Conversion of di­aryl­chalcones into 4,5-di­hydro­pyrazole-1-carbo­thio­amides: mol­ecular and supra­molecular structures of two precursors and three products

1,3-Disubstituted chalcones have been converted into 3,5-disubstituted 4,5-di­hydro­pyrazole-1-carbo­thio­amides by reaction with thio­semicarbazide. Two isomorphous chalcone precursors form hydrogen-bonded sheets, while in two isomorphous reduced pyrazole products, hydrogen-bonded chains of rings are formed: in a third product, the mol­ecules are linked into complex sheets.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.055
• wR factor = 0.132
• Data-to-parameter ratio = 15.3

Structure: II

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.043
• wR factor = 0.089
• Data-to-parameter ratio = 15.5

Structure: IV

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.075
• wR factor = 0.133
• Data-to-parameter ratio = 14.3

Structure: V

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.055
• wR factor = 0.113
• Data-to-parameter ratio = 14.5

Structure: VI

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.051
• wR factor = 0.118
• Data-to-parameter ratio = 15.8

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT220_ALERT_2_C NonSolvent Resd 1  C   Ueq(max) / Ueq(min) Range        3.1 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O34      --C34      .        6.0 s.u.
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00406 Ang.
PLAT372_ALERT_2_C Short  C(sp)-C(sp)   Bond  C38      - C39      .       1.14 Ang.
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -0.464 Report

Alert level G
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          7 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          2 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          1 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 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
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check




Datablock: II


Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections (too) Low ..        45% Check
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -1.153 Report
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -0.275 Report
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         99 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          2 Note

   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
   3 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
   4 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check




Datablock: IV


Alert level C
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00539 Ang.
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......     24.706 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      4.086 Check
PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Theta(Min).          6 Note
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
PLAT793_ALERT_4_G Model has Chirality at C5          (Centro SPGR)          R Verify
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          2 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   2 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
   4 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check




Datablock: V


Alert level C
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00639 Ang.
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      4.941 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         11 Report
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
PLAT793_ALERT_4_G Model has Chirality at C5          (Centro SPGR)          R Verify
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          3 Note

   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
   2 ALERT level G = General information/check it is not something unexpected

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




Datablock: VI


Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections (too) Low ..        49% Check
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
PLAT793_ALERT_4_G Model has Chirality at C5          (Centro SPGR)          R Verify
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         14 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          2 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 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
   2 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


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

For all structures, data collection: APEX2 (Bruker, 2012); cell refinement: APEX2/SAINT (Bruker, 2012); data reduction: SAINT/XPREP (Bruker, 2012); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2020); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b) and PLATON (Spek, 2020).

1-(4-Chlorophenyl)-3-[4-(prop-2-ynyloxy)phenyl]prop-2-en-1-one (I)

Crystal data

C18H13ClO2	F(000) = 616
Mr = 296.73	Dx = 1.314 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.990 (3) Å	Cell parameters from 2914 reflections
b = 14.2529 (16) Å	θ = 1.1–25.9°
c = 5.8661 (8) Å	µ = 0.26 mm^−1
β = 94.419 (4)°	T = 296 K
V = 1499.7 (3) Å^3	Block, orange
Z = 4	0.20 × 0.20 × 0.15 mm

Data collection

Bruker APEXII diffractometer	2912 independent reflections
Radiation source: fine focussealed tube	1777 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
φ and ω scans	θmax = 25.9°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −21→22
Tmin = 0.895, Tmax = 0.962	k = −17→17
20193 measured reflections	l = −7→7

Refinement

Refinement on F^2	Primary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.055	H-atom parameters constrained
wR(F^2) = 0.132	w = 1/[σ^2(Fo^2) + (0.0322P)^2 + 1.191P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
2912 reflections	Δρmax = 0.32 e Å^−3
190 parameters	Δρmin = −0.23 e Å^−3
0 restraints

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.

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

	x	y	z	Uiso*/Ueq
C1	0.50644 (15)	0.37616 (19)	0.0035 (5)	0.0454 (7)
O1	0.49123 (11)	0.37815 (18)	−0.2039 (3)	0.0705 (7)
C2	0.44832 (15)	0.37402 (19)	0.1650 (5)	0.0470 (7)
H2	0.4612	0.3594	0.3175	0.056*
C3	0.37764 (15)	0.39260 (17)	0.0980 (4)	0.0422 (6)
H3	0.3682	0.4115	−0.0532	0.051*
C11	0.58630 (14)	0.37539 (17)	0.0931 (4)	0.0388 (6)
C12	0.60937 (15)	0.40870 (18)	0.3093 (4)	0.0443 (7)
H12	0.5742	0.4301	0.4052	0.053*
C13	0.68450 (16)	0.41034 (18)	0.3840 (5)	0.0464 (7)
H13	0.7000	0.4340	0.5277	0.056*
C14	0.73548 (14)	0.37664 (19)	0.2428 (5)	0.0455 (7)
Cl14	0.82940 (4)	0.37534 (7)	0.33965 (16)	0.0789 (3)
C15	0.71402 (16)	0.34316 (19)	0.0276 (5)	0.0506 (7)
H15	0.7494	0.3208	−0.0665	0.061*
C16	0.63951 (15)	0.34321 (18)	−0.0463 (5)	0.0463 (7)
H16	0.6247	0.3213	−0.1921	0.056*
C31	0.31322 (14)	0.38698 (17)	0.2325 (4)	0.0385 (6)
C32	0.24378 (15)	0.41655 (19)	0.1399 (5)	0.0472 (7)
H32	0.2398	0.4428	−0.0057	0.057*
C33	0.18022 (16)	0.4082 (2)	0.2576 (5)	0.0542 (8)
H33	0.1344	0.4289	0.1926	0.065*
C34	0.18612 (15)	0.36873 (19)	0.4728 (5)	0.0478 (7)
C35	0.25439 (15)	0.33836 (18)	0.5696 (5)	0.0460 (7)
H35	0.2580	0.3117	0.7147	0.055*
C36	0.31671 (15)	0.34757 (17)	0.4517 (4)	0.0429 (7)
H36	0.3624	0.3272	0.5187	0.052*
O34	0.12808 (12)	0.35634 (17)	0.6100 (4)	0.0737 (7)
C37	0.05810 (19)	0.3821 (3)	0.5204 (6)	0.0851 (11)
H37A	0.0428	0.3436	0.3886	0.102*
H37B	0.0579	0.4473	0.4731	0.102*
C38	0.0066 (2)	0.3679 (3)	0.7054 (7)	0.0920 (13)
C39	−0.0365 (2)	0.3578 (4)	0.8370 (9)	0.1210 (18)
H39	−0.0715	0.3496	0.9439	0.145*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0503 (16)	0.0486 (16)	0.0372 (16)	−0.0022 (13)	0.0016 (13)	0.0008 (13)
O1	0.0613 (14)	0.1132 (19)	0.0362 (12)	−0.0033 (13)	−0.0009 (10)	−0.0013 (12)
C2	0.0497 (17)	0.0545 (17)	0.0366 (15)	−0.0013 (14)	0.0012 (13)	0.0043 (13)
C3	0.0512 (16)	0.0407 (15)	0.0343 (15)	−0.0051 (12)	0.0010 (12)	0.0014 (12)
C11	0.0483 (16)	0.0374 (14)	0.0308 (14)	−0.0001 (12)	0.0041 (12)	0.0018 (12)
C12	0.0509 (17)	0.0470 (16)	0.0361 (16)	0.0048 (13)	0.0101 (13)	−0.0026 (12)
C13	0.0573 (18)	0.0476 (16)	0.0340 (15)	−0.0031 (13)	0.0018 (13)	−0.0036 (12)
C14	0.0445 (16)	0.0420 (15)	0.0496 (17)	−0.0016 (12)	0.0009 (13)	0.0031 (14)
Cl14	0.0491 (5)	0.0928 (7)	0.0938 (7)	−0.0010 (4)	−0.0009 (4)	−0.0102 (5)
C15	0.0517 (18)	0.0534 (17)	0.0487 (18)	−0.0009 (14)	0.0155 (14)	−0.0081 (14)
C16	0.0573 (18)	0.0478 (16)	0.0345 (15)	−0.0058 (13)	0.0086 (13)	−0.0037 (12)
C31	0.0479 (16)	0.0349 (14)	0.0320 (14)	−0.0017 (12)	−0.0011 (12)	−0.0018 (11)
C32	0.0562 (18)	0.0474 (16)	0.0373 (16)	0.0020 (14)	−0.0020 (14)	0.0041 (12)
C33	0.0449 (17)	0.0627 (19)	0.0540 (19)	0.0079 (14)	−0.0035 (14)	0.0037 (15)
C34	0.0476 (16)	0.0528 (17)	0.0435 (17)	−0.0019 (13)	0.0077 (13)	−0.0031 (14)
C35	0.0576 (18)	0.0475 (16)	0.0326 (15)	0.0032 (13)	0.0015 (13)	0.0022 (12)
C36	0.0466 (16)	0.0420 (15)	0.0392 (16)	0.0014 (12)	−0.0029 (13)	−0.0020 (12)
O34	0.0523 (13)	0.1029 (18)	0.0666 (15)	0.0097 (12)	0.0101 (11)	0.0078 (13)
C37	0.065 (2)	0.111 (3)	0.079 (3)	0.008 (2)	0.002 (2)	0.019 (2)
C38	0.050 (2)	0.128 (4)	0.099 (3)	−0.001 (2)	0.017 (2)	0.011 (3)
C39	0.062 (3)	0.189 (5)	0.115 (4)	0.007 (3)	0.021 (3)	0.034 (4)

