organic papers
o1946
Li and Tian C9H10BrNO3 doi:10.1107/S160053680601364X Acta Cryst.(2006). E62, o1946–o1947 Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368
(
E
)-2-Bromo-4,5-dimethoxybenzaldehyde oxime
Xiang Li* and Da-Min Tian
Chemistry and Chemical Engineering Depart-ment, Pingdingshan Institute of Technology, Pingdingshan 467000, People’s Republic of China
Correspondence e-mail: lixiang_acta@yahoo.com.cn
Key indicators
Single-crystal X-ray study
T= 291 K
Mean(C–C) = 0.006 A˚
Rfactor = 0.044
wRfactor = 0.107
Data-to-parameter ratio = 14.4
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
Received 1 April 2006 Accepted 15 April 2006
#2006 International Union of Crystallography
All rights reserved
The title compound, C9H10BrNO3, which exists as the E
isomer, crystallizes with two independent molecules in the asymmetric unit. The bond lengths and angles in both molecules are normal. The crystal packing is stabilized by
intermolecular O—H O hydrogen bonds, which link the
molecules into circular tetramers, and by weak–stacking
interactions.
Comment
Substituted benzaldehyde oxime is an important intermediate in organic synthesis (Xu & Jin, 1999), existing in two isomeric forms,viz. ZandE(Sharghi & Sarvari, 2001). We report here the crystal structure of the title compound, (I).
Compound (I) crystallizes with two independent molecules in the asymmetric unit (Fig. 1). The bond lengths and angles in both molecules (Table 1) are in agreement with the values reported previously (Jerslev, 1983; Jensen, 1970). The devia-tion of atom C17 from the mean plane formed by C10–C16/
C18/N2/O4–O6/Br1 is 0.106 (3) A˚ , while in the second
inde-pendent molecule the atoms C1–C9, N1, O1–O3 and Br2 are essentially coplanar, the largest deviation from the mean plane
being 0.040 (2) A˚ for atom C8. Intermolecular O—H O
hydrogen bonds (Table 2) link the molecules into nearly planar circular tetramers (Fig. 2). The relatively short distance
of 3.829 (4) A˚ between the centroids of benzene rings C1–C6
and C10–C15 [at (x,1 2+y,
1
2z)] indicates the presence of
weak–interactions, which contribute to the stability of the crystal packing.
Experimental
dichloromethane, and the organic phase was evaporated to afford the title product in 85% yield (2.21 g). Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a mixture of ethyl acetate and petroleum ether (1:1v/v) at room temperature over a period of two weeks.
Crystal data
C9H10BrNO3
Mr= 260.09
Monoclinic,P21=c
a= 8.0870 (14) A˚
b= 9.6175 (17) A˚
c= 26.795 (5) A˚
= 94.964 (3) V= 2076.2 (6) A˚3
Z= 8
Dx= 1.664 Mg m
3
MoKradiation
= 3.94 mm1
T= 291 (2) K Block, colourless 0.340.310.25 mm
Data collection
Bruker SMART CCD area-detector diffractometer
’and!scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)
Tmin= 0.348,Tmax= 0.439
(expected range = 0.296–0.373)
10481 measured reflections 3653 independent reflections 2458 reflections withI> 2(I)
Rint= 0.035
max= 25.0
Refinement
Refinement onF2
R[F2> 2(F2)] = 0.044
wR(F2) = 0.107
S= 1.04 3653 reflections 253 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0506P)2
+ 0.3059P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001
max= 0.66 e A˚
3
min=0.40 e A˚
[image:2.610.311.564.68.256.2]3
Table 1
Selected geometric parameters (A˚ ,).
Br1—C10 1.913 (4) Br2—C1 1.903 (4)
N1—C9 1.233 (5) N2—C18 1.239 (5)
C3—O1—C7 117.8 (4) C4—O2—C8 117.5 (3)
C9—N1—O3 112.2 (4) C18—N2—O6 112.1 (4)
Table 2
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
O3—H3A O4i
0.84 2.36 3.098 (5) 147 O3—H3A O5i
0.84 2.03 2.747 (5) 142 O6—H6A O1ii
0.84 2.19 2.942 (4) 150 O6—H6A O2ii
0.84 2.33 3.038 (4) 142
Symmetry codes: (i)x1;yþ1 2;zþ
1
2; (ii)x;y 1 2;zþ
1 2.
All H atoms were placed in calculated positions, with C—H = 0.95– 0.98 A˚ and O—H = 0.84 A˚, and included in the final cycles of refinement using a riding model, withUiso(H) = 1.2Ueq(C) for the aryl H atoms and 1.5Ueq(O,C) for the hydroxyl and methyl H atoms.
Data collection:SMART(Bruker, 1998); cell refinement:SAINT
(Bruker, 1999); data reduction: SAINT; program(s) used to solve
structure:SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
SHELXTL (Bruker, 1999); software used to prepare material for publication:SHELXTL.
References
Bruker (1998).SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Bruker (1999). SAINT and SHELXTL. Bruker AXS Inc., Madison,
Wisconsin, USA.
Jensen, K. G. (1970).Acta Chem. Scand.24, 3293–3330. Jerslev, B. (1983).Acta Cryst.C39, 1447–1454. Sharghi, H. & Sarvari, M. H. (2001).Synlett,1, 99–101.
Sheldrick, G. M. (1996).SADABS. University of Go¨ttingen, Germany. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
Go¨ttingen, Germany.
[image:2.610.316.564.300.474.2]Xu, J. & Jin, S. (1999).Acta Cryst.C55, 1579–1581. Figure 1
View of the asymmetric unit of (I), with displacement ellipsoids drawn at the 40% probability level.
Figure 2
[image:2.610.45.296.537.592.2]supporting information
sup-1 Acta Cryst. (2006). E62, o1946–o1947
supporting information
Acta Cryst. (2006). E62, o1946–o1947 [https://doi.org/10.1107/S160053680601364X]
(
E
)-2-Bromo-4,5-dimethoxybenzaldehyde oxime
Xiang Li and Da-Min Tian
(E)-2-Bromo-4,5-dimethoxybenzaldehyde oxime
Crystal data
C9H10BrNO3 Mr = 260.09 Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 8.0870 (14) Å
b = 9.6175 (17) Å
c = 26.795 (5) Å
β = 94.964 (3)°
V = 2076.2 (6) Å3
Z = 8
F(000) = 1040
Dx = 1.664 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 1048 reflections
θ = 2.3–22.3°
µ = 3.94 mm−1
T = 291 K
Block, colourless 0.34 × 0.31 × 0.25 mm
Data collection
Bruker SMART CCD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.348, Tmax = 0.439
10481 measured reflections 3653 independent reflections 2458 reflections with I > 2σ(I) Rint = 0.035
θmax = 25.0°, θmin = 2.3°
h = −9→8
k = −11→11
l = −31→29
Refinement
Refinement on F2
Least-squares matrix: full R[F2 > 2σ(F2)] = 0.044 wR(F2) = 0.107
S = 1.04
3653 reflections 253 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained w = 1/[σ2(F
o2) + (0.0506P)2 + 0.3059P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.66 e Å−3
Δρmin = −0.40 e Å−3
Special details
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)
x y z Uiso*/Ueq
Br1 0.34024 (6) 0.09276 (5) 0.424220 (19) 0.06379 (19)
Br2 0.14045 (6) 0.33461 (6) 0.274671 (19) 0.0723 (2)
O1 0.3145 (4) −0.0338 (3) 0.14501 (12) 0.0607 (8)
O2 0.0363 (4) −0.0329 (3) 0.09324 (11) 0.0633 (8)
O3 −0.4377 (4) 0.4071 (4) 0.19438 (13) 0.0820 (11)
H3A −0.5228 0.4115 0.1741 0.123*
O4 −0.3386 (4) −0.1673 (3) 0.40163 (11) 0.0624 (8)
O5 −0.2648 (4) 0.0223 (4) 0.34159 (12) 0.0678 (9)
O6 0.3021 (4) −0.2738 (4) 0.55941 (12) 0.0802 (10)
H6A 0.2688 −0.3343 0.5789 0.120*
N1 −0.3275 (5) 0.3143 (4) 0.17702 (14) 0.0584 (10)
N2 0.1758 (4) −0.2446 (4) 0.52174 (13) 0.0565 (10)
C1 0.0968 (5) 0.2226 (4) 0.21647 (15) 0.0468 (10)
C2 0.2250 (5) 0.1370 (4) 0.20384 (16) 0.0500 (11)
H2B 0.3283 0.1363 0.2237 0.060*
C3 0.2006 (5) 0.0531 (4) 0.16212 (16) 0.0461 (10)
C4 0.0460 (5) 0.0547 (4) 0.13376 (16) 0.0437 (10)
C5 −0.0766 (5) 0.1407 (4) 0.14686 (15) 0.0437 (10)
H5A −0.1797 0.1421 0.1270 0.052*
C6 −0.0546 (5) 0.2269 (4) 0.18889 (15) 0.0424 (10)
C7 0.4756 (6) −0.0393 (6) 0.17205 (19) 0.0713 (14)
H7A 0.5455 −0.1060 0.1559 0.107*
H7B 0.4645 −0.0687 0.2066 0.107*
H7C 0.5270 0.0530 0.1721 0.107*
C8 −0.1177 (6) −0.0412 (6) 0.06386 (19) 0.0749 (15)
H8A −0.1084 −0.1072 0.0364 0.112*
H8B −0.1473 0.0507 0.0501 0.112*
H8C −0.2038 −0.0729 0.0848 0.112*
C9 −0.1911 (6) 0.3184 (4) 0.20140 (17) 0.0527 (11)
H9A −0.1738 0.3814 0.2286 0.063*
C10 0.1271 (5) 0.0052 (4) 0.42097 (16) 0.0481 (11)
C11 0.0129 (5) 0.0487 (5) 0.38285 (16) 0.0525 (11)
H11A 0.0415 0.1194 0.3604 0.063*
C12 −0.1412 (5) −0.0103 (4) 0.37763 (15) 0.0479 (11)
C13 −0.1806 (5) −0.1147 (4) 0.41042 (16) 0.0484 (11)
C14 −0.0672 (5) −0.1555 (4) 0.44870 (16) 0.0496 (11)
H14A −0.0973 −0.2246 0.4716 0.060*
C15 0.0923 (5) −0.0972 (4) 0.45466 (15) 0.0451 (10)
C16 −0.2379 (7) 0.1353 (6) 0.3082 (2) 0.0884 (18)
supporting information
sup-3 Acta Cryst. (2006). E62, o1946–o1947
H16B −0.1415 0.1148 0.2897 0.133*
H16C −0.2174 0.2209 0.3276 0.133*
C17 −0.3923 (6) −0.2650 (6) 0.43598 (19) 0.0751 (15)
H17A −0.5065 −0.2931 0.4255 0.113*
H17B −0.3879 −0.2230 0.4694 0.113*
H17C −0.3197 −0.3467 0.4369 0.113*
C18 0.2108 (5) −0.1445 (5) 0.49550 (17) 0.0516 (11)
H18A 0.3145 −0.0986 0.5019 0.062*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Br1 0.0507 (3) 0.0681 (3) 0.0717 (4) −0.0100 (2) 0.0005 (2) 0.0010 (3)
Br2 0.0573 (3) 0.0884 (4) 0.0688 (4) −0.0097 (3) −0.0086 (3) −0.0238 (3)
O1 0.0454 (19) 0.0646 (19) 0.070 (2) 0.0136 (16) −0.0073 (16) −0.0066 (17)
O2 0.052 (2) 0.073 (2) 0.062 (2) 0.0043 (16) −0.0151 (16) −0.0174 (18)
O3 0.056 (2) 0.112 (3) 0.076 (2) 0.024 (2) −0.0061 (18) −0.014 (2)
O4 0.0454 (19) 0.078 (2) 0.063 (2) −0.0087 (16) 0.0003 (15) 0.0030 (18)
O5 0.056 (2) 0.084 (2) 0.061 (2) −0.0068 (17) −0.0121 (17) 0.0069 (19)
O6 0.069 (2) 0.090 (3) 0.078 (2) −0.0052 (19) −0.0160 (19) 0.027 (2)
N1 0.046 (2) 0.062 (2) 0.069 (3) 0.0171 (19) 0.013 (2) 0.010 (2)
N2 0.052 (2) 0.063 (3) 0.051 (2) −0.001 (2) −0.0135 (19) 0.001 (2)
C1 0.043 (3) 0.049 (2) 0.047 (3) −0.009 (2) −0.002 (2) 0.002 (2)
C2 0.038 (3) 0.053 (3) 0.057 (3) −0.005 (2) −0.010 (2) 0.001 (2)
C3 0.040 (3) 0.046 (2) 0.051 (3) 0.000 (2) −0.003 (2) 0.008 (2)
C4 0.044 (3) 0.039 (2) 0.047 (3) −0.003 (2) −0.002 (2) 0.003 (2)
C5 0.032 (2) 0.048 (2) 0.050 (3) −0.0014 (19) −0.0067 (19) 0.012 (2)
C6 0.040 (2) 0.045 (2) 0.041 (2) −0.0029 (19) 0.0002 (19) 0.003 (2)
C7 0.043 (3) 0.093 (4) 0.076 (3) 0.012 (3) −0.007 (2) −0.001 (3)
C8 0.058 (3) 0.088 (4) 0.076 (4) 0.003 (3) −0.011 (3) −0.029 (3)
C9 0.053 (3) 0.054 (3) 0.050 (3) −0.003 (2) −0.004 (2) −0.001 (2)
C10 0.043 (3) 0.055 (3) 0.046 (3) 0.000 (2) 0.000 (2) −0.010 (2)
C11 0.049 (3) 0.056 (3) 0.052 (3) 0.001 (2) 0.004 (2) −0.001 (2)
C12 0.048 (3) 0.056 (3) 0.038 (2) 0.006 (2) −0.004 (2) −0.001 (2)
C13 0.038 (2) 0.056 (3) 0.051 (3) −0.002 (2) 0.002 (2) −0.013 (2)
C14 0.048 (3) 0.053 (3) 0.049 (3) 0.005 (2) 0.008 (2) −0.003 (2)
C15 0.044 (3) 0.047 (2) 0.044 (2) 0.001 (2) −0.001 (2) −0.007 (2)
C16 0.098 (5) 0.073 (4) 0.087 (4) −0.002 (3) −0.035 (3) 0.015 (3)
C17 0.054 (3) 0.096 (4) 0.076 (4) −0.023 (3) 0.008 (3) −0.011 (3)
C18 0.040 (3) 0.056 (3) 0.058 (3) −0.002 (2) 0.000 (2) −0.006 (2)
Geometric parameters (Å, º)
Br1—C10 1.913 (4) C6—C9 1.473 (6)
Br2—C1 1.903 (4) C7—H7A 0.9800
O1—C3 1.353 (5) C7—H7B 0.9800
O1—C7 1.436 (5) C7—H7C 0.9800
O2—C8 1.417 (5) C8—H8B 0.9800
O3—N1 1.370 (4) C8—H8C 0.9800
O3—H3A 0.8400 C9—H9A 0.9500
O4—C13 1.375 (5) C10—C11 1.381 (6)
O4—C17 1.410 (6) C10—C15 1.381 (6)
O5—C12 1.365 (5) C10—Br1 1.913 (4)
O5—C16 1.436 (6) C11—C12 1.366 (6)
O6—N2 1.401 (4) C11—H11A 0.9500
O6—H6A 0.8400 C12—C13 1.389 (6)
N1—C9 1.233 (5) C13—C14 1.373 (6)
N2—C18 1.239 (5) C14—C15 1.403 (6)
C1—C6 1.375 (5) C14—H14A 0.9500
C1—C2 1.388 (6) C15—C18 1.463 (6)
C1—Br2 1.903 (4) C16—H16A 0.9800
C2—C3 1.379 (6) C16—H16B 0.9800
C2—H2B 0.9500 C16—H16C 0.9800
C3—C4 1.406 (6) C17—H17A 0.9800
C4—C5 1.360 (6) C17—H17B 0.9800
C5—C6 1.398 (5) C17—H17C 0.9800
C5—H5A 0.9500 C18—H18A 0.9500
C3—O1—C7 117.8 (4) H8B—C8—H8C 109.5
C4—O2—C8 117.5 (3) N1—C9—C6 121.0 (4)
N1—O3—H3A 109.5 N1—C9—H9A 119.5
C13—O4—C17 117.8 (4) C6—C9—H9A 119.5
C12—O5—C16 118.3 (4) C11—C10—C15 122.6 (4)
N2—O6—H6A 109.5 C11—C10—Br1 116.2 (3)
C9—N1—O3 112.2 (4) C15—C10—Br1 121.2 (3)
C18—N2—O6 112.1 (4) C11—C10—Br1 116.2 (3)
C6—C1—C2 122.4 (4) C15—C10—Br1 121.2 (3)
C6—C1—Br2 121.1 (3) C12—C11—C10 119.7 (4)
C2—C1—Br2 116.5 (3) C12—C11—H11A 120.1
C6—C1—Br2 121.1 (3) C10—C11—H11A 120.1
C2—C1—Br2 116.5 (3) O5—C12—C11 125.6 (4)
C3—C2—C1 119.1 (4) O5—C12—C13 114.8 (4)
C3—C2—H2B 120.4 C11—C12—C13 119.5 (4)
C1—C2—H2B 120.4 C14—C13—O4 125.0 (4)
O1—C3—C2 125.6 (4) C14—C13—C12 120.3 (4)
O1—C3—C4 115.1 (4) O4—C13—C12 114.7 (4)
C2—C3—C4 119.3 (4) C13—C14—C15 121.3 (4)
C5—C4—O2 125.8 (4) C13—C14—H14A 119.4
C5—C4—C3 120.1 (4) C15—C14—H14A 119.4
O2—C4—C3 114.1 (4) C10—C15—C14 116.6 (4)
C4—C5—C6 121.6 (4) C10—C15—C18 123.6 (4)
C4—C5—H5A 119.2 C14—C15—C18 119.8 (4)
C6—C5—H5A 119.2 O5—C16—H16A 109.5
C1—C6—C5 117.4 (4) O5—C16—H16B 109.5
supporting information
sup-5 Acta Cryst. (2006). E62, o1946–o1947
C5—C6—C9 119.5 (4) O5—C16—H16C 109.5
O1—C7—H7A 109.5 H16A—C16—H16C 109.5
O1—C7—H7B 109.5 H16B—C16—H16C 109.5
H7A—C7—H7B 109.5 O4—C17—H17A 109.5
O1—C7—H7C 109.5 O4—C17—H17B 109.5
H7A—C7—H7C 109.5 H17A—C17—H17B 109.5
H7B—C7—H7C 109.5 O4—C17—H17C 109.5
O2—C8—H8A 109.5 H17A—C17—H17C 109.5
O2—C8—H8B 109.5 H17B—C17—H17C 109.5
H8A—C8—H8B 109.5 N2—C18—C15 119.9 (4)
O2—C8—H8C 109.5 N2—C18—H18A 120.0
H8A—C8—H8C 109.5 C15—C18—H18A 120.0
C6—C1—C2—C3 0.0 (6) C15—C10—C11—C12 0.1 (6)
Br2—C1—C2—C3 179.8 (3) Br1—C10—C11—C12 179.1 (3)
Br2—C1—C2—C3 179.8 (3) Br1—C10—C11—C12 179.1 (3)
C7—O1—C3—C2 −0.5 (6) C16—O5—C12—C11 −5.1 (6)
C7—O1—C3—C4 179.4 (4) C16—O5—C12—C13 176.0 (4)
C1—C2—C3—O1 179.1 (4) C10—C11—C12—O5 −179.6 (4)
C1—C2—C3—C4 −0.8 (6) C10—C11—C12—C13 −0.7 (6)
C8—O2—C4—C5 −3.9 (6) C17—O4—C13—C14 3.7 (6)
C8—O2—C4—C3 177.6 (4) C17—O4—C13—C12 −174.7 (4)
O1—C3—C4—C5 −178.5 (4) O5—C12—C13—C14 −179.2 (4)
C2—C3—C4—C5 1.4 (6) C11—C12—C13—C14 1.9 (6)
O1—C3—C4—O2 0.1 (5) O5—C12—C13—O4 −0.7 (5)
C2—C3—C4—O2 −180.0 (4) C11—C12—C13—O4 −179.7 (4)
O2—C4—C5—C6 −179.7 (4) O4—C13—C14—C15 179.4 (4)
C3—C4—C5—C6 −1.3 (6) C12—C13—C14—C15 −2.4 (6)
C2—C1—C6—C5 0.1 (6) C11—C10—C15—C14 −0.5 (6)
Br2—C1—C6—C5 −179.6 (3) Br1—C10—C15—C14 −179.4 (3)
Br2—C1—C6—C5 −179.6 (3) Br1—C10—C15—C14 −179.4 (3)
C2—C1—C6—C9 −179.2 (4) C11—C10—C15—C18 −179.7 (4)
Br2—C1—C6—C9 1.1 (6) Br1—C10—C15—C18 1.4 (5)
Br2—C1—C6—C9 1.1 (6) Br1—C10—C15—C18 1.4 (5)
C4—C5—C6—C1 0.5 (6) C13—C14—C15—C10 1.6 (6)
C4—C5—C6—C9 179.8 (4) C13—C14—C15—C18 −179.2 (4)
O3—N1—C9—C6 −180.0 (3) O6—N2—C18—C15 −179.0 (3)
C1—C6—C9—N1 −176.6 (4) C10—C15—C18—N2 −174.1 (4)
C5—C6—C9—N1 4.1 (6) C14—C15—C18—N2 6.8 (6)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
O3—H3A···O4i 0.84 2.36 3.098 (5) 147
O6—H6A···O1ii 0.84 2.19 2.942 (4) 150
O6—H6A···O2ii 0.84 2.33 3.038 (4) 142
