Syntheses, crystal structures, Hirshfeld surface analyses and energy frameworks of two 4-amino­anti­pyrine Schiff base compounds: (E)-4-{[4-(di­ethyl­amino)­benzyl­idene]amino}-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one and (E)-4-[(4-fluoro­benzyl­idene)amino]-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one

Shankar, M.G.; Kumaravel, R.; Subashini, A.; Ramamurthi, K.; Kučeráková, M.; Dušek, M.; Stoeckli-Evans, H.

doi:10.1107/S2056989023004085

Syntheses, crystal structures, Hirshfeld surface analyses and energy frameworks of two 4-aminoantipyrine Schiff base compounds: (E)-4-{[4-(diethylamino)benzylidene]amino}-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one and (E)-4-[(4-fluorobenzylidene)amino]-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one

M. G. Shankar, R. Kumaravel, A. Subashini, K. Ramamurthi, M. Kučeráková, M. Dušek and H. Stoeckli-Evans

The title 4-aminoantipyrine Schiff base compounds both deviate from planarity with the phenyl ring and the substituted benzylidene ring being inclined to the pyrazole ring mean plane by 54.87 (7) and 22.92 (7)°, respectively, in the first compound and by 60.44 (8) and 12.70 (9)° in the second.

Keywords: crystal structure; 4-aminoantipyrine; Hirshfeld surface analysis; energy frameworks.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989023004085/hb8065sup1.cif Contains datablocks I, II, Global
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989023004085/hb8065Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989023004085/hb8065Isup4.cml Supplementary material
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989023004085/hb8065IIsup3.hkl Contains datablock II
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989023004085/hb8065IIsup5.cml Supplementary material
	Portable Document Format (PDF) file https://doi.org/10.1107/S2056989023004085/hb8065sup6.pdf Figures S1-S4

CCDC references: 2261783; 2261784

checkCIF report

Key indicators

Structure: I

Single-crystal X-ray study
T = 120 K
Mean (C-C) = 0.002 Å
R factor = 0.036
wR factor = 0.093
Data-to-parameter ratio = 13.7

Structure: II

Single-crystal X-ray study
T = 95 K
Mean (C-C) = 0.002 Å
R factor = 0.042
wR factor = 0.101
Data-to-parameter ratio = 14.4

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level B
PLAT707_ALERT_1_B D...A   Calc  3.3137(16), Rep    3.318(2), Dev..       2.69 Sigma
              C11      -O1              1_555   1_565 ........     #    1 Check

Alert level C
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.598         22 Report

Alert level G
PLAT717_ALERT_1_G D...A   Unknown or Inconsistent Label ..........        CGB Check
PLAT909_ALERT_3_G Percentage of I>2sig(I) Data at Theta(Max) Still        79% Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT941_ALERT_3_G Average HKL Measurement Multiplicity ...........        4.6 Low
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          2 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   2 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
   4 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check




Datablock: II


Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O1       --C1       .        5.4 s.u.
PLAT715_ALERT_1_C D-H     Unknown or Inconsistent Label ..........        H12 Check
                    C12         H12
PLAT716_ALERT_1_C H...A   Unknown or Inconsistent Label ..........        H12 Check
                    H12         O1
PLAT718_ALERT_1_C D-H..A  Unknown or Inconsistent Label ..........        H12 Check
                    C12         H12         O1
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.251 Check

Alert level G
PLAT717_ALERT_1_G D...A   Unknown or Inconsistent Label ..........        CGB Check
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         17 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         11 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   3 ALERT level G = General information/check it is not something unexpected

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Computing details top

For both structures, data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: Superflip (Palatinus & Chapuis, 2007; JANA2006 (Petříček et al., 2014); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2020) and Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXL2018/3 (Sheldrick, 2015), PLATON (Spek, 2020) and publCIF (Westrip, 2010).

(E)-4-{[4-(Diethylamino)benzylidene]amino}-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one (I) top

Crystal data top

C₂₂H₂₆N₄O	F(000) = 1552
M_r = 362.47	D_x = 1.260 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.5418 Å
a = 17.1588 (7) Å	Cell parameters from 6730 reflections
b = 7.0910 (3) Å	θ = 4.2–67.0°
c = 32.1594 (10) Å	µ = 0.63 mm⁻¹
β = 102.338 (3)°	T = 120 K
V = 3822.6 (3) Å³	Plate, yellow
Z = 8	0.32 × 0.26 × 0.08 mm

Data collection top

Xcalibur, Atlas, Gemini ultra diffractometer	3401 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	2946 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.034
Detector resolution: 10.3784 pixels mm^-1	θ_max = 67.1°, θ_min = 5.3°
ω scans	h = −20→20
Absorption correction: multi-scan (CrysAlisPro; Agilent, 2010)	k = −8→8
T_min = 0.273, T_max = 1.000	l = −32→38
15635 measured reflections

Refinement top

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0498P)² + 1.7059P] where P = (F_o² + 2F_c²)/3
3401 reflections	(Δ/σ)_max = 0.001
248 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.95050 (6)	0.16596 (12)	0.13672 (3)	0.0258 (2)
N1	0.91573 (6)	0.42249 (14)	0.17346 (3)	0.0208 (2)
N2	0.95187 (6)	0.59507 (14)	0.18866 (3)	0.0210 (2)
N3	1.09105 (6)	0.43910 (15)	0.12703 (3)	0.0223 (2)
N4	1.37635 (7)	0.11970 (15)	0.04351 (4)	0.0260 (3)
C1	0.96340 (7)	0.32892 (17)	0.14980 (4)	0.0205 (3)
C2	1.02614 (7)	0.46216 (17)	0.14650 (4)	0.0206 (3)
C3	1.01488 (7)	0.61977 (17)	0.16879 (4)	0.0211 (3)
C4	0.87046 (7)	0.32240 (16)	0.19871 (4)	0.0203 (3)
C5	0.89105 (7)	0.32887 (17)	0.24292 (4)	0.0223 (3)
H5	0.933386	0.407554	0.256954	0.027*
C6	0.84902 (8)	0.21906 (18)	0.26626 (4)	0.0242 (3)
H6	0.862682	0.222736	0.296476	0.029*
C7	0.78720 (8)	0.10388 (17)	0.24593 (4)	0.0246 (3)
H7	0.759273	0.027492	0.262163	0.030*
C8	0.76628 (8)	0.10055 (18)	0.20181 (4)	0.0256 (3)
H8	0.723541	0.022873	0.187820	0.031*
C9	0.80765 (8)	0.21046 (18)	0.17807 (4)	0.0240 (3)
H9	0.793060	0.209089	0.147860	0.029*
C10	0.89517 (9)	0.74834 (18)	0.19053 (5)	0.0283 (3)
H10A	0.859334	0.711170	0.209086	0.042*
H10B	0.863842	0.773905	0.161857	0.042*
H10C	0.924493	0.862223	0.201903	0.042*
C11	1.06192 (8)	0.79734 (18)	0.17469 (4)	0.0265 (3)
H11A	1.083255	0.818394	0.205111	0.040*
H11B	1.027446	0.903218	0.162966	0.040*
H11C	1.106094	0.787545	0.159878	0.040*
C12	1.10770 (8)	0.27332 (18)	0.11476 (4)	0.0230 (3)
H12	1.073861	0.170837	0.118039	0.028*
C13	1.17644 (8)	0.23785 (18)	0.09609 (4)	0.0226 (3)
C14	1.19818 (8)	0.05234 (19)	0.08887 (4)	0.0253 (3)
H14	1.166953	−0.048700	0.095862	0.030*
C15	1.26374 (8)	0.01199 (18)	0.07186 (4)	0.0249 (3)
H15	1.276951	−0.115738	0.067713	0.030*
C16	1.31124 (8)	0.15708 (18)	0.06060 (4)	0.0230 (3)
C17	1.28890 (8)	0.34469 (18)	0.06779 (4)	0.0259 (3)
H17	1.319282	0.446570	0.060432	0.031*
C18	1.22408 (8)	0.38183 (18)	0.08523 (4)	0.0242 (3)
H18	1.211242	0.509177	0.090042	0.029*
C19	1.40771 (8)	−0.07010 (18)	0.04196 (4)	0.0260 (3)
H19A	1.395812	−0.144034	0.065967	0.031*
H19B	1.466432	−0.063114	0.045749	0.031*
C20	1.37361 (9)	−0.1726 (2)	0.00067 (4)	0.0322 (3)
H20A	1.396735	−0.299257	0.001640	0.048*
H20B	1.386511	−0.102288	−0.023225	0.048*
H20C	1.315550	−0.182293	−0.003084	0.048*
C21	1.41662 (8)	0.26801 (19)	0.02481 (4)	0.0267 (3)
H21A	1.376832	0.363552	0.011689	0.032*
H21B	1.440013	0.212963	0.001953	0.032*
C22	1.48234 (9)	0.3647 (2)	0.05712 (5)	0.0325 (3)
H22A	1.509447	0.457307	0.042542	0.049*
H22B	1.520911	0.270251	0.071042	0.049*
H22C	1.458950	0.428731	0.078544	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0313 (5)	0.0211 (4)	0.0271 (5)	−0.0023 (4)	0.0110 (4)	−0.0045 (3)
N1	0.0240 (5)	0.0178 (5)	0.0219 (5)	−0.0019 (4)	0.0078 (4)	−0.0020 (4)
N2	0.0244 (5)	0.0162 (5)	0.0238 (5)	−0.0004 (4)	0.0079 (4)	−0.0014 (4)
N3	0.0229 (5)	0.0243 (5)	0.0202 (5)	0.0009 (4)	0.0058 (4)	0.0007 (4)
N4	0.0271 (6)	0.0242 (6)	0.0295 (6)	0.0001 (4)	0.0123 (5)	−0.0021 (4)
C1	0.0241 (6)	0.0201 (6)	0.0175 (6)	0.0028 (5)	0.0050 (5)	0.0013 (5)
C2	0.0228 (6)	0.0205 (6)	0.0185 (6)	0.0011 (5)	0.0045 (5)	0.0019 (5)
C3	0.0229 (6)	0.0203 (6)	0.0201 (6)	0.0018 (5)	0.0045 (5)	0.0036 (5)
C4	0.0214 (6)	0.0172 (6)	0.0238 (6)	0.0030 (5)	0.0080 (5)	0.0003 (5)
C5	0.0208 (6)	0.0218 (6)	0.0244 (6)	−0.0002 (5)	0.0051 (5)	−0.0028 (5)
C6	0.0273 (7)	0.0241 (6)	0.0224 (6)	0.0014 (5)	0.0082 (5)	−0.0002 (5)
C7	0.0247 (6)	0.0209 (6)	0.0305 (7)	0.0004 (5)	0.0109 (5)	0.0013 (5)
C8	0.0227 (6)	0.0217 (6)	0.0321 (7)	−0.0019 (5)	0.0053 (5)	−0.0031 (5)
C9	0.0250 (6)	0.0239 (6)	0.0225 (6)	0.0002 (5)	0.0035 (5)	−0.0019 (5)
C10	0.0312 (7)	0.0209 (6)	0.0351 (7)	0.0043 (5)	0.0121 (6)	−0.0016 (5)
C11	0.0304 (7)	0.0205 (6)	0.0295 (7)	−0.0026 (5)	0.0084 (5)	0.0001 (5)
C12	0.0249 (6)	0.0242 (6)	0.0201 (6)	−0.0013 (5)	0.0050 (5)	0.0007 (5)
C13	0.0239 (6)	0.0260 (6)	0.0179 (6)	0.0006 (5)	0.0044 (5)	−0.0012 (5)
C14	0.0285 (7)	0.0248 (6)	0.0240 (6)	−0.0032 (5)	0.0083 (5)	−0.0009 (5)
C15	0.0296 (7)	0.0211 (6)	0.0249 (6)	0.0004 (5)	0.0078 (5)	−0.0027 (5)
C16	0.0241 (6)	0.0261 (6)	0.0191 (6)	0.0006 (5)	0.0049 (5)	−0.0014 (5)
C17	0.0277 (7)	0.0234 (6)	0.0284 (7)	−0.0024 (5)	0.0099 (5)	−0.0010 (5)
C18	0.0274 (7)	0.0218 (6)	0.0238 (6)	0.0014 (5)	0.0063 (5)	−0.0016 (5)
C19	0.0258 (7)	0.0272 (7)	0.0261 (7)	0.0032 (5)	0.0078 (5)	−0.0001 (5)
C20	0.0372 (8)	0.0301 (7)	0.0305 (7)	0.0013 (6)	0.0098 (6)	−0.0054 (6)
C21	0.0296 (7)	0.0267 (7)	0.0268 (7)	−0.0008 (5)	0.0126 (5)	−0.0017 (5)
C22	0.0327 (7)	0.0328 (7)	0.0346 (7)	−0.0048 (6)	0.0133 (6)	−0.0063 (6)

Geometric parameters (Å, º) top

O1—C1	1.2335 (15)	C11—H11A	0.9800
N1—C1	1.3978 (16)	C11—H11B	0.9800
N1—N2	1.4112 (14)	C11—H11C	0.9800
N1—C4	1.4269 (16)	C12—C13	1.4551 (18)
N2—C3	1.3796 (16)	C12—H12	0.9500
N2—C10	1.4685 (16)	C13—C18	1.3982 (18)
N3—C12	1.2913 (17)	C13—C14	1.4002 (18)
N3—C2	1.3991 (16)	C14—C15	1.3817 (19)
N4—C16	1.3720 (17)	C14—H14	0.9500
N4—C19	1.4543 (17)	C15—C16	1.4073 (18)
N4—C21	1.4569 (17)	C15—H15	0.9500
C1—C2	1.4533 (18)	C16—C17	1.4172 (18)
C2—C3	1.3635 (17)	C17—C18	1.3737 (19)
C3—C11	1.4858 (18)	C17—H17	0.9500
C4—C9	1.3881 (18)	C18—H18	0.9500
C4—C5	1.3907 (18)	C19—C20	1.5170 (19)
C5—C6	1.3860 (18)	C19—H19A	0.9900
C5—H5	0.9500	C19—H19B	0.9900
C6—C7	1.3868 (19)	C20—H20A	0.9800
C6—H6	0.9500	C20—H20B	0.9800
C7—C8	1.3875 (19)	C20—H20C	0.9800
C7—H7	0.9500	C21—C22	1.523 (2)
C8—C9	1.3877 (19)	C21—H21A	0.9900
C8—H8	0.9500	C21—H21B	0.9900
C9—H9	0.9500	C22—H22A	0.9800
C10—H10A	0.9800	C22—H22B	0.9800
C10—H10B	0.9800	C22—H22C	0.9800
C10—H10C	0.9800

C1—N1—N2	109.58 (9)	H11A—C11—H11C	109.5
C1—N1—C4	121.78 (10)	H11B—C11—H11C	109.5
N2—N1—C4	119.11 (9)	N3—C12—C13	122.35 (12)
C3—N2—N1	106.23 (9)	N3—C12—H12	118.8
C3—N2—C10	121.11 (10)	C13—C12—H12	118.8
N1—N2—C10	114.20 (10)	C18—C13—C14	116.99 (11)
C12—N3—C2	119.50 (11)	C18—C13—C12	123.07 (11)
C16—N4—C19	122.10 (11)	C14—C13—C12	119.93 (11)
C16—N4—C21	121.63 (11)	C15—C14—C13	121.91 (12)
C19—N4—C21	116.24 (10)	C15—C14—H14	119.0
O1—C1—N1	123.17 (11)	C13—C14—H14	119.0
O1—C1—C2	131.75 (11)	C14—C15—C16	121.06 (12)
N1—C1—C2	105.07 (10)	C14—C15—H15	119.5
C3—C2—N3	123.15 (11)	C16—C15—H15	119.5
C3—C2—C1	107.70 (11)	N4—C16—C15	121.87 (11)
N3—C2—C1	129.03 (11)	N4—C16—C17	121.24 (12)
C2—C3—N2	110.64 (11)	C15—C16—C17	116.90 (12)
C2—C3—C11	128.87 (12)	C18—C17—C16	121.17 (12)
N2—C3—C11	120.44 (11)	C18—C17—H17	119.4
C9—C4—C5	120.63 (11)	C16—C17—H17	119.4
C9—C4—N1	118.27 (11)	C17—C18—C13	121.98 (12)
C5—C4—N1	121.01 (11)	C17—C18—H18	119.0
C6—C5—C4	119.15 (12)	C13—C18—H18	119.0
C6—C5—H5	120.4	N4—C19—C20	113.39 (11)
C4—C5—H5	120.4	N4—C19—H19A	108.9
C5—C6—C7	120.64 (12)	C20—C19—H19A	108.9
C5—C6—H6	119.7	N4—C19—H19B	108.9
C7—C6—H6	119.7	C20—C19—H19B	108.9
C6—C7—C8	119.79 (12)	H19A—C19—H19B	107.7
C6—C7—H7	120.1	C19—C20—H20A	109.5
C8—C7—H7	120.1	C19—C20—H20B	109.5
C7—C8—C9	120.14 (12)	H20A—C20—H20B	109.5
C7—C8—H8	119.9	C19—C20—H20C	109.5
C9—C8—H8	119.9	H20A—C20—H20C	109.5
C8—C9—C4	119.62 (12)	H20B—C20—H20C	109.5
C8—C9—H9	120.2	N4—C21—C22	113.00 (11)
C4—C9—H9	120.2	N4—C21—H21A	109.0
N2—C10—H10A	109.5	C22—C21—H21A	109.0
N2—C10—H10B	109.5	N4—C21—H21B	109.0
H10A—C10—H10B	109.5	C22—C21—H21B	109.0
N2—C10—H10C	109.5	H21A—C21—H21B	107.8
H10A—C10—H10C	109.5	C21—C22—H22A	109.5
H10B—C10—H10C	109.5	C21—C22—H22B	109.5
C3—C11—H11A	109.5	H22A—C22—H22B	109.5
C3—C11—H11B	109.5	C21—C22—H22C	109.5
H11A—C11—H11B	109.5	H22A—C22—H22C	109.5
C3—C11—H11C	109.5	H22B—C22—H22C	109.5

C1—N1—N2—C3	9.12 (13)	C4—C5—C6—C7	0.04 (19)
C4—N1—N2—C3	156.03 (10)	C5—C6—C7—C8	−1.04 (19)
C1—N1—N2—C10	145.25 (10)	C6—C7—C8—C9	0.74 (19)
C4—N1—N2—C10	−67.83 (14)	C7—C8—C9—C4	0.54 (19)
N2—N1—C1—O1	171.84 (11)	C5—C4—C9—C8	−1.55 (18)
C4—N1—C1—O1	25.96 (18)	N1—C4—C9—C8	175.24 (11)
N2—N1—C1—C2	−6.89 (13)	C2—N3—C12—C13	−177.11 (11)
C4—N1—C1—C2	−152.77 (11)	N3—C12—C13—C18	−7.96 (19)
C12—N3—C2—C3	164.73 (12)	N3—C12—C13—C14	171.03 (12)
C12—N3—C2—C1	−10.89 (19)	C18—C13—C14—C15	0.13 (19)
O1—C1—C2—C3	−176.49 (13)	C12—C13—C14—C15	−178.92 (12)
N1—C1—C2—C3	2.09 (13)	C13—C14—C15—C16	−0.7 (2)
O1—C1—C2—N3	−0.3 (2)	C19—N4—C16—C15	−9.62 (19)
N1—C1—C2—N3	178.24 (11)	C21—N4—C16—C15	168.66 (12)
N3—C2—C3—N2	−172.83 (11)	C19—N4—C16—C17	170.24 (12)
C1—C2—C3—N2	3.60 (14)	C21—N4—C16—C17	−11.49 (19)
N3—C2—C3—C11	4.6 (2)	C14—C15—C16—N4	−179.73 (12)
C1—C2—C3—C11	−178.95 (12)	C14—C15—C16—C17	0.41 (18)
N1—N2—C3—C2	−7.78 (13)	N4—C16—C17—C18	−179.46 (12)
C10—N2—C3—C2	−140.20 (12)	C15—C16—C17—C18	0.40 (18)
N1—N2—C3—C11	174.52 (11)	C16—C17—C18—C13	−1.0 (2)
C10—N2—C3—C11	42.11 (17)	C14—C13—C18—C17	0.71 (19)
C1—N1—C4—C9	−66.68 (16)	C12—C13—C18—C17	179.72 (12)
N2—N1—C4—C9	150.54 (11)	C16—N4—C19—C20	92.75 (14)
C1—N1—C4—C5	110.10 (13)	C21—N4—C19—C20	−85.62 (14)
N2—N1—C4—C5	−32.67 (16)	C16—N4—C21—C22	88.73 (15)
C9—C4—C5—C6	1.26 (18)	C19—N4—C21—C22	−92.90 (14)
N1—C4—C5—C6	−175.45 (11)

Hydrogen-bond geometry (Å, º) top

CgB is the centroid of ring B (C4–C9).

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11B···O1ⁱ	0.98	2.33	3.314 (2)	177
C12—H12···O1	0.95	2.32	3.028 (2)	131
C22—H22C···O1ⁱⁱ	0.98	2.54	3.466 (2)	157
C7—H7···CgBⁱⁱⁱ	0.95	2.79	3.674 (1)	155

Symmetry codes: (i) x, y+1, z; (ii) x+1/2, y+1/2, z; (iii) −x+3/2, y−1/2, −z+1/2.

(E)-4-[(4-Fluorobenzylidene)amino]-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one (II) top

Crystal data top

C₁₈H₁₆FN₃O	D_x = 1.353 Mg m⁻³
M_r = 309.34	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 3075 reflections
a = 6.7886 (13) Å	θ = 5.3–73.0°
b = 16.6007 (3) Å	µ = 0.10 mm⁻¹
c = 26.9563 (8) Å	T = 95 K
V = 3037.9 (6) Å³	Block, colourless
Z = 8	0.08 × 0.05 × 0.03 mm
F(000) = 1296

Data collection top

SuperNova, AtlasS2 diffractometer	3041 independent reflections
Radiation source: X-ray tube	2346 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.064
Detector resolution: 5.2027 pixels mm^-1	θ_max = 26.2°, θ_min = 1.5°
ω scans	h = −7→8
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2022)	k = −20→20
T_min = 0.074, T_max = 1.000	l = −21→33
16735 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.101	w = 1/[σ²(F_o²) + (0.0413P)² + 0.3986P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
3041 reflections	Δρ_max = 0.21 e Å⁻³
211 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: (SHELXL2018/3; Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0025 (5)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
F1	0.87181 (18)	0.01263 (7)	−0.22907 (4)	0.0355 (3)
O1	0.72869 (16)	0.08876 (7)	0.07747 (4)	0.0227 (3)
N1	0.45169 (19)	0.15388 (8)	0.10880 (5)	0.0191 (3)
N2	0.28459 (19)	0.19055 (8)	0.08765 (5)	0.0199 (3)
N3	0.48528 (19)	0.10471 (8)	−0.02205 (5)	0.0188 (3)
C1	0.5616 (2)	0.11647 (10)	0.07073 (6)	0.0185 (3)
C2	0.4406 (2)	0.12362 (9)	0.02704 (6)	0.0182 (3)
C3	0.2737 (2)	0.16588 (9)	0.03975 (6)	0.0184 (3)
C4	0.5493 (2)	0.19326 (10)	0.14907 (6)	0.0196 (3)
C5	0.5650 (2)	0.27676 (11)	0.15110 (6)	0.0226 (4)
H5	0.504845	0.309414	0.126438	0.027*
C6	0.6700 (2)	0.31165 (12)	0.18982 (7)	0.0274 (4)
H6	0.680539	0.368625	0.191832	0.033*
C7	0.7597 (2)	0.26390 (13)	0.22553 (7)	0.0313 (4)
H7	0.832965	0.288135	0.251573	0.038*
C8	0.7421 (3)	0.18061 (13)	0.22317 (7)	0.0300 (4)
H8	0.802971	0.147933	0.247699	0.036*
C9	0.6357 (2)	0.14503 (11)	0.18500 (6)	0.0242 (4)
H9	0.622161	0.088118	0.183518	0.029*
C10	0.1160 (2)	0.20736 (11)	0.11996 (6)	0.0240 (4)
H10A	0.161622	0.234823	0.150023	0.036*
H10B	0.051684	0.156623	0.129077	0.036*
H10C	0.021908	0.241881	0.102403	0.036*
C11	0.0992 (2)	0.18413 (11)	0.00855 (7)	0.0252 (4)
H11C	0.124258	0.166697	−0.025605	0.038*
H11B	0.073898	0.242251	0.009018	0.038*
H11A	−0.015913	0.155503	0.021628	0.038*
C12	0.6468 (2)	0.06772 (10)	−0.03275 (6)	0.0196 (3)
H12A	0.730837	0.049874	−0.006810	0.024*
C13	0.7020 (2)	0.05290 (9)	−0.08456 (6)	0.0196 (3)
C14	0.8853 (3)	0.01856 (10)	−0.09495 (6)	0.0231 (4)
H14	0.970961	0.004617	−0.068426	0.028*
C15	0.9441 (3)	0.00454 (11)	−0.14364 (6)	0.0257 (4)
H15	1.068284	−0.019112	−0.150837	0.031*
C16	0.8166 (3)	0.02601 (11)	−0.18100 (6)	0.0265 (4)
C17	0.6341 (3)	0.06039 (11)	−0.17255 (6)	0.0248 (4)
H17	0.550125	0.074561	−0.199357	0.030*
C18	0.5772 (2)	0.07358 (10)	−0.12379 (6)	0.0222 (3)
H18	0.452267	0.096883	−0.117004	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0454 (6)	0.0410 (7)	0.0201 (5)	0.0028 (5)	0.0106 (5)	−0.0031 (4)
O1	0.0174 (5)	0.0287 (6)	0.0220 (6)	0.0060 (5)	−0.0013 (5)	−0.0022 (5)
N1	0.0162 (6)	0.0213 (7)	0.0197 (6)	0.0024 (5)	−0.0019 (5)	−0.0016 (5)
N2	0.0145 (6)	0.0222 (7)	0.0231 (7)	0.0029 (5)	−0.0011 (5)	−0.0002 (5)
N3	0.0198 (6)	0.0180 (7)	0.0187 (6)	−0.0020 (5)	0.0014 (5)	0.0002 (5)
C1	0.0189 (7)	0.0171 (8)	0.0196 (8)	−0.0015 (6)	0.0023 (6)	0.0002 (6)
C2	0.0187 (7)	0.0154 (7)	0.0206 (8)	−0.0021 (6)	0.0001 (6)	0.0019 (6)
C3	0.0181 (7)	0.0161 (7)	0.0211 (8)	−0.0032 (6)	−0.0003 (6)	0.0011 (6)
C4	0.0135 (7)	0.0261 (9)	0.0192 (8)	0.0000 (6)	0.0020 (6)	−0.0015 (6)
C5	0.0187 (7)	0.0266 (9)	0.0223 (8)	−0.0009 (7)	0.0020 (6)	−0.0011 (7)
C6	0.0201 (8)	0.0320 (10)	0.0302 (9)	−0.0052 (7)	0.0045 (7)	−0.0079 (8)
C7	0.0190 (8)	0.0497 (12)	0.0251 (9)	−0.0032 (8)	−0.0009 (7)	−0.0106 (8)
C8	0.0217 (8)	0.0458 (12)	0.0227 (8)	0.0046 (8)	−0.0025 (7)	0.0005 (8)
C9	0.0187 (7)	0.0310 (10)	0.0229 (8)	0.0023 (7)	0.0027 (7)	0.0008 (7)
C10	0.0180 (7)	0.0254 (9)	0.0287 (9)	0.0011 (6)	0.0039 (7)	−0.0043 (7)
C11	0.0220 (8)	0.0251 (9)	0.0284 (9)	0.0035 (7)	−0.0046 (7)	−0.0002 (7)
C12	0.0205 (7)	0.0175 (8)	0.0208 (8)	−0.0013 (6)	−0.0019 (6)	0.0006 (6)
C13	0.0227 (8)	0.0151 (8)	0.0210 (8)	−0.0023 (6)	0.0011 (7)	0.0005 (6)
C14	0.0256 (8)	0.0197 (8)	0.0240 (8)	0.0012 (7)	0.0004 (7)	0.0020 (6)
C15	0.0269 (8)	0.0218 (8)	0.0284 (9)	0.0030 (7)	0.0062 (7)	−0.0005 (7)
C16	0.0366 (9)	0.0229 (9)	0.0199 (8)	−0.0027 (7)	0.0083 (7)	−0.0028 (6)
C17	0.0285 (8)	0.0257 (9)	0.0202 (8)	−0.0013 (7)	−0.0014 (7)	0.0002 (7)
C18	0.0227 (8)	0.0201 (8)	0.0238 (8)	0.0001 (6)	0.0015 (7)	−0.0001 (6)

Geometric parameters (Å, º) top

F1—C16	1.367 (2)	C8—H8	0.9500
O1—C1	1.237 (2)	C9—H9	0.9500
N1—N2	1.4080 (18)	C10—H10A	0.9800
N1—C1	1.413 (2)	C10—H10B	0.9800
N1—C4	1.430 (2)	C10—H10C	0.9800
N2—C3	1.356 (2)	C11—H11C	0.9800
N2—C10	1.465 (2)	C11—H11B	0.9800
N3—C12	1.289 (2)	C11—H11A	0.9800
N3—C2	1.394 (2)	C12—C13	1.467 (2)
C1—C2	1.441 (2)	C12—H12A	0.9500
C2—C3	1.376 (2)	C13—C14	1.397 (2)
C3—C11	1.484 (2)	C13—C18	1.398 (2)
C4—C9	1.387 (2)	C14—C15	1.392 (2)
C4—C5	1.391 (2)	C14—H14	0.9500
C5—C6	1.390 (2)	C15—C16	1.375 (3)
C5—H5	0.9500	C15—H15	0.9500
C6—C7	1.388 (3)	C16—C17	1.383 (3)
C6—H6	0.9500	C17—C18	1.387 (2)
C7—C8	1.389 (3)	C17—H17	0.9500
C7—H7	0.9500	C18—H18	0.9500
C8—C9	1.389 (3)

N2—N1—C1	108.75 (12)	N2—C10—H10A	109.5
C1—N1—C4	120.50 (13)	N2—C10—H10B	109.5
N2—N1—C4	118.90 (13)	H10A—C10—H10B	109.5
C3—N2—N1	107.40 (13)	N2—C10—H10C	109.5
C3—N2—C10	125.50 (14)	H10A—C10—H10C	109.5
N1—N2—C10	118.09 (13)	H10B—C10—H10C	109.5
C12—N3—C2	120.32 (14)	C3—C11—H11C	109.5
O1—C1—N1	122.75 (15)	C3—C11—H11B	109.5
O1—C1—C2	132.33 (15)	H11C—C11—H11B	109.5
N1—C1—C2	104.85 (13)	C3—C11—H11A	109.5
C3—C2—N3	122.05 (14)	H11C—C11—H11A	109.5
C3—C2—C1	107.94 (14)	H11B—C11—H11A	109.5
N3—C2—C1	129.30 (14)	N3—C12—C13	120.68 (15)
N2—C3—C2	110.24 (14)	N3—C12—H12A	119.7
N2—C3—C11	121.43 (14)	C13—C12—H12A	119.7
C2—C3—C11	128.33 (15)	C14—C13—C18	119.24 (15)
C9—C4—C5	121.03 (16)	C14—C13—C12	119.14 (15)
C9—C4—N1	117.53 (15)	C18—C13—C12	121.62 (15)
C5—C4—N1	121.38 (15)	C15—C14—C13	120.84 (16)
C6—C5—C4	118.93 (16)	C15—C14—H14	119.6
C6—C5—H5	120.5	C13—C14—H14	119.6
C4—C5—H5	120.5	C16—C15—C14	117.85 (16)
C7—C6—C5	120.50 (18)	C16—C15—H15	121.1
C7—C6—H6	119.7	C14—C15—H15	121.1
C5—C6—H6	119.7	F1—C16—C15	118.67 (16)
C6—C7—C8	119.95 (17)	F1—C16—C17	117.94 (16)
C6—C7—H7	120.0	C15—C16—C17	123.39 (16)
C8—C7—H7	120.0	C16—C17—C18	118.07 (16)
C9—C8—C7	120.12 (18)	C16—C17—H17	121.0
C9—C8—H8	119.9	C18—C17—H17	121.0
C7—C8—H8	119.9	C17—C18—C13	120.62 (16)
C4—C9—C8	119.45 (18)	C17—C18—H18	119.7
C4—C9—H9	120.3	C13—C18—H18	119.7
C8—C9—H9	120.3

C1—N1—N2—C3	9.45 (17)	N2—N1—C4—C5	−36.0 (2)
C4—N1—N2—C3	152.54 (14)	C1—N1—C4—C5	102.73 (18)
C1—N1—N2—C10	158.44 (14)	C9—C4—C5—C6	0.3 (2)
C4—N1—N2—C10	−58.47 (19)	N1—C4—C5—C6	−176.80 (14)
N2—N1—C1—O1	170.21 (15)	C4—C5—C6—C7	0.7 (2)
C4—N1—C1—O1	27.8 (2)	C5—C6—C7—C8	−1.0 (3)
N2—N1—C1—C2	−7.02 (17)	C6—C7—C8—C9	0.3 (3)
C4—N1—C1—C2	−149.42 (14)	C5—C4—C9—C8	−1.0 (2)
C12—N3—C2—C3	177.33 (15)	N1—C4—C9—C8	176.19 (14)
C12—N3—C2—C1	8.2 (3)	C7—C8—C9—C4	0.7 (2)
O1—C1—C2—C3	−174.69 (18)	C2—N3—C12—C13	−175.43 (14)
N1—C1—C2—C3	2.15 (17)	N3—C12—C13—C14	174.82 (15)
O1—C1—C2—N3	−4.3 (3)	N3—C12—C13—C18	−4.0 (2)
N1—C1—C2—N3	172.51 (15)	C18—C13—C14—C15	−0.3 (2)
N1—N2—C3—C2	−8.11 (18)	C12—C13—C14—C15	−179.17 (16)
C10—N2—C3—C2	−154.17 (15)	C13—C14—C15—C16	0.4 (3)
N1—N2—C3—C11	171.33 (14)	C14—C15—C16—F1	−179.96 (16)
C10—N2—C3—C11	25.3 (2)	C14—C15—C16—C17	−0.2 (3)
N3—C2—C3—N2	−167.49 (14)	F1—C16—C17—C18	179.62 (15)
C1—C2—C3—N2	3.71 (18)	C15—C16—C17—C18	−0.2 (3)
N3—C2—C3—C11	13.1 (3)	C16—C17—C18—C13	0.3 (3)
C1—C2—C3—C11	−175.67 (16)	C14—C13—C18—C17	−0.1 (2)
N2—N1—C4—C9	146.82 (14)	C12—C13—C18—C17	178.78 (15)
C1—N1—C4—C9	−74.49 (19)

Hydrogen-bond geometry (Å, º) top

CgB is the centroid of ring B (C4–C9).

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O1ⁱ	0.98	2.55	3.505 (2)	165
C12—H12A···O1	0.95	2.36	3.043 (2)	128
C14—H14···O1ⁱⁱ	0.95	2.57	3.204 (2)	124
C17—H17···F1ⁱⁱⁱ	0.95	2.50	3.291 (2)	141
C7—H7···CgB^iv	0.95	2.90	3.608 (2)	132

Symmetry codes: (i) x−1, y, z; (ii) −x+2, −y, −z; (iii) x−1/2, y, −z−1/2; (iv) x+1/2, y, −z+1/2.

Selected geometric parameters (Å, °) for I and TAYLUB01^a, and for II and KELZIL^b and KEQXOU^c top

	I	TAYLUB01^a	II	KELZIL^b	KEQXOU^c
N3—C12	1.291 (2)	1.288 (2)	1.289 (2)	1.276 (2)	1.279 (5)
C2—N3—C12—C13	–177.11 (11)	173.20 (11)	–175.43 (14)	–176.68 (15)	177.5 (4)

C1—N1—N2	109.58 (9)	109.58 (10)	108.75 (12)	108.58 (13)	106.9 (3)
C1—N1—C4	121.78 (10)	122.30 (10)	120.50 (13)	122.40 (13)	122.4 (3)
N2—N1—C4	119.11 (9)	118.13 (10)	118.90 (13)	119.12 (14)	119.8 (3)
Sum	350.47 (9)	350.0 (1)	348.15 (13)	350.10 (13)	349.1 (3)

C3—N2—N1	106.23 (9)	106.50 (10)	107.40 (13)	107.34 (13)	107.7 (3)
C3—N2—C10	121.11 (10)	122.30 (11)	125.50 (14)	124.77 (14)	125.1 (3)
N1—N2—C10	114.20 (10)	114.68 (10)	118.09 (13)	117.05 (15)	115.9 (3)
Sum	341.54 (10)	343.48 (10)	350.99 (13)	349.16 (14)	348.7 (3)

Notes: (a) Asiri et al. (2010); (b) Sun et al. 2006); (c) Yan et al. 2006).

A comparison of various dihedral angles (°) for I and TAYLUB01^a, and for II and KELZIL^b and KEQXOU^c top

A = ring N1/N2/C1–C3, B = ring C4–C9, C = ring C13–C18 (atom numbering following this paper).

Dihedral angle	I	TAYLUB01^a	II	KELZIL^b	KEQXOU^c
Planes A to B	54.87 (7)	55.01 (7)	60.44 (8)	51.6 (1)	50.8 (2)
Planes A to C	22.92 (7)	19.03 (7)	12.70 (9)	8.7 (1)	9.1 (2)
Planes B to C	73.98 (6)	73.98 (6)	71.28 (8)	59.0 (1)	59.1 (2)

Notes: (a) Asiri et al. (2010); (b) Sun et al. 2006); (c) Yan et al. 2006).

Principal percentage contributions of inter-atomic contacts to the Hirshfeld surfaces of I, TAYLUB01^a, II, KELZIL^b and KEQXOU^c top

Contact	I	TAYLUB01^a	II	KELZIL^b	KEQXOU^c
			X = F	X = Cl	X = Br
H···H	60.6	57.7	43.2	43.7	43.1
C···H/H···C	26.7	27.3	28.6	25.1	25.0
N···H/H···N	4.8	4.5	4.2	3.6	3.5
O···H/H···O	6.8	7.2	8.3	7.3	7.2
X···H/H···X	–	–	10.5	12.9	13.5
C···C	0.2	1.3	2.7	3.9	3.9
N···C/C···N	0.4	1.6	1.7	2.0	2.2
O···C/C···O	0	0	0.3	0.5	0.5
X···X	–	–	0.4	0.9	1.0

Notes: (a) Asiri et al. (2010); (b) Sun et al. 2006); (c) Yan et al. 2006).

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