8-[(Hydrazinyl-idene)meth-yl]-4-methyl-2-oxo-2H-chromen-7-yl 4-methyl-benzene-sulfonate.

In the title compound, C(18)H(16)N(2)O(5)S, the coumarin ring system is nearly planar, with a maximum out-of-plane deviation of 0.078 (1) Å (r.m.s. deviation = 0.046 Å). The dihedral angle between the coumarin ring system and the toluene ring (r.m.s. deviation = 0.004 Å) is 2.77 (1)°. The crystal packing is stabilized by C-H⋯O and N-H⋯O inter-molecular hydrogen bonds generating C(8), C(9) and C(11) chains and R(2) (2)(14), R(2) (2)(23) and R(4) (3)(13) ring graph sets.

Related literature

For the biological activity of coumarins, see: Kulkarni et al. (2006 ▶); Kalkhambkar et al. (2008 ▶); Laakso et al. (1994 ▶); n class="Chemical">Nofal et al. (2000 ▶). For related structures, see: Kokila et al. (1995 ▶); Vasudevan et al. (1990 ▶). For graph-set analysis of hydrogen-bond patterns, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C18H16N2O5S

M = 372.39

Monoclinic,

a = 9.1947 (3) Å

b = 16.1867 (4) Å

c = 11.6538 (3) Å

β = 99.670 (1)°

V = 1709.81 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.22 mm−1

T = 293 K

0.2 × 0.19 × 0.19 mm

Data collection

Bruker SMART CCD area-detector diffractometer

26334 measured reflections

4260 independent reflections

3285 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.116

S = 1.04

4260 reflections

237 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.40 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAIn class="Chemical">NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PARST (Nardelli, 1995 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810054620/si2319sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810054620/si2319Isup2.hkl

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

C18H16N2O5S	F(000) = 776
Mr = 372.39	Dx = 1.447 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7131 reflections
a = 9.1947 (3) Å	θ = 2.2–27.3°
b = 16.1867 (4) Å	µ = 0.22 mm−1
c = 11.6538 (3) Å	T = 293 K
β = 99.670 (1)°	Plate, colorless
V = 1709.81 (8) Å3	0.2 × 0.19 × 0.19 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	3285 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.033
graphite	θmax = 28.3°, θmin = 2.2°
phi and ω scans	h = −12→12
26334 measured reflections	k = −21→21
4260 independent reflections	l = −15→15

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0548P)2 + 0.5733P] where P = (Fo2 + 2Fc2)/3
4260 reflections	(Δ/σ)max = 0.001
237 parameters	Δρmax = 0.35 e Å−3
0 restraints	Δρmin = −0.40 e Å−3

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
S1	0.87241 (5)	0.20073 (3)	0.74789 (4)	0.04805 (14)
O2	0.40215 (11)	−0.02903 (6)	0.69872 (10)	0.0400 (3)
O3	0.83056 (11)	0.12613 (6)	0.65832 (10)	0.0381 (3)
O1	0.21065 (13)	−0.09419 (7)	0.74469 (14)	0.0591 (4)
O4	0.78108 (16)	0.19431 (11)	0.83435 (14)	0.0793 (5)
O5	0.86864 (16)	0.27548 (8)	0.68331 (17)	0.0777 (5)
C11	0.70098 (16)	−0.02353 (9)	0.74255 (14)	0.0371 (3)
H11	0.6508	−0.0599	0.7837	0.045*
C7	0.61790 (16)	0.04122 (9)	0.67270 (13)	0.0330 (3)
C8	0.67779 (16)	0.11089 (9)	0.62748 (13)	0.0357 (3)
C5	0.37380 (16)	0.09308 (9)	0.57881 (13)	0.0355 (3)
C6	0.46285 (16)	0.03608 (9)	0.64762 (13)	0.0331 (3)
C12	1.05418 (18)	0.17468 (10)	0.80513 (14)	0.0409 (4)
C17	1.3108 (2)	0.20553 (11)	0.83220 (17)	0.0488 (4)
H17	1.3876	0.2392	0.8175	0.059*
C2	0.15966 (17)	0.02146 (10)	0.62033 (15)	0.0416 (4)
H2	0.0578	0.0161	0.6127	0.050*
C9	0.59404 (19)	0.16704 (11)	0.55527 (15)	0.0457 (4)
H9	0.6394	0.2107	0.5234	0.055*
C1	0.25173 (17)	−0.03775 (10)	0.69100 (16)	0.0417 (4)
C4	0.11620 (19)	0.14562 (12)	0.49470 (15)	0.0484 (4)
H4A	0.0150	0.1316	0.4958	0.073*
H4B	0.1342	0.1451	0.4159	0.073*
H4C	0.1363	0.1997	0.5272	0.073*
C3	0.21464 (17)	0.08395 (10)	0.56514 (14)	0.0377 (3)
C10	0.44325 (19)	0.15798 (11)	0.53077 (15)	0.0460 (4)
H10	0.3870	0.1955	0.4817	0.055*
C18	1.16766 (19)	0.22511 (11)	0.78238 (16)	0.0453 (4)
H18	1.1480	0.2712	0.7346	0.054*
C14	1.2259 (2)	0.08804 (12)	0.92495 (17)	0.0524 (4)
H14	1.2454	0.0419	0.9725	0.063*
C13	1.0825 (2)	0.10645 (12)	0.87741 (16)	0.0500 (4)
H13	1.0054	0.0736	0.8935	0.060*
C15	1.34283 (19)	0.13723 (11)	0.90328 (16)	0.0468 (4)
C16	1.4988 (2)	0.11716 (14)	0.9572 (2)	0.0643 (5)
H16A	1.5640	0.1583	0.9351	0.096*
H16B	1.5251	0.0640	0.9306	0.096*
H16C	1.5070	0.1164	1.0404	0.096*
N1	0.83982 (14)	−0.03170 (8)	0.74886 (13)	0.0411 (3)
N2	0.90695 (16)	−0.09370 (10)	0.81607 (14)	0.0519 (4)
H2A	0.8559	−0.1258	0.8526	0.062*
H2B	1.0006	−0.1009	0.8222	0.062*

	U11	U22	U33	U12	U13	U23
S1	0.0384 (2)	0.0402 (2)	0.0663 (3)	−0.00432 (16)	0.01104 (19)	−0.01826 (19)
O2	0.0273 (5)	0.0324 (5)	0.0604 (7)	0.0000 (4)	0.0079 (5)	0.0048 (5)
O3	0.0329 (5)	0.0358 (6)	0.0473 (6)	−0.0059 (4)	0.0112 (4)	−0.0073 (5)
O1	0.0357 (6)	0.0406 (7)	0.1039 (11)	−0.0001 (5)	0.0202 (7)	0.0154 (7)
O4	0.0507 (8)	0.1124 (13)	0.0803 (10)	−0.0143 (8)	0.0272 (8)	−0.0508 (10)
O5	0.0566 (9)	0.0329 (7)	0.1361 (15)	−0.0016 (6)	−0.0055 (9)	0.0022 (8)
C11	0.0309 (7)	0.0354 (8)	0.0459 (8)	−0.0009 (6)	0.0084 (6)	0.0008 (6)
C7	0.0311 (7)	0.0332 (7)	0.0355 (7)	−0.0003 (5)	0.0076 (6)	−0.0050 (6)
C8	0.0311 (7)	0.0372 (7)	0.0397 (8)	−0.0035 (6)	0.0084 (6)	−0.0034 (6)
C5	0.0339 (7)	0.0374 (8)	0.0352 (7)	0.0020 (6)	0.0052 (6)	−0.0027 (6)
C6	0.0322 (7)	0.0306 (7)	0.0374 (7)	−0.0006 (5)	0.0085 (6)	−0.0039 (6)
C12	0.0398 (8)	0.0394 (8)	0.0445 (8)	−0.0087 (6)	0.0099 (7)	−0.0108 (7)
C17	0.0415 (9)	0.0480 (9)	0.0580 (10)	−0.0150 (7)	0.0116 (8)	−0.0064 (8)
C2	0.0280 (7)	0.0410 (8)	0.0547 (10)	0.0021 (6)	0.0036 (7)	−0.0080 (7)
C9	0.0455 (9)	0.0460 (9)	0.0467 (9)	−0.0046 (7)	0.0107 (7)	0.0116 (7)
C1	0.0297 (7)	0.0334 (8)	0.0632 (10)	−0.0006 (6)	0.0113 (7)	−0.0047 (7)
C4	0.0412 (9)	0.0561 (10)	0.0459 (9)	0.0102 (8)	0.0012 (7)	0.0019 (8)
C3	0.0340 (7)	0.0396 (8)	0.0381 (8)	0.0050 (6)	0.0024 (6)	−0.0083 (6)
C10	0.0442 (9)	0.0485 (10)	0.0442 (9)	0.0033 (7)	0.0040 (7)	0.0109 (7)
C18	0.0466 (9)	0.0379 (8)	0.0518 (10)	−0.0106 (7)	0.0093 (7)	−0.0047 (7)
C14	0.0549 (11)	0.0502 (10)	0.0505 (10)	−0.0092 (8)	0.0040 (8)	0.0042 (8)
C13	0.0498 (10)	0.0508 (10)	0.0505 (10)	−0.0173 (8)	0.0116 (8)	−0.0010 (8)
C15	0.0433 (9)	0.0492 (10)	0.0481 (9)	−0.0063 (7)	0.0079 (7)	−0.0097 (7)
C16	0.0479 (11)	0.0686 (13)	0.0739 (14)	−0.0012 (9)	0.0030 (10)	−0.0027 (11)
N1	0.0321 (6)	0.0398 (7)	0.0513 (8)	0.0020 (5)	0.0070 (6)	0.0035 (6)
N2	0.0338 (7)	0.0548 (9)	0.0668 (10)	0.0064 (6)	0.0074 (7)	0.0177 (7)

S1—O4	1.4197 (15)	C2—C3	1.342 (2)
S1—O5	1.4222 (16)	C2—C1	1.442 (2)
S1—O3	1.6003 (11)	C2—H2	0.9300
S1—C12	1.7441 (17)	C9—C10	1.376 (2)
O2—C6	1.3742 (18)	C9—H9	0.9300
O2—C1	1.3781 (18)	C4—C3	1.497 (2)
O3—C8	1.4119 (18)	C4—H4A	0.9600
O1—C1	1.203 (2)	C4—H4B	0.9600
C11—N1	1.2732 (19)	C4—H4C	0.9600
C11—C7	1.461 (2)	C10—H10	0.9300
C11—H11	0.9300	C18—H18	0.9300
C7—C8	1.397 (2)	C14—C13	1.374 (3)
C7—C6	1.409 (2)	C14—C15	1.395 (2)
C8—C9	1.382 (2)	C14—H14	0.9300
C5—C6	1.394 (2)	C13—H13	0.9300
C5—C10	1.395 (2)	C15—C16	1.501 (3)
C5—C3	1.453 (2)	C16—H16A	0.9600
C12—C18	1.385 (2)	C16—H16B	0.9600
C12—C13	1.387 (2)	C16—H16C	0.9600
C17—C15	1.383 (3)	N1—N2	1.3561 (19)
C17—C18	1.384 (3)	N2—H2A	0.8600
C17—H17	0.9300	N2—H2B	0.8600
O4—S1—O5	118.24 (11)	O1—C1—C2	126.59 (15)
O4—S1—O3	107.55 (8)	O2—C1—C2	117.10 (14)
O5—S1—O3	108.36 (9)	C3—C4—H4A	109.5
O4—S1—C12	110.73 (10)	C3—C4—H4B	109.5
O5—S1—C12	110.17 (9)	H4A—C4—H4B	109.5
O3—S1—C12	100.20 (7)	C3—C4—H4C	109.5
C6—O2—C1	121.77 (12)	H4A—C4—H4C	109.5
C8—O3—S1	114.70 (9)	H4B—C4—H4C	109.5
N1—C11—C7	122.14 (14)	C2—C3—C5	118.53 (14)
N1—C11—H11	118.9	C2—C3—C4	121.58 (15)
C7—C11—H11	118.9	C5—C3—C4	119.84 (15)
C8—C7—C6	114.76 (13)	C9—C10—C5	120.70 (15)
C8—C7—C11	125.94 (13)	C9—C10—H10	119.7
C6—C7—C11	119.30 (13)	C5—C10—H10	119.7
C9—C8—C7	123.11 (14)	C17—C18—C12	118.61 (17)
C9—C8—O3	117.97 (13)	C17—C18—H18	120.7
C7—C8—O3	118.91 (13)	C12—C18—H18	120.7
C6—C5—C10	117.71 (14)	C13—C14—C15	121.31 (18)
C6—C5—C3	118.63 (14)	C13—C14—H14	119.3
C10—C5—C3	123.60 (14)	C15—C14—H14	119.3
O2—C6—C5	120.98 (13)	C14—C13—C12	119.15 (16)
O2—C6—C7	115.20 (13)	C14—C13—H13	120.4
C5—C6—C7	123.80 (14)	C12—C13—H13	120.4
C18—C12—C13	121.00 (16)	C17—C15—C14	118.17 (17)
C18—C12—S1	119.25 (14)	C17—C15—C16	121.05 (17)
C13—C12—S1	119.67 (13)	C14—C15—C16	120.78 (18)
C15—C17—C18	121.75 (16)	C15—C16—H16A	109.5
C15—C17—H17	119.1	C15—C16—H16B	109.5
C18—C17—H17	119.1	H16A—C16—H16B	109.5
C3—C2—C1	122.85 (14)	C15—C16—H16C	109.5
C3—C2—H2	118.6	H16A—C16—H16C	109.5
C1—C2—H2	118.6	H16B—C16—H16C	109.5
C10—C9—C8	119.70 (15)	C11—N1—N2	117.71 (14)
C10—C9—H9	120.2	N1—N2—H2A	120.0
C8—C9—H9	120.2	N1—N2—H2B	120.0
O1—C1—O2	116.30 (15)	H2A—N2—H2B	120.0
O4—S1—O3—C8	42.38 (14)	C7—C8—C9—C10	3.9 (3)
O5—S1—O3—C8	−86.51 (12)	O3—C8—C9—C10	−174.80 (15)
C12—S1—O3—C8	158.10 (11)	C6—O2—C1—O1	−175.70 (15)
N1—C11—C7—C8	−15.2 (2)	C6—O2—C1—C2	4.0 (2)
N1—C11—C7—C6	165.64 (15)	C3—C2—C1—O1	178.45 (18)
C6—C7—C8—C9	−5.4 (2)	C3—C2—C1—O2	−1.2 (2)
C11—C7—C8—C9	175.39 (15)	C1—C2—C3—C5	−1.0 (2)
C6—C7—C8—O3	173.29 (13)	C1—C2—C3—C4	−178.52 (15)
C11—C7—C8—O3	−5.9 (2)	C6—C5—C3—C2	0.7 (2)
S1—O3—C8—C9	72.10 (16)	C10—C5—C3—C2	−176.51 (16)
S1—O3—C8—C7	−106.67 (13)	C6—C5—C3—C4	178.20 (14)
C1—O2—C6—C5	−4.5 (2)	C10—C5—C3—C4	1.0 (2)
C1—O2—C6—C7	173.91 (13)	C8—C9—C10—C5	0.5 (3)
C10—C5—C6—O2	179.38 (14)	C6—C5—C10—C9	−2.9 (2)
C3—C5—C6—O2	2.0 (2)	C3—C5—C10—C9	174.32 (16)
C10—C5—C6—C7	1.1 (2)	C15—C17—C18—C12	0.2 (3)
C3—C5—C6—C7	−176.24 (14)	C13—C12—C18—C17	0.8 (3)
C8—C7—C6—O2	−175.49 (13)	S1—C12—C18—C17	177.42 (13)
C11—C7—C6—O2	3.8 (2)	C15—C14—C13—C12	1.0 (3)
C8—C7—C6—C5	2.9 (2)	C18—C12—C13—C14	−1.3 (3)
C11—C7—C6—C5	−177.88 (14)	S1—C12—C13—C14	−177.96 (14)
O4—S1—C12—C18	−133.39 (14)	C18—C17—C15—C14	−0.5 (3)
O5—S1—C12—C18	−0.71 (17)	C18—C17—C15—C16	−179.64 (18)
O3—S1—C12—C18	113.30 (14)	C13—C14—C15—C17	0.0 (3)
O4—S1—C12—C13	43.30 (17)	C13—C14—C15—C16	179.07 (19)
O5—S1—C12—C13	175.97 (14)	C7—C11—N1—N2	179.96 (14)
O3—S1—C12—C13	−70.01 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O5i	0.86	2.59	3.303 (2)	141
N2—H2B···O1ii	0.86	2.27	3.045 (2)	150
C10—H10···O4iii	0.93	2.55	3.469 (2)	169
C16—H16A···O4ii	0.96	2.55	3.405 (3)	149
C18—H18···O1iv	0.93	2.53	3.166 (2)	126

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O5i	0.86	2.59	3.303 (2)	141
N2—H2B⋯O1ii	0.86	2.27	3.045 (2)	150
C10—H10⋯O4iii	0.93	2.55	3.469 (2)	169
C16—H16A⋯O4ii	0.96	2.55	3.405 (3)	149
C18—H18⋯O1iv	0.93	2.53	3.166 (2)	126

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .