Benzaldehyde thio­semicarbazone monohydrate

Gu, S.-J.; Zhu, K.-M.

doi:10.1107/S1600536808022769

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1597

doi:10.1107/S1600536808022769

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Benzaldehyde thiosemicarbazone monohydrate

Sheng-Jiu Gu ^a ^* and Kai-Mei Zhu ^a

^aCollege of Pharmacy, Guilin Medical University, Guilin 541004, People's Republic of China
^*Correspondence e-mail: gushengjiu2008@163.com

(Received 2 July 2008; accepted 20 July 2008; online 26 July 2008)

In the title compound, C₈H₉N₃S·H₂O, intramolecular N—H⋯N hydrogen bonding contributes to the molecular conformation. Water molecules are involved in intermolecular N—H⋯O and O—H⋯S hydrogen bonds, which link the molecules into ribbons extended along the a axis. Weak intermolecular N—H⋯S hydrogen bonds link these ribbons into layers parallel to the ab plane with the phenyl rings pointing up and down.

Related literature

For related crystal structures, see Beraldo et al. (2004 ); Bondock et al. (2007 ); Jing et al. (2006 ).

Experimental

Crystal data

C₈H₉N₃S·H₂O
M_r = 197.26
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.1685 (10) Å
b = 7.6733 (12) Å
c = 21.131 (2) Å
V = 1000.2 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 298 (2) K
0.49 × 0.30 × 0.28 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.871, T_max = 0.923
4749 measured reflections
1764 independent reflections
1438 reflections with I > 2σ(I)
R_int = 0.065

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.105
S = 1.07
1764 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ), 689 Friedel pairs
Flack parameter: −0.05 (13)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N1	0.86	2.26	2.613 (4)	105
N2—H2⋯O1ⁱ	0.86	1.95	2.805 (3)	171
N3—H3B⋯S1ⁱⁱ	0.86	2.57	3.423 (3)	170
O1—H1A⋯S1	0.85	2.45	3.276 (2)	164
O1—H1B⋯S1ⁱ	0.85	2.44	3.284 (2)	172
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808022769/cv2428sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808022769/cv2428Isup2.hkl

checkCIF report

Comment top

Aryl-hydrazones, such as semicarbazones, thiosemicarbazones and guanyl hydrazones, exhibit strong biological activity. Therefor,they are important for drug design (Beraldo et al., 2004), organocatalysis and for the preparation of heterocyclic rings (Bondock et al., 2007). In this paper, we present the title compound, (I).

In (I) (Fig. 1), the bond lengths and angles are normal and comparable to those observed in the reported compounds (Jing et al., 2006). Intramolecular N—H···O hydrogen bond (Table 1) contributes to the molecular conformation. Crystalline water molecules are involved in the intermolecular N—H···O and O—H···S hydrogen bonds (Table 1), which link the molecules into ribbons extended along a axis. Weak intermolecular N—H···S hydrogen bonds (Table 1) link further these ribbons into layers parallel to ab plane with the up and down protruding phenyl rings.

Related literature top

For related crystal structures, see Beraldo et al. (2004); Bondock et al. (2007); Jing et al. (2006).

Experimental top

Benzaldehyde (0.3 mmol) and thiosemicarbazide (0.3 mmol) were mixed in 50 ml flash in the presence of aqueous medium. After stirring 30 min at 373 K, the mixture then cooling slowly to room temperature and affording the title compound, then recrystallized from ethanol, affording the title compound as a colorless crystalline solid. Elemental analysis: calculated for C₈H₁₁N₃OS: C 48.71, H 5.62, N 21.30%; found: C 48.58, H 5.65, N 21.24%.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The content of asymmetric unit of the title compound showing the atomic numbering scheme and 30% probability displacement ellipsoids.

Benzaldehyde thiosemicarbazone monohydrate top

Crystal data top

C₈H₉N₃S·H₂O	D_x = 1.310 Mg m⁻³
M_r = 197.26	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 1572 reflections
a = 6.1685 (10) Å	θ = 2.8–22.5°
b = 7.6733 (12) Å	µ = 0.29 mm⁻¹
c = 21.131 (2) Å	T = 298 K
V = 1000.2 (2) Å³	Block, orange
Z = 4	0.49 × 0.30 × 0.28 mm
F(000) = 416

Data collection top

Bruker SMART CCD area-detector diffractometer	1764 independent reflections
Radiation source: fine-focus sealed tube	1438 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.871, T_max = 0.924	k = −9→6
4749 measured reflections	l = −25→24

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.105	w = 1/[σ²(F_o²) + (0.0438P)² + 0.0825P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1764 reflections	Δρ_max = 0.25 e Å⁻³
118 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 689 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.05 (13)

Crystal data top

C₈H₉N₃S·H₂O	V = 1000.2 (2) Å³
M_r = 197.26	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.1685 (10) Å	µ = 0.29 mm⁻¹
b = 7.6733 (12) Å	T = 298 K
c = 21.131 (2) Å	0.49 × 0.30 × 0.28 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1764 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1438 reflections with I > 2σ(I)
T_min = 0.871, T_max = 0.924	R_int = 0.065
4749 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.105	Δρ_max = 0.25 e Å⁻³
S = 1.08	Δρ_min = −0.17 e Å⁻³
1764 reflections	Absolute structure: Flack (1983), 689 Friedel pairs
118 parameters	Absolute structure parameter: −0.05 (13)
0 restraints

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
N1	0.5077 (4)	0.4006 (3)	0.35842 (11)	0.0430 (6)
N2	0.4610 (4)	0.4442 (3)	0.42017 (10)	0.0402 (6)
H2	0.5473	0.5107	0.4412	0.048*
N3	0.1572 (5)	0.2820 (4)	0.41293 (12)	0.0616 (9)
H3A	0.1923	0.2576	0.3746	0.074*
H3B	0.0400	0.2401	0.4289	0.074*
O1	0.2807 (3)	0.8582 (3)	0.51847 (12)	0.0681 (7)
H1A	0.2874	0.7483	0.5138	0.082*
H1B	0.4026	0.9030	0.5091	0.082*
S1	0.22368 (12)	0.43397 (10)	0.52322 (3)	0.0473 (3)
C1	0.2821 (5)	0.3831 (3)	0.44708 (14)	0.0398 (7)
C2	0.6891 (5)	0.4535 (4)	0.33743 (13)	0.0436 (7)
H2A	0.7840	0.5112	0.3645	0.052*
C3	0.7511 (4)	0.4251 (4)	0.27170 (12)	0.0412 (7)
C4	0.6111 (6)	0.3517 (4)	0.22810 (15)	0.0534 (9)
H4	0.4745	0.3146	0.2409	0.064*
C5	0.6728 (7)	0.3333 (5)	0.16566 (16)	0.0640 (11)
H5	0.5766	0.2870	0.1362	0.077*
C6	0.8751 (7)	0.3834 (5)	0.14733 (17)	0.0636 (11)
H6	0.9180	0.3671	0.1056	0.076*
C7	1.0158 (6)	0.4572 (5)	0.18932 (16)	0.0630 (10)
H7	1.1523	0.4940	0.1762	0.076*
C8	0.9527 (5)	0.4761 (4)	0.25132 (15)	0.0536 (9)
H8	1.0490	0.5248	0.2802	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0480 (15)	0.0477 (15)	0.0332 (13)	0.0000 (13)	0.0012 (12)	−0.0020 (11)
N2	0.0443 (14)	0.0422 (14)	0.0342 (12)	−0.0074 (14)	−0.0004 (11)	−0.0034 (12)
N3	0.061 (2)	0.079 (2)	0.0456 (17)	−0.0290 (17)	0.0118 (14)	−0.0121 (15)
O1	0.0524 (15)	0.0609 (13)	0.0910 (19)	0.0017 (12)	0.0204 (15)	−0.0130 (13)
S1	0.0467 (5)	0.0576 (5)	0.0376 (4)	0.0009 (4)	0.0015 (4)	−0.0018 (4)
C1	0.0402 (17)	0.0381 (16)	0.0411 (16)	0.0008 (15)	−0.0035 (15)	0.0036 (12)
C2	0.0415 (17)	0.0469 (17)	0.0422 (16)	0.0035 (17)	−0.0009 (14)	−0.0018 (14)
C3	0.0421 (17)	0.0433 (14)	0.0383 (15)	0.0013 (18)	0.0036 (14)	0.0015 (14)
C4	0.056 (2)	0.061 (2)	0.0429 (19)	−0.0134 (17)	0.0061 (17)	−0.0012 (17)
C5	0.083 (3)	0.065 (2)	0.044 (2)	−0.013 (2)	0.0033 (19)	−0.0067 (18)
C6	0.086 (3)	0.061 (2)	0.043 (2)	0.005 (2)	0.017 (2)	0.0038 (18)
C7	0.053 (2)	0.080 (3)	0.057 (2)	−0.002 (2)	0.0154 (18)	0.010 (2)
C8	0.050 (2)	0.066 (2)	0.0446 (17)	−0.0061 (17)	0.0023 (16)	0.0054 (16)

Geometric parameters (Å, º) top

N1—C2	1.270 (3)	C3—C8	1.373 (4)
N1—N2	1.378 (3)	C3—C4	1.382 (4)
N2—C1	1.327 (3)	C4—C5	1.380 (4)
N2—H2	0.8600	C4—H4	0.9300
N3—C1	1.310 (4)	C5—C6	1.362 (5)
N3—H3A	0.8600	C5—H5	0.9300
N3—H3B	0.8600	C6—C7	1.364 (5)
O1—H1A	0.8499	C6—H6	0.9300
O1—H1B	0.8499	C7—C8	1.375 (5)
S1—C1	1.695 (3)	C7—H7	0.9300
C2—C3	1.457 (4)	C8—H8	0.9300
C2—H2A	0.9300

C2—N1—N2	115.9 (3)	C4—C3—C2	122.2 (3)
C1—N2—N1	119.6 (2)	C5—C4—C3	120.4 (3)
C1—N2—H2	120.2	C5—C4—H4	119.8
N1—N2—H2	120.2	C3—C4—H4	119.8
C1—N3—H3A	120.0	C6—C5—C4	119.7 (4)
C1—N3—H3B	120.0	C6—C5—H5	120.2
H3A—N3—H3B	120.0	C4—C5—H5	120.2
H1A—O1—H1B	109.4	C5—C6—C7	121.0 (3)
N3—C1—N2	117.6 (3)	C5—C6—H6	119.5
N3—C1—S1	122.3 (2)	C7—C6—H6	119.5
N2—C1—S1	120.1 (2)	C6—C7—C8	118.9 (3)
N1—C2—C3	121.1 (3)	C6—C7—H7	120.5
N1—C2—H2A	119.5	C8—C7—H7	120.5
C3—C2—H2A	119.5	C3—C8—C7	121.7 (3)
C8—C3—C4	118.2 (3)	C3—C8—H8	119.2
C8—C3—C2	119.6 (3)	C7—C8—H8	119.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N1	0.86	2.26	2.613 (4)	105
N2—H2···O1ⁱ	0.86	1.95	2.805 (3)	171
N3—H3B···S1ⁱⁱ	0.86	2.57	3.423 (3)	170
O1—H1A···S1	0.85	2.45	3.276 (2)	164
O1—H1B···S1ⁱ	0.85	2.44	3.284 (2)	172

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

Experimental details

Crystal data
Chemical formula	C₈H₉N₃S·H₂O
M_r	197.26
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	6.1685 (10), 7.6733 (12), 21.131 (2)
V (Å³)	1000.2 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.49 × 0.30 × 0.28

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.871, 0.924
No. of measured, independent and observed [I > 2σ(I)] reflections	4749, 1764, 1438
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.105, 1.08
No. of reflections	1764
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.17
Absolute structure	Flack (1983), 689 Friedel pairs
Absolute structure parameter	−0.05 (13)

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N1	0.86	2.26	2.613 (4)	104.7
N2—H2···O1ⁱ	0.86	1.95	2.805 (3)	170.7
N3—H3B···S1ⁱⁱ	0.86	2.57	3.423 (3)	170.4
O1—H1A···S1	0.85	2.45	3.276 (2)	163.5
O1—H1B···S1ⁱ	0.85	2.44	3.284 (2)	172.0

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

Acknowledgements

The authors thank the Nature Science Foundation of Guangxi (No. 0640190 and No. 0728229), the Tackle Key Problem Foundation of Guangxi (No. 0815005-1-17), the Nature Science Foundation of Guilin (No. 20070305 and No. 20080103-5) and the Education Foundation of Guangxi (No. 200710MS144) for financial support.

References

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