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organic compounds
3,7,11,19,23,27-Hexaazatricyclo[27.3.1.113,17]tetratriaconta-1(32),13,15,17(34),29(33),30-hexaene hexachloride tetrahydrate
aDepartment of Chemistry, Northeast Normal University, Changchun 130024, People's Republic of China, and bDepartment of Chemistry and Pharmaceutical Engineering, Suihua University, Suihua 152061, People's Republic of China
*Correspondence e-mail: majf247nenu@yahoo.com.cn
The title compound, C28H52N66+·6Cl−·4H2O, is a dinucleating 28-membered centrosymmetric hexaazamacrocyclic complex. The macrocyclic ligand adopts a chair-like conformation, with the crystallographic inversion center located in the macrocyclic cavity. The six chloride ions and four water molecules are situated symmetrically outside the macrocyclic cavity. The is stabilized by N—H⋯Cl, N—H⋯O and O—H⋯Cl hydrogen bonds.
Related literature
For studies on hexaazamacrocyclic complexes, see: Llobet et al. (1994). For related literature, see: Anda et al. (2000
); Costas et al. (2004
); Lu et al. (1995
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: PROCESS-AUTO (Rigaku, 1998); cell PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997
); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997
); molecular graphics: SHELXTL-Plus (Sheldrick, 1990
); software used to prepare material for publication: SHELXL97.
Supporting information
https://doi.org/10.1107/S1600536807063064/ci2525sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807063064/ci2525Isup2.hkl
A solution of 3,3'-iminobis(propylamine) (1.31 g, 10 mmol) in CH3OH (400 ml) was added dropwise from a dropping funnel to a stirred solution of 97% m-phthalaldehyde (1.34 g, 10 mmol) in CH3OH (400 ml) in a round-bottomed three-neck flask over 12 h at room temperature. Then the volume of the mixture was concentrated to 200 ml. NaBH4 (2 g) was added to the solution and the suspension was magnetically stirred for about 5 h at room temperature. The solvent was removed under reduced pressure, and the product was extracted with CH2Cl2 from an aqueous solution (CH2Cl2/H2O, 120 ml/50 ml). Evaporation of CH2Cl2 under reduced pressure yielded a colourless oil which was then dissolved in 50 ml of 8% HCl. The volume was reduced under low pressure until at approximately 5 ml, a white crystalline solid precipitated.
N-bound H atoms were located in a difference map and refined freely; N—H distances involving atoms N1 and N3 were restrained to 0.85 (1) Å. H atoms bonded to water molecules were located in a difference Fourier map and refined isotropically, with distance restraints of O—H = 0.85 (1) Å and H···H = 1.30 (1) Å, and with Uiso(H) = 1.5 Ueq(O). C-bound H atoms were positioned geometrically (C—H = 0.93 Å) and refined as riding, with Uiso(H) = 1.2Ueq(carrier).
It has been shown that macrocyclic polyamines have numerous advantages as enzyme models. They can participate in molecular recongnition phenomena with different kinds of substrates, such as organic, inorganic, and biologically important anions (Lu et al., 1995; Anda et al., 2000). In addition, hexaaza macrocycles can form dinuclear metal complexes which in turn are capable of coordinating anions (Costas et al., 2004). In this paper, the synthesis and the
of a hexaazamacrocyclic complex, L.6HCl.4H2O [L is 3,7,11,19, 23,27-hexaazztricyclo[27.3.1.113,17]tetratriaconta-1(32),13,15,17 (34),29 (33),30-hexaene] is presented.The structure of the title compound is shown in Fig.1. It consists of a centrosymmetric hexaprotonated macrocycle, six chloride counterions, and four water molecules of crystallization. In the macrocycle, each of the aliphatic chains adopts a planar trans configuration, and each of the benzene rings is tilted from the mean plane of chains by 108.9 (1)°. All six N atoms are protonated with hydrogen atoms directed outside the ring. None of the chloride counterions are situated inside the macrocyclic cavity. The macrocycle adopts a chair conformation, similar to that observed in related compounds (Llobet et al., 1994). The
is stabilized by N—H···Cl, N—H···O and O—H···Cl hydrogen bonds (Table 1).For studies on hexaazamacrocyclic complexes, see: Llobet et al. (1994). For related literature, see: Anda et al. (2000); Costas et al. (2004); Lu et al. (1995).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell
PROCESS-AUTO (Rigaku, 1998; data reduction: PROCESS-AUTO (Rigaku, 1998; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997). ![]() | Fig. 1. The structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Symmetry code: (i) 1 - x, -y, 1 - z. |
C28H52N66+·6Cl−·4H2O | F(000) = 808 |
Mr = 757.52 | Dx = 1.249 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ybc | Cell parameters from 4594 reflections |
a = 17.012 (7) Å | θ = 3.0–27.5° |
b = 7.469 (2) Å | µ = 0.46 mm−1 |
c = 17.329 (7) Å | T = 293 K |
β = 113.841 (13)° | Block, colourless |
V = 2014.0 (13) Å3 | 0.19 × 0.18 × 0.15 mm |
Z = 2 |
Rigaku R-AXIS RAPID diffractometer | 4594 independent reflections |
Radiation source: fine-focus sealed tube | 2416 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.102 |
Detector resolution: 10.0 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ω scans | h = −22→22 |
Absorption correction: multi-scan (Higashi, 1995) | k = −9→8 |
Tmin = 0.895, Tmax = 0.932 | l = −22→22 |
18546 measured 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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0489P)2 + 0.1273P] where P = (Fo2 + 2Fc2)/3 |
4594 reflections | (Δ/σ)max = 0.001 |
235 parameters | Δρmax = 0.24 e Å−3 |
8 restraints | Δρmin = −0.26 e Å−3 |
C28H52N66+·6Cl−·4H2O | V = 2014.0 (13) Å3 |
Mr = 757.52 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 17.012 (7) Å | µ = 0.46 mm−1 |
b = 7.469 (2) Å | T = 293 K |
c = 17.329 (7) Å | 0.19 × 0.18 × 0.15 mm |
β = 113.841 (13)° |
Rigaku R-AXIS RAPID diffractometer | 4594 independent reflections |
Absorption correction: multi-scan (Higashi, 1995) | 2416 reflections with I > 2σ(I) |
Tmin = 0.895, Tmax = 0.932 | Rint = 0.102 |
18546 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 8 restraints |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.24 e Å−3 |
4594 reflections | Δρmin = −0.26 e Å−3 |
235 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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.82877 (18) | 0.1791 (4) | 0.39938 (18) | 0.0355 (7) | |
C2 | 0.84179 (18) | 0.0147 (4) | 0.44031 (19) | 0.0368 (7) | |
H2 | 0.8105 | −0.0843 | 0.4115 | 0.044* | |
C3 | 0.90031 (19) | −0.0047 (4) | 0.52305 (19) | 0.0350 (7) | |
C4 | 0.94848 (19) | 0.1433 (4) | 0.5644 (2) | 0.0400 (8) | |
H4 | 0.9890 | 0.1320 | 0.6196 | 0.048* | |
C5 | 0.9369 (2) | 0.3061 (4) | 0.5244 (2) | 0.0450 (8) | |
H5 | 0.9693 | 0.4044 | 0.5528 | 0.054* | |
C6 | 0.8769 (2) | 0.3245 (4) | 0.4419 (2) | 0.0420 (8) | |
H6 | 0.8692 | 0.4351 | 0.4151 | 0.050* | |
C7 | 0.76289 (18) | 0.1935 (5) | 0.30992 (19) | 0.0431 (8) | |
H7A | 0.7856 | 0.2686 | 0.2781 | 0.052* | |
H7B | 0.7527 | 0.0754 | 0.2845 | 0.052* | |
C8 | 0.63910 (18) | 0.1810 (4) | 0.35545 (18) | 0.0367 (7) | |
H8A | 0.6756 | 0.1954 | 0.4149 | 0.044* | |
H8B | 0.6329 | 0.0539 | 0.3428 | 0.044* | |
C9 | 0.55173 (19) | 0.2631 (4) | 0.33619 (19) | 0.0395 (8) | |
H9A | 0.5580 | 0.3911 | 0.3465 | 0.047* | |
H9B | 0.5149 | 0.2447 | 0.2771 | 0.047* | |
C10 | 0.51067 (18) | 0.1803 (4) | 0.39031 (19) | 0.0385 (7) | |
H10A | 0.5066 | 0.0517 | 0.3820 | 0.046* | |
H10B | 0.5460 | 0.2037 | 0.4493 | 0.046* | |
C11 | 0.37784 (18) | 0.1881 (4) | 0.41939 (19) | 0.0411 (8) | |
H11A | 0.4035 | 0.2392 | 0.4756 | 0.049* | |
H11B | 0.3838 | 0.0590 | 0.4245 | 0.049* | |
C12 | 0.28364 (19) | 0.2373 (4) | 0.3786 (2) | 0.0435 (8) | |
H12A | 0.2782 | 0.3645 | 0.3663 | 0.052* | |
H12B | 0.2566 | 0.1734 | 0.3256 | 0.052* | |
C13 | 0.23772 (18) | 0.1922 (4) | 0.4348 (2) | 0.0412 (8) | |
H13A | 0.2536 | 0.0728 | 0.4577 | 0.049* | |
H13B | 0.2544 | 0.2762 | 0.4814 | 0.049* | |
C14 | 0.08870 (19) | 0.1827 (4) | 0.4337 (2) | 0.0434 (8) | |
H14A | 0.0289 | 0.1977 | 0.3957 | 0.052* | |
H14B | 0.1033 | 0.2769 | 0.4757 | 0.052* | |
N1 | 0.67900 (17) | 0.2703 (4) | 0.30374 (17) | 0.0345 (6) | |
H1A | 0.683 (2) | 0.3817 (17) | 0.3174 (19) | 0.049 (10)* | |
H1B | 0.6425 (19) | 0.256 (4) | 0.2505 (19) | 0.037 (8)* | |
N2 | 0.42311 (16) | 0.2566 (4) | 0.36763 (17) | 0.0341 (6) | |
H2A | 0.4253 (18) | 0.375 (4) | 0.3706 (18) | 0.038 (9)* | |
H2B | 0.391 (2) | 0.238 (4) | 0.309 (2) | 0.052 (10)* | |
N3 | 0.14354 (16) | 0.2017 (4) | 0.38479 (18) | 0.0385 (6) | |
H3A | 0.129 (2) | 0.303 (2) | 0.3601 (18) | 0.053 (11)* | |
H3B | 0.130 (2) | 0.120 (3) | 0.3470 (14) | 0.046 (10)* | |
O1W | 0.2694 (2) | 0.7467 (6) | 0.4322 (2) | 0.1099 (12) | |
H1O | 0.226 (2) | 0.690 (7) | 0.400 (3) | 0.165* | |
H2O | 0.307 (2) | 0.711 (8) | 0.416 (4) | 0.165* | |
O2W | 0.09052 (17) | −0.0279 (3) | 0.24667 (18) | 0.0595 (7) | |
H3O | 0.090 (3) | −0.1386 (18) | 0.256 (3) | 0.089* | |
H4O | 0.0390 (11) | 0.005 (5) | 0.232 (3) | 0.089* | |
Cl1 | 0.43151 (6) | 0.67844 (11) | 0.38468 (5) | 0.0500 (2) | |
Cl2 | 0.68078 (6) | 0.68054 (11) | 0.32358 (5) | 0.0545 (3) | |
Cl3 | 0.10025 (6) | 0.55940 (11) | 0.28508 (6) | 0.0543 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0243 (15) | 0.0496 (19) | 0.0374 (16) | 0.0022 (15) | 0.0175 (13) | 0.0018 (15) |
C2 | 0.0258 (15) | 0.0446 (18) | 0.0432 (17) | −0.0034 (13) | 0.0172 (14) | −0.0063 (15) |
C3 | 0.0252 (15) | 0.0397 (17) | 0.0454 (18) | 0.0035 (13) | 0.0197 (14) | 0.0033 (15) |
C4 | 0.0295 (16) | 0.054 (2) | 0.0393 (17) | −0.0024 (15) | 0.0172 (14) | 0.0001 (16) |
C5 | 0.0406 (19) | 0.0457 (19) | 0.0478 (19) | −0.0110 (15) | 0.0169 (16) | −0.0032 (16) |
C6 | 0.0391 (18) | 0.0430 (18) | 0.0475 (19) | −0.0013 (15) | 0.0213 (15) | 0.0061 (16) |
C7 | 0.0331 (17) | 0.064 (2) | 0.0373 (17) | 0.0027 (16) | 0.0192 (14) | −0.0028 (16) |
C8 | 0.0329 (16) | 0.0444 (17) | 0.0362 (16) | 0.0022 (14) | 0.0174 (14) | 0.0044 (14) |
C9 | 0.0350 (17) | 0.0436 (17) | 0.0449 (18) | 0.0044 (14) | 0.0210 (15) | 0.0038 (15) |
C10 | 0.0293 (16) | 0.0456 (18) | 0.0400 (17) | 0.0042 (14) | 0.0133 (14) | 0.0056 (15) |
C11 | 0.0302 (16) | 0.0512 (19) | 0.0434 (18) | −0.0002 (15) | 0.0165 (14) | 0.0063 (16) |
C12 | 0.0327 (17) | 0.053 (2) | 0.0496 (19) | 0.0028 (15) | 0.0213 (15) | 0.0107 (16) |
C13 | 0.0279 (16) | 0.054 (2) | 0.0423 (17) | −0.0007 (15) | 0.0151 (14) | 0.0043 (16) |
C14 | 0.0343 (17) | 0.0475 (19) | 0.057 (2) | 0.0081 (15) | 0.0279 (16) | 0.0075 (16) |
N1 | 0.0321 (14) | 0.0430 (17) | 0.0290 (14) | −0.0003 (13) | 0.0130 (12) | −0.0010 (13) |
N2 | 0.0267 (14) | 0.0355 (15) | 0.0413 (16) | −0.0016 (12) | 0.0152 (12) | −0.0004 (13) |
N3 | 0.0328 (14) | 0.0379 (16) | 0.0460 (16) | 0.0016 (13) | 0.0170 (13) | 0.0068 (15) |
O1W | 0.077 (2) | 0.147 (3) | 0.101 (3) | −0.015 (2) | 0.031 (2) | −0.065 (2) |
O2W | 0.0507 (16) | 0.0587 (15) | 0.0750 (17) | −0.0019 (14) | 0.0317 (15) | −0.0071 (15) |
Cl1 | 0.0533 (5) | 0.0491 (5) | 0.0392 (4) | −0.0022 (4) | 0.0098 (4) | −0.0021 (4) |
Cl2 | 0.0599 (6) | 0.0452 (5) | 0.0469 (5) | −0.0075 (4) | 0.0096 (4) | −0.0035 (4) |
Cl3 | 0.0492 (5) | 0.0495 (5) | 0.0622 (6) | −0.0017 (4) | 0.0206 (4) | 0.0085 (4) |
C1—C6 | 1.380 (4) | C11—N2 | 1.489 (4) |
C1—C2 | 1.391 (4) | C11—C12 | 1.512 (4) |
C1—C7 | 1.505 (4) | C11—H11A | 0.97 |
C2—C3 | 1.383 (4) | C11—H11B | 0.97 |
C2—H2 | 0.93 | C12—C13 | 1.512 (4) |
C3—C4 | 1.390 (4) | C12—H12A | 0.97 |
C3—C14i | 1.500 (4) | C12—H12B | 0.97 |
C4—C5 | 1.374 (4) | C13—N3 | 1.483 (4) |
C4—H4 | 0.93 | C13—H13A | 0.97 |
C5—C6 | 1.387 (4) | C13—H13B | 0.97 |
C5—H5 | 0.93 | C14—N3 | 1.500 (4) |
C6—H6 | 0.93 | C14—C3i | 1.500 (4) |
C7—N1 | 1.501 (4) | C14—H14A | 0.97 |
C7—H7A | 0.97 | C14—H14B | 0.97 |
C7—H7B | 0.97 | N1—H1A | 0.861 (10) |
C8—N1 | 1.483 (4) | N1—H1B | 0.89 (3) |
C8—C9 | 1.515 (4) | N2—H2A | 0.89 (3) |
C8—H8A | 0.97 | N2—H2B | 0.95 (3) |
C8—H8B | 0.97 | N3—H3A | 0.857 (10) |
C9—C10 | 1.510 (4) | N3—H3B | 0.857 (10) |
C9—H9A | 0.97 | O1W—H1O | 0.84 (4) |
C9—H9B | 0.97 | O1W—H2O | 0.84 (5) |
C10—N2 | 1.492 (4) | O2W—H3O | 0.841 (10) |
C10—H10A | 0.97 | O2W—H4O | 0.84 (3) |
C10—H10B | 0.97 | ||
C6—C1—C2 | 119.0 (3) | N2—C11—H11A | 109.7 |
C6—C1—C7 | 121.9 (3) | C12—C11—H11A | 109.7 |
C2—C1—C7 | 119.1 (3) | N2—C11—H11B | 109.7 |
C3—C2—C1 | 121.4 (3) | C12—C11—H11B | 109.7 |
C3—C2—H2 | 119.3 | H11A—C11—H11B | 108.2 |
C1—C2—H2 | 119.3 | C13—C12—C11 | 111.7 (3) |
C2—C3—C4 | 118.6 (3) | C13—C12—H12A | 109.3 |
C2—C3—C14i | 120.1 (3) | C11—C12—H12A | 109.3 |
C4—C3—C14i | 121.3 (3) | C13—C12—H12B | 109.3 |
C5—C4—C3 | 120.7 (3) | C11—C12—H12B | 109.3 |
C5—C4—H4 | 119.7 | H12A—C12—H12B | 107.9 |
C3—C4—H4 | 119.7 | N3—C13—C12 | 109.3 (3) |
C4—C5—C6 | 120.2 (3) | N3—C13—H13A | 109.8 |
C4—C5—H5 | 119.9 | C12—C13—H13A | 109.8 |
C6—C5—H5 | 119.9 | N3—C13—H13B | 109.8 |
C1—C6—C5 | 120.2 (3) | C12—C13—H13B | 109.8 |
C1—C6—H6 | 119.9 | H13A—C13—H13B | 108.3 |
C5—C6—H6 | 119.9 | N3—C14—C3i | 112.7 (2) |
N1—C7—C1 | 113.0 (2) | N3—C14—H14A | 109.1 |
N1—C7—H7A | 109.0 | C3i—C14—H14A | 109.1 |
C1—C7—H7A | 109.0 | N3—C14—H14B | 109.1 |
N1—C7—H7B | 109.0 | C3i—C14—H14B | 109.1 |
C1—C7—H7B | 109.0 | H14A—C14—H14B | 107.8 |
H7A—C7—H7B | 107.8 | C8—N1—C7 | 116.1 (2) |
N1—C8—C9 | 109.4 (2) | C8—N1—H1A | 106 (2) |
N1—C8—H8A | 109.8 | C7—N1—H1A | 112 (2) |
C9—C8—H8A | 109.8 | C8—N1—H1B | 106 (2) |
N1—C8—H8B | 109.8 | C7—N1—H1B | 106 (2) |
C9—C8—H8B | 109.8 | H1A—N1—H1B | 110 (3) |
H8A—C8—H8B | 108.2 | C11—N2—C10 | 114.5 (2) |
C10—C9—C8 | 110.9 (2) | C11—N2—H2A | 109 (2) |
C10—C9—H9A | 109.5 | C10—N2—H2A | 110.6 (19) |
C8—C9—H9A | 109.5 | C11—N2—H2B | 112 (2) |
C10—C9—H9B | 109.5 | C10—N2—H2B | 108 (2) |
C8—C9—H9B | 109.5 | H2A—N2—H2B | 102 (3) |
H9A—C9—H9B | 108.1 | C13—N3—C14 | 115.9 (3) |
N2—C10—C9 | 110.1 (2) | C13—N3—H3A | 111 (2) |
N2—C10—H10A | 109.6 | C14—N3—H3A | 104 (2) |
C9—C10—H10A | 109.6 | C13—N3—H3B | 108 (2) |
N2—C10—H10B | 109.6 | C14—N3—H3B | 109 (2) |
C9—C10—H10B | 109.6 | H3A—N3—H3B | 108 (3) |
H10A—C10—H10B | 108.2 | H1O—O1W—H2O | 102 (5) |
N2—C11—C12 | 110.0 (2) | H3O—O2W—H4O | 105 (4) |
C6—C1—C2—C3 | 1.6 (5) | C2—C1—C7—N1 | 99.6 (3) |
C7—C1—C2—C3 | −178.7 (3) | N1—C8—C9—C10 | −177.8 (3) |
C1—C2—C3—C4 | −2.0 (5) | C8—C9—C10—N2 | −177.3 (2) |
C1—C2—C3—C14i | 178.4 (3) | N2—C11—C12—C13 | −172.3 (3) |
C2—C3—C4—C5 | 1.4 (5) | C11—C12—C13—N3 | −166.5 (3) |
C14i—C3—C4—C5 | −179.1 (3) | C9—C8—N1—C7 | −174.9 (2) |
C3—C4—C5—C6 | −0.3 (5) | C1—C7—N1—C8 | −53.3 (4) |
C2—C1—C6—C5 | −0.5 (5) | C12—C11—N2—C10 | −166.3 (3) |
C7—C1—C6—C5 | 179.8 (3) | C9—C10—N2—C11 | −178.1 (3) |
C4—C5—C6—C1 | −0.2 (5) | C12—C13—N3—C14 | −172.8 (3) |
C6—C1—C7—N1 | −80.7 (4) | C3i—C14—N3—C13 | −62.0 (4) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl2 | 0.86 (2) | 2.24 (1) | 3.082 (3) | 168 (3) |
N1—H1B···Cl1ii | 0.89 (3) | 2.24 (3) | 3.115 (3) | 169 (3) |
O1W—H1O···Cl3 | 0.84 (4) | 2.46 (5) | 3.287 (4) | 169 (4) |
N2—H2A···Cl1 | 0.89 (3) | 2.28 (3) | 3.162 (3) | 177 (3) |
N2—H2B···Cl2ii | 0.95 (3) | 2.17 (3) | 3.113 (3) | 177 (3) |
O1W—H2O···Cl1 | 0.84 (5) | 2.40 (5) | 3.222 (4) | 166 (5) |
N3—H3A···Cl3 | 0.85 (2) | 2.25 (2) | 3.104 (3) | 173 (3) |
N3—H3B···O2W | 0.86 (2) | 1.94 (2) | 2.782 (4) | 169 (2) |
O2W—H3O···Cl3iii | 0.84 (2) | 2.30 (2) | 3.144 (3) | 176 (6) |
O2W—H4O···Cl3iv | 0.84 (3) | 2.30 (3) | 3.133 (4) | 168 (4) |
Symmetry codes: (ii) −x+1, 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 | C28H52N66+·6Cl−·4H2O |
Mr | 757.52 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 17.012 (7), 7.469 (2), 17.329 (7) |
β (°) | 113.841 (13) |
V (Å3) | 2014.0 (13) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.46 |
Crystal size (mm) | 0.19 × 0.18 × 0.15 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID |
Absorption correction | Multi-scan (Higashi, 1995) |
Tmin, Tmax | 0.895, 0.932 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18546, 4594, 2416 |
Rint | 0.102 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.130, 1.04 |
No. of reflections | 4594 |
No. of parameters | 235 |
No. of restraints | 8 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.26 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO (Rigaku, 1998, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1990).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl2 | 0.86 (2) | 2.24 (1) | 3.082 (3) | 168 (3) |
N1—H1B···Cl1i | 0.89 (3) | 2.24 (3) | 3.115 (3) | 169 (3) |
O1W—H1O···Cl3 | 0.84 (4) | 2.46 (5) | 3.287 (4) | 169 (4) |
N2—H2A···Cl1 | 0.89 (3) | 2.28 (3) | 3.162 (3) | 177 (3) |
N2—H2B···Cl2i | 0.95 (3) | 2.17 (3) | 3.113 (3) | 177 (3) |
O1W—H2O···Cl1 | 0.84 (5) | 2.40 (5) | 3.222 (4) | 166 (5) |
N3—H3A···Cl3 | 0.85 (2) | 2.25 (2) | 3.104 (3) | 173 (3) |
N3—H3B···O2W | 0.86 (2) | 1.94 (2) | 2.782 (4) | 169 (2) |
O2W—H3O···Cl3ii | 0.84 (2) | 2.30 (2) | 3.144 (3) | 176 (6) |
O2W—H4O···Cl3iii | 0.84 (3) | 2.30 (3) | 3.133 (4) | 168 (4) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, y−1, z; (iii) −x, y−1/2, −z+1/2. |
Acknowledgements
The authors thank the Science Foundation for Young Teachers of Northeast Normal University (grant No. 20060304) for supporting this work.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
It has been shown that macrocyclic polyamines have numerous advantages as enzyme models. They can participate in molecular recongnition phenomena with different kinds of substrates, such as organic, inorganic, and biologically important anions (Lu et al., 1995; Anda et al., 2000). In addition, hexaaza macrocycles can form dinuclear metal complexes which in turn are capable of coordinating anions (Costas et al., 2004). In this paper, the synthesis and the crystal structure of a hexaazamacrocyclic complex, L.6HCl.4H2O [L is 3,7,11,19, 23,27-hexaazztricyclo[27.3.1.113,17]tetratriaconta-1(32),13,15,17 (34),29 (33),30-hexaene] is presented.
The structure of the title compound is shown in Fig.1. It consists of a centrosymmetric hexaprotonated macrocycle, six chloride counterions, and four water molecules of crystallization. In the macrocycle, each of the aliphatic chains adopts a planar trans configuration, and each of the benzene rings is tilted from the mean plane of chains by 108.9 (1)°. All six N atoms are protonated with hydrogen atoms directed outside the ring. None of the chloride counterions are situated inside the macrocyclic cavity. The macrocycle adopts a chair conformation, similar to that observed in related compounds (Llobet et al., 1994). The crystal structure is stabilized by N—H···Cl, N—H···O and O—H···Cl hydrogen bonds (Table 1).