Benzyl N′-(1H-indol-2-ylmethyl­ene)hydrazinecarbodithio­ate ethanol hemisolvate

In the crystal of the title compound, C₁₇H₁₅N₃S₂·0.5C₂H₆O, the mol­ecules are linked by a pair of N—H_aliphatic...S hydrogen bonds across a center of inversion, forming a dimer. The ethanol solvent mol­ecule, which is statistically disordered about a crystallographic twofold rotation axis, accepts an N—H_aromatic...O hydrogen bond; the hydr­oxy group of the solvent mol­ecule is not engaged in hydrogen bonding.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• Disorder in solvent or counterion
• R factor = 0.033
• wR factor = 0.088
• Data-to-parameter ratio = 16.8

checkCIF/PLATON results

No syntax errors found



Alert level C
            Value of measurement temperature given =   100.000
            Value of melting point given =     0.000
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S2     --  C8      ..       5.66 su
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          5
PLAT302_ALERT_4_G Anion/Solvent Disorder .........................      50.00 Perc.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

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

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S1. Comment

For background references, see: Khaledi et al. (2008).

Related literature

For references to benzyl esters of hydrazinecarbodithioic acids, see: Khaledi et al. (2008).

S2. Experimental

Indole-2-carbaldehyde (0.36 g, 2.5 mmol) and S-benzyldithiocarbazate (0.495 g, 2.5 mmol) were heated in ethanol (40 ml) for 3 h. The solution was set aside for the formation of yellow blocks of (I).

S3. Refinement

C-bound hydrogen atoms were placed at calculated positions (C–H = 0.95–0.99 Å) and refined as riding with U(H) = 1.2–1.5 times U_eq(C). The amino and hydroxy H atoms were located in a difference map, and were refined with distance restraints of N–H = 0.88±0.01 and O–H = 0.84+_0.01 Å; their U_iso values were freely refined.

The ethanol molecule is statistically disordered about a two-fold axis: the O–C distance was restrained to 1.45±0.01 Å and the C–C distance to 1.50+_0.01 Å; the displacement factors of the two C atoms were restrained to be equal.

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: pubCIF (Westrip, 2008).

Figures

Fig. 1. View of (I) at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius. Only one orientation of the ethanol molecule is shown.

Benzyl N'-(1H-indol-2-ylmethylene)hydrazinecarbodithioate ethanol hemisolvate

Crystal data

C17H15N3S2·0.5C2H6O	F(000) = 1464
Mr = 348.47	Dx = 1.364 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5259 reflections
a = 13.4225 (2) Å	θ = 2.5–28.3°
b = 15.4088 (2) Å	µ = 0.32 mm^−1
c = 16.8120 (3) Å	T = 100 K
β = 102.637 (1)°	Block, yellow
V = 3392.90 (9) Å^3	0.25 × 0.20 × 0.15 mm
Z = 8

Data collection

Bruker SMART APEX CCD diffractometer	3897 independent reflections
Radiation source: fine-focus sealed tube	3332 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→17
Tmin = 0.924, Tmax = 0.954	k = −19→20
14302 measured reflections	l = −21→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0411P)^2 + 3.3308P] where P = (Fo^2 + 2Fc^2)/3
3897 reflections	(Δ/σ)max = 0.001
232 parameters	Δρmax = 0.35 e Å^−3
5 restraints	Δρmin = −0.40 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.58648 (3)	0.69507 (2)	0.36508 (2)	0.01972 (10)
S2	0.56141 (3)	0.50160 (2)	0.38844 (2)	0.02263 (11)
N1	0.48149 (10)	0.62574 (8)	0.46106 (8)	0.0201 (3)
H1N	0.4612 (15)	0.5843 (10)	0.4893 (11)	0.036 (5)*
N2	0.45977 (10)	0.71147 (8)	0.47237 (8)	0.0200 (3)
N3	0.39716 (10)	0.88130 (8)	0.48940 (8)	0.0205 (3)
H3N	0.4341 (14)	0.8771 (13)	0.4528 (10)	0.039 (6)*
C1	0.72885 (12)	0.71544 (9)	0.27832 (9)	0.0199 (3)
C2	0.83286 (12)	0.71386 (11)	0.31290 (10)	0.0254 (3)
H2	0.8608	0.6671	0.3476	0.031*
C3	0.89612 (13)	0.77961 (12)	0.29733 (10)	0.0297 (4)
H3	0.9671	0.7776	0.3212	0.036*
C4	0.85687 (13)	0.84829 (11)	0.24721 (10)	0.0260 (3)
H4	0.9004	0.8937	0.2372	0.031*
C5	0.75366 (13)	0.85010 (10)	0.21189 (10)	0.0242 (3)
H5	0.7263	0.8968	0.1770	0.029*
C6	0.68972 (12)	0.78405 (9)	0.22712 (10)	0.0222 (3)
H6	0.6190	0.7858	0.2024	0.027*
C7	0.66018 (12)	0.64525 (9)	0.29845 (10)	0.0211 (3)
H7A	0.7011	0.5962	0.3264	0.025*
H7B	0.6144	0.6232	0.2482	0.025*
C8	0.53949 (11)	0.60480 (9)	0.40842 (9)	0.0180 (3)
C9	0.40256 (11)	0.72590 (9)	0.52304 (9)	0.0203 (3)
H9	0.3811	0.6794	0.5524	0.024*
C10	0.37149 (11)	0.81355 (9)	0.53466 (9)	0.0197 (3)
C11	0.31225 (12)	0.84426 (9)	0.58549 (9)	0.0208 (3)
H11	0.2848	0.8111	0.6233	0.025*
C12	0.29954 (11)	0.93534 (9)	0.57094 (9)	0.0192 (3)
C13	0.35401 (11)	0.95615 (9)	0.51045 (9)	0.0197 (3)
C14	0.35929 (12)	1.04048 (10)	0.48156 (10)	0.0246 (3)
H14	0.3960	1.0533	0.4407	0.030*
C15	0.30886 (13)	1.10461 (10)	0.51477 (10)	0.0269 (4)
H15	0.3116	1.1628	0.4967	0.032*
C16	0.25378 (13)	1.08549 (10)	0.57456 (10)	0.0259 (3)
H16	0.2196	1.1309	0.5960	0.031*
C17	0.24827 (12)	1.00197 (10)	0.60284 (10)	0.0229 (3)
H17	0.2105	0.9897	0.6431	0.027*
O1	0.48913 (18)	0.92618 (16)	0.34417 (14)	0.0289 (5)	0.50
H1O	0.5523 (10)	0.922 (3)	0.363 (3)	0.045 (13)*	0.50
C18	0.4709 (7)	1.0002 (6)	0.2875 (4)	0.0472 (9)	0.50
H18A	0.3966	1.0099	0.2687	0.057*	0.50
H18B	0.5016	1.0533	0.3157	0.057*	0.50
C19	0.5162 (7)	0.9824 (6)	0.2172 (4)	0.0472 (9)	0.50
H19A	0.5044	1.0320	0.1798	0.071*	0.50
H19B	0.4847	0.9304	0.1888	0.071*	0.50
H19C	0.5898	0.9729	0.2360	0.071*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0245 (2)	0.01412 (17)	0.0230 (2)	0.00081 (13)	0.01047 (15)	0.00013 (13)
S2	0.0342 (2)	0.01388 (17)	0.0233 (2)	−0.00028 (14)	0.01385 (17)	−0.00209 (14)
N1	0.0271 (7)	0.0148 (6)	0.0210 (7)	0.0021 (5)	0.0108 (5)	0.0004 (5)
N2	0.0225 (6)	0.0171 (6)	0.0203 (7)	0.0026 (5)	0.0042 (5)	−0.0024 (5)
N3	0.0223 (6)	0.0210 (6)	0.0204 (7)	0.0009 (5)	0.0092 (5)	−0.0024 (5)
C1	0.0255 (8)	0.0185 (7)	0.0183 (7)	−0.0008 (6)	0.0104 (6)	−0.0024 (5)
C2	0.0261 (8)	0.0299 (8)	0.0217 (8)	0.0038 (6)	0.0082 (7)	0.0082 (6)
C3	0.0207 (8)	0.0439 (10)	0.0241 (9)	−0.0035 (7)	0.0045 (7)	0.0074 (7)
C4	0.0293 (9)	0.0299 (8)	0.0202 (8)	−0.0086 (7)	0.0087 (7)	0.0026 (6)
C5	0.0316 (9)	0.0207 (7)	0.0204 (8)	−0.0001 (6)	0.0062 (7)	0.0028 (6)
C6	0.0229 (8)	0.0213 (7)	0.0222 (8)	−0.0002 (6)	0.0044 (6)	−0.0009 (6)
C7	0.0258 (8)	0.0179 (7)	0.0221 (8)	0.0001 (6)	0.0110 (6)	−0.0025 (6)
C8	0.0199 (7)	0.0170 (6)	0.0169 (7)	−0.0003 (5)	0.0031 (6)	0.0001 (5)
C9	0.0224 (7)	0.0199 (7)	0.0182 (7)	0.0022 (6)	0.0038 (6)	−0.0003 (6)
C10	0.0199 (7)	0.0209 (7)	0.0178 (7)	0.0013 (6)	0.0028 (6)	−0.0012 (6)
C11	0.0242 (8)	0.0206 (7)	0.0181 (8)	0.0021 (6)	0.0057 (6)	−0.0003 (6)
C12	0.0184 (7)	0.0217 (7)	0.0164 (7)	0.0012 (6)	0.0014 (6)	−0.0025 (6)
C13	0.0187 (7)	0.0209 (7)	0.0190 (8)	0.0007 (6)	0.0032 (6)	−0.0043 (6)
C14	0.0281 (8)	0.0227 (7)	0.0235 (8)	−0.0033 (6)	0.0066 (7)	−0.0018 (6)
C15	0.0333 (9)	0.0183 (7)	0.0270 (9)	0.0001 (6)	0.0017 (7)	−0.0020 (6)
C16	0.0265 (8)	0.0234 (7)	0.0262 (9)	0.0053 (6)	0.0020 (7)	−0.0082 (6)
C17	0.0224 (8)	0.0263 (8)	0.0203 (8)	0.0030 (6)	0.0057 (6)	−0.0046 (6)
O1	0.0238 (12)	0.0401 (13)	0.0217 (12)	−0.0033 (10)	0.0026 (10)	0.0035 (10)
C18	0.041 (2)	0.050 (3)	0.0478 (15)	0.0096 (19)	0.0033 (12)	−0.001 (2)
C19	0.041 (2)	0.050 (3)	0.0478 (15)	0.0096 (19)	0.0033 (12)	−0.001 (2)

Geometric parameters (Å, º)

S1—C8	1.7506 (15)	C9—C10	1.439 (2)
S1—C7	1.8187 (15)	C9—H9	0.9500
S2—C8	1.6647 (14)	C10—C11	1.372 (2)
N1—C8	1.3397 (19)	C11—C12	1.428 (2)
N1—N2	1.3748 (16)	C11—H11	0.9500
N1—H1N	0.875 (9)	C12—C17	1.406 (2)
N2—C9	1.285 (2)	C12—C13	1.413 (2)
N3—C13	1.3713 (18)	C13—C14	1.394 (2)
N3—C10	1.3792 (19)	C14—C15	1.383 (2)
N3—H3N	0.873 (9)	C14—H14	0.9500
C1—C2	1.390 (2)	C15—C16	1.403 (2)
C1—C6	1.392 (2)	C15—H15	0.9500
C1—C7	1.507 (2)	C16—C17	1.379 (2)
C2—C3	1.383 (2)	C16—H16	0.9500
C2—H2	0.9500	C17—H17	0.9500
C3—C4	1.383 (2)	O1—C18	1.472 (8)
C3—H3	0.9500	O1—H1O	0.839 (10)
C4—C5	1.383 (2)	C18—C19	1.469 (5)
C4—H4	0.9500	C18—H18A	0.9900
C5—C6	1.391 (2)	C18—H18B	0.9900
C5—H5	0.9500	C19—H19A	0.9800
C6—H6	0.9500	C19—H19B	0.9800
C7—H7A	0.9900	C19—H19C	0.9800
C7—H7B	0.9900
C8—S1—C7	102.42 (7)	C11—C10—N3	109.34 (13)
C8—N1—N2	119.62 (12)	C11—C10—C9	129.24 (14)
C8—N1—H1N	118.6 (13)	N3—C10—C9	121.37 (14)
N2—N1—H1N	121.7 (13)	C10—C11—C12	107.22 (13)
C9—N2—N1	115.70 (13)	C10—C11—H11	126.4
C13—N3—C10	108.88 (12)	C12—C11—H11	126.4
C13—N3—H3N	125.6 (14)	C17—C12—C13	118.83 (14)
C10—N3—H3N	125.5 (14)	C17—C12—C11	134.62 (15)
C2—C1—C6	118.72 (14)	C13—C12—C11	106.55 (13)
C2—C1—C7	120.08 (14)	N3—C13—C14	129.59 (14)
C6—C1—C7	121.17 (14)	N3—C13—C12	108.01 (13)
C3—C2—C1	120.66 (15)	C14—C13—C12	122.40 (14)
C3—C2—H2	119.7	C15—C14—C13	117.29 (15)
C1—C2—H2	119.7	C15—C14—H14	121.4
C4—C3—C2	120.53 (15)	C13—C14—H14	121.4
C4—C3—H3	119.7	C14—C15—C16	121.36 (15)
C2—C3—H3	119.7	C14—C15—H15	119.3
C3—C4—C5	119.29 (15)	C16—C15—H15	119.3
C3—C4—H4	120.4	C17—C16—C15	121.27 (14)
C5—C4—H4	120.4	C17—C16—H16	119.4
C4—C5—C6	120.45 (15)	C15—C16—H16	119.4
C4—C5—H5	119.8	C16—C17—C12	118.83 (15)
C6—C5—H5	119.8	C16—C17—H17	120.6
C5—C6—C1	120.35 (15)	C12—C17—H17	120.6
C5—C6—H6	119.8	C18—O1—H1O	108 (3)
C1—C6—H6	119.8	C19—C18—O1	109.7 (7)
C1—C7—S1	106.10 (10)	C19—C18—H18A	109.7
C1—C7—H7A	110.5	O1—C18—H18A	109.7
S1—C7—H7A	110.5	C19—C18—H18B	109.7
C1—C7—H7B	110.5	O1—C18—H18B	109.7
S1—C7—H7B	110.5	H18A—C18—H18B	108.2
H7A—C7—H7B	108.7	C18—C19—H19A	109.5
N1—C8—S2	121.15 (11)	C18—C19—H19B	109.5
N1—C8—S1	113.45 (10)	H19A—C19—H19B	109.5
S2—C8—S1	125.40 (9)	C18—C19—H19C	109.5
N2—C9—C10	119.03 (14)	H19A—C19—H19C	109.5
N2—C9—H9	120.5	H19B—C19—H19C	109.5
C10—C9—H9	120.5
C8—N1—N2—C9	179.09 (14)	N2—C9—C10—C11	−179.23 (16)
C6—C1—C2—C3	0.6 (2)	N2—C9—C10—N3	3.6 (2)
C7—C1—C2—C3	−177.57 (15)	N3—C10—C11—C12	0.47 (17)
C1—C2—C3—C4	0.2 (3)	C9—C10—C11—C12	−176.97 (15)
C2—C3—C4—C5	−0.8 (3)	C10—C11—C12—C17	179.98 (17)
C3—C4—C5—C6	0.6 (2)	C10—C11—C12—C13	−0.39 (17)
C4—C5—C6—C1	0.2 (2)	C10—N3—C13—C14	179.53 (16)
C2—C1—C6—C5	−0.8 (2)	C10—N3—C13—C12	0.12 (17)
C7—C1—C6—C5	177.36 (14)	C17—C12—C13—N3	179.86 (13)
C2—C1—C7—S1	106.98 (14)	C11—C12—C13—N3	0.16 (16)
C6—C1—C7—S1	−71.14 (16)	C17—C12—C13—C14	0.4 (2)
C8—S1—C7—C1	−163.14 (11)	C11—C12—C13—C14	−179.30 (14)
N2—N1—C8—S2	−176.00 (11)	N3—C13—C14—C15	−179.11 (15)
N2—N1—C8—S1	3.72 (18)	C12—C13—C14—C15	0.2 (2)
C7—S1—C8—N1	179.96 (11)	C13—C14—C15—C16	−0.6 (2)
C7—S1—C8—S2	−0.33 (12)	C14—C15—C16—C17	0.3 (3)
N1—N2—C9—C10	−176.43 (13)	C15—C16—C17—C12	0.3 (2)
C13—N3—C10—C11	−0.38 (17)	C13—C12—C17—C16	−0.7 (2)
C13—N3—C10—C9	177.30 (13)	C11—C12—C17—C16	178.94 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···S2^i	0.88 (1)	2.52 (1)	3.350 (1)	159 (2)
N3—H3n···O1	0.87 (1)	2.25 (1)	3.047 (3)	153 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.