The title compound, [Cu(C24H46N6O2)]Cl2·8H2O, contains a centrosymmetric cation, with the anions and water molecules on general sites. The coordination geometry around the CuII ion is an axially elongated octahedron, with Cu-N distances of 2.0448 (17) and 2.0847 (17) Å, and a Cu-O1 distance of 2.3138 (16) Å.
Supporting information
CCDC reference: 173339
The ligand 2,13-bis(acetamido)-5,16-dimethyl-2,6,13,17-tetraazatricyclo-
[14,4,01.18,07.12]docosane was synthesized according to the method of
Maumela et al. (1995). A methanol solution (20 ml) of
CuCl2·6H2O (185 mg, 0.5 mmol) and the free ligand (225 mg, 0.5 mmol)
was heated under reflux for 1 h and then cooled to room temperature. The
solution was filtered and left at room temperature until deep-blue crystals
formed. The product was filtered and recrystallized from a hot
water–acetonitrile (1:1, 10 ml) mixture.
The eight H atoms of the water molecules were found from a difference Fourier
map, their positions were constrained using DFIX (0.90 0.03) and their
displacement parameters were refined as a common variable [0.079 (4) Å2].
The positions of all remaining H atoms were calculated geometrically and
constrained to ride on their attached atoms, with isotropic displacement
parameters fixed at 1.2 (C or N) or 1.5 (methyl C) times the equivalent
isotropic displacement parameters of their parent atoms. The highest peak and
deepest hole in the final difference density map were 1.09 Å from Cu and
0.76 Å from Cl, respectively.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Crystal data top
[Cu(C24H46N6O2)]Cl2·8H2O | F(000) = 782 |
Mr = 729.24 | Dx = 1.388 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.210 (4) Å | Cell parameters from 25 reflections |
b = 17.709 (3) Å | θ = 11.4–12.7° |
c = 9.2126 (16) Å | µ = 0.84 mm−1 |
β = 107.423 (19)° | T = 293 K |
V = 1745.0 (8) Å3 | Block, dark blue |
Z = 2 | 0.48 × 0.46 × 0.30 mm |
Data collection top
Enraf Nonius CAD-4 diffractometer | 2551 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.044 |
Graphite monochromator | θmax = 25.0°, θmin = 2.2° |
non–profiled ω/2θ scans | h = −13→12 |
Absorption correction: ψ scan North et al. (1968) | k = 0→21 |
Tmin = 0.662, Tmax = 0.778 | l = 0→10 |
3262 measured reflections | 3 standard reflections every 300 min |
3060 independent reflections | intensity decay: 3% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0511P)2 + 0.4858P] where P = (Fo2 + 2Fc2)/3 |
3060 reflections | (Δ/σ)max < 0.001 |
222 parameters | Δρmax = 0.46 e Å−3 |
8 restraints | Δρmin = −0.28 e Å−3 |
Crystal data top
[Cu(C24H46N6O2)]Cl2·8H2O | V = 1745.0 (8) Å3 |
Mr = 729.24 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.210 (4) Å | µ = 0.84 mm−1 |
b = 17.709 (3) Å | T = 293 K |
c = 9.2126 (16) Å | 0.48 × 0.46 × 0.30 mm |
β = 107.423 (19)° | |
Data collection top
Enraf Nonius CAD-4 diffractometer | 2551 reflections with I > 2σ(I) |
Absorption correction: ψ scan North et al. (1968) | Rint = 0.044 |
Tmin = 0.662, Tmax = 0.778 | 3 standard reflections every 300 min |
3262 measured reflections | intensity decay: 3% |
3060 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.035 | 8 restraints |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.46 e Å−3 |
3060 reflections | Δρmin = −0.28 e Å−3 |
222 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu | 0.5000 | 0.0000 | 0.0000 | 0.02560 (13) | |
O1 | 0.44703 (15) | 0.10022 (8) | −0.16824 (18) | 0.0373 (4) | |
N1 | 0.40756 (16) | 0.06110 (10) | 0.12108 (19) | 0.0289 (4) | |
H1 | 0.3766 | 0.1011 | 0.0593 | 0.035* | |
N2 | 0.66258 (16) | 0.04273 (9) | 0.15320 (19) | 0.0281 (4) | |
N3 | 0.2973 (2) | 0.13230 (12) | −0.3816 (3) | 0.0578 (6) | |
H3A | 0.3311 | 0.1754 | −0.3866 | 0.069* | |
H3B | 0.2293 | 0.1197 | −0.4498 | 0.069* | |
C4 | 0.5005 (2) | 0.09631 (12) | 0.2547 (2) | 0.0317 (5) | |
H4 | 0.5222 | 0.0594 | 0.3378 | 0.038* | |
C5 | 0.4492 (2) | 0.16715 (14) | 0.3101 (3) | 0.0461 (6) | |
H5A | 0.4190 | 0.2020 | 0.2258 | 0.055* | |
H5B | 0.3790 | 0.1533 | 0.3457 | 0.055* | |
C6 | 0.5479 (3) | 0.20625 (15) | 0.4380 (3) | 0.0538 (7) | |
H6A | 0.5130 | 0.2519 | 0.4672 | 0.065* | |
H6B | 0.5728 | 0.1732 | 0.5260 | 0.065* | |
C7 | 0.6611 (3) | 0.22610 (14) | 0.3888 (3) | 0.0513 (7) | |
H7A | 0.7239 | 0.2494 | 0.4730 | 0.062* | |
H7B | 0.6374 | 0.2622 | 0.3059 | 0.062* | |
C8 | 0.7155 (2) | 0.15571 (13) | 0.3374 (3) | 0.0452 (6) | |
H8A | 0.7471 | 0.1220 | 0.4235 | 0.054* | |
H8B | 0.7851 | 0.1701 | 0.3012 | 0.054* | |
C9 | 0.6174 (2) | 0.11408 (11) | 0.2105 (2) | 0.0305 (5) | |
H9 | 0.5921 | 0.1488 | 0.1239 | 0.037* | |
C10 | 0.7559 (2) | 0.06315 (13) | 0.0731 (3) | 0.0372 (5) | |
H10A | 0.8287 | 0.0847 | 0.1467 | 0.045* | |
H10B | 0.7199 | 0.1019 | −0.0015 | 0.045* | |
C11 | 0.2017 (2) | 0.00187 (14) | 0.0069 (3) | 0.0432 (6) | |
H11A | 0.1257 | −0.0134 | 0.0285 | 0.052* | |
H11B | 0.1807 | 0.0441 | −0.0632 | 0.052* | |
C12 | 0.2945 (2) | 0.02965 (14) | 0.1549 (3) | 0.0384 (5) | |
H12 | 0.2545 | 0.0713 | 0.1927 | 0.046* | |
C13 | 0.3276 (3) | −0.03044 (17) | 0.2778 (3) | 0.0521 (7) | |
H13A | 0.3753 | −0.0696 | 0.2491 | 0.078* | |
H13B | 0.2523 | −0.0515 | 0.2901 | 0.078* | |
H13C | 0.3762 | −0.0082 | 0.3720 | 0.078* | |
C14 | 0.2820 (2) | 0.01113 (11) | −0.2800 (3) | 0.0347 (5) | |
H14A | 0.1962 | 0.0211 | −0.2831 | 0.042* | |
H14B | 0.2802 | −0.0130 | −0.3751 | 0.042* | |
C15 | 0.3496 (2) | 0.08574 (12) | −0.2698 (2) | 0.0329 (5) | |
Cl | 0.05446 (10) | 0.20212 (5) | 0.14520 (10) | 0.0814 (3) | |
O11 | 0.2494 (2) | 0.20522 (14) | −0.0449 (3) | 0.0703 (6) | |
O12 | −0.0286 (2) | 0.43540 (14) | 0.1453 (3) | 0.0720 (6) | |
O13 | 0.0676 (2) | 0.41444 (13) | −0.1009 (3) | 0.0702 (6) | |
O14 | −0.0969 (3) | 0.31582 (16) | 0.2904 (3) | 0.0853 (8) | |
H111 | 0.192 (3) | 0.2032 (19) | 0.000 (4) | 0.079 (4)* | |
H112 | 0.211 (3) | 0.2286 (18) | −0.129 (3) | 0.079 (4)* | |
H121 | −0.002 (3) | 0.4158 (19) | 0.080 (3) | 0.079 (4)* | |
H122 | −0.048 (3) | 0.3978 (16) | 0.194 (4) | 0.079 (4)* | |
H131 | 0.056 (3) | 0.3884 (18) | −0.177 (3) | 0.079 (4)* | |
H132 | 0.057 (3) | 0.4589 (15) | −0.138 (4) | 0.079 (4)* | |
H141 | −0.061 (3) | 0.307 (2) | 0.386 (3) | 0.079 (4)* | |
H142 | −0.058 (3) | 0.2826 (17) | 0.257 (4) | 0.079 (4)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu | 0.02301 (19) | 0.0240 (2) | 0.0269 (2) | −0.00059 (15) | 0.00319 (14) | −0.00252 (15) |
O1 | 0.0395 (9) | 0.0322 (8) | 0.0371 (9) | −0.0062 (7) | 0.0066 (7) | 0.0018 (7) |
N1 | 0.0288 (9) | 0.0280 (9) | 0.0280 (9) | 0.0021 (7) | 0.0059 (7) | 0.0007 (7) |
N2 | 0.0272 (9) | 0.0221 (9) | 0.0308 (9) | −0.0014 (7) | 0.0021 (7) | 0.0015 (7) |
N3 | 0.0670 (15) | 0.0396 (12) | 0.0507 (13) | −0.0125 (11) | −0.0067 (11) | 0.0183 (11) |
C4 | 0.0377 (12) | 0.0291 (11) | 0.0246 (10) | 0.0004 (9) | 0.0040 (9) | −0.0003 (9) |
C5 | 0.0521 (15) | 0.0420 (14) | 0.0425 (14) | 0.0041 (12) | 0.0116 (12) | −0.0123 (11) |
C6 | 0.0739 (19) | 0.0420 (15) | 0.0403 (14) | 0.0033 (14) | 0.0091 (13) | −0.0160 (12) |
C7 | 0.0646 (18) | 0.0333 (13) | 0.0446 (14) | −0.0053 (12) | −0.0008 (13) | −0.0117 (11) |
C8 | 0.0468 (14) | 0.0335 (13) | 0.0462 (14) | −0.0074 (11) | 0.0002 (11) | −0.0084 (11) |
C9 | 0.0370 (12) | 0.0211 (10) | 0.0282 (11) | 0.0000 (9) | 0.0021 (9) | 0.0006 (9) |
C10 | 0.0310 (12) | 0.0368 (13) | 0.0410 (13) | −0.0078 (10) | 0.0067 (10) | −0.0021 (10) |
C11 | 0.0259 (11) | 0.0487 (14) | 0.0535 (15) | −0.0029 (11) | 0.0096 (10) | −0.0068 (12) |
C12 | 0.0313 (12) | 0.0435 (13) | 0.0433 (14) | 0.0008 (10) | 0.0155 (10) | −0.0055 (11) |
C13 | 0.0508 (16) | 0.0626 (16) | 0.0496 (16) | −0.0119 (14) | 0.0251 (13) | 0.0042 (14) |
C14 | 0.0314 (11) | 0.0279 (12) | 0.0368 (12) | 0.0031 (9) | −0.0018 (9) | 0.0066 (9) |
C15 | 0.0376 (12) | 0.0300 (11) | 0.0313 (12) | 0.0021 (10) | 0.0106 (10) | 0.0010 (10) |
Cl | 0.1048 (7) | 0.0825 (6) | 0.0655 (5) | 0.0051 (5) | 0.0388 (5) | 0.0079 (4) |
O11 | 0.0616 (14) | 0.0821 (16) | 0.0682 (15) | 0.0137 (12) | 0.0211 (11) | 0.0152 (12) |
O12 | 0.0768 (16) | 0.0663 (15) | 0.0810 (17) | −0.0086 (12) | 0.0361 (13) | −0.0051 (12) |
O13 | 0.0833 (16) | 0.0666 (15) | 0.0527 (13) | 0.0038 (13) | 0.0081 (12) | −0.0057 (11) |
O14 | 0.0785 (17) | 0.0862 (19) | 0.0936 (19) | 0.0144 (14) | 0.0294 (15) | 0.0209 (16) |
Geometric parameters (Å, º) top
Cu—N1i | 2.0448 (17) | C8—C9 | 1.533 (3) |
Cu—N1 | 2.0448 (17) | C8—H8A | 0.9700 |
Cu—N2 | 2.0847 (17) | C8—H8B | 0.9700 |
Cu—N2i | 2.0847 (17) | C9—H9 | 0.9800 |
Cu—O1i | 2.3138 (16) | C10—C11i | 1.518 (3) |
Cu—O1 | 2.3138 (16) | C10—H10A | 0.9700 |
O1—C15 | 1.234 (3) | C10—H10B | 0.9700 |
N1—C4 | 1.490 (3) | C11—C10i | 1.518 (3) |
N1—C12 | 1.500 (3) | C11—C12 | 1.527 (3) |
N1—H1 | 0.9100 | C11—H11A | 0.9700 |
N2—C14i | 1.492 (3) | C11—H11B | 0.9700 |
N2—C10 | 1.494 (3) | C12—C13 | 1.517 (4) |
N2—C9 | 1.514 (3) | C12—H12 | 0.9800 |
N3—C15 | 1.312 (3) | C13—H13A | 0.9600 |
N3—H3A | 0.8600 | C13—H13B | 0.9600 |
N3—H3B | 0.8600 | C13—H13C | 0.9600 |
C4—C9 | 1.518 (3) | C14—N2i | 1.492 (3) |
C4—C5 | 1.530 (3) | C14—C15 | 1.512 (3) |
C4—H4 | 0.9800 | C14—H14A | 0.9700 |
C5—C6 | 1.521 (4) | C14—H14B | 0.9700 |
C5—H5A | 0.9700 | O11—H111 | 0.86 (2) |
C5—H5B | 0.9700 | O11—H112 | 0.87 (2) |
C6—C7 | 1.510 (4) | O12—H121 | 0.82 (2) |
C6—H6A | 0.9700 | O12—H122 | 0.86 (2) |
C6—H6B | 0.9700 | O13—H131 | 0.82 (2) |
C7—C8 | 1.525 (4) | O13—H132 | 0.85 (2) |
C7—H7A | 0.9700 | O14—H141 | 0.86 (2) |
C7—H7B | 0.9700 | O14—H142 | 0.84 (2) |
| | | |
N1i—Cu—N1 | 180.00 (11) | C6—C7—H7B | 109.5 |
N1i—Cu—N2 | 94.49 (7) | C8—C7—H7B | 109.5 |
N1—Cu—N2 | 85.51 (7) | H7A—C7—H7B | 108.1 |
N1i—Cu—N2i | 85.51 (7) | C7—C8—C9 | 111.6 (2) |
N1—Cu—N2i | 94.49 (7) | C7—C8—H8A | 109.3 |
N2—Cu—N2i | 180.00 (7) | C9—C8—H8A | 109.3 |
N1i—Cu—O1i | 83.64 (6) | C7—C8—H8B | 109.3 |
N1—Cu—O1i | 96.36 (6) | C9—C8—H8B | 109.3 |
N2—Cu—O1i | 80.09 (6) | H8A—C8—H8B | 108.0 |
N2i—Cu—O1i | 99.91 (6) | N2—C9—C4 | 109.06 (16) |
N1i—Cu—O1 | 96.36 (6) | N2—C9—C8 | 115.39 (18) |
N1—Cu—O1 | 83.64 (6) | C4—C9—C8 | 112.04 (19) |
N2—Cu—O1 | 99.91 (6) | N2—C9—H9 | 106.6 |
N2i—Cu—O1 | 80.09 (6) | C4—C9—H9 | 106.6 |
O1i—Cu—O1 | 180.00 (8) | C8—C9—H9 | 106.6 |
C15—O1—Cu | 109.87 (13) | N2—C10—C11i | 115.05 (18) |
C4—N1—C12 | 114.15 (17) | N2—C10—H10A | 108.5 |
C4—N1—Cu | 109.20 (13) | C11i—C10—H10A | 108.5 |
C12—N1—Cu | 120.96 (14) | N2—C10—H10B | 108.5 |
C4—N1—H1 | 103.4 | C11i—C10—H10B | 108.5 |
C12—N1—H1 | 103.4 | H10A—C10—H10B | 107.5 |
Cu—N1—H1 | 103.4 | C10i—C11—C12 | 116.7 (2) |
C14i—N2—C10 | 110.66 (17) | C10i—C11—H11A | 108.1 |
C14i—N2—C9 | 111.41 (17) | C12—C11—H11A | 108.1 |
C10—N2—C9 | 109.08 (16) | C10i—C11—H11B | 108.1 |
C14i—N2—Cu | 111.87 (12) | C12—C11—H11B | 108.1 |
C10—N2—Cu | 110.66 (13) | H11A—C11—H11B | 107.3 |
C9—N2—Cu | 102.89 (12) | N1—C12—C13 | 112.46 (19) |
C15—N3—H3A | 120.0 | N1—C12—C11 | 109.03 (18) |
C15—N3—H3B | 120.0 | C13—C12—C11 | 112.9 (2) |
H3A—N3—H3B | 120.0 | N1—C12—H12 | 107.4 |
N1—C4—C9 | 108.15 (17) | C13—C12—H12 | 107.4 |
N1—C4—C5 | 112.29 (18) | C11—C12—H12 | 107.4 |
C9—C4—C5 | 111.15 (19) | C12—C13—H13A | 109.5 |
N1—C4—H4 | 108.4 | C12—C13—H13B | 109.5 |
C9—C4—H4 | 108.4 | H13A—C13—H13B | 109.5 |
C5—C4—H4 | 108.4 | C12—C13—H13C | 109.5 |
C6—C5—C4 | 111.9 (2) | H13A—C13—H13C | 109.5 |
C6—C5—H5A | 109.2 | H13B—C13—H13C | 109.5 |
C4—C5—H5A | 109.2 | N2i—C14—C15 | 115.29 (17) |
C6—C5—H5B | 109.2 | N2i—C14—H14A | 108.5 |
C4—C5—H5B | 109.2 | C15—C14—H14A | 108.5 |
H5A—C5—H5B | 107.9 | N2i—C14—H14B | 108.5 |
C7—C6—C5 | 110.8 (2) | C15—C14—H14B | 108.5 |
C7—C6—H6A | 109.5 | H14A—C14—H14B | 107.5 |
C5—C6—H6A | 109.5 | O1—C15—N3 | 123.4 (2) |
C7—C6—H6B | 109.5 | O1—C15—C14 | 122.81 (19) |
C5—C6—H6B | 109.5 | N3—C15—C14 | 113.8 (2) |
H6A—C6—H6B | 108.1 | H111—O11—H112 | 102 (3) |
C6—C7—C8 | 110.7 (2) | H121—O12—H122 | 105 (3) |
C6—C7—H7A | 109.5 | H131—O13—H132 | 102 (3) |
C8—C7—H7A | 109.5 | H141—O14—H142 | 96 (4) |
| | | |
N1i—Cu—O1—C15 | 84.90 (15) | C9—C4—C5—C6 | −54.0 (3) |
N1—Cu—O1—C15 | −95.10 (15) | C4—C5—C6—C7 | 56.8 (3) |
N2—Cu—O1—C15 | −179.39 (15) | C5—C6—C7—C8 | −57.3 (3) |
N2i—Cu—O1—C15 | 0.61 (15) | C6—C7—C8—C9 | 55.9 (3) |
N2—Cu—N1—C4 | −4.59 (13) | C14i—N2—C9—C4 | −72.0 (2) |
N2i—Cu—N1—C4 | 175.41 (13) | C10—N2—C9—C4 | 165.50 (17) |
O1i—Cu—N1—C4 | 74.90 (13) | Cu—N2—C9—C4 | 47.97 (17) |
O1—Cu—N1—C4 | −105.10 (13) | C14i—N2—C9—C8 | 55.1 (2) |
N2—Cu—N1—C12 | −140.16 (16) | C10—N2—C9—C8 | −67.4 (2) |
N2i—Cu—N1—C12 | 39.84 (16) | Cu—N2—C9—C8 | 175.08 (16) |
O1i—Cu—N1—C12 | −60.67 (16) | N1—C4—C9—N2 | −55.0 (2) |
O1—Cu—N1—C12 | 119.33 (16) | C5—C4—C9—N2 | −178.72 (17) |
N1i—Cu—N2—C14i | −83.76 (15) | N1—C4—C9—C8 | 175.99 (17) |
N1—Cu—N2—C14i | 96.24 (15) | C5—C4—C9—C8 | 52.3 (2) |
O1i—Cu—N2—C14i | −1.03 (14) | C7—C8—C9—N2 | −179.30 (19) |
O1—Cu—N2—C14i | 178.97 (14) | C7—C8—C9—C4 | −53.7 (3) |
N1i—Cu—N2—C10 | 40.13 (14) | C14i—N2—C10—C11i | 64.0 (2) |
N1—Cu—N2—C10 | −139.87 (14) | C9—N2—C10—C11i | −173.12 (18) |
O1i—Cu—N2—C10 | 122.86 (14) | Cu—N2—C10—C11i | −60.6 (2) |
O1—Cu—N2—C10 | −57.14 (14) | C4—N1—C12—C13 | −59.0 (3) |
N1i—Cu—N2—C9 | 156.54 (12) | Cu—N1—C12—C13 | 74.5 (2) |
N1—Cu—N2—C9 | −23.46 (12) | C4—N1—C12—C11 | 174.90 (18) |
O1i—Cu—N2—C9 | −120.73 (13) | Cu—N1—C12—C11 | −51.5 (2) |
O1—Cu—N2—C9 | 59.27 (13) | C10i—C11—C12—N1 | 63.9 (3) |
C12—N1—C4—C9 | 171.14 (17) | C10i—C11—C12—C13 | −61.9 (3) |
Cu—N1—C4—C9 | 32.28 (19) | Cu—O1—C15—N3 | −179.8 (2) |
C12—N1—C4—C5 | −65.8 (2) | Cu—O1—C15—C14 | −2.3 (3) |
Cu—N1—C4—C5 | 155.29 (16) | N2i—C14—C15—O1 | 3.3 (3) |
N1—C4—C5—C6 | −175.3 (2) | N2i—C14—C15—N3 | −178.9 (2) |
Symmetry code: (i) −x+1, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O11 | 0.91 | 2.35 | 3.220 (3) | 160 |
N3—H3A···O11ii | 0.86 | 2.58 | 3.217 (3) | 132 |
N3—H3B···O13ii | 0.86 | 2.02 | 2.878 (3) | 177 |
O11—H111···Cl | 0.86 (2) | 2.32 (2) | 3.184 (3) | 174 (3) |
O11—H112···Clii | 0.87 (2) | 2.59 (3) | 3.447 (3) | 167 (3) |
O12—H121···O13 | 0.82 (2) | 2.04 (3) | 2.812 (4) | 156 (4) |
O12—H122···O14 | 0.86 (2) | 1.87 (2) | 2.734 (4) | 177 (4) |
O13—H131···Clii | 0.82 (2) | 2.29 (2) | 3.090 (2) | 167 (3) |
O13—H132···O12iii | 0.85 (2) | 1.90 (3) | 2.706 (4) | 158 (3) |
O14—H141···Cliv | 0.86 (2) | 2.36 (2) | 3.216 (3) | 172 (3) |
O14—H142···Cl | 0.84 (2) | 2.34 (2) | 3.175 (3) | 173 (3) |
Symmetry codes: (ii) x, −y+1/2, z−1/2; (iii) −x, −y+1, −z; (iv) x, −y+1/2, z+1/2. |
Experimental details
Crystal data |
Chemical formula | [Cu(C24H46N6O2)]Cl2·8H2O |
Mr | 729.24 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.210 (4), 17.709 (3), 9.2126 (16) |
β (°) | 107.423 (19) |
V (Å3) | 1745.0 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.84 |
Crystal size (mm) | 0.48 × 0.46 × 0.30 |
|
Data collection |
Diffractometer | Enraf Nonius CAD-4 diffractometer |
Absorption correction | ψ scan North et al. (1968) |
Tmin, Tmax | 0.662, 0.778 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3262, 3060, 2551 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.092, 1.08 |
No. of reflections | 3060 |
No. of parameters | 222 |
No. of restraints | 8 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.46, −0.28 |
Selected geometric parameters (Å, º) topCu—N1i | 2.0448 (17) | Cu—O1i | 2.3138 (16) |
Cu—N1 | 2.0448 (17) | Cu—O1 | 2.3138 (16) |
Cu—N2 | 2.0847 (17) | O1—C15 | 1.234 (3) |
Cu—N2i | 2.0847 (17) | N3—C15 | 1.312 (3) |
| | | |
N1—Cu—O1 | 83.64 (6) | N2—Cu—O1 | 99.91 (6) |
Symmetry code: (i) −x+1, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O11 | 0.91 | 2.35 | 3.220 (3) | 159.5 |
N3—H3A···O11ii | 0.86 | 2.58 | 3.217 (3) | 132.2 |
N3—H3B···O13ii | 0.86 | 2.02 | 2.878 (3) | 176.5 |
O11—H111···Cl | 0.86 (2) | 2.32 (2) | 3.184 (3) | 174 (3) |
O11—H112···Clii | 0.87 (2) | 2.59 (3) | 3.447 (3) | 167 (3) |
O12—H121···O13 | 0.82 (2) | 2.04 (3) | 2.812 (4) | 156 (4) |
O12—H122···O14 | 0.86 (2) | 1.87 (2) | 2.734 (4) | 177 (4) |
O13—H131···Clii | 0.82 (2) | 2.29 (2) | 3.090 (2) | 167 (3) |
O13—H132···O12iii | 0.85 (2) | 1.90 (3) | 2.706 (4) | 158 (3) |
O14—H141···Cliv | 0.86 (2) | 2.36 (2) | 3.216 (3) | 172 (3) |
O14—H142···Cl | 0.84 (2) | 2.34 (2) | 3.175 (3) | 173 (3) |
Symmetry codes: (ii) x, −y+1/2, z−1/2; (iii) −x, −y+1, −z; (iv) x, −y+1/2, z+1/2. |
The transition metal(II) complexes of partially N-functionalized 14-membered tetraaza macrocycles have been studied much less extensively than those of the fully N-functionalized analogs. This may be due to the fact that the synthesis of partially N-substituted macrocycles is complicated and requires several steps (Pallavicini et al., 1987). The crystal structure of the title compound, [2,13-bis(acetamido)-5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.07,12]- docosane]copper(II) dichloride octahydrate, (I), exhibits a tetragonally elongated octahedral geometry with bonds from the CuII atom to the secondary and tertiary amines of the macrocycle and to two O atoms of the pendant acetamide groups.
In the complex [Cu(C24H46N6O2)]2+ cation, the two acetamide groups are attached to the less sterically hindered N atoms of the macrocyclic ligand. The Cu—N2(tertiary amine) distance of 2.0847 (17) Å is slightly longer than the Cu—N1(secondary amine) distance [2.0438 (16) Å]. The axial Cu—O1 distance of 2.3138 (16) Å is considerably longer than the equatorial Cu—N distances. This long axial Cu—O distance may be due to the well established Jahn–Teller effect. The equatorial Cu—N and axial Cu—O bond lengths are typical of tetraaza macrocyclic copper(II) complexes (Choi et al., 1999). The axial N2—Cu—O1 bond angle [99.91 (6)°] on the five-membered chelate ring is expected for the bite angle of this type of macrocyclic ligand. The other angle [N1—Cu—O1 83.64 (6)°] may be due to steric hindrance involving the C13 methyl group. The O1═C15 bond length [1.234 (3) Å] clearly shows double-bond character. The two pendant acetamide groups in the complex are trans with respect to one another, and the configuration of the ligand is trans-III in the solid state. Interestingly, the acetamide N3 and secondary amine N1 atoms of the macrocycle form hydrogen bonds with the water molecules. The hydrogen bonds among N1, N3, four water molecules and a chloride ion form a three-dimensional molecular network and are presumably responsible for the stability of this crystal (Tbale 2).