N′-Isopropyl­idene-6-meth­oxy-2-naphthohydrazide

The geometric parameters of the title compound, C₁₅H₁₆N₂O₂, are in the usual ranges. The mol­ecule is almost planar; only the torsion angles about the N—N bond [164.11 (15)°] and the C—C bond between the naphthyl and the amide group [C—C—C—O = − 157.24 (15)°] differ significantly from 0 or 180°. The crystal packing is characterized by chains of mol­ecules connected by N—H...O hydrogen bonds running along the c axis.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.031
• wR factor = 0.087
• Data-to-parameter ratio = 8.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.66 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.30 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C12

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.53
           From the CIF: _reflns_number_total               1539
           Count of symmetry unique reflns         1543
           Completeness (_total/calc)             99.74%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 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

Hydrazides and the corresponding Schiff bases are useful precursors in the synthesis of several heterocyclic systems. Some substituted hydrazides are reported to exhibit carcinostatic activity against several types of tumors and also possess antimicrobial activity. Some substituted hydrazides and their Schiff bases are reported to exhibit carcinostatic activity against several types of tumors and also possess antimicrobial activity. It is also used as an intermediate in many pharmaceutically important compounds. A new Schiff base of the hydrazide, C₁₅H₁₆N₂O₂, was accidentally formed, when the synthesized hydrazide was recrystallized using a 1:1 mixture of acetone and dimethyl formamide. The crystal structure of the newly formed compound is reported.

Geometric parameters of the title compound (Fig. 1) are in the usual ranges. The crystal packing is characterized by chains of molecules connected by N—H···O hydrogen bonds running along the c axis (Fig. 2).

Related literature

For related structures, see: Narayana et al. (2007); Yathirajan, Sarojini et al. (2007); Yathirajan, Narayana et al. (2007); Sarojini et al. (2007). For related literature, see: Misra et al. (1981); Agarwal et al. (1983); Varma et al. (1986); Singh & Dash (1988); Liu et al. (2006); Flack (1983); Narayana, Ashalatha et al. (2005); Narayana, Vijayaraj et al. (2005).

S2. Experimental

Hydrazine hydrate (100%) (2 ml) was added to methyl 6-methoxy-2-naphthoate (4.3 g, 0.02 mol) in 20 ml e thanol and refluxed for 4 h on a water bath. The precipitate formed was collected and recrystallized from ethyl acetate. X-ray quality crystals were obtained from a mixture of acetone and DMF(1:1) and the compound obtained was a Schiff base of the hydrazide with acetone, C₁₅H₁₆N₂O₂ (m.p.: 445–447 K). Analysis for C₁₅H₁₆N₂O₂: Found (Calculated): C 70.20 (70.29), H 6.22 (6.29), N 10.87% (10.93%).

S3. Refinement

H atoms were found in a difference map, but those bonded to C were refined using a riding model with C—H = 0.95Å and U_iso(H) = 1.2U_eq(C) [C—H = 0.98Å and U_iso(H) = 1.5U_eq(C) for the methyl groups, which were allowed to rotate but not to tip]. The amino H atom was freely refined. In the absence of anomalous scatterers, the Flack [(1983). Acta Cryst. A39, 876–881] parameter is meaningless and therefore, Friedel pairs had been merged prior to refinement.

Computing details

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003) and XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. Perspective view of the title compound with the atom numbering; displacement ellipsoids are at the 50% probability level.
	Fig. 2. Packing diagram of the title compound; hydrogen bonds are shown as dashed lines.
	Fig. 3. the formation of the title compound.

N'-Isopropylidene-6-methoxy-2-naphthohydrazide

Crystal data

C15H16N2O2	F(000) = 544
Mr = 256.30	Dx = 1.270 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 8050 reflections
a = 24.037 (3) Å	θ = 3.6–27.2°
b = 5.9957 (4) Å	µ = 0.09 mm^−1
c = 9.3014 (10) Å	T = 173 K
β = 91.673 (9)°	Rod, colourless
V = 1339.9 (2) Å^3	0.38 × 0.24 × 0.24 mm
Z = 4

Data collection

Stoe IPDS II two-circle diffractometer	1506 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.037
Graphite monochromator	θmax = 27.5°, θmin = 3.5°
ω scans	h = −27→30
8435 measured reflections	k = −7→7
1539 independent reflections	l = −12→12

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.087	w = 1/[σ^2(Fo^2) + (0.0635P)^2 + 0.1264P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
1539 reflections	Δρmax = 0.24 e Å^−3
180 parameters	Δρmin = −0.15 e Å^−3
2 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.014 (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
N1	0.61518 (6)	0.6094 (2)	0.48733 (13)	0.0305 (3)
H1	0.6241 (8)	0.630 (3)	0.398 (2)	0.033 (5)*
N2	0.56452 (7)	0.6965 (3)	0.53277 (15)	0.0438 (4)
O1	0.62273 (6)	0.3857 (2)	0.68512 (13)	0.0409 (3)
O2	0.93004 (5)	0.1401 (2)	0.23424 (16)	0.0483 (4)
C1	0.69319 (6)	0.3547 (2)	0.51132 (14)	0.0274 (3)
C2	0.72496 (6)	0.4663 (2)	0.41240 (16)	0.0282 (3)
H2	0.7124	0.6055	0.3751	0.034*
C3	0.77597 (6)	0.3761 (2)	0.36589 (15)	0.0276 (3)
C4	0.80881 (7)	0.4902 (3)	0.26298 (18)	0.0338 (3)
H4	0.7960	0.6276	0.2234	0.041*
C5	0.85828 (7)	0.4036 (3)	0.22131 (19)	0.0373 (4)
H5	0.8792	0.4789	0.1510	0.045*
C6	0.87878 (7)	0.2009 (3)	0.28263 (18)	0.0363 (4)
C7	0.84830 (7)	0.0842 (3)	0.38110 (17)	0.0344 (3)
H7	0.8622	−0.0514	0.4208	0.041*
C8	0.79556 (6)	0.1691 (2)	0.42301 (15)	0.0284 (3)
C9	0.76168 (7)	0.0543 (2)	0.52314 (16)	0.0315 (3)
H9	0.7735	−0.0858	0.5607	0.038*
C10	0.71221 (7)	0.1449 (2)	0.56560 (15)	0.0308 (3)
H10	0.6903	0.0663	0.6323	0.037*
C11	0.64049 (6)	0.4497 (3)	0.56888 (14)	0.0291 (3)
C12	0.54904 (7)	0.8804 (3)	0.47282 (16)	0.0365 (4)
C13	0.49405 (11)	0.9730 (6)	0.5149 (3)	0.0729 (9)
H13A	0.4769	0.8719	0.5835	0.109*
H13B	0.4697	0.9880	0.4291	0.109*
H13C	0.4996	1.1196	0.5596	0.109*
C14	0.58033 (8)	1.0116 (3)	0.3649 (2)	0.0425 (4)
H14A	0.6202	1.0062	0.3895	0.064*
H14B	0.5676	1.1669	0.3655	0.064*
H14C	0.5736	0.9478	0.2690	0.064*
C15	0.95677 (9)	−0.0466 (4)	0.3035 (3)	0.0538 (5)
H15A	0.9593	−0.0207	0.4075	0.081*
H15B	0.9942	−0.0649	0.2664	0.081*
H15C	0.9350	−0.1820	0.2838	0.081*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0336 (7)	0.0371 (7)	0.0210 (6)	0.0077 (5)	0.0070 (5)	0.0023 (5)
N2	0.0427 (8)	0.0602 (10)	0.0294 (6)	0.0208 (7)	0.0142 (6)	0.0113 (6)
O1	0.0504 (7)	0.0507 (7)	0.0218 (5)	0.0072 (5)	0.0062 (4)	0.0086 (5)
O2	0.0358 (7)	0.0496 (8)	0.0601 (8)	0.0133 (6)	0.0107 (6)	0.0061 (6)
C1	0.0316 (7)	0.0270 (7)	0.0235 (6)	−0.0004 (5)	−0.0019 (5)	−0.0013 (5)
C2	0.0310 (7)	0.0249 (7)	0.0287 (7)	0.0011 (5)	−0.0019 (5)	0.0027 (5)
C3	0.0276 (7)	0.0251 (7)	0.0301 (7)	−0.0007 (5)	−0.0019 (5)	0.0011 (5)
C4	0.0310 (7)	0.0307 (7)	0.0395 (8)	0.0011 (6)	0.0007 (6)	0.0088 (6)
C5	0.0306 (8)	0.0377 (8)	0.0438 (9)	−0.0010 (6)	0.0038 (6)	0.0070 (6)
C6	0.0317 (8)	0.0357 (8)	0.0414 (8)	0.0051 (6)	0.0013 (6)	−0.0001 (7)
C7	0.0358 (8)	0.0283 (7)	0.0392 (8)	0.0064 (6)	0.0006 (6)	−0.0008 (6)
C8	0.0317 (8)	0.0238 (6)	0.0294 (7)	0.0005 (5)	−0.0028 (5)	−0.0013 (5)
C9	0.0393 (8)	0.0225 (6)	0.0326 (8)	0.0016 (5)	−0.0030 (6)	0.0031 (5)
C10	0.0390 (8)	0.0271 (7)	0.0261 (6)	−0.0018 (5)	0.0005 (5)	0.0029 (5)
C11	0.0356 (7)	0.0321 (7)	0.0196 (6)	−0.0007 (6)	0.0007 (5)	−0.0010 (5)
C12	0.0372 (8)	0.0485 (9)	0.0241 (7)	0.0111 (7)	0.0017 (5)	−0.0021 (6)
C13	0.0629 (15)	0.099 (2)	0.0581 (13)	0.0480 (14)	0.0258 (11)	0.0284 (13)
C14	0.0404 (8)	0.0315 (8)	0.0555 (10)	0.0012 (6)	−0.0009 (8)	0.0041 (7)
C15	0.0437 (11)	0.0486 (11)	0.0692 (13)	0.0189 (8)	0.0049 (9)	0.0008 (10)

Geometric parameters (Å, º)

N1—C11	1.355 (2)	C6—C7	1.380 (2)
N1—N2	1.4017 (18)	C7—C8	1.431 (2)
N1—H1	0.88 (2)	C7—H7	0.9500
N2—C12	1.286 (2)	C8—C9	1.431 (2)
O1—C11	1.2352 (19)	C9—C10	1.376 (2)
O2—C6	1.3733 (19)	C9—H9	0.9500
O2—C15	1.434 (2)	C10—H10	0.9500
C1—C2	1.385 (2)	C12—C14	1.496 (3)
C1—C10	1.426 (2)	C12—C13	1.496 (2)
C1—C11	1.502 (2)	C13—H13A	0.9800
C2—C3	1.419 (2)	C13—H13B	0.9800
C2—H2	0.9500	C13—H13C	0.9800
C3—C8	1.4245 (18)	C14—H14A	0.9800
C3—C4	1.432 (2)	C14—H14B	0.9800
C4—C5	1.364 (2)	C14—H14C	0.9800
C4—H4	0.9500	C15—H15A	0.9800
C5—C6	1.424 (2)	C15—H15B	0.9800
C5—H5	0.9500	C15—H15C	0.9800
C11—N1—N2	118.32 (12)	C10—C9—H9	119.7
C11—N1—H1	121.1 (13)	C8—C9—H9	119.7
N2—N1—H1	118.2 (13)	C9—C10—C1	121.18 (13)
C12—N2—N1	115.58 (13)	C9—C10—H10	119.4
C6—O2—C15	117.03 (15)	C1—C10—H10	119.4
C2—C1—C10	118.95 (14)	O1—C11—N1	123.28 (15)
C2—C1—C11	122.73 (13)	O1—C11—C1	120.72 (14)
C10—C1—C11	118.26 (12)	N1—C11—C1	115.98 (12)
C1—C2—C3	121.09 (13)	N2—C12—C14	126.69 (15)
C1—C2—H2	119.5	N2—C12—C13	116.84 (16)
C3—C2—H2	119.5	C14—C12—C13	116.47 (16)
C2—C3—C8	119.83 (12)	C12—C13—H13A	109.5
C2—C3—C4	121.29 (13)	C12—C13—H13B	109.5
C8—C3—C4	118.87 (13)	H13A—C13—H13B	109.5
C5—C4—C3	120.66 (14)	C12—C13—H13C	109.5
C5—C4—H4	119.7	H13A—C13—H13C	109.5
C3—C4—H4	119.7	H13B—C13—H13C	109.5
C4—C5—C6	120.35 (15)	C12—C14—H14A	109.5
C4—C5—H5	119.8	C12—C14—H14B	109.5
C6—C5—H5	119.8	H14A—C14—H14B	109.5
O2—C6—C7	125.58 (15)	C12—C14—H14C	109.5
O2—C6—C5	113.48 (14)	H14A—C14—H14C	109.5
C7—C6—C5	120.94 (14)	H14B—C14—H14C	109.5
C6—C7—C8	119.49 (14)	O2—C15—H15A	109.5
C6—C7—H7	120.3	O2—C15—H15B	109.5
C8—C7—H7	120.3	H15A—C15—H15B	109.5
C3—C8—C7	119.61 (13)	O2—C15—H15C	109.5
C3—C8—C9	118.25 (13)	H15A—C15—H15C	109.5
C7—C8—C9	122.13 (13)	H15B—C15—H15C	109.5
C10—C9—C8	120.66 (13)
C11—N1—N2—C12	164.11 (15)	C4—C3—C8—C9	−178.54 (15)
C10—C1—C2—C3	−0.6 (2)	C6—C7—C8—C3	−1.9 (2)
C11—C1—C2—C3	176.83 (12)	C6—C7—C8—C9	179.15 (14)
C1—C2—C3—C8	−1.0 (2)	C3—C8—C9—C10	−1.6 (2)
C1—C2—C3—C4	179.63 (15)	C7—C8—C9—C10	177.36 (13)
C2—C3—C4—C5	178.74 (14)	C8—C9—C10—C1	0.1 (2)
C8—C3—C4—C5	−0.7 (2)	C2—C1—C10—C9	1.0 (2)
C3—C4—C5—C6	−1.7 (3)	C11—C1—C10—C9	−176.49 (13)
C15—O2—C6—C7	−7.3 (3)	N2—N1—C11—O1	−4.0 (2)
C15—O2—C6—C5	172.53 (17)	N2—N1—C11—C1	177.15 (14)
C4—C5—C6—O2	−177.47 (15)	C2—C1—C11—O1	−157.24 (15)
C4—C5—C6—C7	2.3 (3)	C10—C1—C11—O1	20.2 (2)
O2—C6—C7—C8	179.27 (14)	C2—C1—C11—N1	21.6 (2)
C5—C6—C7—C8	−0.5 (2)	C10—C1—C11—N1	−160.97 (13)
C2—C3—C8—C7	−176.96 (13)	N1—N2—C12—C14	−2.2 (3)
C4—C3—C8—C7	2.4 (2)	N1—N2—C12—C13	177.68 (19)
C2—C3—C8—C9	2.07 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.88 (2)	1.98 (2)	2.8222 (17)	161.3 (19)

Symmetry code: (i) x, −y+1, z−1/2.