research communications
μ-oxalodihydroxamato-bis[(2,2′-bipyridyl)(dimethyl sulfoxide-κO)copper(II)] bis(perchlorate)
ofaO.O. Bohomolets National Medical University, Department of General Chemistry, Pr. Pobedy, 34, Kiev, 03055 , Ukraine, bTaras Shevchenko National University of Kiev, Department of Chemistry, Volodymyrska str. 62, Kiev, 01601 , Ukraine, and cUniversity of Joensuu, Department of Chemistry, PO Box 111, FI-80101 Joensuu, Finland
*Correspondence e-mail: annpavlis@ukr.net
The centrosymmetric binuclear complex, [Cu2(C2H2N2O4)(C10H8N2)2(C2H6OS)2](ClO4)2, contains two copper(II) ions, connected through an N-deprotonated oxalodihydroxamic acid dianion, two terminal 2,2′-bipyridine ligands, and two apically coordinating dimethylsulfoxide molecules. Two non-coordinating perchlorate anions assure electrical neutrality. The copper(II) ions in the complex dication [Cu2(C10H8N2)2(μ-C2H2N2O4)(C2H6SO)2]2+ are in an O2N3 square-pyramidal donor environment, the Cu–Cu separation being 5.2949 (4) Å. Two hydroxamate groups in the deprotonated oxalodihydroxamic acid are located trans to one each other. In the crystal, O—H⋯O and C—H⋯O hydrogen bonds link the complex cations to the perchlorate anions. Further C—H⋯O hydrogen bonds combine with π–π contacts with a centroid-to-centroid separation of 3.6371 (12) Å to stack the molecules along the a-axis direction.
Keywords: crystal structure; Cu(II) complex; oxalodihydroxamic acid.
CCDC reference: 1445115
1. Chemical context
Syntheses of complexes based on functionalized et al., 2014) and luminescence (Jankolovits et al., 2011) properties, potential applications in bioinorganic modeling (Marmion et al., 2004), adsorption (Pavlishchuk et al., 2010, 2011a;), catalysis (Mezei et al., 2007) and the creation of recognition agents (Lim et al., 2011). The majority of complexes obtained with and additional donor ligands belong to different families of metallacrown coordination compounds (Mezei et al., 2007). Other topologies for polydentate hydroxamate-based complexes are more unusual (Gumienna-Kontecka et al., 2013; Golenya et al., 2014). Here we present the structure of the binuclear complex [Cu2(C10H8N2)2(μ-C2H2N2O4)(C2H6SO)2](ClO4)2 (I), obtained from oxalodihydroxamic acid and bipyridine in DMSO solution.
are of particular interest due to their non-trivial magnetic (Pavlishchuk2. Structural commentary
The title compound (I) consists of a centrosymmetric complex di-cation [Cu2(C10H8N2)2(μ-C2H2N2O4)(C2H6SO)2]2+ with two uncoordinating perchlorate counter-anions (Fig. 1). The two copper(II) cations are connected through a doubly deprotonated oxalodihydroxamic acid, which serves as a bridging ligand between the copper ions which are coordinated by two nitrogen atoms from the 2,2′-bipyridine ligand, one carbonyl oxygen atom and the deprotonated hydroxamate nitrogen atom from one half of the oxalodihydroxamato ligand and the O atom of a DMSO molecule. The oxalodihydroxamato dianion is in a trans-form, while for metallacrown formation the cis-form is preferred. The coordination sphere of the copper(II) cation is square-pyramidal (τ = 0.21; Addison et al., 1984) and the copper(II) ion deviates from the mean plane of the O1/N1/N2/N3 donor atoms by 0.1868 (2) Å. The separation between the copper (II) cations is 5.2949 (4) Å. The equatorial Cu—N and Cu—O distances are typical of those for copper(II) complexes with hydroxamate and oxime donor groups (Buvailo et al., 2012; Duda et al., 1997; Pavlishchuk et al., 2011b; Safyanova et al., 2015, Table 1). The elongated apical bond, Cu1—O2 (2.2516 (16) Å), compared to the Cu—O and Cu—N distances in the equatorial plane that range from 1.9848 (16) to 1.9966 (19) Å, Table 1, is most likely due to Jahn–Teller distortion.
The C—N and C—C bond lengths in the 2,2′-bipyridine ligands are also normal for 2-substituted pyridine derivatives (Krämer et al., 2000; Strotmeyer et al., 2003; Fritsky et al., 2004). The coordinating oxalohydroxamate dianion also has C—C, C—N, N—N bond lengths that are typical of N-deprotonated hydroxamate groups (Świątek-Kozłowska et al., 2000; Dobosz et al., 1999).
3. Supramolecular features
In the O⋯O6 together with C12—H12A⋯O9 hydrogen bonds link the cations and associated perchlorate anions. An extensive series of other C—H⋯O contacts, Table 2, link the complex cations to other anions. The O2 atom of the DMSO ligand acts as a bifurcated acceptor forming C4—H4⋯O2 and C7—H7⋯O2 hydrogen bonds. These hydrogen bonds combine with π–π contacts between the N2/C6–C10 ring of the bipyridine and the Cu1/O1/C11/C11i/N3 ring formed by the chelating oxalodihydroxamate ligand with a centroid-to-centroid distance of 3.6371 (12) Å to stack the cations along the a-axis direction, Fig. 2.
O5—H5
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4. Database survey
A search in the Cambridge Structural Database (Version 5.35, May 2014; Groom & Allen, 2014) shows that there are seven reports devoted to the study of crystal structures of oxalodihydroxamic acid and its complexes. In the reported crystal structures of oxalodihydroxamic acid and its salts, the compound crystallized only in the trans-form. The bond lengths in oxalodihydroxamic acid itself and in its ammonium and thallium salts do not differ significantly [C—C bonds are in the range 1.51 (2)–1.528 (3) Å, C=O 1.231 (3)–1.248 (3) Å, C—N 1.310 (4)–1.33 (2) Å while the N—O bond lengths vary from 1.36 (2) to 1.388 (1) Å; Lowe-Ma & Decker, 1986; Sameena Begum et al., 1987, 1988; Huang et al., 1991; Marsh, 1989). Only two structures of coordination compounds with dihydroxyoxamidato ligands were found. Both involved anionic mononuclear NiII complexes with ligands derived from doubly or triply deprotonated oxalodihydroxamic acid. In one of these complexes (Moroz et al., 2006), the dihydroxyoxamidato trianion acts as a simple bidentate chelating ligand forming a square-planar complex. In the second (Świątek-Kozłowska et al., 2000), a square planar NiII complex again forms, but the dihydroxyoxamidato ligand also forms bridges to the potassium counter-ions generating a polymeric system. The structure presented here is the first example in which a dihydroxyoxamidato anion acts as a bridging ligand between two transition metals. The lack of crystal data for complexes with other transition metal cations may be associated with the ease of hydrolysis of the oxalodihydroxamic acid initiated by a metal salt solution.
5. Synthesis and crystallization
To the warm mixture containing 0.060 g (0.5 mmol) of oxalodihydroxamic acid and 0.370 g (1 mmol) of Cu(ClO4)2·6H2O in 10 ml of DMSO the solution of 2,2′-bipyridine (0.156 g, 1 mmol) in 10 ml of methanol was added upon stirring. The resulted solution was stirred for 1 h and then left for slow evaporation.
The resulting blue crystals suitable for X-ray analysis were isolated after one week. The crystals were washed with small amounts of 2-propanol and dried in air, yielding 0.255 g (28%) of the title compound.
6. Refinement
Crystal data, data collection and structure . The OH hydrogen atom was located from a difference Fourier map and was refined isotropically. Other hydrogen atoms were positioned geometrically and were constrained to ride on their parent atoms, with C—H = 0.95–0.98 Å, and Uiso = 1.2–1.5 Ueq(parent atom). The highest peak is located 0.99 Å from atom Cu1 and the deepest hole is located 0.82 Å from atom Cu1.
details are summarized in Table 3
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Supporting information
CCDC reference: 1445115
10.1107/S2056989016000050/sj5487sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016000050/sj5487Isup2.hkl
Syntheses of complexes based on functionalized
are of particular interest due to their non-trivial magnetic (Pavlishchuk et al., 2014) and luminescence (Jankolovits et al., 2011) properties, potential applications in bioinorganic modeling (Marmion et al., 2004), adsorption (Pavlishchuk et al., 2010, 2011a;), catalysis (Mezei et al., 2007) and the creation of recognition agents (Lim et al., 2011). The majority of complexes obtained with and additional donor ligands belong to different families of metallacrown coordination compounds (Mezei et al., 2007). Other topologies for polydentate hydroxamate-based complexes are more unusual (Gumienna-Kontecka et al., 2013; Golenya et al., 2014). Here we present the structure of the binuclear complex [Cu2(C10H8N2)2(µ-C2H2N2O4)(C2H6SO)2](ClO4)2 (I), obtained from oxalodihydroxamic acid and bipyridine in DMSO solution.The title compound (I) consists of a centrosymmetric complex di-cation [Cu2(C10H8N2)2(µ-C2H2N2O4)(C2H6SO)2]2+ with two uncoordinating perchlorate counter-anions (Fig. 1). The two copper(II) cations are connected through a doubly deprotonated oxalodihydroxamic acid, which serves as a bridging ligand between the copper ions which are coordinated by two nitrogen atoms from the 2,2'-bipyridine ligand, one carbonyl oxygen atom and the deprotonated hydroxamate nitrogen atom from one half of the oxalodihydroxamato ligand and the O atom of a DMSO molecule. The oxalodihydroxamato dianion is in a trans-form, while for metallacrown formation the cis-form is preferred. The coordination spheres of the copper(II) cations are square-pyramidal (τ = 0.21; Addison et al., 1984) and the copper(II) ions deviate from the mean plane of the O1/N1/N2/N3 donor atoms by 0.1868 (2) Å. The separation between the copper (II) cations is 5.2949 (4) Å. The equatorial Cu—N and Cu—O distances are typical of those for copper(II) complexes with hydroxamate and oxime donor groups (Buvailo et al., 2012; Duda et al., 1997; Pavlishchuk et al., 2011b; Safyanova et al., 2015, Table 1). The elongated apical bond, Cu1—O2 (2.2516 (16) Å), compared to the Cu—O and Cu—N distances in the equatorial plane that range from 1.9848 (16) to 1.9966 (19) Å, Table 1, is most likely due to Jahn–Teller distortion.
The C—N and C—C bond lengths in the 2,2'-bipyridine ligands are also normal for 2-substituted pyridine derivatives (Krämer et al., 2000; Strotmeyer et al., 2003; Fritsky et al., 2004). The coordinated oxalohydroxamate dianion also has C—C, C—N, N—N bond lengths that are typical of N-deprotonated hydroxamate groups (Świątek-Kozłowska et al., 2000; Dobosz et al., 1999).
In the π–π contacts between the N2/C6–C10 ring of the bipyridine and the Cu1/O1/C11/C11i/N3 ring formed by the chelating oxalodihydroxamate ligand with a centroid–centroid distance of 3.6371 (12) Å to stack the cations along the a-axis direction, Fig. 2.
O5—H5O···O6 together with C12—H12A···O9 hydrogen bonds link the cations and associated perchlorate anions. An extensive series of other C—H···O contacts, Table 2, link the complex cations to other anions. The O2 atom of the DMSO ligand acts as a bifurcated acceptor forming C4—H4···O2 and C7—H7···O2 hydrogen bonds. These hydrogen bonds combine withA search in the Cambridge Structural Database (Version 5.35, May 2014; Groom & Allen, 2014) shows that there are seven reports devoted to the study of crystal structures of oxalodihydroxamic acid and its complexes. In the reported crystal structures of oxalodihydroxamic acid and its salts, the compound crystallized only in the trans-form. The bond distances in oxalodihydroxamic acid itself and in its ammonium and thallium salts do not differ significantly [C—C bonds are in the range 1.51 (2)–1.528 (3) Å, C=O 1.231 (3)–1.248 (3) Å, C—N 1.310 (4)–1.33 (2) Å while the N—O bond lengths vary from 1.36 (2) to 1.388 (1) Å; Lowe-Ma & Decker, 1986; Sameena Begum et al., 1987, 1988; Huang et al., 1991; Marsh, 1989). Only two structures of coordination compounds with dihydroxyoxamidato ligands were found. Both involved anionic mononuclear NiII complexes with ligands derived from doubly or triply deprotonated oxalodihydroxamic acid. In one of these complexes (Moroz et al., 2006), the dihydroxyoxamidato trianion acts as a simple bidentate chelating ligand forming a square-planar complex. In the second (Świątek-Kozłowska et al., 2000), a square planar NiII complex again forms, but the dihydroxyoxamidato ligand also forms bridges to the potassium(I) counter-ions generating a polymeric system. The structure presented here is the first example in which a dihydroxyoxamidato anion acts as a bridging ligand between two transition metals. The lack of crystal data for complexes with other transition metal cations may be associated with the ease of hydrolysis of the oxalodihydroxamic acid initiated by a metal salt solution.
To the warm mixture containing 0.060 g (0.5 mmol) of oxalodihydroxamic acid and 0.370 g (1 mmol) of Cu(ClO4)2.6H2O in 10 ml of DMSO the solution of 2,2 '-bipyridine (0.156 g, 1 mmol) in 10 ml of methanol was added upon stirring. The resulted solution was stirred for 1 h and then left for slow evaporation.
The resulting blue crystals suitable for X-ray analysis were isolated after one week. The crystals were washed with small amounts of 2-propanol and dried in air, yielding 0.255 g (28%) of the title compound.
The OH hydrogen atom was located from a difference Fourier map and was refined isotropically. Other hydrogen atoms were positioned geometrically and were constrained to ride on their parent atoms, with C—H = 0.95–0.98 Å, and Uiso = 1.2–1.5 Ueq(parent atom). The highest peak is located 0.99 Å from atom Cu1 and the deepest hole is located 0.82 Å from atom Cu1.
Syntheses of complexes based on functionalized
are of particular interest due to their non-trivial magnetic (Pavlishchuk et al., 2014) and luminescence (Jankolovits et al., 2011) properties, potential applications in bioinorganic modeling (Marmion et al., 2004), adsorption (Pavlishchuk et al., 2010, 2011a;), catalysis (Mezei et al., 2007) and the creation of recognition agents (Lim et al., 2011). The majority of complexes obtained with and additional donor ligands belong to different families of metallacrown coordination compounds (Mezei et al., 2007). Other topologies for polydentate hydroxamate-based complexes are more unusual (Gumienna-Kontecka et al., 2013; Golenya et al., 2014). Here we present the structure of the binuclear complex [Cu2(C10H8N2)2(µ-C2H2N2O4)(C2H6SO)2](ClO4)2 (I), obtained from oxalodihydroxamic acid and bipyridine in DMSO solution.The title compound (I) consists of a centrosymmetric complex di-cation [Cu2(C10H8N2)2(µ-C2H2N2O4)(C2H6SO)2]2+ with two uncoordinating perchlorate counter-anions (Fig. 1). The two copper(II) cations are connected through a doubly deprotonated oxalodihydroxamic acid, which serves as a bridging ligand between the copper ions which are coordinated by two nitrogen atoms from the 2,2'-bipyridine ligand, one carbonyl oxygen atom and the deprotonated hydroxamate nitrogen atom from one half of the oxalodihydroxamato ligand and the O atom of a DMSO molecule. The oxalodihydroxamato dianion is in a trans-form, while for metallacrown formation the cis-form is preferred. The coordination spheres of the copper(II) cations are square-pyramidal (τ = 0.21; Addison et al., 1984) and the copper(II) ions deviate from the mean plane of the O1/N1/N2/N3 donor atoms by 0.1868 (2) Å. The separation between the copper (II) cations is 5.2949 (4) Å. The equatorial Cu—N and Cu—O distances are typical of those for copper(II) complexes with hydroxamate and oxime donor groups (Buvailo et al., 2012; Duda et al., 1997; Pavlishchuk et al., 2011b; Safyanova et al., 2015, Table 1). The elongated apical bond, Cu1—O2 (2.2516 (16) Å), compared to the Cu—O and Cu—N distances in the equatorial plane that range from 1.9848 (16) to 1.9966 (19) Å, Table 1, is most likely due to Jahn–Teller distortion.
The C—N and C—C bond lengths in the 2,2'-bipyridine ligands are also normal for 2-substituted pyridine derivatives (Krämer et al., 2000; Strotmeyer et al., 2003; Fritsky et al., 2004). The coordinated oxalohydroxamate dianion also has C—C, C—N, N—N bond lengths that are typical of N-deprotonated hydroxamate groups (Świątek-Kozłowska et al., 2000; Dobosz et al., 1999).
In the π–π contacts between the N2/C6–C10 ring of the bipyridine and the Cu1/O1/C11/C11i/N3 ring formed by the chelating oxalodihydroxamate ligand with a centroid–centroid distance of 3.6371 (12) Å to stack the cations along the a-axis direction, Fig. 2.
O5—H5O···O6 together with C12—H12A···O9 hydrogen bonds link the cations and associated perchlorate anions. An extensive series of other C—H···O contacts, Table 2, link the complex cations to other anions. The O2 atom of the DMSO ligand acts as a bifurcated acceptor forming C4—H4···O2 and C7—H7···O2 hydrogen bonds. These hydrogen bonds combine withA search in the Cambridge Structural Database (Version 5.35, May 2014; Groom & Allen, 2014) shows that there are seven reports devoted to the study of crystal structures of oxalodihydroxamic acid and its complexes. In the reported crystal structures of oxalodihydroxamic acid and its salts, the compound crystallized only in the trans-form. The bond distances in oxalodihydroxamic acid itself and in its ammonium and thallium salts do not differ significantly [C—C bonds are in the range 1.51 (2)–1.528 (3) Å, C=O 1.231 (3)–1.248 (3) Å, C—N 1.310 (4)–1.33 (2) Å while the N—O bond lengths vary from 1.36 (2) to 1.388 (1) Å; Lowe-Ma & Decker, 1986; Sameena Begum et al., 1987, 1988; Huang et al., 1991; Marsh, 1989). Only two structures of coordination compounds with dihydroxyoxamidato ligands were found. Both involved anionic mononuclear NiII complexes with ligands derived from doubly or triply deprotonated oxalodihydroxamic acid. In one of these complexes (Moroz et al., 2006), the dihydroxyoxamidato trianion acts as a simple bidentate chelating ligand forming a square-planar complex. In the second (Świątek-Kozłowska et al., 2000), a square planar NiII complex again forms, but the dihydroxyoxamidato ligand also forms bridges to the potassium(I) counter-ions generating a polymeric system. The structure presented here is the first example in which a dihydroxyoxamidato anion acts as a bridging ligand between two transition metals. The lack of crystal data for complexes with other transition metal cations may be associated with the ease of hydrolysis of the oxalodihydroxamic acid initiated by a metal salt solution.
To the warm mixture containing 0.060 g (0.5 mmol) of oxalodihydroxamic acid and 0.370 g (1 mmol) of Cu(ClO4)2.6H2O in 10 ml of DMSO the solution of 2,2 '-bipyridine (0.156 g, 1 mmol) in 10 ml of methanol was added upon stirring. The resulted solution was stirred for 1 h and then left for slow evaporation.
The resulting blue crystals suitable for X-ray analysis were isolated after one week. The crystals were washed with small amounts of 2-propanol and dried in air, yielding 0.255 g (28%) of the title compound.
detailsThe OH hydrogen atom was located from a difference Fourier map and was refined isotropically. Other hydrogen atoms were positioned geometrically and were constrained to ride on their parent atoms, with C—H = 0.95–0.98 Å, and Uiso = 1.2–1.5 Ueq(parent atom). The highest peak is located 0.99 Å from atom Cu1 and the deepest hole is located 0.82 Å from atom Cu1.
Data collection: COLLECT (Bruker, 2004); cell
DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. The crystal structure of complex (I), showing the atom labeling. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. The crystal packing of complex (I). |
[Cu2(C2H2N2O4)(C10H8N2)2(C2H6OS)2](ClO4)2 | Z = 1 |
Mr = 912.66 | F(000) = 464 |
Triclinic, P1 | Dx = 1.760 Mg m−3 |
a = 7.3641 (2) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 10.3759 (5) Å | Cell parameters from 26719 reflections |
c = 12.1358 (5) Å | θ = 1.0–27.5° |
α = 68.853 (2)° | µ = 1.59 mm−1 |
β = 84.803 (3)° | T = 100 K |
γ = 87.825 (3)° | Block, pale blue |
V = 861.27 (6) Å3 | 0.13 × 0.12 × 0.12 mm |
Nonius KappaCCD diffractometer | 3351 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.039 |
ω scans | θmax = 27.5°, θmin = 2.8° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −8→9 |
Tmin = 0.789, Tmax = 0.835 | k = −13→13 |
18205 measured reflections | l = −15→15 |
3943 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.087 | w = 1/[σ2(Fo2) + (0.0388P)2 + 0.7097P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max < 0.001 |
3943 reflections | Δρmax = 0.74 e Å−3 |
241 parameters | Δρmin = −0.55 e Å−3 |
[Cu2(C2H2N2O4)(C10H8N2)2(C2H6OS)2](ClO4)2 | γ = 87.825 (3)° |
Mr = 912.66 | V = 861.27 (6) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.3641 (2) Å | Mo Kα radiation |
b = 10.3759 (5) Å | µ = 1.59 mm−1 |
c = 12.1358 (5) Å | T = 100 K |
α = 68.853 (2)° | 0.13 × 0.12 × 0.12 mm |
β = 84.803 (3)° |
Nonius KappaCCD diffractometer | 3943 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 3351 reflections with I > 2σ(I) |
Tmin = 0.789, Tmax = 0.835 | Rint = 0.039 |
18205 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | Δρmax = 0.74 e Å−3 |
3943 reflections | Δρmin = −0.55 e Å−3 |
241 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.81268 (4) | 0.11133 (3) | 0.38671 (2) | 0.01840 (10) | |
Cl1 | 0.71265 (8) | −0.30071 (6) | 0.19039 (5) | 0.02481 (14) | |
S1 | 0.85060 (7) | 0.28499 (6) | 0.10324 (5) | 0.01997 (14) | |
O1 | 0.6724 (2) | −0.05948 (17) | 0.41752 (15) | 0.0210 (3) | |
O2 | 0.7106 (2) | 0.23761 (17) | 0.21002 (14) | 0.0221 (4) | |
O5 | 0.4262 (2) | −0.26749 (18) | 0.48100 (16) | 0.0243 (4) | |
H5O | 0.528 (6) | −0.253 (5) | 0.428 (4) | 0.083 (14)* | |
O6 | 0.6917 (3) | −0.3371 (2) | 0.31798 (18) | 0.0383 (5) | |
O7 | 0.5444 (3) | −0.3243 (2) | 0.1500 (2) | 0.0423 (5) | |
O8 | 0.8557 (3) | −0.3841 (2) | 0.16071 (18) | 0.0344 (4) | |
O9 | 0.7598 (3) | −0.15753 (19) | 0.13534 (19) | 0.0365 (5) | |
N1 | 0.9922 (3) | 0.2580 (2) | 0.36990 (17) | 0.0192 (4) | |
N2 | 1.0297 (3) | 0.0299 (2) | 0.32626 (17) | 0.0192 (4) | |
N3 | 0.3959 (3) | −0.1523 (2) | 0.51515 (17) | 0.0192 (4) | |
C1 | 0.9598 (3) | 0.3726 (3) | 0.3950 (2) | 0.0238 (5) | |
H1 | 0.8409 | 0.3883 | 0.4252 | 0.029* | |
C2 | 1.0948 (3) | 0.4694 (3) | 0.3781 (2) | 0.0255 (5) | |
H2 | 1.0683 | 0.5499 | 0.3967 | 0.031* | |
C3 | 1.2673 (3) | 0.4473 (3) | 0.3342 (2) | 0.0257 (5) | |
H3 | 1.3624 | 0.5108 | 0.3248 | 0.031* | |
C4 | 1.3010 (3) | 0.3309 (2) | 0.3038 (2) | 0.0222 (5) | |
H4 | 1.4180 | 0.3153 | 0.2708 | 0.027* | |
C5 | 1.1604 (3) | 0.2381 (2) | 0.3224 (2) | 0.0199 (5) | |
C6 | 1.1790 (3) | 0.1118 (2) | 0.2922 (2) | 0.0203 (5) | |
C7 | 1.3330 (3) | 0.0781 (3) | 0.2340 (2) | 0.0241 (5) | |
H7 | 1.4356 | 0.1376 | 0.2100 | 0.029* | |
C8 | 1.3359 (3) | −0.0434 (3) | 0.2112 (2) | 0.0261 (5) | |
H8 | 1.4398 | −0.0679 | 0.1705 | 0.031* | |
C9 | 1.1844 (3) | −0.1290 (3) | 0.2487 (2) | 0.0249 (5) | |
H9 | 1.1846 | −0.2140 | 0.2358 | 0.030* | |
C10 | 1.0341 (3) | −0.0888 (2) | 0.3050 (2) | 0.0231 (5) | |
H10 | 0.9300 | −0.1469 | 0.3295 | 0.028* | |
C11 | 0.5220 (3) | −0.0590 (2) | 0.4801 (2) | 0.0183 (5) | |
C12 | 0.8329 (4) | 0.1655 (3) | 0.0300 (2) | 0.0290 (6) | |
H12A | 0.8580 | 0.0719 | 0.0845 | 0.044* | |
H12B | 0.9215 | 0.1893 | −0.0395 | 0.044* | |
H12C | 0.7095 | 0.1696 | 0.0047 | 0.044* | |
C13 | 0.7529 (4) | 0.4328 (3) | −0.0024 (2) | 0.0266 (5) | |
H13A | 0.6320 | 0.4095 | −0.0173 | 0.040* | |
H13B | 0.8315 | 0.4622 | −0.0766 | 0.040* | |
H13C | 0.7414 | 0.5081 | 0.0286 | 0.040* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.01496 (15) | 0.02100 (16) | 0.01911 (16) | −0.00278 (10) | 0.00203 (10) | −0.00758 (12) |
Cl1 | 0.0209 (3) | 0.0239 (3) | 0.0307 (3) | −0.0023 (2) | 0.0016 (2) | −0.0117 (2) |
S1 | 0.0164 (3) | 0.0234 (3) | 0.0179 (3) | −0.0026 (2) | 0.0010 (2) | −0.0050 (2) |
O1 | 0.0169 (8) | 0.0230 (8) | 0.0234 (9) | −0.0041 (6) | 0.0043 (6) | −0.0097 (7) |
O2 | 0.0165 (8) | 0.0291 (9) | 0.0187 (8) | −0.0036 (7) | 0.0033 (6) | −0.0069 (7) |
O5 | 0.0229 (9) | 0.0232 (9) | 0.0297 (10) | −0.0029 (7) | 0.0045 (7) | −0.0143 (8) |
O6 | 0.0423 (12) | 0.0437 (12) | 0.0292 (10) | 0.0059 (9) | 0.0046 (9) | −0.0157 (9) |
O7 | 0.0267 (10) | 0.0498 (13) | 0.0519 (13) | −0.0114 (9) | −0.0070 (9) | −0.0181 (11) |
O8 | 0.0354 (11) | 0.0327 (10) | 0.0356 (11) | 0.0075 (8) | 0.0041 (8) | −0.0153 (9) |
O9 | 0.0344 (11) | 0.0241 (10) | 0.0488 (13) | −0.0064 (8) | 0.0063 (9) | −0.0120 (9) |
N1 | 0.0182 (9) | 0.0218 (10) | 0.0167 (9) | −0.0023 (7) | 0.0003 (7) | −0.0061 (8) |
N2 | 0.0169 (9) | 0.0204 (10) | 0.0195 (10) | −0.0008 (7) | −0.0016 (8) | −0.0062 (8) |
N3 | 0.0190 (10) | 0.0186 (9) | 0.0207 (10) | −0.0015 (7) | 0.0004 (8) | −0.0083 (8) |
C1 | 0.0218 (12) | 0.0263 (13) | 0.0236 (12) | −0.0007 (9) | 0.0007 (10) | −0.0099 (10) |
C2 | 0.0274 (13) | 0.0210 (12) | 0.0271 (13) | −0.0035 (10) | 0.0017 (10) | −0.0082 (10) |
C3 | 0.0254 (13) | 0.0233 (12) | 0.0264 (13) | −0.0074 (10) | −0.0024 (10) | −0.0057 (10) |
C4 | 0.0175 (11) | 0.0247 (12) | 0.0214 (12) | −0.0029 (9) | 0.0001 (9) | −0.0050 (10) |
C5 | 0.0189 (11) | 0.0239 (12) | 0.0153 (11) | 0.0005 (9) | −0.0026 (9) | −0.0050 (9) |
C6 | 0.0179 (11) | 0.0229 (12) | 0.0187 (11) | −0.0020 (9) | −0.0012 (9) | −0.0058 (9) |
C7 | 0.0173 (11) | 0.0294 (13) | 0.0236 (13) | −0.0014 (9) | 0.0000 (9) | −0.0075 (10) |
C8 | 0.0210 (12) | 0.0315 (13) | 0.0255 (13) | 0.0029 (10) | 0.0026 (10) | −0.0113 (11) |
C9 | 0.0264 (13) | 0.0253 (13) | 0.0248 (13) | 0.0029 (10) | −0.0018 (10) | −0.0115 (10) |
C10 | 0.0224 (12) | 0.0225 (12) | 0.0240 (12) | −0.0004 (9) | −0.0026 (10) | −0.0076 (10) |
C11 | 0.0179 (11) | 0.0195 (11) | 0.0164 (11) | −0.0001 (9) | −0.0019 (9) | −0.0051 (9) |
C12 | 0.0349 (14) | 0.0279 (13) | 0.0244 (13) | −0.0011 (11) | 0.0054 (11) | −0.0114 (11) |
C13 | 0.0306 (13) | 0.0220 (12) | 0.0243 (13) | 0.0015 (10) | −0.0041 (10) | −0.0046 (10) |
Cu1—O1 | 1.9848 (16) | C2—C3 | 1.376 (4) |
Cu1—N2 | 1.985 (2) | C2—H2 | 0.9500 |
Cu1—N3i | 1.986 (2) | C3—C4 | 1.393 (4) |
Cu1—N1 | 1.9966 (19) | C3—H3 | 0.9500 |
Cu1—O2 | 2.2516 (16) | C4—C5 | 1.388 (3) |
Cl1—O9 | 1.4336 (19) | C4—H4 | 0.9500 |
Cl1—O7 | 1.4339 (19) | C5—C6 | 1.481 (3) |
Cl1—O8 | 1.4401 (19) | C6—C7 | 1.382 (3) |
Cl1—O6 | 1.450 (2) | C7—C8 | 1.384 (4) |
S1—O2 | 1.5234 (17) | C7—H7 | 0.9500 |
S1—C12 | 1.781 (3) | C8—C9 | 1.390 (4) |
S1—C13 | 1.783 (2) | C8—H8 | 0.9500 |
O1—C11 | 1.286 (3) | C9—C10 | 1.378 (4) |
O5—N3 | 1.404 (3) | C9—H9 | 0.9500 |
O5—H5O | 0.92 (5) | C10—H10 | 0.9500 |
N1—C1 | 1.338 (3) | C11—C11i | 1.486 (5) |
N1—C5 | 1.359 (3) | C12—H12A | 0.9800 |
N2—C10 | 1.345 (3) | C12—H12B | 0.9800 |
N2—C6 | 1.355 (3) | C12—H12C | 0.9800 |
N3—C11 | 1.296 (3) | C13—H13A | 0.9800 |
N3—Cu1i | 1.986 (2) | C13—H13B | 0.9800 |
C1—C2 | 1.389 (3) | C13—H13C | 0.9800 |
C1—H1 | 0.9500 | ||
O1—Cu1—N2 | 90.36 (7) | C2—C3—H3 | 120.4 |
O1—Cu1—N3i | 82.73 (7) | C4—C3—H3 | 120.4 |
N2—Cu1—N3i | 165.41 (8) | C5—C4—C3 | 118.8 (2) |
O1—Cu1—N1 | 168.93 (7) | C5—C4—H4 | 120.6 |
N2—Cu1—N1 | 81.76 (8) | C3—C4—H4 | 120.6 |
N3i—Cu1—N1 | 103.13 (8) | N1—C5—C4 | 121.6 (2) |
O1—Cu1—O2 | 98.04 (6) | N1—C5—C6 | 114.7 (2) |
N2—Cu1—O2 | 97.53 (7) | C4—C5—C6 | 123.7 (2) |
N3i—Cu1—O2 | 96.15 (7) | N2—C6—C7 | 121.8 (2) |
N1—Cu1—O2 | 90.72 (7) | N2—C6—C5 | 114.2 (2) |
O9—Cl1—O7 | 109.44 (13) | C7—C6—C5 | 124.1 (2) |
O9—Cl1—O8 | 109.53 (12) | C6—C7—C8 | 119.1 (2) |
O7—Cl1—O8 | 110.04 (13) | C6—C7—H7 | 120.4 |
O9—Cl1—O6 | 109.19 (13) | C8—C7—H7 | 120.4 |
O7—Cl1—O6 | 109.47 (13) | C7—C8—C9 | 119.0 (2) |
O8—Cl1—O6 | 109.16 (12) | C7—C8—H8 | 120.5 |
O2—S1—C12 | 105.19 (11) | C9—C8—H8 | 120.5 |
O2—S1—C13 | 105.82 (11) | C10—C9—C8 | 119.1 (2) |
C12—S1—C13 | 98.84 (13) | C10—C9—H9 | 120.5 |
C11—O1—Cu1 | 110.68 (14) | C8—C9—H9 | 120.5 |
S1—O2—Cu1 | 117.43 (9) | N2—C10—C9 | 122.2 (2) |
N3—O5—H5O | 110 (3) | N2—C10—H10 | 118.9 |
C1—N1—C5 | 119.0 (2) | C9—C10—H10 | 118.9 |
C1—N1—Cu1 | 126.77 (16) | O1—C11—N3 | 127.6 (2) |
C5—N1—Cu1 | 114.11 (16) | O1—C11—C11i | 119.6 (2) |
C10—N2—C6 | 118.8 (2) | N3—C11—C11i | 112.8 (2) |
C10—N2—Cu1 | 126.04 (16) | S1—C12—H12A | 109.5 |
C6—N2—Cu1 | 114.74 (16) | S1—C12—H12B | 109.5 |
C11—N3—O5 | 116.51 (19) | H12A—C12—H12B | 109.5 |
C11—N3—Cu1i | 114.16 (16) | S1—C12—H12C | 109.5 |
O5—N3—Cu1i | 129.32 (14) | H12A—C12—H12C | 109.5 |
N1—C1—C2 | 122.0 (2) | H12B—C12—H12C | 109.5 |
N1—C1—H1 | 119.0 | S1—C13—H13A | 109.5 |
C2—C1—H1 | 119.0 | S1—C13—H13B | 109.5 |
C3—C2—C1 | 119.3 (2) | H13A—C13—H13B | 109.5 |
C3—C2—H2 | 120.4 | S1—C13—H13C | 109.5 |
C1—C2—H2 | 120.4 | H13A—C13—H13C | 109.5 |
C2—C3—C4 | 119.2 (2) | H13B—C13—H13C | 109.5 |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5O···O6 | 0.92 (5) | 2.12 (5) | 2.912 (3) | 144 (4) |
C4—H4···O2ii | 0.95 | 2.42 | 3.359 (3) | 171 |
C7—H7···O2ii | 0.95 | 2.31 | 3.226 (3) | 162 |
C3—H3···O7iii | 0.95 | 2.50 | 3.239 (3) | 134 |
C13—H13A···O7iv | 0.98 | 2.56 | 3.409 (3) | 145 |
C13—H13C···O8v | 0.98 | 2.48 | 3.346 (3) | 148 |
C13—H13B···O8vi | 0.98 | 2.65 | 3.442 (3) | 138 |
C12—H12A···O9 | 0.98 | 2.36 | 3.175 (3) | 140 |
C8—H8···O9ii | 0.95 | 2.56 | 3.462 (3) | 159 |
C12—H12B···O9vi | 0.98 | 2.59 | 3.470 (3) | 150 |
Symmetry codes: (ii) x+1, y, z; (iii) x+1, y+1, z; (iv) −x+1, −y, −z; (v) x, y+1, z; (vi) −x+2, −y, −z. |
Cu1—O1 | 1.9848 (16) | Cu1—O2 | 2.2516 (16) |
Cu1—N2 | 1.985 (2) | O1—C11 | 1.286 (3) |
Cu1—N3i | 1.986 (2) | O5—N3 | 1.404 (3) |
Cu1—N1 | 1.9966 (19) | ||
O1—Cu1—N2 | 90.36 (7) | O1—Cu1—O2 | 98.04 (6) |
O1—Cu1—N3i | 82.73 (7) | N2—Cu1—O2 | 97.53 (7) |
N2—Cu1—N1 | 81.76 (8) | N3i—Cu1—O2 | 96.15 (7) |
N3i—Cu1—N1 | 103.13 (8) | N1—Cu1—O2 | 90.72 (7) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5O···O6 | 0.92 (5) | 2.12 (5) | 2.912 (3) | 144 (4) |
C4—H4···O2ii | 0.95 | 2.42 | 3.359 (3) | 170.7 |
C7—H7···O2ii | 0.95 | 2.31 | 3.226 (3) | 161.8 |
C3—H3···O7iii | 0.95 | 2.50 | 3.239 (3) | 134.4 |
C13—H13A···O7iv | 0.98 | 2.56 | 3.409 (3) | 144.9 |
C13—H13C···O8v | 0.98 | 2.48 | 3.346 (3) | 147.5 |
C13—H13B···O8vi | 0.98 | 2.65 | 3.442 (3) | 137.8 |
C12—H12A···O9 | 0.98 | 2.36 | 3.175 (3) | 140.4 |
C8—H8···O9ii | 0.95 | 2.56 | 3.462 (3) | 159.2 |
C12—H12B···O9vi | 0.98 | 2.59 | 3.470 (3) | 149.9 |
Symmetry codes: (ii) x+1, y, z; (iii) x+1, y+1, z; (iv) −x+1, −y, −z; (v) x, y+1, z; (vi) −x+2, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C2H2N2O4)(C10H8N2)2(C2H6OS)2](ClO4)2 |
Mr | 912.66 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 7.3641 (2), 10.3759 (5), 12.1358 (5) |
α, β, γ (°) | 68.853 (2), 84.803 (3), 87.825 (3) |
V (Å3) | 861.27 (6) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.59 |
Crystal size (mm) | 0.13 × 0.12 × 0.12 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.789, 0.835 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18205, 3943, 3351 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.087, 1.11 |
No. of reflections | 3943 |
No. of parameters | 241 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.74, −0.55 |
Computer programs: COLLECT (Bruker, 2004), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL2014/7 (Sheldrick, 2015), Mercury (Macrae et al., 2008), publCIF (Westrip, 2010).
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