mer-(4-Aminobenzenesulfonato-κN)-triaqua(1, 10-phenanthroline-κ2N,N′)-cobalt(II) chloride

Article abstract of DOI:10.1107/S0108270103026957

The hydrogen bonding interaction of the crystal structure in the supramolecular compound of [Co(C₆H₆NO₃S)(C ₁₂H₈N ₂)(H₂O)₃]Cl was discussed. The compound contains a discrete cation formed by one 4-aminobenzenesulfonate ligand, one 1,10-phenanthroline ligand and three coordinated water molecules with one chloride anion. The discrete cations and chloride anions were found to be connected by hydrogen-bonding interactions into a two-dimensional supramolecular motif. It was found that hydrogen-bonding interactions consolidate the structural architecture and extends the two-dimesional supramolecular structure into a three-dimensional network.

Full text of DOI:10.1107/S0108270103026957

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
mode of coordination of 4-abs differ from that observed in
[Co(4-abs)2(4,40-bipy)(H2O)4]ÁH2O (Wang et al., 2002), in
which the 4-abs ligands are not coordinated to CoII and form
one-dimensional head-to-tail zigzag chains via hydrogen-
bonding interactions. The rings of the 4-abs and 1,10-phen
ISSN 0108-2701
mer-(4-Aminobenzenesulfonato-jN)-
triaqua(1,10-phenanthroline-j2N,N0)-
cobalt(II) chloride
Ming-Hua Huang, Li-Hua Bi and Shao-Jun Dong*
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied
Chemistry, Chinese Academy of Sciences, Changchun, Jilin 130022, People's
Republic of China
Correspondence e-mail: dongsj@ns.ciac.jl.cn
groups are not completely parallel to one another, the dihe-
dral angle between their planes being 12.6ꢀ and the average
Ê
ring separation being 3.324 A.
As shown in Fig. 2, the discrete [Co(C6H6NO3S)-
(C12H8N2)(H2O)3]+ cations and chloride anions are connected
into a two-dimensional supramolecular motif. The rings of two
Received 29 October 2003
Accepted 24 November 2003
Online 20 December 2003
Both coordination and hydrogen bonds contribute to
networking in the supramolecular title compound, [Co(C6H6-
NO3S)(C12H8N2)(H2O)3]Cl, which contains a discrete [Co-
(C6H6NO3S)(C12H8N2)(H2O)3]+ complex cation, formed by
one 4-aminobenzenesulfonate ligand, one 1,10-phenanthro-
line ligand and three coordinated water molecules, together
with one uncoordinated chloride anion. These discrete cations
and chloride anions are connected by hydrogen-bonding
interactions into a two-dimensional supramolecular motif.
Further hydrogen-bonding interactions consolidate the struc-
tural architecture and extend the two-dimensional supramol-
ecular structure into a three-dimensional network.
Comment
Supramolecular frameworks based on metal and organic
building blocks that contain diverse topologies with desired
features are receiving increasing attention because of their
promising potential uses in catalysis (Fujita et al., 1994), gas
storage (Kitaura et al., 2003) and magnetism (Inoue et al.,
1996). However, there have been few reports of metal-based
organosulfonate anions containing supramolecular com-
pounds to date (Cai, Chen, Feng et al., 2001; Cai, Chen, Liao et
al., 2001; Wang et al., 2002). We present here a novel
compound, [Co(C6H6NO3S)(C12H8N2)(H2O)3]Cl, (I), built
from discrete [Co(C6H6NO3S)(C12H8N2)(H2O)3]+ cations,
each formed by one 4-aminobenzenesulfonate (4-abs) ligand,
one 1,10-phenanthroline (1,10-phen) ligand and three coor-
dinated water molecules, together with one uncoordinated
chloride anion.
Figure 1
The molecular structure of the title compound, with the atom-numbering
scheme. Displacement ellipsoids are drawn at the 50% probability level.
(The symmetry code is as in Table 2.)
As depicted by Fig. 1, the CoII center exhibits a slightly
distorted octahedral coordination geometry, de®ned by three
Ê
aqua
O
2.083 (2) A and CoÐOW3 = 2.091 (2) A], two N atoms from a
atoms [CoÐOW1 = 2.065 (2) A, CoÐOW2 =
Ê
Ê
Figure 2
The two-dimensional network of [Co(4-abs)(1,10-phen)(H2O)3]+ cations
and chloride anions formed via hydrogen-bonding interactions. The
Ê
1,10-phen ligand [CoÐN1 = 2.119 (2) A and CoÐN2 =
Ê
2.116 (2) A] and an N-atom donor from a 4-abs ligand [CoÐ
Ê
N3 = 2.270 (2) A; Table 1]. The coordination environment and
1
1
symmetry codes are as in Table 2, plus (v) x
1 ‡ x; y; z.
;
y; z 12; (vi)
2
2
m30 # 2004 International Union of Crystallography
DOI: 10.1107/S0108270103026957
Acta Cryst. (2004). C60, m30±m32

metal-organic compounds
Data collection
Siemens P4 diffractometer
! scans
Rint = 0.026
ꢂmax = 26.0ꢀ
Absorption correction: scan
(SHELXTL; Siemens, 1994)
Tmin = 0.561, Tmax = 0.687
5562 measured re¯ections
4060 independent re¯ections
2959 re¯ections with I > 2ꢄ(I)
h = 1 ! 8
k = 1 ! 19
l = 22 ! 22
3 standard re¯ections
every 97 re¯ections
intensity decay: 8.0%
Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.034
wR(F2) = 0.073
S = 1.09
4060 re¯ections
271 parameters
H-atom parameters constrained
w = 1/[ꢄ2(F2o) + (0.02P)2]
where P = (F2o + 2Fc2)/3
(Á/ꢄ)max = 0.001
3
Ê
Áꢅmax = 0.31 e A
3
Ê
0.37 e A
Áꢅmin
=
Figure 3
A packing diagram, showing the three-dimensional structure viewed
along the a axis.
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
CoÐOW1
CoÐOW2
CoÐOW3
CoÐN1
CoÐN2
CoÐN3
SÐO1
2.065 (2)
2.083 (2)
2.091 (2)
2.119 (2)
2.116 (2)
2.270 (2)
1.461 (2)
1.469 (2)
SÐO3
SÐC16
1.4415 (18)
1.767 (2)
1.329 (3)
1.361 (3)
1.333 (3)
1.360 (3)
1.428 (3)
N1ÐC1
N1ÐC5
N2ÐC10
N2ÐC6
N3ÐC13
4-abs and two 1,10-phen ligands from two different discrete
cations lie parallel to one another. In the supramolecular
architecture, unusual hydrogen-bonding interactions play a
crucial role. The OW2 and OW1 water molecules from one
[Co(4-abs)(1,10-phen)(H2O)3]+ cation interact with the SO3
group of the 4-abs ligand from another, thus forming
SÐO2
OW1ÐCoÐOW2
OW1ÐCoÐOW3
OW1ÐCoÐN1
OW1ÐCoÐN2
OW1ÐCoÐN3
OW2ÐCoÐOW3
OW2ÐCoÐN1
OW2ÐCoÐN2
OW2ÐCoÐN3
OW3ÐCoÐN1
OW3ÐCoÐN2
OW3ÐCoÐN3
N1ÐCoÐN2
N1ÐCoÐN3
N2ÐCoÐN3
O1ÐSÐO2
O1ÐSÐO3
O1ÐSÐC16
O2ÐSÐO3
90.81 (8)
92.55 (8)
170.16 (8)
94.96 (8)
82.49 (8)
86.49 (8)
96.43 (8)
92.36 (8)
172.50 (8)
94.52 (8)
172.41 (8)
90.43 (8)
78.14 (8)
90.62 (8)
91.58 (8)
111.23 (11)
114.76 (12)
106.28 (12)
111.67 (12)
O2ÐSÐC16
O3ÐSÐC16
CoÐN1ÐC5
C1ÐN1ÐC5
CoÐN1ÐC1
C6ÐN2ÐC10
CoÐN2ÐC6
CoÐN2ÐC10
CoÐN3ÐC13
N1ÐC1ÐC2
N1ÐC5ÐC6
N1ÐC5ÐC4
N2ÐC6ÐC5
N2ÐC6ÐC7
N2ÐC10ÐC9
N3ÐC13ÐC18
N3ÐC13ÐC14
SÐC16ÐC15
SÐC16ÐC17
105.35 (12)
106.85 (11)
112.67 (16)
117.8 (2)
128.30 (18)
117.8 (2)
113.19 (16)
128.86 (18)
118.20 (17)
122.4 (3)
117.1 (2)
123.3 (2)
117.1 (2)
122.8 (2)
122.4 (2)
120.4 (2)
120.1 (2)
119.86 (18)
120.25 (19)
i
Ê
hydrogen-bonding interactions [OW2Á Á ÁO1 = 2.875 (3) A and
i
Ê
OW1Á Á ÁO2 = 2.664 (3) A; see Table 2 for all symmetry codes].
Furthermore, the OW2 and OW1 water molecules from two
adjacent cations are bridged via hydrogen-bonding inter-
ii
Ê
actions with a chloride anion [Cl Á Á ÁOW1 = 3.072 (2) A and
i
Ê
Cl Á Á ÁOW2 = 3.018 (2) A]. In addition, there are hydrogen-
bonding interactions between the OW3 water molecules and
the SO3 groups of 4-abs anions from two adjacent building
blocks [O1 Á Á ÁOW3 = 2.824 (3) A and O2iiiÁ Á ÁOW3 =
iv
Ê
Ê
2.748 (3) A]. Therefore, such hydrogen-bonding interactions
consolidate the structural architecture and further extend the
two-dimensional supramolecular structure into a three-
dimensional network (see Fig. 3).
Table 2
Hydrogen-bonding geometry (A, ).
ꢀ
Ê
Experimental
To an aqueous solution of CoCl2Á6H2O (0.2379 g, 1.00 mmol) was
added 4-aminobenzenesulfonic acid (0.074 g, 0.54 mmol) with stirring
at 298 K. After the pH of the solution had been adjusted to ꢁ5.5 with
dilute NaOH, 1,10-phen (0.078 g, 0.50 mmol) was added slowly and
the mixture was stirred for 30 min at 333 K. After ®ltration, a clear
orange solution was obtained, which was allowed to stand at room
temperature. Orange crystals were obtained after two weeks.
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
OW1ÐHW1Á Á ÁO2i
OW1ÐHW2Á Á ÁClii
OW2ÐHW3Á Á ÁCli
N3ÐH3AÁ Á ÁO3iii
N3ÐH3BÁ Á ÁClii
0.84
0.95
0.97
0.90
0.90
0.90
0.91
0.93
1.82
2.17
2.06
2.18
2.53
2.01
1.84
1.90
2.664 (3)
3.072 (2)
3.018 (2)
3.062 (3)
3.392 (2)
2.875 (3)
2.748 (3)
2.824 (3)
177
158
170
167
160
161
174
170
OW2ÐHW4Á Á ÁO1i
OW3ÐHW5Á Á ÁO2iii
OW3ÐHW6Á Á ÁO1iv
Crystal data
1
2
1
2
1
2
1 1
Symmetry codes: (i) 12 ‡ x; 21 y; 21 ‡ z; (ii) x
;
y; 12 ‡ z; (iii)
x; y
;
2 2
z; (iv)
[Co(C6H6NO3S)(C12H8N2)-
(H2O)3]Cl
Mr = 500.81
Z = 4
3
1
2
1 1
x; y
;
2 2
z.
Dx = 1.616 Mg m
Mo Kꢁ radiation
Cell parameters from 24 re¯ections
ꢂ = 5.2±10.2ꢀ
ꢃ = 1.11 mm
T = 293 (2) K
Block, orange
0.50 Â 0.38 Â 0.32 mm
Monoclinic, P21=n
Water H atoms were located from difference maps and their
positions were ®xed during re®nement. Other H atoms were placed in
geometric positions using a riding model, with CÐH distances of
Ê
a = 7.0148 (10) A
Ê
1
b = 15.896 (4) A
Ê
c = 18.587 (5) A
ꢀ = 96.548 (18)ꢀ
Ê
V = 2059.0 (8) A
Ê
Ê
0.93 A and NÐH distances of 0.90 A, and with Uiso(H) values equal
to 1.2Ueq(C, N).
3
ꢂ
Acta Cryst. (2004). C60, m30±m32
Huang, Bi and Dong
[Co(C6H6NO3S)(C12H8N2)(H2O)3]Cl m31

metal-organic compounds
Data collection: XSCANS (Siemens, 1994); cell re®nement:
XSCANS; data reduction: XSCANS; program(s) used to solve
structure: SHELXTL (Siemens, 1994); program(s) used to re®ne
structure: SHELXTL; molecular graphics: SHELXTL; software used
to prepare material for publication: SHELXTL.
References
Cai, J. W., Chen, C. H., Feng, X. L., Liao, C. Z. & Chen, X. M. (2001). J. Chem.
Soc. Dalton Trans. pp. 2370±2375.
Cai, J. W., Chen, C. H., Liao, C. Z., Yao, J. H., Hu, H. P. & Chen, X. M. (2001).
J. Chem. Soc. Dalton Trans. pp. 1137±1142.
Fujita, M., Kwon, Y. J., Washizu, S. & Ogura, K. (1994). J. Am. Chem. Soc. 116,
1151±1152.
Inoue, K., Hayamizu, T., Iwamura, H., Hashizume, D. & Ohashi, Y. (1996). J.
Am. Chem. Soc. 118, 1803±1804.
Kitaura, R., Seki, K., Akiyama, G. & Kitagawa, S. (2003). Angew. Chem. Int.
Ed. 42, 428±431.
This work was supported by the National Natural Science
Foundation of China (grant Nos. 20275036 and 2021130506).
Siemens (1994). XSCANS (Version 2.1) and SHELXTL (Release 5.03).
Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Wang, Y. H., Feng, L. Y., Li, Y. G., Hu, C. W., Wang, E. B., Hu, N. H. & Jia, H. Q.
(2002). Inorg. Chem. 41, 6351±6357.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: BM1550). Services for accessing these data are
described at the back of the journal.
ꢂ
m32 Huang, Bi and Dong
[Co(C6H6NO3S)(C12H8N2)(H2O)3]Cl
Acta Cryst. (2004). C60, m30±m32