2-Bromo-4-chloro-6-(cyclo­pentyl­imino­meth­yl)phenol

Hao, Y.-M.

doi:10.1107/S1600536809039142

organic compounds

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Volume 65| Part 11| November 2009| Page o2600

https://doi.org/10.1107/S1600536809039142

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2-Bromo-4-chloro-6-(cyclopentyliminomethyl)phenol

Yu-Mei Hao ^a ^*

^aDepartment of Chemistry, Baicheng Normal University, Baicheng 137000, People's Republic of China
^*Correspondence e-mail: jyxygzb@163.com

(Received 24 September 2009; accepted 26 September 2009; online 3 October 2009)

All atoms of the title molecule, C₁₂H₁₃BrClNO, except the C and H atoms of the cyclopentane methylene groups lie on a crystallographic mirror plane. The cyclopentane ring adopts an envelope conformation and an intramolecular O—H⋯N hydrogen bond is observed. In the crystal, molecules are stacked along the b axis by π–π interactions [centroid–centroid distance = 3.6424 (11) Å].

Related literature

For the pharmaceutical and medicinal activity of Schiff bases, see: Dao et al. (2000 ); Sriram et al. (2006 ); Karthikeyan et al. (2006 ). For the coordination chemistry of Schiff bases, see: Ali et al. (2008 ); Kargar et al. (2009 ); Yeap et al. (2009 ). For the crystal structures of Schiff base compounds, see: Fun et al. (2009 ); Nadeem et al. (2009 ); Eltayeb et al. (2008 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₂H₁₃BrClNO
M_r = 302.59
Orthorhombic, P n m a
a = 12.142 (2) Å
b = 6.8610 (14) Å
c = 15.077 (3) Å
V = 1256.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 3.46 mm⁻¹
T = 298 K
0.20 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.544, T_max = 0.574
10340 measured reflections
1488 independent reflections
1132 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.122
S = 1.08
1488 reflections
93 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.89 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.89 (6)	1.71 (6)	2.577 (5)	162 (5)

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809039142/ci2924sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809039142/ci2924Isup2.hkl

checkCIF report

Comment top

Schiff base compounds are a class of important materials used in pharmaceutical and medicinal appications (Dao et al., 2000; Sriram et al., 2006; Karthikeyan et al., 2006). Schiff bases have also been used as versatile ligands in coordination chemistry (Ali et al., 2008; Kargar et al., 2009; Yeap et al., 2009). Recently, crystal structures of a large number of Schiff base compounds have been reported (Fun et al., 2009; Nadeem et al., 2009; Eltayeb et al., 2008). In this paper, the title new Schiff base compound (Fig. 1) is reported.

All atoms of the title molecule, except the C and H atoms of the four methylene groups lie on a crystallographic mirror plane. The cyclopentane ring adopts a an envelope conformation. An intramolecular O—H···N hydrogen bond (Table 1) is observed. All bond lengths are within normal values (Allen et al., 1987).

In the crystal, molecules are stacked along the b axis with π-π interactions [centroid to centroid distance = 3.6424 (11) Å].

Related literature top

For the pharmaceutical and medicinal activity of Schiff bases, see: Dao et al. (2000); Sriram et al. (2006); Karthikeyan et al. (2006). For the coordination chemistry of Schiff bases, see: Ali et al. (2008); Kargar et al. (2009); Yeap et al. (2009). For the crystal structures of Schiff base compounds, see: Fun et al. (2009); Nadeem et al. (2009); Eltayeb et al. (2008). For bond-length data, see: Allen et al. (1987).

Experimental top

3-Bromo-5-chlorosalicylaldehyde (0.1 mmol, 23.5 mg) and cyclopentylamine (0.1 mmol, 8.5 mg) were refluxed in a 30 ml methanol solution for 30 min to give a clear orange solution. Yellow block-shaped single crystals of the title compound were formed by slow evaporation of the solvent over several days at room temperature.

Structure description top

In the crystal, molecules are stacked along the b axis with π-π interactions [centroid to centroid distance = 3.6424 (11) Å].

For the pharmaceutical and medicinal activity of Schiff bases, see: Dao et al. (2000); Sriram et al. (2006); Karthikeyan et al. (2006). For the coordination chemistry of Schiff bases, see: Ali et al. (2008); Kargar et al. (2009); Yeap et al. (2009). For the crystal structures of Schiff base compounds, see: Fun et al. (2009); Nadeem et al. (2009); Eltayeb et al. (2008). For bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, with 30% probability displacement ellipsoids. The dashed line indicates an intramolecular O—H···N hydrogen bond.

2-Bromo-4-chloro-6-(cyclopentyliminomethyl)phenol top

Crystal data top

C₁₂H₁₃BrClNO	F(000) = 608
M_r = 302.59	D_x = 1.600 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 2255 reflections
a = 12.142 (2) Å	θ = 2.6–24.5°
b = 6.8610 (14) Å	µ = 3.46 mm⁻¹
c = 15.077 (3) Å	T = 298 K
V = 1256.0 (4) Å³	Block, yellow
Z = 4	0.20 × 0.20 × 0.18 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1488 independent reflections
Radiation source: fine-focus sealed tube	1132 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
T_min = 0.544, T_max = 0.574	k = −8→8
10340 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0628P)² + 0.5702P] where P = (F_o² + 2F_c²)/3
1488 reflections	(Δ/σ)_max = 0.001
93 parameters	Δρ_max = 0.40 e Å⁻³
6 restraints	Δρ_min = −0.89 e Å⁻³

Crystal data top

C₁₂H₁₃BrClNO	V = 1256.0 (4) Å³
M_r = 302.59	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 12.142 (2) Å	µ = 3.46 mm⁻¹
b = 6.8610 (14) Å	T = 298 K
c = 15.077 (3) Å	0.20 × 0.20 × 0.18 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1488 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1132 reflections with I > 2σ(I)
T_min = 0.544, T_max = 0.574	R_int = 0.040
10340 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	6 restraints
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.40 e Å⁻³
1488 reflections	Δρ_min = −0.89 e Å⁻³
93 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 > σ(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	−0.24144 (4)	0.2500	0.43777 (4)	0.0689 (3)
Cl1	0.17429 (13)	0.2500	0.29606 (9)	0.0784 (5)
O1	−0.1127 (2)	0.2500	0.60853 (19)	0.0495 (7)
H1	−0.063 (5)	0.2500	0.652 (4)	0.074*
N1	0.0610 (3)	0.2500	0.7067 (2)	0.0529 (9)
C1	0.0712 (3)	0.2500	0.5489 (3)	0.0411 (9)
C2	−0.0460 (3)	0.2500	0.5392 (3)	0.0401 (9)
C3	−0.0878 (4)	0.2500	0.4537 (3)	0.0428 (9)
C4	−0.0210 (4)	0.2500	0.3801 (3)	0.0510 (11)
H4	−0.0517	0.2500	0.3235	0.061*
C5	0.0921 (4)	0.2500	0.3908 (3)	0.0515 (11)
C6	0.1374 (4)	0.2500	0.4740 (3)	0.0498 (10)
H6	0.2136	0.2500	0.4804	0.060*
C7	0.1190 (4)	0.2500	0.6365 (3)	0.0506 (10)
H7	0.1953	0.2500	0.6418	0.061*
C8	0.1145 (4)	0.2500	0.7942 (3)	0.0627 (14)
H8	0.1950	0.2500	0.7893	0.075*
C9	0.0723 (4)	0.0775 (6)	0.8482 (3)	0.0887 (14)
H9A	0.0620	−0.0359	0.8107	0.106*
H9B	0.1237	0.0447	0.8952	0.106*
C10	−0.0323 (5)	0.1421 (10)	0.8850 (4)	0.133 (2)
H10A	−0.0409	0.0934	0.9450	0.159*
H10B	−0.0928	0.0934	0.8493	0.159*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0544 (3)	0.0935 (5)	0.0588 (4)	0.000	−0.0150 (2)	0.000
Cl1	0.0888 (10)	0.0947 (11)	0.0517 (7)	0.000	0.0307 (7)	0.000
O1	0.0437 (16)	0.0639 (19)	0.0409 (16)	0.000	0.0048 (13)	0.000
N1	0.048 (2)	0.072 (3)	0.0388 (19)	0.000	−0.0052 (16)	0.000
C1	0.041 (2)	0.040 (2)	0.042 (2)	0.000	−0.0002 (16)	0.000
C2	0.049 (2)	0.032 (2)	0.039 (2)	0.000	0.0013 (17)	0.000
C3	0.051 (2)	0.035 (2)	0.042 (2)	0.000	−0.0035 (18)	0.000
C4	0.075 (3)	0.043 (2)	0.036 (2)	0.000	0.001 (2)	0.000
C5	0.063 (3)	0.049 (3)	0.042 (2)	0.000	0.015 (2)	0.000
C6	0.046 (2)	0.049 (2)	0.054 (3)	0.000	0.012 (2)	0.000
C7	0.041 (2)	0.061 (3)	0.051 (2)	0.000	−0.0026 (19)	0.000
C8	0.043 (2)	0.100 (4)	0.046 (2)	0.000	−0.010 (2)	0.000
C9	0.134 (4)	0.076 (3)	0.057 (2)	0.008 (3)	−0.034 (2)	0.007 (2)
C10	0.108 (4)	0.180 (6)	0.110 (4)	−0.023 (4)	0.015 (3)	0.040 (4)

Geometric parameters (Å, º) top

Br1—C3	1.881 (5)	C5—C6	1.370 (6)
Cl1—C5	1.743 (4)	C6—H6	0.93
O1—C2	1.322 (5)	C7—H7	0.93
O1—H1	0.89 (6)	C8—C9	1.526 (5)
N1—C7	1.271 (6)	C8—C9ⁱ	1.526 (5)
N1—C8	1.470 (5)	C8—H8	0.98
C1—C6	1.385 (6)	C9—C10	1.455 (7)
C1—C2	1.430 (6)	C9—H9A	0.97
C1—C7	1.443 (6)	C9—H9B	0.97
C2—C3	1.386 (6)	C10—C10ⁱ	1.480 (14)
C3—C4	1.374 (6)	C10—H10A	0.97
C4—C5	1.383 (7)	C10—H10B	0.97
C4—H4	0.93

C2—O1—H1	99 (4)	N1—C7—H7	118.7
C7—N1—C8	120.1 (4)	C1—C7—H7	118.7
C6—C1—C2	119.6 (4)	N1—C8—C9	109.3 (3)
C6—C1—C7	120.8 (4)	N1—C8—C9ⁱ	109.3 (3)
C2—C1—C7	119.5 (4)	C9—C8—C9ⁱ	101.7 (5)
O1—C2—C3	120.7 (4)	N1—C8—H8	112.0
O1—C2—C1	121.9 (4)	C9—C8—H8	112.0
C3—C2—C1	117.3 (4)	C9ⁱ—C8—H8	112.0
C4—C3—C2	122.3 (4)	C10—C9—C8	105.1 (4)
C4—C3—Br1	118.9 (3)	C10—C9—H9A	110.7
C2—C3—Br1	118.8 (3)	C8—C9—H9A	110.7
C3—C4—C5	119.4 (4)	C10—C9—H9B	110.7
C3—C4—H4	120.3	C8—C9—H9B	110.7
C5—C4—H4	120.3	H9A—C9—H9B	108.8
C6—C5—C4	120.4 (4)	C9—C10—C10ⁱ	107.7 (3)
C6—C5—Cl1	121.4 (4)	C9—C10—H10A	110.2
C4—C5—Cl1	118.2 (3)	C10ⁱ—C10—H10A	110.2
C5—C6—C1	120.8 (4)	C9—C10—H10B	110.2
C5—C6—H6	119.6	C10ⁱ—C10—H10B	110.2
C1—C6—H6	119.6	H10A—C10—H10B	108.5
N1—C7—C1	122.7 (4)

C6—C1—C2—O1	180.0	C4—C5—C6—C1	0.0
C7—C1—C2—O1	0.0	Cl1—C5—C6—C1	180.0
C6—C1—C2—C3	0.0	C2—C1—C6—C5	0.0
C7—C1—C2—C3	180.0	C7—C1—C6—C5	180.0
O1—C2—C3—C4	180.0	C8—N1—C7—C1	180.0
C1—C2—C3—C4	0.0	C6—C1—C7—N1	180.0
O1—C2—C3—Br1	0.0	C2—C1—C7—N1	0.000 (1)
C1—C2—C3—Br1	180.0	C7—N1—C8—C9	−124.7 (3)
C2—C3—C4—C5	0.0	C7—N1—C8—C9ⁱ	124.7 (3)
Br1—C3—C4—C5	180.0	N1—C8—C9—C10	−81.8 (4)
C3—C4—C5—C6	0.0	C9ⁱ—C8—C9—C10	33.7 (5)
C3—C4—C5—Cl1	180.0	C8—C9—C10—C10ⁱ	−21.6 (3)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.89 (6)	1.71 (6)	2.577 (5)	162 (5)

Experimental details

Crystal data
Chemical formula	C₁₂H₁₃BrClNO
M_r	302.59
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	298
a, b, c (Å)	12.142 (2), 6.8610 (14), 15.077 (3)
V (Å³)	1256.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.46
Crystal size (mm)	0.20 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.544, 0.574
No. of measured, independent and observed [I > 2σ(I)] reflections	10340, 1488, 1132
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.122, 1.08
No. of reflections	1488
No. of parameters	93
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.89

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.89 (6)	1.71 (6)	2.577 (5)	162 (5)

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2600

https://doi.org/10.1107/S1600536809039142

Open

access