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The whole mol­ecule of the title compound, C19H14N4O2, is essentially planar, with a highly conjugated π system. In the crystal, the mol­ecules are packed as chains along the [011] direction connected by O—H...N intermolecular hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100007988/na1478sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100007988/na1478Isup2.hkl
Contains datablock I

CCDC reference: 150352

Comment top

Schiff-base compounds having extensively conjugated π-electron systems have been reported to display second harmonic generations (Messier et al., 1991; Zyss, 1994). As part of our work in search and study of new materials for nonlinear optical application, we report the crystal structure of the title compound, (I). \sch

Bond lengths and angles observed in this structure agree well with the related structures (Lu et al., 1995, 1997). The diazafluorene substituent does not show relevant distortion from planarity and from C2 symmetry. The whole molecule is essentially planar. The C—N bond lengths in the hydrazone moiety are short compared with those observed in related compound, p-dimethylaminobenzaldehyde 4,5-diaza-9-fluorenylidene hydrazone monohydrate (Lu et al., 1995). This indicates that the π-conjugation along the central hydrazone chain is higher in the present compound. The phenyl group is in anti-periplanar orientation with respect to the N4—C12 bond.

While substitution at the phenyl C13 is angularly symmetric, C12—C13—C18 = 120.5 (2) and C12—C13—C14 = 120.0 (2)°, substitution at the diazafluorenyl C11 shows quite a relevant angular asymmetry; the C1—C11—N3 = 133.1 (2)° angle being larger than C10—C11—N3, 120.8 (2)°. This asymmetry seems to be caused by the tendency of the central hydrazone system to be coplanar with that of the fluorenyl due to π-conjugation, and steric hindrance involving the C2—H group with N4 [C2···N4 = 3.004 (4), H2···N4 = 2.53 Å] and C9—H with N3 [C9···N3 = 3.054 (3), H9···N3 = 2.90 Å]. The asymmetry of the exocyclic angles at C17 [C16—C17—O2 = 116.2 (2) and C18—C17—O2 = 124.4 (2)°] is caused by the tendency the methoxy group has to be coplanar with the phenyl ring as usually found in anisoles. This tendency can be justified by some degree of conjugation between O and phenyl which is shown by some shortening of the Car—O = 1.367 (3) Å bond (Domiano et al., 1979). Some hindrance occurs between one of the methyl H atoms with that bound to C18: H19C···H18 = 2.15 Å. The same kind of asymmetry is observed for the exocyclic angles at C16 [C17—C16—O1 = 117.2 (2) and C15—C16—O1 = 123.6 (2)°] which is common whith phenols, the C16—O1 bond being 1.358 (3) and the H1···H15 contact 2.30 Å.

The dihedral angles formed by the planes of the diazafluorene group and the phenyl ring with the central hydrazone (N3, N4, C12) bridge are 4.6 (2) and 3.0 (2)° and 7.29 (5)° between each other. In the crystal, the molecules are packed as chains along the [011] direction connected by O—H···N intermolecular hydrogen bonds.

Experimental top

The synthesis of the compound was carried out by reaction of 3-methoxy-4-hydroxybenzaldehyde and 4,5-diazafluorene-9-hydrazine in ethanol solution under reflux for 5 h. Single crystals were obtained by recrystallization from ethanol.

Refinement top

Collection of intensity data was as described by Shanmuga Sundara Raj et al. (1999). The Friedel pairs were not included in the refinement.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures top
[Figure 1] Fig. 1. The structure of title compound showing 50% probability displacement ellipsoids and the atom-numbering scheme.
3-Methoxy-4-hydroxyl-benzaldehyde 4,5-Diaza-9-fluorenylidenehydrazone top
Crystal data top
C19H14N4O2Dx = 1.371 Mg m3
Mr = 330.34Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21Cell parameters from 5698 reflections
a = 7.5130 (2) Åθ = 1.5–28.3°
b = 26.9091 (5) ŵ = 0.09 mm1
c = 7.9141 (1) ÅT = 293 K
V = 1599.98 (6) Å3Slab, yellow
Z = 40.38 × 0.30 × 0.12 mm
F(000) = 688
Data collection top
Siemens SMART CCD area detector
diffractometer
1577 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.082
Graphite monochromatorθmax = 28.3°, θmin = 1.5°
Detector resolution: 8.33 pixels mm-1h = 910
ω scansk = 3435
10894 measured reflectionsl = 106
2115 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.093 w = 1/[σ2(Fo2) + (0.0474P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.93(Δ/σ)max < 0.001
2115 reflectionsΔρmax = 0.18 e Å3
227 parametersΔρmin = 0.17 e Å3
1 restraintExtinction correction: SHELXTL (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0096 (18)
Crystal data top
C19H14N4O2V = 1599.98 (6) Å3
Mr = 330.34Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 7.5130 (2) ŵ = 0.09 mm1
b = 26.9091 (5) ÅT = 293 K
c = 7.9141 (1) Å0.38 × 0.30 × 0.12 mm
Data collection top
Siemens SMART CCD area detector
diffractometer
1577 reflections with I > 2σ(I)
10894 measured reflectionsRint = 0.082
2115 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0411 restraint
wR(F2) = 0.093H-atom parameters constrained
S = 0.93Δρmax = 0.18 e Å3
2115 reflectionsΔρmin = 0.17 e Å3
227 parameters
Special details top

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
xyzUiso*/Ueq
O10.7711 (2)0.43423 (6)0.4619 (3)0.0499 (5)
H10.80810.41770.54140.075*
O20.6694 (2)0.49751 (6)0.2260 (2)0.0512 (5)
N10.6434 (3)0.80233 (8)0.0038 (3)0.0445 (5)
N20.7414 (3)0.87917 (7)0.2684 (3)0.0440 (5)
N30.8335 (3)0.71907 (7)0.5134 (3)0.0389 (5)
N40.8097 (3)0.66955 (7)0.4617 (3)0.0404 (5)
C10.7257 (3)0.74481 (8)0.2208 (3)0.0334 (5)
C20.6917 (3)0.70404 (9)0.1185 (4)0.0434 (6)
H20.70850.67170.15710.052*
C30.6319 (4)0.71351 (10)0.0425 (4)0.0494 (7)
H30.60600.68720.11460.059*
C40.6100 (4)0.76198 (10)0.0983 (4)0.0493 (7)
H40.56960.76680.20810.059*
C50.7009 (3)0.79257 (8)0.1516 (3)0.0342 (5)
C60.7472 (3)0.82960 (8)0.2821 (3)0.0336 (5)
C70.7863 (4)0.90388 (9)0.4103 (4)0.0524 (7)
H70.78420.93840.40590.063*
C80.8350 (3)0.88232 (9)0.5610 (4)0.0486 (6)
H80.86240.90200.65420.058*
C90.8426 (3)0.83119 (9)0.5722 (4)0.0420 (6)
H90.87600.81540.67170.050*
C100.7984 (3)0.80459 (8)0.4293 (3)0.0332 (5)
C110.7893 (3)0.75057 (8)0.3973 (3)0.0332 (5)
C120.8597 (3)0.63852 (8)0.5753 (3)0.0370 (5)
H120.90870.65000.67590.044*
C130.8398 (3)0.58524 (8)0.5469 (3)0.0358 (5)
C140.8966 (3)0.55167 (8)0.6688 (3)0.0425 (6)
H140.94850.56290.76840.051*
C150.8747 (3)0.50077 (9)0.6398 (3)0.0431 (6)
H150.91340.47830.72100.052*
C160.7975 (3)0.48325 (8)0.4942 (3)0.0376 (6)
C170.7430 (3)0.51746 (9)0.3687 (3)0.0372 (6)
C180.7640 (3)0.56748 (8)0.3968 (3)0.0362 (5)
H180.72730.59000.31470.043*
C190.6391 (4)0.53099 (10)0.0897 (4)0.0563 (7)
H19A0.58730.51330.00350.084*
H19B0.75010.54540.05510.084*
H19C0.55950.55680.12570.084*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0745 (12)0.0243 (9)0.0509 (12)0.0000 (7)0.0045 (10)0.0032 (8)
O20.0747 (12)0.0345 (10)0.0444 (12)0.0015 (8)0.0094 (10)0.0049 (8)
N10.0568 (12)0.0438 (12)0.0329 (13)0.0005 (9)0.0045 (11)0.0055 (9)
N20.0592 (12)0.0269 (11)0.0460 (14)0.0008 (8)0.0061 (11)0.0048 (9)
N30.0561 (11)0.0250 (10)0.0356 (13)0.0008 (8)0.0094 (10)0.0022 (8)
N40.0584 (12)0.0258 (10)0.0369 (12)0.0009 (8)0.0112 (10)0.0008 (8)
C10.0384 (11)0.0305 (12)0.0313 (13)0.0004 (9)0.0009 (11)0.0018 (10)
C20.0562 (15)0.0331 (13)0.0408 (16)0.0012 (11)0.0119 (12)0.0045 (11)
C30.0645 (15)0.0420 (15)0.0417 (16)0.0029 (12)0.0118 (13)0.0098 (12)
C40.0582 (16)0.0557 (16)0.0340 (15)0.0003 (12)0.0088 (13)0.0018 (13)
C50.0386 (12)0.0328 (12)0.0314 (14)0.0001 (9)0.0001 (11)0.0027 (10)
C60.0413 (12)0.0272 (11)0.0324 (13)0.0002 (9)0.0008 (11)0.0017 (9)
C70.0736 (17)0.0245 (12)0.0589 (19)0.0007 (12)0.0112 (15)0.0026 (13)
