Structure of six organic acid-base adducts from 6-bromobenzo[d]thiazol-2- amine and acidic compounds

Article abstract of DOI:10.1016/j.molstruc.2014.02.064

Six anhydrous organic acid-base adducts of 6-bromobenzo[d]thiazol-2-amine were prepared with organic acids as 2,4,6-trinitrophenol, salicylic acid, 3,5-dinitrobenzoic acid, 3,5-dinitrosalicylic acid, malonic acid and sebacic acid. The compounds 1-6 were c

Full text of DOI:10.1016/j.molstruc.2014.02.064

Journal of Molecular Structure 1065-1066 (2014) 223–234
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Structure of six organic acid–base adducts from 6-bromobenzo[d]
thiazol-2-amine and acidic compounds
a
b
a
a
a
a
Shouwen Jin a, , Jing Zhang , Daqi Wang , Lin Tao , Mengjian Zhou , Yinyan Shen , Quan Chen ,
⇑
Zhanghui Lin a, Xingjun Gao a
a Tianmu College, ZheJiang A&F University, Lin’An 311300, PR China
b Department of Chemistry, Liaocheng University, Liaocheng 252059, PR China
h i g h l i g h t s
ꢀ
ꢀ
ꢀ
ꢀ
Six supramolecular compounds with 1D–3D structure have been prepared and characterized.
The noncovalent interaction between 2-aminothiazole derivative and acids have been discussed.
The NAHꢁ ꢁ ꢁO/OAHꢁ ꢁ ꢁN hydrogen bond is the primary force in a family of structures containing the OHꢁ ꢁ ꢁ2-aminothiazole synthons.
Except 1, all compounds bear the heterosynthon R22ð8Þ.
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 9 May 2013
Received in revised form 14 February 2014
Accepted 25 February 2014
Available online 11 March 2014
Six anhydrous organic acid–base adducts of 6-bromobenzo[d]thiazol-2-amine were prepared with
organic acids as 2,4,6-trinitrophenol, salicylic acid, 3,5-dinitrobenzoic acid, 3,5-dinitrosalicylic acid,
malonic acid and sebacic acid. The compounds 1–6 were characterized by X-ray diffraction analysis,
IR, and elemental analysis. The melting points of all the adducts were given. Of the six adducts, 1, 3, 4,
and 5 are organic salts, while 2, and 6 are cocrystals. The supramolecular arrangement in the crystals
2–6 is based on the R22ð8Þ synthon. Analysis of the crystal packing of 1–6 suggests that there are strong
NAHꢁ ꢁ ꢁO, OAHꢁ ꢁ ꢁN, and OAHꢁ ꢁ ꢁO hydrogen bonds (charge assisted or neutral) between acid and base
components in the supramolecular assemblies. When the hydroxyl group is present in the ortho position
of the carboxy, the intramolecular S6 synthon is present, as expected. Besides the classical hydrogen
bonding interactions, other noncovalent interactions also play important roles in structure extension.
Due to the synergetic effect of these weak interactions, compounds 1–6 display 1D–3D framework
structure.
Keywords:
Crystal structure
Hydrogen bonding
R22ð8Þ synthon
6-Bromobenzo[d]thiazol-2-amine
Acidic compounds
Ó 2014 Elsevier B.V. All rights reserved.
1. Introduction
Thus, the supramolecular synthesis successfully exploits hydro-
gen-bonding and other types of noncovalent interactions in build-
As an important branch of supramolecular chemistry, crystal
engineering has currently attracted many research interests in so-
lid and material science [1,2]. The rapid developments in this field
show that a variety of organic components with specific functional
groups have been used to create supramolecular arrays via either
metal coordination or noncovalent forces, displaying fascinating
structures and useful properties [3–6]. In this context, numerous
examples of acid–base adducts have been documented recently,
the assembly of which is driven through noncovalent interactions,
mainly hydrogen bonding with or without charge assistance [6].
ing supramolecular systems [7]. There are many interesting
topological structures such as one-dimensional (1-D) chains,
two-dimensional (2-D) sheets, and three-dimensional (3-D) net-
works which have been constructed through hydrogen bonding
interactions [8–10]. The carboxylic acid bears the important hydro-
gen bonding functional group COOH for crystal engineering [11].
Carboxylic acids aggregate in the solid state as dimer, catemer,
and bridged motifs [12]. Besides the COOH group, the functional
groups such as NO2 and OH are both good groups in forming organ-
ic solid through noncovalent interactions [13], thus we select some
acids bearing additional groups such as NO2 and OH. It is interest-
ing to exploit the robust and directional recognition of acids with
nitrogen containing heterocyclic compounds [14].
⇑
Corresponding author. Tel./fax: +86 571 6374 6755.
E-mail address: jinsw@zafu.edu.cn (S. Jin).
http://dx.doi.org/10.1016/j.molstruc.2014.02.064
0022-2860/Ó 2014 Elsevier B.V. All rights reserved.

224
S. Jin et al. / Journal of Molecular Structure 1065-1066 (2014) 223–234
As one of the excellent supramolecular synthons, 2-aminoben-
2.3. Similar procedure was employed to obtain compounds 2–6
zothiazole and its derivatives bearing multiple hydrogen-bonding
sites and metal ion binding donors have been extensively utilized
in the new materials, biochemistry, and agriculture chemistry
[15,16]. In addition to containing the 2-aminobenzothiazole back-
bone, the halogen (Br) atom at 6-bromobenzo[d]thiazol-2-amine
can generate halogen–halogen bond which has been widely uti-
lized in crystal engineering [17].
2.3.1. (6-Bromobenzo[d]thiazol-2-amine): (salicylic acid) [(L)ꢁ(Hsal)]
(2)
Colorless. Yield: 34 mg, 92.58% (based on L). m.p. 177–179 °C.
Anal. Calcd for C14H11BrN2O3S (367.22): C, 45.75; H, 2.99; N,
7.62; S, 8.71. Found: C, 45.72; H, 2.94; N, 7.54; S, 8.66. Infrared
spectrum (KBr disc, cmꢂ1): 3665s(
m
(OH)), 3442s(
s(NH)), 3096m, 2996m, 2508m, 1896m, 1702s(
1627m, 1542m, 1490s, 1436s, 1298s( (CAO)), 1186m, 1132m,
m
as(NH)),
The adducts between the acids and 6-bromobenzo[d]thiazol-2-
amine may show the different hydrogen-bonding patterns from
the three different acceptor atoms at 6-bromobenzo[d]thiazol-2-
amine. In recent years, our research group has been involved in
the study of organic acid–base adducts based on carboxylic acids
and organic bases. As an extension of our study of supramolecular
assemblies concerning aromatic N-containing derivatives [18],
herein we report the preparation and structures of six supramolec-
ular compounds assembled from 6-bromobenzo[d]thiazol-2-
amine (L), and the corresponding acidic compounds (Scheme 1),
respectively. The six compounds are (6-bromobenzo[d]thiazol-
2-amine): (2,4,6-trinitrophenol) [(HL)+ꢁ(pic)ꢂ, pic = 2,4,6-trinitro-
phenolate] (1), (6-bromobenzo[d]thiazol-2-amine): (salicylic acid)
[(L)ꢁ(Hsal), Hsal = salicylic acid] (2), (6-bromobenzo[d]thiazol-
2-amine): (3,5-dinitrobenzoic acid) [(HL+)ꢁ(dnbaꢂ), dnbaꢂ = 3,
5-dinitrobenzoate] (3), (6-bromobenzo[d]thiazol-2-amine): (3,
5-dinitrosalicylic acid) [(HL+)ꢁ(dnsaꢂ), dnsaꢂ = 3,5-dinitrosalicy-
late] (4), (6-bromobenzo[d]thiazol-2-amine): (malonic acid)
[(HL+)ꢁ(Hmalꢂ), Hmalꢂ = hydrogen malonate] (5) and (6-bro-
mobenzo[d]thiazol-2-amine)2: (sebacic acid) [(L)2ꢁ(seb), seb =
sebacic acid] (6), respectively (Scheme 2). In this regard, 2 and 6
are cocrystals, 1, 3, 4, and 5 are molecular salts.
3143s(
m
m(C@O)),
m
1115m, 1060m, 1012m, 936m, 859m, 809m, 735m, 686m, 622m.
2.3.2. (6-Bromobenzo[d]thiazol-2-amine): (3,5-dinitrobenzoic acid)
[(HL+)ꢁ(dnbaꢂ)] (3)
Light yellow. Yield: 34 mg, 77.06% (based on L). m.p.
214–215 °C. Anal. Calcd for C14H9BrN4O6S (441.22): C, 38.07; H,
2.04; N, 12.69; S, 7.25. Found: C, 38.02; H, 2.01; N, 12.58; S, 7.18.
Infrared spectrum (KBr disc, cmꢂ1): 3488s(
m
as(NH)), 3296s(
as(COOꢂ)), 1536s(
as(NO2)),
s(COOꢂ)), 1320s(
as(NO2)), 1282m,
ms(-
NH)), 3087m, 2984s, 1626m, 1598s(
m
m
1492m, 1446m, 1382s(
m
m
1246m, 1202m, 1162m, 1094m, 1006m, 952w, 861w, 811m,
767w, 714m, 656w, 618w.
2.3.3. (6-Bromobenzo[d]thiazol-2-amine): (3,5-dinitrosalicylic acid)
[(HL+)ꢁ(dnsaꢂ)] (4)
Light yellow. Yield: 34 mg, 77.06% (based on L). m.p.
188–189 °C. Anal. Calcd for C14H9BrN4O7S (457.22): C, 36.74; H,
1.97; N, 12.25; S, 6.99. Found: C, 36.67; H, 1.92; N, 12.18; S, 6.92.
Infrared spectrum (KBr disc, cmꢂ1): 3631s(
m
(OH)), 3486s(multiple,
s(NH)), 3115m, 3064m, 2960m, 1976w, 1836w,
as(COOꢂ)), 1540s( s(COOꢂ)),
as(NO2)), 1486w, 1394s(
1366m, 1312s( s(NO2)), 1270m, 1195m, 1131m, 1079m, 952m,
m
as(NH)), 3308s(
m
1783w, 1586s(
m
m
m
m
903m, 853m, 806m, 757m, 716m, 680m, 637m.
2. Experimental section
2.1. Materials and physical measurements
2.3.4. (6-Bromobenzo[d]thiazol-2-amine): (malonic acid)
[(HL+)ꢁ(Hmalꢂ)] (5)
The chemicals and solvents used in this work were of analytical
grade and available commercially and were used without further
purification. The FT-IR spectra were recorded from KBr pellets in
range 4000–400 cmꢂ1 on a Mattson Alpha-Centauri spectrometer.
Microanalytical (C, H, and N) data were obtained with a Perkin–El-
mer Model 2400II elemental analyzer. Melting points of new com-
pounds were recorded on an XT-4 thermal apparatus without
correction.
Colorless. Yield: 28 mg, 84.04% (based on L). m.p. 158–159 °C.
Anal. Calcd for C10H9BrN2O4S (333.16): C, 36.02; H, 2.70; N, 8.40;
S, 9.60. Found: C, 35.94; H, 2.61; N, 8.31; S, 9.55. Infrared spectrum
(KBr disc, cmꢂ1): 3659s(
m
m
(OH)), 3454s(multiple,
s(NH)), 3140m, 3060m, 2990m, 2924m, 1698vs(v(C@O)), 1623m,
1588s(
as(COOꢂ)), 1542m, 1488s, 1426s, 1386s( s(COOꢂ)), 1358m,
1300m, 1280s( (CAO)), 1234m, 1192m, 1135m, 1100m, 1063m,
1021m, 936m, 853m, 800m, 742m, 678m, 616m.
mas(NH)), 3352(br,
m
m
m
2.3.5. (6-Bromobenzo[d]thiazol-2-amine)2: (sebacic acid) [(L)2ꢁ(seb)]
(6)
2.2. Typical preparation procedure
Colorless. Yield: 44 mg, 66.62% (based on seb). m.p. 177–178 °C.
Anal. Calcd for C24H28Br2N4O4S2 (660.44): C, 43.61; H, 4.24; N,
8.48; S, 9.69. Found: C, 43.54; H, 4.17; N, 8.39; S, 9.62. Infrared
2.2.1. (6-Bromobenzo[d]thiazol-2-amine): (2,4,6-trinitrophenol)
[(HL)+ꢁ(pic)ꢂ] (1)
spectrum (KBr disc, cmꢂ1): 3585s(
m
(OH)), 3239m(
s(NH)), 3084m, 2988m, 2875m, 2502m, 2449m, 2366m,
1918m, 1656s( (C@O)), 1629m, 1521m, 1447m, 1386m,
1295s( (CAO)), 1277m, 1236m, 1191m, 1106m, 943m, 896m,
mas(NH)),
To a methanol solution (6 ml) of 6-bromobenzo[d]thiazol-2-
amine (22.9 mg, 0.1 mmol) was added 2,4,6-trinitrophenol
(23 mg, 0.1 mmol) in 12 ml methanol. The solution was stirred
for a few minutes, then the solution was filtered into a test tube.
The solution was left standing at room temperature for several
days, light yellow crystals were isolated after slow evaporation of
the methanol solution in air. The crystals were collected and dried
in air to give the title compound [(HL)+ꢁ(pic)ꢂ] (1). Yield: 36 mg,
78.57% (based on L). m.p. 156–157 °C. Anal. Calcd for C13H8BrN5O7S
(458.21): C, 34.04; H, 1.74; N, 15.28; S, 6.98. Found: C, 33.96; H,
1.69; N, 15.21; S, 6.95. Infrared spectrum (KBr disc, cmꢂ1):
3129m(
m
m
m
829m, 777m, 716m, 665m, 621m.
2.4. X-ray crystallography and data collection
Suitable crystals were mounted on glass fibers on a Bruker
SMART 1000 CCD diffractometer operating at 50 kV and 40 mA
using Mo K
a radiation (k = 0.71073 Å). Data collection and reduc-
3457s(
m
as(NH)), 3266s(
m
s(NH)), 3164m, 3101s, 2968m, 1597m,
tion were performed using the SMART and SAINT software [19].
The structures were solved by direct methods, and the non-
hydrogen atoms were subjected to anisotropic refinement by
full-matrix least squares on F2 using SHELXTL package [20].
1528s(
m
as(NO2)), 1479m, 1435m, 1399m, 1348m, 1322s(
ms(NO2)),
1276m, 1234m, 1165m, 1107w, 1073m, 1017m, 975m, 899m,
845m, 815m, 766m, 721m, 673m, 640m, 605m.

