Crystal structure of ethyl 2-(3-amino-5-oxo-2-tosyl-2,5-di­hydro-1H-pyrazol-1-yl)acetate

The N-substituents lie on opposite sides of the pyrazole ring. Inter­molecular hydrogen bonds from the amino group to an S=O group and to the oxo substituent lead to a layer structure.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.001 Å
• R factor = 0.031
• wR factor = 0.094
• Data-to-parameter ratio = 34.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          5 Report

Alert level G
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        331 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          5 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         10 Info

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Cell refinement: CrysAlis PRO (Rigaku OD, 2021); data reduction: CrysAlis PRO (Rigaku OD, 2021); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL2018/3 (Sheldrick, 2015b).

Ethyl 2-[3-amino-2-(4-methylbenzenesulfonyl)-5-oxo-2,5-dihydro-1H-pyrazol-1-yl]acetate

Crystal data

C14H17N3O5S	F(000) = 712
Mr = 339.36	Dx = 1.360 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.1398 (2) Å	Cell parameters from 78897 reflections
b = 11.1525 (2) Å	θ = 2.2–36.1°
c = 16.3795 (3) Å	µ = 0.22 mm^−1
β = 97.081 (2)°	T = 100 K
V = 1656.85 (6) Å^3	Tablet, colourless
Z = 4	0.24 × 0.20 × 0.08 mm

Data collection

XtaLAB Synergy, Single source at offset/far, HyPix diffractometer	7466 independent reflections
Radiation source: micro-focus sealed X-ray tube	6502 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	Rint = 0.040
ω scans	θmax = 35.9°, θmin = 2.2°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2021)	h = −14→15
Tmin = 0.805, Tmax = 1.000	k = −17→18
128543 measured reflections	l = −26→26

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)] = 0.031	Hydrogen site location: mixed
wR(F^2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0543P)^2 + 0.3217P] where P = (Fo^2 + 2Fc^2)/3
7466 reflections	(Δ/σ)max = 0.001
218 parameters	Δρmax = 0.58 e Å^−3
0 restraints	Δρmin = −0.30 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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

- 0.4791 (0.0031) x - 2.3604 (0.0036) y + 15.9693 (0.0013) z = 2.0024 (0.0032)

* 0.0342 (0.0004) N1 * -0.0209 (0.0004) N2 * -0.0003 (0.0004) C3 * 0.0215 (0.0004) C4 * -0.0345 (0.0004) C5 -0.8468 (0.0010) C6 0.0094 (0.0011) N3 -0.1626 (0.0011) O1 1.2344 (0.0008) S1

Rms deviation of fitted atoms = 0.0255

7.3350 (0.0016) x - 0.2526 (0.0037) y + 8.0701 (0.0042) z = 9.4209 (0.0022)

Angle to previous plane (with approximate esd) = 57.006 ( 0.025 )

* -0.0031 (0.0005) C10 * -0.0009 (0.0005) C11 * 0.0057 (0.0006) C12 * -0.0065 (0.0005) C13 * 0.0025 (0.0005) C14 * 0.0022 (0.0005) C15 -0.0668 (0.0010) S1 -0.0236 (0.0012) C16

Rms deviation of fitted atoms = 0.0040

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

	x	y	z	Uiso*/Ueq
N1	0.71924 (7)	0.51318 (5)	0.22496 (4)	0.01525 (10)
N2	0.80727 (6)	0.61874 (5)	0.23976 (3)	0.01313 (9)
C3	0.70693 (7)	0.71323 (6)	0.25200 (4)	0.01349 (10)
C4	0.56556 (7)	0.67098 (6)	0.24288 (4)	0.01709 (11)
H4	0.479736	0.716052	0.249768	0.021*
C5	0.56954 (8)	0.54779 (6)	0.22128 (4)	0.01753 (12)
O1	0.47057 (7)	0.47513 (6)	0.19955 (4)	0.02624 (12)
N3	0.75894 (7)	0.82301 (5)	0.27039 (4)	0.01797 (11)
H01	0.6933 (15)	0.8832 (12)	0.2762 (8)	0.029 (3)*
H02	0.8476 (15)	0.8402 (12)	0.2619 (8)	0.029 (3)*
C6	0.75926 (9)	0.43604 (6)	0.15959 (4)	0.01874 (12)
H6A	0.692061	0.366114	0.153801	0.022*
H6B	0.860733	0.405756	0.174982	0.022*
C7	0.75148 (8)	0.50043 (6)	0.07754 (4)	0.01746 (12)
C8	0.81058 (10)	0.48513 (7)	−0.05858 (5)	0.02349 (14)
H8A	0.884230	0.550504	−0.056465	0.028*
H8B	0.712342	0.518726	−0.078401	0.028*
O2	0.70022 (8)	0.59873 (5)	0.06371 (4)	0.02588 (12)
O3	0.80980 (7)	0.43200 (5)	0.02284 (3)	0.02152 (11)
C9	0.84936 (12)	0.38700 (8)	−0.11506 (5)	0.02858 (17)
H9A	0.856512	0.420399	−0.169766	0.043*
H9B	0.772657	0.325136	−0.119119	0.043*
H9C	0.944187	0.351494	−0.093111	0.043*
S1	0.94519 (2)	0.59188 (2)	0.31853 (2)	0.01400 (4)
O4	1.02319 (6)	0.70299 (5)	0.33031 (4)	0.02030 (10)
O5	1.01852 (6)	0.48758 (5)	0.29250 (3)	0.01987 (10)
C10	0.85810 (7)	0.55582 (6)	0.40445 (4)	0.01440 (10)
C11	0.83563 (9)	0.43557 (6)	0.42138 (4)	0.01902 (12)
H11	0.869968	0.374683	0.387917	0.023*
C12	0.76214 (9)	0.40563 (7)	0.48806 (5)	0.02152 (13)
H12	0.747436	0.323625	0.500452	0.026*
C13	0.70971 (8)	0.49456 (7)	0.53699 (4)	0.01845 (12)
C14	0.73476 (9)	0.61451 (7)	0.51909 (5)	0.02110 (13)
H14	0.700833	0.675486	0.552637	0.025*
C15	0.80858 (9)	0.64644 (6)	0.45295 (4)	0.01932 (12)
H15	0.824955	0.728372	0.441058	0.023*
C16	0.62816 (9)	0.46037 (9)	0.60792 (5)	0.02581 (15)
H16A	0.699167	0.440717	0.655867	0.039*
H16B	0.565744	0.390460	0.592686	0.039*
H16C	0.566462	0.527646	0.621388	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0188 (2)	0.0120 (2)	0.0151 (2)	−0.00278 (17)	0.00269 (18)	−0.00152 (17)
N2	0.0136 (2)	0.0110 (2)	0.0147 (2)	−0.00006 (16)	0.00156 (16)	−0.00001 (16)
C3	0.0135 (2)	0.0126 (2)	0.0146 (2)	0.00057 (18)	0.00261 (18)	0.00023 (18)
C4	0.0130 (2)	0.0188 (3)	0.0197 (3)	−0.0009 (2)	0.0032 (2)	−0.0015 (2)
C5	0.0173 (3)	0.0193 (3)	0.0161 (3)	−0.0050 (2)	0.0029 (2)	−0.0004 (2)
O1	0.0242 (3)	0.0283 (3)	0.0262 (3)	−0.0140 (2)	0.0030 (2)	−0.0038 (2)
N3	0.0167 (2)	0.0115 (2)	0.0261 (3)	−0.00030 (18)	0.0040 (2)	−0.00131 (19)
C6	0.0296 (3)	0.0122 (2)	0.0145 (3)	0.0014 (2)	0.0028 (2)	−0.0007 (2)
C7	0.0228 (3)	0.0151 (3)	0.0142 (3)	0.0014 (2)	0.0011 (2)	−0.0009 (2)
C8	0.0373 (4)	0.0182 (3)	0.0157 (3)	0.0052 (3)	0.0060 (3)	0.0023 (2)
O2	0.0418 (3)	0.0172 (2)	0.0188 (2)	0.0097 (2)	0.0042 (2)	0.00153 (18)
O3	0.0327 (3)	0.0179 (2)	0.0144 (2)	0.0073 (2)	0.00453 (19)	0.00122 (17)
C9	0.0462 (5)	0.0220 (3)	0.0196 (3)	0.0069 (3)	0.0121 (3)	0.0011 (3)
S1	0.01253 (7)	0.01380 (7)	0.01577 (7)	0.00071 (4)	0.00218 (5)	0.00157 (5)
O4	0.0162 (2)	0.0189 (2)	0.0251 (2)	−0.00522 (17)	−0.00029 (18)	0.00314 (18)
O5	0.0189 (2)	0.0205 (2)	0.0210 (2)	0.00769 (18)	0.00564 (18)	0.00221 (18)
C10	0.0165 (3)	0.0128 (2)	0.0139 (2)	0.00007 (19)	0.00173 (19)	−0.00002 (19)
C11	0.0266 (3)	0.0136 (3)	0.0178 (3)	0.0004 (2)	0.0068 (2)	0.0007 (2)
C12	0.0293 (4)	0.0174 (3)	0.0188 (3)	−0.0025 (2)	0.0070 (3)	0.0021 (2)
C13	0.0172 (3)	0.0239 (3)	0.0141 (3)	−0.0017 (2)	0.0014 (2)	−0.0004 (2)
C14	0.0251 (3)	0.0207 (3)	0.0182 (3)	0.0013 (2)	0.0052 (2)	−0.0039 (2)
C15	0.0255 (3)	0.0142 (3)	0.0187 (3)	0.0004 (2)	0.0045 (2)	−0.0026 (2)
C16	0.0223 (3)	0.0393 (4)	0.0165 (3)	−0.0045 (3)	0.0053 (2)	0.0009 (3)

Geometric parameters (Å, º)

N1—C5	1.4157 (9)	C13—C14	1.3944 (11)
N1—N2	1.4296 (8)	C13—C16	1.5046 (10)
N1—C6	1.4549 (9)	C14—C15	1.3913 (11)
N2—C3	1.4273 (8)	C4—H4	0.9500
N2—S1	1.7154 (6)	N3—H01	0.913 (13)
C3—N3	1.3343 (8)	N3—H02	0.861 (13)
C3—C4	1.3661 (9)	C6—H6A	0.9900
C4—C5	1.4203 (10)	C6—H6B	0.9900
C5—O1	1.2337 (8)	C8—H8A	0.9900
C6—C7	1.5177 (10)	C8—H8B	0.9900
C7—O2	1.2027 (8)	C9—H9A	0.9800
C7—O3	1.3367 (9)	C9—H9B	0.9800
C8—O3	1.4601 (9)	C9—H9C	0.9800
C8—C9	1.5033 (11)	C11—H11	0.9500
S1—O4	1.4308 (6)	C12—H12	0.9500
S1—O5	1.4334 (5)	C14—H14	0.9500
S1—C10	1.7470 (7)	C15—H15	0.9500
C10—C11	1.3899 (9)	C16—H16A	0.9800
C10—C15	1.3950 (9)	C16—H16B	0.9800
C11—C12	1.3914 (10)	C16—H16C	0.9800
C12—C13	1.3966 (11)
C5—N1—N2	107.67 (5)	C3—C4—H4	126.0
C5—N1—C6	117.34 (6)	C5—C4—H4	126.0
N2—N1—C6	115.11 (5)	C3—N3—H01	118.5 (8)
C3—N2—N1	105.89 (5)	C3—N3—H02	119.0 (9)
C3—N2—S1	116.65 (4)	H01—N3—H02	119.8 (12)
N1—N2—S1	109.25 (4)	N1—C6—H6A	109.1
N3—C3—C4	130.31 (6)	C7—C6—H6A	109.1
N3—C3—N2	119.47 (6)	N1—C6—H6B	109.1
C4—C3—N2	110.21 (6)	C7—C6—H6B	109.1
C3—C4—C5	107.94 (6)	H6A—C6—H6B	107.8
O1—C5—N1	120.24 (7)	O3—C8—H8A	110.3
O1—C5—C4	131.82 (7)	C9—C8—H8A	110.3
N1—C5—C4	107.90 (6)	O3—C8—H8B	110.3
N1—C6—C7	112.54 (6)	C9—C8—H8B	110.3
O2—C7—O3	124.92 (7)	H8A—C8—H8B	108.5
O2—C7—C6	124.94 (7)	C8—C9—H9A	109.5
O3—C7—C6	110.15 (6)	C8—C9—H9B	109.5
O3—C8—C9	107.14 (6)	H9A—C9—H9B	109.5
C7—O3—C8	115.33 (6)	C8—C9—H9C	109.5
O4—S1—O5	119.96 (4)	H9A—C9—H9C	109.5
O4—S1—N2	104.95 (3)	H9B—C9—H9C	109.5
O5—S1—N2	104.19 (3)	C10—C11—H11	120.5
O4—S1—C10	111.08 (3)	C12—C11—H11	120.5
O5—S1—C10	109.21 (3)	C11—C12—H12	119.6
N2—S1—C10	106.30 (3)	C13—C12—H12	119.6
C11—C10—C15	121.27 (6)	C15—C14—H14	119.4
C11—C10—S1	118.43 (5)	C13—C14—H14	119.4
C15—C10—S1	120.27 (5)	C14—C15—H15	120.6
C10—C11—C12	119.05 (6)	C10—C15—H15	120.6
C11—C12—C13	120.87 (7)	C13—C16—H16A	109.5
C14—C13—C12	118.93 (6)	C13—C16—H16B	109.5
C14—C13—C16	121.02 (7)	H16A—C16—H16B	109.5
C12—C13—C16	120.05 (7)	C13—C16—H16C	109.5
C15—C14—C13	121.14 (7)	H16A—C16—H16C	109.5
C14—C15—C10	118.72 (7)	H16B—C16—H16C	109.5
C5—N1—N2—C3	5.12 (7)	C3—N2—S1—O4	−58.13 (5)
C6—N1—N2—C3	138.08 (6)	N1—N2—S1—O4	−178.12 (4)
C5—N1—N2—S1	131.52 (5)	C3—N2—S1—O5	174.95 (5)
C6—N1—N2—S1	−95.52 (6)	N1—N2—S1—O5	54.96 (5)
N1—N2—C3—N3	177.46 (6)	C3—N2—S1—C10	59.64 (5)
S1—N2—C3—N3	55.69 (7)	N1—N2—S1—C10	−60.35 (5)
N1—N2—C3—C4	−1.86 (7)	O4—S1—C10—C11	−151.48 (6)
S1—N2—C3—C4	−123.63 (5)	O5—S1—C10—C11	−16.96 (7)
N3—C3—C4—C5	178.65 (7)	N2—S1—C10—C11	94.90 (6)
N2—C3—C4—C5	−2.13 (8)	O4—S1—C10—C15	30.51 (7)
N2—N1—C5—O1	171.51 (6)	O5—S1—C10—C15	165.03 (6)
C6—N1—C5—O1	39.75 (9)	N2—S1—C10—C15	−83.11 (6)
N2—N1—C5—C4	−6.48 (7)	C15—C10—C11—C12	0.06 (11)
C6—N1—C5—C4	−138.24 (6)	S1—C10—C11—C12	−177.93 (6)
C3—C4—C5—O1	−172.33 (8)	C10—C11—C12—C13	0.78 (12)
C3—C4—C5—N1	5.35 (8)	C11—C12—C13—C14	−1.31 (12)
C5—N1—C6—C7	69.88 (8)	C11—C12—C13—C16	178.92 (7)
N2—N1—C6—C7	−58.40 (8)	C12—C13—C14—C15	1.01 (12)
N1—C6—C7—O2	−9.23 (11)	C16—C13—C14—C15	−179.22 (7)
N1—C6—C7—O3	170.80 (6)	C13—C14—C15—C10	−0.20 (11)
O2—C7—O3—C8	0.85 (12)	C11—C10—C15—C14	−0.35 (11)
C6—C7—O3—C8	−179.18 (6)	S1—C10—C15—C14	177.60 (6)
C9—C8—O3—C7	−168.27 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H01···O1^i	0.913 (13)	1.897 (13)	2.7884 (8)	164.7 (12)
N3—H02···O4	0.861 (13)	2.394 (13)	2.8291 (8)	111.8 (10)
N3—H02···O5^ii	0.861 (13)	2.294 (13)	3.0139 (8)	141.3 (12)
C6—H6B···O4^iii	0.99	2.50	3.2642 (9)	133
C8—H8B···O1^iv	0.99	2.43	3.2663 (11)	142

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