Tetra-aqua-bis(pyridine-κN)cobalt(II) bis-[4-amino-N-(6-chloro-pyridazin-3-yl)benzene-sulfonamidate].

Abstract

The structure of the title compound, [Co(C(5)H(5)N)(2)(H(2)O)(4)](C(10)H(8)ClN(4)O(2)S)(2), consists of a discrete tetra-aqua-bis(pyridine-κN)cobalt(II) cation and two 4-amino-N-(6-chloro-pyridazin-3-yl)benzene-sulfonamidate anions. In the cation, the Co(II) ion sits on an inversion centre and is octa-hedrally coordinated by two pyridine N atoms and four O atoms. A two-dimensional network parallel to (010) is formed via inter-molecular O-H⋯O, O-H⋯N, N-H⋯N and N-H⋯O hydrogen bonds.

Full text

Page 1

Tetraaquabis(pyridine-jN)cobalt(II)
bis[4-amino-N-(6-chloropyridazin-3-yl)-
benzenesulfonamidate]
Nan Li, Hong-Li Zou, Xiao-Yan Song, Yan-Cheng Liu and
Zhen-Feng Chen*
Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources
(Ministry Education of China), School of Chemistry & Chemical Engineering, Guangxi
Normal University, Guilin 541004, People’s Republic of China
Correspondence e-mail: chenzfgxnu@yahoo.com
Received 16 November 2009; accepted 19 November 2009
Key indicators: single-crystal X-ray study; T = 193 K; mean ?(C–C) = 0.005 A ˚;
R factor = 0.054; wR factor = 0.108; data-to-parameter ratio = 16.4.
The structure of the title compound, [Co(C5H5N)2(H2O)4]-
(C10H8ClN4O2S)2, consists of a discrete tetraaquabis(pyridine-
?N)cobalt(II) cation and two 4-amino-N-(6-chloropyridazin-
3-yl)benzenesulfonamidate anions. In the cation, the CoIIion
sits on an inversion centre and is octahedrally coordinated by
two pyridine N atoms and four O atoms. A two-dimensional
network parallel to (010) is formed via intermolecular O—
H???O, O—H???N, N—H???N and N—H???O hydrogen
bonds.
Related literature
For the structure of sulfachloropyridazine, see: Tan et al.
(2005). For a sulfachloropyridazine–metal complex, see: Fogg
et al. (1995). For an aquapyridine–cobalt(II) complex, see:
Clegg et al. (2006).
Experimental
Crystal data
[Co(C5H5N)2(H2O)4]-
(C10H8ClN4O2S)2
Mr= 856.62
Monoclinic, P21=c
a = 8.5897 (12) A˚
b = 25.807 (3) A˚
c = 8.5338 (12) A˚
? = 101.694 (3)?
V = 1852.5 (4) A˚3
Z = 2
Mo K? radiation
? = 0.78 mm?1
T = 193 K
0.21 ? 0.15 ? 0.12 mm
Data collection
Rigaku Mercury CCD
diffractometer
Absorption correction: multi-scan
(REQAB; Jacobson, 1998)
Tmin= 0.853, Tmax= 0.912
20359 measured reflections
4226 independent reflections
3331 reflections with I > 2?(I)
Rint= 0.050
Refinement
R[F2> 2?(F2)] = 0.054
wR(F2) = 0.108
S = 1.14
4226 reflections
258 parameters
1 restraint
H atoms treated by a mixture of
independent and constrained
refinement
??max= 0.66 e A˚?3
??min= ?0.45 e A˚?3
Table 1
Hydrogen-bond geometry (A˚,?).
D—H???A
N3—H3A???N5i
N3—H3B???O3ii
O1—H1A???O3
O1—H1B???N4iii
O2—H2A???O4
O2—H2B???N2iv
O2—H2B???O4iv
Symmetry
?x þ 1;?y þ 1;?z þ 1.
D—HH???AD???AD—H???A
0.88
0.88
0.81 (4)
0.83 (4)
0.82 (3)
0.82 (4)
0.82 (4)
2.52
2.23
2.07 (4)
2.01 (4)
1.93 (4)
1.96 (4)
2.62 (4)
3.135 (4)
3.001 (3)
2.874 (3)
2.838 (3)
2.726 (3)
2.768 (3)
3.142 (3)
127
147
174 (4)
178 (3)
165 (4)
170 (4)
123 (3)
codes:(i)x þ 1;y;z þ 1; (ii)x;y;z þ 1;(iii)x þ 1;y;z;(iv)
Data collection: CrystalClear (Rigaku, 1999); cell refinement:
CrystalClear; data reduction: CrystalStructure (Rigaku/MSC and
Rigaku, 2000); program(s) used to solve structure: SHELXS97
(Sheldrick, 2008); program(s) used to refine structure: SHELXL97
(Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008);
software used to prepare material for publication: SHELXTL.
The authors thank the National Natural Science Foundation
China(No.20861002),
(2009CB526503) the Natural Science Foundation of Guangxi,
China (Nos. 0991003, 0991012Z) and the Open Foundation of
the Key Laboratory for the Chemistry and Molecular Engin-
eering of Medicinal Resources (Ministry of Education of
China) for financial support.
ofthe 973Plan of China
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: PK2211).
References
Clegg, J. K., Hayter, M. J., Jolliffe, K. A. & Lindoy, L. F. (2006). Acta Cryst.
E62, m873–m874.
Fogg, A. G., Yusoff, A. R. H. M. & Ahmad, R. (1995). Anal. Proc. 32, 337–340.
Jacobson, R. (1998). REQAB. Private communication to the Rigaku
Corporation, Tokyo, Japan.
Rigaku (1999). CrystalClear. Rigaku Corporation, Tokyo, Japan.
Rigaku/MSC and Rigaku (2000). CrystalStrucutre. Rigaku/MSC, The
Woodands, Texas, USA, and Rigaku Coporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Tan, Y.-S., Chen, Z.-F., Liang, H. & Zhang, Y. (2005). Acta Cryst. E61, o1842–
o1844.
metal-organic compounds
m1666
Li et al.
doi:10.1107/S1600536809049599
Acta Cryst. (2009). E65, m1666
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

Page 2

supplementary materials

Page 3

supplementary materials
sup-1
Acta Cryst. (2009). E65, m1666 [ doi:10.1107/S1600536809049599 ]
Tetraaquabis(pyridine- N)cobalt(II)
yl)benzenesulfonamidate]
bis[4-amino-N-(6-chloropyridazin-3-
N. Li, H.-L. Zou, X.-Y. Song, Y.-C. Liu and Z.-F. Chen
Comment
Sulfachloropyridazine [4-amino-N-(6-chloro-3-pyridazinyl)-benzensulfonamide], is a synthetic sulfanilamide antibacterial
drug whose crystal structure is known (Tan et al. 2005). However, as far as we are aware, no crystal structure of a metal
complex containing sulfachloropyridazine has been published, although the electrochemistry of its copper(I) complex has
been described by Fogg et al. (1995). The compound consists of a [Co(H2O)4(py)2]2+ cation and two sulfacholoropyridazine
anions. Similar to tetraaquabis(pyridine-κN)cobalt(II) diacetate (Clegg et al., 2006), the coordination geometry for the CoII
cation (Fig. 1) is close to an ideal octahedron (N1—Co1—N1#1 180.000 (1)°, O1—Co1—O2 92.37 (9)°, O1—Co1—O2#1
87.63 (9)°, #1: -x + 2,-y + 1,-z + 1), with the O atoms of the coordinated water molecules occupying the equatorial positions
and with the axial sites occupied by coordinated pyridine ligands. The sulfachloropyridazine is depronated at sulfamide N2 to
generate anions, whose geometric parameters are comparable to sulfachloropyridazine (Tan et al., 2005). A two-dimensional
network is formed via intermolecular hydrogen bonds of type O—H···O, O—H···N and N—H···O (Table 1).
Experimental
Samples of sulfachloropyridazine (0.2 mmol) and Co(Ac)2.4H2O (0.1 mmol) were placed in a thick-walled Pyrex tube (ca
20 cm long). After addition of ethanol (2.2 ml), H2O (0.2 ml) and pyridine (0.1 ml), the tube was frozen with liquid nitrogen,
evacuated under vacuum and sealed with a torch. The tube was heated at 80°C for 3 days and then was slowly cooled down
to room temperature, and orange-yellow block-shaped crystals were obtained. Yield: 80%.
Refinement
The H atoms bonded to C atoms were positioned geometrically and refined using a riding model with Uiso(H) = 1.2Ueq(C)
(C—H = 0.95 Å). The H atoms attached to amino N were placed in the calculated positions, with N—H distance of 0.88 Å.
The Uiso(H) values were constrained to be 1.2Ueq of the carrier atom for amino H atom. H atom attached to O was located
in an electron-density difference map and refined isotropically.
Figures
Fig. 1. The molecular structure showing the atom-labelling scheme. Displacement ellipsoids
are drawn at the 50% probability level.

Page 4

supplementary materials
sup-2
Fig. 2. A packing diagram of title compound, viewing down the [100] direction. Hydrogen
bonds are shown as dashed lines.
Tetraaquabis(pyridine-κN)cobalt(II) bis[4-amino-N-(6-chloropyridazin-3-yl)benzenesulfonamidate]
Crystal data
[Co(C5H5N)2(H2O)4](C10H8ClN4O2S)2
F(000) = 882
Dx = 1.536 Mg m−3
Mo Kα radiation, λ = 0.71070 Å
Cell parameters from 6394 reflections
θ = 3.1–27.5°
µ = 0.78 mm−1
T = 193 K
Block, orange-yellow
Mr = 856.62
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 8.5897 (12) Å
b = 25.807 (3) Å
c = 8.5338 (12) Å
β = 101.694 (3)°
V = 1852.5 (4) Å3
Z = 2
0.21 × 0.15 × 0.12 mm
Data collection
Rigaku Mercury CCD
diffractometer
Radiation source: fine-focus sealed tube
graphite
Detector resolution: 7.31 pixels mm-1
ω scans
Absorption correction: multi-scan
(REQAB; Jacobson, 1998)
Tmin = 0.853, Tmax = 0.912
20359 measured reflections
4226 independent reflections
3331 reflections with I > 2σ(I)
Rint = 0.050
θmax = 27.5°, θmin = 3.2°
h = −11→9
k = −32→33
l = −10→11
Refinement
Refinement on F2
Primary atom site location: structure-invariant direct
methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring
sites
H atoms treated by a mixture of independent and
constrained refinement
w = 1/[σ2(Fo2) + (0.0291P)2 + 1.7941P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.054
wR(F2) = 0.108
S = 1.14
4226 reflections

Page 5

supplementary materials
sup-3
258 parameters
Δρmax = 0.66 e Å−3
Δρmin = −0.45 e Å−3
1 restraint
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance mat-
rix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations
between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of
cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, convention-
al R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-
factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
1.0000
0.07781 (10)
0.54834 (8)
0.9392 (3)
0.7795 (2)
0.6620 (2)
0.5622 (2)
0.9177 (3)
0.3692 (3)
0.7205 (3)
0.7967
0.6729
0.1620 (3)
0.0921 (3)
0.9858 (4)
1.0705
0.9403 (4)
0.9928
0.8187 (4)
0.7851
0.7458 (4)
0.6609
0.7977 (4)
0.7463
0.5891 (3)
0.7082 (4)
0.7613
0.7499 (4)
0.8307
0.6757 (3)
y
0.5000
0.20506 (3)
0.39936 (3)
0.42160 (8)
0.51495 (9)
0.37878 (8)
0.45443 (7)
0.52499 (9)
0.39029 (9)
0.30830 (10)
0.2850
0.3190
0.34401 (9)
0.30070 (9)
0.56332 (13)
0.5817
0.57775 (15)
0.6054
0.55177 (14)
0.5609
0.51210 (14)
0.4933
0.49995 (12)
0.4726
0.36813 (10)
0.33130 (12)
0.3199
0.31125 (12)
0.2856
0.32790 (11)
z
0.5000
0.22874 (12)
0.61366 (9)
0.4313 (3)
0.5400 (3)
0.5233 (2)
0.6462 (2)
0.2536 (3)
0.5297 (3)
1.2615 (3)
1.2827
1.3377
0.3915 (3)
0.3205 (3)
0.1875 (4)
0.2530
0.0292 (4)
−0.0125
−0.0666 (4)
−0.1760
−0.0018 (4)
−0.0657
0.1575 (4)
0.2015
0.8007 (3)
0.8356 (4)
0.7545
0.9877 (4)
1.0101
1.1094 (3)
Uiso*/Ueq
0.02572 (15)
0.0489 (2)
0.02737 (18)
0.0348 (5)
0.0337 (5)
0.0330 (5)
0.0331 (5)
0.0315 (6)
0.0299 (6)
0.0394 (6)
0.047*
0.047*
0.0309 (6)
0.0323 (6)
0.0405 (8)
0.049*
0.0479 (9)
0.057*
0.0457 (9)
0.055*
0.0469 (9)
0.056*
0.0378 (7)
0.045*
0.0262 (6)
0.0339 (7)
0.041*
0.0355 (7)
0.043*
0.0299 (6)
Co1
Cl1
S1
O1
O2
O3
O4
N1
N2
N3
H3A
H3B
N4
N5
C1
H1C
C2
H2C
C3
H3
C4
H4
C5
H5
C6
C7
H7
C8
H8
C9