S. Jin et al. / Journal of Molecular Structure 1065-1066 (2014) 223–234
225
Scheme 1. Hydrogen bond building blocks discussed in this paper.
Scheme 2. Description of the hetero synthons present in compounds 1–6.
Hydrogen atom positions for all of structures were located in
difference Fourier maps but were allowed to ride on the parent
atoms at geometrically determined positions with OAH = 0.82 Å,
NAH = 0.86 Å, CAH = 0.93 Å (aromatic) or 0.97 Å (methylene) and

226
S. Jin et al. / Journal of Molecular Structure 1065-1066 (2014) 223–234
Table 1
Summary of X-ray crystallographic data for compounds 1–6.
1
2
3
4
5
6
Formula
Fw
C
13H8BrN5O7S
C14H11BrN2O3S
367.22
C14H9BrN4O6S
441.22
C14H9BrN4O7S
457.22
C10H9BrN2O4S
333.16
C24H28Br2N4O4S2
660.44
458.21
T, K
298(2)
298(2)
298(2)
298(2)
298(2)
298(2)
Wavelength, Å
Crystal system
Space group
a, Å
b, Å
c, Å
0.71073
Monoclinic
C2/c
18.2516(17)
16.0985(15)
13.9855(12)
90
127.222(2)
90
3272.2(5)
8
1.860
2.692
1824
0.43 ꢃ 0.39 ꢃ 0.27
2.53–25.02
ꢂ14 6 h 6 21
ꢂ19 6 k 6 18
ꢂ16 6 l 6 15
8044
0.71073
Monoclinic
C2/c
30.773(3)
4.0102(3)
25.039(2)
90
103.3620(10)
90
3006.3(4)
8
1.623
2.884
1472
0.28 ꢃ 0.16 ꢃ 0.13
2.39–25.01
ꢂ36 6 h 6 27
ꢂ4 6 k 6 4
ꢂ28 6 l 6 29
6957
0.71073
Monoclinic
P2(1)/n
7.2172(5)
7.5495(7)
29.874(3)
90
93.7400(10)
90
1624.2(2)
4
1.804
2.702
880
0.48 ꢃ 0.40 ꢃ 0.20
2.78–25.01
ꢂ8 6 h 6 8
ꢂ8 6 k 6 8
ꢂ22 6 l 6 35
7711
0.71073
Monoclinic
C2/c
24.151(2)
14.1491(15)
9.7260(10)
90
101.5800(10)
90
3255.9(6)
8
1.866
2.704
1824
0.43 ꢃ 0.40 ꢃ 0.14
2.58–25.02
ꢂ28 6 h 6 28
ꢂ16 6 k 6 8
ꢂ11 6 l 6 11
7849
0.71073
Monoclinic
P2(1)/c
4.5254(2)
15.8930(10)
16.9641(12)
90
96.2680(10)
90
1212.80(13)
4
1.825
3.569
664
0.40 ꢃ 0.21 ꢃ 0.16
2.42–25.01
ꢂ5 6 h 6 5
ꢂ12 6 k 6 18
ꢂ19 6 l 6 20
6008
0.71073
Triclinic
Pꢂ1
6.9100(5)
11.0219(11)
11.1021(12)
110.076(2)
104.2500(10)
106.6210(10)
703.09(12)
1
a
, deg.
b, deg.
c
, deg.
V, Å3
Z
Dcalcd, Mg/m3
1.560
3.067
334
0.24 ꢃ 0.17 ꢃ 0.13
3.14–25.00
ꢂ8 6 h 6 7
ꢂ13 6 k 6 13
ꢂ6 6 l 6 13
3565
Absorption coefficient, mmꢂ1
F(000)
Crystal size, mm3
h range, deg
Limiting indices
Reflections collected
Reflections independent (Rint
)
2880 (0.0400)
0.995
2644 (0.0487)
0.871
2846 (0.0849)
1.026
2877 (0.1369)
0.981
2146 (0.0354)
1.014
2451 (0.0356)
0.978
Goodness-of-fit on F2
R indices [I > 2
r
I]
0.0378, 0.0872
0.0635, 0.0995
0.575, ꢂ0.578
0.0422, 0.0944
0.0855, 0.1055
0.367, ꢂ0.619
0.0639, 0.1685
0.0897, 0.1856
0.838, ꢂ0.634
0.0590, 0.1384
0.0981, 0.1604
1.328, ꢂ0.672
0.0325, 0.0702
0.0538, 0.0779
0.511, ꢂ0.341
0.0472, 0.1204
0.0598, 0.1279
0.699, ꢂ0.753
R indices (all data)
Largest diff. peak and hole, e Åꢂ3
with Uiso = 1.2Ueq(C,N) and Uiso = 1.5Ueq(O). Further details of the
structural analysis are summarized in Table 1. Selected bond
lengths and angles for the compounds 1–6 are listed in Table 2,
the relevant hydrogen bond parameters are provided in Table 3.
Table 2
Selected bond lengths [Å] and angles [°] for compounds 1–6.
1
3. Results and discussion
N(1)AC(1)
O(1)AC(8)
S(1)AC(3)
C(1)AS(1)AC(3)
1.331(4)
1.247(4)
1.754(3)
90.41(16)
N(2)AC(1)
S(1)AC(1)
C(1)AN(1)AC(2)
1.304(4)
1.731(4)
114.4(3)
3.1. Preparation and general characterization
2
In all of the structures except 2 and 6, the heteroaromatic Lewis
base molecules are protonated, therefore 1, 3, 4, and 5 can be clas-
sified as molecular-salts, while 2 and 6 are cocrystals. The six com-
pounds are not hygroscopic, and they all crystallized with no
solvent molecules. The molecular structures and their atomic
labelling schemes for the six structures are illustrated in Fig. 1,
Fig. 3, Fig. 5, Fig. 8, Fig. 11, and Fig. 14, respectively. The infrared
spectra of the six compounds bear characteristic absorption bands
for amino and carboxyl groups (except 1).
The very strong and broad features at approximately
3700–3100 cmꢂ1 in the IR spectra of the six compounds arise from
OAH or NAH stretching frequencies. Aromatic, and benzo[d]thiazol-
ic ring stretching and bending are attributed to the medium
intensity bands in the regions of 1500–1630 cmꢂ1 and 600–
750 cmꢂ1, respectively. Compounds 3, 4, and 5 show the character-
istic bands for COOꢂ, while compound 5 displays additional strong
IR peaks for COOH groups. The presence of two broad bands at ca.
2500 cmꢂ1 and 1900 cmꢂ1 in compounds 2 and 6, characteristic of
a neutral OAHꢁ ꢁ ꢁN hydrogen-bond interaction, was viewed as
evidence for co-crystal formation [21].
S(1)AC(3)
N(1)AC(1)
O(1)AC(8)
O(3)AC(10)
C(1)AN(1)AC(2)
1.749(4)
1.317(4)
1.305(4)
1.367(4)
110.4(3)
S(1)AC(1)
N(1)AC(2)
O(2)AC(8)
C(3)AS(1)AC(1)
O(2)AC(8)AO(1)
1.768(4)
1.404(4)
1.247(4)
88.86(17)
123.0(3)
3
N(1)AC(1)
O(1)AC(8)
S(1)AC(3)
C(1)AN(1)AC(2)
O(2)AC(8)AO(1)
1.303(7)
1.265(6)
1.747(5)
113.4(4)
125.5(5)
N(1)AC(2)
O(2)AC(8)
S(1)AC(1)
C(3)AS(1)AC(1)
1.411(6)
1.251(6)
1.762(6)
89.6(2)
4
N(1)AC(1)
O(1)AC(8)
O(3)AC(10)
S(1)AC(3)
C(1)AS(1)AC(3)
1.307(7)
1.222(7)
1.309(6)
1.759(6)
89.9(3)
N(1)AC(2)
O(2)AC(8)
S(1)AC(1)
C(1)AN(1)AC(2)
O(1)AC(8)AO(2)
1.400(7)
1.291(7)
1.746(6)
114.5(5)
124.6(6)
5
S(1)AC(1)
N(1)AC(1)
O(1)AC(8)
O(3)AC(10)
C(1)AS(1)AC(3)
O(2)AC(8)AO(1)
1.740(3)
1.320(4)
1.308(4)
1.264(4)
89.94(15)
120.8(3)
S(1)AC(3)
N(1)AC(2)
O(2)AC(8)
O(4)AC(10)
C(1)AN(1)AC(2)
O(4)AC(10)AO(3)
1.750(3)
1.386(4)
1.216(4)
1.239(4)
114.4(3)
124.8(3)
3.2. Structural descriptions
6
S(1)AC(3)
N(1)AC(1)
O(1)AC(8)
C(3)AS(1)AC(1)
O(2)AC(8)AO(1)
1.747(3)
1.313(5)
1.329(4)
88.82(16)
122.6(3)
S(1)AC(1)
N(1)AC(2)
O(2)AC(8)
C(1)AN(1)AC(2)
1.761(4)
1.402(4)
1.223(4)
110.5(3)
3.2.1. X-ray structure of (6-bromobenzo[d]thiazol-2-amine): (2,4,6-
trinitrophenol) [(HL)+ꢁ(pic)ꢂ] (1)
Salt 1 was prepared by reaction of a methanol solution of
2,4,6-trinitrophenol and 6-bromobenzo[d]thiazol-2-amine in 1:1

S. Jin et al. / Journal of Molecular Structure 1065-1066 (2014) 223–234
227
Table 3
O(1)AC(8) (1.247(4) Å) for phenolate (1.24 0.01 Å) [22]. In this
case the ring nitrogen atom of the 6-bromobenzo[d]thiazol-2-
amine is protonated which is similar to the published result [23].
In the asymmetric unit of compound 1, there exist one cation
and one anion without solvent molecules, which is well agreement
with the micro-analysis results. In the solid state, there is consis-
tently hydrogen bond formed between the ionic components of
the thiazolium cation and the 2,4,6-trinitrophenolate anion.
As expected, the benzo[d]thiazol moiety is planar (the mean
deviation from plane is 0.0085(2) Å), the rms deviation of the phe-
nyl ring of the anion is 0.0165(2) Å. The benzo[d]thiazol moiety
and the phenyl unit of the anion are roughly coplanar, in which
both planes inclined at an angle of 11.6(1)° with each other. The
ortho-nitro groups (N3AO3AO2, and N5AO7AO6) deviate from
the phenyl plane of the anion and have dihedral angles of 23(1)°,
and 33.6(2)° with the phenyl plane, which are comparable with
the corresponding values of the reported salt based on picrate
[24]. The two o-nitro groups intersected at an angle of 28.9(2)°
with each other. The para-nitro group [N4AO5AO4] also deviates
by 5.0(1)° from the phenyl plane of the anion, which is comparable
with the corresponding data reported by Muthamizhchelvan et al.
[24]. The para nitro group made dihedral angles of 27.3(2)°, and
38.2(2)° with the two o-nitro groups, respectively.
One anion was bonded to one cation via three NAHꢁ ꢁ ꢁO hydro-
gen bonds, and one CHAO association between the phenyl CH of
the cation and the o-nitro group of the anion with CAO distance
of 3.153 Å to form a bicomponent adduct. For the presence of these
nonbonding interactions, there were close joint R12ð6Þ, R12ð6Þ and
R12ð6Þ motifs. Of the three NAHꢁ ꢁ ꢁO hydrogen bonds, one is be-
tween the amine group of the cation and the phenolate with
NAO distance of 2.768(4) Å, the other two are from the NH+ cation
and the phenolate and the o-nitro group that has a CHAO associa-
tion in which the NAO distances are 2.677(4) Å and 3.056(4) Å,
respectively. The bicomponent adducts were linked together by
the CHABr contact between the phenyl CH of the anion and the
Br of the cation with CABr distance of 3.859 Å, and CHAO contact
between the phenyl CH of the cation and the p-nitro group in the
anion with CAO distance of 3.271 Å to form 1D chain running
along the a axis direction. Two neighboring chains were joined to-
gether by the interchain CHAO interactions between the phenyl
CH of the cation and the p-nitro group with CAO distances of
3.136–3.172 Å to form double chain. In the double chain the
bicomponent adducts at different chains were antiparallel to each
other. The double chains were further held together via the
NAHꢁ ꢁ ꢁO hydrogen bond between the o-nitro group and the NH2
at the cation with NAO distance of 2.975(4) Å and CHAO
Hydrogen bond distances and angles in studied structures of 1–6.
DAHꢁ ꢁ ꢁA
d(DAH)
(Å)
d(Hꢁ ꢁ ꢁA)
d(Dꢁ ꢁ ꢁA)
<(DHA)
(°)
(Å)
(Å)
1
N(2)AH(2B)ꢁ ꢁ ꢁO(3)#1 0.86
2.12
2.06
2.34
1.96
2.975(4)
2.768(4)
3.056(4)
2.677(4)
171
140
141
140
N(2)AH(2A)ꢁ ꢁ ꢁO(1)
N(1)AH(1)ꢁ ꢁ ꢁO(7)
N(1)AH(1)ꢁ ꢁ ꢁO(1)
0.86
0.86
0.86
2
O(3)AH(3)ꢁ ꢁ ꢁO(2)
0.82
1.87
1.83
2.13
2.05
2.589(3)
2.637(3)
2.896(4)
2.887(4)
146
169
148
164
O(1)AH(1A)ꢁ ꢁ ꢁN(1)#1 0.82
N(2)AH(2B)ꢁ ꢁ ꢁO(3)#2 0.86
N(2)AH(2A)ꢁ ꢁ ꢁO(2)#3 0.86
3
N(1)AH(1)ꢁ ꢁ ꢁO(1)#1
0.86
1.71
2.09
2.21
2.568(5)
2.903(6)
2.985(6)
172
158
150
N(2)AH(2A)ꢁ ꢁ ꢁO(2)#1 0.86
N(2)AH(2B)ꢁ ꢁ ꢁO(2)
0.86
4
O(3)AH(3)ꢁ ꢁ ꢁO(2)
0.82
1.66
2.38
2.17
1.98
1.87
2.406(6)
3.142(7)
2.855(6)
2.818(7)
2.725(6)
150
148
136
165
176
N(2)AH(2B)ꢁ ꢁ ꢁO(4)#1 0.86
N(2)AH(2B)ꢁ ꢁ ꢁO(3)#1 0.86
N(2)AH(2A)ꢁ ꢁ ꢁO(2)#2 0.86
N(1)AH(1)ꢁ ꢁ ꢁO(1)#2
0.86
5
O(1)AH(1A)ꢁ ꢁ ꢁO(3)
0.82
1.72
2.00
1.97
1.80
2.487(3)
2.813(4)
2.807(4)
2.656(3)
154
158
163
176
N(2)AH(2B)ꢁ ꢁ ꢁO(2)#1 0.86
N(2)AH(2A)ꢁ ꢁ ꢁO(3)#2 0.86
N(1)AH(1)ꢁ ꢁ ꢁO(4)#2
0.86
6
O(1)AH(1A)ꢁ ꢁ ꢁN(1)#2 0.82
N(2)AH(2B)ꢁ ꢁ ꢁO(2)#3 0.86
N(2)AH(2A)ꢁ ꢁ ꢁO(2)#2 0.86
1.90
2.19
2.06
2.716(4)
2.851(4)
2.897(4)
171
134
163
Symmetry transformations used to generate equivalent atoms for 1: #1 ꢂ x + 3/2,
ꢂy + 1/2, ꢂz + 1. Symmetry transformations used to generate equivalent atoms 2:
#1 x ꢂ 1/2, y ꢂ 1/2, z; #2 ꢂx + 1/2, y ꢂ 1/2, ꢂz + 1/2; #3 x + 1/2, y + 1/2, z. Symmetry
transformations used to generate equivalent atoms for 3: #1 ꢂx + 1/2, y ꢂ 1/2,
ꢂz + 1/2. Symmetry transformations used to generate equivalent atoms for 4: #1
ꢂx, y, ꢂz ꢂ 1/2; #2 x, ꢂy + 1, z ꢂ 1/2. Symmetry transformations used to generate
equivalent atoms for 5: #1 ꢂx + 1, y ꢂ 1/2, ꢂz + 1/2; #2 x + 1, y, z. Symmetry
transformations used to generate equivalent atoms for 6: #2 ꢂx + 1, ꢂy, ꢂz + 1; #3
x ꢂ 1, y, z.
ratio, which crystallizes as monoclinic pale yellow crystals in the
centrosymmetric space group C2/c. The structure of 1 with the
atom numbering scheme is shown in Fig. 1. This is a salt where
the OH group of 2,4,6-trinitrophenol is ionized by proton transfer
to one nitrogen atom (N(1)) of the 6-bromobenzo[d]thiazol-2-
amine moiety, which is also confirmed by the bond distance of
Fig. 1. Molecular structure of 1 showing the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

