Crystal structure of tetra­kis­(μ-n-butyrato-κ2O:O′)bis­[chlorido­rhenium(III)](Re—Re)

Thomson, M.P.; O'Rourke, N.F.; Wang, R.; Aquino, M.A.S.

doi:10.1107/S1600536814020273

metal-organic compounds

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Volume 70| Part 10| October 2014| Pages m349-m350

doi:10.1107/S1600536814020273

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Crystal structure of tetrakis(μ-n-butyrato-κ²O:O′)bis[chloridorhenium(III)](Re—Re)

Michael P. Thomson,^a Natasha F. O'Rourke,^a Ruiyao Wang ^b and Manuel A. S. Aquino ^a ^*

^aDepartment of Chemistry, St. Francis Xavier University, PO Box 5000, Antigonish, Nova Scotia, B2G 2W5, Canada, and ^bDepartment of Chemistry, Queen's University, Kingston, Ontario, K7L 3N6, Canada
^*Correspondence e-mail: maquino@stfx.ca

Edited by M. Weil, Vienna University of Technology, Austria (Received 30 August 2014; accepted 9 September 2014; online 13 September 2014)

With an inversion center at the mid-point of the two Re^III atoms, the title compound, [Re₂Cl₂{O₂C(CH₂)₂CH₃}₄], exhibits a paddle-wheel or lantern-type structure with four n-butyrate groups bridging two Re^III atoms in a syn–syn fashion. The axial chloride ligands together with the Re—Re quadruple bond [2.2330 (3) Å] complete an essentially octahedral geometry around each Re^III atom. There is little distortion, with an Re—Re—Cl bond angle of 176.18 (3)° and typical cis-O—Re—O bond angles ranging from 89.39 (11) to 90.68 (11)°. There are two molecules in the unit cell, and no significant intermolecular interactions were noticed between molecules in the crystal.

Keywords: crystal structure; dirhenium core; butyrate bridging ligand.

CCDC reference: 1023523

1. Related literature

For the synthesis and structure of five related structures, see: Taha & Wilkinson (1963 ); Calvo et al. (1969 ); Collins et al. (1979 ); Lydon et al. (2003 ).

2. Experimental

2.1. Crystal data

[Re₂(C₄H₇O₂)₄Cl₂]
M_r = 791.68
Monoclinic, P 2₁ /n
a = 6.7292 (4) Å
b = 12.0367 (8) Å
c = 14.6737 (9) Å
β = 99.262 (1)°
V = 1173.0 (1) Å³
Z = 2
Mo Kα radiation
μ = 10.57 mm⁻¹
T = 180 K
0.30 × 0.06 × 0.06 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2010 ) T_min = 0.144, T_max = 0.570
4625 measured reflections
2277 independent reflections
2077 reflections with I > 2σ(I)
R_int = 0.016

2.3. Refinement

R[F² > 2σ(F²)] = 0.019
wR(F²) = 0.049
S = 1.06
2277 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.90 e Å⁻³
Δρ_min = −1.32 e Å⁻³

Table 1
Selected bond lengths (Å)

Re1—O2ⁱ	2.008 (3)
Re1—O3	2.019 (2)
Re1—O4ⁱ	2.025 (2)
Re1—O1	2.026 (3)
Re1—Cl1	2.5135 (9)
Symmetry code: (i) -x+2, -y+1, -z+2.

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; 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.

Supporting information

CCDC reference: 1023523

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814020273/wm5055sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814020273/wm5055Isup2.hkl

checkCIF report

Synthesis and crystallization top

This compund was prepared following a method analogous to the procedure used by Taha & Wilkinson (1963). Rhenium trichloride (1.25 g, 4.27 mmol) was reacted with 13 ml of butyric acid and 0.5 ml of butyric anhydride at 423 K, with stirring, under a steady stream of nitrogen for five days. The dark solution was removed from heat and allowed to cool overnight. The brown product was collected via suction filtration and washed with a 50 ml portion of petroleum ether. The product was dried in vacuo for 24 hours and then re-crystallized from dichloromethane. Yield = 0.481g, (56.9 %).

Refinement top

All H atoms were placed in geometrically calculated positions, with C—H = 0.99 Å (CH₂), and 0.98 Å (CH₃), and refined as riding atoms, with U_iso(H) = 1.5U_eq(C) (CH₃) or 1.2U_eq(C) (CH₂).

Related literature top

For the synthesis and structure of five related structures, see: Taha & Wilkinson (1963); Calvo et al. (1969); Collins et al. (1979); Lydon et al. (2003).

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); 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 top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. Hydrogen atoms are drawn as small spheres of arbitrary radius. [Symmetry code i) -x + 2, -y + 1, -z + 2.]
	Fig. 2. The packing diagram for the title compound viewed along [100].

Tetrakis(µ-n-butyrato-κ²O:O')bis[chloridorhenium(III)](Re—Re) top

Crystal data top

[Re₂(C₄H₇O₂)₄Cl₂]	F(000) = 744
M_r = 791.68	D_x = 2.241 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3188 reflections
a = 6.7292 (4) Å	θ = 3.7–27.1°
b = 12.0367 (8) Å	µ = 10.57 mm⁻¹
c = 14.6737 (9) Å	T = 180 K
β = 99.262 (1)°	Needle, orange
V = 1173.0 (1) Å³	0.30 × 0.06 × 0.06 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	2277 independent reflections
Radiation source: fine-focus sealed tube	2077 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 26.0°, θ_min = 3.7°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −8→7
T_min = 0.144, T_max = 0.570	k = −12→14
4625 measured reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.019	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.049	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0278P)² + 0.2053P] where P = (F_o² + 2F_c²)/3
2277 reflections	(Δ/σ)_max = 0.005
129 parameters	Δρ_max = 0.90 e Å⁻³
0 restraints	Δρ_min = −1.32 e Å⁻³

Crystal data top

[Re₂(C₄H₇O₂)₄Cl₂]	V = 1173.0 (1) Å³
M_r = 791.68	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.7292 (4) Å	µ = 10.57 mm⁻¹
b = 12.0367 (8) Å	T = 180 K
c = 14.6737 (9) Å	0.30 × 0.06 × 0.06 mm
β = 99.262 (1)°

Data collection top

Bruker APEXII CCD diffractometer	2277 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2010)	2077 reflections with I > 2σ(I)
T_min = 0.144, T_max = 0.570	R_int = 0.016
4625 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.019	0 restraints
wR(F²) = 0.049	H-atom parameters constrained
S = 1.06	Δρ_max = 0.90 e Å⁻³
2277 reflections	Δρ_min = −1.32 e Å⁻³
129 parameters

Special details top

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.

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 > σ(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 (Å²) top

	x	y	z	U_iso*/U_eq
Re1	0.91824 (2)	0.559012 (11)	1.039538 (10)	0.02050 (7)
Cl1	0.71261 (17)	0.68750 (8)	1.12219 (8)	0.0397 (3)
O1	0.7020 (4)	0.57529 (19)	0.92707 (18)	0.0254 (6)
O2	0.8665 (4)	0.45750 (19)	0.84940 (19)	0.0256 (6)
O3	0.7697 (4)	0.42938 (19)	1.08438 (19)	0.0243 (6)
O4	0.9312 (4)	0.31123 (19)	1.00486 (18)	0.0241 (6)
C1	0.7167 (6)	0.5223 (3)	0.8532 (3)	0.0253 (8)
C2	0.5652 (6)	0.5386 (3)	0.7691 (3)	0.0308 (9)
H2A	0.4565	0.5877	0.7838	0.037*
H2B	0.5045	0.4661	0.7486	0.037*
C3	0.6593 (7)	0.5899 (4)	0.6916 (3)	0.0451 (12)
H3A	0.7561	0.5366	0.6719	0.054*
H3B	0.5526	0.6040	0.6380	0.054*
C4	0.7670 (9)	0.6974 (5)	0.7202 (5)	0.083 (2)
H4A	0.8092	0.7325	0.6662	0.125*
H4B	0.8857	0.6821	0.7666	0.125*
H4C	0.6761	0.7474	0.7464	0.125*
C5	0.8023 (6)	0.3306 (3)	1.0595 (3)	0.0247 (8)
C6	0.6899 (6)	0.2376 (3)	1.0943 (3)	0.0338 (10)
H6A	0.5453	0.2464	1.0688	0.041*
H6B	0.7037	0.2445	1.1623	0.041*
C7	0.7539 (7)	0.1221 (3)	1.0718 (3)	0.0333 (9)
H7A	0.8978	0.1111	1.0975	0.040*
H7B	0.7373	0.1126	1.0040	0.040*
C8	0.6260 (8)	0.0359 (3)	1.1127 (3)	0.0426 (11)
H8A	0.6674	−0.0389	1.0974	0.064*
H8B	0.4836	0.0470	1.0871	0.064*
H8C	0.6449	0.0445	1.1800	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Re1	0.02322 (11)	0.02022 (10)	0.02042 (10)	0.00156 (6)	0.01068 (7)	0.00100 (5)
Cl1	0.0449 (6)	0.0377 (5)	0.0419 (6)	0.0105 (5)	0.0232 (5)	−0.0039 (5)
O1	0.0283 (15)	0.0278 (13)	0.0217 (14)	0.0015 (11)	0.0092 (12)	0.0030 (10)
O2	0.0294 (16)	0.0275 (13)	0.0222 (14)	0.0013 (11)	0.0108 (12)	−0.0003 (10)
O3	0.0256 (15)	0.0252 (13)	0.0243 (14)	−0.0007 (10)	0.0105 (12)	0.0029 (10)
O4	0.0267 (14)	0.0235 (13)	0.0238 (13)	−0.0025 (11)	0.0086 (11)	−0.0006 (11)
C1	0.027 (2)	0.0276 (18)	0.024 (2)	−0.0031 (16)	0.0112 (17)	0.0024 (15)
C2	0.029 (2)	0.041 (2)	0.024 (2)	0.0023 (18)	0.0081 (17)	0.0013 (17)
C3	0.034 (3)	0.071 (3)	0.033 (2)	0.015 (2)	0.012 (2)	0.021 (2)
C4	0.063 (4)	0.095 (5)	0.084 (5)	−0.027 (4)	−0.010 (3)	0.060 (4)
C5	0.0217 (19)	0.0284 (19)	0.0246 (19)	−0.0020 (16)	0.0058 (15)	0.0014 (15)
C6	0.035 (2)	0.031 (2)	0.039 (2)	−0.0015 (18)	0.0177 (19)	0.0082 (17)
C7	0.038 (2)	0.025 (2)	0.038 (2)	−0.0064 (17)	0.011 (2)	0.0019 (17)
C8	0.048 (3)	0.031 (2)	0.049 (3)	−0.012 (2)	0.012 (2)	0.0063 (19)

Geometric parameters (Å, º) top

Re1—O2ⁱ	2.008 (3)	C3—C4	1.509 (7)
Re1—O3	2.019 (2)	C3—H3A	0.9900
Re1—O4ⁱ	2.025 (2)	C3—H3B	0.9900
Re1—O1	2.026 (3)	C4—H4A	0.9800
Re1—Re1ⁱ	2.2330 (3)	C4—H4B	0.9800
Re1—Cl1	2.5135 (9)	C4—H4C	0.9800
O1—C1	1.275 (5)	C5—C6	1.487 (5)
O2—C1	1.283 (4)	C6—C7	1.508 (5)
O2—Re1ⁱ	2.008 (3)	C6—H6A	0.9900
O3—C5	1.273 (4)	C6—H6B	0.9900
O4—C5	1.294 (4)	C7—C8	1.531 (5)
O4—Re1ⁱ	2.025 (2)	C7—H7A	0.9900
C1—C2	1.482 (6)	C7—H7B	0.9900
C2—C3	1.520 (6)	C8—H8A	0.9800
C2—H2A	0.9900	C8—H8B	0.9800
C2—H2B	0.9900	C8—H8C	0.9800

O2ⁱ—Re1—O3	89.39 (11)	C4—C3—H3B	109.2
O2ⁱ—Re1—O4ⁱ	90.26 (10)	C2—C3—H3B	109.2
O3—Re1—O4ⁱ	179.64 (11)	H3A—C3—H3B	107.9
O2ⁱ—Re1—O1	179.70 (10)	C3—C4—H4A	109.5
O3—Re1—O1	90.68 (11)	C3—C4—H4B	109.5
O4ⁱ—Re1—O1	89.67 (10)	H4A—C4—H4B	109.5
O2ⁱ—Re1—Re1ⁱ	90.42 (7)	C3—C4—H4C	109.5
O3—Re1—Re1ⁱ	89.36 (7)	H4A—C4—H4C	109.5
O4ⁱ—Re1—Re1ⁱ	90.55 (7)	H4B—C4—H4C	109.5
O1—Re1—Re1ⁱ	89.29 (7)	O3—C5—O4	120.7 (3)
O2ⁱ—Re1—Cl1	92.90 (8)	O3—C5—C6	118.9 (3)
O3—Re1—Cl1	88.76 (8)	O4—C5—C6	120.4 (3)
O4ⁱ—Re1—Cl1	91.34 (7)	C5—C6—C7	116.1 (3)
O1—Re1—Cl1	87.40 (8)	C5—C6—H6A	108.3
Re1ⁱ—Re1—Cl1	176.18 (3)	C7—C6—H6A	108.3
C1—O1—Re1	120.0 (2)	C5—C6—H6B	108.3
C1—O2—Re1ⁱ	119.6 (2)	C7—C6—H6B	108.3
C5—O3—Re1	120.7 (2)	H6A—C6—H6B	107.4
C5—O4—Re1ⁱ	118.7 (2)	C6—C7—C8	109.9 (4)
O1—C1—O2	120.7 (4)	C6—C7—H7A	109.7
O1—C1—C2	120.3 (3)	C8—C7—H7A	109.7
O2—C1—C2	119.0 (3)	C6—C7—H7B	109.7
C1—C2—C3	111.3 (4)	C8—C7—H7B	109.7
C1—C2—H2A	109.4	H7A—C7—H7B	108.2
C3—C2—H2A	109.4	C7—C8—H8A	109.5
C1—C2—H2B	109.4	C7—C8—H8B	109.5
C3—C2—H2B	109.4	H8A—C8—H8B	109.5
H2A—C2—H2B	108.0	C7—C8—H8C	109.5
C4—C3—C2	112.3 (4)	H8A—C8—H8C	109.5
C4—C3—H3A	109.2	H8B—C8—H8C	109.5
C2—C3—H3A	109.2

O2ⁱ—Re1—O1—C1	13 (19)	Re1ⁱ—O2—C1—O1	−0.9 (5)
O3—Re1—O1—C1	−89.7 (3)	Re1ⁱ—O2—C1—C2	176.6 (2)
O4ⁱ—Re1—O1—C1	90.2 (3)	O1—C1—C2—C3	115.7 (4)
Re1ⁱ—Re1—O1—C1	−0.3 (3)	O2—C1—C2—C3	−61.7 (5)
Cl1—Re1—O1—C1	−178.4 (3)	C1—C2—C3—C4	−55.2 (5)
O2ⁱ—Re1—O3—C5	−90.7 (3)	Re1—O3—C5—O4	−0.1 (5)
O4ⁱ—Re1—O3—C5	−77 (17)	Re1—O3—C5—C6	179.9 (3)
O1—Re1—O3—C5	89.0 (3)	Re1ⁱ—O4—C5—O3	0.5 (5)
Re1ⁱ—Re1—O3—C5	−0.3 (3)	Re1ⁱ—O4—C5—C6	−179.5 (3)
Cl1—Re1—O3—C5	176.4 (3)	O3—C5—C6—C7	−172.7 (4)
Re1—O1—C1—O2	0.8 (5)	O4—C5—C6—C7	7.2 (6)
Re1—O1—C1—C2	−176.6 (2)	C5—C6—C7—C8	179.5 (4)

Symmetry code: (i) −x+2, −y+1, −z+2.

Selected bond lengths (Å) top

Re1—O2ⁱ	2.008 (3)	Re1—O1	2.026 (3)
Re1—O3	2.019 (2)	Re1—Cl1	2.5135 (9)
Re1—O4ⁱ	2.025 (2)

Symmetry code: (i) −x+2, −y+1, −z+2.

Acknowledgements

The authors thank NSERC (Canada) for financial support.

References

Bruker (2010). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Calvo, C., Jayadevan, N. C. & Lock, C. J. L. (1969). Can. J. Chem. 47, 4213–4220. CrossRef CAS Web of Science Google Scholar
Collins, D. M., Cotton, F. A. & Gage, L. D. (1979). Inorg. Chem. 18, 1712–1715. CSD CrossRef CAS Web of Science Google Scholar
Lydon, D. P., Spalding, T. R. & Gallagher, J. F. (2003). Polyhedron, 22, 1281–1287. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Taha, F. & Wilkinson, G. (1963). J. Chem. Soc. pp. 5406–5412. CrossRef Web of Science Google Scholar

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