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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2600.
Published online 2009 October 3. doi:  10.1107/S1600536809039142
PMCID: PMC2971220

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

Abstract

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

An external file that holds a picture, illustration, etc.
Object name is e-65-o2600-scheme1.jpg

Experimental

Crystal data

  • C12H13BrClNO
  • M r = 302.59
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2600-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.122
  • S = 1.08
  • 1488 reflections
  • 93 parameters
  • 6 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.40 e Å−3
  • Δρmin = −0.89 e Å−3

Data collection: SMART (Bruker, 2002 [triangle]); cell refinement: SAINT (Bruker, 2002 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809039142/ci2924Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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].

Experimental

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.

Refinement

Atom H1 was located from a difference map and its positional parameters were refined. The remaining H atoms were constrained to ideal geometries, with C-H = 0.93–0.98 Å. The Uiso(H) values were set at 1.2Ueq(C) and 1.5Ueq(O). The Uij components of atom C10 were restrained to an approximate isotropic behaviour.

Figures

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.

Crystal data

C12H13BrClNOF(000) = 608
Mr = 302.59Dx = 1.600 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 2255 reflections
a = 12.142 (2) Åθ = 2.6–24.5°
b = 6.8610 (14) ŵ = 3.46 mm1
c = 15.077 (3) ÅT = 298 K
V = 1256.0 (4) Å3Block, yellow
Z = 40.20 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer1488 independent reflections
Radiation source: fine-focus sealed tube1132 reflections with I > 2σ(I)
graphiteRint = 0.040
ω scansθmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −15→15
Tmin = 0.544, Tmax = 0.574k = −8→8
10340 measured reflectionsl = −19→19

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122H atoms treated by a mixture of independent and constrained refinement
S = 1.08w = 1/[σ2(Fo2) + (0.0628P)2 + 0.5702P] where P = (Fo2 + 2Fc2)/3
1488 reflections(Δ/σ)max = 0.001
93 parametersΔρmax = 0.40 e Å3
6 restraintsΔρmin = −0.89 e Å3

Special details

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)

xyzUiso*/Ueq
Br1−0.24144 (4)0.25000.43777 (4)0.0689 (3)
Cl10.17429 (13)0.25000.29606 (9)0.0784 (5)
O1−0.1127 (2)0.25000.60853 (19)0.0495 (7)
H1−0.063 (5)0.25000.652 (4)0.074*
N10.0610 (3)0.25000.7067 (2)0.0529 (9)
C10.0712 (3)0.25000.5489 (3)0.0411 (9)
C2−0.0460 (3)0.25000.5392 (3)0.0401 (9)
C3−0.0878 (4)0.25000.4537 (3)0.0428 (9)
C4−0.0210 (4)0.25000.3801 (3)0.0510 (11)
H4−0.05170.25000.32350.061*
C50.0921 (4)0.25000.3908 (3)0.0515 (11)
C60.1374 (4)0.25000.4740 (3)0.0498 (10)
H60.21360.25000.48040.060*
C70.1190 (4)0.25000.6365 (3)0.0506 (10)
H70.19530.25000.64180.061*
C80.1145 (4)0.25000.7942 (3)0.0627 (14)
H80.19500.25000.78930.075*
C90.0723 (4)0.0775 (6)0.8482 (3)0.0887 (14)
H9A0.0620−0.03590.81070.106*
H9B0.12370.04470.89520.106*
C10−0.0323 (5)0.1421 (10)0.8850 (4)0.133 (2)
H10A−0.04090.09340.94500.159*
H10B−0.09280.09340.84930.159*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0544 (3)0.0935 (5)0.0588 (4)0.000−0.0150 (2)0.000
Cl10.0888 (10)0.0947 (11)0.0517 (7)0.0000.0307 (7)0.000
O10.0437 (16)0.0639 (19)0.0409 (16)0.0000.0048 (13)0.000
N10.048 (2)0.072 (3)0.0388 (19)0.000−0.0052 (16)0.000
C10.041 (2)0.040 (2)0.042 (2)0.000−0.0002 (16)0.000
C20.049 (2)0.032 (2)0.039 (2)0.0000.0013 (17)0.000
C30.051 (2)0.035 (2)0.042 (2)0.000−0.0035 (18)0.000
C40.075 (3)0.043 (2)0.036 (2)0.0000.001 (2)0.000
C50.063 (3)0.049 (3)0.042 (2)0.0000.015 (2)0.000
C60.046 (2)0.049 (2)0.054 (3)0.0000.012 (2)0.000
C70.041 (2)0.061 (3)0.051 (2)0.000−0.0026 (19)0.000
C80.043 (2)0.100 (4)0.046 (2)0.000−0.010 (2)0.000
C90.134 (4)0.076 (3)0.057 (2)0.008 (3)−0.034 (2)0.007 (2)
C100.108 (4)0.180 (6)0.110 (4)−0.023 (4)0.015 (3)0.040 (4)

Geometric parameters (Å, °)

Br1—C31.881 (5)C5—C61.370 (6)
Cl1—C51.743 (4)C6—H60.93
O1—C21.322 (5)C7—H70.93
O1—H10.89 (6)C8—C91.526 (5)
N1—C71.271 (6)C8—C9i1.526 (5)
N1—C81.470 (5)C8—H80.98
C1—C61.385 (6)C9—C101.455 (7)
C1—C21.430 (6)C9—H9A0.97
C1—C71.443 (6)C9—H9B0.97
C2—C31.386 (6)C10—C10i1.480 (14)
C3—C41.374 (6)C10—H10A0.97
C4—C51.383 (7)C10—H10B0.97
C4—H40.93
C2—O1—H199 (4)N1—C7—H7118.7
C7—N1—C8120.1 (4)C1—C7—H7118.7
C6—C1—C2119.6 (4)N1—C8—C9109.3 (3)
C6—C1—C7120.8 (4)N1—C8—C9i109.3 (3)
C2—C1—C7119.5 (4)C9—C8—C9i101.7 (5)
O1—C2—C3120.7 (4)N1—C8—H8112.0
O1—C2—C1121.9 (4)C9—C8—H8112.0
C3—C2—C1117.3 (4)C9i—C8—H8112.0
C4—C3—C2122.3 (4)C10—C9—C8105.1 (4)
C4—C3—Br1118.9 (3)C10—C9—H9A110.7
C2—C3—Br1118.8 (3)C8—C9—H9A110.7
C3—C4—C5119.4 (4)C10—C9—H9B110.7
C3—C4—H4120.3C8—C9—H9B110.7
C5—C4—H4120.3H9A—C9—H9B108.8
C6—C5—C4120.4 (4)C9—C10—C10i107.7 (3)
C6—C5—Cl1121.4 (4)C9—C10—H10A110.2
C4—C5—Cl1118.2 (3)C10i—C10—H10A110.2
C5—C6—C1120.8 (4)C9—C10—H10B110.2
C5—C6—H6119.6C10i—C10—H10B110.2
C1—C6—H6119.6H10A—C10—H10B108.5
N1—C7—C1122.7 (4)
C6—C1—C2—O1180.0C4—C5—C6—C10.0
C7—C1—C2—O10.0Cl1—C5—C6—C1180.0
C6—C1—C2—C30.0C2—C1—C6—C50.0
C7—C1—C2—C3180.0C7—C1—C6—C5180.0
O1—C2—C3—C4180.0C8—N1—C7—C1180.0
C1—C2—C3—C40.0C6—C1—C7—N1180.0
O1—C2—C3—Br10.0C2—C1—C7—N10.000 (1)
C1—C2—C3—Br1180.0C7—N1—C8—C9−124.7 (3)
C2—C3—C4—C50.0C7—N1—C8—C9i124.7 (3)
Br1—C3—C4—C5180.0N1—C8—C9—C10−81.8 (4)
C3—C4—C5—C60.0C9i—C8—C9—C1033.7 (5)
C3—C4—C5—Cl1180.0C8—C9—C10—C10i−21.6 (3)

Symmetry codes: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···N10.89 (6)1.71 (6)2.577 (5)162 (5)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2924).

References

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