A Co-crystal strategy to tune the supramolecular patterns and luminescent properties: Ten well-designed salts assembled by arenedisulfonic acid with diverse diamines

Article abstract of DOI:10.1021/cg3004855

Ten salts assembled by arenedisulfonic acid with hydrazine, flexible aliphatic diamines, rigid and semirigid aromatic diamines, namely, (H ₂HA)²⁺?(NDS)^2- (1), (H₂EDA) ²⁺?(NDS)^2- (2), (H₂PDA) ²⁺?(NDS)^2- (3), (H₂BTDA) ²⁺?(NDS)^2- (4), (H₂BDMA) ²⁺?(NDS)^2-?2H₂O (5), 2(o-HBDA) ⁺?(NDS)^2- (6), (m-H₂BDA) ²⁺?(NDS)^2- (7), (H₂MBDA) ²⁺?(NDS)^2-?3H₂O (8), (H ₂SDA)²⁺?(NDS)^2-?H₂O (9), and 2(HSDA)⁺?(NDS)^2-?H₂O (10) (H ₂NDS = 1,5-naphthalenedisulfonic acid, HA = hydrazine, EDA = 1,2-ethanediamine, PDA = 1,3-propanediamine, BTDA = 1,4-butanediamine, BDMA = 1,3-benzenedimethanamine, o-BDA = 1,2-benzenediamine, m-BDA = 1,3-benzenediamine, MBDA = 4-methyl-1,3-benzenediamine, SDA = 4,4′-sulfonyldiamiline), have been constructed and characterized by elemental analysis, infrared, thermogravimetric analysis, phospholuminescence, and powder and single-crystal X-ray diffraction. Structural analyses indicate that the nature of the diamines can effectively influence the final structures of the salts through diverse noncovalent bonding interactions, such as hydrogen bonds, π???π stacking, N-H???π, C-H???π, and lone pair???π interactions, which result in six types of architectures. Crystals 1-3 exhibit a three-dimensional (3-D) pillared layered supramolecular network with the diammonium cations being sandwiched among the sulfonate groups, while crystal 4 exhibits a 3-D honeycomb network with the -(CH₂) ₄- groups being encapsulated among the NDS^2- anions. In comparison with crystal 4, crystals 5, 7, and 8 exhibit a different 3-D supramolecular network, in which the phenylene, phenyl, and methylphenyl groups interpenetrate with the naphthyl rings of NDS^2- anions through continuous π???π interactions. Crystal 6 is two-dimensional pillared layered network with the o-HBDA⁺ cations arranging along the two sides of the layer. Crystal 9 possesses an organic 3-D supramolecular network formed by the C-H???π and sulfonyl involved lone pair???π interactions which encapsulates a one-dimensional (1-D) infinite [-SO₃???H₃N-]_n nanotube in the large voids. By contrast, crystal 10 possesses an organic 3-D supramolecular network formed by intricate C-H???π, π???π, and sulfonyl involved C/N-H???O interactions which encapsulates 1-D centipede-shaped [-SO ₃???H₃N-]_n chains in the large voids. Luminescent investigations demonstrate that the salts containing aliphatic diamines exhibit stronger emission intensity than those containing aromatic diamines. This result indicates that the H₂NDS might be used to distinguish the aliphatic diamine from aromatic diamine qualitatively through the luminescent signal.

Full text of DOI:10.1021/cg3004855

Article
pubs.acs.org/crystal
A Co-Crystal Strategy to Tune the Supramolecular Patterns and
Luminescent Properties: Ten Well-Designed Salts Assembled by
Arenedisulfonic Acid with Diverse Diamines
Zhao-Peng Deng, Li-Hua Huo,* Hui Zhao, and Shan Gao*
Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Heilongjiang University, Harbin 150080,
People’s Republic of China
S
* Supporting Information
ABSTRACT: Ten salts assembled by arenedisulfonic acid with hydrazine,
flexible aliphatic diamines, rigid and semirigid aromatic diamines, namely,
(H2HA)2+·(NDS)2− (1), (H2EDA)2+·(NDS)2− (2), (H2PDA)2+·(NDS)2− (3),
(H2BTDA)2+·(NDS)2− (4), (H2BDMA)2+·(NDS)2−·2H2O (5), 2(o-HBDA)+·
(NDS)2− (6), (m-H2BDA)2+·(NDS)2− (7), (H2MBDA)2+·(NDS)2−·3H2O (8),
(H2SDA)2+·(NDS)2−·H2O (9), and 2(HSDA)+·(NDS)2−·H2O (10) (H2NDS = 1,5-
naphthalenedisulfonic acid, HA = hydrazine, EDA = 1,2-ethanediamine, PDA = 1,3-
propanediamine, BTDA = 1,4-butanediamine, BDMA = 1,3-benzenedimethan-
amine, o-BDA = 1,2-benzenediamine, m-BDA = 1,3-benzenediamine, MBDA = 4-
methyl-1,3-benzenediamine, SDA = 4,4′-sulfonyldiamiline), have been constructed
and characterized by elemental analysis, infrared, thermogravimetric analysis,
phospholuminescence, and powder and single-crystal X-ray diffraction. Structural
analyses indicate that the nature of the diamines can effectively influence the final
structures of the salts through diverse noncovalent bonding interactions, such as
hydrogen bonds, π···π stacking, N−H···π, C−H···π, and lone pair···π interactions, which result in six types of architectures. Crystals 1−
3 exhibit a three-dimensional (3-D) pillared layered supramolecular network with the diammonium cations being sandwiched among
the sulfonate groups, while crystal 4 exhibits a 3-D “honeycomb” network with the −(CH2)4− groups being encapsulated among the
NDS2− anions. In comparison with crystal 4, crystals 5, 7, and 8 exhibit a different 3-D supramolecular network, in which the
phenylene, phenyl, and methylphenyl groups interpenetrate with the naphthyl rings of NDS2− anions through continuous π···π
interactions. Crystal 6 is two-dimensional pillared layered network with the o-HBDA+ cations arranging along the two sides of the
layer. Crystal 9 possesses an organic 3-D supramolecular network formed by the C−H···π and sulfonyl involved lone pair···π
interactions which encapsulates a one-dimensional (1-D) infinite [−SO3···H3N−]n nanotube in the large voids. By contrast, crystal 10
possesses an organic 3-D supramolecular network formed by intricate C−H···π, π···π, and sulfonyl involved C/N−H···O interactions
which encapsulates 1-D “centipede-shaped” [−SO3···H3N−]n chains in the large voids. Luminescent investigations demonstrate that
the salts containing aliphatic diamines exhibit stronger emission intensity than those containing aromatic diamines. This result
indicates that the H2NDS might be used to distinguish the aliphatic diamine from aromatic diamine qualitatively through the
luminescent signal.
Therefore, the choice of supramolecular formers is a crucial
issue for constructing supramolecular architectures and
modifying the properties of organic molecules in the solid state.
The sulfonate group (−SO3), with a symmetry of C3v, is not
only an excellent binding group for constructing metal
complexes10 but also an outstanding synthon for assembling
salts with proper organic amine molecules, such as the primary
INTRODUCTION
■
Rational design and assembly of supramolecules by the co-
crystal strategy has become a subject of growing interest in
recent years owing to their intriguing supramolecular patterns
and potential applications in the field of photochemistry,
biomedicine, and pharmaceutics.1,2 Generally, a co-crystal is a
multicomponent assembly held together by noncovalent
interactions.2a It can be viewed as an addition to the existing
class of crystalline solids (polymorphs, hydrates/solvates, and
salts).3 From the principles of crystal engineering and
supramolecular chemistry,4 formation of supramolecular
patterns relies on intermolecular noncovalent bonding
interactions and molecular packing patterns, in which these
intermolecular interactions include hydrogen bonds,5 π···π
stacking,6 C−H···π,7 cation···π,8 as well as the anion···π inter-
action (and more generally the lone pair-π interaction).9
11
+
ammonium cations (R−NH3 ). As the case for −SO3, the
−NH3+ cation also has the “AB3” form and exhibits a similar C3v
symmetry. The three acceptor oxygen atoms on the −SO3
themselves have a closely related tetrahedral geometry to the
+
three donor H atoms on the −NH3 cations. Thus, the equal
Received: April 9, 2012
Revised: May 6, 2012
Published: May 8, 2012
© 2012 American Chemical Society
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Article
number of separated hydrogen bond donor and acceptor sites
with matched geometry and stereoavailability allows the for-
mation of diverse supramolecular patterns. To date, some
salts of arenesulfonates and primary ammonium cations have
been reported based on the Cambridge Structural Database
CSD search,12 in which most of the primary amines involved
are monoamines and some interesting and synthetic work is
reported. In 2006 and 2009, Tohnai and co-workers reported
salts of anthracene-2,6-disulfonic acid (2,6-ADS) with a wide
variety of primary monoamines, and their studies revealed that
the salts presented seven types of crystal forms and
corresponding molecular arrangements of anthracene moieties
depended on the nature of the monoamine, which then
influenced the fluorescent properties of salts.13 In 2007, the
same work group readily prepared a series of salts from simple
molecules: triphenylmethylamine (TPMA) and a variety of
monosulfonic acids, which exhibited [4 + 4] ion-pair clusters
consisting of four TPMA and four monosulfonic acid
components. Because of their nanoscale sizes, these clusters
might also have potential as quantum dots.14 Five years later, in
2012, they constructed a family of salts with the host comprising
of TPMA and 1,8-ADS which encapsulated different guest
solvent molecules. Interestingly, these salts displayed a wide
range of emission colors from blue to orange-yellow depending
on the included guests under UV irradiation.15 Moreover, the
salts of guanidinium sulfonates (GS) have also been best
investigated in the past few years owing to the matched
geometry and stereoavailability between the guanidinium
cations and the sulfonate anions.16 By contrast, systematic
research on the supramolecular patterns and properties of salts
constructed from arenedisulfonates and diamines is less
common despite crystal structures of some scattered salts
being reported.17
Structural analyses indicate that the nature of the diamines can
effectively influence the final structures of the salts through
different noncovalent bonding interactions. Crystals 1−3 exhibit
a three-dimensional (3-D) pillared layered supramolecular
network, while crystals 4 and 5 present a 3-D supramolecular
network with the H2BTDA2+and H2BDMA2+ cations inter-
penetrated with the NDS2− anions. Crystal 6 is two-dimensional
(2-D) pillared layered network with the o-HBDA+ cations,
whereas crystals 7 and 8 exhibit a 3-D supramolecular network
with the m-H2BDA2+ and H2MBDA2+ cations interpenetrated
with the NDS2− anions. The two protonated amine groups of
semirigid H2SDA2+ cations in crystal 9 form hydrogen bonds
with −SO3 groups, thus generating a 3-D supramolecular
network with the sulfonyl group involved in lone pair···π
interactions. By contrast, in crystal 10, only one amine group of
semirigid HSDA+ cations is protonated, which involves in the
formation of hydrogen bonding interactions with −SO3 groups,
resulting in a 3-D supramolecular network together with the
sulfonyl involved C/N−H···O interactions. Moreover, thermal
stabilities and luminescent properties of the 10 salts are also
investigated.
EXPERIMENTAL SECTION
■
General Procedures. All chemicals and solvents were of A. R.
grade and used without further purification in the syntheses. Elemental
analyses were carried out with a Vario MICRO from Elementar
Analysensysteme GmbH, and the infrared spectra (IR) were recorded
from KBr pellets in the range of 4000−400 cm−1 on a Bruker Equinox
55 FT-IR spectrometer. Powder X-ray diffraction (PXRD) patterns for
the three complexes were measured at 293 K on a Bruker D8
diffractometer (Cu Kα, λ = 1.54059 Å). The TG analyses were carried
out on a Perkin-Elmer TG/DTA 6300 thermal analyzer under flowing
N2 atmosphere, with a heating rate of 10 °C min−1. UV−vis spectra
were measured on a Perkin-Elmer Lambda 900 ultraviolet−visible
spectrometer. Luminescence spectra were measured on a Perkin-Elmer
LS 55 luminescence spectrometer.
Hence, to this contribution, we reported here the supramolecular
patterns and luminescent properties of 10 salts assembled by 1,5-
naphthalenedisulfonic acid (H2NDS) with hydrazine, four flexible
aliphatic diamines, three rigid and one semirigid aromatic diamines
(Scheme 1), namely, (H2HA)2+·(NDS)2‑ (1), (H2EDA)2+·(NDS)2‑
Synthesis of (H2HA)2+·(NDS)2− (1). A 5 mL methanol solution of
hydrazine monohydrate (99% pure, 1 mmol, 0.05 mL) was added to an
aqueous solution (5 mL) of 1,5-naphthalenedisulfonic acid tetrahydrate
(1 mmol, 360 mg). The mixture was stirred for 10 min at 343 K in a
water bath, and then filtered after cooling to room temperature.
Colorless crystals of 1 suitable for X-ray diffraction were isolated from
the filtrate after four days. Yield: 81%. Elemental analysis calcd (%) for
C10H12N2O6S2: C 37.50, H 3.78, N 8.75; found: C 37.44, H 3.83, N
8.78. IR (ν/cm−1): 3446m, 3050−2557br,s, 1571m, 1527m, 1506m,
1241m, 1220s, 1201s, 1157s, 1114m, 1033s, 789s, 765s, 601s.
Scheme 1. Schematic Representation of Molecules Used in
This Article
Synthesis of (H2EDA)2+·(NDS)2− (2). A similar procedure as for
crystal 1 was employed to prepare crystal 2 by changing the hydrazine
hydrate into 1,2-ethanediamine (99% pure, 1 mmol, 0.07 mL). Colorless
crystals of 2 suitable for X-ray diffraction were isolated from the filtrate
after three days. Yield: 61%. Elemental analysis calcd (%) for
C12H16N2O6S2: C 41.37, H 4.63, N 8.04; found: C 41.32, H 4.59, N
7.99. IR (ν/cm−1): 3448 m, 3168−2831br,s, 1614m, 1529m, 1502m,
1334m, 1243s, 1224s, 1195s, 1155s, 1112m, 1031s, 788s, 767s, 609s.
Synthesis of (H2PDA)2+·(NDS)2− (3). A similar procedure as for
crystal 1 was employed to prepare crystal 3 by changing the hydrazine
hydrate into 1,3-propanediamine (98% pure, 1 mmol, 0.08 mL).
Colorless crystals of 3 suitable for X-ray diffraction were isolated from
the filtrate after three days. Yield: 79%. Elemental analysis calcd (%)
for C13H18N2O6S2: C 43.08, H 5.01, N 7.73; found: C 43.12, H 4.95,
N 7.77. IR (ν/cm−1): 3448m, 3148−2897br,s, 1613m, 1527s, 1504m,
1336m, 1243s, 1226s, 1197s, 1155s, 1091m, 1031s, 786s, 765s, 611s.
Synthesis of (H2BTDA)2+·(NDS)2− (4). A similar procedure as for
crystal 1 was employed to prepare crystal 4 by changing the hydrazine
hydrate into 1,4-butanediamine (98% pure, 1 mmol, 0.1 mL).
Colorless crystals of 4 suitable for X-ray diffraction were isolated
from the filtrate after three days. Yield: 83%. Elemental analysis calcd
(2), (H2PDA)2+·(NDS)2− (3), (H2BTDA)2+·(NDS)2− (4),
(H2BDMA)2+·(NDS)2−·2H2O (5), 2(o-HBDA)+·(NDS)2− (6),
(m-H2BDA)2+·(NDS)2− (7), (H2MBDA)2+·(NDS)2−·3H2O
(8), (H2SDA)2+·(NDS)2−·H2O (9), and 2(HSDA)+·
(NDS)2−·H2O (10) (HA = hydrazine, EDA = 1,2-ethanedi-
amine, PDA = 1,3-propanediamine, BTDA = 1,4-butanedi-
amine, BDMA = 1,3-benzenedimethanamine, o-BDA = 1,2-
benzenediamine, m-BDA = 1,3-benzenediamine, MBDA =
4-methyl-1,3-benzenediamine, SDA = 4,4′-sulfonyldiamiline).
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(%) for C14H20N2O6S2: C 44.67, H 5.36, N 7.44; found: C 44.63, H
5.40, N 7.41. IR (ν/cm−1): 3444m, 3190−2908br,m, 1630m, 1595m,
1489s, 1334m, 1233m, 1214s, 1185s, 1153s, 1035s, 788m, 764s, 611s.
Synthesis of (H2BDMA)2+·(NDS)2−·2H2O (5). A similar procedure as
crystal 1 was employed to prepare crystal 5 by changing the hydrazine
hydrate into 1,3-benzenedimethanamine (98% pure, 1 mmol, 0.13 mL).
Colorless crystals of 5 suitable for X-ray diffraction were isolated from
the filtrate after three days. Yield: 78%. Elemental analysis calcd (%) for
C18H24N2O8S2: C 46.95, H 5.25, N 6.08; found: C 46.93, H 5.20, N
6.05. IR (ν/cm−1): 3452m, 3145−2841br,s, 1631m, 1596m, 1525m,
1501m, 1455m, 1384m, 1338m, 1243s, 1213s, 1182s, 1149s, 1035s,
788s, 767s, 607s.
U(H) = 1.5Ueq (N, O). The hydrogen atoms of water molecules in
crystal 9 were fixed by WinGX with O−H = 0.85 Å and U (H) =
1.5Ueq (O). All calculations were carried out with the SHELXTL97
program.18 The CCDC reference numbers are 873407−873416 for
crystals 1−10. Selected hydrogen bond parameters for crystals 1−10
are presented in Table 2.
RESULTS AND DISCUSSION
■
Syntheses. As stated in the introduction, formation of
supramolecules relies on intermolecular noncovalent bonding
interactions and molecular packing patterns. Therefore, the
choice of supramolecular formers is crucial to the final
architectures of supramolecules. Herein, based on the consid-
eration of the structural diversities and the potential ability of
forming noncovalent bonding interactions, hydrazine, four
flexible aliphatic diamines, three rigid, and one semirigid aromatic
diamines were employed to react with 1,5-naphthalenedisulfonic
acid in a mixed methanol−water solution, leading to the
formation of crystals 1−10. It should be clarified that crystal 2
had been incidentally synthesized in our previous work for the
prepared cobalt-sulfonate complex.19 As systematic research of
the supramolecular patterns based on arenedisulfonate and
diamines, we synthesized this crystal by using a simple method
again and an additional single crystal X-ray diffraction experiment
was also carried out. Crystals 1−5 and 7−9 can be easily
obtained as 1:1 salts. By contrast, during the experiments, despite
the ratio of the reactants being changed from 1:1 to 1:3 with an
increasing amount of H2NDS, crystal 6 was only obtained as a
2:1 salt. The main reason may be attributed to the formation of
the strong N−H···π interactions between adjacent o-HBDA+
cations and the steric effect originated from the short distance
between the two amines groups in the rigid o-BDA molecule in
comparison with the flexible EDA molecule. Moreover, for the
long semirigid SDA molecule, a different ratio between the
reactants was accomplished to investigate the influence of the
bonding ability of the sulfonyl group on the final architectures.
Thus, 1:1 (9) and 2:1 (9) salts were synthesized. As anticipated,
various weak forces, that is, hydrogen bonding, π···π stacking,
N−H···π, C−H···π, and lone pair···π interactions, play a key role
in stabilizing the self-assembly process observed for all salts.
Moreover, the final architectures partially depend on the
hydrogen bonding modes of the −SO3 and −NH3 groups.
Structure Description of Crystals 1−3. As illustrated in
Figure 1a−c, the structures of crystals 1−3 all comprise one
diammonium cation and one NDS2− anion, which form
cation···anion pairs through the hydrogen bonding interactions
(Table 2). The diammonium cation and the NDS2− anion are all
located at special positions. The −SO3 groups and −NH3
groups in the three crystals all interact with each other through
the N−H···O hydrogen bonding interactions to form a 2-D
layer structure (Scheme 2). Subsequently, the naphthyl rings of
the NDS2− anions direct alternately to both sides of the layer
and also extend the layers into a 3-D pillared layered supra-
molecular network with the diammonium cations being
sandwiched among the sulfonate groups (Figure 1d−f). The
distances between the two sulfonate walls are 3.970(2),
4.321(2), and 5.917(2) Å (the shortest distances between the
opposite S atoms), respectively. It should be noted that the
naphthyl rings of the NDS2− anions in the three crystals are all
involved in the C−H···π interactions20 between the π electron
density of naphthyl ring and adjacent CH group, resulting in the
formation of a 2-D layer structure as shown in Figure 2, in which
four naphthyl rings form a “dumbbell” like ring. As the length of
Synthesis of 2(o-HBDA)+·(NDS)2− (6). A similar procedure as for
crystal 1 was employed to prepare crystal 6 by changing the hydrazine
hydrate into 1,2-benzenediamine (1 mmol, 108 mg). Colorless crystals
of 6 suitable for X-ray diffraction were isolated from the filtrate after
four days. Yield: 70%. Elemental analysis calcd (%) for C22H24N4O6S2:
C 52.37, H 4.79, N 11.10; found: C 52.40, H 4.83, N 11.07. IR
(ν/cm−1): 3455m, 3378m, 3104−2862br,s, 1633m, 1558m, 1502m,
1462m, 1323m, 1238s, 1216s, 1193s, 1153s, 1037s, 782m, 742m, 613s.
Synthesis of (m-H2BDA)2+·(NDS)2− (7). A similar procedure as for
crystal 1 was employed to prepare crystal 7 by changing the hydrazine
hydrate into 1,3-benzenediamine (1 mmol, 108 mg). Colorless crystals
of 7 suitable for X-ray diffraction were isolated from the filtrate after
five days. Yield: 74%. Elemental analysis calcd (%) for C16H16N2O6S2:
C 48.48, H 4.07, N 7.07; found: C 48.51, H 4.02, N 7.11. IR (ν/cm−1):
3413m, 3120−2895br,m, 1633m, 1589m, 1544s, 1496m, 1336m,
1251s, 1220s, 1187s, 1157s, 1031s, 798m, 765m, 612s.
Synthesis of (H2MBDA)2+·(NDS)2−·3H2O (8). A similar procedure as
for crystal 1 was employed to prepare crystal 8 by changing the
hydrazine hydrate into 4-methyl-1,3-benzenediamine (1 mmol, 122 mg).
Brown crystals of 8 suitable for X-ray diffraction were isolated from the
filtrate after three days. Yield: 78%. Elemental analysis calcd (%) for
C17H24N2O9S2: C 43.96, H 5.21, N 6.03; found: C 43.93, H 5.17, N
6.06. IR (ν/cm−1): 3461m, 3058−2642br,s, 1638m, 1556m, 1508m,
1332m, 1238s, 1216s, 1197s, 1157s, 1035s, 788m, 767m, 619s.
Synthesis of (H2SDA)2+·(NDS)2−·H2O (9). A similar procedure as for
crystal 1 was employed to prepare crystal 9 by changing the hydrazine
hydrate into 4,4′-sulfonyldiamiline (1 mmol, 136 mg). Colorless
crystals of 9 suitable for X-ray diffraction were isolated from the filtrate
after three days. Yield: 78%. Elemental analysis calcd (%) for
C22H22N2O9S3: C 47.65, H 4.00, N 5.05; found: C 47.62, H 3.95, N
5.01. IR (ν/cm−1): 3459m, 3071−2611br,m, 1630m, 1596m, 1521m,
1494m, 1423m, 1323m, 1240m, 1220s, 1191m, 1155s, 1105m, 1029s,
782m, 765m, 678s, 611s.
Synthesis of 2(HSDA)+·(NDS)2−·H2O (10). A similar procedure as
for crystal 9 was employed to prepare crystal 10 by increasing the
amount of 4,4′-sulfonyldiamiline (2 mmol, 272 mg). Yellow crystals
of 10 suitable for X-ray diffraction were isolated from the filtrate
after three days. Yield: 83%. Elemental analysis calcd (%) for
C34H34N4O11S4: C 50.86, H 4.27, N 6.98; found: C 50.83, H 4.32,
N 7.02. IR (ν/cm−1): 3421s, 3344s, 3085−2888br,s, 1632m, 1595m,
1488m, 1455m, 1417m, 1325m, 1232m, 1211s, 1197m, 1155s, 1089s,
1049s, 788m, 765m, 682m, 609m.
X-ray Crystallographic Measurements. Table 1 provides a
summary of the crystal data, data collection, and refinement
parameters for the crystals 1−10. All diffraction data were collected
at 295 K on a RIGAKU RAXIS-RAPID diffractometer with graphite
monochromatized Mo-Kα (λ = 0.71073 Å) radiation in ω scan mode.
All structures were solved by direct method and difference Fourier
syntheses. All non-hydrogen atoms were refined by full-matrix least-
squares techniques on F2 with anisotropic thermal parameters. The
hydrogen atoms attached to carbons were placed in calculated
positions with C−H = 0.93 Å (aromatic H atoms), C−H = 0.97 Å
(methylene H atoms), C−H = 0.96 Å (methyl H atoms), and U (H) =
1.2Ueq (C) in the riding model approximation. The hydrogen atoms of
nitrogen atoms in crystals 1−10 and the hydrogen atoms of water
molecules in crystals 5, 8, and 10 were located in difference Fourier
maps and were also refined in the riding model approximation, with
N−H and O−H distance restraint (0.86(1) or 0.85(1) Å) and
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Table 1. Crystal Data and Structure Refinement Parameters of Crystals 1−10
a
crystals
1
2
3
4
5
empirical formula
formula weight
space group
a (Å)
C10H12N2O6S2
320.34
P21/c
C12H16N2O6S2
348.39
P21/c
C13H18N2O6S2
362.41
C2/c
C14H20N2O6S2
376.44
C2/c
C18H24N2O8S2
460.51
P1
̅
10.837(2)
7.6503(15)
7.2566(15)
90.00
11.187(2)
8.2310(16)
8.5011(17)
90.00
25.475(5)
7.4957(15)
7.9814(16)
90.00
17.786(4)
10.674(2)
9.3039(19)
90.00
8.7396(17)
9.920(2)
13.624(3)
69.27(3)
72.65(3)
77.08(3)
1045.1(4)
2
b (Å)
c (Å)
α (°)
β (°)
γ (°)
V (Å3)
95.41(3)
90.00
100.26(3)
90.00
91.11(3)
90.00
116.72(3)
90.00
598.9(2)
2
770.2(3)
2
1523.8(5)
4
1577.7(7)
4
Z
Dc/g cm−3
μ (Mo Kα)/mm−1
F(000)
1.776
1.502
1.580
1.585
1.463
0.474
0.376
0.383
0.373
0.303
332
364
760
792
484
reflections collected
unique reflections
parameters
R (int)
5616
7301
4943
7585
10374
1358
1755
1724
1809
4754
100
109
114
118
301
0.0434
1.069
0.0593
1.080
0.0994
1.043
0.0453
1.030
0.0368
1.090
GOF on F2
final R indices [I ≥ 2σ(I)]
R1 = 0.0387
wR2 = 0.1041
6
R1 = 0.0508
wR2 = 0.1251
7
R1 = 0.0632
wR2 = 0.1297
8
R1 = 0.0434
wR2 = 0.1118
9
R1 = 0.0559
wR2 = 0.1588
10
complexes
empirical formula
formula weight
space group
a (Å)
C22H24N4O6S2
504.57
C16H16N2O6S2
396.43
C17H24N2O9S2
464.50
C22H22N2O9S3
554.60
C34H34N4O11S4
802.89
C2/c
P2/n
P21/c
P1
̅
C2/c
39.141(8)
7.2708(15)
7.8823(16)
90.00
9.1443(18)
8.0163(16)
12.632(3)
90.00
13.383(3)
12.706(3)
13.944(3)
90.00
5.7543(12)
14.022(3)
14.952(3)
83.94(3)
81.13(3)
84.37(3)
1181.2(4)
2
28.300(6)
7.0286(14)
22.237(4)
90.00
b (Å)
c (Å)
α (°)
β (°)
γ (°)
V (Å3)
92.90(3)
90.00
109.40(3)
90.00
118.35(3)
90.00
126.43(3)
90.00
2240.3(8)
4
873.4(4)
2
2086.7(10)
4
3558.8(18)
4
Z
Dc/g m−3
1.496
1.507
1.478
1.559
1.498
μ (Mo Kα)/mm−1
0.287
0.342
0.308
0.372
0.334
F(000)
1056
412
976
576
1672
reflections collected
unique reflections
parameters
R (int)
10585
8398
20046
18950
16657
2551
2007
4761
5352
4045
169
128
308
343
258
0.0387
0.0412
0.0516
0.0423
0.0533
GOF on F2
1.084
1.093
1.065
1.031
1.064
final R indices [I ≥ 2σ(I)]
R1 = 0.0403
wR2 = 0.1037
R1 = 0.0430
wR2 = 0.1083
R1 = 0.0569
wR2 = 0.1721
R1 = 0.0657
wR2 = 0.1828
R1 = 0.0468
wR2 = 0.1224
a
This structure has been reported in our previous work.19
the three diamines increases, the distances of C···π in C−H···π
interactions exhibit a regular change from 3.488(2) in 1
(∠C−H···π = 138.3°), 3.642(2) in 2 (∠C−H···π = 115.3°), to
3.806(4) Å in 3 (∠C−H···π = 136.8°).
