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The title compound, C17H13BrN4O2, is non-planar, with a dihedral angle between the quinoline and substituted phenyl rings of 20.8 (1)°. The N-N bond distance [1.359 (3) Å] is close to the value of 1.350 (10) Å quoted for the N-N bond in pyridazinium [Allen et al. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803005348/na6207sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803005348/na6207Isup2.hkl
Contains datablock I

CCDC reference: 209959

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.044
  • wR factor = 0.107
  • Data-to-parameter ratio = 15.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

Hydrazones are widely used both in organic syntheses and industrial works because of their reaction abilities, such as ring closure, cycloaddiation, coupling, etc. In addition, because of their biological activities, heteroaromatic hydrazones and derivatives are medicinally important compounds and they are under investigation as potential anticancer and anti-HIV reagents (Kirk-Othmer, 1980; Gürsoy et al., 1997). In view of this, the crystal structure determination of the title compound, (I), has been carried out in order to elucidate the molecular conformation.

The molecular structure of (I) is shown in Fig. 1. The C10N2 bond length of 1.278 (4) Å is longer than typical double bonds observed in similar structures, viz. 1.265 (4) (Öztürk et al., 2001), 1.267 (3) (Akkurt et al., 2001) and 1.265 (4) Å (Özturk et al., 2001). The C16—N4 bond length [1.471 (4) Å] of the nitro group in (I) is close to the standard value for this type of bond (Allen et al., 1987). In the quinoline ring, the C7—C8—C9 angle is larger than 120° [124.4 (3)°] and the N1—C3—C4 angle is smaller than 120° [118.3 (3)°].

The C9—C10N2—N3(C17)—C11 central chain is planar [maximum displacement of −0.037 (3) Å for atom N3] and forms dihedral angles of 18.4 (1) and 12.8 (1)° with the quinoline and phenyl planes, respectively.

There is a weak hydrogen bond calculated by PARST97 (Nardelli, 1995), given in Table 2, and the H···A = 2.53 Å distance is less than the sum of the van der Waals radii.

Experimental top

Quinoline-4-carboxaldehyde (1.0 mmol) was dissolved in hot absolute ethanol (10 ml) and an equimolar amount of N-(4-bromo-2-nitrophenyl)-N-methylhydrazine dissolved in hot absolute ethanol (10 ml) was added. The mixture was refluxed on a steam bath for 3 h. The crude product which precipitated on cooling was recrytallized from ethanol. Yield 97%, m.p.:464–465 K; IR (KBr): ν 3090–3010, 3000–2930, 1585, 1495 and 1375, 1100, 750 cm−1; 1H NMR (DMSO-d6, δ, 200 MHz): 3.66 (s, N—CH3, 3H), 7.53–8.91 (m, ArH and CH, 10H); MS: m/z 385 (M+), 155 (M − 230), 128 (M − 257), 101 (M − 284); UV (CHCl3): λmax 248.1, 351.3 nm; elemental analysis, C17H13BrN4O2 requires/found: C 52.99/52.63, H 3.40/3.43, N 14.54/14.41%.

Refinement top

All H atoms were located geometrically and constrained to ride on their parent atoms. [Please provide a correct description of the H-atom treatment; some atoms appear to have been refined]

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens,1996); 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 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. An ORTEP-3 (Farrugia, 1997) drawing of the title compound, showing the labelling of the non-H atoms. Displacement ellipsoids are shown at the 50% probability level.
N-(4-Bromo-2-nitrophenyl)-N-methyl-N'-(quinolin-4-ylmethylene)hydrazine top
Crystal data top
C17H13BrN4O2F(000) = 776
Mr = 385.22Dx = 1.617 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 12.7415 (11) ÅCell parameters from 9640 reflections
b = 6.9924 (6) Åθ = 2.6–28.3°
c = 17.9671 (15) ŵ = 2.62 mm1
β = 98.641 (2)°T = 293 K
V = 1582.6 (2) Å3Needle, yellow
Z = 40.44 × 0.22 × 0.10 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer
3858 independent reflections
Radiation source: fine-focus sealed tube1982 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.041
Detector resolution: 8.33 pixels mm-1θmax = 28.3°, θmin = 2.6°
ω scansh = 1616
Absorption correction: empirical (using intensity measurements)
(SADABS, Sheldrick, 1996)
k = 99
Tmin = 0.506, Tmax = 0.770l = 2316
9585 measured reflections
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0291P)2 + 1.2305P]
where P = (Fo2 + 2Fc2)/3
3858 reflections(Δ/σ)max < 0.001
245 parametersΔρmax = 0.42 e Å3
0 restraintsΔρmin = 0.58 e Å3
Crystal data top
C17H13BrN4O2V = 1582.6 (2) Å3
Mr = 385.22Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.7415 (11) ŵ = 2.62 mm1
b = 6.9924 (6) ÅT = 293 K
c = 17.9671 (15) Å0.44 × 0.22 × 0.10 mm
β = 98.641 (2)°
Data collection top
Siemens SMART CCD area-detector
diffractometer
3858 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS, Sheldrick, 1996)
1982 reflections with I > 2σ(I)
Tmin = 0.506, Tmax = 0.770Rint = 0.041
9585 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.107H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.42 e Å3
3858 reflectionsΔρmin = 0.58 e Å3
245 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
Br10.64193 (3)0.65227 (7)0.01310 (2)0.06777 (19)
O11.0607 (2)0.6788 (5)0.04704 (16)0.0793 (10)
O21.0303 (2)0.9715 (4)0.08065 (14)0.0597 (8)
N11.4116 (2)0.7395 (5)0.20382 (19)0.0576 (9)
N21.0138 (2)0.7736 (4)0.21982 (14)0.0338 (6)
N30.9069 (2)0.7931 (4)0.23792 (14)0.0355 (7)
N41.0033 (2)0.8046 (5)0.07582 (15)0.0434 (8)
C11.2353 (3)0.7932 (6)0.1750 (2)0.0469 (10)
C21.3460 (3)0.7748 (6)0.1561 (2)0.0593 (11)
H2A1.37480.78890.10570.071*
C31.3683 (3)0.7219 (5)0.2784 (2)0.0443 (9)
C41.4367 (3)0.6844 (6)0.3311 (3)0.0608 (12)
H4A1.50920.67220.31470.073*
C51.3993 (3)0.6655 (6)0.4054 (2)0.0609 (11)
H5A1.44610.64240.43940.073*
C61.2903 (3)0.6808 (6)0.4311 (2)0.0512 (10)
C71.2214 (3)0.7159 (5)0.38148 (19)0.0411 (9)
H7A1.14920.72570.39940.049*
C81.2569 (2)0.7380 (5)0.30326 (19)0.0347 (8)
C91.1892 (3)0.7737 (5)0.24886 (19)0.0372 (8)
C101.0737 (3)0.7900 (5)0.2705 (2)0.0369 (8)
C110.8477 (2)0.7619 (5)0.17985 (18)0.0308 (7)
C120.7378 (3)0.7299 (5)0.19441 (19)0.0386 (8)
H12A0.70460.72940.24420.046*
C130.6773 (3)0.6993 (5)0.1385 (2)0.0447 (9)
H13A0.60430.68340.15050.054*
C140.7253 (3)0.6923 (5)0.06443 (19)0.0404 (9)
C150.8330 (3)0.7183 (5)0.0464 (2)0.0394 (9)
C160.8919 (2)0.7561 (5)0.10334 (18)0.0334 (8)
C170.8576 (3)0.8199 (7)0.3160 (2)0.0443 (10)
H101.052 (3)0.812 (5)0.322 (2)0.054 (11)*
H150.869 (3)0.714 (5)0.0045 (19)0.052 (11)*
H11.195 (3)0.826 (5)0.1413 (19)0.049 (11)*
H61.261 (3)0.665 (6)0.485 (2)0.070 (13)*
H2170.865 (3)0.703 (6)0.345 (2)0.060 (12)*
H1170.790 (3)0.851 (5)0.3194 (19)0.050 (11)*
H3170.894 (3)0.925 (5)0.340 (2)0.062 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0472 (2)0.1000 (4)0.0613 (3)0.0102 (3)0.02513 (19)0.0012 (3)
O10.0403 (16)0.120 (3)0.072 (2)0.0121 (18)0.0099 (14)0.048 (2)
O20.0471 (16)0.068 (2)0.0658 (19)0.0268 (15)0.0133 (13)0.0254 (16)
N10.0310 (17)0.081 (3)0.057 (2)0.0049 (17)0.0046 (16)0.0004 (19)
N20.0251 (14)0.0399 (17)0.0346 (15)0.0005 (12)0.0009 (12)0.0005 (13)
N30.0253 (14)0.0469 (19)0.0322 (15)0.0044 (12)0.0023 (11)0.0017 (13)
N40.0312 (16)0.068 (3)0.0306 (16)0.0049 (16)0.0049 (13)0.0036 (16)
C10.034 (2)0.059 (3)0.047 (2)0.0087 (18)0.0057 (18)0.003 (2)
C20.042 (2)0.084 (3)0.048 (2)0.012 (2)0.0066 (19)0.002 (2)
C30.0276 (18)0.049 (2)0.055 (3)0.0035 (16)0.0033 (17)0.0024 (19)
C40.0260 (19)0.074 (3)0.083 (3)0.0032 (19)0.0102 (19)0.001 (3)
C50.047 (2)0.079 (3)0.062 (3)0.008 (2)0.025 (2)0.004 (2)
C60.045 (2)0.063 (3)0.047 (2)0.005 (2)0.0131 (18)0.001 (2)
C70.0339 (19)0.043 (2)0.047 (2)0.0042 (16)0.0070 (16)0.0026 (17)
C80.0305 (18)0.032 (2)0.041 (2)0.0051 (15)0.0041 (15)0.0067 (16)
C90.0325 (18)0.036 (2)0.043 (2)0.0049 (15)0.0034 (15)0.0044 (16)
C100.0291 (18)0.043 (2)0.038 (2)0.0014 (15)0.0018 (16)0.0016 (17)
C110.0248 (16)0.0308 (19)0.0359 (18)0.0041 (14)0.0014 (14)0.0040 (15)
C120.0289 (18)0.044 (2)0.040 (2)0.0004 (15)0.0044 (15)0.0047 (17)
C130.0253 (17)0.050 (3)0.059 (3)0.0032 (16)0.0059 (16)0.0089 (19)
C140.0296 (18)0.046 (2)0.048 (2)0.0008 (16)0.0112 (16)0.0041 (18)
C150.036 (2)0.044 (2)0.037 (2)0.0004 (16)0.0021 (16)0.0004 (18)
C160.0228 (16)0.038 (2)0.0374 (19)0.0011 (14)0.0009 (14)0.0014 (16)
C170.035 (2)0.061 (3)0.034 (2)0.008 (2)0.0030 (16)0.001 (2)
Geometric parameters (Å, º) top
Br1—C141.895 (3)C6—C71.364 (5)
O1—N41.209 (4)C6—H60.98 (4)
O2—N41.224 (4)C7—C81.418 (5)
N1—C21.308 (5)C7—H7A0.9300
N1—C31.375 (4)C8—C91.419 (4)
N2—C101.278 (4)C9—C101.469 (4)
N2—N31.359 (3)C10—H100.94 (3)
N3—C111.393 (4)C11—C121.403 (4)
N3—C171.460 (4)C11—C161.405 (4)
N4—C161.471 (4)C12—C131.371 (5)
C1—C91.374 (5)C12—H12A0.9300
C1—C21.407 (5)C13—C141.380 (5)
C1—H10.88 (3)C13—H13A0.9300
C2—H2A0.9300C14—C151.373 (5)
C3—C41.405 (5)C15—C161.382 (4)
C3—C81.427 (4)C15—H150.96 (3)
C4—C51.355 (5)C17—H2170.98 (4)
C4—H4A0.9300C17—H1170.88 (4)
C5—C61.401 (5)C17—H3171.00 (4)
C5—H5A0.9300
C2—N1—C3116.9 (3)C9—C8—C3118.5 (3)
C10—N2—N3120.3 (3)C1—C9—C8117.8 (3)
N2—N3—C11116.2 (2)C1—C9—C10120.9 (3)
N2—N3—C17120.9 (3)C8—C9—C10121.3 (3)
C11—N3—C17122.5 (3)N2—C10—C9119.1 (3)
O1—N4—O2124.5 (3)N2—C10—H10127 (2)
O1—N4—C16117.9 (3)C9—C10—H10114 (2)
O2—N4—C16117.6 (3)N3—C11—C12121.5 (3)
C9—C1—C2119.5 (4)N3—C11—C16123.7 (3)
C9—C1—H1119 (2)C12—C11—C16114.8 (3)
C2—C1—H1121 (2)C13—C12—C11122.9 (3)
N1—C2—C1125.1 (4)C13—C12—H12A118.5
N1—C2—H2A117.5C11—C12—H12A118.5
C1—C2—H2A117.5C12—C13—C14119.7 (3)
N1—C3—C4118.3 (3)C12—C13—H13A120.2
N1—C3—C8122.2 (3)C14—C13—H13A120.2
C4—C3—C8119.5 (3)C15—C14—C13120.3 (3)
C5—C4—C3121.4 (3)C15—C14—Br1119.8 (3)
C5—C4—H4A119.3C13—C14—Br1119.9 (2)
C3—C4—H4A119.3C14—C15—C16119.0 (3)
C4—C5—C6120.1 (4)C14—C15—H15122 (2)
C4—C5—H5A119.9C16—C15—H15119 (2)
C6—C5—H5A119.9C15—C16—C11123.2 (3)
C7—C6—C5120.1 (4)C15—C16—N4113.5 (3)
C7—C6—H6118 (2)C11—C16—N4123.1 (3)
C5—C6—H6121 (2)N3—C17—H217110 (2)
C6—C7—C8121.8 (3)N3—C17—H117112 (2)
C6—C7—H7A119.1H217—C17—H117110 (3)
C8—C7—H7A119.1N3—C17—H317111 (2)
C7—C8—C9124.4 (3)H217—C17—H317107 (3)
C7—C8—C3117.1 (3)H117—C17—H317107 (3)
C10—N2—N3—C11176.4 (3)C1—C9—C10—N217.7 (5)
C10—N2—N3—C174.3 (5)C8—C9—C10—N2162.4 (3)
C3—N1—C2—C11.0 (7)N2—N3—C11—C12163.7 (3)
C9—C1—C2—N10.1 (7)C17—N3—C11—C128.3 (5)
C2—N1—C3—C4179.9 (4)N2—N3—C11—C1615.1 (5)
C2—N1—C3—C81.0 (6)C17—N3—C11—C16172.9 (4)
N1—C3—C4—C5180.0 (4)N3—C11—C12—C13179.8 (3)
C8—C3—C4—C50.9 (6)C16—C11—C12—C131.3 (5)
C3—C4—C5—C60.9 (7)C11—C12—C13—C142.4 (6)
C4—C5—C6—C70.4 (6)C12—C13—C14—C150.9 (5)
C5—C6—C7—C80.0 (6)C12—C13—C14—Br1179.5 (3)
C6—C7—C8—C9179.6 (4)C13—C14—C15—C161.5 (5)
C6—C7—C8—C30.0 (5)Br1—C14—C15—C16177.1 (3)
N1—C3—C8—C7179.6 (3)C14—C15—C16—C112.6 (5)
C4—C3—C8—C70.4 (5)C14—C15—C16—N4172.8 (3)
N1—C3—C8—C90.1 (5)N3—C11—C16—C15177.6 (3)
C4—C3—C8—C9179.3 (3)C12—C11—C16—C151.2 (5)
C2—C1—C9—C80.8 (6)N3—C11—C16—N47.4 (5)
C2—C1—C9—C10179.3 (4)C12—C11—C16—N4173.8 (3)
C7—C8—C9—C1179.5 (3)O1—N4—C16—C1569.7 (4)
C3—C8—C9—C10.8 (5)O2—N4—C16—C15107.1 (4)
C7—C8—C9—C100.3 (5)O1—N4—C16—C11114.9 (4)
C3—C8—C9—C10179.4 (3)O2—N4—C16—C1168.3 (4)
N3—N2—C10—C9178.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13—H13A···N1i0.932.533.424 (5)162
Symmetry code: (i) x1, y, z.

Experimental details

Crystal data
Chemical formulaC17H13BrN4O2
Mr385.22
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)12.7415 (11), 6.9924 (6), 17.9671 (15)
β (°) 98.641 (2)
V3)1582.6 (2)
Z4
Radiation typeMo Kα
µ (mm1)2.62
Crystal size (mm)0.44 × 0.22 × 0.10
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS, Sheldrick, 1996)
Tmin, Tmax0.506, 0.770
No. of measured, independent and
observed [I > 2σ(I)] reflections
9585, 3858, 1982
Rint0.041
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.107, 1.04
No. of reflections3858
No. of parameters245
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.42, 0.58

Computer programs: SMART (Siemens, 1996), SAINT (Siemens,1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
Br1—C141.895 (3)N2—C101.278 (4)
O1—N41.209 (4)N2—N31.359 (3)
O2—N41.224 (4)N3—C111.393 (4)
N1—C21.308 (5)N3—C171.460 (4)
N1—C31.375 (4)N4—C161.471 (4)
C2—N1—C3116.9 (3)N1—C3—C8122.2 (3)
C10—N2—N3120.3 (3)C7—C8—C9124.4 (3)
N2—N3—C11116.2 (2)N2—C10—C9119.1 (3)
N2—N3—C17120.9 (3)N3—C11—C12121.5 (3)
C11—N3—C17122.5 (3)N3—C11—C16123.7 (3)
O1—N4—O2124.5 (3)C15—C14—Br1119.8 (3)
O1—N4—C16117.9 (3)C13—C14—Br1119.9 (2)
O2—N4—C16117.6 (3)C15—C16—N4113.5 (3)
N1—C2—C1125.1 (4)C11—C16—N4123.1 (3)
N1—C3—C4118.3 (3)
C10—N2—N3—C11176.4 (3)C12—C13—C14—Br1179.5 (3)
C10—N2—N3—C174.3 (5)Br1—C14—C15—C16177.1 (3)
N3—N2—C10—C9178.2 (3)C14—C15—C16—N4172.8 (3)
C1—C9—C10—N217.7 (5)N3—C11—C16—C15177.6 (3)
C8—C9—C10—N2162.4 (3)N3—C11—C16—N47.4 (5)
N2—N3—C11—C12163.7 (3)C12—C11—C16—N4173.8 (3)
C17—N3—C11—C128.3 (5)O1—N4—C16—C1569.7 (4)
N2—N3—C11—C1615.1 (5)O2—N4—C16—C15107.1 (4)
C17—N3—C11—C16172.9 (4)O1—N4—C16—C11114.9 (4)
N3—C11—C12—C13179.8 (3)O2—N4—C16—C1168.3 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13—H13A···N1i0.932.533.424 (5)162
Symmetry code: (i) x1, y, z.
 

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