Crystal structure of tetra-kis-(μ-n-butyrato-κ(2) O:O')bis-[chlorido-rhenium(III)](Re-Re).

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 octa-hedral 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 mol-ecules in the unit cell, and no significant inter-molecular inter-actions were noticed between mol-ecules in the crystal.

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 ▶).

Experimental

Crystal data

[Re2(C4H7O2)4Cl2]

M = 791.68

Monoclinic,

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

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

Refinement

R[F 2 > 2σ(F 2)] = 0.019

wR(F 2) = 0.049

S = 1.06

2277 reflections

129 parameters

H-atom parameters constrained

Δρmax = 0.90 e Å−3

Δρmin = −1.32 e Å−3

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.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814020273/wm5055sup1.cif

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

Click here for additional data file.

x y z . DOI: 10.1107/S1600536814020273/wm5055fig1.tif

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.]

Click here for additional data file.

. DOI: 10.1107/S1600536814020273/wm5055fig2.tif

The packing diagram for the title compound viewed along [100].

CCDC reference: 1023523

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Re2(C4H7O2)4Cl2]	F(000) = 744
Mr = 791.68	Dx = 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

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

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(Fo2) + (0.0278P)2 + 0.2053P] where P = (Fo2 + 2Fc2)/3
2277 reflections	(Δ/σ)max = 0.005
129 parameters	Δρmax = 0.90 e Å−3
0 restraints	Δρmin = −1.32 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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) .