Reduced 3,4′-bi­pyrazoles carrying thio­phene and thia­zole substituents: structures of two intermediates and two products

Reduced 3,4′-bi­pyrazole-2-carbo­thio­amides are formed in cyclo­addition reactions between chalcones and thio­semicarbazide, and these can undergo further cyclo­addition reactions to form oxothaazole of thia­zole substituents. Structure analysis establishes the regiochemistry of the cyclo­addition reactions and shows the very simple patterns of supra­molecular assembly in these compounds.

Key indicators

Structure: Ia

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.056
• wR factor = 0.112
• Data-to-parameter ratio = 15.4

Structure: Ib

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• Disorder in main residue
• R factor = 0.046
• wR factor = 0.097
• Data-to-parameter ratio = 15.8

Structure: II

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.010 Å
• Disorder in main residue
• R factor = 0.079
• wR factor = 0.143
• Data-to-parameter ratio = 14.1

Structure: III

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.039
• wR factor = 0.095
• Data-to-parameter ratio = 14.4

checkCIF/PLATON results

No syntax errors found



Datablock: Ia


Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C52      --C57      .        5.3 s.u.
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00489 Ang.
PLAT420_ALERT_2_C D-H Without Acceptor       N423     --H42B     .     Please Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      8.699 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      3.013 Check
PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Theta(Min).          6 Note
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          5 Report
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         10 Note
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          5 Report
PLAT175_ALERT_4_G The CIF-Embedded .res File Contains SAME Records          1 Report
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1  )        15% Note
PLAT793_ALERT_4_G Model has Chirality at C43         (Centro SPGR)          R Verify
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............         10 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         42 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          1 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   8 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   8 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
   7 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check




Datablock: Ib


Alert level C
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl52     ..S551     .       3.42 Ang.
                                                 2-x,-y,1-z  =      3_756 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      5.489 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          7 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         10 Note
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          5 Report
PLAT175_ALERT_4_G The CIF-Embedded .res File Contains SAME Records          1 Report
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1  )        15% Note
PLAT793_ALERT_4_G Model has Chirality at C43         (Centro SPGR)          R Verify
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............         10 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          4 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        379 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          6 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          5 Info

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

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




Datablock: II


Alert level B
PLAT026_ALERT_3_B Ratio Observed / Unique Reflections (too) Low ..        31% Check

Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.12
            Rint given   0.138
PLAT020_ALERT_3_C The Value of Rint is Greater Than 0.12 .........      0.138 Report
PLAT220_ALERT_2_C NonSolvent   Resd 1  C   Ueq(max)/Ueq(min) Range        3.3 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C426     --C427     .        5.7 s.u.
PLAT234_ALERT_4_C Large Hirshfeld Difference C52      --C53      .       0.17 Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C53      --C54      .       0.17 Ang.
PLAT241_ALERT_2_C High   'MainMol' Ueq as Compared to Neighbors of        C54 Check
PLAT242_ALERT_2_C Low    'MainMol' Ueq as Compared to Neighbors of        C52 Check
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00991 Ang.
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C424     - C425     .       1.53 Ang.
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......     24.972 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      6.201 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.983 Check
PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Theta(Min).          6 Note
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
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         10 Note
PLAT154_ALERT_1_G The s.u.'s on the Cell Angles are Equal ..(Note)       0.02 Degree
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          5 Report
PLAT175_ALERT_4_G The CIF-Embedded .res File Contains SAME Records          1 Report
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1  )        12% Note
PLAT793_ALERT_4_G Model has Chirality at C43         (Centro SPGR)          R Verify
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............         10 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
   1 ALERT level B = A potentially serious problem, consider carefully
  16 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   8 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 ALERT type 2 Indicator that the structure model may be wrong or deficient
  11 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




Datablock: III



Alert level C
PLAT242_ALERT_2_C Low    'MainMol' Ueq as Compared to Neighbors of       C444 Check
PLAT334_ALERT_2_C Small Aver. Benzene C-C Dist C51      -C56             1.37 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Theta(Min).          6 Note
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          2 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         10 Note
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          5 Report
PLAT175_ALERT_4_G The CIF-Embedded .res File Contains SAME Records          1 Report
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1  )        12% Note
PLAT793_ALERT_4_G Model has Chirality at C43         (Centro SPGR)          R Verify
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............         10 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          2 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
   7 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 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
   3 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: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXT (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).

3'-Methyl-5'-(2-methylphenoxy)-1'-phenyl-5-(thiophen-2-yl)-3,4-dihydro-1'H,2H-3,4'-bipyrazole-2-carbothioamide (Ia)

Crystal data

C25H23N5OS2	Z = 2
Mr = 473.60	F(000) = 496
Triclinic, P1	Dx = 1.324 Mg m^−3
a = 8.6269 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.8418 (9) Å	Cell parameters from 5098 reflections
c = 14.900 (1) Å	θ = 2.9–27.9°
α = 90.588 (7)°	µ = 0.25 mm^−1
β = 106.162 (8)°	T = 296 K
γ = 101.441 (7)°	Needle, yellow
V = 1188.05 (17) Å^3	0.36 × 0.12 × 0.04 mm

Data collection

Oxford Diffraction Xcalibur with Sapphire CCD detector diffractometer	4898 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2524 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ω scans	θmax = 26.6°, θmin = 2.9°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −10→9
Tmin = 0.949, Tmax = 0.990	k = −10→12
8241 measured reflections	l = −16→18

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)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.112	w = 1/[σ^2(Fo^2) + (0.038P)^2 + 0.0763P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
4898 reflections	Δρmax = 0.18 e Å^−3
319 parameters	Δρmin = −0.18 e Å^−3
10 restraints

Special details

Experimental. CrysAlis RED, Oxford Diffraction Ltd., 2009 Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	Occ. (<1)
N1	−0.0795 (2)	0.6663 (2)	0.30851 (14)	0.0406 (6)
N2	−0.2192 (2)	0.6179 (2)	0.23518 (15)	0.0451 (6)
C3	−0.1670 (3)	0.6245 (3)	0.15926 (18)	0.0421 (7)
C4	0.0047 (3)	0.6737 (3)	0.18050 (17)	0.0384 (7)
C5	0.0541 (3)	0.6994 (3)	0.27513 (17)	0.0384 (7)
C11	−0.0885 (3)	0.6605 (3)	0.40219 (18)	0.0445 (7)
C12	0.0024 (3)	0.7654 (4)	0.4690 (2)	0.0625 (9)
H12	0.0687	0.8426	0.4532	0.075*
C13	−0.0067 (4)	0.7541 (5)	0.5603 (2)	0.0816 (12)
H13	0.0563	0.8232	0.6063	0.098*
C14	−0.1073 (5)	0.6421 (5)	0.5835 (2)	0.0838 (12)
H14	−0.1123	0.6354	0.6448	0.101*
C15	−0.2004 (4)	0.5399 (4)	0.5157 (3)	0.0757 (11)
H15	−0.2704	0.4648	0.5310	0.091*
C16	−0.1904 (3)	0.5484 (3)	0.4250 (2)	0.0565 (8)
H16	−0.2524	0.4784	0.3793	0.068*
C31	−0.2869 (3)	0.5831 (3)	0.06491 (18)	0.0615 (9)
H31A	−0.2770	0.6581	0.0249	0.092*
H31B	−0.3970	0.5616	0.0707	0.092*
H31C	−0.2637	0.5027	0.0384	0.092*
N41	0.4015 (2)	0.7247 (3)	0.16104 (14)	0.0415 (6)
N42	0.2565 (2)	0.6253 (2)	0.14876 (14)	0.0393 (6)
C43	0.1056 (3)	0.6826 (3)	0.11269 (17)	0.0412 (7)
H43	0.0379	0.6306	0.0538	0.049*
C44	0.1805 (3)	0.8295 (3)	0.09133 (18)	0.0496 (8)
H44A	0.1515	0.8403	0.0244	0.060*
H44B	0.1441	0.8997	0.1218	0.060*
C45	0.3626 (3)	0.8383 (3)	0.13106 (18)	0.0418 (7)
S421	0.09307 (9)	0.36681 (8)	0.14413 (5)	0.0559 (3)
C422	0.2638 (3)	0.4938 (3)	0.16724 (17)	0.0408 (7)
N423	0.4148 (3)	0.4679 (3)	0.20351 (18)	0.0538 (7)
H42A	0.506 (3)	0.539 (3)	0.2180 (18)	0.065*
H42B	0.426 (3)	0.380 (3)	0.2139 (19)	0.065*
S451	0.69257 (13)	0.96287 (15)	0.18083 (12)	0.0769 (5)	0.866 (3)
C452	0.4879 (3)	0.9623 (3)	0.13580 (19)	0.0515 (8)	0.866 (3)
C453	0.4652 (18)	1.0876 (10)	0.1098 (14)	0.0769 (15)	0.866 (3)
H453	0.3615	1.1067	0.0830	0.092*	0.866 (3)
C454	0.6146 (9)	1.1897 (8)	0.1270 (14)	0.104 (2)	0.866 (3)
H454	0.6204	1.2821	0.1127	0.125*	0.866 (3)
C455	0.7456 (8)	1.1343 (6)	0.1666 (8)	0.099 (2)	0.866 (3)
H455	0.8539	1.1848	0.1844	0.119*	0.866 (3)
S551	0.456 (3)	1.1213 (19)	0.104 (3)	0.0769 (15)	0.134 (3)
C552	0.4879 (3)	0.9623 (3)	0.13580 (19)	0.0515 (8)	0.134 (3)
C553	0.6476 (19)	0.960 (4)	0.159 (4)	0.0769 (5)	0.134 (3)
H553	0.6877	0.8792	0.1740	0.092*	0.134 (3)
C554	0.751 (3)	1.092 (4)	0.158 (6)	0.099 (2)	0.134 (3)
H554	0.8660	1.1083	0.1735	0.119*	0.134 (3)
C555	0.661 (4)	1.189 (4)	0.133 (10)	0.104 (2)	0.134 (3)
H555	0.7062	1.2828	0.1317	0.125*	0.134 (3)
O51	0.20838 (18)	0.73742 (19)	0.33641 (11)	0.0434 (5)
C51	0.2920 (3)	0.8764 (3)	0.34104 (17)	0.0432 (7)
C52	0.4615 (3)	0.8993 (4)	0.37778 (18)	0.0535 (8)
C53	0.5473 (5)	1.0365 (5)	0.3857 (2)	0.0833 (13)
H53	0.6615	1.0564	0.4102	0.100*
C54	0.4682 (7)	1.1423 (5)	0.3583 (3)	0.1011 (15)
H54	0.5291	1.2330	0.3649	0.121*
C55	0.3006 (6)	1.1174 (4)	0.3213 (3)	0.0882 (12)
H55	0.2478	1.1901	0.3018	0.106*
C56	0.2104 (4)	0.9822 (4)	0.3131 (2)	0.0626 (9)
H56	0.0961	0.9634	0.2889	0.075*
C57	0.5475 (4)	0.7841 (4)	0.4051 (2)	0.0804 (11)
H57A	0.6602	0.8211	0.4398	0.121*
H57B	0.5441	0.7310	0.3500	0.121*
H57C	0.4940	0.7253	0.4435	0.121*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0280 (12)	0.0587 (17)	0.0333 (13)	0.0070 (10)	0.0073 (10)	0.0036 (11)
N2	0.0269 (12)	0.0642 (18)	0.0403 (13)	0.0050 (11)	0.0063 (11)	0.0041 (11)
C3	0.0276 (14)	0.057 (2)	0.0382 (16)	0.0036 (12)	0.0073 (12)	0.0040 (13)
C4	0.0265 (14)	0.0520 (19)	0.0335 (16)	0.0026 (12)	0.0072 (12)	0.0031 (13)
C5	0.0237 (14)	0.0491 (19)	0.0400 (16)	0.0047 (12)	0.0073 (12)	0.0048 (13)
C11	0.0319 (15)	0.070 (2)	0.0363 (17)	0.0195 (14)	0.0112 (13)	0.0073 (15)
C12	0.0516 (19)	0.089 (3)	0.049 (2)	0.0129 (17)	0.0179 (16)	−0.0042 (18)
C13	0.071 (2)	0.129 (4)	0.049 (2)	0.029 (2)	0.0175 (19)	−0.011 (2)
C14	0.085 (3)	0.143 (4)	0.047 (2)	0.059 (3)	0.031 (2)	0.023 (2)
C15	0.073 (2)	0.105 (3)	0.069 (2)	0.037 (2)	0.038 (2)	0.039 (2)
C16	0.0508 (18)	0.072 (2)	0.053 (2)	0.0205 (16)	0.0208 (15)	0.0169 (16)
C31	0.0324 (16)	0.095 (3)	0.0440 (18)	−0.0081 (15)	0.0050 (14)	−0.0017 (17)
N41	0.0288 (12)	0.0448 (16)	0.0471 (14)	−0.0054 (11)	0.0141 (10)	−0.0002 (12)
N42	0.0259 (12)	0.0429 (16)	0.0468 (14)	−0.0018 (10)	0.0132 (10)	0.0027 (11)
C43	0.0313 (15)	0.054 (2)	0.0342 (15)	0.0018 (13)	0.0073 (12)	0.0049 (13)
C44	0.0437 (17)	0.060 (2)	0.0465 (17)	0.0070 (14)	0.0172 (14)	0.0109 (15)
C45	0.0369 (16)	0.049 (2)	0.0376 (16)	−0.0023 (14)	0.0154 (13)	0.0021 (14)
S421	0.0477 (5)	0.0563 (6)	0.0525 (5)	−0.0151 (4)	0.0143 (4)	0.0049 (4)
C422	0.0387 (17)	0.049 (2)	0.0340 (16)	−0.0004 (14)	0.0155 (13)	0.0007 (13)
N423	0.0410 (15)	0.0452 (18)	0.0733 (18)	0.0051 (13)	0.0161 (14)	0.0093 (15)
S451	0.0458 (7)	0.0803 (9)	0.0897 (12)	−0.0215 (6)	0.0194 (7)	0.0077 (7)
C452	0.0507 (18)	0.050 (2)	0.0530 (19)	−0.0039 (15)	0.0241 (15)	0.0042 (15)
C453	0.095 (3)	0.050 (5)	0.095 (3)	0.014 (4)	0.041 (2)	0.022 (5)
C454	0.144 (6)	0.050 (3)	0.120 (5)	−0.023 (4)	0.071 (7)	0.013 (3)
C455	0.097 (3)	0.076 (5)	0.106 (4)	−0.048 (3)	0.046 (3)	−0.013 (5)
S551	0.095 (3)	0.050 (5)	0.095 (3)	0.014 (4)	0.041 (2)	0.022 (5)
C552	0.0507 (18)	0.050 (2)	0.0530 (19)	−0.0039 (15)	0.0241 (15)	0.0042 (15)
C553	0.0458 (7)	0.0803 (9)	0.0897 (12)	−0.0215 (6)	0.0194 (7)	0.0077 (7)
C554	0.097 (3)	0.076 (5)	0.106 (4)	−0.048 (3)	0.046 (3)	−0.013 (5)
C555	0.144 (6)	0.050 (3)	0.120 (5)	−0.023 (4)	0.071 (7)	0.013 (3)
O51	0.0265 (10)	0.0521 (13)	0.0445 (11)	0.0054 (8)	0.0009 (8)	0.0032 (9)
C51	0.0373 (16)	0.050 (2)	0.0386 (16)	0.0002 (14)	0.0115 (13)	−0.0033 (14)
C52	0.0380 (17)	0.075 (3)	0.0406 (17)	0.0016 (16)	0.0073 (14)	−0.0046 (16)
C53	0.064 (2)	0.100 (4)	0.065 (2)	−0.028 (2)	0.0160 (19)	−0.015 (2)
C54	0.129 (4)	0.073 (4)	0.085 (3)	−0.032 (3)	0.043 (3)	−0.017 (3)
C55	0.137 (4)	0.054 (3)	0.083 (3)	0.018 (3)	0.048 (3)	0.004 (2)
C56	0.069 (2)	0.057 (3)	0.066 (2)	0.0164 (19)	0.0243 (18)	0.0042 (18)
C57	0.0410 (19)	0.119 (4)	0.072 (2)	0.018 (2)	0.0016 (17)	0.001 (2)

