(E)-4-[(4-Amino-5-bromo­pyridin-3-yl)­iminometh­yl]phenol

Cai, M.; Zhang, M.; Hu, Y.

doi:10.1107/S160053680800812X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1053

doi:10.1107/S160053680800812X

Open

access

(E)-4-[(4-Amino-5-bromopyridin-3-yl)iminomethyl]phenol

Mingjian Cai,^a Mingjie Zhang ^a ^* and Yongliang Hu ^a

^aDepartment of Chemistry, Tianjin University, Tianjin 300072, People's Republic of China
^*Correspondence e-mail: mjzhangtju@163.com

(Received 21 March 2008; accepted 26 March 2008; online 10 May 2008)

In the molecule of the title compound, C₁₂H₁₀BrN₃O, the pyridine and benzene rings are oriented at a dihedral angle of 34.93 (3)°. Intramolecular N—H⋯N and N—H⋯Br hydrogen bonds result in the formation of two non-planar five-membered rings. In the crystal structure, intermolecular O—H⋯N and N—H⋯O hydrogen bonds link the molecules to form a three-dimensional network.

Related literature

For general background, see: Liu et al. (2002 ).

Experimental

Crystal data

C₁₂H₁₀BrN₃O
M_r = 292.14
Monoclinic, P 2₁ /n
a = 4.9607 (10) Å
b = 15.586 (3) Å
c = 14.906 (3) Å
β = 95.65 (3)°
V = 1146.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 3.57 mm⁻¹
T = 113 (2) K
0.10 × 0.08 × 0.06 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (Blessing, 1995 ) T_min = 0.717, T_max = 0.814
14191 measured reflections
2739 independent reflections
2123 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.100
S = 1.02
2739 reflections
163 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.82	1.88	2.688 (3)	167
N3—H3A⋯Br1	0.877 (18)	2.72 (3)	3.125 (4)	110.0 (19)
N3—H3A⋯O1ⁱⁱ	0.877 (18)	2.54 (2)	2.967 (5)	111.0 (19)
N3—H3B⋯N2	0.889 (16)	2.28 (3)	2.700 (5)	109 (2)
Symmetry codes: (i) $[x+{\script{3\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+2, -y+1, -z.

Data collection: CrystalClear (Rigaku/MSC, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680800812X/hk2438sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680800812X/hk2438Isup2.hkl

checkCIF report

Comment top

Schiff bases, as substrates, are important organic intermediates. Their recent applications in asymmetric catalytic hydrogenation, asymmetric chemical reduction and oxidation and asymmetric alkylidation of carbon atom, as well as reactions with Lawessen regent are very active (Liu et al., 2002). We have recently synthesized the novel title compound, (I), and report herein its crystal structure.

In the molecule of the title compound, (I), (Fig. 1) the bond lengths and angles are within normal ranges. Rings A (N1/C1–C5) and B (C7–C12) are, of course, planar and the dihedral angle between them is A/B = 34.93 (3)°. The intramolecular N—H···N and N—H···Br hydrogen bonds (Table 1) result in the formation of two non-planar five-membered rings; C (N2/C4/C5/N3/H3B) and D (Br1/C1/C5/N3/H3A).

In the crystal structure, intermolecular O—H···N and N—H···O hydrogen bonds (Table 1) link the molecules to form a three-dimensional network (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For general background, see: Liu et al. (2002).

Experimental top

5-bromopyridine-3,4-diamine (1.88 g, 10 mmol) was added to a solution of 4-hydroxybenzaldehyde (1.22 g, 10 mmol)in MeOH (50 ml). The solution was refluxed for 10 h, and then dried over magnesium sulfate, filtered and the volatiles were removed under reduced pressure. The crude product was further purified and recystallized from MeOH affording yellow crystals of (I) (yield; 70%).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 35% probability level.
	Fig. 2. A partial packing diagram of (I). Hydrogen bonds are shown as dashed lines.

(E)-4-[(4-amino-5-bromopyridin-3-yl)iminomethyl]phenol top

Crystal data top

C₁₂H₁₀BrN₃O	F(000) = 584
M_r = 292.14	D_x = 1.692 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3259 reflections
a = 4.9607 (10) Å	θ = 1.9–27.8°
b = 15.586 (3) Å	µ = 3.57 mm⁻¹
c = 14.906 (3) Å	T = 113 K
β = 95.65 (3)°	Plate, yellow
V = 1146.9 (4) Å³	0.10 × 0.08 × 0.06 mm
Z = 4

Data collection top

Rigaku Saturn diffractometer	2739 independent reflections
Radiation source: rotating anode	2123 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.053
ω scans	θ_max = 27.9°, θ_min = 2.6°
Absorption correction: multi-scan (Blessing, 1995)	h = −6→6
T_min = 0.717, T_max = 0.814	k = −20→20
14191 measured reflections	l = −19→19

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0558P)² + 0.0115P] where P = (F_o² + 2F_c²)/3
2739 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.53 e Å⁻³
2 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

C₁₂H₁₀BrN₃O	V = 1146.9 (4) Å³
M_r = 292.14	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.9607 (10) Å	µ = 3.57 mm⁻¹
b = 15.586 (3) Å	T = 113 K
c = 14.906 (3) Å	0.10 × 0.08 × 0.06 mm
β = 95.65 (3)°

Data collection top

Rigaku Saturn diffractometer	2739 independent reflections
Absorption correction: multi-scan (Blessing, 1995)	2123 reflections with I > 2σ(I)
T_min = 0.717, T_max = 0.814	R_int = 0.053
14191 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	2 restraints
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.53 e Å⁻³
2739 reflections	Δρ_min = −0.59 e Å⁻³
163 parameters

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Br1	0.22060 (6)	0.579793 (19)	0.40491 (2)	0.03830 (14)
O1	1.2134 (4)	0.29970 (11)	−0.18529 (12)	0.0258 (4)
H1	1.2791	0.2515	−0.1871	0.039*
N1	−0.0149 (4)	0.34708 (13)	0.29398 (14)	0.0207 (5)
N2	0.4754 (4)	0.40060 (14)	0.12855 (15)	0.0214 (5)
N3	0.5400 (5)	0.53733 (15)	0.23987 (17)	0.0263 (5)
C1	0.1953 (5)	0.48149 (16)	0.32940 (17)	0.0213 (5)
C2	0.0159 (5)	0.41727 (16)	0.34483 (18)	0.0220 (6)
H2	−0.0886	0.4231	0.3930	0.026*
C3	0.1392 (5)	0.34101 (15)	0.22483 (17)	0.0197 (5)
H3	0.1206	0.2921	0.1890	0.024*
C4	0.3231 (5)	0.40235 (16)	0.20351 (17)	0.0199 (5)
C5	0.3553 (5)	0.47740 (16)	0.25818 (17)	0.0202 (5)
C6	0.5619 (5)	0.32877 (16)	0.10100 (17)	0.0209 (5)
H6	0.5200	0.2789	0.1310	0.025*
C7	0.7226 (5)	0.32179 (16)	0.02482 (17)	0.0192 (5)
C8	0.7946 (5)	0.39343 (16)	−0.02422 (18)	0.0224 (6)
H8	0.7318	0.4474	−0.0098	0.027*
C9	0.9575 (5)	0.38505 (16)	−0.09363 (18)	0.0232 (6)
H9	1.0021	0.4333	−0.1257	0.028*
C10	1.0566 (5)	0.30420 (16)	−0.11623 (17)	0.0202 (5)
C11	0.9849 (5)	0.23290 (16)	−0.06839 (17)	0.0208 (5)
H11	1.0475	0.1789	−0.0829	0.025*
C12	0.8202 (5)	0.24182 (16)	0.00099 (17)	0.0213 (6)
H12	0.7736	0.1933	0.0324	0.026*
H3A	0.508 (6)	0.5891 (10)	0.2593 (19)	0.028 (8)*
H3B	0.590 (5)	0.5330 (19)	0.1844 (9)	0.027 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0515 (2)	0.02764 (19)	0.0375 (2)	−0.00060 (13)	0.01289 (16)	−0.01098 (13)
O1	0.0335 (11)	0.0214 (9)	0.0253 (10)	0.0049 (8)	0.0168 (8)	0.0036 (8)
N1	0.0210 (11)	0.0234 (11)	0.0186 (11)	0.0013 (9)	0.0061 (9)	0.0025 (9)
N2	0.0192 (11)	0.0245 (11)	0.0212 (12)	0.0001 (9)	0.0060 (9)	0.0012 (9)
N3	0.0292 (13)	0.0188 (12)	0.0321 (14)	−0.0044 (10)	0.0090 (11)	−0.0002 (10)
C1	0.0241 (13)	0.0191 (12)	0.0207 (13)	0.0038 (10)	0.0024 (11)	−0.0032 (10)
C2	0.0235 (14)	0.0238 (13)	0.0195 (13)	0.0042 (11)	0.0067 (11)	0.0009 (11)
C3	0.0220 (13)	0.0181 (12)	0.0194 (13)	0.0009 (10)	0.0038 (10)	−0.0005 (10)
C4	0.0211 (13)	0.0219 (12)	0.0171 (13)	0.0029 (10)	0.0040 (10)	0.0014 (10)
C5	0.0205 (13)	0.0185 (12)	0.0211 (13)	0.0032 (10)	0.0003 (10)	0.0015 (10)
C6	0.0187 (13)	0.0227 (13)	0.0216 (13)	−0.0001 (10)	0.0042 (10)	0.0021 (11)
C7	0.0181 (12)	0.0229 (13)	0.0168 (13)	−0.0019 (10)	0.0030 (10)	0.0001 (10)
C8	0.0235 (13)	0.0191 (12)	0.0253 (14)	0.0027 (11)	0.0063 (11)	0.0031 (11)
C9	0.0269 (14)	0.0180 (12)	0.0259 (14)	0.0019 (11)	0.0093 (11)	0.0058 (11)
C10	0.0196 (13)	0.0223 (12)	0.0193 (13)	−0.0008 (10)	0.0039 (10)	0.0022 (10)
C11	0.0222 (13)	0.0186 (12)	0.0222 (13)	−0.0003 (10)	0.0054 (11)	−0.0001 (10)
C12	0.0228 (13)	0.0187 (12)	0.0229 (14)	−0.0013 (10)	0.0059 (11)	0.0025 (10)

Geometric parameters (Å, º) top

Br1—C1	1.898 (2)	C3—H3	0.9300
O1—C10	1.352 (3)	C4—C5	1.426 (3)
O1—H1	0.8200	C6—C7	1.455 (3)
N1—C2	1.331 (3)	C6—H6	0.9300
N1—C3	1.346 (3)	C7—C12	1.396 (3)
N2—C6	1.281 (3)	C7—C8	1.400 (3)
N2—C4	1.409 (3)	C8—C9	1.380 (4)
N3—C5	1.355 (3)	C8—H8	0.9300
N3—H3A	0.876 (10)	C9—C10	1.406 (3)
N3—H3B	0.889 (10)	C9—H9	0.9300
C1—C2	1.374 (4)	C10—C11	1.386 (3)
C1—C5	1.388 (4)	C11—C12	1.387 (3)
C2—H2	0.9300	C11—H11	0.9300
C3—C4	1.380 (3)	C12—H12	0.9300

C10—O1—H1	109.5	N2—C6—C7	122.8 (2)
C2—N1—C3	116.9 (2)	N2—C6—H6	118.6
C6—N2—C4	119.6 (2)	C7—C6—H6	118.6
C5—N3—H3A	115 (2)	C12—C7—C8	117.8 (2)
C5—N3—H3B	113.1 (19)	C12—C7—C6	119.7 (2)
H3A—N3—H3B	117 (3)	C8—C7—C6	122.4 (2)
C2—C1—C5	121.5 (2)	C9—C8—C7	120.9 (2)
C2—C1—Br1	119.7 (2)	C9—C8—H8	119.5
C5—C1—Br1	118.76 (19)	C7—C8—H8	119.5
N1—C2—C1	122.9 (2)	C8—C9—C10	120.6 (2)
N1—C2—H2	118.5	C8—C9—H9	119.7
C1—C2—H2	118.5	C10—C9—H9	119.7
N1—C3—C4	124.5 (2)	O1—C10—C11	123.1 (2)
N1—C3—H3	117.8	O1—C10—C9	118.0 (2)
C4—C3—H3	117.8	C11—C10—C9	118.8 (2)
C3—C4—N2	126.0 (2)	C10—C11—C12	120.2 (2)
C3—C4—C5	118.4 (2)	C10—C11—H11	119.9
N2—C4—C5	115.5 (2)	C12—C11—H11	119.9
N3—C5—C1	124.8 (2)	C11—C12—C7	121.6 (2)
N3—C5—C4	119.4 (2)	C11—C12—H12	119.2
C1—C5—C4	115.8 (2)	C7—C12—H12	119.2

C3—N1—C2—C1	−0.2 (4)	N2—C4—C5—C1	176.8 (2)
C5—C1—C2—N1	0.7 (4)	C4—N2—C6—C7	−179.3 (2)
Br1—C1—C2—N1	179.2 (2)	N2—C6—C7—C12	177.2 (2)
C2—N1—C3—C4	−0.4 (4)	N2—C6—C7—C8	−0.1 (4)
N1—C3—C4—N2	−175.8 (2)	C12—C7—C8—C9	−0.2 (4)
N1—C3—C4—C5	0.4 (4)	C6—C7—C8—C9	177.1 (2)
C6—N2—C4—C3	−35.7 (4)	C7—C8—C9—C10	−0.5 (4)
C6—N2—C4—C5	148.0 (2)	C8—C9—C10—O1	179.5 (2)
C2—C1—C5—N3	−178.7 (2)	C8—C9—C10—C11	0.8 (4)
Br1—C1—C5—N3	2.9 (3)	O1—C10—C11—C12	−179.1 (2)
C2—C1—C5—C4	−0.7 (4)	C9—C10—C11—C12	−0.6 (4)
Br1—C1—C5—C4	−179.13 (17)	C10—C11—C12—C7	−0.1 (4)
C3—C4—C5—N3	178.2 (2)	C8—C7—C12—C11	0.5 (4)
N2—C4—C5—N3	−5.1 (3)	C6—C7—C12—C11	−176.9 (2)
C3—C4—C5—C1	0.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.82	1.88	2.688 (3)	167
N3—H3A···Br1	0.88 (2)	2.72 (3)	3.125 (4)	110 (2)
N3—H3A···O1ⁱⁱ	0.88 (2)	2.54 (2)	2.967 (5)	111 (2)
N3—H3B···N2	0.89 (2)	2.28 (3)	2.700 (5)	109 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀BrN₃O
M_r	292.14
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	113
a, b, c (Å)	4.9607 (10), 15.586 (3), 14.906 (3)
β (°)	95.65 (3)
V (Å³)	1146.9 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.57
Crystal size (mm)	0.10 × 0.08 × 0.06

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (Blessing, 1995)
T_min, T_max	0.717, 0.814
No. of measured, independent and observed [I > 2σ(I)] reflections	14191, 2739, 2123
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.100, 1.02
No. of reflections	2739
No. of parameters	163
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.59

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Bruker, 1997) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.82	1.88	2.688 (3)	167
N3—H3A···Br1	0.877 (18)	2.72 (3)	3.125 (4)	110.0 (19)
N3—H3A···O1ⁱⁱ	0.877 (18)	2.54 (2)	2.967 (5)	111.0 (19)
N3—H3B···N2	0.889 (16)	2.28 (3)	2.700 (5)	109 (2)

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

References

Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Liu, X.-L., Liu, Y.-H., Shi, Y.-C. & Jian, P.-M. (2002). Chin. J. Org. Chem. 22, 482-488. CAS Google Scholar
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1053

doi:10.1107/S160053680800812X

Open

access