Eight Schiff bases derived from various salicyl­aldehydes: phenol–imine and keto–amine forms, conformational disorder, and supra­molecular assembly in one and two dimensions

Girisha, M.; Sagar, B.K.; Yathirajan, H.S.; Rathore, R.S.; Kaur, M.; Jasinski, J.P.; Glidewell, C.

doi:10.1107/S2053229618012287

Eight Schiff bases derived from various salicylaldehydes: phenol–imine and keto–amine forms, conformational disorder, and supramolecular assembly in one and two dimensions

M. Girisha, B. K. Sagar, H. S. Yathirajan, R. S. Rathore, M. Kaur, J. P. Jasinski and C. Glidewell

Structures are reported for eight Schiff bases derived from various salicylaldehydes: five are newly synthesized and re-investigations are reported for three previously reported structures, leading, in each case, to some revision of previous conclusions. In (E)-N-(3,4-dimethylisoxazol-5-yl)-4-[(2-hydroxybenzylidene)amino]benzenesulfonamide, C₁₈H₁₇N₃O₄S, (I), and (E)-4-[(5-bromo-2-hydroxy-3-methoxybenzylidene)amino]-N-(3,4-dimethylisoxazol-5-yl)benzenesulfonamide. C₁₉H₁₈BrN₃O₅S, (II), the isoxazole rings adopt different orientations relative to the rest of the molecules, despite the additional substituents in (II) being in the aryl ring remote from the isoxazole unit. The molecules of both (E)-4-bromo-2-[(2-hydroxyphenylimino)methyl]-6-methoxyphenol, C₁₄H₁₂BrNO₃, (III), and (E)-4-bromo-2-methoxy-6-[(2-methoxyphenylimino)methyl]phenol, C₁₅H₁₄BrNO₃, (IV), are both effectively planar; while (III) adopts the phenol–imine constitution, (IV) adopts the keto–amine constitution. (E)-2-Methoxy-6-[(2-methoxyphenylimino)methyl]phenol, C₁₅H₁₅NO₃, (V), which was determined previously using powder X-ray data assuming the phenol–imine constitution, has now been refined from single-crystal X-ray data, confirming the phenol–imine constitution. In (E)-3-benzoyl-2-[(5-fluoro-2-hydroxybenzylidene)amino]-4,5,6,7-tetrahydrobenzo[b]thiophene, C₂₂H₁₈FNO₂S, (VI), the fused carbocyclic ring exhibits conformational disorder; both disorder components, having populations of 0.705 (4) and 0.295 (4), adopt half-chair conformations. The isostructural (E)-3-benzoyl-2-[(2-hydroxybenzylidene)amino)]-4,5,6,7-tetrahydrobenzo[b]thiophene, C₂₂H₁₉NO₂S, (VII), which was originally reported as having a fully ordered structure [Kaur et al. (2014). Acta Cryst. E70, o476–o477], has been rerefined using the original data set and found to exhibit the same type of disorder as found in (VI), with disordered populations having occupancies of 0.851 (3) and 0.149 (3). The triclinic polymorph of (E)-[(2-hydroxyphenylimino)methyl]phenol, C₁₃H₁₁NO₂, (VIII), which crystallizes with Z′ = 2 in the space group P $\overline{1}$ , has been described variously as occurring as the keto–amine tautomer [Maciejewska et al. (1999). J. Phys. Org. Chem. 12, 875–880] and as the phenol–imine tautomer [Tunç et al. (2009). J. Chem. Crystallogr. 39, 672–676]. Rerefinement of this structure using one of the original data sets shows that both of the independent molecules exist in the keto–amine form. In the structures of compounds (I), (VI), (VII) and (VIII), hydrogen bonds generate simple chains, while a chain of rings is formed in (V). Sheets are formed by hydrogen bonds in both (II) and (III), while in (IV), the sheet structure is built from aromatic π–π stacking interactions.

Keywords: Schiff bases; molecular structure; molecular conformation; conformational disorder; phenol–imine; keto–amine; tautomer; hydrogen bonding; supramolecular assembly; crystal structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229618012287/fn3266sup1.cif Contains datablocks global, I, II, III, IV, V, VI, VII, VIII
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618012287/fn3266Isup2.hkl Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618012287/fn3266IIsup3.hkl Contains datablock II
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618012287/fn3266IIIsup4.hkl Contains datablock III
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618012287/fn3266IVsup5.hkl Contains datablock IV
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618012287/fn3266Vsup6.hkl Contains datablock V
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618012287/fn3266VIsup7.hkl Contains datablock VI
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618012287/fn3266VIIsup8.hkl Contains datablock VII
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229618012287/fn3266VIIIsup9.hkl Contains datablock VIII
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229618012287/fn3266IIsup10.cml Supplementary material
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229618012287/fn3266IIIsup11.cml Supplementary material
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229618012287/fn3266IVsup12.cml Supplementary material
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229618012287/fn3266Vsup13.cml Supplementary material
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229618012287/fn3266VIIIsup14.cml Supplementary material

CCDC references: 1864481; 1864480; 1864479; 1864478; 1864477; 1864476; 1864475; 1864474

Computing details top

Data collection: APEX2 (Bruker, 2004) for (I), (II), (III), (IV), (V), (VI); CrysAlis PRO (Agilent, 2012) for (VII); X-AREA (Stoe & Cie, 2002) for (VIII). Cell refinement: SAINT (Bruker, 2004) for (I), (II), (III), (IV), (V), (VI); CrysAlis PRO (Agilent, 2012) for (VII); X-AREA (Stoe & Cie, 2002) for (VIII). Data reduction: SAINT (Bruker, 2004) for (I), (II), (III), (IV), (V), (VI); CrysAlis RED (Agilent, 2012) for (VII); X-RED (Stoe & Cie, 2002) for (VIII). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (I), (II), (III), (IV), (V), (VI), (VIII); SUPERFLIP (Palatinus & Chapuis, 2007) for (VII). For all structures, program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

(E)-N-(3,4-Dimethylisoxazol-5-yl)-4-[(2-hydroxybenzylidene)amino]benzenesulfonamide (I) top

Crystal data top

C₁₈H₁₇N₃O₄S	F(000) = 776
M_r = 371.41	D_x = 1.358 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.344 (2) Å	Cell parameters from 3259 reflections
b = 9.6384 (9) Å	θ = 2.0–25.2°
c = 9.443 (1) Å	µ = 0.21 mm⁻¹
β = 101.060 (3)°	T = 296 K
V = 1817.2 (3) Å³	Block, orange
Z = 4	0.20 × 0.15 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	3258 independent reflections
Radiation source: fine focus sealed tube	1971 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
φ and ω scans	θ_max = 25.2°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −24→24
T_min = 0.848, T_max = 0.980	k = −11→10
20651 measured reflections	l = −11→11

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.135	w = 1/[σ²(F_o²) + (0.0301P)² + 2.4078P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
3258 reflections	Δρ_max = 0.26 e Å⁻³
241 parameters	Δρ_min = −0.28 e Å⁻³

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	0.62363 (19)	0.6121 (3)	0.3110 (4)	0.0432 (9)
C2	0.6796 (2)	0.6754 (4)	0.2806 (4)	0.0529 (10)
H2	0.6762	0.7263	0.1958	0.063*
C3	0.7410 (2)	0.6658 (4)	0.3724 (4)	0.0515 (10)
H3	0.7783	0.7102	0.3503	0.062*
C4	0.74613 (18)	0.5890 (3)	0.4979 (3)	0.0401 (9)
C5	0.6905 (2)	0.5242 (4)	0.5295 (4)	0.0525 (10)
H5	0.6943	0.4719	0.6134	0.063*
C6	0.6295 (2)	0.5358 (4)	0.4386 (4)	0.0551 (11)
H6	0.5920	0.4929	0.4620	0.066*
N1	0.56308 (16)	0.6324 (3)	0.2120 (3)	0.0460 (8)
C17	0.5109 (2)	0.5603 (4)	0.2146 (4)	0.0501 (10)
H17	0.5134	0.4900	0.2829	0.060*
C11	0.44825 (19)	0.5821 (4)	0.1172 (4)	0.0477 (9)
C12	0.4417 (2)	0.6827 (4)	0.0077 (4)	0.0506 (10)
C13	0.3810 (2)	0.6998 (4)	−0.0853 (5)	0.0639 (12)
H13	0.3772	0.7637	−0.1603	0.077*
C14	0.3264 (2)	0.6236 (5)	−0.0680 (5)	0.0760 (14)
H14	0.2855	0.6374	−0.1299	0.091*
C15	0.3317 (3)	0.5258 (5)	0.0412 (6)	0.0789 (14)
H15	0.2944	0.4751	0.0539	0.095*
C16	0.3924 (2)	0.5046 (5)	0.1303 (5)	0.0668 (12)
H16	0.3961	0.4365	0.2012	0.080*
O12	0.49378 (15)	0.7636 (3)	−0.0084 (3)	0.0732 (9)
H12	0.5271	0.7405	0.0502	0.110*
S4	0.82316 (5)	0.57701 (10)	0.61683 (10)	0.0494 (3)
O1	0.86074 (14)	0.6983 (3)	0.5966 (3)	0.0657 (8)
O2	0.81221 (15)	0.5410 (3)	0.7568 (2)	0.0662 (8)
N4	0.86257 (15)	0.4427 (3)	0.5655 (3)	0.0411 (8)
H4	0.8547 (17)	0.366 (4)	0.608 (4)	0.049*
O41	0.84031 (13)	0.3227 (2)	0.3499 (2)	0.0475 (6)
N42	0.85711 (17)	0.3240 (3)	0.2119 (3)	0.0522 (8)
C43	0.89615 (19)	0.4321 (4)	0.2091 (3)	0.0437 (9)
C44	0.90760 (17)	0.5044 (3)	0.3423 (3)	0.0378 (8)
C45	0.87241 (16)	0.4321 (3)	0.4238 (3)	0.0347 (8)
C46	0.9242 (2)	0.4639 (4)	0.0783 (4)	0.0716 (13)
H46A	0.9719	0.4518	0.0996	0.107*
H46B	0.9138	0.5581	0.0493	0.107*
H46C	0.9049	0.4024	0.0015	0.107*
C47	0.9523 (2)	0.6282 (4)	0.3802 (4)	0.0597 (11)
H47A	0.9287	0.7107	0.3429	0.090*
H47B	0.9916	0.6178	0.3388	0.090*
H47C	0.9652	0.6353	0.4832	0.090*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.054 (3)	0.036 (2)	0.041 (2)	0.0056 (18)	0.0134 (19)	0.0023 (16)
C2	0.062 (3)	0.051 (2)	0.049 (2)	0.005 (2)	0.018 (2)	0.0191 (19)
C3	0.053 (3)	0.047 (2)	0.057 (2)	−0.0006 (19)	0.018 (2)	0.0134 (19)
C4	0.054 (2)	0.0303 (18)	0.0388 (19)	−0.0002 (17)	0.0158 (17)	−0.0039 (16)
C5	0.067 (3)	0.053 (2)	0.037 (2)	−0.004 (2)	0.012 (2)	0.0098 (18)
C6	0.060 (3)	0.056 (3)	0.051 (2)	−0.011 (2)	0.016 (2)	0.0090 (19)
N1	0.054 (2)	0.0428 (18)	0.0440 (18)	0.0036 (16)	0.0168 (16)	−0.0002 (14)
C17	0.068 (3)	0.047 (2)	0.037 (2)	0.002 (2)	0.012 (2)	0.0001 (17)
C11	0.052 (3)	0.045 (2)	0.047 (2)	−0.0024 (19)	0.0108 (19)	−0.0064 (18)
C12	0.053 (3)	0.043 (2)	0.057 (2)	0.007 (2)	0.014 (2)	−0.0043 (19)
C13	0.067 (3)	0.050 (3)	0.071 (3)	0.011 (2)	0.005 (3)	0.003 (2)
C14	0.061 (3)	0.071 (3)	0.089 (4)	0.007 (3)	−0.003 (3)	−0.018 (3)
C15	0.067 (4)	0.077 (3)	0.092 (4)	−0.020 (3)	0.014 (3)	−0.009 (3)
C16	0.071 (3)	0.068 (3)	0.060 (3)	−0.014 (3)	0.009 (2)	−0.001 (2)
O12	0.066 (2)	0.0674 (19)	0.086 (2)	0.0001 (17)	0.0138 (17)	0.0314 (17)
S4	0.0697 (7)	0.0424 (5)	0.0352 (5)	0.0016 (5)	0.0077 (4)	−0.0103 (4)
O1	0.080 (2)	0.0391 (15)	0.0739 (19)	−0.0134 (14)	0.0050 (16)	−0.0164 (14)
O2	0.090 (2)	0.082 (2)	0.0267 (13)	0.0107 (17)	0.0119 (13)	−0.0108 (13)
N4	0.062 (2)	0.0331 (17)	0.0293 (16)	0.0033 (15)	0.0122 (14)	0.0044 (12)
O41	0.0687 (18)	0.0414 (14)	0.0358 (13)	−0.0092 (13)	0.0183 (12)	−0.0065 (11)
N42	0.081 (2)	0.0492 (19)	0.0310 (16)	−0.0048 (18)	0.0225 (16)	−0.0082 (14)
C43	0.056 (2)	0.042 (2)	0.0361 (19)	0.0072 (19)	0.0168 (17)	0.0041 (16)
C44	0.043 (2)	0.0344 (19)	0.0356 (19)	0.0047 (16)	0.0059 (16)	0.0082 (15)
C45	0.042 (2)	0.0307 (18)	0.0306 (18)	0.0036 (16)	0.0038 (15)	0.0015 (15)
C46	0.103 (4)	0.068 (3)	0.053 (2)	0.005 (3)	0.037 (2)	0.007 (2)
C47	0.061 (3)	0.052 (2)	0.062 (3)	−0.013 (2)	−0.001 (2)	0.011 (2)

Geometric parameters (Å, º) top

C1—C2	1.371 (5)	C15—C16	1.369 (6)
C1—C6	1.397 (5)	C15—H15	0.9300
C1—N1	1.410 (4)	C16—H16	0.9300
C2—C3	1.379 (5)	O12—H12	0.8200
C2—H2	0.9300	S4—O2	1.425 (2)
C3—C4	1.384 (5)	S4—O1	1.430 (3)
C3—H3	0.9300	S4—N4	1.644 (3)
C4—C5	1.374 (5)	N4—C45	1.394 (4)
C4—S4	1.748 (4)	N4—H4	0.87 (3)
C5—C6	1.372 (5)	O41—C45	1.360 (4)
C5—H5	0.9300	O41—N42	1.409 (3)
C6—H6	0.9300	N42—C43	1.313 (4)
N1—C17	1.273 (4)	C43—C44	1.417 (4)
C17—C11	1.437 (5)	C43—C46	1.489 (5)
C17—H17	0.9300	C44—C45	1.342 (4)
C11—C16	1.386 (5)	C44—C47	1.502 (5)
C11—C12	1.405 (5)	C46—H46A	0.9600
C12—O12	1.347 (4)	C46—H46B	0.9600
C12—C13	1.381 (5)	C46—H46C	0.9600
C13—C14	1.368 (6)	C47—H47A	0.9600
C13—H13	0.9300	C47—H47B	0.9600
C14—C15	1.386 (6)	C47—H47C	0.9600
C14—H14	0.9300

C2—C1—C6	118.6 (4)	C15—C16—C11	121.5 (4)
C2—C1—N1	117.0 (3)	C15—C16—H16	119.2
C6—C1—N1	124.3 (3)	C11—C16—H16	119.2
C1—C2—C3	121.8 (3)	C12—O12—H12	109.5
C1—C2—H2	119.1	O2—S4—O1	120.41 (17)
C3—C2—H2	119.1	O2—S4—N4	104.68 (15)
C2—C3—C4	119.0 (3)	O1—S4—N4	107.52 (16)
C2—C3—H3	120.5	O2—S4—C4	109.37 (17)
C4—C3—H3	120.5	O1—S4—C4	107.25 (17)
C5—C4—C3	119.9 (3)	N4—S4—C4	106.88 (15)
C5—C4—S4	120.3 (3)	C45—N4—S4	120.6 (2)
C3—C4—S4	119.8 (3)	C45—N4—H4	117 (2)
C6—C5—C4	120.8 (3)	S4—N4—H4	113 (2)
C6—C5—H5	119.6	C45—O41—N42	106.8 (2)
C4—C5—H5	119.6	C43—N42—O41	106.3 (3)
C5—C6—C1	119.9 (4)	N42—C43—C44	111.7 (3)
C5—C6—H6	120.0	N42—C43—C46	120.6 (3)
C1—C6—H6	120.0	C44—C43—C46	127.7 (3)
C17—N1—C1	122.5 (3)	C45—C44—C43	103.8 (3)
N1—C17—C11	123.2 (4)	C45—C44—C47	129.9 (3)
N1—C17—H17	118.4	C43—C44—C47	126.2 (3)
C11—C17—H17	118.4	C44—C45—O41	111.4 (3)
C16—C11—C12	118.3 (4)	C44—C45—N4	134.7 (3)
C16—C11—C17	120.4 (4)	O41—C45—N4	113.9 (3)
C12—C11—C17	121.3 (4)	C43—C46—H46A	109.5
O12—C12—C13	119.1 (4)	C43—C46—H46B	109.5
O12—C12—C11	121.1 (4)	H46A—C46—H46B	109.5
C13—C12—C11	119.8 (4)	C43—C46—H46C	109.5
C14—C13—C12	120.5 (4)	H46A—C46—H46C	109.5
C14—C13—H13	119.7	H46B—C46—H46C	109.5
C12—C13—H13	119.7	C44—C47—H47A	109.5
C13—C14—C15	120.3 (4)	C44—C47—H47B	109.5
C13—C14—H14	119.8	H47A—C47—H47B	109.5
C15—C14—H14	119.8	C44—C47—H47C	109.5
C16—C15—C14	119.4 (4)	H47A—C47—H47C	109.5
C16—C15—H15	120.3	H47B—C47—H47C	109.5
C14—C15—H15	120.3

C6—C1—C2—C3	−0.1 (6)	C17—C11—C16—C15	178.3 (4)
N1—C1—C2—C3	178.0 (3)	C5—C4—S4—O2	−20.8 (3)
C1—C2—C3—C4	0.6 (6)	C3—C4—S4—O2	158.2 (3)
C2—C3—C4—C5	−0.2 (5)	C5—C4—S4—O1	−153.0 (3)
C2—C3—C4—S4	−179.3 (3)	C3—C4—S4—O1	26.1 (3)
C3—C4—C5—C6	−0.7 (5)	C5—C4—S4—N4	92.0 (3)
S4—C4—C5—C6	178.4 (3)	C3—C4—S4—N4	−89.0 (3)
C4—C5—C6—C1	1.2 (6)	O2—S4—N4—C45	170.0 (3)
C2—C1—C6—C5	−0.8 (6)	O1—S4—N4—C45	−60.8 (3)
N1—C1—C6—C5	−178.8 (3)	C4—S4—N4—C45	54.1 (3)
C2—C1—N1—C17	167.3 (3)	C45—O41—N42—C43	−1.1 (4)
C6—C1—N1—C17	−14.7 (5)	O41—N42—C43—C44	0.9 (4)
C1—N1—C17—C11	178.2 (3)	O41—N42—C43—C46	179.2 (3)
N1—C17—C11—C16	−176.8 (4)	N42—C43—C44—C45	−0.3 (4)
N1—C17—C11—C12	2.6 (6)	C46—C43—C44—C45	−178.5 (4)
C16—C11—C12—O12	178.4 (4)	N42—C43—C44—C47	176.8 (3)
C17—C11—C12—O12	−1.0 (5)	C46—C43—C44—C47	−1.4 (6)
C16—C11—C12—C13	−1.4 (5)	C43—C44—C45—O41	−0.5 (4)
C17—C11—C12—C13	179.2 (3)	C47—C44—C45—O41	−177.4 (3)
O12—C12—C13—C14	−177.1 (4)	C43—C44—C45—N4	178.3 (4)
C11—C12—C13—C14	2.7 (6)	C47—C44—C45—N4	1.4 (7)
C12—C13—C14—C15	−1.5 (7)	N42—O41—C45—C44	1.0 (4)
C13—C14—C15—C16	−1.1 (7)	N42—O41—C45—N4	−178.0 (3)
C14—C15—C16—C11	2.4 (7)	S4—N4—C45—C44	65.5 (5)
C12—C11—C16—C15	−1.1 (6)	S4—N4—C45—O41	−115.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···N42ⁱ	0.87 (4)	2.07 (4)	2.931 (4)	168 (3)
O12—H12···N1	0.82	1.88	2.606 (4)	147

Symmetry code: (i) x, −y+1/2, z+1/2.

(E)-4-[(5-Bromo-2-hydroxy-3-methoxybenzylidene)amino]-N-(3,4-dimethylisoxazol-5-yl)benzenesulfonamide (II) top

Crystal data top

C₁₉H₁₈BrN₃O₅S	F(000) = 976
M_r = 480.32	D_x = 1.524 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.6043 (11) Å	Cell parameters from 6249 reflections
b = 12.2399 (7) Å	θ = 1.5–30.3°
c = 12.9506 (9) Å	µ = 2.10 mm⁻¹
β = 103.854 (2)°	T = 296 K
V = 2093.7 (3) Å³	Block, orange
Z = 4	0.15 × 0.15 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	4840 independent reflections
Radiation source: fine focus sealed tube	3092 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
φ and ω scans	θ_max = 27.6°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −17→17
T_min = 0.673, T_max = 0.811	k = −15→15
22426 measured reflections	l = −16→16

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.123	w = 1/[σ²(F_o²) + (0.0552P)² + 1.263P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
4840 reflections	Δρ_max = 0.56 e Å⁻³
270 parameters	Δρ_min = −0.77 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
C1	0.4671 (2)	0.2968 (2)	0.4272 (2)	0.0357 (6)
C2	0.4592 (2)	0.4004 (2)	0.3834 (2)	0.0405 (7)
H2	0.4189	0.4526	0.4054	0.049*
C3	0.5106 (2)	0.4267 (2)	0.3076 (2)	0.0409 (7)
H3	0.5043	0.4959	0.2772	0.049*
C4	0.5718 (2)	0.3492 (2)	0.2769 (2)	0.0343 (6)
C5	0.5815 (2)	0.2454 (2)	0.3210 (2)	0.0398 (7)
H5	0.6233	0.1941	0.3002	0.048*
C6	0.5285 (2)	0.2188 (2)	0.3963 (2)	0.0410 (7)
H6	0.5340	0.1492	0.4261	0.049*
N1	0.41147 (19)	0.27464 (18)	0.50505 (18)	0.0390 (6)
C17	0.3757 (2)	0.1785 (2)	0.5151 (2)	0.0399 (7)
H17	0.3892	0.1216	0.4730	0.048*
C11	0.3155 (2)	0.1579 (2)	0.5902 (2)	0.0379 (7)
C12	0.2960 (2)	0.2422 (2)	0.6562 (2)	0.0341 (6)
C13	0.2305 (2)	0.2215 (2)	0.7237 (2)	0.0391 (7)
C14	0.1858 (2)	0.1214 (2)	0.7242 (2)	0.0436 (7)
H14	0.1418	0.1085	0.7678	0.052*
C15	0.2072 (3)	0.0386 (2)	0.6583 (3)	0.0467 (8)
Br15	0.14289 (4)	−0.09879 (3)	0.65963 (4)	0.08006 (19)
C16	0.2709 (3)	0.0545 (2)	0.5935 (3)	0.0474 (8)
H16	0.2850	−0.0023	0.5515	0.057*
O12	0.33476 (17)	0.34159 (15)	0.65574 (17)	0.0462 (5)
H12	0.3694	0.3442	0.6120	0.069*
O13	0.21597 (18)	0.30984 (17)	0.78226 (18)	0.0512 (6)
C131	0.1405 (3)	0.3022 (3)	0.8418 (3)	0.0627 (10)
H13A	0.0771	0.2815	0.7953	0.094*
H13B	0.1333	0.3718	0.8734	0.094*
H13C	0.1603	0.2483	0.8966	0.094*
S4	0.64334 (6)	0.38550 (6)	0.18544 (5)	0.0390 (2)
O1	0.58155 (19)	0.45465 (18)	0.10708 (16)	0.0529 (6)
O2	0.68760 (19)	0.28916 (16)	0.15476 (16)	0.0524 (6)
N4	0.7345 (2)	0.4638 (2)	0.2494 (2)	0.0428 (6)
H4	0.717 (3)	0.522 (3)	0.260 (3)	0.055 (11)*
O41	0.8974 (2)	0.3981 (2)	0.2898 (2)	0.0783 (9)
N42	0.9723 (3)	0.3623 (4)	0.3778 (4)	0.1057 (15)
C43	0.9329 (3)	0.3685 (3)	0.4584 (4)	0.0758 (12)
C44	0.8324 (3)	0.4069 (3)	0.4312 (3)	0.0500 (8)
C45	0.8154 (3)	0.4230 (2)	0.3261 (3)	0.0443 (7)
C46	0.9924 (4)	0.3345 (5)	0.5680 (4)	0.127 (2)
H46A	1.0616	0.3215	0.5664	0.191*
H46B	0.9638	0.2688	0.5889	0.191*
H46C	0.9894	0.3915	0.6180	0.191*
C47	0.7629 (3)	0.4266 (4)	0.5036 (3)	0.0736 (12)
H47A	0.6998	0.4557	0.4632	0.110*
H47B	0.7936	0.4778	0.5578	0.110*
H47C	0.7508	0.3590	0.5360	0.110*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0368 (17)	0.0374 (14)	0.0336 (14)	−0.0034 (13)	0.0101 (13)	−0.0004 (12)
C2	0.0378 (18)	0.0369 (15)	0.0495 (17)	0.0033 (13)	0.0158 (14)	−0.0001 (13)
C3	0.0461 (19)	0.0308 (14)	0.0463 (16)	0.0011 (13)	0.0123 (15)	0.0076 (12)
C4	0.0390 (17)	0.0335 (14)	0.0302 (14)	−0.0055 (12)	0.0076 (13)	0.0006 (11)
C5	0.049 (2)	0.0334 (14)	0.0417 (15)	0.0031 (13)	0.0189 (15)	0.0004 (12)
C6	0.052 (2)	0.0345 (14)	0.0400 (15)	0.0048 (14)	0.0183 (15)	0.0086 (12)
N1	0.0439 (16)	0.0374 (13)	0.0396 (13)	−0.0017 (11)	0.0179 (12)	0.0007 (10)
C17	0.0427 (19)	0.0376 (15)	0.0416 (16)	0.0005 (14)	0.0147 (14)	−0.0054 (13)
C11	0.0370 (17)	0.0349 (14)	0.0437 (16)	−0.0016 (13)	0.0134 (14)	0.0019 (12)
C12	0.0320 (17)	0.0319 (13)	0.0389 (15)	−0.0015 (12)	0.0094 (13)	0.0033 (12)
C13	0.0375 (18)	0.0389 (15)	0.0430 (16)	0.0017 (13)	0.0139 (14)	0.0037 (13)
C14	0.0412 (19)	0.0443 (17)	0.0484 (17)	−0.0054 (14)	0.0168 (15)	0.0087 (14)
C15	0.047 (2)	0.0343 (15)	0.0595 (19)	−0.0078 (14)	0.0141 (17)	0.0075 (14)
Br15	0.0931 (4)	0.0425 (2)	0.1170 (4)	−0.0247 (2)	0.0496 (3)	−0.0023 (2)
C16	0.054 (2)	0.0314 (14)	0.0579 (19)	−0.0036 (15)	0.0168 (17)	−0.0039 (14)
O12	0.0552 (15)	0.0354 (10)	0.0585 (13)	−0.0097 (10)	0.0346 (11)	−0.0059 (9)
O13	0.0585 (15)	0.0457 (12)	0.0605 (13)	−0.0100 (11)	0.0358 (12)	−0.0086 (10)
C131	0.061 (2)	0.080 (2)	0.060 (2)	−0.009 (2)	0.0386 (19)	−0.0149 (19)
S4	0.0543 (5)	0.0344 (4)	0.0311 (3)	−0.0054 (3)	0.0160 (3)	0.0003 (3)
O1	0.0706 (17)	0.0508 (12)	0.0350 (11)	−0.0066 (12)	0.0082 (11)	0.0108 (10)
O2	0.0773 (17)	0.0415 (11)	0.0475 (12)	−0.0028 (11)	0.0328 (12)	−0.0071 (9)
N4	0.0513 (18)	0.0346 (14)	0.0461 (15)	−0.0039 (13)	0.0187 (14)	−0.0020 (12)
O41	0.0522 (17)	0.106 (2)	0.0832 (19)	0.0152 (15)	0.0285 (16)	−0.0247 (16)
N42	0.056 (3)	0.130 (4)	0.122 (3)	0.038 (2)	0.005 (3)	−0.039 (3)
C43	0.064 (3)	0.063 (2)	0.087 (3)	0.015 (2)	−0.007 (3)	−0.013 (2)
C44	0.043 (2)	0.0467 (18)	0.055 (2)	−0.0011 (15)	0.0028 (16)	−0.0044 (15)
C45	0.0388 (18)	0.0403 (16)	0.057 (2)	−0.0010 (14)	0.0171 (16)	−0.0091 (14)
C46	0.113 (5)	0.108 (4)	0.121 (4)	0.038 (4)	−0.051 (4)	−0.010 (4)
C47	0.072 (3)	0.106 (3)	0.043 (2)	−0.002 (2)	0.013 (2)	0.002 (2)

Geometric parameters (Å, º) top

C1—C2	1.382 (4)	C16—H16	0.9300
C1—C6	1.390 (4)	O12—H12	0.8200
C1—N1	1.423 (3)	O13—C131	1.427 (4)
C2—C3	1.373 (4)	C131—H13A	0.9600
C2—H2	0.9300	C131—H13B	0.9600
C3—C4	1.381 (4)	C131—H13C	0.9600
C3—H3	0.9300	S4—O2	1.423 (2)
C4—C5	1.386 (4)	S4—O1	1.430 (2)
C4—S4	1.761 (3)	S4—N4	1.628 (3)
C5—C6	1.383 (4)	N4—C45	1.387 (4)
C5—H5	0.9300	N4—H4	0.78 (4)
C6—H6	0.9300	O41—C45	1.345 (4)
N1—C17	1.292 (4)	O41—N42	1.404 (5)
C17—C11	1.435 (4)	N42—C43	1.285 (6)
C17—H17	0.9300	C43—C44	1.408 (5)
C11—C12	1.405 (4)	C43—C46	1.514 (6)
C11—C16	1.408 (4)	C44—C45	1.340 (5)
C12—O12	1.326 (3)	C44—C47	1.502 (5)
C12—C13	1.414 (4)	C46—H46A	0.9600
C13—O13	1.362 (3)	C46—H46B	0.9600
C13—C14	1.368 (4)	C46—H46C	0.9600
C14—C15	1.400 (4)	C47—H47A	0.9600
C14—H14	0.9300	C47—H47B	0.9600
C15—C16	1.358 (4)	C47—H47C	0.9600
C15—Br15	1.897 (3)

C2—C1—C6	120.3 (3)	C12—O12—H12	109.5
C2—C1—N1	117.6 (2)	C13—O13—C131	117.9 (2)
C6—C1—N1	122.1 (2)	O13—C131—H13A	109.5
C3—C2—C1	120.4 (3)	O13—C131—H13B	109.5
C3—C2—H2	119.8	H13A—C131—H13B	109.5
C1—C2—H2	119.8	O13—C131—H13C	109.5
C2—C3—C4	119.3 (3)	H13A—C131—H13C	109.5
C2—C3—H3	120.3	H13B—C131—H13C	109.5
C4—C3—H3	120.3	O2—S4—O1	120.56 (13)
C3—C4—C5	121.0 (3)	O2—S4—N4	107.97 (15)
C3—C4—S4	119.2 (2)	O1—S4—N4	105.01 (14)
C5—C4—S4	119.7 (2)	O2—S4—C4	108.52 (13)
C6—C5—C4	119.5 (3)	O1—S4—C4	107.52 (14)
C6—C5—H5	120.2	N4—S4—C4	106.44 (13)
C4—C5—H5	120.2	C45—N4—S4	122.0 (2)
C5—C6—C1	119.5 (3)	C45—N4—H4	115 (3)
C5—C6—H6	120.3	S4—N4—H4	114 (3)
C1—C6—H6	120.3	C45—O41—N42	106.8 (3)
C17—N1—C1	121.5 (2)	C43—N42—O41	106.2 (3)
N1—C17—C11	121.2 (3)	N42—C43—C44	112.6 (4)
N1—C17—H17	119.4	N42—C43—C46	120.8 (5)
C11—C17—H17	119.4	C44—C43—C46	126.6 (5)
C12—C11—C16	119.8 (3)	C45—C44—C43	103.0 (3)
C12—C11—C17	120.3 (2)	C45—C44—C47	129.0 (3)
C16—C11—C17	119.9 (3)	C43—C44—C47	128.0 (3)
O12—C12—C11	122.6 (2)	C44—C45—O41	111.4 (3)
O12—C12—C13	118.5 (2)	C44—C45—N4	134.0 (3)
C11—C12—C13	118.9 (2)	O41—C45—N4	114.5 (3)
O13—C13—C14	125.8 (3)	C43—C46—H46A	109.5
O13—C13—C12	113.5 (2)	C43—C46—H46B	109.5
C14—C13—C12	120.7 (3)	H46A—C46—H46B	109.5
C13—C14—C15	119.3 (3)	C43—C46—H46C	109.5
C13—C14—H14	120.4	H46A—C46—H46C	109.5
C15—C14—H14	120.4	H46B—C46—H46C	109.5
C16—C15—C14	121.9 (3)	C44—C47—H47A	109.5
C16—C15—Br15	119.8 (2)	C44—C47—H47B	109.5
C14—C15—Br15	118.2 (2)	H47A—C47—H47B	109.5
C15—C16—C11	119.4 (3)	C44—C47—H47C	109.5
C15—C16—H16	120.3	H47A—C47—H47C	109.5
C11—C16—H16	120.3	H47B—C47—H47C	109.5

C6—C1—C2—C3	1.2 (5)	C12—C11—C16—C15	1.8 (5)
N1—C1—C2—C3	−179.7 (3)	C17—C11—C16—C15	−174.4 (3)
C1—C2—C3—C4	−1.2 (5)	C14—C13—O13—C131	−6.6 (5)
C2—C3—C4—C5	0.4 (5)	C12—C13—O13—C131	171.5 (3)
C2—C3—C4—S4	−176.3 (2)	C3—C4—S4—O2	−171.5 (2)
C3—C4—C5—C6	0.5 (5)	C5—C4—S4—O2	11.8 (3)
S4—C4—C5—C6	177.1 (2)	C3—C4—S4—O1	−39.6 (3)
C4—C5—C6—C1	−0.5 (5)	C5—C4—S4—O1	143.7 (2)
C2—C1—C6—C5	−0.3 (5)	C3—C4—S4—N4	72.5 (3)
N1—C1—C6—C5	−179.4 (3)	C5—C4—S4—N4	−104.2 (3)
C2—C1—N1—C17	148.0 (3)	O2—S4—N4—C45	−44.3 (3)
C6—C1—N1—C17	−32.9 (4)	O1—S4—N4—C45	−174.1 (2)
C1—N1—C17—C11	−176.9 (3)	C4—S4—N4—C45	72.1 (3)
N1—C17—C11—C12	−1.3 (5)	C45—O41—N42—C43	−0.5 (5)
N1—C17—C11—C16	174.9 (3)	O41—N42—C43—C44	0.3 (5)
C16—C11—C12—O12	−179.1 (3)	O41—N42—C43—C46	179.2 (4)
C17—C11—C12—O12	−2.9 (5)	N42—C43—C44—C45	0.1 (5)
C16—C11—C12—C13	−0.8 (4)	C46—C43—C44—C45	−178.8 (4)
C17—C11—C12—C13	175.4 (3)	N42—C43—C44—C47	−178.8 (4)
O12—C12—C13—O13	−0.5 (4)	C46—C43—C44—C47	2.4 (7)
C11—C12—C13—O13	−178.9 (3)	C43—C44—C45—O41	−0.4 (4)
O12—C12—C13—C14	177.7 (3)	C47—C44—C45—O41	178.5 (4)
C11—C12—C13—C14	−0.7 (4)	C43—C44—C45—N4	−176.9 (4)
O13—C13—C14—C15	179.1 (3)	C47—C44—C45—N4	1.9 (6)
C12—C13—C14—C15	1.2 (5)	N42—O41—C45—C44	0.6 (4)
C13—C14—C15—C16	−0.1 (5)	N42—O41—C45—N4	177.8 (3)
C13—C14—C15—Br15	−179.3 (2)	S4—N4—C45—C44	−88.8 (4)
C14—C15—C16—C11	−1.4 (5)	S4—N4—C45—O41	94.7 (3)
Br15—C15—C16—C11	177.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O12ⁱ	0.77 (4)	2.20 (4)	2.937 (3)	159 (4)
N4—H4···O13ⁱ	0.77 (4)	2.37 (4)	2.904 (3)	127 (4)
O12—H12···N1	0.82	1.83	2.558 (3)	147
C17—H17···O1ⁱⁱ	0.93	2.37	3.285 (3)	169

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

(E)-4-Bromo-2-[(2-hydroxyphenylimino)methyl]-6-methoxyphenol (III) top

Crystal data top

C₁₄H₁₂BrNO₃	F(000) = 648
M_r = 322.15	D_x = 1.662 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.297 (2) Å	Cell parameters from 3375 reflections
b = 15.095 (3) Å	θ = 1.5–28.9°
c = 6.4166 (13) Å	µ = 3.20 mm⁻¹
β = 91.329 (6)°	T = 296 K
V = 1287.6 (4) Å³	Block, brown
Z = 4	0.25 × 0.20 × 0.15 mm

Data collection top

Bruker APEXII CCD diffractometer	2979 independent reflections
Radiation source: fine focus sealed tube	1807 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
φ and ω scans	θ_max = 27.6°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −17→17
T_min = 0.327, T_max = 0.619	k = −19→19
14568 measured reflections	l = −8→7

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0431P)² + 0.5394P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
2979 reflections	Δρ_max = 0.71 e Å⁻³
173 parameters	Δρ_min = −0.37 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
C1	0.2524 (2)	0.4272 (2)	0.3637 (4)	0.0341 (7)
C2	0.3399 (2)	0.4142 (2)	0.2541 (5)	0.0354 (7)
C3	0.3371 (3)	0.3646 (2)	0.0732 (5)	0.0446 (8)
H3	0.3955	0.3557	−0.0008	0.054*
C4	0.2477 (3)	0.3284 (2)	0.0027 (5)	0.0471 (8)
H4	0.2462	0.2946	−0.1185	0.057*
C5	0.1609 (3)	0.3415 (2)	0.1093 (5)	0.0455 (8)
H5	0.1007	0.3172	0.0596	0.055*
C6	0.1629 (2)	0.3910 (2)	0.2910 (5)	0.0424 (8)
H6	0.1041	0.3998	0.3640	0.051*
N1	0.26220 (18)	0.47903 (16)	0.5459 (4)	0.0366 (6)
H1	0.3226	0.4948	0.5789	0.044*
O2	0.42320 (15)	0.45293 (16)	0.3355 (3)	0.0516 (6)
H2	0.4722	0.4465	0.2580	0.077*
C11	0.2154 (2)	0.5576 (2)	0.8504 (4)	0.0356 (7)
C12	0.3166 (2)	0.5806 (2)	0.9018 (5)	0.0363 (7)
O12	0.38985 (15)	0.55811 (16)	0.7852 (3)	0.0473 (6)
C13	0.3347 (2)	0.6292 (2)	1.0906 (5)	0.0362 (7)
C14	0.2567 (2)	0.6549 (2)	1.2122 (5)	0.0399 (8)
H14	0.2690	0.6880	1.3323	0.048*
C15	0.1582 (2)	0.6309 (2)	1.1542 (5)	0.0412 (8)
Br15	0.05396 (3)	0.66606 (3)	1.33499 (6)	0.06282 (17)
C16	0.1355 (2)	0.5844 (2)	0.9809 (5)	0.0407 (8)
H16	0.0691	0.5701	0.9467	0.049*
C17	0.1936 (2)	0.5064 (2)	0.6711 (5)	0.0387 (7)
H17	0.1269	0.4916	0.6413	0.046*
O13	0.43357 (16)	0.64571 (15)	1.1307 (3)	0.0452 (6)
C113	0.4586 (3)	0.6907 (3)	1.3208 (5)	0.0609 (11)
H11A	0.4322	0.6583	1.4360	0.091*
H11B	0.4300	0.7491	1.3174	0.091*
H11C	0.5304	0.6950	1.3366	0.091*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0349 (17)	0.0357 (18)	0.0315 (15)	−0.0037 (14)	−0.0032 (13)	0.0012 (13)
C2	0.0318 (16)	0.0372 (17)	0.0373 (16)	−0.0016 (14)	−0.0020 (13)	0.0028 (14)
C3	0.051 (2)	0.0426 (19)	0.0410 (18)	0.0057 (17)	0.0090 (16)	−0.0014 (15)
C4	0.063 (2)	0.0391 (19)	0.0393 (18)	−0.0015 (17)	−0.0028 (17)	−0.0057 (15)
C5	0.0426 (19)	0.0414 (19)	0.052 (2)	−0.0111 (16)	−0.0088 (16)	−0.0001 (17)
C6	0.0369 (18)	0.047 (2)	0.0437 (19)	−0.0060 (15)	0.0005 (15)	0.0007 (16)
N1	0.0302 (13)	0.0450 (16)	0.0347 (14)	−0.0051 (12)	0.0017 (11)	−0.0029 (12)
O2	0.0304 (12)	0.0732 (17)	0.0513 (14)	−0.0040 (11)	0.0049 (11)	−0.0160 (12)
C11	0.0351 (17)	0.0379 (18)	0.0338 (16)	0.0019 (14)	0.0007 (13)	0.0016 (14)
C12	0.0406 (18)	0.0368 (18)	0.0318 (15)	−0.0012 (15)	0.0049 (14)	0.0014 (14)
O12	0.0335 (12)	0.0670 (16)	0.0417 (12)	−0.0061 (11)	0.0082 (10)	−0.0150 (11)
C13	0.0375 (18)	0.0334 (17)	0.0379 (17)	−0.0018 (14)	0.0028 (14)	0.0026 (14)
C14	0.047 (2)	0.0414 (19)	0.0314 (16)	0.0014 (15)	0.0043 (14)	−0.0040 (14)
C15	0.0429 (19)	0.0424 (19)	0.0389 (18)	0.0072 (15)	0.0119 (15)	0.0010 (15)
Br15	0.0519 (2)	0.0814 (3)	0.0560 (2)	0.0106 (2)	0.01965 (18)	−0.0126 (2)
C16	0.0324 (17)	0.048 (2)	0.0421 (18)	0.0033 (15)	0.0036 (14)	0.0004 (16)
C17	0.0321 (17)	0.044 (2)	0.0402 (17)	0.0014 (14)	0.0029 (14)	−0.0007 (15)
O13	0.0414 (13)	0.0577 (15)	0.0367 (13)	−0.0072 (11)	0.0038 (10)	−0.0102 (10)
C113	0.055 (2)	0.085 (3)	0.043 (2)	−0.015 (2)	−0.0018 (17)	−0.0154 (19)

Geometric parameters (Å, º) top

C1—C6	1.381 (4)	C11—C12	1.421 (4)
C1—C2	1.388 (4)	C11—C16	1.428 (4)
C1—N1	1.410 (4)	C12—O12	1.287 (3)
C2—O2	1.347 (4)	C12—C13	1.431 (4)
C2—C3	1.381 (4)	C13—O13	1.357 (3)
C3—C4	1.375 (5)	C13—C14	1.368 (4)
C3—H3	0.9300	C14—C15	1.402 (4)
C4—C5	1.369 (5)	C14—H14	0.9300
C4—H4	0.9300	C15—C16	1.343 (4)
C5—C6	1.385 (5)	C15—Br15	1.903 (3)
C5—H5	0.9300	C16—H16	0.9300
C6—H6	0.9300	C17—H17	0.9300
N1—C17	1.297 (4)	O13—C113	1.428 (4)
N1—H1	0.8600	C113—H11A	0.9600
O2—H2	0.8343	C113—H11B	0.9600
C11—C17	1.410 (4)	C113—H11C	0.9600

C6—C1—C2	119.9 (3)	O12—C12—C11	121.7 (3)
C6—C1—N1	124.2 (3)	O12—C12—C13	120.8 (3)
C2—C1—N1	115.8 (3)	C11—C12—C13	117.5 (3)
O2—C2—C3	124.6 (3)	O13—C13—C14	125.7 (3)
O2—C2—C1	115.7 (3)	O13—C13—C12	113.4 (3)
C3—C2—C1	119.7 (3)	C14—C13—C12	120.9 (3)
C4—C3—C2	119.9 (3)	C13—C14—C15	119.4 (3)
C4—C3—H3	120.0	C13—C14—H14	120.3
C2—C3—H3	120.0	C15—C14—H14	120.3
C5—C4—C3	120.7 (3)	C16—C15—C14	123.1 (3)
C5—C4—H4	119.7	C16—C15—Br15	119.8 (2)
C3—C4—H4	119.7	C14—C15—Br15	117.1 (2)
C4—C5—C6	119.9 (3)	C15—C16—C11	118.5 (3)
C4—C5—H5	120.0	C15—C16—H16	120.7
C6—C5—H5	120.0	C11—C16—H16	120.7
C1—C6—C5	119.8 (3)	N1—C17—C11	123.0 (3)
C1—C6—H6	120.1	N1—C17—H17	118.5
C5—C6—H6	120.1	C11—C17—H17	118.5
C17—N1—C1	129.6 (3)	C13—O13—C113	117.1 (3)
C17—N1—H1	115.2	O13—C113—H11A	109.5
C1—N1—H1	115.2	O13—C113—H11B	109.5
C2—O2—H2	111.4	H11A—C113—H11B	109.5
C17—C11—C12	120.0 (3)	O13—C113—H11C	109.5
C17—C11—C16	119.5 (3)	H11A—C113—H11C	109.5
C12—C11—C16	120.6 (3)	H11B—C113—H11C	109.5

C6—C1—C2—O2	179.2 (3)	O12—C12—C13—O13	−1.3 (4)
N1—C1—C2—O2	−0.2 (4)	C11—C12—C13—O13	177.9 (3)
C6—C1—C2—C3	−0.3 (5)	O12—C12—C13—C14	178.5 (3)
N1—C1—C2—C3	−179.7 (3)	C11—C12—C13—C14	−2.3 (4)
O2—C2—C3—C4	−179.5 (3)	O13—C13—C14—C15	−178.2 (3)
C1—C2—C3—C4	0.0 (5)	C12—C13—C14—C15	2.0 (5)
C2—C3—C4—C5	0.5 (5)	C13—C14—C15—C16	−1.1 (5)
C3—C4—C5—C6	−0.6 (5)	C13—C14—C15—Br15	178.3 (2)
C2—C1—C6—C5	0.2 (5)	C14—C15—C16—C11	0.5 (5)
N1—C1—C6—C5	179.5 (3)	Br15—C15—C16—C11	−178.8 (2)
C4—C5—C6—C1	0.3 (5)	C17—C11—C16—C15	178.1 (3)
C6—C1—N1—C17	−3.9 (5)	C12—C11—C16—C15	−0.8 (5)
C2—C1—N1—C17	175.4 (3)	C1—N1—C17—C11	179.3 (3)
C17—C11—C12—O12	2.0 (5)	C12—C11—C17—N1	−0.6 (5)
C16—C11—C12—O12	−179.1 (3)	C16—C11—C17—N1	−179.5 (3)
C17—C11—C12—C13	−177.2 (3)	C14—C13—O13—C113	2.7 (5)
C16—C11—C12—C13	1.7 (4)	C12—C13—O13—C113	−177.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.17	2.588 (3)	109
N1—H1···O12	0.86	1.85	2.558 (3)	139
O2—H2···O12ⁱ	0.82	1.86	2.626 (3)	151
C3—H3···O13ⁱ	0.93	2.44	3.350 (4)	166
C4—H4···Cg1ⁱⁱ	0.93	2.90	3.731 (3)	149

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z−3/2.

(E)-4-Bromo-2-methoxy-6-[(2-methoxyphenylimino)methyl]phenol (IV) top

Crystal data top

C₁₅H₁₄BrNO₃	Z = 2
M_r = 336.17	F(000) = 340
Triclinic, P1	D_x = 1.581 Mg m⁻³
a = 6.4158 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.3886 (4) Å	Cell parameters from 3426 reflections
c = 15.2636 (7) Å	θ = 1.3–28.1°
α = 87.081 (3)°	µ = 2.92 mm⁻¹
β = 87.488 (3)°	T = 296 K
γ = 77.948 (3)°	Block, orange
V = 706.28 (6) Å³	0.30 × 0.25 × 0.20 mm

Data collection top

Bruker APEXII CCD diffractometer	3265 independent reflections
Radiation source: fine focus sealed tube	2240 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
φ and ω scans	θ_max = 27.5°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −8→8
T_min = 0.322, T_max = 0.558	k = −9→9
16535 measured reflections	l = −19→19

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.072	w = 1/[σ²(F_o²) + (0.0262P)² + 0.2214P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
3265 reflections	Δρ_max = 0.37 e Å⁻³
184 parameters	Δρ_min = −0.34 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
C1	0.7059 (3)	0.2769 (3)	0.22114 (15)	0.0378 (5)
C2	0.8316 (4)	0.2335 (3)	0.29478 (16)	0.0430 (6)
C3	1.0360 (4)	0.1298 (4)	0.2861 (2)	0.0562 (7)
H3	1.1201	0.0997	0.3350	0.067*
C4	1.1154 (4)	0.0709 (4)	0.2047 (2)	0.0613 (8)
H4	1.2535	0.0012	0.1994	0.074*
C5	0.9964 (4)	0.1123 (4)	0.1320 (2)	0.0557 (7)
H5	1.0523	0.0720	0.0774	0.067*
C6	0.7903 (4)	0.2157 (3)	0.14060 (17)	0.0483 (6)
H6	0.7076	0.2444	0.0913	0.058*
N1	0.4991 (3)	0.3857 (3)	0.23626 (12)	0.0383 (4)
O2	0.7364 (3)	0.2996 (3)	0.37170 (11)	0.0572 (5)
C21	0.8634 (5)	0.2772 (5)	0.44787 (17)	0.0698 (9)
H21A	0.9097	0.1476	0.4629	0.105*
H21B	0.7802	0.3372	0.4960	0.105*
H21C	0.9856	0.3316	0.4358	0.105*
C11	0.1570 (3)	0.5531 (3)	0.19762 (14)	0.0349 (5)
C12	0.0995 (3)	0.5987 (3)	0.28483 (15)	0.0383 (5)
O12	0.2333 (3)	0.5482 (3)	0.34994 (10)	0.0543 (5)
H12	0.3443	0.4836	0.3310	0.081*
C13	−0.1085 (4)	0.6993 (3)	0.30436 (15)	0.0397 (6)
C14	−0.2496 (4)	0.7521 (3)	0.23830 (15)	0.0408 (6)
H14	−0.3867	0.8181	0.2511	0.049*
C15	−0.1885 (4)	0.7075 (3)	0.15261 (15)	0.0391 (5)
Br15	−0.38932 (4)	0.78676 (4)	0.06357 (2)	0.05846 (12)
C16	0.0101 (4)	0.6106 (3)	0.13123 (14)	0.0386 (5)
H16	0.0481	0.5827	0.0732	0.046*
C17	0.3641 (3)	0.4427 (3)	0.17669 (15)	0.0392 (5)
H17	0.4003	0.4123	0.1188	0.047*
O13	−0.1504 (3)	0.7366 (3)	0.39020 (11)	0.0571 (5)
C113	−0.3642 (4)	0.8120 (5)	0.41627 (19)	0.0740 (9)
H11A	−0.4056	0.9354	0.3911	0.111*
H11B	−0.3762	0.8153	0.4791	0.111*
H11C	−0.4558	0.7364	0.3962	0.111*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0342 (12)	0.0336 (13)	0.0459 (14)	−0.0069 (10)	0.0021 (11)	−0.0065 (11)
C2	0.0375 (13)	0.0395 (14)	0.0508 (15)	−0.0055 (11)	0.0004 (11)	−0.0037 (12)
C3	0.0420 (15)	0.0516 (17)	0.0711 (19)	0.0007 (13)	−0.0099 (14)	−0.0015 (14)
C4	0.0365 (14)	0.0458 (17)	0.097 (2)	0.0020 (12)	0.0068 (16)	−0.0110 (16)
C5	0.0505 (16)	0.0447 (16)	0.0718 (19)	−0.0088 (13)	0.0171 (15)	−0.0216 (14)
C6	0.0468 (15)	0.0464 (16)	0.0517 (16)	−0.0082 (12)	0.0027 (12)	−0.0119 (12)
N1	0.0309 (10)	0.0418 (12)	0.0416 (11)	−0.0045 (8)	−0.0011 (9)	−0.0060 (9)
O2	0.0471 (10)	0.0755 (13)	0.0432 (10)	0.0023 (9)	−0.0091 (8)	−0.0034 (9)
C21	0.0687 (19)	0.091 (2)	0.0463 (16)	−0.0094 (17)	−0.0180 (14)	0.0079 (15)
C11	0.0345 (12)	0.0351 (13)	0.0357 (12)	−0.0081 (10)	−0.0007 (10)	−0.0035 (10)
C12	0.0335 (12)	0.0438 (14)	0.0379 (13)	−0.0073 (10)	−0.0042 (10)	−0.0046 (11)
O12	0.0375 (9)	0.0823 (14)	0.0377 (9)	0.0036 (9)	−0.0064 (7)	−0.0141 (9)
C13	0.0370 (13)	0.0456 (15)	0.0366 (13)	−0.0079 (11)	0.0015 (10)	−0.0084 (11)
C14	0.0331 (12)	0.0388 (14)	0.0484 (15)	−0.0015 (10)	−0.0016 (11)	−0.0049 (11)
C15	0.0381 (13)	0.0404 (14)	0.0382 (13)	−0.0070 (11)	−0.0064 (10)	0.0036 (11)
Br15	0.04838 (17)	0.0752 (2)	0.04735 (17)	−0.00178 (13)	−0.01454 (12)	0.00530 (13)
C16	0.0428 (14)	0.0414 (14)	0.0317 (12)	−0.0089 (11)	−0.0005 (10)	−0.0028 (10)
C17	0.0410 (13)	0.0400 (14)	0.0367 (13)	−0.0078 (11)	0.0021 (11)	−0.0069 (11)
O13	0.0431 (10)	0.0845 (14)	0.0388 (10)	0.0011 (9)	0.0021 (8)	−0.0184 (9)
C113	0.0469 (17)	0.112 (3)	0.0578 (18)	−0.0015 (17)	0.0124 (14)	−0.0313 (18)

Geometric parameters (Å, º) top

C1—C6	1.380 (3)	C11—C12	1.404 (3)
C1—C2	1.397 (3)	C11—C17	1.439 (3)
C1—N1	1.416 (3)	C12—O12	1.329 (3)
C2—O2	1.364 (3)	C12—C13	1.413 (3)
C2—C3	1.379 (3)	O12—H12	0.8200
C3—C4	1.378 (4)	C13—O13	1.356 (3)
C3—H3	0.9300	C13—C14	1.372 (3)
C4—C5	1.361 (4)	C14—C15	1.385 (3)
C4—H4	0.9300	C14—H14	0.9300
C5—C6	1.386 (3)	C15—C16	1.360 (3)
C5—H5	0.9300	C15—Br15	1.899 (2)
C6—H6	0.9300	C16—H16	0.9300
N1—C17	1.277 (3)	C17—H17	0.9300
O2—C21	1.432 (3)	O13—C113	1.416 (3)
C21—H21A	0.9600	C113—H11A	0.9600
C21—H21B	0.9600	C113—H11B	0.9600
C21—H21C	0.9600	C113—H11C	0.9600
C11—C16	1.403 (3)

C6—C1—C2	119.0 (2)	C12—C11—C17	120.0 (2)
C6—C1—N1	125.3 (2)	O12—C12—C11	122.2 (2)
C2—C1—N1	115.7 (2)	O12—C12—C13	118.8 (2)
O2—C2—C3	124.9 (2)	C11—C12—C13	119.0 (2)
O2—C2—C1	115.3 (2)	C12—O12—H12	109.5
C3—C2—C1	119.8 (2)	O13—C13—C14	125.2 (2)
C4—C3—C2	119.7 (3)	O13—C13—C12	114.98 (19)
C4—C3—H3	120.1	C14—C13—C12	119.8 (2)
C2—C3—H3	120.1	C13—C14—C15	120.2 (2)
C5—C4—C3	121.6 (2)	C13—C14—H14	119.9
C5—C4—H4	119.2	C15—C14—H14	119.9
C3—C4—H4	119.2	C16—C15—C14	121.7 (2)
C4—C5—C6	118.8 (3)	C16—C15—Br15	119.87 (17)
C4—C5—H5	120.6	C14—C15—Br15	118.38 (17)
C6—C5—H5	120.6	C15—C16—C11	119.3 (2)
C1—C6—C5	121.1 (2)	C15—C16—H16	120.4
C1—C6—H6	119.4	C11—C16—H16	120.4
C5—C6—H6	119.4	N1—C17—C11	121.1 (2)
C17—N1—C1	124.6 (2)	N1—C17—H17	119.4
C2—O2—C21	118.1 (2)	C11—C17—H17	119.4
O2—C21—H21A	109.5	C13—O13—C113	117.68 (19)
O2—C21—H21B	109.5	O13—C113—H11A	109.5
H21A—C21—H21B	109.5	O13—C113—H11B	109.5
O2—C21—H21C	109.5	H11A—C113—H11B	109.5
H21A—C21—H21C	109.5	O13—C113—H11C	109.5
H21B—C21—H21C	109.5	H11A—C113—H11C	109.5
C16—C11—C12	120.0 (2)	H11B—C113—H11C	109.5
C16—C11—C17	119.9 (2)

C6—C1—C2—O2	179.8 (2)	C17—C11—C12—C13	−176.8 (2)
N1—C1—C2—O2	1.0 (3)	O12—C12—C13—O13	0.7 (3)
C6—C1—C2—C3	−0.5 (4)	C11—C12—C13—O13	179.8 (2)
N1—C1—C2—C3	−179.3 (2)	O12—C12—C13—C14	−179.7 (2)
O2—C2—C3—C4	−179.9 (2)	C11—C12—C13—C14	−0.6 (3)
C1—C2—C3—C4	0.5 (4)	O13—C13—C14—C15	179.4 (2)
C2—C3—C4—C5	−0.1 (4)	C12—C13—C14—C15	−0.2 (4)
C3—C4—C5—C6	−0.3 (4)	C13—C14—C15—C16	0.3 (4)
C2—C1—C6—C5	0.1 (4)	C13—C14—C15—Br15	−179.26 (17)
N1—C1—C6—C5	178.8 (2)	C14—C15—C16—C11	0.4 (3)
C4—C5—C6—C1	0.2 (4)	Br15—C15—C16—C11	179.91 (16)
C6—C1—N1—C17	−0.6 (4)	C12—C11—C16—C15	−1.1 (3)
C2—C1—N1—C17	178.1 (2)	C17—C11—C16—C15	177.0 (2)
C3—C2—O2—C21	6.9 (4)	C1—N1—C17—C11	−179.9 (2)
C1—C2—O2—C21	−173.5 (2)	C16—C11—C17—N1	−178.6 (2)
C16—C11—C12—O12	−179.7 (2)	C12—C11—C17—N1	−0.5 (3)
C17—C11—C12—O12	2.2 (3)	C14—C13—O13—C113	9.7 (4)
C16—C11—C12—C13	1.3 (3)	C12—C13—O13—C113	−170.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12···N1	0.82	1.81	2.543 (3)	147

(E)-2-Methoxy-6-[(2-methoxyphenylimino)methyl]phenol (V) top

Crystal data top

C₁₅H₁₅NO₃	D_x = 1.276 Mg m⁻³
M_r = 257.28	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca2₁	Cell parameters from 2601 reflections
a = 23.689 (2) Å	θ = 1.7–25.9°
b = 7.6951 (7) Å	µ = 0.09 mm⁻¹
c = 7.3488 (7) Å	T = 296 K
V = 1339.6 (2) Å³	Block, orange
Z = 4	0.24 × 0.18 × 0.10 mm
F(000) = 544

Data collection top

Bruker APEXII CCD diffractometer	2600 independent reflections
Radiation source: fine focus sealed tube	1975 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
φ and ω scans	θ_max = 25.9°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −25→29
T_min = 0.859, T_max = 0.991	k = −9→9
16375 measured reflections	l = −9→9

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.037	w = 1/[σ²(F_o²) + (0.0332P)² + 0.1885P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.084	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.11 e Å⁻³
2600 reflections	Δρ_min = −0.14 e Å⁻³
175 parameters	Absolute structure: Flack x determined using 772 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.1 (5)

Special details top

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

	x	y	z	U_iso*/U_eq
C1	0.08903 (10)	0.8870 (4)	0.8423 (4)	0.0426 (6)
C2	0.05117 (11)	0.8302 (3)	0.9757 (4)	0.0440 (6)
C3	0.03195 (12)	0.9445 (4)	1.1060 (4)	0.0536 (8)
H3	0.0065	0.9072	1.1940	0.064*
C4	0.05065 (13)	1.1152 (4)	1.1057 (5)	0.0604 (8)
H4	0.0381	1.1916	1.1949	0.072*
C5	0.08757 (13)	1.1722 (4)	0.9747 (5)	0.0601 (8)
H5	0.0996	1.2872	0.9744	0.072*
C6	0.10676 (12)	1.0587 (4)	0.8435 (4)	0.0520 (7)
H6	0.1318	1.0977	0.7550	0.062*
N1	0.10993 (10)	0.7621 (3)	0.7191 (3)	0.0476 (6)
O2	0.03493 (8)	0.6604 (2)	0.9623 (3)	0.0565 (5)
C21	−0.00134 (18)	0.5945 (4)	1.0988 (5)	0.0867 (12)
H21A	0.0163	0.6069	1.2156	0.130*
H21B	−0.0088	0.4738	1.0758	0.130*
H21C	−0.0362	0.6581	1.0975	0.130*
C11	0.14629 (11)	0.6758 (4)	0.4306 (4)	0.0455 (7)
C12	0.15948 (11)	0.5091 (4)	0.4888 (4)	0.0446 (7)
O12	0.14804 (9)	0.4517 (3)	0.6586 (3)	0.0572 (6)
H12	0.1349	0.5315	0.7193	0.086*
C13	0.18589 (11)	0.3938 (4)	0.3682 (4)	0.0488 (7)
C14	0.19927 (13)	0.4473 (5)	0.1956 (4)	0.0601 (8)
H14	0.2174	0.3711	0.1166	0.072*
C15	0.18608 (14)	0.6141 (5)	0.1373 (4)	0.0675 (9)
H15	0.1953	0.6489	0.0198	0.081*
C16	0.15970 (14)	0.7267 (4)	0.2517 (4)	0.0589 (9)
H16	0.1505	0.8377	0.2117	0.071*
C17	0.12071 (12)	0.8011 (4)	0.5539 (4)	0.0494 (7)
H17	0.1120	0.9118	0.5115	0.059*
O13	0.19690 (9)	0.2318 (3)	0.4367 (3)	0.0650 (6)
C113	0.23182 (15)	0.1230 (4)	0.3301 (6)	0.0888 (12)
H11A	0.2135	0.0985	0.2165	0.133*
H11B	0.2386	0.0163	0.3941	0.133*
H11C	0.2671	0.1805	0.3073	0.133*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0371 (15)	0.0494 (16)	0.0413 (14)	0.0062 (13)	−0.0021 (14)	0.0032 (14)
C2	0.0405 (14)	0.0425 (15)	0.0489 (16)	0.0024 (12)	0.0037 (14)	0.0049 (15)
C3	0.0544 (18)	0.0513 (18)	0.0552 (19)	0.0063 (14)	0.0128 (15)	0.0003 (17)
C4	0.067 (2)	0.0498 (18)	0.064 (2)	0.0061 (16)	0.0085 (18)	−0.0072 (17)
C5	0.0624 (19)	0.0469 (17)	0.071 (2)	−0.0071 (15)	−0.0017 (19)	−0.0025 (19)
C6	0.0426 (16)	0.0571 (19)	0.0564 (18)	−0.0058 (14)	0.0026 (15)	0.0043 (17)
N1	0.0408 (14)	0.0587 (15)	0.0433 (14)	0.0015 (11)	0.0041 (11)	−0.0008 (12)
O2	0.0641 (13)	0.0466 (11)	0.0588 (12)	−0.0035 (10)	0.0163 (12)	−0.0005 (11)
C21	0.111 (3)	0.062 (2)	0.086 (3)	−0.020 (2)	0.047 (3)	0.000 (2)
C11	0.0388 (15)	0.0598 (18)	0.0379 (15)	−0.0012 (13)	−0.0005 (13)	0.0023 (15)
C12	0.0333 (14)	0.0589 (18)	0.0415 (15)	−0.0056 (12)	0.0013 (12)	−0.0016 (15)
O12	0.0651 (14)	0.0602 (12)	0.0463 (12)	0.0025 (11)	0.0135 (10)	0.0059 (10)
C13	0.0421 (15)	0.0571 (18)	0.0473 (17)	−0.0041 (14)	−0.0009 (14)	−0.0083 (15)
C14	0.0545 (19)	0.077 (2)	0.0490 (19)	−0.0030 (17)	0.0061 (15)	−0.0160 (17)
C15	0.071 (2)	0.091 (3)	0.0405 (17)	−0.0070 (19)	0.0064 (16)	−0.0023 (19)
C16	0.061 (2)	0.071 (2)	0.0448 (19)	−0.0006 (17)	−0.0027 (16)	0.0073 (17)
C17	0.0443 (17)	0.0546 (18)	0.0493 (18)	0.0048 (14)	−0.0042 (14)	0.0044 (14)
O13	0.0678 (14)	0.0600 (13)	0.0671 (14)	0.0044 (10)	0.0093 (12)	−0.0085 (12)
C113	0.094 (3)	0.074 (2)	0.098 (3)	0.011 (2)	0.010 (3)	−0.028 (2)

Geometric parameters (Å, º) top

C1—C6	1.387 (4)	C11—C16	1.408 (4)
C1—C2	1.399 (4)	C11—C17	1.455 (4)
C1—N1	1.410 (4)	C12—O12	1.351 (3)
C2—O2	1.366 (3)	C12—C13	1.401 (4)
C2—C3	1.377 (4)	O12—H12	0.8200
C3—C4	1.386 (4)	C13—O13	1.370 (3)
C3—H3	0.9300	C13—C14	1.371 (4)
C4—C5	1.373 (4)	C14—C15	1.389 (4)
C4—H4	0.9300	C14—H14	0.9300
C5—C6	1.378 (4)	C15—C16	1.359 (4)
C5—H5	0.9300	C15—H15	0.9300
C6—H6	0.9300	C16—H16	0.9300
N1—C17	1.276 (3)	C17—H17	0.9300
O2—C21	1.415 (4)	O13—C113	1.414 (4)
C21—H21A	0.9600	C113—H11A	0.9600
C21—H21B	0.9600	C113—H11B	0.9600
C21—H21C	0.9600	C113—H11C	0.9600
C11—C12	1.388 (4)

C6—C1—C2	119.1 (3)	C16—C11—C17	119.4 (3)
C6—C1—N1	123.2 (3)	O12—C12—C11	122.8 (2)
C2—C1—N1	117.6 (2)	O12—C12—C13	117.8 (3)
O2—C2—C3	124.6 (2)	C11—C12—C13	119.4 (3)
O2—C2—C1	115.4 (2)	C12—O12—H12	109.5
C3—C2—C1	120.0 (3)	O13—C13—C14	124.7 (3)
C2—C3—C4	119.9 (3)	O13—C13—C12	115.4 (3)
C2—C3—H3	120.1	C14—C13—C12	119.9 (3)
C4—C3—H3	120.1	C13—C14—C15	120.7 (3)
C5—C4—C3	120.5 (3)	C13—C14—H14	119.6
C5—C4—H4	119.8	C15—C14—H14	119.6
C3—C4—H4	119.8	C16—C15—C14	120.1 (3)
C4—C5—C6	119.9 (3)	C16—C15—H15	120.0
C4—C5—H5	120.0	C14—C15—H15	120.0
C6—C5—H5	120.0	C15—C16—C11	120.3 (3)
C5—C6—C1	120.6 (3)	C15—C16—H16	119.8
C5—C6—H6	119.7	C11—C16—H16	119.8
C1—C6—H6	119.7	N1—C17—C11	121.3 (3)
C17—N1—C1	121.4 (3)	N1—C17—H17	119.3
C2—O2—C21	117.6 (2)	C11—C17—H17	119.3
O2—C21—H21A	109.5	C13—O13—C113	116.5 (3)
O2—C21—H21B	109.5	O13—C113—H11A	109.5
H21A—C21—H21B	109.5	O13—C113—H11B	109.5
O2—C21—H21C	109.5	H11A—C113—H11B	109.5
H21A—C21—H21C	109.5	O13—C113—H11C	109.5
H21B—C21—H21C	109.5	H11A—C113—H11C	109.5
C12—C11—C16	119.6 (3)	H11B—C113—H11C	109.5
C12—C11—C17	120.9 (3)

C6—C1—C2—O2	178.6 (2)	C16—C11—C12—C13	−0.1 (4)
N1—C1—C2—O2	−5.2 (3)	C17—C11—C12—C13	−177.8 (3)
C6—C1—C2—C3	0.0 (4)	O12—C12—C13—O13	0.6 (4)
N1—C1—C2—C3	176.3 (2)	C11—C12—C13—O13	−179.5 (2)
O2—C2—C3—C4	−179.1 (3)	O12—C12—C13—C14	−178.8 (3)
C1—C2—C3—C4	−0.7 (4)	C11—C12—C13—C14	1.1 (4)
C2—C3—C4—C5	1.0 (5)	O13—C13—C14—C15	179.5 (3)
C3—C4—C5—C6	−0.7 (5)	C12—C13—C14—C15	−1.1 (4)
C4—C5—C6—C1	0.1 (5)	C13—C14—C15—C16	0.1 (5)
C2—C1—C6—C5	0.3 (4)	C14—C15—C16—C11	0.9 (5)
N1—C1—C6—C5	−175.7 (3)	C12—C11—C16—C15	−0.9 (4)
C6—C1—N1—C17	−37.9 (4)	C17—C11—C16—C15	176.8 (3)
C2—C1—N1—C17	146.0 (3)	C1—N1—C17—C11	175.2 (2)
C3—C2—O2—C21	−4.3 (4)	C12—C11—C17—N1	0.4 (4)
C1—C2—O2—C21	177.2 (3)	C16—C11—C17—N1	−177.3 (3)
C16—C11—C12—O12	179.8 (3)	C14—C13—O13—C113	9.8 (4)
C17—C11—C12—O12	2.1 (4)	C12—C13—O13—C113	−169.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12···N1	0.82	1.87	2.592 (3)	146
C3—H3···Cg1ⁱ	0.93	2.83	3.646 (3)	148
C16—H16···Cg1ⁱⁱ	0.93	2.88	3.630 (3)	138

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

(E)-3-Benzoyl-2-[(5-fluoro-2-hydroxybenzylidene)amino]-4,5,6,7-tetrahydrobenzo[b]thiophene (VI) top

Crystal data top

C₂₂H₁₈FNO₂S	F(000) = 792
M_r = 379.43	D_x = 1.372 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.5004 (8) Å	Cell parameters from 4428 reflections
b = 14.2911 (11) Å	θ = 2.1–28.0°
c = 13.6497 (9) Å	µ = 0.20 mm⁻¹
β = 97.524 (2)°	T = 296 K
V = 1837.3 (2) Å³	Block, yellow
Z = 4	0.15 × 0.14 × 0.11 mm

Data collection top

Bruker APEXII CCD diffractometer	4250 independent reflections
Radiation source: fine focus sealed tube	2556 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
φ and ω scans	θ_max = 27.6°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −12→12
T_min = 0.921, T_max = 0.978	k = −18→18
31822 measured reflections	l = −17→17

Refinement top

Refinement on F²	12 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.119	w = 1/[σ²(F_o²) + (0.0469P)² + 0.4922P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
4250 reflections	Δρ_max = 0.18 e Å⁻³
258 parameters	Δρ_min = −0.26 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.56580 (6)	0.11525 (4)	0.69220 (4)	0.04948 (18)
C2	0.6399 (2)	0.19223 (14)	0.61476 (14)	0.0389 (5)
C3	0.7107 (2)	0.14473 (14)	0.54891 (13)	0.0383 (5)
C3A	0.7046 (2)	0.04557 (14)	0.56027 (14)	0.0404 (5)	0.705 (4)
C4	0.7730 (16)	−0.0256 (2)	0.5007 (8)	0.0525 (6)	0.705 (4)
H4A	0.8640	−0.0022	0.4865	0.063*	0.705 (4)
H4B	0.7134	−0.0361	0.4384	0.063*	0.705 (4)
C5	0.7945 (4)	−0.1174 (2)	0.5571 (3)	0.0604 (10)	0.705 (4)
H5A	0.8234	−0.1654	0.5137	0.073*	0.705 (4)
H5B	0.8697	−0.1099	0.6119	0.073*	0.705 (4)
C6	0.6592 (4)	−0.1478 (2)	0.5961 (3)	0.0645 (12)	0.705 (4)
H6A	0.5860	−0.1578	0.5406	0.077*	0.705 (4)
H6B	0.6764	−0.2072	0.6300	0.077*	0.705 (4)
C7	0.6049 (9)	−0.0788 (2)	0.6661 (5)	0.0505 (16)	0.705 (4)
H7A	0.5038	−0.0879	0.6663	0.061*	0.705 (4)
H7B	0.6518	−0.0896	0.7326	0.061*	0.705 (4)
C7A	0.6322 (2)	0.01980 (14)	0.63571 (14)	0.0434 (5)	0.705 (4)
C23A	0.7046 (2)	0.04557 (14)	0.56027 (14)	0.0404 (5)	0.295 (4)
C24	0.772 (4)	−0.0272 (4)	0.502 (2)	0.0525 (6)	0.295 (4)
H24A	0.8746	−0.0251	0.5199	0.063*	0.295 (4)
H24B	0.7521	−0.0125	0.4320	0.063*	0.295 (4)
C25	0.7197 (11)	−0.1255 (4)	0.5195 (6)	0.0604 (10)	0.295 (4)
H25A	0.6239	−0.1329	0.4858	0.073*	0.295 (4)
H25B	0.7800	−0.1708	0.4923	0.073*	0.295 (4)
C26	0.7207 (11)	−0.1440 (5)	0.6290 (6)	0.0645 (12)	0.295 (4)
H26A	0.6868	−0.2071	0.6375	0.077*	0.295 (4)
H26B	0.8179	−0.1406	0.6612	0.077*	0.295 (4)
C27	0.631 (3)	−0.0766 (5)	0.6796 (13)	0.0505 (16)	0.295 (4)
H27A	0.5342	−0.0995	0.6734	0.061*	0.295 (4)
H27B	0.6671	−0.0735	0.7494	0.061*	0.295 (4)
C27A	0.6322 (2)	0.01980 (14)	0.63571 (14)	0.0434 (5)	0.295 (4)
N1	0.62359 (17)	0.28869 (11)	0.61552 (11)	0.0403 (4)
C17	0.5359 (2)	0.32940 (15)	0.66555 (14)	0.0429 (5)
H17	0.4811	0.2928	0.7023	0.051*
C11	0.5192 (2)	0.42981 (14)	0.66705 (14)	0.0393 (5)
C12	0.6008 (2)	0.48950 (15)	0.61540 (14)	0.0422 (5)
C13	0.5780 (2)	0.58533 (16)	0.61636 (16)	0.0527 (6)
H13	0.6321	0.6247	0.5819	0.063*
C14	0.4762 (2)	0.62265 (16)	0.66784 (16)	0.0527 (6)
H14	0.4603	0.6869	0.6679	0.063*
C15	0.3985 (2)	0.56345 (17)	0.71917 (15)	0.0487 (6)
F15	0.29897 (15)	0.60168 (10)	0.77035 (10)	0.0706 (4)
C16	0.4178 (2)	0.46901 (15)	0.72061 (14)	0.0453 (5)
H16	0.3643	0.4309	0.7568	0.054*
O12	0.70270 (16)	0.45725 (10)	0.56372 (12)	0.0558 (4)
H12	0.7034	0.3999	0.5651	0.084*
C37	0.7832 (2)	0.19103 (14)	0.47101 (14)	0.0391 (5)
O37	0.75072 (16)	0.16958 (11)	0.38463 (10)	0.0574 (4)
C31	0.8958 (2)	0.26031 (13)	0.50165 (13)	0.0362 (4)
C32	0.9657 (2)	0.26220 (16)	0.59733 (14)	0.0457 (5)
H32	0.9381	0.2216	0.6445	0.055*
C33	1.0760 (2)	0.32384 (17)	0.62318 (16)	0.0554 (6)
H33	1.1239	0.3236	0.6871	0.067*
C34	1.1153 (2)	0.38579 (17)	0.55424 (16)	0.0574 (6)
H34	1.1888	0.4280	0.5718	0.069*
C35	1.0452 (2)	0.38492 (16)	0.45926 (16)	0.0542 (6)
H35	1.0711	0.4271	0.4129	0.065*
C36	0.9374 (2)	0.32224 (15)	0.43251 (14)	0.0449 (5)
H36	0.8920	0.3213	0.3679	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0570 (4)	0.0474 (3)	0.0483 (3)	−0.0084 (3)	0.0229 (3)	0.0002 (3)
C2	0.0380 (11)	0.0401 (12)	0.0397 (10)	−0.0061 (9)	0.0088 (9)	−0.0001 (9)
C3	0.0353 (11)	0.0422 (12)	0.0383 (10)	−0.0055 (9)	0.0078 (9)	−0.0002 (9)
C3A	0.0389 (11)	0.0419 (12)	0.0402 (11)	−0.0039 (9)	0.0047 (9)	−0.0021 (9)
C4	0.0541 (14)	0.0469 (14)	0.0580 (14)	0.0013 (11)	0.0128 (11)	−0.0051 (12)
C5	0.059 (3)	0.0471 (18)	0.074 (3)	0.0081 (19)	0.0052 (19)	−0.0031 (17)
C6	0.073 (3)	0.0391 (16)	0.080 (3)	−0.0122 (19)	0.005 (2)	−0.0029 (18)
C7	0.049 (4)	0.0455 (14)	0.054 (2)	−0.0141 (13)	−0.002 (3)	0.0075 (12)
C7A	0.0423 (12)	0.0430 (12)	0.0450 (11)	−0.0075 (10)	0.0054 (9)	−0.0003 (10)
C23A	0.0389 (11)	0.0419 (12)	0.0402 (11)	−0.0039 (9)	0.0047 (9)	−0.0021 (9)
C24	0.0541 (14)	0.0469 (14)	0.0580 (14)	0.0013 (11)	0.0128 (11)	−0.0051 (12)
C25	0.059 (3)	0.0471 (18)	0.074 (3)	0.0081 (19)	0.0052 (19)	−0.0031 (17)
C26	0.073 (3)	0.0391 (16)	0.080 (3)	−0.0122 (19)	0.005 (2)	−0.0029 (18)
C27	0.049 (4)	0.0455 (14)	0.054 (2)	−0.0141 (13)	−0.002 (3)	0.0075 (12)
C27A	0.0423 (12)	0.0430 (12)	0.0450 (11)	−0.0075 (10)	0.0054 (9)	−0.0003 (10)
N1	0.0407 (10)	0.0383 (10)	0.0429 (9)	−0.0034 (8)	0.0095 (8)	−0.0024 (8)
C17	0.0423 (12)	0.0451 (13)	0.0429 (11)	−0.0064 (10)	0.0116 (9)	0.0011 (9)
C11	0.0366 (11)	0.0419 (12)	0.0393 (11)	−0.0010 (9)	0.0047 (9)	−0.0034 (9)
C12	0.0400 (12)	0.0452 (13)	0.0423 (11)	−0.0048 (10)	0.0090 (9)	−0.0038 (9)
C13	0.0594 (15)	0.0429 (13)	0.0574 (14)	−0.0076 (11)	0.0142 (11)	−0.0012 (11)
C14	0.0649 (15)	0.0409 (13)	0.0520 (13)	0.0055 (11)	0.0063 (11)	−0.0048 (11)
C15	0.0480 (13)	0.0572 (15)	0.0415 (12)	0.0104 (11)	0.0081 (10)	−0.0057 (11)
F15	0.0758 (10)	0.0716 (10)	0.0700 (9)	0.0245 (8)	0.0305 (8)	−0.0028 (7)
C16	0.0448 (12)	0.0506 (14)	0.0418 (11)	−0.0021 (10)	0.0104 (9)	0.0003 (10)
O12	0.0577 (10)	0.0436 (9)	0.0726 (10)	−0.0071 (8)	0.0330 (8)	−0.0034 (8)
C37	0.0400 (11)	0.0412 (12)	0.0373 (11)	−0.0007 (9)	0.0092 (9)	−0.0008 (9)
O37	0.0703 (11)	0.0638 (11)	0.0389 (8)	−0.0181 (8)	0.0104 (8)	−0.0059 (7)
C31	0.0348 (10)	0.0395 (11)	0.0360 (10)	−0.0007 (9)	0.0110 (8)	0.0011 (9)
C32	0.0413 (12)	0.0581 (14)	0.0387 (11)	−0.0066 (10)	0.0086 (9)	0.0068 (10)
C33	0.0474 (13)	0.0770 (18)	0.0414 (12)	−0.0128 (12)	0.0042 (10)	−0.0044 (11)
C34	0.0513 (14)	0.0677 (16)	0.0541 (14)	−0.0199 (12)	0.0102 (11)	−0.0077 (12)
C35	0.0574 (14)	0.0570 (15)	0.0511 (13)	−0.0158 (12)	0.0173 (11)	0.0081 (11)
C36	0.0460 (13)	0.0530 (14)	0.0368 (11)	−0.0051 (10)	0.0093 (9)	0.0036 (10)

Geometric parameters (Å, º) top

S1—C7A	1.726 (2)	C27—H27B	0.9700
S1—C2	1.7374 (19)	N1—C17	1.283 (2)
C2—C3	1.371 (3)	C17—C11	1.444 (3)
C2—N1	1.387 (2)	C17—H17	0.9300
C3—C3A	1.427 (3)	C11—C16	1.400 (3)
C3—C37	1.495 (3)	C11—C12	1.403 (3)
C3A—C7A	1.362 (3)	C12—O12	1.351 (2)
C3A—C4	1.502 (3)	C12—C13	1.387 (3)
C4—C5	1.520 (7)	C13—C14	1.375 (3)
C4—H4A	0.9700	C13—H13	0.9300
C4—H4B	0.9700	C14—C15	1.374 (3)
C5—C6	1.518 (4)	C14—H14	0.9300
C5—H5A	0.9700	C15—F15	1.361 (2)
C5—H5B	0.9700	C15—C16	1.362 (3)
C6—C7	1.510 (4)	C16—H16	0.9300
C6—H6A	0.9700	O12—H12	0.8200
C6—H6B	0.9700	C37—O37	1.218 (2)
C7—C7A	1.501 (3)	C37—C31	1.478 (3)
C7—H7A	0.9700	C31—C32	1.386 (3)
C7—H7B	0.9700	C31—C36	1.388 (3)
C24—C25	1.522 (8)	C32—C33	1.379 (3)
C24—H24A	0.9700	C32—H32	0.9300
C24—H24B	0.9700	C33—C34	1.379 (3)
C25—C26	1.516 (5)	C33—H33	0.9300
C25—H25A	0.9700	C34—C35	1.378 (3)
C25—H25B	0.9700	C34—H34	0.9300
C26—C27	1.511 (5)	C35—C36	1.374 (3)
C26—H26A	0.9700	C35—H35	0.9300
C26—H26B	0.9700	C36—H36	0.9300
C27—H27A	0.9700

C7A—S1—C2	91.59 (10)	C25—C26—H26B	108.7
C3—C2—N1	124.19 (18)	H26A—C26—H26B	107.6
C3—C2—S1	110.98 (15)	C26—C27—H27A	109.3
N1—C2—S1	124.74 (15)	C26—C27—H27B	109.3
C2—C3—C3A	112.97 (17)	H27A—C27—H27B	108.0
C2—C3—C37	123.94 (18)	C17—N1—C2	122.38 (17)
C3A—C3—C37	123.07 (17)	N1—C17—C11	122.56 (18)
C7A—C3A—C3	112.46 (18)	N1—C17—H17	118.7
C7A—C3A—C4	121.5 (2)	C11—C17—H17	118.7
C3—C3A—C4	126.0 (2)	C16—C11—C12	118.83 (19)
C3A—C4—C5	110.5 (4)	C16—C11—C17	119.30 (18)
C3A—C4—H4A	109.6	C12—C11—C17	121.86 (18)
C5—C4—H4A	109.6	O12—C12—C13	117.73 (18)
C3A—C4—H4B	109.6	O12—C12—C11	122.39 (19)
C5—C4—H4B	109.6	C13—C12—C11	119.89 (19)
H4A—C4—H4B	108.1	C14—C13—C12	120.6 (2)
C6—C5—C4	111.2 (6)	C14—C13—H13	119.7
C6—C5—H5A	109.4	C12—C13—H13	119.7
C4—C5—H5A	109.4	C15—C14—C13	118.9 (2)
C6—C5—H5B	109.4	C15—C14—H14	120.6
C4—C5—H5B	109.4	C13—C14—H14	120.6
H5A—C5—H5B	108.0	F15—C15—C16	119.5 (2)
C7—C6—C5	114.2 (4)	F15—C15—C14	118.1 (2)
C7—C6—H6A	108.7	C16—C15—C14	122.5 (2)
C5—C6—H6A	108.7	C15—C16—C11	119.3 (2)
C7—C6—H6B	108.7	C15—C16—H16	120.3
C5—C6—H6B	108.7	C11—C16—H16	120.3
H6A—C6—H6B	107.6	C12—O12—H12	109.5
C7A—C7—C6	110.7 (2)	O37—C37—C31	121.64 (17)
C7A—C7—H7A	109.5	O37—C37—C3	119.70 (18)
C6—C7—H7A	109.5	C31—C37—C3	118.64 (16)
C7A—C7—H7B	109.5	C32—C31—C36	118.96 (18)
C6—C7—H7B	109.5	C32—C31—C37	121.32 (17)
H7A—C7—H7B	108.1	C36—C31—C37	119.65 (17)
C3A—C7A—C7	125.8 (2)	C33—C32—C31	120.53 (19)
C3A—C7A—S1	111.98 (16)	C33—C32—H32	119.7
C7—C7A—S1	122.14 (18)	C31—C32—H32	119.7
C25—C24—H24A	109.1	C34—C33—C32	120.0 (2)
C25—C24—H24B	109.1	C34—C33—H33	120.0
H24A—C24—H24B	107.8	C32—C33—H33	120.0
C26—C25—C24	110.9 (9)	C35—C34—C33	119.7 (2)
C26—C25—H25A	109.5	C35—C34—H34	120.1
C24—C25—H25A	109.5	C33—C34—H34	120.1
C26—C25—H25B	109.5	C36—C35—C34	120.5 (2)
C24—C25—H25B	109.5	C36—C35—H35	119.7
H25A—C25—H25B	108.1	C34—C35—H35	119.7
C27—C26—C25	114.1 (7)	C35—C36—C31	120.23 (19)
C27—C26—H26A	108.7	C35—C36—H36	119.9
C25—C26—H26A	108.7	C31—C36—H36	119.9
C27—C26—H26B	108.7

C7A—S1—C2—C3	0.46 (16)	C16—C11—C12—O12	178.61 (19)
C7A—S1—C2—N1	177.20 (18)	C17—C11—C12—O12	−2.1 (3)
N1—C2—C3—C3A	−176.38 (18)	C16—C11—C12—C13	−1.4 (3)
S1—C2—C3—C3A	0.4 (2)	C17—C11—C12—C13	177.94 (19)
N1—C2—C3—C37	1.8 (3)	O12—C12—C13—C14	−179.8 (2)
S1—C2—C3—C37	178.58 (15)	C11—C12—C13—C14	0.2 (3)
C2—C3—C3A—C7A	−1.3 (3)	C12—C13—C14—C15	0.7 (3)
C37—C3—C3A—C7A	−179.54 (18)	C13—C14—C15—F15	179.48 (19)
C2—C3—C3A—C4	−179.0 (8)	C13—C14—C15—C16	−0.4 (3)
C37—C3—C3A—C4	2.7 (9)	F15—C15—C16—C11	179.33 (17)
C7A—C3A—C4—C5	−19.9 (14)	C14—C15—C16—C11	−0.8 (3)
C3—C3A—C4—C5	157.6 (5)	C12—C11—C16—C15	1.7 (3)
C3A—C4—C5—C6	49.4 (12)	C17—C11—C16—C15	−177.66 (19)
C4—C5—C6—C7	−59.9 (8)	C2—C3—C37—O37	−123.6 (2)
C5—C6—C7—C7A	35.4 (7)	C3A—C3—C37—O37	54.4 (3)
C3—C3A—C7A—C7	179.1 (5)	C2—C3—C37—C31	58.0 (3)
C4—C3A—C7A—C7	−3.0 (9)	C3A—C3—C37—C31	−124.0 (2)
C3—C3A—C7A—S1	1.6 (2)	O37—C37—C31—C32	−157.9 (2)
C4—C3A—C7A—S1	179.5 (8)	C3—C37—C31—C32	20.5 (3)
C6—C7—C7A—C3A	−4.5 (8)	O37—C37—C31—C36	19.2 (3)
C6—C7—C7A—S1	172.8 (3)	C3—C37—C31—C36	−162.43 (18)
C2—S1—C7A—C3A	−1.22 (16)	C36—C31—C32—C33	−0.8 (3)
C2—S1—C7A—C7	−178.8 (4)	C37—C31—C32—C33	176.3 (2)
C24—C25—C26—C27	58.5 (15)	C31—C32—C33—C34	1.6 (3)
C3—C2—N1—C17	166.97 (19)	C32—C33—C34—C35	−0.9 (4)
S1—C2—N1—C17	−9.3 (3)	C33—C34—C35—C36	−0.6 (4)
C2—N1—C17—C11	179.60 (18)	C34—C35—C36—C31	1.4 (3)
N1—C17—C11—C16	177.76 (19)	C32—C31—C36—C35	−0.7 (3)
N1—C17—C11—C12	−1.6 (3)	C37—C31—C36—C35	−177.83 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12···N1	0.82	1.93	2.647 (2)	146
C16—H16···O37ⁱ	0.93	2.60	3.519 (3)	170

Symmetry code: (i) x−1/2, −y+1/2, z+1/2.

(E)-3-Benzoyl-2-[(2-hydroxybenzylidene)amino)]-4,5,6,7-tetrahydrobenzo[b]thiophene (VII) top

Crystal data top

C₂₂H₁₉NO₂S	F(000) = 760
M_r = 361.44	D_x = 1.338 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
a = 9.26395 (15) Å	Cell parameters from 5377 reflections
b = 14.2886 (2) Å	θ = 4.5–71.3°
c = 13.6476 (2) Å	µ = 1.73 mm⁻¹
β = 96.7581 (15)°	T = 173 K
V = 1793.97 (5) Å³	Block, yellow
Z = 4	0.24 × 0.14 × 0.08 mm

Data collection top

Agilent Eos Gemini diffractometer	3115 reflections with I > 2σ(I)
Radiation source: Enhance (Cu) X-ray Source	R_int = 0.053
ω scans	θ_max = 71.5°, θ_min = 4.5°
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	h = −11→10
T_min = 0.529, T_max = 0.871	k = −17→17
11619 measured reflections	l = −16→14
3464 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.042	w = 1/[σ²(F_o²) + (0.0767P)² + 0.2663P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.120	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 0.33 e Å⁻³
3464 reflections	Δρ_min = −0.23 e Å⁻³
250 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
12 restraints	Extinction coefficient: 0.0025 (3)

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.55852 (4)	0.11521 (3)	0.69559 (3)	0.02965 (15)
C2	0.63345 (15)	0.19433 (10)	0.61848 (11)	0.0254 (3)
C3	0.70610 (15)	0.14810 (10)	0.55080 (11)	0.0251 (3)
C3A	0.70094 (15)	0.04847 (10)	0.56033 (11)	0.0258 (3)	0.851 (3)
C4	0.7727 (7)	−0.02081 (13)	0.4986 (4)	0.0312 (4)	0.851 (3)
H4A	0.8668	0.0046	0.4832	0.037*	0.851 (3)
H4B	0.7102	−0.0314	0.4356	0.037*	0.851 (3)
C5	0.7976 (2)	−0.11332 (13)	0.55391 (16)	0.0363 (5)	0.851 (3)
H5A	0.8288	−0.1615	0.5086	0.044*	0.851 (3)
H5B	0.8766	−0.1054	0.6088	0.044*	0.851 (3)
C6	0.6602 (3)	−0.14642 (13)	0.59497 (19)	0.0395 (5)	0.851 (3)
H6A	0.5823	−0.1553	0.5396	0.047*	0.851 (3)
H6B	0.6795	−0.2078	0.6275	0.047*	0.851 (3)
C7	0.6075 (5)	−0.07816 (14)	0.6689 (3)	0.0329 (8)	0.851 (3)
H7A	0.5035	−0.0897	0.6745	0.039*	0.851 (3)
H7B	0.6629	−0.0882	0.7346	0.039*	0.851 (3)
C7A	0.62763 (16)	0.02109 (10)	0.63626 (11)	0.0276 (3)	0.851 (3)
C23A	0.70094 (15)	0.04847 (10)	0.56033 (11)	0.0258 (3)	0.149 (3)
C24	0.768 (4)	−0.0232 (5)	0.498 (2)	0.0312 (4)	0.149 (3)
H24A	0.8754	−0.0207	0.5137	0.037*	0.149 (3)
H24B	0.7437	−0.0075	0.4278	0.037*	0.149 (3)
C25	0.7162 (14)	−0.1225 (5)	0.5165 (7)	0.0363 (5)	0.149 (3)
H25A	0.6157	−0.1304	0.4837	0.044*	0.149 (3)
H25B	0.7791	−0.1679	0.4868	0.044*	0.149 (3)
C26	0.7193 (15)	−0.1433 (6)	0.6260 (7)	0.0395 (5)	0.149 (3)
H26A	0.8208	−0.1392	0.6578	0.047*	0.149 (3)
H26B	0.6851	−0.2081	0.6343	0.047*	0.149 (3)
C27	0.625 (4)	−0.0763 (6)	0.6780 (18)	0.0329 (8)	0.149 (3)
H27A	0.5237	−0.0996	0.6708	0.039*	0.149 (3)
H27B	0.6606	−0.0746	0.7493	0.039*	0.149 (3)
C27A	0.62763 (16)	0.02109 (10)	0.63626 (11)	0.0276 (3)	0.149 (3)
N1	0.61670 (13)	0.29061 (9)	0.62116 (9)	0.0263 (3)
C17	0.52975 (16)	0.33089 (11)	0.67516 (11)	0.0275 (3)
H17	0.4753	0.2934	0.7151	0.033*
C11	0.51262 (15)	0.43149 (11)	0.67676 (11)	0.0264 (3)
C12	0.59258 (16)	0.49131 (11)	0.62112 (11)	0.0284 (3)
C13	0.56826 (19)	0.58760 (12)	0.62206 (13)	0.0359 (4)
H13	0.6216	0.6279	0.5843	0.043*
C14	0.46701 (19)	0.62449 (11)	0.67769 (13)	0.0367 (4)
H14	0.4501	0.6901	0.6771	0.044*
C15	0.38928 (18)	0.56681 (12)	0.73469 (12)	0.0360 (4)
H15	0.3209	0.5930	0.7736	0.043*
C16	0.41197 (17)	0.47130 (11)	0.73444 (12)	0.0311 (3)
H16	0.3591	0.4320	0.7736	0.037*
O12	0.69347 (13)	0.45874 (8)	0.56601 (9)	0.0367 (3)
H12	0.6982	0.4002	0.5708	0.055*
C37	0.77923 (15)	0.19624 (10)	0.47298 (11)	0.0246 (3)
O37	0.74685 (12)	0.17582 (8)	0.38636 (8)	0.0338 (3)
C31	0.89546 (15)	0.26512 (10)	0.50409 (11)	0.0248 (3)
C32	0.96622 (16)	0.26563 (11)	0.59988 (11)	0.0294 (3)
H32	0.9356	0.2243	0.6479	0.035*
C33	1.08136 (17)	0.32642 (13)	0.62539 (12)	0.0348 (4)
H33	1.1308	0.3258	0.6904	0.042*
C34	1.12419 (18)	0.38811 (12)	0.55594 (13)	0.0373 (4)
H34	1.2026	0.4300	0.5735	0.045*
C35	1.05239 (19)	0.38872 (12)	0.46057 (13)	0.0366 (4)
H35	1.0811	0.4316	0.4133	0.044*
C36	0.93955 (17)	0.32723 (12)	0.43432 (11)	0.0307 (3)
H36	0.8918	0.3271	0.3688	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0350 (2)	0.0249 (2)	0.0313 (2)	−0.00451 (13)	0.01304 (16)	−0.00084 (13)
C2	0.0258 (7)	0.0232 (7)	0.0275 (7)	−0.0037 (5)	0.0053 (5)	0.0001 (5)
C3	0.0226 (7)	0.0240 (7)	0.0286 (7)	−0.0023 (5)	0.0027 (5)	−0.0013 (5)
C3A	0.0232 (7)	0.0230 (7)	0.0307 (7)	−0.0017 (5)	0.0017 (5)	−0.0017 (6)
C4	0.0311 (9)	0.0264 (8)	0.0366 (8)	0.0017 (6)	0.0065 (7)	−0.0043 (6)
C5	0.0358 (11)	0.0272 (10)	0.0447 (12)	0.0074 (8)	0.0003 (8)	−0.0042 (8)
C6	0.0437 (13)	0.0222 (8)	0.0516 (14)	−0.0040 (8)	0.0019 (10)	−0.0019 (8)
C7	0.0344 (17)	0.0248 (8)	0.0390 (12)	−0.0067 (7)	0.0025 (13)	0.0036 (7)
C7A	0.0277 (7)	0.0216 (7)	0.0334 (8)	−0.0019 (5)	0.0036 (6)	−0.0019 (6)
C23A	0.0232 (7)	0.0230 (7)	0.0307 (7)	−0.0017 (5)	0.0017 (5)	−0.0017 (6)
C24	0.0311 (9)	0.0264 (8)	0.0366 (8)	0.0017 (6)	0.0065 (7)	−0.0043 (6)
C25	0.0358 (11)	0.0272 (10)	0.0447 (12)	0.0074 (8)	0.0003 (8)	−0.0042 (8)
C26	0.0437 (13)	0.0222 (8)	0.0516 (14)	−0.0040 (8)	0.0019 (10)	−0.0019 (8)
C27	0.0344 (17)	0.0248 (8)	0.0390 (12)	−0.0067 (7)	0.0025 (13)	0.0036 (7)
C27A	0.0277 (7)	0.0216 (7)	0.0334 (8)	−0.0019 (5)	0.0036 (6)	−0.0019 (6)
N1	0.0271 (6)	0.0222 (6)	0.0303 (6)	−0.0026 (5)	0.0057 (5)	−0.0011 (5)
C17	0.0269 (7)	0.0253 (7)	0.0309 (7)	−0.0031 (6)	0.0064 (6)	−0.0007 (6)
C11	0.0246 (7)	0.0248 (7)	0.0293 (7)	−0.0011 (6)	0.0010 (5)	−0.0034 (6)
C12	0.0284 (7)	0.0259 (7)	0.0306 (7)	−0.0031 (6)	0.0026 (6)	−0.0033 (6)
C13	0.0437 (9)	0.0258 (8)	0.0384 (9)	−0.0043 (7)	0.0049 (7)	0.0007 (6)
C14	0.0439 (9)	0.0244 (8)	0.0402 (9)	0.0046 (6)	−0.0017 (7)	−0.0047 (6)
C15	0.0353 (8)	0.0345 (8)	0.0382 (8)	0.0079 (7)	0.0039 (7)	−0.0075 (7)
C16	0.0301 (7)	0.0312 (8)	0.0324 (8)	−0.0008 (6)	0.0051 (6)	−0.0031 (6)
O12	0.0411 (6)	0.0260 (6)	0.0468 (7)	−0.0045 (5)	0.0205 (5)	−0.0018 (5)
C37	0.0238 (7)	0.0239 (7)	0.0266 (7)	0.0024 (5)	0.0047 (5)	0.0005 (5)
O37	0.0393 (6)	0.0361 (6)	0.0264 (6)	−0.0064 (5)	0.0048 (4)	−0.0033 (4)
C31	0.0235 (6)	0.0252 (7)	0.0265 (7)	0.0006 (5)	0.0069 (5)	−0.0001 (5)
C32	0.0284 (7)	0.0348 (8)	0.0256 (7)	−0.0014 (6)	0.0062 (6)	0.0027 (6)
C33	0.0299 (8)	0.0468 (10)	0.0273 (8)	−0.0047 (7)	0.0019 (6)	−0.0027 (7)
C34	0.0321 (8)	0.0432 (10)	0.0372 (9)	−0.0129 (7)	0.0066 (7)	−0.0057 (7)
C35	0.0393 (9)	0.0397 (9)	0.0320 (8)	−0.0113 (7)	0.0093 (7)	0.0042 (6)
C36	0.0325 (8)	0.0358 (8)	0.0239 (7)	−0.0047 (6)	0.0041 (6)	0.0036 (6)

Geometric parameters (Å, º) top

S1—C7A	1.7310 (15)	C27—H27B	0.9900
S1—C2	1.7433 (14)	N1—C17	1.290 (2)
C2—C3	1.374 (2)	C17—C11	1.447 (2)
C2—N1	1.3853 (19)	C17—H17	0.9500
C3—C3A	1.431 (2)	C11—C16	1.409 (2)
C3—C37	1.493 (2)	C11—C12	1.410 (2)
C3A—C7A	1.361 (2)	C12—O12	1.3496 (19)
C3A—C4	1.505 (2)	C12—C13	1.395 (2)
C4—C5	1.527 (4)	C13—C14	1.379 (2)
C4—H4A	0.9900	C13—H13	0.9500
C4—H4B	0.9900	C14—C15	1.391 (3)
C5—C6	1.525 (3)	C14—H14	0.9500
C5—H5A	0.9900	C15—C16	1.381 (2)
C5—H5B	0.9900	C15—H15	0.9500
C6—C7	1.524 (3)	C16—H16	0.9500
C6—H6A	0.9900	O12—H12	0.8400
C6—H6B	0.9900	C37—O37	1.2203 (18)
C7—C7A	1.504 (2)	C37—C31	1.484 (2)
C7—H7A	0.9900	C31—C32	1.392 (2)
C7—H7B	0.9900	C31—C36	1.397 (2)
C24—C25	1.528 (7)	C32—C33	1.388 (2)
C24—H24A	0.9900	C32—H32	0.9500
C24—H24B	0.9900	C33—C34	1.386 (2)
C25—C26	1.521 (5)	C33—H33	0.9500
C25—H25A	0.9900	C34—C35	1.390 (2)
C25—H25B	0.9900	C34—H34	0.9500
C26—C27	1.525 (6)	C35—C36	1.380 (2)
C26—H26A	0.9900	C35—H35	0.9500
C26—H26B	0.9900	C36—H36	0.9500
C27—H27A	0.9900

C7A—S1—C2	91.49 (7)	C27—C26—H26B	109.0
C3—C2—N1	124.07 (13)	H26A—C26—H26B	107.8
C3—C2—S1	110.81 (11)	C26—C27—H27A	109.3
N1—C2—S1	125.04 (11)	C26—C27—H27B	109.3
C2—C3—C3A	113.13 (13)	H27A—C27—H27B	108.0
C2—C3—C37	123.76 (13)	C17—N1—C2	122.53 (13)
C3A—C3—C37	123.08 (13)	N1—C17—C11	121.95 (13)
C7A—C3A—C3	112.34 (13)	N1—C17—H17	119.0
C7A—C3A—C4	122.01 (14)	C11—C17—H17	119.0
C3—C3A—C4	125.59 (14)	C16—C11—C12	118.70 (14)
C3A—C4—C5	110.1 (2)	C16—C11—C17	119.38 (14)
C3A—C4—H4A	109.6	C12—C11—C17	121.92 (13)
C5—C4—H4A	109.6	O12—C12—C13	117.94 (14)
C3A—C4—H4B	109.6	O12—C12—C11	122.23 (14)
C5—C4—H4B	109.6	C13—C12—C11	119.83 (14)
H4A—C4—H4B	108.2	C14—C13—C12	120.22 (16)
C6—C5—C4	111.5 (3)	C14—C13—H13	119.9
C6—C5—H5A	109.3	C12—C13—H13	119.9
C4—C5—H5A	109.3	C13—C14—C15	120.79 (15)
C6—C5—H5B	109.3	C13—C14—H14	119.6
C4—C5—H5B	109.3	C15—C14—H14	119.6
H5A—C5—H5B	108.0	C16—C15—C14	119.68 (15)
C7—C6—C5	113.0 (2)	C16—C15—H15	120.2
C7—C6—H6A	109.0	C14—C15—H15	120.2
C5—C6—H6A	109.0	C15—C16—C11	120.75 (15)
C7—C6—H6B	109.0	C15—C16—H16	119.6
C5—C6—H6B	109.0	C11—C16—H16	119.6
H6A—C6—H6B	107.8	C12—O12—H12	109.5
C7A—C7—C6	110.32 (16)	O37—C37—C31	121.55 (13)
C7A—C7—H7A	109.6	O37—C37—C3	119.91 (13)
C6—C7—H7A	109.6	C31—C37—C3	118.48 (12)
C7A—C7—H7B	109.6	C32—C31—C36	119.58 (14)
C6—C7—H7B	109.6	C32—C31—C37	121.20 (13)
H7A—C7—H7B	108.1	C36—C31—C37	119.13 (13)
C3A—C7A—C7	125.88 (15)	C33—C32—C31	120.13 (14)
C3A—C7A—S1	112.20 (11)	C33—C32—H32	119.9
C7—C7A—S1	121.92 (13)	C31—C32—H32	119.9
C25—C24—H24A	109.1	C34—C33—C32	120.00 (15)
C25—C24—H24B	109.1	C34—C33—H33	120.0
H24A—C24—H24B	107.9	C32—C33—H33	120.0
C26—C25—C24	111.7 (9)	C33—C34—C35	120.02 (15)
C26—C25—H25A	109.3	C33—C34—H34	120.0
C24—C25—H25A	109.3	C35—C34—H34	120.0
C26—C25—H25B	109.3	C36—C35—C34	120.22 (15)
C24—C25—H25B	109.3	C36—C35—H35	119.9
H25A—C25—H25B	107.9	C34—C35—H35	119.9
C25—C26—C27	112.9 (8)	C35—C36—C31	120.04 (14)
C25—C26—H26A	109.0	C35—C36—H36	120.0
C27—C26—H26A	109.0	C31—C36—H36	120.0
C25—C26—H26B	109.0

C7A—S1—C2—C3	0.53 (11)	N1—C17—C11—C12	−1.5 (2)
C7A—S1—C2—N1	177.55 (13)	C16—C11—C12—O12	178.33 (14)
N1—C2—C3—C3A	−176.67 (13)	C17—C11—C12—O12	−2.5 (2)
S1—C2—C3—C3A	0.39 (15)	C16—C11—C12—C13	−1.6 (2)
N1—C2—C3—C37	1.5 (2)	C17—C11—C12—C13	177.53 (14)
S1—C2—C3—C37	178.55 (11)	O12—C12—C13—C14	−179.58 (15)
C2—C3—C3A—C7A	−1.43 (17)	C11—C12—C13—C14	0.4 (2)
C37—C3—C3A—C7A	−179.61 (13)	C12—C13—C14—C15	1.0 (3)
C2—C3—C3A—C4	−178.6 (4)	C13—C14—C15—C16	−1.0 (3)
C37—C3—C3A—C4	3.2 (4)	C14—C15—C16—C11	−0.3 (2)
C7A—C3A—C4—C5	−20.2 (6)	C12—C11—C16—C15	1.6 (2)
C3—C3A—C4—C5	156.8 (2)	C17—C11—C16—C15	−177.61 (14)
C3A—C4—C5—C6	49.3 (5)	C2—C3—C37—O37	−124.18 (16)
C4—C5—C6—C7	−61.3 (4)	C3A—C3—C37—O37	53.80 (19)
C5—C6—C7—C7A	38.6 (4)	C2—C3—C37—C31	58.68 (19)
C3—C3A—C7A—C7	−177.4 (3)	C3A—C3—C37—C31	−123.34 (15)
C4—C3A—C7A—C7	−0.1 (5)	O37—C37—C31—C32	−157.83 (14)
C3—C3A—C7A—S1	1.82 (16)	C3—C37—C31—C32	19.3 (2)
C4—C3A—C7A—S1	179.1 (4)	O37—C37—C31—C36	18.8 (2)
C6—C7—C7A—C3A	−9.0 (5)	C3—C37—C31—C36	−164.15 (13)
C6—C7—C7A—S1	171.9 (2)	C36—C31—C32—C33	−1.0 (2)
C2—S1—C7A—C3A	−1.36 (12)	C37—C31—C32—C33	175.53 (14)
C2—S1—C7A—C7	177.9 (3)	C31—C32—C33—C34	1.3 (3)
C24—C25—C26—C27	58.9 (17)	C32—C33—C34—C35	−0.4 (3)
C3—C2—N1—C17	169.02 (14)	C33—C34—C35—C36	−0.8 (3)
S1—C2—N1—C17	−7.6 (2)	C34—C35—C36—C31	1.1 (3)
C2—N1—C17—C11	−179.59 (13)	C32—C31—C36—C35	−0.1 (2)
N1—C17—C11—C16	177.66 (14)	C37—C31—C36—C35	−176.79 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12···N1	0.84	1.90	2.6400 (17)	146
C16—H16···O37ⁱ	0.95	2.49	3.4357 (19)	174

Symmetry code: (i) x−1/2, −y+1/2, z+1/2.

(E)-[(2-Hydroxyphenylimino)methyl]phenol (VIII) top

Crystal data top

C₁₃H₁₁NO₂	Z = 4
M_r = 213.23	F(000) = 448
Triclinic, P1	D_x = 1.369 Mg m⁻³
a = 9.0479 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.1564 (8) Å	Cell parameters from 4751 reflections
c = 12.3659 (10) Å	θ = 1.8–27.5°
α = 69.677 (6)°	µ = 0.09 mm⁻¹
β = 89.940 (6)°	T = 293 K
γ = 77.004 (6)°	Block, yellow
V = 1034.62 (15) Å³	0.48 × 0.38 × 0.22 mm

Data collection top

Stoe IPDS II CCD diffractometer	4751 independent reflections
Radiation source: fine focus sealed tube	3487 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ω and 2θ scans	θ_max = 27.5°, θ_min = 1.8°
Absorption correction: multi-scan (X-RED; Stoe & Cie, 2002)	h = −11→11
T_min = 0.912, T_max = 0.980	k = −13→13
13249 measured reflections	l = −16→16

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.109	w = 1/[σ²(F_o²) + (0.050P)² + 0.0679P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
4751 reflections	Δρ_max = 0.18 e Å⁻³
291 parameters	Δρ_min = −0.15 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
C1	0.92308 (14)	0.34762 (14)	0.06265 (10)	0.0399 (3)
C2	1.01087 (15)	0.31376 (14)	0.16580 (10)	0.0412 (3)
C3	1.14018 (15)	0.20072 (15)	0.19535 (12)	0.0474 (3)
H3	1.1987	0.1765	0.2643	0.057*
C4	1.18218 (17)	0.12439 (17)	0.12316 (13)	0.0555 (4)
H4	1.2691	0.0489	0.1435	0.067*
C5	1.09625 (18)	0.15913 (19)	0.02095 (14)	0.0634 (4)
H5	1.1257	0.1076	−0.0278	0.076*
C6	0.96670 (17)	0.27004 (17)	−0.00922 (12)	0.0540 (4)
H6	0.9085	0.2928	−0.0780	0.065*
N1	0.79121 (12)	0.46273 (11)	0.03740 (9)	0.0402 (2)
H1	0.7652	0.4951	0.0921	0.048*
O2	0.96512 (12)	0.39546 (12)	0.23130 (9)	0.0589 (3)
H2	1.0320	0.3769	0.2827	0.088*
C11	0.57558 (14)	0.63938 (13)	−0.07642 (10)	0.0400 (3)
C12	0.53017 (15)	0.69214 (14)	0.01471 (11)	0.0440 (3)
O12	0.60181 (11)	0.63258 (11)	0.11722 (8)	0.0526 (2)
C13	0.40299 (19)	0.81114 (17)	−0.01265 (14)	0.0613 (4)
H13	0.3711	0.8505	0.0434	0.074*
C14	0.3257 (2)	0.86974 (18)	−0.11988 (14)	0.0636 (4)
H14	0.2427	0.9485	−0.1351	0.076*
C15	0.36759 (17)	0.81482 (16)	−0.20666 (12)	0.0538 (3)
H15	0.3118	0.8546	−0.2784	0.065*
C16	0.49144 (16)	0.70209 (15)	−0.18540 (11)	0.0469 (3)
H16	0.5211	0.6658	−0.2436	0.056*
C17	0.70537 (14)	0.52471 (14)	−0.05897 (10)	0.0409 (3)
H17	0.7306	0.4920	−0.1197	0.049*
C21	0.34279 (14)	0.64514 (14)	0.44373 (10)	0.0392 (3)
C22	0.41444 (14)	0.67838 (14)	0.34054 (10)	0.0411 (3)
C23	0.48403 (16)	0.79342 (15)	0.31012 (12)	0.0483 (3)
H23	0.5315	0.8173	0.2416	0.058*
C24	0.48302 (19)	0.87163 (18)	0.38061 (14)	0.0598 (4)
H24	0.5295	0.9488	0.3593	0.072*
C25	0.4139 (2)	0.8376 (2)	0.48294 (15)	0.0688 (5)
H25	0.4149	0.8908	0.5307	0.083*
C26	0.34351 (18)	0.72453 (17)	0.51422 (12)	0.0554 (4)
H26	0.2964	0.7017	0.5830	0.066*
N21	0.27014 (11)	0.52960 (11)	0.46926 (8)	0.0392 (2)
H21	0.2624	0.4960	0.4151	0.047*
O22	0.41281 (13)	0.59542 (11)	0.27619 (9)	0.0586 (3)
H22	0.4723	0.6127	0.2260	0.088*
C31	0.14221 (14)	0.35391 (14)	0.58288 (10)	0.0395 (3)
C32	0.12577 (15)	0.29890 (14)	0.49314 (11)	0.0433 (3)
O32	0.16995 (12)	0.35677 (11)	0.39094 (8)	0.0525 (2)
C33	0.05751 (19)	0.18025 (17)	0.52079 (14)	0.0585 (4)
H33	0.0473	0.1393	0.4655	0.070*
C34	0.00618 (19)	0.12459 (17)	0.62719 (14)	0.0596 (4)
H34	−0.0384	0.0466	0.6425	0.072*
C35	0.01871 (17)	0.18111 (16)	0.71306 (12)	0.0531 (3)
H35	−0.0189	0.1428	0.7843	0.064*
C36	0.08676 (16)	0.29333 (15)	0.69180 (11)	0.0465 (3)
H36	0.0969	0.3306	0.7495	0.056*
C37	0.21374 (14)	0.46853 (14)	0.56551 (10)	0.0409 (3)
H37	0.2210	0.5021	0.6259	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0399 (6)	0.0475 (7)	0.0364 (6)	−0.0135 (5)	0.0087 (5)	−0.0180 (5)
C2	0.0464 (7)	0.0470 (7)	0.0361 (6)	−0.0174 (5)	0.0080 (5)	−0.0182 (5)
C3	0.0477 (8)	0.0515 (8)	0.0417 (7)	−0.0131 (6)	0.0007 (6)	−0.0141 (6)
C4	0.0503 (8)	0.0558 (9)	0.0563 (8)	−0.0019 (6)	0.0056 (6)	−0.0219 (7)
C5	0.0651 (10)	0.0730 (10)	0.0559 (9)	0.0025 (8)	0.0054 (7)	−0.0395 (8)
C6	0.0536 (8)	0.0684 (9)	0.0438 (7)	−0.0042 (7)	0.0010 (6)	−0.0311 (7)
N1	0.0432 (6)	0.0490 (6)	0.0346 (5)	−0.0123 (5)	0.0086 (4)	−0.0214 (5)
O2	0.0667 (7)	0.0685 (7)	0.0471 (5)	−0.0031 (5)	−0.0068 (5)	−0.0356 (5)
C11	0.0426 (7)	0.0431 (7)	0.0372 (6)	−0.0154 (5)	0.0103 (5)	−0.0147 (5)
C12	0.0493 (7)	0.0472 (7)	0.0392 (6)	−0.0146 (6)	0.0119 (5)	−0.0180 (6)
O12	0.0583 (6)	0.0632 (6)	0.0380 (5)	−0.0079 (5)	0.0093 (4)	−0.0243 (4)
C13	0.0701 (10)	0.0594 (9)	0.0530 (8)	−0.0009 (7)	0.0126 (7)	−0.0276 (7)
C14	0.0662 (10)	0.0531 (9)	0.0587 (9)	0.0042 (7)	0.0072 (7)	−0.0158 (7)
C15	0.0575 (9)	0.0523 (8)	0.0420 (7)	−0.0086 (6)	0.0025 (6)	−0.0081 (6)
C16	0.0521 (8)	0.0508 (8)	0.0379 (6)	−0.0144 (6)	0.0083 (5)	−0.0148 (6)
C17	0.0449 (7)	0.0492 (7)	0.0349 (6)	−0.0156 (5)	0.0098 (5)	−0.0198 (5)
C21	0.0375 (6)	0.0476 (7)	0.0348 (6)	−0.0104 (5)	0.0021 (5)	−0.0173 (5)
C22	0.0399 (7)	0.0464 (7)	0.0358 (6)	−0.0058 (5)	0.0024 (5)	−0.0159 (5)
C23	0.0481 (8)	0.0527 (8)	0.0416 (7)	−0.0143 (6)	0.0071 (6)	−0.0126 (6)
C24	0.0713 (10)	0.0608 (9)	0.0561 (8)	−0.0333 (8)	0.0070 (7)	−0.0207 (7)
C25	0.0978 (13)	0.0792 (11)	0.0567 (9)	−0.0480 (10)	0.0172 (9)	−0.0408 (9)
C26	0.0688 (9)	0.0704 (10)	0.0435 (7)	−0.0324 (8)	0.0150 (6)	−0.0310 (7)
N21	0.0415 (6)	0.0480 (6)	0.0334 (5)	−0.0122 (4)	0.0040 (4)	−0.0201 (4)
O22	0.0799 (7)	0.0630 (6)	0.0486 (6)	−0.0277 (5)	0.0273 (5)	−0.0325 (5)
C31	0.0379 (6)	0.0441 (7)	0.0351 (6)	−0.0069 (5)	−0.0003 (5)	−0.0141 (5)
C32	0.0443 (7)	0.0481 (7)	0.0383 (6)	−0.0085 (5)	−0.0008 (5)	−0.0179 (6)
O32	0.0656 (6)	0.0643 (6)	0.0381 (5)	−0.0234 (5)	0.0069 (4)	−0.0262 (4)
C33	0.0747 (10)	0.0577 (9)	0.0548 (8)	−0.0244 (7)	0.0037 (7)	−0.0290 (7)
C34	0.0698 (10)	0.0506 (9)	0.0591 (9)	−0.0251 (7)	0.0026 (7)	−0.0138 (7)
C35	0.0580 (9)	0.0531 (8)	0.0426 (7)	−0.0161 (7)	0.0050 (6)	−0.0086 (6)
C36	0.0509 (8)	0.0517 (8)	0.0364 (6)	−0.0121 (6)	0.0025 (5)	−0.0150 (6)
C37	0.0419 (7)	0.0505 (7)	0.0333 (6)	−0.0095 (5)	0.0023 (5)	−0.0194 (5)

Geometric parameters (Å, º) top

C1—C6	1.3828 (18)	C21—C26	1.3786 (18)
C1—C2	1.3967 (17)	C21—C22	1.4001 (17)
C1—N1	1.4169 (17)	C21—N21	1.4135 (16)
C2—O2	1.3518 (15)	C22—O22	1.3471 (15)
C2—C3	1.3878 (19)	C22—C23	1.3886 (19)
C3—C4	1.375 (2)	C23—C24	1.367 (2)
C3—H3	0.9300	C23—H23	0.9300
C4—C5	1.377 (2)	C24—C25	1.380 (2)
C4—H4	0.9300	C24—H24	0.9300
C5—C6	1.377 (2)	C25—C26	1.376 (2)
C5—H5	0.9300	C25—H25	0.9300
C6—H6	0.9300	C26—H26	0.9300
N1—C17	1.2963 (17)	N21—C37	1.3000 (16)
N1—H1	0.8600	N21—H21	0.8600
O2—H2	0.8200	O22—H22	0.8200
C11—C16	1.4104 (18)	C31—C37	1.4089 (18)
C11—C17	1.4117 (18)	C31—C36	1.4163 (17)
C11—C12	1.4302 (17)	C31—C32	1.4263 (17)
C12—O12	1.2983 (16)	C32—O32	1.3004 (15)
C12—C13	1.411 (2)	C32—C33	1.414 (2)
C13—C14	1.367 (2)	C33—C34	1.366 (2)
C13—H13	0.9300	C33—H33	0.9300
C14—C15	1.388 (2)	C34—C35	1.387 (2)
C14—H14	0.9300	C34—H34	0.9300
C15—C16	1.360 (2)	C35—C36	1.362 (2)
C15—H15	0.9300	C35—H35	0.9300
C16—H16	0.9300	C36—H36	0.9300
C17—H17	0.9300	C37—H37	0.9300

C6—C1—C2	119.93 (12)	C26—C21—C22	120.25 (12)
C6—C1—N1	123.23 (12)	C26—C21—N21	123.08 (11)
C2—C1—N1	116.84 (11)	C22—C21—N21	116.66 (11)
O2—C2—C3	123.39 (12)	O22—C22—C23	123.44 (11)
O2—C2—C1	117.45 (12)	O22—C22—C21	117.71 (11)
C3—C2—C1	119.15 (12)	C23—C22—C21	118.84 (12)
C4—C3—C2	120.32 (13)	C24—C23—C22	120.21 (13)
C4—C3—H3	119.8	C24—C23—H23	119.9
C2—C3—H3	119.8	C22—C23—H23	119.9
C3—C4—C5	120.35 (14)	C23—C24—C25	120.83 (13)
C3—C4—H4	119.8	C23—C24—H24	119.6
C5—C4—H4	119.8	C25—C24—H24	119.6
C4—C5—C6	120.13 (14)	C26—C25—C24	119.82 (14)
C4—C5—H5	119.9	C26—C25—H25	120.1
C6—C5—H5	119.9	C24—C25—H25	120.1
C5—C6—C1	120.11 (13)	C25—C26—C21	120.04 (13)
C5—C6—H6	119.9	C25—C26—H26	120.0
C1—C6—H6	119.9	C21—C26—H26	120.0
C17—N1—C1	127.23 (11)	C37—N21—C21	127.21 (11)
C17—N1—H1	116.4	C37—N21—H21	116.4
C1—N1—H1	116.4	C21—N21—H21	116.4
C2—O2—H2	109.5	C22—O22—H22	109.5
C16—C11—C17	119.09 (11)	C37—C31—C36	118.75 (11)
C16—C11—C12	120.28 (12)	C37—C31—C32	121.04 (11)
C17—C11—C12	120.63 (12)	C36—C31—C32	120.21 (12)
O12—C12—C13	122.04 (12)	O32—C32—C33	122.12 (12)
O12—C12—C11	121.54 (12)	O32—C32—C31	121.29 (11)
C13—C12—C11	116.41 (13)	C33—C32—C31	116.58 (12)
C14—C13—C12	121.38 (14)	C34—C33—C32	121.30 (14)
C14—C13—H13	119.3	C34—C33—H33	119.3
C12—C13—H13	119.3	C32—C33—H33	119.3
C13—C14—C15	121.79 (15)	C33—C34—C35	121.83 (14)
C13—C14—H14	119.1	C33—C34—H34	119.1
C15—C14—H14	119.1	C35—C34—H34	119.1
C16—C15—C14	119.09 (14)	C36—C35—C34	119.23 (13)
C16—C15—H15	120.5	C36—C35—H35	120.4
C14—C15—H15	120.5	C34—C35—H35	120.4
C15—C16—C11	121.00 (13)	C35—C36—C31	120.81 (13)
C15—C16—H16	119.5	C35—C36—H36	119.6
C11—C16—H16	119.5	C31—C36—H36	119.6
N1—C17—C11	123.32 (12)	N21—C37—C31	123.22 (12)
N1—C17—H17	118.3	N21—C37—H37	118.4
C11—C17—H17	118.3	C31—C37—H37	118.4

C6—C1—C2—O2	178.34 (12)	C26—C21—C22—O22	178.70 (13)
N1—C1—C2—O2	−1.58 (17)	N21—C21—C22—O22	−2.11 (18)
C6—C1—C2—C3	−0.88 (19)	C26—C21—C22—C23	−0.8 (2)
N1—C1—C2—C3	179.20 (11)	N21—C21—C22—C23	178.35 (12)
O2—C2—C3—C4	−178.34 (13)	O22—C22—C23—C24	−179.05 (14)
C1—C2—C3—C4	0.83 (19)	C21—C22—C23—C24	0.5 (2)
C2—C3—C4—C5	−0.1 (2)	C22—C23—C24—C25	0.3 (2)
C3—C4—C5—C6	−0.5 (3)	C23—C24—C25—C26	−0.7 (3)
C4—C5—C6—C1	0.5 (3)	C24—C25—C26—C21	0.3 (3)
C2—C1—C6—C5	0.2 (2)	C22—C21—C26—C25	0.4 (2)
N1—C1—C6—C5	−179.85 (14)	N21—C21—C26—C25	−178.70 (15)
C6—C1—N1—C17	−9.8 (2)	C26—C21—N21—C37	−10.1 (2)
C2—C1—N1—C17	170.08 (12)	C22—C21—N21—C37	170.70 (12)
C16—C11—C12—O12	177.13 (12)	C37—C31—C32—O32	−3.1 (2)
C17—C11—C12—O12	−3.24 (19)	C36—C31—C32—O32	177.05 (13)
C16—C11—C12—C13	−2.34 (18)	C37—C31—C32—C33	177.69 (13)
C17—C11—C12—C13	177.28 (13)	C36—C31—C32—C33	−2.14 (19)
O12—C12—C13—C14	−177.83 (15)	O32—C32—C33—C34	−177.31 (15)
C11—C12—C13—C14	1.6 (2)	C31—C32—C33—C34	1.9 (2)
C12—C13—C14—C15	0.4 (3)	C32—C33—C34—C35	−0.2 (3)
C13—C14—C15—C16	−1.8 (2)	C33—C34—C35—C36	−1.3 (2)
C14—C15—C16—C11	1.0 (2)	C34—C35—C36—C31	1.0 (2)
C17—C11—C16—C15	−178.57 (13)	C37—C31—C36—C35	−179.09 (13)
C12—C11—C16—C15	1.06 (19)	C32—C31—C36—C35	0.7 (2)
C1—N1—C17—C11	−179.94 (11)	C21—N21—C37—C31	179.61 (12)
C16—C11—C17—N1	178.50 (12)	C36—C31—C37—N21	178.97 (12)
C12—C11—C17—N1	−1.13 (19)	C32—C31—C37—N21	−0.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.29	2.6605 (15)	106
N1—H1···O12	0.86	1.90	2.5955 (16)	137
N21—H21···O22	0.86	2.29	2.6620 (15)	106
N21—H21···O32	0.86	1.90	2.5960 (16)	137
O22—H22···O12	0.82	1.77	2.5882 (15)	174
O2—H2···O32ⁱ	0.82	1.76	2.5744 (15)	174

Symmetry code: (i) x+1, y, z.

Selected bond lengths (Å) top

Parameter	(I)	(II)	(III)	(IV)	(V)	(VI)	(VII)	(VIII), molecule 1	(VIII), molecule 2
C11—C12	1.405 (5)	1.405 (4)	1.421 (4)	1.404 (3)	1.388 (4)	1.403 (3)	1.410 (2)	1.4302 (17)	1.4263 (17)
C12—C13	1.381 (5)	1.414 (4)	1.431 (4)	1.413 (3)	1.401 (4)	1.387 (3)	1.395 (2)	1.411 (2)	1.414 (2)
C13—C14	1.368 (6)	1.368 (4)	1.368 (4)	1.372 (3)	1.371 (4)	1.375 (3)	1.379 (2)	1.367 (2)	1.366 (2)
C14—C15	1.386 (6)	1.400 (4)	1.402 (4)	1.385 (3)	1.389 (4)	1.374 (3)	1.391 (3)	1.388 (2)	1.387 (2)
C15—C16	1.369 (6)	1.358 (4)	1.343 (4)	1.360 (3)	1.359 (4)	1.362 (3)	1.381 (2)	1.360 (2)	1.362 (2)
C16—C11	1.386 (5)	1.408 (4)	1.428 (4)	1.403 (3)	1.408 (4)	1.400 (3)	1.409 (2)	1.4104 (18)	1.4163 (17)
C11—C17	1.437 (5)	1.437 (5)	1.410 (4)	1.439 (3)	1.455 (4)	1.444 (3)	1.447 (2)	1.4117 (18)	1.4089 (18)
C17—N1	1.273 (4)	1.292 (4)	1.297 (4)	1.277 (3)	1.276 (3)	1.283 (2)	1.290 (2)	1.2963 (17)	1.3000 (16)
C12—O12	1.347 (4)	1.326 (3)	1.287 (3)	1.379 (3)	1.351 (3)	1.351 (2)	1.3496 (19)	1.2983 (16)	1.3004 (15)

For molecule 2 in compound (VIII), the atom numbering corresponds to that shown in Fig. 8(b).

Ring-puckering parameters (Å, °) for compounds (VI) and (VII) top

	Q	θ	φ
(VI), major	0.474 (6)	53.1 (7)	133.6 (9)
(VI), minor	0.476 (13)	121.8 (19)	316 (2)
(VII), major	0.478 (3)	50.3 (4)	137.9 (5)
(VII), minor	0.477 (14)	121 (2)	320 (3)

For the major-disorder components, the ring-puckering angles are calculated for the atom sequence C3A–C4–C5–C6–C7–C7A. For the minor-disorder components, the ring-puckering angles are calculated for the atom sequence C23A–C24–C25–C26–C27–C27A.

Hydrogen bonds and short intramolecular contacts (Å, °) for compounds (I)–(VIII) top

Compound	D—H···A	D—H	H···A	D···A	D—H···A
(I)	N4—H4···N42ⁱ	0.87 (4)	2.07 (4)	2.931 (4)	168 (3)
	O12—H12···N1	0.82	1.88	2.606 (4)	147
(II)	N4—H4···O12ⁱⁱ	0.77 (4)	2.20 (4)	2.937 (3)	159 (4)
	N4—H4···O12ⁱⁱ	0.77 (4)	2.37 (4)	2.904 (3)	127 (4)
	O12—H12···N1	0.82	1.83	2.558 (3)	147
	C17—H17···O1ⁱⁱⁱ	0.93	2.37	3.285 (3)	169
(III)	N1—H1···O2	0.86	2.17	2.588 (3)	109
	N1—H1···O12	0.86	1.85	2.558 (3)	139
	O2—H2···O12ⁱⁱ	0.82	1.86	2.626 (3)	151
	C3—H3···O13ⁱⁱ	0.93	2.44	3.350 (4)	166
	C4—H4···Cg1^iv	0.93	2.90	3.731 (3)	149
(IV)	O12—H12···N1	0.82	1.81	2.543 (3)	147
(V)	O12—H12···N1	0.82	1.87	2.592 (3)	146
	C3—H3···Cg1^v	0.93	2.83	3.646 (3)	148
	C16—H16···Cg1^vi	0.93	2.88	3.630 (3)	139
(VI)	O12—H12···N1	0.82	1.93	2.647 (2)	146
	C16—H16···O37^vii	0.93	2.60	3.519 (3)	170
(VII)	O12—H12···N1	0.84	1.90	2.6400 (17)	146
	C16—H16···O37^vii	0.95	2.49	3.4357 (19)	174
(VIII)	N1—H1···O2	0.86	2.29	2.6605 (15)	106
	N1—H1···O12	0.86	1.90	2.5955 (16)	137
	N21—H21···O22	0.86	2.29	2.6620 (15)	106
	N21—H21···O32	0.86	1.90	2.5960 (16)	137
	O22—H22···O12	0.82	1.77	2.5882 (16)	174
	O2—H2···O32^viii	0.82	1.76	2.5744 (15)	174

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

Cg1 represents the centroid of the C1–C6 ring.

Format		BIBTeX
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Format		BIBTeX
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Eight Schiff bases derived from various salicyl­aldehydes: phenol–imine and keto–amine forms, conformational disorder, and supra­molecular assembly in one and two dimensions

Supporting information

Eight Schiff bases derived from various salicylaldehydes: phenol–imine and keto–amine forms, conformational disorder, and supramolecular assembly in one and two dimensions