Crystal structure of (1Z)-1-(4-chloro­benzyl­idene)-5-(4-meth­oxy­phen­yl)-3-oxopyrazolidin-1-ium-2-ide

Mangwala Kimpende, P.; Doan, T.K.O.; Vu, Q.T.; Van Meervelt, L.

doi:10.1107/S1600536814014445

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ISSN: 2056-9890

Volume 70| Part 8| August 2014| Pages 84-86

doi:10.1107/S1600536814014445

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Crystal structure of (1Z)-1-(4-chlorobenzylidene)-5-(4-methoxyphenyl)-3-oxopyrazolidin-1-ium-2-ide

Peter Mangwala Kimpende,^a Thi Kieu Oanh Doan,^b Quoc Trung Vu ^b and Luc Van Meervelt ^c ^*

^aChemistry Department, University of Kinshasa, Kinshasa XI BP 212, Democratic Republic of the Congo, ^bFaculty of Chemistry, Hanoi National University of Education, 136 – Xuan Thuy – Cau Giay, Hanoi, Vietnam, and ^cChemistry Department, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven (Heverlee), Belgium
^*Correspondence e-mail: luc.vanmeervelt@chem.kuleuven.be

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 4 June 2014; accepted 18 June 2014; online 19 July 2014)

The title molecule, C₁₇H₁₅ClN₂O₂, is L-shaped with the 4-chlorobenzylidene ring almost coplanar with the planar pyrazolidine ring (r.m.s. deviation = 0.020 Å), making a dihedral angle of 4.83 (17)°. The 4-methoxyphenyl ring is almost normal to the mean plane of the pyrazolidine ring and the 4-chlorobenzylidene ring, with dihedral angles of 87.36 (17) and 89.23 (16)°, respectively. The pyrazolidine ring occurs in the betaine form with a Z configuration for the exocyclic C=N bond. In the crystal, C—H⋯O and C—H⋯π interactions generate ribbons of molecules along [1-10].

Keywords: crystal structure; pyrazolidinium ylide; betaine structure.

CCDC reference: 1006910

1. Chemical context

Acyclic azomethine imides are difficult to synthesize and have thus rarely been explored. However, cyclic azomethine imides of the 3-oxopyrazolidin-1-um-2-ide type are generated under mild conditions and have largely been used for the novel synthesis of heterocyclic compounds (Schantl, 2004 ; Padwa & Pearson, 2003 ) such as monocyclic and bicyclic pyrazolidinones (Zhou et al., 2013 ; Suarez et al., 2005 ) and other bicyclic heterocycles (Svete, 2006 ; Xu et al., 2013 ). Since numerous pyrazole derivatives have found use in pharmaceutical, agrochemical and other applications, for example, sildenafil or Viagra (Mulhall, 1997 ), lonazolac (Vinge & Bjorkman, 1986 ), merpirizole (Naito et al., 1969 ), the bicyclic pyrazolidinone LY 186826 (Indelicato & Pasini, 1988 ) and the developing agent in photography, phenidone, a part of our studies is focused on the synthesis of functionalized pyrazoles. For this purpose, the title compound was synthesized and the molecular and crystal structure are reported herein.

2. Structural Commentary

The pyrazolidine ring is planar with a maximal deviation of 0.017 (3) Å for atom C10. The 4-chlorobenzyl aromatic ring and the pyrazolidine ring are almost coplanar, making a dihedral angle of 4.83 (17)°, whereas the mean plane through the 4-methoxyphenyl aromatic ring is almost perpendicular [87.36 (17)°] to the pyrazolidine plane. The aromatic rings are inclined to one another at 89.23 (16)°. The configuration of the exocyclic C1=N7 bond is Z. The pyrazolidine ring shows a betaine character with opposite charges located on adjacent nitrogen atoms, N1 and N2. The N1—N2 bond distance of 1.362 (3) Å agrees with the average value of 1.357 (7) Å obtained for N⁺—N⁻ in pyrazolidine rings found in the Cambridge Structural Database (CSD, Version 5.35, February 2014; Allen, 2002 ). The intramolecular C3—H3⋯N2 interaction (Table 1 and Fig. 1) is also observed in similar compounds found in the CSD.

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯N2	0.96 (4)	2.31 (3)	2.934 (4)	122 (1)
C3—H3⋯O1ⁱ	0.96 (4)	2.52 (2)	3.152 (4)	124 (1)
C17—H17C⋯Cgⁱⁱ	1.02 (3)	2.73 (3)	3.551 (4)	138 (2)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x+1, y+1, z.

Figure 1
Molecular structure of the title molecule, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The intramolecular C—H⋯N interaction is drawn as a dashed line (see Table 1

for details).

3. Supramolecular features

In the crystal packing C–H⋯O hydrogen bonds are observed (Table 1 and Fig. 2), resulting in the formation of inversion dimers with R₂²(16) loops. Furthermore, the aromatic ring of the 4-chlorobenzyl substituent is involved in C—H⋯π interactions (Table 1 and Fig. 2), forming ribbons of dimers propagating along [1 $[\overline{1}]$ 0].

Figure 2
Crystal packing for the title compound viewed along the a axis, with the C—H⋯π and C—H⋯O interactions drawn as dashed lines (see Table 1

for details).

4. Database survey

The Cambridge Structural Database contains 15 crystal structures containing a similar 1-methylidene-3-oxopyrazolidin-1-ium-2-ide fragment. For the 12 structures bearing a 1-benzylidene substituent, the dihedral angle between its aromatic ring and the pyrazolidine ring varies from 0.0 to 65.6° depending on the further substitution of the 1-benzylidene substituent. A fit of the common parts of the title compound and (1Z)-1-(4-chlorobenzylidene-5,5-dimethyl-3-oxopyrazolidin-1-ium-2-ide (refcode: BOLJUH; Kulpe et al., 1983 ) results in an r.m.s. deviation of 0.069 Å.

5. Synthesis and crystallization

The starting material, ethyl p-methoxycinnamate, was isolated from Kaempferia galanga L., a traditional medicinal plant in Vietnam (Do, 2011 ). The reaction scheme to synthesize the title compound, (2), is given in Fig. 3.

Figure 3
Reaction scheme for the title compound.

Synthesis of 5-p-methoxyphenylpyrazolidin-3-one (1): A solution of 1.03 g (5 mmol) of ethyl p-methoxycinnamate, 0.5 ml of N₂H₄·H₂O 80% in 5 ml of ethanol was refluxed for 24 h. To the cool mixture 0.2 ml of H₂O was added and allowed to stand. The resulting precipitate was collected and recrystallized from ethanol to give 0.54 g (yield 56%) of (1) in the form of white crystals; m.p. 442–443 K. IR (KBr, cm⁻¹): 3229, 3180 (NH); 3041, 2951, 2834 (C—H), 1675 (C=O); 1605, 1520 (phenyl C=C). ¹H NMR (d₆-DMSO, δ, ppm; J, Hz): 9.14 s (N²H); 5.46 broadened s, (N¹H); 2.63 dd, ²J 15.5, ³J 7.5 (H^4a); 2.37 dd, ²J 15.5, ³J 8.0 (H^4b); 4.52 t, ³J 7.5 (H⁵); 7.32 d, ³J 8.5 (2H, H^o); 6.91 d, ³J 8.5 (2H, H^m); 3.74 s (3H, MeO). ¹³C NMR [d₆-DMSO, δ, p.p.m., according to the HSQC and HMBC spectra of (1)]: 175.37 (C³), 39.00 (C⁴), 59.87 (C⁵), 132.37 (Cⁱ), 127.85 (C^o), 113.66 (C^m), 158.51 (C^p), 55.06 (MeO). Analysis: calculated for C₁₀H₁₂N₂O₂: C, 62.49; H, 6.29; N, 14.57; found: C, 62.71; H, 6.08; N, 14.29.

Synthesis of 1-(p-chlorobenzylidene)-5-(p-methoxyphenyl)-3-oxopyrazolidin-1-ium-2-ide (2): A solution of 0.192 g (1 mmol) of (1) and 0.141 g (1 mmol) of 4-chlorobenzaldehyde in 5 ml of ethanol was refluxed for 6 h. The reaction mixture was allowed to cool. The resulting precipitate was collected and recrystallized from ethanol to give 0.22 g (yield 70%) of (2) as white crystals; m.p. 467–468 K. IR (KBr, cm⁻¹): 3095, 3052, 2930, 2852 (C-H), 1676 (C=O); 1587, 1563, 1512 (phenyl C=C). Analysis: calculated for C₁₇H₁₅ClN₂O₂: C, 64.87; H, 4.80; N, 8.90. Found: C, 65.08; H, 4.59; N, 8.64.

Colourless plate-like crystals of (2) suitable for X-ray diffraction were obtained by slow evaporation from a water solution acidified with HCl at room temperature.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were refined using a riding model with stretchable C—H distances, and with U_iso = 1.5U_eq(C-methyl) and = 1.2U_eq(C) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₅ClN₂O₂
M_r	314.76
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	5.6966 (6), 10.6852 (13), 12.7750 (17)
α, β, γ (°)	101.573 (7), 100.620 (7), 101.311 (6)
V (Å³)	726.47 (15)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	2.40
Crystal size (mm)	0.55 × 0.1 × 0.05

Data collection
Diffractometer	Bruker SMART 6000
Absorption correction	Multi-scan (SADABS; Bruker, 2003 )
T_min, T_max	0.695, 0.887
No. of measured, independent and observed [I > 2σ(I)] reflections	13302, 2723, 2053
R_int	0.093
(sin θ/λ)_max (Å⁻¹)	0.614

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.171, 1.06
No. of reflections	2723
No. of parameters	212
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.52
Computer programs: SMART and SAINT (Bruker, 2003), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1006910

Crystal structure: contains datablock 2. DOI: 10.1107/S1600536814014445/su0007sup1.cif

Structure factors: contains datablock 2. DOI: 10.1107/S1600536814014445/su00072sup2.hkl

Supporting information file. DOI: 10.1107/S1600536814014445/su00072sup3.cml

checkCIF report

Chemical context top

Acyclic azomethine imides are difficult to synthesize and have thus rarely been explored. However, cyclic azomethine imides of the 3-oxopyrazolidin-1-um-2-ide type are generated under mild conditions and have largely been used for the novel synthesis of heterocyclic compounds (Schantl, 2004; Padwa & Pearson, 2003) such as monocyclic and bicyclic pyrazolidinones (Zhou et al., 2013; Suarez et al., 2005) and other bicyclic heterocycles (Svete, 2006; Xu et al., 2013). Since numerous pyrazole derivatives have found use in pharmaceutical, agrochemical and other applications, for example, sildenafil or Viagra (Mulhall, 1997), lonazolac (Vinge & Bjorkman, 1986), merpirizole (Naito et al., 1969), the bicyclic pyrazolidinone LY 186826 (Indelicato & Pasini, 1988) and the developing agent in photography phenidone, a part of our studies is focused on the synthesis of functionalized pyrazoles. For this purpose, the title compound was synthesized and the molecular and crystal structure are reported herein.

Structural Commentary top

The pyrazolidine ring is planar with a maximal deviation of 0.017 (3) Å for atom C10. The 4-chlorobenzyl aromatic ring and the pyrazolidine ring are almost coplanar, making a dihedral angle of 4.83 (17)°, whereas the mean plane through the 4-methoxyphenyl aromatic ring is almost perpendicular [87.36 (17)°] to the pyrazolidine plane. The aromatic rings are inclined to one another at 89.23 (16)°. The conformation of the exocyclic C1═N7 bond is Z. The pyrazolidine ring shows a betaine character with opposite charges located on adjacent nitrogen atoms, N1 and N2. The N1—N2 bond distance of 1.362 (3) Å agrees with the average value of 1.357 (7) Å obtained for N⁺—N^- in pyrazolidine rings found in the Cambridge Structural Database (CSD, Version 5.35, November 2013; Allen, 2002). The intramolecular C3—H3···N2 interaction (Table 1 and Fig. 1) is also observed in similar compounds found in the CSD.

Supramolecular features top

In the crystal packing C–H···O hydrogen bonds are observed (Table 1 and Fig. 2), resulting in the formation of inversion dimers with R²₂(16) loops. Furthermore, the aromatic ring of the 4-chlorobenzyl substituent is involved in C—H···π interactions (Table 1 and Fig. 2), forming ribbons of dimers propagating along [110].

Database survey top

Synthesis and crystallization top

The starting material, ethyl p-methoxycinnamate, was isolated from Kaempferia galanga L., a traditional medicinal plant in Vietnam (Do, 2011).

Synthesis of 5-p-methoxyphenylpyrazolidin-3-one (1)

A solution of 1.03 g (5 mmol) of ethyl p-methoxycinnamate, 0.5 ml of N₂H₄.H₂O 80% in 5 ml of ethanol was refluxed for 24 hours. To the cool mixture 0.2 ml of H₂O was added and allowed to stand. The resulting precipitate was collected and recrystallized from ethanol to give 0.54 g (yield 56%) of (1) in the form of white crystals; m.p. 442–443 K. IR (KBr, cm^-1): 3229, 3180 (NH); 3041, 2951, 2834 (C—H), 1675 (C=O); 1605, 1520 (phenyl C=C). ¹H NMR (d₆-DMSO, δ, ppm; J, Hz): 9.14 s (N²H); 5.46 broadened s, (N¹H); 2.63 dd, ²J 15.5, ³J 7.5 (H^4a); 2.37 dd, ²J 15.5, ³J 8.0 (H^4b); 4.52 t, ³J 7.5 (H⁵); 7.32 d, ³J 8.5 (2H, H^o); 6.91 d, ³J 8.5 (2H, H^m); 3.74 s (3H, MeO). ¹³C NMR [d₆-DMSO, δ, ppm, according to the HSQC and HMBC spectra of (1)]: 175.37 (C³), 39.00 (C⁴), 59.87 (C⁵), 132.37 (Cⁱ), 127.85 (C^o), 113.66 (C^m), 158.51 (C^p), 55.06 (MeO). Analysis: calculated for C₁₀H₁₂N₂O₂: C, 62.49; H, 6.29; N, 14.57. Found: C, 62.71; H, 6.08; N, 14.29.

Synthesis of 1-(p-Chlorobenzylidene)-5-(p-methoxyphenyl)-3-oxopyrazolidin-1-ium-2-ide (2)

A solution of 0.192 g (1 mmol) of (1) and 0.141 g (1 mmol) of 4-chlorobenzaldehyde in 5 ml of ethanol was refluxed for 6 hours. The reaction mixture was allowed to cool. The resulting precipitate was collected and recrystallized from ethanol to give 0.22 g (yield 70%) of (2) as white crystals; m.p. 467–468 K. IR (KBr, cm^-1): 3095, 3052, 2930, 2852 (C—H), 1676 (C=O); 1587, 1563, 1512 (phenyl C=C). Analysis: calculated for C₁₇H₁₅ClN₂O₂: C, 64.87; H, 4.80; N, 8.90. Found: C, 65.08; H, 4.59; N, 8.64.

Colourless plate-like crystals of (2) suitable for x-ray diffraction were obtained by slow evaporation from an water solution acidified with HCl at room temperature.

Refinement top

Related literature top

For related literature, see: Allen (2002); Do (2011); Indelicato & Pasini (1988); Kulpe et al. (1983); Mulhall (1997); Naito et al. (1969); Padwa & Pearson (2003); Schantl (2004); Suarez et al. (2005); Svete (2006); Vinge & Bjorkman (1986); Xu et al. (2013); Zhou et al. (2013).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. Molecular structure of the title molecule, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The intramolecular C—H···N interaction is drawn as a dashed line (see Table 1 for details).
	Fig. 2. Crystal packing for the title compound viewed along the a axis, with the C—H···π and C—H···O interactions drawn as dashed lines (see Table 1 for details).
	Fig. 3. Reaction scheme for the title compound.

(1Z)-1-(4-Chlorobenzylidene)-5-(4-methoxyphenyl)-3-oxopyrazolidin-1-ium-2-ide top

Crystal data top

C₁₇H₁₅ClN₂O₂	Z = 2
M_r = 314.76	F(000) = 328
Triclinic, P1	D_x = 1.439 Mg m⁻³
a = 5.6966 (6) Å	Melting point: 467(1) K
b = 10.6852 (13) Å	Cu Kα radiation, λ = 1.54178 Å
c = 12.7750 (17) Å	µ = 2.40 mm⁻¹
α = 101.573 (7)°	T = 100 K
β = 100.620 (7)°	Plate, colourless
γ = 101.311 (6)°	0.55 × 0.1 × 0.05 mm
V = 726.47 (15) Å³

Data collection top

Bruker SMART 6000 diffractometer	2053 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.093
Graphite monochromator	θ_max = 71.2°, θ_min = 3.6°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −6→6
T_min = 0.695, T_max = 0.887	k = −13→13
13302 measured reflections	l = −13→14
2723 independent reflections

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.171	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0732P)² + 0.2182P] where P = (F_o² + 2F_c²)/3
2723 reflections	(Δ/σ)_max < 0.001
212 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.52 e Å⁻³

Crystal data top

C₁₇H₁₅ClN₂O₂	γ = 101.311 (6)°
M_r = 314.76	V = 726.47 (15) Å³
Triclinic, P1	Z = 2
a = 5.6966 (6) Å	Cu Kα radiation
b = 10.6852 (13) Å	µ = 2.40 mm⁻¹
c = 12.7750 (17) Å	T = 100 K
α = 101.573 (7)°	0.55 × 0.1 × 0.05 mm
β = 100.620 (7)°

Data collection top

Bruker SMART 6000 diffractometer	2723 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	2053 reflections with I > 2σ(I)
T_min = 0.695, T_max = 0.887	R_int = 0.093
13302 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.171	H-atom parameters constrained
S = 1.06	Δρ_max = 0.49 e Å⁻³
2723 reflections	Δρ_min = −0.52 e Å⁻³
212 parameters

Special details top

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	0.3159 (5)	0.3078 (3)	0.0427 (3)	0.0335 (7)
C2	0.3044 (5)	0.3400 (3)	0.1510 (3)	0.0321 (7)
H2	0.161 (7)	0.3085 (15)	0.1716 (10)	0.039*
C3	0.5098 (5)	0.4202 (3)	0.2295 (3)	0.0307 (6)
H3	0.5032 (6)	0.4434 (11)	0.305 (3)	0.037*
C4	0.7274 (5)	0.4666 (3)	0.1972 (3)	0.0300 (6)
C5	0.7338 (6)	0.4289 (3)	0.0867 (3)	0.0334 (7)
H5	0.868 (7)	0.4554 (14)	0.0670 (11)	0.040*
C6	0.5296 (6)	0.3501 (3)	0.0079 (3)	0.0335 (7)
H6	0.5348 (6)	0.3261 (12)	−0.066 (3)	0.040*
C7	0.9528 (5)	0.5525 (3)	0.2711 (3)	0.0318 (7)
H7	1.080 (6)	0.5715 (10)	0.2403 (15)	0.038*
C8	0.9363 (6)	0.6628 (3)	0.5421 (3)	0.0331 (7)
C9	1.2007 (6)	0.7358 (3)	0.5523 (3)	0.0348 (7)
H9A	1.2191 (8)	0.826 (3)	0.5724 (7)	0.042*
H9B	1.309 (3)	0.7121 (7)	0.6044 (16)	0.042*
C10	1.2471 (5)	0.6936 (3)	0.4386 (3)	0.0328 (7)
H10	1.362 (5)	0.644 (2)	0.4414 (3)	0.039*
C11	1.3200 (5)	0.8005 (3)	0.3817 (3)	0.0310 (7)
C12	1.2013 (5)	0.9032 (3)	0.3819 (3)	0.0343 (7)
H12	1.076 (6)	0.9091 (4)	0.4234 (18)	0.041*
C13	1.2591 (6)	0.9962 (3)	0.3244 (3)	0.0349 (7)
H13	1.178 (4)	1.065 (3)	0.3263 (3)	0.042*
C14	1.4372 (5)	0.9886 (3)	0.2629 (3)	0.0324 (7)
C15	1.5645 (6)	0.8904 (3)	0.2644 (3)	0.0332 (7)
H15	1.688 (6)	0.8869 (3)	0.2269 (17)	0.040*
C16	1.5032 (5)	0.7974 (3)	0.3235 (3)	0.0323 (7)
H16	1.590 (4)	0.729 (3)	0.3241 (3)	0.039*
C17	1.6705 (7)	1.0860 (4)	0.1506 (3)	0.0438 (8)
H17A	1.641 (3)	0.998 (3)	0.095 (2)	0.066*
H17B	1.833 (4)	1.103 (3)	0.2060 (15)	0.066*
H17C	1.677 (4)	1.159 (3)	0.110 (2)	0.066*
Cl1	0.05505 (14)	0.21060 (9)	−0.05673 (7)	0.0434 (3)
N1	0.9930 (4)	0.6049 (2)	0.3753 (2)	0.0287 (6)
N2	0.8252 (5)	0.5891 (3)	0.4379 (2)	0.0306 (6)
O1	0.8327 (4)	0.6705 (3)	0.6184 (2)	0.0432 (6)
O2	1.4761 (4)	1.0831 (2)	0.2062 (2)	0.0382 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0211 (14)	0.0340 (16)	0.0422 (19)	0.0060 (12)	0.0036 (12)	0.0064 (13)
C2	0.0210 (14)	0.0334 (15)	0.0425 (19)	0.0047 (11)	0.0088 (12)	0.0111 (13)
C3	0.0239 (14)	0.0326 (15)	0.0347 (18)	0.0048 (12)	0.0077 (12)	0.0077 (12)
C4	0.0240 (14)	0.0277 (14)	0.0389 (18)	0.0045 (11)	0.0094 (12)	0.0095 (12)
C5	0.0215 (14)	0.0340 (16)	0.0456 (19)	0.0043 (12)	0.0111 (12)	0.0113 (13)
C6	0.0286 (15)	0.0367 (16)	0.0357 (18)	0.0082 (12)	0.0098 (12)	0.0077 (13)
C7	0.0199 (14)	0.0322 (15)	0.0438 (19)	0.0040 (11)	0.0115 (12)	0.0091 (13)
C8	0.0293 (16)	0.0328 (15)	0.0389 (18)	0.0057 (12)	0.0096 (13)	0.0128 (12)
C9	0.0259 (15)	0.0343 (16)	0.0419 (19)	0.0024 (12)	0.0065 (12)	0.0101 (13)
C10	0.0185 (14)	0.0316 (15)	0.0463 (19)	0.0029 (12)	0.0056 (12)	0.0100 (13)
C11	0.0181 (13)	0.0316 (15)	0.0383 (17)	0.0019 (11)	0.0028 (11)	0.0049 (12)
C12	0.0200 (14)	0.0408 (17)	0.0414 (19)	0.0050 (12)	0.0092 (12)	0.0089 (13)
C13	0.0239 (15)	0.0328 (16)	0.047 (2)	0.0074 (12)	0.0056 (13)	0.0089 (13)
C14	0.0226 (14)	0.0308 (15)	0.0401 (18)	0.0003 (11)	0.0039 (12)	0.0094 (12)
C15	0.0219 (14)	0.0335 (16)	0.0424 (18)	0.0025 (12)	0.0086 (12)	0.0088 (13)
C16	0.0166 (13)	0.0340 (16)	0.0443 (19)	0.0042 (11)	0.0058 (12)	0.0083 (13)
C17	0.0370 (18)	0.048 (2)	0.050 (2)	0.0084 (15)	0.0136 (15)	0.0193 (16)
Cl1	0.0231 (4)	0.0522 (5)	0.0450 (5)	0.0033 (3)	0.0050 (3)	−0.0024 (3)
N1	0.0187 (12)	0.0307 (13)	0.0374 (15)	0.0043 (9)	0.0089 (10)	0.0094 (10)
N2	0.0230 (12)	0.0348 (13)	0.0355 (15)	0.0049 (10)	0.0108 (10)	0.0103 (10)
O1	0.0362 (13)	0.0502 (14)	0.0420 (14)	0.0023 (10)	0.0156 (10)	0.0105 (10)
O2	0.0303 (11)	0.0371 (12)	0.0484 (14)	0.0055 (9)	0.0088 (9)	0.0161 (10)

Geometric parameters (Å, º) top

C1—C2	1.374 (5)	C10—H10	0.9240
C1—C6	1.395 (4)	C10—C11	1.506 (4)
C1—Cl1	1.752 (3)	C10—N1	1.539 (4)
C2—H2	0.9276	C11—C12	1.398 (5)
C2—C3	1.392 (4)	C11—C16	1.389 (4)
C3—H3	0.9509	C12—H12	0.9660
C3—C4	1.408 (4)	C12—C13	1.375 (5)
C4—C5	1.398 (5)	C13—H13	0.9441
C4—C7	1.458 (4)	C13—C14	1.398 (5)
C5—H5	0.8642	C14—C15	1.388 (5)
C5—C6	1.385 (5)	C14—O2	1.363 (4)
C6—H6	0.9337	C15—H15	0.9229
C7—H7	0.8959	C15—C16	1.394 (5)
C7—N1	1.296 (4)	C16—H16	0.9566
C8—C9	1.523 (4)	C17—H17A	1.0168
C8—N2	1.366 (4)	C17—H17B	1.0168
C8—O1	1.227 (4)	C17—H17C	1.0168
C9—H9A	0.9313	C17—O2	1.420 (4)
C9—H9B	0.9313	N1—N2	1.362 (3)
C9—C10	1.519 (5)

C2—C1—C6	122.3 (3)	C11—C10—H10	109.6
C2—C1—Cl1	119.6 (2)	C11—C10—N1	109.6 (3)
C6—C1—Cl1	118.0 (3)	N1—C10—H10	109.6
C1—C2—H2	120.2	C12—C11—C10	121.6 (3)
C1—C2—C3	119.6 (3)	C16—C11—C10	120.7 (3)
C3—C2—H2	120.2	C16—C11—C12	117.7 (3)
C2—C3—H3	120.2	C11—C12—H12	119.4
C2—C3—C4	119.7 (3)	C13—C12—C11	121.2 (3)
C4—C3—H3	120.2	C13—C12—H12	119.4
C3—C4—C7	124.9 (3)	C12—C13—H13	119.9
C5—C4—C3	119.0 (3)	C12—C13—C14	120.3 (3)
C5—C4—C7	116.1 (3)	C14—C13—H13	119.9
C4—C5—H5	119.2	C15—C14—C13	119.7 (3)
C6—C5—C4	121.7 (3)	O2—C14—C13	115.8 (3)
C6—C5—H5	119.2	O2—C14—C15	124.5 (3)
C1—C6—H6	121.1	C14—C15—H15	120.5
C5—C6—C1	117.7 (3)	C14—C15—C16	119.0 (3)
C5—C6—H6	121.1	C16—C15—H15	120.5
C4—C7—H7	115.7	C11—C16—C15	122.0 (3)
N1—C7—C4	128.5 (3)	C11—C16—H16	119.0
N1—C7—H7	115.7	C15—C16—H16	119.0
N2—C8—C9	112.6 (3)	H17A—C17—H17B	109.5
O1—C8—C9	123.9 (3)	H17A—C17—H17C	109.5
O1—C8—N2	123.5 (3)	H17B—C17—H17C	109.5
C8—C9—H9A	110.8	O2—C17—H17A	109.5
C8—C9—H9B	110.8	O2—C17—H17B	109.5
H9A—C9—H9B	108.9	O2—C17—H17C	109.5
C10—C9—C8	104.7 (3)	C7—N1—C10	120.2 (2)
C10—C9—H9A	110.8	C7—N1—N2	125.3 (3)
C10—C9—H9B	110.8	N2—N1—C10	114.5 (2)
C9—C10—H10	109.6	N1—N2—C8	107.3 (2)
C9—C10—N1	100.9 (2)	C14—O2—C17	117.6 (3)
C11—C10—C9	117.1 (3)

C1—C2—C3—C4	−0.4 (5)	C10—C11—C16—C15	176.0 (3)
C2—C1—C6—C5	−1.0 (5)	C10—N1—N2—C8	1.7 (3)
C2—C3—C4—C5	−1.3 (5)	C11—C10—N1—C7	53.0 (4)
C2—C3—C4—C7	179.0 (3)	C11—C10—N1—N2	−127.0 (3)
C3—C4—C5—C6	1.8 (5)	C11—C12—C13—C14	0.8 (5)
C3—C4—C7—N1	−2.9 (5)	C12—C11—C16—C15	−1.8 (5)
C4—C5—C6—C1	−0.7 (5)	C12—C13—C14—C15	−3.1 (5)
C4—C7—N1—C10	180.0 (3)	C12—C13—C14—O2	178.2 (3)
C4—C7—N1—N2	−0.1 (5)	C13—C14—C15—C16	3.0 (5)
C5—C4—C7—N1	177.4 (3)	C13—C14—O2—C17	174.5 (3)
C6—C1—C2—C3	1.6 (5)	C14—C15—C16—C11	−0.5 (5)
C7—C4—C5—C6	−178.4 (3)	C15—C14—O2—C17	−4.1 (5)
C7—N1—N2—C8	−178.3 (3)	C16—C11—C12—C13	1.7 (5)
C8—C9—C10—C11	121.5 (3)	Cl1—C1—C2—C3	−178.3 (2)
C8—C9—C10—N1	2.6 (3)	Cl1—C1—C6—C5	178.8 (2)
C9—C8—N2—N1	0.2 (3)	N1—C10—C11—C12	70.4 (4)
C9—C10—C11—C12	−43.7 (4)	N1—C10—C11—C16	−107.3 (3)
C9—C10—C11—C16	138.5 (3)	N2—C8—C9—C10	−2.0 (4)
C9—C10—N1—C7	177.1 (3)	O1—C8—C9—C10	178.9 (3)
C9—C10—N1—N2	−2.8 (3)	O1—C8—N2—N1	179.4 (3)
C10—C11—C12—C13	−176.1 (3)	O2—C14—C15—C16	−178.4 (3)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N2	0.96 (4)	2.31 (3)	2.934 (4)	122 (1)
C3—H3···O1ⁱ	0.96 (4)	2.52 (2)	3.152 (4)	124 (1)
C17—H17C···Cgⁱⁱ	1.02 (3)	2.73 (3)	3.551 (4)	138 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y+1, z.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N2	0.96 (4)	2.31 (3)	2.934 (4)	122.2 (8)
C3—H3···O1ⁱ	0.96 (4)	2.521 (17)	3.152 (4)	123.5 (14)
C17—H17C···Cgⁱⁱ	1.02 (3)	2.73 (3)	3.551 (4)	137.9 (18)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₅ClN₂O₂
M_r	314.76
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	5.6966 (6), 10.6852 (13), 12.7750 (17)
α, β, γ (°)	101.573 (7), 100.620 (7), 101.311 (6)
V (Å³)	726.47 (15)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	2.40
Crystal size (mm)	0.55 × 0.1 × 0.05

Data collection
Diffractometer	Bruker SMART 6000 diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.695, 0.887
No. of measured, independent and observed [I > 2σ(I)] reflections	13302, 2723, 2053
R_int	0.093
(sin θ/λ)_max (Å⁻¹)	0.614

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.171, 1.06
No. of reflections	2723
No. of parameters	212
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.52

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Acknowledgements

We thank VLIR–UOS and the Chemistry Department of KU Leuven for support of this work.

References

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Volume 70| Part 8| August 2014| Pages 84-86

doi:10.1107/S1600536814014445

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of (1Z)-1-(4-chloro­benzyl­­idene)-5-(4-meth­­oxy­phen­yl)-3-oxopyrazolidin-1-ium-2-ide

1. Chemical context

2. Structural Commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structure of (1Z)-1-(4-chlorobenzylidene)-5-(4-methoxyphenyl)-3-oxopyrazolidin-1-ium-2-ide

3. Supramolecular features