12-Benzoyl-2,3,5,6,9,10,11,12-octa­hydro-8H-1,4,7,12-benzotrioxa­aza­cyclo­tetradecine

Fallon, G.D.; Ventrice, T.; Jackson, W.R.; Campi, E.M.; Patti, A.F.

doi:10.1107/S1600536801015586

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12-Benzoyl-2,3,5,6,9,10,11,12-octahydro-8H-1,4,7,12-benzotrioxaazacyclotetradecine

G. D. Fallon, T. Ventrice, W. R. Jackson, E. M. Campi and A. F. Patti

The title compound, C₂₁H₂₅NO₄, is the benzoyl derivative of a benzo-aza-crown ether.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801015586/tk6039sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536801015586/tk6039Isup2.hkl Contains datablock I

CCDC reference: 175376

checkCIF report

Key indicators

Single-crystal X-ray study
T = 123 K
Mean (C-C) = 0.002 Å
R factor = 0.050
wR factor = 0.114
Data-to-parameter ratio = 22.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

Comment top

Incorporation of N-donor atoms into the macrocyclic framework of crown ethers gives aza-crown analogues which can display increased binding strength and selectivity towards transition and post-transition metal ions (Bradshaw et al., 1996). We have reported the preparation of a range of benzo-aza-crown ethers by a protocol involving reductive cyclization of nitroarenes bearing aldehyde-containing side chains (Ventrice et al., 1999, 2001). An X-ray structure determination of the benzoyl derivative, (I), was undertaken to establish the conformation of this compound (Fig. 1).

Experimental top

Sodium hydroxide (10% aq.) (10 ml) was added to 2,3,5,6,9,10,11,12-octahydro-8H-1,4,7,12-benzotrioxaazacyclotetradecine (50 mg, 0.20 mmol) dissolved in THF (10 ml). This mixture was allowed to stir for 10 min, benzoyl chloride (56 mg, 0.40 mmol) was added dropwise and the resulting mixture was allowed to stir for 24 h. The reaction was poured into water (50 ml) and extracted into CH₂Cl₂ (3 × 50 ml), dried (Na₂SO₄), filtered and the solvent was removed under reduced pressure to give a yellow oil. Excess benzoyl chloride was removed on the high vacuum pump. Column chromatography of the residue (SiO2, 20% EtOAc/hexane) gave amide (I) as a yellow oil which solidified on standing (70 mg, 99%). Dichloromethane (10 ml) was added to the amide and single crystals suitable for X-ray structure determination were obtained by slow evaporation of the solution; m.p: 415.4–417.6 K.

Computing details top

Data collection: COLLECT (Nonius, 1997-2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. View of (I) (50% probability displacement ellipsoids).

(I) top

Crystal data top

C₂₁H₂₅NO₄	F(000) = 760
M_r = 355.42	D_x = 1.272 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25477 reflections
a = 16.825 (1) Å	θ = 2.4–30.0°
b = 13.550 (1) Å	µ = 0.09 mm⁻¹
c = 8.173 (1) Å	T = 123 K
β = 95.02 (1)°	Tabular, colourless
V = 1856.1 (3) Å³	0.22 × 0.16 × 0.09 mm
Z = 4

Data collection top

KappaCCD diffractometer	R_int = 0.056
CCD rotation images, thick slices scans	θ_max = 30.1°, θ_min = 2.4°
25477 measured reflections	h = −23→23
5351 independent reflections	k = −18→18
3438 reflections with I > 2σ(I)	l = −11→11

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.050	w = 1/[σ²(F_o²) + (0.0485P)² + 0.2125P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.114	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.19 e Å⁻³
5351 reflections	Δρ_min = −0.23 e Å⁻³
235 parameters

Crystal data top

C₂₁H₂₅NO₄	V = 1856.1 (3) Å³
M_r = 355.42	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.825 (1) Å	µ = 0.09 mm⁻¹
b = 13.550 (1) Å	T = 123 K
c = 8.173 (1) Å	0.22 × 0.16 × 0.09 mm
β = 95.02 (1)°

Data collection top

KappaCCD diffractometer	3438 reflections with I > 2σ(I)
25477 measured reflections	R_int = 0.056
5351 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.04	Δρ_max = 0.19 e Å⁻³
5351 reflections	Δρ_min = −0.23 e Å⁻³
235 parameters

Special details top

Experimental. ¹H n.m.r. (CDCl₃): δ 1.59–1.92 (m, 4H, H9,10), 3.44–3.53 (m, 1H), 3.54–3.68 (m, 6H), 3.80–3.86 (m, 2H), 3.94–3.99 (m, 1H), 4.21–4.28 (m, 1H) and 4.34–4.44 (m, 1H) (H2,3,5,6,8,11), 6.69–6.74 (m, 2H, H14,16), 6.88–6.91 (m, 1H, H15), 7.05–7.18 (m, 4H) and 7.22–7.29 (m, 2H)(H13,PhCH).

¹³C n.m.r. (CDCl₃): δ 24.99 (C10); 27.49 (C9); 49.28 (C11); 67.04, 69.17, 69.54, 70.74 (C3,5,6,8); 71.07 (C2) 111.95 (C16); 120.46 (C13,14); 127.29, 127.84, 128.29, 129.07, 130.45 (C15, PhCH); 132.49 (C12a); 137.14 (PhC); 154.01 (C16a); 171.11 (C═O).

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	U_iso*/U_eq
C1	0.33270 (8)	−0.03036 (10)	0.06246 (16)	0.0273 (3)
C2	0.41424 (8)	−0.04709 (10)	0.14610 (17)	0.0280 (3)
C3	0.52608 (8)	0.03753 (11)	0.27160 (17)	0.0308 (3)
C4	0.55638 (8)	0.13789 (12)	0.32476 (17)	0.0348 (4)
C5	0.44193 (8)	0.22314 (10)	0.41630 (17)	0.0293 (3)
C6	0.37354 (8)	0.16489 (9)	0.47678 (16)	0.0237 (3)
C7	0.29531 (8)	0.21973 (9)	0.43657 (16)	0.0250 (3)
C8	0.22182 (8)	0.17255 (9)	0.50053 (16)	0.0241 (3)
C9	0.16537 (8)	0.08104 (9)	0.25157 (15)	0.0197 (3)
C10	0.08929 (8)	0.11721 (9)	0.20970 (16)	0.0246 (3)
C11	0.05658 (8)	0.11546 (10)	0.04824 (17)	0.0282 (3)
C12	0.10080 (8)	0.07750 (10)	−0.07209 (16)	0.0275 (3)
C13	0.17758 (8)	0.04255 (9)	−0.03383 (15)	0.0237 (3)
C14	0.21060 (8)	0.04539 (9)	0.12799 (15)	0.0200 (3)
C15	0.22114 (8)	−0.00879 (9)	0.49285 (15)	0.0205 (3)
C16	0.18803 (8)	−0.10093 (9)	0.41167 (15)	0.0214 (3)
C17	0.10606 (8)	−0.11350 (10)	0.38082 (16)	0.0260 (3)
C18	0.07552 (9)	−0.20174 (10)	0.31630 (17)	0.0322 (3)
C19	0.12668 (9)	−0.27634 (10)	0.27956 (17)	0.0336 (4)
C20	0.20844 (9)	−0.26434 (10)	0.30790 (16)	0.0304 (3)
C21	0.23918 (8)	−0.17713 (10)	0.37636 (15)	0.0247 (3)
N1	0.19814 (6)	0.07855 (7)	0.41986 (12)	0.0197 (2)
O1	0.28600 (5)	0.01530 (6)	0.17972 (10)	0.0230 (2)
O2	0.45117 (5)	0.04608 (7)	0.17720 (11)	0.0270 (2)
O3	0.51846 (6)	0.17873 (8)	0.45874 (12)	0.0338 (3)
O4	0.26358 (6)	−0.01290 (7)	0.62335 (11)	0.0258 (2)
H1A	0.3357	0.013	−0.0343	0.033*
H1B	0.3084	−0.0939	0.025	0.033*
H2A	0.4104	−0.0829	0.2507	0.034*
H2B	0.4464	−0.0874	0.0752	0.034*
H3A	0.565	0.0051	0.2051	0.037*
H3B	0.5201	−0.0039	0.3695	0.037*
H4A	0.6144	0.1333	0.3564	0.042*
H4B	0.5486	0.1835	0.2301	0.042*
H5A	0.4335	0.2295	0.2954	0.035*
H5B	0.4418	0.2904	0.4636	0.035*
H6A	0.3827	0.1552	0.597	0.028*
H6B	0.3706	0.0991	0.4238	0.028*
H7A	0.286	0.2259	0.3157	0.03*
H7B	0.3011	0.2873	0.4822	0.03*
H8A	0.2326	0.1609	0.62	0.029*
H8B	0.1767	0.2194	0.4847	0.029*
H10	0.0592	0.1435	0.2927	0.03*
H11	0.0043	0.1401	0.0204	0.034*
H12	0.0782	0.0754	−0.1827	0.033*
H13	0.2074	0.0168	−0.1176	0.028*
H17	0.0709	−0.0615	0.404	0.031*
H18	0.0195	−0.2107	0.2975	0.039*
H19	0.1057	−0.3365	0.2344	0.04*
H20	0.2434	−0.3157	0.2806	0.036*
H21	0.2952	−0.1695	0.3991	0.03*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0283 (8)	0.0298 (7)	0.0246 (7)	0.0050 (6)	0.0070 (6)	−0.0057 (6)
C2	0.0288 (8)	0.0281 (7)	0.0279 (7)	0.0072 (6)	0.0067 (6)	−0.0005 (6)
C3	0.0207 (7)	0.0475 (9)	0.0243 (7)	0.0099 (6)	0.0032 (6)	0.0080 (6)
C4	0.0199 (7)	0.0554 (10)	0.0291 (8)	−0.0003 (7)	0.0018 (6)	0.0074 (7)
C5	0.0265 (8)	0.0305 (7)	0.0302 (7)	0.0000 (6)	−0.0016 (6)	0.0042 (6)
C6	0.0266 (7)	0.0214 (7)	0.0226 (6)	−0.0014 (5)	−0.0006 (5)	0.0004 (5)
C7	0.0292 (8)	0.0187 (6)	0.0265 (7)	0.0000 (5)	−0.0004 (6)	−0.0005 (5)
C8	0.0275 (7)	0.0203 (7)	0.0244 (6)	0.0029 (5)	0.0019 (5)	−0.0056 (5)
C9	0.0234 (7)	0.0162 (6)	0.0192 (6)	−0.0012 (5)	0.0010 (5)	0.0002 (5)
C10	0.0245 (7)	0.0225 (7)	0.0270 (7)	0.0022 (5)	0.0036 (5)	−0.0001 (5)
C11	0.0230 (7)	0.0290 (7)	0.0319 (7)	0.0037 (6)	−0.0019 (6)	0.0019 (6)
C12	0.0317 (8)	0.0272 (7)	0.0221 (7)	−0.0004 (6)	−0.0050 (6)	0.0012 (6)
C13	0.0285 (8)	0.0237 (7)	0.0193 (6)	−0.0016 (5)	0.0030 (5)	−0.0013 (5)
C14	0.0203 (7)	0.0179 (6)	0.0217 (6)	−0.0013 (5)	0.0012 (5)	0.0014 (5)
C15	0.0207 (7)	0.0232 (7)	0.0181 (6)	0.0003 (5)	0.0050 (5)	−0.0003 (5)
C16	0.0283 (7)	0.0205 (6)	0.0154 (6)	−0.0011 (5)	0.0015 (5)	0.0025 (5)
C17	0.0272 (7)	0.0243 (7)	0.0264 (7)	−0.0014 (6)	0.0011 (6)	0.0037 (6)
C18	0.0336 (8)	0.0290 (8)	0.0324 (8)	−0.0086 (6)	−0.0063 (6)	0.0053 (6)
C19	0.0493 (10)	0.0232 (7)	0.0267 (7)	−0.0092 (7)	−0.0057 (7)	0.0003 (6)
C20	0.0473 (9)	0.0217 (7)	0.0221 (7)	0.0040 (6)	0.0031 (6)	0.0007 (6)
C21	0.0289 (8)	0.0249 (7)	0.0202 (6)	0.0014 (5)	0.0014 (5)	0.0011 (5)
N1	0.0231 (6)	0.0181 (5)	0.0180 (5)	0.0012 (4)	0.0016 (4)	−0.0019 (4)
O1	0.0206 (5)	0.0293 (5)	0.0194 (4)	0.0031 (4)	0.0029 (4)	−0.0030 (4)
O2	0.0220 (5)	0.0322 (5)	0.0265 (5)	0.0042 (4)	0.0004 (4)	0.0051 (4)
O3	0.0245 (6)	0.0494 (7)	0.0268 (5)	0.0005 (4)	−0.0024 (4)	0.0017 (5)
O4	0.0300 (6)	0.0270 (5)	0.0197 (5)	−0.0001 (4)	−0.0014 (4)	−0.0001 (4)

Geometric parameters (Å, º) top

C1—O1	1.4320 (15)	C20—C21	1.3880 (19)
C1—C2	1.4956 (19)	C1—H1A	0.99
C2—O2	1.4201 (17)	C1—H1B	0.99
C3—O2	1.4237 (16)	C2—H2A	0.99
C3—C4	1.503 (2)	C2—H2B	0.99
C4—O3	1.4265 (18)	C3—H3A	0.99
C5—O3	1.4360 (16)	C3—H3B	0.99
C5—C6	1.5135 (18)	C4—H4A	0.99
C6—C7	1.5222 (18)	C4—H4B	0.99
C7—C8	1.5244 (19)	C5—H5A	0.99
C8—N1	1.4731 (16)	C5—H5B	0.99
C9—C10	1.3852 (18)	C6—H6A	0.99
C9—C14	1.4026 (18)	C6—H6B	0.99
C9—N1	1.4367 (16)	C7—H7A	0.99
C10—C11	1.3848 (18)	C7—H7B	0.99
C11—C12	1.383 (2)	C8—H8A	0.99
C12—C13	1.3856 (19)	C8—H8B	0.99
C13—C14	1.3894 (17)	C10—H10	0.95
C14—O1	1.3640 (15)	C11—H11	0.95
C15—O4	1.2318 (15)	C12—H12	0.95
C15—N1	1.3659 (16)	C13—H13	0.95
C15—C16	1.4982 (18)	C17—H17	0.95
C16—C21	1.3905 (18)	C18—H18	0.95
C16—C17	1.3906 (18)	C19—H19	0.95
C17—C18	1.3871 (19)	C20—H20	0.95
C18—C19	1.378 (2)	C21—H21	0.95
C19—C20	1.384 (2)

O1—C1—C2	107.14 (10)	O3—C4—H4A	108.7
O2—C2—C1	108.45 (11)	C3—C4—H4A	108.7
O2—C3—C4	110.17 (12)	O3—C4—H4B	108.7
O3—C4—C3	114.19 (11)	C3—C4—H4B	108.7
O3—C5—C6	113.19 (11)	O3—C5—H5A	108.9
C5—C6—C7	110.04 (11)	C6—C5—H5A	108.9
C6—C7—C8	115.67 (11)	O3—C5—H5B	108.9
N1—C8—C7	113.88 (11)	C6—C5—H5B	108.9
C10—C9—C14	119.46 (11)	C5—C6—H6A	109.7
C10—C9—N1	120.92 (11)	C7—C6—H6A	109.7
C14—C9—N1	119.62 (11)	C5—C6—H6B	109.7
C11—C10—C9	120.73 (12)	C7—C6—H6B	109.7
C12—C11—C10	119.35 (13)	C6—C7—H7A	108.4
C11—C12—C13	121.03 (12)	C8—C7—H7A	108.4
C12—C13—C14	119.51 (12)	C6—C7—H7B	108.4
O1—C14—C13	124.78 (11)	C8—C7—H7B	108.4
O1—C14—C9	115.35 (10)	N1—C8—H8A	108.8
C13—C14—C9	119.87 (12)	C7—C8—H8A	108.8
O4—C15—N1	122.54 (12)	N1—C8—H8B	108.8
O4—C15—C16	120.71 (11)	C7—C8—H8B	108.8
N1—C15—C16	116.64 (11)	C11—C10—H10	119.6
C21—C16—C17	119.57 (12)	C9—C10—H10	119.6
C21—C16—C15	119.85 (12)	C12—C11—H11	120.3
C17—C16—C15	120.46 (12)	C10—C11—H11	120.3
C18—C17—C16	120.20 (13)	C11—C12—H12	119.5
C19—C18—C17	119.84 (14)	C13—C12—H12	119.5
C18—C19—C20	120.53 (13)	C12—C13—H13	120.2
C19—C20—C21	119.82 (13)	C14—C13—H13	120.2
C20—C21—C16	120.02 (13)	C18—C17—H17	119.9
C15—N1—C9	120.59 (10)	C16—C17—H17	119.9
C15—N1—C8	119.90 (10)	C19—C18—H18	120.1
C9—N1—C8	118.31 (10)	C17—C18—H18	120.1
C14—O1—C1	118.14 (9)	C18—C19—H19	119.7
C2—O2—C3	112.17 (10)	C20—C19—H19	119.7
C4—O3—C5	115.40 (10)	C19—C20—H20	120.1
O1—C1—H1A	110.3	C21—C20—H20	120.1
C2—C1—H1A	110.3	C20—C21—H21	120
O1—C1—H1B	110.3	C16—C21—H21	120
C2—C1—H1B	110.3	H1A—C1—H1B	108.5
O2—C2—H2A	110	H2A—C2—H2B	108.4
C1—C2—H2A	110	H3A—C3—H3B	108.1
O2—C2—H2B	110	H4A—C4—H4B	107.6
C1—C2—H2B	110	H5A—C5—H5B	107.8
O2—C3—H3A	109.6	H6A—C6—H6B	108.2
C4—C3—H3A	109.6	H7A—C7—H7B	107.4
O2—C3—H3B	109.6	H8A—C8—H8B	107.7
C4—C3—H3B	109.6

Experimental details

Crystal data
Chemical formula	C₂₁H₂₅NO₄
M_r	355.42
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	123
a, b, c (Å)	16.825 (1), 13.550 (1), 8.173 (1)
β (°)	95.02 (1)
V (Å³)	1856.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.22 × 0.16 × 0.09

Data collection
Diffractometer	KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	25477, 5351, 3438
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.706

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.114, 1.04
No. of reflections	5351
No. of parameters	235
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.23

Computer programs: COLLECT (Nonius, 1997-2000), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

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