research communications
μ3-2-{[1,1-bis(hydroxymethyl)-2-oxidoethyl]iminomethyl}-6-methoxyphenolato)tetrakis[aquacopper(II)]: a redetermination at 200 K
of tetrakis(aDepartment of Inorganic Chemistry, Taras Shevchenko National University of Kyiv, 64/13 Volodymyrska Street, Kyiv 01601, Ukraine, and bCentre for Microscopy, Characterisation and Analysis, M313, University of Western Australia, Perth, WA 6009, Australia
*Correspondence e-mail: vassilyeva@univ.kiev.ua
The 4(C12H15NO5)4(H2O)4], has been previously reported by Back, Oliveira, Canabarro & Iglesias [Z. Anorg. Allg. Chem. (2015), 641, 941–947], based on room-temperature data. In the previously published structure, no standard uncertainties are recorded for the deprotonated hydroxymethyl group and water molecule O atoms coordinating to the metal atom indicating that they were not refined; furthermore, the H atoms of some OH groups and water molecules have not been positioned accurately. Since the current structure was determined at a lower temperature, all atoms, including the H atoms of these hydroxy groups and the water molecule, have been determined more accurately resulting in improved standard uncertainties in the bond lengths and angles. Diffraction data were collected at 200 K, rather than the more usual 100 K, due to apparent disordering at lower temperatures. In addition, it is now possible to report intra- and intermolecular O—H⋯O interactions. In the title complex molecule, which has crystallographic -4 symmetry, the CuII ions are coordinated by the tridentate Schiff base ligands and water molecules, forming a tetranuclear Cu4O4 cubane-like core. The CuII ion adopts a CuNO5 elongated octahedral environment. The coordination environment of CuII at 200 K displays a small contraction of the Cu—N/O bonds, compared with the room-temperature structure. In the the neutral clusters are linked by intermolecular O—H⋯O hydrogen bonds into a one-dimensional hydrogen-bonding network propagating along the b axis.
of the tetranuclear title compound, [CuKeywords: crystal structure; CuII cubane-type complex; Schiff base ligand; o-vanillin; tris(hydroxymethyl)aminomethane; hydrogen bonding.
CCDC reference: 1424781
1. Chemical context
During the last few years, we have been exploring the chemistry of transition metal complexes of Schiff base ligands with the aim of preparing heterometallic polynuclear compounds with diverse potential advantages. In these studies, we continued to apply the direct synthesis of coordination compounds based on spontaneous self-assembly, in which one of the metals is introduced as a powder (zerovalent state) and oxidized during the synthesis (typically by dioxygen from the air) (Pryma et al., 2003; Nesterova et al., 2008; Nesterov et al., 2012). The main advantage of this approach is the generation of building blocks in situ, in one reaction vessel, thus eliminating separate steps in building-block construction. Reactions of a metal powder and another metal salt in air with a solution containing a pre-formed Schiff base ligand have yielded a number of novel Co/Fe and Cu/Fe compounds (Chygorin et al., 2015; Nesterova et al., 2013).
The title compound was prepared in studies of the coordination behavior of the versatile multidentate Schiff base ligand 2-{[(2-hydroxy-3-methoxyphenyl)methylene]amino}-2-(hydroxymethyl)-1,3-propanediol (H4L) (Odabaşoğlu et al., 2003) which results from the condensation between o-vanillin and tris(hydroxymethyl)aminomethane. In the syntheses, the condensation reaction was utilized without isolation of the resulting Schiff base. In an attempt to prepare a heterometallic assembly we reacted Cu powder and Zn(CH3COO)2 with a methanol solution of the Schiff base in a 1:1:2 molar ratio. However, the isolated green microcrystalline product was identified crystallographically to be the tetranuclear CuII Schiff base complex Cu4(H2L)4(H2O)4 (1) of a hetero-cubane type.
The 1) has been reported previously at room temperature by Back et al. (2015) (refcode IGOSUU). In that report of the structure, no standard uncertainties are recorded for the oxygen atoms of the deprotonated hydroxymethyl group, O2, and the water molecule coordinating to the metal atom, O6, indicating that they were not refined. The hydrogen atoms of some OH groups and water molecules have also not been positioned accurately. It is clear from the checkCIF output that at least one of the water molecule hydrogen atoms, H6B, and one OH hydrogen atom, H4, are incorrectly positioned. Since the present structure was determined at a lower temperature, all atoms, including these hydrogen atoms, have been determined more accurately, resulting in improved standard uncertainties in the bond lengths and angles.
of (2. Structural commentary
The neutral [Cu4(C12H15NO5)4(H2O)4] molecule of (1) has crystallographic inversion symmetry. The CuII ions are coordinated by the tridentate Schiff base ligands and water molecules, forming a tetranuclear Cu4O4 cubane-like configuration. The ligand acts in a chelating–bridging mode via phenoxo-, alkoxo-O and imine-N atoms. The two hydroxymethyl groups remain protonated. The coordination about the CuII atom is distorted octahedral as a result of a significant Jahn–Teller distortion, the two axial distances Cu1—O2 2.738 (5) Å (to the water molecule) and the bridging bond, Cu1—O11 2.547 (4) Å, being significantly longer than the remainder which lie in the range 1.912 (4)–1.968 (3) Å (Fig. 1, Table 1). The trans angles at the metal atom lie in the range 159.30 (12)–171.70 (15)°, while the cis ones vary from 73.02 (12) to 116.70 (16)°. The Cu⋯Cu distances within the Cu4O4 core are 3.1724 (8) and 3.4474 (8) Å.
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There are intramolecular O2—H2AO⋯O13 hydrogen bonds between a hydrogen atom of the water molecule and the oxygen atom of one hydroxymethyl group. A further intramolecular hydrogen bond involves the other hydroxymethyl group (O12). Bifurcated intermolecular hydrogen bonds are also present, involving the remaining hydrogen atom of water molecule and the phenolic and methoxyl oxygen atoms. These hydrogen-bond contacts are of weak-to-moderate strength [2.736 (12)–2.892 (7) Å], Table 2.
The title compound appears to be a new solvatomorph of the blue copper(II) complex with the same ligand, [Cu4(C12H15NO5)4(H2O)]·3.75CH3OH·2H2O (refcode SUGKUC; Tabassum & Usman, 2015). Monoclinic SUGKUC crystallizes in the P21/n and has no crystallographically imposed symmetry. It is also a cubane-type complex but with some of the coordinating water molecules replaced by other solvents. The bond lengths and angles of (1) are comparable to those in the NiII analogue (refcode ZEHGUQ; Guo et al., 2008) and a CuII complex with a similar ligand (refcode AFIMUY; Dong et al., 2007). The ligand of the latter does not have the methoxy group and the copper atom is five-coordinate, the structure lacking the coordinating water molecule of (1).
3. Supramolecular features
Interactions between [Cu4(H2L)4(H2O)4] molecules in the are weak, the closest Cu⋯Cu inter-cluster separation exceeds 8.43 Å. The hydrogen on the hydroxymethyl group (O13) is involved in an intermolecular hydrogen bond to the water molecule on the cluster related by a crystallographic twofold axis (Table 2), forming a hydrogen-bonded polymer propagating along the b axis (Fig. 2). No π–π stacking is observed.
4. Database survey
In the solid state, the H4L ligand adopts the keto–amine tautomeric form, with the formal aryl–OH H atom relocated to the N atom, and the NH group and phenolic O atom forming a strong intramolecular N—H⋯O hydrogen bond (Odabaşoğlu et al., 2003). Crystal structures of about 30 metal complexes of this ligand are found in the Cambridge Database (CSD Version 5.36 with one update; Groom & Allen, 2014). These comprise five homometallic mononuclear Mn, Ni and Mo complexes, polynuclear Co2, V2, Cu4, Mn4, Ni4, Ln9 and Ln10 assemblies and heterometallic 1s–3d and 3d–4f clusters of 4–20 nuclearity. The ligand molecules exist in either doubly or triply deprotonated forms and adopt a chelating-bridging mode, forming five- and six-membered rings. Obviously, the H4L ligand favours formation of polynuclear paramagnetic clusters due to the presence of the tripodal alcohol functionality. At the same time, the lack of heterometallic structures with two kinds of 3d metal supported by H4L is also evident. This perhaps explains the failure of the preparation of a Cu/Zn compound in the present study.
5. Synthesis and crystallization
2-Hydroxy-3-methoxy-benzaldehyde (0.30 g, 2 mmol), tris(hydroxymethyl)aminomethane (0.24 g, 2 mmol), NEt3 (0.3 ml, 2 mmol) were added to methanol (20 ml) and stirred magnetically for 30 min. Next copper powder (0.06 g, 1 mmol) and Zn(CH3COO)2 (0.19 g, 1 mmol) were added to the yellow solution and the mixture was heated to 323 K under stirring until total dissolution of the copper powder was observed (1 h). The resulting green solution was filtered and allowed to stand at room temperature. Dark-green rhombic prisms of the title compound were formed in several days. They were collected by filter-suction, washed with dry PriOH and finally dried in vacuo (yield: 59% based on copper).
The IR spectrum of (1) in the range 4000–400 cm−1 shows all the characteristic Schiff base ligand frequencies: ν(OH), ν(CH) and ν(C=N) at 3400, 3066–2840, and 1604 cm−1, respectively. A strong peak at 1628 cm−1 that is due to the bending of H2O molecule provides evidence of the presence of water in (1).
6. Refinement
Crystal data, data collection and structure . Diffraction data were collected at 200 K, rather than the more usual 100 K, due to apparent disordering at lower temperatures. Water molecule hydrogen atoms were refined with geometries restrained to ideal values; the OH hydrogen atoms H12 and H13 were refined using a riding model. All hydrogen atoms bound to carbon were included in calculated positions and refined using a riding model with isotropic displacement parameters based on those of the parent atom [C—H = 0.95 Å, Uiso(H) = 1.2Ueq(C) for CH and CH2, 1.5Ueq(C) for CH3). Anisotropic displacement parameters were employed for the non-hydrogen atoms.
details are summarized in Table 3
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Supporting information
CCDC reference: 1424781
10.1107/S2056989015017314/sj5474sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015017314/sj5474Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015017314/sj5474Isup3.pdf
\ During the last few years, we have been exploring the chemistry of transition metal complexes of Schiff base ligands with the aim of preparing heterometallic polynuclear compounds with diverse potential advantages. In these studies, we continued to apply the direct synthesis of coordination compounds based on spontaneous self-assembly, in which one of the metals is introduced as a powder (zerovalent state) and oxidized during the synthesis (typically by dioxygen from the air) (Pryma et al., 2003; Nesterova et al., 2008; Nesterov et al., 2012). The main advantage of this approach is the generation of building blocks in situ, in one reaction vessel, thus eliminating separate steps in building-block construction. Reactions of a metal powder and another metal salt in air with a solution containing a pre-formed Schiff base ligand have yielded a number of novel Co/Fe and Cu/Fe compounds (Chygorin et al., 2015; Nesterova et al., 2013).
The title compound was prepared in studies of the coordination behavior of the versatile multidentate Schiff base ligand 2-{[(2-hydroxy-3-methoxyphenyl)methylene]amino}-2-(hydroxymethyl)-1,3-\ propanediol (H4L) (Odabaşoğlu et al., 2003) which results from the condensation between o-vanillin and tris(hydroxymethyl)aminomethane. In the syntheses, the condensation reaction was utilized without isolation of the resulting Schiff base. In an attempt to prepare a heterometallic assembly we reacted Cu powder and Zn(CH3COO)2 with a methanol solution of the Schiff base in a 1:1:2 molar ratio. However, the isolated green microcrystalline product was identified crystallographically to be the tetranuclear CuII Schiff base complex Cu4(H2L)4(H2O)4 (1) of a cubane type.
The
of (1) has been reported previously at room temperature by Back et al. (2015) (refcode IGOSUU). In that report of the structure, no standard uncertainties are recorded for the oxygen atoms of the hydroxymethyl group, O2, and the water molecule coordinating to the metal atom, O6, indicating that they were not refined. The hydrogen atoms of some OH groups and water molecules have also not been positioned accurately. It is clear from the checkCIF output that at least one of the water molecule hydrogen atoms, H6B, and one OH hydrogen atom, H4, are incorrectly positioned. Since the present structure was determined at a lower temperature, all atoms, including these hydrogen atoms, have been determined more accurately, resulting in improved standard uncertainties in the bond lengths and angles.The neutral [Cu4(C12H15NO5)4(H2O)4] molecule of (1) has crystallographic 4 inversion symmetry. The CuII ions are coordinated by the tridentate Schiff base ligands and water molecules, forming a tetranuclear Cu4O4 cubane-like configuration. The ligand acts in a chelating–bridging mode via phenoxo-, alkoxo-O and imine-N atoms. The two hydroxymethyl groups remain protonated. The coordination about the Cu atom is distorted octahedral as a result of a significant Jahn–Teller distortion, the two axial distances Cu1—O2 2.738 (5) Å (to the water molecule) and the bridging bond, Cu1—O11 2.547 (4) Å, being significantly longer than the remainder which lie in the range 1.912 (4)–1.968 (3) Å (Fig. 1, Table 1). The trans angles at the metal atom lie in the range 159.30 (12)–171.70 (15)°, while the cis ones vary from 73.02 (12) to 116.70 (16)°. The Cu···Cu distances within the Cu4O4 core are 3.1724 (8) and 3.4474 (8) Å.
There are intramolecular O2—H2AO···O13 hydrogen bonds between a hydrogen atom of the water molecule and the oxygen atom of one hydroxymethyl group. A further intramolecular hydrogen bond involves the other hydroxymethyl group (O12). Bifurcated intermolecular hydrogen bonds are also present, involving the remaining hydrogen atom of water molecule and the phenolic and methoxyl oxygen atoms. These hydrogen-bond contacts are of weak-to-moderate strength [2.736 (12)–2.892 (7) Å], Table 2.
The title compound appears to be a new solvatomorph of the blue copper(II) complex with the same ligand, [Cu4(C12H15NO5)4(H2O)]·3.75CH3OH·2H2O (refcode SUGKUC; Tabassum & Usman, 2015). Monoclinic SUGKUC crystallizes in the P21/n
and has no crystallographically imposed symmetry. It is also a cubane-type complex but with some of the coordinating water molecules replaced by other solvents. The bond lengths and angles of (1) are comparable to those in the isomorphous NiII analogue (refcode ZEHGUQ; Guo et al., 2008) and a CuII complex with a similar ligand (refcode AFIMUY; Dong et al., 2007). The ligand of the latter does not have the methoxy group and the copper atom is five-coordinate, the structure lacking the coordinating water molecule of (1).Interactions between [Cu4(H2L)4(H2O)4] molecules in the π–π stacking is observed.
are weak, the closest Cu···Cu inter-cluster separation exceeds 8.43 Å. The hydrogen on the hydroxymethyl group (O13) is involved in an intermolecular hydrogen bond to the water molecule on the cluster related by a crystallographic twofold axis (Table 2), forming a hydrogen-bonded polymer propagating along the b axis (Fig. 2). NoIn the solid state, the H4L ligand adopts the keto–amine tautomeric form, with the formal aryl–OH H atom relocated to the N atom, and the NH group and phenolic O atom forming a strong intramolecular N—H···O hydrogen bond (Odabaşoğlu et al., 2003). Crystal structures of about 30 metal complexes of this ligand are found in the Cambridge Database (CSD Version 5.36 with one update; Groom & Allen, 2014). These comprise five homometallic mononuclear Mn, Ni and Mo complexes, polynuclear Co2, V2, Cu4, Mn4, Ni4, Ln9 and Ln10 assemblies and heterometallic 1s–3d and 3d–4f clusters of 4–20 nuclearity. The ligand molecules exist in either doubly or triply deprotonated forms and adopt a chelating-bridging mode, forming five- and six-membered rings. Obviously, the H4L ligand favours formation of polynuclear paramagnetic clusters due to the presence of the tripodal alcohol functionality. At the same time, the lack of heterometallic structures with two kinds of 3d metal supported by H4L is also evident. This perhaps explains the failure of the preparation of a Cu/Zn compound in the present study.
2-Hydroxy-3-methoxy-benzaldehyde (0.30 g, 2 mmol), tris(hydroxymethyl)aminomethane (0.24 g, 2 mmol), NEt3 (0.3 ml, 2 mmol) were added to methanol (20 ml) and stirred magnetically for 30 min. Next copper powder (0.06 g, 1 mmol) and Zn(CH3COO)2 (0.19 g, 1 mmol) were added to the yellow solution and the mixture was heated to 323 K under stirring until total dissolution of the copper powder was observed (1 hour). The resulting green solution was filtered and allowed to stand at room temperature. Dark-green rhombic prisms of the title compound were formed in several days. They were collected by filter-suction, washed with dry PriOH and finally dried in vacuo (yield: 59% based on copper).
The IR spectrum of (1) in the range 4000–400 cm–1 shows all the characteristic Schiff base ligand frequencies: ν(OH), ν(CH) and ν(C═N) at 3400, 3066–2840, and 1604 cm–1, respectively. A strong peak at 1628 cm–1 that is due to the bending of H2O molecule provides evidence of the presence of water in (1).
Crystal data, data collection and structure
details are summarized in Table 3. Diffraction data were collected at 200 K, rather than the more usual 100 K, due to apparent disordering at lower temperatures. Water molecule hydrogen atoms were refined with geometries restrained to ideal values; the OH hydrogen atoms H12 and H13 were refined using a riding model. All hydrogen atoms bound to carbon were included in calculated positions and refined using a riding model with isotropic displacement parameters based on those of the parent atom [C—H = 0.95 Å, Uiso(H) = 1.2Ueq(C) for CH and CH2, 1.5Ueq(C) for CH3). Anisotropic displacement parameters were employed for the non-hydrogen atoms.Data collection: CrysAlis CCD (Agilent, 2013); cell
CrysAlis CCD (Agilent, 2013); data reduction: CrysAlis CCD (Agilent, 2013); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).Fig. 1. The molecular structure of the title complex, showing the atom-numbering scheme. Non-H atoms are shown with displacement ellipsoids at the 50% probability level. H atoms are not shown. | |
Fig. 2. Part of the crystal structure with intra- and intermolecular hydrogen bonds shown as blue dashed lines. C—H hydrogens have been omitted for clarity. |
[Cu4(C12H15NO5)4(H2O)4] | Dx = 1.652 Mg m−3 |
Mr = 1339.22 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | Cell parameters from 7964 reflections |
Hall symbol: -I 4ad | θ = 2.8–28.9° |
a = 18.7108 (3) Å | µ = 1.65 mm−1 |
c = 15.3800 (3) Å | T = 200 K |
V = 5384.4 (2) Å3 | Prism, dark green |
Z = 4 | 0.39 × 0.23 × 0.17 mm |
F(000) = 2768 |
Oxford Diffraction Xcalibur diffractometer | 3247 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 2942 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
Detector resolution: 16.0009 pixels mm-1 | θmax = 28.0°, θmin = 2.8° |
ω scans | h = −23→24 |
Absorption correction: analytical (CrysAlis CCD and CrysAlis RED; Agilent, 2013) | k = −23→24 |
Tmin = 0.687, Tmax = 0.843 | l = −19→20 |
25330 measured reflections |
Refinement on F2 | 4 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.076 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.195 | w = 1/[σ2(Fo2) + (0.0811P)2 + 52.6317P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max < 0.001 |
3247 reflections | Δρmax = 1.58 e Å−3 |
188 parameters | Δρmin = −0.98 e Å−3 |
[Cu4(C12H15NO5)4(H2O)4] | Z = 4 |
Mr = 1339.22 | Mo Kα radiation |
Tetragonal, I41/a | µ = 1.65 mm−1 |
a = 18.7108 (3) Å | T = 200 K |
c = 15.3800 (3) Å | 0.39 × 0.23 × 0.17 mm |
V = 5384.4 (2) Å3 |
Oxford Diffraction Xcalibur diffractometer | 3247 independent reflections |
Absorption correction: analytical (CrysAlis CCD and CrysAlis RED; Agilent, 2013) | 2942 reflections with I > 2σ(I) |
Tmin = 0.687, Tmax = 0.843 | Rint = 0.044 |
25330 measured reflections |
R[F2 > 2σ(F2)] = 0.076 | 4 restraints |
wR(F2) = 0.195 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0811P)2 + 52.6317P] where P = (Fo2 + 2Fc2)/3 |
3247 reflections | Δρmax = 1.58 e Å−3 |
188 parameters | Δρmin = −0.98 e Å−3 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Diffraction data were collected at 200 K, rather than the more usual 100 K, due to apparent disordering at lower temperatures. Water molecule hydrogen atoms were refined with geometries restrained to ideal values. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.47922 (3) | 0.66025 (3) | 0.69100 (4) | 0.0279 (2) | |
C1 | 0.5392 (3) | 0.5347 (3) | 0.7698 (3) | 0.0355 (11) | |
O1 | 0.5448 (2) | 0.58332 (19) | 0.7095 (2) | 0.0350 (8) | |
C2 | 0.4880 (3) | 0.5355 (3) | 0.8386 (4) | 0.0384 (12) | |
C3 | 0.4858 (4) | 0.4778 (4) | 0.8971 (4) | 0.0533 (16) | |
H3 | 0.4506 | 0.4777 | 0.9416 | 0.064* | |
C4 | 0.5322 (5) | 0.4225 (4) | 0.8922 (5) | 0.063 (2) | |
H4 | 0.5285 | 0.3839 | 0.9322 | 0.076* | |
C5 | 0.5845 (5) | 0.4218 (3) | 0.8297 (5) | 0.062 (2) | |
H5 | 0.6179 | 0.3836 | 0.8277 | 0.075* | |
C6 | 0.5887 (4) | 0.4770 (3) | 0.7690 (4) | 0.0531 (16) | |
O6 | 0.6377 (4) | 0.4824 (3) | 0.7043 (4) | 0.0781 (18) | |
C61 | 0.6974 (6) | 0.4339 (5) | 0.7031 (7) | 0.094 (3) | |
H61A | 0.7184 | 0.4311 | 0.7614 | 0.14* | |
H61B | 0.7334 | 0.4512 | 0.6619 | 0.14* | |
H61C | 0.681 | 0.3863 | 0.6852 | 0.14* | |
C10 | 0.4376 (3) | 0.5937 (4) | 0.8514 (4) | 0.0453 (14) | |
H10 | 0.4063 | 0.5904 | 0.8999 | 0.054* | |
N10 | 0.4318 (2) | 0.6488 (3) | 0.8033 (3) | 0.0416 (11) | |
C101 | 0.3781 (4) | 0.7071 (4) | 0.8247 (4) | 0.0492 (15) | |
C11 | 0.3629 (3) | 0.7439 (3) | 0.7393 (4) | 0.0384 (12) | |
H11A | 0.3232 | 0.7186 | 0.7099 | 0.046* | |
H11B | 0.3468 | 0.7933 | 0.7513 | 0.046* | |
O11 | 0.42189 (18) | 0.7465 (2) | 0.6827 (2) | 0.0322 (7) | |
C12 | 0.4105 (5) | 0.7622 (4) | 0.8871 (5) | 0.065 (2) | |
H12A | 0.4533 | 0.7841 | 0.8601 | 0.078* | |
H12B | 0.3753 | 0.8006 | 0.8984 | 0.078* | |
O12 | 0.4299 (3) | 0.7293 (3) | 0.9664 (3) | 0.0827 (18) | |
H12 | 0.4473 | 0.76 | 1.0001 | 0.124* | |
C13 | 0.3123 (4) | 0.6764 (4) | 0.8649 (4) | 0.0551 (17) | |
H13A | 0.3232 | 0.6592 | 0.9243 | 0.066* | |
H13B | 0.2751 | 0.7139 | 0.8694 | 0.066* | |
O13 | 0.2862 (3) | 0.6191 (3) | 0.8141 (4) | 0.0724 (16) | |
H13 | 0.2492 | 0.6023 | 0.8374 | 0.109* | |
O2 | 0.3560 (3) | 0.5887 (2) | 0.6505 (3) | 0.0497 (10) | |
H2AO | 0.341 (4) | 0.618 (4) | 0.605 (3) | 0.075* | |
H2BO | 0.326 (4) | 0.601 (4) | 0.699 (3) | 0.075* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0264 (3) | 0.0308 (3) | 0.0265 (3) | −0.0006 (2) | −0.0008 (2) | 0.0045 (2) |
C1 | 0.044 (3) | 0.030 (2) | 0.033 (3) | −0.003 (2) | −0.013 (2) | 0.0002 (19) |
O1 | 0.0390 (19) | 0.0342 (18) | 0.0317 (17) | 0.0055 (15) | 0.0023 (15) | 0.0060 (14) |
C2 | 0.039 (3) | 0.042 (3) | 0.034 (3) | −0.010 (2) | −0.008 (2) | 0.008 (2) |
C3 | 0.062 (4) | 0.051 (4) | 0.046 (3) | −0.017 (3) | −0.009 (3) | 0.019 (3) |
C4 | 0.094 (6) | 0.042 (3) | 0.053 (4) | −0.008 (4) | −0.012 (4) | 0.015 (3) |
C5 | 0.101 (6) | 0.033 (3) | 0.052 (4) | 0.015 (3) | −0.012 (4) | 0.000 (3) |
C6 | 0.082 (5) | 0.033 (3) | 0.044 (3) | 0.014 (3) | −0.004 (3) | −0.004 (2) |
O6 | 0.105 (4) | 0.057 (3) | 0.073 (3) | 0.044 (3) | 0.023 (3) | 0.012 (3) |
C61 | 0.101 (7) | 0.074 (6) | 0.106 (8) | 0.046 (5) | 0.016 (6) | 0.006 (5) |
C10 | 0.033 (3) | 0.067 (4) | 0.036 (3) | 0.000 (3) | 0.002 (2) | 0.019 (3) |
N10 | 0.033 (2) | 0.054 (3) | 0.038 (2) | 0.011 (2) | 0.0041 (19) | 0.013 (2) |
C101 | 0.055 (4) | 0.054 (4) | 0.039 (3) | 0.020 (3) | 0.009 (3) | 0.002 (3) |
C11 | 0.039 (3) | 0.040 (3) | 0.037 (3) | 0.006 (2) | 0.009 (2) | −0.005 (2) |
O11 | 0.0298 (17) | 0.0392 (19) | 0.0274 (17) | 0.0051 (14) | −0.0015 (13) | 0.0032 (14) |
C12 | 0.095 (6) | 0.057 (4) | 0.042 (4) | 0.026 (4) | 0.006 (4) | −0.004 (3) |
O12 | 0.126 (5) | 0.081 (4) | 0.041 (3) | 0.019 (4) | −0.006 (3) | −0.003 (3) |
C13 | 0.060 (4) | 0.058 (4) | 0.047 (3) | 0.015 (3) | 0.025 (3) | 0.003 (3) |
O13 | 0.049 (3) | 0.083 (4) | 0.085 (4) | 0.002 (3) | 0.027 (3) | −0.004 (3) |
O2 | 0.060 (3) | 0.037 (2) | 0.053 (3) | −0.0002 (19) | 0.005 (2) | −0.0109 (19) |
Cu1—O1 | 1.912 (4) | C61—H61C | 0.98 |
Cu1—O11 | 1.941 (4) | C10—N10 | 1.273 (7) |
Cu1—N10 | 1.953 (5) | C10—H10 | 0.95 |
Cu1—O2 | 2.738 (5) | N10—C101 | 1.519 (7) |
Cu1—O11i | 1.968 (3) | C101—C13 | 1.494 (9) |
Cu1—O11ii | 2.547 (4) | C101—C11 | 1.510 (8) |
C1—O1 | 1.303 (6) | C101—C12 | 1.533 (11) |
C1—C6 | 1.422 (8) | C11—O11 | 1.407 (6) |
C1—C2 | 1.427 (8) | C11—H11A | 0.99 |
C2—C3 | 1.406 (8) | C11—H11B | 0.99 |
C2—C10 | 1.455 (9) | O11—Cu1iii | 1.968 (3) |
C3—C4 | 1.353 (11) | C12—O12 | 1.414 (9) |
C3—H3 | 0.95 | C12—H12A | 0.99 |
C4—C5 | 1.373 (11) | C12—H12B | 0.99 |
C4—H4 | 0.95 | O12—H12 | 0.84 |
C5—C6 | 1.394 (9) | C13—O13 | 1.413 (9) |
C5—H5 | 0.95 | C13—H13A | 0.99 |
C6—O6 | 1.356 (9) | C13—H13B | 0.99 |
O6—C61 | 1.439 (9) | O13—H13 | 0.84 |
C61—H61A | 0.98 | O2—H2AO | 0.93 (5) |
C61—H61B | 0.98 | O2—H2BO | 0.96 (5) |
O1—Cu1—O11 | 171.70 (15) | H61A—C61—H61B | 109.5 |
O1—Cu1—N10 | 94.41 (17) | O6—C61—H61C | 109.5 |
O11—Cu1—N10 | 84.16 (17) | H61A—C61—H61C | 109.5 |
N10—Cu1—O2 | 76.41 (16) | H61B—C61—H61C | 109.5 |
O11—Cu1—O2 | 85.77 (14) | N10—C10—C2 | 125.6 (5) |
O1—Cu1—O2 | 101.89 (14) | N10—C10—H10 | 117.2 |
O1—Cu1—O11i | 94.54 (15) | C2—C10—H10 | 117.2 |
O11—Cu1—O11i | 88.41 (16) | C10—N10—C101 | 120.8 (5) |
N10—Cu1—O11i | 166.34 (18) | C10—N10—Cu1 | 124.3 (4) |
O2—Cu1—O11ii | 159.30 (12) | C101—N10—Cu1 | 114.4 (3) |
O1—Cu1—O11i | 94.54 (15) | C13—C101—C11 | 112.3 (6) |
O11—Cu1—O11i | 88.44 (16) | C13—C101—N10 | 111.0 (5) |
O1—Cu1—O11ii | 93.29 (13) | C11—C101—N10 | 105.3 (4) |
N10—Cu1—O11ii | 116.70 (16) | C13—C101—C12 | 109.1 (6) |
O11—Cu1—O11ii | 80.15 (13) | C11—C101—C12 | 108.2 (6) |
O11i—Cu1—O11ii | 73.02 (12) | N10—C101—C12 | 110.9 (5) |
O2—Cu1—O11i | 91.64 (15) | O11—C11—C101 | 113.9 (5) |
O2—Cu1—O11ii | 159.32 (12) | O11—C11—H11A | 108.8 |
O1—C1—C6 | 118.1 (5) | C101—C11—H11A | 108.8 |
O1—C1—C2 | 125.1 (5) | O11—C11—H11B | 108.8 |
C6—C1—C2 | 116.8 (5) | C101—C11—H11B | 108.8 |
C1—O1—Cu1 | 125.5 (3) | H11A—C11—H11B | 107.7 |
C3—C2—C1 | 119.2 (6) | C11—O11—Cu1 | 111.4 (3) |
C3—C2—C10 | 118.0 (6) | C11—O11—Cu1iii | 121.3 (3) |
C1—C2—C10 | 122.9 (5) | Cu1—O11—Cu1iii | 108.47 (17) |
C4—C3—C2 | 122.2 (7) | O12—C12—C101 | 110.4 (6) |
C4—C3—H3 | 118.9 | O12—C12—H12A | 109.6 |
C2—C3—H3 | 118.9 | C101—C12—H12A | 109.6 |
C3—C4—C5 | 120.2 (6) | O12—C12—H12B | 109.6 |
C3—C4—H4 | 119.9 | C101—C12—H12B | 109.6 |
C5—C4—H4 | 119.9 | H12A—C12—H12B | 108.1 |
C4—C5—C6 | 120.2 (7) | C12—O12—H12 | 109.5 |
C4—C5—H5 | 119.9 | O13—C13—C101 | 110.4 (5) |
C6—C5—H5 | 119.9 | O13—C13—H13A | 109.6 |
O6—C6—C5 | 125.7 (6) | C101—C13—H13A | 109.6 |
O6—C6—C1 | 113.0 (5) | O13—C13—H13B | 109.6 |
C5—C6—C1 | 121.3 (7) | C101—C13—H13B | 109.6 |
C6—O6—C61 | 119.2 (6) | H13A—C13—H13B | 108.1 |
O6—C61—H61A | 109.5 | C13—O13—H13 | 109.5 |
O6—C61—H61B | 109.5 | H2AO—O2—H2BO | 105 (3) |
Symmetry codes: (i) −y+5/4, x+1/4, −z+5/4; (ii) −x+1, −y+3/2, z; (iii) y−1/4, −x+5/4, −z+5/4. |
D—H···A | D—H | H···A | D···A | D—H···A |
O12—H12···O12ii | 0.84 | 2.37 | 2.736 (12) | 107 |
O13—H13···O2iv | 0.84 | 1.91 | 2.700 (6) | 156 |
O2—H2AO···O1iii | 0.93 (5) | 1.92 (4) | 2.791 (6) | 155 (8) |
O2—H2AO···O6iii | 0.93 (5) | 2.23 (7) | 2.853 (7) | 124 (6) |
O2—H2BO···O13 | 0.96 (5) | 1.95 (3) | 2.892 (7) | 165 (6) |
Symmetry codes: (ii) −x+1, −y+3/2, z; (iii) y−1/4, −x+5/4, −z+5/4; (iv) −y+3/4, x+1/4, z+1/4. |
Cu1—O1 | 1.912 (4) | Cu1—O2 | 2.738 (5) |
Cu1—O11 | 1.941 (4) | Cu1—O11i | 1.968 (3) |
Cu1—N10 | 1.953 (5) | Cu1—O11ii | 2.547 (4) |
Symmetry codes: (i) −y+5/4, x+1/4, −z+5/4; (ii) −x+1, −y+3/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O12—H12···O12ii | 0.84 | 2.37 | 2.736 (12) | 107.4 |
O13—H13···O2iii | 0.84 | 1.91 | 2.700 (6) | 155.8 |
O2—H2AO···O1iv | 0.93 (5) | 1.92 (4) | 2.791 (6) | 155 (8) |
O2—H2AO···O6iv | 0.93 (5) | 2.23 (7) | 2.853 (7) | 124 (6) |
O2—H2BO···O13 | 0.96 (5) | 1.95 (3) | 2.892 (7) | 165 (6) |
Symmetry codes: (ii) −x+1, −y+3/2, z; (iii) −y+3/4, x+1/4, z+1/4; (iv) y−1/4, −x+5/4, −z+5/4. |
Experimental details
Crystal data | |
Chemical formula | [Cu4(C12H15NO5)4(H2O)4] |
Mr | 1339.22 |
Crystal system, space group | Tetragonal, I41/a |
Temperature (K) | 200 |
a, c (Å) | 18.7108 (3), 15.3800 (3) |
V (Å3) | 5384.4 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.65 |
Crystal size (mm) | 0.39 × 0.23 × 0.17 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur diffractometer |
Absorption correction | Analytical (CrysAlis CCD and CrysAlis RED; Agilent, 2013) |
Tmin, Tmax | 0.687, 0.843 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25330, 3247, 2942 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.660 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.076, 0.195, 1.12 |
No. of reflections | 3247 |
No. of parameters | 188 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
w = 1/[σ2(Fo2) + (0.0811P)2 + 52.6317P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.58, −0.98 |
Computer programs: CrysAlis CCD (Agilent, 2013), SIR92 (Altomare et al., 1994), SHELXL2014 (Sheldrick, 2015), DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 2012).
Acknowledgements
The authors acknowledge the facilities, scientific and technical assistance of the Australian Microscopy & Microanalysis Research Facility at the Centre for Microscopy, Characterization & Analysis, the University of Western Australia, a facility funded by the University, State and Commonwealth Governments.
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