Methyl 2-{[(E)-8-oxo-5,8-dihydro­quinolin-5-yl­idene]hydrazino}benzoate

The non-H atoms in the title compound, C₁₇H₁₃N₃O₃, are almost coplanar, a conformation stabilized by intra­molecular N—H...O and C—H...O inter­actions. A supra­molecular chain mediated by C—H...O inter­actions is found in the crystal structure and these pack side-by-side into layers. The layers are consolidated into the crystal structure by further C—H...O and C—H...N inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 98 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.062
• wR factor = 0.132
• Data-to-parameter ratio = 11.1

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.798     1.000
            Tmin(prime) and Tmax expected:      0.963     0.995
            RR(prime) =      0.825
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.82
PLAT414_ALERT_2_C Short Intra D-H..H-X       H3     ..  H3N     ..       1.92 Ang.

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.995
            Tmax scaled      0.995 Tmin scaled      0.794

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The title compound, C₁₇H₁₃O₃N₃ (I) was prepared during an on-going study of the coordination chemistry of organotin(IV) 5-[(E)-2-((aryl)-1-diazenyl)quinolin-8-olates] (Basu Baul, Mizar, Lyčka et al. (2006); Basu Baul, Mizar, Song et al. (2006).

The crystal structure shows (I), (Fig. 1), to exist as the phenylhydrazone tautomer rather than in the azo form (Sawicki, 1957). The non-H atoms in (I) are effectivlely co-planar and the dihedral angle between the N1/C1—C9 and C10—C15 ring planes is 1.33 (10)°. An intramolecular N3—H···O2 hydrogen bond contributes to the stability of the observed conformation; an intramolecular C12—H···O3 interaction is also noted. Intermolecular C8—H···O1 interactions lead to the formation of supramolecular chains aligned along the b axis (Fig. 2 & Table 1). These stack side-by-side to form layers and interactions between these layers are of the type C—H···O and C—H···N and involve the methyl groups (Fig. 3).

A very closely related molecule characterized in the tautomeric form shown in the Scheme has been observed previously in a dimeric dibenzyltin structure (Basu Baul et al., 2005).

Related literature

For related literature, see: Sawicki (1957); Basu Baul, Mizar, Lyčka et al. (2006); Basu Baul, Mizar, Song et al. (2006). For a related structure, see: Basu Baul et al. (2005).

S2. Experimental

Methyl anthranilate (5.0 g, 33.1 mmol) was mixed with HCl (11 ml) and water (11 ml) and digested in a water bath for 1 h. The hydrochloride was cooled to 278 K and diazotized with ice-cold aqueous NaNO₂ solution (5.0 g, 72.45 mmol, 25 ml). A cold solution of quinolin-8-ol (5.0 g, 34.4 mmol), previously dissolved in methanol solution (70 ml), was then added to the cold diazonium salt solution with vigorous stirring maintaining the temperature around 273 K. A light-orange colour developed and the stirring was continued for 1 h. A saturated solution of potassium acetate was then added to neutralize the hydrochloric acid, thereupon a deep-red precipitate appeared and stirring was continued for an additional hour. The reaction mixture was kept overnight in a refrigerator followed by 2 h at room temperature. The precipitate was filtered, washed several times with water to remove soluble starting materials, and then dried in air. The crude product was washed with hexane to remove any tarry materials, dried in vacuo and recrystallization from a methanol solution afforded orange microcrystalline (I) in 53.6% (5.67 g) yield. Red crystals (m.p. 434–435 K) of (I) suitable for an X-ray crystal structure determination were obtained from the slow evaporation of an ethylacetate/methanol (v/v, 1:1) solution. Elemental analysis, found: C 66.40, H 4.23, N 13.56%; C₁₇H₁₃O₃N₃ requires C 66.44, H 4.26, N 13.67%.

S3. Refinement

All H atoms were included in the riding-model approximation, with N—H = 0.88 Å and C—H = 0.95 to 0.98 Å, and with U_iso(H) = 1.2U_eq(C, N) or 1.5U_eq(methyl-C).

Computing details

Data collection: CrystalClear (Rigaku Americas Corporation, 2005); cell refinement: CrystalClear (Rigaku Americas Corporation, 2005); data reduction: CrystalClear (Rigaku Americas Corporation, 2005); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 50% probability level (arbitrary spheres for the H atoms).
	Fig. 2. View of the supramolecular chain in (I) mediated by hydrogen bonds, shown as orange-dashed lines. Colour code: red (oxygen), blue (nitrogen), grey (carbon) and green (hydrogen).
	Fig. 3. Unit cell packing diagram in (I) highlighting the stacking of layers. Hydrogen bonds are shown as orange-dashed lines. Colour code in Fig. 2.

Methyl 2-{[(E)-8-oxo-5,8-dihydroquinolin-5-ylidene]hydrazino}benzoate

Crystal data

C17H13N3O3	F(000) = 1280
Mr = 307.30	Dx = 1.525 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 7939 reflections
a = 26.695 (3) Å	θ = 2.6–29.6°
b = 8.2513 (9) Å	µ = 0.11 mm^−1
c = 13.5873 (16) Å	T = 98 K
β = 116.589 (5)°	Prism, red
V = 2676.3 (5) Å^3	0.35 × 0.13 × 0.05 mm
Z = 8

Data collection

Rigaku AFC12K/SATURN724 diffractometer	2329 independent reflections
Radiation source: fine-focus sealed tube	2165 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ω scans	θmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = 0→31
Tmin = 0.798, Tmax = 1	k = −9→9
4109 measured reflections	l = −16→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.132	H-atom parameters constrained
S = 1.36	w = 1/[σ^2(Fo^2) + (0.0357P)^2 + 4.7653P] where P = (Fo^2 + 2Fc^2)/3
2329 reflections	(Δ/σ)max < 0.001
209 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.23 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
O1	0.34053 (7)	1.3572 (2)	−0.08723 (14)	0.0274 (4)
O2	0.61943 (7)	1.0578 (2)	0.29517 (13)	0.0204 (4)
O3	0.69937 (6)	0.9308 (2)	0.39955 (13)	0.0206 (4)
N1	0.30057 (8)	1.0510 (3)	−0.15349 (16)	0.0214 (5)
N2	0.48060 (8)	0.8551 (3)	0.09386 (16)	0.0196 (5)
N3	0.53313 (8)	0.8769 (3)	0.16930 (16)	0.0215 (5)
H3N	0.5460	0.9756	0.1903	0.026*
C1	0.37145 (10)	1.2430 (3)	−0.04737 (19)	0.0203 (5)
C2	0.42878 (10)	1.2680 (3)	0.0373 (2)	0.0252 (6)
H2	0.4414	1.3755	0.0604	0.030*
C3	0.46412 (10)	1.1451 (3)	0.0834 (2)	0.0254 (6)
H3	0.5011	1.1680	0.1378	0.030*
C4	0.44828 (9)	0.9807 (3)	0.05351 (19)	0.0189 (5)
C5	0.39130 (10)	0.9464 (3)	−0.02835 (18)	0.0187 (5)
C6	0.37130 (10)	0.7905 (3)	−0.05822 (19)	0.0214 (5)
H6	0.3953	0.7003	−0.0262	0.026*
C7	0.31712 (10)	0.7666 (3)	−0.13366 (19)	0.0232 (6)
H7	0.3028	0.6601	−0.1546	0.028*
C8	0.28330 (10)	0.9001 (3)	−0.17926 (19)	0.0232 (6)
H8	0.2456	0.8822	−0.2320	0.028*
C9	0.35390 (10)	1.0730 (3)	−0.07851 (19)	0.0198 (5)
C10	0.56749 (10)	0.7457 (3)	0.21470 (19)	0.0203 (5)
C11	0.62287 (10)	0.7696 (3)	0.29446 (19)	0.0191 (5)
C12	0.65655 (10)	0.6352 (3)	0.3393 (2)	0.0220 (6)
H12	0.6940	0.6503	0.3941	0.026*
C13	0.63740 (11)	0.4825 (3)	0.3067 (2)	0.0273 (6)
H13	0.6611	0.3919	0.3387	0.033*
C14	0.58308 (11)	0.4604 (3)	0.2267 (2)	0.0317 (6)
H14	0.5697	0.3539	0.2025	0.038*
C15	0.54847 (10)	0.5896 (3)	0.1819 (2)	0.0277 (6)
H15	0.5110	0.5723	0.1279	0.033*
C16	0.64564 (10)	0.9334 (3)	0.32801 (19)	0.0180 (5)
C17	0.72608 (10)	1.0850 (3)	0.4336 (2)	0.0230 (5)
H17A	0.7156	1.1550	0.3691	0.034*
H17B	0.7668	1.0704	0.4703	0.034*
H17C	0.7141	1.1354	0.4849	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0231 (9)	0.0265 (10)	0.0283 (10)	0.0061 (8)	0.0075 (8)	0.0022 (8)
O2	0.0177 (8)	0.0177 (9)	0.0228 (9)	0.0024 (7)	0.0066 (7)	0.0004 (7)
O3	0.0147 (8)	0.0211 (9)	0.0202 (8)	−0.0003 (7)	0.0026 (7)	−0.0005 (7)
N1	0.0138 (10)	0.0327 (12)	0.0159 (10)	0.0013 (9)	0.0050 (8)	−0.0004 (9)
N2	0.0147 (10)	0.0246 (11)	0.0180 (10)	−0.0007 (9)	0.0062 (8)	−0.0007 (9)
N3	0.0143 (10)	0.0199 (11)	0.0247 (11)	−0.0008 (8)	0.0038 (8)	0.0003 (9)
C1	0.0169 (12)	0.0255 (13)	0.0197 (12)	0.0033 (11)	0.0093 (10)	0.0021 (10)
C2	0.0222 (13)	0.0220 (13)	0.0293 (14)	−0.0037 (11)	0.0094 (11)	−0.0024 (11)
C3	0.0173 (12)	0.0280 (14)	0.0235 (13)	−0.0019 (11)	0.0025 (10)	−0.0007 (11)
C4	0.0166 (12)	0.0208 (13)	0.0187 (12)	0.0011 (10)	0.0074 (10)	0.0024 (10)
C5	0.0178 (12)	0.0271 (14)	0.0136 (11)	−0.0016 (10)	0.0091 (10)	−0.0011 (10)
C6	0.0214 (13)	0.0238 (13)	0.0185 (12)	0.0003 (10)	0.0084 (10)	0.0005 (10)
C7	0.0240 (13)	0.0245 (13)	0.0193 (12)	−0.0062 (11)	0.0081 (10)	−0.0032 (10)
C8	0.0174 (12)	0.0335 (15)	0.0176 (12)	−0.0044 (11)	0.0069 (10)	−0.0035 (11)
C9	0.0149 (11)	0.0289 (14)	0.0155 (11)	0.0004 (10)	0.0067 (10)	−0.0009 (10)
C10	0.0173 (12)	0.0225 (13)	0.0207 (12)	0.0001 (10)	0.0081 (10)	0.0028 (10)
C11	0.0170 (12)	0.0215 (13)	0.0189 (11)	0.0003 (10)	0.0082 (10)	0.0006 (10)
C12	0.0190 (12)	0.0235 (14)	0.0212 (12)	0.0023 (10)	0.0069 (10)	0.0024 (10)
C13	0.0250 (14)	0.0199 (13)	0.0321 (14)	0.0040 (11)	0.0085 (12)	0.0050 (11)
C14	0.0273 (14)	0.0191 (13)	0.0420 (16)	−0.0034 (11)	0.0094 (12)	0.0007 (12)
C15	0.0184 (12)	0.0257 (14)	0.0326 (14)	−0.0021 (11)	0.0056 (11)	0.0003 (12)
C16	0.0176 (12)	0.0215 (13)	0.0154 (11)	0.0012 (10)	0.0079 (9)	0.0011 (10)
C17	0.0191 (12)	0.0214 (13)	0.0244 (13)	−0.0048 (10)	0.0061 (10)	−0.0018 (11)

Geometric parameters (Å, º)

O1—C1	1.209 (3)	C6—C7	1.362 (3)
O2—C16	1.210 (3)	C6—H6	0.9500
O3—C16	1.325 (3)	C7—C8	1.382 (4)
O3—C17	1.431 (3)	C7—H7	0.9500
N1—C8	1.320 (3)	C8—H8	0.9500
N1—C9	1.341 (3)	C10—C15	1.383 (4)
N2—N3	1.327 (3)	C10—C11	1.402 (3)
N2—C4	1.302 (3)	C11—C12	1.385 (3)
N3—C10	1.373 (3)	C11—C16	1.468 (3)
N3—H3N	0.8800	C12—C13	1.357 (4)
C1—C2	1.460 (3)	C12—H12	0.9500
C1—C9	1.479 (4)	C13—C14	1.381 (4)
C2—C3	1.335 (4)	C13—H13	0.9500
C2—H2	0.9500	C14—C15	1.363 (4)
C3—C4	1.424 (4)	C14—H14	0.9500
C3—H3	0.9500	C15—H15	0.9500
C4—C5	1.455 (3)	C17—H17A	0.9800
C5—C6	1.383 (4)	C17—H17B	0.9800
C5—C9	1.394 (3)	C17—H17C	0.9800
C16—O3—C17	116.24 (19)	N1—C9—C5	123.7 (2)
C8—N1—C9	117.1 (2)	N1—C9—C1	116.0 (2)
C4—N2—N3	119.3 (2)	C5—C9—C1	120.3 (2)
N2—N3—C10	120.2 (2)	N3—C10—C15	120.9 (2)
N2—N3—H3N	119.9	N3—C10—C11	119.8 (2)
C10—N3—H3N	119.9	C15—C10—C11	119.2 (2)
O1—C1—C2	120.5 (2)	C12—C11—C10	118.7 (2)
O1—C1—C9	123.1 (2)	C12—C11—C16	120.2 (2)
C2—C1—C9	116.4 (2)	C10—C11—C16	121.1 (2)
C3—C2—C1	122.2 (2)	C13—C12—C11	121.6 (2)
C3—C2—H2	118.9	C13—C12—H12	119.2
C1—C2—H2	118.9	C11—C12—H12	119.2
C2—C3—C4	122.2 (2)	C12—C13—C14	119.3 (2)
C2—C3—H3	118.9	C12—C13—H13	120.4
C4—C3—H3	118.9	C14—C13—H13	120.4
N2—C4—C3	125.6 (2)	C15—C14—C13	120.7 (2)
N2—C4—C5	115.8 (2)	C15—C14—H14	119.6
C3—C4—C5	118.6 (2)	C13—C14—H14	119.6
C6—C5—C9	117.1 (2)	C14—C15—C10	120.5 (2)
C6—C5—C4	122.7 (2)	C14—C15—H15	119.8
C9—C5—C4	120.2 (2)	C10—C15—H15	119.8
C7—C6—C5	119.7 (2)	O2—C16—O3	122.8 (2)
C7—C6—H6	120.1	O2—C16—C11	125.2 (2)
C5—C6—H6	120.1	O3—C16—C11	112.0 (2)
C6—C7—C8	118.9 (2)	O3—C17—H17A	109.5
C6—C7—H7	120.6	O3—C17—H17B	109.5
C8—C7—H7	120.6	H17A—C17—H17B	109.5
N1—C8—C7	123.5 (2)	O3—C17—H17C	109.5
N1—C8—H8	118.2	H17A—C17—H17C	109.5
C7—C8—H8	118.2	H17B—C17—H17C	109.5
C4—N2—N3—C10	178.5 (2)	O1—C1—C9—N1	−1.1 (3)
O1—C1—C2—C3	179.9 (2)	C2—C1—C9—N1	177.7 (2)
C9—C1—C2—C3	1.1 (4)	O1—C1—C9—C5	−179.1 (2)
C1—C2—C3—C4	−0.3 (4)	C2—C1—C9—C5	−0.3 (3)
N3—N2—C4—C3	−0.1 (4)	N2—N3—C10—C15	0.9 (4)
N3—N2—C4—C5	−179.75 (19)	N2—N3—C10—C11	−179.9 (2)
C2—C3—C4—N2	179.2 (2)	N3—C10—C11—C12	179.7 (2)
C2—C3—C4—C5	−1.2 (4)	C15—C10—C11—C12	−1.0 (4)
N2—C4—C5—C6	3.1 (3)	N3—C10—C11—C16	−2.1 (3)
C3—C4—C5—C6	−176.5 (2)	C15—C10—C11—C16	177.1 (2)
N2—C4—C5—C9	−178.3 (2)	C10—C11—C12—C13	0.9 (4)
C3—C4—C5—C9	2.0 (3)	C16—C11—C12—C13	−177.3 (2)
C9—C5—C6—C7	0.0 (3)	C11—C12—C13—C14	0.3 (4)
C4—C5—C6—C7	178.5 (2)	C12—C13—C14—C15	−1.3 (4)
C5—C6—C7—C8	0.3 (4)	C13—C14—C15—C10	1.1 (4)
C9—N1—C8—C7	−0.3 (4)	N3—C10—C15—C14	179.3 (3)
C6—C7—C8—N1	−0.2 (4)	C11—C10—C15—C14	0.1 (4)
C8—N1—C9—C5	0.6 (3)	C17—O3—C16—O2	−2.4 (3)
C8—N1—C9—C1	−177.3 (2)	C17—O3—C16—C11	177.35 (19)
C6—C5—C9—N1	−0.5 (3)	C12—C11—C16—O2	−178.7 (2)
C4—C5—C9—N1	−179.1 (2)	C10—C11—C16—O2	3.2 (4)
C6—C5—C9—C1	177.4 (2)	C12—C11—C16—O3	1.6 (3)
C4—C5—C9—C1	−1.2 (3)	C10—C11—C16—O3	−176.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O2	0.88	1.96	2.633 (3)	132
C12—H12···O3	0.95	2.32	2.662 (3)	101
C8—H8···O1^i	0.95	2.51	3.425 (3)	161
C17—H17B···O1^ii	0.98	2.49	3.227 (4)	132
C17—H17C···N1^iii	0.98	2.59	3.379 (3)	138

Symmetry codes: (i) −x+1/2, y−1/2, −z−1/2; (ii) x+1/2, −y+5/2, z+1/2; (iii) −x+1, y, −z+1/2.