Halogen bonding in hypervalent iodine and bromine derivatives: halonium salts

Cavallo, G.; Murray, J.S.; Politzer, P.; Pilati, T.; Ursini, M.; Resnati, G.

doi:10.1107/S2052252517004262

research papers

IUCrJ

Volume 4| Part 4| July 2017| Pages 411-419

ISSN: 2052-2525

https://doi.org/10.1107/S2052252517004262

CHEMISTRY | CRYSTENG

Open

access

Halogen bonding in hypervalent iodine and bromine derivatives: halonium salts

Gabriella Cavallo,^a Jane S. Murray,^b Peter Politzer,^b Tullio Pilati,^a Maurizio Ursini ^a and Giuseppe Resnati ^a ^*

^aNFMLab, Department of Chemistry, Materials and Chemical Engineering `Giulio Natta', via Mancinelli 7, Milan I-20131, Italy, and ^bDepartment of Chemistry, University of New Orleans, New Orleans, LA 70148, USA
^*Correspondence e-mail: giuseppe.resnati@polimi.it

Edited by C. Lecomte, Université de Lorraine, France (Received 19 February 2017; accepted 16 March 2017; online 10 May 2017)

Halogen bonds have been identified in a series of ionic compounds involving bromonium and iodonium cations and several different anions, some also containing hypervalent atoms. The hypervalent bromine and iodine atoms in the examined compounds are found to have positive σ-holes on the extensions of their covalent bonds, while the hypervalent atoms in the anions have negative σ-holes. The positive σ-holes on the halogens of the studied halonium salts determine the linearity of the short contacts between the halogen and neutral or anionic electron donors, as usual in halogen bonds.

Keywords: halogen bond; σ-hole interactions; hypervalent iodine; hypervalent bromine; crystal engineering.

CCDC references: 1532402; 1532403; 1532404; 1532405; 1532406; 1532407

1. Introduction

It is well established that the charge distribution of a covalently bonded atom is anisotropic; the electronic density on the side of the atom opposite the bond is less than on the lateral sides of the atom (Stevens, 1979 ; Nyburg & Wong-Ng, 1979 ; Price et al., 1994 ; Awwadi et al., 2006 ; Hathwar et al., 2014 ; Pavan et al., 2014 ). The region of lower electronic density along the extension of the covalent bond is called a σ-hole (Politzer et al., 2013 , 2015a ). Due to their lower electronic densities, σ-holes often (but not always) have positive electrostatic potentials, while the regions around them are usually negative. The atom can interact attractively through its σ-hole with negative sites, e.g. lone pairs, π-electrons and anions (Politzer et al., 2013 ; Cavallo et al., 2016 ) and through its lateral sides with positive sites, e.g. other σ-holes and cations (Metrangolo & Resnati, 2013 ; Cavallo et al., 2014 ). The geometry of the covalent bonds around an atom thus influences the preferential directions of attractive interactions with nucleophiles and electrophiles. For instance, monovalent halogens can work as donors of electron density when interacting with hydrogen atoms or alkali and alkaline earth metal cations, and as acceptors of electron density when interacting with atoms and anions possessing lone pairs. In former cases, the electrophilic hydrogen, or the cation, enter preferentially the most negative region of the halogen atom X, namely the belt orthogonal to the C—X bond. In latter cases, the nucleophile has a preference for the σ-hole and the resulting interaction tends to form on the extension of and opposite to the C—X bond. In monovalent halogens attractive interactions with electrophiles and nucleophiles thus tend to be geometrically orthogonal to each other.

Interactions formed with negative sites by σ-holes on halogen atoms (Group 17) are called halogen bonds (XBs; Desiraju et al., 2013 ) analogous to interactions wherein H atoms are the acceptors of electronic density which are named hydrogen bonds (HBs). While the first halogen-bonded adduct was reported as early as 1814 (Colin, 1814 ), the nature of the interaction was understood only much later, when positive σ-holes on covalently bonded halogen atoms were discovered (Brinck et al., 1992 , 1993 ). In the same years, the applicative usefulness of the interaction was fully appreciated, in conjunction with the systematization of strategies to tune the interaction strength (Metrangolo & Resnati, 2001 ). Halogen σ-holes become more positive, and halogen bonds stronger, as the halogen atom is more polarizable (F < Cl < Br < I) and as the remainder of the molecule is more electron-attracting (Valerio et al., 2000 ).

Fig. 1(a) shows the linear halogen-bonded chain formed by cyanogen chloride in the solid state (Heiart & Carpenter, 1956 ) via C—Cl⋯N≡C halogen bonds; cyanogen bromide (Geller & Schawlow, 1955) and cyanogen iodide (Ketelaar & Zwartsenberg, 1939 ) behave similarly. Analogous chains are obtained with 4-bromo- and 4-iodobenzonitrile (Desiraju & Harlow, 1989 ; Figs. 1b and 1c), but not with the 4-chloro analogue, possibly as chlorine is a weaker XB donor.

Figure 1
Partial representation (Mercury 3.8, ball and stick) of the infinite chains formed by halogen bonds in crystalline (a) cyanogen chloride, (b) 4-bromo- and (c) 4-iodobenzonitrile and formed by pnictogen bonds in (d) cyano-dimethylarsine. Hydrogen atoms have been omitted for simplicity; halogen and pnictogen bonds are black dotted lines. Color codes: grey, carbon; blue, nitrogen; violet, arsenic; brown, bromine; green, chlorine; purple, iodine.

The anisotropic distribution of the electronic density in an atom due to its involvement in σ-bond formation, the development of σ-holes opposite these bonds, and the directionality of interactions formed on the entrance of electrophiles in these areas of depleted electron density are not limited to monovalent halogens as they also occur with hydrogen (Murray et al., 2010 ; Politzer et al., 2013), and elements of Group 14 (Southern & Bryce, 2015 ), 15 (Politzer et al., 2014 ) and 16 (Ho et al., 2016 ). The maximum number of σ-holes on an atom, namely of directional interactions it may form with nucleophiles, is usually equal to the number of covalent bonds the atom is involved in. Also for elements of any group of the periodic table, σ-holes tend to become more positive as the molecular environment is more electron-withdrawing and as the atom is more polarizable. It should be noted that σ-holes can also have negative electrostatic potentials, especially for the less-polarizable first-row atoms, but then they are less negative than the surrounding regions. Cyanodimethylarsine produces the chain shown in Fig. 1(d) (Britton et al., 2002 ) by means of the NC—As⋯N≡C pnictogen bond, while tellurium dicyanide (Klapötke et al., 2004 ) and dicyanodimethyltin (Konnert et al., 1972 ) form two-dimensional networks via the Te⋯N≡C chalcogen bond and Sn⋯N≡C tetrel bond (Fig. 2). The terms tetrel bond, pnictogen bond and chalcogen bond have been proposed to designate interactions wherein elements of Groups 14, 15 and 16 are the electrophilic site and an IUPAC Project (No. 2016-001-2-300) is pursuing a recommendation proposing a definition for these terms.

Figure 2
Partial representation (Mercury 3.8, ball and stick) of the two-dimensional nets formed by dicyanotelluride under chalcogen bond control (top) and by dicyano-dimethyltin under tetrel bond control (bottom). Hydrogen atoms have been omitted for simplicity; chalcogen and tetrel bonds are black dotted lines. Color codes: grey, carbon; blue, nitrogen; ochre, tellurium; dark green, tin.

Examples reported in Fig. 2 show that elements of Groups 14 and 16, which form more than one covalent bond and have more than one σ-hole, can form more than one directional interaction with nucleophiles, and we thus reasoned that hypervalent halogens, which also form more than one covalent bond, may also have more than one σ-hole and form more than one XB. More generally, any hypervalent atom, which is involved in more than its usual number of covalent bonds, may have σ-holes on the extensions of all its bonds and may form a corresponding number of attractive interactions with sites of opposite polarity. Computationally, this has been confirmed for hypervalent atoms in a number of neutral molecules (Clark et al., 2008 ; Murray et al., 2009 ; O'Hair et al., 2010 ). We have now investigated, both computationally and experimentally, a series of ionic compounds in which the cation and sometimes the anion contain hypervalent atoms. Specifically, we have established the surface electrostatic potential of the cation and anion of some ionic λ³-iodane and λ³-bromane derivatives, and we have checked the contacts below the sum of the van der Waals radii of involved atoms (hereinafter named short contacts) formed by these halogens in the crystalline state. It is known that the electrostatic potential of a cation (anion) is positive (negative) everywhere on its surface, although the values of the electrostatic potential cover ranges of positive (negative) values except on the surfaces of monoatomic cations (anions) (Politzer et al., 2016 ). Accordingly the hypervalent atoms will be positive or negative on their entire surfaces in the cation or anion, respectively, but are these atoms more positive (in the case of cations) or less negative (in the case of anions) on the extensions of the covalent bonds to them, thus forming σ-holes? Moreover, are the positive σ-holes on halogens of hypervalent halonium cations influential in the formation of short contacts with anions in the solid? In this paper we show that answers to these questions are yes for the salts of ionic λ³-iodane and λ³-bromane, and the directionality of the short contacts involving halogen atoms in these hypervalent iodine and bromine compounds fulfill the prerequisites for being considered bona fide XBs. The short contacts involving hypervalent halogens are frequently named in the literature as secondary bondings (Alcock & Countryman, 1977 ); an advantage of naming them halogen bonds is that this terminology is more descriptive of some of the interaction features; for instance, it immediately gives indications of the directionality of the interaction and the relationships between the strength of the interaction and the nature of involved sites (Catalano et al., 2016 ).

2. Experimental

2.1. Materials and methods

Phenyl-2-carbomethoxyphenyl-bromonium tetrafluoroborate, dibenzo[b,d]iodolium chloride, diphenyliodonium perchlorate, diphenyliodonium hexafluorophosphate and di-p-fluorophenylbromonium tetrafluoroborate were purchased from TCI or Vitas-M Laboratory, LTD. Di-p-fluorophenylbromonium chloride and bromide were prepared starting from the corresponding tetrafluoroborate salt by using anion exchange resins, Amberlite IRA 900 (Cl⁻ content: 4.2 mmol g⁻¹) and Amberlyst A-26 Br⁻ form (Br⁻ content: 3.5 mmol g⁻¹), respectively. The starting tetrafluoroborate salt (3.0 mmol) was dissolved in methanol (70 ml) and the solution was left in contact with the resin (enough resin was used in order to have a 3:1 halide/tetrafluoroborate ratio). After 20 h at room temperature, the resin was filtered and substituted with fresh resin four times. On evaporation of the final methanol solution, 4·Cl⁻ and 4·Br⁻ were obtained in pure form; the content of residual 4·BF₄⁻ was established < 0.05% in weight through ¹⁹F NMR after addition of 4·BF₄⁻ as an internal standard.

2.2. X-ray structure analyses

Good quality single crystals of all iodonium and bromonium derivatives were grown by slow solvent evaporation techniques under isothermal conditions at 298 K. In a typical crystallization procedure, a saturated solution of the halonium salt(s) in methanol (in order to obtain 1·ClO₄⁻, 1·PF₆⁻, 3·BF₄⁻, 4₃·(Br⁻)₂·BF₄⁻ and 4₃·(Cl⁻)₂·BF₄⁻) or hexafluoroisopropanol (in order to obtain 2·Cl⁻) was prepared at room temperature in a clear borosilicate glass vial which was left open in a closed cylindrical wide-mouth bottle containing paraffin oil. Solvents were allowed to slowly evaporate at room temperature and to be absorbed by paraffin oil until crystals were formed in a period ranging 3–5 days.

All the crystal data were collected with a Bruker APEX2000 diffractometer, with Mo Kα radiation, λ = 0.71073 Å, and collected at 103 K with the temperature controlled by a Bruker KRYOFLEX device. Data reduction and empirical absorption correction were carried out using SAINT and SADABS (Sheldrick, 1996 ). The structures were solved by direct methods (SIR2002) and refined on F² by SHELXL97. Tables S1 and S2 of the supporting information report the main data of the crystal structures containing cations 1–4. CCDC Nos. 1532402–1532407 contain the supplementary crystallographic data. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via http:www.ccdc.cam.ac.uk/data_request/cif.

3. Results and discussion

The cations upon which we will focus involve hypervalent bromines and hypervalent iodines. Each halogen atom is bonded covalently to two aryl groups, forming diarylbromonium and diaryliodonium cations. Derivatives of these are quite well known (Merritt & Olofsson, 2009 ). We will consider the following cations: diphenyliodonium (1), dibenzo[b,d]iodonium (2), phenyl-2-methoxycarbonylphenylbromonium (3) and di-p-fluorophenylbromonium (4) (Fig. 3). The anions include chloride (Cl^-), bromide (Br^-), perchlorate (ClO₄^-), tetrafluoroborate (BF₄^-) and hexafluorophosphate (PF₆^-). The last three anions contain hypervalent chlorine, boron and phosphorus, respectively.

Figure 3
Structures of studied iodonium and bromonium cations.

3.1. Computational modelling

To determine whether the hypervalent atoms in the cations and anions of interest do have σ-holes on the extensions of the covalent bonds to these atoms, we have computed optimized geometries using GAUSSIAN09 (Frisch et al., 2009 ) and electrostatic potentials on the surfaces of the cations 1–4, as well as the anions that contain hypervalent atoms: ClO₄^-, BF₄^- and PF₆^-. Frequency calculations were performed for each cation and anion to confirm the absence of imaginary frequencies. (The monatomic Cl^- and Br^- anions have uniform negative potentials over their spherical surfaces.) The ionic surfaces were taken to be the 0.001 a.u. contours of the cations' or anions' electronic densities (Bader et al., 1987 ) and the WFA-SAS (wave function analysis-surface analysis suite) code was used to obtain the electrostatic potentials (Bulat et al., 2010 ). The computational procedure was the M06-2X/6-311G(d). The M06-2X is a hybrid meta density functional developed for treating noncovalent interactions (Zhao & Truhlar, 2008 ), while the 6-311G(d) basis set has been found to be effective for molecular surface electrostatic potentials (Riley et al., 2016 ), including systems containing the larger halogens iodine and bromine (Riley et al., 2011 ).

The calculated structure and the surface electrostatic potential of the cation 1 is shown in Figs. 4(a) and (b). 1 has a V-shaped geometry, with a C—I⁺—C angle of about 99° between the two phenyl rings. The potential on the surface is positive everywhere, as is expected for a cation, but the values of the electrostatic potential varies considerably. The most positive regions are on the extensions of the C—I bonds, with maximum values of 111 kcal mol⁻¹. These correspond to σ-holes on the iodine. There are also strongly positive potentials in the cleaves between the two phenyl rings on both sides of 1, with maxima of 106 kcal mol⁻¹. However, they are much less accessible to interactions with negative sites than are the two σ-holes on the iodine.

Figure 4
Calculated ball-and-stick structure of (a) diphenyliodonium cation (1) and of (c) dibenzo[b,d]iodonium cation (2). Color code: gray, carbon; white, hydrogen; purple, iodine. Computed electrostatic potential on the 0.001 a.u. surface of cations 1 (b) and 2 (d) showing the same view as in (a) and (c), respectively. Color ranges, in kcal mol⁻¹: red, greater than 100; yellow, between 100 and 85; green, between 85 and 75; blue, less than 75. The black hemispheres indicate the most positive potentials of the iodine σ-holes on the extensions of the C—I bonds; the black sphere in (b) at the center corresponds to another potential maximum.

The least positive potentials on the surface of 1 are approximately 60 kcal mol⁻¹. They are associated with the π regions of the phenyl rings.

The bromine analogue of 1, the diphenylbromonium cation (not shown), has a structure and surface potential very similar to those of 1. However, the most positive potentials of the two σ-holes, on the extensions of the C—Br bonds, are 108 kcal mol⁻¹, slightly less than the σ-holes of 1. This is consistent with the lesser polarizability of bromine compared with iodine.

Cations 1 and 2 differ in that 2 has a C—C bond linking the two phenyl rings. This has a major effect upon its structure, which is planar (Fig. 4c). The C—I⁺—C angle is 82°. However, the surface electrostatic potential of 2 (Fig. 4d) again has its most positive regions on the extensions of the C—I bonds, denoting σ-holes on the iodine; their maximum values are 127 kcal mol⁻¹.

Cation 3 has an interesting structural feature, which can be seen in Fig. 5(a). While the computed C—Br⁺—C angle of approximately 101° is similar to the C—I⁺—C angle of 99° in 1, the ring that bears the methoxycarbonyl group in 3 is predicted to be considerably rotated. This can be attributed to an attractive interaction (dashed line) between the carbonyl oxygen and the nearby σ-hole of the bromine. The calculated Br⋯O separation is 2.628 Å and the C—Br⋯O angle is nearly linear at 176.9°. This is an intra-ionic XB.

Figure 5
(a) Calculated ball-and-stick structure of the phenyl-2-methoxycarbonylphenyl-bromonium cation, 3. Color code: gray, carbon; white, hydrogen; bright red, oxygen; dark red, bromine. The methoxycarbonyl group is at the bottom. The dashed line indicates the intra-ionic $[{\rm Br \cdots O}]$ interaction. (b) Computed electrostatic potential on the 0.001 a.u. surface of cation 3, showing the same view as in (a). Color ranges, in kcal mol⁻¹: red, greater than 90; yellow, between 90 and 75; green, between 75 and 60; blue, less than 60. The black hemisphere indicates the most positive potential of the lone σ-hole on the bromine, on the extension of the C—Br bond; the black sphere in the center corresponds to another potential maximum.

A close contact is sometimes characterized by means of the corresponding `normalized contact', Nc. This is defined as the ratio of the observed or calculated separation to the sum of the respective van der Waals atomic radii or Pauling ionic radii. Nc < 1 is taken to indicate an attractive interaction. The computed $[{\rm Br \cdots O}]$ distance in 3 gives an Nc of 0.75. Intra-ionic $[{\rm I \cdots O}]$ bonds have also been observed, with Nc of 0.73, in substituted diphenyliodonium cations (Halton et al., 2001 ; Zhdankin et al., 2003 ).

The electrostatic potential on the surface of 3 (Fig. 5B) reflects the rotation and intra-ionic interaction that have been described. The bromine does have a σ-hole, on the extension of the C—Br bond from the rotated ring; its maximum potential is 101 kcal mol⁻¹. However, the other σ-hole that would be expected for this hypervalent bromine is involved in the interaction with the carbonyl oxygen and therefore is not visible. The cation 3 also has strongly positive potentials in the cleaves between the two rings on both sides of 3, analogous to what is in 1. Their largest values are 97 kcal mol⁻¹, but they are rather poorly accessible.

It is interesting that an attractive interaction does occur in 3 between a positive σ-hole and the carbonyl oxygen, since the latter is also positive, although less so than other portions of the cationic surface (Fig. 5b). This may be due to the polarization induced by the strongly positive potential of the σ-hole with which the oxygen is interacting. This draws electronic charge to the oxygen and makes it less positive. This intra-ionic attractive interaction can be viewed as noncovalent (Politzer et al., 2015b ). Analogous effects have been observed in the past (Clark et al., 2014 ; Politzer et al., 2015a).

Cation 4 has a V-shaped geometry (Fig. 6a), similar to that of 1. The C—Br⁺—C angle is 102°. There are σ-holes on the extensions of the C—Br bonds, with maximum values of 114 kcal mol⁻¹ (Fig. 6b). As in 1 and 3, there are also strongly positive regions in the cleaves between the rings, on both sides of 4. Their most positive potentials are 116 kcal mol⁻¹, slightly higher than those of the σ-holes on the bromine. However, these positive regions are buried within the cleaves, whereas those of the bromine are on the outside, easily accessible. The fact that the σ-hole maxima in 4 are greater than the 111 kcal mol⁻¹ in 1, even though iodine is more polarizable than bromine, is due to the electron-attracting fluorines in 4. The fluorines, in turn, are the least positive portions of 4. Their lowest potentials are 45 kcal mol⁻¹.

Figure 6
(a) Calculated ball-and-stick structure of the di-p-fluorophenylbromonium cation, 4. Color code: gray, carbon; white, hydrogen; light blue, fluorine; dark red, bromine. (b) Computed electrostatic potential on the 0.001 a.u. surface of cation 4, showing the same view as in (a). Color ranges, in kcal mol⁻¹: red, greater than 100; yellow, between 100 and 85; green, between 85 and 75; blue, less than 75. The black hemispheres indicate the most positive potentials of the bromine σ-holes, on the extensions of the C—Br bonds; the black sphere in the center corresponds to another potential maximum.

The electrostatic potentials on the surfaces of the anions ClO₄^-, BF₄^- and PF₆^- are displayed in Fig. 7. The two tetrahedral ones, ClO₄^- and BF₄^-, each have eight σ-holes. Four are on the peripheral O atoms or fluorines, on the extensions of the Cl—O or B—F bonds; another four are on the chlorine or boron, on the extensions of the same bonds, Cl—O or B—F, respectively. All of these σ-holes have negative potentials, of course, but they are less negative than the surrounding regions. The most negative potentials on the surfaces of these two anions are between the peripheral atoms.

Figure 7
Computed electrostatic potentials on the 0.001 a.u. surfaces of (a) ClO₄^-, (b) BF₄^- and (c) PF₆^-. Color ranges, in kcal mol⁻¹: red, less negative than −115; yellow, between −115 and −120; green, between −120 and −133; blue, more negative than −133. In (a) and (b), the black hemispheres and sphere indicate the least negative potentials of the σ-holes of the peripheral atoms and the central atom; in (c) they indicate the least negative potentials of the σ-holes of just the peripheral atoms.

The PF₆^- anion presents an interesting feature: There are no visible σ-holes on the phosphorus. This is the result of the octahedral symmetry of the anion; on the extension of each F—P bond is another F—P bond; these block each other's potential σ-holes on the phosphorus. The only visible σ-holes on this anion's surface are on the fluorines, on the extensions of the P—F bonds. The most negative regions are between the fluorines.

Figs. 3–7 confirm that hypervalent atoms in polyatomic cations and anions do have σ-holes on the extensions of their covalent bonds, unless there is some special circumstance such as the intra-ionic interaction in 3 or the octahedral symmetry of PF₆^-. The σ-holes are more positive than the regions around them for the cations, and less negative than the surrounding regions for the anions.

3.2. Structural studies

In all examined structures HBs between aromatic H atoms and anions are present, consistent with the calculated positive electrostatic potential at H atoms of aryl halonium derivatives. However, the intermolecular interactions showing the lowest Nc values are, in all structures, the two most linear XBs between iodine, or bromine, atoms and anions, or lone-pair possessing atoms. The focus of this section will be on these short contacts.

Diphenyliodonium perchlorate (1·ClO₄⁻) forms, in the crystal lattice, tetrameric adducts which are assembled thanks to short $[{\rm I \cdots O}]$ XBs. The asymmetric unit of the crystal contains two independent cation–anion couples which form two different tetrameric adducts around two inversion centers. Topologically speaking, these tetramers are parallelograms wherein two iodine atoms and two ClO₄^- anions are the vertexes and two pairs of $[{\rm I \cdots O}]$ contacts are the sides. Perchlorate anions function as bidentate XB acceptors, two oxygen atoms of the two independent perchlorate anions enter iodonium sites along the prolongation of the two C—I bonds and form short and directional $[{\rm I \cdots O}]$ contacts (black dashed lines in Fig. 8). These $[{\rm I \cdots O}]$ separations are 2.8761 (10) and 3.0089 (12) Å long in one tetramer (Fig. 8, top) and 2.9153 (9) and 3.0147 (11) Å in the other (Fig. 8, bottom), these values corresponding to Nc in the range 0.77–0.81. The respective C—I⋯O angles are 172.36 (4)° and 168.75 (4)° for the former tetramer and 169.52 (3)° and 170.97 (3)° for the latter. Other I⋯O short contacts are present (pink and orange dashed lines in Fig. 8), but they are longer and less linear than those described above (the average I⋯O separation is 3.340 Å (Nc = 0.90), and the average C—I⋯O angle is 103°). These structural features are consistent with the calculated anisotropic distribution of the electron density on iodine where two σ-holes are opposite to the C—I covalent bonds: When anions enter these holes, the resulting I⋯O contacts are shorter than when entering far from the holes. The overall pattern of interactions can be understood as charge-assisted and bifurcated XBs. Cation–anion attraction plays a role in I⋯O short contacts (i.e. they are charge-assisted interactions) and the σ-hole presence accounts for why they are shorter when the C—I⋯O angles are close to linearity.

Figure 8
Representation (Mercury 3.8, ball and stick) of the two different tetrameric adducts formed by the I⋯O XBs in the crystal lattice of 1·ClO₄⁻. Hydrogen atoms have been omitted for simplicity; Nc values of XBs and angles are given close to interactions and at the bottom, respectively. Color code: grey, carbon; red, oxygen; green, chlorine; purple, iodine. In the top representation I1, the I⋯O short contact it forms out of C—I bond elongations and corresponding parameters are in pink. In the bottom representation O8, the I⋯O short contact it forms out of C—I bond elongations and corresponding parameters are in orange; also I⋯O XB formed by O2 out of C—I bond elongations and corresponding parameters are in orange.

Bifurcated XBs are attractive interactions wherein two electron-rich sites enter a σ-hole on a halogen, after either symmetric or dissymmetric geometry (Ji et al., 2011 ). Bifurcated XBs are rarely formed by monovalent halocarbons, possibly as the surface electrostatic potential in these compounds typically changes from positive at the hole to negative at the orthogonal belt. The electrostatic potential remains positive on the whole surface of the halogens in iodonium, and bromonium, derivatives and it may be expected that bifurcated XBs are not as rare for these donors. Diphenyliodonium hexafluorophosphate (1·PF₆⁻) forms tetrameric adducts similar to those in 1·ClO₄⁻. Two $[{\rm {\bf PF_6^-}}]$ units are pinned in their position thanks to two fluorine atoms (F3A and F5A) entering C—I bonds extensions (C1—I1 and C7—I1, respectively) and forming short I⋯F contacts (Nc = 0.91 and 0.93, black dashed lines in Fig. 9). Here too bifurcated XBs are present; in fact, the covalent connectivity within $[{\rm {\bf PF_6^-}}]$ delivers a third fluorine (F1A) close to the iodine atoms. Further I⋯F XBs are formed, but they are much longer than the XBs discussed above (Nc = 0.99, pink dashed lines in Fig. 9).

Figure 9
Representation (Mercury 3.8, ball and stick) of the tetrameric adduct formed by the I⋯F XBs in the crystal lattice of 1·PF₆⁻. Hydrogen atoms have been omitted for simplicity; Nc values of XBs and angles are given close to interactions and at the bottom, respectively. Color code: grey, carbon; yellowish green, fluorine; purple, iodine; orange, phosphorus. Less short I⋯F contacts and corresponding parameters are in pink.

Crystalline 1·PF₆⁻ provides a good example of how the anion can influence the structure of the cation. In fact, in the lattice the cation does not have the equilibrium geometry of the free cation 1 (Fig. 4), possibly due to the presence of a net of attractive H⋯F hydrogen bonds which pin the phenyl rings in their position. Additionally in 1·ClO₄⁻ the cation does not have the equilibrium geometry and the net of H⋯O hydrogen bonds may also be the cause in that case.

Dibenzo[b,d]iodolium chloride (2·ClO⁻) is a cell-permeable, irreversible inhibitor of endothelial nitric oxide synthase (Xu et al., 2014 ) and in the solid it forms discrete tetrameric adducts (Fig. S1) via linear $[{\rm {C-I \cdots Cl^-}}]$ interactions. Each chloride and each iodine is involved in two such interactions and alternates at the vertexes of a parallelogram whose sides, the I⋯Cl⁻ interactions, are in the range 3.0694 (9)–3.1781 (6) Å (Nc being 0.81–0.83). The C—I⋯Cl⁻¹ angles vary between 170.32 (5)° and 174.70 (5)°. C—I⋯Cl⁻ interactions are clearly XBs along the extensions of the C—I bonds and between the iodine σ-holes depicted in Fig. 4 and the chloride ions.

The crystal lattice of phenyl-2-methoxycarbonylphenylbromonium tetrafluoroborate (3·BF₄⁻) shows that the intra-ionic Br⋯O halogen bond that was found computationally in the free cation 3, between the carbonyl oxygen and the nearest bromine σ-hole, remains intact in the tetrafluoroborate salt. The Br⋯O separation observed crystallographically in the salt is 2.6476 (12) Å, with Nc = 0.76; these are close to the calculated values for the free cation, 2.628 Å and Nc = 0.75. The experimental C—Br⋯O angle is 170.98 (6)° in the crystal versus 176.9 (6)° in the computed free cation. The presence of the tetrafluoroborate anion does not disrupt the Br⋯O XB in the cation, probably as this is an intramolecular interaction forming a five-membered ring (Fig. 10).

Figure 10
Representation (Mercury 3.8, ball and stick) of diphenyl bromonium derivative 3·BF₄⁻. The mean square plane through Br1, C1, C2, C13 and O2 (semitransparent yellowish) shows that fluorine and oxygen atoms enter the elongation of C—Br covalent bonds. Hydrogen atoms have been omitted for simplicity; XBs are black dotted lines, the respective Nc values and angles are given close to interactions and at the bottom, in order. Color codes (above mean square plane): grey, carbon; red, oxygen; brown, bromine; yellowish green, fluorine, pink, boron.

Similar intramolecular I⋯O contacts (2.615 and 2.638 Å long, Nc = 0.73) are observed in a phenyl-2-carboxamidophenyliodonium trifluoromethanesulfonate and in a phenyl-2-acylphenyl iodonium trifluoromethanesulfonate (Zhdankin et al., 2003; Halton et al., 2001) where the carbonyl oxygen gets close to the positive halogen on the elongation of the C—I bond. Analogous arrangements are observed in phenyl-alkenyl iodonium trifluoromethanesulfonates bearing a conveniently positioned carbonyl (Williamson et al., 1993 ). It is interesting to observe that a neutral donor of electron density can prevail over poorly nucleophilic anions in entering bromonium or iodonium sites not only when intra- but also intermolecular interactions are formed (Ochiai et al., 2003 ; Suefuji et al., 2006 ).

The other σ-hole on the bromine in 3·BF₄⁻ interacts with a fluorine atom of the anion (Fig. 10). The Br⋯F distance is 2.8900 (12) Å, which yields Nc = 0.87, and the C—Br⋯F angle is 168.88 (5)°. This nearly linear arrangement of atoms in the interaction is consistent with the computed anisotropic distribution of the electron density on bromine and with the two σ-holes opposite the C—Br covalent bonds.

Finally we crystallized solutions containing equimolar amounts of di-p-fluorophenylbromonium tetrafluoroborate and di-p-fluorophenylbromonium chloride, or bromide. We examined initially formed crystals (precipitation of 10–15% of starting materials). The objective was to determine whether (a) different crystals containing a single anion were formed (and if so, what was the ratio of the two different crystals), or (b) the precipitation of a mixed cocrystal containing both anions was preferred (and if so, what was the composition).

The fluoborate/chloride and fluoborate/bromide mixtures behave similarly. DSC analyses showed that both mixtures afford reproducibly a single crystalline species and X-ray analyses revealed that crystals formed by the chloride and bromide mixtures are both containing the halide and fluoborate anions in 2:1 ratio (they are thus denoted 4₃·(Cl⁻)₂·BF₄⁻ and 4₃·(Br⁻)₂·BF₄⁻). In the crystal lattices are trigonal bipyramidal adducts in which the bromine of each cation 4 has short contacts with two chloride ions (Fig. 11), or two bromide ions (Fig. S2), along the extensions of the C—Br bonds. Each halide ion, in turn, interacts with three different bromine σ-holes. These are all C—Br---Cl⁻ or C—Br---Br⁻¹ halogen bonds; the interactions are nearly linear, with the C—Br---Cl⁻ and C—Br---Br⁻ angles being 173.40 (5)° and 174.18 (11)°, respectively. The Br---Cl⁻ separations are 3.0493 (5) Å, the Br---Cl⁻ are 3.1595 (6) Å. Nc is 0.83 in both cases.

Figure 11
Representation (Mercury 3.8, ball and stick) of the trigonal bipyramidal adduct present in 4₃·(Cl⁻)₂·BF₄⁻. Br⋯Cl⁻ XBs are black dashed lines and corresponding Nc values are given; hydrogen atoms have been omitted for simplicity. Color code: grey, carbon; yellowish green, fluorine; pink, boron; brown, bromine; green, chlorine.

The chloride and bromide anions also form hydrogen bonds with the phenyl rings, as do the fluorines of the tetrafluoroborate anions. However, the latter anions do not interact with the σ-holes of the bromines; the BF₄^- fluorines do not enter into Br---F halogen bonds, as they do in the lattice structure shown in Fig. 10. The bromine σ-holes interact preferentially with the chloride and bromide anions. Monovalent halogens show the same preference: They are more prone to halogen bonds with chloride and bromide anions than with the fluorines of the tetrafluoroborate anion (Metrangolo et al., 2009 ).

The C—Br---Br⁻ interactions in crystalline 4-bromopyridium bromide have lower Nc values, 0.95 (Freytag et al., 1999 ), than the C—Br---F in crystalline 4-bromopyridium tetrafluoroborate, Nc = 0.99 (Awwadi et al., 2012 ), which may be interpreted as suggesting that the former interactions are stronger. The preference for the monatomic anions can probably be attributed to their negative charges being more concentrated than that of the polyatomic BF₄^- anion.

4. Conclusions

We have demonstrated that hypervalent atoms that are constituents of polyatomic cations and anions do have a σ-hole on the extension of each covalent bond, unless there is some complicating factor such as the intra-ionic interaction in the cation 3 or the octahedral symmetry in the PF₆^- anion. In the anions, the σ-holes are less negative than the surrounding region and in the cations they are more positive than their surroundings.

The positive σ-holes on the cations can interact attractively with negative sites, as in the lattice of bromonion and iodonium derivatives shown in Figs. 8–11 . The negative σ-holes on the anions can similarly interact with positive sites, and it must be recognized that positive sites may interact preferentially with the more negative regions around the negative σ-holes.

In this context, we emphasize that interpretations concerning attractive interactions within ionic lattices should be made especially cautiously. Crystallographic analyses can reveal close contacts, and computed electrostatic potentials provide insight into the variations of the positive potentials on cationic surfaces and the negative potentials on anionic ones. These variations account for the directional preferences in the XBs between the halogen atom of iodonium and bromonium cations 1–4 and neutral and anionic sites. This preferential directionality is a common feature of halonium derivatives and Fig. 12 shows it for iodonium structures in the Cambridge Crystallographic Data Centre (CCDC).

Figure 12
Distribution of the two C—I⁺⋯electron donor angles (°) versus XB distances for CCDC structures containing the C—I⁺—C moiety. The analysis has been made using the Cambridge Structure Database (CSD, Version 5.37, November 2015, including updates until February 2016). Blue dots and red squares are the two angles associated with any XB; for bi-, trifurcated XBs, the most linear was selected. The mean value of the C—I⁺—C angle in the considered structures is 94.08°; the clustering of the C—I⁺⋯electron donor angles around 90° and 170° is indicative of their preferential linearity.

It must also be kept in mind that the cations are completely positive and anions completely negative; thus any portion of one will interact attractively with any portion of the other, the strength of the interaction depending upon the separation. This feature may play a major role in the occurrence of the bifurcated halogen bonds depicted in Figs. 8 and 9.

Supporting information

CCDC references: 1532402; 1532403; 1532404; 1532405; 1532406; 1532407

Crystal structure: contains datablocks gc131, gc140LT, gc143, gc148, gc154, gc162. DOI: https://doi.org/10.1107/S2052252517004262/lc5079sup1.cif

Structure factors: contains datablock gc131. DOI: https://doi.org/10.1107/S2052252517004262/lc5079gc131sup2.hkl

Structure factors: contains datablock gc140LT. DOI: https://doi.org/10.1107/S2052252517004262/lc5079gc140LTsup3.hkl

Structure factors: contains datablock gc143. DOI: https://doi.org/10.1107/S2052252517004262/lc5079gc143sup4.hkl

Structure factors: contains datablock gc148. DOI: https://doi.org/10.1107/S2052252517004262/lc5079gc148sup5.hkl

Structure factors: contains datablock gc154. DOI: https://doi.org/10.1107/S2052252517004262/lc5079gc154sup6.hkl

Structure factors: contains datablock gc162. DOI: https://doi.org/10.1107/S2052252517004262/lc5079gc162sup7.hkl

Tables of structural data and calculated atomic coordinations, and structural figures. DOI: https://doi.org/10.1107/S2052252517004262/lc5079sup8.pdf

Computing details top

For all compounds, data collection: Bruker APEX2; cell refinement: Bruker SAINT; data reduction: Bruker SAINT; program(s) used to solve structure: SIR2002 (Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Polidori, G. & Spagna, R. (2003). J. Appl. Cryst. 36, 1103.); program(s) used to refine structure: SHELXL (Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122); molecular graphics: ORTEP-3 (Farrugia, L.J. (1997) Jour. Appl. Cryst. 30, 565) Mercury (Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457; software used to prepare material for publication: SHELXTL.

(gc131) top

Crystal data top

(C₁₂H₁₀I⁺·ClO₄⁻	F(000) = 1472
M_r = 380.55	D_x = 1.950 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9287 reflections
a = 12.2320 (12) Å	θ = 2.8–42.5°
b = 12.7073 (15) Å	µ = 2.68 mm⁻¹
c = 17.150 (2) Å	T = 103 K
β = 103.500 (8)°	Needle, colourless
V = 2592.1 (5) Å³	0.43 × 0.16 × 0.08 mm
Z = 8

Data collection top

Bruker APEX-II CCD diffractometer	18783 independent reflections
Radiation source: fine-focus sealed tube	15302 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
φ and ω scans	θ_max = 43.1°, θ_min = 2.6°
Absorption correction: multi-scan Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.	h = −20→22
T_min = 0.420, T_max = 0.516	k = −24→24
162962 measured reflections	l = −32→32

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.054	All H-atom parameters refined
S = 1.06	w = 1/[σ²(F_o²) + (0.0202P)² + 1.2924P] where P = (F_o² + 2F_c²)/3
18783 reflections	(Δ/σ)_max = 0.003
405 parameters	Δρ_max = 2.09 e Å⁻³
190 restraints	Δρ_min = −1.33 e Å⁻³

Special details top

Experimental. Bruker KRYOFLEX low temperature device.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
I1	0.09002 (2)	0.60093 (2)	0.40244 (2)	0.01389 (1)
C1	0.19416 (8)	0.60174 (8)	0.31989 (6)	0.01409 (14)
C2	0.28229 (9)	0.53010 (8)	0.33213 (6)	0.01587 (15)
H2	0.2939 (15)	0.4823 (12)	0.3744 (9)	0.024 (4)*
C3	0.34984 (9)	0.52858 (9)	0.27676 (7)	0.01814 (17)
H3	0.4106 (12)	0.4818 (12)	0.2854 (10)	0.021 (4)*
C4	0.32994 (10)	0.59905 (9)	0.21326 (7)	0.02092 (19)
H4	0.3761 (15)	0.5997 (14)	0.1756 (10)	0.027 (5)*
C5	0.24047 (10)	0.66982 (10)	0.20233 (7)	0.02166 (19)
H5	0.2262 (16)	0.7170 (13)	0.1592 (9)	0.032 (5)*
C6	0.17031 (9)	0.67095 (9)	0.25569 (7)	0.01810 (17)
H6	0.1096 (12)	0.7195 (12)	0.2480 (10)	0.023 (4)*
C7	0.05677 (9)	0.76292 (8)	0.39835 (6)	0.01507 (15)
C8	0.13270 (10)	0.83041 (9)	0.44668 (7)	0.01967 (18)
H8	0.1980 (12)	0.8048 (14)	0.4811 (10)	0.028 (5)*
C9	0.10444 (11)	0.93663 (10)	0.44485 (8)	0.0245 (2)
H9	0.1560 (14)	0.9843 (13)	0.4774 (10)	0.028 (5)*
C10	0.00441 (11)	0.97295 (9)	0.39589 (8)	0.0236 (2)
H10	−0.0150 (16)	1.0459 (10)	0.3954 (11)	0.030 (5)*
C11	−0.06910 (11)	0.90336 (10)	0.34808 (9)	0.0249 (2)
H11	−0.1374 (12)	0.9281 (15)	0.3154 (10)	0.033 (5)*
C12	−0.04398 (10)	0.79639 (9)	0.34918 (8)	0.02159 (19)
H12	−0.0910 (15)	0.7469 (13)	0.3185 (11)	0.033 (5)*
I2	0.38164 (2)	0.38947 (2)	0.57425 (2)	0.01454 (1)
C13	0.30905 (9)	0.39126 (8)	0.67512 (6)	0.01543 (15)
C14	0.22917 (9)	0.46840 (9)	0.67675 (7)	0.01737 (16)
H14	0.2126 (15)	0.5180 (12)	0.6357 (9)	0.025 (4)*
C15	0.17914 (10)	0.46915 (9)	0.74200 (7)	0.02036 (18)
H15	0.1252 (13)	0.5211 (12)	0.7446 (11)	0.025 (4)*
C16	0.20889 (11)	0.39402 (10)	0.80250 (7)	0.0224 (2)
H16	0.1749 (16)	0.3919 (13)	0.8467 (9)	0.025 (5)*
C17	0.28945 (11)	0.31817 (10)	0.79906 (7)	0.0225 (2)
H17	0.3100 (15)	0.2683 (13)	0.8393 (9)	0.030 (5)*
C18	0.34197 (10)	0.31656 (9)	0.73494 (7)	0.01968 (18)
H18	0.3984 (13)	0.2670 (12)	0.7329 (11)	0.025 (4)*
C19	0.43651 (9)	0.23323 (8)	0.58656 (6)	0.01524 (15)
C20	0.36265 (10)	0.15387 (9)	0.55284 (8)	0.02152 (19)
H20	0.2910 (12)	0.1689 (16)	0.5245 (11)	0.035 (5)*
C21	0.40305 (12)	0.05136 (10)	0.56103 (9)	0.0271 (2)
H21	0.3537 (14)	−0.0060 (12)	0.5386 (11)	0.029 (5)*
C22	0.51310 (12)	0.03031 (9)	0.60221 (8)	0.0244 (2)
H22	0.5403 (15)	−0.0407 (10)	0.6084 (11)	0.027 (5)*
C23	0.58461 (11)	0.11143 (10)	0.63479 (9)	0.0250 (2)
H23	0.6590 (12)	0.0972 (15)	0.6635 (12)	0.037 (6)*
C24	0.54694 (10)	0.21531 (9)	0.62685 (8)	0.02128 (19)
H24	0.5916 (14)	0.2721 (12)	0.6455 (11)	0.033 (5)*
Cl1	0.06067 (2)	0.32196 (2)	0.43277 (2)	0.01472 (4)
O1	0.12334 (11)	0.36877 (8)	0.38014 (7)	0.0324 (2)
O2	0.08355 (8)	0.38147 (7)	0.50714 (6)	0.02305 (16)
O3	0.09490 (10)	0.21500 (7)	0.44883 (7)	0.0299 (2)
O4	−0.05744 (9)	0.32702 (10)	0.39747 (7)	0.0355 (2)
Cl2	0.43027 (2)	0.67711 (2)	0.58345 (2)	0.01637 (4)
O5	0.33653 (10)	0.61905 (9)	0.53731 (9)	0.0442 (3)
O6	0.53451 (8)	0.63961 (8)	0.56760 (6)	0.02746 (19)
O7	0.43551 (10)	0.66036 (10)	0.66771 (7)	0.0347 (2)
O8	0.41558 (9)	0.78677 (7)	0.56462 (6)	0.02570 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01299 (2)	0.01339 (2)	0.01580 (3)	−0.00028 (2)	0.00440 (2)	0.00098 (2)
C1	0.0127 (3)	0.0145 (3)	0.0152 (4)	0.0001 (3)	0.0035 (3)	0.0011 (3)
C2	0.0144 (4)	0.0150 (4)	0.0180 (4)	0.0010 (3)	0.0033 (3)	0.0020 (3)
C3	0.0160 (4)	0.0177 (4)	0.0214 (4)	0.0020 (3)	0.0059 (3)	−0.0005 (3)
C4	0.0217 (5)	0.0230 (5)	0.0203 (5)	0.0014 (4)	0.0093 (4)	0.0014 (4)
C5	0.0235 (5)	0.0233 (5)	0.0199 (5)	0.0031 (4)	0.0086 (4)	0.0059 (4)
C6	0.0180 (4)	0.0191 (4)	0.0176 (4)	0.0029 (3)	0.0049 (3)	0.0043 (3)
C7	0.0156 (4)	0.0137 (3)	0.0161 (4)	−0.0001 (3)	0.0042 (3)	−0.0002 (3)
C8	0.0180 (4)	0.0179 (4)	0.0215 (5)	−0.0018 (3)	0.0013 (3)	−0.0014 (3)
C9	0.0257 (5)	0.0174 (4)	0.0291 (6)	−0.0038 (4)	0.0036 (4)	−0.0033 (4)
C10	0.0267 (5)	0.0152 (4)	0.0300 (6)	0.0011 (4)	0.0089 (4)	0.0017 (4)
C11	0.0228 (5)	0.0197 (5)	0.0297 (6)	0.0048 (4)	0.0009 (4)	0.0026 (4)
C12	0.0178 (4)	0.0180 (4)	0.0257 (5)	0.0021 (3)	−0.0015 (4)	−0.0016 (4)
I2	0.01400 (3)	0.01313 (2)	0.01676 (3)	0.00199 (2)	0.00411 (2)	0.00152 (2)
C13	0.0140 (4)	0.0163 (4)	0.0158 (4)	0.0001 (3)	0.0031 (3)	−0.0008 (3)
C14	0.0159 (4)	0.0175 (4)	0.0184 (4)	0.0008 (3)	0.0035 (3)	−0.0024 (3)
C15	0.0177 (4)	0.0224 (5)	0.0217 (5)	−0.0013 (3)	0.0060 (4)	−0.0059 (4)
C16	0.0216 (5)	0.0270 (5)	0.0198 (5)	−0.0044 (4)	0.0072 (4)	−0.0045 (4)
C17	0.0239 (5)	0.0265 (5)	0.0172 (4)	−0.0011 (4)	0.0049 (4)	0.0027 (4)
C18	0.0192 (4)	0.0214 (4)	0.0181 (4)	0.0030 (3)	0.0035 (3)	0.0027 (3)
C19	0.0158 (4)	0.0129 (3)	0.0171 (4)	0.0013 (3)	0.0039 (3)	0.0010 (3)
C20	0.0188 (5)	0.0163 (4)	0.0275 (5)	−0.0019 (3)	0.0014 (4)	−0.0001 (4)
C21	0.0286 (6)	0.0148 (4)	0.0365 (7)	−0.0023 (4)	0.0046 (5)	−0.0004 (4)
C22	0.0297 (6)	0.0148 (4)	0.0296 (6)	0.0042 (4)	0.0087 (5)	0.0038 (4)
C23	0.0224 (5)	0.0204 (5)	0.0297 (6)	0.0072 (4)	0.0009 (4)	0.0023 (4)
C24	0.0173 (4)	0.0173 (4)	0.0264 (5)	0.0030 (3)	−0.0007 (4)	−0.0012 (4)
Cl1	0.01535 (9)	0.01221 (8)	0.01709 (9)	−0.00070 (7)	0.00479 (7)	−0.00096 (7)
O1	0.0503 (7)	0.0232 (4)	0.0335 (5)	−0.0053 (4)	0.0295 (5)	−0.0011 (4)
O2	0.0258 (4)	0.0249 (4)	0.0201 (4)	−0.0068 (3)	0.0086 (3)	−0.0078 (3)
O3	0.0398 (5)	0.0148 (3)	0.0381 (5)	0.0084 (3)	0.0151 (4)	0.0035 (3)
O4	0.0188 (4)	0.0397 (6)	0.0411 (6)	0.0011 (4)	−0.0070 (4)	−0.0055 (5)
Cl2	0.01518 (9)	0.01202 (8)	0.02113 (10)	0.00137 (7)	0.00262 (7)	0.00049 (7)
O5	0.0295 (5)	0.0255 (5)	0.0625 (8)	−0.0006 (4)	−0.0198 (5)	−0.0072 (5)
O6	0.0267 (4)	0.0310 (5)	0.0285 (4)	0.0132 (4)	0.0143 (4)	0.0082 (4)
O7	0.0410 (6)	0.0403 (6)	0.0275 (5)	0.0149 (5)	0.0175 (4)	0.0122 (4)
O8	0.0367 (5)	0.0119 (3)	0.0300 (4)	0.0042 (3)	0.0108 (4)	0.0023 (3)

Geometric parameters (Å, º) top

I1—C7	2.0962 (10)	C14—C15	1.3953 (16)
I1—C1	2.1141 (10)	C14—H14	0.930 (12)
C1—C6	1.3859 (14)	C15—C16	1.3942 (18)
C1—C2	1.3890 (14)	C15—H15	0.942 (12)
C2—C3	1.3969 (15)	C16—C17	1.3895 (18)
C2—H2	0.931 (12)	C16—H16	0.946 (12)
C3—C4	1.3868 (16)	C17—C18	1.3972 (16)
C3—H3	0.936 (12)	C17—H17	0.927 (12)
C4—C5	1.3949 (17)	C18—H18	0.941 (12)
C4—H4	0.952 (12)	C19—C24	1.3849 (15)
C5—C6	1.3932 (16)	C19—C20	1.3869 (16)
C5—H5	0.936 (12)	C20—C21	1.3887 (17)
C6—H6	0.951 (12)	C20—H20	0.918 (12)
C7—C12	1.3876 (15)	C21—C22	1.392 (2)
C7—C8	1.3878 (15)	C21—H21	0.967 (12)
C8—C9	1.3919 (17)	C22—C23	1.3826 (19)
C8—H8	0.934 (12)	C22—H22	0.959 (12)
C9—C10	1.3912 (19)	C23—C24	1.3944 (16)
C9—H9	0.955 (12)	C23—H23	0.946 (13)
C10—C11	1.3852 (19)	C24—H24	0.917 (12)
C10—H10	0.957 (12)	Cl1—O3	1.4299 (9)
C11—C12	1.3928 (17)	Cl1—O4	1.4317 (10)
C11—H11	0.944 (12)	Cl1—O1	1.4418 (10)
C12—H12	0.928 (12)	Cl1—O2	1.4528 (9)
I2—C19	2.0907 (10)	Cl2—O8	1.4322 (9)
I2—C13	2.1210 (11)	Cl2—O5	1.4358 (11)
C13—C18	1.3866 (15)	Cl2—O6	1.4451 (9)
C13—C14	1.3889 (15)	Cl2—O7	1.4473 (11)

C7—I1—C1	96.63 (4)	C15—C14—H14	122.9 (11)
C6—C1—C2	123.24 (9)	C16—C15—C14	120.33 (11)
C6—C1—I1	119.15 (7)	C16—C15—H15	120.6 (11)
C2—C1—I1	117.60 (7)	C14—C15—H15	119.0 (11)
C1—C2—C3	117.88 (9)	C17—C16—C15	120.52 (11)
C1—C2—H2	121.2 (11)	C17—C16—H16	117.6 (11)
C3—C2—H2	120.9 (11)	C15—C16—H16	121.9 (11)
C4—C3—C2	120.11 (10)	C16—C17—C18	120.30 (11)
C4—C3—H3	121.4 (11)	C16—C17—H17	121.0 (12)
C2—C3—H3	118.4 (11)	C18—C17—H17	118.7 (12)
C3—C4—C5	120.68 (10)	C13—C18—C17	117.69 (11)
C3—C4—H4	121.0 (11)	C13—C18—H18	121.3 (11)
C5—C4—H4	118.3 (11)	C17—C18—H18	121.0 (11)
C6—C5—C4	120.18 (10)	C24—C19—C20	123.58 (10)
C6—C5—H5	118.8 (12)	C24—C19—I2	117.34 (8)
C4—C5—H5	121.0 (12)	C20—C19—I2	119.07 (8)
C1—C6—C5	117.87 (10)	C19—C20—C21	117.26 (11)
C1—C6—H6	122.4 (11)	C19—C20—H20	121.2 (13)
C5—C6—H6	119.7 (11)	C21—C20—H20	121.5 (13)
C12—C7—C8	123.31 (10)	C20—C21—C22	120.70 (12)
C12—C7—I1	117.34 (8)	C20—C21—H21	119.5 (11)
C8—C7—I1	119.29 (8)	C22—C21—H21	119.8 (11)
C7—C8—C9	117.24 (11)	C23—C22—C21	120.49 (11)
C7—C8—H8	121.1 (12)	C23—C22—H22	119.1 (11)
C9—C8—H8	121.6 (12)	C21—C22—H22	120.4 (11)
C10—C9—C8	120.94 (11)	C22—C23—C24	120.19 (12)
C10—C9—H9	120.7 (11)	C22—C23—H23	120.6 (12)
C8—C9—H9	118.4 (11)	C24—C23—H23	119.2 (12)
C11—C10—C9	120.23 (11)	C19—C24—C23	117.77 (11)
C11—C10—H10	119.2 (12)	C19—C24—H24	118.5 (12)
C9—C10—H10	120.5 (12)	C23—C24—H24	123.7 (12)
C10—C11—C12	120.29 (12)	O3—Cl1—O4	110.21 (7)
C10—C11—H11	120.1 (12)	O3—Cl1—O1	109.77 (6)
C12—C11—H11	119.6 (13)	O4—Cl1—O1	110.38 (8)
C7—C12—C11	117.98 (11)	O3—Cl1—O2	109.75 (6)
C7—C12—H12	118.8 (12)	O4—Cl1—O2	108.44 (6)
C11—C12—H12	123.2 (12)	O1—Cl1—O2	108.25 (6)
C19—I2—C13	96.52 (4)	O8—Cl2—O5	109.49 (7)
C18—C13—C14	123.54 (10)	O8—Cl2—O6	110.37 (6)
C18—C13—I2	119.44 (8)	O5—Cl2—O6	110.68 (8)
C14—C13—I2	117.02 (8)	O8—Cl2—O7	110.01 (6)
C13—C14—C15	117.60 (10)	O5—Cl2—O7	108.55 (9)
C13—C14—H14	119.5 (11)	O6—Cl2—O7	107.70 (6)

C6—C1—C2—C3	0.16 (16)	C18—C13—C14—C15	−0.72 (17)
I1—C1—C2—C3	178.56 (8)	I2—C13—C14—C15	178.76 (8)
C1—C2—C3—C4	1.74 (16)	C13—C14—C15—C16	−0.42 (17)
C2—C3—C4—C5	−2.06 (18)	C14—C15—C16—C17	0.66 (18)
C3—C4—C5—C6	0.45 (19)	C15—C16—C17—C18	0.23 (19)
C2—C1—C6—C5	−1.71 (17)	C14—C13—C18—C17	1.58 (18)
I1—C1—C6—C5	179.91 (9)	I2—C13—C18—C17	−177.89 (9)
C4—C5—C6—C1	1.38 (18)	C16—C17—C18—C13	−1.30 (18)
C12—C7—C8—C9	0.13 (18)	C24—C19—C20—C21	0.42 (19)
I1—C7—C8—C9	−176.94 (9)	I2—C19—C20—C21	178.78 (10)
C7—C8—C9—C10	−0.50 (19)	C19—C20—C21—C22	0.6 (2)
C8—C9—C10—C11	0.1 (2)	C20—C21—C22—C23	−0.9 (2)
C9—C10—C11—C12	0.6 (2)	C21—C22—C23—C24	0.2 (2)
C8—C7—C12—C11	0.59 (19)	C20—C19—C24—C23	−1.10 (19)
I1—C7—C12—C11	177.71 (10)	I2—C19—C24—C23	−179.48 (10)
C10—C11—C12—C7	−0.9 (2)	C22—C23—C24—C19	0.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1	0.93 (1)	2.56 (2)	3.0674 (14)	115 (1)
C2—H2···O6ⁱ	0.93 (1)	2.61 (2)	3.2909 (14)	130 (1)
C20—H20···O3	0.92 (1)	2.52 (1)	3.4328 (17)	178 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

(gc140LT) top

Crystal data top

C₁₂H₁₀I⁺·F₆P⁻	F(000) = 816
M_r = 426.07	D_x = 2.003 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9828 reflections
a = 5.9721 (5) Å	θ = 2.7–49.9°
b = 12.9442 (12) Å	µ = 2.43 mm⁻¹
c = 18.387 (2) Å	T = 103 K
β = 96.195 (12)°	Irregular block, colourless
V = 1413.1 (2) Å³	0.29 × 0.26 × 0.22 mm
Z = 4

Data collection top

Bruker APEX-II CCD diffractometer	14805 independent reflections
Radiation source: fine-focus sealed tube	12120 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
φ and ω scans	θ_max = 50.3°, θ_min = 2.7°
Absorption correction: multi-scan Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.	h = −12→12
T_min = 0.358, T_max = 0.442	k = −26→27
77147 measured reflections	l = −39→39

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.024	Hydrogen site location: difference Fourier map
wR(F²) = 0.063	Only H-atom coordinates refined
S = 1.03	w = 1/[σ²(F_o²) + (0.0279P)² + 0.5366P], where P = (F_o² + 2F_c²)/3
14804 reflections	(Δ/σ)_max = 0.002
211 parameters	Δρ_max = 1.48 e Å⁻³
0 restraints	Δρ_min = −1.21 e Å⁻³

Special details top

Experimental. Bruker KRYOFLEX low temperature device.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
I1	0.79933 (2)	0.35808 (2)	0.08706 (2)	0.01530 (1)
C1	1.06619 (13)	0.36596 (6)	0.17255 (4)	0.01541 (10)
C2	1.06419 (16)	0.30065 (8)	0.23226 (5)	0.02046 (13)
H2	0.951 (3)	0.2509 (14)	0.2360 (10)	0.025*
C3	1.24265 (18)	0.30726 (9)	0.28747 (5)	0.02374 (16)
H3	1.245 (3)	0.2688 (14)	0.3275 (10)	0.028*
C4	1.41313 (18)	0.37949 (9)	0.28262 (5)	0.02316 (15)
H4	1.535 (3)	0.3816 (15)	0.3184 (11)	0.028*
C5	1.40795 (16)	0.44544 (8)	0.22290 (5)	0.02056 (13)
H5	1.524 (3)	0.4968 (14)	0.2220 (9)	0.025*
C6	1.23337 (14)	0.43901 (7)	0.16599 (5)	0.01693 (11)
H6	1.224 (3)	0.4794 (13)	0.1246 (9)	0.020*
C7	0.71712 (14)	0.20246 (6)	0.10017 (5)	0.01668 (11)
C8	0.5551 (2)	0.17919 (8)	0.14581 (7)	0.02738 (19)
H8	0.485 (3)	0.2319 (15)	0.1718 (10)	0.033*
C9	0.4934 (2)	0.07545 (9)	0.15192 (9)	0.0329 (2)
H9	0.383 (4)	0.0601 (17)	0.1808 (12)	0.039*
C10	0.5913 (2)	0.00037 (8)	0.11244 (7)	0.0313 (2)
H10	0.535 (4)	−0.0735 (16)	0.1203 (11)	0.038*
C11	0.7509 (3)	0.02636 (9)	0.06680 (9)	0.0385 (3)
H11	0.811 (4)	−0.0272 (18)	0.0379 (13)	0.046*
C12	0.8177 (3)	0.12873 (8)	0.06010 (7)	0.0297 (2)
H12	0.924 (4)	0.1414 (15)	0.0297 (12)	0.036*
P1	0.71377 (4)	0.66972 (2)	0.07020 (2)	0.01586 (3)
F1	0.90542 (13)	0.58374 (6)	0.07093 (5)	0.03528 (17)
F2	0.68860 (12)	0.66992 (7)	−0.01761 (3)	0.02809 (13)
F3	0.52572 (13)	0.58121 (6)	0.06858 (5)	0.03232 (15)
F4	0.89906 (16)	0.75815 (7)	0.06994 (5)	0.03556 (17)
F5	0.51598 (17)	0.75441 (6)	0.06717 (5)	0.03828 (19)
F6	0.73559 (19)	0.67010 (10)	0.15711 (4)	0.0457 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01367 (2)	0.01398 (2)	0.01806 (2)	−0.00009 (1)	0.00079 (1)	0.00339 (1)
C1	0.0142 (2)	0.0175 (3)	0.0148 (2)	0.0005 (2)	0.00303 (19)	0.0019 (2)
C2	0.0194 (3)	0.0247 (4)	0.0177 (3)	−0.0015 (3)	0.0038 (2)	0.0059 (3)
C3	0.0249 (4)	0.0304 (4)	0.0157 (3)	0.0011 (3)	0.0015 (3)	0.0057 (3)
C4	0.0223 (4)	0.0287 (4)	0.0177 (3)	0.0006 (3)	−0.0016 (3)	−0.0003 (3)
C5	0.0188 (3)	0.0218 (3)	0.0208 (3)	−0.0008 (3)	0.0008 (2)	−0.0020 (3)
C6	0.0165 (3)	0.0169 (3)	0.0175 (3)	−0.0005 (2)	0.0024 (2)	0.0010 (2)
C7	0.0179 (3)	0.0135 (2)	0.0187 (3)	0.0016 (2)	0.0026 (2)	0.0014 (2)
C8	0.0267 (4)	0.0173 (3)	0.0409 (5)	−0.0034 (3)	0.0165 (4)	−0.0015 (3)
C9	0.0329 (5)	0.0205 (4)	0.0474 (7)	−0.0069 (4)	0.0142 (5)	0.0034 (4)
C10	0.0421 (6)	0.0144 (3)	0.0365 (5)	−0.0017 (4)	0.0006 (5)	0.0032 (3)
C11	0.0626 (9)	0.0160 (3)	0.0398 (6)	0.0071 (5)	0.0193 (6)	−0.0007 (4)
C12	0.0440 (6)	0.0176 (3)	0.0306 (5)	0.0066 (4)	0.0183 (4)	0.0019 (3)
P1	0.01978 (8)	0.01326 (7)	0.01476 (7)	−0.00168 (6)	0.00287 (6)	0.00009 (6)
F1	0.0223 (3)	0.0289 (3)	0.0554 (5)	0.0094 (3)	0.0077 (3)	0.0161 (3)
F2	0.0248 (3)	0.0435 (4)	0.0156 (2)	0.0002 (3)	−0.00002 (19)	−0.0025 (2)
F3	0.0229 (3)	0.0253 (3)	0.0497 (4)	−0.0081 (2)	0.0080 (3)	0.0037 (3)
F4	0.0438 (4)	0.0308 (3)	0.0316 (3)	−0.0224 (3)	0.0020 (3)	−0.0027 (3)
F5	0.0453 (5)	0.0256 (3)	0.0477 (5)	0.0160 (3)	0.0218 (4)	0.0043 (3)
F6	0.0548 (6)	0.0670 (6)	0.0157 (3)	−0.0110 (5)	0.0052 (3)	0.0038 (3)

Geometric parameters (Å, º) top

I1—C7	2.0935 (8)	C8—C9	1.4002 (15)
I1—C1	2.1167 (9)	C8—H8	0.954 (19)
C1—C2	1.3867 (11)	C9—C10	1.3800 (19)
C1—C6	1.3897 (11)	C9—H9	0.91 (2)
C2—C3	1.3929 (14)	C10—C11	1.378 (2)
C2—H2	0.939 (18)	C10—H10	1.03 (2)
C3—C4	1.3922 (16)	C11—C12	1.3931 (17)
C3—H3	0.887 (19)	C11—H11	0.97 (2)
C4—C5	1.3885 (14)	C12—H12	0.90 (2)
C4—H4	0.93 (2)	P1—F6	1.5893 (8)
C5—C6	1.3976 (13)	P1—F4	1.5924 (8)
C5—H5	0.960 (18)	P1—F1	1.5955 (8)
C6—H6	0.920 (17)	P1—F3	1.6024 (7)
C7—C8	1.3806 (13)	P1—F2	1.6053 (7)
C7—C12	1.3821 (13)	P1—F5	1.6080 (8)

C7—I1—C1	97.35 (3)	C10—C9—H9	121.8 (14)
C2—C1—C6	123.45 (8)	C8—C9—H9	118.0 (14)
C2—C1—I1	119.24 (6)	C11—C10—C9	120.55 (10)
C6—C1—I1	117.31 (6)	C11—C10—H10	124.7 (12)
C1—C2—C3	117.92 (9)	C9—C10—H10	114.7 (12)
C1—C2—H2	122.9 (11)	C10—C11—C12	120.64 (11)
C3—C2—H2	119.2 (11)	C10—C11—H11	118.7 (14)
C4—C3—C2	120.13 (9)	C12—C11—H11	120.6 (14)
C4—C3—H3	119.0 (12)	C7—C12—C11	117.68 (11)
C2—C3—H3	120.7 (12)	C7—C12—H12	125.3 (12)
C5—C4—C3	120.63 (9)	C11—C12—H12	117.0 (12)
C5—C4—H4	119.5 (12)	F6—P1—F4	91.10 (5)
C3—C4—H4	119.9 (12)	F6—P1—F1	90.73 (6)
C4—C5—C6	120.43 (9)	F4—P1—F1	90.19 (5)
C4—C5—H5	119.0 (11)	F6—P1—F3	90.12 (6)
C6—C5—H5	120.5 (11)	F4—P1—F3	178.74 (5)
C1—C6—C5	117.41 (8)	F1—P1—F3	90.12 (4)
C1—C6—H6	118.6 (10)	F6—P1—F2	179.28 (6)
C5—C6—H6	124.0 (10)	F4—P1—F2	89.17 (4)
C8—C7—C12	123.15 (9)	F1—P1—F2	89.93 (5)
C8—C7—I1	117.93 (6)	F3—P1—F2	89.60 (5)
C12—C7—I1	118.83 (7)	F6—P1—F5	90.74 (6)
C7—C8—C9	117.75 (10)	F4—P1—F5	91.03 (5)
C7—C8—H8	121.4 (11)	F1—P1—F5	178.07 (6)
C9—C8—H8	120.9 (11)	F3—P1—F5	88.63 (5)
C10—C9—C8	120.22 (11)	F2—P1—F5	88.59 (5)

C6—C1—C2—C3	−1.69 (14)	C12—C7—C8—C9	0.80 (19)
I1—C1—C2—C3	179.68 (7)	I1—C7—C8—C9	177.24 (10)
C1—C2—C3—C4	1.54 (15)	C7—C8—C9—C10	−0.8 (2)
C2—C3—C4—C5	−0.15 (17)	C8—C9—C10—C11	0.2 (2)
C3—C4—C5—C6	−1.20 (16)	C9—C10—C11—C12	0.5 (3)
C2—C1—C6—C5	0.38 (13)	C8—C7—C12—C11	−0.1 (2)
I1—C1—C6—C5	179.04 (6)	I1—C7—C12—C11	−176.54 (12)
C4—C5—C6—C1	1.08 (13)	C10—C11—C12—C7	−0.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···F6ⁱ	0.939 (18)	2.585 (18)	3.3143 (14)	134.8 (14)
C6—H6···F1	0.920 (17)	2.453 (17)	3.1084 (12)	128.4 (13)
C6—H6···F3ⁱⁱ	0.920 (17)	2.538 (17)	3.2124 (11)	130.5 (13)
C12—H12···F4ⁱⁱⁱ	0.90 (2)	2.57 (2)	3.4050 (14)	154.7 (18)

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x+1, y, z; (iii) −x+2, −y+1, −z.

(gc143) top

Crystal data top

2(C₁₂H₈I⁺)·3(C₃H₂F₆O)·2(Cl⁻)	Z = 2
M_r = 1133.21	F(000) = 1092
Triclinic, P1	D_x = 1.967 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.7183 (10) Å	Cell parameters from 9825 reflections
b = 13.4322 (12) Å	θ = 2.9–33.8°
c = 14.8978 (13) Å	µ = 1.91 mm⁻¹
α = 113.429 (11)°	T = 103 K
β = 107.498 (10)°	Needle, colourless
γ = 101.366 (10)°	0.40 × 0.06 × 0.05 mm
V = 1913.0 (3) Å³

Data collection top

Bruker APEX-II CCD diffractometer	15166 independent reflections
Radiation source: fine-focus sealed tube	11243 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
φ and ω scans	θ_max = 35.5°, θ_min = 3.0°
Absorption correction: multi-scan Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.	h = −17→18
T_min = 0.600, T_max = 0.746	k = −21→20
49282 measured reflections	l = −23→22

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.062	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0224P)² + 0.2985P] where P = (F_o² + 2F_c²)/3
15166 reflections	(Δ/σ)_max = 0.003
536 parameters	Δρ_max = 0.73 e Å⁻³
0 restraints	Δρ_min = −0.71 e Å⁻³

Special details top

Experimental. Bruker KRYOFLEX low temperature device.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
I1	0.307877 (11)	0.049887 (10)	0.069750 (9)	0.01416 (3)
C1	0.23531 (18)	0.03277 (16)	0.18019 (16)	0.0166 (4)
C2	0.30159 (19)	0.09395 (17)	0.29093 (16)	0.0198 (4)
H2	0.3859	0.1500	0.3245	0.024*
C3	0.2410 (2)	0.07108 (18)	0.35283 (17)	0.0235 (4)
H3	0.2853	0.1115	0.4293	0.028*
C4	0.1189 (2)	−0.00895 (18)	0.30389 (18)	0.0237 (4)
H4	0.0785	−0.0233	0.3464	0.028*
C5	0.05438 (19)	−0.06868 (17)	0.19272 (17)	0.0202 (4)
H5	−0.0304	−0.1238	0.1595	0.024*
C6	0.11259 (18)	−0.04909 (16)	0.12715 (16)	0.0163 (4)
C7	0.05616 (17)	−0.10786 (15)	0.00940 (16)	0.0150 (4)
C8	−0.06489 (18)	−0.19226 (16)	−0.05664 (17)	0.0190 (4)
H8	−0.1182	−0.2163	−0.0264	0.023*
C9	−0.10786 (18)	−0.24167 (17)	−0.16776 (17)	0.0207 (4)
H9	−0.1915	−0.2994	−0.2128	0.025*
C10	−0.03201 (18)	−0.20932 (17)	−0.21585 (17)	0.0206 (4)
H10	−0.0647	−0.2451	−0.2922	0.025*
C11	0.08923 (18)	−0.12617 (16)	−0.15293 (16)	0.0175 (4)
H11	0.1425	−0.1029	−0.1835	0.021*
C12	0.12961 (17)	−0.07817 (15)	−0.04236 (16)	0.0157 (4)
I2	0.633491 (11)	0.243136 (10)	0.068424 (9)	0.01480 (3)
C13	0.70254 (18)	0.25133 (16)	−0.04638 (16)	0.0162 (4)
C14	0.63143 (18)	0.18861 (16)	−0.15719 (16)	0.0178 (4)
H14	0.5451	0.1373	−0.1881	0.021*
C15	0.69078 (19)	0.20311 (17)	−0.22262 (16)	0.0204 (4)
H15	0.6438	0.1618	−0.2988	0.024*
C16	0.81643 (19)	0.27672 (17)	−0.17726 (17)	0.0207 (4)
H16	0.8560	0.2853	−0.2221	0.025*
C17	0.88482 (19)	0.33808 (16)	−0.06626 (17)	0.0194 (4)
H17	0.9714	0.3886	−0.0357	0.023*
C18	0.82835 (18)	0.32717 (16)	0.00266 (16)	0.0160 (4)
C19	0.88869 (18)	0.38856 (15)	0.12059 (16)	0.0168 (4)
C20	1.01372 (19)	0.46756 (17)	0.18460 (17)	0.0220 (4)
H20	1.0676	0.4850	0.1522	0.026*
C21	1.0596 (2)	0.52069 (18)	0.29534 (18)	0.0256 (5)
H21	1.1451	0.5752	0.3383	0.031*
C22	0.9837 (2)	0.49669 (18)	0.34644 (17)	0.0249 (4)
H22	1.0181	0.5352	0.4230	0.030*
C23	0.85979 (19)	0.41788 (17)	0.28667 (17)	0.0214 (4)
H23	0.8070	0.3995	0.3196	0.026*
C24	0.81625 (17)	0.36688 (16)	0.17571 (16)	0.0174 (4)
Cl1	0.38302 (4)	0.05016 (4)	−0.11800 (4)	0.01886 (9)
Cl2	0.55177 (5)	0.25304 (5)	0.25592 (4)	0.02683 (11)
F1	0.5394 (2)	0.69905 (17)	0.34646 (19)	0.0772 (6)
F2	0.47151 (17)	0.67956 (16)	0.46034 (16)	0.0713 (6)
F3	0.36730 (16)	0.56583 (17)	0.29269 (17)	0.0907 (8)
F4	0.69102 (16)	0.65628 (14)	0.56806 (12)	0.0579 (5)
F5	0.74889 (15)	0.52872 (14)	0.47686 (13)	0.0545 (5)
F6	0.76311 (14)	0.68261 (15)	0.45961 (16)	0.0641 (5)
C26	0.4832 (2)	0.6235 (2)	0.3710 (2)	0.0449 (7)
C27	0.6902 (2)	0.6039 (2)	0.4719 (2)	0.0330 (5)
C25A	0.5569 (2)	0.54386 (19)	0.38260 (19)	0.0304 (5)	0.50
H25A	0.5670	0.5068	0.3139	0.037*	0.50
O1A	0.4793 (3)	0.4585 (3)	0.3847 (3)	0.0337 (8)	0.50
H1AO	0.4964	0.3981	0.3596	0.050*	0.50
C25B	0.5569 (2)	0.54386 (19)	0.38260 (19)	0.0304 (5)	0.50
H25B	0.5069	0.4899	0.3996	0.037*	0.50
O1B	0.5513 (4)	0.4808 (3)	0.2888 (3)	0.0477 (10)	0.50
H1BO	0.5329	0.4112	0.2752	0.072*	0.50
F7	0.94217 (16)	0.2335 (2)	0.40980 (16)	0.0818 (7)
F8	0.95601 (13)	0.21016 (15)	0.54969 (13)	0.0535 (4)
F9	0.90547 (18)	0.06676 (18)	0.39993 (18)	0.0958 (8)
F10	0.55637 (14)	0.06015 (16)	0.40840 (15)	0.0574 (5)
F11	0.68619 (19)	−0.03150 (14)	0.40637 (15)	0.0616 (5)
F12	0.72595 (15)	0.11311 (14)	0.55209 (12)	0.0468 (4)
O2	0.74180 (16)	0.25683 (14)	0.45811 (13)	0.0366 (4)
H1O2	0.6902	0.2657	0.4114	0.055*
C28	0.7494 (2)	0.14957 (19)	0.41064 (17)	0.0262 (5)
H28	0.7059	0.1145	0.3305	0.031*
C29	0.8891 (2)	0.1639 (3)	0.4438 (2)	0.0455 (7)
C30	0.6802 (2)	0.0725 (2)	0.4454 (2)	0.0330 (5)
F13	0.41800 (17)	0.43207 (16)	0.08742 (15)	0.0665 (5)
F14	0.22368 (14)	0.42353 (13)	0.01509 (15)	0.0574 (5)
F15	0.37221 (15)	0.52002 (13)	−0.00857 (17)	0.0664 (6)
F16	0.10445 (14)	0.31088 (15)	−0.20692 (15)	0.0583 (5)
F17	0.20133 (17)	0.21447 (16)	−0.28519 (15)	0.0645 (5)
F18	0.26767 (18)	0.39554 (17)	−0.22320 (18)	0.0721 (6)
O3	0.25523 (15)	0.22610 (13)	−0.08468 (15)	0.0333 (4)
H1O3	0.2827	0.1728	−0.1097	0.050*
C31	0.3081 (2)	0.31910 (18)	−0.0988 (2)	0.0271 (5)
H31	0.3928	0.3192	−0.1006	0.032*
C32	0.2197 (3)	0.3106 (3)	−0.2042 (3)	0.0436 (7)
C33	0.3293 (2)	0.4239 (2)	−0.0015 (2)	0.0427 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01458 (6)	0.01232 (6)	0.01418 (6)	0.00409 (4)	0.00672 (5)	0.00510 (5)
C1	0.0198 (9)	0.0152 (9)	0.0189 (10)	0.0076 (7)	0.0114 (8)	0.0090 (8)
C2	0.0227 (10)	0.0162 (9)	0.0192 (10)	0.0056 (8)	0.0095 (8)	0.0076 (8)
C3	0.0335 (12)	0.0204 (10)	0.0185 (10)	0.0109 (9)	0.0132 (9)	0.0090 (8)
C4	0.0307 (11)	0.0237 (10)	0.0279 (12)	0.0128 (9)	0.0203 (10)	0.0156 (9)
C5	0.0208 (9)	0.0187 (9)	0.0275 (11)	0.0082 (8)	0.0141 (9)	0.0136 (9)
C6	0.0179 (9)	0.0131 (8)	0.0212 (10)	0.0078 (7)	0.0104 (8)	0.0087 (8)
C7	0.0145 (8)	0.0128 (8)	0.0192 (10)	0.0065 (7)	0.0076 (7)	0.0081 (7)
C8	0.0159 (9)	0.0161 (9)	0.0267 (11)	0.0072 (7)	0.0098 (8)	0.0107 (8)
C9	0.0144 (9)	0.0159 (9)	0.0254 (11)	0.0048 (7)	0.0043 (8)	0.0077 (8)
C10	0.0193 (9)	0.0182 (9)	0.0175 (10)	0.0070 (8)	0.0038 (8)	0.0054 (8)
C11	0.0180 (9)	0.0152 (9)	0.0175 (10)	0.0056 (7)	0.0074 (8)	0.0066 (8)
C12	0.0140 (8)	0.0122 (8)	0.0185 (10)	0.0048 (7)	0.0061 (7)	0.0057 (7)
I2	0.01462 (6)	0.01354 (6)	0.01442 (6)	0.00442 (5)	0.00678 (5)	0.00502 (5)
C13	0.0185 (9)	0.0154 (9)	0.0192 (10)	0.0080 (7)	0.0109 (8)	0.0095 (8)
C14	0.0193 (9)	0.0156 (9)	0.0174 (10)	0.0060 (7)	0.0082 (8)	0.0070 (8)
C15	0.0251 (10)	0.0206 (10)	0.0163 (10)	0.0085 (8)	0.0106 (8)	0.0083 (8)
C16	0.0243 (10)	0.0205 (10)	0.0250 (11)	0.0097 (8)	0.0159 (9)	0.0131 (9)
C17	0.0189 (9)	0.0149 (9)	0.0279 (11)	0.0059 (7)	0.0126 (8)	0.0117 (8)
C18	0.0182 (9)	0.0126 (8)	0.0193 (10)	0.0068 (7)	0.0089 (8)	0.0083 (7)
C19	0.0170 (9)	0.0108 (8)	0.0211 (10)	0.0053 (7)	0.0070 (8)	0.0071 (8)
C20	0.0197 (10)	0.0172 (9)	0.0269 (11)	0.0044 (8)	0.0085 (9)	0.0108 (9)
C21	0.0185 (10)	0.0178 (10)	0.0280 (12)	0.0000 (8)	0.0035 (9)	0.0077 (9)
C22	0.0251 (11)	0.0203 (10)	0.0170 (10)	0.0034 (8)	0.0031 (9)	0.0045 (8)
C23	0.0206 (10)	0.0190 (10)	0.0197 (10)	0.0054 (8)	0.0075 (8)	0.0066 (8)
C24	0.0157 (9)	0.0130 (8)	0.0193 (10)	0.0038 (7)	0.0054 (8)	0.0061 (8)
Cl1	0.0176 (2)	0.0183 (2)	0.0168 (2)	0.00416 (18)	0.00791 (18)	0.00571 (18)
Cl2	0.0242 (2)	0.0276 (3)	0.0162 (2)	−0.0006 (2)	0.0073 (2)	0.0049 (2)
F1	0.0858 (14)	0.0667 (13)	0.1142 (18)	0.0489 (12)	0.0452 (13)	0.0634 (13)
F2	0.0643 (12)	0.0623 (12)	0.0723 (13)	0.0446 (10)	0.0323 (10)	0.0068 (10)
F3	0.0383 (10)	0.0645 (13)	0.0895 (15)	0.0261 (9)	−0.0155 (10)	−0.0064 (11)
F4	0.0691 (11)	0.0556 (11)	0.0255 (8)	0.0345 (9)	0.0107 (8)	0.0000 (7)
F5	0.0523 (10)	0.0520 (10)	0.0404 (9)	0.0355 (8)	0.0064 (8)	0.0074 (8)
F6	0.0325 (9)	0.0551 (11)	0.0858 (14)	−0.0002 (8)	0.0234 (9)	0.0259 (10)
C26	0.0296 (13)	0.0315 (14)	0.0487 (17)	0.0126 (11)	0.0074 (12)	0.0032 (13)
C27	0.0320 (12)	0.0297 (12)	0.0288 (13)	0.0129 (10)	0.0121 (11)	0.0064 (10)
C25A	0.0263 (11)	0.0227 (11)	0.0307 (13)	0.0087 (9)	0.0096 (10)	0.0046 (10)
O1A	0.0324 (17)	0.0185 (15)	0.046 (2)	0.0063 (14)	0.0261 (16)	0.0068 (15)
C25B	0.0263 (11)	0.0227 (11)	0.0307 (13)	0.0087 (9)	0.0096 (10)	0.0046 (10)
O1B	0.076 (3)	0.038 (2)	0.0243 (19)	0.026 (2)	0.0196 (19)	0.0094 (17)
F7	0.0443 (10)	0.1168 (18)	0.0588 (12)	−0.0049 (11)	0.0302 (10)	0.0298 (12)
F8	0.0282 (8)	0.0712 (12)	0.0381 (9)	0.0168 (8)	0.0022 (7)	0.0153 (9)
F9	0.0518 (11)	0.0849 (15)	0.0982 (17)	0.0434 (11)	0.0276 (11)	−0.0079 (12)
F10	0.0283 (8)	0.0738 (12)	0.0692 (12)	0.0087 (8)	0.0183 (8)	0.0403 (10)
F11	0.0957 (14)	0.0361 (9)	0.0596 (12)	0.0273 (10)	0.0352 (11)	0.0258 (9)
F12	0.0570 (10)	0.0663 (11)	0.0322 (8)	0.0266 (9)	0.0270 (8)	0.0296 (8)
O2	0.0384 (10)	0.0276 (9)	0.0247 (9)	0.0111 (8)	0.0015 (8)	0.0046 (7)
C28	0.0271 (11)	0.0284 (11)	0.0159 (10)	0.0085 (9)	0.0083 (9)	0.0055 (9)
C29	0.0342 (14)	0.0544 (18)	0.0338 (15)	0.0153 (13)	0.0176 (12)	0.0070 (13)
C30	0.0362 (13)	0.0374 (14)	0.0290 (13)	0.0161 (11)	0.0151 (11)	0.0172 (11)
F13	0.0518 (10)	0.0642 (12)	0.0520 (11)	0.0243 (9)	0.0169 (9)	0.0023 (9)
F14	0.0403 (9)	0.0379 (9)	0.0935 (14)	0.0178 (7)	0.0453 (9)	0.0176 (9)
F15	0.0446 (9)	0.0207 (8)	0.1272 (17)	0.0101 (7)	0.0481 (11)	0.0223 (10)
F16	0.0309 (8)	0.0693 (12)	0.0844 (14)	0.0279 (8)	0.0174 (9)	0.0468 (11)
F17	0.0646 (12)	0.0662 (13)	0.0495 (11)	0.0302 (10)	0.0139 (9)	0.0207 (10)
F18	0.0783 (13)	0.0819 (14)	0.1060 (17)	0.0387 (11)	0.0481 (13)	0.0793 (14)
O3	0.0319 (9)	0.0249 (8)	0.0621 (12)	0.0154 (7)	0.0305 (9)	0.0281 (9)
C31	0.0189 (10)	0.0220 (10)	0.0482 (15)	0.0090 (8)	0.0180 (10)	0.0208 (11)
C32	0.0396 (15)	0.0447 (16)	0.064 (2)	0.0213 (13)	0.0230 (14)	0.0390 (16)
C33	0.0258 (12)	0.0299 (13)	0.067 (2)	0.0110 (11)	0.0235 (14)	0.0163 (14)

Geometric parameters (Å, º) top

I1—C12	2.0768 (19)	C21—C22	1.401 (3)
I1—C1	2.1327 (18)	C21—H21	0.9500
C1—C2	1.378 (3)	C22—C23	1.374 (3)
C1—C6	1.380 (3)	C22—H22	0.9500
C2—C3	1.408 (3)	C23—C24	1.384 (3)
C2—H2	0.9500	C23—H23	0.9500
C3—C4	1.371 (3)	F1—C26	1.331 (3)
C3—H3	0.9500	F2—C26	1.308 (3)
C4—C5	1.382 (3)	F3—C26	1.311 (3)
C4—H4	0.9500	F4—C27	1.317 (3)
C5—C6	1.422 (3)	F5—C27	1.342 (3)
C5—H5	0.9500	F6—C27	1.332 (3)
C6—C7	1.461 (3)	C26—C25A	1.531 (3)
C7—C8	1.380 (3)	C27—C25A	1.504 (3)
C7—C12	1.415 (3)	C25A—O1A	1.332 (4)
C8—C9	1.389 (3)	C25A—H25A	1.0000
C8—H8	0.9500	O1A—H1AO	0.8400
C9—C10	1.404 (3)	O1B—H1BO	0.8400
C9—H9	0.9500	F7—C29	1.361 (3)
C10—C11	1.373 (3)	F8—C29	1.332 (3)
C10—H10	0.9500	F9—C29	1.289 (3)
C11—C12	1.385 (3)	F10—C30	1.337 (3)
C11—H11	0.9500	F11—C30	1.309 (3)
I2—C24	2.0809 (19)	F12—C30	1.339 (3)
I2—C13	2.1305 (19)	O2—C28	1.364 (2)
C13—C18	1.383 (3)	O2—H1O2	0.8400
C13—C14	1.385 (3)	C28—C29	1.509 (3)
C14—C15	1.406 (3)	C28—C30	1.532 (3)
C14—H14	0.9500	C28—H28	1.0000
C15—C16	1.378 (3)	F13—C33	1.363 (3)
C15—H15	0.9500	F14—C33	1.332 (3)
C16—C17	1.384 (3)	F15—C33	1.347 (3)
C16—H16	0.9500	F16—C32	1.339 (3)
C17—C18	1.415 (3)	F17—C32	1.291 (3)
C17—H17	0.9500	F18—C32	1.341 (3)
C18—C19	1.462 (3)	O3—C31	1.404 (2)
C19—C20	1.387 (3)	O3—H1O3	0.8400
C19—C24	1.411 (3)	C31—C33	1.473 (3)
C20—C21	1.378 (3)	C31—C32	1.544 (4)
C20—H20	0.9500	C31—H31	1.0000

C12—I1—C1	81.96 (7)	C23—C22—C21	120.5 (2)
C2—C1—C6	123.35 (18)	C23—C22—H22	119.8
C2—C1—I1	125.06 (14)	C21—C22—H22	119.8
C6—C1—I1	111.59 (14)	C22—C23—C24	116.17 (19)
C1—C2—C3	118.19 (18)	C22—C23—H23	121.9
C1—C2—H2	120.9	C24—C23—H23	121.9
C3—C2—H2	120.9	C23—C24—C19	125.42 (18)
C4—C3—C2	120.6 (2)	C23—C24—I2	123.25 (14)
C4—C3—H3	119.7	C19—C24—I2	111.31 (14)
C2—C3—H3	119.7	F2—C26—F3	107.5 (2)
C3—C4—C5	119.96 (19)	F2—C26—F1	109.8 (2)
C3—C4—H4	120.0	F3—C26—F1	104.7 (3)
C5—C4—H4	120.0	F2—C26—C25A	109.7 (3)
C4—C5—C6	121.19 (18)	F3—C26—C25A	112.5 (2)
C4—C5—H5	119.4	F1—C26—C25A	112.5 (2)
C6—C5—H5	119.4	F4—C27—F6	108.3 (2)
C1—C6—C5	116.66 (18)	F4—C27—F5	104.2 (2)
C1—C6—C7	116.76 (17)	F6—C27—F5	108.0 (2)
C5—C6—C7	126.57 (17)	F4—C27—C25A	112.7 (2)
C8—C7—C12	116.66 (18)	F6—C27—C25A	111.3 (2)
C8—C7—C6	124.67 (17)	F5—C27—C25A	112.13 (19)
C12—C7—C6	118.67 (16)	O1A—C25A—C27	115.4 (3)
C7—C8—C9	119.25 (18)	O1A—C25A—C26	106.6 (2)
C7—C8—H8	120.4	C27—C25A—C26	115.52 (19)
C9—C8—H8	120.4	O1A—C25A—H25A	106.2
C8—C9—C10	122.27 (18)	C27—C25A—H25A	106.2
C8—C9—H9	118.9	C26—C25A—H25A	106.2
C10—C9—H9	118.9	C28—O2—H1O2	109.5
C11—C10—C9	120.24 (19)	O2—C28—C29	108.48 (19)
C11—C10—H10	119.9	O2—C28—C30	108.42 (18)
C9—C10—H10	119.9	C29—C28—C30	112.3 (2)
C10—C11—C12	116.30 (18)	O2—C28—H28	109.2
C10—C11—H11	121.8	C29—C28—H28	109.2
C12—C11—H11	121.8	C30—C28—H28	109.2
C11—C12—C7	125.28 (17)	F9—C29—F8	105.9 (3)
C11—C12—I1	123.69 (14)	F9—C29—F7	107.0 (2)
C7—C12—I1	111.03 (13)	F8—C29—F7	108.9 (2)
C24—I2—C13	81.65 (8)	F9—C29—C28	112.8 (2)
C18—C13—C14	123.31 (18)	F8—C29—C28	114.0 (2)
C18—C13—I2	111.96 (14)	F7—C29—C28	108.0 (2)
C14—C13—I2	124.73 (14)	F11—C30—F10	107.7 (2)
C13—C14—C15	118.03 (18)	F11—C30—F12	104.5 (2)
C13—C14—H14	121.0	F10—C30—F12	108.41 (19)
C15—C14—H14	121.0	F11—C30—C28	112.7 (2)
C16—C15—C14	120.62 (19)	F10—C30—C28	108.16 (19)
C16—C15—H15	119.7	F12—C30—C28	115.0 (2)
C14—C15—H15	119.7	C31—O3—H1O3	109.5
C15—C16—C17	119.90 (18)	O3—C31—C33	104.5 (2)
C15—C16—H16	120.1	O3—C31—C32	111.99 (19)
C17—C16—H16	120.1	C33—C31—C32	113.0 (2)
C16—C17—C18	121.35 (18)	O3—C31—H31	109.1
C16—C17—H17	119.3	C33—C31—H31	109.1
C18—C17—H17	119.3	C32—C31—H31	109.1
C13—C18—C17	116.78 (18)	F17—C32—F16	107.5 (2)
C13—C18—C19	116.40 (17)	F17—C32—F18	105.9 (3)
C17—C18—C19	126.81 (17)	F16—C32—F18	107.2 (2)
C20—C19—C24	116.14 (18)	F17—C32—C31	109.3 (2)
C20—C19—C18	125.23 (18)	F16—C32—C31	112.3 (2)
C24—C19—C18	118.63 (16)	F18—C32—C31	114.4 (2)
C21—C20—C19	119.86 (19)	F14—C33—F15	107.62 (19)
C21—C20—H20	120.1	F14—C33—F13	106.8 (2)
C19—C20—H20	120.1	F15—C33—F13	108.9 (2)
C20—C21—C22	121.92 (19)	F14—C33—C31	113.2 (2)
C20—C21—H21	119.0	F15—C33—C31	110.4 (2)
C22—C21—H21	119.0	F13—C33—C31	109.9 (2)

C12—I1—C1—C2	178.81 (17)	C18—C19—C20—C21	179.49 (18)
C12—I1—C1—C6	−0.47 (13)	C19—C20—C21—C22	0.6 (3)
C6—C1—C2—C3	0.4 (3)	C20—C21—C22—C23	0.3 (3)
I1—C1—C2—C3	−178.83 (13)	C21—C22—C23—C24	−0.9 (3)
C1—C2—C3—C4	−0.8 (3)	C22—C23—C24—C19	0.7 (3)
C2—C3—C4—C5	0.5 (3)	C22—C23—C24—I2	178.96 (14)
C3—C4—C5—C6	0.2 (3)	C20—C19—C24—C23	0.2 (3)
C2—C1—C6—C5	0.3 (3)	C18—C19—C24—C23	179.91 (17)
I1—C1—C6—C5	179.57 (12)	C20—C19—C24—I2	−178.26 (13)
C2—C1—C6—C7	−179.02 (17)	C18—C19—C24—I2	1.4 (2)
I1—C1—C6—C7	0.3 (2)	C13—I2—C24—C23	179.80 (17)
C4—C5—C6—C1	−0.6 (3)	C13—I2—C24—C19	−1.69 (13)
C4—C5—C6—C7	178.66 (18)	F4—C27—C25A—O1A	−62.2 (3)
C1—C6—C7—C8	179.67 (17)	F6—C27—C25A—O1A	176.0 (2)
C5—C6—C7—C8	0.4 (3)	F5—C27—C25A—O1A	55.0 (3)
C1—C6—C7—C12	0.2 (2)	F4—C27—C25A—C26	63.1 (3)
C5—C6—C7—C12	−178.99 (17)	F6—C27—C25A—C26	−58.7 (3)
C12—C7—C8—C9	−0.6 (2)	F5—C27—C25A—C26	−179.7 (2)
C6—C7—C8—C9	179.92 (17)	F2—C26—C25A—O1A	70.1 (3)
C7—C8—C9—C10	0.4 (3)	F3—C26—C25A—O1A	−49.5 (4)
C8—C9—C10—C11	0.0 (3)	F1—C26—C25A—O1A	−167.5 (3)
C9—C10—C11—C12	−0.1 (3)	F2—C26—C25A—C27	−59.6 (3)
C10—C11—C12—C7	−0.2 (3)	F3—C26—C25A—C27	−179.2 (2)
C10—C11—C12—I1	−179.45 (13)	F1—C26—C25A—C27	62.8 (3)
C8—C7—C12—C11	0.6 (3)	O2—C28—C29—F9	−178.1 (2)
C6—C7—C12—C11	−179.96 (17)	C30—C28—C29—F9	62.1 (3)
C8—C7—C12—I1	179.90 (13)	O2—C28—C29—F8	61.1 (3)
C6—C7—C12—I1	−0.6 (2)	C30—C28—C29—F8	−58.7 (3)
C1—I1—C12—C11	179.93 (16)	O2—C28—C29—F7	−60.1 (3)
C1—I1—C12—C7	0.58 (12)	C30—C28—C29—F7	−179.9 (2)
C24—I2—C13—C18	1.76 (13)	O2—C28—C30—F11	−177.90 (19)
C24—I2—C13—C14	−178.40 (16)	C29—C28—C30—F11	−58.0 (3)
C18—C13—C14—C15	0.1 (3)	O2—C28—C30—F10	63.1 (2)
I2—C13—C14—C15	−179.75 (13)	C29—C28—C30—F10	−177.1 (2)
C13—C14—C15—C16	0.7 (3)	O2—C28—C30—F12	−58.2 (2)
C14—C15—C16—C17	−0.7 (3)	C29—C28—C30—F12	61.6 (3)
C15—C16—C17—C18	−0.1 (3)	O3—C31—C32—F17	−59.6 (3)
C14—C13—C18—C17	−0.8 (3)	C33—C31—C32—F17	−177.2 (2)
I2—C13—C18—C17	179.05 (13)	O3—C31—C32—F16	59.6 (3)
C14—C13—C18—C19	178.66 (16)	C33—C31—C32—F16	−58.1 (3)
I2—C13—C18—C19	−1.5 (2)	O3—C31—C32—F18	−178.0 (2)
C16—C17—C18—C13	0.8 (3)	C33—C31—C32—F18	64.3 (3)
C16—C17—C18—C19	−178.58 (17)	O3—C31—C33—F14	−55.1 (3)
C13—C18—C19—C20	179.74 (17)	C32—C31—C33—F14	66.9 (3)
C17—C18—C19—C20	−0.9 (3)	O3—C31—C33—F15	−175.78 (18)
C13—C18—C19—C24	0.1 (2)	C32—C31—C33—F15	−53.8 (3)
C17—C18—C19—C24	179.44 (17)	O3—C31—C33—F13	64.2 (2)
C24—C19—C20—C21	−0.8 (3)	C32—C31—C33—F13	−173.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cl2	0.95	2.83	3.573 (2)	136
C11—H11···Cl1	0.95	2.75	3.530 (2)	139
C14—H14···Cl1	0.95	2.71	3.468 (2)	137
C23—H23···Cl2	0.95	2.86	3.632 (2)	139
C23—H23···F5	0.95	2.68	3.399 (3)	133
O1A—H1AO···Cl2	0.84	2.31	3.116 (3)	163
O1B—H1BO···Cl2	0.84	2.09	2.901 (4)	161
O2—H1O2···Cl2	0.84	2.31	3.1360 (18)	167
C28—H28···Cl1ⁱ	1.00	2.75	3.688 (2)	157
O3—H1O3···Cl1	0.84	2.19	2.9972 (15)	161
C31—H31···F15ⁱⁱ	1.00	2.66	3.423 (3)	134

Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1, −y+1, −z.

(gc148) top

Crystal data top

3(C₁₂H₈BrF₂⁺)·2.5(Br⁻)·0.5(BF₄⁻)	D_x = 1.907 Mg m⁻³
M_r = 1053.46	Mo Kα radiation, λ = 0.71073 Å
Cubic, P4₃32	Cell parameters from 3702 reflections
Hall symbol: P 4acd 2ab	θ = 2.3–25.0°
a = 15.4248 (7) Å	µ = 6.09 mm⁻¹
V = 3669.9 (3) Å³	T = 103 K
Z = 4	Hexagonal truncated bipyramid, colourless
F(000) = 2028	0.13 × 0.12 × 0.10 mm

Data collection top

Bruker APEX-II CCD diffractometer	1462 independent reflections
Radiation source: fine-focus sealed tube	1253 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
φ and ω scans	θ_max = 28.5°, θ_min = 3.2°
Absorption correction: multi-scan Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.	h = −20→18
T_min = 0.344, T_max = 0.399	k = −18→10
13923 measured reflections	l = −20→13

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.054	w = 1/[σ²(F_o²) + (0.0114P)² + 4.9818P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
1462 reflections	Δρ_max = 0.58 e Å⁻³
99 parameters	Δρ_min = −0.42 e Å⁻³
48 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (2)

Special details top

Experimental. Bruker KRYOFLEX low temperature device.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. H atoms were refined with soft restraints on C-H distances and C-C-H angles. B-F distances were restrained to be 1.38 (2) The anion not directly bonded to the bromonium ion was a mixture of BF₄^- and Br^- with refined population factors 0.54/0.46. SHELXL approximate this ratio to 0.5/0.5 when calculated the _chemical_formula_sum, but when we imposed this ratio (without refinement) the results were quite worse. In particular the higher residue around the disordered anion was 4.5 eA%O^-3.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Br1	0.3750	0.22808 (2)	0.97808 (2)	0.02089 (13)
F1	0.19639 (17)	0.56978 (15)	0.95371 (18)	0.0465 (7)
C1	0.3196 (2)	0.3407 (2)	0.9785 (2)	0.0201 (8)
C2	0.3684 (3)	0.4127 (3)	0.9632 (3)	0.0311 (10)
H2	0.4284 (14)	0.4108 (12)	0.958 (3)	0.037*
C3	0.3263 (3)	0.4914 (3)	0.9568 (3)	0.0368 (11)
H3	0.3572 (12)	0.5420 (14)	0.946 (3)	0.044*
C4	0.2371 (3)	0.4932 (3)	0.9642 (3)	0.0309 (10)
C5	0.1892 (3)	0.4210 (3)	0.9803 (3)	0.0342 (10)
H5	0.1293 (14)	0.4231 (12)	0.987 (3)	0.041*
C6	0.2316 (3)	0.3416 (3)	0.9885 (3)	0.0332 (10)
H6	0.2022 (13)	0.2930 (15)	1.008 (3)	0.040*
Br2	0.45808 (2)	0.04192 (2)	0.95808 (2)	0.02050 (16)
B1	0.1250	0.1250	0.1250	0.0389 (9)	0.537 (5)
F2	0.0740 (3)	0.0740 (3)	0.0740 (3)	0.049 (4)	0.268 (3)
F3	0.2041 (6)	0.1119 (12)	0.0880 (8)	0.097 (4)	0.268 (3)
Br3	0.1250	0.1250	0.1250	0.0389 (9)	0.463 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0204 (3)	0.02111 (19)	0.02111 (19)	0.00358 (16)	−0.00358 (16)	−0.0042 (2)
F1	0.0426 (16)	0.0303 (14)	0.0665 (19)	0.0129 (12)	−0.0183 (14)	−0.0053 (13)
C1	0.025 (2)	0.0158 (19)	0.019 (2)	0.0060 (16)	−0.0048 (16)	−0.0050 (16)
C2	0.021 (2)	0.031 (2)	0.041 (3)	0.0018 (18)	−0.002 (2)	−0.001 (2)
C3	0.031 (2)	0.025 (2)	0.054 (3)	−0.0001 (19)	−0.006 (2)	0.001 (2)
C4	0.031 (2)	0.024 (2)	0.038 (2)	0.0101 (19)	−0.010 (2)	−0.008 (2)
C5	0.022 (2)	0.034 (2)	0.047 (3)	0.0090 (18)	−0.004 (2)	−0.007 (2)
C6	0.023 (2)	0.027 (2)	0.050 (3)	0.0002 (18)	0.000 (2)	−0.004 (2)
Br2	0.02050 (16)	0.02050 (16)	0.02050 (16)	0.00118 (16)	−0.00118 (16)	0.00118 (16)
B1	0.0389 (9)	0.0389 (9)	0.0389 (9)	−0.0013 (6)	−0.0013 (6)	−0.0013 (6)
F2	0.049 (4)	0.049 (4)	0.049 (4)	−0.012 (4)	−0.012 (4)	−0.012 (4)
F3	0.070 (7)	0.121 (8)	0.100 (8)	0.022 (7)	0.007 (7)	0.006 (8)
Br3	0.0389 (9)	0.0389 (9)	0.0389 (9)	−0.0013 (6)	−0.0013 (6)	−0.0013 (6)

Geometric parameters (Å, º) top

Br1—C1ⁱ	1.936 (4)	B1—F3ⁱⁱ	1.362 (8)
Br1—C1	1.936 (4)	B1—F3ⁱⁱⁱ	1.362 (8)
F1—C4	1.348 (4)	B1—F3	1.362 (8)
C1—C2	1.364 (5)	B1—F3^iv	1.362 (8)
C1—C6	1.365 (5)	B1—F3^v	1.362 (8)
C2—C3	1.381 (6)	B1—F3^vi	1.362 (8)
C2—H2	0.93 (2)	B1—F2^vi	1.363 (9)
C3—C4	1.381 (6)	B1—F2	1.363 (9)
C3—H3	0.93 (2)	F2—F3ⁱⁱ	1.734 (15)
C4—C5	1.358 (6)	F2—F3^vi	1.734 (15)
C5—C6	1.394 (5)	F2—F3ⁱⁱⁱ	1.734 (15)
C5—H5	0.93 (2)	F3—F3ⁱⁱ	1.00 (2)
C6—H6	0.93 (2)	F3—F2^vi	1.734 (15)

C1ⁱ—Br1—C1	100.9 (2)	F3^iv—B1—F3^v	116.5 (5)
C2—C1—C6	124.0 (4)	F3ⁱⁱ—B1—F3^vi	116.5 (5)
C2—C1—Br1	119.1 (3)	F3ⁱⁱⁱ—B1—F3^vi	116.5 (5)
C6—C1—Br1	116.7 (3)	F3—B1—F3^vi	84.9 (13)
C1—C2—C3	118.0 (4)	F3^iv—B1—F3^vi	157.9 (12)
C1—C2—H2	122.7 (11)	F3^v—B1—F3^vi	43.2 (10)
C3—C2—H2	119.4 (11)	F3ⁱⁱ—B1—F2^vi	100.9 (7)
C2—C3—C4	118.7 (4)	F3ⁱⁱⁱ—B1—F2^vi	100.9 (7)
C2—C3—H3	120.7 (12)	F3—B1—F2^vi	79.1 (7)
C4—C3—H3	120.6 (12)	F3^iv—B1—F2^vi	79.1 (7)
F1—C4—C5	119.1 (4)	F3^v—B1—F2^vi	79.1 (7)
F1—C4—C3	118.1 (4)	F3^vi—B1—F2^vi	100.9 (7)
C5—C4—C3	122.7 (4)	F3ⁱⁱ—B1—F2	79.1 (7)
C4—C5—C6	118.8 (4)	F3ⁱⁱⁱ—B1—F2	79.1 (7)
C4—C5—H5	122.2 (11)	F3—B1—F2	100.9 (7)
C6—C5—H5	119.1 (12)	F3^iv—B1—F2	100.9 (7)
C1—C6—C5	117.8 (4)	F3^v—B1—F2	100.9 (7)
C1—C6—H6	121.0 (12)	F3^vi—B1—F2	79.1 (7)
C5—C6—H6	120.7 (12)	F2^vi—B1—F2	179.997 (2)
F3ⁱⁱ—B1—F3ⁱⁱⁱ	116.5 (5)	B1—F2—F3ⁱⁱ	50.4 (5)
F3ⁱⁱ—B1—F3	43.2 (10)	B1—F2—F3^vi	50.4 (5)
F3ⁱⁱⁱ—B1—F3	157.9 (12)	F3ⁱⁱ—F2—F3^vi	83.8 (7)
F3ⁱⁱ—B1—F3^iv	84.9 (13)	B1—F2—F3ⁱⁱⁱ	50.4 (5)
F3ⁱⁱⁱ—B1—F3^iv	43.2 (10)	F3ⁱⁱ—F2—F3ⁱⁱⁱ	83.8 (7)
F3—B1—F3^iv	116.5 (5)	F3^vi—F2—F3ⁱⁱⁱ	83.8 (7)
F3ⁱⁱ—B1—F3^v	157.9 (12)	F3ⁱⁱ—F3—B1	68.4 (5)
F3ⁱⁱⁱ—B1—F3^v	84.9 (13)	F3ⁱⁱ—F3—F2^vi	96.7 (16)
F3—B1—F3^v	116.5 (5)	B1—F3—F2^vi	50.5 (5)

C1ⁱ—Br1—C1—C2	77.7 (3)	F3^iv—B1—F2—F3^vi	−157.5 (12)
C1ⁱ—Br1—C1—C6	−106.7 (4)	F3^v—B1—F2—F3^vi	−37.5 (12)
C6—C1—C2—C3	−0.5 (7)	F2^vi—B1—F2—F3^vi	11.0 (13)
Br1—C1—C2—C3	174.8 (3)	F3ⁱⁱ—B1—F2—F3ⁱⁱⁱ	−120.0
C1—C2—C3—C4	−1.4 (7)	F3—B1—F2—F3ⁱⁱⁱ	−157.5 (12)
C2—C3—C4—F1	−176.9 (4)	F3^iv—B1—F2—F3ⁱⁱⁱ	−37.5 (12)
C2—C3—C4—C5	2.1 (7)	F3^v—B1—F2—F3ⁱⁱⁱ	82.5 (12)
F1—C4—C5—C6	178.1 (4)	F3^vi—B1—F2—F3ⁱⁱⁱ	120.0
C3—C4—C5—C6	−0.9 (7)	F2^vi—B1—F2—F3ⁱⁱⁱ	131.0 (13)
C2—C1—C6—C5	1.7 (7)	F3ⁱⁱⁱ—B1—F3—F3ⁱⁱ	−27.0 (19)
Br1—C1—C6—C5	−173.7 (3)	F3^iv—B1—F3—F3ⁱⁱ	−47 (3)
C4—C5—C6—C1	−1.0 (7)	F3^v—B1—F3—F3ⁱⁱ	169.0 (11)
F3ⁱⁱⁱ—B1—F2—F3ⁱⁱ	120.0	F3^vi—B1—F3—F3ⁱⁱ	139 (3)
F3—B1—F2—F3ⁱⁱ	−37.5 (12)	F2^vi—B1—F3—F3ⁱⁱ	−119 (2)
F3^iv—B1—F2—F3ⁱⁱ	82.5 (12)	F2—B1—F3—F3ⁱⁱ	61 (2)
F3^v—B1—F2—F3ⁱⁱ	−157.5 (12)	F3ⁱⁱ—B1—F3—F2^vi	119 (2)
F3^vi—B1—F2—F3ⁱⁱ	−120.0	F3ⁱⁱⁱ—B1—F3—F2^vi	92.2 (2)
F2^vi—B1—F2—F3ⁱⁱ	−109.0 (13)	F3^iv—B1—F3—F2^vi	71.8 (11)
F3ⁱⁱ—B1—F2—F3^vi	120.0	F3^v—B1—F3—F2^vi	−71.8 (11)
F3ⁱⁱⁱ—B1—F2—F3^vi	−120.0	F3^vi—B1—F3—F2^vi	−102.2 (7)
F3—B1—F2—F3^vi	82.5 (12)	F2—B1—F3—F2^vi	180.0

Symmetry codes: (i) −x+3/4, z−3/4, y+3/4; (ii) −z+1/4, −y+1/4, −x+1/4; (iii) −x+1/4, −z+1/4, −y+1/4; (iv) z, x, y; (v) y, z, x; (vi) −y+1/4, −x+1/4, −z+1/4.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···F2^vii	0.93 (2)	2.31 (2)	3.228 (7)	170 (2)
C2—H2···F3^viii	0.93 (2)	2.59 (3)	3.356 (16)	140 (3)
C5—H5···Br2^ix	0.93 (2)	2.83 (2)	3.734 (4)	166 (3)
C6—H6···F3^x	0.93 (2)	2.54 (3)	3.435 (17)	163 (2)

Symmetry codes: (vii) x+1/2, −y+1/2, −z+1; (viii) −x+3/4, z+1/4, y+3/4; (ix) x−1/2, −y+1/2, −z+2; (x) −z+1/4, −y+1/4, −x+5/4.

(gc154) top

Crystal data top

3(C₁₂H₈BrF₂⁺)·2(Cl⁻)·(BF₄⁻)	D_x = 1.799 Mg m⁻³
M_r = 967.99	Mo Kα radiation, λ = 0.71073 Å
Cubic, P4₁32	Cell parameters from 8863 reflections
Hall symbol: P 4bd 2ab 3	θ = 2.3–32.1°
a = 15.2905 (8) Å	µ = 3.62 mm⁻¹
V = 3574.9 (3) Å³	T = 103 K
Z = 4	Block, colourless
F(000) = 1896	0.24 × 0.18 × 0.13 mm

Data collection top

Bruker APEX-II CCD diffractometer	2890 independent reflections
Radiation source: fine-focus sealed tube	2467 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
φ and ω scans	θ_max = 36.7°, θ_min = 3.0°
Absorption correction: multi-scan Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.	h = −25→21
T_min = 0.647, T_max = 0.747	k = −24→24
30649 measured reflections	l = −22→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.025	Only H-atom coordinates refined
wR(F²) = 0.052	w = 1/[σ²(F_o²) + (0.0271P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.002
2890 reflections	Δρ_max = 0.51 e Å⁻³
99 parameters	Δρ_min = −0.27 e Å⁻³
34 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.005 (7)

Special details top

Experimental. Bruker KRYOFLEX low temperature device.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Br1	0.272571 (8)	0.522571 (8)	0.1250	0.01486 (4)
C1	0.26923 (9)	0.41112 (8)	0.06662 (8)	0.0160 (2)
F1	0.28474 (8)	0.18182 (6)	−0.06398 (7)	0.0380 (2)
C2	0.25895 (11)	0.41180 (10)	−0.02304 (9)	0.0246 (3)
H2	0.2474 (11)	0.4678 (7)	−0.0519 (8)	0.029*
C3	0.26328 (11)	0.33292 (10)	−0.06774 (10)	0.0276 (3)
H3	0.2560 (11)	0.3288 (9)	−0.1314 (7)	0.033*
C4	0.27799 (11)	0.25783 (9)	−0.02031 (10)	0.0246 (3)
C5	0.28572 (12)	0.25721 (10)	0.06928 (11)	0.0301 (3)
H5	0.3022 (13)	0.2022 (8)	0.0998 (8)	0.036*
C6	0.28254 (11)	0.33568 (9)	0.11446 (10)	0.0254 (3)
H6	0.2906 (11)	0.3387 (8)	0.1780 (7)	0.030*
Cl1	0.454135 (19)	0.545865 (19)	0.045865 (19)	0.01602 (10)
B	0.1250	0.6250	0.8750	0.0181 (6)
F2	0.17800 (14)	0.67800 (14)	0.82200 (14)	0.0456 (9)	0.50
F3	0.1214 (3)	0.54416 (15)	0.83570 (18)	0.0645 (8)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01500 (6)	0.01500 (6)	0.01457 (8)	−0.00219 (6)	0.00213 (4)	−0.00213 (4)
C1	0.0171 (6)	0.0159 (5)	0.0151 (5)	−0.0021 (4)	0.0018 (4)	−0.0027 (4)
F1	0.0610 (7)	0.0204 (4)	0.0327 (5)	−0.0067 (4)	0.0151 (5)	−0.0115 (4)
C2	0.0386 (8)	0.0196 (6)	0.0155 (6)	0.0002 (5)	0.0009 (6)	−0.0006 (5)
C3	0.0414 (9)	0.0248 (7)	0.0167 (6)	−0.0019 (7)	0.0023 (6)	−0.0059 (5)
C4	0.0310 (7)	0.0183 (6)	0.0246 (7)	−0.0050 (6)	0.0079 (6)	−0.0069 (5)
C5	0.0486 (10)	0.0164 (6)	0.0253 (7)	0.0012 (6)	0.0022 (7)	−0.0003 (5)
C6	0.0400 (9)	0.0199 (6)	0.0162 (6)	0.0001 (6)	−0.0004 (6)	−0.0003 (5)
Cl1	0.01602 (10)	0.01602 (10)	0.01602 (10)	0.00108 (10)	0.00108 (10)	−0.00108 (10)
B	0.0181 (6)	0.0181 (6)	0.0181 (6)	0.0002 (8)	−0.0002 (8)	−0.0002 (8)
F2	0.0456 (9)	0.0456 (9)	0.0456 (9)	−0.0112 (9)	0.0112 (9)	0.0112 (9)
F3	0.0825 (19)	0.0309 (12)	0.0803 (19)	−0.0163 (15)	−0.019 (2)	−0.0105 (13)

Geometric parameters (Å, º) top

Br1—C1	1.9245 (12)	B—F3ⁱⁱ	1.375 (2)
Br1—C1ⁱ	1.9245 (12)	B—F3ⁱⁱⁱ	1.375 (2)
C1—C2	1.3800 (18)	B—F3^iv	1.375 (2)
C1—C6	1.3810 (19)	B—F3^v	1.375 (2)
F1—C4	1.3442 (16)	B—F3	1.375 (2)
C2—C3	1.388 (2)	B—F3^vi	1.376 (2)
C2—H2	0.979 (11)	B—F2ⁱⁱ	1.403 (4)
C3—C4	1.377 (2)	B—F2	1.404 (4)
C3—H3	0.982 (11)	F2—F3ⁱⁱ	1.656 (4)
C4—C5	1.375 (2)	F2—F3^vi	1.656 (4)
C5—C6	1.385 (2)	F2—F3^iv	1.656 (4)
C5—H5	0.994 (10)	F3—F3^vi	0.905 (5)
C6—H6	0.981 (11)	F3—F2ⁱⁱ	1.656 (4)

C1—Br1—C1ⁱ	99.68 (8)	F3^v—B—F3	111.96 (12)
C2—C1—C6	123.32 (13)	F3ⁱⁱ—B—F3^vi	111.95 (12)
C2—C1—Br1	117.20 (10)	F3ⁱⁱⁱ—B—F3^vi	105.3 (3)
C6—C1—Br1	119.35 (10)	F3^iv—B—F3^vi	111.96 (12)
C1—C2—C3	118.50 (14)	F3^v—B—F3^vi	140.6 (3)
C1—C2—H2	118.4 (8)	F3—B—F3^vi	38.4 (2)
C3—C2—H2	123.1 (8)	F3ⁱⁱ—B—F2ⁱⁱ	106.86 (13)
C4—C3—C2	118.25 (13)	F3ⁱⁱⁱ—B—F2ⁱⁱ	73.15 (13)
C4—C3—H3	119.2 (8)	F3^iv—B—F2ⁱⁱ	106.85 (13)
C2—C3—H3	122.6 (8)	F3^v—B—F2ⁱⁱ	73.14 (13)
F1—C4—C5	118.84 (14)	F3—B—F2ⁱⁱ	73.15 (13)
F1—C4—C3	118.16 (13)	F3^vi—B—F2ⁱⁱ	106.86 (13)
C5—C4—C3	123.00 (14)	F3ⁱⁱ—B—F2	73.14 (13)
C4—C5—C6	119.20 (14)	F3ⁱⁱⁱ—B—F2	106.85 (13)
C4—C5—H5	119.7 (8)	F3^iv—B—F2	73.15 (13)
C6—C5—H5	120.5 (8)	F3^v—B—F2	106.85 (13)
C1—C6—C5	117.68 (13)	F3—B—F2	106.86 (13)
C1—C6—H6	120.2 (8)	F3^vi—B—F2	73.14 (13)
C5—C6—H6	122.1 (8)	F2ⁱⁱ—B—F2	179.998 (1)
F3ⁱⁱ—B—F3ⁱⁱⁱ	140.5 (3)	B—F2—F3ⁱⁱ	52.65 (13)
F3ⁱⁱ—B—F3^iv	111.96 (12)	B—F2—F3^vi	52.65 (13)
F3ⁱⁱⁱ—B—F3^iv	38.4 (2)	F3ⁱⁱ—F2—F3^vi	87.01 (19)
F3ⁱⁱ—B—F3^v	38.4 (2)	B—F2—F3^iv	52.65 (13)
F3ⁱⁱⁱ—B—F3^v	111.95 (12)	F3ⁱⁱ—F2—F3^iv	87.01 (19)
F3^iv—B—F3^v	105.3 (3)	F3^vi—F2—F3^iv	87.01 (19)
F3ⁱⁱ—B—F3	105.3 (3)	F3^vi—F3—B	70.79 (11)
F3ⁱⁱⁱ—B—F3	111.96 (12)	F3^vi—F3—F2ⁱⁱ	118.3 (3)
F3^iv—B—F3	140.6 (3)	B—F3—F2ⁱⁱ	54.21 (15)

C1ⁱ—Br1—C1—C2	108.85 (13)	F3^v—B—F2—F3^vi	138.7 (3)
C1ⁱ—Br1—C1—C6	−75.19 (12)	F3—B—F2—F3^vi	18.7 (3)
C6—C1—C2—C3	−0.8 (3)	F2ⁱⁱ—B—F2—F3^vi	−177 (20)
Br1—C1—C2—C3	174.95 (12)	F3ⁱⁱ—B—F2—F3^iv	−120.0
C1—C2—C3—C4	−0.3 (2)	F3ⁱⁱⁱ—B—F2—F3^iv	18.7 (3)
C2—C3—C4—F1	−178.06 (15)	F3^v—B—F2—F3^iv	−101.3 (3)
C2—C3—C4—C5	2.2 (3)	F3—B—F2—F3^iv	138.7 (3)
F1—C4—C5—C6	177.29 (15)	F3^vi—B—F2—F3^iv	120.0
C3—C4—C5—C6	−2.9 (3)	F2ⁱⁱ—B—F2—F3^iv	−57 (20)
C2—C1—C6—C5	0.1 (2)	F3ⁱⁱ—B—F3—F3^vi	−106.2 (5)
Br1—C1—C6—C5	−175.60 (12)	F3ⁱⁱⁱ—B—F3—F3^vi	87.1 (6)
C4—C5—C6—C1	1.7 (2)	F3^iv—B—F3—F3^vi	54.2 (4)
F3ⁱⁱⁱ—B—F2—F3ⁱⁱ	138.7 (3)	F3^v—B—F3—F3^vi	−146.3 (4)
F3^iv—B—F2—F3ⁱⁱ	120.0	F2ⁱⁱ—B—F3—F3^vi	150.4 (5)
F3^v—B—F2—F3ⁱⁱ	18.7 (3)	F2—B—F3—F3^vi	−29.6 (5)
F3—B—F2—F3ⁱⁱ	−101.3 (3)	F3ⁱⁱ—B—F3—F2ⁱⁱ	103.38 (10)
F3^vi—B—F2—F3ⁱⁱ	−120.0	F3ⁱⁱⁱ—B—F3—F2ⁱⁱ	−63.33 (18)
F2ⁱⁱ—B—F2—F3ⁱⁱ	63 (20)	F3^iv—B—F3—F2ⁱⁱ	−96.23 (8)
F3ⁱⁱ—B—F2—F3^vi	120.0	F3^v—B—F3—F2ⁱⁱ	63.33 (18)
F3ⁱⁱⁱ—B—F2—F3^vi	−101.3 (3)	F3^vi—B—F3—F2ⁱⁱ	−150.4 (5)
F3^iv—B—F2—F3^vi	−120.0	F2—B—F3—F2ⁱⁱ	180.0

Symmetry codes: (i) y−1/4, x+1/4, −z+1/4; (ii) −y+3/4, −x+3/4, −z+7/4; (iii) y−1/2, −z+3/2, −x+1; (iv) z−3/4, −y+5/4, x+3/4; (v) −z+1, x+1/2, −y+3/2; (vi) −x+1/4, z−1/4, y+1/4.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···F3^vii	0.98 (1)	2.59 (1)	3.545 (4)	164 (1)
C3—H3···Cl1^viii	0.98 (1)	2.68 (1)	3.6477 (15)	167 (1)
C6—H6···F2^ix	0.98 (1)	2.27 (1)	3.237 (3)	170 (1)
C6—H6···F3^x	0.98 (1)	2.45 (1)	3.292 (3)	144 (1)

Symmetry codes: (vii) −y+3/4, −x+3/4, −z+3/4; (viii) −y+3/4, −x+3/4, −z−1/4; (ix) −x+1/2, −y+1, z−1/2; (x) x+1/4, −z+5/4, y−1/4.

(gc162) top

Crystal data top

C₁₄H₁₂BrO₂⁺·BF₄⁻	Z = 2
M_r = 378.96	F(000) = 376
Triclinic, P1	D_x = 1.730 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1574 (11) Å	Cell parameters from 4088 reflections
b = 10.0848 (14) Å	θ = 2.8–32.8°
c = 10.1570 (16) Å	µ = 2.87 mm⁻¹
α = 89.158 (5)°	T = 103 K
β = 72.819 (4)°	Block, colourless
γ = 66.607 (5)°	0.12 × 0.11 × 0.05 mm
V = 727.64 (18) Å³

Data collection top

Bruker APEX-II CCD diffractometer	5592 independent reflections
Radiation source: fine-focus sealed tube	4528 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
φ and ω scans	θ_max = 34.7°, θ_min = 2.9°
Absorption correction: multi-scan Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.	h = −12→12
T_min = 0.463, T_max = 0.537	k = −15→15
10971 measured reflections	l = −16→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H-atom parameters not refined
S = 1.02	w = 1/[σ²(F_o²) + (0.0328P)²] where P = (F_o² + 2F_c²)/3
5592 reflections	(Δ/σ)_max = 0.001
200 parameters	Δρ_max = 0.69 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Special details top

Experimental. Bruker KRYOFLEX low temperature device.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.23886 (2)	0.363833 (19)	0.398584 (17)	0.01684 (5)
O1	0.33198 (17)	0.75681 (14)	0.45943 (14)	0.0214 (3)
O2	0.23365 (17)	0.58347 (14)	0.54188 (12)	0.0187 (2)
C1	0.4244 (2)	0.42018 (18)	0.27067 (17)	0.0146 (3)
C2	0.4436 (2)	0.54292 (17)	0.31247 (17)	0.0140 (3)
C3	0.5851 (2)	0.57673 (18)	0.22307 (18)	0.0168 (3)
H3	0.6041	0.6584	0.2488	0.020*
C4	0.6978 (2)	0.49209 (19)	0.09749 (18)	0.0186 (3)
H4	0.7938	0.5160	0.0381	0.022*
C5	0.6721 (2)	0.37285 (19)	0.05737 (18)	0.0190 (3)
H5	0.7488	0.3166	−0.0298	0.023*
C6	0.5334 (2)	0.33538 (19)	0.14519 (18)	0.0179 (3)
H6	0.5145	0.2537	0.1192	0.021*
C7	0.2342 (2)	0.22537 (18)	0.27345 (18)	0.0158 (3)
C8	0.1314 (2)	0.28052 (18)	0.18324 (18)	0.0166 (3)
H8	0.0640	0.3822	0.1846	0.020*
C9	0.1314 (2)	0.1807 (2)	0.09084 (18)	0.0206 (3)
H9	0.0658	0.2137	0.0253	0.025*
C10	0.2269 (3)	0.0329 (2)	0.0939 (2)	0.0255 (4)
H10	0.2243	−0.0346	0.0312	0.031*
C11	0.3262 (3)	−0.0181 (2)	0.1871 (2)	0.0286 (4)
H11	0.3897	−0.1198	0.1882	0.034*
C12	0.3332 (3)	0.07901 (19)	0.2788 (2)	0.0224 (4)
H12	0.4026	0.0464	0.3421	0.027*
C13	0.3242 (2)	0.62872 (18)	0.44977 (17)	0.0152 (3)
C14	0.2125 (3)	0.8522 (2)	0.5874 (2)	0.0249 (4)
H14A	0.0802	0.8836	0.5933	0.037*
H14B	0.2415	0.9376	0.5886	0.037*
H14C	0.2353	0.7999	0.6668	0.037*
F1	0.02017 (16)	0.25393 (15)	0.61282 (12)	0.0329 (3)
F2	0.29356 (14)	0.16442 (12)	0.66419 (12)	0.0264 (2)
F3	0.03704 (16)	0.13381 (11)	0.80309 (11)	0.0252 (2)
F4	0.04119 (17)	0.35784 (12)	0.80114 (13)	0.0312 (3)
B1	0.0976 (3)	0.2271 (2)	0.7214 (2)	0.0167 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01784 (8)	0.02044 (9)	0.01280 (8)	−0.01087 (6)	−0.00135 (6)	0.00070 (6)
O1	0.0206 (6)	0.0184 (6)	0.0218 (6)	−0.0090 (5)	0.0001 (5)	−0.0045 (5)
O2	0.0204 (6)	0.0210 (6)	0.0133 (6)	−0.0084 (5)	−0.0036 (5)	0.0019 (5)
C1	0.0117 (6)	0.0187 (8)	0.0127 (7)	−0.0066 (6)	−0.0025 (5)	0.0027 (6)
C2	0.0118 (6)	0.0155 (7)	0.0143 (7)	−0.0045 (6)	−0.0050 (6)	0.0026 (6)
C3	0.0126 (7)	0.0184 (8)	0.0199 (8)	−0.0070 (6)	−0.0051 (6)	0.0033 (6)
C4	0.0146 (7)	0.0216 (8)	0.0182 (8)	−0.0073 (6)	−0.0035 (6)	0.0055 (7)
C5	0.0143 (7)	0.0221 (8)	0.0164 (8)	−0.0057 (7)	−0.0014 (6)	0.0003 (7)
C6	0.0146 (7)	0.0181 (8)	0.0183 (8)	−0.0060 (6)	−0.0022 (6)	−0.0021 (6)
C7	0.0152 (7)	0.0151 (7)	0.0170 (8)	−0.0071 (6)	−0.0035 (6)	0.0009 (6)
C8	0.0148 (7)	0.0141 (7)	0.0173 (8)	−0.0039 (6)	−0.0031 (6)	0.0016 (6)
C9	0.0180 (7)	0.0235 (9)	0.0185 (8)	−0.0077 (7)	−0.0040 (6)	−0.0024 (7)
C10	0.0251 (9)	0.0217 (9)	0.0259 (10)	−0.0118 (8)	0.0008 (7)	−0.0074 (7)
C11	0.0277 (9)	0.0121 (8)	0.0379 (12)	−0.0039 (7)	−0.0048 (8)	0.0003 (8)
C12	0.0219 (8)	0.0163 (8)	0.0266 (10)	−0.0051 (7)	−0.0085 (7)	0.0060 (7)
C13	0.0131 (7)	0.0167 (7)	0.0164 (8)	−0.0050 (6)	−0.0073 (6)	0.0014 (6)
C14	0.0239 (9)	0.0212 (9)	0.0237 (9)	−0.0086 (7)	0.0000 (7)	−0.0067 (7)
F1	0.0293 (6)	0.0528 (8)	0.0272 (6)	−0.0226 (6)	−0.0163 (5)	0.0168 (6)
F2	0.0141 (5)	0.0236 (6)	0.0362 (7)	−0.0044 (4)	−0.0053 (4)	0.0010 (5)
F3	0.0377 (6)	0.0216 (5)	0.0173 (5)	−0.0187 (5)	−0.0011 (5)	0.0018 (4)
F4	0.0347 (6)	0.0179 (5)	0.0327 (7)	−0.0123 (5)	0.0033 (5)	−0.0064 (5)
B1	0.0163 (8)	0.0159 (8)	0.0166 (9)	−0.0068 (7)	−0.0032 (7)	0.0019 (7)

Geometric parameters (Å, º) top

Br1—C7	1.9210 (16)	C7—C8	1.385 (2)
Br1—C1	1.9497 (15)	C8—C9	1.386 (2)
O1—C13	1.3248 (19)	C8—H8	0.9500
O1—C14	1.453 (2)	C9—C10	1.386 (3)
O2—C13	1.2147 (19)	C9—H9	0.9500
C1—C6	1.380 (2)	C10—C11	1.387 (3)
C1—C2	1.395 (2)	C10—H10	0.9500
C2—C3	1.399 (2)	C11—C12	1.390 (3)
C2—C13	1.485 (2)	C11—H11	0.9500
C3—C4	1.384 (2)	C12—H12	0.9500
C3—H3	0.9500	C14—H14A	0.9800
C4—C5	1.386 (2)	C14—H14B	0.9800
C4—H4	0.9500	C14—H14C	0.9800
C5—C6	1.398 (2)	F1—B1	1.398 (2)
C5—H5	0.9500	F2—B1	1.397 (2)
C6—H6	0.9500	F3—B1	1.386 (2)
C7—C12	1.382 (2)	F4—B1	1.391 (2)

C7—Br1—C1	98.99 (7)	C10—C9—H9	119.9
C13—O1—C14	116.40 (13)	C8—C9—H9	119.9
C6—C1—C2	123.16 (14)	C9—C10—C11	121.11 (17)
C6—C1—Br1	118.80 (12)	C9—C10—H10	119.4
C2—C1—Br1	118.02 (12)	C11—C10—H10	119.4
C1—C2—C3	117.27 (15)	C10—C11—C12	120.31 (18)
C1—C2—C13	120.73 (14)	C10—C11—H11	119.8
C3—C2—C13	121.92 (14)	C12—C11—H11	119.8
C4—C3—C2	120.56 (15)	C7—C12—C11	116.69 (17)
C4—C3—H3	119.7	C7—C12—H12	121.7
C2—C3—H3	119.7	C11—C12—H12	121.7
C3—C4—C5	120.78 (15)	O2—C13—O1	124.94 (16)
C3—C4—H4	119.6	O2—C13—C2	122.94 (15)
C5—C4—H4	119.6	O1—C13—C2	112.10 (14)
C4—C5—C6	119.97 (16)	O1—C14—H14A	109.5
C4—C5—H5	120.0	O1—C14—H14B	109.5
C6—C5—H5	120.0	H14A—C14—H14B	109.5
C1—C6—C5	118.24 (15)	O1—C14—H14C	109.5
C1—C6—H6	120.9	H14A—C14—H14C	109.5
C5—C6—H6	120.9	H14B—C14—H14C	109.5
C12—C7—C8	124.71 (16)	F3—B1—F4	109.82 (14)
C12—C7—Br1	118.26 (13)	F3—B1—F2	110.36 (15)
C8—C7—Br1	117.03 (12)	F4—B1—F2	109.37 (14)
C7—C8—C9	117.04 (16)	F3—B1—F1	109.60 (14)
C7—C8—H8	121.5	F4—B1—F1	109.35 (16)
C9—C8—H8	121.5	F2—B1—F1	108.31 (15)
C10—C9—C8	120.11 (17)

C7—Br1—C1—C6	−14.38 (15)	C12—C7—C8—C9	−1.0 (2)
C7—Br1—C1—C2	167.21 (13)	Br1—C7—C8—C9	178.61 (12)
C6—C1—C2—C3	−2.1 (2)	C7—C8—C9—C10	1.8 (2)
Br1—C1—C2—C3	176.21 (12)	C8—C9—C10—C11	−1.0 (3)
C6—C1—C2—C13	−179.06 (15)	C9—C10—C11—C12	−0.6 (3)
Br1—C1—C2—C13	−0.7 (2)	C8—C7—C12—C11	−0.6 (3)
C1—C2—C3—C4	1.2 (2)	Br1—C7—C12—C11	179.82 (13)
C13—C2—C3—C4	178.09 (15)	C10—C11—C12—C7	1.4 (3)
C2—C3—C4—C5	0.4 (3)	C14—O1—C13—O2	−4.2 (2)
C3—C4—C5—C6	−1.1 (3)	C14—O1—C13—C2	177.00 (14)
C2—C1—C6—C5	1.4 (3)	C1—C2—C13—O2	15.0 (2)
Br1—C1—C6—C5	−176.90 (13)	C3—C2—C13—O2	−161.80 (16)
C4—C5—C6—C1	0.2 (3)	C1—C2—C13—O1	−166.21 (15)
C1—Br1—C7—C12	101.04 (14)	C3—C2—C13—O1	17.0 (2)
C1—Br1—C7—C8	−78.61 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···F4ⁱ	0.95	2.40	3.334 (2)	166
C12—H12···F2ⁱⁱ	0.95	2.53	3.270 (2)	135
C14—H14B···F3ⁱⁱⁱ	0.98	2.61	3.164 (2)	116

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) x, y+1, z.

References

Alcock, N. W. & Countryman, R. M. (1977). J. Chem. Soc. Dalton Trans. 217, 217–219. CSD CrossRef Web of Science Google Scholar
Awwadi, F. F., Haddad, S. F., Twamley, B. & Willett, R. D. (2012). CrystEngComm, 14, 6761–6769. Web of Science CSD CrossRef CAS Google Scholar
Awwadi, F. F., Willett, R. D., Peterson, K. A. & Twamley, B. (2006). Chem. Eur. J. 12, 8952–8960. Web of Science CrossRef PubMed CAS Google Scholar
Bader, R. F. W., Carroll, M. T., Cheeseman, J. R. & Chang, C. (1987). J. Am. Chem. Soc. 109, 7968–7979. CrossRef CAS Web of Science Google Scholar
Brinck, T., Murray, J. S. & Politzer, P. (1992). Int. J. Quantum Chem. 44, 57–64. CrossRef Google Scholar
Brinck, T., Murray, J. S. & Politzer, P. (1993). Int. J. Quantum Chem. 48, 73–88. CrossRef CAS Web of Science Google Scholar
Britton, D., Young, V. G. & Schlemper, E. O. (2002). Acta Cryst. C58, m307–m309. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Bulat, F. A., Toro-Labbé, A., Brinck, T., Murray, J. S. & Politzer, P. (2010). J. Mol. Model. 16, 1679–1691. Web of Science CrossRef CAS PubMed Google Scholar
Catalano, L., Cavallo, G., Metrangolo, P., Resnati, G. & Terraneo, G. (2016). Top. Curr. Chem. 373, 289–309. CrossRef CAS PubMed Google Scholar
Cavallo, G., Metrangolo, P., Milani, R., Pilati, T., Priimagi, A., Resnati, G. & Terraneo, G. (2016). Chem. Rev. 116, 2478–2601. Web of Science CrossRef CAS PubMed Google Scholar
Cavallo, G., Metrangolo, P., Pilati, T., Resnati, G. & Terraneo, G. (2014). Cryst. Growth Des. 14, 2697–2702. Web of Science CrossRef CAS Google Scholar
Clark, T., Murray, J. S., Lane, P. & Politzer, P. (2008). J. Mol. Model. 14, 689–697. Web of Science CrossRef PubMed CAS Google Scholar
Clark, T., Murray, J. S. & Politzer, P. (2014). Aust. J. Chem. 67, 451–456. Web of Science CrossRef CAS Google Scholar
Colin, J. J. (1814). Ann. Chim. 91, 252–272. Google Scholar
Desiraju, G. R. & Harlow, R. L. (1989). J. Am. Chem. Soc. 111, 6757–6764. CSD CrossRef CAS Web of Science Google Scholar
Desiraju, G. R., Ho, P. S., Kloo, L., Legon, A. C., Marquardt, R., Metrangolo, P., Politzer, P., Resnati, G. & Rissanen, K. (2013). Pure Appl. Chem. 85, 1711–1713. Web of Science CrossRef CAS Google Scholar
Freytag, M., Jones, P. G., Ahrens, B. & Fischer, A. K. (1999). New J. Chem. 23, 1137–1139. Web of Science CSD CrossRef CAS Google Scholar
Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E. & Robb, M. A. (2009). GAUSSIAN09, Revision A.1. Gaussian Inc., Wallingford, CT, USA. Google Scholar
Geller, S. & Schawlow, A. L. (1955). J. Chem. Phys. 23, 779–783. CrossRef CAS Web of Science Google Scholar
Halton, B., Kay, A. J., McNichols, A. T., Stang, P. J., Apeloig, Y., Boese, R., Maulitz, A. H. & Haumann, T. (2001). Arkivoc, 2, 8–31. Google Scholar
Hathwar, V. R., Chopra, D., Panini, P. & Guru Row, T. N. (2014). Cryst. Growth Des. 14, 5366–5369. Web of Science CSD CrossRef CAS Google Scholar
Heiart, R. B. & Carpenter, G. B. (1956). Acta Cryst. 9, 889–895. CrossRef IUCr Journals Web of Science Google Scholar
Ho, P. C., Szydlowski, P., Sinclair, J., Elder, P. J. W., Kübel, J., Gendy, C., Lee, L. M., Jenkins, I., Britten, J. F., Morim, D. R. & Vargas-Baca, I. (2016). Nat. Commun. 7, 11299. Web of Science CSD CrossRef PubMed Google Scholar
Ji, B., Wang, W., Deng, D. & Zhang, Y. (2011). Cryst. Growth Des. 11, 3622–3628. Web of Science CSD CrossRef CAS Google Scholar
Ketelaar, J. A. A. & Zwartsenberg, J. W. (1939). Recl Trav. Chim. Pays Bas, 58, 448–452. CrossRef Google Scholar
Klapötke, T. M., Krumm, B., Gálvez-Ruiz, J. C., Nöth, H. & Schwab, I. (2004). Eur. J. Inorg. Chem. 2004, 4764–4769. Google Scholar
Konnert, J. H., Britton, D. & Chow, Y. M. (1972). Acta Cryst. B28, 180–187. CSD CrossRef IUCr Journals Web of Science Google Scholar
Merritt, E. A. & Olofsson, B. (2009). Angew. Chem. Int. Ed. 48, 9052–9070. Web of Science CrossRef CAS Google Scholar
Metrangolo, P., Pilati, T., Terraneo, G., Biella, S. & Resnati, G. (2009). CrystEngComm, 11, 1187–1196. Web of Science CrossRef CAS Google Scholar
Metrangolo, P. & Resnati, G. (2001). Chem. Eur. J. 7, 2511–2519. CrossRef PubMed CAS Google Scholar
Metrangolo, P. & Resnati, G. (2013). Chem. Commun. 49, 1783–1785. Web of Science CrossRef CAS Google Scholar
Murray, J. S., Lane, P. & Politzer, P. (2009). J. Mol. Model. 15, 723–729. Web of Science CrossRef PubMed CAS Google Scholar
Murray, J. S., Riley, K. E., Politzer, P. & Clark, T. (2010). Aust. J. Chem. 63, 1598–1607. Web of Science CrossRef CAS Google Scholar
Nyburg, S. C. & Wong-Ng, W. (1979). Proc. R. Soc. London Ser. A, 367, 29–45. CrossRef CAS Web of Science Google Scholar
Ochiai, M., Nishi, Y., Goto, S., Shiro, M. & Frohn, H. J. J. (2003). J. Am. Chem. Soc. 125, 15304–15305. Web of Science CSD CrossRef PubMed CAS Google Scholar
O'Hair, R. A. J., Williams, C. M. & Clark, T. (2010). J. Mol. Model. 16, 559–565. Web of Science PubMed CAS Google Scholar
Pavan, M. S., Pal, R., Nagarajan, K. & Guru Row, T. N. (2014). Cryst. Growth Des. 14, 5477–5485. CSD CrossRef CAS Google Scholar
Politzer, P., Lane, P. & Murray, J. S. (2016). Crystals, 6, 7. Web of Science CrossRef Google Scholar
Politzer, P., Murray, J. S. & Clark, T. (2013). Phys. Chem. Chem. Phys. 15, 11178–11189. Web of Science CrossRef CAS PubMed Google Scholar
Politzer, P., Murray, J. S. & Clark, T. (2015a). J. Mol. Model. 21, 52. Web of Science CrossRef PubMed Google Scholar
Politzer, P., Murray, J. S. & Clark, T. (2015b). Top. Curr. Chem. 358, 19–42. Web of Science CrossRef CAS PubMed Google Scholar
Politzer, P., Murray, J. S., Janjić, G. V. & Zarić, S. D. (2014). Crystals, 4, 12–31. Web of Science CrossRef Google Scholar
Price, S. L., Stone, A. J., Lucas, J., Rowland, R. S. & Thornley, A. E. (1994). J. Am. Chem. Soc. 116, 4910–4918. CrossRef CAS Web of Science Google Scholar
Riley, K. E., Murray, J. S., Fanfrlík, J., Řezáč, J., Solá, R. J., Concha, M. C., Ramos, F. M. & Politzer, P. (2011). J. Mol. Model. 17, 3309–3318. Web of Science CrossRef CAS PubMed Google Scholar
Riley, K. E., Tran, K., Lane, P., Murray, J. S. & Politzer, P. (2016). J. Comput. Sci. 17, 273–284. Web of Science CrossRef Google Scholar
Sheldrick, G. M. (1006). SADABS. University of Göttingen, Germany. Google Scholar
Southern, S. A. & Bryce, D. L. (2015). J. Phys. Chem. A, 119, 11891–11899. Web of Science CrossRef CAS PubMed Google Scholar
Stevens, E. D. (1979). Mol. Phys. 37, 27–45. CrossRef CAS Web of Science Google Scholar
Suefuji, T., Shiro, M., Yamaguchi, K. & Ochiai, M. (2006). Heterocycles, 67, 391–397. CAS Google Scholar
Valerio, G., Raos, G., Meille, S. V., Metrangolo, P. & Resnati, G. (2000). J. Phys. Chem. A, 104, 1617–1620. Web of Science CrossRef CAS Google Scholar
Williamson, B. L., Stang, P. J. & Arif, A. M. (1993). J. Am. Chem. Soc. 115, 2590–2597. CSD CrossRef CAS Web of Science Google Scholar
Xu, M., Li, X.-X., Chen, Y., Pitzer, A. L., Zhang, Y. & Li, P.-L. (2014). J. Cell. Mol. Med. 18, 2165–2175. Web of Science CrossRef CAS PubMed Google Scholar
Zhao, Y. & Truhlar, D. G. (2008). Theor. Chem. Acc. 120, 215–241. Web of Science CrossRef CAS Google Scholar
Zhdankin, V. V., Koposov, A. Y., Su, L., Boyarskikh, V. V., Netzel, B. C. & Young, V. G. Jr (2003). Org. Lett. 5, 1583–1586. Web of Science CSD CrossRef PubMed CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

IUCrJ

Volume 4| Part 4| July 2017| Pages 411-419

ISSN: 2052-2525

https://doi.org/10.1107/S2052252517004262

CHEMISTRY | CRYSTENG

Open

access