Twist-chair conformation of the tetra­oxepane ring remains unchanged in tetra­oxa­spiro­dodecane di­amines

Khalilov, L.M.; Mescheryakova, E.S.; Bikmukhametov, K.S.; Makhmudiyarova, N.N.; Shangaraev, K.R.; Tulyabaev, A.R.

doi:10.1107/S2053229620001382

Twist-chair conformation of the tetraoxepane ring remains unchanged in tetraoxaspirododecane diamines

L. M. Khalilov, E. S. Mescheryakova, K. S. Bikmukhametov, N. N. Makhmudiyarova, K. R. Shangaraev and A. R. Tulyabaev

A detailed structural analysis has been performed for N,N′-bis(4-chlorophenyl)-7,8,11,12-tetraoxaspiro[5.6]dodecane-9,10-diamine, C₂₀H₂₂Cl₂N₂O₄, (I), N,N′-bis(2-fluorophenyl)-7,8,11,12-tetraoxaspiro[5.6]dodecane-9,10-diamine, C₂₀H₂₂F₂N₂O₄, (II), and N,N′-bis(4-fluorophenyl)-7,8,11,12-tetraoxaspiro[5.6]dodecane-9,10-diamine, C₂₀H₂₂F₂N₂O₄, (III). The seven-membered ring with two peroxide groups adopts a twist-chair conformation in all three compounds. The lengths of the C—N and O—O bonds are slightly shorter than the average statistical values found in the literature for azepanes and 1,2,4,5-tetraoxepanes. The geometry analysis of compounds (I)–(III), the topological analysis of the electron density at the (3, −1) bond critical points within Bader's quantum theory of `Atoms in molecules' (QTAIM) and NBO (natural bond orbital) analysis at the B3LYP/6-31G(d,2p) level of theory showed that there are n_O→σ*(C—O), n_N→σ*(C—O) and n_O→σ*(C—N) stereoelectronic effects. The molecules of compounds (I) and (III) are packed in the crystals as zigzag chains due to strong N—H

O and C—H

O hydrogen-bond interactions, whereas the molecules of compound (II) form chains in the crystals bound by N—H

O, C—H

π and C—H

O contacts. All these data show that halogen atoms and their positions have a minimal effect on the geometric parameters, stereoelectronic effects and crystal packing of compounds (I)–(III), so that the twist-chair conformation of the tetraoxepane ring remains unchanged.

Keywords: tetraoxepane; tetraoxaspirododecane diamine; lattice energy; computational chemistry; crystal structure; CLP; PIXEL.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229620001382/vp3002sup1.cif Contains datablocks global, compound_I, compound_II, compound_III
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229620001382/vp3002compound_Isup2.hkl Contains datablock compound_I
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229620001382/vp3002compound_IIsup3.hkl Contains datablock compound_II
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229620001382/vp3002compound_IIIsup4.hkl Contains datablock compound_III
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229620001382/vp3002sup5.pdf Geometry details

CCDC references: 1981916; 1981917; 1981918

Computing details top

For all structures, data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014). Program(s) used to solve structure: SHELXT (Sheldrick, 2015a) for compound_I, compound_III; SHELXD (Sheldrick, 2008) for compound_II. For all structures, program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

(compound_I) top

Crystal data top

C₂₀H₂₂Cl₂N₂O₄	F(000) = 888
M_r = 425.30	D_x = 1.413 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.5362 (9) Å	Cell parameters from 3198 reflections
b = 9.4705 (6) Å	θ = 2.4–26.8°
c = 20.3165 (17) Å	µ = 0.35 mm⁻¹
β = 99.462 (8)°	T = 293 K
V = 1999.7 (3) Å³	Prizm
Z = 4	0.72 × 0.54 × 0.28 mm

Data collection top

Agilent Xcalibur Eos diffractometer	4644 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2780 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 16.1709 pixels mm^-1	θ_max = 29.3°, θ_min = 2.0°
ω scans	h = −12→14
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −12→12
T_min = 0.647, T_max = 1.000	l = −24→27
13245 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.059	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.188	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
S = 0.97	(Δ/σ)_max < 0.001
4644 reflections	Δρ_max = 0.36 e Å⁻³
261 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.1040 (3)	0.4237 (3)	0.60376 (12)	0.0401 (6)
C2	0.1259 (3)	0.3086 (3)	0.55582 (14)	0.0539 (8)
H2A	0.217624	0.295086	0.557512	0.065*
H2B	0.089375	0.336911	0.510797	0.065*
C3	0.0650 (4)	0.1692 (3)	0.57237 (18)	0.0659 (10)
H3A	0.073075	0.100386	0.537937	0.079*
H3B	0.110618	0.133207	0.614374	0.079*
C4	−0.0753 (4)	0.1878 (3)	0.57741 (19)	0.0733 (11)
H4A	−0.110567	0.098182	0.588783	0.088*
H4B	−0.122083	0.217472	0.534494	0.088*
C5	−0.0928 (3)	0.2964 (3)	0.62969 (17)	0.0634 (9)
H5A	−0.051376	0.263888	0.673234	0.076*
H5B	−0.183754	0.308703	0.630992	0.076*
C6	−0.0343 (3)	0.4371 (3)	0.61351 (15)	0.0508 (7)
H6A	−0.084610	0.475530	0.573215	0.061*
H6B	−0.039275	0.503006	0.649541	0.061*
C9	0.3026 (3)	0.6716 (3)	0.64838 (13)	0.0407 (6)
H9	0.349226	0.669286	0.610449	0.049*
C10	0.3503 (2)	0.5515 (3)	0.69623 (13)	0.0404 (6)
H10	0.318660	0.564717	0.738561	0.048*
C14	0.3664 (2)	0.9212 (3)	0.65061 (13)	0.0397 (6)
C15	0.4270 (3)	1.0295 (3)	0.69015 (14)	0.0471 (7)
H15	0.433712	1.023756	0.736289	0.057*
C16	0.4768 (3)	1.1441 (3)	0.66243 (15)	0.0529 (8)
H16	0.518498	1.214611	0.689677	0.063*
C17	0.4653 (3)	1.1551 (3)	0.59440 (14)	0.0477 (7)
C18	0.4018 (3)	1.0541 (3)	0.55388 (14)	0.0519 (7)
H18	0.391895	1.063502	0.507751	0.062*
C19	0.3518 (3)	0.9370 (3)	0.58200 (14)	0.0489 (7)
H19	0.308095	0.868413	0.554381	0.059*
C21	0.5605 (2)	0.4661 (3)	0.75524 (13)	0.0406 (6)
C22	0.5104 (3)	0.3963 (3)	0.80536 (13)	0.0434 (6)
H22	0.423220	0.403803	0.807575	0.052*
C23	0.5890 (3)	0.3160 (3)	0.85179 (14)	0.0461 (7)
H23	0.555368	0.270577	0.885680	0.055*
C24	0.7169 (3)	0.3036 (3)	0.84774 (14)	0.0458 (7)
C25	0.7681 (3)	0.3704 (3)	0.79841 (16)	0.0592 (8)
H25	0.854873	0.360056	0.795724	0.071*
C26	0.6904 (3)	0.4527 (3)	0.75295 (15)	0.0571 (8)
H26	0.725529	0.500175	0.720132	0.068*
Cl1	0.53118 (9)	1.30125 (9)	0.56012 (5)	0.0733 (3)
Cl2	0.81568 (8)	0.19855 (9)	0.90578 (4)	0.0632 (3)
N13	0.3226 (2)	0.8028 (2)	0.68056 (13)	0.0469 (6)
H13	0.337 (3)	0.808 (3)	0.7198 (14)	0.039 (8)*
N20	0.4854 (2)	0.5511 (3)	0.70745 (13)	0.0465 (6)
H20	0.518 (3)	0.569 (4)	0.6770 (16)	0.061 (11)*
O7	0.15156 (19)	0.54649 (18)	0.57565 (9)	0.0490 (5)
O8	0.16622 (18)	0.66138 (18)	0.62410 (10)	0.0480 (5)
O11	0.31096 (17)	0.41454 (17)	0.66852 (9)	0.0433 (5)
O12	0.17285 (16)	0.40240 (18)	0.66976 (8)	0.0416 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0413 (14)	0.0399 (13)	0.0367 (13)	0.0000 (11)	−0.0001 (11)	0.0035 (11)
C2	0.0571 (19)	0.0555 (17)	0.0467 (16)	0.0022 (13)	0.0019 (14)	−0.0062 (13)
C3	0.076 (2)	0.0455 (16)	0.071 (2)	0.0005 (15)	−0.0035 (18)	−0.0075 (14)
C4	0.073 (3)	0.0568 (19)	0.080 (2)	−0.0175 (16)	−0.016 (2)	0.0101 (17)
C5	0.0493 (19)	0.070 (2)	0.069 (2)	−0.0101 (15)	0.0038 (15)	0.0122 (17)
C6	0.0429 (15)	0.0549 (16)	0.0514 (16)	0.0039 (13)	−0.0018 (13)	0.0030 (13)
C9	0.0389 (15)	0.0410 (14)	0.0431 (14)	0.0013 (11)	0.0094 (11)	−0.0003 (11)
C10	0.0353 (14)	0.0417 (14)	0.0443 (14)	−0.0013 (11)	0.0071 (11)	−0.0037 (11)
C14	0.0342 (14)	0.0386 (13)	0.0458 (14)	0.0052 (10)	0.0051 (11)	−0.0012 (11)
C15	0.0510 (17)	0.0451 (15)	0.0445 (15)	0.0015 (12)	0.0057 (12)	−0.0082 (12)
C16	0.0539 (18)	0.0408 (14)	0.0619 (19)	−0.0025 (13)	0.0033 (14)	−0.0082 (13)
C17	0.0460 (16)	0.0430 (14)	0.0537 (17)	0.0012 (12)	0.0069 (13)	0.0025 (12)
C18	0.0564 (18)	0.0549 (16)	0.0435 (15)	0.0015 (14)	0.0054 (13)	0.0008 (13)
C19	0.0509 (17)	0.0433 (14)	0.0503 (16)	−0.0023 (12)	0.0011 (13)	−0.0045 (12)
C21	0.0347 (14)	0.0391 (13)	0.0469 (14)	−0.0040 (11)	0.0037 (11)	−0.0045 (11)
C22	0.0308 (13)	0.0468 (14)	0.0535 (15)	−0.0028 (11)	0.0092 (11)	−0.0027 (12)
C23	0.0405 (16)	0.0500 (15)	0.0478 (15)	−0.0032 (12)	0.0076 (12)	−0.0008 (12)
C24	0.0379 (15)	0.0454 (15)	0.0512 (16)	−0.0011 (11)	−0.0009 (12)	−0.0042 (12)
C25	0.0286 (14)	0.074 (2)	0.076 (2)	0.0010 (14)	0.0090 (14)	0.0115 (16)
C26	0.0368 (16)	0.0696 (19)	0.0661 (19)	−0.0047 (14)	0.0124 (14)	0.0166 (15)
Cl1	0.0760 (6)	0.0635 (5)	0.0804 (6)	−0.0202 (4)	0.0132 (5)	0.0081 (4)
Cl2	0.0546 (5)	0.0749 (5)	0.0570 (5)	0.0137 (4)	0.0000 (4)	0.0065 (4)
N13	0.0570 (16)	0.0424 (13)	0.0422 (14)	−0.0049 (10)	0.0108 (11)	−0.0035 (11)
N20	0.0349 (13)	0.0562 (14)	0.0490 (14)	−0.0006 (10)	0.0084 (11)	0.0085 (11)
O7	0.0572 (12)	0.0463 (10)	0.0410 (10)	−0.0055 (9)	0.0004 (9)	0.0043 (8)
O8	0.0413 (11)	0.0405 (10)	0.0605 (12)	0.0048 (8)	0.0031 (9)	0.0006 (8)
O11	0.0325 (10)	0.0436 (10)	0.0528 (11)	0.0020 (8)	0.0041 (8)	−0.0020 (8)
O12	0.0343 (10)	0.0488 (10)	0.0399 (10)	−0.0015 (8)	0.0009 (7)	0.0031 (8)

Geometric parameters (Å, º) top

C1—C2	1.505 (4)	C14—N13	1.390 (3)
C1—C6	1.508 (4)	C15—H15	0.9300
C1—O7	1.423 (3)	C15—C16	1.367 (4)
C1—O12	1.430 (3)	C16—H16	0.9300
C2—H2A	0.9700	C16—C17	1.371 (4)
C2—H2B	0.9700	C17—C18	1.364 (4)
C2—C3	1.529 (4)	C17—Cl1	1.744 (3)
C3—H3A	0.9700	C18—H18	0.9300
C3—H3B	0.9700	C18—C19	1.389 (4)
C3—C4	1.508 (5)	C19—H19	0.9300
C4—H4A	0.9700	C21—C22	1.389 (4)
C4—H4B	0.9700	C21—C26	1.383 (4)
C4—C5	1.511 (5)	C21—N20	1.401 (3)
C5—H5A	0.9700	C22—H22	0.9300
C5—H5B	0.9700	C22—C23	1.377 (4)
C5—C6	1.526 (4)	C23—H23	0.9300
C6—H6A	0.9700	C23—C24	1.368 (4)
C6—H6B	0.9700	C24—C25	1.369 (4)
C9—H9	0.9800	C24—Cl2	1.749 (3)
C9—C10	1.527 (3)	C25—H25	0.9300
C9—N13	1.404 (3)	C25—C26	1.372 (4)
C9—O8	1.444 (3)	C26—H26	0.9300
C10—H10	0.9800	N13—H13	0.79 (3)
C10—N20	1.404 (3)	N20—H20	0.77 (4)
C10—O11	1.447 (3)	O7—O8	1.458 (2)
C14—C15	1.392 (3)	O11—O12	1.464 (2)
C14—C19	1.385 (4)

C2—C1—C6	113.6 (2)	O11—C10—H10	109.9
O7—C1—C2	103.3 (2)	C19—C14—C15	117.7 (2)
O7—C1—C6	113.3 (2)	C19—C14—N13	122.6 (2)
O7—C1—O12	109.49 (18)	N13—C14—C15	119.7 (2)
O12—C1—C2	113.3 (2)	C14—C15—H15	119.4
O12—C1—C6	104.0 (2)	C16—C15—C14	121.2 (3)
C1—C2—H2A	109.3	C16—C15—H15	119.4
C1—C2—H2B	109.3	C15—C16—H16	120.0
C1—C2—C3	111.6 (3)	C15—C16—C17	119.9 (2)
H2A—C2—H2B	108.0	C17—C16—H16	120.0
C3—C2—H2A	109.3	C16—C17—Cl1	119.2 (2)
C3—C2—H2B	109.3	C18—C17—C16	120.6 (3)
C2—C3—H3A	109.3	C18—C17—Cl1	120.2 (2)
C2—C3—H3B	109.3	C17—C18—H18	120.2
H3A—C3—H3B	108.0	C17—C18—C19	119.5 (3)
C4—C3—C2	111.4 (3)	C19—C18—H18	120.2
C4—C3—H3A	109.3	C14—C19—C18	120.9 (2)
C4—C3—H3B	109.3	C14—C19—H19	119.5
C3—C4—H4A	109.4	C18—C19—H19	119.5
C3—C4—H4B	109.4	C22—C21—N20	122.8 (2)
C3—C4—C5	111.2 (3)	C26—C21—C22	118.6 (2)
H4A—C4—H4B	108.0	C26—C21—N20	118.6 (3)
C5—C4—H4A	109.4	C21—C22—H22	119.8
C5—C4—H4B	109.4	C23—C22—C21	120.5 (3)
C4—C5—H5A	109.7	C23—C22—H22	119.8
C4—C5—H5B	109.7	C22—C23—H23	120.2
C4—C5—C6	110.0 (3)	C24—C23—C22	119.6 (3)
H5A—C5—H5B	108.2	C24—C23—H23	120.2
C6—C5—H5A	109.7	C23—C24—C25	121.0 (2)
C6—C5—H5B	109.7	C23—C24—Cl2	119.4 (2)
C1—C6—C5	112.8 (2)	C25—C24—Cl2	119.6 (2)
C1—C6—H6A	109.0	C24—C25—H25	120.3
C1—C6—H6B	109.0	C24—C25—C26	119.5 (3)
C5—C6—H6A	109.0	C26—C25—H25	120.3
C5—C6—H6B	109.0	C21—C26—H26	119.5
H6A—C6—H6B	107.8	C25—C26—C21	120.9 (3)
C10—C9—H9	109.2	C25—C26—H26	119.5
N13—C9—H9	109.2	C9—N13—H13	121 (2)
N13—C9—C10	110.8 (2)	C14—N13—C9	123.0 (2)
N13—C9—O8	106.4 (2)	C14—N13—H13	112 (2)
O8—C9—H9	109.2	C10—N20—H20	116 (2)
O8—C9—C10	111.9 (2)	C21—N20—C10	123.8 (2)
C9—C10—H10	109.9	C21—N20—H20	114 (3)
N20—C10—C9	108.9 (2)	C1—O7—O8	110.13 (18)
N20—C10—H10	109.9	C9—O8—O7	105.63 (18)
N20—C10—O11	106.2 (2)	C10—O11—O12	106.58 (16)
O11—C10—C9	112.13 (19)	C1—O12—O11	109.00 (18)

C1—C2—C3—C4	53.1 (3)	C22—C21—N20—C10	−13.9 (4)
C1—O7—O8—C9	104.2 (2)	C22—C23—C24—C25	0.4 (4)
C2—C1—C6—C5	50.4 (3)	C22—C23—C24—Cl2	−178.7 (2)
C2—C1—O7—O8	−166.28 (19)	C23—C24—C25—C26	1.0 (5)
C2—C1—O12—O11	66.8 (3)	C24—C25—C26—C21	−1.7 (5)
C2—C3—C4—C5	−58.0 (4)	C26—C21—C22—C23	0.3 (4)
C3—C4—C5—C6	57.5 (3)	C26—C21—N20—C10	167.0 (3)
C4—C5—C6—C1	−53.5 (3)	Cl1—C17—C18—C19	178.8 (2)
C6—C1—C2—C3	−49.5 (3)	Cl2—C24—C25—C26	−180.0 (2)
C6—C1—O7—O8	70.3 (2)	N13—C9—C10—N20	−73.0 (3)
C6—C1—O12—O11	−169.39 (18)	N13—C9—C10—O11	169.8 (2)
C9—C10—N20—C21	171.7 (2)	N13—C9—O8—O7	164.42 (19)
C9—C10—O11—O12	−72.8 (2)	N13—C14—C15—C16	176.7 (3)
C10—C9—N13—C14	138.6 (3)	N13—C14—C19—C18	−177.2 (3)
C10—C9—O8—O7	−74.5 (2)	N20—C10—O11—O12	168.35 (19)
C10—O11—O12—C1	103.67 (19)	N20—C21—C22—C23	−178.9 (2)
C14—C15—C16—C17	1.3 (4)	N20—C21—C26—C25	−179.7 (3)
C15—C14—C19—C18	3.0 (4)	O7—C1—C2—C3	−172.7 (2)
C15—C14—N13—C9	−157.1 (3)	O7—C1—C6—C5	168.0 (2)
C15—C16—C17—C18	1.5 (5)	O7—C1—O12—O11	−48.0 (2)
C15—C16—C17—Cl1	−179.3 (2)	O8—C9—C10—N20	168.4 (2)
C16—C17—C18—C19	−2.0 (5)	O8—C9—C10—O11	51.2 (3)
C17—C18—C19—C14	−0.4 (4)	O8—C9—N13—C14	−99.5 (3)
C19—C14—C15—C16	−3.5 (4)	O11—C10—N20—C21	−67.4 (3)
C19—C14—N13—C9	23.2 (4)	O12—C1—C2—C3	68.9 (3)
C21—C22—C23—C24	−1.0 (4)	O12—C1—C6—C5	−73.2 (3)
C22—C21—C26—C25	1.1 (4)	O12—C1—O7—O8	−45.2 (2)

(compound_II) top

Crystal data top

C₂₀H₂₂F₂N₂O₄	F(000) = 824
M_r = 392.40	D_x = 1.386 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.9061 (6) Å	Cell parameters from 2196 reflections
b = 11.4711 (4) Å	θ = 2.1–27.2°
c = 8.7831 (3) Å	µ = 0.11 mm⁻¹
β = 99.134 (3)°	T = 293 K
V = 1880.67 (11) Å³	Prizm, colourless
Z = 4	0.52 × 0.32 × 0.29 mm

Data collection top

Agilent Xcalibur Eos diffractometer	4395 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2718 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
Detector resolution: 16.1709 pixels mm^-1	θ_max = 29.2°, θ_min = 2.1°
ω scans	h = −24→17
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −7→15
T_min = 0.593, T_max = 1.000	l = −11→9
9078 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.162	w = 1/[σ²(F_o²) + (0.0675P)² + 0.4744P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
4395 reflections	Δρ_max = 0.21 e Å⁻³
261 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.23777 (10)	0.02798 (17)	−0.0225 (2)	0.0369 (4)
C2	0.28211 (11)	−0.04452 (18)	−0.1160 (2)	0.0457 (5)
H2A	0.315454	0.005460	−0.158623	0.055*
H2B	0.250958	−0.081051	−0.201090	0.055*
C3	0.32325 (12)	−0.13764 (19)	−0.0161 (3)	0.0545 (6)
H3A	0.357973	−0.100672	0.062297	0.065*
H3B	0.349222	−0.185838	−0.079218	0.065*
C4	0.27386 (13)	−0.2140 (2)	0.0613 (3)	0.0605 (6)
H4A	0.242493	−0.257462	−0.016797	0.073*
H4B	0.302251	−0.269652	0.128259	0.073*
C5	0.22910 (13)	−0.1425 (2)	0.1548 (2)	0.0563 (6)
H5A	0.259943	−0.108501	0.242350	0.068*
H5B	0.194957	−0.192968	0.194093	0.068*
C6	0.18920 (11)	−0.04637 (19)	0.0589 (2)	0.0486 (5)
H6A	0.152393	−0.080860	−0.017277	0.058*
H6B	0.165665	0.002974	0.125347	0.058*
C9	0.20792 (10)	0.29987 (16)	−0.0555 (2)	0.0378 (4)
H9	0.210912	0.314805	−0.164192	0.045*
C10	0.28407 (10)	0.29235 (16)	0.0374 (2)	0.0379 (4)
H10	0.282083	0.305010	0.146988	0.045*
C14	0.11163 (10)	0.44631 (17)	−0.0831 (2)	0.0392 (5)
C15	0.09113 (11)	0.5549 (2)	−0.0374 (3)	0.0501 (5)
C16	0.03490 (13)	0.6159 (2)	−0.1168 (3)	0.0685 (7)
H16	0.022692	0.688800	−0.082704	0.082*
C17	−0.00332 (13)	0.5674 (3)	−0.2479 (3)	0.0716 (8)
H17	−0.041543	0.607759	−0.303745	0.086*
C18	0.01499 (12)	0.4597 (2)	−0.2960 (3)	0.0610 (6)
H18	−0.011045	0.427200	−0.384501	0.073*
C19	0.07163 (11)	0.3989 (2)	−0.2146 (2)	0.0479 (5)
H19	0.083118	0.325425	−0.248192	0.057*
C21	0.38551 (10)	0.42913 (17)	0.0805 (2)	0.0404 (5)
C22	0.41014 (11)	0.53715 (19)	0.0425 (3)	0.0482 (5)
C23	0.46557 (13)	0.5942 (2)	0.1310 (3)	0.0621 (6)
H23	0.480294	0.667047	0.101760	0.075*
C24	0.49904 (13)	0.5420 (3)	0.2635 (3)	0.0696 (7)
H24	0.536664	0.579540	0.325540	0.083*
C25	0.47673 (12)	0.4342 (2)	0.3042 (3)	0.0621 (6)
H25	0.499594	0.398805	0.394034	0.075*
C26	0.42087 (11)	0.3775 (2)	0.2138 (2)	0.0505 (5)
H26	0.406839	0.304043	0.242503	0.061*
F1	0.12913 (8)	0.60095 (12)	0.09316 (17)	0.0742 (4)
F2	0.37700 (8)	0.58683 (12)	−0.09048 (16)	0.0698 (4)
N13	0.17095 (9)	0.39167 (16)	0.0026 (2)	0.0455 (4)
H13	0.1811 (12)	0.409 (2)	0.094 (3)	0.056 (7)*
N20	0.32746 (10)	0.37810 (16)	−0.0150 (2)	0.0463 (4)
H20	0.3156 (13)	0.407 (2)	−0.103 (3)	0.070 (8)*
O7	0.19840 (7)	0.10592 (12)	−0.13077 (14)	0.0440 (4)
O8	0.16646 (7)	0.19510 (11)	−0.04342 (15)	0.0433 (4)
O11	0.31906 (7)	0.18243 (11)	0.01813 (15)	0.0427 (4)
O12	0.28075 (7)	0.09431 (11)	0.09484 (14)	0.0412 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0401 (10)	0.0365 (10)	0.0317 (9)	0.0008 (8)	−0.0014 (8)	−0.0021 (8)
C2	0.0547 (12)	0.0435 (12)	0.0402 (11)	0.0021 (10)	0.0113 (10)	−0.0013 (9)
C3	0.0562 (13)	0.0476 (13)	0.0593 (13)	0.0096 (11)	0.0077 (11)	−0.0013 (11)
C4	0.0800 (17)	0.0417 (12)	0.0592 (14)	0.0044 (12)	0.0089 (13)	0.0071 (11)
C5	0.0729 (15)	0.0517 (14)	0.0440 (12)	−0.0112 (12)	0.0084 (11)	0.0050 (11)
C6	0.0476 (11)	0.0501 (13)	0.0495 (12)	−0.0080 (10)	0.0119 (10)	−0.0047 (10)
C9	0.0377 (10)	0.0381 (10)	0.0365 (10)	0.0033 (8)	0.0023 (8)	−0.0005 (8)
C10	0.0350 (9)	0.0362 (10)	0.0403 (10)	0.0019 (8)	−0.0002 (8)	−0.0012 (8)
C14	0.0359 (10)	0.0404 (11)	0.0412 (10)	0.0026 (8)	0.0057 (8)	0.0051 (9)
C15	0.0427 (11)	0.0454 (12)	0.0605 (14)	0.0013 (10)	0.0029 (10)	−0.0003 (11)
C16	0.0594 (15)	0.0538 (15)	0.0914 (19)	0.0210 (12)	0.0092 (14)	0.0048 (14)
C17	0.0511 (14)	0.081 (2)	0.0780 (17)	0.0211 (13)	−0.0032 (13)	0.0235 (16)
C18	0.0459 (12)	0.0787 (18)	0.0541 (13)	0.0042 (12)	−0.0052 (10)	0.0096 (13)
C19	0.0438 (11)	0.0540 (13)	0.0438 (11)	0.0023 (10)	0.0007 (9)	0.0024 (10)
C21	0.0341 (10)	0.0391 (11)	0.0481 (11)	0.0001 (8)	0.0065 (9)	−0.0067 (9)
C22	0.0424 (11)	0.0433 (12)	0.0586 (13)	0.0013 (10)	0.0075 (10)	−0.0009 (11)
C23	0.0551 (14)	0.0498 (14)	0.0811 (18)	−0.0125 (11)	0.0094 (13)	−0.0090 (13)
C24	0.0520 (13)	0.0794 (19)	0.0739 (17)	−0.0161 (14)	−0.0007 (13)	−0.0204 (15)
C25	0.0482 (13)	0.0773 (18)	0.0562 (14)	0.0001 (12)	−0.0056 (11)	−0.0029 (13)
C26	0.0433 (11)	0.0530 (13)	0.0536 (12)	−0.0007 (10)	0.0030 (10)	0.0013 (11)
F1	0.0708 (9)	0.0568 (9)	0.0887 (10)	0.0090 (7)	−0.0065 (8)	−0.0228 (8)
F2	0.0733 (9)	0.0524 (8)	0.0791 (10)	−0.0037 (7)	−0.0019 (8)	0.0160 (7)
N13	0.0477 (10)	0.0473 (10)	0.0375 (9)	0.0125 (8)	−0.0053 (8)	−0.0075 (8)
N20	0.0467 (10)	0.0452 (10)	0.0440 (10)	−0.0092 (8)	−0.0019 (8)	0.0079 (9)
O7	0.0526 (8)	0.0401 (8)	0.0358 (7)	0.0047 (6)	−0.0036 (6)	−0.0052 (6)
O8	0.0372 (7)	0.0405 (8)	0.0510 (8)	0.0006 (6)	0.0037 (6)	−0.0046 (7)
O11	0.0366 (7)	0.0381 (8)	0.0532 (8)	0.0003 (6)	0.0067 (6)	0.0009 (6)
O12	0.0478 (8)	0.0372 (8)	0.0362 (7)	−0.0041 (6)	−0.0008 (6)	0.0013 (6)

Geometric parameters (Å, º) top

C1—C2	1.512 (3)	C14—N13	1.396 (2)
C1—C6	1.514 (3)	C15—C16	1.367 (3)
C1—O7	1.426 (2)	C15—F1	1.360 (2)
C1—O12	1.427 (2)	C16—H16	0.9300
C2—H2A	0.9700	C16—C17	1.376 (4)
C2—H2B	0.9700	C17—H17	0.9300
C2—C3	1.517 (3)	C17—C18	1.367 (4)
C3—H3A	0.9700	C18—H18	0.9300
C3—H3B	0.9700	C18—C19	1.379 (3)
C3—C4	1.518 (3)	C19—H19	0.9300
C4—H4A	0.9700	C21—C22	1.383 (3)
C4—H4B	0.9700	C21—C26	1.385 (3)
C4—C5	1.512 (3)	C21—N20	1.400 (3)
C5—H5A	0.9700	C22—C23	1.368 (3)
C5—H5B	0.9700	C22—F2	1.360 (2)
C5—C6	1.515 (3)	C23—H23	0.9300
C6—H6A	0.9700	C23—C24	1.371 (3)
C6—H6B	0.9700	C24—H24	0.9300
C9—H9	0.9800	C24—C25	1.373 (3)
C9—C10	1.541 (3)	C25—H25	0.9300
C9—N13	1.404 (2)	C25—C26	1.379 (3)
C9—O8	1.448 (2)	C26—H26	0.9300
C10—H10	0.9800	N13—H13	0.82 (2)
C10—N20	1.405 (2)	N20—H20	0.84 (2)
C10—O11	1.446 (2)	O7—O8	1.4652 (17)
C14—C15	1.383 (3)	O11—O12	1.4680 (17)
C14—C19	1.387 (3)

C2—C1—C6	112.15 (18)	O11—C10—H10	109.5
O7—C1—C2	104.98 (14)	C15—C14—C19	117.00 (19)
O7—C1—C6	112.14 (15)	C15—C14—N13	119.06 (18)
O7—C1—O12	108.93 (15)	C19—C14—N13	123.93 (19)
O12—C1—C2	112.60 (15)	C16—C15—C14	122.9 (2)
O12—C1—C6	106.11 (14)	F1—C15—C14	117.39 (18)
C1—C2—H2A	109.5	F1—C15—C16	119.7 (2)
C1—C2—H2B	109.5	C15—C16—H16	120.6
C1—C2—C3	110.52 (16)	C15—C16—C17	118.8 (2)
H2A—C2—H2B	108.1	C17—C16—H16	120.6
C3—C2—H2A	109.5	C16—C17—H17	120.1
C3—C2—H2B	109.5	C18—C17—C16	119.9 (2)
C2—C3—H3A	109.3	C18—C17—H17	120.1
C2—C3—H3B	109.3	C17—C18—H18	119.6
C2—C3—C4	111.74 (19)	C17—C18—C19	120.7 (2)
H3A—C3—H3B	107.9	C19—C18—H18	119.6
C4—C3—H3A	109.3	C14—C19—H19	119.7
C4—C3—H3B	109.3	C18—C19—C14	120.6 (2)
C3—C4—H4A	109.3	C18—C19—H19	119.7
C3—C4—H4B	109.3	C22—C21—C26	116.83 (19)
H4A—C4—H4B	108.0	C22—C21—N20	119.44 (19)
C5—C4—C3	111.55 (19)	C26—C21—N20	123.7 (2)
C5—C4—H4A	109.3	C23—C22—C21	123.2 (2)
C5—C4—H4B	109.3	F2—C22—C21	117.14 (19)
C4—C5—H5A	109.3	F2—C22—C23	119.6 (2)
C4—C5—H5B	109.3	C22—C23—H23	120.6
C4—C5—C6	111.43 (17)	C22—C23—C24	118.9 (2)
H5A—C5—H5B	108.0	C24—C23—H23	120.6
C6—C5—H5A	109.3	C23—C24—H24	120.2
C6—C5—H5B	109.3	C23—C24—C25	119.7 (2)
C1—C6—C5	112.79 (17)	C25—C24—H24	120.2
C1—C6—H6A	109.0	C24—C25—H25	119.6
C1—C6—H6B	109.0	C24—C25—C26	120.9 (2)
C5—C6—H6A	109.0	C26—C25—H25	119.6
C5—C6—H6B	109.0	C21—C26—H26	119.7
H6A—C6—H6B	107.8	C25—C26—C21	120.5 (2)
C10—C9—H9	109.4	C25—C26—H26	119.7
N13—C9—H9	109.4	C9—N13—H13	118.8 (16)
N13—C9—C10	109.05 (16)	C14—N13—C9	122.94 (17)
N13—C9—O8	106.80 (15)	C14—N13—H13	117.8 (16)
O8—C9—H9	109.4	C10—N20—H20	119.7 (17)
O8—C9—C10	112.70 (15)	C21—N20—C10	122.63 (18)
C9—C10—H10	109.5	C21—N20—H20	117.2 (18)
N20—C10—C9	109.41 (16)	C1—O7—O8	107.68 (12)
N20—C10—H10	109.5	C9—O8—O7	105.55 (12)
N20—C10—O11	105.69 (15)	C10—O11—O12	106.16 (12)
O11—C10—C9	113.15 (15)	C1—O12—O11	107.55 (12)

C1—C2—C3—C4	55.8 (2)	C22—C23—C24—C25	0.3 (4)
C1—O7—O8—C9	106.24 (15)	C23—C24—C25—C26	−0.2 (4)
C2—C1—C6—C5	52.9 (2)	C24—C25—C26—C21	−0.8 (4)
C2—C1—O7—O8	−167.85 (13)	C26—C21—C22—C23	−1.4 (3)
C2—C1—O12—O11	67.08 (18)	C26—C21—C22—F2	178.16 (18)
C2—C3—C4—C5	−56.0 (3)	C26—C21—N20—C10	22.5 (3)
C3—C4—C5—C6	53.4 (3)	F1—C15—C16—C17	−179.4 (2)
C4—C5—C6—C1	−52.1 (3)	F2—C22—C23—C24	−179.1 (2)
C6—C1—C2—C3	−54.1 (2)	N13—C9—C10—N20	−79.4 (2)
C6—C1—O7—O8	70.13 (17)	N13—C9—C10—O11	163.05 (15)
C6—C1—O12—O11	−169.87 (13)	N13—C9—O8—O7	169.53 (13)
C9—C10—N20—C21	150.74 (18)	N13—C14—C15—C16	178.3 (2)
C9—C10—O11—O12	−69.08 (17)	N13—C14—C15—F1	−2.1 (3)
C10—C9—N13—C14	158.18 (18)	N13—C14—C19—C18	−178.02 (19)
C10—C9—O8—O7	−70.73 (17)	N20—C10—O11—O12	171.22 (13)
C10—O11—O12—C1	105.64 (15)	N20—C21—C22—C23	178.7 (2)
C14—C15—C16—C17	0.1 (4)	N20—C21—C22—F2	−1.8 (3)
C15—C14—C19—C18	1.2 (3)	N20—C21—C26—C25	−178.56 (19)
C15—C14—N13—C9	−161.48 (19)	O7—C1—C2—C3	−176.11 (16)
C15—C16—C17—C18	0.4 (4)	O7—C1—C6—C5	170.77 (16)
C16—C17—C18—C19	−0.2 (4)	O7—C1—O12—O11	−48.95 (16)
C17—C18—C19—C14	−0.7 (4)	O8—C9—C10—N20	162.18 (15)
C19—C14—C15—C16	−0.9 (3)	O8—C9—C10—O11	44.6 (2)
C19—C14—C15—F1	178.67 (18)	O8—C9—N13—C14	−79.8 (2)
C19—C14—N13—C9	17.7 (3)	O11—C10—N20—C21	−87.1 (2)
C21—C22—C23—C24	0.5 (4)	O12—C1—C2—C3	65.5 (2)
C22—C21—C26—C25	1.5 (3)	O12—C1—C6—C5	−70.4 (2)
C22—C21—N20—C10	−157.62 (19)	O12—C1—O7—O8	−47.03 (17)

(compound_III) top

Crystal data top

C₂₀H₂₂F₂N₂O₄	F(000) = 824
M_r = 392.40	D_x = 1.402 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.9687 (13) Å	Cell parameters from 2159 reflections
b = 10.0294 (8) Å	θ = 2.0–28.7°
c = 14.5182 (15) Å	µ = 0.11 mm⁻¹
β = 100.068 (9)°	T = 293 K
V = 1859.3 (3) Å³	Plank, yellow
Z = 4	0.77 × 0.34 × 0.16 mm

Data collection top

Agilent Xcalibur Eos diffractometer	4320 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2239 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
Detector resolution: 16.1709 pixels mm^-1	θ_max = 29.1°, θ_min = 2.3°
ω scans	h = −15→16
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −13→12
T_min = 0.332, T_max = 1.000	l = −18→12
9582 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.085	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.235	w = 1/[σ²(F_o²) + (0.084P)² + 1.124P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
4320 reflections	Δρ_max = 0.67 e Å⁻³
261 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.8811 (2)	0.5942 (3)	0.5931 (2)	0.0368 (8)
C2	0.8719 (3)	0.6959 (4)	0.5145 (3)	0.0533 (10)
H2A	0.913404	0.666631	0.468759	0.064*
H2B	0.799494	0.701709	0.483506	0.064*
C3	0.9090 (3)	0.8318 (4)	0.5507 (3)	0.0610 (11)
H3A	0.861890	0.866304	0.590044	0.073*
H3B	0.907587	0.892438	0.498452	0.073*
C4	1.0190 (3)	0.8255 (4)	0.6065 (3)	0.0655 (12)
H4A	1.066814	0.796839	0.565949	0.079*
H4B	1.040186	0.913734	0.629716	0.079*
C5	1.0257 (3)	0.7304 (4)	0.6877 (3)	0.0571 (11)
H5A	0.982144	0.762195	0.730974	0.069*
H5B	1.097433	0.725615	0.720736	0.069*
C6	0.9892 (3)	0.5921 (4)	0.6519 (3)	0.0467 (9)
H6A	1.038300	0.556458	0.614973	0.056*
H6B	0.989011	0.533145	0.704873	0.056*
C9	0.7210 (3)	0.3561 (3)	0.5997 (3)	0.0434 (9)
H9	0.692247	0.356739	0.532622	0.052*
C10	0.6734 (3)	0.4718 (3)	0.6459 (2)	0.0377 (8)
H10	0.694274	0.466935	0.714056	0.045*
C14	0.6771 (3)	0.1182 (4)	0.5797 (3)	0.0471 (9)
C15	0.6325 (3)	0.0115 (4)	0.6155 (3)	0.0528 (10)
H15	0.620186	0.014510	0.676676	0.063*
C16	0.6058 (3)	−0.0992 (4)	0.5628 (3)	0.0565 (10)
H16	0.575579	−0.171836	0.587808	0.068*
C17	0.6233 (3)	−0.1030 (4)	0.4747 (3)	0.0547 (10)
C18	0.6689 (4)	−0.0038 (4)	0.4350 (3)	0.0630 (12)
H18	0.681166	−0.011008	0.373917	0.076*
C19	0.6978 (3)	0.1119 (4)	0.4882 (3)	0.0590 (11)
H19	0.730044	0.182798	0.463195	0.071*
C21	0.4950 (3)	0.5408 (3)	0.6671 (2)	0.0363 (8)
C22	0.3884 (3)	0.5175 (4)	0.6439 (3)	0.0437 (9)
H22	0.363878	0.453892	0.598747	0.052*
C23	0.3188 (3)	0.5861 (4)	0.6862 (3)	0.0519 (10)
H23	0.247271	0.570444	0.669993	0.062*
C24	0.3568 (3)	0.6790 (4)	0.7531 (3)	0.0538 (10)
C25	0.4615 (3)	0.7034 (4)	0.7791 (3)	0.0503 (10)
H25	0.485472	0.765931	0.825169	0.060*
C26	0.5308 (3)	0.6337 (4)	0.7358 (3)	0.0451 (9)
H26	0.602290	0.649131	0.752792	0.054*
F1	0.5926 (2)	−0.2147 (2)	0.4222 (2)	0.0916 (10)
F2	0.28814 (19)	0.7512 (3)	0.7942 (2)	0.0919 (10)
N13	0.7003 (3)	0.2335 (3)	0.6360 (2)	0.0528 (9)
H13	0.684 (7)	0.230 (8)	0.706 (7)	0.21 (4)*
N20	0.5636 (2)	0.4684 (3)	0.6213 (2)	0.0476 (8)
H20	0.538 (4)	0.419 (4)	0.581 (3)	0.069 (15)*
O7	0.8529 (2)	0.4717 (2)	0.54477 (18)	0.0484 (7)
O8	0.83419 (18)	0.3693 (2)	0.61166 (19)	0.0496 (7)
O11	0.70413 (16)	0.5990 (2)	0.61189 (16)	0.0391 (6)
O12	0.81273 (17)	0.6203 (2)	0.65769 (15)	0.0386 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0317 (17)	0.0376 (19)	0.0428 (19)	−0.0013 (14)	0.0109 (13)	−0.0067 (15)
C2	0.054 (2)	0.061 (3)	0.046 (2)	−0.002 (2)	0.0129 (17)	0.0042 (18)
C3	0.060 (3)	0.049 (2)	0.076 (3)	−0.007 (2)	0.016 (2)	0.015 (2)
C4	0.056 (3)	0.050 (3)	0.095 (3)	−0.020 (2)	0.027 (2)	−0.012 (2)
C5	0.032 (2)	0.065 (3)	0.073 (3)	−0.0088 (18)	0.0043 (18)	−0.016 (2)
C6	0.0334 (19)	0.051 (2)	0.056 (2)	0.0017 (16)	0.0073 (15)	−0.0004 (17)
C9	0.0379 (19)	0.0309 (19)	0.062 (2)	0.0020 (15)	0.0095 (16)	0.0000 (16)
C10	0.0324 (18)	0.0368 (19)	0.0442 (19)	−0.0015 (14)	0.0072 (14)	−0.0013 (15)
C14	0.037 (2)	0.044 (2)	0.060 (2)	0.0050 (17)	0.0062 (16)	−0.0159 (18)
C15	0.051 (2)	0.055 (3)	0.051 (2)	0.0030 (19)	0.0035 (17)	0.0009 (19)
C16	0.052 (2)	0.039 (2)	0.073 (3)	0.0025 (18)	−0.0029 (19)	0.003 (2)
C17	0.055 (2)	0.033 (2)	0.071 (3)	0.0036 (18)	−0.0033 (19)	−0.0175 (19)
C18	0.081 (3)	0.056 (3)	0.055 (3)	0.011 (2)	0.018 (2)	−0.009 (2)
C19	0.065 (3)	0.043 (2)	0.074 (3)	0.000 (2)	0.026 (2)	−0.004 (2)
C21	0.0311 (17)	0.0340 (18)	0.0440 (19)	−0.0026 (14)	0.0076 (14)	−0.0033 (14)
C22	0.0349 (19)	0.041 (2)	0.052 (2)	−0.0017 (16)	−0.0015 (15)	−0.0116 (16)
C23	0.0281 (18)	0.063 (3)	0.062 (2)	0.0001 (17)	−0.0003 (16)	−0.014 (2)
C24	0.036 (2)	0.069 (3)	0.057 (2)	0.0047 (19)	0.0108 (17)	−0.018 (2)
C25	0.041 (2)	0.056 (2)	0.053 (2)	−0.0088 (18)	0.0087 (16)	−0.0213 (18)
C26	0.0328 (18)	0.049 (2)	0.053 (2)	−0.0098 (16)	0.0077 (15)	−0.0120 (17)
F1	0.107 (2)	0.0477 (15)	0.110 (2)	−0.0037 (14)	−0.0087 (18)	−0.0347 (15)
F2	0.0452 (15)	0.129 (2)	0.101 (2)	0.0173 (15)	0.0118 (14)	−0.0599 (19)
N13	0.065 (2)	0.0421 (19)	0.051 (2)	−0.0045 (16)	0.0102 (16)	−0.0032 (15)
N20	0.0285 (15)	0.052 (2)	0.061 (2)	−0.0027 (14)	0.0046 (14)	−0.0205 (17)
O7	0.0510 (16)	0.0443 (15)	0.0534 (16)	−0.0061 (12)	0.0188 (12)	−0.0132 (12)
O8	0.0374 (14)	0.0366 (14)	0.0751 (19)	0.0028 (11)	0.0111 (12)	−0.0010 (12)
O11	0.0274 (12)	0.0362 (13)	0.0520 (15)	0.0027 (10)	0.0021 (10)	0.0009 (10)
O12	0.0327 (12)	0.0413 (14)	0.0420 (13)	−0.0062 (10)	0.0071 (9)	−0.0078 (10)

Geometric parameters (Å, º) top

C1—C2	1.519 (5)	C14—N13	1.417 (5)
C1—C6	1.508 (5)	C15—H15	0.9300
C1—O7	1.431 (4)	C15—C16	1.359 (5)
C1—O12	1.423 (4)	C16—H16	0.9300
C2—H2A	0.9700	C16—C17	1.339 (6)
C2—H2B	0.9700	C17—C18	1.339 (6)
C2—C3	1.509 (6)	C17—F1	1.374 (4)
C3—H3A	0.9700	C18—H18	0.9300
C3—H3B	0.9700	C18—C19	1.408 (6)
C3—C4	1.513 (6)	C19—H19	0.9300
C4—H4A	0.9700	C21—C22	1.384 (5)
C4—H4B	0.9700	C21—C26	1.385 (5)
C4—C5	1.507 (6)	C21—N20	1.402 (4)
C5—H5A	0.9700	C22—H22	0.9300
C5—H5B	0.9700	C22—C23	1.363 (5)
C5—C6	1.527 (5)	C23—H23	0.9300
C6—H6A	0.9700	C23—C24	1.374 (5)
C6—H6B	0.9700	C24—C25	1.367 (5)
C9—H9	0.9800	C24—F2	1.363 (4)
C9—C10	1.525 (5)	C25—H25	0.9300
C9—N13	1.382 (5)	C25—C26	1.373 (5)
C9—O8	1.454 (4)	C26—H26	0.9300
C10—H10	0.9800	N13—H13	1.08 (10)
C10—N20	1.407 (4)	N20—H20	0.79 (5)
C10—O11	1.449 (4)	O7—O8	1.462 (3)
C14—C15	1.362 (5)	O11—O12	1.464 (3)
C14—C19	1.402 (5)

C6—C1—C2	112.2 (3)	O11—C10—H10	110.1
O7—C1—C2	103.2 (3)	C15—C14—C19	119.4 (4)
O7—C1—C6	113.5 (3)	C15—C14—N13	118.8 (4)
O12—C1—C2	113.3 (3)	C19—C14—N13	121.8 (4)
O12—C1—C6	104.7 (3)	C14—C15—H15	119.6
O12—C1—O7	110.2 (2)	C16—C15—C14	120.7 (4)
C1—C2—H2A	109.3	C16—C15—H15	119.6
C1—C2—H2B	109.3	C15—C16—H16	120.3
H2A—C2—H2B	108.0	C17—C16—C15	119.5 (4)
C3—C2—C1	111.5 (3)	C17—C16—H16	120.3
C3—C2—H2A	109.3	C16—C17—C18	123.5 (4)
C3—C2—H2B	109.3	C16—C17—F1	118.2 (4)
C2—C3—H3A	109.4	C18—C17—F1	118.3 (4)
C2—C3—H3B	109.4	C17—C18—H18	121.0
C2—C3—C4	111.2 (3)	C17—C18—C19	118.1 (4)
H3A—C3—H3B	108.0	C19—C18—H18	121.0
C4—C3—H3A	109.4	C14—C19—C18	118.7 (4)
C4—C3—H3B	109.4	C14—C19—H19	120.6
C3—C4—H4A	109.3	C18—C19—H19	120.6
C3—C4—H4B	109.3	C22—C21—C26	118.9 (3)
H4A—C4—H4B	108.0	C22—C21—N20	119.1 (3)
C5—C4—C3	111.4 (3)	C26—C21—N20	121.9 (3)
C5—C4—H4A	109.3	C21—C22—H22	119.4
C5—C4—H4B	109.3	C23—C22—C21	121.1 (3)
C4—C5—H5A	109.7	C23—C22—H22	119.4
C4—C5—H5B	109.7	C22—C23—H23	120.7
C4—C5—C6	109.7 (3)	C22—C23—C24	118.5 (3)
H5A—C5—H5B	108.2	C24—C23—H23	120.7
C6—C5—H5A	109.7	C25—C24—C23	122.1 (3)
C6—C5—H5B	109.7	F2—C24—C23	119.3 (3)
C1—C6—C5	112.5 (3)	F2—C24—C25	118.6 (3)
C1—C6—H6A	109.1	C24—C25—H25	120.6
C1—C6—H6B	109.1	C24—C25—C26	118.7 (3)
C5—C6—H6A	109.1	C26—C25—H25	120.6
C5—C6—H6B	109.1	C21—C26—H26	119.7
H6A—C6—H6B	107.8	C25—C26—C21	120.5 (3)
C10—C9—H9	108.6	C25—C26—H26	119.7
N13—C9—H9	108.6	C9—N13—C14	122.8 (4)
N13—C9—C10	112.9 (3)	C9—N13—H13	118 (4)
N13—C9—O8	107.2 (3)	C14—N13—H13	118 (4)
O8—C9—H9	108.6	C10—N20—H20	119 (3)
O8—C9—C10	110.9 (3)	C21—N20—C10	124.4 (3)
C9—C10—H10	110.1	C21—N20—H20	117 (3)
N20—C10—C9	109.9 (3)	C1—O7—O8	109.6 (2)
N20—C10—H10	110.1	C9—O8—O7	105.4 (2)
N20—C10—O11	105.2 (3)	C10—O11—O12	105.9 (2)
O11—C10—C9	111.3 (3)	C1—O12—O11	109.6 (2)

C1—C2—C3—C4	54.4 (4)	C22—C21—N20—C10	−172.4 (3)
C1—O7—O8—C9	103.7 (3)	C22—C23—C24—C25	−0.6 (7)
C2—C1—C6—C5	52.6 (4)	C22—C23—C24—F2	178.1 (4)
C2—C1—O7—O8	−166.8 (2)	C23—C24—C25—C26	0.8 (7)
C2—C1—O12—O11	68.4 (3)	C24—C25—C26—C21	0.1 (6)
C2—C3—C4—C5	−58.0 (5)	C26—C21—C22—C23	1.3 (6)
C3—C4—C5—C6	57.2 (4)	C26—C21—N20—C10	6.7 (6)
C4—C5—C6—C1	−54.8 (4)	F1—C17—C18—C19	178.4 (4)
C6—C1—C2—C3	−52.0 (4)	F2—C24—C25—C26	−178.0 (4)
C6—C1—O7—O8	71.5 (3)	N13—C9—C10—N20	−68.8 (4)
C6—C1—O12—O11	−169.0 (2)	N13—C9—C10—O11	175.1 (3)
C9—C10—N20—C21	165.2 (3)	N13—C9—O8—O7	159.9 (3)
C9—C10—O11—O12	−75.8 (3)	N13—C14—C15—C16	177.8 (4)
C10—C9—N13—C14	141.1 (3)	N13—C14—C19—C18	−177.5 (4)
C10—C9—O8—O7	−76.5 (3)	N20—C10—O11—O12	165.3 (2)
C10—O11—O12—C1	103.5 (3)	N20—C21—C22—C23	−179.6 (4)
C14—C15—C16—C17	−0.2 (6)	N20—C21—C26—C25	179.8 (4)
C15—C14—C19—C18	1.8 (6)	O7—C1—C2—C3	−174.5 (3)
C15—C14—N13—C9	−163.7 (4)	O7—C1—C6—C5	169.1 (3)
C15—C16—C17—C18	1.8 (6)	O7—C1—O12—O11	−46.7 (3)
C15—C16—C17—F1	−178.0 (4)	O8—C9—C10—N20	170.9 (3)
C16—C17—C18—C19	−1.5 (7)	O8—C9—C10—O11	54.8 (4)
C17—C18—C19—C14	−0.4 (6)	O8—C9—N13—C14	−96.6 (4)
C19—C14—C15—C16	−1.5 (6)	O11—C10—N20—C21	−74.9 (4)
C19—C14—N13—C9	15.6 (6)	O12—C1—C2—C3	66.3 (4)
C21—C22—C23—C24	−0.4 (6)	O12—C1—C6—C5	−70.7 (4)
C22—C21—C26—C25	−1.2 (6)	O12—C1—O7—O8	−45.5 (3)

Torsion angles (°) of the tetraoxepane ring top

Torsion angle	(I)	(II)	(III)	QAQFAP	QONLOU
C1—O7—O8—C9	104.2 (2)	106.24 (15)	103.7 (3)	97.69 (14)	102.4 (3)
C10—C9—O8—O7	-74.5 (2)	-70.73 (17)	-76.5 (3)	-76.33 (14)	-70.6 (3)
O8—C9—C10—O11	51.2 (3)	44.6 (2)	54.8 (4)	1.74 (15)	52.6 (3)
C9—C10—O11—O12	-72.8 (2)	-69.08 (17)	-75.8 (3)	74.89 (13)	-77.8 (3)
C10—O11—O12—C1	103.67 (19)	105.64 (15)	103.5 (3)	-98.09 (14)	103.9 (3)
O7—C1—O12—O11	-48.0 (2)	-48.95 (16)	-46.7 (3)	75.39 (17)	-44.5 (3)
O12—C1—O7—O8	-45.2 (2)	-47.03 (17)	-45.5 (3)	-74.84 (15)	-48.3 (3)

Selected bond lengths (Å) in structures (I)–(III) top

Bond	(I)	(II)	(III)
C1—O7	1.423 (3)	1.427 (2)	1.431 (4)
O7—O8	1.458 (2)	1.4652 (17)	1.462 (3)
O8—C9	1.444 (3)	1.448 (2)	1.454 (4)
C9—C10	1.527 (3)	1.541 (3)	1.525 (5)
C10—O11	1.447 (3)	1.446 (2)	1.449 (4)
O11—O12	1.464 (2)	1.468 (17)	1.464 (3)
O12—C1	1.430 (3)	1.427 (2)	1.423 (4)
C9—N13	1.404 (3)	1.404 (2)	1.382 (5)
N13—C14	1.390 (3)	1.396 (2)	1.417 (5)
C10—N20	1.404 (3)	1.405 (2)	1.407 (4)
N20—C21	1.401 (3)	1.400 (2)	1.402 (4)
ΣN13	356.0	359.49	358.8
ΣN20	353.8	359.48	359.4

The second-order perturbation energy E(2) (donor→acceptor) (kJ mol^-1) calculated at the B3LYP/6-31G(d,2p) level top

Interacting fragments	(I)	(II)	(III)
LP(O12)→σ*(C1—O7)	44.81	45.19	45.14
LP(O7)→σ*(C1—O12)	44.02	43.47	44.31
LP(O8)→σ*(C9—C10)	32.64	31.46	30.46
LP(O11)→σ*(C9—C10)	31.17	31.51	29.54
LP(O8)→σ*(C9—N13)	3.35	3.22	3.60
LP(O11)→σ*(C10—N20)	3.68	3.64	3.35
LP(N20)→σ*(C10—O11)	75.48	71.59	76.07
LP(N13)→σ*(C9—O8)	72.47	77.61	86.48

Topological parameters of electron density at the (3, –1) BCPs for some bonds in compounds (I)–(III) top

Bond	10ρ(r) (e au^-3)	-10∇²ρ(r) (e au^-5)	10ε	10ρ(r) (e au^-3)	-10∇²ρ(r) (e au^-5)	10ε	10ρ(r) (e au^-3)	-10∇²ρ(r) (e au^-5)	10ε
	(I)	(II)	(III)
C1—O7	2.64	5.91	1.50	2.62	5.85	1.38	2.60	6.85	1.87
O7—O8	2.74	0.19	0.31	2.68	0.05	0.32	2.68	0.99	0.29
O8—C9	2.55	6.01	1.39	2.52	5.90	1.36	2.47	6.88	1.00
C9—C10	2.63	6.62	0.55	2.56	6.29	0.50	2.61	6.78	0.45
C10—O11	2.51	5.80	1.18	2.52	5.90	1.36	2.45	6.79	0.97
O11—O12	2.69	0.03	0.30	2.70	0.09	0.32	2.69	1.02	0.29
O12—C1	2.59	5.80	1.36	2.63	5.97	1.45	2.59	6.61	1.90
C9—N13	3.01	9.99	0.16	3.01	9.96	0.34	3.18	12.03	0.48
N13—C14	3.03	9.30	0.72	2.97	9.29	0.95	2.92	10.15	0.40
C10—N20	3.02	10.07	0.05	3.00	9.91	0.32	3.03	10.75	0.32
N20—C21	2.97	9.24	0.70	2.98	9.23	0.93	2.96	10.47	0.40

PIXEL lattice energies (kJ mol^-1) divided into Coulombic (E_Coul), polarization (E_Pol), dispersion (E_Disp) and repulsion (E_Rep) components for compounds (I)–(III) top

Compound	E_Coul	E_Pol	E_Disp	E_Rep	E_Tot
(I)	-72.9	-34.9	-227.7	144.6	-190.9
(II)	-57.5	-22.0	-185.9	109.7	-155.8
(III)	-59.4	-24.5	-187.3	101.7	-169.4

Topological parameters of electron density at the (3, –1) BCPs for intermolecular interactions in crystals of compounds (I)–(III) top

Interaction	ρ(r) (e au^-3)	∇²ρ(r) (e au^-5)	ε
(I)
N13—H13···O12ⁱ	0.0133	0.0455	0.0856
C22—H22···N13ⁱ	0.0080	0.0235	0.0257
C23—H23(phenolic)···O8ⁱ	0.0104	0.0378	0.1242
C15—H15(phenolic)···O12ⁱ	0.0092	0.0312	0.0692
C4—H4A···πⁱ	0.0061	0.0183	1.7236
C5—H5A···N20ⁱ	0.0041	0.0133	0.6366
C6—H6A···Cl2ⁱ	0.0037	0.0111	0.7371
C16—H16···πⁱⁱ	0.0085	0.0277	0.6231
N20—H20···Cl1ⁱⁱ	0.0032	0.0108	0.3080
C2—H2A···πⁱⁱ	0.0059	0.0189	0.7406
N20—H20···Cl2ⁱⁱⁱ	0.0019	0.0306	0.0616
C25—H25···N13ⁱⁱⁱ	0.0023	0.0082	1.1784
C25—H25···πⁱⁱⁱ	0.0079	0.0244	0.2723
C26—H26···Cl2ⁱⁱⁱ	0.0052	0.0175	0.1753

(II)
C5—H5B···F1ⁱⁱ	0.0063	0.0277	0.1097
C4—H4B···F2ⁱⁱ	0.0032	0.0162	0.5805
C3—H3B···F2ⁱⁱ	0.0047	0.0220	0.1460
C17—H17···O8^iv	0.0071	0.0263	0.0573
N20—H20···O12^v	0.0082	0.0300	0.0911
N13—H13···O7^v	0.0148	0.0485	0.0798
C6—H6B···π^v	0.0099	0.0298	0.2327
C2—H2A···π^v	0.0083	0.0251	0.5809
C2—H2B···F1^v	0.0057	0.0251	0.0321
C5—H5A···F2^v	0.0099	0.0387	0.0173
C10—H10···O7^v	0.0055	0.0194	0.0913
C9—H9···O12^v	0.0054	0.0194	0.2455

(III)
π–π^vi	0.0050	0.0143	0.4511
C22—H22···F1^vi	0.0095	0.0389	0.0257
N20—H20···F1^vi	0.0080	0.0351	0.0236
C5—H5B···F2^vii	0.0092	0.0355	0.0096
C6—H6A···H23-C23^vii	0.0037	0.0130	0.3114
C25—H25···O8ⁱⁱⁱ	0.0091	0.0326	0.0387
C26—H26···N13ⁱⁱⁱ	0.0065	0.0161	0.0779
N13—H13···O12ⁱⁱⁱ	0.0117	0.0401	0.0854
C5—H5A···N13ⁱⁱⁱ	0.0035	0.0135	0.1107
C5—H5A···N20ⁱⁱⁱ	0.0045	0.0143	0.5693
C15—H15···O12ⁱⁱⁱ	0.0095	0.0313	0.0461
C4—H4B···πⁱⁱⁱ	0.0041	0.0126	2.8071
C23—H23···O7^viii	0.0025	0.0110	0.8347
C22—H22···O11^viii	0.0037	0.0145	0.1839
C19—H19···C23^viii	0.0038	0.0116	0.3165
C9—H9···π^viii	0.0066	0.0199	0.3468

Symmetry codes: (i) -x+1/2, y-1/2, -z+3/2; (ii) x, y-1, z; (iii) -x+3/2, y-1/2, -z+3/2; (iv) -x, y-1/2, -z-1/2; (v) x, -y+1/2, z+1/2; (vi) -x+1, -y, -z+1; (vii) x+1, y, z; (viii) -x+1, -y+1, -z+1.

PIXEL energies (kJ mol^-1) for intermolecular interactions in crystals of compounds (I)–(III) top

D—H···A	-E_Coul	-E_Pol	-E_Disp	E_Rep	-E_tot
(I)
N13—H13···O12ⁱ	35.8	14.1	72.3	55.1	67.1
C19—H19···O12ⁱ	35.8	14.1	72.3	55.1	67.1
C23—H23···O8ⁱ	35.8	14.1	72.3	55.1	67.1
C22—H22···N13ⁱ	35.8	14.1	72.3	55.1	67.1
N20—H20···Cl2ⁱⁱⁱ	12.7	8.4	36.1	23.3	33.8
C18—H18···πⁱⁱ	10.2	6.0	41.7	29.0	28.9
C2—H2A···H6B—C6^ix	9.0	4.9	32.7	18.2	28.4
C16—H16···π^x	7.4	2.0	21.4	11.1	19.8
Cl1..-.Cl2^xi	3.4	2.2	13.4	11.5	7.7

(II)
N13—H13···O7^xii	39.6	13.3	74.0	51.8	75.1
N20—H20···O12^xii	39.6	13.3	74.0	51.8	75.1
C24—H24···O11^xiii	4.1	2.4	19.2	10.5	15.2
C2—H2B···H4B–C4^v	2.8	1.6	18.0	7.5	14.9
C3—H3B···F2ⁱⁱⁱ	3.4	1.1	16.3	6.7	14.1
π–π(C21)^xiv	2.4	1.8	24.4	15.1	13.6
π–π(C15)^xv	4.2	1.8	23.6	17.5	12.1
C17—H17···H18–C18^xvi	2.8	1.3	11.8	7.5	8.4

(III)
N13—H13···O12ⁱⁱⁱ	29.9	10.9	59.6	40.0	60.4
C15—H15···O12ⁱⁱⁱ	29.9	10.9	59.6	40.0	60.4
C25—H25···O8ⁱⁱⁱ	29.9	10.9	59.6	40.0	60.4
C9—H9···π^viii	18.8	6.6	52.6	22.0	56.0
N20—H20···F1^vi	15.3	5.7	37.0	27.6	30.4
C22—H22···F1^vi	15.3	5.7	37.0	27.6	30.4
π–π^vi	15.3	5.7	37.0	27.6	30.4
C6—H6A···O7^xvii	7.4	2.9	25.9	9.7	26.4
C16—H16···O11ⁱⁱ	5.5	2.8	25.9	13.9	20.3
C2—H2B···πⁱⁱ	5.5	2.8	25.9	13.9	20.3
C5—H5B···F2^vii	3.0	1.5	10.4	7.7	7.2
C2—H2B···F2^xviii	1.0	1.2	10.9	6.4	6.7
C5—H5A···F1^xix	–0.2	0.4	6.8	1.9	5.1
C5—H5B···F1^xix	–0.2	0.4	6.8	1.9	5.1

Symmetry codes: (i) -x+1/2, y-1/2, -z+3/2; (ii) x, y-1, z; (iii) -x+3/2, y-1/2, -z+3/2; (v) x, -y+1/2, z+1/2; (vi) -x+1, -y, -z+1; (vii) x+1, y, z; (viii) -x+1, -y+1, -z+1; (ix) -x+3, -y, -z+1; (x) -x+2, -y+1, -z+1; (xi) x+1/2, -y-1/2, z+1/2; (xii) x, -y+3/2, z+1/2; (xiii) -x+1, y-1/2, -z+1/2; (xiv) -x+1, -y+2, -z; (xv) -x, -y+2, -z; (xvi) -x, -y+2, -z+1; (xvii) -x+2, -y+1, -z; (xviii) x+1/2, -y+3/2, -z+1/2; (xix) x+1/2, -y+1/2, z+1/2.

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

Twist-chair conformation of the tetra­oxepane ring remains unchanged in tetra­oxa­spiro­dodecane di­amines

Supporting information

Twist-chair conformation of the tetraoxepane ring remains unchanged in tetraoxaspirododecane diamines