(Z)-N-(2,6-Di­methyl­phen­yl)-1-[(2-meth­oxy­phen­yl)amino]­methanimine oxide methanol monosolvate

Juma, D.O.; Zamisa, S.J.; Munzeiwa, W.; Omondi, B.

doi:10.1107/S2414314624009891

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 9| Part 10| October 2024| x240989

https://doi.org/10.1107/S2414314624009891

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(Z)-N-(2,6-Dimethylphenyl)-1-[(2-methoxyphenyl)amino]methanimine oxide methanol monosolvate

David O. Juma,^a Sizwe J. Zamisa,^a ^* Wisdom Munzeiwa ^b and Bernard Omondi ^a

^aSchool of Chemistry and Physics, University of KwaZulu Natal, Private Bag X54001, Westville, Durban, 4000, South Africa, and ^bChemistry Department, Bindura University of Science Education, Private Bag 1020, Bindura, Zimbabwe
^*Correspondence e-mail: zamisas@ukzn.ac.za

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 4 October 2024; accepted 9 October 2024; online 21 October 2024)

In the title solvate, C₁₆H₁₈N₂O₂·CH₄O, the dihedral angles between the formamidine backbone and the pendant 2-methoxyphenyl and 2,6-dimethylphenyl groups are 14.84 (11) and 81.61 (12)°, respectively. In the crystal, the components are linked by C—H⋯O, O—H⋯O and C—H⋯ π hydrogen bonds, generating a supramolecular chain that extends along the crystallographic a-axis direction.

Keywords: Zwitterion; unsymmetrical hydroxyformamidine; crystal structure.

CCDC reference: 2389686

Structure description

The title compound is categorized in the class of formamidines (Cibian et al., 2011 , Zamisa et al., 2021 ). The formamidine backbone features two nitrogen atoms that provide bidentate coordination sites, making them effective ligands in coordination chemistry (Oshovsky & Pinchuk, 2000 ). These metal complexes have demonstrated biological activities such as antioxidant (Oladipo et al., 2020 ) and antibacterial, and significant catalytic activities in the microwave-assisted Suzuki–Miyaura cross-coupling of aryl bromides (Khormi et al., 2019 ) and ring-opening polymerization reactions (Akpan et al., 2016 ). As part of our studies in this area, we synthesized the title compound, C₁₆H₁₈N₂O₂·CH₄O, (I), and determined its crystal structure.

The asymmetric unit of (I) consists of one substituted formamidine molecule and one methanol solvent molecule as illustrated in Fig. 1. The molecular structure reveals a non-coplanar arrangement between the formamidine backbone and its pendant phenyl rings with a dihedral angle of 14.84 (11)° between the plane of the C3/C4/C11–C14 2-methoxyphenyl group and the C6/N1/N2/O1 formamidine backbone. In contrast, the dihedral angle between the C7–C10/C15/C17 2,6-dimethylphenyl group and the backbone is 81.61 (12)°. The aromatic rings are nearly orthogonal, exhibiting a dihedral angle of 89.25 (5)°.

Figure 1
The molecular structure of (I) showing displacement ellipsoid at the 50% probability level.

In the extended structure of (I), C6—H6⋯O3 and O3—H3⋯O2 hydrogen bonds (Table 1) occur as depicted in Fig. 2. The former interaction involves the solvent O atom as acceptor. The latter hydrogen bond involves the methanol OH group as donor and the formamidine O atom as acceptor. Finally, a C—H⋯π interaction exists between the a methyl H atom of the solvent molecule and the centre of gravity of the dimethylphenyl ring (π_DMP). Together, these generate a one-dimensional supramolecular structure that extends along the crystallographic a-axis direction as shown in Fig. 2.

