Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039049/hb2505sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039049/hb2505Isup2.hkl |
CCDC reference: 660261
Key indicators
- Single-crystal X-ray study
- T = 153 K
- Mean (C-C) = 0.008 Å
- R factor = 0.060
- wR factor = 0.160
- Data-to-parameter ratio = 15.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.90 PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 8 PLAT431_ALERT_2_C Short Inter HL..A Contact Br1 .. O4 .. 3.07 Ang. PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 C8 H6 Br N O2
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 0.904 Tmax scaled 0.904 Tmin scaled 0.289
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 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
In an ice bath and with stirring, aqueous NaOH (30%, 6.4 ml) and 0.2% CuSO4 (4.2 ml) were added to Zn powder (6.36 g, 97.26 mmol). To this mixture was added 4-aminophthalimide (3.47 g, 21.37 mmol) over 30 min. The solid particles turned from yellow to orange, and the cloudy liquid was green. After 30 min stirring at room temperature, water (10 ml) was added and the reaction mixture was stirred at 353 K overnight. After cooling, a green-grey cloudy mixture was obtained. The precipitate was filtered off under reduced pressure. The filtrate was neutralized by 2 N HCl and further acidified with concentrated HCl (20 ml). Some solid precipitate formed when the pH was approximately 2. The mixture was heated to reflux for about 10 min, cooled to room temperature and then placed in a refrigerator. The yellow solid that precipitated was filtered off, washed with water (3 × 6 ml) and dried under vacuum at room temperature (yield 60%).
In a 100 ml round bottom flask, 5-aminophthalide (665.4 mg, 4.46 mmol) was dissolved in benzene (20 ml). After stirring for 5 min at room temperature, N-bromosuccinimide (886.1 mg, 49.8 mmol) and 2,2'-Azobis(2-methylpropionitrile) (AIBN) (108.6 mg, 0.66 mmol) were added to the reaction flask. The reaction mixture was heated overnight in an oil bath set at 348 K. The solvent was removed under reduced pressure. The residual was separated on a silica gel column (dry load), using hexane and ethyl acetate (1:1 v/v; Rf = 0.44). The product portion was collected and evaporated under reduced pressure (yield 48%). Orange needles of (I) were obtained by recrystallization from water/methanol (5:1 v/v).
1H NMR (500 MHz, CDCl3) δ (p.p.m.): 7.62 (d, 1H, aromatic H, J = 8.29 Hz), 6.81 (d, 1H, aromatic H, J = 8.29 Hz), 5.09 (s, 2H, α-CH–), 4.69 (s, 2H, –NH2). 13C NMR (500 MHz, CDCl3) δ (p.p.m.): 165.18 (–CO–), 149.34, 149.30, 125.91, 116.54, 116.12, 100.04, 69.44 (α-C). IR(cm-1) 3470 (–NH2), 3335 (–NH2), 3206, 1725 (–CO–), 1618 (–NH2), 1596, 1492, 1356, 1269, 1257, 1124, 1041, 1012, 953. LCMS (APCI, m/z) 230.1 (100), 228.5 (73), 231.1 (9).
All the H atoms were included in the riding-model approximation, with C—H = 0.95–0.99 Å and N—H = 0.88 Å, and with Uiso(H) = 1.2Ueq(C, N). The maximum and minimum difference peaks are located 1.30 and 0.68 Å, respectively, from Br2.
The title compound (I), was investigated as a part of our ongoing studies into the preparation of polyamides (Wang et al., 2007) and was obtained from a two-step reduction reaction sequence to convert 4-aminophthalimide to 5-aminophthalide (see Experimental). The structure of (I) was confirmed by crystallography (Fig. 1).
Two independent molecules of (I), A and B, comprise the asymmetric unit, which are virtually identical as seen in the RMS-fit of 0.042 Å (Spek, 2003). The nine atoms comprising the framework are co-planar with a maximum deviation of 0.032 (6) Å for the C1 atom in molecule A and 0.015 (4) Å for the O1 atom in molecule B.
The crystal packing is dominated by N—H···O hydrogen bonding (Table 1) between one of the amine-H atoms and carbonyl groups leading to chains aligned along the b-direction. Each chain comprises only molecules A or only molecules B; the second amine-H atom forms an intramolecular contact with the Br atom in each case. Chains stack along the c-direction to form layers. Within layers comprising molecules of A, the connections are of the type π···π with the distance between ring centroids of (C2–C7) being 3.783 (3) Å; symmetry operation: x, 1/2 - y, -1/2 + z. Further stabilization is afforded by C—H···Br contacts.
Within layers comprising molecules of B, there are also π···π contacts, this time between (C10–C15) rings of 3.763 (3) Å for symmetry operation: x, 3/2 - y, 1/2 + z.
The amine-H2a atom is bifurcated in that it also forms a weak interaction to the ring-O1 atom as well as to the Br2 atom. Finally, C—H···O contacts are found in these layers further distinguishing the intermolecular connectivities operating within the layers defined by molecules of A or molecules of B. A view of the crystal packing is shown in Fig. 2.
For related literature, see: Wang et al. (2007); Spek (2003).
Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97.
C8H6BrNO2 | F(000) = 896 |
Mr = 228.05 | Dx = 1.868 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: -P 2ybc | Cell parameters from 7543 reflections |
a = 14.353 (5) Å | θ = 2.7–30.3° |
b = 15.090 (6) Å | µ = 5.02 mm−1 |
c = 7.5017 (18) Å | T = 153 K |
β = 93.287 (10)° | Plate, orange |
V = 1622.0 (9) Å3 | 0.35 × 0.20 × 0.02 mm |
Z = 8 |
Rigaku AFC12κ/SATURN724 diffractometer | 3356 independent reflections |
Radiation source: fine-focus sealed tube | 3076 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
ω scans | θmax = 26.5°, θmin = 2.7° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −13→18 |
Tmin = 0.320, Tmax = 1.000 | k = −18→18 |
19327 measured reflections | l = −8→9 |
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)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.160 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0839P)2 + 5.2755P] where P = (Fo2 + 2Fc2)/3 |
3356 reflections | (Δ/σ)max < 0.001 |
217 parameters | Δρmax = 1.70 e Å−3 |
0 restraints | Δρmin = −0.98 e Å−3 |
C8H6BrNO2 | V = 1622.0 (9) Å3 |
Mr = 228.05 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.353 (5) Å | µ = 5.02 mm−1 |
b = 15.090 (6) Å | T = 153 K |
c = 7.5017 (18) Å | 0.35 × 0.20 × 0.02 mm |
β = 93.287 (10)° |
Rigaku AFC12κ/SATURN724 diffractometer | 3356 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 3076 reflections with I > 2σ(I) |
Tmin = 0.320, Tmax = 1.000 | Rint = 0.043 |
19327 measured reflections |
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.160 | H-atom parameters constrained |
S = 1.12 | Δρmax = 1.70 e Å−3 |
3356 reflections | Δρmin = −0.98 e Å−3 |
217 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.76354 (4) | 0.14582 (4) | 0.55865 (7) | 0.0345 (2) | |
Br2 | 0.70712 (4) | 0.71950 (4) | −0.02499 (8) | 0.0423 (2) | |
O1 | 0.7102 (3) | 0.4535 (3) | 0.5012 (5) | 0.0397 (9) | |
O2 | 0.5859 (3) | 0.5183 (3) | 0.3634 (6) | 0.0498 (11) | |
O3 | 0.9376 (3) | 0.5163 (2) | −0.1914 (6) | 0.0428 (10) | |
O4 | 1.0792 (3) | 0.5531 (3) | −0.2830 (7) | 0.0494 (11) | |
N1 | 0.5726 (4) | 0.0837 (3) | 0.3766 (7) | 0.0432 (12) | |
H1A | 0.5214 | 0.0596 | 0.3282 | 0.052* | |
H1B | 0.6183 | 0.0498 | 0.4202 | 0.052* | |
N2 | 0.8207 (4) | 0.8909 (3) | −0.0956 (7) | 0.0469 (12) | |
H2A | 0.7636 | 0.8882 | −0.0588 | 0.056* | |
H2B | 0.8473 | 0.9427 | −0.1108 | 0.056* | |
C1 | 0.6238 (4) | 0.4504 (4) | 0.4145 (7) | 0.0372 (12) | |
C2 | 0.5946 (4) | 0.3578 (3) | 0.3977 (7) | 0.0291 (10) | |
C3 | 0.5141 (3) | 0.3199 (4) | 0.3205 (7) | 0.0332 (11) | |
H3 | 0.4644 | 0.3560 | 0.2730 | 0.040* | |
C4 | 0.5075 (4) | 0.2281 (4) | 0.3140 (7) | 0.0331 (11) | |
H4 | 0.4525 | 0.2016 | 0.2614 | 0.040* | |
C5 | 0.5810 (4) | 0.1726 (4) | 0.3840 (7) | 0.0317 (11) | |
C6 | 0.6623 (4) | 0.2143 (3) | 0.4641 (7) | 0.0285 (10) | |
C7 | 0.6675 (3) | 0.3056 (4) | 0.4689 (6) | 0.0300 (10) | |
C8 | 0.7448 (4) | 0.3646 (4) | 0.5389 (7) | 0.0315 (11) | |
H8A | 0.7575 | 0.3558 | 0.6688 | 0.038* | |
H8B | 0.8027 | 0.3531 | 0.4771 | 0.038* | |
C9 | 1.0050 (4) | 0.5772 (4) | −0.2323 (8) | 0.0405 (13) | |
C10 | 0.9705 (4) | 0.6654 (3) | −0.2033 (7) | 0.0322 (11) | |
C11 | 1.0098 (4) | 0.7477 (4) | −0.2266 (7) | 0.0345 (11) | |
H11 | 1.0711 | 0.7528 | −0.2669 | 0.041* | |
C12 | 0.9592 (4) | 0.8218 (4) | −0.1906 (8) | 0.0377 (12) | |
H12 | 0.9859 | 0.8785 | −0.2073 | 0.045* | |
C13 | 0.8672 (4) | 0.8159 (4) | −0.1287 (7) | 0.0328 (11) | |
C14 | 0.8289 (4) | 0.7314 (4) | −0.1073 (7) | 0.0314 (11) | |
C15 | 0.8796 (4) | 0.6578 (4) | −0.1420 (7) | 0.0331 (11) | |
C16 | 0.8557 (4) | 0.5614 (4) | −0.1312 (8) | 0.0383 (12) | |
H16A | 0.8438 | 0.5443 | −0.0071 | 0.046* | |
H16B | 0.7999 | 0.5473 | −0.2096 | 0.046* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0283 (3) | 0.0415 (3) | 0.0335 (3) | 0.0073 (2) | −0.0005 (2) | 0.0012 (2) |
Br2 | 0.0261 (3) | 0.0616 (4) | 0.0394 (4) | 0.0013 (2) | 0.0024 (2) | 0.0019 (2) |
O1 | 0.038 (2) | 0.034 (2) | 0.046 (2) | −0.0087 (16) | 0.0001 (17) | 0.0015 (17) |
O2 | 0.050 (3) | 0.038 (2) | 0.062 (3) | 0.0083 (19) | 0.000 (2) | 0.008 (2) |
O3 | 0.038 (2) | 0.0272 (18) | 0.063 (3) | −0.0030 (16) | 0.0041 (19) | −0.0018 (18) |
O4 | 0.036 (2) | 0.042 (2) | 0.070 (3) | 0.0068 (18) | 0.009 (2) | −0.007 (2) |
N1 | 0.041 (3) | 0.038 (3) | 0.050 (3) | −0.009 (2) | −0.005 (2) | −0.004 (2) |
N2 | 0.043 (3) | 0.040 (3) | 0.057 (3) | 0.008 (2) | −0.002 (2) | −0.003 (2) |
C1 | 0.031 (3) | 0.044 (3) | 0.037 (3) | −0.002 (2) | 0.003 (2) | 0.002 (2) |
C2 | 0.025 (2) | 0.034 (3) | 0.029 (2) | 0.0017 (19) | 0.0050 (19) | 0.0019 (19) |
C3 | 0.022 (2) | 0.049 (3) | 0.029 (3) | 0.002 (2) | 0.0000 (19) | 0.003 (2) |
C4 | 0.022 (2) | 0.043 (3) | 0.034 (3) | −0.001 (2) | 0.003 (2) | −0.004 (2) |
C5 | 0.025 (2) | 0.044 (3) | 0.026 (2) | 0.002 (2) | 0.0027 (19) | −0.002 (2) |
C6 | 0.024 (2) | 0.034 (3) | 0.027 (2) | −0.0004 (19) | 0.0029 (19) | 0.0002 (19) |
C7 | 0.023 (2) | 0.041 (3) | 0.026 (2) | 0.000 (2) | 0.0027 (18) | −0.001 (2) |
C8 | 0.026 (3) | 0.040 (3) | 0.028 (3) | −0.002 (2) | 0.0022 (19) | 0.000 (2) |
C9 | 0.036 (3) | 0.041 (3) | 0.044 (3) | 0.004 (2) | −0.001 (2) | 0.000 (2) |
C10 | 0.032 (3) | 0.031 (2) | 0.032 (3) | 0.000 (2) | −0.004 (2) | −0.002 (2) |
C11 | 0.021 (2) | 0.050 (3) | 0.033 (3) | −0.007 (2) | 0.001 (2) | 0.004 (2) |
C12 | 0.041 (3) | 0.035 (3) | 0.036 (3) | −0.002 (2) | −0.003 (2) | 0.001 (2) |
C13 | 0.029 (3) | 0.035 (3) | 0.033 (3) | 0.004 (2) | −0.006 (2) | 0.002 (2) |
C14 | 0.025 (3) | 0.042 (3) | 0.027 (3) | 0.003 (2) | −0.0002 (19) | 0.000 (2) |
C15 | 0.029 (3) | 0.039 (3) | 0.031 (3) | −0.005 (2) | −0.003 (2) | 0.000 (2) |
C16 | 0.034 (3) | 0.034 (3) | 0.047 (3) | −0.003 (2) | 0.003 (2) | 0.002 (2) |
Br1—C6 | 1.888 (5) | C4—C5 | 1.422 (7) |
Br2—C14 | 1.895 (5) | C4—H4 | 0.9500 |
O1—C1 | 1.367 (7) | C5—C6 | 1.427 (7) |
O1—C8 | 1.452 (7) | C6—C7 | 1.379 (7) |
O2—C1 | 1.212 (7) | C7—C8 | 1.495 (7) |
O3—C9 | 1.381 (7) | C8—H8A | 0.9900 |
O3—C16 | 1.453 (7) | C8—H8B | 0.9900 |
O4—C9 | 1.208 (7) | C9—C10 | 1.441 (8) |
N1—C5 | 1.348 (7) | C10—C11 | 1.379 (7) |
N1—H1A | 0.8800 | C10—C15 | 1.412 (8) |
N1—H1B | 0.8800 | C11—C12 | 1.369 (8) |
N2—C13 | 1.344 (7) | C11—H11 | 0.9500 |
N2—H2A | 0.8800 | C12—C13 | 1.427 (8) |
N2—H2B | 0.8800 | C12—H12 | 0.9500 |
C1—C2 | 1.463 (7) | C13—C14 | 1.401 (8) |
C2—C3 | 1.385 (7) | C14—C15 | 1.361 (8) |
C2—C7 | 1.391 (7) | C15—C16 | 1.497 (7) |
C3—C4 | 1.390 (8) | C16—H16A | 0.9900 |
C3—H3 | 0.9500 | C16—H16B | 0.9900 |
C1—O1—C8 | 110.6 (4) | C7—C8—H8A | 110.9 |
C9—O3—C16 | 110.2 (4) | O1—C8—H8B | 110.9 |
C5—N1—H1A | 120.0 | C7—C8—H8B | 110.9 |
C5—N1—H1B | 120.0 | H8A—C8—H8B | 109.0 |
H1A—N1—H1B | 120.0 | O4—C9—O3 | 120.7 (5) |
C13—N2—H2A | 120.0 | O4—C9—C10 | 130.0 (6) |
C13—N2—H2B | 120.0 | O3—C9—C10 | 109.3 (5) |
H2A—N2—H2B | 120.0 | C11—C10—C15 | 120.4 (5) |
O2—C1—O1 | 120.0 (5) | C11—C10—C9 | 131.7 (5) |
O2—C1—C2 | 131.2 (5) | C15—C10—C9 | 107.8 (5) |
O1—C1—C2 | 108.8 (5) | C12—C11—C10 | 119.0 (5) |
C3—C2—C7 | 121.2 (5) | C12—C11—H11 | 120.5 |
C3—C2—C1 | 131.2 (5) | C10—C11—H11 | 120.5 |
C7—C2—C1 | 107.6 (5) | C11—C12—C13 | 121.7 (5) |
C2—C3—C4 | 118.6 (5) | C11—C12—H12 | 119.2 |
C2—C3—H3 | 120.7 | C13—C12—H12 | 119.2 |
C4—C3—H3 | 120.7 | N2—C13—C14 | 122.9 (5) |
C3—C4—C5 | 121.7 (5) | N2—C13—C12 | 119.1 (5) |
C3—C4—H4 | 119.1 | C14—C13—C12 | 118.0 (5) |
C5—C4—H4 | 119.1 | C15—C14—C13 | 120.2 (5) |
N1—C5—C4 | 120.5 (5) | C15—C14—Br2 | 119.8 (4) |
N1—C5—C6 | 121.7 (5) | C13—C14—Br2 | 119.9 (4) |
C4—C5—C6 | 117.8 (5) | C14—C15—C10 | 120.6 (5) |
C7—C6—C5 | 119.5 (5) | C14—C15—C16 | 131.0 (5) |
C7—C6—Br1 | 119.8 (4) | C10—C15—C16 | 108.3 (5) |
C5—C6—Br1 | 120.6 (4) | O3—C16—C15 | 104.3 (4) |
C6—C7—C2 | 121.1 (5) | O3—C16—H16A | 110.9 |
C6—C7—C8 | 130.0 (5) | C15—C16—H16A | 110.9 |
C2—C7—C8 | 108.9 (5) | O3—C16—H16B | 110.9 |
O1—C8—C7 | 104.1 (4) | C15—C16—H16B | 110.9 |
O1—C8—H8A | 110.9 | H16A—C16—H16B | 108.9 |
C8—O1—C1—O2 | −176.0 (5) | C16—O3—C9—O4 | 179.1 (6) |
C8—O1—C1—C2 | 2.7 (6) | C16—O3—C9—C10 | −0.7 (6) |
O2—C1—C2—C3 | −1.1 (11) | O4—C9—C10—C11 | 1.2 (11) |
O1—C1—C2—C3 | −179.6 (5) | O3—C9—C10—C11 | −179.0 (6) |
O2—C1—C2—C7 | 175.7 (6) | O4—C9—C10—C15 | −179.5 (6) |
O1—C1—C2—C7 | −2.8 (6) | O3—C9—C10—C15 | 0.3 (6) |
C7—C2—C3—C4 | −0.5 (8) | C15—C10—C11—C12 | −0.5 (8) |
C1—C2—C3—C4 | 175.9 (5) | C9—C10—C11—C12 | 178.8 (6) |
C2—C3—C4—C5 | −0.1 (8) | C10—C11—C12—C13 | 0.4 (8) |
C3—C4—C5—N1 | 179.7 (5) | C11—C12—C13—N2 | −179.9 (5) |
C3—C4—C5—C6 | 0.7 (7) | C11—C12—C13—C14 | −0.8 (8) |
N1—C5—C6—C7 | −179.8 (5) | N2—C13—C14—C15 | −179.7 (5) |
C4—C5—C6—C7 | −0.8 (7) | C12—C13—C14—C15 | 1.1 (8) |
N1—C5—C6—Br1 | 1.6 (7) | N2—C13—C14—Br2 | −1.0 (7) |
C4—C5—C6—Br1 | −179.5 (4) | C12—C13—C14—Br2 | 179.9 (4) |
C5—C6—C7—C2 | 0.3 (7) | C13—C14—C15—C10 | −1.2 (8) |
Br1—C6—C7—C2 | 179.0 (4) | Br2—C14—C15—C10 | −180.0 (4) |
C5—C6—C7—C8 | −177.9 (5) | C13—C14—C15—C16 | −179.7 (5) |
Br1—C6—C7—C8 | 0.7 (7) | Br2—C14—C15—C16 | 1.6 (8) |
C3—C2—C7—C6 | 0.4 (8) | C11—C10—C15—C14 | 0.9 (8) |
C1—C2—C7—C6 | −176.8 (5) | C9—C10—C15—C14 | −178.6 (5) |
C3—C2—C7—C8 | 179.0 (5) | C11—C10—C15—C16 | 179.6 (5) |
C1—C2—C7—C8 | 1.8 (6) | C9—C10—C15—C16 | 0.2 (6) |
C1—O1—C8—C7 | −1.5 (5) | C9—O3—C16—C15 | 0.8 (6) |
C6—C7—C8—O1 | 178.2 (5) | C14—C15—C16—O3 | 178.0 (5) |
C2—C7—C8—O1 | −0.2 (5) | C10—C15—C16—O3 | −0.6 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.88 | 2.14 | 2.987 (7) | 162 |
N2—H2B···O4ii | 0.88 | 2.15 | 3.006 (7) | 164 |
N1—H1B···Br1 | 0.88 | 2.70 | 3.135 (6) | 112 |
N2—H2A···Br2 | 0.88 | 2.69 | 3.119 (5) | 111 |
N2—H2A···O1iii | 0.88 | 2.56 | 2.948 (7) | 108 |
C8—H8A···Br1iv | 0.99 | 2.92 | 3.895 (5) | 168 |
C12—H12···O3ii | 0.95 | 2.49 | 3.427 (7) | 169 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+2, y+1/2, −z−1/2; (iii) x, −y+3/2, z−1/2; (iv) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C8H6BrNO2 |
Mr | 228.05 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 153 |
a, b, c (Å) | 14.353 (5), 15.090 (6), 7.5017 (18) |
β (°) | 93.287 (10) |
V (Å3) | 1622.0 (9) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 5.02 |
Crystal size (mm) | 0.35 × 0.20 × 0.02 |
Data collection | |
Diffractometer | Rigaku AFC12κ/SATURN724 |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.320, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19327, 3356, 3076 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.160, 1.12 |
No. of reflections | 3356 |
No. of parameters | 217 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.70, −0.98 |
Computer programs: CrystalClear (Rigaku/MSC, 2005), CrystalClear, SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.88 | 2.14 | 2.987 (7) | 162 |
N2—H2B···O4ii | 0.88 | 2.15 | 3.006 (7) | 164 |
N1—H1B···Br1 | 0.88 | 2.70 | 3.135 (6) | 112 |
N2—H2A···Br2 | 0.88 | 2.69 | 3.119 (5) | 111 |
N2—H2A···O1iii | 0.88 | 2.56 | 2.948 (7) | 108 |
C8—H8A···Br1iv | 0.99 | 2.92 | 3.895 (5) | 168 |
C12—H12···O3ii | 0.95 | 2.49 | 3.427 (7) | 169 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+2, y+1/2, −z−1/2; (iii) x, −y+3/2, z−1/2; (iv) x, −y+1/2, z+1/2. |
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The title compound (I), was investigated as a part of our ongoing studies into the preparation of polyamides (Wang et al., 2007) and was obtained from a two-step reduction reaction sequence to convert 4-aminophthalimide to 5-aminophthalide (see Experimental). The structure of (I) was confirmed by crystallography (Fig. 1).
Two independent molecules of (I), A and B, comprise the asymmetric unit, which are virtually identical as seen in the RMS-fit of 0.042 Å (Spek, 2003). The nine atoms comprising the framework are co-planar with a maximum deviation of 0.032 (6) Å for the C1 atom in molecule A and 0.015 (4) Å for the O1 atom in molecule B.
The crystal packing is dominated by N—H···O hydrogen bonding (Table 1) between one of the amine-H atoms and carbonyl groups leading to chains aligned along the b-direction. Each chain comprises only molecules A or only molecules B; the second amine-H atom forms an intramolecular contact with the Br atom in each case. Chains stack along the c-direction to form layers. Within layers comprising molecules of A, the connections are of the type π···π with the distance between ring centroids of (C2–C7) being 3.783 (3) Å; symmetry operation: x, 1/2 - y, -1/2 + z. Further stabilization is afforded by C—H···Br contacts.
Within layers comprising molecules of B, there are also π···π contacts, this time between (C10–C15) rings of 3.763 (3) Å for symmetry operation: x, 3/2 - y, 1/2 + z.
The amine-H2a atom is bifurcated in that it also forms a weak interaction to the ring-O1 atom as well as to the Br2 atom. Finally, C—H···O contacts are found in these layers further distinguishing the intermolecular connectivities operating within the layers defined by molecules of A or molecules of B. A view of the crystal packing is shown in Fig. 2.