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

Abstract

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.

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,

• a = 24.8699 (18) Å

• c = 5.6603 (8) Å

• V = 3031.9 (5) ų

• 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[F ² > 2σ(F ²)] = 0.039

• wR(F ²) = 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

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 ▶).

Supplementary Material

CCDC reference: 1004532

Additional supporting information: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

1. Comment

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.

2. Experimental

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).

3. Refinement

After their location in a difference map, all H atoms were fixed geometrically at ideal positions and allowed to ride on the parent C atoms, with C — H distances of 0.93 (aromaticl CH), O — H distances of 0.84 and N— H distances of 0.86, and with U_iso(H) values of 1.2U_eq(C).

Figures

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.

Crystal data

C16H10N4O2·0.17H2O	F(000) = 1369
Mr = 308.30	Dx = 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

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

Refinement

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(Fo2) + (0.0545P)2 + 2.5765P] where P = (Fo2 + 2Fc2)/3
1547 reflections	(Δ/σ)max < 0.001
103 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.18 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

	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)

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)

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.