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

Buvaylo, E.A.; Vassilyeva, O.Y.; Skelton, B.W.

doi:10.1107/S2056989015017314

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

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

doi:10.1107/S2056989015017314

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

Elena A. Buvaylo,^a Olga Yu. Vassilyeva ^a ^* and Brian W. Skelton ^b

^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 Cu^II ions are coordinated by the tridentate Schiff base ligands and water molecules, forming a tetranuclear Cu₄O₄ cubane-like core. The Cu^II ion adopts a CuNO₅ elongated octahedral environment. The coordination environment of Cu^II 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.

Keywords: crystal structure; Cu^II 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 Cu^II 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 ) (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 Cu^II 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^II 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.

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
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.

Table 2
Hydrogen-bond geometry (Å, °)

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⋯O2ⁱⁱⁱ	0.84	1.91	2.700 (6)	156
O2—H2AO⋯O1^iv	0.93 (5)	1.92 (4)	2.791 (6)	155 (8)
O2—H2AO⋯O6^iv	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 ). 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 Ni^II analogue (refcode ZEHGUQ; Guo et al., 2008 ) and a Cu^II 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 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 π–π stacking is observed.

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). 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 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, U_iso(H) = 1.2U_eq(C) for CH and CH₂, 1.5U_eq(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]
M_r	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
Absorption correction	Analytical (CrysAlis CCD and CrysAlis RED; Agilent, 2013 )
T_min, T_max	0.687, 0.843
No. of measured, independent and observed [I > 2σ(I)] reflections	25330, 3247, 2942
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	1.58, −0.98
Computer programs: CrysAlis CCD (Agilent, 2013), SIR92 (Altomare et al., 1994 ), SHELXL2014 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 1999 ) and WinGX (Farrugia, 2012 ).

Supporting information

CCDC reference: 1424781

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2056989015017314/sj5474sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015017314/sj5474Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015017314/sj5474Isup3.pdf

checkCIF report

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 Cu^II 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 Cu^II 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 Ni^II analogue (refcode ZEHGUQ; Guo et al., 2008) and a Cu^II 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 π–π 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(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).

Refinement top

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

	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.

Tetrakis(µ₃-2-{[1,1-bis(hydroxymethyl)-2-oxidoethyl]iminomethyl}-6-methoxyphenolato)tetrakis[aquacopper(II)] top

Crystal data top

[Cu₄(C₁₂H₁₅NO₅)₄(H₂O)₄]	D_x = 1.652 Mg m⁻³
M_r = 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

Data collection top

Oxford Diffraction Xcalibur diffractometer	3247 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2942 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
Detector resolution: 16.0009 pixels mm^-1	θ_max = 28.0°, θ_min = 2.8°
ω scans	h = −23→24
Absorption correction: analytical (CrysAlis CCD and CrysAlis RED; Agilent, 2013)	k = −23→24
T_min = 0.687, T_max = 0.843	l = −19→20
25330 measured reflections

Refinement top

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(F_o²) + (0.0811P)² + 52.6317P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max < 0.001
3247 reflections	Δρ_max = 1.58 e Å⁻³
188 parameters	Δρ_min = −0.98 e Å⁻³

Crystal data top

[Cu₄(C₁₂H₁₅NO₅)₄(H₂O)₄]	Z = 4
M_r = 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

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)
T_min = 0.687, T_max = 0.843	R_int = 0.044
25330 measured reflections

Refinement top

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(F_o²) + (0.0811P)² + 52.6317P] where P = (F_o² + 2F_c²)/3
3247 reflections	Δρ_max = 1.58 e Å⁻³
188 parameters	Δρ_min = −0.98 e Å⁻³

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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···O2^iv	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.

Selected bond lengths (Å) top

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.

Hydrogen-bond geometry (Å, º) top

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···O1^iv	0.93 (5)	1.92 (4)	2.791 (6)	155 (8)
O2—H2AO···O6^iv	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]
M_r	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)
T_min, T_max	0.687, 0.843
No. of measured, independent and observed [I > 2σ(I)] reflections	25330, 3247, 2942
R_int	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(F_o²) + (0.0811P)² + 52.6317P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (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.

References

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

doi:10.1107/S2056989015017314

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