organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

4,5-Di­bromo­phthalimide forms two centrosymmetric dimers, one linked by C—H⋯O hydrogen bonds and one by N—H⋯O hydrogen bonds

aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 30 January 2007; accepted 31 January 2007; online 17 February 2007)

In the title compound [also called 5,6-dibromo­isoindole-1,3(2H)-dione], C8H3Br2NO2, there are two planar mol­ecules in the asymmetric unit. They both form inversion dimers, one via N—H⋯O links and one via short near-linear C—H⋯O links. The dimers are then linked into chains by further N—H⋯O hydrogen bonds.

Comment

The title compound, (I)[link], was prepared as an inter­mediate en route to potential novel chromophores. This compound was first reported by Hanack & Stihler (2000[Hanack, M. & Stihler, P. (2000). Eur. J. Org. Chem. pp. 303-311.]).

[Scheme 1]

All the geometrical parameters for (I)[link] (Fig. 1[link]) lie within their expected ranges (Allen et al., 1995[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1995). International Tables for Crystallography, Vol. C, Section 9.5, pp. 685-706. Dordrecht: Kluwer.]). There are two mol­ecules in the asymmetric unit of (I)[link]; both are essentially flat, with an r.m.s. deviation from the mean plane of 0.017 Å for the mol­ecule containing C1 and 0.012 Å for the mol­ecule containing C9. The dihedral angle between the two mol­ecules is 7.96 (16)°. The geometries of the six- and five-membered rings in (I)[link] are not significantly different from those in phthalimide, (II) (Zakaria et al., 2002[Zakaria, C. M., Low, J. N. & Glidewell, C. (2002). Acta Cryst. C58, o9-o10.]), with the exception of the C1—C2 and C9—C10 bonds [mean = 1.414 (9) Å], which are slightly longer than the equivalent bond of 1.387 (2) Å in (II), perhaps due to steric repulsion between the ortho Br atoms.

The crystal packing (Fig. 2[link]) for (I)[link] results in hydrogen-bonded inversion dimers for both mol­ecules (Table 1[link]). For the mol­ecule containing C1, two strong near-linear C6—H6⋯O2i (see Table 1[link] for symmetry codes) inter­actions are the linking bonds. The H⋯O separation of 2.36 Å implies a strong inter­action (Taylor & Kennard, 1982[Taylor, R. & Kennard, O. (1982). J. Am. Chem. Soc. 104, 5063-5070.]; Desiraju & Steiner, 1999[Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond in Structural Chemistry and Biology, p. 38. Oxford University Press.]). An R22(10) supra­molecular ring motif (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) arises. For the C9 species, two more conventional, `hard', N—H⋯O bonds fuse the dimeric pair of mol­ecules together. The supra­molecular motif that results is an R22(8) loop. Adjacent C1 and C9 dimers are then linked by the N1—H1⋯O4 bond, resulting in mol­ecular tapes propagating in [210].

A PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]) analysis of (I)[link] identified two short Br⋯O inter­actions, compared with the Bondi (1964[Bondi, A. (1964). J. Phys. Chem. 68, 441-451.]) van der Waals separation of 3.37 Å for these atoms. The close Br1⋯O3iii separation of 3.209 (6) Å probably correlates with the N1—H1⋯O4 hydrogen bond linking the mol­ecules into chains (see Fig. 2[link]). The significance of the second short contact, Br3⋯O1iv [symmetry code: (iv) −x, 1 − y, −z] of 3.117 (6) Å, which occurs between adjacent [110] chains, is less obvious. A short Br4⋯Br2iv contact of 3.59017 (14) Å (the contact radius is 3.7 Å) is also apparent. Any ππ stacking effects in (I)[link] must be exceedingly weak, with a minimum ring-centroid separation of 4.12 Å.

The crystal structure of (II) with one asymmetric mol­ecule (Zakaria et al., 2002[Zakaria, C. M., Low, J. N. & Glidewell, C. (2002). Acta Cryst. C58, o9-o10.]) also shows chains of mol­ecules linked by N—H⋯O and C—H⋯O inter­molecular inter­actions, but the C—H⋯O bonds in (II) (mean H⋯O = 2.55 Å) are much weaker than those in (I)[link]. Although inversion-generated loops featuring C—H⋯O and N—H⋯O inter­actions are present, the chain and overall structures of (I)[link] and (II) are quite different.

[Figure 1]
Figure 1
A view of (I)[link], showing 50% probability displacement ellipsoids (H atoms are drawn as small spheres of arbitrary radii). The N—H⋯O hydrogen bond is shown as a double-dashed line. The C14—H14 group appears to be well aligned to form a C—H⋯O inter­action to O1 (C—H⋯O = 174°), but the H⋯O separation of 2.80 Å is longer than the Bondi (1964[Bondi, A. (1964). J. Phys. Chem. 68, 441-451.]) contact distance of 2.72 Å, suggesting that, at best, this is a very weak inter­action.
[Figure 2]
Figure 2
Detail of the packing of (I)[link], showing part of a [110] tape of dimers linked by C—H⋯O and N—H⋯O hydrogen bonds (40% probability displacement ellipsoids; H atoms involved in hydrogen bonding are drawn as small spheres of arbitrary radii and other H atoms have been omitted). The hydrogen bonds are shown as double-dashed lines. The short Br1⋯O3iii separation of 3.209 (6) Å is discussed in the Comment. [Symmetry codes as in Table 1[link]; additionally (iii) x − 2, y − 1, z.]

Experimental

Rather than the published method of Hanack & Stihler (2000[Hanack, M. & Stihler, P. (2000). Eur. J. Org. Chem. pp. 303-311.]), a modified Wohrle (Wohrle et al., 1993[Wohrle, D., Eskes, M., Shigehara, K. & Yamada, A. (1993). Synthesis (Stuttgart), pp. 194-196.]) synthesis was used to prepare (I)[link]. Dibromo­phthalic anhydride and excess formamide were heated with stirring, at 413 K, without solvent for 5 h. The solution was cooled and filtered, and the residue was washed with cold water. The crude product was recrystallized (50:50 v/v, EtOH–H2O) and dried overnight in a desiccator (P2O5). Slow crystallization from dichloro­methane yielded colourless blocks of (I)[link] (yield 66%; m.p. 508–513 K). Analysis found: C 31.4, H 0.9, N 4.4, Br 52.1%; C8H3Br2NO2 requires: C 31.5, H 1.0, N 4.6, Br 52.4%

Crystal data
  • C8H3Br2NO2

  • Mr = 304.94

  • Triclinic, [P \overline 1]

  • a = 6.7725 (6) Å

  • b = 11.0759 (10) Å

  • c = 12.3543 (10) Å

  • α = 101.734 (2)°

  • β = 91.725 (2)°

  • γ = 97.031 (2)°

  • V = 899.08 (14) Å3

  • Z = 4

  • Dx = 2.253 Mg m−3

  • Mo Kα radiation

  • μ = 8.98 mm−1

  • T = 293 (2) K

  • Block, colourless

  • 0.34 × 0.29 × 0.11 mm

Data collection
  • Bruker SMART1000 CCD diffractometer

  • ω scans

  • Absorption correction: multi-scan (SADABS; Bruker, 1999[Bruker (1999). SMART (Version 5.624), SAINT (Version 6.02A) and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.076, Tmax = 0.373

  • 5395 measured reflections

  • 3154 independent reflections

  • 1994 reflections with I > 2σ(I)

  • Rint = 0.034

  • θmax = 25.1°

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.047

  • wR(F2) = 0.116

  • S = 0.91

  • 3154 reflections

  • 235 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0694P)2] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.96 e Å−3

  • Δρmin = −0.68 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C6—H6⋯O2i 0.93 2.36 3.274 (9) 167
N1—H1⋯O4 0.86 1.95 2.793 (8) 167
N2—H2⋯O3ii 0.86 2.04 2.902 (8) 175
Symmetry codes: (i) -x, -y, -z+1; (ii) -x+2, -y+1, -z+1.

All H atoms were placed in calculated positions, with C—H distances of 0.93 Å and N—H distances of 0.86 Å, and refined as riding, with Uiso(H) values of 1.2Ueq(carrier).

Data collection: SMART (Bruker, 1999[Bruker (1999). SMART (Version 5.624), SAINT (Version 6.02A) and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1999[Bruker (1999). SMART (Version 5.624), SAINT (Version 6.02A) and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

The title compound, (I), was prepared as an intermediate en route to potential novel chromophores. This compound was first reported by Hanack & Stihler (2000).

All the geometrical parameters for (I) (Fig. 1) lie within their expected ranges (Allen et al., 1995). There are two molecules in the asymmetric unit of (I); both are essentially flat, with r.m.s. deviations from the mean plane of 0.017 Å for the molecule containing C1 and 0.012 Å for the molecule containing C9. The dihedral angle between the two molecules is 7.96 (16)°. The geometries of the six- and five-membered rings in (I) are not significantly different from those in phthalimide, C8H5NO2, (II) (Zakaria et al., 2002), with the exception of the C1—C2 and C9—C10 bonds [mean = 1.414 (9) Å], which are slightly longer than the equivalent bond of 1.387 (2) Å in (II), perhaps due to steric repulsion between the ortho-Br atoms.

The crystal packing (Fig. 2) for (I) results in hydrogen-bonded inversion dimers for both molecules (Table 1). For the C1 molecule, two strong, near-linear C6—H6···O2i (see Table 1 for symmetry codes) interactions are the linking bonds. The H···O separation of 2.36 Å implies a strong interaction (Taylor & Kennard; Desiraju & Steiner, 1999). An R22(10) supramolecular ring motif (Bernstein et al., 1995) arises. For the C9 species, two more conventional, `hard', N—H···O bonds fuse the dimeric pair of molecules together. The supramolecular motif that results is an R22(8) loop. Adjacent C1 and C9 dimers are then linked by the N1—H1···O4 bond, to result in molecular tapes propagating in [210].

A PLATON (Spek, 2003) analysis of (I) identified two short Br···O interactions in (I), compared with the Bondi (1964) van der Waals separation of 3.37 Å for these atoms. The close Br1···O3iii separation of 3.209 (6) Å probably correlates with the N1—H1···O4 hydrogen bond linking the molecules into chains (see Fig. 2). The significance of the second short contact, Br3···O1iv [symmetry code: (iv) -x, 1 - y, -z] of 3.117 (6) Å, which occurs between adjacent [110] chains, is less obvious. A short Br4···Br2iv contact of 3.59017 (14) Å (the contact radius is 3.7 Å) is also apparent. Any ππ stacking effects in (I) must be exceedingly weak, with a minimum ring-centroid separation of 4.12 Å.

The crystal structure of (II) with one asymmetric molecule (Zakaria et al., 2002) also shows chains of molecules linked by N—H···O and C—H···O intermolecular interactions, but the C—H···O bonds in (II) (mean H···O = 2.55 Å) are much weaker than those in (I). Although inversion-generated loops featuring C—H···O and N—H···O interactions are present, the chain and overall structures of (I) and (II) are quite different.

Related literature top

For related literature, see: Allen et al. (1995); Bernstein et al. (1995); Bondi (1964); Desiraju & Steiner (1999); Hanack & Stihler (2000); Spek (2003); Wohrle et al. (1993); Zakaria (2002).

Experimental top

Rather than the published method of Hanack & Stihler (2000), a modified Wohrle (Wohrle et al., 1993) synthesis was used to prepare (I). Dibromophthalic anhydride and excess formamide were heated with stirring, at 413 K without solvent for 5 h. The solution was cooled and filtered, and the residue was washed with cold water. The crude product was recrystallized (50:50 v/v EtOH/H2O) and dried overnight in a desiccator (P2O5). Slow crystallization from dichloromethane yielded colourless blocks of (I) (yield 66%, m.p. 508–513 K). Analysis found: C 31.4, H 0.9, N 4.4, Br 52.1%; C8H3Br2NO2 requires: C 31.5, H 1.0, N 4.6, Br 52.4%

Refinement top

All H atoms were placed in calculated positions, with C—H distances of 0.93 Å and N—H of 0.86 Å, and refined as riding with Uiso(H) values of 1.2Ueq(carrier).

Computing details top

Data collection: SMART (Bruker, 1999); 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: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of (I), showing 50% probability displacement ellipsoids (H atoms are drawn as small spheres of arbitrary radii). The N—H···O hydrogen bond is shown as a double-dashed line. The C14/H14 grouping appears to be well aligned to form a C—H···O interaction to O1 (C—H···O = 174°), but the H···O separation of 2.80 Å is longer than the Bondi (1964) contact distance of 2.72 Å, suggesting that, at best, this is a very weak interaction.
[Figure 2] Fig. 2. Detail of the packing of (I), showing part of a [110] tape of dimers linked by C—H···O and N—H···O hydrogen bonds (40% probability displacement ellipsoids; H atoms involved in hydrogen bonding are drawn as small spheres of arbitrary radii and other H atoms have been omitted). The hydrogen bonds are shown as a double-dashed lines. [Symmetry codes as in Table 1; additionally (iii) x - 2, y - 1, z.] The short Br1···O3iii separation of 3.209 (6) Å is discussed in the text.
4,5-Dibromophthalimide top
Crystal data top
C8H3Br2NO2Z = 4
Mr = 304.94F(000) = 576
Triclinic, P1Dx = 2.253 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.7725 (6) ÅCell parameters from 1802 reflections
b = 11.0759 (10) Åθ = 2.3–25.0°
c = 12.3543 (10) ŵ = 8.98 mm1
α = 101.734 (2)°T = 293 K
β = 91.725 (2)°Block, colourless
γ = 97.031 (2)°0.34 × 0.29 × 0.11 mm
V = 899.08 (14) Å3
Data collection top
Bruker SMART1000 CCD
diffractometer
3154 independent reflections
Radiation source: fine-focus sealed tube1994 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
ω scansθmax = 25.1°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
h = 78
Tmin = 0.076, Tmax = 0.373k = 1313
5395 measured reflectionsl = 1413
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 0.91 w = 1/[σ2(Fo2) + (0.0694P)2]
where P = (Fo2 + 2Fc2)/3
3154 reflections(Δ/σ)max < 0.001
235 parametersΔρmax = 0.96 e Å3
0 restraintsΔρmin = 0.68 e Å3
Crystal data top
C8H3Br2NO2γ = 97.031 (2)°
Mr = 304.94V = 899.08 (14) Å3
Triclinic, P1Z = 4
a = 6.7725 (6) ÅMo Kα radiation
b = 11.0759 (10) ŵ = 8.98 mm1
c = 12.3543 (10) ÅT = 293 K
α = 101.734 (2)°0.34 × 0.29 × 0.11 mm
β = 91.725 (2)°
Data collection top
Bruker SMART1000 CCD
diffractometer
3154 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
1994 reflections with I > 2σ(I)
Tmin = 0.076, Tmax = 0.373Rint = 0.034
5395 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.116H-atom parameters constrained
S = 0.91Δρmax = 0.96 e Å3
3154 reflectionsΔρmin = 0.68 e Å3
235 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
xyzUiso*/Ueq
C10.4841 (11)0.0248 (6)0.3083 (6)0.0425 (18)
C20.5376 (10)0.0335 (6)0.2219 (6)0.0383 (17)
C30.4073 (10)0.1283 (6)0.1934 (6)0.0424 (18)
H30.43980.16710.13650.051*
C40.2286 (10)0.1612 (6)0.2539 (6)0.0388 (17)
C50.1778 (10)0.1050 (6)0.3398 (6)0.0404 (18)
C60.3043 (11)0.0101 (6)0.3655 (6)0.0425 (18)
H60.26810.02990.42090.051*
C70.0588 (10)0.2612 (7)0.2477 (7)0.0423 (18)
C80.0218 (11)0.1638 (7)0.3877 (7)0.050 (2)
N10.0793 (9)0.2561 (6)0.3295 (6)0.0505 (17)
H10.19000.30490.34340.061*
O10.0453 (8)0.3337 (5)0.1853 (5)0.0581 (15)
O20.1198 (8)0.1444 (5)0.4647 (5)0.0705 (18)
Br10.66137 (12)0.15287 (7)0.34651 (7)0.0544 (3)
Br20.78341 (11)0.01716 (8)0.13986 (8)0.0585 (3)
C90.4778 (10)0.6184 (6)0.1295 (6)0.0389 (17)
C100.6681 (10)0.6881 (7)0.1340 (6)0.0402 (18)
C110.8177 (10)0.6807 (7)0.2100 (6)0.0431 (19)
H110.94220.72760.21330.052*
C120.7740 (10)0.6000 (6)0.2816 (6)0.0387 (17)
C130.5862 (9)0.5321 (6)0.2781 (6)0.0358 (17)
C140.4366 (10)0.5401 (6)0.2027 (6)0.0377 (17)
H140.31160.49420.20100.045*
C150.9006 (10)0.5710 (7)0.3709 (6)0.0408 (18)
C160.5893 (10)0.4590 (7)0.3646 (6)0.0398 (18)
N20.7780 (8)0.4867 (5)0.4159 (5)0.0453 (16)
H20.81550.45500.46990.054*
O31.0725 (7)0.6080 (5)0.3995 (5)0.0523 (15)
O40.4584 (7)0.3870 (5)0.3914 (5)0.0578 (16)
Br30.27695 (11)0.62958 (8)0.02499 (7)0.0522 (3)
Br40.72908 (12)0.79362 (9)0.03440 (8)0.0620 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.047 (4)0.036 (4)0.045 (5)0.001 (3)0.007 (4)0.013 (4)
C20.036 (4)0.040 (4)0.036 (4)0.000 (3)0.008 (3)0.004 (3)
C30.044 (4)0.038 (4)0.047 (5)0.001 (3)0.002 (4)0.015 (4)
C40.035 (4)0.036 (4)0.047 (5)0.001 (3)0.001 (3)0.018 (3)
C50.038 (4)0.039 (4)0.046 (5)0.003 (3)0.002 (4)0.014 (4)
C60.056 (5)0.039 (4)0.037 (5)0.009 (3)0.003 (4)0.017 (4)
C70.035 (4)0.041 (4)0.052 (5)0.005 (3)0.004 (4)0.014 (4)
C80.046 (4)0.056 (5)0.048 (5)0.002 (4)0.012 (4)0.017 (4)
N10.038 (3)0.050 (4)0.063 (5)0.009 (3)0.013 (3)0.023 (3)
O10.053 (3)0.058 (4)0.067 (4)0.006 (3)0.009 (3)0.033 (3)
O20.062 (4)0.072 (4)0.078 (4)0.012 (3)0.038 (3)0.036 (3)
Br10.0585 (5)0.0480 (5)0.0556 (6)0.0101 (4)0.0080 (4)0.0177 (4)
Br20.0422 (5)0.0593 (5)0.0720 (7)0.0102 (4)0.0153 (4)0.0217 (4)
C90.034 (4)0.046 (4)0.035 (4)0.013 (3)0.008 (3)0.003 (3)
C100.035 (4)0.051 (4)0.040 (5)0.008 (3)0.004 (3)0.021 (4)
C110.032 (4)0.055 (5)0.048 (5)0.003 (3)0.001 (4)0.026 (4)
C120.037 (4)0.043 (4)0.037 (4)0.002 (3)0.001 (3)0.014 (3)
C130.031 (4)0.047 (4)0.033 (4)0.004 (3)0.004 (3)0.017 (3)
C140.028 (4)0.044 (4)0.038 (4)0.001 (3)0.004 (3)0.006 (3)
C150.028 (4)0.054 (5)0.043 (5)0.003 (3)0.000 (3)0.018 (4)
C160.030 (4)0.049 (4)0.041 (5)0.002 (3)0.000 (3)0.016 (4)
N20.029 (3)0.053 (4)0.061 (4)0.002 (3)0.000 (3)0.035 (3)
O30.032 (3)0.069 (4)0.063 (4)0.009 (2)0.007 (3)0.040 (3)
O40.038 (3)0.064 (4)0.075 (4)0.014 (3)0.003 (3)0.035 (3)
Br30.0436 (4)0.0630 (5)0.0515 (5)0.0128 (4)0.0127 (4)0.0143 (4)
Br40.0525 (5)0.0815 (6)0.0616 (6)0.0002 (4)0.0061 (4)0.0437 (5)
Geometric parameters (Å, º) top
C1—C61.361 (10)C9—C141.387 (10)
C1—C21.415 (10)C9—C101.412 (9)
C1—Br11.888 (7)C9—Br31.880 (6)
C2—C31.395 (10)C10—C111.381 (9)
C2—Br21.884 (7)C10—Br41.884 (7)
C3—C41.372 (9)C11—C121.393 (9)
C3—H30.9300C11—H110.9300
C4—C51.390 (9)C12—C131.391 (9)
C4—C71.511 (9)C12—C151.487 (9)
C5—C61.368 (10)C13—C141.379 (9)
C5—C81.477 (10)C13—C161.467 (9)
C6—H60.9300C14—H140.9300
C7—O11.220 (8)C15—O31.203 (8)
C7—N11.370 (9)C15—N21.385 (9)
C8—O21.213 (9)C16—O41.218 (8)
C8—N11.390 (9)C16—N21.380 (8)
N1—H10.8600N2—H20.8600
C6—C1—C2120.8 (6)C14—C9—C10120.1 (6)
C6—C1—Br1118.7 (5)C14—C9—Br3118.9 (5)
C2—C1—Br1120.5 (6)C10—C9—Br3121.0 (5)
C3—C2—C1120.7 (7)C11—C10—C9121.8 (6)
C3—C2—Br2118.2 (5)C11—C10—Br4117.3 (5)
C1—C2—Br2121.1 (5)C9—C10—Br4121.0 (5)
C4—C3—C2116.5 (6)C10—C11—C12117.1 (7)
C4—C3—H3121.8C10—C11—H11121.4
C2—C3—H3121.8C12—C11—H11121.4
C3—C4—C5122.7 (6)C13—C12—C11121.3 (6)
C3—C4—C7130.2 (6)C13—C12—C15108.6 (6)
C5—C4—C7107.1 (6)C11—C12—C15130.2 (6)
C6—C5—C4120.5 (7)C14—C13—C12121.6 (6)
C6—C5—C8131.0 (7)C14—C13—C16131.0 (6)
C4—C5—C8108.4 (6)C12—C13—C16107.4 (6)
C1—C6—C5118.8 (6)C13—C14—C9118.1 (6)
C1—C6—H6120.6C13—C14—H14120.9
C5—C6—H6120.6C9—C14—H14120.9
O1—C7—N1126.1 (7)O3—C15—N2125.5 (6)
O1—C7—C4128.3 (6)O3—C15—C12129.7 (6)
N1—C7—C4105.6 (6)N2—C15—C12104.8 (5)
O2—C8—N1124.0 (7)O4—C16—N2123.4 (6)
O2—C8—C5130.0 (7)O4—C16—C13130.1 (6)
N1—C8—C5105.9 (6)N2—C16—C13106.5 (5)
C7—N1—C8113.0 (6)C16—N2—C15112.7 (5)
C7—N1—H1123.5C16—N2—H2123.6
C8—N1—H1123.5C15—N2—H2123.6
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O2i0.932.363.274 (9)167
N1—H1···O40.861.952.793 (8)167
N2—H2···O3ii0.862.042.902 (8)175
Symmetry codes: (i) x, y, z+1; (ii) x+2, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC8H3Br2NO2
Mr304.94
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)6.7725 (6), 11.0759 (10), 12.3543 (10)
α, β, γ (°)101.734 (2), 91.725 (2), 97.031 (2)
V3)899.08 (14)
Z4
Radiation typeMo Kα
µ (mm1)8.98
Crystal size (mm)0.34 × 0.29 × 0.11
Data collection
DiffractometerBruker SMART1000 CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.076, 0.373
No. of measured, independent and
observed [I > 2σ(I)] reflections
5395, 3154, 1994
Rint0.034
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.116, 0.91
No. of reflections3154
No. of parameters235
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.96, 0.68

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O2i0.932.363.274 (9)167
N1—H1···O40.861.952.793 (8)167
N2—H2···O3ii0.862.042.902 (8)175
Symmetry codes: (i) x, y, z+1; (ii) x+2, y+1, z+1.
 

Acknowledgements

The authors thank M. John Plater for helpful discussions.

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1995). International Tables for Crystallography, Vol. C, Section 9.5, pp. 685–706. Dordrecht: Kluwer.  Google Scholar
First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
First citationBondi, A. (1964). J. Phys. Chem. 68, 441–451.  CrossRef CAS Web of Science Google Scholar
First citationBruker (1999). SMART (Version 5.624), SAINT (Version 6.02A) and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationDesiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond in Structural Chemistry and Biology, p. 38. Oxford University Press.  Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationHanack, M. & Stihler, P. (2000). Eur. J. Org. Chem. pp. 303–311.  CrossRef Google Scholar
First citationSheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.  Google Scholar
First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationTaylor, R. & Kennard, O. (1982). J. Am. Chem. Soc. 104, 5063–5070.  CrossRef CAS Web of Science Google Scholar
First citationWohrle, D., Eskes, M., Shigehara, K. & Yamada, A. (1993). Synthesis (Stuttgart), pp. 194–196.  Google Scholar
First citationZakaria, C. M., Low, J. N. & Glidewell, C. (2002). Acta Cryst. C58, o9–o10.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds