N-[(3-Methyl-5-oxo-1-phenyl-4,5-di­hydro-1H-pyrazol-4-yl­idene)(phenyl)­methyl]­glycine ethyl ester

In the title compound, C₂₁H₂₁N₃O₃, the pyrazolone and the N atom of the glycine ethyl ester group are essentially coplanar. The compound is a neutral tridentate ligand in an en­amine–keto form, stabilized by two strong intramolecular N—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.050
• wR factor = 0.131
• Data-to-parameter ratio = 12.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.98 Ratio

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker,1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1997).

N-[(3-Methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4- ylidene)(phenyl)methyl]glycine ethyl ester

Crystal data

C21H21N3O3	Z = 2
Mr = 363.41	F(000) = 384
Triclinic, P1	Dx = 1.242 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.268 (3) Å	Cell parameters from 905 reflections
b = 9.985 (3) Å	θ = 3.1–24.1°
c = 11.193 (4) Å	µ = 0.09 mm^−1
α = 100.386 (5)°	T = 293 K
β = 92.652 (5)°	Block, pale yellow
γ = 106.543 (5)°	0.40 × 0.20 × 0.15 mm
V = 971.4 (6) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	2551 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.026
Graphite monochromator	θmax = 26.4°, θmin = 1.9°
Detector resolution: 0 pixels mm^-1	h = −11→11
φ and ω scans	k = −12→12
8043 measured reflections	l = −14→14
3957 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0556P)^2 + 0.1991P] where P = (Fo^2 + 2Fc^2)/3
3957 reflections	(Δ/σ)max = 0.001
318 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.06014 (18)	−0.23631 (18)	0.31920 (14)	0.0554 (4)
N2	−0.06109 (19)	−0.24993 (19)	0.39170 (15)	0.0612 (5)
N3	0.01170 (19)	0.09473 (18)	0.16188 (15)	0.0547 (4)
H3	0.097 (2)	0.064 (2)	0.1516 (18)	0.070 (6)*
O1	0.16735 (14)	−0.09293 (15)	0.18269 (12)	0.0598 (4)
O2	0.24614 (18)	0.21423 (18)	0.04764 (15)	0.0780 (5)
O3	0.13754 (17)	0.37183 (16)	−0.00363 (15)	0.0734 (4)
C1	0.0713 (2)	−0.1292 (2)	0.25479 (17)	0.0496 (5)
C2	−0.1259 (2)	−0.1539 (2)	0.37252 (17)	0.0547 (5)
C3	−0.05131 (19)	−0.0730 (2)	0.28740 (16)	0.0483 (4)
C4	−0.08256 (19)	0.0338 (2)	0.23553 (16)	0.0463 (4)
C5	0.1494 (2)	−0.3304 (2)	0.31924 (17)	0.0551 (5)
C6	0.2898 (3)	−0.2996 (3)	0.2760 (2)	0.0705 (6)
H6	0.329 (3)	−0.216 (3)	0.241 (2)	0.081 (7)*
C7	0.3760 (3)	−0.3926 (3)	0.2797 (3)	0.0812 (7)
H7	0.474 (3)	−0.367 (3)	0.247 (2)	0.090 (8)*
C8	0.3239 (4)	−0.5129 (3)	0.3280 (2)	0.0825 (8)
H8	0.391 (3)	−0.573 (3)	0.333 (2)	0.093 (8)*
C9	0.1848 (3)	−0.5423 (3)	0.3713 (2)	0.0776 (7)
H9	0.143 (3)	−0.626 (3)	0.407 (2)	0.100 (9)*
C10	0.0961 (3)	−0.4527 (2)	0.3661 (2)	0.0637 (6)
H10	−0.005 (3)	−0.473 (2)	0.396 (2)	0.079 (7)*
C11	−0.2551 (3)	−0.1378 (4)	0.4432 (3)	0.0733 (7)
H11A	−0.292 (3)	−0.221 (3)	0.482 (3)	0.114 (10)*
H11B	−0.337 (3)	−0.137 (3)	0.393 (2)	0.094 (9)*
H11C	−0.222 (4)	−0.044 (4)	0.500 (3)	0.131 (12)*
C12	−0.2213 (2)	0.0791 (2)	0.25398 (16)	0.0467 (4)
C13	−0.3460 (2)	0.0181 (2)	0.16782 (19)	0.0576 (5)
H13	−0.343 (2)	−0.054 (2)	0.096 (2)	0.075 (7)*
C14	−0.4766 (2)	0.0561 (3)	0.1834 (2)	0.0630 (6)
H14	−0.564 (3)	0.011 (3)	0.125 (2)	0.091 (8)*
C15	−0.4837 (3)	0.1538 (3)	0.2843 (2)	0.0655 (6)
H15	−0.574 (3)	0.179 (2)	0.2963 (19)	0.077 (7)*
C16	−0.3606 (3)	0.2157 (3)	0.3689 (2)	0.0749 (7)
H16	−0.363 (3)	0.286 (3)	0.441 (2)	0.105 (9)*
C17	−0.2285 (3)	0.1790 (2)	0.3544 (2)	0.0643 (6)
H17	−0.143 (3)	0.222 (2)	0.414 (2)	0.082 (7)*
C18	−0.0026 (2)	0.2076 (3)	0.1015 (2)	0.0572 (5)
H18A	−0.020 (2)	0.288 (3)	0.159 (2)	0.080 (7)*
H18B	−0.085 (3)	0.175 (2)	0.039 (2)	0.083 (7)*
C19	0.1419 (2)	0.2628 (2)	0.04627 (18)	0.0576 (5)
C20	0.2720 (4)	0.4334 (4)	−0.0612 (4)	0.0942 (9)
H20A	0.366 (4)	0.473 (4)	0.011 (3)	0.158 (14)*
H20B	0.275 (4)	0.371 (4)	−0.142 (4)	0.167 (16)*
C21	0.2581 (4)	0.5622 (4)	−0.0951 (4)	0.1380 (14)
H21A	0.1715	0.5392	−0.1539	0.207*
H21B	0.3475	0.6070	−0.1299	0.207*
H21C	0.2458	0.6262	−0.0239	0.207*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0533 (10)	0.0642 (11)	0.0581 (10)	0.0276 (8)	0.0128 (8)	0.0188 (8)
N2	0.0577 (10)	0.0723 (12)	0.0621 (10)	0.0264 (9)	0.0163 (8)	0.0217 (9)
N3	0.0477 (10)	0.0655 (11)	0.0618 (10)	0.0287 (8)	0.0134 (8)	0.0192 (8)
O1	0.0480 (8)	0.0742 (9)	0.0682 (9)	0.0277 (7)	0.0160 (7)	0.0245 (7)
O2	0.0671 (10)	0.0881 (11)	0.0972 (12)	0.0419 (9)	0.0329 (9)	0.0295 (9)
O3	0.0653 (10)	0.0745 (10)	0.0903 (11)	0.0238 (8)	0.0179 (8)	0.0343 (9)
C1	0.0412 (10)	0.0581 (12)	0.0504 (11)	0.0172 (9)	0.0025 (9)	0.0103 (9)
C2	0.0475 (11)	0.0667 (13)	0.0539 (11)	0.0217 (10)	0.0073 (9)	0.0142 (10)
C3	0.0401 (10)	0.0575 (11)	0.0490 (10)	0.0187 (9)	0.0039 (8)	0.0085 (9)
C4	0.0396 (10)	0.0536 (11)	0.0431 (10)	0.0150 (8)	0.0022 (8)	0.0021 (8)
C5	0.0587 (12)	0.0589 (12)	0.0513 (11)	0.0275 (10)	0.0011 (9)	0.0050 (9)
C6	0.0671 (15)	0.0726 (16)	0.0840 (16)	0.0361 (13)	0.0171 (12)	0.0199 (13)
C7	0.0741 (17)	0.0885 (19)	0.0925 (18)	0.0456 (15)	0.0161 (14)	0.0110 (15)
C8	0.100 (2)	0.0697 (17)	0.0884 (18)	0.0518 (16)	−0.0021 (15)	0.0033 (14)
C9	0.093 (2)	0.0608 (15)	0.0850 (17)	0.0359 (14)	0.0010 (14)	0.0125 (13)
C10	0.0712 (15)	0.0602 (13)	0.0621 (13)	0.0247 (11)	0.0032 (11)	0.0106 (11)
C11	0.0613 (15)	0.094 (2)	0.0798 (17)	0.0354 (14)	0.0264 (13)	0.0327 (16)
C12	0.0426 (10)	0.0551 (11)	0.0460 (10)	0.0196 (8)	0.0065 (8)	0.0107 (9)
C13	0.0473 (11)	0.0711 (14)	0.0532 (12)	0.0227 (10)	0.0030 (9)	0.0019 (10)
C14	0.0431 (11)	0.0846 (16)	0.0630 (13)	0.0235 (11)	0.0037 (10)	0.0124 (12)
C15	0.0514 (13)	0.0799 (16)	0.0785 (15)	0.0359 (12)	0.0205 (11)	0.0197 (13)
C16	0.0715 (16)	0.0842 (17)	0.0712 (15)	0.0390 (13)	0.0139 (13)	−0.0064 (13)
C17	0.0581 (13)	0.0756 (15)	0.0560 (12)	0.0279 (11)	−0.0008 (10)	−0.0059 (11)
C18	0.0541 (12)	0.0682 (14)	0.0576 (12)	0.0274 (11)	0.0110 (10)	0.0174 (11)
C19	0.0601 (13)	0.0598 (13)	0.0549 (12)	0.0214 (11)	0.0079 (10)	0.0108 (10)
C20	0.084 (2)	0.092 (2)	0.115 (3)	0.0183 (16)	0.0360 (19)	0.049 (2)
C21	0.140 (3)	0.124 (3)	0.178 (4)	0.041 (2)	0.045 (3)	0.093 (3)

Geometric parameters (Å, º)

N1—C1	1.377 (2)	C9—H9	0.98 (3)
N1—N2	1.406 (2)	C10—H10	0.99 (2)
N1—C5	1.417 (2)	C11—H11A	0.99 (3)
N2—C2	1.310 (2)	C11—H11B	0.93 (3)
N3—C4	1.326 (2)	C11—H11C	0.99 (3)
N3—C18	1.447 (3)	C12—C17	1.380 (3)
N3—H3	0.93 (2)	C12—C13	1.386 (3)
O1—C1	1.250 (2)	C13—C14	1.378 (3)
O2—C19	1.199 (2)	C13—H13	0.98 (2)
O3—C19	1.319 (2)	C14—C15	1.370 (3)
O3—C20	1.459 (3)	C14—H14	0.96 (3)
C1—C3	1.437 (2)	C15—C16	1.367 (3)
C2—C3	1.435 (3)	C15—H15	0.95 (2)
C2—C11	1.495 (3)	C16—C17	1.383 (3)
C3—C4	1.393 (3)	C16—H16	0.98 (3)
C4—C12	1.491 (2)	C17—H17	0.95 (2)
C5—C6	1.381 (3)	C18—C19	1.503 (3)
C5—C10	1.387 (3)	C18—H18A	0.99 (2)
C6—C7	1.391 (3)	C18—H18B	0.95 (2)
C6—H6	0.96 (2)	C20—C21	1.442 (4)
C7—C8	1.377 (4)	C20—H20A	1.09 (4)
C7—H7	0.98 (2)	C20—H20B	1.01 (4)
C8—C9	1.370 (4)	C21—H21A	0.9600
C8—H8	0.98 (3)	C21—H21B	0.9600
C9—C10	1.382 (3)	C21—H21C	0.9600
C1—N1—N2	111.69 (15)	H11A—C11—H11C	115 (2)
C1—N1—C5	129.40 (16)	H11B—C11—H11C	106 (2)
N2—N1—C5	118.90 (16)	C17—C12—C13	119.56 (17)
C2—N2—N1	106.39 (15)	C17—C12—C4	121.74 (17)
C4—N3—C18	126.22 (16)	C13—C12—C4	118.70 (16)
C4—N3—H3	116.1 (13)	C14—C13—C12	120.0 (2)
C18—N3—H3	117.6 (13)	C14—C13—H13	119.4 (13)
C19—O3—C20	115.20 (19)	C12—C13—H13	120.6 (13)
O1—C1—N1	126.11 (17)	C15—C14—C13	120.1 (2)
O1—C1—C3	128.88 (17)	C15—C14—H14	120.4 (14)
N1—C1—C3	105.01 (16)	C13—C14—H14	119.4 (14)
N2—C2—C3	111.53 (16)	C16—C15—C14	120.2 (2)
N2—C2—C11	118.61 (19)	C16—C15—H15	119.4 (13)
C3—C2—C11	129.76 (19)	C14—C15—H15	120.4 (13)
C4—C3—C2	132.28 (17)	C15—C16—C17	120.4 (2)
C4—C3—C1	122.28 (17)	C15—C16—H16	121.6 (16)
C2—C3—C1	105.38 (16)	C17—C16—H16	118.0 (16)
N3—C4—C3	118.94 (16)	C12—C17—C16	119.7 (2)
N3—C4—C12	117.76 (16)	C12—C17—H17	120.3 (14)
C3—C4—C12	123.23 (16)	C16—C17—H17	120.0 (14)
C6—C5—C10	119.9 (2)	N3—C18—C19	108.35 (17)
C6—C5—N1	120.74 (19)	N3—C18—H18A	112.1 (13)
C10—C5—N1	119.38 (19)	C19—C18—H18A	108.5 (13)
C5—C6—C7	119.3 (2)	N3—C18—H18B	111.6 (14)
C5—C6—H6	121.7 (14)	C19—C18—H18B	109.6 (14)
C7—C6—H6	119.0 (14)	H18A—C18—H18B	106.6 (18)
C8—C7—C6	120.7 (3)	O2—C19—O3	125.0 (2)
C8—C7—H7	122.8 (14)	O2—C19—C18	124.5 (2)
C6—C7—H7	116.5 (15)	O3—C19—C18	110.47 (18)
C9—C8—C7	119.6 (2)	C21—C20—O3	108.0 (3)
C9—C8—H8	122.3 (14)	C21—C20—H20A	102.9 (19)
C7—C8—H8	118.0 (14)	O3—C20—H20A	106.3 (18)
C8—C9—C10	120.5 (3)	C21—C20—H20B	103 (2)
C8—C9—H9	122.5 (15)	O3—C20—H20B	111 (2)
C10—C9—H9	116.9 (16)	H20A—C20—H20B	124 (3)
C9—C10—C5	119.9 (2)	C20—C21—H21A	109.5
C9—C10—H10	121.7 (13)	C20—C21—H21B	109.5
C5—C10—H10	118.3 (13)	H21A—C21—H21B	109.5
C2—C11—H11A	109.6 (16)	C20—C21—H21C	109.5
C2—C11—H11B	112.3 (16)	H21A—C21—H21C	109.5
H11A—C11—H11B	105 (2)	H21B—C21—H21C	109.5
C2—C11—H11C	108.2 (18)
C1—N1—N2—C2	0.5 (2)	C10—C5—C6—C7	0.2 (3)
C5—N1—N2—C2	−178.42 (17)	N1—C5—C6—C7	178.6 (2)
N2—N1—C1—O1	−179.70 (17)	C5—C6—C7—C8	−1.2 (4)
C5—N1—C1—O1	−0.9 (3)	C6—C7—C8—C9	0.9 (4)
N2—N1—C1—C3	−0.7 (2)	C7—C8—C9—C10	0.5 (4)
C5—N1—C1—C3	178.06 (18)	C8—C9—C10—C5	−1.5 (4)
N1—N2—C2—C3	−0.1 (2)	C6—C5—C10—C9	1.1 (3)
N1—N2—C2—C11	−176.8 (2)	N1—C5—C10—C9	−177.33 (19)
N2—C2—C3—C4	176.6 (2)	N3—C4—C12—C17	−97.9 (2)
C11—C2—C3—C4	−7.0 (4)	C3—C4—C12—C17	85.0 (2)
N2—C2—C3—C1	−0.4 (2)	N3—C4—C12—C13	82.5 (2)
C11—C2—C3—C1	175.9 (2)	C3—C4—C12—C13	−94.7 (2)
O1—C1—C3—C4	2.2 (3)	C17—C12—C13—C14	−0.7 (3)
N1—C1—C3—C4	−176.74 (17)	C4—C12—C13—C14	178.95 (19)
O1—C1—C3—C2	179.58 (19)	C12—C13—C14—C15	−0.3 (3)
N1—C1—C3—C2	0.6 (2)	C13—C14—C15—C16	1.0 (4)
C18—N3—C4—C3	−179.37 (19)	C14—C15—C16—C17	−0.8 (4)
C18—N3—C4—C12	3.4 (3)	C13—C12—C17—C16	0.9 (3)
C2—C3—C4—N3	177.21 (19)	C4—C12—C17—C16	−178.8 (2)
C1—C3—C4—N3	−6.2 (3)	C15—C16—C17—C12	−0.1 (4)
C2—C3—C4—C12	−5.7 (3)	C4—N3—C18—C19	169.71 (18)
C1—C3—C4—C12	170.90 (17)	C20—O3—C19—O2	0.5 (3)
C1—N1—C5—C6	18.0 (3)	C20—O3—C19—C18	−179.5 (2)
N2—N1—C5—C6	−163.33 (19)	N3—C18—C19—O2	3.7 (3)
C1—N1—C5—C10	−163.62 (19)	N3—C18—C19—O3	−176.25 (18)
N2—N1—C5—C10	15.1 (3)	C19—O3—C20—C21	−171.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1	0.93 (2)	1.94 (2)	2.704 (2)	137.9 (18)
N3—H3···O2	0.93 (2)	2.26 (2)	2.666 (2)	105.9 (15)
C6—H6···O1	0.96 (2)	2.33 (2)	2.939 (3)	120.3 (17)
C18—H18B···O1^i	0.95 (2)	2.48 (2)	3.317 (3)	146.5 (18)

Symmetry code: (i) −x, −y, −z.