Se···N Chalcogen Bond and Se···X Halogen Bond Involving F2C Se

Article pubs.acs.org/JPCA

Se···N Chalcogen Bond and Se···X Halogen Bond Involving F2CSe: Influence of Hybridization, Substitution, and Cooperativity Xin Guo,† Xiulin An,‡ and Qingzhong Li*,† †

The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, People’s Republic of China ‡ College of Life Science, Yantai University, Yantai 264005, People’s Republic of China S Supporting Information *

ABSTRACT: Quantum-chemical calculations have been performed for the chalcogen- and halogen-bonded complexes of F2CSe with a series of nitrogen bases (N2, NCH, NH3, NHCH2, NCLi, and NMe3) and dihalogen molecules (BrCl, ClF, and BrF), respectively. Both types of interactions are mainly driven by the electrostatic and orbital interactions. The chalcogen bond becomes stronger in the order of NCH (sp) < NH3 (sp3) < NHCH2 (sp2), showing some inconsistence with the electronegativity of the hybridized N atom. The Li and methyl groups have an enhancing effect on the strength of chalcogen bond; however, the former is jointly achieved through the electrostatic and orbital interactions, whereas the orbital interaction has dominant contribution to the latter enhancement. The halogen bond with F2CX (X = O, S, Se) as the electron donor is stronger for the heavier chalcogen atom, exhibiting a reverse dependence on the chalcogen atom with that in hydrogen bonds. The halogen bond is further strengthened by the presence of chalcogen bond in the ternary complexes. In addition, CSD research confirms the abundance of Se···N interaction in crystal materials.

1. INTRODUCTION Noncovalent interaction is still one of research focus in the fields of chemistry and related sciences because it plays a significant role in molecular recognition, crystal engineering, and biological systems.1−3 Now, many new noncovalent interactions have been proposed and evidenced with both experimental and theoretical methods. Thereinto, halogen bond is one of new noncovalent interactions with increasing attention from scientists due to its potential applications in the previously described fields.4−6 Politizer and Murray provided a logical explanation for the formation of halogen bond via the concept of σ hole.7 The term σ hole refers to a region with positive electrostatic potential on the outer surface of halogen atom.8 In general, the magnitude of the σ hole is dependent on the nature of halogen atom and the electronwithdrawing ability of substituent adjoined with the halogen atom.9 Specifically, the larger halogen atom corresponds to the bigger σ hole, and the stronger electron-withdrawing ability of substituent adjoined with the halogen atom results in an increase in the magnitude of the σ-hole. Dihalogen molecules, particularly the Cl atom of ClF, are often taken as the halogen donor in halogen bonds.10,11 Interestingly, it was found that there is no contraction and subsequent expansion of the F−N distance as the transfer occurs in F−Cl···N halogen bond of FCl···NH3.12 This behavior is different from that observed for proton transfer across a F−H···N hydrogen bond.13 It was demonstrated that © 2015 American Chemical Society

the substitution and hybridization effects in the nitrogen bases have a prominent effect on the strength of F−Cl···N halogen bond.12 It is noted that sp3 is being used synonymously with pyramidal/tetrahedral and not that the precise hybridization is what is being specified. By means of substituent effect, the halogen bond in FCl···CNX (C is the halogen acceptor and X is a substituent) can be changed from a traditional one through a chlorine-shared one to an ion-pair one.14 Similarly, the nature of halogen bond in FCl···PCX (P is the halogen acceptor and X is a substituent) changes from traditional to chlorine-shared as the electron-donating ability of X increases.15 Additionally, the strength of halogen bond can also be regulated by cooperative effects.16−18 It was shown that the cooperative effect of halogen bond is very similar to that in hydrogen-bonded systems.16 The halogen bond also displays anticooperativity when H2CS acts as a double-electron donor to interact with two ClF molecules.17 More importantly, the nature of halogen bond in FCl···CNH complex can be changed by the cooperative effect with hydrogen bond.18 In the previously described studies of halogen bonds, the electron donors are often the lone pairs on N, O, S, C, and P; however, the halogen bonds with selenium as the electron donors are also important with Received: January 25, 2015 Revised: March 16, 2015 Published: March 23, 2015 3518

DOI: 10.1021/acs.jpca.5b00783 J. Phys. Chem. A 2015, 119, 3518−3527

Article

The Journal of Physical Chemistry A

Molecular electrostatic potentials (MEPs) at the 0.001 electrons Bohr−3 isodensity surfaces were calculated at the MP2/aug-cc-pVTZ level using the wave function analysis− surface analysis suite (WFA-SAS) program.37 Natural bond orbital (NBO) analysis38 was implemented at the HF/aug-ccpVTZ level via the procedures contained in Gaussian 09 to analyze orbital interaction, charge transfer, and Wiberg bond index. Topological properties were derived from the theory of atoms in molecules (AIM) at the MP2/aug-cc-pVTZ level with the AIM2000 software.39 To gain insight into the nature of the investigated intermolecular interactions, we performed the energy decomposition analysis (EDA) with the GAMESS program.40

potential biological, pharmaceutical, and electronic materials applications.11 Chalcogen bond is another important σ-hole interaction in which covalently bonded chalcogen atoms (S, Se, and Te) act as Lewis acids.19 This interaction also has extensive applications in crystal engineering and biological systems.20−22 Adhikari and Scheiner23 studied the substituent effect on the S···N chalcogen bond in X(Me)S···NH3 (X = CH3, H, NH2, CF3, NO2, OH, Cl, and F) and unveiled the comparable contribution of electrostatic and induction energies with the symmetry adapted perturbation theory (SAPT) method. More types of nitrogen bases were paired with SOXY (X, Y = F, Cl)24 and SF425 through a chalcogen bonding. It was demonstrated that chalcogen bond shows cooperative effect with other types of interaction.26 The geometries and properties of X2CY (X = H, F, Cl, and Br; Y = O, S, Se, and Te) have been a source of fascination because it was confirmed to play a role in biochemistry and cosmochemistry.27 It has known that X2CY is a multifunctional molecule with a σ hole on the Y atom, a π hole on the C atom, and lone pairs on the Y atom. Consequently, this molecule may participate in different types of noncovalent interactions such as halogen bonds17 and chalcogen bonds.28 It is natural to find the competition and cooperativity between different types of interactions involving X2CY.29−31 Selenocarbonyls are useful building blocks in crystal materials and act as important intermediates in the synthesis of selenium-containing compounds.32 Moreover, the interest in selenocarbonyls also arises from their role of a redox catalyst in the biological function of selenoproteins.33 It was shown that organoselenium compounds exhibit some unconventional properties when selenium atoms are involved in inter- and intramolecular interactions, as compared with their oxygen and sulfur analogues.34 We selected F2CSe as a Lewis acid to form a chalcogen bond with a series of nitrogen-containing bases NZ (NZ = N2, NCH, NH3, NHCH2, NCLi, and NMe3) to investigate the effect of hybridization and substitution on the strength of chalcogen bond. Simultaneously, we studied the halogen bond between F2CSe and dihalogen molecules (BrCl, ClF, and BrF). For comparison, the halogen-bonded complexes of F2CO···ClF and F2CS···ClF were also studied. The formation mechanism and nature of Se···N chalcogen bond and Se···X halogen bond have been analyzed by means of molecular electrostatic potentials, orbital interactions, and energy decomposition. Finally, we paid our attention to interplay between the Se···N chalcogen bond and Se···X halogen bond in three ternary complexes.

3. RESULTS AND DISCUSSION 3.1. Se···N Chalcogen Bonds. Figure 1 is the MEP map of F2CSe, where a red region with a positive MEP (σ hole) is

Figure 1. Molecular electrostatic potentials of F2CSe and XY (XY = BrCl, ClF, and BrF) molecules. Color ranges are red, >0.54; yellow, between 0.54 and 0; blue, BrF; however, it should be careful to estimate the strength of halogen bond with the Se···X distance because the halogen atom is different. To avoid this difficulty, the ratio λ = R2/(rSe + rX)42 is used to measure the strength of halogen bond. The deviation of this ratio from 1 is greater in the order of XY = BrCl < ClF < BrF, which is consistent with the magnitude of the σ hole on the halogen atom (Figure 1). Namely, the halogen bond becomes stronger in the order of XY = BrCl < ClF < BrF like that in other types of halogen bonds.18 The formation of halogen bond results in an elongation of CSe and X−Y bonds. The X−Y bond elongation is attributed to the charge shift from the Se lone pairs to the σ* antibonding orbital of X−Y bond (Table 3). Furthermore, the X−Y bond elongation also confirms the change of halogen bonding strength. Accompanied by the bond elongation, the stretch vibration of X−Y bond exhibits a significant red shift, especially in the case of ClF with a value up to 159 cm−1. The geometries of F2CSe···XY complexes were also optimized at the CCSD(T)/aug-cc-pVDZ level. The results are given in Table S1 in the SI. The C−Se···X angle is almost same at both levels of theory. The Se···X distance is much longer at the CCSD(T)/aug-cc-pVDZ level than that at the MP2/aug-cc-pVTZ level, whereas the elongation of CSe and X−Y bonds shows a reverse change. Thus, the geometries of F2CSe···XY complexes are affected by the calculation methods. Even so, the changing trend of the Se···X distance and the bond lengthening is the same at both levels of theory. The interaction energy of the Se···X halogen bond shows a similar change with the previous results of halogen bonds with dihalogen molecules as the halogen donors.18,52,53 For comparison, the interaction energies of F2CO···ClF and F2CS···ClF are calculated to be −11.93 and −17.87 kJ/mol at the MP2/aug-cc-pVTZ level, respectively. Obviously, the halogen bond becomes stronger in the order of F2CO < F2CS < F2CSe. To confirm the reliability of the order, we calculated the corresponding values at the CCSD(T)/aug-ccpVTZ level, and they are −10.85, −12.76, and −14.37 kJ/mol for F2CO···ClF, F2CS···ClF, and F2CSe···ClF, respectively. 3523

DOI: 10.1021/acs.jpca.5b00783 J. Phys. Chem. A 2015, 119, 3518−3527

Article

The Journal of Physical Chemistry A

with the strength of chalcogen bond. In addition, the enhancement of halogen bond does not change its nature in the light of the negative value of rF−Cl − rCl−Se.12 The strengthening of chalcogen and halogen bond can also be confirmed by the increase in electron density at the Se···N and Se···Cl BCPs as well as the stabilization energy due to the LPN → BD*C−Se and LPSe → BD*F−Cl orbital interactions, respectively. A further analysis indicates that the increase in electron density at the Se···N BCP is not consistent with the strength of chalcogen bond but that at the Se···Cl BCP shows a consistent change with the strength of chalcogen bond; however, the orbital interaction shows a reverse change with the strength of chalcogen bond for the Se···N and Se···Cl interactions. 3.4. CSD Research. It was known that the Se···N interaction exists abundantly in crystal structures. Hence, we want to summarize its geometrical features by researching for Cambridge Structural Database (CSD).56 This research has been performed with the following conditions: not disorder, no error, R-factor is smaller than 0.1, and the distance between the selenium and nitrogen atom is less than the sum of their van der Waals radii. It is found that more than 300 structures exhibit the Se···N interaction with the distance in a range of 2.45 to 3.45 Å. For instance, three structures with Se···N interactions are shown in Figure 7. In NAPSEZ10,57 the Se···N distance is 2.898 Å with the nitrogen atom pointing to the σ hole of the selenium atom. KEKSOI58 has a shorter Se···N distance than does NAPSEZ10 due to the existence of five electron-withdrawing Cl groups in the former structure. A longer Se···N distance is found in YEMCUO,59 in which the sp hybridized N atom acts as the electron donor. Furthermore, the directionality of the interaction in these crystals clearly shows that the σ hole is responsible for the stability of the Se···N interaction.

4. CONCLUSIONS The presence of lone pair and σ hole on the Se atom of F2CSe makes this atom play a dual role of Lewis base and acid. The σ hole was paired with a series of nitrogen bases (N2, NCH, NH3, NHCH2, NCLi, and NMe3) through a chalcogen bond, while the lone pair participates in the halogen bond with dihalogen molecules (BrCl, ClF, and BrF). F2CSe···N2 is a weak complex with the dominant contribution of dispersion energy. The hybridization of N atom has an effect on the strength of chalcogen bond and NHCH2 forms a stronger chalcogen bond than NCH and NH3. The Li atom in NCLi strengthens the chalcogen bond, although its enhancing effect is not larger than that in halogen and pnicogen bonds. The orbital interaction has a comparable contribution to the Li enhancing effect with the electrostatic interaction. The methyl group in trimethylamine also exhibits a strengthening role, but its enhancement effect is

Figure 6. Molecular graphs of trimers FCl···F2CSe···NH3, FCl··· F2CSe···NHCH2, and FCl···F2CSe···NMe3.

the Se atom of F2CSe plays a dual role of Lewis acid and base in the chalcogen and halogen bonds, respectively. Furthermore, the shortening of the Se···Cl distance is prominent, ranging from 0.136 to 0.181 Å; however, its shortening does not have a consistent change with the strength of chalcogen bond. Similarly, the chalcogen bond is also enhancement, characterized by the shortening of the Se···N distance. It is expected that the strengthening of both chalcogen bond and halogen bond results in the bigger elongation of the F−Cl and CSe bonds. Importantly, the increase in the F−Cl and CSe bond elongation is in the ascending order of FCl···F2CSe···NH3 < FCl···F2CSe···NHCH2 < FCl···F2CSe···NMe3, in agreement

Table 5. Angles (α, deg), Binding Distances (R, Å), Changes of Bond Lengths (Δr, Å), Electron Density (ρ, au) at the Intermolecular BCP, and Second-Order Perturbation Energy (E2, kJ/mol) in the Ternary Complexesa α1(α2) R1(R2) Δr1(Δr2) ρ E2 a

FCl···F2CSe···NH3

FCl···F2CSe···NHCH2

FCl···F2CSe···NMe3

170.1(96.4) 2.984(2.600) 0.022(0.095) 0.0163[0.0537] 26.37[307.10]

176.1(96.0) 2.938(2.566) 0.024(0.107) 0.0176[0.0574] 27.13[356.39]

177.8(96.7) 2.761(2.611) 0.045(0.140) 0.0292[0.0611] 40.80[327.08]

Data in and outside brackets are from the Se···N and Se···Cl interactions, respectively. 3524

DOI: 10.1021/acs.jpca.5b00783 J. Phys. Chem. A 2015, 119, 3518−3527

Article

The Journal of Physical Chemistry A

Figure 7. Crystal structures of YEMCUO, KEKSOI, and NASPEZ10. (3) Wu, F. G.; Wang, N. N.; Yu, Z. W. Nonsynchronous Change in the Head and Tail of Dioctadecyldimethylammonium Bromide Molecules during the Liquid Crystalline to Coagel Phase Transformation Process. Langmuir 2009, 25, 13394−13401. (4) Caballero, A.; White, N. G.; Beer, P. D. A Bidentate HalogenBonding Bromoimidazoliophane Receptor for Bromide Ion Recognition in Aqueous Media. Angew. Chem., Int. Ed. 2011, 50, 1845−1848. (5) Politzer, P.; Murray, J. S. Halogen Bonding: An Interim Discussion. ChemPhysChem 2013, 14, 278−294. (6) Auffinger, P.; Hays, F. A.; Westhof, E.; Ho, P. S. Halogen Bonds in Biological Molecules. Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 16789− 16794. (7) Clark, T.; Hennemann, M.; Murray, J. S.; Politzer, P. Halogen Bonding: The σ-Hole. J. Mol. Model. 2007, 13, 291−296. (8) Politzer, P.; Lane, P.; Concha, M. C.; Ma, Y.; Murray, J. S. An Overview of Halogen Bonding. J. Mol. Model. 2007, 13, 305−311. (9) Riley, K. E.; Murray, J. S.; Fanfrlík, J.; Ř ezác,̌ J.; Solá, R. J.; Concha, M. C.; Ramos, F. M.; Politzer, P. Halogen Bond Tunability I: The Effects of Aromatic Fluorine Substitution on the Strengths of Halogen-Bonding Interactions Involving Chlorine, Bromine, and Iodine. J. Mol. Model. 2011, 17, 3309−3318. (10) Legon, A. C. The Interaction of Dihalogens and Hydrogen Halides with Lewis Bases in the Gas Phase: An Experimental Comparison of the Halogen Bond and the Hydrogen Bond. Struct. Bonding (Berlin, Ger.) 2008, 126, 17−64. (11) Pennington, W. T.; Hanks, T. W.; Arman, H. D. Halogen Bonding with Dihalogens and Interhalogens. Struct. Bonding (Berlin, Ger.) 2008, 126, 65−104. (12) Del Bene, J. E.; Alkorta, I.; Elguero, J. Spin-Spin Coupling across Intermolecular F-Cl···N Halogen Bonds. J. Phys. Chem. A 2008, 112, 7925−7929. (13) Buckingham, A. D.; Del Bene, J. E.; McDowell, S. A. C. The Hydrogen Bond. Chem. Phys. Lett. 2008, 463, 1−10. (14) Del Bene, J. E.; Alkorta, I.; Elguero, J. Do Traditional, Chlorineshared, and Ion-Pair Halogen Bonds Exist? An Ab Initio Investigation of FCl:CNX Complexes. J. Phys. Chem. A 2010, 114, 12958−12962. (15) Alkorta, I.; Sanchez-Sanz, G.; Elguero, J.; Del Bene, J. E. FCl:PCX Complexes: Old and New Types of Halogen Bonds. J. Phys. Chem. A 2012, 116, 2300−2308. (16) Grabowski, S. J.; Bilewicz, E. Cooperativity Halogen Bonding Effect − Ab Initio Calculations on H2CO···(ClF)n Complexes. Chem. Phys. Lett. 2006, 427, 51−55. (17) Li, Q. Z.; Ma, S. M.; Liu, X. F.; Li, W. Z.; Cheng, J. B. Cooperative and Substitution Effects in Enhancing Strengths of Halogen Bonds in FCl···CNX Complexes. J. Chem. Phys. 2012, 137, 084314.

dominated by the orbital interaction because the negative electrostatic potential on the N atom of trimethylamine is smaller than that of NH3. The strength of halogen bond involving F2CSe is also proportional to the positive electrostatic potential on the halogen bond. Interestingly, the halogen bond becomes stronger in the order of F2CO < F2CS < F2CSe, which is reverse to that in hydrogen bond. The nature of halogen bond in F2CSe···ClF is not changed, although it can be strengthened by the chalcogen bond in the trimer. Finally, the importance of Se···N interaction in crystal materials has been confirmed by CSD survey.

■

ASSOCIATED CONTENT

* Supporting Information S

Optimized structures of chalcogen- and halogen-bonded dimers as well as f the geometrical and energetic parameters of halogen-bonded dimers at the CCSD(T)/augc-cc-pVDZ level. This material is available free of charge via the Internet at http://pubs.acs.org.

■

AUTHOR INFORMATION

Corresponding Author

*Tel: (+086) 535 6902063. Fax: (+086) 535 6902063. E-mail: [email protected]. Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS This work was supported by the Outstanding Youth Natural Science Foundation of Shandong Province (JQ201006), the Key Project of Natural Science Foundation of Shandong Province of China (ZR2013HZ004), and the National Natural Science Foundation of China (51278443).

■

REFERENCES

(1) Scheiner, S. Hydrogen Bonding: A Theoretical Perspective; Oxford University Press: New York, 1997. (2) Feng, Y.; Rainteau, D.; Chachaty, C.; Yu, Z. W.; Wolf, C.; Quinn, P. J. Characterization of a Quasicrystalline Phase in Codispersions of Phosphatidylethanolamine and Glucocerebroside. Biophys. J. 2004, 86, 2208−2217. 3525

DOI: 10.1021/acs.jpca.5b00783 J. Phys. Chem. A 2015, 119, 3518−3527

Article

The Journal of Physical Chemistry A (18) Li, Q. Z.; Li, R.; Zhou, Z. J.; Li, W. Z.; Cheng, J. B. S···X Halogen Bonds and H···X Hydrogen Bonds in H2CS−XY (XY = FF, ClF, ClCl, BrF, BrCl, and BrBr) Complexes: Cooperativity and Solvent Effect. J. Chem. Phys. 2012, 136, 014302. (19) Wang, W. Z.; Ji, B. M.; Zhang, Y. Chalcogen Bond: A Sister Noncovalent Bond to Halogen Bond. J. Phys. Chem. A 2009, 113, 8132−8135. (20) Iwaoka, M.; Takemoto, S.; Tomoda, S. Statistical and Theoretical Investigations on the Directionality of Nonbonded S···O Interactions. Implications for Molecular Design and Protein Engineering. J. Am. Chem. Soc. 2002, 124, 10613−10620. (21) Metrangolo, P.; Resnati, G. Enzyme Mimics: Halogen and Chalcogen Team Up. Nat. Chem. 2012, 4, 437−438. (22) Bai, M.; Thomas, S. P.; Kottokkaran, R.; Nayak, S. K.; Ramamurthy, P. C.; Row, T. N. G. A Donor−Acceptor−Donor Structured Organic Conductor with S···S Chalcogen Bonding. Cryst. Growth Des. 2014, 14, 459−466. (23) Adhikari, U.; Scheiner, S. Effects of Charge and Substituent on the S···N Chalcogen Bond. J. Phys. Chem. A 2014, 118, 3183−3192. (24) Azofra, L. M.; Alkorta, I.; Scheiner, S. Chalcogen Bonds in Complexes of SOXY (X, Y = F, Cl) with Nitrogen Bases. J. Phys. Chem. A 2015, 119, 535−541. (25) Nziko, V. de P. N.; Scheiner, S. Chalcogen Bonding between Tetravalent SF4 and Amines. J. Phys. Chem. A 2014, 118, 10849− 10856. (26) Esrafili, M. D.; Mohammadian-Sabet, F.; Solimannejad, M. A Theoretical Evidence for Mutual Influence between S···N(C) and Hydrogen/Lithium/Halogen Bonds: Competition and Interplay between π-Hole and σ-Hole Interactions. Struct. Chem. 2014, 25, 1197−1205. (27) Jaufeerally, N. B.; Abdallah, H. H.; Ramasami, P.; Schaefer, H. F., III. Telluroformaldehyde and its Derivatives: Structures, Ionization Potentials, Electron Affinities and Singlet−Triplet Gaps of the X2CTe and XYCTe (X,Y = H, F, Cl, Br, I and CN) Species. Theor. Chem. Acc. 2012, 131, 1127. (28) Li, Q. Z.; Qi, H.; Li, R.; Liu, X. F.; Li, W. Z.; Cheng, J. B. Prediction and Characterization of a Chalcogen−Hydride Interaction with Metal Hybrids as an Electron Donor in F2CS−HM and F2CSe− HM (M = Li, Na, BeH, MgH, MgCH3) Complexes. Phys. Chem. Chem. Phys. 2012, 14, 3025−3030. (29) Guo, X.; Liu, Y. W.; Li, Q. Z.; Li, W. Z.; Cheng, J. B. Competition and Cooperativity between Tetrel Bond and Chalcogen Bond in Complexes Involving F2CX (X = Se and Te). Chem. Phys. Lett. 2015, 620, 7−12. (30) Guo, X.; Cao, L. S.; Li, Q. Z.; Li, W. Z.; Cheng, J. B. Competition between π-Hole Interaction and Hydrogen Bond in the Complexes of F2XO (X = C and Si) and HCN. J. Mol. Model. 2014, 20, 2493. (31) Tang, Q. J.; Li, Q. Z. Interplay between Tetrel Bonding and Hydrogen Bonding Interactions in Complexes Involving F2XO (X = C and Si) and HCN. Comput. Theor. Chem. 2014, 1050, 51−57. (32) Liao, H. Y.; Su, M. D.; Chu, S. Y. Density Functional Studies on the Mechanisms of Unimolecular Reactions of HXCSe (X=H, F, Cl, and Br). Chem. Phys. 2000, 261, 275−287. (33) Kwiatkowski, J. S.; Leszczyski, J. Molecular Structure and Vibrational Infrared Spectra of Formaldehyde, Selenoformaldehyde and their Dihalogenoderivatives by Ab Initio Post-Hartree-Fock Calculation. Mol. Phys. 1994, 81, 119−131. (34) Madzhidov, T. I.; Chmutova, G. A.; Pendas, A. M. The Nature of the Interaction of Organoselenium Molecules with Diiodine. J. Phys. Chem. A 2011, 115, 10069−10077. (35) 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 09, revision A.02; Gaussian, Inc.: Wallingford, CT, 2009. (36) Boys, S. F.; Bernardi, F. The Calculation of Small Molecular Interactions by the Differences of Separate Total Energies. Some Procedures with Reduced Errors. Mol. Phys. 1970, 19, 553−556.

(37) Bulat, F. A.; Toro-Labbé, A.; Brinck, T.; Murray, J. S.; Politzer, P. Quantitative Analysis of Molecular Surfaces: Areas, Volumes, Electrostatic Potentials and Average Local Ionization Energies. J. Mol. Model. 2010, 16, 1679−1691. (38) Reed, A. E.; Curtiss, L. A.; Weinhold, F. Intermolecular Interactions from a Natural Bond Orbital, Donor−Acceptor Viewpoint. Chem. Rev. 1988, 88, 899−926. (39) Bader, R. F. W. AIM2000 Program v.2.0; McMaster University: Hamilton, Canada, 2000. (40) Schmidt, M. W.; Baldridge, K. K.; Boatz, J. A.; Elbert, S. T.; Gordon, M. S.; Jensen, J. H.; Koseki, S.; Matsunaga, N.; Nguyen, K. A.; Su, S. J.; et al. General Atomic and Molecular Electronic Structure System. J. Comput. Chem. 1993, 14, 1347−1363. (41) Pauling, L. The Nature of the Chemical Bond, 3rd ed.; Cornell University Press: New York, 1960. (42) Lommerse, J. P. M.; Stone, A. J.; Taylor, R.; Allen, F. H. The Nature and Geometry of Intermolecular Interactions between Halogens and Oxygen or Nitrogen. J. Am. Chem. Soc. 1996, 118, 3108−3116. (43) Alkorta, I.; Sánchez-Sanz, G.; Elguero, J. Pnicogen Bonds between X=PH3 (X = O, S, NH, CH2) and Phosphorus and Nitrogen Bases. J. Phys. Chem. A 2014, 118, 1527−1537. (44) Tsuzuki, S.; Sato, N. Origin of Attraction in Chalgogen− Nitrogen Interaction of 1,2,5-Chalcogenadiazole Dimers. J. Phys. Chem. B 2013, 117, 6849−6855. (45) Cheng, J. B.; Li, R.; Li, Q. Z.; Jing, B.; Liu, Z. B.; Li, W. Z.; Gong, B. A.; Sun, J. Z. Prominent Effect of Alkali Metals in HalogenBonded Complex of MCCBr−NCM′ (M and M′ = H, Li, Na, F, NH2, and CH3). J. Phys. Chem. A 2010, 114, 10320−10325. (46) Scheiner, S. Effects of Substituents upon the P···N Noncovalent Interaction: The Limits of Its Strength. J. Phys. Chem. A 2011, 115, 11202−11209. (47) Li, Q. Z.; An, X. L.; Luan, F.; Li, W. Z.; Gong, B. A.; Cheng, J. B. Regulating Function of Methyl Group in Strength of CH···O Hydrogen Bond: A High-Level Ab Initio Study. J. Phys. Chem. A 2008, 112, 3985−3990. (48) Koch, U.; Popelier, P. L. A. Characterization of C−H···O Hydrogen Bonds on the Basis of the Charge Density. J. Phys. Chem. A 1995, 99, 9747−9754. (49) Arnold, W. D.; Oldfield, E. The Chemical Nature of Hydrogen Bonding in Proteins via NMR: J-Couplings, Chemical Shifts, and AIM Theory. J. Am. Chem. Soc. 2000, 122, 12835−12841. (50) Bleiholder, C.; Werz, D. B.; Koppel, H.; Gleiter, R. Theoretical Investigations on Chalcogen−Chalcogen Interactions: What Makes These Nonbonded Interactions Bonding? J. Am. Chem. Soc. 2006, 128, 2666−2674. (51) Scheiner, S.; Kar, T. Red- versus Blue-Shifting Hydrogen Bonds: Are There Fundamental Distinctions? J. Phys. Chem. A 2002, 106, 1784−1789. (52) Wang, Z. X.; Zhang, J. C.; Wu, J. Y.; Cao, W. L. Theoretical Study on Intermolecular Interactions between Furan and Dihalogen Molecules XY(X,Y = F, Cl, Br). J. Chem. Phys. 2007, 126, 134301. (53) Wang, Z. X.; Zheng, B. S.; Yu, X. Y.; Li, X. F.; Yi, P. G. Structure, Properties, and Nature of the Pyridine-XY (X, Y = F, Cl, Br) Complexes: An ab Initio Study. J. Chem. Phys. 2010, 132, 164104. (54) Ban, Q. F.; Li, R.; Li, Q. Z.; Li, W. Z.; Cheng, J. B. SymmetryAdapted Perturbation Theory Interaction Energy Decomposition for H2CY-XF (Y = O, S, Se; X = H, Li, Cl) Complex. Comput. Theor. Chem. 2012, 991, 88−92. (55) Su, P. F.; Li, H. Energy Decomposition Analysis of Covalent Bonds and Intermolecular Interactions. J. Chem. Phys. 2009, 131, 014102. (56) Allen, F. H. The Cambridge Structural Database: A Quarter of a Million Crystal Structures and Rising. Acta. Crystallogr., Sect. B 2002, 58, 380−388. (57) Gieren, A.; Lamm, V.; Haddon, R. C.; Kaplan, M. L. Molecular, Electronic, and Crystal Structure of Naphtho[1,8-cd:4,5-c’d’]bis[1,2,6]selenadiazine. J. Am. Chem. Soc. 1980, 102, 5070−5073. 3526

DOI: 10.1021/acs.jpca.5b00783 J. Phys. Chem. A 2015, 119, 3518−3527

Article

The Journal of Physical Chemistry A (58) Gillespie, R. J.; Kent, J. P.; Sawyer, J. F. Reactions of S4N4 and S3N3C13 with Selenium Chlorides. The Preparations and Crystal Structures of SeS2N2C12, (S5N5)(SeCl5), and the Disordered Materials (SexS3‑xN2Cl)(SbC16). Inorg. Chem. 1990, 29, 1251−1259. (59) Geiser, U.; Wang, H. H.; Schlueter, J. A.; Williams, J. M.; Smart, J. L.; Cooper, A. C.; Kumar, S. K.; Caleca, M.; Dudek, J. D.; Carlson, K. D.; et al. Synthesis, Structure, and Properties of the Organic Conductor (BEDT-TTF)2Br2SeCN. Inorg. Chem. 1994, 33, 5101− 5107.

3527

DOI: 10.1021/acs.jpca.5b00783 J. Phys. Chem. A 2015, 119, 3518−3527