6,7,9,10-Tetra-hydro-16,22-ethano-oxyethano-5,8,11,19-tetra-oxa-16,22-diaza-dibenzo[h,q]cyclo-octa-decine-17,21-dione: a benzyl-annelated macrobicyclic diamide.

The macrobicyclic title compound, C(24)H(28)N(2)O(7), has two tertiary diamide bridgehead atoms and is composed of a 12-membered ring (N(2)O(2) donor set) and two 18-membered rings (N(2)O(4) donor sets). The solid-state structure shows that each of the amide groups is not coplanar with the adjacent benzene ring and NMR studies indicate that this conformational relationship persists in solution.

Related literature

For general background, see: Dietrich et al. (1969 ▶); Tummler et al. (1977 ▶); Niklas et al. (2004 ▶); Schickaneder et al. (2006 ▶); Lehn (1973 ▶). For related structures, see: Tarnowska et al. (2004 ▶); Smith et al. (2007 ▶). For the synthesis, see: Dietrich et al. (1973 ▶). For NMR studies, see: Smith et al. (2007 ▶); Silverstein & Webster (1998 ▶).

Experimental

Crystal data

C24H28N2O7

M = 456.48

Monoclinic,

a = 15.125 (2) Å

b = 9.3901 (14) Å

c = 16.446 (2) Å

β = 108.416 (5)°

V = 2216.1 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 87 (2) K

0.58 × 0.56 × 0.52 mm

Data collection

Bruker APEX diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T min = 0.940, T max = 0.950

23465 measured reflections

4352 independent reflections

4142 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.085

S = 1.03

4352 reflections

298 parameters

H-atom parameters constrained

Δρmax = 0.24 e Å−3

Δρmin = −0.23 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808030067/pk2117sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808030067/pk2117Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C24H28N2O7	F(000) = 968
Mr = 456.48	Dx = 1.368 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7313 reflections
a = 15.125 (2) Å	θ = 2.6–28.2°
b = 9.3901 (14) Å	µ = 0.10 mm−1
c = 16.446 (2) Å	T = 87 K
β = 108.416 (5)°	Block, colorless
V = 2216.1 (5) Å3	0.58 × 0.56 × 0.52 mm
Z = 4

Bruker APEX diffractometer	4352 independent reflections
Radiation source: fine-focus sealed tube	4142 reflections with I > 2σ(I)
graphite	Rint = 0.020
Detector resolution: 8.366 pixels mm-1	θmax = 26.0°, θmin = 2.2°
ω scans	h = −18→18
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	k = −11→11
Tmin = 0.940, Tmax = 0.950	l = −20→20
23465 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0451P)2 + 0.7509P] where P = (Fo2 + 2Fc2)/3
4352 reflections	(Δ/σ)max = 0.001
298 parameters	Δρmax = 0.24 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
O1	0.64508 (5)	0.74748 (8)	0.62300 (5)	0.02150 (17)
O2	0.59736 (5)	0.89145 (8)	0.45462 (5)	0.02121 (17)
O3	0.64605 (5)	0.75428 (8)	0.31729 (5)	0.02270 (17)
O4	0.57879 (5)	0.34635 (8)	0.45980 (5)	0.02311 (17)
O5	0.84403 (5)	0.62786 (8)	0.72596 (5)	0.02390 (17)
O6	0.81395 (5)	0.53553 (8)	0.52618 (5)	0.02129 (17)
O7	0.85667 (5)	0.62395 (8)	0.34044 (5)	0.02538 (18)
N1	0.72291 (6)	0.48401 (9)	0.65874 (5)	0.01944 (19)
N2	0.72987 (6)	0.49648 (9)	0.34218 (6)	0.02010 (19)
C1	0.66837 (7)	0.54166 (11)	0.70866 (6)	0.0198 (2)
C2	0.65342 (8)	0.46203 (12)	0.77389 (7)	0.0240 (2)
H2	0.6820	0.3713	0.7877	0.029*
C3	0.59674 (8)	0.51404 (12)	0.81940 (7)	0.0265 (2)
H3	0.5869	0.4593	0.8644	0.032*
C4	0.55497 (8)	0.64576 (12)	0.79873 (7)	0.0249 (2)
H4	0.5157	0.6810	0.8292	0.030*
C5	0.56994 (7)	0.72721 (12)	0.73368 (7)	0.0224 (2)
H5	0.5413	0.8180	0.7203	0.027*
C6	0.62683 (7)	0.67631 (11)	0.68798 (6)	0.0193 (2)
C7	0.60204 (8)	0.88484 (11)	0.60179 (7)	0.0219 (2)
H7A	0.6167	0.9449	0.6539	0.026*
H7B	0.5335	0.8740	0.5785	0.026*
C8	0.63801 (8)	0.95395 (11)	0.53658 (7)	0.0232 (2)
H8A	0.6234	1.0570	0.5336	0.028*
H8B	0.7066	0.9433	0.5540	0.028*
C9	0.63046 (8)	0.96135 (11)	0.39353 (7)	0.0228 (2)
H9A	0.6994	0.9624	0.4140	0.027*
H9B	0.6084	1.0612	0.3869	0.027*
C10	0.59670 (8)	0.88731 (11)	0.30861 (7)	0.0233 (2)
H10A	0.5288	0.8700	0.2924	0.028*
H10B	0.6092	0.9465	0.2637	0.028*
C11	0.68585 (7)	0.35454 (11)	0.60899 (7)	0.0217 (2)
H11A	0.6858	0.2759	0.6491	0.026*
H11B	0.7275	0.3269	0.5758	0.026*
C12	0.58634 (7)	0.37445 (12)	0.54701 (7)	0.0224 (2)
H12A	0.5437	0.3100	0.5644	0.027*
H12B	0.5660	0.4735	0.5517	0.027*
C13	0.61408 (7)	0.45732 (11)	0.41885 (7)	0.0219 (2)
H13A	0.6441	0.5322	0.4609	0.026*
H13B	0.5626	0.5012	0.3726	0.026*
C14	0.68495 (7)	0.39065 (11)	0.38188 (7)	0.0219 (2)
H14A	0.7333	0.3411	0.4282	0.026*
H14B	0.6533	0.3187	0.3384	0.026*
C15	0.80862 (7)	0.53954 (11)	0.67021 (7)	0.0200 (2)
C16	0.86233 (7)	0.49116 (12)	0.61103 (7)	0.0233 (2)
H16A	0.9256	0.5330	0.6299	0.028*
H16B	0.8685	0.3862	0.6131	0.028*
C17	0.86817 (7)	0.50959 (12)	0.47159 (7)	0.0235 (2)
H17A	0.8851	0.4074	0.4745	0.028*
H17B	0.9266	0.5654	0.4919	0.028*
C18	0.81667 (7)	0.54926 (11)	0.37915 (7)	0.0206 (2)
C19	0.67883 (7)	0.54321 (11)	0.25679 (7)	0.0203 (2)
C20	0.67082 (7)	0.45530 (12)	0.18772 (7)	0.0241 (2)
H20	0.6996	0.3642	0.1965	0.029*
C21	0.62088 (8)	0.49929 (13)	0.10519 (7)	0.0270 (2)
H21	0.6153	0.4385	0.0576	0.032*
C22	0.57953 (8)	0.63187 (13)	0.09301 (7)	0.0262 (2)
H22	0.5462	0.6627	0.0366	0.031*
C23	0.58607 (7)	0.72109 (12)	0.16232 (7)	0.0243 (2)
H23	0.5569	0.8119	0.1531	0.029*
C24	0.63543 (7)	0.67709 (11)	0.24507 (7)	0.0207 (2)

