3-{1-[2-(2-Chloro-phen-yl)hydrazinyl-idene]-2,2,2-trifluoro-eth-yl}-7-diethyl-amino-2H-chromen-2-one.

The title compound, C(21)H(19)ClF(3)N(3)O(2), has a structure related to other coumarin derivatives that have been used as fluorescent probes of metal ions. The dihedral angle between the coumarin ring system and the chlorobenzene ring is 42.99 (9)°. Intra-molecular hydrogen bonding occurs via N-H⋯O and N-H⋯Cl inter-actions, generating S(7) and S(5) rings, respectively. The crystal packing is stabilized by weak C-H⋯O hydrogen bonds.

Related literature

For applications of coumarins and coumarin derivatives, see: Trenor et al. (2004 ▶); Starcevic et al. (2011 ▶); Danko et al. (2011 ▶). For the synthesis of the title compound and related structures, see: Li et al. (2011 ▶).

Experimental

Crystal data

C21H19ClF3N3O2

M = 437.84

Orthorhombic,

a = 7.940 (6) Å

b = 12.602 (9) Å

c = 20.233 (15) Å

V = 2025 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.24 mm−1

T = 296 K

0.20 × 0.20 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.954, T max = 0.958

10369 measured reflections

3576 independent reflections

3162 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.078

S = 1.03

3576 reflections

273 parameters

H-atom parameters constrained

Δρmax = 0.15 e Å−3

Δρmin = −0.21 e Å−3

Absolute structure: Flack (1983 ▶), 1511 Friedel pairs

Flack parameter: −0.09 (6)

Data collection: APEX2 (Bruker, 2003 ▶); cell refinement: SAINT-Plus (Bruker, 2003 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811031916/lr2022sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811031916/lr2022Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811031916/lr2022Isup3.cml

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

C21H19ClF3N3O2	Dx = 1.436 Mg m−3
Mr = 437.84	Melting point = 423–425 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
a = 7.940 (6) Å	Cell parameters from 3770 reflections
b = 12.602 (9) Å	θ = 2.6–24.7°
c = 20.233 (15) Å	µ = 0.24 mm−1
V = 2025 (3) Å3	T = 296 K
Z = 4	Block, orange
F(000) = 904	0.20 × 0.20 × 0.18 mm

Bruker APEXII CCD diffractometer	3576 independent reflections
Radiation source: fine-focus sealed tube	3162 reflections with I > 2σ(I)
graphite	Rint = 0.023
φ and ω scans	θmax = 25.1°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→9
Tmin = 0.954, Tmax = 0.958	k = −15→9
10369 measured reflections	l = −24→24

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)] = 0.032	H-atom parameters constrained
wR(F2) = 0.078	w = 1/[σ2(Fo2) + (0.0416P)2 + 0.1045P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
3576 reflections	Δρmax = 0.15 e Å−3
273 parameters	Δρmin = −0.21 e Å−3
0 restraints	Absolute structure: Flack (1983), 1511 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.09 (6)

