(3Z)-3-[(Z)-2-(2-Oxoindolin-3-yl­idene)hydrazin-1-yl­idene]indolin-2-one 0.17-hydrate

Liu, Y.-H.; Zhao, L.; Liu, M.-X.; Lin, H.; Li, J.-J.

doi:10.1107/S1600536814011805

organic compounds

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(3Z)-3-[(Z)-2-(2-Oxoindolin-3-ylidene)hydrazin-1-ylidene]indolin-2-one 0.17-hydrate

Yong-Hong Liu,^a ^* Lei Zhao,^b Ming-Xuan Liu,^b Hai Lin ^b and Jing-Jing Li ^b

^aCollege of Chemistry and Chemical Engineering, Yangzhou University, Jiangsu Provincial Key Laboratory of Environmental Material & Engineering, Yangzhou, 225002, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, People's Republic of China
^*Correspondence e-mail: yhliu@yzu.edu.cn

(Received 4 May 2014; accepted 21 May 2014; online 31 May 2014)

In the title compound, C₁₆H₁₀N₄O₂·0.17H₂O, prepared by the one-step condensation reaction of isatin with hydrazine hydrate under microwave irradiation, the complete organic molecule is generated by crystallographic inversion symmetry and therefore exists in an S-trans conformation. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, generating a three-dimensional framework with [001] channels, which are occupied by the disordered water molecules.

CCDC reference: 1004532

Related literature

For background to microwave synthesis, see: Hoz et al. (2004 ); Jagani et al. (2012 ). For our previous work in this area, see: Liu et al. (2008 ); Wang et al. (2010 ). For the coventional synthesis of the title compound, see: Ali & Alam (1994 ).

Experimental

Crystal data

C₁₆H₁₀N₄O₂·0.17H₂O
M_r = 308.30
Trigonal, $[R \overline 3]$
a = 24.8699 (18) Å
c = 5.6603 (8) Å
V = 3031.9 (5) Å³
Z = 9
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.38 × 0.16 × 0.14 mm

Data collection

Bruker SMART1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.963, T_max = 0.986
8691 measured reflections
1547 independent reflections
1290 reflections with I > 2σigma(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.108
S = 1.01
1547 reflections
103 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.13	2.8951 (17)	148
Symmetry code: (i) $[-y+{\script{1\over 3}}, x-y-{\script{1\over 3}}, z+{\script{2\over 3}}]$ .

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

CCDC reference: 1004532

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814011805/hb7227sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814011805/hb7227Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814011805/hb7227Isup3.cml

checkCIF report

Comment top

Microwave irradiated and solvent-free synthesis have aroused great attention in recent years due to rapid, convenient, green, environment friendly, inexpensive and efficient (Hoz et al., 2004; Jagani et al., 2012). As a continuation of our research work on Schiff bases (Liu et al., 2008; Wang et al.,2010), we report here one step synthesis of the title compound under microwave irradiated and free-solvent condition, which was prepared by two steps in the normal method (Ali & Alam, 1994), and its structure.

In the central symmetric molecule of the compound, the non-hydrogen atoms are conjugated by a couple of double bonds of C7=N2 and C7a=N2a, because whose bond length [1.2891 (17) Å] is shorter than the single bond one of C1—N1or C1a—N1a [1.4022 (17) Å] but longer than normal double one of C=N [1.271 (5) Å]. The molecule exists as the most stable configuration of (E, E)-isomer and conformation of s-trans (Fig. 1, Table 1).

In its pack structure there are two couples of N1–H1···O1 inter-molecular hydrogen bonds in the neighbor molecules which link many molecules into three dimensional net-work frames, and the disorder water molecules merge into the net-work (Fig. 2, Table 1). Thus the guest molecules of the water and the host molecules of the compound form into a super-molecular net-work structure.

Related literature top

For background to microwave synthesis, see: Hoz et al. (2004); Jagani et al. (2012). For our previous work in this area, see: Liu et al. (2008); Wang et al. (2010). For the coventional synthesis of the title compound, see: Ali & Alam (1994).

Experimental top

In refluxing equipment, isatin (2.94 g, 20 mmol), 50% hydrazine hydrate (0.62 ml, 9.5 mmol) were heated under microwave irradiation for 10 min. After cooling, the red crystalline mixture was recrystallized from dimethylformamide to give 2.5 g (86.2%) of the title compound, m.p. 494.5–495.5 K (ref. 494.5~495.5 K, Ali et al., 1994).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 30% probability ellipsoids.
	Fig. 2. Part of the crystal structure of the title compound, showing two couples of N–H···O inter-molecular hydrogen bonds as dashed lines linking the molecules and disorder water molecules into a super-molecular net-work structure. For the sake of clarity, H atoms not involved in hydrogen bonding have been omitted.

(3Z)-3-[(Z)-2-(2-Oxoindolin-3-ylidene)hydrazin-1-ylidene]indolin-2-one 0.17-hydrate top

Crystal data top

C₁₆H₁₀N₄O₂·0.17H₂O	F(000) = 1369
M_r = 308.30	D_x = 1.450 Mg m⁻³
Trigonal, R3	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -R 3	θ = 2.8–27.2°
a = 24.8699 (18) Å	µ = 0.10 mm⁻¹
c = 5.6603 (8) Å	T = 296 K
V = 3031.9 (5) Å³	Block, brown
Z = 9	0.38 × 0.16 × 0.14 mm

Data collection top

Bruker SMART1000 CCD diffractometer	1547 independent reflections
Radiation source: fine-focus sealed tube	1290 reflections with I > 2σigma(I)
Graphite monochromator	R_int = 0.025
thin–slice ω scans	θ_max = 27.5°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −32→32
T_min = 0.963, T_max = 0.986	k = −29→32
8691 measured reflections	l = −7→7

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0545P)² + 2.5765P] where P = (F_o² + 2F_c²)/3
1547 reflections	(Δ/σ)_max < 0.001
103 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₆H₁₀N₄O₂·0.17H₂O	Z = 9
M_r = 308.30	Mo Kα radiation
Trigonal, R3	µ = 0.10 mm⁻¹
a = 24.8699 (18) Å	T = 296 K
c = 5.6603 (8) Å	0.38 × 0.16 × 0.14 mm
V = 3031.9 (5) Å³

Data collection top

Bruker SMART1000 CCD diffractometer	1547 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1290 reflections with I > 2σigma(I)
T_min = 0.963, T_max = 0.986	R_int = 0.025
8691 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.01	Δρ_max = 0.25 e Å⁻³
1547 reflections	Δρ_min = −0.18 e Å⁻³
103 parameters

Special details top

Experimental. The title compound was synthesized under microwave irradiation.

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	Occ. (<1)
C1	0.25001 (6)	0.06795 (6)	0.2063 (2)	0.0345 (3)
C2	0.20279 (7)	0.05119 (7)	0.3672 (3)	0.0429 (3)
H2	0.1975	0.0250	0.4934	0.051*
C3	0.16336 (8)	0.07495 (8)	0.3331 (3)	0.0515 (4)
H3	0.1310	0.0644	0.4390	0.062*
C4	0.17099 (8)	0.11403 (8)	0.1452 (3)	0.0521 (4)
H4	0.1434	0.1286	0.1257	0.063*
C5	0.21929 (7)	0.13147 (7)	−0.0134 (3)	0.0439 (3)
H5	0.2247	0.1581	−0.1379	0.053*
C6	0.25943 (6)	0.10844 (6)	0.0170 (2)	0.0341 (3)
C7	0.31363 (6)	0.11575 (6)	−0.1095 (2)	0.0336 (3)
C8	0.33439 (6)	0.07495 (6)	0.0163 (2)	0.0349 (3)
N1	0.29469 (5)	0.04931 (5)	0.20131 (19)	0.0386 (3)
H1	0.2967	0.0246	0.3026	0.046*
N2	0.34522 (6)	0.14844 (5)	−0.2881 (2)	0.0406 (3)
O1	0.37735 (5)	0.06693 (5)	−0.03535 (18)	0.0459 (3)
O1W	0.0000	0.0000	0.248 (4)	0.177 (8)	0.25

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0402 (7)	0.0309 (6)	0.0306 (6)	0.0163 (5)	0.0026 (5)	0.0005 (5)
C2	0.0495 (8)	0.0409 (7)	0.0372 (7)	0.0217 (6)	0.0112 (6)	0.0069 (6)
C3	0.0532 (9)	0.0532 (9)	0.0516 (9)	0.0291 (8)	0.0181 (7)	0.0037 (7)
C4	0.0582 (9)	0.0549 (9)	0.0574 (10)	0.0388 (8)	0.0097 (7)	0.0033 (7)
C5	0.0547 (9)	0.0410 (7)	0.0422 (8)	0.0287 (7)	0.0055 (6)	0.0060 (6)
C6	0.0412 (7)	0.0297 (6)	0.0297 (6)	0.0165 (5)	0.0034 (5)	0.0017 (5)
C7	0.0385 (7)	0.0309 (6)	0.0281 (6)	0.0149 (5)	0.0011 (5)	0.0005 (5)
C8	0.0394 (7)	0.0345 (6)	0.0292 (6)	0.0173 (5)	0.0018 (5)	0.0003 (5)
N1	0.0461 (6)	0.0415 (6)	0.0327 (6)	0.0252 (5)	0.0067 (5)	0.0103 (5)
N2	0.0460 (7)	0.0416 (6)	0.0335 (6)	0.0214 (5)	0.0066 (5)	0.0095 (5)
O1	0.0479 (6)	0.0568 (6)	0.0415 (6)	0.0325 (5)	0.0074 (4)	0.0050 (5)
O1W	0.093 (6)	0.093 (6)	0.34 (3)	0.047 (3)	0.000	0.000

Geometric parameters (Å, º) top

C1—C2	1.3756 (19)	C5—C6	1.388 (2)
C1—N1	1.4022 (17)	C5—H5	0.9300
C1—C6	1.4073 (17)	C6—C7	1.4554 (18)
C2—C3	1.389 (2)	C7—N2	1.2891 (17)
C2—H2	0.9300	C7—C8	1.5254 (18)
C3—C4	1.388 (2)	C8—O1	1.2165 (17)
C3—H3	0.9300	C8—N1	1.3594 (17)
C4—C5	1.384 (2)	N1—H1	0.8593
C4—H4	0.9300	N2—N2ⁱ	1.404 (2)

C2—C1—N1	127.63 (12)	C6—C5—H5	120.6
C2—C1—C6	122.16 (13)	C5—C6—C1	119.53 (12)
N1—C1—C6	110.21 (11)	C5—C6—C7	134.43 (12)
C1—C2—C3	117.17 (13)	C1—C6—C7	106.04 (11)
C1—C2—H2	121.4	N2—C7—C6	134.34 (12)
C3—C2—H2	121.4	N2—C7—C8	118.92 (12)
C4—C3—C2	121.72 (14)	C6—C7—C8	106.71 (10)
C4—C3—H3	119.1	O1—C8—N1	126.85 (12)
C2—C3—H3	119.1	O1—C8—C7	127.86 (12)
C5—C4—C3	120.64 (14)	N1—C8—C7	105.29 (11)
C5—C4—H4	119.7	C8—N1—C1	111.72 (10)
C3—C4—H4	119.7	C8—N1—H1	124.1
C4—C5—C6	118.75 (13)	C1—N1—H1	124.2
C4—C5—H5	120.6	C7—N2—N2ⁱ	111.89 (14)

N1—C1—C2—C3	−178.92 (14)	C5—C6—C7—C8	−177.99 (15)
C6—C1—C2—C3	1.3 (2)	C1—C6—C7—C8	1.50 (14)
C1—C2—C3—C4	0.0 (2)	N2—C7—C8—O1	−2.8 (2)
C2—C3—C4—C5	−1.1 (3)	C6—C7—C8—O1	178.67 (13)
C3—C4—C5—C6	0.9 (2)	N2—C7—C8—N1	176.85 (12)
C4—C5—C6—C1	0.3 (2)	C6—C7—C8—N1	−1.65 (14)
C4—C5—C6—C7	179.71 (15)	O1—C8—N1—C1	−179.13 (13)
C2—C1—C6—C5	−1.4 (2)	C7—C8—N1—C1	1.18 (14)
N1—C1—C6—C5	178.74 (12)	C2—C1—N1—C8	179.94 (13)
C2—C1—C6—C7	178.98 (12)	C6—C1—N1—C8	−0.26 (15)
N1—C1—C6—C7	−0.83 (14)	C6—C7—N2—N2ⁱ	0.1 (2)
C5—C6—C7—N2	3.8 (3)	C8—C7—N2—N2ⁱ	−177.92 (13)
C1—C6—C7—N2	−176.67 (15)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱⁱ	0.86	2.13	2.8951 (17)	148

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.13	2.8951 (17)	148

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

Acknowledgements

The authors thank the Priority Academic Program Development of Jiangsu Higher Education Institutions and the National Disciplining and Cultivating Key of Physics and Chemistry in Yangzhou University (070304) for financial support of this work.

References

Ali, S. & Alam, M. (1994). Arch. Pharm. Res. 17, 131–133. CrossRef PubMed CAS Google Scholar
Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hoz, A. D. L., Ortiz, A. D. & Moreno, A. (2004). Curr. Org. Chem. 8, 903–918. CrossRef Google Scholar
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doi:10.1107/S1600536814011805

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(3Z)-3-[(Z)-2-(2-Oxoindolin-3-yl­­idene)hydrazin-1-yl­­idene]indolin-2-one 0.17-hydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(3Z)-3-[(Z)-2-(2-Oxoindolin-3-ylidene)hydrazin-1-ylidene]indolin-2-one 0.17-hydrate