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Acta Cryst. (2008). E64, m14    [ doi:10.1107/S1600536807062551 ]

Bis(2,2'-bipyridyl-[kappa]2N,N')(carbonato-[kappa]2O,O')cobalt(III) bromide trihydrate

P.-T. Ma, Y.-X. Wang, G.-Q. Zhang and M.-X. Li

Abstract top

The title complex, [Co(CO3)(C10H8N2)2]Br·3H2O, is isostructural with the chloride analogue. The six-coordinated octahedral [Co(2,2'-bipy)2CO3]+ cation (2,2'-bipy is 2,2'-bipyridyl), bromide ion and water molecules are linked together via O-H...Br and O-H...O hydrogen bonds, generating a one-dimensional chain.

Comment top

Recently, the design and assembly of metal coordination polymers continues attracting chemist's interests and constitutes an important area of research (Thirumurugan & Natarajan, 2004). During the past decades, lots of such compounds have been reported, which present predictable one-, two, three-dimensional frameworks by covalent bonds or hydrogen bonds interactions. Herein, we report the title compound (I).

The title complex (I), [Co(2,2'-bipy)2CO3]Br˙3H2O, contains a [Co(2,2'-bipy)2CO3]+ complex cation, a bromine ion, and three water molecules (Fig.1), which is isostructural with its chloride analogue (Das et al., 1993). In the molecular structure, Co atom resides in a distorted octahedral environment, which is defined by four nitrogen atoms from two 2,2-bipyridyl ligands, two oxygen dornors from the carbonate anion. In addition, the [Co(2,2'-bipy)2CO3]+ cation, bromine ion, and water molecules in the complex are linked together via O—H···Br and O—H···O hydrogen bonds generating a one-dimensional chain (Fig.2, Table 1).

Related literature top

For related literature, see: Das et al. (1993); Thirumurugan & Natarajan (2004).

Experimental top

Solid CoSO4˙7H2O (0.5 mmol, 0.141 g), KBr(1.0 mmol, 0.119 g) and 2,2'-bipy (1 mmol, 0.156 g) was dissolved in 20 ml of the mixed solvent of ethanol and water in a ratio of 1:4(v/v). Under continuous stirring, 5 ml (1 mol/L) solution of Na2CO3 was added dropwise until a purple solution resulted. The solution was filtered and left at room temperature. After slow evaporation over a period of a week, block red crystals of (I) were obtained.

Refinement top

The H atoms of the water molecules were located in a difference synthesis and refined with distance restraints O—H = 0.85 (1)Å and H···H = 1.34 (2) Å. The remaining H atoms were positioned geometrically with C—H = 0.93 Å, and were refined as riding with Uiso(H)=1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. One-dimensional structure of (I) linked by hydrogen bonds.
Bis(2,2'-bipyridyl-κ2N,N')(carbonato- κ2O,O')cobalt(III) bromide trihydrate top
Crystal data top
[Co(CO3)(C10H8N2)2]Br·3H2OZ = 2
Mr = 565.27F000 = 572
Triclinic, P1Dx = 1.668 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 9.1281 (1) ÅCell parameters from 9295 reflections
b = 9.6652 (2) Åθ = 2.6–26.7º
c = 13.0732 (2) ŵ = 2.58 mm−1
α = 92.054 (1)ºT = 296 (2) K
β = 102.315 (1)ºBlock, red
γ = 91.448 (1)º0.18 × 0.12 × 0.09 mm
V = 1125.48 (3) Å3
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		4411 independent reflections
Radiation source: fine-focus sealed tube4000 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.020
T = 296(2) Kθmax = 26.0º
φ and ω scansθmin = 2.1º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→11
Tmin = 0.654, Tmax = 0.801k = −11→11
14734 measured reflectionsl = −16→16
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.084  w = 1/[σ2(Fo2) + (0.0499P)2 + 0.4188P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
4411 reflectionsΔρmax = 0.31 e Å−3
323 parametersΔρmin = −0.56 e Å−3
9 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0160 (12)
Crystal data top
[Co(CO3)(C10H8N2)2]Br·3H2Oγ = 91.448 (1)º
Mr = 565.27V = 1125.48 (3) Å3
Triclinic, P1Z = 2
a = 9.1281 (1) ÅMo Kα
b = 9.6652 (2) ŵ = 2.58 mm−1
c = 13.0732 (2) ÅT = 296 (2) K
α = 92.054 (1)º0.18 × 0.12 × 0.09 mm
β = 102.315 (1)º
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		4411 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		4000 reflections with I > 2σ(I)
Tmin = 0.654, Tmax = 0.801Rint = 0.020
14734 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0289 restraints
wR(F2) = 0.084H atoms treated by a mixture of
independent and constrained refinement
S = 1.08Δρmax = 0.31 e Å−3
4411 reflectionsΔρmin = −0.56 e Å−3
323 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
Co10.26787 (3)0.01455 (3)0.244258 (18)0.02444 (10)
Br10.68362 (3)0.61581 (3)0.14986 (2)0.06088 (12)
C10.3267 (2)−0.2651 (2)0.31331 (18)0.0361 (5)
H10.2315−0.28960.27420.043*
C20.4099 (3)−0.3639 (2)0.37077 (19)0.0421 (5)
H20.3717−0.45420.37020.051*
C30.5510 (3)−0.3268 (2)0.42920 (18)0.0422 (5)
H30.6083−0.39170.46940.051*
C40.6063 (2)−0.1933 (2)0.42761 (17)0.0369 (5)
H40.7016−0.16720.46600.044*
C50.5184 (2)−0.0982 (2)0.36814 (14)0.0278 (4)
C60.5627 (2)0.0465 (2)0.35739 (14)0.0278 (4)
C70.7009 (2)0.1073 (2)0.40451 (17)0.0366 (5)
H70.77270.05690.44780.044*
C80.7303 (3)0.2439 (3)0.38614 (19)0.0436 (5)
H80.82240.28650.41690.052*
C90.6221 (3)0.3167 (2)0.3219 (2)0.0430 (5)
H90.64060.40870.30860.052*
C100.4857 (2)0.2511 (2)0.27730 (17)0.0354 (5)
H100.41260.30040.23420.042*
C110.3835 (2)−0.1361 (2)0.07871 (17)0.0331 (4)
H110.4386−0.18800.13120.040*
C120.3882 (3)−0.1675 (2)−0.02410 (18)0.0390 (5)
H120.4445−0.2404−0.04090.047*
C130.3086 (3)−0.0894 (3)−0.10162 (17)0.0399 (5)
H130.3101−0.1097−0.17150.048*
C140.2262 (2)0.0193 (2)−0.07523 (15)0.0341 (5)
H140.17400.0744−0.12660.041*
C150.2232 (2)0.0443 (2)0.02917 (15)0.0263 (4)
C160.1368 (2)0.1543 (2)0.06733 (15)0.0265 (4)
C170.0429 (2)0.2405 (2)0.00477 (17)0.0338 (4)
H170.03030.2332−0.06770.041*
C18−0.0327 (2)0.3386 (2)0.0514 (2)0.0413 (5)
H18−0.09900.39640.01060.050*
C19−0.0085 (3)0.3493 (2)0.1585 (2)0.0447 (6)
H19−0.05600.41670.19100.054*
C200.0864 (3)0.2598 (2)0.21795 (18)0.0395 (5)
H200.10210.26730.29060.047*
O3−0.0230 (2)−0.0747 (2)0.37222 (16)0.0604 (5)
C210.0755 (2)−0.0408 (2)0.32724 (17)0.0368 (5)
N10.45605 (18)0.11867 (17)0.29456 (13)0.0282 (3)
N20.37927 (18)−0.13463 (17)0.31232 (12)0.0281 (3)
N30.30138 (17)−0.03247 (17)0.10536 (12)0.0265 (3)
N40.15670 (18)0.16221 (17)0.17294 (13)0.0292 (4)
O10.08496 (15)−0.08699 (15)0.23240 (11)0.0321 (3)
O20.18851 (16)0.04514 (16)0.36505 (11)0.0341 (3)
O40.1357 (3)0.4381 (3)0.43419 (18)0.0666 (6)
O50.9249 (3)0.6454 (3)0.37190 (19)0.0676 (6)
O60.3364 (3)0.4743 (3)0.1049 (2)0.0754 (7)
H4A0.109 (4)0.409 (3)0.4873 (19)0.084 (12)*
H4B0.075 (3)0.498 (3)0.410 (2)0.061 (9)*
H6A0.331 (3)0.445 (4)0.0429 (13)0.074 (12)*
H5A0.939 (3)0.7312 (12)0.379 (2)0.055 (9)*
H6B0.423 (2)0.510 (4)0.125 (2)0.082 (12)*
H5B0.856 (3)0.630 (3)0.3190 (19)0.086 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.02552 (15)0.02518 (16)0.02032 (14)0.00563 (10)−0.00088 (10)0.00176 (10)
Br10.05214 (18)0.0591 (2)0.0695 (2)0.00644 (13)0.00614 (14)0.01561 (15)
C10.0349 (11)0.0304 (11)0.0403 (12)0.0004 (8)0.0015 (9)0.0057 (9)
C20.0496 (13)0.0294 (11)0.0486 (13)0.0054 (9)0.0114 (11)0.0107 (10)
C30.0474 (13)0.0386 (13)0.0398 (12)0.0159 (10)0.0036 (10)0.0143 (10)
C40.0358 (11)0.0412 (13)0.0302 (10)0.0108 (9)−0.0025 (8)0.0049 (9)
C50.0287 (9)0.0325 (11)0.0212 (9)0.0064 (8)0.0022 (7)0.0016 (8)
C60.0295 (9)0.0318 (11)0.0210 (9)0.0051 (8)0.0027 (7)0.0001 (8)
C70.0312 (10)0.0439 (13)0.0311 (10)0.0020 (9)−0.0008 (8)−0.0013 (9)
C80.0387 (12)0.0451 (14)0.0438 (13)−0.0090 (10)0.0043 (10)−0.0082 (10)
C90.0501 (13)0.0308 (12)0.0478 (13)−0.0054 (10)0.0111 (11)−0.0022 (10)
C100.0403 (11)0.0289 (11)0.0361 (11)0.0032 (9)0.0054 (9)0.0035 (9)
C110.0323 (10)0.0320 (11)0.0349 (11)0.0084 (8)0.0064 (8)0.0028 (8)
C120.0407 (12)0.0376 (12)0.0410 (12)0.0079 (9)0.0142 (10)−0.0039 (10)
C130.0415 (12)0.0504 (14)0.0286 (10)0.0009 (10)0.0109 (9)−0.0057 (9)
C140.0323 (10)0.0435 (12)0.0245 (10)0.0009 (9)0.0010 (8)0.0048 (9)
C150.0230 (9)0.0283 (10)0.0261 (9)0.0007 (7)0.0017 (7)0.0027 (8)
C160.0235 (9)0.0263 (10)0.0279 (9)0.0004 (7)0.0009 (7)0.0034 (8)
C170.0303 (10)0.0341 (11)0.0351 (11)0.0037 (8)0.0008 (8)0.0110 (9)
C180.0345 (11)0.0324 (12)0.0550 (14)0.0109 (9)0.0016 (10)0.0155 (10)
C190.0439 (12)0.0327 (12)0.0583 (15)0.0143 (10)0.0116 (11)0.0008 (11)
C200.0456 (12)0.0354 (12)0.0377 (11)0.0143 (10)0.0082 (9)−0.0017 (9)
O30.0540 (11)0.0702 (13)0.0655 (12)−0.0069 (9)0.0345 (10)−0.0080 (10)
C210.0353 (11)0.0412 (12)0.0339 (11)0.0074 (9)0.0065 (9)0.0011 (9)
N10.0304 (8)0.0269 (9)0.0257 (8)0.0042 (7)0.0023 (6)0.0010 (6)
N20.0292 (8)0.0282 (9)0.0251 (8)0.0036 (6)0.0012 (6)0.0031 (6)
N30.0264 (8)0.0259 (8)0.0256 (8)0.0043 (6)0.0015 (6)0.0015 (6)
N40.0295 (8)0.0291 (9)0.0274 (8)0.0063 (7)0.0019 (6)0.0005 (7)
O10.0260 (7)0.0374 (8)0.0298 (7)0.0018 (6)−0.0003 (5)−0.0014 (6)
O20.0387 (8)0.0394 (8)0.0229 (7)0.0030 (6)0.0040 (6)−0.0022 (6)
O40.0692 (14)0.0753 (16)0.0579 (13)0.0224 (12)0.0159 (11)0.0070 (11)
O50.0678 (14)0.0646 (15)0.0665 (14)0.0084 (11)0.0022 (11)0.0222 (11)
O60.0618 (14)0.0878 (18)0.0730 (17)−0.0079 (12)0.0045 (11)0.0232 (14)
Geometric parameters (Å, °) top
Co1—O11.8896 (14)C11—C121.377 (3)
Co1—O21.8897 (14)C11—H110.9300
Co1—N21.9195 (16)C12—C131.376 (3)
Co1—N41.9238 (16)C12—H120.9300
Co1—N11.9440 (17)C13—C141.383 (3)
Co1—N31.9447 (16)C13—H130.9300
Co1—C212.314 (2)C14—C151.384 (3)
C1—N21.339 (3)C14—H140.9300
C1—C21.378 (3)C15—N31.352 (2)
C1—H10.9300C15—C161.474 (3)
C2—C31.381 (3)C16—N41.353 (3)
C2—H20.9300C16—C171.373 (3)
C3—C41.377 (3)C17—C181.385 (3)
C3—H30.9300C17—H170.9300
C4—C51.384 (3)C18—C191.370 (4)
C4—H40.9300C18—H180.9300
C5—N21.353 (2)C19—C201.379 (3)
C5—C61.467 (3)C19—H190.9300
C6—N11.357 (2)C20—N41.342 (3)
C6—C71.387 (3)C20—H200.9300
C7—C81.380 (3)O3—C211.219 (3)
C7—H70.9300C21—O21.307 (3)
C8—C91.378 (4)C21—O11.324 (3)
C8—H80.9300O4—H4A0.839 (10)
C9—C101.384 (3)O4—H4B0.841 (10)
C9—H90.9300O5—H5A0.835 (10)
C10—N11.339 (3)O5—H5B0.837 (10)
C10—H100.9300O6—H6A0.841 (10)
C11—N31.346 (3)O6—H6B0.840 (10)
O1—Co1—O269.26 (6)N3—C11—H11119.1
O1—Co1—N291.31 (7)C12—C11—H11119.1
O2—Co1—N288.81 (7)C13—C12—C11119.1 (2)
O1—Co1—N488.69 (7)C13—C12—H12120.4
O2—Co1—N492.44 (7)C11—C12—H12120.4
N2—Co1—N4178.66 (7)C12—C13—C14119.7 (2)
O1—Co1—N1165.27 (7)C12—C13—H13120.2
O2—Co1—N196.93 (7)C14—C13—H13120.2
N2—Co1—N183.06 (7)C13—C14—C15118.66 (19)
N4—Co1—N197.25 (7)C13—C14—H14120.7
O1—Co1—N397.79 (6)C15—C14—H14120.7
O2—Co1—N3166.44 (7)N3—C15—C14121.61 (18)
N2—Co1—N395.69 (7)N3—C15—C16114.35 (16)
N4—Co1—N382.99 (7)C14—C15—C16124.04 (18)
N1—Co1—N396.31 (7)N4—C16—C17121.78 (18)
O1—Co1—C2134.90 (7)N4—C16—C15113.11 (16)
O2—Co1—C2134.39 (7)C17—C16—C15125.10 (18)
N2—Co1—C2189.09 (7)C16—C17—C18118.9 (2)
N4—Co1—C2191.68 (7)C16—C17—H17120.6
N1—Co1—C21131.00 (7)C18—C17—H17120.6
N3—Co1—C21132.64 (7)C19—C18—C17119.2 (2)
N2—C1—C2121.8 (2)C19—C18—H18120.4
N2—C1—H1119.1C17—C18—H18120.4
C2—C1—H1119.1C18—C19—C20119.7 (2)
C1—C2—C3118.9 (2)C18—C19—H19120.1
C1—C2—H2120.5C20—C19—H19120.1
C3—C2—H2120.5N4—C20—C19121.3 (2)
C4—C3—C2119.6 (2)N4—C20—H20119.4
C4—C3—H3120.2C19—C20—H20119.4
C2—C3—H3120.2O3—C21—O2125.6 (2)
C3—C4—C5119.1 (2)O3—C21—O1124.9 (2)
C3—C4—H4120.4O2—C21—O1109.44 (18)
C5—C4—H4120.4O3—C21—Co1177.39 (19)
N2—C5—C4121.01 (19)O2—C21—Co154.74 (10)
N2—C5—C6113.60 (16)O1—C21—Co154.75 (10)
C4—C5—C6125.38 (18)C10—N1—C6119.14 (17)
N1—C6—C7121.44 (19)C10—N1—Co1126.97 (14)
N1—C6—C5114.04 (17)C6—N1—Co1113.81 (14)
C7—C6—C5124.51 (18)C1—N2—C5119.56 (17)
C8—C7—C6118.9 (2)C1—N2—Co1125.30 (14)
C8—C7—H7120.5C5—N2—Co1115.00 (14)
C6—C7—H7120.5C11—N3—C15119.05 (17)
C9—C8—C7119.6 (2)C11—N3—Co1127.02 (14)
C9—C8—H8120.2C15—N3—Co1113.76 (12)
C7—C8—H8120.2C20—N4—C16119.12 (17)
C8—C9—C10119.1 (2)C20—N4—Co1125.47 (14)
C8—C9—H9120.4C16—N4—Co1115.00 (13)
C10—C9—H9120.4C21—O1—Co190.36 (12)
N1—C10—C9121.8 (2)C21—O2—Co190.87 (12)
N1—C10—H10119.1H4A—O4—H4B106.4 (16)
C9—C10—H10119.1H5A—O5—H5B106.9 (16)
N3—C11—C12121.83 (19)H6A—O6—H6B105.4 (16)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H4B···O5i0.841 (10)1.997 (11)2.832 (3)172 (3)
O4—H4A···O5ii0.839 (10)2.016 (12)2.847 (3)171 (4)
O5—H5A···O3iii0.835 (10)1.907 (12)2.735 (3)171 (3)
O5—H5B···Br10.837 (10)2.422 (13)3.247 (2)169 (3)
O6—H6B···Br10.840 (10)2.514 (12)3.345 (2)170 (3)
O6—H6A···Br1iv0.841 (10)2.541 (12)3.378 (3)173 (3)
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+1; (iii) x+1, y+1, z; (iv) −x+1, −y+1, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H4B···O5i0.841 (10)1.997 (11)2.832 (3)172 (3)
O4—H4A···O5ii0.839 (10)2.016 (12)2.847 (3)171 (4)
O5—H5A···O3iii0.835 (10)1.907 (12)2.735 (3)171 (3)
O5—H5B···Br10.837 (10)2.422 (13)3.247 (2)169 (3)
O6—H6B···Br10.840 (10)2.514 (12)3.345 (2)170 (3)
O6—H6A···Br1iv0.841 (10)2.541 (12)3.378 (3)173 (3)
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+1; (iii) x+1, y+1, z; (iv) −x+1, −y+1, −z.
Acknowledgements top

This work was supported by the Basic Research Foundation for Natural Science of Henan University (grant No. 05ZDZR002).

references
References top

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