-triazine derivatives with two pyrazolyl (Pyz) arms (Figure 1) are considered tridentate chelates capable of binding metal ions in a pincer mode, leading to fascinating and stable metal complexes [45,67,68,69,70,71,72,73].
2,4-Bis(3,5-dimethyl-1H-pyrazol-1-yl)-6-diethylamino-1,3,5-triazine is a structurally related pincer ligand analog for the BPMST ligand. The crystal structures of the pesudohalide complexes of 2,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)-6-diethylamino -1,3,5-triazine with the d7–d10 metal ion were reported. It was found that the Co(II) and Cu(II) metal ions formed mononuclear pesudohalide complexes. In the case of Ni(II), dinuclear pesudohalide complexes were obtained. The surface photovoltage (SPV) response suggested these complexes to extend to semiconductor materials [67]. Recently, a number of mononuclear complexes of the BPMST ligand were presented by our research group [45,68,69,70,71,72,73,74]. In order to increase the nuclearity of the complex, a linker such as azide or thiocyanate could be used to achieve this target. In this work, the reaction products of the self-assembly of CdCl2 with BPMST in the presence of azide or thiocyanate as linkers were presented. Their X-ray structures were presented for the first time. In addition, their supramolecular structures were investigated using Hirshfeld analysis.

2. Materials and Methods

All details for chemicals and solvents are mentioned in the Supplementary Data.

2.1. Syntheses

The ligand BPMST was prepared according to the described method by our research team [44,45].

Synthesis of the Cd(II) Complexes[Cd(BPMST)(SCN)]2 (1) and [Cd(BPMST)(N3)Cl]2 (2)

A total of 10 mL of BPMST (0.06 g, 0.2 mmol) in EtOH was mixed with CdCl2 (0.037 g, 0.2 mmol) in 5 mL of distilled H2O in the presence of 0.5 mL of a saturated aqueous KSCN or NaN3 solution. The complexes [Cd(BPMST)(SCN)]2 (1) and [Cd(BPMST)(N3)Cl]2 (2) were assembled from the solution as colorless crystals after 8 and 10 days, respectively.
The yields were as follows: C16H17CdN9OS2 (1): 89.1%. Anal. Calc. N, 23.88; H, 3.25; C, 36.4; Cd, 21.29%. Found: N, 23.67; H, 3.16; C, 36.14; Cd, 21.11%. IR (KBr, cm−1): 3103, 2137, 2033, 1606, 1541; Figure S1 (Supplementary Data). C14H17CdClN10O (2): 82.1%. Anal. Calc. N, 28.63; H, 3.50; C, 34.37; Cd, 22.98. Found: N, 28.40; H, 3.39; C, 34.05; Cd, 22.77%. FTIR (KBr, cm−1): 3115, 3022, 2959, 2048, 1596, 1572, 1538; Figure S2 (Supplementary Data).

2.2. Crystal Structure Determination

The single crystal structure of complexes 1 and 2 was determined using a Bruker D8 Quest diffractometer. The experimental details are provided in Method S1 (Supplementary Data) [75]. Crystal data are depicted in Table S1.

2.3. Hirshfeld Surface Analysis

The Crystal Explorer [76] program was used to generate the 2D fingerprint plots and study the Hirshfeld surfaces.

3. Results and Discussion

3.1. Synthesis and Characterizations

In previous studies, the pincer ligand, 2,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)-6-diethylamino-1,3,5-triazine, gave mononuclear pseudohalide complexes with Cu(II) and Co(II) ions. On the other hand, the dinuclear pesudohalide complexes that are not commonly reported in the literature on this class of ligand were obtained in the case of Ni(II) [74]. In the current study, the two dinuclear Cd(II) complexes, [Cd(BPMST)(SCN)]2 (1) and [Cd(BPMST)(N3)Cl]2 (2), were synthesized by mixing equimolar amounts of BPMST with CdCl2 in the presence of thiocyanate or azide as a linker in a water–ethanol solvent mixture. The two products were isolated in a highly crystalline form and in good yields. Solving the structure with the aid of single-crystal X-ray diffraction confirmed the dinuclear formula of the Cd(II) complexes and the involvement of the pesudohalide as a linker connecting the two Cd(II) ions (Scheme 1). In addition, FTIR spectra showed two sharp bands characteristic of the bridged SCN¯ at 2137 and 2033 cm−1 in the case of complex 1. The sharp band at 2048 cm−1 in the FTIR spectra of complex 2 confirmed the presence of the bridged azide. In the FTIR spectra of complexes 1 and 2, the vibrational characteristics of the BPMST were detected with some variation compared to those of the free BPMST. While the υC=C and υC=N modes of the free BPMST were observed at 1555 and 1593 cm−1, respectively (), the corresponding values in the case of complex 1 were detected at 1606 and 1541 cm−1, respectively. For 2, the υC=N modes were detected as a doubly split band at 1596 and 1572 cm−1, while the υC=C mode was detected at 1538 cm−1 (Figures S1–S3, Supplementary Data).

3.2. Crystal Structure Description

The X-ray structure of the [Cd(BPMST)(SCN)]2 complex is shown in Figure 2. The results indicated a dinuclear structure in which there is one [Cd(BPMST)(SCN)] as an asymmetric formula where two of these units were connected by the bridged μ(1,3) thiocyanate groups. The complex crystallized in the orthorhombic crystal system and space group Pbca with the unit cell parameters were determined to be a = 14.6614(5) Å, b = 15.9147(6) Å and c = 18.0194(7) Å. The unit cell volume was 4204.5(3) Å3 and the calculated crystal density was 1.668 g/cm3.
In this dinuclear complex, the Cd(II) had a CdN5S hexa-coordination environment. There were three short Cd1-N4 (2.402(3) Å), Cd1-N6 (2.454(3) Å) and Cd1-N1 (2.348(3) Å) bonds with the BPMST ligand. Hence, the BPMST ligand acted as tridentate N-chelate via two N-atoms (N4 and N6) from the Pyz moieties and another N-atom (N1) from the s-Trz core. The bite angles N6-Cd1-N1 (66.06(9)°) and N1-Cd1-N4 (66.63(10)°) of the BPMST ligand were almost the same, while the trans-N4-Cd1-N6 was almost twice this value (131.93(10)°). In addition, the Cd(II) was coordinated with three SCN¯ groups. Two of the SCN¯ groups were bridged ligands connecting the two crystallographically dependent Cd(II) centers via Cd1-N9 (2.6170(11) Å) and Cd1-S1 (2.258(3) Å) bonds where the N9-Cd1-S1 angle was 92.07(8)°. The third SCN¯ group was terminal and coordinated with the Cd(II) center via N8, where the respective Cd1-N8 bond distance was 2.287(3) Å, which was shorter than the corresponding Cd1-N9 bond of the bridged thiocyanate. The trans N9-Cd1-N8 angle was 171.72(12)°, while the cis S1-Cd1-N8 angle was 84.40(9)°. Details of the geometric parameters for the coordination sphere are listed in Table 1. It was clear that the CdN5S coordination sphere had a distorted octahedral configuration. Due to the μ(1,3) bridging mode of the thiocyanate group, the distance between the crystallographically related Cd sites was quite large. The Cd1…Cd1 distance was determined to be 5.8033(5) Å.
The supramolecular structure of the [Cd(BPMST)(SCN)]2 complex was dominated by a weak C12-H12A…N8 interaction. The acceptor N8 to donor C12 distance was 3.454(4) Å, while the hydrogen H12A to acceptor N8 distance was 2.660 Å. Views of the C12-H12A…N8 contacts and packing scheme are shown in Figure 3 and Figure 4, respectively.
In addition, the terminal thiocyanate group with the free S2 atom that did not participate in a coordination interaction with the Cd(II) ion was involved in anion-π stacking interactions with the coordinated s-triazine group. The S2…C3 contact distance was 3.497(3) Å and a presentation for this anion-π stacking interaction is shown in Figure 5.
The structure analysis for the single crystal of the [Cd(BPMST)(N3)Cl]2 complex is depicted in Table S1. The formula [Cd(BPMST)(N3)Cl] represents the asymmetric unit of the dinuclear complex. The two [Cd(BPMST)(N3)Cl] units were connected by the bridged azide groups. In this case, the crystal system was triclinic and the space group was P-1. The triclinic crystal parameters were a = 9.323(4) Å, b = 10.936(5) Å, c = 11.312(5) Å, α = 112.637(10)°, β = 104.547(11)° and γ = 105.133(10)°. The unit cell volume was 944.2(12) Å3 and the calculated crystal density was 1.721 g/cm3. The structure of the [Cd(BPMST)(N3)Cl]2 complex is shown in Figure 6.
The structure of the dinuclear azido complex [Cd(BPMST)(N3)Cl]2 was quite different. In this case, the Cd(II) ion was coordinated to one BPMST ligand unit also as a tridentate pincer ligand. The Cd1-N1, Cd1-N4 and Cd1-N6 distances were determined to be 2.411(2), 2.409(2) and 2.451(2) Å, respectively. In this case, the distance between the Cd1 site and the N1-atom of the s-triazine core was not the shortest, while the Cd1-N4 with one of the pyrazolyl moieties was the shortest. Also, the bite angles N1-Cd1-N6 (64.57(7)°) and N1-Cd1-N4 (65.64(7)°) of the BPMST ligand were almost the same, but both were slightly less than those found in the [Cd(BPMST)(SCN)]2 complex. The trans-N4-Cd1-N6 was 130.14(7)°, which was also twice the bite angle values. The coordination sphere of the Cd(II) was accomplished by two μ(1,1) bridged azide ions and one terminal chloride ion (Figure 6). The Cd1-N8 and Cd1-N8# distances were determined to be 2.415(3) and 2.322(3) Å, respectively. In this case, the distance between the crystallographically related Cd sites was significantly small (3.796(2) Å) compared to the corresponding Cd…Cd distance in the [Cd(BPMST)(SCN)]2 complex. The Cd1-Cl1 distance was 2.4700(13) Å, and a list of the angles around the coordination environment is depicted in Table 2. It is clear that all bond angle values deviated significantly from the ideal values of the perfect octahedron. Hence, the CdN5Cl coordination sphere had a distorted octahedral configuration.
The packing of the [Cd(BPMST)(N3)Cl]2 complex was controlled by a weak C12-H12C…N10 interaction. The donor C12 to acceptor N10 distance was 3.547(6) Å, while the hydrogen H12C to acceptor N10 distance was 2.61 Å. Views of the C12-H12C…N10 contacts and packing scheme are shown in Figure 7.
In addition, the [Cd(BPMST)(N3)Cl]2 units were connected by some Cl…H interactions between the coordinated chloride ion as an H-bond acceptor with C14-H14A as an H-bond donor (Figure 8). The acceptor Cl1 to donor C14 distance was 3.638(4) Å.

3.3. Analysis of Molecular Packing

The crystalline materials were characterized by a well-organized arrangement, which kept the crystal stable via a complicated set of non-covalent interactions involving hydrogen bonds, C-H…π, anion-π interactions, etc. Hirshfeld topology analysis is a lead method for detecting all possible non-covalent interactions that control the stability of a crystal structure. The different Hirshfeld surfaces for the complex [Cd(BPMST)(SCN)]2(1) are shown in Figure 9. It is clear that the dnorm map showed some red spots. These red spots are related to regions involved in short non-covalent interactions with neighboring molecules. The most important non-covalent interactions were the C…H, N…H and S…H contacts, which are labeled as A, B and C, respectively. C14…H16C, N8…H12A and S2…H5 were the shortest interactions, where the corresponding contact distances were 2.627, 2.567 and 2.881 Å, respectively.
In addition, Figure 10 shows the characteristic fingerprint plots of the C…H, N…H and S…H interactions. The appearance of these contacts as spikes in the corresponding fingerprint plots indicated their relevance in the molecular packing of the [Cd(BPMST)(SCN)]2 complex. In addition, the area of the colored region of each plot gave an indication of the percentages of these intermolecular contacts. The percentages of the C…H, N…H and S…H interactions were calculated to be 14.7, 17.0 and 13.4%, respectively.
In addition, there were many other weak interactions that affected the supramolecular structure of the [Cd(BPMST)(SCN)]2 complex. A summary of all interactions and their contributions to the molecular packing are shown in Figure 11. The most common interaction was hydrogenic H…H contacts (35.7%). In addition, there was a small number of weak S…C contacts that contributed 3.4% of all interactions. This interaction appears as a white region in the dnorm map, indicating equal interaction distance to the vdWs radii sum of the S and C atoms. Hence, the anion-π interaction in this complex was considered relatively weak.
For the [Cd(BPMST)(N3)Cl]2 complex (2), the different Hirshfeld maps are presented in Figure 12. In this case, the red spots in the dnorm map correspond to the Cl…H, C…H, N…H and H…H interactions. These contacts are labeled as letters A to D, respectively. Cl1…H14A, N10…H12C, C5…H11B and H13A…H13C were the shortest interactions. Their respective contact distances were 2.770, 2.485, 2.657 and 2.515 Å, respectively. Similar to the observation detected in the fingerprint plots of the [Cd(BPMST)(SCN)]2 complex, the decomposed fingerprint plots of Cl…H, C…H and N…H appeared as sharp spikes (Figure 13). This was considered further evidence of the significance of these interactions in the molecular packing of the [Cd(BPMST)(N3)Cl]2 complex (2).
Additionally, the percentages of all possible non-covalent interactions that occurred in the [Cd(BPMST)(N3)Cl]2 complex (2) are shown in Figure 14. The percentages of the Cl…H, C…H, N…H and H…H contacts were 16.5, 9.7, 25.3 and 37.1%, respectively. In addition, there was a small contribution from the polar O…H interaction (6.4%), which appeared to be weak and had less important molecular packing compared to the Cl…H, C…H and N…H interactions.
In addition, the intermolecular interactions were further analyzed based on the enrichment ratio (EXY) parameter [77]. The enrichment ratio (EXY) of a pair of elements (X,Y) gave an indication of their propensity to form contacts in crystals. It is defined by the ratio of the proportion of the contact (CXY) to the theoretical proportion of random contact (RXY) [77]. The enrichment ratio is greater than 1 for atom pairs with a high propensity to form contacts. In contrast, the atom pairs that avoid contacts have an enrichment ratio lower than 1. The enrichment ratio EXY of complexes 1 and 2 was calculated and the results are depicted in Table 3. In the case of the azido complex 2, the enrichment ratio was greater than that for the Cl…H, O…H and N…H contacts and equal to one for the C…H interaction. On the other hand, EXY > 1 for the O…H, N…H, N…S, C…N and C…S contacts, while EXY = 1 for the C…H, S…H and H…H interactions. These results indicate that the atom pairs had a high propensity to form contacts. In contrast, the rest of the intermolecular contacts listed in the table showed a lower propensity to form contacts in the crystal structure.

4. Conclusions

The self-assembly of the functional ligand BPMST with CdCl2 in the presence of a linker such as thiocyanate or azide in a water–ethanol solution gave the dinuclear Cd(II) complexes [Cd(BPMST)(SCN)]2 (1) and [Cd(BPMST)(N3)Cl]2 (2), respectively. The s-triazine/pyrazolo ligand (BPMST) acted as a pincer tridentate N-chelator. The pesudohalides SCN¯ and N3¯ acted as linkers between the two Cd(II) centers in μ(1,3) and μ(1,1) bridging modes, respectively. Analysis of the non-covalent interactions with the aid of Hirshfeld topology calculations indicated the importance of the C…H (14.7%), N…H (17.0) and S…H (13.4%) contacts in the molecular packaging of [Cd(BPMST)(SCN)]2 (1). On the other hand, the Cl…H (16.5%), C…H (9.7%) and N…H (25.3%) interactions were the most significant in the supramolecular structure of [Cd(BPMST)(N3)Cl]2 (2). Enrichment ratio (EXY) calculations were used to inspect the propensity of atom pairs of elements (X,Y) to form contacts in crystals.

Supplementary Materials

The following supporting information can be downloaded at https://www.mdpi.com/article/10.3390/cryst13081198/s1: Method S1 Crystal structure determination; Figure S1 FTIR spectra of 1. Figure S2 FTIR spectra of 2; Figure S3 FTIR spectra of BPMST; Table S1 Crystal data for complexes [Cd(BPMST)(SCN)]2 (1) and [Cd(BPMST)(N3)Cl]2 (2).

Author Contributions

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

Funding

The Deputyship for Research and Innovation, “Ministry of Education”, King Saud University (IFKSUOR3-188-2), Saudi Arabia.

Data Availability Statement

All data generated or analyzed during this study are included in this published article.

Acknowledgments

The authors extend their appreciation to the Deputyship for Research and Innovation, “Ministry of Education” in Saudi Arabia for funding this research (IFKSUOR3-188-2).

Conflicts of Interest

The authors declare no conflict of interest.

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Crystals 13 01198 g001
Figure 1. Structure of the BPMST.
Figure 1. Structure of the BPMST.
Crystals 13 01198 g001
Crystals 13 01198 sch001
Scheme 1. Synthesis of complexes [Cd(BPMST)(SCN)]2 (1) and [Cd(BPMST)(N3)Cl]2 (2).
Scheme 1. Synthesis of complexes [Cd(BPMST)(SCN)]2 (1) and [Cd(BPMST)(N3)Cl]2 (2).
Crystals 13 01198 sch001
Crystals 13 01198 g002
Figure 2. X-ray structure of [Cd(BPMST)(SCN)]2 complex (1). Symmetry code #: 1 − x, 1 − y, −z.
Figure 2. X-ray structure of [Cd(BPMST)(SCN)]2 complex (1). Symmetry code #: 1 − x, 1 − y, −z.
Crystals 13 01198 g002
Crystals 13 01198 g003
Figure 3. The N…H intermolecular contacts in the [Cd(BPMST)(SCN)]2 complex (1).
Figure 3. The N…H intermolecular contacts in the [Cd(BPMST)(SCN)]2 complex (1).
Crystals 13 01198 g003
Crystals 13 01198 g004
Figure 4. Packing structure for the [Cd(BPMST)(SCN)]2 complex (1).
Figure 4. Packing structure for the [Cd(BPMST)(SCN)]2 complex (1).
Crystals 13 01198 g004
Crystals 13 01198 g005
Figure 5. The anion-π stacking interactions in the [Cd(BPMST)(SCN)]2 complex (1).
Figure 5. The anion-π stacking interactions in the [Cd(BPMST)(SCN)]2 complex (1).
Crystals 13 01198 g005
Crystals 13 01198 g006
Figure 6. X-ray structure of [Cd(BPMST)(N3)Cl]2 (2). Symmetry code #: 1 − x, 2 − y, 1 − z.
Figure 6. X-ray structure of [Cd(BPMST)(N3)Cl]2 (2). Symmetry code #: 1 − x, 2 − y, 1 − z.
Crystals 13 01198 g006
Crystals 13 01198 g007
Figure 7. The N…H intermolecular interactions (A) and packing view (B) for the [Cd(BPMST)(N3)Cl]2 complex (2).
Figure 7. The N…H intermolecular interactions (A) and packing view (B) for the [Cd(BPMST)(N3)Cl]2 complex (2).
Crystals 13 01198 g007
Crystals 13 01198 g008
Figure 8. The packing structure of the [Cd(BPMST)(N3)Cl]2 complex via Cl…H intermolecular contacts.
Figure 8. The packing structure of the [Cd(BPMST)(N3)Cl]2 complex via Cl…H intermolecular contacts.
Crystals 13 01198 g008
Crystals 13 01198 g009
Figure 9. Hirshfeld surfaces for [Cd(BPMST)(SCN)]2 (1). A, B and C are related to C…H, N…H and S…H interactions, respectively.
Figure 9. Hirshfeld surfaces for [Cd(BPMST)(SCN)]2 (1). A, B and C are related to C…H, N…H and S…H interactions, respectively.
Crystals 13 01198 g009
Crystals 13 01198 g010
Figure 10. Fingerprint plots for the C…H, N…H and S…H interactions in the complex [Cd(BPMST)(SCN)]2 (1).
Figure 10. Fingerprint plots for the C…H, N…H and S…H interactions in the complex [Cd(BPMST)(SCN)]2 (1).
Crystals 13 01198 g010
Crystals 13 01198 g011
Figure 11. Intermolecular interactions in [Cd(BPMST)(SCN)]2 (1).
Figure 11. Intermolecular interactions in [Cd(BPMST)(SCN)]2 (1).
Crystals 13 01198 g011
Crystals 13 01198 g012
Figure 12. Hirshfeld surfaces for the [Cd(BPMST)(N3)Cl]2 complex (2). The Cl…H (A), C…H (B), N…H (C) and H…H (D) contacts are shown in the dnorm map for clarity.
Figure 12. Hirshfeld surfaces for the [Cd(BPMST)(N3)Cl]2 complex (2). The Cl…H (A), C…H (B), N…H (C) and H…H (D) contacts are shown in the dnorm map for clarity.
Crystals 13 01198 g012
Crystals 13 01198 g013
Figure 13. Fingerprint plots for the Cl…H, C…H, N…H and H…H interactions in the [Cd(BPMST)(N3)Cl]2 complex (2).
Figure 13. Fingerprint plots for the Cl…H, C…H, N…H and H…H interactions in the [Cd(BPMST)(N3)Cl]2 complex (2).
Crystals 13 01198 g013
Crystals 13 01198 g014
Figure 14. Intermolecular interactions in the [Cd(BPMST)(N3)Cl]2 complex (2).
Figure 14. Intermolecular interactions in the [Cd(BPMST)(N3)Cl]2 complex (2).
Crystals 13 01198 g014
Table 1. Bond lengths (Å) and angles (°) for the [Cd(BPMST)(SCN)]2 complex (1).
Table 1. Bond lengths (Å) and angles (°) for the [Cd(BPMST)(SCN)]2 complex (1).
BondLength/ÅBondLength/Å
Bond distances
Cd1-N9 #2.258(3)Cd1-N42.402(3)
Cd1-N82.287(3)Cd1-N62.454(3)
Cd1-N12.348(3)Cd1-S12.6170(11)
Bond angles
N9 #-Cd1-N8171.72(12)N1-Cd1-N666.06(9)
N9 #-Cd1-N199.30(10)N4-Cd1-N6131.93(10)
N8-Cd1-N184.99(11)N9 #-Cd1-S192.07(8)
N9 #-Cd1-N487.14(11)N8-Cd1-S184.40(9)
N8-Cd1-N4101.09(12)N1-Cd1-S1167.45(7)
N1-Cd1-N466.63(10)N4-Cd1-S1108.99(8)
N9 #-Cd1-N692.31(11)N6-Cd1-S1119.06(7)
N8-Cd1-N682.93(12)
# 1 − x, 1 − y, −z.
Table 2. Bond lengths (Å) and angles (°) for the [Cd(BPMST)(N3)Cl]2 complex (2).
Table 2. Bond lengths (Å) and angles (°) for the [Cd(BPMST)(N3)Cl]2 complex (2).
BondLength/ÅBondLength/Å
Bond distances
Cd1-Cl12.4700(13)Cd1-N8 #2.322(3)
Cd1-N42.409(2)Cd1-N12.411(2)
Cd1-N82.415(3)Cd1-N62.451(2)
Bond angles
N8 #-Cd1-N4109.11(10)N8 #-Cd1-N1154.32(9)
N4-Cd1-N165.64(7)N8-Cd1-N8 #73.49(12)
N4-Cd1-N890.55(10)N1-Cd1-N881.31(8)
N8 #-Cd1-N6116.69(10)N4-Cd1-N6130.14(7)
N1-Cd1-N664.57(7)N8-Cd1-N684.58(10)
N8 #-Cd1-Cl195.60(8)N4-Cd1-Cl195.94(6)
N1-Cd1-Cl1109.80(6)N8-Cd1-Cl1168.70(7)
N6-Cd1-Cl198.15(7)
# 1 − x, 1 − y, −z.
Table 3. Enrichment ratio EXY of the different inter-contacts in complexes [Cd(BPMST)(SCN)]2 (1) and [Cd(BPMST)(N3)Cl]2 (2).
Table 3. Enrichment ratio EXY of the different inter-contacts in complexes [Cd(BPMST)(SCN)]2 (1) and [Cd(BPMST)(N3)Cl]2 (2).
Enrichment Ratio (EXY)
[Cd(BPMST)(SCN)]2 (1)[Cd(BPMST)(N3)Cl]2 (2)
O…H1.4O…H1.4
H…H1.0H…H0.8
N…H1.1N…H1.3
C…H1.0C…H1.0
S…S0.3N…O0.1
N…S1.6N…N0.5
C…N1.3C…N0.8
C…S1.2Cl…H1.5
C…C0.7
S…H1.0
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Soliman, S.M.; Al-Rasheed, H.H.; AL-khamis, S.A.; Haukka, M.; El-Faham, A. X-ray Structures and Hirshfeld Studies of Two Dinuclear Cd(II) Complexes with a s-Triazine/Pyrazolo Ligand and Pesudohalides as a Linker. Crystals 2023, 13, 1198. https://doi.org/10.3390/cryst13081198

AMA Style

Soliman SM, Al-Rasheed HH, AL-khamis SA, Haukka M, El-Faham A. X-ray Structures and Hirshfeld Studies of Two Dinuclear Cd(II) Complexes with a s-Triazine/Pyrazolo Ligand and Pesudohalides as a Linker. Crystals. 2023; 13(8):1198. https://doi.org/10.3390/cryst13081198

Chicago/Turabian Style

Soliman, Saied M., Hessa H. Al-Rasheed, Sarah A. AL-khamis, Matti Haukka, and Ayman El-Faham. 2023. "X-ray Structures and Hirshfeld Studies of Two Dinuclear Cd(II) Complexes with a s-Triazine/Pyrazolo Ligand and Pesudohalides as a Linker" Crystals 13, no. 8: 1198. https://doi.org/10.3390/cryst13081198

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