Acta Cryst. (2009). E65, m1659 [ doi:10.1107/S1600536809049149 ]
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 MnII 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.
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).
All H atoms bonded to C atoms were included using the HFIX commands in SHELXL-97 (Sheldrick, 2008b/i>) with C—H distances of 0.93 and 0.96 Å, and were allowed for as riding atoms with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(Cmethyl). The H atoms of the disordered water molecule were found in a difference Fourier map and were refined as riding with O-H fixed at 0.85 Å and Uiso(H) = 1.2Ueq(O).
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).
![[Figure 1]](./lh2953fig1thm.gif)
| 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. |
| [MnCl2(C14H12N2)]·0.5H2O | F(000) = 696 |
| Mr = 343.10 | Dx = 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 |
| Bruker APEXII CCD area-detector diffractometer | 1511 independent reflections |
| Radiation source: fine-focus sealed tube | 1199 reflections with I > 2σ(I) |
| graphite | Rint = 0.020 |
| φ and ω scans | θmax = 25.0°, θmin = 2.2° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2008a) | h = −22→22 |
| Tmin = 0.719, Tmax = 0.813 | k = −8→9 |
| 4794 measured reflections | l = −13→13 |
| 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(Fo2) + (0.1015P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.01 | (Δ/σ)max = 0.001 |
| 1511 reflections | Δρmax = 0.59 e Å−3 |
| 120 parameters | Δρmin = −0.31 e Å−3 |
| 0 restraints |
| [MnCl2(C14H12N2)]·0.5H2O | V = 1615.5 (5) Å3 |
| Mr = 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)° |
| Bruker APEXII CCD area-detector diffractometer | 1511 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2008a) | 1199 reflections with I > 2σ(I) |
| Tmin = 0.719, Tmax = 0.813 | Rint = 0.020 |
| 4794 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.044 | ? |
| wR(F2) = 0.134 | Δρmax = 0.59 e Å−3 |
| S = 1.01 | Δρmin = −0.31 e Å−3 |
| 1511 reflections | Absolute structure: ? |
| 120 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | 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 |
| 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 |
| 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. |
Bruker (2001). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.
McCann, S., McCann, M., Casey, M. T., Jackman, M., Devereux, M. & Mckee, V. (1998). Inorg. Chim. Acta, 279, 24–29.
Pan, T.-T. & Xu, D.-J. (2005). Acta Cryst. E61, m740–m742.
Sheldrick, G. M. (2008a). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008b). Acta Cryst. A64, 112–122.
Xu, M.-L., Sun, S.-B., Li, X.-Y. & Che, G.-B. (2009). Acta Cryst. E65, m136.
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 MnII 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.