trans-Di­aqua­bis­(1,1,1,5,5,5-hexa­fluoropenta­ne-2,4-dionato-κ2O,O′)cobalt(II) dihydrate

Tominaga, T.; Mochida, T.

doi:10.1107/S2414314617000025

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 1| January 2017| x170002

https://doi.org/10.1107/S2414314617000025

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trans-Diaquabis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato-κ²O,O′)cobalt(II) dihydrate

Takumi Tominaga ^a and Tomoyuki Mochida ^a ^*

^aDepartment of Chemistry, Graduate School of Science, Kobe University, Kobe, Hyogo 657-8501, Japan
^*Correspondence e-mail: tmochida@platinum.kobe-u.ac.jp

Edited by M. Weil, Vienna University of Technology, Austria (Received 19 December 2016; accepted 2 January 2017; online 6 January 2017)

The Co^II atom in the mononuclear title compound, [Co(C₅HF₆O₂)₂(H₂O)₂]·2H₂O, is situated on an inversion centre and exhibits a slightly distorted octahedral coordination sphere. In the crystal, molecules are arranged in layers parallel to (100), held together by O—H⋯O and O—H⋯F hydrogen bonds.

Keywords: crystal structure; Co^II complex; 1,1,1,5,5,5-hexafluoropentane-2,4-dionate; hydrogen bonding; hydrate compounds..

CCDC reference: 1525259

Structure description

Metal complexes with hfac⁻ ligands (hfac⁻ = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate, C₅HF₆O₂) can occur with various numbers of aqua ligands [M(hfac)₂(H₂O)_n] (Maverick et al., 2002 ). These compounds are useful precursors of numerous complexes used in supramolecular chemistry (Horikoshi et al., 2005 ).

An isomer of the molecular entity cis-[Co(hfac)₂(H₂O)₂] (Petrukhina et al., 2005 ) was now obtained as a dihydrate with a trans-configuration about the Co^II atom, representing the title compound [Co(hfac)₂(H₂O)₂]·2H₂O (Fig. 1). The metal cation is situated on an inversion centre, hence only half of the complex is present in the asymmetric unit. The symmetry-related hfac⁻ ligands chelate the Co^II atom in the equatorial plane, the slightly distorted coordination sphere being completed by two axially bound water molecules. The hydrogen atoms of the two solvate water molecules hydrogen-bond to the two O atom pairs of the hfac⁻ ligands, whereas the hydrogen atoms of the aqua ligands hydrogen-bond to the oxygen atoms of the solvate water molecules which leads to the formation of a two-dimensional network structure extending parallel to (100) (Table 1, Fig. 2). Additional intralayer O—H⋯F hydrogen bonds between the solvate water molecules and the F atoms of the hfac⁻ ligands are present (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H5⋯O2	0.88 (3)	2.13 (3)	2.853 (2)	140 (3)
O4—H5⋯F6	0.88 (3)	2.32 (3)	3.105 (3)	148 (3)
O4—H4⋯O1ⁱ	0.77 (3)	2.03 (3)	2.766 (2)	160 (3)
O4—H4⋯F3ⁱ	0.77 (3)	2.55 (3)	3.086 (3)	129 (3)
O3—H2⋯O4ⁱⁱ	0.76 (3)	2.00 (3)	2.756 (3)	175 (3)
O3—H1⋯O4ⁱⁱⁱ	0.84 (3)	1.85 (3)	2.687 (3)	175 (3)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x, y+1, z.

Figure 1
The molecular components in the title structure, with displacement ellipsoids drawn at the 50% probability level. Primed atoms are related to the non-primed atoms by the symmetry operation −x + 1, −y + 1, −z + 1.

Figure 2
Packing diagram of the title structure in a view along [100]. O–H⋯O interactions are illustrated as dashed lines.

A search of the Cambridge Structural Database (Groom et al., 2016 ) revealed no other examples of structurally characterized dihydrate crystals with formula [M(hfac)₂(H₂O)_n]·2H₂O. In the monohydrate crystals of trans-[M(hfac)₂(H₂O)₂]·H₂O [M = Zn (Adams et al., 1986 ), Mn (Dickman et al., 1997 ), and Cu (Maverick et al., 2002)], of which the Zn and Mn compounds are isotypic with each other, the solvate water molecule forms hydrogen bonds with two of the four oxygen atoms of the hfac⁻ ligands in the complex, whereas the other two oxygen atoms form hydrogen bonds with the aqua ligands of an adjacent complex. In contrast, cis-[M(hfac)₂(H₂O)₂] [M = Co (Petrukhina et al., 2005), Zn (Adams & Allen, 1986), Ni (Romero et al., 1992 ) and Mn (Troyanov et al., 1999 )] form no crystals with additional solvate water molecules, and the crystals obtained are isotypic with each other. Thus, the cis- and trans-[M(hfac)₂(H₂O)₂] isomers occur as anhydrate and dihydrate crystals, respectively, for the Co, Zn, and Mn complexes.

Synthesis and crystallization

Slow evaporation of a dichloromethane solution of commercially available Co(hfac)₂·nH₂O (12 mg) and a tetranuclear ruthenium complex produced pale orange platy crystals of the title compound (7 mg).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[Co(C₅HF₆O₂)₂(H₂O)]·2H₂O
M_r	545.11
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	11.139 (7), 6.979 (4), 12.546 (8)
β (°)	102.221 (7)
V (Å³)	953.2 (10)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.05
Crystal size (mm)	0.15 × 0.14 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2015 )
T_min, T_max	0.83, 0.90
No. of measured, independent and observed [I > 2σ(I)] reflections	4980, 2085, 1897
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.080, 1.09
No. of reflections	2085
No. of parameters	158
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.33
Computer programs: APEX2 and SAINT (Bruker, 2015), SHELXT (Sheldrick, 2015a ), SHELXL2014/7 (Sheldrick, 2015b ), ORTEP for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1525259

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617000025/wm4036sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617000025/wm4036Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: ORTEP for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

trans-Diaquabis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato-κ²O,O')cobalt(II) dihydrate top

Crystal data top

[Co(C₅HF₆O₂)₂(H₂O)]·2H₂O	F(000) = 538
M_r = 545.11	D_x = 1.899 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.139 (7) Å	Cell parameters from 3472 reflections
b = 6.979 (4) Å	θ = 3.3–28.7°
c = 12.546 (8) Å	µ = 1.05 mm⁻¹
β = 102.221 (7)°	T = 100 K
V = 953.2 (10) Å³	Plate, clear light orange
Z = 2	0.15 × 0.14 × 0.10 mm

Data collection top

Bruker APEXII CCD area detector diffractometer	2085 independent reflections
Bruker Helios multilayer confocal mirror monochromator	1897 reflections with I > 2σ(I)
Detector resolution: 8.3333 pixels mm^-1	R_int = 0.033
phi an_diffrn_radiation_type scans	θ_max = 27.1°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2015)	h = −13→14
T_min = 0.83, T_max = 0.90	k = −8→6
4980 measured reflections	l = −15→16

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.080	w = 1/[σ²(F_o²) + (0.0286P)² + 0.6401P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
2085 reflections	Δρ_max = 0.46 e Å⁻³
158 parameters	Δρ_min = −0.33 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.79557 (17)	0.8251 (3)	0.70389 (15)	0.0275 (4)
C2	0.73400 (16)	0.6744 (3)	0.62063 (14)	0.0215 (4)
C3	0.80755 (17)	0.5324 (3)	0.59026 (16)	0.0259 (4)
H3	0.8933	0.5359	0.6201	0.031*
C4	0.76128 (16)	0.3842 (3)	0.51766 (14)	0.0224 (4)
C5	0.85596 (17)	0.2501 (3)	0.48259 (16)	0.0280 (4)
Co1	0.5	0.5	0.5	0.01650 (11)
F1	0.77683 (13)	0.7802 (2)	0.80271 (10)	0.0447 (3)
F2	0.91612 (11)	0.8405 (2)	0.71227 (11)	0.0430 (3)
F3	0.74684 (13)	0.99850 (17)	0.67922 (12)	0.0421 (3)
F4	0.88486 (14)	0.3160 (2)	0.39182 (12)	0.0557 (4)
F5	0.95906 (12)	0.2319 (2)	0.55607 (13)	0.0543 (4)
F6	0.81060 (12)	0.0745 (2)	0.46112 (13)	0.0465 (4)
H1	0.508 (2)	0.769 (4)	0.362 (2)	0.038 (7)*
H2	0.484 (3)	0.612 (5)	0.304 (2)	0.047 (8)*
H4	0.481 (3)	0.085 (4)	0.366 (2)	0.042 (7)*
H5	0.601 (3)	0.087 (5)	0.388 (2)	0.051 (8)*
O1	0.61928 (11)	0.69704 (18)	0.59076 (10)	0.0219 (3)
O2	0.65242 (11)	0.34813 (19)	0.47266 (10)	0.0234 (3)
O3	0.49099 (16)	0.6521 (2)	0.36142 (12)	0.0318 (3)
O4	0.53489 (14)	0.02958 (19)	0.35107 (11)	0.0238 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0239 (9)	0.0314 (10)	0.0260 (9)	−0.0047 (8)	0.0026 (7)	−0.0066 (8)
C2	0.0218 (8)	0.0226 (9)	0.0197 (8)	−0.0037 (7)	0.0035 (6)	−0.0016 (7)
C3	0.0197 (8)	0.0304 (10)	0.0260 (9)	−0.0010 (7)	0.0018 (7)	−0.0044 (8)
C4	0.0212 (8)	0.0244 (9)	0.0221 (8)	0.0024 (7)	0.0054 (7)	−0.0007 (7)
C5	0.0217 (9)	0.0298 (10)	0.0322 (10)	0.0035 (8)	0.0052 (7)	−0.0047 (8)
Co1	0.01709 (18)	0.01662 (18)	0.01582 (17)	−0.00037 (11)	0.00357 (12)	−0.00182 (11)
F1	0.0567 (8)	0.0541 (9)	0.0234 (6)	−0.0155 (7)	0.0089 (6)	−0.0115 (6)
F2	0.0248 (6)	0.0510 (8)	0.0512 (8)	−0.0109 (6)	0.0037 (5)	−0.0231 (6)
F3	0.0424 (8)	0.0254 (7)	0.0518 (9)	−0.0030 (5)	−0.0048 (6)	−0.0113 (5)
F4	0.0596 (9)	0.0653 (10)	0.0540 (9)	0.0242 (8)	0.0388 (8)	0.0114 (8)
F5	0.0313 (7)	0.0642 (10)	0.0592 (9)	0.0217 (7)	−0.0089 (6)	−0.0226 (8)
F6	0.0346 (7)	0.0317 (7)	0.0748 (10)	0.0046 (6)	0.0148 (6)	−0.0181 (7)
O1	0.0214 (6)	0.0209 (6)	0.0226 (6)	−0.0017 (5)	0.0028 (5)	−0.0047 (5)
O2	0.0199 (6)	0.0241 (7)	0.0261 (6)	0.0006 (5)	0.0044 (5)	−0.0065 (5)
O3	0.0598 (10)	0.0190 (7)	0.0172 (7)	−0.0053 (7)	0.0099 (6)	−0.0018 (5)
O4	0.0297 (7)	0.0202 (6)	0.0214 (6)	0.0008 (6)	0.0056 (6)	−0.0034 (5)

Geometric parameters (Å, º) top

C1—F2	1.329 (2)	C5—F6	1.331 (3)
C1—F3	1.336 (3)	Co1—O3ⁱ	2.0215 (17)
C1—F1	1.337 (2)	Co1—O3	2.0215 (17)
C1—C2	1.538 (3)	Co1—O1	2.0766 (14)
C2—O1	1.263 (2)	Co1—O1ⁱ	2.0766 (14)
C2—C3	1.389 (3)	Co1—O2	2.0904 (15)
C3—C4	1.402 (3)	Co1—O2ⁱ	2.0904 (15)
C3—H3	0.95	O3—H1	0.84 (3)
C4—O2	1.250 (2)	O3—H2	0.76 (3)
C4—C5	1.542 (3)	O4—H4	0.77 (3)
C5—F5	1.318 (2)	O4—H5	0.88 (3)
C5—F4	1.330 (3)

F2—C1—F3	107.40 (17)	O3ⁱ—Co1—O3	180.0
F2—C1—F1	107.40 (16)	O3ⁱ—Co1—O1	88.09 (7)
F3—C1—F1	106.94 (16)	O3—Co1—O1	91.91 (7)
F2—C1—C2	114.03 (16)	O3ⁱ—Co1—O1ⁱ	91.91 (7)
F3—C1—C2	111.18 (16)	O3—Co1—O1ⁱ	88.09 (7)
F1—C1—C2	109.57 (16)	O1—Co1—O1ⁱ	180.00 (5)
O1—C2—C3	128.77 (17)	O3ⁱ—Co1—O2	88.89 (6)
O1—C2—C1	113.18 (16)	O3—Co1—O2	91.11 (6)
C3—C2—C1	118.03 (16)	O1—Co1—O2	88.74 (6)
C2—C3—C4	123.17 (17)	O1ⁱ—Co1—O2	91.26 (6)
C2—C3—H3	118.4	O3ⁱ—Co1—O2ⁱ	91.11 (6)
C4—C3—H3	118.4	O3—Co1—O2ⁱ	88.89 (6)
O2—C4—C3	129.04 (17)	O1—Co1—O2ⁱ	91.26 (6)
O2—C4—C5	113.93 (16)	O1ⁱ—Co1—O2ⁱ	88.74 (6)
C3—C4—C5	116.96 (16)	O2—Co1—O2ⁱ	180.00 (7)
F5—C5—F4	107.42 (18)	C2—O1—Co1	124.71 (12)
F5—C5—F6	106.87 (17)	C4—O2—Co1	124.59 (12)
F4—C5—F6	107.21 (17)	Co1—O3—H1	122.6 (18)
F5—C5—C4	113.96 (17)	Co1—O3—H2	127 (2)
F4—C5—C4	109.78 (17)	H1—O3—H2	110 (3)
F6—C5—C4	111.30 (16)	H4—O4—H5	105 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H5···O2	0.88 (3)	2.13 (3)	2.853 (2)	140 (3)
O4—H5···F6	0.88 (3)	2.32 (3)	3.105 (3)	148 (3)
O4—H4···O1ⁱ	0.77 (3)	2.03 (3)	2.766 (2)	160 (3)
O4—H4···F3ⁱ	0.77 (3)	2.55 (3)	3.086 (3)	129 (3)
O3—H2···O4ⁱⁱ	0.76 (3)	2.00 (3)	2.756 (3)	175 (3)
O3—H1···O4ⁱⁱⁱ	0.84 (3)	1.85 (3)	2.687 (3)	175 (3)

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

Acknowledgements

This work was financially supported by KAKENHI (grant number 16H04132).

Funding information

Funding for this research was provided by: Japan Society for the Promotion of Science (award No. KAKENHI: 16H04132).

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