research communications
H-pyrazol-2-ium) cation and a β-octamolybdate anion
of an organic–inorganic supramolecular salt based on a 4,4′-methylenebis(3,5-dimethyl-1aDepartment of Chemistry, CICECO – Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal
*Correspondence e-mail: filipe.paz@ua.pt
The H-pyrazol-2-ium)] β-octamolybdate, (C11H18N4)2[Mo8O26] or (H4mbdpz)2[Mo8O26], is composed of an H4mbdpz2+ cation and half of the β-octamolybdate anion which is completed by inversion symmetry. The organic molecular units are engaged in a series of N—H⋯O hydrogen bonds with neighbouring anions, with N⋯O distances and N—H⋯O angles in the ranges 2.730 (2)–2.941 (2) Å and 122–166°, respectively. These interactions lead to the formation of a supramolecular two-dimensional network parallel to the (010) plane.
of the title compound, bis[4,4′-methylenebis(3,5-dimethyl-1Keywords: crystal structure; 4,4′-methylenebis(3,5-dimethyl-1H-pyrazol-2-ium) cation; β-octamolybdate anion; hydrogen-bonding network.
CCDC reference: 1443502
1. Chemical context
4,4′-Methylenebis(3,5-dimethylpyrazole) (H2mbdpz) is a flexible organic molecule which has been extensively used in the last few years by various research groups to design coordination-based and organic solids. While, on the one hand, the central methylene moiety confers some conformational flexibility to the entire molecular unit, on the other the two peripheral pyrazole rings permit not only the coordination to various types of metal atoms but also the involvement of these moieties in complex networks based on hydrogen bonds. It is, thus, not surprising to encounter a rich chemistry and structural diversity associated with this molecule. A search in the literature and in the Cambridge Structural Database (CSD; Allen, 2002; Groom & Allen, 2014) reveals, for example, that H2mbdpz has been used as an effective bending spacer to construct a large number of metal-organic frameworks (MOFs) or coordination polymers with various remarkable topologies based on a rather diverse range of d-block metals (Goswami et al., 2013; Mondal et al., 2008; Timokhin et al., 2015). H2mbdpz and its derivatives have also been used to prepare a range of supramolecular networks based on either neutral organic molecules or in the formation of salts with a wide range of anions (since, typically, the two pyrazole moieties appear protonated) (Basu et al., 2009; Basu & Mondal, 2010; Hazra et al., 2010). Most of these structural reports available in the literature either use H2mbdpz purchased from commercial sources or the authors prepare the molecule using published procedures. For the latter case, the standard method dates back to that reported by Trofimenko (1970), but more recent and alternative approaches are also employed to prepare the intended molecule (Kruger et al., 2000).
In this communication, we report the unexpected isolation of a new supramolecular salt in which 4,4′-methylenebis(3,5-dimethyl-1H-pyrazol-2-ium) (H4mbdpz2+) is prepared in situ, inside the autoclave reaction vessel, starting from 3,5-dimethylpyrazole in a reaction catalysed by MoVI ions in the presence of hydrogen peroxide. To balance the cationic charge of the protonated H4mbdpz2+ moiety, the crystal contains the well-known β-octamolybdate anion. It is remarkable to note that, despite the intensive research on supramolecular structures based on H2mbdpz, only a couple of very recent reports contain polyoxidometalate-type anions. Indeed, Tian et al. (2014, 2015) described various Ag+-based MOFs (or coordination polymers) in which MoVI or WVI Keggin and/or Wells–Dawson polyoxidometalates balance the positive charge of the cationic architectures.
2. Structural commentary
The H-pyrazol-2-ium) cation (H4mbdpz2+), and one half of the β-octamolybdate anion, β-[Mo8O26]4− (Fig. 1).
of the title compound is composed of a 4,4′-methylenebis(3,5-dimethyl-1The H4mbdpz2+ cation exhibits the typical structural features found in related compounds. The considerable imposed by the two peripheral 3,5-dimethyl-1H-pyrazol-2-ium moieties induces a tetrahedral angle of the bridging methylene group of 113.56 (17)°, which is very close to the median value found in similar structures (from the CSD: median of 114.7° from 109 hits with range of 111.0–120.0°). Conversely, the dihedral angle subtended by these two peripheral moieties is significantly more dependent on the itself, with the literature values (from 109 hits in the CSD) ranging from as low as 55.1° (a chiral coordination polymer with Cu2+ described by Lin et al., 2014) to 90.0° (an Ni2+ layered network described by Goswami et al., 2013). Nevertheless, the interplanar angle registered for the title compound, 77.85 (15)°, agrees well with the median value of all structures deposited in the CSD (81.1°).
The molecular geometrical parameters for the β-octamolybdate anion are typical, exhibiting the usual four families of Mo—O bonds: Mo—Ot to terminal oxido groups [bond lengths in the 1.6883 (14)–1.7077 (15) Å range]; Mo—Ob to μ2-bridging oxido groups [bond lengths in the 1.7506 (15)–2.2304 (15) Å range]; Mo—Oc to μ3-bridging oxido groups [bond lengths in the 1.9431 (14)–2.4033 (14) Å range]; Mo—Oc to μ5-bridging oxido groups [bond lengths in the 2.1441 (14)–2.3577 (14) Å range]. The four crystallographically independent MoVI metal atoms are hexacoordinated in a typical {MoO6} fashion resembling highly distorted octahedra: while the trans internal O—Mo—O octahedral angles are found in the 142.75 (6)–174.00 (6)° range, the cis angles refine instead in the 71.04 (5)–105.61 (8)° interval. This wide dispersion for the internal octahedral angles is a notable and well-known consequence of the marked trans effect created by the terminal oxido groups, which displace the metal atoms from the center of the octahedra. The intermetallic MoVI distances within the β-octamolybdate anion range from 3.1875 (5) Å (for the Mo1⋯Mo2 distance) to 3.5810 (5) Å [for the Mo1⋯Mo1i distance across the inversion center of the anion; (i) −x, 1 − y, 1 − z].
3. Supramolecular features
The crystal packing of the title compound is essentially mediated by the presence of various N—H⋯O hydrogen-bonding interactions between the H4mbdpz2+ cation (which acts as the donor – D) and the β-octamolybdate anion (the acceptor – A) (Fig. 2a). As depicted in Table 1, the D⋯A distances are relatively short, ranging between 2.730 (2) and 2.977 (2) Å. It is noteworthy that the latter is associated with the N2—H2 group which is engaged in a bifurcated interaction with the neighbouring β-octamolybdate anion (as depicted in Fig. 2a), hence leading to an average increase of the interatomic distances.
Besides these interactions, the
is also rich in weak hydrogen bonds of the C—H⋯O type (not shown) involving mainly the terminal methyl groups of the organic molecule. The various C—H⋯O interactions present in the are rather weak, with C⋯O distances ranging from 3.203 (3) to 3.457 (3) Å, with <(CHO) interaction angles in the 123–168° interval.The aforementioned hydrogen bonds between cations and anions lead to the formation of a two-dimensional supramolecular network parallel to the (010) plane (Fig. 2b). Individual supramolecular entities close-pack perpendicular to (010) to produce the of the title compound (Fig. 3).
4. Synthesis and crystallization
MoO3 (Analar, BDH Chemicals, 99.5%), 3,5-dimethylpyrazole (Aldrich, 99%) and H2O2 (50% in water, Sigma–Aldrich) were obtained from commercial sources and used as received. FT–IR spectra were collected using KBr pellets (Sigma–Aldrich, 99%, FT–IR grade) on a Mattson-7000 infrared spectrophotometer.
A mixture of MoO3 (0.349 g, 2.42 mmol), 3,5-dimethylpyrazole (0.116 g, 1.21 mmol), water (23 mL) and H2O2 (2 mL) was heated in a Teflon-lined stainless steel digestion bomb at 433 K for 26 h, at 373 K for 25 h, and finally slowly cooled down to ambient temperature over a period of 13 h. Single crystals of the title compound were obtained inside the Teflon vessel along with a yellow aqueous mother liquor (pH = 6) and a blueish solid, which was confirmed by powder X-ray diffraction studies to be residues of unreacted MoO3.
FT–IR (cm−1): ν~ = 3218 (vs); 3127 (s); 3008 (s); 2859 (s); 2719 (s); 1606 (m); 1579 (s); 1535 (m); 1517 (m); 1438 (s); 1394 (m); 1365 (m); 1253 (m); 1184 (m); 1153 (w); 1070 (w); 1047 (w); 948 (vs); 925 (s); 908 (vs); 844 (s); 721 (s); 705 (s); 671 (s); 655 (s); 543 (s); 522 (m); 480 (w); 458 (w); 445 (w); 414 (m); 401 (m); 360 (m).
5. details
Crystal data, data collection and structure . Hydrogen atoms bound to carbon were placed at idealized positions with C—H = 0.99 and 0.98 Å for the –CH2– and methyl groups, respectively, and included in the final structural model in the riding-motion approximation with isotropic displacement parameters fixed at 1.2 or 1.5Ueq, respectively, of the carbon atom to which they are attached.
details are summarized in Table 2
|
Hydrogen atoms associated with nitrogen atoms were directly located from difference Fourier maps and included in the model with the N—H distances restrained to 0.95 (1) Å in order to ensure a chemically reasonable environment for these moieties. These hydrogen atoms were modelled with isotropic thermal displacement parameters fixed at 1.5Ueq(N).
Supporting information
CCDC reference: 1443502
10.1107/S2056989015024524/gk2651sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015024524/gk2651Isup2.hkl
4,4'-Methylenebis(3,5-dimethylpyrazole) (H2mbdpz) is a flexible organic molecule which has been extensively used in the last few years by various research groups to design coordination-based and organic solids. While, on the one hand, the central methylene moiety confers some conformational flexibility to the entire molecular unit, on the other the two peripheral pyrazole rings permit not only the coordination to various types of metal atoms but also the involvement of these moieties in complex networks based on hydrogen bonds. It is, thus, not surprising to encounter a rich chemistry and structural diversity associated with this molecule. A search in the literature and in the Cambridge Structural Database (CSD; Allen, 2002; Groom & Allen, 2014) reveals, for example, that H2mbdpz has been used as an effective bending spacer to construct a large number of metal-organic frameworks (MOFs) or coordination polymers with various remarkable topologies based on a rather diverse range of d-block metals (Goswami et al., 2013; Mondal et al., 2008; Timokhin et al., 2015). H2mbdpz and its derivatives have also been used to prepare a range of supramolecular networks based on either neutral organic molecules or in the formation of salts with a wide range of anions (since, typically, the two pyrazole moieties appear protonated) (Basu et al., 2009; Basu & Mondal, 2010; Hazra et al., 2010). Most of these structural reports available in the literature either use H2mbdpz purchased from commercial sources or the authors prepare the molecule using published procedures. For the latter case, the standard method dates back to that reported by Trofimenko (1970), but more recent and alternative approaches are also employed to prepare the intended molecule (Kruger et al., 2000).
In this communication, we report the unexpected isolation of a new supramolecular salt in which 4,4'-methylenebis(3,5-dimethyl-1H-pyrazol-2-ium) (H4mbdpz2+) is prepared in situ, inside the autoclave reaction vessel, starting from 3,5-dimethylpyrazole in a reaction catalysed by MoVI ions in the presence of hydrogen peroxide. To balance the cationic charge of the protonated H4mbdpz2+ moiety, the crystal contains the well known β-octamolybdate anion. It is remarkable to note that, despite the intensive research on supramolecular structures based on H2mbdpz, only a couple of very recent reports contain polyoxidometalate-type anions. Indeed, Tian et al. (2014, 2015) described various Ag+-based MOFs (or coordination polymers) in which MoVI or WVI Keggin and/or Wells–Dawson polyoxidometalates balance the positive charge of the cationic architectures.
The β-octamolybdate anion, β-[Mo8O26]4− (Fig. 1).
of the title compound is composed of a 4,4'-methylenebis(3,5-dimethyl-1H-pyrazol-2-ium) cation (H4mbdpz2+), and one half of theThe H4mbdpz2+ cation exhibits the typical structural features found in related compounds. The considerable
imposed by the two peripheral 3,5-dimethyl-1H-pyrazol-2-ium moieties induces a tetrahedral angle of the bridging methylene group of 113.56 (17)°, which is very close to the median value found in similar structures (from the CSD: median of 114.7° from 109 hits with range of 111.0–120.0°). Conversely, the dihedral angle subtended by these two peripheral moieties is significantly more dependent on the itself, with the literature values (from 109 hits in the CSD) ranging from as low as 55.1° (a chiral coordination polymer with Cu2+ described by Lin et al., 2014) to 90.0° (an Ni2+ layered network described by Goswami et al., 2013). Nevertheless, the interplanar angle registered for the title compound, 77.85 (15)°, agrees well with the median value of all structures deposited in the CSD (81.1°).The molecular geometrical parameters for the β-octamolybdate anion are typical, exhibiting the usual four families of Mo—O bonds: Mo—Ot to terminal oxido groups [bond lengths in the 1.6883 (14)–1.7077 (15) Å range]; Mo—Ob to µ2-bridging oxido groups [bond lengths in the 1.7506 (15)–2.2304 (15) Å range]; Mo—Oc to µ3-bridging oxido groups [bond lengths in the 1.9431 (14)–2.4033 (14) Å range]; Mo—Oc to µ5-bridging oxido groups [bond lengths in the 2.1441 (14)–2.3577 (14) Å range]. The four crystallographically independent MoVI metal centers are hexacoordinated in a typical {MoO6} fashion resembling highly distorted octahedra: while the trans internal O—Mo—O octahedral angles are found in the 142.75 (6)–174.00 (6)° range, the cis angles refine instead in the 71.04 (5)–105.61 (8)° interval. This wide dispersion for the internal octahedral angles is a notable and well known consequence of the marked trans effect created by the terminal oxido groups, which displace the metal atoms from the center of the octahedra. The intermetallic MoVI distances within the β-octamolybdate anion range from 3.1875 (5) Å (for the Mo1···Mo2 distance) to 3.5810 (5) Å [for the Mo1···Mo1i distance across the inversion center of the anion; (i) −x, 1 − y, 1 − z].
The crystal packing of the title compound is essentially mediated by the presence of various N—H···O hydrogen-bonding interactions between the H4mbdpz2+ cation (which acts as the donor – D) and the β-octamolybdate anion (the acceptor – A) (Fig. 2a). As depicted in Table 1, the D···A distances are relatively short, ranging between 2.730 (2) and 2.977 (2) Å. It is noteworthy that the latter is associated with the N2—H2 group which is engaged in a bifurcated interaction with the neighbouring β-octamolybdate anion (as depicted in Fig. 2a), hence leading to an average increase of the interatomic distances.
Besides these interactions, the
is also rich in weak hydrogen bonds of the C—H···O type (not shown) involving mainly the terminal methyl groups of the organic molecule. The various C—H···O interactions present in the are rather weak, with C···O distances ranging from 3.203 (3) to 3.457 (3) Å, with <(CHO) interaction angles in the 123–168° interval.The aforementioned hydrogen bonds between cations and anions lead to the formation of a two-dimensional supramolecular network parallel to the (010) plane (Fig. 2b). Individual supramolecular entities close pack along the [010] direction to produce the
of the title compound (Fig. 3).MoO3 (Analar, BDH Chemicals, 99.5%), 3,5-dimethylpyrazole (Aldrich, 99%) and H2O2 (50% in water, Sigma–Aldrich) were obtained from commercial sources and used as received. FT–IR spectra were collected using KBr pellets (Sigma–Aldrich, 99%, FT–IR grade) on a Mattson-7000 infrared spectrophotometer.
A mixture of MoO3 (0.349 g, 2.42 mmol), 3,5-dimethylpyrazole (0.116 g, 1.21 mmol), water (23 ml) and H2O2 (2 ml) was heated in a Teflon-lined stainless steel digestion bomb at 433 K for 26 h, at 373 K for 25 h, and finally slowly cooled down to ambient temperature over a period of 13 h. Single crystals of the title compound were obtained inside the Teflon vessel along with a yellow aqueous mother liquor (pH = 6) and a blueish solid, which was confirmed by powder X-ray diffraction studies to be residues of unreacted MoO3.
FT–IR (cm−1): ñ = 3218 (vs); 3127 (s); 3008 (s); 2859 (s); 2719 (s); 1606 (m); 1579 (s); 1535 (m); 1517 (m); 1438 (s); 1394 (m); 1365 (m); 1253 (m); 1184 (m); 1153 (w); 1070 (w); 1047 (w); 948 (vs); 925 (s); 908 (vs); 844 (s); 721 (s); 705 (s); 671 (s); 655 (s); 543 (s); 522 (m); 480 (w); 458 (w); 445 (w); 414 (m); 401 (m); 360 (m).
Crystal data, data collection and structure
details are summarized in Table 2. Hydrogen atoms bound to carbon were placed at idealized positions with C—H = 0.99 and 0.98 Å for the –CH2-– and methyl groups, respectively, and included in the final structural model in the riding-motion approximation with the isotropic displacement parameters fixed at 1.2 or 1.5Ueq, respectively, of the carbon atom to which they are attached.Hydrogen atoms associated with nitrogen atoms were directly located from difference Fourier maps and included in the model with the N—H distances restrained to 0.95 (1) Å in order to ensure a chemically reasonable environment for these moieties. These hydrogen atoms were modelled with the isotropic thermal displacement parameters fixed at 1.5Ueq(N).
4,4'-Methylenebis(3,5-dimethylpyrazole) (H2mbdpz) is a flexible organic molecule which has been extensively used in the last few years by various research groups to design coordination-based and organic solids. While, on the one hand, the central methylene moiety confers some conformational flexibility to the entire molecular unit, on the other the two peripheral pyrazole rings permit not only the coordination to various types of metal atoms but also the involvement of these moieties in complex networks based on hydrogen bonds. It is, thus, not surprising to encounter a rich chemistry and structural diversity associated with this molecule. A search in the literature and in the Cambridge Structural Database (CSD; Allen, 2002; Groom & Allen, 2014) reveals, for example, that H2mbdpz has been used as an effective bending spacer to construct a large number of metal-organic frameworks (MOFs) or coordination polymers with various remarkable topologies based on a rather diverse range of d-block metals (Goswami et al., 2013; Mondal et al., 2008; Timokhin et al., 2015). H2mbdpz and its derivatives have also been used to prepare a range of supramolecular networks based on either neutral organic molecules or in the formation of salts with a wide range of anions (since, typically, the two pyrazole moieties appear protonated) (Basu et al., 2009; Basu & Mondal, 2010; Hazra et al., 2010). Most of these structural reports available in the literature either use H2mbdpz purchased from commercial sources or the authors prepare the molecule using published procedures. For the latter case, the standard method dates back to that reported by Trofimenko (1970), but more recent and alternative approaches are also employed to prepare the intended molecule (Kruger et al., 2000).
In this communication, we report the unexpected isolation of a new supramolecular salt in which 4,4'-methylenebis(3,5-dimethyl-1H-pyrazol-2-ium) (H4mbdpz2+) is prepared in situ, inside the autoclave reaction vessel, starting from 3,5-dimethylpyrazole in a reaction catalysed by MoVI ions in the presence of hydrogen peroxide. To balance the cationic charge of the protonated H4mbdpz2+ moiety, the crystal contains the well known β-octamolybdate anion. It is remarkable to note that, despite the intensive research on supramolecular structures based on H2mbdpz, only a couple of very recent reports contain polyoxidometalate-type anions. Indeed, Tian et al. (2014, 2015) described various Ag+-based MOFs (or coordination polymers) in which MoVI or WVI Keggin and/or Wells–Dawson polyoxidometalates balance the positive charge of the cationic architectures.
