organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

Bi­phenyl-4-carbaldehyde azine

aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my

(Received 18 November 2008; accepted 19 November 2008; online 26 November 2008)

The complete mol­ecule of the title compound, C26H20N2, is generated by crystallographic inversion symmetry. The terminal phenyl ring is twisted by 19.2 (1)° with respect to the adjacent phenyl­ene ring.

Related literature

For the synthesis, see: Malkes & Timchenko (1961[Malkes, L. Ya. & Timchenko, A. I. (1961). Zh. Obshch. Khim. 31, 560-562.]). For biological evaluation, see: Cremlyn et al. (1991[Cremlyn, R. J., Swinburne, F. J., Graham, S., Calvaleiro, J. A. S., Domingues, F. J. & Dias, M. (1991). Phosphorus Sulfur Silicon Rel. Elem. 60, 57-65.]). The compound is a formylating agent for aromatic compounds; see: Kantlehner et al. (2004[Kantlehner, W., Haug, E., Scherr, O., Stoyanov, E. V., Mezger, J. & Ziegler, G. (2004). Z. Naturforsch. Teil B, 59, 357-365.]). When treated with cerium ammonium nitrate, the aldehyde is regenerated; see Giurg & Mlochowski (1999[Giurg, M. & Mlochowski, J. (1999). Synth. Commun. 29, 4307-4313.]).

[Scheme 1]

Experimental

Crystal data
  • C26H20N2

  • Mr = 360.44

  • Monoclinic, P 21 /c

  • a = 20.5417 (6) Å

  • b = 7.1358 (2) Å

  • c = 6.3402 (2) Å

  • β = 93.632 (2)°

  • V = 927.49 (5) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 100 (2) K

  • 0.40 × 0.25 × 0.10 mm

Data collection
  • Bruker SMART APEX CCD diffractometer

  • Absorption correction: none

  • 6044 measured reflections

  • 2104 independent reflections

  • 1607 reflections with I > 2σ(I)

  • Rint = 0.025

Refinement
  • R[F2 > 2σ(F2)] = 0.042

  • wR(F2) = 0.127

  • S = 1.05

  • 2104 reflections

  • 127 parameters

  • H-atom parameters constrained

  • Δρmax = 0.31 e Å−3

  • Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2008[Westrip, S. P. (2008). publCIF. In preparation.]).

Supporting information


Comment top

The complete molecule of the title compound, (I) is generated by crystallographic inversion symmetry (Fig. 1). The terminal phenyl ring is twisted by 19.2 (1) ° with respect to the phenylene ring.

Related literature top

For the synthesis, see: Malkes & Timchenko (1961). For biological evaluation, see: Cremlyn et al. (1991). The compound is a formalating agent for aromatic compounds; see: Kantlehner et al. (2004). When treated with cerium ammonium nitrate, the aldehyde is regenerated; see Giurg & Mlochowski (1999).

Experimental top

4-Phenyl benzaldehyde (0.72 g, 4 mmol) and 80% hydrazine hydrate (0.10 g, 2 mmol) were heated in ethanol (25 ml) for 1 h. The resulting product was filtered and washed with ethanol and then recrystallized from hexane to yield yellow prisms of (I).

Refinement top

The H atoms were placed in calculated positions (C—H = 0.95 Å) and refined as riding with U(H) = 1.2U(C).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with atoms shown at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radiius. The unlabelled atoms are generated by the symmetry operation (1–x, 1–y, 1–z).
Biphenyl-4-carbaldehyde azine top
Crystal data top
C26H20N2F(000) = 380
Mr = 360.44Dx = 1.291 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1869 reflections
a = 20.5417 (6) Åθ = 2.9–26.2°
b = 7.1358 (2) ŵ = 0.08 mm1
c = 6.3402 (2) ÅT = 100 K
β = 93.632 (2)°Prism, yellow
V = 927.49 (5) Å30.40 × 0.25 × 0.10 mm
Z = 2
Data collection top
Bruker SMART APEX CCD
diffractometer
1607 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.025
Graphite monochromatorθmax = 27.5°, θmin = 1.0°
ω scansh = 2526
6044 measured reflectionsk = 89
2104 independent reflectionsl = 88
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)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0641P)2 + 0.2493P]
where P = (Fo2 + 2Fc2)/3
2104 reflections(Δ/σ)max = 0.001
127 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.21 e Å3
Crystal data top
C26H20N2V = 927.49 (5) Å3
Mr = 360.44Z = 2
Monoclinic, P21/cMo Kα radiation
a = 20.5417 (6) ŵ = 0.08 mm1
b = 7.1358 (2) ÅT = 100 K
c = 6.3402 (2) Å0.40 × 0.25 × 0.10 mm
β = 93.632 (2)°
Data collection top
Bruker SMART APEX CCD
diffractometer
1607 reflections with I > 2σ(I)
6044 measured reflectionsRint = 0.025
2104 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.127H-atom parameters constrained
S = 1.06Δρmax = 0.31 e Å3
2104 reflectionsΔρmin = 0.21 e Å3
127 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.46654 (6)0.48506 (18)0.47390 (19)0.0260 (3)
C10.45139 (7)0.5211 (2)0.2795 (2)0.0229 (3)
H10.48470.55980.19160.027*
C20.38464 (7)0.50463 (19)0.1880 (2)0.0202 (3)
C30.37032 (7)0.5594 (2)0.0206 (2)0.0218 (3)
H30.40450.60060.10340.026*
C40.30685 (7)0.5548 (2)0.1095 (2)0.0205 (3)
H40.29830.59270.25220.025*
C50.25534 (6)0.49541 (19)0.0078 (2)0.0169 (3)
C60.27039 (7)0.43846 (19)0.2177 (2)0.0198 (3)
H60.23630.39720.30080.024*
C70.33352 (7)0.4412 (2)0.3054 (2)0.0212 (3)
H70.34240.39980.44670.025*
C80.18693 (6)0.49529 (18)0.08434 (19)0.0170 (3)
C90.16848 (7)0.60293 (19)0.2631 (2)0.0202 (3)
H90.20050.67450.32870.024*
C100.10445 (7)0.6072 (2)0.3461 (2)0.0215 (3)
H100.09320.68110.46760.026*
C110.05681 (7)0.5041 (2)0.2529 (2)0.0200 (3)
H110.01280.50830.30840.024*
C120.07425 (6)0.39455 (19)0.0772 (2)0.0197 (3)
H120.04200.32240.01320.024*
C130.13839 (6)0.38970 (19)0.0054 (2)0.0186 (3)
H130.14960.31330.12490.022*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0154 (6)0.0334 (7)0.0285 (7)0.0007 (5)0.0034 (5)0.0004 (5)
C10.0174 (7)0.0249 (8)0.0261 (7)0.0009 (5)0.0003 (5)0.0009 (6)
C20.0171 (7)0.0195 (7)0.0235 (7)0.0013 (5)0.0018 (5)0.0020 (5)
C30.0181 (7)0.0244 (7)0.0231 (7)0.0002 (5)0.0028 (5)0.0015 (5)
C40.0205 (7)0.0229 (7)0.0178 (6)0.0009 (5)0.0002 (5)0.0015 (5)
C50.0168 (7)0.0149 (6)0.0187 (6)0.0012 (5)0.0017 (5)0.0015 (5)
C60.0188 (7)0.0209 (7)0.0196 (6)0.0007 (5)0.0013 (5)0.0015 (5)
C70.0221 (7)0.0225 (7)0.0186 (6)0.0005 (5)0.0020 (5)0.0007 (5)
C80.0185 (7)0.0164 (6)0.0160 (6)0.0012 (5)0.0010 (5)0.0028 (5)
C90.0203 (7)0.0201 (7)0.0200 (6)0.0024 (5)0.0000 (5)0.0025 (5)
C100.0245 (7)0.0213 (7)0.0182 (6)0.0011 (5)0.0036 (5)0.0020 (5)
C110.0170 (7)0.0227 (7)0.0197 (6)0.0018 (5)0.0037 (5)0.0036 (5)
C120.0185 (7)0.0210 (7)0.0196 (6)0.0016 (5)0.0022 (5)0.0010 (5)
C130.0195 (7)0.0191 (7)0.0169 (6)0.0008 (5)0.0004 (5)0.0010 (5)
Geometric parameters (Å, º) top
N1—C11.2784 (19)C6—H60.9500
N1—N1i1.410 (2)C7—H70.9500
C1—C21.4592 (18)C8—C131.3989 (18)
C1—H10.9500C8—C91.4012 (18)
C2—C31.3927 (18)C9—C101.3858 (19)
C2—C71.4006 (19)C9—H90.9500
C3—C41.3874 (18)C10—C111.3863 (19)
C3—H30.9500C10—H100.9500
C4—C51.3969 (19)C11—C121.3888 (19)
C4—H40.9500C11—H110.9500
C5—C61.4073 (18)C12—C131.3870 (18)
C5—C81.4873 (17)C12—H120.9500
C6—C71.3784 (18)C13—H130.9500
C1—N1—N1i111.73 (15)C6—C7—H7119.7
N1—C1—C2122.17 (13)C2—C7—H7119.7
N1—C1—H1118.9C13—C8—C9117.44 (12)
C2—C1—H1118.9C13—C8—C5121.38 (11)
C3—C2—C7118.38 (12)C9—C8—C5121.17 (12)
C3—C2—C1119.45 (13)C10—C9—C8121.38 (12)
C7—C2—C1122.14 (12)C10—C9—H9119.3
C4—C3—C2121.03 (12)C8—C9—H9119.3
C4—C3—H3119.5C9—C10—C11120.34 (12)
C2—C3—H3119.5C9—C10—H10119.8
C3—C4—C5121.01 (12)C11—C10—H10119.8
C3—C4—H4119.5C10—C11—C12119.17 (12)
C5—C4—H4119.5C10—C11—H11120.4
C4—C5—C6117.55 (12)C12—C11—H11120.4
C4—C5—C8121.34 (11)C13—C12—C11120.49 (13)
C6—C5—C8121.11 (12)C13—C12—H12119.8
C7—C6—C5121.48 (12)C11—C12—H12119.8
C7—C6—H6119.3C12—C13—C8121.16 (12)
C5—C6—H6119.3C12—C13—H13119.4
C6—C7—C2120.53 (12)C8—C13—H13119.4
N1i—N1—C1—C2178.70 (14)C4—C5—C8—C13161.70 (13)
N1—C1—C2—C3175.14 (14)C6—C5—C8—C1319.36 (19)
N1—C1—C2—C72.6 (2)C4—C5—C8—C919.07 (19)
C7—C2—C3—C41.2 (2)C6—C5—C8—C9159.86 (13)
C1—C2—C3—C4176.66 (13)C13—C8—C9—C100.99 (19)
C2—C3—C4—C50.1 (2)C5—C8—C9—C10178.27 (12)
C3—C4—C5—C60.8 (2)C8—C9—C10—C110.1 (2)
C3—C4—C5—C8178.21 (13)C9—C10—C11—C120.9 (2)
C4—C5—C6—C70.1 (2)C10—C11—C12—C130.7 (2)
C8—C5—C6—C7178.86 (12)C11—C12—C13—C80.5 (2)
C5—C6—C7—C21.2 (2)C9—C8—C13—C121.26 (19)
C3—C2—C7—C61.8 (2)C5—C8—C13—C12177.99 (12)
C1—C2—C7—C6175.96 (13)
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC26H20N2
Mr360.44
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)20.5417 (6), 7.1358 (2), 6.3402 (2)
β (°) 93.632 (2)
V3)927.49 (5)
Z2
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.40 × 0.25 × 0.10
Data collection
DiffractometerBruker SMART APEX CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
6044, 2104, 1607
Rint0.025
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.127, 1.06
No. of reflections2104
No. of parameters127
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.31, 0.21

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

 

Acknowledgements

We thank the University of Malaya for supporting this study.

References

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCremlyn, R. J., Swinburne, F. J., Graham, S., Calvaleiro, J. A. S., Domingues, F. J. & Dias, M. (1991). Phosphorus Sulfur Silicon Rel. Elem. 60, 57–65.  CrossRef CAS Web of Science Google Scholar
First citationGiurg, M. & Mlochowski, J. (1999). Synth. Commun. 29, 4307–4313.  Web of Science CrossRef CAS Google Scholar
First citationKantlehner, W., Haug, E., Scherr, O., Stoyanov, E. V., Mezger, J. & Ziegler, G. (2004). Z. Naturforsch. Teil B, 59, 357–365.  CAS Google Scholar
First citationMalkes, L. Ya. & Timchenko, A. I. (1961). Zh. Obshch. Khim. 31, 560–562.  CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2008). publCIF. In preparation.  Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds