Crystal structures of trans-acetyl­dicarbon­yl(η5-cyclo­penta­dien­yl)(di­methyl­phenyl­phosphane)molybdenum(II) and trans-acetyl­dicarbon­yl(η5-cyclo­penta­dien­yl)(ethyl­diphenyl­phosphane)molybdenum(II)

Whited, M.T.; Hofmeister, G.E.; Hodges, C.J.; Jensen, L.T.; Keyes, S.H.; Ngamnithiporn, A.; Janzen, D.E.

doi:10.1107/S1600536814020534

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ISSN: 2056-9890

Volume 70| Part 10| October 2014| Pages 216-220

doi:10.1107/S1600536814020534

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Crystal structures of trans-acetyldicarbonyl(η⁵-cyclopentadienyl)(dimethylphenylphosphane)molybdenum(II) and trans-acetyldicarbonyl(η⁵-cyclopentadienyl)(ethyldiphenylphosphane)molybdenum(II)

Matthew T. Whited,^a ^* Gretchen E. Hofmeister,^a Connor J. Hodges,^a Laramie T. Jensen,^a Samuel H. Keyes,^a Aurapat Ngamnithiporn ^a and Daron E. Janzen ^b

^aDepartment of Chemistry, Carleton College, 1 N College St, Northfield, MN 55057, USA, and ^bDepartment of Chemistry and Biochemistry, St. Catherine University, 2004 Randolph Ave., St. Paul, MN 55105, USA
^*Correspondence e-mail: mwhited@carleton.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 1 September 2014; accepted 12 September 2014; online 20 September 2014)

The title compounds, [Mo(C₅H₅)(COCH₃)P(CH₃)₂(C₆H₅)(CO)₂], (1), and [Mo(C₅H₅)(COCH₃)P(C₂H₅)(C₆H₅)₂)(CO)₂], (2), have been prepared by phosphine-induced migratory insertion from [Mo(C₅H₅)(CO)₃(CH₃)]. Both complex molecules exhibit a four-legged piano-stool geometry with trans-disposed carbonyl ligands along with Mo—P bond lengths and C—Mo—P angles that reflect the relative steric pressure of the respective phosphine ligand. The structure of compound (1) exhibits a layered arrangement parallel to (100). Within the layers molecules are linked into chains along [001] by non-classical C—H⋯O interactions between the acetyl ligand of one molecule and the phenyl and methyl phosphine substituents of another. In the structure of complex (2), a chain motif of centrosymmetrical dimers is found along [010] through C—H⋯O interactions.

Keywords: crystal structure; phosphine; acetyl; piano-stool complex; divalent molybdenum.

CCDC references: 1024131; 1024132

1. Chemical context

Cyclopentadienylmolybdenum polycarbonyl complexes [Mo(C₅H₅)(CO)_n] with `piano-stool' geometries have been studied extensively for their fundamental organometallic reactivity. In particular, alkyl complexes of the form [Mo(C₅H₅)(CO)₃(R)] have been studied for their migratory insertion reactivity (Barnett & Treichel, 1967 ; Butler et al., 1967 ), affording [Mo(C₅H₅)(PR₃)(CO)₂(COR)] acetyl complexes on exposure to phosphine ligands. Although the insertion reaction shows little dependence on the nature of the phosphine, the corresponding deinsertion shows a strong dependence on steric bulk of the phosphine, with bulkier groups giving enhanced deinsertion rates (Barnett, 1969 ; Barnett & Pollmann, 1974 ).

We have developed an interest in the solid-state structural properties of a series of piano-stool molybdenum acetyl complexes derived from migratory insertion with various phosphines, with the goal of understanding how modification of the phosphine substituents affects ground-state structure as well as solid-state packing. Recently, we reported an unusual example where orientation of the acetyl group in the solid state can be changed by introduction of furyl substituents on the phosphine ligand (Whited et al., 2013 ). In this study, the structures obtained for dimethylphenylphosphine, [Mo(C₅H₅)(P(CH₃)₂(C₆H₅))(CO)₂(COCH₃)] (1), and ethyldiphenylphosphine, [Mo(C₅H₅)(P(C₂H₅)(C₆H₅)₂))(CO)₂(COCH₃)] (2), derivatives are compared.

2. Structural commentary

The molecular structures of (1) and (2) are illustrated in Figs. 1 and 2. In spite of the somewhat different steric environments provided by the phosphine ligands, the molecular structures are quite similar. Both complexes exhibit a trans disposition of carbonyl ligands common for compounds of this class. Complexes (1) and (2) both have structures where the oxygen atom of the acetyl group points toward the cyclopentadienyl (Cp) ring. This orientation is also consistent with the majority of crystal structures of related complexes, with the exception of the recently reported tri(2-furyl)phosphine derivative, in which the acetyl group points away from the Cp ring, enabling intermolecular O⋯H—C interactions with the furyl group of a neighboring molecule (Whited et al., 2013).

Figure 1
Molecular structure of (1) with displacement ellipsoids drawn at the 50% probability level.

Figure 2
Molecular structure of (2) with displacement ellipsoids drawn at the 50% probability level.

Selected geometric parameters for (1) and (2) are presented in Tables 1 and 2. The Mo1—P1 bond lengths [2.4535 (9) Å for dimethylphenylphosphine derivative (1) and 2.4813 (6) Å for ethyldiphenylphosphine derivative (2)] track with the steric bulk of the ligands and are consistent with the previously reported methyldiphenylphosphine complex (Whited et al., 2012 ), which exhibits an Mo—P bond length [2.4620 (14) Å] that is intermediate between those of (1) and (2). Along with a slightly longer Mo—P distance, the sterically bulkier derivative (2) exhibits a larger C3—Mo1—P1 angle [135.76 (6)°] relative to (1) [131.79 (9)°], again with the methyldiphenylphosphine derivative intermediate [132.27 (2)°]. The steric effects of the phosphine ligands observed in the solid state are consistent with findings regarding decarbonylation rates for this class of complexes (Barnett & Pollmann, 1974), where the steric influence of bulkier phosphines enhances the rate of the decarbonylation reaction.

Table 1
Selected geometric parameters (Å, °) for (1)

Mo1—P1	2.4535 (9)	Mo1—C2	1.973 (4)
Mo1—C1	1.949 (3)	Mo1—C3	2.251 (4)

C1—Mo1—P1	76.95 (9)	C2—Mo1—P1	78.13 (11)
C1—Mo1—C2	106.40 (14)	C2—Mo1—C3	76.05 (15)
C1—Mo1—C3	72.37 (13)	C3—Mo1—P1	131.79 (9)

Table 2
Selected geometric parameters (Å, °) for (2)

Mo1—P1	2.4813 (6)	Mo1—C2	1.960 (2)
Mo1—C1	1.979 (2)	Mo1—C3	2.273 (2)

C1—Mo1—P1	79.07 (6)	C2—Mo1—C1	106.04 (9)
C1—Mo1—C3	75.46 (8)	C2—Mo1—C3	73.53 (9)
C2—Mo1—P1	79.67 (6)	C3—Mo1—P1	135.76 (6)

3. Supramolecular features

The extended structures of (1) and (2) are quite different, but the acetyl oxygen atom (O3) plays an important role in the packing of both structures. For dimethylphenylphosphine complex (1), there are C—H⋯O hydrogen-bonding interactions between O3 of the acetyl carbonyl on one Mo complex and H11C from a phosphine methyl substituent (2.45 Å) and H13 from a phenyl group (2.36 Å) on the same phosphine on a neighboring molecule (Table 3). These short contacts organize the molecules into chains parallel to [001] (Fig. 3). Additional short contacts (2.40 Å) between O1 of a carbonyl ligand and H15 of a phosphine phenyl substituent within the chains are present. The chains are arranged in layers parallel to (100). In contrast to the closely related methyldiphenylphosphine derivative (Whited et al., 2012), (1) does not exhibit any π–π interactions between the Cp ring and a phosphine phenyl substituent. In contrast, the closest phenyl group is oriented perpendicular to the Cp ring with a distance of 3.00 Å between H17 of the phenyl group and the Cp centroid.

Table 3
Hydrogen-bond geometry (Å, °) for (1)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11C⋯O3ⁱ	0.98	2.45	3.344 (5)	152
C13—H13⋯O3ⁱ	0.95	2.36	3.275 (5)	162
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 3
Crystal packing of (1) viewed along [010] showing the layered arrangement parallel to (100). Dashed lines indicate intermolecular C—H⋯O hydrogen-bonding interactions.

The supramolecular organization of ethyldiphenylphosphine derivative (2) is quite different, though it is still partly governed by hydrogen-bonding interactions involving O3 of the acetyl group. In this case, short contacts (2.66 Å) between O3 of the acetyl group and H22 of a phosphine phenyl substituent (Table 4) link the molecules into chains parallel to [010]. An additional set of short contacts between O2 of a carbonyl ligand and H8 from a Cp ring (2.63 Å) and H13 from a phenyl ring (2.71 Å) on an adjacent molecule organize the molecules into centrosymmetrical dimers, joining the unit cells along [010] (Fig. 4). Finally, another set of centrosymmetrical dimers is formed through short contacts between C8/H8 units on Cp rings of adjacent molecules (Fig. 5).

Table 4
Hydrogen-bond geometry (Å, °) for (2)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O2ⁱ	0.93	2.63	3.414 (3)	142
C13—H13⋯O2ⁱ	0.93	2.71	3.282 (3)	121
C22—H22⋯O3ⁱⁱ	0.93	2.66	3.316 (3)	128
Symmetry codes: (i) -x, -y, -z+1; (ii) x, y+1, z.

Figure 4
Crystal packing of (2) viewed along [100] showing chains of centrosymmetrical dimers.

Figure 5
Centrosymmetrical dimers of (2) connected through C8/H8 interactions of Cp rings on adjacent molecules.

4. Database survey

The current version of the Cambridge Structural Database (Version 5.35, updated November 2013; Allen, 2002 ) has nine entries corresponding to molybdenum acyl complexes of the general form [Mo(C₅H₅)(CO)₂(PR₃)(COR)], as well as five tungsten complexes with the same ligand types. No chromium complexes with the same ligand set are in the database. The trans-dicarbonyl structure, as observed for (1) and (2), is preferred except in cases where the phosphine and acyl ligands are covalently linked, forcing them to be cis (Adams et al., 1991 ; Mercier et al., 1993 ; Yan et al., 2009 ). The preference for a trans geometry is likely at least partly steric in nature, since the only example with a cis-dicarbonyl geometry without linked phosphine and acyl ligands is for a molybdenum formyl with a small trimethylphosphine ligand and a bulky pentamethylcyclopentadienyl ligand (Asdar et al., 1989 ).

5. Synthesis and crystallization

CpMo(CO)₃(CH₃). This compound was prepared by a modification of the method used of Gladysz et al. (1979 ), as previously reported by Whited & Hofmeister (2014 ).

CpMo(CO)₂(PMe₂Ph)(COCH₃) (1). In an inert-atmosphere glove box, CpMo(CO)₃(CH₃) (113 mg, 0.435 mmol) was dissolved in 2 ml acetonitrile. In a separate vial, dimethylphenylphosphine (97.0 mg, 0.702 mmol) was dissolved in 2 ml acetonitrile. The vials were combined and the resulting solution was stirred for 1 week. Solvent was removed in vacuo, leaving a yellow–orange solid that was triturated with pentane (5 ml) and isolated by filtration to afford the desired product in pure form as a yellow powder (112 mg, 65%). Crystalline material was obtained as yellow–orange prisms by chilling a concentrated diethyl ether solution at 233 K. ¹H NMR (400 MHz, CDCl₃): δ 7.67–7.58 (m, 2H, Ar–H), 7.50–7.41 (m, 3H, Ar–H), 4.97 (d, J = 1.1 Hz, 5H, Cp H), 2.58 (s, 3H, C(O)CH₃), 1.91 (d, ²J_PH = 8.9 Hz, 6H, P(CH₃)₂). ¹³C{¹H} NMR (101 MHz, CDCl₃): δ 267.3 (d, ²J_PC = 13 Hz, –COCH₃), 237.8 (d, ²J_PC = 24 Hz, –CO), 139.2 (d, ¹J_PC = 40 Hz, C_ipso from Ph–P), 130.3 (d, ⁴J_PC = 2 Hz, C_para from Ph–P), 129.6 (d, ²J_PC = 10 Hz, C_ortho from Ph–P), 128.9 (d, ²J_PC = 10 Hz, C_meta from Ph–P), 96.0 (s, Cp ring), 51.7 (s, –COCH₃), 20.0 (d, ¹J_PC = 33 Hz, P(CH₃)₂). ³¹P{¹H} NMR (162 MHz, CDCl₃): δ 33.1 (s). IR (CH₂Cl₂, NaCl, cm⁻¹) ν(CO): 1931, 1846, 1601 (acetyl).

CpMo(CO)₂(PEtPh₂)(COCH₃) (2). In an inert-atmosphere glove box, CpMo(CO)₃(CH₃) (105 mg, 0.404 mmol) was dissolved in 2 ml acetonitrile. Ethyldiphenylphosphine (129 mg, 0.602 mmol) was added and the resulting solution was stirred for one week. Solvent was removed in vacuo, leaving a yellow solid that was triturated with pentane (5 ml) and isolated by filtration to afford the desired product in pure form as a yellow powder (106 mg, 55%). Crystalline material was obtained as yellow blocks by slow evaporation of diethyl ether from a concentrated solution at ambient temperature. ¹H NMR (400 MHz, CDCl₃): δ 7.50–7.42 (m, 10H, Ar–H), 4.92 (d, J = 1.2 Hz, 5H, Cp H), 2.68 (apparent quint, ²J_PH = ³J_HH = 7.8 Hz, 2H, PCH₂CH₃), 2.63 (s, 3H, C(O)CH₃), 1.17 (dt, ³J_PH = 18.0 Hz, ²J_PH = 7.5 Hz, 3H, PCH₂CH₃). ¹³C{¹H} NMR (101 MHz, CDCl₃): δ 266.4 (d, ²J_PC = 11 Hz, –COCH₃), 238.5 (d, ²J_PC = 23 Hz, –CO), 135.9 (d, ¹J_PC = 40 Hz, C_ipso from Ph–P), 132.1 (d, ²J_PC = 10 Hz, C_ortho from Ph–P), 130.4 (d, ⁴J_PC = 2 Hz, C_para from Ph–P), 128.7 (d, ²J_PC = 9 Hz, C_meta from Ph–P), 96.5 (s, Cp ring), 51.0 (s, –COCH₃), 26.3 (d, ¹J_PC = 32 Hz, PCH₂CH₃), 9.0 (d, ²J_PC = 2 Hz, PCH₂CH₃). ³¹P{¹H} NMR (162 MHz, CDCl₃): δ 59.3 (s). IR (CH₂Cl₂, NaCl, cm⁻¹) ν(CO): 1937, 1859, 1610 (acetyl).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. H-atoms were treated in calculated positions and refined in the riding-model approximation with distances of C—H = 0.95, 1.00 and 0.98 Å for the phenyl, cyclopentadienyl and alkyl groups, respectively, and with U_iso(H) = k×U_eq(C), k = 1.2 for phenyl and cyclopentadienyl groups and 1.5 for alkyl groups. Methyl group H atoms were allowed to rotate in order to find the best rotameric conformation.

Table 5
Experimental details

	(1)	(2)
Crystal data
Chemical formula	[Mo(C₅H₅)(C₂H₃O)(C₈H₁₁P)(CO)₂]	[Mo(C₅H₅)(C₂H₃O)(C₁₄H₁₅P)(CO)₂]
M_r	398.23	474.32
Crystal system, space group	Orthorhombic, Pna2₁	Triclinic, P $[\overline{1}]$
Temperature (K)	173	173
a, b, c (Å)	16.374 (2), 6.8898 (10), 15.208 (2)	8.2451 (8), 11.6132 (11), 12.5265 (12)
α, β, γ (°)	90, 90, 90	63.617 (4), 77.167 (5), 84.671 (6)
V (Å³)	1715.6 (4)	1047.65 (18)
Z	4	2
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.87	0.72
Crystal size (mm)	0.4 × 0.4 × 0.19	0.32 × 0.26 × 0.21

Data collection
Diffractometer	Rigaku XtaLAB mini	Rigaku XtaLAB mini
Absorption correction	Multi-scan (REQAB; Rigaku, 1998 )	Multi-scan (REQAB; Rigaku, 1998)
T_min, T_max	0.707, 0.848	0.712, 0.859
No. of measured, independent and observed [I > 2σ(I)] reflections	17021, 3923, 3639	11081, 4797, 4365
R_int	0.035	0.029
(sin θ/λ)_max (Å⁻¹)	0.649	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.045, 1.05	0.028, 0.068, 1.09
No. of reflections	3923	4797
No. of parameters	202	255
No. of restraints	1	0
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.27	0.30, −0.82
Absolute structure	Flack x determined using 1649 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 ).	–
Absolute structure parameter	0.007 (18)	–
Computer programs: CrystalClear (Rigaku, 2011 ), SHELXS and SHELXL (Sheldrick, 2008 ), SIR2008 (Burla et al., 2007 ) and OLEX2 (Dolomanov et al., 2009 ).

A small number of low-angle reflections [three for (1); six for (2)] were rejected from these high-quality data sets due to the arrangement of the instrument with a conservatively sized beam stop and a fixed-position detector. The large number of reflections in the data sets (and the Fourier-transform relationship of intensities to atoms) ensures that no particular bias was thereby introduced.

Supporting information

CCDC references: 1024131; 1024132

Crystal structure: contains datablocks 1, 2, general. DOI: 10.1107/S1600536814020534/wm5058sup1.cif

Structure factors: contains datablock 1. DOI: 10.1107/S1600536814020534/wm50581sup2.hkl

Structure factors: contains datablock 2. DOI: 10.1107/S1600536814020534/wm50582sup3.hkl

checkCIF report

Chemical context top

Cyclopentadienylmolybdenum polycarbonyl complexes [Mo(C₅H₅)(CO)_n] with `piano-stool' geometries have been studied extensively for their fundamental organometallic reactivity. In particular, alkyl complexes of the form [Mo(C₅H₅)(CO)₃(R)] have been studied for their migratory insertion reactivity (Barnett & Treichel, 1967; Butler et al., 1967), affording [Mo(C₅H₅)(PR₃)(CO)₂(COR)] acetyl complexes on exposure to phosphine ligands. Although the insertion reaction shows little dependence on the nature of the phosphine, the corresponding deinsertion shows a strong dependence on steric bulk of the phosphine, with bulkier groups giving enhanced deinsertion rates (Barnett, 1969; Barnett & Pollmann, 1974).

We have developed an interest in the solid-state structural properties of a series of piano-stool molybdenum acetyl complexes derived from migratory insertion with various phosphines, with the goal of understanding how modification of the phosphine substituents affects ground-state structure as well as solid-state packing. Recently, we reported an unusual example where orientation of the acetyl group in the solid state can be changed by introduction of furyl substituents on the phosphine ligand (Whited et al., 2013). In this study, the structures obtained for dimethylphenylphosphine, [Mo(C₅H₅)(P(CH₃)₂(C₆H₅))(CO)₂(COCH₃)] (1), and ethyldiphenylphosphine, [Mo(C₅H₅)(P(C₂H₅)(C₆H₅)₂))(CO)₂(COCH₃)] (2), derivatives are compared.

Structural commentary top

The molecular structures of (1) and (2) are illustrated in Figs. 1 and 2. In spite of the somewhat different steric environments provided by the phosphine ligands, the molecular structures are quite similar. Both complexes exhibit a trans disposition of carbonyl ligands common for compounds of this class. Complexes (1) and (2) both have structures where the oxygen atom of the acetyl group points toward the cyclopentadienyl (Cp) ring. This orientation is also consistent with the majority of crystal structures of related complexes, with the exception of the recently reported tri(2-furyl)phosphine derivative, in which the acetyl group points away from the Cp ring, enabling intermolecular O···H—C interactions with the furyl group of a neighboring molecule (Whited et al., 2013).

Selected geometric parameters for (1) and (2) are presented in Tables 1 and 2. The Mo1—P1 bond lengths [2.4535 (9) Å for dimethylphenylphosphine derivative (1) and 2.4813 (6) Å for ethyldiphenylphosphine derivative (2)] track with the steric bulk of the ligands and are consistent with the previously reported methyldiphenylphosphine complex (Whited et al., 2012), which exhibits an Mo—P bond length [2.4620 (14) Å] that is intermediate between those of (1) and (2). Along with a slightly longer Mo—P distance, the sterically bulkier derivative (2) exhibits a larger C3—Mo1—P1 angle [135.76 (6)°] relative to (1) [131.79 (9)°], again with the methyldiphenylphosphine derivative intermediate [132.27 (2)°]. The steric effects of the phosphine ligands observed in the solid state are consistent with findings regarding decarbonylation rates for this class of complexes (Barnett & Pollmann, 1974), where the steric influence of bulkier phosphines enhances the rate of the decarbonylation reaction.

Supramolecular features top

The extended structures of (1) and (2) are quite different, but the acetyl oxygen atom (O3) plays an important role in the packing of both structures. For dimethylphenylphosphine complex (1), there are C—H···O hydrogen-bonding interactions between O3 of the acetyl carbonyl on one Mo complex and H11C from a phosphine methyl substituent (2.45 Å) and H13 from a phenyl group (2.36 Å) on the same phosphine on a neighboring molecule (Table 3). These short contacts organize the molecules into chains parallel to [001] (Fig. 3). Additional short contacts (2.40 Å) between O1 of a carbonyl ligand and H15 of a phosphine phenyl substituent within the chains are present. The chains are arranged in layers parallel to (100). In contrast to the closely related methyldiphenylphosphine derivative (Whited et al., 2012), (1) does not exhibit any π–π interactions between the Cp ring and a phosphine phenyl substituent. In contrast, the closest phenyl group is oriented perpendicular to the Cp ring with a distance of 3.00 Å between H17 of the phenyl group and the Cp centroid.

Database survey top

The current version of the Cambridge Structural Database (Version 5.35, updated November 2013; Allen, 2002) has nine entries corresponding to molybdenum acyl complexes of the general form [Mo(C₅H₅)(CO)₂(PR₃)(COR)], as well as five tungsten complexes with the same ligand types. No chromium complexes with the same ligand set are in the database. The trans-dicarbonyl structure, as observed for (1) and (2), is preferred except in cases where the phosphine and acyl ligands are covalently linked, forcing them to be cis (Adams et al., 1991; Mercier et al., 1993; Yan et al., 2009). The preference for a trans geometry is likely at least partly steric in nature, since the only example with a cis-dicarbonyl geometry without linked phosphine and acyl ligands is for a molybdenum formyl with a small trimethylphosphine ligand and a bulky pentamethylcyclopentadienyl ligand (Asdar et al., 1989).

Synthesis and crystallization top

CpMo(CO)₃(CH₃). This compound was prepared by a modification of the method used of Gladysz et al. (1979), as previously reported by Whited & Hofmeister (2014).

Refinement top

Related literature top

For related literature, see: Adams et al. (1991); Allen (2002); Asdar et al. (1989); Barnett (1969); Barnett & Pollmann (1974); Barnett & Treichel (1967); Butler et al. (1967); Gladysz et al. (1979); Mercier et al. (1993); Whited & Hofmeister (2014); Whited et al. (2012, 2013); Yan et al. (2009).

Computing details top

For both compounds, data collection: CrystalClear (Rigaku, 2011); cell refinement: CrystalClear (Rigaku, 2011); data reduction: CrystalClear (Rigaku, 2011). Program(s) used to solve structure: SHELXS (Sheldrick, 2008) for (1); SIR2008 (Burla et al., 2007) for (2). For both compounds, program(s) used to refine structure: SHELXL (Sheldrick, 2008); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. Molecular structure of (1) with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Molecular structure of (2) with displacement ellipsoids drawn at the 50% probability level.
	Fig. 3. Crystal packing of (1) viewed along [010] showing the layered arrangement parallel to (100). Dashed lines indicate intermolecular C—H···O hydrogen-bonding interactions.
	Fig. 4. Crystal packing of (2) viewed along [100] showing chains of centrosymmetrical dimers.
	Fig. 5. Centrosymmetrical dimers of (2) connected through C8/H8 interactions of Cp rings on adjacent molecules.

(1) trans-Acetyldicarbonyl-(η⁵-cyclopentadienyl)-˘dimethylphenylphosphine)-molybdenum(II) top

Crystal data top

[Mo(C₅H₅)(C₂H₃O)(C₈H₁₁P)(CO)₂]	F(000) = 808
M_r = 398.23	D_x = 1.542 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: P 2c -2n	Cell parameters from 16109 reflections
a = 16.374 (2) Å	θ = 3.2–27.6°
b = 6.8898 (10) Å	µ = 0.87 mm⁻¹
c = 15.208 (2) Å	T = 173 K
V = 1715.6 (4) Å³	Prism, yellow
Z = 4	0.4 × 0.4 × 0.19 mm

Data collection top

Rigaku XtaLAB mini diffractometer	3639 reflections with I > 2σ(I)
Detector resolution: 6.849 pixels mm^-1	R_int = 0.035
ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	h = −21→21
T_min = 0.707, T_max = 0.848	k = −8→8
17021 measured reflections	l = −19→19
3923 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.021	w = 1/[σ²(F_o²) + (0.0142P)² + 0.493P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.045	(Δ/σ)_max = 0.002
S = 1.05	Δρ_max = 0.21 e Å⁻³
3923 reflections	Δρ_min = −0.27 e Å⁻³
202 parameters	Absolute structure: Flack x determined using 1649 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013).
1 restraint	Absolute structure parameter: 0.007 (18)
Primary atom site location: heavy-atom method

Crystal data top

[Mo(C₅H₅)(C₂H₃O)(C₈H₁₁P)(CO)₂]	V = 1715.6 (4) Å³
M_r = 398.23	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 16.374 (2) Å	µ = 0.87 mm⁻¹
b = 6.8898 (10) Å	T = 173 K
c = 15.208 (2) Å	0.4 × 0.4 × 0.19 mm

Data collection top

Rigaku XtaLAB mini diffractometer	3923 independent reflections
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	3639 reflections with I > 2σ(I)
T_min = 0.707, T_max = 0.848	R_int = 0.035
17021 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	H-atom parameters constrained
wR(F²) = 0.045	Δρ_max = 0.21 e Å⁻³
S = 1.05	Δρ_min = −0.27 e Å⁻³
3923 reflections	Absolute structure: Flack x determined using 1649 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013).
202 parameters	Absolute structure parameter: 0.007 (18)
1 restraint

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Mo1	0.79993 (2)	0.60128 (3)	0.24997 (2)	0.02038 (7)
P1	0.89764 (5)	0.44416 (12)	0.15052 (5)	0.02144 (17)
O1	0.95421 (15)	0.8609 (4)	0.26796 (19)	0.0403 (8)
O2	0.82922 (19)	0.2063 (4)	0.34585 (19)	0.0449 (7)
O3	0.7578 (2)	0.7896 (5)	0.4257 (2)	0.0533 (8)
C1	0.89797 (19)	0.7587 (4)	0.2637 (2)	0.0238 (7)
C2	0.8215 (2)	0.3542 (5)	0.3113 (2)	0.0278 (8)
C3	0.8089 (2)	0.6869 (5)	0.3925 (2)	0.0300 (8)
C4	0.8795 (3)	0.6224 (6)	0.4511 (3)	0.0439 (11)
H4A	0.8657	0.4984	0.4791	0.066*
H4B	0.8891	0.7206	0.4966	0.066*
H4C	0.9289	0.6067	0.4155	0.066*
C5	0.7040 (2)	0.8435 (6)	0.2268 (3)	0.0432 (13)
H5	0.7125	0.9674	0.2525	0.052*
C6	0.6620 (2)	0.6856 (7)	0.2659 (3)	0.0465 (11)
H6	0.6375	0.6850	0.3225	0.056*
C7	0.6631 (2)	0.5310 (7)	0.2065 (3)	0.0425 (10)
H7	0.6393	0.4069	0.2156	0.051*
C8	0.7056 (2)	0.5909 (6)	0.1309 (3)	0.0368 (9)
H8	0.7156	0.5137	0.0802	0.044*
C9	0.7308 (2)	0.7839 (6)	0.1427 (3)	0.0376 (9)
H9	0.7604	0.8604	0.1017	0.045*
C10	0.9940 (2)	0.3716 (6)	0.2006 (2)	0.0331 (8)
H10A	1.0193	0.4841	0.2292	0.050*
H10B	1.0308	0.3215	0.1551	0.050*
H10C	0.9839	0.2702	0.2444	0.050*
C11	0.8649 (3)	0.2188 (5)	0.0985 (3)	0.0373 (9)
H11A	0.8542	0.1210	0.1439	0.056*
H11B	0.9080	0.1720	0.0591	0.056*
H11C	0.8150	0.2421	0.0646	0.056*
C12	0.9282 (2)	0.5990 (5)	0.0594 (2)	0.0237 (7)
C13	0.8797 (2)	0.6100 (6)	−0.0161 (2)	0.0337 (9)
H13	0.8334	0.5280	−0.0220	0.040*
C14	0.8991 (3)	0.7407 (6)	−0.0823 (3)	0.0452 (10)
H14	0.8653	0.7487	−0.1329	0.054*
C15	0.9663 (3)	0.8582 (6)	−0.0759 (2)	0.0386 (10)
H15	0.9791	0.9467	−0.1218	0.046*
C16	1.0155 (2)	0.8471 (5)	−0.0018 (3)	0.0347 (9)
H16	1.0628	0.9266	0.0027	0.042*
C17	0.9959 (2)	0.7194 (5)	0.0662 (2)	0.0274 (7)
H17	1.0290	0.7148	0.1175	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.01676 (11)	0.02175 (12)	0.02264 (12)	−0.00044 (9)	−0.00022 (16)	0.00141 (16)
P1	0.0228 (4)	0.0208 (4)	0.0207 (4)	0.0008 (3)	−0.0010 (4)	−0.0001 (3)
O1	0.0323 (13)	0.0419 (15)	0.047 (2)	−0.0136 (11)	0.0007 (12)	−0.0156 (13)
O2	0.0580 (18)	0.0296 (15)	0.0471 (18)	0.0000 (13)	−0.0037 (14)	0.0108 (14)
O3	0.056 (2)	0.065 (2)	0.0386 (16)	0.0241 (17)	0.0116 (14)	−0.0095 (16)
C1	0.0267 (15)	0.0265 (15)	0.0183 (19)	0.0055 (12)	0.0014 (14)	−0.0051 (13)
C2	0.0254 (18)	0.029 (2)	0.0285 (18)	−0.0025 (14)	−0.0001 (14)	−0.0009 (15)
C3	0.035 (2)	0.0295 (19)	0.0259 (18)	0.0013 (16)	0.0048 (15)	0.0024 (15)
C4	0.058 (3)	0.046 (3)	0.027 (2)	0.008 (2)	−0.006 (2)	−0.0063 (18)
C5	0.0278 (19)	0.039 (2)	0.063 (4)	0.0139 (16)	−0.0087 (18)	−0.0031 (18)
C6	0.0172 (16)	0.077 (3)	0.046 (3)	0.0088 (18)	−0.0001 (18)	−0.002 (2)
C7	0.020 (2)	0.053 (3)	0.054 (3)	−0.0112 (18)	−0.0108 (17)	0.013 (2)
C8	0.026 (2)	0.048 (2)	0.036 (2)	0.0003 (16)	−0.0141 (16)	0.0018 (17)
C9	0.0264 (19)	0.039 (2)	0.048 (2)	0.0015 (16)	−0.0110 (18)	0.0168 (19)
C10	0.028 (2)	0.040 (2)	0.031 (2)	0.0105 (16)	0.0008 (16)	0.0041 (15)
C11	0.052 (3)	0.0237 (19)	0.036 (2)	−0.0019 (17)	−0.0030 (18)	−0.0057 (17)
C12	0.0227 (17)	0.0273 (18)	0.0210 (16)	0.0045 (14)	0.0005 (14)	−0.0029 (14)
C13	0.032 (2)	0.043 (2)	0.026 (2)	−0.0112 (16)	−0.0042 (15)	0.0037 (16)
C14	0.050 (3)	0.062 (3)	0.025 (2)	−0.009 (2)	−0.0047 (18)	0.0115 (18)
C15	0.046 (2)	0.039 (2)	0.030 (2)	−0.0019 (18)	0.0108 (17)	0.0091 (17)
C16	0.032 (2)	0.031 (2)	0.042 (2)	−0.0065 (16)	0.0104 (17)	−0.0019 (17)
C17	0.0254 (18)	0.0292 (19)	0.0277 (18)	−0.0006 (15)	0.0010 (14)	−0.0034 (15)

Geometric parameters (Å, º) top

Mo1—P1	2.4535 (9)	C6—C7	1.397 (6)
Mo1—C1	1.949 (3)	C7—H7	0.9500
Mo1—C2	1.973 (4)	C7—C8	1.406 (6)
Mo1—C3	2.251 (4)	C8—H8	0.9500
Mo1—C5	2.319 (4)	C8—C9	1.403 (5)
Mo1—C6	2.344 (3)	C9—H9	0.9500
Mo1—C7	2.385 (4)	C10—H10A	0.9800
Mo1—C8	2.382 (4)	C10—H10B	0.9800
Mo1—C9	2.351 (3)	C10—H10C	0.9800
P1—C10	1.822 (4)	C11—H11A	0.9800
P1—C11	1.823 (4)	C11—H11B	0.9800
P1—C12	1.819 (4)	C11—H11C	0.9800
O1—C1	1.161 (4)	C12—C13	1.397 (5)
O2—C2	1.153 (4)	C12—C17	1.388 (5)
O3—C3	1.208 (4)	C13—H13	0.9500
C3—C4	1.525 (5)	C13—C14	1.388 (5)
C4—H4A	0.9800	C14—H14	0.9500
C4—H4B	0.9800	C14—C15	1.370 (6)
C4—H4C	0.9800	C15—H15	0.9500
C5—H5	0.9500	C15—C16	1.387 (6)
C5—C6	1.417 (6)	C16—H16	0.9500
C5—C9	1.413 (6)	C16—C17	1.395 (5)
C6—H6	0.9500	C17—H17	0.9500

C1—Mo1—P1	76.95 (9)	C9—C5—H5	126.0
C1—Mo1—C2	106.40 (14)	C9—C5—C6	107.9 (4)
C1—Mo1—C3	72.37 (13)	Mo1—C6—H6	120.0
C1—Mo1—C5	100.01 (14)	C5—C6—Mo1	71.4 (2)
C1—Mo1—C6	130.12 (14)	C5—C6—H6	126.0
C1—Mo1—C7	156.39 (14)	C7—C6—Mo1	74.5 (2)
C1—Mo1—C8	129.21 (14)	C7—C6—C5	107.9 (4)
C1—Mo1—C9	99.96 (13)	C7—C6—H6	126.0
C2—Mo1—P1	78.13 (11)	Mo1—C7—H7	121.9
C2—Mo1—C3	76.05 (15)	C6—C7—Mo1	71.2 (2)
C2—Mo1—C5	144.49 (15)	C6—C7—H7	125.9
C2—Mo1—C6	109.72 (15)	C6—C7—C8	108.1 (4)
C2—Mo1—C7	97.13 (15)	C8—C7—Mo1	72.7 (2)
C2—Mo1—C8	116.74 (14)	C8—C7—H7	125.9
C2—Mo1—C9	151.18 (14)	Mo1—C8—H8	121.4
C3—Mo1—P1	131.79 (9)	C7—C8—Mo1	73.0 (2)
C3—Mo1—C5	90.13 (14)	C7—C8—H8	125.7
C3—Mo1—C6	84.19 (15)	C9—C8—Mo1	71.5 (2)
C3—Mo1—C7	112.45 (14)	C9—C8—C7	108.6 (4)
C3—Mo1—C8	141.51 (14)	C9—C8—H8	125.7
C3—Mo1—C9	124.02 (14)	Mo1—C9—H9	120.4
C5—Mo1—P1	131.72 (11)	C5—C9—Mo1	71.2 (2)
C5—Mo1—C6	35.38 (15)	C5—C9—H9	126.3
C5—Mo1—C7	57.84 (15)	C8—C9—Mo1	74.0 (2)
C5—Mo1—C8	57.75 (14)	C8—C9—C5	107.5 (4)
C5—Mo1—C9	35.21 (14)	C8—C9—H9	126.3
C6—Mo1—P1	143.25 (12)	P1—C10—H10A	109.5
C6—Mo1—C7	34.36 (15)	P1—C10—H10B	109.5
C6—Mo1—C8	57.40 (15)	P1—C10—H10C	109.5
C6—Mo1—C9	58.34 (15)	H10A—C10—H10B	109.5
C7—Mo1—P1	110.60 (12)	H10A—C10—H10C	109.5
C8—Mo1—P1	86.61 (11)	H10B—C10—H10C	109.5
C8—Mo1—C7	34.30 (14)	P1—C11—H11A	109.5
C9—Mo1—P1	97.03 (11)	P1—C11—H11B	109.5
C9—Mo1—C7	57.58 (14)	P1—C11—H11C	109.5
C9—Mo1—C8	34.49 (13)	H11A—C11—H11B	109.5
C10—P1—Mo1	115.36 (13)	H11A—C11—H11C	109.5
C10—P1—C11	101.66 (18)	H11B—C11—H11C	109.5
C11—P1—Mo1	116.85 (14)	C13—C12—P1	120.1 (3)
C12—P1—Mo1	112.96 (11)	C17—C12—P1	120.8 (3)
C12—P1—C10	103.97 (17)	C17—C12—C13	118.9 (3)
C12—P1—C11	104.47 (17)	C12—C13—H13	120.0
O1—C1—Mo1	175.6 (3)	C14—C13—C12	120.1 (3)
O2—C2—Mo1	175.7 (3)	C14—C13—H13	120.0
O3—C3—Mo1	120.7 (3)	C13—C14—H14	119.5
O3—C3—C4	116.8 (3)	C15—C14—C13	121.0 (4)
C4—C3—Mo1	122.4 (3)	C15—C14—H14	119.5
C3—C4—H4A	109.5	C14—C15—H15	120.3
C3—C4—H4B	109.5	C14—C15—C16	119.5 (4)
C3—C4—H4C	109.5	C16—C15—H15	120.3
H4A—C4—H4B	109.5	C15—C16—H16	119.9
H4A—C4—H4C	109.5	C15—C16—C17	120.2 (3)
H4B—C4—H4C	109.5	C17—C16—H16	119.9
Mo1—C5—H5	119.0	C12—C17—C16	120.3 (3)
C6—C5—Mo1	73.3 (2)	C12—C17—H17	119.8
C6—C5—H5	126.0	C16—C17—H17	119.8
C9—C5—Mo1	73.6 (2)

Mo1—P1—C12—C13	−84.0 (3)	C7—C8—C9—Mo1	64.1 (3)
Mo1—P1—C12—C17	90.8 (3)	C7—C8—C9—C5	0.3 (4)
Mo1—C5—C6—C7	−66.0 (3)	C9—C5—C6—Mo1	66.0 (2)
Mo1—C5—C9—C8	65.6 (2)	C9—C5—C6—C7	0.0 (4)
Mo1—C6—C7—C8	−63.8 (3)	C10—P1—C12—C13	150.3 (3)
Mo1—C7—C8—C9	−63.1 (2)	C10—P1—C12—C17	−35.0 (3)
Mo1—C8—C9—C5	−63.7 (2)	C11—P1—C12—C13	44.0 (3)
P1—C12—C13—C14	174.4 (3)	C11—P1—C12—C17	−141.2 (3)
P1—C12—C17—C16	−175.7 (3)	C12—C13—C14—C15	1.1 (6)
C5—C6—C7—Mo1	64.0 (2)	C13—C12—C17—C16	−0.8 (5)
C5—C6—C7—C8	0.2 (4)	C13—C14—C15—C16	−0.3 (6)
C6—C5—C9—Mo1	−65.8 (3)	C14—C15—C16—C17	−1.1 (6)
C6—C5—C9—C8	−0.2 (4)	C15—C16—C17—C12	1.6 (5)
C6—C7—C8—Mo1	62.8 (3)	C17—C12—C13—C14	−0.5 (6)
C6—C7—C8—C9	−0.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11C···O3ⁱ	0.98	2.45	3.344 (5)	152
C13—H13···O3ⁱ	0.95	2.36	3.275 (5)	162

Symmetry code: (i) −x+3/2, y−1/2, z−1/2.

(2) trans-Acetyldicarbonyl(η⁵-cyclopentadienyl)(ethyldiphenylphosphane)molybdenum(II) top

Crystal data top

[Mo(C₅H₅)(C₂H₃O)(C₁₄H₁₅P)(CO)₂]	Z = 2
M_r = 474.32	F(000) = 484
Triclinic, P1	D_x = 1.504 Mg m⁻³
a = 8.2451 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.6132 (11) Å	Cell parameters from 10268 reflections
c = 12.5265 (12) Å	θ = 3.2–27.6°
α = 63.617 (4)°	µ = 0.72 mm⁻¹
β = 77.167 (5)°	T = 173 K
γ = 84.671 (6)°	Prism, yellow
V = 1047.65 (18) Å³	0.32 × 0.26 × 0.21 mm

Data collection top

Rigaku XtaLAB mini diffractometer	4365 reflections with I > 2σ(I)
Detector resolution: 6.849 pixels mm^-1	R_int = 0.029
ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	h = −10→10
T_min = 0.712, T_max = 0.859	k = −15→15
11081 measured reflections	l = −16→16
4797 independent reflections

Refinement top

Refinement on F²	Primary atom site location: heavy-atom method
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H-atom parameters constrained
wR(F²) = 0.068	w = 1/[σ²(F_o²) + (0.029P)² + 0.4738P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
4797 reflections	Δρ_max = 0.30 e Å⁻³
255 parameters	Δρ_min = −0.82 e Å⁻³
0 restraints

Crystal data top

[Mo(C₅H₅)(C₂H₃O)(C₁₄H₁₅P)(CO)₂]	γ = 84.671 (6)°
M_r = 474.32	V = 1047.65 (18) Å³
Triclinic, P1	Z = 2
a = 8.2451 (8) Å	Mo Kα radiation
b = 11.6132 (11) Å	µ = 0.72 mm⁻¹
c = 12.5265 (12) Å	T = 173 K
α = 63.617 (4)°	0.32 × 0.26 × 0.21 mm
β = 77.167 (5)°

Data collection top

Rigaku XtaLAB mini diffractometer	4797 independent reflections
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	4365 reflections with I > 2σ(I)
T_min = 0.712, T_max = 0.859	R_int = 0.029
11081 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.068	H-atom parameters constrained
S = 1.09	Δρ_max = 0.30 e Å⁻³
4797 reflections	Δρ_min = −0.82 e Å⁻³
255 parameters

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Mo1	0.25391 (2)	0.22164 (2)	0.24017 (2)	0.01783 (6)
P1	0.15696 (6)	0.36677 (5)	0.33857 (5)	0.01874 (11)
O1	0.2231 (2)	0.48000 (14)	0.01116 (14)	0.0328 (4)
O2	−0.1013 (2)	0.10837 (16)	0.37595 (17)	0.0379 (4)
O3	0.2283 (2)	0.07548 (18)	0.09140 (19)	0.0459 (5)
C1	0.2279 (3)	0.3845 (2)	0.0971 (2)	0.0225 (4)
C2	0.0285 (3)	0.1541 (2)	0.3233 (2)	0.0248 (4)
C3	0.1579 (3)	0.1604 (2)	0.1164 (2)	0.0256 (5)
C4	0.0061 (3)	0.2187 (2)	0.0626 (2)	0.0361 (6)
H4A	−0.0914	0.1955	0.1265	0.054*
H4B	−0.0043	0.1869	0.0055	0.054*
H4C	0.0177	0.3106	0.0217	0.054*
C5	0.5510 (3)	0.2184 (2)	0.2032 (2)	0.0313 (5)
H5	0.6164	0.2873	0.1426	0.038*
C6	0.4935 (3)	0.1161 (2)	0.1898 (2)	0.0319 (5)
H6	0.5130	0.1063	0.1183	0.038*
C7	0.4005 (3)	0.0304 (2)	0.3044 (2)	0.0331 (5)
H7	0.3493	−0.0456	0.3213	0.040*
C8	0.4000 (3)	0.0813 (2)	0.3878 (2)	0.0321 (5)
H8	0.3485	0.0450	0.4696	0.039*
C9	0.4922 (3)	0.1978 (2)	0.3243 (2)	0.0309 (5)
H9	0.5107	0.2517	0.3575	0.037*
C10	−0.0688 (3)	0.3899 (2)	0.3745 (2)	0.0247 (4)
H10A	−0.1210	0.3075	0.4308	0.030*
H10B	−0.0899	0.4456	0.4151	0.030*
C11	−0.1500 (3)	0.4481 (2)	0.2632 (2)	0.0347 (5)
H11A	−0.1027	0.5316	0.2084	0.052*
H11B	−0.2675	0.4560	0.2887	0.052*
H11C	−0.1307	0.3934	0.2226	0.052*
C12	0.2069 (3)	0.30616 (19)	0.49000 (19)	0.0219 (4)
C13	0.1367 (3)	0.1892 (2)	0.5807 (2)	0.0273 (5)
H13	0.0644	0.1458	0.5636	0.033*
C14	0.1734 (3)	0.1371 (2)	0.6958 (2)	0.0317 (5)
H14	0.1254	0.0593	0.7554	0.038*
C15	0.2814 (3)	0.2006 (2)	0.7222 (2)	0.0338 (5)
H15	0.3055	0.1660	0.7996	0.041*
C16	0.3534 (3)	0.3154 (2)	0.6333 (2)	0.0347 (5)
H16	0.4268	0.3577	0.6508	0.042*
C17	0.3166 (3)	0.3686 (2)	0.5174 (2)	0.0284 (5)
H17	0.3656	0.4461	0.4580	0.034*
C18	0.2429 (3)	0.53126 (19)	0.26053 (19)	0.0216 (4)
C19	0.4009 (3)	0.5528 (2)	0.18706 (19)	0.0245 (4)
H19	0.4597	0.4851	0.1765	0.029*
C20	0.4719 (3)	0.6756 (2)	0.1291 (2)	0.0272 (5)
H20	0.5786	0.6889	0.0813	0.033*
C21	0.3841 (3)	0.7775 (2)	0.1424 (2)	0.0294 (5)
H21	0.4309	0.8595	0.1028	0.035*
C22	0.2268 (3)	0.7569 (2)	0.2148 (2)	0.0334 (5)
H22	0.1674	0.8253	0.2235	0.040*
C23	0.1566 (3)	0.6340 (2)	0.2749 (2)	0.0306 (5)
H23	0.0514	0.6205	0.3248	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.01765 (10)	0.01435 (9)	0.01900 (10)	0.00154 (6)	−0.00451 (7)	−0.00496 (7)
P1	0.0185 (2)	0.0163 (2)	0.0196 (3)	0.00010 (19)	−0.0039 (2)	−0.0062 (2)
O1	0.0459 (10)	0.0201 (8)	0.0262 (8)	0.0016 (7)	−0.0129 (8)	−0.0023 (7)
O2	0.0284 (9)	0.0325 (9)	0.0484 (11)	−0.0103 (7)	0.0027 (8)	−0.0168 (8)
O3	0.0520 (12)	0.0396 (10)	0.0655 (13)	0.0108 (9)	−0.0235 (10)	−0.0368 (10)
C1	0.0230 (10)	0.0208 (10)	0.0270 (11)	0.0015 (8)	−0.0070 (9)	−0.0126 (9)
C2	0.0264 (11)	0.0180 (10)	0.0297 (11)	0.0006 (8)	−0.0084 (9)	−0.0089 (9)
C3	0.0294 (11)	0.0214 (11)	0.0252 (11)	−0.0043 (9)	−0.0052 (9)	−0.0087 (9)
C4	0.0410 (14)	0.0355 (13)	0.0378 (14)	0.0009 (11)	−0.0194 (12)	−0.0161 (11)
C5	0.0166 (10)	0.0304 (12)	0.0373 (13)	0.0045 (9)	−0.0036 (9)	−0.0077 (10)
C6	0.0258 (12)	0.0348 (13)	0.0348 (13)	0.0148 (10)	−0.0068 (10)	−0.0173 (11)
C7	0.0329 (13)	0.0183 (11)	0.0421 (14)	0.0091 (9)	−0.0128 (11)	−0.0074 (10)
C8	0.0244 (11)	0.0354 (13)	0.0247 (11)	0.0100 (10)	−0.0098 (9)	−0.0022 (10)
C9	0.0190 (11)	0.0379 (13)	0.0396 (13)	0.0083 (9)	−0.0118 (10)	−0.0191 (11)
C10	0.0203 (10)	0.0230 (11)	0.0284 (11)	0.0009 (8)	−0.0025 (9)	−0.0105 (9)
C11	0.0265 (12)	0.0369 (13)	0.0442 (15)	0.0082 (10)	−0.0157 (11)	−0.0184 (12)
C12	0.0228 (10)	0.0208 (10)	0.0213 (10)	0.0024 (8)	−0.0051 (8)	−0.0086 (8)
C13	0.0321 (12)	0.0214 (11)	0.0272 (11)	−0.0026 (9)	−0.0069 (10)	−0.0086 (9)
C14	0.0400 (13)	0.0220 (11)	0.0260 (12)	0.0008 (10)	−0.0070 (10)	−0.0041 (9)
C15	0.0439 (14)	0.0332 (13)	0.0254 (12)	0.0074 (11)	−0.0163 (11)	−0.0110 (10)
C16	0.0403 (14)	0.0349 (13)	0.0348 (13)	−0.0014 (11)	−0.0171 (11)	−0.0157 (11)
C17	0.0320 (12)	0.0259 (11)	0.0267 (11)	−0.0045 (9)	−0.0063 (10)	−0.0100 (9)
C18	0.0246 (10)	0.0175 (10)	0.0215 (10)	−0.0004 (8)	−0.0073 (8)	−0.0062 (8)
C19	0.0267 (11)	0.0219 (11)	0.0255 (11)	−0.0002 (8)	−0.0046 (9)	−0.0111 (9)
C20	0.0281 (11)	0.0283 (12)	0.0234 (11)	−0.0072 (9)	−0.0003 (9)	−0.0105 (9)
C21	0.0398 (13)	0.0193 (11)	0.0269 (12)	−0.0065 (9)	−0.0080 (10)	−0.0063 (9)
C22	0.0392 (14)	0.0199 (11)	0.0418 (14)	0.0019 (10)	−0.0078 (11)	−0.0146 (10)
C23	0.0297 (12)	0.0240 (11)	0.0347 (13)	0.0004 (9)	−0.0020 (10)	−0.0118 (10)

Geometric parameters (Å, º) top

Mo1—P1	2.4813 (6)	C10—H10A	0.9700
Mo1—C1	1.979 (2)	C10—H10B	0.9700
Mo1—C2	1.960 (2)	C10—C11	1.530 (3)
Mo1—C3	2.273 (2)	C11—H11A	0.9600
Mo1—C5	2.390 (2)	C11—H11B	0.9600
Mo1—C6	2.342 (2)	C11—H11C	0.9600
Mo1—C7	2.321 (2)	C12—C13	1.398 (3)
Mo1—C8	2.340 (2)	C12—C17	1.393 (3)
Mo1—C9	2.368 (2)	C13—H13	0.9300
P1—C10	1.839 (2)	C13—C14	1.386 (3)
P1—C12	1.836 (2)	C14—H14	0.9300
P1—C18	1.841 (2)	C14—C15	1.385 (3)
O1—C1	1.158 (3)	C15—H15	0.9300
O2—C2	1.158 (3)	C15—C16	1.380 (3)
O3—C3	1.223 (3)	C16—H16	0.9300
C3—C4	1.514 (3)	C16—C17	1.395 (3)
C4—H4A	0.9600	C17—H17	0.9300
C4—H4B	0.9600	C18—C19	1.389 (3)
C4—H4C	0.9600	C18—C23	1.392 (3)
C5—H5	0.9300	C19—H19	0.9300
C5—C6	1.408 (3)	C19—C20	1.396 (3)
C5—C9	1.403 (3)	C20—H20	0.9300
C6—H6	0.9300	C20—C21	1.384 (3)
C6—C7	1.422 (3)	C21—H21	0.9300
C7—H7	0.9300	C21—C22	1.379 (3)
C7—C8	1.410 (4)	C22—H22	0.9300
C8—H8	0.9300	C22—C23	1.395 (3)
C8—C9	1.417 (3)	C23—H23	0.9300
C9—H9	0.9300

C1—Mo1—P1	79.07 (6)	C6—C7—Mo1	73.06 (12)
C1—Mo1—C3	75.46 (8)	C6—C7—H7	126.2
C1—Mo1—C5	97.88 (8)	C8—C7—Mo1	73.12 (13)
C1—Mo1—C6	109.55 (9)	C8—C7—C6	107.7 (2)
C1—Mo1—C7	144.10 (9)	C8—C7—H7	126.2
C1—Mo1—C8	153.01 (9)	Mo1—C8—H8	120.3
C1—Mo1—C9	118.12 (9)	C7—C8—Mo1	71.68 (12)
C2—Mo1—P1	79.67 (6)	C7—C8—H8	126.2
C2—Mo1—C1	106.04 (9)	C7—C8—C9	107.6 (2)
C2—Mo1—C3	73.53 (9)	C9—C8—Mo1	73.60 (12)
C2—Mo1—C5	155.94 (9)	C9—C8—H8	126.2
C2—Mo1—C6	129.67 (9)	Mo1—C9—H9	121.0
C2—Mo1—C7	99.26 (9)	C5—C9—Mo1	73.70 (13)
C2—Mo1—C8	99.09 (9)	C5—C9—C8	108.7 (2)
C2—Mo1—C9	128.81 (9)	C5—C9—H9	125.7
C3—Mo1—P1	135.76 (6)	C8—C9—Mo1	71.38 (12)
C3—Mo1—C5	110.95 (8)	C8—C9—H9	125.7
C3—Mo1—C6	82.22 (8)	P1—C10—H10A	108.7
C3—Mo1—C7	88.08 (8)	P1—C10—H10B	108.7
C3—Mo1—C8	122.06 (9)	H10A—C10—H10B	107.6
C3—Mo1—C9	139.73 (8)	C11—C10—P1	114.02 (16)
C5—Mo1—P1	107.89 (6)	C11—C10—H10A	108.7
C6—Mo1—P1	140.94 (6)	C11—C10—H10B	108.7
C6—Mo1—C5	34.59 (8)	C10—C11—H11A	109.5
C6—Mo1—C9	57.61 (8)	C10—C11—H11B	109.5
C7—Mo1—P1	131.14 (7)	C10—C11—H11C	109.5
C7—Mo1—C5	58.24 (8)	H11A—C11—H11B	109.5
C7—Mo1—C6	35.51 (8)	H11A—C11—H11C	109.5
C7—Mo1—C8	35.20 (9)	H11B—C11—H11C	109.5
C7—Mo1—C9	58.20 (9)	C13—C12—P1	118.36 (16)
C8—Mo1—P1	96.21 (7)	C17—C12—P1	123.11 (16)
C8—Mo1—C5	57.94 (8)	C17—C12—C13	118.5 (2)
C8—Mo1—C6	58.45 (9)	C12—C13—H13	119.5
C8—Mo1—C9	35.03 (8)	C14—C13—C12	120.9 (2)
C9—Mo1—P1	84.34 (6)	C14—C13—H13	119.5
C9—Mo1—C5	34.29 (8)	C13—C14—H14	120.0
C10—P1—Mo1	117.10 (7)	C15—C14—C13	120.0 (2)
C10—P1—C18	103.97 (10)	C15—C14—H14	120.0
C12—P1—Mo1	112.60 (7)	C14—C15—H15	120.1
C12—P1—C10	100.72 (10)	C16—C15—C14	119.8 (2)
C12—P1—C18	102.90 (9)	C16—C15—H15	120.1
C18—P1—Mo1	117.35 (7)	C15—C16—H16	119.8
O1—C1—Mo1	175.79 (19)	C15—C16—C17	120.4 (2)
O2—C2—Mo1	176.56 (19)	C17—C16—H16	119.8
O3—C3—Mo1	120.13 (17)	C12—C17—C16	120.3 (2)
O3—C3—C4	116.7 (2)	C12—C17—H17	119.8
C4—C3—Mo1	123.19 (16)	C16—C17—H17	119.8
C3—C4—H4A	109.5	C19—C18—P1	118.76 (16)
C3—C4—H4B	109.5	C19—C18—C23	118.97 (19)
C3—C4—H4C	109.5	C23—C18—P1	122.26 (17)
H4A—C4—H4B	109.5	C18—C19—H19	119.8
H4A—C4—H4C	109.5	C18—C19—C20	120.4 (2)
H4B—C4—H4C	109.5	C20—C19—H19	119.8
Mo1—C5—H5	122.7	C19—C20—H20	119.9
C6—C5—Mo1	70.86 (12)	C21—C20—C19	120.2 (2)
C6—C5—H5	126.1	C21—C20—H20	119.9
C9—C5—Mo1	72.01 (13)	C20—C21—H21	120.2
C9—C5—H5	126.1	C22—C21—C20	119.7 (2)
C9—C5—C6	107.7 (2)	C22—C21—H21	120.2
Mo1—C6—H6	119.9	C21—C22—H22	119.8
C5—C6—Mo1	74.56 (13)	C21—C22—C23	120.3 (2)
C5—C6—H6	125.9	C23—C22—H22	119.8
C5—C6—C7	108.3 (2)	C18—C23—C22	120.4 (2)
C7—C6—Mo1	71.43 (12)	C18—C23—H23	119.8
C7—C6—H6	125.9	C22—C23—H23	119.8
Mo1—C7—H7	119.5

Mo1—P1—C10—C11	−60.67 (18)	C9—C5—C6—C7	−1.0 (2)
Mo1—P1—C12—C13	−62.49 (18)	C10—P1—C12—C13	63.03 (19)
Mo1—P1—C12—C17	114.86 (18)	C10—P1—C12—C17	−119.61 (19)
Mo1—P1—C18—C19	−28.34 (19)	C10—P1—C18—C19	−159.42 (17)
Mo1—P1—C18—C23	153.15 (17)	C10—P1—C18—C23	22.1 (2)
Mo1—C5—C6—C7	−63.95 (15)	C12—P1—C10—C11	176.90 (17)
Mo1—C5—C9—C8	63.24 (15)	C12—P1—C18—C19	95.88 (18)
Mo1—C6—C7—C8	−65.44 (15)	C12—P1—C18—C23	−82.6 (2)
Mo1—C7—C8—C9	−65.34 (15)	C12—C13—C14—C15	−0.3 (4)
Mo1—C8—C9—C5	−64.74 (16)	C13—C12—C17—C16	−0.6 (3)
P1—C12—C13—C14	178.29 (18)	C13—C14—C15—C16	−0.5 (4)
P1—C12—C17—C16	−177.99 (18)	C14—C15—C16—C17	0.6 (4)
P1—C18—C19—C20	−178.29 (17)	C15—C16—C17—C12	−0.1 (4)
P1—C18—C23—C22	179.50 (18)	C17—C12—C13—C14	0.8 (3)
C5—C6—C7—Mo1	66.00 (15)	C18—P1—C10—C11	70.56 (18)
C5—C6—C7—C8	0.6 (2)	C18—P1—C12—C13	170.22 (17)
C6—C5—C9—Mo1	−62.23 (15)	C18—P1—C12—C17	−12.4 (2)
C6—C5—C9—C8	1.0 (2)	C18—C19—C20—C21	−1.2 (3)
C6—C7—C8—Mo1	65.40 (15)	C19—C18—C23—C22	1.0 (3)
C6—C7—C8—C9	0.1 (2)	C19—C20—C21—C22	0.9 (3)
C7—C8—C9—Mo1	64.07 (15)	C20—C21—C22—C23	0.3 (4)
C7—C8—C9—C5	−0.7 (2)	C21—C22—C23—C18	−1.3 (4)
C9—C5—C6—Mo1	62.98 (15)	C23—C18—C19—C20	0.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O2ⁱ	0.93	2.63	3.414 (3)	142
C13—H13···O2ⁱ	0.93	2.71	3.282 (3)	121
C22—H22···O3ⁱⁱ	0.93	2.66	3.316 (3)	128

Symmetry codes: (i) −x, −y, −z+1; (ii) x, y+1, z.

Selected geometric parameters (Å, º) for (1) top

Mo1—P1	2.4535 (9)	Mo1—C2	1.973 (4)
Mo1—C1	1.949 (3)	Mo1—C3	2.251 (4)

C1—Mo1—P1	76.95 (9)	C2—Mo1—P1	78.13 (11)
C1—Mo1—C2	106.40 (14)	C2—Mo1—C3	76.05 (15)
C1—Mo1—C3	72.37 (13)	C3—Mo1—P1	131.79 (9)

Selected geometric parameters (Å, º) for (2) top

Mo1—P1	2.4813 (6)	Mo1—C2	1.960 (2)
Mo1—C1	1.979 (2)	Mo1—C3	2.273 (2)

C1—Mo1—P1	79.07 (6)	C2—Mo1—C1	106.04 (9)
C1—Mo1—C3	75.46 (8)	C2—Mo1—C3	73.53 (9)
C2—Mo1—P1	79.67 (6)	C3—Mo1—P1	135.76 (6)

Hydrogen-bond geometry (Å, º) for (1) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11C···O3ⁱ	0.98	2.45	3.344 (5)	151.9
C13—H13···O3ⁱ	0.95	2.36	3.275 (5)	162.2

Symmetry code: (i) −x+3/2, y−1/2, z−1/2.

Hydrogen-bond geometry (Å, º) for (2) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O2ⁱ	0.93	2.63	3.414 (3)	142.0
C13—H13···O2ⁱ	0.93	2.71	3.282 (3)	120.8
C22—H22···O3ⁱⁱ	0.93	2.66	3.316 (3)	128.4

Symmetry codes: (i) −x, −y, −z+1; (ii) x, y+1, z.

Experimental details

	(1)	(2)
Crystal data
Chemical formula	[Mo(C₅H₅)(C₂H₃O)(C₈H₁₁P)(CO)₂]	[Mo(C₅H₅)(C₂H₃O)(C₁₄H₁₅P)(CO)₂]
M_r	398.23	474.32
Crystal system, space group	Orthorhombic, Pna2₁	Triclinic, P1
Temperature (K)	173	173
a, b, c (Å)	16.374 (2), 6.8898 (10), 15.208 (2)	8.2451 (8), 11.6132 (11), 12.5265 (12)
α, β, γ (°)	90, 90, 90	63.617 (4), 77.167 (5), 84.671 (6)
V (Å³)	1715.6 (4)	1047.65 (18)
Z	4	2
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.87	0.72
Crystal size (mm)	0.4 × 0.4 × 0.19	0.32 × 0.26 × 0.21

Data collection
Diffractometer	Rigaku XtaLAB mini diffractometer	Rigaku XtaLAB mini diffractometer
Absorption correction	Multi-scan (REQAB; Rigaku, 1998)	Multi-scan (REQAB; Rigaku, 1998)
T_min, T_max	0.707, 0.848	0.712, 0.859
No. of measured, independent and observed [I > 2σ(I)] reflections	17021, 3923, 3639	11081, 4797, 4365
R_int	0.035	0.029
(sin θ/λ)_max (Å⁻¹)	0.649	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.045, 1.05	0.028, 0.068, 1.09
No. of reflections	3923	4797
No. of parameters	202	255
No. of restraints	1	0
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.27	0.30, −0.82
Absolute structure	Flack x determined using 1649 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013).	?
Absolute structure parameter	0.007 (18)	?

Computer programs: CrystalClear (Rigaku, 2011), SHELXS (Sheldrick, 2008), SIR2008 (Burla et al., 2007), SHELXL (Sheldrick, 2008), Olex2 (Dolomanov et al., 2009).

Acknowledgements

The authors acknowledge St. Catherine University and NSF–MRI award #1125975 "MRI Consortium: Acquisition of a Single Crystal X-ray Diffractometer for a Regional PUI Molecular Structure Facility". Additional funding was provided by a grant to Carleton College from the Howard Hughes Medical Institute.

References

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Volume 70| Part 10| October 2014| Pages 216-220

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