Tetra-μ3-hydroxido-tetra­kis­[tricarbonyl­rhenium(I)] pyridine tetra­solvate

Schutte, M.; Brink, A.; Visser, H.G.; Roodt, A.

doi:10.1107/S1600536812036033

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Pages m1208-m1209

doi:10.1107/S1600536812036033

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Tetra-μ₃-hydroxido-tetrakis[tricarbonylrhenium(I)] pyridine tetrasolvate

M. Schutte,^a ^* A. Brink,^a H. G. Visser ^a and A. Roodt ^a

^aDepartment of Chemistry, University of the Free State, PO Box 339, Bloemfontein 9301, South Africa
^*Correspondence e-mail: schuttem@ufs.ac.za

(Received 15 August 2012; accepted 16 August 2012; online 25 August 2012)

The title compound, [Re₄(μ₃-OH)₄(CO)₁₂]·4C₅H₅N, crystallizes with one tetranuclear rhenium(I) cubane-like molecule and four pyridine molecules in the asymmetric unit. The coordination environment of each Re^I atom is distorted octahedral. Four intramolecular O—H⋯N and four intermolecular C—H⋯O hydrogen-bond interactions are observed. Relatively strong hydrogen bonds are found between the hydrogen-bond donor (μ₃-OH) and acceptor (basic N atom of pyridine), with N⋯O distances between 2.586 (10) and 2.628 (10) Å. Intercube distances of 9.873 (2) and 12.376 (3) Å are observed.

Related literature

For similar structures, see: Herberhold & Süss (1975 ); Nuber et al. (1981 ); Copp et al. (1995 ); Egli et al. (1997 ). For the synthesis of the precursor, see: Alberto et al. (1996 ).

Experimental

Crystal data

[Re₄(OH)₄(CO)₁₂]·4C₅H₅N
M_r = 1465.39
Monoclinic, P 2₁ /c
a = 11.895 (5) Å
b = 21.847 (5) Å
c = 16.245 (5) Å
β = 109.707 (5)°
V = 3974 (2) Å³
Z = 4
Mo Kα radiation
μ = 12.22 mm⁻¹
T = 100 K
0.43 × 0.11 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.211, T_max = 0.271
68439 measured reflections
9594 independent reflections
7966 reflections with I > 2σ(I)
R_int = 0.064

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.099
S = 1.04
9594 reflections
516 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 7.00 e Å⁻³
Δρ_min = −6.09 e Å⁻³

Table 1
Selected bond lengths (Å)

Re3—C32	1.886 (10)
Re3—C31	1.900 (9)
Re3—C33	1.906 (10)
Re3—O1	2.157 (6)
Re3—O3	2.168 (6)
Re3—O4	2.179 (6)
Re4—C43	1.893 (9)
Re4—C42	1.913 (10)
Re4—C41	1.918 (9)
Re4—O2	2.154 (7)
Re4—O3	2.172 (6)
Re4—O4	2.173 (6)
Re2—C23	1.891 (9)
Re2—C22	1.916 (9)
Re2—C21	1.918 (10)
Re2—O3	2.157 (6)
Re2—O2	2.165 (6)
Re2—O1	2.171 (6)
O1—Re1	2.178 (6)
O4—Re1	2.160 (6)
Re1—C12	1.888 (10)
Re1—C13	1.889 (10)
Re1—C11	1.907 (10)
Re1—O2	2.169 (6)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C103—H103⋯O23ⁱ	0.93	2.59	3.249 (12)	128
C203—H203⋯O33ⁱⁱ	0.93	2.42	3.330 (13)	166
C303—H303⋯O42ⁱⁱⁱ	0.93	2.49	3.321 (13)	149
C404—H404⋯O32^iv	0.93	2.47	3.252 (12)	142
O1—H1⋯N2	0.85 (2)	1.76 (4)	2.600 (10)	170 (16)
O2—H2⋯N3	0.85 (2)	1.74 (3)	2.586 (10)	174 (11)
O3—H3⋯N1	0.85 (2)	1.79 (4)	2.627 (10)	165 (14)
O4—H4⋯N4	0.85 (2)	1.78 (4)	2.620 (10)	169 (15)
Symmetry codes: (i) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x, -y+1, -z+2; (iv) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812036033/hg5243sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812036033/hg5243Isup2.hkl

checkCIF report

Comment top

The compound [Re₄(CO)₁₂(µ₃-OH)₄], which is a cubane-like molecule, crystallized with four pyridine ligands (hydrogen bond acceptor molecules or 'spacers') in the asymmetric unit. Four intramolecular hydrogen bonds are observed between the hydroxide bridges in the rhenium cluster and the pyridine molecules. These hydrogen interactions are also found by Copp et al. (1995) with benzene, toluene, p-xylene, p-fluorotoluene, naphthalene, 1-methylnaphthalene etc. surrounding the rhenium cluster as well as DMF and OPPh₃ reported by Egli et al. (1997). Four intermolecular hydrogen interactions are reported between an aromatic carbon of the pyridine molecule to a carbonyl oxygen atom of the next rhenium cluster. The Re—O—Re angles (102.6 (3) ° to 104.7 (3) °) and the Re—O distances (2.154 (7) Å to 2.179 (6) Å) compare well to the structures of Herberhold & Süss (1975), Nuber et al. (1981), Copp et al. (1995) and Egli et al. (1997). The hydrogen bonds between the hydrogen-bond donor (µ₃-OH) and acceptor (basic nitrogen of pyridine) are relatively strong with N···O distances ranging from 2.586 (10) Å to 2.628 (10) Å. This is comparable to the manganese structure by Copp et al. (1995) with a C···O distance of 2.74 Å from the bipyridine ligand to the bridging hydroxide oxygen. However, it does not correspond that well to the structure reported by Copp et al. (1995) with a distance of 3.58/3.59 Å for the C···O distance of the manganese structure with benzene as 'spacer'. Intercube distances of 9.873 (2) Å and 12.376 (3) Å are reported and fits well within the range found by Copp et al. (1995) (9.74 Å - 15.35 Å).

Related literature top

For similar structures, see: Herberhold & Süss (1975); Nuber et al. (1981); Copp et al. (1995); Egli et al. (1997). For the synthesis of the precursor, see: Alberto et al. (1996) for the synthesis of the precursor.

Experimental top

[NEt₄]₂[Re(CO)₃Br₃] (75 mg, 0.097 mmol), as prepared by Alberto et al. (1996), was dissolved in 20 ml of pyridine. The mixture was stirred at room temperature for 3 h and left to stand. The colourless cuboidal crystals formed by evaporation after a few days.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Representation of the title compound, showing the numbering scheme and displacement ellipsoids (50% probability).
	Fig. 2. Packing of the title compound in the unit cell.

Tetra-µ₃-hydroxido-tetrakis[tricarbonylrhenium(I)] pyridine tetrasolvate top

Crystal data top

[Re₄(OH)₄(CO)₁₂]·4C₅H₅N	F(000) = 2688
M_r = 1465.39	D_x = 2.449 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9793 reflections
a = 11.895 (5) Å	θ = 2.7–28.1°
b = 21.847 (5) Å	µ = 12.22 mm⁻¹
c = 16.245 (5) Å	T = 100 K
β = 109.707 (5)°	Cuboid, colourless
V = 3974 (2) Å³	0.43 × 0.11 × 0.11 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	7966 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
ϕ and ω scans	θ_max = 28°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −15→15
T_min = 0.211, T_max = 0.271	k = −28→28
68439 measured reflections	l = −20→21
9594 independent reflections

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0181P)² + 118.6736P] where P = (F_o² + 2F_c²)/3
9594 reflections	(Δ/σ)_max = 0.001
516 parameters	Δρ_max = 7.00 e Å⁻³
4 restraints	Δρ_min = −6.09 e Å⁻³

Crystal data top

[Re₄(OH)₄(CO)₁₂]·4C₅H₅N	V = 3974 (2) Å³
M_r = 1465.39	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.895 (5) Å	µ = 12.22 mm⁻¹
b = 21.847 (5) Å	T = 100 K
c = 16.245 (5) Å	0.43 × 0.11 × 0.11 mm
β = 109.707 (5)°

Data collection top

Bruker APEXII CCD diffractometer	9594 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	7966 reflections with I > 2σ(I)
T_min = 0.211, T_max = 0.271	R_int = 0.064
68439 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	4 restraints
wR(F²) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0181P)² + 118.6736P] where P = (F_o² + 2F_c²)/3
9594 reflections	Δρ_max = 7.00 e Å⁻³
516 parameters	Δρ_min = −6.09 e Å⁻³

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Re3	0.36392 (3)	0.330517 (15)	0.69816 (2)	0.01378 (7)
Re4	0.36579 (3)	0.431796 (15)	0.85997 (2)	0.01378 (7)
Re2	0.16248 (3)	0.316708 (15)	0.80536 (2)	0.01277 (8)
O1	0.1755 (6)	0.3368 (3)	0.6780 (4)	0.0146 (12)
O33	0.6355 (6)	0.3461 (4)	0.7514 (4)	0.0299 (17)
C23	−0.0056 (8)	0.3095 (4)	0.7695 (5)	0.0146 (17)
O4	0.3333 (6)	0.4265 (3)	0.7203 (4)	0.0154 (12)
O23	−0.1098 (6)	0.3044 (3)	0.7458 (4)	0.0235 (14)
Re1	0.14174 (3)	0.434793 (15)	0.66166 (2)	0.01489 (8)
O3	0.3485 (5)	0.3351 (3)	0.8273 (4)	0.0128 (12)
O41	0.3519 (6)	0.5714 (3)	0.8711 (5)	0.0258 (15)
O42	0.3772 (6)	0.4234 (3)	1.0504 (4)	0.0217 (14)
O43	0.6378 (6)	0.4340 (3)	0.9300 (4)	0.0257 (15)
C43	0.5348 (8)	0.4345 (4)	0.9030 (5)	0.0147 (17)
C42	0.3727 (8)	0.4268 (4)	0.9792 (6)	0.0195 (19)
C41	0.3593 (8)	0.5192 (4)	0.8685 (6)	0.0178 (18)
O31	0.3407 (7)	0.3349 (3)	0.5051 (4)	0.0277 (16)
O21	0.1723 (7)	0.3090 (4)	0.9962 (4)	0.0331 (18)
C31	0.3503 (8)	0.3337 (4)	0.5783 (6)	0.0189 (18)
C21	0.1686 (9)	0.3116 (4)	0.9247 (6)	0.022 (2)
C33	0.5327 (9)	0.3392 (5)	0.7306 (5)	0.021 (2)
O22	0.1678 (7)	0.1772 (3)	0.7977 (5)	0.0332 (17)
C22	0.1671 (8)	0.2291 (4)	0.8013 (6)	0.0192 (18)
O32	0.3974 (7)	0.1929 (3)	0.6811 (4)	0.0304 (17)
O11	0.1210 (8)	0.5739 (3)	0.6689 (6)	0.045 (2)
C32	0.3824 (9)	0.2454 (5)	0.6885 (6)	0.021 (2)
C11	0.1278 (9)	0.5215 (5)	0.6665 (7)	0.027 (2)
O12	0.1361 (7)	0.4482 (4)	0.4735 (5)	0.0336 (18)
C12	0.1361 (9)	0.4431 (4)	0.5446 (6)	0.023 (2)
C13	−0.0265 (9)	0.4291 (4)	0.6207 (6)	0.0206 (19)
O13	−0.1292 (7)	0.4231 (3)	0.5947 (5)	0.0320 (17)
N1	0.5054 (7)	0.2663 (4)	0.9429 (5)	0.0211 (17)
N2	0.0085 (8)	0.2811 (4)	0.5546 (5)	0.0247 (18)
N3	0.0328 (7)	0.4768 (4)	0.8558 (5)	0.0226 (17)
N4	0.4824 (7)	0.4935 (4)	0.6715 (5)	0.0224 (17)
C305	−0.0787 (10)	0.4596 (5)	0.8305 (7)	0.032 (2)
H305	−0.0992	0.4236	0.7984	0.038*
C302	−0.0225 (13)	0.5632 (6)	0.9231 (9)	0.047 (3)
H302	0.0003	0.5985	0.9566	0.056*
C304	−0.1692 (11)	0.4915 (6)	0.8484 (8)	0.040 (3)
H304	−0.2472	0.4769	0.83	0.047*
C303	−0.1390 (11)	0.5454 (6)	0.8941 (9)	0.042 (3)
H303	−0.1971	0.5693	0.905	0.05*
C301	0.0622 (11)	0.5286 (5)	0.9025 (8)	0.035 (3)
H301	0.1412	0.5417	0.9216	0.042*
C403	0.6711 (9)	0.5524 (5)	0.6397 (7)	0.026 (2)
H403	0.7338	0.572	0.6285	0.031*
C402	0.6276 (9)	0.4985 (5)	0.5998 (6)	0.024 (2)
H402	0.6607	0.4807	0.5613	0.029*
C401	0.5332 (9)	0.4701 (5)	0.6170 (6)	0.027 (2)
H401	0.5043	0.4332	0.5893	0.032*
C404	0.6207 (10)	0.5777 (5)	0.6972 (7)	0.029 (2)
H404	0.6495	0.6142	0.7261	0.035*
C405	0.5257 (10)	0.5471 (5)	0.7108 (7)	0.028 (2)
H405	0.4905	0.5644	0.7485	0.034*
C205	−0.0490 (10)	0.2326 (5)	0.5699 (7)	0.033 (2)
H205	−0.0253	0.2164	0.6261	0.039*
C201	−0.0277 (11)	0.3038 (5)	0.4733 (7)	0.035 (3)
H201	0.0107	0.3382	0.462	0.042*
C204	−0.1424 (11)	0.2052 (6)	0.5054 (9)	0.048 (4)
H204	−0.181	0.1715	0.5184	0.058*
C203	−0.1781 (12)	0.2284 (7)	0.4218 (9)	0.052 (4)
H203	−0.2405	0.2105	0.3772	0.062*
C202	−0.1194 (13)	0.2784 (7)	0.4058 (8)	0.053 (4)
H202	−0.1412	0.295	0.35	0.063*
C105	0.5525 (9)	0.2822 (5)	1.0269 (6)	0.023 (2)
H105	0.5308	0.3196	1.0443	0.027*
C103	0.6650 (9)	0.1902 (5)	1.0643 (6)	0.024 (2)
H103	0.7184	0.1646	1.1048	0.029*
C104	0.6325 (9)	0.2455 (5)	1.0898 (6)	0.027 (2)
H104	0.6633	0.2581	1.1477	0.032*
C102	0.6167 (10)	0.1732 (5)	0.9773 (6)	0.028 (2)
H102	0.6372	0.136	0.9583	0.034*
C101	0.5376 (10)	0.2124 (5)	0.9189 (6)	0.027 (2)
H101	0.5055	0.2007	0.8606	0.032*
O2	0.1773 (6)	0.4152 (3)	0.7990 (4)	0.0166 (13)
H3	0.395 (10)	0.316 (6)	0.871 (6)	0.06 (4)*
H2	0.134 (8)	0.436 (4)	0.821 (6)	0.02 (3)*
H1	0.127 (11)	0.319 (6)	0.634 (6)	0.07 (5)*
H4	0.376 (11)	0.452 (5)	0.704 (9)	0.07 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Re3	0.01351 (13)	0.01541 (12)	0.01219 (11)	0.00124 (9)	0.00403 (9)	0.00039 (8)
Re4	0.01351 (13)	0.01541 (12)	0.01219 (11)	0.00124 (9)	0.00403 (9)	0.00039 (8)
Re2	0.01148 (17)	0.01394 (16)	0.01229 (15)	−0.00146 (12)	0.00322 (12)	−0.00020 (12)
O1	0.014 (3)	0.014 (3)	0.010 (3)	0.002 (2)	−0.003 (2)	0.000 (2)
O33	0.013 (4)	0.053 (5)	0.023 (3)	0.006 (3)	0.004 (3)	0.005 (3)
C23	0.017 (5)	0.015 (4)	0.010 (4)	−0.005 (3)	0.003 (3)	0.000 (3)
O4	0.019 (3)	0.014 (3)	0.016 (3)	0.001 (3)	0.009 (3)	0.005 (2)
O23	0.016 (4)	0.022 (3)	0.032 (4)	−0.002 (3)	0.008 (3)	0.004 (3)
Re1	0.01131 (17)	0.01397 (16)	0.01761 (16)	0.00153 (13)	0.00254 (13)	0.00234 (12)
O3	0.013 (3)	0.013 (3)	0.011 (3)	−0.001 (2)	0.003 (2)	0.000 (2)
O41	0.028 (4)	0.012 (3)	0.034 (4)	−0.006 (3)	0.006 (3)	−0.004 (3)
O42	0.021 (4)	0.029 (4)	0.017 (3)	−0.006 (3)	0.009 (3)	−0.003 (3)
O43	0.017 (4)	0.030 (4)	0.030 (4)	−0.007 (3)	0.008 (3)	−0.001 (3)
C43	0.015 (4)	0.014 (4)	0.016 (4)	−0.004 (3)	0.007 (3)	−0.004 (3)
C42	0.015 (5)	0.013 (4)	0.029 (5)	−0.003 (3)	0.006 (4)	−0.001 (4)
C41	0.015 (4)	0.016 (4)	0.020 (4)	−0.001 (3)	0.003 (4)	0.002 (3)
O31	0.034 (4)	0.034 (4)	0.016 (3)	0.005 (3)	0.009 (3)	0.002 (3)
O21	0.038 (5)	0.049 (5)	0.016 (3)	−0.012 (4)	0.014 (3)	−0.002 (3)
C31	0.019 (5)	0.022 (4)	0.015 (4)	0.004 (4)	0.003 (3)	0.001 (3)
C21	0.016 (5)	0.019 (4)	0.027 (5)	−0.005 (4)	0.002 (4)	−0.002 (4)
C33	0.023 (5)	0.031 (5)	0.006 (4)	0.008 (4)	0.002 (3)	−0.001 (3)
O22	0.035 (4)	0.018 (4)	0.040 (4)	0.001 (3)	0.005 (3)	0.000 (3)
C22	0.012 (4)	0.018 (4)	0.023 (4)	0.000 (3)	0.001 (4)	0.000 (4)
O32	0.050 (5)	0.017 (3)	0.024 (3)	0.008 (3)	0.012 (3)	0.000 (3)
O11	0.047 (5)	0.013 (4)	0.056 (5)	0.003 (3)	−0.007 (4)	0.003 (3)
C32	0.019 (5)	0.029 (5)	0.014 (4)	−0.004 (4)	0.003 (4)	0.002 (4)
C11	0.016 (5)	0.025 (5)	0.027 (5)	0.003 (4)	−0.008 (4)	0.005 (4)
O12	0.033 (4)	0.039 (4)	0.026 (4)	0.006 (3)	0.006 (3)	0.016 (3)
C12	0.016 (5)	0.023 (5)	0.023 (5)	0.004 (4)	−0.001 (4)	0.010 (4)
C13	0.015 (5)	0.020 (4)	0.021 (4)	0.004 (4)	−0.001 (4)	0.000 (4)
O13	0.022 (4)	0.029 (4)	0.042 (4)	0.002 (3)	0.006 (3)	0.005 (3)
N1	0.020 (4)	0.027 (4)	0.015 (3)	−0.004 (3)	0.004 (3)	0.003 (3)
N2	0.022 (4)	0.022 (4)	0.026 (4)	0.000 (3)	0.003 (3)	−0.007 (3)
N3	0.018 (4)	0.022 (4)	0.029 (4)	0.003 (3)	0.009 (3)	−0.005 (3)
N4	0.022 (4)	0.024 (4)	0.023 (4)	−0.003 (3)	0.009 (3)	0.003 (3)
C305	0.029 (6)	0.032 (6)	0.038 (6)	0.001 (5)	0.016 (5)	0.004 (5)
C302	0.067 (10)	0.029 (6)	0.052 (7)	0.015 (6)	0.030 (7)	−0.011 (5)
C304	0.025 (6)	0.047 (7)	0.052 (7)	0.006 (5)	0.020 (5)	0.014 (6)
C303	0.037 (7)	0.041 (7)	0.057 (8)	0.015 (6)	0.029 (6)	0.000 (6)
C301	0.031 (6)	0.030 (6)	0.047 (7)	0.002 (5)	0.016 (5)	−0.007 (5)
C403	0.026 (5)	0.025 (5)	0.031 (5)	0.000 (4)	0.016 (4)	0.011 (4)
C402	0.019 (5)	0.034 (5)	0.022 (5)	−0.001 (4)	0.010 (4)	0.002 (4)
C401	0.026 (6)	0.031 (5)	0.022 (5)	−0.008 (4)	0.006 (4)	−0.006 (4)
C404	0.031 (6)	0.017 (5)	0.042 (6)	−0.005 (4)	0.015 (5)	−0.005 (4)
C405	0.034 (6)	0.025 (5)	0.034 (5)	0.007 (4)	0.021 (5)	0.002 (4)
C205	0.030 (6)	0.035 (6)	0.034 (6)	0.002 (5)	0.011 (5)	−0.015 (5)
C201	0.041 (7)	0.031 (6)	0.023 (5)	0.013 (5)	−0.001 (5)	−0.005 (4)
C204	0.033 (7)	0.045 (7)	0.069 (9)	−0.017 (6)	0.020 (7)	−0.035 (7)
C203	0.030 (7)	0.062 (9)	0.046 (7)	0.010 (6)	−0.009 (6)	−0.039 (7)
C202	0.054 (9)	0.067 (9)	0.024 (6)	0.016 (7)	−0.005 (6)	−0.024 (6)
C105	0.025 (5)	0.023 (5)	0.020 (4)	0.003 (4)	0.007 (4)	0.001 (4)
C103	0.025 (5)	0.024 (5)	0.022 (5)	0.004 (4)	0.006 (4)	0.005 (4)
C104	0.026 (6)	0.033 (5)	0.015 (4)	−0.001 (4)	−0.002 (4)	0.003 (4)
C102	0.035 (6)	0.029 (5)	0.022 (5)	0.015 (5)	0.010 (4)	0.003 (4)
C101	0.032 (6)	0.026 (5)	0.020 (5)	0.001 (4)	0.005 (4)	0.003 (4)
O2	0.021 (3)	0.015 (3)	0.017 (3)	0.001 (3)	0.010 (3)	−0.002 (2)

Geometric parameters (Å, º) top

Re3—C32	1.886 (10)	N2—C201	1.339 (13)
Re3—C31	1.900 (9)	N3—C305	1.304 (14)
Re3—C33	1.906 (10)	N3—C301	1.342 (13)
Re3—O1	2.157 (6)	N4—C401	1.331 (13)
Re3—O3	2.168 (6)	N4—C405	1.349 (13)
Re3—O4	2.179 (6)	C305—C304	1.392 (16)
Re4—C43	1.893 (9)	C305—H305	0.93
Re4—C42	1.913 (10)	C302—C303	1.362 (19)
Re4—C41	1.918 (9)	C302—C301	1.386 (16)
Re4—O2	2.154 (7)	C302—H302	0.93
Re4—O3	2.172 (6)	C304—C303	1.373 (18)
Re4—O4	2.173 (6)	C304—H304	0.93
Re2—C23	1.891 (9)	C303—H303	0.93
Re2—C22	1.916 (9)	C301—H301	0.93
Re2—C21	1.918 (10)	C403—C402	1.359 (14)
Re2—O3	2.157 (6)	C403—C404	1.385 (14)
Re2—O2	2.165 (6)	C403—H403	0.93
Re2—O1	2.171 (6)	C402—C401	1.392 (14)
O1—Re1	2.178 (6)	C402—H402	0.93
O1—H1	0.85 (2)	C401—H401	0.93
O33—C33	1.164 (12)	C404—C405	1.392 (15)
C23—O23	1.173 (11)	C404—H404	0.93
O4—Re1	2.160 (6)	C405—H405	0.93
O4—H4	0.85 (2)	C205—C204	1.380 (16)
Re1—C12	1.888 (10)	C205—H205	0.93
Re1—C13	1.889 (10)	C201—C202	1.376 (16)
Re1—C11	1.907 (10)	C201—H201	0.93
Re1—O2	2.169 (6)	C204—C203	1.38 (2)
O3—H3	0.85 (2)	C204—H204	0.93
O41—C41	1.146 (11)	C203—C202	1.37 (2)
O42—C42	1.143 (11)	C203—H203	0.93
O43—C43	1.154 (11)	C202—H202	0.93
O31—C31	1.156 (11)	C105—C104	1.391 (13)
O21—C21	1.149 (11)	C105—H105	0.93
O22—C22	1.137 (11)	C103—C104	1.375 (14)
O32—C32	1.172 (12)	C103—C102	1.386 (13)
O11—C11	1.149 (12)	C103—H103	0.93
O12—C12	1.161 (12)	C104—H104	0.93
C13—O13	1.157 (12)	C102—C101	1.384 (14)
N1—C105	1.334 (12)	C102—H102	0.93
N1—C101	1.338 (13)	C101—H101	0.93
N2—C205	1.328 (14)	O2—H2	0.85 (2)

C32—Re3—C31	85.6 (4)	O42—C42—Re4	179.5 (9)
C32—Re3—C33	88.8 (4)	O41—C41—Re4	177.6 (8)
C31—Re3—C33	89.8 (4)	O31—C31—Re3	178.9 (9)
C32—Re3—O1	101.2 (3)	O21—C21—Re2	179.5 (9)
C31—Re3—O1	96.7 (3)	O33—C33—Re3	178.0 (9)
C33—Re3—O1	168.4 (3)	O22—C22—Re2	178.7 (9)
C32—Re3—O3	100.1 (3)	O32—C32—Re3	177.3 (9)
C31—Re3—O3	169.7 (3)	O11—C11—Re1	178.9 (11)
C33—Re3—O3	98.8 (3)	O12—C12—Re1	178.1 (9)
O1—Re3—O3	73.8 (2)	O13—C13—Re1	177.2 (8)
C32—Re3—O4	173.6 (3)	C105—N1—C101	117.7 (8)
C31—Re3—O4	99.9 (3)	C205—N2—C201	117.8 (9)
C33—Re3—O4	94.5 (3)	C305—N3—C301	117.7 (9)
O1—Re3—O4	75.0 (2)	C401—N4—C405	117.5 (9)
O3—Re3—O4	73.9 (2)	N3—C305—C304	124.5 (11)
C43—Re4—C42	87.2 (4)	N3—C305—H305	117.8
C43—Re4—C41	90.3 (4)	C304—C305—H305	117.8
C42—Re4—C41	88.4 (4)	C303—C302—C301	119.8 (12)
C43—Re4—O2	170.3 (3)	C303—C302—H302	120.1
C42—Re4—O2	98.0 (3)	C301—C302—H302	120.1
C41—Re4—O2	98.0 (3)	C303—C304—C305	117.5 (11)
C43—Re4—O3	97.0 (3)	C303—C304—H304	121.3
C42—Re4—O3	99.2 (3)	C305—C304—H304	121.3
C41—Re4—O3	169.6 (3)	C302—C303—C304	118.9 (11)
O2—Re4—O3	74.1 (2)	C302—C303—H303	120.6
C43—Re4—O4	100.4 (3)	C304—C303—H303	120.6
C42—Re4—O4	170.3 (3)	N3—C301—C302	121.6 (11)
C41—Re4—O4	97.5 (3)	N3—C301—H301	119.2
O2—Re4—O4	73.7 (2)	C302—C301—H301	119.2
O3—Re4—O4	74.0 (2)	C402—C403—C404	119.0 (9)
C23—Re2—C22	86.9 (4)	C402—C403—H403	120.5
C23—Re2—C21	89.0 (4)	C404—C403—H403	120.5
C22—Re2—C21	89.2 (4)	C403—C402—C401	119.7 (9)
C23—Re2—O3	170.2 (3)	C403—C402—H402	120.2
C22—Re2—O3	98.7 (3)	C401—C402—H402	120.2
C21—Re2—O3	99.0 (3)	N4—C401—C402	122.7 (9)
C23—Re2—O2	99.4 (3)	N4—C401—H401	118.7
C22—Re2—O2	170.9 (3)	C402—C401—H401	118.7
C21—Re2—O2	97.5 (3)	C403—C404—C405	118.3 (9)
O3—Re2—O2	74.2 (2)	C403—C404—H404	120.8
C23—Re2—O1	97.5 (3)	C405—C404—H404	120.8
C22—Re2—O1	99.0 (3)	N4—C405—C404	122.8 (9)
C21—Re2—O1	169.8 (3)	N4—C405—H405	118.6
O3—Re2—O1	73.8 (2)	C404—C405—H405	118.6
O2—Re2—O1	73.8 (2)	N2—C205—C204	122.5 (12)
Re3—O1—Re2	104.3 (2)	N2—C205—H205	118.8
Re3—O1—Re1	102.7 (3)	C204—C205—H205	118.8
Re2—O1—Re1	104.2 (2)	N2—C201—C202	122.7 (13)
Re3—O1—H1	118 (10)	N2—C201—H201	118.6
Re2—O1—H1	117 (10)	C202—C201—H201	118.6
Re1—O1—H1	108 (10)	C203—C204—C205	119.4 (13)
O23—C23—Re2	178.7 (8)	C203—C204—H204	120.3
Re1—O4—Re4	104.2 (3)	C205—C204—H204	120.3
Re1—O4—Re3	102.6 (3)	C202—C203—C204	118.3 (11)
Re4—O4—Re3	104.0 (2)	C202—C203—H203	120.9
Re1—O4—H4	117 (10)	C204—C203—H203	120.9
Re4—O4—H4	112 (10)	C203—C202—C201	119.3 (13)
Re3—O4—H4	116 (10)	C203—C202—H202	120.3
C12—Re1—C13	88.7 (4)	C201—C202—H202	120.3
C12—Re1—C11	88.4 (4)	N1—C105—C104	123.2 (9)
C13—Re1—C11	89.0 (4)	N1—C105—H105	118.4
C12—Re1—O4	97.2 (3)	C104—C105—H105	118.4
C13—Re1—O4	170.0 (3)	C104—C103—C102	118.7 (9)
C11—Re1—O4	99.1 (3)	C104—C103—H103	120.7
C12—Re1—O2	169.5 (3)	C102—C103—H103	120.7
C13—Re1—O2	99.5 (3)	C103—C104—C105	118.6 (9)
C11—Re1—O2	98.2 (4)	C103—C104—H104	120.7
O4—Re1—O2	73.7 (2)	C105—C104—H104	120.7
C12—Re1—O1	99.2 (3)	C101—C102—C103	119.1 (9)
C13—Re1—O1	96.2 (3)	C101—C102—H102	120.5
C11—Re1—O1	170.8 (3)	C103—C102—H102	120.5
O4—Re1—O1	75.0 (2)	N1—C101—C102	122.8 (9)
O2—Re1—O1	73.5 (2)	N1—C101—H101	118.6
Re2—O3—Re3	104.4 (2)	C102—C101—H101	118.6
Re2—O3—Re4	103.2 (2)	Re4—O2—Re2	103.5 (3)
Re3—O3—Re4	104.4 (2)	Re4—O2—Re1	104.6 (3)
Re2—O3—H3	112 (10)	Re2—O2—Re1	104.7 (2)
Re3—O3—H3	123 (10)	Re4—O2—H2	114 (8)
Re4—O3—H3	107 (10)	Re2—O2—H2	115 (8)
O43—C43—Re4	177.6 (8)	Re1—O2—H2	113 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C103—H103···O23ⁱ	0.93	2.59	3.249 (12)	128
C203—H203···O33ⁱⁱ	0.93	2.42	3.330 (13)	166
C303—H303···O42ⁱⁱⁱ	0.93	2.49	3.321 (13)	149
C404—H404···O32^iv	0.93	2.47	3.252 (12)	142
O1—H1···N2	0.85 (2)	1.76 (4)	2.600 (10)	170 (16)
O2—H2···N3	0.85 (2)	1.74 (3)	2.586 (10)	174 (11)
O3—H3···N1	0.85 (2)	1.79 (4)	2.627 (10)	165 (14)
O4—H4···N4	0.85 (2)	1.78 (4)	2.620 (10)	169 (15)

Symmetry codes: (i) x+1, −y+1/2, z+1/2; (ii) x−1, −y+1/2, z−1/2; (iii) −x, −y+1, −z+2; (iv) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Re₄(OH)₄(CO)₁₂]·4C₅H₅N
M_r	1465.39
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	11.895 (5), 21.847 (5), 16.245 (5)
β (°)	109.707 (5)
V (Å³)	3974 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	12.22
Crystal size (mm)	0.43 × 0.11 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.211, 0.271
No. of measured, independent and observed [I > 2σ(I)] reflections	68439, 9594, 7966
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.099, 1.04
No. of reflections	9594
No. of parameters	516
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ²(F_o²) + (0.0181P)² + 118.6736P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	7.00, −6.09

Computer programs: APEX2 (Bruker, 2008), SAINT-Plus (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

Re3—C32	1.886 (10)	Re2—C23	1.891 (9)
Re3—C31	1.900 (9)	Re2—C22	1.916 (9)
Re3—C33	1.906 (10)	Re2—C21	1.918 (10)
Re3—O1	2.157 (6)	Re2—O3	2.157 (6)
Re3—O3	2.168 (6)	Re2—O2	2.165 (6)
Re3—O4	2.179 (6)	Re2—O1	2.171 (6)
Re4—C43	1.893 (9)	O1—Re1	2.178 (6)
Re4—C42	1.913 (10)	O4—Re1	2.160 (6)
Re4—C41	1.918 (9)	Re1—C12	1.888 (10)
Re4—O2	2.154 (7)	Re1—C13	1.889 (10)
Re4—O3	2.172 (6)	Re1—C11	1.907 (10)
Re4—O4	2.173 (6)	Re1—O2	2.169 (6)

O1—Re3—O3	73.8 (2)	Re1—O4—Re4	104.2 (3)
O1—Re3—O4	75.0 (2)	Re1—O4—Re3	102.6 (3)
O3—Re3—O4	73.9 (2)	Re4—O4—Re3	104.0 (2)
O2—Re4—O3	74.1 (2)	O4—Re1—O2	73.7 (2)
O2—Re4—O4	73.7 (2)	O4—Re1—O1	75.0 (2)
O3—Re4—O4	74.0 (2)	O2—Re1—O1	73.5 (2)
O3—Re2—O2	74.2 (2)	Re2—O3—Re3	104.4 (2)
O3—Re2—O1	73.8 (2)	Re2—O3—Re4	103.2 (2)
O2—Re2—O1	73.8 (2)	Re3—O3—Re4	104.4 (2)
Re3—O1—Re2	104.3 (2)	Re4—O2—Re2	103.5 (3)
Re3—O1—Re1	102.7 (3)	Re4—O2—Re1	104.6 (3)
Re2—O1—Re1	104.2 (2)	Re2—O2—Re1	104.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C103—H103···O23ⁱ	0.93	2.59	3.249 (12)	127.9
C203—H203···O33ⁱⁱ	0.93	2.42	3.330 (13)	166.3
C303—H303···O42ⁱⁱⁱ	0.93	2.49	3.321 (13)	149.4
C404—H404···O32^iv	0.93	2.47	3.252 (12)	141.6
O1—H1···N2	0.85 (2)	1.76 (4)	2.600 (10)	170 (16)
O2—H2···N3	0.85 (2)	1.74 (3)	2.586 (10)	174 (11)
O3—H3···N1	0.85 (2)	1.79 (4)	2.627 (10)	165 (14)
O4—H4···N4	0.85 (2)	1.78 (4)	2.620 (10)	169 (15)

Symmetry codes: (i) x+1, −y+1/2, z+1/2; (ii) x−1, −y+1/2, z−1/2; (iii) −x, −y+1, −z+2; (iv) −x+1, y+1/2, −z+3/2.

Acknowledgements

The University of the Free State, the the Department of Chemistry at the University of the Free State, the NRF and Sasol Ltd. are gratefully acknowledged for funding and Theunis Muller for assistance with the refinement of the data.

References

Alberto, R., Schibli, R. & Schubiger, P. A. (1996). Polyhedron, 15, 1079–1089. CSD CrossRef CAS Web of Science Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2008). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Copp, S. B., Holman, K. T., Sangster, J. O. S., Subramanian, S. & Zaworotko, M. J. (1995). J. Chem. Soc. Dalton Trans. pp. 2233–2243. CSD CrossRef Web of Science Google Scholar
Egli, A., Hegetschweiler, K., Alberto, R., Abram, U., Schibli, R., Hedinger, R., Gramlich, V., Kissner, R. & Schubiger, P. A. (1997). Organometallics, 16, 1833–1940. CSD CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Herberhold, M. & Süss, G. (1975). Angew. Chem. 87, 710–712. CrossRef CAS Google Scholar
Nuber, B., Oberdorfer, F. & Ziegler, M. L. (1981). Acta Cryst. B37, 2062–2064. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar