Comparison of copper imine and amine podates: geometric consequences of podand size and donor type

Coyle, J.L.; Fuller, A.; McKee, V.; Nelson, J.

doi:10.1107/S0108270106034524

metal-organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 62| Part 10| October 2006| Pages m472-m476

doi:10.1107/S0108270106034524

Comparison of copper imine and amine podates: geometric consequences of podand size and donor type

Joanne L. Coyle,^a Anna Fuller,^b Vickie McKee ^b ^* and Jane Nelson ^b

^aChemistry Department, The Open University, Milton Keynes MK7 6AA, England, and ^bChemistry Department, Loughborough University, Loughborough, Leicestershire LE11 3TU, England
^*Correspondence e-mail: v.mckee@lboro.ac.uk

(Received 11 August 2006; accepted 28 August 2006; online 12 September 2006)

The imine podands tris[(2-nitrobenzylidene)aminoethyl]amine and tris[(2-nitrobenzylidene)aminopropyl]amine both stabilize copper(I), forming {tris[(2-nitrobenzylidene)aminoethyl]amine-κ⁴N}copper(I) perchlorate acetonitrile disolvate, [Cu(C₂₇H₂₇N₇O₆)]ClO₄·2CH₃CN, (II), and {tris[(2-nitrobenzylidene)aminopropyl]amine-κ⁴N}copper(I) perchlorate, [Cu(C₃₀H₃₃N₇O₆)]ClO₄, (VI), respectively. The larger propyl-based ligand is a poorer fit for the Cu^I ion. The reduced amine podand tris[(2-nitrobenzyl)aminoethyl]amine binds Cu^II and the resulting compound, chloro{tris[(2-nitrobenzyl)aminoethyl]amine-κ⁴N}copper(II) chloride ethanol solvate, [Cu(C₂₇H₃₃N₇O₆)Cl]Cl·C₂H₅OH, (IV), shows both intra- and intermolecular hydrogen bonding, which gives rise to RRS or SSR conformations in the podand strands rather than the expected pseudo-threefold symmetry.

Comment

We have had a long-standing interest in the chemistry of both imine and amine cryptates derived from tris(aminoethyl)amine (tren) and tris(3-aminoisopropyl)amine (trpn) [see, for example, McKee et al. (2003 ) and Nelson et al. (1998 )]. We have investigated some simple podate complexes derived from the same amines in order to clarify the geometric requirements associated with each (Coyle, 1999 ). A search of the Cambridge Structural Database (Version 5.27; Allen, 2002 ; Fletcher et al., 1996 ) showed that, although many tris(aminoethyl)amine/salicylate complexes have been investigated, surprisingly few simple podates with other substituted benzaldehyde derivatives have been structurally characterized to date. In this paper, we compare the structures of two Cu^I podates, one derived from tris(aminoethyl)amine (tren) and one from tris(aminopropyl)amine (trpn), with the Cu^II amine analogue of the smaller tren-based podate.

In podate and cryptate complexes with potential threefold symmetry, imine donors typically stabilize Cu^I and are easily hydrolysed by Cu^II (Harding et al., 1995 ; Arthurs et al., 2001 ). Reduction of the imine donors to the corresponding amines generates a site in which Cu^I is activated to reaction with dioxygen, as shown elegantly by Suzuki, Schindler and their co-workers (Komiyama et al., 2004 ; Schatz et al., 2001 ). However, Cu^II binds readily to the reduced ligands.

The structure of the imine podand tris[(2-nitrobenzylidene)aminoethyl]amine, (I), was reported recently (McKee et al., 2006 ). Reaction of (I) with Cu(CH₃CN)₄ClO₄ in acetonitrile gave the Cu^I complex [Cu(I)]ClO₄·2CH₃CN, (II), as dark-brown crystals (Fig. 1). The Cu^I ion is coordinated to all four N atoms in an approximately trigonal–pyramidal geometry (Table 1), although the bonds to the imine N atoms [average 2.003 (2) Å] are significantly shorter than that to the bridgehead amine [Cu1—N1 = 2.196 (1) Å], and the Cu^I ion is 0.172 (1) Å out of the mean plane of the imine N atoms in the opposite direction to the bridgehead. The nitro groups are not involved in the coordination of the metal and the three strands are arranged fairly tightly about the approximate threefold axis. There are two important factors controlling this geometry, namely the essentially planar geometry at the imine N atoms [angle sums 359.9 (2), 359.9 (2) and 359.8 (2)° for atoms N11, N21 and N31, respectively] and the steric demands imposed by coordination of all four N donors of the ligand. These result in the C—N=C plane being tilted with respect to the `default' orientation (parallel to the pseudo-threefold axis and perpendicular to the plane of the three sp²-hybridized imine donors); the interplanar angles are 71.6 (1), 73.5 (1) and 74.1 (1)° for the N11, N21 and N31 strands, respectively. In other words, the orientation of the conjugated nitrobenzylidene strands is determined by the orientation of the imine lone pairs. It is therefore not surprising that this geometry is common for tren-based imine podands in the absence of additional intra- or intermolecular interactions. There are no significant interactions between the cation and perchlorate anion or solvent molecules. The anion is disordered and was modelled with approximately 10% occupancy of the minor orientation (Fig. 1).

The amine podand, tris[(2-nitrobenzyl)aminoethyl]amine, (III), was obtained by reduction of (I) with NaBH₄, which reduced the imine groups but not the nitro substituents. Reaction of ligand (III) with CuCl₂ in ethanol yielded the amine complex [Cu(III)Cl]Cl·C₂H₅OH, (IV), as green crystals. The formula unit of (IV) is shown in Fig. 2. The geometry at the Cu^I ion is approximately trigonal–bipyramidal (Table 2), with the bridghead tertiary amine and the coordinated Cl⁻ ion as apical donors. The coordination geometry is similar to that observed for the analogous Cu^II podate derived from benzaldehyde [tris(benzylaminoethyl)amine; Komiyama et al., 2004; Schatz et al., 2001).

Two of the nitro groups of (IV) are hydrogen bonded to the adjacent secondary amines (Table 3), but the third strand is different, with the amine (N31) hydrogen bonded to the ethanol solvent molecule. Consequently, the configuration at N31 is opposite to that at N11 and N21 (SRR in Fig. 2, although, since the structure is centrosymmetric, the RSS configuration is also present). This difference breaks the pseudo-threefold symmetry of the cation. The non-coordinated Cl⁻ ion Cl2 makes a relatively short hydrogen bond to the ethanol solvent molecule [3.105 (4) Å] and shows further interactions with N21 and with N11 of an adjacent molecule. The latter two interactions are long for hydrogen bonds to Cl⁻, at 3.302 (4) and 3.474 (4) Å, respectively (Steiner, 2002 ). However, both are bifurcated and involve coordinated amines. The resulting hydrogen-bond pattern links the structure in chains running parallel to the b axis (Fig. 3). The most notable interaction between these chains is a π–π interaction between the C24–C29 ring and its symmetry equivalent by inversion under (1 − x, −y, 1 − z); the rings are necessarily parallel, the interplanar distance is 3.393 (4) Å and centroid-to-centroid distance is 3.710 (4) Å.

Complex (VI), namely {tris[(2-nitrobenzylidene)aminopropyl]amine}copper(I) perchlorate, is analogous to complex (II), except that the longer tripodal amine tris(aminopropyl)amine (trpn) is used in place of tren. As for (II), the Cu ion is stabliized in the +1 state and has trigonal–pyramidal geometry (Fig. 4 and Table 4). However, the Cu^I ion is displaced from the imine plane by 0.167 (1) Å towards the bridgehead [i.e. in the opposite sense from complex (II)]. As observed for complex (II), the requirement to coordinate the Cu^I ion to all four N-atom donors results in tilting of the C—N=C planes relative to the plane of the three sp²-hybridized imine donors. In complex (VI), however, this effect is much more pronounced [interplanar angles 34.9 (2), 36.3 (2) and 39.4 (2)° for atoms N11, N21 and N31, respectively].

The three-dimensional `podand bite' in the two Cu^I complexes, (II) and (VI), can be compared by considering the dimensions of the trigonal pyramid formed by the four N-atom donors, with the tertiary amine (N1) at the apex and the imine atoms N11, N21 and N31 in the basal plane. As mentioned above, the Cu^I ion is outside the pyramid in complex (II) and inside for (VI). However, the Cu—N1 distances are identical [2.196 (2) Å] and the Cu—N(imine) bonds are only marginally different [mean values 2.003 (2) Å for (II) and 2.018 (2) Å for (VI)]. The mean imine–imine distances in the basal plane are similar [3.456 and 3.483 Å for (II) and (VI), respectively], but the mean base–apex edges are significantly different [2.842 (2) Å for (II) and 3.103 (2) for (VI)]. An indication of steric strain in complex (VI) is given by the N—C—C and C—C—C angles in the saturated chain between N1 and the imine N atoms; the average angle is 114.4 (3)°, compared with 110.5 (2)° for complex (II).

We have observed similar patterns in the geometry of Cu ions in cryptand hosts derived from tren and trpn [see, for example, Farrar et al. (1995 ) and Nelson et al. (1998)], supporting the suggestion that steric constraints mean that the larger podand has more difficulty accommodating bonding between the Cu^I ion and all four donors than the smaller analogue. These results also go some way to explaining the initially counterintuitive finding that, in the dinuclear iminocryptate series, the shortest internuclear distances between cationic guests are found for the larger hosts (Drew et al., 2000 ; Farrar et al., 1995; Nelson et al., 1998). In the case of the cryptand ligands, the twist imposed on each strand by the coordination of the imine donors shortens the distance between the two metal binding sites.

Figure 1
The structure of complex (II)

, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity. The minor component of the disordered ClO₄⁻ ion is indicated by open bonds.

Figure 2
The structure of complex (IV)

, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

Figure 3
A packing plot for complex (IV)

, viewed down the b axis. Hydrogen bonds are shown as dashed lines and the π–π interactions are indicated by open bonds linking ring centroids. Key: Cl atoms are shown cross-hatched, Cu atoms are shaded top left to bottom right, N atoms are dotted, and O atoms are shaded bottom left to upper right.

Figure 4
The structure of complex (VI)

, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms have been omitted for clarity.

Experimental

For the preparation of [Cu^I(I)]ClO₄·2CH₃CN, (II), tris[(2-nitrobenzylidene)aminoethyl]amine, (I) (0.93 g, 1.7 mmol), was dissolved in dry deoxygenated acetonitrile (30 ml) and a solution of Cu(CH₃CN)₄ClO₄ (0.55 g, 1.7 mmol) in deoxygenated acetonitrile (20 ml) was added slowly with stirring. The red–brown solution was stirred for 30 min at 313 K and then cooled, during which time an orange crystalline product precipitated. This was filtered off and dried under nitrogen, losing the acetonitrile solvent in the process (yield 0.70 g, 52%). Analytical results (available in the archived CIF ) are consistent with the stated composition for all compounds reported here.

The amine podand tris[(2-nitrobenzyl)aminoethyl]amine, (III), was prepared by reduction of the imine analogue (Liu et al., 1992 ). The imine (I) (2.15 g, 3.9 mmol) was dissolved in methanol (60 ml). Na₂B₄O₇ (0.81 g, 4.0 mmol) was added, followed by NaBH₄ (0.65 g, 17.2 mmol) in small portions over a period of 30 min. The solution was stirred for 2 h and then the solvent was removed on a rotary evaporator. NH₄Cl (4 g, 76 mmol) in water (40 ml) was added and the mixture was extracted with CHCl₃ (3 × 60 ml). The CHCl₃ solution was washed with water, dried over MgSO₄ and filtered. Finally, the solvent was removed under reduced pressure to yield the amine as a pale-yellow oil (yield ca 88%). The IR spectrum of the oil confirmed that the ligand had been successfully reduced. The imine stretch at ca 1630 cm⁻¹ was no longer present, but symmetric and antisymmetric stretches of the nitro group at 1347 and 1526 cm⁻¹, respectively, confirmed that the substituent remained unchanged. The amine was used in the next step without further purification.

For the preparation of [Cu^II(III)Cl]Cl·C₂H₅OH, (IV), the amine ligand (III) (0.05 g, 0.09 mmol) was dissolved in ethanol (1.5 ml), forming a pale-orange solution. On addition of a solution containing CuCl₂ (0.013 g, 0.09 mmol) in ethanol (1 ml), a turquoise solution was formed. Green crystals of (IV) were obtained on allowing the solution to stand (yield 0.03 g, 48%).

Ligand (V) was prepared by the dropwise addition of tris(3-aminoisopropyl)amine (0.32 g, 1.7 mmol) in methanol (20 ml) with stirring to nitrobenzaldehyde (0.77 g, 5.1 mmol) in methanol (20 ml). The resulting solution was stirred at 313 K for 30 min and the volume was then reduced to yield a yellow oil, viz. (V). The oil was dissolved in deoxygenated acetonitrile (30 ml) and Cu(CH₃CN)₄·ClO₄ (0.55 g, 1.7 mmol) was added. A brown solution formed and dark-red crystals of [Cu^I(V)]ClO₄, (VI), were obtained on allowing the solution to stand (yield 0.69 g, 54%).

Compound (II)

Crystal data

[Cu(C₂₇H₂₇N₇O₆)]ClO₄·2C₂H₃N
M_r = 790.65
Triclinic, $[P \overline 1]$
a = 11.1178 (7) Å
b = 13.3595 (9) Å
c = 13.7998 (9) Å
α = 111.627 (1)°
β = 102.995 (1)°
γ = 103.648 (1)°
V = 1737.8 (2) Å³
Z = 2
D_x = 1.511 Mg m⁻³
Mo Kα radiation
μ = 0.78 mm⁻¹
T = 150 (2) K
Tablet, brown
0.37 × 0.19 × 0.08 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.762, T_max = 0.941
15023 measured reflections
7856 independent reflections
6372 reflections with I > 2σ(I)
R_int = 0.019
θ_max = 28.8°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.082
S = 1.02
7856 reflections
488 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0325P)² + 1.0079P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.025
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Selected geometric parameters (Å, °) for (II)

Cu1—N31	1.9974 (15)
Cu1—N21	1.9981 (15)
Cu1—N11	2.0127 (16)
Cu1—N1	2.1965 (15)

N31—Cu1—N21	120.56 (6)
N31—Cu1—N11	118.99 (6)
N21—Cu1—N11	118.25 (6)
N31—Cu1—N1	85.48 (6)
N21—Cu1—N1	84.85 (6)
N11—Cu1—N1	84.86 (6)

Compound (IV)

Crystal data

[Cu(C₂₇H₃₃N₇O₆)Cl]Cl·C₂H₆O
M_r = 732.11
Monoclinic, P 2₁ /c
a = 13.183 (5) Å
b = 14.485 (6) Å
c = 16.914 (7) Å
β = 95.319 (7)°
V = 3216 (2) Å³
Z = 4
D_x = 1.512 Mg m⁻³
Mo Kα radiation
μ = 0.90 mm⁻¹
T = 150 (2) K
Plate, green
0.23 × 0.21 × 0.07 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) T_min = 0.819, T_max = 0.940
22643 measured reflections
5657 independent reflections
3256 reflections with I > 2σ(I)
R_int = 0.103
θ_max = 25.0°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.153
S = 0.98
5657 reflections
416 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0768P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.76 e Å⁻³

Table 2
Selected geometric parameters (Å, °) for (IV)

Cu1—N1	2.038 (4)
Cu1—N31	2.081 (4)
Cu1—N11	2.105 (4)
Cu1—N21	2.107 (4)
Cu1—Cl1	2.2547 (16)

N1—Cu1—N31	84.44 (16)
N1—Cu1—N11	83.97 (16)
N31—Cu1—N11	127.92 (16)
N1—Cu1—N21	84.35 (15)
N31—Cu1—N21	121.43 (16)
N11—Cu1—N21	107.62 (15)
N1—Cu1—Cl1	176.50 (12)
N31—Cu1—Cl1	92.13 (12)
N11—Cu1—Cl1	97.66 (11)
N21—Cu1—Cl1	98.07 (11)

Table 3
Hydrogen-bond geometry (Å, °) for (IV)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N31—H31N⋯O41	0.93	2.13	2.998 (6)	154
N11—H11N⋯O12	0.93	2.29	2.882 (6)	121
N11—H11N⋯Cl2ⁱ	0.93	2.63	3.474 (4)	152
N21—H21N⋯O22	0.93	2.46	3.023 (6)	119
N21—H21N⋯Cl2	0.93	2.48	3.302 (4)	147
O41—H41⋯Cl2	0.84	2.28	3.105 (5)	170
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Compound (VI)

Crystal data

[Cu(C₃₀H₃₃N₇O₆)]ClO₄
M_r = 750.62
Monoclinic, P 2₁ /c
a = 9.5361 (7) Å
b = 18.6870 (13) Å
c = 19.2367 (13) Å
β = 104.044 (1)°
V = 3325.5 (4) Å³
Z = 4
D_x = 1.499 Mg m⁻³
Mo Kα radiation
μ = 0.80 mm⁻¹
T = 150 (2) K
Lath, red
0.47 × 0.17 × 0.13 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) T_min = 0.704, T_max = 0.903
28475 measured reflections
7892 independent reflections
5773 reflections with I > 2σ(I)
R_int = 0.028
θ_max = 28.8°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.112
S = 1.00
7892 reflections
455 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0534P)² + 2.0893P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 4
Selected geometric parameters (Å, °) for (VI)

Cu1—N21	2.0124 (19)
Cu1—N11	2.0093 (18)
Cu1—N31	2.0326 (17)
Cu1—N1	2.1965 (19)

N21—Cu1—N11	121.49 (8)
N21—Cu1—N31	119.13 (7)
N11—Cu1—N31	117.34 (7)
N21—Cu1—N1	94.59 (8)
N11—Cu1—N1	94.67 (7)
N31—Cu1—N1	95.00 (7)

For all three compounds, H atoms were inserted in calculated positions and refined using a riding model. The constrained distances were 0.95, 0.99, 0.98, 0.93 and 0.84 Å for aryl, methylene, methyl, amine and alcohol H atoms, respectively. They were refined with U_iso(H) = 1.2U_eq(carrier atom). The value of R_int for complex (IV) is high (0.103) due to poor crystal quality resulting in broad diffraction peaks.

For all compounds, data collection: SMART (Bruker, 1998 ); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2001 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks II, IV, VI, global. DOI: 10.1107/S0108270106034524/sq3035sup1.cif

Structure factors: contains datablock II. DOI: 10.1107/S0108270106034524/sq3035IIsup2.hkl

Structure factors: contains datablock IV. DOI: 10.1107/S0108270106034524/sq3035IVsup3.hkl

Structure factors: contains datablock VI. DOI: 10.1107/S0108270106034524/sq3035VIsup4.hkl

Comment top

We have had a long-standing interest in the chemistry of both imine and amine cryptates derived from tris(aminoethyl)amine (tren) and tris(3-aminoisopropyl)amine (trpn) [see, for example, McKee et al. (2003) and Nelson et al. (1998)]. We have investigated some simple podate complexes derived from the same amines in order to clarify the geometric requirements associated with each. A search of the Cambridge Structural Database (Version?; Allen, 2002; Fletcher et al., 1996) showed that, although many tris(aminoethyl)amine/salicylate complexes have been investigated, surprisingly few simple podates with other substituted benzaldehyde derivatives have been structurally characterized to date. In this paper, we compare the structures of two Cu^I podates, one derived from tris(aminoethyl)amine (tren) and one from tris(aminopropyl)amine (trpn), with the Cu^II amine analogue of the smaller tren-based podate.

In podate and cryptate complexes with potential threefold symmetry, imine donors typically stabilize Cu^I and are easily hydrolysed by Cu^II (Harding et al., 1995; Arthurs et al., 2001). Reduction of the imine donors to the corresponding amines generates a site in which Cu^I is activated to reaction with dioxygen, as shown elegantly by Suzuki, Schindler and their co-workers (Komiyama et al., 2004; Schindler, 2001). However, Cu^II binds readily to the reduced ligands.

The structure of the imine podand tris(N-2-nitrobenzylideneaminoethyl)amine, (I), was reported recently (McKee et al., 2006). Reaction of (I) with Cu(CH₃CN)₄ClO₄ in acetonitrile gave the Cu^I complex [Cu(I)]ClO₄·2CH₃CN, (II), as dark-brown crystals (Fig. 1). The Cu^I ion is coordinated to all four N atoms in an approximately trigonal–pyramidal geometry (Table 1), although the bonds to the imine N atoms [average 2.003 (2) Å] are significantly shorter than that to the bridgehead amine [Cu1—N1 = 2.196 (1) Å], and the Cu^I ion is 0.172 (1) Å out of the mean plane of the imine N atoms, in the opposite direction to the bridgehead. The nitro groups are not involved in the coordination of the metal and the three strands are arranged fairly tightly about the approximate threefold axis. There are two important factors controlling this geometry, namely the essentially planar geometry at the imine N atoms [angle sums 359.9 (2), 359.9 (2) and 359.8 (2)° for atoms N11, N21 and N31, respectively] and the steric demands imposed by coordination of all four N donors of the ligand. These result in the C—N═C plane being tilted with respect to the `default' orientation (parallel to the pseudo-threefold axis and perpendicular to the plane of the three sp²-hybridized imine donors); the interplanar angles are 71.6 (1), 73.5 (1) and 74.1 (1)° for the N11, N21 and N31 strands, respectively. In other words, the orientation of the conjugated nitrobenzylidene strands is determined by the orientation of the imine lone pairs. It is therefore not surprising that this geometry is common for tren-based imine podands in the absence of additional intra- or intermolecular interactions. There are no significant interactions between the cation and perchlorate anion or solvent molecules. The anion is disordered and was modelled with approximately 10% occupancy of the minor orientation (Fig. 1).

The amine podand, tris(N-2-nitrobenzylaminoethyl)amine, (III), was obtained by reduction of (I) with NaBH₄, which reduced the imine groups but not the nitro substituents. Reaction of ligand (III) with CuCl₂ in ethanol yielded the amine complex [Cu(III)Cl]Cl·C₂H₅OH, (IV), as green crystals. The formula unit of (IV) is shown in Fig. 2. The geometry at the Cu^I ion is approximately trigonal–bipyramidal (Table 2), with the bridghead tertiary amine and the coordinated Cl⁻ ion as apical donors. The coordination geometry is similar to that observed for the analogous Cu^II podate derived from benzaldehyde [tris(N-benzylaminoethyl)amine; Komiyama et al., 2004; Schatz et al., 2001).

Two of the nitro groups of (IV) are hydrogen-bonded to the adjacent secondary amines (Table 3) but the third strand is different, with the amine (N31) hydrogen-bonded to the ethanol solvate. Consequently the configuration at N31 is opposite to that at N11 and N21 (SRR in Fig. 2, although, since the structure is centrosymmetric, the RSS configuration is also present). This difference breaks the pseudo-threefold symmetry of the cation. The non-coordinated Cl⁻ ion Cl2 makes a relatively short hydrogen bond to the ethanol solvate [3.105 (4) Å] and shows further interactions with N21 and with N11 of an adjacent molecule. The latter two interactions are long for hydrogen bonds to Cl⁻, at 3.302 (4) and 3.474 (4) Å, respectively (Steiner, 2002). However, both are bifurcated and involve coordinated amines. The resulting hydrogen-bond pattern links the structure in chains running parallel to the b axis (Fig. 3). The most notable interaction between these chains is a π–π interaction between the C24–C29 ring and its symmetry equivalent by inversion under (1 − x, −y, 1 − z): the rings are necessarily parallel, the interplanar distance is 3.393 (4) Å and centroid-to-centroid distance is 3.710 (4) Å.

Complex (VI), tris(N-2-nitrobenzylideneaminopropyl)aminecopper(I) perchlorate, is analogous to complex (II), except that the longer tripodal amine tris(aminopropyl)amine (trpn) is used in place of tren. As for (II), the Cu ion is stabliized in the +1 state and has trigonal–pyramidal geometry (Fig. 4 and Table 4). However, the Cu^I ion is displaced from the imine plane by 0.167 (1) Å towards the bridgehead [i.e. in the opposite sense from complex (II)]. As observed for complex (II), the requirement to coordinate the Cu^I ion to all four N donors results in tilting of the C—N═C planes relative to the plane of the three sp²-hybridized imine donors. In complex (VI), however, this effect is much more pronounced [interplanar angles 34.9 (2), 36.3 (2) and 39.4 (2)° for atoms N11, N21 and N31, respectively].

The three-dimensional `podand bite' in the two Cu^I complexes, (II) and (VI), can be compared by considering the dimensions of the trigonal pyramid formed by the four N donors, with the tertiary amine (N1) at the apex and the imine atoms N11, N21 and N31 in the basal plane. As mentioned above, the Cu^I ion is outside the pyramid in complex (II) and inside for (VI). However, the Cu—N1 distances are identical [2.196 (2) Å] and the Cu—N(imine) bonds are only marginally different [mean values 2.003 (2) Å for (II) and 2.018 (2) Å for (VI)]. The mean imine–imine distances in the basal plane are similar [3.456 and 3.483 Å for (II) and (VI), respectively], but the mean base–apex edges are significantly different [2.842 (2) Å for (II) and 3.103 (2) for (VI)]. An indication of steric strain in complex (VI) is given by the N—C—C and C—C—C angles in the saturated chain between N1 and the imine N atoms; the average angle is 114.4 (3)°, compared with 110.5 (2)° for complex (II).

We have observed similar patterns in the geometry of Cu ions in cryptand hosts derived from tren and trpn [see, for example, Farrar et al. (1995) and Nelson et al. (1998)], supporting the suggestion that steric constraints mean that the larger podand has more difficulty accommodating bonding between the Cu^I ion and all four donors than the smaller analogue. These results also go some way to explaining the initially counterintuitive finding that, in the dinuclear iminocryptate series, the shortest internuclear distances between cationic guests are found for the larger hosts (Drew et al., 2000; Farrar et al., 1995; Nelson et al., 1998). In the case of the cryptand ligands, the twist imposed on each strand by the coordination of the imine donors shortens the distance between the two metal binding sites.

Experimental top

For the preparation of [Cu^I(I)]ClO₄·2CH₃CN, (II), ligand (I) [tris(N-2-nitrobenzylideneaminoethyl)amine] (0.93 g, 1.7 mmol) was dissolved in dry deoxygenated acetonitrile (30 ml) and a solution of Cu(CH₃CN)₄ClO₄ (0.55 g, 1.7 mmol) in deoxygenated acetonitrile (20 ml) was added slowly with stirring. The red–brown solution was stirred for 30 min at 313 K and then cooled, during which time an orange crystalline product precipitated. This was filtered off and dried under nitrogen, losing the acetonitrile solvent in the process (yield 0.70 g, 52%). Analytical results (provided in the archived CIF) are consistent with the stated composition for all compounds reported here.

The amine podand, tris(N-2-nitrobenzylaminoethyl)amine, (III), was prepared by reduction of the imine analogue (Liu et al., 1992). The imine (I) (2.15 g, 3.9 mmol) was dissolved in methanol (60 ml). Na₂B₄O₇ (0.81 g, 4.0 mmol) was added, followed by NaBH₄ (0.65 g, 17.2 mmol) in small portions over a period of 30 min. The solution was stirred for 2 h and then the solvent was removed on a rotary evaporator. NH₄Cl (4 g, 76 mmol) in water (40 ml) was added and the mixture was extracted with CHCl₃ (3 × 60 ml). The CHCl₃ solution was washed with water, dried over MgSO₄ and filtered. Finally, the solvent was removed under reduced pressure to yield the amine as a pale-yellow oil (yield ca 88%). The IR spectrum of the oil confirmed that the ligand had been successfully reduced. The imine stretch at ca 1630 cm⁻¹ was no longer present, but symmetric and antisymmetric stretches of the nitro group at 1347 and 1526 cm⁻¹, respectively, confirmed that the substituent remained unchanged. The amine was used in the next step without further purification.

For the preparation of [Cu^II(III)Cl]Cl·C₂H₅OH, (IV), the amine ligand (III) (0.05 g, 0.09 mmol) was dissolved in ethanol (1.5 ml), forming a pale-orange solution. On addition of a solution containing CuCl₂ (0.013 g, 0.09 mmol) in ethanol (1 ml), a turquoise solution was formed. Green crystals of [Cu(II)Cl]Cl·C₂H₅OH, (IV), were obtained on allowing the solution to stand (yield 0.03 g, 48%).

Ligand (V) was prepared by the dropwise addition of tris(3-aminoisopropyl)amine (0.32 g, 1.7 mmol) in methanol (20 ml) with stirring to nitrobenzaldehyde (0.77 g, 5.1 mmol) in methanol (20 ml). The solution was stirred at 313 K for 30 min and the volume was then reduced to yield a yellow oil, (V). The oil was dissolved in deoxygenated acetonitrile (30 ml) and Cu(CH₃CN)₄·ClO₄ (0.55 g, 1.7 mmol) was added. A brown solution formed and dark-red crystals of [Cu^I(V)]ClO₄, (VI), were obtained on allowing the solution to stand (yield 0.69 g, 54%).

Computing details top

For all compounds, data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. The structure of complex (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity. The minor component of the disordered ClO₄⁻ ion is indicated by open bonds.
	Fig. 2. The structure of complex (IV), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.
	Fig. 3. A packing plot for complex (IV), viewed down the b axis. Hydrogen bonds are shown as dashed lines and the π–π interaction is indicated by open bonds linking ring centroids. Cl atoms are shown cross-hatched, Cu atoms are shaded top left to bottom right, N atoms are dotted, and O atoms are shaded bottom left to upper right.
	Fig. 4. The structure of complex (VI), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms have been omitted for clarity.

(II) [tris(2-nitrobenzylideneaminoethyl)amine-κ⁴N]copper(I) perchlorate acetonitrile trisolvate top

Crystal data top

[Cu(C₂₇H₂₇N₇O₆)]ClO₄·2C₂H₃N	Z = 2
M_r = 790.65	F(000) = 816
Triclinic, P1	D_x = 1.511 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.1178 (7) Å	Cell parameters from 6794 reflections
b = 13.3595 (9) Å	θ = 2.7–23.3°
c = 13.7998 (9) Å	µ = 0.78 mm⁻¹
α = 111.627 (1)°	T = 150 K
β = 102.995 (1)°	Tablet, brown
γ = 103.648 (1)°	0.37 × 0.19 × 0.08 mm
V = 1737.8 (2) Å³

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	7856 independent reflections
Radiation source: normal-focus sealed tube	6372 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ϕ and ω scans	θ_max = 28.8°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −14→14
T_min = 0.762, T_max = 0.941	k = −17→17
15023 measured reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0325P)² + 1.0079P] where P = (F_o² + 2F_c²)/3
7856 reflections	(Δ/σ)_max = 0.025
488 parameters	Δρ_max = 0.35 e Å⁻³
10 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Cu(C₂₇H₂₇N₇O₆)]ClO₄·2C₂H₃N	γ = 103.648 (1)°
M_r = 790.65	V = 1737.8 (2) Å³
Triclinic, P1	Z = 2
a = 11.1178 (7) Å	Mo Kα radiation
b = 13.3595 (9) Å	µ = 0.78 mm⁻¹
c = 13.7998 (9) Å	T = 150 K
α = 111.627 (1)°	0.37 × 0.19 × 0.08 mm
β = 102.995 (1)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	7856 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	6372 reflections with I > 2σ(I)
T_min = 0.762, T_max = 0.941	R_int = 0.019
15023 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	10 restraints
wR(F²) = 0.082	H-atom parameters constrained
S = 1.02	Δρ_max = 0.35 e Å⁻³
7856 reflections	Δρ_min = −0.45 e Å⁻³
488 parameters

Special details top

Experimental. Analysis for [Cu^I(I)]ClO₄·2CH₃CN: calculated for [C₂₇H₂₇N₇O₆Cu]ClO₄·2CH₃CN: C 43.6, H 4.2, N 13.2%; found C 42.9, H 3.9, N 13.9%. NMR (CD₃CN, p.p.m., ¹H): 3.00(t, 6, CH₂), 3.75(t, 6, CH₂), 8.49(s, 3, imine), 7.91(d, 3, aromatic), 6.99(d, 3, aromatic), 7.35(t, 3, aromatic), 7.40(t, 3, aromatic). Mass spectrum (FAB): m/e 608, [Cu^I(I)]⁺. IR (KBr, cm⁻¹) inter alia: 1636(m, imine), 1522(s, NO₂), 1348(m, NO₂), 1089(s, ClO₄), 622(m, ClO₄).

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.84793 (2)	0.266571 (19)	0.100555 (18)	0.01969 (7)
N1	0.89898 (15)	0.34676 (13)	0.28179 (13)	0.0220 (3)
C11	0.8893 (2)	0.25018 (17)	0.31090 (16)	0.0273 (4)
H11A	0.8727	0.2699	0.3820	0.033*
H11B	0.9735	0.2356	0.3204	0.033*
N11	0.79556 (15)	0.11701 (13)	0.11093 (13)	0.0221 (3)
C13	0.77203 (18)	0.01231 (16)	0.04674 (16)	0.0236 (4)
H13	0.7397	−0.0454	0.0686	0.028*
C12	0.7769 (2)	0.14202 (17)	0.21900 (16)	0.0269 (4)
H12A	0.7749	0.0760	0.2360	0.032*
H12B	0.6915	0.1536	0.2153	0.032*
C14	0.79366 (18)	−0.02199 (16)	−0.06110 (16)	0.0229 (4)
C15	0.9006 (2)	0.04735 (17)	−0.07126 (17)	0.0271 (4)
H15	0.9560	0.1188	−0.0097	0.033*
C16	0.9280 (2)	0.01443 (18)	−0.16903 (18)	0.0306 (4)
H16	1.0012	0.0635	−0.1739	0.037*
C17	0.8489 (2)	−0.08987 (18)	−0.25998 (17)	0.0301 (4)
H17	0.8674	−0.1118	−0.3272	0.036*
C18	0.7430 (2)	−0.16191 (17)	−0.25245 (17)	0.0280 (4)
H18	0.6887	−0.2339	−0.3139	0.034*
C19	0.71792 (19)	−0.12735 (16)	−0.15418 (16)	0.0242 (4)
N12	0.60017 (17)	−0.20368 (15)	−0.15175 (14)	0.0300 (4)
O11	0.53494 (15)	−0.15857 (14)	−0.10091 (13)	0.0379 (4)
O12	0.57293 (17)	−0.30771 (12)	−0.20192 (13)	0.0410 (4)
C21	0.79875 (19)	0.39911 (17)	0.30149 (16)	0.0252 (4)
H21A	0.8355	0.4649	0.3765	0.030*
H21B	0.7214	0.3418	0.2988	0.030*
C22	0.7549 (2)	0.44077 (16)	0.21513 (15)	0.0248 (4)
H22A	0.6776	0.4633	0.2226	0.030*
H22B	0.8270	0.5093	0.2283	0.030*
N21	0.71998 (15)	0.34950 (13)	0.10146 (12)	0.0203 (3)
C23	0.61804 (18)	0.33684 (16)	0.02728 (16)	0.0224 (4)
H23	0.5664	0.3833	0.0466	0.027*
C24	0.57998 (17)	0.24997 (16)	−0.08869 (15)	0.0218 (4)
C25	0.5744 (2)	0.13817 (17)	−0.11202 (17)	0.0280 (4)
H25	0.5939	0.1179	−0.0526	0.034*
C26	0.5413 (2)	0.05579 (18)	−0.21959 (18)	0.0326 (5)
H26	0.5390	−0.0198	−0.2332	0.039*
C27	0.5114 (2)	0.08298 (19)	−0.30792 (17)	0.0328 (5)
H27	0.4911	0.0268	−0.3816	0.039*
C28	0.5112 (2)	0.19226 (18)	−0.28816 (17)	0.0289 (4)
H28	0.4875	0.2111	−0.3481	0.035*
C29	0.54587 (18)	0.27333 (16)	−0.18018 (16)	0.0224 (4)
N22	0.55437 (17)	0.39003 (15)	−0.16267 (15)	0.0291 (4)
O21	0.62750 (16)	0.47051 (13)	−0.07206 (14)	0.0401 (4)
O22	0.49043 (19)	0.40332 (15)	−0.23847 (14)	0.0488 (4)
C31	1.03322 (19)	0.43013 (17)	0.32290 (16)	0.0267 (4)
H31A	1.0788	0.4460	0.4002	0.032*
H31B	1.0288	0.5033	0.3229	0.032*
C32	1.11152 (19)	0.38375 (17)	0.24995 (16)	0.0263 (4)
H32A	1.1981	0.4441	0.2740	0.032*
H32B	1.1274	0.3171	0.2585	0.032*
N31	1.03786 (15)	0.34801 (13)	0.13175 (13)	0.0214 (3)
C33	1.10587 (18)	0.36714 (16)	0.07316 (16)	0.0230 (4)
H33	1.1992	0.4009	0.1064	0.028*
C34	1.04401 (18)	0.33836 (15)	−0.04505 (16)	0.0216 (4)
C35	0.92335 (19)	0.35076 (17)	−0.08239 (17)	0.0276 (4)
H35	0.8779	0.3735	−0.0322	0.033*
C36	0.8688 (2)	0.33042 (18)	−0.19157 (18)	0.0306 (4)
H36	0.7862	0.3387	−0.2153	0.037*
C37	0.9334 (2)	0.29810 (17)	−0.26663 (17)	0.0284 (4)
H37	0.8947	0.2833	−0.3416	0.034*
C38	1.05460 (19)	0.28758 (16)	−0.23165 (16)	0.0253 (4)
H38	1.1009	0.2670	−0.2816	0.030*
C39	1.10698 (18)	0.30755 (15)	−0.12256 (16)	0.0221 (4)
N32	1.23234 (16)	0.28968 (15)	−0.09099 (14)	0.0286 (4)
O31	1.24753 (15)	0.24577 (13)	−0.02714 (13)	0.0373 (4)
O32	1.31394 (15)	0.31923 (16)	−0.13048 (14)	0.0445 (4)
Cl1	0.60725 (5)	0.25292 (4)	0.47922 (4)	0.02898 (11)	0.906 (7)
O1	0.4861 (2)	0.1771 (3)	0.47097 (17)	0.0418 (6)	0.906 (7)
O2	0.7002 (2)	0.19480 (18)	0.4679 (2)	0.0531 (8)	0.906 (7)
O3	0.5799 (2)	0.2862 (3)	0.3919 (3)	0.0624 (9)	0.906 (7)
O4	0.6611 (2)	0.3515 (2)	0.5855 (2)	0.0591 (8)	0.906 (7)
Cl1'	0.60725 (5)	0.25292 (4)	0.47922 (4)	0.02898 (11)	0.094 (7)
O1'	0.4742 (14)	0.2210 (19)	0.4840 (17)	0.029 (5)*	0.094 (7)
O2'	0.6685 (17)	0.1858 (13)	0.5140 (16)	0.032 (5)*	0.094 (7)
O3'	0.5919 (16)	0.2298 (16)	0.3660 (10)	0.023 (4)*	0.094 (7)
O4'	0.6706 (18)	0.3738 (11)	0.5475 (16)	0.035 (5)*	0.094 (7)
N41	0.8262 (3)	0.7161 (2)	0.4619 (2)	0.0572 (6)
C42	0.7360 (3)	0.6508 (2)	0.45784 (19)	0.0411 (6)
C43	0.6212 (3)	0.5665 (2)	0.4522 (2)	0.0438 (6)
H43A	0.5874	0.4985	0.3802	0.066*
H43B	0.5526	0.6001	0.4610	0.066*
H43C	0.6463	0.5441	0.5118	0.066*
N51	0.8632 (2)	0.9497 (2)	0.3214 (2)	0.0575 (6)
C52	0.8368 (2)	0.9683 (2)	0.3993 (2)	0.0415 (6)
C53	0.8037 (3)	0.9915 (2)	0.4999 (2)	0.0462 (6)
H53A	0.7464	0.9197	0.4938	0.069*
H53B	0.7577	1.0467	0.5093	0.069*
H53C	0.8847	1.0236	0.5643	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01986 (12)	0.01953 (12)	0.01861 (12)	0.00579 (9)	0.00692 (9)	0.00792 (9)
N1	0.0240 (8)	0.0215 (8)	0.0203 (8)	0.0073 (7)	0.0077 (7)	0.0095 (7)
C11	0.0333 (11)	0.0296 (10)	0.0226 (10)	0.0119 (9)	0.0102 (9)	0.0146 (9)
N11	0.0212 (8)	0.0226 (8)	0.0221 (8)	0.0064 (6)	0.0065 (6)	0.0110 (7)
C13	0.0227 (9)	0.0200 (9)	0.0268 (10)	0.0057 (8)	0.0064 (8)	0.0114 (8)
C12	0.0327 (11)	0.0269 (10)	0.0263 (10)	0.0094 (9)	0.0136 (9)	0.0160 (9)
C14	0.0239 (9)	0.0199 (9)	0.0266 (10)	0.0104 (8)	0.0072 (8)	0.0114 (8)
C15	0.0266 (10)	0.0210 (9)	0.0304 (11)	0.0073 (8)	0.0088 (8)	0.0094 (9)
C16	0.0285 (11)	0.0281 (11)	0.0377 (12)	0.0108 (9)	0.0149 (9)	0.0147 (10)
C17	0.0365 (12)	0.0311 (11)	0.0269 (10)	0.0164 (9)	0.0137 (9)	0.0128 (9)
C18	0.0305 (11)	0.0231 (10)	0.0245 (10)	0.0102 (8)	0.0036 (8)	0.0074 (8)
C19	0.0228 (9)	0.0195 (9)	0.0286 (10)	0.0069 (8)	0.0048 (8)	0.0118 (8)
N12	0.0279 (9)	0.0281 (9)	0.0271 (9)	0.0028 (7)	0.0009 (7)	0.0144 (8)
O11	0.0275 (8)	0.0412 (9)	0.0430 (9)	0.0060 (7)	0.0130 (7)	0.0199 (8)
O12	0.0489 (10)	0.0213 (8)	0.0349 (9)	−0.0016 (7)	0.0018 (7)	0.0099 (7)
C21	0.0288 (10)	0.0267 (10)	0.0201 (9)	0.0106 (8)	0.0115 (8)	0.0082 (8)
C22	0.0278 (10)	0.0215 (9)	0.0221 (10)	0.0093 (8)	0.0089 (8)	0.0060 (8)
N21	0.0221 (8)	0.0198 (8)	0.0189 (8)	0.0059 (6)	0.0085 (6)	0.0085 (6)
C23	0.0207 (9)	0.0223 (9)	0.0255 (10)	0.0076 (7)	0.0095 (8)	0.0113 (8)
C24	0.0149 (8)	0.0266 (10)	0.0222 (9)	0.0065 (7)	0.0055 (7)	0.0100 (8)
C25	0.0266 (10)	0.0284 (10)	0.0275 (10)	0.0112 (8)	0.0043 (8)	0.0128 (9)
C26	0.0326 (11)	0.0261 (11)	0.0315 (11)	0.0111 (9)	0.0051 (9)	0.0080 (9)
C27	0.0310 (11)	0.0345 (12)	0.0230 (10)	0.0090 (9)	0.0063 (9)	0.0060 (9)
C28	0.0254 (10)	0.0355 (11)	0.0240 (10)	0.0061 (9)	0.0080 (8)	0.0146 (9)
C29	0.0165 (9)	0.0251 (10)	0.0272 (10)	0.0063 (7)	0.0085 (8)	0.0133 (8)
N22	0.0296 (9)	0.0321 (9)	0.0345 (10)	0.0106 (8)	0.0167 (8)	0.0208 (8)
O21	0.0432 (9)	0.0259 (8)	0.0410 (9)	0.0018 (7)	0.0097 (8)	0.0134 (7)
O22	0.0717 (12)	0.0480 (10)	0.0411 (10)	0.0298 (9)	0.0170 (9)	0.0307 (9)
C31	0.0264 (10)	0.0262 (10)	0.0187 (9)	0.0047 (8)	0.0036 (8)	0.0064 (8)
C32	0.0210 (9)	0.0278 (10)	0.0229 (10)	0.0042 (8)	0.0027 (8)	0.0095 (8)
N31	0.0215 (8)	0.0182 (8)	0.0211 (8)	0.0056 (6)	0.0063 (6)	0.0066 (7)
C33	0.0186 (9)	0.0206 (9)	0.0266 (10)	0.0050 (7)	0.0074 (8)	0.0087 (8)
C34	0.0197 (9)	0.0176 (9)	0.0255 (10)	0.0023 (7)	0.0084 (8)	0.0099 (8)
C35	0.0216 (10)	0.0314 (11)	0.0349 (11)	0.0087 (8)	0.0155 (9)	0.0170 (9)
C36	0.0219 (10)	0.0367 (12)	0.0380 (12)	0.0104 (9)	0.0096 (9)	0.0220 (10)
C37	0.0290 (10)	0.0274 (10)	0.0267 (10)	0.0060 (8)	0.0065 (8)	0.0141 (9)
C38	0.0276 (10)	0.0211 (9)	0.0275 (10)	0.0071 (8)	0.0124 (8)	0.0102 (8)
C39	0.0189 (9)	0.0173 (9)	0.0291 (10)	0.0054 (7)	0.0079 (8)	0.0101 (8)
N32	0.0257 (9)	0.0268 (9)	0.0283 (9)	0.0111 (7)	0.0088 (7)	0.0064 (8)
O31	0.0397 (9)	0.0342 (8)	0.0369 (9)	0.0193 (7)	0.0060 (7)	0.0151 (7)
O32	0.0270 (8)	0.0642 (11)	0.0448 (10)	0.0191 (8)	0.0216 (7)	0.0194 (9)
Cl1	0.0298 (3)	0.0302 (3)	0.0290 (3)	0.0106 (2)	0.0102 (2)	0.0152 (2)
O1	0.0418 (11)	0.0419 (14)	0.0323 (11)	−0.0007 (10)	0.0137 (9)	0.0157 (10)
O2	0.0462 (12)	0.0542 (13)	0.0614 (16)	0.0303 (10)	0.0170 (11)	0.0214 (11)
O3	0.0495 (13)	0.095 (2)	0.0781 (18)	0.0258 (13)	0.0245 (12)	0.0731 (18)
O4	0.0510 (13)	0.0387 (12)	0.0521 (15)	0.0040 (10)	0.0094 (11)	−0.0044 (11)
Cl1'	0.0298 (3)	0.0302 (3)	0.0290 (3)	0.0106 (2)	0.0102 (2)	0.0152 (2)
N41	0.0588 (15)	0.0448 (13)	0.0511 (14)	0.0133 (12)	0.0112 (12)	0.0113 (11)
C42	0.0524 (15)	0.0377 (13)	0.0286 (12)	0.0245 (12)	0.0098 (11)	0.0072 (10)
C43	0.0533 (15)	0.0462 (14)	0.0373 (13)	0.0252 (12)	0.0191 (12)	0.0173 (12)
N51	0.0610 (15)	0.0634 (16)	0.0708 (17)	0.0353 (13)	0.0331 (14)	0.0390 (14)
C52	0.0363 (13)	0.0377 (13)	0.0528 (16)	0.0177 (11)	0.0095 (12)	0.0231 (12)
C53	0.0425 (14)	0.0468 (15)	0.0425 (14)	0.0182 (12)	0.0040 (11)	0.0177 (12)

Geometric parameters (Å, º) top

Cu1—N31	1.9974 (15)	C27—C28	1.384 (3)
Cu1—N21	1.9981 (15)	C27—H27	0.9500
Cu1—N11	2.0127 (16)	C28—C29	1.377 (3)
Cu1—N1	2.1965 (15)	C28—H28	0.9500
N1—C31	1.469 (2)	C29—N22	1.463 (2)
N1—C21	1.473 (2)	N22—O22	1.222 (2)
N1—C11	1.474 (2)	N22—O21	1.233 (2)
C11—C12	1.531 (3)	C31—C32	1.531 (3)
C11—H11A	0.9900	C31—H31A	0.9900
C11—H11B	0.9900	C31—H31B	0.9900
N11—C13	1.273 (2)	C32—N31	1.483 (2)
N11—C12	1.478 (2)	C32—H32A	0.9900
C13—C14	1.481 (3)	C32—H32B	0.9900
C13—H13	0.9500	N31—C33	1.275 (2)
C12—H12A	0.9900	C33—C34	1.480 (3)
C12—H12B	0.9900	C33—H33	0.9500
C14—C15	1.394 (3)	C34—C35	1.396 (3)
C14—C19	1.401 (3)	C34—C39	1.397 (3)
C15—C16	1.384 (3)	C35—C36	1.386 (3)
C15—H15	0.9500	C35—H35	0.9500
C16—C17	1.388 (3)	C36—C37	1.388 (3)
C16—H16	0.9500	C36—H36	0.9500
C17—C18	1.384 (3)	C37—C38	1.383 (3)
C17—H17	0.9500	C37—H37	0.9500
C18—C19	1.378 (3)	C38—C39	1.383 (3)
C18—H18	0.9500	C38—H38	0.9500
C19—N12	1.473 (2)	C39—N32	1.466 (2)
N12—O12	1.225 (2)	N32—O32	1.220 (2)
N12—O11	1.227 (2)	N32—O31	1.229 (2)
C21—C22	1.524 (3)	Cl1—O3	1.4273 (19)
C21—H21A	0.9900	Cl1—O1	1.4333 (18)
C21—H21B	0.9900	Cl1—O4	1.433 (2)
C22—N21	1.480 (2)	Cl1—O2	1.434 (2)
C22—H22A	0.9900	N41—C42	1.139 (3)
C22—H22B	0.9900	C42—C43	1.455 (4)
N21—C23	1.273 (2)	C43—H43A	0.9800
C23—C24	1.477 (3)	C43—H43B	0.9800
C23—H23	0.9500	C43—H43C	0.9800
C24—C25	1.390 (3)	N51—C52	1.132 (3)
C24—C29	1.402 (3)	C52—C53	1.459 (4)
C25—C26	1.382 (3)	C53—H53A	0.9800
C25—H25	0.9500	C53—H53B	0.9800
C26—C27	1.389 (3)	C53—H53C	0.9800
C26—H26	0.9500

N31—Cu1—N21	120.56 (6)	C25—C26—C27	120.3 (2)
N31—Cu1—N11	118.99 (6)	C25—C26—H26	119.8
N21—Cu1—N11	118.25 (6)	C27—C26—H26	119.8
N31—Cu1—N1	85.48 (6)	C28—C27—C26	119.72 (19)
N21—Cu1—N1	84.85 (6)	C28—C27—H27	120.1
N11—Cu1—N1	84.86 (6)	C26—C27—H27	120.1
C31—N1—C21	114.30 (15)	C29—C28—C27	118.90 (19)
C31—N1—C11	114.64 (15)	C29—C28—H28	120.6
C21—N1—C11	113.39 (15)	C27—C28—H28	120.6
C31—N1—Cu1	103.81 (11)	C28—C29—C24	123.00 (18)
C21—N1—Cu1	104.77 (11)	C28—C29—N22	116.97 (17)
C11—N1—Cu1	104.33 (11)	C24—C29—N22	119.92 (17)
N1—C11—C12	109.82 (15)	O22—N22—O21	123.21 (18)
N1—C11—H11A	109.7	O22—N22—C29	118.77 (18)
C12—C11—H11A	109.7	O21—N22—C29	118.02 (17)
N1—C11—H11B	109.7	N1—C31—C32	110.75 (15)
C12—C11—H11B	109.7	N1—C31—H31A	109.5
H11A—C11—H11B	108.2	C32—C31—H31A	109.5
C13—N11—C12	117.14 (16)	N1—C31—H31B	109.5
C13—N11—Cu1	135.24 (14)	C32—C31—H31B	109.5
C12—N11—Cu1	107.56 (11)	H31A—C31—H31B	108.1
N11—C13—C14	121.72 (17)	N31—C32—C31	110.29 (15)
N11—C13—H13	119.1	N31—C32—H32A	109.6
C14—C13—H13	119.1	C31—C32—H32A	109.6
N11—C12—C11	110.07 (15)	N31—C32—H32B	109.6
N11—C12—H12A	109.6	C31—C32—H32B	109.6
C11—C12—H12A	109.6	H32A—C32—H32B	108.1
N11—C12—H12B	109.6	C33—N31—C32	116.77 (16)
C11—C12—H12B	109.6	C33—N31—Cu1	134.94 (14)
H12A—C12—H12B	108.2	C32—N31—Cu1	108.08 (11)
C15—C14—C19	116.25 (18)	N31—C33—C34	122.07 (17)
C15—C14—C13	120.13 (17)	N31—C33—H33	119.0
C19—C14—C13	123.40 (17)	C34—C33—H33	119.0
C16—C15—C14	121.51 (19)	C35—C34—C39	116.43 (18)
C16—C15—H15	119.2	C35—C34—C33	120.85 (17)
C14—C15—H15	119.2	C39—C34—C33	122.49 (17)
C15—C16—C17	120.34 (19)	C36—C35—C34	121.06 (18)
C15—C16—H16	119.8	C36—C35—H35	119.5
C17—C16—H16	119.8	C34—C35—H35	119.5
C18—C17—C16	119.80 (19)	C35—C36—C37	120.79 (19)
C18—C17—H17	120.1	C35—C36—H36	119.6
C16—C17—H17	120.1	C37—C36—H36	119.6
C19—C18—C17	118.78 (19)	C38—C37—C36	119.60 (19)
C19—C18—H18	120.6	C38—C37—H37	120.2
C17—C18—H18	120.6	C36—C37—H37	120.2
C18—C19—C14	123.29 (18)	C39—C38—C37	118.72 (18)
C18—C19—N12	116.97 (17)	C39—C38—H38	120.6
C14—C19—N12	119.63 (17)	C37—C38—H38	120.6
O12—N12—O11	124.47 (18)	C38—C39—C34	123.38 (17)
O12—N12—C19	117.88 (18)	C38—C39—N32	116.65 (17)
O11—N12—C19	117.64 (16)	C34—C39—N32	119.91 (17)
N1—C21—C22	111.36 (15)	O32—N32—O31	124.73 (18)
N1—C21—H21A	109.4	O32—N32—C39	117.45 (17)
C22—C21—H21A	109.4	O31—N32—C39	117.82 (16)
N1—C21—H21B	109.4	O3—Cl1—O1	108.19 (14)
C22—C21—H21B	109.4	O3—Cl1—O4	110.78 (17)
H21A—C21—H21B	108.0	O1—Cl1—O4	109.42 (14)
N21—C22—C21	110.80 (15)	O3—Cl1—O2	109.57 (15)
N21—C22—H22A	109.5	O1—Cl1—O2	109.88 (15)
C21—C22—H22A	109.5	O4—Cl1—O2	109.00 (13)
N21—C22—H22B	109.5	N41—C42—C43	179.5 (3)
C21—C22—H22B	109.5	C42—C43—H43A	109.5
H22A—C22—H22B	108.1	C42—C43—H43B	109.5
C23—N21—C22	117.28 (16)	H43A—C43—H43B	109.5
C23—N21—Cu1	133.34 (13)	C42—C43—H43C	109.5
C22—N21—Cu1	109.35 (11)	H43A—C43—H43C	109.5
N21—C23—C24	120.13 (17)	H43B—C43—H43C	109.5
N21—C23—H23	119.9	N51—C52—C53	179.3 (3)
C24—C23—H23	119.9	C52—C53—H53A	109.5
C25—C24—C29	116.45 (18)	C52—C53—H53B	109.5
C25—C24—C23	120.35 (17)	H53A—C53—H53B	109.5
C29—C24—C23	123.19 (17)	C52—C53—H53C	109.5
C26—C25—C24	121.52 (19)	H53A—C53—H53C	109.5
C26—C25—H25	119.2	H53B—C53—H53C	109.5
C24—C25—H25	119.2

N31—Cu1—N1—C31	10.20 (12)	N1—Cu1—N21—C22	16.47 (12)
N21—Cu1—N1—C31	−111.07 (12)	C22—N21—C23—C24	177.98 (16)
N11—Cu1—N1—C31	129.89 (12)	Cu1—N21—C23—C24	−4.3 (3)
N31—Cu1—N1—C21	130.40 (12)	N21—C23—C24—C25	48.3 (3)
N21—Cu1—N1—C21	9.13 (11)	N21—C23—C24—C29	−132.75 (19)
N11—Cu1—N1—C21	−109.91 (12)	C29—C24—C25—C26	2.1 (3)
N31—Cu1—N1—C11	−110.18 (12)	C23—C24—C25—C26	−178.89 (18)
N21—Cu1—N1—C11	128.54 (12)	C24—C25—C26—C27	−0.5 (3)
N11—Cu1—N1—C11	9.50 (12)	C25—C26—C27—C28	−1.8 (3)
C31—N1—C11—C12	−148.04 (16)	C26—C27—C28—C29	2.5 (3)
C21—N1—C11—C12	78.21 (19)	C27—C28—C29—C24	−0.9 (3)
Cu1—N1—C11—C12	−35.20 (17)	C27—C28—C29—N22	175.30 (18)
N31—Cu1—N11—C13	−82.4 (2)	C25—C24—C29—C28	−1.4 (3)
N21—Cu1—N11—C13	114.32 (19)	C23—C24—C29—C28	179.61 (17)
N1—Cu1—N11—C13	−164.35 (19)	C25—C24—C29—N22	−177.46 (17)
N31—Cu1—N11—C12	100.63 (12)	C23—C24—C29—N22	3.6 (3)
N21—Cu1—N11—C12	−62.63 (13)	C28—C29—N22—O22	24.8 (3)
N1—Cu1—N11—C12	18.70 (12)	C24—C29—N22—O22	−158.90 (18)
C12—N11—C13—C14	−176.99 (17)	C28—C29—N22—O21	−154.27 (18)
Cu1—N11—C13—C14	6.3 (3)	C24—C29—N22—O21	22.0 (3)
C13—N11—C12—C11	138.31 (18)	C21—N1—C31—C32	−148.52 (16)
Cu1—N11—C12—C11	−44.11 (17)	C11—N1—C31—C32	78.1 (2)
N1—C11—C12—N11	55.0 (2)	Cu1—N1—C31—C32	−35.00 (17)
N11—C13—C14—C15	37.0 (3)	N1—C31—C32—N31	53.3 (2)
N11—C13—C14—C19	−148.68 (19)	C31—C32—N31—C33	143.03 (17)
C19—C14—C15—C16	1.4 (3)	C31—C32—N31—Cu1	−41.54 (17)
C13—C14—C15—C16	176.15 (18)	N21—Cu1—N31—C33	−87.46 (19)
C14—C15—C16—C17	−0.3 (3)	N11—Cu1—N31—C33	109.68 (19)
C15—C16—C17—C18	−0.7 (3)	N1—Cu1—N31—C33	−168.75 (19)
C16—C17—C18—C19	0.6 (3)	N21—Cu1—N31—C32	98.31 (12)
C17—C18—C19—C14	0.6 (3)	N11—Cu1—N31—C32	−64.55 (13)
C17—C18—C19—N12	176.77 (17)	N1—Cu1—N31—C32	17.01 (12)
C15—C14—C19—C18	−1.6 (3)	C32—N31—C33—C34	−178.37 (16)
C13—C14—C19—C18	−176.11 (18)	Cu1—N31—C33—C34	7.8 (3)
C15—C14—C19—N12	−177.65 (17)	N31—C33—C34—C35	36.1 (3)
C13—C14—C19—N12	7.8 (3)	N31—C33—C34—C39	−149.65 (18)
C18—C19—N12—O12	37.8 (3)	C39—C34—C35—C36	1.6 (3)
C14—C19—N12—O12	−145.90 (18)	C33—C34—C35—C36	176.17 (18)
C18—C19—N12—O11	−141.16 (19)	C34—C35—C36—C37	−0.6 (3)
C14—C19—N12—O11	35.2 (3)	C35—C36—C37—C38	−0.9 (3)
C31—N1—C21—C22	80.34 (19)	C36—C37—C38—C39	1.3 (3)
C11—N1—C21—C22	−145.74 (16)	C37—C38—C39—C34	−0.2 (3)
Cu1—N1—C21—C22	−32.61 (17)	C37—C38—C39—N32	177.02 (17)
N1—C21—C22—N21	49.7 (2)	C35—C34—C39—C38	−1.2 (3)
C21—C22—N21—C23	138.70 (17)	C33—C34—C39—C38	−175.68 (17)
C21—C22—N21—Cu1	−39.54 (18)	C35—C34—C39—N32	−178.33 (17)
N31—Cu1—N21—C23	116.97 (17)	C33—C34—C39—N32	7.2 (3)
N11—Cu1—N21—C23	−80.04 (18)	C38—C39—N32—O32	38.4 (2)
N1—Cu1—N21—C23	−161.38 (18)	C34—C39—N32—O32	−144.24 (18)
N31—Cu1—N21—C22	−65.18 (13)	C38—C39—N32—O31	−141.33 (18)
N11—Cu1—N21—C22	97.81 (12)	C34—C39—N32—O31	36.0 (3)

(IV) chloro[tris(2-nitrobenzylaminoethyl)amine-κ⁴N]copper(II) chloride ethanol solvate top

Crystal data top

[Cu(C₂₇H₃₃N₇O₆)Cl]Cl·C₂H₆O	F(000) = 1524
M_r = 732.11	D_x = 1.512 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2629 reflections
a = 13.183 (5) Å	θ = 2.3–22.7°
b = 14.485 (6) Å	µ = 0.90 mm⁻¹
c = 16.914 (7) Å	T = 150 K
β = 95.319 (7)°	Plate, green
V = 3216 (2) Å³	0.23 × 0.21 × 0.07 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	5657 independent reflections
Radiation source: normal-focus sealed tube	3256 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.103
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −15→15
T_min = 0.819, T_max = 0.940	k = −16→17
22643 measured reflections	l = −20→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0768P)²] where P = (F_o² + 2F_c²)/3
5657 reflections	(Δ/σ)_max < 0.001
416 parameters	Δρ_max = 0.63 e Å⁻³
0 restraints	Δρ_min = −0.76 e Å⁻³

Crystal data top

[Cu(C₂₇H₃₃N₇O₆)Cl]Cl·C₂H₆O	V = 3216 (2) Å³
M_r = 732.11	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.183 (5) Å	µ = 0.90 mm⁻¹
b = 14.485 (6) Å	T = 150 K
c = 16.914 (7) Å	0.23 × 0.21 × 0.07 mm
β = 95.319 (7)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	5657 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	3256 reflections with I > 2σ(I)
T_min = 0.819, T_max = 0.940	R_int = 0.103
22643 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.153	H-atom parameters constrained
S = 0.98	Δρ_max = 0.63 e Å⁻³
5657 reflections	Δρ_min = −0.76 e Å⁻³
416 parameters

Special details top

Experimental. Analysis for [Cu^II(II)Cl]Cl·C₂H₅OH: calculated for [Cu(C₂₇H₃₃N₇O₆)Cl]Cl·C₂H₅OH: C 47.6, H 5.4, N 13.4%; found C 47.5, H 5.3, N 13.3%. IR (KBr, cm⁻¹) inter alia: 1524(s, NO₂), 1342(m, NO₂).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.28727 (5)	0.04347 (4)	0.77698 (4)	0.0234 (2)
Cl1	0.17505 (10)	0.06292 (9)	0.66933 (8)	0.0327 (4)
N1	0.3832 (3)	0.0309 (3)	0.8781 (2)	0.0211 (9)
C11	0.3957 (4)	−0.0687 (3)	0.8989 (3)	0.0251 (12)
H11A	0.4118	−0.0753	0.9569	0.030*
H11B	0.4530	−0.0949	0.8722	0.030*
C12	0.2997 (4)	−0.1200 (4)	0.8731 (3)	0.0253 (12)
H12A	0.3104	−0.1872	0.8811	0.030*
H12B	0.2444	−0.1001	0.9051	0.030*
N11	0.2714 (3)	−0.1004 (3)	0.7882 (2)	0.0217 (10)
H11N	0.3206	−0.1277	0.7599	0.026*
C13	0.1721 (4)	−0.1397 (4)	0.7575 (3)	0.0289 (13)
H13A	0.1561	−0.1189	0.7020	0.035*
H13B	0.1188	−0.1147	0.7892	0.035*
C14	0.1672 (4)	−0.2433 (4)	0.7595 (3)	0.0249 (12)
C15	0.2134 (4)	−0.3037 (4)	0.7103 (3)	0.0259 (12)
C16	0.2059 (4)	−0.3983 (4)	0.7175 (3)	0.0307 (13)
H16	0.2399	−0.4379	0.6838	0.037*
C17	0.1479 (5)	−0.4354 (4)	0.7748 (3)	0.0404 (15)
H17	0.1419	−0.5004	0.7800	0.048*
C18	0.1007 (5)	−0.3789 (4)	0.8224 (3)	0.0396 (15)
H18	0.0605	−0.4042	0.8608	0.048*
C19	0.1100 (4)	−0.2847 (4)	0.8159 (3)	0.0327 (14)
H19	0.0767	−0.2463	0.8510	0.039*
N12	0.2671 (3)	−0.2704 (4)	0.6425 (3)	0.0339 (12)
O11	0.2921 (3)	−0.3284 (3)	0.5952 (2)	0.0538 (12)
O12	0.2802 (3)	−0.1880 (3)	0.6360 (2)	0.0396 (10)
C21	0.4826 (4)	0.0718 (3)	0.8621 (3)	0.0235 (12)
H21A	0.5366	0.0499	0.9023	0.028*
H21B	0.4789	0.1400	0.8657	0.028*
C22	0.5080 (4)	0.0439 (4)	0.7797 (3)	0.0237 (12)
H22A	0.5702	0.0764	0.7663	0.028*
H22B	0.5209	−0.0234	0.7781	0.028*
N21	0.4219 (3)	0.0682 (3)	0.7223 (2)	0.0182 (9)
H21N	0.4256	0.1310	0.7116	0.022*
C23	0.4236 (4)	0.0170 (3)	0.6459 (3)	0.0242 (12)
H23A	0.3641	0.0363	0.6097	0.029*
H23B	0.4164	−0.0498	0.6563	0.029*
C24	0.5194 (4)	0.0321 (3)	0.6046 (3)	0.0223 (11)
C25	0.5449 (4)	0.1101 (4)	0.5632 (3)	0.0250 (12)
C26	0.6342 (4)	0.1173 (4)	0.5266 (3)	0.0365 (15)
H26	0.6492	0.1720	0.4989	0.044*
C27	0.7000 (4)	0.0448 (5)	0.5309 (3)	0.0405 (16)
H27	0.7611	0.0485	0.5054	0.049*
C28	0.6787 (4)	−0.0341 (4)	0.5722 (3)	0.0379 (15)
H28	0.7252	−0.0843	0.5753	0.045*
C29	0.5900 (4)	−0.0397 (4)	0.6087 (3)	0.0274 (12)
H29	0.5765	−0.0940	0.6375	0.033*
N22	0.4741 (4)	0.1895 (3)	0.5504 (3)	0.0327 (11)
O21	0.5031 (4)	0.2567 (3)	0.5156 (3)	0.0583 (13)
O22	0.3899 (3)	0.1842 (3)	0.5735 (2)	0.0458 (11)
C31	0.3380 (4)	0.0819 (4)	0.9417 (3)	0.0258 (12)
H31A	0.3916	0.0963	0.9849	0.031*
H31B	0.2858	0.0431	0.9640	0.031*
C32	0.2901 (4)	0.1698 (4)	0.9097 (3)	0.0291 (13)
H32A	0.2526	0.2001	0.9506	0.035*
H32B	0.3433	0.2128	0.8944	0.035*
N31	0.2191 (3)	0.1467 (3)	0.8393 (2)	0.0242 (10)
H31N	0.2142	0.1987	0.8069	0.029*
C33	0.1151 (4)	0.1251 (4)	0.8597 (3)	0.0290 (13)
H33A	0.1193	0.0746	0.8993	0.035*
H33B	0.0745	0.1023	0.8115	0.035*
C34	0.0591 (4)	0.2070 (4)	0.8932 (3)	0.0260 (12)
C35	−0.0190 (4)	0.1988 (4)	0.9428 (3)	0.0279 (13)
C36	−0.0674 (4)	0.2740 (4)	0.9718 (3)	0.0367 (15)
H36	−0.1209	0.2653	1.0051	0.044*
C37	−0.0385 (4)	0.3616 (4)	0.9527 (3)	0.0392 (15)
H37	−0.0708	0.4139	0.9731	0.047*
C38	0.0374 (4)	0.3721 (4)	0.9039 (4)	0.0382 (15)
H38	0.0573	0.4325	0.8897	0.046*
C39	0.0858 (4)	0.2963 (4)	0.8747 (3)	0.0324 (14)
H39	0.1388	0.3058	0.8412	0.039*
N32	−0.0568 (4)	0.1097 (4)	0.9645 (3)	0.0387 (13)
O31	−0.0953 (3)	0.1025 (3)	1.0282 (3)	0.0626 (14)
O32	−0.0505 (3)	0.0436 (3)	0.9195 (3)	0.0441 (11)
Cl2	0.50809 (11)	0.28124 (9)	0.74712 (8)	0.0341 (4)
O41	0.2750 (3)	0.3124 (3)	0.7463 (2)	0.0465 (11)
H41	0.3377	0.3014	0.7527	0.06 (2)*
C42	0.2477 (6)	0.3371 (5)	0.6668 (4)	0.065 (2)
H42A	0.2850	0.2978	0.6313	0.078*
H42B	0.2670	0.4022	0.6582	0.078*
C43	0.1383 (6)	0.3259 (5)	0.6474 (5)	0.085 (3)
H43A	0.1201	0.3443	0.5922	0.127*
H43B	0.1015	0.3647	0.6827	0.127*
H43C	0.1197	0.2610	0.6543	0.127*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0236 (4)	0.0272 (4)	0.0193 (3)	0.0020 (3)	0.0020 (3)	−0.0025 (3)
Cl1	0.0319 (8)	0.0368 (9)	0.0280 (8)	0.0061 (6)	−0.0047 (6)	−0.0011 (6)
N1	0.023 (2)	0.022 (2)	0.019 (2)	−0.0011 (19)	0.0062 (18)	−0.0009 (19)
C11	0.031 (3)	0.027 (3)	0.018 (3)	0.005 (2)	0.005 (2)	0.001 (2)
C12	0.025 (3)	0.031 (3)	0.021 (3)	−0.003 (2)	0.007 (2)	0.002 (2)
N11	0.018 (2)	0.029 (3)	0.018 (2)	−0.0024 (19)	0.0018 (18)	0.0008 (19)
C13	0.026 (3)	0.032 (3)	0.029 (3)	−0.005 (3)	0.003 (2)	−0.002 (3)
C14	0.014 (3)	0.033 (3)	0.026 (3)	−0.009 (2)	−0.004 (2)	0.000 (2)
C15	0.025 (3)	0.034 (3)	0.019 (3)	−0.007 (3)	0.001 (2)	0.001 (2)
C16	0.029 (3)	0.034 (3)	0.029 (3)	−0.007 (3)	0.002 (3)	−0.005 (3)
C17	0.050 (4)	0.030 (4)	0.040 (4)	−0.010 (3)	−0.002 (3)	0.003 (3)
C18	0.047 (4)	0.043 (4)	0.030 (3)	−0.010 (3)	0.007 (3)	0.004 (3)
C19	0.032 (3)	0.036 (4)	0.030 (3)	−0.003 (3)	0.005 (3)	−0.004 (3)
N12	0.030 (3)	0.048 (3)	0.023 (3)	0.000 (3)	0.002 (2)	−0.001 (2)
O11	0.067 (3)	0.055 (3)	0.043 (3)	0.006 (2)	0.026 (2)	−0.012 (2)
O12	0.046 (3)	0.042 (3)	0.032 (2)	−0.012 (2)	0.0091 (19)	0.002 (2)
C21	0.022 (3)	0.024 (3)	0.025 (3)	−0.004 (2)	0.004 (2)	0.002 (2)
C22	0.022 (3)	0.027 (3)	0.023 (3)	−0.003 (2)	0.004 (2)	−0.001 (2)
N21	0.025 (2)	0.017 (2)	0.013 (2)	0.0018 (18)	0.0024 (18)	0.0003 (17)
C23	0.028 (3)	0.022 (3)	0.024 (3)	−0.001 (2)	0.007 (2)	−0.003 (2)
C24	0.024 (3)	0.023 (3)	0.020 (3)	−0.009 (2)	0.003 (2)	−0.004 (2)
C25	0.031 (3)	0.028 (3)	0.016 (3)	−0.002 (3)	0.002 (2)	−0.004 (2)
C26	0.037 (4)	0.049 (4)	0.023 (3)	−0.014 (3)	0.000 (3)	0.003 (3)
C27	0.025 (3)	0.065 (5)	0.032 (3)	−0.010 (3)	0.011 (3)	−0.016 (3)
C28	0.029 (3)	0.050 (4)	0.034 (3)	0.011 (3)	0.001 (3)	−0.008 (3)
C29	0.032 (3)	0.031 (3)	0.019 (3)	0.005 (3)	0.004 (2)	−0.003 (2)
N22	0.048 (3)	0.027 (3)	0.021 (3)	0.000 (2)	−0.006 (2)	−0.002 (2)
O21	0.077 (4)	0.034 (3)	0.064 (3)	−0.006 (2)	0.007 (3)	0.022 (2)
O22	0.046 (3)	0.038 (3)	0.054 (3)	0.014 (2)	0.008 (2)	0.003 (2)
C31	0.021 (3)	0.034 (3)	0.023 (3)	0.008 (2)	0.004 (2)	−0.005 (2)
C32	0.023 (3)	0.035 (3)	0.029 (3)	0.005 (3)	0.000 (2)	−0.008 (3)
N31	0.021 (2)	0.025 (2)	0.027 (2)	0.0025 (19)	0.0018 (19)	−0.003 (2)
C33	0.022 (3)	0.038 (3)	0.027 (3)	0.004 (3)	0.006 (2)	−0.004 (3)
C34	0.020 (3)	0.033 (3)	0.024 (3)	0.003 (2)	0.000 (2)	−0.003 (2)
C35	0.025 (3)	0.034 (3)	0.024 (3)	0.000 (3)	0.001 (2)	0.010 (3)
C36	0.029 (3)	0.056 (4)	0.026 (3)	0.010 (3)	0.009 (3)	0.004 (3)
C37	0.034 (3)	0.045 (4)	0.040 (4)	0.013 (3)	0.010 (3)	−0.004 (3)
C38	0.034 (3)	0.030 (3)	0.052 (4)	0.003 (3)	0.010 (3)	−0.002 (3)
C39	0.024 (3)	0.037 (4)	0.038 (3)	0.002 (3)	0.013 (3)	0.002 (3)
N32	0.030 (3)	0.048 (3)	0.039 (3)	0.011 (3)	0.010 (2)	0.007 (3)
O31	0.061 (3)	0.068 (3)	0.066 (3)	0.016 (3)	0.041 (3)	0.026 (3)
O32	0.040 (2)	0.040 (3)	0.052 (3)	−0.007 (2)	0.000 (2)	0.008 (2)
Cl2	0.0379 (8)	0.0259 (8)	0.0390 (8)	−0.0060 (6)	0.0059 (6)	0.0003 (6)
O41	0.039 (3)	0.065 (3)	0.035 (3)	−0.010 (2)	0.003 (2)	−0.006 (2)
C42	0.070 (5)	0.065 (5)	0.060 (5)	0.033 (4)	0.006 (4)	−0.009 (4)
C43	0.092 (7)	0.071 (6)	0.085 (6)	0.013 (5)	−0.027 (5)	0.000 (5)

Geometric parameters (Å, º) top

Cu1—N1	2.038 (4)	C24—C29	1.394 (7)
Cu1—N31	2.081 (4)	C25—C26	1.384 (7)
Cu1—N11	2.105 (4)	C25—N22	1.484 (7)
Cu1—N21	2.107 (4)	C26—C27	1.360 (8)
Cu1—Cl1	2.2547 (16)	C26—H26	0.9500
N1—C31	1.476 (6)	C27—C28	1.382 (8)
N1—C21	1.486 (6)	C27—H27	0.9500
N1—C11	1.490 (6)	C28—C29	1.375 (7)
C11—C12	1.498 (7)	C28—H28	0.9500
C11—H11A	0.9900	C29—H29	0.9500
C11—H11B	0.9900	N22—O22	1.213 (6)
C12—N11	1.478 (6)	N22—O21	1.216 (6)
C12—H12A	0.9900	C31—C32	1.501 (7)
C12—H12B	0.9900	C31—H31A	0.9900
N11—C13	1.477 (6)	C31—H31B	0.9900
N11—H11N	0.9300	C32—N31	1.483 (6)
C13—C14	1.502 (7)	C32—H32A	0.9900
C13—H13A	0.9900	C32—H32B	0.9900
C13—H13B	0.9900	N31—C33	1.478 (6)
C14—C15	1.387 (7)	N31—H31N	0.9300
C14—C19	1.405 (7)	C33—C34	1.533 (7)
C15—C16	1.380 (7)	C33—H33A	0.9900
C15—N12	1.483 (6)	C33—H33B	0.9900
C16—C17	1.395 (7)	C34—C39	1.384 (7)
C16—H16	0.9500	C34—C35	1.393 (7)
C17—C18	1.341 (8)	C35—C36	1.376 (7)
C17—H17	0.9500	C35—N32	1.443 (7)
C18—C19	1.375 (8)	C36—C37	1.372 (8)
C18—H18	0.9500	C36—H36	0.9500
C19—H19	0.9500	C37—C38	1.363 (8)
N12—O12	1.212 (6)	C37—H37	0.9500
N12—O11	1.226 (6)	C38—C39	1.385 (7)
C21—C22	1.519 (6)	C38—H38	0.9500
C21—H21A	0.9900	C39—H39	0.9500
C21—H21B	0.9900	N32—O32	1.231 (6)
C22—N21	1.467 (6)	N32—O31	1.237 (6)
C22—H22A	0.9900	O41—C42	1.406 (8)
C22—H22B	0.9900	O41—H41	0.8400
N21—C23	1.491 (6)	C42—C43	1.458 (10)
N21—H21N	0.9300	C42—H42A	0.9900
C23—C24	1.514 (7)	C42—H42B	0.9900
C23—H23A	0.9900	C43—H43A	0.9800
C23—H23B	0.9900	C43—H43B	0.9800
C24—C25	1.386 (7)	C43—H43C	0.9800

N1—Cu1—N31	84.44 (16)	N21—C23—H23B	108.7
N1—Cu1—N11	83.97 (16)	C24—C23—H23B	108.7
N31—Cu1—N11	127.92 (16)	H23A—C23—H23B	107.6
N1—Cu1—N21	84.35 (15)	C25—C24—C29	116.2 (5)
N31—Cu1—N21	121.43 (16)	C25—C24—C23	127.0 (5)
N11—Cu1—N21	107.62 (15)	C29—C24—C23	116.8 (5)
N1—Cu1—Cl1	176.50 (12)	C26—C25—C24	123.0 (5)
N31—Cu1—Cl1	92.13 (12)	C26—C25—N22	115.1 (5)
N11—Cu1—Cl1	97.66 (11)	C24—C25—N22	121.8 (5)
N21—Cu1—Cl1	98.07 (11)	C27—C26—C25	118.8 (5)
C31—N1—C21	110.8 (4)	C27—C26—H26	120.6
C31—N1—C11	110.9 (4)	C25—C26—H26	120.6
C21—N1—C11	110.4 (4)	C26—C27—C28	120.5 (5)
C31—N1—Cu1	107.8 (3)	C26—C27—H27	119.8
C21—N1—Cu1	107.5 (3)	C28—C27—H27	119.8
C11—N1—Cu1	109.3 (3)	C29—C28—C27	119.9 (5)
N1—C11—C12	109.9 (4)	C29—C28—H28	120.1
N1—C11—H11A	109.7	C27—C28—H28	120.1
C12—C11—H11A	109.7	C28—C29—C24	121.6 (5)
N1—C11—H11B	109.7	C28—C29—H29	119.2
C12—C11—H11B	109.7	C24—C29—H29	119.2
H11A—C11—H11B	108.2	O22—N22—O21	122.9 (5)
N11—C12—C11	108.5 (4)	O22—N22—C25	119.0 (5)
N11—C12—H12A	110.0	O21—N22—C25	118.0 (5)
C11—C12—H12A	110.0	N1—C31—C32	110.2 (4)
N11—C12—H12B	110.0	N1—C31—H31A	109.6
C11—C12—H12B	110.0	C32—C31—H31A	109.6
H12A—C12—H12B	108.4	N1—C31—H31B	109.6
C13—N11—C12	113.8 (4)	C32—C31—H31B	109.6
C13—N11—Cu1	116.3 (3)	H31A—C31—H31B	108.1
C12—N11—Cu1	105.1 (3)	N31—C32—C31	108.2 (4)
C13—N11—H11N	107.1	N31—C32—H32A	110.1
C12—N11—H11N	107.1	C31—C32—H32A	110.1
Cu1—N11—H11N	107.1	N31—C32—H32B	110.1
N11—C13—C14	114.6 (4)	C31—C32—H32B	110.1
N11—C13—H13A	108.6	H32A—C32—H32B	108.4
C14—C13—H13A	108.6	C33—N31—C32	112.9 (4)
N11—C13—H13B	108.6	C33—N31—Cu1	114.8 (3)
C14—C13—H13B	108.6	C32—N31—Cu1	107.4 (3)
H13A—C13—H13B	107.6	C33—N31—H31N	107.1
C15—C14—C19	115.5 (5)	C32—N31—H31N	107.1
C15—C14—C13	126.5 (5)	Cu1—N31—H31N	107.1
C19—C14—C13	117.9 (5)	N31—C33—C34	114.3 (4)
C16—C15—C14	122.3 (5)	N31—C33—H33A	108.7
C16—C15—N12	115.8 (5)	C34—C33—H33A	108.7
C14—C15—N12	121.7 (5)	N31—C33—H33B	108.7
C15—C16—C17	119.5 (5)	C34—C33—H33B	108.7
C15—C16—H16	120.2	H33A—C33—H33B	107.6
C17—C16—H16	120.2	C39—C34—C35	115.7 (5)
C18—C17—C16	119.7 (5)	C39—C34—C33	119.9 (5)
C18—C17—H17	120.1	C35—C34—C33	124.4 (5)
C16—C17—H17	120.1	C36—C35—C34	122.7 (5)
C17—C18—C19	120.5 (6)	C36—C35—N32	115.8 (5)
C17—C18—H18	119.7	C34—C35—N32	121.4 (5)
C19—C18—H18	119.7	C37—C36—C35	120.0 (5)
C18—C19—C14	122.4 (5)	C37—C36—H36	120.0
C18—C19—H19	118.8	C35—C36—H36	120.0
C14—C19—H19	118.8	C38—C37—C36	118.8 (6)
O12—N12—O11	124.5 (5)	C38—C37—H37	120.6
O12—N12—C15	118.2 (5)	C36—C37—H37	120.6
O11—N12—C15	117.2 (5)	C37—C38—C39	121.0 (6)
N1—C21—C22	109.5 (4)	C37—C38—H38	119.5
N1—C21—H21A	109.8	C39—C38—H38	119.5
C22—C21—H21A	109.8	C34—C39—C38	121.7 (5)
N1—C21—H21B	109.8	C34—C39—H39	119.1
C22—C21—H21B	109.8	C38—C39—H39	119.1
H21A—C21—H21B	108.2	O32—N32—O31	122.0 (5)
N21—C22—C21	108.7 (4)	O32—N32—C35	119.5 (5)
N21—C22—H22A	109.9	O31—N32—C35	118.4 (5)
C21—C22—H22A	109.9	C42—O41—H41	109.5
N21—C22—H22B	109.9	O41—C42—C43	110.2 (7)
C21—C22—H22B	109.9	O41—C42—H42A	109.6
H22A—C22—H22B	108.3	C43—C42—H42A	109.6
C22—N21—C23	112.5 (4)	O41—C42—H42B	109.6
C22—N21—Cu1	107.5 (3)	C43—C42—H42B	109.6
C23—N21—Cu1	112.2 (3)	H42A—C42—H42B	108.1
C22—N21—H21N	108.2	C42—C43—H43A	109.5
C23—N21—H21N	108.2	C42—C43—H43B	109.5
Cu1—N21—H21N	108.2	H43A—C43—H43B	109.5
N21—C23—C24	114.1 (4)	C42—C43—H43C	109.5
N21—C23—H23A	108.7	H43A—C43—H43C	109.5
C24—C23—H23A	108.7	H43B—C43—H43C	109.5

N31—Cu1—N1—C31	13.4 (3)	N11—Cu1—N21—C23	54.1 (3)
N11—Cu1—N1—C31	−115.8 (3)	Cl1—Cu1—N21—C23	−46.7 (3)
N21—Cu1—N1—C31	135.8 (3)	C22—N21—C23—C24	−58.3 (5)
N31—Cu1—N1—C21	−106.1 (3)	Cu1—N21—C23—C24	−179.6 (3)
N11—Cu1—N1—C21	124.7 (3)	N21—C23—C24—C25	−74.9 (6)
N21—Cu1—N1—C21	16.3 (3)	N21—C23—C24—C29	104.7 (5)
N31—Cu1—N1—C11	134.0 (3)	C29—C24—C25—C26	1.0 (7)
N11—Cu1—N1—C11	4.8 (3)	C23—C24—C25—C26	−179.4 (5)
N21—Cu1—N1—C11	−103.6 (3)	C29—C24—C25—N22	176.5 (4)
C31—N1—C11—C12	86.9 (5)	C23—C24—C25—N22	−3.8 (8)
C21—N1—C11—C12	−150.0 (4)	C24—C25—C26—C27	0.2 (8)
Cu1—N1—C11—C12	−31.9 (4)	N22—C25—C26—C27	−175.6 (5)
N1—C11—C12—N11	53.1 (5)	C25—C26—C27—C28	−1.0 (8)
C11—C12—N11—C13	−174.2 (4)	C26—C27—C28—C29	0.4 (8)
C11—C12—N11—Cu1	−45.9 (4)	C27—C28—C29—C24	0.8 (8)
N1—Cu1—N11—C13	149.4 (3)	C25—C24—C29—C28	−1.5 (7)
N31—Cu1—N11—C13	71.2 (4)	C23—C24—C29—C28	178.9 (5)
N21—Cu1—N11—C13	−128.5 (3)	C26—C25—N22—O22	172.4 (5)
Cl1—Cu1—N11—C13	−27.5 (3)	C24—C25—N22—O22	−3.5 (7)
N1—Cu1—N11—C12	22.6 (3)	C26—C25—N22—O21	−6.3 (7)
N31—Cu1—N11—C12	−55.5 (3)	C24—C25—N22—O21	177.8 (5)
N21—Cu1—N11—C12	104.7 (3)	C21—N1—C31—C32	78.3 (5)
Cl1—Cu1—N11—C12	−154.3 (3)	C11—N1—C31—C32	−158.8 (4)
C12—N11—C13—C14	−63.3 (6)	Cu1—N1—C31—C32	−39.1 (5)
Cu1—N11—C13—C14	174.4 (3)	N1—C31—C32—N31	52.8 (5)
N11—C13—C14—C15	−72.7 (7)	C31—C32—N31—C33	88.9 (5)
N11—C13—C14—C19	107.7 (5)	C31—C32—N31—Cu1	−38.7 (5)
C19—C14—C15—C16	−1.5 (7)	N1—Cu1—N31—C33	−112.2 (3)
C13—C14—C15—C16	178.8 (5)	N11—Cu1—N31—C33	−34.3 (4)
C19—C14—C15—N12	173.5 (4)	N21—Cu1—N31—C33	167.9 (3)
C13—C14—C15—N12	−6.1 (8)	Cl1—Cu1—N31—C33	67.1 (3)
C14—C15—C16—C17	1.7 (8)	N1—Cu1—N31—C32	14.3 (3)
N12—C15—C16—C17	−173.7 (5)	N11—Cu1—N31—C32	92.1 (3)
C15—C16—C17—C18	−0.4 (9)	N21—Cu1—N31—C32	−65.6 (4)
C16—C17—C18—C19	−0.9 (9)	Cl1—Cu1—N31—C32	−166.4 (3)
C17—C18—C19—C14	1.0 (9)	C32—N31—C33—C34	66.0 (6)
C15—C14—C19—C18	0.2 (8)	Cu1—N31—C33—C34	−170.4 (3)
C13—C14—C19—C18	179.9 (5)	N31—C33—C34—C39	24.8 (7)
C16—C15—N12—O12	−176.2 (5)	N31—C33—C34—C35	−154.8 (5)
C14—C15—N12—O12	8.4 (7)	C39—C34—C35—C36	0.3 (8)
C16—C15—N12—O11	6.1 (7)	C33—C34—C35—C36	179.9 (5)
C14—C15—N12—O11	−169.2 (5)	C39—C34—C35—N32	177.8 (5)
C31—N1—C21—C22	−159.0 (4)	C33—C34—C35—N32	−2.6 (8)
C11—N1—C21—C22	77.8 (5)	C34—C35—C36—C37	−0.7 (9)
Cu1—N1—C21—C22	−41.4 (4)	N32—C35—C36—C37	−178.3 (5)
N1—C21—C22—N21	53.4 (5)	C35—C36—C37—C38	1.0 (9)
C21—C22—N21—C23	−161.0 (4)	C36—C37—C38—C39	−0.9 (9)
C21—C22—N21—Cu1	−37.0 (4)	C35—C34—C39—C38	−0.2 (8)
N1—Cu1—N21—C22	11.8 (3)	C33—C34—C39—C38	−179.8 (5)
N31—Cu1—N21—C22	91.7 (3)	C37—C38—C39—C34	0.5 (9)
N11—Cu1—N21—C22	−70.0 (3)	C36—C35—N32—O32	150.6 (5)
Cl1—Cu1—N21—C22	−170.8 (3)	C34—C35—N32—O32	−27.1 (8)
N1—Cu1—N21—C23	135.9 (3)	C36—C35—N32—O31	−29.1 (7)
N31—Cu1—N21—C23	−144.2 (3)	C34—C35—N32—O31	153.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N31—H31N···O41	0.93	2.13	2.998 (6)	154
N11—H11N···O12	0.93	2.29	2.882 (6)	121
N11—H11N···Cl2ⁱ	0.93	2.63	3.474 (4)	152
N21—H21N···O22	0.93	2.46	3.023 (6)	119
N21—H21N···Cl2	0.93	2.48	3.302 (4)	147
O41—H41···Cl2	0.84	2.28	3.105 (5)	170

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

(VI) [tris(2-nitrobenzylideneaminopropyl)amine-κ⁴N]copper(I) perchlorate top

Crystal data top

[Cu(C₃₀H₃₃N₇O₆)]ClO₄	F(000) = 1552
M_r = 750.62	D_x = 1.499 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9345 reflections
a = 9.5361 (7) Å	θ = 2.2–27.6°
b = 18.6870 (13) Å	µ = 0.80 mm⁻¹
c = 19.2367 (13) Å	T = 150 K
β = 104.044 (1)°	Lath, red
V = 3325.5 (4) Å³	0.47 × 0.17 × 0.13 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	7892 independent reflections
Radiation source: normal-focus sealed tube	5773 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 28.8°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −12→12
T_min = 0.704, T_max = 0.903	k = −24→23
28475 measured reflections	l = −25→24

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0534P)² + 2.0893P] where P = (F_o² + 2F_c²)/3
7892 reflections	(Δ/σ)_max = 0.001
455 parameters	Δρ_max = 0.50 e Å⁻³
62 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

[Cu(C₃₀H₃₃N₇O₆)]ClO₄	V = 3325.5 (4) Å³
M_r = 750.62	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.5361 (7) Å	µ = 0.80 mm⁻¹
b = 18.6870 (13) Å	T = 150 K
c = 19.2367 (13) Å	0.47 × 0.17 × 0.13 mm
β = 104.044 (1)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	7892 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	5773 reflections with I > 2σ(I)
T_min = 0.704, T_max = 0.903	R_int = 0.028
28475 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	62 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 1.00	Δρ_max = 0.50 e Å⁻³
7892 reflections	Δρ_min = −0.33 e Å⁻³
455 parameters

Special details top

Experimental. Analysis for [Cu^I(V)]ClO₄: calculated for [C₃₀H₃₃N₇O₆Cu]ClO₄: C 48.0, H 4.4, N 13.1%; found C 47.2, H 4.3, N 12.8%. NMR (CDCl₃, p.p.m., ¹H): 1.95(m, 6, CH₂), 2.70(t, 6, CH₂), 3.10(t, 6, CH₂), 8.30(s, 3, imine), 8.05(d, 3, aromatic), 8.1(d, 3, aromatic), 7.6(t, 3, aromatic), 8.4(t, 3, aromatic). Mass spectrum (FAB): m/e 651, [Cu^I(V)]⁺. IR (KBr, cm⁻¹) inter alia: 1636(m, imine), 1524(s, NO₂), 1343(m, NO₂), 1090(s, ClO₄), 622(m, ClO₄).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.02157 (3)	0.223560 (14)	0.910299 (13)	0.02903 (9)
N1	−0.1161 (2)	0.15678 (11)	0.96041 (10)	0.0389 (5)
C11	−0.0686 (3)	0.16289 (17)	1.03977 (13)	0.0497 (7)
H11A	−0.1262	0.1288	1.0609	0.060*
H11B	−0.0923	0.2117	1.0535	0.060*
C12	0.0901 (3)	0.14910 (16)	1.07336 (13)	0.0505 (7)
H12A	0.1150	0.1011	1.0581	0.061*
H12B	0.1042	0.1479	1.1261	0.061*
C13	0.1955 (3)	0.20316 (15)	1.05538 (12)	0.0429 (6)
H13A	0.1628	0.2522	1.0630	0.051*
H13B	0.2921	0.1960	1.0880	0.051*
N11	0.2066 (2)	0.19578 (10)	0.98013 (10)	0.0326 (4)
C14	0.3129 (2)	0.15948 (12)	0.97089 (13)	0.0369 (5)
H14	0.3767	0.1385	1.0114	0.044*
C15	0.3412 (2)	0.14859 (13)	0.89963 (13)	0.0372 (5)
C16	0.3357 (3)	0.20614 (14)	0.85352 (14)	0.0424 (6)
H16	0.3070	0.2518	0.8669	0.051*
C17	0.3713 (3)	0.19835 (19)	0.78834 (16)	0.0623 (9)
H17	0.3652	0.2381	0.7570	0.075*
C18	0.4155 (3)	0.1325 (2)	0.7690 (2)	0.0759 (12)
H18	0.4406	0.1274	0.7243	0.091*
C19	0.4238 (3)	0.0745 (2)	0.8136 (2)	0.0693 (10)
H19	0.4548	0.0293	0.8003	0.083*
C20	0.3865 (3)	0.08298 (15)	0.87755 (16)	0.0502 (7)
N12	0.3846 (3)	0.01910 (13)	0.92271 (16)	0.0681 (8)
O11	0.2900 (3)	0.01515 (13)	0.95421 (15)	0.0798 (8)
O12	0.4765 (3)	−0.02615 (13)	0.92152 (15)	0.1085 (11)
C21	−0.2703 (3)	0.17882 (16)	0.93795 (15)	0.0492 (6)
H21A	−0.3246	0.1526	0.9678	0.059*
H21B	−0.3092	0.1636	0.8877	0.059*
C22	−0.2999 (3)	0.25835 (16)	0.94312 (15)	0.0478 (6)
H22A	−0.4059	0.2656	0.9325	0.057*
H22B	−0.2591	0.2740	0.9931	0.057*
C23	−0.2391 (3)	0.30596 (15)	0.89354 (13)	0.0437 (6)
H23A	−0.2592	0.2842	0.8452	0.052*
H23B	−0.2872	0.3533	0.8894	0.052*
N21	−0.0814 (2)	0.31535 (10)	0.92116 (9)	0.0331 (4)
C24	−0.0449 (3)	0.37267 (13)	0.95633 (12)	0.0398 (5)
H24	−0.1194	0.4050	0.9604	0.048*
C25	0.1052 (3)	0.39227 (12)	0.99124 (12)	0.0403 (6)
C26	0.2140 (3)	0.38701 (14)	0.95509 (14)	0.0479 (6)
H26	0.1925	0.3673	0.9082	0.058*
C27	0.3534 (4)	0.40983 (18)	0.98594 (17)	0.0646 (8)
H27	0.4266	0.4047	0.9605	0.078*
C28	0.3864 (4)	0.43999 (18)	1.05364 (18)	0.0712 (10)
H28	0.4821	0.4556	1.0746	0.085*
C29	0.2800 (4)	0.44736 (16)	1.09061 (16)	0.0645 (9)
H29	0.3009	0.4691	1.1366	0.077*
C30	0.1432 (4)	0.42269 (14)	1.05965 (14)	0.0512 (7)
N22	0.0358 (4)	0.42517 (15)	1.10307 (13)	0.0671 (8)
O21	−0.0603 (3)	0.38050 (14)	1.09181 (12)	0.0779 (7)
O22	0.0495 (4)	0.47159 (16)	1.14926 (13)	0.1033 (10)
C31	−0.1053 (3)	0.08058 (13)	0.93970 (15)	0.0483 (6)
H31A	−0.1750	0.0524	0.9592	0.058*
H31B	−0.0073	0.0631	0.9633	0.058*
C32	−0.1328 (3)	0.06489 (13)	0.86035 (14)	0.0456 (6)
H32A	−0.2276	0.0855	0.8361	0.055*
H32B	−0.1397	0.0124	0.8536	0.055*
C33	−0.0198 (3)	0.09314 (12)	0.82358 (13)	0.0374 (5)
H33A	0.0777	0.0802	0.8524	0.045*
H33B	−0.0336	0.0703	0.7760	0.045*
N31	−0.02942 (19)	0.17141 (9)	0.81474 (9)	0.0300 (4)
C34	−0.0817 (2)	0.19367 (12)	0.75154 (11)	0.0334 (5)
H34	−0.1073	0.1601	0.7134	0.040*
C35	−0.1036 (2)	0.27078 (12)	0.73611 (11)	0.0315 (5)
C36	0.0049 (3)	0.31971 (13)	0.76432 (12)	0.0360 (5)
H36	0.0955	0.3026	0.7915	0.043*
C37	−0.0154 (3)	0.39285 (14)	0.75396 (12)	0.0406 (5)
H37	0.0608	0.4252	0.7736	0.049*
C38	−0.1463 (3)	0.41817 (14)	0.71510 (14)	0.0456 (6)
H38	−0.1622	0.4683	0.7100	0.055*
C39	−0.2544 (3)	0.37147 (14)	0.68358 (13)	0.0434 (6)
H39	−0.3435	0.3890	0.6551	0.052*
C40	−0.2322 (2)	0.29902 (13)	0.69361 (11)	0.0344 (5)
N32	−0.3508 (2)	0.25103 (13)	0.65973 (12)	0.0447 (5)
O31	−0.3632 (2)	0.19473 (12)	0.68929 (12)	0.0647 (6)
O32	−0.4299 (2)	0.26989 (12)	0.60247 (12)	0.0665 (6)
Cl1	0.40434 (14)	0.42079 (12)	0.77914 (7)	0.0409 (4)	0.727 (6)
O1	0.5533 (2)	0.43696 (13)	0.79311 (13)	0.0719 (6)	0.727 (6)
O2	0.3833 (3)	0.36790 (12)	0.82863 (13)	0.0839 (8)	0.727 (6)
O3	0.3536 (6)	0.3974 (3)	0.70869 (18)	0.125 (2)	0.727 (6)
O4	0.3304 (4)	0.4854 (2)	0.7881 (2)	0.0979 (16)	0.727 (6)
O1'	0.5533 (2)	0.43696 (13)	0.79311 (13)	0.0719 (6)	0.273 (6)
O2'	0.3833 (3)	0.36790 (12)	0.82863 (13)	0.0839 (8)	0.273 (6)
Cl1'	0.4221 (3)	0.3989 (2)	0.76720 (19)	0.0342 (8)*	0.273 (6)
O3'	0.4398 (9)	0.3488 (4)	0.7175 (4)	0.056 (2)*	0.273 (6)
O4'	0.3141 (9)	0.4512 (5)	0.7380 (5)	0.068 (3)*	0.273 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.02987 (14)	0.03104 (14)	0.02508 (13)	−0.00160 (11)	0.00455 (10)	0.00186 (10)
N1	0.0372 (11)	0.0431 (11)	0.0366 (10)	−0.0068 (9)	0.0096 (9)	0.0055 (9)
C11	0.0507 (15)	0.0668 (18)	0.0345 (13)	−0.0101 (13)	0.0159 (11)	0.0105 (12)
C12	0.0573 (16)	0.0645 (18)	0.0284 (12)	−0.0032 (14)	0.0080 (11)	0.0141 (12)
C13	0.0427 (13)	0.0570 (16)	0.0248 (11)	−0.0017 (11)	0.0001 (10)	0.0034 (10)
N11	0.0304 (9)	0.0350 (10)	0.0295 (9)	−0.0047 (8)	0.0016 (8)	0.0020 (8)
C14	0.0298 (11)	0.0356 (12)	0.0396 (12)	−0.0057 (9)	−0.0030 (9)	0.0033 (10)
C15	0.0212 (10)	0.0413 (13)	0.0467 (13)	−0.0060 (9)	0.0036 (9)	−0.0070 (11)
C16	0.0332 (12)	0.0487 (14)	0.0476 (14)	−0.0106 (11)	0.0144 (11)	−0.0060 (11)
C17	0.0607 (18)	0.079 (2)	0.0553 (17)	−0.0341 (16)	0.0297 (15)	−0.0147 (16)
C18	0.061 (2)	0.101 (3)	0.080 (2)	−0.0427 (19)	0.0445 (18)	−0.054 (2)
C19	0.0364 (15)	0.071 (2)	0.103 (3)	−0.0168 (14)	0.0221 (16)	−0.049 (2)
C20	0.0291 (12)	0.0470 (15)	0.0686 (18)	−0.0063 (11)	0.0005 (12)	−0.0233 (14)
N12	0.0596 (16)	0.0357 (13)	0.082 (2)	0.0038 (12)	−0.0350 (15)	−0.0195 (13)
O11	0.0775 (17)	0.0524 (14)	0.0935 (19)	−0.0160 (13)	−0.0101 (15)	0.0199 (13)
O12	0.112 (2)	0.0635 (15)	0.109 (2)	0.0413 (15)	−0.0540 (17)	−0.0451 (15)
C21	0.0331 (13)	0.0598 (17)	0.0558 (16)	−0.0126 (12)	0.0127 (12)	0.0007 (13)
C22	0.0302 (12)	0.0634 (18)	0.0508 (15)	−0.0018 (12)	0.0118 (11)	−0.0059 (13)
C23	0.0364 (13)	0.0522 (15)	0.0399 (13)	0.0101 (11)	0.0042 (10)	−0.0007 (11)
N21	0.0370 (10)	0.0360 (10)	0.0259 (9)	0.0033 (8)	0.0071 (8)	0.0018 (8)
C24	0.0543 (15)	0.0367 (13)	0.0312 (11)	0.0066 (11)	0.0156 (11)	0.0025 (10)
C25	0.0626 (16)	0.0282 (11)	0.0293 (11)	−0.0064 (11)	0.0096 (11)	−0.0014 (9)
C26	0.0584 (16)	0.0479 (15)	0.0371 (13)	−0.0150 (13)	0.0107 (12)	−0.0069 (11)
C27	0.0641 (19)	0.070 (2)	0.0579 (18)	−0.0260 (16)	0.0124 (15)	−0.0059 (16)
C28	0.078 (2)	0.066 (2)	0.0579 (19)	−0.0324 (18)	−0.0064 (17)	−0.0040 (16)
C29	0.097 (3)	0.0477 (17)	0.0400 (15)	−0.0187 (17)	−0.0008 (16)	−0.0052 (13)
C30	0.082 (2)	0.0358 (13)	0.0342 (13)	−0.0058 (13)	0.0113 (13)	−0.0034 (11)
N22	0.110 (2)	0.0592 (16)	0.0355 (12)	0.0014 (16)	0.0247 (14)	−0.0087 (12)
O21	0.115 (2)	0.0789 (17)	0.0520 (13)	−0.0152 (15)	0.0436 (13)	−0.0069 (12)
O22	0.158 (3)	0.097 (2)	0.0623 (15)	−0.0051 (19)	0.0406 (17)	−0.0410 (15)
C31	0.0553 (16)	0.0373 (13)	0.0528 (15)	−0.0116 (12)	0.0143 (13)	0.0115 (12)
C32	0.0471 (15)	0.0317 (12)	0.0536 (15)	−0.0090 (11)	0.0034 (12)	0.0023 (11)
C33	0.0414 (13)	0.0274 (11)	0.0388 (12)	0.0011 (10)	0.0007 (10)	−0.0035 (9)
N31	0.0305 (9)	0.0279 (9)	0.0294 (9)	−0.0002 (7)	0.0030 (7)	−0.0014 (7)
C34	0.0357 (12)	0.0370 (12)	0.0265 (10)	0.0011 (10)	0.0056 (9)	−0.0043 (9)
C35	0.0388 (12)	0.0356 (12)	0.0222 (9)	0.0026 (9)	0.0110 (9)	0.0027 (9)
C36	0.0405 (13)	0.0381 (12)	0.0281 (11)	0.0028 (10)	0.0058 (9)	0.0028 (9)
C37	0.0491 (14)	0.0410 (13)	0.0320 (12)	−0.0032 (11)	0.0103 (11)	0.0018 (10)
C38	0.0580 (16)	0.0373 (13)	0.0416 (13)	0.0044 (12)	0.0124 (12)	0.0084 (11)
C39	0.0441 (14)	0.0467 (14)	0.0377 (13)	0.0098 (12)	0.0068 (11)	0.0122 (11)
C40	0.0361 (12)	0.0430 (13)	0.0247 (10)	−0.0007 (10)	0.0085 (9)	0.0047 (9)
N32	0.0362 (11)	0.0532 (13)	0.0434 (12)	0.0016 (10)	0.0070 (9)	0.0039 (10)
O31	0.0543 (12)	0.0640 (13)	0.0710 (14)	−0.0212 (10)	0.0059 (10)	0.0180 (11)
O32	0.0519 (12)	0.0741 (15)	0.0588 (13)	0.0025 (10)	−0.0151 (10)	0.0065 (11)
Cl1	0.0379 (5)	0.0469 (8)	0.0359 (5)	−0.0129 (5)	0.0050 (4)	0.0023 (5)
O1	0.0490 (12)	0.0745 (15)	0.0832 (16)	−0.0188 (11)	−0.0015 (11)	0.0127 (12)
O2	0.120 (2)	0.0602 (14)	0.0898 (17)	−0.0138 (14)	0.0616 (16)	0.0163 (13)
O3	0.134 (4)	0.174 (5)	0.044 (2)	−0.029 (4)	−0.022 (2)	−0.034 (2)
O4	0.101 (3)	0.080 (3)	0.110 (3)	0.033 (2)	0.019 (2)	0.014 (2)
O1'	0.0490 (12)	0.0745 (15)	0.0832 (16)	−0.0188 (11)	−0.0015 (11)	0.0127 (12)
O2'	0.120 (2)	0.0602 (14)	0.0898 (17)	−0.0138 (14)	0.0616 (16)	0.0163 (13)

Geometric parameters (Å, º) top

Cu1—N21	2.0124 (19)	C25—C26	1.386 (4)
Cu1—N11	2.0093 (18)	C25—C30	1.398 (3)
Cu1—N31	2.0326 (17)	C26—C27	1.385 (4)
Cu1—N1	2.1965 (19)	C26—H26	0.9500
N1—C11	1.488 (3)	C27—C28	1.383 (4)
N1—C21	1.487 (3)	C27—H27	0.9500
N1—C31	1.489 (3)	C28—C29	1.380 (5)
C11—C12	1.516 (4)	C28—H28	0.9500
C11—H11A	0.9900	C29—C30	1.376 (4)
C11—H11B	0.9900	C29—H29	0.9500
C12—C13	1.523 (4)	C30—N22	1.471 (4)
C12—H12A	0.9900	N22—O21	1.219 (4)
C12—H12B	0.9900	N22—O22	1.226 (3)
C13—N11	1.483 (3)	C31—C32	1.513 (4)
C13—H13A	0.9900	C31—H31A	0.9900
C13—H13B	0.9900	C31—H31B	0.9900
N11—C14	1.267 (3)	C32—C33	1.520 (4)
C14—C15	1.474 (3)	C32—H32A	0.9900
C14—H14	0.9500	C32—H32B	0.9900
C15—C16	1.387 (4)	C33—N31	1.473 (3)
C15—C20	1.400 (3)	C33—H33A	0.9900
C16—C17	1.384 (4)	C33—H33B	0.9900
C16—H16	0.9500	N31—C34	1.267 (3)
C17—C18	1.380 (5)	C34—C35	1.476 (3)
C17—H17	0.9500	C34—H34	0.9500
C18—C19	1.373 (5)	C35—C36	1.389 (3)
C18—H18	0.9500	C35—C40	1.401 (3)
C19—C20	1.371 (4)	C36—C37	1.388 (3)
C19—H19	0.9500	C36—H36	0.9500
C20—N12	1.479 (4)	C37—C38	1.374 (4)
N12—O11	1.205 (4)	C37—H37	0.9500
N12—O12	1.222 (3)	C38—C39	1.374 (4)
C21—C22	1.521 (4)	C38—H38	0.9500
C21—H21A	0.9900	C39—C40	1.377 (3)
C21—H21B	0.9900	C39—H39	0.9500
C22—C23	1.519 (4)	C40—N32	1.466 (3)
C22—H22A	0.9900	N32—O31	1.215 (3)
C22—H22B	0.9900	N32—O32	1.226 (3)
C23—N21	1.479 (3)	Cl1—O3	1.394 (4)
C23—H23A	0.9900	Cl1—O1	1.413 (2)
C23—H23B	0.9900	Cl1—O2	1.420 (2)
N21—C24	1.270 (3)	Cl1—O4	1.430 (4)
C24—C25	1.472 (4)	Cl1'—O3'	1.378 (7)
C24—H24	0.9500	Cl1'—O4'	1.432 (8)

N21—Cu1—N11	121.49 (8)	C23—N21—Cu1	109.94 (15)
N21—Cu1—N31	119.13 (7)	N21—C24—C25	124.3 (2)
N11—Cu1—N31	117.34 (7)	N21—C24—H24	117.9
N21—Cu1—N1	94.59 (8)	C25—C24—H24	117.9
N11—Cu1—N1	94.67 (7)	C26—C25—C30	116.5 (3)
N31—Cu1—N1	95.00 (7)	C26—C25—C24	121.1 (2)
C11—N1—C21	108.1 (2)	C30—C25—C24	122.1 (2)
C11—N1—C31	108.9 (2)	C27—C26—C25	121.4 (3)
C21—N1—C31	108.3 (2)	C27—C26—H26	119.3
C11—N1—Cu1	109.95 (15)	C25—C26—H26	119.3
C21—N1—Cu1	111.68 (15)	C28—C27—C26	120.3 (3)
C31—N1—Cu1	109.79 (15)	C28—C27—H27	119.9
N1—C11—C12	116.6 (2)	C26—C27—H27	119.9
N1—C11—H11A	108.1	C29—C28—C27	119.9 (3)
C12—C11—H11A	108.1	C29—C28—H28	120.1
N1—C11—H11B	108.1	C27—C28—H28	120.1
C12—C11—H11B	108.1	C28—C29—C30	118.8 (3)
H11A—C11—H11B	107.3	C28—C29—H29	120.6
C11—C12—C13	115.8 (2)	C30—C29—H29	120.6
C11—C12—H12A	108.3	C29—C30—C25	123.1 (3)
C13—C12—H12A	108.3	C29—C30—N22	117.5 (3)
C11—C12—H12B	108.3	C25—C30—N22	119.3 (3)
C13—C12—H12B	108.3	O21—N22—O22	123.8 (3)
H12A—C12—H12B	107.4	O21—N22—C30	118.3 (2)
N11—C13—C12	111.6 (2)	O22—N22—C30	117.9 (3)
N11—C13—H13A	109.3	N1—C31—C32	116.7 (2)
C12—C13—H13A	109.3	N1—C31—H31A	108.1
N11—C13—H13B	109.3	C32—C31—H31A	108.1
C12—C13—H13B	109.3	N1—C31—H31B	108.1
H13A—C13—H13B	108.0	C32—C31—H31B	108.1
C14—N11—C13	115.8 (2)	H31A—C31—H31B	107.3
C14—N11—Cu1	130.32 (16)	C31—C32—C33	115.7 (2)
C13—N11—Cu1	111.66 (15)	C31—C32—H32A	108.4
N11—C14—C15	122.5 (2)	C33—C32—H32A	108.4
N11—C14—H14	118.7	C31—C32—H32B	108.4
C15—C14—H14	118.7	C33—C32—H32B	108.4
C16—C15—C20	116.9 (2)	H32A—C32—H32B	107.4
C16—C15—C14	120.1 (2)	N31—C33—C32	111.56 (19)
C20—C15—C14	122.9 (2)	N31—C33—H33A	109.3
C17—C16—C15	121.2 (3)	C32—C33—H33A	109.3
C17—C16—H16	119.4	N31—C33—H33B	109.3
C15—C16—H16	119.4	C32—C33—H33B	109.3
C18—C17—C16	119.8 (3)	H33A—C33—H33B	108.0
C18—C17—H17	120.1	C34—N31—C33	115.83 (19)
C16—C17—H17	120.1	C34—N31—Cu1	131.49 (16)
C17—C18—C19	120.6 (3)	C33—N31—Cu1	112.16 (13)
C17—C18—H18	119.7	N31—C34—C35	121.1 (2)
C19—C18—H18	119.7	N31—C34—H34	119.4
C20—C19—C18	118.8 (3)	C35—C34—H34	119.4
C20—C19—H19	120.6	C36—C35—C40	116.3 (2)
C18—C19—H19	120.6	C36—C35—C34	120.6 (2)
C19—C20—C15	122.7 (3)	C40—C35—C34	123.1 (2)
C19—C20—N12	118.5 (3)	C37—C36—C35	121.9 (2)
C15—C20—N12	118.7 (3)	C37—C36—H36	119.1
O11—N12—O12	126.5 (4)	C35—C36—H36	119.1
O11—N12—C20	117.5 (2)	C38—C37—C36	119.6 (2)
O12—N12—C20	115.9 (4)	C38—C37—H37	120.2
N1—C21—C22	116.0 (2)	C36—C37—H37	120.2
N1—C21—H21A	108.3	C37—C38—C39	120.4 (2)
C22—C21—H21A	108.3	C37—C38—H38	119.8
N1—C21—H21B	108.3	C39—C38—H38	119.8
C22—C21—H21B	108.3	C38—C39—C40	119.3 (2)
H21A—C21—H21B	107.4	C38—C39—H39	120.3
C23—C22—C21	115.2 (2)	C40—C39—H39	120.3
C23—C22—H22A	108.5	C39—C40—C35	122.3 (2)
C21—C22—H22A	108.5	C39—C40—N32	117.6 (2)
C23—C22—H22B	108.5	C35—C40—N32	120.0 (2)
C21—C22—H22B	108.5	O31—N32—O32	124.1 (2)
H22A—C22—H22B	107.5	O31—N32—C40	118.3 (2)
N21—C23—C22	110.7 (2)	O32—N32—C40	117.6 (2)
N21—C23—H23A	109.5	O3—Cl1—O1	110.3 (3)
C22—C23—H23A	109.5	O3—Cl1—O2	111.2 (3)
N21—C23—H23B	109.5	O1—Cl1—O2	108.70 (17)
C22—C23—H23B	109.5	O3—Cl1—O4	108.5 (3)
H23A—C23—H23B	108.1	O1—Cl1—O4	107.4 (2)
C24—N21—C23	114.5 (2)	O2—Cl1—O4	110.6 (2)
C24—N21—Cu1	134.18 (17)	O3'—Cl1'—O4'	112.9 (6)

N21—Cu1—N1—C11	−79.89 (17)	N1—Cu1—N21—C23	−50.09 (15)
N11—Cu1—N1—C11	42.27 (18)	C23—N21—C24—C25	177.6 (2)
N31—Cu1—N1—C11	160.29 (17)	Cu1—N21—C24—C25	12.7 (4)
N21—Cu1—N1—C21	40.08 (17)	N21—C24—C25—C26	47.6 (4)
N11—Cu1—N1—C21	162.25 (17)	N21—C24—C25—C30	−138.0 (3)
N31—Cu1—N1—C21	−79.74 (17)	C30—C25—C26—C27	1.0 (4)
N21—Cu1—N1—C31	160.29 (16)	C24—C25—C26—C27	175.6 (3)
N11—Cu1—N1—C31	−77.55 (16)	C25—C26—C27—C28	−1.3 (5)
N31—Cu1—N1—C31	40.47 (16)	C26—C27—C28—C29	0.0 (5)
C21—N1—C11—C12	−174.7 (2)	C27—C28—C29—C30	1.6 (5)
C31—N1—C11—C12	67.7 (3)	C28—C29—C30—C25	−2.0 (5)
Cu1—N1—C11—C12	−52.6 (3)	C28—C29—C30—N22	174.4 (3)
N1—C11—C12—C13	66.2 (3)	C26—C25—C30—C29	0.7 (4)
C11—C12—C13—N11	−71.9 (3)	C24—C25—C30—C29	−173.9 (3)
C12—C13—N11—C14	−97.6 (3)	C26—C25—C30—N22	−175.6 (2)
C12—C13—N11—Cu1	67.3 (2)	C24—C25—C30—N22	9.7 (4)
N21—Cu1—N11—C14	−149.4 (2)	C29—C30—N22—O21	−150.6 (3)
N31—Cu1—N11—C14	14.2 (2)	C25—C30—N22—O21	26.0 (4)
N1—Cu1—N11—C14	112.3 (2)	C29—C30—N22—O22	28.4 (4)
N21—Cu1—N11—C13	48.45 (18)	C25—C30—N22—O22	−155.0 (3)
N31—Cu1—N11—C13	−147.92 (15)	C11—N1—C31—C32	−173.2 (2)
N1—Cu1—N11—C13	−49.84 (16)	C21—N1—C31—C32	69.5 (3)
C13—N11—C14—C15	−178.5 (2)	Cu1—N1—C31—C32	−52.7 (3)
Cu1—N11—C14—C15	20.0 (3)	N1—C31—C32—C33	68.2 (3)
N11—C14—C15—C16	46.6 (3)	C31—C32—C33—N31	−73.0 (3)
N11—C14—C15—C20	−139.1 (2)	C32—C33—N31—C34	−106.8 (2)
C20—C15—C16—C17	1.0 (4)	C32—C33—N31—Cu1	65.9 (2)
C14—C15—C16—C17	175.6 (2)	N21—Cu1—N31—C34	25.4 (2)
C15—C16—C17—C18	−1.2 (4)	N11—Cu1—N31—C34	−138.6 (2)
C16—C17—C18—C19	0.4 (5)	N1—Cu1—N31—C34	123.5 (2)
C17—C18—C19—C20	0.4 (5)	N21—Cu1—N31—C33	−145.80 (14)
C18—C19—C20—C15	−0.5 (4)	N11—Cu1—N31—C33	50.17 (17)
C18—C19—C20—N12	175.3 (3)	N1—Cu1—N31—C33	−47.72 (15)
C16—C15—C20—C19	−0.2 (4)	C33—N31—C34—C35	177.0 (2)
C14—C15—C20—C19	−174.6 (2)	Cu1—N31—C34—C35	6.1 (3)
C16—C15—C20—N12	−176.0 (2)	N31—C34—C35—C36	46.8 (3)
C14—C15—C20—N12	9.6 (3)	N31—C34—C35—C40	−132.7 (2)
C19—C20—N12—O11	−141.9 (3)	C40—C35—C36—C37	3.1 (3)
C15—C20—N12—O11	34.1 (3)	C34—C35—C36—C37	−176.5 (2)
C19—C20—N12—O12	34.9 (3)	C35—C36—C37—C38	0.4 (4)
C15—C20—N12—O12	−149.2 (2)	C36—C37—C38—C39	−3.3 (4)
C11—N1—C21—C22	72.1 (3)	C37—C38—C39—C40	2.5 (4)
C31—N1—C21—C22	−170.0 (2)	C38—C39—C40—C35	1.2 (4)
Cu1—N1—C21—C22	−49.0 (3)	C38—C39—C40—N32	179.3 (2)
N1—C21—C22—C23	65.0 (3)	C36—C35—C40—C39	−3.9 (3)
C21—C22—C23—N21	−76.3 (3)	C34—C35—C40—C39	175.7 (2)
C22—C23—N21—C24	−97.4 (3)	C36—C35—C40—N32	178.01 (19)
C22—C23—N21—Cu1	71.1 (2)	C34—C35—C40—N32	−2.5 (3)
N11—Cu1—N21—C24	17.0 (2)	C39—C40—N32—O31	−148.9 (2)
N31—Cu1—N21—C24	−146.4 (2)	C35—C40—N32—O31	29.3 (3)
N1—Cu1—N21—C24	115.3 (2)	C39—C40—N32—O32	32.3 (3)
N11—Cu1—N21—C23	−148.42 (14)	C35—C40—N32—O32	−149.5 (2)
N31—Cu1—N21—C23	48.23 (16)

Experimental details

	(II)	(IV)	(VI)
Crystal data
Chemical formula	[Cu(C₂₇H₂₇N₇O₆)]ClO₄·2C₂H₃N	[Cu(C₂₇H₃₃N₇O₆)Cl]Cl·C₂H₆O	[Cu(C₃₀H₃₃N₇O₆)]ClO₄
M_r	790.65	732.11	750.62
Crystal system, space group	Triclinic, P1	Monoclinic, P2₁/c	Monoclinic, P2₁/c
Temperature (K)	150	150	150
a, b, c (Å)	11.1178 (7), 13.3595 (9), 13.7998 (9)	13.183 (5), 14.485 (6), 16.914 (7)	9.5361 (7), 18.6870 (13), 19.2367 (13)
α, β, γ (°)	111.627 (1), 102.995 (1), 103.648 (1)	90, 95.319 (7), 90	90, 104.044 (1), 90
V (Å³)	1737.8 (2)	3216 (2)	3325.5 (4)
Z	2	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα
µ (mm⁻¹)	0.78	0.90	0.80
Crystal size (mm)	0.37 × 0.19 × 0.08	0.23 × 0.21 × 0.07	0.47 × 0.17 × 0.13

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer	Bruker SMART 1000 CCD area-detector diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)	Multi-scan (SADABS; Sheldrick, 2003)	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.762, 0.941	0.819, 0.940	0.704, 0.903
No. of measured, independent and observed [I > 2σ(I)] reflections	15023, 7856, 6372	22643, 5657, 3256	28475, 7892, 5773
R_int	0.019	0.103	0.028
(sin θ/λ)_max (Å⁻¹)	0.678	0.595	0.677

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.082, 1.02	0.055, 0.153, 0.98	0.040, 0.112, 1.00
No. of reflections	7856	5657	7892
No. of parameters	488	416	455
No. of restraints	10	0	62
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.45	0.63, −0.76	0.50, −0.33

Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2001), SHELXTL.

Selected geometric parameters (Å, º) for (II) top

Cu1—N31	1.9974 (15)	Cu1—N11	2.0127 (16)
Cu1—N21	1.9981 (15)	Cu1—N1	2.1965 (15)

N31—Cu1—N21	120.56 (6)	N31—Cu1—N1	85.48 (6)
N31—Cu1—N11	118.99 (6)	N21—Cu1—N1	84.85 (6)
N21—Cu1—N11	118.25 (6)	N11—Cu1—N1	84.86 (6)

Selected geometric parameters (Å, º) for (IV) top

Cu1—N1	2.038 (4)	Cu1—N21	2.107 (4)
Cu1—N31	2.081 (4)	Cu1—Cl1	2.2547 (16)
Cu1—N11	2.105 (4)

N1—Cu1—N31	84.44 (16)	N11—Cu1—N21	107.62 (15)
N1—Cu1—N11	83.97 (16)	N1—Cu1—Cl1	176.50 (12)
N31—Cu1—N11	127.92 (16)	N31—Cu1—Cl1	92.13 (12)
N1—Cu1—N21	84.35 (15)	N11—Cu1—Cl1	97.66 (11)
N31—Cu1—N21	121.43 (16)	N21—Cu1—Cl1	98.07 (11)

Hydrogen-bond geometry (Å, º) for (IV) top

D—H···A	D—H	H···A	D···A	D—H···A
N31—H31N···O41	0.93	2.13	2.998 (6)	154.0
N11—H11N···O12	0.93	2.29	2.882 (6)	121.3
N11—H11N···Cl2ⁱ	0.93	2.63	3.474 (4)	151.7
N21—H21N···O22	0.93	2.46	3.023 (6)	118.8
N21—H21N···Cl2	0.93	2.48	3.302 (4)	147.2
O41—H41···Cl2	0.84	2.28	3.105 (5)	169.6

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

Selected geometric parameters (Å, º) for (VI) top

Cu1—N21	2.0124 (19)	Cu1—N31	2.0326 (17)
Cu1—N11	2.0093 (18)	Cu1—N1	2.1965 (19)

N21—Cu1—N11	121.49 (8)	N21—Cu1—N1	94.59 (8)
N21—Cu1—N31	119.13 (7)	N11—Cu1—N1	94.67 (7)
N11—Cu1—N31	117.34 (7)	N31—Cu1—N1	95.00 (7)

Acknowledgements

The authors thank the Leverhulme Foundation, Unilever Research and Development and the Open University for support. They also acknowledge the use of the EPSRC Chemical Database Service at Daresbury.

References

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Volume 62| Part 10| October 2006| Pages m472-m476

doi:10.1107/S0108270106034524

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Comparison of copper imine and amine podates: geometric consequences of podand size and donor type

Comment

Experimental

Compound (II)

Crystal data

Data collection

Refinement

Compound (IV)

Crystal data

Data collection

Refinement

Compound (VI)

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds