3-[2-(5-tert-Butyl-1,2-oxazol-3-yl)hydrazinyl-idene]chroman-2,4-dione.

In the title compound, C(16)H(15)N(3)O(4), the dihedral angle between the chromane and isoxazole rings [r.m.s. deviations = 0.042 and 0.007 Å, respectively] is 20.33 (12)°. The mol-ecular geometry is stabilized by an intra-molecular N-H⋯O hydrogen bond. In the crystal, N-H⋯O hydrogen bonds generate chains along the c-axis direction. The crystal studied was a non-morohedral twin.

Related literature

For general background to the use of coumarin derivatives in organic synthesis and as biologically active compounds see: Adavi et al. (2004 ▶); Shi & Zhou (2011 ▶); Toshihiro et al. (2005 ▶).

Experimental

Crystal data

C16H15N3O4

M = 313.31

Monoclinic,

a = 13.431 (14) Å

b = 9.1803 (9) Å

c = 12.638 (4) Å

β = 100.49 (8)°

V = 1532.3 (17) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 290 K

0.28 × 0.26 × 0.21 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T min = 0.584, T max = 1.000

13050 measured reflections

3010 independent reflections

2148 reflections with I > 2σ(I)

R int = 0.085

Refinement

R[F 2 > 2σ(F 2)] = 0.072

wR(F 2) = 0.181

S = 1.09

3010 reflections

215 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.23 e Å−3

Δρmin = −0.16 e Å−3

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813000858/kp2443sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813000858/kp2443Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813000858/kp2443Isup3.cml

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

C16H15N3O4	F(000) = 656
Mr = 313.31	Dx = 1.358 Mg m−3
Monoclinic, P21/c	Melting point: 419 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.7107 Å
a = 13.431 (14) Å	Cell parameters from 4079 reflections
b = 9.1803 (9) Å	θ = 3.0–29.4°
c = 12.638 (4) Å	µ = 0.10 mm−1
β = 100.49 (8)°	T = 290 K
V = 1532.3 (17) Å3	Prism, yellow
Z = 4	0.28 × 0.26 × 0.21 mm

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	3010 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2148 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.085
Detector resolution: 10.3974 pixels mm-1	θmax = 29.4°, θmin = 3.0°
ω scans	h = −16→18
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −11→12
Tmin = 0.584, Tmax = 1.000	l = −15→16
13050 measured reflections

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)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.181	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0555P)2 + 1.4334P] where P = (Fo2 + 2Fc2)/3
3010 reflections	(Δ/σ)max < 0.001
215 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.16 e Å−3

Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31) FTIR (KBr): 1377 cm-1 (CH3δs), 1467.5 cm-1 (N=N), 1740 cm-1 (C=O). NMR atom numbering is according to IUPAC13C NMR (62.9 MHz, DMSO-d6): δ 28.2 (CH3), 32.1 (C t-but), 91.2 (NCCH), 117.4 (C8 of the coumarin ring), 120.4 (C4a of the coumarin ring), 124.9 (C6 of the coumarin ring), 125.7 (C3 of the coumarin ring), 126.8 (C5 of the coumarin ring), 137.0 (C7 of the coumarin ring), 154.1(C8a of the coumarin ring), 157.6 (C2 of the coumarin ring), 162.4 (NCCH), 178.3 (C4 of the coumarin ring), 182.8 (NC).1H NMR (250 MHz, DMSO-d6): δ 1.35 (s, 9H, t-but.), 6.57 (s,1H of the isoxazol ring), 7.37 (dd, J = 8.0, 1.5 Hz, 1H, H8 of the coumarin ring), 7.39 (ddd, J = 8.0, 8.0, 1.5 Hz, 1H, H6 of the coumarin ring), 7.80 (ddd, J = 8.0, 8.0, 1.5 Hz, 1H, C7 of the coumarin ring), 8.00 (dd,1H, dd, J = 8.0, 1.5 Hz, C5 of the coumarin ring). Elemental analysis: C, 61.34; H, 4.83; N, 13.41. TOF MS ES+: m/e: 336[M+Na]+.

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	0.1628 (2)	0.3116 (3)	0.0511 (2)	0.0362 (6)
C2	0.1605 (2)	0.4578 (3)	0.0958 (2)	0.0384 (6)
C3	0.1281 (2)	0.5746 (3)	0.0182 (2)	0.0369 (6)
C4	0.1307 (2)	0.7207 (3)	0.0498 (3)	0.0467 (7)
H4	0.1511	0.7448	0.1219	0.056*
C5	0.1035 (3)	0.8282 (3)	−0.0247 (3)	0.0571 (9)
H5	0.1074	0.9254	−0.0035	0.068*
C6	0.0701 (3)	0.7922 (4)	−0.1321 (3)	0.0580 (9)
H6	0.0509	0.8657	−0.1823	0.070*
C7	0.0651 (3)	0.6488 (4)	−0.1651 (3)	0.0508 (8)
H7	0.0421	0.6250	−0.2369	0.061*
C8	0.0948 (2)	0.5405 (3)	−0.0893 (2)	0.0389 (6)
C9	0.1240 (2)	0.2823 (3)	−0.0636 (2)	0.0402 (6)
C10	0.2869 (2)	0.0916 (3)	0.2637 (2)	0.0408 (6)
C11	0.3172 (2)	−0.0401 (3)	0.2229 (2)	0.0421 (7)
H11	0.3060	−0.0719	0.1519	0.051*
C12	0.3667 (2)	−0.1101 (3)	0.3116 (2)	0.0432 (7)
C13	0.4211 (3)	−0.2535 (3)	0.3317 (3)	0.0494 (8)
C14	0.5276 (3)	−0.2268 (4)	0.3960 (3)	0.0741 (12)
H14A	0.5637	−0.1627	0.3563	0.111*
H14B	0.5630	−0.3178	0.4080	0.111*
H14C	0.5229	−0.1831	0.4639	0.111*
C15	0.3615 (4)	−0.3513 (5)	0.3961 (4)	0.0790 (12)
H15A	0.3550	−0.3036	0.4621	0.118*
H15B	0.3967	−0.4419	0.4119	0.118*
H15C	0.2954	−0.3696	0.3546	0.118*
C16	0.4268 (4)	−0.3246 (5)	0.2235 (3)	0.0769 (12)
H16A	0.3597	−0.3363	0.1827	0.115*
H16B	0.4586	−0.4183	0.2356	0.115*
H16C	0.4657	−0.2640	0.1844	0.115*
N1	0.20237 (19)	0.1960 (3)	0.10479 (18)	0.0390 (5)
N2	0.2352 (2)	0.2092 (3)	0.20786 (19)	0.0429 (6)
N3	0.3136 (2)	0.1048 (3)	0.3673 (2)	0.0549 (7)
O1	0.08744 (16)	0.3990 (2)	−0.12688 (14)	0.0433 (5)
O2	0.18801 (19)	0.4820 (2)	0.19257 (15)	0.0562 (6)
O3	0.36552 (18)	−0.0258 (3)	0.39890 (16)	0.0558 (6)
O9	0.1194 (2)	0.1661 (2)	−0.10662 (17)	0.0594 (7)
H2	0.231 (3)	0.296 (5)	0.238 (3)	0.076 (13)*

	U11	U22	U33	U12	U13	U23
C1	0.0388 (15)	0.0349 (14)	0.0353 (14)	−0.0036 (11)	0.0082 (11)	0.0027 (10)
C2	0.0438 (16)	0.0395 (15)	0.0313 (13)	−0.0033 (12)	0.0057 (11)	0.0029 (11)
C3	0.0358 (14)	0.0379 (14)	0.0372 (13)	−0.0038 (11)	0.0071 (11)	0.0043 (11)
C4	0.0489 (18)	0.0393 (16)	0.0515 (17)	−0.0027 (13)	0.0079 (14)	−0.0030 (13)
C5	0.064 (2)	0.0336 (16)	0.076 (2)	−0.0014 (14)	0.0165 (19)	0.0061 (14)
C6	0.055 (2)	0.0499 (19)	0.067 (2)	0.0043 (15)	0.0054 (17)	0.0252 (16)
C7	0.0509 (19)	0.0549 (19)	0.0435 (16)	0.0002 (15)	0.0000 (14)	0.0131 (14)
C8	0.0362 (14)	0.0378 (14)	0.0420 (14)	−0.0032 (11)	0.0047 (12)	0.0046 (11)
C9	0.0434 (16)	0.0399 (15)	0.0374 (14)	−0.0035 (12)	0.0072 (12)	0.0014 (12)
C10	0.0366 (14)	0.0439 (16)	0.0408 (14)	0.0000 (12)	0.0043 (11)	0.0022 (12)
C11	0.0395 (15)	0.0507 (17)	0.0341 (13)	−0.0037 (13)	0.0011 (11)	0.0016 (12)
C12	0.0389 (16)	0.0498 (18)	0.0394 (15)	0.0017 (12)	0.0034 (12)	−0.0018 (12)
C13	0.0468 (18)	0.0475 (18)	0.0500 (17)	0.0080 (14)	−0.0015 (14)	−0.0013 (13)
C14	0.048 (2)	0.070 (2)	0.091 (3)	0.0149 (18)	−0.0216 (19)	−0.004 (2)
C15	0.088 (3)	0.060 (2)	0.087 (3)	0.002 (2)	0.011 (2)	0.016 (2)
C16	0.082 (3)	0.072 (3)	0.073 (3)	0.025 (2)	0.006 (2)	−0.018 (2)
N1	0.0403 (13)	0.0437 (13)	0.0329 (11)	−0.0042 (10)	0.0064 (10)	0.0017 (9)
N2	0.0500 (15)	0.0410 (14)	0.0355 (12)	0.0030 (11)	0.0022 (11)	0.0009 (10)
N3	0.0614 (18)	0.0571 (17)	0.0414 (14)	0.0205 (13)	−0.0029 (12)	−0.0005 (12)
O1	0.0517 (12)	0.0418 (11)	0.0336 (10)	−0.0026 (9)	0.0000 (9)	0.0015 (8)
O2	0.0862 (18)	0.0425 (12)	0.0360 (11)	−0.0027 (11)	0.0010 (11)	−0.0033 (9)
O3	0.0627 (15)	0.0603 (14)	0.0393 (11)	0.0232 (11)	−0.0041 (10)	0.0009 (10)
O9	0.0917 (19)	0.0402 (12)	0.0429 (12)	−0.0031 (11)	0.0028 (12)	−0.0056 (9)

C1—N1	1.319 (4)	C10—N2	1.403 (4)
C1—C2	1.459 (4)	C11—C12	1.356 (4)
C1—C9	1.473 (4)	C11—H11	0.9300
C2—O2	1.231 (3)	C12—O3	1.350 (4)
C2—C3	1.465 (4)	C12—C13	1.505 (4)
C3—C8	1.386 (4)	C13—C16	1.530 (5)
C3—C4	1.397 (4)	C13—C14	1.531 (5)
C4—C5	1.367 (5)	C13—C15	1.531 (6)
C4—H4	0.9300	C14—H14A	0.9600
C5—C6	1.390 (5)	C14—H14B	0.9600
C5—H5	0.9300	C14—H14C	0.9600
C6—C7	1.379 (5)	C15—H15A	0.9600
C6—H6	0.9300	C15—H15B	0.9600
C7—C8	1.388 (4)	C15—H15C	0.9600
C7—H7	0.9300	C16—H16A	0.9600
C8—O1	1.381 (3)	C16—H16B	0.9600
C9—O9	1.194 (3)	C16—H16C	0.9600
C9—O1	1.373 (3)	N1—N2	1.303 (3)
C10—N3	1.299 (4)	N2—H2	0.89 (4)
C10—C11	1.404 (4)	N3—O3	1.408 (3)
N1—C1—C2	125.2 (2)	O3—C12—C13	116.1 (2)
N1—C1—C9	113.4 (2)	C11—C12—C13	134.8 (3)
C2—C1—C9	121.4 (2)	C12—C13—C16	108.9 (3)
O2—C2—C1	121.8 (2)	C12—C13—C14	109.1 (3)
O2—C2—C3	122.1 (3)	C16—C13—C14	110.4 (3)
C1—C2—C3	116.0 (2)	C12—C13—C15	108.6 (3)
C8—C3—C4	118.9 (3)	C16—C13—C15	109.9 (3)
C8—C3—C2	119.6 (2)	C14—C13—C15	109.9 (3)
C4—C3—C2	121.5 (3)	C13—C14—H14A	109.5
C5—C4—C3	120.5 (3)	C13—C14—H14B	109.5
C5—C4—H4	119.8	H14A—C14—H14B	109.5
C3—C4—H4	119.8	C13—C14—H14C	109.5
C4—C5—C6	119.9 (3)	H14A—C14—H14C	109.5
C4—C5—H5	120.0	H14B—C14—H14C	109.5
C6—C5—H5	120.0	C13—C15—H15A	109.5
C7—C6—C5	120.8 (3)	C13—C15—H15B	109.5
C7—C6—H6	119.6	H15A—C15—H15B	109.5
C5—C6—H6	119.6	C13—C15—H15C	109.5
C6—C7—C8	118.9 (3)	H15A—C15—H15C	109.5
C6—C7—H7	120.5	H15B—C15—H15C	109.5
C8—C7—H7	120.5	C13—C16—H16A	109.5
O1—C8—C3	122.7 (2)	C13—C16—H16B	109.5
O1—C8—C7	116.3 (3)	H16A—C16—H16B	109.5
C3—C8—C7	121.0 (3)	C13—C16—H16C	109.5
O9—C9—O1	116.7 (3)	H16A—C16—H16C	109.5
O9—C9—C1	126.2 (3)	H16B—C16—H16C	109.5
O1—C9—C1	117.1 (2)	N2—N1—C1	118.1 (2)
N3—C10—C11	113.9 (3)	N1—N2—C10	118.5 (3)
N3—C10—N2	117.1 (3)	N1—N2—H2	118 (3)
C11—C10—N2	129.0 (3)	C10—N2—H2	123 (3)
C12—C11—C10	103.6 (2)	C10—N3—O3	103.7 (2)
C12—C11—H11	128.2	C9—O1—C8	122.6 (2)
C10—C11—H11	128.2	C12—O3—N3	109.6 (2)
O3—C12—C11	109.1 (3)
N1—C1—C2—O2	−7.1 (5)	N2—C10—C11—C12	177.9 (3)
C9—C1—C2—O2	176.2 (3)	C10—C11—C12—O3	0.2 (3)
N1—C1—C2—C3	170.3 (3)	C10—C11—C12—C13	−178.8 (4)
C9—C1—C2—C3	−6.4 (4)	O3—C12—C13—C16	−172.7 (3)
O2—C2—C3—C8	−177.9 (3)	C11—C12—C13—C16	6.2 (5)
C1—C2—C3—C8	4.8 (4)	O3—C12—C13—C14	−52.1 (4)
O2—C2—C3—C4	2.7 (4)	C11—C12—C13—C14	126.8 (4)
C1—C2—C3—C4	−174.7 (3)	O3—C12—C13—C15	67.7 (4)
C8—C3—C4—C5	−1.8 (5)	C11—C12—C13—C15	−113.4 (4)
C2—C3—C4—C5	177.7 (3)	C2—C1—N1—N2	5.7 (4)
C3—C4—C5—C6	1.9 (5)	C9—C1—N1—N2	−177.3 (3)
C4—C5—C6—C7	−0.7 (6)	C1—N1—N2—C10	−173.5 (3)
C5—C6—C7—C8	−0.6 (5)	N3—C10—N2—N1	−176.1 (3)
C4—C3—C8—O1	−178.3 (3)	C11—C10—N2—N1	5.8 (5)
C2—C3—C8—O1	2.2 (4)	C11—C10—N3—O3	0.2 (4)
C4—C3—C8—C7	0.5 (4)	N2—C10—N3—O3	−178.2 (2)
C2—C3—C8—C7	−179.0 (3)	O9—C9—O1—C8	−175.2 (3)
C6—C7—C8—O1	179.6 (3)	C1—C9—O1—C8	6.2 (4)
C6—C7—C8—C3	0.7 (5)	C3—C8—O1—C9	−8.2 (4)
N1—C1—C9—O9	5.7 (5)	C7—C8—O1—C9	173.0 (3)
C2—C1—C9—O9	−177.3 (3)	C11—C12—O3—N3	−0.1 (4)
N1—C1—C9—O1	−175.9 (2)	C13—C12—O3—N3	179.1 (3)
C2—C1—C9—O1	1.2 (4)	C10—N3—O3—C12	−0.1 (4)
N3—C10—C11—C12	−0.2 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.89 (4)	1.86 (4)	2.581 (3)	137 (4)
N2—H2···O9i	0.89 (4)	2.70 (4)	3.249 (4)	121 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2	0.89 (4)	1.86 (4)	2.581 (3)	137 (4)
N2—H2⋯O9i	0.89 (4)	2.70 (4)	3.249 (4)	121 (3)

Symmetry code: (i) .