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In the title salt, 1,3-bis­{[2-(2-pyridinio)eth­yl][2-(2-pyrid­yl)ethyl]amino}benzene diperchlorate dihydrate, C34H38N62+·2ClO4-·2H2O, the cation contains two ethyl­pyrid­yl and two ethyl­pyridinium pendant pairs anchored to the two N atoms of 1,3-phenyl­enediamine. The pyrid­yl and pyridinium N atoms are flanked by a mol­ecule of water through strong hydrogen-bonding inter­actions [N-H...O = 2.762 (6) and 2.758 (6) Å, and O-H...N = 2.834 (6) and 2.839 (6) Å]. The water mol­ecules have weak hydrogen-bonding inter­actions with the perchlorate anions as well. One of the perchlorate anions is severely disordered.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010501245X/ta1487sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010501245X/ta1487Isup2.hkl
Contains datablock I

CCDC reference: 275531

Comment top

Binucleating multidentate N,O-donor ligands, which can bind two metal ions in close proximity, have received considerable attention as synthetic models for the multinuclear metallobiosites involved in many catalytic transformations (Tshuva & Lippard, 2004). The hexadentate ligand 1,3-tetrakis{[2-(2-pyridyl)ethyl]amino}benzene, PD (Murthy et al., 1993), is one of these. An attempted synthesis of an iron(III)–oxo/hydroxo–acetato-bridged complex of PD by its reaction with ferric perchlorate Fe(ClO4)3.10H2O, acetic acid and triethylamine (1:2:2:2 ratio) in ethanol gave a pale-yellow crystalline solid, at first thought to be an Fe complex. An X-ray diffraction study showed that the product did not contain Fe but was the title compound, [PDH2]2+(ClO4)2·2H2O, (I), in which the two pyridyl groups, one on each amino N atom, are protonated. The selective protonation of these, as opposed to the aromatic ring-substituted amine N atoms, suggests that they are more basic, as expected. A similar protonated salt of a tetradentate aminoethylpyridyl ligand formed under identical reaction conditions has been reported previously (Britton et al., 1991). It is of interest that hydrogen-bonded tertiary aminopyridyl compounds are found to be antidotes for poisoning by organophosphorus compounds (Takeshi et al., 2002).

A view of the hydrogen-bonded structure of (I) and its atom-numbering scheme is shown in Fig. 1. The structure includes a [PDH2]2+ dication, two perchlorate anions (one severely disordered) and two molecules of water. The packing diagram is given in Fig. 2. Compound (I) has two aromatic ring-substituted amine N atoms (N1 and N4) and four pyridyl N atoms (N2, N3, N5 and N6), of which two pyridyl N atoms are protonated (H3N and H5N). The amino N atoms, N1 and N4, are planar; the angles around them are close to 120°, indicating a π-delocalization of their lone pairs with the phenyl ring, which prevents their protonation or involvement in hydrogen bonds. In general, aminopyridyls are protonated in acidic solutions. In the present case, the protonation may be due to the acidic nature of the hydrated ferric perchlorate salt.

Notably, each pair of protonated pyridinium and non-protonated pyridyl groups trap a molecule of water (H2O5 and H2O6), one on each side, through strong hydrogen-bonding interactions (Table 1). The interactions are similar on both sides, with N3—H3N····O5 = 2.762 (6) and O5—H5B···N2 = 2.834 (6) Å, and N5—H5N····O6 = 2.758 (6) O6—H6B···N6 = 2.839 (6) Å]. These water molecules also have additional weak hydrogen-bonding interactions with perchlorate anions. A subtle difference in their interaction is apparent, as atom H5A on O5 interacts with two O atoms, while atom H6A interacts with only one of the O atoms of the perchlorate anions (Table 1). These factors appear to have an effect on the relative orientations of the pyridyl and pyridinium rings. Rings N6/C61–C65 and N5/C51–C55, with stronger hydrogen-bonding interactions with perchlorate, deviate from coplanarity (dihedral angle 28.2 °), while rings N2/C21–C25 and N3/C31–C35, with weaker perchlorate hydrogen-bonding interactions, are coplanar (dihedral angle 1.76 °). By contrast, in another similar instance, a hexadentate ligand with methylpyridyl pendants (Buchen et al., 1997), the two pyridine N atoms at each end of the molecule are mutually hydrogen bonded, with no intervening H2O molecule. The reason for the difference in compound (I) may be due to the longer arm length of the pendants allowing the accommodation of a molecule of water. These two examples clearly exemplify the key role of structure on the type and nature of hydrogen-bonding interactions.

The C—C and C—N bond distances in (I) are very close to the corresponding values reported for an analogous ligand system (Buchen et al., 1997).

Experimental top

The reaction of the binucleating ligand 1,3-tetrakis{[2-(2-pyridyl)ethyl]amino}benzene, PD, and ferric perchlorate decahydrate, Fe(ClO4)3.10H2O, in the presence of acetic acid and triethylamine (1:2:2:2 molar? ratio) in ethanol resulted in the formation of the title salt, (I), as pale-yellow needles in 86% yield. UV–vis [MeOH, λmax, nm (ε, LM−1cm−1)]: 305 (632); IR (Nujol, cm−1): 3488 (s, H2O), 1100 (s, ClO4); 1H NMR (CD3NO2, 400 MHz, δ, p.p.m.): 3.42 (overlapping triplets, 8H, CH2), 3.92 (overlapping triplets, 8H, CH2py), 5.4 (s, b, –NH), 6.58 (d, 2H), 7.20 (s, 1H), 7.99–8.01 (m, 9H), 8.54 (t, 4H, 4-pyridyl), 8.68 (d, 4H, 6-pyridinium/pyridyl). Crystals suitable for X-ray diffraction were obtained from the original sample.

Refinement top

H atoms attached to aromatic C atoms were fixed at C—H distances of 0.93 Å, while those attached to aliphatic methylene C atoms were fixed at C—H distances of 0.97 Å, and they were all refined using a riding-model approximation, with Uiso(H) = 1.2Ueq(C). H atoms attached to the pyridyl N atoms (N3 and N5) were identified from the difference maps and refined isotropically. The Fourier map gave a set of eight disordered positions for the O atoms of one of the perchlorate anions (Cl2O4). Initially, four of those peaks satisfying nearly tetrahedral geometry were assigned as O atoms (O7, O8, O9 and O10) with partial site occupancy. Refinement, and hence the subsequent difference map, showed three more O-atom positions (O7', O9' and O10'). Thus, atom O8 was found common to two approximate tetrahedra. The constrained refinements were performed on these partial positions such that the atoms of the two tetrahedra remained in chemically meaningful positions. Two common occupancy factors were given to each disordered set with the sum constrained to 1. The H atoms of the two water molecules were located in a difference map and their positions were fixed during the refinement such that they remained in chemically meaningful positions. Both the water molecules are hydrogen bonded to pyridine N atoms and perchlorate O atoms. Atom H6A of water molecule H2O6, which is hydrogen-bonded to the disordered perchlorate group Cl2O4, is also disordered; its position was fixed at a geometrically meaningful position and was not refined.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995) in WinGX (Farrugia, 1999); program(s) used to solve structure: SIR92 in WinGX (Altomare et al., 1994) in WinGX; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and WinGX.

