metal-organic compounds
5-Ferrocenylmethyl-2,2-dimethyl-5-(prop-2-ynyl)-1,3-dioxane-4,6-dione
aUniversity of Innsbruck, Faculty of Chemistry and Pharmacy, Innrain 80, 6020 Innsbruck, Austria
*Correspondence e-mail: herwig.schottenberger@uibk.ac.at
The title compound, [Fe(C5H5)(C15H15O4)], was obtained by hydrogenation and subsequent alkylation of 5-ferrocenylmethylene-2,2-dimethyl-1,3-dioxane-4,6-dione. Apart from C—H⋯O=C hydrogen bonds, C C—H⋯π interactions forming crosswise chains of the molecules are observed in the crystal structure.
Keywords: crystal structure; hydrogen bonding; alkyne C—H⋯π interactions; ferrocene.
CCDC reference: 1472572
Structure description
The molecular structure of the title compound is shown in Fig. 1. The cyclopentadienyl groups in the ferrocene unit adopt an eclipsed conformation. The 1,3-dioxane ring is almost planar, with atom C14 displaying a maximum deviation of 0.098 (3) Å from the least-squares plane. In the crystal, weak C—H⋯O=C hydrogen bonds generate a three-dimensional network (Table 1, Fig. 2). An intriguing intermolecular interaction between the acidic proton of the terminal alkyne group and the π system of the ferrocene moiety is observed. The pertinent distances are H18⋯Cg = 2.637 Å and C18⋯Cg = 3.533 Å, where Cg is the centroid of the unsubstituted cyclopentadienyl group. This interaction is directional with a C18—H18⋯Cg angle of 157°, and the resulting chains are arranged crosswise as shown in Fig. 3.
Interactions involving cyclopentadienide anions as hydrogen-bond acceptors have been reluctantly identified as hydrogen bonds (Harder, 1999). Using the query `C C—H⋯Cg(ferrocene) non-bonded contact with H⋯Cg distance ≤ 2.7 Å′, several related structures have been found in the Cambridge Structure Database (Groom & Allen, 2014), see: Lin et al. (1996); Buchmeiser et al. (1998); Wong et al. (2001); Li et al. (2006); Busetto et al. (2012). Although not explicitly described as such by the respective authors, these structures exhibited the C C—H⋯π interactions mentioned, and the corresponding C⋯Cg distances are ≤ 3.58 Å with C—H⋯Cg angles ranging from 152 to 176°.
Synthesis and crystallization
(1) 5-Ferrocenylmethylene-2,2-dimethyl-1,3-dioxane-4,6-dione (2.50 g, 7.34 mmol) (Bai et al., 2004) in MeOH (80 ml) was hydrogenated (3 atm) for 30 min at room temperature using Pd/C (0.24 g, 5 wt.% Pd) as catalyst. Crystallization from MeOH yielded a brown product (1.66 g, 66%). 1H NMR (300 MHz, CDCl3): δ 4.20 (m, 2H), 4.13 (s, 5H), 4.04 (m, 2H), 3.60 (t, J = 4.3 Hz, 1H), 3.23 (d, J = 4.3 Hz, 2H), 1.67 (s, 3H), 1.52 (s, 3H) p.p.m. 13C NMR (75 MHz, CDCl3): δ 165.8, 105.4, 83.4, 70.2, 69.9, 69.1, 68.9, 68.3, 48.6, 28.8, 27.8, 27.6 p.p.m. IR (neat, ATR): ν 3086 (w), 2992 (w), 1560 (s), 1405 (m), 1258 (m), 1199 (m), 1103 (m), 1035 (w), 1019 (w), 996 (w), 925 (w), 879 (w), 815 (w), 785 (w), 755 (w), 744 (w), 654 (w), 525 (w), 479 (w), 446 (w) cm−1.
(2) A mixture of 5-ferrocenylmethyl-2,2-dimethyl-1,3-dioxane-4,6-dione (0.34 g, 1.0 mmol) and anhydrous K2CO3 (0.21 g, 1.5 mmol) in DMF (20 ml) was stirred for 30 min. A solution of 3-bromo-1-propyne (80 wt.% in toluene, 0.23 g, 1.5 mmol) was added, and stirring was continued for 48 h. After removal of the solvent, the residue was partitioned twice between CH2Cl2 (10 ml) and 2 M HCl (10 ml). The organic solution was concentrated and cooled at 278 K to yield yellow crystals (0.30 g, 76%). 1H NMR (300 MHz, CDCl3): δ 4.19 (m, 2H), 4.16 (m, 5H), 4.10 (m, 2H), 3.05 (s, 2H), 2.92 (d, J = 2.6 Hz, 2H), 2.11 (t, J = 2.6 Hz, 1H), 1.63 (s, 3H), 1.05 (s, 3H) p.p.m. 13C NMR (75 MHz, CDCl3): δ 168.1, 106.7, 80.5, 78.4, 77.4, 73.0, 70.2, 69.1, 57.0, 40.4, 30.4, 29.2, 28.4 p.p.m. IR (neat, ATR): ν 3266 (m), 3086 (w), 2934 (w), 1765 (m), 1732 (s), 1641 (m), 1431 (w), 1394 (m), 1381 (m), 1348 (s), 1269 (s), 1228 (s), 1199 (m), 1172 (m), 1054 (s), 1037 (m), 1022 (m), 1000 (m), 955 (m), 917 (w), 832 (m), 813 (m), 702 (m), 678 (m), 664 (m), 498 (s), 482 (m), 465 (m), 421 (s) cm−1.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2
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Structural data
CCDC reference: 1472572
10.1107/S2414314616005691/wm4012sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616005691/wm4012Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616005691/wm4012Isup3.mol
Supporting information file. DOI: 10.1107/S2414314616005691/wm4012Isup4.cml
(1) 5-Ferrocenylmethylene-2,2-dimethyl-1,3-dioxane-4,6-dione (2.50 g, 7.34 mmol) (Bai et al., 2004) in MeOH (80 ml) was hydrogenated (3 atm) for 30 min at room temperature using Pd/C (0.24 g, 5 wt.% Pd) as catalyst. Crystallization from MeOH yielded a brown product (1.66 g, 66%). 1H NMR (300 MHz, CDCl3): δ 4.20 (m, 2H), 4.13 (s, 5H), 4.04 (m, 2H), 3.60 (t, J = 4.3 Hz, 1H), 3.23 (d, J = 4.3 Hz, 2H), 1.67 (s, 3H), 1.52 (s, 3H) p.p.m. 13C NMR (75 MHz, CDCl3): δ 165.8, 105.4, 83.4, 70.2, 69.9, 69.1, 68.9, 68.3, 48.6, 28.8, 27.8, 27.6 p.p.m. IR (neat, ATR): ν 3086 (w), 2992 (w), 1560 (s), 1405 (m), 1258 (m), 1199 (m), 1103 (m), 1035 (w), 1019 (w), 996 (w), 925 (w), 879 (w), 815 (w), 785 (w), 755 (w), 744 (w), 654 (w), 525 (w), 479 (w), 446 (w) cm-1.
(2) A mixture of 5-ferrocenylmethyl-2,2-dimethyl-1,3-dioxane-4,6-dione (0.34 g, 1.0 mmol) and anhydrous K2CO3 (0.21 g, 1.5 mmol) in DMF (20 ml) was stirred for 30 min. A solution of 3-bromo-1-propyne (80 wt.% in toluene, 0.23 g, 1.5 mmol) was added, and stirring was continued for 48 h. After removal of the solvent, the residue was partitioned twice between CH2Cl2 (10 ml) and 2 M HCl (10 ml). The organic solution was concentrated and cooled at 278 K to yield yellow crystals (0.30 g, 76%). 1H NMR (300 MHz, CDCl3): δ 4.19 (m, 2H), 4.16 (m, 5H), 4.10 (m, 2H), 3.05 (s, 2H), 2.92 (d, J = 2.6 Hz, 2H), 2.11 (t, J = 2.6 Hz, 1H), 1.63 (s, 3H), 1.05 (s, 3H) p.p.m. 13C NMR (75 MHz, CDCl3): δ 168.1, 106.7, 80.5, 78.4, 77.4, 73.0, 70.2, 69.1, 57.0, 40.4, 30.4, 29.2, 28.4 p.p.m. IR (neat, ATR): ν 3266 (m), 3086 (w), 2934 (w), 1765 (m), 1732 (s), 1641 (m), 1431 (w), 1394 (m), 1381 (m), 1348 (s), 1269 (s), 1228 (s), 1199 (m), 1172 (m), 1054 (s), 1037 (m), 1022 (m), 1000 (m), 955 (m), 917 (w), 832 (m), 813 (m), 702 (m), 678 (m), 664 (m), 498 (s), 482 (m), 465 (m), 421 (s) cm-1.
The molecular structure of the title compound is shown in Fig. 1. The cyclopentadienyl groups in the ferrocene unit adopt an eclipsed conformation. The 1,3-dioxane ring is almost planar, with atom C14 displaying a maximum deviation of 0.098 (3) Å from the least-squares plane. In the crystal, weak C—H···O═C hydrogen bonds generate a three-dimensional network (Table 1, Fig. 2). An intriguing intermolecular interaction between the acidic proton of the terminal alkyne group and the π system of the ferrocene moiety is observed. The pertinent distances are H18···Cg = 2.637 Å and C18···Cg = 3.533 Å, where Cg is the centroid of the unsubstituted cyclopentadienyl group. This interaction is directional with a C18—H18···Cg angle of 157°, and the resulting chains are arranged crosswise as shown in Fig. 3.
Interactions involving cyclopentadienide anions as hydrogen-bond acceptors have been reluctantly identified as hydrogen bonds (Harder, 1999). Using the query `C≡C—H···Cg(ferrocene) non-bonded contact with H···Cg distance ≤ 2.7 Å', several related structures have been found in the Cambridge Structure Database (Groom & Allen, 2014), see: Lin et al. (1996); Buchmeiser et al. (1998); Wong et al. (2001); Li et al. (2006); Busetto et al. (2012). Although not explicitly described as such by the respective authors, these structures exhibited the C≡C—H···π interactions mentioned, and the corresponding C···Cg distances are ≤ 3.58 Å with C—H···Cg angles ranging from 152 to 176°.
Data collection: APEX2 (Bruker, 2012); cell
SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. The asymmetric unit of the title compound, showing the atom labels and 50% probability displacement ellipsoids for non-H atoms. | |
Fig. 2. The crystal packing of the title compound viewed along the b axis. C—H···O═C hydrogen bonds are shown as dotted lines (see Table 1 for numerical details. | |
Fig. 3. Chains of the title compound formed by C≡C—H···π interactions. The centroids of the rings are drawn as red spheres, and the contacts are drawn as dashed lines. The symmetry code refers to Table 1. |
[Fe(C5H5)(C15H15O4)] | F(000) = 396 |
Mr = 380.21 | Dx = 1.437 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.8263 (4) Å | Cell parameters from 9930 reflections |
b = 7.4617 (2) Å | θ = 5.2–50.6° |
c = 11.9888 (4) Å | µ = 0.88 mm−1 |
β = 91.956 (1)° | T = 173 K |
V = 878.52 (5) Å3 | Plate, yellow |
Z = 2 | 0.18 × 0.11 × 0.07 mm |
Bruker D8 Quest diffractometer | 3215 independent reflections |
Radiation source: Incoatec Microfocus | 3078 reflections with I > 2σ(I) |
Detector resolution: 10.4 pixels mm-1 | Rint = 0.031 |
phi– and ω–scans | θmax = 25.5°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −11→11 |
Tmin = 0.896, Tmax = 0.942 | k = −9→9 |
17890 measured reflections | l = −14→14 |
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0281P)2 + 0.1144P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.021 | (Δ/σ)max < 0.001 |
wR(F2) = 0.052 | Δρmax = 0.28 e Å−3 |
S = 1.05 | Δρmin = −0.16 e Å−3 |
3215 reflections | Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
227 parameters | Extinction coefficient: 0.019 (2) |
1 restraint | Absolute structure: Flack x determined using 1346 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Hydrogen site location: inferred from neighbouring sites | Absolute structure parameter: 0.009 (6) |
[Fe(C5H5)(C15H15O4)] | V = 878.52 (5) Å3 |
Mr = 380.21 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.8263 (4) Å | µ = 0.88 mm−1 |
b = 7.4617 (2) Å | T = 173 K |
c = 11.9888 (4) Å | 0.18 × 0.11 × 0.07 mm |
β = 91.956 (1)° |
Bruker D8 Quest diffractometer | 3215 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | 3078 reflections with I > 2σ(I) |
Tmin = 0.896, Tmax = 0.942 | Rint = 0.031 |
17890 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | H-atom parameters constrained |
wR(F2) = 0.052 | Δρmax = 0.28 e Å−3 |
S = 1.05 | Δρmin = −0.16 e Å−3 |
3215 reflections | Absolute structure: Flack x determined using 1346 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
227 parameters | Absolute structure parameter: 0.009 (6) |
1 restraint |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Fe | 0.00210 (3) | 0.24448 (7) | 0.24251 (3) | 0.01943 (12) | |
O1 | 0.4427 (2) | −0.0935 (3) | 0.12458 (16) | 0.0345 (5) | |
O2 | 0.3366 (2) | −0.3154 (2) | 0.23702 (15) | 0.0353 (5) | |
O3 | 0.51239 (19) | 0.1619 (2) | 0.19227 (16) | 0.0319 (5) | |
O4 | 0.30812 (17) | −0.2766 (3) | 0.41503 (13) | 0.0308 (4) | |
C1 | 0.0061 (3) | 0.5163 (4) | 0.2564 (3) | 0.0325 (9) | |
H1 | 0.0702 | 0.5942 | 0.2239 | 0.039* | |
C2 | −0.1185 (3) | 0.4599 (4) | 0.2063 (2) | 0.0296 (6) | |
H2 | −0.1530 | 0.4933 | 0.1343 | 0.036* | |
C3 | −0.1829 (3) | 0.3452 (4) | 0.2818 (3) | 0.0320 (7) | |
H3 | −0.2684 | 0.2878 | 0.2695 | 0.038* | |
C4 | −0.0984 (3) | 0.3308 (4) | 0.3784 (2) | 0.0347 (7) | |
H4 | −0.1167 | 0.2618 | 0.4428 | 0.042* | |
C5 | 0.0192 (3) | 0.4373 (4) | 0.3630 (3) | 0.0328 (7) | |
H5 | 0.0934 | 0.4525 | 0.4151 | 0.039* | |
C6 | 0.1633 (3) | 0.1703 (4) | 0.1508 (2) | 0.0270 (6) | |
H6 | 0.2298 | 0.2475 | 0.1210 | 0.032* | |
C7 | 0.0384 (3) | 0.1171 (4) | 0.0963 (3) | 0.0369 (7) | |
H7 | 0.0069 | 0.1530 | 0.0239 | 0.044* | |
C8 | −0.0302 (3) | 0.0016 (4) | 0.1691 (3) | 0.0366 (7) | |
H8 | −0.1163 | −0.0532 | 0.1543 | 0.044* | |
C9 | 0.0515 (3) | −0.0183 (4) | 0.2677 (3) | 0.0286 (7) | |
H9 | 0.0303 | −0.0903 | 0.3301 | 0.034* | |
C10 | 0.1709 (3) | 0.0877 (3) | 0.2576 (2) | 0.0220 (6) | |
C11 | 0.2850 (3) | 0.1041 (4) | 0.3429 (2) | 0.0236 (6) | |
H11A | 0.2495 | 0.0805 | 0.4178 | 0.028* | |
H11B | 0.3201 | 0.2285 | 0.3425 | 0.028* | |
C12 | 0.4048 (2) | −0.0280 (3) | 0.32172 (19) | 0.0182 (5) | |
C13 | 0.4606 (2) | 0.0193 (3) | 0.2093 (2) | 0.0193 (5) | |
C14 | 0.4027 (3) | −0.2778 (4) | 0.13503 (18) | 0.0232 (6) | |
C15 | 0.3494 (2) | −0.2168 (3) | 0.32999 (19) | 0.0198 (6) | |
C16 | 0.5180 (3) | 0.0005 (4) | 0.4130 (2) | 0.0256 (6) | |
H16A | 0.5477 | 0.1272 | 0.4119 | 0.031* | |
H16B | 0.4803 | −0.0239 | 0.4870 | 0.031* | |
C17 | 0.6361 (3) | −0.1157 (4) | 0.3974 (2) | 0.0252 (6) | |
C18 | 0.7276 (3) | −0.2127 (4) | 0.3801 (2) | 0.0310 (7) | |
H18 | 0.8014 | −0.2909 | 0.3662 | 0.037* | |
C19 | 0.2962 (3) | −0.3082 (4) | 0.0440 (2) | 0.0392 (8) | |
H19A | 0.3354 | −0.2845 | −0.0287 | 0.059* | |
H19B | 0.2647 | −0.4327 | 0.0465 | 0.059* | |
H19C | 0.2192 | −0.2273 | 0.0546 | 0.059* | |
C20 | 0.5268 (3) | −0.3920 (4) | 0.1287 (3) | 0.0369 (7) | |
H20A | 0.5726 | −0.3669 | 0.0591 | 0.055* | |
H20B | 0.5888 | −0.3656 | 0.1924 | 0.055* | |
H20C | 0.5006 | −0.5187 | 0.1306 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe | 0.01545 (17) | 0.01707 (17) | 0.02571 (19) | 0.00290 (14) | −0.00022 (12) | −0.00182 (17) |
O1 | 0.0594 (14) | 0.0230 (10) | 0.0220 (10) | −0.0103 (10) | 0.0163 (9) | −0.0017 (8) |
O2 | 0.0580 (13) | 0.0232 (10) | 0.0256 (10) | −0.0160 (9) | 0.0154 (9) | −0.0040 (8) |
O3 | 0.0342 (11) | 0.0232 (9) | 0.0384 (12) | −0.0119 (9) | 0.0015 (9) | 0.0036 (9) |
O4 | 0.0305 (9) | 0.0416 (12) | 0.0206 (8) | −0.0025 (10) | 0.0048 (7) | 0.0098 (9) |
C1 | 0.0259 (19) | 0.0139 (15) | 0.059 (2) | 0.0020 (11) | 0.0155 (17) | −0.0054 (13) |
C2 | 0.0258 (15) | 0.0260 (15) | 0.0369 (16) | 0.0116 (12) | −0.0006 (12) | −0.0005 (12) |
C3 | 0.0150 (12) | 0.0284 (16) | 0.0530 (19) | 0.0018 (11) | 0.0062 (12) | −0.0071 (14) |
C4 | 0.0404 (17) | 0.0325 (15) | 0.0323 (16) | 0.0081 (13) | 0.0165 (13) | 0.0016 (12) |
C5 | 0.0257 (14) | 0.0328 (15) | 0.0397 (17) | 0.0091 (12) | −0.0044 (12) | −0.0156 (13) |
C6 | 0.0261 (14) | 0.0316 (14) | 0.0235 (14) | 0.0125 (12) | 0.0035 (11) | −0.0019 (11) |
C7 | 0.0359 (17) | 0.0468 (18) | 0.0272 (16) | 0.0220 (14) | −0.0113 (12) | −0.0136 (13) |
C8 | 0.0275 (16) | 0.0256 (15) | 0.056 (2) | 0.0052 (13) | −0.0143 (15) | −0.0158 (15) |
C9 | 0.0273 (17) | 0.0160 (14) | 0.0421 (17) | 0.0038 (13) | −0.0024 (13) | −0.0006 (12) |
C10 | 0.0186 (13) | 0.0209 (13) | 0.0263 (14) | 0.0068 (11) | −0.0015 (10) | −0.0060 (11) |
C11 | 0.0235 (14) | 0.0251 (13) | 0.0221 (14) | 0.0069 (11) | −0.0007 (11) | −0.0068 (11) |
C12 | 0.0181 (12) | 0.0205 (13) | 0.0159 (12) | 0.0025 (10) | −0.0008 (9) | −0.0013 (10) |
C13 | 0.0152 (11) | 0.0220 (13) | 0.0206 (12) | 0.0029 (10) | −0.0020 (10) | 0.0004 (10) |
C14 | 0.0327 (13) | 0.0196 (15) | 0.0177 (11) | −0.0022 (12) | 0.0056 (9) | −0.0029 (11) |
C15 | 0.0146 (11) | 0.0248 (16) | 0.0200 (12) | 0.0063 (9) | −0.0017 (9) | 0.0027 (10) |
C16 | 0.0209 (13) | 0.0332 (15) | 0.0224 (13) | 0.0050 (11) | −0.0059 (10) | −0.0070 (11) |
C17 | 0.0236 (14) | 0.0319 (14) | 0.0195 (13) | −0.0008 (12) | −0.0063 (10) | −0.0013 (11) |
C18 | 0.0260 (13) | 0.0392 (19) | 0.0276 (13) | 0.0054 (12) | −0.0018 (11) | −0.0012 (12) |
C19 | 0.0347 (16) | 0.047 (2) | 0.0361 (16) | −0.0046 (13) | −0.0032 (13) | 0.0043 (13) |
C20 | 0.0330 (17) | 0.0367 (16) | 0.0406 (19) | 0.0070 (14) | −0.0037 (14) | −0.0018 (14) |
Fe—C10 | 2.032 (2) | C6—H6 | 0.9500 |
Fe—C6 | 2.035 (2) | C7—C8 | 1.414 (5) |
Fe—C8 | 2.035 (3) | C7—H7 | 0.9500 |
Fe—C2 | 2.035 (3) | C8—C9 | 1.414 (5) |
Fe—C1 | 2.035 (3) | C8—H8 | 0.9500 |
Fe—C7 | 2.036 (3) | C9—C10 | 1.423 (4) |
Fe—C3 | 2.037 (3) | C9—H9 | 0.9500 |
Fe—C4 | 2.038 (3) | C10—C11 | 1.497 (4) |
Fe—C9 | 2.040 (3) | C11—C12 | 1.563 (3) |
Fe—C5 | 2.041 (3) | C11—H11A | 0.9900 |
O1—C13 | 1.326 (3) | C11—H11B | 0.9900 |
O1—C14 | 1.437 (3) | C12—C13 | 1.514 (3) |
O2—C15 | 1.338 (3) | C12—C15 | 1.515 (3) |
O2—C14 | 1.432 (3) | C12—C16 | 1.548 (3) |
O3—C13 | 1.200 (3) | C14—C20 | 1.492 (4) |
O4—C15 | 1.196 (3) | C14—C19 | 1.504 (4) |
C1—C5 | 1.409 (4) | C16—C17 | 1.466 (4) |
C1—C2 | 1.409 (4) | C16—H16A | 0.9900 |
C1—H1 | 0.9500 | C16—H16B | 0.9900 |
C2—C3 | 1.411 (4) | C17—C18 | 1.178 (4) |
C2—H2 | 0.9500 | C18—H18 | 0.9500 |
C3—C4 | 1.406 (4) | C19—H19A | 0.9800 |
C3—H3 | 0.9500 | C19—H19B | 0.9800 |
C4—C5 | 1.420 (4) | C19—H19C | 0.9800 |
C4—H4 | 0.9500 | C20—H20A | 0.9800 |
C5—H5 | 0.9500 | C20—H20B | 0.9800 |
C6—C10 | 1.420 (4) | C20—H20C | 0.9800 |
C6—C7 | 1.427 (4) | ||
C10—Fe—C6 | 40.87 (10) | Fe—C5—H5 | 126.3 |
C10—Fe—C8 | 68.95 (11) | C10—C6—C7 | 108.0 (3) |
C6—Fe—C8 | 68.73 (12) | C10—C6—Fe | 69.46 (14) |
C10—Fe—C2 | 160.22 (11) | C7—C6—Fe | 69.51 (15) |
C6—Fe—C2 | 123.91 (11) | C10—C6—H6 | 126.0 |
C8—Fe—C2 | 122.02 (12) | C7—C6—H6 | 126.0 |
C10—Fe—C1 | 123.56 (11) | Fe—C6—H6 | 126.6 |
C6—Fe—C1 | 107.58 (11) | C8—C7—C6 | 107.9 (3) |
C8—Fe—C1 | 157.70 (13) | C8—C7—Fe | 69.65 (17) |
C2—Fe—C1 | 40.51 (12) | C6—C7—Fe | 69.45 (15) |
C10—Fe—C7 | 69.00 (11) | C8—C7—H7 | 126.0 |
C6—Fe—C7 | 41.04 (12) | C6—C7—H7 | 126.0 |
C8—Fe—C7 | 40.64 (14) | Fe—C7—H7 | 126.4 |
C2—Fe—C7 | 107.64 (12) | C7—C8—C9 | 108.1 (3) |
C1—Fe—C7 | 122.17 (13) | C7—C8—Fe | 69.70 (16) |
C10—Fe—C3 | 157.47 (11) | C9—C8—Fe | 69.88 (15) |
C6—Fe—C3 | 160.44 (11) | C7—C8—H8 | 126.0 |
C8—Fe—C3 | 107.53 (12) | C9—C8—H8 | 126.0 |
C2—Fe—C3 | 40.55 (11) | Fe—C8—H8 | 126.0 |
C1—Fe—C3 | 68.17 (11) | C8—C9—C10 | 108.5 (3) |
C7—Fe—C3 | 123.72 (12) | C8—C9—Fe | 69.52 (16) |
C10—Fe—C4 | 121.80 (11) | C10—C9—Fe | 69.25 (15) |
C6—Fe—C4 | 157.64 (12) | C8—C9—H9 | 125.8 |
C8—Fe—C4 | 123.67 (13) | C10—C9—H9 | 125.8 |
C2—Fe—C4 | 68.05 (12) | Fe—C9—H9 | 127.1 |
C1—Fe—C4 | 68.16 (12) | C6—C10—C9 | 107.4 (2) |
C7—Fe—C4 | 159.97 (13) | C6—C10—C11 | 126.5 (2) |
C3—Fe—C4 | 40.37 (12) | C9—C10—C11 | 126.0 (3) |
C10—Fe—C9 | 40.92 (12) | C6—C10—Fe | 69.67 (14) |
C6—Fe—C9 | 68.46 (12) | C9—C10—Fe | 69.83 (15) |
C8—Fe—C9 | 40.60 (13) | C11—C10—Fe | 127.14 (17) |
C2—Fe—C9 | 157.63 (12) | C10—C11—C12 | 112.8 (2) |
C1—Fe—C9 | 160.38 (12) | C10—C11—H11A | 109.0 |
C7—Fe—C9 | 68.33 (13) | C12—C11—H11A | 109.0 |
C3—Fe—C9 | 122.02 (12) | C10—C11—H11B | 109.0 |
C4—Fe—C9 | 107.76 (13) | C12—C11—H11B | 109.0 |
C10—Fe—C5 | 107.18 (11) | H11A—C11—H11B | 107.8 |
C6—Fe—C5 | 121.79 (12) | C13—C12—C15 | 114.63 (19) |
C8—Fe—C5 | 160.31 (13) | C13—C12—C16 | 108.9 (2) |
C2—Fe—C5 | 68.12 (12) | C15—C12—C16 | 109.4 (2) |
C1—Fe—C5 | 40.43 (13) | C13—C12—C11 | 107.2 (2) |
C7—Fe—C5 | 157.73 (13) | C15—C12—C11 | 107.58 (19) |
C3—Fe—C5 | 68.23 (12) | C16—C12—C11 | 108.99 (19) |
C4—Fe—C5 | 40.74 (12) | O3—C13—O1 | 118.6 (2) |
C9—Fe—C5 | 124.02 (13) | O3—C13—C12 | 121.8 (2) |
C13—O1—C14 | 124.78 (19) | O1—C13—C12 | 119.4 (2) |
C15—O2—C14 | 124.80 (19) | O2—C14—O1 | 113.30 (19) |
C5—C1—C2 | 108.2 (3) | O2—C14—C20 | 109.1 (2) |
C5—C1—Fe | 70.02 (18) | O1—C14—C20 | 108.4 (2) |
C2—C1—Fe | 69.74 (17) | O2—C14—C19 | 105.4 (2) |
C5—C1—H1 | 125.9 | O1—C14—C19 | 105.5 (2) |
C2—C1—H1 | 125.9 | C20—C14—C19 | 115.3 (2) |
Fe—C1—H1 | 125.9 | O4—C15—O2 | 118.7 (2) |
C1—C2—C3 | 108.1 (3) | O4—C15—C12 | 122.4 (2) |
C1—C2—Fe | 69.76 (17) | O2—C15—C12 | 118.7 (2) |
C3—C2—Fe | 69.81 (15) | C17—C16—C12 | 112.5 (2) |
C1—C2—H2 | 126.0 | C17—C16—H16A | 109.1 |
C3—C2—H2 | 126.0 | C12—C16—H16A | 109.1 |
Fe—C2—H2 | 126.0 | C17—C16—H16B | 109.1 |
C4—C3—C2 | 108.0 (2) | C12—C16—H16B | 109.1 |
C4—C3—Fe | 69.84 (15) | H16A—C16—H16B | 107.8 |
C2—C3—Fe | 69.64 (15) | C18—C17—C16 | 176.5 (3) |
C4—C3—H3 | 126.0 | C17—C18—H18 | 180.0 |
C2—C3—H3 | 126.0 | C14—C19—H19A | 109.5 |
Fe—C3—H3 | 126.1 | C14—C19—H19B | 109.5 |
C3—C4—C5 | 108.1 (3) | H19A—C19—H19B | 109.5 |
C3—C4—Fe | 69.79 (15) | C14—C19—H19C | 109.5 |
C5—C4—Fe | 69.76 (16) | H19A—C19—H19C | 109.5 |
C3—C4—H4 | 126.0 | H19B—C19—H19C | 109.5 |
C5—C4—H4 | 126.0 | C14—C20—H20A | 109.5 |
Fe—C4—H4 | 126.1 | C14—C20—H20B | 109.5 |
C1—C5—C4 | 107.6 (3) | H20A—C20—H20B | 109.5 |
C1—C5—Fe | 69.56 (18) | C14—C20—H20C | 109.5 |
C4—C5—Fe | 69.50 (17) | H20A—C20—H20C | 109.5 |
C1—C5—H5 | 126.2 | H20B—C20—H20C | 109.5 |
C4—C5—H5 | 126.2 | ||
C5—C1—C2—C3 | −0.1 (3) | C8—C9—C10—Fe | 58.59 (19) |
Fe—C1—C2—C3 | 59.52 (18) | C6—C10—C11—C12 | −83.2 (3) |
C5—C1—C2—Fe | −59.7 (2) | C9—C10—C11—C12 | 94.8 (3) |
C1—C2—C3—C4 | 0.0 (3) | Fe—C10—C11—C12 | −174.29 (17) |
Fe—C2—C3—C4 | 59.53 (18) | C10—C11—C12—C13 | 61.6 (3) |
C1—C2—C3—Fe | −59.49 (19) | C10—C11—C12—C15 | −62.1 (3) |
C2—C3—C4—C5 | 0.1 (3) | C10—C11—C12—C16 | 179.3 (2) |
Fe—C3—C4—C5 | 59.47 (19) | C14—O1—C13—O3 | 169.6 (2) |
C2—C3—C4—Fe | −59.40 (18) | C14—O1—C13—C12 | −15.6 (4) |
C2—C1—C5—C4 | 0.2 (3) | C15—C12—C13—O3 | −177.1 (2) |
Fe—C1—C5—C4 | −59.31 (19) | C16—C12—C13—O3 | −54.2 (3) |
C2—C1—C5—Fe | 59.5 (2) | C11—C12—C13—O3 | 63.6 (3) |
C3—C4—C5—C1 | −0.1 (3) | C15—C12—C13—O1 | 8.3 (3) |
Fe—C4—C5—C1 | 59.3 (2) | C16—C12—C13—O1 | 131.2 (2) |
C3—C4—C5—Fe | −59.49 (19) | C11—C12—C13—O1 | −111.1 (2) |
C10—C6—C7—C8 | −0.3 (3) | C15—O2—C14—O1 | −22.3 (3) |
Fe—C6—C7—C8 | −59.23 (19) | C15—O2—C14—C20 | 98.5 (3) |
C10—C6—C7—Fe | 58.95 (18) | C15—O2—C14—C19 | −137.1 (3) |
C6—C7—C8—C9 | −0.5 (3) | C13—O1—C14—O2 | 21.3 (4) |
Fe—C7—C8—C9 | −59.57 (19) | C13—O1—C14—C20 | −99.9 (3) |
C6—C7—C8—Fe | 59.10 (19) | C13—O1—C14—C19 | 136.1 (2) |
C7—C8—C9—C10 | 1.0 (3) | C14—O2—C15—O4 | −167.7 (2) |
Fe—C8—C9—C10 | −58.42 (18) | C14—O2—C15—C12 | 17.4 (3) |
C7—C8—C9—Fe | 59.45 (19) | C13—C12—C15—O4 | 176.3 (2) |
C7—C6—C10—C9 | 0.9 (3) | C16—C12—C15—O4 | 53.6 (3) |
Fe—C6—C10—C9 | 59.89 (18) | C11—C12—C15—O4 | −64.6 (3) |
C7—C6—C10—C11 | 179.2 (2) | C13—C12—C15—O2 | −9.0 (3) |
Fe—C6—C10—C11 | −121.8 (2) | C16—C12—C15—O2 | −131.7 (2) |
C7—C6—C10—Fe | −58.98 (18) | C11—C12—C15—O2 | 110.1 (2) |
C8—C9—C10—C6 | −1.2 (3) | C13—C12—C16—C17 | −61.9 (3) |
Fe—C9—C10—C6 | −59.79 (18) | C15—C12—C16—C17 | 64.1 (3) |
C8—C9—C10—C11 | −179.5 (2) | C11—C12—C16—C17 | −178.5 (2) |
Fe—C9—C10—C11 | 121.9 (2) |
Cg is the centroid of the unsubstituted cyclopentadienyl ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C20—H20C···O3i | 0.98 | 2.50 | 3.419 (3) | 157 |
C3—H3···O3ii | 0.95 | 2.50 | 3.431 (3) | 167 |
C19—H19A···O3iii | 0.98 | 2.54 | 3.460 (3) | 157 |
C16—H16A···O4iv | 0.99 | 2.57 | 3.114 (3) | 114 |
C4—H4···O4v | 0.95 | 2.60 | 3.372 (3) | 139 |
C18—H18···Cgvi | 0.95 | 2.64 | 3.533 | 157 |
Symmetry codes: (i) x, y−1, z; (ii) x−1, y, z; (iii) −x+1, y−1/2, −z; (iv) −x+1, y+1/2, −z+1; (v) −x, y+1/2, −z+1; (vi) x+1, y−1, z. |
Cg is the centroid of the unsubstituted cyclopentadienyl ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C20—H20C···O3i | 0.980 | 2.497 | 3.419 (3) | 157 |
C3—H3···O3ii | 0.950 | 2.499 | 3.431 (3) | 167 |
C19—H19A···O3iii | 0.981 | 2.538 | 3.460 (3) | 157 |
C16—H16A···O4iv | 0.990 | 2.574 | 3.114 (3) | 114 |
C4—H4···O4v | 0.950 | 2.597 | 3.372 (3) | 139 |
C18—H18···Cgvi | 0.950 | 2.637 | 3.533 | 157 |
Symmetry codes: (i) x, y−1, z; (ii) x−1, y, z; (iii) −x+1, y−1/2, −z; (iv) −x+1, y+1/2, −z+1; (v) −x, y+1/2, −z+1; (vi) x+1, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C5H5)(C15H15O4)] |
Mr | 380.21 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 173 |
a, b, c (Å) | 9.8263 (4), 7.4617 (2), 11.9888 (4) |
β (°) | 91.956 (1) |
V (Å3) | 878.52 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.88 |
Crystal size (mm) | 0.18 × 0.11 × 0.07 |
Data collection | |
Diffractometer | Bruker D8 Quest |
Absorption correction | Multi-scan (SADABS; Bruker, 2012) |
Tmin, Tmax | 0.896, 0.942 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17890, 3215, 3078 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.605 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.052, 1.05 |
No. of reflections | 3215 |
No. of parameters | 227 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.16 |
Absolute structure | Flack x determined using 1346 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Absolute structure parameter | 0.009 (6) |
Computer programs: APEX2 (Bruker, 2012), SAINT (Bruker, 2012), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006), publCIF (Westrip, 2010).
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The molecular structure of the title compound is shown in Fig. 1. The cyclopentadienyl groups in the ferrocene unit adopt an eclipsed conformation. The 1,3-dioxane ring is almost planar, with atom C14 displaying a maximum deviation of 0.098 (3) Å from the least-squares plane. In the crystal, weak C—H···O═C hydrogen bonds generate a three-dimensional network (Table 1, Fig. 2). An intriguing intermolecular interaction between the acidic proton of the terminal alkyne group and the π system of the ferrocene moiety is observed. The pertinent distances are H18···Cg = 2.637 Å and C18···Cg = 3.533 Å, where Cg is the centroid of the unsubstituted cyclopentadienyl group. This interaction is directional with a C18—H18···Cg angle of 157°, and the resulting chains are arranged crosswise as shown in Fig. 3.
Interactions involving cyclopentadienide anions as H bond acceptors have been reluctantly identified as hydrogen bonds (Harder, 1999). Using the query 'C≡C—H···Cg(ferrocene) non-bonded contact with H···Cg distance ≤ 2.7 Å', several related structures have been found in the Cambridge Structure Database (Groom & Allen, 2014), see: Lin et al. (1996); Buchmeiser et al. (1998); Wong et al. (2001); Li et al. (2006); Busetto et al. (2012). Although not explicitly described as such by the respective authors, these structures exhibited the C≡C—H···π interactions mentioned, and the corresponding C···Cg distances are ≤ 3.58 Å with C—H···Cg angles ranging from 152 to 176°.