
![[mu]](/logos/entities/mu_rmgif.gif)
![[kappa]](/logos/entities/kappa_rmgif.gif)
Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102006297/sk1547sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S0108270102006297/sk1547Isup2.hkl |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S0108270102006297/sk1547IIsup3.hkl |
CCDC references: 187918; 187919
The Schiff base ligand N,N'-hexamethylenebis(salicylaldimine) was prepared by the condensation of salicylaldehyde with 1,6-diaminohexane in the molar ratio 2:1 in methanol. The yellow product so obtained was identified by FT—IR, and 1H and 13 C NMR spectroscopy. The copper(II) complex was obtained as a brown powder by slow simultaneous dropwise addition of ethanol solutions of the Schiff base (containing an equimolar amount of triethylamine) and copper(II) nitrate trihydrate into a small volume of ethanol. The concentrations of the reactants varied from 0.05 to 0.10 mol dm-3. It was observed that the rate of addition, as well as the concentration of the reacting solutions, strongly influenced the nature of the product. Higher addition rates and reagent concentrations favoured the formation of green precipitates of unknown composition. The title compound was separated from the insoluble products by extraction with chloroform and subsequent precipitation with n-hexane or diethyl ether. The compound was crystallized by evaporation from dioxane solution, giving red crystals of (II) in the shape of bicapped tetragonal prisms. As the compound dissolved in dioxane tends to decompose, yielding an insoluble green precipitate (of currently unknown compostion), another method of preparation of the compound by slow diffusion of solutions of the Schiff base and copper(II) nitrate was used. As a result, long red needle-like crystals of (I) were obtained. As mentioned above, we initially considered that the crystals of (I) and (II) might be polymorphs, but the present X-ray structure determinations establish that the different preparation and crystallization conditions have instead yielded crystals of the same compound in enantiomorphic space groups, (I) in P41 and (II) in P43. The DSC measurements performed in an inert gas flow atmosphere (Ar, 200 cm3 min-1) in the temperature range 298–873 K using aluminium crucibles revealed a weak exothermic change at 499 K, followed by melting combined with decomposition at 587 K, for both crystal forms. The thermogravimetric analyses made in an oxygen gas flow atmosphere (200 cm3 min-1) in the temperature range 298–873 K gave the expected copper content of 15.73% (calculated copper content 16.38%) in both crystal forms and confirmed the chemical composition.
The crystal structure determination of both crystal forms using room-temperature data indicated a hardly resolvable disorder in one of the bridging hexamethylene chains. Therefore, low-temperature diffraction experiments were performed. Crystals of (I) and (II) were significantly different in appearance and both crystallized in the tetragonal system, space groups either P41 or P43 from the systematic absences. P41 was shown to be correct for (I) and P43 for (II) from the Flack parameters (Flack, 1983). H atoms were treated as riding atoms, with aromatic C—H = 0.95 Å and aliphatic C—H = 0.99 Å. Both structures were solved independently and it soon became apparent that, in each case, there was essentially identical disorder of one of the (CH2)6 chains. The occupancies of the major and minor chains were 0.714 (6) and 0.286 (6), respectively, for (I), and 0.747 (6) and 0.253 (6), respectively, for (II). Minor occupancy atoms were assigned an overall Uiso value of 0.06 Å2 and their geometry was restrained to reasonable values via SHELXL97 (Sheldrick, 1997) DFIX restraints.
For both compounds, data collection: COLLECT (Nonius, 1997-2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).
[Cu2(C20H22N2O2)2] | Dx = 1.405 Mg m−3 |
Mr = 771.81 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P41 | Cell parameters from 4153 reflections |
Hall symbol: P 4w | θ = 2.9–27.5° |
a = 13.2963 (2) Å | µ = 1.21 mm−1 |
c = 20.6366 (5) Å | T = 150 K |
V = 3648.38 (12) Å3 | Needle, red |
Z = 4 | 0.22 × 0.21 × 0.20 mm |
F(000) = 1608 |
Nonius KappaCCD area-detector diffractometer | 7755 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 5429 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.072 |
ϕ scans and ω scans with κ offsets | θmax = 27.5°, θmin = 2.9° |
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997) | h = −17→17 |
Tmin = 0.776, Tmax = 0.794 | k = −12→12 |
20156 measured reflections | l = −23→26 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.108 | w = 1/[σ2(Fo2) + (0.0485P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.003 |
7755 reflections | Δρmax = 0.32 e Å−3 |
470 parameters | Δρmin = −0.36 e Å−3 |
59 restraints | Absolute structure: Flack (1983), 3489 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.007 (14) |
[Cu2(C20H22N2O2)2] | Z = 4 |
Mr = 771.81 | Mo Kα radiation |
Tetragonal, P41 | µ = 1.21 mm−1 |
a = 13.2963 (2) Å | T = 150 K |
c = 20.6366 (5) Å | 0.22 × 0.21 × 0.20 mm |
V = 3648.38 (12) Å3 |
Nonius KappaCCD area-detector diffractometer | 7755 independent reflections |
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997) | 5429 reflections with I > 2σ(I) |
Tmin = 0.776, Tmax = 0.794 | Rint = 0.072 |
20156 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.108 | Δρmax = 0.32 e Å−3 |
S = 1.00 | Δρmin = −0.36 e Å−3 |
7755 reflections | Absolute structure: Flack (1983), 3489 Friedel pairs |
470 parameters | Absolute structure parameter: 0.007 (14) |
59 restraints |
Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G. C. & Holmes, K. C. (1966). Acta Cryst. 20, 886–891.] which effectively corrects for absorption effects. High-redundancy data were used in the scaling program, hence the `multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the `size' command in the SHELXL97 input file. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.16386 (4) | 0.30277 (4) | 0.50000 (3) | 0.04489 (14) | |
Cu2 | 0.67705 (4) | 0.15144 (4) | 0.35702 (3) | 0.04434 (14) | |
O1 | 0.2104 (2) | 0.3276 (2) | 0.58530 (16) | 0.0562 (8) | |
O2 | 0.0627 (2) | 0.2975 (2) | 0.43576 (18) | 0.0588 (9) | |
O3 | 0.6758 (2) | 0.2798 (2) | 0.31628 (16) | 0.0541 (8) | |
O4 | 0.7161 (2) | 0.0190 (2) | 0.37971 (15) | 0.0526 (8) | |
N1 | 0.1553 (3) | 0.1561 (3) | 0.5128 (2) | 0.0502 (9) | |
N2 | 0.2202 (3) | 0.4295 (3) | 0.46793 (19) | 0.0465 (8) | |
N3 | 0.5825 (2) | 0.0945 (3) | 0.29262 (19) | 0.0484 (9) | |
N4 | 0.7407 (3) | 0.2084 (3) | 0.4347 (2) | 0.0560 (10) | |
C11 | 0.1983 (3) | 0.1618 (3) | 0.6278 (2) | 0.0524 (12) | |
C12 | 0.2139 (3) | 0.2642 (3) | 0.6342 (2) | 0.0472 (11) | |
C13 | 0.2344 (3) | 0.3028 (4) | 0.6971 (3) | 0.0570 (12) | |
C14 | 0.2404 (4) | 0.2401 (4) | 0.7499 (3) | 0.0664 (13) | |
C15 | 0.2262 (4) | 0.1396 (4) | 0.7435 (3) | 0.0754 (16) | |
C16 | 0.2058 (4) | 0.1001 (4) | 0.6832 (3) | 0.0721 (15) | |
C17 | 0.1727 (3) | 0.1129 (3) | 0.5675 (3) | 0.0522 (12) | |
C21 | 0.0935 (3) | 0.4579 (3) | 0.3848 (2) | 0.0460 (10) | |
C22 | 0.0398 (3) | 0.3653 (3) | 0.3925 (2) | 0.0475 (10) | |
C23 | −0.0409 (3) | 0.3479 (3) | 0.3500 (3) | 0.0577 (12) | |
C24 | −0.0695 (4) | 0.4160 (4) | 0.3053 (3) | 0.0634 (13) | |
C25 | −0.0188 (4) | 0.5074 (4) | 0.2991 (3) | 0.0705 (14) | |
C26 | 0.0612 (4) | 0.5274 (4) | 0.3380 (2) | 0.0600 (13) | |
C27 | 0.1806 (3) | 0.4822 (3) | 0.4219 (2) | 0.0513 (11) | |
C31 | 0.5938 (3) | 0.2348 (3) | 0.2171 (2) | 0.0502 (11) | |
C32 | 0.6464 (3) | 0.3013 (3) | 0.2572 (2) | 0.0479 (11) | |
C33 | 0.6673 (3) | 0.3979 (3) | 0.2321 (2) | 0.0543 (11) | |
C34 | 0.6403 (4) | 0.4252 (4) | 0.1702 (3) | 0.0639 (13) | |
C35 | 0.5906 (4) | 0.3588 (4) | 0.1303 (3) | 0.0681 (15) | |
C36 | 0.5677 (4) | 0.2646 (4) | 0.1541 (2) | 0.0596 (13) | |
C37 | 0.5614 (3) | 0.1370 (3) | 0.2380 (2) | 0.0510 (11) | |
C41 | 0.8196 (3) | 0.0527 (3) | 0.4713 (2) | 0.0489 (11) | |
C42 | 0.7748 (3) | −0.0122 (3) | 0.4263 (2) | 0.0454 (10) | |
C43 | 0.7928 (3) | −0.1166 (3) | 0.4337 (3) | 0.0531 (11) | |
C44 | 0.8550 (4) | −0.1517 (4) | 0.4811 (3) | 0.0563 (13) | |
C45 | 0.9020 (4) | −0.0878 (4) | 0.5239 (3) | 0.0642 (14) | |
C46 | 0.8840 (4) | 0.0133 (4) | 0.5189 (3) | 0.0618 (13) | |
C47 | 0.8000 (4) | 0.1587 (4) | 0.4729 (2) | 0.0583 (12) | |
C1 | 0.1276 (3) | 0.0906 (3) | 0.4576 (2) | 0.0495 (11) | |
C2 | 0.2046 (3) | 0.0959 (4) | 0.4038 (2) | 0.0617 (13) | |
C3 | 0.3093 (3) | 0.0583 (3) | 0.4183 (2) | 0.0563 (12) | |
C4 | 0.3767 (3) | 0.0605 (3) | 0.3592 (2) | 0.0625 (13) | |
C5 | 0.4721 (3) | 0.0002 (3) | 0.3678 (2) | 0.0605 (13) | |
C6 | 0.5357 (3) | −0.0044 (3) | 0.3071 (2) | 0.0540 (11) | |
C61 | 0.3109 (4) | 0.4735 (8) | 0.4995 (7) | 0.0546 (17) | 0.714 (6) |
C62 | 0.4067 (5) | 0.4349 (5) | 0.4689 (4) | 0.072 (2) | 0.714 (6) |
C63 | 0.4265 (5) | 0.3248 (4) | 0.4815 (5) | 0.083 (3) | 0.714 (6) |
C64 | 0.5256 (4) | 0.2896 (6) | 0.4531 (4) | 0.081 (3) | 0.714 (6) |
C65 | 0.6183 (4) | 0.3293 (6) | 0.4872 (4) | 0.091 (3) | 0.714 (6) |
C66 | 0.7162 (4) | 0.3150 (4) | 0.4509 (3) | 0.0499 (18) | 0.714 (6) |
N72 | 0.2202 (3) | 0.4295 (3) | 0.46793 (19) | 0.0465 (8) | 0.00 |
C71 | 0.3190 (12) | 0.456 (2) | 0.496 (2) | 0.060* | 0.286 (6) |
C72 | 0.3939 (7) | 0.3745 (14) | 0.4812 (10) | 0.060* | 0.286 (6) |
C73 | 0.4943 (7) | 0.3867 (11) | 0.5132 (7) | 0.060* | 0.286 (6) |
C74 | 0.5758 (8) | 0.3251 (14) | 0.4809 (9) | 0.060* | 0.286 (6) |
C75 | 0.6795 (8) | 0.3482 (10) | 0.4989 (7) | 0.060* | 0.286 (6) |
C76 | 0.7587 (10) | 0.3165 (9) | 0.4497 (10) | 0.060* | 0.286 (6) |
N74 | 0.7407 (3) | 0.2084 (3) | 0.4347 (2) | 0.0560 (10) | 0.00 |
H13 | 0.2440 | 0.3731 | 0.7027 | 0.068* | |
H14 | 0.2547 | 0.2674 | 0.7914 | 0.080* | |
H15 | 0.2303 | 0.0968 | 0.7802 | 0.090* | |
H16 | 0.1967 | 0.0296 | 0.6788 | 0.086* | |
H17 | 0.1683 | 0.0416 | 0.5682 | 0.063* | |
H23 | −0.0765 | 0.2862 | 0.3529 | 0.069* | |
H24 | −0.1248 | 0.4015 | 0.2776 | 0.076* | |
H25 | −0.0401 | 0.5554 | 0.2678 | 0.085* | |
H26 | 0.0958 | 0.5895 | 0.3335 | 0.072* | |
H27 | 0.2130 | 0.5438 | 0.4117 | 0.062* | |
H33 | 0.7010 | 0.4454 | 0.2587 | 0.065* | |
H34 | 0.6561 | 0.4906 | 0.1548 | 0.077* | |
H35 | 0.5725 | 0.3774 | 0.0874 | 0.082* | |
H36 | 0.5331 | 0.2184 | 0.1270 | 0.072* | |
H37 | 0.5204 | 0.0999 | 0.2088 | 0.061* | |
H43 | 0.7611 | −0.1628 | 0.4052 | 0.064* | |
H44 | 0.8662 | −0.2221 | 0.4846 | 0.068* | |
H45 | 0.9459 | −0.1133 | 0.5562 | 0.077* | |
H46 | 0.9160 | 0.0579 | 0.5484 | 0.074* | |
H47 | 0.8340 | 0.1964 | 0.5052 | 0.070* | |
H51A | 0.0612 | 0.1115 | 0.4406 | 0.059* | |
H51B | 0.1218 | 0.0203 | 0.4729 | 0.059* | |
H52A | 0.1783 | 0.0571 | 0.3665 | 0.074* | |
H52B | 0.2099 | 0.1669 | 0.3898 | 0.074* | |
H53A | 0.3052 | −0.0115 | 0.4348 | 0.068* | |
H53B | 0.3394 | 0.1005 | 0.4527 | 0.068* | |
H54A | 0.3390 | 0.0336 | 0.3216 | 0.075* | |
H54B | 0.3946 | 0.1311 | 0.3494 | 0.075* | |
H55A | 0.4542 | −0.0691 | 0.3810 | 0.073* | |
H55B | 0.5123 | 0.0305 | 0.4031 | 0.073* | |
H56A | 0.5892 | −0.0555 | 0.3128 | 0.065* | |
H56B | 0.4933 | −0.0252 | 0.2700 | 0.065* | |
H61A | 0.3106 | 0.4563 | 0.5462 | 0.066* | 0.714 (6) |
H61B | 0.3086 | 0.5477 | 0.4956 | 0.066* | 0.714 (6) |
H62A | 0.4032 | 0.4460 | 0.4215 | 0.086* | 0.714 (6) |
H62B | 0.4641 | 0.4746 | 0.4858 | 0.086* | 0.714 (6) |
H63A | 0.3712 | 0.2846 | 0.4625 | 0.099* | 0.714 (6) |
H63B | 0.4269 | 0.3128 | 0.5288 | 0.099* | 0.714 (6) |
H64A | 0.5273 | 0.2152 | 0.4543 | 0.098* | 0.714 (6) |
H64B | 0.5285 | 0.3104 | 0.4070 | 0.098* | 0.714 (6) |
H65A | 0.6089 | 0.4020 | 0.4954 | 0.109* | 0.714 (6) |
H65B | 0.6240 | 0.2955 | 0.5298 | 0.109* | 0.714 (6) |
H66A | 0.7132 | 0.3542 | 0.4102 | 0.060* | 0.714 (6) |
H66B | 0.7716 | 0.3430 | 0.4775 | 0.060* | 0.714 (6) |
H71A | 0.3126 | 0.4641 | 0.5433 | 0.072* | 0.286 (6) |
H71B | 0.3425 | 0.5204 | 0.4774 | 0.072* | 0.286 (6) |
H72A | 0.3649 | 0.3092 | 0.4946 | 0.072* | 0.286 (6) |
H72B | 0.4042 | 0.3719 | 0.4337 | 0.072* | 0.286 (6) |
H73A | 0.4887 | 0.3663 | 0.5591 | 0.072* | 0.286 (6) |
H73B | 0.5137 | 0.4586 | 0.5121 | 0.072* | 0.286 (6) |
H74A | 0.5632 | 0.2533 | 0.4907 | 0.072* | 0.286 (6) |
H74B | 0.5693 | 0.3335 | 0.4334 | 0.072* | 0.286 (6) |
H75A | 0.6945 | 0.3148 | 0.5407 | 0.072* | 0.286 (6) |
H75B | 0.6852 | 0.4217 | 0.5059 | 0.072* | 0.286 (6) |
H76A | 0.7528 | 0.3575 | 0.4098 | 0.072* | 0.286 (6) |
H76B | 0.8270 | 0.3258 | 0.4678 | 0.072* | 0.286 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0510 (3) | 0.0394 (3) | 0.0443 (3) | 0.0007 (2) | 0.0004 (3) | 0.0010 (2) |
Cu2 | 0.0548 (3) | 0.0423 (3) | 0.0359 (3) | −0.0028 (2) | −0.0008 (2) | −0.0034 (2) |
O1 | 0.069 (2) | 0.0516 (18) | 0.048 (2) | 0.0041 (15) | −0.0071 (16) | 0.0006 (15) |
O2 | 0.066 (2) | 0.0464 (17) | 0.065 (2) | −0.0055 (14) | −0.0157 (17) | 0.0010 (17) |
O3 | 0.073 (2) | 0.0482 (17) | 0.041 (2) | −0.0017 (14) | −0.0077 (16) | −0.0008 (14) |
O4 | 0.0646 (19) | 0.0478 (17) | 0.045 (2) | −0.0018 (13) | −0.0066 (15) | −0.0011 (14) |
N1 | 0.050 (2) | 0.046 (2) | 0.054 (3) | 0.0012 (15) | 0.0092 (19) | 0.0016 (19) |
N2 | 0.050 (2) | 0.045 (2) | 0.044 (2) | −0.0010 (15) | −0.0005 (17) | −0.0051 (17) |
N3 | 0.0429 (19) | 0.058 (2) | 0.044 (3) | −0.0050 (16) | 0.0035 (17) | −0.0020 (18) |
N4 | 0.076 (3) | 0.045 (2) | 0.047 (3) | −0.0016 (18) | 0.002 (2) | −0.0057 (18) |
C11 | 0.045 (2) | 0.060 (3) | 0.052 (3) | 0.005 (2) | 0.007 (2) | 0.009 (2) |
C12 | 0.038 (2) | 0.055 (3) | 0.048 (3) | 0.0043 (19) | 0.004 (2) | 0.007 (2) |
C13 | 0.053 (3) | 0.066 (3) | 0.052 (3) | −0.001 (2) | −0.005 (2) | 0.002 (2) |
C14 | 0.064 (3) | 0.088 (4) | 0.047 (3) | −0.010 (2) | −0.003 (3) | 0.012 (3) |
C15 | 0.079 (4) | 0.090 (4) | 0.057 (4) | −0.012 (3) | −0.010 (3) | 0.026 (3) |
C16 | 0.087 (4) | 0.068 (3) | 0.060 (4) | 0.001 (3) | 0.003 (3) | 0.016 (3) |
C17 | 0.051 (3) | 0.042 (2) | 0.064 (4) | 0.0043 (19) | 0.011 (2) | 0.008 (2) |
C21 | 0.054 (3) | 0.050 (2) | 0.035 (3) | 0.0006 (19) | 0.0001 (19) | −0.006 (2) |
C22 | 0.053 (3) | 0.048 (2) | 0.041 (3) | 0.002 (2) | 0.002 (2) | −0.008 (2) |
C23 | 0.059 (3) | 0.052 (3) | 0.062 (4) | 0.006 (2) | −0.014 (3) | −0.011 (2) |
C24 | 0.065 (3) | 0.076 (4) | 0.049 (3) | 0.009 (3) | −0.012 (3) | −0.015 (3) |
C25 | 0.078 (3) | 0.086 (4) | 0.048 (3) | 0.019 (3) | 0.000 (3) | 0.014 (3) |
C26 | 0.072 (3) | 0.059 (3) | 0.048 (3) | 0.005 (2) | −0.001 (3) | 0.007 (2) |
C27 | 0.060 (3) | 0.046 (2) | 0.048 (3) | 0.002 (2) | 0.010 (2) | −0.002 (2) |
C31 | 0.047 (2) | 0.057 (3) | 0.047 (3) | −0.002 (2) | 0.003 (2) | −0.002 (2) |
C32 | 0.046 (2) | 0.055 (3) | 0.043 (3) | 0.0053 (18) | 0.007 (2) | 0.005 (2) |
C33 | 0.065 (3) | 0.052 (3) | 0.046 (3) | 0.003 (2) | −0.012 (2) | 0.000 (2) |
C34 | 0.065 (3) | 0.063 (3) | 0.064 (4) | −0.008 (2) | −0.001 (3) | 0.012 (3) |
C35 | 0.080 (4) | 0.082 (4) | 0.042 (3) | −0.015 (3) | −0.011 (3) | 0.015 (3) |
C36 | 0.062 (3) | 0.072 (3) | 0.045 (3) | −0.013 (2) | −0.009 (2) | −0.001 (2) |
C37 | 0.047 (2) | 0.065 (3) | 0.041 (3) | −0.003 (2) | 0.000 (2) | −0.002 (2) |
C41 | 0.057 (3) | 0.047 (2) | 0.043 (3) | −0.004 (2) | 0.009 (2) | −0.002 (2) |
C42 | 0.046 (2) | 0.046 (2) | 0.044 (3) | 0.0010 (18) | 0.008 (2) | 0.003 (2) |
C43 | 0.062 (3) | 0.044 (2) | 0.053 (3) | −0.004 (2) | 0.007 (2) | −0.001 (2) |
C44 | 0.058 (3) | 0.051 (3) | 0.060 (4) | 0.004 (2) | 0.012 (3) | 0.010 (2) |
C45 | 0.058 (3) | 0.079 (4) | 0.056 (3) | 0.011 (3) | 0.003 (2) | 0.015 (3) |
C46 | 0.062 (3) | 0.066 (3) | 0.058 (4) | −0.007 (2) | −0.008 (2) | 0.002 (2) |
C47 | 0.080 (3) | 0.057 (3) | 0.038 (3) | −0.008 (2) | −0.009 (3) | −0.009 (2) |
C1 | 0.053 (3) | 0.042 (2) | 0.054 (3) | −0.0054 (18) | 0.003 (2) | −0.001 (2) |
C2 | 0.066 (3) | 0.066 (3) | 0.053 (3) | −0.009 (2) | 0.001 (3) | −0.010 (3) |
C3 | 0.071 (3) | 0.053 (3) | 0.046 (3) | −0.007 (2) | −0.001 (2) | −0.002 (2) |
C4 | 0.065 (3) | 0.071 (3) | 0.051 (3) | −0.013 (2) | 0.009 (3) | −0.013 (3) |
C5 | 0.069 (3) | 0.059 (3) | 0.054 (3) | −0.019 (2) | 0.002 (3) | 0.001 (2) |
C6 | 0.062 (3) | 0.048 (2) | 0.052 (3) | −0.011 (2) | 0.008 (2) | −0.006 (2) |
C61 | 0.056 (4) | 0.051 (5) | 0.057 (5) | −0.009 (3) | −0.006 (4) | 0.002 (5) |
C62 | 0.052 (4) | 0.074 (5) | 0.089 (6) | −0.008 (3) | −0.005 (4) | 0.008 (4) |
C63 | 0.063 (5) | 0.059 (5) | 0.126 (8) | −0.007 (3) | 0.012 (5) | −0.009 (5) |
C64 | 0.063 (5) | 0.072 (5) | 0.109 (8) | 0.006 (4) | 0.002 (5) | −0.030 (5) |
C65 | 0.035 (4) | 0.065 (4) | 0.172 (10) | 0.010 (3) | −0.031 (5) | −0.060 (5) |
C66 | 0.056 (4) | 0.039 (3) | 0.055 (5) | 0.000 (3) | −0.015 (4) | −0.015 (3) |
N72 | 0.050 (2) | 0.045 (2) | 0.044 (2) | −0.0010 (15) | −0.0005 (17) | −0.0051 (17) |
N74 | 0.076 (3) | 0.045 (2) | 0.047 (3) | −0.0016 (18) | 0.002 (2) | −0.0057 (18) |
Cu1—O2 | 1.890 (3) | C43—C44 | 1.363 (7) |
Cu1—O1 | 1.895 (3) | C43—H43 | 0.9500 |
Cu1—N2 | 1.959 (4) | C44—C45 | 1.375 (7) |
Cu1—N1 | 1.972 (3) | C44—H44 | 0.9500 |
Cu2—O4 | 1.895 (3) | C45—C46 | 1.370 (7) |
Cu2—O3 | 1.903 (3) | C45—H45 | 0.9500 |
Cu2—N4 | 1.965 (4) | C46—H46 | 0.9500 |
Cu2—N3 | 1.980 (4) | C47—H47 | 0.9500 |
O1—C12 | 1.316 (5) | C1—C2 | 1.512 (3) |
O2—C22 | 1.305 (5) | C1—H51A | 0.9900 |
O3—C32 | 1.311 (6) | C1—H51B | 0.9900 |
O4—C42 | 1.306 (5) | C2—C3 | 1.509 (3) |
N1—C17 | 1.286 (6) | C2—H52A | 0.9900 |
N1—C1 | 1.480 (6) | C2—H52B | 0.9900 |
N2—C27 | 1.293 (6) | C3—C4 | 1.515 (3) |
N2—C61 | 1.491 (8) | C3—H53A | 0.9900 |
N3—C37 | 1.291 (6) | C3—H53B | 0.9900 |
N3—C6 | 1.485 (5) | C4—C5 | 1.511 (3) |
N4—C47 | 1.295 (6) | C4—H54A | 0.9900 |
N4—C66 | 1.492 (7) | C4—H54B | 0.9900 |
C11—C12 | 1.383 (6) | C5—C6 | 1.513 (3) |
C11—C16 | 1.411 (7) | C5—H55A | 0.9900 |
C11—C17 | 1.445 (7) | C5—H55B | 0.9900 |
C12—C13 | 1.422 (7) | C6—H56A | 0.9900 |
C13—C14 | 1.374 (7) | C6—H56B | 0.9900 |
C13—H13 | 0.9500 | C61—C62 | 1.512 (3) |
C14—C15 | 1.356 (8) | C61—H61A | 0.9900 |
C14—H14 | 0.9500 | C61—H61B | 0.9900 |
C15—C16 | 1.376 (8) | C62—C63 | 1.510 (3) |
C15—H15 | 0.9500 | C62—H62A | 0.9900 |
C16—H16 | 0.9500 | C62—H62B | 0.9900 |
C17—H17 | 0.9500 | C63—C64 | 1.516 (3) |
C21—C26 | 1.404 (6) | C63—H63A | 0.9900 |
C21—C27 | 1.426 (6) | C63—H63B | 0.9900 |
C21—C22 | 1.432 (6) | C64—C65 | 1.515 (3) |
C22—C23 | 1.406 (6) | C64—H64A | 0.9900 |
C23—C24 | 1.347 (7) | C64—H64B | 0.9900 |
C23—H23 | 0.9500 | C65—C66 | 1.513 (3) |
C24—C25 | 1.396 (7) | C65—H65A | 0.9900 |
C24—H24 | 0.9500 | C65—H65B | 0.9900 |
C25—C26 | 1.359 (7) | C66—H66A | 0.9900 |
C25—H25 | 0.9500 | C66—H66B | 0.9900 |
C26—H26 | 0.9500 | C71—C72 | 1.501 (10) |
C27—H27 | 0.9500 | C71—H71A | 0.9900 |
C31—C32 | 1.399 (6) | C71—H71B | 0.9900 |
C31—C36 | 1.402 (7) | C72—C73 | 1.498 (9) |
C31—C37 | 1.437 (6) | C72—H72A | 0.9900 |
C32—C33 | 1.412 (6) | C72—H72B | 0.9900 |
C33—C34 | 1.375 (7) | C73—C74 | 1.514 (9) |
C33—H33 | 0.9500 | C73—H73A | 0.9900 |
C34—C35 | 1.376 (7) | C73—H73B | 0.9900 |
C34—H34 | 0.9500 | C74—C75 | 1.461 (9) |
C35—C36 | 1.380 (7) | C74—H74A | 0.9900 |
C35—H35 | 0.9500 | C74—H74B | 0.9900 |
C36—H36 | 0.9500 | C75—C76 | 1.523 (9) |
C37—H37 | 0.9500 | C75—H75A | 0.9900 |
C41—C42 | 1.402 (6) | C75—H75B | 0.9900 |
C41—C46 | 1.404 (7) | C76—H76A | 0.9900 |
C41—C47 | 1.433 (6) | C76—H76B | 0.9900 |
C42—C43 | 1.416 (6) | ||
O2—Cu1—O1 | 152.95 (15) | C45—C46—H46 | 119.2 |
O2—Cu1—N2 | 93.86 (14) | C41—C46—H46 | 119.2 |
O1—Cu1—N2 | 92.23 (15) | N4—C47—C41 | 126.8 (4) |
O2—Cu1—N1 | 90.93 (15) | N4—C47—H47 | 116.6 |
O1—Cu1—N1 | 93.82 (16) | C41—C47—H47 | 116.6 |
N2—Cu1—N1 | 156.66 (15) | N1—C1—C2 | 111.7 (3) |
O4—Cu2—O3 | 160.99 (14) | N1—C1—H51A | 109.3 |
O4—Cu2—N4 | 92.23 (15) | C2—C1—H51A | 109.3 |
O3—Cu2—N4 | 91.06 (15) | N1—C1—H51B | 109.3 |
O4—Cu2—N3 | 89.09 (14) | C2—C1—H51B | 109.3 |
O3—Cu2—N3 | 92.34 (14) | H51A—C1—H51B | 107.9 |
N4—Cu2—N3 | 165.62 (16) | C3—C2—C1 | 117.6 (4) |
C12—O1—Cu1 | 127.7 (3) | C3—C2—H52A | 107.9 |
C22—O2—Cu1 | 128.3 (3) | C1—C2—H52A | 107.9 |
C32—O3—Cu2 | 127.5 (3) | C3—C2—H52B | 107.9 |
C42—O4—Cu2 | 129.9 (3) | C1—C2—H52B | 107.9 |
C17—N1—C1 | 117.2 (4) | H52A—C2—H52B | 107.2 |
C17—N1—Cu1 | 123.3 (4) | C2—C3—C4 | 112.3 (4) |
C1—N1—Cu1 | 119.5 (3) | C2—C3—H53A | 109.1 |
C27—N2—C61 | 115.9 (7) | C4—C3—H53A | 109.1 |
C27—N2—Cu1 | 124.0 (3) | C2—C3—H53B | 109.1 |
C61—N2—Cu1 | 120.0 (6) | C4—C3—H53B | 109.1 |
C37—N3—C6 | 118.1 (4) | H53A—C3—H53B | 107.9 |
C37—N3—Cu2 | 123.8 (3) | C5—C4—C3 | 113.1 (4) |
C6—N3—Cu2 | 118.0 (3) | C5—C4—H54A | 109.0 |
C47—N4—C66 | 118.8 (5) | C3—C4—H54A | 109.0 |
C47—N4—Cu2 | 124.1 (3) | C5—C4—H54B | 109.0 |
C66—N4—Cu2 | 117.1 (4) | C3—C4—H54B | 109.0 |
C12—C11—C16 | 118.9 (5) | H54A—C4—H54B | 107.8 |
C12—C11—C17 | 124.1 (4) | C4—C5—C6 | 113.2 (4) |
C16—C11—C17 | 117.0 (5) | C4—C5—H55A | 108.9 |
O1—C12—C11 | 123.5 (5) | C6—C5—H55A | 108.9 |
O1—C12—C13 | 118.4 (4) | C4—C5—H55B | 108.9 |
C11—C12—C13 | 118.1 (4) | C6—C5—H55B | 108.9 |
C14—C13—C12 | 121.0 (5) | H55A—C5—H55B | 107.8 |
C14—C13—H13 | 119.5 | N3—C6—C5 | 111.4 (3) |
C12—C13—H13 | 119.5 | N3—C6—H56A | 109.4 |
C15—C14—C13 | 120.9 (6) | C5—C6—H56A | 109.4 |
C15—C14—H14 | 119.6 | N3—C6—H56B | 109.4 |
C13—C14—H14 | 119.6 | C5—C6—H56B | 109.4 |
C14—C15—C16 | 119.4 (5) | H56A—C6—H56B | 108.0 |
C14—C15—H15 | 120.3 | N2—C61—C62 | 111.5 (6) |
C16—C15—H15 | 120.3 | N2—C61—H61A | 109.3 |
C15—C16—C11 | 121.6 (5) | C62—C61—H61A | 109.3 |
C15—C16—H16 | 119.2 | N2—C61—H61B | 109.3 |
C11—C16—H16 | 119.2 | C62—C61—H61B | 109.3 |
N1—C17—C11 | 126.7 (4) | H61A—C61—H61B | 108.0 |
N1—C17—H17 | 116.7 | C63—C62—C61 | 113.8 (7) |
C11—C17—H17 | 116.7 | C63—C62—H62A | 108.8 |
C26—C21—C27 | 117.9 (4) | C61—C62—H62A | 108.8 |
C26—C21—C22 | 119.3 (4) | C63—C62—H62B | 108.8 |
C27—C21—C22 | 122.7 (4) | C61—C62—H62B | 108.8 |
O2—C22—C23 | 119.4 (4) | H62A—C62—H62B | 107.7 |
O2—C22—C21 | 123.6 (4) | C62—C63—C64 | 112.6 (6) |
C23—C22—C21 | 116.9 (4) | C62—C63—H63A | 109.1 |
C24—C23—C22 | 122.2 (4) | C64—C63—H63A | 109.1 |
C24—C23—H23 | 118.9 | C62—C63—H63B | 109.1 |
C22—C23—H23 | 118.9 | C64—C63—H63B | 109.1 |
C23—C24—C25 | 120.7 (5) | H63A—C63—H63B | 107.8 |
C23—C24—H24 | 119.6 | C65—C64—C63 | 114.9 (6) |
C25—C24—H24 | 119.6 | C65—C64—H64A | 108.5 |
C26—C25—C24 | 119.6 (5) | C63—C64—H64A | 108.6 |
C26—C25—H25 | 120.2 | C65—C64—H64B | 108.6 |
C24—C25—H25 | 120.2 | C63—C64—H64B | 108.6 |
C25—C26—C21 | 121.1 (5) | H64A—C64—H64B | 107.5 |
C25—C26—H26 | 119.4 | C66—C65—C64 | 115.2 (6) |
C21—C26—H26 | 119.4 | C66—C65—H65A | 108.5 |
N2—C27—C21 | 127.1 (4) | C64—C65—H65A | 108.5 |
N2—C27—H27 | 116.5 | C66—C65—H65B | 108.5 |
C21—C27—H27 | 116.5 | C64—C65—H65B | 108.5 |
C32—C31—C36 | 119.6 (4) | H65A—C65—H65B | 107.5 |
C32—C31—C37 | 123.0 (5) | N4—C66—C65 | 114.8 (5) |
C36—C31—C37 | 117.4 (4) | N4—C66—H66A | 108.6 |
O3—C32—C31 | 124.1 (4) | C65—C66—H66A | 108.6 |
O3—C32—C33 | 118.7 (4) | N4—C66—H66B | 108.6 |
C31—C32—C33 | 117.1 (5) | C65—C66—H66B | 108.6 |
C34—C33—C32 | 122.0 (5) | H66A—C66—H66B | 107.6 |
C34—C33—H33 | 119.0 | C72—C71—H71A | 109.7 |
C32—C33—H33 | 119.0 | C72—C71—H71B | 109.7 |
C35—C34—C33 | 120.8 (5) | H71A—C71—H71B | 108.2 |
C35—C34—H34 | 119.6 | C73—C72—C71 | 115.1 (9) |
C33—C34—H34 | 119.6 | C73—C72—H72A | 108.5 |
C34—C35—C36 | 118.4 (5) | C71—C72—H72A | 108.5 |
C34—C35—H35 | 120.8 | C73—C72—H72B | 108.5 |
C36—C35—H35 | 120.8 | C71—C72—H72B | 108.5 |
C35—C36—C31 | 122.1 (5) | H72A—C72—H72B | 107.5 |
C35—C36—H36 | 118.9 | C72—C73—C74 | 112.7 (9) |
C31—C36—H36 | 118.9 | C72—C73—H73A | 109.0 |
N3—C37—C31 | 126.4 (4) | C74—C73—H73A | 109.1 |
N3—C37—H37 | 116.8 | C72—C73—H73B | 109.1 |
C31—C37—H37 | 116.8 | C74—C73—H73B | 109.0 |
C42—C41—C46 | 119.5 (4) | H73A—C73—H73B | 107.8 |
C42—C41—C47 | 122.9 (4) | C75—C74—C73 | 116.7 (10) |
C46—C41—C47 | 117.5 (4) | C75—C74—H74A | 108.1 |
O4—C42—C41 | 123.1 (4) | C73—C74—H74A | 108.1 |
O4—C42—C43 | 119.5 (4) | C75—C74—H74B | 108.2 |
C41—C42—C43 | 117.4 (4) | C73—C74—H74B | 108.2 |
C44—C43—C42 | 121.1 (5) | H74A—C74—H74B | 107.3 |
C44—C43—H43 | 119.4 | C74—C75—C76 | 115.1 (9) |
C42—C43—H43 | 119.4 | C74—C75—H75A | 108.6 |
C43—C44—C45 | 121.6 (5) | C76—C75—H75A | 108.5 |
C43—C44—H44 | 119.2 | C74—C75—H75B | 108.5 |
C45—C44—H44 | 119.2 | C76—C75—H75B | 108.5 |
C46—C45—C44 | 118.7 (5) | H75A—C75—H75B | 107.5 |
C46—C45—H45 | 120.7 | C75—C76—H76A | 110.3 |
C44—C45—H45 | 120.7 | C75—C76—H76B | 110.3 |
C45—C46—C41 | 121.7 (5) | H76A—C76—H76B | 108.5 |
O2—Cu1—O1—C12 | 89.0 (4) | C24—C25—C26—C21 | −0.4 (8) |
N2—Cu1—O1—C12 | −168.0 (3) | C27—C21—C26—C25 | 177.3 (5) |
N1—Cu1—O1—C12 | −10.6 (4) | C22—C21—C26—C25 | −1.4 (7) |
O1—Cu1—O2—C22 | 96.3 (5) | C61—N2—C27—C21 | −179.1 (5) |
N2—Cu1—O2—C22 | −6.3 (4) | Cu1—N2—C27—C21 | −2.6 (6) |
N1—Cu1—O2—C22 | −163.5 (4) | C26—C21—C27—N2 | 178.2 (4) |
O4—Cu2—O3—C32 | 76.1 (5) | C22—C21—C27—N2 | −3.2 (7) |
N4—Cu2—O3—C32 | 176.1 (4) | Cu2—O3—C32—C31 | 11.9 (6) |
N3—Cu2—O3—C32 | −17.9 (4) | Cu2—O3—C32—C33 | −169.2 (3) |
O3—Cu2—O4—C42 | 92.3 (5) | C36—C31—C32—O3 | −178.7 (4) |
N4—Cu2—O4—C42 | −7.5 (4) | C37—C31—C32—O3 | 3.5 (7) |
N3—Cu2—O4—C42 | −173.2 (4) | C36—C31—C32—C33 | 2.3 (6) |
O2—Cu1—N1—C17 | −149.1 (4) | C37—C31—C32—C33 | −175.5 (4) |
O1—Cu1—N1—C17 | 4.3 (4) | O3—C32—C33—C34 | 178.9 (4) |
N2—Cu1—N1—C17 | 108.9 (5) | C31—C32—C33—C34 | −2.1 (7) |
O2—Cu1—N1—C1 | 30.8 (3) | C32—C33—C34—C35 | 0.6 (8) |
O1—Cu1—N1—C1 | −175.8 (3) | C33—C34—C35—C36 | 0.6 (8) |
N2—Cu1—N1—C1 | −71.1 (5) | C34—C35—C36—C31 | −0.3 (8) |
O2—Cu1—N2—C27 | 6.1 (4) | C32—C31—C36—C35 | −1.2 (7) |
O1—Cu1—N2—C27 | −147.6 (4) | C37—C31—C36—C35 | 176.7 (5) |
N1—Cu1—N2—C27 | 107.5 (5) | C6—N3—C37—C31 | 175.8 (4) |
O2—Cu1—N2—C61 | −177.5 (4) | Cu2—N3—C37—C31 | −6.2 (6) |
O1—Cu1—N2—C61 | 28.8 (4) | C32—C31—C37—N3 | −6.0 (7) |
N1—Cu1—N2—C61 | −76.2 (6) | C36—C31—C37—N3 | 176.1 (4) |
O4—Cu2—N3—C37 | −146.2 (4) | Cu2—O4—C42—C41 | 1.7 (6) |
O3—Cu2—N3—C37 | 14.8 (4) | Cu2—O4—C42—C43 | 180.0 (3) |
N4—Cu2—N3—C37 | 118.3 (6) | C46—C41—C42—O4 | −178.2 (4) |
O4—Cu2—N3—C6 | 31.7 (3) | C47—C41—C42—O4 | 4.2 (7) |
O3—Cu2—N3—C6 | −167.2 (3) | C46—C41—C42—C43 | 3.5 (6) |
N4—Cu2—N3—C6 | −63.7 (7) | C47—C41—C42—C43 | −174.1 (4) |
O4—Cu2—N4—C47 | 10.6 (4) | O4—C42—C43—C44 | 178.8 (4) |
O3—Cu2—N4—C47 | −150.7 (4) | C41—C42—C43—C44 | −2.8 (6) |
N3—Cu2—N4—C47 | 105.6 (7) | C42—C43—C44—C45 | 0.6 (7) |
O4—Cu2—N4—C66 | −167.7 (4) | C43—C44—C45—C46 | 1.0 (7) |
O3—Cu2—N4—C66 | 31.0 (4) | C44—C45—C46—C41 | −0.2 (7) |
N3—Cu2—N4—C66 | −72.7 (8) | C42—C41—C46—C45 | −2.1 (7) |
Cu1—O1—C12—C11 | 11.0 (6) | C47—C41—C46—C45 | 175.7 (5) |
Cu1—O1—C12—C13 | −168.7 (3) | C66—N4—C47—C41 | 169.4 (5) |
C16—C11—C12—O1 | 178.6 (4) | Cu2—N4—C47—C41 | −8.9 (8) |
C17—C11—C12—O1 | −2.4 (7) | C42—C41—C47—N4 | −0.1 (8) |
C16—C11—C12—C13 | −1.7 (6) | C46—C41—C47—N4 | −177.7 (5) |
C17—C11—C12—C13 | 177.3 (4) | C17—N1—C1—C2 | −116.9 (4) |
O1—C12—C13—C14 | −179.0 (4) | Cu1—N1—C1—C2 | 63.1 (4) |
C11—C12—C13—C14 | 1.3 (7) | N1—C1—C2—C3 | 64.2 (5) |
C12—C13—C14—C15 | −0.6 (7) | C1—C2—C3—C4 | 175.7 (4) |
C13—C14—C15—C16 | 0.2 (8) | C2—C3—C4—C5 | −165.7 (4) |
C14—C15—C16—C11 | −0.7 (9) | C3—C4—C5—C6 | 175.5 (4) |
C12—C11—C16—C15 | 1.4 (8) | C37—N3—C6—C5 | −120.0 (4) |
C17—C11—C16—C15 | −177.6 (5) | Cu2—N3—C6—C5 | 61.9 (4) |
C1—N1—C17—C11 | −178.3 (4) | C4—C5—C6—N3 | 70.5 (5) |
Cu1—N1—C17—C11 | 1.6 (6) | C27—N2—C61—C62 | −94.2 (9) |
C12—C11—C17—N1 | −4.2 (7) | Cu1—N2—C61—C62 | 89.2 (10) |
C16—C11—C17—N1 | 174.8 (4) | N2—C61—C62—C63 | −68.4 (11) |
Cu1—O2—C22—C23 | −178.0 (3) | C61—C62—C63—C64 | −177.1 (7) |
Cu1—O2—C22—C21 | 2.8 (6) | C62—C63—C64—C65 | 70.6 (10) |
C26—C21—C22—O2 | −178.1 (4) | C63—C64—C65—C66 | −166.5 (7) |
C27—C21—C22—O2 | 3.2 (7) | C47—N4—C66—C65 | −96.2 (7) |
C26—C21—C22—C23 | 2.6 (6) | Cu2—N4—C66—C65 | 82.3 (6) |
C27—C21—C22—C23 | −176.0 (4) | C64—C65—C66—N4 | −58.0 (9) |
O2—C22—C23—C24 | 178.5 (5) | C71—C72—C73—C74 | −161 (3) |
C21—C22—C23—C24 | −2.2 (7) | C72—C73—C74—C75 | 166.9 (18) |
C22—C23—C24—C25 | 0.4 (8) | C73—C74—C75—C76 | −157.7 (16) |
C23—C24—C25—C26 | 0.9 (8) |
[Cu2(C20H22N2O2)2] | Dx = 1.402 Mg m−3 |
Mr = 771.81 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P43 | Cell parameters from 4153 reflections |
Hall symbol: P 4cw | θ = 2.9–27.5° |
a = 13.3288 (2) Å | µ = 1.21 mm−1 |
c = 20.5834 (7) Å | T = 150 K |
V = 3656.78 (15) Å3 | Prism, red |
Z = 4 | 0.20 × 0.18 × 0.10 mm |
F(000) = 1608 |
Nonius KappaCCD area-detector diffractometer | 7763 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 4824 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.103 |
ϕ scans and ω scans with κ offsets | θmax = 27.5°, θmin = 2.9° |
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997) | h = −17→17 |
Tmin = 0.794, Tmax = 0.889 | k = −12→12 |
20308 measured reflections | l = −26→23 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0212P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.96 | (Δ/σ)max < 0.001 |
7763 reflections | Δρmax = 0.35 e Å−3 |
470 parameters | Δρmin = −0.47 e Å−3 |
59 restraints | Absolute structure: Flack (1983), 3505 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.000 (14) |
[Cu2(C20H22N2O2)2] | Z = 4 |
Mr = 771.81 | Mo Kα radiation |
Tetragonal, P43 | µ = 1.21 mm−1 |
a = 13.3288 (2) Å | T = 150 K |
c = 20.5834 (7) Å | 0.20 × 0.18 × 0.10 mm |
V = 3656.78 (15) Å3 |
Nonius KappaCCD area-detector diffractometer | 7763 independent reflections |
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997) | 4824 reflections with I > 2σ(I) |
Tmin = 0.794, Tmax = 0.889 | Rint = 0.103 |
20308 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.098 | Δρmax = 0.35 e Å−3 |
S = 0.96 | Δρmin = −0.47 e Å−3 |
7763 reflections | Absolute structure: Flack (1983), 3505 Friedel pairs |
470 parameters | Absolute structure parameter: 0.000 (14) |
59 restraints |
Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G. C. & Holmes, K. C. (1966). Acta Cryst. 20, 886–891.] which effectively corrects for absorption effects. High-redundancy data were used in the scaling program, hence the `multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the `size' command in the SHELXL97 input file. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.19609 (4) | 0.33581 (4) | 0.49998 (3) | 0.03574 (16) | |
Cu2 | 0.34869 (4) | −0.17673 (4) | 0.35611 (3) | 0.03360 (16) | |
O1 | 0.1703 (2) | 0.2884 (2) | 0.58532 (18) | 0.0410 (9) | |
O2 | 0.2022 (2) | 0.4367 (2) | 0.43572 (19) | 0.0471 (10) | |
O3 | 0.2201 (2) | −0.1761 (2) | 0.31595 (17) | 0.0388 (9) | |
O4 | 0.4817 (2) | −0.2143 (2) | 0.37788 (17) | 0.0383 (9) | |
N1 | 0.3429 (3) | 0.3433 (3) | 0.5133 (2) | 0.0354 (10) | |
N2 | 0.0692 (3) | 0.2809 (3) | 0.4675 (2) | 0.0334 (9) | |
N3 | 0.4046 (3) | −0.0810 (3) | 0.2919 (2) | 0.0348 (10) | |
N4 | 0.2922 (3) | −0.2400 (3) | 0.4335 (2) | 0.0408 (11) | |
C21 | 0.0427 (3) | 0.4077 (3) | 0.3839 (2) | 0.0326 (11) | |
C22 | 0.1346 (3) | 0.4608 (3) | 0.3919 (3) | 0.0361 (12) | |
C23 | 0.1531 (3) | 0.5418 (3) | 0.3505 (3) | 0.0432 (13) | |
C24 | 0.0854 (4) | 0.5711 (4) | 0.3044 (3) | 0.0502 (14) | |
C25 | −0.0068 (4) | 0.5208 (4) | 0.2977 (3) | 0.0503 (14) | |
C26 | −0.0261 (4) | 0.4408 (4) | 0.3367 (3) | 0.0425 (14) | |
C27 | 0.0176 (3) | 0.3207 (4) | 0.4217 (3) | 0.0385 (13) | |
C11 | 0.3371 (4) | 0.3014 (3) | 0.6283 (3) | 0.0376 (13) | |
C12 | 0.2329 (3) | 0.2854 (3) | 0.6353 (3) | 0.0338 (12) | |
C13 | 0.1940 (4) | 0.2659 (4) | 0.6974 (3) | 0.0437 (13) | |
C14 | 0.2567 (4) | 0.2613 (4) | 0.7507 (3) | 0.0500 (14) | |
C15 | 0.3579 (4) | 0.2741 (4) | 0.7449 (3) | 0.0560 (15) | |
C16 | 0.3974 (4) | 0.2934 (4) | 0.6845 (3) | 0.0526 (15) | |
C17 | 0.3846 (4) | 0.3274 (3) | 0.5682 (3) | 0.0401 (14) | |
C41 | 0.4493 (3) | −0.3197 (3) | 0.4700 (3) | 0.0357 (12) | |
C42 | 0.5127 (3) | −0.2735 (3) | 0.4247 (2) | 0.0310 (11) | |
C43 | 0.6173 (3) | −0.2920 (3) | 0.4319 (3) | 0.0377 (12) | |
C44 | 0.6533 (3) | −0.3532 (3) | 0.4796 (3) | 0.0389 (13) | |
C45 | 0.5891 (4) | −0.4011 (4) | 0.5228 (3) | 0.0443 (14) | |
C46 | 0.4881 (4) | −0.3835 (4) | 0.5177 (3) | 0.0435 (14) | |
C47 | 0.3434 (4) | −0.2991 (4) | 0.4721 (3) | 0.0439 (14) | |
C31 | 0.2630 (3) | −0.0914 (3) | 0.2165 (3) | 0.0350 (12) | |
C32 | 0.1973 (3) | −0.1459 (3) | 0.2572 (3) | 0.0349 (13) | |
C33 | 0.1007 (3) | −0.1666 (3) | 0.2323 (3) | 0.0365 (12) | |
C34 | 0.0727 (4) | −0.1390 (4) | 0.1703 (3) | 0.0435 (13) | |
C35 | 0.1394 (4) | −0.0881 (4) | 0.1299 (3) | 0.0444 (14) | |
C36 | 0.2326 (4) | −0.0643 (3) | 0.1532 (3) | 0.0418 (13) | |
C37 | 0.3620 (3) | −0.0590 (3) | 0.2375 (3) | 0.0368 (13) | |
C1 | 0.4079 (3) | 0.3716 (3) | 0.4581 (2) | 0.0376 (12) | |
C2 | 0.4011 (4) | 0.2955 (3) | 0.4034 (2) | 0.0414 (13) | |
C3 | 0.4413 (3) | 0.1916 (3) | 0.4187 (2) | 0.0383 (13) | |
C4 | 0.4391 (3) | 0.1239 (3) | 0.3593 (2) | 0.0396 (12) | |
C5 | 0.4994 (3) | 0.0280 (3) | 0.3666 (2) | 0.0418 (13) | |
C6 | 0.5032 (3) | −0.0352 (3) | 0.3053 (2) | 0.0378 (12) | |
C61 | 0.0247 (7) | 0.1899 (4) | 0.4985 (6) | 0.0362 (18) | 0.747 (6) |
C62 | 0.0642 (4) | 0.0930 (4) | 0.4691 (4) | 0.047 (2) | 0.747 (6) |
C63 | 0.1749 (4) | 0.0737 (4) | 0.4809 (4) | 0.054 (2) | 0.747 (6) |
C64 | 0.2097 (5) | −0.0253 (4) | 0.4518 (4) | 0.052 (2) | 0.747 (6) |
C65 | 0.1737 (5) | −0.1179 (4) | 0.4881 (4) | 0.053 (2) | 0.747 (6) |
C66 | 0.1864 (4) | −0.2165 (4) | 0.4519 (3) | 0.0348 (18) | 0.747 (6) |
N72 | 0.0692 (3) | 0.2809 (3) | 0.4675 (2) | 0.0334 (9) | 0.00 |
C71 | 0.040 (2) | 0.1806 (12) | 0.491 (3) | 0.060* | 0.253 (6) |
C72 | 0.1225 (17) | 0.1066 (8) | 0.4754 (13) | 0.060* | 0.253 (6) |
C73 | 0.1144 (15) | 0.0076 (8) | 0.5086 (9) | 0.060* | 0.253 (6) |
C74 | 0.1749 (19) | −0.0746 (9) | 0.4762 (13) | 0.060* | 0.253 (6) |
C75 | 0.1505 (13) | −0.1784 (9) | 0.4970 (10) | 0.060* | 0.253 (6) |
C76 | 0.1853 (10) | −0.2594 (12) | 0.4509 (14) | 0.060* | 0.253 (6) |
N74 | 0.2922 (3) | −0.2400 (3) | 0.4335 (2) | 0.0408 (11) | 0.00 |
H23 | 0.2144 | 0.5775 | 0.3544 | 0.052* | |
H24 | 0.1007 | 0.6258 | 0.2766 | 0.060* | |
H25 | −0.0547 | 0.5424 | 0.2666 | 0.060* | |
H26 | −0.0879 | 0.4061 | 0.3320 | 0.051* | |
H27 | −0.0444 | 0.2890 | 0.4116 | 0.046* | |
H13 | 0.1240 | 0.2559 | 0.7028 | 0.052* | |
H14 | 0.2287 | 0.2488 | 0.7924 | 0.060* | |
H15 | 0.4002 | 0.2698 | 0.7820 | 0.067* | |
H16 | 0.4679 | 0.3016 | 0.6804 | 0.063* | |
H17 | 0.4556 | 0.3336 | 0.5694 | 0.048* | |
H43 | 0.6631 | −0.2610 | 0.4028 | 0.045* | |
H44 | 0.7236 | −0.3633 | 0.4834 | 0.047* | |
H45 | 0.6146 | −0.4450 | 0.5551 | 0.053* | |
H46 | 0.4435 | −0.4154 | 0.5471 | 0.052* | |
H47 | 0.3064 | −0.3321 | 0.5053 | 0.053* | |
H33 | 0.0536 | −0.2006 | 0.2591 | 0.044* | |
H34 | 0.0073 | −0.1547 | 0.1551 | 0.052* | |
H35 | 0.1205 | −0.0703 | 0.0870 | 0.053* | |
H36 | 0.2780 | −0.0287 | 0.1260 | 0.050* | |
H37 | 0.3988 | −0.0178 | 0.2083 | 0.044* | |
H1A | 0.4783 | 0.3763 | 0.4732 | 0.045* | |
H1B | 0.3875 | 0.4384 | 0.4417 | 0.045* | |
H2A | 0.3298 | 0.2890 | 0.3905 | 0.050* | |
H2B | 0.4382 | 0.3221 | 0.3655 | 0.050* | |
H3A | 0.4004 | 0.1611 | 0.4537 | 0.046* | |
H3B | 0.5111 | 0.1973 | 0.4346 | 0.046* | |
H4A | 0.3685 | 0.1060 | 0.3497 | 0.048* | |
H4B | 0.4653 | 0.1618 | 0.3215 | 0.048* | |
H5A | 0.4698 | −0.0126 | 0.4021 | 0.050* | |
H5B | 0.5688 | 0.0456 | 0.3795 | 0.050* | |
H6A | 0.5233 | 0.0074 | 0.2681 | 0.045* | |
H6B | 0.5542 | −0.0887 | 0.3104 | 0.045* | |
H61A | −0.0492 | 0.1920 | 0.4936 | 0.043* | 0.747 (6) |
H61B | 0.0401 | 0.1908 | 0.5456 | 0.043* | 0.747 (6) |
H62A | 0.0253 | 0.0362 | 0.4872 | 0.056* | 0.747 (6) |
H62B | 0.0521 | 0.0945 | 0.4217 | 0.056* | 0.747 (6) |
H63A | 0.1878 | 0.0731 | 0.5283 | 0.065* | 0.747 (6) |
H63B | 0.2144 | 0.1292 | 0.4617 | 0.065* | 0.747 (6) |
H64A | 0.1856 | −0.0292 | 0.4063 | 0.062* | 0.747 (6) |
H64B | 0.2839 | −0.0258 | 0.4507 | 0.062* | 0.747 (6) |
H65A | 0.2108 | −0.1224 | 0.5297 | 0.064* | 0.747 (6) |
H65B | 0.1018 | −0.1091 | 0.4986 | 0.064* | 0.747 (6) |
H66A | 0.1604 | −0.2716 | 0.4795 | 0.042* | 0.747 (6) |
H66B | 0.1451 | −0.2144 | 0.4120 | 0.042* | 0.747 (6) |
H71A | −0.0231 | 0.1593 | 0.4703 | 0.072* | 0.253 (6) |
H71B | 0.0295 | 0.1828 | 0.5388 | 0.072* | 0.253 (6) |
H72A | 0.1227 | 0.0952 | 0.4279 | 0.072* | 0.253 (6) |
H72B | 0.1877 | 0.1372 | 0.4871 | 0.072* | 0.253 (6) |
H73A | 0.0430 | −0.0129 | 0.5097 | 0.072* | 0.253 (6) |
H73B | 0.1373 | 0.0150 | 0.5541 | 0.072* | 0.253 (6) |
H74A | 0.1648 | −0.0698 | 0.4287 | 0.072* | 0.253 (6) |
H74B | 0.2469 | −0.0622 | 0.4849 | 0.072* | 0.253 (6) |
H75A | 0.0769 | −0.1840 | 0.5023 | 0.072* | 0.253 (6) |
H75B | 0.1814 | −0.1905 | 0.5401 | 0.072* | 0.253 (6) |
H76A | 0.1789 | −0.3260 | 0.4718 | 0.072* | 0.253 (6) |
H76B | 0.1433 | −0.2590 | 0.4112 | 0.072* | 0.253 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0316 (3) | 0.0402 (3) | 0.0354 (4) | 0.0011 (3) | −0.0025 (3) | 0.0014 (3) |
Cu2 | 0.0306 (3) | 0.0403 (3) | 0.0299 (4) | −0.0006 (3) | 0.0009 (3) | 0.0012 (3) |
O1 | 0.0400 (18) | 0.050 (2) | 0.033 (2) | 0.0018 (16) | −0.0033 (16) | 0.0049 (17) |
O2 | 0.0348 (18) | 0.048 (2) | 0.058 (3) | −0.0052 (16) | −0.0046 (19) | 0.0154 (19) |
O3 | 0.0333 (17) | 0.055 (2) | 0.028 (3) | −0.0017 (15) | 0.0022 (16) | 0.0041 (17) |
O4 | 0.0345 (17) | 0.0455 (19) | 0.035 (2) | 0.0024 (14) | 0.0028 (16) | 0.0082 (17) |
N1 | 0.036 (2) | 0.036 (2) | 0.035 (3) | 0.0049 (17) | 0.000 (2) | −0.004 (2) |
N2 | 0.038 (2) | 0.035 (2) | 0.027 (3) | 0.0037 (18) | 0.0013 (19) | 0.0017 (19) |
N3 | 0.037 (2) | 0.032 (2) | 0.035 (3) | −0.0064 (17) | −0.003 (2) | −0.005 (2) |
N4 | 0.028 (2) | 0.061 (3) | 0.034 (3) | −0.0002 (19) | 0.0052 (19) | 0.001 (2) |
C21 | 0.035 (3) | 0.040 (3) | 0.022 (3) | 0.003 (2) | 0.002 (2) | 0.002 (2) |
C22 | 0.036 (3) | 0.038 (3) | 0.034 (4) | 0.005 (2) | 0.004 (2) | 0.003 (2) |
C23 | 0.043 (3) | 0.042 (3) | 0.045 (4) | 0.004 (2) | 0.008 (3) | 0.013 (3) |
C24 | 0.063 (4) | 0.047 (3) | 0.041 (4) | 0.012 (3) | 0.011 (3) | 0.009 (3) |
C25 | 0.063 (4) | 0.056 (3) | 0.032 (4) | 0.013 (3) | −0.012 (3) | 0.000 (3) |
C26 | 0.045 (3) | 0.047 (3) | 0.036 (4) | 0.001 (2) | −0.005 (3) | 0.000 (3) |
C27 | 0.030 (3) | 0.042 (3) | 0.044 (4) | −0.002 (2) | −0.001 (2) | −0.006 (3) |
C11 | 0.042 (3) | 0.034 (3) | 0.036 (4) | 0.006 (2) | −0.007 (3) | −0.003 (2) |
C12 | 0.038 (3) | 0.029 (2) | 0.035 (4) | 0.001 (2) | −0.008 (2) | −0.001 (2) |
C13 | 0.042 (3) | 0.044 (3) | 0.044 (4) | −0.001 (2) | 0.000 (3) | 0.006 (3) |
C14 | 0.068 (4) | 0.050 (3) | 0.032 (4) | −0.011 (3) | −0.001 (3) | 0.001 (3) |
C15 | 0.068 (4) | 0.069 (4) | 0.031 (4) | −0.015 (3) | −0.020 (3) | 0.011 (3) |
C16 | 0.043 (3) | 0.068 (4) | 0.048 (4) | 0.004 (3) | −0.012 (3) | −0.008 (3) |
C17 | 0.034 (3) | 0.039 (3) | 0.047 (4) | 0.004 (2) | 0.000 (3) | −0.006 (3) |
C41 | 0.034 (3) | 0.041 (3) | 0.032 (3) | 0.000 (2) | 0.002 (2) | −0.001 (2) |
C42 | 0.032 (2) | 0.034 (3) | 0.028 (3) | −0.003 (2) | 0.001 (2) | −0.003 (2) |
C43 | 0.031 (3) | 0.044 (3) | 0.038 (4) | −0.006 (2) | 0.001 (2) | −0.001 (3) |
C44 | 0.031 (2) | 0.042 (3) | 0.043 (4) | 0.004 (2) | −0.011 (2) | −0.009 (3) |
C45 | 0.046 (3) | 0.039 (3) | 0.048 (4) | 0.006 (2) | −0.010 (3) | 0.002 (3) |
C46 | 0.044 (3) | 0.047 (3) | 0.039 (4) | −0.002 (2) | 0.003 (3) | 0.007 (3) |
C47 | 0.041 (3) | 0.052 (3) | 0.039 (4) | −0.008 (2) | 0.005 (3) | 0.005 (3) |
C31 | 0.038 (3) | 0.032 (2) | 0.035 (3) | −0.002 (2) | 0.001 (2) | −0.001 (2) |
C32 | 0.035 (3) | 0.031 (2) | 0.039 (4) | 0.006 (2) | −0.003 (3) | −0.002 (2) |
C33 | 0.037 (3) | 0.037 (3) | 0.036 (4) | 0.003 (2) | 0.001 (2) | 0.002 (2) |
C34 | 0.049 (3) | 0.045 (3) | 0.036 (4) | −0.002 (2) | −0.007 (3) | −0.001 (3) |
C35 | 0.057 (3) | 0.051 (3) | 0.025 (3) | −0.008 (3) | −0.010 (3) | 0.005 (3) |
C36 | 0.054 (3) | 0.036 (3) | 0.036 (4) | −0.005 (2) | 0.005 (3) | 0.001 (3) |
C37 | 0.036 (3) | 0.032 (2) | 0.043 (4) | 0.000 (2) | 0.004 (2) | −0.004 (2) |
C1 | 0.032 (3) | 0.038 (3) | 0.043 (4) | −0.008 (2) | 0.000 (2) | 0.003 (2) |
C2 | 0.042 (3) | 0.042 (3) | 0.040 (4) | −0.002 (2) | 0.006 (3) | 0.001 (3) |
C3 | 0.038 (3) | 0.042 (3) | 0.035 (4) | −0.004 (2) | −0.003 (2) | 0.005 (3) |
C4 | 0.044 (3) | 0.044 (3) | 0.031 (3) | −0.007 (2) | 0.000 (3) | −0.003 (3) |
C5 | 0.038 (3) | 0.041 (3) | 0.046 (4) | −0.006 (2) | −0.007 (3) | 0.000 (3) |
C6 | 0.036 (3) | 0.037 (3) | 0.041 (4) | −0.006 (2) | 0.004 (2) | 0.000 (3) |
C61 | 0.038 (4) | 0.033 (3) | 0.038 (5) | 0.001 (3) | −0.004 (4) | 0.004 (4) |
C62 | 0.050 (4) | 0.035 (4) | 0.055 (6) | 0.001 (3) | −0.010 (4) | −0.002 (4) |
C63 | 0.037 (4) | 0.043 (4) | 0.083 (7) | −0.011 (3) | 0.001 (4) | 0.000 (4) |
C64 | 0.042 (4) | 0.043 (4) | 0.069 (7) | 0.000 (3) | 0.019 (4) | 0.007 (4) |
C65 | 0.043 (4) | 0.036 (4) | 0.081 (7) | 0.009 (4) | 0.034 (4) | 0.005 (5) |
C66 | 0.022 (3) | 0.049 (4) | 0.034 (5) | 0.007 (3) | 0.012 (3) | 0.013 (4) |
N72 | 0.038 (2) | 0.035 (2) | 0.027 (3) | 0.0037 (18) | 0.0013 (19) | 0.0017 (19) |
N74 | 0.028 (2) | 0.061 (3) | 0.034 (3) | −0.0002 (19) | 0.0052 (19) | 0.001 (2) |
Cu1—O2 | 1.887 (4) | C33—C34 | 1.379 (7) |
Cu1—O1 | 1.898 (4) | C33—H33 | 0.9500 |
Cu1—N2 | 1.961 (4) | C34—C35 | 1.394 (7) |
Cu1—N1 | 1.979 (4) | C34—H34 | 0.9500 |
Cu2—O4 | 1.896 (3) | C35—C36 | 1.368 (7) |
Cu2—O3 | 1.903 (3) | C35—H35 | 0.9500 |
Cu2—N4 | 1.954 (4) | C36—H36 | 0.9500 |
Cu2—N3 | 1.983 (4) | C37—H37 | 0.9500 |
O1—C12 | 1.325 (6) | C1—C2 | 1.519 (3) |
O2—C22 | 1.314 (6) | C1—H1A | 0.9900 |
O3—C32 | 1.311 (6) | C1—H1B | 0.9900 |
O4—C42 | 1.312 (5) | C2—C3 | 1.518 (3) |
N1—C17 | 1.278 (6) | C2—H2A | 0.9900 |
N1—C1 | 1.476 (6) | C2—H2B | 0.9900 |
N2—C27 | 1.281 (6) | C3—C4 | 1.521 (3) |
N2—C61 | 1.493 (7) | C3—H3A | 0.9900 |
N3—C37 | 1.288 (6) | C3—H3B | 0.9900 |
N3—C6 | 1.475 (5) | C4—C5 | 1.518 (3) |
N4—C47 | 1.310 (6) | C4—H4A | 0.9900 |
N4—C66 | 1.493 (6) | C4—H4B | 0.9900 |
C21—C26 | 1.406 (6) | C5—C6 | 1.519 (3) |
C21—C22 | 1.424 (6) | C5—H5A | 0.9900 |
C21—C27 | 1.437 (7) | C5—H5B | 0.9900 |
C22—C23 | 1.397 (6) | C6—H6A | 0.9900 |
C23—C24 | 1.366 (7) | C6—H6B | 0.9900 |
C23—H23 | 0.9500 | C61—C62 | 1.520 (3) |
C24—C25 | 1.406 (7) | C61—H61A | 0.9900 |
C24—H24 | 0.9500 | C61—H61B | 0.9900 |
C25—C26 | 1.360 (7) | C62—C63 | 1.517 (3) |
C25—H25 | 0.9500 | C62—H62A | 0.9900 |
C26—H26 | 0.9500 | C62—H62B | 0.9900 |
C27—H27 | 0.9500 | C63—C64 | 1.522 (3) |
C11—C12 | 1.412 (6) | C63—H63A | 0.9900 |
C11—C16 | 1.414 (7) | C63—H63B | 0.9900 |
C11—C17 | 1.431 (7) | C64—C65 | 1.521 (3) |
C12—C13 | 1.404 (7) | C64—H64A | 0.9900 |
C13—C14 | 1.380 (7) | C64—H64B | 0.9900 |
C13—H13 | 0.9500 | C65—C66 | 1.520 (3) |
C14—C15 | 1.365 (7) | C65—H65A | 0.9900 |
C14—H14 | 0.9500 | C65—H65B | 0.9900 |
C15—C16 | 1.375 (8) | C66—H66A | 0.9900 |
C15—H15 | 0.9500 | C66—H66B | 0.9900 |
C16—H16 | 0.9500 | C71—C72 | 1.509 (10) |
C17—H17 | 0.9500 | C71—H71A | 0.9900 |
C41—C46 | 1.398 (6) | C71—H71B | 0.9900 |
C41—C42 | 1.400 (6) | C72—C73 | 1.491 (10) |
C41—C47 | 1.439 (6) | C72—H72A | 0.9900 |
C42—C43 | 1.424 (6) | C72—H72B | 0.9900 |
C43—C44 | 1.363 (7) | C73—C74 | 1.515 (10) |
C43—H43 | 0.9500 | C73—H73A | 0.9900 |
C44—C45 | 1.389 (7) | C73—H73B | 0.9900 |
C44—H44 | 0.9500 | C74—C75 | 1.484 (9) |
C45—C46 | 1.370 (6) | C74—H74A | 0.9900 |
C45—H45 | 0.9500 | C74—H74B | 0.9900 |
C46—H46 | 0.9500 | C75—C76 | 1.511 (9) |
C47—H47 | 0.9500 | C75—H75A | 0.9900 |
C31—C32 | 1.412 (7) | C75—H75B | 0.9900 |
C31—C36 | 1.413 (7) | C76—H76A | 0.9900 |
C31—C37 | 1.453 (6) | C76—H76B | 0.9900 |
C32—C33 | 1.413 (6) | ||
O2—Cu1—O1 | 153.28 (15) | C35—C36—H36 | 119.2 |
O2—Cu1—N2 | 93.64 (15) | C31—C36—H36 | 119.2 |
O1—Cu1—N2 | 92.05 (16) | N3—C37—C31 | 126.2 (5) |
O2—Cu1—N1 | 91.07 (15) | N3—C37—H37 | 116.9 |
O1—Cu1—N1 | 93.88 (17) | C31—C37—H37 | 116.9 |
N2—Cu1—N1 | 156.81 (16) | N1—C1—C2 | 111.4 (4) |
O4—Cu2—O3 | 161.09 (14) | N1—C1—H1A | 109.4 |
O4—Cu2—N4 | 93.08 (15) | C2—C1—H1A | 109.4 |
O3—Cu2—N4 | 90.52 (15) | N1—C1—H1B | 109.4 |
O4—Cu2—N3 | 88.64 (14) | C2—C1—H1B | 109.4 |
O3—Cu2—N3 | 92.63 (15) | H1A—C1—H1B | 108.0 |
N4—Cu2—N3 | 165.10 (17) | C3—C2—C1 | 115.7 (4) |
C12—O1—Cu1 | 127.9 (3) | C3—C2—H2A | 108.3 |
C22—O2—Cu1 | 128.7 (3) | C1—C2—H2A | 108.3 |
C32—O3—Cu2 | 127.7 (3) | C3—C2—H2B | 108.3 |
C42—O4—Cu2 | 128.8 (3) | C1—C2—H2B | 108.3 |
C17—N1—C1 | 117.9 (4) | H2A—C2—H2B | 107.4 |
C17—N1—Cu1 | 122.9 (4) | C2—C3—C4 | 111.6 (4) |
C1—N1—Cu1 | 119.1 (3) | C2—C3—H3A | 109.3 |
C27—N2—C61 | 116.0 (6) | C4—C3—H3A | 109.3 |
C27—N2—Cu1 | 124.0 (3) | C2—C3—H3B | 109.3 |
C61—N2—Cu1 | 120.0 (6) | C4—C3—H3B | 109.3 |
C37—N3—C6 | 117.5 (4) | H3A—C3—H3B | 108.0 |
C37—N3—Cu2 | 124.0 (3) | C5—C4—C3 | 114.1 (4) |
C6—N3—Cu2 | 118.4 (3) | C5—C4—H4A | 108.7 |
C47—N4—C66 | 117.7 (5) | C3—C4—H4A | 108.7 |
C47—N4—Cu2 | 123.6 (3) | C5—C4—H4B | 108.7 |
C66—N4—Cu2 | 118.7 (4) | C3—C4—H4B | 108.7 |
C26—C21—C22 | 119.1 (4) | H4A—C4—H4B | 107.6 |
C26—C21—C27 | 118.3 (4) | C4—C5—C6 | 113.7 (4) |
C22—C21—C27 | 122.6 (4) | C4—C5—H5A | 108.8 |
O2—C22—C23 | 119.2 (4) | C6—C5—H5A | 108.8 |
O2—C22—C21 | 123.2 (4) | C4—C5—H5B | 108.8 |
C23—C22—C21 | 117.6 (5) | C6—C5—H5B | 108.8 |
C24—C23—C22 | 121.9 (5) | H5A—C5—H5B | 107.7 |
C24—C23—H23 | 119.1 | N3—C6—C5 | 110.8 (4) |
C22—C23—H23 | 119.1 | N3—C6—H6A | 109.5 |
C23—C24—C25 | 120.6 (5) | C5—C6—H6A | 109.5 |
C23—C24—H24 | 119.7 | N3—C6—H6B | 109.5 |
C25—C24—H24 | 119.7 | C5—C6—H6B | 109.5 |
C26—C25—C24 | 118.8 (5) | H6A—C6—H6B | 108.1 |
C26—C25—H25 | 120.6 | N2—C61—C62 | 112.5 (5) |
C24—C25—H25 | 120.6 | N2—C61—H61A | 109.1 |
C25—C26—C21 | 122.0 (5) | C62—C61—H61A | 109.1 |
C25—C26—H26 | 119.0 | N2—C61—H61B | 109.1 |
C21—C26—H26 | 119.0 | C62—C61—H61B | 109.1 |
N2—C27—C21 | 127.4 (4) | H61A—C61—H61B | 107.8 |
N2—C27—H27 | 116.3 | C63—C62—C61 | 114.6 (6) |
C21—C27—H27 | 116.3 | C63—C62—H62A | 108.6 |
C12—C11—C16 | 117.7 (5) | C61—C62—H62A | 108.6 |
C12—C11—C17 | 124.1 (5) | C63—C62—H62B | 108.6 |
C16—C11—C17 | 118.3 (5) | C61—C62—H62B | 108.6 |
O1—C12—C13 | 118.7 (4) | H62A—C62—H62B | 107.6 |
O1—C12—C11 | 122.3 (5) | C62—C63—C64 | 112.3 (5) |
C13—C12—C11 | 119.0 (5) | C62—C63—H63A | 109.1 |
C14—C13—C12 | 120.6 (5) | C64—C63—H63A | 109.1 |
C14—C13—H13 | 119.7 | C62—C63—H63B | 109.1 |
C12—C13—H13 | 119.7 | C64—C63—H63B | 109.1 |
C15—C14—C13 | 121.5 (6) | H63A—C63—H63B | 107.9 |
C15—C14—H14 | 119.2 | C65—C64—C63 | 114.4 (5) |
C13—C14—H14 | 119.2 | C65—C64—H64A | 108.7 |
C14—C15—C16 | 118.8 (6) | C63—C64—H64A | 108.7 |
C14—C15—H15 | 120.6 | C65—C64—H64B | 108.7 |
C16—C15—H15 | 120.6 | C63—C64—H64B | 108.7 |
C15—C16—C11 | 122.4 (5) | H64A—C64—H64B | 107.6 |
C15—C16—H16 | 118.8 | C66—C65—C64 | 115.2 (5) |
C11—C16—H16 | 118.8 | C66—C65—H65A | 108.5 |
N1—C17—C11 | 127.8 (5) | C64—C65—H65A | 108.5 |
N1—C17—H17 | 116.1 | C66—C65—H65B | 108.5 |
C11—C17—H17 | 116.1 | C64—C65—H65B | 108.5 |
C46—C41—C42 | 120.8 (4) | H65A—C65—H65B | 107.5 |
C46—C41—C47 | 117.2 (5) | N4—C66—C65 | 114.2 (5) |
C42—C41—C47 | 121.9 (5) | N4—C66—H66A | 108.7 |
O4—C42—C41 | 124.3 (4) | C65—C66—H66A | 108.7 |
O4—C42—C43 | 119.2 (4) | N4—C66—H66B | 108.7 |
C41—C42—C43 | 116.4 (5) | C65—C66—H66B | 108.7 |
C44—C43—C42 | 121.6 (5) | H66A—C66—H66B | 107.6 |
C44—C43—H43 | 119.2 | C72—C71—H71A | 109.8 |
C42—C43—H43 | 119.2 | C72—C71—H71B | 109.8 |
C43—C44—C45 | 121.2 (4) | H71A—C71—H71B | 108.3 |
C43—C44—H44 | 119.4 | C73—C72—C71 | 115.3 (10) |
C45—C44—H44 | 119.4 | C73—C72—H72A | 108.5 |
C46—C45—C44 | 118.5 (5) | C71—C72—H72A | 108.5 |
C46—C45—H45 | 120.7 | C73—C72—H72B | 108.5 |
C44—C45—H45 | 120.7 | C71—C72—H72B | 108.5 |
C45—C46—C41 | 121.4 (5) | H72A—C72—H72B | 107.5 |
C45—C46—H46 | 119.3 | C72—C73—C74 | 113.6 (10) |
C41—C46—H46 | 119.3 | C72—C73—H73A | 108.9 |
N4—C47—C41 | 127.4 (5) | C74—C73—H73A | 108.8 |
N4—C47—H47 | 116.3 | C72—C73—H73B | 108.8 |
C41—C47—H47 | 116.3 | C74—C73—H73B | 108.8 |
C32—C31—C36 | 120.0 (4) | H73A—C73—H73B | 107.7 |
C32—C31—C37 | 122.7 (5) | C75—C74—C73 | 115.5 (10) |
C36—C31—C37 | 117.3 (5) | C75—C74—H74A | 108.4 |
O3—C32—C31 | 124.1 (4) | C73—C74—H74A | 108.4 |
O3—C32—C33 | 119.0 (5) | C75—C74—H74B | 108.4 |
C31—C32—C33 | 116.8 (5) | C73—C74—H74B | 108.4 |
C34—C33—C32 | 122.0 (5) | H74A—C74—H74B | 107.5 |
C34—C33—H33 | 119.0 | C74—C75—C76 | 114.7 (10) |
C32—C33—H33 | 119.0 | C74—C75—H75A | 108.6 |
C33—C34—C35 | 120.6 (5) | C76—C75—H75A | 108.6 |
C33—C34—H34 | 119.7 | C74—C75—H75B | 108.6 |
C35—C34—H34 | 119.7 | C76—C75—H75B | 108.6 |
C36—C35—C34 | 118.9 (5) | H75A—C75—H75B | 107.6 |
C36—C35—H35 | 120.5 | C75—C76—H76A | 110.0 |
C34—C35—H35 | 120.5 | C75—C76—H76B | 110.0 |
C35—C36—C31 | 121.6 (5) | H76A—C76—H76B | 108.4 |
O2—Cu1—O1—C12 | −88.3 (5) | C14—C15—C16—C11 | 0.6 (9) |
N2—Cu1—O1—C12 | 169.4 (4) | C12—C11—C16—C15 | −2.1 (8) |
N1—Cu1—O1—C12 | 11.9 (4) | C17—C11—C16—C15 | 176.5 (5) |
O1—Cu1—O2—C22 | −95.5 (5) | C1—N1—C17—C11 | 178.6 (4) |
N2—Cu1—O2—C22 | 6.4 (4) | Cu1—N1—C17—C11 | 0.6 (7) |
N1—Cu1—O2—C22 | 163.7 (4) | C12—C11—C17—N1 | 2.4 (8) |
O4—Cu2—O3—C32 | −76.0 (6) | C16—C11—C17—N1 | −176.1 (5) |
N4—Cu2—O3—C32 | −177.0 (4) | Cu2—O4—C42—C41 | −1.5 (7) |
N3—Cu2—O3—C32 | 17.5 (4) | Cu2—O4—C42—C43 | 179.5 (3) |
O3—Cu2—O4—C42 | −92.8 (6) | C46—C41—C42—O4 | 178.6 (4) |
N4—Cu2—O4—C42 | 7.8 (4) | C47—C41—C42—O4 | −5.4 (8) |
N3—Cu2—O4—C42 | 173.0 (4) | C46—C41—C42—C43 | −2.4 (7) |
O2—Cu1—N1—C17 | 147.7 (4) | C47—C41—C42—C43 | 173.6 (5) |
O1—Cu1—N1—C17 | −6.0 (4) | O4—C42—C43—C44 | −179.7 (4) |
N2—Cu1—N1—C17 | −110.4 (5) | C41—C42—C43—C44 | 1.3 (7) |
O2—Cu1—N1—C1 | −30.2 (3) | C42—C43—C44—C45 | 0.8 (8) |
O1—Cu1—N1—C1 | 176.1 (3) | C43—C44—C45—C46 | −1.7 (8) |
N2—Cu1—N1—C1 | 71.6 (5) | C44—C45—C46—C41 | 0.5 (8) |
O2—Cu1—N2—C27 | −6.1 (4) | C42—C41—C46—C45 | 1.6 (8) |
O1—Cu1—N2—C27 | 147.8 (4) | C47—C41—C46—C45 | −174.6 (5) |
N1—Cu1—N2—C27 | −107.4 (5) | C66—N4—C47—C41 | −169.8 (5) |
O2—Cu1—N2—C61 | 176.9 (4) | Cu2—N4—C47—C41 | 7.4 (8) |
O1—Cu1—N2—C61 | −29.2 (4) | C46—C41—C47—N4 | 178.2 (5) |
N1—Cu1—N2—C61 | 75.6 (6) | C42—C41—C47—N4 | 2.0 (9) |
O4—Cu2—N3—C37 | 146.4 (4) | Cu2—O3—C32—C31 | −11.7 (7) |
O3—Cu2—N3—C37 | −14.7 (4) | Cu2—O3—C32—C33 | 169.6 (3) |
N4—Cu2—N3—C37 | −116.7 (7) | C36—C31—C32—O3 | 178.4 (4) |
O4—Cu2—N3—C6 | −30.6 (3) | C37—C31—C32—O3 | −2.9 (7) |
O3—Cu2—N3—C6 | 168.3 (3) | C36—C31—C32—C33 | −3.0 (7) |
N4—Cu2—N3—C6 | 66.3 (7) | C37—C31—C32—C33 | 175.7 (4) |
O4—Cu2—N4—C47 | −10.2 (4) | O3—C32—C33—C34 | −178.5 (4) |
O3—Cu2—N4—C47 | 151.2 (4) | C31—C32—C33—C34 | 2.7 (7) |
N3—Cu2—N4—C47 | −106.5 (7) | C32—C33—C34—C35 | −0.6 (7) |
O4—Cu2—N4—C66 | 166.8 (4) | C33—C34—C35—C36 | −1.3 (8) |
O3—Cu2—N4—C66 | −31.7 (4) | C34—C35—C36—C31 | 1.0 (8) |
N3—Cu2—N4—C66 | 70.6 (8) | C32—C31—C36—C35 | 1.2 (7) |
Cu1—O2—C22—C23 | 177.2 (4) | C37—C31—C36—C35 | −177.6 (4) |
Cu1—O2—C22—C21 | −3.4 (7) | C6—N3—C37—C31 | −176.3 (4) |
C26—C21—C22—O2 | 178.4 (5) | Cu2—N3—C37—C31 | 6.6 (7) |
C27—C21—C22—O2 | −2.2 (7) | C32—C31—C37—N3 | 5.2 (7) |
C26—C21—C22—C23 | −2.2 (7) | C36—C31—C37—N3 | −176.0 (5) |
C27—C21—C22—C23 | 177.2 (5) | C17—N1—C1—C2 | 119.2 (4) |
O2—C22—C23—C24 | −179.4 (5) | Cu1—N1—C1—C2 | −62.7 (5) |
C21—C22—C23—C24 | 1.2 (8) | N1—C1—C2—C3 | −65.8 (5) |
C22—C23—C24—C25 | 0.9 (9) | C1—C2—C3—C4 | −175.2 (4) |
C23—C24—C25—C26 | −1.9 (9) | C2—C3—C4—C5 | 166.7 (4) |
C24—C25—C26—C21 | 0.8 (8) | C3—C4—C5—C6 | −175.6 (4) |
C22—C21—C26—C25 | 1.2 (7) | C37—N3—C6—C5 | 120.2 (4) |
C27—C21—C26—C25 | −178.2 (5) | Cu2—N3—C6—C5 | −62.5 (4) |
C61—N2—C27—C21 | −179.9 (5) | C4—C5—C6—N3 | −70.5 (5) |
Cu1—N2—C27—C21 | 3.0 (7) | C27—N2—C61—C62 | 95.4 (8) |
C26—C21—C27—N2 | −178.4 (5) | Cu1—N2—C61—C62 | −87.4 (9) |
C22—C21—C27—N2 | 2.3 (8) | N2—C61—C62—C63 | 66.2 (11) |
Cu1—O1—C12—C13 | 167.7 (3) | C61—C62—C63—C64 | 178.7 (6) |
Cu1—O1—C12—C11 | −12.1 (6) | C62—C63—C64—C65 | −72.9 (9) |
C16—C11—C12—O1 | −178.0 (4) | C63—C64—C65—C66 | 166.4 (6) |
C17—C11—C12—O1 | 3.5 (7) | C47—N4—C66—C65 | 96.4 (6) |
C16—C11—C12—C13 | 2.1 (7) | Cu2—N4—C66—C65 | −80.8 (6) |
C17—C11—C12—C13 | −176.4 (4) | C64—C65—C66—N4 | 58.9 (8) |
O1—C12—C13—C14 | 179.4 (4) | C71—C72—C73—C74 | 161 (3) |
C11—C12—C13—C14 | −0.7 (7) | C72—C73—C74—C75 | −166 (2) |
C12—C13—C14—C15 | −0.8 (8) | C73—C74—C75—C76 | 161 (2) |
C13—C14—C15—C16 | 0.9 (8) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Cu2(C20H22N2O2)2] | [Cu2(C20H22N2O2)2] |
Mr | 771.81 | 771.81 |
Crystal system, space group | Tetragonal, P41 | Tetragonal, P43 |
Temperature (K) | 150 | 150 |
a, c (Å) | 13.2963 (2), 20.6366 (5) | 13.3288 (2), 20.5834 (7) |
V (Å3) | 3648.38 (12) | 3656.78 (15) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.21 | 1.21 |
Crystal size (mm) | 0.22 × 0.21 × 0.20 | 0.20 × 0.18 × 0.10 |
Data collection | ||
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan DENZO-SMN (Otwinowski & Minor, 1997) | Multi-scan DENZO-SMN (Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.776, 0.794 | 0.794, 0.889 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20156, 7755, 5429 | 20308, 7763, 4824 |
Rint | 0.072 | 0.103 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.108, 1.00 | 0.049, 0.098, 0.96 |
No. of reflections | 7755 | 7763 |
No. of parameters | 470 | 470 |
No. of restraints | 59 | 59 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.36 | 0.35, −0.47 |
Absolute structure | Flack (1983), 3489 Friedel pairs | Flack (1983), 3505 Friedel pairs |
Absolute structure parameter | 0.007 (14) | 0.000 (14) |
Computer programs: COLLECT (Nonius, 1997-2000), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976) and PLATON (Spek, 2002), SHELXL97 and PRPKAPPA (Ferguson, 1999).
Cu1—O2 | 1.890 (3) | Cu2—O4 | 1.895 (3) |
Cu1—O1 | 1.895 (3) | Cu2—O3 | 1.903 (3) |
Cu1—N2 | 1.959 (4) | Cu2—N4 | 1.965 (4) |
Cu1—N1 | 1.972 (3) | Cu2—N3 | 1.980 (4) |
Cu1—O2 | 1.887 (4) | Cu2—O4 | 1.896 (3) |
Cu1—O1 | 1.898 (4) | Cu2—O3 | 1.903 (3) |
Cu1—N2 | 1.961 (4) | Cu2—N4 | 1.954 (4) |
Cu1—N1 | 1.979 (4) | Cu2—N3 | 1.983 (4) |
Although copper(II) and nickel(II) complexes with Schiff base ligands containing bridging aliphatic chains containing two, three or four methylene groups have been the subject of several crystallographic investigations (Freiburg et al., 1980; Akhtar, 1981; Akhtar & Drew, 1982; Drew et al., 1985; Yao et al., 1997), less work has been done on homologous compounds containing longer bridging chains (Martin et al., 1978; Kitajima et al., 1986). The aliphatic chain length can have a pronounced influence on the coordination polyhedron of the metal ion, and also on intermolecular oligomerization and polymerization in the solid state and in solution.
Previous work (Duggal & Agarwala, 1988) carried out on the complex of copper(II) with N,N'-hexamethylenebis(salicylaldimine) concluded, on the basis of IR and diffuse-reflectance spectroscopy measurements, that the complex should be monomeric, with the CuII ion in a cis-square-planar environment. We concluded that it would be interesting to examine the folding of the rather long polymethylene chain in such a compound, so the title complex was prepared and crystallized, either by a diffusion reaction technique, to give (I), or by evaporation of a dioxane solution of the complex, to give (II). The results obtained by the present structure determinations are not in agreement with the structure proposed previously by Duggal & Agarwala (1988). The title complex was found to be dimeric in the solid state, with anions of N,N'-hexamethylenebis(salicylaldimine) functioning as bridging bis-bidentate ligands. \sch
One set of crystals of the title copper complex was grown by evaporation from a dioxane solution, and the compound obtained, (II), was found to crystallize in the space group P43. However, crystals obtained by a slow interdiffusion of methanolic basic N,N'-hexamethylenebis(salicylaldimine) solution and a copper(II) nitrate solution, (I), exhibited the space group P41. Structure determination from room-temperature data indicated that the molecular geometries were the same in both crystals, the only difference being in the direction of the polar axis.
Space-group determinations and data collection were performed on several crystals from each set at room temperature, and the Flack data (Flack, 1983) were always consistent with space group P41 for diffusion-grown and P43 for dioxane-grown crystals. However, the data collected at room temperature indicated the existence of disorder in one of the bridging aliphatic chains of the dimeric complex molecule; the final structure determinations reported here were undertaken using low-temperature data, which enabled the resolution of the disorder (see Experimental).
The molecular geometry in both (I) (Fig. 1) and (II) (Fig. 2) is identical. The CuII ions in the dimers are coordinated in the form of very flattened tetrahedra, with the N and O donor atoms in a trans arrangement around each CuII centre. There is similar significant disorder in one of the two hexamethylene chains in each compound; a view of the pair of disordered chains in (I) is shown in Fig. 3.
The distance between the two CuII centres in the dimer is 7.7019 (8) Å in (I) and 7.7186 (8) Å in (II). The degree of the distortion of the metal coordination tetrahedron can be expressed by the dihedral angle between the corresponding O—Cu—N planes; in (I), this is 35.0 (2)° for atom Cu1 and 23.3 (2)° for Cu2, and in (II) the angle is 34.5 (2)° for Cu1 and 23.6 (2) for Cu2. These values fall in the range of the previously reported angles in similar complexes (Bear et al., 1970; Elder & Hill, 1979). Details of the bond lengths at the Cu atoms are given in Tables 1 and 2. The molecular dimensions in both complexes are all in accordance with values previously reported for copper(II) salicylaldiminates (Bhadbhade & Srinivas, 1993; Kani et al., 1998).
The reasons for the observed dependence of the orientation of the polar axis on crystallization conditions are, as yet, unclear.