Figures top
[Figure 1] Fig. 1. The crystal structure of the [PDH2]2+ cation of (I), showing the intramolecular hydrogen bonding (dashed lines) and the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms bonded to C atoms have been omitted for clarity. The perchlorate anions are not shown.
[Figure 2] Fig. 2. A partial packing diagram for (I). Disordered O-atom positions about Cl2 are shown. Selected atoms are labelled. Hydrogen bonds are shown as dashed lines.
1,3-bis{[2-(2-pyridinio)ethyl][2-(2-pyridyl)ethyl]amino}benzene diperchlorate dihydrate top
Crystal data top
C34H38N62+·2ClO4·2H2OZ = 2
Mr = 765.64F(000) = 804
Triclinic, P1Dx = 1.394 Mg m3
a = 9.264 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.937 (6) ÅCell parameters from 25 reflections
c = 20.751 (8) Åθ = 10–15°
α = 78.28 (4)°µ = 0.24 mm1
β = 87.01 (3)°T = 293 K
γ = 77.31 (4)°Needle, pale yellow
V = 1824.6 (15) Å30.3 × 0.2 × 0.2 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer
3517 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.031
Graphite monochromatorθmax = 25.0°, θmin = 2.0°
ω/2θ scansh = 010
Absorption correction: ψ scan
(North et al., 1968). Number of ψ-scan sets used was 5. θ correction was applied. Averaged transmission function was used. No Fourier smoothing was applied.
k = 1111
Tmin = 0.946, Tmax = 1.000l = 2424
6833 measured reflections2 standard reflections every 60 min
6397 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.068Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.212H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.1022P)2 + 1.7559P]
where P = (Fo2 + 2Fc2)/3
6397 reflections(Δ/σ)max < 0.001
518 parametersΔρmax = 0.57 e Å3
94 restraintsΔρmin = 0.43 e Å3
Crystal data top
C34H38N62+·2ClO4·2H2Oγ = 77.31 (4)°
Mr = 765.64V = 1824.6 (15) Å3
Triclinic, P1Z = 2
a = 9.264 (4) ÅMo Kα radiation
b = 9.937 (6) ŵ = 0.24 mm1
c = 20.751 (8) ÅT = 293 K
α = 78.28 (4)°0.3 × 0.2 × 0.2 mm
β = 87.01 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer
3517 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968). Number of ψ-scan sets used was 5. θ correction was applied. Averaged transmission function was used. No Fourier smoothing was applied.
Rint = 0.031
Tmin = 0.946, Tmax = 1.0002 standard reflections every 60 min
6833 measured reflections intensity decay: none
6397 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.06894 restraints
wR(F2) = 0.212H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.57 e Å3
6397 reflectionsΔρmin = 0.43 e Å3
518 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
xyzUiso*/UeqOcc. (<1)
C10.6496 (5)0.4208 (4)0.7296 (2)0.0416 (10)
C20.6481 (5)0.2957 (4)0.7743 (2)0.0422 (10)
H20.57110.25010.77280.051*
C30.7591 (5)0.2365 (4)0.8214 (2)0.0402 (10)
C40.8700 (5)0.3105 (5)0.8246 (2)0.0486 (11)
H40.94360.27540.85620.058*
C50.8703 (5)0.4344 (5)0.7813 (2)0.0514 (12)
H50.94490.48210.78410.062*
C60.7634 (5)0.4910 (5)0.7335 (2)0.0479 (11)
H60.76710.57460.70430.058*
C210.4155 (7)0.8555 (6)0.4437 (3)0.0690 (15)
H210.32100.87470.42630.083*
C220.5059 (9)0.9416 (6)0.4180 (3)0.0767 (18)
H220.47491.01730.38360.092*
C230.6457 (8)0.9154 (6)0.4437 (3)0.0801 (19)
H230.71140.97260.42680.096*
C240.6867 (6)0.8014 (6)0.4955 (3)0.0664 (15)
H240.77980.78240.51430.080*
C250.5878 (6)0.7174 (5)0.5184 (2)0.0507 (12)
C260.6243 (6)0.5910 (5)0.5740 (3)0.0608 (14)
H26A0.72860.57340.58400.073*
H26B0.60650.50920.55950.073*
C270.5344 (5)0.6089 (5)0.6364 (2)0.0489 (12)
H27A0.57230.67200.65790.059*
H27B0.43240.65220.62460.059*
C310.0203 (6)0.3555 (6)0.5922 (3)0.0619 (14)
H310.02000.39750.55100.074*
C320.0215 (6)0.2390 (6)0.6269 (3)0.0675 (15)
H320.08990.20030.60950.081*
C330.0378 (6)0.1790 (6)0.6873 (3)0.0660 (15)
H330.00980.09910.71160.079*
C340.1387 (6)0.2367 (5)0.7123 (3)0.0592 (13)
H340.18000.19470.75340.071*
C350.1798 (5)0.3560 (5)0.6774 (2)0.0490 (12)
C360.2874 (6)0.4286 (5)0.7004 (2)0.0547 (13)
H36A0.29850.39920.74780.066*
H36B0.24920.52950.69060.066*
C370.4379 (5)0.3942 (5)0.6672 (2)0.0506 (12)
H37A0.48100.29480.68120.061*
H37B0.42480.41280.61990.061*
C511.1883 (7)0.3575 (6)0.9881 (3)0.0696 (16)
H511.16490.44381.00610.083*
C521.3124 (6)0.3268 (6)1.0073 (3)0.0721 (16)
H521.37410.39051.03870.087*
C531.3458 (6)0.1993 (6)0.9794 (3)0.0668 (15)
H531.43200.17670.99090.080*
C541.2511 (6)0.1059 (5)0.9345 (3)0.0563 (13)
H541.27260.01880.91640.068*
C551.1264 (5)0.1380 (5)0.9158 (2)0.0450 (11)
C561.0150 (5)0.0426 (5)0.8687 (2)0.0527 (12)
H56A0.97910.09700.84160.063*
H56B1.06150.02580.84000.063*
C570.8832 (5)0.0351 (5)0.9052 (2)0.0482 (11)
H57A0.85150.03300.94040.058*
H57B0.91730.10230.92530.058*
C610.4943 (7)0.3488 (6)0.8381 (3)0.0731 (16)
H610.51490.43800.86480.088*
C620.3684 (7)0.3114 (7)0.8025 (3)0.0756 (17)
H620.30490.37270.80450.091*
C630.3382 (7)0.1804 (8)0.7636 (3)0.0790 (18)
H630.25210.15020.73880.095*
C640.4360 (6)0.0935 (6)0.7612 (3)0.0635 (14)
H640.41690.00450.73440.076*
C650.5623 (6)0.1386 (5)0.7987 (2)0.0515 (12)
C660.6707 (6)0.0483 (5)0.7993 (2)0.0556 (13)
H66A0.66240.02120.75860.067*
H66B0.77010.10610.80120.067*
C670.6463 (5)0.0273 (5)0.8578 (2)0.0474 (11)
H67A0.54940.08990.85360.057*
H67B0.64540.04250.89790.057*
N10.5386 (5)0.4760 (4)0.6827 (2)0.0557 (11)
N20.4523 (5)0.7435 (4)0.4928 (2)0.0582 (11)
N30.1199 (4)0.4102 (5)0.6173 (2)0.0528 (10)
N40.7558 (4)0.1091 (4)0.86469 (18)0.0455 (9)
N51.0986 (5)0.2650 (4)0.9436 (2)0.0567 (11)
N60.5919 (5)0.2661 (4)0.8376 (2)0.0615 (11)
O10.0048 (7)0.7770 (8)0.7199 (3)0.160 (3)
O20.1565 (7)0.9274 (7)0.6492 (3)0.163 (3)
O30.0544 (6)0.7073 (5)0.6282 (3)0.126 (2)
O40.0881 (7)0.8688 (7)0.6189 (4)0.166 (3)
O50.1939 (5)0.6395 (4)0.5337 (2)0.0660 (10)
O60.8706 (5)0.3617 (4)0.9008 (2)0.0875 (13)
O80.2719 (5)0.2284 (4)0.86017 (18)0.0859 (13)
O70.1464 (10)0.2502 (10)0.9534 (4)0.089 (3)0.494 (4)
O90.3684 (9)0.3198 (11)0.9375 (5)0.119 (5)0.494 (4)
O100.1684 (9)0.4420 (7)0.8782 (5)0.094 (4)0.494 (4)
O7'0.2776 (17)0.1994 (10)0.9721 (4)0.138 (5)0.506 (4)
O9'0.3638 (11)0.3796 (11)0.9088 (6)0.125 (6)0.506 (4)
O10'0.1132 (9)0.3894 (15)0.9143 (8)0.216 (12)0.506 (4)
Cl10.03294 (17)0.82241 (15)0.65273 (8)0.0741 (5)
Cl20.24922 (15)0.30465 (14)0.91146 (7)0.0628 (4)
H3N0.135 (5)0.495 (6)0.590 (3)0.061 (15)*
H5N1.023 (7)0.291 (6)0.933 (3)0.08 (2)*
H5B0.281 (3)0.663 (6)0.522 (3)0.11 (3)*
H5A0.130 (6)0.709 (5)0.548 (4)0.16 (4)*
H6A0.88270.45020.89430.180*
H6B0.777 (3)0.314 (4)0.893 (5)0.20 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.041 (2)0.036 (2)0.045 (3)0.006 (2)0.004 (2)0.004 (2)
C20.039 (2)0.038 (2)0.050 (3)0.013 (2)0.005 (2)0.003 (2)
C30.037 (2)0.036 (2)0.047 (3)0.0081 (19)0.004 (2)0.005 (2)
C40.041 (3)0.049 (3)0.056 (3)0.010 (2)0.009 (2)0.008 (2)
C50.048 (3)0.047 (3)0.062 (3)0.020 (2)0.002 (2)0.006 (2)
C60.050 (3)0.037 (2)0.054 (3)0.013 (2)0.006 (2)0.003 (2)
C210.088 (4)0.060 (3)0.052 (3)0.010 (3)0.010 (3)0.000 (3)
C220.115 (6)0.058 (4)0.049 (3)0.014 (4)0.011 (4)0.000 (3)
C230.108 (5)0.065 (4)0.072 (4)0.039 (4)0.039 (4)0.014 (3)
C240.064 (3)0.069 (4)0.068 (4)0.018 (3)0.009 (3)0.015 (3)
C250.057 (3)0.046 (3)0.048 (3)0.011 (2)0.008 (2)0.011 (2)
C260.059 (3)0.051 (3)0.064 (3)0.000 (2)0.002 (3)0.004 (3)
C270.055 (3)0.037 (2)0.050 (3)0.008 (2)0.009 (2)0.003 (2)
C310.056 (3)0.069 (4)0.059 (3)0.013 (3)0.014 (3)0.006 (3)
C320.054 (3)0.075 (4)0.077 (4)0.025 (3)0.011 (3)0.010 (3)
C330.070 (4)0.062 (3)0.070 (4)0.029 (3)0.004 (3)0.007 (3)
C340.066 (3)0.061 (3)0.048 (3)0.018 (3)0.000 (3)0.000 (3)
C350.049 (3)0.050 (3)0.048 (3)0.009 (2)0.002 (2)0.010 (2)
C360.071 (3)0.049 (3)0.045 (3)0.017 (3)0.003 (2)0.007 (2)
C370.055 (3)0.047 (3)0.047 (3)0.014 (2)0.013 (2)0.003 (2)
C510.070 (4)0.046 (3)0.079 (4)0.004 (3)0.007 (3)0.013 (3)
C520.061 (4)0.069 (4)0.071 (4)0.007 (3)0.022 (3)0.003 (3)
C530.050 (3)0.071 (4)0.079 (4)0.007 (3)0.015 (3)0.017 (3)
C540.054 (3)0.048 (3)0.064 (3)0.009 (2)0.002 (3)0.008 (3)
C550.043 (3)0.044 (3)0.043 (3)0.002 (2)0.000 (2)0.004 (2)
C560.052 (3)0.057 (3)0.042 (3)0.007 (2)0.002 (2)0.002 (2)
C570.049 (3)0.045 (3)0.044 (3)0.005 (2)0.007 (2)0.003 (2)
C610.099 (5)0.053 (3)0.074 (4)0.032 (3)0.003 (4)0.011 (3)
C620.087 (5)0.084 (5)0.075 (4)0.046 (4)0.009 (4)0.034 (4)
C630.058 (4)0.112 (6)0.080 (4)0.021 (4)0.005 (3)0.041 (4)
C640.063 (3)0.065 (3)0.058 (3)0.009 (3)0.007 (3)0.004 (3)
C650.056 (3)0.049 (3)0.050 (3)0.014 (2)0.004 (2)0.010 (2)
C660.056 (3)0.053 (3)0.057 (3)0.017 (2)0.004 (2)0.005 (2)
C670.047 (3)0.039 (2)0.052 (3)0.009 (2)0.001 (2)0.000 (2)
N10.063 (3)0.045 (2)0.057 (3)0.022 (2)0.023 (2)0.0138 (19)
N20.066 (3)0.052 (2)0.054 (3)0.015 (2)0.000 (2)0.002 (2)
N30.052 (3)0.050 (2)0.053 (3)0.011 (2)0.007 (2)0.001 (2)
N40.043 (2)0.040 (2)0.050 (2)0.0096 (17)0.0092 (18)0.0024 (17)
N50.049 (3)0.051 (3)0.067 (3)0.014 (2)0.006 (2)0.001 (2)
N60.074 (3)0.046 (2)0.064 (3)0.016 (2)0.010 (2)0.004 (2)
O10.122 (5)0.240 (8)0.104 (4)0.027 (5)0.044 (4)0.005 (5)
O20.143 (5)0.148 (5)0.155 (6)0.057 (5)0.020 (4)0.022 (5)
O30.139 (5)0.103 (4)0.166 (5)0.068 (4)0.037 (4)0.061 (4)
O40.173 (6)0.145 (5)0.216 (7)0.109 (5)0.091 (5)0.056 (5)
O50.069 (3)0.065 (2)0.063 (2)0.021 (2)0.000 (2)0.001 (2)
O60.088 (3)0.064 (2)0.109 (4)0.023 (2)0.029 (3)0.001 (2)
O80.103 (3)0.082 (3)0.070 (3)0.006 (2)0.002 (2)0.021 (2)
O70.070 (6)0.141 (10)0.055 (5)0.030 (6)0.019 (5)0.016 (6)
O90.074 (7)0.125 (11)0.156 (12)0.015 (7)0.079 (8)0.006 (9)
O100.068 (8)0.040 (4)0.167 (10)0.003 (5)0.022 (7)0.009 (5)
O7'0.249 (17)0.123 (9)0.059 (6)0.099 (11)0.016 (8)0.010 (6)
O9'0.111 (10)0.089 (8)0.182 (14)0.067 (8)0.027 (9)0.011 (9)
O10'0.038 (7)0.26 (2)0.39 (3)0.049 (11)0.057 (12)0.23 (2)
Cl10.0699 (10)0.0576 (8)0.0967 (12)0.0151 (7)0.0055 (8)0.0164 (8)
Cl20.0571 (8)0.0628 (8)0.0732 (9)0.0211 (7)0.0009 (7)0.0153 (7)
Geometric parameters (Å, º) top
C1—C21.394 (6)C52—C531.375 (8)
C1—N11.395 (6)C52—H520.9300
C1—C61.399 (6)C53—C541.369 (7)
C2—C31.402 (6)C53—H530.9300
C2—H20.9300C54—C551.359 (7)
C3—C41.399 (6)C54—H540.9300
C3—N41.401 (5)C55—N51.351 (6)
C4—C51.370 (6)C55—C561.489 (6)
C4—H40.9300C56—C571.544 (7)
C5—C61.383 (6)C56—H56A0.9700
C5—H50.9300C56—H56B0.9700
C6—H60.9300C57—N41.453 (6)
C21—C221.342 (8)C57—H57A0.9700
C21—N21.343 (6)C57—H57B0.9700
C21—H210.9300C61—N61.347 (7)
C22—C231.377 (9)C61—C621.353 (9)
C22—H220.9300C61—H610.9300
C23—C241.394 (8)C62—C631.364 (9)
C23—H230.9300C62—H620.9300
C24—C251.375 (7)C63—C641.375 (8)
C24—H240.9300C63—H630.9300
C25—N21.340 (6)C64—C651.378 (7)
C25—C261.512 (7)C64—H640.9300
C26—C271.523 (7)C65—N61.337 (6)
C26—H26A0.9700C65—C661.488 (7)
C26—H26B0.9700C66—C671.536 (7)
C27—N11.461 (5)C66—H66A0.9700
C27—H27A0.9700C66—H66B0.9700
C27—H27B0.9700C67—N41.461 (6)
C31—N31.344 (6)C67—H67A0.9700
C31—C321.355 (8)C67—H67B0.9700
C31—H310.9300N3—H3N0.95 (5)
C32—C331.362 (7)N5—H5N0.85 (6)
C32—H320.9300O1—Cl11.412 (5)
C33—C341.371 (7)O2—Cl11.363 (5)
C33—H330.9300O3—Cl11.398 (4)
C34—C351.377 (7)O4—Cl11.406 (5)
C34—H340.9300O5—H5B0.90 (4)
C35—N31.348 (6)O5—H5A0.90 (4)
C35—C361.500 (7)O6—H6A0.90
C36—C371.524 (7)O6—H6B0.90 (4)
C36—H36A0.9700O8—Cl21.409 (4)
C36—H36B0.9700O7—Cl21.380 (6)
C37—N11.452 (6)O9—Cl21.305 (7)
C37—H37A0.9700O10—Cl21.457 (7)
C37—H37B0.9700O7'—Cl21.457 (8)
C51—N51.337 (7)O9'—Cl21.417 (8)
C51—C521.351 (8)O10'—Cl21.359 (8)
C51—H510.9300
C2—C1—N1120.6 (4)C52—C53—H53120.3
C2—C1—C6118.7 (4)C55—C54—C53121.3 (5)
N1—C1—C6120.7 (4)C55—C54—H54119.3
C1—C2—C3122.0 (4)C53—C54—H54119.3
C1—C2—H2119.0N5—C55—C54117.5 (4)
C3—C2—H2119.0N5—C55—C56117.2 (4)
C4—C3—N4121.6 (4)C54—C55—C56125.3 (4)
C4—C3—C2117.9 (4)C55—C56—C57111.4 (4)
N4—C3—C2120.5 (4)C55—C56—H56A109.3
C5—C4—C3120.1 (4)C57—C56—H56A109.3
C5—C4—H4120.0C55—C56—H56B109.3
C3—C4—H4120.0C57—C56—H56B109.3
C4—C5—C6122.2 (4)H56A—C56—H56B108.0
C4—C5—H5118.9N4—C57—C56115.4 (4)
C6—C5—H5118.9N4—C57—H57A108.4
C5—C6—C1119.2 (4)C56—C57—H57A108.4
C5—C6—H6120.4N4—C57—H57B108.4
C1—C6—H6120.4C56—C57—H57B108.4
C22—C21—N2124.4 (6)H57A—C57—H57B107.5
C22—C21—H21117.8N6—C61—C62124.6 (6)
N2—C21—H21117.8N6—C61—H61117.7
C21—C22—C23118.4 (6)C62—C61—H61117.7
C21—C22—H22120.8C61—C62—C63117.6 (6)
C23—C22—H22120.8C61—C62—H62121.2
C22—C23—C24118.7 (6)C63—C62—H62121.2
C22—C23—H23120.7C62—C63—C64119.5 (6)
C24—C23—H23120.7C62—C63—H63120.2
C25—C24—C23119.1 (6)C64—C63—H63120.2
C25—C24—H24120.4C63—C64—C65119.8 (5)
C23—C24—H24120.4C63—C64—H64120.1
N2—C25—C24121.7 (5)C65—C64—H64120.1
N2—C25—C26115.9 (4)N6—C65—C64121.0 (5)
C24—C25—C26122.4 (5)N6—C65—C66116.6 (5)
C25—C26—C27113.4 (4)C64—C65—C66122.3 (5)
C25—C26—H26A108.9C65—C66—C67112.3 (4)
C27—C26—H26A108.9C65—C66—H66A109.1
C25—C26—H26B108.9C67—C66—H66A109.1
C27—C26—H26B108.9C65—C66—H66B109.1
H26A—C26—H26B107.7C67—C66—H66B109.1
N1—C27—C26113.0 (4)H66A—C66—H66B107.9
N1—C27—H27A109.0N4—C67—C66115.5 (4)
C26—C27—H27A109.0N4—C67—H67A108.4
N1—C27—H27B109.0C66—C67—H67A108.4
C26—C27—H27B109.0N4—C67—H67B108.4
H27A—C27—H27B107.8C66—C67—H67B108.4
N3—C31—C32120.0 (5)H67A—C67—H67B107.5
N3—C31—H31120.0C1—N1—C37122.5 (4)
C32—C31—H31120.0C1—N1—C27122.1 (4)
C31—C32—C33119.3 (5)C37—N1—C27114.3 (4)
C31—C32—H32120.3C25—N2—C21117.6 (5)
C33—C32—H32120.3C31—N3—C35122.8 (5)
C32—C33—C34119.9 (5)C31—N3—H3N112 (3)
C32—C33—H33120.1C35—N3—H3N125 (3)
C34—C33—H33120.1C3—N4—C57120.4 (4)
C33—C34—C35120.8 (5)C3—N4—C67121.2 (4)
C33—C34—H34119.6C57—N4—C67116.2 (4)
C35—C34—H34119.6C51—N5—C55122.5 (5)
N3—C35—C34117.2 (4)C51—N5—H5N117 (4)
N3—C35—C36117.7 (4)C55—N5—H5N121 (4)
C34—C35—C36125.1 (4)C65—N6—C61117.4 (5)
C35—C36—C37111.1 (4)H5B—O5—H5A112 (5)
C35—C36—H36A109.4H6A—O6—H6B111
C37—C36—H36A109.4O2—Cl1—O3113.1 (4)
C35—C36—H36B109.4O2—Cl1—O4112.4 (5)
C37—C36—H36B109.4O3—Cl1—O4107.8 (4)
H36A—C36—H36B108.0O2—Cl1—O1107.0 (5)
N1—C37—C36112.1 (4)O3—Cl1—O1108.6 (4)
N1—C37—H37A109.2O4—Cl1—O1107.8 (5)
C36—C37—H37A109.2O9—Cl2—O7117.6 (5)
N1—C37—H37B109.2O9—Cl2—O8116.0 (5)
C36—C37—H37B109.2O10'—Cl2—O8116.0 (5)
H37A—C37—H37B107.9O7—Cl2—O8106.0 (4)
N5—C51—C52120.7 (5)O10'—Cl2—O9'111.8 (5)
N5—C51—H51119.6O8—Cl2—O9'108.6 (5)
C52—C51—H51119.6O9—Cl2—O10109.0 (5)
C51—C52—C53118.6 (5)O7—Cl2—O10104.5 (4)
C51—C52—H52120.7O8—Cl2—O10101.9 (4)
C53—C52—H52120.7O10'—Cl2—O7'110.0 (6)
C54—C53—C52119.4 (5)O8—Cl2—O7'105.6 (4)
C54—C53—H53120.3O9'—Cl2—O7'104.0 (5)
N1—C1—C2—C3179.1 (4)C61—C62—C63—C640.9 (9)
C6—C1—C2—C31.9 (7)C62—C63—C64—C650.9 (9)
C1—C2—C3—C42.9 (7)C63—C64—C65—N60.1 (8)
C1—C2—C3—N4178.7 (4)C63—C64—C65—C66178.8 (5)
N4—C3—C4—C5179.7 (4)N6—C65—C66—C6781.9 (6)
C2—C3—C4—C51.9 (7)C64—C65—C66—C6797.0 (6)
C3—C4—C5—C60.0 (7)C65—C66—C67—N4175.3 (4)
C4—C5—C6—C11.0 (7)C2—C1—N1—C3714.8 (7)
C2—C1—C6—C50.0 (7)C6—C1—N1—C37166.2 (4)
N1—C1—C6—C5178.9 (4)C2—C1—N1—C27178.2 (4)
N2—C21—C22—C230.6 (9)C6—C1—N1—C270.7 (7)
C21—C22—C23—C240.5 (9)C36—C37—N1—C1101.1 (5)
C22—C23—C24—C251.2 (8)C36—C37—N1—C2791.0 (5)
C23—C24—C25—N20.9 (8)C26—C27—N1—C187.4 (6)
C23—C24—C25—C26179.4 (5)C26—C27—N1—C3780.6 (5)
N2—C25—C26—C2767.4 (6)C24—C25—N2—C210.1 (7)
C24—C25—C26—C27112.3 (6)C26—C25—N2—C21179.5 (4)
C25—C26—C27—N1163.9 (4)C22—C21—N2—C251.0 (8)
N3—C31—C32—C330.4 (9)C32—C31—N3—C351.5 (8)
C31—C32—C33—C340.1 (9)C34—C35—N3—C312.2 (7)
C32—C33—C34—C350.9 (9)C36—C35—N3—C31178.7 (5)
C33—C34—C35—N31.9 (8)C4—C3—N4—C5712.8 (6)
C33—C34—C35—C36179.1 (5)C2—C3—N4—C57168.9 (4)
N3—C35—C36—C3776.6 (5)C4—C3—N4—C67175.3 (4)
C34—C35—C36—C37102.4 (6)C2—C3—N4—C676.3 (6)
C35—C36—C37—N1173.2 (4)C56—C57—N4—C375.1 (5)
N5—C51—C52—C530.9 (9)C56—C57—N4—C6788.3 (5)
C51—C52—C53—C541.7 (9)C66—C67—N4—C372.6 (5)
C52—C53—C54—C551.5 (8)C66—C67—N4—C5790.6 (5)
C53—C54—C55—N50.6 (7)C52—C51—N5—C550.0 (9)
C53—C54—C55—C56178.3 (5)C54—C55—N5—C510.2 (7)
N5—C55—C56—C5781.0 (5)C56—C55—N5—C51177.8 (5)
C54—C55—C56—C5796.7 (6)C64—C65—N6—C610.6 (8)
C55—C56—C57—N4168.5 (4)C66—C65—N6—C61179.5 (5)
N6—C61—C62—C630.3 (9)C62—C61—N6—C650.5 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3N···O50.95 (5)1.82 (5)2.762 (6)170 (5)
N5—H5N···O60.85 (6)1.91 (6)2.758 (6)172 (6)
O5—H5B···N20.90 (4)1.95 (4)2.834 (6)172 (6)
O5—H5A···O30.90 (4)2.32 (5)2.996 (7)132 (6)
O5—H5A···O40.90 (4)2.33 (5)3.123 (8)147 (7)
O6—H6A···O10i0.902.372.931 (10)121
O6—H6B···N60.90 (4)2.02 (4)2.839 (6)150 (7)
Symmetry code: (i) x+1, y1, z.

Experimental details

Crystal data
Chemical formulaC34H38N62+·2ClO4·2H2O
Mr765.64
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)9.264 (4), 9.937 (6), 20.751 (8)
α, β, γ (°)78.28 (4), 87.01 (3), 77.31 (4)
V3)1824.6 (15)
Z2
Radiation typeMo Kα
µ (mm1)0.24
Crystal size (mm)0.3 × 0.2 × 0.2
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968). Number of ψ-scan sets used was 5. θ correction was applied. Averaged transmission function was used. No Fourier smoothing was applied.
Tmin, Tmax0.946, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
6833, 6397, 3517
Rint0.031
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.068, 0.212, 1.02
No. of reflections6397
No. of parameters518
No. of restraints94
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.57, 0.43

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), CAD-4 Software, XCAD4 (Harms & Wocadlo, 1995) in WinGX (Farrugia, 1999), SIR92 in WinGX (Altomare et al., 1994) in WinGX, SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003), SHELXL97 and WinGX.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3N···O50.95 (5)1.82 (5)2.762 (6)170 (5)
N5—H5N···O60.85 (6)1.91 (6)2.758 (6)172 (6)
O5—H5B···N20.90 (4)1.95 (4)2.834 (6)172 (6)
O5—H5A···O30.90 (4)2.32 (5)2.996 (7)132 (6)
O5—H5A···O40.90 (4)2.33 (5)3.123 (8)147 (7)
O6—H6A···O10'i0.902.3662.931 (10)121
O6—H6B···N60.90 (4)2.02 (4)2.839 (6)150 (7)
Symmetry code: (i) x+1, y1, z.
 

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