Supramolecular organic frameworks of brominated bisphenol derivatives with organoamines

Article abstract of DOI:10.1021/cg200520w

Reactions of two brominated bisphenol derivatives, tetrabromobisphenol-F (TBBPF) and tetrabromobisphenol-A (TBBPA), with various organoamines resulted in six supramolecular organic frameworks (SOFs), formulated as (TBBPF ^2-)₂·(HPZ⁺)₂· (H ₂PZ²⁺) (1), (TBBPF^-)₂· (H₂PZ²⁺)·2H₂O·2MeOH (2), (TBBPF) · (TBBPF^-)· (HDABCO⁺)·H₂O (3), (TBBPF) · (HMTA) (4), (TBBPA) · (HMTA) (5), and (TBBPA) ₃· (HMTA)₃·H₂O (6) (PZ = piperazine; DABCO = diazabicyclo[2.2.2]octane; HMTA = hexamethylenetetramine). Compounds 1-6 were characterized by single-crystal and powder X-ray diffractions. The predominant driving forces in 1-6 are hydrogen bonds (H-bonds), by which the compounds assemble into supramolecular organic frameworks with versatile topological structures. Compound 1 contains TBBPF/PZ in a 2:3 ratio and exhibits 2D (two-dimensional) H-bonded supramolecular 4 ⁴-sql layer structure built by the four-connected {H ₂PZ²⁺} moieties and {TBBPF^2-}. Compound 2 shows a 2-fold interpenetrated 3D (three-dimensional) H-bonded networks comprised by TBBPF/PZ in 2:1 ratio with the presence of solvent H₂O and MeOH molecules, in which two identical pcu topological nets are recognized by choosing a decamer synthons as nodes. Compound 3 displays H-bonded 4 ⁴-sql layer structure built by 2:1 TBBPF and DABCO, as well as one H₂O per formula unit. Compounds 4 and 5 assemble into 1D (one-dimensional) H-bonded zigzag chains via the alternate linkage of HMTA with TBBPF/TBBPA in a similar fashion. Compound 6 generates an interesting hexamer subunit (HMTA ...TBBPA ...HMTA ...TBBPA ...HMTA...TBBPA), which can be viewed as a fragment of three repeating units for a zigzag chain observed in compound 5. A pair of the hexamer subunits is further connected by two water molecules to form an H-bonded molecular oligomer. Importantly, halogen bonds (X-bonds) have been observed in compounds 4-6 that exhibit 1D and 0D H-bonded supramolecular structures.

Full text of DOI:10.1021/cg200520w

ARTICLE
pubs.acs.org/crystal
Supramolecular Organic Frameworks of Brominated Bisphenol
Derivatives with Organoamines
Jian L€u,† Li-Wei Han,†,‡ Jing-Xiang Lin,† and Rong Cao*,†
†State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences,
Fujian, Fuzhou 350002, P. R. China
‡Graduate School, Chinese Academy of Sciences, Beijing 100039, P. R. China
S Supporting Information
b
ABSTRACT: Reactions of two brominated bisphenol derivatives, tetrabromobisphenol-F
(TBBPF) and tetrabromobisphenol-A (TBBPA), with various organoamines resulted in six
supramolecular organic frameworks (SOFs), formulated as (TBBPF2À)2 (HPZ+)2 (H2PZ2+)
3
3
(1), (TBBPFÀ)2 (H2PZ2+) 2H2O 2MeOH (2), (TBBPF) (TBBPFÀ) (HDABCO+) H2O
3
3
3
3
3
3
(3), (TBBPF) (HMTA) (4), (TBBPA) (HMTA) (5), and (TBBPA)3 (HMTA)3 H2O (6)
(PZ = piperazine; DABCO = diazabicyclo[2.2.2]octane; HMTA = hexamethylenetetramine).
3
3
3
3
Compounds 1À6 were characterized by single-crystal and powder X-ray diffractions. The
predominant driving forces in 1À6 are hydrogen bonds (H-bonds), by which the compounds
assemble into supramolecular organic frameworks with versatile topological structures.
Compound 1 contains TBBPF/PZ in a 2:3 ratio and exhibits 2D (two-dimensional) H-bonded
supramolecular 44-sql layer structure built by the four-connected {H2PZ2+} moieties and
{TBBPF2À}. Compound 2 shows a 2-fold interpenetrated 3D (three-dimensional) H-bonded
networks comprised by TBBPF/PZ in 2:1 ratio with the presence of solvent H2O and MeOH
molecules, in which two identical pcu topological nets are recognized by choosing a decamer synthons as nodes. Compound 3 displays
H-bonded 44-sql layer structure built by 2:1 TBBPF and DABCO, as well as one H2O per formula unit. Compounds 4and 5assemble into
1D (one-dimensional) H-bonded zigzag chains via the alternate linkage of HMTA with TBBPF/TBBPA in a similar fashion. Compound 6
generates an interesting hexamer subunit (HMTA TBBPA HMTA TBBPA HMTA TBBPA), which can be viewed as a
3 3 3
3 3 3
3 3 3
3 3 3
3 3 3
fragment of three repeating units for a zigzag chain observed in compound 5. A pair of the hexamer subunits is further connected by two
water molecules to form an H-bonded molecular oligomer. Importantly, halogen bonds (X-bonds) have been observed in compounds
4À6 that exhibit 1D and 0D H-bonded supramolecular structures.
’ INTRODUCTION
molecular packing.6 Among others, H-bonds as main driving
forces in supramolecular assemblies of organic modules featuring
functional carboxyl, pyridyl, or a mixture of the two have been
comprehensively explored.2d,f,h,3e,3f,3h,7,8 It should also be noted
that phenolÀamine interplay has been confirmed to be a type of
stable and robust driving forces for the exploitation of new solid
Crystalline materials of supramolecular organic frameworks
(SOFs) are notable representatives in supramolecular chemistry
because of both their structural complexity and physical proper-
ties of interest, in which the role of hydrogen bonds (H-bonds),
as predominant driving forces, has been well-established.1
Investigation on compounds of organic entities built by para-
digms of supramolecular synthons is currently undergoing a
burgeoning development taken full advantage of crystal engi-
neering concepts.2À4 However, predetermination of even the
simplest molecular structure is a daunting challenge because the
intermolecular forces for upholding the molecules are poorly
understood and difficult to predict, especially for organic solids.5
Any step taken into predictable molecular assemblies is thereby a
practical impetus toward the ultimate goal of solid-based crystal
engineering.
materials, and the well-defined OÀH N bonds furnished in
3 3 3
molecular compounds have been found productive for the
generation of a wide variety of supramolecular aggregates.9
During the course of our investigations in crystal engineering
of phenolÀamine salts and adducts, we recently discovered that
halogenations of bis(4Àhydroxyphenyl)sulfone (BPS) would
boost the abilities of the functional phenols to form H-bonds
in directing molecular assembly and recognition.10 Moreover, the
halogenated bisphenol molecules tetrabromobisphenol-S
(TBBPS) and tetrachlorobisphenol-S (TCBPS) were capable of
cocrystallization with organoamines and dramatically resulted in
organic compounds with fascinating structures and interesting
Most H-bonds are primarily electrostatic in nature and flexible
in strength according to the different electron donors and
acceptors. At the same time, notwithstanding their weak bonding
and angular spreading pattern, H-bonds have been approved as
directional and predictive intermolecular cohesive forces in
Received: April 24, 2011
Revised:
June 23, 2011
Published: July 11, 2011
r
2011 American Chemical Society
3551
dx.doi.org/10.1021/cg200520w Cryst. Growth Des. 2011, 11, 3551–3557
|

Crystal Growth & Design
ARTICLE
Scheme 1. Structures of the Bisphenol Derivatives and
Organoamines
1200m, 1174s, 1145m, 1122s, 1064w, 1037w, 926w, 913w, 875m, 859w,
825w, 792w, 738s, 713m, 660w, 576w, 559w, 501w. 1H NMR (DMSO-d6):
σ 9.773 (s, ArÀOH) ppm, σ 7.461 (s, ArÀH) ppm, σ 3.738 (s, ArÀ
CH2ÀAr) ppm.
[(C6H2OHBr2)2C(CH3)2] (TBBPA, tetrabromobisphenol-A). Bis(4-hy-
droxyphenyl)propane (BPA) (0.02 mol, 5.01 g) was dissolved in glacial
acetic acid and kept at about 45 °C until the white solid completely
dissolved, and Br2 (0.08 mol, 12.8 g) was added to the solution with
magnetic stirring for 2 h. White precipitate TBBPA was collected by
filtration and washed severaltimeswith cold ethanol. Yield ca. 56%(6.1 g).
Anal. Calcd for C15H12O2Br4 (%) (M= 543.88): C, 33.13; H, 2.22. Found (%):
C, 33.42; H, 2.07. IR characteristics (KBr, cmÀ1): 1774w, 1753w, 1557m,
1474vs, 1398s, 1365m, 1323s, 1274s, 1241s, 1198m, 1176s, 1161s, 1132s,
939w, 868s, 780m, 733s, 713m, 706m, 650w, 616m, 574m, 563w, 540w,
484w. 1H NMR (DMSO-d6): σ 9.819 (s, ArÀOH) ppm, σ 7.328
(s, ArÀH) ppm, σ 1.562 (s, ArÀCÀCH3) ppm.
[(C6H2OBr2)2CH2]2 (C4H8N2H)2 (C4H8N2H2) (1). A mixture of 1:2
3
3
TBBPF and piperazine (PZ) was added to 6 mL of methanol and sealed
into a Teflon-lined autoclave (20 mL) and kept at 90 °C for 3 days. After
slow cooling to room temperature within 2 days, a clear solution formed
and was allowed to evaporate in air. Colorless block crystals of 1 were
obtained within a day with a yield of ca. 38% (24.5 mg). Anal. Calcd for
C38H46N6O4Br8 (%) (M= 1290.09): C, 35.38; H, 3.59; N, 6.51. Found (%):
C, 35.17; H, 3.53; N, 6.47. IR characteristics (KBr, cmÀ1): 1635w, 1533w,
1435m, 1013s, 922m, 811m, 737m, 600w.
physical properties.10 On the other hand, it is only recent that
heuristic principles have been presented to develop a rational
crystal engineering of organic complexes relying on halogen
bonds as intermolecular cohesive interactions.11 As a matter of
fact, halogen bonding was soon proven as an effective supramo-
lecular interaction in self-assembly processes and inspired con-
siderable research interest in many realms including molecular
recognition, drugÀreceptor interaction, supramolecular organic
conductors, and liquid crystals.12
In order to enrich phenolÀamine-based organic solids as well
as to study the rules of molecular assemblies in this system and
related ones, we have developed two new bisphenol derivatives,
tetrabromobisphenol-F (TBBPF) and tetrabromobisphenol-A
(TBBPA), which hold similar sizes, shapes, and arrangements
of functional groups as their precedents, TBBPS and TCBPS. In
this study, the brominated TBBPF and TBBPA molecules have
shown reliable ability, due to the significant enhancement of
hydroxyl groups in forming H-bonds, to react with various
organoamines having sp3 N donors (Scheme 1), including
piperazine (PZ), diazabicyclo[2.2.2]octane (DABCO), and hex-
amethylenetetramine (HMTA).
[(C6H2OHBr2)CH2(C6H2OBr2)]2 (C4H8N2H2) (CH3OH)2 (H2O)2 (2).
3
3
3
A mixture of 1:1 TBBPF and PZ was added to 6 mL of methanol and
sealed into a Teflon-lined autoclave (20 mL) and kept at 90 °C for 3
days. After slow cooling to room temperature within 2 days, a clear
solution formed and was allowed to evaporate in air. Colorless block
crystals of 2 were obtained within 2 days with a yield of ca. 33% (20.1
mg). Anal. Calcd for C32H38N2O8Br8 (%) (M = 1217.92): C, 31.56; H,
3.14; N, 2.30. Found (%): C, 30.38; H, 3.09; N, 2.28. IR characteristics
(KBr, cmÀ1): 1645w, 1433m, 1295w, 1238w, 1179w, 1095w, 1016w,
990m, 926w, 816m, 788w, 728m, 596m, 581w.
[(C6H2OHBr2)2CH2] [(C6H2OHBr2)CH2(C6H2OBr2)] (C6H12N2H) (H2O)
3
3
3
(3). A mixture of 1:1 TBBPF and diazabicyclo[2.2.2]octane (DABCO) was
added to 6 mL of methanol and sealed into a Teflon-lined autoclave
(20 mL) and kept at 90 °C for 3 days. After slow cooling to room
temperature within 2 days, a clear solution formed and was allowed to
evaporate in air. Colorless block crystals of 3 were obtained within 2 days
with a yield of ca. 25% (14.5 mg). Anal. Calcd for C32H30N2O5Br8 (%)
(M= 1161.86): C, 33.08; H, 2.60; N, 2.41. Found (%): C, 32.55; H, 2.67; N,
2.44. IR characteristics (KBr, cmÀ1): 1782w, 1637w, 1555m, 1465s, 1394m,
1314s, 1232m, 1126s, 1052m, 995w, 896w, 869m, 792w, 740s, 655w,
601s, 527s.
’ EXPERIMENTAL SECTION
General. Elemental analyses (C, H, and N) were carried out with an
Elementar Vario EL III analyzer. Infrared (IR) spectra were recorded
with a PerkinElmer Spectrum One with KBr pellets in the range
1
400À4000 cmÀ1. H NMR was performed on a 400 MHz AVANCE
[(C6H2OHBr2)2CH2] (C6H12N4) (4). A mixture of 1:2 TBBPF and
3
III nuclear magnetic resonance spectrometer (BRUKER BIOSPIN).
Thermogravimetric (TG) analysis was recorded with a TA SDT Q600
unit at a heating rate of 10 °C minÀ1 under nitrogen flow. X-ray powder
diffractions (XRPD) of all samples were recorded on a Rigaku DMAX
2500 diffractometer using Cu KR radiation (λ = 1.54056 Å) at 40 kV and
30 mA, and diffraction patterns were collected over a 2θ range of 5À35°.
Single-crystal X-ray diffractions were performed on an Oxford Xcalibur
Eos diffractometer.
hexamethylenetetramine (HMTA) was added to 6 mL of methanol and
sealed into a Teflon-lined autoclave (20 mL) and kept at 90 °C for
3 days. After slow cooling to room temperature within 2 days, a clear
solution formed and was allowed to evaporate in air. Colorless block crystals
of 4 were obtained within a day with a yield of ca. 36% (23.6 mg). Anal.
Calcd for C19H20N4O2Br4 (%) (M = 656.03): C, 34.79; H, 3.07; N, 8.54.
Found (%): C, 35.72; H, 3.03; N, 8.48. IR characteristics (KBr, cmÀ1):
1633w, 1555m, 1511w, 1478s, 1326s, 1297m, 1178w, 1065w, 988m, 924w,
868w, 814m, 782w, 740m, 729m, 654m, 595m, 580m, 516m.
Synthesis. [(C6H2OHBr2)2CH2] (TBBPF, tetrabromobisphenol-F).
Bis(4-hydroxyphenyl)methane (BPF) (0.02 mol, 5.01 g) was dissolved
in glacial acetic acid, and Br2 (0.08 mol, 12.8 g) was added to the above
solution with magnetic stirring for 2 h. CAUTION: liquid Br2 should be
handled with care. White precipitate TBBPF was collected by filtration
and washed several times with cold ethanol. Yield ca. 84% (8.65 g). Anal.
Calcd for C13H8O2Br4 (%) (M= 515.82): C, 30.27; H, 1.56. Found (%): C,
31.36; H, 1.54. IR characteristics (KBr, cmÀ1): 1801w, 1763w, 1737w,
1600w, 1554m, 1471s, 1435w, 1410m, 1328s, 1298m, 1269m, 1247s,
[(C6H2OHBr2)2C(CH3)2] (C6H12N4) (5). A mixture of 1:2 TBBPA and
3
HMTA was added to 6 mL of methanol and sealed into a Teflon-lined
autoclave (20 mL) and kept at 110 °C for 3 days. After slow cooling to
room temperature within 2 days, a clear solution formed and was
allowed to evaporate in air. Colorless block crystals of 5 were obtained
within a day with a yield of ca. 22% (15.1 mg). Anal. Calcd for
C21H24N4O2Br4 (%) (M = 684.08): C, 36.87; H, 3.54; N, 8.19. Found (%):
C, 36.07; H, 3.42; N, 8.13. IR characteristics (KBr, cmÀ1): 1658w, 1526w,
3552
dx.doi.org/10.1021/cg200520w |Cryst. Growth Des. 2011, 11, 3551–3557

Crystal Growth & Design
ARTICLE
Table 1. Crystal Data and Structure Refinement for Complexes 1À6
complexes
formula
1
2
3
4
5
6
C38H46Br8N6O4
C32H38Br8N2O8
C32H30Br8N2O5
C19H24Br4N4O2
C21H24Br4N4O2
C63H74Br12N12O7
formula weight
temp (K)
wavelength (A)
cryst syst
space group
a (Å)
1290.09
1217.92
1161.86
293(2)
0.71073
monoclinic
P21/c
656.03
684 08
2070 26
monoclinic
P21/c
monoclinic
P21/c
triclinic
P1
triclinic
triclinic
P1
P1
12.1305(4)
12.3277(3)
15.7747(5)
90
12.557(4)
19.349(5)
8.173(3)
90
13.9298(5)
15.3719(5)
17.7673(8)
90
8.0454(3)
11.2431(6)
12.4087(7)
99 128(4)
104.349(4)
91.335(4)
1071.34(9)
2
7.3315(4)
11.6404(8)
14.9647(1)
103.659(6)
102.636(5)
90.701(5)
1208.18(14)
2
13.5750(2)
16.7167(2)
18.585(3)
64.667(4)
81.375(6)
72.956(6)
3643.1(8)
2
b (Å)
c (Å)
R (deg)
β (deg)
106.318(4)
90
97.837(4)
90
105.553(4)
90
γ (deg)
vol (Å3)
2263.94(1)
2
1967.3(1)
2
3665.2(2)
4
Z
GOF
0.858
1.095
0.574
0.902
0.908
0.809
R1a [I > 2σ(I)]
0.0416
0.0425
0.0323
0.0364
0.0452
0.0397
a
wR2
0.0595
0.0973
2
0.0689
0.0698
0.0958
0.0774
a R1 = ∑||Fo| À |Fc||/∑|Fo|; wR2 = {∑[w(Fo À Fc2)2]/∑[w(Fo ) ]}1/2
.
2 2
1472w, 1392w, 1274w, 1234m, 1173m, 1132m, 1051w, 1014s, 802m,
734w, 693w.
Crystal Structures of the Brominated Bisphenol Deriva-
tives with Organoamines. (TBBPF2À (HPZ+)2 (H2PZ2+) (1).
)
2
3
3
[(C6H2OHBr2)2C(CH3)2]3 (C6H12N4)3 (H2O) (6). A mixture of 1:1
In the structure of compound 1, the ratio of TBBPF and PZ is 2:3
and the asymmetric unit contains one TBBPF and one and a half
PZ moieties (Figure 1a). The crystallographically independent
TBBPF molecule is fully deprotonated with its two hydroxyl
protonstransferred to the oneand a half PZ moieties, respectively.
Thus, there are both singly and doubly protonated PZ (HPZ+ and
H2PZ2+) molecules in 1. Each TBBPF connects four PZ mol-
ecules (including two HPZ+ and two H2PZ2+), and each H2PZ2+
3
3
TBBPA and hexamethylenetetramine (HMTA) was added to 6 mL of
methanol and sealed into a Teflon-lined autoclave (20 mL) and kept at
110 °C for 3 days. After slow cooling to room temperature within 2 days,
a clear solution formed and was allowed to evaporate in air. Colorless
block crystals of 6 were obtained within 2 days with a yield of ca. 18%
(12.4 mg). Anal. Calcd for C63H74N12O7Br12 (%) (M = 2070.26): C,
36.55; H, 3.60; N, 8.12. Found (%): C, 37.39; H, 3.53; N, 8.04. IR
characteristics (KBr, cmÀ1): 1652w, 1536w, 1470w, 1393w, 1275w,
1230m, 1171m, 1132m, 1010s, 808m, 731w, 689w.
interacts with four TBBPF molecules via Ohydroxyl HÀN
3 3 3
hydrogen bonds (2.634À2.831 Å; Figure 2a,b),14 whereas the
HPZ+ molecule connects to TBBPF with one N donor in an end-
on fashion (Figure 2c). In such a way, compound 1 is extended by
H-bonds into a 2D supramolecular 44-sql layer in which the
H2PZ2+ moieties act as nodes and TBBPF as linkers (Figure 2c).
(TBBPFÀ)2 (H2PZ2+) 2H2O 2MeOH (2). The asymmetric unit
X-ray Crystallography. Diffraction intensities for compounds
1À6 were collected on Oxford Xcalibur Eos diffractometer with
graphite-monochromated Mo KR radiation (λ = 0.71073). Multiscan
absorption corrections were performed with the CrysAlisPro program
(Oxford Diffraction Ltd., Version 1.171.33.66). Empirical absorption
corrections were carried out using spherical harmonics, implemented in
SCALE3 ABSPACK scaling algorithm. Structures were solved by direct
methods and refined on F2 by full-matrix least-squares with the
SHELXTL-97 program package.13 All the non-hydrogen atoms were
refined anisotropically. CCDC 821470À821475 (1À6) contain the
supplementary crystallographic data for this paper. Data can be obtained
free of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. A summary of the crystallo-
graphic data for compounds 1À6 is given in Table 1.
3
3
3
of compound 2 includes one TBBPF, one half of a PZ moiety, one
methanol, and one water molecule (Figure 1b). The TBBPF mol-
ecule is singly deprotonated with one hydroxyl proton transferred to
the half PZ moiety; thus the PZ molecules are doubly protonated
(with a TBBPF/PZ ratio of 2:1). The hydrogen bonds
(O
H
N and O
H
O) in compound 2 are somewhat
3 3 3 3 3 3
3 3 3 3 3 3
intricate, in which a decamer supramolecular synthon built by four
TBBPF, two PZ, two methanol, and two water molecules has been
identified (Figure 3a). The decamer supramolecular synthon con-
tains two 4-rings and four 5-rings comprising a double-corner-on
cube. The network can be simplified as a six-connected uninodal
’ RESULTS AND DISCUSSION
(412 63)-pcu net (R-Po)15,16 by considering the decamer synthons
TBBPF and TBBPA were prepared from the reactions of
bisphenol-F (BPF) and bisphenol-A (BPA) with bromine in glacial
acetic acid, respectively. Cocrystallization of the bisphenol deriva-
tives TBBPF and TBBPA with organoamines resulted in six organic
compounds, formulated as (TBBPF2À)2 (HPZ+)2 (H2PZ2+)
3
as nodes (Figure 3b,c). Notably, the overall framework of compound
2shows 2-fold interpenetration of two identical pcu nets(Figure3c).
(TBBPF) (TBBPFÀ) (HDABCO+) H2O (3). The asymmetric
3
3
3
unit of compound 3 contains two TBBPF, one DABCO, and a
water molecule (Figure 1c). One of the two TBBPF molecules is
singly deprotonated with one proton transferred to the DABCO
molecule. The water molecules act as bridges to connect the TBBPF
3
3
(1), (TBBPFÀ)2 (H2PZ2+) 2H2O 2MeOH (2), (TBBPF)
3
3
3
3
(TBBPFÀ) (HDABCO+) H2O (3), (TBBPF) (HMTA) (4),
(TBBPA) (HMTA) (5), and (TBBPA)3 (HMTA)3 H2O (6)
(PZ = piperazine; DABCO = diazabicyclo[2.2.2]octane; HMTA=
hexamethylenetetramine).
3
3
3
3
3
3
and TBBPFÀ molecules via Ow
H
Ophenol interacttions
3 3 3 3 3 3
(2.684À2.897 Å) and result in a double-chain subunit
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Crystal Growth & Design
ARTICLE
Figure 1. ORTEP drawing of the basic building units in compounds 1À6 (aÀf) with thermal ellipsoids at 30% probability.
Figure 2. View of the hydrogen bonds between TBBPF and PZ (a, b) and the 2D supramolecular 44-sql layer of compound 1 (c, the end-on PZ
molecules are highlighted in green).
Figure 3. View of the interconnection between the decamer synthon (a), the 3D supramolecular structure of compound 2 (b), and the topological pcu
net simplified from 2 (c).
(Figure 4a), which is further linked by HDABCO+ into a 44-sql layer
through Ohydroxyl N interactions (2.552 and 2.677 Å)
(Figure 4b). Furthermore, the 2D structure is reinforced by halogen
(TBBPF) (HMTA) (4) and (TBBPA) (HMTA) (5). Cocrystalli-
3
3
H
zation of HMTA with TBBPF and TBBPA resulted in 1:1
adducts of 4 and 5, respectively (Figure 1d,e). Structures of 4
and 5 contain similar zigzag chain subunits built by alternate
3 3 3 3 3 3
bonds (X-bonds) with Br N distance of (3.478 Å).
3 3 3
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Crystal Growth & Design
ARTICLE
Figure 6. View of the 1D supramolecular zigzag chain (a) and the 1D
supramolecular zigzag ladder of compound 5 (b).
Figure 4. View of the 1D supramolecular ribbon (a) and the 2D
supramolecular 44-sql layer of compound 3 (b).
Figure 5. View of the 1D supramolecular zigzag chain (a) and the 2D
supramolecular 44-sql layer of compound 4 (b).
Figure 7. View of the hexamer subunit (a), the connection between
hexamer subunits and water molecules (b), and the 1D supramolecular
ribbon of compound 6 (c).
connection of TBBPF/TBBPA and HMTA via Ohydroxyl
H
3 3 3 3 3 3
N (O
H
N of 2.736 and 2.964 Å for 4; 2.676 and 2.709 Å for
transfer was determined from the Fourier difference map of
electron density as well as from the CÀOphenol bond lengths
(Table S1, Supporting Information). Generally speaking, the
bisphenol molecules exhibit shorter bonds (1.299À1.309 Å) for
the ionized phenol groups than the nonionized ones
3 3 3 3 3 3
5) hydrogen bonds (Figure 5a and 6a). The remaining two N
donors of HMTA in 4 are involved in strong Br N halogen
3 3 3
bonding interactions (Br N of 3.201 and 3.431 Å) and result in a
3 3 3
wavy 44-sql layer structure built by mixed hydrogen and halogen
bonds (Figure 5b). However, only one of the remaining two N
(1.338À1.363 Å). Furthermore, the distances of Ohydroxyl
3 3 3
N hydrogen bonds17 (Table S2, Supporting Information) in
donors of HMTA in 5 is involved in strong Br N halogen
H
3 3 3
3 3 3
bonding interactions (Br N of 3.446 Å) and this results in the
formation of a zigzag ladder structure (Figure 6b).
compounds 1À3(salts) are shorter than the ordinary H-bond (2.8/
3 3 3
2.9 Å, minimum/average distances), and they are thus considered as
(TBBPA)3 (HMTA)3 H2O (6). There are three TBBPA, three
double charge-assisted H-bonds comprised by strong 1/2ÀD
3
3
3 3 3
H+ A1/2À interactions (D = H-bond donor; A = H-bond
HMTA, anda water moleculein theasymmetric unitofcompound
6 (Figure 1f). The six crystallographically independent modules
(three TBBPA and three HMTA) form a hexamer subunit
3 3 3
acceptor).18 However, in the cases of compounds 4À6, which are
built by TBBPF/TBBPA with HMTA, no proton transfer from
TBBPF/TBBPA to HMTA has been observed, which is also in
agreement with the judgment of CÀOphenol bond lengths (Table
S1, Supporting Information); thus compounds 4À6 are cocrystals.
The H-bond dominated structural dimensionalities of com-
pounds 1À6 decrease from 3D and 2D (compounds 2, 1, and 3)
to 1D (4 and 5) and 0D (6) with the varieties of organoamines. It
is not intricate to understand: In compounds 1 and 2, each N
atom on PZ has two lone pair electrons; therefore PZ molecules
provide four possibilities of connections, which is a potential
factor to generate 2D and 3D nets when TBBPF behaves as
through Ohydroxyl
H
N hydrogen bonds (2.683À2.738 Å)
3 3 3 3 3 3
(Figure 7a). Interestingly, the hexamer subunits in 6 can be viewed
as a fragment of three repeating units for a zigzag chain observed in
compound 5. Two such hexamer subunits are connected by a
pair of water molecules (Ow
H
N of 2.853 Å and Ohydroxyl
3 3 3 3 3 3
3 3 3
H
Ow of 2.665 Å) and give birth to a molecular oligomer, as
3 3 3
shown in Figure 7b, which is further extended into a 1D ribbon by
Br N X-bonds (3.267 and 3.318 Å) (Figure 7c).
3 3 3
Proton transfer from TBBPF to PZ/DABCO was observed in
compounds 1À3; therefore they are organic salts. Proton
3555
dx.doi.org/10.1021/cg200520w |Cryst. Growth Des. 2011, 11, 3551–3557

Crystal Growth & Design
ARTICLE
linkers. We would also expect that HMTA, comprising four N
donors locating in a tetrahedral pattern, is sufficient to form 3D
structures although HMTA has only one lone pair electron on each
of its four N atoms. However, HMTA produces cocrystals with
TBBPF/TBBPA primarily in 1:1 stoichiometric ratio; thus only
’ CONCLUSION
In summary, we have prepared two bisphenol derivatives, tetra-
bromobisphenol-F (TBBPF) and tetrabromobisphenol-A
(TBBPA), by bromination reactions of bisphenol-F (BPF) and
bisphenol-A (BPA), respectively. TBBPF and TBBPA were utilized
to assemble with various organoamines and resulted in a series of six
supramolecular organic frameworks (SOFs) with versatile topolo-
two of its N donors are involved in Ohydroxyl
H
N H-bonds to
3 3 3 3 3 3
reinforce the two O donors of TBBPF/TBBPA. In this way, both
HMTA and TBBPF/TBBPA behave as linkers (geometrically) and
lead to low-dimensional (1D) structures. Once 1D and 0D
H-bonded structures are assembled, as in the case of compounds
gical structures, including three organic salts, (TBBPF2À
)
2
3
(HPZ+)2 (H2PZ2+) (1), (TBBPFÀ)2 (H2PZ2+) 2H2O 2MeOH
3
3
3
3
3
(2), and (TBBPF) (TBBPFÀ) (HDABCO+) H2O (3), and
3
3
4À6, auxiliary Br N X-bonds (3.201À3.478 Å) have been
3 3 3
three cocrystals, (TBBPF) (HMTA) (4), (TBBPA) (HMTA)
(5), and (TBBPA)3 (HMTA)3 H2O (6). Structures of the six
3
3
extensively observed and found robust to direct the hierarchical
molecular assemblies into higher dimensionalities.
3
3
SOFs are defined by predominant hydrogen bonds (H-bonds). It is
found that dimensionalities of the H-bonded structures vary based
on the geometries as well as the different pattern of electron
configurations of organoamines. Moreover, bromination on bi-
sphenol molecules not only boosts the ability of hydroxyl O donors
to form H-bonds but also introduces supportive X-bonds to direct
the hierarchical molecular assemblies, which has been demonstrated
as a successful synthetic strategy to build new supramolecular
organic frameworks.
It is now clear that molecular design based on the assembly of
comparable secondary building units may result in different
architectures by virtue of the effect of molecular shape, size,
and substituent. In this current system, for example, compounds
4 and 5 are built by similar organic modules, TBBPF/TBBPA,
with the same organoamine HMTA. However, the overall
packing diagrams of 4 and 5 differ from 44-sql layer to 1D zigzag
ladder. A careful examination of the structures indicates that the
CbenzeneÀCcentralÀCbenzene angle around the central sp3 carbon
of the TBBPF is somewhat distorted (115.9°; 115.2°À117.7° in
compounds 1À4), whereas the CbenzeneÀCcentralÀCbenzene angle
around the central sp3 carbon of the TBBPA is standard (109.9°;
108.5°À110.2° in compounds 5 and 6). This means that TBBPF
’ ASSOCIATED CONTENT
Supporting Information. 1H NMR, IR, XRPD, TGA,
S
b
is somewhat flat, and thus the Ophenol Ophenol distance of
and crystallographic data in CIF format. This material is available
free of charge via the Internet at http://pubs.acs.org.
3 3 3
TBBPF (9.73 Å; 9.73À9.99 Å in compounds 1À4) is longer than
the one in TBBPA (9.39 Å; 9.36À9.60 Å). Furthermore, the
methyl on the central sp3 carbon of the TBBPA molecules leads
to steric hindrance of the molecular packing. Indeed, the methyl
points outward from the ladder structures in compound 5, which
deters its further connection into layers. On the other hand, we
notice that inclusion of solvent MeOH or H2O molecules (likely
captured from air) would dramatically influence the molecular
packing as in the cases of TBBPF/PZ (compounds 1 and 2) and
TBBPA/HMTA (compounds 5 and 6). It is intelligible that time
of crystallization, which is related to the concentration and mol
ratio of starting materials, accounts for the inclusion of solvent
molecules; that is, the higher the concentration and mol ratio of
starting materials is (in compounds 1 and 5), the shorter the time
needed for crystallization is and the less likely solvent molecules,
especially H2O in atmosphere, will be present (in compounds 2
and 6).
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: rcao@fjirsm.ac.cn.
’ ACKNOWLEDGMENT
Financial support from the 973 Program (Grants 2011CB932504
and 2007CB815303), NSFC (Grants 20731005, 20821061, and
21001105), Fujian Key Laboratory of Nanomaterials (Grant
2006L2005), and Key Project from CAS are gratefully acknowledged.
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