Bis(2,2′-bipyridyl-κ2N,N′)(carbonato-κ2O,O′)cobalt(III) bromide trihydrate

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

doi:10.1107/S1600536807062551

metal-organic compounds

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Volume 64| Part 1| January 2008| Page m14

https://doi.org/10.1107/S1600536807062551

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Bis(2,2′-bipyridyl-κ²N,N′)(carbonato-κ²O,O′)cobalt(III) bromide trihydrate

Peng-Tao Ma,^a Yu-Xia Wang,^a Guo-Qian Zhang ^a and Ming-Xue Li ^a ^*

^aInstitute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, People's Republic of China
^*Correspondence e-mail: mptonline@163.com

(Received 20 November 2007; accepted 23 November 2007; online 6 December 2007)

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 ); Thirumurugan & Natarajan (2004 ).

Experimental

Crystal data

[Co(CO₃)(C₁₀H₈N₂)₂]Br·3H₂O
M_r = 565.27
Triclinic, $[P \overline 1]$
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 ) 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[F² > 2σ(F²)] = 0.028
wR(F²) = 0.084
S = 1.08
4411 reflections
323 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4B⋯O5ⁱ	0.841 (10)	1.997 (11)	2.832 (3)	172 (3)
O4—H4A⋯O5ⁱⁱ	0.839 (10)	2.016 (12)	2.847 (3)	171 (4)
O5—H5A⋯O3ⁱⁱⁱ	0.835 (10)	1.907 (12)	2.735 (3)	171 (3)
O5—H5B⋯Br1	0.837 (10)	2.422 (13)	3.247 (2)	169 (3)
O6—H6B⋯Br1	0.840 (10)	2.514 (12)	3.345 (2)	170 (3)
O6—H6A⋯Br1^iv	0.841 (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.

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.

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807062551/at2506Isup2.hkl

checkCIF report

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.

Structure description top

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

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

	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.

Bis(2,2'-bipyridyl-κ²N,N')(carbonato- κ²O,O')cobalt(III) bromide trihydrate top

Crystal data top

[Co(CO₃)(C₁₀H₈N₂)₂]Br·3H₂O	Z = 2
M_r = 565.27	F(000) = 572
Triclinic, P1	D_x = 1.668 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1281 (1) Å	Cell parameters from 9295 reflections
b = 9.6652 (2) Å	θ = 2.6–26.7°
c = 13.0732 (2) Å	µ = 2.58 mm⁻¹
α = 92.054 (1)°	T = 296 K
β = 102.315 (1)°	Block, red
γ = 91.448 (1)°	0.18 × 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 tube	4000 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
φ and ω scans	θ_max = 26.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→11
T_min = 0.654, T_max = 0.801	k = −11→11
14734 measured reflections	l = −16→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.0499P)² + 0.4188P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
4411 reflections	Δρ_max = 0.31 e Å⁻³
323 parameters	Δρ_min = −0.57 e Å⁻³
9 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0160 (12)

Crystal data top

[Co(CO₃)(C₁₀H₈N₂)₂]Br·3H₂O	γ = 91.448 (1)°
M_r = 565.27	V = 1125.48 (3) Å³
Triclinic, P1	Z = 2
a = 9.1281 (1) Å	Mo Kα radiation
b = 9.6652 (2) Å	µ = 2.58 mm⁻¹
c = 13.0732 (2) Å	T = 296 K
α = 92.054 (1)°	0.18 × 0.12 × 0.09 mm
β = 102.315 (1)°

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)
T_min = 0.654, T_max = 0.801	R_int = 0.020
14734 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	9 restraints
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.31 e Å⁻³
4411 reflections	Δρ_min = −0.57 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

	x	y	z	U_iso*/U_eq
Co1	0.26787 (3)	0.01455 (3)	0.244258 (18)	0.02444 (10)
Br1	0.68362 (3)	0.61581 (3)	0.14986 (2)	0.06088 (12)
C1	0.3267 (2)	−0.2651 (2)	0.31331 (18)	0.0361 (5)
H1	0.2315	−0.2896	0.2742	0.043*
C2	0.4099 (3)	−0.3639 (2)	0.37077 (19)	0.0421 (5)
H2	0.3717	−0.4542	0.3702	0.051*
C3	0.5510 (3)	−0.3268 (2)	0.42920 (18)	0.0422 (5)
H3	0.6083	−0.3917	0.4694	0.051*
C4	0.6063 (2)	−0.1933 (2)	0.42761 (17)	0.0369 (5)
H4	0.7016	−0.1672	0.4660	0.044*
C5	0.5184 (2)	−0.0982 (2)	0.36814 (14)	0.0278 (4)
C6	0.5627 (2)	0.0465 (2)	0.35739 (14)	0.0278 (4)
C7	0.7009 (2)	0.1073 (2)	0.40451 (17)	0.0366 (5)
H7	0.7727	0.0569	0.4478	0.044*
C8	0.7303 (3)	0.2439 (3)	0.38614 (19)	0.0436 (5)
H8	0.8224	0.2865	0.4169	0.052*
C9	0.6221 (3)	0.3167 (2)	0.3219 (2)	0.0430 (5)
H9	0.6406	0.4087	0.3086	0.052*
C10	0.4857 (2)	0.2511 (2)	0.27730 (17)	0.0354 (5)
H10	0.4126	0.3004	0.2342	0.042*
C11	0.3835 (2)	−0.1361 (2)	0.07871 (17)	0.0331 (4)
H11	0.4386	−0.1880	0.1312	0.040*
C12	0.3882 (3)	−0.1675 (2)	−0.02410 (18)	0.0390 (5)
H12	0.4445	−0.2404	−0.0409	0.047*
C13	0.3086 (3)	−0.0894 (3)	−0.10162 (17)	0.0399 (5)
H13	0.3101	−0.1097	−0.1715	0.048*
C14	0.2262 (2)	0.0193 (2)	−0.07523 (15)	0.0341 (5)
H14	0.1740	0.0744	−0.1266	0.041*
C15	0.2232 (2)	0.0443 (2)	0.02917 (15)	0.0263 (4)
C16	0.1368 (2)	0.1543 (2)	0.06733 (15)	0.0265 (4)
C17	0.0429 (2)	0.2405 (2)	0.00477 (17)	0.0338 (4)
H17	0.0303	0.2332	−0.0677	0.041*
C18	−0.0327 (2)	0.3386 (2)	0.0514 (2)	0.0413 (5)
H18	−0.0990	0.3964	0.0106	0.050*
C19	−0.0085 (3)	0.3493 (2)	0.1585 (2)	0.0447 (6)
H19	−0.0560	0.4167	0.1910	0.054*
C20	0.0864 (3)	0.2598 (2)	0.21795 (18)	0.0395 (5)
H20	0.1021	0.2673	0.2906	0.047*
O3	−0.0230 (2)	−0.0747 (2)	0.37222 (16)	0.0604 (5)
C21	0.0755 (2)	−0.0408 (2)	0.32724 (17)	0.0368 (5)
N1	0.45605 (18)	0.11867 (17)	0.29456 (13)	0.0282 (3)
N2	0.37927 (18)	−0.13463 (17)	0.31232 (12)	0.0281 (3)
N3	0.30138 (17)	−0.03247 (17)	0.10536 (12)	0.0265 (3)
N4	0.15670 (18)	0.16221 (17)	0.17294 (13)	0.0292 (4)
O1	0.08496 (15)	−0.08699 (15)	0.23240 (11)	0.0321 (3)
O2	0.18851 (16)	0.04514 (16)	0.36505 (11)	0.0341 (3)
O4	0.1357 (3)	0.4381 (3)	0.43419 (18)	0.0666 (6)
O5	0.9249 (3)	0.6454 (3)	0.37190 (19)	0.0676 (6)
O6	0.3364 (3)	0.4743 (3)	0.1049 (2)	0.0754 (7)
H4A	0.109 (4)	0.409 (3)	0.4873 (19)	0.084 (12)*
H4B	0.075 (3)	0.498 (3)	0.410 (2)	0.061 (9)*
H6A	0.331 (3)	0.445 (4)	0.0429 (13)	0.074 (12)*
H5A	0.939 (3)	0.7312 (12)	0.379 (2)	0.055 (9)*
H6B	0.423 (2)	0.510 (4)	0.125 (2)	0.082 (12)*
H5B	0.856 (3)	0.630 (3)	0.3190 (19)	0.086 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.02552 (15)	0.02518 (16)	0.02032 (14)	0.00563 (10)	−0.00088 (10)	0.00176 (10)
Br1	0.05214 (18)	0.0591 (2)	0.0695 (2)	0.00644 (13)	0.00614 (14)	0.01561 (15)
C1	0.0349 (11)	0.0304 (11)	0.0403 (12)	0.0004 (8)	0.0015 (9)	0.0057 (9)
C2	0.0496 (13)	0.0294 (11)	0.0486 (13)	0.0054 (9)	0.0114 (11)	0.0107 (10)
C3	0.0474 (13)	0.0386 (13)	0.0398 (12)	0.0159 (10)	0.0036 (10)	0.0143 (10)
C4	0.0358 (11)	0.0412 (13)	0.0302 (10)	0.0108 (9)	−0.0025 (8)	0.0049 (9)
C5	0.0287 (9)	0.0325 (11)	0.0212 (9)	0.0064 (8)	0.0022 (7)	0.0016 (8)
C6	0.0295 (9)	0.0318 (11)	0.0210 (9)	0.0051 (8)	0.0027 (7)	0.0001 (8)
C7	0.0312 (10)	0.0439 (13)	0.0311 (10)	0.0020 (9)	−0.0008 (8)	−0.0013 (9)
C8	0.0387 (12)	0.0451 (14)	0.0438 (13)	−0.0090 (10)	0.0043 (10)	−0.0082 (10)
C9	0.0501 (13)	0.0308 (12)	0.0478 (13)	−0.0054 (10)	0.0111 (11)	−0.0022 (10)
C10	0.0403 (11)	0.0289 (11)	0.0361 (11)	0.0032 (9)	0.0054 (9)	0.0035 (9)
C11	0.0323 (10)	0.0320 (11)	0.0349 (11)	0.0084 (8)	0.0064 (8)	0.0028 (8)
C12	0.0407 (12)	0.0376 (12)	0.0410 (12)	0.0079 (9)	0.0142 (10)	−0.0039 (10)
C13	0.0415 (12)	0.0504 (14)	0.0286 (10)	0.0009 (10)	0.0109 (9)	−0.0057 (9)
C14	0.0323 (10)	0.0435 (12)	0.0245 (10)	0.0009 (9)	0.0010 (8)	0.0048 (9)
C15	0.0230 (9)	0.0283 (10)	0.0261 (9)	0.0007 (7)	0.0017 (7)	0.0027 (8)
C16	0.0235 (9)	0.0263 (10)	0.0279 (9)	0.0004 (7)	0.0009 (7)	0.0034 (8)
C17	0.0303 (10)	0.0341 (11)	0.0351 (11)	0.0037 (8)	0.0008 (8)	0.0110 (9)
C18	0.0345 (11)	0.0324 (12)	0.0550 (14)	0.0109 (9)	0.0016 (10)	0.0155 (10)
C19	0.0439 (12)	0.0327 (12)	0.0583 (15)	0.0143 (10)	0.0116 (11)	0.0008 (11)
C20	0.0456 (12)	0.0354 (12)	0.0377 (11)	0.0143 (10)	0.0082 (9)	−0.0017 (9)
O3	0.0540 (11)	0.0702 (13)	0.0655 (12)	−0.0069 (9)	0.0345 (10)	−0.0080 (10)
C21	0.0353 (11)	0.0412 (12)	0.0339 (11)	0.0074 (9)	0.0065 (9)	0.0011 (9)
N1	0.0304 (8)	0.0269 (9)	0.0257 (8)	0.0042 (7)	0.0023 (6)	0.0010 (6)
N2	0.0292 (8)	0.0282 (9)	0.0251 (8)	0.0036 (6)	0.0012 (6)	0.0031 (6)
N3	0.0264 (8)	0.0259 (8)	0.0256 (8)	0.0043 (6)	0.0015 (6)	0.0015 (6)
N4	0.0295 (8)	0.0291 (9)	0.0274 (8)	0.0063 (7)	0.0019 (6)	0.0005 (7)
O1	0.0260 (7)	0.0374 (8)	0.0298 (7)	0.0018 (6)	−0.0003 (5)	−0.0014 (6)
O2	0.0387 (8)	0.0394 (8)	0.0229 (7)	0.0030 (6)	0.0040 (6)	−0.0022 (6)
O4	0.0692 (14)	0.0753 (16)	0.0579 (13)	0.0224 (12)	0.0159 (11)	0.0070 (11)
O5	0.0678 (14)	0.0646 (15)	0.0665 (14)	0.0084 (11)	0.0022 (11)	0.0222 (11)
O6	0.0618 (14)	0.0878 (18)	0.0730 (17)	−0.0079 (12)	0.0045 (11)	0.0232 (14)

