1-Methyl-3-(2-oxo-2H-chromen-3-yl)-1H-imidazol-3-ium picrate.

The title salt, C13H11N2O2 (+)·C6H2N3O7 (-), is the unexpected product of a domino reaction of 3-cyano-methyl-1-methyl-imidazolium chloride with salicylic aldehyde in the presence of picric acid. In the cation, the 1H-imidazole ring is twisted by 63.2 (1)° from the 2H-chromen plane. In the crystal, cations and anions are alternately stacked along the a axis through π-π stacking inter-actions between the almost parallel aromatic rings [centroid-centroid distances = 3.458 (2) and 3.678 (2) Å]. The stacks are further linked by C-H⋯O hydrogen bonds into a two-tier layer parallel to (001).

Related literature

For a recent review on coumarin-based drug patents, see: Kontogiorgis et al. (2012 ▶). For analogous domino reactions, see: Voskressensky et al. (2012a ▶,b ▶). For related compounds, see: Yu et al. (2006 ▶); Morris et al. (2011 ▶).

Experimental

Crystal data

C13H11N2O2 +·C6H2N3O7 −

M = 455.34

Monoclinic,

a = 6.8142 (12) Å

b = 8.1942 (14) Å

c = 16.832 (3) Å

β = 100.081 (4)°

V = 925.3 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.13 mm−1

T = 100 K

0.30 × 0.21 × 0.03 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T min = 0.961, T max = 0.996

10390 measured reflections

4415 independent reflections

3734 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.063

wR(F 2) = 0.165

S = 1.00

4415 reflections

299 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.46 e Å−3

Δρmin = −0.36 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813011690/is5268sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813011690/is5268Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813011690/is5268Isup3.cml

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

C13H11N2O2+·C6H2N3O7−	F(000) = 468
Mr = 455.34	Dx = 1.634 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3018 reflections
a = 6.8142 (12) Å	θ = 2.5–30.2°
b = 8.1942 (14) Å	µ = 0.13 mm−1
c = 16.832 (3) Å	T = 100 K
β = 100.081 (4)°	Plate, yellow
V = 925.3 (3) Å3	0.30 × 0.21 × 0.03 mm
Z = 2

Bruker APEXII CCD diffractometer	4415 independent reflections
Radiation source: fine-focus sealed tube	3734 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
φ and ω scans	θmax = 28.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −9→9
Tmin = 0.961, Tmax = 0.996	k = −10→10
10390 measured reflections	l = −22→22

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.165	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0754P)2 + 1.86P] where P = (Fo2 + 2Fc2)/3
4415 reflections	(Δ/σ)max < 0.001
299 parameters	Δρmax = 0.46 e Å−3
1 restraint	Δρmin = −0.36 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
O1	0.8777 (4)	0.6678 (3)	0.68430 (15)	0.0183 (5)
O2	0.8003 (4)	0.5232 (4)	0.57153 (15)	0.0233 (6)
N1	0.9223 (4)	0.2275 (4)	0.64703 (18)	0.0166 (6)
N2	0.8021 (5)	0.0278 (4)	0.57071 (17)	0.0166 (6)
C2	0.8643 (5)	0.5224 (5)	0.6430 (2)	0.0168 (7)
C3	0.9351 (5)	0.3784 (5)	0.6911 (2)	0.0161 (7)
C4	1.0105 (5)	0.3861 (5)	0.7702 (2)	0.0171 (7)
H4	1.0561	0.2899	0.7992	0.021*
C4A	1.0217 (5)	0.5408 (5)	0.8103 (2)	0.0165 (7)
C5	1.0926 (5)	0.5595 (5)	0.8937 (2)	0.0178 (7)
H5	1.1365	0.4666	0.9257	0.021*
C6	1.0989 (5)	0.7124 (5)	0.9295 (2)	0.0205 (8)
H6	1.1461	0.7240	0.9857	0.025*
C7	1.0352 (6)	0.8501 (5)	0.8821 (2)	0.0223 (8)
H7	1.0420	0.9552	0.9063	0.027*
C8	0.9623 (6)	0.8333 (5)	0.8001 (2)	0.0208 (8)
H8	0.9169	0.9257	0.7681	0.025*
C8A	0.9570 (5)	0.6794 (5)	0.7661 (2)	0.0172 (7)
C9	0.7529 (5)	0.1610 (5)	0.6077 (2)	0.0163 (7)
H9	0.6218	0.2018	0.6064	0.020*
C10	1.0046 (6)	0.0076 (5)	0.5862 (2)	0.0198 (7)
H10	1.0772	−0.0786	0.5671	0.024*
C11	1.0826 (5)	0.1338 (5)	0.6341 (2)	0.0200 (7)
H11	1.2195	0.1536	0.6546	0.024*
C12	0.6615 (6)	−0.0810 (5)	0.5195 (2)	0.0218 (8)
H12A	0.5247	−0.0517	0.5245	0.033*
H12B	0.6878	−0.1942	0.5369	0.033*
H12C	0.6784	−0.0694	0.4632	0.033*
O3	0.4485 (4)	0.3812 (3)	0.67659 (15)	0.0185 (5)
O4	0.7273 (4)	0.1650 (4)	0.85805 (18)	0.0293 (7)
O5	0.4224 (5)	0.1338 (4)	0.79424 (19)	0.0310 (7)
O6	0.6970 (5)	0.6752 (4)	1.02204 (16)	0.0283 (7)
O7	0.5824 (4)	0.8942 (3)	0.95546 (17)	0.0245 (6)
O8	0.4486 (4)	0.8736 (3)	0.66647 (16)	0.0239 (6)
O9	0.2690 (4)	0.6684 (4)	0.61602 (16)	0.0257 (6)
N3	0.5653 (5)	0.2192 (4)	0.82445 (19)	0.0197 (6)
N4	0.6210 (5)	0.7472 (4)	0.95962 (18)	0.0183 (6)
N5	0.3876 (5)	0.7341 (4)	0.67024 (19)	0.0185 (6)
C13	0.4738 (5)	0.4649 (4)	0.7400 (2)	0.0134 (7)
C14	0.5419 (5)	0.3960 (5)	0.8190 (2)	0.0173 (7)
C15	0.5962 (5)	0.4837 (4)	0.8896 (2)	0.0155 (7)
H15	0.6481	0.4310	0.9391	0.019*
C16	0.5717 (5)	0.6527 (5)	0.8853 (2)	0.0159 (7)
C17	0.5037 (5)	0.7321 (5)	0.8138 (2)	0.0161 (7)
H17	0.4908	0.8476	0.8125	0.019*
C18	0.4542 (5)	0.6419 (5)	0.7437 (2)	0.0170 (7)

	U11	U22	U33	U12	U13	U23
O1	0.0207 (13)	0.0180 (13)	0.0157 (12)	0.0025 (11)	0.0020 (9)	−0.0013 (10)
O2	0.0339 (16)	0.0201 (14)	0.0150 (12)	−0.0014 (12)	0.0016 (11)	0.0006 (11)
N1	0.0142 (14)	0.0172 (15)	0.0181 (14)	−0.0001 (12)	0.0019 (11)	−0.0001 (12)
N2	0.0237 (16)	0.0131 (14)	0.0130 (13)	−0.0004 (12)	0.0036 (11)	−0.0013 (11)
C2	0.0155 (17)	0.0147 (16)	0.0212 (17)	0.0007 (14)	0.0062 (13)	0.0011 (14)
C3	0.0155 (16)	0.0133 (16)	0.0195 (17)	0.0007 (13)	0.0035 (13)	−0.0003 (14)
C4	0.0178 (16)	0.0163 (17)	0.0175 (16)	0.0021 (14)	0.0042 (13)	0.0010 (14)
C4A	0.0121 (16)	0.0192 (18)	0.0181 (16)	−0.0026 (14)	0.0024 (13)	−0.0024 (14)
C5	0.0141 (17)	0.0206 (18)	0.0175 (17)	0.0014 (14)	−0.0002 (13)	0.0014 (14)
C6	0.0167 (17)	0.022 (2)	0.0212 (18)	−0.0030 (14)	−0.0002 (13)	−0.0036 (15)
C7	0.0167 (18)	0.022 (2)	0.028 (2)	−0.0007 (15)	0.0040 (15)	−0.0101 (16)
C8	0.0208 (19)	0.0158 (18)	0.0256 (19)	0.0011 (14)	0.0038 (15)	−0.0010 (14)
C8A	0.0176 (17)	0.0215 (18)	0.0117 (15)	−0.0002 (14)	0.0010 (12)	−0.0012 (14)
C9	0.0165 (16)	0.0163 (17)	0.0157 (16)	0.0008 (14)	0.0018 (12)	−0.0001 (13)
C10	0.0222 (18)	0.0217 (19)	0.0169 (16)	0.0009 (15)	0.0072 (13)	0.0022 (14)
C11	0.0163 (17)	0.0250 (19)	0.0192 (18)	0.0025 (15)	0.0047 (13)	0.0031 (14)
C12	0.029 (2)	0.0186 (19)	0.0155 (17)	−0.0051 (15)	−0.0025 (14)	−0.0030 (14)
O3	0.0197 (13)	0.0201 (13)	0.0150 (12)	0.0018 (11)	0.0011 (9)	−0.0049 (11)
O4	0.0266 (15)	0.0243 (15)	0.0361 (16)	0.0091 (12)	0.0032 (12)	0.0054 (13)
O5	0.0455 (18)	0.0140 (14)	0.0279 (15)	−0.0041 (13)	−0.0089 (13)	0.0022 (11)
O6	0.0429 (17)	0.0229 (15)	0.0172 (13)	−0.0014 (13)	0.0000 (12)	−0.0038 (11)
O7	0.0348 (15)	0.0170 (14)	0.0207 (13)	−0.0002 (12)	0.0022 (11)	−0.0069 (11)
O8	0.0346 (16)	0.0162 (13)	0.0212 (13)	−0.0008 (12)	0.0061 (11)	0.0041 (11)
O9	0.0310 (15)	0.0231 (14)	0.0195 (13)	0.0036 (12)	−0.0057 (11)	−0.0036 (11)
N3	0.0268 (17)	0.0144 (15)	0.0179 (15)	0.0034 (13)	0.0041 (12)	0.0003 (12)
N4	0.0204 (15)	0.0182 (16)	0.0172 (15)	−0.0036 (12)	0.0060 (12)	−0.0042 (12)
N5	0.0173 (15)	0.0213 (16)	0.0170 (15)	0.0028 (13)	0.0036 (12)	−0.0008 (12)
C13	0.0079 (16)	0.0186 (18)	0.0135 (15)	−0.0004 (12)	0.0015 (12)	−0.0022 (12)
C14	0.0168 (17)	0.0131 (17)	0.0212 (18)	0.0002 (14)	0.0011 (13)	0.0017 (14)
C15	0.0147 (17)	0.0144 (17)	0.0184 (17)	−0.0013 (13)	0.0051 (13)	−0.0006 (13)
C16	0.0157 (16)	0.0160 (17)	0.0159 (16)	−0.0011 (14)	0.0023 (12)	−0.0057 (14)
C17	0.0129 (16)	0.0159 (17)	0.0205 (17)	−0.0002 (14)	0.0062 (13)	−0.0020 (14)
C18	0.0148 (17)	0.0170 (18)	0.0182 (17)	−0.0003 (14)	0.0002 (13)	0.0003 (14)

O1—C2	1.374 (5)	C10—C11	1.361 (6)
O1—C8A	1.391 (4)	C10—H10	0.9500
O2—C2	1.206 (5)	C11—H11	0.9500
N1—C9	1.342 (5)	C12—H12A	0.9800
N1—C11	1.383 (5)	C12—H12B	0.9800
N1—C3	1.437 (5)	C12—H12C	0.9800
N2—C9	1.328 (5)	O3—C13	1.255 (4)
N2—C10	1.369 (5)	O4—N3	1.232 (4)
N2—C12	1.472 (5)	O5—N3	1.235 (4)
C2—C3	1.464 (5)	O6—N4	1.237 (4)
C3—C4	1.342 (5)	O7—N4	1.232 (4)
C4—C4A	1.433 (5)	O8—N5	1.222 (4)
C4—H4	0.9500	O9—N5	1.232 (4)
C4A—C8A	1.387 (5)	N3—C14	1.458 (5)
C4A—C5	1.410 (5)	N4—C16	1.460 (4)
C5—C6	1.387 (6)	N5—C18	1.452 (5)
C5—H5	0.9500	C13—C14	1.445 (5)
C6—C7	1.405 (6)	C13—C18	1.458 (5)
C6—H6	0.9500	C14—C15	1.383 (5)
C7—C8	1.389 (6)	C15—C16	1.395 (5)
C7—H7	0.9500	C15—H15	0.9500
C8—C8A	1.383 (5)	C16—C17	1.376 (5)
C8—H8	0.9500	C17—C18	1.383 (5)
C9—H9	0.9500	C17—H17	0.9500
C2—O1—C8A	122.7 (3)	C11—C10—H10	126.4
C9—N1—C11	109.4 (3)	N2—C10—H10	126.4
C9—N1—C3	125.0 (3)	C10—C11—N1	106.1 (3)
C11—N1—C3	125.5 (3)	C10—C11—H11	126.9
C9—N2—C10	109.8 (3)	N1—C11—H11	126.9
C9—N2—C12	125.5 (3)	N2—C12—H12A	109.5
C10—N2—C12	124.7 (3)	N2—C12—H12B	109.5
O2—C2—O1	118.7 (3)	H12A—C12—H12B	109.5
O2—C2—C3	125.7 (4)	N2—C12—H12C	109.5
O1—C2—C3	115.6 (3)	H12A—C12—H12C	109.5
C4—C3—N1	122.0 (3)	H12B—C12—H12C	109.5
C4—C3—C2	122.9 (4)	O4—N3—O5	124.3 (3)
N1—C3—C2	115.1 (3)	O4—N3—C14	117.8 (3)
C3—C4—C4A	119.3 (4)	O5—N3—C14	117.9 (3)
C3—C4—H4	120.4	O7—N4—O6	124.6 (3)
C4A—C4—H4	120.4	O7—N4—C16	117.1 (3)
C8A—C4A—C5	117.8 (3)	O6—N4—C16	118.3 (3)
C8A—C4A—C4	119.1 (3)	O8—N5—O9	123.7 (3)
C5—C4A—C4	123.1 (4)	O8—N5—C18	118.2 (3)
C6—C5—C4A	120.6 (4)	O9—N5—C18	118.0 (3)
C6—C5—H5	119.7	O3—C13—C14	122.9 (3)
C4A—C5—H5	119.7	O3—C13—C18	125.4 (3)
C5—C6—C7	119.7 (3)	C14—C13—C18	111.5 (3)
C5—C6—H6	120.1	C15—C14—C13	125.6 (3)
C7—C6—H6	120.1	C15—C14—N3	116.9 (3)
C8—C7—C6	120.3 (4)	C13—C14—N3	117.4 (3)
C8—C7—H7	119.8	C14—C15—C16	117.4 (3)
C6—C7—H7	119.8	C14—C15—H15	121.3
C8A—C8—C7	118.7 (4)	C16—C15—H15	121.3
C8A—C8—H8	120.6	C17—C16—C15	122.3 (3)
C7—C8—H8	120.6	C17—C16—N4	119.4 (3)
C8—C8A—C4A	122.8 (3)	C15—C16—N4	118.3 (3)
C8—C8A—O1	116.8 (3)	C16—C17—C18	119.2 (3)
C4A—C8A—O1	120.5 (3)	C16—C17—H17	120.4
N2—C9—N1	107.4 (3)	C18—C17—H17	120.4
N2—C9—H9	126.3	C17—C18—N5	116.2 (3)
N1—C9—H9	126.3	C17—C18—C13	123.9 (3)
C11—C10—N2	107.3 (3)	N5—C18—C13	119.9 (3)
C8A—O1—C2—O2	−177.4 (3)	C12—N2—C10—C11	178.7 (3)
C8A—O1—C2—C3	1.3 (5)	N2—C10—C11—N1	0.6 (4)
C9—N1—C3—C4	120.5 (4)	C9—N1—C11—C10	−0.5 (4)
C11—N1—C3—C4	−64.0 (5)	C3—N1—C11—C10	−176.6 (3)
C9—N1—C3—C2	−60.9 (5)	O3—C13—C14—C15	171.5 (4)
C11—N1—C3—C2	114.6 (4)	C18—C13—C14—C15	−4.2 (5)
O2—C2—C3—C4	177.9 (4)	O3—C13—C14—N3	−5.2 (5)
O1—C2—C3—C4	−0.7 (5)	C18—C13—C14—N3	179.1 (3)
O2—C2—C3—N1	−0.7 (5)	O4—N3—C14—C15	−50.5 (5)
O1—C2—C3—N1	−179.4 (3)	O5—N3—C14—C15	130.3 (4)
N1—C3—C4—C4A	179.1 (3)	O4—N3—C14—C13	126.5 (4)
C2—C3—C4—C4A	0.6 (5)	O5—N3—C14—C13	−52.7 (5)
C3—C4—C4A—C8A	−1.0 (5)	C13—C14—C15—C16	4.2 (5)
C3—C4—C4A—C5	177.9 (3)	N3—C14—C15—C16	−179.1 (3)
C8A—C4A—C5—C6	−0.7 (5)	C14—C15—C16—C17	−2.4 (5)
C4—C4A—C5—C6	−179.6 (3)	C14—C15—C16—N4	177.7 (3)
C4A—C5—C6—C7	−0.4 (5)	O7—N4—C16—C17	6.1 (5)
C5—C6—C7—C8	1.3 (6)	O6—N4—C16—C17	−174.2 (3)
C6—C7—C8—C8A	−1.1 (6)	O7—N4—C16—C15	−174.1 (3)
C7—C8—C8A—C4A	−0.1 (6)	O6—N4—C16—C15	5.6 (5)
C7—C8—C8A—O1	178.3 (3)	C15—C16—C17—C18	1.2 (5)
C5—C4A—C8A—C8	1.0 (5)	N4—C16—C17—C18	−179.0 (3)
C4—C4A—C8A—C8	179.9 (4)	C16—C17—C18—N5	−178.7 (3)
C5—C4A—C8A—O1	−177.3 (3)	C16—C17—C18—C13	−1.5 (5)
C4—C4A—C8A—O1	1.6 (5)	O8—N5—C18—C17	27.9 (5)
C2—O1—C8A—C8	179.8 (3)	O9—N5—C18—C17	−150.4 (3)
C2—O1—C8A—C4A	−1.8 (5)	O8—N5—C18—C13	−149.4 (3)
C10—N2—C9—N1	0.1 (4)	O9—N5—C18—C13	32.3 (5)
C12—N2—C9—N1	−179.0 (3)	O3—C13—C18—C17	−172.8 (3)
C11—N1—C9—N2	0.3 (4)	C14—C13—C18—C17	2.8 (5)
C3—N1—C9—N2	176.4 (3)	O3—C13—C18—N5	4.3 (5)
C9—N2—C10—C11	−0.4 (4)	C14—C13—C18—N5	179.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O7i	0.95	2.58	3.349 (4)	138
C9—H9···O3	0.95	2.33	3.122 (5)	140
C10—H10···O9ii	0.95	2.51	3.303 (5)	141
C11—H11···O3iii	0.95	2.42	3.196 (5)	139
C11—H11···O5iii	0.95	2.51	3.231 (5)	132
C12—H12A···O2iv	0.98	2.58	3.360 (5)	137
C12—H12B···O2v	0.98	2.48	3.448 (5)	171
C12—H12C···O3iv	0.98	2.39	3.269 (4)	148
C12—H12C···O9iv	0.98	2.42	3.160 (5)	132
C17—H17···O5vi	0.95	2.40	3.345 (5)	172

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O7i	0.95	2.58	3.349 (4)	138
C9—H9⋯O3	0.95	2.33	3.122 (5)	140
C10—H10⋯O9ii	0.95	2.51	3.303 (5)	141
C11—H11⋯O3iii	0.95	2.42	3.196 (5)	139
C11—H11⋯O5iii	0.95	2.51	3.231 (5)	132
C12—H12A⋯O2iv	0.98	2.58	3.360 (5)	137
C12—H12B⋯O2v	0.98	2.48	3.448 (5)	171
C12—H12C⋯O3iv	0.98	2.39	3.269 (4)	148
C12—H12C⋯O9iv	0.98	2.42	3.160 (5)	132
C17—H17⋯O5vi	0.95	2.40	3.345 (5)	172

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