research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 10| October 2015| Pages 1203-1206

Crystal structure of tetra­kis­(μ3-2-{[1,1-bis­­(hy­dr­oxy­meth­yl)-2-oxidoeth­yl]imino­meth­yl}-6-meth­­oxy­phenolato)tetra­kis­[aqua­copper(II)]: a redetermination at 200 K

CROSSMARK_Color_square_no_text.svg

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

Edited by J. Simpson, University of Otago, New Zealand (Received 10 September 2015; accepted 16 September 2015; online 26 September 2015)

The crystal structure of the tetra­nuclear title compound, [Cu4(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 crystal lattice, the neutral clusters are linked by inter­molecular O—H⋯O hydrogen bonds into a one-dimensional hydrogen-bonding network propagating along the b axis.

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[Pryma, O. V., Petrusenko, S. R., Kokozay, V. N., Skelton, B. W., Shishkin, O. V. & Teplytska, T. S. (2003). Eur. J. Inorg. Chem. pp. 1426-1432.]; Nesterova et al., 2008[Nesterova, O. V., Petrusenko, S. R., Kokozay, V. N., Skelton, B. W., Jezierska, J., Linert, W. & Ozarowski, A. (2008). Dalton Trans. pp. 1431-1436.]; Nesterov et al., 2012[Nesterov, D. S., Chygorin, E. N., Kokozay, V. N., Bon, V. V., Boča, R., Kozlov, Y. N., Shul'pina, L. S., Jezierska, J., Ozarowski, A., Pombeiro, A. J. L. & Shul'pin, G. B. (2012). Inorg. Chem. 51, 9110-9122.]). 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[Chygorin, E. N., Kokozay, V. N., Omelchenko, I. V., Shishkin, O. V., Titiš, J., Boča, R. & Nesterov, D. S. (2015). Dalton Trans. 44, 10918-10922.]; Nesterova et al., 2013[Nesterova, O. V., Chygorin, E. N., Kokozay, V. N., Bon, V. V., Omelchenko, I. V., Shishkin, O. V., Titiš, J., Boča, R., Pombeiro, A. J. & Ozarowski, A. (2013). Dalton Trans. 42, 16909-16919.]).

[Scheme 1]

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[Odabas˛oǧlu, M., Albayrak, Ç., Büyükgüngör, O. & Lönnecke, P. (2003). Acta Cryst. C59, o616-o619.]) 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 crystal structure of (1) has been reported previously at room temperature by Back et al. (2015[Back, D. F., Oliveira, G. M., Canabarro, C. M. & Iglesias, B. A. (2015). Z. Anorg. Allg. Chem. 641, 941-947.]) (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.

2. Structural commentary

The neutral [Cu4(C12H15NO5)4(H2O)4] mol­ecule of (1) has crystallographic [\overline{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 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[link], Table 1[link]). 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.

Table 1
Selected bond lengths (Å)

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+{\script{5\over 4}}, x+{\script{1\over 4}}, -z+{\script{5\over 4}}]; (ii) [-x+1, -y+{\script{3\over 2}}, z].
[Figure 1]
Figure 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.

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[link].

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O12—H12⋯O12ii 0.84 2.37 2.736 (12) 107
O13—H13⋯O2iii 0.84 1.91 2.700 (6) 156
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+{\script{3\over 2}}, z]; (iii) [-y+{\script{3\over 4}}, x+{\script{1\over 4}}, z+{\script{1\over 4}}]; (iv) [y-{\script{1\over 4}}, -x+{\script{5\over 4}}, -z+{\script{5\over 4}}].

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[Tabassum, S. & Usman, M. (2015). Private communication.]). Monoclinic SUGKUC crystallizes in the P21/n space group 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[Guo, Y., Li, L., Liu, Y., Dong, J. & Wang, D. (2008). Acta Cryst. E64, m675-m676.]) and a CuII complex with a similar ligand (refcode AFIMUY; Dong et al., 2007[Dong, J.-F., Li, L.-Z., Xu, H.-Y. & Wang, D.-Q. (2007). Acta Cryst. E63, m2300.]). 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 crystal lattice 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[link]), forming a hydrogen-bonded polymer propagating along the b axis (Fig. 2[link]). No ππ stacking is observed.

[Figure 2]
Figure 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.

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[Odabas˛oǧlu, M., Albayrak, Ç., Büyükgüngör, O. & Lönnecke, P. (2003). Acta Cryst. C59, o616-o619.]). 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[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]). 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 refinement details are summarized in Table 3[link]. 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.

Table 3
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)
V3) 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
Absorption correction Analytical (CrysAlis CCD and CrysAlis RED; Agilent, 2013[Agilent (2013). CrysAlis CCD and CrysAlis RED. Agilent Corporation, Yarnton, England.])
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−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
Δρmax, Δρmin (e Å−3) 1.58, −0.98
Computer programs: CrysAlis CCD (Agilent, 2013[Agilent (2013). CrysAlis CCD and CrysAlis RED. Agilent Corporation, Yarnton, England.]), SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]) and WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]).

Supporting information


Chemical context top

\ 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 crystal structure 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.

Structural commentary top

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 space group 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).

Supra­molecular features top

Inter­actions between [Cu4(H2L)4(H2O)4] molecules in the crystal lattice 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 ππ stacking is observed.

Database survey top

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.

Synthesis and crystallization top

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(CN) 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).

Refinement top

Crystal data, data collection and structure refinement 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.

Computing details top

Data collection: CrysAlis CCD (Agilent, 2013); cell refinement: 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).

Figures top
[Figure 1] 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.
[Figure 2] 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.
Tetrakis(µ3-2-{[1,1-bis(hydroxymethyl)-2-oxidoethyl]iminomethyl}-6-methoxyphenolato)tetrakis[aquacopper(II)] top
Crystal data top
[Cu4(C12H15NO5)4(H2O)4]Dx = 1.652 Mg m3
Mr = 1339.22Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/aCell parameters from 7964 reflections
Hall symbol: -I 4adθ = 2.8–28.9°
a = 18.7108 (3) ŵ = 1.65 mm1
c = 15.3800 (3) ÅT = 200 K
V = 5384.4 (2) Å3Prism, dark green
Z = 40.39 × 0.23 × 0.17 mm
F(000) = 2768
Data collection top
Oxford Diffraction Xcalibur
diffractometer
3247 independent reflections
Radiation source: Enhance (Mo) X-ray Source2942 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
Detector resolution: 16.0009 pixels mm-1θmax = 28.0°, θmin = 2.8°
ω scansh = 2324
Absorption correction: analytical
(CrysAlis CCD and CrysAlis RED; Agilent, 2013)
k = 2324
Tmin = 0.687, Tmax = 0.843l = 1920
25330 measured reflections
Refinement top
Refinement on F24 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.076H 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 reflectionsΔρmax = 1.58 e Å3
188 parametersΔρmin = 0.98 e Å3
Crystal data top
[Cu4(C12H15NO5)4(H2O)4]Z = 4
Mr = 1339.22Mo Kα radiation
Tetragonal, I41/aµ = 1.65 mm1
a = 18.7108 (3) ÅT = 200 K
c = 15.3800 (3) Å0.39 × 0.23 × 0.17 mm
V = 5384.4 (2) Å3
Data collection top
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 = 0.843Rint = 0.044
25330 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0764 restraints
wR(F2) = 0.195H 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 reflectionsΔρmax = 1.58 e Å3
188 parametersΔρmin = 0.98 e Å3
Special details top

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

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.47922 (3)0.66025 (3)0.69100 (4)0.0279 (2)
C10.5392 (3)0.5347 (3)0.7698 (3)0.0355 (11)
O10.5448 (2)0.58332 (19)0.7095 (2)0.0350 (8)
C20.4880 (3)0.5355 (3)0.8386 (4)0.0384 (12)
C30.4858 (4)0.4778 (4)0.8971 (4)0.0533 (16)
H30.45060.47770.94160.064*
C40.5322 (5)0.4225 (4)0.8922 (5)0.063 (2)
H40.52850.38390.93220.076*
C50.5845 (5)0.4218 (3)0.8297 (5)0.062 (2)
H50.61790.38360.82770.075*
C60.5887 (4)0.4770 (3)0.7690 (4)0.0531 (16)
O60.6377 (4)0.4824 (3)0.7043 (4)0.0781 (18)
C610.6974 (6)0.4339 (5)0.7031 (7)0.094 (3)
H61A0.71840.43110.76140.14*
H61B0.73340.45120.66190.14*
H61C0.6810.38630.68520.14*
C100.4376 (3)0.5937 (4)0.8514 (4)0.0453 (14)
H100.40630.59040.89990.054*
N100.4318 (2)0.6488 (3)0.8033 (3)0.0416 (11)
C1010.3781 (4)0.7071 (4)0.8247 (4)0.0492 (15)
C110.3629 (3)0.7439 (3)0.7393 (4)0.0384 (12)
H11A0.32320.71860.70990.046*
H11B0.34680.79330.75130.046*
O110.42189 (18)0.7465 (2)0.6827 (2)0.0322 (7)
C120.4105 (5)0.7622 (4)0.8871 (5)0.065 (2)
H12A0.45330.78410.86010.078*
H12B0.37530.80060.89840.078*
O120.4299 (3)0.7293 (3)0.9664 (3)0.0827 (18)
H120.44730.761.00010.124*
C130.3123 (4)0.6764 (4)0.8649 (4)0.0551 (17)
H13A0.32320.65920.92430.066*
H13B0.27510.71390.86940.066*
O130.2862 (3)0.6191 (3)0.8141 (4)0.0724 (16)
H130.24920.60230.83740.109*
O20.3560 (3)0.5887 (2)0.6505 (3)0.0497 (10)
H2AO0.341 (4)0.618 (4)0.605 (3)0.075*
H2BO0.326 (4)0.601 (4)0.699 (3)0.075*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0264 (3)0.0308 (3)0.0265 (3)0.0006 (2)0.0008 (2)0.0045 (2)
C10.044 (3)0.030 (2)0.033 (3)0.003 (2)0.013 (2)0.0002 (19)
O10.0390 (19)0.0342 (18)0.0317 (17)0.0055 (15)0.0023 (15)0.0060 (14)
C20.039 (3)0.042 (3)0.034 (3)0.010 (2)0.008 (2)0.008 (2)
C30.062 (4)0.051 (4)0.046 (3)0.017 (3)0.009 (3)0.019 (3)
C40.094 (6)0.042 (3)0.053 (4)0.008 (4)0.012 (4)0.015 (3)
C50.101 (6)0.033 (3)0.052 (4)0.015 (3)0.012 (4)0.000 (3)
C60.082 (5)0.033 (3)0.044 (3)0.014 (3)0.004 (3)0.004 (2)
O60.105 (4)0.057 (3)0.073 (3)0.044 (3)0.023 (3)0.012 (3)
C610.101 (7)0.074 (6)0.106 (8)0.046 (5)0.016 (6)0.006 (5)
C100.033 (3)0.067 (4)0.036 (3)0.000 (3)0.002 (2)0.019 (3)
N100.033 (2)0.054 (3)0.038 (2)0.011 (2)0.0041 (19)0.013 (2)
C1010.055 (4)0.054 (4)0.039 (3)0.020 (3)0.009 (3)0.002 (3)
C110.039 (3)0.040 (3)0.037 (3)0.006 (2)0.009 (2)0.005 (2)
O110.0298 (17)0.0392 (19)0.0274 (17)0.0051 (14)0.0015 (13)0.0032 (14)
C120.095 (6)0.057 (4)0.042 (4)0.026 (4)0.006 (4)0.004 (3)
O120.126 (5)0.081 (4)0.041 (3)0.019 (4)0.006 (3)0.003 (3)
C130.060 (4)0.058 (4)0.047 (3)0.015 (3)0.025 (3)0.003 (3)
O130.049 (3)0.083 (4)0.085 (4)0.002 (3)0.027 (3)0.004 (3)
O20.060 (3)0.037 (2)0.053 (3)0.0002 (19)0.005 (2)0.0109 (19)
Geometric parameters (Å, º) top
Cu1—O11.912 (4)C61—H61C0.98
Cu1—O111.941 (4)C10—N101.273 (7)
Cu1—N101.953 (5)C10—H100.95
Cu1—O22.738 (5)N10—C1011.519 (7)
Cu1—O11i1.968 (3)C101—C131.494 (9)
Cu1—O11ii2.547 (4)C101—C111.510 (8)
C1—O11.303 (6)C101—C121.533 (11)
C1—C61.422 (8)C11—O111.407 (6)
C1—C21.427 (8)C11—H11A0.99
C2—C31.406 (8)C11—H11B0.99
C2—C101.455 (9)O11—Cu1iii1.968 (3)
C3—C41.353 (11)C12—O121.414 (9)
C3—H30.95C12—H12A0.99
C4—C51.373 (11)C12—H12B0.99
C4—H40.95O12—H120.84
C5—C61.394 (9)C13—O131.413 (9)
C5—H50.95C13—H13A0.99
C6—O61.356 (9)C13—H13B0.99
O6—C611.439 (9)O13—H130.84
C61—H61A0.98O2—H2AO0.93 (5)
C61—H61B0.98O2—H2BO0.96 (5)
O1—Cu1—O11171.70 (15)H61A—C61—H61B109.5
O1—Cu1—N1094.41 (17)O6—C61—H61C109.5
O11—Cu1—N1084.16 (17)H61A—C61—H61C109.5
N10—Cu1—O276.41 (16)H61B—C61—H61C109.5
O11—Cu1—O285.77 (14)N10—C10—C2125.6 (5)
O1—Cu1—O2101.89 (14)N10—C10—H10117.2
O1—Cu1—O11i94.54 (15)C2—C10—H10117.2
O11—Cu1—O11i88.41 (16)C10—N10—C101120.8 (5)
N10—Cu1—O11i166.34 (18)C10—N10—Cu1124.3 (4)
O2—Cu1—O11ii159.30 (12)C101—N10—Cu1114.4 (3)
O1—Cu1—O11i94.54 (15)C13—C101—C11112.3 (6)
O11—Cu1—O11i88.44 (16)C13—C101—N10111.0 (5)
O1—Cu1—O11ii93.29 (13)C11—C101—N10105.3 (4)
N10—Cu1—O11ii116.70 (16)C13—C101—C12109.1 (6)
O11—Cu1—O11ii80.15 (13)C11—C101—C12108.2 (6)
O11i—Cu1—O11ii73.02 (12)N10—C101—C12110.9 (5)
O2—Cu1—O11i91.64 (15)O11—C11—C101113.9 (5)
O2—Cu1—O11ii159.32 (12)O11—C11—H11A108.8
O1—C1—C6118.1 (5)C101—C11—H11A108.8
O1—C1—C2125.1 (5)O11—C11—H11B108.8
C6—C1—C2116.8 (5)C101—C11—H11B108.8
C1—O1—Cu1125.5 (3)H11A—C11—H11B107.7
C3—C2—C1119.2 (6)C11—O11—Cu1111.4 (3)
C3—C2—C10118.0 (6)C11—O11—Cu1iii121.3 (3)
C1—C2—C10122.9 (5)Cu1—O11—Cu1iii108.47 (17)
C4—C3—C2122.2 (7)O12—C12—C101110.4 (6)
C4—C3—H3118.9O12—C12—H12A109.6
C2—C3—H3118.9C101—C12—H12A109.6
C3—C4—C5120.2 (6)O12—C12—H12B109.6
C3—C4—H4119.9C101—C12—H12B109.6
C5—C4—H4119.9H12A—C12—H12B108.1
C4—C5—C6120.2 (7)C12—O12—H12109.5
C4—C5—H5119.9O13—C13—C101110.4 (5)
C6—C5—H5119.9O13—C13—H13A109.6
O6—C6—C5125.7 (6)C101—C13—H13A109.6
O6—C6—C1113.0 (5)O13—C13—H13B109.6
C5—C6—C1121.3 (7)C101—C13—H13B109.6
C6—O6—C61119.2 (6)H13A—C13—H13B108.1
O6—C61—H61A109.5C13—O13—H13109.5
O6—C61—H61B109.5H2AO—O2—H2BO105 (3)
Symmetry codes: (i) y+5/4, x+1/4, z+5/4; (ii) x+1, y+3/2, z; (iii) y1/4, x+5/4, z+5/4.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O12—H12···O12ii0.842.372.736 (12)107
O13—H13···O2iv0.841.912.700 (6)156
O2—H2AO···O1iii0.93 (5)1.92 (4)2.791 (6)155 (8)
O2—H2AO···O6iii0.93 (5)2.23 (7)2.853 (7)124 (6)
O2—H2BO···O130.96 (5)1.95 (3)2.892 (7)165 (6)
Symmetry codes: (ii) x+1, y+3/2, z; (iii) y1/4, x+5/4, z+5/4; (iv) y+3/4, x+1/4, z+1/4.
Selected bond lengths (Å) top
Cu1—O11.912 (4)Cu1—O22.738 (5)
Cu1—O111.941 (4)Cu1—O11i1.968 (3)
Cu1—N101.953 (5)Cu1—O11ii2.547 (4)
Symmetry codes: (i) y+5/4, x+1/4, z+5/4; (ii) x+1, y+3/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O12—H12···O12ii0.842.372.736 (12)107.4
O13—H13···O2iii0.841.912.700 (6)155.8
O2—H2AO···O1iv0.93 (5)1.92 (4)2.791 (6)155 (8)
O2—H2AO···O6iv0.93 (5)2.23 (7)2.853 (7)124 (6)
O2—H2BO···O130.96 (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) y1/4, x+5/4, z+5/4.

Experimental details

Crystal data
Chemical formula[Cu4(C12H15NO5)4(H2O)4]
Mr1339.22
Crystal system, space groupTetragonal, I41/a
Temperature (K)200
a, c (Å)18.7108 (3), 15.3800 (3)
V3)5384.4 (2)
Z4
Radiation typeMo Kα
µ (mm1)1.65
Crystal size (mm)0.39 × 0.23 × 0.17
Data collection
DiffractometerOxford Diffraction Xcalibur
diffractometer
Absorption correctionAnalytical
(CrysAlis CCD and CrysAlis RED; Agilent, 2013)
Tmin, Tmax0.687, 0.843
No. of measured, independent and
observed [I > 2σ(I)] reflections
25330, 3247, 2942
Rint0.044
(sin θ/λ)max1)0.660
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.076, 0.195, 1.12
No. of reflections3247
No. of parameters188
No. of restraints4
H-atom treatmentH 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 Å3)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.

References

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Volume 71| Part 10| October 2015| Pages 1203-1206
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