Acta Cryst. (2007). E63, m3095 [ doi:10.1107/S1600536807059508 ]
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O)manganese(II)The title complex, [MnCl2(C3H7NO)2(H2O)2], was obtained upon dissolution of a dimethoxyethane adduct of MnCl2 in N,N-dimethylformamide. In the crystal structure, each MnII ion is located on a crystallographic inversion center, coordinated by two Cl [Mn-Cl = 2.53423 (17) Å] and four O [Mn-O = 2.1847 (5) and 2.2199 (6) Å] atoms in a distorted octahedral geometry. The complexes are linked into chains by complementary pairs of O-H
Cl hydrogen bonds. Adjacent chains pack via weaker O-HCl interactions or by interdigitation of -NMe2 groups. The H atoms of two symmetry-related methyl groups are disordered between two orientations in a 0.51:0.49 ratio.
A sample of 10 mg of the dimethoxyethane adduct of MnCl2, [MnCl2(C4H10O2)] (Fowles et al., 1969) was dissolved in wet N,N-dimethylformamide, and the solution was allowed to slowly evaporate. Over the course of 3 weeks, clusters of pale pink, rodlike crystals formed. The specimen used in this study was excized from a longer rod and mounted on a glass fiber for x-ray diffraction analysis. The crystals were washed with hexanes and dried prior to melting point determination and analysis by IR spectroscopy. These characterization data matched those previously reported reported for (I) (Kim et al., 1981; Kim et al., 1985).
The amide C—H distance was fixed at 0.93 Å and refined as riding, with Uiso(H) = 1.2Ueq(C). Water H atoms were located in the difference Fourier map. The O—H distances were restrained to 0.85 (1) Å with Uiso(H) = 1.5Ueq(O), and the other positional parameters were allowed to refine freely. Use of a longer O—H distance of 0.95 (1) Å resulted in a better match of standard uncertainties of anisotropic displacement parameters along the Mn—O1 bond (Hirshfeld test), but this also gave higher values of R[F2>2σ(F2)] and wR(F2), so the shorter O—H distance restraint was chosen. Methyl H atoms were placed with idealized threefold symmetry and fixed C—H distances of 0.96 Å, and they were refined in a riding model with Uiso(H) = 1.5Ueq(C). For C2, the locations of difference Fourier peaks suggested a disorder model in which two orientations of the methyl group were rotated by 60° relative to each other. Application of this disorder model resulted in improvements of 0.21% in R[F2>2σ(F2)] and 0.84% in wR(F2), with the occupancy ratio of the two orientations refining to 0.51:0.49.
Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL (Sheldrick, 2000); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL (Sheldrick, 2000).
![[Figure 1]](./cv2357fig1thm.gif)
| Fig. 1. The molecular structure of the title compound with displacement ellipsoids at the 50% probability level and the atomic numbering [symmetry code: (A) 1 − x, 1 − y, 1 − z]. Dashed lines indicate the second orientation of a rotationally disordered methyl group. |
![[Figure 2]](./cv2357fig2thm.gif)
| Fig. 2. Packing diagram of (I) showing part of an infinite chain of complexes linked by complementary O—H···Cl hydrogen bonding (dashed lines) along the a axis. Methyl H-atoms omitted for clarity. |
| [MnCl2(C3H7NO)2(H2O)2] | Z = 1 |
| Mr = 308.06 | F000 = 159 |
| Triclinic, P1 | Dx = 1.594 Mg m−3 |
| Hall symbol: -P 1 | Melting point = 362–364 K |
| a = 6.1224 (1) Å | Mo Kα radiation λ = 0.71073 Å |
| b = 6.8021 (1) Å | Cell parameters from 5092 reflections |
| c = 8.7056 (1) Å | θ = 2.6–40.4º |
| α = 110.539 (1)º | µ = 1.44 mm−1 |
| β = 105.431 (1)º | T = 298 (2) K |
| γ = 94.732 (1)º | Block, light pink |
| V = 320.992 (8) Å3 | 0.48 × 0.25 × 0.20 mm |
| Bruker SMART APEX II CCD diffractometer | 2435 independent reflections |
| Radiation source: fine-focus sealed tube | 2300 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.016 |
| Detector resolution: 0.75 pixels mm-1 | θmax = 33.1º |
| T = 298(2) K | θmin = 2.6º |
| phi and ω scans | h = −9→9 |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | k = −10→10 |
| Tmin = 0.534, Tmax = 0.746 | l = −13→13 |
| 10584 measured reflections |
| Refinement on F2 | 2 restraints |
| Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
| R[F2 > 2σ(F2)] = 0.017 | w = 1/[σ2(Fo2) + (0.0303P)2 + 0.0323P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.051 | (Δ/σ)max = 0.001 |
| S = 1.06 | Δρmax = 0.28 e Å−3 |
| 2435 reflections | Δρmin = −0.19 e Å−3 |
| 79 parameters | Extinction correction: none |
| [MnCl2(C3H7NO)2(H2O)2] | γ = 94.732 (1)º |
| Mr = 308.06 | V = 320.992 (8) Å3 |
| Triclinic, P1 | Z = 1 |
| a = 6.1224 (1) Å | Mo Kα |
| b = 6.8021 (1) Å | µ = 1.44 mm−1 |
| c = 8.7056 (1) Å | T = 298 (2) K |
| α = 110.539 (1)º | 0.48 × 0.25 × 0.20 mm |
| β = 105.431 (1)º |
| Bruker SMART APEX II CCD diffractometer | 2435 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 2300 reflections with I > 2σ(I) |
| Tmin = 0.534, Tmax = 0.746 | Rint = 0.016 |
| 10584 measured reflections |
| R[F2 > 2σ(F2)] = 0.017 | 2 restraints |
| wR(F2) = 0.051 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.06 | Δρmax = 0.28 e Å−3 |
| 2435 reflections | Δρmin = −0.19 e Å−3 |
| 79 parameters |
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. Restraints used: the O1—H11 and O1—H12 distances were restrained to 0.85 (1) Å. |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Mn1 | 0.5000 | 0.5000 | 0.5000 | 0.02292 (5) | |
| Cl1 | 0.73368 (3) | 0.20741 (3) | 0.43902 (2) | 0.03151 (5) | |
| O1 | 0.72383 (10) | 0.71285 (10) | 0.43607 (9) | 0.03632 (13) | |
| H11 | 0.8667 (15) | 0.729 (2) | 0.4685 (17) | 0.054* | |
| H12 | 0.691 (2) | 0.8319 (16) | 0.4380 (17) | 0.054* | |
| O2 | 0.71479 (10) | 0.63553 (10) | 0.77117 (7) | 0.03374 (12) | |
| C1 | 0.92887 (12) | 0.66040 (12) | 0.82274 (9) | 0.02796 (13) | |
| H1 | 1.0043 | 0.6194 | 0.7402 | 0.034* | |
| N1 | 1.05599 (11) | 0.74139 (10) | 0.98734 (8) | 0.02987 (12) | |
| C2 | 0.94941 (19) | 0.80913 (15) | 1.12328 (10) | 0.04124 (18) | |