C80.0654 (16)0.0342 (14)0.0461 (16)0.0011 (12)0.0107 (15)0.0079 (13)
C90.0556 (14)0.0337 (13)0.0367 (15)0.0008 (11)0.0072 (12)0.0025 (11)
C100.0408 (11)0.0272 (11)0.0317 (14)0.0008 (9)0.0032 (10)0.0007 (10)
C110.0392 (12)0.0293 (11)0.0312 (13)0.0006 (9)0.0019 (11)0.0004 (10)
C120.0469 (13)0.0317 (12)0.0325 (13)0.0013 (9)0.0062 (11)0.0013 (11)
C130.0435 (12)0.0270 (11)0.0367 (14)0.0009 (9)0.0054 (11)0.0039 (10)
C140.0544 (14)0.0349 (13)0.0381 (14)0.0038 (10)0.0104 (12)0.0090 (11)
C150.0510 (13)0.0312 (12)0.0471 (16)0.0020 (10)0.0044 (13)0.0159 (11)
C160.0447 (12)0.0246 (12)0.0435 (16)0.0001 (9)0.0054 (12)0.0066 (11)
C170.0433 (13)0.0315 (13)0.0368 (14)0.0003 (9)0.0003 (12)0.0008 (10)
C180.0474 (13)0.0270 (11)0.0342 (13)0.0023 (9)0.0053 (12)0.0045 (10)
C190.0717 (17)0.0542 (17)0.0429 (17)0.0089 (14)0.0183 (15)0.0053 (14)
Geometric parameters (Å, º) top
O1—C161.358 (3)C7—C81.376 (4)
O1—H10.8200C7—H70.9300
O2—C171.367 (3)C8—C91.380 (3)
O2—C191.424 (3)C8—H80.9300
N1—C51.329 (3)C9—C101.379 (4)
N1—C41.342 (3)C9—H90.9300
N2—C61.339 (3)C10—C111.477 (3)
N2—C71.348 (4)C12—C131.459 (3)
N3—C111.294 (3)C12—H120.9300
N3—N41.405 (3)C13—C141.389 (3)
N4—C121.283 (3)C13—C181.402 (3)
C1—C21.387 (3)C14—C151.398 (3)
C1—C51.409 (3)C14—H140.9300
C1—C111.484 (3)C15—C161.373 (4)
C2—C31.375 (4)C15—H150.9300
C2—H20.9300C16—C171.415 (3)
C3—C41.387 (4)C17—C181.374 (3)
C3—H30.9300C18—H180.9300
C4—H40.9300C19—H19A0.9600
C5—C61.477 (3)C19—H19B0.9600
C6—C101.399 (3)C19—H19C0.9600
C16—O1—H1109.5C9—C10—C6120.0 (2)
C17—O2—C19116.2 (2)C9—C10—C11131.5 (2)
C5—N1—C4114.6 (2)C6—C10—C11108.6 (2)
C6—N2—C7114.6 (2)N3—C11—C10120.8 (2)
C11—N3—N4112.5 (2)N3—C11—C1133.1 (2)
C12—N4—N3112.1 (2)C10—C11—C1106.2 (2)
C2—C1—C5118.0 (2)N4—C12—C13120.1 (2)
C2—C1—C11133.7 (2)N4—C12—H12119.9
C5—C1—C11108.3 (2)C13—C12—H12119.9
C3—C2—C1117.0 (2)C14—C13—C18119.5 (2)
C3—C2—H2121.5C14—C13—C12120.1 (2)
C1—C2—H2121.5C18—C13—C12120.5 (2)
C2—C3—C4120.5 (3)C13—C14—C15119.1 (2)
C2—C3—H3119.7C13—C14—H14120.4
C4—C3—H3119.7C15—C14—H14120.4
N1—C4—C3124.1 (3)C16—C15—C14121.6 (2)
N1—C4—H4117.9C16—C15—H15119.2
C3—C4—H4117.9C14—C15—H15119.2
N1—C5—C1125.6 (2)O1—C16—C15123.6 (2)
N1—C5—C6126.2 (2)O1—C16—C17117.2 (2)
C1—C5—C6108.2 (2)C15—C16—C17119.2 (2)
N2—C6—C10123.7 (2)O2—C17—C18124.4 (2)
N2—C6—C5127.5 (2)O2—C17—C16116.2 (2)
C10—C6—C5108.81 (18)C18—C17—C16119.4 (2)
N2—C7—C8125.5 (2)C17—C18—C13121.2 (2)
N2—C7—H7117.2C17—C18—H18119.4
C8—C7—H7117.2C13—C18—H18119.4
C7—C8—C9119.1 (3)O2—C19—H19A109.5
