G.J. Perpétuo, J. Janczak / Journal of Molecular Structure 1041 (2013) 127–138
137
Table 5
donation of iminium and amine groups lined to the C@S and the
oxygen atoms of carboxylate group. The three-dimensional hydro-
gen-bonding supramolecular structure in 1 and in 2 is very similar,
but different to that in the crystal 3, in which the 3,4,5-trihydroxy-
benzoate anions interact each other via OAHꢁ ꢁ ꢁO hydrogen bonds
forming two-dimensional layers that are interconnected by 1-
(diaminomethylene)thiouron-1-ium cations and water molecules
forming three-dimensional network. The proton transfer from
COOH group of the respective acid 1-(diaminomethylene)thiourea
with the formation of 1-(diaminomethylene)thiouron-1-ium cat-
ion is demonstrated by appearance of the iminium bond vibration
at ꢄ1722 cmꢀ1. The presence of the OH group(s) in these crystals is
manifested in the IR-spectrum as a relatively strong narrow band
FT IR spectral data for 1-(diaminomethylene) thiouron-1-ium 4-hydroxybenzoate (1),
3,4-dihydroxybenzoate (2) and 3,4,5-trihydroxybenzoate monohydrate (3).
1/
m
2/
m
3/
m
(cmꢀ1
)
Assignment
(cmꢀ1
)
(cmꢀ1
)
3607w and
ꢄ3510sh
3429m
ma and ms (OH of water)
3479s
3403w
3437s
3390m
m
(OH) of respective anion
3347s
ma and ms of the three NH2 groups of
the cation
3222s
3183m
3291m
3202m
3200m
3138m
2668w
1723m
1664s
1638vs
1618s
1560
1527m
1498s
1466s
1395vs
1377s
1355s
1334s
1295m
1722s
1613vs
1598vs
1723s
1620vs
1605s
Imine bond stretch
m
(CAC)arom
at wavenumber above 3400 cmꢀ1. The wavenumber of the
m
(OH) correlates well with the strength of the OAHꢁ ꢁ ꢁO hydrogen
bonds in which the OH is involved. The presence of the NAHꢁ ꢁ ꢁO
and OAHꢁ ꢁ ꢁO hydrogen bonds is manifested in the IR spectrum
as a broad band between 3300 and 2700 cmꢀ1 and in the range
1564m
1532m
1569m
1530m
m
m
a(COOꢀ)
(CAN) overlapped with d(NH2)
1464s
1388vs
1378s
1356s
1342s
1292m
1264m
1210m
1161m
1100m
975w
1463s
1386s
1377s
1355s
1322s
1294m
1266w
1194m
1141w
1101m
949w
m
m
m
m
s(COOꢀ)
(CAN)
(CAN)
of 1400–1100 cmꢀ1
.
(CAC)arom
d(NH2)
d(NH2)
Appendix A. Supplementary material
m
m
m
c
(CAN)
(CAN)
(CAN)
Additional material comprising full details of the X-ray data col-
lection and final refinement parameters including anisotropic ther-
mal parameters and full list of the bond lengths and angles have
been deposited with the Cambridge Crystallographic Data Center
in the CIF format as supplementary publications no. CCDC
917240, 917242 and 917241 for 1, 2 and 3 crystals. Copies of the
data can be obtained free of charge on the application to CCDC,
12 Union Road, Cambridge, CB21EZ, UK, (fax: (+44) 1223-336-
033; email: deposit@ccdc.cam.ac.uk), Supplementary data associ-
ated with this article can be found, in the online version, at
1212m
1155w
1101w
1093w
1041s
998w
930w
876w
835w
771m
752m
732m
(NH2) overlapped with m(CAN)
b(CAH)
858m
846m
817w
c
c
c
c
(CAH)
(CAH)
(CAH)
(CAH)
777m
769w
ba(COOꢀ)
c
m
(CAC)
(C@S)
739m
692m
640m
621m
550sh
524m
499m
436m
739w
700w
651w
607w
552w
528w
498w
431w
Skeletal NACAN, CANAC, CACAC
Skeletal NACAN, CANAC, CACAC
/(CAC)
643w
602sh
558m
530w
498w
431w
ba(COOꢀ)
References
d(CACOO) out of plane
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wavenumber while the
number. The frequency of the asymmetric carboxylate vibration in
m
s(COOꢀ) band is observed at lower wave-
the IR spectra,
tween the carboxylate stretches,
ten used as spectroscopic criteria to determine the carboxylate
m
a(COOꢀ) and the magnitude of the separation be-
D
=
m
(COOꢀ) ꢀ
m
s(COOꢀ), are of-
binding mode. In the present structures the
m is equal to
ꢄ100 cmꢀ1, while in several metal complexes with chelating coor-
dination the
D is about two times greater [38–40]. The weak band
at ꢄ3607 cmꢀ1, which is observed only in the spectrum of 3 could
be assigned to the m(OH) of water molecule, since the compound 3
is monohydrate. In the spectrum of the compound 1 and 2 the this
band is not observed, both crystals are anhydrous.
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This study confirms the usefulness of 1-(diaminomethyl-
ene)thiourea as a building block in the crystal engineering and
demonstrates its interaction with mono-, di- and trihydroxybezoic
acids forming of extended supramolecular hydrogen bonding net-
works. The R22(8) hydrogen bonding motif describes the interac-
tion between the oppositely charged units of these crystals. In 1
and 2 this motif is formed between the amine groups, as donors,
joined to the same C atom of the cation and the oxygen atoms of
carboxylate group, whereas in 3, the R22(8) motif is created by