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In the title compound, [Co(C9H8NO4)2(H2O)4]·4H2O, the Co atom lies on an inversion centre in an octa­hedral environment that is formed from two O atoms of two 2,6-dimethyl­pyridinium-3,5-dicarboxyl­ate monoanions and four water mol­ecules. Hydrogen bonds that involve the pyridinium NH groups and both coordinated and uncoordinated water mol­ecules give rise to an infinite three-dimensional network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049161/ng2335sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049161/ng2335Isup2.hkl
Contains datablock I

CCDC reference: 667151

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.029
  • wR factor = 0.100
  • Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Co1 - O5 .. 5.98 su PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.04
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Co1 (9) 1.54
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

Recently, we reported the crystal structure of trans-tetraaqua-bis(2,6-dimethylpyridinium-3,5-dicarboxylato) copper(II) tetrahydrate (Shi et al. 2007). The title cobalt analog (Fig. 1) is centrosymmetric, and the metal exists in an octahedral coordination geometry. Molecules are linked by O—H···O and N—H···O hydrogen bonds involving allpotential donors to generate infinite three-dimensional network. (Table 1; Fig. 2). The two compounds are not isostructural although both have the same formula.

Related literature top

For the synthesis of the ligand, see: Checchi (1959). For the crystal structure of the copper compound (which is not isostructural), see: Shi et al. (2007)

Experimental top

2,6-Dimethylpyridine-3,5-dicarboxylic acid was prepared by basic hydrolysis of diethyl 2,6-dimethylpyridine-3,5-dicarboxylate (Checchi, 1959). Diethyl 2,6-dimethylpyridine-3,5-dicarboxylate (25.1 g, 0.1 mol) and potassium hydroxide (13.44 g, 0.24 mol) were dissolved in 150 ml e thanol and 150 ml water. The solution was stirred for three hours under reflux conditions. 2,6-Dimethylpyridine-3,5-dicarboxylic acid (10.5 g), a white precipitate, was formed by adjusting the pH of the solution to 3 with 0.1 M HCl after ethanol was removed by evaporation.

The complex was synthesized with cobalt(II) dinitrate hexahydrate (0.582 g, 2 mmol) and 2,6-dimethylpyridine-3,5-dicarboxylic acid (0.390 g, 2 mmol) in water; the pH was adjusted to 6 with 0.01 M sodium hydroxide. Pink crystals separated from the filtered solution after several days.

Refinement top

H atoms bound to C atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å, 0.97 Å for aromatic and methyl H atoms respectively; Uiso(H) was set to = 1.2Ueq of the carrier atom (1.5 Ueq for methyl H atoms). Water H atoms were initially located in a difference Fourier map; they were treated as riding on their parent atoms. The H4 atom bond to N1 atoms was located in a difference Fourier map and refined isotropically.

Structure description top

Recently, we reported the crystal structure of trans-tetraaqua-bis(2,6-dimethylpyridinium-3,5-dicarboxylato) copper(II) tetrahydrate (Shi et al. 2007). The title cobalt analog (Fig. 1) is centrosymmetric, and the metal exists in an octahedral coordination geometry. Molecules are linked by O—H···O and N—H···O hydrogen bonds involving allpotential donors to generate infinite three-dimensional network. (Table 1; Fig. 2). The two compounds are not isostructural although both have the same formula.

For the synthesis of the ligand, see: Checchi (1959). For the crystal structure of the copper compound (which is not isostructural), see: Shi et al. (2007)