Table 1
Experimental details

Crystal data
Chemical formula	C₁₆H₁₈N₂O₂·CH₄O
M_r	302.36
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	7.3519 (5), 28.4173 (19), 7.8982 (5)
β (°)	94.481 (2)
V (Å³)	1645.06 (19)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.28 × 0.23 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9891, 3421, 2988
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.635

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.095, 1.04
No. of reflections	3421
No. of parameters	204
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.19
Computer programs: APEX2 and SAINT (Bruker, 2016 ), SHELXL2018/3 (Sheldrick, 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

Figure 2
Representation of hydrogen bonds (dotted lines) in the crystal packing of (I).

Synthesis and crystallization

The title compound was synthesized following the literature procedure (Munzeiwa et al., 2018 ). The crude solid was then recrystallized from methanol solution to produce colourless blocks of (I) suitable for X-ray diffraction.

Refinement

Crystallographic data and structure refinement details are summarized in Table 2.

Table 2
Hydrogen-bond geometry (Å, °)

π is the centroid of the C7–C10/C15/C17 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O3ⁱ	0.95	2.20	3.1134 (14)	160
O3—H3⋯O2ⁱⁱ	0.84	1.85	2.6887 (12)	173
C1—H1C⋯πⁱ	0.98	2.66	3.5182 (16)	148
Symmetry codes: (i) ; (ii) .

Structural data

CCDC reference: 2389686

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314624009891/hb4489sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314624009891/hb4489Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314624009891/hb4489Isup3.cml

checkCIF report

Computing details top

(Z)-N-(2,6-Dimethylphenyl)-1-[(2-methoxyphenyl)amino]methanimine oxide methanol monosolvate top

Crystal data top

C₁₆H₁₈N₂O₂·CH₄O	F(000) = 648
M_r = 302.36	D_x = 1.221 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.3519 (5) Å	Cell parameters from 5449 reflections
b = 28.4173 (19) Å	θ = 2.9–26.8°
c = 7.8982 (5) Å	µ = 0.08 mm⁻¹
β = 94.481 (2)°	T = 296 K
V = 1645.06 (19) Å³	Block, colourless
Z = 4	0.28 × 0.23 × 0.14 mm

Data collection top

Bruker APEXII CCD diffractometer	R_int = 0.016
Graphite monochromator	θ_max = 26.8°, θ_min = 2.7°
φ and ω scans	h = −5→9
9891 measured reflections	k = −35→29
3421 independent reflections	l = −10→7
2988 reflections with I > 2σ(I)

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.095	w = 1/[σ²(F_o²) + (0.0379P)² + 0.7025P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3421 reflections	Δρ_max = 0.24 e Å⁻³
204 parameters	Δρ_min = −0.19 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
O1	0.95025 (12)	0.23202 (3)	0.86095 (11)	0.0234 (2)
O2	0.68659 (11)	0.13040 (3)	0.54807 (11)	0.0253 (2)
N1	0.99859 (13)	0.15522 (4)	0.69356 (13)	0.0196 (2)
H1	0.891940	0.165508	0.721129	0.023*
N2	0.83888 (13)	0.11068 (3)	0.49709 (12)	0.0172 (2)
C2	0.9131 (2)	0.27445 (5)	0.9498 (2)	0.0360 (4)
H2A	0.929940	0.268838	1.072488	0.054*
H2B	0.787040	0.284311	0.919371	0.054*
H2C	0.996864	0.299228	0.918477	0.054*
C3	1.12632 (17)	0.21578 (4)	0.87530 (15)	0.0204 (3)
C4	1.15367 (16)	0.17426 (4)	0.78411 (14)	0.0183 (2)
C6	0.99662 (16)	0.12294 (4)	0.56934 (15)	0.0177 (2)
H6	1.106504	0.109551	0.535504	0.021*
C7	0.82105 (15)	0.07864 (4)	0.35527 (15)	0.0190 (3)
C8	0.77144 (16)	0.03222 (5)	0.38559 (18)	0.0252 (3)
C9	0.74859 (19)	0.00278 (5)	0.2439 (2)	0.0362 (4)
H9	0.714657	−0.029146	0.258361	0.043*
C10	0.7747 (2)	0.01942 (6)	0.0827 (2)	0.0407 (4)
H10	0.759648	−0.001348	−0.011605	0.049*
C11	1.27136 (19)	0.23666 (5)	0.96940 (17)	0.0273 (3)
H11	1.253247	0.264546	1.032260	0.033*
C12	1.44422 (19)	0.21639 (5)	0.97109 (17)	0.0299 (3)
H12	1.543994	0.230569	1.035715	0.036*
C13	1.47188 (17)	0.17590 (5)	0.87973 (16)	0.0265 (3)
H13	1.590666	0.162711	0.880300	0.032*
C14	1.32620 (17)	0.15440 (5)	0.78691 (15)	0.0214 (3)
H14	1.344791	0.126243	0.725748	0.026*
C15	0.84516 (16)	0.09678 (5)	0.19363 (16)	0.0241 (3)
C16	0.89151 (19)	0.14775 (5)	0.16957 (17)	0.0309 (3)
H16A	0.884152	0.155090	0.047995	0.046*
H16B	1.015574	0.153864	0.219298	0.046*
H16C	0.805035	0.167507	0.225731	0.046*
C17	0.82203 (19)	0.06565 (6)	0.05721 (18)	0.0347 (3)
H17	0.839093	0.076404	−0.054328	0.042*
C18	0.7448 (2)	0.01537 (5)	0.5626 (2)	0.0330 (3)
H18A	0.695056	−0.016641	0.557656	0.050*
H18B	0.659657	0.036362	0.615160	0.050*
H18C	0.862325	0.015410	0.630341	0.050*
O3	0.63925 (12)	−0.10123 (3)	0.59154 (11)	0.0256 (2)
H3	0.533296	−0.108674	0.553427	0.038*
C1	0.64434 (18)	−0.09642 (5)	0.76969 (17)	0.0300 (3)
H1A	0.765090	−0.085163	0.813127	0.045*
H1B	0.620195	−0.126986	0.820810	0.045*
H1C	0.551275	−0.073758	0.798853	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0260 (5)	0.0184 (5)	0.0257 (5)	0.0002 (4)	0.0019 (4)	−0.0049 (4)
O2	0.0162 (4)	0.0293 (5)	0.0304 (5)	0.0031 (4)	0.0026 (4)	−0.0106 (4)
N1	0.0170 (5)	0.0210 (5)	0.0205 (5)	−0.0002 (4)	0.0003 (4)	−0.0037 (4)
N2	0.0166 (5)	0.0168 (5)	0.0185 (5)	0.0007 (4)	0.0021 (4)	−0.0021 (4)
C2	0.0344 (8)	0.0243 (7)	0.0503 (9)	−0.0006 (6)	0.0086 (7)	−0.0147 (7)
C3	0.0235 (6)	0.0200 (6)	0.0180 (6)	−0.0033 (5)	0.0027 (5)	0.0017 (5)
C4	0.0216 (6)	0.0189 (6)	0.0144 (5)	−0.0040 (5)	0.0008 (4)	0.0021 (4)
C6	0.0183 (5)	0.0165 (6)	0.0185 (6)	−0.0002 (5)	0.0019 (4)	0.0003 (4)
C7	0.0127 (5)	0.0213 (6)	0.0229 (6)	0.0011 (4)	−0.0001 (4)	−0.0066 (5)
C8	0.0168 (6)	0.0213 (6)	0.0369 (7)	0.0019 (5)	−0.0015 (5)	−0.0044 (5)
C9	0.0250 (7)	0.0239 (7)	0.0588 (10)	0.0003 (6)	−0.0032 (6)	−0.0180 (7)
C10	0.0286 (7)	0.0509 (10)	0.0420 (9)	0.0018 (7)	−0.0005 (6)	−0.0304 (8)
C11	0.0319 (7)	0.0255 (7)	0.0246 (7)	−0.0082 (6)	0.0031 (5)	−0.0062 (5)
C12	0.0258 (7)	0.0395 (8)	0.0238 (7)	−0.0119 (6)	−0.0026 (5)	−0.0037 (6)
C13	0.0208 (6)	0.0369 (8)	0.0215 (6)	−0.0015 (5)	−0.0001 (5)	0.0021 (5)
C14	0.0231 (6)	0.0235 (6)	0.0173 (6)	−0.0001 (5)	0.0007 (5)	0.0010 (5)
C15	0.0148 (6)	0.0353 (7)	0.0220 (6)	−0.0001 (5)	0.0007 (5)	−0.0051 (5)
C16	0.0290 (7)	0.0396 (8)	0.0241 (7)	−0.0030 (6)	0.0024 (5)	0.0067 (6)
C17	0.0240 (7)	0.0541 (10)	0.0262 (7)	−0.0006 (6)	0.0030 (5)	−0.0156 (7)
C18	0.0295 (7)	0.0216 (7)	0.0472 (9)	−0.0033 (6)	−0.0022 (6)	0.0078 (6)
O3	0.0190 (4)	0.0304 (5)	0.0278 (5)	−0.0047 (4)	0.0041 (4)	−0.0061 (4)
C1	0.0239 (6)	0.0385 (8)	0.0273 (7)	−0.0006 (6)	0.0001 (5)	0.0000 (6)

Geometric parameters (Å, º) top

O1—C2	1.4323 (15)	C10—C17	1.378 (2)
O1—C3	1.3706 (15)	C11—H11	0.9500
O2—N2	1.3417 (13)	C11—C12	1.394 (2)
N1—H1	0.8800	C12—H12	0.9500
N1—C4	1.4061 (15)	C12—C13	1.382 (2)
N1—C6	1.3423 (15)	C13—H13	0.9500
N2—C6	1.2995 (15)	C13—C14	1.3911 (18)
N2—C7	1.4415 (15)	C14—H14	0.9500
C2—H2A	0.9800	C15—C16	1.503 (2)
C2—H2B	0.9800	C15—C17	1.3943 (19)
C2—H2C	0.9800	C16—H16A	0.9800
C3—C4	1.4049 (17)	C16—H16B	0.9800
C3—C11	1.3847 (18)	C16—H16C	0.9800
C4—C14	1.3870 (17)	C17—H17	0.9500
C6—H6	0.9500	C18—H18A	0.9800
C7—C8	1.3941 (18)	C18—H18B	0.9800
C7—C15	1.4008 (17)	C18—H18C	0.9800
C8—C9	1.397 (2)	O3—H3	0.8400
C8—C18	1.505 (2)	O3—C1	1.4113 (16)
C9—H9	0.9500	C1—H1A	0.9800
C9—C10	1.386 (2)	C1—H1B	0.9800
C10—H10	0.9500	C1—H1C	0.9800

C3—O1—C2	117.25 (10)	C12—C11—H11	120.3
C4—N1—H1	116.7	C11—C12—H12	119.7
C6—N1—H1	116.7	C13—C12—C11	120.68 (12)
C6—N1—C4	126.64 (10)	C13—C12—H12	119.7
O2—N2—C7	118.01 (9)	C12—C13—H13	119.9
C6—N2—O2	119.55 (10)	C12—C13—C14	120.15 (12)
C6—N2—C7	122.31 (10)	C14—C13—H13	119.9
O1—C2—H2A	109.5	C4—C14—C13	119.68 (12)
O1—C2—H2B	109.5	C4—C14—H14	120.2
O1—C2—H2C	109.5	C13—C14—H14	120.2
H2A—C2—H2B	109.5	C7—C15—C16	121.06 (11)
H2A—C2—H2C	109.5	C17—C15—C7	117.02 (13)
H2B—C2—H2C	109.5	C17—C15—C16	121.92 (13)
O1—C3—C4	114.35 (10)	C15—C16—H16A	109.5
O1—C3—C11	125.65 (11)	C15—C16—H16B	109.5
C11—C3—C4	120.00 (12)	C15—C16—H16C	109.5
C3—C4—N1	116.18 (11)	H16A—C16—H16B	109.5
C14—C4—N1	123.75 (11)	H16A—C16—H16C	109.5
C14—C4—C3	120.07 (11)	H16B—C16—H16C	109.5
N1—C6—H6	121.2	C10—C17—C15	120.59 (14)
N2—C6—N1	117.55 (11)	C10—C17—H17	119.7
N2—C6—H6	121.2	C15—C17—H17	119.7
C8—C7—N2	118.24 (11)	C8—C18—H18A	109.5
C8—C7—C15	123.93 (12)	C8—C18—H18B	109.5
C15—C7—N2	117.74 (11)	C8—C18—H18C	109.5
C7—C8—C9	116.49 (13)	H18A—C18—H18B	109.5
C7—C8—C18	121.02 (12)	H18A—C18—H18C	109.5
C9—C8—C18	122.49 (13)	H18B—C18—H18C	109.5
C8—C9—H9	119.5	C1—O3—H3	109.5
C10—C9—C8	121.00 (14)	O3—C1—H1A	109.5
C10—C9—H9	119.5	O3—C1—H1B	109.5
C9—C10—H10	119.5	O3—C1—H1C	109.5
C17—C10—C9	120.96 (13)	H1A—C1—H1B	109.5
C17—C10—H10	119.5	H1A—C1—H1C	109.5
C3—C11—H11	120.3	H1B—C1—H1C	109.5
C3—C11—C12	119.41 (12)

O1—C3—C4—N1	−0.57 (15)	C6—N1—C4—C14	−16.25 (19)
O1—C3—C4—C14	179.46 (10)	C6—N2—C7—C8	102.55 (13)
O1—C3—C11—C12	−179.40 (12)	C6—N2—C7—C15	−80.82 (14)
O2—N2—C6—N1	0.11 (16)	C7—N2—C6—N1	175.94 (10)
O2—N2—C7—C8	−81.55 (14)	C7—C8—C9—C10	0.08 (19)
O2—N2—C7—C15	95.08 (13)	C7—C15—C17—C10	1.02 (19)
N1—C4—C14—C13	179.74 (11)	C8—C7—C15—C16	177.54 (12)
N2—C7—C8—C9	177.55 (11)	C8—C7—C15—C17	−1.69 (18)
N2—C7—C8—C18	−2.53 (17)	C8—C9—C10—C17	−0.7 (2)
N2—C7—C15—C16	1.12 (17)	C9—C10—C17—C15	0.1 (2)
N2—C7—C15—C17	−178.12 (11)	C11—C3—C4—N1	179.35 (11)
C2—O1—C3—C4	−179.56 (11)	C11—C3—C4—C14	−0.62 (18)
C2—O1—C3—C11	0.52 (18)	C11—C12—C13—C14	−1.1 (2)
C3—C4—C14—C13	−0.30 (18)	C12—C13—C14—C4	1.14 (19)
C3—C11—C12—C13	0.2 (2)	C15—C7—C8—C9	1.15 (18)
C4—N1—C6—N2	−178.00 (11)	C15—C7—C8—C18	−178.94 (12)
C4—C3—C11—C12	0.69 (19)	C16—C15—C17—C10	−178.21 (13)
C6—N1—C4—C3	163.79 (11)	C18—C8—C9—C10	−179.84 (13)

Hydrogen-bond geometry (Å, º) top

π is the centroid of the C7–C10/C15/C17 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O3ⁱ	0.95	2.20	3.1134 (14)	160
O3—H3···O2ⁱⁱ	0.84	1.85	2.6887 (12)	173
C1—H1C···πⁱ	0.98	2.66	3.5182 (16)	148

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

Acknowledgements

The authors thank the University of KwaZulu Natal for the research facilities.

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