N,N′-Dibenzyl-2,2′-(3,6-dioxaoctane-1,8-diyldi­oxy)dibenzamide

Abstract

The title compound, C₃₄H₃₆N₂O₆, located on a center of inversion, crystallizes with one half-mol­ecule in the asymmetric unit. The dihedral angle between the benzene rings is 86.19 (2)°. An intra­molecular N—H⋯O hydrogen bond forms a six-membered ring; it affects the conformation of the mol­ecule which adopts a folded rather than open conformation. The crystal packing is stabilized by inter­molecular C—H⋯O inter­actions.

Related literature

For background to the applications of amide-type acyclic polyethers, see: Wen et al. (2002 ▶, 2008 ▶); Lehn et al. (1995 ▶). For related structures of amide-type acyclic polyethers, see: Wen et al. (2005 ▶, 2008 ▶).

Experimental

Crystal data

• C₃₄H₃₆N₂O₆

• M _r = 568.65

• Monoclinic,

• a = 12.065 (3) Å

• b = 15.964 (4) Å

• c = 8.251 (2) Å

• β = 104.820 (5)°

• V = 1536.3 (7) ų

• Z = 2

• Mo Kα radiation

• μ = 0.08 mm⁻¹

• T = 294 K

• 0.24 × 0.20 × 0.16 mm

Data collection

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.976, T _max = 0.983

• 7850 measured reflections

• 2707 independent reflections

• 1284 reflections with I > 2σ(I)

• R _int = 0.041

Refinement

• R[F ² > 2σ(F ²)] = 0.048

• wR(F ²) = 0.149

• S = 1.00

• 2707 reflections

• 190 parameters

• 36 restraints

• H-atom parameters constrained

• Δρ_max = 0.21 e Å⁻³

• Δρ_min = −0.17 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.86	1.97	2.645 (3)	135
C15—H15B⋯O1i	0.97	2.69	3.580 (5)	152

Symmetry code: (i) .

supplementary crystallographic information

Comment

Increasing attention has focused on acyclic polyether compounds, due to their complexing ability (Wen et al., 2008), selectivity (Wen et al., 2002) to metal ions and their potential application in supramolecular chemistry (Lehn et al., 1995). In our ongoing studies of structures and properties of diamide-type acyclic polyethers, a new flexible acyclic polyether ligand 3,6-dioxa-1,8-octylenedi(N-benzyl-salicylamide) was synthesized. Herein we report the synthesis and structure of the title compound, (Fig. 1).

The title compound crystallizes in the monoclinic space group P2₁/c. The asymmetric unit of the title compound contains one half-molecule, the other half being related by a crystallographic center of inversion (Fig. 1). All bond lengths and angles in the title compound are within normal ranges, and comparable with those in the related compounds (Wen et al., 2005, & Wen et al., 2008). In the asymmetric unit, the dihedral angle between two benzene rings is 86.19 (2)°. An intramolecular N(1)—H(1)···O(2) hydrogen bond (Table 1) forms a six-numbered ring, and affects the conformation of the molecule which thus adopts a folded rather than open conformation. The crystal packing is stabilized by intermolecular C(15)—H(15B)···O(1) short-contact interactions (Table 1).

Experimental

The title compound was synthesized according to literature method (Wen et al., 2008). Colourless single cystals suitable for X-ray diffraction were obtained by slow evaporation of an ethanol solution over a period of 5 d.

Refinement

H atoms were positioned geometrically, with N—H = 0.86 Å and C—H = 0.95–0.99 Å, respectively, and constrained to ride on their parent atoms, with U_iso(H) = 1.2 U_eq(C,N). In the refinement, SIMU was used to restraint the displacement parameters of the atoms N1, C7, C6, C5, C1, C2 and C3 to move similarly.

Figures

Fig. 1.

The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids, Unlabelled atoms are related to labelled atoms by the symmetry operator (1 - x,2 - y,-z).

Fig. 2.

The packing diagram of the title compound, viewed down the a axis.

Crystal data

C34H36N2O6	F(000) = 604
Mr = 568.65	Dx = 1.229 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1307 reflections
a = 12.065 (3) Å	θ = 2.6–20.3°
b = 15.964 (4) Å	µ = 0.08 mm−1
c = 8.251 (2) Å	T = 294 K
β = 104.820 (5)°	Prism, colourless
V = 1536.3 (7) Å3	0.24 × 0.20 × 0.16 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	2707 independent reflections
Radiation source: fine-focus sealed tube	1284 reflections with I > 2σ(I)
graphite	Rint = 0.041
φ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
Tmin = 0.976, Tmax = 0.983	k = −18→18
7850 measured reflections	l = −7→9

Refinement

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.149	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0574P)2 + 0.3181P] where P = (Fo2 + 2Fc2)/3
2707 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.21 e Å−3
36 restraints	Δρmin = −0.17 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.8814 (2)	0.90823 (13)	0.7723 (3)	0.1004 (8)
O2	0.83284 (14)	1.05219 (11)	0.3438 (2)	0.0662 (5)
O3	0.63670 (17)	1.03915 (16)	0.0958 (3)	0.0971 (8)
N1	0.7835 (2)	0.91898 (14)	0.5028 (3)	0.0738 (7)
H1	0.7665	0.9504	0.4152	0.089*
C1	0.5392 (3)	0.7869 (2)	0.3307 (5)	0.1097 (13)
H1A	0.5756	0.7521	0.2699	0.132*
C2	0.4202 (4)	0.7860 (3)	0.2970 (5)	0.1218 (14)
H2	0.3780	0.7504	0.2147	0.146*
C3	0.3657 (3)	0.8361 (2)	0.3827 (5)	0.0925 (10)
H3	0.2861	0.8355	0.3603	0.111*
C4	0.4281 (3)	0.88690 (19)	0.5011 (4)	0.0820 (10)
H4	0.3913	0.9219	0.5611	0.098*
C5	0.5463 (3)	0.88771 (18)	0.5347 (4)	0.0750 (9)
H5	0.5878	0.9235	0.6172	0.090*
C6	0.6031 (3)	0.83769 (17)	0.4504 (4)	0.0670 (8)
C7	0.7328 (3)	0.83619 (18)	0.4915 (5)	0.0901 (10)
H7B	0.7619	0.8074	0.5974	0.108*
H7A	0.7564	0.8045	0.4057	0.108*
C8	0.8553 (3)	0.94947 (19)	0.6421 (4)	0.0679 (8)
C9	0.9030 (2)	1.03553 (16)	0.6358 (3)	0.0562 (7)
C10	0.9664 (3)	1.0684 (2)	0.7883 (4)	0.0741 (9)
H10	0.9754	1.0363	0.8848	0.089*
C11	1.0157 (3)	1.1460 (2)	0.8009 (4)	0.0831 (10)
H11	1.0576	1.1658	0.9045	0.100*
C12	1.0031 (2)	1.1942 (2)	0.6606 (4)	0.0752 (9)
H12	1.0360	1.2472	0.6687	0.090*
C13	0.9419 (2)	1.16458 (18)	0.5074 (4)	0.0644 (8)
H13	0.9334	1.1978	0.4124	0.077*
C14	0.8926 (2)	1.08525 (17)	0.4938 (3)	0.0549 (7)
C15	0.8169 (2)	1.09965 (18)	0.1928 (3)	0.0706 (8)
H15B	0.8901	1.1111	0.1691	0.085*
H15A	0.7796	1.1525	0.2029	0.085*
C16	0.7438 (2)	1.0481 (2)	0.0572 (4)	0.0816 (9)
H16B	0.7341	1.0755	−0.0504	0.098*
H16A	0.7786	0.9936	0.0524	0.098*
C17	0.5563 (2)	0.9992 (3)	−0.0245 (4)	0.1032 (12)
H17A	0.5797	0.9418	−0.0352	0.124*
H17B	0.5477	1.0270	−0.1316	0.124*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.1298 (19)	0.0877 (16)	0.0854 (16)	0.0126 (13)	0.0307 (15)	0.0363 (13)
O2	0.0697 (12)	0.0723 (12)	0.0529 (12)	−0.0104 (10)	0.0088 (10)	0.0102 (10)
O3	0.0592 (12)	0.166 (2)	0.0638 (13)	−0.0177 (13)	0.0111 (11)	−0.0132 (14)
N1	0.0729 (15)	0.0547 (15)	0.094 (2)	−0.0021 (12)	0.0223 (15)	0.0136 (13)
C1	0.104 (3)	0.111 (3)	0.135 (3)	−0.023 (2)	0.070 (3)	−0.057 (3)
C2	0.109 (3)	0.143 (4)	0.123 (3)	−0.039 (3)	0.048 (3)	−0.060 (3)
C3	0.078 (2)	0.095 (3)	0.112 (3)	−0.005 (2)	0.038 (2)	0.004 (2)
C4	0.093 (3)	0.063 (2)	0.104 (3)	0.0074 (18)	0.052 (2)	0.0007 (19)
C5	0.088 (2)	0.060 (2)	0.082 (2)	0.0002 (16)	0.0303 (19)	−0.0095 (15)
C6	0.080 (2)	0.0470 (17)	0.084 (2)	−0.0002 (15)	0.0404 (18)	0.0021 (15)
C7	0.082 (2)	0.061 (2)	0.136 (3)	0.0042 (17)	0.042 (2)	0.0050 (19)
C8	0.0675 (18)	0.069 (2)	0.072 (2)	0.0162 (16)	0.0270 (17)	0.0122 (18)
C9	0.0540 (15)	0.0587 (17)	0.0592 (18)	0.0141 (13)	0.0206 (14)	0.0100 (14)
C10	0.085 (2)	0.082 (2)	0.056 (2)	0.0255 (18)	0.0178 (17)	0.0048 (17)
C11	0.085 (2)	0.090 (3)	0.072 (2)	0.015 (2)	0.0155 (19)	−0.021 (2)
C12	0.0698 (19)	0.075 (2)	0.083 (2)	−0.0045 (16)	0.0235 (18)	−0.021 (2)
C13	0.0664 (17)	0.0639 (19)	0.068 (2)	−0.0026 (15)	0.0261 (16)	0.0025 (15)
C14	0.0453 (14)	0.0676 (19)	0.0531 (17)	0.0065 (13)	0.0152 (13)	0.0018 (14)
C15	0.0653 (18)	0.087 (2)	0.0589 (18)	−0.0016 (16)	0.0151 (15)	0.0157 (16)
C16	0.0552 (18)	0.129 (3)	0.060 (2)	−0.0024 (18)	0.0141 (16)	0.0139 (19)
C17	0.077 (2)	0.161 (3)	0.071 (2)	−0.031 (2)	0.0201 (19)	−0.019 (2)

Geometric parameters (Å, °)

O1—C8	1.231 (3)	C7—H7A	0.9700
O2—C14	1.369 (3)	C8—C9	1.496 (4)
O2—C15	1.429 (3)	C9—C14	1.394 (3)
O3—C17	1.356 (3)	C9—C10	1.397 (4)
O3—C16	1.415 (3)	C10—C11	1.365 (4)
N1—C8	1.341 (3)	C10—H10	0.9300
N1—C7	1.449 (3)	C11—C12	1.366 (4)
N1—H1	0.8600	C11—H11	0.9300
C1—C6	1.356 (4)	C12—C13	1.374 (4)
C1—C2	1.392 (5)	C12—H12	0.9300
C1—H1A	0.9300	C13—C14	1.391 (4)
C2—C3	1.345 (4)	C13—H13	0.9300
C2—H2	0.9300	C15—C16	1.484 (4)
C3—C4	1.343 (4)	C15—H15B	0.9700
C3—H3	0.9300	C15—H15A	0.9700
C4—C5	1.381 (4)	C16—H16B	0.9700
C4—H4	0.9300	C16—H16A	0.9700
C5—C6	1.355 (4)	C17—C17i	1.514 (6)
C5—H5	0.9300	C17—H17A	0.9700
C6—C7	1.514 (4)	C17—H17B	0.9700
C7—H7B	0.9700
C14—O2—C15	120.4 (2)	C10—C9—C8	116.2 (3)
C17—O3—C16	113.9 (2)	C11—C10—C9	122.5 (3)
C8—N1—C7	123.7 (3)	C11—C10—H10	118.8
C8—N1—H1	118.1	C9—C10—H10	118.8
C7—N1—H1	118.1	C10—C11—C12	119.6 (3)
C6—C1—C2	121.1 (3)	C10—C11—H11	120.2
C6—C1—H1A	119.4	C12—C11—H11	120.2
C2—C1—H1A	119.4	C11—C12—C13	120.2 (3)
C3—C2—C1	120.5 (3)	C11—C12—H12	119.9
C3—C2—H2	119.8	C13—C12—H12	119.9
C1—C2—H2	119.8	C12—C13—C14	120.3 (3)
C4—C3—C2	118.9 (3)	C12—C13—H13	119.8
C4—C3—H3	120.5	C14—C13—H13	119.8
C2—C3—H3	120.5	O2—C14—C13	122.6 (2)
C3—C4—C5	120.6 (3)	O2—C14—C9	117.0 (2)
C3—C4—H4	119.7	C13—C14—C9	120.4 (3)
C5—C4—H4	119.7	O2—C15—C16	106.5 (2)
C6—C5—C4	121.6 (3)	O2—C15—H15B	110.4
C6—C5—H5	119.2	C16—C15—H15B	110.4
C4—C5—H5	119.2	O2—C15—H15A	110.4
C5—C6—C1	117.3 (3)	C16—C15—H15A	110.4
C5—C6—C7	121.6 (3)	H15B—C15—H15A	108.6
C1—C6—C7	121.1 (3)	O3—C16—C15	106.7 (2)
N1—C7—C6	113.2 (2)	O3—C16—H16B	110.4
N1—C7—H7B	108.9	C15—C16—H16B	110.4
C6—C7—H7B	108.9	O3—C16—H16A	110.4
N1—C7—H7A	108.9	C15—C16—H16A	110.4
C6—C7—H7A	108.9	H16B—C16—H16A	108.6
H7B—C7—H7A	107.7	O3—C17—C17i	108.6 (3)
O1—C8—N1	121.3 (3)	O3—C17—H17A	110.0
O1—C8—C9	120.5 (3)	C17i—C17—H17A	110.0
N1—C8—C9	118.3 (3)	O3—C17—H17B	110.0
C14—C9—C10	117.0 (3)	C17i—C17—H17B	110.0
C14—C9—C8	126.8 (3)	H17A—C17—H17B	108.3
C6—C1—C2—C3	0.3 (6)	C14—C9—C10—C11	0.7 (4)
C1—C2—C3—C4	0.0 (6)	C8—C9—C10—C11	179.5 (3)
C2—C3—C4—C5	−0.1 (5)	C9—C10—C11—C12	0.2 (5)
C3—C4—C5—C6	−0.1 (5)	C10—C11—C12—C13	−0.5 (5)
C4—C5—C6—C1	0.4 (5)	C11—C12—C13—C14	−0.2 (4)
C4—C5—C6—C7	−177.7 (3)	C15—O2—C14—C13	−1.1 (4)
C2—C1—C6—C5	−0.5 (5)	C15—O2—C14—C9	179.1 (2)
C2—C1—C6—C7	177.6 (3)	C12—C13—C14—O2	−178.7 (2)
C8—N1—C7—C6	119.0 (3)	C12—C13—C14—C9	1.2 (4)
C5—C6—C7—N1	−48.7 (4)	C10—C9—C14—O2	178.5 (2)
C1—C6—C7—N1	133.4 (3)	C8—C9—C14—O2	−0.2 (4)
C7—N1—C8—O1	−1.2 (4)	C10—C9—C14—C13	−1.3 (4)
C7—N1—C8—C9	179.0 (2)	C8—C9—C14—C13	180.0 (2)
O1—C8—C9—C14	171.6 (3)	C14—O2—C15—C16	−176.8 (2)
N1—C8—C9—C14	−8.5 (4)	C17—O3—C16—C15	174.7 (3)
O1—C8—C9—C10	−7.1 (4)	O2—C15—C16—O3	63.9 (3)
N1—C8—C9—C10	172.7 (2)	C16—O3—C17—C17i	−174.9 (4)

Symmetry codes: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	1.97	2.645 (3)	135
C15—H15B···O1ii	0.97	2.69	3.580 (5)	152

Symmetry codes: (ii) −x+2, −y+2, −z+1.