Crystal structure of (tert-butyl-carbamo-yl)(4-chloro-2-oxo-2H-chromen-3-yl)methyl acetate.

In the title compound, C17H18ClNO5, which was synthesized by reacting 4-chloro-3-formyl-coumarin, acetic acid and tert-butyl isocyanide, the acetamido side chain is convoluted with ring-to-side chain C-C-C-C, C-C-C-N and C-C-N-C torsion angles of -123.30 (14), -135.73 (12) and 176.10 (12)°, respectively. In the crystal, N-H⋯O and weak C-H⋯O hydrogen bonds are present, which together with π-π coumarin-ring inter-actions [ring centroid separations = 3.4582 (8) and 3.6421 (9) Å], give rise to a layered structure lying parallel to (001).

Related literature

For applications of coumarin derivatives, see: Luo et al. (2012 ▸); Medina-Franco et al. (2011 ▸); Sun et al. (2013 ▸); Zen et al. (2014 ▸).

Experimental

Crystal data

C17H18ClNO5

M = 351.77

Trigonal,

a = 29.831 (2) Å

c = 9.7983 (8) Å

V = 7551.2 (14) Å3

Z = 18

Mo Kα radiation

μ = 0.25 mm−1

T = 90 K

0.50 × 0.45 × 0.45 mm

Data collection

Bruker APEXII diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T min = 0.746, T max = 0.892

24469 measured reflections

2975 independent reflections

2742 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.094

S = 1.12

2975 reflections

221 parameters

H-atom parameters constrained

Δρmax = 0.41 e Å−3

Δρmin = −0.31 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: Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015021982/zs2353sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015021982/zs2353Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015021982/zs2353Isup3.pdf

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015021982/zs2353Isup4.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015021982/zs2353fig1.tif

Mol­ecular configuration and atom-numbering scheme for the title compound with displacement ellipsoids drawn at the 50% probability level.

Click here for additional data file.

c . DOI: 10.1107/S2056989015021982/zs2353fig2.tif

Crystal packing diagram of the title compound, viewed along the c axis, with hydrogen atoms omitted for clarity.

Click here for additional data file.

. DOI: 10.1107/S2056989015021982/zs2353fig3.tif

Reaction scheme for the synthesis of the title compound.

CCDC reference: 1437533

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

C17H18ClNO5	Dx = 1.392 Mg m−3
Mr = 351.77	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 24469 reflections
a = 29.831 (2) Å	θ = 1.4–25.0°
c = 9.7983 (8) Å	µ = 0.25 mm−1
V = 7551.2 (14) Å3	T = 90 K
Z = 18	Prism, colorless
F(000) = 3312	0.50 × 0.45 × 0.45 mm

Bruker APEXII diffractometer	2975 independent reflections
Radiation source: fine focus sealed tube	2742 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 8.333 pixels mm-1	θmax = 25.0°, θmin = 1.4°
ω scans	h = −35→35
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −35→35
Tmin = 0.746, Tmax = 0.892	l = −11→11
24469 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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094	H-atom parameters constrained
S = 1.12	w = 1/[σ2(Fo2) + (0.0575P)2 + 6.6693P] where P = (Fo2 + 2Fc2)/3
2975 reflections	(Δ/σ)max = 0.001
221 parameters	Δρmax = 0.41 e Å−3
0 restraints	Δρmin = −0.31 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
C1	0.21876 (5)	−0.00044 (5)	0.08087 (13)	0.0160 (3)
C2	0.26499 (5)	0.05104 (5)	0.07629 (13)	0.0157 (3)
C3	0.31212 (5)	0.05536 (5)	0.08748 (13)	0.0155 (3)
C4	0.31867 (5)	0.01052 (5)	0.09456 (13)	0.0158 (3)
C5	0.27379 (5)	−0.03793 (5)	0.09425 (13)	0.0160 (3)
C6	0.27504 (6)	−0.08370 (5)	0.09608 (14)	0.0188 (3)
H6	0.2446	−0.1155	0.0958	0.023*
C7	0.32278 (6)	−0.08086 (5)	0.09835 (14)	0.0208 (3)
H7	0.3244	−0.1112	0.0992	0.025*
C8	0.36839 (6)	−0.03316 (6)	0.09933 (14)	0.0206 (3)
H8	0.4002	−0.0318	0.1015	0.025*
C9	0.36650 (5)	0.01214 (5)	0.09716 (14)	0.0180 (3)
H9	0.3971	0.0439	0.0974	0.022*
C10	0.25496 (5)	0.09571 (5)	0.06509 (14)	0.0168 (3)
H10	0.2879	0.1281	0.0746	0.02*
C11	0.26696 (6)	0.12189 (5)	−0.16856 (15)	0.0206 (3)
C12	0.23933 (6)	0.12088 (6)	−0.29691 (15)	0.0268 (3)
H12A	0.2642	0.139	−0.3676	0.04*
H12B	0.2191	0.1373	−0.281	0.04*
H12C	0.2169	0.0856	−0.3244	0.04*
C13	0.21854 (5)	0.09265 (5)	0.17996 (14)	0.0168 (3)
C14	0.13982 (5)	0.09650 (6)	0.24241 (15)	0.0217 (3)
C15	0.16453 (7)	0.13872 (7)	0.35092 (18)	0.0346 (4)
H15A	0.1901	0.1347	0.4003	0.052*
H15B	0.1384	0.136	0.4129	0.052*
H15C	0.1807	0.1721	0.3078	0.052*
C16	0.10059 (6)	0.10327 (7)	0.15898 (18)	0.0307 (4)
H16A	0.1175	0.1366	0.1155	0.046*
H16B	0.0738	0.1008	0.218	0.046*
H16C	0.0857	0.0767	0.0907	0.046*
C17	0.11322 (7)	0.04277 (7)	0.3076 (2)	0.0368 (4)
H17A	0.1003	0.0169	0.2373	0.055*
H17B	0.0849	0.0387	0.3633	0.055*
H17C	0.1377	0.039	0.3631	0.055*
Cl1	0.367571 (12)	0.115323 (12)	0.09482 (3)	0.01946 (13)
N1	0.18014 (4)	0.10112 (4)	0.14609 (12)	0.0179 (3)
H1	0.1787	0.1098	0.0632	0.021*
O1	0.17497 (4)	−0.00851 (4)	0.07831 (10)	0.0197 (2)
O2	0.22535 (4)	−0.04259 (3)	0.09066 (10)	0.0168 (2)
O3	0.23274 (4)	0.09548 (4)	−0.06642 (9)	0.0183 (2)
O4	0.31297 (4)	0.14258 (4)	−0.15359 (11)	0.0286 (3)
O5	0.22830 (4)	0.08419 (4)	0.29548 (10)	0.0231 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0201 (7)	0.0159 (7)	0.0134 (6)	0.0101 (6)	−0.0014 (5)	−0.0015 (5)
C2	0.0187 (7)	0.0151 (6)	0.0130 (6)	0.0083 (5)	0.0001 (5)	−0.0016 (5)
C3	0.0177 (7)	0.0143 (6)	0.0114 (6)	0.0056 (5)	0.0001 (5)	−0.0021 (5)
C4	0.0200 (7)	0.0183 (7)	0.0099 (7)	0.0102 (6)	−0.0009 (5)	−0.0018 (5)
C5	0.0181 (7)	0.0206 (7)	0.0116 (6)	0.0114 (6)	−0.0006 (5)	−0.0014 (5)
C6	0.0239 (7)	0.0165 (7)	0.0159 (7)	0.0102 (6)	−0.0007 (5)	−0.0004 (5)
C7	0.0307 (8)	0.0228 (7)	0.0163 (7)	0.0188 (6)	−0.0025 (6)	−0.0023 (5)
C8	0.0233 (7)	0.0304 (8)	0.0147 (7)	0.0184 (6)	−0.0024 (5)	−0.0032 (6)
C9	0.0190 (7)	0.0211 (7)	0.0130 (7)	0.0094 (6)	−0.0017 (5)	−0.0031 (5)
C10	0.0179 (7)	0.0148 (6)	0.0174 (7)	0.0081 (5)	−0.0018 (5)	−0.0018 (5)
C11	0.0276 (8)	0.0137 (6)	0.0229 (7)	0.0120 (6)	0.0069 (6)	0.0028 (5)
C12	0.0358 (9)	0.0211 (7)	0.0211 (7)	0.0122 (7)	0.0023 (6)	0.0034 (6)
C13	0.0186 (7)	0.0116 (6)	0.0195 (7)	0.0069 (5)	−0.0002 (5)	−0.0019 (5)
C14	0.0190 (7)	0.0223 (7)	0.0256 (8)	0.0117 (6)	0.0062 (6)	0.0052 (6)
C15	0.0316 (9)	0.0434 (10)	0.0342 (9)	0.0227 (8)	0.0053 (7)	−0.0095 (7)
C16	0.0223 (8)	0.0373 (9)	0.0371 (9)	0.0184 (7)	0.0061 (7)	0.0098 (7)
C17	0.0294 (9)	0.0349 (9)	0.0464 (10)	0.0163 (8)	0.0151 (8)	0.0199 (8)
Cl1	0.01575 (19)	0.01499 (19)	0.0235 (2)	0.00460 (13)	0.00001 (12)	−0.00316 (12)
N1	0.0199 (6)	0.0183 (6)	0.0176 (6)	0.0112 (5)	0.0021 (4)	0.0023 (4)
O1	0.0155 (5)	0.0169 (5)	0.0262 (5)	0.0077 (4)	−0.0018 (4)	−0.0009 (4)
O2	0.0161 (5)	0.0133 (4)	0.0215 (5)	0.0077 (4)	−0.0002 (4)	−0.0008 (4)
O3	0.0212 (5)	0.0165 (5)	0.0171 (5)	0.0094 (4)	0.0007 (4)	0.0023 (4)
O4	0.0242 (6)	0.0313 (6)	0.0299 (6)	0.0137 (5)	0.0078 (4)	0.0079 (5)
O5	0.0262 (5)	0.0297 (6)	0.0193 (5)	0.0184 (5)	−0.0013 (4)	−0.0007 (4)

C1—O1	1.2045 (16)	C11—O3	1.3638 (17)
C1—O2	1.3695 (16)	C11—C12	1.496 (2)
C1—C2	1.4644 (18)	C12—H12A	0.96
C2—C3	1.3507 (19)	C12—H12B	0.96
C2—C10	1.5085 (18)	C12—H12C	0.96
C3—C4	1.4469 (18)	C13—O5	1.2260 (17)
C3—Cl1	1.7269 (13)	C13—N1	1.3325 (18)
C4—C5	1.3952 (19)	C14—N1	1.4802 (17)
C4—C9	1.4033 (19)	C14—C16	1.521 (2)
C5—O2	1.3814 (16)	C14—C15	1.527 (2)
C5—C6	1.3843 (19)	C14—C17	1.528 (2)
C6—C7	1.384 (2)	C15—H15A	0.96
C6—H6	0.93	C15—H15B	0.96
C7—C8	1.393 (2)	C15—H15C	0.96
C7—H7	0.93	C16—H16A	0.96
C8—C9	1.380 (2)	C16—H16B	0.96
C8—H8	0.93	C16—H16C	0.96
C9—H9	0.93	C17—H17A	0.96
C10—O3	1.4475 (16)	C17—H17B	0.96
C10—C13	1.5352 (19)	C17—H17C	0.96
C10—H10	0.98	N1—H1	0.86
C11—O4	1.1998 (18)
O1—C1—O2	117.20 (12)	C11—C12—H12B	109.5
O1—C1—C2	124.58 (12)	H12A—C12—H12B	109.5
O2—C1—C2	118.21 (11)	C11—C12—H12C	109.5
C3—C2—C1	119.15 (12)	H12A—C12—H12C	109.5
C3—C2—C10	125.34 (12)	H12B—C12—H12C	109.5
C1—C2—C10	115.46 (11)	O5—C13—N1	125.74 (13)
C2—C3—C4	122.08 (12)	O5—C13—C10	117.08 (12)
C2—C3—Cl1	120.95 (10)	N1—C13—C10	117.14 (12)
C4—C3—Cl1	116.97 (10)	N1—C14—C16	106.75 (12)
C5—C4—C9	117.92 (12)	N1—C14—C15	109.41 (12)
C5—C4—C3	117.02 (12)	C16—C14—C15	110.54 (13)
C9—C4—C3	125.02 (12)	N1—C14—C17	109.62 (12)
O2—C5—C6	116.35 (12)	C16—C14—C17	109.48 (13)
O2—C5—C4	121.20 (11)	C15—C14—C17	110.95 (14)
C6—C5—C4	122.45 (12)	C14—C15—H15A	109.5
C7—C6—C5	118.30 (13)	C14—C15—H15B	109.5
C7—C6—H6	120.8	H15A—C15—H15B	109.5
C5—C6—H6	120.8	C14—C15—H15C	109.5
C6—C7—C8	120.80 (13)	H15A—C15—H15C	109.5
C6—C7—H7	119.6	H15B—C15—H15C	109.5
C8—C7—H7	119.6	C14—C16—H16A	109.5
C9—C8—C7	120.20 (13)	C14—C16—H16B	109.5
C9—C8—H8	119.9	H16A—C16—H16B	109.5
C7—C8—H8	119.9	C14—C16—H16C	109.5
C8—C9—C4	120.32 (13)	H16A—C16—H16C	109.5
C8—C9—H9	119.8	H16B—C16—H16C	109.5
C4—C9—H9	119.8	C14—C17—H17A	109.5
O3—C10—C2	110.68 (10)	C14—C17—H17B	109.5
O3—C10—C13	110.09 (11)	H17A—C17—H17B	109.5
C2—C10—C13	109.95 (11)	C14—C17—H17C	109.5
O3—C10—H10	108.7	H17A—C17—H17C	109.5
C2—C10—H10	108.7	H17B—C17—H17C	109.5
C13—C10—H10	108.7	C13—N1—C14	124.00 (12)
O4—C11—O3	122.73 (13)	C13—N1—H1	118.0
O4—C11—C12	126.18 (13)	C14—N1—H1	118.0
O3—C11—C12	111.08 (12)	C1—O2—C5	122.19 (10)
C11—C12—H12A	109.5	C11—O3—C10	116.22 (11)
O1—C1—C2—C3	176.34 (13)	C3—C4—C9—C8	−177.79 (12)
O2—C1—C2—C3	−2.70 (19)	C3—C2—C10—O3	114.86 (14)
O1—C1—C2—C10	−1.13 (19)	C1—C2—C10—O3	−67.85 (14)
O2—C1—C2—C10	179.83 (11)	C3—C2—C10—C13	−123.30 (14)
C1—C2—C3—C4	4.3 (2)	C1—C2—C10—C13	53.99 (15)
C10—C2—C3—C4	−178.51 (12)	O3—C10—C13—O5	168.64 (11)
C1—C2—C3—Cl1	−175.38 (9)	C2—C10—C13—O5	46.45 (16)
C10—C2—C3—Cl1	1.81 (19)	O3—C10—C13—N1	−13.54 (16)
C2—C3—C4—C5	−2.2 (2)	C2—C10—C13—N1	−135.73 (12)
Cl1—C3—C4—C5	177.46 (9)	O5—C13—N1—C14	−6.3 (2)
C2—C3—C4—C9	175.57 (13)	C10—C13—N1—C14	176.10 (12)
Cl1—C3—C4—C9	−4.74 (19)	C16—C14—N1—C13	−173.64 (13)
C9—C4—C5—O2	−179.48 (11)	C15—C14—N1—C13	66.72 (17)
C3—C4—C5—O2	−1.52 (19)	C17—C14—N1—C13	−55.16 (18)
C9—C4—C5—C6	−0.1 (2)	O1—C1—O2—C5	179.92 (11)
C3—C4—C5—C6	177.82 (12)	C2—C1—O2—C5	−0.97 (18)
O2—C5—C6—C7	179.39 (11)	C6—C5—O2—C1	−176.28 (11)
C4—C5—C6—C7	0.0 (2)	C4—C5—O2—C1	3.10 (19)
C5—C6—C7—C8	0.3 (2)	O4—C11—O3—C10	2.96 (18)
C6—C7—C8—C9	−0.4 (2)	C12—C11—O3—C10	−177.30 (11)
C7—C8—C9—C4	0.3 (2)	C2—C10—O3—C11	−89.05 (13)
C5—C4—C9—C8	0.0 (2)	C13—C10—O3—C11	149.19 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3	0.86	2.25	2.6627 (17)	109
N1—H1···O1i	0.86	2.33	3.0787 (16)	145
C9—H9···Cl1	0.93	2.68	3.0623 (15)	105
C10—H10···Cl1	0.98	2.60	3.1220 (17)	114
C15—H15A···O5	0.96	2.52	3.107 (3)	120
C16—H16A···O1i	0.96	2.56	3.287 (2)	133
C17—H17C···O5	0.96	2.43	3.014 (3)	119

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.86	2.33	3.0787 (16)	145
C16—H16A⋯O1i	0.96	2.56	3.287 (2)	133

Symmetry code: (i) .