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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1433.
Published online 2008 July 9. doi:  10.1107/S1600536808020266
PMCID: PMC2962065

2,4-Dichloro­benzaldehyde 2,4-dinitro­phenyl­hydrazone

Abstract

The asymmetric unit of the title compound, C13H8Cl2N4O4, contains two independent but similar and almost planar mol­ecules. An intra­molecular N—H(...)O hydrogen bond is observed in each mol­ecule.

Related literature

For background, see: Okabe et al. (1993 [triangle]); Ohba (1996 [triangle]).

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Object name is e-64-o1433-scheme1.jpg

Experimental

Crystal data

  • C13H8Cl2N4O4
  • M r = 355.14
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1433-efi1.jpg
  • a = 13.3814 (7) Å
  • b = 28.9980 (13) Å
  • c = 7.3996 (3) Å
  • β = 92.422 (4)°
  • V = 2868.7 (2) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.48 mm−1
  • T = 291 (2) K
  • 0.16 × 0.11 × 0.09 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1998 [triangle]) T min = 0.927, T max = 0.958
  • 21827 measured reflections
  • 5060 independent reflections
  • 2794 reflections with I > 2σ(I)
  • R int = 0.092

Refinement

  • R[F 2 > 2σ(F 2)] = 0.061
  • wR(F 2) = 0.187
  • S = 1.02
  • 5060 reflections
  • 415 parameters
  • H-atom parameters constrained
  • Δρmax = 0.70 e Å−3
  • Δρmin = −0.36 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 1998 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808020266/hb2743sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808020266/hb2743Isup2.hkl

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

supplementary crystallographic information

Comment

Several phenylhydrazone derivatives have been shown to be potentially DNA-damaging and are mutagenic agents (Okabe et al.,1993). As part of our work in this area, we have synthesized the title compound, (I), and we report its crystal structure here.

The two molecules in the asymmetric unit of (I) are almost planar, the dihedral angles between the the dichlorobenzene ring and the dinitrobenzene ring are 4.4 (2)° and 3.7 (2)°, in the C1 and C14 molecules, respectively. Otherwise, bond lengths and angles agree with those of other dinitrophenylhydrazone derivatives (Ohba, 1996). Intramolecular N—H···O hydrogen bonds (Fig. 1, Table 1) help to establish these molecular conformations.

Experimental

2,4-Dinitrophenylhydrazine (1 mmol, 0.198 g) was dissolved in anhydrous methanol, H2SO4 (98% 0.5 ml) was added to this, the mixture was stirred for several minitutes at 351 K, then 2,4-dichlorobenzyaldehyde (1 mmol, 0.175 g) in methanol (8 ml) was added dropwise and the mixture was stirred at refluxing temperature for 2 h. The product was isolated and recrystallized from DMF, yielding brown blocks of (I) after 6 d.

Refinement

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

Figures

Fig. 1.
The molecular structure of (I) with displacement ellipsoids drawn at the 30% probability level (arbitrary spheres for the H atoms). The hydrogen bonds are indicated by dashed lines.

Crystal data

C13H8Cl2N4O4F000 = 1440
Mr = 355.14Dx = 1.645 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 721 reflections
a = 13.3814 (7) Åθ = 2.5–20.6º
b = 28.9980 (13) ŵ = 0.48 mm1
c = 7.3996 (3) ÅT = 291 (2) K
β = 92.422 (4)ºBlock, brown
V = 2868.7 (2) Å30.16 × 0.11 × 0.09 mm
Z = 8

Data collection

Bruker SMART APEX CCD diffractometer5060 independent reflections
Radiation source: sealed tube2794 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.093
T = 291(2) Kθmax = 25.0º
ω scansθmin = 1.4º
Absorption correction: multi-scan(SADABS; Bruker, 1998)h = −15→15
Tmin = 0.927, Tmax = 0.958k = −34→34
21827 measured reflectionsl = −8→8

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.061H-atom parameters constrained
wR(F2) = 0.187  w = 1/[σ2(Fo2) + (0.0939P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.018
5060 reflectionsΔρmax = 0.70 e Å3
415 parametersΔρmin = −0.36 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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
C10.5169 (3)0.79565 (15)0.8938 (6)0.0525 (11)
C20.4504 (4)0.76034 (15)0.8543 (6)0.0568 (12)
H2A0.46810.72990.87980.068*
C30.3594 (4)0.77030 (16)0.7782 (6)0.0567 (12)
C40.3307 (4)0.81536 (17)0.7419 (7)0.0649 (13)
H4A0.26700.82170.69260.078*
C50.3956 (4)0.85013 (17)0.7786 (6)0.0630 (13)
H5A0.37550.88020.75320.076*
C60.4926 (4)0.84239 (14)0.8539 (6)0.0508 (11)
C70.5828 (4)0.95479 (14)0.8532 (6)0.0522 (11)
H7A0.64580.95030.90850.063*
C80.5499 (3)1.00103 (14)0.7955 (5)0.0483 (11)
C90.4563 (3)1.00735 (15)0.7104 (6)0.0526 (11)
H9A0.41510.98180.69130.063*
C100.4222 (3)1.05004 (15)0.6533 (6)0.0535 (11)
H10A0.35951.05340.59590.064*
C110.4836 (4)1.08737 (14)0.6836 (6)0.0495 (11)
C120.5769 (3)1.08302 (15)0.7673 (6)0.0519 (11)
H12A0.61811.10860.78480.062*
C130.6078 (3)1.03998 (14)0.8247 (6)0.0496 (11)
C140.0562 (3)0.40012 (14)0.2229 (5)0.0453 (10)
C15−0.0068 (3)0.43582 (15)0.1708 (6)0.0501 (11)
H15A0.01420.46620.18540.060*
C16−0.1000 (3)0.42650 (15)0.0978 (6)0.0509 (11)
C17−0.1325 (4)0.38143 (16)0.0780 (6)0.0572 (12)
H17A−0.19720.37540.03300.069*
C18−0.0705 (4)0.34611 (16)0.1240 (6)0.0590 (12)
H18A−0.09300.31600.10620.071*
C190.0269 (3)0.35334 (14)0.1980 (5)0.0479 (11)
C200.1045 (4)0.23951 (15)0.2590 (6)0.0535 (12)
H20A0.16810.24400.31170.064*
C210.0647 (3)0.19295 (14)0.2269 (5)0.0472 (11)
C220.1187 (3)0.15381 (15)0.2772 (5)0.0506 (11)
C230.0818 (4)0.10936 (14)0.2470 (6)0.0517 (11)
H23A0.11930.08360.28180.062*
C24−0.0113 (4)0.10474 (15)0.1644 (6)0.0513 (11)
C25−0.0668 (4)0.14258 (16)0.1099 (6)0.0588 (12)
H25A−0.12960.13880.05280.071*
C26−0.0283 (4)0.18613 (15)0.1409 (6)0.0552 (12)
H26A−0.06570.21160.10310.066*
N10.1514 (3)0.41294 (14)0.3070 (5)0.0577 (10)
N2−0.1667 (3)0.46460 (16)0.0431 (5)0.0612 (11)
N30.2910 (3)0.73221 (16)0.7304 (6)0.0708 (12)
N40.6139 (3)0.78294 (14)0.9750 (6)0.0659 (11)
N50.5238 (3)0.92107 (12)0.8261 (5)0.0546 (10)
N60.5553 (3)0.87810 (12)0.8820 (5)0.0541 (10)
H6A0.61340.87420.93360.065*
N70.0487 (3)0.27372 (12)0.2123 (5)0.0529 (10)
N80.0870 (3)0.31688 (11)0.2431 (5)0.0532 (9)
H8A0.14650.32080.28900.064*
O10.2127 (3)0.74172 (14)0.6467 (6)0.0950 (13)
O20.3142 (3)0.69353 (13)0.7743 (6)0.0985 (13)
O30.6762 (3)0.81245 (11)1.0089 (5)0.0726 (10)
O40.6286 (3)0.74302 (14)1.0074 (8)0.135 (2)
O5−0.1387 (3)0.50380 (12)0.0700 (5)0.0796 (11)
O6−0.2487 (3)0.45419 (12)−0.0264 (5)0.0833 (11)
O70.1687 (3)0.45318 (12)0.3374 (6)0.0913 (13)
O80.2111 (3)0.38253 (11)0.3504 (5)0.0731 (10)
Cl10.44331 (10)1.14207 (4)0.61744 (18)0.0689 (4)
Cl2−0.05792 (11)0.04957 (4)0.12777 (17)0.0700 (4)
Cl30.23487 (9)0.15728 (4)0.38772 (18)0.0705 (4)
Cl40.72292 (10)1.03677 (4)0.94132 (19)0.0724 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.054 (3)0.047 (3)0.057 (3)0.004 (2)0.000 (2)−0.002 (2)
C20.061 (3)0.041 (3)0.069 (3)0.001 (2)0.002 (3)0.002 (2)
C30.055 (3)0.052 (3)0.064 (3)−0.006 (2)0.004 (2)0.004 (2)
C40.054 (3)0.060 (3)0.080 (3)0.007 (3)−0.005 (3)0.012 (3)
C50.066 (3)0.049 (3)0.073 (3)0.002 (3)−0.005 (3)0.008 (2)
C60.061 (3)0.038 (3)0.053 (3)0.000 (2)0.005 (2)−0.0013 (19)
C70.058 (3)0.045 (3)0.053 (3)0.001 (2)0.004 (2)0.002 (2)
C80.050 (3)0.047 (3)0.048 (2)0.001 (2)0.003 (2)0.0021 (19)
C90.055 (3)0.048 (3)0.055 (3)−0.011 (2)−0.001 (2)0.000 (2)
C100.050 (3)0.055 (3)0.055 (3)0.001 (2)−0.002 (2)0.008 (2)
C110.060 (3)0.039 (2)0.050 (3)0.004 (2)0.003 (2)0.0070 (19)
C120.054 (3)0.045 (3)0.057 (3)−0.002 (2)0.003 (2)0.006 (2)
C130.048 (3)0.048 (3)0.052 (3)−0.002 (2)−0.005 (2)0.003 (2)
C140.051 (3)0.044 (2)0.041 (2)−0.003 (2)0.003 (2)−0.0004 (18)
C150.055 (3)0.044 (3)0.051 (3)−0.007 (2)0.002 (2)−0.003 (2)
C160.052 (3)0.048 (3)0.053 (3)0.000 (2)0.004 (2)0.003 (2)
C170.051 (3)0.058 (3)0.062 (3)−0.008 (2)−0.007 (2)−0.001 (2)
C180.063 (3)0.048 (3)0.066 (3)−0.010 (2)−0.002 (3)−0.002 (2)
C190.053 (3)0.046 (3)0.045 (2)−0.006 (2)0.003 (2)0.0022 (19)
C200.062 (3)0.047 (3)0.052 (3)−0.004 (2)0.002 (2)0.000 (2)
C210.056 (3)0.044 (3)0.042 (2)0.004 (2)0.003 (2)0.0053 (18)
C220.054 (3)0.055 (3)0.043 (2)0.001 (2)0.002 (2)−0.0008 (19)
C230.059 (3)0.042 (3)0.054 (3)0.006 (2)−0.002 (2)0.006 (2)
C240.058 (3)0.051 (3)0.044 (2)−0.006 (2)−0.001 (2)0.001 (2)
C250.058 (3)0.064 (3)0.053 (3)−0.001 (3)−0.008 (2)0.003 (2)
C260.066 (3)0.045 (3)0.054 (3)−0.004 (2)−0.003 (2)0.003 (2)
N10.058 (3)0.049 (3)0.065 (2)−0.001 (2)−0.007 (2)−0.0022 (19)
N20.057 (3)0.063 (3)0.062 (2)0.008 (2)−0.008 (2)0.007 (2)
N30.059 (3)0.064 (3)0.089 (3)−0.011 (2)0.000 (3)0.002 (2)
N40.069 (3)0.039 (2)0.088 (3)0.008 (2)−0.014 (2)0.006 (2)
N50.068 (3)0.035 (2)0.060 (2)0.0043 (19)0.0047 (19)0.0060 (17)
N60.064 (3)0.043 (2)0.056 (2)0.0031 (19)0.0001 (19)0.0027 (17)
N70.068 (3)0.038 (2)0.053 (2)−0.0054 (19)0.0012 (19)−0.0002 (16)
N80.058 (2)0.039 (2)0.063 (2)−0.0008 (18)−0.0017 (19)0.0015 (17)
O10.072 (3)0.090 (3)0.121 (3)−0.011 (2)−0.027 (3)0.002 (2)
O20.085 (3)0.053 (2)0.157 (4)−0.008 (2)−0.013 (3)0.006 (2)
O30.069 (2)0.052 (2)0.096 (3)−0.0040 (18)−0.019 (2)−0.0004 (17)
O40.094 (3)0.048 (3)0.256 (6)0.001 (2)−0.075 (4)0.023 (3)
O50.087 (3)0.046 (2)0.105 (3)0.0062 (19)−0.012 (2)0.0089 (19)
O60.066 (3)0.084 (3)0.098 (3)0.005 (2)−0.016 (2)0.007 (2)
O70.081 (3)0.047 (2)0.142 (4)−0.0054 (19)−0.036 (3)−0.012 (2)
O80.070 (2)0.053 (2)0.095 (3)0.0059 (18)−0.019 (2)−0.0025 (18)
Cl10.0721 (9)0.0489 (7)0.0843 (9)0.0067 (6)−0.0118 (7)0.0137 (6)
Cl20.0824 (10)0.0512 (7)0.0750 (8)−0.0133 (6)−0.0150 (7)−0.0007 (6)
Cl30.0564 (8)0.0704 (9)0.0833 (9)−0.0032 (6)−0.0139 (7)−0.0004 (6)
Cl40.0567 (8)0.0676 (8)0.0911 (9)−0.0022 (6)−0.0189 (7)0.0157 (7)

Geometric parameters (Å, °)

C1—C21.379 (6)C16—N21.467 (6)
C1—C61.422 (6)C17—C181.352 (6)
C1—N41.455 (6)C17—H17A0.9300
C2—C31.352 (6)C18—C191.408 (6)
C2—H2A0.9300C18—H18A0.9300
C3—C41.385 (6)C19—N81.361 (5)
C3—N31.468 (6)C20—N71.280 (5)
C4—C51.351 (7)C20—C211.467 (6)
C4—H4A0.9300C20—H20A0.9300
C5—C61.409 (7)C21—C261.388 (6)
C5—H5A0.9300C21—C221.388 (6)
C6—N61.343 (5)C22—C231.395 (6)
C7—N51.267 (5)C22—Cl31.728 (5)
C7—C81.469 (6)C23—C241.371 (6)
C7—H7A0.9300C23—H23A0.9300
C8—C131.381 (6)C24—C251.376 (6)
C8—C91.390 (6)C24—Cl21.734 (4)
C9—C101.379 (6)C25—C261.380 (6)
C9—H9A0.9300C25—H25A0.9300
C10—C111.372 (6)C26—H26A0.9300
C10—H10A0.9300N1—O71.209 (4)
C11—C121.375 (6)N1—O81.224 (5)
C11—Cl11.739 (4)N2—O51.211 (5)
C12—C131.376 (6)N2—O61.229 (5)
C12—H12A0.9300N3—O21.204 (5)
C13—Cl41.736 (5)N3—O11.226 (5)
C14—C151.379 (6)N4—O41.197 (5)
C14—C191.422 (6)N4—O31.213 (5)
C14—N11.443 (6)N5—N61.373 (5)
C15—C161.365 (6)N6—H6A0.8600
C15—H15A0.9300N7—N81.368 (5)
C16—C171.384 (6)N8—H8A0.8600
C2—C1—C6121.6 (4)C18—C17—H17A119.9
C2—C1—N4117.1 (4)C16—C17—H17A119.9
C6—C1—N4121.3 (4)C17—C18—C19122.2 (4)
C3—C2—C1119.4 (4)C17—C18—H18A118.9
C3—C2—H2A120.3C19—C18—H18A118.9
C1—C2—H2A120.3N8—C19—C18120.5 (4)
C2—C3—C4121.3 (4)N8—C19—C14123.5 (4)
C2—C3—N3118.7 (4)C18—C19—C14116.0 (4)
C4—C3—N3119.9 (5)N7—C20—C21117.8 (4)
C5—C4—C3119.6 (5)N7—C20—H20A121.1
C5—C4—H4A120.2C21—C20—H20A121.1
C3—C4—H4A120.2C26—C21—C22116.9 (4)
C4—C5—C6122.3 (4)C26—C21—C20121.2 (4)
C4—C5—H5A118.8C22—C21—C20121.9 (4)
C6—C5—H5A118.8C21—C22—C23122.4 (4)
N6—C6—C5119.8 (4)C21—C22—Cl3121.8 (3)
N6—C6—C1124.6 (4)C23—C22—Cl3115.8 (3)
C5—C6—C1115.6 (4)C24—C23—C22118.1 (4)
N5—C7—C8118.7 (4)C24—C23—H23A120.9
N5—C7—H7A120.6C22—C23—H23A120.9
C8—C7—H7A120.6C23—C24—C25121.5 (4)
C13—C8—C9116.8 (4)C23—C24—Cl2118.3 (3)
C13—C8—C7122.8 (4)C25—C24—Cl2120.2 (4)
C9—C8—C7120.4 (4)C24—C25—C26119.2 (4)
C10—C9—C8122.5 (4)C24—C25—H25A120.4
C10—C9—H9A118.8C26—C25—H25A120.4
C8—C9—H9A118.8C25—C26—C21121.9 (4)
C9—C10—C11118.0 (4)C25—C26—H26A119.0
C9—C10—H10A121.0C21—C26—H26A119.0
C11—C10—H10A121.0O7—N1—O8121.9 (4)
C12—C11—C10121.8 (4)O7—N1—C14119.2 (4)
C12—C11—Cl1118.4 (3)O8—N1—C14118.8 (4)
C10—C11—Cl1119.8 (4)O5—N2—O6124.3 (4)
C11—C12—C13118.5 (4)O5—N2—C16118.7 (4)
C11—C12—H12A120.8O6—N2—C16116.9 (4)
C13—C12—H12A120.8O2—N3—O1123.4 (5)
C12—C13—C8122.3 (4)O2—N3—C3119.0 (5)
C12—C13—Cl4116.8 (3)O1—N3—C3117.6 (4)
C8—C13—Cl4120.9 (3)O4—N4—O3122.3 (4)
C15—C14—C19121.2 (4)O4—N4—C1117.7 (4)
C15—C14—N1116.4 (4)O3—N4—C1120.0 (4)
C19—C14—N1122.4 (4)C7—N5—N6118.1 (4)
C16—C15—C14119.9 (4)C6—N6—N5118.1 (4)
C16—C15—H15A120.0C6—N6—H6A120.9
C14—C15—H15A120.0N5—N6—H6A120.9
C15—C16—C17120.5 (4)C20—N7—N8117.0 (4)
C15—C16—N2119.7 (4)C19—N8—N7117.2 (4)
C17—C16—N2119.8 (4)C19—N8—H8A121.4
C18—C17—C16120.1 (4)N7—N8—H8A121.4

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N6—H6A···O30.862.052.645 (5)126
N8—H8A···O80.862.032.627 (5)126

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2743).

References

  • Bruker (1998). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Ohba, S. (1996). Acta Cryst. C52, 2118–2119.
  • Okabe, N., Nakamura, T. & Fukuda, H. (1993). Acta Cryst. C49, 1678–1680.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography