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metal-organic compounds
Comparison of copper imine and amine podates: geometric consequences of podand size and donor type
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
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 CuI ion. The reduced amine podand tris[(2-nitrobenzyl)aminoethyl]amine binds CuII 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 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 CuI podates, one derived from tris(aminoethyl)amine (tren) and one from tris(aminopropyl)amine (trpn), with the CuII amine analogue of the smaller tren-based podate.
In podate and I and are easily hydrolysed by CuII (Harding et al., 1995; Arthurs et al., 2001
). Reduction of the imine donors to the corresponding generates a site in which CuI 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, CuII 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 CuI complex [Cu(I)]ClO4·2CH3CN, (II)
, as dark-brown crystals (Fig. 1
). The CuI 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 CuI 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 CuI 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 CuII 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 (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 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 CuI 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 CuI 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 CuI 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 CuI 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 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 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 CuI 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 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) ![]() |
![]() | Figure 2 The structure of complex (IV) ![]() |
![]() | Figure 3 A packing plot for complex (IV) ![]() |
![]() | Figure 4 The structure of complex (VI) ![]() |
Experimental
For the preparation of [CuI(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 [CuII(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 [CuI(V)]ClO4, (VI), were obtained on allowing the solution to stand (yield 0.69 g, 54%).
Compound (II)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
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Refinement
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Compound (IV)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
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Refinement
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Compound (VI)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
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Refinement
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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 Uiso(H) = 1.2Ueq(carrier atom). The value of Rint 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 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
10.1107/S0108270106034524/sq3035sup1.cif
contains datablocks II, IV, VI, global. DOI: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
For the preparation of [CuI(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 [CuII(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 [CuI(V)]ClO4, (VI), were obtained on allowing the solution to stand (yield 0.69 g, 54%).
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 Uiso(H) = 1.2Ueq(carrier atom). The value of Rint 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
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.[Cu(C27H27N7O6)]ClO4·2C2H3N | Z = 2 |
Mr = 790.65 | F(000) = 816 |
Triclinic, P1 | Dx = 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 |
Bruker SMART 1000 CCD area-detector diffractometer | 7856 independent reflections |
Radiation source: normal-focus sealed tube | 6372 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
ϕ and ω scans | θmax = 28.8°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −14→14 |
Tmin = 0.762, Tmax = 0.941 | k = −17→17 |
15023 measured reflections | l = −18→18 |
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(Fo2) + (0.0325P)2 + 1.0079P] where P = (Fo2 + 2Fc2)/3 |
7856 reflections | (Δ/σ)max = 0.025 |
488 parameters | Δρmax = 0.35 e Å−3 |
10 restraints | Δρmin = −0.45 e Å−3 |
[Cu(C27H27N7O6)]ClO4·2C2H3N | γ = 103.648 (1)° |
Mr = 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)° |
Bruker SMART 1000 CCD area-detector diffractometer | 7856 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 6372 reflections with I > 2σ(I) |
Tmin = 0.762, Tmax = 0.941 | Rint = 0.019 |
15023 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 10 restraints |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.35 e Å−3 |
7856 reflections | Δρmin = −0.45 e Å−3 |
488 parameters |
Experimental. Analysis for [CuI(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, [CuI(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. |
x | y | z | Uiso*/Ueq | 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* |
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) |
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) |
[Cu(C27H33N7O6)Cl]Cl·C2H6O | F(000) = 1524 |
Mr = 732.11 | Dx = 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 |
Bruker SMART 1000 CCD area-detector diffractometer | 5657 independent reflections |
Radiation source: normal-focus sealed tube | 3256 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.103 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −15→15 |
Tmin = 0.819, Tmax = 0.940 | k = −16→17 |
22643 measured reflections | l = −20→20 |
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(Fo2) + (0.0768P)2] where P = (Fo2 + 2Fc2)/3 |
5657 reflections | (Δ/σ)max < 0.001 |
416 parameters | Δρmax = 0.63 e Å−3 |
0 restraints | Δρmin = −0.76 e Å−3 |
[Cu(C27H33N7O6)Cl]Cl·C2H6O | V = 3216 (2) Å3 |
Mr = 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)° |
Bruker SMART 1000 CCD area-detector diffractometer | 5657 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3256 reflections with I > 2σ(I) |
Tmin = 0.819, Tmax = 0.940 | Rint = 0.103 |
22643 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.63 e Å−3 |
5657 reflections | Δρmin = −0.76 e Å−3 |
416 parameters |
Experimental. Analysis for [CuII(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). |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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. |
[Cu(C30H33N7O6)]ClO4 | F(000) = 1552 |
Mr = 750.62 | Dx = 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 |
Bruker SMART 1000 CCD area-detector diffractometer | 7892 independent reflections |
Radiation source: normal-focus sealed tube | 5773 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ϕ and ω scans | θmax = 28.8°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −12→12 |
Tmin = 0.704, Tmax = 0.903 | k = −24→23 |
28475 measured reflections | l = −25→24 |
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(Fo2) + (0.0534P)2 + 2.0893P] where P = (Fo2 + 2Fc2)/3 |
7892 reflections | (Δ/σ)max = 0.001 |
455 parameters | Δρmax = 0.50 e Å−3 |
62 restraints | Δρmin = −0.33 e Å−3 |
[Cu(C30H33N7O6)]ClO4 | V = 3325.5 (4) Å3 |
Mr = 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)° |
Bruker SMART 1000 CCD area-detector diffractometer | 7892 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 5773 reflections with I > 2σ(I) |
Tmin = 0.704, Tmax = 0.903 | Rint = 0.028 |
28475 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 62 restraints |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.50 e Å−3 |
7892 reflections | Δρmin = −0.33 e Å−3 |
455 parameters |
Experimental. Analysis for [CuI(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, [CuI(V)]+. IR (KBr, cm−1) inter alia: 1636(m, imine), 1524(s, NO2), 1343(m, NO2), 1090(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. |
x | y | z | Uiso*/Ueq | 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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 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 |
Rint | 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 |
Δρmax, Δρmin (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.
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) |
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) |
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. |
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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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 CuI podates, one derived from tris(aminoethyl)amine (tren) and one from tris(aminopropyl)amine (trpn), with the CuII amine analogue of the smaller tren-based podate.
In podate and cryptate complexes with potential threefold symmetry, imine donors typically stabilize CuI and are easily hydrolysed by CuII (Harding et al., 1995; Arthurs et al., 2001). Reduction of the imine donors to the corresponding amines generates a site in which CuI is activated to reaction with dioxygen, as shown elegantly by Suzuki, Schindler and their co-workers (Komiyama et al., 2004; Schindler, 2001). However, CuII 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 CuI complex [Cu(I)]ClO4·2CH3CN, (II), as dark-brown crystals (Fig. 1). The CuI 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 CuI 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 CuI 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 CuII 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 CuI 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 CuI 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 CuI 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 CuI 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 CuI 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.