supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

Acta Cryst. (2009). E65, m1393    [ doi:10.1107/S1600536809042238 ]

Aqua[N-(2,5-dihydroxybenzyl)iminodiacetato]copper(II)

X.-Q. Zhang, F.-P. Huang, H.-D. Bian, Q. Yu and H. Liang

Abstract top

The title complex, [Cu(C11H11NO6)(H2O)], contains a CuII atom in a distorted square-pyramidal geometry. The metal centre is coordinated in the basal sites by one water molecule and two carboxylate O atoms and one N atom of the tetradentate ligand [Cu-O range, 1.9376 (11)-1.9541 (12), Cu-N, 1.9929 (12) Å] while the apical site is occupied by a hydroquinone O donor atom [Cu-O, 2.3746 (12) Å]. Intermolecular hydrogen bonding interactions involving both hydroquinone hydroxy groups and the coordinated water as donors give a three-dimensional framework structure.

Comment top

p-Hydroquinones, along with their oxidation products p-semiquinones and p-quinones, are very important in the oxidative maintenance of biological amine levels (Dooley et al., 1998), tissue formation (Wang et al., 1996), photosynthesis (Calvo et al., 2000) and aerobic respiration (Iwata et al., 1998). These compounds are involved in interesting organic electron- and hydrogen-transfer systems, e.g. electron-transfer reactions between transition metal centers and p-quinone cofactors are vital for all life (Drouza et al., 2002), occurring in key biological processes. As part of a series of the studies (Huang et al., 2008), we report here the synthesis and structure of the title compound, a new CuII complex with the related ligand 2-[N,N-bis(carboxylatomethyl)aminomethyl]hydroquinone. The molecular structure of the title compound [Cu(C11H11NO6)(H2O)] (I) is shown in Fig. 1. The CuII atom has a distorted square-pyramidal geometry with a τ parameter of 0.09 (Addison et al., 1984). The basal sites are occupied by one water molecule, as well as two carboxylate O atoms and one N atom of the ligand. In the apical position, the O atom of the hydroxybenzene coordinates to the CuII atom. All bond distances and bond angles have normal values. The crystal packing of (I) (Fig. 2) involves intermolecular O—H···O hydrogen bonds (Table 1). The non-coordinated carboxylate O2 atom accepts intermolecular hydrogen bonds from the coordinated hydroxy O (O5) of the hydroquinone ligand and from the coordinated water (O7). The non-coordinated carboxylate O4 atom is also an acceptor for a water H donor in an intermolecular hydrogen bond. The coordinated atom O3 accepts a hydrogen bond from the non-coordinated hydroquinone O (O6). These interactions result in a three-dimensional hydrogen-bonded framework structure.

Related literature top

For general background to p-hydroquinones and their oxidation products p-semiquinones and p-quinones, see: Dooley et al. (1998); Wang et al. (1996); Calvo et al. (2000); Iwata et al. (1998); Drouza et al. (2002); Huang et al. (2008); Addison et al. (1984). For the synthesis, see Fan (1992).

Experimental top

The ligand 2-[N,N-bis(carboxylatomethyl)aminomethyl]hydroquinone was prepared according to a literature procedure (Fan et al., 1992). The title complex was synthesized by the addition of CuCl2.2H2O (0.0850 g, 0.5 mmol) to 20 ml of a methanol solution containing the ligand (0.1275 g, 0.5 mmol). The resulting solution was stirred for 3 h at 60°C, and then cooled and filtered. Blue single crystal blocks were isolated from the solution at room temperature over six days.

Refinement top

H atoms on C atoms were positoned geometrically with C—Haromatic = 0.93 Å and C—Haliphatic = 0.97 Å and treated as riding with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2005).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of (I) with the atom-numbering scheme and 30% displacement ellipsoids.
[Figure 2] Fig. 2. The packing for (I), showing hydrogen bonds as dashed lines.
Aqua[N-(2,5-dihydroxybenzyl)iminodiacetato]copper(II) top
Crystal data top
[Cu(C11H11NO6)(H2O)]F(000) = 1368
Mr = 334.76Dx = 1.797 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ac 2abCell parameters from 6907 reflections
a = 13.0461 (16) Åθ = 1.6–27.9°
b = 9.7919 (12) ŵ = 1.80 mm−1
c = 19.374 (2) ÅT = 294 K
V = 2474.9 (5) Å3Block, blue
Z = 80.22 × 0.18 × 0.12 mm
Data collection top
Rigaku Saturn
diffractometer		2929 independent reflections
Radiation source: rotating anode2662 reflections with I > 2σ(I)
confocalRint = 0.026
Detector resolution: 7.31 pixels mm-1θmax = 27.9°, θmin = 2.1°
ω scansh = −17→17
Absorption correction: multi-scan
(Jacobson, 1998)		k = −12→11
Tmin = 0.693, Tmax = 0.813l = −25→22
17710 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.070H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0451P)2 + 0.7209P]
where P = (Fo2 + 2Fc2)/3
2929 reflections(Δ/σ)max = 0.001
198 parametersΔρmax = 0.31 e Å−3
0 restraintsΔρmin = −0.56 e Å−3
Crystal data top
[Cu(C11H11NO6)(H2O)]V = 2474.9 (5) Å3
Mr = 334.76Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 13.0461 (16) ŵ = 1.80 mm−1
b = 9.7919 (12) ÅT = 294 K
c = 19.374 (2) Å0.22 × 0.18 × 0.12 mm
Data collection top
Rigaku Saturn
diffractometer		2929 independent reflections
Absorption correction: multi-scan
(Jacobson, 1998)		2662 reflections with I > 2σ(I)
Tmin = 0.693, Tmax = 0.813Rint = 0.026
17710 measured reflectionsθmax = 27.9°
Refinement top
R[F2 > 2σ(F2)] = 0.025H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.070Δρmax = 0.31 e Å−3
S = 1.04Δρmin = −0.56 e Å−3
2929 reflectionsAbsolute structure: ?
198 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.566322 (13)0.226573 (19)0.381922 (9)0.01771 (8)
O10.68631 (9)0.23223 (12)0.44079 (6)0.0273 (3)
O20.83131 (8)0.34779 (12)0.45719 (6)0.0275 (3)
O30.47226 (9)0.23658 (11)0.30369 (5)0.0214 (2)
O40.43813 (9)0.36157 (13)0.21087 (6)0.0300 (3)
O50.43629 (9)0.31326 (14)0.45565 (6)0.0259 (3)
H50.402 (2)0.269 (3)0.4779 (13)0.049 (7)*
O60.24306 (11)0.69678 (15)0.29249 (7)0.0402 (3)
H40.179 (2)0.700 (3)0.3008 (12)0.046 (6)*
O70.54070 (9)0.03204 (12)0.39637 (7)0.0242 (2)
H7A0.5782 (16)−0.006 (2)0.4227 (12)0.039 (6)*
H7B0.5424 (18)−0.010 (3)0.3566 (13)0.046 (7)*
N10.60886 (9)0.41382 (12)0.35356 (6)0.0164 (2)
C10.74866 (11)0.32885 (16)0.42719 (7)0.0205 (3)
C20.72035 (11)0.42214 (16)0.36733 (8)0.0225 (3)
H2A0.73890.51550.37840.027*
H2B0.75810.39520.32640.027*
C30.48912 (11)0.33842 (16)0.26298 (7)0.0200 (3)
C40.58171 (11)0.42657 (17)0.27948 (7)0.0209 (3)
H4A0.63940.39830.25130.025*
H4B0.56650.52120.26880.025*
C50.55454 (11)0.51871 (16)0.39631 (8)0.0212 (3)
H5A0.57880.60870.38320.025*
H5B0.57180.50460.44450.025*
C60.44000 (11)0.51419 (17)0.38847 (7)0.0203 (3)
C70.38238 (12)0.41397 (16)0.42132 (7)0.0214 (3)
C80.27640 (12)0.41627 (18)0.41733 (8)0.0268 (3)
H80.23790.35300.44200.032*
C90.22764 (13)0.51300 (19)0.37651 (8)0.0288 (4)
H90.15650.51490.37420.035*
C100.28474 (13)0.60661 (17)0.33916 (9)0.0275 (3)
C110.39017 (12)0.60955 (16)0.34741 (9)0.0268 (3)
H110.42820.67660.32510.032*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01778 (12)0.01416 (12)0.02119 (11)−0.00129 (6)−0.00341 (6)0.00288 (6)
O10.0249 (6)0.0251 (6)0.0320 (6)−0.0065 (5)−0.0100 (5)0.0112 (4)
O20.0206 (5)0.0312 (6)0.0306 (6)−0.0049 (5)−0.0093 (4)0.0097 (5)
O30.0218 (5)0.0199 (5)0.0226 (5)−0.0030 (4)−0.0037 (4)0.0019 (4)
O40.0303 (6)0.0343 (7)0.0254 (6)−0.0017 (5)−0.0107 (4)0.0048 (5)
O50.0266 (6)0.0260 (6)0.0251 (6)0.0021 (5)0.0062 (4)0.0086 (5)
O60.0264 (7)0.0411 (8)0.0532 (8)0.0104 (6)−0.0013 (6)0.0175 (6)
O70.0251 (5)0.0158 (5)0.0317 (6)−0.0001 (5)−0.0054 (5)0.0033 (5)
N10.0135 (5)0.0169 (6)0.0187 (5)0.0001 (4)−0.0009 (4)0.0026 (4)
C10.0194 (6)0.0198 (7)0.0223 (6)0.0012 (6)−0.0013 (5)0.0025 (5)
C20.0150 (6)0.0240 (7)0.0285 (7)−0.0019 (6)−0.0034 (5)0.0084 (6)
C30.0190 (7)0.0212 (7)0.0200 (7)0.0024 (5)0.0003 (5)−0.0017 (5)
C40.0200 (7)0.0239 (8)0.0188 (7)−0.0013 (6)−0.0007 (5)0.0054 (5)
C50.0212 (7)0.0156 (7)0.0266 (7)−0.0005 (5)−0.0002 (6)−0.0034 (6)
C60.0199 (7)0.0172 (7)0.0236 (7)0.0014 (5)0.0027 (5)−0.0022 (5)
C70.0248 (7)0.0207 (7)0.0186 (6)0.0031 (6)0.0041 (5)−0.0009 (5)
C80.0231 (7)0.0309 (9)0.0263 (8)−0.0033 (7)0.0063 (6)0.0022 (6)
C90.0190 (7)0.0348 (9)0.0327 (8)0.0027 (7)0.0036 (6)−0.0010 (6)
C100.0250 (8)0.0245 (8)0.0329 (8)0.0074 (6)0.0014 (6)0.0016 (6)
C110.0239 (8)0.0201 (8)0.0363 (8)0.0020 (6)0.0049 (6)0.0059 (6)
Geometric parameters (Å, °) top
Cu1—O11.9376 (11)C1—C21.522 (2)
Cu1—O31.9526 (11)C2—H2A0.9700
Cu1—O71.9541 (12)C2—H2B0.9700
Cu1—N11.9929 (12)C3—C41.519 (2)
Cu1—O52.3746 (12)C4—H4A0.9700
O1—C11.2752 (19)C4—H4B0.9700
O2—C11.2390 (18)C5—C61.503 (2)
O3—C31.2903 (18)C5—H5A0.9700
O4—C31.2302 (18)C5—H5B0.9700
O5—C71.3818 (19)C6—C111.388 (2)
O5—H50.76 (3)C6—C71.390 (2)
O6—C101.376 (2)C7—C81.385 (2)
O6—H40.86 (3)C8—C91.388 (2)
O7—H7A0.80 (2)C8—H80.9300
O7—H7B0.87 (3)C9—C101.385 (2)
N1—C21.4810 (18)C9—H90.9300
N1—C41.4834 (17)C10—C111.385 (2)
N1—C51.4976 (19)C11—H110.9300
O1—Cu1—O3164.41 (5)O4—C3—O3123.49 (14)
O1—Cu1—O794.69 (5)O4—C3—C4119.88 (14)
O3—Cu1—O793.01 (5)O3—C3—C4116.50 (12)
O1—Cu1—N184.90 (5)N1—C4—C3110.22 (11)
O3—Cu1—N185.11 (5)N1—C4—H4A109.6
O7—Cu1—N1169.72 (5)C3—C4—H4A109.6
O1—Cu1—O5102.29 (5)N1—C4—H4B109.6
O3—Cu1—O590.00 (5)C3—C4—H4B109.6
O7—Cu1—O598.05 (5)H4A—C4—H4B108.1
N1—Cu1—O592.06 (5)N1—C5—C6113.23 (12)
C1—O1—Cu1114.51 (9)N1—C5—H5A108.9
C3—O3—Cu1113.96 (9)C6—C5—H5A108.9
C7—O5—Cu1109.22 (9)N1—C5—H5B108.9
C7—O5—H5112 (2)C6—C5—H5B108.9
Cu1—O5—H5124 (2)H5A—C5—H5B107.7
C10—O6—H4106.8 (16)C11—C6—C7118.94 (14)
Cu1—O7—H7A116.0 (17)C11—C6—C5120.25 (14)
Cu1—O7—H7B109.1 (17)C7—C6—C5120.81 (14)
H7A—O7—H7B109 (2)O5—C7—C8123.13 (14)
C2—N1—C4113.83 (11)O5—C7—C6116.67 (13)
C2—N1—C5109.11 (11)C8—C7—C6120.18 (14)
C4—N1—C5111.37 (11)C7—C8—C9120.03 (15)
C2—N1—Cu1105.92 (9)C7—C8—H8120.0
C4—N1—Cu1106.12 (9)C9—C8—H8120.0
C5—N1—Cu1110.28 (9)C10—C9—C8120.18 (16)
O2—C1—O1124.70 (14)C10—C9—H9119.9
O2—C1—C2118.61 (13)C8—C9—H9119.9
O1—C1—C2116.62 (13)O6—C10—C11117.07 (15)
N1—C2—C1110.04 (12)O6—C10—C9123.74 (15)
N1—C2—H2A109.7C11—C10—C9119.17 (15)
C1—C2—H2A109.7C10—C11—C6121.15 (15)
N1—C2—H2B109.7C10—C11—H11119.4
C1—C2—H2B109.7C6—C11—H11119.4
H2A—C2—H2B108.2
O3—Cu1—O1—C136.6 (3)O2—C1—C2—N1−161.79 (13)
O7—Cu1—O1—C1155.93 (11)O1—C1—C2—N121.11 (19)
N1—Cu1—O1—C1−13.76 (11)Cu1—O3—C3—O4179.80 (12)
O5—Cu1—O1—C1−104.76 (11)Cu1—O3—C3—C43.87 (16)
O1—Cu1—O3—C3−38.9 (2)C2—N1—C4—C3145.89 (13)
O7—Cu1—O3—C3−158.44 (11)C5—N1—C4—C3−90.25 (14)
N1—Cu1—O3—C311.43 (10)Cu1—N1—C4—C329.79 (13)
O5—Cu1—O3—C3103.49 (11)O4—C3—C4—N1160.38 (13)
O1—Cu1—O5—C7130.89 (10)O3—C3—C4—N1−23.53 (18)
O3—Cu1—O5—C7−39.44 (10)C2—N1—C5—C6−177.33 (12)
O7—Cu1—O5—C7−132.48 (10)C4—N1—C5—C656.17 (16)
N1—Cu1—O5—C745.67 (10)Cu1—N1—C5—C6−61.38 (14)
O1—Cu1—N1—C223.76 (9)N1—C5—C6—C11−102.16 (17)
O3—Cu1—N1—C2−144.26 (9)N1—C5—C6—C777.03 (17)
O7—Cu1—N1—C2−64.4 (3)Cu1—O5—C7—C8129.74 (13)
O5—Cu1—N1—C2125.92 (9)Cu1—O5—C7—C6−48.69 (15)
O1—Cu1—N1—C4145.08 (9)C11—C6—C7—O5173.46 (14)
O3—Cu1—N1—C4−22.93 (9)C5—C6—C7—O5−5.7 (2)
O7—Cu1—N1—C456.9 (3)C11—C6—C7—C8−5.0 (2)
O5—Cu1—N1—C4−112.75 (9)C5—C6—C7—C8175.78 (14)
O1—Cu1—N1—C5−94.17 (9)O5—C7—C8—C9−173.82 (15)
O3—Cu1—N1—C597.81 (9)C6—C7—C8—C94.6 (2)
O7—Cu1—N1—C5177.7 (2)C7—C8—C9—C100.6 (3)
O5—Cu1—N1—C57.99 (9)C8—C9—C10—O6173.45 (16)
Cu1—O1—C1—O2−177.60 (12)C8—C9—C10—C11−5.2 (3)
Cu1—O1—C1—C2−0.69 (18)O6—C10—C11—C6−174.02 (15)
C4—N1—C2—C1−145.39 (13)C9—C10—C11—C64.7 (3)
C5—N1—C2—C189.54 (15)C7—C6—C11—C100.4 (2)
Cu1—N1—C2—C1−29.17 (14)C5—C6—C11—C10179.58 (15)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5···O2i0.76 (3)1.93 (3)2.6859 (16)172 (3)
O6—H4···O3ii0.86 (3)2.00 (3)2.8442 (18)168 (2)
O7—H7A···O2iii0.80 (2)1.97 (2)2.7261 (16)157 (2)
O7—H7B···O4iv0.87 (3)1.83 (3)2.6794 (18)163 (2)
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) −x+1/2, y+1/2, z; (iii) −x+3/2, y−1/2, z; (iv) −x+1, y−1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5···O2i0.76 (3)1.93 (3)2.6859 (16)172 (3)
O6—H4···O3ii0.86 (3)2.00 (3)2.8442 (18)168 (2)
O7—H7A···O2iii0.80 (2)1.97 (2)2.7261 (16)157 (2)
O7—H7B···O4iv0.87 (3)1.83 (3)2.6794 (18)163 (2)
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) −x+1/2, y+1/2, z; (iii) −x+3/2, y−1/2, z; (iv) −x+1, y−1/2, −z+1/2.
Acknowledgements top

We gratefully acknowledge the Science Foundation of Guangxi (No.0832098, 0731052) and the Teaching and Research Award Programme for Outstanding Young Teachers in Higher Education Institutions of MOE, China.

references
References top

Addison, A. W., Rao, T. N., Reedijk, J., Rijn, V. J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356.

Calvo, R., Abresch, E. C., Bittl, R., Feher, G., Hofbauer, W., Isaacson, R. A., Lubitz, W., Okamura, M. Y. & Paddock, M. L. (2000). J. Am. Chem. Soc. 122, 7327–7341.

Dooley, D. M., Scott, R. A., Knowles, P. F., Colanglo, C. M., McGuirl, M. A. & Brown, D. E. (1998). J. Am. Chem. Soc. 120, 2599-2605.

Drouza, C., Tolis, V., Gramlich, V., Raptopoulou, C., Terzis, A., Sigalas, M. P., Kabanos, T. A. & Keramidas, A. D. (2002). Chem. Commun., pp. 2786–2787.

Fan, N.-T. (1992). Handbook of Organic Synthesis. Beijing Institute of Technology Press.

Huang, F.-P., Wang, Y.-X., Zhao, J., Bian, H.-D., Yu, Q. & Liang, H. (2008). Chin. J. Inorg. Chem. 24, 1523–1526.

Iwata, S., Lee, L. W., Okada, K., Lee, J. K., Iwata, M., Rasmussen, B., Link, T. A., Ramaswamy, S. & Jap, B. K. (1998). Science, 281, 64-71.

Jacobson, R. (1998). Private communication to the Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2005). CrystalClear and CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Wang, S. X., Mure, M., Medzihradsky, K. F., Burlingame, A. L., Brown, D. E., Dooley, D. M., Smith, A. J., Kagan, H. M. & Klinman, J. P. (1996). Science, 273, 1078–1084.