Bis(acetyl­acetonato-κ²O,O′)(methanol-κO)(thio­cyanato-κN)manganese(III)

In the title complex, [Mn(C₅H₇O₂)₂(NCS)(CH₄O)], the Mn^III atom has a slightly distorted octa­hedral coordination formed by five O atoms and one N atom. The equatorial positions are occupied by four O atoms of two acetyl­acetonate ligands, while the axial positions are occupied by the N atom of the thio­cyanate anion and the O atom of the methanol mol­ecule. In the crystal structure, complex mol­ecules are linked by an inter­molecular O—H...S hydrogen bond, forming a chain running along [101].

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.058
• wR factor = 0.148
• Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.112
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.11
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         45 Perc.
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         N1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C1
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          9

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 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

Octahedral complexes of high-spin Mn^III are good examples for investigating the Jahn-Teller distortions, because their geometry are always distorted from the ideal octahedron to the distorted one by the axial ligands. Here, we report the structure of an octahedral Mn^III complex, whose synthesis has been reported early (Stults et al., 1975).

The molecular structure of the title complex is shown in Figure 1. The Mn^III atom is six coordinated by five O atoms and one N atom. The geometry can be described as a distorted octahedron. Four equational positions are occupied by four O atoms coming from two acetylacetonate ligands with the average Mn—O bond length 1.909 Å, which is in agreement well with the corresponding distance in [Mn(acac)₂(OH₂)₂]ClO₄].2H₂O. (Swarnabala et al., 1994). One SCN^- ion and one methanol molecule are coordinated to the Mn^III atom with trans positions, so that forming an octahedral geometry. The distance of Mn—O_methanol [2.289 (5) Å] is obviously longer than the bond lengths of Mn—O_{acetylacetonate}. The bond length of Mn—N_SCN is 2.187 (6) Å, which is also consistent with that found in [Mn(acac)₂(SCN)] (Stults et al., 1979). In the crystal structure, a molecular chain along the [101] direction is formed by an intermolecular H-bond between the O atom of the methanol molecule and the S atom of the SCN^- ion (Table 1).

Related literature

For the synthesis, see: Stults et al. (1975). For related structures, see: Stults et al. (1979); Swarnabala et al. (1994). Please check changes.

S2. Experimental

The title complex was synthesized according to the literature method (Stults et al. 1975). The single crystals suitable for X-ray diffraction were grown from a methanol solution after the solvent was partial evaporated. Anal. Calcd for C₁₂H₁₈MnNO₅S: C 41.99, H 5.29, N 4.08; found: C 42.04, H 5.26, N, 4.11.

S3. Refinement

The O-bound H atom of the methanol molecule was located in a difference Fourier map and its coordinates were refined, with U_iso(H) = 1.5U_eq(O). The H atoms bound to C atoms were placed geometrically (C—H = 0.93–0.96 Å) and were refined as riding, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C).

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004); 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

Fig. 1. A view of the title complex with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted.

Bis(acetylacetonato-κ²O,O')(methanol-κO)(thiocyanato-κN)manganese(III)

Crystal data

[Mn(C5H7O2)2(NCS)(CH4O)]	F(000) = 712
Mr = 343.27	Dx = 1.412 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2yn	Cell parameters from 1347 reflections
a = 7.4795 (13) Å	θ = 2.8?–16.2°
b = 12.420 (2) Å	µ = 0.96 mm^−1
c = 17.586 (3) Å	T = 293 K
β = 98.673 (4)°	Block, brown
V = 1614.9 (5) Å^3	0.21 × 0.19 × 0.15 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	2830 independent reflections
Radiation source: fine-focus sealed tube	1276 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.112
ϕ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→8
Tmin = 0.824, Tmax = 0.869	k = −14→14
7925 measured reflections	l = −16→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.058	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.148	w = 1/[σ^2(Fo^2) + (0.0541P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.91	(Δ/σ)max < 0.001
2830 reflections	Δρmax = 0.33 e Å^−3
189 parameters	Δρmin = −0.33 e Å^−3
0 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
Mn	0.86466 (12)	0.33696 (7)	0.64488 (5)	0.0398 (3)
S1	1.1860 (3)	0.34036 (15)	0.90976 (10)	0.0749 (7)
O1	1.0806 (5)	0.3054 (3)	0.6035 (2)	0.0504 (12)
O2	0.7813 (5)	0.1923 (3)	0.6275 (2)	0.0446 (11)
O3	0.6418 (5)	0.3674 (3)	0.6806 (2)	0.0458 (11)
O4	0.9347 (5)	0.4844 (3)	0.6515 (2)	0.0485 (12)
O5	0.7201 (7)	0.3709 (4)	0.5230 (3)	0.0682 (16)
H5A	0.701 (11)	0.325 (6)	0.491 (4)	0.102*
C1	1.0772 (9)	0.3201 (5)	0.8239 (4)	0.0455 (17)
C2	0.7403 (12)	0.4605 (6)	0.4764 (4)	0.100 (3)
H2A	0.7848	0.5205	0.5082	0.150*
H2B	0.6253	0.4788	0.4471	0.150*
H2C	0.8245	0.4437	0.4420	0.150*
C3	1.3234 (9)	0.2126 (6)	0.5642 (5)	0.084 (3)
H3A	1.3176	0.2455	0.5144	0.126*
H3B	1.3652	0.1398	0.5620	0.126*
H3C	1.4055	0.2524	0.6011	0.126*
C4	1.1395 (9)	0.2130 (6)	0.5877 (4)	0.0491 (17)
C5	1.0421 (9)	0.1195 (5)	0.5885 (4)	0.0537 (19)
H5	1.0977	0.0559	0.5768	0.064*
C6	0.8682 (10)	0.1122 (5)	0.6054 (3)	0.0472 (18)
C7	0.7645 (9)	0.0081 (4)	0.5966 (4)	0.061 (2)
H7A	0.7050	−0.0029	0.6407	0.091*
H7B	0.8463	−0.0504	0.5924	0.091*
H7C	0.6758	0.0110	0.5511	0.091*
C8	0.4019 (8)	0.4572 (5)	0.7255 (4)	0.058 (2)
H8A	0.3125	0.4324	0.6842	0.088*
H8B	0.3704	0.5280	0.7408	0.088*
H8C	0.4067	0.4089	0.7684	0.088*
C9	0.5827 (8)	0.4605 (5)	0.6990 (3)	0.0415 (16)
C10	0.6804 (9)	0.5539 (5)	0.6967 (4)	0.0531 (19)
H10	0.6281	0.6168	0.7118	0.064*
C11	0.8462 (10)	0.5633 (5)	0.6743 (4)	0.0510 (18)
C12	0.9380 (10)	0.6708 (5)	0.6760 (5)	0.092 (3)
H12A	1.0490	0.6684	0.7114	0.138*
H12B	0.8603	0.7250	0.6922	0.138*
H12C	0.9636	0.6880	0.6255	0.138*
N1	0.9996 (8)	0.3080 (5)	0.7624 (3)	0.0617 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn	0.0393 (6)	0.0339 (5)	0.0471 (6)	−0.0035 (5)	0.0093 (4)	−0.0032 (5)
S1	0.1019 (17)	0.0683 (13)	0.0490 (12)	−0.0013 (13)	−0.0060 (11)	0.0010 (11)
O1	0.043 (3)	0.046 (3)	0.065 (3)	−0.007 (2)	0.017 (2)	−0.012 (2)
O2	0.043 (3)	0.035 (2)	0.055 (3)	−0.003 (2)	0.005 (2)	−0.004 (2)
O3	0.041 (3)	0.041 (2)	0.057 (3)	−0.001 (2)	0.013 (2)	−0.003 (2)
O4	0.052 (3)	0.034 (2)	0.063 (3)	−0.003 (2)	0.016 (2)	−0.005 (2)
O5	0.090 (4)	0.069 (4)	0.043 (3)	−0.006 (3)	0.001 (3)	0.000 (3)
C1	0.041 (4)	0.042 (4)	0.056 (5)	−0.002 (3)	0.015 (4)	0.006 (4)
C2	0.135 (8)	0.097 (7)	0.061 (6)	−0.012 (6)	−0.003 (5)	0.024 (5)
C3	0.052 (5)	0.096 (6)	0.108 (7)	0.002 (4)	0.029 (5)	−0.041 (5)
C4	0.045 (5)	0.057 (4)	0.044 (4)	0.005 (4)	0.001 (3)	−0.013 (4)
C5	0.049 (5)	0.040 (4)	0.073 (5)	0.008 (4)	0.011 (4)	−0.010 (4)
C6	0.064 (5)	0.042 (4)	0.034 (4)	−0.002 (4)	0.001 (4)	−0.007 (3)
C7	0.076 (5)	0.038 (4)	0.066 (5)	−0.009 (4)	0.004 (4)	−0.007 (4)
C8	0.048 (5)	0.072 (5)	0.059 (5)	0.001 (4)	0.022 (4)	−0.014 (4)
C9	0.043 (4)	0.048 (4)	0.031 (4)	0.005 (3)	0.001 (3)	−0.006 (3)
C10	0.073 (6)	0.036 (4)	0.055 (5)	0.001 (4)	0.026 (4)	−0.011 (3)
C11	0.063 (5)	0.042 (4)	0.051 (5)	−0.010 (4)	0.019 (4)	−0.001 (4)
C12	0.109 (7)	0.039 (4)	0.140 (8)	−0.012 (5)	0.061 (6)	−0.015 (5)
N1	0.062 (4)	0.067 (4)	0.054 (4)	−0.015 (3)	0.001 (3)	0.003 (3)

Geometric parameters (Å, º)

Mn—O4	1.903 (4)	C3—H3C	0.9600
Mn—O2	1.911 (4)	C4—C5	1.372 (8)
Mn—O3	1.906 (4)	C5—C6	1.380 (8)
Mn—O1	1.910 (4)	C5—H5	0.9300
Mn—N1	2.189 (6)	C6—C7	1.505 (8)
Mn—O5	2.289 (5)	C7—H7A	0.9600
S1—C1	1.623 (8)	C7—H7B	0.9600
O1—C4	1.275 (6)	C7—H7C	0.9600
O2—C6	1.280 (7)	C8—C9	1.495 (8)
O3—C9	1.296 (6)	C8—H8A	0.9600
O4—C11	1.281 (7)	C8—H8B	0.9600
O5—C2	1.405 (8)	C8—H8C	0.9600
O5—H5A	0.80 (7)	C9—C10	1.375 (8)
C1—N1	1.157 (7)	C10—C11	1.361 (8)
C2—H2A	0.9600	C10—H10	0.9300
C2—H2B	0.9600	C11—C12	1.501 (8)
C2—H2C	0.9600	C12—H12A	0.9600
C3—C4	1.494 (8)	C12—H12B	0.9600
C3—H3A	0.9600	C12—H12C	0.9600
C3—H3B	0.9600
O4—Mn—O2	173.85 (19)	O1—C4—C5	123.9 (6)
O4—Mn—O3	92.02 (17)	O1—C4—C3	115.2 (6)
O2—Mn—O3	87.66 (16)	C5—C4—C3	120.8 (6)
O4—Mn—O1	88.83 (17)	C4—C5—C6	125.2 (6)
O2—Mn—O1	91.17 (17)	C4—C5—H5	117.4
O3—Mn—O1	176.83 (18)	C6—C5—H5	117.4
O4—Mn—N1	91.0 (2)	O2—C6—C5	123.6 (6)
O2—Mn—N1	95.16 (19)	O2—C6—C7	114.9 (6)
O3—Mn—N1	91.32 (19)	C5—C6—C7	121.5 (6)
O1—Mn—N1	91.7 (2)	C6—C7—H7A	109.5
O4—Mn—O5	88.09 (17)	C6—C7—H7B	109.5
O2—Mn—O5	85.76 (18)	H7A—C7—H7B	109.5
O3—Mn—O5	87.65 (18)	C6—C7—H7C	109.5
O1—Mn—O5	89.33 (18)	H7A—C7—H7C	109.5
N1—Mn—O5	178.6 (2)	H7B—C7—H7C	109.5
C4—O1—Mn	127.4 (4)	C9—C8—H8A	109.5
C6—O2—Mn	127.6 (4)	C9—C8—H8B	109.5
C9—O3—Mn	127.4 (4)	H8A—C8—H8B	109.5
C11—O4—Mn	127.2 (4)	C9—C8—H8C	109.5
C2—O5—Mn	128.0 (4)	H8A—C8—H8C	109.5
C2—O5—H5A	100 (6)	H8B—C8—H8C	109.5
Mn—O5—H5A	123 (6)	O3—C9—C10	122.8 (6)
N1—C1—S1	178.5 (7)	O3—C9—C8	114.3 (5)
O5—C2—H2A	109.5	C10—C9—C8	122.9 (6)
H5A—C2—H2A	136.0	C11—C10—C9	126.3 (6)
O5—C2—H2B	109.5	C11—C10—H10	116.8
H5A—C2—H2B	98.6	C9—C10—H10	116.8
H2A—C2—H2B	109.5	O4—C11—C10	124.2 (6)
O5—C2—H2C	109.5	O4—C11—C12	115.5 (6)
H5A—C2—H2C	91.3	C10—C11—C12	120.3 (6)
H2A—C2—H2C	109.5	C11—C12—H12A	109.5
H2B—C2—H2C	109.5	C11—C12—H12B	109.5
C4—C3—H3A	109.5	H12A—C12—H12B	109.5
C4—C3—H3B	109.5	C11—C12—H12C	109.5
H3A—C3—H3B	109.5	H12A—C12—H12C	109.5
C4—C3—H3C	109.5	H12B—C12—H12C	109.5
H3A—C3—H3C	109.5	C1—N1—Mn	162.9 (6)
H3B—C3—H3C	109.5
O4—Mn—O1—C4	174.8 (5)	Mn—O1—C4—C5	9.1 (9)
O2—Mn—O1—C4	−11.4 (5)	Mn—O1—C4—C3	−173.5 (4)
N1—Mn—O1—C4	83.8 (5)	O1—C4—C5—C6	0.8 (11)
O5—Mn—O1—C4	−97.1 (5)	C3—C4—C5—C6	−176.4 (6)
O3—Mn—O2—C6	−175.2 (5)	Mn—O2—C6—C5	−1.7 (8)
O1—Mn—O2—C6	7.7 (5)	Mn—O2—C6—C7	−179.7 (4)
N1—Mn—O2—C6	−84.2 (5)	C4—C5—C6—O2	−4.7 (10)
O5—Mn—O2—C6	96.9 (5)	C4—C5—C6—C7	173.2 (6)
O4—Mn—O3—C9	0.7 (5)	Mn—O3—C9—C10	−1.7 (8)
O2—Mn—O3—C9	−173.2 (5)	Mn—O3—C9—C8	−179.9 (3)
N1—Mn—O3—C9	91.7 (5)	O3—C9—C10—C11	1.3 (10)
O5—Mn—O3—C9	−87.3 (5)	C8—C9—C10—C11	179.4 (6)
O3—Mn—O4—C11	0.8 (5)	Mn—O4—C11—C10	−1.3 (9)
O1—Mn—O4—C11	177.8 (5)	Mn—O4—C11—C12	177.7 (4)
N1—Mn—O4—C11	−90.5 (5)	C9—C10—C11—O4	0.3 (11)
O5—Mn—O4—C11	88.4 (5)	C9—C10—C11—C12	−178.7 (6)
O4—Mn—O5—C2	15.3 (5)	O4—Mn—N1—C1	5.2 (18)
O3—Mn—O5—C2	107.5 (5)	O3—Mn—N1—C1	−86.9 (18)
O1—Mn—O5—C2	−73.5 (5)	O1—Mn—N1—C1	94.0 (18)
O2—Mn—O5—C2	−164.7 (5)	O2—Mn—N1—C1	−174.6 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···S1^i	0.78 (7)	2.51 (6)	3.281 (4)	168 (7)

Symmetry code: (i) x−1/2, −y+1/2, z−1/2.