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The ReI centre in the title compound, [Re(C11H9N2O2)(CO)3] or fac-Re(CO)3(dpkO,OH) [dpkO,OH is hydroxybis(2-pyridyl)methanolato], (I), is in a pseudo-octahedral environment in which the major distortion is due to the constraints associated with the tridentate binding of the dpkO,OH anion. The carbonyl groups are orthogonal, with an average C—Re—C angle of 90.2 (3)°. The mol­ecules pack in stacks of antiparallel tapes of (I) interlocked via a network of hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101019527/da1212sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101019527/da1212Isup2.hkl
Contains datablock I

CCDC reference: 181980

Comment top

Several examples of the addition of nucleophiles at the ketonic C atom of rhenium compounds of di-2-pyridylketone (dpk) have been reported (Bakir & McKenzie, 1997; Gerber et al., 1995, 1993). Structural studies on ReOCl2(dpkO,OH) (Gerber et al., 1993) and fac-Re(CO)3(dpk-o)Cl (dpk-o is di-2-pyridylketone oxime; Bakir, 2001) revealed a pseudo-octahedral coordination about Re, in which the major distortion was due to the coordination of dpk-o/dpkO,OH. The structure of fac-Re(CO)3(dpkO,OH), (I), is reported here and compared with the structures of rhenium compounds of dpk-o, dpkO,OH and other related compounds. \sch

The molecular structure of (I) is shown in Fig. 1, and selected bond distances and angles are given in Table 1. The molecule adopts a pseudo-octahedral geometry about Re, with two N atoms and one O atom from the dpkO,OH anion, and three C atoms from the carbonyl groups, occupying the coordinated sites. The three carbonyl groups are orthogonal, with an average C—Re—C angle of 90.2 (3)°.

The Re—C bond distances to the carbonyl groups (Table 1) are longer for the carbonyl groups trans to the pyridine rings than for the carbonyl group trans to the oxo group. This elongation of the Re—C bonds trans to the pyridine rings may be due to the π acidity of the pyridine rings and the increased bond strength of the Re—N bond due to its synergic bonding, whilst the decrease in the Re—C bond trans to the oxo group may be due to the π donation of the oxo group and increased electron density around the Re. This variation in Re—C bond distances is consistent with the three carbonyl stretching bands observed in the IR spectrum (Bakir & McKenzie, 1997). The distances are similar to those observed in a variety of rhenium carbonyl compounds of the type fac-Re(CO)3(L—L)X, where L—L is dpk-o (Bakir, 2001), and other related α-diimine ligands (Xue et al., 1998; Horn & Snow, 1980). For example, in fac-Re(CO)3(dpk-o)Cl, the average Re—C bond distance is 1.91 (6) Å and the average C—Re—C angle is 88.5 (6)° (Bakir, 2001).

Distortion from octahedral geometry in (I) is due to the constraints associated with the tridentate chelation of dpkO,OH, as is apparent from the N—N and N—O bite angles (Table 1). The coordinated dpkO,OH anion forms a six-membered metallocyclic ring (Re1/N1/C15/C4/C25/N2), and two five-membered metallocyclic rings (Re1/Nn/Cn5/C4/O4, where n = 1 or 2) fused along the Re1—O4—C4 bond, with the pyridine rings bent away from the chelating oxide anion. This arrangement leaves one pyridine ring in the equatorial plane and the other in the axial plane, and the oxide atom (O4) and hydroxy group (O5—H5) exposed for potential intermolecular interactions.

The N—N bite angle of 81.6 (2)° for the coordinated dpkO,OH is of the same order as the angle of 80.3 (2)° for dpk-o in fac-Re(CO)3(dpk-o)Cl (Bakir, 2001), smaller than the value of 84.6 (4)° reported for dpkO,OH in ReOCl2(dpkO,OH) (Gerber, 1993) and larger than the value of 74.3 (4)° reported for bipy in fac-Re(CO)3(bipy)(OPOF2) (bipy is 2,2'-bipyridine Is this correct?; Horn & Snow, 1980). These results confirm that the five-membered metallocyclic rings in rhenium compounds of α-diimine ligands are more constrained than the six-membered metallocyclic rings.

The Re—O and Re—N bond distances in (I) (Table 1) are slightly longer than those reported for the high valent ReOCl2(dpkO,OH), which is consistent with the change in Re oxidation state. The steric constraints imposed on the tridentate chelating dpkO,OH anion in both high and low valent rhenium compounds are severe and are associated with the N—O five-membered metallocyclic rings.

The packing of (I) (Fig. 2) shows stacks of interlocked antiparallel tapes of (I), in which the oxide atom (O4) and the hydroxy group (H5—O5) from adjacent stacks are face-to-face (Fig. 3). This arrangement leads to the formation of classical O···H—O hydrogen bonds between adjacent stacks, and non-classical C—H···O hydrogen bonds between atom H12 on the equatorial pyridine ring and the adjacent chelating axial oxide atoms (O4) in each tape (Fig. 3). The bond distances and angles for these hydrogen bonds are similar to those reported for fac-Re(CO)3(dpk-o)Cl, ReOCl2(dpkO,OH) and other compounds containing such bonds. For example, in fac-Re(CO)3(dpk-o)Cl (Bakir, 2001), hydrogen-bond parameters of 0.93, 2.50 and 3.21 (9) Å, and 133° were observed for the soft non-classical hydrogen bond C21—H21···O5, and parameters of 0.82, 1.88 and 2.681 (9) Å, and 164° were observed for the classical hydrogen bond O4—H4···O5.

Due to interest in their rich physicochemical properties, reactivity patterns and application in molecular sensing, work is now in progress to grow crystals of a variety of free bipyridyl-like ligands and their metal compounds in order to explore their solid-state structures, conformations and electro-optical properties.

Experimental top

Compound (I) was synthesized as described earlier by Bakir & McKenzie (1997). The CH3CN used for the crystallization was reagent grade and thoroughly deoxygenated prior to use. When (I) was allowed to stand in CH3CN for several days at room temperature, yellow crystals of (I) were obtained. A single-crystal was selected and mounted on a glass fibre with epoxy cement, and used for data collection.

Refinement top

H atoms were assigned by assuming idealized geometry, with O—H and C—H distances of 0.82 and 0.93 Å, respectively. The position of atom H5 was confirmed in a difference Fourier map, and was then fixed and allowed to ride on atom O5. In the final refinement, two peaks with residual electron density more than 1 e Å-3 appeared at 1.21 and 1.15 Å from Re1. The deepest hole, with an electron density of -1.34 e Å-3, appeared at 1.42 Å from Re1.

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of the molecule of (I), with displacement ellipsoids drawn at the 30% probability level and H atoms shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A packing diagram for (I), viewed along the ? axis.
[Figure 3] Fig. 3. The classical and non-classical hydrogen bonds in (I).
fac-Tricarbonyl[hydroxybis(2-pyridyl)methanolato-κ3N,O,N')rhenium(I) top
Crystal data top
[Re(CO)3(C11H9N2O2)]F(000) = 1776
Mr = 471.43Dx = 2.181 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 27.742 (2) ÅCell parameters from 23 reflections
b = 7.8344 (16) Åθ = 6.3–26.4°
c = 16.2658 (18) ŵ = 8.49 mm1
β = 125.679 (5)°T = 298 K
V = 2871.7 (7) Å3Rectangular, yellow
Z = 80.4 × 0.3 × 0.2 mm
Data collection top
Bruker P4
diffractometer
2359 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.026
Graphite monochromatorθmax = 25.0°, θmin = 2.5°
2θ/ω scansh = 132
Absorption correction: empirical (using intensity measurements) via ψ-scans
(XSCANS; Siemens, 1996)
k = 19
Tmin = 0.061, Tmax = 0.183l = 1915
3138 measured reflections3 standard reflections every 97 reflections
2535 independent reflections intensity decay: 0.0%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.093 w = 1/[σ2(Fo2) + (0.075P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
2535 reflectionsΔρmax = 1.75 e Å3
200 parametersΔρmin = 1.34 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00143 (11)
Crystal data top
[Re(CO)3(C11H9N2O2)]V = 2871.7 (7) Å3
Mr = 471.43Z = 8
Monoclinic, C2/cMo Kα radiation
a = 27.742 (2) ŵ = 8.49 mm1
b = 7.8344 (16) ÅT = 298 K
c = 16.2658 (18) Å0.4 × 0.3 × 0.2 mm
β = 125.679 (5)°
Data collection top
Bruker P4
diffractometer
2359 reflections with I > 2σ(I)
Absorption correction: empirical (using intensity measurements) via ψ-scans
(XSCANS; Siemens, 1996)
Rint = 0.026
Tmin = 0.061, Tmax = 0.1833 standard reflections every 97 reflections
3138 measured reflections intensity decay: 0.0%
2535 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.093H-atom parameters constrained
S = 1.02Δρmax = 1.75 e Å3
2535 reflectionsΔρmin = 1.34 e Å3
200 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
xyzUiso*/Ueq
Re10.108968 (8)0.85564 (3)0.019674 (13)0.02688 (15)
C10.1236 (3)1.0687 (8)0.0919 (4)0.0396 (13)
C20.0436 (3)0.7983 (10)0.0267 (4)0.0422 (14)
C30.1605 (3)0.7392 (9)0.1448 (4)0.0446 (15)
O10.1331 (3)1.1947 (7)0.1313 (4)0.0607 (13)
O20.0055 (2)0.7633 (9)0.0307 (4)0.0684 (15)
O30.1926 (3)0.6640 (8)0.2191 (4)0.084 (2)
N10.0918 (2)0.6455 (5)0.0814 (4)0.0286 (10)
C110.0896 (2)0.4770 (7)0.0681 (4)0.0341 (12)
H110.09600.43910.00830.041*
C120.0783 (3)0.3589 (7)0.1400 (6)0.0442 (17)
H120.07700.24310.12890.053*
C130.0688 (2)0.4145 (8)0.2289 (5)0.0403 (14)
H130.06140.33590.27790.048*
C140.0704 (2)0.5869 (7)0.2451 (4)0.0315 (11)
H140.06450.62600.30430.038*
C150.0809 (2)0.7004 (7)0.1706 (4)0.0275 (10)
C40.0845 (2)0.8944 (7)0.1741 (4)0.0240 (10)
N20.17479 (18)0.9199 (6)0.0092 (3)0.0286 (9)
C210.2329 (2)0.9539 (8)0.0594 (4)0.0399 (13)
H210.24980.94020.12790.048*
C220.2676 (2)1.0084 (9)0.0297 (5)0.0483 (15)
H220.30771.03040.07770.058*
C230.2427 (3)1.0302 (10)0.0711 (5)0.0522 (16)
H230.26571.06940.09180.063*
C240.1830 (2)0.9935 (9)0.1422 (4)0.0396 (13)
H240.16561.00400.21110.048*
C250.15068 (19)0.9413 (6)0.1078 (3)0.0260 (10)
O40.05917 (14)0.9619 (4)0.1269 (2)0.0251 (7)
O50.05923 (15)0.9579 (5)0.2702 (2)0.0314 (8)
H50.02300.95870.30130.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Re10.0321 (2)0.0250 (2)0.0235 (2)0.00341 (7)0.01616 (14)0.00235 (6)
C10.046 (3)0.041 (4)0.026 (2)0.003 (3)0.018 (2)0.005 (2)
C20.048 (3)0.045 (4)0.035 (3)0.002 (3)0.025 (3)0.006 (3)
C30.047 (3)0.047 (4)0.036 (3)0.009 (3)0.021 (3)0.004 (3)
O10.090 (4)0.039 (3)0.051 (3)0.001 (3)0.040 (3)0.014 (2)
O20.059 (3)0.100 (5)0.066 (3)0.004 (3)0.048 (3)0.015 (3)
O30.104 (5)0.080 (4)0.042 (3)0.036 (3)0.028 (3)0.035 (3)
N10.032 (2)0.027 (3)0.030 (2)0.0021 (16)0.019 (2)0.0004 (16)
C110.037 (3)0.018 (3)0.047 (3)0.002 (2)0.024 (2)0.006 (2)
C120.037 (3)0.019 (3)0.072 (5)0.003 (2)0.029 (3)0.004 (2)
C130.035 (3)0.028 (3)0.051 (3)0.004 (2)0.022 (3)0.017 (3)
C140.032 (2)0.031 (3)0.034 (3)0.002 (2)0.020 (2)0.007 (2)
C150.028 (2)0.023 (2)0.032 (2)0.002 (2)0.019 (2)0.001 (2)
C40.023 (2)0.022 (2)0.026 (2)0.0002 (19)0.0141 (19)0.001 (2)
N20.0260 (19)0.026 (2)0.029 (2)0.0015 (18)0.0136 (17)0.0030 (18)
C210.028 (2)0.039 (3)0.036 (3)0.006 (2)0.009 (2)0.009 (2)
C220.030 (3)0.052 (4)0.056 (3)0.010 (3)0.021 (3)0.009 (3)
C230.037 (3)0.057 (4)0.067 (4)0.007 (3)0.033 (3)0.002 (3)
C240.042 (3)0.041 (3)0.038 (3)0.007 (3)0.024 (2)0.002 (3)
C250.024 (2)0.020 (2)0.031 (2)0.0007 (19)0.0149 (19)0.0007 (19)
O40.0269 (15)0.0207 (18)0.0276 (16)0.0027 (13)0.0158 (14)0.0018 (13)
O50.0277 (16)0.041 (2)0.0233 (16)0.0032 (16)0.0139 (14)0.0060 (15)
Geometric parameters (Å, º) top
Re1—C31.904 (6)C14—C151.390 (8)
Re1—C21.936 (6)C14—H140.9300
Re1—C11.942 (6)C15—C41.526 (7)
Re1—O42.108 (3)C4—O51.379 (6)
Re1—N12.175 (4)C4—O41.413 (6)
Re1—N22.192 (5)C4—C251.535 (6)
C1—O11.122 (8)N2—C251.341 (7)
C2—O21.129 (8)N2—C211.348 (7)
C3—O31.159 (7)C21—C221.372 (9)
N1—C111.344 (7)C21—H210.9300
N1—C151.367 (7)C22—C231.369 (9)
C11—C121.376 (9)C22—H220.9300
C11—H110.9300C23—C241.389 (8)
C12—C131.381 (10)C23—H230.9300
C12—H120.9300C24—C251.368 (8)
C13—C141.381 (8)C24—H240.9300
C13—H130.9300O5—H50.8200
C3—Re1—C288.3 (3)C13—C14—H14120.9
C3—Re1—C190.2 (3)C15—C14—H14120.9
C2—Re1—C192.1 (3)N1—C15—C14121.8 (5)
C3—Re1—O4170.6 (2)N1—C15—C4112.0 (4)
C2—Re1—O498.05 (19)C14—C15—C4126.1 (5)
C1—Re1—O496.48 (18)O5—C4—O4113.3 (4)
C3—Re1—N198.2 (2)O5—C4—C15113.6 (4)
C2—Re1—N194.0 (2)O4—C4—C15106.7 (4)
C1—Re1—N1169.8 (2)O5—C4—C25108.7 (4)
O4—Re1—N174.55 (14)O4—C4—C25107.4 (4)
C3—Re1—N298.0 (2)C15—C4—C25106.8 (4)
C2—Re1—N2172.74 (19)C25—N2—C21119.1 (5)
C1—Re1—N291.4 (2)C25—N2—Re1112.8 (3)
O4—Re1—N275.26 (14)C21—N2—Re1127.8 (4)
N1—Re1—N281.61 (17)N2—C21—C22121.1 (5)
O1—C1—Re1176.8 (6)N2—C21—H21119.4
O2—C2—Re1179.4 (7)C22—C21—H21119.4
O3—C3—Re1177.2 (6)C23—C22—C21119.5 (5)
C11—N1—C15118.5 (5)C23—C22—H22120.2
C11—N1—Re1129.2 (4)C21—C22—H22120.2
C15—N1—Re1112.3 (3)C22—C23—C24119.7 (6)
N1—C11—C12122.2 (6)C22—C23—H23120.2
N1—C11—H11118.9C24—C23—H23120.2
C12—C11—H11118.9C25—C24—C23118.0 (5)
C11—C12—C13119.1 (5)C25—C24—H24121.0
C11—C12—H12120.4C23—C24—H24121.0
C13—C12—H12120.4N2—C25—C24122.6 (4)
C12—C13—C14120.0 (5)N2—C25—C4111.6 (4)
C12—C13—H13120.0C24—C25—C4125.8 (4)
C14—C13—H13120.0C4—O4—Re1105.2 (3)
C13—C14—C15118.3 (6)C4—O5—H5109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5···O4i0.821.862.679 (5)179
C12—H12···O4ii0.932.263.183 (7)171
Symmetry codes: (i) x, y, z1/2; (ii) x, y1, z.

Experimental details

Crystal data
Chemical formula[Re(CO)3(C11H9N2O2)]
Mr471.43
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)27.742 (2), 7.8344 (16), 16.2658 (18)
β (°) 125.679 (5)
V3)2871.7 (7)
Z8
Radiation typeMo Kα
µ (mm1)8.49
Crystal size (mm)0.4 × 0.3 × 0.2
Data collection
DiffractometerBruker P4
diffractometer
Absorption correctionEmpirical (using intensity measurements) via ψ-scans
(XSCANS; Siemens, 1996)
Tmin, Tmax0.061, 0.183
No. of measured, independent and
observed [I > 2σ(I)] reflections
3138, 2535, 2359
Rint0.026
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.093, 1.02
No. of reflections2535
No. of parameters200
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.75, 1.34

Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.

Selected geometric parameters (Å, º) top
Re1—C31.904 (6)C1—O11.122 (8)
Re1—C21.936 (6)C2—O21.129 (8)
Re1—C11.942 (6)C3—O31.159 (7)
Re1—O42.108 (3)C4—O51.379 (6)
Re1—N12.175 (4)C4—O41.413 (6)
Re1—N22.192 (5)
C3—Re1—C288.3 (3)C1—Re1—N291.4 (2)
C3—Re1—C190.2 (3)O4—Re1—N275.26 (14)
C2—Re1—C192.1 (3)N1—Re1—N281.61 (17)
C3—Re1—O4170.6 (2)O1—C1—Re1176.8 (6)
C2—Re1—O498.05 (19)O2—C2—Re1179.4 (7)
C1—Re1—O496.48 (18)O3—C3—Re1177.2 (6)
C3—Re1—N198.2 (2)O5—C4—O4113.3 (4)
C2—Re1—N194.0 (2)O5—C4—C15113.6 (4)
C1—Re1—N1169.8 (2)O4—C4—C15106.7 (4)
O4—Re1—N174.55 (14)O5—C4—C25108.7 (4)
C3—Re1—N298.0 (2)O4—C4—C25107.4 (4)
C2—Re1—N2172.74 (19)C4—O4—Re1105.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5···O4i0.821.862.679 (5)179
C12—H12···O4ii0.932.263.183 (7)171
Symmetry codes: (i) x, y, z1/2; (ii) x, y1, z.
 

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