metal-organic compounds
Bis(2-hydroxyiminomethyl-6-methoxyphenolato-κ2N,O1)copper(II)
aDepartment of Inorganic Chemistry, Taras Shevchenko National University of Kyiv, 64 Volodymyrs'ka St, Kyiv 01601, Ukraine, and bSTC `Institute for Single Crystals', National Academy of Sciences of Ukraine, 60 Lenina Ave, Kharkiv 61001, Ukraine
*Correspondence e-mail: spetrusenko@yahoo.com
In the title compound, [Cu(C8H8NO3)2], the nearly planar molecule (r.m.s. deviation = 0.037 Å) is centrosymmetric with the CuII atom lying on an inversion center. The CuII atom is tetracoordinated, displaying a slightly distorted square-planar geometry. The main deviation from the ideal geometry is seen in the differences in the Cu—O [1.8833 (10) Å] and Cu—N [1.9405 (13) Å] bond lengths, while angular deviations are less than 3°. Intramolecular O—H⋯O and intermolecular Csp2—H⋯O hydrogen bonds form S(5) and R22(8) ring motifs, respectively. The latter interaction results in chains of molecules along [100].
Related literature
For related structures, see: Zhang et al. (2008); Li et al. (2004), 2009). For bond-valence-sum calculations, see: Brown & Altermatt (1985). For in situ formation of polydentate ligands, see: Coxall et al. (2000). For background to direct synthesis, see: Makhankova (2011).
Experimental
Crystal data
|
Refinement
|
Data collection: CrysAlis CCD (Oxford Diffraction, 2010); cell CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
10.1107/S1600536812032187/lr2071sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812032187/lr2071Isup2.hkl
Copper powder (0.06 g, 1 mmol), manganese powder (0.05 g, 1 mmol), o-vainillin (0.46 g, 3 mmol), hydroxylamine hydrochloride (0.21 g, mmol) and NH4Br (0.20 g, 2 mmol) were added to 10 ml of dimethylsulfoxide. The mixture was stirred magnetically at 323 – 333 K until total dissolution of metal powders was observed (ca5 h). Goldish-green needle crystals that precipitated after 1 day, were collected by filtration, washed with methanol and dried in air; yield 32% based on Cu. IR(KBr, cm-1): 3080(m), 3057(m), 3006(m), 2959(m), 2936(m), 2834(m), 1649(m), 1598(m), 1554(w), 1510(m), 1468(s), 1451(s), 1353(w), 1332(m), 1302(s), 1247(s), 1216(s), 1195(m), 1101(m), 1081(m), 1018(m), 969(s), 932(w), 863(m), 778(m), 755(m), 735(s), 712(s), 624(m), 575(w), 546(w), 502(w).
Structure was solved by direct method and refined against F2 within anisotropic approximation for all non-hydrogen atoms. All hydrogen atoms were located from difference Fourier map and refined isotropically, except phenyl (H(3) - H(5)) and hydroxyl (H(3O)) H atoms that were allowed to ride on their attached atoms with C—H = 0.93 (1) Å and Uiso(H)= 1.2Ueq(C) for phenyl, and C—H = 0.82 (1) Å and Uiso(H)= 1.5Ueq(C) for hydroxyl H atoms. Coordinates of Cu(1) were constrained to special position (x=0.5000, y=0.5000, z=0.5000).
Data collection: CrysAlis CCD (Oxford Diffraction, 2010); cell
CrysAlis CCD (Oxford Diffraction, 2010); data reduction: CrysAlis RED (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).[Cu(C8H8NO3)2] | F(000) = 406 |
Mr = 395.85 | Dx = 1.675 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2721 reflections |
a = 8.4906 (4) Å | θ = 3.1–32.2° |
b = 4.8997 (2) Å | µ = 1.43 mm−1 |
c = 18.9309 (9) Å | T = 293 K |
β = 94.906 (4)° | Needle, gold–green |
V = 784.67 (6) Å3 | 0.50 × 0.20 × 0.10 mm |
Z = 2 |
Oxford Diffraction Xcalibur/Sapphire3 diffractometer | 2245 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 1816 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
Detector resolution: 16.1827 pixels mm-1 | θmax = 30.0°, θmin = 3.9° |
ω scans | h = −11→11 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010) | k = −6→6 |
Tmin = 0.535, Tmax = 0.763 | l = −26→26 |
8497 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.028 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0486P)2] where P = (Fo2 + 2Fc2)/3 |
2245 reflections | (Δ/σ)max = 0.001 |
132 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
11 constraints |
[Cu(C8H8NO3)2] | V = 784.67 (6) Å3 |
Mr = 395.85 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.4906 (4) Å | µ = 1.43 mm−1 |
b = 4.8997 (2) Å | T = 293 K |
c = 18.9309 (9) Å | 0.50 × 0.20 × 0.10 mm |
β = 94.906 (4)° |
Oxford Diffraction Xcalibur/Sapphire3 diffractometer | 2245 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010) | 1816 reflections with I > 2σ(I) |
Tmin = 0.535, Tmax = 0.763 | Rint = 0.020 |
8497 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.39 e Å−3 |
2245 reflections | Δρmin = −0.19 e Å−3 |
132 parameters |
Experimental. CrysAlis RED, Oxford Diffraction Ltd., 2010. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.5000 | 0.5000 | 0.5000 | 0.03633 (10) | |
N1 | 0.27576 (15) | 0.5566 (3) | 0.50728 (7) | 0.0398 (3) | |
C1 | 0.60680 (18) | 0.0698 (3) | 0.59715 (8) | 0.0378 (3) | |
O1 | 0.49066 (12) | 0.2223 (2) | 0.56829 (5) | 0.0446 (2) | |
O2 | 0.41409 (14) | −0.1275 (2) | 0.66227 (6) | 0.0541 (3) | |
C2 | 0.56941 (19) | −0.1252 (3) | 0.64921 (7) | 0.0416 (3) | |
O3 | 0.20159 (13) | 0.3924 (3) | 0.55453 (6) | 0.0518 (3) | |
H3O | 0.2665 | 0.2879 | 0.5745 | 0.078* | |
C3 | 0.6860 (2) | −0.2899 (3) | 0.68168 (8) | 0.0488 (4) | |
H3 | 0.6603 | −0.4164 | 0.7155 | 0.059* | |
C4 | 0.8415 (2) | −0.2687 (3) | 0.66435 (8) | 0.0512 (4) | |
H4 | 0.9189 | −0.3814 | 0.6865 | 0.061* | |
C5 | 0.8809 (2) | −0.0838 (4) | 0.61520 (9) | 0.0467 (3) | |
H5 | 0.9853 | −0.0700 | 0.6043 | 0.056* | |
C6 | 0.76430 (18) | 0.0881 (3) | 0.58031 (8) | 0.0393 (3) | |
C7 | 0.81554 (18) | 0.2753 (3) | 0.52815 (8) | 0.0420 (3) | |
H7 | 0.920 (2) | 0.279 (4) | 0.5214 (9) | 0.054 (5)* | |
C8 | 0.3647 (3) | −0.3339 (4) | 0.70831 (10) | 0.0572 (4) | |
H8A | 0.392 (3) | −0.514 (4) | 0.6925 (12) | 0.050 (6)* | |
H8B | 0.418 (3) | −0.314 (4) | 0.7595 (12) | 0.072 (6)* | |
H8C | 0.255 (3) | −0.322 (4) | 0.7053 (10) | 0.064 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.03102 (14) | 0.03680 (14) | 0.04131 (15) | −0.00245 (9) | 0.00388 (9) | 0.00387 (9) |
N1 | 0.0332 (6) | 0.0452 (6) | 0.0413 (6) | −0.0056 (5) | 0.0060 (5) | 0.0017 (5) |
C1 | 0.0405 (7) | 0.0349 (6) | 0.0379 (7) | −0.0014 (6) | 0.0017 (6) | −0.0020 (5) |
O1 | 0.0358 (5) | 0.0457 (5) | 0.0525 (5) | 0.0010 (4) | 0.0052 (4) | 0.0134 (5) |
O2 | 0.0521 (7) | 0.0494 (6) | 0.0621 (7) | −0.0034 (5) | 0.0118 (5) | 0.0163 (6) |
C2 | 0.0463 (8) | 0.0360 (7) | 0.0422 (7) | −0.0041 (6) | 0.0021 (6) | −0.0008 (6) |
O3 | 0.0370 (5) | 0.0640 (7) | 0.0550 (6) | −0.0058 (6) | 0.0083 (5) | 0.0176 (6) |
C3 | 0.0611 (10) | 0.0393 (7) | 0.0451 (7) | −0.0020 (7) | −0.0013 (7) | 0.0044 (6) |
C4 | 0.0554 (9) | 0.0464 (8) | 0.0499 (8) | 0.0099 (7) | −0.0072 (7) | −0.0004 (7) |
C5 | 0.0402 (8) | 0.0483 (7) | 0.0505 (8) | 0.0060 (7) | −0.0024 (7) | −0.0055 (7) |
C6 | 0.0391 (7) | 0.0369 (6) | 0.0410 (7) | 0.0000 (6) | −0.0009 (6) | −0.0049 (6) |
C7 | 0.0320 (7) | 0.0477 (8) | 0.0463 (7) | −0.0020 (6) | 0.0033 (6) | −0.0023 (6) |
C8 | 0.0656 (12) | 0.0517 (9) | 0.0560 (10) | −0.0083 (9) | 0.0151 (9) | 0.0089 (8) |
Cu1—O1i | 1.8833 (10) | C3—C4 | 1.392 (3) |
Cu1—O1 | 1.8833 (10) | C3—H3 | 0.9300 |
Cu1—N1 | 1.9405 (13) | C4—C5 | 1.361 (2) |
Cu1—N1i | 1.9405 (13) | C4—H4 | 0.9300 |
N1—C7i | 1.281 (2) | C5—C6 | 1.419 (2) |
N1—O3 | 1.3928 (17) | C5—H5 | 0.9300 |
C1—O1 | 1.3179 (17) | C6—C7 | 1.442 (2) |
C1—C6 | 1.404 (2) | C7—N1i | 1.281 (2) |
C1—C2 | 1.428 (2) | C7—H7 | 0.903 (19) |
O2—C2 | 1.362 (2) | C8—H8A | 0.965 (18) |
O2—C8 | 1.422 (2) | C8—H8B | 1.04 (2) |
C2—C3 | 1.380 (2) | C8—H8C | 0.93 (2) |
O3—H3O | 0.8200 | ||
O1i—Cu1—O1 | 180.0 | C4—C3—H3 | 119.7 |
O1i—Cu1—N1 | 92.56 (5) | C5—C4—C3 | 120.27 (15) |
O1—Cu1—N1 | 87.44 (5) | C5—C4—H4 | 119.9 |
O1i—Cu1—N1i | 87.44 (5) | C3—C4—H4 | 119.9 |
O1—Cu1—N1i | 92.56 (5) | C4—C5—C6 | 120.76 (16) |
N1—Cu1—N1i | 180.00 (8) | C4—C5—H5 | 119.6 |
C7i—N1—O3 | 114.91 (13) | C6—C5—H5 | 119.6 |
C7i—N1—Cu1 | 127.46 (11) | C1—C6—C5 | 119.77 (15) |
O3—N1—Cu1 | 117.60 (10) | C1—C6—C7 | 123.03 (14) |
O1—C1—C6 | 124.28 (14) | C5—C6—C7 | 117.20 (15) |
O1—C1—C2 | 117.57 (14) | N1i—C7—C6 | 124.28 (14) |
C6—C1—C2 | 118.15 (14) | N1i—C7—H7 | 117.8 (12) |
C1—O1—Cu1 | 128.33 (10) | C6—C7—H7 | 117.8 (12) |
C2—O2—C8 | 117.25 (14) | O2—C8—H8A | 111.8 (14) |
O2—C2—C3 | 125.65 (14) | O2—C8—H8B | 112.2 (12) |
O2—C2—C1 | 113.99 (13) | H8A—C8—H8B | 106.2 (18) |
C3—C2—C1 | 120.35 (15) | O2—C8—H8C | 105.2 (13) |
N1—O3—H3O | 109.5 | H8A—C8—H8C | 107.6 (19) |
C2—C3—C4 | 120.69 (15) | H8B—C8—H8C | 113.9 (17) |
C2—C3—H3 | 119.7 | ||
O1i—Cu1—N1—C7i | 2.42 (14) | C6—C1—C2—C3 | 0.0 (2) |
O1—Cu1—N1—C7i | −177.58 (14) | O2—C2—C3—C4 | −179.65 (14) |
O1i—Cu1—N1—O3 | −179.73 (11) | C1—C2—C3—C4 | 0.1 (2) |
O1—Cu1—N1—O3 | 0.27 (11) | C2—C3—C4—C5 | 0.3 (2) |
C6—C1—O1—Cu1 | −0.8 (2) | C3—C4—C5—C6 | −0.6 (2) |
C2—C1—O1—Cu1 | 178.82 (10) | O1—C1—C6—C5 | 179.24 (14) |
N1—Cu1—O1—C1 | −177.96 (12) | C2—C1—C6—C5 | −0.4 (2) |
N1i—Cu1—O1—C1 | 2.04 (12) | O1—C1—C6—C7 | −1.0 (2) |
C8—O2—C2—C3 | −6.2 (2) | C2—C1—C6—C7 | 179.38 (13) |
C8—O2—C2—C1 | 174.03 (14) | C4—C5—C6—C1 | 0.7 (2) |
O1—C1—C2—O2 | 0.10 (19) | C4—C5—C6—C7 | −179.06 (14) |
C6—C1—C2—O2 | 179.74 (13) | C1—C6—C7—N1i | 0.6 (2) |
O1—C1—C2—C3 | −179.64 (13) | C5—C6—C7—N1i | −179.65 (15) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3O···O1 | 0.82 | 1.94 | 2.5840 (16) | 134 |
C7—H7···O3ii | 0.903 (19) | 2.49 (2) | 3.3231 (19) | 154.3 (15) |
Symmetry code: (ii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C8H8NO3)2] |
Mr | 395.85 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 8.4906 (4), 4.8997 (2), 18.9309 (9) |
β (°) | 94.906 (4) |
V (Å3) | 784.67 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.43 |
Crystal size (mm) | 0.50 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur/Sapphire3 diffractometer |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2010) |
Tmin, Tmax | 0.535, 0.763 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8497, 2245, 1816 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.077, 1.01 |
No. of reflections | 2245 |
No. of parameters | 132 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.39, −0.19 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3O···O1 | 0.82 | 1.94 | 2.5840 (16) | 134.3 |
C7—H7···O3i | 0.903 (19) | 2.49 (2) | 3.3231 (19) | 154.3 (15) |
Symmetry code: (i) x+1, y, z. |
References
Brown, I. D. & Altermatt, D. (1985). Acta Cryst. B41, 244–247. CrossRef CAS Web of Science IUCr Journals Google Scholar
Coxall, R. A., Harris, S. G., Henderson, D. K., Parsons, S., Tasker, P. A. & Winpenny, R. E. P. (2000). J. Chem. Soc. Dalton Trans. pp. 2349–2356. Web of Science CSD CrossRef Google Scholar
Li, L.-Z., Xu, T., Wang, D.-Q., Niu, M.-J. & Ji, H.-W. (2004). Chin. J. Struct. Chem. 23, 865–869. CAS Google Scholar
Li, B.-W., Zeng, M.-H. & Ng, S. W. (2009). Acta Cryst. E65, m318. Web of Science CSD CrossRef IUCr Journals Google Scholar
Makhankova, V. G. (2011). Glob. J. Inorg. Chem. 2, 265–285. CAS Google Scholar
Oxford Diffraction (2010). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, S. H., Ge, C. M. & Feng, C. (2008). Acta Cryst. E64, m1627. Web of Science CSD CrossRef IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Aiming to prepare Cu/Mn heterometallic complexes with an ONO donor Shiff base (H2L = 2-hydroxyiminomethyl-6-methoxyphenol) the following system based on "direct synthesis" methodology (Makhankova, 2011) has been investigated: Cu0 – Mn0 – o-vianillin– NH2OH.HCl – NH4X – solv (in open air), where o-vainillin = 2-hydroxy-3-methoxybenzaldehyde; X = Cl, Br, I; solv = CH3OH, dymethylformamide(dmf), dymethylsulfoxide(dmso).
In all cases the total dissolution of copper and manganese powders was observed within 5 - 6 h resulting into intensive dark green solutions. X-ray quality crystalls were obtained from the systems with NH4Br in dmso and NH4Cl in dmf, but in the former one the yield was some better.
The asymmetric unit of [Cu(HL)2] includes one-half of the molecule with Cu atom occupying the (1/2 1/2 1/2) special position of multiplicity 2. The coordination geometry of the metal atom is square-planar, with the CuN2O2 chromophore, formed by means of two imine nitrogen atoms and two phenolate oxygen atoms of the two monodeptotonated Schiff base ligands realising their bidentate chelate function, [1.11110] by Harris notation (Coxall et al., 2000) (Fig. 1). Difference between Cu–O and Cu–N bond lengths (Table 1) causes significant linear distortion of the square. Deviations in bond angles at the Cu atom are less than 3°. The bond valence sum analysis applied to the appropriate bond lengths supports the +2 oxidation state for copper, BVS(Cu) = 2.003 (Brown & Altermatt, 1985).
Hydrogen bonds(HBs) play the principal role in the crystal structure of [Cu(HL)2]. The N–OH group takes part in simultaneous formation of a strong intramolecular O(3)–H(3O)···O(1) hydrogen bond with Ophenolate of the second ligand and a weak inter-molecular C(7)–H(7)···O(3)' hydrogen bond with C(sp2)–H group of the neighboring molecule (Fig. 2, Table 2). As a result, two ligands being coordinated to the CuII ion form some analogue of a macrocyclic ligand [R14] based on HBs which binds to the copper center generating two 6-membered (with only covalent bonds) and two 5-membered (with covalent and hydrogen bonds) rings (Fig. 1). It is worth noting that all known structures with H2L, namely Co(HL)2 (Zhang et al., 2008), Ni(HL)2 (Li et al., 2009) and VO(HL)2 (Li et al., 2004), are built in the same manner demonstrating high thermodynamic stability of such structure.
The adjacent molecules join through complementary C–H···O HBs, [R22(8)] synthon, forming one-dimentional stair-like ribbons along (100) direction (Fig. 2).