Bis[di­hydro­bis­(pyrazol-1-yl-κN2)borato]bis(methanol-κO)iron(II)

Ossinger, S.; Näther, C.; Tuczek, F.

doi:10.1107/S2414314616012529

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 8| August 2016| x161252

doi:10.1107/S2414314616012529

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Bis[dihydrobis(pyrazol-1-yl-κN²)borato]bis(methanol-κO)iron(II)

Sascha Ossinger,^a ^* Christian Näther ^a and Felix Tuczek ^a

^aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth-Strasse 2, 24118 Kiel, Germany
^*Correspondence e-mail: sossinger@ac.uni-kiel.de

Edited by M. Bolte, Goethe-Universität Frankfurt Germany (Received 29 July 2016; accepted 3 August 2016; online 9 August 2016)

The structure determination was undertaken as part of a project on the synthesis of new spin-crossover compounds based on octahedral Fe^II bis(pyrazolyl)borate complexes. The asymmetric unit of the title compound, [Fe(H₂B(pz)₂)₂(CH₃OH)₂] [H₂B(pz)₂ = dihydrobis(pyrazol-1-yl)borate, C₆H₈BN₄], consists of one Fe^II cation that is located on a centre of inversion, as well as one methanol molecule and one H₂B(pz)₂ dianion that occupy general positions. In the crystal, the Fe^II cations are coordinated by two methanol molecules and four N atoms of two H₂B(pz)₂ anions within a slightly distorted octahedron. Bond lengths and angles between the Fe^II atom and the H₂B(pz)₂ anion are comparable to those in related Fe^II complexes.

Keywords: crystal structure; discrete complex; iron(II) bis(pyrazolyl)borate.

CCDC reference: 1497420

Structure description

Concerning the background of this project, see Naggert et al. (2015 ). For related crystal structures of discrete octahedral Fe^II bis(pyrazolyl)borate complexes with N-donor ligands, see: Real et al. (1997 ); Thompson et al. (2004 ); Milek et al. (2013 ); Nihei et al. (2013 ); Kulmaczewski et al. (2014 ); Naggert et al. (2015). The title compound is illustrated in Fig. 1. Despite the presence of a hydroxy group, classical hydrogen-bonding interactions are not evident in the crystal structure.

Figure 1
Perspective view of the title compound with the atom labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry code for the generation of equivalent atoms: (i) −x, −y + 1, −z + 1.]

Synthesis and crystallization

Iron(II) perchlorate hydrate and solvents were purchased by Sigma–Aldrich. All reactions were carried out using dry solvents and under an inert atmosphere. Potassium dihydrobis(pyrazolyl)borate K[H₂B(pz)₂] and [Fe(H₂B(pz)₂)₂(CH₃OH)₂] were prepared according to literature methods (Trofimenko, 1967 ; Real et al., 1997).

A solution of K[H₂B(pz)₂] (283 mg, 1.52 mmol) in methanol (3 ml) was added dropwise to a solution of Fe(ClO₄)₂·6H₂O (276 mg, 0.76 mmol) in methanol (1 ml). The yellow Fe[H₂B(pz)₂]₂ solution was stirred for 10 min at room temperature. The resulting KClO₄ precipitate was removed by filtration and washed with methanol (6 ml). After further stirring for one h the solution was stored at 245 K. After four days colorless crystals of [Fe(H₂B(pz)₂)₂(CH₃OH)₂] were collected by suction filtration. They decompose in air within a few days.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	[Fe(C₆H₈BN₄)₂(CH₄O)₂]
M_r	413.88
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	170
a, b, c (Å)	9.7430 (5), 8.6535 (3), 12.3173 (6)
β (°)	111.670 (4)
V (Å³)	965.09 (8)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.81
Crystal size (mm)	0.20 × 0.12 × 0.06

Data collection
Diffractometer	Stoe IPDS2
Absorption correction	Numerical (X-RED and X-SHAPE; Stoe & Cie, 2008 )
T_min, T_max	0.781, 0.898
No. of measured, independent and observed [I > 2σ(I)] reflections	11312, 2103, 1898
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.089, 1.07
No. of reflections	2103
No. of parameters	125
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.45
Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), XP in SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1497420

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2414314616012529/bt4021sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616012529/bt4021Isup2.hkl

checkCIF report

Computing details top

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: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis[dihydrobis(pyrazol-1-yl-κN²)borato]bis(methanol-κO)iron(II) top

Crystal data top

[Fe(C₆H₈B₂N₄)₂(CH₄O)₂]	F(000) = 432
M_r = 413.88	D_x = 1.424 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.7430 (5) Å	Cell parameters from 11751 reflections
b = 8.6535 (3) Å	θ = 2.3–27.0°
c = 12.3173 (6) Å	µ = 0.81 mm⁻¹
β = 111.670 (4)°	T = 170 K
V = 965.09 (8) Å³	Block, colorless
Z = 2	0.20 × 0.12 × 0.06 mm

Data collection top

Stoe IPDS-2 diffractometer	1898 reflections with I > 2σ(I)
ω scans	R_int = 0.026
Absorption correction: numerical (X-RED and X-SHAPE; Stoe & Cie, 2008)	θ_max = 27.0°, θ_min = 2.3°
T_min = 0.781, T_max = 0.898	h = −12→12
11312 measured reflections	k = −11→11
2103 independent reflections	l = −15→15

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.0485P)² + 0.3892P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2103 reflections	Δρ_max = 0.25 e Å⁻³
125 parameters	Δρ_min = −0.45 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
Fe1	0.0000	0.5000	0.5000	0.02887 (12)
N1	0.20696 (15)	0.55724 (18)	0.64018 (12)	0.0315 (3)
N2	0.31387 (15)	0.64416 (17)	0.62205 (13)	0.0306 (3)
N3	0.09829 (15)	0.55320 (19)	0.37541 (13)	0.0314 (3)
N4	0.22449 (15)	0.63870 (17)	0.40243 (13)	0.0310 (3)
B1	0.2792 (2)	0.7456 (2)	0.51128 (18)	0.0339 (4)
H1A	0.3691	0.8017	0.5143	0.041*
H1B	0.2021	0.8225	0.5069	0.041*
C1	0.44303 (18)	0.6245 (2)	0.71101 (16)	0.0344 (4)
H1	0.5336	0.6730	0.7186	0.041*
C2	0.4231 (2)	0.5218 (2)	0.79007 (16)	0.0365 (4)
H2	0.4947	0.4860	0.8614	0.044*
C3	0.2736 (2)	0.4828 (2)	0.74114 (16)	0.0350 (4)
H3	0.2258	0.4128	0.7750	0.042*
C4	0.2818 (2)	0.6172 (2)	0.32000 (17)	0.0361 (4)
H4	0.3698	0.6636	0.3193	0.043*
C5	0.1932 (2)	0.5174 (2)	0.23664 (17)	0.0383 (4)
H5	0.2059	0.4823	0.1679	0.046*
C6	0.0806 (2)	0.4795 (2)	0.27593 (16)	0.0353 (4)
H6	0.0019	0.4105	0.2372	0.042*
O1	0.09492 (14)	0.26492 (15)	0.51071 (11)	0.0370 (3)
H1O1	0.0844	0.2074	0.5620	0.056*
C11	0.2429 (2)	0.2333 (2)	0.51817 (19)	0.0433 (4)
H11A	0.2564	0.2732	0.4483	0.065*
H11B	0.2599	0.1214	0.5236	0.065*
H11C	0.3133	0.2836	0.5877	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.02591 (19)	0.0335 (2)	0.02633 (19)	−0.00137 (13)	0.00856 (13)	−0.00076 (13)
N1	0.0277 (7)	0.0358 (8)	0.0289 (7)	−0.0039 (6)	0.0082 (6)	−0.0006 (6)
N2	0.0269 (7)	0.0315 (7)	0.0317 (7)	−0.0026 (5)	0.0090 (6)	−0.0022 (6)
N3	0.0286 (7)	0.0362 (7)	0.0296 (7)	−0.0034 (6)	0.0111 (6)	−0.0008 (6)
N4	0.0287 (7)	0.0330 (7)	0.0320 (7)	−0.0015 (6)	0.0121 (6)	0.0018 (6)
B1	0.0330 (9)	0.0320 (10)	0.0357 (10)	−0.0018 (8)	0.0115 (8)	0.0011 (8)
C1	0.0267 (8)	0.0381 (9)	0.0350 (9)	−0.0009 (7)	0.0072 (7)	−0.0035 (7)
C2	0.0331 (9)	0.0401 (10)	0.0310 (8)	0.0034 (7)	0.0055 (7)	−0.0008 (7)
C3	0.0366 (9)	0.0369 (9)	0.0299 (8)	−0.0016 (7)	0.0105 (7)	0.0010 (7)
C4	0.0350 (9)	0.0369 (9)	0.0406 (9)	0.0015 (7)	0.0190 (7)	0.0038 (7)
C5	0.0440 (10)	0.0388 (10)	0.0367 (9)	0.0022 (8)	0.0203 (8)	−0.0005 (7)
C6	0.0365 (9)	0.0363 (9)	0.0325 (9)	−0.0010 (7)	0.0122 (7)	−0.0033 (7)
O1	0.0362 (6)	0.0355 (7)	0.0398 (7)	−0.0003 (5)	0.0144 (5)	0.0009 (5)
C11	0.0380 (10)	0.0438 (11)	0.0480 (11)	0.0066 (8)	0.0157 (9)	−0.0003 (9)

Geometric parameters (Å, º) top

Fe1—N3ⁱ	2.1376 (14)	C1—C2	1.384 (3)
Fe1—N3	2.1376 (14)	C1—H1	0.9500
Fe1—N1ⁱ	2.1728 (14)	C2—C3	1.396 (3)
Fe1—N1	2.1729 (14)	C2—H2	0.9500
Fe1—O1	2.2183 (13)	C3—H3	0.9500
Fe1—O1ⁱ	2.2183 (13)	C4—C5	1.375 (3)
N1—C3	1.337 (2)	C4—H4	0.9500
N1—N2	1.368 (2)	C5—C6	1.392 (3)
N2—C1	1.340 (2)	C5—H5	0.9500
N2—B1	1.551 (2)	C6—H6	0.9500
N3—C6	1.335 (2)	O1—C11	1.437 (2)
N3—N4	1.367 (2)	O1—H1O1	0.8400
N4—C4	1.340 (2)	C11—H11A	0.9800
N4—B1	1.552 (2)	C11—H11B	0.9800
B1—H1A	0.9900	C11—H11C	0.9800
B1—H1B	0.9900

N3ⁱ—Fe1—N3	180.0	N2—B1—H1B	110.0
N3ⁱ—Fe1—N1ⁱ	89.49 (5)	N4—B1—H1B	110.0
N3—Fe1—N1ⁱ	90.51 (5)	H1A—B1—H1B	108.4
N3ⁱ—Fe1—N1	90.51 (5)	N2—C1—C2	108.88 (16)
N3—Fe1—N1	89.49 (5)	N2—C1—H1	125.6
N1ⁱ—Fe1—N1	180.0	C2—C1—H1	125.6
N3ⁱ—Fe1—O1	92.71 (5)	C1—C2—C3	104.27 (16)
N3—Fe1—O1	87.29 (5)	C1—C2—H2	127.9
N1ⁱ—Fe1—O1	94.73 (5)	C3—C2—H2	127.9
N1—Fe1—O1	85.27 (5)	N1—C3—C2	110.88 (16)
N3ⁱ—Fe1—O1ⁱ	87.29 (5)	N1—C3—H3	124.6
N3—Fe1—O1ⁱ	92.71 (5)	C2—C3—H3	124.6
N1ⁱ—Fe1—O1ⁱ	85.27 (5)	N4—C4—C5	109.31 (16)
N1—Fe1—O1ⁱ	94.73 (5)	N4—C4—H4	125.3
O1—Fe1—O1ⁱ	180.0	C5—C4—H4	125.3
C3—N1—N2	106.20 (14)	C4—C5—C6	104.27 (17)
C3—N1—Fe1	128.24 (12)	C4—C5—H5	127.9
N2—N1—Fe1	122.32 (11)	C6—C5—H5	127.9
C1—N2—N1	109.77 (14)	N3—C6—C5	110.81 (17)
C1—N2—B1	128.69 (15)	N3—C6—H6	124.6
N1—N2—B1	121.54 (13)	C5—C6—H6	124.6
C6—N3—N4	106.37 (14)	C11—O1—Fe1	124.41 (12)
C6—N3—Fe1	128.01 (13)	C11—O1—H1O1	103.7
N4—N3—Fe1	122.89 (11)	Fe1—O1—H1O1	115.1
C4—N4—N3	109.23 (15)	O1—C11—H11A	109.5
C4—N4—B1	129.11 (15)	O1—C11—H11B	109.5
N3—N4—B1	121.61 (13)	H11A—C11—H11B	109.5
N2—B1—N4	108.45 (15)	O1—C11—H11C	109.5
N2—B1—H1A	110.0	H11A—C11—H11C	109.5
N4—B1—H1A	110.0	H11B—C11—H11C	109.5

Symmetry code: (i) −x, −y+1, −z+1.

Acknowledgements

This work was supported by the DFG (SFB 677 Function by Switching). We gratefully acknowledge financial support by the State of Schleswig–Holstein.

References

Kulmaczewski, R., Shepherd, H. J., Cespedes, O. & Halcrow, M. A. (2014). Inorg. Chem. 53, 9809–9817. CSD CrossRef CAS PubMed Google Scholar
Milek, M., Heinemann, F. W. & Khusniyarov, M. M. (2013). Inorg. Chem. 52, 11585–11592. CSD CrossRef CAS PubMed Google Scholar
Naggert, H., Rudnik, J., Kipgen, L., Bernien, M., Nickel, F., Arruda, L. M., Kuch, W., Näther, C. & Tuczek, F. (2015). J. Mater. Chem. C, 3, 7870–7877. CSD CrossRef CAS Google Scholar
Nihei, M., Suzuki, Y., Kimura, N., Kera, Y. & Oshio, H. (2013). Chem. Eur. J. 19, 6946–6949. CSD CrossRef CAS PubMed Google Scholar
Real, J. A., Muñoz, M. C., Faus, J. & Solans, X. (1997). Inorg. Chem. 36, 3008–3013. CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Stoe & Cie (2008). X-AREA, X-RED and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Thompson, A. L., Goeta, A. E., Real, J. A., Galet, A. & Muñoz, M. C. (2004). Chem. Commun. pp. 1390–1391. Web of Science CSD CrossRef Google Scholar
Trofimenko, S. (1967). J. Am. Chem. Soc. 89, 3170–3177. CrossRef CAS Web of Science Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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