(E)-2-(2-Hy­droxy-3-methyl­benzyl­idene)-N-methyl­hydrazine-1-carbo­thio­amide: supra­molecular assemblies in two-dimensions mediated by N—H⋯S and C—H⋯π inter­actions

Arafath, M.A.; Kwong, H.C.; Adam, F.

doi:10.1107/S2056989019004444

(E)-2-(2-Hydroxy-3-methylbenzylidene)-N-methylhydrazine-1-carbothioamide: supramolecular assemblies in two-dimensions mediated by N—HS and C—Hπ interactions

The character of the methylhydrazine carbothioamide moiety in the title compound is a thiosemicarbazone Schiff base was confirmed by its bond lengths and bond angles. In the crystal, molecules of the title compound are mediated into sheets parallel to the ab plane by N—H

S hydrogen bonds and C—H

π interactions.

Keywords: crystal structure; hydrazine carbothioamide; Schiff base; intermolecular interaction.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989019004444/nr2074sup1.cif Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989019004444/nr2074Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989019004444/nr2074Isup3.cml Supplementary material

CCDC reference: 1485713

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.003 Å
R factor = 0.033
wR factor = 0.094
Data-to-parameter ratio = 22.4

checkCIF/PLATON results

No syntax errors found



Alert level G
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          3 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          3 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
   0 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   3 ALERT level G = General information/check it is not something unexpected

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

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: SHELXL2013 (Sheldrick, 2015) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2015) and PLATON (Spek, 2009).

(E)-2-(2-Hydroxy-3-methylbenzylidene)-N-methylhydrazine-1-carbothioamide top

Crystal data top

C₁₀H₁₃N₃OS	D_x = 1.298 Mg m⁻³
M_r = 223.29	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Iba2	Cell parameters from 5563 reflections
a = 14.6474 (14) Å	θ = 2.3–29.5°
b = 17.522 (2) Å	µ = 0.26 mm⁻¹
c = 8.9048 (8) Å	T = 296 K
V = 2285.4 (4) Å³	Block, yellow
Z = 8	0.46 × 0.26 × 0.16 mm
F(000) = 944

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	3359 independent reflections
Radiation source: fine-focus sealed tube	2949 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
φ and ω scans	θ_max = 30.1°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −20→20
T_min = 0.853, T_max = 0.879	k = −23→24
14825 measured reflections	l = −12→12

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.033	w = 1/[σ²(F_o²) + (0.0497P)² + 0.3888P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.094	(Δ/σ)_max = 0.001
S = 1.06	Δρ_max = 0.17 e Å⁻³
3359 reflections	Δρ_min = −0.15 e Å⁻³
150 parameters	Absolute structure: Flack parameter determined using 1222 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.04 (3)

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
S1	0.35594 (4)	0.50006 (3)	0.20442 (10)	0.05018 (16)
O1	0.45729 (12)	0.77741 (11)	0.6162 (3)	0.0621 (6)
N1	0.48391 (12)	0.65142 (9)	0.4511 (3)	0.0414 (4)
N2	0.46275 (13)	0.59332 (10)	0.3526 (2)	0.0436 (4)
N3	0.31035 (13)	0.60707 (11)	0.4029 (2)	0.0459 (4)
C1	0.69785 (15)	0.72085 (14)	0.6081 (2)	0.0443 (5)
H1A	0.735599	0.683585	0.567182	0.053*
C2	0.73506 (15)	0.77658 (13)	0.6987 (3)	0.0493 (5)
H2A	0.797160	0.776261	0.720393	0.059*
C3	0.67936 (16)	0.83287 (14)	0.7568 (3)	0.0492 (5)
H3A	0.704945	0.871242	0.815398	0.059*
C4	0.58596 (16)	0.83349 (12)	0.7297 (3)	0.0479 (5)
C5	0.54896 (14)	0.77591 (12)	0.6405 (3)	0.0424 (4)
C6	0.60427 (14)	0.71939 (12)	0.5768 (2)	0.0380 (4)
C7	0.5255 (2)	0.89533 (18)	0.7931 (5)	0.0783 (10)
H7A	0.491901	0.918970	0.713173	0.117*
H7B	0.562565	0.932944	0.842504	0.117*
H7C	0.483746	0.873420	0.864103	0.117*
C8	0.56962 (15)	0.65960 (11)	0.4793 (3)	0.0410 (4)
H8A	0.610876	0.625925	0.435625	0.049*
C9	0.37548 (14)	0.57095 (11)	0.3289 (2)	0.0397 (4)
C10	0.21430 (16)	0.58990 (19)	0.3892 (4)	0.0647 (7)
H10A	0.179253	0.629791	0.435460	0.097*
H10B	0.201496	0.542285	0.438227	0.097*
H10C	0.198298	0.586205	0.284940	0.097*
H1N2	0.5065 (18)	0.5680 (16)	0.307 (4)	0.056 (8)*
H1N3	0.3243 (19)	0.6428 (16)	0.471 (4)	0.054 (7)*
H1O1	0.444 (3)	0.7429 (19)	0.555 (5)	0.076 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0523 (3)	0.0455 (3)	0.0527 (3)	−0.0030 (2)	−0.0095 (3)	−0.0097 (2)
O1	0.0328 (8)	0.0601 (11)	0.0936 (16)	−0.0015 (7)	−0.0014 (8)	−0.0230 (10)
N1	0.0439 (9)	0.0367 (7)	0.0436 (8)	−0.0042 (6)	−0.0024 (9)	0.0006 (9)
N2	0.0412 (9)	0.0404 (9)	0.0491 (10)	0.0001 (7)	−0.0030 (8)	−0.0060 (8)
N3	0.0409 (9)	0.0495 (10)	0.0475 (9)	0.0000 (8)	−0.0055 (7)	−0.0078 (8)
C1	0.0380 (10)	0.0490 (12)	0.0460 (11)	0.0012 (9)	0.0008 (9)	0.0009 (9)
C2	0.0379 (9)	0.0576 (12)	0.0525 (11)	−0.0059 (9)	−0.0058 (10)	0.0016 (12)
C3	0.0478 (12)	0.0485 (11)	0.0513 (11)	−0.0119 (10)	−0.0057 (10)	−0.0017 (9)
C4	0.0446 (11)	0.0416 (10)	0.0575 (15)	−0.0049 (9)	0.0020 (9)	−0.0064 (9)
C5	0.0327 (10)	0.0401 (10)	0.0544 (12)	−0.0048 (8)	0.0031 (8)	0.0002 (9)
C6	0.0357 (9)	0.0380 (10)	0.0401 (10)	−0.0037 (8)	0.0010 (8)	0.0033 (8)
C7	0.0642 (17)	0.0641 (17)	0.107 (3)	0.0081 (14)	−0.0021 (18)	−0.0325 (17)
C8	0.0413 (10)	0.0387 (9)	0.0428 (11)	−0.0008 (8)	−0.0006 (8)	0.0020 (8)
C9	0.0439 (10)	0.0365 (9)	0.0387 (9)	−0.0016 (8)	−0.0064 (8)	0.0033 (8)
C10	0.0403 (12)	0.0802 (18)	0.0736 (17)	−0.0043 (12)	−0.0015 (12)	−0.0148 (15)

Geometric parameters (Å, º) top

S1—C9	1.689 (2)	C2—H2A	0.9300
O1—C5	1.360 (3)	C3—C4	1.389 (3)
O1—H1O1	0.84 (4)	C3—H3A	0.9300
N1—C8	1.288 (3)	C4—C5	1.393 (3)
N1—N2	1.379 (3)	C4—C7	1.509 (4)
N2—C9	1.354 (3)	C5—C6	1.400 (3)
N2—H1N2	0.88 (3)	C6—C8	1.452 (3)
N3—C9	1.321 (3)	C7—H7A	0.9600
N3—C10	1.444 (3)	C7—H7B	0.9600
N3—H1N3	0.90 (3)	C7—H7C	0.9600
C1—C2	1.379 (3)	C8—H8A	0.9300
C1—C6	1.399 (3)	C10—H10A	0.9600
C1—H1A	0.9300	C10—H10B	0.9600
C2—C3	1.381 (4)	C10—H10C	0.9600

C5—O1—H1O1	108 (3)	C4—C5—C6	121.21 (19)
C8—N1—N2	115.18 (18)	C1—C6—C5	118.25 (19)
C9—N2—N1	121.68 (18)	C1—C6—C8	118.35 (19)
C9—N2—H1N2	118.0 (19)	C5—C6—C8	123.40 (18)
N1—N2—H1N2	120.2 (19)	C4—C7—H7A	109.5
C9—N3—C10	124.2 (2)	C4—C7—H7B	109.5
C9—N3—H1N3	120.5 (18)	H7A—C7—H7B	109.5
C10—N3—H1N3	115.1 (18)	C4—C7—H7C	109.5
C2—C1—C6	121.1 (2)	H7A—C7—H7C	109.5
C2—C1—H1A	119.4	H7B—C7—H7C	109.5
C6—C1—H1A	119.4	N1—C8—C6	122.5 (2)
C1—C2—C3	119.4 (2)	N1—C8—H8A	118.7
C1—C2—H2A	120.3	C6—C8—H8A	118.7
C3—C2—H2A	120.3	N3—C9—N2	117.8 (2)
C2—C3—C4	121.5 (2)	N3—C9—S1	123.86 (17)
C2—C3—H3A	119.3	N2—C9—S1	118.37 (16)
C4—C3—H3A	119.3	N3—C10—H10A	109.5
C3—C4—C5	118.4 (2)	N3—C10—H10B	109.5
C3—C4—C7	121.2 (2)	H10A—C10—H10B	109.5
C5—C4—C7	120.3 (2)	N3—C10—H10C	109.5
O1—C5—C4	117.4 (2)	H10A—C10—H10C	109.5
O1—C5—C6	121.4 (2)	H10B—C10—H10C	109.5

C8—N1—N2—C9	170.4 (2)	O1—C5—C6—C1	−179.2 (2)
C6—C1—C2—C3	−1.4 (4)	C4—C5—C6—C1	1.7 (3)
C1—C2—C3—C4	1.9 (4)	O1—C5—C6—C8	1.1 (3)
C2—C3—C4—C5	−0.6 (3)	C4—C5—C6—C8	−178.0 (2)
C2—C3—C4—C7	−179.8 (3)	N2—N1—C8—C6	178.06 (19)
C3—C4—C5—O1	179.6 (2)	C1—C6—C8—N1	176.1 (2)
C7—C4—C5—O1	−1.1 (4)	C5—C6—C8—N1	−4.2 (3)
C3—C4—C5—C6	−1.2 (3)	C10—N3—C9—N2	179.9 (2)
C7—C4—C5—C6	178.0 (3)	C10—N3—C9—S1	1.2 (3)
C2—C1—C6—C5	−0.3 (3)	N1—N2—C9—N3	0.4 (3)
C2—C1—C6—C8	179.4 (2)	N1—N2—C9—S1	179.17 (16)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···N1	0.84 (4)	1.94 (4)	2.681 (3)	147 (4)
N2—H1N2···S1ⁱ	0.89 (3)	2.51 (3)	3.387 (2)	173 (3)
C10—H10A···Cg1ⁱⁱ	0.96	2.70	3.577 (4)	152

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

Torsion angles τ₁, τ₂, τ₃ and τ₄ (°) top

Compound	R₁	R₂	τ₁	τ₂	τ₃	τ₄
(I)	2-hydroxy-3-methylbenzylidenyl	methyl	4	170	0	180
AWAZOP (Hussein & Guan, 2015)	5-bromo-2-hydroxybenzylidenyl	methyl	1	175	12	179
AWEBEL (Hussein & Guan, 2015)	3-ethoxy-2-hydroxybenzylidenyl	methyl	176	174	4	180
CIVZAK (Hussein et al., 2014b)	5-(tert-butyl)-2-hydroxybenzylidenyl	ethyl	2	174	15	180
CIWBAN (Hussein et al., 2014b)	5-allyl-3-ethyl-2-hydroxybenzylidenyl	methyl	169	173	5	178
DAGVOZ (Arafath et al., 2017b)	2-hydroxy-5-methoxy-3-nitrobenzylidenyl	methyl	177	176	7	179
EFUPAX (Rubcic et al., 2008)	2-hydroxy-4-methoxybenzylidenyl	phenyl	2	173	4	174
EROVIR (Lo & Ng, 2011)	5-chloro-2-hydroxybenzylidenyl	ethyl	8	172	14	176
GOZQIX (Hussein et al., 2015a)	2-hydroxy-5-methoxybenzylidenyl	methyl	3	175	14	180
GOZQIX01 (Salam et al., 2016)	2-hydroxy-5-methoxybenzylidenyl	methyl	3	175	15	180
GOZQIX02 (Subhashree et al., 2017)	2-hydroxy-5-methoxybenzylidenyl	methyl	2	175	13	180
HABDEW (Hussein et al., 2015c)	3-ethoxy-2-hydroxybenzylidenyl	ethyl	177	176	5	180
HABFEY (Hussein et al., 2015c)	5-allyl-2-hydroxy-3-methoxybenzylidenyl	ethyl	173, 173	176, 179	6, 8	178, 177
HAXROO (Vrdoljak et al., 2005)	2-hydroxybenzylidenyl	methyl	1	176	11	178
HAXROO01 (Liu, 2015)	2-hydroxybenzylidenyl	methyl	2	175	11	178
HAXSAB (Vrdoljak et al., 2005)	2-hydroxy-3-methoxybenzylidenyl	methyl	177	174	5	178
IBAZUJ (Haque et al., 2015)	2,3-dihydroxybenzyliden	methyl	1	170	1	175
IBEDOL (Haque et al., 2015)	2-hydroxy-5-methylbenzylidenyl	methyl	3, 2	175, 173	16, 16	175, 175
IFUXEN (Tan et al., 2008b)	2,4-dihydroxybenzylidenyl	ethyl	2	179	0	176
IFUXEN01 (Hussein et al., 2014b)	2,4-dihydroxybenzylidenyl	ethyl	2	179	0	176
IFUXEN02 (Ramaiyer & Frank, 2015)	2,4-dihydroxybenzylidenyl	ethyl	1	175	4	179
IFUXEN03 (Ramaiyer & Frank, 2015)	2,4-dihydroxybenzylidenyl	ethyl	5	171	6	178
IGALUY (Tan et al., 2008c)	2,4-dihydroxybenzylidenyl	methyl	5	174	9	176
IGALUY01 (Salam et al., 2015)	2,4-dihydroxybenzylidenyl	methyl	2	177	16	178
IMAFIN (El-Asmy et al., 2016)	2-hydroxybenzylidenyl	ethyl	1	177	13	177
JAJHUA (Li et al., 2016)	5-bromo-2-hydroxybenzylidenyl	methyl	1	175	12	179
JOFHIW (Tan et al., 2008a)	2,5-dihydroxybenzyliden	methyl	1	175	11	178
KOCLIY (Đilović et al., 2008)	4-(diethylamino)-2-hydroxybenzylidenyl	phenyl	2	172	12	174
LAQCIR (Jacob & Kurup, 2012)	5-bromo-2-hydroxy-3-methoxybenzylidenyl	cyclohexyl	172	177	4	179
NUQNAP (Shawish et al., 2010)	2,3,4-trihydroxybenzylidenyl	ethyl	167	176	8	174
OBOLOJ (Arafath et al., 2017a)	5-chloro-2-hydroxybenzylidenyl	cyclohexyl	175	176	6	177
PAXCAU (Jacob et al., 2012)	5-bromo-2-hydroxy-3-methoxybenzylidenyl	phenyl	177	180	6	177
RIVFAE (Seena et al., 2008)	2-hydroxybenzylidenyl	phenyl	2, 5, 2	179, 175, 178	12, 9, 2	171, 177, 180
RIVFAE01 (Rubcic et al., 2008)	2-hydroxybenzylidenyl	phenyl	11, 3	177, 171	2, 2	175, 170
SUKQOG (Hussein et al., 2015d)	5-allyl-2-hydroxy-3-methoxybenzylidenyl	phenyl	168	172	4	179
WEXDAG (Orysyk et al., 2013)	2-hydroxybenzylidenyl	allyl	4	170	7	173
XOTPED (Hussein et al., 2015b)	2-hydroxy-3-methylbenzylidenyl	ethyl	2	179	7	179
YOCJOR (Chumakov et al., 2014)	5-bromo-2-hydroxybenzylidenyl	pyridin-2-yl	0	179	178	1
YOCJUX (Chumakov et al., 2014)	2-hydroxy-3-methoxybenzylidenyl	pyridin-2-yl	3	178	177	3
YOPHUI (Hussein et al., 2014a)	3-(tert-butyl)-2-hydroxybenzylidenyl	ethyl	4, 8	171, 169	4, 18	179, 180
YOPLIA (Hussein et al., 2014a)	2-hydroxy-5-methylbenzylidenyl	ethyl	4	171	10	180
YUKYOU (Salam & Haque, 2015)	3,5-dichloro-2-hydroxybenzylidenyl	ethyl	179	180	2	178
YUXJOS (Arafath et al., 2018a)	3-(tert-butyl)-2-hydroxybenzylidenyl	cyclohexyl	12	170	12	176
ZIJKIO (Li & Sato, 2013)	5-bromo-2-hydroxybenzylidenyl	ethyl	6	172	12	176
ZIJKIO02 (Hussein et al., 2015b)	5-bromo-2-hydroxybenzylidenyl	ethyl	7	173	13	177

Note: there is more than one torsion angle for compounds HABFEY, IBEDOL, RIVFAE, RIVFAE01 and YOPHUI because there are more than one independent molecules in their asymmetric units.

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(E)-2-(2-Hy­droxy-3-methyl­benzyl­idene)-N-methyl­hydrazine-1-carbo­thio­amide: supra­molecular assemblies in two-dimensions mediated by N—HS and C—Hπ inter­actions

Supporting information

Key indicators

checkCIF/PLATON results

(E)-2-(2-Hydroxy-3-methylbenzylidene)-N-methylhydrazine-1-carbothioamide: supramolecular assemblies in two-dimensions mediated by N—HS and C—Hπ interactions