4-(4-Chloro­phen­yl)-3-cyano-7-(4-meth­oxy­phen­yl)-5-oxo-5,6,7,8-tetra­hydro-4H-chromen-2-aminium methano­late

Sun, R.; Wang, K.; Wu, D.-D.; Huang, W.; Ou, Y.-B.

doi:10.1107/S1600536812007088

4-(4-Chlorophenyl)-3-cyano-7-(4-methoxyphenyl)-5-oxo-5,6,7,8-tetrahydro-4H-chromen-2-aminium methanolate

R. Sun, K. Wang, D.-D. Wu, W. Huang and Y.-B. Ou

In the cation of the title organic ion pair compound, C₂₃H₂₀ClN₂O₃⁺·CH₃O⁻, the cyclohexyl 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 R₂²(12) ring motif. The anion interacts with the dimer through an N—H

O hydrogen bond. π–π interactions between pyran rings of adjacent dimers, with a centroid–centroid distance of 3.861 (2) Å, are also observed.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536812007088/rz2709sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536812007088/rz2709Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S1600536812007088/rz2709Isup3.cml Supplementary material

CCDC reference: 872576

checkCIF report

Key indicators

Single-crystal X-ray study
T = 291 K
Mean (C-C) = 0.004 Å
R factor = 0.056
wR factor = 0.132
Data-to-parameter ratio = 16.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT309_ALERT_2_C Single Bonded Oxygen (C-O .GT. 1.3 Ang) ........         O4
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1C    ...          ?
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          8
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          5
PLAT918_ALERT_3_C Reflection(s) # with I(obs) much smaller I(calc)          2
PLAT939_ALERT_3_C Large Value of Not (SHELXL) Weight Optimized S .      23.69

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          1
PLAT003_ALERT_2_G Number of Uiso or Uij Restrained Atom Sites ....         10
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............          3
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n
PLAT793_ALERT_4_G The Model has Chirality at C7      (Verify) ....          R
PLAT793_ALERT_4_G The Model has Chirality at C14     (Verify) ....          S
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          9
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......          !

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   7 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   9 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check

Comment top

Chromenes and their benzo-derivatives are very important heterocyclic compounds, in particular due to their application in a variety of industrial, biological and chemical syntheses (Geen et al., 1996; Ercole et al., 2009; Takakazu et al., 2001). Herein, we report the synthesis and crystal structure of a new chromene derivative.

The molecular structure of the title compound is shown in Figure 1. In the cation of this novel organic ion pair compound, the cyclohexyl ring shows in a half-boat conformation. The dihedral angles between the C1–C6 and C16–C21 benzene rings and the pyran ring are 83.14 (7) and 73.18 (9)°, respectively. In the crystal structure (Fig. 2), centrosymmetrically related cations form a dimer by two intermolecular N—H···N hydrogen bonds (Table 1). Between neighbouring dimers, π–π interactions between pyran rings (centroid-centroid distance = 3.861 (2) Å) are observed. Furthermore, the organic cations and the methanolate anion are linked by intermolecular N—H···O hydrogen bonds.

Related literature top

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 top

The title compound were synthesized by the reaction of 4-chlorobenzaldehyde (10 mmol), malononitrile (10 mmol) and 5-(4-methoxyphenyl)-1,3-cyclo-hexane-dione (10 mmol) according to the similar synthesis route reported in the literature (Wen et al., 2006; Kidwai et al., 2005). Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of a methanol solution at room temperature for one week.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement.
	Fig. 2. Packing diagram of the title compound viewed along the a axis. Intermolecular hydrogen bonds are shown as dashed lines.

4-(4-Chlorophenyl)-3-cyano-7-(4-methoxyphenyl)-5-oxo-5,6,7,8-tetrahydro- 4H-chromen-2-aminium methanolate top

Crystal data top

C₂₃H₂₀ClN₂O₃⁺·CH₃O⁻	F(000) = 920
M_r = 438.89	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0457P)² + 1.6707P] where P = (F_o² + 2F_c²)/3
4566 reflections	(Δ/σ)_max = 0.001
283 parameters	Δρ_max = 0.18 e Å⁻³
9 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₂₃H₂₀ClN₂O₃⁺·CH₃O⁻	V = 2331.5 (5) Å³
M_r = 438.89	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.4408 (12) Å	µ = 0.20 mm⁻¹
b = 26.844 (4) Å	T = 291 K
c = 10.4615 (13) Å	0.28 × 0.24 × 0.20 mm
β = 100.398 (3)°

Data collection top

Bruker SMART APEX CCD diffractometer	4566 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3554 reflections with I > 2σ(I)
T_min = 0.949, T_max = 0.963	R_int = 0.042
12431 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	9 restraints
wR(F²) = 0.132	H-atom parameters constrained
S = 1.07	Δρ_max = 0.18 e Å⁻³
4566 reflections	Δρ_min = −0.19 e Å⁻³
283 parameters

Special details top

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) C6

Rms 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) C11

Rms 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) C21

Rms 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) −x+2, −y+1, −z+1; (ii) −x+3, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₂₃H₂₀ClN₂O₃⁺·CH₃O⁻
M_r	438.89
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	291
a, b, c (Å)	8.4408 (12), 26.844 (4), 10.4615 (13)
β (°)	100.398 (3)
V (Å³)	2331.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.28 × 0.24 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.949, 0.963
No. of measured, independent and observed [I > 2σ(I)] reflections	12431, 4566, 3554
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.132, 1.07
No. of reflections	4566
No. of parameters	283
No. of restraints	9
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.19

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).