The crystal structures of ten supramolecular adducts of benzylamine and organic acids

Article abstract of DOI:10.1016/j.molstruc.2019.127538

This article demonstrates the benzylamine based supramolecular adducts formation in ten crystalline solids 1–10, in which the acidic moiety have been integrated. Addition of the organic acid to the solution of benzylamine generates the corresponding supramolecular assemblies. All the compounds crystallize as their organic salts with the acidic H at the acids transferred to the NH₂ of the benzylamine. All salts have been characterized via infrared spectroscopy, melting point, elemental analysis and X-ray diffraction analysis technique. The major driving force in 1–10 is attributed to the classical H-bonds from benzylamine and the acids. The other extensive non-covalent interactions also play great functions in space association of the molecular counterparts in relevant crystals. The homo or hetero supramolecular synthons or both were found at these salts and the common R₄ ²(8), R₄ ³(10) and R₄ ⁴(12) graph sets have been frequently observed in the salts due to the H-bonds and non-covalent associations. For the synergistic effects of the classical H-bonds and the various non-covalent bonds, these salts displayed 2D/3D structures.

Full text of DOI:10.1016/j.molstruc.2019.127538

Journal Pre-proof
The crystal structures of ten supramolecular adducts of benzylamine and organic
acids
Linfang Mo, Shouwen Jin, Weiting Zhang, Jianzhong Guo, Hui Liu, Daqi Wang
PII:
S0022-2860(19)31647-3
DOI:
https://doi.org/10.1016/j.molstruc.2019.127538
MOLSTR 127538
Reference:
To appear in: Journal of Molecular Structure
Received Date: 2 November 2017
Revised Date: 2 December 2019
Accepted Date: 3 December 2019
Please cite this article as: L. Mo, S. Jin, W. Zhang, J. Guo, H. Liu, D. Wang, The crystal structures of ten
supramolecular adducts of benzylamine and organic acids, Journal of Molecular Structure (2020), doi:
https://doi.org/10.1016/j.molstruc.2019.127538.
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Graphical abstract
Title: The Crystal Structures of Ten Supramolecular Adducts of Benzylamine
and Organic Acids
a
a
a
a
a
Linfang Mo , Shouwen Jin *, Weiting Zhang , Jianzhong Guo , Hui Liu , and Daqi
b
Wang
a
ZheJiang A & F University, Donghu campus, Lin'An 311300, China. *E-mail:
jinsw@zafu.edu.cn
b
Department of Chemical engineering, Liaocheng University, 252059, China.

The Crystal Structures of Ten Supramolecular Adducts of Benzylamine and
Organic Acids
a
a
a
a
a
Linfang Mo , Shouwen Jin *, Weiting Zhang , Jianzhong Guo , Hui Liu , and Daqi
b
Wang
a
ZheJiang A & F University, Donghu campus, Lin'An 311300, China. *E-mail:
jinsw@zafu.edu.cn
b
Department of Chemical engineering, Liaocheng University, 252059, China.
Abstract:
This article demonstrates the benzylamine based supramolecular adducts
formation in ten crystalline solids 1-10, in which the acidic moiety have been
integrated. Addition of the organic acid to the solution of benzylamine generates the
corresponding supramolecular assemblies. All the compounds crystallize as their
organic salts with the acidic H at the acids transferred to the NH of the benzylamine.
2
All salts have been characterized via infrared spectroscopy, melting point, elemental
analysis and X-ray diffraction analysis technique. The major driving force in 1-10 is
attributed to the classical H-bonds from benzylamine and the acids. The other
extensive non-covalent interactions also play great functions in space association of
the molecular counterparts in relevant crystals. The homo or hetero supramolecular
2
3
4
4
4
synthons or both were found at these salts and the common R (8), R (10) and R (12)
4
graph sets have been frequently observed in the salts due to the H-bonds and
non-covalent associations. For the synergistic effects of the classical H-bonds and the
various non-covalent bonds, these salts displayed 2D/3D structures.
Keywords: Structure characterization; H-bonding; benzylamine; Organic acids;
Supramolecular interactions.

Introduction
Noncovalent interactions such as electrostatic forces, H-bonds, CH-π, π-π
stacking, cation-π, anion-π and lone pair-π contacts, as well as other weak forces play
significant roles in various fields ranging from molecular recognition, host-guest
chemistry, crystal engineering, supramolecular chemistry, biochemistry,
pharmaceutical chemistry, to materials science [1-4]. The phenomenon of
noncovalent interactions provided much intrinsic information on the molecular
recognition and crystal-engineering and there have been great interest in preparing
organic ensembles. In the past few years, great efforts have been made to illuminate
these interactions and their relationship to the final supramolecular architectures [5].
In the case of pharmaceutical ingredients, solid cocrystals/salts formation being
an effective method in regulating such biopharmaceutical properties as solubility,
stability and hygroscopicity have been studied systematically and these properties are
relevant to the non-covalent interactions [6-7]. The organic acid bears the nice
donor-acceptor groups for the supramolecular crystal engineering [8] and they
aggregate in the crystalline solid as dimer, catemer and bridged motifs [9]. It is very
significative to study the powerful and directional recognition behavior between the
organic acids and the basic components of aromatic amine, aliphatic amine and
pyridyl derivatives [10]. In addition to the acidic groups, the CH O, CH , X (halogen),
3
2
OH and aryl moieties are all excellent groups in making the organic crystalline solids
by a wide variety of non-covalent interactions [11], thus we select the ten acids
bearing the above mentioned side groups. As a common primary amine, except the
basic NH , benzylamine with the additional rigid aryl ring and the somewhat flexible
2
CH linker can produce more intricate noncovalent associations when it interacted
2
with the organic acids. To the best of our knowledge there are few reports dealing
with the organic acid-base salts concerning the benzylamine [12, 13].
In continuation with our endeavour towards the study of the H-bonding, π-π
interaction and halogen bonding from the given N-bearing derivatives with varying
the organic acids [14], so we will demonstrate the preparation and structure
characterizations of ten salts based on benzylamine (L) and organic acids (Scheme 1).

+
-
-
The ten salts are (benzylamine) : (dichloroacetic acid) (1) [(HL) · (dca ), dca =
+
-
-
dichloroacetate], (benzylamine) : (1-naphthoic acid) (2) [(HL) · (napa ), napa =
+
-
-
1
-naphthoate], (benzylamine) : (vanillic acid) (3) [(HL) · (vana ), vana = vanillate],
+
2-
2-
(
benzylamine)2 : (5-hydroxy-isophthalic acid) (4) [(HL)2 · (ipa ), ipa
=
5
-hydroxy-isophthalate], (benzylamine) : (4-bromo-3,5-dimethoxy-benzoic acid) (5)
+
2-
2-
[
(
(
[
(
(
(
(
(HL) · (bdmba ), bdmba = 4-bromo-3,5-dimethoxy-benzoate], (benzylamine) :
+
-
-
3,5,6-trichlorosalicylic acid) (6) [(HL) · (tcsal ), tcsal = 3,5,6-trichlorosalicylate],
benzylamine)2
:
(1,4-naphthalenedicarboxylic
acid)
:
(H O)
(7)
2
+
2-
2-
(HL ) · (napt) · (H O), (napt) = 1,4-naphthalenedicarboxylate], (benzylamine) :
2
2
2
+
2-
dodecanedioic acid) (8) [(HL ) · (doda) , doda = dodecanedioate], (benzylamine) :
2
+
tribromophenol) (9) [(HL ) · (tbpl), tbpl = tribromophenolate] and (benzylamine) :
+
2-naphthalene sulfonic acid) (10) [(HL ) · (napsa), napsa = 2-naphthalene sulfonate]
Scheme 2). The synthons in 1-10 were provided in Scheme 3.
O
O
OH
COOH
OH
H N
2
Cl
OCH3
Cl
dichloroacetic acid
OH
benzylamine
1-naphthoic acid
vanillic acid
HO
Cl
O
COOH
O
OH
O
HO
H CO
3
OCH3
HO
Cl
Cl
OH
-hydroxy-isophthalic acid
Br
5
4-bromo-3,5-dimethoxy-benzoic acid
3,5,6-trichlorosalicylic acid
HO
O
O
OH
Br
O
HO
HO
Br
Br
HO
O
tribromophenol
dodecanedioic acid
1,4-naphthalenedicarboxylic acid
O
S
OH
O
2
-naphthalene sulfonic acid
Scheme 1 Molecular structures of the components in 1-10.

Scheme 2 The organic salts 1-10 in this paper from the XRD data.

Scheme 3 Supramolecular synthons in 1-10 from the XRD analysis.
Experimental part
Materials and Instrumentation
The chemicals and solvents utilized in this manuscript are analytical grade
commercial products and used without purification. FT-IR spectra in range 4000-400
-1
cm were recorded on a Mattson Alpha-Centauri spectrometer from KBr discs and the
IR bands were marked as s = strong, m = medium and w = weak at the preparation
part. The C, H, N and S data were measured micro-analytically on a Perkin-Elmer
elemental analyzer with Model 2400II and the melting points of the salts were
measured by an XT-4 thermal instrument without correction.

Synthesis of salts 1-10
Typical preparation procedure
To a methanol solution (8 mL) of dichloroacetic acid (25.8 mg, 0.2 mmol) was
added benzylamine (21.4 mg, 0.2 mmol) with constant stirring for 5 minutes, then the
solution was filtered into a test tube. The solution was left standing at room
temperature for 12 days, colorless crystals were isolated after slow evaporation of the
methanol solution in air. The crystals were collected and dried in air to give
+
-
(
benzylamine) : (dichloroacetic acid) [(HL) · (dca )] (1). Yield: 36 mg, 76.24%. m. p.
8
9-90 °C. Anal. Calcd for C H Cl NO (236.09): C, 45.74; H, 4.66; N, 5.93. Found:
9
11
2
2
-1
C, 45.62; H, 4.59; N, 5.80. Infrared spectrum (KBr disc, cm ): 3455s(ν (NH)),
as
3
1
1
8
374s(ν (NH)), 3226m, 3148m, 3054m, 2966m, 2872m, 2828m, 2777m, 2735m,
s
-
-
628m, 1594s(ν (COO )), 1550m, 1508m, 1464m, 1422m, 1382s(ν (COO )), 1340m,
as
s
297m, 1256m, 1214m, 1172m, 1130m, 1088m, 1048m, 1010m, 968m, 925m, 883m,
41m, 798m, 756m, 714m, 672m, 636m, 610m.
Similar procedure was utilized to prepare 2-10
+
-
(
benzylamine) : (1-naphthoic acid) [(HL) · (napa )] (2). Yield: 44 mg, 78.76%. m.
p. 182-184 °C. Anal. Calcd for C H NO (279.33): C, 77.33; H, 6.08; N, 5.01.
1
8
17
2
-1
Found: C, 77.16; H, 5.94; N, 4.86. Infrared spectrum (KBr disc, cm ):
-
3
1
1
7
472w(ν (NH)), 3350m(ν (NH)), 3270w, 3154m, 3048m, 2970m, 1616s(υ (CO )),
as
s
as
2
-
554m, 1512m, 1468m, 1426m, 1384s(υ (CO )), 1342m, 1300m, 1258m, 1215m,
s
2
173m, 1132m, 1088m, 1046m, 1004m, 964m, 922m, 878m, 836m, 794m, 752m,
10m, 666m, 624m, 602m.
+
-
(
benzylamine) : (vanillic acid) [(HL) · (vana )] (3). Yield: 46 mg, 83.54%. m. p.
1
94-196 °C. Anal. Calcd for C H NO (275.30): C, 65.38; H, 6.18; N, 5.08. Found:
1
5
17
4
-1
C, 65.26; H, 5.94; N, 4.88. Infrared spectrum (KBr disc, cm ): 3722w(ν(OH)),
3
1
1
450s(ν (NH)), 3372s(ν (NH)), 3264m, 3167m, 3076m, 2944m, 2868m,
as s
-
-
618s(ν (COO )), 1574m, 1532m, 1488m, 1444m, 1402s(ν (COO )), 1358m, 1315m,
as
s
272m, 1230m, 1186m, 1148m, 1106m, 1064m, 1022m, 978m, 934m, 888m, 846m,

8
04m, 760m, 718m, 676m, 634m, 608m.
+
2-
(
benzylamine) : (5-hydroxy-isophthalic acid) [(HL) · (ipa )] (4). Yield: 50 mg,
2
2
6
3.06% (based on benzylamine). m. p. 219-220 °C. Anal. Calcd for C H N O
5
22
24
2
(396.43): C, 66.59; H, 6.05; N, 7.06. Found: C, 66.52; H, 5.86; N, 6.88. Infrared
-1
spectrum (KBr disc, cm ): 3584w(ν(OH)), 3476s(ν (NH)), 3358s(ν (NH)), 3252m,
as
s
-
3
1
1
184m, 2988m, 2864m, 1614s(ν (COO )), 1566m, 1530m, 1488m, 1446m,
as
-
404s(ν (COO )), 1358m, 1318m, 1275m, 1232m, 1190m, 1145w, 1104m, 1062m,
s
020m, 978m, 936m, 894m, 850m, 808m, 764m, 722m, 676m, 646m, 620m, 608m.
+
2-
(
benzylamine) : (4-bromo-3,5-dimethoxy-benzoic acid) [(HL) · (bdmba )] (5).
Yield: 52 mg, 70.61%. m. p. 198-200 °C. Anal. Calcd for C H BrNO (368.22): C,
1
6
18
4
5
2.14; H, 4.89; N, 3.80. Found: C, 52.02; H, 4.78; N, 3.66. Infrared spectrum (KBr
-1
disc, cm ): 3472s((ν (NH))), 3355s(ν (NH)), 3260m, 3176m, 2945m, 2867m, 2788m,
as
s
1
1
7
624m, 1582s(ν (COO)), 1540m, 1498m, 1454m, 1406s(ν (COO)), 1362m, 1320m,
a
s
s
278m, 1235m, 1194m, 1152m, 1110m, 1065m, 1022m, 877m, 833m, 792m, 750m,
06m, 666m, 628m, 604m.
+
-
(
benzylamine) : (3,5,6-trichlorosalicylic acid) [(HL) · (tcsal )] (6). Yield: 58 mg,
8
3.19%. m. p. 184-186 °C. Anal. Calcd for C H Cl NO (348.60): C, 48.19; H, 3.44;
1
4
12
3
3
-1
N, 4.02. Found: C, 48.10; H, 3.32; N, 3.92. Infrared spectrum (KBr disc, cm ):
3
2
1
8
702w(ν(HO), 3440m(ν (NH)), 3380w(ν (NH)), 3264m, 3149m, 2988m, 2846w,
as s
-
-
784w, 1597s(ν (COO )), 1554m, 1515m, 1474m, 1433m, 1391s(ν (COO )), 1346m,
as
s
304m, 1263m, 1220m,, 1179m, 1136m, 1094m, 1053m, 1009m, 965m, 917m, 875m,
33m, 787m, 746m, 700m, 656m, 621m, 600m.
(benzylamine)2
:
(1,4-naphthalenedicarboxylic
acid)
:
(H O)
2
+
2-
[
(HL ) · (napt) · (H O)] (7). Yield: 36 mg, 80.27% (based on benzylamine). m. p.
2
2
2
08-210°C. Anal. Calcd for C H N O (448.50): C, 69.56; H, 6.24; N, 6.24. Found:
26 28 2 5
-1
C, 69.47; H, 6.16; N, 6.18. Infrared spectrum (KBr disc, cm ): 3652m(broad, ν(OH)),

3
1
1
7
446s(ν (NH)), 3352s(ν (NH)), 3258m, 3164m, 3062m, 2974m, 2880m, 2770m,
as s
610s(ν (COO)), 1568m, 1526m, 1484m, 1440m, 1398s(ν (COO)), 1355m, 1312m,
as
s
270m, 1228m, 1186m, 1142m, 1098m, 1054m, 1016m, 972m, 928m, 884m, 842m,
98m, 753m, 710m, 668m, 626m, 604m.
+
2-
(
benzylamine) : (dodecanedioic acid) [(HL ) · (doda) ] (8). Yield: 30 mg,
2
2
6
7.48% (based on benzylamine). m. p. 108-110°C. Anal. Calcd for C H N O
26 40 2 4
(444.60): C, 70.18; H, 9.00; N, 6.30. Found: C, 69.98; H, 8.86; N, 6.18. Infrared
-1
spectrum (KBr disc, cm ): 3448s(ν (NH)), 3362s(ν (NH)), 3270m, 3168m, 3090m,
as
s
-
-
2
1
8
944m, 2864m, 1618s(ν (COO )), 1560m, 1515m, 1474m, 1432m, 1380s(ν (COO )),
as s
336m, 1292m, 1250m, 1208m, 1166m, 1123m, 1082m, 1040m, 998m, 958m, 918m,
75m, 832m, 788m, 746m, 704m, 662m, 625m, 604m.
+
(
benzylamine) : (tribromophenol) [(HL ) · (tbpl)] (9). Yield: 32 mg, 73.06%. m. p.
7
9-81°C. Anal. Calcd for C H Br NO (437.97): C, 35.62; H, 2.74; N, 3.20. Found:
13 12 3
-1
C, 35.50; H, 2.62; N, 3.06. Infrared spectrum (KBr disc, cm ): 3465s(ν (NH)),
as
3
1
1
6
338s(ν (NH)), 3254m, 3188m, 3136m, 2962m, 2888m, 2846m, 2820m, 1622m,
s
568m, 1526m, 1484m, 1440m, 1400m, 1358m, 1314m, 1272m, 1228m, 1180m,
136m, 1092m, 1046m, 1004m, 960m, 915m, 870m, 826m, 782m, 744m, 696m,
55m, 632m, 608m.
+
(
benzylamine) : (2-naphthalene sulfonic acid) [(HL ) · (napsa)] (10). Yield: 18 mg,
5
4
3
2
1
8
7.07%. m. p. 104-106°C. Anal. Calcd for C H NO S (315.38): C, 64.68; H, 5.39; N,
17 17 3
-1
.44. Found: C, 64.54; H, 5.28; N, 4.32. Infrared spectrum (KBr disc, cm ):
438s(ν (NH)), 3340s(ν (NH)), 3236m, 3144m, 3052m, 2968m, 2866m, 2824m,
as
s
776m, 2732m, 1626m, 1584m, 1537m, 1495m, 1454m, 1412m, 1370m, 1330m,
286m, 1242m, 1198m, 1156m, 1114m, 1070m, 1028m, 986m, 942m, 900m, 858m,
16m, 772m, 732m, 688m, 646m, 622m.
X-ray Crystallography
The single crystals of suitable quality were mounted on a glass fiber on a Bruker

SMART 1000 CCD diffractometer operating at 50 kV and 40 mA using graphite
monochromatized Mo Kα radiation (0.71073 Å). Data collection and reduction were
carried out by SMART and SAINT softwares [15]. The structures were solved
directly and the non-Hs were refined anisotropically via full-matrix least squares on
2
F with SHELXL program of the SHELXTL package [16]. H-atom positions for the
1
0 structures were located in a difference map and refined independently. The
summaries of the key crystallographic information are given in Tables 1-2, selected
bond lengths and angles are tabulated in Table 3 and the relevant H-bonds in Table 4.
Table 1. should be inserted here.
Table 2. should be inserted here.
Results and Discussion
Preparation and General Characterization
During the preparation of 1-10, the acids were mixed directly with benzylamine
with 1:1 of the acidic group and the benzylamine in methanol and the crystalline
products were formed via the solvent evaporation method. Except 7, all compounds
crystallized without H O in the lattice and neither the compounds are sensitive to the
2
humidity. The EA data and the IR of the ten salts fit highly with their chemical
components measured by the XRD. Hs attached to O/N are well found via the
difference electron density map.
-
1
The N-H/O-H stretchings were at 3722-3338 cm as strong and broad bands in the
-1
IR of the ten salts. The respective moderate bands at 1500-1630 and 600-750 cm
arise from the aryl ring stretching and bending. IR is also very useful for diagnosing
-
2
the carboxylates [17]. The existence of the CO in 1-8 is supported by the strong
-1
-1
asymmetrical (1582-1618 cm ) and symmetrical (1380-1404 cm ) stretching bands
-
for CO [18].
2
Table 3. should be inserted here.
Table 4. should be inserted here.
Molecular and supramolecular structure of (benzylamine) : (dichloroacetic acid)
+
-
[
(HL) · (dca )] (1)
Fig. 1 should be inserted here.

+
-
Salt 1 with the composition [(HL) · (dca )] was obtained by reacting equal mol
of L with dichloroacetic acid, in which dichloroacetic acid donated the H at the CO H
2
+
-
to the NH of the L. The asymmetric unit of 1 consists of one HL and one dca (Fig.
2
1
s). The dichloroacetic acid exists in the ionized mode with C-O bonds of 1.249(4) Å
(O(1)-C(8)) and 1.219(4) Å (O(2)-C(8)), which differs significantly from that at the
parent crystal of dichloroacetic acid [19], but it is comparable with the corresponding
values at 4-dimethylaminopyridinium dichloroacetate dichloroacetic acid [20] and
1
,3-dihydroxy-2-(hydroxymethyl)-propan-2-aminium 2,2-dichloroacetate [21].
+
-
One HL and one dca make a heteroadduct by the N-H···O H-bond with N-O
separation of 2.792(3) Å. Along the b axis the heteroadducts were constituted into 1D
+
-
chain by the N-H···O H-bonds from the remaining H of the NH and the CO with
3
2
N-O distances of 2.765(4)-2.799(4) Å and N-H···Cl H-bond with N-Cl separation of
3
.420(3) Å. Within the crystal, the chains were arranged into 2D sheet extending
-
parallel to the ab plane (Fig. 1) by the CH-O association from the CHCl and the CO
2
2
with C-O separation of 3.287 Å. In addition, the 2D sheet is stabilized further by the
CH-Cl association between the CHCl units with C-Cl separation of 3.662 Å and
2
+
CH -Cl association from the CH linker at the HL and the Cl with C-Cl separation of
2
2
3
.783 Å. The C-Cl distances at CH-Cl/CH -Cl contacts are comparable with the
2
2
2
2
3
3
known results [22]. The sheet have the I R (5), II R (5), III R (9), IV R (12), V
1
1
3
3
4
3
3
4
4
4
4
4
5
5
R (10), VI R (10), VII R (12), VIII R (13), IX R (15), X R (14), XI R (17), XII
4
4
5
6
6
6
6
R (22), XIII R (22) and XIV R (23) rings.
6
6
Molecular and supramolecular structure of (benzylamine) : (1-naphthoic acid)
+
-
[
(HL) · (napa )] (2)
Fig. 2 should be inserted here.
Compound 2 crystallizes in triclinic P-1 space group and the crystal structure of 2
showing the atom-numbering scheme is depicted in Fig. 2s. Compound 2 is classified
as a salt in which COOH of the 1-naphthoic acids are absolutely ionized by H transfer
to the N (N(1), N(2), N(3) and N(4)) of the L, which is also supported by the
O(1)-C(29) (1.235(11) Å), O(2)-C(29) (1.251(11) Å), O(3)-C(40) (1.241(10) Å),

O(4)-C(40) (1.225(10) Å), O(5)-C(51) (1.245(9) Å), O(6)-C(51) (1.249(10) Å),
O(7)-C(62) (1.251(10) Å) and O(8)-C(62) (1.238(11) Å).
One cation was bonded to one anion by the bifurcated N-H···O H-bonds from one
+
-
H of the NH and both O of the COO with N-O separations of 2.810(10)-3.319(9) Å
3
to produce a bicomponent adduct A. The other cation was bonded to the other anion
+
-
by the N-H···O H-bond between one H of the NH and one O of the COO with N-O
3
separation of 2.766(9) Å and one CH-O association from the aryl CH of the cation
-
and the same O of the COO involved in the N-H···O H-bond with C-O separation of
3
.262 Å to form a bicomponent adduct B. The bicomponent adducts A and B produce
+
a tetracomponent adduct AB by the N-H···O H-bonds from one H of the NH and the
3
-
COO with N-O separations of 2.717(8)-2.743(9) Å. The third cation was bonded to
+
the third anion by the bifurcated N-H···O H-bonds from one H of the NH and both
3
-
O of the COO with N-O separations of 2.835(9)-3.300(10) Å to produce a
bicomponent adduct A’. The fourth cation was bonded to the fourth anion by the
+
-
N-H···O H-bond from one H of the NH and one O of the COO with N-O separation
3
of 2.774(8) Å and one CH-O association between the aryl CH of the cation and the
-
same O of the COO involved in the N-H···O H-bond with C-O separation of 3.239 Å
to form a bicomponent adduct B’. The bicomponent adducts A’ and B’ were combined
into a tetracomponent adduct A’B’ by the N-H···O H-bonds between the second H of
+
-
the NH3 and the COO with N-O separations of 2.693(8)-2.746(9) Å. The
tetracomponent adducts AB and A’B’ were glued together to give an eight-component
+
-
aggregate under the N-H···O H-bonds between the third H of the NH and the COO
3
with N-O separations of 2.727(10)-2.794(10) Å, CH -O associations from the CH
2
2
-
spacer and the COO with C-O separations of 3.180-3.387 Å and CH-π associations
between the aryl CH of the cation and the naphthalene nucleus with C-Cg separations
of 3.573-3.786 Å. Along the a axis the eight-component aggregates extended into 1D
+
chain with the help of the N-H···O H-bonds between the third H of the NH at the
3
-
bicomponent adduct B’ and the COO with N-O separations of 2.734(10)-2.784(10) Å,
-
CH -O associations from the CH spacer and the COO with C-O separations of
2
2
3
.203-3.384 Å and CH-π associations between the aryl CH of the cation and the

naphthalene nucleus with C-Cg separations being 3.565-3.686 Å. The interchain
CH-π associations from the naphthalene CH and the naphthalene nucleus with C-Cg
separations of 3.602-3.675 Å glued the chains into 2D sheet extending at the ab plane
2
1
2
(
Fig. 2). At the sheet there found the XV R (4), XVI R (7), XVII R (9), XVIII
1 2 4
3
4
3
3
4
4
4
R (10), XIX R (11), XX R (13), XXI R (12), XXII R (13) and XXIII R (15)
4
4
4
4
4
synthons.
Molecular and supramolecular structure of (benzylamine) : (vanillic acid)
+
-
[
(HL) · (vana )] (3)
Fig. 3 should be inserted here.
The crystal structure of 3 was found to crystallize in monoclinic P2(1)/n space
group as anhydrous salt, X-ray analysis displays that the compound 3 contains one HL,
-
and one vana (Fig. 3s). The result clearly tells that the positive charge from the CO H
2
of the vanillic acid is on the NH2.
-
Aryl rings of the vana and HL are almost planar and they intersected at 55.4°
-
-
with each other. The COO rotated by 6.4° from the aryl ring of the vana and the
CH O-/-OH substituents take orientations agreement with the minimum steric
3
interactions, which is the same as that in 5-hydroxymethyl-2-methoxyphenol [23].
The C-O bonds (O(1)-C(8), 1.257(2) Å; O(2)-C(8), 1.252(2) Å) at O1-C8-O2 are
almost equal to each other, suggesting the negative charge on both O was equally
distributed.
-
One HL was bonded to the vana to form a binary unit by the bifurcated N-H···O
+
-
H-bonds from one H of the NH3 and both O of the COO with N-O distances of
-
2
.932(2)-2.966(2) Å and CH -O association from the CH spacer and the COO with
2
2
+
C-O separation of 3.195 Å. The N-H···O H-bond between the second H of the NH3
-
and the COO with N-O distance of 2.750(2) Å brought two binary units into a
tetramer with the corresponding units in the tetramer antiparallelly arranged. Salt 3
displayed 2D grid sheet extending at the direction that made an angle of ca. 60° with
the ab plane (Fig. 3) based on the interlinked tetramers via the N-H···O H-bonds
+
between the third H of the NH and the O at the -OH and -OCH with N-O distances
3
3

of 2.851(2)-3.030(2) Å and the neighboring tetramers were perpendicular to each
other. The 2D grid sheets were further arranged as 3D net with reduced channels by
-
the O-H···O H-bond between the phenol and the COO with O-O distance of 2.522(2)
-
Å. The intersheet CH-O association between the aryl CH of the vana and the -OH
with C-O separation of 3.563 Å, CH-O association from the aryl CH of the HL and
-
the COO with C-O separation of 3.515 Å and CH-π association from the aryl CH of
-
the HL and the aryl nucleus of the vana with C-Cg separation of 3.596 Å also
contributed to the formation and stabilization of the final 3D net. It should be said that
the adjacent sheets were moved some distances from each other along the extending
2
2
1
direction. For the above interactions there had the XXIV R (4), XXV R (5), XXVI
1
1
2
2
4
4
6
R (5), XXVII R (7), XXVIII R (12) and XXIX R (12) ring graphs in the net.
2
4
Molecular
and
supramolecular
structure
of
(benzylamine)2
:
+
2-
(
5-hydroxy-isophthalic acid) [(HL) · (ipa )] (4)
2
Fig. 4 should be inserted here.
+
2-
Salt [(HL) · (ipa )] (4) was obtained by reacting L with 5-hydroxy-isophthalic
2
acid, in which the 5-hydroxy-isophthalic acid donated both Hs of the COOH to the L
2
-
and the asymmetric unit of 4 consists of two HL and one ipa (Fig. 4s). The C-O
bonds O(1)-C(15) (1.256(5) Å), O(2)-C(15) (1.253(5) Å), O(3)-C(16) (1.255(5) Å)
and O(4)-C(16) (1.261(5) Å) are close to each other, reflecting the highly delocalized
π-bonds, the O(5)-C(21) (1.362(5) Å) is for unionized phenol, and all these bonds
/
were comparable with the respective bonds at 4,4 -iminodipyridinium
5
-hydroxyisophthalate trihydrate [24].
-
At one COO there was bonded a HL via the N-H···O H-bond with N-O distance
-
2-
of 2.707(5) Å; at the other COO of the same ipa there was also bonded a HL via the
N-H···O H-bond with N-O distance of 2.757(5) Å together with the bifurcated CH-O
-
associations from the aryl CH of the HL and both O of the COO with C-O
separations of 3.415-3.424 Å, attaining a trinary unit. At the b axis the trinary units
were converted into 1D chain under the N-H···O, O-H···O H-bonds, CH -π and O-π
2
+
-
associations. Here the N-H···O H-bond was from NH3 and the COO with N-O

distance of 2.779(5) Å and the O-H···O H-bond existed between the OH and the
-
COO with O-O distance of 2.762(4) Å. The CH -π associations were established from
2
the CH of the HL and the aryl ring of the HL with C-Cg separations of 3.579-3.721
2
Å and the O-π association was found between the O at the OH and the aryl ring of the
2
-
ipa with O-Cg separation of 3.180 Å. Two chains produced a double chain by the
N-H···O H-bonds with N-O distances of 2.757(5)-2.789(5) Å and NH -π association
3
+
2-
from the NH and the aryl nucleus of the ipa with N-Cg separation of 3.309 Å and
3
the N-Cg separation was agreement with the documented results [25]. The respective
units at two different chains of the double chain were antiparallelly arranged.
Within the 2D sheet extending at the direction that made ca. 60° with the ab plane
(Fig. 8), the neighboring double chains were bridged together by the N-H···O H-bond
2
1
with N-O distance of 2.734(5). The sheets have the XXX R (4), XXXI R (7),
1
2
2
3
4
4
XXXII R (8), XXXIII R (10) and XXXIV R (12) rings. In the third dimension, the
4
4
2
D sheets were bundled together to attain 3D layer network via the independent
2
-
CH-O association between the aryl CH of the HL and the -OH of the ipa with C-O
2
-
separation of 3.272 Å and OH-π association from the -OH of the ipa and the aryl
nucleus of the HL with O-Cg separation of 3.306 Å.
Molecular
and
supramolecular
structure
of
(benzylamine)
:
+
-
(
4-bromo-3,5-dimethoxy-benzoic acid) [(HL) · (bdmba )] (5)
Fig. 5 should be inserted here.
For 5, the single crystals suitable for XRD were obtained by cocrystallization of
L and 4-bromo-3,5-dimethoxy-benzoic acid in 1:1. The compound 5 is an organic salt,
in which the 4-bromo-3,5-dimethoxy-benzoic acid was fully deprotonated and
transferred to the NH of L, the asymmetric unit of 5 consisted of one HL and one
2
-
-
bdmba (Fig. 5s). The C-O bonds in COO were 1.264(5) Å (O(1)-C(8)) and 1.240(5)
Å (O(2)-C(8)), the unequal of the two bonds was due to the different H-bonds the two
O are participated in: for the longer O(1)-C(8) bond the O(1) accepted two N-H···O
H-bonds, while the O(2) only accepted one N-H···O H-bond. The two CH O- adopted
3
the anti-anti orientation with respect to the Br in the para position, which are similar

to methyl 2,6-bis[(5-bromo-4,6-dimethoxypyrimidin-2-yl)oxy]benzoate and methyl
,6-bis[(5-chloro-4,6-dimethoxypyrimidin-2-yl)oxy]benzoate [26], but which are
different from methyl
E)-3,5-dimethoxy-2-{[2-(4-methoxybenzoyl)hydrazin-1-ylidene]-methyl}benzoate
27]. The fact can be explained by the different crowding effect at the corresponding
2
(
[
compounds.
One HL was bonded to one bdmba by the N-H···O H-bond from one H of the
-
+
-
NH and one O of the COO with N-O distance of 2.781(4) Å and CH-O association
3
-
from the same O of the COO that accepted the N-H···O H-bond and the aryl CH of
the HL with C-O separation of 3.472 Å to attain a binary unit. Along the a-axis the
binary units propagated in the form of chain by the N-H···O H-bond from the second
+
-
H of the NH3 and the other O of the COO with N-O distance of 2.814(4) Å and
-
-
CH -O association from the CH O- of the bdmba and the COO with C-O separation
3
3
of 3.638 Å. There existed the additional N-H···O H-bond from the third H of the
+
-
NH3 and the O of the COO that did not have the CH-O association with N-O
distance of 2.735(4) Å, which brought two chains into a double chain. Further
connection by the CH -O, CH-Br, CH -Br, Br-O and CH-π associations from the aryl
2
2
-
CH of the HL and the aryl nucleus of the bdmba with C-Cg separation of 3.652 Å
constructs a 2D corrugated sheet (Fig. 5) extending at the direction that made an angle
of ca. 60° with the ac plane with the neighboring chains perpendicular to each other.
Here the CH -O association was from the CH spacer of the HL and one of the CH O-
2
2
3
with C-O separation of 3.491 Å, the CH-Br association existed between the aryl CH
-
-
of the bdmba and the Br at the bdmba with C-Br separation of 3.869 Å, CH -Br
2
-
association was found between the CH spacer of the HL and the Br at the bdmba
2
with C-Br separation of 3.826 Å and the Br-O contact was resulted from the Br and
-
the COO with Br-O separation of 3.239 Å. The 2D corrugated sheet have the XXXV
2
1
1
2
2
3
R (5), XXXVI R (7), XXXVII R (12), XXXVIII R (15) and XXXIX R (10) ring
2
3
3
4
motifs. Three dimensionally, the 2D corrugated sheets were further expanded by the
CH -O association from the CH at the HL and one of the CH O- units with C-O
2
2
3
-
separation of 3.491 Å, CH-Br association between the aryl CH of the bdmba and the

Br with C-Br separation of 3.869 Å, CH -Br association from the CH of the HL and
2
2
-
the Br with C-Br separation of 3.826 Å, Br-O contact from the Br and the COO with
Br-O separation of 3.239 Å and CH-π association from the aryl CH of the HL and the
-
aryl ring of the bdmba with C-Cg separation of 3.652 Å to form 3D ABAB layer net.
The Br-O separations were close to the reported result [28].
Molecular
and
supramolecular
structure
of
(benzylamine)
:
+
-
(
3,5,6-trichlorosalicylic acid) [(HL) · (tcsal )] (6)
Fig. 6 should be inserted here.
-
The asymmetric unit of 6 bears one HL and one tcsal (Fig. 6s). The C-O bonds at
-
the COO ranged from 1.222(4) Å (C(8)-O(1)) to 1.281(4) Å (C(8)-O(2)), the relative
large ꢀ is resulted from the different H-bonds the O1 and O2 are involved in.
Structural and conformational characters similar to those already found are existed at
-
the tcsal also [29]. The anticipated intramolecular H-bond is established between the
1
phenol and a carboxyl O (O(3)-H(3)···O(2), 2.401(3) Å, 149.6º), generating a S (6)
1
-
circle, due to the planarity of the H-bonded COO unit (C10-C9-C8-O1 = 175.32 °) ,
the O-O separation is in the lower range of the reported data [2.489-2.509 Å] [30].
+
-
The bifurcated N-H···O H-bonds from one H of the NH and both O of the COO
3
-
with N-O distances of 2.844(3)-3.285(4) Å brought one HL and one tcsal into a
heteroadduct. Two heteroadducts were coupled together by the N-H···O H-bond from
+
the second H of the NH and the phenol with N-O distance of 2.909(3) Å to form a
3
tetracomponent adduct, together with the N-H···Cl H-bond from the same H as the
-
N-H···O H-bond and the 3-Cl of the tcsal with N-Cl separation of 3.554(3) Å. There
-
also established the intramolecular Cl-O contact from the 6-Cl and the COO with
Cl-O separation of 2.842 Å being significantly shorter than the archived value [31].
In the a axis, the tetracomponent adducts expanded into chain by the N-H···O
+
-
H-bond of 2.776(3) Å from the third H of the NH3 and the CO and CH -O
2
2
-
association from the CH spacer and the CO with C-O distance of 3.163 Å. The
2
2
2
2
1
2
4
chains show the XL R (4), XLI R (5), XLII R (5), XLIII R (8) and XLIV R (12)
1
1
2
4
6
rings. The CH-O association from the para-CH of the HL and the phenol with C-O

separation of 3.453 Å and face to face π-π association between the aryl rings of the
HL with Cg-Cg separation of 3.359 Å brought the chains into 2D sheet extending
parallel to the ab plane (Fig. 6). At the c-axis, the 2D sheets were converted into 3D
net under the CH -Cl association of 3.605 Å from the CH of the HL and the 5-Cl of
2
2
-
the tcsal .
Molecular
and
supramolecular
structure
of
(benzylamine)2
:
+
2-
(
1,4-naphthalenedicarboxylic acid) : (H O) [(HL ) · (napt) · (H O)] (7)
2
2
2
Fig. 7 should be inserted here.
Similar to the di-acids in 4, the dicarboxylic acid at 7 is also completely
deprotonated, causing a 1,4-naphthalene dicarboxylate salt with the composition of
+
2-
[
(HL ) · (napt) · (H O)]. Salt 7 belongs to the monoclinic space group C2/c with
2 2
two HL, one napt and one H O in the asymmetric unit (Fig. 7s). The two pairs of C-O
2
-
bonds at the COO [1.256(7) Å for O(1)-C(15), 1.249(7) Å for O(2)-C(15), 1.240(7) Å
-
for O(3)-C(16) and 1.254(7) Å for O(4)-C(16)] resembled each other. The two COO
deviated by 51.8° (for C15-O1-O2) and 122.1° (for C16-O3-O4) from the napt ring
and they intersected at 71.5° with each other. The rings C2-C7/C9-C14 made angles
of 30.2/46.5° with the anion ring and the two rings subtended at 57.3° with each other.
-
At one COO of the napt there was attached a HL by the N-H···O H-bond with
-
N-O distance of 2.722(6) Å, at the other COO of the napt there was also attached a
HL by the N-H···O H-bond with N-O distance of 2.744(6) Å and a H O by the
2
O-H···O H-bond with O-O distance of 2.745(5) Å, yielding a tetracomponent adduct.
Along the b-axis the tetracomponent adducts were held together by the N-H···O
+
-
H-bonds between the second H of the NH and the other O of the COO with N-O
3
distances of 2.754(7)-2.760(7) Å to form 1D chain. Under the N-H···O H-bond
+
between the third H of the NH and the H O with N-O distance of 2.838(6) Å, CH -π
3
2
2
association between the CH spacer and the naphthalene nucleus with C-Cg
2
separation of 3.371 Å and CH-CH contact between the aryl CH of the HL with
respective H-H and C-C separations of 2.398 Å and 3.823 Å, the 1D chains were
combined into 2D sheet extending parallel to the bc plane (Fig. 7).

The naphthalene rings at the adjacent chains inclined at 60.2° to each other and
the aryl rings of the HL intersected at 57.3° with each other. The HL at the first chain
was parallel to the HL at the third chain, so did the napt. Two sheets were brought into
a double sheet via the same face of the sheet by the N-H···O H-bond of 2.822(6) Å
+
from the third H of the NH and the H O and O-H···O H-bond from the H O and the
3
2
2
-
4
COO with O-O distance of 2.752(6) Å. The doublesheet have the XLV R (12), XLVI
4
3
6
5
6
R (12), XLVII R (19) and XLVIII R (21) graph sets.
6
6
Molecular and supramolecular structure of (benzylamine) : (dodecanedioic acid)
2
+
2-
[
(HL ) · (doda) ] (8)
2
Fig. 8 should be inserted here.
Similar to 7, the dicarboxylic acid in 8 is also completely deprotonated, causing a
+
2-
dodecanedioate salt of [(HL ) · (doda) ]. Salt 8 belongs to triclinic space group P-1,
2
2
-
having a HL and a half of doda in the asymmetric unit (Fig. 8s).
The doda took the extended trans conformation, the torsion angles around the
-
C-backbone were 177.64-179.18°. At every COO of the doda there each attached a
+
-
HL by the N-H···O H-bond from one H of the NH and one O of the COO with N-O
3
separation of 2.700(4) Å, making a tricomponent aggregate. By the aid of the
+
-
N-H···O H-bond from the second H of the NH and the second O of the COO with
3
N-O separation of 2.970(5) Å, the tricomponent aggregates were connected into chain.
There established the interchain CH -O association from the CH of the HL and the
2
2
-
COO with C-O separation of 3.413 Å, which united the chains into 2D sheet
extending at the direction that oriented ca. 60° with the bc plane (Fig. 8). At the third
direction the sheets were further piled by the N-H···O H-bond from the third H of the
+
-
NH3 and the COO with N-O separation of 2.823(5) Å and CH-O association of
-
3
.377 Å from the aryl CH of the HL and the COO , establishing the final 3D net. The
1
2
2
4
4
net possess the XLIX R (7), L R (8), LI R (10), LII R (12) and LIII R (34) rings.
2
4
4
4
4
Molecular
and
supramolecular
structure
of
(benzylamine)
:
+
(
2,4,6-tribromophenol) [(HL ) · (tbpl)] (9)

Fig. 9 should be inserted here.
SCRD analysis of the isolated 2,4,6-tribromophenol salt of benzylamine
supramolecular complex reveals a 1 : 1 stoichiometry between the two molecules
+
rendering the formulation of 9 to be [(HL ) · (tbpl)]. The crystal structure of 9 is
occupied by four fourths of HL and four fourths of 2,4,6-tribromophenolate in the
asymmetric unit (Fig. 9s). Like the published organic salt bearing
2
,4,6-trichlorophenol [32], in 9 the OH of 2,4,6-tribromophenol are fully ionized via
phenol H transfer to the L.
The C-O bonds in 2,4,6-tribromophenolate are 1.320(9) Å for O(1)-C(29),
1
.323(9) Å for O(2)-C(35), 1.319(9) Å for O(3)-C(41) and 1.266(9) Å for O(4)-C(47),
the first three C-O bonds were akin to that in
diamminebis(2,4,6-tribromophenolato-O)copper(II) [33]. Compared with the first
three C-O bonds, the O(3)-C(41) is strikingly shorter which may be caused by the
different H-bonds the O(3) is involved in.
One cation contacted with one anion by the N-H···O H-bond from one H of the
+
NH3 and the phenolate with N-O separation of 2.703(8) Å and CH-O association
from the aryl CH of the cation and the phenolate with C-O separation of 3.491 Å to
form a heteroadduct A. The second cation was bonded to the second anion by the
+
N-H···O H-bond from one H of the NH3 with N-O separation of 3.002(8) Å,
+
N-H···Br H-bond from the same H of the NH and the o-Br with N-Br separation of
3
3
.618(6) Å and Br-π associations from the same o-Br as above and the aryl ring of the
cation with Br-Cg separations of 3.451-3.474 Å to form a heteroadduct A’. The
heteroadduct A and A’ were adhered together by the N-H···O H-bond from the second
+
H of the NH at the heteroadduct A and the phenolate at the heteroadduct A’ with
3
+
N-O separation of 2.783(8) Å, N-H···Br H-bond from the second H of the NH at the
3
heteroadduct A and the o-Br at the heteroadduct A’ with N-Br separation of 3.460(6)
+
Å, N-H···O H-bond from the second H of the NH at the heteroadduct A’ and the
3
phenolate at the heteroadduct A with N-O separation of 2.721(8) Å, N-H···Br H-bond
+
from the second H of the NH at the heteroadduct A and the o-Br at the heteroadduct
3
A’ with N-Br separation of 3.472(6) Å, CH -Br contact from the CH spacer at the
2
2

heteroadduct A’ and the o-Br at the heteroadduct A with C-Br separation of 3.721 Å to
form a tetracomponent aggregate AA’. The third cation associated with the third
+
anion by the N-H···O H-bond from one H of the NH and the phenolate with N-O
3
separation of 2.708(8) Å and CH-π association from the aryl CH of the cation and the
aryl nucleus of the anion with C-Cg separation of 3.504 Å to form a heteroadduct B.
The fourth cation associated with the fourth anion by the N-H···O H-bond from one H
+
of the NH3 and the phenolate with N-O separation of 3.032(8) Å and N-H···Br
H-bond from the same NH of the cation and the o-Br with N-Br separation of 3.816(6)
Å to form a heteroadduct B’. The heteroadduct B and B’ were held together by the
+
N-H···O H-bond from the second H of the NH3 at the heteroadduct B and the
phenolate at the heteroadduct B’ with N-O separation of 2.749(7) Å, N-H···O H-bond
+
from the second H of the NH3 at the heteroadduct B’ and the phenolate at the
heteroadduct B with N-O separation of 2.725(7) Å, N-H···Br H-bond from the second
+
H of the NH at the heteroadduct B and the o-Br at the heteroadduct B’ with N-Br
3
separation of 3.476(6) Å to get a tetracomponent aggregate BB’.
The tetracomponent aggregate AA’ and BB’ thus produced were combined
together by the N-H···O, N-H···Br H-bonds, Br-π, CH-π associations from the aryl
CH at the heteroadduct A’ and the aryl ring at the heteroadduct B’ with C-Cg
separations of 3.538-3.647 Å and Br-Br bond between the o-Br at the heteroadduct A
and the o-Br at the heteroadduct B’ with Br-Br separation of 3.676 Å to form an
eight-component assembly. Here the N-H···O H-bonds were from the third H of the
+
NH and the phenolate with N-O separations of 2.727(8) - 3.191(8) Å, N-H···Br
3
+
H-bonds were from the third H of the NH and the o-Br of the anions N-Br
3
separations of 3.568(6) - 3.711(6) Å. The Br-π associations were built on the o-Br of
the anions and the aryl nucleus of the cation with Br-Cg separations of 3.370-3.461 Å.
The Br-Br separation was much shorter than the known values of 4.0-4.2 Å [34].
At the a-axis, the CH-Br contacts from the CH of the cation and the o-Br with
C-Br separations of 3.846-3.880 Å linked the eight-component assemblies into chain
which were further brought into a doublechain by the CH-CH contact between the
aryl CH of the cations with H-H/C-C separations of 2.287/3.948 Å. There established

the independent Br-π associations from the p-Br and the aryl rings of the cation and
anion with Br-Cg separations of 3.391-3.482 Å, which made the doublechains into 2D
sheet extending parallel to the ab plane (Fig. 9). In this regard the Br-Cg separations
2
1
were in the range of the known ones [35]. The sheet exhibit the LIV R (5), LV R (5),
1
2
1
2
2
LVI R (7), LVII R (8) and LVIII R (8) rings.
2
2
4
Molecular and supramolecular structure of (benzylamine) : (2-naphthalene
+
sulfonic acid) [(HL ) · (napsa)] (10)
Fig. 10 should be inserted here.
The 2-naphthalene sulfonic acid in 10 is deprotonated, causing a naphthalene
+
sulfonate salt with the composition of [(HL ) · (napsa)] (Fig. 10s), which is also
verified by the O-S bonds (1.424(2)-1.448(2) Å) at the deprotonated SO H. These
3
O-S bonds are comparable to those in other documented sulfonate salt [36]. Salt 10
belongs to the monoclinic P2(1)/c space group. The respective rms deviations of the
aryl rings of the HL and the napsa are 0.0028 and 0.0139 Å and both rings subtended
at 35.2° with each other. The plane made by the N and CH spacer at the same HL
2
was roughly orthogonal to the aryl plane they are attached.
One napsa was bonded to one HL by the bifurcated N-H···O H-bonds from one H
+
-
of the NH and both O from the SO with N-O distances of 2.979(3)-3.120(3) Å and
3
3
+
N-H···S H-bond from the same H of the NH with N-S distance of 3.616(2) Å to get
3
a heteroadduct. Two heteroadducts were united into a tetracomponent aggregate by
+
the N-H···O and N-H···S H-bonds from the second H of the NH with N-O and N-S
3
distances of 2.838(3)-3.726(3) Å. The tetracomponent aggregates thus formed
propagate further as 2D sheet (Fig. 10) at the ab plane by the CH-CH contacts with
H-H/C-C separations of 2.390/3.947 Å. In the c-axis, the 2D sheets were spanned into
3
D net with the help of the N-H···O and N-H···S H-bonds from the third H of the
+
-
NH and the SO with N-O and N-S distances of 2.800(3) and 3.680(3) Å, CH -O
3
3
2
and CH-π associations. The CH -O association was from the CH of the HL and the
2
2
-
SO with C-O separation of 3.223 Å and the CH-π association was occurred between
3
the naphthalene CH and the naphthalene nucleus with C-Cg separation of 3.663 Å.

2
1
4
4
4
4
The net display the LIX R (3), LX R (12), LXI R (13) and LXII R (14) rings.
4
4
Influence of the organic acids on the architectures of 1-10
In this study, an array of rigid and flexible acids, which has additional functional
groups, were used to prepare supramolecular salts, making ten compounds with 2D
sheet (for 1-2, 7 and 9) to 3D net (for 3-6, 8 and 10) structures. Our research indicates
that organic acids have a significant effect on the architectures of 1-10. In 1-10, the
acids are essential in making the salts. The different acids not only have an effect on
the protonation of L, but also play an important role in establishing the final
architectures with different dimensionalities via H-bonds and various non-covalent
bonds. All compounds have the non-covalent bonded 2D sheet. The major classical
H-bonds had similar role in expanding 1-10.
All the negatively charged O of the anion at the anhydrous salts participated in
the CH -O (n = 1, 2, 3) association except the hydrate salt 7. All the aryl nucleus of
n
-
the anions produced the π-interactions. In 1 the CHCl unit at dca plays a key role in
2
forming the 2D sheet via CH-O and CH-Cl/CH -Cl contacts. For 2 it is the CH-π
2
association from the naphthalene nucleus of the anion that extends the 1D chains into
-
the final 2D sheet. Both OH and OCH at vana in 3 have the interchain N-H···O
3
H-bonds and the OH have the intersheet O-H···O H-bond. For 4 the complete 3D
2
-
structure is dependent solely on the CH-O association from the OH of the ipa . At 5
-
2-
the CH O, Br, COO and aryl ring of the bdmba participate in the 2D sheet
3
expansion into 3D ABAB layer net. In 6 the further expansion of the 2D sheet into 3D
-
net was completed via the CH -Cl association from 5-Cl of the tcsal . The naphthalene
2
nucleus at 7 participated in the 2D sheet construction via CH -π association. In 8 only
2
-
COO participated in structure extension. Salt 9 have the Br-π associations from the
p-Br of tbpl which take doublechains into 2D sheet. The CH-CH contacts from the
anion support the 2D sheet and the aryl CH of the anion take part in the intersheet
CH-π associations at 10. The results tell that the different species of functional groups,
as well as their number and position at the acids, have crucial effects on both the sub
and the final structures in 1-10.