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Acta Crystallogr Sect E Struct Rep Online. 2009 February 1; 65(Pt 2): o241.
Published online 2009 January 8. doi:  10.1107/S1600536808044164
PMCID: PMC2968274

(E)-2-[(2-Amino-4,5-dibromo­phen­yl)imino­meth­yl]-6-methoxy­phenol

Abstract

The title compound, C14H12Br2N2O2, was prepared from the condensation of 4,5-dibromo-1,2-phenyl­enediamine and 2-hydr­oxy-3-methoxy­benzaldehyde in methanol. The N=C double bond shows a trans conformation and the dihedral angle between the aromatic ring planes is 5.9 (4)°. In the crystal structure, there are intra­molecular O—H(...)N and N—H(...)N and inter­molecular N—H(...)O hydrogen bonds, the latter resulting in inversion dimers.

Related literature

For related literature on the design of ligands for polynuclear coordination complexes with novel magnetic properties, see: Fernández et al. (2001 [triangle]); Pardo et al. (2003 [triangle]); Yu et al. (2007 [triangle]). For the synthesis and structure of a related compound, see: Xia et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o241-scheme1.jpg

Experimental

Crystal data

  • C14H12Br2N2O2
  • M r = 400.08
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o241-efi1.jpg
  • a = 6.9500 (4) Å
  • b = 7.4383 (4) Å
  • c = 14.7877 (10) Å
  • α = 100.351 (5)°
  • β = 97.218 (5)°
  • γ = 109.967 (3)°
  • V = 692.21 (8) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 5.86 mm−1
  • T = 292 (3) K
  • 0.50 × 0.40 × 0.22 mm

Data collection

  • Bruker SMART 1K CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.072, T max = 0.275
  • 6557 measured reflections
  • 3154 independent reflections
  • 2695 reflections with I > 2σ(I)
  • R int = 0.018

Refinement

  • R[F 2 > 2σ(F 2)] = 0.025
  • wR(F 2) = 0.071
  • S = 1.02
  • 3154 reflections
  • 190 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.60 e Å−3
  • Δρmin = −0.46 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808044164/hg2454sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808044164/hg2454Isup2.hkl

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

Acknowledgments

This work was supported by the Natural Science Foundation of China (grant No. 50873093).

supplementary crystallographic information

Comment

The design and synthesis of new ligands with the potential for forming polynuclear coordination complexes with novel magnetic properties is of current research interest (Pardo, et al., 2003; Yu, et al., 2007; Fernández,et al., 2001) and we report here the synthesis and crystal structure of the title complex (I).

The molecular structure of title compound is showing in Fig. 1. In the structure, there are intramolecular O—H···N, N—H···N and intermolecular N—H···O hydrogen bonds in the crystal lattice.

Experimental

The title compound was synthesized according to modified reported methods (Xia, et al., 2007). 1 mmol (265.9 mg) 4,5-dibromo-1,2-phenylenediamine and 1.1 mmol (167.4 mg) 2-hydroxy-3-methoxybenzaldehyde were dissolved in 30 ml solution of methanol, then refluxed for 2 h. The solution was cooled and filtered. Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation at room temperature for 10 days.

Refinement

All H atoms were placed in geometrically calculated positions with C—H = 0.96 Å for methyl H atoms, C—H = 0.93 Å for aromatic H atoms and 0.82 Å for N—H. H atoms and were refined isotropic with Uiso(H) = 1.2Ueq(C) of parent atom using a riding model. The H atom of the hydroxy group was located from difference maps and refined with a distance restraint O—H = 0.82 (1) Å. Uiso(H) = 1.2Ueq(O).

Figures

Fig. 1.
A view of complex (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
Fig. 2.
The crystal packing of title compound, viewed along the a axis. Hydrogen bonds are shown as dashed lines.

Crystal data

C14H12Br2N2O2Z = 2
Mr = 400.08F(000) = 392
Triclinic, P1Dx = 1.919 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.9500 (4) ÅCell parameters from 3154 reflections
b = 7.4383 (4) Åθ = 1.4–27.6°
c = 14.7877 (10) ŵ = 5.86 mm1
α = 100.351 (5)°T = 292 K
β = 97.218 (5)°Block, colourless
γ = 109.967 (3)°0.50 × 0.40 × 0.22 mm
V = 692.21 (8) Å3

Data collection

Bruker SMART 1K CCD area-detector diffractometer3154 independent reflections
Radiation source: fine-focus sealed tube2695 reflections with I > 2σ(I)
graphiteRint = 0.018
[var phi] and ω scansθmax = 27.6°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2000)h = −9→8
Tmin = 0.072, Tmax = 0.275k = −9→9
6557 measured reflectionsl = −12→19

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.025H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.071w = 1/[σ2(Fo2) + (0.0379P)2 + 0.3429P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
3154 reflectionsΔρmax = 0.60 e Å3
190 parametersΔρmin = −0.46 e Å3
0 restraintsExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0093 (11)

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
Br10.04544 (4)0.75243 (4)0.476886 (17)0.05025 (11)
Br20.48830 (4)0.77615 (4)0.397735 (17)0.04846 (10)
O2−0.2559 (2)0.1156 (3)−0.08390 (11)0.0429 (4)
H2−0.22480.1805−0.02950.064*
O1−0.3008 (3)−0.0863 (3)−0.25537 (11)0.0458 (4)
N1−0.0125 (3)0.3290 (3)0.07626 (12)0.0310 (4)
C90.0126 (3)0.4297 (3)0.17005 (14)0.0287 (4)
C50.2944 (3)0.2066 (4)−0.09082 (17)0.0378 (5)
H50.42650.2712−0.05250.045*
N2−0.3662 (3)0.2994 (3)0.14823 (17)0.0429 (5)
C2−0.0994 (3)0.0097 (3)−0.20552 (14)0.0318 (4)
C80.1432 (3)0.3179 (3)0.04022 (15)0.0334 (5)
H80.27700.37940.07710.040*
C14−0.1716 (3)0.4098 (3)0.20455 (15)0.0314 (4)
C60.1178 (3)0.2131 (3)−0.05579 (14)0.0298 (4)
C100.2057 (3)0.5418 (3)0.22926 (15)0.0316 (4)
H100.32740.55410.20670.038*
C7−0.0805 (3)0.1144 (3)−0.11378 (14)0.0298 (4)
C13−0.1544 (3)0.5092 (3)0.29647 (16)0.0351 (5)
H13−0.27500.50030.31950.042*
C30.0768 (4)0.0078 (3)−0.23831 (16)0.0375 (5)
H30.0639−0.0598−0.29950.045*
C1−0.3285 (4)−0.1801 (4)−0.35196 (16)0.0471 (6)
H1A−0.4751−0.2415−0.37920.071*
H1B−0.2670−0.2781−0.35660.071*
H1C−0.2621−0.0836−0.38490.071*
C110.2199 (3)0.6352 (3)0.32091 (15)0.0320 (4)
C120.0382 (4)0.6204 (3)0.35391 (15)0.0329 (4)
C40.2745 (4)0.1064 (4)−0.18074 (17)0.0403 (5)
H40.39270.1039−0.20350.048*
H2A−0.360 (4)0.212 (4)0.105 (2)0.043 (7)*
H2B−0.455 (5)0.251 (4)0.177 (2)0.049 (8)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.05665 (18)0.04947 (16)0.03545 (15)0.01522 (13)0.01513 (11)−0.00727 (10)
Br20.03535 (14)0.06002 (18)0.03276 (14)0.01257 (11)−0.00551 (10)−0.01218 (11)
O20.0239 (7)0.0630 (11)0.0291 (8)0.0100 (7)0.0034 (6)−0.0066 (7)
O10.0331 (8)0.0600 (11)0.0258 (8)0.0038 (8)0.0011 (6)−0.0050 (7)
N10.0293 (9)0.0321 (9)0.0252 (8)0.0078 (7)0.0017 (7)0.0010 (7)
C90.0290 (10)0.0287 (9)0.0243 (9)0.0093 (8)0.0021 (8)0.0015 (8)
C50.0263 (10)0.0465 (12)0.0367 (12)0.0122 (10)0.0043 (9)0.0047 (10)
N20.0267 (10)0.0477 (12)0.0423 (12)0.0055 (9)0.0046 (9)−0.0001 (10)
C20.0313 (10)0.0340 (10)0.0246 (10)0.0078 (9)0.0036 (8)0.0040 (8)
C80.0266 (10)0.0377 (11)0.0286 (11)0.0094 (9)−0.0016 (8)−0.0001 (8)
C140.0290 (10)0.0294 (10)0.0332 (11)0.0093 (8)0.0040 (8)0.0059 (8)
C60.0273 (10)0.0325 (10)0.0270 (10)0.0101 (8)0.0031 (8)0.0042 (8)
C100.0279 (10)0.0339 (10)0.0285 (10)0.0103 (9)0.0042 (8)0.0003 (8)
C70.0264 (10)0.0346 (10)0.0263 (10)0.0099 (8)0.0052 (8)0.0049 (8)
C130.0305 (11)0.0338 (10)0.0389 (12)0.0106 (9)0.0108 (9)0.0039 (9)
C30.0444 (13)0.0399 (12)0.0285 (11)0.0164 (10)0.0110 (9)0.0048 (9)
C10.0529 (15)0.0477 (14)0.0236 (11)0.0061 (12)−0.0004 (10)−0.0025 (10)
C110.0305 (10)0.0312 (10)0.0275 (10)0.0095 (8)−0.0008 (8)−0.0011 (8)
C120.0396 (11)0.0299 (10)0.0275 (10)0.0137 (9)0.0075 (8)0.0010 (8)
C40.0329 (11)0.0523 (14)0.0405 (13)0.0196 (11)0.0141 (10)0.0107 (10)

Geometric parameters (Å, °)

Br1—C121.891 (2)C2—C71.404 (3)
Br2—C111.890 (2)C8—C61.449 (3)
O2—C71.350 (3)C8—H80.9300
O2—H20.8200C14—C131.395 (3)
O1—C21.372 (3)C6—C71.400 (3)
O1—C11.430 (3)C10—C111.382 (3)
N1—C81.285 (3)C10—H100.9300
N1—C91.411 (3)C13—C121.379 (3)
C9—C101.393 (3)C13—H130.9300
C9—C141.408 (3)C3—C41.394 (3)
C5—C41.368 (3)C3—H30.9300
C5—C61.403 (3)C1—H1A0.9600
C5—H50.9300C1—H1B0.9600
N2—C141.382 (3)C1—H1C0.9600
N2—H2A0.84 (3)C11—C121.388 (3)
N2—H2B0.81 (3)C4—H40.9300
C2—C31.376 (3)
C7—O2—H2109.5C9—C10—H10119.3
C2—O1—C1117.15 (19)O2—C7—C6121.88 (18)
C8—N1—C9122.27 (18)O2—C7—C2118.60 (18)
C10—C9—C14119.32 (18)C6—C7—C2119.52 (19)
C10—C9—N1124.08 (19)C12—C13—C14121.3 (2)
C14—C9—N1116.59 (18)C12—C13—H13119.4
C4—C5—C6120.7 (2)C14—C13—H13119.4
C4—C5—H5119.6C2—C3—C4120.7 (2)
C6—C5—H5119.6C2—C3—H3119.7
C14—N2—H2A111.2 (19)C4—C3—H3119.7
C14—N2—H2B114 (2)O1—C1—H1A109.5
H2A—N2—H2B111 (3)O1—C1—H1B109.5
O1—C2—C3125.3 (2)H1A—C1—H1B109.5
O1—C2—C7114.79 (19)O1—C1—H1C109.5
C3—C2—C7119.9 (2)H1A—C1—H1C109.5
N1—C8—C6122.43 (19)H1B—C1—H1C109.5
N1—C8—H8118.8C10—C11—C12119.28 (19)
C6—C8—H8118.8C10—C11—Br2118.48 (16)
N2—C14—C13120.2 (2)C12—C11—Br2122.23 (16)
N2—C14—C9121.2 (2)C13—C12—C11120.21 (19)
C13—C14—C9118.57 (19)C13—C12—Br1118.15 (16)
C7—C6—C5119.27 (19)C11—C12—Br1121.63 (16)
C7—C6—C8121.15 (19)C5—C4—C3119.9 (2)
C5—C6—C8119.57 (19)C5—C4—H4120.0
C11—C10—C9121.3 (2)C3—C4—H4120.0
C11—C10—H10119.3

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2···N10.821.882.608 (2)147
N2—H2A···N10.84 (3)2.39 (3)2.756 (3)107 (2)
N2—H2B···O1i0.81 (3)2.30 (3)3.114 (3)174.19

Symmetry codes: (i) −x−1, −y, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2454).

References

  • Bruker (2000). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Fernández, I., Ruiz, R., Faus, J., Julve, M., Lloret, F., Cano, J., Ottenwaelder, X., Journaux, Y. & Muñoz, C. (2001). Angew. Chem. Int. Ed.40, 3039–3042. [PubMed]
  • Pardo, E., Faus, J., Julve, M., Lloret, F., Muñoz, C., Cano, J., Ottenwaelder, X., Journaux, Y., Carrasco, R., Blay, G., Fernàndez, I. & Ruiz-Garcìa, R. (2003). J. Am. Chem. Soc.125, 10770–10771. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Xia, H.-T., Liu, Y.-F., Yang, S.-P. & Wang, D.-Q. (2007). Acta Cryst. E63, o40–o41.
  • Yu, M.-M., Ni, Z.-H., Zhao, C.-C., Cui, A.-L. & Kou, H.-Z. (2007). Eur. J. Inorg. Chem. pp. 5670–5676.

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