Geometric parameters (Å, º)

C1—O1	1.226 (3)	C31—C32	1.389 (3)
C1—C2	1.465 (4)	C31—C36	1.400 (3)
C1—C11	1.491 (4)	C32—C33	1.386 (4)
C2—C3	1.328 (3)	C32—H32	0.9300
C2—H2	0.9300	C33—C34	1.379 (4)
C3—C31	1.454 (4)	C33—H33	0.9300
C3—H3	0.9300	C34—O34	1.378 (3)
C11—C16	1.385 (3)	C34—C35	1.382 (4)
C11—C12	1.387 (3)	C35—C36	1.368 (4)
C12—C13	1.388 (4)	C35—H35	0.9300
C12—H12	0.9300	C36—H36	0.9300
C13—C14	1.369 (4)	O34—C37	1.376 (4)
C13—H13	0.9300	C37—C38	1.494 (5)
C14—C15	1.377 (4)	C37—H37A	0.9700
C14—Cl14	1.741 (3)	C37—H37B	0.9700
C15—C16	1.377 (4)	C38—C39	1.144 (5)
C15—H15	0.9300	C39—H39	0.9300
C16—H16	0.9300
O1—C1—C2	121.8 (3)	C32—C31—C36	117.2 (2)
O1—C1—C11	119.0 (2)	C32—C31—C3	120.1 (2)
C2—C1—C11	119.2 (2)	C36—C31—C3	122.6 (2)
C3—C2—C1	121.3 (2)	C33—C32—C31	122.1 (3)
C3—C2—H2	119.4	C33—C32—H32	119.0
C1—C2—H2	119.4	C31—C32—H32	119.0
C2—C3—C31	127.8 (2)	C34—C33—C32	118.9 (3)
C2—C3—H3	116.1	C34—C33—H33	120.5
C31—C3—H3	116.1	C32—C33—H33	120.5
C16—C11—C12	118.8 (2)	O34—C34—C33	125.4 (3)
C16—C11—C1	119.0 (2)	O34—C34—C35	114.2 (2)
C12—C11—C1	122.2 (2)	C33—C34—C35	120.5 (3)
C11—C12—C13	120.6 (2)	C36—C35—C34	119.9 (3)
C11—C12—H12	119.7	C36—C35—H35	120.0
C13—C12—H12	119.7	C34—C35—H35	120.0
C14—C13—C12	119.0 (3)	C35—C36—C31	121.5 (3)
C14—C13—H13	120.5	C35—C36—H36	119.3
C12—C13—H13	120.5	C31—C36—H36	119.3
C13—C14—C15	121.5 (3)	C37—O34—C34	117.1 (3)
C13—C14—Cl14	119.0 (2)	O34—C37—C38	106.7 (3)
C15—C14—Cl14	119.5 (2)	O34—C37—H37A	110.4
C16—C15—C14	119.1 (3)	C38—C37—H37A	110.4
C16—C15—H15	120.5	O34—C37—H37B	110.4
C14—C15—H15	120.5	C38—C37—H37B	110.4
C15—C16—C11	121.0 (2)	H37A—C37—H37B	108.6
C15—C16—H16	119.5	C39—C38—C37	175.7 (5)
C11—C16—H16	119.5	C38—C39—H39	180.0
O1—C1—C2—C3	−13.4 (4)	C1—C11—C16—C15	178.6 (2)
C11—C1—C2—C3	166.9 (2)	C2—C3—C31—C32	174.7 (3)
C1—C2—C3—C31	175.3 (2)	C2—C3—C31—C36	−9.0 (4)
O1—C1—C11—C16	−23.3 (4)	C36—C31—C32—C33	0.2 (4)
C2—C1—C11—C16	156.4 (2)	C3—C31—C32—C33	176.8 (2)
O1—C1—C11—C12	154.6 (3)	C31—C32—C33—C34	−0.4 (4)
C2—C1—C11—C12	−25.7 (4)	C32—C33—C34—O34	179.7 (3)
C16—C11—C12—C13	0.4 (4)	C32—C33—C34—C35	0.2 (4)
C1—C11—C12—C13	−177.5 (2)	O34—C34—C35—C36	−179.4 (2)
C11—C12—C13—C14	−1.4 (4)	C33—C34—C35—C36	0.1 (4)
C12—C13—C14—C15	1.4 (4)	C34—C35—C36—C31	−0.3 (4)
C12—C13—C14—Cl14	−178.0 (2)	C32—C31—C36—C35	0.1 (4)
C13—C14—C15—C16	−0.4 (4)	C3—C31—C36—C35	−176.3 (2)
Cl14—C14—C15—C16	179.1 (2)	C33—C34—O34—C37	2.8 (4)
C14—C15—C16—C11	−0.7 (4)	C35—C34—O34—C37	−177.8 (3)
C12—C11—C16—C15	0.6 (4)	C34—O34—C37—C38	−176.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···Cg1^i	0.93	2.90	3.554 (3)	128
C35—H35···Cg1^ii	0.93	2.83	3.508 (3)	131

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

1-(4-Bromophenyl)-3-[4-(prop-2-ynyloxy)phenyl]prop-2-en-1-one (II)

Crystal data

C18H13BrO2	F(000) = 688
Mr = 341.18	Dx = 1.489 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.286 (6) Å	Cell parameters from 2047 reflections
b = 14.277 (4) Å	θ = 1.1–26.2°
c = 5.8489 (17) Å	µ = 2.70 mm^−1
β = 94.521 (7)°	T = 296 K
V = 1522.2 (8) Å^3	Block, colourless
Z = 4	0.20 × 0.15 × 0.15 mm

Data collection

Bruker APEXII diffractometer	2945 independent reflections
Radiation source: fine focussealed tube	1335 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.119
φ and ω scans	θmax = 26.2°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −22→22
Tmin = 0.491, Tmax = 0.667	k = −17→17
23006 measured reflections	l = −7→7

Refinement

Refinement on F^2	Primary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.089	w = 1/[σ^2(Fo^2) + (0.0262P)^2 + 0.1591P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
2945 reflections	Δρmax = 0.43 e Å^−3
190 parameters	Δρmin = −0.50 e Å^−3
0 restraints

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.

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

	x	y	z	Uiso*/Ueq
C1	0.5049 (2)	0.3768 (3)	0.0000 (7)	0.0455 (10)
O1	0.48975 (14)	0.3791 (2)	−0.2076 (4)	0.0658 (8)
C2	0.4477 (2)	0.3747 (3)	0.1628 (6)	0.0428 (10)
H2	0.4606	0.3605	0.3158	0.051*
C3	0.3782 (2)	0.3926 (2)	0.0970 (6)	0.0398 (10)
H3	0.3689	0.4117	−0.0545	0.048*
C11	0.5835 (2)	0.3755 (2)	0.0928 (6)	0.0355 (9)
C12	0.6067 (2)	0.4089 (2)	0.3083 (6)	0.0420 (11)
H12	0.5723	0.4309	0.4041	0.050*
C13	0.6798 (2)	0.4103 (2)	0.3835 (6)	0.0433 (11)
H13	0.6948	0.4337	0.5281	0.052*
C14	0.7306 (2)	0.3767 (3)	0.2425 (6)	0.0431 (10)
Br14	0.83135 (2)	0.37416 (4)	0.34974 (8)	0.0703 (2)
C15	0.7097 (2)	0.3428 (2)	0.0268 (7)	0.0458 (11)
H15	0.7444	0.3200	−0.0668	0.055*
C16	0.6364 (2)	0.3435 (2)	−0.0474 (6)	0.0444 (11)
H16	0.6218	0.3223	−0.1942	0.053*
C31	0.3145 (2)	0.3864 (2)	0.2299 (6)	0.0350 (9)
C32	0.2465 (2)	0.4154 (2)	0.1353 (6)	0.0448 (11)
H32	0.2433	0.4417	−0.0107	0.054*
C33	0.1829 (2)	0.4070 (3)	0.2489 (7)	0.0472 (11)
H33	0.1379	0.4273	0.1818	0.057*
C34	0.1890 (2)	0.3672 (3)	0.4658 (6)	0.0433 (10)
C35	0.2557 (2)	0.3374 (2)	0.5652 (6)	0.0404 (10)
H35	0.2588	0.3107	0.7107	0.049*
C36	0.3175 (2)	0.3473 (2)	0.4488 (6)	0.0390 (10)
H36	0.3624	0.3275	0.5175	0.047*
O34	0.13136 (16)	0.35477 (19)	0.6007 (4)	0.0638 (8)
C37	0.0619 (2)	0.3799 (3)	0.5085 (7)	0.0726 (13)
H37A	0.0474	0.3410	0.3766	0.087*
H37B	0.0616	0.4448	0.4596	0.087*
C38	0.0106 (3)	0.3664 (4)	0.6897 (9)	0.0806 (15)
C39	−0.0320 (3)	0.3582 (4)	0.8233 (9)	0.106 (2)
H39	−0.0664	0.3516	0.9312	0.127*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.050 (3)	0.045 (3)	0.041 (3)	−0.001 (2)	0.003 (2)	0.002 (2)
O1	0.058 (2)	0.110 (2)	0.0289 (16)	−0.0013 (18)	−0.0015 (14)	−0.0012 (17)
C2	0.044 (3)	0.050 (2)	0.034 (2)	−0.005 (2)	−0.002 (2)	0.004 (2)
C3	0.051 (3)	0.035 (3)	0.032 (2)	−0.008 (2)	−0.002 (2)	0.0031 (18)
C11	0.044 (3)	0.033 (2)	0.030 (2)	0.002 (2)	0.005 (2)	0.004 (2)
C12	0.048 (3)	0.046 (3)	0.032 (2)	0.006 (2)	0.007 (2)	−0.0007 (18)
C13	0.054 (3)	0.042 (3)	0.034 (2)	−0.003 (2)	0.000 (2)	−0.0056 (18)
C14	0.040 (3)	0.039 (2)	0.050 (3)	−0.001 (2)	0.001 (2)	0.001 (2)
Br14	0.0455 (3)	0.0781 (3)	0.0860 (4)	−0.0015 (3)	−0.0030 (2)	−0.0081 (3)
C15	0.045 (3)	0.047 (3)	0.048 (3)	0.001 (2)	0.014 (2)	−0.010 (2)
C16	0.058 (3)	0.043 (3)	0.032 (2)	−0.005 (2)	0.003 (2)	−0.0052 (18)
C31	0.044 (3)	0.033 (2)	0.028 (2)	−0.001 (2)	0.000 (2)	−0.0026 (19)
C32	0.051 (3)	0.047 (3)	0.034 (2)	0.006 (2)	−0.008 (2)	0.0047 (18)
C33	0.037 (3)	0.057 (3)	0.047 (3)	0.010 (2)	−0.001 (2)	0.004 (2)
C34	0.046 (3)	0.046 (2)	0.039 (2)	−0.001 (2)	0.009 (2)	−0.005 (2)
C35	0.048 (3)	0.041 (3)	0.031 (2)	0.001 (2)	0.000 (2)	0.0030 (18)
C36	0.038 (3)	0.040 (3)	0.037 (2)	−0.0017 (19)	−0.006 (2)	−0.0015 (18)
O34	0.0415 (19)	0.091 (2)	0.0588 (19)	0.0127 (17)	0.0053 (16)	0.0078 (16)
C37	0.060 (4)	0.088 (4)	0.070 (3)	0.009 (3)	0.000 (3)	0.008 (3)
C38	0.047 (4)	0.109 (4)	0.086 (4)	0.003 (4)	0.009 (3)	0.004 (4)
C39	0.065 (4)	0.162 (6)	0.093 (4)	0.014 (4)	0.024 (3)	0.023 (4)

Geometric parameters (Å, º)

C1—O1	1.225 (4)	C31—C32	1.383 (5)
C1—C2	1.470 (5)	C31—C36	1.394 (5)
C1—C11	1.496 (5)	C32—C33	1.390 (5)
C2—C3	1.323 (5)	C32—H32	0.9300
C2—H2	0.9300	C33—C34	1.386 (5)
C3—C31	1.453 (5)	C33—H33	0.9300
C3—H3	0.9300	C34—C35	1.376 (5)
C11—C12	1.383 (5)	C34—O34	1.377 (4)
C11—C16	1.393 (5)	C35—C36	1.373 (5)
C12—C13	1.373 (5)	C35—H35	0.9300
C12—H12	0.9300	C36—H36	0.9300
C13—C14	1.376 (5)	O34—C37	1.388 (4)
C13—H13	0.9300	C37—C38	1.483 (6)
C14—C15	1.377 (5)	C37—H37A	0.9700
C14—Br14	1.899 (4)	C37—H37B	0.9700
C15—C16	1.376 (5)	C38—C39	1.152 (6)
C15—H15	0.9300	C39—H39	0.9300
C16—H16	0.9300
O1—C1—C2	121.7 (4)	C32—C31—C36	117.1 (3)
O1—C1—C11	119.8 (3)	C32—C31—C3	120.0 (3)
C2—C1—C11	118.5 (3)	C36—C31—C3	122.7 (4)
C3—C2—C1	121.6 (3)	C31—C32—C33	122.8 (4)
C3—C2—H2	119.2	C31—C32—H32	118.6
C1—C2—H2	119.2	C33—C32—H32	118.6
C2—C3—C31	128.6 (3)	C34—C33—C32	117.6 (4)
C2—C3—H3	115.7	C34—C33—H33	121.2
C31—C3—H3	115.7	C32—C33—H33	121.2
C12—C11—C16	118.1 (4)	C35—C34—O34	114.2 (3)
C12—C11—C1	123.0 (3)	C35—C34—C33	121.1 (4)
C16—C11—C1	118.8 (3)	O34—C34—C33	124.6 (4)
C13—C12—C11	121.2 (3)	C36—C35—C34	119.7 (3)
C13—C12—H12	119.4	C36—C35—H35	120.1
C11—C12—H12	119.4	C34—C35—H35	120.1
C12—C13—C14	119.3 (3)	C35—C36—C31	121.5 (4)
C12—C13—H13	120.4	C35—C36—H36	119.2
C14—C13—H13	120.4	C31—C36—H36	119.2
C13—C14—C15	121.3 (4)	C34—O34—C37	117.5 (3)
C13—C14—Br14	119.5 (3)	O34—C37—C38	107.5 (4)
C15—C14—Br14	119.2 (3)	O34—C37—H37A	110.2
C16—C15—C14	118.7 (3)	C38—C37—H37A	110.2
C16—C15—H15	120.7	O34—C37—H37B	110.2
C14—C15—H15	120.7	C38—C37—H37B	110.2
C15—C16—C11	121.4 (3)	H37A—C37—H37B	108.5
C15—C16—H16	119.3	C39—C38—C37	176.5 (6)
C11—C16—H16	119.3	C38—C39—H39	180.0
O1—C1—C2—C3	−12.7 (6)	C1—C11—C16—C15	178.4 (3)
C11—C1—C2—C3	167.6 (4)	C2—C3—C31—C32	174.8 (4)
C1—C2—C3—C31	174.6 (3)	C2—C3—C31—C36	−8.7 (6)
O1—C1—C11—C12	153.8 (4)	C36—C31—C32—C33	0.0 (5)
C2—C1—C11—C12	−26.5 (6)	C3—C31—C32—C33	176.7 (3)
O1—C1—C11—C16	−22.9 (6)	C31—C32—C33—C34	−0.3 (6)
C2—C1—C11—C16	156.8 (3)	C32—C33—C34—C35	0.2 (6)
C16—C11—C12—C13	−0.4 (5)	C32—C33—C34—O34	179.4 (3)
C1—C11—C12—C13	−177.1 (3)	O34—C34—C35—C36	−179.1 (3)
C11—C12—C13—C14	−0.8 (5)	C33—C34—C35—C36	0.2 (6)
C12—C13—C14—C15	0.8 (5)	C34—C35—C36—C31	−0.5 (5)
C12—C13—C14—Br14	−177.7 (3)	C32—C31—C36—C35	0.4 (5)
C13—C14—C15—C16	0.4 (5)	C3—C31—C36—C35	−176.2 (3)
Br14—C14—C15—C16	178.9 (3)	C35—C34—O34—C37	−177.6 (3)
C14—C15—C16—C11	−1.6 (5)	C33—C34—O34—C37	3.1 (6)
C12—C11—C16—C15	1.6 (5)	C34—O34—C37—C38	−176.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···Cg1^i	0.93	2.95	3.602 (4)	128
C35—H35···Cg1^ii	0.93	2.80	3.484 (3)	131

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

(RS)-3-(4-Chlorophenyl)-5-[4-(prop-2-ynyloxy)phenyl]-4,5-dihydropyrazole-1-carbothioamide (IV)

Crystal data

C19H16ClN3OS	F(000) = 768
Mr = 369.86	Dx = 1.385 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 15.0182 (9) Å	Cell parameters from 4932 reflections
b = 6.0579 (3) Å	θ = 2.9–29.5°
c = 20.8286 (12) Å	µ = 0.35 mm^−1
β = 110.573 (2)°	T = 298 K
V = 1774.11 (17) Å^3	Needle, colourless
Z = 4	0.20 × 0.15 × 0.10 mm

Data collection

Bruker APEXII diffractometer	3326 independent reflections
Radiation source: fine focussealed tube	2571 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
φ and ω scans	θmax = 25.6°, θmin = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −18→18
Tmin = 0.870, Tmax = 0.966	k = −7→7
25833 measured reflections	l = −25→25

Refinement

Refinement on F^2	Primary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.075	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.133	w = 1/[σ^2(Fo^2) + (0.0304P)^2 + 1.7629P] where P = (Fo^2 + 2Fc^2)/3
S = 1.24	(Δ/σ)max < 0.001
3326 reflections	Δρmax = 0.19 e Å^−3
232 parameters	Δρmin = −0.28 e Å^−3
0 restraints

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.

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

	x	y	z	Uiso*/Ueq
N1	0.5173 (2)	0.7308 (4)	0.34225 (14)	0.0412 (7)
N2	0.45647 (18)	0.5533 (4)	0.31707 (14)	0.0410 (7)
C3	0.4545 (2)	0.5106 (6)	0.25593 (17)	0.0409 (8)
C4	0.5122 (2)	0.6700 (6)	0.23130 (17)	0.0458 (9)
H4A	0.4717	0.7751	0.1990	0.055*
H4	0.5513	0.5935	0.2100	0.055*
C5	0.5734 (2)	0.7840 (6)	0.29827 (17)	0.0427 (8)
H5	0.5753	0.9439	0.2916	0.051*
C11	0.5230 (2)	0.8250 (6)	0.40229 (17)	0.0402 (8)
S11	0.59292 (7)	1.04457 (15)	0.43338 (5)	0.0499 (3)
N11	0.4696 (3)	0.7346 (6)	0.43395 (18)	0.0623 (10)
H11B	0.466 (3)	0.803 (7)	0.470 (2)	0.075*
H11A	0.439 (3)	0.628 (7)	0.417 (2)	0.075*
C31	0.3970 (2)	0.3293 (6)	0.21696 (17)	0.0411 (8)
C32	0.3691 (3)	0.3240 (7)	0.14614 (19)	0.0619 (11)
H32	0.3909	0.4320	0.1236	0.074*
C33	0.3095 (3)	0.1608 (8)	0.1088 (2)	0.0668 (12)
H33	0.2907	0.1593	0.0612	0.080*
C34	0.2781 (2)	0.0015 (6)	0.1419 (2)	0.0531 (10)
Cl34	0.20074 (7)	−0.2014 (2)	0.09434 (6)	0.0773 (4)
C35	0.3074 (3)	−0.0024 (6)	0.2126 (2)	0.0535 (10)
H35	0.2874	−0.1146	0.2348	0.064*
C36	0.3663 (2)	0.1615 (6)	0.24951 (19)	0.0475 (9)
H36	0.3861	0.1600	0.2971	0.057*
C51	0.6726 (2)	0.6900 (5)	0.32626 (16)	0.0397 (8)
C52	0.6902 (3)	0.4924 (6)	0.36169 (18)	0.0497 (9)
H52	0.6404	0.4210	0.3698	0.060*
C53	0.7795 (2)	0.3978 (6)	0.38544 (18)	0.0468 (9)
H53	0.7896	0.2643	0.4090	0.056*
C54	0.8535 (2)	0.5047 (6)	0.37368 (16)	0.0417 (8)
C55	0.8367 (3)	0.6981 (6)	0.33696 (17)	0.0457 (9)
H55	0.8863	0.7672	0.3278	0.055*
C56	0.7476 (3)	0.7905 (6)	0.31355 (17)	0.0436 (8)
H56	0.7374	0.9219	0.2889	0.052*
O54	0.94624 (17)	0.4330 (4)	0.39776 (13)	0.0540 (7)
C57	0.9668 (3)	0.2523 (6)	0.4444 (2)	0.0563 (10)
H57A	0.9342	0.1209	0.4211	0.068*
H57B	0.9446	0.2847	0.4818	0.068*
C58	1.0686 (3)	0.2143 (6)	0.47095 (19)	0.0526 (9)
C59	1.1497 (3)	0.1775 (7)	0.4949 (2)	0.0631 (11)
H59	1.2145	0.1481	0.5141	0.076*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0464 (16)	0.0399 (16)	0.0436 (16)	−0.0078 (14)	0.0237 (13)	−0.0016 (13)
N2	0.0408 (16)	0.0402 (16)	0.0450 (16)	−0.0051 (14)	0.0186 (13)	0.0003 (14)
C3	0.0390 (19)	0.043 (2)	0.0432 (19)	0.0045 (16)	0.0169 (16)	0.0046 (16)
C4	0.048 (2)	0.050 (2)	0.0420 (19)	0.0046 (18)	0.0192 (17)	0.0044 (17)
C5	0.052 (2)	0.0373 (19)	0.047 (2)	−0.0016 (17)	0.0278 (17)	0.0068 (16)
C11	0.0413 (19)	0.0395 (19)	0.0426 (19)	0.0000 (16)	0.0181 (16)	0.0028 (16)
S11	0.0589 (6)	0.0428 (5)	0.0537 (6)	−0.0133 (5)	0.0268 (5)	−0.0037 (5)
N11	0.079 (3)	0.068 (2)	0.057 (2)	−0.0352 (19)	0.044 (2)	−0.0192 (18)
C31	0.0377 (19)	0.0428 (19)	0.0401 (19)	0.0067 (16)	0.0103 (15)	0.0007 (16)
C32	0.072 (3)	0.066 (3)	0.045 (2)	−0.010 (2)	0.017 (2)	0.001 (2)
C33	0.073 (3)	0.076 (3)	0.044 (2)	−0.003 (3)	0.013 (2)	−0.011 (2)
C34	0.038 (2)	0.055 (2)	0.064 (3)	0.0043 (18)	0.0144 (19)	−0.016 (2)
Cl34	0.0552 (6)	0.0823 (8)	0.0933 (8)	−0.0106 (6)	0.0247 (6)	−0.0430 (7)
C35	0.051 (2)	0.047 (2)	0.066 (3)	0.0004 (18)	0.025 (2)	−0.0029 (19)
C36	0.050 (2)	0.047 (2)	0.046 (2)	0.0060 (18)	0.0171 (17)	0.0010 (18)
C51	0.047 (2)	0.0379 (19)	0.0382 (18)	−0.0054 (16)	0.0199 (16)	0.0000 (15)
C52	0.049 (2)	0.044 (2)	0.063 (2)	−0.0090 (18)	0.0285 (19)	0.0071 (18)
C53	0.049 (2)	0.0379 (19)	0.057 (2)	−0.0033 (17)	0.0227 (18)	0.0087 (17)
C54	0.042 (2)	0.046 (2)	0.0390 (18)	−0.0056 (17)	0.0177 (16)	−0.0067 (16)
C55	0.048 (2)	0.050 (2)	0.047 (2)	−0.0132 (18)	0.0275 (17)	0.0027 (18)
C56	0.055 (2)	0.0383 (19)	0.0429 (19)	−0.0081 (17)	0.0241 (17)	0.0071 (16)
O54	0.0466 (15)	0.0592 (16)	0.0609 (16)	0.0010 (13)	0.0247 (13)	0.0083 (14)
C57	0.056 (2)	0.056 (2)	0.058 (2)	0.0017 (19)	0.022 (2)	−0.003 (2)
C58	0.055 (3)	0.056 (2)	0.049 (2)	−0.001 (2)	0.021 (2)	−0.0060 (19)
C59	0.058 (3)	0.078 (3)	0.053 (2)	0.002 (2)	0.019 (2)	0.001 (2)

Geometric parameters (Å, º)

N1—C11	1.350 (4)	C34—Cl34	1.741 (4)
N1—N2	1.389 (4)	C35—C36	1.372 (5)
N1—C5	1.481 (4)	C35—H35	0.9300
N2—C3	1.290 (4)	C36—H36	0.9300
C3—C31	1.456 (5)	C51—C52	1.382 (5)
C3—C4	1.502 (5)	C51—C56	1.385 (4)
C4—C5	1.539 (5)	C52—C53	1.380 (5)
C4—H4A	0.9700	C52—H52	0.9300
C4—H4	0.9700	C53—C54	1.380 (4)
C5—C51	1.507 (5)	C53—H53	0.9300
C5—H5	0.9800	C54—C55	1.373 (5)
C11—N11	1.323 (4)	C54—O54	1.375 (4)
C11—S11	1.677 (3)	C55—C56	1.373 (5)
N11—H11B	0.87 (4)	C55—H55	0.9300
N11—H11A	0.80 (4)	C56—H56	0.9300
C31—C32	1.385 (5)	O54—C57	1.423 (4)
C31—C36	1.387 (5)	C57—C58	1.450 (5)
C32—C33	1.376 (6)	C57—H57A	0.9700
C32—H32	0.9300	C57—H57B	0.9700
C33—C34	1.364 (6)	C58—C59	1.164 (5)
C33—H33	0.9300	C59—H59	0.9300
C34—C35	1.380 (5)
C11—N1—N2	119.7 (3)	C33—C34—Cl34	119.5 (3)
C11—N1—C5	128.1 (3)	C35—C34—Cl34	119.6 (3)
N2—N1—C5	112.1 (2)	C36—C35—C34	119.1 (4)
C3—N2—N1	108.1 (3)	C36—C35—H35	120.4
N2—C3—C31	120.3 (3)	C34—C35—H35	120.4
N2—C3—C4	113.1 (3)	C35—C36—C31	121.0 (3)
C31—C3—C4	126.5 (3)	C35—C36—H36	119.5
C3—C4—C5	102.2 (3)	C31—C36—H36	119.5
C3—C4—H4A	111.3	C52—C51—C56	117.8 (3)
C5—C4—H4A	111.3	C52—C51—C5	120.8 (3)
C3—C4—H4	111.3	C56—C51—C5	121.3 (3)
C5—C4—H4	111.3	C53—C52—C51	122.1 (3)
H4A—C4—H4	109.2	C53—C52—H52	119.0
N1—C5—C51	112.2 (3)	C51—C52—H52	119.0
N1—C5—C4	100.0 (3)	C54—C53—C52	118.9 (3)
C51—C5—C4	112.1 (3)	C54—C53—H53	120.6
N1—C5—H5	110.7	C52—C53—H53	120.6
C51—C5—H5	110.7	C55—C54—O54	115.9 (3)
C4—C5—H5	110.7	C55—C54—C53	119.9 (3)
N11—C11—N1	115.8 (3)	O54—C54—C53	124.2 (3)
N11—C11—S11	122.9 (3)	C54—C55—C56	120.7 (3)
N1—C11—S11	121.3 (2)	C54—C55—H55	119.7
C11—N11—H11B	117 (3)	C56—C55—H55	119.7
C11—N11—H11A	118 (3)	C55—C56—C51	120.7 (3)
H11B—N11—H11A	124 (4)	C55—C56—H56	119.7
C32—C31—C36	118.4 (3)	C51—C56—H56	119.7
C32—C31—C3	120.6 (3)	C54—O54—C57	116.2 (3)
C36—C31—C3	121.0 (3)	O54—C57—C58	109.2 (3)
C33—C32—C31	120.8 (4)	O54—C57—H57A	109.8
C33—C32—H32	119.6	C58—C57—H57A	109.8
C31—C32—H32	119.6	O54—C57—H57B	109.8
C34—C33—C32	119.6 (4)	C58—C57—H57B	109.8
C34—C33—H33	120.2	H57A—C57—H57B	108.3
C32—C33—H33	120.2	C59—C58—C57	176.5 (4)
C33—C34—C35	121.0 (4)	C58—C59—H59	180.0
C11—N1—N2—C3	172.1 (3)	C32—C33—C34—Cl34	178.7 (3)
C5—N1—N2—C3	−11.1 (4)	C33—C34—C35—C36	2.3 (5)
N1—N2—C3—C31	179.3 (3)	Cl34—C34—C35—C36	−178.3 (3)
N1—N2—C3—C4	−3.4 (4)	C34—C35—C36—C31	−0.2 (5)
N2—C3—C4—C5	15.3 (4)	C32—C31—C36—C35	−2.1 (5)
C31—C3—C4—C5	−167.6 (3)	C3—C31—C36—C35	176.1 (3)
C11—N1—C5—C51	77.1 (4)	N1—C5—C51—C52	32.9 (4)
N2—N1—C5—C51	−99.5 (3)	C4—C5—C51—C52	−78.7 (4)
C11—N1—C5—C4	−164.0 (3)	N1—C5—C51—C56	−151.4 (3)
N2—N1—C5—C4	19.5 (3)	C4—C5—C51—C56	97.0 (4)
C3—C4—C5—N1	−19.2 (3)	C56—C51—C52—C53	1.4 (5)
C3—C4—C5—C51	99.8 (3)	C5—C51—C52—C53	177.3 (3)
N2—N1—C11—N11	1.3 (5)	C51—C52—C53—C54	0.3 (5)
C5—N1—C11—N11	−175.0 (3)	C52—C53—C54—C55	−2.1 (5)
N2—N1—C11—S11	−178.0 (2)	C52—C53—C54—O54	176.5 (3)
C5—N1—C11—S11	5.6 (5)	O54—C54—C55—C56	−176.7 (3)
N2—C3—C31—C32	158.8 (3)	C53—C54—C55—C56	2.1 (5)
C4—C3—C31—C32	−18.1 (5)	C54—C55—C56—C51	−0.3 (5)
N2—C3—C31—C36	−19.3 (5)	C52—C51—C56—C55	−1.5 (5)
C4—C3—C31—C36	163.8 (3)	C5—C51—C56—C55	−177.3 (3)
C36—C31—C32—C33	2.5 (6)	C55—C54—O54—C57	170.8 (3)
C3—C31—C32—C33	−175.7 (4)	C53—C54—O54—C57	−7.9 (5)
C31—C32—C33—C34	−0.5 (6)	C54—O54—C57—C58	−173.3 (3)
C32—C33—C34—C35	−1.9 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11A···N2	0.80 (4)	2.23 (4)	2.614 (5)	110 (4)
N11—H11B···S11^i	0.88 (4)	2.63 (4)	3.483 (4)	164 (4)
C52—H52···S11^ii	0.93	2.85	3.641 (4)	144

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

(RS)-3-(4-Bromophenyl)-5-[4-(prop-2-ynyloxy)phenyl]-4,5-dihydropyrazole-1-carbothioamide (V)

Crystal data

C19H16BrN3OS	F(000) = 840
Mr = 414.31	Dx = 1.529 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 15.1255 (13) Å	Cell parameters from 3513 reflections
b = 6.0426 (5) Å	θ = 2.9–26.0°
c = 21.026 (2) Å	µ = 2.41 mm^−1
β = 110.555 (3)°	T = 296 K
V = 1799.4 (3) Å^3	Needle, colourless
Z = 4	0.20 × 0.15 × 0.10 mm

Data collection

Bruker APEXII diffractometer	3365 independent reflections
Radiation source: fine focussealed tube	2559 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
φ and ω scans	θmax = 25.5°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −18→18
Tmin = 0.584, Tmax = 0.786	k = −7→7
18295 measured reflections	l = −25→25

Refinement

Refinement on F^2	Primary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.026P)^2 + 3.0352P] where P = (Fo^2 + 2Fc^2)/3
S = 1.16	(Δ/σ)max < 0.001
3365 reflections	Δρmax = 0.50 e Å^−3
232 parameters	Δρmin = −0.46 e Å^−3
0 restraints

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.

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

	x	y	z	Uiso*/Ueq
N1	0.5170 (2)	0.7430 (5)	0.34130 (16)	0.0407 (8)
N2	0.4573 (2)	0.5650 (5)	0.31602 (17)	0.0402 (8)
C3	0.4559 (3)	0.5230 (7)	0.2555 (2)	0.0398 (9)
C4	0.5136 (3)	0.6835 (7)	0.2315 (2)	0.0451 (10)
H4A	0.4737	0.7891	0.1994	0.054*
H4	0.5531	0.6073	0.2108	0.054*
C5	0.5736 (3)	0.7972 (7)	0.2985 (2)	0.0406 (9)
H5	0.5759	0.9575	0.2922	0.049*
C11	0.5228 (3)	0.8343 (6)	0.4015 (2)	0.0387 (9)
S11	0.59333 (9)	1.05265 (18)	0.43388 (6)	0.0490 (3)
N11	0.4689 (3)	0.7426 (8)	0.4319 (2)	0.0596 (12)
H11B	0.467 (4)	0.803 (8)	0.467 (3)	0.071*
H11A	0.438 (4)	0.632 (9)	0.415 (3)	0.071*
C31	0.3993 (3)	0.3401 (7)	0.2168 (2)	0.0408 (10)
C32	0.3746 (4)	0.3310 (8)	0.1462 (2)	0.0583 (13)
H32	0.3983	0.4365	0.1243	0.070*
C33	0.3154 (4)	0.1675 (9)	0.1088 (2)	0.0634 (14)
H33	0.2992	0.1628	0.0619	0.076*
C34	0.2812 (3)	0.0132 (8)	0.1412 (2)	0.0481 (11)
Br34	0.19753 (4)	−0.20866 (10)	0.08901 (3)	0.0711 (2)
C35	0.3073 (3)	0.0108 (8)	0.2113 (2)	0.0522 (11)
H35	0.2854	−0.0992	0.2330	0.063*
C36	0.3664 (3)	0.1757 (7)	0.2483 (2)	0.0469 (11)
H36	0.3845	0.1758	0.2953	0.056*
C51	0.6719 (3)	0.7015 (7)	0.3267 (2)	0.0392 (9)
C52	0.6889 (3)	0.5033 (7)	0.3620 (2)	0.0469 (11)
H52	0.6393	0.4331	0.3703	0.056*
C53	0.7771 (3)	0.4068 (7)	0.3853 (2)	0.0478 (11)
H53	0.7865	0.2730	0.4086	0.057*
C54	0.8517 (3)	0.5110 (7)	0.3737 (2)	0.0414 (10)
C55	0.8359 (3)	0.7055 (7)	0.3372 (2)	0.0443 (10)
H55	0.8855	0.7741	0.3284	0.053*
C56	0.7474 (3)	0.7991 (7)	0.3137 (2)	0.0425 (10)
H56	0.7378	0.9296	0.2887	0.051*
O54	0.9434 (2)	0.4368 (5)	0.39764 (15)	0.0508 (8)
C57	0.9628 (3)	0.2555 (7)	0.4439 (2)	0.0517 (11)
H57A	0.9304	0.1240	0.4207	0.062*
H57B	0.9402	0.2887	0.4807	0.062*
C58	1.0635 (3)	0.2166 (8)	0.4707 (2)	0.0501 (11)
C59	1.1443 (4)	0.1780 (8)	0.4958 (2)	0.0589 (13)
H59	1.2084	0.1474	0.5157	0.071*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0450 (19)	0.045 (2)	0.0376 (19)	−0.0074 (16)	0.0215 (16)	−0.0019 (16)
N2	0.0406 (19)	0.0416 (19)	0.039 (2)	−0.0028 (16)	0.0142 (16)	−0.0026 (16)
C3	0.039 (2)	0.044 (2)	0.035 (2)	0.0038 (19)	0.0108 (19)	0.0046 (19)
C4	0.049 (2)	0.052 (3)	0.037 (2)	0.004 (2)	0.019 (2)	0.007 (2)
C5	0.047 (2)	0.039 (2)	0.042 (2)	−0.005 (2)	0.024 (2)	0.0069 (19)
C11	0.040 (2)	0.037 (2)	0.040 (2)	−0.0015 (18)	0.0150 (19)	0.0032 (18)
S11	0.0598 (7)	0.0428 (6)	0.0489 (7)	−0.0136 (5)	0.0247 (6)	−0.0035 (5)
N11	0.071 (3)	0.068 (3)	0.053 (3)	−0.033 (2)	0.038 (2)	−0.019 (2)
C31	0.037 (2)	0.046 (2)	0.038 (2)	0.0051 (19)	0.0122 (19)	−0.0017 (19)
C32	0.067 (3)	0.067 (3)	0.040 (3)	−0.008 (3)	0.018 (2)	0.002 (2)
C33	0.068 (3)	0.078 (4)	0.038 (3)	0.000 (3)	0.011 (3)	−0.007 (3)
C34	0.036 (2)	0.051 (3)	0.054 (3)	0.000 (2)	0.012 (2)	−0.017 (2)
Br34	0.0495 (3)	0.0782 (4)	0.0824 (4)	−0.0050 (3)	0.0191 (3)	−0.0385 (3)
C35	0.052 (3)	0.050 (3)	0.059 (3)	−0.003 (2)	0.024 (2)	−0.006 (2)
C36	0.047 (2)	0.052 (3)	0.043 (3)	0.001 (2)	0.017 (2)	−0.002 (2)
C51	0.047 (2)	0.037 (2)	0.038 (2)	−0.0083 (19)	0.019 (2)	−0.0013 (18)
C52	0.046 (3)	0.044 (2)	0.058 (3)	−0.008 (2)	0.027 (2)	0.010 (2)
C53	0.053 (3)	0.039 (2)	0.055 (3)	−0.002 (2)	0.022 (2)	0.010 (2)
C54	0.045 (2)	0.045 (2)	0.038 (2)	−0.006 (2)	0.019 (2)	−0.0059 (19)
C55	0.046 (2)	0.051 (3)	0.042 (2)	−0.011 (2)	0.023 (2)	0.000 (2)
C56	0.054 (3)	0.041 (2)	0.036 (2)	−0.010 (2)	0.021 (2)	0.0056 (19)
O54	0.0446 (17)	0.061 (2)	0.0516 (18)	0.0007 (15)	0.0223 (15)	0.0057 (15)
C57	0.053 (3)	0.049 (3)	0.055 (3)	−0.002 (2)	0.021 (2)	−0.003 (2)
C58	0.057 (3)	0.055 (3)	0.042 (3)	−0.002 (2)	0.021 (2)	−0.009 (2)
C59	0.055 (3)	0.072 (3)	0.052 (3)	0.005 (3)	0.023 (3)	0.003 (3)

Geometric parameters (Å, º)

N1—C11	1.354 (5)	C34—Br34	1.904 (4)
N1—N2	1.385 (4)	C35—C36	1.381 (6)
N1—C5	1.480 (5)	C35—H35	0.9300
N2—C3	1.292 (5)	C36—H36	0.9300
C3—C31	1.458 (6)	C51—C52	1.385 (6)
C3—C4	1.505 (5)	C51—C56	1.396 (5)
C4—C5	1.542 (6)	C52—C53	1.378 (6)
C4—H4A	0.9700	C52—H52	0.9300
C4—H4	0.9700	C53—C54	1.387 (6)
C5—C51	1.509 (6)	C53—H53	0.9300
C5—H5	0.9800	C54—O54	1.374 (5)
C11—N11	1.323 (5)	C54—C55	1.378 (6)
C11—S11	1.683 (4)	C55—C56	1.375 (6)
N11—H11B	0.83 (5)	C55—H55	0.9300
N11—H11A	0.82 (5)	C56—H56	0.9300
C31—C36	1.380 (6)	O54—C57	1.425 (5)
C31—C32	1.398 (6)	C57—C58	1.446 (6)
C32—C33	1.379 (7)	C57—H57A	0.9700
C32—H32	0.9300	C57—H57B	0.9700
C33—C34	1.360 (6)	C58—C59	1.172 (6)
C33—H33	0.9300	C59—H59	0.9300
C34—C35	1.387 (6)
C11—N1—N2	119.6 (3)	C33—C34—Br34	119.2 (4)
C11—N1—C5	128.0 (3)	C35—C34—Br34	119.3 (4)
N2—N1—C5	112.1 (3)	C36—C35—C34	118.5 (4)
C3—N2—N1	108.2 (3)	C36—C35—H35	120.8
N2—C3—C31	120.1 (4)	C34—C35—H35	120.8
N2—C3—C4	113.1 (4)	C31—C36—C35	121.4 (4)
C31—C3—C4	126.7 (4)	C31—C36—H36	119.3
C3—C4—C5	101.9 (3)	C35—C36—H36	119.3
C3—C4—H4A	111.4	C52—C51—C56	117.3 (4)
C5—C4—H4A	111.4	C52—C51—C5	121.0 (3)
C3—C4—H4	111.4	C56—C51—C5	121.5 (4)
C5—C4—H4	111.4	C53—C52—C51	122.0 (4)
H4A—C4—H4	109.3	C53—C52—H52	119.0
N1—C5—C51	112.1 (3)	C51—C52—H52	119.0
N1—C5—C4	100.2 (3)	C52—C53—C54	119.5 (4)
C51—C5—C4	111.7 (3)	C52—C53—H53	120.3
N1—C5—H5	110.8	C54—C53—H53	120.3
C51—C5—H5	110.8	O54—C54—C55	116.0 (3)
C4—C5—H5	110.8	O54—C54—C53	124.5 (4)
N11—C11—N1	115.6 (4)	C55—C54—C53	119.5 (4)
N11—C11—S11	122.9 (3)	C56—C55—C54	120.5 (4)
N1—C11—S11	121.5 (3)	C56—C55—H55	119.7
C11—N11—H11B	117 (4)	C54—C55—H55	119.7
C11—N11—H11A	119 (4)	C55—C56—C51	121.1 (4)
H11B—N11—H11A	124 (5)	C55—C56—H56	119.5
C36—C31—C32	118.2 (4)	C51—C56—H56	119.5
C36—C31—C3	121.2 (4)	C54—O54—C57	116.1 (3)
C32—C31—C3	120.5 (4)	O54—C57—C58	109.1 (4)
C33—C32—C31	120.9 (5)	O54—C57—H57A	109.9
C33—C32—H32	119.6	C58—C57—H57A	109.9
C31—C32—H32	119.6	O54—C57—H57B	109.9
C34—C33—C32	119.4 (4)	C58—C57—H57B	109.9
C34—C33—H33	120.3	H57A—C57—H57B	108.3
C32—C33—H33	120.3	C59—C58—C57	175.8 (5)
C33—C34—C35	121.5 (4)	C58—C59—H59	180.0
C11—N1—N2—C3	173.1 (4)	C32—C33—C34—Br34	178.7 (4)
C5—N1—N2—C3	−11.5 (4)	C33—C34—C35—C36	2.7 (7)
N1—N2—C3—C31	179.2 (3)	Br34—C34—C35—C36	−178.7 (3)
N1—N2—C3—C4	−3.1 (5)	C32—C31—C36—C35	−2.7 (6)
N2—C3—C4—C5	15.1 (5)	C3—C31—C36—C35	175.3 (4)
C31—C3—C4—C5	−167.3 (4)	C34—C35—C36—C31	0.1 (6)
C11—N1—C5—C51	76.1 (5)	N1—C5—C51—C52	32.2 (5)
N2—N1—C5—C51	−98.8 (4)	C4—C5—C51—C52	−79.4 (5)
C11—N1—C5—C4	−165.2 (4)	N1—C5—C51—C56	−153.0 (4)
N2—N1—C5—C4	19.8 (4)	C4—C5—C51—C56	95.5 (4)
C3—C4—C5—N1	−19.2 (4)	C56—C51—C52—C53	1.6 (6)
C3—C4—C5—C51	99.6 (4)	C5—C51—C52—C53	176.6 (4)
N2—N1—C11—N11	−0.1 (6)	C51—C52—C53—C54	0.5 (7)
C5—N1—C11—N11	−174.8 (4)	C52—C53—C54—O54	176.2 (4)
N2—N1—C11—S11	−179.2 (3)	C52—C53—C54—C55	−2.1 (6)
C5—N1—C11—S11	6.1 (6)	O54—C54—C55—C56	−177.0 (4)
N2—C3—C31—C36	−17.0 (6)	C53—C54—C55—C56	1.5 (6)
C4—C3—C31—C36	165.6 (4)	C54—C55—C56—C51	0.7 (6)
N2—C3—C31—C32	161.0 (4)	C52—C51—C56—C55	−2.2 (6)
C4—C3—C31—C32	−16.4 (6)	C5—C51—C56—C55	−177.2 (4)
C36—C31—C32—C33	2.8 (7)	C55—C54—O54—C57	170.7 (4)
C3—C31—C32—C33	−175.3 (4)	C53—C54—O54—C57	−7.6 (6)
C31—C32—C33—C34	−0.2 (8)	C54—O54—C57—C58	−172.7 (3)
C32—C33—C34—C35	−2.6 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11A···N2	0.82 (5)	2.24 (6)	2.611 (5)	108 (5)
N11—H11A···Br34^i	0.82 (5)	2.89 (6)	3.632 (5)	152 (5)
N11—H11B···S11^ii	0.83 (6)	2.70 (6)	3.500 (5)	162 (6)
C52—H52···S11^iii	0.93	2.87	3.650 (5)	143

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

(RS)-3-(4-Methoxyphenyl)-5-[4-(prop-2-ynyloxy)phenyl]-4,5-dihydropyrazole-1-carbothioamide (VI)

Crystal data

C20H19N3O2S	F(000) = 768
Mr = 365.44	Dx = 1.330 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.7852 (15) Å	Cell parameters from 3824 reflections
b = 7.5345 (11) Å	θ = 1.7–26.6°
c = 20.599 (3) Å	µ = 0.20 mm^−1
β = 93.555 (4)°	T = 296 K
V = 1825.6 (4) Å^3	Block, colourless
Z = 4	0.20 × 0.20 × 0.15 mm

Data collection

Bruker APEXII diffractometer	3822 independent reflections
Radiation source: fine focussealed tube	1864 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.100
φ and ω scans	θmax = 26.6°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −14→14
Tmin = 0.908, Tmax = 0.971	k = −9→9
20467 measured reflections	l = −23→25

Refinement

Refinement on F^2	Primary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.118	w = 1/[σ^2(Fo^2) + (0.0424P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max < 0.001
3822 reflections	Δρmax = 0.21 e Å^−3
242 parameters	Δρmin = −0.24 e Å^−3
0 restraints

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.

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

	x	y	z	Uiso*/Ueq
N1	0.32812 (16)	0.5906 (3)	0.30356 (11)	0.0359 (6)
N2	0.39265 (16)	0.4472 (3)	0.32813 (11)	0.0359 (6)
C3	0.3292 (2)	0.3478 (3)	0.36206 (13)	0.0358 (7)
C4	0.2109 (2)	0.4218 (4)	0.36538 (14)	0.0431 (8)
H4A	0.2006	0.4759	0.4073	0.052*
H4B	0.1538	0.3303	0.3573	0.052*
C5	0.20546 (19)	0.5611 (3)	0.31084 (15)	0.0396 (7)
H5	0.1699	0.6702	0.3257	0.047*
C11	0.3763 (2)	0.7190 (3)	0.26933 (13)	0.0341 (7)
S11	0.29954 (5)	0.88567 (9)	0.23445 (4)	0.0462 (3)
N11	0.48918 (18)	0.7072 (3)	0.26592 (12)	0.0398 (7)
H11A	0.529 (2)	0.614 (3)	0.2788 (13)	0.048*
H11B	0.520 (2)	0.781 (3)	0.2386 (13)	0.048*
C31	0.3722 (2)	0.1830 (3)	0.39094 (13)	0.0375 (7)
C32	0.3004 (2)	0.0594 (4)	0.41761 (14)	0.0452 (8)
H32	0.2243	0.0881	0.4213	0.054*
C33	0.3393 (2)	−0.1033 (4)	0.43855 (14)	0.0499 (8)
H33	0.2898	−0.1834	0.4563	0.060*
C34	0.4514 (3)	−0.1485 (4)	0.43337 (14)	0.0456 (8)
C35	0.5260 (2)	−0.0259 (4)	0.40995 (14)	0.0444 (8)
H35	0.6026	−0.0541	0.4083	0.053*
C36	0.4869 (2)	0.1379 (3)	0.38909 (14)	0.0414 (7)
H36	0.5376	0.2198	0.3735	0.050*
O34	0.48126 (17)	−0.3164 (3)	0.45311 (10)	0.0614 (6)
C37	0.5942 (3)	−0.3754 (4)	0.44406 (16)	0.0660 (10)
H37A	0.6085	−0.3691	0.3987	0.099*
H37B	0.6028	−0.4958	0.4588	0.099*
H37C	0.6474	−0.3010	0.4685	0.099*
C51	0.1451 (2)	0.4974 (3)	0.24816 (14)	0.0350 (7)
C52	0.1993 (2)	0.4027 (4)	0.20147 (15)	0.0476 (8)
H52	0.2764	0.3777	0.2083	0.057*
C53	0.1417 (2)	0.3442 (4)	0.14482 (15)	0.0493 (8)
H53	0.1798	0.2815	0.1140	0.059*
C54	0.0272 (2)	0.3798 (3)	0.13462 (15)	0.0394 (7)
C55	−0.0289 (2)	0.4687 (3)	0.18155 (15)	0.0408 (8)
H55	−0.1065	0.4899	0.1754	0.049*
C56	0.0297 (2)	0.5260 (3)	0.23739 (15)	0.0406 (8)
H56	−0.0094	0.5855	0.2687	0.049*
O54	−0.03798 (14)	0.3313 (3)	0.07948 (10)	0.0550 (6)
C57	0.0190 (3)	0.2607 (4)	0.02690 (16)	0.0612 (9)
H57A	0.0538	0.1482	0.0395	0.073*
H57B	0.0787	0.3414	0.0154	0.073*
C58	−0.0612 (3)	0.2348 (4)	−0.02888 (19)	0.0612 (10)
C59	−0.1219 (3)	0.2176 (5)	−0.0749 (2)	0.0854 (12)
H59	−0.1707	0.2038	−0.1119	0.102*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0287 (12)	0.0365 (13)	0.0423 (17)	−0.0015 (10)	0.0015 (11)	0.0019 (12)
N2	0.0345 (12)	0.0368 (13)	0.0361 (16)	−0.0009 (11)	−0.0003 (11)	0.0000 (11)
C3	0.0376 (15)	0.0399 (17)	0.0298 (19)	−0.0063 (13)	0.0020 (13)	−0.0049 (14)
C4	0.0382 (16)	0.0501 (18)	0.042 (2)	−0.0060 (13)	0.0076 (14)	−0.0019 (16)
C5	0.0267 (14)	0.0425 (17)	0.050 (2)	−0.0007 (13)	0.0072 (14)	−0.0051 (16)
C11	0.0336 (15)	0.0344 (15)	0.0344 (19)	−0.0045 (13)	0.0017 (13)	−0.0058 (14)
S11	0.0388 (4)	0.0429 (4)	0.0565 (6)	0.0027 (3)	0.0007 (4)	0.0048 (4)
N11	0.0334 (14)	0.0378 (15)	0.0482 (19)	0.0000 (11)	0.0028 (12)	0.0077 (13)
C31	0.0434 (16)	0.0404 (17)	0.0287 (19)	−0.0072 (14)	0.0021 (13)	0.0002 (14)
C32	0.0457 (16)	0.056 (2)	0.034 (2)	−0.0095 (15)	0.0025 (15)	0.0001 (16)
C33	0.062 (2)	0.0484 (19)	0.039 (2)	−0.0154 (16)	0.0031 (16)	0.0061 (16)
C34	0.061 (2)	0.0429 (19)	0.032 (2)	−0.0076 (16)	−0.0019 (15)	0.0014 (15)
C35	0.0454 (17)	0.0462 (19)	0.041 (2)	−0.0009 (15)	−0.0015 (15)	0.0031 (16)
C36	0.0452 (17)	0.0422 (18)	0.037 (2)	−0.0067 (14)	0.0016 (14)	0.0024 (15)
O34	0.0796 (15)	0.0455 (13)	0.0592 (17)	−0.0021 (11)	0.0061 (12)	0.0134 (12)
C37	0.087 (2)	0.048 (2)	0.063 (3)	0.0078 (18)	0.000 (2)	0.0058 (18)
C51	0.0295 (14)	0.0343 (15)	0.041 (2)	−0.0005 (12)	0.0029 (14)	0.0024 (14)
C52	0.0303 (15)	0.0586 (19)	0.054 (2)	0.0087 (14)	0.0045 (15)	−0.0084 (18)
C53	0.0416 (17)	0.063 (2)	0.044 (2)	0.0055 (15)	0.0041 (15)	−0.0163 (17)
C54	0.0345 (16)	0.0405 (17)	0.043 (2)	−0.0038 (13)	−0.0021 (15)	0.0003 (15)
C55	0.0283 (14)	0.0414 (17)	0.052 (2)	0.0005 (13)	0.0005 (15)	−0.0002 (16)
C56	0.0325 (15)	0.0390 (16)	0.051 (2)	0.0005 (13)	0.0083 (15)	−0.0066 (15)
O54	0.0442 (12)	0.0752 (15)	0.0446 (16)	−0.0039 (10)	−0.0042 (11)	−0.0093 (12)
C57	0.067 (2)	0.063 (2)	0.053 (3)	0.0021 (18)	−0.0025 (19)	−0.0076 (19)
C58	0.075 (2)	0.054 (2)	0.053 (3)	0.0026 (18)	−0.009 (2)	−0.0034 (19)
C59	0.111 (3)	0.075 (3)	0.066 (3)	0.001 (2)	−0.029 (2)	−0.005 (2)

Geometric parameters (Å, º)

N1—C11	1.343 (3)	C35—H35	0.9300
N1—N2	1.398 (3)	C36—H36	0.9300
N1—C5	1.479 (3)	O34—C37	1.426 (3)
N2—C3	1.294 (3)	C37—H37A	0.9600
C3—C31	1.455 (3)	C37—H37B	0.9600
C3—C4	1.507 (3)	C37—H37C	0.9600
C4—C5	1.536 (4)	C51—C56	1.381 (3)
C4—H4A	0.9700	C51—C52	1.385 (3)
C4—H4B	0.9700	C52—C53	1.385 (4)
C5—C51	1.513 (4)	C52—H52	0.9300
C5—H5	0.9800	C53—C54	1.379 (3)
C11—N11	1.339 (3)	C53—H53	0.9300
C11—S11	1.683 (3)	C54—C55	1.378 (4)
N11—H11A	0.88 (2)	C54—O54	1.380 (3)
N11—H11B	0.89 (3)	C55—C56	1.374 (4)
C31—C32	1.394 (3)	C55—H55	0.9300
C31—C36	1.396 (3)	C56—H56	0.9300
C32—C33	1.369 (4)	O54—C57	1.413 (3)
C32—H32	0.9300	C57—C58	1.455 (4)
C33—C34	1.375 (4)	C57—H57A	0.9700
C33—H33	0.9300	C57—H57B	0.9700
C34—O34	1.368 (3)	C58—C59	1.160 (4)
C34—C35	1.383 (3)	C59—H59	0.9300
C35—C36	1.377 (3)
C11—N1—N2	120.55 (19)	C34—C35—H35	120.0
C11—N1—C5	127.5 (2)	C35—C36—C31	121.0 (2)
N2—N1—C5	111.11 (19)	C35—C36—H36	119.5
C3—N2—N1	108.86 (19)	C31—C36—H36	119.5
N2—C3—C31	121.1 (2)	C34—O34—C37	118.3 (2)
N2—C3—C4	112.2 (2)	O34—C37—H37A	109.5
C31—C3—C4	126.7 (2)	O34—C37—H37B	109.5
C3—C4—C5	102.5 (2)	H37A—C37—H37B	109.5
C3—C4—H4A	111.3	O34—C37—H37C	109.5
C5—C4—H4A	111.3	H37A—C37—H37C	109.5
C3—C4—H4B	111.3	H37B—C37—H37C	109.5
C5—C4—H4B	111.3	C56—C51—C52	117.4 (3)
H4A—C4—H4B	109.2	C56—C51—C5	119.6 (2)
N1—C5—C51	111.8 (2)	C52—C51—C5	122.9 (2)
N1—C5—C4	100.4 (2)	C51—C52—C53	121.7 (2)
C51—C5—C4	113.8 (2)	C51—C52—H52	119.1
N1—C5—H5	110.2	C53—C52—H52	119.1
C51—C5—H5	110.2	C54—C53—C52	119.3 (3)
C4—C5—H5	110.2	C54—C53—H53	120.3
N11—C11—N1	115.7 (2)	C52—C53—H53	120.3
N11—C11—S11	122.4 (2)	C55—C54—C53	119.6 (3)
N1—C11—S11	121.85 (18)	C55—C54—O54	116.1 (2)
C11—N11—H11A	123.2 (16)	C53—C54—O54	124.3 (3)
C11—N11—H11B	116.0 (16)	C56—C55—C54	120.2 (2)
H11A—N11—H11B	118 (2)	C56—C55—H55	119.9
C32—C31—C36	117.4 (3)	C54—C55—H55	119.9
C32—C31—C3	121.7 (2)	C55—C56—C51	121.6 (3)
C36—C31—C3	120.7 (2)	C55—C56—H56	119.2
C33—C32—C31	121.5 (3)	C51—C56—H56	119.2
C33—C32—H32	119.3	C54—O54—C57	117.6 (2)
C31—C32—H32	119.3	O54—C57—C58	109.9 (3)
C32—C33—C34	120.1 (3)	O54—C57—H57A	109.7
C32—C33—H33	119.9	C58—C57—H57A	109.7
C34—C33—H33	119.9	O54—C57—H57B	109.7
O34—C34—C33	115.9 (3)	C58—C57—H57B	109.7
O34—C34—C35	124.3 (3)	H57A—C57—H57B	108.2
C33—C34—C35	119.8 (3)	C59—C58—C57	177.2 (4)
C36—C35—C34	120.0 (3)	C58—C59—H59	180.0
C36—C35—H35	120.0
C11—N1—N2—C3	176.5 (2)	O34—C34—C35—C36	177.7 (3)
C5—N1—N2—C3	−13.2 (3)	C33—C34—C35—C36	−3.0 (4)
N1—N2—C3—C31	176.8 (2)	C34—C35—C36—C31	−0.2 (4)
N1—N2—C3—C4	−1.8 (3)	C32—C31—C36—C35	3.1 (4)
N2—C3—C4—C5	15.0 (3)	C3—C31—C36—C35	−172.9 (3)
C31—C3—C4—C5	−163.6 (3)	C33—C34—O34—C37	175.1 (3)
C11—N1—C5—C51	69.8 (3)	C35—C34—O34—C37	−5.5 (4)
N2—N1—C5—C51	−99.7 (2)	N1—C5—C51—C56	−155.6 (2)
C11—N1—C5—C4	−169.2 (2)	C4—C5—C51—C56	91.5 (3)
N2—N1—C5—C4	21.3 (3)	N1—C5—C51—C52	27.6 (4)
C3—C4—C5—N1	−20.3 (3)	C4—C5—C51—C52	−85.3 (3)
C3—C4—C5—C51	99.3 (2)	C56—C51—C52—C53	2.4 (4)
N2—N1—C11—N11	−5.7 (4)	C5—C51—C52—C53	179.2 (3)
C5—N1—C11—N11	−174.3 (2)	C51—C52—C53—C54	−0.5 (5)
N2—N1—C11—S11	175.50 (18)	C52—C53—C54—C55	−1.7 (4)
C5—N1—C11—S11	6.9 (4)	C52—C53—C54—O54	178.6 (3)
N2—C3—C31—C32	−168.5 (3)	C53—C54—C55—C56	1.9 (4)
C4—C3—C31—C32	10.0 (4)	O54—C54—C55—C56	−178.4 (2)
N2—C3—C31—C36	7.4 (4)	C54—C55—C56—C51	0.2 (4)
C4—C3—C31—C36	−174.2 (3)	C52—C51—C56—C55	−2.3 (4)
C36—C31—C32—C33	−2.9 (4)	C5—C51—C56—C55	−179.2 (2)
C3—C31—C32—C33	173.1 (3)	C55—C54—O54—C57	172.0 (2)
C31—C32—C33—C34	−0.2 (5)	C53—C54—O54—C57	−8.3 (4)
C32—C33—C34—O34	−177.4 (3)	C54—O54—C57—C58	−174.1 (2)
C32—C33—C34—C35	3.2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11A···N2	0.88 (2)	2.32 (2)	2.637 (3)	101.2 (18)
N11—H11A···S11^i	0.88 (2)	2.68 (2)	3.474 (2)	151 (2)
N11—H11B···N2^ii	0.89 (2)	2.17 (2)	3.049 (3)	175 (2)
C37—H37B···O34^iii	0.96	2.55	3.302 (4)	135
C56—H56···Cg2^iv	0.93	2.93	3.717 (3)	143

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