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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1745.
Published online 2009 July 4. doi:  10.1107/S1600536809024489
PMCID: PMC2977460

Benzil bis­(ketazine)

Abstract

The title compound (systematic name: 1,1′,2,2′-tetra­phenyl-2,2′-azinodiethanone), C28H20N2O2, was obtained by the reaction of benzil monohydrazone with chromium(III) nitrate. The dibenzyl­idene hydrazine unit is nearly planar (r.m.s. deviation = 0.073 Å) and the two benzoyl units are oriented almost perpendicular to it [dihedral angle = 87.81 (2), 87.81 (2)°]. The mol­ecules are linked into chains along the c axis by C—H(...)O hydrogen bonds and the chains are cross-linked via C—H(...)π inter­actions involving the benzoyl phenyl rings.

Related literature

For the synthesis of title compound using copper bis­(acetyl­acetonate) as catalyst, see: Ibata & Singh (1994 [triangle]); Singh (1983 [triangle]).

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Object name is e-65-o1745-scheme1.jpg

Experimental

Crystal data

  • C28H20N2O2
  • M r = 416.46
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1745-efi1.jpg
  • a = 8.2875 (2) Å
  • b = 22.1023 (4) Å
  • c = 11.6602 (2) Å
  • β = 97.539 (1)°
  • V = 2117.37 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 140 K
  • 0.30 × 0.04 × 0.03 mm

Data collection

  • Bruker SMART APEX area-detector diffractometer
  • Absorption correction: none
  • 17323 measured reflections
  • 4857 independent reflections
  • 3510 reflections with I > 2σ(I)
  • R int = 0.030

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.107
  • S = 1.03
  • 4857 reflections
  • 289 parameters
  • H-atom parameters constrained
  • Δρmax = 0.24 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [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: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809024489/ci2835sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809024489/ci2835Isup2.hkl

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

Acknowledgments

The authors thank Vijaygarh Jyotish Ray College and the University of Malaya for supporting this study.

supplementary crystallographic information

Experimental

Benzil monohydrazone (0.224 g, 1 mmol) was dissolved in acetonitrile (20 ml) and to this was added chromium nitrate nonahyrate (0.40 g, 1 mmol). The greenish yellowish mixture was stirred at room temperature for 6 h. Bright yellow prisms were collected in 40% yield.

Refinement

H-atoms were placed in calculated positions (C-H = 0.95 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2Ueq(C).

Figures

Fig. 1.
Displacement ellipsoid plot (Barbour, 2001) of C28H20N2O2 at the 70% probability level; H atoms are drawn as spheres of arbitrary radius.

Crystal data

C28H20N2O2F(000) = 872
Mr = 416.46Dx = 1.306 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3878 reflections
a = 8.2875 (2) Åθ = 2.5–27.9°
b = 22.1023 (4) ŵ = 0.08 mm1
c = 11.6602 (2) ÅT = 140 K
β = 97.539 (1)°Prism, yellow
V = 2117.37 (7) Å30.30 × 0.04 × 0.03 mm
Z = 4

Data collection

Bruker SMART APEX area-detector diffractometer3510 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.030
graphiteθmax = 27.5°, θmin = 1.8°
ω scansh = −10→10
17323 measured reflectionsk = −28→27
4857 independent reflectionsl = −15→15

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.0486P)2 + 0.4715P] where P = (Fo2 + 2Fc2)/3
4857 reflections(Δ/σ)max = 0.001
289 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = −0.21 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O10.37058 (13)0.75630 (5)0.13158 (8)0.0366 (3)
O20.17265 (13)0.56277 (5)0.47749 (8)0.0336 (3)
N10.34699 (13)0.66169 (5)0.33697 (11)0.0257 (3)
N20.18382 (13)0.66513 (5)0.28286 (10)0.0252 (3)
C10.27649 (16)0.81384 (6)0.40407 (11)0.0215 (3)
H10.32940.78350.45310.026*
C20.20231 (17)0.86230 (7)0.45113 (13)0.0303 (3)
H20.20430.86530.53260.036*
C30.12519 (19)0.90640 (7)0.37938 (15)0.0377 (4)
H30.07440.93970.41180.045*
C40.12170 (19)0.90223 (7)0.26063 (15)0.0370 (4)
H40.06780.93250.21190.044*
C50.19592 (17)0.85447 (6)0.21267 (13)0.0278 (3)
H50.19450.85200.13120.033*
C60.27335 (15)0.80970 (6)0.28467 (11)0.0198 (3)
C70.35415 (15)0.75841 (6)0.23347 (11)0.0219 (3)
C80.42829 (16)0.70877 (6)0.31371 (11)0.0211 (3)
C90.59933 (16)0.71554 (6)0.36520 (11)0.0211 (3)
C100.66251 (18)0.67959 (7)0.45829 (13)0.0318 (3)
H100.59490.65040.48810.038*
C110.82226 (18)0.68586 (7)0.50792 (14)0.0349 (4)
H110.86390.66120.57170.042*
C120.92181 (17)0.72815 (7)0.46459 (13)0.0296 (3)
H121.03190.73240.49850.036*
C130.86090 (17)0.76404 (7)0.37219 (13)0.0312 (3)
H130.92940.79290.34220.037*
C140.70016 (17)0.75823 (6)0.32287 (12)0.0267 (3)
H140.65860.78350.25990.032*
C150.10218 (16)0.61745 (6)0.30204 (11)0.0215 (3)
C16−0.06870 (16)0.61175 (6)0.24937 (11)0.0215 (3)
C17−0.16874 (17)0.56676 (6)0.28567 (13)0.0279 (3)
H17−0.12740.53980.34600.033*
C18−0.32831 (18)0.56134 (7)0.23374 (14)0.0327 (3)
H18−0.39610.53060.25860.039*
C19−0.38917 (17)0.60026 (7)0.14627 (13)0.0307 (3)
H19−0.49870.59620.11100.037*
C20−0.29147 (17)0.64511 (7)0.10965 (13)0.0302 (3)
H20−0.33380.67200.04950.036*
C21−0.13179 (17)0.65073 (6)0.16090 (12)0.0269 (3)
H21−0.06460.68150.13550.032*
C220.17830 (16)0.56479 (6)0.37387 (11)0.0222 (3)
C230.25313 (16)0.51611 (6)0.31005 (12)0.0215 (3)
C240.34362 (17)0.47038 (7)0.37097 (13)0.0299 (3)
H240.35540.46970.45310.036*
C250.4161 (2)0.42613 (7)0.31128 (15)0.0372 (4)
H250.48000.39560.35280.045*
C260.39637 (19)0.42599 (7)0.19180 (14)0.0344 (4)
H260.44590.39520.15160.041*
C270.30485 (18)0.47042 (7)0.13063 (13)0.0309 (3)
H270.29030.47000.04840.037*
C280.23428 (17)0.51564 (6)0.18982 (12)0.0242 (3)
H280.17250.54660.14780.029*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0392 (6)0.0513 (7)0.0191 (5)0.0020 (5)0.0023 (4)−0.0069 (5)
O20.0389 (6)0.0379 (6)0.0238 (5)0.0007 (5)0.0037 (4)−0.0048 (4)
N10.0177 (6)0.0207 (6)0.0374 (7)−0.0007 (4)−0.0007 (5)−0.0034 (5)
N20.0167 (6)0.0214 (6)0.0366 (7)−0.0006 (4)0.0000 (5)−0.0056 (5)
C10.0188 (6)0.0230 (6)0.0220 (7)−0.0012 (5)−0.0003 (5)0.0008 (5)
C20.0244 (7)0.0341 (8)0.0317 (8)−0.0013 (6)0.0009 (6)−0.0103 (6)
C30.0286 (8)0.0273 (8)0.0549 (11)0.0056 (6)−0.0034 (7)−0.0120 (7)
C40.0334 (8)0.0229 (7)0.0501 (10)0.0023 (6)−0.0119 (7)0.0057 (7)
C50.0265 (7)0.0266 (7)0.0278 (7)−0.0057 (6)−0.0051 (6)0.0066 (6)
C60.0162 (6)0.0200 (6)0.0227 (7)−0.0044 (5)0.0004 (5)0.0012 (5)
C70.0171 (6)0.0267 (7)0.0206 (6)−0.0055 (5)−0.0017 (5)−0.0039 (5)
C80.0199 (7)0.0202 (6)0.0230 (7)−0.0002 (5)0.0026 (5)−0.0061 (5)
C90.0187 (6)0.0207 (6)0.0238 (7)−0.0006 (5)0.0018 (5)−0.0055 (5)
C100.0245 (7)0.0319 (8)0.0380 (8)−0.0049 (6)−0.0002 (6)0.0069 (6)
C110.0291 (8)0.0367 (8)0.0363 (8)0.0007 (6)−0.0058 (7)0.0049 (7)
C120.0178 (7)0.0347 (8)0.0350 (8)−0.0014 (6)−0.0014 (6)−0.0115 (6)
C130.0231 (7)0.0346 (8)0.0358 (8)−0.0082 (6)0.0029 (6)−0.0029 (6)
C140.0244 (7)0.0276 (7)0.0275 (7)−0.0033 (6)0.0010 (6)−0.0008 (6)
C150.0206 (7)0.0192 (6)0.0252 (7)−0.0008 (5)0.0045 (5)−0.0066 (5)
C160.0197 (6)0.0192 (6)0.0261 (7)−0.0010 (5)0.0045 (5)−0.0064 (5)
C170.0244 (7)0.0256 (7)0.0332 (8)−0.0025 (6)0.0025 (6)−0.0012 (6)
C180.0242 (7)0.0331 (8)0.0413 (9)−0.0104 (6)0.0064 (6)−0.0038 (7)
C190.0185 (7)0.0386 (8)0.0343 (8)−0.0021 (6)0.0002 (6)−0.0102 (6)
C200.0254 (7)0.0341 (8)0.0300 (8)0.0014 (6)−0.0004 (6)−0.0013 (6)
C210.0232 (7)0.0257 (7)0.0320 (8)−0.0030 (6)0.0041 (6)−0.0009 (6)
C220.0180 (6)0.0241 (7)0.0240 (7)−0.0051 (5)0.0013 (5)−0.0032 (5)
C230.0186 (6)0.0189 (6)0.0270 (7)−0.0030 (5)0.0027 (5)−0.0001 (5)
C240.0288 (8)0.0319 (8)0.0295 (8)0.0032 (6)0.0060 (6)0.0076 (6)
C250.0386 (9)0.0268 (8)0.0485 (10)0.0117 (7)0.0140 (8)0.0129 (7)
C260.0374 (9)0.0232 (7)0.0455 (9)0.0040 (6)0.0166 (7)−0.0017 (6)
C270.0326 (8)0.0313 (8)0.0295 (8)0.0000 (6)0.0063 (6)−0.0050 (6)
C280.0238 (7)0.0221 (7)0.0264 (7)0.0009 (5)0.0016 (6)0.0000 (5)

Geometric parameters (Å, °)

O1—C71.2143 (16)C13—H130.95
O2—C221.2160 (16)C14—H140.95
N1—C81.2878 (17)C15—C161.4733 (18)
N1—N21.4173 (15)C15—C221.5216 (19)
N2—C151.2877 (17)C16—C211.3922 (19)
C1—C21.3839 (19)C16—C171.3955 (19)
C1—C61.3920 (18)C17—C181.385 (2)
C1—H10.95C17—H170.95
C2—C31.385 (2)C18—C191.378 (2)
C2—H20.95C18—H180.95
C3—C41.384 (2)C19—C201.383 (2)
C3—H30.95C19—H190.95
C4—C51.377 (2)C20—C211.384 (2)
C4—H40.95C20—H200.95
C5—C61.3980 (18)C21—H210.95
C5—H50.95C22—C231.4890 (18)
C6—C71.4814 (18)C23—C281.3902 (19)
C7—C81.5185 (18)C23—C241.3959 (19)
C8—C91.4727 (18)C24—C251.383 (2)
C9—C101.3908 (19)C24—H240.95
C9—C141.3929 (19)C25—C261.381 (2)
C10—C111.380 (2)C25—H250.95
C10—H100.95C26—C271.381 (2)
C11—C121.385 (2)C26—H260.95
C11—H110.95C27—C281.3869 (19)
C12—C131.379 (2)C27—H270.95
C12—H120.95C28—H280.95
C13—C141.386 (2)
C8—N1—N2110.97 (11)C9—C14—H14119.9
C15—N2—N1111.78 (11)N2—C15—C16119.72 (12)
C2—C1—C6119.77 (13)N2—C15—C22122.16 (12)
C2—C1—H1120.1C16—C15—C22118.06 (11)
C6—C1—H1120.1C21—C16—C17119.04 (12)
C1—C2—C3119.93 (14)C21—C16—C15120.20 (12)
C1—C2—H2120.0C17—C16—C15120.75 (12)
C3—C2—H2120.0C18—C17—C16120.00 (14)
C4—C3—C2120.32 (14)C18—C17—H17120.0
C4—C3—H3119.8C16—C17—H17120.0
C2—C3—H3119.8C19—C18—C17120.34 (13)
C5—C4—C3120.37 (14)C19—C18—H18119.8
C5—C4—H4119.8C17—C18—H18119.8
C3—C4—H4119.8C18—C19—C20120.25 (13)
C4—C5—C6119.54 (14)C18—C19—H19119.9
C4—C5—H5120.2C20—C19—H19119.9
C6—C5—H5120.2C19—C20—C21119.76 (14)
C1—C6—C5120.06 (13)C19—C20—H20120.1
C1—C6—C7120.21 (12)C21—C20—H20120.1
C5—C6—C7119.71 (12)C20—C21—C16120.61 (13)
O1—C7—C6122.57 (13)C20—C21—H21119.7
O1—C7—C8119.13 (12)C16—C21—H21119.7
C6—C7—C8118.18 (11)O2—C22—C23122.88 (13)
N1—C8—C9119.89 (12)O2—C22—C15120.51 (12)
N1—C8—C7122.21 (12)C23—C22—C15116.58 (11)
C9—C8—C7117.89 (11)C28—C23—C24119.31 (12)
C10—C9—C14118.78 (12)C28—C23—C22120.68 (12)
C10—C9—C8120.25 (12)C24—C23—C22120.01 (12)
C14—C9—C8120.96 (12)C25—C24—C23119.74 (14)
C11—C10—C9120.80 (14)C25—C24—H24120.1
C11—C10—H10119.6C23—C24—H24120.1
C9—C10—H10119.6C26—C25—C24120.49 (14)
C10—C11—C12119.94 (14)C26—C25—H25119.8
C10—C11—H11120.0C24—C25—H25119.8
C12—C11—H11120.0C25—C26—C27120.26 (14)
C13—C12—C11119.90 (13)C25—C26—H26119.9
C13—C12—H12120.0C27—C26—H26119.9
C11—C12—H12120.0C26—C27—C28119.63 (14)
C12—C13—C14120.27 (14)C26—C27—H27120.2
C12—C13—H13119.9C28—C27—H27120.2
C14—C13—H13119.9C23—C28—C27120.55 (13)
C13—C14—C9120.30 (13)C23—C28—H28119.7
C13—C14—H14119.9C27—C28—H28119.7
C8—N1—N2—C15177.82 (12)N1—N2—C15—C16−177.87 (11)
C6—C1—C2—C30.1 (2)N1—N2—C15—C22−0.55 (17)
C1—C2—C3—C40.1 (2)N2—C15—C16—C2113.52 (19)
C2—C3—C4—C5−0.5 (2)C22—C15—C16—C21−163.92 (12)
C3—C4—C5—C60.8 (2)N2—C15—C16—C17−167.62 (13)
C2—C1—C6—C50.20 (19)C22—C15—C16—C1714.95 (18)
C2—C1—C6—C7179.23 (12)C21—C16—C17—C180.1 (2)
C4—C5—C6—C1−0.6 (2)C15—C16—C17—C18−178.82 (13)
C4—C5—C6—C7−179.66 (12)C16—C17—C18—C19−0.1 (2)
C1—C6—C7—O1−171.53 (13)C17—C18—C19—C20−0.1 (2)
C5—C6—C7—O17.51 (19)C18—C19—C20—C210.2 (2)
C1—C6—C7—C84.51 (18)C19—C20—C21—C16−0.2 (2)
C5—C6—C7—C8−176.45 (12)C17—C16—C21—C200.1 (2)
N2—N1—C8—C9177.59 (11)C15—C16—C21—C20178.98 (12)
N2—N1—C8—C7−2.72 (17)N2—C15—C22—O291.73 (16)
O1—C7—C8—N1−93.45 (16)C16—C15—C22—O2−90.91 (15)
C6—C7—C8—N190.38 (15)N2—C15—C22—C23−90.28 (15)
O1—C7—C8—C986.25 (15)C16—C15—C22—C2387.09 (14)
C6—C7—C8—C9−89.92 (14)O2—C22—C23—C28169.79 (13)
N1—C8—C9—C10−15.03 (19)C15—C22—C23—C28−8.15 (18)
C7—C8—C9—C10165.26 (12)O2—C22—C23—C24−10.4 (2)
N1—C8—C9—C14165.69 (13)C15—C22—C23—C24171.70 (12)
C7—C8—C9—C14−14.01 (18)C28—C23—C24—C251.4 (2)
C14—C9—C10—C11−0.2 (2)C22—C23—C24—C25−178.43 (13)
C8—C9—C10—C11−179.45 (13)C23—C24—C25—C26−1.6 (2)
C9—C10—C11—C12−0.3 (2)C24—C25—C26—C270.5 (2)
C10—C11—C12—C130.2 (2)C25—C26—C27—C280.7 (2)
C11—C12—C13—C140.4 (2)C24—C23—C28—C27−0.2 (2)
C12—C13—C14—C9−0.8 (2)C22—C23—C28—C27179.65 (13)
C10—C9—C14—C130.7 (2)C26—C27—C28—C23−0.9 (2)
C8—C9—C14—C13−179.97 (13)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C1—H1···O1i0.952.243.0832 (16)147
C13—H13···Cg1ii0.952.683.5705 (16)157
C18—H18···Cg2iii0.952.663.5304 (16)153

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x+1, y, z; (iii) x−1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2835).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2008). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Ibata, T. & Singh, G. S. (1994). Tetrahedron Lett.35, 2581–2584.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Singh, S. B. (1983). Indian J. Chem. Sect. B, 20, 810.
  • Westrip, S. P. (2009). publCIF In preparation.

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