(Carbonato-κ2O,O′)bis­(5,5′-dimethyl-2,2′-bipyridyl-κ2N,N′)cobalt(III) bromide trihydrate

Arun Kumar, K.; Meera, P.; Amutha Selvi, M.; Dayalan, A.

doi:10.1107/S160053681200894X

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 4| April 2012| Pages m383-m384

doi:10.1107/S160053681200894X

Open

access

(Carbonato-κ²O,O′)bis(5,5′-dimethyl-2,2′-bipyridyl-κ²N,N′)cobalt(III) bromide trihydrate

Kannan Arun Kumar,^a Parthsarathi Meera,^a Madhavan Amutha Selvi ^a and Arunachalam Dayalan ^a ^*

^aDepartment of Chemistry, Loyola College (Autonomous), Chennai 600 034, India
^*Correspondence e-mail: dayalan77@gmail.com

(Received 4 February 2012; accepted 29 February 2012; online 7 March 2012)

In the title complex, [Co(CO₃)(C₁₂H₁₂N₂)₂]Br·3H₂O, the Co^III cation has a distorted octahedral coordination environment. It is chelated by four N atoms of two different 5,5′-dimethyl-2,2′-bipyridyl (dmbpy) ligands in axial and equatorial positions, and by two O atoms of a carbonate anion completing the equatorial positions. Although the water molecules are disordered and their H atoms were not located, there are typical O⋯O distances between 2.8 and 3.0 Å, indicating O—H⋯O hydrogen bonding. The crystal packing is consolidated by C—H⋯O and C—H⋯Br hydrogen bonds, as well as π–π stacking interactions between adjacent pyridine rings of the dmbpy ligands, with centroid–centroid distances of 3.694 (3) and 3.7053 (3) Å.

Related literature

For background to this class of compounds, see: Momeni et al. (2009 ); Harding et al. (2008 ); Kusrini et al. (2008 ). For applications of this class of compounds in various fields, see: Carol et al. (2006 ); Eddie et al. (2010 ); Raj et al. (2008 ); Vitushkina et al. (2006 ); Hyung et al. (2006 ); Jayaweera et al. (2002 ), Shi et al. (2010 ); For similar structures, see: Ma et al. (2008 ); Phatchimkun & Chaichit (2011 ).

Experimental

Crystal data

[Co(CO₃)(C₁₂H₁₂N₂)₂]Br·3H₂O
M_r = 621.32
Monoclinic, P 2₁ /c
a = 11.5802 (15) Å
b = 15.958 (2) Å
c = 14.3921 (17) Å
β = 100.143 (3)°
V = 2618.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 2.23 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.555, T_max = 0.664
23769 measured reflections
5033 independent reflections
3111 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.145
S = 1.02
5033 reflections
346 parameters
H-atom parameters constrained
Δρ_max = 0.77 e Å⁻³
Δρ_min = −1.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1	0.93	2.43	2.931 (5)	114
C3—H3⋯Br1ⁱ	0.93	2.80	3.718 (4)	168
C4—H4⋯O1ⁱⁱ	0.93	2.51	3.257 (4)	138
C11—H11A⋯Br1ⁱⁱⁱ	0.96	2.91	3.810 (4)	157
C19—H19⋯O3^iv	0.93	2.52	3.284 (4)	140
C20—H20⋯Br1^iv	0.93	2.85	3.778 (4)	172
C22—H22⋯O3	0.93	2.44	2.939 (4)	113
C23—H23B⋯O4^v	0.96	2.42	3.330 (6)	158
C24—H24A⋯Br1	0.96	2.93	3.836 (5)	158
Symmetry codes: (i) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) x-1, y, z; (iv) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (v) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681200894X/wm2590sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681200894X/wm2590Isup2.hkl

checkCIF report

Comment top

2,2'-Bipyridyl and 1,10-phenanthroline are versatile ligands capable of forming stable complexes with different metals in their various oxidation states (Momeni et al., 2009; Harding et al., 2008; Kusrini et al., 2008; Phatchimkun & Chaichit, 2011; Ma et al., 2008). These complexes have interesting electrical, magnetic, thermal, optical and antimicrobial properties. Hence, they are widely studied in various fields like medicine (Carol et al., 2006; Eddie et al., 2010), crystallography (Raj et al., 2008; Vitushkina et al.,2006;) chemistry (Hyung et al., 2006; Jayaweera et al., 2002) or biology (Shi et al., 2010). The crystal structures of a large number of metal complexes with the above mentioned ligands have been reported, including substituted ligands with various moieties like halogens, methyl, phenyl, acetyl at various positions.

The title complex [Co(C₁₂H₁₂N₂)₂CO₃]Br^.3H₂O, consists of a complex cation [Co(C₁₂H₁₂N₂)₂CO₃]⁺, a bromide counter anion and three molecules of lattice water. The cobalt(III) ion is six coordinated by four nitrogen atoms of the two 5,5'-dimethyl-2,2'-bipyridyl (dmbpy) ligands and two oxygen atoms of the carbonato ligands in a distorted octahedral environment (Fig. 1). The water molecules are disordered in the crystal packing, but O···O distances indicate O—H···O hydrogen bonding. The dihedral angle between the two dmbpy ligands is 85.8 (2)°. The major distortion from the ideal geometry is due to a narrow bite angle of the carbonato ligand, i.e. O1–Co—O3 = 69.44 (11)°. The bromide ion and solvated water molecules are dispersed between cationic layers. The crystal packing is stabilized by extensive series of C—H···O and C—H···Br hydrogen bonds (Fig.2, Table.1) In addition, π—π stacking interactions between adjacent pyridine rings are present with centroid to centroid distances of 3.694 (3) A° and 3.7053 (3) A°.

Related literature top

For background to this class of compounds, see: Momeni et al. (2009); Harding et al. (2008); Kusrini et al. (2008). For applications of this class of compounds in various fields, see: Carol et al. (2006); Eddie et al. (2010); Raj et al. (2008); Vitushkina et al. (2006); Hyung et al. (2006); Jayaweera et al. (2002), Shi et al. (2010); For similar structures, see: Ma et al. (2008); Phatchimkun & Chaichit (2011).

Experimental top

The title complex was prepared by mixing 0.005 mol of finely crushed cobalt(II) bromide, exposed to microwave radiation and dissolved in 75 ml of acetone, with 0.005 mol of sodium carbonate, 0.01 mol of dmbpy and 2 ml hydrogen peroxide (30% v/v). The reaction mixture was stirred and allowed to react for one hour. The resultant pink coloured precipitate was filtered, washed with excess acetone and dried over vacuum desicator (yield: 60%). Dark red coloured single crystals were grown from a 90% v/v ethanolic solution by slow evoparation.

Structure description top

For background to this class of compounds, see: Momeni et al. (2009); Harding et al. (2008); Kusrini et al. (2008). For applications of this class of compounds in various fields, see: Carol et al. (2006); Eddie et al. (2010); Raj et al. (2008); Vitushkina et al. (2006); Hyung et al. (2006); Jayaweera et al. (2002), Shi et al. (2010); For similar structures, see: Ma et al. (2008); Phatchimkun & Chaichit (2011).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Ellipsoid plot (50% probability) of the cationic complex and the bromide anion. Disordered water molecules were omitted for clarity.
	Fig. 2. Crystal packing of the complex, showing also the hydrogen bonding interactions (dotted lines)

(Carbonato-κ²O,O')bis(5,5'-dimethyl-2,2'-bipyridyl- κ²N,N')cobalt(III) bromide trihydrate top

Crystal data top

[Co(CO₃)(C₁₂H₁₂N₂)₂]Br·3H₂O	F(000) = 1248
M_r = 621.32	D_x = 1.561 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4593 reflections
a = 11.5802 (15) Å	θ = 2.2–25.6°
b = 15.958 (2) Å	µ = 2.23 mm⁻¹
c = 14.3921 (17) Å	T = 293 K
β = 100.143 (3)°	Block, red
V = 2618.0 (6) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	5033 independent reflections
Radiation source: fine-focus sealed tube	3111 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ω and φ scan	θ_max = 25.9°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −14→14
T_min = 0.555, T_max = 0.664	k = −19→19
23769 measured reflections	l = −17→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0686P)² + 2.4848P] where P = (F_o² + 2F_c²)/3
5033 reflections	(Δ/σ)_max < 0.001
346 parameters	Δρ_max = 0.77 e Å⁻³
0 restraints	Δρ_min = −1.43 e Å⁻³

Crystal data top

[Co(CO₃)(C₁₂H₁₂N₂)₂]Br·3H₂O	V = 2618.0 (6) Å³
M_r = 621.32	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.5802 (15) Å	µ = 2.23 mm⁻¹
b = 15.958 (2) Å	T = 293 K
c = 14.3921 (17) Å	0.30 × 0.25 × 0.20 mm
β = 100.143 (3)°

Data collection top

Bruker APEXII CCD diffractometer	5033 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	3111 reflections with I > 2σ(I)
T_min = 0.555, T_max = 0.664	R_int = 0.048
23769 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 1.02	Δρ_max = 0.77 e Å⁻³
5033 reflections	Δρ_min = −1.43 e Å⁻³
346 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	Occ. (<1)
C1	0.3712 (3)	0.2890 (2)	0.7720 (3)	0.0345 (8)
H1	0.3549	0.3252	0.8186	0.041*
C2	0.2916 (3)	0.2835 (2)	0.6885 (3)	0.0360 (9)
C3	0.3182 (4)	0.2288 (2)	0.6203 (3)	0.0402 (10)
H3	0.2675	0.2237	0.5627	0.048*
C4	0.4194 (3)	0.1824 (2)	0.6379 (2)	0.0374 (9)
H4	0.4366	0.1450	0.5926	0.045*
C5	0.4953 (3)	0.1909 (2)	0.7222 (2)	0.0301 (8)
C6	0.6068 (3)	0.1471 (2)	0.7492 (2)	0.0300 (8)
C7	0.6501 (3)	0.0889 (2)	0.6939 (3)	0.0389 (9)
H7	0.6063	0.0731	0.6360	0.047*
C8	0.7597 (3)	0.0539 (2)	0.7250 (3)	0.0406 (9)
H8	0.7893	0.0140	0.6884	0.049*
C9	0.8246 (3)	0.0785 (2)	0.8104 (3)	0.0372 (9)
C10	0.7749 (3)	0.1367 (2)	0.8627 (2)	0.0342 (8)
H10	0.8176	0.1539	0.9203	0.041*
C11	0.1830 (3)	0.3362 (3)	0.6723 (3)	0.0497 (11)
H11A	0.1417	0.3292	0.7241	0.074*
H11B	0.1334	0.3193	0.6148	0.074*
H11C	0.2041	0.3940	0.6678	0.074*
C12	0.9454 (4)	0.0463 (3)	0.8466 (3)	0.0533 (11)
H12A	1.0005	0.0917	0.8510	0.080*
H12B	0.9654	0.0045	0.8041	0.080*
H12C	0.9478	0.0219	0.9079	0.080*
C13	0.4108 (3)	0.1317 (2)	0.9421 (2)	0.0337 (8)
H13	0.3688	0.1440	0.8825	0.040*
C14	0.3629 (3)	0.0754 (2)	0.9986 (3)	0.0344 (8)
C15	0.4271 (3)	0.0582 (2)	1.0863 (3)	0.0382 (9)
H15	0.3983	0.0201	1.1255	0.046*
C16	0.5334 (3)	0.0966 (2)	1.1166 (2)	0.0346 (8)
H16	0.5761	0.0852	1.1763	0.042*
C17	0.5761 (3)	0.1526 (2)	1.0571 (2)	0.0294 (8)
C18	0.6864 (3)	0.1986 (2)	1.0812 (2)	0.0298 (8)
C19	0.7652 (3)	0.1912 (2)	1.1642 (2)	0.0373 (9)
H19	0.7504	0.1541	1.2105	0.045*
C20	0.8656 (3)	0.2384 (2)	1.1787 (3)	0.0387 (9)
H20	0.9190	0.2335	1.2348	0.046*
C21	0.8874 (3)	0.2938 (2)	1.1092 (2)	0.0369 (9)
C22	0.8051 (3)	0.2976 (2)	1.0263 (2)	0.0350 (9)
H22	0.8187	0.3337	0.9787	0.042*
C23	0.2454 (3)	0.0377 (3)	0.9622 (3)	0.0474 (10)
H23A	0.2341	−0.0107	0.9992	0.071*
H23B	0.2414	0.0215	0.8975	0.071*
H23C	0.1852	0.0781	0.9665	0.071*
C24	0.9940 (3)	0.3485 (3)	1.1216 (3)	0.0508 (11)
H24A	1.0361	0.3387	1.0709	0.076*
H24B	1.0436	0.3356	1.1806	0.076*
H24C	0.9706	0.4062	1.1214	0.076*
N1	0.4700 (2)	0.24492 (18)	0.78871 (19)	0.0301 (7)
N2	0.6678 (2)	0.16936 (18)	0.83404 (19)	0.0313 (7)
N3	0.5147 (2)	0.16874 (18)	0.96982 (18)	0.0294 (7)
N4	0.7072 (3)	0.25148 (17)	1.01256 (19)	0.0304 (6)
C25	0.5843 (3)	0.3968 (2)	0.8970 (3)	0.0398 (9)
Co1	0.58872 (4)	0.25212 (3)	0.90051 (3)	0.02805 (16)
O1	0.5219 (2)	0.34952 (16)	0.94414 (17)	0.0381 (6)
O2	0.5824 (3)	0.47344 (18)	0.8941 (2)	0.0651 (9)
O3	0.6496 (2)	0.34948 (15)	0.85188 (16)	0.0365 (6)
Br1	1.09456 (5)	0.26057 (4)	0.90092 (4)	0.0860 (2)
O4	0.7273 (5)	0.5300 (3)	0.7641 (3)	0.1209 (16)
O5	0.9316 (14)	0.4389 (5)	0.8542 (6)	0.140 (4)	0.80 (2)
O5'	1.012 (5)	0.436 (2)	0.869 (3)	0.140 (4)	0.20 (2)
O6	0.8141 (11)	0.5262 (7)	1.0104 (8)	0.158 (5)	0.761 (18)
O6'	0.745 (3)	0.560 (2)	1.046 (3)	0.158 (5)	0.239 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.039 (2)	0.031 (2)	0.033 (2)	0.0002 (17)	0.0044 (16)	0.0027 (16)
C2	0.040 (2)	0.034 (2)	0.032 (2)	−0.0010 (17)	−0.0007 (16)	0.0069 (16)
C3	0.044 (2)	0.043 (2)	0.029 (2)	−0.0060 (18)	−0.0069 (16)	0.0008 (16)
C4	0.045 (2)	0.039 (2)	0.0268 (19)	−0.0022 (18)	0.0016 (16)	−0.0030 (16)
C5	0.037 (2)	0.0279 (19)	0.0262 (18)	−0.0059 (16)	0.0075 (15)	0.0007 (14)
C6	0.037 (2)	0.0311 (19)	0.0220 (18)	−0.0066 (16)	0.0049 (14)	0.0014 (14)
C7	0.044 (2)	0.039 (2)	0.033 (2)	−0.0071 (18)	0.0070 (16)	−0.0048 (17)
C8	0.046 (2)	0.038 (2)	0.040 (2)	0.0014 (18)	0.0135 (18)	−0.0051 (17)
C9	0.035 (2)	0.035 (2)	0.042 (2)	−0.0011 (17)	0.0090 (17)	0.0055 (17)
C10	0.038 (2)	0.034 (2)	0.0287 (19)	−0.0032 (17)	0.0016 (15)	0.0057 (15)
C11	0.043 (2)	0.049 (3)	0.052 (3)	0.006 (2)	−0.0060 (19)	0.004 (2)
C12	0.041 (2)	0.055 (3)	0.064 (3)	0.004 (2)	0.009 (2)	0.003 (2)
C13	0.038 (2)	0.035 (2)	0.0273 (19)	−0.0020 (17)	0.0049 (15)	0.0004 (15)
C14	0.038 (2)	0.0292 (19)	0.037 (2)	0.0040 (16)	0.0106 (16)	−0.0027 (16)
C15	0.042 (2)	0.035 (2)	0.040 (2)	0.0020 (17)	0.0137 (18)	0.0056 (16)
C16	0.039 (2)	0.038 (2)	0.0273 (19)	0.0040 (17)	0.0057 (15)	0.0096 (15)
C17	0.036 (2)	0.0291 (19)	0.0234 (18)	0.0054 (16)	0.0057 (14)	0.0016 (14)
C18	0.036 (2)	0.031 (2)	0.0222 (17)	0.0027 (16)	0.0039 (14)	0.0000 (14)
C19	0.040 (2)	0.044 (2)	0.0263 (19)	0.0027 (18)	0.0026 (15)	0.0016 (16)
C20	0.039 (2)	0.047 (2)	0.027 (2)	0.0045 (19)	−0.0020 (16)	−0.0030 (17)
C21	0.037 (2)	0.038 (2)	0.035 (2)	0.0012 (17)	0.0043 (16)	−0.0079 (17)
C22	0.041 (2)	0.035 (2)	0.028 (2)	−0.0053 (18)	0.0032 (15)	0.0011 (15)
C23	0.040 (2)	0.046 (2)	0.057 (3)	−0.0114 (19)	0.0104 (19)	0.000 (2)
C24	0.044 (2)	0.057 (3)	0.050 (3)	−0.009 (2)	0.0020 (19)	−0.009 (2)
N1	0.0346 (16)	0.0322 (16)	0.0231 (15)	−0.0002 (14)	0.0044 (12)	0.0045 (12)
N2	0.0353 (17)	0.0325 (17)	0.0256 (15)	−0.0027 (14)	0.0035 (12)	0.0018 (12)
N3	0.0345 (17)	0.0310 (16)	0.0229 (15)	0.0016 (13)	0.0053 (12)	0.0015 (12)
N4	0.0379 (17)	0.0295 (15)	0.0233 (15)	−0.0034 (14)	0.0040 (12)	−0.0011 (12)
C25	0.051 (2)	0.034 (2)	0.033 (2)	−0.001 (2)	0.0039 (17)	0.0021 (18)
Co1	0.0354 (3)	0.0294 (3)	0.0184 (3)	−0.0015 (2)	0.00190 (18)	0.0018 (2)
O1	0.0463 (16)	0.0376 (15)	0.0312 (14)	0.0005 (12)	0.0087 (11)	−0.0018 (11)
O2	0.082 (2)	0.0318 (17)	0.086 (2)	0.0046 (16)	0.0279 (19)	0.0062 (16)
O3	0.0474 (16)	0.0339 (14)	0.0289 (14)	−0.0032 (12)	0.0084 (11)	0.0051 (11)
Br1	0.0908 (5)	0.1163 (6)	0.0404 (3)	0.0077 (4)	−0.0173 (3)	−0.0045 (3)
O4	0.181 (5)	0.098 (3)	0.093 (3)	−0.033 (3)	0.049 (3)	−0.006 (3)
O5	0.149 (11)	0.099 (4)	0.165 (6)	−0.033 (6)	0.005 (7)	0.029 (4)
O5'	0.149 (11)	0.099 (4)	0.165 (6)	−0.033 (6)	0.005 (7)	0.029 (4)
O6	0.118 (8)	0.152 (8)	0.184 (8)	−0.041 (7)	−0.032 (7)	0.093 (7)
O6'	0.118 (8)	0.152 (8)	0.184 (8)	−0.041 (7)	−0.032 (7)	0.093 (7)

Geometric parameters (Å, º) top

C1—N1	1.328 (4)	C15—C16	1.376 (5)
C1—C2	1.383 (5)	C15—H15	0.9300
C1—H1	0.9300	C16—C17	1.388 (5)
C2—C3	1.387 (5)	C16—H16	0.9300
C2—C11	1.497 (5)	C17—N3	1.355 (4)
C3—C4	1.372 (5)	C17—C18	1.461 (5)
C3—H3	0.9300	C18—N4	1.353 (4)
C4—C5	1.375 (5)	C18—C19	1.374 (5)
C4—H4	0.9300	C19—C20	1.371 (5)
C5—N1	1.358 (4)	C19—H19	0.9300
C5—C6	1.459 (5)	C20—C21	1.390 (5)
C6—N2	1.346 (4)	C20—H20	0.9300
C6—C7	1.374 (5)	C21—C22	1.391 (5)
C7—C8	1.386 (5)	C21—C24	1.496 (5)
C7—H7	0.9300	C22—N4	1.337 (4)
C8—C9	1.381 (5)	C22—H22	0.9300
C8—H8	0.9300	C23—H23A	0.9600
C9—C10	1.382 (5)	C23—H23B	0.9600
C9—C12	1.495 (5)	C23—H23C	0.9600
C10—N2	1.341 (4)	C24—H24A	0.9600
C10—H10	0.9300	C24—H24B	0.9600
C11—H11A	0.9600	C24—H24C	0.9600
C11—H11B	0.9600	N1—Co1	1.927 (3)
C11—H11C	0.9600	N2—Co1	1.951 (3)
C12—H12A	0.9600	N3—Co1	1.950 (3)
C12—H12B	0.9600	N4—Co1	1.925 (3)
C12—H12C	0.9600	C25—O2	1.225 (5)
C13—N3	1.337 (4)	C25—O1	1.312 (4)
C13—C14	1.391 (5)	C25—O3	1.318 (4)
C13—H13	0.9300	C25—Co1	2.309 (4)
C14—C15	1.374 (5)	Co1—O3	1.891 (2)
C14—C23	1.496 (5)	Co1—O1	1.892 (2)

N1—C1—C2	123.0 (3)	C19—C20—C21	119.8 (3)
N1—C1—H1	118.5	C19—C20—H20	120.1
C2—C1—H1	118.5	C21—C20—H20	120.1
C1—C2—C3	117.3 (3)	C20—C21—C22	117.4 (3)
C1—C2—C11	120.8 (4)	C20—C21—C24	122.3 (3)
C3—C2—C11	121.9 (3)	C22—C21—C24	120.2 (4)
C4—C3—C2	119.8 (3)	N4—C22—C21	122.6 (3)
C4—C3—H3	120.1	N4—C22—H22	118.7
C2—C3—H3	120.1	C21—C22—H22	118.7
C3—C4—C5	120.2 (4)	C14—C23—H23A	109.5
C3—C4—H4	119.9	C14—C23—H23B	109.5
C5—C4—H4	119.9	H23A—C23—H23B	109.5
N1—C5—C4	120.0 (3)	C14—C23—H23C	109.5
N1—C5—C6	114.0 (3)	H23A—C23—H23C	109.5
C4—C5—C6	125.9 (3)	H23B—C23—H23C	109.5
N2—C6—C7	121.1 (3)	C21—C24—H24A	109.5
N2—C6—C5	114.4 (3)	C21—C24—H24B	109.5
C7—C6—C5	124.5 (3)	H24A—C24—H24B	109.5
C6—C7—C8	119.5 (3)	C21—C24—H24C	109.5
C6—C7—H7	120.3	H24A—C24—H24C	109.5
C8—C7—H7	120.3	H24B—C24—H24C	109.5
C9—C8—C7	119.8 (4)	C1—N1—C5	119.7 (3)
C9—C8—H8	120.1	C1—N1—Co1	125.8 (2)
C7—C8—H8	120.1	C5—N1—Co1	114.5 (2)
C8—C9—C10	117.5 (3)	C10—N2—C6	119.0 (3)
C8—C9—C12	122.8 (4)	C10—N2—Co1	126.9 (2)
C10—C9—C12	119.7 (4)	C6—N2—Co1	114.0 (2)
N2—C10—C9	123.0 (3)	C13—N3—C17	119.4 (3)
N2—C10—H10	118.5	C13—N3—Co1	127.1 (2)
C9—C10—H10	118.5	C17—N3—Co1	113.4 (2)
C2—C11—H11A	109.5	C22—N4—C18	119.4 (3)
C2—C11—H11B	109.5	C22—N4—Co1	125.6 (2)
H11A—C11—H11B	109.5	C18—N4—Co1	115.0 (2)
C2—C11—H11C	109.5	O2—C25—O1	125.7 (4)
H11A—C11—H11C	109.5	O2—C25—O3	124.3 (4)
H11B—C11—H11C	109.5	O1—C25—O3	110.0 (3)
C9—C12—H12A	109.5	O2—C25—Co1	179.2 (3)
C9—C12—H12B	109.5	O1—C25—Co1	55.03 (18)
H12A—C12—H12B	109.5	O3—C25—Co1	54.97 (17)
C9—C12—H12C	109.5	O3—Co1—O1	69.44 (11)
H12A—C12—H12C	109.5	O3—Co1—N4	93.28 (11)
H12B—C12—H12C	109.5	O1—Co1—N4	89.95 (11)
N3—C13—C14	122.8 (3)	O3—Co1—N1	89.86 (11)
N3—C13—H13	118.6	O1—Co1—N1	93.03 (11)
C14—C13—H13	118.6	N4—Co1—N1	176.27 (12)
C15—C14—C13	117.4 (3)	O3—Co1—N3	167.52 (11)
C15—C14—C23	123.5 (3)	O1—Co1—N3	98.53 (12)
C13—C14—C23	119.1 (3)	N4—Co1—N3	83.14 (12)
C14—C15—C16	120.8 (3)	N1—Co1—N3	94.19 (12)
C14—C15—H15	119.6	O3—Co1—N2	97.86 (12)
C16—C15—H15	119.6	O1—Co1—N2	166.77 (11)
C15—C16—C17	119.1 (3)	N4—Co1—N2	94.61 (12)
C15—C16—H16	120.4	N1—Co1—N2	82.98 (12)
C17—C16—H16	120.4	N3—Co1—N2	94.34 (12)
N3—C17—C16	120.6 (3)	O3—Co1—C25	34.81 (12)
N3—C17—C18	114.8 (3)	O1—Co1—C25	34.63 (12)
C16—C17—C18	124.6 (3)	N4—Co1—C25	91.91 (13)
N4—C18—C19	120.8 (3)	N1—Co1—C25	91.82 (12)
N4—C18—C17	113.6 (3)	N3—Co1—C25	133.08 (13)
C19—C18—C17	125.6 (3)	N2—Co1—C25	132.58 (13)
C20—C19—C18	120.1 (4)	C25—O1—Co1	90.3 (2)
C20—C19—H19	120.0	C25—O3—Co1	90.2 (2)
C18—C19—H19	120.0

N1—C1—C2—C3	0.1 (6)	C22—N4—Co1—N3	179.6 (3)
N1—C1—C2—C11	−178.4 (3)	C18—N4—Co1—N3	0.0 (2)
C1—C2—C3—C4	0.8 (6)	C22—N4—Co1—N2	85.7 (3)
C11—C2—C3—C4	179.3 (4)	C18—N4—Co1—N2	−93.9 (3)
C2—C3—C4—C5	−1.1 (6)	C22—N4—Co1—C25	−47.3 (3)
C3—C4—C5—N1	0.5 (5)	C18—N4—Co1—C25	133.2 (3)
C3—C4—C5—C6	−178.4 (3)	C1—N1—Co1—O3	−80.4 (3)
N1—C5—C6—N2	−1.9 (4)	C5—N1—Co1—O3	97.7 (2)
C4—C5—C6—N2	177.0 (3)	C1—N1—Co1—O1	−11.0 (3)
N1—C5—C6—C7	179.3 (3)	C5—N1—Co1—O1	167.1 (2)
C4—C5—C6—C7	−1.8 (6)	C1—N1—Co1—N3	87.8 (3)
N2—C6—C7—C8	−1.5 (5)	C5—N1—Co1—N3	−94.2 (2)
C5—C6—C7—C8	177.2 (3)	C1—N1—Co1—N2	−178.3 (3)
C6—C7—C8—C9	−0.8 (6)	C5—N1—Co1—N2	−0.3 (2)
C7—C8—C9—C10	1.4 (5)	C1—N1—Co1—C25	−45.6 (3)
C7—C8—C9—C12	−177.3 (4)	C5—N1—Co1—C25	132.4 (2)
C8—C9—C10—N2	0.1 (5)	C13—N3—Co1—O3	103.1 (5)
C12—C9—C10—N2	178.9 (3)	C17—N3—Co1—O3	−73.0 (6)
N3—C13—C14—C15	−0.1 (5)	C13—N3—Co1—O1	88.1 (3)
N3—C13—C14—C23	179.2 (3)	C17—N3—Co1—O1	−88.0 (2)
C13—C14—C15—C16	1.1 (5)	C13—N3—Co1—N4	177.0 (3)
C23—C14—C15—C16	−178.3 (4)	C17—N3—Co1—N4	0.9 (2)
C14—C15—C16—C17	−0.7 (5)	C13—N3—Co1—N1	−5.6 (3)
C15—C16—C17—N3	−0.6 (5)	C17—N3—Co1—N1	178.3 (2)
C15—C16—C17—C18	178.9 (3)	C13—N3—Co1—N2	−88.8 (3)
N3—C17—C18—N4	1.6 (4)	C17—N3—Co1—N2	95.1 (2)
C16—C17—C18—N4	−178.0 (3)	C13—N3—Co1—C25	90.9 (3)
N3—C17—C18—C19	−178.2 (3)	C17—N3—Co1—C25	−85.3 (3)
C16—C17—C18—C19	2.3 (6)	C10—N2—Co1—O3	87.5 (3)
N4—C18—C19—C20	0.7 (5)	C6—N2—Co1—O3	−89.7 (2)
C17—C18—C19—C20	−179.5 (3)	C10—N2—Co1—O1	103.4 (5)
C18—C19—C20—C21	0.0 (6)	C6—N2—Co1—O1	−73.9 (6)
C19—C20—C21—C22	−0.8 (5)	C10—N2—Co1—N4	−6.4 (3)
C19—C20—C21—C24	178.5 (4)	C6—N2—Co1—N4	176.3 (2)
C20—C21—C22—N4	0.9 (6)	C10—N2—Co1—N1	176.4 (3)
C24—C21—C22—N4	−178.5 (3)	C6—N2—Co1—N1	−0.8 (2)
C2—C1—N1—C5	−0.7 (5)	C10—N2—Co1—N3	−89.9 (3)
C2—C1—N1—Co1	177.2 (3)	C6—N2—Co1—N3	92.9 (2)
C4—C5—N1—C1	0.5 (5)	C10—N2—Co1—C25	90.4 (3)
C6—C5—N1—C1	179.4 (3)	C6—N2—Co1—C25	−86.8 (3)
C4—C5—N1—Co1	−177.7 (3)	O1—C25—Co1—O3	179.8 (3)
C6—C5—N1—Co1	1.3 (4)	O3—C25—Co1—O1	−179.8 (3)
C9—C10—N2—C6	−2.4 (5)	O1—C25—Co1—N4	−87.1 (2)
C9—C10—N2—Co1	−179.5 (3)	O3—C25—Co1—N4	93.0 (2)
C7—C6—N2—C10	3.0 (5)	O1—C25—Co1—N1	92.7 (2)
C5—C6—N2—C10	−175.8 (3)	O3—C25—Co1—N1	−87.1 (2)
C7—C6—N2—Co1	−179.5 (3)	O1—C25—Co1—N3	−4.8 (3)
C5—C6—N2—Co1	1.7 (4)	O3—C25—Co1—N3	175.40 (17)
C14—C13—N3—C17	−1.2 (5)	O1—C25—Co1—N2	174.82 (18)
C14—C13—N3—Co1	−177.1 (3)	O3—C25—Co1—N2	−5.0 (3)
C16—C17—N3—C13	1.5 (5)	O2—C25—O1—Co1	179.6 (4)
C18—C17—N3—C13	−178.0 (3)	O3—C25—O1—Co1	0.1 (3)
C16—C17—N3—Co1	178.0 (3)	O3—Co1—O1—C25	−0.1 (2)
C18—C17—N3—Co1	−1.6 (4)	N4—Co1—O1—C25	93.4 (2)
C21—C22—N4—C18	−0.2 (5)	N1—Co1—O1—C25	−88.8 (2)
C21—C22—N4—Co1	−179.7 (3)	N3—Co1—O1—C25	176.5 (2)
C19—C18—N4—C22	−0.7 (5)	N2—Co1—O1—C25	−16.9 (6)
C17—C18—N4—C22	179.6 (3)	O2—C25—O3—Co1	−179.6 (4)
C19—C18—N4—Co1	178.9 (3)	O1—C25—O3—Co1	−0.1 (3)
C17—C18—N4—Co1	−0.8 (4)	O1—Co1—O3—C25	0.1 (2)
C22—N4—Co1—O3	−12.4 (3)	N4—Co1—O3—C25	−88.6 (2)
C18—N4—Co1—O3	168.0 (2)	N1—Co1—O3—C25	93.4 (2)
C22—N4—Co1—O1	−81.8 (3)	N3—Co1—O3—C25	−15.7 (6)
C18—N4—Co1—O1	98.6 (2)	N2—Co1—O3—C25	176.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1	0.93	2.43	2.931 (5)	114
C3—H3···Br1ⁱ	0.93	2.80	3.718 (4)	168
C4—H4···O1ⁱⁱ	0.93	2.51	3.257 (4)	138
C10—H10···N4	0.93	2.53	3.036 (4)	114
C11—H11A···Br1ⁱⁱⁱ	0.96	2.91	3.810 (4)	157
C13—H13···N1	0.93	2.52	3.023 (4)	114
C19—H19···O3^iv	0.93	2.52	3.284 (4)	140
C20—H20···Br1^iv	0.93	2.85	3.778 (4)	172
C22—H22···O3	0.93	2.44	2.939 (4)	113
C23—H23B···O4^v	0.96	2.42	3.330 (6)	158
C24—H24A···Br1	0.96	2.93	3.836 (5)	158

