3-Hydr­oxy-N′-phenyl­naphthalene-2-carbohydrazide

The dihedral angle between the naphthalene and benzene planes in the title compound, C₁₈H₁₄N₂O₃, is 4.3 (2)°. The mol­ecular conformation is characterized by an N—H...O hydrogen bond and the crystal packing is stabilized by N—H...O and O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.054
• wR factor = 0.117
• Data-to-parameter ratio = 9.0

checkCIF/PLATON results

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Alert level C
REFNR01_ALERT_3_C  Ratio of reflections to parameters is < 10 for a
            centrosymmetric structure
            sine(theta)/lambda                0.6516
            Proportion of unique data used    0.5516
            Ratio reflections to parameters   9.0192
PLAT088_ALERT_3_C Poor Data / Parameter Ratio ....................       9.02

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Metallacrowns are a new class of metallamacrocycles, which have gained increasing attention over the past decade because of their unique properties (Alexiou et al., 2002; Gaynor et al., 2002; Lah & Pecoraro, 1989; Lehaire et al., 2002; Liu et al., 2001; Saalfrank et al., 2001). These metallacrowns exhibit selective recognition of cations and anions (Saalfrank et al., 2001; Lehaire et al., 2002), can display intramolecular magnetic exchange interactions (Liu et al., 2001), and can be used as building blocks for twodimensional or three-dimensional network structures (Gaynor et al., 2002; Lah & Pecoraro, 1989; Lehaire et al., 2002). The ability to control the generation of metallacrowns with different nuclear numbers, desired structures, and properties is still a substantial challenge. We now report structure of a designed pentadentate ligand.

The molecular structure of the title compound is illustrated in Fig.1. The bond lengths and bond angles are within normal ranges. The dihedral angel between the naphthalene and benzene planes is 4.3 (2)°. The molecular conformation is characterized by an N—H···O hydrogen bond and the crystal packing is stabilized by N—H···O and O—H···O hydrogen bonds.

Related literature

For related literature, see: Alexiou et al. (2002); Gaynor et al. (2002); Lah & Pecoraro (1989); Lehaire et al. (2002); Liu et al. (2001); Saalfrank et al. (2001).

S2. Experimental

Benzoic acid anhydride (13.56 g, 60.0 mmol) and 3-hydroxynaphthalene-2-carbohydrazide (11.3 g, 56.0 mmol) were added to 120 ml of chloroform with an external ice-water bath. The reaction mixture was slowly warmed to room temperature and stirred for 8 h. After leaving overnight in a refrigerator, the resulting white precipitate was filtered off and rinsed with chloroform and diethyl ether (yield: 95.3%; m.p. 492–496 K). Calculatedd for C₁₈H₁₄N₂O₃: C 70.58, H 4.61, N 9.15%; found: C 70.24, H 4.75, N 9.02%.

S3. Refinement

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms (C—H = 0.93%A; N—H = 0.86 Å; O—H = 0.82 Å) and U_iso(H) values weren set equal to 1.2 U_eq(C, N) and 1.5U_eq(O).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998).

Figures

Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.

3-Hydroxy-N'-phenylnaphthalene-2-carbohydrazide

Crystal data

C18H14N2O3	F(000) = 640
Mr = 306.31	Dx = 1.389 Mg m^−3
Monoclinic, P21/c	Melting point = 219–223 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 4.8473 (10) Å	Cell parameters from 8325 reflections
b = 33.907 (7) Å	θ = 6.0–27.6°
c = 8.9148 (18) Å	µ = 0.10 mm^−1
β = 91.61 (3)°	T = 273 K
V = 1464.6 (5) Å^3	Block, colourless
Z = 4	0.57 × 0.39 × 0.31 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	3401 independent reflections
Radiation source: fine-focus sealed tube	2414 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.069
Detector resolution: 0 pixels mm^-1	θmax = 27.6°, θmin = 3.3°
ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 1998)	k = −44→44
Tmin = 0.936, Tmax = 0.976	l = −11→11
7743 measured reflections

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0502P)^2 + 0.5358P] where P = (Fo^2 + 2Fc^2)/3
3401 reflections	(Δ/σ)max = 0.001
208 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.18 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	0.3553 (9)	0.97519 (9)	0.8154 (4)	0.0902 (12)
H1B	0.4486	0.9957	0.8639	0.108*
C2	0.0784 (6)	0.91469 (9)	0.6775 (4)	0.0685 (9)
H2B	−0.0180	0.8943	0.6301	0.082*
C3	0.0072 (7)	0.95336 (11)	0.6456 (4)	0.0884 (11)
H3B	−0.1360	0.9589	0.5773	0.106*
C4	0.1484 (9)	0.98325 (10)	0.7151 (5)	0.0905 (12)
H4A	0.1025	1.0093	0.6935	0.109*
C5	0.4286 (7)	0.93649 (8)	0.8464 (4)	0.0707 (9)
H5A	0.5734	0.9311	0.9140	0.085*
C6	0.2887 (5)	0.90608 (7)	0.7777 (3)	0.0464 (7)
C7	0.3757 (5)	0.86499 (7)	0.8103 (3)	0.0435 (6)
C8	0.1220 (5)	0.76940 (7)	0.7606 (3)	0.0403 (6)
C9	0.2169 (5)	0.72870 (7)	0.7964 (3)	0.0385 (6)
C10	0.5067 (5)	0.68088 (7)	0.9256 (3)	0.0469 (7)
H10A	0.6467	0.6752	0.9957	0.056*
C11	0.4322 (5)	0.71903 (7)	0.9015 (3)	0.0417 (6)
C12	0.0889 (5)	0.69841 (7)	0.7208 (3)	0.0454 (7)
H12A	−0.0537	0.7044	0.6527	0.054*
C13	0.1627 (5)	0.65876 (7)	0.7414 (3)	0.0431 (6)
C14	0.3760 (5)	0.64988 (7)	0.8464 (3)	0.0457 (7)
C15	0.4518 (6)	0.60999 (8)	0.8667 (4)	0.0624 (8)
H15A	0.5928	0.6036	0.9353	0.075*
C16	0.0314 (6)	0.62774 (8)	0.6613 (3)	0.0576 (8)
H16A	−0.1112	0.6333	0.5927	0.069*
C17	0.1121 (6)	0.58983 (8)	0.6841 (3)	0.0638 (8)
H17A	0.0261	0.5696	0.6299	0.077*
C18	0.3226 (6)	0.58093 (8)	0.7879 (4)	0.0673 (9)
H18A	0.3750	0.5548	0.8033	0.081*
O1	0.6144 (3)	0.85645 (5)	0.8467 (2)	0.0635 (6)
O2	−0.0689 (4)	0.77662 (5)	0.6712 (2)	0.0607 (6)
O3	0.5609 (3)	0.74934 (5)	0.9766 (2)	0.0548 (5)
H3A	0.6758	0.7404	1.0367	0.082*
N1	0.1807 (4)	0.83749 (6)	0.7983 (2)	0.0471 (6)
H1A	0.0145	0.8436	0.7710	0.056*
N2	0.2512 (4)	0.79894 (6)	0.8305 (2)	0.0474 (6)
H2A	0.3797	0.7940	0.8963	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.135 (3)	0.045 (2)	0.090 (3)	−0.012 (2)	0.001 (3)	−0.0035 (19)
C2	0.0663 (19)	0.0537 (18)	0.085 (2)	−0.0009 (15)	−0.0127 (18)	0.0181 (16)
C3	0.086 (2)	0.068 (2)	0.110 (3)	0.012 (2)	−0.015 (2)	0.032 (2)
C4	0.119 (3)	0.054 (2)	0.100 (3)	0.021 (2)	0.020 (3)	0.020 (2)
C5	0.083 (2)	0.0514 (19)	0.077 (2)	−0.0081 (17)	−0.0127 (18)	0.0005 (16)
C6	0.0409 (15)	0.0427 (15)	0.0557 (18)	0.0002 (12)	0.0008 (14)	0.0035 (13)
C7	0.0352 (15)	0.0459 (15)	0.0488 (16)	−0.0003 (13)	−0.0062 (12)	−0.0019 (12)
C8	0.0356 (13)	0.0444 (15)	0.0404 (15)	−0.0007 (12)	−0.0094 (13)	−0.0014 (12)
C9	0.0350 (13)	0.0407 (14)	0.0394 (15)	0.0005 (11)	−0.0060 (12)	0.0016 (12)
C10	0.0439 (14)	0.0448 (16)	0.0511 (16)	0.0045 (12)	−0.0141 (13)	0.0051 (13)
C11	0.0411 (14)	0.0410 (15)	0.0424 (15)	−0.0030 (12)	−0.0070 (12)	−0.0020 (12)
C12	0.0426 (15)	0.0472 (16)	0.0457 (16)	−0.0019 (12)	−0.0101 (13)	0.0019 (13)
C13	0.0447 (15)	0.0402 (15)	0.0443 (15)	−0.0039 (12)	0.0011 (13)	−0.0016 (12)
C14	0.0426 (15)	0.0427 (15)	0.0518 (16)	0.0031 (12)	−0.0001 (13)	0.0031 (13)
C15	0.0633 (19)	0.0454 (17)	0.078 (2)	0.0051 (14)	−0.0099 (16)	0.0045 (15)
C16	0.0643 (19)	0.0491 (18)	0.0589 (18)	−0.0085 (14)	−0.0060 (15)	−0.0029 (14)
C17	0.072 (2)	0.0476 (18)	0.072 (2)	−0.0113 (15)	0.0003 (18)	−0.0118 (15)
C18	0.074 (2)	0.0413 (16)	0.087 (2)	0.0031 (16)	0.0009 (19)	−0.0037 (16)
O1	0.0357 (10)	0.0544 (12)	0.0995 (17)	0.0012 (9)	−0.0154 (10)	0.0020 (11)
O2	0.0610 (12)	0.0479 (11)	0.0709 (14)	0.0019 (9)	−0.0377 (11)	−0.0008 (9)
O3	0.0550 (11)	0.0443 (10)	0.0634 (12)	0.0041 (9)	−0.0303 (10)	0.0009 (9)
N1	0.0340 (11)	0.0389 (12)	0.0673 (15)	0.0032 (10)	−0.0172 (10)	0.0033 (11)
N2	0.0442 (12)	0.0371 (12)	0.0593 (14)	0.0040 (10)	−0.0249 (11)	0.0021 (11)

Geometric parameters (Å, º)

C1—C4	1.352 (5)	C10—C14	1.407 (3)
C1—C5	1.385 (4)	C10—H10A	0.9300
C1—H1B	0.9300	C11—O3	1.368 (3)
C2—C6	1.368 (4)	C12—C13	1.402 (3)
C2—C3	1.383 (4)	C12—H12A	0.9300
C2—H2B	0.9300	C13—C14	1.408 (4)
C3—C4	1.362 (5)	C13—C16	1.413 (4)
C3—H3B	0.9300	C14—C15	1.412 (4)
C4—H4A	0.9300	C15—C18	1.353 (4)
C5—C6	1.369 (4)	C15—H15A	0.9300
C5—H5A	0.9300	C16—C17	1.357 (4)
C6—C7	1.482 (3)	C16—H16A	0.9300
C7—O1	1.227 (3)	C17—C18	1.392 (4)
C7—N1	1.330 (3)	C17—H17A	0.9300
C8—O2	1.229 (3)	C18—H18A	0.9300
C8—N2	1.327 (3)	O3—H3A	0.8200
C8—C9	1.487 (3)	N1—N2	1.379 (3)
C9—C12	1.367 (3)	N1—H1A	0.8600
C9—C11	1.421 (3)	N2—H2A	0.8600
C10—C11	1.358 (3)
C4—C1—C5	120.3 (3)	C10—C11—C9	120.7 (2)
C4—C1—H1B	119.8	O3—C11—C9	117.8 (2)
C5—C1—H1B	119.8	C9—C12—C13	123.0 (2)
C6—C2—C3	120.9 (3)	C9—C12—H12A	118.5
C6—C2—H2B	119.6	C13—C12—H12A	118.5
C3—C2—H2B	119.6	C12—C13—C14	118.2 (2)
C4—C3—C2	119.5 (3)	C12—C13—C16	122.6 (2)
C4—C3—H3B	120.2	C14—C13—C16	119.3 (2)
C2—C3—H3B	120.2	C10—C14—C13	119.1 (2)
C1—C4—C3	120.3 (3)	C10—C14—C15	122.7 (2)
C1—C4—H4A	119.9	C13—C14—C15	118.3 (2)
C3—C4—H4A	119.9	C18—C15—C14	121.1 (3)
C6—C5—C1	120.2 (3)	C18—C15—H15A	119.5
C6—C5—H5A	119.9	C14—C15—H15A	119.5
C1—C5—H5A	119.9	C17—C16—C13	120.4 (3)
C2—C6—C5	118.8 (3)	C17—C16—H16A	119.8
C2—C6—C7	122.1 (2)	C13—C16—H16A	119.8
C5—C6—C7	119.0 (2)	C16—C17—C18	120.5 (3)
O1—C7—N1	121.2 (2)	C16—C17—H17A	119.7
O1—C7—C6	122.3 (2)	C18—C17—H17A	119.7
N1—C7—C6	116.4 (2)	C15—C18—C17	120.5 (3)
O2—C8—N2	119.4 (2)	C15—C18—H18A	119.8
O2—C8—C9	123.1 (2)	C17—C18—H18A	119.8
N2—C8—C9	117.4 (2)	C11—O3—H3A	109.5
C12—C9—C11	117.8 (2)	C7—N1—N2	118.4 (2)
C12—C9—C8	117.3 (2)	C7—N1—H1A	120.8
C11—C9—C8	124.9 (2)	N2—N1—H1A	120.8
C11—C10—C14	121.2 (2)	C8—N2—N1	120.4 (2)
C11—C10—H10A	119.4	C8—N2—H2A	119.8
C14—C10—H10A	119.4	N1—N2—H2A	119.8
C10—C11—O3	121.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1^i	0.86	2.12	2.864 (3)	145
N2—H2A···O3	0.86	1.88	2.582 (3)	138
O3—H3A···O2^ii	0.82	1.79	2.613 (3)	177

Symmetry codes: (i) x−1, y, z; (ii) x+1, −y+3/2, z+1/2.