Geometric parameters (Å, º) top

Co1—O1	1.8896 (14)	C11—C12	1.377 (3)
Co1—O2	1.8897 (14)	C11—H11	0.9300
Co1—N2	1.9195 (16)	C12—C13	1.376 (3)
Co1—N4	1.9238 (16)	C12—H12	0.9300
Co1—N1	1.9440 (17)	C13—C14	1.383 (3)
Co1—N3	1.9447 (16)	C13—H13	0.9300
Co1—C21	2.314 (2)	C14—C15	1.384 (3)
C1—N2	1.339 (3)	C14—H14	0.9300
C1—C2	1.378 (3)	C15—N3	1.352 (2)
C1—H1	0.9300	C15—C16	1.474 (3)
C2—C3	1.381 (3)	C16—N4	1.353 (3)
C2—H2	0.9300	C16—C17	1.373 (3)
C3—C4	1.377 (3)	C17—C18	1.385 (3)
C3—H3	0.9300	C17—H17	0.9300
C4—C5	1.384 (3)	C18—C19	1.370 (4)
C4—H4	0.9300	C18—H18	0.9300
C5—N2	1.353 (2)	C19—C20	1.379 (3)
C5—C6	1.467 (3)	C19—H19	0.9300
C6—N1	1.357 (2)	C20—N4	1.342 (3)
C6—C7	1.387 (3)	C20—H20	0.9300
C7—C8	1.380 (3)	O3—C21	1.219 (3)
C7—H7	0.9300	C21—O2	1.307 (3)
C8—C9	1.378 (4)	C21—O1	1.324 (3)
C8—H8	0.9300	O4—H4A	0.839 (10)
C9—C10	1.384 (3)	O4—H4B	0.841 (10)
C9—H9	0.9300	O5—H5A	0.835 (10)
C10—N1	1.339 (3)	O5—H5B	0.837 (10)
C10—H10	0.9300	O6—H6A	0.841 (10)
C11—N3	1.346 (3)	O6—H6B	0.840 (10)

O1—Co1—O2	69.26 (6)	N3—C11—H11	119.1
O1—Co1—N2	91.31 (7)	C12—C11—H11	119.1
O2—Co1—N2	88.81 (7)	C13—C12—C11	119.1 (2)
O1—Co1—N4	88.69 (7)	C13—C12—H12	120.4
O2—Co1—N4	92.44 (7)	C11—C12—H12	120.4
N2—Co1—N4	178.66 (7)	C12—C13—C14	119.7 (2)
O1—Co1—N1	165.27 (7)	C12—C13—H13	120.2
O2—Co1—N1	96.93 (7)	C14—C13—H13	120.2
N2—Co1—N1	83.06 (7)	C13—C14—C15	118.66 (19)
N4—Co1—N1	97.25 (7)	C13—C14—H14	120.7
O1—Co1—N3	97.79 (6)	C15—C14—H14	120.7
O2—Co1—N3	166.44 (7)	N3—C15—C14	121.61 (18)
N2—Co1—N3	95.69 (7)	N3—C15—C16	114.35 (16)
N4—Co1—N3	82.99 (7)	C14—C15—C16	124.04 (18)
N1—Co1—N3	96.31 (7)	N4—C16—C17	121.78 (18)
O1—Co1—C21	34.90 (7)	N4—C16—C15	113.11 (16)
O2—Co1—C21	34.39 (7)	C17—C16—C15	125.10 (18)
N2—Co1—C21	89.09 (7)	C16—C17—C18	118.9 (2)
N4—Co1—C21	91.68 (7)	C16—C17—H17	120.6
N1—Co1—C21	131.00 (7)	C18—C17—H17	120.6
N3—Co1—C21	132.64 (7)	C19—C18—C17	119.2 (2)
N2—C1—C2	121.8 (2)	C19—C18—H18	120.4
N2—C1—H1	119.1	C17—C18—H18	120.4
C2—C1—H1	119.1	C18—C19—C20	119.7 (2)
C1—C2—C3	118.9 (2)	C18—C19—H19	120.1
C1—C2—H2	120.5	C20—C19—H19	120.1
C3—C2—H2	120.5	N4—C20—C19	121.3 (2)
C4—C3—C2	119.6 (2)	N4—C20—H20	119.4
C4—C3—H3	120.2	C19—C20—H20	119.4
C2—C3—H3	120.2	O3—C21—O2	125.6 (2)
C3—C4—C5	119.1 (2)	O3—C21—O1	124.9 (2)
C3—C4—H4	120.4	O2—C21—O1	109.44 (18)
C5—C4—H4	120.4	O3—C21—Co1	177.39 (19)
N2—C5—C4	121.01 (19)	O2—C21—Co1	54.74 (10)
N2—C5—C6	113.60 (16)	O1—C21—Co1	54.75 (10)
C4—C5—C6	125.38 (18)	C10—N1—C6	119.14 (17)
N1—C6—C7	121.44 (19)	C10—N1—Co1	126.97 (14)
N1—C6—C5	114.04 (17)	C6—N1—Co1	113.81 (14)
C7—C6—C5	124.51 (18)	C1—N2—C5	119.56 (17)
C8—C7—C6	118.9 (2)	C1—N2—Co1	125.30 (14)
C8—C7—H7	120.5	C5—N2—Co1	115.00 (14)
C6—C7—H7	120.5	C11—N3—C15	119.05 (17)
C9—C8—C7	119.6 (2)	C11—N3—Co1	127.02 (14)
C9—C8—H8	120.2	C15—N3—Co1	113.76 (12)
C7—C8—H8	120.2	C20—N4—C16	119.12 (17)
C8—C9—C10	119.1 (2)	C20—N4—Co1	125.47 (14)
C8—C9—H9	120.4	C16—N4—Co1	115.00 (13)
C10—C9—H9	120.4	C21—O1—Co1	90.36 (12)
N1—C10—C9	121.8 (2)	C21—O2—Co1	90.87 (12)
N1—C10—H10	119.1	H4A—O4—H4B	106.4 (16)
C9—C10—H10	119.1	H5A—O5—H5B	106.9 (16)
N3—C11—C12	121.83 (19)	H6A—O6—H6B	105.4 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4B···O5ⁱ	0.84 (1)	2.00 (1)	2.832 (3)	172 (3)
O4—H4A···O5ⁱⁱ	0.84 (1)	2.02 (1)	2.847 (3)	171 (4)
O5—H5A···O3ⁱⁱⁱ	0.84 (1)	1.91 (1)	2.735 (3)	171 (3)
O5—H5B···Br1	0.84 (1)	2.42 (1)	3.247 (2)	169 (3)
O6—H6B···Br1	0.84 (1)	2.51 (1)	3.345 (2)	170 (3)
O6—H6A···Br1^iv	0.84 (1)	2.54 (1)	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.

Experimental details

Crystal data
Chemical formula	[Co(CO₃)(C₁₀H₈N₂)₂]Br·3H₂O
M_r	565.27
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	9.1281 (1), 9.6652 (2), 13.0732 (2)
α, β, γ (°)	92.054 (1), 102.315 (1), 91.448 (1)
V (Å³)	1125.48 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.58
Crystal size (mm)	0.18 × 0.12 × 0.09

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.654, 0.801
No. of measured, independent and observed [I > 2σ(I)] reflections	14734, 4411, 4000
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.084, 1.08
No. of reflections	4411
No. of parameters	323
No. of restraints	9
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.57

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SAINT-Plus, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4B···O5ⁱ	0.841 (10)	1.997 (11)	2.832 (3)	172 (3)
O4—H4A···O5ⁱⁱ	0.839 (10)	2.016 (12)	2.847 (3)	171 (4)
O5—H5A···O3ⁱⁱⁱ	0.835 (10)	1.907 (12)	2.735 (3)	171 (3)
O5—H5B···Br1	0.837 (10)	2.422 (13)	3.247 (2)	169 (3)
O6—H6B···Br1	0.840 (10)	2.514 (12)	3.345 (2)	170 (3)
O6—H6A···Br1^iv	0.841 (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

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

References

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