Extremely Strong Halogen Bond. The Case of a Double-Charge-Assisted Halogen Bridge

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1 Supporting Information Extremely Strong Halogen Bond. The Case of a Double-Charge-Assisted Halogen Bridge Małgorzata Domagała*, Aneta Lutyńska, Marcin Palusiak Theoretical and Structural Chemistry Group, Faculty of Chemistry, University of Lodz, Pomorska 163/165, Lodz, Poland malgorzata.domagala@chemia.uni.lodz.pl Contents: page S2 page S6 page S6 page S7 page S7 page S8 page S8 page S12 page S15 page S20 page S24 Figure S1. Molecular graphs of studied (+/-)CAXB complexes. Figure S2. Molecular graphs of studied (+/-)CAXB complexes, view along halogen bond directions to quinuclidine cage (left) and its unsaturated derivative (right). Figure S3. Linear relation between CT in Quin_I and Quin_II (+/-)CAXB complexes. Figure S4. Linear relation between CT NBO vs CT AIM in Quin_I (full black circles) and Quin_II (empty black circles) (+/-)CAXB complexes. Figure S5. Molecular graphs of studied neutral complexes Quin_II-Br NCH and Quin_II-Cl NCH. Table S1. Bond length changes [Å] in cage of Quin_I and Quin_II (+/-)CAXB complexes. Table S2. Atom coordinates of (+/-)CAXB dimers with Quinu_I corresponding to optimized geometries with CP-correction at ωb97xd/aug-cc-pvtz level of theory. Table S3. Atom coordinates of (+/-)CAXB dimers with Quinu_II corresponding to optimized geometries with CP-correction at ωb97xd/aug-cc-pvtz level of theory. Table S4. Atom coordinates of partially charged dimers with Quinu_I corresponding to optimized geometries with CP-correction at ωb97xd/aug-cc-pvtz level of theory. Table S5. Atom coordinates of partially charged dimers with Quinu_II corresponding to optimized geometries with CP-correction at ωb97xd/aug-cc-pvtz level of theory. Table S6. Atom coordinates of neutral dimers with Quinu_II corresponding to optimized geometries with CP-correction at ωb97xd/aug-cc-pvtz level of theory. S1

2 H-Quin_I-Cl F CN-Quin_I-Cl F H-Quin_I-Cl Cl CN-Quin_I-Cl Cl H-Quin_I-Cl Br CN-Quin_I-Cl Br H-Quin_I-Cl CN CN-Quin_I-Cl CN S2

3 H-Quin_I-Br F CN-Quin_I-Br F H-Quin_I-Br Cl CN-Quin_I-Br Cl H-Quin_I-Br Br CN-Quin_I-Br Br H-Quin_I-Br CN CN-Quin_I-Br CN S3

4 H-Quin_II-Cl F CN-Quin_II-Cl F H-Quin_II-Cl Cl CN-Quin_II-Cl Cl H-Quin_II-Cl Br CN-Quin_II-Cl Br H-Quin_II-Cl CN CN-Quin_II-Cl CN S4

5 H-Quin_II-Br F CN-Quin_II-Br F H-Quin_II-Br Cl CN-Quin_II-Br Cl H-Quin_II-Br Br CN-Quin_II-Br Br H-Quin_II-Br CN CN-Quin_II-Br CN Figure S1. Molecular graphs of studied (+/-)CAXB complexes. S5

6 Figure S2. Molecular graphs of studied (+/-)CAXB complexes. View along halogen bond directions to quinuclidine cage (left) and its unsaturated derivative (right) CT Quin_II y = x R² = CT Quin_I Figure S3. Linear relation between CT in Quin_I and Quin_II (+/-)CAXB complexes. S6

7 CT AIM y = x R² = y = 0.788x R² = CT NBO Figure S4. Linear relation between CT NBO vs CT AIM in Quin_I (full black circles) and Quin_II (empty black circles) (+/-)CAXB complexes. Figure S5. Molecular graphs of studied neutral complexes Quin_II-Br NCH and Quin_II- Cl NCH. S7

8 Table S1. Bond length changes [Å] in cage Quin_I and Quin_II (+/-)CAXB complexes. Quin_I Quin_II N-C C-C C-C N-C C=C C-C H/Cl F H/Cl Cl H/Cl Br H/Cl NC H/Br F H/Br Cl H/Br Br H/Br NC CN/Cl F CN/Cl Cl CN/Cl Br CN/Cl NC CN/Br F CN/Br Cl CN/Br Br CN/Br NC Table S2. Atom coordinates of (+/-)CAXB dimers with Quinu_I corresponding to optimized geometries with CP-correction at ωb97xd/aug-cc-pvtz level of theory. H-Quin_I-Cl F C C C H H H H C H H C H H C H H C H CN-Quin_I-Cl F C C C H H H H C H H C H H C H H C H S8

9 H N H Cl F HF= H-Quin_I-Cl Cl C C C H H H H C H H C H H C H H C H H N H Cl Cl HF= H-Quin_I-Cl Br C C C H H H H C H H C H H C H H C H H N H H N C N Cl F HF= CN-Quin_I-Cl Cl C C C H H H H C H H C H H C H H C H H N C N Cl Cl HF= CN-Quin_I-Cl Br C C C H H H H C H H C H H C H H C H H N C S9

10 Cl Br HF= H-Quin_I-Cl NC C C C H H H H C H H C H H C H H C H H N N C Cl H HF= H-Quin_I-Br F C C C H H H H C H H C H H C H H C H H N H Br F N Br Cl HF= CN-Quin_I-Cl NC C C C H H H H C H H C H H C H H C H H N C N N C Cl HF= CN-Quin_I-Br F C C C H H H H C H H C H H C H H C H H Br N C N S10

11 HF= H-Quin_I-Br Cl C C C H H H H C H H C H H C H H C H H N H Br Cl HF= H-Quin_I-Br Br C C C H H H H C H H C H H C H H C H H N H Br Br HF= F HF= CN-Quin_I-Br Cl C C C H H H H C H H C H H C H H C H H Br N C N Cl HF= CN-Quin_I-Br Br C C C H H H H C H H C H H C H H C H H Br N C N Br HF= S11

12 H-Quin_I-Br NC C C C H H H H C H H C H H C H H C H H N N C H Br HF= CN-Quin_I-Br NC C C C H H H H C H H C H H C H H C H H Br N C N N C HF= Table S3. Atom coordinates of (+/-)CAXB dimers with Quinu_II corresponding to optimized geometries with CP-correction at ωb97xd/aug-cc-pvtz level of theory. H-Quin_II-Cl F C C C H H C H C H C H C H N H F Cl HF= CN-Quin_II-Cl F C C C H H C H C H C H C H N C N Cl F S12

13 HF= H-Quin_II-Cl Cl C C C H H C H C H C H C H N H Cl Cl HF= H-Quin_II-Cl Br C C C H H C H C H C H C H N H Br Cl HF= H-Quin_II-Cl NC C C C H H C H C H C H C CN-Quin_II-Cl Cl C C C H H C H C H C H C H N C N Cl Cl HF= CN-Quin_II-Cl Br C C C H H C H C H C H C H N C N Br Cl HF= CN-Quin_II-Cl NC C C C H H C H C H C H C S13

14 H N N C Cl H HF= H-Quin_II-Br F C C C H H C H C H C H C H N H Br F HF= H-Quin_II-Br Cl C C C H H C H C H C H C H N H Cl Br HF= H-Quin_II-Br Br C C C H H H N C N N C Cl HF= CN-Quin_II-Br F C C C H H C H C H C H C H Br N C N F HF= CN-Quin_II-Br Cl C C C H H C H C H C H C H Br N C N Cl HF= CN-Quin_II-Br Br C C C H H S14

15 C H C H C H C H N H Br Cl HF= H-Quin_II-Br NC C C C H H C H C H C H C H N N C H Br HF= C H C H C H C H Br N C N Br HF= CN-Quin_II-Br NC C C C H H C H C H C H C H Br N C N N C HF= Table S4. Atom coordinates of partially charged dimers with Quinu_I corresponding to optimized geometries with CP-correction at ωb97xd/aug-cc-pvtz level of theory. (+)CAXB H-Quin_I-Cl ClH C C C H H H H C H CN-Quin_I-Cl BrH C C C H H H H C H S15

16 H C H H C H H C H H N Cl Cl H H HF= H-Quin_I-Cl BrH C C C H H H H C H H C H H C H H C H H N Br Cl H H HF= H-Quin_I-Br FH C C C H H H H C H H H C H H C H H C H H N C N Br Cl H HF= CN-Quin_I-Br FH C C C H H H H C H H C H H C H H C H H Br N C N F H HF= CN-Quin_I-Br ClH C C C H H H H C H H S16

17 C H H C H H C H H Br N F H H HF= H-Quin_I-Br ClH C C C H H H H C H H C H H C H H C H H Br N Cl H H HF= H-Quin_I-Br BrH C C C H H H H C H H C C H H C H H C H H Br N C N Cl H HF= CN-Quin_I-Br BrH C C C H H H H C H H C H H C H H C H H Br N C N Br H HF= CN-Quin_I-Br NCH C C C H H H H C H H C S17

18 H H C H H C H H Br N Br H H HF= H-Quin_I-Br NCH C C C H H C H C H H C H H C H H C H H Br N N C H H HF= H H C H H C H H Br N C N N C H HF= ( _ )CAXB Quin_I-Cl F C C C H H H H C H H C Quin_I-Br F C C C H H H H C H H C S18

19 H H C H H C H H N Cl F HF= Quin_I-Br Cl C C C H H H H C H H C H H C H H C H H Br N Cl HF= H H C H H C H H Br N F HF= Quin_I-Br Br C C C H H H H C H H C H H C H H C H H Br N Br HF= Quin_I-Br NC C C C H H H H C H H C H H C H H C H H S19

20 Br N N C HF= Table S5. Atom coordinates of partially charged dimers with Quinu_II corresponding to optimized geometries with CP-correction at ωb97xd/aug-cc-pvtz level of theory. (+)CAXB H-Quin_II-Cl FH C C C H H C H C H C H C H N Cl F H H HF= H-Quin_II-Cl ClH C C C H H C H C H C H C H N Cl CN-Quin_II-Cl FH C C C H H C H C H C H C H N C N Cl F H HF= CN-Quin_II-Cl ClH C C C H H C H C H C H C H N C S20

21 Cl H H HF= H-Quin_II-Cl BrH C C C H H C H C H C H C H N Br Cl H H HF= H-Quin_II-Cl NCH C C C H H C H C H C H C H N N C Cl H H HF= H-Quin_II-Br FH C C C H H N Cl Cl H HF= CN-Quin_II-Cl BrH C C C H H C H C H C H C H N C N Br Cl H HF= CN-Quin_II-Cl NCH C C C H H C H C H C H C H N C N N C Cl H HF= CN-Quin_II-Br FH C C C H H S21

22 C H C H C H C H Br N F H H HF= H-Quin_II-Br ClH C C C H H C H C H C H C H Br N Cl H H HF= H-Quin_II-Br BrH C C C H H C H C H C H C H Br N Br H H C H C H C H C H Br N C N F H HF= CN-Quin_II-Br ClH C C C H H C H C H C H C H Br N C N Cl H HF= CN-Quin_II-Br BrH C C C H H C H C H C H C H Br N C N Br S22

23 HF= H-Quin_II-Br NCH C C C H H C H C H C H C H Br N N C H H HF= H HF= CN-Quin_II-Br NCH C C C H H C H C H C H C H Br N C N N C H HF= ( _ )CAXB Quin_II-Cl F C C C H H C H C H C H C H N Cl F HF= Quin_II-Cl Cl C C C H H C H C H C Quin_II-Br F C C C H H C H C H C H C H Br N F HF= Quin_II-Br Cl C C C H H C H C H C S23

24 H C H N Cl Cl HF= Quin_II-Cl Br C C C H H C H C H C H C H N Br Cl HF= Quin_II-Cl NC C C C H H C H C H C H C H N N C Cl HF= H C H Br N Cl HF= Quin_II-Br Br C C C H H C H C H C H C H Br N Br HF= Quin_II-Br NC C C C H H C H C H C H C H Br N N C HF= Table S6. Atom coordinates of neutral dimers with Quinu_II corresponding to optimized geometries with CP-correction at ωb97xd/aug-cc-pvtz level of theory. Quin_II-Cl NCH C C Quin_II-Br NCH C C S24

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