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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1933.
Published online 2009 July 18. doi:  10.1107/S1600536809027780
PMCID: PMC2977180

Ethyl 5-[(2,3-dimethyl-5-oxo-1-phenyl-2,5-dihydro-1H-pyrazol-4-yl)imino­meth­yl]-3,4-dimethyl-1H-pyrrole-2-carboxyl­ate

Abstract

In the title compound, C21H24N4O3, the mol­ecule has an E configuration about the imine C=N double bond. Inter­molecular N—H(...)O hydrogen bonds assemble mol­ecules into centrosymmetric dimers.

Related literature

For studies on the complexes of bis­(pyrrol-2-yl-methyl­ene­amine) ligands, see: Wang et al. (2008 [triangle]); Yang et al. (2003 [triangle]). For the structure of 5-formyl-3,4-dimethyl-1H-pyrrole-2-carb­oxyl­ate, see: Wu et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1933-scheme1.jpg

Experimental

Crystal data

  • C21H24N4O3
  • M r = 380.44
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1933-efi1.jpg
  • a = 13.421 (2) Å
  • b = 20.141 (3) Å
  • c = 7.5477 (13) Å
  • β = 96.147 (2)°
  • V = 2028.5 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 296 K
  • 0.30 × 0.21 × 0.08 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1997 [triangle]) T min = 0.979, T max = 0.993
  • 23826 measured reflections
  • 4717 independent reflections
  • 2622 reflections with I > 2σ(I)
  • R int = 0.051

Refinement

  • R[F 2 > 2σ(F 2)] = 0.050
  • wR(F 2) = 0.149
  • S = 1.01
  • 4717 reflections
  • 258 parameters
  • H-atom parameters constrained
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [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 I, global. DOI: 10.1107/S1600536809027780/gk2222sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809027780/gk2222Isup2.hkl

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

supplementary crystallographic information

Comment

Due to the excellent fluorescent properties and good solubilities of their complexes, linear spaced bis(pyrrol-2-yl-methyleneamine) ligands have attracted much recent attention (Yang et al., 2003). As part of our ongoing studies of pyrrol-2-yl-methyleneamine ligand (Wu et al., 2008), the title compound was synthesized and characterized by X-ray diffraction.

In the title compound (Fig. 1), the molecule adopts an E configuration at the C=N double bond. The dihedral angle between dihydropyrazole ring (N3,4/C11–C13, r.m.s. deviation 0.026 Å) and pyrrole ring (N1/C4–C7, r.m.s. deviation 0.002 Å) is 9.6 (2)°. The phenyl ring (C16–C20) makes the dihedral angle of 42.4 (1)° with dihydropyrazole ring. In the crystal, th molecules are linked into a centrosymmetric dimer by two intermolecular N—H···O hydrogen bonds, forming a R22(10) ring motif (Table1, Fig. 2). The dimers stack alternately like letter "V" (Fig. 3) and the dihedral angle of the adjacent phenyl rings is 37.1 (3)°. Intermolecular C14—H14A···π (N1/C4–C7) interaction (C14-centroid distance 3.4992 Å). is also present.

Experimental

4-Amino-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one (0.203 g, 1 mmol) was dissolved in ethanol (10 ml), then an ethanol solution (10 ml) containing ethyl 5-formyl-3,4-dimethyl-1H-pyrrole-2-carboxylate (0.195 g, 1 mmol) was added dropwise at room temperature. After stirring for 24 h, the precipitate was separated from the solution by suction filtration, washed with ethanol, and dried in a vacuum to yield the title compound 0.198 g (52%).Yellow blocks of the title compound were obtained by slow evaporation of an ethanol/THF (1:1) solution.

Refinement

All H atoms were placed in calculated positions, with C—H = 0.93–0.97 Å and N—H = 0.86 Å, and were thereafter treated as riding, with Uiso(H) values of 1.5Ueq(C) for methyl groups and 1.2Ueq(C,N) for others.

Figures

Fig. 1.
The molecular structure shown with 50% probability displacement ellipsoids.
Fig. 2.
A centrosymmetric dimer via intermolecular hydrogen bonds (dashed lines)..
Fig. 3.
The crystal packing for the title compound viewed down the a axis

Crystal data

C21H24N4O3F(000) = 808
Mr = 380.44Dx = 1.246 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2702 reflections
a = 13.421 (2) Åθ = 2.5–20.3°
b = 20.141 (3) ŵ = 0.09 mm1
c = 7.5477 (13) ÅT = 296 K
β = 96.147 (2)°Block, yellow
V = 2028.5 (6) Å30.30 × 0.21 × 0.08 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer4717 independent reflections
Radiation source: fine-focus sealed tube2622 reflections with I > 2σ(I)
graphiteRint = 0.051
[var phi] and ω scansθmax = 27.8°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1997)h = −17→17
Tmin = 0.979, Tmax = 0.993k = −26→26
23826 measured reflectionsl = −9→9

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)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.149H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.07P)2 + 0.1292P] where P = (Fo2 + 2Fc2)/3
4717 reflections(Δ/σ)max < 0.001
258 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = −0.20 e Å3

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
N10.89926 (11)0.04791 (7)0.2730 (2)0.0489 (4)
H1D0.95570.02970.30940.059*
O30.73311 (9)0.00819 (7)0.59614 (18)0.0606 (4)
O20.89663 (10)−0.01469 (7)0.60113 (19)0.0637 (4)
C30.82077 (14)0.01047 (9)0.5289 (3)0.0489 (5)
N41.09462 (11)0.18926 (7)−0.46225 (19)0.0497 (4)
N20.94408 (12)0.13164 (8)−0.1322 (2)0.0525 (4)
C111.02102 (14)0.14408 (9)−0.2378 (2)0.0475 (4)
C100.95909 (14)0.09456 (9)0.0064 (2)0.0493 (5)
H10A1.02110.07440.03410.059*
C40.81529 (13)0.04502 (9)0.3599 (3)0.0498 (5)
C131.00552 (14)0.17709 (8)−0.3956 (2)0.0477 (4)
C50.88044 (13)0.08391 (9)0.1198 (2)0.0491 (5)
O11.17701 (10)0.11051 (8)−0.06507 (18)0.0692 (4)
N31.16917 (11)0.15719 (8)−0.3468 (2)0.0530 (4)
C121.12710 (15)0.13275 (9)−0.1985 (2)0.0514 (5)
C211.30141 (16)0.23522 (10)−0.4062 (3)0.0590 (5)
H211.25400.2680−0.43770.071*
C161.27191 (14)0.17312 (10)−0.3532 (2)0.0525 (5)
C60.78108 (14)0.10470 (10)0.1085 (3)0.0548 (5)
C20.73181 (15)−0.02886 (11)0.7614 (3)0.0643 (6)
H2A0.7713−0.00590.85770.077*
H2B0.7604−0.07260.74890.077*
C70.74006 (13)0.08006 (10)0.2585 (3)0.0568 (5)
C171.34292 (17)0.12484 (11)−0.3051 (3)0.0674 (6)
H171.32330.0831−0.26930.081*
C140.90956 (15)0.20130 (10)−0.4891 (3)0.0620 (5)
H14A0.89510.1776−0.59920.093*
H14B0.91490.2479−0.51340.093*
H14C0.85660.1941−0.41530.093*
C80.72684 (15)0.14606 (12)−0.0377 (3)0.0767 (7)
H8A0.65590.1425−0.03280.115*
H8B0.74330.1304−0.15120.115*
H8C0.74680.1916−0.02240.115*
C151.10435 (16)0.18288 (10)−0.6526 (2)0.0603 (5)
H15A1.09970.1369−0.68610.091*
H15B1.16810.2002−0.67720.091*
H15C1.05170.2074−0.71950.091*
C201.40162 (18)0.24783 (13)−0.4116 (3)0.0772 (7)
H201.42170.2893−0.44850.093*
C90.63467 (16)0.09116 (14)0.3014 (4)0.0903 (9)
H9A0.62860.13530.34690.135*
H9B0.61890.05960.38950.135*
H9C0.58910.08570.19540.135*
C191.47261 (19)0.20031 (16)−0.3638 (4)0.0883 (8)
H191.54030.2095−0.36730.106*
C181.44268 (19)0.13905 (14)−0.3105 (4)0.0855 (8)
H181.49050.1067−0.27770.103*
C10.62731 (18)−0.03477 (16)0.8013 (4)0.1050 (10)
H1A0.60350.00790.83480.157*
H1B0.6237−0.06550.89760.157*
H1C0.5865−0.05050.69760.157*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0397 (8)0.0527 (9)0.0546 (10)−0.0008 (7)0.0066 (7)0.0072 (7)
O30.0435 (7)0.0775 (9)0.0624 (9)0.0040 (6)0.0131 (6)0.0224 (7)
O20.0434 (8)0.0757 (10)0.0724 (10)0.0066 (7)0.0081 (7)0.0203 (7)
C30.0405 (10)0.0491 (11)0.0578 (12)−0.0047 (8)0.0087 (9)0.0025 (9)
N40.0550 (10)0.0537 (9)0.0399 (9)0.0003 (7)0.0025 (7)0.0056 (7)
N20.0564 (10)0.0528 (9)0.0482 (9)−0.0069 (7)0.0058 (8)0.0030 (8)
C110.0518 (11)0.0460 (10)0.0450 (11)−0.0055 (8)0.0061 (8)0.0008 (8)
C100.0479 (11)0.0499 (11)0.0500 (11)−0.0051 (8)0.0048 (9)−0.0004 (9)
C40.0383 (10)0.0536 (11)0.0578 (12)−0.0046 (8)0.0065 (8)0.0067 (9)
C130.0542 (11)0.0418 (10)0.0463 (11)−0.0030 (8)0.0018 (9)−0.0016 (8)
C50.0484 (11)0.0502 (11)0.0483 (11)−0.0068 (8)0.0028 (8)0.0020 (9)
O10.0629 (9)0.0895 (11)0.0536 (9)0.0007 (8)−0.0006 (7)0.0250 (8)
N30.0522 (10)0.0610 (10)0.0449 (9)0.0004 (8)0.0015 (7)0.0101 (8)
C120.0590 (12)0.0524 (11)0.0425 (11)−0.0035 (9)0.0048 (9)0.0066 (9)
C210.0619 (13)0.0662 (14)0.0510 (12)−0.0007 (10)0.0154 (10)0.0034 (10)
C160.0536 (12)0.0608 (12)0.0435 (10)−0.0006 (9)0.0078 (9)−0.0018 (9)
C60.0438 (11)0.0610 (12)0.0580 (12)−0.0050 (9)−0.0018 (9)0.0093 (10)
C20.0563 (12)0.0795 (15)0.0589 (13)0.0055 (11)0.0142 (10)0.0197 (11)
C70.0402 (10)0.0644 (13)0.0653 (13)−0.0036 (9)0.0033 (9)0.0100 (10)
C170.0686 (15)0.0661 (14)0.0673 (15)0.0066 (11)0.0061 (11)0.0011 (11)
C140.0622 (13)0.0608 (12)0.0610 (13)−0.0004 (10)−0.0020 (10)0.0048 (10)
C80.0532 (13)0.0964 (18)0.0782 (16)−0.0009 (12)−0.0035 (11)0.0289 (14)
C150.0747 (14)0.0643 (13)0.0417 (11)0.0035 (11)0.0049 (10)0.0040 (10)
C200.0709 (16)0.0917 (17)0.0721 (16)−0.0158 (14)0.0214 (12)0.0067 (13)
C90.0450 (13)0.122 (2)0.105 (2)0.0141 (13)0.0165 (13)0.0387 (17)
C190.0566 (15)0.120 (2)0.0905 (19)−0.0054 (16)0.0181 (13)−0.0016 (17)
C180.0608 (16)0.104 (2)0.0924 (19)0.0211 (14)0.0100 (13)0.0017 (16)
C10.0648 (16)0.146 (3)0.108 (2)−0.0029 (16)0.0275 (15)0.0547 (19)

Geometric parameters (Å, °)

N1—C41.364 (2)C6—C81.507 (3)
N1—C51.366 (2)C2—C11.471 (3)
N1—H1D0.8600C2—H2A0.9700
O3—C31.331 (2)C2—H2B0.9700
O3—C21.455 (2)C7—C91.501 (3)
O2—C31.213 (2)C17—C181.374 (3)
C3—C41.448 (3)C17—H170.9300
N4—C131.368 (2)C14—H14A0.9600
N4—N31.411 (2)C14—H14B0.9600
N4—C151.462 (2)C14—H14C0.9600
N2—C101.284 (2)C8—H8A0.9600
N2—C111.393 (2)C8—H8B0.9600
C11—C131.361 (2)C8—H8C0.9600
C11—C121.441 (3)C15—H15A0.9600
C10—C51.444 (3)C15—H15B0.9600
C10—H10A0.9300C15—H15C0.9600
C4—C71.392 (3)C20—C191.371 (3)
C13—C141.483 (3)C20—H200.9300
C5—C61.392 (3)C9—H9A0.9600
O1—C121.233 (2)C9—H9B0.9600
N3—C121.396 (2)C9—H9C0.9600
N3—C161.422 (2)C19—C181.371 (4)
C21—C201.374 (3)C19—H190.9300
C21—C161.384 (3)C18—H180.9300
C21—H210.9300C1—H1A0.9600
C16—C171.383 (3)C1—H1B0.9600
C6—C71.402 (3)C1—H1C0.9600
C4—N1—C5110.02 (15)H2A—C2—H2B108.4
C4—N1—H1D125.0C4—C7—C6107.40 (16)
C5—N1—H1D125.0C4—C7—C9126.99 (18)
C3—O3—C2115.88 (15)C6—C7—C9125.61 (18)
O2—C3—O3123.23 (18)C18—C17—C16119.5 (2)
O2—C3—C4123.89 (17)C18—C17—H17120.3
O3—C3—C4112.88 (16)C16—C17—H17120.3
C13—N4—N3106.31 (14)C13—C14—H14A109.5
C13—N4—C15121.26 (15)C13—C14—H14B109.5
N3—N4—C15115.75 (15)H14A—C14—H14B109.5
C10—N2—C11120.64 (17)C13—C14—H14C109.5
C13—C11—N2122.38 (17)H14A—C14—H14C109.5
C13—C11—C12108.20 (16)H14B—C14—H14C109.5
N2—C11—C12129.10 (16)C6—C8—H8A109.5
N2—C10—C5120.56 (18)C6—C8—H8B109.5
N2—C10—H10A119.7H8A—C8—H8B109.5
C5—C10—H10A119.7C6—C8—H8C109.5
N1—C4—C7107.58 (16)H8A—C8—H8C109.5
N1—C4—C3118.50 (16)H8B—C8—H8C109.5
C7—C4—C3133.90 (17)N4—C15—H15A109.5
C11—C13—N4110.59 (16)N4—C15—H15B109.5
C11—C13—C14128.38 (18)H15A—C15—H15B109.5
N4—C13—C14120.98 (16)N4—C15—H15C109.5
N1—C5—C6107.48 (16)H15A—C15—H15C109.5
N1—C5—C10120.00 (16)H15B—C15—H15C109.5
C6—C5—C10132.51 (18)C21—C20—C19121.2 (2)
C12—N3—N4109.60 (15)C21—C20—H20119.4
C12—N3—C16125.72 (15)C19—C20—H20119.4
N4—N3—C16120.13 (15)C7—C9—H9A109.5
O1—C12—N3123.51 (18)C7—C9—H9B109.5
O1—C12—C11131.60 (17)H9A—C9—H9B109.5
N3—C12—C11104.78 (15)C7—C9—H9C109.5
C20—C21—C16119.1 (2)H9A—C9—H9C109.5
C20—C21—H21120.4H9B—C9—H9C109.5
C16—C21—H21120.4C18—C19—C20119.2 (2)
C17—C16—C21120.1 (2)C18—C19—H19120.4
C17—C16—N3118.44 (18)C20—C19—H19120.4
C21—C16—N3121.49 (18)C19—C18—C17120.9 (2)
C5—C6—C7107.52 (16)C19—C18—H18119.6
C5—C6—C8126.55 (18)C17—C18—H18119.6
C7—C6—C8125.93 (18)C2—C1—H1A109.5
O3—C2—C1108.44 (17)C2—C1—H1B109.5
O3—C2—H2A110.0H1A—C1—H1B109.5
C1—C2—H2A110.0C2—C1—H1C109.5
O3—C2—H2B110.0H1A—C1—H1C109.5
C1—C2—H2B110.0H1B—C1—H1C109.5
C2—O3—C3—O2−2.1 (3)C16—N3—C12—C11162.58 (17)
C2—O3—C3—C4176.86 (16)C13—C11—C12—O1172.6 (2)
C10—N2—C11—C13172.78 (17)N2—C11—C12—O1−0.9 (3)
C10—N2—C11—C12−14.5 (3)C13—C11—C12—N3−3.6 (2)
C11—N2—C10—C5177.46 (16)N2—C11—C12—N3−177.11 (17)
C5—N1—C4—C70.3 (2)C20—C21—C16—C170.6 (3)
C5—N1—C4—C3−178.24 (16)C20—C21—C16—N3−179.38 (18)
O2—C3—C4—N12.1 (3)C12—N3—C16—C1754.9 (3)
O3—C3—C4—N1−176.84 (16)N4—N3—C16—C17−151.52 (18)
O2—C3—C4—C7−175.9 (2)C12—N3—C16—C21−125.1 (2)
O3—C3—C4—C75.1 (3)N4—N3—C16—C2128.4 (3)
N2—C11—C13—N4173.11 (15)N1—C5—C6—C7−0.3 (2)
C12—C11—C13—N4−0.9 (2)C10—C5—C6—C7−179.24 (19)
N2—C11—C13—C14−4.2 (3)N1—C5—C6—C8179.8 (2)
C12—C11—C13—C14−178.26 (18)C10—C5—C6—C80.8 (3)
N3—N4—C13—C115.04 (19)C3—O3—C2—C1−171.5 (2)
C15—N4—C13—C11140.06 (17)N1—C4—C7—C6−0.5 (2)
N3—N4—C13—C14−177.38 (16)C3—C4—C7—C6177.7 (2)
C15—N4—C13—C14−42.4 (2)N1—C4—C7—C9−179.3 (2)
C4—N1—C5—C60.0 (2)C3—C4—C7—C9−1.1 (4)
C4—N1—C5—C10179.11 (16)C5—C6—C7—C40.5 (2)
N2—C10—C5—N1−175.74 (16)C8—C6—C7—C4−179.6 (2)
N2—C10—C5—C63.1 (3)C5—C6—C7—C9179.3 (2)
C13—N4—N3—C12−7.40 (19)C8—C6—C7—C9−0.7 (4)
C15—N4—N3—C12−145.27 (16)C21—C16—C17—C18−0.1 (3)
C13—N4—N3—C16−164.82 (15)N3—C16—C17—C18179.88 (19)
C15—N4—N3—C1657.3 (2)C16—C21—C20—C19−0.7 (3)
N4—N3—C12—O1−169.83 (18)C21—C20—C19—C180.4 (4)
C16—N3—C12—O1−14.0 (3)C20—C19—C18—C170.1 (4)
N4—N3—C12—C116.73 (19)C16—C17—C18—C19−0.3 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1D···O2i0.862.052.880 (2)163

Symmetry codes: (i) −x+2, −y, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2222).

References

  • Bruker (1997). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
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