4-(4-Chloro-phen-yl)-3-cyano-7-(4-meth-oxy-phen-yl)-5-oxo-5,6,7,8-tetra-hydro-4H-chromen-2-aminium methano-late.

In the cation of the title organic ion pair compound, C(23)H(20)ClN(2)O(3) (+)·CH(3)O(-), the cyclo-hexyl ring shows a half-boat conformation and the dihedral angles between two benzene rings and the pyran ring are 83.14 (7) and 73.18 (9)°. In the crystal, centrosymmetrically related cations are linked into a dimer by pairs of N-H⋯N hydrogen bonds, generating an R(2) (2)(12) ring motif. The anion inter-acts with the dimer through an N-H⋯O hydrogen bond. π-π inter-actions between pyran rings of adjacent dimers, with a centroid-centroid distance of 3.861 (2) Å, are also observed.

Related literature

For background to chromene and its derivatives, see: Geen et al. (1996 ▶); Ercole et al. (2009 ▶); Takakazu et al. (2001 ▶). For the synthesis, see: Wen et al. (2006 ▶); Kidwai et al. (2005 ▶).

Experimental

Crystal data

C23H20ClN2O3 +·CH3O−

M = 438.89

Monoclinic,

a = 8.4408 (12) Å

b = 26.844 (4) Å

c = 10.4615 (13) Å

β = 100.398 (3)°

V = 2331.5 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.20 mm−1

T = 291 K

0.28 × 0.24 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.949, T max = 0.963

12431 measured reflections

4566 independent reflections

3554 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.132

S = 1.07

4566 reflections

283 parameters

9 restraints

H-atom parameters constrained

Δρmax = 0.18 e Å−3

Δρmin = −0.19 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812007088/rz2709sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812007088/rz2709Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812007088/rz2709Isup3.cml

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

C23H20ClN2O3+·CH3O−	F(000) = 920
Mr = 438.89	Dx = 1.250 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1476 reflections
a = 8.4408 (12) Å	θ = 2.6–19.7°
b = 26.844 (4) Å	µ = 0.20 mm−1
c = 10.4615 (13) Å	T = 291 K
β = 100.398 (3)°	Block, colourless
V = 2331.5 (5) Å3	0.28 × 0.24 × 0.20 mm
Z = 4

Bruker SMART APEX CCD diffractometer	4566 independent reflections
Radiation source: sealed tube	3554 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
φ and ω scans	θmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
Tmin = 0.949, Tmax = 0.963	k = −26→33
12431 measured reflections	l = −8→12

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0457P)2 + 1.6707P] where P = (Fo2 + 2Fc2)/3
4566 reflections	(Δ/σ)max = 0.001
283 parameters	Δρmax = 0.18 e Å−3
9 restraints	Δρmin = −0.19 e Å−3

Experimental. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)7.1912 (0.0049) x + 12.2668 (0.0260) y - 4.2393 (0.0113) z = 8.2055 (0.0187)* -0.0076 (0.0019) C1 * -0.0037 (0.0019) C2 * 0.0134 (0.0020) C3 * -0.0120 (0.0019) C4 * 0.0003 (0.0019) C5 * 0.0095 (0.0020) C6Rms deviation of fitted atoms = 0.0090- 4.4632 (0.0075) x + 22.2337 (0.0159) y + 2.9074 (0.0097) z = 7.7773 (0.0151)Angle to previous plane (with approximate e.s.d.) = 83.14 (7)* -0.0358 (0.0017) C7 * 0.0190 (0.0018) C8 * 0.0065 (0.0017) C9 * -0.0138 (0.0016) O1 * -0.0093 (0.0017) C10 * 0.0334 (0.0018) C11Rms deviation of fitted atoms = 0.0227- 4.8454 (0.0082) x - 5.2426 (0.0307) y + 9.2662 (0.0059) z = 3.3249 (0.0131)Angle to previous plane (with approximate e.s.d.) = 73.18 (9)* -0.0166 (0.0021) C16 * 0.0117 (0.0020) C17 * 0.0054 (0.0019) C18 * -0.0182 (0.0020) C19 * 0.0126 (0.0020) C20 * 0.0050 (0.0021) C21Rms deviation of fitted atoms = 0.0126

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	1.1955 (3)	0.37698 (10)	1.1850 (2)	0.0370 (6)
C2	1.2679 (3)	0.38035 (10)	1.3165 (3)	0.0414 (6)
H2	1.2491	0.4078	1.3661	0.050*
C3	1.3696 (3)	0.34133 (10)	1.3721 (3)	0.0420 (6)
H3	1.4215	0.3430	1.4584	0.050*
C4	1.3903 (3)	0.30112 (10)	1.2970 (3)	0.0397 (6)
C5	1.3237 (3)	0.29740 (10)	1.1703 (3)	0.0404 (6)
H5	1.3429	0.2697	1.1220	0.048*
C6	1.2232 (3)	0.33683 (10)	1.1117 (3)	0.0422 (6)
H6	1.1767	0.3353	1.0242	0.051*
C7	1.0925 (3)	0.42032 (10)	1.1254 (2)	0.0348 (5)
H7	1.0677	0.4414	1.1957	0.042*
C8	1.1785 (3)	0.45122 (9)	1.0401 (2)	0.0335 (5)
C9	1.1299 (3)	0.45753 (9)	0.9128 (2)	0.0357 (5)
C10	0.8945 (3)	0.40928 (10)	0.9150 (2)	0.0371 (5)
C11	0.9333 (3)	0.40222 (10)	1.0433 (2)	0.0349 (5)
C12	0.8178 (3)	0.37688 (10)	1.1067 (3)	0.0395 (6)
C13	0.6618 (3)	0.35784 (12)	1.0346 (3)	0.0461 (7)
H13A	0.6427	0.3248	1.0659	0.055*
H13B	0.5755	0.3793	1.0512	0.055*
C14	0.6599 (4)	0.35575 (12)	0.8962 (3)	0.0492 (7)
H14	0.7259	0.3259	0.8936	0.059*
C15	0.7507 (3)	0.39052 (10)	0.8273 (2)	0.0384 (5)
H15A	0.7831	0.3736	0.7543	0.046*
H15B	0.6821	0.4183	0.7938	0.046*
C16	0.5059 (3)	0.33767 (11)	0.8126 (3)	0.0454 (7)
C17	0.3746 (3)	0.37013 (10)	0.7654 (3)	0.0420 (6)
H17	0.3815	0.4034	0.7903	0.050*
C18	0.2351 (3)	0.35330 (10)	0.6822 (3)	0.0422 (6)
H18	0.1502	0.3747	0.6512	0.051*
C19	0.2300 (3)	0.30415 (9)	0.6492 (3)	0.0382 (6)
C20	0.3501 (3)	0.27166 (10)	0.6969 (3)	0.0409 (6)
H20	0.3393	0.2381	0.6751	0.049*
C21	0.4885 (3)	0.28832 (11)	0.7779 (3)	0.0475 (7)
H21	0.5704	0.2659	0.8090	0.057*
C22	1.3256 (3)	0.47351 (9)	1.0965 (2)	0.0336 (5)
C23	−0.0285 (3)	0.31490 (11)	0.5070 (3)	0.0453 (7)
H23A	−0.0693	0.3324	0.5742	0.068*
H23B	−0.1129	0.2951	0.4581	0.068*
H23C	0.0094	0.3384	0.4503	0.068*
C24	0.7601 (4)	0.45139 (11)	0.4691 (3)	0.0514 (7)
H24A	0.6616	0.4430	0.4118	0.077*
H24B	0.7419	0.4792	0.5224	0.077*
H24C	0.7964	0.4233	0.5234	0.077*
Cl1	1.51263 (8)	0.25245 (3)	1.36958 (7)	0.04615 (19)
N1	1.2003 (3)	0.48469 (10)	0.8308 (3)	0.0576 (7)
H1A	1.1508	0.4791	0.7496	0.086*
H1B	1.3035	0.4761	0.8393	0.086*
H1C	1.1932	0.5169	0.8494	0.086*
N2	1.4468 (3)	0.49159 (8)	1.1468 (2)	0.0406 (5)
O1	0.9900 (2)	0.43720 (7)	0.84663 (16)	0.0390 (4)
O2	0.8398 (2)	0.37310 (7)	1.22654 (17)	0.0427 (5)
O3	0.1011 (2)	0.28334 (7)	0.56417 (18)	0.0450 (5)
O4	0.8804 (2)	0.46438 (8)	0.3939 (2)	0.0527 (5)

	U11	U22	U33	U12	U13	U23
C1	0.0339 (13)	0.0411 (14)	0.0363 (13)	−0.0051 (11)	0.0073 (11)	0.0039 (11)
C2	0.0393 (14)	0.0445 (15)	0.0361 (14)	0.0022 (12)	−0.0043 (11)	0.0039 (11)
C3	0.0450 (15)	0.0428 (15)	0.0342 (13)	0.0036 (12)	−0.0037 (11)	0.0025 (11)
C4	0.0350 (13)	0.0454 (15)	0.0416 (12)	0.0154 (12)	0.0149 (10)	0.0110 (11)
C5	0.0438 (14)	0.0379 (14)	0.0395 (12)	0.0075 (12)	0.0075 (11)	0.0056 (11)
C6	0.0412 (14)	0.0376 (14)	0.0425 (14)	0.0144 (12)	−0.0063 (11)	−0.0016 (11)
C7	0.0243 (11)	0.0400 (14)	0.0390 (13)	−0.0040 (10)	0.0023 (10)	0.0052 (11)
C8	0.0336 (12)	0.0288 (12)	0.0365 (13)	0.0003 (10)	0.0022 (10)	0.0025 (10)
C9	0.0287 (12)	0.0336 (13)	0.0423 (14)	−0.0044 (10)	−0.0005 (10)	−0.0013 (11)
C10	0.0327 (12)	0.0427 (14)	0.0348 (13)	0.0024 (10)	0.0032 (9)	0.0024 (10)
C11	0.0294 (12)	0.0444 (14)	0.0324 (12)	0.0032 (11)	0.0091 (10)	−0.0027 (11)
C12	0.0320 (13)	0.0447 (15)	0.0429 (15)	−0.0038 (11)	0.0095 (11)	0.0070 (12)
C13	0.0394 (15)	0.0538 (17)	0.0440 (15)	−0.0005 (13)	0.0042 (12)	0.0026 (13)
C14	0.0443 (15)	0.0549 (17)	0.0443 (16)	−0.0075 (12)	−0.0028 (12)	0.0041 (13)
C15	0.0368 (12)	0.0387 (14)	0.0363 (13)	−0.0032 (10)	−0.0020 (10)	0.0004 (10)
C16	0.0443 (15)	0.0448 (16)	0.0416 (15)	0.0130 (12)	−0.0069 (12)	−0.0059 (12)
C17	0.0387 (13)	0.0426 (15)	0.0444 (15)	0.0020 (11)	0.0067 (11)	0.0074 (12)
C18	0.0410 (14)	0.0388 (14)	0.0446 (15)	−0.0056 (11)	0.0023 (11)	0.0068 (11)
C19	0.0335 (13)	0.0352 (13)	0.0418 (14)	0.0139 (11)	−0.0038 (11)	−0.0037 (11)
C20	0.0331 (13)	0.0365 (14)	0.0500 (15)	0.0051 (11)	−0.0009 (11)	0.0061 (11)
C21	0.0398 (14)	0.0450 (16)	0.0517 (16)	−0.0135 (12)	−0.0074 (12)	0.0141 (13)
C22	0.0317 (13)	0.0297 (12)	0.0410 (13)	−0.0070 (10)	0.0106 (11)	0.0027 (10)
C23	0.0370 (14)	0.0477 (16)	0.0441 (15)	0.0007 (12)	−0.0122 (11)	0.0103 (12)
C24	0.0565 (18)	0.0480 (17)	0.0529 (17)	0.0150 (14)	0.0186 (14)	0.0118 (14)
Cl1	0.0419 (4)	0.0492 (4)	0.0497 (4)	0.0160 (3)	0.0148 (3)	0.0153 (3)
N1	0.0484 (14)	0.0671 (17)	0.0570 (15)	−0.0033 (13)	0.0080 (12)	0.0131 (13)
N2	0.0376 (12)	0.0419 (12)	0.0391 (12)	−0.0072 (10)	−0.0020 (9)	0.0002 (10)
O1	0.0356 (9)	0.0435 (10)	0.0372 (10)	−0.0063 (8)	0.0046 (7)	0.0024 (8)
O2	0.0417 (10)	0.0461 (11)	0.0390 (10)	−0.0109 (8)	0.0037 (8)	0.0156 (8)
O3	0.0397 (10)	0.0438 (11)	0.0458 (11)	0.0018 (8)	−0.0075 (8)	0.0069 (8)
O4	0.0561 (12)	0.0491 (12)	0.0532 (12)	0.0147 (10)	0.0108 (10)	0.0063 (9)

C1—C6	1.367 (4)	C14—C15	1.476 (4)
C1—C2	1.404 (4)	C14—C16	1.509 (4)
C1—C7	1.518 (4)	C14—H14	0.9800
C2—C3	1.411 (4)	C15—H15A	0.9700
C2—H2	0.9300	C15—H15B	0.9700
C3—C4	1.365 (4)	C16—C21	1.375 (4)
C3—H3	0.9300	C16—C17	1.426 (4)
C4—C5	1.347 (4)	C17—C18	1.407 (4)
C4—Cl1	1.751 (3)	C17—H17	0.9300
C5—C6	1.424 (3)	C18—C19	1.363 (4)
C5—H5	0.9300	C18—H18	0.9300
C6—H6	0.9300	C19—C20	1.362 (3)
C7—C8	1.499 (3)	C19—O3	1.392 (3)
C7—C11	1.537 (3)	C20—C21	1.388 (4)
C7—H7	0.9800	C20—H20	0.9300
C8—C9	1.331 (3)	C21—H21	0.9300
C8—C22	1.408 (3)	C22—N2	1.168 (3)
C9—N1	1.343 (3)	C23—O3	1.427 (3)
C9—O1	1.370 (3)	C23—H23A	0.9600
C10—C11	1.336 (3)	C23—H23B	0.9600
C10—O1	1.390 (3)	C23—H23C	0.9600
C10—C15	1.472 (3)	C24—O4	1.435 (3)
C11—C12	1.445 (3)	C24—H24A	0.9600
C12—O2	1.238 (3)	C24—H24B	0.9600
C12—C13	1.485 (4)	C24—H24C	0.9600
C13—C14	1.446 (4)	N1—H1A	0.8900
C13—H13A	0.9700	N1—H1B	0.8900
C13—H13B	0.9700	N1—H1C	0.8900
C6—C1—C2	120.8 (2)	C13—C14—H14	98.9
C6—C1—C7	121.2 (2)	C15—C14—H14	98.9
C2—C1—C7	118.0 (2)	C16—C14—H14	98.9
C1—C2—C3	118.7 (3)	C10—C15—C14	110.8 (2)
C1—C2—H2	120.6	C10—C15—H15A	109.5
C3—C2—H2	120.6	C14—C15—H15A	109.5
C4—C3—C2	118.8 (2)	C10—C15—H15B	109.5
C4—C3—H3	120.6	C14—C15—H15B	109.5
C2—C3—H3	120.6	H15A—C15—H15B	108.1
C5—C4—C3	123.4 (2)	C21—C16—C17	117.3 (3)
C5—C4—Cl1	118.7 (2)	C21—C16—C14	120.2 (3)
C3—C4—Cl1	117.8 (2)	C17—C16—C14	122.6 (3)
C4—C5—C6	118.6 (3)	C18—C17—C16	122.0 (3)
C4—C5—H5	120.7	C18—C17—H17	119.0
C6—C5—H5	120.7	C16—C17—H17	119.0
C1—C6—C5	119.6 (2)	C19—C18—C17	116.9 (3)
C1—C6—H6	120.2	C19—C18—H18	121.6
C5—C6—H6	120.2	C17—C18—H18	121.6
C8—C7—C1	111.4 (2)	C20—C19—C18	122.7 (3)
C8—C7—C11	108.1 (2)	C20—C19—O3	114.9 (2)
C1—C7—C11	111.4 (2)	C18—C19—O3	122.4 (2)
C8—C7—H7	108.6	C19—C20—C21	120.4 (3)
C1—C7—H7	108.6	C19—C20—H20	119.8
C11—C7—H7	108.6	C21—C20—H20	119.8
C9—C8—C22	117.0 (2)	C16—C21—C20	120.7 (3)
C9—C8—C7	124.8 (2)	C16—C21—H21	119.7
C22—C8—C7	118.1 (2)	C20—C21—H21	119.7
C8—C9—N1	128.0 (2)	N2—C22—C8	178.0 (3)
C8—C9—O1	122.5 (2)	O3—C23—H23A	109.5
N1—C9—O1	109.5 (2)	O3—C23—H23B	109.5
C11—C10—O1	122.2 (2)	H23A—C23—H23B	109.5
C11—C10—C15	127.1 (2)	O3—C23—H23C	109.5
O1—C10—C15	110.7 (2)	H23A—C23—H23C	109.5
C10—C11—C12	117.7 (2)	H23B—C23—H23C	109.5
C10—C11—C7	123.2 (2)	O4—C24—H24A	109.5
C12—C11—C7	119.1 (2)	O4—C24—H24B	109.5
O2—C12—C11	120.9 (2)	H24A—C24—H24B	109.5
O2—C12—C13	116.3 (2)	O4—C24—H24C	109.5
C11—C12—C13	122.6 (2)	H24A—C24—H24C	109.5
C14—C13—C12	111.8 (2)	H24B—C24—H24C	109.5
C14—C13—H13A	109.3	C9—N1—H1A	109.5
C12—C13—H13A	109.3	C9—N1—H1B	109.5
C14—C13—H13B	109.3	H1A—N1—H1B	109.5
C12—C13—H13B	109.3	C9—N1—H1C	109.5
H13A—C13—H13B	107.9	H1A—N1—H1C	109.5
C13—C14—C15	123.5 (3)	H1B—N1—H1C	109.5
C13—C14—C16	116.5 (3)	C9—O1—C10	118.80 (19)
C15—C14—C16	112.9 (2)	C19—O3—C23	118.8 (2)
C6—C1—C2—C3	−0.2 (4)	C7—C11—C12—O2	5.7 (4)
C7—C1—C2—C3	−177.4 (2)	C10—C11—C12—C13	1.3 (4)
C1—C2—C3—C4	−1.8 (4)	C7—C11—C12—C13	−179.5 (2)
C2—C3—C4—C5	2.7 (4)	O2—C12—C13—C14	−169.7 (3)
C2—C3—C4—Cl1	−178.2 (2)	C11—C12—C13—C14	15.3 (4)
C3—C4—C5—C6	−1.5 (4)	C12—C13—C14—C15	−30.8 (4)
Cl1—C4—C5—C6	179.5 (2)	C12—C13—C14—C16	−179.1 (2)
C2—C1—C6—C5	1.4 (4)	C11—C10—C15—C14	−7.9 (4)
C7—C1—C6—C5	178.5 (2)	O1—C10—C15—C14	172.8 (2)
C4—C5—C6—C1	−0.6 (4)	C13—C14—C15—C10	27.5 (4)
C6—C1—C7—C8	−72.7 (3)	C16—C14—C15—C10	176.7 (2)
C2—C1—C7—C8	104.4 (3)	C13—C14—C16—C21	−94.4 (4)
C6—C1—C7—C11	48.2 (3)	C15—C14—C16—C21	114.1 (3)
C2—C1—C7—C11	−134.7 (2)	C13—C14—C16—C17	86.3 (4)
C1—C7—C8—C9	117.3 (3)	C15—C14—C16—C17	−65.2 (4)
C11—C7—C8—C9	−5.5 (3)	C21—C16—C17—C18	−2.6 (4)
C1—C7—C8—C22	−59.6 (3)	C14—C16—C17—C18	176.7 (3)
C11—C7—C8—C22	177.6 (2)	C16—C17—C18—C19	0.5 (4)
C22—C8—C9—N1	−3.3 (4)	C17—C18—C19—C20	2.4 (4)
C7—C8—C9—N1	179.7 (3)	C17—C18—C19—O3	−177.8 (2)
C22—C8—C9—O1	179.2 (2)	C18—C19—C20—C21	−3.1 (4)
C7—C8—C9—O1	2.3 (4)	O3—C19—C20—C21	177.0 (3)
O1—C10—C11—C12	173.9 (2)	C17—C16—C21—C20	1.9 (4)
C15—C10—C11—C12	−5.3 (4)	C14—C16—C21—C20	−177.4 (3)
O1—C10—C11—C7	−5.2 (4)	C19—C20—C21—C16	0.8 (4)
C15—C10—C11—C7	175.6 (2)	C8—C9—O1—C10	0.6 (4)
C8—C7—C11—C10	6.9 (3)	N1—C9—O1—C10	−177.3 (2)
C1—C7—C11—C10	−115.9 (3)	C11—C10—O1—C9	1.0 (4)
C8—C7—C11—C12	−172.2 (2)	C15—C10—O1—C9	−179.7 (2)
C1—C7—C11—C12	65.0 (3)	C20—C19—O3—C23	−178.5 (2)
C10—C11—C12—O2	−173.5 (3)	C18—C19—O3—C23	1.6 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4i	0.89	2.12	2.698 (4)	122
N1—H1B···N2ii	0.89	2.26	3.014 (5)	142

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4i	0.89	2.12	2.698 (4)	122
N1—H1B⋯N2ii	0.89	2.26	3.014 (5)	142

Symmetry codes: (i) ; (ii) .