Triaqua­chlorido(1,10-phenanthroline-κ2N,N′)cobalt(II) chloride monohydrate

Liu, Y.; Pan, Y.; Sun, J.; Zhang, C.

doi:10.1107/S1600536808042591

metal-organic compounds

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Volume 65| Part 1| January 2009| Page m114

doi:10.1107/S1600536808042591

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Triaquachlorido(1,10-phenanthroline-κ²N,N′)cobalt(II) chloride monohydrate

Yaru Liu,^a ^* Yutian Pan,^b Junshan Sun ^c and Chuan Zhang ^c

^aSchool of Science, North University of China, Taiyuan 030051, People's Republic of China, ^bSchool of Mechatronic Engineering, North University of China, Taiyuan 030051, People's Republic of China, and ^cDepartment of Materials Science and Chemical Engineering, Taishan University, 271021 Taian, Shandong, People's Republic of China
^*Correspondence e-mail: xiangyz_2008@163.com

(Received 14 November 2008; accepted 15 December 2008; online 20 December 2008)

In the title compound, [CoCl(C₁₂H₈N₂)(H₂O)₃]Cl·H₂O, the Co^II ion is coordinated by two N atoms from the 1,10-phenanthroline ligand [Co—N = 2.125 (6) and 2.146 (6) Å], one chloride ligand [Co—Cl = 2.459 (2)Å] and three water molecules [Co—O = 2.070 (5)–2.105 (5)Å] in a distorted octahedral geometry. Intermolecular O—H⋯Cl and O—H⋯O hydrogen bonds form an extensive three-dimensional hydrogen-bonding network, which consolidates the crystal packing.

Related literature

For related crystal structures, see: Liu et al. (2006 ); Zhang et al. (1999 ).

Experimental

Crystal data

[CoCl(C₁₂H₈N₂)(H₂O)₃]Cl·H₂O
M_r = 382.10
Monoclinic, P 2₁ /c
a = 7.646 (4) Å
b = 12.426 (6) Å
c = 16.987 (8) Å
β = 103.54 (2)°
V = 1569.1 (13) Å³
Z = 4
Mo Kα radiation
μ = 1.45 mm⁻¹
T = 273 (2) K
0.37 × 0.25 × 0.19 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.616, T_max = 0.770
6533 measured reflections
2733 independent reflections
1564 reflections with I > 2σ(I)
R_int = 0.080

Refinement

R[F² > 2σ(F²)] = 0.071
wR(F²) = 0.177
S = 1.04
2733 reflections
198 parameters
13 restraints
H-atom parameters constrained
Δρ_max = 0.67 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
O1—H1A⋯O4	0.85	1.93	2.693 (9)	149
O1—H1B⋯Cl2	0.85	2.55	3.258 (6)	141
O2—H2A⋯Cl1ⁱ	0.85	2.31	3.139 (6)	166
O2—H2B⋯Cl2ⁱ	0.85	2.29	3.119 (6)	164
O3—H3A⋯Cl2ⁱⁱ	0.85	2.33	3.114 (6)	153
O3—H3B⋯Cl1ⁱⁱ	0.85	2.30	3.128 (6)	166
O4—H4A⋯Cl2ⁱⁱⁱ	0.85	2.34	3.185 (8)	170
O4—H4B⋯Cl1ⁱⁱ	0.85	2.58	3.278 (8)	141
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) -x+2, -y+1, -z+2; (iii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{5\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808042591/cv2481sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808042591/cv2481Isup2.hkl

checkCIF report

Comment top

The structures of some tetraaqua(1,10-phenanthroline) metal ionic complexes with different anions have been reported (Liu et al., 2006; Zhang et al., 1999). In our study in this field, we select 1,10-phenanthroline as the co-ligand to continue our exploration of the Co complexes. Herein we report the structure of the title compound (I), which was characterized by elemental analyses and X-ray crystallography diffraction.

In (I) (Fig. 1), each Co^II ion is coordinated by two N atoms from 1,10-phenanthroline ligand [Co—N 2.125 (6), 2.146 (6) Å], one chlorine anion [Co—Cl 2.459 (2) Å] and three water molecules [Co—O 2.070 (5)–2.105 (5) Å] in a distorted octahedral geometry. Two aqua O atoms and two N atoms from 1,10-phenanthroline ligand define the special position on a mirror plane. One aqua group and chlorine anion fill the axial apical positions. The intermolecular O—H···Cl and O—H···O hydrogen bonds (Table 1) form an extensive three-dimensional hydrogen-bonding network, which consolidate the crystal packing.

Related literature top

For related crystal structures, see: Liu et al. (2006); Zhang et al. (1999).

Experimental top

A mixture of Cu(Cl)2*3H2O(168 mg, 1 mmol) and 1,10-phenanthroline(185 mg, 1 mmol) in methanol(30 ml) was placed in a Teflon-lined stainless steel Parr bomb that was heated at 423 K for 72 h. The bomb was then cooled down to the room temperature, the solution was filtered. The solvent was removed from the filtrate under vacuum, and the solid residue was recrystallized from diethyl ether; blue crystals suitable for X-Ray diffraction study were obtained. Yield, 0.724 g, 81%. m.p. 566 K. Analysis, calculated for C₁₂H₁₆Cl₂CoN₂O₄: C 37.72, H 4.22, N 7.33; found: C 37.53, H 4.68, N 7.17%. The elemental analyses were performed with a Perkine Elemer PE2400II instrument.

Computing details top

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

Figures top

Fig. 1. The structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme. Dashed lines denote hydrogen bonds.

Triaquachlorido(1,10-phenanthroline-κ²N,N')cobalt(II) chloride monohydrate top

Crystal data top

[CoCl(C₁₂H₈N₂)(H₂O)₃]Cl·H₂O	F(000) = 780
M_r = 382.10	D_x = 1.617 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.646 (4) Å	Cell parameters from 580 reflections
b = 12.426 (6) Å	θ = 3.0–20.1°
c = 16.987 (8) Å	µ = 1.45 mm⁻¹
β = 103.54 (2)°	T = 273 K
V = 1569.1 (13) Å³	Block, blue
Z = 4	0.37 × 0.25 × 0.19 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2733 independent reflections
Radiation source: fine-focus sealed tube	1564 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.080
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→5
T_min = 0.616, T_max = 0.770	k = −10→14
6533 measured reflections	l = −17→20

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)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.177	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0517P)² + 4.0479P] where P = (F_o² + 2F_c²)/3
2733 reflections	(Δ/σ)_max < 0.001
198 parameters	Δρ_max = 0.67 e Å⁻³
13 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

[CoCl(C₁₂H₈N₂)(H₂O)₃]Cl·H₂O	V = 1569.1 (13) Å³
M_r = 382.10	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.646 (4) Å	µ = 1.45 mm⁻¹
b = 12.426 (6) Å	T = 273 K
c = 16.987 (8) Å	0.37 × 0.25 × 0.19 mm
β = 103.54 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2733 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1564 reflections with I > 2σ(I)
T_min = 0.616, T_max = 0.770	R_int = 0.080
6533 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.071	13 restraints
wR(F²) = 0.177	H-atom parameters constrained
S = 1.04	Δρ_max = 0.67 e Å⁻³
2733 reflections	Δρ_min = −0.56 e Å⁻³
198 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	0.75359 (13)	0.66886 (9)	0.99070 (6)	0.0342 (3)
Cl1	0.6997 (3)	0.49910 (16)	0.91423 (11)	0.0431 (5)
Cl2	0.8145 (3)	0.34056 (18)	1.16347 (12)	0.0536 (6)
N1	0.6918 (8)	0.7697 (5)	0.8867 (4)	0.0360 (15)
N2	0.7887 (8)	0.8255 (5)	1.0452 (4)	0.0405 (16)
O1	0.8190 (8)	0.5892 (4)	1.1032 (3)	0.0478 (15)
H1A	0.9003	0.5920	1.1469	0.15 (6)*
H1B	0.7797	0.5251	1.0958	0.10 (4)*
O2	0.4845 (7)	0.6729 (4)	0.9965 (3)	0.0459 (13)
H2A	0.4527	0.6214	1.0231	0.06 (3)*
H2B	0.4185	0.6755	0.9488	0.05 (3)*
O3	1.0230 (7)	0.6657 (4)	0.9883 (3)	0.0456 (14)
H3A	1.0372	0.6788	0.9411	0.05 (3)*
H3B	1.1121	0.6289	1.0137	0.09 (4)*
O4	1.1261 (10)	0.6517 (6)	1.2062 (4)	0.075 (2)
H4A	1.1566	0.7013	1.2412	0.06 (3)*
H4B	1.2171	0.6296	1.1901	0.16 (7)*
C1	0.6476 (11)	0.7393 (8)	0.8103 (5)	0.049 (2)
H1	0.6394	0.6664	0.7979	0.059*
C2	0.6123 (11)	0.8160 (7)	0.7468 (5)	0.050 (2)
H2	0.5810	0.7933	0.6931	0.060*
C3	0.6243 (11)	0.9222 (7)	0.7645 (5)	0.052 (2)
H3	0.6017	0.9726	0.7228	0.062*
C4	0.6706 (11)	0.9573 (7)	0.8456 (5)	0.046 (2)
C5	0.7032 (10)	0.8787 (6)	0.9056 (5)	0.037 (2)
C6	0.7525 (9)	0.9047 (6)	0.9885 (5)	0.0338 (17)
C7	0.7636 (10)	1.0150 (7)	1.0107 (5)	0.044 (2)
C8	0.8142 (12)	1.0398 (8)	1.0931 (6)	0.062 (3)
H8	0.8232	1.1111	1.1102	0.075*
C9	0.8501 (13)	0.9583 (8)	1.1481 (6)	0.062 (3)
H9	0.8841	0.9740	1.2031	0.074*
C10	0.8363 (10)	0.8527 (7)	1.1225 (5)	0.049 (2)
H10	0.8616	0.7985	1.1612	0.058*
C11	0.6849 (12)	1.0667 (7)	0.8682 (6)	0.058 (3)
H11	0.6645	1.1199	0.8285	0.070*
C12	0.7284 (13)	1.0944 (7)	0.9475 (6)	0.063 (3)
H12	0.7357	1.1669	0.9614	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0399 (6)	0.0288 (6)	0.0335 (6)	−0.0003 (5)	0.0080 (4)	0.0012 (5)
Cl1	0.0576 (13)	0.0299 (11)	0.0394 (12)	−0.0009 (9)	0.0068 (9)	−0.0034 (10)
Cl2	0.0673 (14)	0.0495 (14)	0.0443 (12)	0.0020 (11)	0.0133 (10)	0.0060 (12)
N1	0.040 (4)	0.033 (4)	0.036 (4)	0.000 (3)	0.011 (3)	0.002 (3)
N2	0.043 (4)	0.034 (4)	0.045 (4)	−0.001 (3)	0.009 (3)	−0.003 (4)
O1	0.068 (4)	0.040 (4)	0.034 (3)	−0.006 (3)	0.009 (3)	0.002 (3)
O2	0.050 (3)	0.042 (4)	0.048 (3)	0.000 (3)	0.016 (3)	0.004 (3)
O3	0.043 (3)	0.055 (4)	0.042 (3)	0.006 (3)	0.015 (2)	0.007 (3)
O4	0.080 (5)	0.080 (5)	0.058 (4)	0.008 (4)	0.001 (4)	−0.028 (4)
C1	0.058 (6)	0.059 (6)	0.030 (5)	0.005 (4)	0.010 (4)	0.004 (4)
C2	0.061 (6)	0.055 (6)	0.032 (4)	0.003 (4)	0.008 (4)	0.004 (4)
C3	0.062 (6)	0.040 (6)	0.052 (6)	0.003 (4)	0.012 (4)	0.005 (5)
C4	0.046 (5)	0.044 (6)	0.047 (5)	0.005 (4)	0.009 (4)	0.006 (4)
C5	0.036 (4)	0.025 (4)	0.055 (6)	0.000 (3)	0.018 (4)	−0.009 (4)
C6	0.038 (4)	0.022 (4)	0.042 (5)	−0.001 (3)	0.010 (3)	−0.001 (4)
C7	0.043 (5)	0.032 (5)	0.057 (6)	0.001 (4)	0.013 (4)	−0.005 (4)
C8	0.078 (7)	0.034 (6)	0.074 (7)	−0.002 (5)	0.014 (5)	−0.023 (5)
C9	0.080 (7)	0.045 (6)	0.059 (6)	−0.001 (5)	0.016 (5)	−0.021 (5)
C10	0.053 (5)	0.054 (6)	0.038 (5)	0.004 (4)	0.009 (4)	−0.004 (5)
C11	0.072 (7)	0.038 (6)	0.062 (7)	0.009 (5)	0.012 (5)	0.020 (5)
C12	0.075 (7)	0.030 (5)	0.082 (7)	0.002 (5)	0.013 (5)	0.004 (6)

Geometric parameters (Å, º) top

Co1—O3	2.071 (5)	C1—H1	0.9300
Co1—O2	2.084 (5)	C2—C3	1.35 (1)
Co1—O1	2.106 (5)	C2—H2	0.9301
Co1—N1	2.127 (6)	C3—C4	1.41 (1)
Co1—N2	2.145 (7)	C3—H3	0.9300
Co1—Cl1	2.461 (2)	C4—C5	1.39 (1)
N1—C1	1.317 (9)	C4—C11	1.41 (1)
N1—C5	1.390 (9)	C5—C6	1.41 (1)
N2—C10	1.321 (9)	C6—C7	1.42 (1)
N2—C6	1.361 (9)	C7—C8	1.40 (1)
O1—H1A	0.8500	C7—C12	1.44 (1)
O1—H1B	0.8501	C8—C9	1.36 (1)
O2—H2A	0.8500	C8—H8	0.9301
O2—H2B	0.8498	C9—C10	1.38 (1)
O3—H3A	0.8500	C9—H9	0.9301
O3—H3B	0.8500	C10—H10	0.9300
O4—H4A	0.8500	C11—C12	1.36 (1)
O4—H4B	0.8500	C11—H11	0.9300
C1—C2	1.42 (1)	C12—H12	0.9300

