PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): m14.
Published online 2007 December 6. doi:  10.1107/S1600536807062551
PMCID: PMC2914907

Bis(2,2′-bipyridyl-κ2 N,N′)(carbonato-κ2 O,O′)cobalt(III) bromide trihydrate

Abstract

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.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-64-00m14-scheme1.jpg

Experimental

Crystal data

  • [Co(CO3)(C10H8N2)2]Br·3H2O
  • M r = 565.27
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-00m14-efi1.jpg
  • a = 9.1281 (1) Å
  • b = 9.6652 (2) Å
  • c = 13.0732 (2) Å
  • α = 92.054 (1)°
  • β = 102.315 (1)°
  • γ = 91.448 (1)°
  • V = 1125.48 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.58 mm−1
  • T = 296 (2) K
  • 0.18 × 0.12 × 0.09 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.654, T max = 0.801
  • 14734 measured reflections
  • 4411 independent reflections
  • 4000 reflections with I > 2σ(I)
  • R int = 0.020

Refinement

  • R[F 2 > 2σ(F 2)] = 0.028
  • wR(F 2) = 0.084
  • S = 1.08
  • 4411 reflections
  • 323 parameters
  • 9 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.56 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807062551/at2506sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062551/at2506Isup2.hkl

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

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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

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).

Figures

Fig. 1.
The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
One-dimensional structure of (I) linked by hydrogen bonds.

Crystal data

[Co(CO3)(C10H8N2)2]Br·3H2OZ = 2
Mr = 565.27F000 = 572
Triclinic, P1Dx = 1.668 Mg m3
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 mm1
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

Bruker SMART APEX CCD area-detector diffractometer4411 independent reflections
Radiation source: fine-focus sealed tube4000 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.020
T = 296(2) Kθmax = 26.0º
[var phi] 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

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 Å3
323 parametersΔρmin = −0.56 e Å3
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)

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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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 andgoodness of fit S are based on F2, conventional R-factors R are basedon F, with F set to zero for negative F2. The threshold expression ofF2 > σ(F2) is used only for calculating R-factors(gt) etc. and isnot relevant to the choice of reflections for refinement. R-factors basedon 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
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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2506).

References

  • Bruker (2001). SMART, SAINT-Plus and SHELXTL Bruker AXS Inc., Madison, Wisconsin, USA.
  • Das, K., Sinha, U. C., Chaterjee, C. & Mishnev, A. (1993). Z. Kristallogr.205, 316–318.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.
  • Thirumurugan, A. & Natarajan, S. (2004). Dalton Trans. pp. 2923–2928. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography