π-hole interactions involving nitro compounds: directionality of nitrate esters Antonio Báuza, a Antonio Frontera*,a and Tiddo J.

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1 Supporting Information accompanying: π-hole interactions involving nitro compounds: directionality of nitrate esters Antonio Báuza, a Antonio Frontera*,a and Tiddo J. Mooibroek*,b a Department of Chemistry, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, Palma (Baleares), SPAIN; Fax: (+) ; toni.frontera@uib.es b van t Hoff Institute for Molecular Sciences, Universiteit van Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands; t.j.mooibroek@uva.nl 1

2 Table of Contents: 1. Additional computational details AIM analysis of selected complexes Data on structural isomers of some R NO 2 molecules Cartesian coordinates of optimized geometries CSD Analysis Description of queries used to retrieve data from the CSD Deriving geometric parameters (XYZ, r) Additional CSD data

3 1. Additional computational details 1.1. AIM analysis of selected complexes Figure S1. Graphical renderings of an Atoms in Molecules analysis for several selected complexes, computed at the MP2/6-311+G** level of theory using the AIMAll program Data on structural isomers of some R NO 2 molecules Figure S2. Molecular Electrostatic Potential maps (MEPs) of structural isomers of R-NO 2 molecules derived from MP2/6-311+G** energy optimized geometries. The energetic values are in kcal/mol and ΔE quantifies by what margin these isomers are less stable. 1 AIMAll (Version ), Todd A. Keith, TK Gristmill Software, Overland Park KS, USA,

4 1.3. Cartesian coordinates of optimized geometries 1 N O O H N O O F Isomer of 2 N O O F N O O Cl Isomer of 3 N O O Cl N O O Br Isomer of 4 N O O Br N O

5 O I Isomer of 5 N O O I N O O C N Isomer of 6 N O O C N C C C C C C H H H H H N O O N O O O C F F

6 F N O O O C H H H N O O C F F F N O O C H H H N O O N O O [2 + F ] N O O F F [2 + Cl ] N

7 O O F Cl [2 + NC ] N O O F N C [2 + NCCH 3 ] N O O F N C C H H H [2 + O(CH 3 ) 2 ] N O O F O C H H H C H H H [6 + F ] N O O C N F

8 [6 + Cl ] N O O C N Cl [6 + NC ] N O O C N C N [6 + NCCH 3 ] N O O C N N C C H H H [6 + O(CH 3 ) 2 ] N O O C N O C H H H C H H H

9 [8 + F ] N O O O C F F F F [8 + Cl ] N O O O C F F F Cl [8 + NC ] N O O O C F F F C N [8 + NCCH 3 ] N O O O C F F F N C C H

10 H H [8 + O(CH 3 ) 2 ] N O O O C F F F O C H H H C H H H [10 + F ] N O O C F F F F [10 + Cl ] N O O C F F F Cl [10 + NC ] N O O C

11 F F F C N [10 + NCCH 3 ] N O O C F F F N C C H H H [10 + O(CH 3 ) 2 ] N O O C F F F O C H H H C H H H [12 + F ] N O O N O O F

12 [12 + Cl ] N O O N O O Cl [12 + NC ] N O O N O O C N [12 + NCCH 3 ] N O O N O O N C C H H H [12 + O(CH 3 ) 2 ] N O O N O O O C H H H C

13 H H H

14 2. CSD Analysis 2.1. Description of queries used to retrieve data from the CSD The CSD (version 5.37 (Nov including two updates) was inspected using ConQuest (version 1.18). All searches were limited to high quality structures (R 0.1) and powder structures and structures containing errors were omitted. Two of the N-O bonds were set as any type, while the N-O2C bond was set as a single bond. All covalent bond distances and selected triatomic angles were collected to reconstruct the average models used for the inset nitrate ester models in Figure 3, Figure S4 and Figure S5. The interatomic distance between the interacting atom (F, Cl, Br, I, At, O, S, Se, Te, N, P or As in ElR ( electron rich ) or O in O=X and the nitro s N-atom (e, highlighted in red in Figure S3) was set as 5 Å so that the data was confined within a 10 Å diameter sphere centred on N. Figure S3. Illustration of the query used to extract (geometric) data from the PDB and CSD Deriving geometric parameters (XYZ, r) The interatomic distances between the interacting atom and O1 and O3, as well as the O1- O3 distance were also collected. The triangle formed by O1-N-O3 was chosen as the base, and the interacting atom as the tip of a tetrahedron (see Figure S3) so that Cartesian Coordinates {X,Y,Z} of all the atoms could be derived as follows: the N-atom was taken as the centre {0,0,0}, O1 as {0,c,0}, O3 as {x,y,0}, and the interacting atom at {l,m,n}. Distances a-f were measured, from which y, x, m, l and n can be derived using equations (S1) - (S5) respectively. (S1) (S2) (S3) (S4) (S5) a c b y 2c x a y c e d m 2c (= X-value) a e f 2my l 2x (= Y-value) n e m l (= Z-value) Thus, the distance between the interacting atom and the plane defined by O1-N-O3 is n, i.e. the Z-value. With this and the N interacting atom distance (e) the parallel displacement parameter (r) could be derived according to equation (S6): (S6) 2 2 r e n 14

To obtain all {X,Y,Z} coordinates of the average models, it was assumed that O2 and C were coplanar with O1-N-O3.

15 With this procedure the sign of n (i.e. the Z-axis) is always positive, meaning that data in one half of the sphere were reflected to the other half of the sphere to obtain the data within a 5 Å high and 10 Å wide hemisphere. To obtain all {X,Y,Z} coordinates of the average models, it was assumed that O2 and C were coplanar with O1-N-O3. The averages of relevant distances and angles were then used together with the rules of sine and cosine to obtain the {X,Y,Z} coordinates. The relative standard deviations of the parameters used were typically below 5% Additional CSD data Figure S4. Data from the CSD of ElR entities enveloping a central nitrate ester as with N ElR 5 Å. Within these data, 346 hits were characterized by a parallel displacement of 1 Å from N (golden body in the inset figure) and these data were plotted as a function of the van der Waals corrected N ElR distance). Of these data, 33% (114) hits displayed van der Waals overlap. Figure S5. Perspective (left) and top (right) views of the distribution of H-atoms (of X H) enveloping a central nitrate ester as found within the CSD with N H 5 Å. These data span 3,515 hits found in 149 Crystallographic Information Files (CIFs). Of these data, only 1.7% (54 hits) are characterized by a parallel displacement of 1 Å from N (black circle in the righthand figure). 15

Electronic Supporting Information. for:

Electronic Supplementary Material (ESI) for CrystEngComm. This journal is The Royal Society of Chemistry 2016 Electronic Supporting Information for: Synthesis, X-ray characterization, DFT calculations