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

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ISSN: 2056-9890

5-Imino-3,4-di­phenyl-1H-pyrrol-2-one

aDepartment of Chemistry, Saint Petersburg State University, Universitetsky Pr. 26, 198504 Stary Petergof, Russian Federation, and bDepartment of Chemistry, University of Jyvaskyla, PO Box 35 FI-40014 Jyväskylä, Finland
*Correspondence e-mail: t.chulkova@spbu.ru

(Received 7 January 2014; accepted 15 January 2014; online 18 January 2014)

The title compound, C16H12N2O, exists in the crystalline state as the 5-imino-3,4-di­phenyl­-1H-pyrrol-2-one tautomer. The dihedral angles between the pyrrole and phenyl rings are 35.3 (2) and 55.3 (2)°. In the crystal, inversion dimers linked by pairs of N—H⋯N hydrogen bonds generate a graph-set motif of R22(8) via N—H⋯N hydrogen bonds.

Related literature

For general background to 5-imino­pyrrol-2-ones, see: Alves et al. (2009[Alves, M. J., Carvalho, M. A., Proença, M. F. J. R. P. & Booth, B. L. (2009). J. Heterocycl. Chem. 37, 1041-1048.]). For crystal structures of related compounds, see: Zhang et al. (2004[Zhang, Z.-Q., Uth, S., Sandman, D. J. & Foxman, B. M. (2004). J. Phys. Org. Chem. 17, 769-776.]).

[Scheme 1]

Experimental

Crystal data
  • C16H12N2O

  • Mr = 248.28

  • Monoclinic, C 2/n

  • a = 19.687 (3) Å

  • b = 6.3064 (10) Å

  • c = 20.611 (3) Å

  • β = 97.850 (3)°

  • V = 2534.8 (7) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 100 K

  • 0.12 × 0.10 × 0.07 mm

Data collection
  • Bruker KappaAPEXII diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2008b[Sheldrick, G. M. (2008b). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.990, Tmax = 0.994

  • 8351 measured reflections

  • 2178 independent reflections

  • 1360 reflections with I > 2σ(I)

  • Rint = 0.050

Refinement
  • R[F2 > 2σ(F2)] = 0.043

  • wR(F2) = 0.097

  • S = 1.00

  • 2178 reflections

  • 180 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.17 e Å−3

  • Δρmin = −0.18 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯N2i 0.93 (2) 1.96 (2) 2.882 (3) 172 (2)
Symmetry code: (i) -x+1, -y+3, -z+1.

Data collection: APEX2 (Bruker, 2010[Bruker (2010). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008a[Sheldrick, G. M. (2008a). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008a[Sheldrick, G. M. (2008a). Acta Cryst. A64, 112-122.]) and SHELXLE (Hübschle et al., 2011[Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281-1284.]); molecular graphics: OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

The goal of this work was to determine which of the possible tautomers, viz. 5-Imino-3,4-di­phenyl-1H-pyrrol-2-one or 5-amino-3,4-di­phenyl-2H-pyrrol-2-one, is stabilized in the solid state.

In the title compound, the C1–N1 and C4–N1 bonds have the same length (1.380 (3) Å), which is longer than the C4–N2 bond length (1.271 (2) Å). In combination with the features of the difference Fourier map, this allows the unambiguous location of the hydrogen atom at the N1 atom. Thus, the title compound exists as 5-Imino-3,4-di­phenyl-1H-pyrrol-2-one in the crystalline state. Two monomeric title compounds are linked together by hydrogen bonds N–H•••N making a graph-set motif of R22(8) (Table 1, Fig. 2).

Experimental top

3,4-Di­phenyl-1H-pyrrol-2,5-di­imine (0.121 mmol, 0.030 g) was hydrolyzed in undried chloro­form (1 mL) for 1 week at room temperature. The yellow crystals of 5-Imino-3,4-di­phenyl-1H-pyrrol-2-one were obtained from the reaction mixture.

Refinement top

The crystal of the title compound was immersed in cryo-oil, mounted in a Nylon loop, and measured at a temperature of 100 K. The X-ray diffraction data was collected on a Bruker Kappa Apex II diffractometer using MoKα radiation (λ = 0.71073 Å). The APEX2 (Bruker AXS, 2010) program package was used for cell refinements and data reductions. The structure was solved by direct methods using the SHELXS-97 (Sheldrick, 2008a) program. A multi-scan absorption correction based on equivalent reflections (SADABS, Sheldrick, 2008b) was applied to the data. Structural refinement was carried out using SHELXL-97 (Sheldrick, 2008a) with the Olex2 (Dolomanov et al., 2009) and SHELXLE (Hübschle et al., 2011) graphical user inter­faces.

The NH hydrogen atoms were located from a difference Fourier map and refined isotropically. Other hydrogen atoms were positioned geometrically and were also constrained to ride on their parent atoms, with C–H = 0.95 Å and Uiso = 1.2 Ueq (parent atom). The highest peak is located 1.08 Å from atom H6 and the deepest hole is located 0.98 Å from atom N1.

Related literature top

For general background to 5-iminopyrrol-2-ones, see: Alves et al. (2009). For crystal structures of related compounds, see: Zhang et al. (2004).

Structure description top

The goal of this work was to determine which of the possible tautomers, viz. 5-Imino-3,4-di­phenyl-1H-pyrrol-2-one or 5-amino-3,4-di­phenyl-2H-pyrrol-2-one, is stabilized in the solid state.

In the title compound, the C1–N1 and C4–N1 bonds have the same length (1.380 (3) Å), which is longer than the C4–N2 bond length (1.271 (2) Å). In combination with the features of the difference Fourier map, this allows the unambiguous location of the hydrogen atom at the N1 atom. Thus, the title compound exists as 5-Imino-3,4-di­phenyl-1H-pyrrol-2-one in the crystalline state. Two monomeric title compounds are linked together by hydrogen bonds N–H•••N making a graph-set motif of R22(8) (Table 1, Fig. 2).

3,4-Di­phenyl-1H-pyrrol-2,5-di­imine (0.121 mmol, 0.030 g) was hydrolyzed in undried chloro­form (1 mL) for 1 week at room temperature. The yellow crystals of 5-Imino-3,4-di­phenyl-1H-pyrrol-2-one were obtained from the reaction mixture.

For general background to 5-iminopyrrol-2-ones, see: Alves et al. (2009). For crystal structures of related compounds, see: Zhang et al. (2004).

Refinement details top

The crystal of the title compound was immersed in cryo-oil, mounted in a Nylon loop, and measured at a temperature of 100 K. The X-ray diffraction data was collected on a Bruker Kappa Apex II diffractometer using MoKα radiation (λ = 0.71073 Å). The APEX2 (Bruker AXS, 2010) program package was used for cell refinements and data reductions. The structure was solved by direct methods using the SHELXS-97 (Sheldrick, 2008a) program. A multi-scan absorption correction based on equivalent reflections (SADABS, Sheldrick, 2008b) was applied to the data. Structural refinement was carried out using SHELXL-97 (Sheldrick, 2008a) with the Olex2 (Dolomanov et al., 2009) and SHELXLE (Hübschle et al., 2011) graphical user inter­faces.

The NH hydrogen atoms were located from a difference Fourier map and refined isotropically. Other hydrogen atoms were positioned geometrically and were also constrained to ride on their parent atoms, with C–H = 0.95 Å and Uiso = 1.2 Ueq (parent atom). The highest peak is located 1.08 Å from atom H6 and the deepest hole is located 0.98 Å from atom N1.

Computing details top

Data collection: APEX2 (Bruker AXS, 2010); cell refinement: APEX2 (Bruker AXS, 2010); data reduction: APEX2 (Bruker AXS, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008a); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008a) and SHELXLE (Hübschle et al., 2011); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008a).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. The structure of the R22(8) dimeric graph-set motif of the title compound.
5-Imino-3,4-diphenyl-1H-pyrrol-2-one top
Crystal data top
C16H12N2OF(000) = 1040
Mr = 248.28Dx = 1.301 Mg m3
Monoclinic, C2/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ybcCell parameters from 1492 reflections
a = 19.687 (3) Åθ = 3.1–22.6°
b = 6.3064 (10) ŵ = 0.08 mm1
c = 20.611 (3) ÅT = 100 K
β = 97.850 (3)°Plate, yellow
V = 2534.8 (7) Å30.12 × 0.10 × 0.07 mm
Z = 8
Data collection top
Bruker KappaAPEXII
diffractometer
2178 independent reflections
Radiation source: fine-focus sealed tube1360 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromatorRint = 0.050
Detector resolution: 9 pixels mm-1θmax = 25.1°, θmin = 2.0°
φ scans and ω scans with κ offseth = 2320
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008b)
k = 77
Tmin = 0.990, Tmax = 0.994l = 2424
8351 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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.045P)2 + 0.1005P]
where P = (Fo2 + 2Fc2)/3
2178 reflections(Δ/σ)max < 0.001
180 parametersΔρmax = 0.17 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C16H12N2OV = 2534.8 (7) Å3
Mr = 248.28Z = 8
Monoclinic, C2/nMo Kα radiation
a = 19.687 (3) ŵ = 0.08 mm1
b = 6.3064 (10) ÅT = 100 K
c = 20.611 (3) Å0.12 × 0.10 × 0.07 mm
β = 97.850 (3)°
Data collection top
Bruker KappaAPEXII
diffractometer
2178 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008b)
1360 reflections with I > 2σ(I)
Tmin = 0.990, Tmax = 0.994Rint = 0.050
8351 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.17 e Å3
2178 reflectionsΔρmin = 0.18 e Å3
180 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
O10.57199 (8)1.0248 (2)0.40578 (7)0.0350 (4)
N10.50193 (9)1.2453 (3)0.45727 (8)0.0223 (4)
H10.5344 (12)1.344 (4)0.4747 (11)0.051 (8)*
N20.40778 (11)1.4207 (3)0.48842 (8)0.0247 (5)
H20.3658 (11)1.411 (3)0.4860 (10)0.024 (7)*
C10.51464 (11)1.0785 (3)0.41730 (9)0.0222 (5)
C20.44609 (10)0.9837 (3)0.39176 (9)0.0205 (5)
C30.39760 (10)1.0984 (3)0.41626 (9)0.0202 (5)
C40.43240 (11)1.2715 (3)0.45738 (9)0.0208 (5)
C50.43756 (10)0.8056 (3)0.34521 (9)0.0219 (5)
C60.48541 (11)0.6423 (3)0.34911 (10)0.0257 (5)
H60.52420.64660.38200.031*
C70.47724 (11)0.4730 (3)0.30569 (10)0.0290 (6)
H70.51050.36310.30860.035*
C80.42056 (12)0.4650 (4)0.25831 (10)0.0331 (6)
H80.41430.34770.22920.040*
C90.37286 (12)0.6268 (4)0.25302 (10)0.0358 (6)
H90.33410.62150.22000.043*
C100.38148 (11)0.7966 (3)0.29575 (10)0.0289 (6)
H100.34890.90860.29140.035*
C110.32263 (10)1.0668 (3)0.40864 (9)0.0203 (5)
C120.29601 (11)0.8701 (4)0.42262 (9)0.0266 (5)
H120.32630.75840.43830.032*
C130.22600 (11)0.8354 (4)0.41389 (10)0.0310 (6)
H130.20840.70040.42350.037*
C140.18171 (11)0.9967 (4)0.39126 (10)0.0337 (6)
H140.13370.97190.38420.040*
C150.20730 (12)1.1938 (4)0.37900 (11)0.0381 (6)
H150.17661.30610.36490.046*
C160.27750 (11)1.2298 (4)0.38699 (10)0.0303 (6)
H160.29471.36560.37770.036*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0264 (10)0.0386 (10)0.0404 (9)0.0027 (8)0.0056 (7)0.0014 (8)
N10.0190 (11)0.0212 (11)0.0262 (10)0.0010 (9)0.0010 (8)0.0029 (9)
N20.0183 (12)0.0277 (12)0.0279 (10)0.0014 (10)0.0024 (9)0.0032 (9)
C10.0191 (13)0.0234 (13)0.0240 (11)0.0016 (10)0.0029 (10)0.0030 (10)
C20.0218 (12)0.0175 (12)0.0214 (10)0.0006 (10)0.0000 (9)0.0029 (9)
C30.0224 (13)0.0185 (12)0.0192 (10)0.0001 (10)0.0005 (9)0.0034 (9)
C40.0217 (13)0.0224 (13)0.0181 (11)0.0010 (10)0.0023 (9)0.0039 (10)
C50.0219 (12)0.0232 (13)0.0212 (11)0.0012 (10)0.0046 (10)0.0008 (9)
C60.0254 (13)0.0268 (13)0.0242 (11)0.0004 (11)0.0006 (10)0.0012 (10)
C70.0319 (14)0.0263 (14)0.0292 (11)0.0058 (11)0.0058 (11)0.0002 (10)
C80.0404 (15)0.0331 (15)0.0260 (12)0.0016 (12)0.0054 (12)0.0078 (11)
C90.0346 (15)0.0417 (15)0.0288 (12)0.0064 (13)0.0043 (11)0.0087 (12)
C100.0267 (13)0.0318 (14)0.0278 (12)0.0069 (11)0.0017 (11)0.0029 (11)
C110.0225 (12)0.0191 (13)0.0193 (11)0.0016 (10)0.0026 (9)0.0031 (9)
C120.0249 (14)0.0271 (14)0.0278 (12)0.0023 (11)0.0034 (10)0.0020 (10)
C130.0255 (14)0.0345 (15)0.0333 (13)0.0083 (12)0.0045 (11)0.0052 (11)
C140.0186 (13)0.0455 (17)0.0366 (13)0.0004 (13)0.0020 (10)0.0098 (12)
C150.0264 (15)0.0378 (16)0.0474 (15)0.0089 (12)0.0050 (12)0.0044 (12)
C160.0277 (14)0.0243 (14)0.0373 (13)0.0023 (11)0.0014 (11)0.0002 (11)
Geometric parameters (Å, º) top
O1—C11.233 (2)C8—C91.381 (3)
N1—C41.379 (3)C8—H80.9500
N1—C11.380 (3)C9—C101.382 (3)
N1—H10.93 (2)C9—H90.9500
N2—C41.271 (2)C10—H100.9500
N2—H20.82 (2)C11—C161.392 (3)
C1—C21.504 (3)C11—C121.392 (3)
C2—C31.350 (3)C12—C131.383 (3)
C2—C51.472 (3)C12—H120.9500
C3—C111.476 (3)C13—C141.378 (3)
C3—C41.490 (3)C13—H130.9500
C5—C61.391 (3)C14—C151.378 (3)
C5—C101.398 (3)C14—H140.9500
C6—C71.388 (3)C15—C161.388 (3)
C6—H60.9500C15—H150.9500
C7—C81.380 (3)C16—H160.9500
C7—H70.9500
C4—N1—C1110.67 (19)C7—C8—H8119.9
C4—N1—H1123.5 (14)C9—C8—H8119.9
C1—N1—H1124.7 (14)C8—C9—C10120.0 (2)
C4—N2—H2111.4 (15)C8—C9—H9120.0
O1—C1—N1124.8 (2)C10—C9—H9120.0
O1—C1—C2128.67 (19)C9—C10—C5120.8 (2)
N1—C1—C2106.56 (18)C9—C10—H10119.6
C3—C2—C5129.01 (19)C5—C10—H10119.6
C3—C2—C1107.61 (17)C16—C11—C12118.9 (2)
C5—C2—C1123.28 (18)C16—C11—C3121.32 (19)
C2—C3—C11129.49 (19)C12—C11—C3119.81 (19)
C2—C3—C4108.16 (18)C13—C12—C11120.7 (2)
C11—C3—C4122.32 (18)C13—C12—H12119.7
N2—C4—N1122.4 (2)C11—C12—H12119.7
N2—C4—C3130.6 (2)C14—C13—C12120.0 (2)
N1—C4—C3106.92 (18)C14—C13—H13120.0
C6—C5—C10118.24 (19)C12—C13—H13120.0
C6—C5—C2120.76 (19)C15—C14—C13119.8 (2)
C10—C5—C2120.99 (19)C15—C14—H14120.1
C7—C6—C5120.96 (19)C13—C14—H14120.1
C7—C6—H6119.5C14—C15—C16120.6 (2)
C5—C6—H6119.5C14—C15—H15119.7
C8—C7—C6119.7 (2)C16—C15—H15119.7
C8—C7—H7120.1C15—C16—C11119.9 (2)
C6—C7—H7120.1C15—C16—H16120.0
C7—C8—C9120.3 (2)C11—C16—H16120.0
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.93 (2)1.96 (2)2.882 (3)172 (2)
Symmetry code: (i) x+1, y+3, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.93 (2)1.96 (2)2.882 (3)172 (2)
Symmetry code: (i) x+1, y+3, z+1.
 

Acknowledgements

The authors are obliged to the Ministry of Education and Science of the Russian Federation for the Scholarship of the President of the Russian Federation for Students and PhD Students Training Abroad (2013–2014).

References

First citationAlves, M. J., Carvalho, M. A., Proença, M. F. J. R. P. & Booth, B. L. (2009). J. Heterocycl. Chem. 37, 1041–1048.  Google Scholar
First citationBruker (2010). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationDolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationHübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281–1284.  Web of Science CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008a). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008b). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationZhang, Z.-Q., Uth, S., Sandman, D. J. & Foxman, B. M. (2004). J. Phys. Org. Chem. 17, 769–776.  Web of Science CSD CrossRef CAS Google Scholar

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