Geometric parameters (Å, º)

N1—C5	1.362 (3)	S421—C422	1.682 (3)
N1—N2	1.379 (2)	C422—N423	1.341 (3)
N1—C11	1.421 (3)	N423—H42A	0.91 (3)
N2—C3	1.326 (3)	N423—H42B	0.90 (3)
C3—C4	1.407 (3)	S451—C455	1.690 (6)
C3—C31	1.491 (3)	S451—C452	1.704 (3)
C4—C5	1.360 (3)	C452—C453	1.331 (8)
C4—C43	1.499 (3)	C453—C454	1.426 (13)
C5—O51	1.366 (3)	C453—H453	0.9300
C11—C12	1.376 (4)	C454—C455	1.343 (7)
C11—C16	1.376 (4)	C454—H454	0.9300
C12—C13	1.389 (4)	C455—H455	0.9300
C12—H12	0.9300	S551—C555	1.690 (12)
C13—C14	1.372 (5)	C553—C554	1.428 (16)
C13—H13	0.9300	C553—H553	0.9300
C14—C15	1.372 (5)	C554—C555	1.344 (12)
C14—H14	0.9300	C554—H554	0.9300
C15—C16	1.382 (4)	C555—H555	0.9300
C15—H15	0.9300	O51—C51	1.406 (3)
C16—H16	0.9300	C51—C56	1.374 (4)
C31—H31A	0.9600	C51—C52	1.382 (4)
C31—H31B	0.9600	C52—C53	1.392 (5)
C31—H31C	0.9600	C52—C57	1.475 (4)
N41—C45	1.280 (3)	C53—C54	1.361 (5)
N41—N42	1.392 (3)	C53—H53	0.9300
N42—C422	1.336 (3)	C54—C55	1.366 (5)
N42—C43	1.487 (3)	C54—H54	0.9300
C43—C44	1.537 (3)	C55—C56	1.387 (4)
C43—H43	0.9800	C55—H55	0.9300
C44—C45	1.501 (3)	C56—H56	0.9300
C44—H44A	0.9700	C57—H57A	0.9600
C44—H44B	0.9700	C57—H57B	0.9600
C45—C452	1.447 (4)	C57—H57C	0.9600
C5—N1—N2	109.56 (19)	N41—C45—C44	114.4 (2)
C5—N1—C11	130.2 (2)	C452—C45—C44	124.5 (3)
N2—N1—C11	119.8 (2)	N42—C422—N423	116.4 (2)
C3—N2—N1	105.00 (18)	N42—C422—S421	121.8 (2)
N2—C3—C4	112.4 (2)	N423—C422—S421	121.7 (2)
N2—C3—C31	120.2 (2)	C422—N423—H42A	120.3 (18)
C4—C3—C31	127.4 (2)	C422—N423—H42B	119.2 (18)
C5—C4—C3	103.8 (2)	H42A—N423—H42B	121 (3)
C5—C4—C43	129.7 (2)	C455—S451—C452	91.8 (3)
C3—C4—C43	126.3 (2)	C453—C452—C45	127.5 (7)
C4—C5—N1	109.2 (2)	C453—C452—S451	111.0 (6)
C4—C5—O51	130.8 (2)	C45—C452—S451	121.5 (3)
N1—C5—O51	119.7 (2)	C452—C453—C454	113.8 (8)
C12—C11—C16	120.5 (3)	C452—C453—H453	123.1
C12—C11—N1	120.6 (3)	C454—C453—H453	123.1
C16—C11—N1	118.8 (3)	C455—C454—C453	110.7 (6)
C11—C12—C13	118.8 (3)	C455—C454—H454	124.7
C11—C12—H12	120.6	C453—C454—H454	124.7
C13—C12—H12	120.6	C454—C455—S451	112.7 (5)
C14—C13—C12	120.8 (3)	C454—C455—H455	123.6
C14—C13—H13	119.6	S451—C455—H455	123.6
C12—C13—H13	119.6	C554—C553—H553	123.2
C15—C14—C13	119.8 (3)	C555—C554—C553	110.8 (13)
C15—C14—H14	120.1	C555—C554—H554	124.6
C13—C14—H14	120.1	C553—C554—H554	124.6
C14—C15—C16	120.1 (3)	C554—C555—S551	112.2 (12)
C14—C15—H15	119.9	C554—C555—H555	123.9
C16—C15—H15	119.9	S551—C555—H555	123.9
C11—C16—C15	119.9 (3)	C5—O51—C51	117.9 (2)
C11—C16—H16	120.0	C56—C51—C52	122.6 (3)
C15—C16—H16	120.0	C56—C51—O51	122.3 (2)
C3—C31—H31A	109.5	C52—C51—O51	115.1 (3)
C3—C31—H31B	109.5	C51—C52—C53	116.4 (3)
H31A—C31—H31B	109.5	C51—C52—C57	121.8 (3)
C3—C31—H31C	109.5	C53—C52—C57	121.7 (3)
H31A—C31—H31C	109.5	C54—C53—C52	121.7 (4)
H31B—C31—H31C	109.5	C54—C53—H53	119.2
C45—N41—N42	108.1 (2)	C52—C53—H53	119.2
C422—N42—N41	119.9 (2)	C53—C54—C55	121.0 (4)
C422—N42—C43	127.2 (2)	C53—C54—H54	119.5
N41—N42—C43	112.9 (2)	C55—C54—H54	119.5
N42—C43—C4	112.3 (2)	C54—C55—C56	119.2 (4)
N42—C43—C44	101.01 (19)	C54—C55—H55	120.4
C4—C43—C44	116.4 (2)	C56—C55—H55	120.4
N42—C43—H43	108.9	C51—C56—C55	119.2 (3)
C4—C43—H43	108.9	C51—C56—H56	120.4
C44—C43—H43	108.9	C55—C56—H56	120.4
C45—C44—C43	102.9 (2)	C52—C57—H57A	109.5
C45—C44—H44A	111.2	C52—C57—H57B	109.5
C43—C44—H44A	111.2	H57A—C57—H57B	109.5
C45—C44—H44B	111.2	C52—C57—H57C	109.5
C43—C44—H44B	111.2	H57A—C57—H57C	109.5
H44A—C44—H44B	109.1	H57B—C57—H57C	109.5
N41—C45—C452	121.1 (3)
C5—N1—N2—C3	−0.7 (3)	N42—C43—C44—C45	−7.5 (2)
C11—N1—N2—C3	−173.9 (2)	C4—C43—C44—C45	114.3 (2)
N1—N2—C3—C4	1.1 (3)	N42—N41—C45—C452	179.1 (2)
N1—N2—C3—C31	−178.5 (2)	N42—N41—C45—C44	−1.3 (3)
N2—C3—C4—C5	−1.1 (3)	C43—C44—C45—N41	6.1 (3)
C31—C3—C4—C5	178.5 (3)	C43—C44—C45—C452	−174.4 (2)
N2—C3—C4—C43	174.5 (3)	N41—N42—C422—N423	4.6 (3)
C31—C3—C4—C43	−5.8 (5)	C43—N42—C422—N423	−177.0 (2)
C3—C4—C5—N1	0.6 (3)	N41—N42—C422—S421	−174.18 (16)
C43—C4—C5—N1	−174.8 (3)	C43—N42—C422—S421	4.2 (3)
C3—C4—C5—O51	173.7 (3)	N41—C45—C452—C453	−178.0 (11)
C43—C4—C5—O51	−1.7 (5)	C44—C45—C452—C453	2.5 (12)
N2—N1—C5—C4	0.0 (3)	N41—C45—C452—S451	0.3 (4)
C11—N1—C5—C4	172.3 (3)	C44—C45—C452—S451	−179.2 (2)
N2—N1—C5—O51	−174.0 (2)	C455—S451—C452—C453	1.4 (10)
C11—N1—C5—O51	−1.7 (4)	C455—S451—C452—C45	−177.2 (4)
C5—N1—C11—C12	45.3 (4)	C45—C452—C453—C454	177.6 (11)
N2—N1—C11—C12	−143.1 (3)	S451—C452—C453—C454	−0.9 (18)
C5—N1—C11—C16	−135.0 (3)	C452—C453—C454—C455	0 (2)
N2—N1—C11—C16	36.6 (4)	C453—C454—C455—S451	1.4 (18)
C16—C11—C12—C13	2.0 (5)	C452—S451—C455—C454	−1.6 (11)
N1—C11—C12—C13	−178.3 (3)	C553—C554—C555—S551	−4 (13)
C11—C12—C13—C14	−1.6 (5)	C4—C5—O51—C51	76.6 (4)
C12—C13—C14—C15	−0.1 (6)	N1—C5—O51—C51	−110.9 (3)
C13—C14—C15—C16	1.3 (5)	C5—O51—C51—C56	22.5 (3)
C12—C11—C16—C15	−0.8 (4)	C5—O51—C51—C52	−158.9 (2)
N1—C11—C16—C15	179.5 (3)	C56—C51—C52—C53	0.2 (4)
C14—C15—C16—C11	−0.9 (5)	O51—C51—C52—C53	−178.3 (2)
C45—N41—N42—C422	174.3 (2)	C56—C51—C52—C57	−178.4 (3)
C45—N41—N42—C43	−4.4 (3)	O51—C51—C52—C57	3.1 (4)
C422—N42—C43—C4	64.4 (3)	C51—C52—C53—C54	−0.2 (5)
N41—N42—C43—C4	−117.0 (2)	C57—C52—C53—C54	178.4 (3)
C422—N42—C43—C44	−170.8 (2)	C52—C53—C54—C55	−0.5 (6)
N41—N42—C43—C44	7.7 (3)	C53—C54—C55—C56	1.1 (6)
C5—C4—C43—N42	41.7 (4)	C52—C51—C56—C55	0.4 (4)
C3—C4—C43—N42	−132.8 (3)	O51—C51—C56—C55	178.8 (2)
C5—C4—C43—C44	−74.0 (4)	C54—C55—C56—C51	−1.0 (5)
C3—C4—C43—C44	111.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N423—H42A···N2^i	0.92 (3)	2.28 (3)	3.111 (3)	150 (2)
N423—H42A···N41	0.92 (3)	2.27 (3)	2.628 (4)	103 (2)

Symmetry code: (i) x+1, y, z.

5'-(2,4-Dichlorophenoxy)-3'-methyl-1'-phenyl-5-(thiophen-2-yl)-3,4-dihydro-1'H,2H-3,4'-bipyrazole-2-carbothioamide hemihydrate (Ib)

Crystal data

2C24H19Cl2N5OS2·H2O	F(000) = 1108
Mr = 1074.94	Dx = 1.456 Mg m^−3
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.037 (1) Å	Cell parameters from 5307 reflections
b = 8.4266 (6) Å	θ = 2.6–27.9°
c = 19.471 (1) Å	µ = 0.47 mm^−1
β = 96.246 (6)°	T = 296 K
V = 2452.5 (3) Å^3	Needle, orange
Z = 2	0.36 × 0.12 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur with Sapphire CCD detector diffractometer	5290 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3075 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω scans	θmax = 27.6°, θmin = 2.6°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −19→13
Tmin = 0.922, Tmax = 0.946	k = −10→10
10494 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)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2) + (0.0411P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max = 0.001
5290 reflections	Δρmax = 0.26 e Å^−3
335 parameters	Δρmin = −0.30 e Å^−3
10 restraints

Special details

Experimental. CrysAlis RED, Oxford Diffraction Ltd., 2009 Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	Occ. (<1)
N1	0.68939 (13)	0.4363 (2)	0.37947 (9)	0.0343 (5)
N2	0.61354 (13)	0.3752 (2)	0.34400 (9)	0.0356 (5)
C3	0.59656 (15)	0.2419 (3)	0.37692 (11)	0.0318 (5)
C4	0.66061 (15)	0.2149 (3)	0.43422 (11)	0.0296 (5)
C5	0.71767 (15)	0.3404 (3)	0.43322 (11)	0.0308 (5)
C11	0.72930 (16)	0.5768 (3)	0.35564 (11)	0.0354 (6)
C12	0.81789 (18)	0.5775 (3)	0.34460 (15)	0.0602 (8)
H12	0.8535	0.4889	0.3557	0.072*
C13	0.8538 (2)	0.7111 (4)	0.31678 (17)	0.0748 (10)
H13	0.9137	0.7127	0.3089	0.090*
C14	0.8006 (2)	0.8415 (3)	0.30086 (14)	0.0580 (8)
H14	0.8244	0.9307	0.2815	0.070*
C15	0.7138 (2)	0.8410 (3)	0.31316 (13)	0.0471 (7)
H15	0.6788	0.9306	0.3028	0.057*
C16	0.67667 (17)	0.7089 (3)	0.34090 (11)	0.0384 (6)
H16	0.6170	0.7092	0.3495	0.046*
C31	0.51811 (17)	0.1418 (3)	0.35213 (13)	0.0438 (6)
H31A	0.4846	0.1180	0.3901	0.066*
H31B	0.5384	0.0447	0.3332	0.066*
H31C	0.4807	0.1979	0.3171	0.066*
N41	0.75120 (13)	0.0972 (2)	0.59603 (9)	0.0355 (5)
N42	0.67049 (13)	0.1362 (2)	0.55799 (9)	0.0344 (5)
C43	0.66437 (16)	0.0806 (3)	0.48505 (11)	0.0335 (6)
H43	0.6115	0.0131	0.4751	0.040*
C44	0.74925 (17)	−0.0209 (3)	0.48690 (12)	0.0404 (6)
H44A	0.7346	−0.1326	0.4813	0.048*
H44B	0.7855	0.0110	0.4510	0.048*
C45	0.79663 (16)	0.0117 (3)	0.55736 (11)	0.0336 (6)
S421	0.50684 (4)	0.25555 (8)	0.54387 (3)	0.0477 (2)
C422	0.60539 (16)	0.2113 (3)	0.58829 (12)	0.0361 (6)
N423	0.62484 (18)	0.2475 (3)	0.65504 (11)	0.0512 (7)
H42A	0.585 (2)	0.293 (3)	0.6745 (14)	0.061*
H42B	0.675 (2)	0.220 (3)	0.6753 (14)	0.061*
S451	0.93613 (5)	−0.02351 (9)	0.66256 (4)	0.0493 (3)	0.951 (3)
C452	0.88401 (16)	−0.0510 (3)	0.58006 (12)	0.0365 (6)	0.951 (3)
C453	0.9356 (3)	−0.1417 (6)	0.5435 (2)	0.0475 (9)	0.951 (3)
H453	0.9188	−0.1700	0.4977	0.057*	0.951 (3)
C454	1.0167 (2)	−0.1900 (7)	0.5800 (2)	0.0524 (14)	0.951 (3)
H454	1.0593	−0.2517	0.5612	0.063*	0.951 (3)
C455	1.0251 (2)	−0.1363 (4)	0.64507 (18)	0.0537 (12)	0.951 (3)
H455	1.0740	−0.1580	0.6772	0.064*	0.951 (3)
S551	0.937 (2)	−0.159 (4)	0.5215 (11)	0.0475 (9)	0.049 (3)
C552	0.88401 (16)	−0.0510 (3)	0.58006 (12)	0.0365 (6)	0.049 (3)
C553	0.944 (2)	−0.005 (7)	0.633 (2)	0.0493 (3)	0.049 (3)
H553	0.9341	0.0767	0.6631	0.059*	0.049 (3)
C554	1.024 (3)	−0.094 (11)	0.637 (3)	0.0537 (12)	0.049 (3)
H554	1.0649	−0.1006	0.6763	0.064*	0.049 (3)
C555	1.032 (4)	−0.169 (16)	0.577 (4)	0.0524 (14)	0.049 (3)
H555	1.0839	−0.2211	0.5676	0.063*	0.049 (3)
O51	0.79155 (10)	0.37875 (17)	0.47791 (7)	0.0338 (4)
C51	0.77558 (16)	0.4711 (3)	0.53498 (11)	0.0326 (6)
C52	0.84468 (16)	0.4851 (3)	0.58742 (12)	0.0366 (6)
Cl52	0.94533 (5)	0.39239 (9)	0.58023 (4)	0.0618 (2)
C53	0.83348 (19)	0.5733 (3)	0.64567 (13)	0.0464 (7)
H53	0.8799	0.5827	0.6811	0.056*
C54	0.7533 (2)	0.6467 (3)	0.65044 (13)	0.0453 (7)
Cl54	0.73886 (6)	0.75872 (9)	0.72375 (4)	0.0733 (3)
C55	0.68368 (19)	0.6329 (3)	0.59891 (14)	0.0496 (7)
H55	0.6294	0.6826	0.6032	0.060*
C56	0.69494 (17)	0.5446 (3)	0.54082 (13)	0.0424 (6)
H56	0.6482	0.5348	0.5057	0.051*
O61	0.5000	0.5746 (3)	0.2500	0.0605 (9)
H61	0.532 (2)	0.511 (3)	0.2784 (15)	0.091*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0301 (11)	0.0402 (12)	0.0312 (11)	−0.0022 (9)	−0.0028 (9)	0.0066 (9)
N2	0.0304 (12)	0.0441 (12)	0.0306 (11)	−0.0018 (10)	−0.0039 (9)	0.0035 (9)
C3	0.0300 (13)	0.0390 (14)	0.0263 (12)	0.0011 (11)	0.0029 (10)	−0.0019 (11)
C4	0.0306 (13)	0.0325 (13)	0.0254 (12)	0.0022 (11)	0.0013 (10)	0.0006 (10)
C5	0.0259 (13)	0.0372 (14)	0.0280 (12)	0.0040 (11)	−0.0024 (10)	−0.0010 (11)
C11	0.0334 (14)	0.0411 (15)	0.0309 (13)	−0.0047 (12)	0.0001 (11)	0.0056 (11)
C12	0.0372 (17)	0.0615 (19)	0.082 (2)	0.0038 (15)	0.0074 (16)	0.0298 (17)
C13	0.0392 (18)	0.087 (2)	0.098 (3)	−0.0103 (18)	0.0100 (18)	0.039 (2)
C14	0.058 (2)	0.0583 (19)	0.0562 (18)	−0.0216 (17)	−0.0028 (16)	0.0207 (15)
C15	0.0563 (19)	0.0407 (16)	0.0432 (15)	−0.0018 (14)	0.0001 (14)	0.0049 (13)
C16	0.0383 (15)	0.0438 (15)	0.0332 (14)	−0.0012 (12)	0.0046 (12)	−0.0012 (12)
C31	0.0385 (15)	0.0491 (16)	0.0421 (15)	−0.0018 (13)	−0.0030 (12)	−0.0019 (12)
N41	0.0348 (12)	0.0398 (12)	0.0314 (11)	0.0032 (10)	0.0015 (9)	0.0036 (9)
N42	0.0341 (12)	0.0424 (12)	0.0264 (10)	0.0080 (10)	0.0017 (9)	0.0004 (9)
C43	0.0367 (14)	0.0345 (13)	0.0286 (12)	−0.0024 (11)	0.0009 (11)	−0.0001 (11)
C44	0.0496 (16)	0.0359 (14)	0.0348 (13)	0.0073 (13)	0.0010 (12)	−0.0001 (11)
C45	0.0412 (15)	0.0284 (13)	0.0313 (13)	0.0013 (12)	0.0047 (12)	0.0032 (11)
S421	0.0361 (4)	0.0614 (5)	0.0457 (4)	0.0054 (3)	0.0045 (3)	0.0036 (3)
C422	0.0382 (15)	0.0369 (14)	0.0336 (13)	−0.0021 (12)	0.0062 (12)	0.0045 (11)
N423	0.0508 (16)	0.0714 (17)	0.0317 (13)	0.0165 (13)	0.0051 (11)	−0.0039 (12)
S451	0.0460 (5)	0.0588 (5)	0.0412 (5)	0.0101 (4)	−0.0039 (4)	−0.0069 (4)
C452	0.0382 (15)	0.0347 (14)	0.0361 (13)	0.0032 (12)	0.0026 (12)	0.0038 (11)
C453	0.0523 (18)	0.057 (2)	0.035 (3)	0.0135 (15)	0.009 (2)	0.000 (2)
C454	0.041 (2)	0.058 (3)	0.0590 (19)	0.013 (2)	0.0074 (17)	−0.0020 (17)
C455	0.0405 (17)	0.056 (3)	0.061 (2)	0.0099 (16)	−0.0100 (15)	0.0011 (18)
S551	0.0523 (18)	0.057 (2)	0.035 (3)	0.0135 (15)	0.009 (2)	0.000 (2)
C552	0.0382 (15)	0.0347 (14)	0.0361 (13)	0.0032 (12)	0.0026 (12)	0.0038 (11)
C553	0.0460 (5)	0.0588 (5)	0.0412 (5)	0.0101 (4)	−0.0039 (4)	−0.0069 (4)
C554	0.0405 (17)	0.056 (3)	0.061 (2)	0.0099 (16)	−0.0100 (15)	0.0011 (18)
C555	0.041 (2)	0.058 (3)	0.0590 (19)	0.013 (2)	0.0074 (17)	−0.0020 (17)
O51	0.0261 (9)	0.0424 (10)	0.0317 (9)	0.0033 (7)	−0.0025 (7)	−0.0042 (8)
C51	0.0356 (14)	0.0287 (13)	0.0333 (13)	−0.0006 (11)	0.0031 (11)	0.0024 (11)
C52	0.0320 (14)	0.0378 (14)	0.0392 (14)	0.0002 (11)	−0.0004 (12)	0.0004 (12)
Cl52	0.0389 (4)	0.0757 (5)	0.0665 (5)	0.0146 (4)	−0.0133 (4)	−0.0190 (4)
C53	0.0496 (18)	0.0501 (17)	0.0385 (15)	−0.0095 (14)	0.0007 (13)	−0.0065 (13)
C54	0.0579 (19)	0.0391 (15)	0.0411 (15)	−0.0095 (14)	0.0155 (14)	−0.0061 (12)
Cl54	0.0881 (6)	0.0778 (6)	0.0589 (5)	−0.0104 (5)	0.0293 (4)	−0.0278 (4)
C55	0.0437 (17)	0.0510 (17)	0.0564 (18)	0.0062 (13)	0.0157 (15)	−0.0078 (14)
C56	0.0352 (15)	0.0455 (16)	0.0454 (15)	0.0029 (12)	−0.0004 (13)	−0.0032 (13)
O61	0.064 (2)	0.0498 (18)	0.0594 (19)	0.000	−0.0293 (15)	0.000

Geometric parameters (Å, º)

N1—C5	1.354 (3)	C45—C452	1.440 (3)
N1—N2	1.368 (2)	S421—C422	1.675 (2)
N1—C11	1.427 (3)	C422—N423	1.336 (3)
N2—C3	1.332 (3)	N423—H42A	0.83 (3)
C3—C4	1.411 (3)	N423—H42B	0.84 (3)
C3—C31	1.488 (3)	S451—C455	1.705 (3)
C4—C5	1.363 (3)	S451—C452	1.725 (2)
C4—C43	1.500 (3)	C452—C453	1.347 (5)
C5—O51	1.373 (2)	C453—C454	1.404 (5)
C11—C12	1.372 (3)	C453—H453	0.9300
C11—C16	1.378 (3)	C454—C455	1.339 (4)
C12—C13	1.385 (4)	C454—H454	0.9300
C12—H12	0.9300	C455—H455	0.9300
C13—C14	1.375 (4)	S551—C555	1.707 (11)
C13—H13	0.9300	C553—C554	1.407 (11)
C14—C15	1.352 (4)	C553—H553	0.9300
C14—H14	0.9300	C554—C555	1.342 (10)
C15—C16	1.382 (3)	C554—H554	0.9300
C15—H15	0.9300	C555—H555	0.9300
C16—H16	0.9300	O51—C51	1.399 (3)
C31—H31A	0.9600	C51—C56	1.377 (3)
C31—H31B	0.9600	C51—C52	1.380 (3)
C31—H31C	0.9600	C52—C53	1.382 (3)
N41—C45	1.290 (3)	C52—Cl52	1.722 (2)
N41—N42	1.391 (2)	C53—C54	1.366 (4)
N42—C422	1.354 (3)	C53—H53	0.9300
N42—C43	1.489 (3)	C54—C55	1.374 (4)
C43—C44	1.534 (3)	C54—Cl54	1.745 (3)
C43—H43	0.9800	C55—C56	1.379 (3)
C44—C45	1.501 (3)	C55—H55	0.9300
C44—H44A	0.9700	C56—H56	0.9300
C44—H44B	0.9700	O61—H61	0.88 (3)
C5—N1—N2	109.89 (18)	C43—C44—H44B	111.1
C5—N1—C11	129.69 (19)	H44A—C44—H44B	109.1
N2—N1—C11	120.32 (17)	N41—C45—C452	123.3 (2)
C3—N2—N1	105.50 (17)	N41—C45—C44	114.0 (2)
N2—C3—C4	111.5 (2)	C452—C45—C44	122.7 (2)
N2—C3—C31	120.6 (2)	N423—C422—N42	116.0 (2)
C4—C3—C31	127.9 (2)	N423—C422—S421	122.6 (2)
C5—C4—C3	103.90 (19)	N42—C422—S421	121.36 (18)
C5—C4—C43	128.0 (2)	C422—N423—H42A	117.2 (19)
C3—C4—C43	128.1 (2)	C422—N423—H42B	118.9 (19)
N1—C5—C4	109.20 (19)	H42A—N423—H42B	124 (3)
N1—C5—O51	120.9 (2)	C455—S451—C452	91.49 (14)
C4—C5—O51	129.8 (2)	C453—C452—C45	127.2 (3)
C12—C11—C16	120.6 (2)	C453—C452—S451	109.8 (2)
C12—C11—N1	120.3 (2)	C45—C452—S451	122.94 (19)
C16—C11—N1	119.1 (2)	C452—C453—C454	114.6 (3)
C11—C12—C13	119.5 (3)	C452—C453—H453	122.7
C11—C12—H12	120.3	C454—C453—H453	122.7
C13—C12—H12	120.3	C455—C454—C453	111.6 (3)
C14—C13—C12	119.7 (3)	C455—C454—H454	124.2
C14—C13—H13	120.1	C453—C454—H454	124.2
C12—C13—H13	120.1	C454—C455—S451	112.5 (2)
C15—C14—C13	120.5 (3)	C454—C455—H455	123.7
C15—C14—H14	119.8	S451—C455—H455	123.7
C13—C14—H14	119.8	C554—C553—H553	123.6
C14—C15—C16	120.7 (3)	C555—C554—C553	111.1 (15)
C14—C15—H15	119.6	C555—C554—H554	124.5
C16—C15—H15	119.6	C553—C554—H554	124.5
C11—C16—C15	119.0 (2)	C554—C555—S551	112.1 (11)
C11—C16—H16	120.5	C554—C555—H555	123.9
C15—C16—H16	120.5	S551—C555—H555	123.9
C3—C31—H31A	109.5	C5—O51—C51	115.94 (17)
C3—C31—H31B	109.5	C56—C51—C52	120.0 (2)
H31A—C31—H31B	109.5	C56—C51—O51	123.0 (2)
C3—C31—H31C	109.5	C52—C51—O51	117.0 (2)
H31A—C31—H31C	109.5	C51—C52—C53	120.2 (2)
H31B—C31—H31C	109.5	C51—C52—Cl52	119.92 (18)
C45—N41—N42	107.92 (18)	C53—C52—Cl52	119.83 (19)
C422—N42—N41	120.58 (18)	C54—C53—C52	119.1 (2)
C422—N42—C43	126.17 (19)	C54—C53—H53	120.4
N41—N42—C43	113.19 (18)	C52—C53—H53	120.4
N42—C43—C4	112.72 (18)	C53—C54—C55	121.3 (2)
N42—C43—C44	100.84 (17)	C53—C54—Cl54	119.3 (2)
C4—C43—C44	114.06 (19)	C55—C54—Cl54	119.3 (2)
N42—C43—H43	109.6	C54—C55—C56	119.5 (2)
C4—C43—H43	109.6	C54—C55—H55	120.2
C44—C43—H43	109.6	C56—C55—H55	120.2
C45—C44—C43	103.32 (18)	C51—C56—C55	119.9 (2)
C45—C44—H44A	111.1	C51—C56—H56	120.1
C43—C44—H44A	111.1	C55—C56—H56	120.1
C45—C44—H44B	111.1
C5—N1—N2—C3	0.0 (2)	C4—C43—C44—C45	113.3 (2)
C11—N1—N2—C3	176.76 (19)	N42—N41—C45—C452	−179.7 (2)
N1—N2—C3—C4	0.3 (2)	N42—N41—C45—C44	−1.3 (3)
N1—N2—C3—C31	−179.6 (2)	C43—C44—C45—N41	6.2 (3)
N2—C3—C4—C5	−0.5 (2)	C43—C44—C45—C452	−175.4 (2)
C31—C3—C4—C5	179.4 (2)	N41—N42—C422—N423	1.5 (3)
N2—C3—C4—C43	178.8 (2)	C43—N42—C422—N423	178.6 (2)
C31—C3—C4—C43	−1.4 (4)	N41—N42—C422—S421	−178.60 (16)
N2—N1—C5—C4	−0.3 (3)	C43—N42—C422—S421	−1.5 (3)
C11—N1—C5—C4	−176.7 (2)	N41—C45—C452—C453	179.5 (4)
N2—N1—C5—O51	−178.18 (18)	C44—C45—C452—C453	1.3 (5)
C11—N1—C5—O51	5.4 (3)	N41—C45—C452—S451	2.1 (3)
C3—C4—C5—N1	0.4 (2)	C44—C45—C452—S451	−176.17 (18)
C43—C4—C5—N1	−178.8 (2)	C455—S451—C452—C453	−0.4 (3)
C3—C4—C5—O51	178.1 (2)	C455—S451—C452—C45	177.4 (2)
C43—C4—C5—O51	−1.1 (4)	C45—C452—C453—C454	−177.9 (4)
C5—N1—C11—C12	50.0 (3)	S451—C452—C453—C454	−0.2 (6)
N2—N1—C11—C12	−126.0 (3)	C452—C453—C454—C455	0.9 (7)
C5—N1—C11—C16	−132.9 (2)	C453—C454—C455—S451	−1.2 (6)
N2—N1—C11—C16	51.0 (3)	C452—S451—C455—C454	0.9 (4)
C16—C11—C12—C13	−1.6 (4)	C553—C554—C555—S551	−10 (12)
N1—C11—C12—C13	175.4 (2)	N1—C5—O51—C51	89.3 (2)
C11—C12—C13—C14	0.3 (5)	C4—C5—O51—C51	−88.1 (3)
C12—C13—C14—C15	1.0 (5)	C5—O51—C51—C56	−11.5 (3)
C13—C14—C15—C16	−1.0 (4)	C5—O51—C51—C52	167.5 (2)
C12—C11—C16—C15	1.6 (4)	C56—C51—C52—C53	−0.4 (3)
N1—C11—C16—C15	−175.40 (19)	O51—C51—C52—C53	−179.4 (2)
C14—C15—C16—C11	−0.3 (4)	C56—C51—C52—Cl52	179.72 (18)
C45—N41—N42—C422	172.8 (2)	O51—C51—C52—Cl52	0.7 (3)
C45—N41—N42—C43	−4.6 (2)	C51—C52—C53—C54	−0.2 (4)
C422—N42—C43—C4	68.7 (3)	Cl52—C52—C53—C54	179.7 (2)
N41—N42—C43—C4	−114.0 (2)	C52—C53—C54—C55	0.7 (4)
C422—N42—C43—C44	−169.3 (2)	C52—C53—C54—Cl54	−179.85 (18)
N41—N42—C43—C44	8.0 (2)	C53—C54—C55—C56	−0.7 (4)
C5—C4—C43—N42	52.6 (3)	Cl54—C54—C55—C56	179.89 (19)
C3—C4—C43—N42	−126.5 (2)	C52—C51—C56—C55	0.4 (4)
C5—C4—C43—C44	−61.7 (3)	O51—C51—C56—C55	179.4 (2)
C3—C4—C43—C44	119.3 (3)	C54—C55—C56—C51	0.1 (4)
N42—C43—C44—C45	−7.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O61—H61···N2	0.88 (3)	2.03 (3)	2.900 (2)	176 (2)
N423—H42A···O61^i	0.84 (3)	2.33 (3)	3.154 (3)	167 (3)
N423—H42B···N41	0.85 (3)	2.27 (3)	2.648 (3)	107 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Ethyl (Z)-2-{2-[3'-methyl-1'-phenyl-5-(thiophen-2-yl)-5'-(2-methylphenoxy)-3,4-dihydro-1'H,2H-3,4'-bipyrazole-2-yl]-4-oxo-4,5-dihydrothiazol-5-ylidene}acetate (II)

Crystal data

C31H27N5O4S2	Z = 2
Mr = 597.69	F(000) = 624
Triclinic, P1	Dx = 1.331 Mg m^−3
a = 10.783 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.683 (3) Å	Cell parameters from 6462 reflections
c = 13.577 (3) Å	θ = 2.5–28.2°
α = 93.54 (2)°	µ = 0.22 mm^−1
β = 105.17 (2)°	T = 296 K
γ = 113.20 (2)°	Needle, yellow
V = 1490.9 (6) Å^3	0.48 × 0.12 × 0.06 mm

Data collection

Oxford Diffraction Xcalibur with Sapphire CCD detector diffractometer	5561 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1730 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.138
ω scans	θmax = 25.6°, θmin = 2.5°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −7→13
Tmin = 0.849, Tmax = 0.987	k = −14→12
10433 measured reflections	l = −16→16

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)] = 0.079	H-atom parameters constrained
wR(F^2) = 0.143	w = 1/[σ^2(Fo^2) + (0.0319P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.88	(Δ/σ)max < 0.001
5561 reflections	Δρmax = 0.26 e Å^−3
395 parameters	Δρmin = −0.24 e Å^−3
10 restraints