The β-octamolybdate anion, β-[Mo8O26]4− (Fig. 1).
of the title compound is composed of a 4,4'-methylenebis(3,5-dimethyl-1H-pyrazol-2-ium) cation (H4mbdpz2+), and one half of theThe H4mbdpz2+ cation exhibits the typical structural features found in related compounds. The considerable
imposed by the two peripheral 3,5-dimethyl-1H-pyrazol-2-ium moieties induces a tetrahedral angle of the bridging methylene group of 113.56 (17)°, which is very close to the median value found in similar structures (from the CSD: median of 114.7° from 109 hits with range of 111.0–120.0°). Conversely, the dihedral angle subtended by these two peripheral moieties is significantly more dependent on the itself, with the literature values (from 109 hits in the CSD) ranging from as low as 55.1° (a chiral coordination polymer with Cu2+ described by Lin et al., 2014) to 90.0° (an Ni2+ layered network described by Goswami et al., 2013). Nevertheless, the interplanar angle registered for the title compound, 77.85 (15)°, agrees well with the median value of all structures deposited in the CSD (81.1°).The molecular geometrical parameters for the β-octamolybdate anion are typical, exhibiting the usual four families of Mo—O bonds: Mo—Ot to terminal oxido groups [bond lengths in the 1.6883 (14)–1.7077 (15) Å range]; Mo—Ob to µ2-bridging oxido groups [bond lengths in the 1.7506 (15)–2.2304 (15) Å range]; Mo—Oc to µ3-bridging oxido groups [bond lengths in the 1.9431 (14)–2.4033 (14) Å range]; Mo—Oc to µ5-bridging oxido groups [bond lengths in the 2.1441 (14)–2.3577 (14) Å range]. The four crystallographically independent MoVI metal centers are hexacoordinated in a typical {MoO6} fashion resembling highly distorted octahedra: while the trans internal O—Mo—O octahedral angles are found in the 142.75 (6)–174.00 (6)° range, the cis angles refine instead in the 71.04 (5)–105.61 (8)° interval. This wide dispersion for the internal octahedral angles is a notable and well known consequence of the marked trans effect created by the terminal oxido groups, which displace the metal atoms from the center of the octahedra. The intermetallic MoVI distances within the β-octamolybdate anion range from 3.1875 (5) Å (for the Mo1···Mo2 distance) to 3.5810 (5) Å [for the Mo1···Mo1i distance across the inversion center of the anion; (i) −x, 1 − y, 1 − z].
The crystal packing of the title compound is essentially mediated by the presence of various N—H···O hydrogen-bonding interactions between the H4mbdpz2+ cation (which acts as the donor – D) and the β-octamolybdate anion (the acceptor – A) (Fig. 2a). As depicted in Table 1, the D···A distances are relatively short, ranging between 2.730 (2) and 2.977 (2) Å. It is noteworthy that the latter is associated with the N2—H2 group which is engaged in a bifurcated interaction with the neighbouring β-octamolybdate anion (as depicted in Fig. 2a), hence leading to an average increase of the interatomic distances.
Besides these interactions, the
is also rich in weak hydrogen bonds of the C—H···O type (not shown) involving mainly the terminal methyl groups of the organic molecule. The various C—H···O interactions present in the are rather weak, with C···O distances ranging from 3.203 (3) to 3.457 (3) Å, with <(CHO) interaction angles in the 123–168° interval.The aforementioned hydrogen bonds between cations and anions lead to the formation of a two-dimensional supramolecular network parallel to the (010) plane (Fig. 2b). Individual supramolecular entities close pack along the [010] direction to produce the
of the title compound (Fig. 3).MoO3 (Analar, BDH Chemicals, 99.5%), 3,5-dimethylpyrazole (Aldrich, 99%) and H2O2 (50% in water, Sigma–Aldrich) were obtained from commercial sources and used as received. FT–IR spectra were collected using KBr pellets (Sigma–Aldrich, 99%, FT–IR grade) on a Mattson-7000 infrared spectrophotometer.
A mixture of MoO3 (0.349 g, 2.42 mmol), 3,5-dimethylpyrazole (0.116 g, 1.21 mmol), water (23 ml) and H2O2 (2 ml) was heated in a Teflon-lined stainless steel digestion bomb at 433 K for 26 h, at 373 K for 25 h, and finally slowly cooled down to ambient temperature over a period of 13 h. Single crystals of the title compound were obtained inside the Teflon vessel along with a yellow aqueous mother liquor (pH = 6) and a blueish solid, which was confirmed by powder X-ray diffraction studies to be residues of unreacted MoO3.
FT–IR (cm−1): ñ = 3218 (vs); 3127 (s); 3008 (s); 2859 (s); 2719 (s); 1606 (m); 1579 (s); 1535 (m); 1517 (m); 1438 (s); 1394 (m); 1365 (m); 1253 (m); 1184 (m); 1153 (w); 1070 (w); 1047 (w); 948 (vs); 925 (s); 908 (vs); 844 (s); 721 (s); 705 (s); 671 (s); 655 (s); 543 (s); 522 (m); 480 (w); 458 (w); 445 (w); 414 (m); 401 (m); 360 (m).
detailsCrystal data, data collection and structure
details are summarized in Table 2. Hydrogen atoms bound to carbon were placed at idealized positions with C—H = 0.99 and 0.98 Å for the –CH2-– and methyl groups, respectively, and included in the final structural model in the riding-motion approximation with the isotropic displacement parameters fixed at 1.2 or 1.5Ueq, respectively, of the carbon atom to which they are attached.Hydrogen atoms associated with nitrogen atoms were directly located from difference Fourier maps and included in the model with the N—H distances restrained to 0.95 (1) Å in order to ensure a chemically reasonable environment for these moieties. These hydrogen atoms were modelled with the isotropic thermal displacement parameters fixed at 1.5Ueq(N).
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: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).Fig. 1. Schematic representation of the molecular entities composing the asymmetric unit of the title compound. The β-octamolybdate anion has been completed by inversion symmetry for the sake of chemical accuracy. All non-hydrogen atoms are represented as displacement ellipsoids drawn at the 60% probability level and hydrogen atoms as small spheres with arbitrary radii. Non-hydrogen atoms belonging to the asymmetric unit have been labelled for clarity. Dashed violet lines indicate N—H···O hydrogen-bonding interactions (see Table 1 for geometrical details). | |
Fig. 2. Schematic representation of the type and role of N—H···O hydrogen bond interactions present in the crystal structure of the title compound: (a) description of all interactions which connect the crystallographically independent 4,4'-methylenebis(3,5-dimethyl-1H-pyrazol-2-ium) cation to two neighbouring β-octamolybdate anions; (b) portion of the two-dimensional supramolecular layer placed in the ac plane of the unit cell formed by the connection between the molecular units present in the title compound. For geometrical details of the represented hydrogen bonds (as violet dashed lines) see Table 1. Symmetry operations used to generate equivalent atoms: (i) −x, 1 − y, 1 − z; (ii) −x, 1 − y, −z. | |
Fig. 3. Ball-and-stick schematic representation of the crystal packing of the title compound viewed in perspective along the [100] direction. The figure emphasizes, on the one hand, how the inorganic component of the crystal structure is fully embedded into an organic matrix based on the 4,4'-methylenebis(3,5-dimethyl-1H-pyrazol-2-ium) cation. On the other it shows how supramolecular hydrogen-bonded layers pack closely along the [010] direction. |
(C11H18N4)[Mo8O26] | Z = 1 |
Mr = 1596.11 | F(000) = 768 |
Triclinic, P1 | Dx = 2.532 Mg m−3 |
a = 8.6394 (10) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.0694 (13) Å | Cell parameters from 9149 reflections |
c = 12.2249 (14) Å | θ = 2.5–29.0° |
α = 113.343 (3)° | µ = 2.42 mm−1 |
β = 110.629 (4)° | T = 180 K |
γ = 96.540 (4)° | Plate, colourless |
V = 1046.6 (2) Å3 | 0.28 × 0.18 × 0.15 mm |
Bruker D8 QUEST diffractometer | 5605 independent reflections |
Radiation source: Sealed tube | 4669 reflections with I > 2σ(I) |
Multi-layer X-ray mirror monochromator | Rint = 0.032 |
Detector resolution: 10.4167 pixels mm-1 | θmax = 29.1°, θmin = 3.6° |
ω / φ scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | k = −16→15 |
Tmin = 0.595, Tmax = 0.746 | l = −16→16 |
58761 measured reflections |
Refinement on F2 | 4 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.021 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.045 | w = 1/[σ2(Fo2) + (0.0188P)2 + 0.8837P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.002 |
5605 reflections | Δρmax = 0.45 e Å−3 |
305 parameters | Δρmin = −0.38 e Å−3 |
(C11H18N4)[Mo8O26] | γ = 96.540 (4)° |
Mr = 1596.11 | V = 1046.6 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.6394 (10) Å | Mo Kα radiation |
b = 12.0694 (13) Å | µ = 2.42 mm−1 |
c = 12.2249 (14) Å | T = 180 K |
α = 113.343 (3)° | 0.28 × 0.18 × 0.15 mm |
β = 110.629 (4)° |
Bruker D8 QUEST diffractometer | 5605 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 4669 reflections with I > 2σ(I) |
Tmin = 0.595, Tmax = 0.746 | Rint = 0.032 |
58761 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 4 restraints |
wR(F2) = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.45 e Å−3 |
5605 reflections | Δρmin = −0.38 e Å−3 |
305 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 | ||
Mo1 | −0.21482 (2) | 0.51375 (2) | 0.44384 (2) | 0.01325 (5) | |
Mo2 | −0.03289 (2) | 0.47766 (2) | 0.25116 (2) | 0.01588 (5) | |
Mo3 | 0.09806 (2) | 0.76466 (2) | 0.66882 (2) | 0.01539 (5) | |
Mo4 | 0.29881 (2) | 0.72827 (2) | 0.48193 (2) | 0.01568 (5) | |
O1 | 0.03817 (17) | 0.59486 (13) | 0.47061 (13) | 0.0144 (3) | |
O2 | 0.20451 (18) | 0.57180 (14) | 0.31700 (14) | 0.0173 (3) | |
O3 | 0.5019 (2) | 0.78869 (15) | 0.50477 (16) | 0.0241 (3) | |
O4 | 0.30714 (18) | 0.80224 (14) | 0.65515 (14) | 0.0181 (3) | |
O5 | 0.1782 (2) | 0.81272 (15) | 0.42422 (15) | 0.0231 (3) | |
O6 | 0.1581 (2) | 0.85684 (15) | 0.83252 (15) | 0.0250 (4) | |
O7 | −0.10203 (18) | 0.63200 (13) | 0.63336 (13) | 0.0154 (3) | |
O8 | −0.0215 (2) | 0.83770 (14) | 0.59176 (15) | 0.0221 (3) | |
O9 | −0.37025 (18) | 0.41295 (14) | 0.45016 (14) | 0.0171 (3) | |
O10 | −0.32215 (19) | 0.60161 (14) | 0.38551 (14) | 0.0194 (3) | |
O11 | −0.20542 (18) | 0.39078 (13) | 0.28676 (13) | 0.0158 (3) | |
O12 | −0.0557 (2) | 0.35530 (15) | 0.10928 (15) | 0.0250 (4) | |
O13 | −0.1414 (2) | 0.57098 (15) | 0.20309 (16) | 0.0240 (3) | |
N1 | 0.3125 (3) | 0.17745 (19) | −0.33840 (19) | 0.0245 (4) | |
H1 | 0.327 (3) | 0.200 (2) | −0.400 (2) | 0.037* | |
N2 | 0.1581 (3) | 0.15545 (18) | −0.33513 (19) | 0.0236 (4) | |
H2 | 0.065 (2) | 0.170 (3) | −0.391 (2) | 0.035* | |
N3 | 0.2863 (2) | 0.27594 (18) | 0.22445 (18) | 0.0216 (4) | |
H3 | 0.242 (3) | 0.280 (2) | 0.285 (2) | 0.032* | |
N4 | 0.3249 (2) | 0.37686 (18) | 0.20751 (19) | 0.0222 (4) | |
H4 | 0.302 (3) | 0.4503 (16) | 0.255 (2) | 0.033* | |
C1 | 0.6179 (3) | 0.2024 (3) | −0.2101 (3) | 0.0315 (6) | |
H1A | 0.6526 | 0.2767 | −0.2201 | 0.047* | |
H1B | 0.6313 | 0.1287 | −0.2749 | 0.047* | |
H1C | 0.6910 | 0.2175 | −0.1205 | 0.047* | |
C2 | 0.4340 (3) | 0.1784 (2) | −0.2327 (2) | 0.0208 (5) | |
C3 | 0.3525 (3) | 0.1549 (2) | −0.1608 (2) | 0.0167 (4) | |
C4 | 0.1777 (3) | 0.1416 (2) | −0.2286 (2) | 0.0190 (4) | |
C5 | 0.0296 (3) | 0.1179 (2) | −0.1979 (2) | 0.0279 (5) | |
H5A | −0.0785 | 0.0794 | −0.2794 | 0.042* | |
H5B | 0.0260 | 0.1980 | −0.1351 | 0.042* | |
H5C | 0.0434 | 0.0607 | −0.1587 | 0.042* | |
C6 | 0.4344 (3) | 0.1463 (2) | −0.0344 (2) | 0.0188 (4) | |
H6A | 0.5618 | 0.1776 | 0.0017 | 0.023* | |
H6B | 0.4039 | 0.0565 | −0.0549 | 0.023* | |
C7 | 0.2913 (3) | 0.0554 (2) | 0.1437 (2) | 0.0265 (5) | |
H7A | 0.2436 | 0.0594 | 0.2065 | 0.040* | |
H7B | 0.4020 | 0.0367 | 0.1703 | 0.040* | |
H7C | 0.2101 | −0.0113 | 0.0548 | 0.040* | |
C8 | 0.3187 (3) | 0.1786 (2) | 0.1426 (2) | 0.0181 (4) | |
C9 | 0.3792 (3) | 0.2204 (2) | 0.0700 (2) | 0.0167 (4) | |
C10 | 0.3814 (3) | 0.3458 (2) | 0.1134 (2) | 0.0194 (4) | |
C11 | 0.4314 (3) | 0.4388 (2) | 0.0725 (2) | 0.0280 (5) | |
H11A | 0.4545 | 0.5243 | 0.1415 | 0.042* | |
H11B | 0.3371 | 0.4233 | −0.0105 | 0.042* | |
H11C | 0.5359 | 0.4305 | 0.0594 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo1 | 0.01265 (9) | 0.01485 (9) | 0.01065 (9) | 0.00461 (7) | 0.00402 (7) | 0.00530 (7) |
Mo2 | 0.01593 (9) | 0.01973 (10) | 0.01075 (9) | 0.00480 (7) | 0.00481 (7) | 0.00702 (7) |
Mo3 | 0.01680 (9) | 0.01357 (9) | 0.01255 (9) | 0.00375 (7) | 0.00645 (7) | 0.00330 (7) |
Mo4 | 0.01521 (9) | 0.01665 (10) | 0.01562 (9) | 0.00504 (7) | 0.00687 (7) | 0.00775 (7) |
O1 | 0.0138 (7) | 0.0161 (7) | 0.0114 (7) | 0.0040 (6) | 0.0047 (6) | 0.0055 (6) |
O2 | 0.0176 (7) | 0.0210 (8) | 0.0145 (7) | 0.0060 (6) | 0.0081 (6) | 0.0083 (6) |
O3 | 0.0201 (8) | 0.0265 (9) | 0.0267 (9) | 0.0054 (7) | 0.0115 (7) | 0.0127 (7) |
O4 | 0.0158 (7) | 0.0176 (8) | 0.0151 (7) | 0.0020 (6) | 0.0045 (6) | 0.0050 (6) |
O5 | 0.0253 (8) | 0.0244 (9) | 0.0235 (8) | 0.0106 (7) | 0.0105 (7) | 0.0139 (7) |
O6 | 0.0301 (9) | 0.0218 (8) | 0.0158 (8) | 0.0046 (7) | 0.0092 (7) | 0.0036 (7) |
O7 | 0.0154 (7) | 0.0162 (7) | 0.0121 (7) | 0.0039 (6) | 0.0061 (6) | 0.0044 (6) |
O8 | 0.0229 (8) | 0.0200 (8) | 0.0229 (8) | 0.0075 (7) | 0.0098 (7) | 0.0094 (7) |
O9 | 0.0145 (7) | 0.0192 (8) | 0.0156 (7) | 0.0049 (6) | 0.0051 (6) | 0.0075 (6) |
O10 | 0.0193 (8) | 0.0207 (8) | 0.0182 (8) | 0.0082 (6) | 0.0067 (6) | 0.0098 (6) |
O11 | 0.0147 (7) | 0.0175 (8) | 0.0112 (7) | 0.0039 (6) | 0.0038 (6) | 0.0049 (6) |
O12 | 0.0259 (9) | 0.0284 (9) | 0.0159 (8) | 0.0052 (7) | 0.0085 (7) | 0.0072 (7) |
O13 | 0.0219 (8) | 0.0309 (9) | 0.0236 (8) | 0.0101 (7) | 0.0081 (7) | 0.0177 (7) |
N1 | 0.0309 (11) | 0.0266 (11) | 0.0215 (10) | 0.0096 (9) | 0.0126 (9) | 0.0151 (9) |
N2 | 0.0243 (10) | 0.0250 (11) | 0.0203 (10) | 0.0107 (8) | 0.0055 (8) | 0.0123 (8) |
N3 | 0.0214 (10) | 0.0241 (10) | 0.0181 (9) | 0.0042 (8) | 0.0127 (8) | 0.0059 (8) |
N4 | 0.0198 (10) | 0.0206 (10) | 0.0201 (10) | 0.0071 (8) | 0.0083 (8) | 0.0042 (8) |
C1 | 0.0293 (13) | 0.0458 (16) | 0.0349 (14) | 0.0136 (12) | 0.0208 (12) | 0.0265 (13) |
C2 | 0.0255 (12) | 0.0210 (12) | 0.0194 (11) | 0.0087 (9) | 0.0107 (9) | 0.0115 (9) |
C3 | 0.0201 (11) | 0.0164 (11) | 0.0150 (10) | 0.0071 (8) | 0.0089 (9) | 0.0069 (8) |
C4 | 0.0215 (11) | 0.0148 (11) | 0.0199 (11) | 0.0074 (9) | 0.0084 (9) | 0.0074 (9) |
C5 | 0.0215 (12) | 0.0335 (14) | 0.0304 (13) | 0.0101 (10) | 0.0128 (10) | 0.0148 (11) |
C6 | 0.0214 (11) | 0.0247 (12) | 0.0178 (11) | 0.0103 (9) | 0.0121 (9) | 0.0127 (9) |
C7 | 0.0346 (14) | 0.0221 (12) | 0.0201 (12) | 0.0007 (10) | 0.0132 (10) | 0.0084 (10) |
C8 | 0.0157 (10) | 0.0216 (11) | 0.0131 (10) | 0.0028 (8) | 0.0058 (8) | 0.0057 (9) |
C9 | 0.0132 (10) | 0.0215 (11) | 0.0136 (10) | 0.0041 (8) | 0.0049 (8) | 0.0078 (9) |
C10 | 0.0143 (10) | 0.0237 (12) | 0.0156 (10) | 0.0051 (8) | 0.0029 (8) | 0.0083 (9) |
C11 | 0.0323 (13) | 0.0220 (12) | 0.0236 (12) | 0.0038 (10) | 0.0048 (10) | 0.0125 (10) |
Mo1—O10 | 1.6883 (14) | N2—C4 | 1.332 (3) |
Mo1—O9 | 1.7506 (15) | N2—H2 | 0.935 (10) |
Mo1—O11 | 1.9431 (14) | N3—N4 | 1.339 (3) |
Mo1—O7 | 1.9561 (14) | N3—C8 | 1.342 (3) |
Mo1—O1 | 2.1441 (14) | N3—H3 | 0.937 (10) |
Mo1—O1i | 2.3577 (14) | N4—C10 | 1.341 (3) |
Mo1—Mo2 | 3.1874 (4) | N4—H4 | 0.937 (10) |
Mo1—Mo3 | 3.2153 (4) | C1—C2 | 1.485 (3) |
Mo2—O13 | 1.6939 (15) | C1—H1A | 0.9800 |
Mo2—O12 | 1.7005 (16) | C1—H1B | 0.9800 |
Mo2—O2 | 1.9304 (15) | C1—H1C | 0.9800 |
Mo2—O11 | 1.9933 (15) | C2—C3 | 1.391 (3) |
Mo2—O1 | 2.2824 (14) | C3—C4 | 1.397 (3) |
Mo2—O7i | 2.4033 (14) | C3—C6 | 1.508 (3) |
Mo3—O6 | 1.6984 (15) | C4—C5 | 1.484 (3) |
Mo3—O8 | 1.7063 (15) | C5—H5A | 0.9800 |
Mo3—O4 | 1.8928 (15) | C5—H5B | 0.9800 |
Mo3—O7 | 2.0078 (15) | C5—H5C | 0.9800 |
Mo3—O1 | 2.2975 (14) | C6—C9 | 1.509 (3) |
Mo3—O11i | 2.3502 (14) | C6—H6A | 0.9900 |
Mo4—O3 | 1.6999 (15) | C6—H6B | 0.9900 |
Mo4—O5 | 1.7077 (15) | C7—C8 | 1.485 (3) |
Mo4—O4 | 1.9147 (15) | C7—H7A | 0.9800 |
Mo4—O2 | 1.9416 (15) | C7—H7B | 0.9800 |
Mo4—O9i | 2.2304 (15) | C7—H7C | 0.9800 |
O1—Mo1i | 2.3577 (14) | C8—C9 | 1.393 (3) |
O7—Mo2i | 2.4033 (14) | C9—C10 | 1.386 (3) |
O9—Mo4i | 2.2304 (15) | C10—C11 | 1.477 (3) |
O11—Mo3i | 2.3502 (14) | C11—H11A | 0.9800 |
N1—C2 | 1.342 (3) | C11—H11B | 0.9800 |
N1—N2 | 1.347 (3) | C11—H11C | 0.9800 |
N1—H1 | 0.935 (10) | ||
O10—Mo1—O9 | 104.79 (7) | O4—Mo4—O9i | 78.01 (6) |
O10—Mo1—O11 | 101.71 (7) | O2—Mo4—O9i | 77.29 (6) |
O9—Mo1—O11 | 97.75 (6) | Mo1—O1—Mo2 | 92.07 (5) |
O10—Mo1—O7 | 100.07 (7) | Mo1—O1—Mo3 | 92.69 (5) |
O9—Mo1—O7 | 96.20 (6) | Mo2—O1—Mo3 | 160.42 (7) |
O11—Mo1—O7 | 150.11 (6) | Mo1—O1—Mo1i | 105.30 (6) |
O10—Mo1—O1 | 99.34 (7) | Mo2—O1—Mo1i | 99.34 (5) |
O9—Mo1—O1 | 155.85 (6) | Mo3—O1—Mo1i | 97.70 (5) |
O11—Mo1—O1 | 78.04 (6) | Mo2—O2—Mo4 | 116.88 (7) |
O7—Mo1—O1 | 78.43 (6) | Mo3—O4—Mo4 | 117.46 (7) |
O10—Mo1—O1i | 174.00 (6) | Mo1—O7—Mo3 | 108.41 (7) |
O9—Mo1—O1i | 81.15 (6) | Mo1—O7—Mo2i | 108.04 (6) |
O11—Mo1—O1i | 78.01 (5) | Mo3—O7—Mo2i | 103.79 (6) |
O7—Mo1—O1i | 78.19 (5) | Mo1—O9—Mo4i | 120.16 (7) |
O1—Mo1—O1i | 74.70 (6) | Mo1—O11—Mo2 | 108.13 (7) |
O10—Mo1—Mo2 | 89.83 (5) | Mo1—O11—Mo3i | 109.11 (6) |
O9—Mo1—Mo2 | 134.21 (5) | Mo2—O11—Mo3i | 106.18 (6) |
O11—Mo1—Mo2 | 36.46 (4) | C2—N1—N2 | 109.03 (18) |
O7—Mo1—Mo2 | 124.12 (4) | C2—N1—H1 | 128.8 (17) |
O1—Mo1—Mo2 | 45.69 (4) | N2—N1—H1 | 121.5 (17) |
O1i—Mo1—Mo2 | 86.48 (3) | C4—N2—N1 | 109.52 (18) |
O10—Mo1—Mo3 | 89.84 (5) | C4—N2—H2 | 129.5 (17) |
O9—Mo1—Mo3 | 132.50 (5) | N1—N2—H2 | 119.3 (17) |
O11—Mo1—Mo3 | 123.58 (4) | N4—N3—C8 | 109.53 (18) |
O7—Mo1—Mo3 | 36.33 (4) | N4—N3—H3 | 120.5 (16) |
O1—Mo1—Mo3 | 45.54 (4) | C8—N3—H3 | 129.9 (16) |
O1i—Mo1—Mo3 | 85.40 (4) | N3—N4—C10 | 109.06 (18) |
Mo2—Mo1—Mo3 | 89.640 (10) | N3—N4—H4 | 118.4 (16) |
O13—Mo2—O12 | 105.61 (8) | C10—N4—H4 | 132.4 (16) |
O13—Mo2—O2 | 101.67 (7) | C2—C1—H1A | 109.5 |
O12—Mo2—O2 | 99.58 (7) | C2—C1—H1B | 109.5 |
O13—Mo2—O11 | 99.61 (7) | H1A—C1—H1B | 109.5 |
O12—Mo2—O11 | 99.06 (7) | C2—C1—H1C | 109.5 |
O2—Mo2—O11 | 146.63 (6) | H1A—C1—H1C | 109.5 |
O13—Mo2—O1 | 95.07 (7) | H1B—C1—H1C | 109.5 |
O12—Mo2—O1 | 159.06 (7) | N1—C2—C3 | 107.6 (2) |
O2—Mo2—O1 | 78.95 (5) | N1—C2—C1 | 120.7 (2) |
O11—Mo2—O1 | 73.82 (5) | C3—C2—C1 | 131.8 (2) |
O13—Mo2—O7i | 165.12 (6) | C2—C3—C4 | 106.25 (19) |
O12—Mo2—O7i | 87.62 (6) | C2—C3—C6 | 127.50 (19) |
O2—Mo2—O7i | 82.35 (6) | C4—C3—C6 | 126.25 (19) |
O11—Mo2—O7i | 71.04 (5) | N2—C4—C3 | 107.61 (19) |
O1—Mo2—O7i | 71.46 (5) | N2—C4—C5 | 121.7 (2) |
O13—Mo2—Mo1 | 86.49 (5) | C3—C4—C5 | 130.7 (2) |
O12—Mo2—Mo1 | 134.42 (6) | C4—C5—H5A | 109.5 |
O2—Mo2—Mo1 | 121.20 (4) | C4—C5—H5B | 109.5 |
O11—Mo2—Mo1 | 35.40 (4) | H5A—C5—H5B | 109.5 |
O1—Mo2—Mo1 | 42.24 (4) | C4—C5—H5C | 109.5 |
O7i—Mo2—Mo1 | 79.26 (3) | H5A—C5—H5C | 109.5 |
O6—Mo3—O8 | 104.89 (8) | H5B—C5—H5C | 109.5 |
O6—Mo3—O4 | 102.17 (7) | C3—C6—C9 | 113.56 (17) |
O8—Mo3—O4 | 101.97 (7) | C3—C6—H6A | 108.9 |
O6—Mo3—O7 | 97.97 (7) | C9—C6—H6A | 108.9 |
O8—Mo3—O7 | 96.88 (7) | C3—C6—H6B | 108.9 |
O4—Mo3—O7 | 147.68 (6) | C9—C6—H6B | 108.9 |
O6—Mo3—O1 | 161.95 (7) | H6A—C6—H6B | 107.7 |
O8—Mo3—O1 | 92.20 (6) | C8—C7—H7A | 109.5 |
O4—Mo3—O1 | 79.39 (6) | C8—C7—H7B | 109.5 |
O7—Mo3—O1 | 73.84 (5) | H7A—C7—H7B | 109.5 |
O6—Mo3—O11i | 90.45 (7) | C8—C7—H7C | 109.5 |
O8—Mo3—O11i | 162.37 (6) | H7A—C7—H7C | 109.5 |
O4—Mo3—O11i | 82.78 (6) | H7B—C7—H7C | 109.5 |
O7—Mo3—O11i | 71.98 (5) | N3—C8—C9 | 107.23 (19) |
O1—Mo3—O11i | 71.81 (5) | N3—C8—C7 | 120.65 (19) |
O6—Mo3—Mo1 | 133.10 (6) | C9—C8—C7 | 132.1 (2) |
O8—Mo3—Mo1 | 84.13 (5) | C10—C9—C8 | 106.44 (19) |
O4—Mo3—Mo1 | 121.16 (4) | C10—C9—C6 | 126.00 (19) |
O7—Mo3—Mo1 | 35.26 (4) | C8—C9—C6 | 127.6 (2) |
O1—Mo3—Mo1 | 41.77 (3) | N4—C10—C9 | 107.7 (2) |
O11i—Mo3—Mo1 | 78.97 (4) | N4—C10—C11 | 121.0 (2) |
O3—Mo4—O5 | 105.36 (8) | C9—C10—C11 | 131.3 (2) |
O3—Mo4—O4 | 105.00 (7) | C10—C11—H11A | 109.5 |
O5—Mo4—O4 | 96.53 (7) | C10—C11—H11B | 109.5 |
O3—Mo4—O2 | 104.14 (7) | H11A—C11—H11B | 109.5 |
O5—Mo4—O2 | 97.61 (7) | C10—C11—H11C | 109.5 |
O4—Mo4—O2 | 142.75 (6) | H11A—C11—H11C | 109.5 |
O3—Mo4—O9i | 94.00 (6) | H11B—C11—H11C | 109.5 |
O5—Mo4—O9i | 160.64 (7) | ||
O6—Mo3—O4—Mo4 | −175.31 (8) | N1—N2—C4—C5 | 179.2 (2) |
O8—Mo3—O4—Mo4 | −66.98 (9) | C2—C3—C4—N2 | 0.6 (2) |
O7—Mo3—O4—Mo4 | 57.37 (15) | C6—C3—C4—N2 | −179.9 (2) |
O1—Mo3—O4—Mo4 | 23.03 (8) | C2—C3—C4—C5 | −178.8 (2) |
O11i—Mo3—O4—Mo4 | 95.79 (8) | C6—C3—C4—C5 | 0.7 (4) |
Mo1—Mo3—O4—Mo4 | 23.37 (10) | C2—C3—C6—C9 | 133.1 (2) |
O10—Mo1—O9—Mo4i | 178.98 (8) | C4—C3—C6—C9 | −46.3 (3) |
O11—Mo1—O9—Mo4i | 74.63 (8) | N4—N3—C8—C9 | −0.5 (2) |
O7—Mo1—O9—Mo4i | −78.87 (8) | N4—N3—C8—C7 | 178.4 (2) |
O1—Mo1—O9—Mo4i | −3.4 (2) | N3—C8—C9—C10 | 0.3 (2) |
O1i—Mo1—O9—Mo4i | −1.88 (7) | C7—C8—C9—C10 | −178.5 (2) |
Mo2—Mo1—O9—Mo4i | 74.35 (9) | N3—C8—C9—C6 | 179.6 (2) |
Mo3—Mo1—O9—Mo4i | −77.24 (9) | C7—C8—C9—C6 | 0.7 (4) |
C2—N1—N2—C4 | −0.2 (3) | C3—C6—C9—C10 | −50.6 (3) |
C8—N3—N4—C10 | 0.6 (2) | C3—C6—C9—C8 | 130.3 (2) |
N2—N1—C2—C3 | 0.6 (3) | N3—N4—C10—C9 | −0.4 (2) |
N2—N1—C2—C1 | −179.2 (2) | N3—N4—C10—C11 | 179.19 (19) |
N1—C2—C3—C4 | −0.7 (2) | C8—C9—C10—N4 | 0.0 (2) |
C1—C2—C3—C4 | 179.0 (2) | C6—C9—C10—N4 | −179.2 (2) |
N1—C2—C3—C6 | 179.8 (2) | C8—C9—C10—C11 | −179.5 (2) |
C1—C2—C3—C6 | −0.4 (4) | C6—C9—C10—C11 | 1.3 (4) |
N1—N2—C4—C3 | −0.2 (2) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O10ii | 0.94 | 2.34 | 2.941 (2) | 122 |
N2—H2···O5ii | 0.94 | 2.05 | 2.852 (2) | 143 |
N2—H2···O8ii | 0.94 | 2.31 | 2.977 (2) | 127 |
N3—H3···O7i | 0.94 | 1.97 | 2.759 (2) | 141 |
N4—H4···O2 | 0.94 | 1.81 | 2.730 (2) | 166 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O10i | 0.94 | 2.34 | 2.941 (2) | 122 |
N2—H2···O5i | 0.94 | 2.05 | 2.852 (2) | 143 |
N2—H2···O8i | 0.94 | 2.31 | 2.977 (2) | 127 |
N3—H3···O7ii | 0.94 | 1.97 | 2.759 (2) | 141 |
N4—H4···O2 | 0.94 | 1.81 | 2.730 (2) | 166 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C11H18N4)[Mo8O26] |
Mr | 1596.11 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 180 |
a, b, c (Å) | 8.6394 (10), 12.0694 (13), 12.2249 (14) |
α, β, γ (°) | 113.343 (3), 110.629 (4), 96.540 (4) |
V (Å3) | 1046.6 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 2.42 |
Crystal size (mm) | 0.28 × 0.18 × 0.15 |
Data collection | |
Diffractometer | Bruker D8 QUEST |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.595, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 58761, 5605, 4669 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.685 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.045, 1.05 |
No. of reflections | 5605 |
No. of parameters | 305 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.45, −0.38 |
Computer programs: APEX2 (Bruker, 2012), SAINT (Bruker, 2012), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), DIAMOND (Brandenburg, 1999).
Acknowledgements
Funding Sources and Entities: the Fundação para a Ciência e a Tecnologia (FCT, Portugal), the European Union, QREN, FEDER through Programa Operacional Factores de Competitividade (COMPETE), CICECO–Aveiro Institute of Materials (Ref. FCT UID/CTM/50011/2013) financed by national funds through the FCT/MEC and when applicable co-financed by FEDER under the PT2020 Partnership Agreement.Projects and Individual grants: We wish to thank the FCT for funding the R&D project FCOMP-01–0124-FEDER-041282 (reference FCT EXPL/CTM-NAN/0013/2013), and also CICECO for specific funding towards the purchase of the single-crystal diffractometer. The FCT is gratefully acknowledged for the post-doctoral research grant No. SFRH/BPD/97660/2013 (to TRA).
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