Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109035902/sq3211sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109035902/sq3211Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109035902/sq3211IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109035902/sq3211IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109035902/sq3211IVsup5.hkl |
CCDC references: 760062; 760063; 760064; 760065
Compounds (I)–(IV) were prepared according to the standard literature procedure (Sterzo et al., 1989). Crystals of (I) and (III) were obtained by slow evaporation of hexane solutions. Crystals of (II) and (IV) were grown by slow evaporation of chloroform solutions at room temperature.
All H atoms were positioned geometrically, with C—H = 1.00 Å, and included in riding mode, with Uiso(H) = 1.2Ueq(C).
One of the rapidly growing fields in metalloorganic chemistry is the synthesis of new materials. Such examples include dendrimers (Tomalia et al., 1990; Stulgies et al., 2004; Astruc et al., 2008), staffanes (Kaszynski et al., 1992), Diederich's carbon nets (Diederich & Rubin, 1992), and various novel electronic, photonic and magnetic materials (Barlow & O'Hare, 1997; Elschenbroich et al., 2005; Kinnibrugh et al., 2009). Because of the increasing interest in this area, we have focused our studies on structural investigations of the title compounds, (I)–(IV) (Figs. 1 and 2), which can be used as starting compounds for the construction of new materials (Sterzo et al., 1989). This work reports the first structural studies of monohalogenated derivatives of (η5-C5H4X)M(CO)3 [for (I), M = Mn and X = I; for (III), M = Re and X = I] and the dinuclear [(CO)3MC5H4]C≡C[C5H4M(CO)3] compounds [for (II), M = Mn; for (IV), M = Re].
The mean values of the geometric parameters for compounds (I)–(IV) are in accordance with those previously reported (Table 1) for 89 mono-substituted cymantrenes and 27 (η5-C5H4X)Re(CO)3 compounds, which were retrieved from the 2009 version of the Cambridge Structural Database (CSD; Allen, 2002) using ConQuest (Version 1.11; Macrae et al., 2006), as well as with the unsubstituted compounds C5H5M(CO)3 (M = Mn, Re) (Fitzpatrick, Le Page & Butler, 1981 or Fitzpatrick, Le Page et al., 1981; Cowie et al., 1990). The mono-substituted complexes (η5-C5H4X)M(CO)3 (X is any atom, M = Mn, Re) were considered with the following search criteria: (a) three-dimensional coordinates and R < 0.10; (b) no errors; (c) no crystallographic disorder; (d) no polymer structures. The (O)C—Mn—C(O) angle is in accord with a tendency for decreasing the pyramidality of the M(CO)3 fragment with increasing π-donor capacity of the cyclic polyene (Fitzpatrick, Le Page & Butler, 1981 or Fitzpatrick, Le Page et al., 1981): (C6H6)Cr(CO)3 88.22 (8)° (Rees & Coppens, 1973), CpRe(CO)3 90.0 (2)° (Fitzpatrick, Le Page & Butler, 1981 or Fitzpatrick, Le Page et al., 1981), CpMn(CO)3 92.02 (5)° (Cowie et al., 1990), (C4H4)Fe(CO)3 95.6° (Hall et al., 1975) and (C4Ph4)Fe(CO)3 97.03 (3)° (Dodge & Schomaker, 1965). The M—C—O bond angles do not differ significantly from 180°.
The M(CO)3 (M = Mn, Re) fragment possess approximate C3v symmetry, while coordination to the η5-C5H4X ring lowers the molecular symmetry to C1 (Fig. 3). Compounds (I)–(IV) possess different mutual dispositions of the carbonyl groups and η5-C5H4X rings: the C6≡O1 carbonyl group for (I) and (III) is in an eclipsed position relative to the substituted C atom of the η5-C5H4I ring, while the C7≡O1 carbonyl group of (II) and (IV) is in the transoid position to the substitutent-bearing C atom (Figs. 3 and 4).
Compounds (II) and (IV) crystallize with the molecules occupying a special position on an inversion center. Each molecule consists of two identical [(CO)3M(C5H4)C≡] (M = Mn, Re) parts with the M(CO)3 moieties in transoid positions. We suggest that (II) and (IV) adopt the transoid structure due to the realisation of strong attractive intermolecular π(CO)–π(CO) interactions in the sheared parallel packing motif (see below). In contrast, the only analogous compound found in the literature, [(CO)3Mn(C5H4)C≡C(C7H5)Cr(CO)3]BF4, possesses a syn-facial (cisoid) conformation of M(CO)3 moieties, due to the formation of strong attractive intermolecular π(CO)–π(CO) interactions with a perpendicular packing motif (Tamm et al., 2000). The conformation of [(CO)3M(C5H4)] moieties thus appears to depend, at least in part, on the type of π(CO)–π(CO) interactions formed.
The molecules in all four structures form zigzag chains due to the formation of strong attractive interactions. For (I) and (III), the zigzag chains implemented along the crystallographic b axis involve strong attractive I···O interactions [I1···O2A(2 - x, -1/2 + y, 3/2 - z) = 3.233 (2) Å and I1···O2A–C7A = 112.1 (2)° for (I), and I1···O2A(2 - x, -1/2 + y, 3/2 - z) = 3.231 (4) Å and I1···O2A–C7A 110.6 (3)° for (III)] (Fig. 5). The attractive nature of halogen···oxygen interactions is caused by electrostatic effects, polarization, charge transfer and dispersion contributions. The tendency to form short X···E (E = O, N) interactions (X = I > Br > Cl) increases with the magnitude of their polarizabilities (Lommerse et al., 1996). The directionality of that type of interaction has been interpreted in terms of charge transfer between the highest occupied molecular orbital of E and the lowest unoccupied molecular orbital of X (Ramasubbu et al., 1986). The strength of halogen–carbonyl interactions has been characterized as a function of two geometric parameters, the halogen–oxygen distance (X···O) and the halogen–oxygen–carbon angle (X···O—C). The interaction energy of the most strongly bound system was found to be 2.39 kcal mol-1 (1 kcal mol-1 = 4.184 kJ mol-1) (iodobenzene–formaldehyde; I···O = 3.2 Å and I···O—C 110°), of the same magnitude as those for C—H···O hydrogen bonds (Riley & Merz, 2007). The observed interactions in (I) and (III) are consistent in geometry with these calculated strong interactions.
According to a systematic CSD analysis (Allen et al., 1998) of interactions between ketonic (C2—C═O) carbonyl groups, three types of interaction motifs were identified: a predominant slightly sheared antiparallel motif, a perpendicular motif, and a highly sheared parallel motif. For transition metal carbonyls, a higher percentage of the perpendicular motif has been reported (Allen et al., 2006). Compounds (II) and (IV) contain strong attractive antiparallel intermolecular π(CO)–π(CO) interactions between the carbonyl groups of neighboring molecules [O2···C8A(2 - x, -y, z) = 3.138 (2) Å, C8—O2···C8A = 105.00 (10)° for (II), and O2···C8A(2 - x, -y, z) = 3.211 (6) Å and C8—O2···C8A = 101.8 (3)° for (IV)], forming pairwise interactions in a sheared antiparallel dimer motif along the crystallographic b axis (Fig. 6). These antiparallel π(CO)–π(CO) interactions are a driving force for the formation of zigzag chains along the b axis. Comparison of the parameters obtained for (II) and (IV) with distances and angles reported for similar interactions in other transition metal carbonyls (2.95–3.60 Å/80–135°) indicates that the π(CO)–π(CO) interactions are relatively strong in (II) and (IV) (Allen et al., 2006). Also, intermolecular π(CO)–π(CO) interactions are not rare, and sheared antiparallel and perpendicular motifs can be found for 14 of the 89 hits for mono-substituted cymantrenes and for 3 of the 27 hits for (η5-C5H4X)Re(CO)3 compounds in the CSD search (see above). The mean van der Waals radii used to identify intermolecular interactions and contacts were taken as C = 1.53, O = 1.42 and I = 2.04 Å (Bondi, 1964).
The zigzag chains in (I) and (III) are bound to each other by weak intermolecular C—H···O hydrogen bonds, while those in (II) and (IV) associate by a combination of weak C—H···O hydrogen bonds and π(Csp2)–π(Csp2) and π(Csp2)–π(Csp) stacking interactions between pairs of inversion-related molecules (C···C distances ca 3.4 Å), leading to a ladder-type packing (Fig. 7).
For all compounds, data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Mn(C5H4I)(CO)3] | F(000) = 616 |
Mr = 329.95 | Dx = 2.325 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 4583 reflections |
a = 7.2696 (5) Å | θ = 2.5–30.5° |
b = 10.7776 (7) Å | µ = 4.64 mm−1 |
c = 12.0288 (8) Å | T = 100 K |
V = 942.44 (11) Å3 | Plate, yellow |
Z = 4 | 0.20 × 0.15 × 0.07 mm |
Bruker SMART APEXII CCD area-detector diffractometer | 2278 independent reflections |
Radiation source: fine-focus sealed tube | 2161 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
φ and ω scans | θmax = 28.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −9→9 |
Tmin = 0.427, Tmax = 0.717 | k = −14→14 |
9507 measured reflections | l = −15→15 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.020 | H-atom parameters constrained |
wR(F2) = 0.048 | w = 1/[σ2(Fo2) + (0.021P)2 + 0.223P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
2278 reflections | Δρmax = 0.54 e Å−3 |
118 parameters | Δρmin = −0.38 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.05 (3) |
[Mn(C5H4I)(CO)3] | V = 942.44 (11) Å3 |
Mr = 329.95 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.2696 (5) Å | µ = 4.64 mm−1 |
b = 10.7776 (7) Å | T = 100 K |
c = 12.0288 (8) Å | 0.20 × 0.15 × 0.07 mm |
Bruker SMART APEXII CCD area-detector diffractometer | 2278 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2161 reflections with I > 2σ(I) |
Tmin = 0.427, Tmax = 0.717 | Rint = 0.031 |
9507 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | H-atom parameters constrained |
wR(F2) = 0.048 | Δρmax = 0.54 e Å−3 |
S = 1.06 | Δρmin = −0.38 e Å−3 |
2278 reflections | Absolute structure: Flack (1983), with how many Friedel pairs? |
118 parameters | Absolute structure parameter: 0.05 (3) |
0 restraints |
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 | ||
I1 | 1.25297 (3) | −0.142841 (19) | 0.649202 (17) | 0.02989 (7) | |
Mn1 | 0.81740 (6) | 0.01925 (4) | 0.55665 (4) | 0.01790 (10) | |
O1 | 0.7565 (3) | −0.2275 (2) | 0.6561 (2) | 0.0353 (5) | |
O2 | 0.5588 (3) | 0.1308 (2) | 0.7161 (2) | 0.0325 (6) | |
O3 | 0.5279 (4) | −0.0189 (2) | 0.38760 (19) | 0.0386 (6) | |
C1 | 1.1108 (4) | 0.0017 (3) | 0.5717 (3) | 0.0231 (7) | |
C2 | 1.0538 (4) | 0.1133 (3) | 0.6233 (3) | 0.0257 (7) | |
H2 | 1.0741 | 0.1376 | 0.7026 | 0.031* | |
C3 | 0.9711 (5) | 0.1874 (3) | 0.5383 (3) | 0.0303 (8) | |
H3 | 0.9218 | 0.2734 | 0.5479 | 0.036* | |
C4 | 0.9765 (5) | 0.1201 (3) | 0.4377 (3) | 0.0300 (7) | |
H4 | 0.9312 | 0.1505 | 0.3641 | 0.036* | |
C5 | 1.0619 (4) | 0.0048 (3) | 0.4572 (3) | 0.0257 (7) | |
H5 | 1.0891 | −0.0605 | 0.4005 | 0.031* | |
C6 | 0.7812 (4) | −0.1319 (3) | 0.6158 (3) | 0.0232 (7) | |
C7 | 0.6585 (4) | 0.0867 (3) | 0.6528 (3) | 0.0236 (6) | |
C8 | 0.6403 (4) | −0.0049 (3) | 0.4541 (3) | 0.0256 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.02248 (10) | 0.03315 (12) | 0.03405 (11) | 0.00062 (10) | −0.00482 (11) | 0.00482 (9) |
Mn1 | 0.0205 (2) | 0.01662 (19) | 0.0166 (2) | −0.00072 (17) | 0.00021 (18) | 0.00113 (18) |
O1 | 0.0321 (12) | 0.0239 (11) | 0.0498 (14) | −0.0032 (11) | −0.0041 (16) | 0.0130 (10) |
O2 | 0.0393 (14) | 0.0289 (13) | 0.0293 (13) | 0.0030 (12) | 0.0110 (11) | −0.0051 (11) |
O3 | 0.0402 (15) | 0.0458 (16) | 0.0297 (13) | 0.0017 (13) | −0.0133 (11) | −0.0020 (12) |
C1 | 0.0203 (15) | 0.0268 (17) | 0.0223 (15) | −0.0043 (12) | 0.0002 (12) | 0.0014 (13) |
C2 | 0.0250 (16) | 0.0241 (16) | 0.0280 (17) | −0.0094 (13) | 0.0006 (13) | −0.0041 (13) |
C3 | 0.0291 (17) | 0.0199 (15) | 0.042 (2) | −0.0073 (14) | 0.0055 (16) | 0.0059 (15) |
C4 | 0.0282 (17) | 0.0338 (18) | 0.0281 (17) | −0.0077 (14) | 0.0038 (15) | 0.0104 (15) |
C5 | 0.0251 (16) | 0.0330 (18) | 0.0189 (15) | −0.0009 (13) | 0.0047 (12) | −0.0012 (14) |
C6 | 0.0168 (17) | 0.0272 (16) | 0.0257 (14) | 0.0027 (12) | 0.0005 (11) | 0.0011 (12) |
C7 | 0.0276 (16) | 0.0195 (14) | 0.0238 (15) | −0.0034 (13) | −0.0040 (14) | 0.0046 (13) |
C8 | 0.0299 (18) | 0.0262 (17) | 0.0205 (15) | 0.0026 (13) | 0.0052 (13) | 0.0014 (14) |
I1—C1 | 2.089 (3) | O3—C8 | 1.153 (4) |
Mn1—C7 | 1.789 (3) | C1—C2 | 1.415 (4) |
Mn1—C6 | 1.797 (3) | C1—C5 | 1.423 (4) |
Mn1—C8 | 1.802 (3) | C5—C4 | 1.409 (5) |
Mn1—C4 | 2.136 (3) | C5—H5 | 1.0000 |
Mn1—C3 | 2.141 (3) | C4—C3 | 1.411 (5) |
Mn1—C5 | 2.148 (3) | C4—H4 | 1.0000 |
Mn1—C1 | 2.149 (3) | C3—C2 | 1.430 (5) |
Mn1—C2 | 2.150 (3) | C3—H3 | 1.0000 |
O1—C6 | 1.153 (4) | C2—H2 | 1.0000 |
O2—C7 | 1.153 (4) | ||
C7—Mn1—C6 | 91.04 (14) | C2—C1—I1 | 125.7 (2) |
C7—Mn1—C8 | 92.29 (14) | C5—C1—I1 | 124.9 (2) |
C6—Mn1—C8 | 92.02 (14) | C2—C1—Mn1 | 70.82 (19) |
C7—Mn1—C4 | 125.15 (14) | C5—C1—Mn1 | 70.62 (18) |
C6—Mn1—C4 | 143.64 (13) | I1—C1—Mn1 | 126.46 (15) |
C8—Mn1—C4 | 90.11 (14) | O3—C8—Mn1 | 179.0 (3) |
C7—Mn1—C3 | 93.42 (14) | C4—C5—C1 | 107.0 (3) |
C6—Mn1—C3 | 152.23 (14) | C4—C5—Mn1 | 70.36 (18) |
C8—Mn1—C3 | 115.14 (14) | C1—C5—Mn1 | 70.70 (18) |
C4—Mn1—C3 | 38.53 (14) | C4—C5—H5 | 126.5 |
C7—Mn1—C5 | 157.48 (13) | C1—C5—H5 | 126.5 |
C6—Mn1—C5 | 106.00 (13) | Mn1—C5—H5 | 126.5 |
C8—Mn1—C5 | 101.51 (13) | C5—C4—C3 | 108.9 (3) |
C4—Mn1—C5 | 38.39 (12) | C5—C4—Mn1 | 71.25 (18) |
C3—Mn1—C5 | 64.66 (13) | C3—C4—Mn1 | 70.90 (19) |
C7—Mn1—C1 | 128.47 (13) | C5—C4—H4 | 125.6 |
C6—Mn1—C1 | 91.84 (12) | C3—C4—H4 | 125.6 |
C8—Mn1—C1 | 138.95 (13) | Mn1—C4—H4 | 125.6 |
C4—Mn1—C1 | 64.15 (13) | C4—C3—C2 | 108.3 (3) |
C3—Mn1—C1 | 64.22 (13) | C4—C3—Mn1 | 70.56 (18) |
C5—Mn1—C1 | 38.67 (12) | C2—C3—Mn1 | 70.88 (18) |
C7—Mn1—C2 | 94.79 (13) | C4—C3—H3 | 125.8 |
C6—Mn1—C2 | 113.37 (13) | C2—C3—H3 | 125.8 |
C8—Mn1—C2 | 153.45 (14) | Mn1—C3—H3 | 125.8 |
C4—Mn1—C2 | 65.00 (13) | C1—C2—C3 | 106.5 (3) |
C3—Mn1—C2 | 38.94 (13) | C1—C2—Mn1 | 70.75 (18) |
