Supramolecular interactions in the adduct of di-triethylammonium, tetrachlorobenzene-1,4-dicarboxylate and tetrachlorobenzene-1,4-dicarboxylic acid

Article abstract of DOI:10.1007/s10870-008-9380-4

The adduct of di-triethylammonium, tetrachlorobenzene-1,4-dicarboxylate and tetrachlorobenzene-1,4-dicarboxylic acid, i.e. {2(C₂H ₅)₃NH⁺ C₈Cl₄O ₄ ^2- H₂C

Full text of DOI:10.1007/s10870-008-9380-4

J Chem Crystallogr (2008) 38:743–747
DOI 10.1007/s10870-008-9380-4
ORIGINAL PAPER
Supramolecular Interactions in the Adduct
of Di-triethylammonium, tetrachlorobenzene-1,4-dicarboxylate
and tetrachlorobenzene-1,4-dicarboxylic acid
Fei-Fei Lan Æ Xiao-Bin Xu Æ Shi-Yao Yang Æ
Rong-Bing Huang
Received: 9 September 2007 / Accepted: 27 March 2008 / Published online: 10 April 2008
Ó Springer Science+Business Media, LLC 2008
Abstract The adduct of di-triethylammonium, tetrachloro-
benzene-1,4-dicarboxylate and tetrachlorobenzene-1,4-
[4–9]. When substituted aromatic carboxylic acids are
applied, the interactions between the substituents can be
utilized as a controllable factor to tune the structures. For
example, in the crystal structures of substituted benzoic
acids, the crystal packing modes are entirely different when
there are ClÁÁÁCl interactions between benzoic acids [4].
Although coordination compound synthesized with tetra-
chlorobenzene-1,4-dicarboxylic acid has been reported [9],
to the best of our knowledge, the study on its supramolecular
interactions has not been reported. A better understanding of
the influence of the weak supramolecular interactions
involving halogens is necessary in the field of supramolec-
ular chemistry. Here we report a case of crystalline adduct of
tetrachlorobenzene-1,4-dicarboxylic acid, in which a variety
of intermolecular interactions are observed.
+
dicarboxylic acid, i.e. {2(C H ) NH C Cl O H C Cl O },
2-
4
2
5 3
8
4
2
8
4 4
crystallizes in triclinic, P-1 with cell dimensions of a =
˚
˚
˚
8
.5080(5) A, b = 8.9789(6) A, c = 12.5212(8) A, a =
3.301(1)°, b = 109.107(1)°, c = 103.565(1)°, V = 869.2
9
3
2-
˚
1) A and Z = 2. The C Cl O and H C Cl O moieties
8 4 4 2 8 4 4
(
link with each other by O–HÁÁÁO along c axis, C–ClÁÁÁO=C
along b axis and C–ClÁÁÁCl–C along a axis to form the 3D
+
framework of the crystal structure. The (C H ) NH cations
2
5 3
reside in the cavities of the 3D framework via various
intermolecular interactions such as N–HÁÁÁO, C–HÁÁÁO and
C–HÁÁÁp.
Keywords Triethylammonium Á
Tetrachlorobenzene-1,4-dicarboxylic acid Á
Hydrogen bond Á Intermolecular interaction
Experimental
Introduction
Synthesis of Tetrachlorobenzene-1,4-dicarboxylic acid
(H C Cl O )
2 8 4 4
Supramolecular interactions have attracted significant
attention in crystallography and crystal engineering [1–5].
And among the interactions, hydrogen bonds such as
O–HÁÁÁO, N–HÁÁÁO, C–HÁÁÁO and C–HÁÁÁp have been found to
play key roles in the determination of crystal structures. The
supramolecular interactions involving halogen atoms such
as ClÁÁÁCl and ClÁÁÁO are also important influential factors in
crystal engineering [3, 4]. Aromatic carboxylic acids have
been widely used as tectons in the field of crystal engineering
Tetrachloroterephthalic nitrile (C Cl N , 13.3g, 50 mmol)
8 4 2
was suspended in a mixture of 98% H SO (90 mL),
2
4
CH COOH (90 mL) and H O (20 mL), and refluxed at
3
2
190 °C for 72 h. The mixture was cooled down and poured
into ice water (80 mL), filtrated and washed with water
(2 9 10 mL) and ethanol (2 9 10 mL). Gray powder
(13.9 g, yield 91.2%) of tetrachlorobenzene-1,4-dicarbox-
-
1
ylic acid was obtained. IR (cm ): 3442s, 2750 * 3250s,
2932, 2613, 2502, 2064, 1718s, 1653s, 1595 m, 1444s, 1365,
1
343, 1253s, 1126, 891s, 811, 788, 704, 610s. The broad and
-1
F.-F. Lan Á X.-B. Xu Á S.-Y. Yang (&) Á R.-B. Huang
Department of Chemistry, College of Chemistry and Chemical
Engineering, Xiamen University, Xiamen 361005, China
e-mail: syyang@xmu.edu.cn
strong band at 2750*3250 cm is attributed to the car-
boxyl O–H, and the bands at 1718 and 1653 cm are
attributed to the carboxyl of the tetrachlorobenzene-1,4-
-
1
123

7
44
J Chem Crystallogr (2008) 38:743–747
dicarboxylic acid. The absence of the characteristic bands of
-
Table 2 Fractional coordinates and equivalent isotropic thermal
parameters for 1
1
nitrile at 2220*2240 cm indicates that the nitrile has been
hydrolyzed completely.
x
y
z
U
eq
O1
O2
O3
O4
N1
C1
7499(3)
7224(3)
6704(3)
6174(4)
6804(3)
3257(3)
4197(3)
5943(3)
6954(3)
6080(3)
6685(3)
5595(3)
6217(3)
7152(4)
8776(5)
8242(4)
8657(5)
5149(4)
3591(5)
1072(1)
3218(1)
7433(1)
8787(1)
7300(50)
6660(40)
2488(3)
2081(3)
4091(2)
2050(2)
9415(3)
4562(3)
3485(3)
3924(3)
2730(3)
5645(3)
4932(3)
4265(3)
3384(3)
8970(4)
9990(6)
9444(3)
7927(4)
8445(5)
8668(6)
4025(1)
1573(1)
6464(1)
4880(1)
3120(50)
4423(2)
6066(2)
2889(2)
1636(2)
2384(2)
4415(2)
4539(2)
5123(2)
5250(2)
-552(2)
391(2)
52(1)
66(1)
51(1)
65(1)
41(1)
36(1)
38(1)
35(1)
43(1)
37(1)
36(1)
34(1)
38(1)
55(1)
87(1)
50(1)
68(1)
68(1)
84(1)
57(1)
58(1)
65(1)
63(1)
78(12)
61(10)
Synthesis of Di-triethylammonium tetrachlorobenzene-
1
,4-dicarboxylate tetrachlorobenzene-1,4-dicarboxylic
+
acid, {2(C H ) NH C Cl O H C Cl O }, 1
2-
4
2
5 3
8
4
2
8
4 4
Tetrachlorobenzene-1,4-dicarboxylic acid 0.15 g (0.50
mmol) was dissolved in n-octanol (15 mL), and vapor of
triethylamine was diffused into the solution. Colorless
single crystals of 1 were formed after forty days.
C2
C3
C4
C5
X-ray Crystallography
C6
A single crystal of 1 was mounted on a Bruker APEX area-
˚
C7
942(2)
detector diffractometer with MoKa k = 0.71073 A. Data
was collected at 296(2) K. The structure was solved by
C8
1918(2)
1347(2)
1286(4)
3470(2)
3607(3)
2405(3)
1503(4)
3697(1)
3980(1)
C9
direct methods using SHELXS97 and refined by the full
C10
C11
C12
C13
C14
Cl1
Cl2
Cl3
Cl4
H1
H2
2
matrix least-squares procedure (on F ) with SHELXL97.
The position of O–H and N–H hydrogen atoms were
Table 1 Crystal data for 1
Empirical formula
CCDC deposit no.
Formula weight
Crystal size (mm)
Crystal system
14 4 4
C H17Cl NO
659449
405.09
-1242(1)
897(1)
0.40 9 0.28 9 0.11
3900(30)
2330(30)
Triclinic
10380(40)
Space group
P-1
˚
a (A)
8.5080(5)
located in difference Fourier map and refined. The other
hydrogen atoms were placed in idealized locations and
˚
refined as riding (C–H = 0.97 A for methylene and
˚
C–H = 0.96 A for methyl). Crystal data for 1 are listed in
Table 1. Fractional coordinates and equivalent isotropic
˚
b (A)
8.9789(6)
˚
c (A)
12.5212(8)
a (°)
b (°)
c (°)
93.301(1)
109.107(1)
103.565(1)
thermal parameters for 1 are listed in Table 2.
3
˚
V (A )
869.2(1)
Z
2
3
Density (calculated) (Mg/m )
1.548
Result and Discussion
F(000)
416
-
1
Absorption coefficient (mm
Index ranges
)
0.698
+
The unit cell of 1, {2(C H ) NH C Cl O H C Cl O },
2-
4
2
5 3
8
4
2
8
4 4
-11 B h B 11, -12 B k B 11,
contains two triethylammonium cations, one tetrachloroben-
zene-1,4-dicarboxylate dianion and one tetrachlorobenzene-
-16 B l B 16
Ref. collected/unique
Parameters
8811/4033 (Rint = 0.0230)
219
1,4-dicarboxylic acid molecule. The selected bond lengths
andanglesarelistedinTable 3. ThelengthsoftwoC–Obonds
˚
for H C Cl O are obviously different (1.292(3) A for C–OH
Max./min. transmissions
Final R indices[I[2r(I)]
R indices (all data)
0.9272/0.7677
2
8
4 4
R
R
1
1
= 0.0616, wR
= 0.0725, wR
2
2
= 0.1504
= 0.1582
˚
and 1.188(3) A for C=O), while the two C–O bonds for
2-
4 4
˚
C Cl O are almost equal (1.229(3) and 1.218(3) A) show-
8
2
Goodness-of-fit on F
˚
1.141
ing that one tetrachlorobenzene-1,4-dicarboxylic acid is fully
protonated and the other one is fully deprotonated. The car-
boxyl groups are almost perpendicular to the benzene rings
-
3
Max./min., Dq (e A
)
0.502/-0.255
99.1
Completeness (%)
2
2
o
2
) + (0.0822P) + 0.2159P] where P = (F
2
2
c
2-
4 4
w = 1/[r (F
o
+ 2F
)/3
(86.8° for H C Cl O and 83.6° for C Cl O ) due to the
2
8
4
4
8
1
23

J Chem Crystallogr (2008) 38:743–747
745
˚
Table 3 Bond lengths (A) and
angles (°) for 1
2-
4
+
2
H C
8
Cl
O
4 4
8
C Cl
4
O
2 5 3
(C H ) NH
O1–H1
O1–C4
O2–C4
0.90(4)
1.292(3)
1.188(3)
1.713(2)
1.715(3)
114(2)
N1–H2
N1–C9
0.90(4)
1.476(4)
1.496(3)
1.481(4)
O3–C8
O4–C8
C5–Cl3
C6–Cl4
1.229(3)
1.218(3)
1.714(2)
1.703(2)
N1–C11
N1–C13
C1–Cl1
C2–Cl2
C4–O1–H1
a
C3 –C1–C2
a
C3 –C1–Cl1
C9–N1–H2
105(2)
110(2)
b
C7 –C5–C6
b
C7 –C5–Cl3
120.2(2)
119.0(2)
120.8(2)
120.3(2)
118.6(2)
121.1(2)
123.5(3)
121.2(2)
115.3(2)
121.0(2)
118.7(2)
120.3(2)
120.3(2)
119.1(2)
120.6(2)
128.1(2)
115.2(2)
116.7(2)
C11–N1–H2
C13–N1–H2
C9–N1–C13
C9–N1–C11
C13–N1–C11
N1–C9–C10
C12–C11–N1
N1–C13–C14
106(2)
C2–C1–Cl1
C3–C2–C1
C3–C2–Cl2
C1–C2–Cl2
O2–C4–O1
O2–C4–C3
O1–C4–C3
C6–C5–Cl3
C7–C6–C5
C7–C6–Cl4
C5–C6–Cl4
O4–C8–O3
O4–C8–C7
O3–C8–C7
112.6(3)
113.4(2)
110.2(2)
113.2(3)
113.8(2)
113.7(3)
a
Symmetry codes: -x + 1,
b
-
-
y + 1, -z + 1; -x +1,
y + 1, -z
stereo hindrance of the chlorine substituents. The average C–
˚
C bond length of H C Cl O benzene ring is 0.007 A (0.5%)
framework via various intermolecular interactions. The
interactions between the moieties are discussed below
(Table 4):
2
8
4 4
2
-
shorter than that of C Cl O , indicating the difference in
8
4 4
2
4
-
p electron densities between H C Cl O and C Cl O
.
2
8
4
4
8
4
2-
4 4
(
1) O–HÁÁÁO Hydrogen bonds link C Cl O
and
2
-
8
In the crystal structure of 1, the C Cl O
and
H C Cl O link with each other by intermolecular inter-
8
4 4
H C Cl O alternatively to form zigzag chains along
2
8
4 4
2
8
4
4
2
2
c axis, (Fig. 1) with graph-set notation C (18). This
kind of motif has been reported in a recent literature
˚
actions to form the 3D framework of the crystal structure.
+
The (C H ) NH cations reside in the cavities of the 3D
2
5 3
[
6]. According to the distance of DÁÁÁA (2.479(3) A)
and \DHA (172(4)°) of O1–H1ÁÁÁO3, this hydrogen
˚
Table 4 Intermolecular interactions for 1 (A and °)
bond can be classified as ‘‘strong’’ [1].
D–HÁÁÁA
d(D–H) d(HÁÁÁA) d(DÁÁÁA) \DHA
(2) C–ClÁÁÁO=C Interactions link H C Cl O molecules
2
8
4 4
˚
along b axis (Fig. 2). The ClÁÁÁO distance of 3.209 A
O1–H1ÁÁÁO3
N1–H2ÁÁÁO4
0.90(4) 1.59(4) 2.479(3) 172(4)
0.90(4) 1.84(4) 2.698(3) 158(3)
is slightly shorter than the van der Waals distance
a
b
C9–H9aÁÁÁO4
0.97
0.96
2.88
2.66
2.59
2.67
2.89
2.65
2.44
2.88
3.08
2.60
2.882
3.436
3.655
3.638
3.778(4) 153.5
3.313(5) 125.7
3.198(3) 120.9
3.509(4) 146.5
3.394(4) 114.1
3.378(4) 132.5
3.187(4) 133.3
3.406(5) 115.8
4.023(5) 167.9
3.263(5) 126.7
c
c
C10–H10cÁÁÁO4
C11–H11bÁÁÁO1
0.97
d
C12–H12aÁÁÁO1
C12–H12bÁÁÁO2
C12–H12cÁÁÁO3
0.96
d
0.96
0.96
a
C13-H13aÁÁÁO2
C14–H14aÁÁÁO2
0.97
a
0.96
b
C14–H14bÁÁÁO4
0.96
c
C14–H14cÁÁÁO4
C9–H9bÁÁÁp (C
0.96
2
4
-
8
Cl
4
O
)
2
0.97
3.623
4.141
4.295
4.458
134.0
131.4
126.4
144.9
-
C13–H13bÁÁÁp (C
C14–H14bÁÁÁp (C
C12–H12cÁÁÁp
8
Cl
4
O
4
) 0.97
) 0.96
0.96
2
4
-
8
Cl
4
O
2 8 4 4
(H C Cl O )
\
154.2
C–ClÁÁÁO
C–ClÁÁÁO=C
C–ClÁÁÁCl–C
3.209
3.498
Fig. 1 Ortep plot of 1 showing 50% probability displacement
2-
ellipsoids. O–HÁÁÁO hydrogen bonds link C
8
Cl
4
O
4
2 8 4 4
and H C Cl O
a
Symmetry code: -x + 1, -y + 1, -z + 1; -x + 1, -y + 1, -z;
b
i
to form a zigzag chain along c axis. Symmetry code: -x + 1,
c
d
x, y + 1, z; -x + 2, -y + 1, -z + 1
ii iii
-y + 1, -z + 1; -x + 1, -y + 1, -z; x, y + 1, z
123

7
46
J Chem Crystallogr (2008) 38:743–747
Fig. 2 Ortep plot of 1 showing
ClÁÁÁO interactions between
2 8 4 4
H C Cl O along b axis.
Fig. 3 Ortep plot of 1 showing
ClÁÁÁCl interactions between
2
4
-
C
8 4
Cl O
along a axis
1
23

J Chem Crystallogr (2008) 38:743–747
˚
747
(
3.2 * 3.3 A) [2, 10], but longer than other ClÁÁÁO=N
Acknowledgments We are grateful for the financial support of the
National Natural Science Foundation of China (Grant No. 20471049)
and Xiamen University.
or ClÁÁÁO=C [11–14].
2
4 4
-
(
3) C–ClÁÁÁCl–C Interactions link C Cl O
dianions
8
along a axis (Fig. 3). The ClÁÁÁCl distance of
˚
.498 A is slightly shorter than the van der Waals
3
References
˚
distance 3.5 * 3.6 A) [2–4, 10].
4) The voids in the 3D framework are filled with
(
1. Steiner T (2002) Ange Chem Int Ed 41:48
2. Dance I (2003) New J Chem 27:22
+
C H ) NH cations via the interactions with car-
(
2
5 3
3
4
. Desiraju GR, Pathasarathy RJ (1999) Am Chem Soc 111:8725
. Moorthy JN, Natarajan R, Mal P, Venugopalan P (2002) J Am
Chem Soc 124:6530
boxyl oxygen atoms by N–HÁÁÁO hydrogen bonds, in
addition to numerous C–HÁÁÁO and C–HÁÁÁp hydrogen
bonds. The distances and angles are comparable with
those reported in recent literatures [15, 16]. The
5. Stanley N, Sethuraman V, Muthiah PT, Luger P, Weber M (2002)
Cryst Growth Des 2:631
6. Hemamalini M, Muthiah PT, Bocelli G, Cantoni A (2003) Acta
Cryst E59:o14
+
2-
C–HÁÁÁp between (C H ) NH and C Cl O
are
2
5 3
8
+
4 4
shorter than that between (C H ) NH and H C
2 8
2
5 3
7
. Yang S-Y, Long L-S, Wu Z-Y, Zhan M-X, Huang R-B, Zheng L-S
(2002) Transition Met Chem 27:546
Cl O . The difference in C–HÁÁÁp hydrogen bonds
4
4
may caused by the higher p electron density of
8. Liang M, Liao D-Z, Jiang Z-H, Yan S-P, Cheng P (2004) Inorg
Chem Commun 7:173
9
2
-
C Cl O .
4 4
8
. Bickley JF, Bonar-Law RP, Femoni C, MacLean EJ, Steiner A,
Teat SJ (2000) J Chem Soc Dalton Trans 4025
1
1
0. Nyburg SC, Faerman CH (1985) Acta Cryst B41:B274
1. Glidewell C, Low JN, Skakle JMS, Wardell JL (2005) Acta Cryst
C61:o276
Supplementary Material
1
1
1
1
1
2. Mossakowska I, W o´ jcik G (2007) Acta Cryst C63:o123
3. Fujii I, Mano Y, Hirayama N (2005) Acta Cryst E61:o1456
4. Kubicki MJ (2004) Mol Struct 698:67
5. Czugler M, B a´ thori N (2004) CrystEngComm 6:494
6. Goswami S, Gupta VK, Brahmbhatt DI, Pandya UR (2007)
J Chem Cryst 37:213
CCDC 659449 contains the supplementary crystallographic
data for this paper. These data can be obtained free of
charge via (please use the link below) by e-mailing
data_request@ccdc.cam.ac.uk, or by contacting: The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; Fax: +44-1223-336033.
www.ccdc.cam.ac.uk/data_request/cif.
123