2-[(5-Chloro­pyridin-2-yl­imino)­meth­yl]phenol

Mamallan, K.; Gomathi, S.; Soundararajan, K.; Sethuraman, V.

doi:10.1107/S2414314620000115

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 5| Part 1| January 2020| x200011

https://doi.org/10.1107/S2414314620000115

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2-[(5-Chloropyridin-2-ylimino)methyl]phenol

Krishnasamy Mamallan,^a Sundaramoorthy Gomathi,^a Krishnan Soundararajan ^a and Velusamy Sethuraman ^a ^*

^aDepartment of Chemistry, Periyar Maniammai Institute of Science & Technology, Thanjavur 613 403, Tamil Nadu, India
^*Correspondence e-mail: lvsethu13@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 3 December 2019; accepted 6 January 2020; online 31 January 2020)

In the title compound, C₁₂H₉ClN₂O, the dihedral angle between the aromatic rings is 1.78 (4)° and an intramolecular O—H⋯N hydrogen bond closes an S(6) ring. In the crystal, C—H⋯O and C—H⋯N hydrogen bonds connect the molecules into [001] chains.

Keywords: crystal structure; hydrogen bonds.

CCDC reference: 1975774

Structure description

The dihedral angle between the N1/C2–C6 pyridine ring and C7–C12 benzene ring is 1.78 (4)° and an intramolecular O—H⋯N hydrogen bond closes an S(6) ring. The disposition of the aromatic rings is trans as indicated by the C2—N2—C13—C7 torsion angle of −179.7 (2)° (Fig. 1). In the crystal, centrosymmetric dimers linked by pairs of weak C6—H6⋯N1 hydrogen bonds (Table 1) generate R₂²(6) loops. These dimers are linked by two pairs of C3—H3⋯O1 hydrogen bonds to form R₆⁶(42) loops (Fig. 2). These alternating loops lead to wave-like supramolecular strands propagating along [001]. Intermolecular Cl⋯Cl [3.476 (4)] and Cl⋯π [3.528 (4) Å] contacts slightly shorter than van der Waals separations are also observed (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H8⋯N2	0.89 (5)	1.89 (5)	2.627 (4)	140 (4)
C3—H3⋯O1ⁱ	0.93	2.50	3.361 (5)	154
C6—H6⋯N1ⁱⁱ	0.93	2.59	3.365 (5)	141
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z.

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. The O—H⋯N hydrogen bond is indicated by a dashed line.

Figure 2
Supramolecular strands formed by weak C—H⋯N and C—H⋯O hydrogen bonds. Symmetry codes: (i) 1 − x, 1 − y, −z; (ii) $[{1\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z.

Figure 3
Left: Supramolecular chain arising from Cl⋯Cl and C—Cl⋯π contacts. [Symmetry code: (iii) $[{3\over 2}]$ − x,- $[{1\over 2}]$ + y,1/2 − z; (iv) x,-1 + y, z]. Right: Honeycomb architecture formed by the weak non-covalent interactions.

For the pharmaceutical behavior of Schiff bases, see: Mounika et al. (2010 ); Miri et al. (2013 ); Aboul-Fadl et al. (2003 ); Wei et al. (2006 ). For ring-opening reactions of pyrroles, see: Mannaert et al. (1997 ); . For halogen–halogen reactions, see: Pedireddi et al. (1994 ) and for halogen⋯π reactions, see: Rahman et al. (2003 ).

Synthesis and crystallization

2-Amino-5-chloropyridine (1 mmol) and 2-hydroxy benzaldehyde (1.2 mmol) were mixed in 20 ml of absolute ethanol with the addition of few drops of piperidine as catalyst. The mixture was refluxed for 5 h at 60–70°C. Colourless blocks of the title compound were obtained from the mother solution on cooling.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₉ClN₂O
M_r	232.66
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	14.753 (12), 4.639 (3), 16.379 (16)
β (°)	105.35 (4)
V (Å³)	1081.0 (16)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.33
Crystal size (mm)	0.14 × 0.12 × 0.09

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.955, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	22920, 3033, 1878
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.695

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.071, 0.219, 1.12
No. of reflections	3033
No. of parameters	154
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.38
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), Mercury (Macrae et al., 2008 ), POV-RAY (Cason, 2004 ), PLATON (Spek, 2020 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1975774

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314620000115/hb4333sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620000115/hb4333Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314620000115/hb4333Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2020), Mercury (Macrae et al., 2008) and POV-RAY (Cason, 2004); software used to prepare material for publication: PLATON (Spek, 2020) and publCIF (Westrip, 2010).

2-[(5-Chloropyridin-2-ylimino)methyl]phenol top

Crystal data top

C₁₂H₉ClN₂O	F(000) = 480
M_r = 232.66	D_x = 1.430 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71076 Å
Hall symbol: -P 2yn	Cell parameters from 3033 reflections
a = 14.753 (12) Å	θ = 2.9–29.6°
b = 4.639 (3) Å	µ = 0.33 mm⁻¹
c = 16.379 (16) Å	T = 294 K
β = 105.35 (4)°	Block, colourless
V = 1081.0 (16) Å³	0.14 × 0.12 × 0.09 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	3033 independent reflections
Radiation source: fine-focus sealed tube	1878 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
ω and φ scan	θ_max = 29.6°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −20→20
T_min = 0.955, T_max = 0.971	k = −6→6
22920 measured reflections	l = −22→22

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.071	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.219	w = 1/[σ²(F_o²) + (0.0991P)² + 0.6777P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max < 0.001
3033 reflections	Δρ_max = 0.36 e Å⁻³
154 parameters	Δρ_min = −0.38 e Å⁻³
0 restraints	Extinction correction: shelxl, FC^*=KFC[1+0.001XFC²Λ³/SIN(2Θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.096 (14)

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > 2sigma(F²) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Cl1	0.66137 (5)	0.10505 (17)	0.21103 (5)	0.0569 (3)
O1	0.22420 (18)	1.2528 (6)	0.17721 (15)	0.0632 (9)
N1	0.46749 (16)	0.6578 (5)	0.09207 (14)	0.0458 (7)
N2	0.35223 (15)	0.9377 (5)	0.13429 (14)	0.0407 (7)
C2	0.42598 (17)	0.7322 (5)	0.15259 (16)	0.0372 (8)
C3	0.4511 (2)	0.6134 (6)	0.23285 (18)	0.0455 (9)
C4	0.5240 (2)	0.4173 (6)	0.25253 (18)	0.0478 (9)
C5	0.56824 (18)	0.3459 (6)	0.19071 (17)	0.0405 (8)
C6	0.5382 (2)	0.4667 (7)	0.11164 (18)	0.0463 (9)
C7	0.25370 (18)	1.2702 (6)	0.03971 (17)	0.0417 (8)
C8	0.2054 (2)	1.3599 (6)	0.0985 (2)	0.0476 (9)
C9	0.1342 (2)	1.5664 (7)	0.0744 (3)	0.0614 (13)
C10	0.1122 (2)	1.6815 (8)	−0.0058 (3)	0.0657 (13)
C11	0.1594 (2)	1.5959 (7)	−0.0644 (2)	0.0625 (11)
C12	0.2300 (2)	1.3929 (6)	−0.04133 (19)	0.0505 (9)
C13	0.32852 (19)	1.0574 (6)	0.06114 (18)	0.0413 (8)
H3	0.41950	0.66460	0.27280	0.0550*
H4	0.54300	0.33510	0.30610	0.0570*
H6	0.56780	0.41440	0.07030	0.0560*
H8	0.266 (3)	1.111 (10)	0.186 (3)	0.091 (15)*
H9	0.10170	1.62620	0.11280	0.0740*
H10	0.06480	1.81910	−0.02100	0.0790*
H11	0.14380	1.67410	−0.11860	0.0750*
H12	0.26230	1.33660	−0.08030	0.0610*
H13	0.358 (2)	1.009 (7)	0.015 (2)	0.047 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0455 (5)	0.0518 (5)	0.0695 (6)	0.0066 (3)	0.0084 (3)	0.0004 (3)
O1	0.0711 (15)	0.0624 (15)	0.0660 (15)	0.0137 (12)	0.0356 (12)	0.0063 (12)
N1	0.0448 (12)	0.0539 (14)	0.0402 (12)	0.0083 (11)	0.0138 (10)	−0.0007 (10)
N2	0.0410 (12)	0.0376 (11)	0.0460 (13)	−0.0020 (9)	0.0158 (10)	−0.0057 (9)
C2	0.0376 (13)	0.0363 (13)	0.0387 (13)	−0.0046 (10)	0.0118 (10)	−0.0065 (10)
C3	0.0542 (16)	0.0452 (15)	0.0414 (14)	−0.0010 (12)	0.0202 (12)	−0.0029 (12)
C4	0.0560 (16)	0.0466 (15)	0.0396 (14)	−0.0020 (13)	0.0107 (12)	0.0037 (12)
C5	0.0360 (12)	0.0377 (13)	0.0451 (15)	−0.0032 (10)	0.0060 (11)	−0.0027 (11)
C6	0.0453 (15)	0.0528 (16)	0.0426 (15)	0.0070 (12)	0.0147 (12)	−0.0052 (12)
C7	0.0391 (13)	0.0357 (13)	0.0499 (15)	−0.0057 (11)	0.0110 (11)	−0.0058 (11)
C8	0.0404 (14)	0.0424 (15)	0.0636 (18)	−0.0047 (11)	0.0200 (13)	−0.0048 (13)
C9	0.0480 (16)	0.0505 (17)	0.092 (3)	0.0043 (14)	0.0296 (16)	−0.0033 (17)
C10	0.0445 (16)	0.0496 (17)	0.097 (3)	0.0057 (14)	0.0080 (17)	0.0017 (18)
C11	0.0592 (19)	0.0510 (17)	0.066 (2)	0.0043 (15)	−0.0034 (16)	0.0012 (15)
C12	0.0520 (16)	0.0459 (15)	0.0513 (16)	0.0032 (13)	0.0095 (13)	−0.0043 (13)
C13	0.0405 (13)	0.0388 (13)	0.0453 (15)	−0.0025 (11)	0.0125 (11)	−0.0055 (11)

Geometric parameters (Å, º) top

Cl1—C5	1.733 (3)	C7—C8	1.404 (4)
O1—C8	1.340 (4)	C8—C9	1.399 (5)
O1—H8	0.89 (5)	C9—C10	1.375 (7)
N1—C6	1.342 (4)	C10—C11	1.385 (5)
N1—C2	1.341 (4)	C11—C12	1.381 (5)
N2—C13	1.282 (4)	C3—H3	0.9300
N2—C2	1.418 (4)	C4—H4	0.9300
C2—C3	1.383 (4)	C6—H6	0.9300
C3—C4	1.380 (4)	C9—H9	0.9300
C4—C5	1.382 (4)	C10—H10	0.9300
C5—C6	1.373 (4)	C11—H11	0.9300
C7—C12	1.401 (4)	C12—H12	0.9300
C7—C13	1.453 (4)	C13—H13	0.99 (3)

Cl1···C6ⁱ	3.627 (5)	C8···N2^vi	3.398 (5)
Cl1···Cl1ⁱⁱ	3.476 (4)	C8···C2^vi	3.582 (5)
Cl1···H11ⁱⁱⁱ	3.1500	C10···C13^vi	3.546 (6)
O1···N2	2.627 (4)	C10···C7^vi	3.398 (6)
O1···C3^iv	3.361 (5)	C11···C13^vi	3.510 (5)
O1···H3^iv	2.5000	C13···N1^vi	3.416 (5)
O1···H8^iv	2.76 (5)	C13···C6^vi	3.536 (5)
N1···C13ⁱ	3.416 (5)	C13···C10ⁱ	3.546 (6)
N1···C6^v	3.365 (5)	C13···C11ⁱ	3.510 (5)
N2···O1	2.627 (4)	C4···H11^viii	3.0300
N2···C8ⁱ	3.398 (5)	C6···H6^v	3.0300
N1···H6^v	2.5900	C11···H4^ix	3.0800
N1···H13	2.40 (3)	C13···H8	2.47 (5)
N2···H8	1.89 (5)	H3···O1^vii	2.5000
C2···C5^vi	3.494 (5)	H4···C11ⁱⁱⁱ	3.0800
C2···C7ⁱ	3.462 (5)	H6···N1^v	2.5900
C2···C8ⁱ	3.582 (5)	H6···C6^v	3.0300
C3···O1^vii	3.361 (5)	H8···N2	1.89 (5)
C5···C2ⁱ	3.494 (5)	H8···C13	2.47 (5)
C6···C13ⁱ	3.536 (5)	H8···O1^vii	2.76 (5)
C6···Cl1^vi	3.627 (5)	H11···Cl1^ix	3.1500
C6···N1^v	3.365 (5)	H11···C4^x	3.0300
C6···C6^v	3.544 (5)	H12···H13	2.3600
C7···C2^vi	3.462 (5)	H13···N1	2.40 (3)
C7···C10ⁱ	3.398 (6)	H13···H12	2.3600

C8—O1—H8	113 (3)	C10—C11—C12	119.2 (3)
C2—N1—C6	118.2 (2)	C7—C12—C11	121.2 (3)
C2—N2—C13	119.5 (2)	N2—C13—C7	121.5 (3)
N1—C2—N2	119.5 (2)	C2—C3—H3	121.00
N1—C2—C3	122.7 (2)	C4—C3—H3	121.00
N2—C2—C3	117.8 (2)	C3—C4—H4	121.00
C2—C3—C4	118.8 (3)	C5—C4—H4	121.00
C3—C4—C5	118.5 (3)	N1—C6—H6	119.00
Cl1—C5—C6	119.1 (2)	C5—C6—H6	119.00
C4—C5—C6	119.8 (3)	C8—C9—H9	120.00
Cl1—C5—C4	121.2 (2)	C10—C9—H9	120.00
N1—C6—C5	122.1 (3)	C9—C10—H10	120.00
C8—C7—C12	119.0 (3)	C11—C10—H10	119.00
C12—C7—C13	119.2 (3)	C10—C11—H11	120.00
C8—C7—C13	121.8 (3)	C12—C11—H11	120.00
O1—C8—C7	122.4 (3)	C7—C12—H12	119.00
C7—C8—C9	119.3 (3)	C11—C12—H12	119.00
O1—C8—C9	118.3 (3)	N2—C13—H13	123.2 (19)
C8—C9—C10	120.4 (3)	C7—C13—H13	115.3 (19)
C9—C10—C11	121.1 (3)

C6—N1—C2—N2	178.8 (2)	C12—C7—C8—O1	−179.9 (3)
C6—N1—C2—C3	−2.1 (4)	C12—C7—C8—C9	0.8 (4)
C2—N1—C6—C5	0.4 (4)	C13—C7—C8—O1	−0.9 (4)
C13—N2—C2—N1	−2.5 (4)	C13—C7—C8—C9	179.8 (3)
C13—N2—C2—C3	178.4 (3)	C8—C7—C12—C11	−1.0 (4)
C2—N2—C13—C7	−179.7 (2)	C13—C7—C12—C11	−180.0 (3)
N1—C2—C3—C4	2.2 (4)	C8—C7—C13—N2	1.5 (4)
N2—C2—C3—C4	−178.7 (3)	C12—C7—C13—N2	−179.5 (3)
C2—C3—C4—C5	−0.6 (4)	O1—C8—C9—C10	−179.7 (3)
C3—C4—C5—Cl1	179.1 (2)	C7—C8—C9—C10	−0.4 (5)
C3—C4—C5—C6	−1.0 (4)	C8—C9—C10—C11	0.2 (5)
Cl1—C5—C6—N1	−179.0 (2)	C9—C10—C11—C12	−0.4 (5)
C4—C5—C6—N1	1.1 (5)	C10—C11—C12—C7	0.8 (5)

Symmetry codes: (i) x, y−1, z; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x+1/2, −y+3/2, z+1/2; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x+1, −y+1, −z; (vi) x, y+1, z; (vii) −x+1/2, y−1/2, −z+1/2; (viii) x+1/2, −y+5/2, z+1/2; (ix) x−1/2, −y+3/2, z−1/2; (x) x−1/2, −y+5/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H8···N2	0.89 (5)	1.89 (5)	2.627 (4)	140 (4)
C3—H3···O1^vii	0.93	2.50	3.361 (5)	154
C6—H6···N1^v	0.93	2.59	3.365 (5)	141

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

Acknowledgements

The authors thank Dr J. S. Nirmalram, Assistant Professor, Center for Research and Development, PRIST University, for the help rendered during manuscript preparation.

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