3-(2,5-Di­chloro­thio­phen-3-yl)-5-(2,4-di­meth­oxy­phen­yl)-1-methyl-4,5-di­hydro-1H-pyrazole

In the title compound, C₁₆H₁₆Cl₂N₂O₂S, the pyrazole ring has an envelope conformation with the C atom bearing the phenyl ring being the flap. The dihedral angles between the central pyrazole ring (all atoms) and pendant thio­phene and phenyl rings are 2.00 (14) and 81.49 (12)°, respectively. In the crystal, weak C—H...O, Cl...π and π–π stacking inter­actions link the mol­ecules into a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.050
• wR factor = 0.137
• Data-to-parameter ratio = 14.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C9       --C10      .        6.2 s.u.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H11C     ..O2       .       2.70 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H18C     ..O2       .       2.68 Ang.
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         29 Report

Alert level G
PLAT072_ALERT_2_G SHELXL First  Parameter in WGHT  Unusually Large       0.12 Report
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          1 Note
PLAT793_ALERT_4_G Model has Chirality at C3          (Centro SPGR)          R Verify
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         68 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          9 Info

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

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


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

Computing details

Data collection: X-AREA Pilatus3_SV (Stoe & Cie, 2016); cell refinement: X-AREA Recipe (Stoe & Cie, 2016); data reduction: X-AREA Integrate and LANA (Stoe & Cie, 2016); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: DIAMOND (Crystal Impact); software used to prepare material for publication: X-AREA (Stoe & Cie, 2016).

3-(2,5-Dichlorothiophen-3-yl)-5-(2,4-dimethoxyphenyl)-1-methyl-4,5-dihydro-1H-pyrazole

Crystal data

C16H16Cl2N2O2S	Z = 2
Mr = 371.27	F(000) = 384
Triclinic, P1	Dx = 1.519 Mg m^−3
a = 8.3836 (3) Å	Cu Kα radiation, λ = 1.54178 Å
b = 8.4780 (3) Å	Cell parameters from 30941 reflections
c = 13.3050 (4) Å	θ = 3.5–71.7°
α = 97.779 (3)°	µ = 4.89 mm^−1
β = 101.929 (2)°	T = 100 K
γ = 114.967 (2)°	Block, yellow
V = 811.94 (5) Å^3	0.17 × 0.14 × 0.12 mm

Data collection

Stoe Stadivari diffractometer	3062 independent reflections
Radiation source: GeniX 3D HF Cu	2794 reflections with I > 2σ(I)
Detector resolution: 5.81 pixels mm^-1	Rint = 0.045
rotation method, ω scans	θmax = 71.3°, θmin = 3.5°
Absorption correction: multi-scan (LANA; Stoe & Cie, 2016)	h = −10→8
Tmin = 0.260, Tmax = 1.000	k = −4→10
21767 measured reflections	l = −16→15

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.137	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.117P)^2] where P = (Fo^2 + 2Fc^2)/3
3062 reflections	(Δ/σ)max = 0.001
211 parameters	Δρmax = 0.79 e Å^−3
0 restraints	Δρmin = −0.50 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. The H atoms were included at calculated positions and refined using the riding model with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C). Thr CH₃ groups were allowed to rotate about the bond to their next atom to best fit the electron density.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.0524 (2)	0.3616 (2)	0.24617 (13)	0.0167 (4)
O1	0.63312 (18)	0.79340 (19)	0.17276 (12)	0.0201 (3)
Cl1	0.40982 (6)	0.63165 (6)	0.59685 (4)	0.02134 (19)
Cl2	−0.26047 (7)	−0.01538 (6)	0.52260 (4)	0.02362 (19)
O2	0.46909 (19)	1.27080 (19)	0.12925 (12)	0.0202 (3)
N2	0.1173 (2)	0.4670 (2)	0.17701 (13)	0.0161 (4)
C3	0.3126 (3)	0.6004 (3)	0.22968 (15)	0.0150 (4)
H3	0.394688	0.551101	0.210416	0.018*
C4	0.3262 (3)	0.6153 (3)	0.34763 (16)	0.0163 (4)
H4A	0.442394	0.620750	0.388101	0.020*
H4AB	0.315841	0.721586	0.379923	0.020*
C5	0.1609 (3)	0.4417 (3)	0.34130 (16)	0.0153 (4)
C6	0.1101 (3)	0.3698 (3)	0.42980 (16)	0.0157 (4)
C7	0.2065 (3)	0.4389 (3)	0.53541 (16)	0.0164 (4)
S8	0.10142 (7)	0.31227 (6)	0.61630 (4)	0.01945 (19)
C9	−0.0797 (3)	0.1644 (3)	0.50664 (17)	0.0195 (4)
C10	−0.0603 (3)	0.2079 (3)	0.41399 (17)	0.0168 (4)
H10	−0.147743	0.140421	0.346684	0.020*
C11	0.0802 (3)	0.3591 (3)	0.07189 (16)	0.0199 (4)
H11A	0.114750	0.438012	0.024226	0.030*
H11B	−0.051175	0.273750	0.044120	0.030*
H11C	0.152208	0.293102	0.076627	0.030*
C12	0.3582 (3)	0.7768 (3)	0.19820 (15)	0.0150 (4)
C13	0.5195 (3)	0.8720 (3)	0.17247 (15)	0.0155 (4)
C14	0.5623 (3)	1.0375 (3)	0.14841 (15)	0.0165 (4)
H14	0.672513	1.100335	0.130663	0.020*
C15	0.4406 (3)	1.1093 (3)	0.15080 (15)	0.0161 (4)
C16	0.2790 (3)	1.0170 (3)	0.17691 (16)	0.0186 (4)
H16	0.196574	1.066391	0.178851	0.022*
C17	0.2401 (3)	0.8534 (3)	0.19987 (16)	0.0183 (4)
H17	0.129522	0.790838	0.217385	0.022*
C18	0.7935 (3)	0.8799 (3)	0.13908 (17)	0.0194 (4)
H18A	0.855409	0.804449	0.136606	0.029*
H18B	0.877631	0.996621	0.189289	0.029*
H18C	0.757239	0.897638	0.068323	0.029*
C19	0.6361 (3)	1.3732 (3)	0.10549 (18)	0.0213 (4)
H19A	0.641455	1.486915	0.094107	0.032*
H19B	0.639749	1.304878	0.041167	0.032*
H19C	0.741558	1.397937	0.164924	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0173 (8)	0.0128 (8)	0.0178 (9)	0.0038 (7)	0.0070 (7)	0.0052 (7)
O1	0.0160 (7)	0.0155 (7)	0.0316 (8)	0.0061 (6)	0.0122 (6)	0.0105 (6)
Cl1	0.0178 (3)	0.0155 (3)	0.0190 (3)	−0.0003 (2)	0.0012 (2)	0.0018 (2)
Cl2	0.0234 (3)	0.0144 (3)	0.0280 (3)	0.0009 (2)	0.0143 (2)	0.0063 (2)
O2	0.0196 (7)	0.0142 (7)	0.0285 (8)	0.0066 (6)	0.0097 (6)	0.0106 (6)
N2	0.0158 (8)	0.0112 (8)	0.0158 (8)	0.0007 (7)	0.0057 (7)	0.0041 (6)
C3	0.0137 (9)	0.0110 (9)	0.0184 (10)	0.0031 (7)	0.0059 (8)	0.0052 (7)
C4	0.0155 (10)	0.0122 (10)	0.0181 (10)	0.0030 (8)	0.0047 (8)	0.0062 (7)
C5	0.0143 (9)	0.0096 (9)	0.0200 (10)	0.0033 (8)	0.0056 (8)	0.0039 (7)
C6	0.0150 (9)	0.0106 (10)	0.0196 (10)	0.0040 (8)	0.0060 (8)	0.0035 (7)
C7	0.0157 (10)	0.0116 (10)	0.0189 (10)	0.0025 (8)	0.0061 (8)	0.0056 (8)
S8	0.0213 (3)	0.0164 (3)	0.0162 (3)	0.0042 (2)	0.0062 (2)	0.0050 (2)
C9	0.0174 (10)	0.0117 (10)	0.0252 (11)	0.0027 (8)	0.0078 (8)	0.0028 (8)
C10	0.0157 (9)	0.0155 (10)	0.0182 (10)	0.0048 (8)	0.0073 (8)	0.0058 (8)
C11	0.0215 (10)	0.0177 (10)	0.0164 (10)	0.0051 (8)	0.0064 (8)	0.0046 (8)
C12	0.0137 (9)	0.0125 (10)	0.0143 (9)	0.0025 (7)	0.0028 (8)	0.0039 (7)
C13	0.0142 (9)	0.0137 (10)	0.0136 (9)	0.0026 (8)	0.0033 (8)	0.0025 (7)
C14	0.0138 (9)	0.0141 (10)	0.0165 (9)	0.0014 (8)	0.0055 (8)	0.0036 (7)
C15	0.0166 (10)	0.0114 (10)	0.0148 (9)	0.0020 (8)	0.0026 (8)	0.0044 (7)
C16	0.0174 (10)	0.0182 (11)	0.0227 (11)	0.0088 (8)	0.0082 (8)	0.0073 (8)
C17	0.0143 (9)	0.0166 (10)	0.0204 (10)	0.0031 (8)	0.0064 (8)	0.0056 (8)
C18	0.0139 (10)	0.0159 (10)	0.0264 (11)	0.0035 (8)	0.0097 (8)	0.0053 (8)
C19	0.0201 (10)	0.0130 (10)	0.0280 (11)	0.0032 (8)	0.0089 (9)	0.0087 (8)

Geometric parameters (Å, º)

N1—C5	1.289 (3)	C9—C10	1.355 (3)
N1—N2	1.400 (2)	C10—H10	0.9500
O1—C13	1.373 (2)	C11—H11A	0.9800
O1—C18	1.433 (2)	C11—H11B	0.9800
Cl1—C7	1.719 (2)	C11—H11C	0.9800
Cl2—C9	1.713 (2)	C12—C13	1.394 (3)
O2—C15	1.368 (2)	C12—C17	1.397 (3)
O2—C19	1.430 (2)	C13—C14	1.394 (3)
N2—C11	1.457 (3)	C14—C15	1.394 (3)
N2—C3	1.483 (2)	C14—H14	0.9500
C3—C12	1.520 (3)	C15—C16	1.393 (3)
C3—C4	1.534 (3)	C16—C17	1.377 (3)
C3—H3	1.0000	C16—H16	0.9500
C4—C5	1.513 (3)	C17—H17	0.9500
C4—H4A	0.9900	C18—H18A	0.9800
C4—H4AB	0.9900	C18—H18B	0.9800
C5—C6	1.457 (3)	C18—H18C	0.9800
C6—C7	1.371 (3)	C19—H19A	0.9800
C6—C10	1.453 (3)	C19—H19B	0.9800
C7—S8	1.730 (2)	C19—H19C	0.9800
S8—C9	1.728 (2)
C5—N1—N2	109.43 (16)	N2—C11—H11B	109.5
C13—O1—C18	117.89 (15)	H11A—C11—H11B	109.5
C15—O2—C19	117.63 (15)	N2—C11—H11C	109.5
N1—N2—C11	112.53 (15)	H11A—C11—H11C	109.5
N1—N2—C3	108.77 (15)	H11B—C11—H11C	109.5
C11—N2—C3	115.30 (15)	C13—C12—C17	117.67 (18)
N2—C3—C12	111.22 (15)	C13—C12—C3	122.64 (17)
N2—C3—C4	102.37 (15)	C17—C12—C3	119.61 (17)
C12—C3—C4	113.81 (16)	O1—C13—C12	116.01 (17)
N2—C3—H3	109.7	O1—C13—C14	122.38 (17)
C12—C3—H3	109.7	C12—C13—C14	121.62 (17)
C4—C3—H3	109.7	C13—C14—C15	118.95 (18)
C5—C4—C3	100.78 (16)	C13—C14—H14	120.5
C5—C4—H4A	111.6	C15—C14—H14	120.5
C3—C4—H4A	111.6	O2—C15—C16	115.63 (17)
C5—C4—H4AB	111.6	O2—C15—C14	123.92 (17)
C3—C4—H4AB	111.6	C16—C15—C14	120.44 (18)
H4A—C4—H4AB	109.4	C17—C16—C15	119.31 (18)
N1—C5—C6	119.76 (18)	C17—C16—H16	120.3
N1—C5—C4	113.11 (18)	C15—C16—H16	120.3
C6—C5—C4	126.93 (18)	C16—C17—C12	122.01 (18)
C7—C6—C10	110.74 (18)	C16—C17—H17	119.0
C7—C6—C5	127.51 (18)	C12—C17—H17	119.0
C10—C6—C5	121.75 (18)	O1—C18—H18A	109.5
C6—C7—Cl1	129.46 (16)	O1—C18—H18B	109.5
C6—C7—S8	113.62 (15)	H18A—C18—H18B	109.5
Cl1—C7—S8	116.90 (12)	O1—C18—H18C	109.5
C9—S8—C7	90.03 (10)	H18A—C18—H18C	109.5
C10—C9—Cl2	126.69 (17)	H18B—C18—H18C	109.5
C10—C9—S8	113.60 (16)	O2—C19—H19A	109.5
Cl2—C9—S8	119.71 (13)	O2—C19—H19B	109.5
C9—C10—C6	112.00 (19)	H19A—C19—H19B	109.5
C9—C10—H10	124.0	O2—C19—H19C	109.5
C6—C10—H10	124.0	H19A—C19—H19C	109.5
N2—C11—H11A	109.5	H19B—C19—H19C	109.5
C5—N1—N2—C11	146.57 (17)	S8—C9—C10—C6	0.1 (2)
C5—N1—N2—C3	17.5 (2)	C7—C6—C10—C9	−1.0 (2)
N1—N2—C3—C12	−145.62 (15)	C5—C6—C10—C9	179.62 (17)
C11—N2—C3—C12	86.9 (2)	N2—C3—C12—C13	−136.48 (18)
N1—N2—C3—C4	−23.72 (19)	C4—C3—C12—C13	108.5 (2)
C11—N2—C3—C4	−151.19 (16)	N2—C3—C12—C17	46.9 (2)
N2—C3—C4—C5	20.12 (18)	C4—C3—C12—C17	−68.1 (2)
C12—C3—C4—C5	140.24 (16)	C18—O1—C13—C12	175.41 (17)
N2—N1—C5—C6	172.21 (17)	C18—O1—C13—C14	−4.8 (3)
N2—N1—C5—C4	−3.1 (2)	C17—C12—C13—O1	179.32 (16)
C3—C4—C5—N1	−11.6 (2)	C3—C12—C13—O1	2.7 (3)
C3—C4—C5—C6	173.50 (18)	C17—C12—C13—C14	−0.4 (3)
N1—C5—C6—C7	−178.71 (18)	C3—C12—C13—C14	−177.10 (17)
C4—C5—C6—C7	−4.1 (3)	O1—C13—C14—C15	−179.39 (17)
N1—C5—C6—C10	0.6 (3)	C12—C13—C14—C15	0.3 (3)
C4—C5—C6—C10	175.16 (16)	C19—O2—C15—C16	177.97 (18)
C10—C6—C7—Cl1	−177.09 (14)	C19—O2—C15—C14	−1.6 (3)
C5—C6—C7—Cl1	2.3 (3)	C13—C14—C15—O2	179.59 (17)
C10—C6—C7—S8	1.5 (2)	C13—C14—C15—C16	0.0 (3)
C5—C6—C7—S8	−179.20 (16)	O2—C15—C16—C17	−179.91 (18)
C6—C7—S8—C9	−1.20 (16)	C14—C15—C16—C17	−0.3 (3)
Cl1—C7—S8—C9	177.54 (12)	C15—C16—C17—C12	0.2 (3)
C7—S8—C9—C10	0.60 (17)	C13—C12—C17—C16	0.2 (3)
C7—S8—C9—Cl2	−179.08 (13)	C3—C12—C17—C16	176.92 (18)
Cl2—C9—C10—C6	179.76 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1	1.00	2.39	2.817 (3)	105
C11—H11C···O2^i	0.98	2.70	3.600 (3)	153
C18—H18C···O2^ii	0.98	2.68	3.517 (2)	144

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