C-H?F, C-H?O interactions in the crystal structure of 2-(2-nitrophenyl)-3-pentafluorophenyl-oxirane and 2-pentafluorophenyl-3-phenyl- 1-(p-tosyl)-aziridine

Article abstract of DOI:10.1016/j.molstruc.2011.10.055

Existence and nature of C-H?F, C-H?O interactions in 2-(2-nitrophenyl)-3-pentafluorophenyl-oxirane (1) and 2-pentafluorophenyl-3- phenyl-1-(p-tosyl)-aziridine (2) are discussed. In compound 1 with a linear molecule, C-H?F, C-H?O hydrogen bonds assemble ad

Full text of DOI:10.1016/j.molstruc.2011.10.055

Journal of Molecular Structure 1007 (2012) 252–256
Contents lists available at SciVerse ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
C–Hꢀ ꢀ ꢀF, C–Hꢀ ꢀ ꢀO interactions in the crystal structure
of 2-(2-nitrophenyl)-3-pentafluorophenyl-oxirane
and 2-pentafluorophenyl-3-phenyl-1-(p-tosyl)-aziridine
a,
⇑
a
b
a
b,
⇑
Xiu-Lian Zhang , Wei Yin , Shi-fa Zhu , Man Li Cao , Shi-Zheng Zhu
a
Department of Chemistry, Guangdong University of Education, Guangzhou 510310, China
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 6 October 2011
Received in revised form 29 October 2011
Accepted 29 October 2011
Available online 19 November 2011
Existence and nature of C–Hꢀ ꢀ ꢀF, C–Hꢀ ꢀ ꢀO interactions in 2-(2-nitrophenyl)-3-pentafluorophenyl-oxirane
(
1) and 2-pentafluorophenyl-3-phenyl-1-(p-tosyl)-aziridine (2) are discussed. In compound 1 with a lin-
ear molecule, C–Hꢀ ꢀ ꢀF, C–Hꢀ ꢀ ꢀO hydrogen bonds assemble adjacent molecules into the two-dimensional
layers, Fꢀ ꢀ ꢀF, Oꢀ ꢀ ꢀF interactions connect adjacent layers into three-dimensional supramolecular networks.
Owing to the inductive effect of nitro group, the C–H acidity of nitrophenyl increases and the numbers of
C–Hꢀ ꢀ ꢀF, C–Hꢀ ꢀ ꢀO hydrogen bonds also increase, C–Hꢀ ꢀ ꢀF, C–Hꢀ ꢀ ꢀO interactions become stronger and more
important. 1D ribbons of compound 2 are stabilized by C–Hꢀ ꢀ ꢀF, C–Hꢀ ꢀ ꢀO intermolecular interactions.
Keywords:
Self-assembly
Hydrogen bonding
Oxirane and aziridine derivatives
Nonplanar tritopic molecule would demand the formation of a
zene rings and pentafluorobenzene rings in 2.
p
ꢀ ꢀ ꢀp
packing interactions between ben-
Ó 2011 Published by Elsevier B.V.
1
. Introduction
synthesized, with the intent of finding reproducible assembly
strategies.
Intermolecular interactions play an important role in the forma-
tion of stable and structurally well-defined supramolecular struc-
tures [1–4]. Halogen atoms are typically located at the periphery of
organic molecules and are thus ideally positioned to be involved in
intermolecular interactions [5] and halogen atoms are much larger
and polarizable than hydrogen atoms; thus halogen bonds are more
sensitive to steric hindrance than hydrogen bonds [6]. Some results of
studies prove it is possible to carefully tune the strength of the halo-
gen bond in a given halocarbon by modifying the substituents on the
carbon skeleton [7,8]. With the exception of halogen bonds, the C–H
group is known to be a hydrogen-bond donor as well as weak but
directional C–Hꢀ ꢀ ꢀF, C–Hꢀ ꢀ ꢀO intermolecular interactions are serve
as tools in engineering molecular assemblies [9–12]. Organic fluorine
and its role as a hydrogen-bond acceptor are of recent interest
2. Experimental section
2.1. Synthesis
In the
a dry Schrock tube, tetrahydrothiophene (44 mg,
0.5 mmol) for 1, triphenylarsenic (31 mg, 0.1 mmol) for 2, aromatic
aldehyde (75.5 mg, 0.5 mmol) for 1, imino (129.5 mg, 0.5 mmol)
for 2, Rh (OAc) (4 mg, 10 mmol), anhydrous THF (2 ml) were
2
4
added in turn under N2 atmosphere. Then pentafluorophenyldia-
zomethane (156 mg, 0.75 mmol) in THF solution was added drop-
wise with injection pump over 2 h. After addition, the reaction
mixture was stirred and refluxed for another 2 h at room temper-
ature. After filtered and concentrated under reduced pressure
using a rotary evaporator, the solvent was evaporated and the res-
idue was purified by column chromatography. The crude crystals
thus obtained were recrystallized.
