Phenazine and 10H-phenothiazine cocrystal stabilized by N-H···N and C-H···S hydrogen bonds European Journal of Chemistry 13 (2) (2022) 230-233 European Journal of Chemistry ISSN 2153-2249 (Print) / ISSN 2153-2257 (Online) – Copyright © 2022 The Authors – Atlanta Publishing House LLC – Printed in the USA. This work is published and licensed by Atlanta Publishing House LLC – CC BY NC – Some Rights Reserved. https://dx.doi.org/10.5155/eurjchem.13.2.230-233.2256 European Journal of Chemistry View Journal Online View Article Online Phenazine and 10H-phenothiazine cocrystal stabilized by N-H···N and C-H···S hydrogen bonds Tahir Mehmood 1, Bhumiben Chandubhai Patel 1 and Jayarama Prakasha Reddy 1,2,* 1 Department of Chemistry, School of Sciences, Indrashil University, Rajpur, Gujarat 382740, India 2 School of Applied Material Sciences, Central University of Gujarat, Gandhinagar 382030, India * Corresponding author at: Department of Chemistry, School of Sciences, Indrashil University, Rajpur, Gujarat 382740, India. e-mail: jprakasha.reddy@indrashiluniversity.edu.in (J.P. Reddy). 10.5155/eurjchem.13.2.230-233.2256 Received: 09 March 2022 Received in revised form: 23 April 2022 Accepted: 27 April 2022 Published online: 30 June 2022 Printed: 30 June 2022 A 1:1 co-crystal of phenazine and phenothiazine was prepared. The crystal structure was determined by using a single crystal X-ray crystallography technique. Analysis of the crystal revealed that the molecular complex crystallizes in monoclinic P21/n space group, C12H8N2·C12H9NS, a = 9.068(2) Å, b = 8.872(2) Å, c = 23.935(4) Å, β = 92.16(4)°, V = 1924.1(6) Å3, Z = 4, T = 293(2) K, μ(MoKα) = 0.182 mm-1, Dcalc = 1.310 g/cm3, 8057 reflections measured (3.4° ≤ 2Θ ≤ 46.54°), 2751 unique (Rint = 0.0559, Rsigma = 0.0618) which were used in all calculations. The final R1 was 0.0548 (>2sigma(I)) and wR2 was 0.1029 (all data). The molecules recognize each other through N-H···N and C-H···N hydrogen bonds, thus producing a tetramer unit. These units further interact with one another via C-H···S hydrogen bonds. Co-crystal Phenazine Phenothiazine Hydrogen bonding X-ray crystallography Supramolecular assembly Cite this: Eur. J. Chem. 2022, 13(2), 230-233 Journal website: www.eurjchem.com 1. Introduction The supramolecular structures of simple organic molecules, peptides, proteins, etc., that occur due to hydrogen bonding, have attracted a lot of attention due to their fascinating, aesthetic architectures, and potential applications [1-5]. In recent times, hydrogen bonded foldamers inhibiting human immunodeficiency virus HIV and mimicking charge surface of double stranded DNA have also been reported [6,7]. Synthesis of more than two-component systems (three and four- component systems) [8,9] has been reported using hydrogen bonding as a tool. As part of our ongoing research program aimed at creating novel supramolecular assemblies [10], we were interested in synthesizing a ternary assembly based on molecular recognition principles [11]. For this purpose, and taking into account the fact that 3,5-dinitrobenzamide (i) forms molecular complexes with aza-donor compounds such as 4,4'- bipyridine (ii), we chose to cocrystallize (i) with phenazine (iii) and phenothiazine (iv), hoping that a ternary assembly would result (Scheme 1). However, characterization of the single crystals obtained from a methanol solution by X-ray diffraction method revealed that only (iii) and (iv) co-crystallized. We have determined the crystal structure and analyzed the packing arrangement of the molecules in this complex, as neither three- dimensional coordinates nor analyses of non-covalent interac- tions are available from the preliminary information reported in the literature [12,13], although unit cell parameters are available. 2. Experimental 2.1. Synthesis Commercially available (Aldrich) 3,5-dinitrobenzamide (0.5 mmol), phenazine (0.5 mmol), and phenothiazine (0.5 mmol) were mixed in a methanol solution. Crystals suitable for X-ray diffraction analysis were obtained at ambient tempera- ture over a period of four days. 2.2. Crystal structure determination and refinement All operations were performed on a Bruker-Nonius Kappa APEX1 diffractometer [14], using graphite-monochromated MoKα radiation. All diffractometer manipulations, including data collection, integration, and absorption corrections, were carried out using Bruker APEX1 software [15]. The preliminary cell constants were obtained from three sets of 16 frames. Data collection was carried out at 298 K, using a frame time of 5 s and a detector distance of 50 mm. ABSTRACT RESEARCH ARTICLE KEYWORDS https://dx.doi.org/10.5155/eurjchem.13.2.230-233.2256 https://www.eurjchem.com/ https://dx.doi.org/10.5155/eurjchem.13.2.230-233.2256 mailto:jprakasha.reddy@indrashiluniversity.edu.in http://www.eurjchem.com/ https://crossmark.crossref.org/dialog/?doi=10.5155/eurjchem.13.2.230-233.2256&domain=pdf&date_stamp=2022-06-30 Mehmood et al. / European Journal of Chemistry 13 (2) (2022) 230-233 231 2022 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.13.2.230-233.2256 Table 1. Crystal data and details of the structure refinement for the molecular complex. Empirical formula C24H17N3S Formula weight 379.4784 Temperature (K) 298(2) Crystal system Monoclinic Space group P21/n a, (Å) 9.068(2) b, (Å) 8.872(2) c, (Å) 23.935(4) β (°) 92.16(4) Volume (Å3) 1924.1(6) Z 4 ρcalc (g/cm3) 1.310 μ (mm-1) 0.182 F(000) 792.0 Crystal size (mm3) 0.21 × 0.18 × 0.11 Radiation MoKα (λ = 0.71073) 2Θ range for data collection (°) 3.4 to 46.54 Index ranges -10 ≤ h ≤ 10, -9 ≤ k ≤ 9, -26 ≤ l ≤ 15 Reflections collected 8057 Independent reflections 2751 [Rint = 0.0559, Rsigma = 0.0618] Data/restraints/parameters 2751/0/321 Goodness-of-fit on F2 0.951 Final R indexes [I≥2σ (I)] R1 = 0.0548, wR2 = 0.0883 Final R indexes [all data] R1 = 0.1008, wR2 = 0.1029 Largest diff. peak/hole (e.Å-3) 0.15/-0.14 NO2O2N CONH2 N N N N N H S (i) (ii) (iii) (iv) Scheme 1 The optimized strategy used for data collection consisted of four phi and six omega scan sets, with 0.5 steps in phi or omega; completeness was 99.2 %. The structure was obtained and solved by direct methods using SHELXTL [16]. All non- hydrogen atoms of the molecule were refined anisotropically. All hydrogen atoms were located from the difference Fourier map, and their parameters were refined in the isotropic approximation of atomic displacements. The crystallographic data are summarized in Table 1. 3. Results and discussion The single-crystal X-ray structure revealed that the title compound crystallizes in a 1:1 molar ratio, in the space group P21/n with Z = 4. Figure 1 shows the asymmetric unit and atomic labeling scheme of the molecular complex. Selected bond lengths and angles are given in Table 2. The packing analysis reveals that the phenazine and phenothiazine molecules interact with one another through the formation of centrosymmetric N-H···N (H···N = 2.34 (2) Å, N···N = 3.12 (5) Å, and N-H···N = 176°) and C-H···N (H···N = 2.64 (7) Å, C···N = 3.12 (4) Å, and C-H···N = 176°) hydrogen bonds, to form tetrameric unit as shown in Figure 2a. This recognition pattern further interacts with one another through C-H···S (H···S = 2.92 (3) Å, C···S = 3.85 (6) Å, and C-H···S = 167°) hydrogen bonding (see Table 3). The characteristics of these hydrogen bonds are consistent with the values reported in the literature [17,18]. For instance, Desiraju et al. reported a 1:1 molecular complex of a co-crystal in which the structure is stabilized by N-H···N and C-H···S hydrogen bonding forming a herring-bone pattern [19]. Three-dimensional arrangement of the molecular complex is shown in Figure 3. Figure 1. A view of the title complex, showing displacement ellipsoids at the 40% probability level and the atom-numbering scheme. (a) (b) Figure 2. The packing (a) between the four molecules forming a tetramer and (b) molecules extending further by CH···S hydrogen bonding. 232 Mehmood et al. / European Journal of Chemistry 13 (2) (2022) 230-233 2022 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.13.2.230-233.2256 Table 2. Bond lengths and angles for the molecular complex. Atom Atom Length (Å) Atom Atom Length (Å) C1 C2 1.424(5) C21 C22 1.378(4) C1 C6 1.419(4) C21 C26 1.391(4) C1 N1 1.333(4) C21 N21 1.386(4) C2 C3 1.335(6) C22 C23 1.371(5) C3 C4 1.397(6) C23 C24 1.365(6) C4 C5 1.346(6) C24 C25 1.373(6) C5 C6 1.423(5) C25 C26 1.376(5) C6 N2 1.334(3) C26 S21 1.757(3) C7 C8 1.408(5) C27 C28 1.385(5) C7 C12 1.419(4) C27 C32 1.384(4) C7 N2 1.340(3) C27 S21 1.760(3) C8 C9 1.332(6) C28 C29 1.370(5) C9 C10 1.395(7) C29 C30 1.378(5) C10 C11 1.353(6) C30 C31 1.368(5) C11 C12 1.416(4) C31 C32 1.378(4) C12 N1 1.331(4) C32 N21 1.393(4) Atom Atom Atom Angle (°) Atom Atom Atom Angle (°) C6 C1 C2 118.5(4) N21 C21 C26 120.3(3) N1 C1 C2 119.6(4) C23 C22 C21 121.4(4) N1 C1 C6 121.9(3) C24 C23 C22 119.2(5) C3 C2 C1 120.8(5) C23 C24 C25 120.3(5) C2 C3 C4 120.8(5) C24 C25 C26 120.9(5) C5 C4 C3 120.9(5) C21 C26 S21 121.7(3) C4 C5 C6 120.7(5) C25 C26 C21 119.0(4) C1 C6 C5 118.2(4) C25 C26 S21 119.3(3) N2 C6 C1 121.6(3) C28 C27 S21 119.6(3) N2 C6 C5 120.2(3) C32 C27 C28 118.7(3) C8 C7 C12 119.4(4) C32 C27 S21 121.5(3) N2 C7 C8 119.2(3) C29 C28 C27 121.1(4) N2 C7 C12 121.4(3) C28 C29 C30 120.2(4) C9 C8 C7 120.0(5) C31 C30 C29 118.9(4) C8 C9 C10 121.4(5) C30 C31 C32 121.6(4) C11 C10 C9 121.0(5) C27 C32 N21 120.6(3) C10 C11 C12 119.6(5) C31 C32 C27 119.5(3) C11 C12 C7 118.5(4) C31 C32 N21 119.9(3) N1 C12 C7 122.0(3) C12 N1 C1 116.5(3) N1 C12 C11 119.5(3) C6 N2 C7 116.6(3) C22 C21 C26 119.1(4) C21 N21 C32 124.3(3) C22 C21 N21 120.6(3) C26 S21 C27 100.80(16) Table 3. Hydrogen bond parameters (distances, Å and angles, °). Hydrogen bonds D-H H···A D···A ∠ D-H···A N-H···N i 0.78 2.345 3.119(6) 175 C-H···N ii 0.94 2.637 3.394(9) 138 C4-H4···S21 iii 0.95 2.921 3.852(11) 167 Symmetry code: (i) x, -1+y, z; (ii) x, y, z; (iii) 1-x, 1-y, -z. Figure 3. View of the molecular complex along the b axis in three dimensions. 4. Conclusions Preparation of a 1:1 co-crystal formed between phenazine and 10H-phenothiazine is reported. Single crystal X-ray crystal- lographic studies of the co-crystal revealed that the structure is stabilized by N-H···N and C-H···N hydrogen bonds, which further interact through C-H···S hydrogen bonds between phenazine and 10H-phenothiazine to form supramolecular assembly. Acknowledgements Tahir Mehmood is thankful to Scheme of Developing High Quality Research (SHODH), Government of Gujarat, for financial support and Indrashil University for providing infrastructure. Supporting information CCDC-2096713 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/, or by e-mailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallo- https://www.ccdc.cam.ac.uk/structures/ mailto:data_request@ccdc.cam.ac.uk Mehmood et al. / European Journal of Chemistry 13 (2) (2022) 230-233 233 2022 – European Journal of Chemistry – CC BY NC – DOI: 10.5155/eurjchem.13.2.230-233.2256 graphic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033. Disclosure statement Conflict of interest: The authors declare that they have no conflict of interest. Ethical approval: All ethical guidelines have been adhered. Sample