228
S. Jin et al. / Journal of Molecular Structure 1065-1066 (2014) 223–234
Fig. 2. The 2D sheet structure of 1 extending at the direction that made a dihedral angle of ca. 30° with the ab plane.
Fig. 3. Molecular structure of 2 showing the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
associations between the p-nitro group and the phenyl CH of the
cation with CAO distances of 3.136–3.172 Å to form 2D sheet
extending at the direction that made a dihedral angle of ca. 30°
with the ab plane (Fig. 2).
graph set. This feature is similar to that found in the parent com-
pound of salicylic acid [27].
The adjacent heteroadducts were joined together via the
NAHꢁ ꢁ ꢁO hydrogen bond between the amino group of the L mole-
cule and the phenol group of the salicylic acid with NAO separa-
tion of 2.896(4) Å to form a 1D zigzag chain running along the b
axis direction (Fig. 4). Herein the neighboring heteroadducts in
the chain made an angle of ca. 60° with each other. And the first
heteroadduct is parallel to the third heteroadduct, so does the sec-
ond heteroadduct and the fourth heteroadduct.
3.2.2. X-ray structure of (6-bromobenzo[d]thiazol-2-amine): (salicylic
acid) [(L)ꢁ(Hsal)] (2)
Different from 1, no protons of the salicylic acid were trans-
ferred to the N atoms of the L in the compound 2. Thus 2 can be
classified as an organic cocrystal. In the asymmetric unit of 2 there
existed one molecule of L, and one molecule of salicylic acid, as
shown in Fig. 3. The ratio of CAO(long) to C@O (short) bond dis-
tances is 1.046, for the carboxyl group on C(8). The value is charac-
teristic for unionized COOH (ionized COOH groups have a lower
ratio of about 1.030) [25], which are also confirming the reliability
of adding H atoms experimentally by different electron density
onto O atoms as mentioned above.
3.2.3. X-ray structure of (6-bromobenzo[d]thiazol-2-amine): (3,5-
dinitrobenzoic acid) [(HL+)ꢁ(dnbaꢂ)] (3)
X-ray analysis reveals that the compound 3 consists of one
6-bromobenzo[d]thiazolium-2-amine cation, and one 3,5-dinitro-
benzoate anion (Fig. 5). The present investigation clearly shows
that the positive charge (coming from the carboxylic H of the
3,5-dinitrobenzoic acid) in the title compound is on the ring nitro-
gen atom not at the extra-ring amine group, forming an ion pair.
Different from compound 2, compound 3 is an organic salt.
The CAO distances of the COOꢂ are 1.251(6) and 1.265(6) Å
One Hsal and one L form a heteroadduct by the neutral hydro-
gen bonds (N(2)AH(2A)ꢁ ꢁ ꢁO(2)#3, 2.887(4) Å, and O(1)AH(1A)
ꢁ ꢁ ꢁN(1)#1, 2.637(3) Å). In this regard the two components in the
heteroadduct are coplanar. The N(2)AH(2A)ꢁ ꢁ ꢁO(2)#3 hydrogen
bond is between the amino group of L and the carbonyl moiety
of the salicylic acid, and the O(1)AH(1A)ꢁ ꢁ ꢁN(1)#1 association is
formed between the OH of the COOH group in the salicylic acid
and the ring N atom of L. For the presence of these two kinds of
intermolecular hydrogen bonds, the COOH unit and the thiazole
moiety generated a heteromeric R22ð8Þ motif which was similar to
the hydrogen-bonded ring motif found in cocrystal from 2-ami-
no-6-methoxybenzothiazole, and sebacic acid [26]. Because of
the presence of the intramolecular hydrogen bond (O(3)AH(3)ꢁ ꢁ ꢁ
O(2), 2.589(3) Å) between the carbonyl group (acceptor) of the
COOH and the phenol group (donor) in the Hsal, it is generally ex-
pected and found that the carboxyl group is essentially coplanar
with the benzene ring [torsion angle C10AC9AC8AO1, 176.28°].
The Hsal molecule in 2 bears a hydrogen-bonded ring with S11ð6Þ
with the
D = 0.014 Å, which confirms the deprotonation of the car-
boxyl H. In the compound, there are consistently ionic hydrogen
bonds formed between the NH+ cations and the COꢂ2 anions, which
is to be expected [28]. The anion was bonded to the cation through
a pair of NAHꢁ ꢁ ꢁO hydrogen bonds to form a bicomponent adduct.
In these NAHꢁ ꢁ ꢁO hydrogen bonds, one is arised from the NH+ cat-
ion and one O atom of the COOꢂ with NAO distance of 2.568(5) Å,
the other is produced between the amino unit and the other O
atom of the same carboxylate with NAO distance of 2.903(6) Å.
For the presence of the two hydrogen bonds there exists the hydro-
gen bonded ring with descriptor of R22ð8Þ. The adjacent parallel
bicomponent adducts were joined together through the CHAO
association between the benzene CH of the cation and the nitro
group of the anion with CAO distance of 3.492 Å to form a 1D chain

S. Jin et al. / Journal of Molecular Structure 1065-1066 (2014) 223–234
229
Fig. 4. The adjacent heteroadducts were joined together via the NAHꢁ ꢁ ꢁO hydrogen bond to form a 1D zigzag chain running along the b axis direction.
Fig. 5. Molecular structure of 3 showing the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
running along the a axis direction. Two such 1D chains were held
together by the CHAO (with CAO distance of 3.331 Å), and
CAHꢁ ꢁ ꢁBr interactions to form a double chain structure (Fig. 6).
Herein, there are a pair of CAHꢁ ꢁ ꢁBr interactions between the cat-
ions of the two neighboring 1D chains in the double chain with
CABr distance of 3.902 Å. Under the CAHꢁ ꢁ ꢁBr interactions the
two cations form a R22ð8Þ ring motif. In this case the CAHꢁ ꢁ ꢁBr inter-
actions were stronger than that found in 1-Methyl-3-n-tetradecy-
limidazolium bromide monohydrate in which the CABr distance
was 3.659 Å [29]. The corresponding cations and anions at the

230
S. Jin et al. / Journal of Molecular Structure 1065-1066 (2014) 223–234
Fig. 6. The double chain of 3 formed via interchain CAHꢁ ꢁ ꢁBr interactions.
Fig. 7. 2D sheet running parallel to the ab plane.
Fig. 8. Molecular structure of 4 showing the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
two different chains in the double chains were antiparallel to each
other. The double chains were further stacked along the b axis
NAO distance of 2.985 Å) to form 3D ABAB layer network struc-
ture. In this regard the neighboring layers made an angle of ca.
60° with each other. While the third layer was parallel to the first
layer, so did the second layer and the fourth layer.
direction via the
p–p interaction between the benzene ring of
the anion and the aromatic ring of the cation with Cg–Cg distance
of 3.342 Å to form a 2D sheet running parallel to the ab plane
(Fig. 7). The thickness of the sheet was ca. 12.116 Å. The sheets
were further stacked along the c axis direction via the NAHꢁ ꢁ ꢁO
interaction (between the amino group of the cation and the nitro
group of the anion with NAO distance of 2.958 Å, and between
the same amino group of the cation and the carboxylate with
3.2.4. X-ray structure of (6-bromobenzo[d]thiazol-2-amine): (3,5-
dinitrosalicylic acid) [(HL+)ꢁ(dnsaꢂ)] (4)
The asymmetric unit of
4 consists of one cation of
6-bromobenzo[d]thiazolium-2-amine, and one monoanion of

S. Jin et al. / Journal of Molecular Structure 1065-1066 (2014) 223–234
231
Fig. 9. The double chain structure of 4 produced by interchain NAHꢁ ꢁ ꢁO and OAS interactions.
Fig. 10. 2D sheet structure of 4 extending in the plane that made an angle of ca 45° with the ab plane.
3,5-dinitrosalicylate, as shown in Fig. 8. Similar to 3, compound 4 is
also an organic salt.
organic acid–base adduct such as the above compound 2 discussed
in this manuscript. Similar to 2, there are also hydrogen bonded
S11ð6Þ motifs in the anions.
For the COOꢂ group, two CAO bond lengths (The CAO bond dis-
tances of the COOꢂ of the 3,5-dinitrosalicylate are 1.222(7)
One anion and one cation form a heteroadduct via two NAHꢁ ꢁ ꢁO
hydrogen bonds with hydrogen bonded ring graph set of R22ð8Þ.
Such kind of adjacent heteroadducts were joined together in head
to tail fashion by the CHAO association between the benzene CH of
the cation and the O atom of the 5-nitro group with CAO distance
of 3.330 Å, and OAS contact between the same O atom of the 5-ni-
tro group and the ring S atom of the cation with OAS separation of
2.940 Å to form a 1D chain running along the b axis direction. Here
the OAS separation is significantly shorter than the sum of the van
der Waals radii of S and O (3.3 Å) and the documented OAS sepa-
ration [34].
(O(1)AC(8)) and 1.291(7) Å (O(2)AC(8) with
D = 0.069 Å) are basi-
cally not equal with an average value of 1.256 (6) Å. The CAO bond
length concerning the phenol group is 1.309(6) Å which has a un-
ionized character. The torsion angles O7AN4AC13AC14, and
O5AN3AC11AC12 are 21.24°, and ꢂ29.56°, respectively. In this
regard, the 3-nitro group (O5AN3AO4) deviates more from the
phenyl plane of the anion than the 5-nitro (O7AN4AO6) group,
which is due to the fact that the 3-nitro group is involved in form-
ing more strong hydrogen bonds than that of the 5-nitro group,
this phenomenon also fits well with the published results [30].
Since the potentially hydrogen bonding hydroxyl group is pres-
ent in the ortho position to the carboxyl group in the anion, it
forms the more facile intramolecular hydrogen bonding. Thus the
usual intramolecular hydrogen bond is found between the phenol
group and a carboxylate O atom (O(3)AH(3)ꢁ ꢁ ꢁO(2), 2.406(6) Å,
150.2°) with OAO distance of 2.406(6) Å which is similar to the
corresponding value (2.409 Å) in proton-transfer compound of
[(hmt)+ꢁ[(dnsa)ꢂ] [31,32]. Yet the value is as expected generally
smaller than the distance found for the parent dnsa acid monohy-
drate [2.566(3) Å] [33], and in the neutral species found in the
Such kind of two neighboring chains were linked together via
the NAHꢁ ꢁ ꢁO interactions with NAO distances of 2.855(6)–
3.142(7) Å, and OAS interaction with OAS distance of 3.127 Å be-
tween the cations and the anions at these two neighboring chains
to form a double chain structure (Fig. 9). Herein the bicomponent
adducts at the same chain were parallel to each other, while the
bicomponent adducts at different chains in the double chain were
antiparallelly arranged. The double chains were joined together by
the CHAO association with CAO distance of 3.344 Å, and CAHꢁ ꢁ ꢁBr
interactions with CABr distances of 3.910–3.916 Å to form 2D

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S. Jin et al. / Journal of Molecular Structure 1065-1066 (2014) 223–234
Fig. 11. Molecular structure of 5 showing the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 12. The 1D chain of 5 constructed by the four-component aggregates through the BrAS interactions.
Fig. 13. 2D sheet structure of 5 extending parallel to the ab plane.
sheet extending in the direction that made an angle of ca. 45° with
the ab plane (Fig. 10). The sheets were further stacked along the
direction that is perpendicular with its extending direction via
suitable for X-ray diffraction analysis. In the asymmetric unit of
5, there are one cation of 6-bromobenzo[d]thiazolium-2-amine,
and one anion of hydrogen malonate, as shown in Fig. 11. Com-
pound 5 is also an organic salt. The X-ray structure analysis shows
that the positive charge in the title compound is also on the ring
nitrogen atom, which is similar to compounds 3, and 4. Only one
carboxylic group of the malonic acid is deprotonated which is in
accordance with the bond distance values within carboxylic groups
of acid (Table 2).
p–p interaction (between the aromatic ring of the cation and the
benzene ring of the anion with Cg–Cg distance of 3.381 Å) and
OAN contact (between the 5-nitro group of one sheet layer and
the 3-nitro group of its neighboring sheet layer with OAN distance
of 3.004 Å) to form 3D network structure.
3.2.5. X-ray structure of (6-bromobenzo[d]thiazol-2-amine): (malonic
acid) [(HL+)ꢁ(Hmalꢂ)] (5)
In the COOH (O(1)AC(8)AO(2)) group, the two CAO bond
lengths are obviously different between O(1)AC(8) (1.308(4) Å)
Crystallization of 6-bromobenzo[d]thiazol-2-amine with
malonic acid in 1:1 ratio gave single crystals of compound 5
and C(8)AO(2) (1.216(4) Å) with the
D
value of 0.092 Å, indicating
value which is
protonized COOH group. The relatively larger
D

S. Jin et al. / Journal of Molecular Structure 1065-1066 (2014) 223–234
233
Fig. 14. Molecular structure of 6 showing the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 15. Packing diagram of compound 6 showing the 1D zigzag chain running along the diagonal direction of the ab plane.
expected for neutral CAO and C@O bond distances [35] is also con-
firming the reliability of adding H atoms experimentally by differ-
ent electron density onto O atoms. But for the COOꢂ group, the two
CAO bond lengths (The CAO distances of COOꢂ of the hydrogen
3.2.6. (6-bromobenzo[d]thiazol-2-amine)2: (sebacic acid) [(L)2ꢁ(seb)]
(6)
The compound 6 was also prepared by reaction of 6-bro-
mobenzo[d]thiazol-2-amine with sebacic acid in 1:1 ratio, which
crystallizes as triclinic block crystals in the space group Pꢂ1. The
crystal structure of 6 consists of half molecule of sebacic acid
and one molecule of 6-bromobenzo[d]thiazol-2-amine in the
asymmetric unit (Fig. 14). Similar to compound 2, compound 6 is
also a cocrystal. The carboxyl groups have C@O and CAO bond dis-
tances, indicative of a protonized character, in which no Hs transfer
to the 6-bromobenzo[d]thiazol-2-amine molecules has occurred.
The ratio of CAO(long) to CAO(short) bond distances is 1.086, for
the carboxyl group on C(8). These values are characteristic for un-
ionized COOH also [25].
malonate are 1.239(4) and 1.264(4) Å,
D = 0.025 Å) are basically
not equal with an average value of 1.251 (2) Å, which is shorter
than that of the single bond of O(1)AC(8)(1.308(4) Å), but longer
than that of the double bond of C(8)AO(2) (1.216(4) Å) in the car-
boxyl group of the hydrogen malonate. It is clear that the differ-
ence in bond lengths of CAO within the carboxyl group (0.092 Å)
is greatly larger than the one found in the carboxylate group
(0.025 Å), which also confirms the deprotonation of only one car-
boxylic H.
One anion is bonded to one cation via the NAHꢁ ꢁ ꢁO associations
to form a bicomponent heteroadduct. The NAHꢁ ꢁ ꢁO hydrogen
bonds are formed between the NH+, NH2, and the O atom of the
carboxylate with NAO distances of 2.656(3)–2.807(4) Å, leading
to a R22ð8Þ graph set also. In the anions there are intramolecular
OAHꢁ ꢁ ꢁO hydrogen bonds between the carboxyl unit and the car-
boxylate with OAO distance of 2.487(3) Å. The intramolecular
OAHꢁ ꢁ ꢁO hydrogen bond also produced a S11ð6Þ ring. Two neighbor-
ing heteroadducts were held together via the CH2AO association
between the CH2 spacer of the anion and the carboxylate with
CAO distance of 3.461 Å to form a four-component aggregate.
The four-component aggregates were further linked together by
the BrAS interaction between the Br atom and the S atom of the
cations at adjacent four-component aggregates with BrAS distance
of 3.641 Å to form a 1D chain extending along the direction that
made an angle of 60° with the bc plane (Fig. 12). In this regard
the BrAS distance is somewhat longer than the value (3.4787
(7) Å) found in 2-(5-Bromo-3-methylsulfanyl-1-benzofuran-2-
yl)acetic acid [36].
Such kind of 1D chains were further stacked along the direction
that is perpendicular with its extending direction by the CH2AO
interaction with CAO distance of 3.483 Å to form a 2D sheet
extending parallel to the ab plane (Fig. 13). The sheets were further
stacked along the c axis direction by the intersheet NAHꢁ ꢁ ꢁO asso-
ciation between the amino group of the cation and the carbonyl
group of the COOH unit with NAO distance of 2.818(7) Å to form
3D ABAB layer network structure. Herein the adjacent sheets made
an angle of ca. 60° with each other. Yet the third sheet was parallel
to the first sheet, so did the second sheet and the fourth sheet.
At every carboxyl there was bonded a 6-bromobenzo[d]thiazol-
2-amine molecule via one OAHꢁ ꢁ ꢁN hydrogen bond involving the
OAH protons on the carboxylic acid moieties in the sebacic acid
and the ring nitrogen atoms on the 6-bromobenzo[d]thiazol-2-
amine (O(1)AH(1A)ꢁ ꢁ ꢁN(1)#2, 2.716(4) Å, 170.6°), and one
NAHꢁ ꢁ ꢁO hydrogen bond between the NH2 and the carbonyl unit
at the sebacic acid with NAO distance of 2.897(4) Å to form a tri-
component adduct. In the tricomponent adduct there existed an
inversion centre located at the middle point of the C12AC12A.
The tricomponent adducts were linked together by the NAHꢁ ꢁ ꢁO
hydrogen bond between the NH2 and the carbonyl unit at the seba-
cic acid with NAO distance of 2.851(4) Å to form 1D zigzag chain
running along the diagonal direction of the ab plane (Fig. 15).
4. Conclusions
Single crystal X-ray diffraction has enabled the elucidation of
six examples of 6-bromobenzo[d]thiazol-2-amine-acid adducts,
novel contributions to the extensive research into the occurrence
of acid-benzo[d]thiazol-2-amine compound motifs in organic salts
or cocrystals. In their place are a series of motifs in which extensive
strong classical NAHꢁ ꢁ ꢁO/OAHꢁ ꢁ ꢁO/OAHꢁ ꢁ ꢁN hydrogen bonds (io-
nic or neutral) combine with nonclassical weak interactions. This
variety, coupled with the varying geometries and number of the
acidic groups of the acids employed, has led to the creation of a
range of supramolecular arrays, from 1D zigzag chain, 2D sheet,
3D network structure, to 3D ABAB layer network structure. In all
of the compounds except 1, the most common hydrogen-bonded

234
S. Jin et al. / Journal of Molecular Structure 1065-1066 (2014) 223–234
hetero R22ð8Þ graph set for 2-aminoheterocyclic derivatives has
been observed. The S11ð6Þ motif was observed in 2, 4, and 5.
The formation of a salt or a cocrystal can be predicted from the
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D
pKa value of an acid (A) and a base (B). In the pharmaceutical
industry,
D
pKa ðpKa ꢂ pKa Þ > 3 is typically used as a criterion
base
acid
for selecting counterions for salt formation. In adducts 2 and 6, the
pKa for salicylic acid (2.97) and sebacic acid (pKa ¼ 4:720) are lar-
1
ger than other acids used in this manuscript (0.38 for 2,4,6-trinitro-
phenol, 2.82 for 3,5-dinitrobenzoic acid, 2.2 for 3,5-dinitrosalicylic
acid, and 1.19 (pKa ) for malonic acid). Thus in the compounds 1, 3,
1
4, and 5, the 6-bromobenzo[d]thiazolium-2-amine cations func-
tion as acceptors for ionic hydrogen bonds that organize and orient
the anions, while in compounds 2 and 6, the 6-bromobenzo[d]thia-
zol-2-amine fragments function as acceptors for neutral hydrogen
bonds. This phenomenon may be explained by the rule ‘‘strongest
donor to strongest acceptor’’. For the acids present in 1–6, the sal-
icylic acid and sebacic acid have the relatively larger pKa which
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D
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Different motives of supramolecular interactions that play
important roles in the construction of networks in the crystal sys-
tem, such as N+AHꢁ ꢁ ꢁOꢂ, OAHꢁ ꢁ ꢁO, and OAHꢁ ꢁ ꢁN hydrogen bonds
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DpKa values of
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Supporting information available
Crystallographic data for the structural analysis have been
deposited with the Cambridge Crystallographic data center, CCDC
Nos. 895433 for 1, 852951 for 2, for 851152 3, 856716 for 4,
852743 for 5, and 882645 for 6. Copies of this information may
be obtained free of charge from the +44 (1223)336 033 or Email:
deposit@ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk.
Acknowledgments
We gratefully acknowledge the financial support of the Educa-
tion Office Foundation of Zhejiang Province (Project No.
Y201017321) and the financial support of the Xinmiao project of
the Education Office Foundation of Zhejiang Province.
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