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The title complex, [Co(pyet)2(H2O)2](sac)2 (sac is the saccharinate anion, C7H4NO3S, and pyet is 2-pyridyl­ethanol, C7H9NO) contains sac ions and [Co(H2O)2(pyet)2]2+ cations, in which the Co2+ ion lies on a centre of symmetry and is octahedrally coordinated by two water and two neutral pyet mol­ecules, which act as N- and O-donor bidentate ligands forming two symmetrically-related six-membered chelate rings. The crystal packing is determined by hydrogen bonding, as well as weak sac–sac π–π-stacking interactions, resulting in a three-dimensional network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802020081/bt6212sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802020081/bt6212Isup2.hkl
Contains datablock I

CCDC reference: 202279

Key indicators

  • Single-crystal X-ray study
  • T = 133 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.026
  • wR factor = 0.074
  • Data-to-parameter ratio = 19.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes

ABSTM_02 When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.949 Tmax scaled 0.880 Tmin scaled 0.790

Comment top

Saccharin, chemically known o-sulfobenzimide, is the most widely used artificial sweetener. Its deprotonated form, the saccharinate anion (C7H4NO3S) (sac), readily coordinates to metal ions, forming stable metal complexes in the solid state. This study is a continuation of our research on the synthesis and structural characterization of complexes of metal saccharinates with other ligands containing hydroxymethyl and hydroxyethyl groups, such as monoethanolamine (Andac et al., 2000, Yilmaz, Andac et al., 2001; Yilmaz, Topcu et al., 2001), monoethanolethylenediamine (Yilmaz et al., 2002), diethanolamine (Yilmaz, Topcu et al., 2001), triethanolamine (Topcu et al., 2001), dimethanolpyridine (Andac et al., 2002) and 2-pyridylethanol (Hamamci et al., 2002a). In this paper, we report the crystal structure of 2-pyridylethanol (pyet) complex of cobalt(II) saccharinate, viz. [Co(H2O)2(pyet)2](sac)2, (I).

The structure of (I) is shown in Fig. 1, and consists of a complex cation, [Co(H2O)2(pyet)2]2+, and two sac anions. In the complex cation, the CoII ion lies on an inversion centre and is octahedrally coordinated by a pair of neutral pyet ligands and two water molecules, forming a CoN2O4 core. The sac ions are not in the primary coordination sphere, being as a counter-ion. Each pyet ligand behaves as a bidentate ligand through the N and hydroxyl O atoms, forming a six-membered chelate ring around the CoII ions. The two pyet ligands form the equatorial plane of the coordination octahedron, while two water molecules occupy the axial positions with a trans configuration. Some distortion of the metal coordination sphere from regular octahedral geometry is apparent, especially at the Owater—Co—Npyet angles (Table 1).

Both sac (C11–C16/C21/O21/N1/S1) and pyet (C31–C36/N2) are essentially planar, with an r.m.s. deviation of ca 0.01 and 0.04 Å, respectively, but the OH group deviates significantly from the pyet plane by ca 1.00 Å. Furthermore, the Co2+ ion is coplanar with the pyet plane. The crystal packing of the title compound is shown in Fig. 2. The crystal packing exhibits parallel stacking of pairs of the sac ions and therefore, results in weak ππ interactions (Cg···Cg > 4.0 Å). The H atoms of the water molecules (O4) and hydroxyl group (O3) of pyet form O—H···O hydrogen bonds with the sulfonyl O (O1) and carbonyl (O21) O atom of neighbouring sac anions. Additionally, two weak C—H···O interactions between H atoms of the pyridine ring and the carbonyl and sulfonyl O atoms of the adjacent sac ions occur. The hydrogen bonds and weak π-π interactions stabilize the crystal structure, forming a three-dimensional network.

The title compound is isostructural with the corresponding cobalt(II) complex (Hamamci et al., 2002b).

Experimental top

Previously prepared [Co(sac)2(H2O)4]·2H2O (1.0 mmol, 0.53 g) was dissolved in methanol (30 ml) at 303 K with stirring. Pyet (0.25 g, 2.0 mmol) was then added to the solution dropwise. The resulting solution was left to stand at room temperature and allowed to evaporate slowly for crystallization. Yellow single crystals, obtained within a week, were collected by suction filtration, washed with acetone and dried in air.

Refinement top

The H atoms of the hydroxyl group and water molecules were refined freely, while H atoms bonded to carbon were included using a riding model, starting from calculated positions.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A molecular view of [Co(H2O)2(pyet)2](sac)2 (40% displacement ellipsoids). [Symmetry code: (i) −x, −y, −z.]
[Figure 2] Fig. 2. Packing diagram of [Co(H2O)2(pyet)2](sac)2, showing the hydrogen-bonding scheme.
trans-Diaquabis(2-pyridylethanol-N,O)cobalt(II) disaccharinate top
Crystal data top
[Co(C7H9NO)2(H2O)2]·(C7H4NO3S)2F(000) = 730
Mr = 705.61Dx = 1.603 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 8.8391 (6) ÅCell parameters from 7972 reflections
b = 8.7910 (6) Åθ = 2.2–30.5°
c = 19.1564 (12) ŵ = 0.80 mm1
β = 100.876 (3)°T = 133 K
V = 1461.80 (17) Å3Prism, yellow
Z = 20.24 × 0.21 × 0.16 mm
Data collection top
Bruker SMART 1000CCD
diffractometer
4281 independent reflections
Radiation source: fine-focus sealed tube3827 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
Detector resolution: 8.192 pixels mm-1θmax = 30.0°, θmin = 2.2°
ω and ψ scansh = 1212
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
k = 1212
Tmin = 0.833, Tmax = 0.928l = 2626
27599 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0486P)2 + 0.2616P]
where P = (Fo2 + 2Fc2)/3
4281 reflections(Δ/σ)max = 0.001
217 parametersΔρmax = 0.48 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
[Co(C7H9NO)2(H2O)2]·(C7H4NO3S)2V = 1461.80 (17) Å3
Mr = 705.61Z = 2
Monoclinic, P21/nMo Kα radiation
a = 8.8391 (6) ŵ = 0.80 mm1
b = 8.7910 (6) ÅT = 133 K
c = 19.1564 (12) Å0.24 × 0.21 × 0.16 mm
β = 100.876 (3)°
Data collection top
Bruker SMART 1000CCD
diffractometer
4281 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
3827 reflections with I > 2σ(I)
Tmin = 0.833, Tmax = 0.928Rint = 0.024
27599 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0260 restraints
wR(F2) = 0.074H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.48 e Å3
4281 reflectionsΔρmin = 0.26 e Å3
217 parameters
Special details top

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) top
xyzUiso*/Ueq
Co0.00000.00000.00000.01265 (6)
N20.02941 (10)0.15987 (10)0.08506 (5)0.01490 (17)
C310.01232 (13)0.30566 (12)0.07006 (6)0.0175 (2)
H310.05320.33180.02210.021*
C320.00145 (14)0.41910 (13)0.12106 (6)0.0222 (2)
H320.02990.52030.10840.027*
C330.06199 (14)0.38164 (14)0.19102 (7)0.0241 (2)
H330.07480.45710.22710.029*
C340.10366 (13)0.23149 (14)0.20731 (6)0.0206 (2)
H340.14550.20340.25490.025*
C350.08391 (12)0.12232 (12)0.15362 (5)0.01612 (19)
C360.11448 (13)0.04329 (13)0.17096 (6)0.0191 (2)
H36A0.14550.05470.22310.023*
H36B0.20150.07790.14910.023*
C370.02479 (14)0.14470 (13)0.14480 (6)0.0198 (2)
H37A0.01300.24250.17090.024*
H37B0.11970.09440.15360.024*
O30.03640 (10)0.17190 (9)0.07002 (4)0.01774 (16)
H30.112 (2)0.226 (2)0.0539 (9)0.032 (4)*
O40.23746 (9)0.04935 (9)0.01561 (4)0.01771 (15)
H4A0.2684 (19)0.077 (2)0.0203 (9)0.031 (4)*
H4B0.294 (2)0.026 (2)0.0285 (10)0.036 (5)*
C110.41880 (13)0.62431 (13)0.07653 (6)0.0213 (2)
H110.33900.66370.04080.026*
C120.51630 (14)0.72119 (13)0.12240 (7)0.0233 (2)
H120.50320.82820.11770.028*
C130.63265 (14)0.66257 (13)0.17506 (6)0.0220 (2)
H130.69730.73070.20570.026*
C140.65615 (13)0.50620 (12)0.18372 (6)0.0189 (2)
H140.73540.46610.21950.023*
C150.55799 (12)0.41189 (12)0.13750 (5)0.01575 (19)
C160.44227 (12)0.46856 (12)0.08480 (6)0.0166 (2)
C210.35517 (12)0.34171 (12)0.04223 (6)0.0168 (2)
O210.24834 (9)0.36658 (10)0.00873 (4)0.02187 (17)
N10.40596 (11)0.20193 (11)0.06525 (5)0.01859 (18)
S10.54759 (3)0.21147 (3)0.132127 (13)0.01590 (7)
O10.50754 (11)0.14871 (10)0.19589 (5)0.02510 (18)
O20.68657 (10)0.14789 (10)0.11397 (5)0.02422 (18)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.01476 (10)0.01067 (10)0.01197 (10)0.00001 (6)0.00116 (7)0.00045 (6)
N20.0152 (4)0.0141 (4)0.0150 (4)0.0006 (3)0.0017 (3)0.0011 (3)
C310.0178 (5)0.0147 (5)0.0195 (5)0.0001 (4)0.0022 (4)0.0017 (4)
C320.0236 (5)0.0153 (5)0.0268 (6)0.0022 (4)0.0023 (4)0.0053 (4)
C330.0245 (6)0.0220 (5)0.0247 (6)0.0007 (4)0.0014 (4)0.0102 (4)
C340.0208 (5)0.0241 (5)0.0160 (5)0.0001 (4)0.0010 (4)0.0048 (4)
C350.0144 (4)0.0177 (5)0.0158 (5)0.0005 (4)0.0014 (4)0.0018 (4)
C360.0226 (5)0.0184 (5)0.0146 (5)0.0020 (4)0.0013 (4)0.0002 (4)
C370.0275 (5)0.0165 (5)0.0152 (5)0.0036 (4)0.0036 (4)0.0011 (4)
O30.0220 (4)0.0161 (4)0.0141 (3)0.0044 (3)0.0007 (3)0.0001 (3)
O40.0169 (4)0.0155 (4)0.0202 (4)0.0012 (3)0.0022 (3)0.0030 (3)
C110.0219 (5)0.0170 (5)0.0242 (5)0.0004 (4)0.0019 (4)0.0021 (4)
C120.0270 (6)0.0145 (5)0.0287 (6)0.0013 (4)0.0057 (5)0.0006 (4)
C130.0233 (5)0.0196 (5)0.0234 (5)0.0052 (4)0.0048 (4)0.0058 (4)
C140.0181 (5)0.0203 (5)0.0176 (5)0.0021 (4)0.0018 (4)0.0026 (4)
C150.0172 (5)0.0140 (5)0.0164 (5)0.0016 (3)0.0039 (4)0.0011 (3)
C160.0165 (5)0.0156 (5)0.0177 (5)0.0023 (4)0.0030 (4)0.0005 (4)
C210.0166 (5)0.0178 (5)0.0159 (5)0.0036 (4)0.0028 (4)0.0001 (4)
O210.0200 (4)0.0230 (4)0.0202 (4)0.0044 (3)0.0021 (3)0.0017 (3)
N10.0197 (4)0.0157 (4)0.0189 (4)0.0035 (3)0.0001 (3)0.0017 (3)
S10.01744 (12)0.01355 (12)0.01630 (12)0.00060 (8)0.00215 (9)0.00014 (8)
O10.0318 (4)0.0233 (4)0.0201 (4)0.0033 (3)0.0050 (3)0.0057 (3)
O20.0207 (4)0.0230 (4)0.0286 (4)0.0040 (3)0.0037 (3)0.0057 (3)
Geometric parameters (Å, º) top
Co—O32.0855 (8)O3—H30.827 (18)
Co—O42.1087 (8)O4—H4A0.823 (17)
Co—N22.1303 (9)O4—H4B0.839 (19)
N2—C311.3495 (13)C11—C161.3894 (15)
N2—C351.3517 (13)C11—C121.3980 (16)
C31—C321.3853 (15)C11—H110.9500
C31—H310.9500C12—C131.3963 (17)
C32—C331.3857 (17)C12—H120.9500
C32—H320.9500C13—C141.3955 (16)
C33—C341.3899 (17)C13—H130.9500
C33—H330.9500C14—C151.3908 (14)
C34—C351.3934 (15)C14—H140.9500
C34—H340.9500C15—C161.3871 (15)
C35—C361.5064 (15)C15—S11.7663 (11)
C36—C371.5260 (16)C16—C211.5047 (15)
C36—H36A0.9900C21—O211.2429 (13)
C36—H36B0.9900C21—N11.3533 (14)
C37—O31.4368 (13)N1—S11.6156 (10)
C37—H37A0.9900S1—O11.4439 (9)
C37—H37B0.9900S1—O21.4505 (9)
O3i—Co—O3180.00C36—C37—H37B109.9
O3i—Co—O488.28 (3)H37A—C37—H37B108.3
O3—Co—O491.72 (3)C37—O3—Co122.01 (6)
O4i—Co—O4180.00C37—O3—H3111.6 (11)
O3i—Co—N290.15 (3)Co—O3—H3112.6 (12)
O3—Co—N289.85 (3)Co—O4—H4A114.9 (12)
O4i—Co—N286.98 (3)Co—O4—H4B113.5 (13)
O4—Co—N293.02 (3)H4A—O4—H4B102.0 (17)
N2i—Co—N2180.00C16—C11—C12117.88 (11)
C31—N2—C35118.16 (9)C16—C11—H11121.1
C31—N2—Co118.33 (7)C12—C11—H11121.1
C35—N2—Co123.49 (7)C13—C12—C11120.79 (11)
N2—C31—C32123.32 (10)C13—C12—H12119.6
N2—C31—H31118.3C11—C12—H12119.6
C32—C31—H31118.3C14—C13—C12121.48 (11)
C31—C32—C33118.52 (11)C14—C13—H13119.3
C31—C32—H32120.7C12—C13—H13119.3
C33—C32—H32120.7C15—C14—C13116.78 (10)
C32—C33—C34118.71 (10)C15—C14—H14121.6
C32—C33—H33120.6C13—C14—H14121.6
C34—C33—H33120.6C16—C15—C14122.35 (10)
C33—C34—C35119.82 (10)C16—C15—S1107.02 (8)
C33—C34—H34120.1C14—C15—S1130.62 (9)
C35—C34—H34120.1C15—C16—C11120.71 (10)
N2—C35—C34121.40 (10)C15—C16—C21111.09 (9)
N2—C35—C36117.81 (9)C11—C16—C21128.20 (10)
C34—C35—C36120.70 (10)O21—C21—N1124.88 (10)
C35—C36—C37113.09 (9)O21—C21—C16122.04 (10)
C35—C36—H36A109.0N1—C21—C16113.08 (9)
C37—C36—H36A109.0C21—N1—S1111.78 (7)
C35—C36—H36B109.0O1—S1—O2114.18 (5)
C37—C36—H36B109.0O1—S1—N1111.96 (5)
H36A—C36—H36B107.8O2—S1—N1110.76 (5)
O3—C37—C36109.03 (9)O1—S1—C15110.51 (5)
O3—C37—H37A109.9O2—S1—C15111.17 (5)
C36—C37—H37A109.9N1—S1—C1597.01 (5)
O3—C37—H37B109.9
O3i—Co—N2—C3130.65 (8)C16—C11—C12—C130.45 (18)
O3—Co—N2—C31149.35 (8)C11—C12—C13—C140.19 (19)
O4i—Co—N2—C3161.06 (8)C12—C13—C14—C150.12 (18)
O4—Co—N2—C31118.94 (8)C13—C14—C15—C160.34 (16)
O3i—Co—N2—C35151.16 (8)C13—C14—C15—S1178.67 (9)
O3—Co—N2—C3528.84 (8)C14—C15—C16—C110.62 (17)
O4i—Co—N2—C35117.13 (8)S1—C15—C16—C11178.59 (9)
O4—Co—N2—C3562.87 (8)C14—C15—C16—C21179.35 (10)
C35—N2—C31—C321.63 (16)S1—C15—C16—C211.44 (11)
Co—N2—C31—C32179.93 (9)C12—C11—C16—C150.66 (17)
N2—C31—C32—C330.42 (18)C12—C11—C16—C21179.30 (11)
C31—C32—C33—C341.18 (18)C15—C16—C21—O21178.52 (10)
C32—C33—C34—C350.07 (18)C11—C16—C21—O211.44 (18)
C31—N2—C35—C342.93 (15)C15—C16—C21—N11.26 (13)
Co—N2—C35—C34178.88 (8)C11—C16—C21—N1178.77 (11)
C31—N2—C35—C36173.71 (10)O21—C21—N1—S1179.40 (9)
Co—N2—C35—C364.49 (13)C16—C21—N1—S10.38 (12)
C33—C34—C35—N22.19 (17)C21—N1—S1—O1115.05 (8)
C33—C34—C35—C36174.34 (10)C21—N1—S1—O2116.26 (8)
N2—C35—C36—C3754.12 (13)C21—N1—S1—C150.42 (9)
C34—C35—C36—C37122.54 (11)C16—C15—S1—O1115.50 (8)
C35—C36—C37—O379.19 (11)C14—C15—S1—O163.62 (12)
C36—C37—O3—Co41.79 (12)C16—C15—S1—O2116.64 (8)
O4i—Co—O3—C3790.33 (8)C14—C15—S1—O264.24 (12)
O4—Co—O3—C3789.67 (8)C16—C15—S1—N11.13 (8)
N2i—Co—O3—C37176.65 (8)C14—C15—S1—N1179.74 (11)
N2—Co—O3—C373.35 (8)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C32—H32···O21ii0.952.643.3559 (15)133
C33—H33···O1iii0.952.443.3295 (14)156
O4—H4A···O2iv0.823 (17)2.010 (18)2.8270 (12)172 (1)
O3—H3···O21i0.827 (18)1.830 (18)2.6433 (11)168 (1)
Symmetry codes: (i) x, y, z; (ii) x, y+1, z; (iii) x+1/2, y+1/2, z+1/2; (iv) x+1, y, z.

Experimental details

Crystal data
Chemical formula[Co(C7H9NO)2(H2O)2]·(C7H4NO3S)2
Mr705.61
Crystal system, space groupMonoclinic, P21/n
Temperature (K)133
a, b, c (Å)8.8391 (6), 8.7910 (6), 19.1564 (12)
β (°) 100.876 (3)
V3)1461.80 (17)
Z2
Radiation typeMo Kα
µ (mm1)0.80
Crystal size (mm)0.24 × 0.21 × 0.16
Data collection
DiffractometerBruker SMART 1000CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1998)
Tmin, Tmax0.833, 0.928
No. of measured, independent and
observed [I > 2σ(I)] reflections
27599, 4281, 3827
Rint0.024
(sin θ/λ)max1)0.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.074, 1.04
No. of reflections4281
No. of parameters217
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.48, 0.26

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.

Selected geometric parameters (Å, º) top
Co—O32.0855 (8)Co—N22.1303 (9)
Co—O42.1087 (8)
O3i—Co—O488.28 (3)O3—Co—N289.85 (3)
O3—Co—O491.72 (3)O4i—Co—N286.98 (3)
O3i—Co—N290.15 (3)O4—Co—N293.02 (3)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C32—H32···O21ii0.952.643.3559 (15)133
C33—H33···O1iii0.952.443.3295 (14)156
O4—H4A···O2iv0.823 (17)2.010 (18)2.8270 (12)172 (1)
O3—H3···O21i0.827 (18)1.830 (18)2.6433 (11)168 (1)
Symmetry codes: (i) x, y, z; (ii) x, y+1, z; (iii) x+1/2, y+1/2, z+1/2; (iv) x+1, y, z.
 

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