Supramolecular assemblies of 2-hydroxy-3-naphthoic acid and N-heterocycles via various strong hydrogen bonds and weak X...π (X = C-H, π) interactions

Article abstract of DOI:10.1039/c5ra03837e

The analysis of weak interactions, including hydrogen bonds and aromatic stacking interactions, and primary hydrogen bonded synthons in the crystals of 2-hydroxy-3-naphthoic acid with various N-containing cocrystal formers (coformers) is presented. Molecu

Full text of DOI:10.1039/c5ra03837e

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Table of contents
Supramolecular Assemblies of 2ꢀhydroxyꢀ3ꢀnaphthoic Acid and
NꢀHeterocycles via Various Strong Hydrogen Bonds and Weak X···π
(X= C–H, π) Interactions
Yanyan Pang, Peiqi Xing, Xiujuan Geng, Yu Yang,* Faqian Liu, and Lei Wang,*
Hydrogen bonds and weak X···π (X= C–H, π) Interactions in a series of
multiꢀcomponent molecular constructed by 2ꢀhydroxyꢀ3ꢀnaphthoic acid with
Nꢀheterocycles were discussed in the context.

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ARTICLE
Supramolecular Assemblies of 2ꢀhydroxyꢀ3ꢀnaphthoic
Acid and NꢀHeterocycles via Various Strong
Hydrogen Bonds and Weak X···π (X= C–H, π)
Interactions
Cite this: DOI: 10.1039/x0xx00000x
Received 00th January 2012,
Accepted 00th January 2012
Yanyan Pang, Peiqi Xing, Xiujuan Geng, Yujing Zhu, Faqian Liu, and Lei
Wang,*
DOI: 10.1039/x0xx00000x
www.rsc.org/
The analysis of weak interactions, including hydrogen bonds and aromatic stacking
interactions, and primary hydrogenꢀbonded synthons in the crystals of 2ꢀhydroxyꢀ3ꢀnaphthoic
acid with various Nꢀcontaining cocrystal formers (coformers) is presented. Molecular
complexes of 2ꢀhydroxyꢀ3ꢀnaphthoic acid with 3ꢀhydroxy pyridine
pyrimidine , 2ꢀaminoꢀ4,6ꢀdimethyl pyrimidine , 1ꢀphenyl piperazine
dicyclohexylamine , 1,10ꢀphenanthroline have been obtained as single crystals in slow
1
, 2ꢀaminoꢀ4,6ꢀdimethoxy
2
3
4
, cyclohexylamine 5,
6
7
solvent evaporation approach, and investigated utilizing Xꢀray diffraction techniques. Single
crystal Xꢀray diffraction studies show total proton transfer from 2ꢀhydroxyꢀ3ꢀnaphthoic acid to
coformer in crystals
supramolecular networks extended by various hydrogen bonds, C–H···π and π···π stacking;
while crystals and exhibit 2ꢀD supramolecular structures via hydrogen honds. In every
1–6 and partial proton transfer in 7. Crystals 1, 2, 3, 5 and 7 exhibit 3ꢀD
4
6
crystal structure, hydrogen bonds (N–H···O, O–H···N, C–H···O, etc) and aromatic stacking
interactions (C–H···π, π···π stacking, etc) direct the packing modes of molecular crystals
together. Some classical supramolecular synthons, such as R2 (8) and R4 (12), usually
2
4
observed in organic solids of carboxylic acids with other Nꢀheterocycles, are again shown to be
involved in constructing most of these hydrogenꢀbonding networks. Moreover, these
multicomponent samples are characterized by infrared and thermogravimetric analysis.
Thermogravimetric analysis of mass loss for seven compounds has been shown to correlate
with the strength of hydrogen bonds in the packing fraction.
† Electronic Supplementary Information (ESI) available: IR data and
synthons. CCDC reference numbers 1032721ꢀ1032727. For ESI and
crystallographic data in CIF or other electronic format see DOI: XXXXXXX
Introduction
Stable organic solid with potentially tailorꢀmade properties
based on weak nonꢀcovalent intermolecular interactions is one
of the main research directions of crystal engineering. That how
to obtain desired product with predetermined connectivities and
stoichiometries is still
comparatively weak and reversible nature of weak nonꢀcovalent
intermolecular.1 From the point of view of crystal engineering,
A complete understanding of the supramolecular chemistry of
functional groups in a compound is precondition for the rational
design of cocrystals and salts with desired structure features.2
As one kind of numerous organic supramolecular building
blocks, aromatic carboxylic acid has aroused high degree of
attention on account of its capability for the creation of
extended architectures through directional noncovalent forces,
mainly hydrogen bonding.3 It is generally known that
carboxylic acid ligands could facilitate selfꢀassociation with
supramolecular homosynthons that are made up of selfsame
complementary functional groups.4 Furthermore, aromatic
carboxylic acids also could form persistent supramolecular
heterosynthons with different but complementary functional
groups (aromatic nitrogen, amide, etc). Indeed, in the literature,
a great challenge, due to the
Laboratory of Inorganic Synthesis and Applied Chemistry, College of
Chemistry and Molecular Engineering, Qingdao University of Science and
Technology, Qingdao 266042, P. R. China. Eꢀmail: inorchemwl@126.com;
Fax: (+86) 532ꢀ840ꢀ22681
J. Name., 2013, 00, 1-3 |
1
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DOI: 10.1039/C5RA03837E
supramolecular heterosynthons containing carboxylic acids
such as carboxylic acid···amide, carboxylic acid···pyridine are
used generally as robust yet versatile supramolecular synthetic
tools for the design and synthesize of cocrystals.5
O
O
OH
OH
N
N
N
N
N
NH2
NH2
OH
O
In the past few decades, hydroxybenzoic acids have been
selected widely as building blocks for study in crystal
engineering since they represent one of the most ubiquitous
aromatic carboxylic acids.6 For example, as far as salicylic acid
is concerned, an analysis of the Cambridge Structural Database
(CSD) data shows that, from 1971 H. S. Kim and G. A. Jeffrey
synthesized the salt [(C10H15N2+)1.5·(C7H5O3ꢀ)]7 to H. C.
Stephen Chan, G. R. Woollam, T. Wagner, M. U. Schmidt and
2ꢀamionꢀ4,6ꢀdimethyl
pyrimidine
3ꢀhydroxy pyridine 2ꢀamionꢀ4,6ꢀdimethoxy
pyrimidine
2ꢀhydroxyꢀ3ꢀnapthoic
acid
N
N
NH2
N
N
N
H
cyclohexylamine dicyclohexylamine
1ꢀphenyl piperazine
1,10ꢀphenanthroline
Scheme 1 Structural formulas of the organic crystals components in this work
R. A. Lewis composed the cocrystal [(C7H6O3)·(C6H6N2O2)] in To further understand the role of C–H···O/ C–H···N/ C–H···π/
20148, approximate 460 compounds which used salicylic acid π···π stacking interactions and the effect of coꢀexistence of
as the linker ligand have been reported. On the other hand, up various noncovalent interactions between synthons on
to the present only twelve multicomponent molecular solids of supramolecular selfꢀassembly process, we will report herein the
2ꢀhydroxyꢀ3ꢀnaphthoic acid which is salicylic acid derivative preparations, structures, and thermal stabilities of seven new
have been reported in the structural database, although some organic crystals consisting of 2ꢀhydroxyꢀ3ꢀnaphthoic acid and
related metal complexes have been reported recently.9
some typical Nꢀcontaining coformers, including 3ꢀhydroxy
In this context, we chose 2ꢀhydroxyꢀ3ꢀnaphthoic acid as major pyridine, 2ꢀaminoꢀ4,6ꢀdimethoxy pyrimidine, 2ꢀaminoꢀ4,6ꢀ
organic building block mainly considering its advantages dimethyl pyrimidine, 1ꢀphenyl piperazine, cyclohexylamine,
compared with the usual and shorter hydroxybenzoic acids (e.g., dicyclohexylamine, 1,10ꢀphenanthroline (structural formulas
the ubiquitous salicylic acid): (i) Like salicylic acid, 2ꢀhydroxyꢀ given in Scheme 1).
3ꢀnaphthoic acid also has many position isomers and each of
them has two main potential hydrogen bonding donors: strong
Experimental
carboxyl and weak hydroxyl. Besides, they have more weak
Materials and General Procedures
hydrogen bonding donors (C–H) and thus are anticipated to
form new supramolecular networks with aza compounds via
All reagents and solvents for synthesis were purchased commercially
weak C–H···N/C–H···O. Weaker interactions like the C–H···O
and used without further purification. Single crystals of these novel
play a key role in directing the packing modes of molecular
supramolecular compounds were prepared via slow solvent
crystals in chemical systems, in spite of their comparatively
evaporation method of suitable stoichiometric amounts of various
weak and reversible nature.10 In addition, the coꢀexistence of
coformers in an appropriate solvent or solvent mixture and isolated
various nonꢀcovalent interactions between the synthons makes
from their mother liquor several days later. Respective compositions
the selfꢀassembly process more stable.11 (ii) The structural
were confirmed by a PerkinꢀElmer 2400 elemental analyzer. Fourier
geometry of this building block adds another benzene ring upon
transform infrared (FTꢀIR) spectra were performed with a Nicolet
salicylic acid and makes the aromatic stacking interactions
Impact 410 FTIR spectrometer, and the samples were made as KBr
more obvious. Aromatic stacking interactions which are
pellets in range 4000ꢀ400 cmꢀ1. Absorptions were signified as
regarded as weak hydrogen bonds occurring between soft acids
follows: strong (s), medium (m), and weak (w) in the synthesis
and soft bases also have a vital role in directing supramolecular
section. All products were air stable and their thermal stability was
assembly, especially in crystal packing of aromatic
investigated by thermogravimetric analysis (TGA) experiment which
compounds.12 They are usually considered in two main
was carried out on a PerkinꢀElmer TGA 7 thermogravimetric
prototypical systems of the benzene dimer: faceꢀtoꢀface (π···π
analyzer in the temperature range of 0ꢀ900 ºC under N2 atmosphere
interactions) and edgeꢀtoꢀface (C−H···π interactions).13 As with
at a heating rate of 10 ºC/min. The crystals were prepared as follows.
other weak interactions, these two modes are nowadays widely
studied and aimed at gaining an insight into the interaction
Preparation of complexes 1–7
patterns and generating a variety of crystal structures.14
2ꢀhydroxyꢀ3ꢀnaphthoic acid:3ꢀhydroxy pyridine 1:1 salt (1) 3ꢀ
hydroxy pyridine (0.0190g, 0.2mmol) and 2ꢀhydroxyꢀ3ꢀnaphthoic
acid (0.0376g, 0.2mmol) were weighed out in a beaker containing an
ethanolꢀdistilled water mixture (5:5mL), the mixture was stirred for
10ꢀ15 min until a homogeneous solution was obtained. The solution
was filtered through a qualitative filter paper and allowed to slowly
evaporate at room temperature. Large, clubbed, yellow crystals
appeared concomitantly two weeks later. Single crystals suitable for
Xꢀray diffraction were separated from the mother liquor by filtration,
and dried under vacuum. Yield: 72%. Anal. calcd for C16H13NO4 : C,
2
| J. Name., 2012, 00, 1-3
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DOI: 10.1039/C5RA03837E
67.78; H, 4.59; N, 4.94%. Found: C, 68.21; H, 4.93; N, 4.50%. 1469m, 1449m,1397m, 1372m, 1357m, 1315m, 1246m, 1209w,
Infrared spectrum (KBr disc, cmꢀ1): 3439w, 3053w, 2749m, 2601m, 1148w, 984w, 940w, 919w, 887w, 843m, 781m, 746w, 595m, 519m.
2132w, 1838w, 1638m, 1575m, 1505s, 1453s, 1397s, 1328s, 1286s, 2ꢀhydroxyꢀ3ꢀnaphthoic acid:1ꢀphenyl piperazine 1:1 salt (4) A
1246s, 1207m, 1153m, 1111m, 1005w, 914w, 845m, 812m, 781m, 1:1 stoichiometric amount of 2ꢀhydroxyꢀ3ꢀnaphthoic acid (0.0188g,
678m, 617m, 478m.
0.1mmol) and 1ꢀphenyl piperazine (15ul, 0.1mmol) was dissolved in
2ꢀhydroxyꢀ3ꢀnaphthoic acid:2ꢀaminoꢀ4,6ꢀdimethoxy pyrimidine 5mL methanol. Another five milliliter of distilled water was added to
1:2 salt (2) A methanol solution (7mL) of 2ꢀhydroxyꢀ3ꢀnaphthoic the above solution with stirring for 15 min until gained a light
acid (0.0188g, 0.1mmol) was added to a stirred distilled water yellow homogeneous solution. The resulting solution was left to
solution (3mL) of 2ꢀaminoꢀ4,6ꢀdimethoxy pyrimidine (0.0310g, stand at ambient temperature. Yellow, irregular, sheet crystals of
0.2mmol) and the reaction mixture stirred for 30 min. The resulting compound 4 were harvested after one week in a yield of 85%. Single
light yellow solution was filtered through a qualitative filter paper crystals suitable for Xꢀray analysis were picked up from their mother
and allowed to stand in air at room temperature for 15 days yielding liquor by filtration and dried under vacuum. Anal. calcd for
yellow, diamond crystals in about 84% yield. Single crystals suitable C21H22N2O3 : C, 71.92; H, 6.28; N, 7.99%. Found: C, 72.32; H, 6.87;
for Xꢀray diffraction were separated from the mother liquor by N, 8.36%. Infrared spectrum (KBr disc, cmꢀ1): 3443w, 3025m,
filtration, and dried under vacuum. Anal. calcd for C17H17N3O5 : C, 2977m, 2842m, 2642m, 2520m, 1925w, 1648s, 1617s, 1599m,
59.42; H, 4.95; N, 12.23%. Found: C, 59.77; H, 5.38; N, 11.97%. 1578s, 1509s, 1456s, 1398m, 1331m, 1308s, 1258m, 1210w, 1033w,
Infrared spectrum (KBr disc, cmꢀ1): 3325m, 2950m, 2809w, 1694s, 921m, 873m, 842m, 747m, 689m, 525m.
1628s, 1579m, 1553m, 1519m, 1455s, 1368s, 1313m, 1245m, 1218s, 2ꢀhydroxyꢀ3ꢀnaphthoic acid:cyclohexylamine 1:2 salt (5)
1167m, 1070m, 882m, 842m, 782m, 746m, 597m.
Cyclohexylamine (24ul, 0.2mmol) and 2ꢀhydroxyꢀ3ꢀnaphthoic acid
2ꢀhydroxyꢀ3ꢀnaphthoic acid:2ꢀaminoꢀ4,6ꢀdimethyl pyrimidine (0.0188g, 0.1mmol) were mixed in acetone/distilled water
1:1 salt (3) 2ꢀhydroxyꢀ3ꢀnaphthoic acid (0.0188g, 0.1mmol) was solution(v/v=4:1, 10mL) with stirring for 30min. Upon slow
dissolved in methanol (5mL), to which a distilled water solution of evaporation of the dark yellow, homogeneous solution, yellow,
2ꢀaminoꢀ4,6ꢀdimethyl pyrimidine (5mL, 0.2mmol/mL) was added irregular, block crystals were produced over ten days. Single crystals
with stirring for 10ꢀ15 min. The mixture was then filtered to a suitable for Xꢀray diffraction were culled from the mother liquor by
beaker, and allowed to slowly evaporate at room temperature, upon filtration, and dried under vacuum. Yield: 73%. Anal. calcd for
which yellow, irregular, clubbed single crystals fitted for Xꢀray C17H21NO3 : C, 70.99; H, 7.31; N, 4.87%. Found: C, 70.75; H, 7.58;
diffraction were culled from the mother solution by filtration several N, 4.53%. Infrared spectrum (KBr disc, cmꢀ1): 3446m, 3055m, 2932s,
days later. The crystals were dried under vacuum. Yield: 79%. Anal. 2857s, 2602m, 1662s, 1623m, 1577s, 1515s, 1450s, 1397s, 1373s,
calcd for C34H34N6O6 : C, 65.52; H, 5.46; N, 13.49%. Found: C, 1327s, 1237m, 1205w, 1066w, 924w, 868m, 783m, 742m, 596m.
65.09; H, 5.80; N, 13.31%. Infrared spectrum (KBr disc, cmꢀ1): 2ꢀhydroxyꢀ3ꢀnaphthoic acid:dicyclohexylamine 2:1 salt (6) A
3411w, 3185w, 2992w, 2791w, 1948w, 1707m, 1629m, 1514m, solution of 2ꢀhydroxyꢀ3ꢀnaphthoic acid (0.0188g, 0.1mmol) in
Table 1 Crystallographic Parameters of structures 1–7
1
2
C17H17N3O5
343.33
3
C34H34N6O6
622.67
4
C21H22N2O3
350.40
5
C17H21NO3
287.35
6
C46H62N2O6
738.98
7
C34H24N2O6
556.55
Empirical formula C16H13NO4
M
283.27
monoclinic
P21/n
Crystal system
Space group
a/Å
triclinic
triclinic
orthorhombic
P212121
6.2836(6)
8.1666(10)
34.870(3)
90
monoclinic
P21/n
monoclinic
P21/c
monoclinic
P21/c
Pī
Pī
6.970(4)
16.371(8)
11.719(6)
90
7.8075(6)
9.3259(5)
12.6323(10)
97.038(6)
107.168(7)
109.563(6)
7.6965(5)
9.3446(6)
11.9676(9)
76.523(6)
86.187(6)
67.033(7)
7.0998(11)
16.265(3)
14.012(3)
90
13.1744(4)
14.8970(4)
21.1083(7)
90
16.409(1)
11.6515(4)
15.1195(10)
90
b/Å
c/Å
α/deg
β/deg
100.000(8)
90
90
97.333(18)
90
90.01
114.910(7)
90
γ/deg
90
90
V/Å3
1316.8(11)
802.65(11)
770.38(10)
1789.4(3)
4
1604.9(5)
4
4142.7(2)
4
2621.8(3)
4
Z
4
2
1
ρcalcd (g/cm3)
1.429
1.421
1.342
1.301
1.189
1.185
1.410
µ(mmꢀ1)
0.104
0.106
0.094
0.088
0.081
0.077
0.098
F(000)
592.0
360.0
328.0
744.0
616.0
1600.0
1160.0
Total/Independent
reflections
7994/2994
5318/2817
4770/2716
5111/2979
6499/2832
27764/7316
14293/6182
This journal is © The Royal Society of Chemistry 2012
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VJieowuArrtnicalelONnlainme e
DOI: 10.1039/C5RA03837E
Data/Restraints/
Parameters
Rint
2994/0/242
2817/1/241
2716/0/208
2979/0/236
2832/0/192
7316/0/487
6182/1/475
0.1166
0.0216
0.0153
0.0298
0.0290
0.0345
0.0292
b
R,a Rw
0.0484, 0.1240
1.047
0.0644, 0.1119
0.959
0.0663, 0.1467
1.046
0.0710, 0.1138
1.049
0.1102, 0.1966
1.018
0.0734, 0.1141
1.031
0.0882, 0.1151
1.042
GOF on F2
methanol (7mL) was carefully layered onto a distilled water (3mL)
solution of dicyclohexylamine (0.0090g, 0.05mmol) in a beaker.
The resulting solution was stirred for 30 min and allowed to stand
at room temperature. Two weeks later, dark yellow, irregular, block
crystals which was fit for Xꢀray determination were collected from
the mother liquor by filtration and dried under vacuum. Yield:
70%. Anal. calcd for C46H62N2O6 : C, 74.70; H, 8.39; N, 3.79%.
Found: C, 75.35; H, 8.83; N, 3.35%. Infrared spectrum (KBr disc,
cmꢀ1): 3439w, 3016w, 2934m, 2861m, 2750w, 2563w, 1651m,
1620m, 1594w, 1576w, 1513m, 1449m, 1401m, 1368m, 1346s,
1312m, 1243w, 1206w, 1147w, 1062w, 867w, 840m, 778w, 739m,
594w.
2ꢀhydroxyꢀ3ꢀnaphthoic acid:1,10ꢀphenanthroline 1:2 cocrystal
(7) A methanol (7mL) solution of 2ꢀhydroxyꢀ3ꢀnaphthoic acid
(0.0188g, 0.1mmol) was added to a distilled water (3mL) solution
of 1,10ꢀphenanthroline (0.0396g, 0.2mmol) with constant stirring
for 10ꢀ15 min until a homogeneous solution was obtained. Light
yellow, rodlike crystals suitable for Xꢀray analysis were facilely
obtained after a period of one week upon slow evaporation of the
solvents. Good quality single crystals, suitable for diffraction, were
gathered from their mother solution by filtration and dried under
vacuum. Yield: 88%. Anal. calcd for C34H24N2O6 : C, 73.31; H,
4.31; N, 5.03%. Found: C, 73.90; H, 4.67; N, 5.52%. Infrared
spectrum (KBr disc, cmꢀ1): 3425m, 3056w, 2921w, 2852w, 1651m,
1617m, 1595w, 1510m, 1450m, 1420m, 1368w, 1327w, 1217w,
1141w 880w, 841m, 765m, 716m, 618w, 591w, 482m.
Seven novel multicomponent organic crystals of 2ꢀhydroxyꢀ3ꢀ
naphthoic acid with common Nꢀcontaining heterocycles, including
3ꢀhydroxy pyridine, 2ꢀaminoꢀ4,6ꢀdimethoxy pyrimidine, 2ꢀaminoꢀ
4,6ꢀdimethyl pyrimidine, 1ꢀphenyl piperazine, cyclohexylamine,
dicyclohexylamine, 1,10ꢀphenanthroline, were discovered by
common solvent evaporation method (Table 1). These new organic
solids were characterized by single crystal Xꢀray diffraction, IR and
TGA. The outcome of single crystal Xꢀray diffraction reveals the
formation of one new cocrystal and six salts. The crystal structures
of compounds 1–7 contain extensive hydrogen bond networks in
which the 2ꢀhydroxyꢀ3ꢀnaphthoic acid and base components form a
range of possible synthons shown in Scheme 2 and supporting
information. Details of lengths and angles of selected hydrogen
bonds for 1–7 are listed in Table 2. In these structures, various
weak forces, i.e. hydrogen bonds, C–H···π and π···π stacking
interactions, play an important role as anticipated in stabilizing the
supramolecular selfꢀassembly process observed for all organic
solids. We now detailedly discuss the structural aspects and thermal
stabilities of these new multicomponent molecular complexes.
Crystal Structure of 2ꢀhydroxyꢀ3ꢀnaphthoic acid:3ꢀhydroxy
pyridine 1:1 salt (1). As depicted in Figure 1a, the molecular
structure of 1 which belongs to the monoclinic P21/n space group,
crystallizes with one molecule of 2ꢀhydroxyꢀ3ꢀnaphthoic acid
which is absolutely deprotonated and one molecule of protonated
3ꢀhydroxy pyridine. Within each 2ꢀhydroxyꢀ3ꢀnaphthoic acid
anion, the carboxyl makes dihedral angle of 6.328(1)° with the
naphthalene ring, and the dihedral angle between the naphthalene
XꢀRay crystallography
Table 2 Hydrogen Bond Metrics for Complexes 1–7
The samples for Xꢀray singleꢀcrystal diffraction of compounds 1–7
were synthesised through the procedure described above and
selected under a microscope. Then the suitable crystals were
mounted on a goniometer by gluing to a glass fiber with
cyanoacrylate adhesive, and crystal data for 1ꢀ7 were collected on a
Siemens Smart CCD diffractometer equipped with a normalꢀfocus,
2.4 kW sealedꢀtube Xꢀray source (graphiteꢀmonochromatic MoKa
radiation (l = 0.71073 Å)) operating at 50 kV and 40 mA. The
structures were solved by direct methods with Shelxs9715 and
refined against F2 by fullꢀmatrix leastꢀsquares techniques using the
Shelxs97 software package and Olex216. All the nonꢀhydrogen
atoms were refined with anisotropic displacement parameters. The
Hydrogen atoms attached to 2ꢀ6 were placed in geometrically
idealized positions and refined using a riding models. The
Hydrogen atoms residing on the atoms of 1 and 7 were located by
Fourier maps. Crystallographic parameters for 1ꢀ7 are summarized
in Table 1.
DꢀH···A(Å)
DꢀH(Å)
H···A(Å)
D···A(Å)
DꢀH··A
(deg)
149
172
178
173
144
179
177
162
127
160
177
177
137
156
131
152
168
159
1 N1–H1A···O2a
O1–H1···O3b
C15–H15···O4a
2 N1–H1B···N3c
C24–H24B···O4c
N2–H2···O3d
N1–H1A···O2d
C21–H21···O1d
C20–H20A···O1e
3 C10–H10···O1d
N15–H15B···O2d
N15–H15A···N7f
C21–H21C···O3d
C22–H22B···O2d
4 C9–H9B···O3g
N2–H2A···O1h
N2–H2B···O2h
5 N1–H1C···O3i
0.97
1.01
0.95
0.98
0.96
0.86
0.83
0.93
0.96
0.93
0.86
0.86
0.96
0.96
0.97
0.97
0.97
0.89
1.69
1.51
2.81
2.15
2.73
1.74
1.97
2.54
2.78
2.49
1.89
2.12
2.88
2.81
2.69
1.86
1.79
2.04
2.612(3)
2.519(1)
3.769(1)
3.124(2)
3.555(2)
2.604(2)
2.804(2)
3.440(2)
3.438(3)
3.375(2)
2.745(2)
2.983(2)
3.637(2)
3.713(3)
3.409(2)
2.749(2)
2.743(3)
2.888(5)
Results and discussion
4
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N1–H1B···O2i
C15–H15···O3i
N1–H1A···O1j
6 N1–H1A···O17k
N1–H1B···O27k
C47–H47A···O11l
C22–H22···O27m
7 N1–H1···O5d
O6–H6···N2k
0.89
0.93
0.89
0.97
0.97
0.97
0.93
0.92
0.95
0.99
1.90
2.81
1.88
1.83
1.82
2.54
2.88
1.87
2.62
2.58
2.786(5)
3.644(5)
2.746(4)
2.724(1)
2.758(1)
3.384(1)
3.592(1)
2.738(2)
3.182(2)
3.234(1)
174
150
163
157
161
145
134
157
117
123
O4–H4···O1d
0.88
0.98
0.96
0.99
0.94
1.62
2.39
2.64
2.52
2.52
2.491(3)
3.295(1)
3.602(1)
3.185(3)
3.301(1)
168
C28–H28···O1d
C29–H29···O1d
C24–H24···O2d
C18–H18···O2d
151
172
123
141
a ꢀx, 1ꢀy, ꢀz b 1ꢀx, 1ꢀy, ꢀz c ꢀx, ꢀy, 1ꢀz d x, ꢀ1+y, z e x, y, z f x, y, ꢀ1+z g ꢀ1+x,
2+y, z h x, ꢀ2+y, z i ꢀx, 1ꢀy, ꢀ1ꢀz j ꢀx, ꢀy, ꢀz k ꢀx, ꢀ0.5+y, 0.5ꢀz l ꢀx, 0.5+y, 0.5ꢀz
m 1+x, 1+y, z
C24–H24···O6d
O
HO
H
H
O
HN H
O
O
-OOC
H
H
O
N
N
H
N
N
O
N
O
N
N
N H
O
COO-
H
O
H
O
H
H
H
II R2 (8)
III R2 (8)
I R2 (8)
2
2
2
OH
O
O
H
O
H
H2N
N
H NH
H N
H
COO-
H
N
N
O
N
O
O
-OOC
O
H
H
N
H
H
NH2
O
VI R2 (8)
IV R2 (6)
V R2 (8)
2
2
2
H
N
O H
O
HN H
N
H
N
O
N
N
N
H
H
N
H
H NH
COOH
HN
OH
VIII R2 (5)
VII R2 (8)
IX R2 (11)
2
2
2
HO
O
H
HN
H
N
N
OH
H
H
H
O
O
O
O
H
H
O
O
H
HO
NH
O
OH
X R4 (12)
XI R4 (12)
4
4
Scheme 2
.
Main Synthons Anticipated and/or Observed in the Crystal Structures of
2ꢀhydroxyꢀ3ꢀnaphthoic acid Solid Forms
ring and the pyridine ring of 3ꢀhydroxy pyridine is 23.697(7)°.
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As illustrated in Figure 1b, each 3ꢀhydroxy pyridine cation
connects neighboring 2ꢀhydroxyꢀ3ꢀnaphthoic acid anions via
hydrogen bond N1–H1A···O2 (2.612(3) Å) and hydrogen bond
O1–H1···O3 (2.519(1) Å) forming 1D chain along the
crystallographic [001] direction. Furthermore, Hydrogenꢀbondings
C15–H15···O4 (3.769(1) Å) and weak interactions C–H···π
connect 1D chains to form 3D networks along the crystallographic
3D structure along the crystallographic [001] direction, containing
synthon XII R3 (20), which is shown in supporting information.
4
Crystal Structure of 2ꢀhydroxyꢀ3ꢀnaphthoic acid:2ꢀaminoꢀ4,6ꢀ
dimethoxy pyrimidine 1:2 salt (2). In the local structure of salt 2
as shown in Figure 2a, the molecular structure of 2 contains one 2ꢀ
aminoꢀ4,6ꢀdimethoxy pyrimidine monocation and one 2ꢀhydroxyꢀ
3ꢀnaphthoic acid monoanion in the triclinic Pī space group. The
mean plane of 2ꢀhydroxyꢀ3ꢀnaphthoic acid anion makes a dihedral
angle of 2.645° with the 2ꢀaminoꢀ4,6ꢀdimethoxy pyrimidine cation.
The carboxylic group in each acid anion makes the dihedral angle
of 4.233° with the naphthalene ring.
[001] direction (Figure 1c). The distance of C17–H17···π stacking
between C17 and the centroid Cg of the aromatic group C15, C16,
C7, C5, C13 and C19 is 3.472(2) Å, as shown in Figure 1d. The
angle of C17–H17···Cg is approximately 146°. Besides, weak
hydrogenꢀbonding interactions C–H···O further consolidating this
Figure 1. (a) Molecular structure of 1 with atom labeling of the asymmetric unit; (b) 1D chain via O−H···O and N–H···O hydrogen bonds; (c) 3ꢀD
supramolecular network extended by C–H···O hydrogen bonds and weak C–H···π interaction; (d) the weak C–H···π interaction (O, red; N, blue; C, gray; H,
turquoise in this and the subsequent figures)
6
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Figure 2. (a) Molecular structure of 2 with atom labeling of the asymmetric unit; (b) 1D wavelike chain via synthons III R2 (8) and IV R2 (6); (c) 2D layer
2
2
structure extended by hydrogen bonding interactions (d) the resultant 3D network connected by C–H···O hydrogen bonds (green broken lines)
As shown in Figure 2b, adjacent 2ꢀaminoꢀ4,6ꢀdimethoxy
pyrimidine cations are linked each other into 1D chains by
and XV R1010(50) are observed in this 3D array and described in
supporting information.
pyrimidineꢀpyrimidine homosynthons III R2 (8) (N1–H1B···N3,
Crystal Structure of 2ꢀhydroxyꢀ3ꢀnaphthoic acid:2ꢀaminoꢀ4,6ꢀ
dimethyl pyrimidine 1:1 salt (3). In regard to compound 3, it is a
monosalt as the same with crystal of 2. In the structure of 3,
crystallizing in the triclinic space group Pī, the asymmetric unit is
consisted of one 2ꢀhydroxyꢀ3ꢀnaphthoic acid monoanion and one 2ꢀ
aminoꢀ4,6ꢀdimethyl pyrimidine monocation (shown in Fig.3a).
Within each 2ꢀhydroxyꢀ3ꢀnaphthoic acid subunit, the dihedral angle
between the carboxylic group and the naphthalene nucleus is
6.911(101)°, and the dihedral angle between acid and base
components is 7.301(49)°.
2
3.124(2) Å) and IV R2 (6) (C24–H24B···O4, 3.555(2) Å). These
2
1D pyrimidine chains are connected by the 2ꢀhydroxyꢀ3ꢀnaphthoic
acid anion via pyrimidineꢀcarboxylic acid heterosynthons II R2 (8)
2
(N1–H1A···O2, 2.804(2) Å and N2–H2···O3, 2.604(2) Å) and
homosynthons I R2 (8) (C21–H21···O1, 3.440(2) Å) (Figure 2c),
2
thus, 2D planar layered structure are formed. Meanwhile, there
exist interlayer C20–H20A···O1 hydrogenꢀbonding interactions
between C20–H20A donors of acid anions and O1 acceptors of
base cations, which connect the adjoining 2D layers to general a 3ꢀ
D supramolecular network along the crystallographic [001]
direction (see Figure 2d). It is to be noted, in previous work, the
In this study, for compound 3, the classical pyridineꢀcarboxylic
acid heterosynthons R2 (8) and pyridineꢀpyridine homosynthons
2
pyridineꢀcarboxylic acid heterosynthon R2 (7) for its stable and
R2 (8) are furnished as well as 2. Similar to the oneꢀdimensional
2
2
reliable as the best combination of hydrogenꢀbonding
donor/acceptor, has been proved to be an effective tool in
synthesizing the predictable hydrogenꢀbonding networks.17
chains of the compound 2, in crystal of 3, the 2ꢀaminoꢀ4,6ꢀdimethyl
pyrimidine cations are selfꢀassembled into an infinite waved chain
(shown in Fig.3b) via synthons V R2 (8) (based on two weak C
–
2
Compared to synthon R2 (7), pyrimidineꢀcarboxylic acid
H···O interactions), VI R2 (8) (based on two strong N
–
H···O
H···N interactions).
Then these 1D chains are linked into a ladderꢀshaped twoꢀ
dimensional layer through secondary C H···O hydrogen bonds
2
2
heterosynthon II R2 (8), and pyrimidineꢀpyrimidine homosynthon
interactions) and VII R2 (8) (based on two N
–
2
2
III R2 (8) have been found in a large number of cocrystals and
2
salts,18 also may be used as effective tools to construct the desired
supramolecular architectures. Here, as expected, these two different
–
(C21···O3, 3.637(2) Å) (shown in Fig. 3c). Further analysis of the
crystal packing of 3 indicates that the additional interlayered C22–
H22B···O2 hydrogenꢀbonding interactions between the acid anions
synthons R2 (8) are also observed in the structure of 2. In addition,
2
three types of large synthons, notated as XIII R6 (26), XIV R4 (30)
6
6
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Figure 3 (a) Molecular structure of 3 with atom labeling of the asymmetric unit; (b) 1D supramolecular tape via synthons V R2 (8), VI R2 (8) and XII R2 (8);
2
2
2
(c) Perspective view of the 2D hydrogenꢀbonded layer connected by C–H···O hydrogen bonds (yellow broken lines); (d) The resultant 2D layer in the other
direction; (e) 3D network via C–H···O hydrogen bond
Figure 4 (a) Molecular structure of 4 with atom labeling of the asymmetric unit; (b) 1D supramolecular tape via N−H···O and C–H···O hydrogen bonds; (c)
Corrugated 2D layer assembled exclusively via C–H···O hydrogen bonds (blue broken lines)
8
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Figure 5 (a) Molecular structure of 5 with atom labeling of the asymmetric unit; (b) 1D chain via N–H···O hydrogen bonds; (c) 2D wave
overlapped layer connected by C–H···O hydrogen bonds; (d) The overlapped 2D layer in the other direction in two colors; (e) 3D network via
N–H···O hydrogen bonds
and base cations link two adjoining 2D ladderꢀshaped layers to give
a 3D network motif (shown in Fig. 3d). Additionally, related
Crystal
acid:cyclohexylamine 1:2 salt (5). Crystal structure of
compound crystallizes in the monoclinic space group 21/
Structure
of
2ꢀhydroxyꢀ3ꢀnaphthoic
heterodimers are connected to each other through weak C
–
H···O to
5
P
n
form some large ring motifs, such as XVI R8 (40), XVII R4 (16)
(Z=4) with one of the host molecule of 2ꢀhydroxyꢀ3ꢀnaphthoic
acid which is absolutely deprotonated and one molecule of
protonated cyclohexylamine in the asymmetric unit which is
displayed in Figure 5a. The protonated cyclohexylamine
molecule keeps the chair conformation. Within each acid
subunit, two benzene rings of 2ꢀhydroxyꢀ3ꢀnaphthoic acid
form the dihedral angles of 2.390°and the carboxylic group is
nearly coplanar with the naphthalene ring.
8
6
and XVIII R4 (20) (shown in supporting information).
4
Crystal Structure of 2ꢀhydroxyꢀ3ꢀnaphthoic acid:1ꢀphenyl
piperazine 1:1 salt (4). Structure determination of 4 reveals that
acid and base are present in a 1:1 ratio in the compound 4, and the
asymmetric unit is shown in Fig. 4a. The crystal structure of 4
reveals a salt compound with one monoanion of 2ꢀhydroxyꢀ3ꢀ
naphthoic acid and one monocation of 1ꢀphenyl piperazine in the
asymmetric unit in orthorhombic space group P212121. Within each
2ꢀhydroxyꢀ3ꢀnaphthoic acid anion, the carboxyl makes dihedral
angle of 11.340° with the naphthalene ring, and the dihedral angle
between the naphthalene ring and the aromatic ring of 1ꢀphenyl
piperazine is 20.728°.
The molecular packing analysis shows that each amino group
of cyclohexylamine cations can form two hydrogen bonds
with neighbouring acid anions, i.e. N1–H1C···O3 (2.888(5)
Å), N1–H1B···O2 (2.786(5) Å). These hydrogen bonds
connect the coformers into a 1D linear chain (see Fig. 5b).
Then neighbouring 1D chains are linked together and
continued into a 2D wavelike supramolecular layer via
auxiliary weak hydrogen bonds C15–H15···O3 (3.644(5) Å)
(see Fig. 5c). The adjacent layers are bridged by hydrogen
bonds N1–H1A···O1 (2.746(4) Å) and extended to a 3D
supramolecular network (see Fig. 5d), forming three types of
synthons, notated as X R4 (12) (Scheme 2), XX R4 (16) and
The crystal packing of
4 can be envisaged as an interesting 2D
network resulted from the packing of infinite 1D undulated
chains by strong hydrogen bonds N2–H2B···O2 (2.743(3) Å)
(shown in Fig. 4c). The 1D wavelike chains are further
composed of acid monocations alternating with base
monoanions, connecting via strong N2–H2A···O1 (2.749(2)
Å) and auxiliary weak C9–H9B···O3 (3.409(2) Å) interactions
4
4
(shown in Fig. 4b), meanwhile, synthon XIX R6 (24)
XXI R5 (28) (supporting information), respectively.
6
6
(supporting information) is observed in this structure.
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Figure 6 (a) Molecular structure of
6
with atom labeling of the asymmetric unit; (b) Synthon R4 (12) between 2ꢀhydroxyꢀ3ꢀ
4
naphthoic acid and dicyclohexylamine; (c) Twoꢀdimensional layer via synthon R4 (12) (each synthon is expressed as a different
4
color)
Crystal
acid:dicyclohexylamine 2:1 salt (6). As shown in Fig. 6a, the
crystal structure of reveals a salt compound with one
Structure
of
2ꢀhydroxyꢀ3ꢀnaphthoic
organic solids of carboxylic acids with other heterocyclic
bases, is again shown to be involved in constructing of
6
hydrogenꢀbonding networks
5
and 6 19
.
Moreover, two
monoanion of 2ꢀhydroxyꢀ3ꢀnaphthoic acid and one
monocation of dicyclohexylamine in the asymmetric unit in
different S(6) synthons (XXII and XXIII, described in
supporting information) have been found in this structure.
Crystal Structure of 2ꢀhydroxyꢀ3ꢀnaphthoic acid:1,10ꢀ
phenanthroline cocrystal 1:2 (7). Different from salts 1–
monoclinic space group
P21/c. Within each 2ꢀhydroxyꢀ3ꢀ
naphthoic acid anion, the carboxyl makes dihedral angle of
8.203° with the naphthalene ring.
6
,the molecular structure of cocrystal
7 crystallizes in space
Firstly, two dicyclohexylamine monocations and two 2ꢀ
hydroxyꢀ3ꢀnaphthoic acid monoanions are selfꢀassembled to
form a stable tetramer by two pairs of hydrogen bonds N1–
H1A···O17 (2.724(1) Å) and N1–H1B···O27 (2.758(1) Å)
group 21/c and contains one crystallographically independent
P
1,10ꢀphenanthroline monocation, one 2ꢀhydroxyꢀ3ꢀnaphthoic
acid monoanion and one 2ꢀhydroxyꢀ3ꢀnaphthoic acid neutral
molecule (Figure 7a). In this structure, the dihedral angles
between the aryl ring plane of 2ꢀhydroxyꢀ3ꢀnaphthoic acids
and the 1,10ꢀphenanthroline ring are 17.977° and 88.806°,
respectively. And the dihedral angle between two naphthalene
rings is 75.241°.
with an R4 (12) motif (see Fig. 6b). Then the acid anions in
4
each tetramer can form two hydrogen bonds with
neighbouring tetramers (C47–H47A···O11= 3.384(1) Å, C22–
H22···O27= 3.592(1) Å), connecting the tetramers to form a
2D supramolecular layer along
c
axis (see Fig. 6c). The
As shown in Fig. 7b, the two coformers are connected through
supramolecular synthon X R4 (12) or XI R4 (12) is made up of
three hydrogen bonds, N1–H1···O5, O6
–H6···N2 and C24–
4
4
two classical N–H···O hydrogen bonds, usually observed in
H24···O6, together creating synthons VIII R2 (5) and IX R2 (11),
2
2
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Figure 7 (a) Molecular structure of 7 with atom labeling of the asymmetric unit; (b) 1D banded chain extended by hydrogen bonds; (c) 2D bilayer
connected by C–H···π interactions (C–H···π interactions were denoted as green dashed lines); (d) Space filling representation of the stacking of 3D
network via π···π interactions; (e) The π···π interaction between 1,10ꢀphenanthroline monocations (centroidꢀtoꢀcentroid distance of 3.62Å)
resulting in a dimer motif. These dimer motifs are linked through
weak hydrogen bonds C26–H26···O4 to form a 1D banded chain
100
along a axis. Then deprotonated 2ꢀhydroxyꢀ3ꢀnaphthoic acid
1
2
3
4
5
6
7
ꢀ
molecules connect adjacent 1D chains into a stable 1D double chain
via hydrogen bonds O4–H4···O1 and C18–H18···O2. Furthermore,
weak interaction C–H···π connect 1D double chains to form 2D
doubleꢀdeck sheet (see Fig. 7c). As a consequence, hydrogenꢀbonded
pattern marked as synthons XXIV R2 (9), XXV R2 (8), XXVI
80
60
40
20
0
ꢀ
ꢀ
ꢀ
3
3
R2 (13) (illustrated in supporting information) come into being. As
3
illustrated in Figure 7d, the 1,10ꢀphenanthroline rings of the adjacent
layers come very close to each other and result in strong π···π
stacking (centroidꢀtoꢀcentroid distance of 3.617(2)Å) and lead to
final 3D tessellateꢀtype supramolecular architecture. In this 3D array,
-20
100
200
300
)
400
500
two large types of synthons, notated as XXVII R4 (21), and XXVIII
T(
4
R4 (22) are observed and expressed in supporting informatin.
4
Figure. 8 The thermogravimetric analysis for compounds 1–7
Thermal Stability
All compounds 1–7 are stable in air and can retain their
structural integrity at ambient conditions for a considerable
length of time. The thermogravimetric analysis (TGA) was
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implemented to confirm the thermal stability of these
crystalline materials between 0 and 900°C in nitrogen
Acknowledgements
atmosphere, and the TGA curves are shown in Fig. 8. The TGA We are grateful to the financial support by the National Natural
curve of compound shows two consecutive weight losses of Science Foundation of China (No. 51372125, 21371105 and
2
all crystalline samples from 100°C to 500°C (peaking at 169°C 21203106), and the Natural Science Foundation of Shandong
and 218°C, respectively). Both the two weight losses are 99.8%, Province, China (No. ZR2011BL015)
which is in accord with the losses of the base and acid
molecules (calcd: 100%). For
remains intact until 158°C, and then there is a sharp weight loss
ending at 280°C (peak: 253°C for crystal ), corresponding to
the explosion of all base and acid components. The TGA curve
of compounds and indicate that they have a similar trend
of decomposition. They are stable up to about 130°C at which
temperature they start to melt and decompose. The curves show
single weight losses of the three crystalline samples from 130 to
7, the TGA result indicates that it Notes and references
1
(a) Y. He, S. Xiang and B. Chen, J. Am. Chem. Soc., 2011, 133
,
7
14570ꢀ14573; (b) G. R. Desiraju, J. Am. Chem. Soc., 2013, 135
,
9952ꢀ9967; (c) C. B. Aakeröy, P. D. Chopade, C. Ganser and J.
Desper, Chem. Commun., 2011, 47, 4688ꢀ4690; (d) K. M. Dethlefs
and P. Hobza, Chem. Rev., 2000, 100, 143ꢀ167; (e) S. Ebenezer and
P. T. Muthiah, Cryst. Growth Des., 2012, 12, 3766ꢀ3785; (f) M. J.
3
,
5
6
Zaworotko, Cryst. Growth Des., 2007, 7, 4ꢀ9.
260 °C (peaking at 222°C for
3
, 237°C for
5, and 240°C for 6,
2
3
(a) S. Aitipamula, R. Banerjee, A. K. Bansal, K. Bansal, K.
Biradha, M. L. Cheney, A. R. Choudhury and G. R. Desiraju,
Cryst. Growth Des., 2012, 12, 2147ꢀ2152; (b) L. J. Thompson, N.
respectively). The TGA curves of
1
and indicate that there are
4
single weight losses of the two samples. Compound
decomposes from 160°C to 280°C (peaking at 256°C), while
4
1
Elias, L. Male and M. Tremayne, Cryst. Growth Des., 2013, 13
,
is less stable than compound
4 and decomposition of the
1464ꢀ1472.
framework begins at 134 °C (peaking at 219°C).
(a) T. R. Shattock, K. K. Arora, D. Vishweshwar and M. J.
Zaworotko, Cryst. Growth Des., 2008, , 4533ꢀ4545; (b) B. M. Ji,
8
Conclusions
D. S. Deng, N. Ma, S. B. Miao, X. G. Yang, L. G. Ji and M. Du,
Cryst. Growth Des., 2010, 10, 3060ꢀ3069; (c) N. Schultheiss, M.
Roe and S. X. M. Boerrigter, CrystEngComm, 2011, 13, 611ꢀ619;
Seven new solid forms of 2ꢀhydroxyꢀ3ꢀnaphthoic acid were
obtained in the form of six salts and one cocrystal. Their crystal
structures were determined by single crystal Xꢀray diffraction.
2ꢀhydroxyꢀ3ꢀnaphthoic acid is shown to form cocrystal with
1,10ꢀphenanthroline and salts with 3ꢀhydroxy pyridine, 2ꢀ
(d) T. S. Thakur and G. R. Desiraju, Cryst. Growth Des., 2008, 8,
4031ꢀ4044; (e) L. Wang, L. Zhao, Y. Hu, W. Wang, R. Chen and
Y. Yang, CrystEngComm, 2013, 15, 2835ꢀ2852; (f) L. Wang, Y.
Hu, W. Wang, F. Liu and K. Huang, CrystEngComm, 2014, 16
,
aminoꢀ4,6ꢀdimethoxy
pyrimidine, 1ꢀphenyl piperazine, cyclohexylamine, and
dicyclohexylamine. From Crystal structures , we can
observed that the strong intermolecular hydrogen bondings (N
H···O, O H···N, O H···O) are still the main force that selfꢀ
pyrimidine,
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