Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011301768X/eg3130sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011301768X/eg31302sup2.hkl |
CCDC reference: 958930
The ease and versatility of Schiff base condensation has led to its extensive use over many years in coordination chemistry (Tamburini et al., 2004; Vigato et al., 2012). Recently, the reversibility of Schiff base condensation has led to its exploitation in studies of dynamic covalent chemistry (Hafezi & Lehn, 2012; Nitschke, 2007) and to renewed interest in the mechanisms of self-assembly in Schiff base reactions, with a view to improving control and manipulation of the product assembly (Akine & Nabeshima, 2009).
[Ba2(µ1,2-ClO4)2(H2L1)2](ClO4)2, (1), was prepared as described previously (James et al., 2011). In the transmetallation reaction, the barium complex (0.194 g, 0.271 mmol) was dissolved in acetonitrile (15 ml) and heated to reflux. Copper acetate monohydrate (0.109 g, 0.545 mmol) dissolved in acetonitrile (10 ml) was added to the refluxing solution with stirring. The resulting dark-blue solution was refluxed for 6 h, after which time a brown, as yet unidentified, precipitate (yield 0.160 g) was removed by filtration. Green crystals of [Cu(CH3COO)(L2)]ClO4, (2), grew in the dark-blue filtrate on standing overnight and were collected by filtration (yield 0.028 g, 0.047 mmol, 17%). Elemental analysis, calculated for (2): C 44.0, H 4.2, N 14.0%; found: C 43.5, H 4.1, N 13.9%.
Crystal data, data collection and structure refinement details are summarized in Table 1. C-bound H atoms were inserted at calculated positions riding on their carrier atoms, with C—H = 0.95, 0.98, 0.99 and 1.00 Å for aryl, methyl, methylene and tertiary H atoms, respectively. N-bound H atoms were located from difference maps and their coordinates refined. The H atoms of the aryl, methylene and tertiary C—H groups had Uiso(H) = 1.2Ueq(C), and those of the methyl or N—H groups had Uiso(H) = 1.5Ueq(C,N).
The [2+2] Schiff base macrocycle L1 (Scheme 1) is conveniently obtained as the BaII complex, [Ba2(µ1,2-ClO4)2(H2L1)2](ClO4)2, (1), by condensation of 2,6-diformylpyridine and 1,3-diaminopropan-2-ol in the presence of a BaII template ion (James et al., 2011). Complexes of this type are often considered as synthetic equivalents of the free [2+2] macrocycles, as the BaII cation can be readily transmetallated by transition metal ions with hard–soft acid–base (HSAB) properties better matched to those of the ligand. Since the transition metal ions are generally smaller than the BaII cation, dinuclear complexes often result (Brooker & McKee, 1989; Bailey et al., 1987). In other cases, where the radius of the metal ion and the size of the macrocyclic cavity are poorly compatable, the macrocycle may undergo ring-contraction (Adams et al. 1987; Bailey et al., 1983) or ring-expansion (Brooker et al. 1987) reactions. In this paper, we report a new derivative of L1 obtained via three successive ring-contraction reactions on a CuII template ion to give the title complex, (2), of the new macrocycle L2 [systematic name: 26,28-dioxa-3,7,15,19,25,27-hexaazahexacyclo[19.3.1.12,5.19,13.117,20.03,8]octacosa-1(25),9(27),10,12,14,21,23-heptaene; see Schemes 1 and 2].
Transmetallation of BaII complex (1) using copper(II) acetate in acetonitrile yielded well formed green crystals of [Cu(L2)(CH3COO)]ClO4, (2); the formula unit is shown Scheme 2 and the structure of the cation is shown in Fig. 1. The CuII cation is six-coordinate, bonded to five N atoms of the macrocycle and to one O atom of the acetate anion. A long interaction with the second O atom of the acetate ligand might suggest it has some bidentate character [Cu—O22 = 2.946 (2) Å]. The angular geometry at the metal ion is irregular (Table 2), and the bond lengths cover a range including three normal Cu—N bonds, two somewhat longer bonds and one very long bond to the imine N atom [Cu1—N6 = 2.532 (2) Å].
The macrocycle has undergone three distinct ring-contraction processes (shown in Scheme 1). First, both pendant alcohol groups have attacked the imine carbon centres at the same pyridine group, forming two perhydropyrimidine groups. One of the newly formed secondary amine groups then attacks one of the remaining imine C atoms, forming an oxazolidine ring and resulting in an overall ring contraction from a 20-membered ring to a 16-membered macrocycle. The ligand has a distinct fold [N1—Cu1—N4 = 103.57 (7)°], imposed primarily by the geometry of the fused perhydropyrimidine and oxazolidine rings at atom N2. The monodentate acetate anions link pairs of cations via hydrogen bonding [N5···O22i = 2.843 (3) Å; symmetry code: (i) -x, -y, -z + 2; Table 3 and Fig. 2]. The perchlorate anions are also linked to the cations via hydrogen bonds involving the uncoordinated N atom of the perhydropyrimidine ring [N3···O12 = 3.111 (3) Å]. There are no other particularly striking intermolecular interactions. The hydrogen-bonded dimers lie with the Cu···Cu vector parallel to the c axis (Fig. 3).
The behaviour of (2) contrasts with the analogous system derived from 2,6-diacetylpyridine, where a very similar barium complex of the [2+2] complex (H2L3) can be prepared (Adams et al., 1987). This ketone-derived system is less susceptible to ring-contraction reactions than the aldehyde-derived equivalent L1, due to the increased steric hindrance and decreased polarity of the C═N bond, and transmetallation with CuII in methanol yields a dicopper(II) complex of the same [2+2] macrocycle, (3) (Fig. 4; Bailey et al., 1987). In the absence of ring-contraction reactions, transmetallation of (1) with copper(II) acetate would be expected to yield a structurally similar analogue of complex (3).
The driving force for macrocyclic ring-contraction reactions is usually ascribed to an improved fit between the radius of the metal ion and the macrocycle cavity (Drew et al., 1981). It is not immediately obvious from the structures of (2) and (3) (Figs. 1 and 4) that the ring contraction has resulted in an improved fit in this case, since (3) shows a reasonably conventional tetragonal-based geometry at the CuII cation, with unexceptional bond lengths. Instead, the situation should be viewed as a dynamic chemical system (Lehn, 2007), in which the solvent, counter-ions, ligation available to those CuII cations not coordinated to the macrocyclic ligand, covalent bond formation etc. all influence the structure of the macrocyclic product isolated.
For related literature, see: Adams et al. (1987); Akine & Nabeshima (2009); Bailey et al. (1983, 1987); Brooker & McKee (1989); Brooker et al. (1987); Drew et al. (1981); Hafezi & Lehn (2012); James et al. (2011); Lehn (2007); Nitschke (2007); Tamburini et al. (2004); Vigato et al. (2012).
Data collection: APEX2 (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2012); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Cu(C2H3O2)(C20H22N6O2)]ClO4 | F(000) = 1236 |
Mr = 600.47 | Dx = 1.637 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.9252 (8) Å | Cell parameters from 7293 reflections |
b = 16.9606 (15) Å | θ = 2.4–28.0° |
c = 16.5461 (14) Å | µ = 1.07 mm−1 |
β = 103.350 (1)° | T = 150 K |
V = 2437.0 (4) Å3 | Block, green |
Z = 4 | 0.37 × 0.33 × 0.27 mm |
Bruker APEXII CCD area-detector diffractometer | 5050 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.033 |
ω rotation with narrow frames scans | θmax = 28.4°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2009) | h = −11→11 |
Tmin = 0.639, Tmax = 0.746 | k = −22→22 |
24778 measured reflections | l = −22→22 |
6075 independent reflections |
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)] = 0.041 | Hydrogen site location: mixed |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.058P)2 + 2.621P] where P = (Fo2 + 2Fc2)/3 |
6075 reflections | (Δ/σ)max = 0.001 |
350 parameters | Δρmax = 1.53 e Å−3 |
0 restraints | Δρmin = −1.10 e Å−3 |
[Cu(C2H3O2)(C20H22N6O2)]ClO4 | V = 2437.0 (4) Å3 |
Mr = 600.47 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.9252 (8) Å | µ = 1.07 mm−1 |
b = 16.9606 (15) Å | T = 150 K |
c = 16.5461 (14) Å | 0.37 × 0.33 × 0.27 mm |
β = 103.350 (1)° |
Bruker APEXII CCD area-detector diffractometer | 6075 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2009) | 5050 reflections with I > 2σ(I) |
Tmin = 0.639, Tmax = 0.746 | Rint = 0.033 |
24778 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 1.53 e Å−3 |
6075 reflections | Δρmin = −1.10 e Å−3 |
350 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.00676 (3) | 0.01697 (2) | 0.81242 (2) | 0.01841 (9) | |
N1 | −0.0850 (2) | 0.04068 (11) | 0.67681 (12) | 0.0200 (4) | |
C1 | 0.0001 (3) | 0.07678 (15) | 0.63030 (15) | 0.0256 (5) | |
C2 | −0.0615 (3) | 0.09853 (18) | 0.54831 (16) | 0.0356 (6) | |
H2 | 0.0016 | 0.1212 | 0.5154 | 0.043* | |
C3 | −0.2176 (3) | 0.08638 (17) | 0.51575 (17) | 0.0358 (6) | |
H3 | −0.2632 | 0.1018 | 0.4603 | 0.043* | |
C4 | −0.3060 (3) | 0.05184 (15) | 0.56404 (16) | 0.0283 (5) | |
H4 | −0.4135 | 0.0444 | 0.5431 | 0.034* | |
C5 | −0.2345 (3) | 0.02793 (13) | 0.64434 (15) | 0.0211 (5) | |
C6 | −0.3209 (3) | −0.01375 (14) | 0.70116 (15) | 0.0209 (4) | |
H6 | −0.3680 | 0.0277 | 0.7305 | 0.025* | |
