5-Chloro-3-methyl-1-phenyl-1H-pyrazole-4-carb­aldehyde: sheets built from C—H⋯O and C—H⋯π(arene) hydrogen bonds

Trilleras, J.; Quiroga, J.; Cobo, J.; Low, J.N.; Glidewell, C.

doi:10.1107/S1600536805007981

organic compounds

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ISSN: 2056-9890

Volume 61| Part 4| April 2005| Pages o1055-o1057

https://doi.org/10.1107/S1600536805007981

5-Chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde: sheets built from C—H⋯O and C—H⋯π(arene) hydrogen bonds

Jorge Trilleras,^a Jairo Quiroga,^a Justo Cobo,^b John N. Low ^c and Christopher Glidewell ^d ^*

^aGrupo de Investigación de Compuestos Heterocíclicos, Departamento de Química, Universidad de Valle, AA 25360 Cali, Colombia, ^bDepartamento de Química Inorgánica y Orgánica, Universidad de Jaén, 23071 Jaén, Spain, ^cDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^dSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 11 March 2005; accepted 14 March 2005; online 25 March 2005)

Molecules of the title compound, C₁₁H₉ClN₂O, are linked into sheets by a combination of one C—H⋯O hydrogen bond and one C—H⋯π(arene) hydrogen bond.

Comment

The title compound, (I), was prepared under Vilsmeyer conditions in which chlorination of C5 occurs in addition to the expected formylation, giving a versatile intermediate for the synthesis of fused pyrazolo heterocycles via cyclocondensation reactions (Paul et al., 2001 ).

The aldehydic fragment is almost coplanar with the adjacent pyrazole ring, but the two ring planes are inclined at 71.3 (2)° (Table 1). Within the pyrazolecarbaldehyde portion of the molecule, the bonds N1—C5 and C4—C41 are both short for their types (Allen et al., 1987 ), while bonds C4—C5 and C41—O4 are both long for their types, suggesting some contribution to the overall molecular–electronic structure from the charge-separated form (Ia) (see scheme).

The molecules of (I) are linked into sheets by a combination of one C—H⋯O hydrogen bond and one C—H⋯π(arene) hydrogen bond (Table 2); each of these hydrogen bonds generates a characteristic simple substructure and the sheet formation is most readily analysed in terms of these two substructures. In the first substructure, aryl atom C12 in the molecule at (x, y, z) acts as hydrogen-bond donor to aldehydic atom O4 in the molecule at (1 − x, 1 − y, 1 − z), so generating a centrosymmetric R₂²(16) ring (Bernstein et al., 1995 ) centred at ( $[1\over2]$ , $[1\over2]$ , $[1\over2]$ ) (Fig. 2). In the second substructure, aryl atom C15 in the molecule at (x, y, z) acts as hydrogen-bond donor to the ring C11–C16 in the molecule at (2 − x, $[1\over2]$ + y, $[3\over2]$ − z), so forming a chain running parallel to the [010] direction and generated by the 2₁ screw axis along (1, y, $[3\over4]$ ) (Fig. 3). Each R₂²(16) dimer thus acts as a double donor and a double acceptor of C—H⋯π(arene) hydrogen bonds, such that the dimer centred at ( $[1\over2]$ , $[1\over2]$ , $[1\over2]$ ) acts as donor to the dimers centred at ( $[3\over2]$ , 1, 1) and (− $[1\over2]$ , 0, 0) and as acceptor from the dimers centred at ( $[3\over2]$ , 0, 1) and (− $[1\over2]$ , 1, 0). In this manner, a sheet parallel to (10 $[\overline 2]$ ) is formed (Fig. 4); taking the R₂²(16) dimers as the nodes of the resulting net, this is then of (6,3)-type. However, there are no direction-specific interactions between adjacent sheets.

Figure 1
The molecule of compound (I

), showing the atom-labelling scheme. For the sake of clarity, only one set of methyl H atoms is shown; displacement ellipsoids are drawn at the 30% probability level.

Figure 2
Part of the crystal structure of compound (I

), showing the formation of an R₂²(16) ring centred at ( $[1\over2]$ , $[1\over2]$ , $[1\over2]$ ). For the sake of clarity, H atoms not involved in this motif have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).

Figure 3
Part of the crystal structure of compound (I

), showing the formation of a hydrogen-bonded chain along [010]. For the sake of clarity, H atoms not involved in this motif have been omitted. Atoms marked with an asterisk (*), a hash (#) or an ampersand (&) are at the symmetry positions (1 − x, $[1\over2]$ + y, $[1\over2]$ − z), (x, 1 + y, z) and (1 − x, − $[1\over2]$ + y, $[1\over2]$ − z), respectively.

Figure 4
Stereoview of part of the crystal structure of compound (I

), showing the formation of a (10 $[\overline 2]$ ) sheet. For the sake of clarity, H atoms not involved in these motifs have been omitted.

Experimental

For the preparation of (I), phosphoryl chloride (0.35 mol, 32 ml) was added dropwise to ice-cold dimethylformamide (0.16 mol, 12 ml). To this mixture was added 3-methyl-1-phenyl-5-pyrazolone (0.05 mol) and the reaction mixture was then heated under reflux for 1 h. After cooling, the reaction mixture was poured into ice-cold water (300 ml). The solid which precipitated was collected by filtration, washed with water, dried and recrystallized from ethanol to give pale-yellow crystals (m.p. 417 K) suitable for single-crystal X-ray diffraction (yield 90%). MS (70 eV) m/z (%): 221 (38), 222/220 (31/94, M⁺), 77 (100), 51 (98).

Crystal data

C₁₁H₉ClN₂O
M_r = 220.65
Monoclinic, P2₁/c
a = 6.5683 (2) Å
b = 6.7921 (2) Å
c = 22.4418 (6) Å
β = 94.206 (2)°
V = 998.49 (5) Å³
Z = 4
D_x = 1.468 Mg m⁻³
Mo Kα radiation
Cell parameters from 2291 reflections
θ = 3.1–27.5°
μ = 0.35 mm⁻¹
T = 120 (2) K
Lath, colourless
0.42 × 0.24 × 0.10 mm

Data collection

Bruker–Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.866, T_max = 0.966
10 853 measured reflections
2291 independent reflections
1995 reflections with I > 2σ(I)
R_int = 0.031
θ_max = 27.5°
h = −8 → 8
k = −8 → 8
l = −28 → 29

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.085
S = 1.02
2289 reflections
137 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.037P)² + 0.5856P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.002
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.011 (2)

Table 1
Selected geometric parameters (Å, °)

N1—N2	1.3759 (16)
N2—C3	1.3276 (18)
C3—C4	1.423 (2)
C4—C5	1.3892 (18)
C5—N1	1.3394 (18)
N1—C11	1.4372 (17)
C4—C41	1.4471 (19)
C41—O4	1.2239 (17)
C5—Cl5	1.7009 (14)

N2—N1—C11—C12	109.18 (15)
C3—C4—C41—O4	0.0 (2)

Table 2
Hydrogen-bonding geometry (Å, °)

Cg is the centroid of ring C11–C16.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯O4ⁱ	0.95	2.51	3.371 (2)	151
C15—H15⋯Cgⁱⁱ	0.95	2.72	3.498 (2)	140
Symmetry codes: (i) 1-x,1-y,1-z; (ii) $[2-x,{\script{1\over 2}}+y,{\script{3\over 2}}-z]$ .

Two very low angle reflections ( $[\overline 2]$ 02) and (01 ) were omitted from the final refinement because of partial attenuation and/or extinction.All H atoms were located in difference maps and then treated as riding atoms, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for aromatic and aldehyde H atoms or C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms. The methyl group was modelled using six H-atom sites, all with occupancy 0.5.

Data collection: COLLECT (Hooft, 1999 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003 ) and SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: OSCAIL and SHELXL97; molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536805007981/lh6388sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805007981/lh6388Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97; molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

5-Chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde top

Crystal data top

C₁₁H₉ClN₂O	F(000) = 456
M_r = 220.65	D_x = 1.468 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2291 reflections
a = 6.5683 (2) Å	θ = 3.1–27.5°
b = 6.7921 (2) Å	µ = 0.35 mm⁻¹
c = 22.4418 (6) Å	T = 120 K
β = 94.206 (2)°	Lath, colourless
V = 998.49 (5) Å³	0.42 × 0.24 × 0.10 mm
Z = 4

Data collection top

Bruker–Nonius 95mm CCD camera on κ goniostat diffractometer	2291 independent reflections
Radiation source: Bruker–Nonius FR91 rotating anode	1995 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
φ and ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −8→8
T_min = 0.866, T_max = 0.966	l = −28→29
10853 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.085	w = 1/[σ²(F_o²) + (0.037P)² + 0.5856P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.002
2289 reflections	Δρ_max = 0.31 e Å⁻³
137 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.011 (2)

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl5	0.76255 (6)	0.36211 (5)	0.624349 (15)	0.02455 (13)
O4	0.74674 (16)	0.36571 (16)	0.42194 (4)	0.0228 (2)
N1	0.76095 (17)	0.73981 (17)	0.59171 (5)	0.0162 (3)
N2	0.75951 (18)	0.86419 (18)	0.54330 (5)	0.0187 (3)
C3	0.7526 (2)	0.7469 (2)	0.49587 (6)	0.0174 (3)
C4	0.7505 (2)	0.5448 (2)	0.51250 (6)	0.0154 (3)
C5	0.7562 (2)	0.5510 (2)	0.57448 (6)	0.0157 (3)
C11	0.7702 (2)	0.8177 (2)	0.65140 (6)	0.0165 (3)
C12	0.5997 (2)	0.8051 (2)	0.68381 (6)	0.0221 (3)
C13	0.6118 (2)	0.8772 (2)	0.74201 (7)	0.0258 (3)
C14	0.7905 (2)	0.9625 (2)	0.76634 (6)	0.0228 (3)
C15	0.9595 (2)	0.9760 (2)	0.73277 (6)	0.0207 (3)
C16	0.9504 (2)	0.9021 (2)	0.67492 (6)	0.0179 (3)
C31	0.7486 (3)	0.8339 (2)	0.43451 (6)	0.0253 (3)
C41	0.7478 (2)	0.3679 (2)	0.47649 (6)	0.0180 (3)
H12	0.4767	0.7485	0.6667	0.026*
H13	0.4968	0.8678	0.7652	0.031*
H14	0.7976	1.0119	0.8060	0.027*
H15	1.0815	1.0359	0.7494	0.025*
H16	1.0659	0.9094	0.6519	0.022*
H31A	0.7515	0.9778	0.4374	0.038*	0.50
H31B	0.6237	0.7925	0.4113	0.038*	0.50
H31C	0.8679	0.7882	0.4146	0.038*	0.50
H31D	0.7439	0.7279	0.4048	0.038*	0.50
H31E	0.8717	0.9132	0.4309	0.038*	0.50
H31F	0.6275	0.9174	0.4276	0.038*	0.50
H41	0.7467	0.2449	0.4966	0.022*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl5	0.0400 (2)	0.0170 (2)	0.01678 (19)	0.00039 (15)	0.00269 (14)	0.00238 (13)
O4	0.0258 (5)	0.0266 (6)	0.0159 (5)	−0.0007 (4)	0.0003 (4)	−0.0060 (4)
N1	0.0203 (6)	0.0159 (6)	0.0124 (5)	−0.0006 (5)	0.0009 (4)	0.0001 (4)
N2	0.0256 (6)	0.0164 (6)	0.0144 (5)	−0.0007 (5)	0.0022 (4)	0.0018 (4)
C3	0.0183 (7)	0.0189 (7)	0.0150 (6)	−0.0007 (6)	0.0018 (5)	−0.0009 (5)
C4	0.0140 (6)	0.0166 (7)	0.0156 (6)	−0.0009 (5)	0.0006 (5)	−0.0010 (5)
C5	0.0157 (6)	0.0158 (7)	0.0156 (6)	−0.0010 (5)	0.0008 (5)	0.0003 (5)
C11	0.0236 (7)	0.0138 (7)	0.0122 (6)	0.0010 (5)	0.0005 (5)	−0.0007 (5)
C12	0.0214 (7)	0.0251 (8)	0.0197 (7)	−0.0021 (6)	0.0020 (5)	−0.0049 (6)
C13	0.0263 (8)	0.0305 (9)	0.0216 (7)	0.0002 (7)	0.0081 (6)	−0.0053 (6)
C14	0.0324 (8)	0.0206 (8)	0.0153 (6)	0.0025 (6)	0.0013 (6)	−0.0048 (6)
C15	0.0262 (7)	0.0165 (7)	0.0185 (7)	−0.0022 (6)	−0.0040 (5)	−0.0002 (5)
C16	0.0221 (7)	0.0153 (7)	0.0165 (6)	−0.0008 (6)	0.0018 (5)	0.0022 (5)
C31	0.0374 (9)	0.0237 (8)	0.0149 (7)	−0.0008 (7)	0.0023 (6)	0.0009 (6)
C41	0.0166 (7)	0.0182 (7)	0.0192 (7)	−0.0006 (6)	0.0006 (5)	−0.0018 (5)

Geometric parameters (Å, º) top

N1—N2	1.3759 (16)	C13—H13	0.95
N2—C3	1.3276 (18)	C14—C15	1.389 (2)
C3—C4	1.423 (2)	C14—H14	0.95
C4—C5	1.3892 (18)	C15—C16	1.3889 (19)
C5—N1	1.3394 (18)	C15—H15	0.95
N1—C11	1.4372 (17)	C16—H16	0.95
C4—C41	1.4471 (19)	C3—C31	1.4969 (19)
C41—O4	1.2239 (17)	C31—H31A	0.98
C5—Cl5	1.7009 (14)	C31—H31B	0.98
C11—C12	1.382 (2)	C31—H31C	0.98
C11—C16	1.385 (2)	C31—H31D	0.98
C12—C13	1.392 (2)	C31—H31E	0.98
C12—H12	0.95	C31—H31F	0.98
C13—C14	1.385 (2)	C41—H41	0.95

C5—N1—N2	111.17 (11)	C3—C31—H31C	109.5
C5—N1—C11	128.32 (11)	H31A—C31—H31C	109.5
N2—N1—C11	120.50 (11)	H31B—C31—H31C	109.5
C12—C11—C16	121.87 (13)	C3—C31—H31D	109.5
C12—C11—N1	119.16 (12)	H31A—C31—H31D	141.1
C16—C11—N1	118.97 (12)	H31B—C31—H31D	56.3
C11—C12—C13	118.65 (14)	H31C—C31—H31D	56.3
C11—C12—H12	120.7	C3—C31—H31E	109.5
C13—C12—H12	120.7	H31A—C31—H31E	56.3
C14—C13—C12	120.37 (14)	H31B—C31—H31E	141.1
C14—C13—H13	119.8	H31C—C31—H31E	56.3
C12—C13—H13	119.8	H31D—C31—H31E	109.5
C13—C14—C15	120.11 (13)	C3—C31—H31F	109.5
C13—C14—H14	119.9	H31A—C31—H31F	56.3
C15—C14—H14	119.9	H31B—C31—H31F	56.3
C16—C15—C14	120.11 (13)	H31C—C31—H31F	141.1
C16—C15—H15	119.9	H31D—C31—H31F	109.5
C14—C15—H15	119.9	H31E—C31—H31F	109.5
C11—C16—C15	118.88 (13)	C5—C4—C3	103.49 (12)
C11—C16—H16	120.6	C5—C4—C41	125.64 (13)
C15—C16—H16	120.6	C3—C4—C41	130.86 (12)
C3—N2—N1	105.22 (11)	O4—C41—C4	124.60 (13)
N2—C3—C4	111.66 (12)	O4—C41—H41	117.7
N2—C3—C31	119.86 (13)	C4—C41—H41	117.7
C4—C3—C31	128.48 (12)	N1—C5—C4	108.45 (12)
C3—C31—H31A	109.5	N1—C5—Cl5	122.23 (10)
C3—C31—H31B	109.5	C4—C5—Cl5	129.31 (11)
H31A—C31—H31B	109.5

C5—N1—C11—C12	−72.01 (19)	N1—N2—C3—C31	179.84 (12)
N2—N1—C11—C12	109.18 (15)	N2—C3—C4—C5	0.17 (16)
C5—N1—C11—C16	107.61 (17)	C31—C3—C4—C5	180.00 (14)
N2—N1—C11—C16	−71.21 (17)	N2—C3—C4—C41	−178.57 (13)
C16—C11—C12—C13	−1.0 (2)	C31—C3—C4—C41	1.3 (2)
N1—C11—C12—C13	178.63 (13)	C5—C4—C41—O4	−178.50 (13)
C11—C12—C13—C14	1.1 (2)	C3—C4—C41—O4	0.0 (2)
C12—C13—C14—C15	−0.3 (2)	N2—N1—C5—C4	−0.25 (15)
C13—C14—C15—C16	−0.7 (2)	C11—N1—C5—C4	−179.15 (13)
C12—C11—C16—C15	0.1 (2)	N2—N1—C5—Cl5	178.44 (9)
N1—C11—C16—C15	−179.54 (12)	C11—N1—C5—Cl5	−0.5 (2)
C14—C15—C16—C11	0.8 (2)	C3—C4—C5—N1	0.05 (15)
C5—N1—N2—C3	0.35 (15)	C41—C4—C5—N1	178.88 (12)
C11—N1—N2—C3	179.35 (12)	C3—C4—C5—Cl5	−178.52 (11)
N1—N2—C3—C4	−0.31 (15)	C41—C4—C5—Cl5	0.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O4ⁱ	0.95	2.51	3.371 (2)	151
C15—H15···Cgⁱⁱ	0.95	2.72	3.498 (2)	140

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, y+1/2, −z+3/2.

Acknowledgements

X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England. JC thanks the Consejería de Innovación, Ciencia y Empresa (Junta de Andalucía, Spain) and the Universidad de Jaén for financial support. JQ and HS thank COLCIENCIAS and UNIVALLE (Universidad del Valle, Colombia) for financial support.

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