Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615023773/lg3178sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615023773/lg3178I_vCM14088sup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615023773/lg3178II_vcm14089sup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615023773/lg3178III_vCM14087twin5sup4.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2053229615023773/lg3178sup5.pdf |
CCDC references: 1441734; 1441733; 1441732
Polypyridyl multidentate ligands based on ethylenediamine backbones are an important class of metal-binding agent with particular applications in biomimetics and homogenous catalysis. We have introduced derivatives of this class of ligand which incorporate a single amino acid group and employed them to prepare model complexes for redox-active nonheme sites in metalloenzymes. Functional biomimetic and catalytic reactivity, for example, in the activation of O2 and H2O has been demonstrated (Poulsen et al. 2005; Nielsen et al. 2006; Vad et al., 2011, 2012; Lennartson & McKenzie, 2012; de Sousa et al., 2015; Deville et al., 2015). Dangling pyridines and the carboxylate groups are proposed to assist in proton transfer and the carboxylate group can be either terminal or bridge between metal ions to form oligomers and polymers (Berggren et al., 2009; Egdal et al., 2011). The latter has proved to be an advantage for achieving stability of MnII complexes towards air oxidation. If bridging does not occur, noncoordinated carboxyl O atoms are usually involved in hydrogen bonding in the solid-state structures and these interactions may be important for solution state reactivity for example in proton transfers (Vad et al., 2012).
The structures of the redox-stable copper(II) and zinc(II) complexes of the ligand N,N,N'-tris(pyridin-2-ylmethyl)ethylenediamine-N'-acetate (tpena-) reported below are important for predicting the structures of more reactive redox-active systems of earlier transition metal ions. They reveal two new structural prototypes, albeit with identical stoichiometry, thereby illustrating the coordinative flexibility of this ligand (see Scheme).
The copper and zinc halide complexes of N,N,N'-tris(pyridin-2-ylmethyl)ethylenediamine-N'-acetate (tpena-) were prepared by mixing an aqueous solution (1 ml) of Na(tpena)(CH3CH2OH) (0.048 mmol) (Vad et al., 2011) with two equivalents of the appropriate dibromide or dichloride (0.097 mmol) dissolved in MeOH (2 ml). Upon slow evaporation of the solvent, either colourless crystals of the zinc or turquoise crystals of the copper complexes formed over a period of several days. These were isolated by filtration and washed with cold H2O (yields 70–90%). IR (KBr disc): Zn2(tpena)Cl3, νas(COO) = 1602 cm-1. Zn2(tpena)Br3 νas(COO) = 1605 cm-1. Cu2(tpena)Cl3 νas(COO) = 1611 cm-1.
ESI–MS (CH3CN, 10-6 M); [Zn(tpena)]+ m/z 454.121 (calculated: 454.122, C22H24N5O2Zn) appears in the spectrum of both the chloride and the bromide zinc species. Two peaks are seen for the copper species one for the isostoichiometric [Cu(tpena)]+ at m/z 453.119 (453.133, C22H24CuN5O2) and an additional signal for [Cu(tpena-CH2COO-CH2Py)]+ m/z 317.080 (317.083, C15H18CuN4), for which no analog was observed in the spectra of the zinc complexes.
Analysis calculated for Zn2(tpena)Cl3 found (calculated) C22H24Cl3N5O2Zn2: C 41.89 (42.11), H 3.76 (3.85), N 10.91 (11.16). For Zn2(tpena)Br3 found (calculated.) C22H24Br3N5O2Zn2: C 35.26 (34.73), H 3.09 (3.18), N 9.19 (9.20). [Cu2(tpena)Br3][Cu2(tpena)Br3(H2O)]·6.5H2O, which has overall formula Cu2(tpena)Br3(H2O)3.75, analysed as Cu2(tpena)Br3(H2O)2, indicating some loss of water solvate during drying; found (calculated) C22H28Br3Cu2N5O4: C 33.58 (33.30), H 3.28 (3.55), N 8.72 (8.83).
Crystal data, data collection and structure refinement details for Zn2(tpena)Cl3, (I), Zn2(tpena)Br3, (II), and [Cu2(tpena)Br3][Cu2(tpena)Br3(H2O)].6.5H2O, (III), are summarized in Table 1. Complex (II) was refined as a racemic twin with a Flack parameter of 0.244 (13) (Flack, 1983). Complex (III) was found to be twinned by rotation of 180° about reciprocal axis [001]. The data were processed as a two-component twin using TWINABS (Sheldrick, 2012) and refined using a HKLF 5 data set constructed from all observations involving domain 1 [BASF = 0.4366 (8)]. In each structure, all H atoms bonded to C atoms were added in calculated positions, with C—H = 0.99 (CH2) or 0.95 Å (aromatic) and Uiso(H) = 1.2Ueq(C). Complex (III) contains hydrogen-bonded water molecules. Most of the H atoms were not evident in difference maps but the water O atoms are within hydrogen bonding-distance of each other. Attempts to develop a self-consistent model starting from the acceptors (carbonyls and bromides) that could not be hydrogen-bond donors were only partially successful, suggesting at least some of the H-atom sites may be disordered. These H atoms were not included in the model. One of the water molecules (O12) is disordered about a centre of symmetry and was refined with 50% occupancy.
The copper and zinc halides of tpena are prepared easily by direct reaction of the metal salts with Na(tpena) in methanol. Regardless of reaction stoichiometry, i.e. a 1:1 or a 1:2 ligand–metal salt reaction, elemental (CHN) analyses suggested that we had not obtained the desired complexes [M(tpena)]X (M = Cu2+ or Zn2+ and X = Br- or Cl-); where tpena acted as a straightforward hexadentate ligand for a six-coordinated metal ion. The elemental analyses data suggested that the three compounds all have the same tpena–M–Cl 1:2:3 stoichiometry, while at first sight confusingly ESI mass spectra recorded in acetonitrile, however, showed simple [M(tpena)]+ at m/z 454.121 and 453.119 as the only ion, or a major ion, for the zinc and copper complexes, respectively (Fig. 1). The presence of a dominant [M(tpena)]+ ion in these spectra was entirely comparable to the spectra for the simple CrIII and CoIII salts containing the [M(tpena)]+ cation (Vad et al., 2011; de Sousa et al., 2015).
Thus, the usual characterization methods gave no indication of the significant structural differences between the copper and zinc complexes that we have found in the solid state. However, close (and retrospective) inspection of IR spectra reveal small differences in the νas(OCO) carbonyl stretches just above 1600 cm-1 . With the hindsight from the crystal structures these are indicative of the anti-µ-OCO arrangement of the bridging carboxylate donor in the zinc complexes and the monodendate terminal carboxylate in the copper complex. Further, the ESI mass spectrum of the copper complex indicates that this complex is more easily fragmented. A prominent daughter ion at m/z 317.080 is due to decarboxylation and loss of a methylpyridyl arm. A proposed structure for the daughter ion is given in Fig. 2.
The complexes crystallized as Zn2(tpena)Cl3, (I), Zn2Br3(tpena), (II), and [Cu2Br3(tpena)][Cu2Br3(tpena)(H2O)].6.5H2O, (III), all containing neutral complex molecules; selected bond length and angle data are presented in Tables 2-4.
The asymmetric unit of complex (I) comprises one Zn2(tpena)Cl3 formula unit (Fig. 3). The Zn1 ion occupies the six-coordinate N5O site with irregular geometry imposed by the five five-membered chelate rings. The second metal ion, Zn2, has an approximately tetrahedral Cl3O coordination sphere, being linked to the tpena ligand through a single coordinate bond to O2. The carboxylate group acts as an anti-1,3-bridge between the two ZnII ions. The pyridine groups in the N4 plane link the molecules into π-stacked columns generated by symmetry operations (-x+1, -y+1, -z+1) and (-x+2, -y+1, -z+1) (Fig. 4), though the interacting rings are not parallel.
The asymmetric unit of complex (II) comprises two independent Zn2Br3(tpena) formula units (Fig. 5), each with the same connectivity as described for chloride complex (I). The two independent molecules are linked by π-stacking between the pyridine groups in the N4 planes [centroid–centroid distances = 3.673 (4) and 3.803 (4) Å], but, in contrast to complex (I), the stacking does not extend through the structure. The crystal packing is dominated by a substantal number of C—H······Br hydrogen bonds in the range 3.58–3.94 Å (Table 5) .
In copper complex (III), there are two independent molecular units, as shown in Fig 6. In contrast to complexes (I) and (II), the central ethylenediamine section of the tpena ligand is extended, providing two separate tridentate binding sites, i.e. one N3 and one N2O. In each molecule, one CuII ion (Cu1 or Cu3) is in the N3 site [where the N-atom donors are from the bis(pyridin-2-ylmethyl)amine group at N4 or N9] with two additional bromide ligands. The geometry at these CuII ions is trigonal bipyramidal, with the pyridine donors axial and τ values (Addison et al., 1984) of 0.60 and 0.38 for Cu1 and Cu3, respectively. The second CuII ion in each molecule (Cu2 or Cu4) is bound by the tpena ligand N2O donor set (amine, pyridine and carboxylate) along with a bromide ion. Atom Cu4 is four-coordinate and approaching square planar [the angle between the N—Cu—N and O—Cu—Br planes is 35.05 (16)°], while atom Cu2 has a coordinated water molecule as the fifth ligand and is closest to square pyramidal (τ = 0.29). There is no convincing π-stacking in complex (III), instead the packing is apparently controlled by hydrogen bonding in columns parallel to the a axis, involving the water molecules, the uncoordinated carboxylate O atoms and some of the bromide ions (Table 6 and Fig 7).
All previously published complexes containing tpena have been ionic species with a 1:1 metal–tpena ratio in which the metal ion binds either all six tpena donors in six or seven-coordinated complexes (Vad et al., 2011; Lennartson & McKenzie, 2012; de Sousa et al., 2015) or releases one pyridine donor to bind an exogenous ligand (Vad et al., 2012; Lennartson & McKenzie, 2012; de Sousa et al., 2015). Carboxylate bridging to another metal ion has also been observed previously in related systems, but in those cases the link has resulted in polynuclear manganese(II) ionic assemblies with all the metal ions in similar environments (Berggren et al., 2009; Egdal et al., 2011). The presence of halides and less oxophilic metal ions has driven the formation of halide complexes and different phases. In the current complexes, the 2:1 metal–tpena stoichiometry and availability of relatively strongly coordinating halide anions provide the conditions required for the isolation of neutral dinuclear compounds. In zinc complexes (I) and (II), tpena acts as a hexadentate ligand and the encapsulated metal binding site is essentially the same as that previously reported for the mononuclear CoIII and CrIII complexes (Vad et al., 2011; de Sousa et al., 2015). The tetrahedral OX3 coordination of the second zinc ion is quite common (Cambridge Structural Database, Version 5.36; Groom & Allen, 2014). A few examples of M–(OCO)–ZnCl3 linkages involving pendant carboxylate groups are known (Panneerselvam, Lu, Chi, Liao & Chung, 2000; Panneerselvam, Lu, Chi, Tung & Chung, 2000; Barfod et al., 2005) and their geometry is similar to that of complex (I); no bromide analogs of (II) were found.
The structure of (III) is unexpected and is perhaps a consequence of the preference of copper(II) for pentacoordination and the difficulty of accommodating a Jahn–Teller ion in the N5O site. The structure might suggest that the incorporation of stiffening backbones could be advisable when designing catalysts based on ligands of this type if reactivity is dependent on catalytically competent mononuclear metal species.
The separation and purification of polypyridyl ligands, typically from reactions between amines and alkyl halides, in pure forms is often difficult. Sticky brown oils not amenable to chromatography or distillation, containing related ligands, are the standard products. With the introduction of carboxylate groups this problem is only exacerbated since their zwitterionic character introduces considerable separation and purification issues in work up. The isolation and characterisation of Zn2(tpena)Cl3 has opened up for a significant improved methodology for the preparation of the pro-catalyst iron complex, [FeIII2(µ-O)(tpenaH)2](ClO4)4 (Lennartson & McKenzie, 2012). If zinc chloride is used in the final stage of ligand synthesis, Zn2(tpena)Cl3 can be isolated directly from dirty reaction mixtures without prior separation of the tpenaH. A subsequent metathesis reaction in water with the more oxophilic iron(III) results in the clean conversion to [FeIII2(µ-O)(tpenaH)2](ClO4)4 (Fig 8). Zinc-doped products can be an issue reactions like this; however, this is not in this case here due to the inherent and metal-specific structural differences; specifically the requirement of an oxide-bridging group for the diiron(III) complex. It is an elegant metathesis reaction since zinc can simply not form the same oxide-bridged structures as iron. Crystallization is a key however; precipitations will yield a powder containing both [FeIII2(µ-O)(tpenaH)2](ClO4)4 and Zn2(tpena)Cl3 as conveniently checked by ESI mass spectrometry. However, if these precipitates are allowed to stand in their mother liquor, over a few days all the metathesis is completed and large crystals of [FeIII2(µ-O)(tpenaH)2](ClO4)4 are easily recovered.
Polypyridyl multidentate ligands based on ethylenediamine backbones are an important class of metal-binding agent with particular applications in biomimetics and homogenous catalysis. We have introduced derivatives of this class of ligand which incorporate a single amino acid group and employed them to prepare model complexes for redox-active nonheme sites in metalloenzymes. Functional biomimetic and catalytic reactivity, for example, in the activation of O2 and H2O has been demonstrated (Poulsen et al. 2005; Nielsen et al. 2006; Vad et al., 2011, 2012; Lennartson & McKenzie, 2012; de Sousa et al., 2015; Deville et al., 2015). Dangling pyridines and the carboxylate groups are proposed to assist in proton transfer and the carboxylate group can be either terminal or bridge between metal ions to form oligomers and polymers (Berggren et al., 2009; Egdal et al., 2011). The latter has proved to be an advantage for achieving stability of MnII complexes towards air oxidation. If bridging does not occur, noncoordinated carboxyl O atoms are usually involved in hydrogen bonding in the solid-state structures and these interactions may be important for solution state reactivity for example in proton transfers (Vad et al., 2012).
The structures of the redox-stable copper(II) and zinc(II) complexes of the ligand N,N,N'-tris(pyridin-2-ylmethyl)ethylenediamine-N'-acetate (tpena-) reported below are important for predicting the structures of more reactive redox-active systems of earlier transition metal ions. They reveal two new structural prototypes, albeit with identical stoichiometry, thereby illustrating the coordinative flexibility of this ligand (see Scheme).
The copper and zinc halides of tpena are prepared easily by direct reaction of the metal salts with Na(tpena) in methanol. Regardless of reaction stoichiometry, i.e. a 1:1 or a 1:2 ligand–metal salt reaction, elemental (CHN) analyses suggested that we had not obtained the desired complexes [M(tpena)]X (M = Cu2+ or Zn2+ and X = Br- or Cl-); where tpena acted as a straightforward hexadentate ligand for a six-coordinated metal ion. The elemental analyses data suggested that the three compounds all have the same tpena–M–Cl 1:2:3 stoichiometry, while at first sight confusingly ESI mass spectra recorded in acetonitrile, however, showed simple [M(tpena)]+ at m/z 454.121 and 453.119 as the only ion, or a major ion, for the zinc and copper complexes, respectively (Fig. 1). The presence of a dominant [M(tpena)]+ ion in these spectra was entirely comparable to the spectra for the simple CrIII and CoIII salts containing the [M(tpena)]+ cation (Vad et al., 2011; de Sousa et al., 2015).
Thus, the usual characterization methods gave no indication of the significant structural differences between the copper and zinc complexes that we have found in the solid state. However, close (and retrospective) inspection of IR spectra reveal small differences in the νas(OCO) carbonyl stretches just above 1600 cm-1 . With the hindsight from the crystal structures these are indicative of the anti-µ-OCO arrangement of the bridging carboxylate donor in the zinc complexes and the monodendate terminal carboxylate in the copper complex. Further, the ESI mass spectrum of the copper complex indicates that this complex is more easily fragmented. A prominent daughter ion at m/z 317.080 is due to decarboxylation and loss of a methylpyridyl arm. A proposed structure for the daughter ion is given in Fig. 2.
The complexes crystallized as Zn2(tpena)Cl3, (I), Zn2Br3(tpena), (II), and [Cu2Br3(tpena)][Cu2Br3(tpena)(H2O)].6.5H2O, (III), all containing neutral complex molecules; selected bond length and angle data are presented in Tables 2-4.
The asymmetric unit of complex (I) comprises one Zn2(tpena)Cl3 formula unit (Fig. 3). The Zn1 ion occupies the six-coordinate N5O site with irregular geometry imposed by the five five-membered chelate rings. The second metal ion, Zn2, has an approximately tetrahedral Cl3O coordination sphere, being linked to the tpena ligand through a single coordinate bond to O2. The carboxylate group acts as an anti-1,3-bridge between the two ZnII ions. The pyridine groups in the N4 plane link the molecules into π-stacked columns generated by symmetry operations (-x+1, -y+1, -z+1) and (-x+2, -y+1, -z+1) (Fig. 4), though the interacting rings are not parallel.
The asymmetric unit of complex (II) comprises two independent Zn2Br3(tpena) formula units (Fig. 5), each with the same connectivity as described for chloride complex (I). The two independent molecules are linked by π-stacking between the pyridine groups in the N4 planes [centroid–centroid distances = 3.673 (4) and 3.803 (4) Å], but, in contrast to complex (I), the stacking does not extend through the structure. The crystal packing is dominated by a substantal number of C—H······Br hydrogen bonds in the range 3.58–3.94 Å (Table 5) .
In copper complex (III), there are two independent molecular units, as shown in Fig 6. In contrast to complexes (I) and (II), the central ethylenediamine section of the tpena ligand is extended, providing two separate tridentate binding sites, i.e. one N3 and one N2O. In each molecule, one CuII ion (Cu1 or Cu3) is in the N3 site [where the N-atom donors are from the bis(pyridin-2-ylmethyl)amine group at N4 or N9] with two additional bromide ligands. The geometry at these CuII ions is trigonal bipyramidal, with the pyridine donors axial and τ values (Addison et al., 1984) of 0.60 and 0.38 for Cu1 and Cu3, respectively. The second CuII ion in each molecule (Cu2 or Cu4) is bound by the tpena ligand N2O donor set (amine, pyridine and carboxylate) along with a bromide ion. Atom Cu4 is four-coordinate and approaching square planar [the angle between the N—Cu—N and O—Cu—Br planes is 35.05 (16)°], while atom Cu2 has a coordinated water molecule as the fifth ligand and is closest to square pyramidal (τ = 0.29). There is no convincing π-stacking in complex (III), instead the packing is apparently controlled by hydrogen bonding in columns parallel to the a axis, involving the water molecules, the uncoordinated carboxylate O atoms and some of the bromide ions (Table 6 and Fig 7).
All previously published complexes containing tpena have been ionic species with a 1:1 metal–tpena ratio in which the metal ion binds either all six tpena donors in six or seven-coordinated complexes (Vad et al., 2011; Lennartson & McKenzie, 2012; de Sousa et al., 2015) or releases one pyridine donor to bind an exogenous ligand (Vad et al., 2012; Lennartson & McKenzie, 2012; de Sousa et al., 2015). Carboxylate bridging to another metal ion has also been observed previously in related systems, but in those cases the link has resulted in polynuclear manganese(II) ionic assemblies with all the metal ions in similar environments (Berggren et al., 2009; Egdal et al., 2011). The presence of halides and less oxophilic metal ions has driven the formation of halide complexes and different phases. In the current complexes, the 2:1 metal–tpena stoichiometry and availability of relatively strongly coordinating halide anions provide the conditions required for the isolation of neutral dinuclear compounds. In zinc complexes (I) and (II), tpena acts as a hexadentate ligand and the encapsulated metal binding site is essentially the same as that previously reported for the mononuclear CoIII and CrIII complexes (Vad et al., 2011; de Sousa et al., 2015). The tetrahedral OX3 coordination of the second zinc ion is quite common (Cambridge Structural Database, Version 5.36; Groom & Allen, 2014). A few examples of M–(OCO)–ZnCl3 linkages involving pendant carboxylate groups are known (Panneerselvam, Lu, Chi, Liao & Chung, 2000; Panneerselvam, Lu, Chi, Tung & Chung, 2000; Barfod et al., 2005) and their geometry is similar to that of complex (I); no bromide analogs of (II) were found.
The structure of (III) is unexpected and is perhaps a consequence of the preference of copper(II) for pentacoordination and the difficulty of accommodating a Jahn–Teller ion in the N5O site. The structure might suggest that the incorporation of stiffening backbones could be advisable when designing catalysts based on ligands of this type if reactivity is dependent on catalytically competent mononuclear metal species.
The separation and purification of polypyridyl ligands, typically from reactions between amines and alkyl halides, in pure forms is often difficult. Sticky brown oils not amenable to chromatography or distillation, containing related ligands, are the standard products. With the introduction of carboxylate groups this problem is only exacerbated since their zwitterionic character introduces considerable separation and purification issues in work up. The isolation and characterisation of Zn2(tpena)Cl3 has opened up for a significant improved methodology for the preparation of the pro-catalyst iron complex, [FeIII2(µ-O)(tpenaH)2](ClO4)4 (Lennartson & McKenzie, 2012). If zinc chloride is used in the final stage of ligand synthesis, Zn2(tpena)Cl3 can be isolated directly from dirty reaction mixtures without prior separation of the tpenaH. A subsequent metathesis reaction in water with the more oxophilic iron(III) results in the clean conversion to [FeIII2(µ-O)(tpenaH)2](ClO4)4 (Fig 8). Zinc-doped products can be an issue reactions like this; however, this is not in this case here due to the inherent and metal-specific structural differences; specifically the requirement of an oxide-bridging group for the diiron(III) complex. It is an elegant metathesis reaction since zinc can simply not form the same oxide-bridged structures as iron. Crystallization is a key however; precipitations will yield a powder containing both [FeIII2(µ-O)(tpenaH)2](ClO4)4 and Zn2(tpena)Cl3 as conveniently checked by ESI mass spectrometry. However, if these precipitates are allowed to stand in their mother liquor, over a few days all the metathesis is completed and large crystals of [FeIII2(µ-O)(tpenaH)2](ClO4)4 are easily recovered.
The copper and zinc halide complexes of N,N,N'-tris(pyridin-2-ylmethyl)ethylenediamine-N'-acetate (tpena-) were prepared by mixing an aqueous solution (1 ml) of Na(tpena)(CH3CH2OH) (0.048 mmol) (Vad et al., 2011) with two equivalents of the appropriate dibromide or dichloride (0.097 mmol) dissolved in MeOH (2 ml). Upon slow evaporation of the solvent, either colourless crystals of the zinc or turquoise crystals of the copper complexes formed over a period of several days. These were isolated by filtration and washed with cold H2O (yields 70–90%). IR (KBr disc): Zn2(tpena)Cl3, νas(COO) = 1602 cm-1. Zn2(tpena)Br3 νas(COO) = 1605 cm-1. Cu2(tpena)Cl3 νas(COO) = 1611 cm-1.
ESI–MS (CH3CN, 10-6 M); [Zn(tpena)]+ m/z 454.121 (calculated: 454.122, C22H24N5O2Zn) appears in the spectrum of both the chloride and the bromide zinc species. Two peaks are seen for the copper species one for the isostoichiometric [Cu(tpena)]+ at m/z 453.119 (453.133, C22H24CuN5O2) and an additional signal for [Cu(tpena-CH2COO-CH2Py)]+ m/z 317.080 (317.083, C15H18CuN4), for which no analog was observed in the spectra of the zinc complexes.
Analysis calculated for Zn2(tpena)Cl3 found (calculated) C22H24Cl3N5O2Zn2: C 41.89 (42.11), H 3.76 (3.85), N 10.91 (11.16). For Zn2(tpena)Br3 found (calculated.) C22H24Br3N5O2Zn2: C 35.26 (34.73), H 3.09 (3.18), N 9.19 (9.20). [Cu2(tpena)Br3][Cu2(tpena)Br3(H2O)]·6.5H2O, which has overall formula Cu2(tpena)Br3(H2O)3.75, analysed as Cu2(tpena)Br3(H2O)2, indicating some loss of water solvate during drying; found (calculated) C22H28Br3Cu2N5O4: C 33.58 (33.30), H 3.28 (3.55), N 8.72 (8.83).
Crystal data, data collection and structure refinement details for Zn2(tpena)Cl3, (I), Zn2(tpena)Br3, (II), and [Cu2(tpena)Br3][Cu2(tpena)Br3(H2O)].6.5H2O, (III), are summarized in Table 1. Complex (II) was refined as a racemic twin with a Flack parameter of 0.244 (13) (Flack, 1983). Complex (III) was found to be twinned by rotation of 180° about reciprocal axis [001]. The data were processed as a two-component twin using TWINABS (Sheldrick, 2012) and refined using a HKLF 5 data set constructed from all observations involving domain 1 [BASF = 0.4366 (8)]. In each structure, all H atoms bonded to C atoms were added in calculated positions, with C—H = 0.99 (CH2) or 0.95 Å (aromatic) and Uiso(H) = 1.2Ueq(C). Complex (III) contains hydrogen-bonded water molecules. Most of the H atoms were not evident in difference maps but the water O atoms are within hydrogen bonding-distance of each other. Attempts to develop a self-consistent model starting from the acceptors (carbonyls and bromides) that could not be hydrogen-bond donors were only partially successful, suggesting at least some of the H-atom sites may be disordered. These H atoms were not included in the model. One of the water molecules (O12) is disordered about a centre of symmetry and was refined with 50% occupancy.
Data collection: APEX2 (Bruker, 2012) for II_vcm14089, III_vCM14087twin5. For all compounds, cell refinement: APEX2 (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Bruker, 2012) and Mercury (Macrae et al., 2006). Software used to prepare material for publication: SHELXTL (Bruker, 2012) and publCIF (Westrip, 2010) for I_vCM14088; publCIF (Westrip, 2010) for II_vcm14089, III_vCM14087twin5.
[Zn2(C22H24N5O2)Cl3] | F(000) = 1272 |
Mr = 627.55 | Dx = 1.673 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4985 (8) Å | Cell parameters from 9964 reflections |
b = 11.3423 (10) Å | θ = 2.5–26.0° |
c = 23.3697 (18) Å | µ = 2.28 mm−1 |
β = 98.263 (4)° | T = 180 K |
V = 2491.6 (4) Å3 | Rhomb, colourless |
Z = 4 | 0.31 × 0.19 × 0.15 mm |
Bruker–Nonius X8 APEXII CCD diffractometer | 5051 independent reflections |
Radiation source: fine-focus sealed-tube | 4340 reflections with I > 2σ(I) |
Detector resolution: 9.1 pixels mm-1 | Rint = 0.084 |
thin–slice ω and φ scans | θmax = 26.5°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −11→11 |
Tmin = 0.469, Tmax = 0.745 | k = −14→13 |
77315 measured reflections | l = −29→29 |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Secondary atom site location: dual |
R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0406P)2 + 4.0296P] where P = (Fo2 + 2Fc2)/3 |
5051 reflections | (Δ/σ)max = 0.001 |
307 parameters | Δρmax = 0.85 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
[Zn2(C22H24N5O2)Cl3] | V = 2491.6 (4) Å3 |
Mr = 627.55 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.4985 (8) Å | µ = 2.28 mm−1 |
b = 11.3423 (10) Å | T = 180 K |
c = 23.3697 (18) Å | 0.31 × 0.19 × 0.15 mm |
β = 98.263 (4)° |
Bruker–Nonius X8 APEXII CCD diffractometer | 5051 independent reflections |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | 4340 reflections with I > 2σ(I) |
Tmin = 0.469, Tmax = 0.745 | Rint = 0.084 |
77315 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.14 | Δρmax = 0.85 e Å−3 |
5051 reflections | Δρmin = −0.48 e Å−3 |
307 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.66652 (4) | 0.59825 (3) | 0.60251 (2) | 0.02094 (11) | |
Zn2 | 0.30820 (4) | 0.23885 (3) | 0.63634 (2) | 0.02351 (12) | |
Cl1 | 0.14357 (10) | 0.19496 (9) | 0.69401 (4) | 0.0385 (2) | |
Cl2 | 0.52626 (9) | 0.16828 (9) | 0.66938 (4) | 0.0345 (2) | |
Cl3 | 0.22696 (9) | 0.18402 (8) | 0.54590 (4) | 0.0324 (2) | |
N1 | 0.8417 (3) | 0.7254 (3) | 0.62309 (12) | 0.0279 (6) | |
C1 | 0.8453 (4) | 0.8372 (3) | 0.60389 (16) | 0.0345 (8) | |
H1 | 0.7708 | 0.8637 | 0.5753 | 0.041* | |
C2 | 0.9529 (5) | 0.9145 (4) | 0.62419 (19) | 0.0465 (11) | |
H2 | 0.9531 | 0.9927 | 0.6096 | 0.056* | |
C3 | 1.0607 (5) | 0.8762 (4) | 0.66625 (19) | 0.0484 (11) | |
H3 | 1.1352 | 0.9282 | 0.6815 | 0.058* | |
C4 | 1.0586 (4) | 0.7627 (4) | 0.68558 (17) | 0.0382 (9) | |
H4 | 1.1319 | 0.7347 | 0.7143 | 0.046* | |
C5 | 0.9481 (4) | 0.6887 (3) | 0.66285 (14) | 0.0283 (8) | |
C6 | 0.9470 (4) | 0.5620 (3) | 0.68158 (14) | 0.0280 (7) | |
H6A | 1.0138 | 0.5170 | 0.6611 | 0.034* | |
H6B | 0.9825 | 0.5577 | 0.7235 | 0.034* | |
N2 | 0.7699 (3) | 0.4872 (2) | 0.55245 (11) | 0.0205 (6) | |
C7 | 0.7788 (3) | 0.4962 (3) | 0.49628 (13) | 0.0222 (7) | |
H7 | 0.7341 | 0.5612 | 0.4754 | 0.027* | |
C8 | 0.8506 (4) | 0.4148 (3) | 0.46702 (14) | 0.0261 (7) | |
H8 | 0.8532 | 0.4227 | 0.4267 | 0.031* | |
C9 | 0.9181 (4) | 0.3222 (3) | 0.49781 (15) | 0.0290 (8) | |
H9 | 0.9692 | 0.2655 | 0.4791 | 0.035* | |
C10 | 0.9106 (4) | 0.3129 (3) | 0.55629 (15) | 0.0272 (7) | |
H10 | 0.9573 | 0.2500 | 0.5782 | 0.033* | |
C11 | 0.8346 (3) | 0.3959 (3) | 0.58251 (13) | 0.0227 (7) | |
C12 | 0.8161 (4) | 0.3865 (3) | 0.64569 (14) | 0.0255 (7) | |
H12A | 0.7288 | 0.3410 | 0.6493 | 0.031* | |
H12B | 0.8982 | 0.3440 | 0.6672 | 0.031* | |
N3 | 0.5252 (3) | 0.7228 (2) | 0.56335 (11) | 0.0237 (6) | |
C13 | 0.4827 (4) | 0.7363 (3) | 0.50673 (14) | 0.0245 (7) | |
H13 | 0.5119 | 0.6799 | 0.4808 | 0.029* | |
C14 | 0.3984 (4) | 0.8289 (3) | 0.48440 (16) | 0.0318 (8) | |
H14 | 0.3717 | 0.8375 | 0.4439 | 0.038* | |
C15 | 0.3537 (4) | 0.9086 (3) | 0.52233 (17) | 0.0383 (9) | |
H15 | 0.2954 | 0.9734 | 0.5083 | 0.046* | |
C16 | 0.3944 (4) | 0.8937 (3) | 0.58117 (16) | 0.0344 (8) | |
H16 | 0.3628 | 0.9474 | 0.6078 | 0.041* | |
C17 | 0.4803 (4) | 0.8010 (3) | 0.60065 (15) | 0.0273 (7) | |
C18 | 0.5345 (4) | 0.7817 (3) | 0.66431 (14) | 0.0285 (8) | |
H18A | 0.6236 | 0.8267 | 0.6753 | 0.034* | |
H18B | 0.4632 | 0.8106 | 0.6880 | 0.034* | |
N4 | 0.8056 (3) | 0.5049 (2) | 0.67066 (11) | 0.0227 (6) | |
C19 | 0.7306 (4) | 0.5083 (3) | 0.72180 (13) | 0.0262 (7) | |
H19A | 0.7987 | 0.4909 | 0.7570 | 0.031* | |
H19B | 0.6556 | 0.4470 | 0.7180 | 0.031* | |
C20 | 0.6636 (4) | 0.6291 (3) | 0.72779 (13) | 0.0261 (7) | |
H20A | 0.6140 | 0.6299 | 0.7623 | 0.031* | |
H20B | 0.7388 | 0.6902 | 0.7330 | 0.031* | |
N5 | 0.5612 (3) | 0.6555 (2) | 0.67545 (11) | 0.0232 (6) | |
C21 | 0.4267 (4) | 0.5897 (3) | 0.67386 (14) | 0.0256 (7) | |
H21A | 0.3469 | 0.6421 | 0.6584 | 0.031* | |
H21B | 0.4142 | 0.5685 | 0.7139 | 0.031* | |
C22 | 0.4185 (3) | 0.4788 (3) | 0.63779 (13) | 0.0221 (7) | |
O1 | 0.5077 (2) | 0.4605 (2) | 0.60434 (9) | 0.0226 (5) | |
O2 | 0.3147 (3) | 0.4129 (2) | 0.64417 (10) | 0.0296 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0241 (2) | 0.0201 (2) | 0.01841 (18) | 0.00186 (15) | 0.00241 (14) | −0.00207 (14) |
Zn2 | 0.0262 (2) | 0.0227 (2) | 0.02098 (19) | −0.00089 (16) | 0.00127 (14) | 0.00260 (14) |
Cl1 | 0.0316 (5) | 0.0514 (6) | 0.0328 (5) | −0.0075 (4) | 0.0055 (4) | 0.0157 (4) |
Cl2 | 0.0292 (5) | 0.0429 (5) | 0.0292 (4) | 0.0040 (4) | −0.0037 (3) | 0.0089 (4) |
Cl3 | 0.0313 (5) | 0.0362 (5) | 0.0272 (4) | 0.0111 (4) | −0.0037 (3) | −0.0084 (3) |
N1 | 0.0342 (17) | 0.0266 (16) | 0.0237 (14) | −0.0046 (13) | 0.0071 (12) | −0.0033 (11) |
C1 | 0.043 (2) | 0.028 (2) | 0.0338 (19) | −0.0038 (17) | 0.0086 (16) | −0.0009 (15) |
C2 | 0.059 (3) | 0.030 (2) | 0.052 (3) | −0.013 (2) | 0.015 (2) | −0.0004 (18) |
C3 | 0.043 (2) | 0.048 (3) | 0.054 (3) | −0.018 (2) | 0.008 (2) | −0.011 (2) |
C4 | 0.032 (2) | 0.047 (3) | 0.035 (2) | −0.0099 (18) | 0.0024 (16) | −0.0059 (17) |
C5 | 0.0273 (18) | 0.034 (2) | 0.0251 (17) | −0.0026 (15) | 0.0095 (13) | −0.0049 (14) |
C6 | 0.0231 (17) | 0.037 (2) | 0.0238 (16) | −0.0012 (15) | 0.0020 (13) | −0.0026 (14) |
N2 | 0.0208 (14) | 0.0188 (14) | 0.0215 (13) | −0.0005 (11) | 0.0024 (10) | −0.0006 (10) |
C7 | 0.0205 (16) | 0.0241 (17) | 0.0214 (15) | −0.0015 (13) | 0.0004 (12) | 0.0000 (12) |
C8 | 0.0233 (17) | 0.034 (2) | 0.0208 (15) | −0.0014 (15) | 0.0036 (12) | −0.0045 (13) |
C9 | 0.0252 (18) | 0.030 (2) | 0.0318 (18) | 0.0069 (15) | 0.0052 (14) | −0.0071 (14) |
C10 | 0.0250 (18) | 0.0248 (18) | 0.0309 (18) | 0.0046 (14) | 0.0006 (13) | 0.0008 (14) |
C11 | 0.0200 (16) | 0.0246 (17) | 0.0231 (15) | −0.0026 (14) | 0.0018 (12) | −0.0007 (13) |
C12 | 0.0264 (18) | 0.0251 (18) | 0.0246 (16) | 0.0048 (14) | 0.0027 (13) | 0.0024 (13) |
N3 | 0.0272 (15) | 0.0199 (14) | 0.0236 (14) | −0.0001 (12) | 0.0026 (11) | −0.0031 (11) |
C13 | 0.0267 (18) | 0.0221 (17) | 0.0243 (16) | −0.0005 (14) | 0.0027 (13) | −0.0002 (13) |
C14 | 0.034 (2) | 0.029 (2) | 0.0315 (18) | −0.0011 (16) | 0.0008 (14) | 0.0031 (15) |
C15 | 0.047 (2) | 0.024 (2) | 0.044 (2) | 0.0087 (17) | 0.0020 (17) | 0.0049 (16) |
C16 | 0.043 (2) | 0.0213 (19) | 0.041 (2) | 0.0065 (16) | 0.0109 (16) | −0.0052 (15) |
C17 | 0.0309 (19) | 0.0211 (18) | 0.0298 (18) | −0.0025 (15) | 0.0046 (14) | −0.0052 (13) |
C18 | 0.035 (2) | 0.0234 (18) | 0.0274 (17) | −0.0002 (15) | 0.0052 (14) | −0.0073 (13) |
N4 | 0.0238 (15) | 0.0250 (15) | 0.0190 (12) | 0.0004 (12) | 0.0021 (10) | −0.0021 (10) |
C19 | 0.0258 (18) | 0.0317 (19) | 0.0207 (15) | 0.0017 (15) | 0.0016 (12) | 0.0019 (13) |
C20 | 0.0252 (18) | 0.034 (2) | 0.0192 (15) | −0.0028 (15) | 0.0034 (12) | −0.0044 (13) |
N5 | 0.0247 (14) | 0.0223 (15) | 0.0226 (13) | −0.0007 (12) | 0.0032 (11) | −0.0042 (11) |
C21 | 0.0251 (18) | 0.0268 (18) | 0.0259 (16) | −0.0014 (14) | 0.0066 (13) | −0.0057 (13) |
C22 | 0.0259 (18) | 0.0206 (17) | 0.0187 (15) | 0.0024 (14) | −0.0007 (12) | 0.0015 (12) |
O1 | 0.0256 (12) | 0.0200 (12) | 0.0227 (11) | −0.0004 (10) | 0.0049 (9) | −0.0037 (9) |
O2 | 0.0286 (14) | 0.0234 (13) | 0.0385 (14) | −0.0031 (11) | 0.0107 (10) | −0.0035 (10) |
Zn1—N1 | 2.203 (3) | C10—H10 | 0.9500 |
Zn1—N2 | 2.061 (3) | C11—C12 | 1.516 (4) |
Zn1—N3 | 2.069 (3) | C12—N4 | 1.473 (4) |
Zn1—O1 | 2.177 (2) | C12—H12A | 0.9900 |
Zn1—N4 | 2.190 (3) | C12—H12B | 0.9900 |
Zn1—N5 | 2.195 (3) | N3—C13 | 1.336 (4) |
Zn2—O2 | 1.982 (2) | N3—C17 | 1.355 (4) |
Zn2—Cl1 | 2.2618 (10) | C13—C14 | 1.377 (5) |
Zn2—Cl2 | 2.2511 (9) | C13—H13 | 0.9500 |
Zn2—Cl3 | 2.2317 (9) | C14—C15 | 1.375 (5) |
N1—C5 | 1.338 (5) | C14—H14 | 0.9500 |
N1—C1 | 1.346 (5) | C15—C16 | 1.384 (5) |
C1—C2 | 1.379 (6) | C15—H15 | 0.9500 |
C1—H1 | 0.9500 | C16—C17 | 1.368 (5) |
C2—C3 | 1.383 (6) | C16—H16 | 0.9500 |
C2—H2 | 0.9500 | C17—C18 | 1.518 (5) |
C3—C4 | 1.366 (6) | C18—N5 | 1.470 (4) |
C3—H3 | 0.9500 | C18—H18A | 0.9900 |
C4—C5 | 1.388 (5) | C18—H18B | 0.9900 |
C4—H4 | 0.9500 | N4—C19 | 1.477 (4) |
C5—C6 | 1.502 (5) | C19—C20 | 1.526 (5) |
C6—N4 | 1.480 (4) | C19—H19A | 0.9900 |
C6—H6A | 0.9900 | C19—H19B | 0.9900 |
C6—H6B | 0.9900 | C20—N5 | 1.480 (4) |
N2—C7 | 1.331 (4) | C20—H20A | 0.9900 |
N2—C11 | 1.349 (4) | C20—H20B | 0.9900 |
C7—C8 | 1.385 (5) | N5—C21 | 1.475 (4) |
C7—H7 | 0.9500 | C21—C22 | 1.511 (4) |
C8—C9 | 1.378 (5) | C21—H21A | 0.9900 |
C8—H8 | 0.9500 | C21—H21B | 0.9900 |
C9—C10 | 1.383 (5) | C22—O1 | 1.250 (4) |
C9—H9 | 0.9500 | C22—O2 | 1.263 (4) |
C10—C11 | 1.382 (5) | ||
N2—Zn1—N3 | 119.85 (10) | N4—C12—H12A | 109.6 |
N2—Zn1—O1 | 87.74 (9) | C11—C12—H12A | 109.6 |
N3—Zn1—O1 | 95.22 (10) | N4—C12—H12B | 109.6 |
N2—Zn1—N4 | 80.25 (10) | C11—C12—H12B | 109.6 |
N3—Zn1—N4 | 159.51 (10) | H12A—C12—H12B | 108.1 |
O1—Zn1—N4 | 89.19 (9) | C13—N3—C17 | 118.9 (3) |
N2—Zn1—N5 | 158.26 (11) | C13—N3—Zn1 | 127.0 (2) |
N3—Zn1—N5 | 78.60 (10) | C17—N3—Zn1 | 114.0 (2) |
O1—Zn1—N5 | 78.60 (9) | N3—C13—C14 | 122.7 (3) |
N4—Zn1—N5 | 82.70 (10) | N3—C13—H13 | 118.7 |
N2—Zn1—N1 | 96.75 (11) | C14—C13—H13 | 118.7 |
N3—Zn1—N1 | 94.10 (11) | C15—C14—C13 | 118.3 (3) |
O1—Zn1—N1 | 165.91 (9) | C15—C14—H14 | 120.9 |
N4—Zn1—N1 | 78.48 (11) | C13—C14—H14 | 120.9 |
N5—Zn1—N1 | 92.94 (10) | C14—C15—C16 | 119.5 (3) |
O2—Zn2—Cl3 | 111.52 (8) | C14—C15—H15 | 120.3 |
O2—Zn2—Cl2 | 107.91 (8) | C16—C15—H15 | 120.3 |
Cl3—Zn2—Cl2 | 113.68 (4) | C17—C16—C15 | 119.5 (3) |
O2—Zn2—Cl1 | 100.32 (8) | C17—C16—H16 | 120.3 |
Cl3—Zn2—Cl1 | 109.17 (4) | C15—C16—H16 | 120.3 |
Cl2—Zn2—Cl1 | 113.46 (4) | N3—C17—C16 | 121.1 (3) |
C5—N1—C1 | 118.2 (3) | N3—C17—C18 | 116.2 (3) |
C5—N1—Zn1 | 114.8 (2) | C16—C17—C18 | 122.6 (3) |
C1—N1—Zn1 | 126.7 (3) | N5—C18—C17 | 109.8 (3) |
N1—C1—C2 | 122.5 (4) | N5—C18—H18A | 109.7 |
N1—C1—H1 | 118.7 | C17—C18—H18A | 109.7 |
C2—C1—H1 | 118.7 | N5—C18—H18B | 109.7 |
C1—C2—C3 | 118.7 (4) | C17—C18—H18B | 109.7 |
C1—C2—H2 | 120.6 | H18A—C18—H18B | 108.2 |
C3—C2—H2 | 120.6 | C12—N4—C19 | 114.3 (3) |
C4—C3—C2 | 119.1 (4) | C12—N4—C6 | 110.8 (3) |
C4—C3—H3 | 120.4 | C19—N4—C6 | 112.3 (2) |
C2—C3—H3 | 120.4 | C12—N4—Zn1 | 102.76 (18) |
C3—C4—C5 | 119.3 (4) | C19—N4—Zn1 | 105.39 (19) |
C3—C4—H4 | 120.3 | C6—N4—Zn1 | 110.6 (2) |
C5—C4—H4 | 120.3 | N4—C19—C20 | 110.7 (3) |
N1—C5—C4 | 122.1 (4) | N4—C19—H19A | 109.5 |
N1—C5—C6 | 117.7 (3) | C20—C19—H19A | 109.5 |
C4—C5—C6 | 120.2 (3) | N4—C19—H19B | 109.5 |
N4—C6—C5 | 114.4 (3) | C20—C19—H19B | 109.5 |
N4—C6—H6A | 108.7 | H19A—C19—H19B | 108.1 |
C5—C6—H6A | 108.7 | N5—C20—C19 | 109.8 (3) |
N4—C6—H6B | 108.7 | N5—C20—H20A | 109.7 |
C5—C6—H6B | 108.7 | C19—C20—H20A | 109.7 |
H6A—C6—H6B | 107.6 | N5—C20—H20B | 109.7 |
C7—N2—C11 | 118.9 (3) | C19—C20—H20B | 109.7 |
C7—N2—Zn1 | 128.0 (2) | H20A—C20—H20B | 108.2 |
C11—N2—Zn1 | 113.1 (2) | C18—N5—C21 | 111.2 (3) |
N2—C7—C8 | 122.8 (3) | C18—N5—C20 | 114.8 (3) |
N2—C7—H7 | 118.6 | C21—N5—C20 | 112.5 (3) |
C8—C7—H7 | 118.6 | C18—N5—Zn1 | 103.7 (2) |
C9—C8—C7 | 118.4 (3) | C21—N5—Zn1 | 108.71 (19) |
C9—C8—H8 | 120.8 | C20—N5—Zn1 | 105.24 (19) |
C7—C8—H8 | 120.8 | N5—C21—C22 | 114.2 (3) |
C8—C9—C10 | 119.2 (3) | N5—C21—H21A | 108.7 |
C8—C9—H9 | 120.4 | C22—C21—H21A | 108.7 |
C10—C9—H9 | 120.4 | N5—C21—H21B | 108.7 |
C11—C10—C9 | 119.3 (3) | C22—C21—H21B | 108.7 |
C11—C10—H10 | 120.3 | H21A—C21—H21B | 107.6 |
C9—C10—H10 | 120.3 | O1—C22—O2 | 125.9 (3) |
N2—C11—C10 | 121.4 (3) | O1—C22—C21 | 120.1 (3) |
N2—C11—C12 | 117.0 (3) | O2—C22—C21 | 113.9 (3) |
C10—C11—C12 | 121.7 (3) | C22—O1—Zn1 | 115.3 (2) |
N4—C12—C11 | 110.2 (3) | C22—O2—Zn2 | 126.4 (2) |
[Zn2Br3(C22H24N5O2)] | Dx = 1.982 Mg m−3 |
Mr = 760.93 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pca21 | Cell parameters from 9941 reflections |
a = 18.7061 (12) Å | θ = 2.7–23.0° |
b = 13.3342 (9) Å | µ = 6.61 mm−1 |
c = 20.4516 (13) Å | T = 180 K |
V = 5101.3 (6) Å3 | Block, colourless |
Z = 8 | 0.17 × 0.08 × 0.05 mm |
F(000) = 2976 |
Bruker–Nonius X8 APEXII CCD diffractometer | 11284 independent reflections |
Radiation source: fine-focus sealed-tube | 8558 reflections with I > 2σ(I) |
Detector resolution: 9.1 pixels mm-1 | Rint = 0.081 |
thin–slice ω and φ scans | θmax = 28.4°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −24→23 |
Tmin = 0.365, Tmax = 0.431 | k = −17→17 |
127653 measured reflections | l = −26→25 |
Refinement on F2 | Secondary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.078 | w = 1/[σ2(Fo2) + (0.0394P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
11284 reflections | Δρmax = 1.26 e Å−3 |
614 parameters | Δρmin = −0.61 e Å−3 |
1 restraint | Absolute structure: Refined as an inversion twin. |
Primary atom site location: dual | Absolute structure parameter: 0.245 (12) |
[Zn2Br3(C22H24N5O2)] | V = 5101.3 (6) Å3 |
Mr = 760.93 | Z = 8 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 18.7061 (12) Å | µ = 6.61 mm−1 |
b = 13.3342 (9) Å | T = 180 K |
c = 20.4516 (13) Å | 0.17 × 0.08 × 0.05 mm |
Bruker–Nonius X8 APEXII CCD diffractometer | 11284 independent reflections |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | 8558 reflections with I > 2σ(I) |
Tmin = 0.365, Tmax = 0.431 | Rint = 0.081 |
127653 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.078 | Δρmax = 1.26 e Å−3 |
S = 1.02 | Δρmin = −0.61 e Å−3 |
11284 reflections | Absolute structure: Refined as an inversion twin. |
614 parameters | Absolute structure parameter: 0.245 (12) |
1 restraint |
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. |
Refinement. Refined as a 2-component inversion twin. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.51652 (5) | 0.85593 (6) | 0.52058 (4) | 0.0149 (2) | |
Zn2 | 0.32893 (5) | 1.05847 (6) | 0.35826 (4) | 0.0168 (2) | |
Br1 | 0.43284 (5) | 1.02792 (8) | 0.29484 (5) | 0.0322 (2) | |
Br2 | 0.29001 (5) | 1.22925 (6) | 0.35104 (5) | 0.0332 (2) | |
Br3 | 0.23405 (5) | 0.94323 (7) | 0.33985 (5) | 0.0339 (2) | |
N1 | 0.6162 (3) | 0.8210 (5) | 0.5730 (3) | 0.0176 (16) | |
C1 | 0.6226 (5) | 0.7788 (6) | 0.6332 (4) | 0.023 (2) | |
H1 | 0.5806 | 0.7669 | 0.6581 | 0.028* | |
C2 | 0.6875 (5) | 0.7527 (6) | 0.6592 (5) | 0.030 (2) | |
H2 | 0.6906 | 0.7239 | 0.7016 | 0.035* | |
C3 | 0.7479 (5) | 0.7692 (6) | 0.6225 (5) | 0.031 (2) | |
H3 | 0.7934 | 0.7507 | 0.6392 | 0.037* | |
C4 | 0.7427 (5) | 0.8121 (6) | 0.5619 (5) | 0.022 (2) | |
H4 | 0.7842 | 0.8228 | 0.5361 | 0.027* | |
C5 | 0.6757 (4) | 0.8399 (5) | 0.5388 (4) | 0.0176 (18) | |
C6 | 0.6692 (4) | 0.8887 (6) | 0.4726 (4) | 0.0195 (19) | |
H6A | 0.7013 | 0.9477 | 0.4713 | 0.023* | |
H6B | 0.6861 | 0.8407 | 0.4391 | 0.023* | |
N2 | 0.5234 (3) | 0.7410 (5) | 0.4511 (3) | 0.0161 (15) | |
C7 | 0.5005 (4) | 0.6454 (6) | 0.4554 (4) | 0.0161 (18) | |
H7 | 0.4769 | 0.6244 | 0.4942 | 0.019* | |
C8 | 0.5101 (4) | 0.5766 (6) | 0.4052 (4) | 0.022 (2) | |
H8 | 0.4927 | 0.5100 | 0.4093 | 0.026* | |
C9 | 0.5451 (5) | 0.6062 (6) | 0.3494 (5) | 0.028 (2) | |
H9 | 0.5518 | 0.5606 | 0.3142 | 0.033* | |
C10 | 0.5704 (4) | 0.7030 (6) | 0.3452 (5) | 0.022 (2) | |
H10 | 0.5965 | 0.7239 | 0.3078 | 0.027* | |
C11 | 0.5575 (4) | 0.7694 (6) | 0.3956 (4) | 0.0173 (18) | |
C12 | 0.5759 (4) | 0.8801 (6) | 0.3901 (4) | 0.0192 (18) | |
H12A | 0.6163 | 0.8888 | 0.3594 | 0.023* | |
H12B | 0.5343 | 0.9172 | 0.3725 | 0.023* | |
N3 | 0.4549 (3) | 0.8323 (5) | 0.6038 (3) | 0.0148 (14) | |
C13 | 0.4144 (4) | 0.7523 (6) | 0.6177 (4) | 0.022 (2) | |
H13 | 0.4148 | 0.6969 | 0.5884 | 0.027* | |
C14 | 0.3721 (4) | 0.7470 (6) | 0.6726 (4) | 0.023 (2) | |
H14 | 0.3453 | 0.6882 | 0.6821 | 0.027* | |
C15 | 0.3696 (4) | 0.8285 (6) | 0.7133 (4) | 0.0218 (19) | |
H15 | 0.3393 | 0.8277 | 0.7505 | 0.026* | |
C16 | 0.4112 (5) | 0.9126 (6) | 0.7002 (4) | 0.024 (2) | |
H16 | 0.4095 | 0.9695 | 0.7281 | 0.029* | |
C17 | 0.4554 (4) | 0.9119 (6) | 0.6457 (4) | 0.0164 (18) | |
C18 | 0.5059 (6) | 0.9957 (6) | 0.6296 (5) | 0.020 (2) | |
H18A | 0.4895 | 1.0584 | 0.6507 | 0.024* | |
H18B | 0.5542 | 0.9797 | 0.6464 | 0.024* | |
N4 | 0.5957 (3) | 0.9218 (5) | 0.4550 (3) | 0.0170 (15) | |
C19 | 0.5845 (5) | 1.0319 (7) | 0.4607 (4) | 0.023 (2) | |
H19A | 0.5423 | 1.0521 | 0.4345 | 0.027* | |
H19B | 0.6268 | 1.0679 | 0.4435 | 0.027* | |
C20 | 0.5727 (4) | 1.0593 (6) | 0.5321 (4) | 0.0217 (19) | |
H20A | 0.6149 | 1.0387 | 0.5581 | 0.026* | |
H20B | 0.5674 | 1.1329 | 0.5362 | 0.026* | |
N5 | 0.5087 (4) | 1.0098 (5) | 0.5578 (4) | 0.0147 (17) | |
C21 | 0.4424 (4) | 1.0583 (6) | 0.5336 (4) | 0.0176 (18) | |
H21A | 0.4543 | 1.1266 | 0.5182 | 0.021* | |
H21B | 0.4086 | 1.0650 | 0.5705 | 0.021* | |
C22 | 0.4051 (5) | 1.0019 (6) | 0.4781 (5) | 0.017 (2) | |
O1 | 0.4279 (3) | 0.9160 (4) | 0.4632 (3) | 0.0194 (13) | |
O2 | 0.3538 (3) | 1.0478 (4) | 0.4532 (3) | 0.0214 (13) | |
Zn3 | 0.23936 (4) | 0.64110 (6) | 0.48274 (4) | 0.0143 (2) | |
Zn4 | 0.42713 (5) | 0.44178 (6) | 0.65074 (4) | 0.0162 (2) | |
Br4 | 0.52339 (4) | 0.54973 (6) | 0.67998 (4) | 0.0257 (2) | |
Br5 | 0.31994 (4) | 0.46711 (7) | 0.71173 (4) | 0.0252 (2) | |
Br6 | 0.46490 (4) | 0.26880 (6) | 0.65729 (4) | 0.0263 (2) | |
N6 | 0.1355 (3) | 0.6728 (5) | 0.4359 (3) | 0.0148 (15) | |
C23 | 0.1242 (5) | 0.7156 (6) | 0.3771 (4) | 0.025 (2) | |
H23 | 0.1642 | 0.7288 | 0.3498 | 0.031* | |
C24 | 0.0579 (5) | 0.7407 (6) | 0.3554 (5) | 0.030 (2) | |
H24 | 0.0522 | 0.7676 | 0.3127 | 0.036* | |
C25 | −0.0018 (5) | 0.7274 (6) | 0.3951 (5) | 0.028 (2) | |
H25 | −0.0480 | 0.7481 | 0.3814 | 0.034* | |
C26 | 0.0092 (5) | 0.6825 (7) | 0.4555 (4) | 0.021 (2) | |
H26 | −0.0298 | 0.6696 | 0.4841 | 0.025* | |
C27 | 0.0783 (4) | 0.6569 (5) | 0.4732 (4) | 0.0159 (17) | |
C28 | 0.0898 (4) | 0.6051 (6) | 0.5389 (4) | 0.0187 (18) | |
H28A | 0.0720 | 0.6500 | 0.5738 | 0.022* | |
H28B | 0.0603 | 0.5435 | 0.5399 | 0.022* | |
N7 | 0.2992 (3) | 0.6594 (5) | 0.3974 (3) | 0.0158 (15) | |
C29 | 0.3422 (4) | 0.7366 (6) | 0.3811 (4) | 0.0175 (18) | |
H29 | 0.3430 | 0.7943 | 0.4083 | 0.021* | |
C30 | 0.3849 (4) | 0.7344 (6) | 0.3264 (4) | 0.0200 (19) | |
H30 | 0.4133 | 0.7910 | 0.3153 | 0.024* | |
C31 | 0.3863 (4) | 0.6482 (6) | 0.2871 (4) | 0.0204 (19) | |
H31 | 0.4174 | 0.6430 | 0.2505 | 0.025* | |
C32 | 0.3404 (4) | 0.5710 (6) | 0.3039 (4) | 0.0219 (19) | |
H32 | 0.3384 | 0.5126 | 0.2773 | 0.026* | |
C33 | 0.2975 (4) | 0.5775 (6) | 0.3584 (4) | 0.0168 (17) | |
C34 | 0.2455 (6) | 0.4961 (5) | 0.3786 (4) | 0.015 (2) | |
H34A | 0.1964 | 0.5142 | 0.3648 | 0.018* | |
H34B | 0.2586 | 0.4318 | 0.3575 | 0.018* | |
N8 | 0.2348 (3) | 0.7597 (5) | 0.5497 (3) | 0.0157 (15) | |
C35 | 0.2587 (4) | 0.8531 (6) | 0.5418 (4) | 0.0203 (19) | |
H35 | 0.2797 | 0.8712 | 0.5012 | 0.024* | |
C36 | 0.2540 (5) | 0.9247 (6) | 0.5906 (4) | 0.0229 (19) | |
H36 | 0.2739 | 0.9896 | 0.5846 | 0.027* | |
C37 | 0.2194 (4) | 0.8996 (6) | 0.6484 (4) | 0.0229 (19) | |
H37 | 0.2133 | 0.9485 | 0.6817 | 0.027* | |
C38 | 0.1945 (4) | 0.8047 (6) | 0.6572 (5) | 0.0215 (19) | |
H38 | 0.1703 | 0.7866 | 0.6963 | 0.026* | |
C39 | 0.2053 (4) | 0.7337 (6) | 0.6070 (4) | 0.0178 (18) | |
C40 | 0.1860 (4) | 0.6243 (6) | 0.6167 (4) | 0.0193 (18) | |
H40A | 0.2276 | 0.5879 | 0.6349 | 0.023* | |
H40B | 0.1462 | 0.6191 | 0.6485 | 0.023* | |
N9 | 0.2484 (4) | 0.4857 (5) | 0.4501 (4) | 0.0145 (16) | |
C41 | 0.1855 (4) | 0.4353 (5) | 0.4796 (4) | 0.0183 (18) | |
H41A | 0.1920 | 0.3617 | 0.4777 | 0.022* | |
H41B | 0.1420 | 0.4525 | 0.4544 | 0.022* | |
C42 | 0.1759 (4) | 0.4677 (7) | 0.5504 (4) | 0.0208 (19) | |
H42A | 0.1344 | 0.4324 | 0.5697 | 0.025* | |
H42B | 0.2190 | 0.4494 | 0.5759 | 0.025* | |
N10 | 0.1644 (3) | 0.5775 (5) | 0.5540 (3) | 0.0146 (15) | |
C44 | 0.3512 (5) | 0.4995 (5) | 0.5274 (5) | 0.015 (2) | |
C43 | 0.3159 (4) | 0.4406 (6) | 0.4729 (4) | 0.0176 (18) | |
H43A | 0.3495 | 0.4359 | 0.4356 | 0.021* | |
H43B | 0.3063 | 0.3717 | 0.4885 | 0.021* | |
O3 | 0.3294 (3) | 0.5853 (4) | 0.5418 (3) | 0.0187 (13) | |
O4 | 0.4032 (3) | 0.4543 (4) | 0.5554 (3) | 0.0245 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0149 (5) | 0.0143 (5) | 0.0154 (5) | −0.0011 (4) | 0.0003 (4) | −0.0014 (4) |
Zn2 | 0.0171 (5) | 0.0170 (5) | 0.0162 (5) | 0.0004 (4) | −0.0009 (4) | −0.0012 (4) |
Br1 | 0.0265 (5) | 0.0433 (5) | 0.0267 (5) | 0.0071 (5) | 0.0106 (4) | 0.0044 (5) |
Br2 | 0.0410 (6) | 0.0192 (4) | 0.0392 (6) | 0.0071 (4) | 0.0088 (5) | 0.0060 (4) |
Br3 | 0.0244 (5) | 0.0330 (5) | 0.0442 (6) | −0.0057 (4) | −0.0005 (4) | −0.0171 (4) |
N1 | 0.020 (4) | 0.013 (3) | 0.020 (4) | −0.001 (3) | 0.000 (3) | 0.000 (3) |
C1 | 0.027 (5) | 0.015 (4) | 0.027 (5) | 0.000 (4) | −0.001 (4) | 0.001 (4) |
C2 | 0.027 (5) | 0.033 (5) | 0.029 (5) | −0.001 (4) | −0.010 (5) | 0.014 (5) |
C3 | 0.016 (5) | 0.023 (5) | 0.053 (6) | 0.006 (4) | −0.011 (5) | 0.005 (4) |
C4 | 0.020 (5) | 0.011 (4) | 0.037 (6) | 0.000 (4) | 0.002 (4) | −0.001 (4) |
C5 | 0.017 (4) | 0.012 (4) | 0.024 (5) | −0.003 (3) | −0.002 (4) | −0.006 (3) |
C6 | 0.014 (4) | 0.015 (4) | 0.030 (5) | −0.002 (3) | 0.001 (4) | 0.001 (4) |
N2 | 0.015 (4) | 0.017 (4) | 0.016 (4) | −0.001 (3) | 0.002 (3) | −0.001 (3) |
C7 | 0.014 (4) | 0.012 (4) | 0.022 (4) | 0.005 (3) | −0.001 (4) | 0.003 (3) |
C8 | 0.020 (5) | 0.016 (4) | 0.030 (5) | 0.006 (3) | −0.009 (4) | −0.007 (4) |
C9 | 0.028 (5) | 0.034 (5) | 0.021 (5) | 0.014 (4) | −0.006 (4) | −0.008 (4) |
C10 | 0.019 (5) | 0.027 (5) | 0.021 (5) | 0.001 (4) | −0.002 (4) | −0.004 (4) |
C11 | 0.009 (4) | 0.027 (5) | 0.016 (4) | −0.001 (3) | −0.003 (3) | 0.005 (4) |
C12 | 0.022 (4) | 0.021 (4) | 0.015 (4) | −0.005 (4) | 0.002 (4) | 0.000 (3) |
N3 | 0.016 (3) | 0.015 (3) | 0.014 (4) | 0.003 (3) | −0.004 (3) | −0.003 (3) |
C13 | 0.019 (5) | 0.021 (5) | 0.026 (5) | −0.002 (4) | 0.003 (4) | 0.003 (4) |
C14 | 0.019 (4) | 0.029 (5) | 0.019 (5) | 0.003 (4) | −0.002 (4) | 0.000 (4) |
C15 | 0.018 (4) | 0.035 (5) | 0.013 (4) | 0.006 (4) | 0.009 (4) | 0.005 (4) |
C16 | 0.031 (5) | 0.027 (5) | 0.016 (5) | 0.008 (4) | −0.007 (4) | −0.004 (4) |
C17 | 0.015 (4) | 0.020 (4) | 0.014 (4) | 0.005 (3) | −0.004 (4) | 0.004 (3) |
C18 | 0.023 (5) | 0.020 (5) | 0.016 (5) | 0.003 (3) | −0.006 (5) | −0.005 (3) |
N4 | 0.016 (4) | 0.024 (4) | 0.012 (3) | 0.001 (3) | −0.002 (3) | 0.003 (3) |
C19 | 0.027 (5) | 0.017 (5) | 0.024 (5) | −0.001 (4) | −0.004 (4) | 0.003 (4) |
C20 | 0.019 (4) | 0.014 (4) | 0.032 (5) | −0.005 (4) | −0.002 (4) | −0.003 (4) |
N5 | 0.015 (4) | 0.014 (4) | 0.015 (4) | 0.000 (3) | −0.008 (3) | −0.002 (3) |
C21 | 0.016 (4) | 0.014 (4) | 0.023 (5) | 0.001 (3) | −0.004 (4) | −0.001 (4) |
C22 | 0.018 (5) | 0.027 (6) | 0.007 (5) | 0.000 (3) | −0.001 (4) | 0.001 (3) |
O1 | 0.017 (3) | 0.020 (3) | 0.021 (3) | 0.001 (2) | −0.003 (3) | −0.005 (3) |
O2 | 0.016 (3) | 0.032 (4) | 0.017 (3) | 0.006 (3) | −0.003 (3) | −0.001 (3) |
Zn3 | 0.0142 (5) | 0.0139 (4) | 0.0150 (5) | −0.0012 (4) | 0.0002 (4) | 0.0006 (4) |
Zn4 | 0.0164 (5) | 0.0166 (5) | 0.0156 (5) | 0.0021 (4) | −0.0021 (4) | −0.0003 (4) |
Br4 | 0.0217 (5) | 0.0213 (4) | 0.0342 (5) | −0.0025 (3) | −0.0037 (4) | −0.0038 (4) |
Br5 | 0.0210 (5) | 0.0323 (5) | 0.0223 (5) | 0.0037 (4) | 0.0039 (4) | 0.0021 (4) |
Br6 | 0.0315 (5) | 0.0161 (4) | 0.0312 (5) | 0.0030 (4) | 0.0020 (4) | 0.0002 (4) |
N6 | 0.013 (4) | 0.015 (3) | 0.017 (4) | −0.001 (3) | −0.001 (3) | 0.003 (3) |
C23 | 0.026 (5) | 0.024 (5) | 0.026 (5) | 0.001 (4) | 0.007 (4) | 0.011 (4) |
C24 | 0.025 (5) | 0.035 (5) | 0.030 (6) | 0.002 (4) | −0.004 (5) | 0.015 (5) |
C25 | 0.016 (5) | 0.027 (5) | 0.042 (6) | 0.001 (4) | −0.007 (4) | 0.008 (4) |
C26 | 0.016 (5) | 0.026 (5) | 0.021 (5) | 0.002 (4) | 0.001 (4) | 0.001 (4) |
C27 | 0.015 (4) | 0.013 (4) | 0.019 (4) | 0.000 (3) | −0.004 (4) | 0.000 (3) |
C28 | 0.013 (4) | 0.026 (5) | 0.017 (4) | −0.004 (3) | 0.002 (4) | 0.006 (3) |
N7 | 0.019 (4) | 0.015 (3) | 0.013 (4) | 0.002 (3) | 0.002 (3) | −0.002 (3) |
C29 | 0.014 (4) | 0.018 (4) | 0.020 (5) | −0.004 (3) | −0.002 (4) | 0.002 (3) |
C30 | 0.014 (4) | 0.025 (5) | 0.022 (5) | −0.003 (3) | 0.001 (4) | 0.009 (4) |
C31 | 0.018 (4) | 0.032 (5) | 0.012 (4) | 0.001 (4) | −0.005 (4) | 0.001 (4) |
C32 | 0.018 (4) | 0.030 (5) | 0.018 (5) | 0.006 (4) | −0.005 (4) | −0.004 (4) |
C33 | 0.014 (4) | 0.017 (4) | 0.019 (4) | 0.005 (3) | −0.005 (4) | −0.002 (4) |
C34 | 0.022 (5) | 0.010 (5) | 0.013 (5) | 0.000 (3) | 0.002 (5) | −0.002 (3) |
N8 | 0.010 (3) | 0.019 (4) | 0.018 (4) | 0.003 (3) | 0.001 (3) | 0.008 (3) |
C35 | 0.017 (4) | 0.025 (5) | 0.019 (4) | 0.001 (4) | 0.001 (4) | 0.005 (4) |
C36 | 0.020 (5) | 0.014 (4) | 0.034 (5) | 0.002 (3) | −0.008 (4) | 0.002 (4) |
C37 | 0.029 (5) | 0.018 (4) | 0.022 (5) | 0.007 (4) | −0.006 (4) | −0.007 (4) |
C38 | 0.018 (4) | 0.029 (5) | 0.018 (4) | 0.005 (4) | −0.002 (4) | −0.003 (4) |
C39 | 0.016 (4) | 0.016 (4) | 0.021 (5) | 0.006 (3) | −0.002 (4) | −0.001 (4) |
C40 | 0.020 (4) | 0.022 (4) | 0.015 (4) | 0.004 (4) | 0.003 (4) | 0.002 (3) |
N9 | 0.018 (4) | 0.012 (3) | 0.014 (4) | 0.004 (3) | −0.001 (3) | 0.001 (3) |
C41 | 0.018 (4) | 0.011 (4) | 0.026 (5) | −0.001 (3) | −0.003 (4) | 0.001 (4) |
C42 | 0.014 (4) | 0.020 (5) | 0.029 (5) | −0.008 (4) | −0.001 (4) | 0.006 (4) |
N10 | 0.016 (4) | 0.013 (4) | 0.016 (4) | −0.005 (3) | −0.001 (3) | 0.002 (3) |
C44 | 0.017 (5) | 0.012 (5) | 0.015 (5) | −0.001 (3) | 0.008 (4) | 0.006 (3) |
C43 | 0.016 (4) | 0.014 (4) | 0.023 (5) | 0.002 (3) | −0.001 (4) | 0.000 (4) |
O3 | 0.022 (3) | 0.017 (3) | 0.017 (3) | −0.002 (2) | −0.003 (3) | −0.003 (2) |
O4 | 0.025 (3) | 0.033 (4) | 0.015 (3) | 0.013 (3) | −0.007 (3) | −0.008 (3) |
Zn1—N1 | 2.200 (7) | Zn3—N6 | 2.207 (6) |
Zn1—N2 | 2.094 (7) | Zn3—N7 | 2.088 (6) |
Zn1—N3 | 2.080 (7) | Zn3—N8 | 2.094 (7) |
Zn1—N4 | 2.182 (7) | Zn3—N9 | 2.183 (7) |
Zn1—N5 | 2.192 (6) | Zn3—N10 | 2.194 (6) |
Zn1—O1 | 2.184 (5) | Zn3—O3 | 2.202 (5) |
Zn2—O2 | 2.001 (6) | Zn4—O4 | 2.008 (6) |
Zn2—Br1 | 2.3721 (13) | Zn4—Br4 | 2.3816 (12) |
Zn2—Br2 | 2.3953 (12) | Zn4—Br5 | 2.3856 (12) |
Zn2—Br3 | 2.3776 (12) | Zn4—Br6 | 2.4161 (11) |
N1—C5 | 1.339 (10) | N6—C27 | 1.332 (10) |
N1—C1 | 1.359 (10) | N6—C23 | 1.347 (10) |
C1—C2 | 1.370 (12) | C23—C24 | 1.360 (12) |
C1—H1 | 0.9500 | C23—H23 | 0.9500 |
C2—C3 | 1.375 (13) | C24—C25 | 1.391 (13) |
C2—H2 | 0.9500 | C24—H24 | 0.9500 |
C3—C4 | 1.368 (12) | C25—C26 | 1.389 (13) |
C3—H3 | 0.9500 | C25—H25 | 0.9500 |
C4—C5 | 1.390 (11) | C26—C27 | 1.384 (11) |
C4—H4 | 0.9500 | C26—H26 | 0.9500 |
C5—C6 | 1.507 (11) | C27—C28 | 1.524 (11) |
C6—N4 | 1.489 (10) | C28—N10 | 1.476 (10) |
C6—H6A | 0.9900 | C28—H28A | 0.9900 |
C6—H6B | 0.9900 | C28—H28B | 0.9900 |
N2—C7 | 1.347 (9) | N7—C29 | 1.348 (9) |
N2—C11 | 1.356 (10) | N7—C33 | 1.352 (9) |
C7—C8 | 1.390 (11) | C29—C30 | 1.374 (11) |
C7—H7 | 0.9500 | C29—H29 | 0.9500 |
C8—C9 | 1.374 (13) | C30—C31 | 1.404 (11) |
C8—H8 | 0.9500 | C30—H30 | 0.9500 |
C9—C10 | 1.377 (12) | C31—C32 | 1.384 (12) |
C9—H9 | 0.9500 | C31—H31 | 0.9500 |
C10—C11 | 1.380 (11) | C32—C33 | 1.377 (11) |
C10—H10 | 0.9500 | C32—H32 | 0.9500 |
C11—C12 | 1.520 (11) | C33—C34 | 1.516 (11) |
C12—N4 | 1.485 (10) | C34—N9 | 1.469 (11) |
C12—H12A | 0.9900 | C34—H34A | 0.9900 |
C12—H12B | 0.9900 | C34—H34B | 0.9900 |
N3—C13 | 1.340 (10) | N8—C35 | 1.334 (10) |
N3—C17 | 1.363 (10) | N8—C39 | 1.341 (10) |
C13—C14 | 1.375 (11) | C35—C36 | 1.383 (12) |
C13—H13 | 0.9500 | C35—H35 | 0.9500 |
C14—C15 | 1.370 (11) | C36—C37 | 1.389 (12) |
C14—H14 | 0.9500 | C36—H36 | 0.9500 |
C15—C16 | 1.392 (12) | C37—C38 | 1.361 (11) |
C15—H15 | 0.9500 | C37—H37 | 0.9500 |
C16—C17 | 1.387 (11) | C38—C39 | 1.410 (11) |
C16—H16 | 0.9500 | C38—H38 | 0.9500 |
C17—C18 | 1.500 (12) | C39—C40 | 1.516 (11) |
C18—N5 | 1.482 (12) | C40—N10 | 1.483 (10) |
C18—H18A | 0.9900 | C40—H40A | 0.9900 |
C18—H18B | 0.9900 | C40—H40B | 0.9900 |
N4—C19 | 1.487 (10) | N9—C43 | 1.475 (11) |
C19—C20 | 1.522 (12) | N9—C41 | 1.484 (11) |
C19—H19A | 0.9900 | C41—C42 | 1.522 (12) |
C19—H19B | 0.9900 | C41—H41A | 0.9900 |
C20—N5 | 1.465 (11) | C41—H41B | 0.9900 |
C20—H20A | 0.9900 | C42—N10 | 1.482 (10) |
C20—H20B | 0.9900 | C42—H42A | 0.9900 |
N5—C21 | 1.484 (11) | C42—H42B | 0.9900 |
C21—C22 | 1.530 (12) | C44—O3 | 1.249 (9) |
C21—H21A | 0.9900 | C44—O4 | 1.279 (10) |
C21—H21B | 0.9900 | C44—C43 | 1.515 (12) |
C22—O2 | 1.247 (10) | C43—H43A | 0.9900 |
C22—O1 | 1.259 (9) | C43—H43B | 0.9900 |
N3—Zn1—N2 | 118.6 (2) | N7—Zn3—N8 | 118.7 (2) |
N3—Zn1—N4 | 160.0 (2) | N7—Zn3—N9 | 79.3 (3) |
N2—Zn1—N4 | 80.6 (3) | N8—Zn3—N9 | 156.9 (3) |
N3—Zn1—O1 | 94.3 (2) | N7—Zn3—N10 | 160.7 (2) |
N2—Zn1—O1 | 87.2 (2) | N8—Zn3—N10 | 80.3 (2) |
N4—Zn1—O1 | 92.1 (2) | N9—Zn3—N10 | 83.5 (3) |
N3—Zn1—N5 | 79.7 (3) | N7—Zn3—O3 | 95.0 (2) |
N2—Zn1—N5 | 157.6 (3) | N8—Zn3—O3 | 85.9 (2) |
N4—Zn1—N5 | 83.2 (3) | N9—Zn3—O3 | 77.8 (3) |
O1—Zn1—N5 | 78.0 (2) | N10—Zn3—O3 | 89.7 (2) |
N3—Zn1—N1 | 92.2 (2) | N7—Zn3—N6 | 95.0 (2) |
N2—Zn1—N1 | 97.1 (2) | N8—Zn3—N6 | 95.9 (2) |
N4—Zn1—N1 | 79.0 (2) | N9—Zn3—N6 | 96.7 (3) |
O1—Zn1—N1 | 169.4 (2) | N10—Zn3—N6 | 78.4 (2) |
N5—Zn1—N1 | 94.9 (3) | O3—Zn3—N6 | 167.5 (2) |
O2—Zn2—Br1 | 109.13 (16) | O4—Zn4—Br4 | 111.24 (18) |
O2—Zn2—Br3 | 106.34 (17) | O4—Zn4—Br5 | 107.97 (16) |
Br1—Zn2—Br3 | 114.46 (5) | Br4—Zn4—Br5 | 114.75 (5) |
O2—Zn2—Br2 | 101.41 (17) | O4—Zn4—Br6 | 101.45 (17) |
Br1—Zn2—Br2 | 112.24 (5) | Br4—Zn4—Br6 | 110.00 (4) |
Br3—Zn2—Br2 | 112.20 (5) | Br5—Zn4—Br6 | 110.60 (5) |
C5—N1—C1 | 118.5 (7) | C27—N6—C23 | 116.9 (7) |
C5—N1—Zn1 | 114.2 (5) | C27—N6—Zn3 | 115.4 (5) |
C1—N1—Zn1 | 127.2 (6) | C23—N6—Zn3 | 127.3 (6) |
N1—C1—C2 | 122.4 (9) | N6—C23—C24 | 122.6 (8) |
N1—C1—H1 | 118.8 | N6—C23—H23 | 118.7 |
C2—C1—H1 | 118.8 | C24—C23—H23 | 118.7 |
C1—C2—C3 | 118.4 (9) | C23—C24—C25 | 120.6 (9) |
C1—C2—H2 | 120.8 | C23—C24—H24 | 119.7 |
C3—C2—H2 | 120.8 | C25—C24—H24 | 119.7 |
C4—C3—C2 | 120.2 (9) | C26—C25—C24 | 117.1 (8) |
C4—C3—H3 | 119.9 | C26—C25—H25 | 121.4 |
C2—C3—H3 | 119.9 | C24—C25—H25 | 121.4 |
C3—C4—C5 | 119.0 (8) | C27—C26—C25 | 118.5 (9) |
C3—C4—H4 | 120.5 | C27—C26—H26 | 120.7 |
C5—C4—H4 | 120.5 | C25—C26—H26 | 120.7 |
N1—C5—C4 | 121.5 (7) | N6—C27—C26 | 124.1 (7) |
N1—C5—C6 | 118.9 (7) | N6—C27—C28 | 117.6 (7) |
C4—C5—C6 | 119.6 (7) | C26—C27—C28 | 118.3 (7) |
N4—C6—C5 | 114.8 (7) | N10—C28—C27 | 115.5 (6) |
N4—C6—H6A | 108.6 | N10—C28—H28A | 108.4 |
C5—C6—H6A | 108.6 | C27—C28—H28A | 108.4 |
N4—C6—H6B | 108.6 | N10—C28—H28B | 108.4 |
C5—C6—H6B | 108.6 | C27—C28—H28B | 108.4 |
H6A—C6—H6B | 107.5 | H28A—C28—H28B | 107.5 |
C7—N2—C11 | 117.9 (7) | C29—N7—C33 | 119.0 (7) |
C7—N2—Zn1 | 128.9 (6) | C29—N7—Zn3 | 128.0 (5) |
C11—N2—Zn1 | 113.1 (5) | C33—N7—Zn3 | 112.7 (5) |
N2—C7—C8 | 122.3 (8) | N7—C29—C30 | 122.1 (7) |
N2—C7—H7 | 118.8 | N7—C29—H29 | 118.9 |
C8—C7—H7 | 118.8 | C30—C29—H29 | 118.9 |
C9—C8—C7 | 119.1 (8) | C29—C30—C31 | 119.6 (7) |
C9—C8—H8 | 120.4 | C29—C30—H30 | 120.2 |
C7—C8—H8 | 120.4 | C31—C30—H30 | 120.2 |
C8—C9—C10 | 118.9 (8) | C32—C31—C30 | 117.1 (8) |
C8—C9—H9 | 120.5 | C32—C31—H31 | 121.5 |
C10—C9—H9 | 120.5 | C30—C31—H31 | 121.5 |
C9—C10—C11 | 119.7 (9) | C33—C32—C31 | 121.0 (8) |
C9—C10—H10 | 120.2 | C33—C32—H32 | 119.5 |
C11—C10—H10 | 120.2 | C31—C32—H32 | 119.5 |
N2—C11—C10 | 121.9 (8) | N7—C33—C32 | 121.0 (7) |
N2—C11—C12 | 116.0 (7) | N7—C33—C34 | 115.7 (7) |
C10—C11—C12 | 121.9 (7) | C32—C33—C34 | 123.3 (7) |
N4—C12—C11 | 110.8 (7) | N9—C34—C33 | 108.3 (7) |
N4—C12—H12A | 109.5 | N9—C34—H34A | 110.0 |
C11—C12—H12A | 109.5 | C33—C34—H34A | 110.0 |
N4—C12—H12B | 109.5 | N9—C34—H34B | 110.0 |
C11—C12—H12B | 109.5 | C33—C34—H34B | 110.0 |
H12A—C12—H12B | 108.1 | H34A—C34—H34B | 108.4 |
C13—N3—C17 | 119.4 (7) | C35—N8—C39 | 119.0 (7) |
C13—N3—Zn1 | 127.4 (5) | C35—N8—Zn3 | 127.8 (6) |
C17—N3—Zn1 | 113.1 (5) | C39—N8—Zn3 | 113.2 (5) |
N3—C13—C14 | 122.6 (8) | N8—C35—C36 | 122.5 (8) |
N3—C13—H13 | 118.7 | N8—C35—H35 | 118.8 |
C14—C13—H13 | 118.7 | C36—C35—H35 | 118.8 |
C15—C14—C13 | 118.3 (8) | C35—C36—C37 | 118.5 (7) |
C15—C14—H14 | 120.8 | C35—C36—H36 | 120.8 |
C13—C14—H14 | 120.8 | C37—C36—H36 | 120.8 |
C14—C15—C16 | 120.3 (8) | C38—C37—C36 | 119.8 (8) |
C14—C15—H15 | 119.9 | C38—C37—H37 | 120.1 |
C16—C15—H15 | 119.9 | C36—C37—H37 | 120.1 |
C17—C16—C15 | 118.8 (8) | C37—C38—C39 | 118.6 (8) |
C17—C16—H16 | 120.6 | C37—C38—H38 | 120.7 |
C15—C16—H16 | 120.6 | C39—C38—H38 | 120.7 |
N3—C17—C16 | 120.4 (7) | N8—C39—C38 | 121.5 (7) |
N3—C17—C18 | 116.5 (7) | N8—C39—C40 | 117.4 (7) |
C16—C17—C18 | 123.1 (7) | C38—C39—C40 | 121.1 (7) |
N5—C18—C17 | 109.6 (7) | N10—C40—C39 | 110.9 (6) |
N5—C18—H18A | 109.8 | N10—C40—H40A | 109.5 |
C17—C18—H18A | 109.8 | C39—C40—H40A | 109.5 |
N5—C18—H18B | 109.8 | N10—C40—H40B | 109.5 |
C17—C18—H18B | 109.8 | C39—C40—H40B | 109.5 |
H18A—C18—H18B | 108.2 | H40A—C40—H40B | 108.1 |
C12—N4—C19 | 113.9 (6) | C34—N9—C43 | 112.7 (7) |
C12—N4—C6 | 109.6 (6) | C34—N9—C41 | 114.7 (7) |
C19—N4—C6 | 113.8 (6) | C43—N9—C41 | 111.5 (6) |
C12—N4—Zn1 | 103.2 (5) | C34—N9—Zn3 | 102.2 (4) |
C19—N4—Zn1 | 104.7 (5) | C43—N9—Zn3 | 110.9 (5) |
C6—N4—Zn1 | 111.0 (5) | C41—N9—Zn3 | 104.1 (5) |
N4—C19—C20 | 109.4 (7) | N9—C41—C42 | 110.6 (6) |
N4—C19—H19A | 109.8 | N9—C41—H41A | 109.5 |
C20—C19—H19A | 109.8 | C42—C41—H41A | 109.5 |
N4—C19—H19B | 109.8 | N9—C41—H41B | 109.5 |
C20—C19—H19B | 109.8 | C42—C41—H41B | 109.5 |
H19A—C19—H19B | 108.2 | H41A—C41—H41B | 108.1 |
N5—C20—C19 | 110.7 (7) | N10—C42—C41 | 110.1 (7) |
N5—C20—H20A | 109.5 | N10—C42—H42A | 109.6 |
C19—C20—H20A | 109.5 | C41—C42—H42A | 109.6 |
N5—C20—H20B | 109.5 | N10—C42—H42B | 109.6 |
C19—C20—H20B | 109.5 | C41—C42—H42B | 109.6 |
H20A—C20—H20B | 108.1 | H42A—C42—H42B | 108.1 |
C20—N5—C18 | 116.2 (7) | C28—N10—C42 | 111.9 (6) |
C20—N5—C21 | 111.5 (6) | C28—N10—C40 | 109.6 (6) |
C18—N5—C21 | 110.8 (7) | C42—N10—C40 | 114.7 (6) |
C20—N5—Zn1 | 104.1 (5) | C28—N10—Zn3 | 111.6 (5) |
C18—N5—Zn1 | 103.2 (4) | C42—N10—Zn3 | 104.8 (5) |
C21—N5—Zn1 | 110.3 (5) | C40—N10—Zn3 | 103.8 (4) |
N5—C21—C22 | 114.5 (6) | O3—C44—O4 | 125.1 (9) |
N5—C21—H21A | 108.6 | O3—C44—C43 | 120.4 (8) |
C22—C21—H21A | 108.6 | O4—C44—C43 | 114.6 (7) |
N5—C21—H21B | 108.6 | N9—C43—C44 | 113.3 (6) |
C22—C21—H21B | 108.6 | N9—C43—H43A | 108.9 |
H21A—C21—H21B | 107.6 | C44—C43—H43A | 108.9 |
O2—C22—O1 | 127.5 (8) | N9—C43—H43B | 108.9 |
O2—C22—C21 | 114.4 (7) | C44—C43—H43B | 108.9 |
O1—C22—C21 | 118.1 (8) | H43A—C43—H43B | 107.7 |
C22—O1—Zn1 | 117.5 (6) | C44—O3—Zn3 | 115.5 (6) |
C22—O2—Zn2 | 127.6 (6) | C44—O4—Zn4 | 130.0 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···Br4 | 0.95 | 3.12 | 3.700 (8) | 121 |
C6—H6A···Br3i | 0.99 | 3.12 | 3.724 (8) | 121 |
C6—H6B···Br2i | 0.99 | 2.81 | 3.710 (8) | 152 |
C12—H12B···Br1 | 0.99 | 2.88 | 3.853 (8) | 167 |
C13—H13···O3 | 0.95 | 2.38 | 3.145 (10) | 137 |
C14—H14···Br5 | 0.95 | 3.05 | 3.939 (9) | 157 |
C15—H15···Br3ii | 0.95 | 2.76 | 3.578 (8) | 145 |
C18—H18A···Br6iii | 0.99 | 2.85 | 3.764 (8) | 155 |
C18—H18B···Br1iv | 0.99 | 3.05 | 3.583 (10) | 115 |
C19—H19B···Br3i | 0.99 | 2.92 | 3.747 (9) | 141 |
C26—H26···O4v | 0.95 | 2.54 | 3.381 (11) | 148 |
C28—H28A···Br6v | 0.99 | 2.85 | 3.762 (8) | 154 |
C29—H29···O1 | 0.95 | 2.53 | 3.334 (9) | 142 |
C34—H34B···Br2ii | 0.99 | 2.77 | 3.698 (7) | 157 |
C40—H40A···Br5 | 0.99 | 2.84 | 3.801 (8) | 165 |
C42—H42A···Br4v | 0.99 | 3.07 | 3.900 (8) | 142 |
Symmetry codes: (i) x+1/2, −y+2, z; (ii) x, y−1, z; (iii) x, y+1, z; (iv) −x+1, −y+2, z+1/2; (v) x−1/2, −y+1, z. |
[Cu2Br3(C22H24N5O2)][Cu2Br3(C22H24N5O2)(H2O)]·6.5H2O | Z = 2 |
Mr = 1649.66 | F(000) = 1630 |
Triclinic, P1 | Dx = 1.912 Mg m−3 |
a = 11.2516 (9) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 15.0606 (10) Å | Cell parameters from 7803 reflections |
c = 18.3213 (14) Å | θ = 2.4–26.2° |
α = 112.087 (3)° | µ = 5.71 mm−1 |
β = 94.380 (3)° | T = 180 K |
γ = 90.486 (3)° | Needle, pale blue |
V = 2866.1 (4) Å3 | 0.20 × 0.11 × 0.05 mm |
Bruker–Nonius X8 APEXII CCD diffractometer | 11068 independent reflections |
Radiation source: fine-focus sealed-tube | 7261 reflections with I > 2σ(I) |
Detector resolution: 9.1 pixels mm-1 | Rint = 0.077 |
thin–slice ω and φ scans | θmax = 26.4°, θmin = 2.1° |
Absorption correction: multi-scan (TWINABS; Sheldrick, 2012) | h = −14→13 |
Tmin = 0.303, Tmax = 0.430 | k = −18→17 |
11068 measured reflections | l = 0→22 |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0462P)2] where P = (Fo2 + 2Fc2)/3 |
11068 reflections | (Δ/σ)max = 0.001 |
686 parameters | Δρmax = 0.99 e Å−3 |
0 restraints | Δρmin = −0.88 e Å−3 |
[Cu2Br3(C22H24N5O2)][Cu2Br3(C22H24N5O2)(H2O)]·6.5H2O | γ = 90.486 (3)° |
Mr = 1649.66 | V = 2866.1 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.2516 (9) Å | Mo Kα radiation |
b = 15.0606 (10) Å | µ = 5.71 mm−1 |
c = 18.3213 (14) Å | T = 180 K |
α = 112.087 (3)° | 0.20 × 0.11 × 0.05 mm |
β = 94.380 (3)° |
Bruker–Nonius X8 APEXII CCD diffractometer | 11068 independent reflections |
Absorption correction: multi-scan (TWINABS; Sheldrick, 2012) | 7261 reflections with I > 2σ(I) |
Tmin = 0.303, Tmax = 0.430 | Rint = 0.077 |
11068 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.99 e Å−3 |
11068 reflections | Δρmin = −0.88 e Å−3 |
686 parameters |
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. |
Refinement. Refined as a 2-component twin.H atoms of the water molecules were not located and are not included in the model. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.40326 (9) | 0.55531 (7) | 0.18085 (6) | 0.0173 (2) | |
Cu2 | −0.00160 (9) | 0.57391 (7) | 0.30625 (6) | 0.0177 (2) | |
Br1 | 0.62240 (8) | 0.53381 (7) | 0.16191 (6) | 0.0290 (2) | |
Br2 | 0.25880 (9) | 0.43804 (6) | 0.08770 (5) | 0.0256 (2) | |
Br3 | 0.07600 (9) | 0.45736 (7) | 0.35413 (6) | 0.0337 (3) | |
N1 | 0.4155 (6) | 0.4927 (4) | 0.2587 (4) | 0.0172 (16) | |
C1 | 0.4096 (7) | 0.3982 (6) | 0.2432 (6) | 0.027 (2) | |
H1 | 0.3994 | 0.3541 | 0.1899 | 0.032* | |
C2 | 0.4181 (8) | 0.3639 (6) | 0.3029 (5) | 0.026 (2) | |
H2 | 0.4154 | 0.2967 | 0.2905 | 0.031* | |
C3 | 0.4306 (8) | 0.4261 (7) | 0.3804 (6) | 0.033 (3) | |
H3 | 0.4349 | 0.4026 | 0.4219 | 0.040* | |
C4 | 0.4368 (7) | 0.5242 (6) | 0.3974 (5) | 0.021 (2) | |
H4 | 0.4453 | 0.5692 | 0.4504 | 0.026* | |
C5 | 0.4302 (7) | 0.5545 (6) | 0.3340 (5) | 0.017 (2) | |
C6 | 0.4458 (7) | 0.6589 (6) | 0.3450 (5) | 0.018 (2) | |
H6A | 0.4237 | 0.7006 | 0.3980 | 0.022* | |
H6B | 0.5302 | 0.6741 | 0.3409 | 0.022* | |
N2 | 0.3931 (6) | 0.6521 (4) | 0.1311 (4) | 0.0206 (17) | |
C7 | 0.3885 (8) | 0.6315 (6) | 0.0521 (5) | 0.024 (2) | |
H7 | 0.3887 | 0.5666 | 0.0163 | 0.028* | |
C8 | 0.3836 (8) | 0.7044 (7) | 0.0230 (5) | 0.026 (2) | |
H8 | 0.3831 | 0.6898 | −0.0322 | 0.031* | |
C9 | 0.3794 (7) | 0.7961 (6) | 0.0738 (5) | 0.024 (2) | |
H9 | 0.3729 | 0.8462 | 0.0543 | 0.029* | |
C10 | 0.3846 (7) | 0.8171 (6) | 0.1534 (5) | 0.023 (2) | |
H10 | 0.3822 | 0.8817 | 0.1894 | 0.027* | |
C11 | 0.3934 (7) | 0.7424 (6) | 0.1817 (5) | 0.017 (2) | |
C12 | 0.4091 (7) | 0.7620 (6) | 0.2687 (5) | 0.018 (2) | |
H12A | 0.4942 | 0.7779 | 0.2881 | 0.022* | |
H12B | 0.3622 | 0.8176 | 0.2978 | 0.022* | |
N3 | −0.0465 (6) | 0.4914 (4) | 0.1950 (4) | 0.0139 (16) | |
C13 | −0.0614 (7) | 0.3968 (6) | 0.1625 (5) | 0.020 (2) | |
H13 | −0.0500 | 0.3615 | 0.1957 | 0.024* | |
C14 | −0.0924 (7) | 0.3465 (6) | 0.0828 (5) | 0.023 (2) | |
H14 | −0.1036 | 0.2787 | 0.0620 | 0.027* | |
C15 | −0.1066 (8) | 0.3972 (6) | 0.0350 (6) | 0.025 (2) | |
H15 | −0.1264 | 0.3645 | −0.0202 | 0.030* | |
C16 | −0.0918 (7) | 0.4979 (6) | 0.0672 (5) | 0.019 (2) | |
H16 | −0.1010 | 0.5345 | 0.0349 | 0.023* | |
C17 | −0.0633 (7) | 0.5415 (5) | 0.1482 (5) | 0.0138 (19) | |
C18 | −0.0544 (7) | 0.6486 (6) | 0.1890 (5) | 0.0166 (19) | |
H18A | −0.0254 | 0.6774 | 0.1529 | 0.020* | |
H18B | −0.1343 | 0.6731 | 0.2032 | 0.020* | |
N4 | 0.3688 (6) | 0.6764 (4) | 0.2834 (4) | 0.0154 (16) | |
C19 | 0.2442 (7) | 0.6811 (6) | 0.3058 (5) | 0.019 (2) | |
H19A | 0.2357 | 0.7414 | 0.3517 | 0.023* | |
H19B | 0.2266 | 0.6268 | 0.3218 | 0.023* | |
C20 | 0.1540 (7) | 0.6772 (6) | 0.2375 (5) | 0.0160 (19) | |
H20A | 0.1680 | 0.7336 | 0.2234 | 0.019* | |
H20B | 0.1648 | 0.6187 | 0.1905 | 0.019* | |
N5 | 0.0282 (6) | 0.6766 (4) | 0.2611 (4) | 0.0157 (16) | |
C21 | 0.0019 (8) | 0.7690 (6) | 0.3243 (5) | 0.021 (2) | |
H21A | −0.0816 | 0.7850 | 0.3150 | 0.025* | |
H21B | 0.0550 | 0.8208 | 0.3226 | 0.025* | |
C22 | 0.0199 (7) | 0.7629 (7) | 0.4043 (5) | 0.023 (2) | |
O1 | 0.0330 (5) | 0.6793 (4) | 0.4075 (3) | 0.0194 (13) | |
O2 | 0.0222 (6) | 0.8370 (4) | 0.4656 (4) | 0.0398 (18) | |
Cu3 | 0.70717 (10) | 0.09427 (7) | 0.22562 (6) | 0.0212 (3) | |
Cu4 | 1.13409 (10) | −0.01614 (7) | 0.21751 (6) | 0.0203 (3) | |
Br4 | 0.47160 (8) | 0.09019 (6) | 0.25193 (6) | 0.0282 (2) | |
Br5 | 0.75962 (11) | 0.13000 (7) | 0.11421 (6) | 0.0422 (3) | |
Br6 | 1.04997 (9) | −0.15919 (6) | 0.12065 (6) | 0.0312 (2) | |
N6 | 0.6954 (6) | −0.0484 (5) | 0.1715 (4) | 0.0221 (17) | |
C23 | 0.6770 (8) | −0.0997 (6) | 0.0939 (6) | 0.029 (2) | |
H23 | 0.6677 | −0.0671 | 0.0584 | 0.035* | |
C24 | 0.6709 (8) | −0.1985 (6) | 0.0638 (5) | 0.027 (2) | |
H24 | 0.6598 | −0.2335 | 0.0084 | 0.032* | |
C25 | 0.6813 (8) | −0.2461 (6) | 0.1149 (6) | 0.034 (3) | |
H25 | 0.6769 | −0.3142 | 0.0956 | 0.040* | |
C26 | 0.6983 (8) | −0.1920 (6) | 0.1953 (6) | 0.027 (2) | |
H26 | 0.7056 | −0.2229 | 0.2320 | 0.032* | |
C27 | 0.7044 (7) | −0.0942 (6) | 0.2219 (5) | 0.020 (2) | |
C28 | 0.7169 (8) | −0.0307 (6) | 0.3085 (5) | 0.023 (2) | |
H28A | 0.6370 | −0.0169 | 0.3284 | 0.027* | |
H28B | 0.7617 | −0.0635 | 0.3390 | 0.027* | |
N7 | 0.7297 (6) | 0.2275 (5) | 0.3049 (4) | 0.0227 (17) | |
C29 | 0.7216 (8) | 0.3103 (6) | 0.2910 (6) | 0.026 (2) | |
H29 | 0.7055 | 0.3064 | 0.2382 | 0.031* | |
C30 | 0.7361 (8) | 0.3986 (6) | 0.3508 (6) | 0.033 (3) | |
H30 | 0.7288 | 0.4549 | 0.3394 | 0.040* | |
C31 | 0.7617 (9) | 0.4058 (7) | 0.4281 (6) | 0.036 (3) | |
H31 | 0.7733 | 0.4668 | 0.4699 | 0.043* | |
C32 | 0.7698 (8) | 0.3229 (6) | 0.4433 (6) | 0.029 (2) | |
H32 | 0.7872 | 0.3255 | 0.4957 | 0.034* | |
C33 | 0.7519 (8) | 0.2354 (6) | 0.3800 (5) | 0.022 (2) | |
C34 | 0.7577 (8) | 0.1416 (6) | 0.3937 (5) | 0.024 (2) | |
H34A | 0.8218 | 0.1472 | 0.4355 | 0.029* | |
H34B | 0.6811 | 0.1282 | 0.4116 | 0.029* | |
N8 | 1.1389 (6) | 0.0651 (4) | 0.1559 (4) | 0.0178 (16) | |
C35 | 1.1268 (7) | 0.0387 (6) | 0.0774 (5) | 0.025 (2) | |
H35 | 1.1173 | −0.0276 | 0.0452 | 0.030* | |
C36 | 1.1276 (8) | 0.1046 (6) | 0.0412 (5) | 0.026 (2) | |
H36 | 1.1193 | 0.0837 | −0.0148 | 0.031* | |
C37 | 1.1404 (8) | 0.1997 (6) | 0.0873 (5) | 0.024 (2) | |
H37 | 1.1396 | 0.2457 | 0.0633 | 0.029* | |
C38 | 1.1546 (8) | 0.2298 (6) | 0.1681 (5) | 0.025 (2) | |
H38 | 1.1648 | 0.2961 | 0.2003 | 0.029* | |
C39 | 1.1537 (7) | 0.1612 (6) | 0.2020 (5) | 0.0167 (19) | |
C40 | 1.1735 (7) | 0.1829 (6) | 0.2884 (5) | 0.017 (2) | |
H40A | 1.2602 | 0.1862 | 0.3039 | 0.021* | |
H40B | 1.1414 | 0.2461 | 0.3181 | 0.021* | |
N9 | 0.7818 (6) | 0.0607 (5) | 0.3187 (4) | 0.0193 (17) | |
C41 | 0.9123 (8) | 0.0428 (6) | 0.3136 (5) | 0.024 (2) | |
H41A | 0.9230 | −0.0129 | 0.2644 | 0.028* | |
H41B | 0.9426 | 0.0261 | 0.3587 | 0.028* | |
C42 | 0.9868 (7) | 0.1289 (5) | 0.3140 (5) | 0.0170 (19) | |
H42A | 0.9572 | 0.1457 | 0.2687 | 0.020* | |
H42B | 0.9766 | 0.1848 | 0.3632 | 0.020* | |
N10 | 1.1149 (6) | 0.1089 (5) | 0.3091 (4) | 0.0173 (16) | |
C43 | 1.1735 (8) | 0.0994 (6) | 0.3815 (5) | 0.027 (2) | |
H43A | 1.1176 | 0.1179 | 0.4235 | 0.032* | |
H43B | 1.2446 | 0.1437 | 0.4010 | 0.032* | |
C44 | 1.2112 (8) | −0.0036 (7) | 0.3646 (6) | 0.032 (3) | |
O3 | 1.1880 (5) | −0.0656 (4) | 0.2950 (4) | 0.0292 (16) | |
O4 | 1.2605 (7) | −0.0207 (5) | 0.4205 (5) | 0.062 (2) | |
O5 | −0.1995 (5) | 0.6110 (4) | 0.3193 (3) | 0.0311 (16) | |
O6 | 0.2956 (6) | 0.3206 (4) | 0.5363 (3) | 0.0319 (16) | |
O7 | 0.0772 (5) | 0.3326 (4) | 0.4671 (3) | 0.0292 (16) | |
O8 | 0.3234 (6) | 0.1477 (5) | 0.5765 (4) | 0.0442 (19) | |
O9 | 0.4745 (6) | 0.2287 (4) | 0.4432 (4) | 0.0351 (17) | |
O10 | 0.5598 (6) | 0.1138 (5) | 0.5236 (4) | 0.0429 (19) | |
O11 | 0.4555 (9) | 0.1661 (7) | 0.0956 (5) | 0.094 (3) | |
O12 | 0.1109 (12) | 0.0290 (8) | 0.5442 (7) | 0.038 (3) | 0.5 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0169 (6) | 0.0168 (5) | 0.0175 (6) | −0.0018 (4) | 0.0010 (5) | 0.0058 (5) |
Cu2 | 0.0179 (6) | 0.0187 (5) | 0.0179 (6) | 0.0006 (5) | 0.0014 (5) | 0.0085 (5) |
Br1 | 0.0149 (5) | 0.0429 (6) | 0.0292 (6) | 0.0012 (4) | 0.0023 (4) | 0.0136 (5) |
Br2 | 0.0259 (6) | 0.0201 (5) | 0.0273 (5) | −0.0046 (4) | −0.0076 (4) | 0.0071 (4) |
Br3 | 0.0416 (7) | 0.0325 (6) | 0.0337 (6) | 0.0059 (5) | −0.0020 (5) | 0.0212 (5) |
N1 | 0.014 (4) | 0.013 (4) | 0.023 (4) | −0.002 (3) | −0.005 (3) | 0.006 (3) |
C1 | 0.012 (5) | 0.038 (6) | 0.036 (6) | −0.002 (4) | −0.004 (4) | 0.022 (5) |
C2 | 0.028 (6) | 0.024 (5) | 0.028 (6) | 0.001 (4) | −0.006 (5) | 0.014 (5) |
C3 | 0.015 (6) | 0.044 (6) | 0.056 (7) | −0.013 (5) | −0.012 (5) | 0.038 (6) |
C4 | 0.017 (5) | 0.031 (5) | 0.013 (5) | 0.000 (4) | −0.002 (4) | 0.006 (4) |
C5 | 0.012 (5) | 0.020 (5) | 0.015 (5) | 0.006 (4) | 0.002 (4) | 0.004 (4) |
C6 | 0.009 (5) | 0.025 (5) | 0.014 (5) | −0.004 (4) | 0.002 (4) | 0.000 (4) |
N2 | 0.012 (4) | 0.012 (4) | 0.037 (5) | 0.000 (3) | 0.004 (3) | 0.007 (4) |
C7 | 0.025 (6) | 0.025 (5) | 0.018 (5) | −0.006 (4) | −0.003 (4) | 0.007 (4) |
C8 | 0.019 (6) | 0.044 (6) | 0.022 (5) | −0.007 (5) | 0.002 (4) | 0.023 (5) |
C9 | 0.018 (6) | 0.031 (5) | 0.036 (6) | 0.001 (4) | 0.001 (4) | 0.026 (5) |
C10 | 0.015 (5) | 0.025 (5) | 0.031 (6) | −0.003 (4) | 0.011 (4) | 0.013 (4) |
C11 | 0.007 (5) | 0.027 (5) | 0.025 (5) | 0.000 (4) | 0.005 (4) | 0.018 (4) |
C12 | 0.011 (5) | 0.018 (4) | 0.023 (5) | 0.000 (4) | 0.007 (4) | 0.004 (4) |
N3 | 0.013 (4) | 0.014 (4) | 0.016 (4) | 0.000 (3) | 0.004 (3) | 0.007 (3) |
C13 | 0.011 (5) | 0.022 (5) | 0.033 (6) | 0.005 (4) | 0.008 (4) | 0.015 (5) |
C14 | 0.010 (5) | 0.016 (5) | 0.035 (6) | −0.002 (4) | 0.009 (4) | 0.000 (4) |
C15 | 0.013 (5) | 0.029 (5) | 0.033 (6) | 0.003 (4) | 0.007 (4) | 0.009 (5) |
C16 | 0.011 (5) | 0.033 (5) | 0.013 (5) | 0.008 (4) | 0.004 (4) | 0.007 (4) |
C17 | 0.011 (5) | 0.011 (4) | 0.017 (5) | 0.002 (3) | 0.010 (4) | 0.000 (4) |
C18 | 0.008 (5) | 0.029 (5) | 0.019 (5) | 0.006 (4) | 0.002 (4) | 0.015 (4) |
N4 | 0.013 (4) | 0.012 (3) | 0.018 (4) | −0.002 (3) | 0.003 (3) | 0.001 (3) |
C19 | 0.014 (5) | 0.025 (5) | 0.018 (5) | 0.006 (4) | 0.004 (4) | 0.005 (4) |
C20 | 0.011 (5) | 0.021 (4) | 0.020 (5) | −0.002 (4) | 0.000 (4) | 0.013 (4) |
N5 | 0.009 (4) | 0.017 (4) | 0.017 (4) | 0.002 (3) | −0.002 (3) | 0.003 (3) |
C21 | 0.016 (5) | 0.016 (5) | 0.024 (5) | −0.001 (4) | 0.000 (4) | 0.002 (4) |
C22 | 0.004 (5) | 0.037 (6) | 0.021 (5) | 0.003 (4) | −0.002 (4) | 0.005 (5) |
O1 | 0.016 (4) | 0.027 (3) | 0.016 (3) | −0.004 (3) | −0.002 (3) | 0.009 (3) |
O2 | 0.052 (5) | 0.034 (4) | 0.027 (4) | 0.003 (3) | 0.010 (4) | 0.002 (3) |
Cu3 | 0.0218 (7) | 0.0166 (5) | 0.0248 (6) | 0.0003 (5) | 0.0058 (5) | 0.0066 (5) |
Cu4 | 0.0207 (7) | 0.0143 (5) | 0.0272 (6) | 0.0030 (5) | 0.0062 (5) | 0.0087 (5) |
Br4 | 0.0209 (6) | 0.0246 (5) | 0.0360 (6) | 0.0025 (4) | 0.0038 (4) | 0.0076 (4) |
Br5 | 0.0682 (9) | 0.0290 (5) | 0.0333 (6) | −0.0026 (5) | 0.0200 (6) | 0.0132 (5) |
Br6 | 0.0423 (7) | 0.0168 (5) | 0.0332 (6) | −0.0038 (4) | 0.0032 (5) | 0.0081 (4) |
N6 | 0.018 (4) | 0.018 (4) | 0.030 (5) | 0.001 (3) | 0.006 (3) | 0.007 (4) |
C23 | 0.030 (6) | 0.029 (5) | 0.027 (6) | −0.011 (4) | 0.006 (5) | 0.011 (5) |
C24 | 0.014 (5) | 0.028 (5) | 0.031 (6) | 0.001 (4) | 0.007 (4) | 0.002 (5) |
C25 | 0.030 (6) | 0.017 (5) | 0.058 (8) | 0.000 (4) | 0.013 (5) | 0.016 (5) |
C26 | 0.017 (6) | 0.022 (5) | 0.050 (7) | 0.003 (4) | 0.007 (5) | 0.022 (5) |
C27 | 0.006 (5) | 0.028 (5) | 0.029 (6) | −0.001 (4) | 0.006 (4) | 0.012 (5) |
C28 | 0.012 (5) | 0.027 (5) | 0.034 (6) | 0.000 (4) | 0.008 (4) | 0.015 (4) |
N7 | 0.022 (5) | 0.017 (4) | 0.027 (5) | 0.006 (3) | 0.006 (4) | 0.006 (3) |
C29 | 0.017 (5) | 0.031 (5) | 0.038 (6) | −0.005 (4) | 0.002 (4) | 0.021 (5) |
C30 | 0.033 (7) | 0.014 (5) | 0.047 (7) | −0.003 (4) | 0.003 (5) | 0.006 (5) |
C31 | 0.027 (6) | 0.022 (5) | 0.043 (7) | −0.003 (4) | 0.009 (5) | −0.005 (5) |
C32 | 0.013 (5) | 0.034 (6) | 0.031 (6) | −0.002 (4) | 0.003 (4) | 0.004 (5) |
C33 | 0.014 (5) | 0.023 (5) | 0.028 (6) | −0.002 (4) | 0.010 (4) | 0.005 (4) |
C34 | 0.021 (6) | 0.031 (5) | 0.026 (5) | 0.003 (4) | 0.012 (4) | 0.014 (4) |
N8 | 0.012 (4) | 0.016 (4) | 0.022 (4) | −0.003 (3) | 0.003 (3) | 0.003 (3) |
C35 | 0.015 (5) | 0.033 (5) | 0.023 (6) | −0.006 (4) | −0.001 (4) | 0.008 (5) |
C36 | 0.027 (6) | 0.033 (6) | 0.027 (5) | 0.005 (4) | 0.008 (4) | 0.020 (5) |
C37 | 0.029 (6) | 0.019 (5) | 0.033 (6) | 0.008 (4) | 0.007 (5) | 0.017 (4) |
C38 | 0.025 (6) | 0.023 (5) | 0.026 (6) | −0.003 (4) | 0.008 (4) | 0.009 (4) |
C39 | 0.009 (5) | 0.016 (4) | 0.022 (5) | −0.002 (4) | 0.008 (4) | 0.002 (4) |
C40 | 0.016 (5) | 0.017 (4) | 0.022 (5) | −0.003 (4) | 0.005 (4) | 0.011 (4) |
N9 | 0.009 (4) | 0.026 (4) | 0.026 (4) | 0.000 (3) | 0.002 (3) | 0.012 (4) |
C41 | 0.019 (6) | 0.025 (5) | 0.023 (5) | −0.002 (4) | 0.003 (4) | 0.004 (4) |
C42 | 0.012 (5) | 0.014 (4) | 0.023 (5) | −0.006 (4) | 0.007 (4) | 0.004 (4) |
N10 | 0.003 (4) | 0.022 (4) | 0.027 (4) | −0.001 (3) | 0.001 (3) | 0.010 (3) |
C43 | 0.028 (6) | 0.024 (5) | 0.033 (6) | −0.006 (4) | −0.004 (5) | 0.018 (5) |
C44 | 0.016 (6) | 0.046 (7) | 0.049 (7) | −0.009 (5) | −0.008 (5) | 0.036 (6) |
O3 | 0.021 (4) | 0.025 (3) | 0.047 (5) | −0.001 (3) | 0.002 (3) | 0.020 (3) |
O4 | 0.077 (6) | 0.050 (5) | 0.064 (6) | −0.005 (4) | −0.034 (5) | 0.036 (4) |
O5 | 0.016 (4) | 0.043 (4) | 0.027 (4) | −0.001 (3) | 0.003 (3) | 0.006 (3) |
O6 | 0.027 (4) | 0.042 (4) | 0.023 (4) | −0.001 (3) | 0.003 (3) | 0.009 (3) |
O7 | 0.025 (4) | 0.030 (4) | 0.030 (4) | 0.000 (3) | 0.003 (3) | 0.008 (3) |
O8 | 0.056 (5) | 0.047 (4) | 0.037 (4) | −0.009 (4) | −0.001 (4) | 0.024 (4) |
O9 | 0.027 (4) | 0.042 (4) | 0.036 (4) | 0.010 (3) | 0.011 (3) | 0.014 (3) |
O10 | 0.051 (5) | 0.042 (4) | 0.043 (4) | 0.007 (4) | 0.006 (4) | 0.025 (4) |
O11 | 0.101 (9) | 0.129 (9) | 0.076 (7) | 0.025 (7) | 0.002 (6) | 0.065 (7) |
O12 | 0.056 (10) | 0.022 (7) | 0.037 (8) | 0.000 (6) | −0.002 (7) | 0.015 (6) |
Cu1—N1 | 1.982 (7) | Cu3—N6 | 1.998 (7) |
Cu1—N2 | 1.989 (7) | Cu3—N7 | 1.986 (7) |
Cu1—N4 | 2.133 (6) | Cu3—N9 | 2.075 (7) |
Cu2—O1 | 1.944 (5) | Cu3—Br4 | 2.7342 (15) |
Cu1—Br2 | 2.4361 (13) | Cu3—Br5 | 2.4102 (14) |
Cu1—Br1 | 2.5228 (14) | Cu4—N8 | 1.955 (7) |
Cu2—N3 | 1.970 (6) | Cu4—N10 | 2.023 (7) |
Cu2—N5 | 2.046 (6) | Cu4—O3 | 1.900 (6) |
Cu2—O5 | 2.309 (6) | Cu4—Br6 | 2.3496 (14) |
Cu2—Br3 | 2.3832 (13) | N6—C23 | 1.337 (11) |
N1—C5 | 1.340 (10) | N6—C27 | 1.343 (11) |
N1—C1 | 1.343 (10) | C23—C24 | 1.378 (12) |
C1—C2 | 1.371 (11) | C23—H23 | 0.9500 |
C1—H1 | 0.9500 | C24—C25 | 1.375 (12) |
C2—C3 | 1.371 (13) | C24—H24 | 0.9500 |
C2—H2 | 0.9500 | C25—C26 | 1.387 (13) |
C3—C4 | 1.391 (12) | C25—H25 | 0.9500 |
C3—H3 | 0.9500 | C26—C27 | 1.365 (11) |
C4—C5 | 1.395 (11) | C26—H26 | 0.9500 |
C4—H4 | 0.9500 | C27—C28 | 1.509 (12) |
C5—C6 | 1.515 (11) | C28—N9 | 1.494 (10) |
C6—N4 | 1.475 (10) | C28—H28A | 0.9900 |
C6—H6A | 0.9900 | C28—H28B | 0.9900 |
C6—H6B | 0.9900 | N7—C33 | 1.340 (11) |
N2—C11 | 1.326 (10) | N7—C29 | 1.365 (10) |
N2—C7 | 1.359 (11) | C29—C30 | 1.367 (12) |
C7—C8 | 1.389 (11) | C29—H29 | 0.9500 |
C7—H7 | 0.9500 | C30—C31 | 1.386 (13) |
C8—C9 | 1.347 (12) | C30—H30 | 0.9500 |
C8—H8 | 0.9500 | C31—C32 | 1.381 (12) |
C9—C10 | 1.369 (12) | C31—H31 | 0.9500 |
C9—H9 | 0.9500 | C32—C33 | 1.390 (12) |
C10—C11 | 1.405 (11) | C32—H32 | 0.9500 |
C10—H10 | 0.9500 | C33—C34 | 1.527 (11) |
C11—C12 | 1.504 (11) | C34—N9 | 1.500 (10) |
C12—N4 | 1.487 (10) | C34—H34A | 0.9900 |
C12—H12A | 0.9900 | C34—H34B | 0.9900 |
C12—H12B | 0.9900 | N8—C35 | 1.336 (10) |
N3—C13 | 1.325 (10) | N8—C39 | 1.375 (10) |
N3—C17 | 1.343 (9) | C35—C36 | 1.385 (11) |
C13—C14 | 1.383 (12) | C35—H35 | 0.9500 |
C13—H13 | 0.9500 | C36—C37 | 1.362 (11) |
C14—C15 | 1.364 (12) | C36—H36 | 0.9500 |
C14—H14 | 0.9500 | C37—C38 | 1.371 (12) |
C15—C16 | 1.409 (11) | C37—H37 | 0.9500 |
C15—H15 | 0.9500 | C38—C39 | 1.392 (11) |
C16—C17 | 1.388 (11) | C38—H38 | 0.9500 |
C16—H16 | 0.9500 | C39—C40 | 1.489 (11) |
C17—C18 | 1.500 (10) | C40—N10 | 1.471 (10) |
C18—N5 | 1.474 (10) | C40—H40A | 0.9900 |
C18—H18A | 0.9900 | C40—H40B | 0.9900 |
C18—H18B | 0.9900 | N9—C41 | 1.498 (10) |
N4—C19 | 1.485 (10) | C41—C42 | 1.535 (11) |
C19—C20 | 1.532 (11) | C41—H41A | 0.9900 |
C19—H19A | 0.9900 | C41—H41B | 0.9900 |
C19—H19B | 0.9900 | C42—N10 | 1.477 (10) |
C20—N5 | 1.513 (10) | C42—H42A | 0.9900 |
C20—H20A | 0.9900 | C42—H42B | 0.9900 |
C20—H20B | 0.9900 | N10—C43 | 1.492 (10) |
N5—C21 | 1.488 (9) | C43—C44 | 1.534 (12) |
C21—C22 | 1.501 (11) | C43—H43A | 0.9900 |
C21—H21A | 0.9900 | C43—H43B | 0.9900 |
C21—H21B | 0.9900 | C44—O4 | 1.240 (11) |
C22—O2 | 1.248 (10) | C44—O3 | 1.271 (11) |
C22—O1 | 1.292 (10) | ||
N1—Cu1—N2 | 163.4 (3) | O1—C22—C21 | 118.1 (7) |
N1—Cu1—N4 | 81.7 (3) | C22—O1—Cu2 | 113.7 (5) |
N2—Cu1—N4 | 82.1 (3) | N7—Cu3—N6 | 164.5 (3) |
N1—Cu1—Br2 | 95.53 (19) | N7—Cu3—N9 | 82.7 (3) |
N2—Cu1—Br2 | 97.3 (2) | N6—Cu3—N9 | 82.1 (3) |
N4—Cu1—Br2 | 127.66 (18) | N7—Cu3—Br5 | 96.3 (2) |
N1—Cu1—Br1 | 90.5 (2) | N6—Cu3—Br5 | 97.4 (2) |
N2—Cu1—Br1 | 92.5 (2) | N9—Cu3—Br5 | 141.93 (19) |
N4—Cu1—Br1 | 113.38 (18) | N7—Cu3—Br4 | 91.0 (2) |
Br2—Cu1—Br1 | 118.91 (5) | N6—Cu3—Br4 | 88.7 (2) |
O1—Cu2—N3 | 166.6 (2) | N9—Cu3—Br4 | 99.52 (19) |
O1—Cu2—N5 | 83.8 (2) | Br5—Cu3—Br4 | 118.54 (5) |
N3—Cu2—N5 | 84.0 (3) | O3—Cu4—N8 | 156.6 (3) |
O1—Cu2—O5 | 86.6 (2) | O3—Cu4—N10 | 86.3 (3) |
N3—Cu2—O5 | 88.4 (2) | N8—Cu4—N10 | 84.2 (3) |
N5—Cu2—O5 | 92.0 (2) | O3—Cu4—Br6 | 98.34 (19) |
O1—Cu2—Br3 | 93.36 (17) | N8—Cu4—Br6 | 100.6 (2) |
N3—Cu2—Br3 | 99.98 (19) | N10—Cu4—Br6 | 149.85 (19) |
N5—Cu2—Br3 | 148.96 (19) | C23—N6—C27 | 119.2 (7) |
O5—Cu2—Br3 | 118.76 (16) | C23—N6—Cu3 | 127.5 (6) |
C5—N1—C1 | 119.1 (7) | C27—N6—Cu3 | 113.3 (6) |
C5—N1—Cu1 | 113.8 (5) | N6—C23—C24 | 121.8 (9) |
C1—N1—Cu1 | 127.1 (6) | N6—C23—H23 | 119.1 |
N1—C1—C2 | 121.3 (8) | C24—C23—H23 | 119.1 |
N1—C1—H1 | 119.3 | C25—C24—C23 | 119.4 (9) |
C2—C1—H1 | 119.3 | C25—C24—H24 | 120.3 |
C3—C2—C1 | 120.4 (8) | C23—C24—H24 | 120.3 |
C3—C2—H2 | 119.8 | C24—C25—C26 | 118.2 (8) |
C1—C2—H2 | 119.8 | C24—C25—H25 | 120.9 |
C2—C3—C4 | 119.0 (8) | C26—C25—H25 | 120.9 |
C2—C3—H3 | 120.5 | C27—C26—C25 | 120.0 (9) |
C4—C3—H3 | 120.5 | C27—C26—H26 | 120.0 |
C3—C4—C5 | 117.9 (8) | C25—C26—H26 | 120.0 |
C3—C4—H4 | 121.0 | N6—C27—C26 | 121.4 (8) |
C5—C4—H4 | 121.0 | N6—C27—C28 | 115.7 (8) |
N1—C5—C4 | 122.3 (7) | C26—C27—C28 | 122.9 (8) |
N1—C5—C6 | 115.1 (7) | N9—C28—C27 | 108.8 (7) |
C4—C5—C6 | 122.6 (7) | N9—C28—H28A | 109.9 |
N4—C6—C5 | 108.8 (6) | C27—C28—H28A | 109.9 |
N4—C6—H6A | 109.9 | N9—C28—H28B | 109.9 |
C5—C6—H6A | 109.9 | C27—C28—H28B | 109.9 |
N4—C6—H6B | 109.9 | H28A—C28—H28B | 108.3 |
C5—C6—H6B | 109.9 | C33—N7—C29 | 117.5 (8) |
H6A—C6—H6B | 108.3 | C33—N7—Cu3 | 115.4 (5) |
C11—N2—C7 | 120.3 (7) | C29—N7—Cu3 | 127.1 (6) |
C11—N2—Cu1 | 114.8 (6) | N7—C29—C30 | 122.0 (9) |
C7—N2—Cu1 | 124.9 (6) | N7—C29—H29 | 119.0 |
N2—C7—C8 | 120.6 (8) | C30—C29—H29 | 119.0 |
N2—C7—H7 | 119.7 | C29—C30—C31 | 119.9 (9) |
C8—C7—H7 | 119.7 | C29—C30—H30 | 120.1 |
C9—C8—C7 | 119.4 (9) | C31—C30—H30 | 120.1 |
C9—C8—H8 | 120.3 | C32—C31—C30 | 119.0 (9) |
C7—C8—H8 | 120.3 | C32—C31—H31 | 120.5 |
C8—C9—C10 | 120.1 (8) | C30—C31—H31 | 120.5 |
C8—C9—H9 | 120.0 | C31—C32—C33 | 118.2 (9) |
C10—C9—H9 | 120.0 | C31—C32—H32 | 120.9 |
C9—C10—C11 | 119.5 (8) | C33—C32—H32 | 120.9 |
C9—C10—H10 | 120.2 | N7—C33—C32 | 123.4 (8) |
C11—C10—H10 | 120.2 | N7—C33—C34 | 116.2 (7) |
N2—C11—C10 | 120.0 (8) | C32—C33—C34 | 120.4 (8) |
N2—C11—C12 | 118.3 (7) | N9—C34—C33 | 110.1 (7) |
C10—C11—C12 | 121.6 (8) | N9—C34—H34A | 109.6 |
N4—C12—C11 | 110.0 (6) | C33—C34—H34A | 109.6 |
N4—C12—H12A | 109.7 | N9—C34—H34B | 109.6 |
C11—C12—H12A | 109.7 | C33—C34—H34B | 109.6 |
N4—C12—H12B | 109.7 | H34A—C34—H34B | 108.2 |
C11—C12—H12B | 109.7 | C35—N8—C39 | 118.5 (7) |
H12A—C12—H12B | 108.2 | C35—N8—Cu4 | 128.3 (6) |
C13—N3—C17 | 118.3 (7) | C39—N8—Cu4 | 113.2 (6) |
C13—N3—Cu2 | 128.9 (6) | N8—C35—C36 | 122.4 (8) |
C17—N3—Cu2 | 112.8 (5) | N8—C35—H35 | 118.8 |
N3—C13—C14 | 123.6 (8) | C36—C35—H35 | 118.8 |
N3—C13—H13 | 118.2 | C37—C36—C35 | 118.8 (9) |
C14—C13—H13 | 118.2 | C37—C36—H36 | 120.6 |
C15—C14—C13 | 118.1 (8) | C35—C36—H36 | 120.6 |
C15—C14—H14 | 121.0 | C36—C37—C38 | 120.7 (8) |
C13—C14—H14 | 121.0 | C36—C37—H37 | 119.7 |
C14—C15—C16 | 120.1 (8) | C38—C37—H37 | 119.7 |
C14—C15—H15 | 120.0 | C37—C38—C39 | 118.6 (8) |
C16—C15—H15 | 120.0 | C37—C38—H38 | 120.7 |
C17—C16—C15 | 117.2 (8) | C39—C38—H38 | 120.7 |
C17—C16—H16 | 121.4 | N8—C39—C38 | 121.0 (8) |
C15—C16—H16 | 121.4 | N8—C39—C40 | 114.4 (7) |
N3—C17—C16 | 122.7 (7) | C38—C39—C40 | 124.5 (7) |
N3—C17—C18 | 116.0 (7) | N10—C40—C39 | 110.9 (7) |
C16—C17—C18 | 121.3 (7) | N10—C40—H40A | 109.5 |
N5—C18—C17 | 110.3 (6) | C39—C40—H40A | 109.5 |
N5—C18—H18A | 109.6 | N10—C40—H40B | 109.5 |
C17—C18—H18A | 109.6 | C39—C40—H40B | 109.5 |
N5—C18—H18B | 109.6 | H40A—C40—H40B | 108.0 |
C17—C18—H18B | 109.6 | C28—N9—C41 | 108.8 (6) |
H18A—C18—H18B | 108.1 | C28—N9—C34 | 112.6 (6) |
C6—N4—C19 | 107.8 (6) | C41—N9—C34 | 112.1 (6) |
C6—N4—C12 | 112.9 (6) | C28—N9—Cu3 | 103.6 (5) |
C19—N4—C12 | 113.4 (6) | C41—N9—Cu3 | 112.4 (5) |
C6—N4—Cu1 | 101.2 (4) | C34—N9—Cu3 | 107.1 (5) |
C19—N4—Cu1 | 115.2 (5) | N9—C41—C42 | 113.5 (7) |
C12—N4—Cu1 | 105.9 (5) | N9—C41—H41A | 108.9 |
N4—C19—C20 | 111.8 (7) | C42—C41—H41A | 108.9 |
N4—C19—H19A | 109.3 | N9—C41—H41B | 108.9 |
C20—C19—H19A | 109.3 | C42—C41—H41B | 108.9 |
N4—C19—H19B | 109.3 | H41A—C41—H41B | 107.7 |
C20—C19—H19B | 109.3 | N10—C42—C41 | 112.1 (6) |
H19A—C19—H19B | 107.9 | N10—C42—H42A | 109.2 |
N5—C20—C19 | 110.1 (6) | C41—C42—H42A | 109.2 |
N5—C20—H20A | 109.6 | N10—C42—H42B | 109.2 |
C19—C20—H20A | 109.6 | C41—C42—H42B | 109.2 |
N5—C20—H20B | 109.6 | H42A—C42—H42B | 107.9 |
C19—C20—H20B | 109.6 | C40—N10—C42 | 108.2 (6) |
H20A—C20—H20B | 108.1 | C40—N10—C43 | 112.9 (6) |
C18—N5—C21 | 114.4 (6) | C42—N10—C43 | 113.5 (7) |
C18—N5—C20 | 108.2 (6) | C40—N10—Cu4 | 105.3 (5) |
C21—N5—C20 | 111.8 (6) | C42—N10—Cu4 | 109.3 (5) |
C18—N5—Cu2 | 104.4 (5) | C43—N10—Cu4 | 107.2 (5) |
C21—N5—Cu2 | 105.4 (5) | N10—C43—C44 | 111.2 (7) |
C20—N5—Cu2 | 112.5 (4) | N10—C43—H43A | 109.4 |
N5—C21—C22 | 110.9 (7) | C44—C43—H43A | 109.4 |
N5—C21—H21A | 109.5 | N10—C43—H43B | 109.4 |
C22—C21—H21A | 109.5 | C44—C43—H43B | 109.4 |
N5—C21—H21B | 109.5 | H43A—C43—H43B | 108.0 |
C22—C21—H21B | 109.5 | O4—C44—O3 | 124.6 (9) |
H21A—C21—H21B | 108.1 | O4—C44—C43 | 117.4 (9) |
O2—C22—O1 | 121.5 (8) | O3—C44—C43 | 118.0 (8) |
O2—C22—C21 | 120.4 (8) | C44—O3—Cu4 | 115.6 (6) |
Experimental details
(I_vCM14088) | (II_vcm14089) | (III_vCM14087twin5) | |
Crystal data | |||
Chemical formula | [Zn2(C22H24N5O2)Cl3] | [Zn2Br3(C22H24N5O2)] | [Cu2Br3(C22H24N5O2)][Cu2Br3(C22H24N5O2)(H2O)]·6.5H2O |
Mr | 627.55 | 760.93 | 1649.66 |
Crystal system, space group | Monoclinic, P21/n | Orthorhombic, Pca21 | Triclinic, P1 |
Temperature (K) | 180 | 180 | 180 |
a, b, c (Å) | 9.4985 (8), 11.3423 (10), 23.3697 (18) | 18.7061 (12), 13.3342 (9), 20.4516 (13) | 11.2516 (9), 15.0606 (10), 18.3213 (14) |
α, β, γ (°) | 90, 98.263 (4), 90 | 90, 90, 90 | 112.087 (3), 94.380 (3), 90.486 (3) |
V (Å3) | 2491.6 (4) | 5101.3 (6) | 2866.1 (4) |
Z | 4 | 8 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 2.28 | 6.61 | 5.71 |
Crystal size (mm) | 0.31 × 0.19 × 0.15 | 0.17 × 0.08 × 0.05 | 0.20 × 0.11 × 0.05 |
Data collection | |||
Diffractometer | Bruker–Nonius X8 APEXII CCD | Bruker–Nonius X8 APEXII CCD | Bruker–Nonius X8 APEXII CCD |
Absorption correction | Multi-scan (SADABS; Krause et al., 2015) | Multi-scan (SADABS; Krause et al., 2015) | Multi-scan (TWINABS; Sheldrick, 2012) |
Tmin, Tmax | 0.469, 0.745 | 0.365, 0.431 | 0.303, 0.430 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 77315, 5051, 4340 | 127653, 11284, 8558 | 11068, 11068, 7261 |
Rint | 0.084 | 0.081 | 0.077 |
(sin θ/λ)max (Å−1) | 0.629 | 0.669 | 0.625 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.099, 1.14 | 0.040, 0.078, 1.02 | 0.054, 0.114, 1.00 |
No. of reflections | 5051 | 11284 | 11068 |
No. of parameters | 307 | 614 | 686 |
No. of restraints | 0 | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.85, −0.48 | 1.26, −0.61 | 0.99, −0.88 |
Absolute structure | ? | Refined as an inversion twin. | ? |
Absolute structure parameter | ? | 0.245 (12) | ? |
Computer programs: APEX2 (Bruker, 2012), SAINT (Bruker, 2012), SHELXT2014 (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), SHELXTL (Bruker, 2012) and Mercury (Macrae et al., 2006), SHELXTL (Bruker, 2012) and publCIF (Westrip, 2010), publCIF (Westrip, 2010).
Zn1—N1 | 2.203 (3) | Zn2—O2 | 1.982 (2) |
Zn1—N2 | 2.061 (3) | Zn2—Cl1 | 2.2618 (10) |
Zn1—N3 | 2.069 (3) | Zn2—Cl2 | 2.2511 (9) |
Zn1—O1 | 2.177 (2) | Zn2—Cl3 | 2.2317 (9) |
N2—Zn1—N3 | 119.85 (10) | N3—Zn1—N1 | 94.10 (11) |
N2—Zn1—O1 | 87.74 (9) | O1—Zn1—N1 | 165.91 (9) |
N3—Zn1—O1 | 95.22 (10) | N4—Zn1—N1 | 78.48 (11) |
N2—Zn1—N4 | 80.25 (10) | N5—Zn1—N1 | 92.94 (10) |
N3—Zn1—N4 | 159.51 (10) | O2—Zn2—Cl3 | 111.52 (8) |
O1—Zn1—N4 | 89.19 (9) | O2—Zn2—Cl2 | 107.91 (8) |
N2—Zn1—N5 | 158.26 (11) | Cl3—Zn2—Cl2 | 113.68 (4) |
N3—Zn1—N5 | 78.60 (10) | O2—Zn2—Cl1 | 100.32 (8) |
O1—Zn1—N5 | 78.60 (9) | Cl3—Zn2—Cl1 | 109.17 (4) |
N4—Zn1—N5 | 82.70 (10) | Cl2—Zn2—Cl1 | 113.46 (4) |
N2—Zn1—N1 | 96.75 (11) |
Zn1—N1 | 2.200 (7) | Zn3—N6 | 2.207 (6) |
Zn1—N2 | 2.094 (7) | Zn3—N7 | 2.088 (6) |
Zn1—N3 | 2.080 (7) | Zn3—N8 | 2.094 (7) |
Zn1—N4 | 2.182 (7) | Zn3—N9 | 2.183 (7) |
Zn1—N5 | 2.192 (6) | Zn3—N10 | 2.194 (6) |
Zn1—O1 | 2.184 (5) | Zn3—O3 | 2.202 (5) |
Zn2—O2 | 2.001 (6) | Zn4—O4 | 2.008 (6) |
Zn2—Br1 | 2.3721 (13) | Zn4—Br4 | 2.3816 (12) |
Zn2—Br2 | 2.3953 (12) | Zn4—Br5 | 2.3856 (12) |
Zn2—Br3 | 2.3776 (12) | Zn4—Br6 | 2.4161 (11) |
N3—Zn1—N2 | 118.6 (2) | N7—Zn3—N8 | 118.7 (2) |
N3—Zn1—N4 | 160.0 (2) | N7—Zn3—N9 | 79.3 (3) |
N2—Zn1—N4 | 80.6 (3) | N8—Zn3—N9 | 156.9 (3) |
N3—Zn1—O1 | 94.3 (2) | N7—Zn3—N10 | 160.7 (2) |
N2—Zn1—O1 | 87.2 (2) | N8—Zn3—N10 | 80.3 (2) |
N4—Zn1—O1 | 92.1 (2) | N9—Zn3—N10 | 83.5 (3) |
N3—Zn1—N5 | 79.7 (3) | N7—Zn3—O3 | 95.0 (2) |
N2—Zn1—N5 | 157.6 (3) | N8—Zn3—O3 | 85.9 (2) |
N4—Zn1—N5 | 83.2 (3) | N9—Zn3—O3 | 77.8 (3) |
O1—Zn1—N5 | 78.0 (2) | N10—Zn3—O3 | 89.7 (2) |
N3—Zn1—N1 | 92.2 (2) | N7—Zn3—N6 | 95.0 (2) |
N2—Zn1—N1 | 97.1 (2) | N8—Zn3—N6 | 95.9 (2) |
N4—Zn1—N1 | 79.0 (2) | N9—Zn3—N6 | 96.7 (3) |
O1—Zn1—N1 | 169.4 (2) | N10—Zn3—N6 | 78.4 (2) |
N5—Zn1—N1 | 94.9 (3) | O3—Zn3—N6 | 167.5 (2) |
O2—Zn2—Br1 | 109.13 (16) | O4—Zn4—Br4 | 111.24 (18) |
O2—Zn2—Br3 | 106.34 (17) | O4—Zn4—Br5 | 107.97 (16) |
Br1—Zn2—Br3 | 114.46 (5) | Br4—Zn4—Br5 | 114.75 (5) |
O2—Zn2—Br2 | 101.41 (17) | O4—Zn4—Br6 | 101.45 (17) |
Br1—Zn2—Br2 | 112.24 (5) | Br4—Zn4—Br6 | 110.00 (4) |
Br3—Zn2—Br2 | 112.20 (5) | Br5—Zn4—Br6 | 110.60 (5) |
Cu1—N1 | 1.982 (7) | Cu3—N6 | 1.998 (7) |
Cu1—N2 | 1.989 (7) | Cu3—N7 | 1.986 (7) |
Cu1—N4 | 2.133 (6) | Cu3—N9 | 2.075 (7) |
Cu2—O1 | 1.944 (5) | Cu3—Br4 | 2.7342 (15) |
Cu1—Br2 | 2.4361 (13) | Cu3—Br5 | 2.4102 (14) |
Cu1—Br1 | 2.5228 (14) | Cu4—N8 | 1.955 (7) |
Cu2—N3 | 1.970 (6) | Cu4—N10 | 2.023 (7) |
Cu2—N5 | 2.046 (6) | Cu4—O3 | 1.900 (6) |
Cu2—O5 | 2.309 (6) | Cu4—Br6 | 2.3496 (14) |
Cu2—Br3 | 2.3832 (13) | ||
N1—Cu1—N2 | 163.4 (3) | N5—Cu2—Br3 | 148.96 (19) |
N1—Cu1—N4 | 81.7 (3) | O5—Cu2—Br3 | 118.76 (16) |
N2—Cu1—N4 | 82.1 (3) | N7—Cu3—N6 | 164.5 (3) |
N1—Cu1—Br2 | 95.53 (19) | N7—Cu3—N9 | 82.7 (3) |
N2—Cu1—Br2 | 97.3 (2) | N6—Cu3—N9 | 82.1 (3) |
N4—Cu1—Br2 | 127.66 (18) | N7—Cu3—Br5 | 96.3 (2) |
N1—Cu1—Br1 | 90.5 (2) | N6—Cu3—Br5 | 97.4 (2) |
N2—Cu1—Br1 | 92.5 (2) | N9—Cu3—Br5 | 141.93 (19) |
N4—Cu1—Br1 | 113.38 (18) | N7—Cu3—Br4 | 91.0 (2) |
Br2—Cu1—Br1 | 118.91 (5) | N6—Cu3—Br4 | 88.7 (2) |
O1—Cu2—N3 | 166.6 (2) | N9—Cu3—Br4 | 99.52 (19) |
O1—Cu2—N5 | 83.8 (2) | Br5—Cu3—Br4 | 118.54 (5) |
N3—Cu2—N5 | 84.0 (3) | O3—Cu4—N8 | 156.6 (3) |
O1—Cu2—O5 | 86.6 (2) | O3—Cu4—N10 | 86.3 (3) |
N3—Cu2—O5 | 88.4 (2) | N8—Cu4—N10 | 84.2 (3) |
N5—Cu2—O5 | 92.0 (2) | O3—Cu4—Br6 | 98.34 (19) |
O1—Cu2—Br3 | 93.36 (17) | N8—Cu4—Br6 | 100.6 (2) |
N3—Cu2—Br3 | 99.98 (19) | N10—Cu4—Br6 | 149.85 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···Br4 | 0.95 | 3.12 | 3.700 (8) | 121 |
C6—H6A···Br3i | 0.99 | 3.12 | 3.724 (8) | 121 |
C6—H6B···Br2i | 0.99 | 2.81 | 3.710 (8) | 152 |
C12—H12B···Br1 | 0.99 | 2.88 | 3.853 (8) | 167 |
C13—H13···O3 | 0.95 | 2.38 | 3.145 (10) | 137 |
C14—H14···Br5 | 0.95 | 3.05 | 3.939 (9) | 157 |
C15—H15···Br3ii | 0.95 | 2.76 | 3.578 (8) | 145 |
C18—H18A···Br6iii | 0.99 | 2.85 | 3.764 (8) | 155 |
C18—H18B···Br1iv | 0.99 | 3.05 | 3.583 (10) | 115 |
C19—H19B···Br3i | 0.99 | 2.92 | 3.747 (9) | 141 |
C26—H26···O4v | 0.95 | 2.54 | 3.381 (11) | 148 |
C28—H28A···Br6v | 0.99 | 2.85 | 3.762 (8) | 154 |
C29—H29···O1 | 0.95 | 2.53 | 3.334 (9) | 142 |
C34—H34B···Br2ii | 0.99 | 2.77 | 3.698 (7) | 157 |
C40—H40A···Br5 | 0.99 | 2.84 | 3.801 (8) | 165 |
C42—H42A···Br4v | 0.99 | 3.07 | 3.900 (8) | 142 |
Symmetry codes: (i) x+1/2, −y+2, z; (ii) x, y−1, z; (iii) x, y+1, z; (iv) −x+1, −y+2, z+1/2; (v) x−1/2, −y+1, z. |
Hydrogen bond | D···A | Hydrogen bond | D···A |
O5 ···O6i | 2.764 (8) | O9···Br4 | 3.335 (6) |
O5···Br1ii | 3.199 (6) | O9···O10 | 2.794 (9) |
O6···O8 | 2.973 (8) | O10···O4iii | 2.813 (10) |
O6···O9 | 2.770 (8) | O10···O8 | 2.885 (10) |
O7···O6 | 2.717 (8) | O11···Br4 | 3.455 (8) |
O7···Br3 | 3.275 (6) | O11···Br5 | 3.480 (10) |
O8···O4ii | 3.052 (10) | O12···O2i | 2.575 (14) |
O8···O12 | 2.860 (15) | O12···O2iv | 2.834 (13) |
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x-1, y, z; (iii) -x+2, -y, -z+1; (iv) x, y-1, z. |