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997a).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for all atoms. H atoms are represented as spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines; [symmetry codes: (i): -x + 2,-y + 1,-z].
[Figure 2] Fig. 2. Packing diagram for the crystal of the title compound, showing the three-dimensional hydrogen-bonding network. H-bonds are drawn as dashed lines; H atoms not involved in hydrogen bonds have been omitted for clarity.
trans-Tetraaquabis(2,6-dimethylpyridinium-3,5-dicarboxylato- κO)cobalt(II) tetrahydrate top
Crystal data top
[Co(C9H8NO4)2(H2O)4]·4H2OZ = 1
Mr = 591.39F(000) = 309
Triclinic, P1Dx = 1.583 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.597 (5) ÅCell parameters from 5838 reflections
b = 8.651 (7) Åθ = 3.4–27.5°
c = 10.715 (7) ŵ = 0.77 mm1
α = 69.90 (3)°T = 295 K
β = 69.75 (2)°Block, pink
γ = 83.58 (2)°0.48 × 0.39 × 0.31 mm
V = 620.4 (8) Å3
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2803 independent reflections
Radiation source: fine-focus sealed tube2631 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.015
ω scansθmax = 27.5°, θmin = 3.4°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 98
Tmin = 0.706, Tmax = 0.794k = 1111
6106 measured reflectionsl = 1313
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)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100H atoms treated by a mixture of independent and constrained refinement
S = 1.21 w = 1/[σ2(Fo2) + (0.0531P)2 + 0.2698P]
where P = (Fo2 + 2Fc2)/3
2803 reflections(Δ/σ)max = 0.004
175 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = 0.30 e Å3
Crystal data top
[Co(C9H8NO4)2(H2O)4]·4H2Oγ = 83.58 (2)°
Mr = 591.39V = 620.4 (8) Å3
Triclinic, P1Z = 1
a = 7.597 (5) ÅMo Kα radiation
b = 8.651 (7) ŵ = 0.77 mm1
c = 10.715 (7) ÅT = 295 K
α = 69.90 (3)°0.48 × 0.39 × 0.31 mm
β = 69.75 (2)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2803 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
2631 reflections with I > 2σ(I)
Tmin = 0.706, Tmax = 0.794Rint = 0.015
6106 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.100H atoms treated by a mixture of independent and constrained refinement
S = 1.21Δρmax = 0.46 e Å3
2803 reflectionsΔρmin = 0.30 e Å3
175 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
O70.6205 (2)0.66640 (19)0.29668 (15)0.0360 (3)
Co11.00000.50000.00000.01986 (12)
O10.9067 (2)0.33848 (17)0.20120 (14)0.0325 (3)
O20.9725 (3)0.08988 (19)0.17835 (15)0.0469 (4)
O30.5899 (2)0.39084 (16)0.78211 (14)0.0282 (3)
O40.5555 (2)0.34851 (18)0.57558 (15)0.0348 (3)
O60.7258 (2)0.5352 (2)0.00197 (15)0.0364 (4)
H110.63950.48930.07850.055*
H100.69400.57710.07130.055*
O51.0344 (2)0.30316 (17)0.08666 (14)0.0291 (3)
H81.03550.21920.01630.044*
H91.14120.31140.15010.044*
N10.7321 (2)0.11394 (18)0.63709 (16)0.0228 (3)
H40.728 (4)0.167 (3)0.691 (3)0.029 (6)*
C10.9123 (3)0.1843 (2)0.24754 (18)0.0239 (4)
C20.8308 (2)0.1072 (2)0.40626 (17)0.0205 (3)
C30.8208 (2)0.1904 (2)0.49864 (18)0.0212 (3)
C40.9000 (3)0.3567 (2)0.4621 (2)0.0319 (4)
H20.80690.43880.44620.048*
H11.00780.37720.37830.048*
H30.93640.36100.53820.048*
C50.6508 (3)0.0367 (2)0.69532 (18)0.0221 (3)
C60.5440 (3)0.0842 (3)0.8498 (2)0.0356 (5)
H60.62580.14050.90190.053*
H70.44130.15550.87230.053*
H50.49630.01290.87400.053*
C70.6681 (2)0.1265 (2)0.60701 (17)0.0197 (3)
C80.5976 (2)0.3021 (2)0.65888 (18)0.0213 (3)
C90.7573 (2)0.0511 (2)0.46273 (17)0.0211 (3)
H160.76770.10960.40210.025*
O80.7410 (3)0.2787 (2)0.81069 (18)0.0437 (4)
H140.68000.36620.81550.066*
H150.83500.27790.83670.066*
H130.59240.67090.37930.066*
H120.57740.57210.31410.066*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O70.0431 (8)0.0336 (8)0.0282 (7)0.0047 (6)0.0064 (6)0.0101 (6)
Co10.02236 (19)0.01968 (18)0.01346 (17)0.00420 (12)0.00471 (12)0.00036 (12)
O10.0482 (9)0.0219 (7)0.0171 (6)0.0023 (6)0.0052 (6)0.0013 (5)
O20.0793 (13)0.0293 (8)0.0188 (7)0.0015 (8)0.0021 (7)0.0054 (6)
O30.0373 (7)0.0235 (6)0.0198 (6)0.0074 (5)0.0110 (6)0.0015 (5)
O40.0510 (9)0.0302 (7)0.0246 (7)0.0152 (6)0.0114 (6)0.0070 (6)
O60.0247 (7)0.0553 (10)0.0211 (6)0.0045 (6)0.0080 (5)0.0007 (6)
O50.0333 (7)0.0284 (7)0.0221 (6)0.0036 (5)0.0051 (6)0.0067 (5)
N10.0297 (8)0.0188 (7)0.0193 (7)0.0003 (6)0.0066 (6)0.0069 (6)
C10.0259 (9)0.0239 (8)0.0165 (8)0.0053 (7)0.0050 (7)0.0003 (6)
C20.0241 (8)0.0188 (8)0.0157 (7)0.0002 (6)0.0069 (6)0.0016 (6)
C30.0230 (8)0.0168 (8)0.0210 (8)0.0002 (6)0.0073 (7)0.0026 (6)
C40.0420 (11)0.0203 (9)0.0313 (10)0.0068 (8)0.0102 (9)0.0059 (7)
C50.0261 (8)0.0192 (8)0.0179 (8)0.0001 (6)0.0055 (7)0.0040 (6)
C60.0512 (13)0.0297 (10)0.0173 (8)0.0049 (9)0.0006 (8)0.0077 (7)
C70.0225 (8)0.0174 (7)0.0166 (7)0.0017 (6)0.0052 (6)0.0031 (6)
C80.0231 (8)0.0182 (8)0.0190 (8)0.0026 (6)0.0038 (6)0.0040 (6)
C90.0259 (8)0.0196 (8)0.0159 (7)0.0012 (6)0.0061 (6)0.0039 (6)
O80.0581 (10)0.0410 (9)0.0516 (10)0.0106 (7)0.0325 (9)0.0276 (8)
Geometric parameters (Å, º) top
O7—H130.8497N1—H40.84 (3)
O7—H120.8491C1—C21.518 (2)
Co1—O12.0483 (18)C2—C91.386 (3)
Co1—O1i2.0483 (18)C2—C31.389 (2)
Co1—O6i2.0652 (19)C3—C41.492 (3)
Co1—O62.0652 (19)C4—H20.9600
Co1—O52.1562 (19)C4—H10.9600
Co1—O5i2.1562 (19)C4—H30.9600
O1—C11.254 (2)C5—C71.384 (2)
O2—C11.235 (3)C5—C61.498 (3)
O3—C81.263 (2)C6—H60.9600
O4—C81.238 (2)C6—H70.9600
O6—H110.8500C6—H50.9600
O6—H100.8500C7—C91.398 (2)
O5—H80.8499C7—C81.516 (3)
O5—H90.8500C9—H160.9300
N1—C51.350 (2)O8—H140.8499
N1—C31.351 (2)O8—H150.8501
H13—O7—H12101.1C9—C2—C1119.22 (15)
O1—Co1—O1i180.00 (8)C3—C2—C1122.83 (16)
O1—Co1—O6i90.73 (7)N1—C3—C2117.51 (16)
O1i—Co1—O6i89.28 (7)N1—C3—C4115.52 (16)
O1—Co1—O689.27 (7)C2—C3—C4126.97 (17)
O1i—Co1—O690.73 (7)C3—C4—H2109.5
O6i—Co1—O6180.00 (8)C3—C4—H1109.5
O1—Co1—O591.39 (8)H2—C4—H1109.5
O1i—Co1—O588.61 (8)C3—C4—H3109.5
O6i—Co1—O588.52 (7)H2—C4—H3109.5
O6—Co1—O591.48 (7)H1—C4—H3109.5
O1—Co1—O5i88.61 (8)N1—C5—C7117.54 (16)
O1i—Co1—O5i91.39 (8)N1—C5—C6115.12 (16)
O6i—Co1—O5i91.48 (7)C7—C5—C6127.28 (17)
O6—Co1—O5i88.52 (7)C5—C6—H6109.5
O5—Co1—O5i180.0C5—C6—H7109.5
C1—O1—Co1131.02 (13)H6—C6—H7109.5
Co1—O6—H11117.8C5—C6—H5109.5
Co1—O6—H10124.3H6—C6—H5109.5
H11—O6—H10116.9H7—C6—H5109.5
Co1—O5—H8101.7C5—C7—C9117.86 (16)
Co1—O5—H9109.8C5—C7—C8123.42 (15)
H8—O5—H9108.2C9—C7—C8118.72 (15)
C5—N1—C3126.27 (16)O4—C8—O3124.96 (17)
C5—N1—H4118.0 (17)O4—C8—C7117.14 (16)
C3—N1—H4115.7 (17)O3—C8—C7117.87 (16)
O2—C1—O1127.22 (17)C2—C9—C7122.72 (16)
O2—C1—C2117.17 (17)C2—C9—H16118.6
O1—C1—C2115.59 (16)C7—C9—H16118.6
C9—C2—C3117.92 (16)H14—O8—H15107.8
Symmetry code: (i) x+2, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H4···O80.84 (3)1.89 (3)2.726 (3)175 (2)
O5—H8···O20.851.912.712 (3)156
O5—H9···O7i0.851.922.769 (3)179
O6—H11···O3ii0.851.912.740 (2)165
O6—H10···O3iii0.851.922.743 (2)163
O7—H13···O4iv0.851.972.814 (3)171
O7—H12···O4ii0.852.052.862 (3)160
O8—H14···O3iv0.852.082.914 (3)165
O8—H15···O5v0.852.022.861 (3)171
Symmetry codes: (i) x+2, y+1, z; (ii) x+1, y, z+1; (iii) x, y+1, z1; (iv) x, y+1, z; (v) x, y, z+1.

Experimental details

Crystal data
Chemical formula[Co(C9H8NO4)2(H2O)4]·4H2O
Mr591.39
Crystal system, space groupTriclinic, P1
Temperature (K)295
a, b, c (Å)7.597 (5), 8.651 (7), 10.715 (7)
α, β, γ (°)69.90 (3), 69.75 (2), 83.58 (2)
V3)620.4 (8)
Z1
Radiation typeMo Kα
µ (mm1)0.77
Crystal size (mm)0.48 × 0.39 × 0.31
Data collection
DiffractometerRigaku R-AXIS RAPID
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.706, 0.794
No. of measured, independent and
observed [I > 2σ(I)] reflections
6106, 2803, 2631
Rint0.015
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.100, 1.21
No. of reflections2803
No. of parameters175
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.46, 0.30

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H4···O80.84 (3)1.89 (3)2.726 (3)175 (2)
O5—H8···O20.851.912.712 (3)156.4
O5—H9···O7i0.851.922.769 (3)178.6
O6—H11···O3ii0.851.912.740 (2)165.0
O6—H10···O3iii0.851.922.743 (2)163.2
O7—H13···O4iv0.851.972.814 (3)170.7
O7—H12···O4ii0.852.052.862 (3)160.3
O8—H14···O3iv0.852.082.914 (3)165.1
O8—H15···O5v0.852.022.861 (3)170.6
Symmetry codes: (i) x+2, y+1, z; (ii) x+1, y, z+1; (iii) x, y+1, z1; (iv) x, y+1, z; (v) x, y, z+1.
 

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