trans-Diaqua­dichloridobis(N,N-dimethyl­formamide-κO)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 Mn^II 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—H...Cl 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.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](N-C) = 0.001 Å
• R factor = 0.017
• wR factor = 0.051
• Data-to-parameter ratio = 30.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Mn1    -   O2      ..      10.93 su

Alert level C
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)         10 Ang.
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        100 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          6

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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 Mn^II 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 Mn^II 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 Mn^II.

Related literature

For the initial synthesis and characterization of the title compound and its precursor, see: Kim et al. (1981, 1985); Fowles et al. (1969). For recent examples of related coordination polymers, see: Chan et al. (2007); Deng et al. (2007).

S2. Experimental

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).

S3. Refinement

The amide C—H distance was fixed at 0.93 Å and refined as riding, with U_iso(H) = 1.2U_eq(C). Water H atoms were located in the difference Fourier map. The O—H distances were restrained to 0.85 (1) Å with U_iso(H) = 1.5U_eq(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 U_iso(H) = 1.5U_eq(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.

Computing details

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).

Figures

	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.
	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.

trans-Diaquadichloridobis(N,N-dimethylformamide-\kO)manganese(II)

Crystal data

[MnCl2(C3H7NO)2(H2O)2]	Z = 1
Mr = 308.06	F(000) = 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 = 2.6–40.4°
α = 110.539 (1)°	µ = 1.44 mm^−1
β = 105.431 (1)°	T = 298 K
γ = 94.732 (1)°	Block, light pink
V = 320.99 (1) Å^3	0.48 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEX II CCD diffractometer	2435 independent reflections
Radiation source: fine-focus sealed tube	2300 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
Detector resolution: 0.75 pixels mm^-1	θmax = 33.1°, θmin = 2.6°
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

Refinement on F^2	2 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.017	w = 1/[σ^2(Fo^2) + (0.0303P)^2 + 0.0323P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Mn1—O2^i	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—O1^i	2.2199 (6)	C2—H22	0.9600
Mn1—Cl1^i	2.5342 (2)	C2—H23	0.9600
Mn1—Cl1	2.5342 (2)	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
O2^i—Mn1—O2	180.0	N1—C2—H22	109.5
O2^i—Mn1—O1	88.54 (2)	H21—C2—H22	109.5
O2—Mn1—O1	91.46 (2)	N1—C2—H23	109.5
O2^i—Mn1—O1^i	91.46 (2)	H21—C2—H23	109.5
O2—Mn1—O1^i	88.54 (2)	H22—C2—H23	109.5
O1—Mn1—O1^i	180.0	N1—C2—H24	109.5
O2^i—Mn1—Cl1^i	89.920 (17)	H21—C2—H24	141.1
O2—Mn1—Cl1^i	90.081 (17)	H22—C2—H24	56.3
O1—Mn1—Cl1^i	87.097 (17)	H23—C2—H24	56.3
O1^i—Mn1—Cl1^i	92.903 (17)	N1—C2—H25	109.5
O2^i—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
O1^i—Mn1—Cl1	87.096 (17)	H24—C2—H25	109.5
Cl1^i—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)
O1^i—Mn1—O2—C1	131.27 (7)	O2—C1—N1—C2	−0.08 (12)
Cl1^i—Mn1—O2—C1	−135.83 (6)	O2—C1—N1—C3	−178.88 (8)
Cl1—Mn1—O2—C1	44.17 (6)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H11···Cl1^ii	0.83 (1)	2.31 (1)	3.1424 (6)	177 (1)
O1—H12···Cl1^iii	0.85 (1)	2.54 (1)	3.3505 (6)	160 (1)

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