Crystal structure of 3-meth-oxy-carbonyl-2-(4-meth-oxy-phen-yl)-8-oxo-1-aza-spiro[4.5]deca-1,6,9-trien-1-ium-1-olate.

The title compound, C18H17NO5, was prepared by a synthetic strategy based on the Heck reaction from Morita-Baylis-Hillman adducts. The five-membered ring adopts a slightly twisted conformation on the Ca-Cm (a = aromatic and m = methyl-ene) bond. The dihedral angle between the five-membered ring and the spiro aromatic ring is 89.35 (7)°; that between the five-membered ring and the 4-meth-oxy-benzene ring is 4.65 (7)°. Two short intra-molecular C-H⋯O contacts occur. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds to generate a three-dimensional network.

Related literature

For compounds that contain a spiro­hexa­dienone moiety in their structures, see: Wright & König (1993 ▶); König et al. (1990 ▶); Beil et al. (1998 ▶) and for their biological activities, see: Glushkov et al. (2010 ▶); Pereira et al. (2007 ▶). For strategies for the synthesis of spiro-hexa­dienones from Morita–Baylis–Hillman adducts, see: Coelho et al. (2002 ▶); Ferreira et al. (2009 ▶); Pirovani et al. (2009 ▶); Martins et al. (2014 ▶). For the biological activity of compounds containing a nitrone group, see: Fangour et al. (2009 ▶); Floyd et al. (2008 ▶); Halliwell & Gutteridge (1999 ▶); Fevig et al. (1996 ▶). For a discussion about non-classical hydrogen bonds, see: Desiraju (2005 ▶).

Experimental

Crystal data

C18H17NO5

M = 327.32

Triclinic,

a = 6.0916 (11) Å

b = 8.7713 (16) Å

c = 15.167 (3) Å

α = 80.255 (6)°

β = 81.703 (6)°

γ = 80.122 (6)°

V = 781.3 (2) Å3

Z = 2

Cu Kα radiation

μ = 0.85 mm−1

T = 100 K

0.47 × 0.20 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2010 ▶) T min = 0.813, T max = 1.000

14656 measured reflections

2771 independent reflections

2727 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.105

S = 1.11

2771 reflections

220 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.35 e Å−3

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008 ▶); molecular graphics: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814023277/hb7301sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814023277/hb7301Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814023277/hb7301Isup3.cdx

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814023277/hb7301Isup4.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814023277/hb7301fig1.tif

The mol­ecular structure of the title compound with 50% probability displacement ellipsoids.

Click here for additional data file.

. DOI: 10.1107/S1600536814023277/hb7301fig2.tif

Crystal packing of the title compound, showing hydrogen bonding inter­actions.

CCDC reference: 1030399

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

C18H17NO5	Z = 2
Mr = 327.32	F(000) = 344
Triclinic, P1	Dx = 1.391 Mg m−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 6.0916 (11) Å	Cell parameters from 109 reflections
b = 8.7713 (16) Å	θ = 9.0–38.4°
c = 15.167 (3) Å	µ = 0.85 mm−1
α = 80.255 (6)°	T = 100 K
β = 81.703 (6)°	Prismatic, colourless
γ = 80.122 (6)°	0.47 × 0.20 × 0.17 mm
V = 781.3 (2) Å3

Bruker APEXII CCD diffractometer	2771 independent reflections
Radiation source: fine-focus sealed tube	2727 reflections with I > 2σ(I)
Detector resolution: 8.3333 pixels mm-1	Rint = 0.033
φ and ω scans	θmax = 67.7°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −5→7
Tmin = 0.813, Tmax = 1.000	k = −10→10
14656 measured reflections	l = −18→17

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.042	w = 1/[σ2(Fo2) + (0.0542P)2 + 0.3281P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.105	(Δ/σ)max < 0.001
S = 1.11	Δρmax = 0.28 e Å−3
2771 reflections	Δρmin = −0.35 e Å−3
220 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2014), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.043 (2)

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.

	x	y	z	Uiso*/Ueq
O2	0.20642 (16)	0.89397 (12)	0.62486 (6)	0.0247 (3)
O5	0.19082 (18)	0.28804 (12)	0.01392 (7)	0.0309 (3)
O1	0.19910 (14)	0.44109 (11)	0.32280 (6)	0.0199 (2)
O4	0.91693 (15)	0.79511 (11)	0.19091 (7)	0.0228 (3)
O3	0.54105 (16)	0.85337 (11)	0.19863 (7)	0.0281 (3)
N1	0.38917 (17)	0.48769 (12)	0.29230 (7)	0.0166 (3)
C8	−0.0287 (2)	0.92550 (17)	0.65513 (10)	0.0252 (3)
H1A	−0.1106	0.9720	0.6036	0.038*
H1B	−0.0535	0.9985	0.6991	0.038*
H1C	−0.0827	0.8276	0.6833	0.038*
C5	0.2673 (2)	0.80731 (16)	0.55566 (9)	0.0202 (3)
C4	0.1260 (2)	0.72330 (16)	0.52570 (9)	0.0200 (3)
H3	−0.0222	0.7203	0.5551	0.024*
C3	0.2017 (2)	0.64391 (15)	0.45269 (9)	0.0189 (3)
H4	0.1048	0.5855	0.4333	0.023*
C2	0.4179 (2)	0.64816 (15)	0.40712 (9)	0.0177 (3)
C1	0.4981 (2)	0.57613 (15)	0.32644 (9)	0.0173 (3)
C13	0.4972 (2)	0.44582 (15)	0.20162 (9)	0.0180 (3)
C14	0.3688 (2)	0.55382 (15)	0.13203 (9)	0.0186 (3)
H8	0.3569	0.6635	0.1312	0.022*
C15	0.2712 (2)	0.50353 (16)	0.07177 (9)	0.0202 (3)
H9	0.1934	0.5777	0.0293	0.024*
C16	0.2811 (2)	0.33526 (16)	0.06944 (9)	0.0216 (3)
C7	0.5596 (2)	0.73034 (16)	0.44026 (9)	0.0207 (3)
H11	0.7083	0.7332	0.4114	0.025*
C6	0.4867 (2)	0.80683 (16)	0.51396 (9)	0.0223 (3)
H12	0.5863	0.8593	0.5363	0.027*
C18	0.4924 (2)	0.27616 (15)	0.20004 (9)	0.0197 (3)
H13	0.5580	0.2010	0.2454	0.024*
C17	0.4002 (2)	0.22581 (16)	0.13799 (9)	0.0213 (3)
H14	0.4117	0.1164	0.1379	0.026*
C12	0.7367 (2)	0.48121 (15)	0.20051 (9)	0.0196 (3)
H15A	0.7956	0.5274	0.1394	0.024*
H15B	0.8389	0.3846	0.2199	0.024*
C9	0.7139 (2)	0.59949 (15)	0.26787 (9)	0.0186 (3)
H16	0.8422	0.5732	0.3049	0.022*
C10	0.7081 (2)	0.76464 (16)	0.21684 (9)	0.0195 (3)
C11	0.9377 (3)	0.93704 (17)	0.12808 (10)	0.0270 (3)
H18A	0.8704	0.9329	0.0738	0.040*
H18B	1.0968	0.9470	0.1118	0.040*
H18C	0.8601	1.0274	0.1561	0.040*

	U11	U22	U33	U12	U13	U23
O2	0.0232 (5)	0.0323 (6)	0.0211 (5)	−0.0051 (4)	−0.0046 (4)	−0.0084 (4)
O5	0.0324 (6)	0.0323 (6)	0.0319 (6)	−0.0051 (5)	−0.0150 (5)	−0.0066 (4)
O1	0.0130 (5)	0.0267 (5)	0.0208 (5)	−0.0079 (4)	−0.0007 (4)	−0.0017 (4)
O4	0.0166 (5)	0.0233 (5)	0.0272 (5)	−0.0063 (4)	0.0016 (4)	−0.0003 (4)
O3	0.0188 (5)	0.0246 (5)	0.0372 (6)	−0.0016 (4)	−0.0037 (4)	0.0044 (4)
N1	0.0128 (5)	0.0199 (5)	0.0161 (5)	−0.0027 (4)	−0.0024 (4)	0.0005 (4)
C8	0.0252 (7)	0.0298 (7)	0.0210 (7)	−0.0038 (6)	−0.0018 (6)	−0.0061 (6)
C5	0.0233 (7)	0.0216 (7)	0.0158 (6)	−0.0023 (5)	−0.0067 (5)	−0.0005 (5)
C4	0.0179 (6)	0.0231 (7)	0.0183 (6)	−0.0047 (5)	−0.0025 (5)	0.0008 (5)
C3	0.0180 (6)	0.0209 (6)	0.0184 (6)	−0.0057 (5)	−0.0048 (5)	0.0004 (5)
C2	0.0163 (6)	0.0187 (6)	0.0174 (6)	−0.0028 (5)	−0.0051 (5)	0.0022 (5)
C1	0.0143 (6)	0.0185 (6)	0.0182 (6)	−0.0023 (5)	−0.0051 (5)	0.0019 (5)
C13	0.0139 (6)	0.0229 (7)	0.0166 (6)	−0.0016 (5)	−0.0014 (5)	−0.0023 (5)
C14	0.0140 (6)	0.0202 (6)	0.0190 (6)	−0.0005 (5)	0.0006 (5)	−0.0004 (5)
C15	0.0148 (6)	0.0250 (7)	0.0184 (6)	−0.0002 (5)	−0.0023 (5)	0.0011 (5)
C16	0.0156 (6)	0.0280 (7)	0.0214 (7)	−0.0036 (5)	−0.0017 (5)	−0.0039 (6)
C7	0.0153 (6)	0.0238 (7)	0.0229 (7)	−0.0043 (5)	−0.0045 (5)	−0.0001 (5)
C6	0.0199 (7)	0.0245 (7)	0.0246 (7)	−0.0054 (5)	−0.0094 (5)	−0.0019 (5)
C18	0.0159 (6)	0.0216 (7)	0.0195 (6)	0.0000 (5)	−0.0017 (5)	0.0000 (5)
C17	0.0180 (7)	0.0208 (7)	0.0243 (7)	−0.0027 (5)	−0.0017 (5)	−0.0021 (5)
C12	0.0136 (6)	0.0226 (7)	0.0219 (7)	−0.0013 (5)	−0.0027 (5)	−0.0017 (5)
C9	0.0130 (6)	0.0218 (7)	0.0204 (6)	−0.0021 (5)	−0.0037 (5)	−0.0006 (5)
C10	0.0159 (6)	0.0231 (7)	0.0197 (7)	−0.0041 (5)	−0.0013 (5)	−0.0033 (5)
C11	0.0275 (8)	0.0252 (7)	0.0277 (7)	−0.0109 (6)	0.0023 (6)	0.0002 (6)

O2—C5	1.3705 (17)	C13—C14	1.5066 (18)
O2—C8	1.4339 (17)	C13—C12	1.5395 (17)
O5—C16	1.2301 (17)	C14—C15	1.3289 (19)
O1—N1	1.2905 (14)	C14—H8	0.9500
O4—C10	1.3345 (16)	C15—C16	1.473 (2)
O4—C11	1.4462 (17)	C15—H9	0.9500
O3—C10	1.2059 (17)	C16—C17	1.4732 (19)
N1—C1	1.3121 (17)	C7—C6	1.380 (2)
N1—C13	1.5121 (16)	C7—H11	0.9500
C8—H1A	0.9800	C6—H12	0.9500
C8—H1B	0.9800	C18—C17	1.332 (2)
C8—H1C	0.9800	C18—H13	0.9500
C5—C4	1.3908 (19)	C17—H14	0.9500
C5—C6	1.393 (2)	C12—C9	1.5519 (18)
C4—C3	1.3884 (19)	C12—H15A	0.9900
C4—H3	0.9500	C12—H15B	0.9900
C3—C2	1.3996 (19)	C9—C10	1.5197 (18)
C3—H4	0.9500	C9—H16	1.0000
C2—C7	1.4067 (18)	C11—H18A	0.9800
C2—C1	1.4554 (19)	C11—H18B	0.9800
C1—C9	1.5014 (18)	C11—H18C	0.9800
C13—C18	1.4977 (19)
C5—O2—C8	116.78 (10)	C16—C15—H9	119.3
C10—O4—C11	115.74 (11)	O5—C16—C15	121.67 (13)
O1—N1—C1	128.90 (11)	O5—C16—C17	121.42 (13)
O1—N1—C13	116.85 (10)	C15—C16—C17	116.89 (12)
C1—N1—C13	114.09 (10)	C6—C7—C2	121.25 (12)
O2—C8—H1A	109.5	C6—C7—H11	119.4
O2—C8—H1B	109.5	C2—C7—H11	119.4
H1A—C8—H1B	109.5	C7—C6—C5	120.13 (12)
O2—C8—H1C	109.5	C7—C6—H12	119.9
H1A—C8—H1C	109.5	C5—C6—H12	119.9
H1B—C8—H1C	109.5	C17—C18—C13	123.01 (12)
O2—C5—C4	124.47 (12)	C17—C18—H13	118.5
O2—C5—C6	115.89 (12)	C13—C18—H13	118.5
C4—C5—C6	119.64 (12)	C18—C17—C16	121.73 (13)
C3—C4—C5	119.90 (12)	C18—C17—H14	119.1
C3—C4—H3	120.1	C16—C17—H14	119.1
C5—C4—H3	120.1	C13—C12—C9	105.07 (10)
C4—C3—C2	121.34 (12)	C13—C12—H15A	110.7
C4—C3—H4	119.3	C9—C12—H15A	110.7
C2—C3—H4	119.3	C13—C12—H15B	110.7
C3—C2—C7	117.62 (12)	C9—C12—H15B	110.7
C3—C2—C1	123.04 (12)	H15A—C12—H15B	108.8
C7—C2—C1	119.31 (12)	C1—C9—C10	112.58 (11)
N1—C1—C2	125.30 (12)	C1—C9—C12	103.83 (10)
N1—C1—C9	110.32 (11)	C10—C9—C12	109.86 (11)
C2—C1—C9	124.32 (11)	C1—C9—H16	110.1
C18—C13—C14	113.42 (11)	C10—C9—H16	110.1
C18—C13—N1	109.22 (10)	C12—C9—H16	110.1
C14—C13—N1	106.44 (10)	O3—C10—O4	124.52 (12)
C18—C13—C12	112.45 (11)	O3—C10—C9	125.53 (12)
C14—C13—C12	113.17 (11)	O4—C10—C9	109.87 (11)
N1—C13—C12	101.15 (10)	O4—C11—H18A	109.5
C15—C14—C13	123.35 (12)	O4—C11—H18B	109.5
C15—C14—H8	118.3	H18A—C11—H18B	109.5
C13—C14—H8	118.3	O4—C11—H18C	109.5
C14—C15—C16	121.39 (12)	H18A—C11—H18C	109.5
C14—C15—H9	119.3	H18B—C11—H18C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
C8—H1C···O1i	0.98	2.59	3.4941 (18)	153
C4—H3···O1i	0.95	2.38	3.1345 (16)	136
C3—H4···O1	0.95	2.22	2.8725 (17)	125
C14—H8···O3	0.95	2.57	3.3431 (18)	138
C15—H9···O5ii	0.95	2.56	3.3821 (17)	146
C18—H13···O2iii	0.95	2.54	3.4309 (17)	155
C17—H14···O3iv	0.95	2.38	3.2408 (18)	151
C12—H15A···O5v	0.99	2.60	3.5402 (18)	159
C9—H16···O1vi	1.00	2.31	3.2045 (16)	148

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C8H1CO1i	0.98	2.59	3.4941(18)	153
C4H3O1i	0.95	2.38	3.1345(16)	136
C3H4O1	0.95	2.22	2.8725(17)	125
C14H8O3	0.95	2.57	3.3431(18)	138
C15H9O5ii	0.95	2.56	3.3821(17)	146
C18H13O2iii	0.95	2.54	3.4309(17)	155
C17H14O3iv	0.95	2.38	3.2408(18)	151
C12H15AO5v	0.99	2.60	3.5402(18)	159
C9H16O1vi	1.00	2.31	3.2045(16)	148

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