High-temperature phase of trans-tetra­aqua­bis­(tri­fluoro­acetato-O)­manganese(II)

The title compound, [Mn(CF₃COO)₂(H₂O)₄], crystallizes in the monoclinic space group C2/c. At about 215 K, it undergoes a reversible phase transition, which leads to crystal twinning. The crystal structure of the high-temperature phase was determined at 220 K. The Mn²⁺ ion lies on a twofold axis and is octahedrally coordinated by two monodentate tri­fluoro­acetate ligands in apical positions and by four equatorial aqua ligands, two of which lie on the twofold axis. Hydro­gen-bonding interactions connect the complex mol­ecules, generating a three-dimensional network.

Computing details

Data collection: KM4CCD Software (Kuma Diffraction, 1995–1999); cell refinement: KM4CCD Software (Kuma Diffraction, 1995–1999); data reduction: KM4CCD Software (Kuma Diffraction, 1995–1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 1990).

trans-tetraaquabis(trifluoroacetato)manganese(II)

Crystal data

[Mn(C2F3O2)2(H2O)4]	F(000) = 700
Mr = 353.04	Dx = 1.888 Mg m^−3 Dm = 1.875 Mg m^−3 Dm measured by flotation in dibromoethane/cyclohexane
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.383 (5) Å	Cell parameters from 1518 reflections
b = 13.038 (4) Å	θ = 4–27°
c = 8.372 (3) Å	µ = 1.17 mm^−1
β = 121.76 (4)°	T = 220 K
V = 1242.1 (7) Å^3	Sphere, pale-pink
Z = 4	0.1 mm (radius)

Data collection

Kuma KM4CCD κ-geometry diffractometer	1331 independent reflections
Radiation source: fine-focus sealed tube	1144 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ω scans	θmax = 27°, θmin = 4°
Absorption correction: for a sphere International Tables for Crystallography, 1992, Vol. C	h = −16→16
Tmin = 0.840, Tmax = 0.841	k = −16→16
3808 measured reflections	l = −10→8

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)] = 0.042	Hydrogen site location: difference Fourier map
wR(F^2) = 0.109	All H-atom parameters refined
S = 1.11	Calculated w = 1/[σ^2(Fo^2) + (0.0497P)^2 + 1.7678P] where P = (Fo^2 + 2Fc^2)/3
1331 reflections	(Δ/σ)max = 0.001
117 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.40 e Å^−3

Special details

Experimental. The data collection strategy nominally covered a full Ewald sphere by a combination of four set of exposures. Each set had a different φ angle for the crystal and each exposure of 40 s covered 0.75 ° in ω. The crystal–to–detector distance was 65 mm and the detector swing angle was 30 °. There were 612 frames. Crystal decay was monitored by repeating the initial frames at the end of data collection and analyzing the duplicate reflections.

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn	0.5000	0.39739 (4)	0.2500	0.0374 (2)
O1	0.35033 (16)	0.40385 (14)	0.2888 (3)	0.0424 (5)
O2	0.28522 (19)	0.24231 (16)	0.2210 (3)	0.0553 (6)
O3	0.61625 (17)	0.40168 (16)	0.5573 (3)	0.0406 (5)
O4	0.5000	0.5628 (2)	0.2500	0.0452 (7)
O5	0.5000	0.2336 (3)	0.2500	0.0741 (13)
C1	0.2799 (2)	0.3321 (2)	0.2585 (4)	0.0414 (6)
C2	0.1738 (3)	0.3653 (3)	0.2714 (6)	0.0605 (9)
F1	0.1033 (4)	0.4225 (5)	0.1326 (8)	0.150 (2)	0.876 (6)
F2	0.2068 (3)	0.4170 (4)	0.4259 (6)	0.1206 (19)	0.876 (6)
F3	0.1138 (3)	0.2873 (3)	0.2753 (7)	0.1189 (19)	0.876 (6)
F4	0.1614 (16)	0.4643 (13)	0.277 (3)	0.058 (5)*	0.124 (6)
F5	0.176 (2)	0.339 (2)	0.411 (4)	0.096 (8)*	0.124 (6)
F6	0.0758 (16)	0.3412 (17)	0.130 (3)	0.062 (6)*	0.124 (6)
H3	0.647 (3)	0.460 (3)	0.608 (5)	0.054 (10)*
H31	0.667 (4)	0.357 (3)	0.618 (6)	0.077 (13)*
H4	0.468 (3)	0.595 (2)	0.295 (5)	0.055 (10)*
H5	0.445 (4)	0.212 (4)	0.236 (7)	0.103 (18)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn	0.0349 (3)	0.0312 (3)	0.0554 (4)	0.000	0.0301 (3)	0.000
O1	0.0365 (10)	0.0403 (10)	0.0609 (12)	−0.0058 (7)	0.0329 (9)	−0.0050 (8)
O2	0.0459 (12)	0.0477 (13)	0.0830 (15)	−0.0131 (9)	0.0413 (12)	−0.0144 (11)
O3	0.0364 (10)	0.0356 (11)	0.0522 (11)	0.0060 (8)	0.0250 (9)	0.0027 (9)
O4	0.0568 (18)	0.0308 (14)	0.0683 (19)	0.000	0.0468 (16)	0.000
O5	0.070 (3)	0.0344 (17)	0.152 (4)	0.000	0.082 (3)	0.000
C1	0.0344 (13)	0.0479 (16)	0.0459 (15)	−0.0051 (11)	0.0238 (12)	−0.0035 (12)
C2	0.0439 (17)	0.068 (2)	0.081 (2)	−0.0141 (16)	0.0410 (17)	−0.0196 (19)
F1	0.092 (3)	0.197 (5)	0.182 (5)	0.089 (3)	0.087 (3)	0.085 (4)
F2	0.093 (2)	0.161 (4)	0.160 (4)	−0.051 (2)	0.102 (3)	−0.097 (3)
F3	0.103 (2)	0.088 (2)	0.241 (5)	−0.047 (2)	0.142 (3)	−0.057 (3)

Geometric parameters (Å, º)

Mn—O5	2.136 (4)	O4—H4	0.82 (3)
Mn—O4	2.157 (3)	O5—H5	0.74 (5)
Mn—O1^i	2.193 (2)	C1—C2	1.541 (4)
Mn—O1	2.193 (2)	C2—F5	1.21 (2)
Mn—O3	2.198 (2)	C2—F6	1.261 (18)
Mn—O3^i	2.198 (2)	C2—F1	1.281 (6)
O1—C1	1.255 (3)	C2—F4	1.306 (18)
O2—C1	1.224 (3)	C2—F3	1.308 (4)
O3—H3	0.86 (4)	C2—F2	1.312 (5)
O3—H31	0.83 (4)
O5—Mn—O4	180.0	F1—C2—F3	107.8 (4)
O5—Mn—O1^i	92.20 (5)	F4—C2—F3	132.5 (8)
O4—Mn—O1^i	87.80 (5)	F5—C2—F2	50.6 (14)
O5—Mn—O1	92.20 (5)	F6—C2—F2	134.4 (9)
O4—Mn—O1	87.80 (5)	F1—C2—F2	107.5 (5)
O1^i—Mn—O1	175.60 (10)	F4—C2—F2	55.9 (8)
O5—Mn—O3	91.46 (6)	F3—C2—F2	105.4 (4)
O4—Mn—O3	88.54 (6)	F5—C2—C1	115.8 (12)
O1^i—Mn—O3	91.92 (9)	F6—C2—C1	113.9 (9)
O1—Mn—O3	87.97 (9)	F1—C2—C1	111.5 (3)
O5—Mn—O3^i	91.46 (6)	F4—C2—C1	114.9 (8)
O4—Mn—O3^i	88.54 (6)	F3—C2—C1	112.6 (3)
O1^i—Mn—O3^i	87.97 (9)	F2—C2—C1	111.7 (3)
O1—Mn—O3^i	91.92 (9)	F6—F1—F4	119.8 (14)
O3—Mn—O3^i	177.08 (12)	F6—F1—C2	63.0 (10)
C1—O1—Mn	126.04 (18)	F4—F1—C2	64.1 (9)
Mn—O3—H3	118 (2)	F5—F2—F4	113.8 (16)
Mn—O3—H31	123 (3)	F5—F2—C2	59.7 (13)
H3—O3—H31	107 (4)	F4—F2—C2	61.8 (9)
Mn—O4—H4	121 (2)	F5—F3—F6	109.3 (16)
Mn—O5—H5	112 (4)	F5—F3—C2	57.3 (13)
O2—C1—O1	128.8 (3)	F6—F3—C2	58.8 (9)
O2—C1—C2	117.8 (3)	F1—F4—F2	121.2 (15)
O1—C1—C2	113.4 (3)	F1—F4—C2	62.0 (9)
F5—C2—F6	108.9 (17)	F2—F4—C2	62.3 (9)
F5—C2—F1	132.5 (12)	F2—F5—F3	132 (2)
F6—C2—F1	52.1 (10)	F2—F5—C2	69.7 (16)
F5—C2—F4	100.7 (15)	F3—F5—C2	65.8 (14)
F6—C2—F4	101.0 (12)	F1—F6—F3	123.1 (15)
F1—C2—F4	53.9 (8)	F1—F6—C2	64.9 (10)
F5—C2—F3	56.9 (14)	F3—F6—C2	62.5 (9)
F6—C2—F3	58.7 (10)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1^ii	0.86 (4)	1.97 (4)	2.772 (3)	155 (3)
O3—H31···O2^iii	0.83 (4)	1.87 (4)	2.693 (3)	170 (4)
O4—H4···O3^ii	0.82 (3)	2.07 (3)	2.807 (2)	150 (3)
O5—H5···O2	0.74 (5)	2.11 (5)	2.757 (2)	146 (5)

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