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New copper(II) 1D polymer containing dimethyl(phenylsulfonyl)amidophosphate: Synthesis, crystal structure and magnetic properties
Polyhedron 28 (2009) 1331–1335
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New copper(II) 1D polymer containing dimethyl(phenylsulfonyl)amidophosphate: Synthesis, crystal structure and magnetic properties Olesia V. Moroz a,*, Victor A. Trush a, Irina S. Konovalova b, Oleg V. Shishkin b,c, Yurii S. Moroz a, Serhiy Demeshko d, Vladimir M. Amirkhanov a a
Department of Chemistry, National Taras Shevchenko University, Volodymyrska Str. 64, Kyiv 01601, Ukraine STC ‘‘Institute for Single Crystals”, National Academy of Science of Ukraine, 60 Lenina Ave., Kharkiv 61001, Ukraine c V.N. Karazin Kharkiv National University, 4 Svobody Sq., Kharkiv 61077, Ukraine d Georg-August-University, Institute of Inorganic Chemistry, Tammannstr. 4, Goettingen D-37077, Germany b
a r t i c l e
i n f o
Article history: Received 28 November 2008 Accepted 7 February 2009 Available online 20 February 2009 Keywords: Sulfonyl phosphoramides One-dimensional polymeric structure Antiferromagnetic behavior
a b s t r a c t The reaction of sodium dimethyl(phenylsulfonyl)amidophosphate NaL (HL = C6H5SO2NHP(O)(OCH3)2) with Cu(NO3)2 6H2O and o-bpe (1,2-bis(pyridine-2-yl)ethane) in appropriate ratios, afford the formation of 1D coordination polymer [Cu(L)2 o-bpe]n in good yield. The crystal structures of HL (1) and [Cu(L)2 o-bpe]n (2) are reported. In the crystal package the molecules of 1 are linked by intermolecular hydrogen bonds formed by the phosphoryl oxygen atoms which serve as acceptors and nitrogen atoms of amide groups as donors. The crystal structure of 2 indicates the presence of unsaturated Cu(L)2 unit bridged by o-bpe ligand in the one-dimensional polymeric chain. The Cu(II) atoms have distorted 4 + 2 octahedral CuO4N2 environment formed by the oxygen atoms belonging to the sulfonyl and phosphoryl groups of two deprotonated chelate ligands and nitrogen atoms of the bridging o-bpe ligands. The magnetic study of 2 has revealed the presence of a weak intrachain antiferromagnetic exchange interaction between copper ions. Ó 2009 Elsevier Ltd. All rights reserved.
1. Introduction In the past few decades the investigation of new polydentate chelate ligands has attracted considerable attention in the field of modern inorganic chemistry because of the formation of kinetic, thermodynamic and thermic stable coordination compounds based on these ligands with potentially useful properties. Up to date azo- and hetero-analogues of b-diketones such as N-thiophosphorylated thioureas [1], N-(thio)acylamido(thio)phosphates [2] and amidophosphates [3] have been well investigated. The main interest concerning these ligands connected with antivirus [4] and anticancer [5] activity, their using as components of ionselective electrodes [6], extragents [7] and as building blocks for obtaining new polydentate ligands, such as phosphorylated carbamides, which contain five- and six-membered N-heterocyclic fragments: 2-aminotyazole and 2-aminopiridine [8]. Using coordination compounds based on them as complexing and masking reagents in analytical chemistry [9]. In this context, during past few years many efforts have been devoted to the investigation of coordination behavior of P, N-substituted analogues of b-diketones with the general formula RC(O)NHP(O)(R0 )2 – carbacylamidophosphates (CAPh). A variety of new coordination compounds with s-, * Corresponding author. Tel.: +380 44 239 3392; fax: +380 44 239 3393. E-mail address: [email protected] (O.V. Moroz). 0277-5387/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.poly.2009.02.012
p-, d- and f-metals based on the CAPh have been synthesized. It was shown that the ligands of this type formed preferentially six-membered metalocycles in neutral [10] and deprotonated [11] forms. On the other hand, the examples of monodentate coordination have been observed (via nitrogen atom for the compound Na[Ag(CAPh)2] CH3CN [12] and via oxygen atom of phosphoryl group in case of neutral ligand coordination to Ln3+ ion [13]. In this context mono-, bi- and polynuclear coordination compounds have been obtained using 3d-metals and CAPh [14]. Moreover, many efforts have been devoted to the synthesis of another type of derivatives of b-diketones – sulfonyl phosphoramides – SAPh (RS(O)2NHP(O)(R0 )2) and their coordination chemistry (Chart 1). This type of phosphoramides with different substituents at sulfur and phosphorus atoms was first synthesized by Kirsanov [15]. One of the simplest representative of this class of ligands is dimethyl(phenylsulfonyl)amidophosphate (HL) of general formula C6H5S(O)2NHP(O)(OCH3)2. This type of compounds is widely used as bactericidal agents in medicine and toxicology [16], some SAPh are used as pesticides [17]. But the information concerning coordination compounds based on the sulfonyl phosphoramides and their potential use presented is very poor to date [18]. In this paper we report the synthesis, crystal structure, spectral and magnetic properties of the ligand HL (1) and coordination polymer [Cu(L)2 o-bpe]n (2), where 1,2-bis(pyridine-2-yl)ethane (o-bpe) is used as spacer.
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Chart 1. P, N-substituted analogues of b-diketones.
2. Experimental 2.1. Synthesis of HL (1) The dimethyl(phenylsulfonyl)amidophosphate was prepared according to the early published procedures [19]. Anal. Calc. for C8H12NO5PS (Mr = 265.22): C, 36.23; H, 4.56; N, 5.28; S, 12.09. Found: C, 36.12; H, 4.39; N, 5.24; S, 12.1%. IR (KBr, cm1): 3000(s), 2745(m), 1455(m), 1410(s), 1320(vs), 1260(vs), 1185(vs), 1100(s), 1075(vs), 1060(vs), 955(vs), 885(m), 855(s), 780(s), 695(m), 605(m), 585(s), 535(s), 495(w), 435(w) cm1. M.p. 121 °C. 1H NMR (DMSO): 3.57 (d, 6H, CH3, 3JP–H = 12 Hz), 7.58 (m, b-H, 2H, C6H5), 7.65 (m, c-H, 1H, C6H5), 7.91 (m, a-H, 2H, C6H5) ppm. 31P NMR (DMSO): 2.17 (g, 3JP–H=12 Hz) ppm.
265.22, Z = 4, space group P212121, Dcalc = 1.515 g/cm3, l (Mo Ka) = 0.421 mm1, F(0 0 0) = 552. Intensities of 5011 reflections (3154 independent, Rint = 0.0198) were measured on the «Xcalibur-3» diffractometer (graphite monochromated Mo Ka radiation, CCD detector, x-scaning, 2Hmax = 60°). The crystals of 2 (C28H32N4O10P2S2Cu) are monoclinic. At 293 K a = 28.255(2), b = 7.764(6), c = 18.600(6) Å, b = 125.57(3)°; V = 3318.9(3) Å3, Mr = 774.18, Z = 4, space group C2/c, Dcalc = 1.549 g/cm3, l (Mo Ka) = 0.941 mm1, F(0 0 0) = 1596. Intensities of 12 937 reflections (4628 independent, Rint = 0.028) were measured on the «Xcalibur-3» diffractometer (graphite monochromated Mo Ka radiation, CCD detector, x-scaning, 2Hmax = 60°). The structures were solved by direct method using SHELXTL package [21]. Positions of the hydrogen atoms were located from electron density difference maps and refined by ‘‘riding” model with Uiso = nUeq of the carrier atom (n = 1.5 for methyl group and n = 1.2 for other hydrogen atoms). Full-matrix least-squares refinement of the structures against F2 in anisotropic approximation for non-hydrogen atoms using 3108 (1) and 4594 (2) reflections was converged to: wR2 = 0.073 (R1 = 0.032 for 2500 reflections with F > 4r(F), S = 0.928) for structure 1 and wR2 = 0.105 (R1 = 0.040 for 3404 reflections with F > 4r(F), S = 1.028) for structure 2.
2.2. Synthesis of [Cu(L)2 o-bpe]n (2) A solution of HL (2 mmol) in isopropanol (10 ml) was mixed with isopropanol solution of sodium (2 mmol). To the resulting sodium salt the methanol solution of Cu(NO3)2 6H2O (5 ml) (1 mmol) was added. After 20 min the precipitate of NaNO3 was filtered off and was added to 10 ml of isopropanol solution of o-bpe (1 mmol). The resulting clear solution was left at ambient temperature for crystallization in air. The blue/green fine crystals were collected by filtration after 20 min, washed thoroughly with cool isopropanol and finally dried on filter. A well-formed crystal was used for the single X-ray structural analysis. Yield: 0.65 g (85%). Anal. Calc. for C28H32N4O10P2S2Cu (Mr = 774.2): C, 43.44; H, 4.17; N, 7.24; S, 8.28. Found: C, 43.31; H, 4.08; N, 7.22; S, 8.49%. IR (KBr, cm1): 2965(w), 2865(w), 1610(w), 1575(w), 1485(m), 1455(m), 1255(s), 1230(vs), 1185(vs), 1075(s), 1040(vs), 940(w), 840(s), 790(m), 750(m), 740(m), 720(m), 700(m), 615(s), 580(m), 555(s), 510(w), 450(m) cm1. The compound 2 is soluble in MeOH, EtOH, DMSO and DMF. 2.3. Physical measurements Elemental analysis (C, H, N and S) were performed using EL III Universal CHNOS Elemental Analyzer. IR spectra were recorded as KBr pellets using UR-10 spectrometer in the 4000–400 cm1 region using conventional techniques. NMR spectra were obtained using Varian Mercury 400 NMR spectrometer at 25 °C. 1H and 31P spectra were recorded at 400 and 162.1 MHz, respectively. Chemical shifts are reported with reference to SiMe4 (1H) and H3PO4 (31P). Electron paramagnetic resonance (EPR) spectra were recorded using CMS 8400 spectrometer at X-band frequency (9.38 GHz) at 298 and 77 K. The solid sample for EPR measurements was carefully pounded with pestle. Variable-temperature magnetic susceptibility data (2–300 K) were acquired on a powdered sample with the use of a Quantum Design MPMS-5 SQUID magnetometer. Corrections for the diamagnetism of the ligand were applied using Pascal’s constants [20]. 2.4. X-ray structure determination and refinement The crystals of 1 (C8H12NO5PS) are orthorhombic. At 293 K a = 7.521(3), b = 8.174(3), c = 18.919(5) Å, V = 1163.09(7) Å3, Mr =
3. Results and discussion 3.1. Synthesis and spectroscopic characterization Sodium salt NaL was obtained by the reaction of i-PrONa with iPrOH solution of HL. Cu(L)2 was prepared by the reaction of NaL with Cu(NO3)2 in alcohol solution. The presence of unsaturated coordination sphere of copper ion in Cu(L)2 can be used for obtaining a wide number of mix-ligand compounds by interaction of Cu(L)2 with various donor agents. In our work we used o-bpe as the bidentate bridging ligand. The reaction of Cu(L)2 with an equimolar amount of o-bpe in i-PrOH leads to the formation of polymeric complex with the general formula [Cu(L)2 o-bpe]n (2). Syntheses of all compounds were carried out in air. The vibration of the amide group m(N–H) in IR spectra of HL appears in the region of 2800–3200 cm1 with the maxima at 3000 cm1. This band absents in the spectra of NaL and [Cu(L)2 o-bpe]n, which can be consequence of the ligand’s coordination in deprotonated form (L). Two sharp bands which are observed in the spectrum of free ligand with maxima at 1260 and 1320 cm1 are assigned to m(PO) and m(SO) vibrations [22]. In the spectra of sodium salt and 2 these bands are shifted to lower frequencies (1185, 1230 and 1250 cm1 for NaL, 1180, 1230 and 1250 cm1 for 2) that can be explained by coordination to the metal ion. The analysis of IR spectra suggests a bidentate coordination of the anionic form L via the oxygen atoms of phosphoryl and sulfonyl groups. 3.2. Crystal structure of 1 White needle-shaped crystals of HL were grown over a period of 5 days from the i-PrOH–hexane solution. The molecular structure and the numbering scheme of 1 and crystal packing diagram are shown in Fig. 1, selected bond lengths and angles are listed in Table 1. Thus as CAPh, namely CCl3C(O)NHP(O)(OCH3)2 [23], the geometry around the phosphorus atom in HL (1) can be described as a distorted tetrahedron. The P(1)–O(3) and P(1)–N(1) bond lengths for 1 have values 1.456(1) and 1.662(2) Å, which are typical for CAPh with ether-type substituents [23–25]. The S(1)–O(1) (1.418(2) Å), S(1)–O(2) (1.428(2) Å) and S(1)–N(1) (1.642(2) Å)
O.V. Moroz et al. / Polyhedron 28 (2009) 1331–1335
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Fig. 1. Structural representation of 1 (a) with atom numbering scheme and 30% probability thermal ellipsoids, and fragments of the crystal packing in the structure of 1 (b). The hydrogen atoms are omitted for clarity. Hydrogen bonds are indicated by dashed lines.
Table 1 Selected geometrical parameters (distances (Å) and angles (°)) for 1. P(1)–O(3) P(1)–O(4) P(1)–O(5) P(1)–N(1) S(1)–O(1)
1.456(1) 1.550(1) 1.548(2) 1.662(2) 1.418(2)
S(1)–O(2) S(1)–N(1) S(1)–C(1) O(4)–C(7) O(5)–C(8)
1.428(1) 1.642(2) 1.760(2) 1.426(3) 1.433(3)
O(3)–P(1)–O(4) O(3)–P(1)–O(5) O(4)–P(1)–O(5) O(3)–P(1)–N(1) O(4)–P(1)–N(1) O(5)–P(1)–N(1) O(1)–S(1)–O(2) O(1)–S(1)–N(1)
115.6(1) 116.0(1) 103.7(1) 108.1(1) 108.4(1) 104.4(1) 119.7(1) 106.6(1)
O(2)–S(1)–N(1) O(1)–S(1)–C(1) O(2)–S(1)–C(1) N(1)–S(1)–C(1) C(7)–O(4)–P(1) C(8)–O(5)–P(1) S(1)–N(1)–P(1)
107.4(1) 108.0(1) 108.7(1) 105.6(1) 120.9(1) 127.7(2) 125.1(1)
bond lengths values depend on the substituent near the sulfur atom and have the typical values for sulfonylamide derivatives [26]. The values of the O–P–N bond angles are 108.4(1)°, 104.4(1)° and 108.1(1)° for the O(4)–P(1)–N(1), O(5)–P(1)–N(1) and O(3)– P(1)–N(1), respectively. It was early published that the presence of small substituents at phosphorus atom possesses a weak effect on the value of the O–P–N angle which falls in the range 107.5– 108.9° [27]. Due to the steric effects the O(3)–P(1)–O(4) and O(3)–P(1)–O(5) angles are 115.6(1)° and 116.0(1)°, respectively, which are usually more than those in the ideal tetrahedron. The sulfur atom in the sulfonyl group has a distorted tetrahedral environment too (Table 1). The O(2) and O(3) oxygen atoms of sulfonyl and phosphoryl groups are located in anti-positions to each other similar to most of CAPh [27]. The P@O bond adopts conformation with respect to
the N(1)–S(1) bond, O(3)–P(1)–N(1)–S(1) fragment is practically planar (the torsion angle is 167.0(1)°). The deviations of the O(1) and O(2) from the P(1)–N(1)–S(1) plane are 0.583 and 0.579 Å, respectively. In the crystal packing molecules of 1 are linked to each other by intermolecular hydrogen bonds where amide nitrogen atom of one molecule acts as donor and oxygen atom of phosphoryl group of neighboring molecule acts as acceptor (HO0 1.96 Å, N–HO0 170°) and form the infinite zigzag chains along [1 0 0] crystallographic direction. Neighboring chains are connected by the C(7)– H(7A)p0 (x 1, y 1, z) hydrogen bonds (HC0 2.84 Å, C–Hp0 153°). 3.3. Crystal structure of 2 The molecular structure of 2 is shown in Fig. 2 (H atoms are omitted for clarity); selected bond distances and angles are presented in Table 2. The compound has 1D polymer chain structure along [0 1 0] crystallographic direction and consists of Cu(L)2 units bridged by o-bpe ligands. Two sulfamide ligands are coordinated to metal ion in trans-positions because of the presence of steric effects concerning to the asymmetric (chiral) feature of coordinated SO-group. The Cu(1) atom is located in the special position in the center of symmetry. The coordination environment of Cu(II) ion can be described as a distorted square-bipyramidal polyhedron (4 + 2). The CuO4N2 chromophore is constructed from two pyridyl nitrogen atoms from two o-bpe linkers and four oxygen atoms of phosphoryl and sulfonyl groups from two ligands which are coordinated in bidentate chelate mode forming with central ion sixmembered chelate rings. The Cu–O and Cu–N bond distances and O–Cu–O0 , O–Cu–N, N–Cu–N0 angles (Table 2) are typical for square-bipyramidal copper complexes with clear presence of
Fig. 2. Structural representation of 2 (a) with atom numbering scheme and 20% probability thermal ellipsoids, and fragments of the crystal packing in the structure of 2 (b). The hydrogen atoms are omitted for clarity.
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Table 2 Selected geometrical parameters (distances (Å) and angles (°)) for 2. Cu(1)–O(3) Cu(1)–N(2) Cu(1)–O(2) S(1)–O(2) S(1)–O(1) S(1)–N(1) S(1)–C(1)
1.950(1) 2.053(1) 2.589(1) 1.450(2) 1.440(2) 1.554(2) 1.775(2)
P(1)–O(5) P(1)–O(4) P(1)–O(3) P(1)–N(1) O(4)–C(7) O(5)–C(8)
1.566(2) 1.576(2) 1.496(2) 1.591(2) 1.407(3) 1.441(4)
O(3)–Cu(1)–O(3)#1 O(3)–Cu(1)–N(2)#1 O(3)#1–Cu(1)–N(2)#1 O(3)–Cu(1)–N(2) O(3)#1–Cu(1)–N(2) N(2)#1–Cu(1)–N(2) O(2)–Cu(1)–O(3) O(2)#1–Cu(1)–O(3) N(2)#1–Cu(1)–O(2) N(2)–Cu(1)–O(3) O(2)–S(1)–O(1) O(2)–S(1)–N(1) O(1)–S(1)–N(1) O(2)–S(1)–C(1) O(1)–S(1)–C(1)
180.0(1) 90.6(1) 89.4(1) 89.4(1) 90.6(1) 180.0(1) 82.5(1) 97.58(7) 99.3(1) 89.4(1) 114.8(1) 111.6(1) 109.6(1) 106.0(1) 106.9(1)
N(1)–S(1)–C(1) O(5)–P(1)–O(4) O(4)–P(1)–O(3) O(5)–P(1)–O(4) O(3)–P(1)–N(1) O(5)–P(1)–N(1) O(4)–P(1)–N(1) P(1)–O(3)–Cu(1) S(1)–O(2)–Cu(1) C(7)–O(4)–P(1) C(8)–O(5)–P(1) C(9)–N(2)–C(13) C(9)–N(2)–Cu(1) C(13)–N(2)–Cu(1) S(1)–N(1)–P(1)
107.7(1) 107.3(1) 106.5(1) 107.3(1) 119.7(1) 106.5(1) 106.8(1) 129.7(1) 125.3(1) 123.9(2) 121.2(2) 118.5(2) 115.6(1) 125.7(1) 126.4(1)
Symmetry transformations used to generate equivalent atoms: (#1) <x + 1/2, y + 1/2, z + 1>.
Jahn–Teller distortion. The Cu–O(S), Cu–O(P) and Cu–N bond values are 2.588(2), 1.950(1) and 2.053(2) Å, respectively. The sixmembered chelate ring adopts a twist-boat conformation (the puckering parameters are S = 0.67, h = 86.32, w = 17.43) [28]. The deviations of the N(1) and Cu(1) atoms from the O(1)–S(1)–P(1)– O(5) mean plane are 0.40 and 0.74 Å, respectively. The chelate angles values fall in the range 82.5(6)–99.3(6)° which are typical for Cu(II) complexes with octahedral coordination. The amide nitrogen atom of ligand is deprotonated that leads to the decrease of the S(1)–N(1) and N(1)–P(1) bond length values (Table 2) in comparison with the same values for neutral ligand (structure 1). In spite of the deprotonation of amide group the O–P–N–S–O backbone is not flat. The P(1)–O(3) and S(1)–O(2) bond values are elongated due to the coordination, the conformation of the O–P–N–S–O fragment is changed owing to the turn of the phosphoryl group relatively the N(1)–S(1) bond (the O(3)– P(1)–N(1)–S(1) is 35.1(2)°). In the crystal packing neighboring polymer chains are connected by the C(11)–H(11)p0 (x, 1 y, z 0.5) weak hydrogen bonds (HC0 2.85 Å, C–Hp0 130°) and form layers which are parallel to OYZ plane. The o-bpe ligands are coordinated to the 3dmetals forming trans-isomers of complexes which are typical for the ligands of this type [29]. The CuCu0 separations in chain are 7.75 Å. 3.4. EPR studies and magnetochemistry The X-band EPR spectrum of a solid sample of 2 at 77 K shows the presence of elongated axial symmetry signal with not resolved hyperfine structure (Fig. 3a). The values of anisotropic parameters of the spectrum are g|| = 2.365, g\ = 2.095, which are typical for copper(II) ions with dx2 y2 ground state. The ‘‘half-field” signal is not observed which can be suggested as the absence of magnetic exchange interaction between copper(II) ions or the value of it is very weak. The EPR spectrum of frozen diluted solution at 77 K (Fig. 3b) is not similar to that observed in the solid state with the presence of hyperfine splitting in the parallel orientation region. The values of parameters are g|| = 2.450, g\ = 2.105 and A|| = 126 104 cm1 which are typical for CuO6 octahedral coordination environment [30]. Such behavior can be explained by dissociation of polymeric
Fig. 3. X-band EPR spectra of compound 2: (a) solid 2 at 77 K and (b) frozen CHCl3/ CH3OH (1:1, v/v) solution of 2 at 77 K.
complexes in solution and ligand exchange (o-bpe molecules to solvent alcohol molecules). Variable-temperature magnetic susceptibility studies for compound 2 were carried out over the temperature range 2–295 K. The magnetic moment of 2 at room temperature was 1.94lB (corresponds to vMT of 0.467 cm3 K mol1) which is a typical value for copper(II) and slightly greater than the expected spin-only value. The susceptibility (vM) of 2 showed steady increase upon cooling, without maximum (h in Fig. 4). The plot of vMT (per mole) versus temperature (d in Fig. 4) shows that vMT first negligible decreased from 0.467 cm3 K mol1 at 295 K to 0.439 cm3 K mol1 at 10 K (1.94lB and 1.88lB, respectively), then sharply decreased to 0.404 cm3 K mol1 at 2 K (1.80lB). This is clearly indicative the presence of week antiferromagnetic behavior within the chain. A simulation of these data was based on the Hamiltonian (Eq. (1)) and derived by Bonner and Fisher for infinite chain model with magnetically identical S = ½ metal centers (Eq. (2)) [31]:
^ ¼ J H
X
^i S ^iþ1 S
ð1Þ
0 1 2 ! jJj jJj 2 2 þ 0:075235 0:25 þ 0:074975 kT kT Ng b B C v0 ¼ @ 2 3 A kT jJj jJj jJj 1 þ 0:9931 kT þ 0:757825 kT þ 0:172135 kT ð2Þ In Eq. (2) J,N, g, b and k have their usual meanings. However, the presence of unlinked copper ions and/or short odd-numbered
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Supplementary data CCDC 710779 and 710780 contains the supplementary crystallographic data for 1 and 2. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: [email protected]. Acknowledgement This work was supported in part by Fundamental Researches State Fund of Ukraine (Project F25/193 – 2008). References Fig. 4. Plot of vM and vMT vs. T for 2; the solid line represents the simulated curve.
chains was taken into account; the experimental vMT of 2 was fitted using the Eq. (3) in which q – the fraction of paramagnetic impurity. Temperature independent paramagnetism (PTI) was also added in calculations:
v ¼ ð1 qÞv0 þ
Ng 2 b2 q þ PTI 4kT
ð3Þ
The best fit calculated for 2 gave the following parameter values: g = 2.180(1), J = 0.21(1) cm1, q = 0%, PTI = 74(1) 106 P P cm3 mol1, R = 1.49 103, where R = [ (Xobs Xcalc)2/ X 2calc ]1/2. The small negative value of J confirms the presence of weak predominant antiferromagnetic coupling within the chain. The small decreasing in vMT in the 10–300 K temperature range can be explained by existence of temperature independent paramagnetism. The obtaining value of isotropic g-factor is close to those calculated from EPR spectrum as gav (Eq. (4)):
g av ¼
ðg k þ 2g ? Þ 3
ð4Þ
However, the CuCu0 distance in chain is sizeable enough the exchange interaction between copper(II) ions are mediated by the system of conjugated C@C bonds of o-bpe. The value of J cannot be compared because there is only one record concerning using o-bpe for bridging copper(I) [31] and no records for copper(II) ions reported to date. 4. Conclusion The paper is devoted to coordination chemistry of sulfonyl phosphoramide ligands and their complex with copper(II). The new copper(II) complex containing deprotonated sulfamide ligands and o-bpe as bridging ligand has been obtained. The X-ray crystal structures for HL and [Cu(L)2 o-bpe]n have been determined. In contrast to fully characterized CAPh ligands, which usually form dimer structure by means of hydrogen bonds, the molecules of 1 form a hydrogen bonded chain in which they are linked to each other due to identical (P)OH–N contacts. The compound 2 has 1D polymeric chain structure. The magnetic study of 2 shows the presence of weak intrachain antiferromagnetic exchange interaction between copper(II) ions.
[1] F.D. Sokolov, V.V. Brusko, N.G. Zabirov, R.A. Cherkasov, Curr. Org. Chem. 10 (2006) 27. [2] D.A. Safin, F.D. Sokolov, N.G. Zabirov, V.V. Brusko, D.B. Krivolapov, I.A. Litvinov, R.C. Luckay, R.A. Cherkasov, Polyhedron 25 (2006) 3330. [3] F.D. Sokolov, D.A. Safin, N.G. Zabirov, V.V. Brusko, B.I. Khairutdinov, D.B. Krivolapov, I.A. Litvinov, Eur. J. Inorg. Chem. 10 (2006) 2027. [4] N.G. Zabirov, O.K. Pozdeev, F.M. Shamsevaleev, R.A. Cherkasov, G.H. Gilmanova, Pharm. Chem. J. 23 (1989) 423. [5] (a) V. Amirkhanov, C. Janczak, L. Macalik, J. Hanuza, J. Legendziewicz, J. Appl. Spectros. 62 (1995) 5; (b) V. Amirkhanov, V. Ovchinnikov, J. Legendziewicz, A. Graczyk, J. Hanuza, L. Macalik, Acta Phys. Polon. 90 (1996) 455. [6] L.G. Shaidarova, A.V. Gedmina, N.A. Ulahovich, G.K. Budnikov, N.G. Zabirov, Zh. Obshch. Khim. 72 (2002) 1662. [7] O. Navratil, E. Herrmann, N.T.T. Chau, Ch. Tea, J. Smola, Collect. Czech. Chem. Commun. 58 (1993) 798. [8] K.O. Znovjyak, V.A. Ovchynnikov, S.V. Shishkina, T.Yu. Sliva, V.M. Amirkhanov, Doklady Akademii Nauk 9 (2006) 151. [9] M.G. Zimin, G.A. Lazareva, N.I. Savelieva, R.G. Islamov, N.G. Zabirov, V.F. Toropova, A.N. Pudovik, Zh. Obshch. Khim. (J. Gen. Chem. USSR) 52 (1982) 1573. [10] K.E. Gubina, V.A. Ovchynnikov, V.M. Amirkhanov, H. Fischer, R. Stumpf, V.V. Skopenko, Z. Naturforsch. 55b (2000) 576. [11] V. Skopenko, V. Amirkhanov, T. Sliva, I. Vasilchenko, E. Anpilova, A. Garnovskii, Usp. Khim. 73 (2004) 797. [12] V.A. Trush, K.V. Domasevitch, V.M. Amirkhanov, Doklady Akademii Nauk 7 (2007) 147. [13] V.A. Ovchynnikov, T.P. Timoshenko, V.M. Amirkhanov, J. Sieler, V.V. Skopenko, Z. Naturforsch. 55b (2000) 262. [14] (a) E.A. Trush, V.M. Amirkhanov, V.A. Ovchynnikov, J. Swiatek-Kozlowska, K.A. Lanikina, K.V. Domasevitch, Polyhedron 00 (2003) 1; (b) V.A. Ovchynnikov, V.M. Amirkhanov, A.A. Kapshuk, T.Yu. Sliva, T. Glowiak, H. Kozlowski, Z. Naturforsch. 53b (1998) 836. [15] A.V. Kirsanov, Fosfazosoedineniya (Phosphazo Compounds) Naukova Dumka, Kiev, 1965. [16] K. Xu, C. Angell, Inorg. Chim. Acta 298 (2000) 16. [17] S. Kishino, S. Saito, US Patent 4 161 524, 1979. [18] O.V. Moroz, S.V. Shishkina, V.A. Trush, T.Yu. Sliva, V.M. Amirkhanov, Acta Crystallogr., Sect. E 63 (2007) m3175. [19] A. Kirsanov, V. Shevchenko, Zh. Obshch. Khim. 26 (1956) 504. [20] G.A. Bain, J.F. Berry, J. Chem. Edu. 85 (2008) 532. [21] G.M. Sheldrick, SHELXL97 and SHELXS97, University of Göttingen, Germany, 1997. [22] S. Boudjabi, G. Dewynter, J.-L. Montero, Synlett 5 (2000) 716. [23] V.M. Amirkhanov, V.A. Trush, Zh. Obsch. Khim. 65 (1995) 1120. [24] K.E. Gubina, V.M. Amirkhanov, Naturforsch 55b (2000) 1015. [25] V. Miztahi, T.A. Modro, Cryst. Struct. Commun. 11 (1982) 627. [26] H.-B. Burgi, J.D. Dunitz, Structure Correlation, vol. 2, VCH, Weinheim, 1997. [27] V.M. Amirkhanov, V.A. Ovchinnikov, T. Glowiak, H. Kozlowski, Naturforsch 52b (1997) 1331. [28] N.S. Zefirov, V.A. Palyulin, E.E. Dashevskaya, J. Phys. Org. Chem. 3 (1990) 147. [29] S. Kitagawa, S. Matsuyama, M. Munakata, T. Emori, J. Chem. Soc., Dalton Trans. (1991) 2869. [30] (a) B. Kozlevcar, A. Golobic, P. Strauch, Polyhedron 25 (2006) 2824; (b) V.E. Petrashen, Y.V. Yablokov, R.L. Davidovich, Phys. Status Solids B 101 (1980) 117; (c) D.K. De, J. Magn. Reson. 47 (1982) 181. [31] W.E. Estes, D.P. Gavel, W.E. Hatfield, D.J. Hodgson, Inorg. Chem. 17 (1978) 1415.
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New copper(II) 1D polymer containing dimethyl(phenylsulfonyl)amidophosphate: Synthesis, crystal structure and magnetic properties Olesia V. Moroz a,*, Victor A. Trush a, Irina S. Konovalova b, Oleg V. Shishkin b,c, Yurii S. Moroz a, Serhiy Demeshko d, Vladimir M. Amirkhanov a a
Department of Chemistry, National Taras Shevchenko University, Volodymyrska Str. 64, Kyiv 01601, Ukraine STC ‘‘Institute for Single Crystals”, National Academy of Science of Ukraine, 60 Lenina Ave., Kharkiv 61001, Ukraine c V.N. Karazin Kharkiv National University, 4 Svobody Sq., Kharkiv 61077, Ukraine d Georg-August-University, Institute of Inorganic Chemistry, Tammannstr. 4, Goettingen D-37077, Germany b
a r t i c l e
i n f o
Article history: Received 28 November 2008 Accepted 7 February 2009 Available online 20 February 2009 Keywords: Sulfonyl phosphoramides One-dimensional polymeric structure Antiferromagnetic behavior
a b s t r a c t The reaction of sodium dimethyl(phenylsulfonyl)amidophosphate NaL (HL = C6H5SO2NHP(O)(OCH3)2) with Cu(NO3)2 6H2O and o-bpe (1,2-bis(pyridine-2-yl)ethane) in appropriate ratios, afford the formation of 1D coordination polymer [Cu(L)2 o-bpe]n in good yield. The crystal structures of HL (1) and [Cu(L)2 o-bpe]n (2) are reported. In the crystal package the molecules of 1 are linked by intermolecular hydrogen bonds formed by the phosphoryl oxygen atoms which serve as acceptors and nitrogen atoms of amide groups as donors. The crystal structure of 2 indicates the presence of unsaturated Cu(L)2 unit bridged by o-bpe ligand in the one-dimensional polymeric chain. The Cu(II) atoms have distorted 4 + 2 octahedral CuO4N2 environment formed by the oxygen atoms belonging to the sulfonyl and phosphoryl groups of two deprotonated chelate ligands and nitrogen atoms of the bridging o-bpe ligands. The magnetic study of 2 has revealed the presence of a weak intrachain antiferromagnetic exchange interaction between copper ions. Ó 2009 Elsevier Ltd. All rights reserved.
1. Introduction In the past few decades the investigation of new polydentate chelate ligands has attracted considerable attention in the field of modern inorganic chemistry because of the formation of kinetic, thermodynamic and thermic stable coordination compounds based on these ligands with potentially useful properties. Up to date azo- and hetero-analogues of b-diketones such as N-thiophosphorylated thioureas [1], N-(thio)acylamido(thio)phosphates [2] and amidophosphates [3] have been well investigated. The main interest concerning these ligands connected with antivirus [4] and anticancer [5] activity, their using as components of ionselective electrodes [6], extragents [7] and as building blocks for obtaining new polydentate ligands, such as phosphorylated carbamides, which contain five- and six-membered N-heterocyclic fragments: 2-aminotyazole and 2-aminopiridine [8]. Using coordination compounds based on them as complexing and masking reagents in analytical chemistry [9]. In this context, during past few years many efforts have been devoted to the investigation of coordination behavior of P, N-substituted analogues of b-diketones with the general formula RC(O)NHP(O)(R0 )2 – carbacylamidophosphates (CAPh). A variety of new coordination compounds with s-, * Corresponding author. Tel.: +380 44 239 3392; fax: +380 44 239 3393. E-mail address: [email protected] (O.V. Moroz). 0277-5387/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.poly.2009.02.012
p-, d- and f-metals based on the CAPh have been synthesized. It was shown that the ligands of this type formed preferentially six-membered metalocycles in neutral [10] and deprotonated [11] forms. On the other hand, the examples of monodentate coordination have been observed (via nitrogen atom for the compound Na[Ag(CAPh)2] CH3CN [12] and via oxygen atom of phosphoryl group in case of neutral ligand coordination to Ln3+ ion [13]. In this context mono-, bi- and polynuclear coordination compounds have been obtained using 3d-metals and CAPh [14]. Moreover, many efforts have been devoted to the synthesis of another type of derivatives of b-diketones – sulfonyl phosphoramides – SAPh (RS(O)2NHP(O)(R0 )2) and their coordination chemistry (Chart 1). This type of phosphoramides with different substituents at sulfur and phosphorus atoms was first synthesized by Kirsanov [15]. One of the simplest representative of this class of ligands is dimethyl(phenylsulfonyl)amidophosphate (HL) of general formula C6H5S(O)2NHP(O)(OCH3)2. This type of compounds is widely used as bactericidal agents in medicine and toxicology [16], some SAPh are used as pesticides [17]. But the information concerning coordination compounds based on the sulfonyl phosphoramides and their potential use presented is very poor to date [18]. In this paper we report the synthesis, crystal structure, spectral and magnetic properties of the ligand HL (1) and coordination polymer [Cu(L)2 o-bpe]n (2), where 1,2-bis(pyridine-2-yl)ethane (o-bpe) is used as spacer.
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Chart 1. P, N-substituted analogues of b-diketones.
2. Experimental 2.1. Synthesis of HL (1) The dimethyl(phenylsulfonyl)amidophosphate was prepared according to the early published procedures [19]. Anal. Calc. for C8H12NO5PS (Mr = 265.22): C, 36.23; H, 4.56; N, 5.28; S, 12.09. Found: C, 36.12; H, 4.39; N, 5.24; S, 12.1%. IR (KBr, cm1): 3000(s), 2745(m), 1455(m), 1410(s), 1320(vs), 1260(vs), 1185(vs), 1100(s), 1075(vs), 1060(vs), 955(vs), 885(m), 855(s), 780(s), 695(m), 605(m), 585(s), 535(s), 495(w), 435(w) cm1. M.p. 121 °C. 1H NMR (DMSO): 3.57 (d, 6H, CH3, 3JP–H = 12 Hz), 7.58 (m, b-H, 2H, C6H5), 7.65 (m, c-H, 1H, C6H5), 7.91 (m, a-H, 2H, C6H5) ppm. 31P NMR (DMSO): 2.17 (g, 3JP–H=12 Hz) ppm.
265.22, Z = 4, space group P212121, Dcalc = 1.515 g/cm3, l (Mo Ka) = 0.421 mm1, F(0 0 0) = 552. Intensities of 5011 reflections (3154 independent, Rint = 0.0198) were measured on the «Xcalibur-3» diffractometer (graphite monochromated Mo Ka radiation, CCD detector, x-scaning, 2Hmax = 60°). The crystals of 2 (C28H32N4O10P2S2Cu) are monoclinic. At 293 K a = 28.255(2), b = 7.764(6), c = 18.600(6) Å, b = 125.57(3)°; V = 3318.9(3) Å3, Mr = 774.18, Z = 4, space group C2/c, Dcalc = 1.549 g/cm3, l (Mo Ka) = 0.941 mm1, F(0 0 0) = 1596. Intensities of 12 937 reflections (4628 independent, Rint = 0.028) were measured on the «Xcalibur-3» diffractometer (graphite monochromated Mo Ka radiation, CCD detector, x-scaning, 2Hmax = 60°). The structures were solved by direct method using SHELXTL package [21]. Positions of the hydrogen atoms were located from electron density difference maps and refined by ‘‘riding” model with Uiso = nUeq of the carrier atom (n = 1.5 for methyl group and n = 1.2 for other hydrogen atoms). Full-matrix least-squares refinement of the structures against F2 in anisotropic approximation for non-hydrogen atoms using 3108 (1) and 4594 (2) reflections was converged to: wR2 = 0.073 (R1 = 0.032 for 2500 reflections with F > 4r(F), S = 0.928) for structure 1 and wR2 = 0.105 (R1 = 0.040 for 3404 reflections with F > 4r(F), S = 1.028) for structure 2.
2.2. Synthesis of [Cu(L)2 o-bpe]n (2) A solution of HL (2 mmol) in isopropanol (10 ml) was mixed with isopropanol solution of sodium (2 mmol). To the resulting sodium salt the methanol solution of Cu(NO3)2 6H2O (5 ml) (1 mmol) was added. After 20 min the precipitate of NaNO3 was filtered off and was added to 10 ml of isopropanol solution of o-bpe (1 mmol). The resulting clear solution was left at ambient temperature for crystallization in air. The blue/green fine crystals were collected by filtration after 20 min, washed thoroughly with cool isopropanol and finally dried on filter. A well-formed crystal was used for the single X-ray structural analysis. Yield: 0.65 g (85%). Anal. Calc. for C28H32N4O10P2S2Cu (Mr = 774.2): C, 43.44; H, 4.17; N, 7.24; S, 8.28. Found: C, 43.31; H, 4.08; N, 7.22; S, 8.49%. IR (KBr, cm1): 2965(w), 2865(w), 1610(w), 1575(w), 1485(m), 1455(m), 1255(s), 1230(vs), 1185(vs), 1075(s), 1040(vs), 940(w), 840(s), 790(m), 750(m), 740(m), 720(m), 700(m), 615(s), 580(m), 555(s), 510(w), 450(m) cm1. The compound 2 is soluble in MeOH, EtOH, DMSO and DMF. 2.3. Physical measurements Elemental analysis (C, H, N and S) were performed using EL III Universal CHNOS Elemental Analyzer. IR spectra were recorded as KBr pellets using UR-10 spectrometer in the 4000–400 cm1 region using conventional techniques. NMR spectra were obtained using Varian Mercury 400 NMR spectrometer at 25 °C. 1H and 31P spectra were recorded at 400 and 162.1 MHz, respectively. Chemical shifts are reported with reference to SiMe4 (1H) and H3PO4 (31P). Electron paramagnetic resonance (EPR) spectra were recorded using CMS 8400 spectrometer at X-band frequency (9.38 GHz) at 298 and 77 K. The solid sample for EPR measurements was carefully pounded with pestle. Variable-temperature magnetic susceptibility data (2–300 K) were acquired on a powdered sample with the use of a Quantum Design MPMS-5 SQUID magnetometer. Corrections for the diamagnetism of the ligand were applied using Pascal’s constants [20]. 2.4. X-ray structure determination and refinement The crystals of 1 (C8H12NO5PS) are orthorhombic. At 293 K a = 7.521(3), b = 8.174(3), c = 18.919(5) Å, V = 1163.09(7) Å3, Mr =
3. Results and discussion 3.1. Synthesis and spectroscopic characterization Sodium salt NaL was obtained by the reaction of i-PrONa with iPrOH solution of HL. Cu(L)2 was prepared by the reaction of NaL with Cu(NO3)2 in alcohol solution. The presence of unsaturated coordination sphere of copper ion in Cu(L)2 can be used for obtaining a wide number of mix-ligand compounds by interaction of Cu(L)2 with various donor agents. In our work we used o-bpe as the bidentate bridging ligand. The reaction of Cu(L)2 with an equimolar amount of o-bpe in i-PrOH leads to the formation of polymeric complex with the general formula [Cu(L)2 o-bpe]n (2). Syntheses of all compounds were carried out in air. The vibration of the amide group m(N–H) in IR spectra of HL appears in the region of 2800–3200 cm1 with the maxima at 3000 cm1. This band absents in the spectra of NaL and [Cu(L)2 o-bpe]n, which can be consequence of the ligand’s coordination in deprotonated form (L). Two sharp bands which are observed in the spectrum of free ligand with maxima at 1260 and 1320 cm1 are assigned to m(PO) and m(SO) vibrations [22]. In the spectra of sodium salt and 2 these bands are shifted to lower frequencies (1185, 1230 and 1250 cm1 for NaL, 1180, 1230 and 1250 cm1 for 2) that can be explained by coordination to the metal ion. The analysis of IR spectra suggests a bidentate coordination of the anionic form L via the oxygen atoms of phosphoryl and sulfonyl groups. 3.2. Crystal structure of 1 White needle-shaped crystals of HL were grown over a period of 5 days from the i-PrOH–hexane solution. The molecular structure and the numbering scheme of 1 and crystal packing diagram are shown in Fig. 1, selected bond lengths and angles are listed in Table 1. Thus as CAPh, namely CCl3C(O)NHP(O)(OCH3)2 [23], the geometry around the phosphorus atom in HL (1) can be described as a distorted tetrahedron. The P(1)–O(3) and P(1)–N(1) bond lengths for 1 have values 1.456(1) and 1.662(2) Å, which are typical for CAPh with ether-type substituents [23–25]. The S(1)–O(1) (1.418(2) Å), S(1)–O(2) (1.428(2) Å) and S(1)–N(1) (1.642(2) Å)
O.V. Moroz et al. / Polyhedron 28 (2009) 1331–1335
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Fig. 1. Structural representation of 1 (a) with atom numbering scheme and 30% probability thermal ellipsoids, and fragments of the crystal packing in the structure of 1 (b). The hydrogen atoms are omitted for clarity. Hydrogen bonds are indicated by dashed lines.
Table 1 Selected geometrical parameters (distances (Å) and angles (°)) for 1. P(1)–O(3) P(1)–O(4) P(1)–O(5) P(1)–N(1) S(1)–O(1)
1.456(1) 1.550(1) 1.548(2) 1.662(2) 1.418(2)
S(1)–O(2) S(1)–N(1) S(1)–C(1) O(4)–C(7) O(5)–C(8)
1.428(1) 1.642(2) 1.760(2) 1.426(3) 1.433(3)
O(3)–P(1)–O(4) O(3)–P(1)–O(5) O(4)–P(1)–O(5) O(3)–P(1)–N(1) O(4)–P(1)–N(1) O(5)–P(1)–N(1) O(1)–S(1)–O(2) O(1)–S(1)–N(1)
115.6(1) 116.0(1) 103.7(1) 108.1(1) 108.4(1) 104.4(1) 119.7(1) 106.6(1)
O(2)–S(1)–N(1) O(1)–S(1)–C(1) O(2)–S(1)–C(1) N(1)–S(1)–C(1) C(7)–O(4)–P(1) C(8)–O(5)–P(1) S(1)–N(1)–P(1)
107.4(1) 108.0(1) 108.7(1) 105.6(1) 120.9(1) 127.7(2) 125.1(1)
bond lengths values depend on the substituent near the sulfur atom and have the typical values for sulfonylamide derivatives [26]. The values of the O–P–N bond angles are 108.4(1)°, 104.4(1)° and 108.1(1)° for the O(4)–P(1)–N(1), O(5)–P(1)–N(1) and O(3)– P(1)–N(1), respectively. It was early published that the presence of small substituents at phosphorus atom possesses a weak effect on the value of the O–P–N angle which falls in the range 107.5– 108.9° [27]. Due to the steric effects the O(3)–P(1)–O(4) and O(3)–P(1)–O(5) angles are 115.6(1)° and 116.0(1)°, respectively, which are usually more than those in the ideal tetrahedron. The sulfur atom in the sulfonyl group has a distorted tetrahedral environment too (Table 1). The O(2) and O(3) oxygen atoms of sulfonyl and phosphoryl groups are located in anti-positions to each other similar to most of CAPh [27]. The P@O bond adopts conformation with respect to
the N(1)–S(1) bond, O(3)–P(1)–N(1)–S(1) fragment is practically planar (the torsion angle is 167.0(1)°). The deviations of the O(1) and O(2) from the P(1)–N(1)–S(1) plane are 0.583 and 0.579 Å, respectively. In the crystal packing molecules of 1 are linked to each other by intermolecular hydrogen bonds where amide nitrogen atom of one molecule acts as donor and oxygen atom of phosphoryl group of neighboring molecule acts as acceptor (HO0 1.96 Å, N–HO0 170°) and form the infinite zigzag chains along [1 0 0] crystallographic direction. Neighboring chains are connected by the C(7)– H(7A)p0 (x 1, y 1, z) hydrogen bonds (HC0 2.84 Å, C–Hp0 153°). 3.3. Crystal structure of 2 The molecular structure of 2 is shown in Fig. 2 (H atoms are omitted for clarity); selected bond distances and angles are presented in Table 2. The compound has 1D polymer chain structure along [0 1 0] crystallographic direction and consists of Cu(L)2 units bridged by o-bpe ligands. Two sulfamide ligands are coordinated to metal ion in trans-positions because of the presence of steric effects concerning to the asymmetric (chiral) feature of coordinated SO-group. The Cu(1) atom is located in the special position in the center of symmetry. The coordination environment of Cu(II) ion can be described as a distorted square-bipyramidal polyhedron (4 + 2). The CuO4N2 chromophore is constructed from two pyridyl nitrogen atoms from two o-bpe linkers and four oxygen atoms of phosphoryl and sulfonyl groups from two ligands which are coordinated in bidentate chelate mode forming with central ion sixmembered chelate rings. The Cu–O and Cu–N bond distances and O–Cu–O0 , O–Cu–N, N–Cu–N0 angles (Table 2) are typical for square-bipyramidal copper complexes with clear presence of
Fig. 2. Structural representation of 2 (a) with atom numbering scheme and 20% probability thermal ellipsoids, and fragments of the crystal packing in the structure of 2 (b). The hydrogen atoms are omitted for clarity.
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Table 2 Selected geometrical parameters (distances (Å) and angles (°)) for 2. Cu(1)–O(3) Cu(1)–N(2) Cu(1)–O(2) S(1)–O(2) S(1)–O(1) S(1)–N(1) S(1)–C(1)
1.950(1) 2.053(1) 2.589(1) 1.450(2) 1.440(2) 1.554(2) 1.775(2)
P(1)–O(5) P(1)–O(4) P(1)–O(3) P(1)–N(1) O(4)–C(7) O(5)–C(8)
1.566(2) 1.576(2) 1.496(2) 1.591(2) 1.407(3) 1.441(4)
O(3)–Cu(1)–O(3)#1 O(3)–Cu(1)–N(2)#1 O(3)#1–Cu(1)–N(2)#1 O(3)–Cu(1)–N(2) O(3)#1–Cu(1)–N(2) N(2)#1–Cu(1)–N(2) O(2)–Cu(1)–O(3) O(2)#1–Cu(1)–O(3) N(2)#1–Cu(1)–O(2) N(2)–Cu(1)–O(3) O(2)–S(1)–O(1) O(2)–S(1)–N(1) O(1)–S(1)–N(1) O(2)–S(1)–C(1) O(1)–S(1)–C(1)
180.0(1) 90.6(1) 89.4(1) 89.4(1) 90.6(1) 180.0(1) 82.5(1) 97.58(7) 99.3(1) 89.4(1) 114.8(1) 111.6(1) 109.6(1) 106.0(1) 106.9(1)
N(1)–S(1)–C(1) O(5)–P(1)–O(4) O(4)–P(1)–O(3) O(5)–P(1)–O(4) O(3)–P(1)–N(1) O(5)–P(1)–N(1) O(4)–P(1)–N(1) P(1)–O(3)–Cu(1) S(1)–O(2)–Cu(1) C(7)–O(4)–P(1) C(8)–O(5)–P(1) C(9)–N(2)–C(13) C(9)–N(2)–Cu(1) C(13)–N(2)–Cu(1) S(1)–N(1)–P(1)
107.7(1) 107.3(1) 106.5(1) 107.3(1) 119.7(1) 106.5(1) 106.8(1) 129.7(1) 125.3(1) 123.9(2) 121.2(2) 118.5(2) 115.6(1) 125.7(1) 126.4(1)
Symmetry transformations used to generate equivalent atoms: (#1) <x + 1/2, y + 1/2, z + 1>.
Jahn–Teller distortion. The Cu–O(S), Cu–O(P) and Cu–N bond values are 2.588(2), 1.950(1) and 2.053(2) Å, respectively. The sixmembered chelate ring adopts a twist-boat conformation (the puckering parameters are S = 0.67, h = 86.32, w = 17.43) [28]. The deviations of the N(1) and Cu(1) atoms from the O(1)–S(1)–P(1)– O(5) mean plane are 0.40 and 0.74 Å, respectively. The chelate angles values fall in the range 82.5(6)–99.3(6)° which are typical for Cu(II) complexes with octahedral coordination. The amide nitrogen atom of ligand is deprotonated that leads to the decrease of the S(1)–N(1) and N(1)–P(1) bond length values (Table 2) in comparison with the same values for neutral ligand (structure 1). In spite of the deprotonation of amide group the O–P–N–S–O backbone is not flat. The P(1)–O(3) and S(1)–O(2) bond values are elongated due to the coordination, the conformation of the O–P–N–S–O fragment is changed owing to the turn of the phosphoryl group relatively the N(1)–S(1) bond (the O(3)– P(1)–N(1)–S(1) is 35.1(2)°). In the crystal packing neighboring polymer chains are connected by the C(11)–H(11)p0 (x, 1 y, z 0.5) weak hydrogen bonds (HC0 2.85 Å, C–Hp0 130°) and form layers which are parallel to OYZ plane. The o-bpe ligands are coordinated to the 3dmetals forming trans-isomers of complexes which are typical for the ligands of this type [29]. The CuCu0 separations in chain are 7.75 Å. 3.4. EPR studies and magnetochemistry The X-band EPR spectrum of a solid sample of 2 at 77 K shows the presence of elongated axial symmetry signal with not resolved hyperfine structure (Fig. 3a). The values of anisotropic parameters of the spectrum are g|| = 2.365, g\ = 2.095, which are typical for copper(II) ions with dx2 y2 ground state. The ‘‘half-field” signal is not observed which can be suggested as the absence of magnetic exchange interaction between copper(II) ions or the value of it is very weak. The EPR spectrum of frozen diluted solution at 77 K (Fig. 3b) is not similar to that observed in the solid state with the presence of hyperfine splitting in the parallel orientation region. The values of parameters are g|| = 2.450, g\ = 2.105 and A|| = 126 104 cm1 which are typical for CuO6 octahedral coordination environment [30]. Such behavior can be explained by dissociation of polymeric
Fig. 3. X-band EPR spectra of compound 2: (a) solid 2 at 77 K and (b) frozen CHCl3/ CH3OH (1:1, v/v) solution of 2 at 77 K.
complexes in solution and ligand exchange (o-bpe molecules to solvent alcohol molecules). Variable-temperature magnetic susceptibility studies for compound 2 were carried out over the temperature range 2–295 K. The magnetic moment of 2 at room temperature was 1.94lB (corresponds to vMT of 0.467 cm3 K mol1) which is a typical value for copper(II) and slightly greater than the expected spin-only value. The susceptibility (vM) of 2 showed steady increase upon cooling, without maximum (h in Fig. 4). The plot of vMT (per mole) versus temperature (d in Fig. 4) shows that vMT first negligible decreased from 0.467 cm3 K mol1 at 295 K to 0.439 cm3 K mol1 at 10 K (1.94lB and 1.88lB, respectively), then sharply decreased to 0.404 cm3 K mol1 at 2 K (1.80lB). This is clearly indicative the presence of week antiferromagnetic behavior within the chain. A simulation of these data was based on the Hamiltonian (Eq. (1)) and derived by Bonner and Fisher for infinite chain model with magnetically identical S = ½ metal centers (Eq. (2)) [31]:
^ ¼ J H
X
^i S ^iþ1 S
ð1Þ
0 1 2 ! jJj jJj 2 2 þ 0:075235 0:25 þ 0:074975 kT kT Ng b B C v0 ¼ @ 2 3 A kT jJj jJj jJj 1 þ 0:9931 kT þ 0:757825 kT þ 0:172135 kT ð2Þ In Eq. (2) J,N, g, b and k have their usual meanings. However, the presence of unlinked copper ions and/or short odd-numbered
O.V. Moroz et al. / Polyhedron 28 (2009) 1331–1335
1335
Supplementary data CCDC 710779 and 710780 contains the supplementary crystallographic data for 1 and 2. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: [email protected]. Acknowledgement This work was supported in part by Fundamental Researches State Fund of Ukraine (Project F25/193 – 2008). References Fig. 4. Plot of vM and vMT vs. T for 2; the solid line represents the simulated curve.
chains was taken into account; the experimental vMT of 2 was fitted using the Eq. (3) in which q – the fraction of paramagnetic impurity. Temperature independent paramagnetism (PTI) was also added in calculations:
v ¼ ð1 qÞv0 þ
Ng 2 b2 q þ PTI 4kT
ð3Þ
The best fit calculated for 2 gave the following parameter values: g = 2.180(1), J = 0.21(1) cm1, q = 0%, PTI = 74(1) 106 P P cm3 mol1, R = 1.49 103, where R = [ (Xobs Xcalc)2/ X 2calc ]1/2. The small negative value of J confirms the presence of weak predominant antiferromagnetic coupling within the chain. The small decreasing in vMT in the 10–300 K temperature range can be explained by existence of temperature independent paramagnetism. The obtaining value of isotropic g-factor is close to those calculated from EPR spectrum as gav (Eq. (4)):
g av ¼
ðg k þ 2g ? Þ 3
ð4Þ
However, the CuCu0 distance in chain is sizeable enough the exchange interaction between copper(II) ions are mediated by the system of conjugated C@C bonds of o-bpe. The value of J cannot be compared because there is only one record concerning using o-bpe for bridging copper(I) [31] and no records for copper(II) ions reported to date. 4. Conclusion The paper is devoted to coordination chemistry of sulfonyl phosphoramide ligands and their complex with copper(II). The new copper(II) complex containing deprotonated sulfamide ligands and o-bpe as bridging ligand has been obtained. The X-ray crystal structures for HL and [Cu(L)2 o-bpe]n have been determined. In contrast to fully characterized CAPh ligands, which usually form dimer structure by means of hydrogen bonds, the molecules of 1 form a hydrogen bonded chain in which they are linked to each other due to identical (P)OH–N contacts. The compound 2 has 1D polymeric chain structure. The magnetic study of 2 shows the presence of weak intrachain antiferromagnetic exchange interaction between copper(II) ions.
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