Supplementary Material 1: Occurrence of the CP1 pattern in the structures of CSD

Fragments searched

(Filters of the CSD search: 3D coordinates determined, not disordered, only organics, solvent free)

CSD refcode / Pattern / Operation
AHEKUT / CP1 + / glide + i
ALAZAO / CP1 / translation
ATTDAZ / other
CANCAW / CP1 / translation
COJMUJ / / i
COYVER / / i
COYVIV / / i
FELRUJ / CP1 + / 2 ind. mol.
GEGZIB / / 21
GEMMER / other
HISCIW / CP1 + / translation + i
HOTFOM / CP1 + / 21 + i
LECLOU / CP1 + / translation + i
LIDYEC / other
LOSJIN / CP1 / 21
MAZZIX / CP1 + / glide + i
MOSPIU / CP1 + / glide + i
NIYDOO / CP1 + / translation + i
NOTSAQ / CP1 + / glide + i
PAWNOR / other
QEXSOC / CP1 + / 4 ind. mol.
QOTQOG / CP1 + / 2 ind. mol.
ROFCUL / CP1 / glide
ROFYER / CP1 + / translation + i
SESROY / CP1 + / glide + i
TIGWEM / other
TIJLAZ / CP1 + / glide + i
UDESEB / CP1 + / glide + i
VIFRUX / CP1 + / glide + i
WACJIT / CP1 / glide
WEPJUX / CP1 + / 21 + 21
WIKQOX / CP1 / translation
WOSGIU / CP1 / glide
BOTZOA / CP1 + / glide + i
XOSNAV / / i
XOYWIS / CP1 + / glide + i
YOTHOF / CP1 + / glide + i
YOVDAP / CP1 + / glide + i
YOVJAV / CP1 + / glide + i
RUGQAM / CP1 + / glide + i
RUJPOC / CP1 + / translation + i
XUVPEK / CP1 + / glide + i
XUVSAJ / other
XUVTAK / CP1 + / glide + i

Supplementary Material 2: Occurrence of the CP2 pattern in the structures of CSD

Fragment searched

(Filters of the CSD search: 3D coordinates determined, not disordered, only organics, solvent free)

CSD refcode / Pattern / Operation
AMAPTZ / CP2 / glide
CIRXAD / other
CIRXIL / CP2 / translation
FOFBOS / other
GOMCAN / other
HOFLAQ / CP2 / glide
IDUSAC / CP2 / glide
ILOQAB / CP2 / translation
ILOQEF / CP2 / translation
JAHGOO / CP2 / 4 indep. mol.
JESTOR / other
JESTUX / CP2 / translation
JESVIN / other
KEQFUI / CP2 / translation
KESMUQ / CP2 / glide
KIRKVAC / other
KUTHAI / CP2 / glide
OMOQEM / CP2 / glide
RIGNOL / CP2 / 4 indep. mol.
RIZFAI / CP2 / translation + 21
SEDNIY / other
UGUGAE / CP2 / glide
UKANOJ / other
VOMMOZ / other
YODNUB / other
UKANOJ01 / CP2 / glide
DUNBUK / other
NUGZEV / CP2 / glide
NUGZEV01 / CP2 / translation
NUGZOF / other
QUJZAX / CP2 / translation

Supplementary Material 3: CSD analysis of the F∙∙∙F contact between translated molecules

Fragment searched:

(Filters of the CSD search: 3D coordinates determined, not disordered, no ions, only organics)

CSD REFCODE / Chain length / Number of chains / Number of contacts / Translation axis
ACAPID / 2 / 1 / 2 / a
BAJSAH / 8 / 1 / 2 / b
BOCXUN / 3 / 8 / 1 / a
CIKNIT / 6 / 1 / 1 / a
COHJOZ / 4 / 1 / 1 / a
COKNUM / 8 / 0.5 / 1 / b
COMXUX / 2 / 2 / 2 / a+c
DOFDIM / 2 / 1 / 1 / a
EBIHIH / 2 / 1 / 1 / b
EBIHON / 8 / 1 / 2 / a+b
EBIJAB / 6 / 0.5 / 1 / a-b
EBIJEF / 4 / 0.5 / 1 / b
EBIJOP / 8 / 0.5 / 2 / a-b
EDIWOE / 2 / 10 / 3 / a, b
EDIWUK / 2 / 10 / 2 / a
EDIXOF / 2 / 10 / 1 / b
EFOZOP / 2 / 4 / 3 / a, b
FILMIW / 4 / 1 / 1 / a
FITLOJ / 2 / 3 / 1 / c
FOLSEE / 4 / 1 / 1 / c
FUSTIW / 4 / 1 / 1 / b
GETJUL / 2 / 1 / 3 / a, b
HILBUZ / 2 / 0.5 / 1 / a+b
JEFPUG / 2 / 8 / 1 / b
JEMWUT / 2 / 1 / 2 / a+b, b
KISPUY / 3 / 1 / 2 / b
LARTAA / 2 / 1 / 1 / b
LEQYUC / 2 / 4 / 1 / a
LIBMOY / 2 / 1 / 1 / a
LUSYAZ / 4 / 2 / 2 / a
MERFEV / 7 / 1 / 1 / a
MERFIZ / 7 / 1 / 3 / b
MIMPAA / 2 / 4 / 1 / c
NAYPUZ / 2 / 1 / 1 / a
NEJYAD / 8 / 1 / 2 / b
OFUCIC / 2 / 4 / 2 / a
OFUCOI / 2 / 8 / 1 / b
OFUCUO / 2 / 4 / 1 / a-b
OGELUI / 3 / 1 / 2 / b-c
PARCUH / 2 / 2 / 1 / b
QAHSAT / 8 / 0.5 / 1 / a+c
QANRUS / 6 / 0.5 / 1 / b
QELWUZ / 3 / 1 / 1 / b
QODWIQ / 2 / 6 / 1 / a
QODXAJ / 2 / 8 / 5 / a, b
QODXIR / 2 / 8 / 2 / c
RAJHAM / 6 / 1 / 1 / b
RISCIF / 3 / 2 / 1 / b
SEGLEV / 4 / 1 / 1 / b
SIQQIT / 4 / 0.5 / 1 / a
TFBCBE / 2 / 0.5 / 1 / a
VAYJOU / 4 / 2 / 1 / b
WADJOA / 4 / 0.5 / 2 / c
WIFBOD / 8 / 3 / 5 / b
XATDEC / 4 / 0.5 / 1 / a
XATDIG / 6 / 0.5 / 2 / a
XEXSAV / 2 / 2 / 2 / a
XIFCEU / 2 / 1 / 1 / b
XORMAS / 4 / 1 / 1 / b
XOSLEW / 8 / 1 / 3 / a, c
YIDCAP / 6 / 0.5 / 1 / c
YOJMOA / 2 / 4 / 1 / a
YOJNAN / 2 / 4 / 1 / b
YOMCUZ / 2 / 4 / 1 / b-a
YUJGOZ / 3 / 2 / 1 / c
ZAPXUJ / 4 / 1 / 1 / a
ZOFRAN / 6 / 4 / 4 / a
QUBPIN / 3 / 2 / 1 / a
KUCGAR / 3 / 1 / 2 / a
MUCQEH / 2 / 12 / 2 / a
TUJZOO / 2 / 1 / 1 / a
TUKBAD / 2 / 2 / 1 / a
TUKBEH / 2 / 2 / 1 / a

Chain length = number of consecutive CF2 units in the chain;

Number of chains = number of chains present in the molecule;

Number of contacts = number of F∙∙∙F contacts between translated molecules present in the crystal structure.

Number of chains and number of contacts are only those crystallographically independent.

Altogether we have 249 hits in the CSD, in which is present a chain with at least 2 consecutive CF2 units. In 73 structures of this set there is a short F∙∙∙F contact between translated molecules so, according to Allen et al. (F. H. Allen, W. D. S. Motherwell, P. R. Raithby, G. P. Shields and R.Taylor, New J. Chem., 1999, 23, 25–34), the structural probabilityPs is

Of course, the structural probability can be evaluated for subsets containing chains of fixed length. In this case it is found:

The probability of the motif, Pm, is given by the ratio of the number of motifs found in the set, and the number of motifs that could have occurred.

Evaluation of is straightforward, i. e. we must simply count in the column headed ”Number of contacts” in the Table above. The evaluation of is more subtle. In practice, considering only simple contacts by translation (i. e. not bifurcated), it is evident that each CF2 unit of the chain

can give only two contacts with translated molecules, of which only one is independent. So, for a chain of n CF2 units, it is. In this way we evaluate

Also in this case the probability can be calculated for subsets containing chains of fixed length. We find

.

1