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The title compound features a doubly protonated di­methyl- and bis­(methyl­carbox­amide)-substituted tetra­aza­cyclo­tetra­decane with the pendant arms disposed over the cavity, an arrangement that is facilitated by intramolecular hydrogen-bonding interactions. The dication occupies a special position about an inversion centre, whereas the ClO4- anion and the water mol­ecule are in general positions, thus forming a crystal with the overall composition C16H36N6O22+·2ClO4-·2H2O. The crystal structure is stabilized by a variety of hydrogen-bonding contacts involving the dication, perchlorate anion and solvent water mol­ecule.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801007073/ya6022sup1.cif
Contains datablocks general, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801007073/ya6022Isup2.hkl
Contains datablock I

CCDC reference: 165678

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.043
  • wR factor = 0.130
  • Data-to-parameter ratio = 20.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

The crystal structure of the title compound, (I), comprises dications, perchlorate anions and solvent water molecules in the ratio 1:2:2. The cation (Fig. 1) occupies a special position about an inversion centre so that the four N atoms within the macrocycle are coplanar. Protonation occurs at the N1 atom and this is reflected in the systematic differences in the N1—C and N4—C bond distances (Table 1). The pendant acetamide groups lie to either side of the N4 plane and are orientated so as to place the carbonyl O atoms over the cavity of the macrocycle.

This configuration is stabilized by hydrogen-bonding interactions involving the N1-bound H1n atoms which are directed towards the inside of the cavity. Thus, O4'' is equally separated from H1n and the symmetry-related H1ni atoms, indicating that each H1n atom is bifurcated and that a hydrogen-bonded H2O2 square is formed perpendicular to the N4 plane [symmetry code: (i) -x, -y, -z]. Geometric details of the hydrogen-bonding system in the structure of the title compound are given in Table 2.

The O4'' atom also forms an acceptor interaction with the solvent water molecule and the other water-bound H atom forms a donor interaction to a perchlorate O atom. The solvent water molecule is also involved in an acceptor interaction with the cationic NH2 group of the macrocycle. Each of the amide H atoms forms a donor interaction with one of the perchlorate O atoms.

The aforementioned hydrogen-bonding network results in a structure that may be described as being comprised of alternating stacks of cations, and anions and water molecules aligned along the c direction.

Experimental top

The 1,8-bis(acetamido)-7,14-dimethyl-1,4,8,11-tetraazacyclotetradecane was prepared in the following manner: 7,14-dimethyl-1,4,8,11-tetraazacyclotetradecane (Fairbank et al., 1985) (2.28 g, 0.01 mol) in ethanol (20 ml) was added to a solution of 2-chloroacetamide (4.68 g, 0.05 mol) and triethylamine (6.07 g, 0.06 mol) also in ethanol (30 ml). The mixture was then refluxed for one day. After the solution had been allowed to stand for three days, a quantity of colourless crystals prepcipitated. These were recrystallized from a water/acetonitrile (1:1, 20 ml) mixture. Crystals of the title compound were isolated as colourless blocks from the attempted reaction of 1,8-bis(acetamido)-7,14-dimethyl-1,4,8,11-tetraazacyclotetradecane and zinc perchlorate in aqueous medium.

Refinement top

The C-bound H atoms were placed in geometrically calculated positions and included in the final refinement in the riding-model approximation with an overall displacement parameter. The O– and N-bound H atoms were located from a difference Fourier map but were not refined.

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1996); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1997); program(s) used to solve structure: PATTY in DIRDIF92 (Beurskens et al., 1992); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure and crystallographic numbering scheme for the dication in (I). Displacement ellipsoids are shown at the 50% probability level (Johnson, 1976).
(I) top
Crystal data top
C16H36N6O22+·2ClO4·2H2OF(000) = 1232
Mr = 579.43Dx = 1.491 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2ycCell parameters from 20 reflections
a = 16.576 (3) Åθ = 7.5–14.6°
b = 10.877 (6) ŵ = 0.32 mm1
c = 14.314 (2) ÅT = 173 K
β = 90.25 (1)°Block, colourless
V = 2581 (1) Å30.36 × 0.23 × 0.13 mm
Z = 4
Data collection top
Rigaku AFC-7R
diffractometer
Rint = 0.049
Radiation source: Rotating anodeθmax = 27.5°, θmin = 3.6°
Graphite monochromatorh = 218
ω–2θ scansk = 014
4647 measured reflectionsl = 1818
2965 independent reflections3 standard reflections every 400 reflections
1545 reflections with I > 2σ(I) intensity decay: 1.8%
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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130H-atom parameters constrained
S = 0.98 w = 1/[σ2(Fo2) + (0.061P)2]
where P = (Fo2 + 2Fc2)/3
2965 reflections(Δ/σ)max < 0.001
144 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.38 e Å3
Crystal data top
C16H36N6O22+·2ClO4·2H2OV = 2581 (1) Å3
Mr = 579.43Z = 4
Monoclinic, C2/cMo Kα radiation
a = 16.576 (3) ŵ = 0.32 mm1
b = 10.877 (6) ÅT = 173 K
c = 14.314 (2) Å0.36 × 0.23 × 0.13 mm
β = 90.25 (1)°
Data collection top
Rigaku AFC-7R
diffractometer
Rint = 0.049
4647 measured reflections3 standard reflections every 400 reflections
2965 independent reflections intensity decay: 1.8%
1545 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.130H-atom parameters constrained
S = 0.98Δρmax = 0.30 e Å3
2965 reflectionsΔρmin = 0.38 e Å3
144 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*/Ueq
Cl10.13959 (4)0.47165 (7)0.18647 (5)0.02354 (19)
O1W0.13431 (13)0.0929 (2)0.26604 (14)0.0342 (6)
O4''0.03602 (12)0.13000 (19)0.11388 (13)0.0249 (5)
O110.08741 (14)0.4592 (2)0.10686 (16)0.0364 (6)
O120.21217 (13)0.4016 (2)0.16933 (16)0.0373 (6)
O130.15959 (14)0.59953 (19)0.19927 (14)0.0333 (6)
O140.10018 (15)0.4256 (2)0.26829 (16)0.0418 (6)
N10.10757 (14)0.0416 (2)0.07287 (15)0.0191 (5)
N40.06031 (14)0.1575 (2)0.04446 (15)0.0174 (5)
N4''0.04112 (16)0.3352 (2)0.13912 (18)0.0292 (6)
C20.08223 (18)0.1679 (3)0.1021 (2)0.0221 (7)
H2A0.11380.19320.15740.0286 (19)*
H2B0.09410.22650.05090.0286 (19)*
C30.00716 (17)0.1732 (3)0.12561 (19)0.0198 (6)
H3A0.01910.25350.15520.0286 (19)*
H3B0.01960.10820.17190.0286 (19)*
C4'0.05155 (18)0.2586 (3)0.02220 (19)0.0213 (6)
H4'A0.10380.27190.05390.0286 (19)*
H4'B0.03830.33470.01240.0286 (19)*
C4''0.01313 (17)0.2359 (3)0.09541 (18)0.0195 (5)
C50.14479 (17)0.1499 (3)0.07815 (19)0.0214 (5)
H5A0.14660.09770.13480.0286 (19)*
H5B0.16330.23320.09600.0286 (19)*
C60.20235 (17)0.0973 (3)0.0059 (2)0.0221 (4)
H6A0.19900.14820.05130.0286 (19)*
H6B0.25810.10400.03050.0286 (19)*
C70.18652 (16)0.0361 (3)0.02043 (19)0.0203 (4)
H70.18110.08520.03830.0286 (19)*
C7'0.25457 (18)0.0905 (3)0.0780 (2)0.0319 (8)
H7'A0.24190.17620.09330.0286 (19)*
H7'B0.30490.08720.04190.0286 (19)*
H7'C0.26070.04320.13580.0286 (19)*
H1O0.18500.10100.24460.0286 (19)*
H2O0.09810.10980.21260.0286 (19)*
H1N0.06210.01990.03890.0286 (19)*
H2N0.10540.00150.12440.0286 (19)*
H3N0.08100.32080.18590.0286 (19)*
H4N0.01890.41180.12050.0286 (19)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0234 (4)0.0209 (3)0.0262 (4)0.0003 (3)0.0021 (3)0.0017 (3)
O1W0.0283 (12)0.0495 (15)0.0246 (11)0.0001 (11)0.0007 (9)0.0103 (10)
O4''0.0276 (12)0.0244 (12)0.0226 (10)0.0038 (9)0.0065 (9)0.0002 (8)
O110.0401 (14)0.0278 (13)0.0416 (13)0.0058 (11)0.0160 (11)0.0072 (10)
O120.0259 (12)0.0386 (14)0.0472 (14)0.0101 (11)0.0005 (10)0.0089 (11)
O130.0443 (15)0.0233 (12)0.0323 (12)0.0057 (11)0.0029 (11)0.0032 (10)
O140.0475 (16)0.0356 (14)0.0420 (14)0.0084 (12)0.0193 (12)0.0046 (11)
N10.0190 (12)0.0198 (12)0.0185 (11)0.0008 (11)0.0007 (9)0.0007 (10)
N40.0175 (12)0.0174 (12)0.0172 (11)0.0018 (10)0.0012 (9)0.0027 (9)
N4''0.0292 (15)0.0275 (14)0.0307 (14)0.0003 (12)0.0062 (12)0.0057 (11)
C20.0256 (16)0.0179 (15)0.0226 (15)0.0010 (13)0.0026 (12)0.0023 (12)
C30.0235 (15)0.0188 (15)0.0170 (13)0.0001 (12)0.0018 (12)0.0022 (11)
C4'0.0257 (16)0.0144 (14)0.0237 (14)0.0047 (12)0.0001 (12)0.0028 (11)
C4''0.0197 (14)0.0210.0180.0010.0020.006
C50.0215 (14)0.0210.0210.0050.0060.000
C60.0181 (13)0.0240.0240.0040.0020.005
C70.0171 (13)0.0220.0220.0010.0010.001
C7'0.0197 (16)0.042 (2)0.0340 (17)0.0012 (15)0.0036 (14)0.0018 (15)
Geometric parameters (Å, º) top
Cl1—O141.429 (2)N4—C51.481 (3)
Cl1—O131.442 (2)N4''—C4''1.331 (4)
Cl1—O111.440 (2)C2—C31.519 (4)
Cl1—O121.444 (2)C4'—C4''1.516 (4)
O4''—C4''1.241 (3)C5—C61.521 (4)
N1—C21.495 (4)C6—C71.521 (4)
N1—C7i1.507 (3)C7—C7'1.520 (4)
N4—C31.471 (3)C7—N1i1.507 (3)
N4—C4'1.463 (3)
O14—Cl1—O13109.79 (14)N4—C3—C2114.0 (2)
O14—Cl1—O11109.97 (15)N4—C4'—C4''113.3 (2)
O13—Cl1—O11109.30 (13)O4''—C4''—N4''123.2 (3)
O14—Cl1—O12109.37 (15)O4''—C4''—C4'120.9 (2)
O13—Cl1—O12109.79 (14)N4''—C4''—C4'115.9 (3)
O11—Cl1—O12108.60 (14)N4—C5—C6113.3 (2)
C2—N1—C7i114.7 (2)C7—C6—C5114.8 (2)
C4'—N4—C3111.7 (2)C7'—C7—C6112.2 (2)
C4'—N4—C5110.2 (2)C7'—C7—N1i111.1 (2)
C3—N4—C5108.6 (2)C6—C7—N1i108.1 (2)
N1—C2—C3111.7 (2)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1n···O40.932.533.083 (3)118
N1—H1n···O4i0.932.543.079 (3)118
O1w—H2o···O40.991.762.744 (3)176
O1w—H1o···O12ii0.902.022.903 (3)166
N1—H2n···O1wiii0.881.922.768 (3)163
N4—H3n···O13iv0.952.273.110 (4)148
N4—H4n···O11v0.952.263.122 (4)151
Symmetry codes: (i) x, y, z; (ii) x1/2, y+1/2, z; (iii) x, y, z+1/2; (iv) x, y+1, z1/2; (v) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC16H36N6O22+·2ClO4·2H2O
Mr579.43
Crystal system, space groupMonoclinic, C2/c
Temperature (K)173
a, b, c (Å)16.576 (3), 10.877 (6), 14.314 (2)
β (°) 90.25 (1)
V3)2581 (1)
Z4
Radiation typeMo Kα
µ (mm1)0.32
Crystal size (mm)0.36 × 0.23 × 0.13
Data collection
DiffractometerRigaku AFC-7R
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4647, 2965, 1545
Rint0.049
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.130, 0.98
No. of reflections2965
No. of parameters144
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.30, 0.38

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1996), MSC/AFC Diffractometer Control Software, TEXSAN for Windows (Molecular Structure Corporation, 1997), PATTY in DIRDIF92 (Beurskens et al., 1992), SHELXL97 (Sheldrick, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
O4''—C4''1.241 (3)N4''—C4''1.331 (4)
N1—C21.495 (4)C2—C31.519 (4)
N1—C7i1.507 (3)C4'—C4''1.516 (4)
N4—C31.471 (3)C5—C61.521 (4)
N4—C4'1.463 (3)C6—C71.521 (4)
N4—C51.481 (3)C7—C7'1.520 (4)
C2—N1—C7i114.7 (2)O4''—C4''—C4'120.9 (2)
C4'—N4—C3111.7 (2)N4''—C4''—C4'115.9 (3)
C4'—N4—C5110.2 (2)N4—C5—C6113.3 (2)
C3—N4—C5108.6 (2)C7—C6—C5114.8 (2)
N1—C2—C3111.7 (2)C7'—C7—C6112.2 (2)
N4—C3—C2114.0 (2)C7'—C7—N1i111.1 (2)
N4—C4'—C4''113.3 (2)C6—C7—N1i108.1 (2)
O4''—C4''—N4''123.2 (3)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1n···O4''0.932.533.083 (3)118
N1—H1n···O4''i0.932.543.079 (3)118
O1w—H2o···O4''0.991.762.744 (3)176
O1w—H1o···O12ii0.902.022.903 (3)166
N1—H2n···O1wiii0.881.922.768 (3)163
N4''—H3n···O13iv0.952.273.110 (4)148
N4''—H4n···O11v0.952.263.122 (4)151
Symmetry codes: (i) x, y, z; (ii) x1/2, y+1/2, z; (iii) x, y, z+1/2; (iv) x, y+1, z1/2; (v) x, y+1, z.
 

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