availability: Samples of the compounds are available from the author. CRediT authorship contribution statement Conceptualization: Jayarama Prakasha Reddy; Methodology: Jayarama Prakasha Reddy, Tahir Mehmood, Bhumiben Chandubhai Patel; Software: Jayarama Prakasha Reddy; Validation: Jayarama Prakasha Reddy, Tahir Mehmood, Bhumiben Chandubhai Patel; Formal Analysis: Jayarama Prakasha Reddy, Tahir Mehmood, Bhumiben Chandubhai Patel; Investigation: Jayarama Prakasha Reddy, Tahir Mehmood, Bhumiben Chandubhai Patel; Resources: NIL; Data Curation: Jayarama Prakasha Reddy; Writing - Original Draft: Jayarama Prakasha Reddy; Writing - Review and Editing: Jayarama Prakasha Reddy; Visualization: Jayarama Prakasha Reddy, Tahir Mehmood, Bhumiben Chandubhai Patel; Funding acquisition: Jayarama Prakasha Reddy; Supervision: Jayarama Prakasha Reddy; Project Administration: Jayarama Prakasha Reddy. Funding Scheme of developing high quality research https://mysy.guj.nic.in/shodh/ ORCID and Email Tahir Mehmood tahirmahmoodisu@gmail.com https://orcid.org/0000-0001-6790-9970 Bhumiben Chandubhai Patel pbhumi141@gmail.com https://orcid.org/0000-0003-2836-0254 Jayarama Prakasha Reddy j.prakashareddy@gmail.com jprakasha.reddy@indrashiluniversity.edu.in https://orcid.org/0000-0003-4550-2525 References [1]. Gellman, S. H. Foldamers: A manifesto. Acc. Chem. Res. 1998, 31, 173– 180. [2]. Selvanathan, S.; Peters, M. V.; Schwarz, J.; Hecht, S.; Grill, L. Formation and manipulation of discrete supramolecular azobenzene assemblies. Appl. Phys. A Mater. Sci. Process. 2008, 93, 247–252. [3]. Prabhakaran, P.; Puranik, V. G.; Chandran, J. N.; Rajamohanan, P. R.; Hofmann, H.-J.; Sanjayan, G. J. Novel foldamer structural architecture from cofacial aromatic building blocks. Chem. Commun. (Camb.) 2009, 3446–3448. [4]. Cuccia, L. A.; Lehn, J. M.; Homo, J. C.; Schmutz, M. 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Org. Biomol. Chem. 2013, 11, 8348–8356. [19]. Vangala, V. R.; Desiraju, G. R.; Jetti, R. K. R.; Bläser, D.; Boese, R. A 1:1 molecular complex of bis(4-aminophenyl) disulfide and 4- aminothiophenol. Acta Crystallogr. C 2002, 58, o635-6. Copyright © 2022 by Authors. This work is published and licensed by Atlanta Publishing House LLC, Atlanta, GA, USA. The full terms of this license are available at http://www.eurjchem.com/index.php/eurjchem/pages/view/terms and incorporate the Creative Commons Attribution-Non Commercial (CC BY NC) (International, v4.0) License (http://creativecommons.org/licenses/by-nc/4.0). By accessing the work, you hereby accept the Terms. 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Permissions for commercial use of this work beyond the scope of the License (http://www.eurjchem.com/index.php/eurjchem/pages/view/terms) are administered by Atlanta Publishing House LLC (European Journal of Chemistry). https://mysy.guj.nic.in/shodh/ mailto:tahirmahmoodisu@gmail.com https://orcid.org/0000-0001-6790-9970 mailto:pbhumi141@gmail.com https://orcid.org/0000-0003-2836-0254 mailto:j.prakashareddy@gmail.com mailto:jprakasha.reddy@indrashiluniversity.edu.in https://orcid.org/0000-0003-4550-2525 https://doi.org/10.1524/zkri.1983.162.14.i http://www.eurjchem.com/index.php/eurjchem/pages/view/terms http://creativecommons.org/licenses/by-nc/4.0 http://www.eurjchem.com/index.php/eurjchem/pages/view/terms 1. Introduction 2. Experimental 2.1. Synthesis 2.2. Crystal structure determination and refinement 3. Results and discussion 4. Conclusions Acknowledgements Supporting information Disclosure statement CRediT authorship contribution statement Funding ORCID and Email References PrintField10: PrintField11: PrintField12: PrintField13: PrintField20: PrintField21: PrintField22: PrintField23: