6-Eth­oxy­carbonyl-5,7-dihy­droxy-2,3-dihydro-1H-pyrido[3,2,1-ij]quinolinium tribromide

Rybakov, V.B.; Shishkina, S.V.; Ukrainets, I.V.; Golik, N.Y.; Chernenok, I.N.

doi:10.1107/S1600536812049276

organic compounds

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ISSN: 2056-9890

Volume 69| Part 1| January 2013| Page o82

https://doi.org/10.1107/S1600536812049276

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6-Ethoxycarbonyl-5,7-dihydroxy-2,3-dihydro-1H-pyrido[3,2,1-ij]quinolinium tribromide

Victor B. Rybakov,^a ^* Svitlana V. Shishkina,^b Igor V. Ukrainets,^c Nikolai Yu. Golik ^c and Igor N. Chernenok ^c

^aDepartment of Chemistry, Moscow State University, Moscow 119992, Russian Federation, ^bSTC `Institute for Single Crystals', National Academy of Sciences of Ukraine, 60 Lenina Avenue, Kharkiv 61001, Ukraine, and ^cNational University of Pharmacy, 4 Blyukhera Street, Kharkiv 61002, Ukraine
^*Correspondence e-mail: rybakov20021@yandex.ru

(Received 23 November 2012; accepted 30 November 2012; online 15 December 2012)

In the title salt, C₁₅H₁₆NO₄^+.Br₃⁻, classical intramolecular O—H⋯O hydrogen bonds are found, which results in the co-planarity of the ester substituents with the quinolinium residue [C—C—C—O torsion angle = 1.0 (10)°]. The bromine anions are placed on both sides of heterocyclic cation and form Br⋯N contacts of 3.674 (9) and 3.860 (9) Å, which confirms the location of positive charge on the N atom. Non-classical intermolecular C—H⋯Br interactions stabilize the three-dimensional crystal structure. Moreover, anion⋯π interactions are noted [Br⋯ring centroid range = 3.367 (9)–3.697 (9) Å]. The partly saturated heterocycle is disordered over two sofa conformations with occupancies in the ratio 0.56 (2):0.44 (2).

Related literature

For general background, see: Ukrainets et al. (2004 , 2007 ). For chemical bond lengths, see: Bürgi & Dunitz (1994 ).

Experimental

Crystal data

C₁₅H₁₆NO₄⁺·Br₃⁻
M_r = 513.99
Triclinic, $[P \overline 1]$
a = 7.6491 (8) Å
b = 9.1729 (10) Å
c = 13.3722 (14) Å
α = 102.355 (9)°
β = 98.777 (9)°
γ = 98.093 (9)°
V = 891.06 (17) Å³
Z = 2
Mo Kα radiation
μ = 6.81 mm⁻¹
T = 295 K
0.20 × 0.05 × 0.05 mm

Data collection

Agilent Xcalibur-3 CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2011 ) T_min = 0.343, T_max = 0.727
10147 measured reflections
5106 independent reflections
1855 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.217
S = 0.90
5106 reflections
224 parameters
5 restraints
H-atom parameters constrained
Δρ_max = 1.02 e Å⁻³
Δρ_min = −0.74 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O4	0.82	1.93	2.631 (7)	142
O1—H1⋯O3	0.82	1.73	2.459 (10)	147
C3—H3⋯Br1ⁱ	0.93	2.90	3.810 (9)	168
C4—H4⋯Br2ⁱⁱ	0.93	3.06	3.846 (9)	143
C10—H10B⋯Br2	0.97	2.99	3.936 (8)	166
C10—H10C⋯Br4ⁱⁱⁱ	0.97	2.92	3.752 (8)	144
C11A—H11B⋯Br4ⁱⁱⁱ	0.97	3.02	3.797 (17)	138
Symmetry codes: (i) x-1, y, z; (ii) x-1, y-1, z; (iii) -x, -y, -z.

Data collection: CrysAlis CCD (Agilent, 2011); cell refinement: CrysAlis RED (Agilent, 2011); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812049276/aa2080sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812049276/aa2080Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812049276/aa2080Isup3.cml

checkCIF report

Comment top

Bromination of alkyl 1-R-4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carboxylates (R = H, alkyl, phenyl) by molecular bromine in the environment of acetic acid can pass on two directions (Ukrainets et al., 2004, 2007). However, the reaction of ethyl 7-hydroxy-5-oxo-2,3-dihydro-1H,5H-pyrido[3,2,1-ij]quinoline-6-carboxylate with bromine results in the 6-ethyloxycarbonyl-5,7-dihydroxy-2,3-dihydro-1H-pyrido[3,2,1-ij]quinolinium tribromide, I.

Two tribromide anions are located in special positions, the coordinates of the central atoms coincide with the center of symmetry so the asymmetric part of unit cell contains one cation and two halves of anions. The positive charge of the cation is located on the N atom which is bonded with three atoms and the N1═C9 bond (1.335 (6) Å) has double character (the mean value for Csp²═N bond is 1.329 (1) Å (Bürgi & Dunitz, 1994)).

The partly saturated heterocycle is disordered over two sofa conformations (A and B) with population in the ratio 0.56 (2)/0.44 (2). The deviations of the C11 atom from main plane C1/C2/N1/C10/C12 are -0.57 (1) and 0.59 (1) Å for conformers A and B, respectively. The ester substituent is coplanar to the planar fragment of tricycle (C9—C8—C13—O3 torsion angle is 1.0 (10)°) owing to the formation of the strong intramolecular hydrogen bonds O1—H1···O3 and O2—H2···O4 (Table 1). The formation of hydrogen bonds causes the elongation of the C13═O3 (1.243 (10) Å) and C7═C8 (1.376 (9) Å) bonds (the mean values are 1.210 (1) Å and 1.326 (1) Å, respectively) and the shortening of the C9—O1 (1.307 (8) Å), C7—O2 (1.299 (8) Å) bonds (the mean value is 1.333 (1) Å). The methylene atom from ethyl group of the substituent has ap-orientation relative to the C8—C13 bond and is turned relative to the C13—O4 bond (the C14—O4—C13—C8 and C13—O4—C14—C15 torsion angles are 175.7 (6)° and -155.4 (8)°, respectively).

Related literature top

For general background, see: Ukrainets et al. (2004, 2007). For chemical bond lengths, see: Bürgi & Dunitz (1994).

Experimental top

A solution of anhydrous bromine (0.52 ml, 0.01 mol) in anhydrous acetic acid (5 ml) was added with vigorous stirring to a solution of the ethyl 7-hydroxy-5-oxo-2,3-dihydro-1H,5H-pyrido[3,2,1-ij]quinoline-6-carboxylate (2.73 g, 0.01 mol) in anhydrous acetic acid (20 ml). A light-yellow precipitate was formed immediately. The crystals of I were filtered off, washed with acetic acid and dried to give the product (2.26 g, 44%); m.p. 360–362 K.

Structure description top

For general background, see: Ukrainets et al. (2004, 2007). For chemical bond lengths, see: Bürgi & Dunitz (1994).

Computing details top

Data collection: CrysAlis CCD (Agilent, 2011); cell refinement: CrysAlis RED (Agilent, 2011); data reduction: CrysAlis RED (Agilent, 2011); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. View of the title compound with the atom numbering scheme. The displacement ellipsoids are drawn at the 15% probability level. H atoms are presented as a small spheres of arbitrary radius. Intramolecular hydrogen bonds are indicated by dashed lines. Only major moiety of disorder group [s.o.f. = 0.56 (2)] are presented. Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) -x, -y, -z.

6-Ethoxycarbonyl-5,7-dihydroxy-2,3-dihydro-1H- pyrido[3,2,1-ij]quinolinium tribromide top

Crystal data top

C₁₅H₁₆NO₄⁺·Br₃⁻	Z = 2
M_r = 513.99	F(000) = 500
Triclinic, P1	D_x = 1.916 Mg m⁻³
Hall symbol: -P 1	Melting point = 360–362 K
a = 7.6491 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.1729 (10) Å	Cell parameters from 1363 reflections
c = 13.3722 (14) Å	θ = 3.1–32.0°
α = 102.355 (9)°	µ = 6.81 mm⁻¹
β = 98.777 (9)°	T = 295 K
γ = 98.093 (9)°	Rod, light yellow
V = 891.06 (17) Å³	0.20 × 0.05 × 0.05 mm

Data collection top

Agilent Xcalibur-3 CCD diffractometer	5106 independent reflections
Radiation source: Enhance (Mo) X-Ray Source	1855 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 16.1827 pixels mm^-1	θ_max = 30.0°, θ_min = 3.1°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2011)	k = −12→12
T_min = 0.343, T_max = 0.727	l = −18→18
10147 measured reflections

Refinement top

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)] = 0.068	Hydrogen site location: difference Fourier map
wR(F²) = 0.217	H-atom parameters constrained
S = 0.90	w = 1/[σ²(F_o²) + (0.108P)²] where P = (F_o² + 2F_c²)/3
5106 reflections	(Δ/σ)_max < 0.001
224 parameters	Δρ_max = 1.02 e Å⁻³
5 restraints	Δρ_min = −0.74 e Å⁻³

Crystal data top

C₁₅H₁₆NO₄⁺·Br₃⁻	γ = 98.093 (9)°
M_r = 513.99	V = 891.06 (17) Å³
Triclinic, P1	Z = 2
a = 7.6491 (8) Å	Mo Kα radiation
b = 9.1729 (10) Å	µ = 6.81 mm⁻¹
c = 13.3722 (14) Å	T = 295 K
α = 102.355 (9)°	0.20 × 0.05 × 0.05 mm
β = 98.777 (9)°

Data collection top

Agilent Xcalibur-3 CCD diffractometer	5106 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2011)	1855 reflections with I > 2σ(I)
T_min = 0.343, T_max = 0.727	R_int = 0.034
10147 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	5 restraints
wR(F²) = 0.217	H-atom parameters constrained
S = 0.90	Δρ_max = 1.02 e Å⁻³
5106 reflections	Δρ_min = −0.74 e Å⁻³
224 parameters

Special details top

Experimental. Absorption correction: CrysAlis RED (Agilent Technologies, 2011). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wRand 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 > 2σ(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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Br1	0.5000	0.5000	0.5000	0.0803 (3)
Br2	0.56781 (11)	0.74499 (9)	0.44305 (6)	0.1062 (4)
Br3	0.0000	0.0000	0.0000	0.1391 (6)
Br4	0.06301 (17)	−0.24813 (17)	0.03287 (9)	0.1666 (6)
N1	0.1821 (7)	0.3314 (6)	0.2533 (4)	0.0753 (14)
O1	0.4153 (7)	0.3418 (7)	0.1698 (5)	0.1109 (17)
H1	0.4995	0.2986	0.1580	0.166*
O2	0.2437 (8)	−0.0849 (6)	0.3048 (4)	0.0989 (14)
H2	0.3201	−0.1217	0.2760	0.148*
O3	0.5774 (8)	0.1288 (8)	0.1341 (4)	0.131 (2)
O4	0.5025 (7)	−0.0768 (7)	0.1961 (4)	0.1052 (16)
C1	0.0665 (9)	0.2577 (8)	0.3053 (4)	0.0726 (17)
C2	−0.0723 (9)	0.3279 (8)	0.3413 (6)	0.0848 (19)
C3	−0.1792 (11)	0.2510 (11)	0.3935 (6)	0.108 (2)
H3	−0.2679	0.2972	0.4209	0.129*
C4	−0.1624 (11)	0.1110 (10)	0.4074 (6)	0.095 (2)
H4	−0.2438	0.0610	0.4394	0.114*
C5	−0.0296 (10)	0.0449 (8)	0.3754 (5)	0.0853 (19)
H5	−0.0136	−0.0483	0.3888	0.102*
C6	0.0867 (9)	0.1169 (8)	0.3211 (4)	0.0747 (17)
C7	0.2325 (9)	0.0461 (8)	0.2845 (5)	0.0774 (17)
C8	0.3425 (9)	0.1203 (8)	0.2317 (5)	0.0772 (17)
C9	0.3130 (10)	0.2649 (9)	0.2176 (5)	0.085 (2)
C10	0.1679 (10)	0.4818 (9)	0.2325 (7)	0.110 (3)
H10A	0.1998	0.4849	0.1654	0.132*	0.56 (2)
H10B	0.2520	0.5597	0.2855	0.132*	0.56 (2)
H10C	0.1017	0.4691	0.1624	0.132*	0.44 (2)
H10D	0.2871	0.5389	0.2378	0.132*	0.44 (2)
C11A	−0.0241 (14)	0.515 (2)	0.2325 (11)	0.113 (7)	0.56 (2)
H11A	−0.0223	0.6214	0.2353	0.136*	0.56 (2)
H11B	−0.1011	0.4569	0.1675	0.136*	0.56 (2)
C11B	0.0704 (18)	0.5691 (14)	0.3120 (14)	0.117 (9)	0.44 (2)
H11C	0.1506	0.6019	0.3793	0.141*	0.44 (2)
H11D	0.0431	0.6591	0.2904	0.141*	0.44 (2)
C12	−0.1052 (12)	0.4752 (10)	0.3240 (7)	0.126 (3)
H12A	−0.0535	0.5536	0.3869	0.151*	0.56 (2)
H12B	−0.2338	0.4734	0.3099	0.151*	0.56 (2)
H12C	−0.1499	0.5296	0.3825	0.151*	0.44 (2)
H12D	−0.1956	0.4597	0.2615	0.151*	0.44 (2)
C13	0.4866 (11)	0.0567 (11)	0.1831 (5)	0.092 (2)
C14	0.6366 (11)	−0.1428 (11)	0.1409 (8)	0.140 (4)
H14A	0.7564	−0.1079	0.1829	0.167*
H14B	0.6352	−0.1137	0.0752	0.167*
C15	0.5833 (15)	−0.3161 (11)	0.1218 (10)	0.173 (5)
H15A	0.6558	−0.3649	0.0772	0.260*
H15B	0.4588	−0.3470	0.0893	0.260*
H15C	0.6020	−0.3444	0.1872	0.260*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0730 (5)	0.0913 (7)	0.0716 (5)	0.0189 (5)	0.0020 (4)	0.0143 (5)
Br2	0.1086 (6)	0.0994 (7)	0.1052 (6)	0.0040 (5)	0.0010 (4)	0.0359 (5)
Br3	0.0870 (7)	0.2340 (17)	0.0652 (6)	−0.0272 (9)	−0.0029 (5)	0.0175 (7)
Br4	0.1423 (10)	0.2122 (13)	0.1221 (8)	−0.0008 (9)	0.0014 (6)	0.0283 (8)
N1	0.071 (3)	0.071 (4)	0.077 (3)	−0.003 (3)	0.004 (3)	0.019 (3)
O1	0.098 (4)	0.133 (5)	0.108 (4)	−0.009 (3)	0.022 (3)	0.061 (4)
O2	0.112 (4)	0.082 (3)	0.116 (4)	0.034 (3)	0.040 (3)	0.028 (3)
O3	0.107 (4)	0.179 (6)	0.104 (4)	−0.004 (4)	0.050 (3)	0.027 (4)
O4	0.083 (3)	0.110 (4)	0.114 (4)	0.011 (3)	0.031 (3)	0.002 (3)
C1	0.076 (4)	0.076 (4)	0.055 (3)	−0.003 (3)	−0.006 (3)	0.017 (3)
C2	0.084 (4)	0.082 (5)	0.099 (5)	0.026 (4)	0.020 (4)	0.034 (4)
C3	0.095 (5)	0.125 (7)	0.103 (5)	0.021 (5)	0.035 (4)	0.016 (5)
C4	0.096 (5)	0.104 (6)	0.095 (5)	0.029 (5)	0.040 (4)	0.024 (4)
C5	0.097 (5)	0.083 (5)	0.081 (4)	0.009 (4)	0.023 (4)	0.030 (4)
C6	0.086 (4)	0.080 (5)	0.052 (3)	0.007 (4)	−0.002 (3)	0.019 (3)
C7	0.080 (4)	0.076 (5)	0.069 (4)	0.007 (4)	0.008 (3)	0.012 (3)
C8	0.076 (4)	0.084 (5)	0.062 (3)	0.002 (4)	0.006 (3)	0.010 (3)
C9	0.085 (5)	0.096 (6)	0.059 (3)	−0.017 (4)	−0.002 (3)	0.019 (4)
C10	0.113 (6)	0.086 (6)	0.113 (6)	−0.014 (5)	−0.012 (5)	0.027 (5)
C11A	0.115 (13)	0.103 (12)	0.127 (14)	0.022 (10)	0.004 (10)	0.052 (11)
C11B	0.111 (16)	0.081 (14)	0.17 (2)	0.015 (11)	0.018 (16)	0.060 (14)
C12	0.141 (8)	0.099 (6)	0.146 (8)	0.029 (6)	0.034 (6)	0.038 (6)
C13	0.092 (5)	0.102 (6)	0.072 (4)	0.014 (5)	0.008 (4)	0.009 (4)
C14	0.097 (6)	0.154 (10)	0.151 (8)	0.033 (6)	0.043 (6)	−0.019 (7)
C15	0.176 (11)	0.169 (12)	0.232 (13)	0.074 (10)	0.106 (10)	0.096 (11)

Geometric parameters (Å, º) top

Br1—Br2ⁱ	2.5346 (8)	C7—C8	1.376 (9)
Br1—Br2	2.5346 (8)	C8—C9	1.423 (10)
Br3—Br4ⁱⁱ	2.5057 (16)	C8—C13	1.489 (11)
Br3—Br4	2.5057 (16)	C10—C11A	1.5398 (10)
N1—C9	1.340 (9)	C10—C11B	1.5398 (10)
N1—C1	1.394 (8)	C10—H10A	0.9700
N1—C10	1.479 (9)	C10—H10B	0.9700
O1—C9	1.307 (8)	C10—H10C	0.9700
O1—H1	0.8200	C10—H10D	0.9700
O2—C7	1.299 (8)	C11A—C12	1.5396 (10)
O2—H2	0.8200	C11A—H11A	0.9700
O3—C13	1.243 (10)	C11A—H11B	0.9700
O4—C13	1.292 (9)	C11B—C12	1.5397 (10)
O4—C14	1.476 (9)	C11B—H11C	0.9700
C1—C6	1.378 (9)	C11B—H11D	0.9700
C1—C2	1.411 (10)	C12—H12A	0.9700
C2—C3	1.370 (10)	C12—H12B	0.9700
C2—C12	1.467 (11)	C12—H12C	0.9700
C3—C4	1.358 (10)	C12—H12D	0.9700
C3—H3	0.9300	C14—C15	1.5395 (10)
C4—C5	1.334 (10)	C14—H14A	0.9700
C4—H4	0.9300	C14—H14B	0.9700
C5—C6	1.411 (9)	C15—H15A	0.9600
C5—H5	0.9300	C15—H15B	0.9600
C6—C7	1.462 (10)	C15—H15C	0.9600

Br2ⁱ—Br1—Br2	180.0	C11B—C10—H10D	109.7
Br4ⁱⁱ—Br3—Br4	180.00 (8)	H10A—C10—H10D	66.6
C9—N1—C1	120.0 (6)	H10C—C10—H10D	108.2
C9—N1—C10	116.4 (6)	C12—C11A—C10	113.6 (7)
C1—N1—C10	123.6 (6)	C12—C11A—H11A	108.9
C9—O1—H1	109.5	C10—C11A—H11A	108.9
C7—O2—H2	109.5	C12—C11A—H11B	108.9
C13—O4—C14	112.8 (7)	C10—C11A—H11B	108.9
C6—C1—N1	120.4 (6)	H11A—C11A—H11B	107.7
C6—C1—C2	120.1 (6)	C12—C11B—C10	113.6 (7)
N1—C1—C2	119.5 (6)	C12—C11B—H11C	108.9
C3—C2—C1	116.7 (7)	C10—C11B—H11C	108.9
C3—C2—C12	120.4 (8)	C12—C11B—H11D	108.9
C1—C2—C12	122.9 (6)	C10—C11B—H11D	108.9
C4—C3—C2	123.5 (8)	H11C—C11B—H11D	107.7
C4—C3—H3	118.3	C2—C12—C11A	112.3 (9)
C2—C3—H3	118.3	C2—C12—C11B	109.9 (10)
C5—C4—C3	120.2 (7)	C2—C12—H12A	109.1
C5—C4—H4	119.9	C11A—C12—H12A	109.1
C3—C4—H4	119.9	C11B—C12—H12A	68.9
C4—C5—C6	119.7 (7)	C2—C12—H12B	109.1
C4—C5—H5	120.1	C11A—C12—H12B	109.1
C6—C5—H5	120.1	C11B—C12—H12B	139.4
C1—C6—C5	119.7 (7)	H12A—C12—H12B	107.9
C1—C6—C7	119.5 (6)	C2—C12—H12C	109.7
C5—C6—C7	120.7 (7)	C11A—C12—H12C	136.4
O2—C7—C8	126.0 (7)	C11B—C12—H12C	109.7
O2—C7—C6	115.3 (6)	H12B—C12—H12C	66.2
C8—C7—C6	118.7 (7)	C2—C12—H12D	109.7
C7—C8—C9	118.7 (7)	C11A—C12—H12D	67.7
C7—C8—C13	124.5 (7)	C11B—C12—H12D	109.7
C9—C8—C13	116.7 (7)	H12A—C12—H12D	138.7
O1—C9—N1	116.0 (7)	H12B—C12—H12D	45.0
O1—C9—C8	121.3 (8)	H12C—C12—H12D	108.2
N1—C9—C8	122.6 (6)	O3—C13—O4	125.5 (8)
N1—C10—C11A	111.1 (8)	O3—C13—C8	120.9 (9)
N1—C10—C11B	109.7 (9)	O4—C13—C8	113.6 (7)
N1—C10—H10A	109.4	O4—C14—C15	106.3 (8)
C11A—C10—H10A	109.4	O4—C14—H14A	110.5
C11B—C10—H10A	139.2	C15—C14—H14A	110.5
N1—C10—H10B	109.4	O4—C14—H14B	110.5
C11A—C10—H10B	109.4	C15—C14—H14B	110.5
C11B—C10—H10B	68.8	H14A—C14—H14B	108.7
H10A—C10—H10B	108.0	C14—C15—H15A	109.5
N1—C10—H10C	109.7	C14—C15—H15B	109.5
C11A—C10—H10C	68.1	H15A—C15—H15B	109.5
C11B—C10—H10C	109.7	C14—C15—H15C	109.5
H10B—C10—H10C	138.4	H15A—C15—H15C	109.5
N1—C10—H10D	109.7	H15B—C15—H15C	109.5
C11A—C10—H10D	137.5

C9—N1—C1—C6	0.6 (8)	C10—N1—C9—C8	−179.9 (6)
C10—N1—C1—C6	179.4 (5)	C7—C8—C9—O1	178.7 (6)
C9—N1—C1—C2	−179.1 (6)	C13—C8—C9—O1	−4.2 (9)
C10—N1—C1—C2	−0.3 (9)	C7—C8—C9—N1	−0.2 (9)
C6—C1—C2—C3	1.5 (9)	C13—C8—C9—N1	176.9 (6)
N1—C1—C2—C3	−178.8 (6)	C9—N1—C10—C11A	155.4 (8)
C6—C1—C2—C12	−177.9 (7)	C1—N1—C10—C11A	−23.5 (10)
N1—C1—C2—C12	1.8 (10)	C9—N1—C10—C11B	−157.4 (8)
C1—C2—C3—C4	−3.0 (12)	C1—N1—C10—C11B	23.7 (10)
C12—C2—C3—C4	176.4 (7)	N1—C10—C11A—C12	45.2 (15)
C2—C3—C4—C5	4.4 (13)	C11B—C10—C11A—C12	−51.8 (8)
C3—C4—C5—C6	−4.0 (11)	N1—C10—C11B—C12	−48.6 (16)
N1—C1—C6—C5	178.9 (5)	C11A—C10—C11B—C12	51.8 (8)
C2—C1—C6—C5	−1.4 (9)	C3—C2—C12—C11A	−158.5 (10)
N1—C1—C6—C7	1.0 (8)	C1—C2—C12—C11A	20.9 (12)
C2—C1—C6—C7	−179.3 (6)	C3—C2—C12—C11B	154.1 (9)
C4—C5—C6—C1	2.6 (10)	C1—C2—C12—C11B	−26.5 (11)
C4—C5—C6—C7	−179.5 (7)	C10—C11A—C12—C2	−44.3 (16)
C1—C6—C7—O2	178.5 (5)	C10—C11A—C12—C11B	51.8 (8)
C5—C6—C7—O2	0.6 (9)	C10—C11B—C12—C2	50.2 (17)
C1—C6—C7—C8	−2.2 (8)	C10—C11B—C12—C11A	−51.8 (8)
C5—C6—C7—C8	179.9 (6)	C14—O4—C13—O3	−3.2 (11)
O2—C7—C8—C9	−179.0 (6)	C14—O4—C13—C8	175.7 (6)
C6—C7—C8—C9	1.8 (9)	C7—C8—C13—O3	178.0 (7)
O2—C7—C8—C13	4.1 (11)	C9—C8—C13—O3	1.0 (10)
C6—C7—C8—C13	−175.1 (6)	C7—C8—C13—O4	−1.0 (10)
C1—N1—C9—O1	180.0 (5)	C9—C8—C13—O4	−177.9 (6)
C10—N1—C9—O1	1.1 (8)	C13—O4—C14—C15	−155.4 (8)
C1—N1—C9—C8	−1.0 (8)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O4	0.82	1.93	2.631 (7)	142
O1—H1···O3	0.82	1.73	2.459 (10)	147
C3—H3···Br1ⁱⁱⁱ	0.93	2.90	3.810 (9)	168
C4—H4···Br2^iv	0.93	3.06	3.846 (9)	143
C10—H10B···Br2	0.97	2.99	3.936 (8)	166
C10—H10C···Br4ⁱⁱ	0.97	2.92	3.752 (8)	144
C11A—H11B···Br4ⁱⁱ	0.97	3.02	3.797 (17)	138

Symmetry codes: (ii) −x, −y, −z; (iii) x−1, y, z; (iv) x−1, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₆NO₄⁺·Br₃⁻
M_r	513.99
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	7.6491 (8), 9.1729 (10), 13.3722 (14)
α, β, γ (°)	102.355 (9), 98.777 (9), 98.093 (9)
V (Å³)	891.06 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	6.81
Crystal size (mm)	0.20 × 0.05 × 0.05

Data collection
Diffractometer	Agilent Xcalibur-3 CCD
Absorption correction	Multi-scan (CrysAlis RED; Agilent, 2011)
T_min, T_max	0.343, 0.727
No. of measured, independent and observed [I > 2σ(I)] reflections	10147, 5106, 1855
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.217, 0.90
No. of reflections	5106
No. of parameters	224
No. of restraints	5
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.02, −0.74

Computer programs: CrysAlis CCD (Agilent, 2011), CrysAlis RED (Agilent, 2011), SHELXTL (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O4	0.82	1.93	2.631 (7)	142.3
O1—H1···O3	0.82	1.73	2.459 (10)	147.1
C3—H3···Br1ⁱ	0.93	2.90	3.810 (9)	167.6
C4—H4···Br2ⁱⁱ	0.93	3.06	3.846 (9)	142.7
C10—H10B···Br2	0.97	2.99	3.936 (8)	166.4
C10—H10C···Br4ⁱⁱⁱ	0.97	2.92	3.752 (8)	144.4
C11A—H11B···Br4ⁱⁱⁱ	0.97	3.02	3.797 (17)	137.8

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

References

Agilent (2011). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, Oxfordshire, England. Google Scholar
Bürgi, H.-B. & Dunitz, J. D. (1994). Structure Correlation, Vol. 2, pp. 767–784. Weinheim: VCH. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ukrainets, I. V., Petrushova, L. A., Sidorenko, L. V., Rybakov, V. B. & Chernyshev, V. V. (2004). Zh. Org. Farm. Khim. 2, 26–31. CAS Google Scholar
Ukrainets, I. V., Sidorenko, L. V. & Golovchenko, O. S. (2007). Chem. Heterocycl. Compd, pp. 1008–1013. Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

6-Eth­­oxy­carbonyl-5,7-dihy­dr­oxy-2,3-di­hydro-1H-pyrido[3,2,1-ij]quinolinium tribromide

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Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

6-Ethoxycarbonyl-5,7-dihydroxy-2,3-dihydro-1H-pyrido[3,2,1-ij]quinolinium tribromide