research communications
fac-tricarbonyl(cyclohexyl isocyanide-κC)(quinoline-2-carboxylato-κ2N,O)rhenium(I)
ofaInstitute of Nuclear and Radiological Sciences and Technology, Energy and Safety, National Centre for Scientific Research `Demokritos', 15310 Athens, Greece, bInstitute of Nanoscience and Nanotechnology, National Centre for Scientific Research `Demokritos', 15310 Athens, Greece, and cInstitute of Biosciences & Applications, National Centre for Scientific Research `Demokritos', 15310 Athens, Greece
*Correspondence e-mail: v.psycharis@inn.demokritos.gr
In the title compound, [Re(C10H6NO2)(C7H11N)(CO)3], the ReI atom is coordinated by three carbonyl ligands in a facial arrangement and by the N, O and C atoms from a chelating quinaldate anion and a monodentate isocyanide ligand, respectively. The resultant C4NO coordination sphere is distorted octahedral. A lengthening of the axial Re—CO bond trans to the isocyanide ligand is indicative of the trans effect. Individual complexes are stacked into rods parallel to [001] through displaced π–π interactions. Weak C—H⋯O hydrogen-bonding interactions between the rods lead to the formation of layers parallel to (010). These layers are stacked along [010] by C—H⋯H—C van der Waals contacts.
Keywords: crystal structure; rhenium(I) tricarbonyl complex; rhenium(I) cyclohexyl isocyanide and quinaldic acid complex; structural trans effect; Hirshfeld surface analysis.
CCDC reference: 1451823
1. Chemical context
Tricarbonylrhenium(I) compounds are being explored as luminescent probes for cell imaging, photosensitizers in et al., 2015; Bertrand et al., 2014), and as potential radiopharmaceuticals based on the already extensive use of radioactive 186/188Re compounds in nuclear medicine for pain palliation and radiosynovectomy (Schneider et al., 2005; Bodei et al., 2008). Recent studies have also revealed the potential of cold tricarbonylrhenium(I) complexes as anticancer agents (Leodinova & Gasser, 2014).
(LyczkoAs part of our ongoing research in the field of Re/Tc coordination compounds, the fac-[M(CO)3(L)(QA-NO)], where M is Re,Tc, L is the monodentate ligand cyclohexylisocyanide, and QA-NO is deprotonated quinaldic acid, is presented. As a result of of the versatility of the `2 + 1' system, fac-[M(CO)3(L)(QA-NO)] complexes can be used as model compounds in the development of targeted radiopharmaceuticals or anticancer agents by suitable replacement of either the bidentate or monodentate ligand. For example, the monodentate ligand may be the isocyanide derivative of a pharmacophore with affinity for a certain receptor. Alternatively, the bidentate ligand may be a more extensive to act as a DNA intercalator. Both quinaldate- and isocyanide-based ligands have been used as possible DNA intercalators (Li et al., 2009; Agorastos et al., 2007).
of a new `2 + 1' tricarbonyl rhenium complex,2. Structural commentary
The molecular structure of the title compound, [Re(C10H6NO2)(C7H11N)(CO)3], is shown in Fig. 1. The ReI atom is six-coordinated by four C, one N and one O atoms in a distorted octahedral coordination sphere. The carbonyl C atoms are in a facial arrangement, with distances in the range 1.903 (8)–1.960 (8) Å, resulting in a cis arrangement of the bi- and monodentate ligands. The longest distance involving the carbonyl ligands [1.960 (8) Å; Re—C11] corresponds to the ligand trans to the isocyanide cyclohexyl ligand, defining the axial direction of the octahedral complex. The ReI atom almost lies in the equatorial plane (deviation, 0.006 Å) defined by the C12, C13, O1 and N1 atoms. The bite angle (N1—Re—O1) of the chelating ligand, corresponding to a five-membered ring, has a typical value of 75.2 (2)° (Lyczko et al., 2015). The Re—N1 and Re—O1 bond lengths are 2.273 (5) and 2.149 (5) Å, respectively. The isocyanide carbon atom, C14, is at a distance of 2.107 (8) Å from the metal site. All these values are close to those of a complex with the same core (Agorastos et al., 2007). The isocyanide group is oriented within the equatorial plane of the cyclohexyl ring which exhibits a chair conformation.
3. Supramolecular features
Figs. 2 and 3 show the supramolecular interactions of each complex molecule with its neighbours. Displaced π–π interactions between the phenyl and pyridine rings of quinaldate ligands of neighbouring complexes are present, with a Cg1⋯Cg2i distance of 3.650 Å [Cg1 and Cg2 are the centroids of the (C5–C10) and (N1,C2,C3,C4,C5,C10) rings, respectively; symmetry code: (i): 4 − x, 1 − y, 2 − z]. These interactions help to consolidate the stacking of the molecules into rods parallel to [001] (Figs. 3 and 4). Weak intermolecular C—H⋯O hydrogen-bonding interactions (Table 1), including supramolecular R22(7) loops (C20—H20A⋯O1 and C15—H15⋯O2) join neighbouring rods into sheets parallel to (010) (Fig. 4). An additional type of interactions, viz. short of the C—H⋯H—C type (Sankolli et al., 2015), is realized through C18—H18⋯H18—C18 contacts. The cyclohexyl end of the isocyanide ligands is hanging above and below the sheets of molecules (Figs. 3 and 4), creating a perhydrogenated outer wall (Sankolli et al., 2015) at both sides of the layers. Such layers are stacked along [010] (through centres of symmetry located at b/2) and interact through the aforementioned C—H⋯H—C contacts (Fig. 5).
4. Hirshfeld surface analysis
The packing of the complexes in the structure was further investigated with Hirshfeld surface analysis using the Crystal Explorer package (Wolff et al., 2012). The dnorm and curvedness (Spackman & Jayatilaka, 2009) surface mappings are presented in Fig. 6a, 6b and 6c, respectively. All C—H⋯O and C—H⋯H—C contacts are recognized on the dnorm mapped surface as deep-red depression areas in Fig. 6a and 6b, which represent two different upper views of the complex. Arrows at these figures indicate the specific type of contacts at each red point. A bottom view of the surface mapped with curvedness (Fig. 6c) shows broad, relatively flat regions (indicated by letter A) characteristic of planar stacking of complexes (Spackman & Jayatilaka, 2009), corresponding to the π–π interactions. In the fingerprint plot (Rohl et al., 2008), shown in Fig. 6d, the points indicated by 1, 2A & 2B, 3A & 3B and 4 correspond to H⋯H, H⋯O, C⋯H and C⋯C interactions with relative contributions of 25.1, 44.2, 18.1 and 4.3%, respectively. These types of interactions add to 91.7% of the intermolecular contacts of the Hirshfeld surface area. The remaining contributions (8.3%) correspond to N⋯H (2.1%), O⋯C (2.8%) and other less-important interactions (<1%).
5. NMR investigation
In the solution NMR spectra of the complex, both the quinaldate and isocyanocyclohexane moieties are distinguishable. Coordination by the quinaldate is evident from the downfield shifts of all its protons ranging from 0.10 to 0.44 p.p.m. compared to free quinaldic acid under the same conditions (our data). Downfield shifts are also recorded for most of the C atoms of quinaldic acid, the most notable one (4.8 p.p.m.) being the one of the carboxylate carbonyl carbon. For the isocyanocyclohexane moiety, downfield shifts are recorded for the C atom (2.7 p.p.m.) bearing the isocyanide group and for its H atom (0.31 p.p.m.) compared to the free ligand. The most characteristic sign of coordination of the isocyanocyclohexane moiety is the sizable upfield shift of the isocyanide C atom of 15.5 p.p.m., attributed to an increased carbene character upon coordination (Stephany et al., 1974; Sagnou et al., 2010, 2011). In the 13C NMR spectrum of the complex, one of the carbonyl ligands of the Re(CO)3+ core appears shielded (by 2.8 p.p.m. on average) compared to the other two, an observation that may also be attributed to the trans effect of the isocyanide ligand.
6. Database survey
A search of the Cambridge Structural Database (Groom & Allen, 2014) has revealed eight tricarbonyl complexes in facial arrangement and different N,O-bidentate ligands with a pyridine carboxylato-2 group at the binding side of the corresponding ligand. The N,O-binding sites together with the two carbonyl groups trans to N and O atoms define an equatorial plane, and the third together with the monodentate ligand define the axial position. The Re—C bond lengths of axial carbonyl ligands (1.883–1.922 Å) trans to the monodentate ligand have values equal or smaller than the equatorial ones (1.892–1.945 Å) when the ligand is an aqua ligand (Schutte & Visser, 2008; Mundwiler et al., 2004). The carbonyl Re—C bond lengths are intermediate (1.914–1.917 Å) between the values of the Re—C bonds trans to the equatorial O (1.886–1.916 Å) and N (1.921–1.926 Å) atoms, if the trans ligand is bonded to Re through an N atom (Benny et al., 2009; Mundwiler et al., 2004). Finally, the respective bond length, 1.947 Å, is longer than both Re—C bonds trans to equatorial O (1.912 Å) and N (1.914 Å) atoms if the Re atom is bonded to a P atom of a phosphine ligand (Hayes et al., 2014). In the case of the isocyanide group trans to the axial Re—C bond (Agorastos et al., 2007), the results are indistinct. In one case (XIDPUW), the axial bond length (1.756 Å) is shorter than the equatorial one (1.849 Å trans to O and 1.901 Å trans to N) whereas in the other case (XIDQAD), the corresponding length (1.914 Å) is longer than the equatorial one (1.495 Å trans to O and 1.885 Å trans to N). In the present structure, the Re—C11 bond (1.960 Å), is longer than the Re—C13 (1.903 Å, trans to O) and Re—C12 (1.912 Å, trans to N) bonds. This result is supported by the NMR analysis and is indicative of the structural trans effect (Coe & Glenwright, 2000).
7. Synthesis and crystallization
To a stirred solution of quinaldic acid (17.3 mg, 0.1 mmol) in 5 ml methanol, a solution of [NEt4]2[ReBr3(CO)3] (77 mg, 0.1 mmol) in 5 ml methanol was added. The mixture was heated at 333 K, and after 30 min a solution of cyclohexyl isocyanide (0.1 mmol) in 3 ml methanol was added. The mixture was stirred at room temperature for 2 h and the reaction progress was monitored by HPLC. The solvent was removed under reduced pressure and the solid residue was recrystallized from dichloromethane/hexane. The resulting solid was redissolved in a minimum volume of dichloromethane, layered with hexane and left to stand at room temperature. After a few days crystals suitable for X-ray analysis were isolated (yield: 44 mg, 80%). 1H NMR (DMSO-d6, p.p.m.): 8.93 (1H), 8.58 (1H), 8.32 (1H), 8.28 (1H), 8.18 (1H), 7.94 (1H), 4.08 (1H), 1.50 (2H), 1.40 (2H), 1.13(2H), 1.08 (2H), 0.88 (2H); 13C NMR (DMSO-d6, p.p.m.): 193.65, 193.12, 190.54, 172.06, 152.63, 146.23, 142.09, 138.85, 133.04, 130.47, 129.67, 129.61, 127.78, 122.78, 53.72, 30.48, 23.91, 20.70.
8. Refinement
Crystal data, data collection and structure . C-bound H atoms were placed in idealized positions and refined using a riding model with C—H = 0.95 Å (aromatic H atoms), C—H = 0.99 Å (methylene H atoms), and with Uiso(H) = 1.2Ueq(C).
details are summarized in Table 2Supporting information
CCDC reference: 1451823
10.1107/S2056989016002206/wm5257sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016002206/wm5257Isup2.hkl
Tricarbonylrhenium(I) compounds are being explored as luminescent probes for cell imaging, photosensitizers in
(Lyczko et al., 2015; Bertrand et al., 2014), and as potential radiopharmaceuticals based on the already extensive use of radioactive 186/188Re compounds in nuclear medicine for pain palliation and radiosynovectomy (Schneider et al. 2005; Bodei et al. 2008). Recent studies have also revealed the potential of cold tricarbonylrhenium(I) complexes as anticancer agents (Leodinova & Gasser, 2014).As part of our ongoing research in the field of Re/Tc coordination compounds, the
of a new `2 + 1' tricarbonyl rhenium complex, fac-[M(CO)3(L)(QA—NO)], where M is Re,Tc, L is the monodentate ligand cyclohexylisocyanide, and QA—NO is deprotonated quinaldic acid, is presented. Because of the versatility of the `2 + 1' system, fac-[M(CO)3(L)(QA—NO)] complexes can be used as model compounds in the development of targeted radiopharmaceuticals or anticancer agents by suitable replacement of either the bidentate or monodentate ligand. For example, the monodentate ligand may be the isocyanide derivative of a pharmacophore with affinity for a certain receptor. Alternatively, the bidentate ligand may be a more extensive to act as a DNA intercalator. Both quinaldate- and isocyanide-based ligands have been used as possible DNA intercalators (Li et al., 2009; Agorastos et al., 2007).The molecular structure of the title compound, [Re(C10H6NO2)(C7H11N)(CO)3], is shown in Fig. 1. The ReI atom is six-coordinated by four C, one N and one O atoms in a distorted octahedral coordination sphere. The carbonyl C atoms are in a facial arrangement, with distances in the range 1.903 (8)–1.960 (8) Å, resulting in a cis arrangement of the bi- and monodentate ligands. The longest distance involving the carbonyl ligands [1.960 (8) Å; Re—C11] corresponds to the ligand trans to the isocyanide cyclohexyl ligand, defining the axial direction of the octahedral complex. The ReI atom almost lies in the equatorial plane (deviation, 0.006 Å) defined by the C12, C13, O1 and N1 atoms. The bite angle (N1—Re—O1) of the chelating ligand, corresponding to a five-membered ring, has a typical value of 75.2 (2)° (Lyczko et al., 2015). The Re—N1 and Re—O1 bond lengths are 2.273 (5) and 2.149 (5) Å, respectively. The isocyanide carbon atom, C14, is at a distance of 2.107 (8) Å from the metal site. All these values are close to those of a complex with the same core (Agorastos et al., 2007). The isocyanide group is oriented within the equatorial plane of the cyclohexyl ring which exhibits a chair conformation.
Figs. 2 and 3 show the supramolecular interactions of each complex molecule with its neighbours. Displaced π–π interactions between the phenyl and pyridine rings of quinaldate ligands of neighbouring complexes are present, with a Cg1···Cg2i distance of 3.650 Å [Cg1 and Cg2 are the centroids of the (C5–C10) and (N1,C2,C3,C4,C5,C10) rings, respectively; symmetry code: (i): 4 − x, 1 − y, 2 − z)]. These interactions help to consolidate the stacking of the molecules into rods parallel to [001] (Figs. 3 and 4). Weak intermolecular C—H···O hydrogen-bonding interactions (Table 1), including supramolecular R22(7) loops (C20—H20A···O1 and C15—H15···O2) join neighbouring rods into sheets parallel to (010) (Fig. 4). An additional type of interactions, viz. short of the C—H···H—C type (Sankolli et al., 2015), is realised through C18—H18···H18—C18 contacts. The cyclohexyl end of the isocyanide ligands is hanging above and below the sheets of molecules (Figs. 3 and 4), creating a perhydrogenated outer wall (Sankolli et al., 2015) at both sides of the layers. Such layers are stacked along [010] (through centres of symmetry located at b/2) and interact through the aforementioned C—H···H—C contacts (Fig. 5).
The packing of the complexes in the structure was further investigated with Hirshfeld surface analysis using the Crystal Explorer package (Wolff et al., 2012). The dnorm and curvedness (Spackman & Jayatilaka, 2009) surface mappings are presented in Figs. 6a, 6b and 6c, respectively. All C—H···O and C—H···H—C contacts are recognized on the dnorm mapped surface as deep-red depression areas in Figs. 6a and 6b, which represent two different upper views of the complex. Arrows at these figures indicate the specific type of contacts at each red point. A bottom view of the surface mapped with curvedness (Fig. 6c) shows broad, relatively flat regions (indicated by letter A) characteristic of planar stacking of complexes (Spackman & Jayatilaka, 2009), corresponding to the π–π interactions. In the fingerprint plot (Rohl et al., 2008), shown in Fig. 6d, the points indicated by 1, 2 A & 2B, 3 A & 3B and 4 correspond to H···H, H···O, C···H and C···C interactions with relative contributions of 25.1, 44.2, 18.1 and 4.3%, respectively. These types of interactions add to 91.7% of the intermolecular contacts of the Hirshfeld surface area. The remaining contributions (8.3%) correspond to N···H (2.1%), O···C (2.8%) and other less-important interactions (<1%).
In the solution NMR spectra of the complex, both the quinaldate and isocyanocyclohexane moieties are distinguishable. Coordination by the quinaldate is evident from the downfield shifts of all its protons ranging from 0.10 to 0.44 p.p.m. compared to free quinaldic acid under the same conditions (our data). Downfield shifts are also recorded for most of the C atoms of quinaldic acid, the most notable one (4.8 p.p.m.) being the one of the carboxylate carbonyl carbon. For the isocyanocyclohexane moiety, downfield shifts are recorded for the C atom (2.7 p.p.m.) bearing the isocyanide group and for its H atom (0.31 p.p.m.) compared to the free ligand. The most characteristic sign of coordination of the isocyanocyclohexane moiety is the sizable upfield shift of the isocyanide C atom of 15.5 p.p.m., attributed to an increased carbene character upon coordination (Stephany et al., 1974; Sagnou et al., 2010, 2011). In the 13C NMR spectrum of the complex, one of the carbonyl ligands of the Re(CO)3+ core appears shielded (by 2.8 p.p.m. on average) compared to the other two, an observation that may also be attributed to the trans effect of the isocyanide ligand.
A search of the Cambridge Structural Database (Groom & Allen, 2014) has revealed eight tricarbonyl complexes in facial arrangement and different N,O-bidentate ligands with a pyridine carboxylato-2 group at the binding side of the corresponding ligand. The N,O-binding sites together with the two carbonyl groups trans to N and O atoms define an equatorial plane, and the third together with the monodentate ligand define the axial position. The Re—C bond lengths of axial carbonyl ligands (1.883–1.922 Å) trans to the monodentate ligand have values equal or smaller than the equatorial ones (1.892–1.945 Å) when the ligand is an aqua ligand (Schutte & Visser, 2008; Mundwiler et al., 2004). The carbonyl Re—C bond lengths are intermediate (1.914–1.917 Å) between the values of the Re—C bonds trans to the equatorial O (1.886–1.916 Å) and N (1.921–1.926 Å) atoms, if the trans ligand is bonded to Re through an N atom (Benny et al., 2009; Mundwiler et al., 2004). Finally, the respective bond length, 1.947 Å, is longer than both Re—C bonds trans to equatorial O (1.912 Å) and N (1.914 Å) atoms if the Re atom is bonded to a P atom of a phosphine ligand (Hayes et al., 2014). In the case of the isocyanide group trans to the axial Re—C bond (Agorastos et al., 2007), the results are indistinct. In one case (XIDPUW), the axial bond length (1.756 Å) is shorter than the equatorial one (1.849 Å trans to O and 1.901 Å trans to N) whereas in the other case (XIDQAD), the corresponding length (1.914 Å) is longer than the equatorial one (1.495 Å trans to O and 1.885 Å trans to N). In the present structure, the Re—C11 bond (1.960 Å), is longer than the Re—C13 (1.903 Å, trans to O) and Re—C12 (1.912 Å, trans to N) bonds. This result is supported by the NMR analysis and is indicative of the structural trans effect (Coe & Glenwright, 2000).
To a stirred solution of quinaldic acid (17.3 mg, 0.1 mmol) in 5 ml me thanol, a solution of [NEt4]2[ReBr3(CO)3] (77 mg, 0.1 mmol) in 5 ml me thanol was added. The mixture was heated at 333 K, and after 30 min a solution of cyclohexyl isocyanide (0.1 mmol) in 3 ml me thanol was added. The mixture was stirred at room temperature for 2 h and the reaction progress was monitored by HPLC. The solvent was removed under reduced pressure and the solid residue was recrystallized from dichloromethane/hexane. The resulting solid was redissolved in a minimum volume of dichloromethane, layered with hexane and left to stand at room temperature. After a few days crystals suitable for X-ray analysis were isolated (yield: 44 mg, 80%). 1H NMR (DMSO-d6, p.p.m.): 8.93 (1H), 8.58 (1H), 8.32 (1H), 8.28 (1H), 8.18 (1H), 7.94 (1H), 4.08 (1H), 1.50 (2H), 1.40 (2H), 1.13(2H), 1.08 (2H), 0.88 (2H); 13C NMR (DMSO-d6, p.p.m.): 193.65, 193.12, 190.54, 172.06, 152.63, 146.23, 142.09, 138.85, 133.04, 130.47, 129.67, 129.61, 127.78, 122.78, 53.72, 30.48, 23.91, 20.70.
Tricarbonylrhenium(I) compounds are being explored as luminescent probes for cell imaging, photosensitizers in
(Lyczko et al., 2015; Bertrand et al., 2014), and as potential radiopharmaceuticals based on the already extensive use of radioactive 186/188Re compounds in nuclear medicine for pain palliation and radiosynovectomy (Schneider et al. 2005; Bodei et al. 2008). Recent studies have also revealed the potential of cold tricarbonylrhenium(I) complexes as anticancer agents (Leodinova & Gasser, 2014).As part of our ongoing research in the field of Re/Tc coordination compounds, the
of a new `2 + 1' tricarbonyl rhenium complex, fac-[M(CO)3(L)(QA—NO)], where M is Re,Tc, L is the monodentate ligand cyclohexylisocyanide, and QA—NO is deprotonated quinaldic acid, is presented. Because of the versatility of the `2 + 1' system, fac-[M(CO)3(L)(QA—NO)] complexes can be used as model compounds in the development of targeted radiopharmaceuticals or anticancer agents by suitable replacement of either the bidentate or monodentate ligand. For example, the monodentate ligand may be the isocyanide derivative of a pharmacophore with affinity for a certain receptor. Alternatively, the bidentate ligand may be a more extensive to act as a DNA intercalator. Both quinaldate- and isocyanide-based ligands have been used as possible DNA intercalators (Li et al., 2009; Agorastos et al., 2007).The molecular structure of the title compound, [Re(C10H6NO2)(C7H11N)(CO)3], is shown in Fig. 1. The ReI atom is six-coordinated by four C, one N and one O atoms in a distorted octahedral coordination sphere. The carbonyl C atoms are in a facial arrangement, with distances in the range 1.903 (8)–1.960 (8) Å, resulting in a cis arrangement of the bi- and monodentate ligands. The longest distance involving the carbonyl ligands [1.960 (8) Å; Re—C11] corresponds to the ligand trans to the isocyanide cyclohexyl ligand, defining the axial direction of the octahedral complex. The ReI atom almost lies in the equatorial plane (deviation, 0.006 Å) defined by the C12, C13, O1 and N1 atoms. The bite angle (N1—Re—O1) of the chelating ligand, corresponding to a five-membered ring, has a typical value of 75.2 (2)° (Lyczko et al., 2015). The Re—N1 and Re—O1 bond lengths are 2.273 (5) and 2.149 (5) Å, respectively. The isocyanide carbon atom, C14, is at a distance of 2.107 (8) Å from the metal site. All these values are close to those of a complex with the same core (Agorastos et al., 2007). The isocyanide group is oriented within the equatorial plane of the cyclohexyl ring which exhibits a chair conformation.
Figs. 2 and 3 show the supramolecular interactions of each complex molecule with its neighbours. Displaced π–π interactions between the phenyl and pyridine rings of quinaldate ligands of neighbouring complexes are present, with a Cg1···Cg2i distance of 3.650 Å [Cg1 and Cg2 are the centroids of the (C5–C10) and (N1,C2,C3,C4,C5,C10) rings, respectively; symmetry code: (i): 4 − x, 1 − y, 2 − z)]. These interactions help to consolidate the stacking of the molecules into rods parallel to [001] (Figs. 3 and 4). Weak intermolecular C—H···O hydrogen-bonding interactions (Table 1), including supramolecular R22(7) loops (C20—H20A···O1 and C15—H15···O2) join neighbouring rods into sheets parallel to (010) (Fig. 4). An additional type of interactions, viz. short of the C—H···H—C type (Sankolli et al., 2015), is realised through C18—H18···H18—C18 contacts. The cyclohexyl end of the isocyanide ligands is hanging above and below the sheets of molecules (Figs. 3 and 4), creating a perhydrogenated outer wall (Sankolli et al., 2015) at both sides of the layers. Such layers are stacked along [010] (through centres of symmetry located at b/2) and interact through the aforementioned C—H···H—C contacts (Fig. 5).
The packing of the complexes in the structure was further investigated with Hirshfeld surface analysis using the Crystal Explorer package (Wolff et al., 2012). The dnorm and curvedness (Spackman & Jayatilaka, 2009) surface mappings are presented in Figs. 6a, 6b and 6c, respectively. All C—H···O and C—H···H—C contacts are recognized on the dnorm mapped surface as deep-red depression areas in Figs. 6a and 6b, which represent two different upper views of the complex. Arrows at these figures indicate the specific type of contacts at each red point. A bottom view of the surface mapped with curvedness (Fig. 6c) shows broad, relatively flat regions (indicated by letter A) characteristic of planar stacking of complexes (Spackman & Jayatilaka, 2009), corresponding to the π–π interactions. In the fingerprint plot (Rohl et al., 2008), shown in Fig. 6d, the points indicated by 1, 2 A & 2B, 3 A & 3B and 4 correspond to H···H, H···O, C···H and C···C interactions with relative contributions of 25.1, 44.2, 18.1 and 4.3%, respectively. These types of interactions add to 91.7% of the intermolecular contacts of the Hirshfeld surface area. The remaining contributions (8.3%) correspond to N···H (2.1%), O···C (2.8%) and other less-important interactions (<1%).
In the solution NMR spectra of the complex, both the quinaldate and isocyanocyclohexane moieties are distinguishable. Coordination by the quinaldate is evident from the downfield shifts of all its protons ranging from 0.10 to 0.44 p.p.m. compared to free quinaldic acid under the same conditions (our data). Downfield shifts are also recorded for most of the C atoms of quinaldic acid, the most notable one (4.8 p.p.m.) being the one of the carboxylate carbonyl carbon. For the isocyanocyclohexane moiety, downfield shifts are recorded for the C atom (2.7 p.p.m.) bearing the isocyanide group and for its H atom (0.31 p.p.m.) compared to the free ligand. The most characteristic sign of coordination of the isocyanocyclohexane moiety is the sizable upfield shift of the isocyanide C atom of 15.5 p.p.m., attributed to an increased carbene character upon coordination (Stephany et al., 1974; Sagnou et al., 2010, 2011). In the 13C NMR spectrum of the complex, one of the carbonyl ligands of the Re(CO)3+ core appears shielded (by 2.8 p.p.m. on average) compared to the other two, an observation that may also be attributed to the trans effect of the isocyanide ligand.
A search of the Cambridge Structural Database (Groom & Allen, 2014) has revealed eight tricarbonyl complexes in facial arrangement and different N,O-bidentate ligands with a pyridine carboxylato-2 group at the binding side of the corresponding ligand. The N,O-binding sites together with the two carbonyl groups trans to N and O atoms define an equatorial plane, and the third together with the monodentate ligand define the axial position. The Re—C bond lengths of axial carbonyl ligands (1.883–1.922 Å) trans to the monodentate ligand have values equal or smaller than the equatorial ones (1.892–1.945 Å) when the ligand is an aqua ligand (Schutte & Visser, 2008; Mundwiler et al., 2004). The carbonyl Re—C bond lengths are intermediate (1.914–1.917 Å) between the values of the Re—C bonds trans to the equatorial O (1.886–1.916 Å) and N (1.921–1.926 Å) atoms, if the trans ligand is bonded to Re through an N atom (Benny et al., 2009; Mundwiler et al., 2004). Finally, the respective bond length, 1.947 Å, is longer than both Re—C bonds trans to equatorial O (1.912 Å) and N (1.914 Å) atoms if the Re atom is bonded to a P atom of a phosphine ligand (Hayes et al., 2014). In the case of the isocyanide group trans to the axial Re—C bond (Agorastos et al., 2007), the results are indistinct. In one case (XIDPUW), the axial bond length (1.756 Å) is shorter than the equatorial one (1.849 Å trans to O and 1.901 Å trans to N) whereas in the other case (XIDQAD), the corresponding length (1.914 Å) is longer than the equatorial one (1.495 Å trans to O and 1.885 Å trans to N). In the present structure, the Re—C11 bond (1.960 Å), is longer than the Re—C13 (1.903 Å, trans to O) and Re—C12 (1.912 Å, trans to N) bonds. This result is supported by the NMR analysis and is indicative of the structural trans effect (Coe & Glenwright, 2000).
To a stirred solution of quinaldic acid (17.3 mg, 0.1 mmol) in 5 ml me thanol, a solution of [NEt4]2[ReBr3(CO)3] (77 mg, 0.1 mmol) in 5 ml me thanol was added. The mixture was heated at 333 K, and after 30 min a solution of cyclohexyl isocyanide (0.1 mmol) in 3 ml me thanol was added. The mixture was stirred at room temperature for 2 h and the reaction progress was monitored by HPLC. The solvent was removed under reduced pressure and the solid residue was recrystallized from dichloromethane/hexane. The resulting solid was redissolved in a minimum volume of dichloromethane, layered with hexane and left to stand at room temperature. After a few days crystals suitable for X-ray analysis were isolated (yield: 44 mg, 80%). 1H NMR (DMSO-d6, p.p.m.): 8.93 (1H), 8.58 (1H), 8.32 (1H), 8.28 (1H), 8.18 (1H), 7.94 (1H), 4.08 (1H), 1.50 (2H), 1.40 (2H), 1.13(2H), 1.08 (2H), 0.88 (2H); 13C NMR (DMSO-d6, p.p.m.): 193.65, 193.12, 190.54, 172.06, 152.63, 146.23, 142.09, 138.85, 133.04, 130.47, 129.67, 129.61, 127.78, 122.78, 53.72, 30.48, 23.91, 20.70.
detailsCrystal data, data collection and structure
details are summarized in Table 2. C-bound H atoms were placed in idealized positions and refined using a riding model with C—H = 0.95 Å (aromatic H atoms), C—H = 0.99 Å (methylene H atoms), and with Uiso(H) = 1.2Ueq(C).Data collection: CrystalClear (Rigaku, 2005); cell
CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Crystal Impact, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).Fig. 1. The molecular structure and atom-labelling scheme of the title compound. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. Intermolecular interactions of the title complex with its neighbours. π–π interactions, weak C—H···O hydrogen bonds and short van der Waals contacts are shown with green, orange and turquoise dashed lines, respectively. [Symmetry codes: (') x + 1, y, z; ('') 1 + x, 1/2 − y, −1/2 + z; (''') 4 − x,1 − y, 2 − z.] | |
Fig. 3. A rod of complexes extending parallel to [001] through π–π interactions. The colour code is as in Fig. 2. | |
Fig. 4. Sheet of complexes arranged parallel to (010) showing π–π and weak C—H···O interactions. The colour code is as in Fig. 2. | |
Fig. 5. Stack of layers along [010] with C—H···H—C van der Waals contacts (light-blue dashed lines) developed among them, shown along the opposite [201] direction (see Fig. 4). | |
Fig. 6. Views of Hirshfeld surfaces mapped with dnorm (a)/(b), curvedness (c) properties and (d) fingerprint plots for the title complex. de and di are the distances to the nearest atom centre exterior and interior to the surface. 1, 2, 3 and 4 indicate H···H, H···O, C···H and C···C interactions, and A and B stand for acceptor and donor atoms, respectively. |
[Re(C10H6NO2)(C7H11N)(CO)3] | F(000) = 1064 |
Mr = 551.55 | Dx = 1.867 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
a = 7.1529 (1) Å | Cell parameters from 17036 reflections |
b = 29.5703 (5) Å | θ = 6.6–71.9° |
c = 9.6309 (2) Å | µ = 12.41 mm−1 |
β = 105.572 (1)° | T = 170 K |
V = 1962.29 (6) Å3 | Parallelepiped, colorless |
Z = 4 | 0.49 × 0.12 × 0.04 mm |
Rigaku R-AXIS SPIDER IPDS diffractometer | 2723 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.069 |
θ scans | θmax = 65.0°, θmin = 6.6° |
Absorption correction: multi-scan (CrystalClear; Rigaku 2005) | h = −8→8 |
Tmin = 0.374, Tmax = 1.000 | k = −33→27 |
21436 measured reflections | l = −11→11 |
3283 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.102 | w = 1/[σ2(Fo2) + (0.0314P)2 + 5.6979P] where P = (Fo2 + 2Fc2)/3 |
S = 1.17 | (Δ/σ)max = 0.001 |
3283 reflections | Δρmax = 1.30 e Å−3 |
253 parameters | Δρmin = −1.43 e Å−3 |
[Re(C10H6NO2)(C7H11N)(CO)3] | V = 1962.29 (6) Å3 |
Mr = 551.55 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 7.1529 (1) Å | µ = 12.41 mm−1 |
b = 29.5703 (5) Å | T = 170 K |
c = 9.6309 (2) Å | 0.49 × 0.12 × 0.04 mm |
β = 105.572 (1)° |
Rigaku R-AXIS SPIDER IPDS diffractometer | 3283 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku 2005) | 2723 reflections with I > 2σ(I) |
Tmin = 0.374, Tmax = 1.000 | Rint = 0.069 |
21436 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.17 | Δρmax = 1.30 e Å−3 |
3283 reflections | Δρmin = −1.43 e Å−3 |
253 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Re | 0.92831 (4) | 0.37585 (2) | 0.37372 (3) | 0.03094 (14) | |
N1 | 0.9723 (7) | 0.30250 (18) | 0.4300 (5) | 0.0284 (12) | |
O1 | 0.7817 (7) | 0.36522 (17) | 0.5387 (5) | 0.0416 (12) | |
O2 | 0.6499 (7) | 0.31296 (18) | 0.6478 (5) | 0.0484 (13) | |
C1 | 0.7486 (9) | 0.3239 (2) | 0.5673 (7) | 0.0355 (16) | |
C2 | 0.8488 (9) | 0.2879 (2) | 0.5021 (6) | 0.0301 (14) | |
C3 | 0.8153 (10) | 0.2429 (2) | 0.5234 (7) | 0.0346 (15) | |
H3 | 0.7263 | 0.2344 | 0.5762 | 0.042* | |
C4 | 0.9110 (9) | 0.2111 (2) | 0.4680 (7) | 0.0364 (16) | |
H4 | 0.8825 | 0.1799 | 0.4757 | 0.044* | |
C5 | 1.0531 (9) | 0.2242 (2) | 0.3988 (7) | 0.0350 (16) | |
C6 | 1.1665 (10) | 0.1931 (2) | 0.3467 (7) | 0.0413 (17) | |
H6 | 1.1444 | 0.1616 | 0.3549 | 0.050* | |
C7 | 1.3075 (10) | 0.2069 (3) | 0.2848 (7) | 0.0421 (18) | |
H7 | 1.3827 | 0.1855 | 0.2496 | 0.051* | |
C8 | 1.3385 (10) | 0.2532 (2) | 0.2742 (7) | 0.0395 (17) | |
H8 | 1.4385 | 0.2629 | 0.2332 | 0.047* | |
C9 | 1.2302 (9) | 0.2851 (2) | 0.3207 (6) | 0.0344 (15) | |
H9 | 1.2542 | 0.3164 | 0.3112 | 0.041* | |
C10 | 1.0834 (8) | 0.2709 (2) | 0.3826 (6) | 0.0279 (14) | |
C11 | 0.6948 (11) | 0.3602 (2) | 0.2213 (8) | 0.0386 (16) | |
O3 | 0.5615 (7) | 0.3509 (2) | 0.1301 (6) | 0.0588 (16) | |
C12 | 0.8592 (10) | 0.4384 (3) | 0.3514 (8) | 0.0419 (17) | |
O4 | 0.8223 (8) | 0.47647 (18) | 0.3391 (6) | 0.0549 (14) | |
C13 | 1.0602 (10) | 0.3846 (2) | 0.2285 (8) | 0.0381 (17) | |
O5 | 1.1396 (8) | 0.39159 (19) | 0.1404 (6) | 0.0529 (13) | |
C14 | 1.1806 (11) | 0.3915 (2) | 0.5378 (8) | 0.0381 (16) | |
N2 | 1.3213 (8) | 0.40084 (19) | 0.6200 (6) | 0.0353 (13) | |
C15 | 1.5026 (9) | 0.4170 (2) | 0.7131 (7) | 0.0365 (16) | |
H15 | 1.5983 | 0.3916 | 0.7321 | 0.044* | |
C16 | 1.4738 (12) | 0.4329 (3) | 0.8551 (7) | 0.057 (2) | |
H16A | 1.4335 | 0.4071 | 0.9061 | 0.068* | |
H16B | 1.3704 | 0.4561 | 0.8376 | 0.068* | |
C17 | 1.6631 (17) | 0.4527 (4) | 0.9473 (10) | 0.098 (4) | |
H17A | 1.6427 | 0.4645 | 1.0384 | 0.117* | |
H17B | 1.7629 | 0.4287 | 0.9717 | 0.117* | |
C18 | 1.7339 (18) | 0.4906 (4) | 0.8689 (17) | 0.133 (6) | |
H18A | 1.6382 | 0.5155 | 0.8505 | 0.160* | |
H18B | 1.8582 | 0.5024 | 0.9302 | 0.160* | |
C19 | 1.7628 (14) | 0.4744 (4) | 0.7288 (17) | 0.111 (5) | |
H19A | 1.8662 | 0.4512 | 0.7479 | 0.133* | |
H19B | 1.8056 | 0.5001 | 0.6788 | 0.133* | |
C20 | 1.5778 (10) | 0.4546 (3) | 0.6321 (9) | 0.055 (2) | |
H20A | 1.6038 | 0.4421 | 0.5437 | 0.066* | |
H20B | 1.4784 | 0.4786 | 0.6032 | 0.066* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Re | 0.0284 (2) | 0.0315 (2) | 0.0323 (2) | 0.00254 (11) | 0.00704 (15) | 0.00250 (11) |
N1 | 0.025 (3) | 0.034 (3) | 0.024 (3) | 0.003 (2) | 0.003 (2) | 0.002 (2) |
O1 | 0.044 (3) | 0.041 (3) | 0.046 (3) | 0.011 (2) | 0.022 (2) | 0.004 (2) |
O2 | 0.050 (3) | 0.055 (3) | 0.051 (3) | 0.007 (3) | 0.032 (3) | 0.007 (3) |
C1 | 0.031 (4) | 0.037 (4) | 0.036 (4) | 0.007 (3) | 0.006 (3) | −0.002 (3) |
C2 | 0.023 (3) | 0.035 (4) | 0.029 (3) | 0.002 (3) | 0.001 (3) | −0.001 (3) |
C3 | 0.038 (4) | 0.040 (4) | 0.029 (3) | 0.001 (3) | 0.015 (3) | 0.003 (3) |
C4 | 0.037 (4) | 0.028 (4) | 0.041 (4) | −0.001 (3) | 0.007 (3) | 0.002 (3) |
C5 | 0.027 (3) | 0.040 (4) | 0.034 (4) | 0.002 (3) | −0.001 (3) | −0.005 (3) |
C6 | 0.044 (4) | 0.029 (4) | 0.048 (4) | 0.007 (3) | 0.007 (3) | −0.005 (3) |
C7 | 0.033 (4) | 0.049 (5) | 0.046 (4) | 0.007 (3) | 0.014 (3) | −0.005 (4) |
C8 | 0.031 (4) | 0.049 (5) | 0.040 (4) | 0.005 (3) | 0.012 (3) | −0.004 (3) |
C9 | 0.027 (3) | 0.044 (4) | 0.032 (3) | 0.002 (3) | 0.008 (3) | 0.006 (3) |
C10 | 0.023 (3) | 0.034 (4) | 0.023 (3) | 0.005 (3) | −0.001 (3) | 0.001 (3) |
C11 | 0.047 (4) | 0.031 (4) | 0.042 (4) | 0.002 (3) | 0.019 (4) | 0.006 (3) |
O3 | 0.038 (3) | 0.059 (4) | 0.066 (4) | −0.003 (3) | −0.010 (3) | 0.001 (3) |
C12 | 0.032 (4) | 0.049 (5) | 0.044 (4) | −0.006 (4) | 0.008 (3) | −0.001 (4) |
O4 | 0.063 (4) | 0.036 (3) | 0.067 (4) | 0.010 (3) | 0.021 (3) | 0.013 (3) |
C13 | 0.036 (4) | 0.033 (4) | 0.042 (4) | 0.001 (3) | 0.004 (4) | 0.004 (3) |
O5 | 0.052 (3) | 0.057 (4) | 0.055 (3) | −0.004 (3) | 0.024 (3) | 0.008 (3) |
C14 | 0.042 (4) | 0.028 (4) | 0.044 (4) | 0.004 (3) | 0.012 (4) | 0.001 (3) |
N2 | 0.039 (3) | 0.036 (3) | 0.032 (3) | −0.003 (3) | 0.009 (3) | −0.002 (2) |
C15 | 0.034 (4) | 0.035 (4) | 0.038 (4) | 0.003 (3) | 0.005 (3) | −0.004 (3) |
C16 | 0.077 (6) | 0.055 (6) | 0.029 (4) | 0.013 (5) | −0.002 (4) | −0.005 (4) |
C17 | 0.123 (9) | 0.068 (7) | 0.064 (6) | 0.021 (7) | −0.042 (6) | −0.025 (5) |
C18 | 0.093 (9) | 0.073 (9) | 0.172 (14) | −0.017 (7) | −0.072 (9) | −0.035 (9) |
C19 | 0.051 (6) | 0.066 (8) | 0.203 (15) | −0.020 (5) | 0.009 (8) | 0.001 (9) |
C20 | 0.047 (5) | 0.037 (5) | 0.085 (7) | −0.005 (3) | 0.023 (5) | 0.012 (4) |
Re—C13 | 1.903 (8) | C9—C10 | 1.404 (8) |
Re—C12 | 1.912 (8) | C9—H9 | 0.9500 |
Re—C11 | 1.960 (8) | C11—O3 | 1.144 (8) |
Re—C14 | 2.107 (8) | C12—O4 | 1.155 (8) |
Re—O1 | 2.149 (5) | C13—O5 | 1.159 (8) |
Re—N1 | 2.237 (5) | C14—N2 | 1.135 (8) |
N1—C2 | 1.333 (8) | N2—C15 | 1.446 (8) |
N1—C10 | 1.380 (7) | C15—C16 | 1.512 (9) |
O1—C1 | 1.289 (8) | C15—C20 | 1.537 (9) |
O2—C1 | 1.224 (8) | C15—H15 | 1.0000 |
C1—C2 | 1.510 (9) | C16—C17 | 1.523 (12) |
C2—C3 | 1.376 (9) | C16—H16A | 0.9900 |
C3—C4 | 1.356 (9) | C16—H16B | 0.9900 |
C3—H3 | 0.9500 | C17—C18 | 1.512 (17) |
C4—C5 | 1.411 (9) | C17—H17A | 0.9900 |
C4—H4 | 0.9500 | C17—H17B | 0.9900 |
C5—C6 | 1.405 (9) | C18—C19 | 1.496 (17) |
C5—C10 | 1.413 (9) | C18—H18A | 0.9900 |
C6—C7 | 1.365 (9) | C18—H18B | 0.9900 |
C6—H6 | 0.9500 | C19—C20 | 1.516 (13) |
C7—C8 | 1.394 (10) | C19—H19A | 0.9900 |
C7—H7 | 0.9500 | C19—H19B | 0.9900 |
C8—C9 | 1.371 (9) | C20—H20A | 0.9900 |
C8—H8 | 0.9500 | C20—H20B | 0.9900 |
C13—Re—C12 | 87.2 (3) | C10—C9—H9 | 120.5 |
C13—Re—C11 | 88.4 (3) | N1—C10—C9 | 120.1 (6) |
C12—Re—C11 | 90.1 (3) | N1—C10—C5 | 120.4 (6) |
C13—Re—C14 | 91.6 (3) | C9—C10—C5 | 119.6 (6) |
C12—Re—C14 | 90.9 (3) | O3—C11—Re | 178.3 (6) |
C11—Re—C14 | 179.1 (3) | O4—C12—Re | 178.3 (7) |
C13—Re—O1 | 179.2 (2) | O5—C13—Re | 177.4 (6) |
C12—Re—O1 | 93.5 (2) | N2—C14—Re | 175.9 (6) |
C11—Re—O1 | 91.8 (2) | C14—N2—C15 | 173.2 (7) |
C14—Re—O1 | 88.1 (2) | N2—C15—C16 | 110.3 (6) |
C13—Re—N1 | 104.1 (2) | N2—C15—C20 | 107.6 (5) |
C12—Re—N1 | 168.7 (2) | C16—C15—C20 | 112.7 (6) |
C11—Re—N1 | 89.4 (2) | N2—C15—H15 | 108.7 |
C14—Re—N1 | 89.7 (2) | C16—C15—H15 | 108.7 |
O1—Re—N1 | 75.16 (18) | C20—C15—H15 | 108.7 |
C2—N1—C10 | 118.3 (5) | C15—C16—C17 | 109.4 (8) |
C2—N1—Re | 111.7 (4) | C15—C16—H16A | 109.8 |
C10—N1—Re | 129.2 (4) | C17—C16—H16A | 109.8 |
C1—O1—Re | 116.8 (4) | C15—C16—H16B | 109.8 |
O2—C1—O1 | 123.8 (6) | C17—C16—H16B | 109.8 |
O2—C1—C2 | 119.8 (6) | H16A—C16—H16B | 108.2 |
O1—C1—C2 | 116.4 (6) | C18—C17—C16 | 111.0 (8) |
N1—C2—C3 | 123.8 (6) | C18—C17—H17A | 109.4 |
N1—C2—C1 | 116.4 (6) | C16—C17—H17A | 109.4 |
C3—C2—C1 | 119.8 (6) | C18—C17—H17B | 109.4 |
C4—C3—C2 | 119.1 (6) | C16—C17—H17B | 109.4 |
C4—C3—H3 | 120.4 | H17A—C17—H17B | 108.0 |
C2—C3—H3 | 120.4 | C19—C18—C17 | 111.2 (10) |
C3—C4—C5 | 119.8 (6) | C19—C18—H18A | 109.4 |
C3—C4—H4 | 120.1 | C17—C18—H18A | 109.4 |
C5—C4—H4 | 120.1 | C19—C18—H18B | 109.4 |
C6—C5—C4 | 123.1 (7) | C17—C18—H18B | 109.4 |
C6—C5—C10 | 118.7 (6) | H18A—C18—H18B | 108.0 |
C4—C5—C10 | 118.2 (6) | C18—C19—C20 | 111.6 (9) |
C7—C6—C5 | 121.7 (7) | C18—C19—H19A | 109.3 |
C7—C6—H6 | 119.2 | C20—C19—H19A | 109.3 |
C5—C6—H6 | 119.2 | C18—C19—H19B | 109.3 |
C6—C7—C8 | 118.4 (7) | C20—C19—H19B | 109.3 |
C6—C7—H7 | 120.8 | H19A—C19—H19B | 108.0 |
C8—C7—H7 | 120.8 | C19—C20—C15 | 109.5 (8) |
C9—C8—C7 | 122.6 (7) | C19—C20—H20A | 109.8 |
C9—C8—H8 | 118.7 | C15—C20—H20A | 109.8 |
C7—C8—H8 | 118.7 | C19—C20—H20B | 109.8 |
C8—C9—C10 | 119.0 (7) | C15—C20—H20B | 109.8 |
C8—C9—H9 | 120.5 | H20A—C20—H20B | 108.2 |
D—H···A | D—H | H···A | D···A | D—H···A |
C20—H20A···O1i | 0.99 | 2.61 | 3.260 (10) | 123 |
C15—H15···O2i | 0.99 | 2.52 | 3.365 | 142 |
C7—H7···O2ii | 0.99 | 2.37 | 3.133 | 137 |
Symmetry codes: (i) x+1, y, z; (ii) x+1, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C20—H20A···O1i | 0.99 | 2.61 | 3.260 (10) | 123.1 |
C15—H15···O2i | 0.99 | 2.52 | 3.365 | 141.8 |
C7—H7···O2ii | 0.99 | 2.37 | 3.133 | 137 |
Symmetry codes: (i) x+1, y, z; (ii) x+1, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Re(C10H6NO2)(C7H11N)(CO)3] |
Mr | 551.55 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 170 |
a, b, c (Å) | 7.1529 (1), 29.5703 (5), 9.6309 (2) |
β (°) | 105.572 (1) |
V (Å3) | 1962.29 (6) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 12.41 |
Crystal size (mm) | 0.49 × 0.12 × 0.04 |
Data collection | |
Diffractometer | Rigaku R-AXIS SPIDER IPDS |
Absorption correction | Multi-scan (CrystalClear; Rigaku 2005) |
Tmin, Tmax | 0.374, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21436, 3283, 2723 |
Rint | 0.069 |
(sin θ/λ)max (Å−1) | 0.588 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.102, 1.17 |
No. of reflections | 3283 |
No. of parameters | 253 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.30, −1.43 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), DIAMOND (Crystal Impact, 2012), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
Acknowledgements
CT would like to thank the State Scholarships Foundation (IKY) in Greece for financial support during his postgraduate studies in the framework of `IKY fellowships Excellence for postgraduate studies in Greece – Siemens program'.
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