[
13,14]. We have previously reported that the self-assemblies of mel-
amine with aromatic carboxylic acids, 1,5-naphthalenedisulfonic
acid were assisted by an interplay of strong N–Hꢀ ꢀ ꢀO and N–Hꢀ ꢀ ꢀN
hydrogen bonds interactions and the geometry of the molecules
[
15,16]. Here, organic molecules equipped with fluorine atoms and
oxygen atoms, which have linear and nonplanar tritopic geometries,
respectively, 2-(2-nitrophenyl)-3-pentafluorophenyl-oxirane (1) and
2.1.1. Compound 1
2
-pentafluorophenyl-3-phenyl-1-(p-tosyl)-aziridine (2) have been
Colorless crystal. m.p. 82–84 °C. Anal. Calcd for C14
6 5 3
H F NO : C;
5
0.76, H; 1.81, N; 4.23%. Found: C; 50.70, H; 1.83, N; 4.25%. IR (KBr)
ꢁ1
1
cm : 3107, 1657, 1611, 1577, 1521, 1501, 1348, 1332, 1122.
NMR (CDCl3, 300 MHz) d H NMR (in CDCl
H
1
⇑
Corresponding authors.
E-mail address: xiulianzhang64@yahoo.com (X.-L. Zhang).
3
) d: 8.23 (m, 1H, Ar–
H), 7.72 (m, 2H, Ar–H), 7.55 (d, J = 1.8 Hz, Ar–H), 5.15 (d,
0
022-2860/$ - see front matter Ó 2011 Published by Elsevier B.V.
doi:10.1016/j.molstruc.2011.10.055

X.-L. Zhang et al. / Journal of Molecular Structure 1007 (2012) 252–256
253
J = 1.8 Hz, CH), 3.98 (s, 1H, CH). 19F NMR (in CDCl
152.3 (t, J = 21.2 Hz, 1F), ꢁ161.2 (m, 2F).
) d-144.2 (m, 2F),
using SADABS [17]. The structures were solved by direct methods and
refined with full-matrix least-squares technique using SHELXS-97
and SHELXL-97 programs, respectively [18]. The organic hydrogen
atoms were generated geometrically (C–H 0.96 Å). Crystal data as
well as details of data collection and refinement for the compounds
1 and 2 are summarized in Table 1. A summary of hydrogen bonding
interactions observed in 1 and 2 is provided in Table 2.
3
ꢁ
2
.1.2. Compound 2
Colorless crystal. m.p. 139–141 °C. Anal. Calcd for C21
C; 57.40, H; 3.18, N; 3.19%. Found: C; 57.40, H; 3.17, N; 3.18%. IR
14 5 2
H F NO S:
ꢁ1 1
(
KBr) 1930, 1658, 1596, 1525, 1500, 1458, 1335, 1324 cm . H
2
3
NMR (in CDCl ) d7.95 (d, J = 8.1 Hz, 2H, Ar–H), 7.30 (m, 7H, Ar–
H), 4.71 (d, J = 3.9 Hz, 1H, CH), 3.79 (d, J = 4.2 Hz, 1H, CH), 2.42 (s,
3
. Results and discussion
1
9
3
H, Ar–CH
3 3
). F NMR (in CDCl ) d-137.4 (d, J = 17.5 Hz, 2F),
ꢁ151.5 (t, J = 20.6 Hz, 1F), ꢁ161.4 (m, 2F).
The compounds 1 and 2 were synthesized from pentafluorophe-
nyldiazomethane and aromatic aldehyde for 1, imino for 2 (Scheme
). The nature of their self-assembly was investigated using single
2.2. Structural characterizations
1
crystal X-ray diffraction studies. We are interested in examining
the difference of C–Hꢀ ꢀ ꢀF, C–Hꢀ ꢀ ꢀO interactions in 1 and 2. Conse-
quently, the compounds 1 and 2 were prepared and characterized.
Diffraction intensities for 1 and 2 were collected at 293 K on a Bru-
ker Smart Apex CCD diffractometer with graphite-monochromated
MoK radiation (k = 0.71073 Å). Absorption corrections were applied
a
3
.1. Crystal structure of 2-(2-nitrophenyl)-3-pentafluorophenyl-
Table 1
Crystal data and structure refinement for compounds 1 and 2.
oxirane (1)
Compound
1
2
Compound 1 is a linear molecule and the pentafluorobenzene
rings are approximately coplanar with the aromatic rings [dihedral
angle 5.2°], which promote to form a 2D net (Fig. 1a). Indeed, indi-
vidual molecules are aligned in vertical rows and in a ‘‘head-to-tail’’
fashion, with adjacent vertical rows running in antiparallel direc-
tions as shown in Fig. 2. Fluorine atoms in 1 are extremely activated
toward participation in intermolecular interactions, four of the five
fluorine atoms are engaged in halogen bonding and weak hydrogen
bonds, including examples of two C–Hꢀ ꢀ ꢀF hydrogen bonds, one
Oꢀ ꢀ ꢀF interaction and four Fꢀ ꢀ ꢀF halogen bonds. Interestingly, three
of five fluorine atoms (F1, F3, F5) of pentafluorophenyl moieties
form bifurcated contacts with fluorine atoms (F3, F1, F2) and hydro-
gen atoms (H4–C11, H5–C12) or oxygen atom (O3) from different
molecules, respectively. Thus, this fluorine atoms (F1, F3, F5) func-
tion as C–Hꢀ ꢀ ꢀF hydrogen bond and halogen bond acceptors (nucle-
ophile, Lewis bases) toward neighboring electrophilic fluorine
atoms or oxygen atoms, hydrogen atoms as donors (Lewis acids)
as shown in Figs. 2 and 3a. A similar bifurcated hydrogen bonding
motif was encountered in a structure of phloroglucinol ester [9]. It
is to be noted that the atom F4 in 1 also did not participate in any
intermolecular interactions, owing to not match with hydrogen do-
nors in geometry. Careful examination of the intermolecular inter-
actions of compound 1 reveal that C–H groups on the benzene
ring of nitrophenyl moiety strong ability to form attractive C–
Hꢀ ꢀ ꢀF or C–Hꢀ ꢀ ꢀO interactions. Three hydrogen atoms of four hydro-
gen atoms on the benzene ring of nitrophenyl moiety are involved in
the formation of intermolecular C–Hꢀ ꢀ ꢀO interactions. Owing to the
inductive effect of nitro group, which is electron withdrawing, it will
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal color
Crystal size (mm)
Crystal system
Space group
a (Å)
C
14
H
6
F
5
NO
3
C
21 14 5 2
H F NO S
331.20
293(2)
0.71073
439.39
293(2)
0.71073
Colorless
Colorless
0.32 ꢂ 0.23 ꢂ 18
0.42 ꢂ 0.22 ꢂ 0.09
Monoclinic
Triclinic
P2
1
/n
P1ꢀ
7.298(1)
12.616(2)
13.957(2)
90.00
95.331(3)
90.00
1279.4(4)
1.719
4
7.747(2)
9.419(2)
14.952(3)
74.701(5)
76.265(5)
66.196(4)
952.2(4)
1.533
b (Å)
c (Å)
a
(°)
b (°)
(°)
Volume (Å )
Dc (Mg/m )
c
3
3
Z
2
No. of data/params
2938/233
0.169
4166/280
0.236
ꢁ
1
l
(mm )
Range for data collection
h range
k range
l range
Reflns collected
Reflns unique
Observed reflns
2.18° < h < 28.28°
ꢁ9 to 9
ꢁ15 to 16
ꢁ18 to 13
7535
2938
1318
0.0917
0.0452
99.8%
0.0886
664
1.057
4.81° < h < 38.93°
ꢁ8 to 10
ꢁ11 to 12
ꢁ19 to 17
5749
4166
1661
0.0690
0.0718
97.9%
0.1523
448
1.090
R
R
int
a
1
Completeness (to h = 26°)
b
wR
2
F(000)
Goodness-of-fit
ꢁ
D
q
max
/
D
q
min (eÅ 3
)
0.19/ꢁ0.20
0.36/ꢁ0.38
P
P
a
R
1
=
||F
0
| ꢁ |F
C
||/ |F
0
|.
h
i.
h
i
P
P
1=2
O
b
2
2
2
2
2
1mol%Rh (OAc) , THT
wR
2
¼
wðF0 ꢁ F Þ
wðF Þ
.
2
4
C
0
C6F5CHN2 + ArCHO
THF
C6F5
Table 2
Hydrogen bonding parameters in 1 and 2.
1
DꢁHꢀ ꢀ ꢀA
1
DꢁH (Å)
Hꢀ ꢀ ꢀA (Å)
Dꢀ ꢀ ꢀA (Å)
\DꢁHꢀ ꢀ ꢀA (°)
1
mol%Rh (OAc)4
2
Ts
N
20% Ph As
3
C17ꢁH17ꢀ ꢀ ꢀO1#1
0.93
0.98
2.54
2.51
3.427(2)
3.170(2)
158.7
124.4
C6F5CHN2
+
ArCH=NTs
C7ꢁH7ꢀ ꢀ ꢀF4#1
THF, r.t.
C F
6 5
2
C10ꢁH3ꢀ ꢀ ꢀO3#2
C11ꢁH4ꢀ ꢀ ꢀF3#3
C12ꢁH5ꢀ ꢀ ꢀF1#4
0.94
1.02
1.00
2.51
2.59
2.58
3.289(2)
3.608(2)
3.290(2)
141.3
170.6
127.3
2
Symm. code: 1, #1: 1 + x,y,z; 2, #2: 1/2 + x,1/2 ꢁ y,1/2 + z; #3: x, ꢁ1 + y, z; #4:
1/2 + x, 1/2 ꢁ y, ꢁ1/2 + z.
ꢁ
Scheme 1. Synthesis of the compounds (1–2).

2
54
X.-L. Zhang et al. / Journal of Molecular Structure 1007 (2012) 252–256
(
a)
(b)
Fig. 1. (a) ORTEP of 1 drawn with 30% ellipsoidal probability. (b) ORTEP of 2 drawn with 30% ellipsoidal probability.
C–Hꢀ ꢀ ꢀF interactions in a ‘‘head-to-tail’’ fashion, with pentafluoro-
benzene ring of one molecule and adjacent pentafluorobenzene ring
of another molecule in following row are held by a pair of type Fꢀ ꢀ ꢀF
halogen bonds involving F2 and F5 atoms. Notable, Fꢀ ꢀ ꢀF instance
(
d
Fꢀ ꢀ ꢀF = 2.844 Å) is shorter than those of 1,2,3,5-tetrafluorobenzene
Fꢀ ꢀ ꢀF = 2.923, dFꢀ ꢀ ꢀF = 2.987 Å) [19]. Two type C–Hꢀ ꢀ ꢀF intermolecu-
(d
lar interactions are formed between each phenyl moiety and adja-
cent two pentafluorobenzene moieties from different rows as
shown in Fig. 2. The 2D sheet extends in the bc plane. In 1, nitro oxy-
gen atom O2 and the oxygen atom O1 on triatomic cycle skeleton
did not participate in any contacts due to space steric effects. Results
of studies of Gautam R. Desiraju and co-workers in 10 fluorobenz-
enes showed that fluorine would form C–Hꢀ ꢀ ꢀF interactions rather
than Fꢀ ꢀ ꢀF contacts [20]. However, it should be noted that in this
study, Fꢀ ꢀ ꢀF and Oꢀ ꢀ ꢀF halogen bonding interactions seemingly play
a central role in stabilizing the crystal structure of 1. The Fꢀ ꢀ ꢀF hal-
ogen bond (dF1ꢀ ꢀ ꢀF3 = 2.925 Å) from different layers serves to connect
adjacent 2D sheet as shown in Fig. 3a., which are further stacked
into 3D structures by Oꢀ ꢀ ꢀF and Fꢀ ꢀ ꢀF interactions (Fig. 3b). The
Fꢀ ꢀ ꢀF and Oꢀ ꢀ ꢀF interactions to connect adjacent 2D sheet
(dFꢀ ꢀ ꢀF = 2.925 Å, dOꢀ ꢀ ꢀF = 2.964 Å) are similar and longer than those
to connect adjacent molecules in same layers (dFꢀ ꢀ ꢀF = 2.844 Å).
Fig. 2. 2D sheet exhibiting C–Hꢀ ꢀ ꢀF, C–Hꢀ ꢀ ꢀO hydrogen bonding and Fꢀ ꢀ ꢀF interac-
tions in the structure of 1.
3.2. Crystal structure of 2-pentafluorophenyl-3-phenyl-1-(p-tosyl)-
aziridine (2)
decrease the electronic density on the benzene ring, which means
that benzene ring of nitrophenyl moiety has the more acidic protons
to form C–Hꢀ ꢀ ꢀF or C–Hꢀ ꢀ ꢀO hydrogen bonds. In two-dimensional
sheets of 1, the adjacent molecules are connected via C–Hꢀ ꢀ ꢀO and
Compound 2 exhibits nonplanar tritopic molecule compared to
linear compound 1 owing to the introduction of the tosyl moiety
on the triatomic cycle skeletons (Fig. 1b), pentafluorobenzene rings
Fig. 3. (a) Adjacent layers are connected via Fꢀ ꢀ ꢀF and Oꢀ ꢀ ꢀF interactions to form 3D structures in 1. (b) Packing in 1.

X.-L. Zhang et al. / Journal of Molecular Structure 1007 (2012) 252–256
255
are not coplanar with the aromatic rings. The angle between the
mean planes of the benzene ring and the pentafluorobenzene ring
is 22.1° with the angle between the mean planes of the benzene
ring and methylbenzene ring being 13.5°, and the angle between
the mean planes of pentafluorobenzene ring and methylbenzene
ring is 10.7°. The packing of the molecules in the crystalline lattice
of 2 with nonplanar tritopic molecule is not made most compact
ꢁ3
ꢁ3
(qcalc of 2 = 1.533 g cm
, qcalc of 1 = 1.719 g cm ) compared to 1
of linear molecule. Owing to the introduction of the bulky tosyl
moiety, it is so incompatible with geometry shape in 2 that fluorine
atoms bonding patterns in 2 reveal significant differences as com-
pared to those in 1. Only one (F4) of five fluorine atoms in 2 partic-
ipates in C–Hꢀ ꢀ ꢀF hydrogen bond, other four fluorine atoms did not
participates in any intermolecular interactions due to not match
with hydrogen bonding donors in process of molecular self-assem-
bly. Fluorine atoms in 2 are extremely deactivated toward partici-
pation in intermolecular interactions. It is to be noted that only one
Fig. 5. Aromatic
ring in 2.
pꢀ ꢀ ꢀ
p
interactions between benzene rings and pentafluorobenzene
(
O1) of two oxygen atoms of tosyl moiety engages in C–Hꢀ ꢀ ꢀO
hydrogen bond, while another oxygen atoms of tosyl moiety did
not participate in any intermolecular interactions similar to those
of nitro group in 1, as well as the nitrogen atom on triatomic cycle
skeleton did not exhibit any intermolecular interaction similar to
the oxygen atom on triatomic cycle skeleton in 1.
Compound 2 crystallizes as 1D ribbon structures seemingly by
various C–Hꢀ ꢀ ꢀF and C–Hꢀ ꢀ ꢀO hydrogen bonds and the network
assemblies found in 2 and 1 differ significantly, not just in their
overall topology but also by the presence of significant Fꢀ ꢀ ꢀF and
Oꢀ ꢀ ꢀF close contacts in 1 and the complete absence of such interac-
tions in 2. Meanwhile, the adjacent molecules are held through a
well-defined C–Hꢀ ꢀ ꢀF hydrogen bonds and C–Hꢀ ꢀ ꢀO hydrogen
bonds to form undulate ribbons running a axis as shown in
Fig. 4. The introduction of the tosyl moiety increases the angle
Fig. 6. Extended packing in 2 showing.
(
22.1°) between the mean planes of the benzene ring and the pen-
tafluorobenzene ring compared to those (dihedral angle 5.2°) of 1,
resulting to an additional stacking interactions between aro-
this could be one of the reasons why it does not form very effective
C–Hꢀ ꢀ ꢀF hydrogen bonds [20].
pꢀ ꢀ ꢀp
It is to be noted that C–Hꢀ ꢀ ꢀF hydrogen bonding interactions
found in 1 and 2 differ significantly, the hydrogen atoms of benzene
rings in 1 serve to hydrogen boning donors. In contrast, hydrogen
boning donors in 2 are the hydrogen atoms of aziridine ring. The dis-
tance and geometry of C–Hꢀ ꢀ ꢀO hydrogen bond (dHꢀ ꢀ ꢀO = 2.54 Å, C–
Hꢀ ꢀ ꢀO = 158.7°) presents in the structure is similar to those of 1
matic rings and pentafluorobenzene rings (Fig. 5).
A comparison of 2 with compound 1 indicates the importance
difference in intermolecular interaction of C–H group on the ben-
zene ring, only one hydrogen atom of four hydrogen atoms on
the benzene ring of tosyl moiety is involved in the formation of
intermolecular interaction (C–Hꢀ ꢀ ꢀO hydrogen bond). It may appar-
ently be attributed to the fact that the inductive effect of methyl
group is electron donating and the methyl group of tosyl moiety
enhances the electronic density on the benzene ring, making
hydrogen atoms on benzene ring of tosyl moiety a weaker acid
than those of nitrophenyl moiety in 1. In addition to, the structure
of 2 demonstrates that the C–H group on benzene ring of tosyl
moiety prefers to form C–Hꢀ ꢀ ꢀO interactions rather than C–Hꢀ ꢀ ꢀF
interactions. The C–Hꢀ ꢀ ꢀO hydrogen bonds are considered to arise
from the interactions between a soft donor (C–H) and a soft accep-
tor (O) while the F atom in the C–F group is a hard acceptor, and
(
d
Hꢀ ꢀ ꢀO = 2.51 Å, C–Hꢀ ꢀ ꢀO = 141.3°), but both contacts fall within the
range of attractive interactions. Similar distances and angles were
found in the structure of 3-iodotriaroylbenzenes (dHꢀ ꢀ ꢀO = 2.46 Å,
C–Hꢀ ꢀ ꢀO = 160.3°), and 3-bromoacetophenone (dHꢀ ꢀ ꢀO = 2.42 Å, C–
Hꢀ ꢀ ꢀO = 133.8, 167.7°) [9]. The association of two such ribbons via
p p interactions is illustrated in Fig. 5 in which pentafluoroben-
ꢀ ꢀ ꢀ
zene donors have been tilted toward the benzene ring acceptors.
The distance of centroid to centroid is 4.365 Å, but the shortest con-
tact distance of pentafluorobenzene ring and benzene ring is 3.307 Å
involving C1 on pentafluorobenzene ring and C12 on benzene ring. A
view of the extended packing observed in 2 is shown in Fig. 6 to illus-
trate the aromatic
allel rows. Examination of the extend network present in 2 reveals
p pinteractions between double ribbons in par-
ꢀ ꢀ ꢀ
no significant halogen bonding.
4
. Conclusions
The acidity of C–H groups on the benzene ring and geometric
shape of molecule are essential in controlling the final supramolec-
ular architecture. Owing to the inductive effect of nitro group,
stronger acidity of C–H groups on the benzene ring, more C–H
groups participate in intermolecular interactions in 1. Linear mol-
ecule 1 forms 2D networks while nonplanar tritopic molecule 2
self-assembles into one dimension ribbons. In 1, four of the five
fluorine atoms are engaged in intermolecular interactions while
Fig. 4. Ribbon motif maintained by C–Hꢀ ꢀ ꢀO and C–Hꢀ ꢀ ꢀF hydrogen bonds in 2.

2
56
X.-L. Zhang et al. / Journal of Molecular Structure 1007 (2012) 252–256
only one of five fluorine atoms in 2 participates in intermolecular
contact. Fluorine atoms in 1 and 2 are found to be two distinct
types of bonding patterns are prominently featured in this work.
In contrast, the linear molecule 1 gives rise to 3D network struc-
tures in which Fꢀ ꢀ ꢀF and Oꢀ ꢀ ꢀF interacts seemingly play a central
role, while in 2, C–Hꢀ ꢀ ꢀO and C–Hꢀ ꢀ ꢀF hydrogen interactions assem-
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This project was financially supported by the National Natural
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Basic Research Program (No. 2007BC80800), and the Project of
for Higher-level Talents in University of Guangdong Province under
Grant No. 201079.
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