The benzoannelated diazapolyether macrocycles 6,7,9,10,17,18-hexahydro-5H,11H-8,16,19-trioxa-5,11-diazadibenzo[a,g]cyclopentadecene, C18H22N2O3, (I), 6,7,9,10,12,13,20,21-octahydro-5H,14H-8,11,19,22-tetraoxa-5,14-diazadibenzo[a,g]cyclooctadecene, C20H26N2O4, (II), and 6,7,9,10,17,18,20,21-octahydro-16H,22H-5,8,11,19-tetraoxa-16,22-diazadibenzo[a,j]cyclooctadecene 0.3-hydrate, C20H26N2O4·0.304H2O, (III), show different patterns of hydrogen bonding. In (I), the amine H atoms participate only in intramolecular hydrogen bonds with ether O atoms. In (II), the amine H atoms form intramolecular hydrogen bonds with the phenoxy ether O atoms and intermolecular hydrogen bonds with alkyl ether O atoms in an adjacent molecule, forming a chain linking the macrocycles together via an R22(10) motif. Molecules of (II) were found on a crystallographic twofold axis. In (III), the amine H atoms participate in a hydrogen-bond network with adjacent ether O atoms and with a water molecule [having a partial occupancy of 0.304 (6)] that links the molecules together via a C22(7) motif.
Supporting information
CCDC references: 655500; 655501; 655502
Monocyclic diamines (I), (II) and (III) were prepared by condensation of the
appropriate α,ω-polyoxadianiline with the corresponding diacid chloride
ether under high-dilution conditions (Dietrich et al., 1973) according
to reported methods (Lockhart & Thompson, 1977; Aguilar et al., 2001;
Formanovskii & Murakhovskaya, 1985; Formanovskii et al., 1988; Crossley
et al., 1994). The resulting dilactams were purified by
recrystallization from ethanol [for (I) and (II)] or benzene/toluene [for
(III)] (Smith et al., 2006). Reduction of the dilactams using BH3 in
THF and subsequent work-up (Smith et al., 1986, 1988) gave the title
compounds. Compound (I) was obtained in 58% overall yield; ESI–MS:
m/z = 315.2 (M+H+), 337.2 (M+Na+), 651.4
(2M+Na+). Compound (II) was obtained in 51% overall yield; ESI–MS:
m/z = 359.2 (M+H+), 381.2 (M+Na+). Compound
(III) was obtained in 70% overall yield; ESI–MS: m/z = 359.2
(M+H+), 381.2 (M+Na+). 1H NMR spectra were consistent with
previously reported values for (I) (Formanovskii & Murakhovskaya, 1985) and
(III) (Aguilar et al., 2001). Crystals suitable for X-ray
crystallographic analysis were grown by vapor diffusion of heptane into a
solution of (I) in benzene, by vapor diffusion of water into a solution of
(II) in benzene, and by slow evaporation of a solution of (III) in methanol.
H atoms attached to C were positioned geometrically and refined using a riding
model, with C—H distances of 0.95 (phenyl) or 0.99 Å (ethylene). H atoms
attached to N or O atoms were located initially in a difference map and
refined independently in (I) and (II) and with distances restraints applied
in (III). The Uiso(H) parameters for all H atoms were set to
1.2Ueq(C,N,O). The water O atom in (III) was located in
a difference map. After initial refinements that lead to an implausibly large
displacement parameter for this O atom, the occupancy of the atom was refined
with a fixed displacement parameter. After a converged refinement with both
occupancy and isotropic displacement parameter for the water O atom, a
difference map revealed two peaks in chemically reasonable positions for the H
atoms. The positional parameters of the water H atoms were restrained to be
0.82 (2) Å and have a nearly tetrahedral angle in the molecule. The N—H
bonds in (III) were restrained to be 0.85 (2) Å. One polar axis restraint for
(III) was applied in the manner of Flack & Schwarzenbach (1988).
For all compounds, data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
(I) 6,7,9,10,17,18-hexahydro-5H,11
H-8,16,19-trioxa-5,11-
diazadibenzo[a,g]cyclopentadecene
top
Crystal data top
C18H22N2O3 | F(000) = 672 |
Mr = 314.38 | Dx = 1.316 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 5823 reflections |
a = 7.8995 (8) Å | θ = 3.2–26.9° |
b = 9.5228 (10) Å | µ = 0.09 mm−1 |
c = 21.093 (2) Å | T = 100 K |
V = 1586.7 (3) Å3 | Prism, colourless |
Z = 4 | 0.32 × 0.26 × 0.20 mm |
Data collection top
Bruker APEX CCD diffractometer | 1809 independent reflections |
Radiation source: fine-focus sealed tube | 1788 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.014 |
ω scans | θmax = 26.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −9→9 |
Tmin = 0.971, Tmax = 0.984 | k = −11→11 |
16397 measured reflections | l = −25→25 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.026 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.071 | w = 1/[σ2(Fo2) + (0.048P)2 + 0.240P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
1809 reflections | Δρmax = 0.17 e Å−3 |
215 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.017 (2) |
Crystal data top
C18H22N2O3 | V = 1586.7 (3) Å3 |
Mr = 314.38 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.8995 (8) Å | µ = 0.09 mm−1 |
b = 9.5228 (10) Å | T = 100 K |
c = 21.093 (2) Å | 0.32 × 0.26 × 0.20 mm |
Data collection top
Bruker APEX CCD diffractometer | 1809 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 1788 reflections with I > 2σ(I) |
Tmin = 0.971, Tmax = 0.984 | Rint = 0.014 |
16397 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.17 e Å−3 |
1809 reflections | Δρmin = −0.18 e Å−3 |
215 parameters | |
Special details top
Experimental. All intensity X-ray data were collected on a Bruker diffractometer with a D8
goniometer, an APEX CCD detector, a sealed-tube Mo Kα source, and an
Oxford Cryosystems Cryostream 700 low temperature device (Bruker, 1998). |
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. Although the Flack parameter was refined, the lack of a strong anomalous scatter
makes this parameter inappropriate. The Friedel related data were merged. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.34334 (19) | 0.51249 (16) | 0.31794 (7) | 0.0241 (3) | |
H1 | 0.2496 | 0.4506 | 0.3140 | 0.029* | |
C2 | 0.3866 (2) | 0.60177 (16) | 0.26794 (7) | 0.0267 (3) | |
H2 | 0.3225 | 0.6010 | 0.2298 | 0.032* | |
C3 | 0.5232 (2) | 0.69111 (16) | 0.27429 (7) | 0.0268 (3) | |
H3 | 0.5529 | 0.7514 | 0.2402 | 0.032* | |
C4 | 0.6182 (2) | 0.69411 (16) | 0.33005 (7) | 0.0248 (3) | |
H4 | 0.7115 | 0.7565 | 0.3336 | 0.030* | |
N5 | 0.66061 (16) | 0.60605 (13) | 0.43879 (6) | 0.0220 (3) | |
H5 | 0.635 (2) | 0.531 (2) | 0.4616 (8) | 0.026* | |
C6 | 0.83714 (19) | 0.64872 (16) | 0.44346 (7) | 0.0258 (3) | |
H6A | 0.8511 | 0.7450 | 0.4266 | 0.031* | |
H6B | 0.9091 | 0.5845 | 0.4182 | 0.031* | |
C7 | 0.8900 (2) | 0.64430 (16) | 0.51234 (7) | 0.0264 (3) | |
H7A | 1.0123 | 0.6652 | 0.5163 | 0.032* | |
H7B | 0.8261 | 0.7152 | 0.5369 | 0.032* | |
O8 | 0.85488 (13) | 0.50656 (10) | 0.53601 (5) | 0.0231 (2) | |
C9 | 0.87951 (19) | 0.49346 (17) | 0.60301 (7) | 0.0254 (3) | |
H9A | 0.9929 | 0.5302 | 0.6142 | 0.031* | |
H9B | 0.8761 | 0.3929 | 0.6148 | 0.031* | |
C10 | 0.74524 (18) | 0.57277 (16) | 0.64093 (7) | 0.0248 (3) | |
H10A | 0.7635 | 0.5549 | 0.6867 | 0.030* | |
H10B | 0.7595 | 0.6748 | 0.6336 | 0.030* | |
N11 | 0.57172 (16) | 0.53277 (14) | 0.62434 (6) | 0.0221 (3) | |
H11 | 0.549 (2) | 0.551 (2) | 0.5837 (8) | 0.027* | |
C12 | 0.55390 (18) | 0.33648 (16) | 0.70008 (7) | 0.0223 (3) | |
H12 | 0.6409 | 0.3763 | 0.7254 | 0.027* | |
C13 | 0.47728 (19) | 0.21172 (15) | 0.71933 (6) | 0.0237 (3) | |
H13 | 0.5124 | 0.1674 | 0.7575 | 0.028* | |
C14 | 0.3503 (2) | 0.15238 (15) | 0.68306 (6) | 0.0236 (3) | |
H14 | 0.2986 | 0.0671 | 0.6961 | 0.028* | |
C15 | 0.29838 (19) | 0.21812 (15) | 0.62724 (6) | 0.0217 (3) | |
H15 | 0.2100 | 0.1782 | 0.6026 | 0.026* | |
O16 | 0.33415 (14) | 0.41261 (10) | 0.55285 (4) | 0.0218 (2) | |
C17 | 0.23723 (18) | 0.33597 (15) | 0.50683 (6) | 0.0198 (3) | |
H17A | 0.1197 | 0.3231 | 0.5220 | 0.024* | |
H17B | 0.2879 | 0.2422 | 0.4998 | 0.024* | |
C18 | 0.23809 (17) | 0.41882 (15) | 0.44624 (6) | 0.0209 (3) | |
H18A | 0.1632 | 0.3738 | 0.4146 | 0.025* | |
H18B | 0.1966 | 0.5154 | 0.4541 | 0.025* | |
O19 | 0.40834 (12) | 0.42266 (11) | 0.42325 (5) | 0.0229 (2) | |
C20 | 0.43795 (18) | 0.51466 (15) | 0.37326 (7) | 0.0210 (3) | |
C21 | 0.57665 (17) | 0.60541 (15) | 0.38088 (7) | 0.0206 (3) | |
C22 | 0.50516 (18) | 0.40398 (14) | 0.64422 (6) | 0.0196 (3) | |
C23 | 0.37543 (18) | 0.34158 (14) | 0.60772 (6) | 0.0195 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0235 (7) | 0.0238 (7) | 0.0251 (7) | 0.0028 (6) | 0.0005 (6) | 0.0012 (6) |
C2 | 0.0296 (7) | 0.0274 (7) | 0.0232 (7) | 0.0083 (7) | 0.0008 (6) | 0.0027 (6) |
C3 | 0.0302 (8) | 0.0251 (7) | 0.0251 (7) | 0.0079 (7) | 0.0085 (6) | 0.0056 (6) |
C4 | 0.0239 (7) | 0.0206 (7) | 0.0299 (7) | 0.0026 (6) | 0.0063 (6) | 0.0021 (6) |
N5 | 0.0204 (6) | 0.0201 (6) | 0.0254 (6) | −0.0007 (5) | 0.0019 (5) | 0.0006 (5) |
C6 | 0.0226 (7) | 0.0255 (7) | 0.0293 (7) | −0.0055 (6) | 0.0024 (6) | −0.0022 (6) |
C7 | 0.0251 (7) | 0.0232 (7) | 0.0309 (7) | −0.0065 (7) | 0.0016 (6) | −0.0049 (6) |
O8 | 0.0236 (5) | 0.0216 (5) | 0.0242 (5) | −0.0016 (4) | −0.0022 (4) | −0.0043 (4) |
C9 | 0.0215 (7) | 0.0288 (8) | 0.0260 (7) | −0.0012 (6) | −0.0049 (6) | −0.0040 (6) |
C10 | 0.0241 (7) | 0.0247 (7) | 0.0256 (7) | −0.0061 (7) | −0.0011 (6) | −0.0048 (6) |
N11 | 0.0224 (6) | 0.0208 (6) | 0.0232 (6) | −0.0031 (5) | −0.0020 (5) | −0.0006 (5) |
C12 | 0.0202 (6) | 0.0251 (7) | 0.0215 (6) | 0.0018 (6) | −0.0025 (5) | −0.0046 (6) |
C13 | 0.0268 (8) | 0.0248 (7) | 0.0196 (6) | 0.0047 (7) | −0.0004 (6) | 0.0005 (6) |
C14 | 0.0281 (7) | 0.0197 (7) | 0.0232 (6) | −0.0022 (6) | 0.0036 (6) | −0.0005 (5) |
C15 | 0.0221 (7) | 0.0217 (6) | 0.0211 (6) | −0.0032 (6) | −0.0003 (5) | −0.0028 (6) |
O16 | 0.0270 (5) | 0.0191 (5) | 0.0194 (5) | −0.0040 (4) | −0.0046 (4) | −0.0002 (4) |
C17 | 0.0174 (6) | 0.0232 (7) | 0.0189 (6) | −0.0035 (6) | −0.0006 (5) | −0.0019 (5) |
C18 | 0.0157 (6) | 0.0246 (7) | 0.0224 (6) | −0.0001 (6) | −0.0007 (5) | 0.0006 (6) |
O19 | 0.0171 (5) | 0.0268 (5) | 0.0249 (5) | 0.0016 (4) | 0.0019 (4) | 0.0079 (4) |
C20 | 0.0210 (7) | 0.0193 (6) | 0.0228 (6) | 0.0047 (6) | 0.0038 (5) | 0.0027 (6) |
C21 | 0.0203 (6) | 0.0179 (6) | 0.0236 (6) | 0.0058 (6) | 0.0051 (5) | −0.0014 (5) |
C22 | 0.0181 (6) | 0.0183 (6) | 0.0225 (6) | 0.0006 (6) | 0.0024 (5) | −0.0048 (5) |
C23 | 0.0214 (7) | 0.0188 (6) | 0.0183 (6) | 0.0027 (6) | −0.0001 (5) | −0.0030 (5) |
Geometric parameters (Å, º) top
C1—C20 | 1.386 (2) | C10—H10B | 0.9900 |
C1—C2 | 1.397 (2) | N11—C22 | 1.3988 (19) |
C1—H1 | 0.9500 | N11—H11 | 0.893 (17) |
C2—C3 | 1.380 (2) | C12—C13 | 1.394 (2) |
C2—H2 | 0.9500 | C12—C22 | 1.396 (2) |
C3—C4 | 1.396 (2) | C12—H12 | 0.9500 |
C3—H3 | 0.9500 | C13—C14 | 1.382 (2) |
C4—C21 | 1.4037 (19) | C13—H13 | 0.9500 |
C4—H4 | 0.9500 | C14—C15 | 1.395 (2) |
N5—C21 | 1.3900 (18) | C14—H14 | 0.9500 |
N5—C6 | 1.4558 (19) | C15—C23 | 1.386 (2) |
N5—H5 | 0.887 (19) | C15—H15 | 0.9500 |
C6—C7 | 1.512 (2) | O16—C23 | 1.3796 (16) |
C6—H6A | 0.9900 | O16—C17 | 1.4357 (16) |
C6—H6B | 0.9900 | C17—C18 | 1.5018 (18) |
C7—O8 | 1.4306 (18) | C17—H17A | 0.9900 |
C7—H7A | 0.9900 | C17—H17B | 0.9900 |
C7—H7B | 0.9900 | C18—O19 | 1.4301 (16) |
O8—C9 | 1.4319 (17) | C18—H18A | 0.9900 |
C9—C10 | 1.528 (2) | C18—H18B | 0.9900 |
C9—H9A | 0.9900 | O19—C20 | 1.3906 (17) |
C9—H9B | 0.9900 | C20—C21 | 1.405 (2) |
C10—N11 | 1.4651 (18) | C22—C23 | 1.4129 (19) |
C10—H10A | 0.9900 | | |
| | | |
C20—C1—C2 | 119.63 (14) | C22—N11—H11 | 112.7 (12) |
C20—C1—H1 | 120.2 | C10—N11—H11 | 111.5 (12) |
C2—C1—H1 | 120.2 | C13—C12—C22 | 121.23 (14) |
C3—C2—C1 | 119.55 (14) | C13—C12—H12 | 119.4 |
C3—C2—H2 | 120.2 | C22—C12—H12 | 119.4 |
C1—C2—H2 | 120.2 | C14—C13—C12 | 120.16 (13) |
C2—C3—C4 | 120.97 (13) | C14—C13—H13 | 119.9 |
C2—C3—H3 | 119.5 | C12—C13—H13 | 119.9 |
C4—C3—H3 | 119.5 | C13—C14—C15 | 119.81 (13) |
C3—C4—C21 | 120.38 (14) | C13—C14—H14 | 120.1 |
C3—C4—H4 | 119.8 | C15—C14—H14 | 120.1 |
C21—C4—H4 | 119.8 | C23—C15—C14 | 120.13 (13) |
C21—N5—C6 | 121.18 (12) | C23—C15—H15 | 119.9 |
C21—N5—H5 | 111.5 (12) | C14—C15—H15 | 119.9 |
C6—N5—H5 | 113.8 (12) | C23—O16—C17 | 116.36 (10) |
N5—C6—C7 | 108.76 (12) | O16—C17—C18 | 107.81 (11) |
N5—C6—H6A | 109.9 | O16—C17—H17A | 110.1 |
C7—C6—H6A | 109.9 | C18—C17—H17A | 110.1 |
N5—C6—H6B | 109.9 | O16—C17—H17B | 110.1 |
C7—C6—H6B | 109.9 | C18—C17—H17B | 110.1 |
H6A—C6—H6B | 108.3 | H17A—C17—H17B | 108.5 |
O8—C7—C6 | 107.91 (12) | O19—C18—C17 | 107.84 (11) |
O8—C7—H7A | 110.1 | O19—C18—H18A | 110.1 |
C6—C7—H7A | 110.1 | C17—C18—H18A | 110.1 |
O8—C7—H7B | 110.1 | O19—C18—H18B | 110.1 |
C6—C7—H7B | 110.1 | C17—C18—H18B | 110.1 |
H7A—C7—H7B | 108.4 | H18A—C18—H18B | 108.5 |
C7—O8—C9 | 113.46 (11) | C20—O19—C18 | 115.56 (10) |
O8—C9—C10 | 112.28 (12) | C1—C20—O19 | 122.57 (13) |
O8—C9—H9A | 109.1 | C1—C20—C21 | 121.74 (13) |
C10—C9—H9A | 109.1 | O19—C20—C21 | 115.60 (12) |
O8—C9—H9B | 109.1 | N5—C21—C4 | 123.85 (13) |
C10—C9—H9B | 109.1 | N5—C21—C20 | 118.38 (13) |
H9A—C9—H9B | 107.9 | C4—C21—C20 | 117.73 (13) |
N11—C10—C9 | 113.32 (12) | C12—C22—N11 | 123.57 (13) |
N11—C10—H10A | 108.9 | C12—C22—C23 | 117.79 (13) |
C9—C10—H10A | 108.9 | N11—C22—C23 | 118.56 (13) |
N11—C10—H10B | 108.9 | O16—C23—C15 | 124.14 (12) |
C9—C10—H10B | 108.9 | O16—C23—C22 | 114.99 (12) |
H10A—C10—H10B | 107.7 | C15—C23—C22 | 120.88 (13) |
C22—N11—C10 | 120.53 (13) | | |
| | | |
C20—C1—C2—C3 | 0.0 (2) | C6—N5—C21—C20 | 154.70 (13) |
C1—C2—C3—C4 | −0.3 (2) | C3—C4—C21—N5 | −177.33 (13) |
C2—C3—C4—C21 | 0.2 (2) | C3—C4—C21—C20 | 0.2 (2) |
C21—N5—C6—C7 | 177.61 (13) | C1—C20—C21—N5 | 177.12 (13) |
N5—C6—C7—O8 | 55.00 (15) | O19—C20—C21—N5 | −6.27 (18) |
C6—C7—O8—C9 | −172.63 (12) | C1—C20—C21—C4 | −0.5 (2) |
C7—O8—C9—C10 | 70.25 (16) | O19—C20—C21—C4 | 176.07 (12) |
O8—C9—C10—N11 | 54.75 (17) | C13—C12—C22—N11 | 176.67 (13) |
C9—C10—N11—C22 | 74.11 (17) | C13—C12—C22—C23 | 0.0 (2) |
C22—C12—C13—C14 | −0.1 (2) | C10—N11—C22—C12 | 30.1 (2) |
C12—C13—C14—C15 | −0.3 (2) | C10—N11—C22—C23 | −153.20 (13) |
C13—C14—C15—C23 | 0.9 (2) | C17—O16—C23—C15 | −15.83 (19) |
C23—O16—C17—C18 | −168.02 (11) | C17—O16—C23—C22 | 164.22 (12) |
O16—C17—C18—O19 | 65.29 (14) | C14—C15—C23—O16 | 179.01 (13) |
C17—C18—O19—C20 | −169.60 (11) | C14—C15—C23—C22 | −1.0 (2) |
C2—C1—C20—O19 | −175.91 (13) | C12—C22—C23—O16 | −179.44 (12) |
C2—C1—C20—C21 | 0.5 (2) | N11—C22—C23—O16 | 3.68 (18) |
C18—O19—C20—C1 | −53.32 (18) | C12—C22—C23—C15 | 0.6 (2) |
C18—O19—C20—C21 | 130.10 (13) | N11—C22—C23—C15 | −176.28 (12) |
C6—N5—C21—C4 | −27.8 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···O8 | 0.887 (19) | 2.349 (18) | 2.7310 (16) | 106.0 (14) |
N5—H5···O19 | 0.887 (19) | 2.220 (19) | 2.6699 (17) | 111.0 (14) |
N11—H11···O16 | 0.893 (17) | 2.246 (18) | 2.6655 (16) | 108.3 (14) |
(II) 6,7,9,10,12,13,20,21-octahydro-5H,14
H-8,11,19,22-tetraoxa-
5,14-diazadibenzo[a,g]cyclooctadecene
top
Crystal data top
C20H26N2O4 | F(000) = 768 |
Mr = 358.43 | Dx = 1.272 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 5690 reflections |
a = 11.837 (2) Å | θ = 2.1–26.4° |
b = 18.116 (3) Å | µ = 0.09 mm−1 |
c = 9.2565 (18) Å | T = 120 K |
β = 109.485 (5)° | Prism, colourless |
V = 1871.3 (6) Å3 | 0.28 × 0.18 × 0.14 mm |
Z = 4 | |
Data collection top
Bruker APEX CCD diffractometer | 1839 independent reflections |
Radiation source: fine-focus sealed tube | 1726 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ω scans | θmax = 26.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −14→14 |
Tmin = 0.973, Tmax = 0.989 | k = −22→22 |
9314 measured reflections | l = −11→11 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.091 | w = 1/[σ2(Fo2) + (0.054P)2 + 1.P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