N2 | −0.2054 (2) | −0.05758 (11) | 0.76516 (11) | 0.0177 (4) | |
N3 | −0.4449 (2) | −0.06170 (13) | 0.65356 (14) | 0.0262 (4) | |
H3A | −0.416 (4) | −0.086 (2) | 0.616 (2) | 0.039* | |
C7 | −0.5055 (3) | −0.11883 (16) | 0.70521 (17) | 0.0288 (5) | |
H7A | −0.5635 | −0.1604 | 0.6690 | 0.035* | |
H7B | −0.5779 | −0.0916 | 0.7330 | 0.035* | |
C8 | −0.3775 (3) | −0.15712 (15) | 0.77105 (16) | 0.0267 (5) | |
H8 | −0.4187 | −0.1974 | 0.8043 | 0.032* | |
C9 | −0.2858 (3) | −0.09337 (15) | 0.82580 (15) | 0.0235 (5) | |
H9A | −0.3537 | −0.0550 | 0.8449 | 0.028* | |
H9B | −0.2123 | −0.1160 | 0.8744 | 0.028* | |
O1 | −0.2626 (2) | −0.19016 (10) | 0.73131 (11) | 0.0256 (4) | |
C10 | −0.1551 (3) | −0.12867 (13) | 0.72681 (14) | 0.0196 (4) | |
H10 | −0.1547 | −0.1178 | 0.6675 | 0.023* | |
C11 | 0.0045 (3) | −0.15142 (13) | 0.77419 (14) | 0.0204 (4) | |
C12 | 0.0607 (3) | −0.22789 (14) | 0.77751 (16) | 0.0264 (5) | |
H12 | 0.0008 | −0.2691 | 0.7471 | 0.032* | |
C13 | 0.2073 (3) | −0.24281 (15) | 0.82651 (18) | 0.0306 (6) | |
H13 | 0.2508 | −0.2941 | 0.8281 | 0.037* | |
C14 | 0.2892 (3) | −0.18215 (14) | 0.87298 (16) | 0.0264 (5) | |
H14 | 0.3866 | −0.1919 | 0.9093 | 0.032* | |
C15 | 0.2265 (3) | −0.10703 (13) | 0.86550 (14) | 0.0205 (4) | |
N4 | 0.0887 (2) | −0.09210 (11) | 0.81478 (11) | 0.0180 (4) | |
C16 | 0.3014 (3) | −0.03686 (14) | 0.91445 (15) | 0.0207 (4) | |
H16 | 0.3551 | −0.0532 | 0.9719 | 0.025* | |
O2 | 0.40728 (19) | −0.00096 (10) | 0.87330 (11) | 0.0247 (4) | |
C17 | 0.3967 (3) | 0.08382 (14) | 0.87928 (15) | 0.0221 (5) | |
H17 | 0.4982 | 0.1056 | 0.9097 | 0.026* | |
C18 | 0.2766 (3) | 0.09766 (14) | 0.93034 (15) | 0.0233 (5) | |
H18A | 0.3261 | 0.1056 | 0.9898 | 0.028* | |
H18B | 0.2114 | 0.1439 | 0.9096 | 0.028* | |
N5 | 0.1857 (2) | 0.02381 (11) | 0.91742 (13) | 0.0191 (4) | |
H5 | 0.147 (4) | 0.0143 (18) | 0.959 (2) | 0.029* | |
C19 | 0.3540 (3) | 0.11819 (14) | 0.79237 (15) | 0.0240 (5) | |
H19A | 0.3566 | 0.1765 | 0.7953 | 0.029* | |
H19B | 0.4291 | 0.1008 | 0.7604 | 0.029* | |
N6 | 0.1993 (2) | 0.09167 (12) | 0.75073 (12) | 0.0217 (4) | |
C20 | 0.1598 (3) | 0.09575 (16) | 0.67273 (16) | 0.0293 (5) | |
H20 | 0.2322 | 0.1109 | 0.6416 | 0.035* | |
O21 | −0.0892 (2) | 0.11513 (10) | 0.83097 (10) | 0.0243 (4) | |
O22 | −0.1335 (3) | 0.06843 (13) | 0.94826 (14) | 0.0459 (6) | |
C21 | −0.1343 (3) | 0.12219 (14) | 0.89891 (16) | 0.0238 (5) | |
C22 | −0.1870 (4) | 0.20378 (17) | 0.9163 (2) | 0.0422 (7) | |
H22A | −0.2533 | 0.2002 | 0.9558 | 0.063* | |
H22B | −0.2447 | 0.2275 | 0.8644 | 0.063* | |
H22C | −0.0971 | 0.2365 | 0.9399 | 0.063* | |
Cl1 | −0.34875 (7) | −0.19938 (4) | 0.48008 (4) | 0.03087 (15) | |
O11 | −0.2261 (3) | −0.24779 (15) | 0.46888 (19) | 0.0631 (8) | |
O12 | −0.2962 (3) | −0.12426 (13) | 0.51353 (14) | 0.0457 (6) | |
O13 | −0.4472 (3) | −0.18456 (15) | 0.39730 (14) | 0.0481 (6) | |
O14 | −0.4383 (2) | −0.23729 (13) | 0.53157 (13) | 0.0381 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.02038 (15) | 0.01567 (14) | 0.01789 (15) | 0.00440 (10) | 0.00181 (10) | −0.00089 (10) |
N1 | 0.0195 (9) | 0.0201 (9) | 0.0195 (9) | 0.0015 (7) | 0.0026 (7) | 0.0022 (7) |
C1 | 0.0251 (12) | 0.0284 (12) | 0.0218 (11) | −0.0020 (10) | 0.0028 (9) | 0.0068 (9) |
C2 | 0.0370 (15) | 0.0447 (16) | 0.0226 (13) | −0.0115 (12) | 0.0019 (11) | 0.0114 (11) |
C3 | 0.0401 (15) | 0.0382 (15) | 0.0227 (12) | −0.0077 (12) | −0.0060 (11) | 0.0113 (11) |
C4 | 0.0283 (13) | 0.0233 (12) | 0.0275 (12) | −0.0018 (10) | −0.0056 (10) | 0.0041 (10) |
C5 | 0.0218 (11) | 0.0176 (10) | 0.0220 (11) | 0.0007 (8) | 0.0012 (9) | 0.0010 (8) |
C6 | 0.0161 (10) | 0.0224 (11) | 0.0229 (11) | 0.0018 (8) | 0.0019 (9) | −0.0003 (9) |
N2 | 0.0179 (9) | 0.0180 (9) | 0.0177 (9) | 0.0012 (7) | 0.0047 (7) | 0.0004 (7) |
N3 | 0.0216 (10) | 0.0299 (11) | 0.0250 (11) | −0.0058 (8) | 0.0012 (8) | −0.0009 (9) |
C7 | 0.0201 (11) | 0.0345 (14) | 0.0315 (13) | −0.0082 (10) | 0.0052 (10) | 0.0006 (11) |
C8 | 0.0266 (12) | 0.0269 (12) | 0.0279 (12) | −0.0050 (10) | 0.0091 (10) | 0.0019 (10) |
C9 | 0.0245 (12) | 0.0275 (12) | 0.0200 (11) | −0.0016 (9) | 0.0081 (9) | 0.0025 (9) |
O1 | 0.0265 (9) | 0.0193 (8) | 0.0312 (9) | −0.0061 (7) | 0.0070 (7) | −0.0023 (7) |
C10 | 0.0227 (11) | 0.0158 (10) | 0.0201 (10) | −0.0015 (8) | 0.0047 (9) | −0.0022 (8) |
C11 | 0.0247 (11) | 0.0173 (10) | 0.0208 (11) | 0.0009 (8) | 0.0081 (9) | 0.0005 (8) |
C12 | 0.0323 (13) | 0.0167 (10) | 0.0317 (13) | 0.0008 (9) | 0.0103 (10) | −0.0025 (9) |
C13 | 0.0340 (14) | 0.0179 (11) | 0.0416 (15) | 0.0085 (10) | 0.0118 (12) | 0.0022 (10) |
C14 | 0.0251 (12) | 0.0227 (11) | 0.0323 (13) | 0.0067 (9) | 0.0082 (10) | 0.0055 (10) |
C15 | 0.0204 (11) | 0.0206 (11) | 0.0218 (11) | 0.0035 (8) | 0.0075 (9) | 0.0041 (9) |
N4 | 0.0207 (9) | 0.0151 (8) | 0.0185 (9) | 0.0026 (7) | 0.0050 (7) | 0.0019 (7) |
C16 | 0.0181 (10) | 0.0213 (10) | 0.0218 (11) | 0.0028 (8) | 0.0029 (9) | 0.0050 (9) |
O2 | 0.0195 (8) | 0.0218 (8) | 0.0345 (10) | 0.0027 (6) | 0.0095 (7) | 0.0042 (7) |
C17 | 0.0179 (10) | 0.0204 (10) | 0.0257 (11) | −0.0011 (8) | 0.0005 (9) | 0.0019 (9) |
C18 | 0.0231 (11) | 0.0216 (11) | 0.0238 (11) | −0.0036 (9) | 0.0030 (9) | −0.0033 (9) |
N5 | 0.0197 (9) | 0.0191 (9) | 0.0189 (9) | −0.0001 (7) | 0.0055 (7) | 0.0004 (7) |
C19 | 0.0180 (11) | 0.0250 (11) | 0.0280 (12) | −0.0003 (9) | 0.0037 (9) | 0.0066 (9) |
N6 | 0.0179 (9) | 0.0243 (10) | 0.0225 (10) | 0.0008 (7) | 0.0041 (7) | 0.0036 (8) |
C20 | 0.0248 (12) | 0.0381 (14) | 0.0249 (12) | −0.0045 (10) | 0.0056 (10) | 0.0108 (11) |
O21 | 0.0313 (9) | 0.0191 (8) | 0.0240 (8) | 0.0075 (7) | 0.0094 (7) | 0.0030 (6) |
O22 | 0.0664 (15) | 0.0365 (11) | 0.0461 (13) | 0.0160 (10) | 0.0363 (11) | 0.0180 (9) |
C21 | 0.0238 (11) | 0.0216 (11) | 0.0280 (12) | 0.0023 (9) | 0.0104 (10) | 0.0016 (9) |
C22 | 0.059 (2) | 0.0289 (14) | 0.0479 (18) | 0.0102 (13) | 0.0310 (15) | −0.0012 (13) |
Cl1 | 0.0327 (3) | 0.0236 (3) | 0.0407 (4) | −0.0064 (2) | 0.0174 (3) | −0.0033 (2) |
O11 | 0.0666 (17) | 0.0455 (14) | 0.091 (2) | 0.0156 (12) | 0.0464 (16) | 0.0182 (14) |
O12 | 0.0669 (15) | 0.0354 (11) | 0.0379 (11) | −0.0225 (10) | 0.0188 (11) | −0.0131 (9) |
O13 | 0.0501 (13) | 0.0599 (15) | 0.0333 (11) | −0.0184 (11) | 0.0075 (10) | −0.0022 (10) |
O14 | 0.0365 (11) | 0.0436 (12) | 0.0369 (11) | −0.0104 (9) | 0.0139 (9) | 0.0040 (9) |
Cu1—O21 | 1.9290 (16) | C11—N4 | 1.339 (3) |
Cu1—N4 | 1.9861 (18) | C11—C12 | 1.387 (3) |
Cu1—N5 | 2.074 (2) | C12—C13 | 1.394 (4) |
Cu1—N1 | 2.2402 (19) | C12—H12 | 0.9500 |
Cu1—N2 | 2.2611 (19) | C13—C14 | 1.387 (4) |
Cu1—N6 | 2.532 (2) | C13—H13 | 0.9500 |
Cu1—O22 | 2.946 (2) | C14—C15 | 1.386 (3) |
N1—C5 | 1.336 (3) | C14—H14 | 0.9500 |
N1—C1 | 1.347 (3) | C15—N4 | 1.343 (3) |
C1—C2 | 1.391 (3) | C15—C16 | 1.507 (3) |
C1—C20 | 1.471 (3) | C16—O2 | 1.423 (3) |
C2—C3 | 1.388 (4) | C16—N5 | 1.467 (3) |
C2—H2 | 0.9500 | C16—H16 | 1.0000 |
C3—C4 | 1.377 (4) | O2—C17 | 1.446 (3) |
C3—H3 | 0.9500 | C17—C19 | 1.517 (3) |
C4—C5 | 1.395 (3) | C17—C18 | 1.528 (3) |
C4—H4 | 0.9500 | C17—H17 | 1.0000 |
C5—C6 | 1.521 (3) | C18—N5 | 1.481 (3) |
C6—N3 | 1.451 (3) | C18—H18A | 0.9900 |
C6—N2 | 1.494 (3) | C18—H18B | 0.9900 |
C6—H6 | 1.0000 | N5—H5 | 0.85 (3) |
N2—C10 | 1.480 (3) | C19—N6 | 1.464 (3) |
N2—C9 | 1.491 (3) | C19—H19A | 0.9900 |
N3—C7 | 1.475 (3) | C19—H19B | 0.9900 |
N3—H3A | 0.84 (3) | N6—C20 | 1.259 (3) |
C7—C8 | 1.530 (4) | C20—H20 | 0.9500 |
C7—H7A | 0.9900 | O21—C21 | 1.284 (3) |
C7—H7B | 0.9900 | O22—C21 | 1.223 (3) |
C8—O1 | 1.452 (3) | C21—C22 | 1.510 (3) |
C8—C9 | 1.522 (3) | C22—H22A | 0.9800 |
C8—H8 | 1.0000 | C22—H22B | 0.9800 |
C9—H9A | 0.9900 | C22—H22C | 0.9800 |
C9—H9B | 0.9900 | Cl1—O11 | 1.415 (2) |
O1—C10 | 1.431 (3) | Cl1—O12 | 1.425 (2) |
C10—C11 | 1.509 (3) | Cl1—O14 | 1.446 (2) |
C10—H10 | 1.0000 | Cl1—O13 | 1.468 (2) |
O21—Cu1—N4 | 167.34 (7) | N2—C10—C11 | 109.22 (18) |
O21—Cu1—N5 | 95.90 (7) | O1—C10—H10 | 109.9 |
N4—Cu1—N5 | 80.03 (8) | N2—C10—H10 | 109.9 |
O21—Cu1—N1 | 86.06 (7) | C11—C10—H10 | 109.9 |
N4—Cu1—N1 | 103.57 (7) | N4—C11—C12 | 121.8 (2) |
N5—Cu1—N1 | 149.52 (8) | N4—C11—C10 | 114.90 (19) |
O21—Cu1—N2 | 99.81 (7) | C12—C11—C10 | 123.3 (2) |
N4—Cu1—N2 | 76.17 (7) | C11—C12—C13 | 118.4 (2) |
N5—Cu1—N2 | 137.94 (7) | C11—C12—H12 | 120.8 |
N1—Cu1—N2 | 70.77 (7) | C13—C12—H12 | 120.8 |
O21—Cu1—N6 | 89.99 (7) | C14—C13—C12 | 119.4 (2) |
N4—Cu1—N6 | 101.13 (7) | C14—C13—H13 | 120.3 |
N5—Cu1—N6 | 81.18 (7) | C12—C13—H13 | 120.3 |
N1—Cu1—N6 | 68.39 (7) | C15—C14—C13 | 118.8 (2) |
N2—Cu1—N6 | 137.11 (7) | C15—C14—H14 | 120.6 |
O21—Cu1—O22 | 48.74 (6) | C13—C14—H14 | 120.6 |
N4—Cu1—O22 | 118.70 (7) | N4—C15—C14 | 121.5 (2) |
N5—Cu1—O22 | 74.04 (7) | N4—C15—C16 | 114.56 (19) |
N1—Cu1—O22 | 126.12 (7) | C14—C15—C16 | 123.9 (2) |
N2—Cu1—O22 | 87.72 (7) | C11—N4—C15 | 119.9 (2) |
N6—Cu1—O22 | 127.36 (7) | C11—N4—Cu1 | 121.91 (15) |
C5—N1—C1 | 119.1 (2) | C15—N4—Cu1 | 117.88 (15) |
C5—N1—Cu1 | 118.31 (15) | O2—C16—N5 | 105.45 (18) |
C1—N1—Cu1 | 121.98 (16) | O2—C16—C15 | 110.01 (19) |
N1—C1—C2 | 122.0 (2) | N5—C16—C15 | 110.10 (18) |
N1—C1—C20 | 116.0 (2) | O2—C16—H16 | 110.4 |
C2—C1—C20 | 121.9 (2) | N5—C16—H16 | 110.4 |
C3—C2—C1 | 118.3 (2) | C15—C16—H16 | 110.4 |
C3—C2—H2 | 120.8 | C16—O2—C17 | 109.36 (17) |
C1—C2—H2 | 120.8 | O2—C17—C19 | 108.9 (2) |
C4—C3—C2 | 119.8 (2) | O2—C17—C18 | 104.83 (18) |
C4—C3—H3 | 120.1 | C19—C17—C18 | 114.24 (19) |
C2—C3—H3 | 120.1 | O2—C17—H17 | 109.6 |
C3—C4—C5 | 118.6 (2) | C19—C17—H17 | 109.6 |
C3—C4—H4 | 120.7 | C18—C17—H17 | 109.6 |
C5—C4—H4 | 120.7 | N5—C18—C17 | 102.77 (18) |
N1—C5—C4 | 122.1 (2) | N5—C18—H18A | 111.2 |
N1—C5—C6 | 115.4 (2) | C17—C18—H18A | 111.2 |
C4—C5—C6 | 122.6 (2) | N5—C18—H18B | 111.2 |
N3—C6—N2 | 114.89 (19) | C17—C18—H18B | 111.2 |
N3—C6—C5 | 110.92 (19) | H18A—C18—H18B | 109.1 |
N2—C6—C5 | 107.72 (18) | C16—N5—C18 | 103.40 (18) |
N3—C6—H6 | 107.7 | C16—N5—Cu1 | 110.17 (14) |
N2—C6—H6 | 107.7 | C18—N5—Cu1 | 117.29 (15) |
C5—C6—H6 | 107.7 | C16—N5—H5 | 108 (2) |
C10—N2—C9 | 101.40 (17) | C18—N5—H5 | 111 (2) |
C10—N2—C6 | 109.23 (17) | Cu1—N5—H5 | 106 (2) |
C9—N2—C6 | 108.63 (17) | N6—C19—C17 | 109.34 (19) |
C10—N2—Cu1 | 106.92 (13) | N6—C19—H19A | 109.8 |
C9—N2—Cu1 | 119.32 (14) | C17—C19—H19A | 109.8 |
C6—N2—Cu1 | 110.63 (13) | N6—C19—H19B | 109.8 |
C6—N3—C7 | 112.9 (2) | C17—C19—H19B | 109.8 |
C6—N3—H3A | 110 (2) | H19A—C19—H19B | 108.3 |
C7—N3—H3A | 109 (2) | C20—N6—C19 | 118.4 (2) |
N3—C7—C8 | 112.21 (19) | C20—N6—Cu1 | 112.66 (16) |
N3—C7—H7A | 109.2 | C19—N6—Cu1 | 128.17 (14) |
C8—C7—H7A | 109.2 | N6—C20—C1 | 119.2 (2) |
N3—C7—H7B | 109.2 | N6—C20—H20 | 120.4 |
C8—C7—H7B | 109.2 | C1—C20—H20 | 120.4 |
H7A—C7—H7B | 107.9 | C21—O21—Cu1 | 117.40 (15) |
O1—C8—C9 | 101.82 (19) | O22—C21—O21 | 124.1 (2) |
O1—C8—C7 | 109.3 (2) | O22—C21—C22 | 120.7 (2) |
C9—C8—C7 | 109.4 (2) | O21—C21—C22 | 115.2 (2) |
O1—C8—H8 | 111.9 | C21—C22—H22A | 109.5 |
C9—C8—H8 | 111.9 | C21—C22—H22B | 109.5 |
C7—C8—H8 | 111.9 | H22A—C22—H22B | 109.5 |
N2—C9—C8 | 99.49 (18) | C21—C22—H22C | 109.5 |
N2—C9—H9A | 111.9 | H22A—C22—H22C | 109.5 |
C8—C9—H9A | 111.9 | H22B—C22—H22C | 109.5 |
N2—C9—H9B | 111.9 | O11—Cl1—O12 | 111.98 (17) |
C8—C9—H9B | 111.9 | O11—Cl1—O14 | 111.64 (14) |
H9A—C9—H9B | 109.6 | O12—Cl1—O14 | 110.25 (13) |
C10—O1—C8 | 107.12 (17) | O11—Cl1—O13 | 106.96 (17) |
O1—C10—N2 | 107.34 (17) | O12—Cl1—O13 | 106.37 (14) |
O1—C10—C11 | 110.53 (18) | O14—Cl1—O13 | 109.42 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O12 | 0.84 (3) | 2.29 (4) | 3.111 (3) | 165 (3) |
N5—H5···O22 | 0.85 (3) | 2.63 (3) | 3.102 (3) | 116 (2) |
N5—H5···O22i | 0.85 (3) | 2.11 (3) | 2.843 (3) | 145 (3) |
Symmetry code: (i) −x, −y, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C2H3O2)(C20H22N6O2)]ClO4 |
Mr | 600.47 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 8.9252 (8), 16.9606 (15), 16.5461 (14) |
β (°) | 103.350 (1) |
V (Å3) | 2437.0 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.07 |
Crystal size (mm) | 0.37 × 0.33 × 0.27 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2009) |
Tmin, Tmax | 0.639, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24778, 6075, 5050 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.668 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.115, 1.06 |
No. of reflections | 6075 |
No. of parameters | 350 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.53, −1.10 |
Computer programs: APEX2 (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL2012 (Sheldrick, 2012), SHELXTL (Sheldrick, 2008).
Cu1—O21 | 1.9290 (16) | Cu1—N2 | 2.2611 (19) |
Cu1—N4 | 1.9861 (18) | Cu1—N6 | 2.532 (2) |
Cu1—N5 | 2.074 (2) | Cu1—O22 | 2.946 (2) |
Cu1—N1 | 2.2402 (19) | ||
O21—Cu1—N4 | 167.34 (7) | N5—Cu1—N2 | 137.94 (7) |
O21—Cu1—N5 | 95.90 (7) | N1—Cu1—N2 | 70.77 (7) |
N4—Cu1—N5 | 80.03 (8) | O21—Cu1—N6 | 89.99 (7) |
O21—Cu1—N1 | 86.06 (7) | N4—Cu1—N6 | 101.13 (7) |
N4—Cu1—N1 | 103.57 (7) | N5—Cu1—N6 | 81.18 (7) |
N5—Cu1—N1 | 149.52 (8) | N1—Cu1—N6 | 68.39 (7) |
O21—Cu1—N2 | 99.81 (7) | N2—Cu1—N6 | 137.11 (7) |
N4—Cu1—N2 | 76.17 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O12 | 0.84 (3) | 2.29 (4) | 3.111 (3) | 165 (3) |
N5—H5···O22 | 0.85 (3) | 2.63 (3) | 3.102 (3) | 116 (2) |
N5—H5···O22i | 0.85 (3) | 2.11 (3) | 2.843 (3) | 145 (3) |
Symmetry code: (i) −x, −y, −z+2. |
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