Dichlorido(2,9-dimethyl-1,10-phenanthroline)manganese(II) hemihydrate

Wang, X.

doi:10.1107/S1600536809049149

metal-organic compounds

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Volume 65| Part 12| December 2009| Page m1659

doi:10.1107/S1600536809049149

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Dichlorido(2,9-dimethyl-1,10-phenanthroline)manganese(II) hemihydrate

Xinfang Wang ^a ^*

^aDepartment of Chemistry, Dezhou University, Dezhou 253023, People's Republic of China
^*Correspondence e-mail: dzxfwang@yahoo.com.cn

(Received 12 November 2009; accepted 18 November 2009; online 21 November 2009)

In the title compound, [MnCl₂(C₁₄H₁₂N₂)]·0.5H₂O, all of the non-H atoms apart from the Cl atom lie on a mirror plane and the methyl H atoms are disordered over two sites of equal occupancy about the mirror plane. The Mn^II ion is coordinated in a distorted tetrahedral environment by two N atoms of the phenanthroline ligand and two chloride ions. A half-occupancy solvent water molecule lies on a mirror plane and close to an inversion center.

Related literature

For related crystal structures, see: McCann et al. (1998 ); Pan & Xu (2005 ); Xu et al. (2009 ).

Experimental

Crystal data

[MnCl₂(C₁₄H₁₂N₂)]·0.5H₂O
M_r = 343.10
Monoclinic, C 2/m
a = 18.763 (4) Å
b = 7.7343 (15) Å
c = 11.362 (2) Å
β = 101.532 (3)°
V = 1615.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.14 mm⁻¹
T = 293 K
0.31 × 0.23 × 0.19 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ) T_min = 0.719, T_max = 0.813
4794 measured reflections
1511 independent reflections
1199 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.134
S = 1.01
1511 reflections
120 parameters
.
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809049149/lh2953sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809049149/lh2953Isup2.hkl

checkCIF report

Comment top

1,10-phenanthroline is a good bidentate chelating ligand and here, we present the crystal structure of the title complex based on 2,9-dimethyl-1,10-phenanthroline.

The crystal structure of the title compound is shown in Fig. 1. The coordination environment of the Mn^II ion is distorted tetrahedral, in which two sites are occupied by the two N atoms of the chelating 2,9-dimethyl-1,10-phenanthroline ligand and the other two from two chloride ions. For Mn—N and Mn—Cl bond lengths in other manganese biphenanthroline complexes, see e.g. McCann, et al. (1998); Pan & Xu (2005); Xu et al. (2009). The location of the water H atoms is such that they are disordered over several sites imposed by the crystal symmetry and hence any potential hydrogen bonding is not discussed.

Related literature top

For related crystal structures, see: McCann et al. (1998); Pan & Xu (2005); Xu et al. (2009).

Experimental top

A mixture of 2,9-dimethyl-1,10-phenanthroline, MnCl₂.4H₂O (1:2, molar ratio) and water (20 ml) was sealed in a Teflon-lined autoclave (25 ml) and heated 393 K for two days. Upon cooling slowly and opening the bomb, yellow crystals suitable for X-ray diffraction were obtained with a yield about 40% (based on phenanthroline).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures top

Fig. 1. The molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. The disordered water molecule and all the H-atoms are omitted for clarity.

Dichlorido(2,9-dimethyl-1,10-phenanthroline)manganese(II) hemihydrate top

Crystal data top

[MnCl₂(C₁₄H₁₂N₂)]·0.5H₂O	F(000) = 696
M_r = 343.10	D_x = 1.411 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 1089 reflections
a = 18.763 (4) Å	θ = 2.9–26.8°
b = 7.7343 (15) Å	µ = 1.14 mm⁻¹
c = 11.362 (2) Å	T = 293 K
β = 101.532 (3)°	Block, yellow
V = 1615.5 (5) Å³	0.31 × 0.23 × 0.19 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	1511 independent reflections
Radiation source: fine-focus sealed tube	1199 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −22→22
T_min = 0.719, T_max = 0.813	k = −8→9
4794 measured reflections	l = −13→13

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	w = 1/[σ²(F_o²) + (0.1015P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
1511 reflections	Δρ_max = 0.59 e Å⁻³
120 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints

Crystal data top

[MnCl₂(C₁₄H₁₂N₂)]·0.5H₂O	V = 1615.5 (5) Å³
M_r = 343.10	Z = 4
Monoclinic, C2/m	Mo Kα radiation
a = 18.763 (4) Å	µ = 1.14 mm⁻¹
b = 7.7343 (15) Å	T = 293 K
c = 11.362 (2) Å	0.31 × 0.23 × 0.19 mm
β = 101.532 (3)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1511 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	1199 reflections with I > 2σ(I)
T_min = 0.719, T_max = 0.813	R_int = 0.020
4794 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	120 parameters
wR(F²) = 0.134	0 restraints
S = 1.01	Δρ_max = 0.59 e Å⁻³
1511 reflections	Δρ_min = −0.31 e Å⁻³

