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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): m1465.
Published online 2009 October 31. doi:  10.1107/S1600536809043918
PMCID: PMC2971130

Bis[2-(2-pyridylmethyl­eneamino)benzene­sulfonato-κ3 N,N′,O]cobalt(II) dihydrate

Abstract

The title complex, [Co(C12H9N2O3S)2]·2H2O, has site symmetry 2 with the CoII cation located on a twofold rotation axis. Two tridentate 2-(2-pyridylmethyl­eneamino)benzene­sulfonate (paba) ligands chelate to the CoII cation in a distorted octa­hedral geometry. The pyridine and benzene rings in the paba ligand are oriented at a dihedral angle of 42.86 (13)°. Inter­molecular O—H(...)O and C—H(...)O hydrogen bonding is present in the crystal structure.

Related literature

For general background to the coordination chemistry of the sulfonate ligands, see: Jiang et al. (2006 [triangle]). For the isostructural Zn and Cd complexes, see: Cai et al. (2008 [triangle]); Ou-Yang et al. (2008 [triangle]). For the synthesis, see: Casella & Gullotti (1986 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-m1465-scheme1.jpg

Experimental

Crystal data

  • [Co(C12H9N2O3S)2]·2H2O
  • M r = 617.53
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1465-efi2.jpg
  • a = 19.636 (2) Å
  • b = 8.0973 (8) Å
  • c = 16.2819 (16) Å
  • V = 2588.8 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.88 mm−1
  • T = 291 K
  • 0.31 × 0.25 × 0.07 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.771, T max = 0.939
  • 17970 measured reflections
  • 2410 independent reflections
  • 1960 reflections with I > 2σ(I)
  • R int = 0.039

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.089
  • S = 1.02
  • 2410 reflections
  • 177 parameters
  • H-atom parameters constrained
  • Δρmax = 0.44 e Å−3
  • Δρmin = −0.46 e Å−3

Data collection: SMART (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809043918/xu2642sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809043918/xu2642Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by the Science Foundation of the Guangxi Zhuang Autonomous Region of China (grant No. 0731053).

supplementary crystallographic information

Comment

The design of supermolecular coordination complexes in which both coordination bonds and hydrogen bonds take part in the self-assembly chemistry have recently generated increasing interest. Our group have focused on the exploration of the coordination chemistry of the sulfonate ligands (Jiang et al.., 2006). We report here the structure of the title complex (Fig. 1).

The CoII complex is isostructural with [Zn(Paba)2].2H2O and [Cd(Paba)2].2H2O whose structure has been described in detail (Cai et al.., 2008; Ou-Yang et al.., 2008). The Co(II) atom lies on the twofold rotation axis and is coordinated by pyridine N, imine N and sulfonate O atoms from two paba- ligands with a distorted octahedral geometry (Table 1). This structure is similar to complexes with N,N',O-tridentate donor ligands (Casella et al.., 1986). The O—H···O and C—H···O hydrogen bonding (Table 2) is present in the crystal structure.

Experimental

The potassium salt of 2-(pyridylmethyl)imine-2-benzenesulfonic acid (pabaK) was synthesized according to the literature method (Casella & Gullotti, 1986). To prepare the title complex, pabaK (1 mmol, 0.30 g) was dissolved in methanol (10 ml) at 333 k and an aqueous solution (10 ml) containing Co(AcO)2.4H2O (0.5 mmol, 0.125 g) was added. The mixture was stirred at 333 K for 4 h, then cooled to room temperature and filtered. Red crystals suitable for X-ray diffraction were obtained by slowly evaporation over several days, with a yield of 60%. Elemental analysis, found (%): C: 46.59; H: 4.04; N: 9.11; S: 10.25, calc (%): C: 46.64; H: 3.56; N: 9.07; S: 10.36.

Refinement

H atoms bonded to C atoms were positioned geometrically with the C—H distance of 0.93 A, and treated as riding atoms, with Uiso(H) = 1.2Ueq(C). Water H atoms were placed in a difference Fourier map and refined as riding in as-found relative positions with Uiso(H) = 1.5Ueq(O).

Figures

Fig. 1.
The molecular structure of the complex, showing the atom-numbering scheme. Symmetry code: -x + 2, y, -z + 1/2.

Crystal data

[Co(C12H9N2O3S)2]·2H2OF(000) = 1268
Mr = 617.53Dx = 1.584 Mg m3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 4317 reflections
a = 19.636 (2) Åθ = 2.5–24.7°
b = 8.0973 (8) ŵ = 0.88 mm1
c = 16.2819 (16) ÅT = 291 K
V = 2588.8 (4) Å3Block, red
Z = 40.31 × 0.25 × 0.07 mm

Data collection

Bruker SMART CCD area-detector diffractometer2410 independent reflections
Radiation source: fine-focus sealed tube1960 reflections with I > 2σ(I)
graphiteRint = 0.039
[var phi] and ω scansθmax = 25.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −23→23
Tmin = 0.771, Tmax = 0.939k = −9→9
17970 measured reflectionsl = −19→19

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.0467P)2 + 1.5384P] where P = (Fo2 + 2Fc2)/3
2410 reflections(Δ/σ)max = 0.001
177 parametersΔρmax = 0.44 e Å3
0 restraintsΔρmin = −0.46 e Å3

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 matrix. 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, conventional 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)

xyzUiso*/Ueq
Co11.00000.68407 (5)0.25000.02746 (14)
S10.87615 (3)0.82456 (8)0.34750 (3)0.03191 (17)
O10.79780 (13)0.4090 (4)0.44814 (16)0.1166 (13)
H1W0.75500.41210.44000.175*
H2W0.81880.44250.40640.175*
O20.84711 (9)0.6617 (2)0.34011 (11)0.0477 (5)
O30.95125 (8)0.8220 (2)0.34231 (9)0.0350 (4)
O40.85336 (9)0.9170 (2)0.41814 (10)0.0438 (4)
N10.90902 (9)0.7307 (2)0.17616 (11)0.0297 (4)
N20.99827 (10)0.4858 (3)0.16249 (12)0.0335 (5)
C10.85084 (11)0.9367 (3)0.25933 (13)0.0310 (5)
C20.81355 (13)1.0800 (3)0.26678 (15)0.0413 (6)
H20.80161.11890.31860.050*
C30.79387 (15)1.1660 (4)0.19754 (18)0.0534 (8)
H30.76911.26340.20270.064*
C40.81090 (14)1.1074 (4)0.12064 (16)0.0538 (8)
H40.79741.16530.07410.065*
C50.84796 (13)0.9631 (4)0.11249 (15)0.0444 (7)
H50.85930.92460.06040.053*
C60.86829 (11)0.8756 (3)0.18134 (14)0.0309 (5)
C70.89905 (12)0.6270 (3)0.11848 (14)0.0362 (6)
H70.86240.63990.08280.043*
C80.94554 (12)0.4883 (3)0.10895 (13)0.0330 (5)
C90.93760 (15)0.3705 (3)0.04869 (16)0.0469 (7)
H90.90080.37490.01280.056*
C100.98533 (16)0.2455 (4)0.04253 (18)0.0534 (7)
H100.98080.16390.00270.064*
C111.03915 (16)0.2432 (3)0.09565 (18)0.0503 (7)
H111.07220.16120.09190.060*
C121.04376 (14)0.3648 (3)0.15512 (16)0.0428 (6)
H121.08020.36180.19150.051*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Co10.0260 (2)0.0333 (3)0.0231 (2)0.000−0.00434 (16)0.000
S10.0305 (3)0.0415 (4)0.0238 (3)−0.0001 (3)0.0004 (2)0.0016 (2)
O10.0579 (15)0.193 (3)0.099 (2)−0.0322 (18)−0.0192 (14)0.079 (2)
O20.0511 (11)0.0469 (11)0.0452 (11)−0.0111 (9)−0.0011 (9)0.0076 (9)
O30.0292 (8)0.0485 (10)0.0272 (8)0.0047 (7)−0.0040 (7)−0.0038 (7)
O40.0425 (10)0.0625 (12)0.0263 (9)0.0069 (9)0.0045 (7)−0.0037 (8)
N10.0253 (9)0.0408 (11)0.0231 (10)0.0000 (8)−0.0006 (7)−0.0016 (9)
N20.0383 (11)0.0336 (11)0.0287 (10)0.0019 (9)−0.0042 (8)−0.0010 (8)
C10.0238 (11)0.0400 (13)0.0293 (12)−0.0001 (10)−0.0006 (9)0.0029 (10)
C20.0354 (14)0.0526 (16)0.0357 (13)0.0096 (12)0.0024 (11)−0.0009 (12)
C30.0490 (16)0.0553 (18)0.0560 (18)0.0229 (14)0.0011 (14)0.0072 (14)
C40.0512 (17)0.072 (2)0.0377 (15)0.0214 (15)−0.0016 (12)0.0139 (14)
C50.0389 (14)0.0639 (19)0.0305 (13)0.0118 (13)0.0013 (11)0.0054 (12)
C60.0229 (11)0.0433 (13)0.0266 (11)0.0005 (10)−0.0010 (9)0.0015 (11)
C70.0301 (12)0.0503 (15)0.0282 (12)−0.0005 (11)−0.0073 (10)−0.0023 (11)
C80.0342 (12)0.0382 (13)0.0265 (12)−0.0024 (11)−0.0032 (10)−0.0016 (10)
C90.0526 (16)0.0487 (16)0.0395 (15)−0.0023 (13)−0.0109 (12)−0.0098 (13)
C100.073 (2)0.0435 (16)0.0433 (17)0.0039 (15)−0.0087 (15)−0.0127 (13)
C110.0646 (19)0.0376 (15)0.0488 (17)0.0134 (14)−0.0012 (14)−0.0036 (13)
C120.0492 (16)0.0410 (15)0.0381 (14)0.0070 (12)−0.0085 (12)−0.0004 (12)

Geometric parameters (Å, °)

Co1—O32.1029 (16)C2—C31.380 (4)
Co1—O3i2.1029 (16)C2—H20.9300
Co1—N1i2.1862 (18)C3—C41.380 (4)
Co1—N12.1863 (18)C3—H30.9300
Co1—N22.147 (2)C4—C51.383 (4)
Co1—N2i2.147 (2)C4—H40.9300
S1—O21.4421 (18)C5—C61.385 (3)
S1—O41.4433 (17)C5—H50.9300
S1—O31.4773 (17)C7—C81.456 (3)
S1—C11.770 (2)C7—H70.9300
O1—H1W0.8502C8—C91.378 (3)
O1—H2W0.8402C9—C101.383 (4)
N1—C71.275 (3)C9—H90.9300
N1—C61.422 (3)C10—C111.366 (4)
N2—C121.331 (3)C10—H100.9300
N2—C81.354 (3)C11—C121.384 (4)
C1—C21.377 (3)C11—H110.9300
C1—C61.406 (3)C12—H120.9300
O3—Co1—O3i115.85 (9)C1—C2—H2119.9
O3—Co1—N2149.80 (7)C3—C2—H2119.9
O3i—Co1—N285.98 (7)C2—C3—C4120.0 (3)
O3—Co1—N2i85.98 (7)C2—C3—H3120.0
O3i—Co1—N2i149.80 (7)C4—C3—H3120.0
N2—Co1—N2i83.20 (11)C3—C4—C5120.3 (2)
O3—Co1—N1i83.51 (6)C3—C4—H4119.8
O3i—Co1—N1i85.95 (6)C5—C4—H4119.8
N2—Co1—N1i120.48 (7)C4—C5—C6120.4 (2)
N2i—Co1—N1i75.60 (7)C4—C5—H5119.8
O3—Co1—N185.95 (6)C6—C5—H5119.8
O3i—Co1—N183.51 (6)C5—C6—C1118.7 (2)
N2—Co1—N175.60 (7)C5—C6—N1122.4 (2)
N2i—Co1—N1120.48 (7)C1—C6—N1118.78 (19)
N1i—Co1—N1160.09 (11)N1—C7—C8119.4 (2)
O2—S1—O4114.72 (11)N1—C7—H7120.3
O2—S1—O3112.14 (11)C8—C7—H7120.3
O4—S1—O3111.25 (10)N2—C8—C9122.3 (2)
O2—S1—C1106.90 (11)N2—C8—C7115.0 (2)
O4—S1—C1107.06 (11)C9—C8—C7122.6 (2)
O3—S1—C1103.96 (10)C8—C9—C10118.8 (2)
H1W—O1—H2W110.5C8—C9—H9120.6
S1—O3—Co1120.19 (9)C10—C9—H9120.6
C7—N1—C6120.03 (19)C11—C10—C9119.2 (3)
C7—N1—Co1114.63 (16)C11—C10—H10120.4
C6—N1—Co1124.72 (14)C9—C10—H10120.4
C12—N2—C8117.8 (2)C10—C11—C12118.9 (3)
C12—N2—Co1126.85 (16)C10—C11—H11120.5
C8—N2—Co1115.36 (16)C12—C11—H11120.5
C2—C1—C6120.4 (2)N2—C12—C11122.9 (2)
C2—C1—S1120.67 (18)N2—C12—H12118.6
C6—C1—S1118.91 (18)C11—C12—H12118.6
C1—C2—C3120.1 (2)

Symmetry codes: (i) −x+2, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1W···O4ii0.852.163.009 (3)179
O1—H2W···O20.842.152.867 (3)143
C7—H7···O1iii0.932.563.425 (3)154
C11—H11···O4iv0.932.463.389 (3)172

Symmetry codes: (ii) −x+3/2, y−1/2, z; (iii) x, −y+1, z−1/2; (iv) −x+2, y−1, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2642).

References

  • Bruker (2004). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Cai, C.-X., Ou-Yang, M., Zhao, Z.-Y. & Jiang, Y.-M. (2008). Acta Cryst. E64, m1195. [PMC free article] [PubMed]
  • Casella, L. & Gullotti, M. (1986). Inorg. Chem.25, 1293–1303.
  • Jiang, Y.-M., Li, J.-M., Xie, F.-Q. & Wang, Y.-F. (2006). Chin. J. Struct. Chem.25, 767–770.
  • Ou-Yang, M., Huang, X.-R., Zhang, Y.-L. & Jiang, Y.-M. (2008). Acta Cryst. E64, m1461. [PMC free article] [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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