1839 reflections | Δρmax = 0.24 e Å−3 |
122 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0083 (10) |
Crystal data top
C20H26N2O4 | V = 1871.3 (6) Å3 |
Mr = 358.43 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 11.837 (2) Å | µ = 0.09 mm−1 |
b = 18.116 (3) Å | T = 120 K |
c = 9.2565 (18) Å | 0.28 × 0.18 × 0.14 mm |
β = 109.485 (5)° | |
Data collection top
Bruker APEX CCD diffractometer | 1839 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 1726 reflections with I > 2σ(I) |
Tmin = 0.973, Tmax = 0.989 | Rint = 0.018 |
9314 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.24 e Å−3 |
1839 reflections | Δρmin = −0.21 e Å−3 |
122 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.18564 (9) | 0.31043 (6) | 0.63215 (11) | 0.0262 (2) | |
H1 | 0.2085 | 0.2682 | 0.6961 | 0.031* | |
C2 | 0.06692 (10) | 0.33518 (6) | 0.58493 (12) | 0.0302 (3) | |
H2 | 0.0092 | 0.3101 | 0.6177 | 0.036* | |
C3 | 0.03388 (9) | 0.39600 (6) | 0.49067 (13) | 0.0300 (3) | |
H3 | −0.0468 | 0.4127 | 0.4585 | 0.036* | |
C4 | 0.11801 (9) | 0.43320 (6) | 0.44222 (12) | 0.0254 (2) | |
H4 | 0.0939 | 0.4750 | 0.3772 | 0.030* | |
N5 | 0.32358 (8) | 0.44260 (5) | 0.44061 (10) | 0.0237 (2) | |
H5 | 0.3953 (12) | 0.4283 (7) | 0.4856 (14) | 0.028* | |
C6 | 0.30872 (9) | 0.51483 (6) | 0.36939 (11) | 0.0250 (2) | |
H6A | 0.2312 | 0.5161 | 0.2844 | 0.030* | |
H6B | 0.3731 | 0.5224 | 0.3247 | 0.030* | |
C7 | 0.31192 (9) | 0.57776 (6) | 0.47855 (12) | 0.0258 (2) | |
H7A | 0.2899 | 0.6246 | 0.4208 | 0.031* | |
H7B | 0.2536 | 0.5685 | 0.5322 | 0.031* | |
O8 | 0.42944 (6) | 0.58316 (4) | 0.58670 (8) | 0.0255 (2) | |
C9 | 0.43885 (10) | 0.64274 (6) | 0.68967 (12) | 0.0280 (3) | |
H9A | 0.3767 | 0.6379 | 0.7389 | 0.034* | |
H9B | 0.4256 | 0.6900 | 0.6328 | 0.034* | |
C21 | 0.43311 (9) | 0.26993 (5) | 0.73029 (11) | 0.0239 (2) | |
H21A | 0.3988 | 0.2227 | 0.6812 | 0.029* | |
H21B | 0.4113 | 0.2766 | 0.8238 | 0.029* | |
O22 | 0.38886 (6) | 0.33012 (4) | 0.62683 (8) | 0.0249 (2) | |
C23 | 0.26966 (9) | 0.34751 (5) | 0.58562 (10) | 0.0216 (2) | |
C24 | 0.23705 (8) | 0.40991 (5) | 0.48789 (11) | 0.0208 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0311 (5) | 0.0257 (5) | 0.0206 (5) | −0.0069 (4) | 0.0070 (4) | −0.0027 (4) |
C2 | 0.0293 (5) | 0.0345 (6) | 0.0308 (5) | −0.0102 (4) | 0.0152 (4) | −0.0074 (4) |
C3 | 0.0223 (5) | 0.0325 (6) | 0.0362 (6) | −0.0007 (4) | 0.0109 (4) | −0.0081 (4) |
C4 | 0.0232 (5) | 0.0245 (5) | 0.0270 (5) | 0.0013 (4) | 0.0063 (4) | −0.0027 (4) |
N5 | 0.0197 (4) | 0.0242 (5) | 0.0263 (4) | 0.0023 (3) | 0.0066 (3) | 0.0044 (3) |
C6 | 0.0247 (5) | 0.0266 (5) | 0.0227 (5) | 0.0004 (4) | 0.0064 (4) | 0.0057 (4) |
C7 | 0.0237 (5) | 0.0240 (5) | 0.0288 (5) | 0.0032 (4) | 0.0074 (4) | 0.0066 (4) |
O8 | 0.0238 (4) | 0.0258 (4) | 0.0266 (4) | 0.0008 (3) | 0.0081 (3) | −0.0013 (3) |
C9 | 0.0356 (6) | 0.0218 (5) | 0.0277 (5) | 0.0032 (4) | 0.0121 (5) | 0.0019 (4) |
C21 | 0.0290 (6) | 0.0183 (5) | 0.0202 (5) | −0.0010 (4) | 0.0027 (4) | 0.0013 (4) |
O22 | 0.0218 (4) | 0.0231 (4) | 0.0258 (4) | −0.0008 (3) | 0.0026 (3) | 0.0053 (3) |
C23 | 0.0222 (5) | 0.0223 (5) | 0.0179 (4) | −0.0024 (4) | 0.0035 (4) | −0.0047 (3) |
C24 | 0.0219 (5) | 0.0217 (5) | 0.0182 (4) | −0.0015 (4) | 0.0057 (4) | −0.0041 (4) |
Geometric parameters (Å, º) top
C1—C23 | 1.3826 (14) | C6—H6B | 0.9900 |
C1—C2 | 1.3990 (15) | C7—O8 | 1.4205 (12) |
C1—H1 | 0.9500 | C7—H7A | 0.9900 |
C2—C3 | 1.3786 (16) | C7—H7B | 0.9900 |
C2—H2 | 0.9500 | O8—C9 | 1.4196 (12) |
C3—C4 | 1.3946 (15) | C9—C9i | 1.505 (2) |
C3—H3 | 0.9500 | C9—H9A | 0.9900 |
C4—C24 | 1.3946 (14) | C9—H9B | 0.9900 |
C4—H4 | 0.9500 | C21—O22 | 1.4303 (11) |
N5—C24 | 1.3749 (13) | C21—C21i | 1.502 (2) |
N5—C6 | 1.4493 (13) | C21—H21A | 0.9900 |
N5—H5 | 0.851 (14) | C21—H21B | 0.9900 |
C6—C7 | 1.5155 (14) | O22—C23 | 1.3699 (12) |
C6—H6A | 0.9900 | C23—C24 | 1.4185 (14) |
| | | |
C23—C1—C2 | 119.93 (10) | O8—C7—H7B | 109.9 |
C23—C1—H1 | 120.0 | C6—C7—H7B | 109.9 |
C2—C1—H1 | 120.0 | H7A—C7—H7B | 108.3 |
C3—C2—C1 | 119.81 (9) | C9—O8—C7 | 111.39 (8) |
C3—C2—H2 | 120.1 | O8—C9—C9i | 109.81 (8) |
C1—C2—H2 | 120.1 | O8—C9—H9A | 109.7 |
C2—C3—C4 | 120.50 (10) | C9i—C9—H9A | 109.7 |
C2—C3—H3 | 119.8 | O8—C9—H9B | 109.7 |
C4—C3—H3 | 119.8 | C9i—C9—H9B | 109.7 |
C24—C4—C3 | 120.93 (10) | H9A—C9—H9B | 108.2 |
C24—C4—H4 | 119.5 | O22—C21—C21i | 106.48 (7) |
C3—C4—H4 | 119.5 | O22—C21—H21A | 110.4 |
C24—N5—C6 | 122.91 (8) | C21i—C21—H21A | 110.4 |
C24—N5—H5 | 116.1 (9) | O22—C21—H21B | 110.4 |
C6—N5—H5 | 116.6 (9) | C21i—C21—H21B | 110.4 |
N5—C6—C7 | 113.81 (8) | H21A—C21—H21B | 108.6 |
N5—C6—H6A | 108.8 | C23—O22—C21 | 118.35 (8) |
C7—C6—H6A | 108.8 | O22—C23—C1 | 125.63 (9) |
N5—C6—H6B | 108.8 | O22—C23—C24 | 113.38 (8) |
C7—C6—H6B | 108.8 | C1—C23—C24 | 120.99 (9) |
H6A—C6—H6B | 107.7 | N5—C24—C4 | 123.91 (9) |
O8—C7—C6 | 108.81 (8) | N5—C24—C23 | 118.23 (9) |
O8—C7—H7A | 109.9 | C4—C24—C23 | 117.83 (9) |
C6—C7—H7A | 109.9 | | |
| | | |
C23—C1—C2—C3 | 0.74 (15) | C2—C1—C23—O22 | 178.24 (9) |
C1—C2—C3—C4 | −0.14 (15) | C2—C1—C23—C24 | −1.14 (15) |
C2—C3—C4—C24 | −0.06 (15) | C6—N5—C24—C4 | 15.54 (15) |
C24—N5—C6—C7 | 70.84 (12) | C6—N5—C24—C23 | −166.26 (9) |
N5—C6—C7—O8 | 67.58 (10) | C3—C4—C24—N5 | 177.90 (9) |
C6—C7—O8—C9 | 178.31 (8) | C3—C4—C24—C23 | −0.31 (14) |
C7—O8—C9—C9i | 175.21 (9) | O22—C23—C24—N5 | 3.15 (12) |
C21i—C21—O22—C23 | −173.01 (8) | C1—C23—C24—N5 | −177.40 (9) |
C21—O22—C23—C1 | −1.91 (14) | O22—C23—C24—C4 | −178.54 (8) |
C21—O22—C23—C24 | 177.52 (8) | C1—C23—C24—C4 | 0.91 (14) |
Symmetry code: (i) −x+1, y, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···O8ii | 0.851 (14) | 2.392 (13) | 3.0530 (12) | 134.9 (11) |
N5—H5···O22 | 0.851 (14) | 2.223 (13) | 2.6138 (11) | 107.9 (10) |
Symmetry code: (ii) −x+1, −y+1, −z+1. |
(III) 6,7,9,10,17,18,20,21-octahydro-16H,22
H-5,8,11,19-tetraoxa-16,22-
diazadibenzo[a,j]cyclooctadecene 0.3-hydrate
top
Crystal data top
C20H26N2O4·0.304H2O | F(000) = 390 |
Mr = 363.92 | Dx = 1.287 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 13.507 (8) Å | Cell parameters from 972 reflections |
b = 5.133 (3) Å | θ = 2.6–24.6° |
c = 14.644 (8) Å | µ = 0.09 mm−1 |
β = 112.336 (9)° | T = 100 K |
V = 939.1 (9) Å3 | Needle, colourless |
Z = 2 | 0.22 × 0.05 × 0.04 mm |
Data collection top
Bruker APEX CCD diffractometer | 2037 independent reflections |
Radiation source: fine-focus sealed tube | 1223 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
ω scans | θmax = 26.0°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −16→16 |
Tmin = 0.979, Tmax = 0.997 | k = −5→6 |
4546 measured reflections | l = −18→14 |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.032P)2] where P = (Fo2 + 2Fc2)/3 |
2037 reflections | (Δ/σ)max < 0.001 |
257 parameters | Δρmax = 0.23 e Å−3 |
6 restraints | Δρmin = −0.20 e Å−3 |
Crystal data top
C20H26N2O4·0.304H2O | V = 939.1 (9) Å3 |
Mr = 363.92 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 13.507 (8) Å | µ = 0.09 mm−1 |
b = 5.133 (3) Å | T = 100 K |
c = 14.644 (8) Å | 0.22 × 0.05 × 0.04 mm |
β = 112.336 (9)° | |
Data collection top
Bruker APEX CCD diffractometer | 2037 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 1223 reflections with I > 2σ(I) |
Tmin = 0.979, Tmax = 0.997 | Rint = 0.064 |
4546 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 6 restraints |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.23 e Å−3 |
2037 reflections | Δρmin = −0.20 e Å−3 |
257 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. Although the Flack parameter was refined, the lack of a strong anomalous scatter
makes this parameter inappropriate. The Friedel related data were merged. Restraints on the N—H and O—H distances were required. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.6694 (4) | 0.2589 (10) | 1.1212 (3) | 0.0355 (13) | |
H1 | 0.6153 | 0.1293 | 1.0987 | 0.043* | |
C2 | 0.7342 (4) | 0.2733 (10) | 1.2211 (3) | 0.0357 (13) | |
H2 | 0.7242 | 0.1539 | 1.2664 | 0.043* | |
C3 | 0.8125 (4) | 0.4597 (11) | 1.2542 (3) | 0.0340 (13) | |
H3 | 0.8563 | 0.4701 | 1.3224 | 0.041* | |
C4 | 0.8282 (4) | 0.6343 (10) | 1.1877 (3) | 0.0331 (13) | |
H4 | 0.8827 | 0.7628 | 1.2106 | 0.040* | |
O5 | 0.7732 (2) | 0.7817 (6) | 1.0176 (2) | 0.0330 (8) | |
C6 | 0.8615 (3) | 0.9623 (10) | 1.0469 (3) | 0.0284 (12) | |
H6A | 0.9301 | 0.8671 | 1.0757 | 0.034* | |
H6B | 0.8562 | 1.0844 | 1.0972 | 0.034* | |
C7 | 0.8565 (4) | 1.1092 (10) | 0.9569 (3) | 0.0296 (12) | |
H7A | 0.7837 | 1.1807 | 0.9223 | 0.036* | |
H7B | 0.9077 | 1.2562 | 0.9762 | 0.036* | |
O8 | 0.8825 (2) | 0.9370 (7) | 0.89319 (19) | 0.0329 (8) | |
C9 | 0.8712 (4) | 1.0595 (9) | 0.8038 (3) | 0.0264 (12) | |
H9A | 0.9166 | 1.2175 | 0.8174 | 0.032* | |
H9B | 0.7958 | 1.1131 | 0.7684 | 0.032* | |
C10 | 0.9037 (3) | 0.8757 (9) | 0.7409 (3) | 0.0260 (12) | |
H10A | 0.9174 | 0.9730 | 0.6885 | 0.031* | |
H10B | 0.9701 | 0.7829 | 0.7816 | 0.031* | |
O11 | 0.8187 (2) | 0.6939 (6) | 0.6979 (2) | 0.0315 (8) | |
C12 | 0.9164 (4) | 0.4963 (9) | 0.6039 (3) | 0.0323 (13) | |
H12 | 0.9764 | 0.6077 | 0.6333 | 0.039* | |
C13 | 0.9170 (4) | 0.3112 (9) | 0.5354 (3) | 0.0312 (12) | |
H13 | 0.9769 | 0.2980 | 0.5167 | 0.037* | |
C14 | 0.8319 (4) | 0.1473 (10) | 0.4944 (3) | 0.0343 (12) | |
H14 | 0.8335 | 0.0200 | 0.4479 | 0.041* | |
C15 | 0.7425 (4) | 0.1646 (10) | 0.5200 (3) | 0.0324 (12) | |
H15 | 0.6840 | 0.0490 | 0.4911 | 0.039* | |
N16 | 0.6530 (3) | 0.3813 (8) | 0.6161 (2) | 0.0254 (9) | |
H16 | 0.670 (3) | 0.484 (7) | 0.666 (2) | 0.030* | |
C17 | 0.5757 (3) | 0.1761 (10) | 0.5971 (3) | 0.0327 (12) | |
H17A | 0.6130 | 0.0084 | 0.6205 | 0.039* | |
H17B | 0.5344 | 0.1620 | 0.5251 | 0.039* | |
C18 | 0.5006 (3) | 0.2295 (10) | 0.6490 (3) | 0.0325 (12) | |
H18A | 0.4716 | 0.4083 | 0.6335 | 0.039* | |
H18B | 0.4399 | 0.1058 | 0.6256 | 0.039* | |
O19 | 0.5558 (2) | 0.2027 (7) | 0.7526 (2) | 0.0371 (9) | |
C20 | 0.4862 (3) | 0.2611 (10) | 0.8032 (3) | 0.0326 (12) | |
H20A | 0.4229 | 0.1454 | 0.7789 | 0.039* | |
H20B | 0.4611 | 0.4435 | 0.7896 | 0.039* | |
C21 | 0.5446 (3) | 0.2233 (10) | 0.9127 (3) | 0.0321 (12) | |
H21A | 0.4922 | 0.2162 | 0.9450 | 0.038* | |
H21B | 0.5838 | 0.0557 | 0.9251 | 0.038* | |
N22 | 0.6186 (3) | 0.4321 (8) | 0.9545 (2) | 0.0269 (10) | |
H22 | 0.650 (3) | 0.523 (7) | 0.925 (3) | 0.032* | |
C23 | 0.6832 (3) | 0.4316 (9) | 1.0546 (3) | 0.0258 (11) | |
C24 | 0.7644 (4) | 0.6197 (9) | 1.0891 (3) | 0.0254 (12) | |
C25 | 0.8270 (4) | 0.5186 (9) | 0.6298 (3) | 0.0254 (12) | |
C26 | 0.7392 (3) | 0.3500 (9) | 0.5874 (3) | 0.0259 (12) | |
O1S | 0.6568 (8) | 0.703 (2) | 0.7943 (8) | 0.032 (4) | 0.304 (6) |
H1S | 0.7225 (19) | 0.72 (2) | 0.818 (9) | 0.038* | 0.304 (6) |
H2S | 0.623 (8) | 0.840 (14) | 0.779 (10) | 0.038* | 0.304 (6) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.045 (3) | 0.040 (4) | 0.030 (3) | −0.005 (3) | 0.024 (3) | −0.003 (3) |
C2 | 0.037 (3) | 0.045 (3) | 0.028 (3) | 0.005 (3) | 0.016 (2) | 0.008 (3) |
C3 | 0.038 (3) | 0.043 (3) | 0.019 (3) | 0.009 (3) | 0.008 (2) | 0.003 (3) |
C4 | 0.030 (3) | 0.039 (3) | 0.030 (3) | 0.002 (3) | 0.010 (2) | −0.002 (3) |
O5 | 0.040 (2) | 0.033 (2) | 0.0262 (18) | −0.0023 (17) | 0.0134 (16) | 0.0036 (16) |
C6 | 0.026 (3) | 0.031 (3) | 0.027 (3) | −0.003 (3) | 0.008 (2) | −0.002 (2) |
C7 | 0.032 (3) | 0.032 (3) | 0.026 (3) | −0.003 (2) | 0.012 (2) | −0.002 (2) |
O8 | 0.045 (2) | 0.035 (2) | 0.0232 (17) | 0.0066 (17) | 0.0183 (16) | 0.0059 (17) |
C9 | 0.031 (3) | 0.027 (3) | 0.019 (3) | −0.002 (2) | 0.006 (2) | −0.002 (2) |
C10 | 0.023 (3) | 0.028 (3) | 0.023 (3) | −0.002 (2) | 0.004 (2) | 0.002 (2) |
O11 | 0.040 (2) | 0.030 (2) | 0.0269 (17) | −0.0042 (18) | 0.0152 (16) | −0.0038 (16) |
C12 | 0.046 (3) | 0.027 (3) | 0.027 (3) | 0.000 (3) | 0.018 (3) | 0.007 (2) |
C13 | 0.046 (3) | 0.028 (3) | 0.030 (3) | 0.005 (3) | 0.026 (3) | 0.008 (2) |
C14 | 0.048 (3) | 0.032 (3) | 0.028 (3) | 0.009 (3) | 0.019 (3) | 0.003 (3) |
C15 | 0.037 (3) | 0.034 (3) | 0.023 (3) | 0.002 (3) | 0.009 (2) | −0.002 (3) |
N16 | 0.026 (2) | 0.024 (2) | 0.023 (2) | −0.003 (2) | 0.006 (2) | −0.0111 (19) |
C17 | 0.035 (3) | 0.035 (3) | 0.025 (3) | 0.000 (3) | 0.007 (2) | −0.002 (2) |
C18 | 0.027 (3) | 0.039 (3) | 0.026 (3) | −0.004 (3) | 0.003 (2) | −0.002 (3) |
O19 | 0.0320 (18) | 0.054 (2) | 0.0220 (17) | 0.0037 (19) | 0.0059 (16) | −0.0026 (18) |
C20 | 0.030 (3) | 0.039 (3) | 0.031 (3) | 0.000 (2) | 0.014 (2) | −0.001 (3) |
C21 | 0.030 (3) | 0.038 (3) | 0.028 (3) | −0.003 (3) | 0.010 (2) | 0.003 (3) |
N22 | 0.030 (2) | 0.035 (3) | 0.017 (2) | −0.010 (2) | 0.0096 (19) | 0.0043 (19) |
C23 | 0.027 (3) | 0.024 (3) | 0.027 (3) | 0.007 (2) | 0.012 (2) | −0.003 (2) |
C24 | 0.031 (3) | 0.028 (3) | 0.020 (3) | 0.005 (3) | 0.013 (2) | 0.003 (2) |
C25 | 0.040 (3) | 0.019 (3) | 0.019 (3) | −0.001 (2) | 0.013 (2) | −0.002 (2) |
C26 | 0.030 (3) | 0.026 (3) | 0.019 (3) | 0.003 (2) | 0.006 (2) | 0.002 (2) |
O1S | 0.039 (7) | 0.032 (8) | 0.028 (7) | −0.002 (6) | 0.016 (6) | 0.003 (6) |
Geometric parameters (Å, º) top
C1—C23 | 1.382 (6) | C13—C14 | 1.365 (6) |
C1—C2 | 1.393 (6) | C13—H13 | 0.9500 |
C1—H1 | 0.9500 | C14—C15 | 1.396 (6) |
C2—C3 | 1.371 (7) | C14—H14 | 0.9500 |
C2—H2 | 0.9500 | C15—C26 | 1.384 (6) |
C3—C4 | 1.397 (6) | C15—H15 | 0.9500 |
C3—H3 | 0.9500 | N16—C26 | 1.390 (5) |
C4—C24 | 1.373 (5) | N16—C17 | 1.433 (6) |
C4—H4 | 0.9500 | N16—H16 | 0.861 (19) |
O5—C24 | 1.378 (5) | C17—C18 | 1.506 (5) |
O5—C6 | 1.441 (5) | C17—H17A | 0.9900 |
C6—C7 | 1.498 (5) | C17—H17B | 0.9900 |
C6—H6A | 0.9900 | C18—O19 | 1.419 (4) |
C6—H6B | 0.9900 | C18—H18A | 0.9900 |
C7—O8 | 1.423 (5) | C18—H18B | 0.9900 |
C7—H7A | 0.9900 | O19—C20 | 1.432 (4) |
C7—H7B | 0.9900 | C20—C21 | 1.507 (5) |
O8—C9 | 1.407 (4) | C20—H20A | 0.9900 |
C9—C10 | 1.495 (5) | C20—H20B | 0.9900 |
C9—H9A | 0.9900 | C21—N22 | 1.434 (6) |
C9—H9B | 0.9900 | C21—H21A | 0.9900 |
C10—O11 | 1.427 (5) | C21—H21B | 0.9900 |
C10—H10A | 0.9900 | N22—C23 | 1.393 (5) |
C10—H10B | 0.9900 | N22—H22 | 0.842 (19) |
O11—C25 | 1.379 (5) | C23—C24 | 1.403 (6) |
C12—C13 | 1.385 (6) | C25—C26 | 1.407 (6) |
C12—C25 | 1.400 (6) | O1S—H1S | 0.83 (2) |
C12—H12 | 0.9500 | O1S—H2S | 0.82 (2) |
| | | |
C23—C1—C2 | 120.5 (5) | C26—C15—C14 | 120.1 (5) |
C23—C1—H1 | 119.7 | C26—C15—H15 | 120.0 |
C2—C1—H1 | 119.7 | C14—C15—H15 | 120.0 |
C3—C2—C1 | 120.0 (5) | C26—N16—C17 | 119.2 (4) |
C3—C2—H2 | 120.0 | C26—N16—H16 | 110 (3) |
C1—C2—H2 | 120.0 | C17—N16—H16 | 123 (3) |
C2—C3—C4 | 120.2 (4) | N16—C17—C18 | 110.4 (4) |
C2—C3—H3 | 119.9 | N16—C17—H17A | 109.6 |
C4—C3—H3 | 119.9 | C18—C17—H17A | 109.6 |
C24—C4—C3 | 119.8 (5) | N16—C17—H17B | 109.6 |
C24—C4—H4 | 120.1 | C18—C17—H17B | 109.6 |
C3—C4—H4 | 120.1 | H17A—C17—H17B | 108.1 |
C24—O5—C6 | 117.5 (3) | O19—C18—C17 | 110.0 (3) |
O5—C6—C7 | 107.8 (3) | O19—C18—H18A | 109.7 |
O5—C6—H6A | 110.1 | C17—C18—H18A | 109.7 |
C7—C6—H6A | 110.1 | O19—C18—H18B | 109.7 |
O5—C6—H6B | 110.1 | C17—C18—H18B | 109.7 |
C7—C6—H6B | 110.1 | H18A—C18—H18B | 108.2 |
H6A—C6—H6B | 108.5 | C18—O19—C20 | 110.6 (3) |
O8—C7—C6 | 109.0 (4) | O19—C20—C21 | 110.1 (4) |
O8—C7—H7A | 109.9 | O19—C20—H20A | 109.6 |
C6—C7—H7A | 109.9 | C21—C20—H20A | 109.6 |
O8—C7—H7B | 109.9 | O19—C20—H20B | 109.6 |
C6—C7—H7B | 109.9 | C21—C20—H20B | 109.6 |
H7A—C7—H7B | 108.3 | H20A—C20—H20B | 108.2 |
C9—O8—C7 | 111.5 (3) | N22—C21—C20 | 110.8 (4) |
O8—C9—C10 | 109.7 (4) | N22—C21—H21A | 109.5 |
O8—C9—H9A | 109.7 | C20—C21—H21A | 109.5 |
C10—C9—H9A | 109.7 | N22—C21—H21B | 109.5 |
O8—C9—H9B | 109.7 | C20—C21—H21B | 109.5 |
C10—C9—H9B | 109.7 | H21A—C21—H21B | 108.1 |
H9A—C9—H9B | 108.2 | C23—N22—C21 | 120.3 (4) |
O11—C10—C9 | 108.0 (3) | C23—N22—H22 | 108 (3) |
O11—C10—H10A | 110.1 | C21—N22—H22 | 127 (3) |
C9—C10—H10A | 110.1 | C1—C23—N22 | 123.1 (4) |
O11—C10—H10B | 110.1 | C1—C23—C24 | 118.9 (4) |
C9—C10—H10B | 110.1 | N22—C23—C24 | 118.0 (4) |
H10A—C10—H10B | 108.4 | C4—C24—O5 | 124.5 (4) |
C25—O11—C10 | 118.3 (3) | C4—C24—C23 | 120.6 (4) |
C13—C12—C25 | 119.6 (5) | O5—C24—C23 | 115.0 (4) |
C13—C12—H12 | 120.2 | O11—C25—C12 | 124.3 (4) |
C25—C12—H12 | 120.2 | O11—C25—C26 | 115.6 (4) |
C14—C13—C12 | 120.4 (4) | C12—C25—C26 | 120.0 (4) |
C14—C13—H13 | 119.8 | C15—C26—N16 | 123.6 (4) |
C12—C13—H13 | 119.8 | C15—C26—C25 | 119.1 (4) |
C13—C14—C15 | 120.8 (5) | N16—C26—C25 | 117.3 (4) |
C13—C14—H14 | 119.6 | H1S—O1S—H2S | 114 (6) |
C15—C14—H14 | 119.6 | | |
| | | |
C23—C1—C2—C3 | 0.0 (7) | C21—N22—C23—C24 | 171.3 (4) |
C1—C2—C3—C4 | −0.5 (7) | C3—C4—C24—O5 | −179.9 (4) |
C2—C3—C4—C24 | 0.4 (7) | C3—C4—C24—C23 | 0.4 (7) |
C24—O5—C6—C7 | 178.0 (3) | C6—O5—C24—C4 | 6.0 (6) |
O5—C6—C7—O8 | −69.7 (4) | C6—O5—C24—C23 | −174.2 (4) |
C6—C7—O8—C9 | 175.5 (4) | C1—C23—C24—C4 | −0.9 (6) |
C7—O8—C9—C10 | 177.6 (3) | N22—C23—C24—C4 | 177.8 (4) |
O8—C9—C10—O11 | 77.0 (4) | C1—C23—C24—O5 | 179.3 (4) |
C9—C10—O11—C25 | 174.4 (3) | N22—C23—C24—O5 | −2.0 (6) |
C25—C12—C13—C14 | −1.3 (6) | C10—O11—C25—C12 | 3.9 (6) |
C12—C13—C14—C15 | 0.6 (7) | C10—O11—C25—C26 | −177.9 (4) |
C13—C14—C15—C26 | 0.2 (7) | C13—C12—C25—O11 | 179.2 (4) |
C26—N16—C17—C18 | 170.3 (4) | C13—C12—C25—C26 | 1.2 (6) |
N16—C17—C18—O19 | −69.9 (5) | C14—C15—C26—N16 | 179.4 (4) |
C17—C18—O19—C20 | 178.2 (4) | C14—C15—C26—C25 | −0.3 (6) |
C18—O19—C20—C21 | 178.1 (4) | C17—N16—C26—C15 | 16.9 (6) |
O19—C20—C21—N22 | 74.6 (5) | C17—N16—C26—C25 | −163.3 (4) |
C20—C21—N22—C23 | −178.2 (4) | O11—C25—C26—C15 | −178.6 (4) |
C2—C1—C23—N22 | −177.9 (4) | C12—C25—C26—C15 | −0.4 (6) |
C2—C1—C23—C24 | 0.7 (6) | O11—C25—C26—N16 | 1.6 (6) |
C21—N22—C23—C1 | −10.1 (6) | C12—C25—C26—N16 | 179.9 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N16—H16···O11 | 0.86 (2) | 2.17 (4) | 2.643 (5) | 114 (3) |
N16—H16···O1S | 0.86 (2) | 2.25 (3) | 3.073 (11) | 160 (4) |
N22—H22···O5 | 0.84 (2) | 2.16 (4) | 2.639 (5) | 116 (3) |
N22—H22···O1S | 0.84 (2) | 2.17 (3) | 2.937 (11) | 152 (4) |
O1S—H1S···O8 | 0.83 (2) | 2.30 (6) | 3.078 (10) | 157 (12) |
O1S—H1S···O11 | 0.83 (2) | 2.56 (12) | 3.021 (10) | 117 (11) |
O1S—H2S···O19i | 0.82 (2) | 2.04 (3) | 2.859 (12) | 173 (13) |
Symmetry code: (i) x, y+1, z. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C18H22N2O3 | C20H26N2O4 | C20H26N2O4·0.304H2O |
Mr | 314.38 | 358.43 | 363.92 |
Crystal system, space group | Orthorhombic, P212121 | Monoclinic, C2/c | Monoclinic, P21 |
Temperature (K) | 100 | 120 | 100 |
a, b, c (Å) | 7.8995 (8), 9.5228 (10), 21.093 (2) | 11.837 (2), 18.116 (3), 9.2565 (18) | 13.507 (8), 5.133 (3), 14.644 (8) |
α, β, γ (°) | 90, 90, 90 | 90, 109.485 (5), 90 | 90, 112.336 (9), 90 |
V (Å3) | 1586.7 (3) | 1871.3 (6) | 939.1 (9) |
Z | 4 | 4 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.09 | 0.09 |
Crystal size (mm) | 0.32 × 0.26 × 0.20 | 0.28 × 0.18 × 0.14 | 0.22 × 0.05 × 0.04 |
|
Data collection |
Diffractometer | Bruker APEX CCD diffractometer | Bruker APEX CCD diffractometer | Bruker APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2002) | Multi-scan (SADABS; Sheldrick, 2002) | Multi-scan (SADABS; Sheldrick, 2002) |
Tmin, Tmax | 0.971, 0.984 | 0.973, 0.989 | 0.979, 0.997 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16397, 1809, 1788 | 9314, 1839, 1726 | 4546, 2037, 1223 |
Rint | 0.014 | 0.018 | 0.064 |
(sin θ/λ)max (Å−1) | 0.617 | 0.617 | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.071, 1.07 | 0.033, 0.091, 1.00 | 0.053, 0.095, 1.00 |
No. of reflections | 1809 | 1839 | 2037 |
No. of parameters | 215 | 122 | 257 |
No. of restraints | 0 | 0 | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.17, −0.18 | 0.24, −0.21 | 0.23, −0.20 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···O8 | 0.887 (19) | 2.349 (18) | 2.7310 (16) | 106.0 (14) |
N5—H5···O19 | 0.887 (19) | 2.220 (19) | 2.6699 (17) | 111.0 (14) |
N11—H11···O16 | 0.893 (17) | 2.246 (18) | 2.6655 (16) | 108.3 (14) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···O8i | 0.851 (14) | 2.392 (13) | 3.0530 (12) | 134.9 (11) |
N5—H5···O22 | 0.851 (14) | 2.223 (13) | 2.6138 (11) | 107.9 (10) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N16—H16···O11 | 0.861 (19) | 2.17 (4) | 2.643 (5) | 114 (3) |
N16—H16···O1S | 0.861 (19) | 2.25 (3) | 3.073 (11) | 160 (4) |
N22—H22···O5 | 0.842 (19) | 2.16 (4) | 2.639 (5) | 116 (3) |
N22—H22···O1S | 0.842 (19) | 2.17 (3) | 2.937 (11) | 152 (4) |
O1S—H1S···O8 | 0.83 (2) | 2.30 (6) | 3.078 (10) | 157 (12) |
O1S—H1S···O11 | 0.83 (2) | 2.56 (12) | 3.021 (10) | 117 (11) |
O1S—H2S···O19i | 0.82 (2) | 2.04 (3) | 2.859 (12) | 173 (13) |
Symmetry code: (i) x, y+1, z. |
Macrocyclic diaminopolyethers, which serve as precursors in the synthesis of cryptands, also are of interest for their potential as receptors for molecules and anions (Kang et al., 2006). In the process of preparing cryptands with aniline-type nitrogen as the bridgehead atoms we have isolated several related benzoannelated macrocyclic diamines, and we report the structures of (I)–(III) here. These closely related compounds reveal the effects of ring size [comparing (I) and (II)] and position of the benzo groups [comparing (II) and (III)] on the orientation of the NH H atoms, an important consideration for the design of anion and molecular receptors. Among the factors that contribute to the conformation of the macrocycle, and thus the orientation of the NH H atoms, are the torsion angles for the X—CH2—CH2—O (X = N and O) segments, macrocycle ring size and the position of the benzo groups in the macrocycle backbone. For (I)–(III) the torsion angles for the alkyl X—CH2—CH2—O groups lie in the range 54.77 (13)–76.9 (6)° [cf. values in CIF, should this be 55.00 (15)–74.6 (5)?], thus adopting the gauche conformation preferred when such subunits contain N or O atoms (Herceg & Weiss, 1970; Wolf et al., 1987). The N—C═C—O torsion angles for the heteroatoms attached to the benzene ring are geometrically restricted and range from 1.50 (6)° to 6.23 (14)° [or 1.6 (6)–6.27 (18)?]. The N atoms are essentially coplanar with the associated benzo group [with deviations of 0.0055 (13)–0.071 (6) Å], while the amino H atoms show a slightly greater range of deviation (0.0478 (13)–0.193 (6) Å]. Therefore, the orientation of the NH H atoms will be defined by the associated benzo group, and, as shown in Figs. 1–3, the NH H atoms have an endodentate conformation with respect to the macrocycle cavity.
For (I) the gauche conformation of the X—CH2—CH2—O subunits, the smaller ring size and the short five-atom bridge (CCOCC) connecting atoms N5 and N11 result in the molecule adopting a relatively flat conformation (Fig. 1), although the least-squares plane defined by the atoms N5, O8, N11, O16 and O19 [the mean deviation is 0.4288 (14) Å] is the least well defined among the three compounds. Benzene rings A and B have dihedral angles of 28.5 (2) and 137.7 (2)°, respectively, with the plane defined by the heteroatoms and 166.2 (2)° with each other. Atom H5 forms hydrogen bonds with atoms O8 and O19, while H11 has reasonable hydrogen bond geometry only with O16 (Fig. 1 and Table 1).
Molecule (II) lies on a twofold rotation axis. The eight-atom chain (CCOCCOCC) between the N atoms allows the benzo groups to rotate out the plane defined by atoms N5, O8 and O22 [the mean deviation is 0.2513 (12) Å] to a much greater extent than for (I). The resulting conformation has the benzo groups on opposite sides of the hetero-atom plane (Fig. 4), forming a dihedral angle of 72.9 (2)° with one another and 112.1 (2)° with the hetero-atom plane. As a result, one NH H atom is oriented above and the other below the hetero-atom plane. Each forms an intramolecular hydrogen bond with the proximal phenoxy ether O atom (Fig. 2 and Table 2). In addition, each NH H atom forms a hydrogen bond to ether atom O8(1 - x, 1 - y, 1 - z) in an adjacent molecule, linking the macrocycles together in a chain-like fashion via an R22(10) motif (Bernstein et al., 1995) along the c axis (Fig. 4).
The macrocycle ring size of (III) is the same as that of (II) but the position of the benzo groups and N atoms in the ring differs, and a molecule of water [with a fractional occupancy of 0.304 (6)] is present above the center of the macrocycle cavity. The positions of the benzo groups and gauche conformation of all the X—CH2—CH2—O subunits allow the molecule to adopt a folded conformation defined by an axis passing through O8 and O19 (Fig. 5). The benzo groups are located on the same side of the plane defined by atoms O5, O8, O11, N16, O19 and N22 [the mean deviation is 0.0557 (6) Å]. Benzene rings A and B form dihedral angles of 33.5 (2) and 148.0 (2)°, respectively, with the hetero-atom plane and 114.6 (2)° with one another. Both NH H atoms are on the same side of the macrocycle plane and are oriented toward, but above, the center of the cavity. Each NH H atom forms an intramolecular hydrogen bond with the adjacent phenoxy ether O atom (Fig. 3 and Table 3). In addition, both NH H atoms interact with atom O1S of the water molecule. Atom H1S1 forms a hydrogen bond to atom O8, while H1S2 forms a hydrogen bond with atom O19(x, 1 + y, z) in an adjacent molecule, linking the crown ethers in a chain via a C22(7) motif (Bernstein et al., 1995) along the b axis (Fig. 5).
The NH H atoms for (I)–(III) all form weak intramolecular hydrogen bonds with one or more ether O atoms in the macrocycle; however, the N—H···O angles [106.0 (14)–116 (3)°] cannot achieve optimal geometry due to conformational restrictions imposed by the ring structure and the presence of the benzo groups in the macrocycle backbone. The intermolecular N—H···O angels for (III) [152 (4)–173 (13)°] fall in the conventional range except for O1S—H1S···O11 [117 (11)°], while those for (II) [134.9 (11)°] are somewhat lower. Comparison of the structural characteristics of (I)–(III) suggests that a macrocycle with NH groups separated by a five-atom bridge and a ring size of 18 atoms, as in (III), provides hydrogen-bond donors with the spacing and orientation suitable to interact preferably with an external hydrogen-bond acceptor guest.