Synthesis, Crystal Structure, Density Functional Theory (DFT) Calculations and Molecular Orbital Calculations of 4-Bromoanilinium Perchlorate Single Crystal
Abstract
:1. Introduction
2. Materials and Methods
2.1. Synthesis Procedure
2.2. Computational Details
3. Results and Discussion
3.1. Crystal Structure Description
3.2. Structural Analysis
3.3. Frontier Molecular Orbital Analysis
3.4. NBO Analysis
3.5. Hirshfeld Surface Analysis
3.6. NLO Analysis
4. Conclusions
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
- Christopherson, J.-C.; Topić, F.; Barrett, C.J.; Friščić, T. Halogen-Bonded Cocrystals as Optical Materials: Next-Generation Control over Light–Matter Interactions. Cryst. Growth Des. 2018, 18, 1245–1259. [Google Scholar] [CrossRef]
- Targema, M.; Obi-Egbedi, N.O.; Adeoye, M.D. Molecular structure and solvent effects on the dipole moments and polarizabilities of some aniline derivatives. Comput. Theor. Chem. 2013, 1012, 47–53. [Google Scholar] [CrossRef]
- Anitha, R.; Athimoolam, S.; Gunasekaran, M.; Anitha, K. X-ray, vibrational spectra and quantum chemical studies on a new semiorganic crystal: 4-Chloroanilinium perchlorate. J. Mol. Struct. 2014, 1076, 115–125. [Google Scholar] [CrossRef]
- Krishnamoorthy, B.R.; Kannan, S.; Sivaperuman, K. Synthesis and crystal growth of 2, 3-dimethyl-N-[2-(hydroxy) benzylidene]. aniline: An organic second-order non-linear optical crystal for non-linear optical (NLO) applications. Opt. Mater. 2021, 113, 110864. [Google Scholar] [CrossRef]
- Anbarasan, R.; Eniya, P.; Lakshmi, M.A.; Sundar, J.K. Experimental and quantum chemical investigations of 4-bromoanilinium hydrogen phthalate crystal for optoelectronic applications. Mater. Res. Express. 2019, 6, 095105. [Google Scholar] [CrossRef]
- Anbarasan, R.; Eniya, P.; Kalyana Sundar, J.; Menberu Woldemariam, M. Crystal structure and Hirshfeld surface analysis of 4-bromoanilinium nitrate. Acta Crystallogr. Sect. E Crystallogr. Commun. 2020, 76, 973–976. [Google Scholar] [CrossRef] [PubMed]
- Mirosław, B.; Mahmoudi, G.; Ferenc, W.; Cristóvão, B.; Osypiuk, D.; Sarzyński, J.; Głuchowska, H.; Franconetti, A.; Frontera, A. Halogen interactions in dinuclear copper(ii) 2,4-dibromophenoxyacetate–crystal structure and quantum chemical calculations. J. Mol. Struct. 2020, 1202, 127227. [Google Scholar] [CrossRef]
- Arshad, M.N.; Al-Dies, A.A.M.; Asiri, A.M.; Khalid, M.; Birinji, A.S.; Al-Amry, K.A.; Braga, A.A. Synthesis, crystal structures, spectroscopic and nonlinear optical properties of chalcone derivatives: A combined experimental and theoretical study. J. Mol. Struct. 2017, 1141, 142–156. [Google Scholar] [CrossRef]
- Liu, S.; Schauer, C.K. Origin of molecular conformational stability: Perspectives from molecular orbital interactions and density functional reactivity theory. J. Chem. Phys. 2015, 142, 054107. [Google Scholar] [CrossRef]
- Katz, H.E.; Singer, K.D.; Sohn, J.E.; Dirk, C.W.; King, L.A.; Gordon, H.M. Greatly enhanced second-order nonlinear optical susceptibilities in donor-acceptor organic molecules. J. Am. Chem. Soc. 1987, 109, 6561–6563. [Google Scholar] [CrossRef]
- Bosshard, C. Organic Nonlinear Optical Materials; CRC Press: Boca Raton, FL, USA, 1998. [Google Scholar] [CrossRef]
- Vivek, P.; Suvitha, A.; Murugakoothan, P. Growth, spectral, anisotropic, second and third order nonlinear optical studies on potential nonlinear optical crystal anilinium perchlorate (AP) for NLO device fabrications, Spectrochim. Acta Part A Mol. Biomol. Spectrosc. 2015, 134, 517–525. [Google Scholar] [CrossRef] [PubMed]
- Vivek, P.; Murugakoothan, P. Second- and third-order optical studies of 4-Bromoanilinium hydrogen phthalate single crystal for nonlinear optical device applications. Appl. Phys. A 2014, 115, 1139–1146. [Google Scholar] [CrossRef]
- Anbarasan, R.; Eniya, P.; Lakshmi, M.A.; Sundar, J.K. Structural, spectral, optical, thermal and quantum chemical investigations on ethylenediammonium tetrachloro zinc crystal for optoelectronic applications. J. Mol. Struct. 2019, 1188, 165–172. [Google Scholar] [CrossRef]
- Haydock, S. Poisoning, overdose, antidotes. In Clinical Pharmacology; Elsevier: Amsterdam, The Netherlands, 2012; pp. 122–135. [Google Scholar] [CrossRef]
- Frisch, M.J.; Trucks, G.W.; Schlegel, H.B.; Scuseria, G.E.; Robb, M.A.; Cheeseman, J.R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G.A.; et al. Gaussian 09w, Gaussian 09, Rev, A.02; Gaussian, Inc.: Wallingford, CT, USA, 2010. [Google Scholar]
- Patterson, J.D. Density-Functional Theory of Atoms and Molecules; Springer: Dordrecht, The Netherlands, 1989. [Google Scholar] [CrossRef]
- Spackman, P.R.; Turner, M.J.; McKinnon, J.J.; Wolff, S.K.; Grimwood, D.J.; Jayatilaka, D.; Spackman, M.A. CrystalExplorer: A program for Hirshfeld surface analysis, visualization and quantitative analysis of molecular crystals. J. Appl. Cryst. 2021, 54, 1006–1011. [Google Scholar] [CrossRef]
- Spackman, M.A.; Jayatilaka, D. Hirshfeld surface analysis. Crystengcomm 2009, 11, 19–32. [Google Scholar] [CrossRef]
- Spackman, M.A.; Mckinnon, J.J. Fingerprinting intermolecular interactions in molecular crystals. Crystengcomm 2002, 4, 378–392. [Google Scholar] [CrossRef]
- Jacquemin, D.; Preat, J.; Charlot, M.; Wathelet, V.; André, J.M.; Perpète, E.A. Theoretical investigation of substituted anthraquinone dyes. J. Chem. Phys. 2004, 121, 1736–1743. [Google Scholar] [CrossRef] [PubMed]
- Sheldrick, G.M. Crystal structure refinement with SHELXL. Acta Crystallogr. Sect. C Struct. Chem. 2015, 71, 3–8. [Google Scholar] [CrossRef]
- Sheldrick, G.M. SHELXT–Integrated space-group and crystal-structure determination. Acta Crystallogr. Sect. A Found. Adv. 2015, 71, 3–8. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Farrugia, L.J. WINGX and ORTEP for Windows: An update. J. Appl. Crystallogr. 2012, 45, 849–854. [Google Scholar] [CrossRef]
- Glendening, E.D.; Landis, C.R.; Weinhold, F. Nbo 6.0: Natural bond orbital analysis program. J. Comput. Chem. 2013, 34, 1429–1437. [Google Scholar] [CrossRef] [PubMed]
- Nalwa, H.S. Organometallic materials for nonlinear optics. Appl. Organomet. Chem. 1991, 5, 349–377. [Google Scholar] [CrossRef]
Crystal Data | |
Chemical formula | C6H7BrN+·ClO4− |
Molecular weight | 272.49 |
Crystal system, space group | Triclinic, P-1 |
Temperature (K) | 296 |
a, b, c (Å) | 5.0752 (8), 7.0540 (11), 13.536 (2) |
α, β, γ (°) | 91.073 (5), 90.991 (5), 105.052 (5) |
V (Å3) | 467.77 (13) |
Z | 2 |
Radiation type | Mo-Kα |
µ (mm−1) | 4.66 |
Crystal size (mm) | 0.42 × 0.18 × 0.12 |
Data Collection | |
Diffractometer | Bruker SMART APEXII CCD |
Absorption correction | Multi-scan |
Tmin, Tmax | 0.380, 0.572 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8194, 2579, 2008 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.696 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.119, 1.05 |
No. of reflections | 2579 |
No. of parameters | 119 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.42−0.67 |
Atoms | CIF Bond Length (Å) | DFT Bond Length (Å) | Atoms | CIF Bond Angles (°) | DFT Bond Angles (°) |
---|---|---|---|---|---|
Br1-C1 | 1.8997 | 1.9412 | O2-Cl1-O4 | 109.23 | 109.74 |
Cl1-O2 | 1.4216 | 1.4825 | O2-Cl1-O1 | 109.31 | 109.74 |
Cl1-O4 | 1.4226 | 1.5168 | O2-Cl1-O3 | 109.57 | 110.91 |
Cl1-O1 | 1.4324 | 1.5169 | O4-Cl1-O1 | 109.5 | 107.27 |
Cl1-O3 | 1.4261 | 1.4840 | O4-Cl1-O3 | 110.54 | 109.56 |
N1-H3 | 0.89 | 1.0554 | O1-Cl1-O3 | 108.68 | 109.557 |
N1-H2 | 0.89 | 1.0314 | H3-N1-H2 | 109.47 | 106.19 |
N1-H1 | 0.89 | 1.0314 | H3-N1-H1 | 109.47 | 106.19 |
N1-C4 | 1.4731 | 1.4669 | H3-N1-C4 | 109.47 | 114.06 |
C4-C3 | 1.3674 | 1.4279 | H2-N1-H1 | 109.47 | 101.25 |
C4-C5 | 1.3712 | 1.4279 | H2-N1-C4 | 109.47 | 113.99 |
C3-H4 | 0.93 | 1.0860 | H1-N1-C4 | 109.47 | 113.99 |
C3-C2 | 1.3846 | 1.3796 | N1-C4-C3 | 118.58 | 117.03 |
C5-H7 | 0.93 | 1.0859 | N1-C4-C5 | 119.09 | 117.03 |
C5-C6 | 1.3798 | 1.3796 | C3-C4-C5 | 122.33 | 118.31 |
C2-H5 | 0.93 | 1.0836 | C4-C3-H4 | 120.6 | 119.89 |
C2-C1 | 1.3777 | 1.4118 | C4-C3-C2 | 118.81 | 120.38 |
C1-C6 | 1.3694 | 1.4117 | H4-C3-C2 | 120.6 | 119.54 |
C6-H6 | 0.93 | 1.0836 | C4-C5-H7 | 120.67 | 119.89 |
C4-C5-C6 | 118.66 | 120.37 | |||
H7-C5-C6 | 120.66 | 119.55 | |||
C3-C2-H5 | 120.39 | 120.109 | |||
C3-C2-C1 | 119.2 | 119.78 | |||
H5-C2-C1 | 120.4 | 120.07 | |||
Br1-C1-C2 | 119.95 | 118.99 | |||
Br1-C1-C6 | 118.75 | 118.99 | |||
C2-C1-C6 | 121.29 | 120.23 | |||
C5-C6-C1 | 119.68 | 119.78 | |||
C5-C6-H6 | 120.16 | 120.11 | |||
C1-C6-H6 | 120.16 | 120.07 |
D—H···A | D—H (Å) | H···A (Å) | D···A (Å) | D—H···A (°) |
---|---|---|---|---|
N1-H3···O4 | 0.890 | 2.064 | 2.944 | 169.81 |
N1-H2···O1 | 0.890 | 2.130 | 2.908 | 145.62 |
N1-H1···C11 | 0.890 | 2.949 | 2.3.809 | 163.10 |
N1-H1···O1 | 0.890 | 2.288 | 3.126 | 156.78 |
N1-H1···O3 | 0.890 | 2.288 | 3.282 | 137.03 |
C5-H7···O4 | 0.930 | 2.574 | 3.369 | 137.89 |
C2-H5···Br1 | 0.930 | 3.108 | 4.014 | 164.89 |
Donor (i) | Acceptor (j) | E(2) (Kcal/mol) | E(j)-E(i) (a.u.) | F(i,j) (a.u.) |
---|---|---|---|---|
BD (2) C11–C13 | BD*(2) C6–C7 | 24.93 | 0.26 | 0.072 |
BD (2) C6–C7 | BD*(2) C11–C13 | 19.64 | 0.28 | 0.067 |
BD (2) C9–C14 | BD*(2) C11–C13 | 19.08 | 0.27 | 0.065 |
BD (2) C6–C7 | BD*(2) C 9–C14 | 18.53 | 0.3 | 0.066 |
BD (2) C11–C13 | BD*(2) C 9–C14 | 18.33 | 0.29 | 0.066 |
LP (2) O17 | BD*(1) Cl16–O20 | 17.6 | 0.45 | 0.081 |
LP (2) O20 | BD*(1) Cl16–O17 | 17.43 | 0.45 | 0.08 |
BD (2) C9–C14 | BD*(2) C6–C7 | 17.12 | 0.26 | 0.061 |
LP (3) O17 | BD*(1) Cl16–O18 | 14.13 | 0.41 | 0.069 |
LP (3) O17 | BD*(1) Cl16–O19 | 14.13 | 0.41 | 0.069 |
LP (3) O20 | BD*(1) Cl16–O18 | 14 | 0.41 | 0.069 |
LP (3) O20 | BD*(1) Cl16–O19 | 14 | 0.41 | 0.069 |
LP (3) O18 | BD*(1) Cl16–O19 | 13.9 | 0.43 | 0.072 |
LP (3) O19 | BD*(1) Cl16–O18 | 13.9 | 0.43 | 0.072 |
LP (2) O18 | BD*(1) Cl16–O17 | 11.66 | 0.47 | 0.068 |
LP (2) O19 | BD*(1) Cl16–O17 | 11.66 | 0.47 | 0.068 |
LP (2) O18 | BD*(1) Cl16–O20 | 9.87 | 0.47 | 0.062 |
LP (2) O19 | BD*(1) Cl16–O20 | 9.87 | 0.47 | 0.062 |
LP (3) O18 | BD*(1) N 2–H 3 | 7.34 | 0.61 | 0.061 |
LP (3) O19 | BD*(1) N 2–H 4 | 7.34 | 0.61 | 0.061 |
Components | Calc. Value (a.u.) | Calc. Value (esu) | Components | Calc. Value (a.u.) | Calc. Value (esu) |
---|---|---|---|---|---|
μx | 13.1418 D | βxxx | 128.09 | 1.1066 | |
μy | −0.0013 D | βxxy | −0.0508 | −0.0004 | |
μz | 3.1012 D | βxyy | 35.9347 | 0.3105 | |
μtotal | 13.5028 D | βyyy | −0.0049 | −0.00004 | |
αxx | 202.8530 | 30.0628 | βxxz | 76.9752 | 0.6650 |
αxy | 0.0019 | 0.0003 | βxyz | −0.0083 | −0.00007 |
αyy | 120.7010 | 17.8879 | βyyz | −8.1640 | −0.0705 |
αxz | −4.5846 | −0.6794 | βxzz | 62.6529 | 0.5413 |
αzz | 91.5069 | 13.5613 | βyzz | −0.0115 | −0.00009 |
αyz | 0.0005 | −0.00006 | βzzz | 25.7094 | 0.2221 |
αtotal | 138.3536 | 20.5040 | βtotal | 245.5949 | 2.1218 |
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Waqas Alam, M.; Farhan, M.; Souayeh, B.; Aamir, M.; Khan, M.S. Synthesis, Crystal Structure, Density Functional Theory (DFT) Calculations and Molecular Orbital Calculations of 4-Bromoanilinium Perchlorate Single Crystal. Crystals 2021, 11, 1070. https://doi.org/10.3390/cryst11091070
Waqas Alam M, Farhan M, Souayeh B, Aamir M, Khan MS. Synthesis, Crystal Structure, Density Functional Theory (DFT) Calculations and Molecular Orbital Calculations of 4-Bromoanilinium Perchlorate Single Crystal. Crystals. 2021; 11(9):1070. https://doi.org/10.3390/cryst11091070
Chicago/Turabian StyleWaqas Alam, Mir, Mohd Farhan, Basma Souayeh, Muhammad Aamir, and Muhammad Shuaib Khan. 2021. "Synthesis, Crystal Structure, Density Functional Theory (DFT) Calculations and Molecular Orbital Calculations of 4-Bromoanilinium Perchlorate Single Crystal" Crystals 11, no. 9: 1070. https://doi.org/10.3390/cryst11091070
APA StyleWaqas Alam, M., Farhan, M., Souayeh, B., Aamir, M., & Khan, M. S. (2021). Synthesis, Crystal Structure, Density Functional Theory (DFT) Calculations and Molecular Orbital Calculations of 4-Bromoanilinium Perchlorate Single Crystal. Crystals, 11(9), 1070. https://doi.org/10.3390/cryst11091070