Redetermination of bis­­(acetyl­acetonato-κ²O,O′)(1,10-phenanthroline-κ²N,N′)manganese(II)

In the crystal structure of the title compound, [Mn(C₅H₇O₂)₂(C₁₂H₈N₂)], the Mn²⁺ cation is coordinated by one bidentate 1,10-phenanthroline ligand and two acetyl­acetonate anions within a slightly distorted N₂O₄ octa­hedron. The asymmetric unit consists of one Mn²⁺ cation situated on a twofold rotation axis, one half of a 1,10-phenanthroline ligand and one acetyl­acetonate anion. In comparison with the previous determination based on visually estimated intensities recorded on precession photographs, the current redetermination with image-plate data reveals bond lengths and angles with much higher precision.

Related literature

For the previous determination of the crystal structure, see: Stephens (1977).

Experimental

Crystal data

• [Mn(C₅H₇O₂)₂(C₁₂H₈N₂)]

• M_r = 433.36

• Orthorhombic, P b c n

• a = 15.8353 (7) Å

• b = 10.2260 (4) Å

• c = 12.6532 (4) Å

• V = 2048.96 (14) ų

• Z = 4

• Mo Kα radiation

• μ = 0.68 mm⁻¹

• T = 200 K

• 0.31 × 0.19 × 0.08 mm

Data collection

• Stoe IPDS-2 diffractometer

• 14233 measured reflections

• 2007 independent reflections

• 1742 reflections with I > 2σ(I)

• R_int = 0.086

Refinement

• R[F² > 2σ(F²)] = 0.047

• wR(F²) = 0.103

• S = 1.16

• 2007 reflections

• 134 parameters

• H-atom parameters constrained

• Δρ_max = 0.26 e Å⁻³

• Δρ_min = −0.26 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA; data reduction: X-AREA); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010).

Supporting information

S1. Comment

The title compound was serendipitously obtained within a project on the synthesis of manganese(III) coordination polymers containing cyanate anions and neutral N-donor co-ligands. Within this project manganese(III) acetylacetonate was reacted with 1,10-phenanthroline and potassium cyanate in acetonitrile leading to the formation of crystals of the title compound, the composition of which was determined by X-ray structure analysis. The crystal structure of this compound has already been reported by Stephens (1977) from visually estimated intensity data recorded on precession photographs. We decided to redetermine the structure on basis of image plate intensity data to achieve higher precision with respect to lattice parameters, atomic coordinates and resulting bond lengths and angles.

The manganese(II) cation is coordinated by two nitrogen atoms of the 1,10-phenanthroline ligand and four oxygen atoms of two symmetry-related acetylacetonate anions into discrete complexes that are located on twofold rotation axes (Fig. 1). The coordination polyhedron of the manganese(II) cation can be described as a slightly distorted MnN₄O₂ octahedron. Bond lengths and angles are comparable to those of the previous determination (Stephens, 1977), however with much higher precision, e.g. 2.2962 (18) Å for the Mn—N, and 2.1139 (16) and 2.1543 (16) Å for the two Mn—O bond lengths determined during the present redetermination versus 2.307 (5), 2.116 (5) and 2.152 (5) Å, respectively, of the previous determination.

Individual complex molecules are mainly held together by van der Waals forces. In the crystal structure, the discrete complexes are arranged in columns extending parallel to [001] (Fig. 2). Within these columns neighbouring complexes are related by centers of inversion.

Related literature

For the previous determination of the crystal structure, see: Stephens (1977).

S2. Experimental

Manganese(III) 2,4-pentadionate and 1,10-phenanthroline were purchased from Alfa Aesar. Potassium cyanate was purchased from Fluka. The title compound was obtained by the reaction of 70.5 mg Mn(III) 2,4-pentadionate (0.20 mmol), 48.7 mg potassium cyanate (0.6 mmol) and 144.32 mg 1,10-phenanthroline (0.8 mmol) in 1.5 ml acetonitrile at RT in a closed 3 ml snap cap vial. After three days brown crystals of the title compound, mostly in the form of needles, were obtained by slow evaporation of the solvent.

S3. Refinement

The aromatic hydrogen atoms were positioned with idealized geometry, methyl H atoms were allowed to rotate but not to tip, and were refined with U_eq(H) = 1.2 U_eq(C) for aromatic H atoms (1.5 for methyl H atoms) using a riding model with C—H = 0.95 Å (aromatic) and with C—H = 0.98 Å (methyl).

Computing details

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structure of the title compound with labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry code: i) -x+1,y,-z+3/2.]
	Fig. 2. The crystal structure of the title compound in a projection along [001].

Bis(acetylacetonato-κ²O,O')(1,10-phenanthroline-κ²N,N')manganese(II)

Crystal data

[Mn(C5H7O2)2(C12H8N2)]	F(000) = 900
Mr = 433.36	Dx = 1.405 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 17733 reflections
a = 15.8353 (7) Å	θ = 1.9–26.0°
b = 10.2260 (4) Å	µ = 0.68 mm^−1
c = 12.6532 (4) Å	T = 200 K
V = 2048.96 (14) Å^3	Plate, brown
Z = 4	0.31 × 0.19 × 0.08 mm

Data collection

Stoe IPDS-2 diffractometer	1742 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.086
Graphite monochromator	θmax = 26.0°, θmin = 2.4°
ω scans	h = −19→19
14233 measured reflections	k = −10→12
2007 independent reflections	l = −14→15

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	H-atom parameters constrained
S = 1.16	w = 1/[σ^2(Fo^2) + (0.0406P)^2 + 0.9028P] where P = (Fo^2 + 2Fc^2)/3
2007 reflections	(Δ/σ)max < 0.001
134 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

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
Mn1	0.5000	0.52826 (5)	0.7500	0.03271 (17)
C1	0.23055 (17)	0.4974 (4)	0.8396 (3)	0.0658 (9)
H1A	0.2197	0.4070	0.8179	0.099*
H1B	0.1819	0.5521	0.8213	0.099*
H1C	0.2398	0.5004	0.9162	0.099*
C2	0.30819 (15)	0.5480 (3)	0.7834 (2)	0.0425 (6)
C3	0.29703 (16)	0.6189 (3)	0.6895 (2)	0.0502 (7)
H3	0.2406	0.6335	0.6668	0.060*
C4	0.36143 (15)	0.6699 (2)	0.6268 (2)	0.0432 (6)
C5	0.3379 (2)	0.7457 (3)	0.5282 (3)	0.0675 (9)
H5A	0.3697	0.8279	0.5261	0.101*
H5B	0.2772	0.7648	0.5291	0.101*
H5C	0.3515	0.6935	0.4655	0.101*
O1	0.37816 (10)	0.52168 (17)	0.82556 (13)	0.0406 (4)
O2	0.43944 (10)	0.65765 (17)	0.64402 (14)	0.0435 (4)
N11	0.53476 (11)	0.34743 (18)	0.84839 (14)	0.0328 (4)
C11	0.56836 (14)	0.3481 (2)	0.94437 (18)	0.0362 (5)
H11	0.5787	0.4300	0.9775	0.043*
C12	0.58922 (14)	0.2340 (2)	0.99889 (19)	0.0386 (5)
H12	0.6137	0.2388	1.0673	0.046*
C13	0.57416 (14)	0.1155 (2)	0.95299 (18)	0.0377 (5)
H13	0.5884	0.0371	0.9892	0.045*
C14	0.53730 (13)	0.1099 (2)	0.85136 (18)	0.0341 (5)
C15	0.51892 (13)	0.2298 (2)	0.80233 (17)	0.0315 (5)
C16	0.51771 (14)	−0.0106 (2)	0.7983 (2)	0.0378 (5)
H16	0.5300	−0.0915	0.8319	0.045*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0362 (3)	0.0284 (3)	0.0335 (3)	0.000	−0.00258 (19)	0.000
C1	0.0468 (15)	0.088 (3)	0.063 (2)	−0.0034 (15)	0.0073 (13)	0.0081 (17)
C2	0.0378 (12)	0.0447 (14)	0.0448 (14)	0.0015 (10)	0.0007 (10)	−0.0077 (11)
C3	0.0371 (12)	0.0531 (16)	0.0603 (18)	0.0019 (11)	−0.0077 (12)	0.0058 (13)
C4	0.0458 (13)	0.0320 (12)	0.0517 (15)	−0.0019 (10)	−0.0132 (11)	0.0024 (11)
C5	0.0617 (17)	0.0625 (19)	0.078 (2)	−0.0140 (15)	−0.0290 (16)	0.0291 (17)
O1	0.0387 (8)	0.0461 (10)	0.0370 (9)	0.0003 (7)	0.0000 (7)	−0.0026 (7)
O2	0.0406 (8)	0.0395 (9)	0.0504 (10)	−0.0021 (7)	−0.0056 (8)	0.0119 (8)
N11	0.0391 (9)	0.0296 (9)	0.0297 (10)	−0.0001 (7)	−0.0014 (7)	−0.0005 (8)
C11	0.0407 (11)	0.0359 (12)	0.0320 (12)	0.0009 (9)	−0.0012 (9)	−0.0016 (10)
C12	0.0422 (12)	0.0417 (13)	0.0320 (12)	0.0024 (10)	−0.0046 (9)	0.0014 (10)
C13	0.0411 (12)	0.0373 (13)	0.0348 (12)	0.0049 (10)	0.0005 (9)	0.0075 (10)
C14	0.0374 (11)	0.0330 (11)	0.0320 (12)	0.0028 (9)	0.0026 (9)	0.0021 (10)
C15	0.0346 (10)	0.0301 (11)	0.0297 (12)	0.0000 (8)	0.0016 (8)	0.0005 (9)
C16	0.0419 (12)	0.0289 (11)	0.0426 (14)	0.0024 (9)	0.0049 (10)	0.0051 (10)

Geometric parameters (Å, º)

Mn1—O2^i	2.1139 (16)	C5—H5A	0.9800
Mn1—O2	2.1139 (16)	C5—H5B	0.9800
Mn1—O1^i	2.1543 (16)	C5—H5C	0.9800
Mn1—O1	2.1543 (16)	N11—C11	1.326 (3)
Mn1—N11^i	2.2962 (18)	N11—C15	1.360 (3)
Mn1—N11	2.2962 (18)	C11—C12	1.395 (3)
C1—C2	1.512 (4)	C11—H11	0.9500
C1—H1A	0.9800	C12—C13	1.366 (3)
C1—H1B	0.9800	C12—H12	0.9500
C1—H1C	0.9800	C13—C14	1.413 (3)
C2—O1	1.259 (3)	C13—H13	0.9500
C2—C3	1.403 (4)	C14—C15	1.405 (3)
C3—C4	1.394 (4)	C14—C16	1.437 (3)
C3—H3	0.9500	C15—C15^i	1.453 (4)
C4—O2	1.261 (3)	C16—C16^i	1.344 (5)
C4—C5	1.515 (4)	C16—H16	0.9500
O2^i—Mn1—O2	102.50 (10)	C4—C5—H5A	109.5
O2^i—Mn1—O1^i	83.96 (6)	C4—C5—H5B	109.5
O2—Mn1—O1^i	98.30 (6)	H5A—C5—H5B	109.5
O2^i—Mn1—O1	98.30 (6)	C4—C5—H5C	109.5
O2—Mn1—O1	83.96 (6)	H5A—C5—H5C	109.5
O1^i—Mn1—O1	176.42 (10)	H5B—C5—H5C	109.5
O2^i—Mn1—N11^i	163.09 (7)	C2—O1—Mn1	126.41 (16)
O2—Mn1—N11^i	92.95 (7)	C4—O2—Mn1	128.08 (16)
O1^i—Mn1—N11^i	87.07 (6)	C11—N11—C15	118.14 (19)
O1—Mn1—N11^i	90.04 (7)	C11—N11—Mn1	126.04 (15)
O2^i—Mn1—N11	92.95 (7)	C15—N11—Mn1	115.82 (14)
O2—Mn1—N11	163.09 (7)	N11—C11—C12	122.9 (2)
O1^i—Mn1—N11	90.04 (6)	N11—C11—H11	118.5
O1—Mn1—N11	87.07 (6)	C12—C11—H11	118.5
N11^i—Mn1—N11	72.71 (9)	C13—C12—C11	119.4 (2)
C2—C1—H1A	109.5	C13—C12—H12	120.3
C2—C1—H1B	109.5	C11—C12—H12	120.3
H1A—C1—H1B	109.5	C12—C13—C14	119.7 (2)
C2—C1—H1C	109.5	C12—C13—H13	120.2
H1A—C1—H1C	109.5	C14—C13—H13	120.2
H1B—C1—H1C	109.5	C15—C14—C13	116.9 (2)
O1—C2—C3	125.5 (2)	C15—C14—C16	119.8 (2)
O1—C2—C1	116.3 (2)	C13—C14—C16	123.3 (2)
C3—C2—C1	118.2 (2)	N11—C15—C14	123.0 (2)
C4—C3—C2	125.7 (2)	N11—C15—C15^i	117.82 (12)
C4—C3—H3	117.1	C14—C15—C15^i	119.19 (13)
C2—C3—H3	117.1	C16^i—C16—C14	120.99 (13)
O2—C4—C3	125.5 (2)	C16^i—C16—H16	119.5
O2—C4—C5	115.8 (2)	C14—C16—H16	119.5
C3—C4—C5	118.7 (2)

Symmetry code: (i) −x+1, y, −z+3/2.