O3—Co1—O2	178.4 (2)	C1—C2—H2	120.2
O3—Co1—O1	89.0 (2)	C2—C3—C4	120.5 (8)
O2—Co1—O1	89.7 (2)	C2—C3—H3	119.7
O3—Co1—N1	91.3 (2)	C4—C3—H3	119.7
O2—Co1—N1	89.8 (2)	C5—C4—C3	117.4 (8)
O1—Co1—N1	171.9 (2)	C5—C4—C11	119.3 (8)
O3—Co1—N2	90.1 (2)	C3—C4—C11	123.3 (8)
O2—Co1—N2	89.0 (2)	N1—C5—C4	121.6 (8)
O1—Co1—N2	93.2 (2)	N1—C5—C6	116.3 (7)
N1—Co1—N2	78.8 (2)	C4—C5—C6	122.0 (7)
C1—N1—C5	119.6 (7)	N2—C6—C5	120.3 (7)
C1—N1—Co1	127.3 (6)	N2—C6—C7	121.4 (7)
C5—N1—Co1	113.1 (5)	C5—C6—C7	118.3 (7)
C10—N2—C6	118.8 (7)	C8—C7—C6	117.7 (8)
C10—N2—Co1	129.7 (6)	C8—C7—C12	123.8 (8)
C6—N2—Co1	111.5 (5)	C6—C7—C12	118.4 (8)
Co1—O1—H1A	138.0	C9—C8—C7	119.2 (8)
Co1—O1—H1B	107.8	C9—C8—H8	120.4
H1A—O1—H1B	109.2	C7—C8—H8	120.4
Co1—O2—H2A	114.5	C8—C9—C10	120.2 (9)
Co1—O2—H2B	109.1	C8—C9—H9	119.9
H2A—O2—H2B	110.8	C10—C9—H9	119.9
Co1—O3—H3A	111.3	N2—C10—C9	122.7 (9)
Co1—O3—H3B	133.1	N2—C10—H10	118.7
H3A—O3—H3B	108.6	C9—C10—H10	118.7
H4A—O4—H4B	110.4	C12—C11—C4	120.0 (8)
N1—C1—C2	121.2 (8)	C12—C11—H11	120.0
N1—C1—H1	119.4	C4—C11—H11	120.0
C2—C1—H1	119.4	C11—C12—C7	121.9 (9)
C3—C2—C1	119.7 (8)	C11—C12—H12	119.1
C3—C2—H2	120.2	C7—C12—H12	119.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O4	0.85	1.93	2.693 (9)	149
O1—H1B···Cl2	0.85	2.55	3.258 (6)	141
O2—H2A···Cl1ⁱ	0.85	2.31	3.139 (6)	166
O2—H2B···Cl2ⁱ	0.85	2.29	3.119 (6)	164
O3—H3A···Cl2ⁱⁱ	0.85	2.33	3.114 (6)	153
O3—H3B···Cl1ⁱⁱ	0.85	2.30	3.128 (6)	166
O4—H4A···Cl2ⁱⁱⁱ	0.85	2.34	3.185 (8)	170
O4—H4B···Cl1ⁱⁱ	0.85	2.58	3.278 (8)	141

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+2, −y+1, −z+2; (iii) −x+2, y+1/2, −z+5/2.

Experimental details

Crystal data
Chemical formula	[CoCl(C₁₂H₈N₂)(H₂O)₃]Cl·H₂O
M_r	382.10
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	7.646 (4), 12.426 (6), 16.987 (8)
β (°)	103.54 (2)
V (Å³)	1569.1 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.45
Crystal size (mm)	0.37 × 0.25 × 0.19

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.616, 0.770
No. of measured, independent and observed [I > 2σ(I)] reflections	6533, 2733, 1564
R_int	0.080
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.071, 0.177, 1.04
No. of reflections	2733
No. of parameters	198
No. of restraints	13
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.56

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O4	0.85	1.93	2.693 (9)	148.50
O1—H1B···Cl2	0.85	2.55	3.258 (6)	141.22
O2—H2A···Cl1ⁱ	0.85	2.31	3.139 (6)	166.35
O2—H2B···Cl2ⁱ	0.85	2.29	3.119 (6)	164.31
O3—H3A···Cl2ⁱⁱ	0.85	2.33	3.114 (6)	153.01
O3—H3B···Cl1ⁱⁱ	0.85	2.30	3.128 (6)	166.26
O4—H4A···Cl2ⁱⁱⁱ	0.85	2.34	3.185 (8)	169.75
O4—H4B···Cl1ⁱⁱ	0.85	2.58	3.278 (8)	140.74

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+2, −y+1, −z+2; (iii) −x+2, y+1/2, −z+5/2.

Acknowledgements

The authors thank the National Natural Science Foundation of China for financial support.

References

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