Special details

Experimental. CrysAlis RED, Oxford Diffraction Ltd., 2009 Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	Occ. (<1)
N1	1.0895 (5)	0.0030 (4)	0.1894 (3)	0.0436 (12)
N2	1.1527 (4)	0.1065 (4)	0.1476 (4)	0.0459 (12)
C3	1.0468 (6)	0.1321 (4)	0.0945 (4)	0.0430 (15)
C4	0.9141 (5)	0.0459 (5)	0.0992 (4)	0.0401 (14)
C5	0.9473 (6)	−0.0321 (5)	0.1612 (4)	0.0424 (15)
C11	1.1772 (6)	−0.0460 (5)	0.2534 (4)	0.0420 (14)
C12	1.1198 (6)	−0.1658 (5)	0.2763 (5)	0.0571 (17)
H12	1.0229	−0.2171	0.2490	0.068*
C13	1.2090 (7)	−0.2083 (5)	0.3410 (5)	0.0644 (18)
H13	1.1707	−0.2886	0.3570	0.077*
C14	1.3536 (7)	−0.1337 (6)	0.3821 (5)	0.0657 (18)
H14	1.4123	−0.1629	0.4256	0.079*
C15	1.4082 (6)	−0.0162 (6)	0.3573 (5)	0.0596 (17)
H15	1.5054	0.0343	0.3832	0.071*
C16	1.3214 (6)	0.0286 (5)	0.2947 (4)	0.0459 (14)
H16	1.3602	0.1096	0.2801	0.055*
C31	1.0776 (5)	0.2433 (4)	0.0406 (4)	0.0609 (17)
H31A	1.0234	0.2153	−0.0317	0.091*
H31B	1.1770	0.2823	0.0477	0.091*
H31C	1.0520	0.3037	0.0711	0.091*
N41	0.5871 (4)	−0.0182 (4)	0.1331 (3)	0.0455 (12)
N42	0.7101 (4)	0.0797 (4)	0.1249 (4)	0.0482 (13)
C43	0.7718 (6)	0.0410 (4)	0.0483 (4)	0.0487 (16)
H43	0.7777	0.0954	−0.0040	0.058*
C44	0.6507 (5)	−0.0938 (4)	−0.0010 (4)	0.0511 (16)
H44A	0.6003	−0.0969	−0.0724	0.061*
H44B	0.6884	−0.1568	0.0005	0.061*
C45	0.5547 (5)	−0.1162 (5)	0.0651 (4)	0.0439 (15)
S421	0.68139 (15)	0.21639 (13)	0.27511 (12)	0.0544 (5)
C422	0.7658 (6)	0.1937 (5)	0.1848 (5)	0.0505 (16)
N423	0.8776 (5)	0.2867 (4)	0.1773 (4)	0.0558 (14)
C424	0.9084 (6)	0.3951 (6)	0.2437 (5)	0.0622 (18)
O424	1.0021 (4)	0.4986 (4)	0.2506 (3)	0.0877 (15)
C425	0.8101 (5)	0.3718 (5)	0.3113 (5)	0.0482 (15)
C426	0.8307 (6)	0.4611 (5)	0.3868 (5)	0.0636 (18)
H426	0.9061	0.5406	0.3996	0.076*
C427	0.7337 (7)	0.4347 (6)	0.4514 (5)	0.0637 (19)
O427	0.6309 (5)	0.3363 (4)	0.4379 (3)	0.0842 (15)
O428	0.7767 (4)	0.5339 (4)	0.5256 (4)	0.0852 (14)
C428	0.6931 (7)	0.5170 (6)	0.5969 (6)	0.094 (2)
H48A	0.7096	0.4595	0.6416	0.112*
H48B	0.5928	0.4809	0.5580	0.112*
C429	0.7352 (7)	0.6415 (7)	0.6602 (6)	0.119 (3)
H49A	0.6803	0.6314	0.7071	0.179*
H49B	0.7184	0.6980	0.6155	0.179*
H49C	0.8342	0.6763	0.6992	0.179*
S451	0.3311 (4)	−0.2531 (3)	0.1357 (3)	0.0655 (10)	0.768 (6)
C452	0.4337 (6)	−0.2339 (5)	0.0544 (4)	0.0499 (15)	0.768 (6)
C453	0.398 (3)	−0.339 (2)	−0.0103 (19)	0.073 (3)	0.768 (6)
H453	0.4475	−0.3467	−0.0552	0.087*	0.768 (6)
C454	0.270 (2)	−0.4427 (17)	−0.002 (2)	0.075 (5)	0.768 (6)
H454	0.2228	−0.5220	−0.0449	0.090*	0.768 (6)
C455	0.2293 (14)	−0.4072 (9)	0.0772 (15)	0.073 (4)	0.768 (6)
H455	0.1540	−0.4614	0.0971	0.087*	0.768 (6)
S551	0.383 (3)	−0.3635 (19)	−0.0394 (18)	0.073 (3)	0.232 (6)
C552	0.4337 (6)	−0.2339 (5)	0.0544 (4)	0.0499 (15)	0.232 (6)
C553	0.349 (5)	−0.251 (4)	0.112 (4)	0.0655 (10)	0.232 (6)
H553	0.3652	−0.1924	0.1690	0.079*	0.232 (6)
C554	0.224 (5)	−0.375 (3)	0.073 (5)	0.073 (4)	0.232 (6)
H554	0.1462	−0.4003	0.0973	0.087*	0.232 (6)
C555	0.239 (9)	−0.446 (5)	−0.002 (8)	0.075 (5)	0.232 (6)
H555	0.1772	−0.5306	−0.0298	0.090*	0.232 (6)
O51	0.8569 (3)	−0.1355 (3)	0.1888 (3)	0.0513 (10)
C51	0.8251 (6)	−0.1159 (6)	0.2805 (5)	0.0543 (16)
C52	0.7268 (7)	−0.2241 (7)	0.3002 (6)	0.073 (2)
C53	0.6939 (8)	−0.2041 (10)	0.3902 (8)	0.116 (3)
H53	0.6310	−0.2738	0.4086	0.140*
C54	0.7476 (11)	−0.0898 (13)	0.4529 (8)	0.132 (4)
H54	0.7183	−0.0825	0.5107	0.158*
C55	0.8442 (10)	0.0144 (10)	0.4315 (6)	0.105 (3)
H55	0.8838	0.0924	0.4756	0.125*
C56	0.8832 (6)	0.0023 (6)	0.3421 (5)	0.0704 (19)
H56	0.9468	0.0725	0.3247	0.084*
C57	0.6674 (7)	−0.3502 (6)	0.2333 (6)	0.105 (3)
H57A	0.5900	−0.4086	0.2528	0.158*
H57B	0.7399	−0.3803	0.2416	0.158*
H57C	0.6337	−0.3435	0.1620	0.158*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.042 (3)	0.044 (3)	0.045 (3)	0.016 (3)	0.016 (3)	0.008 (2)
N2	0.043 (3)	0.043 (3)	0.053 (3)	0.011 (2)	0.028 (3)	0.011 (3)
C3	0.047 (4)	0.041 (3)	0.046 (4)	0.017 (3)	0.025 (3)	0.007 (3)
C4	0.039 (4)	0.047 (3)	0.039 (4)	0.020 (3)	0.017 (3)	0.009 (3)
C5	0.040 (4)	0.042 (3)	0.036 (4)	0.007 (3)	0.016 (3)	0.000 (3)
C11	0.040 (4)	0.045 (3)	0.037 (4)	0.016 (3)	0.011 (3)	0.001 (3)
C12	0.050 (4)	0.048 (4)	0.065 (5)	0.014 (3)	0.016 (4)	0.009 (3)
C13	0.076 (5)	0.053 (4)	0.068 (5)	0.029 (4)	0.024 (4)	0.019 (4)
C14	0.062 (5)	0.075 (4)	0.058 (5)	0.032 (4)	0.010 (4)	0.015 (4)
C15	0.052 (4)	0.068 (4)	0.050 (5)	0.018 (4)	0.013 (4)	0.010 (4)
C16	0.051 (4)	0.050 (3)	0.035 (4)	0.015 (3)	0.020 (3)	0.015 (3)
C31	0.068 (4)	0.051 (3)	0.067 (5)	0.019 (3)	0.034 (4)	0.019 (3)
N41	0.047 (3)	0.042 (3)	0.047 (3)	0.015 (2)	0.021 (3)	0.012 (2)
N42	0.047 (3)	0.046 (3)	0.057 (4)	0.022 (2)	0.022 (3)	0.006 (3)
C43	0.057 (4)	0.051 (3)	0.043 (4)	0.021 (3)	0.027 (3)	0.003 (3)
C44	0.043 (4)	0.061 (4)	0.046 (4)	0.021 (3)	0.014 (3)	0.001 (3)
C45	0.047 (4)	0.047 (3)	0.041 (4)	0.024 (3)	0.013 (3)	0.013 (3)
S421	0.0588 (11)	0.0465 (8)	0.0573 (12)	0.0175 (8)	0.0263 (9)	0.0045 (8)
C422	0.063 (4)	0.051 (4)	0.052 (4)	0.034 (3)	0.027 (4)	0.013 (3)
N423	0.059 (3)	0.042 (3)	0.061 (4)	0.009 (2)	0.030 (3)	0.005 (3)
C424	0.061 (5)	0.055 (4)	0.058 (5)	0.014 (4)	0.018 (4)	0.007 (4)
O424	0.087 (3)	0.056 (2)	0.089 (4)	−0.008 (2)	0.043 (3)	−0.005 (3)
C425	0.056 (4)	0.038 (3)	0.051 (4)	0.017 (3)	0.021 (3)	0.010 (3)
C426	0.074 (5)	0.053 (4)	0.064 (5)	0.020 (3)	0.035 (4)	0.001 (4)
C427	0.074 (5)	0.053 (4)	0.052 (5)	0.030 (4)	0.001 (4)	−0.013 (4)
O427	0.093 (4)	0.071 (3)	0.074 (4)	0.018 (3)	0.033 (3)	−0.005 (3)
O428	0.101 (4)	0.074 (3)	0.075 (4)	0.030 (3)	0.036 (3)	−0.011 (3)
C428	0.102 (6)	0.107 (6)	0.076 (6)	0.048 (5)	0.033 (5)	−0.006 (5)
C429	0.147 (7)	0.131 (6)	0.083 (6)	0.073 (6)	0.028 (5)	−0.020 (5)
S451	0.0732 (19)	0.0564 (14)	0.068 (2)	0.0167 (12)	0.0389 (13)	0.0163 (14)
C452	0.058 (4)	0.040 (3)	0.048 (4)	0.017 (3)	0.018 (3)	0.004 (3)
C453	0.085 (6)	0.043 (7)	0.053 (11)	0.002 (5)	0.007 (7)	−0.003 (5)
C454	0.080 (13)	0.046 (4)	0.066 (6)	−0.001 (5)	0.017 (9)	−0.002 (4)
C455	0.083 (5)	0.046 (7)	0.079 (6)	0.016 (5)	0.026 (5)	0.014 (7)
S551	0.085 (6)	0.043 (7)	0.053 (11)	0.002 (5)	0.007 (7)	−0.003 (5)
C552	0.058 (4)	0.040 (3)	0.048 (4)	0.017 (3)	0.018 (3)	0.004 (3)
C553	0.0732 (19)	0.0564 (14)	0.068 (2)	0.0167 (12)	0.0389 (13)	0.0163 (14)
C554	0.083 (5)	0.046 (7)	0.079 (6)	0.016 (5)	0.026 (5)	0.014 (7)
C555	0.080 (13)	0.046 (4)	0.066 (6)	−0.001 (5)	0.017 (9)	−0.002 (4)
O51	0.049 (2)	0.056 (2)	0.048 (3)	0.0145 (19)	0.024 (2)	0.010 (2)
C51	0.058 (4)	0.075 (4)	0.042 (5)	0.037 (4)	0.020 (4)	0.020 (4)
C52	0.065 (5)	0.110 (6)	0.068 (6)	0.041 (5)	0.042 (4)	0.065 (5)
C53	0.098 (7)	0.169 (9)	0.110 (10)	0.054 (7)	0.068 (7)	0.081 (7)
C54	0.140 (10)	0.248 (15)	0.078 (8)	0.125 (10)	0.068 (7)	0.074 (9)
C55	0.136 (8)	0.182 (9)	0.049 (6)	0.107 (7)	0.047 (5)	0.035 (6)
C56	0.077 (5)	0.102 (5)	0.055 (5)	0.052 (4)	0.034 (4)	0.019 (4)
C57	0.092 (6)	0.082 (5)	0.129 (7)	0.013 (4)	0.041 (5)	0.070 (5)

Geometric parameters (Å, º)

N1—C5	1.358 (6)	C426—C427	1.489 (8)
N1—N2	1.374 (5)	C426—H426	0.9300
N1—C11	1.426 (6)	C427—O427	1.203 (6)
N2—C3	1.333 (6)	C427—O428	1.327 (6)
C3—C4	1.409 (6)	O428—C428	1.458 (7)
C3—C31	1.497 (6)	C428—C429	1.477 (7)
C4—C5	1.364 (7)	C428—H48A	0.9700
C4—C43	1.485 (6)	C428—H48B	0.9700
C5—O51	1.367 (6)	C429—H49A	0.9600
C11—C16	1.382 (6)	C429—H49B	0.9600
C11—C12	1.382 (7)	C429—H49C	0.9600
C12—C13	1.390 (7)	S451—C455	1.699 (9)
C12—H12	0.9300	S451—C452	1.723 (6)
C13—C14	1.384 (7)	C452—C453	1.320 (16)
C13—H13	0.9300	C453—C454	1.47 (2)
C14—C15	1.367 (7)	C453—H453	0.9300
C14—H14	0.9300	C454—C455	1.359 (10)
C15—C16	1.377 (7)	C454—H454	0.9300
C15—H15	0.9300	C455—H455	0.9300
C16—H16	0.9300	S551—C555	1.698 (14)
C31—H31A	0.9600	C553—C554	1.48 (2)
C31—H31B	0.9600	C553—H553	0.9300
C31—H31C	0.9600	C554—C555	1.359 (13)
N41—C45	1.293 (5)	C554—H554	0.9300
N41—N42	1.405 (5)	C555—H555	0.9300
N42—C422	1.333 (5)	O51—C51	1.405 (6)
N42—C43	1.507 (6)	C51—C56	1.379 (7)
C43—C44	1.557 (6)	C51—C52	1.387 (8)
C43—H43	0.9800	C52—C53	1.390 (10)
C44—C45	1.499 (7)	C52—C57	1.481 (8)
C44—H44A	0.9700	C53—C54	1.355 (10)
C44—H44B	0.9700	C53—H53	0.9300
C45—C452	1.441 (6)	C54—C55	1.362 (11)
S421—C425	1.736 (5)	C54—H54	0.9300
S421—C422	1.771 (5)	C55—C56	1.400 (9)
C422—N423	1.300 (6)	C55—H55	0.9300
N423—C424	1.378 (6)	C56—H56	0.9300
C424—O424	1.211 (6)	C57—H57A	0.9600
C424—C425	1.534 (7)	C57—H57B	0.9600
C425—C426	1.325 (6)	C57—H57C	0.9600
C5—N1—N2	109.6 (4)	C424—C425—S421	109.7 (4)
C5—N1—C11	131.7 (5)	C425—C426—C427	120.3 (5)
N2—N1—C11	118.6 (4)	C425—C426—H426	119.9
C3—N2—N1	105.2 (4)	C427—C426—H426	119.9
N2—C3—C4	112.1 (5)	O427—C427—O428	125.0 (7)
N2—C3—C31	120.0 (5)	O427—C427—C426	124.2 (6)
C4—C3—C31	127.9 (6)	O428—C427—C426	110.7 (6)
C5—C4—C3	103.6 (5)	C427—O428—C428	115.7 (5)
C5—C4—C43	128.2 (5)	O428—C428—C429	108.9 (6)
C3—C4—C43	128.2 (5)	O428—C428—H48A	109.9
N1—C5—C4	109.4 (5)	C429—C428—H48A	109.9
N1—C5—O51	122.3 (5)	O428—C428—H48B	109.9
C4—C5—O51	128.2 (5)	C429—C428—H48B	109.9
C16—C11—C12	119.6 (5)	H48A—C428—H48B	108.3
C16—C11—N1	119.3 (5)	C428—C429—H49A	109.5
C12—C11—N1	121.1 (5)	C428—C429—H49B	109.5
C11—C12—C13	119.0 (5)	H49A—C429—H49B	109.5
C11—C12—H12	120.5	C428—C429—H49C	109.5
C13—C12—H12	120.5	H49A—C429—H49C	109.5
C14—C13—C12	121.4 (6)	H49B—C429—H49C	109.5
C14—C13—H13	119.3	C455—S451—C452	91.1 (5)
C12—C13—H13	119.3	C453—C452—C45	124.6 (12)
C15—C14—C13	118.5 (6)	C453—C452—S451	113.6 (11)
C15—C14—H14	120.7	C45—C452—S451	121.6 (4)
C13—C14—H14	120.7	C452—C453—C454	111.2 (14)
C14—C15—C16	121.0 (6)	C452—C453—H453	124.4
C14—C15—H15	119.5	C454—C453—H453	124.4
C16—C15—H15	119.5	C455—C454—C453	111.1 (10)
C15—C16—C11	120.4 (5)	C455—C454—H454	124.5
C15—C16—H16	119.8	C453—C454—H454	124.5
C11—C16—H16	119.8	C454—C455—S451	112.8 (10)
C3—C31—H31A	109.5	C454—C455—H455	123.6
C3—C31—H31B	109.5	S451—C455—H455	123.6
H31A—C31—H31B	109.5	C554—C553—H553	124.6
C3—C31—H31C	109.5	C555—C554—C553	111.3 (16)
H31A—C31—H31C	109.5	C555—C554—H554	124.4
H31B—C31—H31C	109.5	C553—C554—H554	124.4
C45—N41—N42	107.5 (4)	C554—C555—S551	112.2 (17)
C422—N42—N41	120.5 (4)	C554—C555—H555	123.9
C422—N42—C43	125.3 (4)	S551—C555—H555	123.9
N41—N42—C43	114.2 (4)	C5—O51—C51	117.5 (4)
C4—C43—N42	112.5 (4)	C56—C51—C52	123.9 (6)
C4—C43—C44	115.7 (4)	C56—C51—O51	122.0 (6)
N42—C43—C44	98.8 (4)	C52—C51—O51	114.0 (6)
C4—C43—H43	109.8	C51—C52—C53	114.0 (7)
N42—C43—H43	109.8	C51—C52—C57	122.7 (7)
C44—C43—H43	109.8	C53—C52—C57	123.3 (7)
C45—C44—C43	104.6 (4)	C54—C53—C52	124.3 (10)
C45—C44—H44A	110.8	C54—C53—H53	117.8
C43—C44—H44A	110.8	C52—C53—H53	117.8
C45—C44—H44B	110.8	C53—C54—C55	120.1 (11)
C43—C44—H44B	110.8	C53—C54—H54	119.9
H44A—C44—H44B	108.9	C55—C54—H54	119.9
N41—C45—C452	121.4 (5)	C54—C55—C56	119.1 (9)
N41—C45—C44	114.0 (5)	C54—C55—H55	120.5
C452—C45—C44	124.5 (5)	C56—C55—H55	120.5
C425—S421—C422	87.3 (3)	C51—C56—C55	118.5 (7)
N423—C422—N42	121.8 (5)	C51—C56—H56	120.7
N423—C422—S421	120.3 (4)	C55—C56—H56	120.7
N42—C422—S421	117.9 (4)	C52—C57—H57A	109.5
C422—N423—C424	110.0 (5)	C52—C57—H57B	109.5
O424—C424—N423	125.4 (6)	H57A—C57—H57B	109.5
O424—C424—C425	122.0 (6)	C52—C57—H57C	109.5
N423—C424—C425	112.5 (5)	H57A—C57—H57C	109.5
C426—C425—C424	121.8 (5)	H57B—C57—H57C	109.5
C426—C425—S421	128.4 (5)
C5—N1—N2—C3	−0.1 (5)	C43—N42—C422—S421	−176.4 (4)
C11—N1—N2—C3	−178.6 (4)	C425—S421—C422—N423	−0.2 (5)
N1—N2—C3—C4	−1.0 (5)	C425—S421—C422—N42	−179.4 (4)
N1—N2—C3—C31	178.2 (4)	N42—C422—N423—C424	176.8 (5)
N2—C3—C4—C5	1.6 (5)	S421—C422—N423—C424	−2.4 (7)
C31—C3—C4—C5	−177.5 (5)	C422—N423—C424—O424	−176.2 (6)
N2—C3—C4—C43	−178.3 (4)	C422—N423—C424—C425	4.1 (7)
C31—C3—C4—C43	2.7 (8)	O424—C424—C425—C426	−6.1 (9)
N2—N1—C5—C4	1.1 (5)	N423—C424—C425—C426	173.5 (5)
C11—N1—C5—C4	179.4 (4)	O424—C424—C425—S421	176.0 (5)
N2—N1—C5—O51	177.6 (4)	N423—C424—C425—S421	−4.3 (6)
C11—N1—C5—O51	−4.2 (7)	C422—S421—C425—C426	−175.3 (6)
C3—C4—C5—N1	−1.6 (5)	C422—S421—C425—C424	2.4 (4)
C43—C4—C5—N1	178.3 (4)	C424—C425—C426—C427	−179.5 (6)
C3—C4—C5—O51	−177.8 (5)	S421—C425—C426—C427	−2.0 (8)
C43—C4—C5—O51	2.1 (8)	C425—C426—C427—O427	−2.8 (10)
C5—N1—C11—C16	−160.7 (5)	C425—C426—C427—O428	176.9 (5)
N2—N1—C11—C16	17.5 (6)	O427—C427—O428—C428	2.3 (9)
C5—N1—C11—C12	18.0 (7)	C426—C427—O428—C428	−177.4 (5)
N2—N1—C11—C12	−163.8 (4)	C427—O428—C428—C429	−168.6 (5)
C16—C11—C12—C13	0.2 (8)	N41—C45—C452—C453	−177.0 (19)
N1—C11—C12—C13	−178.5 (4)	C44—C45—C452—C453	5 (2)
C11—C12—C13—C14	−0.4 (8)	N41—C45—C452—S451	−3.3 (7)
C12—C13—C14—C15	−0.3 (9)	C44—C45—C452—S451	178.4 (5)
C13—C14—C15—C16	1.3 (9)	C455—S451—C452—C453	−2.9 (18)
C14—C15—C16—C11	−1.6 (8)	C455—S451—C452—C45	−177.2 (8)
C12—C11—C16—C15	0.8 (7)	C45—C452—C453—C454	180 (2)
N1—C11—C16—C15	179.5 (5)	S451—C452—C453—C454	5 (3)
C45—N41—N42—C422	178.4 (5)	C452—C453—C454—C455	−6 (4)
C45—N41—N42—C43	−4.1 (6)	C453—C454—C455—S451	4 (4)
C5—C4—C43—N42	70.7 (6)	C452—S451—C455—C454	−1 (2)
C3—C4—C43—N42	−109.5 (6)	C553—C554—C555—S551	−8 (12)
C5—C4—C43—C44	−41.9 (7)	N1—C5—O51—C51	92.8 (5)
C3—C4—C43—C44	138.0 (5)	C4—C5—O51—C51	−91.4 (6)
C422—N42—C43—C4	62.7 (6)	C5—O51—C51—C56	−0.8 (7)
N41—N42—C43—C4	−114.6 (5)	C5—O51—C51—C52	176.7 (5)
C422—N42—C43—C44	−174.7 (5)	C56—C51—C52—C53	−1.7 (9)
N41—N42—C43—C44	8.0 (5)	O51—C51—C52—C53	−179.1 (5)
C4—C43—C44—C45	111.9 (5)	C56—C51—C52—C57	−179.3 (6)
N42—C43—C44—C45	−8.3 (5)	O51—C51—C52—C57	3.3 (8)
N42—N41—C45—C452	179.2 (5)	C51—C52—C53—C54	2.1 (12)
N42—N41—C45—C44	−2.3 (6)	C57—C52—C53—C54	179.6 (8)
C43—C44—C45—N41	7.3 (6)	C52—C53—C54—C55	−2.4 (15)
C43—C44—C45—C452	−174.3 (5)	C53—C54—C55—C56	2.2 (14)
N41—N42—C422—N423	−178.4 (5)	C52—C51—C56—C55	1.7 (9)
C43—N42—C422—N423	4.4 (8)	O51—C51—C56—C55	178.9 (5)
N41—N42—C422—S421	0.7 (6)	C54—C55—C56—C51	−1.9 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O424^i	0.93	2.49	3.200 (7)	133
C54—H54···Cg1^ii	0.93	2.91	3.714 (12)	146
C553—H553···Cg1^iii	0.93	2.92	3.76 (5)	151

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

4-(4-Bromophenyl)-2-[5'-(2,4-dichlorophenoxy)-3'-methyl-1'-phenyl-5-(thiophen-2-yl)-3,4-dihydro-1'H,2H-3,4'-bipyrazole-2-yl]-4-thiazole (III)

Crystal data

C32H22BrCl2N5OS2	Z = 2
Mr = 707.47	F(000) = 716
Triclinic, P1	Dx = 1.517 Mg m^−3
a = 12.3200 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.5700 (9) Å	Cell parameters from 6664 reflections
c = 12.7742 (9) Å	θ = 2.6–27.8°
α = 117.202 (8)°	µ = 1.67 mm^−1
β = 102.879 (7)°	T = 296 K
γ = 105.727 (7)°	Plate, yellow
V = 1548.4 (2) Å^3	0.40 × 0.40 × 0.08 mm

Data collection

Oxford Diffraction Xcalibur with Sapphire CCD detector diffractometer	5773 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3158 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ω scans	θmax = 25.6°, θmin = 2.6°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −13→14
Tmin = 0.779, Tmax = 0.875	k = −15→10
10549 measured reflections	l = −10→15

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)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0475P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.93	(Δ/σ)max < 0.001
5773 reflections	Δρmax = 0.47 e Å^−3
402 parameters	Δρmin = −0.34 e Å^−3
10 restraints

Special details

Experimental. CrysAlis RED, Oxford Diffraction Ltd., 2009 Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	Occ. (<1)
N1	0.5457 (2)	0.3735 (2)	0.86216 (19)	0.0478 (5)
N2	0.4327 (2)	0.3754 (2)	0.8277 (2)	0.0514 (6)
C3	0.4368 (3)	0.4319 (2)	0.7616 (2)	0.0495 (7)
C4	0.5508 (3)	0.4674 (2)	0.7522 (2)	0.0477 (7)
C5	0.6162 (2)	0.4278 (2)	0.8157 (2)	0.0446 (6)
C11	0.5693 (3)	0.3119 (2)	0.9294 (2)	0.0449 (6)
C12	0.6877 (3)	0.3383 (3)	0.9963 (3)	0.0552 (7)
H12	0.7546	0.3982	0.9997	0.066*
C13	0.7064 (3)	0.2750 (3)	1.0586 (3)	0.0591 (8)
H13	0.7863	0.2915	1.1029	0.071*
C14	0.6089 (3)	0.1887 (3)	1.0558 (3)	0.0630 (8)
H14	0.6221	0.1465	1.0978	0.076*
C15	0.4917 (3)	0.1647 (3)	0.9907 (3)	0.0719 (9)
H15	0.4252	0.1064	0.9893	0.086*
C16	0.4707 (3)	0.2257 (3)	0.9271 (3)	0.0617 (8)
H16	0.3906	0.2088	0.8830	0.074*
C31	0.3270 (3)	0.4476 (3)	0.7047 (3)	0.0686 (8)
H31A	0.3053	0.4075	0.6140	0.103*
H31B	0.3464	0.5402	0.7453	0.103*
H31C	0.2589	0.4054	0.7181	0.103*
N41	0.7375 (3)	0.5162 (3)	0.5905 (3)	0.0661 (7)
N42	0.6211 (2)	0.4547 (3)	0.5794 (2)	0.0670 (7)
C43	0.5928 (3)	0.5358 (3)	0.6881 (3)	0.0576 (7)
H43	0.5288	0.5591	0.6567	0.069*
C44	0.7168 (3)	0.6608 (3)	0.7729 (3)	0.0672 (8)
H44A	0.7058	0.7390	0.7866	0.081*
H44B	0.7546	0.6741	0.8558	0.081*
C45	0.7931 (3)	0.6315 (3)	0.6965 (3)	0.0622 (8)
S421	0.59658 (8)	0.25102 (9)	0.35914 (8)	0.0776 (3)
C422	0.5442 (3)	0.3311 (3)	0.4739 (3)	0.0576 (8)
N423	0.4313 (2)	0.2671 (2)	0.4522 (2)	0.0554 (6)
C424	0.3781 (3)	0.1417 (3)	0.3379 (3)	0.0568 (7)
C425	0.4545 (3)	0.1182 (3)	0.2773 (3)	0.0724 (9)
H425	0.4325	0.0394	0.2004	0.087*
C441	0.2509 (3)	0.0523 (3)	0.2964 (3)	0.0557 (7)
C442	0.1828 (3)	0.0877 (3)	0.3669 (3)	0.0663 (8)
H442	0.2188	0.1712	0.4429	0.080*
C443	0.0635 (3)	0.0037 (3)	0.3287 (3)	0.0738 (9)
H443	0.0196	0.0310	0.3783	0.089*
C444	0.0085 (3)	−0.1208 (3)	0.2172 (3)	0.0667 (8)
Br44	−0.15403 (3)	−0.23859 (4)	0.16704 (4)	0.09399 (17)
C445	0.0740 (4)	−0.1594 (3)	0.1453 (3)	0.0803 (10)
H445	0.0378	−0.2435	0.0700	0.096*
C446	0.1919 (4)	−0.0751 (3)	0.1836 (3)	0.0778 (9)
H446	0.2349	−0.1030	0.1331	0.093*
S451	0.99714 (13)	0.68706 (13)	0.64070 (13)	0.1055 (6)	0.947 (4)
C452	0.9177 (3)	0.7199 (4)	0.7353 (4)	0.0739 (9)	0.947 (4)
C453	0.9844 (6)	0.8384 (6)	0.8487 (6)	0.0934 (17)	0.947 (4)
H453	0.9561	0.8733	0.9127	0.112*	0.947 (4)
C454	1.1069 (5)	0.9043 (5)	0.8577 (6)	0.1124 (18)	0.947 (4)
H454	1.1665	0.9865	0.9289	0.135*	0.947 (4)
C455	1.1232 (5)	0.8339 (6)	0.7532 (7)	0.1145 (18)	0.947 (4)
H455	1.1955	0.8612	0.7421	0.137*	0.947 (4)
S551	1.025 (3)	0.871 (2)	0.863 (3)	0.0934 (17)	0.053 (4)
C552	0.9177 (3)	0.7199 (4)	0.7353 (4)	0.0739 (9)	0.053 (4)
C553	0.966 (5)	0.658 (5)	0.654 (6)	0.1055 (6)	0.053 (4)
H553	0.9264	0.5696	0.5857	0.127*	0.053 (4)
C554	1.090 (5)	0.750 (6)	0.687 (7)	0.1145 (18)	0.053 (4)
H554	1.1374	0.7270	0.6403	0.137*	0.053 (4)
C555	1.126 (7)	0.868 (8)	0.790 (10)	0.1124 (18)	0.053 (4)
H555	1.1972	0.9419	0.8192	0.135*	0.053 (4)
O51	0.73172 (16)	0.43438 (16)	0.83109 (15)	0.0493 (4)
C51	0.7387 (2)	0.3304 (2)	0.7303 (2)	0.0440 (6)
C52	0.8521 (2)	0.3502 (3)	0.7240 (3)	0.0488 (7)
Cl52	0.97805 (7)	0.50033 (8)	0.83960 (9)	0.0895 (3)
C53	0.8662 (3)	0.2526 (3)	0.6269 (3)	0.0586 (8)
H53	0.9429	0.2664	0.6230	0.070*
C54	0.7648 (3)	0.1344 (3)	0.5356 (3)	0.0563 (7)
Cl54	0.77954 (9)	0.01019 (9)	0.41070 (8)	0.0873 (3)
C55	0.6533 (3)	0.1136 (3)	0.5414 (3)	0.0634 (8)
H55	0.5856	0.0330	0.4793	0.076*
C56	0.6397 (3)	0.2115 (3)	0.6391 (3)	0.0576 (7)
H56	0.5628	0.1966	0.6428	0.069*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0546 (15)	0.0491 (13)	0.0455 (13)	0.0245 (12)	0.0228 (11)	0.0279 (12)
N2	0.0558 (15)	0.0592 (14)	0.0494 (14)	0.0323 (12)	0.0271 (12)	0.0304 (12)
C3	0.0627 (19)	0.0521 (17)	0.0406 (16)	0.0336 (15)	0.0240 (14)	0.0241 (14)
C4	0.0656 (19)	0.0472 (16)	0.0404 (16)	0.0306 (15)	0.0266 (14)	0.0257 (14)
C5	0.0547 (18)	0.0403 (15)	0.0406 (15)	0.0226 (14)	0.0252 (14)	0.0198 (13)
C11	0.0557 (18)	0.0434 (15)	0.0406 (15)	0.0250 (14)	0.0224 (14)	0.0235 (13)
C12	0.062 (2)	0.0595 (18)	0.0545 (17)	0.0272 (16)	0.0278 (15)	0.0363 (16)
C13	0.065 (2)	0.070 (2)	0.0525 (18)	0.0350 (18)	0.0262 (16)	0.0367 (17)
C14	0.090 (2)	0.060 (2)	0.0539 (19)	0.0401 (19)	0.0315 (18)	0.0366 (16)
C15	0.079 (2)	0.068 (2)	0.080 (2)	0.0250 (19)	0.0351 (19)	0.0506 (19)
C16	0.0580 (18)	0.066 (2)	0.067 (2)	0.0224 (17)	0.0225 (16)	0.0438 (18)
C31	0.085 (2)	0.083 (2)	0.065 (2)	0.054 (2)	0.0393 (18)	0.0460 (18)
N41	0.080 (2)	0.0741 (19)	0.0642 (18)	0.0358 (17)	0.0382 (16)	0.0471 (17)
N42	0.0780 (19)	0.0714 (18)	0.0550 (17)	0.0272 (16)	0.0397 (15)	0.0343 (15)
C43	0.074 (2)	0.0604 (19)	0.0558 (18)	0.0365 (18)	0.0330 (17)	0.0377 (16)
C44	0.089 (2)	0.0558 (19)	0.066 (2)	0.0305 (19)	0.0310 (19)	0.0409 (17)
C45	0.078 (2)	0.071 (2)	0.068 (2)	0.039 (2)	0.036 (2)	0.054 (2)
S421	0.0958 (7)	0.0867 (6)	0.0679 (5)	0.0459 (6)	0.0536 (5)	0.0425 (5)
C422	0.080 (2)	0.067 (2)	0.0479 (19)	0.0399 (19)	0.0355 (17)	0.0392 (18)
N423	0.0729 (18)	0.0614 (16)	0.0449 (14)	0.0360 (15)	0.0317 (13)	0.0311 (13)
C424	0.080 (2)	0.062 (2)	0.0451 (18)	0.0416 (19)	0.0316 (17)	0.0329 (17)
C425	0.095 (2)	0.072 (2)	0.059 (2)	0.044 (2)	0.0440 (19)	0.0326 (17)
C441	0.081 (2)	0.0597 (19)	0.0423 (17)	0.0442 (18)	0.0298 (16)	0.0295 (15)
C442	0.078 (2)	0.060 (2)	0.0572 (19)	0.041 (2)	0.0311 (18)	0.0224 (16)
C443	0.077 (2)	0.070 (2)	0.070 (2)	0.042 (2)	0.0344 (19)	0.0274 (19)
C444	0.076 (2)	0.069 (2)	0.068 (2)	0.0457 (19)	0.0303 (19)	0.0385 (19)
Br44	0.0795 (3)	0.0793 (3)	0.1006 (3)	0.0331 (2)	0.0273 (2)	0.0381 (2)
C445	0.092 (3)	0.061 (2)	0.064 (2)	0.031 (2)	0.031 (2)	0.0186 (18)
C446	0.101 (3)	0.078 (3)	0.061 (2)	0.048 (2)	0.048 (2)	0.031 (2)
S451	0.0958 (12)	0.1464 (12)	0.1214 (10)	0.0581 (10)	0.0620 (8)	0.0961 (9)
C452	0.074 (2)	0.078 (2)	0.088 (3)	0.030 (2)	0.028 (2)	0.062 (2)
C453	0.067 (4)	0.080 (4)	0.124 (4)	0.012 (3)	0.028 (3)	0.065 (3)
C454	0.076 (4)	0.112 (4)	0.155 (5)	0.026 (3)	0.034 (3)	0.091 (4)
C455	0.075 (3)	0.149 (5)	0.171 (6)	0.044 (4)	0.046 (4)	0.128 (5)
S551	0.067 (4)	0.080 (4)	0.124 (4)	0.012 (3)	0.028 (3)	0.065 (3)
C552	0.074 (2)	0.078 (2)	0.088 (3)	0.030 (2)	0.028 (2)	0.062 (2)
C553	0.0958 (12)	0.1464 (12)	0.1214 (10)	0.0581 (10)	0.0620 (8)	0.0961 (9)
C554	0.075 (3)	0.149 (5)	0.171 (6)	0.044 (4)	0.046 (4)	0.128 (5)
C555	0.076 (4)	0.112 (4)	0.155 (5)	0.026 (3)	0.034 (3)	0.091 (4)
O51	0.0512 (12)	0.0460 (11)	0.0451 (11)	0.0196 (9)	0.0208 (9)	0.0212 (9)
C51	0.0533 (18)	0.0436 (16)	0.0432 (16)	0.0229 (15)	0.0241 (14)	0.0266 (14)
C52	0.0421 (16)	0.0517 (17)	0.0502 (17)	0.0159 (14)	0.0166 (14)	0.0299 (15)
Cl52	0.0503 (5)	0.0766 (6)	0.0886 (6)	0.0101 (4)	0.0132 (4)	0.0238 (5)
C53	0.0549 (19)	0.077 (2)	0.064 (2)	0.0381 (18)	0.0339 (17)	0.0431 (19)
C54	0.073 (2)	0.062 (2)	0.0535 (18)	0.0405 (18)	0.0372 (17)	0.0341 (17)
Cl54	0.1139 (7)	0.0907 (6)	0.0691 (5)	0.0620 (6)	0.0543 (5)	0.0350 (5)
C55	0.063 (2)	0.0437 (17)	0.064 (2)	0.0156 (15)	0.0306 (16)	0.0180 (15)
C56	0.0493 (17)	0.0473 (18)	0.068 (2)	0.0167 (15)	0.0322 (16)	0.0242 (16)

Geometric parameters (Å, º)

N1—C5	1.361 (3)	C425—H425	0.9300
N1—N2	1.374 (3)	C441—C442	1.373 (4)
N1—C11	1.428 (3)	C441—C446	1.400 (4)
N2—C3	1.330 (3)	C442—C443	1.372 (4)
C3—C4	1.404 (3)	C442—H442	0.9300
C3—C31	1.495 (3)	C443—C444	1.377 (4)
C4—C5	1.361 (3)	C443—H443	0.9300
C4—C43	1.506 (3)	C444—C445	1.366 (4)
C5—O51	1.367 (3)	C444—Br44	1.888 (3)
C11—C12	1.375 (3)	C445—C446	1.359 (4)
C11—C16	1.375 (3)	C445—H445	0.9300
C12—C13	1.385 (3)	C446—H446	0.9300
C12—H12	0.9300	S451—C452	1.696 (4)
C13—C14	1.364 (4)	S451—C455	1.706 (6)
C13—H13	0.9300	C452—C453	1.351 (7)
C14—C15	1.366 (4)	C453—C454	1.461 (10)
C14—H14	0.9300	C453—H453	0.9300
C15—C16	1.379 (4)	C454—C455	1.321 (7)
C15—H15	0.9300	C454—H454	0.9300
C16—H16	0.9300	C455—H455	0.9300
C31—H31A	0.9600	S551—C555	1.707 (12)
C31—H31B	0.9600	C553—C554	1.461 (14)
C31—H31C	0.9600	C553—H553	0.9300
N41—C45	1.287 (4)	C554—C555	1.322 (12)
N41—N42	1.372 (3)	C554—H554	0.9300
N42—C422	1.359 (4)	C555—H555	0.9300
N42—C43	1.484 (3)	O51—C51	1.395 (3)
C43—C44	1.543 (4)	C51—C56	1.366 (3)
C43—H43	0.9800	C51—C52	1.379 (3)
C44—C45	1.496 (4)	C52—C53	1.377 (4)
C44—H44A	0.9700	C52—Cl52	1.730 (3)
C44—H44B	0.9700	C53—C54	1.374 (4)
C45—C452	1.439 (4)	C53—H53	0.9300
S421—C425	1.717 (3)	C54—C55	1.353 (4)
S421—C422	1.734 (3)	C54—Cl54	1.737 (3)
C422—N423	1.295 (3)	C55—C56	1.379 (4)
N423—C424	1.399 (3)	C55—H55	0.9300
C424—C425	1.356 (4)	C56—H56	0.9300
C424—C441	1.460 (4)
C5—N1—N2	109.84 (19)	C425—C424—C441	127.3 (3)
C5—N1—C11	130.5 (2)	N423—C424—C441	118.8 (3)
N2—N1—C11	119.5 (2)	C424—C425—S421	112.0 (2)
C3—N2—N1	105.3 (2)	C424—C425—H425	124.0
N2—C3—C4	111.7 (2)	S421—C425—H425	124.0
N2—C3—C31	120.5 (2)	C442—C441—C446	116.2 (3)
C4—C3—C31	127.7 (2)	C442—C441—C424	121.8 (3)
C5—C4—C3	104.5 (2)	C446—C441—C424	122.0 (3)
C5—C4—C43	127.4 (3)	C443—C442—C441	122.0 (3)
C3—C4—C43	128.1 (2)	C443—C442—H442	119.0
C4—C5—N1	108.7 (2)	C441—C442—H442	119.0
C4—C5—O51	128.6 (2)	C442—C443—C444	120.1 (3)
N1—C5—O51	122.7 (2)	C442—C443—H443	119.9
C12—C11—C16	120.1 (2)	C444—C443—H443	119.9
C12—C11—N1	121.3 (2)	C445—C444—C443	119.3 (3)
C16—C11—N1	118.6 (2)	C445—C444—Br44	120.4 (3)
C11—C12—C13	119.4 (3)	C443—C444—Br44	120.3 (3)
C11—C12—H12	120.3	C446—C445—C444	120.1 (3)
C13—C12—H12	120.3	C446—C445—H445	120.0
C14—C13—C12	120.7 (3)	C444—C445—H445	120.0
C14—C13—H13	119.7	C445—C446—C441	122.3 (3)
C12—C13—H13	119.7	C445—C446—H446	118.9
C13—C14—C15	119.5 (3)	C441—C446—H446	118.9
C13—C14—H14	120.2	C452—S451—C455	92.0 (3)
C15—C14—H14	120.2	C453—C452—C45	124.7 (4)
C14—C15—C16	120.9 (3)	C453—C452—S451	112.1 (3)
C14—C15—H15	119.6	C45—C452—S451	123.2 (3)
C16—C15—H15	119.6	C452—C453—C454	111.1 (6)
C11—C16—C15	119.4 (3)	C452—C453—H453	124.4
C11—C16—H16	120.3	C454—C453—H453	124.4
C15—C16—H16	120.3	C455—C454—C453	112.2 (5)
C3—C31—H31A	109.5	C455—C454—H454	123.9
C3—C31—H31B	109.5	C453—C454—H454	123.9
H31A—C31—H31B	109.5	C454—C455—S451	112.5 (4)
C3—C31—H31C	109.5	C454—C455—H455	123.8
H31A—C31—H31C	109.5	S451—C455—H455	123.8
H31B—C31—H31C	109.5	C554—C553—H553	124.5
C45—N41—N42	108.5 (3)	C555—C554—C553	111.9 (12)
C422—N42—N41	119.3 (3)	C555—C554—H554	124.0
C422—N42—C43	126.7 (3)	C553—C554—H554	124.0
N41—N42—C43	114.0 (2)	C554—C555—S551	112.0 (15)
N42—C43—C4	113.5 (2)	C554—C555—H555	124.0
N42—C43—C44	100.3 (2)	S551—C555—H555	124.0
C4—C43—C44	115.3 (2)	C5—O51—C51	115.95 (19)
N42—C43—H43	109.1	C56—C51—C52	119.1 (2)
C4—C43—H43	109.1	C56—C51—O51	123.4 (2)
C44—C43—H43	109.1	C52—C51—O51	117.5 (2)
C45—C44—C43	103.5 (2)	C53—C52—C51	120.9 (3)
C45—C44—H44A	111.1	C53—C52—Cl52	119.7 (2)
C43—C44—H44A	111.1	C51—C52—Cl52	119.4 (2)
C45—C44—H44B	111.1	C54—C53—C52	118.8 (3)
C43—C44—H44B	111.1	C54—C53—H53	120.6
H44A—C44—H44B	109.0	C52—C53—H53	120.6
N41—C45—C452	121.5 (3)	C55—C54—C53	120.7 (3)
N41—C45—C44	113.6 (3)	C55—C54—Cl54	119.5 (2)
C452—C45—C44	124.8 (3)	C53—C54—Cl54	119.8 (2)
C425—S421—C422	87.62 (16)	C54—C55—C56	120.3 (3)
N423—C422—N42	123.9 (3)	C54—C55—H55	119.8
N423—C422—S421	116.5 (2)	C56—C55—H55	119.8
N42—C422—S421	119.6 (3)	C51—C56—C55	120.1 (3)
C422—N423—C424	109.9 (3)	C51—C56—H56	119.9
C425—C424—N423	113.9 (3)	C55—C56—H56	119.9
C5—N1—N2—C3	−0.4 (3)	N42—C422—N423—C424	−178.4 (2)
C11—N1—N2—C3	−176.7 (2)	S421—C422—N423—C424	1.8 (3)
N1—N2—C3—C4	−0.1 (3)	C422—N423—C424—C425	−1.0 (3)
N1—N2—C3—C31	178.2 (2)	C422—N423—C424—C441	179.2 (2)
N2—C3—C4—C5	0.6 (3)	N423—C424—C425—S421	−0.1 (3)
C31—C3—C4—C5	−177.6 (2)	C441—C424—C425—S421	179.6 (2)
N2—C3—C4—C43	−178.6 (2)	C422—S421—C425—C424	0.9 (2)
C31—C3—C4—C43	3.2 (4)	C425—C424—C441—C442	179.8 (3)
C3—C4—C5—N1	−0.8 (3)	N423—C424—C441—C442	−0.5 (4)
C43—C4—C5—N1	178.3 (2)	C425—C424—C441—C446	0.8 (4)
C3—C4—C5—O51	177.3 (2)	N423—C424—C441—C446	−179.5 (2)
C43—C4—C5—O51	−3.5 (4)	C446—C441—C442—C443	−0.5 (4)
N2—N1—C5—C4	0.8 (3)	C424—C441—C442—C443	−179.6 (3)
C11—N1—C5—C4	176.5 (2)	C441—C442—C443—C444	0.5 (5)
N2—N1—C5—O51	−177.4 (2)	C442—C443—C444—C445	−0.1 (5)
C11—N1—C5—O51	−1.7 (4)	C442—C443—C444—Br44	178.1 (2)
C5—N1—C11—C12	22.9 (4)	C443—C444—C445—C446	−0.3 (5)
N2—N1—C11—C12	−161.7 (2)	Br44—C444—C445—C446	−178.5 (2)
C5—N1—C11—C16	−157.7 (3)	C444—C445—C446—C441	0.3 (5)
N2—N1—C11—C16	17.7 (3)	C442—C441—C446—C445	0.1 (4)
C16—C11—C12—C13	1.5 (4)	C424—C441—C446—C445	179.2 (3)
N1—C11—C12—C13	−179.1 (2)	N41—C45—C452—C453	−175.4 (5)
C11—C12—C13—C14	−1.0 (4)	C44—C45—C452—C453	3.4 (6)
C12—C13—C14—C15	0.0 (4)	N41—C45—C452—S451	5.6 (4)
C13—C14—C15—C16	0.5 (5)	C44—C45—C452—S451	−175.5 (2)
C12—C11—C16—C15	−1.0 (4)	C455—S451—C452—C453	−0.1 (4)
N1—C11—C16—C15	179.6 (2)	C455—S451—C452—C45	179.0 (3)
C14—C15—C16—C11	0.0 (4)	C45—C452—C453—C454	−179.4 (4)
C45—N41—N42—C422	179.6 (2)	S451—C452—C453—C454	−0.3 (6)
C45—N41—N42—C43	0.5 (3)	C452—C453—C454—C455	0.6 (7)
C422—N42—C43—C4	55.9 (4)	C453—C454—C455—S451	−0.6 (7)
N41—N42—C43—C4	−125.0 (3)	C452—S451—C455—C454	0.4 (5)
C422—N42—C43—C44	179.5 (2)	C553—C554—C555—S551	8 (16)
N41—N42—C43—C44	−1.4 (3)	C4—C5—O51—C51	−84.1 (3)
C5—C4—C43—N42	63.0 (4)	N1—C5—O51—C51	93.9 (3)
C3—C4—C43—N42	−118.0 (3)	C5—O51—C51—C56	−17.9 (3)
C5—C4—C43—C44	−51.9 (4)	C5—O51—C51—C52	162.1 (2)
C3—C4—C43—C44	127.1 (3)	C56—C51—C52—C53	0.5 (4)
N42—C43—C44—C45	1.7 (2)	O51—C51—C52—C53	−179.5 (2)
C4—C43—C44—C45	124.0 (2)	C56—C51—C52—Cl52	−179.80 (19)
N42—N41—C45—C452	179.8 (2)	O51—C51—C52—Cl52	0.2 (3)
N42—N41—C45—C44	0.8 (3)	C51—C52—C53—C54	0.1 (4)
C43—C44—C45—N41	−1.7 (3)	Cl52—C52—C53—C54	−179.63 (19)
C43—C44—C45—C452	179.3 (2)	C52—C53—C54—C55	−0.5 (4)
N41—N42—C422—N423	−177.2 (2)	C52—C53—C54—Cl54	179.2 (2)
C43—N42—C422—N423	1.9 (4)	C53—C54—C55—C56	0.3 (4)
N41—N42—C422—S421	2.6 (3)	Cl54—C54—C55—C56	−179.3 (2)
C43—N42—C422—S421	−178.31 (19)	C52—C51—C56—C55	−0.7 (4)
C425—S421—C422—N423	−1.6 (2)	O51—C51—C56—C55	179.4 (2)
C425—S421—C422—N42	178.6 (2)	C54—C55—C56—C51	0.3 (4)