Symmetry codes: (i) x−1, −y+1/2, z−1/2; (ii) x, −y+1/2, z−1/2; (iii) x−1, y, z; (iv) x, −y+1/2, z+1/2; (v) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Co(CO₃)(C₁₂H₁₂N₂)₂]Br·3H₂O
M_r	621.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.5802 (15), 15.958 (2), 14.3921 (17)
β (°)	100.143 (3)
V (Å³)	2618.0 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.23
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.555, 0.664
No. of measured, independent and observed [I > 2σ(I)] reflections	23769, 5033, 3111
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.145, 1.02
No. of reflections	5033
No. of parameters	346
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.77, −1.43

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1	0.93	2.43	2.931 (5)	114
C3—H3···Br1ⁱ	0.93	2.80	3.718 (4)	168
C4—H4···O1ⁱⁱ	0.93	2.51	3.257 (4)	138
C10—H10···N4	0.93	2.53	3.036 (4)	114
C11—H11A···Br1ⁱⁱⁱ	0.96	2.91	3.810 (4)	157
C13—H13···N1	0.93	2.52	3.023 (4)	114
C19—H19···O3^iv	0.93	2.52	3.284 (4)	140
C20—H20···Br1^iv	0.93	2.85	3.778 (4)	172
C22—H22···O3	0.93	2.44	2.939 (4)	113
C23—H23B···O4^v	0.96	2.42	3.330 (6)	158
C24—H24A···Br1	0.96	2.93	3.836 (5)	158

Symmetry codes: (i) x−1, −y+1/2, z−1/2; (ii) x, −y+1/2, z−1/2; (iii) x−1, y, z; (iv) x, −y+1/2, z+1/2; (v) −x+1, y−1/2, −z+3/2.

Acknowledgements

The authors are thankful to Rev. Dr C. Joe Arun, SJ, Secretary, and Rev. Dr B. Jeyaraj, SJ, Principal, Loyola College (Autonomous), Chennai-34, India, for providing the necessary facilities and the Head, SAIF, IIT Madras, Chennai-36, India, for recording the X-ray data.

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Bruker (2004). SADABS, APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Carol, D., Barry, C., Malachy, M. C., Michael, D. & Denise, A. E. (2006). Chem. Biol. Int. 164, 115–125. Google Scholar
Eddie, L. C., Christa, S. & Andrew, D. K. (2010). J. Chem. Pharm. Res. 3, 1711–1728. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Harding, D. J., Harding, P. & Adams, H. (2008). Acta Cryst. E64, m1538. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hyung, J. K., Yong, C. J., Jong, I. R. & Taek, H. K. (2006). Bull. Kor. Chem. 27, 2084–2086. Google Scholar
Jayaweera, P. M, Palayangoda, S. S., Tennakone. & Gamage, R. G. C. R. (2002). Curr. Sci. 83, 1368–1371. Google Scholar
Kusrini, E., Saleh, M. I., Kia, R. & Fun, H.-K. (2008). Acta Cryst. E64, m1014–m1015. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ma, P.-T., Wang, Y.-X., Zhang, G.-Q. & Li, M.-X. (2008). Acta Cryst. E64, m14. Web of Science CSD CrossRef IUCr Journals Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Momeni, B. Z., Rominger, F. & Hosseini, S. S. (2009). Acta Cryst. E65, m690. Web of Science CSD CrossRef IUCr Journals Google Scholar
Phatchimkun, J. & Chaichit, N. (2011). Acta Cryst. E67, m516–m517. Web of Science CSD CrossRef IUCr Journals Google Scholar
Raj, P. S., Ajnesh, S., Paula, B., Vitor, F. & Paloth, V. (2008). J. Mol. Struct. 888, 291–299. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shi, Y., Toms, B. B., Dixit, N., Kumari, N., Mishra, L., Goodisman, J. & Dabrowiak, J. C. (2010). Chem. Res. Toxicol. 23, 1417–1426. Web of Science CSD CrossRef CAS PubMed Google Scholar
Vitushkina, S. V., Starodub, V. A. & Pyshkin, O. S. (2006). Russ. J. Coord. Chem. 32–34, 237–241. Web of Science CrossRef Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.