Tris(2,2'-bipyridine-κN:N')cobalt(III) trichloride tetra-hydrate.

The title compound, [Co(C(10)H(8)N(2))(3)]Cl(3)·4H(2)O, contains discrete [Co(bpy)(3)](3+) cations (bpy is 2,2'-bipyridine), Cl(-) anions and water mol-ecules. The [Co(bpy)(3)](3+) complex cation exhibits C(2) symmetry with the twofold axis through the central Co atom and bis-ecting one bpy ligand and one of the Cl(-) anions. The four solvent water mol-ecules and the remaining two Cl(-) anions lie on a mirror plane. Hydrogen-bond inter-actions define a two-dimensional layer structure parallel to (100), which consists of seven-membered [Cl(2)(H(2)O)(5)], eight-membered [Cl(4)(H(2)O)(4)] and ten-membered [Cl(2)(H(2)O)(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 = 705.90

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.162

S = 1.03

2824 reflections

225 parameters

12 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.01 e Å−3

Δρmin = −0.66 e Å−3

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.

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

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

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

[Co(C10H8N2)3]Cl3·4H2O	F000 = 2912
Mr = 705.90	Dx = 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 = 5.0–12.5º
b = 23.170 (5) Å	µ = 0.86 mm−1
c = 13.316 (3) Å	T = 295 (2) K
V = 6223 (2) Å3	Block, yellow
Z = 8	0.12 × 0.10 × 0.08 mm

Bruker P4 diffractometer	Rint = 0.049
Radiation source: fine-focus sealed tube	θmax = 25.0º
Monochromator: graphite	θmin = 1.8º
T = 295(2) K	h = −23→1
θ/2θ scans	k = −1→27
Absorption correction: ψ scan(XSCANS; Siemens, 1996)	l = −1→15
Tmin = 0.905, Tmax = 0.929	3 standard reflections
3430 measured reflections	every 97 reflections
2824 independent reflections	intensity decay: none
1980 reflections with I > 2σ(I)

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)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.162	w = 1/[σ2(Fo2) + (0.1023P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
2824 reflections	Δρmax = 1.01 e Å−3
225 parameters	Δρmin = −0.66 e Å−3
12 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···Cl2iv	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···Cl1iv	0.93	2.79	3.710 (5)	172
C12—H12A···Cl3v	0.93	2.58	3.477 (4)	162
C14—H14A···Cl2v	0.93	2.77	3.526 (4)	139
C15—H15A···N1i	0.93	2.49	2.991 (5)	114

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) ; (ii) ; (iii) ; (iv) ; (v) .