	U11	U22	U33	U12	U13	U23
O1	0.0234 (4)	0.0199 (4)	0.0218 (4)	0.0037 (3)	0.0079 (3)	0.0030 (3)
O2	0.0234 (4)	0.0210 (4)	0.0195 (4)	−0.0021 (3)	0.0071 (3)	−0.0003 (3)
O3	0.0257 (4)	0.0211 (4)	0.0209 (4)	0.0051 (3)	0.0067 (3)	0.0006 (3)
O4	0.0239 (4)	0.0256 (4)	0.0195 (4)	−0.0087 (3)	0.0064 (3)	−0.0022 (3)
O5	0.0218 (4)	0.0226 (4)	0.0245 (4)	−0.0028 (3)	0.0034 (3)	−0.0016 (3)
O6	0.0177 (3)	0.0262 (4)	0.0196 (4)	0.0040 (3)	0.0055 (3)	0.0019 (3)
O7	0.0231 (4)	0.0266 (4)	0.0282 (4)	−0.0026 (3)	0.0105 (3)	0.0011 (3)
N1	0.0182 (4)	0.0184 (4)	0.0203 (4)	−0.0004 (3)	0.0040 (3)	−0.0012 (3)
N2	0.0188 (4)	0.0201 (4)	0.0217 (4)	0.0006 (3)	0.0068 (4)	0.0016 (3)
C1	0.0174 (5)	0.0209 (5)	0.0191 (5)	−0.0032 (4)	0.0030 (4)	−0.0029 (4)
C2	0.0240 (5)	0.0215 (5)	0.0241 (5)	−0.0041 (4)	0.0043 (4)	0.0005 (4)
C3	0.0278 (6)	0.0297 (6)	0.0225 (5)	−0.0089 (5)	0.0086 (4)	0.0004 (4)
C4	0.0210 (5)	0.0315 (6)	0.0229 (5)	−0.0066 (4)	0.0078 (4)	−0.0069 (4)
C5	0.0198 (5)	0.0239 (5)	0.0217 (5)	−0.0005 (4)	0.0037 (4)	−0.0035 (4)
C6	0.0171 (5)	0.0216 (5)	0.0170 (5)	−0.0034 (4)	0.0023 (4)	−0.0015 (4)
C7	0.0250 (5)	0.0183 (5)	0.0207 (5)	0.0037 (4)	0.0047 (4)	−0.0008 (4)
C8	0.0261 (5)	0.0186 (5)	0.0221 (5)	−0.0018 (4)	0.0035 (4)	−0.0014 (4)
C9	0.0248 (5)	0.0195 (5)	0.0271 (6)	0.0012 (4)	0.0127 (4)	0.0026 (4)
C10	0.0248 (5)	0.0221 (5)	0.0246 (5)	0.0062 (4)	0.0101 (4)	0.0043 (4)
C11	0.0231 (5)	0.0181 (5)	0.0220 (5)	−0.0001 (4)	0.0043 (4)	−0.0021 (4)
C12	0.0204 (5)	0.0266 (5)	0.0201 (5)	−0.0034 (4)	0.0062 (4)	−0.0018 (4)
C13	0.0191 (5)	0.0224 (5)	0.0234 (5)	−0.0018 (4)	0.0057 (4)	0.0022 (4)
C14	0.0220 (5)	0.0189 (5)	0.0246 (5)	−0.0016 (4)	0.0071 (4)	0.0013 (4)
C15	0.0186 (5)	0.0191 (5)	0.0196 (5)	0.0021 (4)	0.0022 (4)	0.0041 (4)
C16	0.0174 (5)	0.0291 (6)	0.0210 (5)	0.0028 (4)	0.0026 (4)	0.0025 (4)
C17	0.0179 (5)	0.0282 (6)	0.0245 (5)	0.0034 (4)	0.0070 (4)	0.0001 (4)
C18	0.0194 (5)	0.0193 (5)	0.0245 (5)	0.0024 (4)	0.0087 (4)	−0.0015 (4)
C19	0.0161 (5)	0.0233 (5)	0.0221 (5)	−0.0024 (4)	0.0068 (4)	0.0011 (4)
C20	0.0200 (5)	0.0246 (5)	0.0291 (6)	−0.0017 (4)	0.0098 (4)	−0.0033 (4)
C21	0.0240 (5)	0.0335 (6)	0.0244 (5)	−0.0070 (5)	0.0090 (4)	−0.0072 (5)
C22	0.0224 (5)	0.0350 (6)	0.0202 (5)	−0.0047 (5)	0.0052 (4)	0.0018 (4)
C23	0.0217 (5)	0.0263 (5)	0.0251 (5)	0.0003 (4)	0.0076 (4)	0.0033 (4)
C24	0.0182 (5)	0.0236 (5)	0.0218 (5)	−0.0023 (4)	0.0085 (4)	−0.0003 (4)

O1—C6	1.3606 (13)	C8—H8B	0.9900
O1—C7	1.4373 (12)	C9—C10	1.4979 (15)
O2—C9	1.4173 (12)	C9—H9A	0.9900
O2—C8	1.4197 (12)	C9—H9B	0.9900
O3—C24	1.3570 (13)	C10—H10A	0.9900
O3—C10	1.4390 (12)	C10—H10B	0.9900
O4—C12	1.4270 (12)	C11—C12	1.5395 (14)
O4—C13	1.4323 (13)	C11—H11A	0.9900
O5—C15	1.2268 (13)	C11—H11B	0.9900
O6—C17	1.4151 (12)	C12—H12A	0.9900
O6—C16	1.4181 (12)	C12—H12B	0.9900
O7—C18	1.2274 (13)	C13—C14	1.5238 (15)
N1—C15	1.3540 (14)	C13—H13A	0.9900
N1—C1	1.4407 (13)	C13—H13B	0.9900
N1—C11	1.4738 (13)	C14—H14A	0.9900
N2—C18	1.3544 (14)	C14—H14B	0.9900
N2—C19	1.4408 (13)	C15—C16	1.5211 (15)
N2—C14	1.4683 (13)	C16—H16A	0.9900
C1—C2	1.3835 (15)	C16—H16B	0.9900
C1—C6	1.4050 (15)	C17—C18	1.5195 (15)
C2—C3	1.3925 (16)	C17—H17A	0.9900
C2—H2	0.9500	C17—H17B	0.9900
C3—C4	1.3815 (17)	C19—C20	1.3782 (15)
C3—H3	0.9500	C19—C24	1.4030 (15)
C4—C5	1.3906 (16)	C20—C21	1.3914 (16)
C4—H4	0.9500	C20—H20	0.9500
C5—C6	1.3937 (15)	C21—C22	1.3792 (17)
C5—H5	0.9500	C21—H21	0.9500
C7—C8	1.4953 (15)	C22—C23	1.3927 (16)
C7—H7A	0.9900	C22—H22	0.9500
C7—H7B	0.9900	C23—C24	1.3923 (15)
C8—H8A	0.9900	C23—H23	0.9500
C6—O1—C7	116.27 (8)	C12—C11—H11B	109.0
C9—O2—C8	109.73 (8)	H11A—C11—H11B	107.8
C24—O3—C10	117.56 (8)	O4—C12—C11	113.21 (9)
C12—O4—C13	114.50 (8)	O4—C12—H12A	108.9
C17—O6—C16	110.57 (8)	C11—C12—H12A	108.9
C15—N1—C1	118.12 (9)	O4—C12—H12B	108.9
C15—N1—C11	125.07 (9)	C11—C12—H12B	108.9
C1—N1—C11	116.13 (8)	H12A—C12—H12B	107.7
C18—N2—C19	118.10 (9)	O4—C13—C14	107.60 (8)
C18—N2—C14	124.55 (9)	O4—C13—H13A	110.2
C19—N2—C14	117.31 (8)	C14—C13—H13A	110.2
C2—C1—C6	120.26 (10)	O4—C13—H13B	110.2
C2—C1—N1	120.14 (10)	C14—C13—H13B	110.2
C6—C1—N1	119.53 (9)	H13A—C13—H13B	108.5
C1—C2—C3	120.42 (10)	N2—C14—C13	112.46 (8)
C1—C2—H2	119.8	N2—C14—H14A	109.1
C3—C2—H2	119.8	C13—C14—H14A	109.1
C4—C3—C2	119.54 (10)	N2—C14—H14B	109.1
C4—C3—H3	120.2	C13—C14—H14B	109.1
C2—C3—H3	120.2	H14A—C14—H14B	107.8
C3—C4—C5	120.58 (10)	O5—C15—N1	122.50 (10)
C3—C4—H4	119.7	O5—C15—C16	119.00 (9)
C5—C4—H4	119.7	N1—C15—C16	118.50 (9)
C4—C5—C6	120.30 (10)	O6—C16—C15	109.15 (8)
C4—C5—H5	119.8	O6—C16—H16A	109.9
C6—C5—H5	119.8	C15—C16—H16A	109.9
O1—C6—C5	124.62 (9)	O6—C16—H16B	109.9
O1—C6—C1	116.48 (9)	C15—C16—H16B	109.9
C5—C6—C1	118.89 (10)	H16A—C16—H16B	108.3
O1—C7—C8	108.90 (9)	O6—C17—C18	112.08 (8)
O1—C7—H7A	109.9	O6—C17—H17A	109.2
C8—C7—H7A	109.9	C18—C17—H17A	109.2
O1—C7—H7B	109.9	O6—C17—H17B	109.2
C8—C7—H7B	109.9	C18—C17—H17B	109.2
H7A—C7—H7B	108.3	H17A—C17—H17B	107.9
O2—C8—C7	110.79 (9)	O7—C18—N2	122.89 (10)
O2—C8—H8A	109.5	O7—C18—C17	118.56 (9)
C7—C8—H8A	109.5	N2—C18—C17	118.51 (9)
O2—C8—H8B	109.5	C20—C19—C24	120.53 (10)
C7—C8—H8B	109.5	C20—C19—N2	120.09 (10)
H8A—C8—H8B	108.1	C24—C19—N2	119.35 (9)
O2—C9—C10	110.69 (9)	C19—C20—C21	120.36 (11)
O2—C9—H9A	109.5	C19—C20—H20	119.8
C10—C9—H9A	109.5	C21—C20—H20	119.8
O2—C9—H9B	109.5	C22—C21—C20	119.42 (10)
C10—C9—H9B	109.5	C22—C21—H21	120.3
H9A—C9—H9B	108.1	C20—C21—H21	120.3
O3—C10—C9	107.28 (8)	C21—C22—C23	120.83 (10)
O3—C10—H10A	110.3	C21—C22—H22	119.6
C9—C10—H10A	110.3	C23—C22—H22	119.6
O3—C10—H10B	110.3	C24—C23—C22	119.93 (11)
C9—C10—H10B	110.3	C24—C23—H23	120.0
H10A—C10—H10B	108.5	C22—C23—H23	120.0
N1—C11—C12	112.85 (8)	O3—C24—C23	125.15 (10)
N1—C11—H11A	109.0	O3—C24—C19	115.95 (9)
C12—C11—H11A	109.0	C23—C24—C19	118.90 (10)
N1—C11—H11B	109.0
C15—N1—C1—C2	−108.91 (11)	C1—N1—C15—O5	6.14 (15)
C11—N1—C1—C2	62.11 (12)	C11—N1—C15—O5	−164.00 (9)
C15—N1—C1—C6	74.13 (12)	C1—N1—C15—C16	−173.30 (9)
C11—N1—C1—C6	−114.85 (10)	C11—N1—C15—C16	16.55 (14)
C6—C1—C2—C3	0.33 (16)	C17—O6—C16—C15	171.97 (8)
N1—C1—C2—C3	−176.61 (9)	O5—C15—C16—O6	−114.72 (10)
C1—C2—C3—C4	0.33 (16)	N1—C15—C16—O6	64.74 (12)
C2—C3—C4—C5	−0.75 (16)	C16—O6—C17—C18	177.25 (9)
C3—C4—C5—C6	0.51 (16)	C19—N2—C18—O7	−7.04 (15)
C7—O1—C6—C5	0.33 (14)	C14—N2—C18—O7	170.73 (10)
C7—O1—C6—C1	179.68 (8)	C19—N2—C18—C17	175.37 (9)
C4—C5—C6—O1	179.49 (9)	C14—N2—C18—C17	−6.86 (15)
C4—C5—C6—C1	0.15 (15)	O6—C17—C18—O7	130.66 (10)
C2—C1—C6—O1	−179.96 (9)	O6—C17—C18—N2	−51.64 (13)
N1—C1—C6—O1	−3.01 (13)	C18—N2—C19—C20	103.13 (12)
C2—C1—C6—C5	−0.57 (15)	C14—N2—C19—C20	−74.81 (12)
N1—C1—C6—C5	176.39 (9)	C18—N2—C19—C24	−78.59 (12)
C6—O1—C7—C8	173.66 (8)	C14—N2—C19—C24	103.47 (11)
C9—O2—C8—C7	178.33 (8)	C24—C19—C20—C21	1.14 (16)
O1—C7—C8—O2	75.03 (10)	N2—C19—C20—C21	179.40 (9)
C8—O2—C9—C10	173.86 (8)	C19—C20—C21—C22	0.11 (16)
C24—O3—C10—C9	−171.74 (8)	C20—C21—C22—C23	−0.92 (16)
O2—C9—C10—O3	−71.12 (10)	C21—C22—C23—C24	0.48 (16)
C15—N1—C11—C12	−133.07 (10)	C10—O3—C24—C23	5.01 (15)
C1—N1—C11—C12	56.61 (12)	C10—O3—C24—C19	−175.35 (9)
C13—O4—C12—C11	−76.49 (11)	C22—C23—C24—O3	−179.61 (10)
N1—C11—C12—O4	122.34 (10)	C22—C23—C24—C19	0.76 (15)
C12—O4—C13—C14	125.90 (9)	C20—C19—C24—O3	178.77 (9)
C18—N2—C14—C13	101.99 (11)	N2—C19—C24—O3	0.50 (13)
C19—N2—C14—C13	−80.22 (11)	C20—C19—C24—C23	−1.56 (15)
O4—C13—C14—N2	−176.83 (8)	N2—C19—C24—C23	−179.83 (9)