Crystal structure of N-hy-droxy-quinoline-2-carboxamide monohydrate.

The title compound, C10H8N2O2·H2O, consists of an N-hy-droxy-quinoline-2-carboxamide mol-ecule in the keto tautomeric form and a water mol-ecule connected through an O-H⋯O hydrogen bond. The N-hy-droxy-quinoline-2-carboxamide mol-ecule has a nearly planar structure [maximum deviation = 0.062 (1) Å] and only the hy-droxy H atom deviates significantly from the mol-ecule plane. In the crystal, π-π stacking between the aromatic rings [inter-centroid distance = 3.887 (1) Å] and inter-molecular O-H⋯O hydrogen bonds organize the crystal components into columns extending along the b-axis direction.

Chemical context

Hydroxamic acids are important bioligands that exhibit enzyme-inhibitory properties (Marmion et al., 2013 ▸) and they have been studied extensively in coordination and bioinorganic chemistry (Ostrowska et al., 2016 ▸; Golenya et al., 2012b ▸; Świątek-Kozłowska et al., 2000 ▸; Dobosz et al., 1999 ▸). They are widely used in the preparation of metallacrowns (Golenya et al., 2012a ▸; Gumienna-Kontecka et al., 2013 ▸; Safyanova et al., 2015 ▸) and as building blocks for synthesis of metal–organic frameworks and coordination polymers (Gumienna-Kontecka et al., 2007 ▸; Golenya et al., 2014 ▸; Pavlishchuk et al., 2010 ▸, 2011 ▸).

N-Hy­droxy­quinoline-2-carboxamide, also known as quinoline-2-hydroxamic acid (QuinHA), has been used for the preparation of various metallacrown complexes (Stemmler et al., 1999 ▸; Trivedi et al., 2014 ▸; Jankolovits et al., 2013 ▸). Presently, the Cambridge Structural Database (Groom et al., 2016 ▸) contains ten entries on coordination compounds based on N-hy­droxy­quinoline-2-carboxamide, nine of which have been reported within the past four years.

Structural information about the title compound is absent in the literature, however, and this will be useful in controlling the purity of the synthesized ligand and metal complexes by powder diffraction. It is well known that the products of such syntheses can be contaminated with impurities that result from hydrolysis or oxidation of the hydroxamic groups to the carb­oxy­lic group. In addition, syntheses of polynuclear complexes are often carried out with various metal-to-ligand ratios, so that in some cases an excessive qu­antity of the hydroxamic ligand can be present in the isolated samples.

Structural commentary

The mol­ecular structure of the title compound is presented in Fig. 1 ▸. It consists of an N-hy­droxy­quinoline-2-carboxamide mol­ecule in the keto tautomeric form {which is supported by the C=O [1.227 (2) Å] and C—N [1.317 (2) Å] bond lengths} and a water mol­ecule. The carbonyl group possesses a Z conformation against the N1 atom of the quinoline moiety and E conformation against the hy­droxy oxygen atom [torsion angles O2—N2—C10—O1 = 0.8 (2)° and N1—C9—C10—O1 −177.33 (14)°]. The N-hy­droxy­quinoline-2-carboxamide mol­ecule has an almost planar structure (non-hydrogen atoms are planar to within 0.03 Å). Only the H atom of the OH group deviates significantly from the mol­ecular plane: the C—N—O—H torsion angle of −75.1 (13)° is defined by the O—H⋯O hydrogen bond between hy­droxy group and the water mol­ecule. The C—N and C—C bond lengths in the quinoline moiety are typical for 2-substituted pyridine derivatives (Moroz et al., 2012 ▸; Strotmeyer et al., 2003 ▸; Krämer & Fritsky, 2000 ▸).

Figure 1

The asymmetric unit of the title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius. The dashed line indicates a hydrogen bond.

Supra­molecular features

In the crystal, mol­ecules form columns along the b axis as a result of the π–π stacking inter­action between parallel quinoline moieties [symmetry operation x, y + 1, z; inter­planar separation 3.420 (1) Å, inter­centroid distance 3.887 (1) Å, displacement 1.846 (1) Å]. These columns are linked pairwise by the O—H⋯O hydrogen bonds (Table 1 ▸) via the bridging water mol­ecules (see Fig. 2 ▸). Each water mol­ecule forms two donor hydrogen bonds [H⋯O1 = 1.85 (2) and 2.15 (2) Å] with the carbonyl oxygen atom O1 and one acceptor hydrogen bond with the O—H group of the hydroxamic function that is the strongest hydrogen bond in the crystal [H⋯O2 = 1.67 (2) Å]. This latter hydrogen bond results in a shortened H⋯H contact between the water and hy­droxy hydrogen atoms [2.05 (3) Å]. The doubled columns are linked by weak N—H⋯π (2.71 Å, 159°) as well as van der Waals inter­actions. Weak inter­molecular C—H⋯O contacts (Table 1 ▸) are also observed in the crystal.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1S—H1SA⋯O1i	0.85 (2)	2.15 (3)	2.9404 (19)	155 (2)
O1S—H1SA⋯O2i	0.85 (2)	2.54 (2)	3.0850 (18)	124 (2)
O1S—H1SB⋯O1ii	0.93 (2)	1.85 (2)	2.7783 (18)	176 (2)
O2—H2⋯O1S	0.97 (2)	1.67 (2)	2.6407 (18)	175 (2)
C3—H3⋯O2iii	0.999 (16)	2.518 (16)	3.493 (2)	165.0 (15)
C4—H4⋯O2iv	0.975 (19)	2.589 (18)	3.273 (2)	127.3 (12)
C5—H5⋯O1S v	0.967 (17)	2.593 (17)	3.547 (2)	169.0 (13)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

Figure 2

A packing diagram of the title compound. Hydrogen bonds (see Table 1 ▸) are indicated by dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

Database survey

A search of the Cambridge Structural Database (Groom et al., 2016 ▸) reveals no crystal structures of isomeric N-hy­droxy­quinoline-carboxamides or their homologues. Two independent studies on the crystal structure of N-hy­droxy­picolinamide have been published recently (Chaiyaveij et al., 2015 ▸; Safyanova et al., 2016 ▸).

Synthesis and crystallization

The title compound was obtained by the reaction of a methanol solution of hy­droxy­amine with a mixture of quinaldic acid and ethyl chloro­formate in dry methyl­ene chloride in the presence of N-methyl­morpholine according to the reported procedure (Trivedi et al., 2014 ▸). Light-yellow crystals suitable for X-ray diffraction were obtained from aqueous solution by slow evaporation at room temperature (yield 76%).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All hydrogen atoms were found from the difference-Fourier maps and refined isotropically.

Table 2

Experimental details

Crystal data
Chemical formula	C10H8N2O2·H2O
M r	206.20
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	21.613 (4), 3.8867 (4), 25.081 (5)
β (°)	115.37 (2)
V (Å3)	1903.7 (6)
Z	8
Radiation type	Mo Kα
μ (mm−1)	0.11
Crystal size (mm)	0.4 × 0.1 × 0.1
Data collection
Diffractometer	Agilent Xcalibur, Sapphire3
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 ▸)
T min, T max	0.730, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7711, 2167, 1387
R int	0.040
(sin θ/λ)max (Å−1)	0.650
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.040, 0.098, 0.97
No. of reflections	2167
No. of parameters	173
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.14, −0.17

Computer programs: CrysAlis PRO (Agilent, 2014 ▸), SHELXS97 and SHELXL97 (Sheldrick, 2008 ▸) and OLEX2 (Dolomanov et al., 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017005618/xu5902sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017005618/xu5902Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989017005618/xu5902Isup3.cml

CCDC reference: 1543825

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

C10H8N2O2·H2O	F(000) = 864
Mr = 206.20	Dx = 1.439 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 21.613 (4) Å	Cell parameters from 1341 reflections
b = 3.8867 (4) Å	θ = 3.8–27.4°
c = 25.081 (5) Å	µ = 0.11 mm−1
β = 115.37 (2)°	T = 298 K
V = 1903.7 (6) Å3	Needle, clear light yellow
Z = 8	0.4 × 0.1 × 0.1 mm

Agilent Xcalibur, Sapphire3 diffractometer	2167 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1387 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
Detector resolution: 16.1827 pixels mm-1	θmax = 27.5°, θmin = 3.3°
ω scans	h = −28→28
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −5→4
Tmin = 0.730, Tmax = 1.000	l = −32→32
7711 measured reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ2(Fo2) + (0.0454P)2] where P = (Fo2 + 2Fc2)/3
2167 reflections	(Δ/σ)max < 0.001
173 parameters	Δρmax = 0.14 e Å−3
0 restraints	Δρmin = −0.17 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

	x	y	z	Uiso*/Ueq
O1	0.32060 (5)	0.1130 (3)	0.55333 (5)	0.0582 (3)
O2	0.27884 (5)	0.3220 (3)	0.63530 (5)	0.0604 (4)
N1	0.46916 (5)	0.5267 (3)	0.65622 (5)	0.0381 (3)
N2	0.34314 (6)	0.3877 (4)	0.63808 (6)	0.0523 (4)
H2A	0.3705 (8)	0.508 (4)	0.6691 (8)	0.060 (5)*
H2	0.2492 (10)	0.479 (5)	0.6052 (10)	0.090*
H1SA	0.2274 (11)	0.899 (6)	0.5506 (10)	0.090*
H1SB	0.1922 (10)	0.628 (5)	0.5141 (10)	0.090*
C1	0.53537 (6)	0.6016 (3)	0.66788 (6)	0.0359 (3)
C2	0.57630 (7)	0.7759 (4)	0.72050 (7)	0.0424 (4)
H2B	0.5567 (7)	0.834 (4)	0.7473 (7)	0.050 (4)*
C3	0.64285 (8)	0.8497 (4)	0.73422 (8)	0.0469 (4)
H3	0.6734 (8)	0.966 (4)	0.7719 (7)	0.060 (5)*
C4	0.67118 (8)	0.7562 (4)	0.69502 (8)	0.0491 (4)
H4	0.7190 (8)	0.810 (4)	0.7053 (7)	0.055 (4)*
C5	0.63321 (8)	0.5923 (4)	0.64395 (8)	0.0476 (4)
H5	0.6504 (8)	0.527 (4)	0.6156 (7)	0.059 (5)*
C6	0.56373 (7)	0.5090 (3)	0.62831 (7)	0.0391 (3)
C7	0.52127 (8)	0.3386 (4)	0.57617 (7)	0.0461 (4)
H7	0.5385 (8)	0.275 (4)	0.5474 (7)	0.058 (5)*
C8	0.45526 (8)	0.2675 (4)	0.56466 (7)	0.0453 (4)
H8	0.4245 (8)	0.161 (4)	0.5306 (7)	0.054 (5)*
C9	0.43182 (7)	0.3633 (3)	0.60679 (6)	0.0380 (3)
C10	0.35991 (7)	0.2754 (4)	0.59651 (7)	0.0409 (4)
O1S	0.20068 (6)	0.7378 (3)	0.54961 (6)	0.0609 (4)

	U11	U22	U33	U12	U13	U23
O1	0.0489 (6)	0.0750 (8)	0.0461 (7)	−0.0163 (5)	0.0158 (6)	−0.0158 (6)
O2	0.0396 (6)	0.0884 (9)	0.0583 (8)	−0.0119 (5)	0.0259 (6)	0.0006 (6)
N1	0.0342 (6)	0.0446 (7)	0.0360 (7)	−0.0008 (5)	0.0153 (5)	0.0006 (6)
N2	0.0363 (7)	0.0751 (10)	0.0480 (9)	−0.0148 (7)	0.0206 (7)	−0.0130 (8)
C1	0.0326 (7)	0.0384 (7)	0.0380 (8)	0.0029 (6)	0.0163 (6)	0.0065 (6)
C2	0.0378 (8)	0.0501 (9)	0.0412 (9)	−0.0006 (7)	0.0187 (7)	0.0014 (7)
C3	0.0376 (8)	0.0518 (9)	0.0488 (11)	−0.0046 (7)	0.0162 (8)	0.0013 (8)
C4	0.0363 (8)	0.0525 (10)	0.0616 (12)	0.0015 (7)	0.0240 (8)	0.0078 (8)
C5	0.0442 (9)	0.0510 (9)	0.0588 (11)	0.0057 (7)	0.0328 (9)	0.0065 (8)
C6	0.0395 (7)	0.0395 (8)	0.0430 (9)	0.0062 (6)	0.0221 (7)	0.0062 (7)
C7	0.0522 (9)	0.0505 (9)	0.0438 (10)	0.0055 (7)	0.0282 (8)	0.0008 (7)
C8	0.0481 (9)	0.0490 (9)	0.0385 (9)	−0.0015 (7)	0.0182 (8)	−0.0058 (7)
C9	0.0374 (7)	0.0387 (7)	0.0371 (9)	0.0003 (6)	0.0154 (7)	0.0025 (6)
C10	0.0391 (8)	0.0453 (8)	0.0357 (9)	−0.0023 (6)	0.0135 (7)	0.0020 (7)
O1S	0.0549 (7)	0.0724 (8)	0.0607 (8)	−0.0107 (6)	0.0298 (7)	−0.0151 (7)

O1—C10	1.2266 (17)	C4—H4	0.974 (16)
O2—N2	1.3851 (15)	C4—C5	1.349 (2)
O2—H2	0.97 (2)	C5—H5	0.966 (16)
N1—C1	1.3635 (17)	C5—C6	1.417 (2)
N1—C9	1.3169 (17)	C6—C7	1.401 (2)
N2—H2A	0.884 (18)	C7—H7	0.976 (17)
N2—C10	1.316 (2)	C7—C8	1.357 (2)
C1—C2	1.408 (2)	C8—H8	0.927 (16)
C1—C6	1.4183 (19)	C8—C9	1.404 (2)
C2—H2B	0.962 (16)	C9—C10	1.5017 (19)
C2—C3	1.358 (2)	O1S—H1SA	0.84 (2)
C3—H3	0.999 (17)	O1S—H1SB	0.93 (2)
C3—C4	1.410 (2)
N2—O2—H2	103.8 (12)	C4—C5—C6	120.80 (15)
C9—N1—C1	117.93 (12)	C6—C5—H5	115.6 (10)
O2—N2—H2A	114.9 (11)	C5—C6—C1	118.21 (14)
C10—N2—O2	120.66 (14)	C7—C6—C1	117.81 (13)
C10—N2—H2A	124.5 (11)	C7—C6—C5	123.98 (14)
N1—C1—C2	118.95 (13)	C6—C7—H7	120.4 (9)
N1—C1—C6	121.61 (13)	C8—C7—C6	120.22 (14)
C2—C1—C6	119.44 (13)	C8—C7—H7	119.4 (9)
C1—C2—H2B	118.7 (9)	C7—C8—H8	124.1 (10)
C3—C2—C1	120.73 (15)	C7—C8—C9	118.11 (15)
C3—C2—H2B	120.6 (9)	C9—C8—H8	117.8 (10)
C2—C3—H3	122.3 (9)	N1—C9—C8	124.30 (13)
C2—C3—C4	119.85 (16)	N1—C9—C10	116.29 (12)
C4—C3—H3	117.8 (9)	C8—C9—C10	119.41 (14)
C3—C4—H4	119.2 (9)	O1—C10—N2	123.24 (14)
C5—C4—C3	120.96 (15)	O1—C10—C9	122.90 (13)
C5—C4—H4	119.8 (9)	N2—C10—C9	113.86 (13)
C4—C5—H5	123.6 (10)	H1SA—O1S—H1SB	102.7 (19)
O2—N2—C10—O1	0.8 (2)	C2—C3—C4—C5	−0.3 (2)
O2—N2—C10—C9	−178.96 (12)	C3—C4—C5—C6	−0.1 (2)
N1—C1—C2—C3	178.81 (13)	C4—C5—C6—C1	−0.2 (2)
N1—C1—C6—C5	−179.24 (12)	C4—C5—C6—C7	−179.86 (15)
N1—C1—C6—C7	0.4 (2)	C5—C6—C7—C8	179.76 (14)
N1—C9—C10—O1	−177.33 (14)	C6—C1—C2—C3	−1.3 (2)
N1—C9—C10—N2	2.48 (19)	C6—C7—C8—C9	−1.2 (2)
C1—N1—C9—C8	−1.4 (2)	C7—C8—C9—N1	1.9 (2)
C1—N1—C9—C10	178.08 (11)	C7—C8—C9—C10	−177.53 (13)
C1—C2—C3—C4	1.0 (2)	C8—C9—C10—O1	2.2 (2)
C1—C6—C7—C8	0.1 (2)	C8—C9—C10—N2	−178.00 (14)
C2—C1—C6—C5	0.91 (19)	C9—N1—C1—C2	−179.94 (12)
C2—C1—C6—C7	−179.44 (13)	C9—N1—C1—C6	0.20 (19)

D—H···A	D—H	H···A	D···A	D—H···A
O1S—H1SA···O1i	0.85 (2)	2.15 (3)	2.9404 (19)	155 (2)
O1S—H1SA···O2i	0.85 (2)	2.54 (2)	3.0850 (18)	124 (2)
O1S—H1SB···O1ii	0.93 (2)	1.85 (2)	2.7783 (18)	176 (2)
O2—H2···O1S	0.97 (2)	1.67 (2)	2.6407 (18)	175 (2)
C3—H3···O2iii	0.999 (16)	2.518 (16)	3.493 (2)	165.0 (15)
C4—H4···O2iv	0.975 (19)	2.589 (18)	3.273 (2)	127.3 (12)
C5—H5···O1Sv	0.967 (17)	2.593 (17)	3.547 (2)	169.0 (13)