Different packing motifs of isomeric (E)-N′-(halo­phenyl­methyl­idene)-N-methyl-2-(thio­phen-2-yl)acetohydrazides controlled by C—H⋯O inter­actions

Cardoso, L.N.F.; Noguiera, T.C.M.; Wardell, J.L.; Souza, M.V.N. de; Harrison, W.T.A.

doi:10.1107/S2056989018001251

Different packing motifs of isomeric (E)-N′-(halophenylmethylidene)-N-methyl-2-(thiophen-2-yl)acetohydrazides controlled by C—HO interactions

L. N. F. Cardoso, T. C. M. Noguiera, J. L. Wardell, M. V. N. de Souza and W. T. A. Harrison

The packing motifs in the isomeric title compounds feature inversion dimers or chains, mediated by C—H

O interactions, one of which is unusually short (H

O = 2.18 Å).

Keywords: crystal structure; carbohydrazide; methylation; weak hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989018001251/sj5543sup1.cif Contains datablocks I, II, III, IV, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989018001251/sj5543Isup2.hkl Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989018001251/sj5543IIsup3.hkl Contains datablock II
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989018001251/sj5543IIIsup4.hkl Contains datablock III
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989018001251/sj5543IVsup5.hkl Contains datablock IV

CCDC references: 1818231; 1818230; 1818229; 1818228

checkCIF report

Key indicators

Structure: I

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.004 Å
Disorder in main residue
R factor = 0.052
wR factor = 0.117
Data-to-parameter ratio = 17.1

Structure: II

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.002 Å
Disorder in main residue
R factor = 0.025
wR factor = 0.064
Data-to-parameter ratio = 18.2

Structure: III

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.011 Å
Disorder in main residue
R factor = 0.116
wR factor = 0.297
Data-to-parameter ratio = 17.0

Structure: IV

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.002 Å
Disorder in main residue
R factor = 0.033
wR factor = 0.091
Data-to-parameter ratio = 18.2

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      8.566 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.443 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         96 Report

Alert level G
PLAT019_ALERT_1_G _diffrn_measured_fraction_theta_full/*_max < 1.0      0.996 Report
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          2 Report
PLAT230_ALERT_2_G Hirshfeld Test Diff for   S1       --C14       .        5.4 s.u.
PLAT230_ALERT_2_G Hirshfeld Test Diff for   S1A      --C11       .       11.9 s.u.
PLAT230_ALERT_2_G Hirshfeld Test Diff for   S1A      --C13       .       16.0 s.u.
PLAT230_ALERT_2_G Hirshfeld Test Diff for   C11      --C12       .       11.9 s.u.
PLAT230_ALERT_2_G Hirshfeld Test Diff for   C12      --C13       .       16.0 s.u.
PLAT230_ALERT_2_G Hirshfeld Test Diff for   C14      --C12A      .        5.4 s.u.
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1  )        11% Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         16 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...         13 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
  13 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
   5 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




Datablock: II


Alert level B
PLAT340_ALERT_3_B Low Bond Precision on  C-C Bonds ...............     0.0106 Ang.

Alert level C
PLAT020_ALERT_3_C The Value of Rint is Greater Than 0.12 .........      0.127 Report
PLAT082_ALERT_2_C High R1 Value ..................................       0.12 Report
PLAT084_ALERT_3_C High wR2 Value (i.e. > 0.25) ...................       0.30 Report
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.22 Report
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6       ..O1               2.62 Ang.
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......     19.261 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.610 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         26 Report
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          2 Report
PLAT230_ALERT_2_G Hirshfeld Test Diff for   S1       --C14       .        8.0 s.u.
PLAT230_ALERT_2_G Hirshfeld Test Diff for   S1A      --C11       .       17.4 s.u.
PLAT230_ALERT_2_G Hirshfeld Test Diff for   S1A      --C13       .       17.5 s.u.
PLAT230_ALERT_2_G Hirshfeld Test Diff for   C11      --C12       .       17.4 s.u.
PLAT230_ALERT_2_G Hirshfeld Test Diff for   C12      --C13       .       17.5 s.u.
PLAT230_ALERT_2_G Hirshfeld Test Diff for   C14      --C12A      .        8.0 s.u.
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1  )        11% Note
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          2 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          7 Info

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

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




Datablock: III



Alert level B
PLAT340_ALERT_3_B Low Bond Precision on  C-C Bonds ...............     0.0106 Ang.

Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.12
            Rint given   0.127
PLAT020_ALERT_3_C The Value of Rint is Greater Than 0.12 .........      0.127 Report
PLAT082_ALERT_2_C High R1 Value ..................................       0.12 Report
PLAT084_ALERT_3_C High wR2 Value (i.e. > 0.25) ...................       0.30 Report
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.22 Report
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6       ..O1               2.62 Ang.
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......     19.261 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.610 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         26 Report
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
PLAT019_ALERT_1_G _diffrn_measured_fraction_theta_full/*_max < 1.0      0.998 Report
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT  Unusually Large       8.00 Why ?
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          2 Report
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1  )        16% Note
PLAT773_ALERT_2_G Check long C-C Bond in CIF: C11      --C12A            1.72 Ang.
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... #         15 Check
              CL2  -C4   -H4      1.555   1.555   1.555             10.50 Deg.
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... #         21 Check
              CL1  -C5   -H5      1.555   1.555   1.555              0.50 Deg.
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... #         65 Check
              C5   -CL1  -H5      1.555   1.555   1.555              0.60 Deg.
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... #         67 Check
              C4   -CL2  -H4      1.555   1.555   1.555             12.40 Deg.
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          3 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          3 Note

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

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




Datablock: IV


Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3       ..CL1              2.95 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H12      ..CL1              2.98 Ang.
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          4 Report

Alert level G
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          2 Report
PLAT230_ALERT_2_G Hirshfeld Test Diff for   S1       --C14       .       16.9 s.u.
PLAT230_ALERT_2_G Hirshfeld Test Diff for   S1A      --C11       .       18.9 s.u.
PLAT230_ALERT_2_G Hirshfeld Test Diff for   S1A      --C13       .        7.1 s.u.
PLAT230_ALERT_2_G Hirshfeld Test Diff for   C11      --C12       .       18.9 s.u.
PLAT230_ALERT_2_G Hirshfeld Test Diff for   C12      --C13       .        7.1 s.u.
PLAT230_ALERT_2_G Hirshfeld Test Diff for   C14      --C12A      .       16.9 s.u.
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1  )        11% Note
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          3 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          3 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          8 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
  13 ALERT level G = General information/check it is not something unexpected

   0 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
   4 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

Computing details top

For all structures, data collection: CrystalClear (Rigaku, 2012); cell refinement: CrystalClear (Rigaku, 2012); data reduction: CrystalClear (Rigaku, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2010).

(E)-N'-(2-Chlorophenylmethylidene)-N-methyl-2-(thiophen-2-yl)acetohydrazide (I) top

Crystal data top

C₁₄H₁₃ClN₂OS	F(000) = 608
M_r = 292.77	D_x = 1.438 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.1918 (7) Å	Cell parameters from 18890 reflections
b = 20.3575 (14) Å	θ = 2.0–27.5°
c = 7.2721 (5) Å	µ = 0.43 mm⁻¹
β = 96.360 (2)°	T = 100 K
V = 1352.40 (17) Å³	Block, colourless
Z = 4	0.53 × 0.24 × 0.18 mm

Data collection top

Rigaku Mercury CCD diffractometer	2553 reflections with I > 2σ(I)
ω scans	R_int = 0.032
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 27.5°, θ_min = 2.2°
T_min = 0.710, T_max = 1.000	h = −11→11
18992 measured reflections	k = −26→26
2988 independent reflections	l = −9→9

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.052	w = 1/[σ²(F_o²) + (0.0254P)² + 1.9705P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.117	(Δ/σ)_max < 0.001
S = 1.22	Δρ_max = 0.37 e Å⁻³
2988 reflections	Δρ_min = −0.41 e Å⁻³
175 parameters	Extinction correction: SHELXL-2014/7 (Sheldrick 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0035 (9)
Primary atom site location: structure-invariant direct methods

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.4009 (3)	0.30066 (11)	0.2999 (3)	0.0205 (5)
C2	0.2682 (3)	0.32749 (12)	0.2216 (4)	0.0238 (5)
H2	0.1913	0.2989	0.1741	0.029*
C3	0.2462 (3)	0.39464 (12)	0.2116 (4)	0.0261 (5)
H3	0.1551	0.4117	0.1578	0.031*
C4	0.3576 (3)	0.43717 (12)	0.2804 (4)	0.0264 (6)
H4	0.3421	0.4833	0.2749	0.032*
C5	0.4909 (3)	0.41239 (12)	0.3568 (3)	0.0249 (5)
H5	0.5680	0.4413	0.4017	0.030*
C6	0.5107 (3)	0.34485 (12)	0.3669 (3)	0.0216 (5)
C7	0.4218 (3)	0.22913 (11)	0.3101 (3)	0.0219 (5)
H7	0.5122	0.2109	0.3624	0.026*
C8	0.4721 (3)	0.09617 (12)	0.3393 (4)	0.0264 (5)
H8A	0.4937	0.1124	0.4663	0.040*
H8B	0.5519	0.1084	0.2671	0.040*
H8C	0.4625	0.0482	0.3408	0.040*
C9	0.2211 (3)	0.08562 (12)	0.1850 (4)	0.0250 (5)
C10	0.0768 (3)	0.11842 (12)	0.1155 (4)	0.0273 (6)
H10A	0.0953	0.1628	0.0676	0.033*
H10B	0.0252	0.0923	0.0136	0.033*
C11	−0.0155 (3)	0.12331 (12)	0.2724 (4)	0.0242 (5)
C12	−0.08888 (16)	0.06244 (7)	0.3623 (2)	0.0380 (5)	0.658 (4)
H12	−0.0897	0.0174	0.3275	0.046*	0.658 (4)
S1A	−0.08888 (16)	0.06244 (7)	0.3623 (2)	0.0380 (5)	0.342 (4)
C13	−0.1560 (3)	0.09474 (17)	0.5151 (5)	0.0457 (9)
H13	−0.2067	0.0702	0.5989	0.055*
C14	−0.1418 (3)	0.16036 (16)	0.5300 (4)	0.0382 (7)
H14	−0.1818	0.1853	0.6227	0.046*
N1	0.3152 (2)	0.19186 (9)	0.2469 (3)	0.0214 (4)
N2	0.3356 (2)	0.12514 (9)	0.2554 (3)	0.0230 (4)
O1	0.2336 (2)	0.02600 (9)	0.1856 (3)	0.0337 (5)
Cl1	0.67905 (7)	0.31638 (3)	0.47232 (10)	0.03056 (18)
S1	−0.04886 (10)	0.19336 (4)	0.37322 (13)	0.0294 (3)	0.658 (4)
C12A	−0.04886 (10)	0.19336 (4)	0.37322 (13)	0.0294 (3)	0.342 (4)
H12A	−0.0232	0.2375	0.3490	0.035*	0.342 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0228 (13)	0.0230 (11)	0.0163 (11)	0.0015 (9)	0.0041 (9)	0.0001 (8)
C2	0.0236 (13)	0.0232 (12)	0.0245 (13)	−0.0008 (9)	0.0014 (10)	−0.0001 (9)
C3	0.0240 (13)	0.0255 (12)	0.0285 (14)	0.0041 (9)	0.0020 (11)	0.0030 (10)
C4	0.0313 (14)	0.0212 (11)	0.0271 (14)	0.0010 (10)	0.0049 (11)	0.0015 (9)
C5	0.0263 (14)	0.0259 (12)	0.0231 (13)	−0.0046 (9)	0.0059 (11)	−0.0019 (9)
C6	0.0177 (12)	0.0288 (12)	0.0187 (12)	0.0019 (9)	0.0039 (10)	0.0005 (9)
C7	0.0227 (13)	0.0240 (12)	0.0196 (12)	0.0042 (9)	0.0045 (10)	0.0007 (9)
C8	0.0264 (14)	0.0255 (12)	0.0276 (14)	0.0070 (10)	0.0046 (11)	0.0036 (10)
C9	0.0274 (14)	0.0244 (12)	0.0244 (13)	0.0000 (9)	0.0080 (11)	0.0007 (9)
C10	0.0264 (14)	0.0279 (12)	0.0268 (14)	−0.0028 (10)	−0.0006 (11)	0.0007 (10)
C11	0.0180 (12)	0.0245 (12)	0.0290 (14)	−0.0007 (9)	−0.0023 (10)	0.0032 (9)
C12	0.0284 (8)	0.0372 (8)	0.0476 (10)	0.0021 (6)	0.0006 (7)	−0.0009 (6)
S1A	0.0284 (8)	0.0372 (8)	0.0476 (10)	0.0021 (6)	0.0006 (7)	−0.0009 (6)
C13	0.0185 (15)	0.058 (2)	0.060 (2)	−0.0021 (12)	0.0017 (14)	0.0294 (16)
C14	0.0324 (16)	0.0531 (18)	0.0287 (16)	0.0180 (13)	0.0023 (13)	0.0023 (12)
N1	0.0252 (11)	0.0203 (9)	0.0193 (10)	0.0035 (8)	0.0053 (8)	0.0014 (7)
N2	0.0249 (11)	0.0198 (10)	0.0249 (11)	0.0045 (8)	0.0049 (9)	0.0016 (8)
O1	0.0355 (12)	0.0219 (9)	0.0453 (12)	−0.0006 (7)	0.0115 (9)	0.0001 (8)
Cl1	0.0200 (3)	0.0360 (3)	0.0346 (4)	0.0024 (2)	−0.0017 (3)	−0.0010 (3)
S1	0.0278 (5)	0.0300 (5)	0.0302 (5)	0.0010 (3)	0.0021 (4)	−0.0037 (3)
C12A	0.0278 (5)	0.0300 (5)	0.0302 (5)	0.0010 (3)	0.0021 (4)	−0.0037 (3)

Geometric parameters (Å, º) top

C1—C6	1.399 (3)	C9—N2	1.378 (3)
C1—C2	1.399 (3)	C9—C10	1.520 (4)
C1—C7	1.469 (3)	C10—C11	1.499 (4)
C2—C3	1.383 (3)	C10—H10A	0.9900
C2—H2	0.9500	C10—H10B	0.9900
C3—C4	1.391 (4)	C11—S1A	1.586 (3)
C3—H3	0.9500	C11—C12	1.586 (3)
C4—C5	1.383 (4)	C11—C12A	1.648 (3)
C4—H4	0.9500	C11—S1	1.648 (3)
C5—C6	1.388 (3)	C12—C13	1.483 (4)
C5—H5	0.9500	C12—H12	0.9500
C6—Cl1	1.748 (3)	S1A—C13	1.483 (4)
C7—N1	1.283 (3)	C13—C14	1.345 (5)
C7—H7	0.9500	C13—H13	0.9500
C8—N2	1.457 (3)	C14—C12A	1.642 (3)
C8—H8A	0.9800	C14—S1	1.642 (3)
C8—H8B	0.9800	C14—H14	0.9500
C8—H8C	0.9800	N1—N2	1.372 (3)
C9—O1	1.219 (3)	C12A—H12A	0.9500

C6—C1—C2	117.0 (2)	C11—C10—H10A	109.9
C6—C1—C7	122.3 (2)	C9—C10—H10A	109.9
C2—C1—C7	120.7 (2)	C11—C10—H10B	109.9
C3—C2—C1	121.6 (2)	C9—C10—H10B	109.9
C3—C2—H2	119.2	H10A—C10—H10B	108.3
C1—C2—H2	119.2	C10—C11—S1A	124.4 (2)
C2—C3—C4	119.9 (2)	C10—C11—C12	124.4 (2)
C2—C3—H3	120.0	C10—C11—C12A	123.04 (19)
C4—C3—H3	120.0	S1A—C11—C12A	112.59 (17)
C5—C4—C3	120.1 (2)	C10—C11—S1	123.04 (19)
C5—C4—H4	119.9	C12—C11—S1	112.59 (17)
C3—C4—H4	119.9	C13—C12—C11	101.16 (18)
C4—C5—C6	119.2 (2)	C13—C12—H12	129.4
C4—C5—H5	120.4	C11—C12—H12	129.4
C6—C5—H5	120.4	C13—S1A—C11	101.16 (18)
C5—C6—C1	122.2 (2)	C14—C13—C12	117.1 (3)
C5—C6—Cl1	117.13 (19)	C14—C13—S1A	117.1 (3)
C1—C6—Cl1	120.61 (18)	C14—C13—H13	121.4
N1—C7—C1	118.5 (2)	C12—C13—H13	121.4
N1—C7—H7	120.7	C13—C14—C12A	113.8 (2)
C1—C7—H7	120.7	C13—C14—S1	113.8 (2)
N2—C8—H8A	109.5	C13—C14—H14	123.1
N2—C8—H8B	109.5	S1—C14—H14	123.1
H8A—C8—H8B	109.5	C7—N1—N2	118.3 (2)
N2—C8—H8C	109.5	N1—N2—C9	117.8 (2)
H8A—C8—H8C	109.5	N1—N2—C8	121.8 (2)
H8B—C8—H8C	109.5	C9—N2—C8	120.4 (2)
O1—C9—N2	120.8 (2)	C14—S1—C11	95.27 (15)
O1—C9—C10	121.1 (2)	C14—C12A—C11	95.27 (15)
N2—C9—C10	118.0 (2)	C14—C12A—H12A	132.4
C11—C10—C9	108.8 (2)	C11—C12A—H12A	132.4

C6—C1—C2—C3	−0.3 (4)	S1—C11—C12—C13	−2.6 (2)
C7—C1—C2—C3	179.6 (2)	C10—C11—S1A—C13	176.2 (2)
C1—C2—C3—C4	0.0 (4)	C12A—C11—S1A—C13	−2.6 (2)
C2—C3—C4—C5	0.8 (4)	C11—C12—C13—C14	2.0 (3)
C3—C4—C5—C6	−1.2 (4)	C11—S1A—C13—C14	2.0 (3)
C4—C5—C6—C1	1.0 (4)	S1A—C13—C14—C12A	−0.6 (3)
C4—C5—C6—Cl1	−177.7 (2)	C12—C13—C14—S1	−0.6 (3)
C2—C1—C6—C5	−0.2 (4)	C1—C7—N1—N2	179.5 (2)
C7—C1—C6—C5	179.9 (2)	C7—N1—N2—C9	−179.2 (2)
C2—C1—C6—Cl1	178.47 (18)	C7—N1—N2—C8	2.1 (3)
C7—C1—C6—Cl1	−1.5 (3)	O1—C9—N2—N1	178.6 (2)
C6—C1—C7—N1	179.4 (2)	C10—C9—N2—N1	−4.2 (3)
C2—C1—C7—N1	−0.5 (4)	O1—C9—N2—C8	−2.7 (4)
O1—C9—C10—C11	87.0 (3)	C10—C9—N2—C8	174.4 (2)
N2—C9—C10—C11	−90.1 (3)	C13—C14—S1—C11	−1.0 (3)
C9—C10—C11—S1A	−70.0 (3)	C10—C11—S1—C14	−176.6 (2)
C9—C10—C11—C12	−70.0 (3)	C12—C11—S1—C14	2.24 (19)
C9—C10—C11—C12A	108.7 (2)	C13—C14—C12A—C11	−1.0 (3)
C9—C10—C11—S1	108.7 (2)	C10—C11—C12A—C14	−176.6 (2)
C10—C11—C12—C13	176.2 (2)	S1A—C11—C12A—C14	2.24 (19)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the thiophene ring, Cg2 is the centroid of the benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O1ⁱ	0.95	2.54	3.410 (4)	153
C3—H3···Cg1ⁱⁱ	0.95	2.83	3.612 (3)	140
C8—H8A···Cg2ⁱⁱⁱ	0.98	2.71	3.544 (3)	144

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

(II) top

Crystal data top

C₁₄H₁₃BrN₂OS	F(000) = 680
M_r = 337.23	D_x = 1.628 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.4479 (7) Å	Cell parameters from 14004 reflections
b = 20.2175 (14) Å	θ = 2.4–27.5°
c = 7.2552 (5) Å	µ = 3.13 mm⁻¹
β = 96.9343 (13)°	T = 100 K
V = 1375.70 (17) Å³	Rod, light brown
Z = 4	0.26 × 0.06 × 0.05 mm

Data collection top

Rigaku Mercury CCD diffractometer	2897 reflections with I > 2σ(I)
ω scans	R_int = 0.040
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 27.5°, θ_min = 2.4°
T_min = 0.756, T_max = 1.000	h = −12→11
14778 measured reflections	k = −26→26
3163 independent reflections	l = −8→9

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.025	H-atom parameters constrained
wR(F²) = 0.064	w = 1/[σ²(F_o²) + (0.029P)² + 0.8865P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
3163 reflections	Δρ_max = 0.48 e Å⁻³
174 parameters	Δρ_min = −0.43 e Å⁻³
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.09809 (17)	0.30257 (8)	0.1963 (2)	0.0165 (3)
C2	0.22907 (18)	0.32858 (8)	0.2763 (2)	0.0187 (3)
H2	0.3031	0.2991	0.3235	0.022*
C3	0.25292 (18)	0.39601 (9)	0.2878 (2)	0.0206 (3)
H3	0.3425	0.4124	0.3426	0.025*
C4	0.14614 (19)	0.43993 (8)	0.2194 (2)	0.0207 (3)
H4	0.1633	0.4862	0.2257	0.025*
C5	0.01471 (18)	0.41630 (8)	0.1420 (2)	0.0193 (3)
H5	−0.0594	0.4461	0.0973	0.023*
C6	−0.00727 (17)	0.34818 (9)	0.1306 (2)	0.0173 (3)
C7	0.07642 (17)	0.23064 (8)	0.1846 (2)	0.0171 (3)
H7	−0.0121	0.2128	0.1309	0.020*
C8	0.02550 (18)	0.09658 (9)	0.1503 (3)	0.0208 (3)
H8A	0.0048	0.1134	0.0232	0.031*
H8B	−0.0523	0.1087	0.2217	0.031*
H8C	0.0345	0.0483	0.1475	0.031*
C9	0.26952 (19)	0.08518 (9)	0.3080 (2)	0.0203 (3)
C10	0.41014 (18)	0.11767 (9)	0.3834 (3)	0.0218 (4)
H10A	0.3923	0.1624	0.4309	0.026*
H10B	0.4585	0.0911	0.4870	0.026*
C11	0.50282 (17)	0.12232 (8)	0.2296 (3)	0.0199 (3)
C12	0.57818 (11)	0.06159 (5)	0.14775 (16)	0.0320 (3)	0.677 (3)
H12	0.5796	0.0166	0.1856	0.038*	0.677 (3)
S1A	0.57818 (11)	0.06159 (5)	0.14775 (16)	0.0320 (3)	0.323 (3)
C13	0.6464 (2)	0.09279 (12)	−0.0038 (3)	0.0368 (5)
H13	0.6988	0.0675	−0.0828	0.044*
C14	0.6306 (2)	0.15886 (11)	−0.0243 (3)	0.0316 (4)
H14	0.6708	0.1834	−0.1168	0.038*
N1	0.17897 (15)	0.19243 (7)	0.2481 (2)	0.0171 (3)
N2	0.15849 (15)	0.12529 (7)	0.2374 (2)	0.0177 (3)
O1	0.25756 (14)	0.02499 (6)	0.3042 (2)	0.0272 (3)
S1	0.53516 (6)	0.19288 (3)	0.12608 (9)	0.02306 (19)	0.677 (3)
C12A	0.53516 (6)	0.19288 (3)	0.12608 (9)	0.02306 (19)	0.323 (3)
H12A	0.5082	0.2373	0.1464	0.028*	0.323 (3)
Br1	−0.18904 (2)	0.31960 (2)	0.01542 (3)	0.02297 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0183 (8)	0.0179 (8)	0.0135 (8)	−0.0010 (6)	0.0025 (6)	−0.0001 (6)
C2	0.0183 (8)	0.0192 (8)	0.0179 (8)	0.0008 (6)	−0.0001 (6)	0.0008 (6)
C3	0.0201 (8)	0.0207 (8)	0.0206 (9)	−0.0030 (6)	0.0012 (7)	−0.0018 (6)
C4	0.0256 (8)	0.0163 (8)	0.0207 (9)	−0.0019 (6)	0.0050 (7)	−0.0011 (6)
C5	0.0213 (8)	0.0189 (8)	0.0181 (9)	0.0042 (6)	0.0043 (6)	0.0018 (6)
C6	0.0164 (7)	0.0215 (8)	0.0140 (8)	−0.0010 (6)	0.0019 (6)	0.0004 (6)
C7	0.0185 (7)	0.0183 (8)	0.0145 (8)	−0.0031 (6)	0.0021 (6)	−0.0008 (6)
C8	0.0203 (8)	0.0184 (8)	0.0239 (9)	−0.0048 (6)	0.0038 (7)	−0.0028 (7)
C9	0.0236 (8)	0.0192 (8)	0.0191 (9)	0.0005 (7)	0.0074 (7)	−0.0006 (6)
C10	0.0219 (8)	0.0211 (8)	0.0219 (9)	0.0030 (7)	0.0002 (7)	−0.0001 (7)
C11	0.0150 (7)	0.0200 (8)	0.0236 (9)	0.0010 (6)	−0.0020 (6)	−0.0026 (7)
C12	0.0259 (5)	0.0317 (6)	0.0370 (6)	−0.0031 (4)	−0.0013 (4)	0.0004 (4)
S1A	0.0259 (5)	0.0317 (6)	0.0370 (6)	−0.0031 (4)	−0.0013 (4)	0.0004 (4)
C13	0.0170 (8)	0.0462 (13)	0.0465 (14)	0.0014 (8)	0.0012 (8)	−0.0239 (10)
C14	0.0305 (10)	0.0408 (12)	0.0240 (10)	−0.0174 (9)	0.0047 (8)	−0.0038 (8)
N1	0.0208 (7)	0.0141 (7)	0.0168 (7)	−0.0024 (5)	0.0043 (6)	−0.0013 (5)
N2	0.0196 (7)	0.0132 (6)	0.0205 (7)	−0.0027 (5)	0.0036 (6)	−0.0017 (5)
O1	0.0291 (7)	0.0167 (6)	0.0371 (8)	0.0010 (5)	0.0099 (6)	0.0005 (5)
S1	0.0217 (3)	0.0234 (3)	0.0237 (3)	−0.0004 (2)	0.0013 (2)	0.0023 (2)
C12A	0.0217 (3)	0.0234 (3)	0.0237 (3)	−0.0004 (2)	0.0013 (2)	0.0023 (2)
Br1	0.01578 (10)	0.02638 (11)	0.02587 (12)	−0.00184 (6)	−0.00109 (7)	0.00178 (7)

Geometric parameters (Å, º) top

C1—C6	1.398 (2)	C9—N2	1.375 (2)
C1—C2	1.404 (2)	C9—C10	1.523 (2)
C1—C7	1.470 (2)	C10—C11	1.502 (2)
C2—C3	1.383 (2)	C10—H10A	0.9900
C2—H2	0.9500	C10—H10B	0.9900
C3—C4	1.390 (2)	C11—S1A	1.571 (2)
C3—H3	0.9500	C11—C12	1.571 (2)
C4—C5	1.385 (2)	C11—C12A	1.6576 (19)
C4—H4	0.9500	C11—S1	1.6576 (19)
C5—C6	1.394 (2)	C12—C13	1.481 (3)
C5—H5	0.9500	C12—H12	0.9500
C6—Br1	1.9064 (16)	S1A—C13	1.481 (3)
C7—N1	1.281 (2)	C13—C14	1.350 (3)
C7—H7	0.9500	C13—H13	0.9500
C8—N2	1.457 (2)	C14—C12A	1.648 (2)
C8—H8A	0.9800	C14—S1	1.648 (2)
C8—H8B	0.9800	C14—H14	0.9500
C8—H8C	0.9800	N1—N2	1.3720 (19)
C9—O1	1.222 (2)	C12A—H12A	0.9500

C6—C1—C2	116.73 (15)	C11—C10—H10A	109.9
C6—C1—C7	122.98 (15)	C9—C10—H10A	109.9
C2—C1—C7	120.28 (15)	C11—C10—H10B	109.9
C3—C2—C1	121.56 (16)	C9—C10—H10B	109.9
C3—C2—H2	119.2	H10A—C10—H10B	108.3
C1—C2—H2	119.2	C10—C11—S1A	124.27 (14)
C2—C3—C4	120.15 (16)	C10—C11—C12	124.27 (14)
C2—C3—H3	119.9	C10—C11—C12A	123.11 (13)
C4—C3—H3	119.9	S1A—C11—C12A	112.62 (12)
C5—C4—C3	120.09 (16)	C10—C11—S1	123.11 (13)
C5—C4—H4	120.0	C12—C11—S1	112.62 (12)
C3—C4—H4	120.0	C13—C12—C11	101.85 (12)
C4—C5—C6	119.01 (15)	C13—C12—H12	129.1
C4—C5—H5	120.5	C11—C12—H12	129.1
C6—C5—H5	120.5	C13—S1A—C11	101.85 (12)
C5—C6—C1	122.46 (15)	C14—C13—C12	116.81 (17)
C5—C6—Br1	116.44 (12)	C14—C13—S1A	116.81 (17)
C1—C6—Br1	121.09 (13)	C14—C13—H13	121.6
N1—C7—C1	118.82 (15)	C12—C13—H13	121.6
N1—C7—H7	120.6	C13—C14—C12A	113.69 (17)
C1—C7—H7	120.6	C13—C14—S1	113.69 (17)
N2—C8—H8A	109.5	C13—C14—H14	123.2
N2—C8—H8B	109.5	S1—C14—H14	123.2
H8A—C8—H8B	109.5	C7—N1—N2	118.76 (14)
N2—C8—H8C	109.5	N1—N2—C9	117.80 (14)
H8A—C8—H8C	109.5	N1—N2—C8	121.80 (14)
H8B—C8—H8C	109.5	C9—N2—C8	120.38 (14)
O1—C9—N2	120.96 (16)	C14—S1—C11	94.95 (10)
O1—C9—C10	120.78 (16)	C14—C12A—C11	94.95 (10)
N2—C9—C10	118.20 (15)	C14—C12A—H12A	132.5
C11—C10—C9	108.77 (14)	C11—C12A—H12A	132.5

C6—C1—C2—C3	−0.5 (3)	S1—C11—C12—C13	−2.72 (14)
C7—C1—C2—C3	179.45 (16)	C10—C11—S1A—C13	176.72 (15)
C1—C2—C3—C4	0.0 (3)	C12A—C11—S1A—C13	−2.72 (14)
C2—C3—C4—C5	1.0 (3)	C11—C12—C13—C14	1.9 (2)
C3—C4—C5—C6	−1.3 (3)	C11—S1A—C13—C14	1.9 (2)
C4—C5—C6—C1	0.7 (3)	S1A—C13—C14—C12A	−0.4 (2)
C4—C5—C6—Br1	−178.15 (13)	C12—C13—C14—S1	−0.4 (2)
C2—C1—C6—C5	0.2 (2)	C1—C7—N1—N2	179.85 (14)
C7—C1—C6—C5	−179.79 (16)	C7—N1—N2—C9	−179.36 (15)
C2—C1—C6—Br1	179.02 (12)	C7—N1—N2—C8	2.2 (2)
C7—C1—C6—Br1	−1.0 (2)	O1—C9—N2—N1	179.36 (16)
C6—C1—C7—N1	179.85 (16)	C10—C9—N2—N1	−3.3 (2)
C2—C1—C7—N1	−0.1 (2)	O1—C9—N2—C8	−2.2 (2)
O1—C9—C10—C11	85.9 (2)	C10—C9—N2—C8	175.12 (15)
N2—C9—C10—C11	−91.44 (18)	C13—C14—S1—C11	−1.24 (17)
C9—C10—C11—S1A	−72.27 (19)	C10—C11—S1—C14	−177.05 (15)
C9—C10—C11—C12	−72.27 (19)	C12—C11—S1—C14	2.39 (13)
C9—C10—C11—C12A	107.11 (16)	C13—C14—C12A—C11	−1.24 (17)
C9—C10—C11—S1	107.11 (16)	C10—C11—C12A—C14	−177.05 (15)
C10—C11—C12—C13	176.72 (15)	S1A—C11—C12A—C14	2.39 (13)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the thiophene ring, Cg2 is the centroid of the benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O1ⁱ	0.95	2.53	3.424 (2)	156
C3—H3···Cg1ⁱⁱ	0.95	2.82	3.6021 (18)	141
C8—H8A···Cg2ⁱⁱⁱ	0.98	2.67	3.495 (2)	142

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

(III) top

Crystal data top

C₁₄H₁₃ClN₂OS	F(000) = 608
M_r = 292.77	D_x = 1.415 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71075 Å
a = 4.2194 (2) Å	Cell parameters from 9584 reflections
b = 13.0131 (9) Å	θ = 2.9–27.5°
c = 25.0758 (18) Å	µ = 0.42 mm⁻¹
β = 93.752 (4)°	T = 100 K
V = 1373.90 (15) Å³	Needle, colourless
Z = 4	0.22 × 0.01 × 0.01 mm

Data collection top

Rigaku Mercury CCD diffractometer	1766 reflections with I > 2σ(I)
ω scans	R_int = 0.127
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 27.4°, θ_min = 2.9°
T_min = 0.615, T_max = 1.000	h = −5→5
12868 measured reflections	k = −16→16
3121 independent reflections	l = −32→32

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.116	H-atom parameters constrained
wR(F²) = 0.297	w = 1/[σ²(F_o²) + (0.0832P)² + 8.0037P] where P = (F_o² + 2F_c²)/3
S = 1.16	(Δ/σ)_max = 0.006
3121 reflections	Δρ_max = 1.00 e Å⁻³
184 parameters	Δρ_min = −0.45 e Å⁻³
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.2176 (17)	0.2480 (6)	0.1409 (2)	0.0278 (15)
C2	0.0167 (16)	0.2955 (6)	0.1012 (3)	0.0281 (15)
H2	−0.0133	0.3679	0.1017	0.034*
C3	−0.1373 (17)	0.2366 (6)	0.0613 (3)	0.0339 (18)
H3	−0.2716	0.2690	0.0344	0.041*
C4	−0.0966 (18)	0.1304 (6)	0.0603 (3)	0.0352 (17)
H4	−0.2041	0.0901	0.0332	0.042*	0.854 (7)
C5	0.098 (2)	0.0838 (6)	0.0994 (3)	0.0383 (18)
H5	0.1284	0.0115	0.0987	0.046*	0.146 (7)
C6	0.2538 (18)	0.1414 (6)	0.1398 (3)	0.0322 (17)
H6	0.3852	0.1082	0.1668	0.039*
C7	0.3910 (16)	0.3074 (5)	0.1837 (3)	0.0258 (15)
H7	0.5213	0.2733	0.2105	0.031*
C8	0.7209 (18)	0.4074 (6)	0.2680 (3)	0.0335 (17)
H8A	0.5903	0.3557	0.2847	0.050*
H8B	0.7949	0.4582	0.2949	0.050*
H8C	0.9042	0.3739	0.2534	0.050*
C9	0.5187 (17)	0.5634 (6)	0.2228 (3)	0.0307 (17)
C10	0.3000 (17)	0.6118 (6)	0.1778 (3)	0.0324 (17)
H10A	0.1189	0.5651	0.1691	0.039*
H10B	0.2137	0.6774	0.1907	0.039*
C11	0.4715 (15)	0.6322 (5)	0.1277 (2)	0.0245 (14)
C12	0.5901 (13)	0.7328 (5)	0.11266 (19)	0.048 (2)	0.795 (9)
H12	0.5807	0.7956	0.1319	0.058*	0.795 (9)
S1A	0.5901 (13)	0.7328 (5)	0.11266 (19)	0.048 (2)	0.205 (9)
C13	0.7313 (18)	0.7147 (6)	0.0596 (3)	0.0353 (17)
H13	0.8266	0.7681	0.0404	0.042*
C14	0.7127 (17)	0.6182 (6)	0.0416 (3)	0.0342 (17)
H14	0.7921	0.5975	0.0087	0.041*
N1	0.3638 (13)	0.4055 (4)	0.1843 (2)	0.0250 (13)
N2	0.5314 (14)	0.4588 (5)	0.2249 (2)	0.0302 (13)
O1	0.6759 (12)	0.6183 (4)	0.25450 (18)	0.0362 (13)
Cl1	0.1534 (7)	−0.04694 (19)	0.09763 (10)	0.0537 (9)	0.854 (7)
Cl2	−0.296 (5)	0.0407 (14)	0.0203 (7)	0.067 (7)	0.146 (7)
S1	0.5363 (5)	0.53654 (16)	0.08241 (8)	0.0261 (7)	0.795 (9)
C12A	0.5363 (5)	0.53654 (16)	0.08241 (8)	0.0261 (7)	0.205 (9)
H12A	0.4903	0.4651	0.0810	0.031*	0.205 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.035 (4)	0.031 (4)	0.018 (3)	0.001 (3)	0.007 (3)	0.000 (3)
C2	0.026 (4)	0.026 (4)	0.033 (4)	0.000 (3)	0.008 (3)	0.001 (3)
C3	0.025 (4)	0.053 (5)	0.024 (3)	−0.002 (3)	0.001 (3)	0.000 (3)
C4	0.032 (4)	0.035 (4)	0.038 (4)	−0.006 (3)	−0.001 (3)	−0.010 (4)
C5	0.046 (5)	0.030 (4)	0.039 (4)	−0.002 (4)	0.001 (3)	−0.007 (3)
C6	0.042 (4)	0.028 (4)	0.027 (3)	0.000 (3)	0.003 (3)	0.001 (3)
C7	0.027 (4)	0.029 (4)	0.022 (3)	0.003 (3)	0.002 (3)	0.001 (3)
C8	0.041 (4)	0.035 (4)	0.024 (3)	−0.008 (3)	−0.003 (3)	0.004 (3)
C9	0.029 (4)	0.045 (5)	0.019 (3)	−0.004 (3)	0.007 (3)	−0.005 (3)
C10	0.030 (4)	0.035 (4)	0.032 (4)	0.004 (3)	0.002 (3)	−0.008 (3)
C11	0.024 (3)	0.025 (4)	0.024 (3)	0.005 (3)	−0.004 (3)	−0.001 (3)
C12	0.051 (4)	0.063 (4)	0.029 (3)	−0.004 (3)	−0.008 (2)	0.013 (2)
S1A	0.051 (4)	0.063 (4)	0.029 (3)	−0.004 (3)	−0.008 (2)	0.013 (2)
C13	0.041 (4)	0.035 (4)	0.029 (4)	−0.003 (4)	−0.007 (3)	0.008 (3)
C14	0.032 (4)	0.045 (5)	0.024 (3)	−0.001 (3)	−0.007 (3)	0.004 (3)
N1	0.030 (3)	0.028 (3)	0.017 (2)	−0.001 (2)	0.001 (2)	−0.005 (2)
N2	0.035 (3)	0.034 (3)	0.020 (3)	−0.001 (3)	−0.003 (2)	−0.004 (3)
O1	0.047 (3)	0.042 (3)	0.020 (2)	−0.005 (3)	0.003 (2)	−0.008 (2)
Cl1	0.085 (2)	0.0220 (12)	0.0519 (15)	−0.0009 (12)	−0.0112 (13)	−0.0015 (11)
Cl2	0.086 (13)	0.059 (11)	0.059 (10)	−0.023 (9)	0.028 (9)	−0.035 (9)
S1	0.0310 (12)	0.0240 (11)	0.0228 (10)	0.0019 (9)	−0.0021 (7)	−0.0015 (8)
C12A	0.0310 (12)	0.0240 (11)	0.0228 (10)	0.0019 (9)	−0.0021 (7)	−0.0015 (8)

Geometric parameters (Å, º) top

C1—C6	1.395 (10)	C9—C10	1.545 (10)
C1—C2	1.408 (10)	C10—C11	1.514 (9)
C1—C7	1.478 (10)	C10—H10A	0.9900
C2—C3	1.388 (10)	C10—H10B	0.9900
C2—H2	0.9500	C11—S1A	1.461 (9)
C3—C4	1.394 (11)	C11—C12	1.461 (9)
C3—H3	0.9500	C11—C12A	1.718 (7)
C4—C5	1.377 (11)	C11—S1	1.718 (7)
C4—Cl2	1.724 (17)	C12—C13	1.511 (9)
C4—H4	0.9500	C12—H12	0.9500
C5—C6	1.392 (10)	S1A—C13	1.511 (9)
C5—Cl1	1.718 (8)	C13—C14	1.334 (11)
C5—H5	0.9500	C13—H13	0.9500
C6—H6	0.9500	C14—C12A	1.682 (8)
C7—N1	1.281 (9)	C14—S1	1.682 (8)
C7—H7	0.9500	C14—H14	0.9500
C8—N2	1.464 (9)	N1—N2	1.387 (8)
C8—H8A	0.9800	Cl1—H5	0.7679
C8—H8B	0.9800	Cl2—Cl2ⁱ	2.21 (3)
C8—H8C	0.9800	Cl2—H4	0.8086
C9—O1	1.229 (8)	C12A—H12A	0.9500
C9—N2	1.364 (10)

C6—C1—C2	119.0 (7)	C11—C10—C9	112.5 (6)
C6—C1—C7	119.0 (7)	C11—C10—H10A	109.1
C2—C1—C7	122.0 (7)	C9—C10—H10A	109.1
C3—C2—C1	119.9 (7)	C11—C10—H10B	109.1
C3—C2—H2	120.0	C9—C10—H10B	109.1
C1—C2—H2	120.0	H10A—C10—H10B	107.8
C2—C3—C4	120.5 (7)	S1A—C11—C10	124.1 (6)
C2—C3—H3	119.7	C12—C11—C10	124.1 (6)
C4—C3—H3	119.7	S1A—C11—C12A	114.0 (5)
C5—C4—C3	119.5 (7)	C10—C11—C12A	121.8 (5)
C5—C4—Cl2	111.2 (9)	C12—C11—S1	114.0 (5)
C3—C4—Cl2	128.8 (10)	C10—C11—S1	121.8 (5)
C5—C4—H4	120.0	C11—C12—C13	104.4 (6)
C3—C4—H4	120.4	C11—C12—H12	127.8
Cl2—C4—H4	10.5	C13—C12—H12	127.8
C4—C5—C6	120.8 (7)	C11—S1A—C13	104.4 (6)
C4—C5—Cl1	119.6 (6)	C14—C13—C12	115.3 (7)
C6—C5—Cl1	119.6 (6)	C14—C13—S1A	115.3 (7)
C4—C5—H5	120.0	C14—C13—H13	122.4
C6—C5—H5	119.2	C12—C13—H13	122.4
Cl1—C5—H5	0.5	C13—C14—C12A	114.1 (6)
C5—C6—C1	120.2 (7)	C13—C14—S1	114.1 (6)
C5—C6—H6	119.9	C13—C14—H14	123.0
C1—C6—H6	119.9	S1—C14—H14	123.0
N1—C7—C1	119.3 (6)	C7—N1—N2	117.7 (6)
N1—C7—H7	120.3	C9—N2—N1	117.0 (6)
C1—C7—H7	120.3	C9—N2—C8	120.2 (6)
N2—C8—H8A	109.5	N1—N2—C8	122.7 (6)
N2—C8—H8B	109.5	C5—Cl1—H5	0.6
H8A—C8—H8B	109.5	C4—Cl2—Cl2ⁱ	158.2 (15)
N2—C8—H8C	109.5	C4—Cl2—H4	12.4
H8A—C8—H8C	109.5	Cl2ⁱ—Cl2—H4	154.9
H8B—C8—H8C	109.5	C14—S1—C11	92.3 (4)
O1—C9—N2	122.5 (7)	C14—C12A—C11	92.3 (4)
O1—C9—C10	120.5 (7)	C14—C12A—H12A	133.9
N2—C9—C10	117.1 (6)	C11—C12A—H12A	133.9

C6—C1—C2—C3	−1.1 (10)	S1—C11—C12—C13	0.5 (6)
C7—C1—C2—C3	179.0 (6)	C10—C11—S1A—C13	−178.3 (6)
C1—C2—C3—C4	0.4 (10)	C12A—C11—S1A—C13	0.5 (6)
C2—C3—C4—C5	0.1 (11)	C11—C12—C13—C14	−0.1 (8)
C2—C3—C4—Cl2	171.4 (9)	C11—S1A—C13—C14	−0.1 (8)
C3—C4—C5—C6	0.1 (12)	S1A—C13—C14—C12A	−0.3 (8)
Cl2—C4—C5—C6	−172.7 (8)	C12—C13—C14—S1	−0.3 (8)
C3—C4—C5—Cl1	−179.0 (6)	C1—C7—N1—N2	−179.6 (6)
Cl2—C4—C5—Cl1	8.3 (10)	O1—C9—N2—N1	−174.7 (6)
C4—C5—C6—C1	−0.8 (11)	C10—C9—N2—N1	4.3 (9)
Cl1—C5—C6—C1	178.3 (6)	O1—C9—N2—C8	4.1 (10)
C2—C1—C6—C5	1.3 (10)	C10—C9—N2—C8	−176.9 (6)
C7—C1—C6—C5	−178.8 (7)	C7—N1—N2—C9	175.3 (6)
C6—C1—C7—N1	178.6 (6)	C7—N1—N2—C8	−3.5 (9)
C2—C1—C7—N1	−1.5 (10)	C5—C4—Cl2—Cl2ⁱ	123 (4)
O1—C9—C10—C11	88.1 (8)	C3—C4—Cl2—Cl2ⁱ	−49 (5)
N2—C9—C10—C11	−90.9 (8)	C13—C14—S1—C11	0.6 (6)
C9—C10—C11—S1A	−100.6 (8)	C12—C11—S1—C14	−0.6 (5)
C9—C10—C11—C12	−100.6 (8)	C10—C11—S1—C14	178.3 (6)
C9—C10—C11—C12A	80.6 (7)	C13—C14—C12A—C11	0.6 (6)
C9—C10—C11—S1	80.6 (7)	S1A—C11—C12A—C14	−0.6 (5)
C10—C11—C12—C13	−178.3 (6)	C10—C11—C12A—C14	178.3 (6)

Symmetry code: (i) −x−1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1ⁱⁱ	0.95	2.62	3.474 (9)	150
C7—H7···O1ⁱⁱ	0.95	2.52	3.381 (9)	152
C12—H12···Cl1ⁱⁱⁱ	0.95	2.83	3.415 (7)	121

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

(IV) top

Crystal data top

C₁₄H₁₃ClN₂OS	F(000) = 608
M_r = 292.77	D_x = 1.410 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.7454 (5) Å	Cell parameters from 14502 reflections
b = 20.2993 (14) Å	θ = 2.3–27.5°
c = 10.1592 (7) Å	µ = 0.42 mm⁻¹
β = 97.510 (2)°	T = 100 K
V = 1379.14 (17) Å³	Block, colourless
Z = 4	0.30 × 0.17 × 0.10 mm

Data collection top

Rigaku Mercury CCD diffractometer	2929 reflections with I > 2σ(I)
ω scans	R_int = 0.033
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 27.5°, θ_min = 2.9°
T_min = 0.843, T_max = 1.000	h = −7→8
14763 measured reflections	k = −25→26
3165 independent reflections	l = −12→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.091	w = 1/[σ²(F_o²) + (0.0494P)² + 0.4663P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
3165 reflections	Δρ_max = 0.53 e Å⁻³
174 parameters	Δρ_min = −0.40 e Å⁻³
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.30559 (18)	0.18484 (6)	0.17665 (11)	0.0232 (2)
C2	0.29278 (19)	0.11619 (6)	0.16729 (12)	0.0258 (3)
H2	0.4040	0.0899	0.2020	0.031*
C3	0.1195 (2)	0.08611 (6)	0.10784 (13)	0.0277 (3)
H3	0.1109	0.0395	0.1019	0.033*
C4	−0.04180 (18)	0.12533 (6)	0.05692 (12)	0.0251 (2)
C5	−0.03348 (19)	0.19335 (7)	0.06381 (12)	0.0266 (3)
H5	−0.1446	0.2194	0.0281	0.032*
C6	0.14082 (19)	0.22248 (6)	0.12410 (12)	0.0260 (3)
H6	0.1484	0.2691	0.1298	0.031*
C7	0.48613 (18)	0.21894 (6)	0.23753 (11)	0.0245 (2)
H7	0.4946	0.2655	0.2313	0.029*
C8	0.8228 (2)	0.29167 (6)	0.32415 (13)	0.0273 (3)
H8A	0.7962	0.2998	0.2284	0.041*
H8B	0.9595	0.3055	0.3571	0.041*
H8C	0.7279	0.3168	0.3695	0.041*
C9	0.94915 (18)	0.18717 (6)	0.42531 (11)	0.0236 (2)
C10	0.91435 (19)	0.11392 (6)	0.44594 (13)	0.0266 (3)
H10A	0.7816	0.1076	0.4756	0.032*
H10B	0.9145	0.0905	0.3605	0.032*
C11	1.0726 (2)	0.08513 (6)	0.54718 (13)	0.0259 (3)
C12	1.03317 (13)	0.06569 (4)	0.68966 (8)	0.0410 (3)	0.671 (2)
H12	0.9132	0.0677	0.7291	0.049*	0.671 (2)
S1A	1.03317 (13)	0.06569 (4)	0.68966 (8)	0.0410 (3)	0.329 (2)
C13	1.2424 (3)	0.04236 (7)	0.74842 (14)	0.0396 (3)
H13	1.2706	0.0278	0.8378	0.048*
C14	1.3836 (2)	0.04368 (7)	0.66669 (16)	0.0395 (3)
H14	1.5174	0.0298	0.6934	0.047*
N1	0.63255 (15)	0.18647 (5)	0.29910 (10)	0.0232 (2)
N2	0.80022 (16)	0.22142 (5)	0.35017 (10)	0.0236 (2)
O1	1.10231 (14)	0.21470 (5)	0.47402 (9)	0.0312 (2)
Cl1	−0.26110 (5)	0.08829 (2)	−0.01956 (3)	0.03259 (11)
S1	1.30619 (7)	0.07115 (3)	0.51710 (5)	0.03532 (17)	0.671 (2)
C12A	1.30619 (7)	0.07115 (3)	0.51710 (5)	0.03532 (17)	0.329 (2)
H12A	1.3712	0.0770	0.4405	0.042*	0.329 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0233 (6)	0.0282 (6)	0.0185 (5)	0.0020 (5)	0.0043 (4)	0.0013 (4)
C2	0.0234 (6)	0.0285 (6)	0.0252 (6)	0.0048 (5)	0.0019 (4)	0.0040 (5)
C3	0.0269 (6)	0.0266 (6)	0.0293 (6)	0.0026 (5)	0.0024 (5)	0.0024 (5)
C4	0.0214 (6)	0.0320 (6)	0.0220 (5)	0.0012 (5)	0.0031 (4)	0.0006 (5)
C5	0.0235 (6)	0.0321 (6)	0.0242 (6)	0.0077 (5)	0.0034 (5)	0.0020 (5)
C6	0.0273 (6)	0.0259 (6)	0.0253 (6)	0.0047 (5)	0.0054 (5)	0.0012 (4)
C7	0.0268 (6)	0.0260 (6)	0.0212 (5)	0.0016 (5)	0.0052 (4)	0.0000 (4)
C8	0.0329 (7)	0.0230 (6)	0.0257 (6)	−0.0020 (5)	0.0027 (5)	0.0011 (4)
C9	0.0260 (6)	0.0250 (6)	0.0196 (5)	−0.0025 (5)	0.0025 (4)	−0.0024 (4)
C10	0.0261 (6)	0.0239 (6)	0.0283 (6)	−0.0027 (5)	−0.0026 (5)	−0.0009 (5)
C11	0.0279 (6)	0.0225 (6)	0.0261 (6)	−0.0031 (5)	−0.0008 (5)	−0.0014 (4)
C12	0.0490 (5)	0.0350 (4)	0.0364 (4)	−0.0036 (3)	−0.0046 (3)	0.0007 (3)
S1A	0.0490 (5)	0.0350 (4)	0.0364 (4)	−0.0036 (3)	−0.0046 (3)	0.0007 (3)
C13	0.0586 (10)	0.0293 (7)	0.0281 (6)	−0.0053 (6)	−0.0050 (6)	0.0039 (5)
C14	0.0347 (7)	0.0341 (7)	0.0459 (8)	0.0038 (6)	−0.0088 (6)	−0.0062 (6)
N1	0.0231 (5)	0.0272 (5)	0.0191 (5)	−0.0023 (4)	0.0026 (4)	−0.0017 (4)
N2	0.0256 (5)	0.0227 (5)	0.0221 (5)	−0.0025 (4)	0.0019 (4)	−0.0009 (4)
O1	0.0304 (5)	0.0282 (5)	0.0325 (5)	−0.0069 (4)	−0.0050 (4)	−0.0004 (4)
Cl1	0.02389 (17)	0.03644 (19)	0.03586 (19)	0.00052 (12)	−0.00205 (12)	−0.00053 (12)
S1	0.0304 (3)	0.0429 (3)	0.0313 (3)	0.00544 (19)	−0.00098 (18)	0.00246 (18)
C12A	0.0304 (3)	0.0429 (3)	0.0313 (3)	0.00544 (19)	−0.00098 (18)	0.00246 (18)

Geometric parameters (Å, º) top

C1—C6	1.3961 (17)	C9—N2	1.3693 (16)
C1—C2	1.3987 (18)	C9—C10	1.5241 (17)
C1—C7	1.4656 (17)	C10—C11	1.5007 (17)
C2—C3	1.3851 (18)	C10—H10A	0.9900
C2—H2	0.9500	C10—H10B	0.9900
C3—C4	1.3922 (18)	C11—S1A	1.5564 (15)
C3—H3	0.9500	C11—C12	1.5564 (15)
C4—C5	1.3834 (19)	C11—C12A	1.6679 (14)
C4—Cl1	1.7484 (13)	C11—S1	1.6679 (14)
C5—C6	1.3852 (18)	C12—C13	1.5337 (19)
C5—H5	0.9500	C12—H12	0.9500
C6—H6	0.9500	S1A—C13	1.5337 (19)
C7—N1	1.2805 (16)	C13—C14	1.343 (2)
C7—H7	0.9500	C13—H13	0.9500
C8—N2	1.4619 (16)	C14—C12A	1.6388 (16)
C8—H8A	0.9800	C14—S1	1.6388 (16)
C8—H8B	0.9800	C14—H14	0.9500
C8—H8C	0.9800	N1—N2	1.3778 (14)
C9—O1	1.2210 (15)	C12A—H12A	0.9500

C6—C1—C2	118.70 (11)	C11—C10—H10A	109.3
C6—C1—C7	118.62 (11)	C9—C10—H10A	109.3
C2—C1—C7	122.67 (11)	C11—C10—H10B	109.3
C3—C2—C1	120.66 (11)	C9—C10—H10B	109.3
C3—C2—H2	119.7	H10A—C10—H10B	108.0
C1—C2—H2	119.7	C10—C11—S1A	122.91 (11)
C2—C3—C4	118.94 (12)	C10—C11—C12	122.91 (11)
C2—C3—H3	120.5	C10—C11—C12A	123.03 (10)
C4—C3—H3	120.5	S1A—C11—C12A	114.06 (9)
C5—C4—C3	121.82 (12)	C10—C11—S1	123.03 (10)
C5—C4—Cl1	118.56 (10)	C12—C11—S1	114.06 (9)
C3—C4—Cl1	119.61 (10)	C13—C12—C11	100.36 (9)
C4—C5—C6	118.35 (11)	C13—C12—H12	129.8
C4—C5—H5	120.8	C11—C12—H12	129.8
C6—C5—H5	120.8	C13—S1A—C11	100.36 (9)
C5—C6—C1	121.52 (12)	C14—C13—C12	116.37 (12)
C5—C6—H6	119.2	C14—C13—S1A	116.37 (12)
C1—C6—H6	119.2	C14—C13—H13	121.8
N1—C7—C1	120.55 (11)	C12—C13—H13	121.8
N1—C7—H7	119.7	C13—C14—C12A	114.47 (12)
C1—C7—H7	119.7	C13—C14—S1	114.47 (12)
N2—C8—H8A	109.5	C13—C14—H14	122.8
N2—C8—H8B	109.5	S1—C14—H14	122.8
H8A—C8—H8B	109.5	C7—N1—N2	117.49 (11)
N2—C8—H8C	109.5	C9—N2—N1	117.06 (10)
H8A—C8—H8C	109.5	C9—N2—C8	120.64 (10)
H8B—C8—H8C	109.5	N1—N2—C8	122.29 (10)
O1—C9—N2	120.92 (11)	C14—S1—C11	94.72 (8)
O1—C9—C10	121.88 (11)	C14—C12A—C11	94.72 (8)
N2—C9—C10	117.20 (10)	C14—C12A—H12A	132.6
C11—C10—C9	111.45 (10)	C11—C12A—H12A	132.6

C6—C1—C2—C3	−0.44 (18)	C10—C11—S1A—C13	−178.00 (11)
C7—C1—C2—C3	−179.43 (11)	C12A—C11—S1A—C13	1.98 (11)
C1—C2—C3—C4	0.27 (19)	C11—C12—C13—C14	−1.60 (14)
C2—C3—C4—C5	0.17 (19)	C11—S1A—C13—C14	−1.60 (14)
C2—C3—C4—Cl1	179.53 (9)	S1A—C13—C14—C12A	0.63 (17)
C3—C4—C5—C6	−0.41 (19)	C12—C13—C14—S1	0.63 (17)
Cl1—C4—C5—C6	−179.78 (9)	C1—C7—N1—N2	177.91 (10)
C4—C5—C6—C1	0.23 (18)	O1—C9—N2—N1	−179.97 (11)
C2—C1—C6—C5	0.18 (18)	C10—C9—N2—N1	−0.43 (15)
C7—C1—C6—C5	179.22 (11)	O1—C9—N2—C8	1.27 (18)
C6—C1—C7—N1	172.64 (11)	C10—C9—N2—C8	−179.20 (11)
C2—C1—C7—N1	−8.36 (17)	C7—N1—N2—C9	174.66 (10)
O1—C9—C10—C11	8.78 (17)	C7—N1—N2—C8	−6.59 (16)
N2—C9—C10—C11	−170.75 (11)	C13—C14—S1—C11	0.60 (13)
C9—C10—C11—S1A	106.71 (12)	C10—C11—S1—C14	178.36 (11)
C9—C10—C11—C12	106.71 (12)	C12—C11—S1—C14	−1.62 (10)
C9—C10—C11—C12A	−73.26 (14)	C13—C14—C12A—C11	0.60 (13)
C9—C10—C11—S1	−73.26 (14)	C10—C11—C12A—C14	178.36 (11)
C10—C11—C12—C13	−178.00 (11)	S1A—C11—C12A—C14	−1.62 (10)
S1—C11—C12—C13	1.98 (11)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1ⁱ	0.95	2.18	3.1250 (15)	172
C3—H3···Cl1ⁱⁱ	0.95	2.95	3.8044 (14)	151
C12—H12···Cl1ⁱⁱⁱ	0.95	2.98	3.7960 (10)	145
C8—H8C···Cg1^iv	0.98	2.73	3.5592 (14)	142

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

Hirshfeld contact interactions (%) top

Contact type	(I)	(II)	(III)	(IV)
H···H	43.6	43.0	38.5	41.5
C···H/H···C	21.3	20.8	18.1	23.5
Hal···H/H···Hal	12.5	13.0	15.2	16.0
O···H/H···O	9.4	9.6	9.7	7.1
C···C	2.5	2.4	4.7	1.6
N···H/H···N	1.4	1.3	3.9	3.3
S···H/H···S	1.9	1.8	2.9	2.0

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Different packing motifs of isomeric (E)-N′-(halo­phenyl­methyl­idene)-N-methyl-2-(thio­phen-2-yl)acetohydrazides controlled by C—HO inter­actions

Supporting information

Key indicators

checkCIF/PLATON results

Different packing motifs of isomeric (E)-N′-(halophenylmethylidene)-N-methyl-2-(thiophen-2-yl)acetohydrazides controlled by C—HO interactions