5-Chloro-8-hydroxy­quinolinium nitrate

Abstract

The 5-chloro-8-hydroxy­quinolinium cation in the the title ion pair, C₉H₇ClNO⁺·NO₃ ⁻, is approximately coplanar with the nitrate anion [dihedral angle = 16.1 (1)°]. Two ion pairs are hydrogen bonded (2 × O—H⋯O and 2 × N—H⋯O) about a center of inversion, generating an R ₄ ⁴(14) ring.

Related literature

The 8-hydroxy­quinolinium cation has been isolated as a number of salts; for the 8-hydroxy­quinolinium chloride hydrate, see: Skakle et al. (2006 ▶). For the crystal structure of 5-chloro-8-hydroxy­quinoline, see: Banerjee & Saha (1986 ▶).

Experimental

Crystal data

• C₉H₇ClNO⁺·NO₃ ⁻

• M _r = 242.62

• Monoclinic,

• a = 7.4379 (3) Å

• b = 11.5518 (6) Å

• c = 11.2288 (5) Å

• β = 95.831 (3)°

• V = 959.80 (8) ų

• Z = 4

• Mo Kα radiation

• μ = 0.40 mm⁻¹

• T = 123 K

• 0.20 × 0.05 × 0.05 mm

Data collection

• Bruker SMART APEX diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.925, T _max = 0.980

• 6472 measured reflections

• 2196 independent reflections

• 1574 reflections with I > 2˘I)

• R _int = 0.049

Refinement

• R[F ² > 2σ(F ²)] = 0.062

• wR(F ²) = 0.192

• S = 1.07

• 2196 reflections

• 153 parameters

• 2 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 1.20 e Å⁻³

• Δρ_min = −0.34 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1o⋯O2i	0.84 (1)	1.87 (1)	2.695 (3)	169 (4)
N1—H1n⋯O2	0.88 (1)	1.95 (1)	2.816 (3)	167 (4)

Symmetry code: (i) .

supplementary crystallographic information

Experimental

Zinc acetate (0.19 g, 1 mmol) and 5-chloro-8-hydroxyquinoline (0.36 g, 2 mmol) were loaded into a convection tube; the tube was filled with dry methanol and kept at 333 K. Yellow crystals were collected from the side-arm after several days.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C–H 0.95 Å) and were included in the refinement in the riding model approximation with U(H) fixed at 1.2U(C). The ammonium and hydroxy H-atoms were located in a difference Fourier map, and were refined with distance restraints of N–H = 0.88±0.01 Å and O–H = 0.84±0.01 Å; their isotropic temperature factors were refined.

The final difference Fourier map had a large peak at about 1 Å from the Cl1 atom.

Figures

Fig. 1.

Thermal ellipsoid plot (Barbour, 2001) of a pair of hydrogen-bonded [C9H7ClNO][NO3] ion pairs drawn at the 70% probability level. Hydrogen atoms are drawn spheres of arbitrary radius and dashed lines denote hydrogen bonds.

Crystal data

C9H7ClNO+·NO3−	F(000) = 496
Mr = 242.62	Dx = 1.679 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1079 reflections
a = 7.4379 (3) Å	θ = 2.5–26.4°
b = 11.5518 (6) Å	µ = 0.40 mm−1
c = 11.2288 (5) Å	T = 123 K
β = 95.831 (3)°	Prism, yellow
V = 959.80 (8) Å3	0.20 × 0.05 × 0.05 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer	2196 independent reflections
Radiation source: fine-focus sealed tube	1574 reflections with I > 2˘I)
graphite	Rint = 0.049
ω scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.925, Tmax = 0.980	k = −15→12
6472 measured reflections	l = −14→14

Refinement

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.192	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.1164P)2 + 0.1797P] where P = (Fo2 + 2Fc2)/3
2196 reflections	(Δ/σ)max = 0.001
153 parameters	Δρmax = 1.20 e Å−3
2 restraints	Δρmin = −0.34 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	−0.30656 (11)	0.30338 (8)	0.76985 (8)	0.0321 (3)
O1	0.3429 (3)	0.4706 (2)	0.5632 (2)	0.0279 (6)
H1O	0.350 (6)	0.5423 (11)	0.553 (4)	0.042 (12)*
O2	0.5861 (3)	0.30211 (18)	0.4592 (2)	0.0261 (6)
O3	0.6434 (3)	0.12125 (19)	0.4947 (2)	0.0325 (6)
O4	0.8190 (3)	0.2201 (2)	0.3904 (2)	0.0286 (6)
N1	0.2829 (4)	0.2424 (2)	0.5774 (2)	0.0203 (6)
H1N	0.385 (3)	0.265 (4)	0.552 (3)	0.037 (11)*
N2	0.6849 (4)	0.2125 (2)	0.4472 (2)	0.0220 (6)
C1	0.2635 (4)	0.1291 (3)	0.5806 (3)	0.0250 (7)
H1A	0.3516	0.0806	0.5504	0.030*
C2	0.1155 (5)	0.0794 (3)	0.6278 (3)	0.0277 (7)
H2	0.1012	−0.0023	0.6295	0.033*
C3	−0.0094 (4)	0.1513 (3)	0.6720 (3)	0.0265 (7)
H3	−0.1093	0.1185	0.7063	0.032*
C4	0.0084 (4)	0.2727 (3)	0.6672 (3)	0.0213 (7)
C5	−0.1144 (4)	0.3518 (3)	0.7089 (3)	0.0254 (7)
C6	−0.0849 (5)	0.4687 (3)	0.7003 (3)	0.0325 (8)
H6	−0.1694	0.5213	0.7282	0.039*
C7	0.0666 (5)	0.5118 (3)	0.6513 (3)	0.0297 (8)
H7	0.0832	0.5931	0.6460	0.036*
C8	0.1920 (4)	0.4385 (3)	0.6108 (3)	0.0231 (7)
C9	0.1613 (4)	0.3178 (3)	0.6184 (3)	0.0204 (7)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0219 (5)	0.0405 (6)	0.0359 (5)	−0.0012 (3)	0.0128 (3)	−0.0003 (4)
O1	0.0275 (13)	0.0173 (12)	0.0413 (14)	0.0001 (9)	0.0147 (10)	0.0025 (10)
O2	0.0276 (13)	0.0138 (11)	0.0388 (13)	0.0032 (9)	0.0124 (10)	−0.0010 (9)
O3	0.0337 (14)	0.0145 (11)	0.0513 (16)	−0.0003 (9)	0.0135 (12)	0.0044 (10)
O4	0.0270 (13)	0.0265 (13)	0.0342 (13)	0.0027 (9)	0.0121 (10)	−0.0009 (10)
N1	0.0173 (14)	0.0205 (13)	0.0235 (14)	0.0010 (10)	0.0046 (11)	0.0003 (10)
N2	0.0214 (14)	0.0175 (13)	0.0274 (14)	0.0005 (10)	0.0038 (11)	−0.0025 (10)
C1	0.0241 (17)	0.0199 (16)	0.0320 (18)	0.0020 (12)	0.0073 (13)	−0.0003 (13)
C2	0.0278 (17)	0.0205 (16)	0.0356 (18)	−0.0003 (13)	0.0066 (14)	0.0058 (14)
C3	0.0227 (17)	0.0272 (17)	0.0300 (17)	−0.0079 (13)	0.0043 (13)	0.0027 (13)
C4	0.0208 (16)	0.0253 (16)	0.0180 (15)	−0.0034 (12)	0.0034 (12)	0.0000 (12)
C5	0.0182 (16)	0.0337 (19)	0.0252 (16)	−0.0003 (13)	0.0074 (12)	0.0025 (13)
C6	0.0271 (18)	0.0279 (18)	0.045 (2)	0.0074 (14)	0.0137 (15)	−0.0051 (15)
C7	0.0291 (19)	0.0210 (17)	0.0405 (19)	0.0021 (13)	0.0111 (15)	−0.0024 (14)
C8	0.0240 (16)	0.0201 (16)	0.0258 (16)	−0.0012 (12)	0.0058 (12)	0.0006 (12)
C9	0.0239 (17)	0.0171 (15)	0.0203 (15)	0.0021 (12)	0.0021 (12)	0.0009 (11)

Geometric parameters (Å, °)

Cl1—C5	1.739 (3)	C2—H2	0.9500
O1—C8	1.343 (4)	C3—C4	1.410 (5)
O1—H1O	0.84 (1)	C3—H3	0.9500
O2—N2	1.285 (3)	C4—C5	1.405 (4)
O3—N2	1.234 (3)	C4—C9	1.411 (4)
O4—N2	1.240 (4)	C5—C6	1.374 (5)
N1—C1	1.318 (4)	C6—C7	1.395 (5)
N1—C9	1.368 (4)	C6—H6	0.9500
N1—H1N	0.88 (1)	C7—C8	1.371 (4)
C1—C2	1.393 (5)	C7—H7	0.9500
C1—H1A	0.9500	C8—C9	1.417 (4)
C2—C3	1.375 (5)
C8—O1—H1O	113 (3)	C5—C4—C3	124.6 (3)
C1—N1—C9	123.0 (3)	C9—C4—C3	117.7 (3)
C1—N1—H1N	114 (3)	C6—C5—C4	120.1 (3)
C9—N1—H1N	123 (3)	C6—C5—Cl1	119.2 (3)
O3—N2—O4	122.1 (3)	C4—C5—Cl1	120.7 (3)
O3—N2—O2	118.2 (3)	C5—C6—C7	121.3 (3)
O4—N2—O2	119.7 (3)	C5—C6—H6	119.3
N1—C1—C2	120.8 (3)	C7—C6—H6	119.3
N1—C1—H1A	119.6	C8—C7—C6	120.9 (3)
C2—C1—H1A	119.6	C8—C7—H7	119.5
C3—C2—C1	118.5 (3)	C6—C7—H7	119.5
C3—C2—H2	120.7	O1—C8—C7	125.8 (3)
C1—C2—H2	120.7	O1—C8—C9	116.3 (3)
C2—C3—C4	121.2 (3)	C7—C8—C9	118.0 (3)
C2—C3—H3	119.4	N1—C9—C4	118.8 (3)
C4—C3—H3	119.4	N1—C9—C8	119.3 (3)
C5—C4—C9	117.8 (3)	C4—C9—C8	121.9 (3)
C9—N1—C1—C2	−0.5 (5)	C6—C7—C8—O1	−179.4 (3)
N1—C1—C2—C3	−0.5 (5)	C6—C7—C8—C9	1.0 (5)
C1—C2—C3—C4	1.6 (5)	C1—N1—C9—C4	0.5 (4)
C2—C3—C4—C5	179.2 (3)	C1—N1—C9—C8	−179.6 (3)
C2—C3—C4—C9	−1.7 (5)	C5—C4—C9—N1	179.8 (3)
C9—C4—C5—C6	0.8 (5)	C3—C4—C9—N1	0.6 (4)
C3—C4—C5—C6	179.9 (3)	C5—C4—C9—C8	−0.2 (4)
C9—C4—C5—Cl1	179.8 (2)	C3—C4—C9—C8	−179.4 (3)
C3—C4—C5—Cl1	−1.1 (5)	O1—C8—C9—N1	−0.4 (4)
C4—C5—C6—C7	−0.6 (5)	C7—C8—C9—N1	179.3 (3)
Cl1—C5—C6—C7	−179.5 (3)	O1—C8—C9—C4	179.6 (3)
C5—C6—C7—C8	−0.4 (6)	C7—C8—C9—C4	−0.7 (5)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···O2i	0.84 (1)	1.87 (1)	2.695 (3)	169 (4)
N1—H1n···O2	0.88 (1)	1.95 (1)	2.816 (3)	167 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1.