organic compounds
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
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.
CCDC reference: 978372
Related literature
For general background to 5-iminopyrrol-2-ones, see: Alves et al. (2009). For crystal structures of related compounds, see: Zhang et al. (2004).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2010); cell APEX2; data reduction: APEX2; 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.
Supporting information
CCDC reference: 978372
10.1107/S1600536814001032/jj2181sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814001032/jj2181Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814001032/jj2181Isup3.cml
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.
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 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 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.
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).
detailsThe 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 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 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.
Data collection: APEX2 (Bruker AXS, 2010); cell
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).C16H12N2O | F(000) = 1040 |
Mr = 248.28 | Dx = 1.301 Mg m−3 |
Monoclinic, C2/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2ybc | Cell parameters from 1492 reflections |
a = 19.687 (3) Å | θ = 3.1–22.6° |
b = 6.3064 (10) Å | µ = 0.08 mm−1 |
c = 20.611 (3) Å | T = 100 K |
β = 97.850 (3)° | Plate, yellow |
V = 2534.8 (7) Å3 | 0.12 × 0.10 × 0.07 mm |
Z = 8 |
Bruker KappaAPEXII diffractometer | 2178 independent reflections |
Radiation source: fine-focus sealed tube | 1360 reflections with I > 2σ(I) |
Horizontally mounted graphite crystal monochromator | Rint = 0.050 |
Detector resolution: 9 pixels mm-1 | θmax = 25.1°, θmin = 2.0° |
φ scans and ω scans with κ offset | h = −23→20 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b) | k = −7→7 |
Tmin = 0.990, Tmax = 0.994 | l = −24→24 |
8351 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | H 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 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C16H12N2O | V = 2534.8 (7) Å3 |
Mr = 248.28 | Z = 8 |
Monoclinic, C2/n | Mo Kα radiation |
a = 19.687 (3) Å | µ = 0.08 mm−1 |
b = 6.3064 (10) Å | T = 100 K |
c = 20.611 (3) Å | 0.12 × 0.10 × 0.07 mm |
β = 97.850 (3)° |
Bruker KappaAPEXII diffractometer | 2178 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b) | 1360 reflections with I > 2σ(I) |
Tmin = 0.990, Tmax = 0.994 | Rint = 0.050 |
8351 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.097 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.17 e Å−3 |
2178 reflections | Δρmin = −0.18 e Å−3 |
180 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.57199 (8) | 1.0248 (2) | 0.40578 (7) | 0.0350 (4) | |
N1 | 0.50193 (9) | 1.2453 (3) | 0.45727 (8) | 0.0223 (4) | |
H1 | 0.5344 (12) | 1.344 (4) | 0.4747 (11) | 0.051 (8)* | |
N2 | 0.40778 (11) | 1.4207 (3) | 0.48842 (8) | 0.0247 (5) | |
H2 | 0.3658 (11) | 1.411 (3) | 0.4860 (10) | 0.024 (7)* | |
C1 | 0.51464 (11) | 1.0785 (3) | 0.41730 (9) | 0.0222 (5) | |
C2 | 0.44609 (10) | 0.9837 (3) | 0.39176 (9) | 0.0205 (5) | |
C3 | 0.39760 (10) | 1.0984 (3) | 0.41626 (9) | 0.0202 (5) | |
C4 | 0.43240 (11) | 1.2715 (3) | 0.45738 (9) | 0.0208 (5) | |
C5 | 0.43756 (10) | 0.8056 (3) | 0.34521 (9) | 0.0219 (5) | |
C6 | 0.48541 (11) | 0.6423 (3) | 0.34911 (10) | 0.0257 (5) | |
H6 | 0.5242 | 0.6466 | 0.3820 | 0.031* | |
C7 | 0.47724 (11) | 0.4730 (3) | 0.30569 (10) | 0.0290 (6) | |
H7 | 0.5105 | 0.3631 | 0.3086 | 0.035* | |
C8 | 0.42056 (12) | 0.4650 (4) | 0.25831 (10) | 0.0331 (6) | |
H8 | 0.4143 | 0.3477 | 0.2292 | 0.040* | |
C9 | 0.37286 (12) | 0.6268 (4) | 0.25302 (10) | 0.0358 (6) | |
H9 | 0.3341 | 0.6215 | 0.2200 | 0.043* | |
C10 | 0.38148 (11) | 0.7966 (3) | 0.29575 (10) | 0.0289 (6) | |
H10 | 0.3489 | 0.9086 | 0.2914 | 0.035* | |
C11 | 0.32263 (10) | 1.0668 (3) | 0.40864 (9) | 0.0203 (5) | |
C12 | 0.29601 (11) | 0.8701 (4) | 0.42262 (9) | 0.0266 (5) | |
H12 | 0.3263 | 0.7584 | 0.4383 | 0.032* | |
C13 | 0.22600 (11) | 0.8354 (4) | 0.41389 (10) | 0.0310 (6) | |
H13 | 0.2084 | 0.7004 | 0.4235 | 0.037* | |
C14 | 0.18171 (11) | 0.9967 (4) | 0.39126 (10) | 0.0337 (6) | |
H14 | 0.1337 | 0.9719 | 0.3842 | 0.040* | |
C15 | 0.20730 (12) | 1.1938 (4) | 0.37900 (11) | 0.0381 (6) | |
H15 | 0.1766 | 1.3061 | 0.3649 | 0.046* | |
C16 | 0.27750 (11) | 1.2298 (4) | 0.38699 (10) | 0.0303 (6) | |
H16 | 0.2947 | 1.3656 | 0.3777 | 0.036* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0264 (10) | 0.0386 (10) | 0.0404 (9) | 0.0027 (8) | 0.0056 (7) | −0.0014 (8) |
N1 | 0.0190 (11) | 0.0212 (11) | 0.0262 (10) | −0.0010 (9) | 0.0010 (8) | −0.0029 (9) |
N2 | 0.0183 (12) | 0.0277 (12) | 0.0279 (10) | −0.0014 (10) | 0.0024 (9) | −0.0032 (9) |
C1 | 0.0191 (13) | 0.0234 (13) | 0.0240 (11) | 0.0016 (10) | 0.0029 (10) | 0.0030 (10) |
C2 | 0.0218 (12) | 0.0175 (12) | 0.0214 (10) | −0.0006 (10) | 0.0000 (9) | 0.0029 (9) |
C3 | 0.0224 (13) | 0.0185 (12) | 0.0192 (10) | 0.0001 (10) | 0.0005 (9) | 0.0034 (9) |
C4 | 0.0217 (13) | 0.0224 (13) | 0.0181 (11) | 0.0010 (10) | 0.0023 (9) | 0.0039 (10) |
C5 | 0.0219 (12) | 0.0232 (13) | 0.0212 (11) | −0.0012 (10) | 0.0046 (10) | 0.0008 (9) |
C6 | 0.0254 (13) | 0.0268 (13) | 0.0242 (11) | 0.0004 (11) | 0.0006 (10) | 0.0012 (10) |
C7 | 0.0319 (14) | 0.0263 (14) | 0.0292 (11) | 0.0058 (11) | 0.0058 (11) | −0.0002 (10) |
C8 | 0.0404 (15) | 0.0331 (15) | 0.0260 (12) | 0.0016 (12) | 0.0054 (12) | −0.0078 (11) |
C9 | 0.0346 (15) | 0.0417 (15) | 0.0288 (12) | 0.0064 (13) | −0.0043 (11) | −0.0087 (12) |
C10 | 0.0267 (13) | 0.0318 (14) | 0.0278 (12) | 0.0069 (11) | 0.0017 (11) | −0.0029 (11) |
C11 | 0.0225 (12) | 0.0191 (13) | 0.0193 (11) | 0.0016 (10) | 0.0026 (9) | −0.0031 (9) |
C12 | 0.0249 (14) | 0.0271 (14) | 0.0278 (12) | 0.0023 (11) | 0.0034 (10) | 0.0020 (10) |
C13 | 0.0255 (14) | 0.0345 (15) | 0.0333 (13) | −0.0083 (12) | 0.0045 (11) | −0.0052 (11) |
C14 | 0.0186 (13) | 0.0455 (17) | 0.0366 (13) | −0.0004 (13) | 0.0020 (10) | −0.0098 (12) |
C15 | 0.0264 (15) | 0.0378 (16) | 0.0474 (15) | 0.0089 (12) | −0.0050 (12) | −0.0044 (12) |
C16 | 0.0277 (14) | 0.0243 (14) | 0.0373 (13) | 0.0023 (11) | −0.0014 (11) | −0.0002 (11) |
O1—C1 | 1.233 (2) | C8—C9 | 1.381 (3) |
N1—C4 | 1.379 (3) | C8—H8 | 0.9500 |
N1—C1 | 1.380 (3) | C9—C10 | 1.382 (3) |
N1—H1 | 0.93 (2) | C9—H9 | 0.9500 |
N2—C4 | 1.271 (2) | C10—H10 | 0.9500 |
N2—H2 | 0.82 (2) | C11—C16 | 1.392 (3) |
C1—C2 | 1.504 (3) | C11—C12 | 1.392 (3) |
C2—C3 | 1.350 (3) | C12—C13 | 1.383 (3) |
C2—C5 | 1.472 (3) | C12—H12 | 0.9500 |
C3—C11 | 1.476 (3) | C13—C14 | 1.378 (3) |
C3—C4 | 1.490 (3) | C13—H13 | 0.9500 |
C5—C6 | 1.391 (3) | C14—C15 | 1.378 (3) |
C5—C10 | 1.398 (3) | C14—H14 | 0.9500 |
C6—C7 | 1.388 (3) | C15—C16 | 1.388 (3) |
C6—H6 | 0.9500 | C15—H15 | 0.9500 |
C7—C8 | 1.380 (3) | C16—H16 | 0.9500 |
C7—H7 | 0.9500 | ||
C4—N1—C1 | 110.67 (19) | C7—C8—H8 | 119.9 |
C4—N1—H1 | 123.5 (14) | C9—C8—H8 | 119.9 |
C1—N1—H1 | 124.7 (14) | C8—C9—C10 | 120.0 (2) |
C4—N2—H2 | 111.4 (15) | C8—C9—H9 | 120.0 |
O1—C1—N1 | 124.8 (2) | C10—C9—H9 | 120.0 |
O1—C1—C2 | 128.67 (19) | C9—C10—C5 | 120.8 (2) |
N1—C1—C2 | 106.56 (18) | C9—C10—H10 | 119.6 |
C3—C2—C5 | 129.01 (19) | C5—C10—H10 | 119.6 |
C3—C2—C1 | 107.61 (17) | C16—C11—C12 | 118.9 (2) |
C5—C2—C1 | 123.28 (18) | C16—C11—C3 | 121.32 (19) |
C2—C3—C11 | 129.49 (19) | C12—C11—C3 | 119.81 (19) |
C2—C3—C4 | 108.16 (18) | C13—C12—C11 | 120.7 (2) |
C11—C3—C4 | 122.32 (18) | C13—C12—H12 | 119.7 |
N2—C4—N1 | 122.4 (2) | C11—C12—H12 | 119.7 |
N2—C4—C3 | 130.6 (2) | C14—C13—C12 | 120.0 (2) |
N1—C4—C3 | 106.92 (18) | C14—C13—H13 | 120.0 |
C6—C5—C10 | 118.24 (19) | C12—C13—H13 | 120.0 |
C6—C5—C2 | 120.76 (19) | C15—C14—C13 | 119.8 (2) |
C10—C5—C2 | 120.99 (19) | C15—C14—H14 | 120.1 |
C7—C6—C5 | 120.96 (19) | C13—C14—H14 | 120.1 |
C7—C6—H6 | 119.5 | C14—C15—C16 | 120.6 (2) |
C5—C6—H6 | 119.5 | C14—C15—H15 | 119.7 |
C8—C7—C6 | 119.7 (2) | C16—C15—H15 | 119.7 |
C8—C7—H7 | 120.1 | C15—C16—C11 | 119.9 (2) |
C6—C7—H7 | 120.1 | C15—C16—H16 | 120.0 |
C7—C8—C9 | 120.3 (2) | C11—C16—H16 | 120.0 |
D—H···A | D—H | H···A | D···A | 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. |
D—H···A | D—H | H···A | D···A | 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. |
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
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