C5—Mn1—C2 | 65.19 (12) | C3—C2—Mn1 | 70.18 (18) |
C1—Mn1—C2 | 38.43 (12) | C1—C2—H2 | 126.7 |
O1—C6—Mn1 | 178.3 (3) | C3—C2—H2 | 126.7 |
O2—C7—Mn1 | 178.7 (3) | Mn1—C2—H2 | 126.7 |
C2—C1—C5 | 109.4 (3) | ||
C8—Mn1—C1—C2 | 138.1 (2) | C2—Mn1—C4—C5 | 81.0 (2) |
C4—Mn1—C1—C2 | 81.7 (2) | C7—Mn1—C4—C3 | 39.9 (3) |
C3—Mn1—C1—C2 | 38.7 (2) | C6—Mn1—C4—C3 | −133.6 (2) |
C5—Mn1—C1—C2 | 119.6 (3) | C8—Mn1—C4—C3 | 132.8 (2) |
C7—Mn1—C1—C5 | −153.6 (2) | C5—Mn1—C4—C3 | −118.6 (3) |
C6—Mn1—C1—C5 | 113.7 (2) | C1—Mn1—C4—C3 | −80.4 (2) |
C8—Mn1—C1—C5 | 18.5 (3) | C2—Mn1—C4—C3 | −37.6 (2) |
C4—Mn1—C1—C5 | −38.0 (2) | C5—C4—C3—C2 | −0.3 (4) |
C3—Mn1—C1—C5 | −81.0 (2) | Mn1—C4—C3—C2 | 61.2 (2) |
C2—Mn1—C1—C5 | −119.6 (3) | C5—C4—C3—Mn1 | −61.5 (2) |
C7—Mn1—C1—I1 | 86.8 (2) | C7—Mn1—C3—C4 | −148.3 (2) |
C6—Mn1—C1—I1 | −6.0 (2) | C6—Mn1—C3—C4 | 112.9 (3) |
C8—Mn1—C1—I1 | −101.2 (2) | C8—Mn1—C3—C4 | −54.1 (2) |
C4—Mn1—C1—I1 | −157.6 (2) | C5—Mn1—C3—C4 | 37.1 (2) |
C3—Mn1—C1—I1 | 159.4 (2) | C1—Mn1—C3—C4 | 80.2 (2) |
C5—Mn1—C1—I1 | −119.7 (3) | C2—Mn1—C3—C4 | 118.3 (3) |
C2—Mn1—C1—I1 | 120.7 (3) | C7—Mn1—C3—C2 | 93.4 (2) |
C2—C1—C5—C4 | 0.9 (4) | C6—Mn1—C3—C2 | −5.4 (4) |
I1—C1—C5—C4 | −177.1 (2) | C8—Mn1—C3—C2 | −172.5 (2) |
Mn1—C1—C5—C4 | 61.4 (2) | C4—Mn1—C3—C2 | −118.3 (3) |
C2—C1—C5—Mn1 | −60.5 (2) | C5—Mn1—C3—C2 | −81.2 (2) |
I1—C1—C5—Mn1 | 121.5 (2) | C1—Mn1—C3—C2 | −38.15 (19) |
C7—Mn1—C5—C4 | −51.4 (4) | C5—C1—C2—C3 | −1.1 (4) |
C6—Mn1—C5—C4 | 170.8 (2) | I1—C1—C2—C3 | 176.9 (2) |
C8—Mn1—C5—C4 | 75.3 (2) | Mn1—C1—C2—C3 | −61.4 (2) |
C3—Mn1—C5—C4 | −37.2 (2) | C5—C1—C2—Mn1 | 60.4 (2) |
C1—Mn1—C5—C4 | −117.0 (3) | I1—C1—C2—Mn1 | −121.7 (2) |
C2—Mn1—C5—C4 | −80.4 (2) | C4—C3—C2—C1 | 0.8 (4) |
C7—Mn1—C5—C1 | 65.5 (4) | Mn1—C3—C2—C1 | 61.8 (2) |
C6—Mn1—C5—C1 | −72.3 (2) | C4—C3—C2—Mn1 | −61.0 (2) |
C8—Mn1—C5—C1 | −167.7 (2) | C7—Mn1—C2—C1 | 154.0 (2) |
C4—Mn1—C5—C1 | 117.0 (3) | C6—Mn1—C2—C1 | 60.8 (2) |
C3—Mn1—C5—C1 | 79.7 (2) | C8—Mn1—C2—C1 | −101.1 (3) |
C2—Mn1—C5—C1 | 36.53 (19) | C4—Mn1—C2—C1 | −79.3 (2) |
C1—C5—C4—C3 | −0.3 (4) | C3—Mn1—C2—C1 | −116.5 (3) |
Mn1—C5—C4—C3 | 61.2 (2) | C5—Mn1—C2—C1 | −36.76 (18) |
C1—C5—C4—Mn1 | −61.6 (2) | C7—Mn1—C2—C3 | −89.5 (2) |
C7—Mn1—C4—C5 | 158.5 (2) | C6—Mn1—C2—C3 | 177.3 (2) |
C6—Mn1—C4—C5 | −15.0 (3) | C8—Mn1—C2—C3 | 15.4 (4) |
C8—Mn1—C4—C5 | −108.6 (2) | C4—Mn1—C2—C3 | 37.2 (2) |
C3—Mn1—C4—C5 | 118.6 (3) | C5—Mn1—C2—C3 | 79.7 (2) |
C1—Mn1—C4—C5 | 38.24 (19) | C1—Mn1—C2—C3 | 116.5 (3) |
[Mn2(C12H8)(CO)6] | F(000) = 428 |
Mr = 430.12 | Dx = 1.720 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4260 reflections |
a = 6.4096 (10) Å | θ = 3.2–30.3° |
b = 10.9991 (16) Å | µ = 1.55 mm−1 |
c = 11.9798 (18) Å | T = 100 K |
β = 100.507 (2)° | Needle, brown |
V = 830.4 (2) Å3 | 0.31 × 0.11 × 0.10 mm |
Z = 2 |
Bruker SMART APEXII CCD area-detector diffractometer | 2552 independent reflections |
Radiation source: fine-focus sealed tube | 2211 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
φ and ω scans | θmax = 30.6°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −9→9 |
Tmin = 0.645, Tmax = 0.860 | k = −15→15 |
12974 measured reflections | l = −17→17 |
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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.035P)2 + 0.228P] where P = (Fo2 + 2Fc2)/3 |
2552 reflections | (Δ/σ)max < 0.001 |
118 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
[Mn2(C12H8)(CO)6] | V = 830.4 (2) Å3 |
Mr = 430.12 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.4096 (10) Å | µ = 1.55 mm−1 |
b = 10.9991 (16) Å | T = 100 K |
c = 11.9798 (18) Å | 0.31 × 0.11 × 0.10 mm |
β = 100.507 (2)° |
Bruker SMART APEXII CCD area-detector diffractometer | 2552 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2211 reflections with I > 2σ(I) |
Tmin = 0.645, Tmax = 0.860 | Rint = 0.037 |
12974 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.42 e Å−3 |
2552 reflections | Δρmin = −0.24 e Å−3 |
118 parameters |
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 | ||
Mn1 | 0.73992 (3) | 0.218855 (18) | 0.083569 (17) | 0.01607 (7) | |
O1 | 0.5602 (2) | −0.01184 (11) | 0.14847 (11) | 0.0351 (3) | |
O2 | 0.95402 (19) | 0.10271 (11) | −0.08650 (10) | 0.0299 (3) | |
O3 | 1.12258 (19) | 0.18853 (12) | 0.25993 (10) | 0.0320 (3) | |
C1 | 0.7458 (2) | 0.40662 (12) | 0.03320 (12) | 0.0191 (3) | |
C2 | 0.6812 (2) | 0.39868 (13) | 0.14142 (13) | 0.0207 (3) | |
H2 | 0.7550 | 0.4373 | 0.2135 | 0.025* | |
C3 | 0.4911 (2) | 0.33056 (14) | 0.12793 (14) | 0.0237 (3) | |
H3 | 0.4074 | 0.3126 | 0.1888 | 0.028* | |
C4 | 0.4361 (2) | 0.29473 (14) | 0.01166 (14) | 0.0242 (3) | |
H4 | 0.3070 | 0.2477 | −0.0231 | 0.029* | |
C5 | 0.5918 (2) | 0.34167 (13) | −0.04681 (13) | 0.0221 (3) | |
H5 | 0.5917 | 0.3334 | −0.1300 | 0.027* | |
C6 | 0.9254 (2) | 0.47140 (13) | 0.00959 (12) | 0.0205 (3) | |
C7 | 0.6307 (2) | 0.07756 (14) | 0.12334 (13) | 0.0232 (3) | |
C8 | 0.8700 (2) | 0.14608 (13) | −0.01941 (12) | 0.0209 (3) | |
C9 | 0.9722 (2) | 0.20100 (13) | 0.19186 (13) | 0.0212 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.01592 (11) | 0.01522 (11) | 0.01650 (11) | −0.00088 (7) | 0.00146 (8) | 0.00127 (7) |
O1 | 0.0439 (7) | 0.0282 (6) | 0.0344 (6) | −0.0132 (5) | 0.0105 (6) | 0.0036 (5) |
O2 | 0.0363 (6) | 0.0307 (6) | 0.0244 (6) | 0.0073 (5) | 0.0103 (5) | 0.0022 (5) |
O3 | 0.0256 (6) | 0.0386 (7) | 0.0283 (6) | 0.0013 (5) | −0.0042 (5) | 0.0047 (5) |
C1 | 0.0182 (6) | 0.0161 (6) | 0.0227 (7) | 0.0015 (5) | 0.0029 (5) | 0.0034 (5) |
C2 | 0.0216 (7) | 0.0178 (6) | 0.0230 (7) | 0.0019 (5) | 0.0053 (5) | −0.0003 (5) |
C3 | 0.0199 (7) | 0.0232 (7) | 0.0298 (8) | 0.0023 (5) | 0.0090 (6) | 0.0020 (6) |
C4 | 0.0157 (6) | 0.0236 (7) | 0.0314 (8) | 0.0003 (5) | −0.0010 (6) | 0.0035 (6) |
C5 | 0.0219 (7) | 0.0211 (7) | 0.0214 (7) | 0.0024 (5) | −0.0012 (5) | 0.0037 (5) |
C6 | 0.0224 (7) | 0.0163 (6) | 0.0226 (7) | 0.0035 (5) | 0.0036 (5) | 0.0032 (5) |
C7 | 0.0245 (7) | 0.0232 (7) | 0.0217 (7) | −0.0040 (6) | 0.0036 (6) | −0.0003 (5) |
C8 | 0.0231 (7) | 0.0180 (6) | 0.0211 (7) | 0.0010 (5) | 0.0027 (5) | 0.0050 (5) |
C9 | 0.0228 (7) | 0.0196 (7) | 0.0215 (7) | −0.0009 (5) | 0.0049 (5) | 0.0015 (5) |
Mn1—C8 | 1.7980 (15) | C2—C1 | 1.434 (2) |
Mn1—C9 | 1.7983 (16) | C2—H2 | 1.0000 |
Mn1—C7 | 1.8040 (15) | C7—O1 | 1.1450 (19) |
Mn1—C4 | 2.1490 (15) | C1—C6 | 1.4252 (19) |
Mn1—C5 | 2.1505 (14) | C1—C5 | 1.435 (2) |
Mn1—C2 | 2.1515 (15) | C6—C6i | 1.201 (3) |
Mn1—C1 | 2.1538 (14) | C5—C4 | 1.417 (2) |
Mn1—C3 | 2.1554 (15) | C5—H5 | 1.0000 |
C9—O3 | 1.1516 (19) | C4—C3 | 1.428 (2) |
O2—C8 | 1.1497 (18) | C4—H4 | 1.0000 |
C2—C3 | 1.415 (2) | C3—H3 | 1.0000 |
C8—Mn1—C9 | 91.14 (7) | C1—C2—Mn1 | 70.63 (8) |
C8—Mn1—C7 | 92.79 (7) | C3—C2—H2 | 125.8 |
C9—Mn1—C7 | 91.47 (7) | C1—C2—H2 | 125.8 |
C8—Mn1—C4 | 113.42 (7) | Mn1—C2—H2 | 125.8 |
C9—Mn1—C4 | 154.43 (7) | O1—C7—Mn1 | 179.63 (16) |
C7—Mn1—C4 | 94.21 (6) | C6—C1—C2 | 125.93 (13) |
C8—Mn1—C5 | 88.84 (6) | C6—C1—C5 | 126.76 (14) |
C9—Mn1—C5 | 142.21 (6) | C2—C1—C5 | 107.26 (12) |
C7—Mn1—C5 | 126.28 (6) | C6—C1—Mn1 | 126.24 (10) |
C4—Mn1—C5 | 38.49 (6) | C2—C1—Mn1 | 70.46 (8) |
C8—Mn1—C2 | 139.51 (6) | C5—C1—Mn1 | 70.40 (8) |
C9—Mn1—C2 | 92.20 (6) | C6i—C6—C1 | 178.4 (2) |
C7—Mn1—C2 | 127.43 (6) | C4—C5—C1 | 108.17 (13) |
C4—Mn1—C2 | 64.74 (6) | C4—C5—Mn1 | 70.70 (8) |
C5—Mn1—C2 | 64.95 (6) | C1—C5—Mn1 | 70.65 (8) |
C8—Mn1—C1 | 101.57 (6) | C4—C5—H5 | 125.9 |
C9—Mn1—C1 | 104.61 (6) | C1—C5—H5 | 125.9 |
C7—Mn1—C1 | 158.06 (6) | Mn1—C5—H5 | 125.9 |
C4—Mn1—C1 | 64.93 (5) | O2—C8—Mn1 | 178.07 (13) |
C5—Mn1—C1 | 38.94 (5) | C5—C4—C3 | 108.12 (13) |
C2—Mn1—C1 | 38.90 (6) | C5—C4—Mn1 | 70.81 (8) |
C8—Mn1—C3 | 151.59 (6) | C3—C4—Mn1 | 70.86 (9) |
C9—Mn1—C3 | 115.91 (6) | C5—C4—H4 | 125.9 |
C7—Mn1—C3 | 94.91 (6) | C3—C4—H4 | 125.9 |
C4—Mn1—C3 | 38.76 (6) | Mn1—C4—H4 | 125.9 |
C5—Mn1—C3 | 64.69 (6) | C2—C3—C4 | 108.15 (13) |
C2—Mn1—C3 | 38.35 (6) | C2—C3—Mn1 | 70.68 (8) |
C1—Mn1—C3 | 64.79 (6) | C4—C3—Mn1 | 70.38 (9) |
O3—C9—Mn1 | 178.86 (14) | C2—C3—H3 | 125.9 |
C3—C2—C1 | 108.29 (13) | C4—C3—H3 | 125.9 |
C3—C2—Mn1 | 70.97 (8) | Mn1—C3—H3 | 125.9 |
C8—Mn1—C2—C3 | 134.65 (11) | C7—Mn1—C5—C4 | 39.02 (12) |
C9—Mn1—C2—C3 | −131.01 (9) | C2—Mn1—C5—C4 | −80.27 (10) |
C7—Mn1—C2—C3 | −37.48 (12) | C1—Mn1—C5—C4 | −118.25 (13) |
C4—Mn1—C2—C3 | 37.52 (9) | C3—Mn1—C5—C4 | −37.70 (9) |
C5—Mn1—C2—C3 | 80.22 (10) | C8—Mn1—C5—C1 | −110.14 (9) |
C1—Mn1—C2—C3 | 118.24 (12) | C9—Mn1—C5—C1 | −19.77 (14) |
C8—Mn1—C2—C1 | 16.41 (13) | C7—Mn1—C5—C1 | 157.26 (9) |
C9—Mn1—C2—C1 | 110.75 (9) | C4—Mn1—C5—C1 | 118.25 (13) |
C7—Mn1—C2—C1 | −155.71 (9) | C2—Mn1—C5—C1 | 37.98 (8) |
C4—Mn1—C2—C1 | −80.72 (9) | C3—Mn1—C5—C1 | 80.54 (9) |
C5—Mn1—C2—C1 | −38.01 (8) | C1—C5—C4—C3 | 0.35 (17) |
C3—Mn1—C2—C1 | −118.24 (12) | Mn1—C5—C4—C3 | 61.38 (11) |
C3—C2—C1—C6 | 177.53 (13) | C1—C5—C4—Mn1 | −61.02 (10) |
Mn1—C2—C1—C6 | −121.16 (14) | C8—Mn1—C4—C5 | −54.54 (11) |
C3—C2—C1—C5 | −0.18 (16) | C9—Mn1—C4—C5 | 108.27 (16) |
Mn1—C2—C1—C5 | 61.12 (9) | C7—Mn1—C4—C5 | −149.41 (10) |
C3—C2—C1—Mn1 | −61.30 (10) | C2—Mn1—C4—C5 | 80.86 (9) |
C8—Mn1—C1—C6 | −48.41 (14) | C1—Mn1—C4—C5 | 37.68 (9) |
C9—Mn1—C1—C6 | 45.85 (14) | C3—Mn1—C4—C5 | 117.98 (13) |
C7—Mn1—C1—C6 | −178.28 (15) | C8—Mn1—C4—C3 | −172.52 (9) |
C4—Mn1—C1—C6 | −159.03 (15) | C9—Mn1—C4—C3 | −9.72 (19) |
C5—Mn1—C1—C6 | −121.78 (17) | C7—Mn1—C4—C3 | 92.60 (10) |
C2—Mn1—C1—C6 | 120.79 (16) | C5—Mn1—C4—C3 | −117.98 (13) |
C3—Mn1—C1—C6 | 157.96 (15) | C2—Mn1—C4—C3 | −37.13 (9) |
C8—Mn1—C1—C2 | −169.21 (9) | C1—Mn1—C4—C3 | −80.30 (9) |
C9—Mn1—C1—C2 | −74.94 (9) | C1—C2—C3—C4 | 0.40 (16) |
C7—Mn1—C1—C2 | 60.93 (19) | Mn1—C2—C3—C4 | −60.69 (10) |
C4—Mn1—C1—C2 | 80.18 (9) | C1—C2—C3—Mn1 | 61.09 (10) |
C5—Mn1—C1—C2 | 117.43 (12) | C5—C4—C3—C2 | −0.46 (17) |
C3—Mn1—C1—C2 | 37.17 (8) | Mn1—C4—C3—C2 | 60.88 (10) |
C8—Mn1—C1—C5 | 73.37 (9) | C5—C4—C3—Mn1 | −61.35 (10) |
C9—Mn1—C1—C5 | 167.63 (9) | C8—Mn1—C3—C2 | −103.86 (14) |
C7—Mn1—C1—C5 | −56.50 (19) | C9—Mn1—C3—C2 | 56.96 (10) |
C4—Mn1—C1—C5 | −37.25 (9) | C7—Mn1—C3—C2 | 150.99 (9) |
C2—Mn1—C1—C5 | −117.43 (12) | C4—Mn1—C3—C2 | −118.39 (13) |
C3—Mn1—C1—C5 | −80.25 (9) | C5—Mn1—C3—C2 | −80.95 (9) |
C6—C1—C5—C4 | −177.80 (14) | C1—Mn1—C3—C2 | −37.70 (9) |
C2—C1—C5—C4 | −0.11 (16) | C8—Mn1—C3—C4 | 14.53 (17) |
Mn1—C1—C5—C4 | 61.05 (10) | C9—Mn1—C3—C4 | 175.35 (9) |
C6—C1—C5—Mn1 | 121.15 (14) | C7—Mn1—C3—C4 | −90.61 (10) |
C2—C1—C5—Mn1 | −61.16 (9) | C5—Mn1—C3—C4 | 37.44 (9) |
C8—Mn1—C5—C4 | 131.62 (10) | C2—Mn1—C3—C4 | 118.39 (13) |
C9—Mn1—C5—C4 | −138.02 (11) | C1—Mn1—C3—C4 | 80.70 (9) |
Symmetry code: (i) −x+2, −y+1, −z. |
[Re(C5H4I)(CO)3] | F(000) = 816 |
Mr = 461.21 | Dx = 3.157 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 7360 reflections |
a = 7.4117 (14) Å | θ = 2.5–30.6° |
b = 10.922 (2) Å | µ = 15.67 mm−1 |
c = 11.987 (2) Å | T = 100 K |
V = 970.3 (3) Å3 | Plate, white |
Z = 4 | 0.14 × 0.10 × 0.07 mm |
Bruker SMART APEXII CCD area-detector diffractometer | 2342 independent reflections |
Radiation source: fine-focus sealed tube | 2276 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
φ and ω scans | θmax = 28.0°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −9→9 |
Tmin = 0.218, Tmax = 0.407 | k = −14→14 |
9533 measured reflections | l = −15→15 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.018 | H-atom parameters constrained |
wR(F2) = 0.041 | w = 1/[σ2(Fo2) + (0.0017P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max = 0.002 |
2342 reflections | Δρmax = 1.60 e Å−3 |
118 parameters | Δρmin = −1.39 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.015 (7) |
[Re(C5H4I)(CO)3] | V = 970.3 (3) Å3 |
Mr = 461.21 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.4117 (14) Å | µ = 15.67 mm−1 |
b = 10.922 (2) Å | T = 100 K |
c = 11.987 (2) Å | 0.14 × 0.10 × 0.07 mm |
Bruker SMART APEXII CCD area-detector diffractometer | 2342 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2276 reflections with I > 2σ(I) |
Tmin = 0.218, Tmax = 0.407 | Rint = 0.036 |
9533 measured reflections |
R[F2 > 2σ(F2)] = 0.018 | H-atom parameters constrained |
wR(F2) = 0.041 | Δρmax = 1.60 e Å−3 |
S = 0.99 | Δρmin = −1.39 e Å−3 |
2342 reflections | Absolute structure: Flack (1983), with how many Friedel pairs? |
118 parameters | Absolute structure parameter: 0.015 (7) |
0 restraints |
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 | ||
I1 | 1.25872 (5) | −0.14876 (3) | 0.64470 (3) | 0.02327 (9) | |
Re1 | 0.82029 (2) | 0.016956 (17) | 0.557459 (15) | 0.01389 (5) | |
O1 | 0.7512 (5) | −0.2349 (4) | 0.6594 (3) | 0.0263 (8) | |
O2 | 0.5514 (5) | 0.1292 (4) | 0.7213 (3) | 0.0271 (9) | |
O3 | 0.5203 (5) | −0.0199 (4) | 0.3849 (3) | 0.0303 (9) | |
C1 | 1.1291 (6) | −0.0015 (5) | 0.5693 (4) | 0.0180 (10) | |
C2 | 1.0774 (7) | 0.1082 (5) | 0.6235 (5) | 0.0222 (11) | |
H2 | 1.1028 | 0.1303 | 0.7029 | 0.027* | |
C3 | 0.9997 (7) | 0.1866 (5) | 0.5408 (5) | 0.0258 (12) | |
H3 | 0.9608 | 0.2734 | 0.5523 | 0.031* | |
C4 | 1.0025 (7) | 0.1234 (5) | 0.4378 (5) | 0.0256 (11) | |
H4 | 0.9649 | 0.1581 | 0.3642 | 0.031* | |
C5 | 1.0841 (6) | 0.0050 (5) | 0.4548 (4) | 0.0210 (10) | |
H5 | 1.1136 | −0.0568 | 0.3961 | 0.025* | |
C6 | 0.7733 (7) | −0.1414 (5) | 0.6196 (4) | 0.0194 (11) | |
C7 | 0.6516 (7) | 0.0852 (5) | 0.6592 (4) | 0.0206 (11) | |
C8 | 0.6305 (7) | −0.0086 (5) | 0.4506 (4) | 0.0215 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.01673 (16) | 0.02980 (19) | 0.02327 (17) | 0.00055 (14) | −0.00373 (14) | 0.00321 (13) |
Re1 | 0.01472 (9) | 0.01598 (9) | 0.01096 (8) | −0.00039 (7) | 0.00082 (7) | 0.00066 (7) |
O1 | 0.0227 (19) | 0.023 (2) | 0.033 (2) | −0.0025 (16) | −0.0006 (18) | 0.0129 (17) |
O2 | 0.031 (2) | 0.027 (2) | 0.0234 (19) | 0.0036 (18) | 0.0093 (17) | −0.0061 (16) |
O3 | 0.026 (2) | 0.043 (2) | 0.0209 (18) | −0.002 (2) | −0.0081 (16) | 0.0020 (18) |
C1 | 0.012 (2) | 0.026 (3) | 0.016 (2) | −0.0050 (19) | 0.0006 (17) | −0.001 (2) |
C2 | 0.018 (3) | 0.024 (3) | 0.024 (3) | −0.006 (2) | −0.002 (2) | −0.001 (2) |
C3 | 0.023 (3) | 0.026 (3) | 0.029 (3) | −0.008 (2) | 0.007 (2) | 0.003 (2) |
C4 | 0.025 (3) | 0.033 (3) | 0.019 (2) | −0.005 (2) | 0.005 (2) | 0.012 (2) |
C5 | 0.015 (2) | 0.030 (3) | 0.018 (2) | 0.001 (2) | 0.0026 (19) | −0.001 (2) |
C6 | 0.014 (3) | 0.025 (3) | 0.019 (2) | 0.004 (2) | −0.0025 (19) | −0.003 (2) |
C7 | 0.027 (3) | 0.016 (2) | 0.018 (2) | −0.002 (2) | −0.007 (2) | 0.0055 (19) |
C8 | 0.020 (2) | 0.024 (3) | 0.020 (2) | 0.001 (2) | 0.004 (2) | 0.004 (2) |
I1—C1 | 2.080 (5) | O3—C8 | 1.142 (6) |
Re1—C7 | 1.899 (5) | C1—C5 | 1.413 (6) |
Re1—C6 | 1.915 (5) | C1—C2 | 1.416 (7) |
Re1—C8 | 1.923 (5) | C5—C4 | 1.442 (7) |
Re1—C4 | 2.288 (5) | C5—H5 | 1.0000 |
Re1—C3 | 2.290 (5) | C4—C3 | 1.415 (8) |
Re1—C5 | 2.313 (5) | C4—H4 | 1.0000 |
Re1—C2 | 2.292 (5) | C3—C2 | 1.431 (8) |
Re1—C1 | 2.302 (5) | C3—H3 | 1.0000 |
O1—C6 | 1.139 (6) | C2—H2 | 1.0000 |
O2—C7 | 1.155 (6) | ||
C7—Re1—C6 | 89.1 (2) | C5—C1—I1 | 124.7 (4) |
C7—Re1—C8 | 90.2 (2) | C2—C1—I1 | 125.4 (4) |
C6—Re1—C8 | 89.7 (2) | C5—C1—Re1 | 72.6 (3) |
C7—Re1—C4 | 126.3 (2) | C2—C1—Re1 | 71.7 (3) |
C6—Re1—C4 | 144.1 (2) | I1—C1—Re1 | 123.6 (2) |
C8—Re1—C4 | 95.0 (2) | O3—C8—Re1 | 177.3 (5) |
C7—Re1—C3 | 96.9 (2) | C1—C5—C4 | 106.4 (5) |
C6—Re1—C3 | 150.5 (2) | C1—C5—Re1 | 71.7 (3) |
C8—Re1—C3 | 119.0 (2) | C4—C5—Re1 | 70.8 (3) |
C4—Re1—C3 | 36.0 (2) | C1—C5—H5 | 126.7 |
C7—Re1—C5 | 156.9 (2) | C4—C5—H5 | 126.7 |
C6—Re1—C5 | 108.0 (2) | Re1—C5—H5 | 126.7 |
C8—Re1—C5 | 104.82 (19) | C3—C4—C5 | 108.6 (5) |
C4—Re1—C5 | 36.53 (18) | C3—C4—Re1 | 72.1 (3) |
C3—Re1—C5 | 60.55 (19) | C5—C4—Re1 | 72.7 (3) |
C7—Re1—C2 | 98.9 (2) | C3—C4—H4 | 125.6 |
C6—Re1—C2 | 114.2 (2) | C5—C4—H4 | 125.6 |
C8—Re1—C2 | 154.37 (19) | Re1—C4—H4 | 125.6 |
C4—Re1—C2 | 60.3 (2) | C4—C3—C2 | 107.9 (5) |
C3—Re1—C2 | 36.41 (19) | C4—C3—Re1 | 71.9 (3) |
C5—Re1—C2 | 60.37 (19) | C2—C3—Re1 | 71.9 (3) |
C7—Re1—C1 | 130.50 (19) | C4—C3—H3 | 126.0 |
C6—Re1—C1 | 94.45 (19) | C2—C3—H3 | 126.0 |
C8—Re1—C1 | 139.08 (19) | Re1—C3—H3 | 126.0 |
C4—Re1—C1 | 59.74 (18) | C1—C2—C3 | 107.3 (5) |
C3—Re1—C1 | 59.91 (19) | C1—C2—Re1 | 72.4 (3) |
C5—Re1—C1 | 35.66 (16) | C3—C2—Re1 | 71.7 (3) |
C2—Re1—C1 | 35.91 (18) | C1—C2—H2 | 126.2 |
O1—C6—Re1 | 177.2 (4) | C3—C2—H2 | 126.2 |
O2—C7—Re1 | 178.4 (5) | Re1—C2—H2 | 126.2 |
C5—C1—C2 | 109.8 (5) | ||
C7—Re1—C1—C5 | −152.2 (3) | C2—Re1—C4—C3 | −37.7 (3) |
C6—Re1—C1—C5 | 115.1 (3) | C1—Re1—C4—C3 | −79.4 (3) |
C8—Re1—C1—C5 | 20.3 (5) | C7—Re1—C4—C5 | 157.9 (3) |
C4—Re1—C1—C5 | −38.5 (3) | C6—Re1—C4—C5 | −11.7 (5) |
C3—Re1—C1—C5 | −80.4 (3) | C8—Re1—C4—C5 | −108.2 (3) |
C2—Re1—C1—C5 | −118.6 (4) | C3—Re1—C4—C5 | 116.9 (5) |
C7—Re1—C1—C2 | −33.7 (4) | C2—Re1—C4—C5 | 79.2 (3) |
C6—Re1—C1—C2 | −126.3 (3) | C1—Re1—C4—C5 | 37.6 (3) |
C8—Re1—C1—C2 | 138.9 (3) | C5—C4—C3—C2 | −0.6 (6) |
C4—Re1—C1—C2 | 80.1 (3) | Re1—C4—C3—C2 | 63.3 (4) |
C3—Re1—C1—C2 | 38.2 (3) | C5—C4—C3—Re1 | −64.0 (3) |
C5—Re1—C1—C2 | 118.6 (4) | C7—Re1—C3—C4 | −147.9 (3) |
C7—Re1—C1—I1 | 87.2 (3) | C6—Re1—C3—C4 | 111.5 (4) |
C6—Re1—C1—I1 | −5.5 (3) | C8—Re1—C3—C4 | −53.8 (4) |
C8—Re1—C1—I1 | −100.2 (3) | C5—Re1—C3—C4 | 37.5 (3) |
C4—Re1—C1—I1 | −159.1 (3) | C2—Re1—C3—C4 | 116.5 (5) |
C3—Re1—C1—I1 | 159.0 (3) | C1—Re1—C3—C4 | 78.9 (3) |
C5—Re1—C1—I1 | −120.6 (4) | C7—Re1—C3—C2 | 95.6 (3) |
C2—Re1—C1—I1 | 120.8 (4) | C6—Re1—C3—C2 | −5.0 (6) |
C2—C1—C5—C4 | 0.3 (6) | C8—Re1—C3—C2 | −170.3 (3) |
I1—C1—C5—C4 | −178.0 (3) | C4—Re1—C3—C2 | −116.5 (5) |
Re1—C1—C5—C4 | 62.7 (3) | C5—Re1—C3—C2 | −79.0 (3) |
C2—C1—C5—Re1 | −62.4 (3) | C1—Re1—C3—C2 | −37.7 (3) |
I1—C1—C5—Re1 | 119.3 (3) | C5—C1—C2—C3 | −0.7 (6) |
C7—Re1—C5—C1 | 64.6 (6) | I1—C1—C2—C3 | 177.6 (3) |
C6—Re1—C5—C1 | −71.7 (3) | Re1—C1—C2—C3 | −63.7 (4) |
C8—Re1—C5—C1 | −166.4 (3) | C5—C1—C2—Re1 | 63.0 (3) |
C4—Re1—C5—C1 | 115.4 (5) | I1—C1—C2—Re1 | −118.7 (3) |
C3—Re1—C5—C1 | 78.4 (3) | C4—C3—C2—C1 | 0.8 (6) |
C2—Re1—C5—C1 | 36.3 (3) | Re1—C3—C2—C1 | 64.2 (3) |
C7—Re1—C5—C4 | −50.8 (6) | C4—C3—C2—Re1 | −63.3 (4) |
C6—Re1—C5—C4 | 172.8 (3) | C7—Re1—C2—C1 | 154.7 (3) |
C8—Re1—C5—C4 | 78.2 (3) | C6—Re1—C2—C1 | 61.7 (4) |
C3—Re1—C5—C4 | −37.0 (3) | C8—Re1—C2—C1 | −95.7 (5) |
C2—Re1—C5—C4 | −79.1 (3) | C4—Re1—C2—C1 | −78.4 (3) |
C1—Re1—C5—C4 | −115.4 (5) | C3—Re1—C2—C1 | −115.6 (4) |
C1—C5—C4—C3 | 0.2 (6) | C5—Re1—C2—C1 | −36.1 (3) |
Re1—C5—C4—C3 | 63.5 (4) | C7—Re1—C2—C3 | −89.6 (3) |
C1—C5—C4—Re1 | −63.3 (3) | C6—Re1—C2—C3 | 177.3 (3) |
C7—Re1—C4—C3 | 40.9 (4) | C8—Re1—C2—C3 | 19.9 (6) |
C6—Re1—C4—C3 | −128.6 (4) | C4—Re1—C2—C3 | 37.3 (3) |
C8—Re1—C4—C3 | 134.9 (3) | C5—Re1—C2—C3 | 79.5 (3) |
C5—Re1—C4—C3 | −116.9 (5) | C1—Re1—C2—C3 | 115.6 (4) |
[Re2(C12H8)(CO)6] | F(000) = 628 |
Mr = 692.64 | Dx = 2.671 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4303 reflections |
a = 6.2633 (10) Å | θ = 2.5–30.6° |
b = 11.7262 (18) Å | µ = 14.08 mm−1 |
c = 11.8471 (18) Å | T = 100 K |
β = 98.206 (2)° | Plate, brown |
V = 861.2 (2) Å3 | 0.20 × 0.11 × 0.09 mm |
Z = 2 |
Bruker SMART APEXII CCD area-detector diffractometer | 2068 independent reflections |
Radiation source: fine-focus sealed tube | 1817 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
φ and ω scans | θmax = 28.0°, θmin = 3.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −8→8 |
Tmin = 0.165, Tmax = 0.364 | k = −15→15 |
8399 measured reflections | l = −15→15 |
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)] = 0.021 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.051 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.025P)2] where P = (Fo2 + 2Fc2)/3 |
2068 reflections | (Δ/σ)max < 0.001 |
118 parameters | Δρmax = 1.48 e Å−3 |
0 restraints | Δρmin = −0.80 e Å−3 |
[Re2(C12H8)(CO)6] | V = 861.2 (2) Å3 |
Mr = 692.64 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.2633 (10) Å | µ = 14.08 mm−1 |
b = 11.7262 (18) Å | T = 100 K |
c = 11.8471 (18) Å | 0.20 × 0.11 × 0.09 mm |
β = 98.206 (2)° |
Bruker SMART APEXII CCD area-detector diffractometer | 2068 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1817 reflections with I > 2σ(I) |
Tmin = 0.165, Tmax = 0.364 | Rint = 0.035 |
8399 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 0 restraints |
wR(F2) = 0.051 | H-atom parameters constrained |
S = 1.02 | Δρmax = 1.48 e Å−3 |
2068 reflections | Δρmin = −0.80 e Å−3 |
118 parameters |
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 | 0.74258 (2) | 0.218800 (13) | 0.084967 (13) | 0.02216 (7) | |
O1 | 0.5423 (6) | −0.0079 (3) | 0.1446 (3) | 0.0466 (9) | |
O2 | 0.9769 (5) | 0.0997 (3) | −0.0921 (3) | 0.0373 (7) | |
O3 | 1.1325 (5) | 0.1744 (3) | 0.2670 (3) | 0.0423 (8) | |
C1 | 0.7431 (6) | 0.4100 (3) | 0.0351 (4) | 0.0257 (8) | |
C2 | 0.6730 (7) | 0.4011 (4) | 0.1448 (4) | 0.0299 (9) | |
H2 | 0.7440 | 0.4381 | 0.2165 | 0.036* | |
C3 | 0.4795 (7) | 0.3398 (4) | 0.1331 (4) | 0.0336 (10) | |
H3 | 0.3885 | 0.3263 | 0.1946 | 0.040* | |
C4 | 0.4242 (7) | 0.3087 (4) | 0.0155 (4) | 0.0339 (10) | |
H4 | 0.2878 | 0.2701 | −0.0188 | 0.041* | |
C5 | 0.5849 (6) | 0.3506 (4) | −0.0451 (4) | 0.0300 (9) | |
H5 | 0.5824 | 0.3472 | −0.1296 | 0.036* | |
C6 | 0.9269 (6) | 0.4727 (3) | 0.0098 (4) | 0.0263 (8) | |
C7 | 0.6214 (7) | 0.0771 (4) | 0.1214 (4) | 0.0315 (9) | |
C8 | 0.8900 (6) | 0.1422 (4) | −0.0234 (4) | 0.0275 (9) | |
C9 | 0.9832 (7) | 0.1898 (4) | 0.1989 (4) | 0.0297 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Re1 | 0.02302 (10) | 0.02099 (10) | 0.02179 (10) | −0.00216 (6) | 0.00085 (6) | 0.00178 (6) |
O1 | 0.061 (2) | 0.038 (2) | 0.0429 (19) | −0.0198 (17) | 0.0157 (17) | 0.0025 (16) |
O2 | 0.0482 (19) | 0.0342 (17) | 0.0309 (16) | 0.0066 (15) | 0.0104 (14) | 0.0049 (14) |
O3 | 0.0393 (18) | 0.048 (2) | 0.0352 (18) | 0.0038 (16) | −0.0111 (14) | 0.0087 (17) |
C1 | 0.026 (2) | 0.0202 (19) | 0.030 (2) | 0.0042 (16) | 0.0004 (16) | 0.0020 (17) |
C2 | 0.033 (2) | 0.025 (2) | 0.032 (2) | 0.0043 (18) | 0.0055 (18) | −0.0014 (18) |
C3 | 0.027 (2) | 0.034 (2) | 0.041 (2) | 0.0004 (19) | 0.0089 (18) | 0.003 (2) |
C4 | 0.024 (2) | 0.033 (2) | 0.043 (3) | −0.0007 (18) | −0.0035 (19) | 0.005 (2) |
C5 | 0.029 (2) | 0.033 (2) | 0.026 (2) | 0.0023 (18) | −0.0031 (16) | 0.0063 (19) |
C6 | 0.031 (2) | 0.0174 (19) | 0.030 (2) | 0.0057 (15) | 0.0030 (17) | 0.0006 (17) |
C7 | 0.034 (2) | 0.033 (2) | 0.028 (2) | −0.0051 (19) | 0.0054 (18) | −0.0017 (19) |
C8 | 0.028 (2) | 0.025 (2) | 0.028 (2) | −0.0016 (17) | 0.0002 (17) | 0.0061 (17) |
C9 | 0.032 (2) | 0.024 (2) | 0.032 (2) | −0.0029 (17) | 0.0022 (18) | 0.0035 (18) |
Re1—C8 | 1.909 (4) | C2—C3 | 1.399 (6) |
Re1—C9 | 1.905 (4) | C2—H2 | 1.0000 |
Re1—C7 | 1.902 (4) | C7—O1 | 1.163 (5) |
Re1—C3 | 2.307 (4) | C1—C6 | 1.434 (6) |
Re1—C4 | 2.302 (4) | C1—C5 | 1.450 (6) |
Re1—C5 | 2.303 (4) | C6—C6i | 1.167 (8) |
Re1—C2 | 2.313 (4) | C5—C4 | 1.405 (6) |
Re1—C1 | 2.319 (4) | C5—H5 | 1.0000 |
C9—O3 | 1.158 (5) | C4—C3 | 1.434 (7) |
O2—C8 | 1.156 (5) | C4—H4 | 1.0000 |
C2—C1 | 1.433 (6) | C3—H3 | 1.0000 |
C8—Re1—C9 | 89.01 (18) | C3—C2—Re1 | 72.1 (3) |
C8—Re1—C7 | 89.34 (18) | C1—C2—H2 | 125.6 |
C9—Re1—C7 | 89.10 (18) | C3—C2—H2 | 125.6 |
C8—Re1—C3 | 152.44 (17) | Re1—C2—H2 | 125.6 |
C9—Re1—C3 | 117.10 (18) | O1—C7—Re1 | 178.1 (4) |
C7—Re1—C3 | 99.15 (17) | C2—C1—C6 | 125.9 (4) |
C8—Re1—C4 | 116.92 (17) | C2—C1—C5 | 106.8 (4) |
C9—Re1—C4 | 153.21 (19) | C6—C1—C5 | 127.1 (4) |
C7—Re1—C4 | 97.35 (18) | C2—C1—Re1 | 71.7 (2) |
C3—Re1—C4 | 36.24 (16) | C6—C1—Re1 | 125.4 (3) |
C8—Re1—C5 | 93.93 (16) | C5—C1—Re1 | 71.1 (2) |
C9—Re1—C5 | 144.53 (16) | C6i—C6—C1 | 177.6 (6) |
C7—Re1—C5 | 126.23 (16) | C4—C5—C1 | 107.8 (4) |
C3—Re1—C5 | 59.94 (16) | C4—C5—Re1 | 72.2 (2) |
C4—Re1—C5 | 35.54 (16) | C1—C5—Re1 | 72.3 (2) |
C8—Re1—C2 | 140.46 (16) | C4—C5—H5 | 126.0 |
C9—Re1—C2 | 96.46 (17) | C1—C5—H5 | 126.0 |
C7—Re1—C2 | 129.73 (18) | Re1—C5—H5 | 126.0 |
C3—Re1—C2 | 35.25 (15) | O2—C8—Re1 | 177.0 (3) |
C4—Re1—C2 | 59.65 (16) | C5—C4—C3 | 108.4 (4) |
C5—Re1—C2 | 60.22 (15) | C5—C4—Re1 | 72.3 (2) |
C8—Re1—C1 | 105.40 (16) | C3—C4—Re1 | 72.1 (2) |
C9—Re1—C1 | 108.87 (16) | C5—C4—H4 | 125.7 |
C7—Re1—C1 | 156.59 (17) | C3—C4—H4 | 125.7 |
C3—Re1—C1 | 59.67 (15) | Re1—C4—H4 | 125.7 |
C4—Re1—C1 | 59.90 (15) | C2—C3—C4 | 108.2 (4) |
C5—Re1—C1 | 36.56 (14) | C2—C3—Re1 | 72.6 (2) |
C2—Re1—C1 | 36.05 (15) | C4—C3—Re1 | 71.7 (3) |
O3—C9—Re1 | 178.2 (4) | C2—C3—H3 | 125.8 |
C1—C2—C3 | 108.7 (4) | C4—C3—H3 | 125.8 |
C1—C2—Re1 | 72.2 (2) | Re1—C3—H3 | 125.8 |
C8—Re1—C2—C1 | 17.1 (4) | C7—Re1—C5—C4 | 41.1 (3) |
C9—Re1—C2—C1 | 113.4 (3) | C3—Re1—C5—C4 | −37.5 (3) |
C7—Re1—C2—C1 | −152.4 (2) | C2—Re1—C5—C4 | −78.4 (3) |
C3—Re1—C2—C1 | −117.2 (4) | C1—Re1—C5—C4 | −116.0 (4) |
C4—Re1—C2—C1 | −79.5 (3) | C8—Re1—C5—C1 | −110.7 (3) |
C5—Re1—C2—C1 | −38.2 (2) | C9—Re1—C5—C1 | −16.9 (4) |
C8—Re1—C2—C3 | 134.3 (3) | C7—Re1—C5—C1 | 157.2 (3) |
C9—Re1—C2—C3 | −129.4 (3) | C3—Re1—C5—C1 | 78.5 (3) |
C7—Re1—C2—C3 | −35.2 (4) | C4—Re1—C5—C1 | 116.0 (4) |
C4—Re1—C2—C3 | 37.7 (3) | C2—Re1—C5—C1 | 37.6 (2) |
C5—Re1—C2—C3 | 79.0 (3) | C1—C5—C4—C3 | −0.6 (5) |
C1—Re1—C2—C3 | 117.2 (4) | Re1—C5—C4—C3 | 63.4 (3) |
C3—C2—C1—C6 | 175.7 (4) | C1—C5—C4—Re1 | −64.0 (3) |
Re1—C2—C1—C6 | −121.0 (4) | C8—Re1—C4—C5 | −54.6 (3) |
C3—C2—C1—C5 | −0.5 (5) | C9—Re1—C4—C5 | 109.6 (4) |
Re1—C2—C1—C5 | 62.9 (3) | C7—Re1—C4—C5 | −147.6 (3) |
C3—C2—C1—Re1 | −63.4 (3) | C3—Re1—C4—C5 | 116.9 (4) |
C8—Re1—C1—C2 | −168.8 (2) | C2—Re1—C4—C5 | 80.2 (3) |
C9—Re1—C1—C2 | −74.5 (3) | C1—Re1—C4—C5 | 38.2 (3) |
C7—Re1—C1—C2 | 63.9 (5) | C8—Re1—C4—C3 | −171.5 (3) |
C3—Re1—C1—C2 | 36.5 (2) | C9—Re1—C4—C3 | −7.2 (5) |
C4—Re1—C1—C2 | 78.7 (3) | C7—Re1—C4—C3 | 95.5 (3) |
C5—Re1—C1—C2 | 115.8 (3) | C5—Re1—C4—C3 | −116.9 (4) |
C8—Re1—C1—C6 | −47.2 (4) | C2—Re1—C4—C3 | −36.7 (3) |
C9—Re1—C1—C6 | 47.1 (4) | C1—Re1—C4—C3 | −78.7 (3) |
C7—Re1—C1—C6 | −174.5 (4) | C1—C2—C3—C4 | 0.1 (5) |
C3—Re1—C1—C6 | 158.0 (4) | Re1—C2—C3—C4 | −63.3 (3) |
C4—Re1—C1—C6 | −159.8 (4) | C1—C2—C3—Re1 | 63.4 (3) |
C5—Re1—C1—C6 | −122.6 (5) | C5—C4—C3—C2 | 0.3 (5) |
C2—Re1—C1—C6 | 121.5 (5) | Re1—C4—C3—C2 | 63.9 (3) |
C8—Re1—C1—C5 | 75.4 (3) | C5—C4—C3—Re1 | −63.6 (3) |
C9—Re1—C1—C5 | 169.7 (3) | C8—Re1—C3—C2 | −100.2 (4) |
C7—Re1—C1—C5 | −51.9 (5) | C9—Re1—C3—C2 | 59.7 (3) |
C3—Re1—C1—C5 | −79.3 (3) | C7—Re1—C3—C2 | 153.4 (3) |
C4—Re1—C1—C5 | −37.1 (2) | C4—Re1—C3—C2 | −116.7 (4) |
C2—Re1—C1—C5 | −115.8 (3) | C5—Re1—C3—C2 | −79.9 (3) |
C2—C1—C5—C4 | 0.7 (5) | C1—Re1—C3—C2 | −37.3 (3) |
C6—C1—C5—C4 | −175.4 (4) | C8—Re1—C3—C4 | 16.5 (5) |
Re1—C1—C5—C4 | 64.0 (3) | C9—Re1—C3—C4 | 176.3 (3) |
C2—C1—C5—Re1 | −63.3 (3) | C7—Re1—C3—C4 | −90.0 (3) |
C6—C1—C5—Re1 | 120.6 (4) | C5—Re1—C3—C4 | 36.8 (3) |
C8—Re1—C5—C4 | 133.2 (3) | C2—Re1—C3—C4 | 116.7 (4) |
C9—Re1—C5—C4 | −133.0 (3) | C1—Re1—C3—C4 | 79.4 (3) |
Symmetry code: (i) −x+2, −y+1, −z. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | [Mn(C5H4I)(CO)3] | [Mn2(C12H8)(CO)6] | [Re(C5H4I)(CO)3] | [Re2(C12H8)(CO)6] |
Mr | 329.95 | 430.12 | 461.21 | 692.64 |
Crystal system, space group | Orthorhombic, P212121 | Monoclinic, P21/c | Orthorhombic, P212121 | Monoclinic, P21/c |
Temperature (K) | 100 | 100 | 100 | 100 |
a, b, c (Å) | 7.2696 (5), 10.7776 (7), 12.0288 (8) | 6.4096 (10), 10.9991 (16), 11.9798 (18) | 7.4117 (14), 10.922 (2), 11.987 (2) | 6.2633 (10), 11.7262 (18), 11.8471 (18) |
α, β, γ (°) | 90, 90, 90 | 90, 100.507 (2), 90 | 90, 90, 90 | 90, 98.206 (2), 90 |
V (Å3) | 942.44 (11) | 830.4 (2) | 970.3 (3) | 861.2 (2) |
Z | 4 | 2 | 4 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 4.64 | 1.55 | 15.67 | 14.08 |
Crystal size (mm) | 0.20 × 0.15 × 0.07 | 0.31 × 0.11 × 0.10 | 0.14 × 0.10 × 0.07 | 0.20 × 0.11 × 0.09 |
Data collection | ||||
Diffractometer | Bruker SMART APEXII CCD area-detector | Bruker SMART APEXII CCD area-detector | Bruker SMART APEXII CCD area-detector | Bruker SMART APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.427, 0.717 | 0.645, 0.860 | 0.218, 0.407 | 0.165, 0.364 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9507, 2278, 2161 | 12974, 2552, 2211 | 9533, 2342, 2276 | 8399, 2068, 1817 |
Rint | 0.031 | 0.037 | 0.036 | 0.035 |
(sin θ/λ)max (Å−1) | 0.660 | 0.717 | 0.661 | 0.661 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.048, 1.06 | 0.028, 0.071, 1.05 | 0.018, 0.041, 0.99 | 0.021, 0.051, 1.02 |
No. of reflections | 2278 | 2552 | 2342 | 2068 |
No. of parameters | 118 | 118 | 118 | 118 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.54, −0.38 | 0.42, −0.24 | 1.60, −1.39 | 1.48, −0.80 |
Absolute structure | Flack (1983), with how many Friedel pairs? | ? | Flack (1983), with how many Friedel pairs? | ? |
Absolute structure parameter | 0.05 (3) | ? | 0.015 (7) | ? |
Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2001), SHELXTL (Sheldrick, 2008).
Parameter | (I) | (II) | CSD (M = Mn) |
C—C for Cp' | 1.417 (5) | 1.425 (2) | 1.415 |
M—C for Cp' | 2.144 (3) | 2.152 (2) | 2.138 |
M—C(O) | 1.796 (3) | 1.800 (2) | 1.790 |
C—O | 1.153 (4) | 1.149 (2) | 1.148 |
M1···Cg1 | 1.773 (2) | 1.777 (1) | 1.771 |
(O)C—M—C(O) | 91.78 (15) | 91.79 (6) | 91.94 |
M—C—O | 178.6 (3) | 178.84 (13) | 178.2 |
Parameter | (III) | (IV) | CSD (M = Re) |
C—C for Cp' | 1.423 (8) | 1.423 (6) | 1.419 |
M—C for Cp' | 2.297 (5) | 2.307 (5) | 2.299 |
M—C(O) | 1.912 (5) | 1.907 (5) | 1.902 |
C—O | 1.145 (6) | 1.157 (6) | 1.156 |
M1···Cg1 | 1.952 (2) | 1.964 (2) | 1.957 |
(O)C—M—C(O) | 89.6 (2) | 89.2 (2) | 89.8 |
M—C—O | 177.6 (5) | 178.0 (4) | 177.1 |
Cp' is the C5H4X ring. M is Mn or Re. Cg1 is the centroid of the C5H4X ring. |
One of the rapidly growing fields in metalloorganic chemistry is the synthesis of new materials. Such examples include dendrimers (Tomalia et al., 1990; Stulgies et al., 2004; Astruc et al., 2008), staffanes (Kaszynski et al., 1992), Diederich's carbon nets (Diederich & Rubin, 1992), and various novel electronic, photonic and magnetic materials (Barlow & O'Hare, 1997; Elschenbroich et al., 2005; Kinnibrugh et al., 2009). Because of the increasing interest in this area, we have focused our studies on structural investigations of the title compounds, (I)–(IV) (Figs. 1 and 2), which can be used as starting compounds for the construction of new materials (Sterzo et al., 1989). This work reports the first structural studies of monohalogenated derivatives of (η5-C5H4X)M(CO)3 [for (I), M = Mn and X = I; for (III), M = Re and X = I] and the dinuclear [(CO)3MC5H4]C≡C[C5H4M(CO)3] compounds [for (II), M = Mn; for (IV), M = Re].
The mean values of the geometric parameters for compounds (I)–(IV) are in accordance with those previously reported (Table 1) for 89 mono-substituted cymantrenes and 27 (η5-C5H4X)Re(CO)3 compounds, which were retrieved from the 2009 version of the Cambridge Structural Database (CSD; Allen, 2002) using ConQuest (Version 1.11; Macrae et al., 2006), as well as with the unsubstituted compounds C5H5M(CO)3 (M = Mn, Re) (Fitzpatrick, Le Page & Butler, 1981 or Fitzpatrick, Le Page et al., 1981; Cowie et al., 1990). The mono-substituted complexes (η5-C5H4X)M(CO)3 (X is any atom, M = Mn, Re) were considered with the following search criteria: (a) three-dimensional coordinates and R < 0.10; (b) no errors; (c) no crystallographic disorder; (d) no polymer structures. The (O)C—Mn—C(O) angle is in accord with a tendency for decreasing the pyramidality of the M(CO)3 fragment with increasing π-donor capacity of the cyclic polyene (Fitzpatrick, Le Page & Butler, 1981 or Fitzpatrick, Le Page et al., 1981): (C6H6)Cr(CO)3 88.22 (8)° (Rees & Coppens, 1973), CpRe(CO)3 90.0 (2)° (Fitzpatrick, Le Page & Butler, 1981 or Fitzpatrick, Le Page et al., 1981), CpMn(CO)3 92.02 (5)° (Cowie et al., 1990), (C4H4)Fe(CO)3 95.6° (Hall et al., 1975) and (C4Ph4)Fe(CO)3 97.03 (3)° (Dodge & Schomaker, 1965). The M—C—O bond angles do not differ significantly from 180°.
The M(CO)3 (M = Mn, Re) fragment possess approximate C3v symmetry, while coordination to the η5-C5H4X ring lowers the molecular symmetry to C1 (Fig. 3). Compounds (I)–(IV) possess different mutual dispositions of the carbonyl groups and η5-C5H4X rings: the C6≡O1 carbonyl group for (I) and (III) is in an eclipsed position relative to the substituted C atom of the η5-C5H4I ring, while the C7≡O1 carbonyl group of (II) and (IV) is in the transoid position to the substitutent-bearing C atom (Figs. 3 and 4).
Compounds (II) and (IV) crystallize with the molecules occupying a special position on an inversion center. Each molecule consists of two identical [(CO)3M(C5H4)C≡] (M = Mn, Re) parts with the M(CO)3 moieties in transoid positions. We suggest that (II) and (IV) adopt the transoid structure due to the realisation of strong attractive intermolecular π(CO)–π(CO) interactions in the sheared parallel packing motif (see below). In contrast, the only analogous compound found in the literature, [(CO)3Mn(C5H4)C≡C(C7H5)Cr(CO)3]BF4, possesses a syn-facial (cisoid) conformation of M(CO)3 moieties, due to the formation of strong attractive intermolecular π(CO)–π(CO) interactions with a perpendicular packing motif (Tamm et al., 2000). The conformation of [(CO)3M(C5H4)] moieties thus appears to depend, at least in part, on the type of π(CO)–π(CO) interactions formed.
The molecules in all four structures form zigzag chains due to the formation of strong attractive interactions. For (I) and (III), the zigzag chains implemented along the crystallographic b axis involve strong attractive I···O interactions [I1···O2A(2 - x, -1/2 + y, 3/2 - z) = 3.233 (2) Å and I1···O2A–C7A = 112.1 (2)° for (I), and I1···O2A(2 - x, -1/2 + y, 3/2 - z) = 3.231 (4) Å and I1···O2A–C7A 110.6 (3)° for (III)] (Fig. 5). The attractive nature of halogen···oxygen interactions is caused by electrostatic effects, polarization, charge transfer and dispersion contributions. The tendency to form short X···E (E = O, N) interactions (X = I > Br > Cl) increases with the magnitude of their polarizabilities (Lommerse et al., 1996). The directionality of that type of interaction has been interpreted in terms of charge transfer between the highest occupied molecular orbital of E and the lowest unoccupied molecular orbital of X (Ramasubbu et al., 1986). The strength of halogen–carbonyl interactions has been characterized as a function of two geometric parameters, the halogen–oxygen distance (X···O) and the halogen–oxygen–carbon angle (X···O—C). The interaction energy of the most strongly bound system was found to be 2.39 kcal mol-1 (1 kcal mol-1 = 4.184 kJ mol-1) (iodobenzene–formaldehyde; I···O = 3.2 Å and I···O—C 110°), of the same magnitude as those for C—H···O hydrogen bonds (Riley & Merz, 2007). The observed interactions in (I) and (III) are consistent in geometry with these calculated strong interactions.
According to a systematic CSD analysis (Allen et al., 1998) of interactions between ketonic (C2—C═O) carbonyl groups, three types of interaction motifs were identified: a predominant slightly sheared antiparallel motif, a perpendicular motif, and a highly sheared parallel motif. For transition metal carbonyls, a higher percentage of the perpendicular motif has been reported (Allen et al., 2006). Compounds (II) and (IV) contain strong attractive antiparallel intermolecular π(CO)–π(CO) interactions between the carbonyl groups of neighboring molecules [O2···C8A(2 - x, -y, z) = 3.138 (2) Å, C8—O2···C8A = 105.00 (10)° for (II), and O2···C8A(2 - x, -y, z) = 3.211 (6) Å and C8—O2···C8A = 101.8 (3)° for (IV)], forming pairwise interactions in a sheared antiparallel dimer motif along the crystallographic b axis (Fig. 6). These antiparallel π(CO)–π(CO) interactions are a driving force for the formation of zigzag chains along the b axis. Comparison of the parameters obtained for (II) and (IV) with distances and angles reported for similar interactions in other transition metal carbonyls (2.95–3.60 Å/80–135°) indicates that the π(CO)–π(CO) interactions are relatively strong in (II) and (IV) (Allen et al., 2006). Also, intermolecular π(CO)–π(CO) interactions are not rare, and sheared antiparallel and perpendicular motifs can be found for 14 of the 89 hits for mono-substituted cymantrenes and for 3 of the 27 hits for (η5-C5H4X)Re(CO)3 compounds in the CSD search (see above). The mean van der Waals radii used to identify intermolecular interactions and contacts were taken as C = 1.53, O = 1.42 and I = 2.04 Å (Bondi, 1964).
The zigzag chains in (I) and (III) are bound to each other by weak intermolecular C—H···O hydrogen bonds, while those in (II) and (IV) associate by a combination of weak C—H···O hydrogen bonds and π(Csp2)–π(Csp2) and π(Csp2)–π(Csp) stacking interactions between pairs of inversion-related molecules (C···C distances ca 3.4 Å), leading to a ladder-type packing (Fig. 7).