Buvaylo

Dolomanov

Irina V. Omelchenko

Julia A. Rusanova

Kovbasyuk

Makhankova

Nataliya I. Plyuta

Nesterova

Nikitina

Pryma

Sheldrick

Svitlana R. Petrusenko

Vassilyeva

Westrip

Acta Crystallographica Section E

In the mononuclear copper(II) title complex, [Cu(C11H16N3O)(H2O)]Br, the CuIIatom is coordinated by one O and three N atoms of the Schiff base ligand that forms together with one water molecule a slightly distorted [CuN3O2] square-pyramidal polyhedron. The deviation of the CuIIatom from the mean equatorial plane is 0.182 (2) Å. The equatorial plane is nearly coplanar to the aromatic ring of the ligand [angle between planes = 10.4 (1)°], and the water molecule is situated in the apical site. All coordinating atoms (except the imine nitrogen) and the bromide ion contribute to the formation of the N—H...Br, O—H...Br and O—H...O hydrogen bonds, which link molecules into chains along [01-1].</jats:p

Crossref

Crystal structure of {2-[({2-[(2-aminoeth-yl)amino]ethyl}imino)methyl]phenolato}-aquacopper(II) bromideNataliya I. Plyuta,a Julia A. Rusanova,a Svitlana R.Petrusenkoa* and Irina V. OmelchenkobaTaras Shevchenko National University of Kyiv, Department of Inorganic Chemistry,Volodymyrska str. 64/13, 01601 Kyiv, Ukraine, and bInstitute for ScintillationMaterials, "Institute for Single Crystals", National Academy of Sciences of Ukraine,Lenina ave. 60, Kharkov 61001, Ukraine. *Correspondence e-mail:spetrusenko@yahoo.comReceived 14 May 2014; accepted 31 July 2014Edited by G. M. Rosair, Heriot-Watt University, ScotlandIn the mononuclear copper(II) title complex, [Cu(C11H16-N3O)(H2O)]Br, the CuII atom is coordinated by one O andthree N atoms of the Schiff base ligand that forms togetherwith one water molecule a slightly distorted [CuN3O2] square-pyramidal polyhedron. The deviation of the CuII atom fromthe mean equatorial plane is 0.182 (2) A˚. The equatorial planeis nearly coplanar to the aromatic ring of the ligand [anglebetween planes = 10.4 (1)], and the water molecule is situatedin the apical site. All coordinating atoms (except the iminenitrogen) and the bromide ion contribute to the formation ofthe N—H  Br, O—H  Br and O—H  O hydrogen bonds,which link molecules into chains along [011].Keywords: crystal structure; copper(II) complex; Schiff base ligand;bromide; hydrogen bonding.CCDC reference: 10172091. Related literatureFor structures isotypic with that of the title compound, see:Zhu et al. (2002, 2004); He (2003). For the direct synthesis ofcopper-containing coordination compounds using the saltroute, see: Kovbasyuk et al. (1997); Pryma et al. (2003);Buvaylo et al. (2005); Nikitina et al. (2008); Vassilyeva et al.(1997); Makhankova et al. (2002). For the direct synthesis ofpolynuclear copper-containing complexes, see: Nesterova(Pryma) et al. (2004); Nesterova et al. (2005).2. Experimental2.1. Crystal data[Cu(C11H16N3O)(H2O)]BrMr = 367.73Monoclinic, P21=ca = 9.2226 (11) A˚b = 14.0333 (13) A˚c = 10.9206 (11) A˚ = 102.355 (11)V = 1380.7 (3) A˚3Z = 4Mo K radiation = 4.47 mm1T = 293 K0.40  0.40  0.40 mm2.2. Data collectionAgilent Xcalibur Sapphire3diffractometerAbsorption correction: multi-scan(CrysAlis PRO; Agilent, 2011)Tmin = 0.268, Tmax = 0.2687804 measured reflections4004 independent reflections2334 reflections with I > 2(I)Rint = 0.0452.3. RefinementR[F 2 > 2(F 2)] = 0.052wR(F 2) = 0.097S = 0.954004 reflections163 parametersH-atom parameters constrainedmax = 0.98 e A˚3min = 0.38 e A˚3Table 1Hydrogen-bond geometry (A˚, ).D—H  A D—H H  A D  A D—H  AO2—H2OB  Br1 0.82 2.51 3.323 (3) 173N2—H2N  Br1 0.85 2.58 3.429 (3) 177O2—H2OA  O1i 0.82 1.90 2.712 (4) 171N3—H3NA  Br1ii 0.85 2.68 3.499 (3) 164Symmetry codes: (i) xþ 1;yþ 1;zþ 1; (ii) xþ 1; yþ 12;z þ 32.Data collection: CrysAlis PRO (Agilent, 2011); cell refinement:CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2011);program(s) used to solve structure: SHELXTL (Sheldrick, 2008);program(s) used to refine structure: OLEX2 (Dolomanov et al.,2009); molecular graphics: SHELXTL; software used to preparematerial for publication: publCIF (Westrip, 2010).AcknowledgementsThis work was partly supported by the State Fund forFundamental Researches of Ukraine (project 54.3/005).Supporting information for this paper is available from the IUCrelectronic archives (Reference: RN2126).data reportsm330 Plyuta et al. doi:10.1107/S1600536814017590 Acta Cryst. (2014). E70, m330–m331ISSN 1600-5368ReferencesAgilent (2011). CrysAlis PRO and CrysAlis RED. Agilent Technologies,Yarnton, England.Buvaylo, E. A., Kokozay, V. N., Vassilyeva, O. Yu., Skelton, B. W., Jezierska, J.,Brunel, L. C. & Ozarowski, A. (2005). Chem. Commun. pp. 4976–4978.Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann,H. (2009). J. Appl. Cryst. 42, 339–341.He, G.-F. (2003). Chin. J. Spectrosc. Lab. 5, 647–649.Kovbasyuk, L. A., Babich, O. A. &Kokozay, V. N. (1997). Polyhedron, 16, 161–163.Makhankova, V. G., Vassilyeva, O. Yu., Kokozay, V. N., Skelton, B. W., Sorace,L. & Gatteschi, D. (2002). J. Chem. Soc. Dalton Trans. pp. 4253–4259.Nesterova, O. V., Lipetskaya, A. V., Petrusenko, S. R., Kokozay, V. N., Skelton,B. W. & Jezierska, J. (2005). Polyhedron, 24, 1425–1434.Nesterova (Pryma), O. V., Petrusenko, S. R., Kokozay, V. N., Skelton, B. W. &Linert, W. (2004). Inorg. Chem. Commun. 7, 450–454.Nikitina, V. M., Nesterova, O. V., Kokozay, V. N., Goreshnik, E. A. & Jezierska,J. (2008). Polyhedron, 27, 2426–2430.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.Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.Vassilyeva, O. Yu., Kokozay, V. N., Zhukova, N. I. & Kovbasyuk, L. A. (1997).Polyhedron, 16, 263–266.Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.Zhu, H.-L., Li, S.-Y., He, W.-M. & Yu, K.-B. (2002). Z. Kristallogr. New Cryst.Struct. 217, 599–600.Zhu, H.-L., Li, S.-Y., Wang, Zh.-D. & Yang, F. (2004). J. Chem. Crystallogr. 34,203–206.data reportsActa Cryst. (2014). E70, m330–m331 Plyuta et al.  [Cu(C11H16N3O)(H2O)]Br m331supporting informationsup-1Acta Cryst. (2014). E70, m330–m331    supporting informationActa Cryst. (2014). E70, m330–m331    [doi:10.1107/S1600536814017590]Crystal structure of {2-[({2-[(2-aminoethyl)amino]ethyl}imino)methyl]-phenolato}aquacopper(II) bromideNataliya I. Plyuta, Julia A. Rusanova, Svitlana R. Petrusenko and Irina V. OmelchenkoS1. Comment It has been shown that the direct synthesis is an efficient method to obtain novel homo and heterometallic mono/polynuclear coordination compounds (Kovbasyuk et al., 1997; Vassilyeva et al., 1997; Makhankova et al., 2002; Pryma et al., 2003; Nesterova (Pryma) et al., 2004; Nesterova et al., 2005; Buvaylo et al., 2005; Nikitina et al., 2008). The title compound, [Cu(C11H18N3O2)(H2O)]Br, was obtained unintentionally as the product of an attempted synthesis of a Cu/ Mn heterometallic complex using zerovalent copper and manganese powders, ammonium bromide, salicylic aldehyde and diethylenetriamine in dimethylformamide on air.As shown in Fig. 1, the CuII atom has a slightly distorted square-pyramidal geometry formed by one oxygen and three nitrogen atoms of the Schiff base ligand as well one oxygen atom of the coordinated water molecule. The deviation of the copper atom from the mean equatorial plane is 0.182 (2) Å. The range of Cu–N and Cu–O bond distances in the equatorial plane is 1.918 (3) - 2.018 (3) Å, while the Cu–O axial distance is 2.333 (2) Å. These data are in a good agreement with literature values (Zhu et al.,2002, 2004; He et al., 2003). The equatorial plane is nearly coplanar to the aromatic ring of the ligand [angle between planes is 10.4 (1)°].In the crystal, OH···O hydrogen bonds form molecular dimers. OH···Br and NH···Br hydrogen bonds link the dimers into chains along the [011] crystallographic direction (See Table containing Hydrogen-bond geometry and Fig.2).S2. Experimental The title compound was synthesized by addition of manganese powder 0.055 g (1 mmol), copper powder 0.06 g (1 mmol) and NH4Br 0.392 g (4 mmol) to the previously prepared Schiff base ligand solution [mixture of salicylic aldehyde 0.21 ml (2 mmol) and diethylenetriamine 0.108 ml (1 mmol) in dimethylformamide (10 ml) which was stirred about 15 min at 323–333 K until the mixture turned yellow]. The total reaction mixture was stirred magnetically for 4 h until the complete dissolution of manganese and copper powders was observed. Dark green crystals that precipitated after 1 day were collected by filtration and dried in air.S3. Refinement Structure was solved by direct method and refined against F2 with anisotropic refinement for all non-hydrogen atoms. All H atoms were placed in idealized positions (C–H = 0.93 – 0.97 Å, O–H = 0.82 Å, N–H 0.85 Å) and constrained to ride on their parent atoms, with Uiso = 1.2Ueq (except Uiso = 1.5Ueq for water).supporting informationsup-2Acta Cryst. (2014). E70, m330–m331    Figure 1Structure of the title compound, with displacement ellipsoids drawn at the 50% probability level for non-H atoms with hydrogen bonds shown as dashed lines. supporting informationsup-3Acta Cryst. (2014). E70, m330–m331    Figure 2Crystal packing of the title compound with hydrogen bonds shown as dashed lines. {2-[({2-[(2-Aminoethyl)amino]ethyl}imino)methyl]phenolato}aquacopper(II) bromide Crystal data [Cu(C11H16N3O)(H2O)]BrMr = 367.73Monoclinic, P21/cHall symbol: -P 2ybca = 9.2226 (11) Åb = 14.0333 (13) Åc = 10.9206 (11) Åβ = 102.355 (11)°V = 1380.7 (3) Å3Z = 4F(000) = 740Dx = 1.769 Mg m−3Mo Kα radiation, λ = 0.71073 ÅCell parameters from 1502 reflectionsθ = 2.9–32.2°µ = 4.47 mm−1T = 293 KBlock, green0.40 × 0.40 × 0.40 mmsupporting informationsup-4Acta Cryst. (2014). E70, m330–m331    Data collection Agilent Xcalibur Sapphire3 diffractometerRadiation source: Enhance (Mo) X-ray SourceGraphite monochromatorDetector resolution: 16.1827 pixels mm-1ω scansAbsorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)Tmin = 0.268, Tmax = 0.2687804 measured reflections4004 independent reflections2334 reflections with I > 2σ(I)Rint = 0.045θmax = 30.0°, θmin = 2.9°h = −7→12k = −16→19l = −15→12Refinement Refinement on F2Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.052wR(F2) = 0.097S = 0.954004 reflections163 parameters0 restraintsPrimary atom site location: structure-invariant direct methodsSecondary atom site location: difference Fourier mapHydrogen site location: inferred from neighbouring sitesH-atom parameters constrainedw = 1/[σ2(Fo2) + (0.0308P)2] where P = (Fo2 + 2Fc2)/3(Δ/σ)max = 0.001Δρmax = 0.98 e Å−3Δρmin = −0.38 e Å−3Special details Experimental. Absorption correction: CrysAlis PRO (Agilent, 2011) 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.Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) x y z Uiso*/UeqCu1 0.67287 (6) 0.58118 (3) 0.65849 (4) 0.03317 (14)Br1 0.70894 (6) 0.32849 (3) 0.91251 (4) 0.04828 (15)O1 0.6489 (3) 0.61004 (19) 0.4836 (2) 0.0412 (7)O2 0.6414 (3) 0.41770 (17) 0.6240 (2) 0.0401 (7)H2OA 0.5548 0.4032 0.5949 0.060*H2OB 0.6614 0.3912 0.6920 0.060*N1 0.8883 (4) 0.5872 (2) 0.6891 (3) 0.0346 (8)N2 0.7031 (4) 0.5675 (2) 0.8462 (3) 0.0387 (8)H2N 0.7059 0.5079 0.8604 0.046*N3 0.4595 (4) 0.6068 (2) 0.6646 (3) 0.0399 (8)H3NA 0.4358 0.6632 0.6411 0.048*H3NB 0.4087 0.5679 0.6132 0.048*C1 0.9071 (4) 0.6273 (2) 0.4771 (3) 0.0302 (8)C2 0.7532 (5) 0.6287 (2) 0.4219 (3) 0.0313 (9)supporting informationsup-5Acta Cryst. (2014). E70, m330–m331    C3 0.7118 (5) 0.6529 (2) 0.2942 (3) 0.0349 (9)H3 0.6117 0.6542 0.2556 0.042*C4 0.8153 (5) 0.6747 (3) 0.2252 (4) 0.0424 (11)H4 0.7837 0.6912 0.1412 0.051*C5 0.9668 (5) 0.6727 (3) 0.2784 (4) 0.0463 (11)H5 1.0368 0.6864 0.2309 0.056*C6 1.0092 (5) 0.6498 (3) 0.4026 (4) 0.0419 (10)H6 1.1100 0.6491 0.4394 0.050*C7 0.9648 (5) 0.6070 (2) 0.6085 (4) 0.0366 (9)H7 1.0673 0.6085 0.6364 0.044*C8 0.9587 (5) 0.5675 (3) 0.8202 (4) 0.0467 (11)H8A 1.0528 0.6007 0.8429 0.056*H8B 0.9771 0.4997 0.8320 0.056*C9 0.8548 (5) 0.6011 (3) 0.9012 (4) 0.0411 (10)H9A 0.8868 0.5762 0.9855 0.049*H9B 0.8561 0.6702 0.9058 0.049*C10 0.5790 (5) 0.6137 (3) 0.8863 (4) 0.0440 (11)H10A 0.5935 0.6822 0.8899 0.053*H10B 0.5728 0.5915 0.9691 0.053*C11 0.4385 (5) 0.5896 (3) 0.7935 (4) 0.0492 (11)H11A 0.4132 0.5233 0.8027 0.059*H11B 0.3576 0.6287 0.8092 0.059*Atomic displacement parameters (Å2) U11 U22 U33 U12 U13 U23Cu1 0.0316 (3) 0.0396 (3) 0.0258 (2) 0.0004 (2) 0.00050 (19) 0.0017 (2)Br1 0.0532 (3) 0.0425 (2) 0.0456 (3) −0.0024 (2) 0.0028 (2) 0.0084 (2)O1 0.0259 (16) 0.0651 (18) 0.0285 (14) −0.0052 (14) −0.0029 (12) 0.0099 (13)O2 0.0341 (17) 0.0430 (15) 0.0378 (15) −0.0046 (13) −0.0039 (12) −0.0007 (13)N1 0.032 (2) 0.0361 (17) 0.0306 (17) 0.0052 (15) −0.0046 (14) −0.0041 (15)N2 0.053 (2) 0.0278 (16) 0.0327 (18) −0.0054 (16) 0.0025 (16) 0.0013 (14)N3 0.037 (2) 0.0425 (18) 0.0396 (19) −0.0004 (16) 0.0076 (16) −0.0011 (15)C1 0.027 (2) 0.0261 (17) 0.036 (2) 0.0005 (17) 0.0039 (17) −0.0055 (16)C2 0.033 (2) 0.0300 (19) 0.031 (2) −0.0043 (18) 0.0052 (17) −0.0009 (16)C3 0.035 (2) 0.037 (2) 0.029 (2) −0.0076 (18) 0.0001 (17) −0.0034 (16)C4 0.058 (3) 0.036 (2) 0.035 (2) −0.004 (2) 0.014 (2) −0.0020 (18)C5 0.047 (3) 0.047 (2) 0.052 (3) 0.002 (2) 0.026 (2) −0.012 (2)C6 0.032 (3) 0.040 (2) 0.055 (3) −0.0030 (19) 0.012 (2) −0.010 (2)C7 0.024 (2) 0.036 (2) 0.046 (2) 0.0033 (17) −0.0014 (19) −0.0055 (18)C8 0.047 (3) 0.052 (3) 0.032 (2) 0.014 (2) −0.0111 (19) 0.0004 (19)C9 0.047 (3) 0.043 (2) 0.028 (2) 0.003 (2) −0.0043 (19) 0.0004 (18)C10 0.054 (3) 0.045 (2) 0.036 (2) −0.002 (2) 0.015 (2) −0.0047 (18)C11 0.048 (3) 0.059 (3) 0.043 (3) −0.008 (2) 0.016 (2) −0.005 (2)supporting informationsup-6Acta Cryst. (2014). E70, m330–m331    Geometric parameters (Å, º) Cu1—O1 1.919 (3) C2—C3 1.407 (5)Cu1—N1 1.945 (3) C3—C4 1.371 (5)Cu1—N3 2.016 (3) C3—H3 0.9300Cu1—N2 2.018 (3) C4—C5 1.395 (6)Cu1—O2 2.333 (2) C4—H4 0.9300O1—C2 1.313 (4) C5—C6 1.367 (6)O2—H2OA 0.8197 C5—H5 0.9300O2—H2OB 0.8159 C6—H6 0.9300N1—C7 1.271 (5) C7—H7 0.9300N1—C8 1.466 (5) C8—C9 1.512 (6)N2—C10 1.461 (5) C8—H8A 0.9700N2—C9 1.477 (5) C8—H8B 0.9700N2—H2N 0.8495 C9—H9A 0.9700N3—C11 1.481 (5) C9—H9B 0.9700N3—H3NA 0.8455 C10—C11 1.503 (6)N3—H3NB 0.8494 C10—H10A 0.9700C1—C6 1.407 (5) C10—H10B 0.9700C1—C2 1.418 (5) C11—H11A 0.9700C1—C7 1.447 (5) C11—H11B 0.9700O1—Cu1—N1 93.31 (12) C2—C3—H3 119.1O1—Cu1—N3 95.17 (12) C3—C4—C5 121.3 (4)N1—Cu1—N3 162.80 (13) C3—C4—H4 119.3O1—Cu1—N2 173.18 (12) C5—C4—H4 119.3N1—Cu1—N2 85.17 (14) C6—C5—C4 117.8 (4)N3—Cu1—N2 84.65 (14) C6—C5—H5 121.1O1—Cu1—O2 93.61 (10) C4—C5—H5 121.1N1—Cu1—O2 99.09 (11) C5—C6—C1 122.8 (4)N3—Cu1—O2 95.29 (11) C5—C6—H6 118.6N2—Cu1—O2 93.20 (10) C1—C6—H6 118.6C2—O1—Cu1 127.7 (2) N1—C7—C1 126.1 (4)Cu1—O2—H2OA 112.6 N1—C7—H7 117.0Cu1—O2—H2OB 107.8 C1—C7—H7 117.0H2OA—O2—H2OB 104.6 N1—C8—C9 108.0 (3)C7—N1—C8 121.5 (4) N1—C8—H8A 110.1C7—N1—Cu1 126.0 (3) C9—C8—H8A 110.1C8—N1—Cu1 112.5 (3) N1—C8—H8B 110.1C10—N2—C9 118.1 (3) C9—C8—H8B 110.1C10—N2—Cu1 108.4 (2) H8A—C8—H8B 108.4C9—N2—Cu1 107.2 (2) N2—C9—C8 109.0 (3)C10—N2—H2N 112.2 N2—C9—H9A 109.9C9—N2—H2N 104.5 C8—C9—H9A 109.9Cu1—N2—H2N 105.7 N2—C9—H9B 109.9C11—N3—Cu1 109.3 (3) C8—C9—H9B 109.9C11—N3—H3NA 111.3 H9A—C9—H9B 108.3Cu1—N3—H3NA 110.3 N2—C10—C11 108.4 (3)supporting informationsup-7Acta Cryst. (2014). E70, m330–m331    C11—N3—H3NB 111.0 N2—C10—H10A 110.0Cu1—N3—H3NB 105.5 C11—C10—H10A 110.0H3NA—N3—H3NB 109.3 N2—C10—H10B 110.0C6—C1—C2 119.0 (4) C11—C10—H10B 110.0C6—C1—C7 117.9 (4) H10A—C10—H10B 108.4C2—C1—C7 123.1 (4) N3—C11—C10 109.5 (4)O1—C2—C3 118.9 (4) N3—C11—H11A 109.8O1—C2—C1 123.7 (3) C10—C11—H11A 109.8C3—C2—C1 117.3 (4) N3—C11—H11B 109.8C4—C3—C2 121.7 (4) C10—C11—H11B 109.8C4—C3—H3 119.1 H11A—C11—H11B 108.2Hydrogen-bond geometry (Å, º) D—H···A D—H H···A D···A D—H···AO2—H2OB···Br1 0.82 2.51 3.323 (3) 173N2—H2N···Br1 0.85 2.58 3.429 (3) 177O2—H2OA···O1i 0.82 1.90 2.712 (4) 171N3—H3NA···Br1ii 0.85 2.68 3.499 (3) 164Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+3/2.

Acta Crystallographica Section E Structure Reports Online

Crystal structure of {2-[({2-[(2-aminoethyl)amino]ethyl}imino)methyl]phenolato}aquacopper(II) bromide

http://journals.iucr.org/e/issues/2014/09/00/rn2126/rn2126.pdf

Crystal structure of {2-[({2-[(2-aminoethyl)amino]ethyl}imino)methyl]phenolato}aquacopper(II) bromide

Abstract

Similar works

Full text

Available Versions

Crossref