Insight into the structures of [M(C₅H₄I)(CO)₃] and [M₂(C₁₂H₈)(CO)₆] (M = Mn and Re) containing strong I...O and [pi](CO)-[pi](CO) inter­actions

The compounds tricarbonyl([eta]⁵-1-iodo­cyclo­penta­dienyl)­man­gan­ese(I), [Mn(C₅H₄I)(CO)₃], (I), and tricarbonyl([eta]⁵-1-iodo­cyclo­penta­dienyl)rhenium(I), [Re(C₅H₄I)(CO)₃], (III), are isostructural and isomorphous. The compounds [[mu]-1,2([eta]⁵)-acetyl­enedicyclo­penta­dienyl]bis­[tricarbonyl­manganese(I)] or bis­(cymantrenyl)acetyl­ene, [Mn₂(C₁₂H₈)(CO)₆], (II), and [[mu]-1,2([eta]⁵)-acetyl­enedicyclo­penta­dienyl]bis­[tri­carbonyl­rhenium(I)], [Re₂(C₁₂H₈)(CO)₆], (IV), are isostructural and isomorphous, and their mol­ecules display inversion symmetry about the mid-point of the ligand C[triple bond]C bond, with the (CO)₃M(C₅H₄) (M = Mn and Re) moieties adopting a transoid conformation. The mol­ecules in all four compounds form zigzag chains due to the formation of strong attractive I...O [in (I) and (III)] or [pi](CO)-[pi](CO) [in (I) and (IV)] inter­actions along the crystallographic b axis. The zigzag chains are bound to each other by weak inter­molecular C-H...O hydrogen bonds for (I) and (III), while for (II) and (IV) the chains are bound to each other by a combination of weak C-H...O hydrogen bonds and [pi](Csp²)-[pi](Csp²) stacking inter­actions between pairs of mol­ecules. The [pi](CO)-[pi](CO) contacts in (II) and (IV) between carbonyl groups of neighboring mol­ecules, forming pairwise inter­actions in a sheared anti­parallel dimer motif, are encountered in only 35% of all carbonyl inter­actions for transition metal-carbonyl compounds.

S1. Comment

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 C_3v 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).

S2. Experimental

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.

S3. Refinement

All H atoms were positioned geometrically, with C—H = 1.00 Å, and included in riding mode, with U_iso(H) = 1.2U_eq(C).

Computing details

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).

Figures

	Fig. 1. A view of the molecule of (I), with the atom-numbering scheme. The Re analog, (III), is isostructural. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A view of the molecule of (II), with the atom-numbering scheme. The Re analog, (IV), is isostructural. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Atoms labelled with the suffix A are at the symmetry position (2 - x, 1 - y, -z).
	Fig. 3. The conformation of (I), showing one CO group eclipsed by the halogen substituent on the C5 ring.
	Fig. 4. The conformation of (II), showing the CO group in a transoid position relative to the substituent on the C5 ring.
	Fig. 5. The zigzag chains formed along the b axis for (I). Dashed lines indicate the I···O interactions. [Symmetry codes: (A) 2 - x, -1/2 + y, 3/2 - z; (B) ?; (AA) ? Please complete]
	Fig. 6. The zigzag chains formed along the b axis for (II). Dashed lines indicate the π(CO)–π(CO) interactions. [Symmetry codes: (A) 2 - x, -y, z; (B) ?; (C) ? Please complete]
	Fig. 7. The π(Csp^2)–π(Csp) stacking interactions (dashed lines) between pairs of molecules in (II). [Symmetry codes: (A) 1 - x, 1 - y, -z; (B) ?; (C) ?; (D) ?; (E) ?; (AA) ? Please complete]

(I) Tricarbonyl(η⁵-1-iodocyclopentadienyl)manganese(I)

Crystal data

[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) Å^3	Plate, yellow
Z = 4	0.20 × 0.15 × 0.07 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.020	H-atom parameters constrained
wR(F^2) = 0.048	w = 1/[σ^2(Fo^2) + (0.021P)^2 + 0.223P] where P = (Fo^2 + 2Fc^2)/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)

Special details

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 (Ų)

	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

(II) [µ-1,2(η⁵)-Acetylenedicyclopentadienyl]bis[tricarbonylmanganese(I)]

Crystal data

[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) Å^3	0.31 × 0.11 × 0.10 mm
Z = 2

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.071	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.035P)^2 + 0.228P] where P = (Fo^2 + 2Fc^2)/3
2552 reflections	(Δ/σ)max < 0.001
118 parameters	Δρmax = 0.42 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

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 (Ų)

	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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—C6^i	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)	C6^i—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.

(III) Tricarbonyl(η⁵-1-iodocyclopentadienyl)rhenium(I)

Crystal data

[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) Å^3	Plate, white
Z = 4	0.14 × 0.10 × 0.07 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.018	H-atom parameters constrained
wR(F^2) = 0.041	w = 1/[σ^2(Fo^2) + (0.0017P)^2] where P = (Fo^2 + 2Fc^2)/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)

Special details

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 (Ų)

	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

(IV) [µ-1,2(η⁵)-Acetylenedicyclopentadienyl]bis[tricarbonylrhenium(I)]

Crystal data

[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) Å^3	0.20 × 0.11 × 0.09 mm
Z = 2

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.051	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.025P)^2] where P = (Fo^2 + 2Fc^2)/3
2068 reflections	(Δ/σ)max < 0.001
118 parameters	Δρmax = 1.48 e Å^−3
0 restraints	Δρmin = −0.80 e Å^−3

Special details

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 (Ų)

	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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—C6^i	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)	C6^i—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.