C7—C8—H8120.4O2—C19—H19B109.5
C9—C8—H8120.4H19A—C19—H19B109.5
C10—C9—C8117.1 (3)O2—C19—H19C109.5
C10—C9—H9121.5H19A—C19—H19C109.5
C8—C9—H9121.5H19B—C19—H19C109.5
C11—N3—N4—C12177.7 (2)N4—N3—C11—C12.6 (4)
C5—C1—C2—C31.5 (3)C9—C10—C11—N32.8 (4)
C11—C1—C2—C3179.8 (3)C6—C10—C11—N3178.7 (2)
C1—C2—C3—C40.9 (4)C9—C10—C11—C1177.5 (3)
C5—N1—C4—C30.1 (4)C6—C10—C11—C11.0 (3)
C2—C3—C4—N10.1 (4)C2—C1—C11—N30.1 (5)
C4—N1—C5—C10.8 (4)C5—C1—C11—N3178.9 (2)
C4—N1—C5—C6179.8 (2)C2—C1—C11—C10179.5 (3)
C2—C1—C5—N11.6 (3)C5—C1—C11—C100.7 (2)
C11—C1—C5—N1179.4 (2)N3—N4—C12—C13178.0 (2)
C2—C1—C5—C6179.3 (2)N4—C12—C13—C14179.0 (2)
C11—C1—C5—C60.2 (2)N4—C12—C13—C180.9 (4)
C7—N2—C6—C101.1 (4)C18—C13—C14—C150.8 (4)
C7—N2—C6—C5178.1 (2)C12—C13—C14—C15179.4 (2)
N1—C5—C6—N20.5 (4)C13—C14—C15—C160.4 (4)
C1—C5—C6—N2179.7 (2)C14—C15—C16—O1179.0 (2)
N1—C5—C6—C10178.8 (2)C14—C15—C16—C171.7 (4)
C1—C5—C6—C100.4 (3)C19—O2—C17—C1810.0 (4)
C6—N2—C7—C80.2 (4)C19—O2—C17—C16170.9 (2)
N2—C7—C8—C91.0 (5)O1—C16—C17—O20.3 (3)
C7—C8—C9—C100.6 (4)C15—C16—C17—O2179.1 (2)
C8—C9—C10—C60.5 (4)O1—C16—C17—C18178.9 (2)
C8—C9—C10—C11178.9 (2)C15—C16—C17—C181.7 (4)
N2—C6—C10—C91.5 (4)O2—C17—C18—C13179.6 (2)
C5—C6—C10—C9177.8 (2)C16—C17—C18—C130.5 (3)
N2—C6—C10—C11179.8 (2)C14—C13—C18—C170.7 (4)
C5—C6—C10—C110.8 (3)C12—C13—C18—C17179.4 (2)
N4—N3—C11—C10177.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N2i0.822.112.844 (3)150
Symmetry code: (i) x+3/2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC19H14N4O2
Mr330.34
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)293
a, b, c (Å)7.5130 (2), 26.9091 (5), 7.9141 (1)
V3)1599.98 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.38 × 0.30 × 0.12
Data collection
DiffractometerSiemens SMART CCD area detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
10894, 2115, 1577
Rint0.082
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.093, 0.93
No. of reflections2115
No. of parameters227
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.18, 0.17

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Selected geometric parameters (Å, º) top
O2—C191.424 (3)N3—N41.405 (3)
N3—C111.294 (3)N4—C121.283 (3)
C17—O2—C19116.2 (2)C12—N4—N3112.1 (2)
C11—N3—N4112.5 (2)N4—C12—C13120.1 (2)
N4—N3—C11—C10177.8 (2)N4—C12—C13—C14179.0 (2)
N3—N4—C12—C13178.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N2i0.822.112.844 (3)150
Symmetry code: (i) x+3/2, y1/2, z+1/2.
 

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