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)
Mn1	0.35177 (3)	0.0000	0.27709 (5)	0.0558 (3)
Cl1	0.40493 (4)	0.25282 (10)	0.24304 (8)	0.0815 (3)
O1	0.5351 (5)	1.0000	0.0528 (9)	0.155 (4)	0.50
H2A	0.5257	0.9426	0.1128	0.186*	0.25
H1A	0.5745	0.9558	0.0399	0.186*	0.25
N1	0.30817 (15)	0.0000	0.4374 (3)	0.0555 (8)
N2	0.24030 (17)	0.0000	0.2034 (3)	0.0601 (8)
C1	0.3433 (2)	0.0000	0.5521 (4)	0.0625 (10)
C2	0.3066 (2)	0.0000	0.6486 (4)	0.0715 (12)
H2	0.3329	0.0000	0.7272	0.086*
C3	0.2337 (2)	0.0000	0.6273 (4)	0.0715 (12)
H3	0.2089	0.0000	0.6905	0.086*
C4	0.1951 (2)	0.0000	0.5056 (3)	0.0604 (10)
C5	0.1191 (2)	0.0000	0.4745 (4)	0.0781 (13)
H5	0.0919	0.0000	0.5346	0.094*
C6	0.0848 (2)	0.0000	0.3584 (4)	0.0768 (13)
H6	0.0342	0.0000	0.3399	0.092*
C7	0.1240 (2)	0.0000	0.2635 (4)	0.0655 (11)
C8	0.0910 (3)	0.0000	0.1374 (4)	0.0840 (15)
H8	0.0406	0.0000	0.1136	0.101*
C9	0.1330 (3)	0.0000	0.0535 (4)	0.0875 (15)
H9	0.1113	0.0000	−0.0276	0.105*
C10	0.2073 (3)	0.0000	0.0872 (4)	0.0703 (11)
C11	0.1985 (2)	0.0000	0.2896 (3)	0.0562 (9)
C12	0.2350 (2)	0.0000	0.4153 (3)	0.0532 (9)
C13	0.4239 (2)	0.0000	0.5734 (4)	0.0819 (14)
H13A	0.4397	−0.0724	0.5150	0.123*	0.50
H13B	0.4431	−0.0434	0.6525	0.123*	0.50
H13C	0.4410	0.1158	0.5666	0.123*	0.50
C14	0.2542 (3)	0.0000	−0.0069 (4)	0.0933 (17)
H14A	0.2713	0.1152	−0.0163	0.140*	0.50
H14B	0.2260	−0.0395	−0.0820	0.140*	0.50
H14C	0.2950	−0.0756	0.0181	0.140*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0481 (4)	0.0703 (5)	0.0501 (4)	0.000	0.0127 (3)	0.000
Cl1	0.0781 (6)	0.0818 (7)	0.0876 (6)	−0.0094 (4)	0.0235 (4)	0.0054 (4)
O1	0.108 (7)	0.226 (12)	0.134 (9)	0.000	0.031 (6)	0.000
N1	0.0413 (15)	0.074 (2)	0.0503 (17)	0.000	0.0063 (13)	0.000
N2	0.0572 (17)	0.073 (2)	0.0483 (17)	0.000	0.0069 (14)	0.000
C1	0.056 (2)	0.076 (3)	0.053 (2)	0.000	0.0032 (17)	0.000
C2	0.061 (2)	0.100 (4)	0.049 (2)	0.000	−0.0002 (18)	0.000
C3	0.064 (2)	0.101 (4)	0.050 (2)	0.000	0.0127 (19)	0.000
C4	0.053 (2)	0.077 (3)	0.052 (2)	0.000	0.0100 (17)	0.000
C5	0.055 (2)	0.112 (4)	0.071 (3)	0.000	0.020 (2)	0.000
C6	0.045 (2)	0.110 (4)	0.073 (3)	0.000	0.006 (2)	0.000
C7	0.047 (2)	0.080 (3)	0.064 (3)	0.000	−0.0017 (18)	0.000
C8	0.062 (3)	0.111 (4)	0.070 (3)	0.000	−0.008 (2)	0.000
C9	0.078 (3)	0.120 (4)	0.056 (3)	0.000	−0.010 (2)	0.000
C10	0.078 (3)	0.076 (3)	0.054 (2)	0.000	0.006 (2)	0.000
C11	0.051 (2)	0.070 (3)	0.0456 (19)	0.000	0.0040 (16)	0.000
C12	0.053 (2)	0.054 (2)	0.052 (2)	0.000	0.0073 (16)	0.000
C13	0.049 (2)	0.127 (4)	0.064 (3)	0.000	0.000 (2)	0.000
C14	0.095 (3)	0.133 (5)	0.052 (2)	0.000	0.014 (2)	0.000

Geometric parameters (Å, º) top

Mn1—N2	2.092 (3)	C5—C6	1.347 (6)
Mn1—N1	2.140 (3)	C5—H5	0.9300
Mn1—Cl1	2.2633 (9)	C6—C7	1.421 (6)
Mn1—Cl1ⁱ	2.2633 (9)	C6—H6	0.9300
O1—O1ⁱⁱ	1.59 (2)	C7—C11	1.371 (5)
O1—H2A	0.8610	C7—C8	1.443 (6)
O1—H1A	0.8530	C8—C9	1.353 (7)
N1—C1	1.338 (5)	C8—H8	0.9300
N1—C12	1.345 (5)	C9—C10	1.370 (7)
N2—C10	1.342 (5)	C9—H9	0.9300
N2—C11	1.371 (5)	C10—C14	1.514 (7)
C1—C2	1.407 (6)	C11—C12	1.454 (5)
C1—C13	1.482 (6)	C13—H13A	0.9600
C2—C3	1.341 (6)	C13—H13B	0.9600
C2—H2	0.9300	C13—H13C	0.9600
C3—C4	1.428 (6)	C14—H14A	0.9600
C3—H3	0.9300	C14—H14B	0.9600
C4—C12	1.387 (5)	C14—H14C	0.9600
C4—C5	1.399 (6)

N2—Mn1—N1	79.57 (12)	C7—C6—H6	119.2
N2—Mn1—Cl1	111.79 (4)	C11—C7—C6	119.7 (4)
N1—Mn1—Cl1	113.70 (4)	C11—C7—C8	115.5 (4)
N2—Mn1—Cl1ⁱ	111.79 (4)	C6—C7—C8	124.8 (4)
N1—Mn1—Cl1ⁱ	113.70 (4)	C9—C8—C7	120.4 (4)
Cl1—Mn1—Cl1ⁱ	119.53 (5)	C9—C8—H8	119.8
O1ⁱⁱ—O1—H2A	109.0	C7—C8—H8	119.8
O1ⁱⁱ—O1—H1A	119.0	C8—C9—C10	120.4 (4)
H2A—O1—H1A	104.5	C8—C9—H9	119.8
C1—N1—C12	117.9 (3)	C10—C9—H9	119.8
C1—N1—Mn1	129.1 (3)	N2—C10—C9	121.2 (4)
C12—N1—Mn1	113.0 (2)	N2—C10—C14	118.4 (4)
C10—N2—C11	119.1 (3)	C9—C10—C14	120.3 (4)
C10—N2—Mn1	128.4 (3)	C7—C11—N2	123.3 (3)
C11—N2—Mn1	112.5 (2)	C7—C11—C12	118.2 (3)
N1—C1—C2	122.5 (3)	N2—C11—C12	118.5 (3)
N1—C1—C13	116.6 (4)	N1—C12—C4	123.0 (3)
C2—C1—C13	121.0 (4)	N1—C12—C11	116.5 (3)
C3—C2—C1	120.0 (4)	C4—C12—C11	120.5 (3)
C3—C2—H2	120.0	C1—C13—H13A	109.5
C1—C2—H2	120.0	C1—C13—H13B	109.5
C2—C3—C4	118.5 (4)	H13A—C13—H13B	109.5
C2—C3—H3	120.8	C1—C13—H13C	109.5
C4—C3—H3	120.8	H13A—C13—H13C	109.5
C12—C4—C5	119.2 (4)	H13B—C13—H13C	109.5
C12—C4—C3	118.2 (4)	C10—C14—H14A	109.5
C5—C4—C3	122.6 (4)	C10—C14—H14B	109.5
C6—C5—C4	120.7 (4)	H14A—C14—H14B	109.5
C6—C5—H5	119.7	C10—C14—H14C	109.5
C4—C5—H5	119.7	H14A—C14—H14C	109.5
C5—C6—C7	121.7 (4)	H14B—C14—H14C	109.5
C5—C6—H6	119.2

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

Experimental details

Crystal data
Chemical formula	[MnCl₂(C₁₄H₁₂N₂)]·0.5H₂O
M_r	343.10
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	293
a, b, c (Å)	18.763 (4), 7.7343 (15), 11.362 (2)
β (°)	101.532 (3)
V (Å³)	1615.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.14
Crystal size (mm)	0.31 × 0.23 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008a)
T_min, T_max	0.719, 0.813
No. of measured, independent and observed [I > 2σ(I)] reflections	4794, 1511, 1199
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.134, 1.01
No. of reflections	1511
No. of parameters	120
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.31

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008b), SHELXL97 (Sheldrick, 2008b), SHELXTL (Sheldrick, 2008b).

References

Bruker (2001). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Pan, T.-T. & Xu, D.-J. (2005). Acta Cryst. E61, m740–m742. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008a). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008b). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, M.-L., Sun, S.-B., Li, X.-Y. & Che, G.-B. (2009). Acta Cryst. E65, m136. Web of Science CSD CrossRef IUCr Journals Google Scholar