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
C1	−0.0571 (3)	0.51038 (15)	0.15673 (9)	0.0426 (5)
C2	−0.0012 (3)	0.46256 (15)	0.09683 (10)	0.0479 (5)
H2	0.0292	0.3913	0.0970	0.058*
C3	0.0088 (3)	0.51828 (14)	0.03965 (10)	0.0450 (5)
H3	0.0447	0.4842	0.0014	0.054*
C4	−0.0343 (2)	0.62689 (14)	0.03692 (9)	0.0382 (4)
C5	−0.0249 (2)	0.69109 (14)	−0.01980 (10)	0.0391 (4)
H5	0.0082	0.6604	−0.0595	0.047*
C6	−0.0629 (2)	0.79729 (14)	−0.01872 (9)	0.0358 (4)
C7	−0.1134 (3)	0.84426 (14)	0.04343 (9)	0.0392 (4)
C8	−0.0900 (2)	0.67227 (13)	0.09569 (9)	0.0366 (4)
C9	−0.1056 (3)	0.61729 (14)	0.15382 (9)	0.0415 (5)
H9	−0.1481	0.6508	0.1912	0.050*
C10	−0.0636 (2)	0.86150 (14)	−0.08005 (8)	0.0363 (4)
C11	0.1033 (2)	1.12141 (14)	−0.06355 (9)	0.0382 (4)
C12	0.1722 (3)	1.18859 (16)	−0.01670 (10)	0.0471 (5)
C13	0.2242 (3)	1.29033 (17)	−0.03257 (12)	0.0564 (6)
H13	0.2701	1.3341	−0.0003	0.068*
C14	0.2075 (3)	1.32630 (17)	−0.09657 (12)	0.0613 (6)
H14	0.2430	1.3942	−0.1080	0.074*
C15	0.1377 (3)	1.26061 (16)	−0.14320 (11)	0.0559 (6)
H15	0.1242	1.2851	−0.1862	0.067*
C16	0.0874 (3)	1.15921 (15)	−0.12760 (10)	0.0456 (5)
H16	0.0424	1.1157	−0.1603	0.055*
C17	−0.1226 (3)	0.80735 (15)	−0.14206 (10)	0.0434 (5)
C18	0.0107 (3)	0.34867 (17)	0.21991 (12)	0.0607 (6)
H18A	−0.0171	0.3080	0.1807	0.073*
H18B	−0.0374	0.3124	0.2578	0.073*
C19	0.1987 (3)	0.3531 (2)	0.22744 (16)	0.0921 (9)
H19A	0.2465	0.3907	0.1907	0.138*
H19B	0.2431	0.2823	0.2287	0.138*
H19C	0.2266	0.3892	0.2678	0.138*
C20	−0.1199 (3)	0.50530 (18)	0.27618 (10)	0.0596 (6)
H20A	−0.0763	0.5772	0.2778	0.071*
H20B	−0.0738	0.4667	0.3135	0.071*
C21	−0.3098 (3)	0.50846 (19)	0.28210 (12)	0.0698 (7)
H21A	−0.3558	0.5489	0.2462	0.105*
H21B	−0.3405	0.5411	0.3233	0.105*
H21C	−0.3535	0.4375	0.2807	0.105*
Cl1	0.19498 (10)	1.14505 (5)	0.06447 (3)	0.0753 (2)
F1	−0.24651 (16)	0.73715 (9)	−0.13101 (6)	0.0567 (3)
F2	0.00093 (17)	0.75115 (10)	−0.17132 (6)	0.0632 (4)
F3	−0.17985 (19)	0.87363 (10)	−0.18810 (5)	0.0661 (4)
N1	−0.0641 (2)	0.45457 (13)	0.21455 (9)	0.0514 (4)
N2	−0.0139 (2)	0.95674 (12)	−0.09268 (8)	0.0397 (4)
N3	0.0552 (2)	1.01831 (12)	−0.04584 (8)	0.0437 (4)
H3A	0.0694	0.9952	−0.0062	0.052*
O1	−0.12920 (18)	0.77888 (9)	0.09745 (6)	0.0415 (3)
O2	−0.1471 (2)	0.93702 (10)	0.05297 (6)	0.0522 (4)

	U11	U22	U33	U12	U13	U23
C1	0.0369 (11)	0.0411 (11)	0.0499 (11)	−0.0028 (9)	−0.0021 (9)	0.0060 (9)
C2	0.0502 (13)	0.0323 (10)	0.0613 (12)	0.0059 (10)	0.0028 (11)	0.0016 (9)
C3	0.0496 (12)	0.0335 (10)	0.0520 (11)	0.0050 (9)	0.0082 (10)	−0.0049 (9)
C4	0.0382 (11)	0.0322 (9)	0.0441 (10)	0.0007 (8)	0.0012 (8)	−0.0024 (8)
C5	0.0382 (11)	0.0361 (10)	0.0430 (10)	0.0023 (8)	0.0020 (9)	−0.0069 (8)
C6	0.0337 (10)	0.0334 (9)	0.0404 (10)	−0.0007 (8)	0.0015 (8)	−0.0041 (8)
C7	0.0395 (11)	0.0338 (10)	0.0441 (10)	0.0006 (9)	0.0034 (9)	−0.0006 (8)
C8	0.0356 (11)	0.0283 (9)	0.0458 (11)	0.0003 (8)	−0.0020 (9)	−0.0039 (8)
C9	0.0448 (12)	0.0373 (10)	0.0423 (11)	−0.0002 (9)	0.0035 (9)	−0.0008 (8)
C10	0.0359 (11)	0.0332 (10)	0.0398 (10)	0.0001 (8)	−0.0001 (8)	−0.0045 (8)
C11	0.0341 (11)	0.0338 (9)	0.0467 (10)	0.0001 (8)	0.0010 (9)	−0.0045 (9)
C12	0.0439 (12)	0.0480 (12)	0.0493 (11)	−0.0006 (9)	−0.0033 (10)	−0.0109 (9)
C13	0.0489 (14)	0.0448 (12)	0.0755 (15)	−0.0057 (11)	0.0002 (12)	−0.0199 (11)
C14	0.0652 (17)	0.0379 (11)	0.0809 (16)	−0.0099 (11)	0.0106 (14)	−0.0033 (12)
C15	0.0653 (15)	0.0442 (12)	0.0584 (12)	−0.0021 (11)	0.0072 (12)	0.0072 (11)
C16	0.0494 (12)	0.0402 (11)	0.0470 (11)	−0.0022 (9)	0.0002 (10)	−0.0045 (9)
C17	0.0439 (12)	0.0416 (10)	0.0448 (11)	0.0006 (10)	0.0007 (10)	−0.0035 (9)
C18	0.0596 (15)	0.0501 (13)	0.0723 (14)	0.0051 (12)	0.0076 (13)	0.0251 (12)
C19	0.0581 (18)	0.098 (2)	0.120 (2)	0.0182 (16)	0.0011 (17)	0.0512 (19)
C20	0.0794 (18)	0.0557 (13)	0.0437 (12)	0.0008 (13)	−0.0060 (11)	0.0080 (10)
C21	0.0807 (19)	0.0722 (16)	0.0566 (14)	0.0012 (15)	0.0098 (13)	0.0013 (12)
Cl1	0.0938 (5)	0.0819 (4)	0.0501 (3)	−0.0075 (4)	−0.0206 (3)	−0.0080 (3)
F1	0.0522 (7)	0.0562 (7)	0.0616 (7)	−0.0130 (6)	−0.0040 (6)	−0.0129 (6)
F2	0.0581 (8)	0.0710 (8)	0.0604 (7)	0.0048 (7)	0.0106 (6)	−0.0272 (6)
F3	0.0926 (11)	0.0582 (8)	0.0474 (7)	0.0008 (7)	−0.0190 (7)	−0.0007 (6)
N1	0.0567 (12)	0.0434 (9)	0.0542 (10)	0.0047 (9)	0.0003 (9)	0.0121 (8)
N2	0.0408 (10)	0.0356 (9)	0.0429 (8)	0.0006 (7)	0.0006 (7)	−0.0048 (7)
N3	0.0537 (11)	0.0375 (8)	0.0398 (9)	−0.0064 (8)	−0.0056 (7)	−0.0017 (7)
O1	0.0534 (9)	0.0311 (6)	0.0401 (7)	0.0056 (6)	0.0076 (6)	−0.0014 (6)
O2	0.0747 (11)	0.0300 (7)	0.0519 (8)	0.0090 (7)	0.0138 (8)	−0.0026 (6)

C1—N1	1.366 (3)	C13—H13	0.9300
C1—C9	1.402 (3)	C14—C15	1.372 (3)
C1—C2	1.424 (3)	C14—H14	0.9300
C2—C3	1.356 (3)	C15—C16	1.376 (3)
C2—H2	0.9300	C15—H15	0.9300
C3—C4	1.412 (3)	C16—H16	0.9300
C3—H3	0.9300	C17—F3	1.331 (2)
C4—C8	1.392 (3)	C17—F1	1.342 (2)
C4—C5	1.406 (3)	C17—F2	1.347 (2)
C5—C6	1.372 (3)	C18—N1	1.465 (3)
C5—H5	0.9300	C18—C19	1.501 (4)
C6—C7	1.447 (3)	C18—H18A	0.9700
C6—C10	1.481 (3)	C18—H18B	0.9700
C7—O2	1.215 (2)	C19—H19A	0.9600
C7—O1	1.374 (2)	C19—H19B	0.9600
C8—C9	1.371 (3)	C19—H19C	0.9600
C8—O1	1.380 (2)	C20—N1	1.470 (3)
C9—H9	0.9300	C20—C21	1.513 (4)
C10—N2	1.289 (2)	C20—H20A	0.9700
C10—C17	1.503 (3)	C20—H20B	0.9700
C11—C12	1.384 (3)	C21—H21A	0.9600
C11—C16	1.387 (3)	C21—H21B	0.9600
C11—N3	1.401 (2)	C21—H21C	0.9600
C12—C13	1.385 (3)	N2—N3	1.342 (2)
C12—Cl1	1.741 (2)	N3—H3A	0.8600
C13—C14	1.378 (3)
N1—C1—C9	121.30 (18)	C14—C15—H15	119.3
N1—C1—C2	121.56 (18)	C16—C15—H15	119.3
C9—C1—C2	117.14 (17)	C15—C16—C11	120.48 (19)
C3—C2—C1	121.68 (18)	C15—C16—H16	119.8
C3—C2—H2	119.2	C11—C16—H16	119.8
C1—C2—H2	119.2	F3—C17—F1	106.26 (17)
C2—C3—C4	121.42 (17)	F3—C17—F2	105.71 (17)
C2—C3—H3	119.3	F1—C17—F2	105.10 (15)
C4—C3—H3	119.3	F3—C17—C10	113.93 (16)
C8—C4—C5	118.53 (16)	F1—C17—C10	112.88 (16)
C8—C4—C3	116.23 (16)	F2—C17—C10	112.26 (17)
C5—C4—C3	125.24 (17)	N1—C18—C19	112.1 (2)
C6—C5—C4	122.46 (18)	N1—C18—H18A	109.2
C6—C5—H5	118.8	C19—C18—H18A	109.2
C4—C5—H5	118.8	N1—C18—H18B	109.2
C5—C6—C7	118.29 (18)	C19—C18—H18B	109.2
C5—C6—C10	121.36 (17)	H18A—C18—H18B	107.9
C7—C6—C10	120.22 (16)	C18—C19—H19A	109.5
O2—C7—O1	115.49 (16)	C18—C19—H19B	109.5
O2—C7—C6	126.37 (17)	H19A—C19—H19B	109.5
O1—C7—C6	118.12 (15)	C18—C19—H19C	109.5
C9—C8—O1	116.72 (16)	H19A—C19—H19C	109.5
C9—C8—C4	123.65 (17)	H19B—C19—H19C	109.5
O1—C8—C4	119.61 (16)	N1—C20—C21	112.3 (2)
C8—C9—C1	119.79 (17)	N1—C20—H20A	109.1
C8—C9—H9	120.1	C21—C20—H20A	109.1
C1—C9—H9	120.1	N1—C20—H20B	109.1
N2—C10—C6	132.33 (16)	C21—C20—H20B	109.1
N2—C10—C17	110.65 (16)	H20A—C20—H20B	107.9
C6—C10—C17	116.90 (16)	C20—C21—H21A	109.5
C12—C11—C16	117.78 (18)	C20—C21—H21B	109.5
C12—C11—N3	120.01 (18)	H21A—C21—H21B	109.5
C16—C11—N3	122.20 (17)	C20—C21—H21C	109.5
C11—C12—C13	121.7 (2)	H21A—C21—H21C	109.5
C11—C12—Cl1	119.64 (16)	H21B—C21—H21C	109.5
C13—C12—Cl1	118.65 (17)	C1—N1—C18	121.08 (18)
C14—C13—C12	119.6 (2)	C1—N1—C20	120.98 (17)
C14—C13—H13	120.2	C18—N1—C20	117.11 (18)
C12—C13—H13	120.2	C10—N2—N3	121.57 (16)
C15—C14—C13	119.1 (2)	N2—N3—C11	117.85 (16)
C15—C14—H14	120.4	N2—N3—H3A	121.1
C13—C14—H14	120.4	C11—N3—H3A	121.1
C14—C15—C16	121.3 (2)	C7—O1—C8	122.86 (14)
N1—C1—C2—C3	−178.8 (2)	Cl1—C12—C13—C14	179.90 (18)
C9—C1—C2—C3	1.5 (3)	C12—C13—C14—C15	0.7 (4)
C1—C2—C3—C4	0.7 (3)	C13—C14—C15—C16	−1.3 (4)
C2—C3—C4—C8	−1.1 (3)	C14—C15—C16—C11	1.2 (3)
C2—C3—C4—C5	178.8 (2)	C12—C11—C16—C15	−0.5 (3)
C8—C4—C5—C6	2.4 (3)	N3—C11—C16—C15	−179.3 (2)
C3—C4—C5—C6	−177.6 (2)	N2—C10—C17—F3	−27.1 (2)
C4—C5—C6—C7	0.3 (3)	C6—C10—C17—F3	156.38 (17)
C4—C5—C6—C10	−175.63 (17)	N2—C10—C17—F1	−148.43 (17)
C5—C6—C7—O2	178.2 (2)	C6—C10—C17—F1	35.1 (2)
C10—C6—C7—O2	−5.8 (3)	N2—C10—C17—F2	93.0 (2)
C5—C6—C7—O1	−3.3 (3)	C6—C10—C17—F2	−83.5 (2)
C10—C6—C7—O1	172.71 (16)	C9—C1—N1—C18	−170.4 (2)
C5—C4—C8—C9	179.41 (19)	C2—C1—N1—C18	9.9 (3)
C3—C4—C8—C9	−0.6 (3)	C9—C1—N1—C20	−1.1 (3)
C5—C4—C8—O1	−2.0 (3)	C2—C1—N1—C20	179.2 (2)
C3—C4—C8—O1	177.93 (18)	C19—C18—N1—C1	77.9 (3)
O1—C8—C9—C1	−175.76 (18)	C19—C18—N1—C20	−91.8 (3)
C4—C8—C9—C1	2.8 (3)	C21—C20—N1—C1	82.7 (3)
N1—C1—C9—C8	177.09 (18)	C21—C20—N1—C18	−107.6 (2)
C2—C1—C9—C8	−3.2 (3)	C6—C10—N2—N3	0.4 (3)
C5—C6—C10—N2	−140.5 (2)	C17—C10—N2—N3	−175.39 (17)
C7—C6—C10—N2	43.6 (3)	C10—N2—N3—C11	−178.98 (17)
C5—C6—C10—C17	35.1 (3)	C12—C11—N3—N2	178.80 (17)
C7—C6—C10—C17	−140.80 (19)	C16—C11—N3—N2	−2.4 (3)
C16—C11—C12—C13	−0.1 (3)	O2—C7—O1—C8	−177.57 (17)
N3—C11—C12—C13	178.75 (19)	C6—C7—O1—C8	3.7 (3)
C16—C11—C12—Cl1	−179.98 (15)	C9—C8—O1—C7	177.61 (18)
N3—C11—C12—Cl1	−1.2 (3)	C4—C8—O1—C7	−1.1 (3)
C11—C12—C13—C14	0.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···Cl1	0.86	2.57	2.960 (2)	109.
N3—H3A···O2	0.86	2.22	2.761 (3)	121.
C14—H14···O2i	0.93	2.55	3.316 (3)	140.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯Cl1	0.86	2.57	2.960 (2)	109
N3—H3A⋯O2	0.86	2.22	2.761 (3)	121
C14—H14⋯O2i	0.93	2.55	3.316 (3)	140

Symmetry code: (i) .