Syntheses and structures of discrete copper(II) and cadmium(II) supra­molecular complexes based on 1,4-di­acyl­thio­semicarbazone ligands

Thio­semicarbazides and their metal complexes have attracted considerable inter­est because of their biological activities and their flexibility, which allows the ligands to bend and rotate freely to accommodate the coordination geom­etries of various metal centres. Discrete copper(II) and cad­mium(II) complexes have been prepared by crystallization of N-[2-(2-hy­droxy­benzo­yl)hydrazinecarbono­thio­yl]propanamide (H₃L) with Cu(CH₃COO)₂ or Cd(NO₃)₂ in a di­methyl­formamide/methanol mixed-solvent system at room temperature, affording the complexes di-[mu]-acetato-bis­{[mu]₄-1-[(2-oxidophen­yl)carbon­yl]-2-(pro­panamido­methane­thio­yl)hydrazine-1,2-diido}tetra­copper(II) di­methyl­form­amide disolvate, [Cu₄(C₁₁H₁₀N₃O₃S)₂(C₂H₃O₂)₂]·2C₃H₇NO, (I), and bis­{[mu]₂-[(2-hy­droxy­phen­yl)formamido](propanamido­methane­thio­yl)aza­nido}bis­[(4,4'-bi­pyri­dine)­nitratocadmium(II)] dihydrate, [Cd₂(C₁₁H₁₂N₃O₃S)₂(NO₃)₂(C₁₀H₈N₂)₂]·2H₂O, (II). Complex (I) consists of four Cu^II cations, two [mu]₄-brid­ging trianionic ligands and two [mu]₂-bridging acetate ligands, while complex (II) is composed of two Cd^II cations, two [mu]₂-bridging monoanionic ligands, two nitrate ligands and two 4,4'-bi­pyridine ligands. These discrete complexes are connected by hydrogen bonds and van der Waals inter­actions to form a three-dimensional supra­molecular architecture. Compared with (I), the phenolic hy­droxy group and hydrazide N atom of the thio­semicarbazide ligand of (II) are not involved in coordination and lead to a binuclear Cd^II complex. This different coordination mode may be attributed to the larger ionic radius of the Cd^II ion compared with the Cu^II ion.

S1. Introduction

Thio­semicarbazides and their derivatives have attracted considerable inter­est because of not only their biological activities, including anti­bacterial, anti­malarial, anti­viral, and anti­tumor activities (Quiroga & Ranninger, 2004; Kasuga et al., 2003; Easmon et al., 2001), but also their flexibility, which allows the ligands to bend and rotate freely to accommodate the coordination geometries of various metal centres. Many metal complexes derived from thio­semicarbazones have been structurally characterized, and they possess a wide variety of biological activities (Leovac et al., 2009; Hassanien et al., 2008; Latheef et al., 2006; Babb et al., 2003; Simonov et al. , 2002; Belicchi-Ferrari et al., 2000).

Acyl­thio­semicarbazide ligands contain O, S, and N atoms as potential donors, and can support mono- and multinuclear structural complexes. Most of these activities mainly depend on their electronic and redox properties, which could be tuned by the attached substituent numbers and positions, and the conformation of ligands (Dearling et al., 2002; Maurer et al., 2002; Fetrrai et al., 2000). In order to figure out the structure–property relationships, a great number of metal complexes based on thio­semicarbazone derivatives, particularly the 1,4-disubstituted derivatives, have been prepared and their biological activities investigated systematically (Floquet et al., 2009; Hassanien et al., 2008; Latheef et al., 2006; Babb et al., 2003; Simonov et al., 2002; Belicchi-Ferrari et al., 2000). Among these, only a few examples have dealt with 1,4-di­acyl-thio­semicarbazone derivatives (Xue et al., 2006; Ali et al., 2004; Yamin & Yusof, 2003; Liu et al., 2013). Recently, much attention has been paid to multinuclear complexes as a result of their magnetic properties and theoretical significance (Li & Jin, 2013; Wei et al., 2012; Pradeep & Leroy, 2007; Moon et al., 2006). Thio­semicarbazide derivatives contain an N—N unit which can bridge two metal atoms, enabling them to form dinuclear or multinuclear complexes. However, reports on multinuclear complexes with the 1,4-di­acyl­thio­semicarbazide ligand are rare. In order to obtain such multinuclear complexes, we have synthesized a new acyl­thio­semicarbazide ligand, namely N-[2-(2-hy­droxy­benzoyl)­hydrazinecarbono­thioyl]propanamide (H₃L). The combination of H₃L with Cu(CH₃COO)₂ or Cd(NO₃)₂ afforded [Cu₄L₂(CH₃COO)₂]·2DMF, (I), and [Cd₂(HL)₂(C₁₀H₈N₂)₂]·2H₂O, (II), respectively, whose structures are reported herein.

S2. Experimental

S2.1. Synthesis and crystallization

All analytical grade chemicals were obtained commercially and were used without further purifiation. N-{[2-(2-Hy­droxy­benzoyl)­hydrazine]carbono­thioyl}propanamide (H₃L) was prepared according to the literature procedure of Wang et al. (2000).

S2.1.1. Preparation of complex (I)

A mixture of Cu(CH₃COO)₂·2H₂O (0.0402 g, 0.20 mmol) and H₃L (0.0268 g, 0.10 mmol) were dissolved in a mixed solvent of methanol and di­methyl­formamide (12 ml, 5:1 v/v), and the solution was stirred for 3 h at room temperature. The resulting blue solution was filtered. After standing for several days, black block-shaped crystals were obtained from the filtrate. IR data (KBr, cm^-1): 3268 (w), 3059 (w), 2944 (w), 2876 (w), 1610 (m), 1634 (m), 1603 (s), 1551 (s), 1514 (m), 1477 (s), 1404 (s), 1269 (m), 1107 (m), 861 (m), 757 (m), 668 (m).

S2.1.2. Preparation of complex (II)

H₃L (0.0268 g, 0.10 mmol) and Cd(NO₃)₂ (0.0475 g, 0.20 mmol) were dissolved in a mixed solvent of methanol and di­methyl­formamide (12 ml, 5:1 v/v). 4,4'-Bi­pyridine (0.0080 g 0.05 mmol) was added and the solution was stirred for 3 h at room temperature. The resulting white suspension mixture was filtered and the filtrate allowed to evaporate in air at room temperature. Colourless crystals of (II) were separated from the filtrate after a period of one week. IR data (KBr, cm^-1): 3513 (m), 3080 (w), 2991 (w), 1675 (s), 1597 (s), 1561 (s), 1467 (s), 1383 (s), 1294 (s), 1221 (s), 1070 (m), 997 (m), 898 (m), 815 (m), 762 (m), 642 (s).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The H atoms of water were located in difference Fourier maps and their positions were refined with O—H bond-length restraints of 0.84 Å and with U_iso(H) = 1.2U_eq(O). The remaining H atoms were positioned in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.93 (aryl) or 0.96 Å (methyl), and with U_iso(H) = 1.5U_eq(C) for methyl groups and 1.2U_eq(C) otherwise.

S3. Results and discussion

Complex (I) crystallizes in the triclinic space group P1 (No. 2). The asymmetric unit contains two Cu^II ions, one µ₄-bridging deprotonated L^3- ligand {systematic name: 1-[(2-oxido­phenyl)­carbonyl]-2-(propanamido­methane­thioyl)hydrazine-1,2-diide}, one µ₂-bridging acetate ligand and one free di­methyl­formamide (DMF) molecule. As shown in Fig. 1, the Cu1 atom adopts a significantly re­cta­ngular pyramidal coordination geometry involving two L^3- ligands and one O atom from an acetate ligand; the equatorial plane is occupied by a phenolate O atom (O1), one deprotonated hydrazide N atom (N1), one S atom from the L^3- ligand (S1) and one O atom from an acetate ligand [O5ⁱ; symmetry code: (i) -x, -y, -z+1], while the axial position is occupied by a carbonyl O atom of another L^3- ligand (O2ⁱ). In the equatorial plane, the Cu1—O and Cu1—N bond lengths are 1.898 (3)–1.955 (3) and 1.927 (3) Å, respectively (Table 2). The apical Cu—O distance [Cu1—O2ⁱ = 2.719 (3) Å] is slightly longer than a common Cu—O distance (Liu et al., 2013). Atom Cu2 has a similar five-coordination and is triply chelated by two carbonyl O atoms (O2 and O3) and one deprotonated hydrazide N atom (N2) from L^3- ligands and by one O atom from an acetate anion (O4). The axial position is occupied by one phenolate O atom from another L^3- ligand (O1ⁱ), with a Cu2—O1ⁱ distance of 2.465 (3) Å, forming an elongated re­cta­ngular pyramidal geometry.

In complex (I), the L^3- ligand chelates two Cu^II cations via three O atoms, two hydrazinide N atoms and one S atom, and connects neighbouring Cu^II cations through two acetate anions to form a tetra­nuclear structure (Fig. 2). Neighbouring Cu···Cu inter­atomic separations are Cu1···Cu2 = 4.586 (2) Å and Cu1···Cu2ⁱ = 3.059 (2) Å. The tetra­nuclear units and adjacent di­methyl­formamide (DMF) solvent molecules are held together through hydrogen-bonding inter­actions between the amide group of the L^3- ligand and the O atom of the DMF molecule [N3—H3···O6ⁱ = 2.812 (4) Å; Table 3] (Fig. 3).

The asymmetric unit of complex (II) consists of one Cd^II cation, one µ₂-bridging HL^2- ligand {systematic name: [(2-hy­droxy­phenyl)­formamido](propanamido­methane­thioyl)aza­nide}, one 4,4'-bi­pyridine ligand, one nitrate ligand and one water molecule (Fig. 1). In the structure, each Cd^II anion adopts a distorted o­cta­hedral coordination geometry, with the equatorial plane formed by two O (O2 and O3) and one N atom (N2) from an HL^2- ligand, and by one N atom (N4) from the 4,4'-bi­pyridine ligand. Atoms O2, N2, O3 and N4 and the Cd1 atom are nearly planar, with a maximum deviation from the least-squares plane of 0.6194 (3) Å for atom O3. The Cd1—O2 and Cd1—O3 bond lengths (Table 4) are similar to values reported previously (Lashgari et al., 1998). Along the axial positions, the two coordination sites are occupied by nitrate atom O4 and HL^2- atom S1ⁱⁱ [symmetry code: (ii) -x+1, -y+1, -z+1]. The Cd1—O4 bond length is 2.324 (2) Å, while the Cd1—S1ⁱ bond lengths is 2.6551 (12) Å, which is slightly shorter than that reported previously [2.7364 (8) Å] for Cd complexes with thio­semicarbazones (Wang et al., 2010).

Due to the axial coordination of the S atoms, neighbouring Cd^II cations are connected to generate a centrosymmetric binuclear molecule with a Cd···S···Cd angle of 87.11 (4)° and a Cd···Cd distance of 5.5558 (14) Å (Fig. 2). In the structure of (II), hydrogen bonds play an important role in the compact stacking. As shown in Fig. 3, the H atom on atom O1 of the HL^2- ligand is involved in an inter­molecular O1—H1···N5ⁱⁱⁱ [symmetry code: (iii) x, y+1, z+1] hydrogen bond with an N atom of the 4,4'-bi­pyridine ligand [O1···N5ⁱⁱⁱ = 2.670 (4) Å] (Table 5). The binuclear units are held together by this hydrogen bond to form a one-dimensional coordination polymer. The H atom on atom N3 of the HL^2- ligand is involved in an inter­molecular N3—H3A···O7^iv [symmetry code: (iv) -x+1, -y+1, -z+1] hydrogen bond with atom O7 of the free water molecule [N3···O7^iv = 2.865 (4) Å [or 2.841 (4)]]. Besides the inter­molecular inter­actions, some intra­molecular hydrogen bonds, such as N1—H1A···O1 and N1—H1A···S1, are also found involving the organic di­acyl­thio­semicarbazone ligands, with N···O and N···S distances of 2.597 (3) and 2.878 (2) Å, respectively. [Table 5 added; OK?]

In these structures, the combination of the L^3- ligands with Cu^II cations led to a discrete tetra­nuclear cluster. In the cluster, each ligand chelates two Cu^II cations to form a binuclear subunit, which was inter­connected by O atoms of acetate anion to get a tetra­nuclear structure. [The scheme shows the L^3- ligands as µ₄-bridging?] However, the combination of the H₂L^- ligands with Cd^II cations produces a discrete dinuclear molecule. In (II), each H₂L^- ligand is linked to one Cd^II cation [scheme shows the H₂L^- ligands linked to two Cd cations?], while each H₃L ligand is linked two four?] Cu^II cations in (I). As stated above, the remarkable difference in (I) and (II) is the coordination mode of the acyl­thio­semicarbazide ligand. In (II), the phenolic hy­droxy group and hydrazide N atom of the H₂L^- ligands are not involved in coordination, which may be attributed to the larger ionic radius of Cd^II cations compared with Cu^II cations. The distance between atoms O2 and O3 is 4.343 (3) Å in complex (II), while the distance between atoms O1 and S1 is 3.620 (3) Å (Fig. 4). Due to the ionic radius of Cu^II being smaller than that of Cd^II (0.73 Å for Cu²⁺ versus 0.95 Å for Cd²⁺), this short distance can chelate Cu^II cations, but cannot inter­play with Cd^II cations of larger radius.

Structure description

Thio­semicarbazides and their derivatives have attracted considerable inter­est because of not only their biological activities, including anti­bacterial, anti­malarial, anti­viral, and anti­tumor activities (Quiroga & Ranninger, 2004; Kasuga et al., 2003; Easmon et al., 2001), but also their flexibility, which allows the ligands to bend and rotate freely to accommodate the coordination geometries of various metal centres. Many metal complexes derived from thio­semicarbazones have been structurally characterized, and they possess a wide variety of biological activities (Leovac et al., 2009; Hassanien et al., 2008; Latheef et al., 2006; Babb et al., 2003; Simonov et al. , 2002; Belicchi-Ferrari et al., 2000).

Acyl­thio­semicarbazide ligands contain O, S, and N atoms as potential donors, and can support mono- and multinuclear structural complexes. Most of these activities mainly depend on their electronic and redox properties, which could be tuned by the attached substituent numbers and positions, and the conformation of ligands (Dearling et al., 2002; Maurer et al., 2002; Fetrrai et al., 2000). In order to figure out the structure–property relationships, a great number of metal complexes based on thio­semicarbazone derivatives, particularly the 1,4-disubstituted derivatives, have been prepared and their biological activities investigated systematically (Floquet et al., 2009; Hassanien et al., 2008; Latheef et al., 2006; Babb et al., 2003; Simonov et al., 2002; Belicchi-Ferrari et al., 2000). Among these, only a few examples have dealt with 1,4-di­acyl-thio­semicarbazone derivatives (Xue et al., 2006; Ali et al., 2004; Yamin & Yusof, 2003; Liu et al., 2013). Recently, much attention has been paid to multinuclear complexes as a result of their magnetic properties and theoretical significance (Li & Jin, 2013; Wei et al., 2012; Pradeep & Leroy, 2007; Moon et al., 2006). Thio­semicarbazide derivatives contain an N—N unit which can bridge two metal atoms, enabling them to form dinuclear or multinuclear complexes. However, reports on multinuclear complexes with the 1,4-di­acyl­thio­semicarbazide ligand are rare. In order to obtain such multinuclear complexes, we have synthesized a new acyl­thio­semicarbazide ligand, namely N-[2-(2-hy­droxy­benzoyl)­hydrazinecarbono­thioyl]propanamide (H₃L). The combination of H₃L with Cu(CH₃COO)₂ or Cd(NO₃)₂ afforded [Cu₄L₂(CH₃COO)₂]·2DMF, (I), and [Cd₂(HL)₂(C₁₀H₈N₂)₂]·2H₂O, (II), respectively, whose structures are reported herein.

A mixture of Cu(CH₃COO)₂·2H₂O (0.0402 g, 0.20 mmol) and H₃L (0.0268 g, 0.10 mmol) were dissolved in a mixed solvent of methanol and di­methyl­formamide (12 ml, 5:1 v/v), and the solution was stirred for 3 h at room temperature. The resulting blue solution was filtered. After standing for several days, black block-shaped crystals were obtained from the filtrate. IR data (KBr, cm^-1): 3268 (w), 3059 (w), 2944 (w), 2876 (w), 1610 (m), 1634 (m), 1603 (s), 1551 (s), 1514 (m), 1477 (s), 1404 (s), 1269 (m), 1107 (m), 861 (m), 757 (m), 668 (m).

H₃L (0.0268 g, 0.10 mmol) and Cd(NO₃)₂ (0.0475 g, 0.20 mmol) were dissolved in a mixed solvent of methanol and di­methyl­formamide (12 ml, 5:1 v/v). 4,4'-Bi­pyridine (0.0080 g 0.05 mmol) was added and the solution was stirred for 3 h at room temperature. The resulting white suspension mixture was filtered and the filtrate allowed to evaporate in air at room temperature. Colourless crystals of (II) were separated from the filtrate after a period of one week. IR data (KBr, cm^-1): 3513 (m), 3080 (w), 2991 (w), 1675 (s), 1597 (s), 1561 (s), 1467 (s), 1383 (s), 1294 (s), 1221 (s), 1070 (m), 997 (m), 898 (m), 815 (m), 762 (m), 642 (s).

Complex (I) crystallizes in the triclinic space group P1 (No. 2). The asymmetric unit contains two Cu^II ions, one µ₄-bridging deprotonated L^3- ligand {systematic name: 1-[(2-oxido­phenyl)­carbonyl]-2-(propanamido­methane­thioyl)hydrazine-1,2-diide}, one µ₂-bridging acetate ligand and one free di­methyl­formamide (DMF) molecule. As shown in Fig. 1, the Cu1 atom adopts a significantly re­cta­ngular pyramidal coordination geometry involving two L^3- ligands and one O atom from an acetate ligand; the equatorial plane is occupied by a phenolate O atom (O1), one deprotonated hydrazide N atom (N1), one S atom from the L^3- ligand (S1) and one O atom from an acetate ligand [O5ⁱ; symmetry code: (i) -x, -y, -z+1], while the axial position is occupied by a carbonyl O atom of another L^3- ligand (O2ⁱ). In the equatorial plane, the Cu1—O and Cu1—N bond lengths are 1.898 (3)–1.955 (3) and 1.927 (3) Å, respectively (Table 2). The apical Cu—O distance [Cu1—O2ⁱ = 2.719 (3) Å] is slightly longer than a common Cu—O distance (Liu et al., 2013). Atom Cu2 has a similar five-coordination and is triply chelated by two carbonyl O atoms (O2 and O3) and one deprotonated hydrazide N atom (N2) from L^3- ligands and by one O atom from an acetate anion (O4). The axial position is occupied by one phenolate O atom from another L^3- ligand (O1ⁱ), with a Cu2—O1ⁱ distance of 2.465 (3) Å, forming an elongated re­cta­ngular pyramidal geometry.

In complex (I), the L^3- ligand chelates two Cu^II cations via three O atoms, two hydrazinide N atoms and one S atom, and connects neighbouring Cu^II cations through two acetate anions to form a tetra­nuclear structure (Fig. 2). Neighbouring Cu···Cu inter­atomic separations are Cu1···Cu2 = 4.586 (2) Å and Cu1···Cu2ⁱ = 3.059 (2) Å. The tetra­nuclear units and adjacent di­methyl­formamide (DMF) solvent molecules are held together through hydrogen-bonding inter­actions between the amide group of the L^3- ligand and the O atom of the DMF molecule [N3—H3···O6ⁱ = 2.812 (4) Å; Table 3] (Fig. 3).

The asymmetric unit of complex (II) consists of one Cd^II cation, one µ₂-bridging HL^2- ligand {systematic name: [(2-hy­droxy­phenyl)­formamido](propanamido­methane­thioyl)aza­nide}, one 4,4'-bi­pyridine ligand, one nitrate ligand and one water molecule (Fig. 1). In the structure, each Cd^II anion adopts a distorted o­cta­hedral coordination geometry, with the equatorial plane formed by two O (O2 and O3) and one N atom (N2) from an HL^2- ligand, and by one N atom (N4) from the 4,4'-bi­pyridine ligand. Atoms O2, N2, O3 and N4 and the Cd1 atom are nearly planar, with a maximum deviation from the least-squares plane of 0.6194 (3) Å for atom O3. The Cd1—O2 and Cd1—O3 bond lengths (Table 4) are similar to values reported previously (Lashgari et al., 1998). Along the axial positions, the two coordination sites are occupied by nitrate atom O4 and HL^2- atom S1ⁱⁱ [symmetry code: (ii) -x+1, -y+1, -z+1]. The Cd1—O4 bond length is 2.324 (2) Å, while the Cd1—S1ⁱ bond lengths is 2.6551 (12) Å, which is slightly shorter than that reported previously [2.7364 (8) Å] for Cd complexes with thio­semicarbazones (Wang et al., 2010).

Due to the axial coordination of the S atoms, neighbouring Cd^II cations are connected to generate a centrosymmetric binuclear molecule with a Cd···S···Cd angle of 87.11 (4)° and a Cd···Cd distance of 5.5558 (14) Å (Fig. 2). In the structure of (II), hydrogen bonds play an important role in the compact stacking. As shown in Fig. 3, the H atom on atom O1 of the HL^2- ligand is involved in an inter­molecular O1—H1···N5ⁱⁱⁱ [symmetry code: (iii) x, y+1, z+1] hydrogen bond with an N atom of the 4,4'-bi­pyridine ligand [O1···N5ⁱⁱⁱ = 2.670 (4) Å] (Table 5). The binuclear units are held together by this hydrogen bond to form a one-dimensional coordination polymer. The H atom on atom N3 of the HL^2- ligand is involved in an inter­molecular N3—H3A···O7^iv [symmetry code: (iv) -x+1, -y+1, -z+1] hydrogen bond with atom O7 of the free water molecule [N3···O7^iv = 2.865 (4) Å [or 2.841 (4)]]. Besides the inter­molecular inter­actions, some intra­molecular hydrogen bonds, such as N1—H1A···O1 and N1—H1A···S1, are also found involving the organic di­acyl­thio­semicarbazone ligands, with N···O and N···S distances of 2.597 (3) and 2.878 (2) Å, respectively. [Table 5 added; OK?]

In these structures, the combination of the L^3- ligands with Cu^II cations led to a discrete tetra­nuclear cluster. In the cluster, each ligand chelates two Cu^II cations to form a binuclear subunit, which was inter­connected by O atoms of acetate anion to get a tetra­nuclear structure. [The scheme shows the L^3- ligands as µ₄-bridging?] However, the combination of the H₂L^- ligands with Cd^II cations produces a discrete dinuclear molecule. In (II), each H₂L^- ligand is linked to one Cd^II cation [scheme shows the H₂L^- ligands linked to two Cd cations?], while each H₃L ligand is linked two four?] Cu^II cations in (I). As stated above, the remarkable difference in (I) and (II) is the coordination mode of the acyl­thio­semicarbazide ligand. In (II), the phenolic hy­droxy group and hydrazide N atom of the H₂L^- ligands are not involved in coordination, which may be attributed to the larger ionic radius of Cd^II cations compared with Cu^II cations. The distance between atoms O2 and O3 is 4.343 (3) Å in complex (II), while the distance between atoms O1 and S1 is 3.620 (3) Å (Fig. 4). Due to the ionic radius of Cu^II being smaller than that of Cd^II (0.73 Å for Cu²⁺ versus 0.95 Å for Cd²⁺), this short distance can chelate Cu^II cations, but cannot inter­play with Cd^II cations of larger radius.

Synthesis and crystallization

All analytical grade chemicals were obtained commercially and were used without further purifiation. N-{[2-(2-Hy­droxy­benzoyl)­hydrazine]carbono­thioyl}propanamide (H₃L) was prepared according to the literature procedure of Wang et al. (2000).

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1. The H atoms of water were located in difference Fourier maps and their positions were refined with O—H bond-length restraints of 0.84 Å and with U_iso(H) = 1.2U_eq(O). The remaining H atoms were positioned in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.93 (aryl) or 0.96 Å (methyl), and with U_iso(H) = 1.5U_eq(C) for methyl groups and 1.2U_eq(C) otherwise.

Computing details

For both compounds, data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalClear (Rigaku, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The coordination environment of the Cu^II cation centre in (I), with displacement ellipsoids drawn at the 50% probability level. [Symmetry code: (i) -x, -y, -z + 1.]
	Fig. 2. The two acetate-bridgedasymmetric units forming a tetranuclear molecule in (I).
	Fig. 3. A packing diagram for (I), showing the N—H···O interactions (purple dashed lines). All H atoms, except for those involved in the weak interactions, have been omitted.
	Fig. 4. Coordination environment of the Cd^II cation centre in (II), with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) -x + 1, -y + 1, -z + 1.]
	Fig. 5. The two S-atom-bridged asymmetric units forming a binuclear molecule in (II).
	Fig. 6. The one-dimensional structure of (II) and the hydrogen-bond interactions (dashed lines).

(I) Di-µ-acetato-bis{µ₄-1-[(2-oxidophenyl)carbonyl]-2-(propanamidomethanethioyl)hydrazine-1,2-diido}tetracopper(II) dimethylformamide disolvate

Crystal data

[Cu4(C11H10N3O3S)2(C2H3O2)2]·2C3H7NO	Z = 1
Mr = 1047.00	F(000) = 532
Triclinic, P1	Dx = 1.761 Mg m^−3
a = 8.4421 (17) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.435 (2) Å	Cell parameters from 2965 reflections
c = 11.909 (2) Å	θ = 3.2–27.5°
α = 111.67 (3)°	µ = 2.30 mm^−1
β = 107.76 (3)°	T = 293 K
γ = 95.87 (3)°	Block, black
V = 987.0 (4) Å^3	0.28 × 0.20 × 0.15 mm

Data collection

Rigaku Saturn 724 CCD area-detector diffractometer	3779 reflections with I > 2σ(I)
ω scans	Rint = 0.036
Absorption correction: numerical (RAPID-AUTO; Rigaku, 1998)	θmax = 27.5°, θmin = 3.2°
Tmin = 0.715, Tmax = 0.919	h = −10→10
8309 measured reflections	k = −14→14
4355 independent reflections	l = −15→15

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.106	w = 1/[σ^2(Fo^2) + (0.0342P)^2 + 1.232P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max < 0.001
4355 reflections	Δρmax = 0.38 e Å^−3
266 parameters	Δρmin = −0.50 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.30091 (14)	−0.21492 (9)	0.48375 (10)	0.0428 (2)
Cu1	0.17118 (6)	−0.11507 (4)	0.62211 (4)	0.03556 (13)
Cu2	0.19996 (6)	0.12971 (4)	0.39528 (4)	0.03636 (13)
O1	0.0974 (3)	−0.0171 (2)	0.7556 (2)	0.0394 (6)
O2	0.1568 (3)	0.2107 (2)	0.5535 (2)	0.0400 (6)
O3	0.2854 (3)	0.0413 (2)	0.2591 (2)	0.0404 (6)
O4	0.1590 (4)	0.2701 (2)	0.3473 (3)	0.0449 (6)
O5	−0.1058 (4)	0.2701 (2)	0.3527 (3)	0.0437 (6)
O6	0.4395 (5)	0.6377 (3)	0.2128 (3)	0.0651 (9)
N1	0.2097 (4)	0.0277 (3)	0.5768 (3)	0.0337 (6)
N2	0.2482 (4)	0.0051 (3)	0.4654 (3)	0.0329 (6)
N3	0.3370 (4)	−0.1308 (3)	0.3097 (3)	0.0377 (7)
H3	0.3718	−0.2007	0.2846	0.045*
N4	0.5064 (5)	0.4571 (4)	0.2321 (4)	0.0568 (10)
C1	0.1089 (5)	0.1099 (3)	0.8028 (3)	0.0354 (7)
C2	0.0844 (5)	0.1688 (4)	0.9206 (4)	0.0441 (9)
H4	0.0707	0.1197	0.9657	0.053*
C3	0.0802 (6)	0.2974 (4)	0.9712 (4)	0.0527 (10)
H3A	0.0632	0.3337	1.0492	0.063*
C4	0.1013 (6)	0.3736 (4)	0.9061 (4)	0.0544 (11)
H2	0.0978	0.4603	0.9397	0.065*
C5	0.1274 (5)	0.3189 (4)	0.7918 (4)	0.0449 (9)
H1	0.1402	0.3694	0.7478	0.054*
C6	0.1355 (4)	0.1888 (3)	0.7392 (3)	0.0355 (8)
C7	0.1674 (4)	0.1409 (3)	0.6178 (3)	0.0334 (7)
C8	0.2930 (4)	−0.1032 (3)	0.4187 (3)	0.0331 (7)
C9	0.3320 (5)	−0.0617 (4)	0.2381 (3)	0.0374 (8)
C10	0.3912 (6)	−0.1179 (5)	0.1266 (4)	0.0550 (11)
H10A	0.5148	−0.0873	0.1587	0.066*
H10B	0.3647	−0.2116	0.0952	0.066*
C11	0.3140 (8)	−0.0853 (6)	0.0159 (5)	0.0836 (18)
H11A	0.1918	−0.1176	−0.0188	0.125*
H11B	0.3585	−0.1243	−0.0506	0.125*
H11C	0.3417	0.0071	0.0452	0.125*
C12	0.0276 (6)	0.3158 (4)	0.3427 (4)	0.0416 (9)
C13	0.0351 (6)	0.4398 (4)	0.3253 (5)	0.0596 (12)
H13A	−0.0673	0.4308	0.2560	0.089*
H13B	0.1332	0.4580	0.3042	0.089*
H13C	0.0441	0.5098	0.4044	0.089*
C14	0.5265 (10)	0.3825 (8)	0.3076 (9)	0.128 (3)
H14A	0.5328	0.4355	0.3937	0.192*
H14B	0.6300	0.3531	0.3128	0.192*
H14C	0.4302	0.3090	0.2668	0.192*
C15	0.5271 (7)	0.4010 (5)	0.1085 (5)	0.0760 (15)
H15A	0.5081	0.4582	0.0662	0.114*
H15B	0.4456	0.3188	0.0546	0.114*
H15C	0.6412	0.3888	0.1227	0.114*
C16	0.4658 (6)	0.5703 (5)	0.2711 (5)	0.0641 (13)
H16	0.4565	0.6013	0.3523	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0582 (6)	0.0339 (5)	0.0537 (6)	0.0257 (4)	0.0298 (5)	0.0258 (4)
Cu1	0.0433 (3)	0.0289 (2)	0.0430 (3)	0.01628 (19)	0.0188 (2)	0.01989 (19)
Cu2	0.0465 (3)	0.0278 (2)	0.0432 (3)	0.01498 (19)	0.0202 (2)	0.01943 (19)
O1	0.0543 (16)	0.0299 (12)	0.0411 (14)	0.0157 (12)	0.0227 (12)	0.0169 (11)
O2	0.0582 (16)	0.0272 (12)	0.0430 (14)	0.0162 (12)	0.0229 (13)	0.0190 (11)
O3	0.0500 (15)	0.0374 (14)	0.0440 (14)	0.0176 (12)	0.0219 (12)	0.0225 (12)
O4	0.0584 (17)	0.0362 (14)	0.0568 (17)	0.0199 (13)	0.0293 (14)	0.0288 (13)
O5	0.0572 (17)	0.0358 (14)	0.0577 (17)	0.0232 (13)	0.0305 (14)	0.0300 (13)
O6	0.087 (2)	0.0515 (19)	0.079 (2)	0.0400 (18)	0.041 (2)	0.0370 (18)
N1	0.0408 (16)	0.0279 (14)	0.0361 (16)	0.0131 (12)	0.0157 (13)	0.0149 (12)
N2	0.0362 (15)	0.0292 (14)	0.0354 (15)	0.0109 (12)	0.0131 (13)	0.0152 (12)
N3	0.0435 (17)	0.0344 (16)	0.0416 (17)	0.0199 (14)	0.0192 (14)	0.0172 (13)
N4	0.058 (2)	0.055 (2)	0.079 (3)	0.0326 (19)	0.036 (2)	0.038 (2)
C1	0.0382 (19)	0.0298 (17)	0.0362 (18)	0.0113 (15)	0.0116 (15)	0.0127 (14)
C2	0.049 (2)	0.043 (2)	0.040 (2)	0.0109 (18)	0.0176 (18)	0.0173 (17)
C3	0.065 (3)	0.043 (2)	0.046 (2)	0.017 (2)	0.028 (2)	0.0085 (18)
C4	0.072 (3)	0.037 (2)	0.056 (3)	0.022 (2)	0.032 (2)	0.0119 (19)
C5	0.059 (2)	0.0293 (18)	0.047 (2)	0.0187 (18)	0.0207 (19)	0.0138 (16)
C6	0.0357 (18)	0.0318 (18)	0.0369 (19)	0.0113 (15)	0.0112 (15)	0.0133 (15)
C7	0.0338 (18)	0.0267 (16)	0.0383 (18)	0.0072 (14)	0.0109 (15)	0.0141 (14)
C8	0.0325 (17)	0.0289 (17)	0.0402 (19)	0.0105 (14)	0.0137 (15)	0.0160 (15)
C9	0.0352 (18)	0.043 (2)	0.0361 (19)	0.0150 (16)	0.0121 (15)	0.0188 (16)
C10	0.071 (3)	0.059 (3)	0.052 (2)	0.035 (2)	0.033 (2)	0.028 (2)
C11	0.113 (5)	0.115 (5)	0.066 (3)	0.064 (4)	0.056 (3)	0.056 (4)
C12	0.064 (3)	0.0325 (18)	0.040 (2)	0.0192 (18)	0.0226 (18)	0.0220 (16)
C13	0.081 (3)	0.041 (2)	0.084 (3)	0.028 (2)	0.041 (3)	0.043 (2)
C14	0.152 (7)	0.164 (7)	0.215 (9)	0.119 (6)	0.137 (7)	0.159 (7)
C15	0.075 (3)	0.058 (3)	0.080 (4)	0.029 (3)	0.029 (3)	0.010 (3)
C16	0.070 (3)	0.066 (3)	0.075 (3)	0.037 (3)	0.039 (3)	0.034 (3)

Geometric parameters (Å, º)

S1—C8	1.719 (3)	C1—C2	1.405 (5)
Cu1—S1	2.2771 (12)	C1—C6	1.416 (5)
Cu1—N1	1.927 (3)	C2—C3	1.377 (5)
Cu1—O1	1.898 (3)	C2—H4	0.9300
Cu1—O2^i	2.719 (3)	C3—C4	1.394 (6)
Cu1—O5^i	1.957 (2)	C3—H3A	0.9300
Cu1—Cu2^i	3.0592 (9)	C4—C5	1.369 (6)
Cu2—N2	1.919 (3)	C4—H2	0.9300
Cu2—O1^i	2.645 (3)	C5—C6	1.403 (5)
Cu2—O2	1.934 (3)	C5—H1	0.9300
Cu2—O3	1.955 (3)	C6—C7	1.464 (5)
Cu2—O4	1.922 (2)	C9—C10	1.506 (5)
Cu2—Cu1^i	3.0592 (9)	C10—C11	1.480 (6)
O1—C1	1.330 (4)	C10—H10A	0.9700
O2—C7	1.287 (4)	C10—H10B	0.9700
O3—C9	1.241 (4)	C11—H11A	0.9600
O4—C12	1.269 (5)	C11—H11B	0.9600
O5—C12	1.251 (5)	C11—H11C	0.9600
O5—Cu1^i	1.957 (2)	C12—C13	1.505 (5)
O6—C16	1.209 (5)	C13—H13A	0.9600
N1—C7	1.332 (4)	C13—H13B	0.9600
N1—N2	1.399 (4)	C13—H13C	0.9600
N2—C8	1.304 (4)	C14—H14A	0.9600
N3—C9	1.354 (4)	C14—H14B	0.9600
N3—C8	1.393 (4)	C14—H14C	0.9600
N3—H3	0.8600	C15—H15A	0.9600
N4—C16	1.323 (6)	C15—H15B	0.9600
N4—C14	1.439 (6)	C15—H15C	0.9600
N4—C15	1.446 (6)	C16—H16	0.9300
C8—S1—Cu1	93.93 (12)	C4—C5—H1	119.1
O1—Cu1—N1	92.53 (11)	C6—C5—H1	119.1
O1—Cu1—O5^i	89.60 (11)	C5—C6—C1	119.3 (3)
N1—Cu1—O5^i	172.58 (12)	C5—C6—C7	117.4 (3)
O1—Cu1—S1	171.24 (9)	C1—C6—C7	123.3 (3)
N1—Cu1—S1	85.48 (9)	O2—C7—N1	121.0 (3)
O5^i—Cu1—S1	93.46 (8)	O2—C7—C6	118.9 (3)
O1—Cu1—Cu2^i	53.58 (9)	N1—C7—C6	120.0 (3)
N1—Cu1—Cu2^i	100.31 (9)	N2—C8—N3	118.5 (3)
O5^i—Cu1—Cu2^i	75.30 (8)	N2—C8—S1	123.9 (3)
S1—Cu1—Cu2^i	135.18 (4)	N3—C8—S1	117.6 (2)
N2—Cu2—O4	172.78 (12)	O3—C9—N3	125.2 (3)
N2—Cu2—O2	81.04 (11)	O3—C9—C10	119.9 (3)
O4—Cu2—O2	92.43 (11)	N3—C9—C10	114.9 (3)
N2—Cu2—O3	89.95 (11)	C11—C10—C9	114.7 (4)
O4—Cu2—O3	96.06 (11)	C11—C10—H10A	108.6
O2—Cu2—O3	167.88 (11)	C9—C10—H10A	108.6
N2—Cu2—Cu1^i	98.75 (9)	C11—C10—H10B	108.6
O4—Cu2—Cu1^i	80.60 (9)	C9—C10—H10B	108.6
O2—Cu2—Cu1^i	61.18 (9)	H10A—C10—H10B	107.6
O3—Cu2—Cu1^i	128.80 (9)	C10—C11—H11A	109.5
C1—O1—Cu1	126.9 (2)	C10—C11—H11B	109.5
C7—O2—Cu2	112.7 (2)	H11A—C11—H11B	109.5
C9—O3—Cu2	126.9 (2)	C10—C11—H11C	109.5
C12—O4—Cu2	124.9 (2)	H11A—C11—H11C	109.5
C12—O5—Cu1^i	131.1 (2)	H11B—C11—H11C	109.5
C7—N1—N2	110.9 (3)	O5—C12—O4	127.2 (3)
C7—N1—Cu1	128.7 (2)	O5—C12—C13	116.7 (4)
N2—N1—Cu1	118.5 (2)	O4—C12—C13	116.0 (4)
C8—N2—N1	115.3 (3)	C12—C13—H13A	109.5
C8—N2—Cu2	130.4 (2)	C12—C13—H13B	109.5
N1—N2—Cu2	113.8 (2)	H13A—C13—H13B	109.5
C9—N3—C8	128.3 (3)	C12—C13—H13C	109.5
C9—N3—H3	115.9	H13A—C13—H13C	109.5
C8—N3—H3	115.9	H13B—C13—H13C	109.5
C16—N4—C14	122.1 (5)	N4—C14—H14A	109.5
C16—N4—C15	121.0 (4)	N4—C14—H14B	109.5
C14—N4—C15	116.9 (5)	H14A—C14—H14B	109.5
O1—C1—C2	117.8 (3)	N4—C14—H14C	109.5
O1—C1—C6	124.5 (3)	H14A—C14—H14C	109.5
C2—C1—C6	117.6 (3)	H14B—C14—H14C	109.5
C3—C2—C1	121.7 (4)	N4—C15—H15A	109.5
C3—C2—H4	119.1	N4—C15—H15B	109.5
C1—C2—H4	119.1	H15A—C15—H15B	109.5
C2—C3—C4	120.4 (4)	N4—C15—H15C	109.5
C2—C3—H3A	119.8	H15A—C15—H15C	109.5
C4—C3—H3A	119.8	H15B—C15—H15C	109.5
C5—C4—C3	119.0 (4)	O6—C16—N4	127.2 (5)
C5—C4—H2	120.5	O6—C16—H16	116.4
C3—C4—H2	120.5	N4—C16—H16	116.4
C4—C5—C6	121.9 (4)
N1—Cu1—O1—C1	−10.5 (3)	Cu1—N1—C7—C6	21.1 (5)
O5^i—Cu1—O1—C1	176.6 (3)	C5—C6—C7—O2	−12.0 (5)
Cu2^i—Cu1—O1—C1	−111.4 (3)	C1—C6—C7—O2	166.5 (3)
C7—N1—N2—C8	179.3 (3)	C5—C6—C7—N1	166.8 (3)
Cu1—N1—N2—C8	−15.1 (4)	C1—C6—C7—N1	−14.7 (5)
C7—N1—N2—Cu2	−7.6 (3)	N1—N2—C8—N3	−178.5 (3)
Cu1—N1—N2—Cu2	157.98 (15)	Cu2—N2—C8—N3	9.8 (5)
Cu1—O1—C1—C2	−165.4 (3)	N1—N2—C8—S1	1.5 (4)
Cu1—O1—C1—C6	17.9 (5)	Cu2—N2—C8—S1	−170.12 (18)
O1—C1—C2—C3	−174.7 (4)	C9—N3—C8—N2	−3.7 (6)
C6—C1—C2—C3	2.2 (6)	C9—N3—C8—S1	176.3 (3)
C1—C2—C3—C4	−0.3 (7)	Cu1—S1—C8—N2	9.3 (3)
C2—C3—C4—C5	−0.4 (7)	Cu1—S1—C8—N3	−170.7 (3)
C3—C4—C5—C6	−0.7 (7)	Cu2—O3—C9—N3	−2.2 (6)
C4—C5—C6—C1	2.7 (6)	Cu2—O3—C9—C10	178.7 (3)
C4—C5—C6—C7	−178.8 (4)	C8—N3—C9—O3	0.0 (6)
O1—C1—C6—C5	173.3 (4)	C8—N3—C9—C10	179.1 (4)
C2—C1—C6—C5	−3.3 (5)	O3—C9—C10—C11	−28.5 (6)
O1—C1—C6—C7	−5.1 (6)	N3—C9—C10—C11	152.3 (5)
C2—C1—C6—C7	178.2 (3)	Cu1^i—O5—C12—O4	−0.3 (6)
Cu2—O2—C7—N1	2.0 (4)	Cu1^i—O5—C12—C13	−179.3 (3)
Cu2—O2—C7—C6	−179.2 (2)	Cu2—O4—C12—O5	−9.2 (6)
N2—N1—C7—O2	3.7 (5)	Cu2—O4—C12—C13	169.9 (3)
Cu1—N1—C7—O2	−160.1 (3)	C14—N4—C16—O6	−176.9 (6)
N2—N1—C7—C6	−175.1 (3)	C15—N4—C16—O6	1.1 (9)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O6^ii	0.86	1.95	2.812 (4)	175

Symmetry code: (ii) x, y−1, z.

(II) Bis{µ₂-[(2-hydroxyphenyl)formamido](propanamidomethanethioyl)azanido}bis[(4,4'-bipyridine)nitratocadmium(II)] dihydrate

Crystal data

[Cd2(C11H12N3O3S)2(NO3)2(C10H8N2)2]·2H2O	Z = 1
Mr = 1229.81	F(000) = 620
Triclinic, P1	Dx = 1.720 Mg m^−3
a = 9.959 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.531 (2) Å	Cell parameters from 11746 reflections
c = 12.617 (3) Å	θ = 3.1–27.5°
α = 81.35 (3)°	µ = 1.06 mm^−1
β = 82.13 (3)°	T = 293 K
γ = 65.60 (3)°	Rod, colourless
V = 1187.2 (5) Å^3	0.42 × 0.18 × 0.15 mm

Data collection

Rigaku Saturn 724 CCD area-detector diffractometer	4586 reflections with I > 2σ(I)
ω scans	Rint = 0.028
Absorption correction: multi-scan (RAPID-AUTO; Rigaku, 1998)	θmax = 27.5°, θmin = 3.1°
Tmin = 0.767, Tmax = 1.000	h = −12→11
11746 measured reflections	k = −13→13
5381 independent reflections	l = −16→16

Refinement

Refinement on F^2	4 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.071	w = 1/[σ^2(Fo^2) + (0.0392P)^2 + 1.3103P] where P = (Fo^2 + 2Fc^2)/3
S = 0.86	(Δ/σ)max = 0.012
5381 reflections	Δρmax = 0.39 e Å^−3
333 parameters	Δρmin = −0.32 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.63555 (7)	0.68589 (7)	0.53201 (5)	0.03255 (14)
Cd1	0.36946 (2)	0.51522 (2)	0.31490 (2)	0.02971 (7)
O1	0.2601 (2)	0.8687 (3)	0.64393 (18)	0.0505 (6)
H1	0.2606	0.9166	0.6893	0.076*
O2	0.17715 (19)	0.6674 (2)	0.41878 (15)	0.0347 (4)
O3	0.6031 (2)	0.4882 (2)	0.23662 (16)	0.0439 (5)
O4	0.3002 (2)	0.7033 (2)	0.18197 (17)	0.0476 (5)
O5	0.1061 (3)	0.6607 (3)	0.1880 (2)	0.0680 (7)
O6	0.1247 (3)	0.8347 (3)	0.0831 (2)	0.0731 (8)
O7	0.0007 (3)	0.4697 (3)	0.6234 (2)	0.0713 (8)
HWA	−0.052 (2)	0.474 (4)	0.5776 (9)	0.086*
HWB	0.028 (5)	0.385 (3)	0.654 (3)	0.086*
N1	0.3494 (2)	0.7113 (2)	0.48707 (16)	0.0288 (4)
H1A	0.3708	0.7483	0.5351	0.035*
N2	0.4593 (2)	0.6358 (2)	0.41346 (15)	0.0261 (4)
N3	0.7092 (2)	0.5545 (2)	0.35505 (16)	0.0300 (5)
H3A	0.7941	0.5474	0.3694	0.036*
N4	0.3782 (2)	0.3719 (2)	0.18970 (17)	0.0330 (5)
N5	0.3037 (3)	0.0096 (3)	−0.21434 (19)	0.0434 (6)
N6	0.1747 (3)	0.7337 (3)	0.14999 (19)	0.0411 (6)
C1	0.1197 (3)	0.8866 (3)	0.6352 (2)	0.0332 (6)
C2	0.0011 (3)	0.9717 (3)	0.6990 (2)	0.0408 (7)
H2	0.0181	1.0180	0.7496	0.049*
C3	−0.1409 (3)	0.9883 (3)	0.6885 (2)	0.0431 (7)
H3	−0.2193	1.0467	0.7312	0.052*
C4	−0.1682 (3)	0.9186 (3)	0.6145 (2)	0.0415 (7)
H4	−0.2641	0.9286	0.6083	0.050*
C5	−0.0515 (3)	0.8343 (3)	0.5505 (2)	0.0346 (6)
H5A	−0.0699	0.7885	0.5002	0.041*
C6	0.0939 (3)	0.8160 (3)	0.55913 (19)	0.0279 (5)
C7	0.2098 (3)	0.7265 (3)	0.48321 (19)	0.0271 (5)
C8	0.5912 (3)	0.6221 (3)	0.42860 (19)	0.0261 (5)
C9	0.7107 (3)	0.4980 (3)	0.2643 (2)	0.0315 (5)
C10	0.8566 (3)	0.4509 (4)	0.1973 (2)	0.0448 (7)
H10A	0.9325	0.3835	0.2416	0.054*
H10B	0.8819	0.5311	0.1750	0.054*
C11	0.8576 (4)	0.3855 (5)	0.0987 (3)	0.0630 (10)
H11A	0.8435	0.3001	0.1202	0.094*
H11B	0.9508	0.3653	0.0569	0.094*
H11C	0.7791	0.4493	0.0563	0.094*
C12	0.4676 (3)	0.3536 (3)	0.0995 (2)	0.0436 (7)
H12	0.5375	0.3925	0.0898	0.052*
C13	0.4622 (3)	0.2799 (4)	0.0197 (2)	0.0433 (7)
H13	0.5280	0.2693	−0.0415	0.052*
C14	0.3586 (3)	0.2218 (3)	0.03107 (19)	0.0277 (5)
C15	0.2673 (3)	0.2397 (3)	0.1256 (2)	0.0414 (7)
H15	0.1972	0.2008	0.1380	0.050*
C16	0.2799 (3)	0.3149 (3)	0.2012 (2)	0.0450 (7)
H16	0.2162	0.3263	0.2636	0.054*
C17	0.3431 (3)	0.1453 (3)	−0.05365 (19)	0.0296 (5)
C18	0.4125 (3)	0.1499 (3)	−0.1572 (2)	0.0410 (7)
H18	0.4739	0.1980	−0.1746	0.049*
C19	0.3885 (4)	0.0818 (3)	−0.2334 (2)	0.0466 (7)
H19	0.4345	0.0867	−0.3023	0.056*
C20	0.2410 (4)	0.0033 (4)	−0.1154 (2)	0.0494 (8)
H20	0.1828	−0.0482	−0.0999	0.059*
C21	0.2569 (4)	0.0684 (3)	−0.0338 (2)	0.0448 (7)
H21	0.2099	0.0606	0.0343	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0367 (3)	0.0406 (4)	0.0317 (3)	−0.0233 (3)	−0.0040 (3)	−0.0133 (3)
Cd1	0.03003 (10)	0.03742 (11)	0.02890 (10)	−0.01691 (8)	0.00113 (7)	−0.01796 (8)
O1	0.0380 (10)	0.0683 (15)	0.0533 (13)	−0.0168 (10)	−0.0032 (9)	−0.0440 (12)
O2	0.0292 (9)	0.0438 (11)	0.0391 (10)	−0.0167 (8)	−0.0004 (8)	−0.0237 (9)
O3	0.0322 (10)	0.0689 (14)	0.0415 (11)	−0.0247 (10)	0.0045 (8)	−0.0318 (10)
O4	0.0455 (12)	0.0558 (13)	0.0414 (11)	−0.0207 (10)	0.0000 (9)	−0.0069 (10)
O5	0.0724 (17)	0.0825 (19)	0.0654 (16)	−0.0501 (15)	0.0074 (13)	−0.0114 (14)
O6	0.0839 (19)	0.0619 (17)	0.0569 (15)	−0.0145 (15)	−0.0193 (14)	0.0116 (13)
O7	0.0497 (14)	0.108 (2)	0.0822 (19)	−0.0510 (16)	−0.0001 (13)	−0.0344 (17)
N1	0.0267 (10)	0.0351 (11)	0.0297 (10)	−0.0121 (9)	−0.0014 (8)	−0.0197 (9)
N2	0.0259 (9)	0.0314 (11)	0.0256 (9)	−0.0134 (8)	0.0000 (8)	−0.0125 (8)
N3	0.0245 (10)	0.0429 (13)	0.0293 (10)	−0.0176 (9)	−0.0002 (8)	−0.0134 (9)
N4	0.0375 (11)	0.0382 (12)	0.0296 (11)	−0.0188 (10)	0.0001 (9)	−0.0141 (10)
N5	0.0545 (15)	0.0479 (15)	0.0354 (12)	−0.0225 (12)	−0.0065 (11)	−0.0186 (11)
N6	0.0451 (14)	0.0444 (14)	0.0311 (12)	−0.0144 (12)	0.0036 (10)	−0.0119 (11)
C1	0.0350 (13)	0.0343 (14)	0.0310 (12)	−0.0118 (11)	0.0006 (11)	−0.0148 (11)
C2	0.0481 (16)	0.0428 (16)	0.0338 (14)	−0.0172 (13)	0.0020 (12)	−0.0189 (13)
C3	0.0405 (15)	0.0423 (16)	0.0401 (15)	−0.0108 (13)	0.0143 (12)	−0.0181 (13)
C4	0.0303 (13)	0.0457 (17)	0.0497 (16)	−0.0172 (12)	0.0080 (12)	−0.0132 (14)
C5	0.0326 (13)	0.0353 (14)	0.0397 (14)	−0.0163 (11)	0.0027 (11)	−0.0126 (12)
C6	0.0295 (12)	0.0287 (13)	0.0264 (11)	−0.0110 (10)	0.0011 (10)	−0.0106 (10)
C7	0.0293 (11)	0.0275 (12)	0.0266 (11)	−0.0117 (10)	−0.0009 (9)	−0.0094 (10)
C8	0.0285 (11)	0.0288 (12)	0.0256 (11)	−0.0145 (10)	−0.0011 (9)	−0.0080 (10)
C9	0.0285 (12)	0.0390 (14)	0.0305 (12)	−0.0149 (11)	0.0001 (10)	−0.0117 (11)
C10	0.0311 (13)	0.067 (2)	0.0387 (15)	−0.0192 (14)	0.0070 (12)	−0.0220 (15)
C11	0.0463 (18)	0.089 (3)	0.0476 (18)	−0.0146 (18)	0.0056 (15)	−0.0342 (19)
C12	0.0530 (17)	0.065 (2)	0.0335 (14)	−0.0418 (16)	0.0048 (13)	−0.0191 (14)
C13	0.0517 (17)	0.067 (2)	0.0300 (13)	−0.0408 (16)	0.0091 (12)	−0.0224 (14)
C14	0.0324 (12)	0.0285 (12)	0.0252 (11)	−0.0127 (10)	−0.0046 (10)	−0.0083 (10)
C15	0.0491 (16)	0.0538 (18)	0.0375 (14)	−0.0349 (15)	0.0095 (12)	−0.0225 (13)
C16	0.0520 (17)	0.063 (2)	0.0364 (14)	−0.0365 (16)	0.0141 (13)	−0.0305 (14)
C17	0.0336 (12)	0.0301 (13)	0.0268 (11)	−0.0117 (10)	−0.0046 (10)	−0.0097 (10)
C18	0.0514 (16)	0.0486 (17)	0.0331 (14)	−0.0283 (14)	0.0027 (12)	−0.0150 (13)
C19	0.066 (2)	0.0553 (19)	0.0277 (13)	−0.0312 (17)	0.0041 (13)	−0.0174 (13)
C20	0.065 (2)	0.063 (2)	0.0414 (16)	−0.0438 (18)	−0.0007 (14)	−0.0198 (15)
C21	0.0592 (18)	0.0601 (19)	0.0331 (14)	−0.0395 (16)	0.0035 (13)	−0.0182 (14)

Geometric parameters (Å, º)

S1—C8	1.736 (2)	C3—C4	1.387 (4)
S1—Cd1^i	2.6551 (12)	C3—H3	0.9300
Cd1—N4	2.313 (2)	C4—C5	1.378 (4)
Cd1—O2	2.3156 (19)	C4—H4	0.9300
Cd1—O3	2.3192 (19)	C5—C6	1.397 (4)
Cd1—O4	2.324 (2)	C5—H5A	0.9300
Cd1—N2	2.3823 (19)	C6—C7	1.486 (3)
Cd1—S1^i	2.6550 (12)	C9—C10	1.505 (4)
O1—C1	1.350 (3)	C10—C11	1.507 (4)
O1—H1	0.8200	C10—H10A	0.9700
O2—C7	1.244 (3)	C10—H10B	0.9700
O3—C9	1.219 (3)	C11—H11A	0.9600
O4—N6	1.263 (3)	C11—H11B	0.9600
O5—N6	1.234 (4)	C11—H11C	0.9600
O6—N6	1.225 (3)	C12—C13	1.380 (4)
O7—HWA	0.819 (18)	C12—H12	0.9300
O7—HWB	0.861 (18)	C13—C14	1.384 (4)
N1—C7	1.340 (3)	C13—H13	0.9300
N1—N2	1.385 (3)	C14—C15	1.383 (3)
N1—H1A	0.8600	C14—C17	1.490 (3)
N2—C8	1.299 (3)	C15—C16	1.377 (3)
N3—C9	1.363 (3)	C15—H15	0.9300
N3—C8	1.399 (3)	C16—H16	0.9300
N3—H3A	0.8600	C17—C21	1.382 (4)
N4—C16	1.328 (4)	C17—C18	1.396 (4)
N4—C12	1.331 (3)	C18—C19	1.381 (4)
N5—C20	1.322 (4)	C18—H18	0.9300
N5—C19	1.331 (4)	C19—H19	0.9300
C1—C2	1.389 (4)	C20—C21	1.380 (4)
C1—C6	1.406 (3)	C20—H20	0.9300
C2—C3	1.375 (4)	C21—H21	0.9300
C2—H2	0.9300
C8—S1—Cd1^i	97.01 (9)	C5—C6—C7	116.7 (2)
N4—Cd1—O2	132.99 (7)	C1—C6—C7	124.9 (2)
N4—Cd1—O3	84.56 (8)	O2—C7—N1	121.5 (2)
O2—Cd1—O3	139.10 (7)	O2—C7—C6	120.6 (2)
N4—Cd1—O4	88.51 (8)	N1—C7—C6	117.9 (2)
O2—Cd1—O4	83.86 (8)	N2—C8—N3	118.8 (2)
O3—Cd1—O4	81.36 (8)	N2—C8—S1	125.44 (18)
N4—Cd1—N2	157.09 (7)	N3—C8—S1	115.72 (17)
O2—Cd1—N2	69.60 (6)	O3—C9—N3	123.8 (2)
O3—Cd1—N2	72.73 (7)	O3—C9—C10	121.5 (2)
O4—Cd1—N2	90.93 (8)	N3—C9—C10	114.7 (2)
N4—Cd1—S1^i	88.19 (6)	C9—C10—C11	114.1 (3)
O2—Cd1—S1^i	86.19 (6)	C9—C10—H10A	108.7
O3—Cd1—S1^i	114.94 (7)	C11—C10—H10A	108.7
O4—Cd1—S1^i	162.95 (6)	C9—C10—H10B	108.7
N2—Cd1—S1^i	98.54 (6)	C11—C10—H10B	108.7
C1—O1—H1	109.5	H10A—C10—H10B	107.6
C7—O2—Cd1	117.45 (15)	C10—C11—H11A	109.5
C9—O3—Cd1	135.86 (17)	C10—C11—H11B	109.5
N6—O4—Cd1	113.76 (18)	H11A—C11—H11B	109.5
HWA—O7—HWB	104 (2)	C10—C11—H11C	109.5
C7—N1—N2	119.79 (19)	H11A—C11—H11C	109.5
C7—N1—H1A	120.1	H11B—C11—H11C	109.5
N2—N1—H1A	120.1	N4—C12—C13	123.5 (3)
C8—N2—N1	114.17 (18)	N4—C12—H12	118.2
C8—N2—Cd1	133.30 (16)	C13—C12—H12	118.2
N1—N2—Cd1	110.59 (13)	C12—C13—C14	119.8 (2)
C9—N3—C8	130.2 (2)	C12—C13—H13	120.1
C9—N3—H3A	114.9	C14—C13—H13	120.1
C8—N3—H3A	114.9	C15—C14—C13	116.4 (2)
C16—N4—C12	116.8 (2)	C15—C14—C17	121.0 (2)
C16—N4—Cd1	119.32 (17)	C13—C14—C17	122.6 (2)
C12—N4—Cd1	123.56 (18)	C16—C15—C14	120.1 (3)
C20—N5—C19	116.6 (2)	C16—C15—H15	119.9
O6—N6—O5	122.1 (3)	C14—C15—H15	119.9
O6—N6—O4	119.2 (3)	N4—C16—C15	123.4 (2)
O5—N6—O4	118.6 (3)	N4—C16—H16	118.3
O1—C1—C2	122.0 (2)	C15—C16—H16	118.3
O1—C1—C6	118.5 (2)	C21—C17—C18	116.8 (2)
C2—C1—C6	119.5 (2)	C21—C17—C14	121.4 (2)
C3—C2—C1	120.9 (3)	C18—C17—C14	121.8 (2)
C3—C2—H2	119.6	C19—C18—C17	119.0 (3)
C1—C2—H2	119.6	C19—C18—H18	120.5
C2—C3—C4	120.4 (2)	C17—C18—H18	120.5
C2—C3—H3	119.8	N5—C19—C18	124.0 (3)
C4—C3—H3	119.8	N5—C19—H19	118.0
C5—C4—C3	119.2 (3)	C18—C19—H19	118.0
C5—C4—H4	120.4	N5—C20—C21	123.9 (3)
C3—C4—H4	120.4	N5—C20—H20	118.0
C4—C5—C6	121.6 (2)	C21—C20—H20	118.0
C4—C5—H5A	119.2	C20—C21—C17	119.7 (3)
C6—C5—H5A	119.2	C20—C21—H21	120.2
C5—C6—C1	118.4 (2)	C17—C21—H21	120.2
C7—N1—N2—C8	−176.6 (2)	Cd1^i—S1—C8—N3	−103.11 (19)
C7—N1—N2—Cd1	−10.3 (3)	Cd1—O3—C9—N3	−11.3 (5)
Cd1—O4—N6—O6	177.1 (2)	Cd1—O3—C9—C10	170.4 (2)
Cd1—O4—N6—O5	−2.4 (3)	C8—N3—C9—O3	−6.3 (5)
O1—C1—C2—C3	179.9 (3)	C8—N3—C9—C10	172.1 (3)
C6—C1—C2—C3	−0.3 (5)	O3—C9—C10—C11	−3.0 (5)
C1—C2—C3—C4	0.9 (5)	N3—C9—C10—C11	178.5 (3)
C2—C3—C4—C5	−1.1 (5)	C16—N4—C12—C13	0.1 (5)
C3—C4—C5—C6	0.8 (5)	Cd1—N4—C12—C13	−173.0 (3)
C4—C5—C6—C1	−0.3 (4)	N4—C12—C13—C14	0.6 (5)
C4—C5—C6—C7	−178.0 (3)	C12—C13—C14—C15	−1.4 (5)
O1—C1—C6—C5	179.8 (3)	C12—C13—C14—C17	177.8 (3)
C2—C1—C6—C5	0.0 (4)	C13—C14—C15—C16	1.5 (5)
O1—C1—C6—C7	−2.7 (4)	C17—C14—C15—C16	−177.7 (3)
C2—C1—C6—C7	177.5 (3)	C12—N4—C16—C15	0.0 (5)
Cd1—O2—C7—N1	4.8 (3)	Cd1—N4—C16—C15	173.4 (3)
Cd1—O2—C7—C6	−174.75 (18)	C14—C15—C16—N4	−0.8 (5)
N2—N1—C7—O2	4.3 (4)	C15—C14—C17—C21	−11.8 (4)
N2—N1—C7—C6	−176.1 (2)	C13—C14—C17—C21	169.0 (3)
C5—C6—C7—O2	−2.8 (4)	C15—C14—C17—C18	167.0 (3)
C1—C6—C7—O2	179.7 (3)	C13—C14—C17—C18	−12.2 (4)
C5—C6—C7—N1	177.6 (2)	C21—C17—C18—C19	1.7 (4)
C1—C6—C7—N1	0.1 (4)	C14—C17—C18—C19	−177.2 (3)
N1—N2—C8—N3	−176.4 (2)	C20—N5—C19—C18	−0.7 (5)
Cd1—N2—C8—N3	21.3 (4)	C17—C18—C19—N5	−0.8 (5)
N1—N2—C8—S1	1.6 (3)	C19—N5—C20—C21	1.2 (5)
Cd1—N2—C8—S1	−160.68 (13)	N5—C20—C21—C17	−0.3 (6)
C9—N3—C8—N2	0.8 (4)	C18—C17—C21—C20	−1.2 (5)
C9—N3—C8—S1	−177.4 (2)	C14—C17—C21—C20	177.6 (3)
Cd1^i—S1—C8—N2	78.9 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N5^ii	0.82	1.86	2.670 (4)	168
O7—HwA···O2^iii	0.82 (2)	2.30 (3)	2.847 (4)	125 (3)
O7—HwA···O7^iii	0.82 (2)	2.55 (1)	3.084 (4)	125 (2)
N1—H1A···S1	0.86	2.44	2.878 (2)	113
N1—H1A···O1	0.86	1.91	2.597 (3)	135
O7—HwB···O5^iii	0.86 (3)	2.35 (4)	2.865 (4)	119 (3)
N3—H3A···O7^i	0.86	1.99	2.841 (4)	171
C12—H12···O3	0.93	2.51	3.127 (4)	124
C20—H20···O6^iv	0.93	2.56	3.215 (4)	128

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z+1; (iii) −x, −y+1, −z+1; (iv) x, y−1, z.