Crystal structure of 4-azido-methyl-6-tert-butyl-2H-chromen-2-one.

In the title compound, C14H15N3O2, one of the methyl C atoms of the tert-butyl group lies almost in the plane of the chromene ring system [deviation = -0.097 (2) Å], one lies above and one lies below [deviations = 1.460 (3) and 1.006 (3) Å, respectively]. The C-C-N-N torsion angle is 142.33 (17)°. In the crystal, moelcules are linked by weak C-H⋯O hydrogen bonds to generate C(6) chains propagating in the [010] direction.

Related literature

For background to the biological properties of coumarins, see: Basanagouda et al. (2009 ▸); Liu et al. (2008 ▸); Mustafa et al. (2011 ▸); Ronad et al. (2008 ▸); Tian et al. (2000 ▸); Puttaraju et al. (2013 ▸). For a related structure, see: Chandra et al. (2014 ▸).

Experimental

Crystal data

C14H15N3O2

M = 257.29

Monoclinic,

a = 10.6816 (7) Å

b = 11.1416 (8) Å

c = 11.5409 (8) Å

β = 100.674 (4)°

V = 1349.72 (16) Å3

Z = 4

Cu Kα radiation

μ = 0.71 mm−1

T = 293 K

0.30 × 0.25 × 0.20 mm

Data collection

Bruker X8 Proteum diffractometer

5911 measured reflections

2165 independent reflections

1949 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.132

S = 1.04

2165 reflections

175 parameters

H-atom parameters constrained

Δρmax = 0.13 e Å−3

Δρmin = −0.17 e Å−3

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; 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: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S205698901500290X/hb7363sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901500290X/hb7363Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S205698901500290X/hb7363Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S205698901500290X/hb7363fig1.tif

Perspective diagram of the mol­ecule with 50% probability displacement ellipsoids.

Click here for additional data file.

b . DOI: 10.1107/S205698901500290X/hb7363fig2.tif

Packing diagram of the mol­ecule viewed parallel to the b axis.

CCDC reference: 1048730

Additional supporting information: crystallographic information; 3D view; checkCIF report

C14H15N3O2	F(000) = 544
Mr = 257.29	Dx = 1.266 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 2165 reflections
a = 10.6816 (7) Å	θ = 5.6–64.5°
b = 11.1416 (8) Å	µ = 0.71 mm−1
c = 11.5409 (8) Å	T = 293 K
β = 100.674 (4)°	Block, pale yellow
V = 1349.72 (16) Å3	0.30 × 0.25 × 0.20 mm
Z = 4

Bruker X8 Proteum diffractometer	1949 reflections with I > 2σ(I)
Radiation source: Bruker MicroStar microfocus rotating anode	Rint = 0.037
Helios multilayer optics monochromator	θmax = 64.5°, θmin = 5.6°
Detector resolution: 10.7 pixels mm-1	h = −12→12
φ and ω scans	k = −12→12
5911 measured reflections	l = −13→13
2165 independent 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0667P)2 + 0.2532P] where P = (Fo2 + 2Fc2)/3
2165 reflections	(Δ/σ)max < 0.001
175 parameters	Δρmax = 0.13 e Å−3
0 restraints	Δρmin = −0.17 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
O1	0.59056 (12)	0.02266 (11)	0.31873 (10)	0.0633 (4)
O2	0.43714 (15)	0.00517 (14)	0.16423 (12)	0.0886 (6)
N1	0.32064 (15)	−0.31631 (13)	0.42079 (19)	0.0852 (7)
N2	0.29968 (12)	−0.42384 (13)	0.41655 (12)	0.0581 (5)
N3	0.26741 (17)	−0.51960 (15)	0.40562 (16)	0.0784 (7)
C1	0.79791 (14)	−0.09815 (13)	0.63907 (13)	0.0464 (5)
C2	0.68585 (13)	−0.15469 (12)	0.58820 (12)	0.0441 (4)
C3	0.61248 (13)	−0.11775 (12)	0.48071 (12)	0.0429 (4)
C4	0.49582 (14)	−0.17576 (13)	0.42299 (13)	0.0478 (5)
C5	0.43662 (16)	−0.13424 (15)	0.31759 (14)	0.0585 (6)
C6	0.48347 (19)	−0.03397 (17)	0.26019 (15)	0.0642 (6)
C7	0.65570 (15)	−0.01975 (13)	0.42495 (13)	0.0493 (5)
C8	0.76681 (17)	0.03930 (15)	0.47367 (16)	0.0593 (6)
C9	0.83629 (16)	−0.00013 (14)	0.57861 (16)	0.0566 (5)
C10	0.88114 (15)	−0.14115 (14)	0.75389 (14)	0.0553 (5)
C11	0.9105 (3)	−0.0370 (2)	0.8404 (2)	0.0925 (9)
C12	1.0051 (2)	−0.1916 (3)	0.7259 (2)	0.0969 (10)
C13	0.8160 (2)	−0.2375 (2)	0.81437 (18)	0.0840 (8)
C14	0.44697 (15)	−0.27965 (14)	0.48332 (16)	0.0581 (5)
H2	0.65810	−0.21990	0.62690	0.0530*
H5	0.36230	−0.17200	0.28040	0.0700*
H8	0.79420	0.10520	0.43560	0.0710*
H9	0.91130	0.03960	0.61060	0.0680*
H11A	0.83230	−0.00230	0.85410	0.1390*
H11B	0.95900	0.02280	0.80810	0.1390*
H11C	0.95890	−0.06580	0.91360	0.1390*
H12A	1.05700	−0.22160	0.79690	0.1450*
H12B	1.05020	−0.12930	0.69340	0.1450*
H12C	0.98610	−0.25570	0.66980	0.1450*
H13A	0.73560	−0.20790	0.82820	0.1260*
H13B	0.86890	−0.25830	0.88820	0.1260*
H13C	0.80210	−0.30740	0.76490	0.1260*
H14A	0.50560	−0.34650	0.48640	0.0700*
H14B	0.44200	−0.25750	0.56360	0.0700*

	U11	U22	U33	U12	U13	U23
O1	0.0776 (8)	0.0686 (8)	0.0471 (7)	0.0085 (6)	0.0204 (6)	0.0127 (5)
O2	0.1016 (11)	0.1144 (12)	0.0476 (8)	0.0252 (9)	0.0082 (7)	0.0190 (7)
N1	0.0611 (9)	0.0489 (9)	0.1292 (15)	−0.0037 (7)	−0.0249 (9)	−0.0015 (8)
N2	0.0521 (8)	0.0577 (9)	0.0598 (9)	−0.0068 (6)	−0.0019 (6)	−0.0048 (6)
N3	0.0802 (11)	0.0653 (11)	0.0841 (12)	−0.0237 (8)	0.0010 (9)	−0.0092 (8)
C1	0.0489 (8)	0.0428 (8)	0.0493 (8)	−0.0053 (6)	0.0141 (6)	−0.0055 (6)
C2	0.0509 (8)	0.0375 (7)	0.0453 (8)	−0.0036 (6)	0.0128 (6)	−0.0017 (6)
C3	0.0502 (8)	0.0387 (7)	0.0419 (8)	0.0032 (6)	0.0143 (6)	−0.0056 (6)
C4	0.0539 (8)	0.0422 (8)	0.0467 (8)	0.0079 (6)	0.0080 (6)	−0.0100 (6)
C5	0.0616 (10)	0.0630 (10)	0.0482 (9)	0.0110 (8)	0.0030 (7)	−0.0106 (7)
C6	0.0770 (12)	0.0753 (11)	0.0424 (9)	0.0209 (9)	0.0166 (8)	0.0016 (8)
C7	0.0617 (9)	0.0488 (8)	0.0422 (8)	0.0082 (7)	0.0223 (7)	0.0029 (6)
C8	0.0679 (10)	0.0516 (9)	0.0653 (11)	−0.0080 (8)	0.0307 (8)	0.0070 (7)
C9	0.0556 (9)	0.0527 (9)	0.0644 (10)	−0.0122 (7)	0.0189 (8)	−0.0018 (7)
C10	0.0535 (9)	0.0556 (9)	0.0541 (9)	−0.0116 (7)	0.0027 (7)	−0.0021 (7)
C11	0.1146 (18)	0.0844 (14)	0.0685 (13)	−0.0236 (13)	−0.0093 (12)	−0.0150 (11)
C12	0.0754 (13)	0.1139 (19)	0.0993 (17)	0.0241 (12)	0.0111 (12)	0.0184 (14)
C13	0.0873 (13)	0.0933 (15)	0.0614 (11)	−0.0298 (11)	−0.0126 (10)	0.0242 (10)
C14	0.0529 (9)	0.0432 (8)	0.0715 (10)	−0.0048 (7)	−0.0059 (7)	−0.0042 (7)

O1—C6	1.370 (2)	C10—C12	1.527 (3)
O1—C7	1.3763 (19)	C10—C13	1.518 (3)
O2—C6	1.208 (2)	C2—H2	0.9300
N1—N2	1.218 (2)	C5—H5	0.9300
N1—C14	1.466 (2)	C8—H8	0.9300
N2—N3	1.121 (2)	C9—H9	0.9300
C1—C2	1.384 (2)	C11—H11A	0.9600
C1—C9	1.398 (2)	C11—H11B	0.9600
C1—C10	1.530 (2)	C11—H11C	0.9600
C2—C3	1.4008 (19)	C12—H12A	0.9600
C3—C4	1.452 (2)	C12—H12B	0.9600
C3—C7	1.389 (2)	C12—H12C	0.9600
C4—C5	1.345 (2)	C13—H13A	0.9600
C4—C14	1.494 (2)	C13—H13B	0.9600
C5—C6	1.435 (3)	C13—H13C	0.9600
C7—C8	1.382 (2)	C14—H14A	0.9700
C8—C9	1.370 (3)	C14—H14B	0.9700
C10—C11	1.525 (3)
C6—O1—C7	121.29 (13)	C3—C2—H2	119.00
N2—N1—C14	116.07 (15)	C4—C5—H5	119.00
N1—N2—N3	172.26 (18)	C6—C5—H5	119.00
C2—C1—C9	117.04 (14)	C7—C8—H8	120.00
C2—C1—C10	122.92 (13)	C9—C8—H8	120.00
C9—C1—C10	120.01 (14)	C1—C9—H9	119.00
C1—C2—C3	122.70 (13)	C8—C9—H9	119.00
C2—C3—C4	124.58 (13)	C10—C11—H11A	110.00
C2—C3—C7	117.50 (13)	C10—C11—H11B	110.00
C4—C3—C7	117.91 (13)	C10—C11—H11C	109.00
C3—C4—C5	118.81 (14)	H11A—C11—H11B	109.00
C3—C4—C14	118.39 (13)	H11A—C11—H11C	109.00
C5—C4—C14	122.81 (15)	H11B—C11—H11C	109.00
C4—C5—C6	122.65 (16)	C10—C12—H12A	109.00
O1—C6—O2	116.67 (17)	C10—C12—H12B	110.00
O1—C6—C5	117.49 (15)	C10—C12—H12C	109.00
O2—C6—C5	125.85 (18)	H12A—C12—H12B	109.00
O1—C7—C3	121.73 (14)	H12A—C12—H12C	109.00
O1—C7—C8	116.95 (14)	H12B—C12—H12C	109.00
C3—C7—C8	121.31 (14)	C10—C13—H13A	109.00
C7—C8—C9	119.38 (15)	C10—C13—H13B	110.00
C1—C9—C8	122.06 (16)	C10—C13—H13C	109.00
C1—C10—C11	110.18 (14)	H13A—C13—H13B	109.00
C1—C10—C12	108.64 (14)	H13A—C13—H13C	109.00
C1—C10—C13	112.18 (14)	H13B—C13—H13C	109.00
C11—C10—C12	109.72 (19)	N1—C14—H14A	109.00
C11—C10—C13	107.06 (16)	N1—C14—H14B	109.00
C12—C10—C13	109.04 (17)	C4—C14—H14A	109.00
N1—C14—C4	110.84 (14)	C4—C14—H14B	109.00
C1—C2—H2	119.00	H14A—C14—H14B	108.00
C7—O1—C6—O2	−175.54 (16)	C2—C3—C4—C5	−177.54 (15)
C7—O1—C6—C5	4.2 (2)	C2—C3—C4—C14	2.2 (2)
C6—O1—C7—C3	−3.5 (2)	C7—C3—C4—C14	−178.75 (14)
C6—O1—C7—C8	176.23 (16)	C2—C3—C7—O1	179.59 (13)
N2—N1—C14—C4	142.33 (17)	C2—C3—C7—C8	−0.1 (2)
C10—C1—C2—C3	−177.49 (14)	C4—C3—C7—O1	0.5 (2)
C2—C1—C9—C8	0.1 (2)	C4—C3—C7—C8	−179.21 (15)
C10—C1—C9—C8	177.99 (15)	C7—C3—C4—C5	1.5 (2)
C2—C1—C10—C11	−128.80 (18)	C3—C4—C5—C6	−0.6 (2)
C2—C1—C10—C12	110.99 (19)	C14—C4—C5—C6	179.65 (16)
C2—C1—C10—C13	−9.6 (2)	C5—C4—C14—N1	−7.9 (2)
C9—C1—C2—C3	0.3 (2)	C3—C4—C14—N1	172.35 (14)
C9—C1—C10—C12	−66.8 (2)	C4—C5—C6—O1	−2.2 (3)
C9—C1—C10—C13	172.62 (15)	C4—C5—C6—O2	177.53 (19)
C9—C1—C10—C11	53.5 (2)	C3—C7—C8—C9	0.5 (2)
C1—C2—C3—C4	178.72 (14)	O1—C7—C8—C9	−179.18 (15)
C1—C2—C3—C7	−0.3 (2)	C7—C8—C9—C1	−0.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14A···O2i	0.97	2.55	3.311 (2)	135

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C14H14AO2i	0.97	2.55	3.311(2)	135

Symmetry code: (i) .