Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801010236/ob6057sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801010236/ob6057Isup2.hkl |
CCDC reference: 170783
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.006 Å
- R factor = 0.058
- wR factor = 0.051
- Data-to-parameter ratio = 12.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
The title compound, (I), was synthesized according to the literature method of Kılıç & Tüzün (1990). Crystals suitable for X-ray crystallography were obtained from dichloromethane–ethyl acetate (m.p. 518 K).
The positions of the H atoms were calculated geometrically at a distance of 0.95 Å from the corresponding C atom, and a riding model was used during their refinement.
Data collection: MolEN (Fair, 1990); cell refinement: MolEN; data reduction: MolEN; program(s) used to solve structure: SHELX86 (Sheldrick, 1990); program(s) used to refine structure: MolEN; molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: MolEN.
Fig. 1. An ORTEPII (Johnson, 1976) drawing of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. |
C12H7BrN2O | F(000) = 544 |
Mr = 275.10 | Dx = 1.813 Mg m−3 |
Monoclinic, P21/a | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yab | Cell parameters from 25 reflections |
a = 14.446 (3) Å | θ = 10–11° |
b = 3.963 (1) Å | µ = 4.05 mm−1 |
c = 17.807 (7) Å | T = 298 K |
β = 98.59 (2)° | Rod-shaped, yellow |
V = 1008.0 (5) Å3 | 0.30 × 0.10 × 0.10 mm |
Z = 4 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.014 |
ω/2θ scans | θmax = 26.3° |
Absorption correction: ψ scan (Fair, 1990) | h = −18→17 |
Tmin = 0.621, Tmax = 0.667 | k = 0→4 |
2420 measured reflections | l = 0→22 |
2031 independent reflections | 3 standard reflections every 120 min |
1764 reflections with F > 0 | intensity decay: 1% |
Refinement on F | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.058 | w = 1 / [σ(F)2 + (0.02 F)2 + 1.0] |
wR(F2) = 0.051 | (Δ/σ)max = 0.01 |
S = 1.12 | Δρmax = 0.46 e Å−3 |
1764 reflections | Δρmin = −0.51 e Å−3 |
145 parameters |
C12H7BrN2O | V = 1008.0 (5) Å3 |
Mr = 275.10 | Z = 4 |
Monoclinic, P21/a | Mo Kα radiation |
a = 14.446 (3) Å | µ = 4.05 mm−1 |
b = 3.963 (1) Å | T = 298 K |
c = 17.807 (7) Å | 0.30 × 0.10 × 0.10 mm |
β = 98.59 (2)° |
Enraf-Nonius CAD-4 diffractometer | 1764 reflections with F > 0 |
Absorption correction: ψ scan (Fair, 1990) | Rint = 0.014 |
Tmin = 0.621, Tmax = 0.667 | 3 standard reflections every 120 min |
2420 measured reflections | intensity decay: 1% |
2031 independent reflections |
R[F2 > 2σ(F2)] = 0.058 | 145 parameters |
wR(F2) = 0.051 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.46 e Å−3 |
1764 reflections | Δρmin = −0.51 e Å−3 |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.59995 (4) | 0.4533 (1) | 0.06961 (3) | 0.0558 (3) | |
O1 | 1.0726 (2) | 0.917 (1) | 0.3468 (2) | 0.0683 (4) | |
C1 | 0.7222 (3) | 0.718 (1) | 0.1946 (2) | 0.0360 (3) | |
C2 | 0.7178 (3) | 0.556 (1) | 0.1263 (2) | 0.0394 (4) | |
C3 | 0.7983 (3) | 0.458 (1) | 0.0970 (3) | 0.0482 (4) | |
C4 | 0.8832 (3) | 0.523 (1) | 0.1385 (3) | 0.0469 (3) | |
C5 | 0.8906 (3) | 0.687 (1) | 0.2083 (2) | 0.0359 (3) | |
N5 | 0.9804 (2) | 0.731 (1) | 0.2456 (2) | 0.0467 (3) | |
N6 | 0.9907 (2) | 0.882 (1) | 0.3109 (2) | 0.0445 (3) | |
C6 | 0.9150 (3) | 1.012 (1) | 0.3455 (2) | 0.0385 (3) | |
C7 | 0.9343 (3) | 1.171 (1) | 0.4156 (3) | 0.0436 (3) | |
C8 | 0.8623 (3) | 1.290 (1) | 0.4496 (3) | 0.0482 (4) | |
C9 | 0.7710 (3) | 1.254 (1) | 0.4137 (2) | 0.0421 (5) | |
C10 | 0.7512 (3) | 1.096 (1) | 0.3448 (2) | 0.0356 (4) | |
C11 | 0.8234 (3) | 0.966 (1) | 0.3086 (2) | 0.0309 (4) | |
C12 | 0.8100 (3) | 0.793 (1) | 0.2368 (2) | 0.0313 (3) | |
H1 | 0.666 | 0.783 | 0.213 | 0.0431 | |
H3 | 0.793 | 0.346 | 0.049 | 0.0571 | |
H4 | 0.938 | 0.454 | 0.119 | 0.0583 | |
H71 | 0.997 | 1.197 | 0.440 | 0.0659 | |
H81 | 0.875 | 1.397 | 0.498 | 0.0659 | |
H91 | 0.721 | 1.340 | 0.437 | 0.0659 | |
H101 | 0.688 | 1.075 | 0.321 | 0.0659 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0526 (3) | 0.0628 (3) | 0.0505 (2) | −0.0129 (3) | −0.0008 (2) | −0.0069 (3) |
O1 | 0.026 (1) | 0.093 (3) | 0.083 (2) | 0.004 (2) | −0.003 (2) | −0.010 (2) |
C1 | 0.030 (2) | 0.041 (2) | 0.038 (2) | 0.000 (2) | 0.007 (2) | 0.005 (2) |
C2 | 0.044 (2) | 0.036 (2) | 0.039 (2) | −0.006 (2) | 0.009 (2) | 0.007 (2) |
C3 | 0.056 (2) | 0.047 (3) | 0.042 (2) | 0.000 (2) | 0.014 (2) | −0.003 (2) |
C4 | 0.043 (2) | 0.048 (3) | 0.052 (2) | 0.006 (2) | 0.019 (2) | 0.001 (2) |
C5 | 0.035 (2) | 0.036 (2) | 0.039 (2) | 0.003 (2) | 0.013 (2) | 0.007 (2) |
N5 | 0.028 (2) | 0.057 (2) | 0.055 (2) | 0.007 (2) | 0.010 (2) | 0.002 (2) |
N6 | 0.024 (2) | 0.052 (2) | 0.057 (2) | 0.000 (2) | 0.006 (2) | 0.011 (2) |
C6 | 0.029 (2) | 0.042 (3) | 0.045 (2) | −0.001 (2) | 0.005 (2) | 0.010 (2) |
C7 | 0.034 (2) | 0.045 (3) | 0.048 (2) | −0.008 (2) | −0.006 (2) | 0.005 (2) |
C8 | 0.054 (3) | 0.049 (3) | 0.039 (2) | −0.006 (2) | 0.004 (2) | −0.001 (2) |
C9 | 0.041 (2) | 0.044 (3) | 0.043 (2) | −0.004 (2) | 0.012 (2) | −0.001 (2) |
C10 | 0.028 (2) | 0.040 (2) | 0.039 (2) | 0.001 (2) | 0.009 (2) | 0.007 (2) |
C11 | 0.028 (2) | 0.030 (2) | 0.035 (2) | −0.001 (2) | 0.003 (2) | 0.010 (2) |
C12 | 0.031 (2) | 0.030 (2) | 0.035 (2) | 0.002 (2) | 0.009 (2) | 0.008 (2) |
Br1—C2 | 1.892 (4) | C4—H4 | 0.950 |
N6—O1 | 1.268 (4) | C7—C8 | 1.358 (7) |
C12—C5 | 1.401 (6) | C7—H71 | 0.950 |
C12—C11 | 1.438 (5) | C1—C2 | 1.368 (6) |
C12—C1 | 1.404 (5) | C2—C3 | 1.396 (6) |
C5—N5 | 1.377 (5) | C3—H3 | 0.950 |
C4—C5 | 1.393 (6) | C9—C10 | 1.367 (6) |
N5—N6 | 1.298 (5) | C8—H81 | 0.950 |
C6—C11 | 1.397 (5) | C8—C9 | 1.386 (6) |
C6—C7 | 1.389 (6) | C1—H1 | 0.950 |
C6—N6 | 1.426 (5) | C10—H101 | 0.950 |
C11—C10 | 1.402 (6) | C9—H91 | 0.950 |
C3—C4 | 1.359 (6) | ||
C2—C1—C12 | 119.6 (4) | C7—C8—H81 | 120.5 |
C2—C1—H1 | 120.1 | C9—C8—H81 | 119.9 |
C12—C1—H1 | 120.3 | C8—C9—C10 | 121.3 (4) |
Br1—C2—C1 | 119.9 (3) | C8—C9—H91 | 119.5 |
Br1—C2—C3 | 118.1 (3) | C10—C9—H91 | 119.1 |
C1—C2—C3 | 122.0 (4) | C9—C10—C11 | 120.6 (3) |
C2—C3—C4 | 118.7 (4) | C9—C10—H101 | 119.9 |
C2—C3—H3 | 120.3 | C11—C10—H101 | 119.5 |
C4—C3—H3 | 121.0 | N5—C5—C12 | 124.2 (4) |
C3—C4—C5 | 121.1 (4) | C5—N5—N6 | 117.6 (3) |
C3—C4—H4 | 119.2 | N5—N6—C6 | 124.1 (3) |
C5—C4—H4 | 119.7 | N5—N6—O1 | 118.5 (3) |
C4—C5—N5 | 115.6 (4) | C6—N6—O1 | 117.4 (4) |
C4—C5—C12 | 120.2 (3) | N6—C6—C7 | 119.1 (3) |
N6—C6—C11 | 118.7 (4) | C6—C11—C10 | 116.7 (3) |
C7—C6—C11 | 122.2 (4) | C6—C11—C12 | 118.4 (4) |
C6—C7—C8 | 119.5 (4) | C10—C11—C12 | 124.9 (3) |
C6—C7—H71 | 119.7 | C1—C12—C5 | 118.5 (4) |
C8—C7—H71 | 120.8 | C1—C12—C11 | 124.6 (4) |
C7—C8—C9 | 119.7 (4) | C5—C12—C11 | 116.9 (3) |
C12—C1—C2—Br1 | 179.7 (3) | N5—N6—C6—C11 | 2.4 (6) |
C12—C1—C2—C3 | 0.8 (7) | O1—N6—C6—C7 | 0.3 (6) |
C2—C1—C12—C5 | −2.3 (6) | O1—N6—C6—C11 | −177.6 (4) |
C2—C1—C12—C11 | 179.0 (4) | N6—C6—C7—C8 | −178.7 (4) |
Br1—C2—C3—C4 | −178.1 (4) | C11—C6—C7—C8 | −0.9 (7) |
C1—C2—C3—C4 | 0.9 (7) | N6—C6—C11—C10 | 179.7 (4) |
C2—C3—C4—C5 | −0.9 (7) | N6—C6—C11—C12 | −1.0 (6) |
C3—C4—C5—N5 | 178.6 (4) | C7—C6—C11—C10 | 1.8 (6) |
C3—C4—C5—C12 | −0.7 (7) | C7—C6—C11—C12 | −178.8 (4) |
C4—C5—N5—N6 | −179.9 (4) | C6—C7—C8—C9 | −0.5 (7) |
C12—C5—N5—N6 | −0.7 (7) | C7—C8—C9—C10 | 0.8 (7) |
C4—C5—C12—C1 | 2.2 (6) | C8—C9—C10—C11 | 0.1 (7) |
C4—C5—C12—C11 | −179.0 (4) | C9—C10—C11—C6 | −1.4 (6) |
N5—C5—C12—C1 | −176.9 (4) | C9—C10—C11—C12 | 179.3 (4) |
N5—C5—C12—C11 | 1.9 (6) | C6—C11—C12—C1 | 177.8 (4) |
C5—N5—N6—C6 | −1.5 (6) | C6—C11—C12—C5 | −0.9 (6) |
C5—N5—N6—O1 | 178.4 (4) | C10—C11—C12—C1 | −2.9 (7) |
N5—N6—C6—C7 | −179.8 (4) | C10—C11—C12—C5 | 178.4 (4) |
Experimental details
Crystal data | |
Chemical formula | C12H7BrN2O |
Mr | 275.10 |
Crystal system, space group | Monoclinic, P21/a |
Temperature (K) | 298 |
a, b, c (Å) | 14.446 (3), 3.963 (1), 17.807 (7) |
β (°) | 98.59 (2) |
V (Å3) | 1008.0 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.05 |
Crystal size (mm) | 0.30 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (Fair, 1990) |
Tmin, Tmax | 0.621, 0.667 |
No. of measured, independent and observed (F > 0) reflections | 2420, 2031, 1764 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.623 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.051, 1.12 |
No. of reflections | 1764 |
No. of parameters | 145 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.46, −0.51 |
Computer programs: MolEN (Fair, 1990), MolEN, SHELX86 (Sheldrick, 1990), ORTEPII (Johnson, 1976).
Br1—C2 | 1.892 (4) | C6—N6 | 1.426 (5) |
N6—O1 | 1.268 (4) | C3—C4 | 1.359 (6) |
C5—N5 | 1.377 (5) | C7—C8 | 1.358 (7) |
N5—N6 | 1.298 (5) | C1—C2 | 1.368 (6) |
C6—C7 | 1.389 (6) | C9—C10 | 1.367 (6) |
Angles | (I) | (III) | (IV) | (V) | (VI) | (VII) | (VIII) | |
C5-C12-C11 | 116.9 (3) | 115.1 (2) | 117.7 (4) | 116.0 (2) | 116.1 (2) | 117.0 (2) | 116.5 (1) | |
C5-C12-C1 | 118.5 (4) | 116.7 (2) | 115.9 (4) | 119.4 (2) | 120.3 (2) | 118.5 (3) | 115.2 (2) | |
C11-C12-C1 | 124.6 (4) | 128.0 (2) | 126.3 (4) | 124.7 (2) | 123.7 (2) | 124.5 (3) | 128.4 (1) | |
C12-C11-C10 | 124.9 (3) | 126.4 (2) | 125.7 (4) | 125.5 (2) | 124.4 (2) | 124.8 (2) | 126.9 (2) | |
C12-C1-C2 | 119.6 (4) | 119.2 (3) | 121.6 (4) | 120.6 (2) | 118.4 (2) | 117.7 (3) | 123.5 (2) | |
C1-C2-C3 | 122.0 (4) | 122.1 (3) | 122.5 (4) | 118.8 (2) | 122.9 (2) | 124.9 (3) | 119.6 (2) | |
C2-C3-C4 | 118.7 (4) | 119.8 (3) | 116.6 (4) | 120.8 (2) | 121.6 (2) | 118.3 (3) | 119.7 (2) | |
C3-C4-C5 | 121.1 (4) | 120.2 (3) | 121.2 (4) | 120.5 (2) | 115.9 (2) | 119.3 (3) | 120.5 (2) | |
C6-C11-C12 | 118.4 (4) | 117.3 (2) | 116.7 (4) | 116.3 (2) | 127.1 (2) | 116.4 (2) | 115.6 (1) | |
C6-C11-C10 | 116.7 (3) | 116.0 (2) | 117.6 (5) | 118.2 (2) | 118.4 (2) | 118.8 (3) | 117.5 (2) | |
N5-N6-C6 | 124.1 (3) | 119.6 (2) | 119.5 (4) | 119.7 (2) | 119.9 (2) | 120.5 (2) | 120.6 (1) | |
N6-C6-C11 | 118.7 (4) | 122.9 (2) | 123.5 (4) | 123.7 (2) | 123.0 (2) | 123.1 (3) | 123.5 (2) | |
N6-C6-C7 | 119.1 (3) | 115.2 (2) | 115.4 (2) | 116.2 (2) | 116.2 (2) | 116.7 (3) | 115.9 (2) | |
C7-C6-C11 | 122.2 (4) | 121.8 (2) | 121.0 (5) | 120.1 (2) | 120.8 (2) | 120.2 (3) | 120.7 (2) | |
C5-N5-N6 | 117.6 (3) | 121.5 (2) | 121.1 (4) | 120.3 (2) | 121.5 (2) | 120.2 (3) | 120.0 (2) | |
N5-C5-C12 | 124.4 (4) | 122.9 (4) | 121.4 (4) | 123.9 (2) | 122.2 (2) | 122.8 (3) | 123.4 (2) |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
The structures of benzo[c]cinnoline derivatives with different substituents bonded at different positions of the benzo[c]cinnoline skeleton have been the subject of much interest in our laboratory. Examples include 1-morpholinobenzo[c]cinnoline, (II) (Hökelek et al., 1990), 1-piperidinobenzo[c]cinnoline, (III), and 3-piperidinobenzo[c]cinnoline, (IV) (Hökelek et al., 1991a), 2-pyrrolidinobenzo[c]cinnoline, (V), and 4-pyrrolidinobenzo[c]cinnoline, (VI) (Hökelek et al., 1991b), 2-fluorobenzo[c]cinnoline, (VII) (Hökelek, 1991), and 1-nitrobenzo[c]cinnoline, (VIII) (Hökelek et al., 1999).
Benzo[c]cinnoline and some of its derivatives are known to have mutagenic (Leary et al., 1983), antirheumatic (Matter, 1957; Erlenmeyer, 1958), herbicidial (Entwistle et al., 1981) and carcinogenic (Ashby et al., 1980) physiological activities. They have also been used as bleach catalysts in the processing of photographic silver-dye bleach materials (Jan, 1980). The structures of benzo[c]cinnoline (Van der Meer, 1972) and octachlorobenzo[c]cinnoline (King et al., 1983) have been described as complexes with bis(tricarbonyliron) (Doedens, 1970) and benzoatocopper(I) (Toth et al., 1987).
Benzo[c]cinnoline derivatives including N-oxides have been reviewed by Barton & Cockett (1962). As far as we know, there are no reports on the structures of benzo[c]cinnolines substituted with alkyl, alkoxy, aminoalkyl, nitro or N-oxide groups. The structure determination of the title compound, (I), was undertaken in order to understand the effects of changing the types and positions of the substituent and to permit a comparison of its structure with those of previously reported benzo[c]cinnolines to be made.
Fig. 1 shows compound (I) with the atomic numbering. It is a 2-bromo, N6-oxide derivative of the ligand benzod[c]cinnoline. The benzo[c]cinnoline skeleton consists of almost planar rings. The maximum distances from the least-squares planes are 0.014 (4), -0.013 (4) and -0.010 (4) Å for rings α(C1–C5,C12), β(C5,N5,N6,C6,C11,C12) and γ(C6–C11), respectively. The rings are twisted slightly with respect to each other. The dihedral angles between their least-squares planes are α-β = 2.2 (1)°, α-γ = 2.1 (1)° and β-γ = 0.5 (1)°. In benzo[c]cinnoline (Van der Meer, 1972), the dihedral angle between the two benzenoid rings is α-γ = 2.5°. The dihedral angle α-γ depends on the steric interactions between the benzo[c]cinnoline and the substituents at different positions. The interaction is greatest with the substituents at position 1. The corresponding α-γ angles are reported as 11.7° in (II), 14.32 (6) and 3.4 (1)° in (III), 1.8 (1)° in (IV), 1.32 (6)° in (V), 4.95 (7)° in (VI), 0.50 (7)° in (VII) and 8.4 (2)° in (VIII).
There are steric interactions between the H atoms at C1 and C10 (H1···H101 = 2.23 Å), and between the H atom at C7 and the O atom at N6 (O1···H71 = 2.38 Å). The benzo[c]cinnoline skeleton has enlarged C1—C12—C11 [124.6 (4)°] and C10—C11—C12 [124.9 (3)°] angles and smaller ones at the opposite side. The 6-oxide substituent generated enlarged N5—N6—C6 [124.1 (3)°], N6—C6—C7 [119.1 (3)°], C7—C6—C11 [122.2 (4)°] and N5—C5—C12 [124.2 (4)°], and narrowed N6—C6—C11 [118.7 (4)°] and C5—N5—N6 [117.6 (3)°] angles in the benzo[c]cinnoline skeleton with respect to the previously reported corresponding ones (Table 2).
The N6—O1 [1.268 (4) Å] bond length is highly shorter than the pyridine N-oxide N—O [1.304 (15) Å; Allen et al., 1987], probably due to the electron resonating between the O atom and the benzo[c]cinnoline skeleton.
As a general trend, the C1—C2, C3—C4, C9—C10 and C11—C12 bonds, in the benzo[c]cinnoline skeleton are shorter than the other bonds as determined crystallographically in all of the benzo[c]cinnoline ligands. This determination is in agreement with the theoretical calculations made by Mulliken (1955) and Hoffman (1963).