Tris(2,2′-bipyridine-κ2N:N′)cobalt(III) trichloride tetra­hydrate

Liu, W.; Xu, W.; Lin, J.-L.; Xie, H.-Z.

doi:10.1107/S1600536808038154

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page m1586

doi:10.1107/S1600536808038154

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Tris(2,2′-bipyridine-κ²N:N′)cobalt(III) trichloride tetrahydrate

Wen Liu,^a Wei Xu,^a ^* Jian-Li Lin ^a and Hong-Zhen Xie ^a

^aState Key Laboratory Base of Novel Functional Materials and Preparation Science, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, People's Republic of China
^*Correspondence e-mail: zhengyueqing@nbu.edu.cn

(Received 14 October 2008; accepted 16 November 2008; online 22 November 2008)

The title compound, [Co(C₁₀H₈N₂)₃]Cl₃·4H₂O, contains discrete [Co(bpy)₃]³⁺ cations (bpy is 2,2′-bipyridine), Cl⁻ anions and water molecules. The [Co(bpy)₃]³⁺ complex cation exhibits C₂ symmetry with the twofold axis through the central Co atom and bisecting one bpy ligand and one of the Cl⁻ anions. The four solvent water molecules and the remaining two Cl⁻ anions lie on a mirror plane. Hydrogen-bond interactions define a two-dimensional layer structure parallel to (100), which consists of seven-membered [Cl₂(H₂O)₅], eight-membered [Cl₄(H₂O)₄] and ten-membered [Cl₂(H₂O)₈] rings.

Related literature

For general background, see: Liu et al. (1996 ); Nauta & Miller (2000 ); Ludwig (2001 ); Saha & Bernal (2005 ); Reger et al. (2006 ); Li et al. (2007 ); Mir & Vittal (2007 ). For related structures, see: Hernández-Molina et al. (1998 ).

Experimental

Crystal data

[Co(C₁₀H₈N₂)₃]Cl₃·4H₂O
M_r = 705.90
Orthorhombic, C m c a
a = 20.171 (4) Å
b = 23.170 (5) Å
c = 13.316 (3) Å
V = 6223 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.86 mm⁻¹
T = 295 (2) K
0.12 × 0.10 × 0.08 mm

Data collection

Bruker P4 diffractometer
Absorption correction: ψ scan (XSCANS; Siemens, 1996 ) T_min = 0.905, T_max = 0.929
3430 measured reflections
2824 independent reflections
1980 reflections with I > 2σ(I)
R_int = 0.049
3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.162
S = 1.03
2824 reflections
225 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.01 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1W2⋯O2	0.85 (4)	2.04 (5)	2.885 (9)	176 (9)
O1—H1W1⋯Cl1	0.83 (4)	2.30 (4)	3.127 (7)	180 (9)
O2—H2W1⋯Cl1ⁱ	0.84 (4)	2.48 (4)	3.317 (7)	175 (6)
O2—H2W2⋯Cl2	0.84 (3)	2.33 (3)	3.165 (5)	173 (7)
O3—H3W1⋯Cl1ⁱⁱ	0.85 (6)	2.33 (6)	3.161 (5)	166 (6)
O3—H3W2⋯Cl2ⁱⁱⁱ	0.84 (4)	2.27 (5)	3.095 (5)	170 (7)
O4—H4W1⋯O1	0.79 (5)	2.06 (5)	2.841 (8)	169 (5)
O4—H4W2⋯O3	0.81 (3)	2.00 (3)	2.795 (8)	168 (7)
Symmetry codes: (i) $[-x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) x, -y+1, -z+1; (iv) $[-x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (v) $[-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ .

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808038154/bg2219sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808038154/bg2219Isup2.hkl

checkCIF report

Comment top

Due to the central role that water plays in biological and chemical processes, research on its structure, properties and functions has attracted the scientist's attention (Liu, et al., 1996; Nauta & Miller, 2000; Ludwig, 2001; Mir & Vittal, 2007). However, there are only a few reports focused on the experimental identificaion and analysis of hydrogen-bond networks between water of crystallization and chloride counterions in crystalline materials. As a few examples we can mention [cis-α-(trine)CoCl₂]Cl.3H₂O (Saha & Bernal, 2005) where a two-dimensional layered structure containing [Cl₂(H₂O)₄] six-membered rings build up. In the crystal structure of {p-C₆H₄[CH₂OCH₂C(pz)₃]₂[Ru(p-cymene)]₂}Cl₄.14H₂O two-dimensional layers built from four-membered [Cl(H₂O)₃], five-membered [Cl(H₂O)₄], six-membered [Cl(H₂O)₅] and seven-membered [Cl₃(H₂O)₄] rings formed through hydrogen bond self-assembly (Reger, et al., 2006). A hybrid water-chloride structure of 14 water molecules and 4 Cl^- anions connected into layers is formed in the crystal structure of an europium complex [Eu₃(BDC)₃(phen)₃Cl(H₂O)₆]Cl₂.4H₂O (Li, et al., 2007). The references suggest that a great variety of mixed water-chloride supramolecular self-assemblies is possible. Herein, we describe a structure of a cobalt(III) complex containing discrete tris(2,2'-bipyridine)cobalt(III) cations and infinite layers of water and chloride anions, and where seven-membered (Cl₂(H₂O)₅), eight-membered (Cl₄(H₂O)₄) and ten-membered (Cl₂(H₂O)₈) rings can be found.

The crystal structure of the title compound is composed of [Co(bpy)₃]³⁺ complex cations, Cl^- anions and crystal H₂O molecules (Fig. 1). Within the trivalent complex cations, the Co atoms are each surrounded by six N atoms of three chelating bpy ligands to complete a distorted octahedral coordination with d(Co—N) = 1,928 (3)–1.939 (3) Å, the cis and trans N—Co—N bond angles in the range 83.50 (19)–93.82 (14) and 175.23 (14)–176.38 (19)°, respectively. Such distances are similar to those found in other related structures (Hernández-Molina, et al., 1998). The complex cation exhibits C₂ symmetry with the twofold axis through the central Co atom and bisecting the C5—C5ⁱ bond of one bpy ligand (i = -x + 1/2, y, -z + 3/2), as well as one of the Cl^- anions (Cl3). Through a C—H···Cl weak hydrogen bond the [Co(phen)₃]³⁺ moieties are interlink into one-dimensional chains along the [001] direction (Fig.2). There are no π-π stacking interactions in the chains.

The most starling feature of the solid-state structure of 1 is the hydrogen-bonding interactions of the four water molecules and the remaining two Cl^- anions (Cl1 and Cl2), which lay on a mirror plane. The four crystal water molecules (O1, O2, O3,and O4) locate at the crystallographic 8f position and through intermolecular hydrogen bonds determine a linear water tetramer (H₂O)₄. The O···O distances span the range 2.795 (8)–2.885 (9) Å. Interestingly, such tetrameric water groups are further hydrogen-bond-interacting with the Cl^- anions to complete a two-dimensional water-chloride framework parallel to (100). As Shown in Fig. 3, the two-dimensional layers are composed by seven- (five water molecules and two Cl^- anions), eight- (four water molecules and four Cl^- anions) and ten-membered (eight water molecules and two Cl^- anions) rings through O—H···O and O—H···Cl interactions (Table 1). The O···Cl distances range from 3.095 (5) to 3.317 (7) Å and O—H···Cl angles span the range 166 (6) to 180 (9)°. The water-chloride layer can be viewed as building blocks, which are pillared by [Co(bpy)₃]³⁺ spacers to produce an infinite three-dimensional supramolecular edifice. In this sense, the layer is different from already reported water clusters and other morphologies, which are situated within the host cavities or channels generated by organic and inorganic moieties (Fig. 4).

Related literature top

For general background, see: Liu et al. (1996); Nauta & Miller (2000); Ludwig (2001); Saha & Bernal (2005); Reger et al. (2006); Li et al. (2007); Mir & Vittal (2007). For related structures, see: Hernández-Molina et al. (1998).

Experimental top

Addition of 10 ml CH₃OH containing 0.162 g (1.04 mmol) 2,2'-bipyridine (bpy) to an aqueous solution of 0.238 g (1.00 mmol) CoCl₂.6H₂O in 10 ml H₂O gave a yellow solution, then dropwise added 3 ml 30% H₂O₂ solution to the mixture, stirred for ca half an hour. The resulting light-yellow solution (PH = 6.48) was allowed to stand at room temperature. After 8 days, a small amount of yellow block crystals had grown.

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP view of the title compound. The dispalcement ellipsoids are drawn at 40% probability level. [Symmetry code: (i) -x + 1/2, y, -z + 3/2]
	Fig. 2. The one-dimensional chain of the [Co(phen)₃]³⁺ cations along with [001] direction.
	Fig. 3. The two-dimensional water-chloride framework parallel to (100). [Symmetry codes: (ii) -x, -y + 3/2, z - 1/2; (iii) -x, -y + 3/2, z + 1/2; (iv): x, -y + 1, -z + 1]
	Fig. 4. Packing diagram of the supramolecular edifice viewed along the crystallographic c axis.

Tris(2,2'-bipyridine-κ²N:N')cobalt(III) trichloride tetrahydrate top

Crystal data top

[Co(C₁₀H₈N₂)₃]Cl₃·4H₂O	F(000) = 2912
M_r = 705.90	D_x = 1.507 Mg m⁻³
Orthorhombic, Cmca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2bc 2	Cell parameters from 25 reflections
a = 20.171 (4) Å	θ = 5.0–12.5°
b = 23.170 (5) Å	µ = 0.86 mm⁻¹
c = 13.316 (3) Å	T = 295 K
V = 6223 (2) Å³	Block, yellow
Z = 8	0.12 × 0.10 × 0.08 mm

Data collection top

Bruker P4 diffractometer	1980 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.049
Graphite monochromator	θ_max = 25.0°, θ_min = 1.8°
θ/2θ scans	h = −23→1
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −1→27
T_min = 0.905, T_max = 0.929	l = −1→15
3430 measured reflections	3 standard reflections every 97 reflections
2824 independent reflections	intensity decay: none

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.1023P)²] where P = (F_o² + 2F_c²)/3
2824 reflections	(Δ/σ)_max < 0.001
225 parameters	Δρ_max = 1.01 e Å⁻³
12 restraints	Δρ_min = −0.66 e Å⁻³

Crystal data top

[Co(C₁₀H₈N₂)₃]Cl₃·4H₂O	V = 6223 (2) Å³
M_r = 705.90	Z = 8
Orthorhombic, Cmca	Mo Kα radiation
a = 20.171 (4) Å	µ = 0.86 mm⁻¹
b = 23.170 (5) Å	T = 295 K
c = 13.316 (3) Å	0.12 × 0.10 × 0.08 mm

Data collection top

Bruker P4 diffractometer	1980 reflections with I > 2σ(I)
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	R_int = 0.049
T_min = 0.905, T_max = 0.929	3 standard reflections every 97 reflections
3430 measured reflections	intensity decay: none
2824 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	12 restraints
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 1.01 e Å⁻³
2824 reflections	Δρ_min = −0.66 e Å⁻³
225 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	0.2500	0.40805 (3)	0.7500	0.0230 (2)
Cl1	0.0000	0.80958 (8)	0.57842 (16)	0.0580 (5)
Cl2	0.0000	0.52160 (8)	0.83302 (13)	0.0487 (5)
Cl3	0.2500	0.71245 (7)	0.7500	0.0508 (5)
N1	0.19627 (15)	0.47048 (14)	0.6973 (2)	0.0254 (7)
N2	0.19583 (15)	0.34934 (14)	0.6871 (3)	0.0278 (8)
N3	0.29820 (15)	0.40542 (14)	0.6251 (2)	0.0267 (8)
C1	0.13885 (18)	0.46643 (19)	0.6478 (3)	0.0328 (10)
H1A	0.1227	0.4300	0.6316	0.039*
C2	0.1025 (2)	0.51433 (19)	0.6198 (3)	0.0367 (11)
H2A	0.0628	0.5100	0.5852	0.044*
C3	0.1256 (2)	0.5687 (2)	0.6436 (3)	0.0382 (11)
H3A	0.1016	0.6014	0.6257	0.046*
C4	0.1849 (2)	0.57363 (18)	0.6944 (3)	0.0370 (11)
H4A	0.2019	0.6098	0.7102	0.044*
C5	0.21896 (19)	0.52388 (17)	0.7216 (3)	0.0267 (9)
C6	0.1430 (2)	0.32196 (18)	0.7267 (4)	0.0368 (11)
H6A	0.1316	0.3286	0.7934	0.044*
C7	0.1052 (2)	0.28387 (19)	0.6695 (4)	0.0453 (12)
H7A	0.0695	0.2646	0.6983	0.054*
C8	0.1204 (2)	0.27501 (19)	0.5722 (4)	0.0486 (13)
H8A	0.0939	0.2512	0.5330	0.058*
C9	0.1750 (2)	0.30103 (18)	0.5309 (4)	0.0407 (11)
H9A	0.1867	0.2940	0.4645	0.049*
C10	0.2128 (2)	0.33844 (17)	0.5904 (3)	0.0300 (9)
C11	0.27255 (19)	0.36858 (17)	0.5557 (3)	0.0284 (9)
C12	0.3015 (2)	0.3604 (2)	0.4646 (3)	0.0410 (11)
H12A	0.2824	0.3358	0.4176	0.049*
C13	0.3601 (2)	0.3892 (2)	0.4427 (4)	0.0452 (12)
H13A	0.3813	0.3835	0.3815	0.054*
C14	0.3861 (2)	0.4261 (2)	0.5121 (3)	0.0397 (11)
H14A	0.4251	0.4459	0.4984	0.048*
C15	0.3545 (2)	0.43360 (18)	0.6017 (3)	0.0329 (10)
H15A	0.3725	0.4591	0.6482	0.039*
O1	0.0000	0.6769 (3)	0.6215 (5)	0.092 (2)
H1W1	0.0000	0.7122 (17)	0.610 (8)	0.138*
H1W2	0.0000	0.673 (5)	0.685 (3)	0.138*
O2	0.0000	0.6582 (2)	0.8357 (5)	0.0643 (15)
H2W1	0.0000	0.664 (3)	0.898 (3)	0.096*
H2W2	0.0000	0.6220 (14)	0.829 (6)	0.096*
O3	0.0000	0.6013 (2)	0.2581 (4)	0.0701 (17)
H3W1	0.0000	0.620 (3)	0.203 (4)	0.105*
H3W2	0.0000	0.5664 (14)	0.241 (6)	0.105*
O4	0.0000	0.5921 (2)	0.4674 (4)	0.0566 (13)
H4W1	0.0000	0.619 (2)	0.504 (4)	0.085*
H4W2	0.0000	0.600 (3)	0.408 (2)	0.085*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0243 (4)	0.0150 (4)	0.0297 (4)	0.000	−0.0016 (3)	0.000
Cl1	0.0727 (12)	0.0362 (10)	0.0651 (12)	0.000	0.000	−0.0075 (9)
Cl2	0.0512 (9)	0.0463 (10)	0.0486 (10)	0.000	0.000	−0.0087 (8)
Cl3	0.0791 (12)	0.0197 (8)	0.0537 (10)	0.000	0.0244 (9)	0.000
N1	0.0284 (17)	0.0208 (17)	0.0269 (17)	−0.0004 (14)	0.0009 (14)	0.0003 (15)
N2	0.0262 (17)	0.0184 (17)	0.039 (2)	−0.0013 (14)	−0.0021 (14)	0.0005 (15)
N3	0.0277 (17)	0.0194 (16)	0.0331 (18)	0.0035 (14)	0.0010 (14)	0.0009 (15)
C1	0.026 (2)	0.030 (2)	0.042 (2)	0.0006 (18)	−0.0036 (19)	−0.002 (2)
C2	0.031 (2)	0.043 (3)	0.037 (2)	0.0062 (19)	−0.0053 (19)	0.007 (2)
C3	0.037 (2)	0.032 (2)	0.046 (3)	0.0104 (19)	−0.002 (2)	0.007 (2)
C4	0.043 (3)	0.016 (2)	0.052 (3)	0.0019 (18)	0.000 (2)	0.003 (2)
C5	0.0297 (19)	0.022 (2)	0.028 (2)	−0.0002 (18)	0.0029 (17)	0.0022 (17)
C6	0.034 (2)	0.022 (2)	0.054 (3)	−0.0020 (19)	−0.001 (2)	0.001 (2)
C7	0.034 (2)	0.026 (2)	0.076 (4)	−0.0095 (19)	−0.005 (2)	−0.002 (2)
C8	0.045 (3)	0.029 (3)	0.072 (4)	−0.005 (2)	−0.018 (3)	−0.015 (3)
C9	0.044 (3)	0.028 (2)	0.051 (3)	0.000 (2)	−0.008 (2)	−0.012 (2)
C10	0.031 (2)	0.022 (2)	0.038 (2)	0.0031 (17)	−0.0054 (19)	−0.0041 (19)
C11	0.034 (2)	0.021 (2)	0.030 (2)	0.0027 (17)	−0.0067 (18)	−0.0040 (18)
C12	0.049 (3)	0.037 (2)	0.037 (3)	0.007 (2)	−0.005 (2)	−0.006 (2)
C13	0.044 (3)	0.056 (3)	0.036 (3)	0.014 (2)	0.008 (2)	0.003 (2)
C14	0.038 (2)	0.037 (2)	0.044 (3)	0.000 (2)	0.006 (2)	0.007 (2)
C15	0.033 (2)	0.027 (2)	0.040 (3)	−0.0023 (18)	0.0043 (19)	0.000 (2)
O1	0.168 (7)	0.043 (3)	0.064 (4)	0.000	0.000	0.000 (3)
O2	0.069 (3)	0.053 (3)	0.071 (4)	0.000	0.000	0.016 (3)
O3	0.112 (5)	0.038 (3)	0.060 (4)	0.000	0.000	0.004 (3)
O4	0.078 (3)	0.043 (3)	0.048 (3)	0.000	0.000	−0.006 (3)

Geometric parameters (Å, º) top

Co1—N3ⁱ	1.928 (3)	C7—C8	1.347 (7)
Co1—N3	1.928 (3)	C7—H7A	0.9300
Co1—N2ⁱ	1.935 (3)	C8—C9	1.370 (7)
Co1—N2	1.935 (3)	C8—H8A	0.9300
Co1—N1	1.939 (3)	C9—C10	1.401 (6)
Co1—N1ⁱ	1.939 (3)	C9—H9A	0.9300
N1—C1	1.336 (5)	C10—C11	1.467 (6)
N1—C5	1.358 (5)	C11—C12	1.360 (6)
N2—C6	1.348 (5)	C12—C13	1.388 (7)
N2—C10	1.355 (5)	C12—H12A	0.9300
N3—C15	1.347 (5)	C13—C14	1.363 (7)
N3—C11	1.360 (5)	C13—H13A	0.9300
C1—C2	1.381 (6)	C14—C15	1.363 (6)
C1—H1A	0.9300	C14—H14A	0.9300
C2—C3	1.379 (6)	C15—H15A	0.9300
C2—H2A	0.9300	O1—H1W1	0.83 (3)
C3—C4	1.379 (6)	O1—H1W2	0.85 (3)
C3—H3A	0.9300	O2—H2W1	0.85 (3)
C4—C5	1.390 (6)	O2—H2W2	0.84 (3)
C4—H4A	0.9300	O3—H3W1	0.85 (3)
C5—C5ⁱ	1.462 (8)	O3—H3W2	0.84 (3)
C6—C7	1.394 (6)	O4—H4W1	0.80 (3)
C6—H6A	0.9300	O4—H4W2	0.81 (3)

N3ⁱ—Co1—N3	176.38 (19)	N1—C5—C5ⁱ	114.3 (2)
N3ⁱ—Co1—N2ⁱ	83.63 (14)	C4—C5—C5ⁱ	123.9 (3)
N3—Co1—N2ⁱ	93.82 (14)	N2—C6—C7	121.1 (4)
N3ⁱ—Co1—N2	93.82 (14)	N2—C6—H6A	119.4
N3—Co1—N2	83.63 (14)	C7—C6—H6A	119.4
N2ⁱ—Co1—N2	90.69 (19)	C8—C7—C6	119.8 (4)
N3ⁱ—Co1—N1	93.09 (13)	C8—C7—H7A	120.1
N3—Co1—N1	89.61 (13)	C6—C7—H7A	120.1
N2ⁱ—Co1—N1	175.23 (14)	C7—C8—C9	120.2 (4)
N2—Co1—N1	92.99 (13)	C7—C8—H8A	119.9
N3ⁱ—Co1—N1ⁱ	89.61 (13)	C9—C8—H8A	119.9
N3—Co1—N1ⁱ	93.09 (13)	C8—C9—C10	118.9 (5)
N2ⁱ—Co1—N1ⁱ	92.99 (13)	C8—C9—H9A	120.6
N2—Co1—N1ⁱ	175.23 (14)	C10—C9—H9A	120.6
N1—Co1—N1ⁱ	83.50 (19)	N2—C10—C9	121.0 (4)
C1—N1—C5	118.3 (3)	N2—C10—C11	114.7 (3)
C1—N1—Co1	127.6 (3)	C9—C10—C11	124.3 (4)
C5—N1—Co1	113.9 (2)	N3—C11—C12	122.0 (4)
C6—N2—C10	119.0 (4)	N3—C11—C10	113.4 (3)
C6—N2—Co1	127.4 (3)	C12—C11—C10	124.6 (4)
C10—N2—Co1	113.5 (3)	C11—C12—C13	119.1 (4)
C15—N3—C11	117.9 (4)	C11—C12—H12A	120.5
C15—N3—Co1	127.6 (3)	C13—C12—H12A	120.5
C11—N3—Co1	114.5 (3)	C14—C13—C12	119.1 (4)
N1—C1—C2	122.5 (4)	C14—C13—H13A	120.5
N1—C1—H1A	118.8	C12—C13—H13A	120.5
C2—C1—H1A	118.8	C13—C14—C15	119.6 (4)
C3—C2—C1	119.5 (4)	C13—C14—H14A	120.2
C3—C2—H2A	120.3	C15—C14—H14A	120.2
C1—C2—H2A	120.3	N3—C15—C14	122.3 (4)
C2—C3—C4	118.8 (4)	N3—C15—H15A	118.9
C2—C3—H3A	120.6	C14—C15—H15A	118.9
C4—C3—H3A	120.6	H1W1—O1—H1W2	107 (7)
C3—C4—C5	119.2 (4)	H2W1—O2—H2W2	106 (5)
C3—C4—H4A	120.4	H3W1—O3—H3W2	106 (5)
C5—C4—H4A	120.4	H4W1—O4—H4W2	114 (5)
N1—C5—C4	121.8 (4)

Symmetry code: (i) −x+1/2, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W2···O2	0.85 (4)	2.04 (5)	2.885 (9)	176 (9)
O1—H1W1···Cl1	0.83 (4)	2.30 (4)	3.127 (7)	180 (9)
O2—H2W1···Cl1ⁱⁱ	0.84 (4)	2.48 (4)	3.317 (7)	175 (6)
O2—H2W2···Cl2	0.84 (3)	2.33 (3)	3.165 (5)	173 (7)
O3—H3W1···Cl1ⁱⁱⁱ	0.85 (6)	2.33 (6)	3.161 (5)	166 (6)
O3—H3W2···Cl2^iv	0.84 (4)	2.27 (5)	3.095 (5)	170 (7)
O4—H4W1···O1	0.79 (5)	2.06 (5)	2.841 (8)	169 (5)
O4—H4W2···O3	0.81 (3)	2.00 (3)	2.795 (8)	168 (7)
C1—H1A···N2	0.93	2.49	2.993 (5)	114
C4—H4A···Cl3	0.93	2.62	3.552 (4)	179
C6—H6A···N3ⁱ	0.93	2.52	3.007 (6)	113
C8—H8A···Cl1^iv	0.93	2.79	3.710 (5)	172
C12—H12A···Cl3^v	0.93	2.58	3.477 (4)	162
C14—H14A···Cl2^v	0.93	2.77	3.526 (4)	139
C15—H15A···N1ⁱ	0.93	2.49	2.991 (5)	114

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

Experimental details

Crystal data
Chemical formula	[Co(C₁₀H₈N₂)₃]Cl₃·4H₂O
M_r	705.90
Crystal system, space group	Orthorhombic, Cmca
Temperature (K)	295
a, b, c (Å)	20.171 (4), 23.170 (5), 13.316 (3)
V (Å³)	6223 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.86
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	ψ scan (XSCANS; Siemens, 1996)
T_min, T_max	0.905, 0.929
No. of measured, independent and observed [I > 2σ(I)] reflections	3430, 2824, 1980
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.162, 1.03
No. of reflections	2824
No. of parameters	225
No. of restraints	12
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.01, −0.66

Computer programs: XSCANS (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W2···O2	0.85 (4)	2.04 (5)	2.885 (9)	176 (9)
O1—H1W1···Cl1	0.83 (4)	2.30 (4)	3.127 (7)	180 (9)
O2—H2W1···Cl1ⁱ	0.84 (4)	2.48 (4)	3.317 (7)	175 (6)
O2—H2W2···Cl2	0.84 (3)	2.33 (3)	3.165 (5)	173 (7)
O3—H3W1···Cl1ⁱⁱ	0.85 (6)	2.33 (6)	3.161 (5)	166 (6)
O3—H3W2···Cl2ⁱⁱⁱ	0.84 (4)	2.27 (5)	3.095 (5)	170 (7)
O4—H4W1···O1	0.79 (5)	2.06 (5)	2.841 (8)	169 (5)
O4—H4W2···O3	0.81 (3)	2.00 (3)	2.795 (8)	168 (7)

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

Acknowledgements

This project was sponsored by the K. C. Wong Magna Fund of Ningbo University, the Expert Project of Key Basic Research of the Ministry of Science and Technology of China (grant No. 2003CCA00800), the Ningbo Municipal Natural Science Foundation (grant No. 2006 A610061), and the Newer Training Program Foundation for Talent of the Science and Technology Department of Zhejiang Province (grant No. 2007R40G2070020).

References

Hernández-Molina, M., Lloret, F., Ruiz-Pérez, C. & Julve, M. (1998). Inorg. Chem. 37, 4131–4135. Web of Science CSD CrossRef PubMed CAS Google Scholar
Li, P., Qiu, Y. C., Liu, J. Q., Ling, Y., Cai, Y. P. & Yue, S. T. (2007). Inorg. Chem. Commun. 10, 705–708. Web of Science CSD CrossRef CAS Google Scholar
Liu, K., Brown, M. G., Carter, C., Saykally, R. J., Gregory, J. K. & Clary, D. C. (1996). Nature (London), 381, 501–503. CrossRef CAS Web of Science Google Scholar
Ludwig, R. (2001). Angew. Chem. Int. Ed. 40, 1808–1827. CrossRef CAS Google Scholar
Mir, M. H. & Vittal, J. J. (2007). Angew. Chem. Int. Ed. 46, 5925–5928. Web of Science CSD CrossRef CAS Google Scholar
Nauta, K. & Miller, R. E. (2000). Science, 287, 293–295. Web of Science CrossRef PubMed CAS Google Scholar
Reger, D. L., Semeniuc, R. F., Pettinari, C., Luna-Giles, F. & Smith, M. D. (2006). Cryst. Growth Des. 6, 1068–1070. Web of Science CSD CrossRef CAS Google Scholar
Saha, M. K. & Bernal, I. (2005). Inorg. Chem. Commun. 8, 871–873. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). XSCANS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar