2,4-Dibromo-6-(cyclo­propyl­imino­methyl)phenol

Yang, D.-S.

doi:10.1107/S1600536807038494

2,4-Dibromo-6-(cyclopropyliminomethyl)phenol

The asymmetric unit of the title compound, C₁₀H₉Br₂NO, consists of two molecules. In both molecules, the benzene and cyclopropyl rings are nearly perpendicular, with dihedral angles of 85.8 (4) and 75.5 (4)°. In the crystal structure, there are no obviously short intermolecular contacts. Each molecule has an intramolecular O—H

N hydrogen bond.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038494/om2147sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038494/om2147Isup2.hkl Contains datablock I

CCDC reference: 660232

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.007 Å
R factor = 0.045
wR factor = 0.105
Data-to-parameter ratio = 18.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.96

Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.72
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)       3000 Deg.
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.717
            Tmax scaled      0.231 Tmin scaled      0.113

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Schiff base compounds have been of great interest for a long time. These compounds play an important role in the development of coordination chemistry (Musie et al., 2001; Bernardo et al., 1996; Paul et al., 2002). Recently, we have reported a few Schiff base compounds (Yang, 2006a,b,c,d,e, 2007; Yang & Guo, 2006). As a further investigation of this work, the crystal structure of the title compound is reported here.

The asymmetric unit of the title compound consists of two molecules (Fig. 1). In both molecules, the benzene ring and the cyclopropyl ring are nearly perpendicular, with the dihedral angles of 85.8 (4) and 75.5 (4)°, respectively. All the bond lengths in the molecules are within normal ranges (Allen et al., 1987), and comparable to those of the similar compounds (Zhao, 2005, You & Chi, 2006). The C7═N1 and C17═N2 bond lengths of 1.272 (5) and 1.276 (5) Å conform to the values for double bonds. In the crystal structure, there are no obviously short contacts among the molecules.

Related literature top

For related structures see Yang (2006a,b,c,d,e, 2007); Yang & Guo (2006); Zhao (2005); You & Chi (2006). For related literature, see: Allen et al. (1987); Bernardo et al. (1996); Musie et al. (2001); Paul et al. (2002).

Experimental top

3,5-Dibromosalicylaldehyde (0.1 mmol, 18.0 mg) and cyclopropylamine (0.1 mmol, 5.7 mg) were dissolved in MeOH (10 ml). The mixture was stirred at room temperature to give a clear yellow solution. Crystals of the title compound were formed by gradual evaporation of the solvent over a period of about one week at room temperature.

Structure description top

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97.

Figures top

Fig. 1. The structure of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Intramolecular hydrogen bonds are shown as dashed lines.

2,4-Dibromo-6-(cyclopropyliminomethyl)phenol top

Crystal data top

C₁₀H₉Br₂NO	Z = 4
M_r = 319.00	F(000) = 616
Triclinic, P1	D_x = 1.926 Mg m⁻³
a = 9.1840 (18) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.495 (2) Å	Cell parameters from 2313 reflections
c = 12.265 (3) Å	θ = 2.4–25.1°
α = 70.85 (3)°	µ = 7.33 mm⁻¹
β = 68.62 (3)°	T = 298 K
γ = 69.69 (3)°	Block, yellow
V = 1100.2 (4) Å³	0.40 × 0.20 × 0.20 mm

Data collection top

Bruker SMART CCD diffractometer	4830 independent reflections
Radiation source: fine-focus sealed tube	2945 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ω scans	θ_max = 27.5°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.157, T_max = 0.322	k = −14→14
9324 measured reflections	l = −15→15

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 0.95	w = 1/[σ²(F_o²) + (0.0426P)²] where P = (F_o² + 2F_c²)/3
4830 reflections	(Δ/σ)_max < 0.001
255 parameters	Δρ_max = 0.64 e Å⁻³
0 restraints	Δρ_min = −0.69 e Å⁻³

Crystal data top

C₁₀H₉Br₂NO	γ = 69.69 (3)°
M_r = 319.00	V = 1100.2 (4) Å³
Triclinic, P1	Z = 4
a = 9.1840 (18) Å	Mo Kα radiation
b = 11.495 (2) Å	µ = 7.33 mm⁻¹
c = 12.265 (3) Å	T = 298 K
α = 70.85 (3)°	0.40 × 0.20 × 0.20 mm
β = 68.62 (3)°

Data collection top

Bruker SMART CCD diffractometer	4830 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2945 reflections with I > 2σ(I)
T_min = 0.157, T_max = 0.322	R_int = 0.039
9324 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 0.95	Δρ_max = 0.64 e Å⁻³
4830 reflections	Δρ_min = −0.69 e Å⁻³
255 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	−0.11261 (8)	−0.17137 (5)	0.31199 (6)	0.0654 (2)
Br2	0.54050 (7)	−0.29887 (5)	0.31061 (5)	0.05466 (18)
Br3	0.48615 (7)	0.32486 (6)	0.37844 (5)	0.0631 (2)
Br4	0.67363 (7)	0.01999 (5)	0.04642 (5)	0.05876 (19)
O1	−0.1149 (4)	0.0760 (3)	0.3466 (3)	0.0472 (8)
H1	−0.1128	0.1446	0.3518	0.071*
O2	0.3037 (4)	0.5125 (3)	0.2034 (3)	0.0462 (8)
H2	0.2358	0.5531	0.1669	0.069*
N1	0.0071 (5)	0.2383 (3)	0.3665 (3)	0.0427 (10)
N2	0.1932 (4)	0.5883 (3)	0.0169 (3)	0.0384 (9)
C1	0.1612 (6)	0.0265 (4)	0.3465 (4)	0.0363 (11)
C2	0.0329 (6)	−0.0049 (4)	0.3375 (4)	0.0361 (11)
C3	0.0627 (6)	−0.1257 (4)	0.3186 (4)	0.0400 (11)
C4	0.2121 (6)	−0.2115 (4)	0.3086 (4)	0.0418 (12)
H4	0.2293	−0.2909	0.2950	0.050*
C5	0.3354 (6)	−0.1783 (4)	0.3188 (4)	0.0407 (11)
C6	0.3111 (6)	−0.0607 (4)	0.3378 (4)	0.0405 (11)
H6	0.3958	−0.0397	0.3449	0.049*
C7	0.1393 (6)	0.1521 (4)	0.3654 (4)	0.0411 (11)
H7	0.2241	0.1690	0.3767	0.049*
C8	−0.0023 (6)	0.3593 (4)	0.3822 (5)	0.0461 (13)
H8	0.0894	0.3654	0.4011	0.055*
C9	−0.0850 (7)	0.4753 (5)	0.3070 (5)	0.0587 (15)
H9A	−0.0430	0.5497	0.2794	0.070*
H9B	−0.1274	0.4635	0.2507	0.070*
C10	−0.1668 (7)	0.4377 (5)	0.4370 (5)	0.0597 (15)
H10A	−0.2586	0.4026	0.4600	0.072*
H10B	−0.1741	0.4890	0.4887	0.072*
C11	0.3820 (5)	0.3853 (4)	0.0594 (4)	0.0347 (10)
C12	0.3856 (5)	0.4019 (4)	0.1673 (4)	0.0340 (10)
C13	0.4791 (5)	0.3044 (4)	0.2334 (4)	0.0372 (11)
C14	0.5632 (5)	0.1906 (4)	0.1997 (4)	0.0384 (11)
H14	0.6235	0.1251	0.2467	0.046*
C15	0.5562 (5)	0.1755 (4)	0.0950 (4)	0.0380 (11)
C16	0.4685 (5)	0.2713 (4)	0.0247 (4)	0.0401 (12)
H16	0.4669	0.2599	−0.0465	0.048*
C17	0.2896 (5)	0.4881 (4)	−0.0175 (4)	0.0391 (11)
H17	0.3018	0.4798	−0.0935	0.047*
C18	0.1096 (6)	0.6847 (4)	−0.0628 (4)	0.0445 (12)
H18	0.1489	0.6790	−0.1471	0.053*
C19	−0.0688 (6)	0.7366 (5)	−0.0140 (5)	0.0579 (15)
H19A	−0.1357	0.7597	−0.0673	0.069*
H19B	−0.1192	0.7019	0.0698	0.069*
C20	0.0415 (6)	0.8155 (4)	−0.0400 (5)	0.0476 (13)
H20A	0.0586	0.8294	0.0277	0.057*
H20B	0.0422	0.8872	−0.1093	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0728 (4)	0.0560 (4)	0.0896 (5)	−0.0173 (3)	−0.0424 (4)	−0.0221 (3)
Br2	0.0543 (4)	0.0474 (3)	0.0566 (4)	0.0070 (2)	−0.0191 (3)	−0.0225 (3)
Br3	0.0665 (4)	0.0767 (4)	0.0512 (4)	0.0029 (3)	−0.0293 (3)	−0.0300 (3)
Br4	0.0586 (4)	0.0438 (3)	0.0791 (4)	0.0062 (2)	−0.0294 (3)	−0.0304 (3)
O1	0.050 (2)	0.0368 (19)	0.057 (2)	−0.0050 (16)	−0.0227 (18)	−0.0119 (17)
O2	0.048 (2)	0.043 (2)	0.051 (2)	−0.0001 (15)	−0.0168 (17)	−0.0238 (17)
N1	0.049 (3)	0.030 (2)	0.047 (3)	−0.0089 (19)	−0.013 (2)	−0.0089 (18)
N2	0.035 (2)	0.036 (2)	0.043 (2)	−0.0059 (18)	−0.0137 (19)	−0.0076 (18)
C1	0.044 (3)	0.029 (2)	0.036 (3)	−0.010 (2)	−0.010 (2)	−0.007 (2)
C2	0.043 (3)	0.029 (2)	0.029 (3)	−0.003 (2)	−0.010 (2)	−0.0046 (19)
C3	0.058 (3)	0.036 (3)	0.035 (3)	−0.016 (2)	−0.023 (2)	−0.004 (2)
C4	0.055 (3)	0.031 (3)	0.040 (3)	−0.001 (2)	−0.021 (2)	−0.012 (2)
C5	0.045 (3)	0.033 (3)	0.040 (3)	0.000 (2)	−0.014 (2)	−0.011 (2)
C6	0.039 (3)	0.045 (3)	0.038 (3)	−0.013 (2)	−0.008 (2)	−0.010 (2)
C7	0.041 (3)	0.033 (3)	0.044 (3)	−0.008 (2)	−0.008 (2)	−0.009 (2)
C8	0.047 (3)	0.027 (2)	0.066 (3)	−0.005 (2)	−0.019 (3)	−0.015 (2)
C9	0.077 (4)	0.037 (3)	0.062 (4)	−0.021 (3)	−0.019 (3)	−0.005 (3)
C10	0.062 (4)	0.040 (3)	0.066 (4)	−0.003 (3)	−0.008 (3)	−0.019 (3)
C11	0.028 (3)	0.039 (3)	0.038 (3)	−0.007 (2)	−0.008 (2)	−0.014 (2)
C12	0.029 (3)	0.036 (3)	0.040 (3)	−0.008 (2)	−0.008 (2)	−0.014 (2)
C13	0.034 (3)	0.048 (3)	0.034 (3)	−0.014 (2)	−0.008 (2)	−0.013 (2)
C14	0.028 (3)	0.041 (3)	0.044 (3)	−0.009 (2)	−0.012 (2)	−0.005 (2)
C15	0.031 (3)	0.036 (3)	0.047 (3)	−0.007 (2)	−0.007 (2)	−0.015 (2)
C16	0.037 (3)	0.041 (3)	0.047 (3)	−0.004 (2)	−0.015 (2)	−0.019 (2)
C17	0.040 (3)	0.041 (3)	0.040 (3)	−0.009 (2)	−0.017 (2)	−0.010 (2)
C18	0.045 (3)	0.039 (3)	0.043 (3)	0.001 (2)	−0.019 (2)	−0.008 (2)
C19	0.038 (3)	0.060 (4)	0.072 (4)	−0.007 (3)	−0.025 (3)	−0.006 (3)
C20	0.045 (3)	0.040 (3)	0.051 (3)	−0.005 (2)	−0.015 (3)	−0.006 (2)

Geometric parameters (Å, º) top

Br1—C3	1.894 (5)	C8—H8	0.9800
Br2—C5	1.903 (4)	C9—C10	1.481 (7)
Br3—C13	1.895 (4)	C9—H9A	0.9700
Br4—C15	1.899 (4)	C9—H9B	0.9700
O1—C2	1.342 (5)	C10—H10A	0.9700
O1—H1	0.8200	C10—H10B	0.9700
O2—C12	1.356 (5)	C11—C16	1.389 (6)
O2—H2	0.8200	C11—C12	1.410 (6)
N1—C7	1.272 (5)	C11—C17	1.471 (6)
N1—C8	1.436 (5)	C12—C13	1.377 (6)
N2—C17	1.276 (5)	C13—C14	1.379 (6)
N2—C18	1.421 (5)	C14—C15	1.376 (6)
C1—C6	1.384 (6)	C14—H14	0.9300
C1—C2	1.396 (6)	C15—C16	1.368 (6)
C1—C7	1.470 (6)	C16—H16	0.9300
C2—C3	1.398 (6)	C17—H17	0.9300
C3—C4	1.375 (6)	C18—C20	1.492 (6)
C4—C5	1.371 (6)	C18—C19	1.496 (7)
C4—H4	0.9300	C18—H18	0.9800
C5—C6	1.374 (6)	C19—C20	1.470 (7)
C6—H6	0.9300	C19—H19A	0.9700
C7—H7	0.9300	C19—H19B	0.9700
C8—C9	1.485 (6)	C20—H20A	0.9700
C8—C10	1.503 (6)	C20—H20B	0.9700

C2—O1—H1	109.5	C8—C10—H10B	117.8
C12—O2—H2	109.5	H10A—C10—H10B	114.9
C7—N1—C8	117.8 (4)	C16—C11—C12	119.6 (4)
C17—N2—C18	118.9 (4)	C16—C11—C17	119.6 (4)
C6—C1—C2	120.1 (4)	C12—C11—C17	120.7 (4)
C6—C1—C7	119.2 (4)	O2—C12—C13	120.5 (4)
C2—C1—C7	120.7 (4)	O2—C12—C11	121.2 (4)
O1—C2—C1	122.3 (4)	C13—C12—C11	118.3 (4)
O1—C2—C3	120.1 (4)	C12—C13—C14	122.0 (4)
C1—C2—C3	117.6 (4)	C12—C13—Br3	119.0 (3)
C4—C3—C2	122.1 (4)	C14—C13—Br3	118.9 (3)
C4—C3—Br1	120.0 (3)	C15—C14—C13	118.8 (4)
C2—C3—Br1	117.9 (4)	C15—C14—H14	120.6
C5—C4—C3	118.9 (4)	C13—C14—H14	120.6
C5—C4—H4	120.6	C16—C15—C14	121.2 (4)
C3—C4—H4	120.6	C16—C15—Br4	119.6 (3)
C4—C5—C6	120.8 (4)	C14—C15—Br4	119.2 (3)
C4—C5—Br2	119.1 (3)	C15—C16—C11	120.1 (4)
C6—C5—Br2	120.0 (4)	C15—C16—H16	120.0
C5—C6—C1	120.4 (4)	C11—C16—H16	120.0
C5—C6—H6	119.8	N2—C17—C11	122.0 (4)
C1—C6—H6	119.8	N2—C17—H17	119.0
N1—C7—C1	121.5 (5)	C11—C17—H17	119.0
N1—C7—H7	119.2	N2—C18—C20	118.0 (4)
C1—C7—H7	119.2	N2—C18—C19	117.6 (4)
N1—C8—C9	117.2 (4)	C20—C18—C19	59.0 (3)
N1—C8—C10	117.4 (4)	N2—C18—H18	116.6
C9—C8—C10	59.4 (3)	C20—C18—H18	116.6
N1—C8—H8	116.8	C19—C18—H18	116.6
C9—C8—H8	116.8	C20—C19—C18	60.4 (3)
C10—C8—H8	116.8	C20—C19—H19A	117.7
C10—C9—C8	60.9 (3)	C18—C19—H19A	117.7
C10—C9—H9A	117.7	C20—C19—H19B	117.7
C8—C9—H9A	117.7	C18—C19—H19B	117.7
C10—C9—H9B	117.7	H19A—C19—H19B	114.9
C8—C9—H9B	117.7	C19—C20—C18	60.7 (3)
H9A—C9—H9B	114.8	C19—C20—H20A	117.7
C9—C10—C8	59.7 (3)	C18—C20—H20A	117.7
C9—C10—H10A	117.8	C19—C20—H20B	117.7
C8—C10—H10A	117.8	C18—C20—H20B	117.7
C9—C10—H10B	117.8	H20A—C20—H20B	114.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N2	0.82	1.90	2.607 (5)	143
O1—H1···N1	0.82	1.87	2.597 (5)	147

Experimental details

Crystal data
Chemical formula	C₁₀H₉Br₂NO
M_r	319.00
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	9.1840 (18), 11.495 (2), 12.265 (3)
α, β, γ (°)	70.85 (3), 68.62 (3), 69.69 (3)
V (Å³)	1100.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	7.33
Crystal size (mm)	0.40 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.157, 0.322
No. of measured, independent and observed [I > 2σ(I)] reflections	9324, 4830, 2945
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.105, 0.95
No. of reflections	4830
No. of parameters	255
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.69

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXL97.