generates 2-D layers (Scheme 2), which are pillared by the
naphthyl rings of the NDS2− anions to generate a 3-D
“honeycomb” network with the H2BTDA2+ cations being
encapsulated among the NDS2− anions (Figure 3b). Alternately,
this 3-D “honeycomb” network can also be understood in the
following manner. First, the −NH3 groups of the H2BTDA2+
cations interlink with the NDS2− anions through hydrogen
bonding interactions between O2, O3, H1N2, and H1N3
(N1−H1N2···O2iv, 2.955(2) Å, N1−H1N3···O3, 2.961(2) Å),
giving rise to a one-dimensional (1-D) nanotube along the c-axis
(Figure S1, Supporting Information). The −(CH2)4− groups
are encapsulated in the channels. Then, adjacent nanotubes are
further joined by the hydrogen bonding interactions between
O1, O3, H1N1, H1N2, and H1N3 (N1−H1N1···O1iii, 2.755(2)
Å, N1−H1N2···O1v, 3.001(2) Å, N1−H1N3···O3v, 2.963(2) Å),
Structure Description of Crystals 4 and 5. Increasing
the length of the aliphatic diamine leads to the formation of a
3-D supramolecular network in crystals 4 and 5. The structure
of crystal 4 consists of one H2BTDA2+ cation and one NDS2−
anion (Figure 3a), while the structure of crystal 5 consists of
one H2BDMA2+ cation, two NDS2− anions, and two water
molecules (Figure 4a). The H2BTDA2+ cation and the NDS2−
anions in the two crystals are all located at special positions.
All the components in the unit cell connect with each other
through the hydrogen bonding interactions (Table 2). In
crystal 4, the linkage of −SO3 groups and −NH3 groups
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Article
a
Table 2. Hydrogen Bond Parameters for Crystals 1−10
D−H···A
d(D−H) d(H···A) d(D···A) ∠(DHA)
D−H···A
d(D−H) d(H···A) d(D···A) ∠(DHA)
1
N(1)−H(1N3)···O(1)
N(2)−H(2N1)···O(3)ii
7
0.86
0.86
1.997
2.53
2.854
3.222
176.5
139
N(1)−H(1N1)···O(1)iii
N(1)−H(1N2)···O(2)iv
N(1)−H(1N2)···O(3)v
N(1)−H(1N3)···O(3)
2
0.86
0.85
0.85
0.86
1.845
2.042
2.426
1.893
2.701
2.780
3.035
2.748
176.5
144.2
128.8
177.1
N(1)−H(1N1)···O(3)
N(1)−H(1N2)···O(1)iii
N(1)−H(1N3)···O(2)iv
8
0.86
0.86
0.86
1.88
1.94
1.92
2.734
2.785
2.756
176
164
162
N(1)−H(1N1)···O(2)
N(1)−H(1N1)···O(1)
N(1)−H(1N2)···O(2)iii
N(1)−H(1N3)···O(1)iv
3
N(1)−H(1N1)···O(3)iii
N(1)−H(1N1)···O(1)iv
N(1)−H(1N2)···O(3)
N(1)−H(1N3)···O(2)v
4
N(1)−H(1N1)···O(1)iii
N(1)−H(1N2)···O(2)iv
N(1)−H(1N2)···O(1)v
N(1)−H(1N3)···O(3)
N(1)−H(1N3)···O(3)v
5
0.86
0.86
0.87
0.86
2.32
2.37
1.94
1.94
3.060
3.141
2.777
2.795
145
149
162
173
O(1W)−H(1W1)···O(3W)iii
O(1W)−H(1W2)···O(3W)iv
O(2W)−H(2W1)···O(6)v
O(2W)−H(2W2)···O(6)ii
O(3W)−H(3W1)···O(2W)
O(3W)−H(3W2)···O(1)
N(1)−H(1N1)···O(1W)
N(1)−H(1N2)···O(4)ii
N(1)−H(1N3)···O(1)
N(2)−H(2N1)···O(3)iv
N(2)−H(2N2)···O(2)i
N(2)−H(2N3)···O(5)
9
O(1W)−H(1W2)···O(6)iii
N(1)−H(1N1)···O(2)iii
N(1)−H(1N2)···O(1)
N(1)−H(1N3)···O(4)iv
N(2)−H(2N1)···O(5)
N(2)−H(2N2)···O(1W)
N(2)−H(2N3)···O(1)v
10
0.86
0.86
0.85
0.85
0.85
0.85
0.87
0.87
0.87
0.86
0.86
0.86
2.00
2.826
2.846
3.014
3.058
2.764
2.837
2.722
2.769
2.770
2.758
2.749
2.729
162
157
169
146
165
170
175
177
169
169
168
159
2.04
2.175
2.31
0.85
0.85
0.86
0.85
2.09
2.52
2.04
2.05
2.920
2.948
2.876
2.818
164
112
165
150
1.938
1.994
1.849
1.903
1.909
1.909
1.900
1.904
0.86
0.85
0.85
0.86
0.86
1.920
2.229
2.43
2.755
2.955
3.001
2.961
2.963
163
143.1
124.6
142
2.235
2.39
124.8
0.85
0.86
0.86
0.86
0.86
0.86
0.86
2.55
3.063
2.868
2.915
2.773
2.754
2.792
2.806
119.7
155
153
165
171
166
177
2.070
2.124
1.91
O(1W)−H(1W1)···O(2W)
O(1W)−H(1W2)···O(6)iii
O(2W)−H(2W1)···O(3)
O(2W)−H(2W2)···O(1)iv
N(1)−H(1N1)···O(1)
N(1)−H(1N2)···O(1W)v
N(1)−H(1N3)···O(4)vi
N(2)−H(2N1)···O(6)
N(2)−H(2N2)···O(5)vii
N(2)−H(2N3)···O(2)viii
6
0.85
0.85
0.87
0.87
0.86
0.87
0.87
0.86
0.86
0.86
2.64
3.245
2.892
2.836
3.177
2.868
2.791
2.823
2.826
2.795
2.731
129
163
142
168
174
151
163
163
176
169
2.07
2.10
1.898
1.953
1.944
2.316
2.012
1.997
1.976
1.994
1.934
1.878
O(1W)−H(1W)···O(3)ii
N(1)−H(1N1)···O(5)iii
N(1)−H(1N2)···O(1W)iv
N(1)−H(1N3)···O(1)iii
N(2)−H(2N1)···O(3)v
N(2)−H(2N2)···O(2)vi
0.85
0.86
0.86
0.86
0.85
0.85
1.940
2.118
2.098
1.933
2.20
2.763
2.922
2.941
2.775
2.991
2.981
162
155
165
163
156
158
N(1)−H(1N1)···O(2)ii
0.86
0.86
1.964
2.049
2.811
2.898
171.2
168.8
2.172
N(1)−H(1N2)···O(1)iii
a
Symmetry operations: For 1, iii −x, y − 1/2, −z + 1/2; iv x, y, z − 1; v x, −y + 1/2, z − 1/2. For 2, iii −x + 1, y + 1/2, −z + 3/2; iv x, −y + 3/2, z +
1/2. For 3, iii x, −y, z + 1/2; iv x, y, z + 1; v x, −y + 1, z + 1/2. For 4, iii −x + 1/2, y + 1/2, −z + 1/2; iv x, −y + 1, z + 1/2; v −x + 1/2, −y + 1/2, −z
+ 1. For 5, iii −x, −y, −z + 1; iv −x, −y, −z; v x + 1, y, z; vi x, y − 1, z; vii −x + 1, −y + 1, −z + 1; viii x, y + 1, z. For 6, ii x, −y, z + 1/2; iii x, −y + 1,
z + 1/2. For 7, iii −x + 1, −y, −z + 1; iv −x + 3/2, y, −z + 3/2. For 8, i −x + 1, −y + 1, −z + 1; ii −x, −y + 1, −z; iii x, −y + 3/2, z − 1/2; iv −x + 1,
y − 1/2, −z + 1/2; v x, y + 1, z. For 9, iii x − 1, y, z; iv −x, −y + 1, −z + 1; v x, y + 1, z. For 10, ii −x, y, −z + 1/2; iii −x + 1/2, −y + 1/2, −z + 1;
iv −x + 1/2, −y + 3/2, −z + 1; v x + 1/2, y − 1/2, z; vi x + 1/2, y + 1/2, z.
thus generating the 3-D “honeycomb” network (Figure 3b).
Different from the above three crystals 1−3, the naphthyl rings
in crystal 4 are parallel with each other in an interlaced mode
with the shortest centroid-to-centroid distance being 4.257(6) Å.
Thus, no π···π and C−H···π interactions are detected during the
supramolecular assembly.
Different from crystal 4, the −SO3 groups and −NH3 groups
here interact with each other through the N−H···O hydrogen
bonding interactions to form finite [(SO3)4(NH3)4] clusters,
which are subsequently bridged by pairs of O2w molecules
at the points of O1 atoms and the remaining O3 atoms to
generate another R44(12) graph set which then connect the
clusters into a 1-D tape (Figure S2, Supporting Information).
The other water molecule, O1w, forms hydrogen bonding
interactions with O6, O2w, and the remaining H1N2 atoms
and extends the aforementioned 1-D tape into a 2-D layer motif
(Figure 4b). Meanwhile, another two types of rings with the
graph sets R68(16) and R180(24) are formed. Moreover, the
naphthyl rings of the NDS2− anions and the phenyl rings of the
H2BDMA2+ cations direct alternately to both sides of the layer
and extend the layers into a 3-D supramolecular network
(Figure 4c). It should be noted that extensive π···π interactions
among these aromatic rings are observed. The centroid-to-
centroid distance between the S1-containing naphthyl ring and
phenyl ring is 3.898(2) Å, while the centroid-to-centroid
distance between the S2-containing naphthyl ring and phenyl
ring is 3.675(2) Å (Figure 4c). Such continuous π···π inter-
actions strengthen the stability of the 3-D network and lead to a
different 3-D network from crystal 4.
Structure Description of Crystal 6. As shown in
Figure 5a, the structure of crystal 6 consists of two o-HBDA+
cations and one NDS2− anion which is located at a special
position. The three parts connect to each other through the
hydrogen bonding interactions (Table 2). Adjacent −SO3
groups and −N1H3 groups interact with each other through
hydrogen bonding interactions to form a 2-D (6,3) layer
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Figure 1. Structures of crystals 1 (a), 2 (b), and 3 (c), and the 3-D pillared layered supramolecular networks of crystals 1 (d), 2 (e), and 3
(f) showing the diammonium cations sandwiched by the sulfonate groups.
(Scheme 2). The naphthyl rings of the NDS2− anions direct
to only one side of the layer, whereas the phenyl rings of the
o-HBDA+ cations direct to the other side. Such arrangement
extends the above single layer into a 2-D pillared layered
network (Figure 5b). It is interesting to note that the H2N2
atoms of the unprotonated −N2H2 groups form strong
N−H···π interactions (3.426(2) Å, ∠N−H···π = 154.7°) with
the phenyl rings instead of participating in the formation of
hydrogen bonding interactions, and thus generating a 1-D chain
structure along the c-axis (Figure 5b). Owing to the existence of
such interactions, the phenyl rings of the o-HBDA+ cations are
not intercrossed with the naphthyl rings of the NDS2− anions
as observed in crystal 5. Instead, the C−H···π interactions20
(C1−H1···π, 3.750(2) Å, ∠C−H···π = 135.3°) between the π
electron density of naphthyl ring and adjacent CH group are
observed as the case in crystals 1−3, which also result in the
formation of a 2-D layer structure as shown in Figure 2. Owing
to such interactions, the phenyl rings of the adjacent layers
arrange in head-to-head mode along the a-axis (Figure 5b).
Structure Description of Crystals 7 and 8. Reaction of
H2NDS with two similar aromatic diamines, m-BDA and
MBDA, results in two different crystals 7 and 8. The structure
of crystal 7 consists of one m-HBDA2+ cation and one NDS2−
anion (Figure 6a), while the structure of crystal 8 consists of
one H2MBDA2+ cation, two NDS2− anions, and three water
molecules (Figure 7a). The m-HBDA2+ cation and the NDS2−
anions in the two crystals are all located at special positions.
All the components in the unit cell connect with each other
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Scheme 2. Diverse Supramolecular Patterns Formed by Sulfonic and Ammonium Ions in Crystals 1−10
motif (Scheme 2). Adjacent layers are further linked into a 3-D
supramolecular network through the hydrogen bonding
interactions involving the remaining H1N1, O6, and (H2O)6
cluster formed by pairs of water molecules (Figure 7b).
As the case in crystal 5, the phenyl and naphthyl rings in the
two crystals 7 and 8 are all intercrossed with each other, which
provides the chance for the formation of π···π interactions.
The centroid-to-centroid distance in crystal 7 is 3.595(1) Å,
while the centroid-to-centroid distances in crystal 8 are
3.621(2), 3.875(2) (S1-containing naphthyl ring) and
3.678(2), 3.864(2) Å (S2-containing naphthyl ring), respec-
tively. Such π···π interactions strengthen the stability of the 3-D
network and result in a similar 3-D network as observed in
crystal 5 (Figures 6c and 7c).
Structure Description of Crystals 9 and 10. In order to
investigate the influence of the bonding ability of the sulfonyl
group in the semirigid aromatic diamine on the final archi-
tectures, a different ratio between the reactants is accomplished,
which leads to the formation of two monohydrate 1:1 and 2:1
salts. The structure of crystal 9 consists of one H2SDA2+ cation,
two NDS2− anions, and one water molecule (Figure 8a), while
the structure of crystal 10 consists of one HSDA+ cation, one
NDS2− anion, and one water molecule (Figure 9a). The NDS2−
anions in the two crystals and water molecule in crystal 10 are
all located at special positions. All the components in the unit
cell connect with each other through the hydrogen bonding
interactions (Table 2). The bent angles occurring at the point
of the sulfonyl group are 105.5° and 104.5°, respectively.
In crystal 9, adjacent −SO3 groups and −NH3 groups interact
with each other through the N−H···O hydrogen bonding
interactions to form a 1-D nanotube along the a-axis with the
water molecules filled in the channels and connected to the
inner wall through O1w−H1w2···O6iii and N2−H2N2···O1w
Figure 2. 2-D layer structure formed by C−H···π interactions with the
red shadow showing the differences of bonds and angles among
crystals 1−3 and 6.
through the hydrogen bonding interactions (Table 2). In
crystal 7, the −SO3 groups and −NH3 groups interact with each
other through the N−H···O hydrogen bonding interactions
to form 1-D ribbons (Scheme 2), which are further linked
into a 2-D layer through the phenyl rings of the protonated
m-HBDA2+ cations, leading to larger rings described by the
graph set R44(20) (Figure 6b). Moreover, the naphthyl rings of
the NDS2− anions insert into the space formed by the phenyl
rings and extend adjacent layers into 3-D supramolecular
network (Figure 6c). By contrast, the −SO3 groups and −NH3
groups in crystal 8 interact with each other through the
N−H···O hydrogen bonding interactions to form a 2-D layer
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Figure 3. (a) Structure of crystal 4. (b) 3-D “honeycomb” network of
crystal 4.
interactions (Figure 8b). Meanwhile, the organic parts also
interact with each other through the noncovalent bonding
interactions to generate a 3-D network with huge 1-D channels
(Figure 8c). On the one hand, the sulfonyl group points to the
phenyl ring of adjacent cation, which indicates the possible
existence of lone pair···π interactions. A careful inspection
following this speculation finds that the distances of 3.760(3)
and 3.529(3) Å between the O7, O8 and the centroid of the
phenyl ring (plane-centroid-anion angle α = 75.3 and 75.8 o) are
below the maximum bonding interaction distance of 3.82 Å as
calculated from Pythagoras’ theorem,21 suggesting the existence
of lone pair···π interactions. On the other hand, the C−H···π
interactions20 (C19−H19···π, 3.649(4) Å, ∠C−H···π = 129.3°,
C6−H6···π, 3.760(5) Å, ∠C−H···π = 129.2°) between the π
electron density of aryl ring and adjacent CH group are
observed. The combination of these lone pair···π and C−H···π
interactions, not involving any hydrogen bonding interactions,
results in the formation of the 3-D supramolecular network with
large channels. Moreover, the aforementioned 1-D nanotubes
fill in the channels, thus giving rise to the final 3-D network
(Figure S3, Supporting Information).
Figure 4. (a) Structure of crystal 5. (b) 2-D layer formed by O1w
molecules linking 1-D tapes. (c) 3-D supramolecular framework
strengthened by π···π interactions between the naphthyl rings and the
phenyl rings.
Adjacent sulfonate groups and unprotonated −N2H2 groups
in crystal 10 interact with each other through the N−H···O
hydrogen bonding interactions to form a 1-D chain motif along
the b-axis, which is decorated by the “arms” formed by sulfonyl
group and protonated −N1H3 group (Figure S4, Supporting
Information). Subsequently, the water molecules, as tetrapod
synthons, join adjacent two 1-D chains at the points of
H1N2 and O3 to generate a 1-D “centipede-shaped” chain
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Figure 5. (a) Structure of crystal 6. (b) Packing diagram of crystal 6
showing the N−H···π interactions denoted as white dashed lines.
(Figure 9b). In comparison with crystal 9, the O atoms of
the sulfonyl groups here form C/N−H···O interactions with
adjacent HSDA+ cations (C7−H7···O4, 3.191(6) Å, N1−
H1N1···O5, 2.922(3) Å), leading to 2-D layer motifs together
with the π···π interactions between two HSDA+ cations
(centroid-to-centroid distance being 3.928(2) Å), which are
further extended into 3-D supramolecular network with huge
1-D channels (Figure 9c) through C−H···π interactions20 among
phenyl rings and naphthyl rings (C14−H14···π, 3.747(4) Å,
∠C−H···π = 148.3°; C17−H17···π, 3.649(2) Å, ∠C−H···π =
147.0°). As observed in crystal 9, the aforementioned 1-D
“centipede-shaped” chains fill in the channels, thus giving rise
to the 3-D supramolecular network (Figure S5, Supporting
Information).
Hydrogen Bonding Modes of the −SO3 and −NH3
Groups. Both −SO3 and −NH3 groups have three sites to
form hydrogen bonding interactions; hence, multiple hydrogen
bonding modes could be generated according to the different
environments. For clarity, the hydrogen bonding modes of the
two −SO3 and −NH3 groups are denoted as AnAnAn (A = O or
H, n = 0, 1, 2). As shown in Scheme 2, the −SO3 and −NH3
groups in the 10 salts exhibit different hydrogen bonding modes,
which then leads to the formation of diverse [−SO3···H3N−]n
motifs. In crystal 10, the −SO3 and −NH3 groups exhibit a
simple A1A0A0 hydrogen bonding mode and interconnect with
each other to form the smallest [−SO3···H3N−] units, which are
interlinked through the unprotonated −N2H2 groups to form a
1-D chain. Two −SO3 and two −NH3 groups in crystal 5 exhibit
A1A1A0 (S1, N1) and A1A1A1 (S2, N2) hydrogen bonding
modes. The interconnection among the four groups generates
a finite [−SO3···H3N−]4 cluster which contains three identical
R44(12) graph sets consisting of two −SO3 and two −NH3
groups, that is, [2 + 2] ring. While the −SO3 and −NH3 groups
Figure 6. (a) Structure of crystal 7. (b) 2-D layer extended by the phenyl
rings of the m-HBDA2+ cations bridging 1-D [−SO3···H3N−]n ribbons.
(c) 3-D supramolecular network strengthened by π···π interactions
between the naphthyl rings and the phenyl rings.
in crystal 7 both present A1A1A1 hydrogen bonding mode, and
they connect each other to form a 1-D chain, which contains
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Figure 7. (a) Structure of crystal 8. (b) 3-D supramolecular network formed by (H2O)6 clusters (red shadow) bridging 2-D [−SO3···H3N−]n layer.
(c) 3-D supramolecular network strengthened by π···π interactions between the naphthyl rings and the phenyl rings.
continuous 12-membered rings described by the graph set
R44(12) ([2 + 2] ring). In crystal 9, two pairs of −SO3 and
−NH3 groups show different A2A1A0 (S1) and A1A1A1 (S2, N1,
N2) hydrogen bonding modes. Such intricate modes join
adjacent donors and acceptors to generate a 1-D nanotube. The
wall of the nanotube is composed of identical [5 + 5] rings
described by the graph set R190(28). It should be noted that the
same hydrogen bonding modes can also result in different
motifs due to the different connection direction. For example,
the −SO3 and −NH3 groups in crystal 6 present the same
modes as observed in crystal 9. However, adjacent donors and
acceptors link each other to form a 2-D planar layer containing
identical [3 + 3] rings described by the graph set R56(16).
Similarly, the two −SO3 and two −NH3 groups in crystal 8 also
exhibit A1A1A0 (S2, N1) and A1A1A1 (S1, N2) modes as
obseved in crystal 5. Owing to the different connection
direction, a 2-D planar layer consisting of [5 + 5] rings de-
10
10
scribed by the graph set R (30) is formed instead of the finite
[−SO3···H3N−]4 cluster. In crystals 1−3, the −NH3 groups all
exhibit the A2A1A1 mode, while the −SO3 groups exhibit the
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Figure 9. (a) Structure of crystal 10. (b) Side view and upward view of
the 1-D “centipede-shaped” chain bridging by the tetrapod water
molecules. (c) 3-D supramolecular network formed by the naphthyl
and phenyl rings through C−H···π, π···π, and sulfonyl involved C/N−
H···O interactions with huge 1-D channels.
Figure 8. (a) Structure of crystal 9. (b) 1-D [−SO3···H3N−]n
nanotube with the water molecules encapsulated. (c) 3-D supra-
molecular network formed by the naphthyl and phenyl rings through
C−H···π and sulfonyl involved lone pair···π interactions with huge 1-D
channels.
crystals, the interactions between the −SO3 and −NH3 groups
generate 2-D layer motifs, in which the −NH3 groups in crystals
1 and 2 are sandwiched between the −SO3 groups. The −NH3
groups in crystal 3 are only involved in a single planar layer due
A2A1A1 mode in crystals 1 and 3 and A2A2A0 mode in crystal 2.
Because of the similar hydrogen bonding modes in the three
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to the long aliphatic spacer between the two −NH3 groups.
However, despite the similar modes, they exhibit different
hydrogen bonding rings. For 1, the layers contain [2 + 4] and
[2 + 2] rings described by the graph set R44(14) and R33(8). For
2, the layers contain [2 + 4] and [4 + 4] rings described by the
graph set R46(12) and R48(16). For 3, the layers contain two types
of [2 + 2] rings described by the graph set R33(8) and R44(12). In
contrast to the above nine crystals, −SO3 and −NH3 groups in
crystal 4 present more intricate modes of A2A2A1 and connect
with each other to give rise to a 2-D planar layer motif which
contains [1 + 1] and three types of [3 + 3] rings described by
the graph set R22(4), R22(6), R33(8), and R44(12) (Scheme 2).
From these discussions, we can conclude that the diverse
hydrogen bonding modes of the sulfonate and −NH3 groups are
prone to form high dimensional hydrogen bonding motifs,
which then influence the final supramolecular networks.
interactions. The semirigid SDA molecule can provide addi-
tional supramolecular interaction site of the sulfonyl group and
result in different structures from the flexible aliphatic diamines
and rigid aromatic diamines. In crystal 9, the two protonated
amine groups are involved in the hydrogen bonding interactions
with sulfonate groups, which leads to the formation of a 1-D
nanotube. Adjacent nanotubes link to each other through eight
H2SDA2+ cations and NDS2− anions, thus generating a 3-D
supramolecular network with four H2SDA2+ cations captured
S1-containing NDS2− anions and two H2SDA2+ cations captured
S2-containing NDS2− anions through the C−H···π and lone
pair···π interactions. By contrast, in crystal 10, the hydrogen
bonding interactions among sulfonates, water molecules,
protonated and unprotonated amine groups link them into
a 1-D “centipede-shaped” chain. Adjacent chains link to each
other through six HSDA+ cations and NDS2− anions, generating
a 3-D supramolecular network with two HSDA+ cations
capturing one NDS2− anion through the C−H···π and π···π
interactions. In a word, as a result of the existence of the sulfonyl
group, crystal 9 possesses an organic 3-D supramolecular
network formed by the C−H···π and lone pair···π interactions
which encapsulates a 1-D infinite [−SO3···H3N−]n nanotube as
guests, while crystal 10 possesses an organic 3-D supramolecular
network formed by intricate C−H···π, π···π, and C/N−H···O
interactions which encapsulates a 1-D “centipede-shaped”
[−SO3···H3N−]n chain as guests. Accordingly, the nature of
the diamines can effectively influence the final architectures of
the salts through different noncovalent bonding interactions.
IR Spectroscopy. The stretching bands around 3400 cm−1
in the IR spectra of crystals 1−10, as well as the broad and
strong stretching bands appearing in the range of 3190−
2557 cm−1, can be attributed to the existence of the primary
ammonium cations, water molecules, as well as the formation of
extensive hydrogen bonding interactions. The bands appearing
in the range of 1638−1455 cm−1 in crystals 1−10 are ascribed
to the νCC and νC−N stretching vibrations of the NDS2−
anions and aromatic diamines. The IR spectra of the 10 crystals
Structural Diversities Tuned by Various Diamines.
From the standpoint of crystal engineering, the construction of
salts mainly depends on the intermolecular noncovalent
bonding interactions. Therefore, the properties of the organic
molecules involved will influence the structural diversities of the
final salts. In this article, hydrazine, four flexible aliphatic
diamines, three rigid and one semirigid aromatic diamines are
employed to construct salts with H2NDS. Structural analyses
indicate that six types of architectures are formed with the above
diamines. For crystals 1−5, three types of architectures are
formed owing to the different length of the aliphatic spacers,
−(CH2)n− (n = 0, 2−4) and −CH2−Ph−CH2−. In crystals
1−3, the protonated HA, EDA, and PDA molecules are all
sandwiched between the −SO3 groups through hydrogen
bonding interactions owing to the short and flexible or no
spacer, which further link by the naphthyl rings of the NDS2−
anions into a 3-D pillared layered supramolecular network.
Meanwhile, the C−H···π interactions among the naphthyl rings
of the NDS2− anions are detected in the three crystals. However,
owing to the long and flexible −(CH2)4− and −CH2−Ph−
CH2− spacers, the distances of 6.253 and 6.742 Å in crystals 4
and 5 between the two terminal −NH3 groups are close to that
of the two terminal −SO3 groups of NDS2− anions (6.854 and
6.873 Å), which lead to the formation of another two types of 3-
D supramolecular network instead of the 3-D pillared layered
network. Because of the shorter distances of 6.253 Å between
the two terminal −NH3 groups than that of 6.854 Å between
the two terminal −SO3 groups, crystal 4 exhibits a “honeycomb”
network. However, crystal 5 shows a different supramolecular
network from crystal 4 due to the existence of π···π interactions
among the intercrossed naphthyl rings and phenyl rings. In
comparison, crystals 6−10 containing aromatic diamines exhibit
another three types of architectures. In crystal 6, only one of the
two amines is protonated and interacts with the sulfonate group
through hydrogen bonding interactions to form a 2-D (6,3)
layer. Then, the naphthyl rings extend adjacent two layers into
2-D pillared layered network with the o-HBDA+ cations
arranging along the two sides of the layer. The other
unprotonated amine group forms strong N−H···π interactions
with the phenyl ring instead of participating in the formation of
hydrogen bonding interactions. The C−H···π interactions
between the naphthyl groups of the NDS2− anions are also
detected as observed in crystals 1−3. Different from crystal 6,
both the m-HBDA2+ and the H2MBDA2+ cations in crystals 7
and 8 interpenetrate with the NDS2− anions, thus leading to the
formation of a similar 3-D supramolecular network as observed
in crystal 5 through the hydrogen bonding and π···π stacking
−
show that the characteristic vibrations of νas(SO3 ) in crystals
1−10 are in the range of 1251−1149 cm−1, whereas the
10b,c
νs(SO3 ) absorptions are in the range of 1049−1029 cm−1.
−
Moreover, the separated sharp and strong bands of 3378 cm−1
in crystal 6 and 3344 cm−1 in crystal 10 are attributed to the
νN−H stretching vibrations, because the diamines in the two
crystal are only monoprotonated.
Thermogravimetric Analysis. To examine the thermal
stability of the 10 crystals, powder X-ray diffraction (PXRD)
patterns for solid samples of crystals 1−10 are first measured at
room temperature as illustrated in Figure S6, Supporting
Information. The patterns are highly similar to their simulated
ones (based on the single-crystal X-ray diffraction data),
indicating that the single-crystal structures are really representa-
tive of the bulk of the corresponding samples. Their stabilities
were analyzed on crystalline samples by thermogravimetric
analyses (TGA) from room temperature to 500 °C at a rate of
10 °C min−1, under N2 atmosphere. As shown in Figure S7,
Supporting Information, the sharp weight losses of crystals 1−4
occurred in the range of 310−350, 312−420, 315−380, and
360−430 °C, respectively. Crystal 5 lost the water molecules
in the range of 50−172 °C with the observed weight loss of
7.68% (calcd 7.83%), and then the following sharp weight loss
occurred between 310 and 390 °C. Meanwhile, Figure S8,
Supporting Information shows the TG curves of crystals 6−10,
in which crystals 6 and 7 exhibit a sharp weight loss in the range
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of 256−320 and 300−360 °C, respectively. For the three
hydrate crystals 8−10, gradually weight losses of water
molecules were observed. The loss of water molecules in
crystals 8−10 began at 65, 54, and 48 °C and finished at 120,
160, and 180 °C, respectively. The observed weight loss of
11.75% in 8, 3.51% in 9, and 2.39% in 10 is reasonably close to
the calculated value (11.64% in 8, 3.25% in 9, and 2.24% in 10).
Then, the sharp weight losses occurred in the range of 270−320,
300−325 and 280−330 °C for crystals 8−10.
transfer and the quantum efficiency, thus affording the strong
emission intensity of the final crystal. On the other hand, for
crystal 5, the π···π interactions among the naphthyl and phenyl
rings increase the mobility of the electrons, thus enhancing
the chance of intraligand charging transfer and the quantum
efficiency. Therefore, crystal 5 exhibits the strongest emission
intensity among the five crystals constructed from aliphatic
diamines.
For series II, as shown in Figure S10, Supporting Information,
upon the different excitations, the emission spectra of crystals
Luminescent Property. The luminescent properties of
crystals 1−10 and the reactants at room temperature were
investigated. The HA, EDA, PDA, BTDA, and BDMA molecules
cannot exhibit obvious emission under UV irradiation, while the
o-BDA, m-BDA, MBDA, and SDA molecules exhibit strong
emissions at 354 (λex = 285 nm), 342 (λex = 313 nm), 341 (λex =
279 nm), and 377 nm (λex = 248 nm), respectively. For clarity,
the 10 salts are divided into series I (crystals 1−5), II (crystals
6−8), and III (crystals 9, 10) to be discussed.
6−8 exhibit a maximum at 345 (λex = 241 nm), 337 (λex
=
241 nm), and 340 (λex = 287 nm), respectively. In contrast
to the reactants, the emission bands of crystals 6−8 are
probably assigned to the intraligand (IL) π−π* transitions of
their corresponding aromatic diamine molecules. Different
from series I, the emission intensities of the three crystals in
series II are all obviously decreased in comparison with the
corresponding aromatic diamine molecules, which could be
explained as follows. For crystals 7 and 8, partial excited
electrons of m-H2BDA2+ and H2MBDA2+ transfer to the excited
state of NDS2− through the π···π interactions, which are then
quenched through the nonradioactive transition. The quantum
efficiency is subsequently reduced, thus resulting in the
decrease of the emission intensity. The nearly quenching
luminescent emission of the monoprotonated crystal 6 could be
ascribed to the formation of the strong N−H···π interactions
and the asymmetric amine group and ammonium cation
attached to the phenyl ring, which result in the asymmetric
charge distribution in the phenyl ring of the o-HBDA+, and
subsequently effectively limit the charge transfer and decrease
the quantum efficiency.
For series I, as shown in Figure S9, Supporting Information,
upon the different excitations, the emission spectra of crystals
1−5 exhibit a similar shape and maximum at 376 (λex
=
345 nm), 388 (λex = 250 nm), 397 (λex = 340 nm), 359 (λex =
243 nm), and 348 nm (λex = 243 nm), respectively. The emission
bands of these crystals are probably assigned to the intraligand
(IL) π−π* transitions of H2NDS because the resemblance of
the emission spectra in comparison with free H2NDS molecules
(λex = 353 nm, λem = 407 nm). Meanwhile, the emission
intensities of the five crystals are significantly larger than that
of H2NDS molecules, especially for crystals 1, 4, and 5
(Figure 10). The increasing emission intensity of crystals is
For series III, as shown in Figure S10, Supporting Information,
upon the different excitations, the emission spectra of crystals 9
and 10 exhibit maximum at 344 (λex = 288 nm) and 407 nm
(λex = 330 nm). Although the mechanism for the emission is
not clear at this moment, the adscription of the emission can
be achieved according to those of series I and II. In contrast
to the emission spectrum of SDA, the emission band of crystal
9 is probably assigned to the intraligand (IL) π−π* transitions
of SDA molecule because the resemblance of their emission
spectra. The decreasing of the emission intensity of this crystal
is similar as the case in series II. By contrast, the emission band
of crystal 10 is probably be assigned to the intraligand (IL)
π−π* transitions of H2NDS because of the resemblance of
the emission spectra in comparison with free H2NDS mole-
cules. The increase of the emission intensity of this crystal is
similar as the case in series I and can be probably attributed to
the formation of the continuous C−H···π interactions among
adjacent NDS2− and HSDA+, which effectively restrict the
flexibility and increase the rigidity of the NDS2− anions, thus
reducing the loss of energy.22 Owing to the visibly emission
differences between the aliphatic diamines containing series and
rigid aromatic diamines containing series, H2NDS might be
used to distinguish the aliphatic diamine from aromatic diamine
qualitatively through the luminescent signal.
Figure 10. Comparison of the emission intensities among the
reactants and crystals 1−10.
probably attributed to the formation of extensive hydrogen
bonds, which effectively restrict the flexibility and increase the
rigidity of the NDS2− anions, such as the parallel naphthyl rings
in crystal 4, thus reducing the loss of energy.22 Moreover, it is
interesting to note that the emission intensities and the blue
shift values of crystals 1−3 exhibit a regular decreasing with the
sequence of 1−3. This change may be mainly ascribed to the
diverse structures of the three crystals. As depicted above, all
the three crystals exhibit a similar 3-D pillared layered supra-
molecular network extended by the hydrogen bonding inter-
actions and the C−H···π interactions. However, the C···π
distances in the three crystals are increased from 3.488(2)
(in 1), to 3.642(2) (in 2), and 3.806(4) Å (in 3). The short
C···π distance increases the chance of intraligand charging
CONCLUSIONS
■
In summary, 10 well-designed supramolecular patterns of salts
assembled by 1,5-naphthalenedisulfonic acid with hydrazine,
four flexible aliphatic diamines, three rigid and one semirigid
aromatic diamines have been synthesized and characterized.
The nature of the diamines can effectively influence the final
architectures of the salts through different hydrogen bonding
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(8) (a) Ma, J. C.; Dougherty, D. A. Chem. Rev. 1997, 97, 1303.
(b) Schneider, H. J. Angew. Chem., Int. Ed. 2009, 48, 3924.
(9) (a) Egli, M.; Sarkhel, S. Acc. Chem. Res. 2007, 40, 197.
(b) Schottel, B. L.; Chifotides, H. T.; Dunbar, K. R. Chem. Soc. Rev.
2008, 37, 68.
(10) (a) Shimizu, G. K. H.; Vaidhyanathan, R.; Taylor, J. M. Chem.
Soc. Rev. 2009, 38, 1430. (b) Deng, Z.-P.; Huo, L.-H.; Li, M.-S.; Zhang,
L.-W.; Zhu, Z.-B.; Zhao, H.; Gao, S. Cryst. Growth Des. 2011, 11, 3090.
(c) Fang, X.-Q.; Deng, Z.-P.; Huo, L.-H.; Wan, W.; Zhu, Z.-B.; Zhao,
H.; Gao, S. Inorg. Chem. 2011, 50, 12562.
interactions and other noncovalent bonding interactions, such
as π···π stacking, N−H···π, C−H···π, as well as the lone pair···π
interactions. Different hydrogen bonding modes formed by −SO3
and −NH3 groups result in diverse [1 + 1], [2 + 2], [2 + 4],
[3 + 3], [4 + 4], and [5 + 5] hydrogen bonding rings, which
then generate six types of architectures with the assistance of
the above noncovalent bonding interactions. Luminescent in-
vestigations demonstrate that the salts containing aliphatic
diamines exhibit stronger emission intensity than those con-
taining aromatic diamines. This result indicates that the H2NDS
might be used to distinguish the aliphatic diamine from
aromatic diamine qualitatively through the luminescent signal.
The present study provides a strategy to tune the supra-
molecular patterns and modify the luminescent properties of
salts assembled by arenesulfonic acids and diamines. Further
investigation on syntheses, structures, and properties of salts
constructed from other arenesulfonic acids and amines are also
underway in our laboratory.
(11) (a) Reddy, D. S.; Duncan, S.; Shimizu, G. K. H. Angew. Chem.,
Int. Ed. 2003, 42, 1360. (b) Videnova-Adrabinska, V. Coord. Chem. Rev.
2007, 251, 1987. (c) Chandrasekhar, V.; Singh, P. Cryst. Growth Des.
2010, 10, 3077.
(12) Cambridge Structure Database search, CSD Version 5.27
(November 2005) with 19 updates (January 2006-Nov 2011).
(13) (a) Mizobe, Y.; Ito, H.; Hisaki, I.; Miyata, M.; Hasegawa, Y.;
Tohnai, N. Chem. Commun. 2006, 2126. (b) Mizobe, Y.; Hinoue, T.;
Yamamoto, A.; Hisaki, I.; Miyata, M.; Hasegawa, Y.; Tohnai, N.
Chem.Eur. J. 2009, 15, 8175.
(14) Tohnai, N.; Mizobe, Y.; Doi, M.; Sukata, S.; Hinoue, T.; Yuge,
T.; Hisaki, I.; Matsukawa, Y.; Miyata, M. Angew. Chem., Int. Ed. 2007,
46, 2220.
ASSOCIATED CONTENT
■
S
* Supporting Information
(15) Hinoue, T.; Miyata, M.; Hisaki, I.; Tohnai, N. Angew. Chem., Int.
Ed. 2012, 51, 155.
Additional figures, PXRD patterns, TG curves, UV spectra,
emission spectra for all crystals, as well as the X-ray
crystallographic files in CIF format. This material is available
free of charge via the Internet at http://pubs.acs.org.
(16) (a) Russell, V. A.; Evans, C. C.; Li, W. J.; Ward, M. D. Science
1997, 276, 575. (b) Pivovar, A. M.; Holman, K. T.; Ward, M. D. Chem.
Mater. 2001, 13, 3018. (c) Holman, K. T.; Pivovar, A. M.; M. Ward, D.
Science 2001, 294, 1907. (d) Holman, K. T.; Pivovar, A. M.; Swift, J. A.;
Ward, M. D. Acc. Chem. Res. 2001, 34, 107. (e) Custelcean, R.; Ward,
M. D. Angew. Chem., Int. Ed. 2002, 41, 1724. (f) Burke, N. J.; Burrows,
A. D.; Mahon, M. F.; Warren, J. E. CrystEngComm 2006, 8, 931.
(17) (a) Leverd, P. C.; Berthault, P.; Lance, M.; Nierlich, M. Eur. J.
Inorg. Chem. 2000, 133. (b) Perret, F.; Bonnard, V.; Danylyuk, O.;
Suwinska, K.; Coleman, A. W. New J. Chem. 2006, 30, 987. (c) Su, X.;
Guo, D.-S.; Liu, Y. CrystEngComm 2010, 12, 947. (d) Yin, W.-X.;
Huang, X.-Y.; Xu, X.-M.; Meng, X.-G. Acta Crystallogr. 2010, C66,
o508.
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: shangao67@yahoo.com (S. G.); E-mail: lhhuo68@
yahoo.com (L-H. H.).
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
(18) Sheldrick, G. M. SHELXTL-97, Program for Crystal Structure
■
Solution and Refinement; University of Gottingen: Gottingen, Germany,
̈
This work is financial supported by the Key Project of
Natural Science Foundation of Heilongjiang Province (No.
ZD200903), Key Project of Education Bureau of Heilongjiang
Province (No. 12511z023, No. 2011CJHB006), the Innovation
team of Education Bureau of Heilongjiang Province (No.
2010td03) and Program for New Century Excellent Talents in
University (NCET-06-0349). We thank the University of
Heilongjiang (Hdtd2010-04) for supporting this study.
1997.
(19) Zhu, Z.-B.; Gao, S.; Ng, S. W. Acta Crystallogr. 2009, E65,
o2658.
(20) (a) Shi, Y.-Y.; Sun, J.; Huang, Z.-T.; Zheng, Q.-Y. Cryst. Growth
Des. 2010, 10, 314. (b) Hazra, S.; Sarkar, B.; Naiya, S.; Drew, M. G. B.;
Frontera, A.; Escudero, D.; Ghosh, A. Cryst. Growth Des. 2010, 10,
1677.
(21) Mooibroek, T. J.; Black, C. A.; Gamez, P.; Reedijk, J. Cryst.
Growth Des. 2008, 8, 1082.
(22) Rendell, D. Fluorescence and Phosphorescence; Wiley: New York,
1987.
REFERENCES
(1) (a) Yan, D.; Delori, A.; Lloyd, G. O.; Frisc
Jones, W.; Lu, J.; Wei, M.; Evans, D. G.; Duan, X. Angew. Chem., Int.
■
̌
i
̌
c,
́
T.; Day, G. M.;
Ed. 2011, 50, 12483. (b) Frisc
(2) (a) Schultheiss, N.; Newman, A. Cryst. Growth Des. 2009, 9, 2950.
(b) Fabían, L.; Hamill, N.; Eccles, Moynihan, K. S. H. A.; Maguire, A.
R.; McCausland, L.; Lawrence, S. E. Cryst. Growth Des. 2011, 11, 3522.
(c) Arenas-García, J. I.; Herrera-Ruiz, D.; Mondragon-Vasquez, K.;
̌ ̌ ́
ic, T. Chem. Soc. Rev. 2012, 41, 3493.
́
́
́
Morales-Rojas, H.; Hopfl, H. Cryst. Growth Des. 2012, 12, 811.
̈
̈
(3) Almarsson, O.; Zaworotko, M. Chem. Commun. 2004, 1889.
(4) Desiraju, G. Angew. Chem., Int. Ed. 2003, 34, 2311.
(5) (a) Parthasarathi, R.; Subramanian, V.; Sathyamurthy, N. J. Phys.
Chem. A 2006, 110, 3349. (b) Jeffrey, G. A. An Introduction to
Hydrogen Bonding; Oxford University Press: Oxford, 1997.
(6) (a) Janiak, C. J. Chem. Soc., Dalton Trans. 2000, 3885.
(b) Grimme, S.; Antony, J.; Schwabe, T.; Muck-Lichtenfeld, C. Org.
Biomol. Chem. 2007, 5, 741.
(7) (a) Takahashi, H.; Tsuboyama, S.; Umezawa, Y.; Honda, K.;
Nishio, M. Tetrahedron 2000, 56, 6185. (b) Nishio, M. CrystEngComm
2004, 6, 130.
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