| H21 | 0.8188 | 0.8697 | 1.0868 | 0.062* | 0.494 (15) |
| H22 | 1.0597 | 0.9145 | 1.2264 | 0.062* | 0.494 (15) |
| H23 | 0.8994 | 0.6879 | 1.1463 | 0.062* | 0.494 (15) |
| H24 | 1.0332 | 0.7783 | 1.2196 | 0.062* | 0.506 (15) |
| H25 | 0.7922 | 0.7336 | 1.0800 | 0.062* | 0.506 (15) |
| H26 | 0.9525 | 0.9602 | 1.1600 | 0.062* | 0.506 (15) |
| C3 | 1.30653 (16) | 0.76926 (19) | 1.03786 (14) | 0.0492 (2) | |
| H31 | 1.3537 | 0.7207 | 0.9362 | 0.074* | |
| H32 | 1.3573 | 0.6875 | 1.1062 | 0.074* | |
| H33 | 1.3739 | 0.9179 | 1.1045 | 0.074* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Mn1 | 0.01952 (7) | 0.02749 (8) | 0.01909 (7) | 0.00350 (5) | 0.00352 (4) | 0.00810 (5) |
| Cl1 | 0.02622 (8) | 0.03127 (9) | 0.03567 (9) | 0.00895 (6) | 0.00892 (6) | 0.01130 (7) |
| O1 | 0.0272 (3) | 0.0381 (3) | 0.0503 (3) | 0.0061 (2) | 0.0137 (2) | 0.0240 (3) |
| O2 | 0.0293 (2) | 0.0414 (3) | 0.0225 (2) | 0.0053 (2) | 0.00112 (18) | 0.0085 (2) |
| C1 | 0.0300 (3) | 0.0289 (3) | 0.0214 (3) | 0.0024 (2) | 0.0043 (2) | 0.0091 (2) |
| N1 | 0.0294 (3) | 0.0306 (3) | 0.0227 (2) | 0.0009 (2) | 0.0000 (2) | 0.0096 (2) |
| C2 | 0.0568 (5) | 0.0390 (4) | 0.0228 (3) | 0.0113 (4) | 0.0092 (3) | 0.0082 (3) |
| C3 | 0.0294 (4) | 0.0592 (6) | 0.0472 (5) | −0.0032 (4) | −0.0046 (3) | 0.0217 (4) |
| Mn1—O2i | 2.1847 (5) | N1—C2 | 1.4549 (12) |
| Mn1—O2 | 2.1847 (5) | N1—C3 | 1.4549 (11) |
| Mn1—O1 | 2.2199 (6) | C2—H21 | 0.9600 |
| Mn1—O1i | 2.2199 (6) | C2—H22 | 0.9600 |
| Mn1—Cl1i | 2.53419 (17) | C2—H23 | 0.9600 |
| Mn1—Cl1 | 2.53423 (17) | C2—H24 | 0.9600 |
| O1—H11 | 0.830 (8) | C2—H25 | 0.9600 |
| O1—H12 | 0.846 (8) | C2—H26 | 0.9600 |
| O2—C1 | 1.2430 (9) | C3—H31 | 0.9600 |
| C1—N1 | 1.3208 (9) | C3—H32 | 0.9600 |
| C1—H1 | 0.9300 | C3—H33 | 0.9600 |
| O2i—Mn1—O2 | 180.0 | N1—C2—H22 | 109.5 |
| O2i—Mn1—O1 | 88.54 (2) | H21—C2—H22 | 109.5 |
| O2—Mn1—O1 | 91.46 (2) | N1—C2—H23 | 109.5 |
| O2i—Mn1—O1i | 91.46 (2) | H21—C2—H23 | 109.5 |
| O2—Mn1—O1i | 88.54 (2) | H22—C2—H23 | 109.5 |
| O1—Mn1—O1i | 180.0 | N1—C2—H24 | 109.5 |
| O2i—Mn1—Cl1i | 89.920 (17) | H21—C2—H24 | 141.1 |
| O2—Mn1—Cl1i | 90.081 (17) | H22—C2—H24 | 56.3 |
| O1—Mn1—Cl1i | 87.097 (17) | H23—C2—H24 | 56.3 |
| O1i—Mn1—Cl1i | 92.903 (17) | N1—C2—H25 | 109.5 |
| O2i—Mn1—Cl1 | 90.080 (17) | H21—C2—H25 | 56.3 |
| O2—Mn1—Cl1 | 89.920 (17) | H22—C2—H25 | 141.1 |
| O1—Mn1—Cl1 | 92.903 (17) | H23—C2—H25 | 56.3 |
| O1i—Mn1—Cl1 | 87.096 (17) | H24—C2—H25 | 109.5 |
| Cl1i—Mn1—Cl1 | 180.000 (6) | N1—C2—H26 | 109.5 |
| Mn1—O1—H11 | 122.5 (10) | H21—C2—H26 | 56.3 |
| Mn1—O1—H12 | 119.7 (10) | H22—C2—H26 | 56.3 |
| H11—O1—H12 | 107.3 (13) | H23—C2—H26 | 141.1 |
| C1—O2—Mn1 | 124.95 (5) | H24—C2—H26 | 109.5 |
| O2—C1—N1 | 124.15 (7) | H25—C2—H26 | 109.5 |
| O2—C1—H1 | 117.9 | N1—C3—H31 | 109.5 |
| N1—C1—H1 | 117.9 | N1—C3—H32 | 109.5 |
| C1—N1—C2 | 120.85 (7) | H31—C3—H32 | 109.5 |
| C1—N1—C3 | 121.02 (8) | N1—C3—H33 | 109.5 |
| C2—N1—C3 | 118.12 (7) | H31—C3—H33 | 109.5 |
| N1—C2—H21 | 109.5 | H32—C3—H33 | 109.5 |
| O1—Mn1—O2—C1 | −48.73 (7) | Mn1—O2—C1—N1 | −179.54 (5) |
| O1i—Mn1—O2—C1 | 131.27 (7) | O2—C1—N1—C2 | −0.08 (12) |
| Cl1i—Mn1—O2—C1 | −135.83 (6) | O2—C1—N1—C3 | −178.88 (8) |
| Cl1—Mn1—O2—C1 | 44.17 (6) |
| Symmetry codes: (i) −x+1, −y+1, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H11···Cl1ii | 0.830 (8) | 2.314 (9) | 3.1424 (6) | 177.2 (13) |
| O1—H12···Cl1iii | 0.846 (8) | 2.543 (9) | 3.3505 (6) | 159.9 (13) |
| Symmetry codes: (ii) −x+2, −y+1, −z+1; (iii) x, y+1, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H11···Cl1i | 0.830 (8) | 2.314 (9) | 3.1424 (6) | 177.2 (13) |
| O1—H12···Cl1ii | 0.846 (8) | 2.543 (9) | 3.3505 (6) | 159.9 (13) |
| Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, y+1, z. |
The authors thank the Oklahoma State Regents for Higher Education for providing funds to purchase the APEXII diffractometer. IMS was supported by a Freshman Research Scholarship from Oklahoma State University.
Bruker (2006). APEX2 (Version 2.0) and SAINT (Version 7.23A). Bruker AXS Inc., Madison, Wisconsin, USA.
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Deng, Z.-P., Gao, S., Huo, L.-H. & Zhao, H. (2007). Acta Cryst. C63, m225–m227.
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Kim et al. (1981) reported that [MnCl2(H2O)2(C3H7NO)2] crystallized from solutions of MnCl2 in water—N,N-dimethylformamide (DMF) mixtures containing greater than 10.4% DMF by mass, with [MnCl2(H2O)4] becoming predominant at lower DMF concentrations. These authors characterized the complex by elemental analysis, thermal analysis, and infrared spectroscopy (Kim et al., 1985), but no structural data or other subsequent studies have been reported.
The title compound, (I), is centrosymmetric with all-trans stereochemistry about the metal center (Fig. 1), reflecting the absence of any high-field ligand that would disfavor such an arrangement. The DMF ligands are O-bound as previously proposed on the basis of infrared spectral data (Kim et al., 1981). The Mn—O distances of 2.2199 (6) Å (H2O) and 2.1847 (5) Å (DMF) and the Mn—Cl distance of 2.53423 (17) Å are normal for MnII complexes, and the angles between coordinated atoms are in the range 90.080 (17)—92.903 (17)°. Molecules of (I) form hydrogen-bonded chains along the crystallographic a axis via complementary pairs of O—H···Cl interactions with O···Cl separations of 3.1424 (6) Å (Fig. 2). Weaker complementary O—H···Cl hydrogen bonds with O···Cl distances of 3.3505 (6) Å connect neighboring chains in the b direction. The —NMe2 groups are interdigitated with those of adjacent complexes lying along the [101] and [111] directions.
Although DMF complexes of first row transition metals are not as well known as complexes of other common donor solvents, some interesting examples of MnII coordination polymers containing O-bound DMF have recently appeared (Chan et al., 2007; Deng et al., 2007), suggesting that DMF is a useful ligand for stabilizing MnII.