Crystal structure of 1-((1E)-{(E)-2-[(2-hydroxy­naphthalen-1-yl)methyl­idene]hydrazin-1-yl­idene}meth­yl)naphthalen-2-ol

Abstract

The complete mol­ecule of the title compound, C₂₂H₁₆N₂O₂, is generated by a crystallographic inversion centre at the mid-point of the central N—N bond. Two intra­molecular O—H⋯N hydrogen bonds occur.

Related literature  

For general background to Schiff base derivatives, see: Hoshino (1998 ▸); Kalaivani et al. (2013 ▸); Vijayan et al. (2014 ▸).

Experimental  

Crystal data  

• C₂₂H₁₆N₂O₂

• M _r = 340.37

• Monoclinic,

• a = 8.5680 (7) Å

• b = 6.1020 (5) Å

• c = 15.9870 (6) Å

• β = 91.191 (5)°

• V = 835.65 (10) ų

• Z = 2

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 293 K

• 0.22 × 0.20 × 0.18 mm

Data collection  

• Bruker SMART APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T _min = 0.981, T _max = 0.984

• 1907 measured reflections

• 1907 independent reflections

• 1859 reflections with I > 2σ(I)

Refinement  

• R[F ² > 2σ(F ²)] = 0.007

• wR(F ²) = 0.019

• S = 1.03

• 1907 reflections

• 122 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.02 e Å⁻³

• Δρ_min = −0.08 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▸); cell refinement: SAINT (Bruker, 2008 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▸).

Supplementary Material

CCDC reference: 1401958

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O1H1N1	0.98	1.67(1)	2.5671(3)	151(1)

supplementary crystallographic information

S1. Comment

Schiff bases are important ligands, as moderate electron donors with a chelating structure and control the behaviour of metal ions in a diverse range of applications (Hoshino, 1998). Dithiocarbazate compounds are an important class of Schiff bases which can be easily obtained by condensation of dithiocarbazides with aldehydes or ketones. In particular hydrazone containing naphthalene ring compounds have drawn much attention because of their biological activities such as DNA/BSA binding affinities and anticancer activities in vitro (Kalaivani et al., 2013; Vijayan et al., 2014).

The ORTEP plot of the molecule is shown in Fig.1. The title compound (I), crystallized in the monoclinic spacegroup P2₁/n with half molecule in the asymmetric unit. Pair of molecules related by an crystallographic inversion centre generate another half of the molecule.

S2. Experimental

The title compound was obtained by the reaction of S-benzyldithiocarbazate and 2-Hydroxy-1-napthaldehyde in boiling ethanol. The unexpected formation of the hydrazone was probably due to the decomposition of S-benzyldithiocarbazate in solution resulting in the formation of hydrazine, which then reacted with 2-hydroxy-1-napthaldehyde to form the corresponding hydrazone. The dithiocarbazates are known to decompose on heating.

S3. Refinement

All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were located geometrically (aromatic C—H 0.95 Å, secondary alkane C—H 0.99 Å, tertiary alkane C—H 1.0 Å) and refined using a riding model with the isotropic displacement parameters fixed at U_iso= 1.2 times U_eq of the parent carbon for all of the hydrogen atoms.

Figures

Fig. 1.

The molecular structure of the title compound, showing displacement ellipsoids drawn at 50% probability level.

Crystal data

C22H16N2O2	F(000) = 356
Mr = 340.37	Dx = 1.353 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1859 reflections
a = 8.5680 (7) Å	θ = 2.6–27.5°
b = 6.1020 (5) Å	µ = 0.09 mm−1
c = 15.9870 (6) Å	T = 293 K
β = 91.191 (5)°	Block, yellow
V = 835.65 (10) Å3	0.22 × 0.20 × 0.18 mm
Z = 2

Data collection

Bruker SMART APEXII CCD diffractometer	1907 independent reflections
Radiation source: fine-focus sealed tube	1859 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.0000
ω and φ scans	θmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −11→11
Tmin = 0.981, Tmax = 0.984	k = 0→7
1907 measured reflections	l = 0→20

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)] = 0.007	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.019	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.008P)2where P = (Fo2 + 2Fc2)/3
1907 reflections	(Δ/σ)max = 0.001
122 parameters	Δρmax = 0.02 e Å−3
1 restraint	Δρmin = −0.08 e Å−3

Special details

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
C1	0.37033 (2)	0.02490 (3)	0.395255 (11)	0.03120 (4)
C2	0.32482 (2)	−0.16485 (3)	0.350605 (13)	0.03653 (5)
H2	0.2610	−0.2683	0.3755	0.044*
C3	0.37391 (2)	−0.19647 (3)	0.271551 (13)	0.03672 (5)
H3	0.3450	−0.3240	0.2434	0.044*
C4	0.46786 (2)	−0.04107 (3)	0.230675 (12)	0.03129 (5)
C5	0.51123 (3)	−0.06977 (4)	0.146509 (13)	0.04195 (5)
H5	0.4815	−0.1967	0.1182	0.050*
C6	0.59566 (3)	0.08510 (5)	0.106276 (13)	0.04842 (6)
H6	0.6213	0.0654	0.0505	0.058*
C7	0.64395 (3)	0.27462 (5)	0.149184 (13)	0.04576 (6)
H7	0.7021	0.3802	0.1217	0.055*
C8	0.60616 (2)	0.30547 (4)	0.231137 (12)	0.03661 (5)
H8	0.6408	0.4310	0.2588	0.044*
C9	0.51573 (2)	0.15099 (3)	0.274652 (11)	0.02726 (4)
C10	0.46705 (2)	0.18089 (3)	0.359484 (10)	0.02658 (4)
C11	0.51614 (2)	0.37178 (3)	0.406697 (11)	0.02991 (4)
H11	0.5827	0.4727	0.3824	0.036*
N1	0.46961 (2)	0.40510 (3)	0.481933 (10)	0.03414 (4)
O1	0.31470 (2)	0.04548 (3)	0.472921 (9)	0.04471 (5)
H1	0.3596 (5)	0.1824 (7)	0.4943 (2)	0.0995 (13)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.03470 (9)	0.03336 (10)	0.02553 (9)	0.00099 (8)	0.00052 (7)	−0.00058 (7)
C2	0.03940 (11)	0.03200 (10)	0.03805 (11)	−0.00574 (8)	−0.00259 (8)	0.00167 (8)
C3	0.03929 (11)	0.03106 (10)	0.03943 (11)	0.00132 (8)	−0.00822 (8)	−0.00859 (8)
C4	0.02942 (9)	0.03540 (10)	0.02889 (9)	0.00595 (8)	−0.00317 (7)	−0.00776 (8)
C5	0.04097 (11)	0.05126 (13)	0.03346 (11)	0.00604 (10)	−0.00287 (8)	−0.01694 (9)
C6	0.04610 (12)	0.07303 (17)	0.02636 (10)	0.00235 (12)	0.00672 (9)	−0.01219 (10)
C7	0.04615 (12)	0.06073 (15)	0.03086 (10)	−0.00308 (11)	0.01184 (9)	−0.00236 (10)
C8	0.03867 (10)	0.04315 (12)	0.02823 (10)	−0.00353 (9)	0.00582 (8)	−0.00574 (8)
C9	0.02591 (8)	0.03176 (9)	0.02405 (8)	0.00337 (7)	−0.00108 (6)	−0.00519 (7)
C10	0.02861 (9)	0.02830 (9)	0.02281 (8)	0.00107 (7)	−0.00030 (6)	−0.00319 (7)
C11	0.03341 (9)	0.03091 (10)	0.02545 (9)	−0.00130 (7)	0.00150 (7)	−0.00289 (7)
N1	0.04353 (9)	0.03257 (9)	0.02637 (8)	−0.00328 (7)	0.00204 (7)	−0.00689 (7)
O1	0.05713 (10)	0.04698 (10)	0.03052 (8)	−0.01041 (8)	0.01283 (7)	−0.00151 (7)

Geometric parameters (Å, º)

C1—O1	1.3451 (2)	C6—H6	0.9300
C1—C10	1.3927 (3)	C7—C8	1.3691 (3)
C1—C2	1.4109 (3)	C7—H7	0.9300
C2—C3	1.3541 (3)	C8—C9	1.4125 (3)
C2—H2	0.9300	C8—H8	0.9300
C3—C4	1.4129 (3)	C9—C10	1.4388 (2)
C3—H3	0.9300	C10—C11	1.4458 (3)
C4—C5	1.4142 (3)	C11—N1	1.2911 (2)
C4—C9	1.4226 (3)	C11—H11	0.9300
C5—C6	1.3600 (4)	N1—N1i	1.3906 (3)
C5—H5	0.9300	O1—H1	0.978 (4)
C6—C7	1.4026 (4)
O1—C1—C10	122.721 (18)	C8—C7—C6	120.54 (2)
O1—C1—C2	116.367 (18)	C8—C7—H7	119.7
C10—C1—C2	120.911 (18)	C6—C7—H7	119.7
C3—C2—C1	120.079 (19)	C7—C8—C9	121.51 (2)
C3—C2—H2	120.0	C7—C8—H8	119.2
C1—C2—H2	120.0	C9—C8—H8	119.2
C2—C3—C4	121.809 (19)	C8—C9—C4	117.502 (17)
C2—C3—H3	119.1	C8—C9—C10	123.528 (18)
C4—C3—H3	119.1	C4—C9—C10	118.951 (18)
C3—C4—C5	121.360 (19)	C1—C10—C9	119.145 (17)
C3—C4—C9	119.045 (17)	C1—C10—C11	120.359 (17)
C5—C4—C9	119.570 (19)	C9—C10—C11	120.491 (17)
C6—C5—C4	121.12 (2)	N1—C11—C10	121.408 (18)
C6—C5—H5	119.4	N1—C11—H11	119.3
C4—C5—H5	119.4	C10—C11—H11	119.3
C5—C6—C7	119.739 (19)	C11—N1—N1i	113.45 (2)
C5—C6—H6	120.1	C1—O1—H1	104.9 (2)
C7—C6—H6	120.1
O1—C1—C2—C3	179.043 (18)	C3—C4—C9—C10	0.06 (3)
C10—C1—C2—C3	−0.64 (3)	C5—C4—C9—C10	178.266 (17)
C1—C2—C3—C4	−1.51 (3)	O1—C1—C10—C9	−177.234 (17)
C2—C3—C4—C5	−176.393 (19)	C2—C1—C10—C9	2.43 (3)
C2—C3—C4—C9	1.78 (3)	O1—C1—C10—C11	1.96 (3)
C3—C4—C5—C6	176.95 (2)	C2—C1—C10—C11	−178.377 (17)
C9—C4—C5—C6	−1.21 (3)	C8—C9—C10—C1	176.247 (18)
C4—C5—C6—C7	1.46 (4)	C4—C9—C10—C1	−2.11 (3)
C5—C6—C7—C8	−0.31 (4)	C8—C9—C10—C11	−2.94 (3)
C6—C7—C8—C9	−1.12 (4)	C4—C9—C10—C11	178.703 (16)
C7—C8—C9—C4	1.33 (3)	C1—C10—C11—N1	−1.45 (3)
C7—C8—C9—C10	−177.044 (19)	C9—C10—C11—N1	177.730 (17)
C3—C4—C9—C8	−178.391 (18)	C10—C11—N1—N1i	179.073 (19)
C5—C4—C9—C8	−0.19 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.98	1.67 (1)	2.5671 (3)	151 (1)