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
CCDC reference: 165678
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (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
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.
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.
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.
Crystal data top
C16H36N6O22+·2ClO4−·2H2O | F(000) = 1232 |
Mr = 579.43 | Dx = 1.491 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -C 2yc | Cell parameters from 20 reflections |
a = 16.576 (3) Å | θ = 7.5–14.6° |
b = 10.877 (6) Å | µ = 0.32 mm−1 |
c = 14.314 (2) Å | T = 173 K |
β = 90.25 (1)° | Block, colourless |
V = 2581 (1) Å3 | 0.36 × 0.23 × 0.13 mm |
Z = 4 | |
Data collection top
Rigaku AFC-7R diffractometer | Rint = 0.049 |
Radiation source: Rotating anode | θmax = 27.5°, θmin = 3.6° |
Graphite monochromator | h = −21→8 |
ω–2θ scans | k = 0→14 |
4647 measured reflections | l = −18→18 |
2965 independent reflections | 3 standard reflections every 400 reflections |
1545 reflections with I > 2σ(I) | intensity decay: 1.8% |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H-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 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
Crystal data top
C16H36N6O22+·2ClO4−·2H2O | V = 2581 (1) Å3 |
Mr = 579.43 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 16.576 (3) Å | µ = 0.32 mm−1 |
b = 10.877 (6) Å | T = 173 K |
c = 14.314 (2) Å | 0.36 × 0.23 × 0.13 mm |
β = 90.25 (1)° | |
Data collection top
Rigaku AFC-7R diffractometer | Rint = 0.049 |
4647 measured reflections | 3 standard reflections every 400 reflections |
2965 independent reflections | intensity decay: 1.8% |
1545 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.30 e Å−3 |
2965 reflections | Δρmin = −0.38 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Cl1 | −0.13959 (4) | 0.47165 (7) | 0.18647 (5) | 0.02354 (19) | |
O1W | −0.13431 (13) | 0.0929 (2) | −0.26604 (14) | 0.0342 (6) | |
O4'' | −0.03602 (12) | 0.13000 (19) | −0.11388 (13) | 0.0249 (5) | |
O11 | −0.08741 (14) | 0.4592 (2) | 0.10686 (16) | 0.0364 (6) | |
O12 | −0.21217 (13) | 0.4016 (2) | 0.16933 (16) | 0.0373 (6) | |
O13 | −0.15959 (14) | 0.59953 (19) | 0.19927 (14) | 0.0333 (6) | |
O14 | −0.10018 (15) | 0.4256 (2) | 0.26829 (16) | 0.0418 (6) | |
N1 | −0.10757 (14) | 0.0416 (2) | 0.07287 (15) | 0.0191 (5) | |
N4 | 0.06031 (14) | 0.1575 (2) | 0.04446 (15) | 0.0174 (5) | |
N4'' | −0.04112 (16) | 0.3352 (2) | −0.13912 (18) | 0.0292 (6) | |
C2 | −0.08223 (18) | 0.1679 (3) | 0.1021 (2) | 0.0221 (7) | |
H2A | −0.1138 | 0.1932 | 0.1574 | 0.0286 (19)* | |
H2B | −0.0941 | 0.2265 | 0.0509 | 0.0286 (19)* | |
C3 | 0.00716 (17) | 0.1732 (3) | 0.12561 (19) | 0.0198 (6) | |
H3A | 0.0191 | 0.2535 | 0.1552 | 0.0286 (19)* | |
H3B | 0.0196 | 0.1082 | 0.1719 | 0.0286 (19)* | |
C4' | 0.05155 (18) | 0.2586 (3) | −0.02220 (19) | 0.0213 (6) | |
H4'A | 0.1038 | 0.2719 | −0.0539 | 0.0286 (19)* | |
H4'B | 0.0383 | 0.3347 | 0.0124 | 0.0286 (19)* | |
C4'' | −0.01313 (17) | 0.2359 (3) | −0.09541 (18) | 0.0195 (5) | |
C5 | 0.14479 (17) | 0.1499 (3) | 0.07815 (19) | 0.0214 (5) | |
H5A | 0.1466 | 0.0977 | 0.1348 | 0.0286 (19)* | |
H5B | 0.1633 | 0.2332 | 0.0960 | 0.0286 (19)* | |
C6 | 0.20235 (17) | 0.0973 (3) | 0.0059 (2) | 0.0221 (4) | |
H6A | 0.1990 | 0.1482 | −0.0513 | 0.0286 (19)* | |
H6B | 0.2581 | 0.1040 | 0.0305 | 0.0286 (19)* | |
C7 | 0.18652 (16) | −0.0361 (3) | −0.02043 (19) | 0.0203 (4) | |
H7 | 0.1811 | −0.0852 | 0.0383 | 0.0286 (19)* | |
C7' | 0.25457 (18) | −0.0905 (3) | −0.0780 (2) | 0.0319 (8) | |
H7'A | 0.2419 | −0.1762 | −0.0933 | 0.0286 (19)* | |
H7'B | 0.3049 | −0.0872 | −0.0419 | 0.0286 (19)* | |
H7'C | 0.2607 | −0.0432 | −0.1358 | 0.0286 (19)* | |
H1O | −0.1850 | 0.1010 | −0.2446 | 0.0286 (19)* | |
H2O | −0.0981 | 0.1098 | −0.2126 | 0.0286 (19)* | |
H1N | −0.0621 | 0.0199 | 0.0389 | 0.0286 (19)* | |
H2N | −0.1054 | −0.0015 | 0.1244 | 0.0286 (19)* | |
H3N | −0.0810 | 0.3208 | −0.1859 | 0.0286 (19)* | |
H4N | −0.0189 | 0.4118 | −0.1205 | 0.0286 (19)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0234 (4) | 0.0209 (3) | 0.0262 (4) | 0.0003 (3) | −0.0021 (3) | −0.0017 (3) |
O1W | 0.0283 (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) |
O11 | 0.0401 (14) | 0.0278 (13) | 0.0416 (13) | −0.0058 (11) | 0.0160 (11) | −0.0072 (10) |
O12 | 0.0259 (12) | 0.0386 (14) | 0.0472 (14) | −0.0101 (11) | 0.0005 (10) | −0.0089 (11) |
O13 | 0.0443 (15) | 0.0233 (12) | 0.0323 (12) | 0.0057 (11) | −0.0029 (11) | −0.0032 (10) |
O14 | 0.0475 (16) | 0.0356 (14) | 0.0420 (14) | 0.0084 (12) | −0.0193 (12) | 0.0046 (11) |
N1 | 0.0190 (12) | 0.0198 (12) | 0.0185 (11) | 0.0008 (11) | −0.0007 (9) | 0.0007 (10) |
N4 | 0.0175 (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) |
C2 | 0.0256 (16) | 0.0179 (15) | 0.0226 (15) | 0.0010 (13) | 0.0026 (12) | −0.0023 (12) |
C3 | 0.0235 (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) | 0.021 | 0.018 | 0.001 | 0.002 | 0.006 |
C5 | 0.0215 (14) | 0.021 | 0.021 | −0.005 | −0.006 | 0.000 |
C6 | 0.0181 (13) | 0.024 | 0.024 | −0.004 | −0.002 | 0.005 |
C7 | 0.0171 (13) | 0.022 | 0.022 | 0.001 | −0.001 | 0.001 |
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—O14 | 1.429 (2) | N4—C5 | 1.481 (3) |
Cl1—O13 | 1.442 (2) | N4''—C4'' | 1.331 (4) |
Cl1—O11 | 1.440 (2) | C2—C3 | 1.519 (4) |
Cl1—O12 | 1.444 (2) | C4'—C4'' | 1.516 (4) |
O4''—C4'' | 1.241 (3) | C5—C6 | 1.521 (4) |
N1—C2 | 1.495 (4) | C6—C7 | 1.521 (4) |
N1—C7i | 1.507 (3) | C7—C7' | 1.520 (4) |
N4—C3 | 1.471 (3) | C7—N1i | 1.507 (3) |
N4—C4' | 1.463 (3) | | |
| | | |
O14—Cl1—O13 | 109.79 (14) | N4—C3—C2 | 114.0 (2) |
O14—Cl1—O11 | 109.97 (15) | N4—C4'—C4'' | 113.3 (2) |
O13—Cl1—O11 | 109.30 (13) | O4''—C4''—N4'' | 123.2 (3) |
O14—Cl1—O12 | 109.37 (15) | O4''—C4''—C4' | 120.9 (2) |
O13—Cl1—O12 | 109.79 (14) | N4''—C4''—C4' | 115.9 (3) |
O11—Cl1—O12 | 108.60 (14) | N4—C5—C6 | 113.3 (2) |
C2—N1—C7i | 114.7 (2) | C7—C6—C5 | 114.8 (2) |
C4'—N4—C3 | 111.7 (2) | C7'—C7—C6 | 112.2 (2) |
C4'—N4—C5 | 110.2 (2) | C7'—C7—N1i | 111.1 (2) |
C3—N4—C5 | 108.6 (2) | C6—C7—N1i | 108.1 (2) |
N1—C2—C3 | 111.7 (2) | | |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1n···O4′′ | 0.93 | 2.53 | 3.083 (3) | 118 |
N1—H1n···O4′′i | 0.93 | 2.54 | 3.079 (3) | 118 |
O1w—H2o···O4′′ | 0.99 | 1.76 | 2.744 (3) | 176 |
O1w—H1o···O12ii | 0.90 | 2.02 | 2.903 (3) | 166 |
N1—H2n···O1wiii | 0.88 | 1.92 | 2.768 (3) | 163 |
N4′′—H3n···O13iv | 0.95 | 2.27 | 3.110 (4) | 148 |
N4′′—H4n···O11v | 0.95 | 2.26 | 3.122 (4) | 151 |
Symmetry codes: (i) −x, −y, −z; (ii) −x−1/2, −y+1/2, −z; (iii) x, −y, z+1/2; (iv) x, −y+1, z−1/2; (v) −x, −y+1, −z. |
Experimental details
Crystal data |
Chemical formula | C16H36N6O22+·2ClO4−·2H2O |
Mr | 579.43 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 173 |
a, b, c (Å) | 16.576 (3), 10.877 (6), 14.314 (2) |
β (°) | 90.25 (1) |
V (Å3) | 2581 (1) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.32 |
Crystal size (mm) | 0.36 × 0.23 × 0.13 |
|
Data collection |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4647, 2965, 1545 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.130, 0.98 |
No. of reflections | 2965 |
No. of parameters | 144 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.38 |
Selected geometric parameters (Å, º) topO4''—C4'' | 1.241 (3) | N4''—C4'' | 1.331 (4) |
N1—C2 | 1.495 (4) | C2—C3 | 1.519 (4) |
N1—C7i | 1.507 (3) | C4'—C4'' | 1.516 (4) |
N4—C3 | 1.471 (3) | C5—C6 | 1.521 (4) |
N4—C4' | 1.463 (3) | C6—C7 | 1.521 (4) |
N4—C5 | 1.481 (3) | C7—C7' | 1.520 (4) |
| | | |
C2—N1—C7i | 114.7 (2) | O4''—C4''—C4' | 120.9 (2) |
C4'—N4—C3 | 111.7 (2) | N4''—C4''—C4' | 115.9 (3) |
C4'—N4—C5 | 110.2 (2) | N4—C5—C6 | 113.3 (2) |
C3—N4—C5 | 108.6 (2) | C7—C6—C5 | 114.8 (2) |
N1—C2—C3 | 111.7 (2) | C7'—C7—C6 | 112.2 (2) |
N4—C3—C2 | 114.0 (2) | C7'—C7—N1i | 111.1 (2) |
N4—C4'—C4'' | 113.3 (2) | C6—C7—N1i | 108.1 (2) |
O4''—C4''—N4'' | 123.2 (3) | | |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1n···O4'' | 0.93 | 2.53 | 3.083 (3) | 118 |
N1—H1n···O4''i | 0.93 | 2.54 | 3.079 (3) | 118 |
O1w—H2o···O4'' | 0.99 | 1.76 | 2.744 (3) | 176 |
O1w—H1o···O12ii | 0.90 | 2.02 | 2.903 (3) | 166 |
N1—H2n···O1wiii | 0.88 | 1.92 | 2.768 (3) | 163 |
N4''—H3n···O13iv | 0.95 | 2.27 | 3.110 (4) | 148 |
N4''—H4n···O11v | 0.95 | 2.26 | 3.122 (4) | 151 |
Symmetry codes: (i) −x, −y, −z; (ii) −x−1/2, −y+1/2, −z; (iii) x, −y, z+1/2; (iv) x, −y+1, z−1/2; (v) −x, −y+1, −z. |
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.