supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportcited insimilar papers buy article online

Acta Cryst. (2007). E63, o3353-o3354    [ doi:10.1107/S1600536807030802 ]

1,2,3,4-Tetrahydroisoquinolinium hydrogensquarate

T. Kolev, B. Shivachev, R. Petrova, I. Ivanov, S. Atanasova and S. Statkova

Abstract top

The asymmetric unit of the title compound, C9H12N+·C4H4O-, contains two independent 1,2,3,4-tetrahydroisoquinolinium cations and two independent hydrogensquarate anions. In one of the cations, the N atom is disordered over two positions with occupancies of approximately 0.8 and 0.2. The pyridinium rings adopt envelope conformations. The hydrogensquarate anions are linked to form cyclic tetramers through strong O-H...O hydrogen bonds. The tetrahydroisoquinolinium and hydrogensquarate ions are linked via N-H...O hydrogen bonds, forming a three-dimensional framework.

Comment top

Isoquinoline derivatives have been used as building blocks in the synthesis of natural products (Roqué-Rosell et al., 2006) and are of great interest due to their biological and pharmacological properties (Said et al., 2005; Matsuhashi et al., 2002; Alexandrova et al., 2000; Anderson et al., 1998; Gargett & Wiley, 1997; Brzezinska, 1994, Loesel et al., 1987). In continuation of our investigations of biologically active hydrogensquarates (Kolev et al., 1997; Kolev, Spiteller, Sheldrick & Mayer-Figge, 2005, 2006; Kolev, Spiteller, Sheldrick, Mayer-Figge & Van Almsick, 2005; Kolev, Yancheva et al., 2006), we report here the structure of 1,2,3,4-tetrahydroisoquinolinium 2-hydroxy-3,4-dioxocyclobut-1-en-1-olate, (I).

There are two independent 1,2,3,4-tetrahydroisoquinolinium cations (A and B) and two independent hydrogensquarate anions in the asymmetric unit of (I) (Fig. 1). There are very few structural differences between the identical pairs of ions (A/B and C/D). The hydrogensquarate ions C and D are each planar with r.m.s. deviations of 0.031 and 0.010 Å, respectively. The C═O bonds have typical values around 1.22 Å while the different lengths for the C—O single bonds (Table 1) show the presence of a negative charge located on one of the oxygen atoms. In both isoquinolinium ions A and B the aromatic ring is nearly planar. The pyridinium rings adopt envelope conformations with atoms N1, N2 and N22 deviating from the mean planes through the remaining five atoms of the rings by 0.644 (4), 0.564 (7) and 0.25 (3) Å, respectively. The partial protonation of the secondary amino group in both A and B could be inferred from C—N bonds lengths (Table 1).

An extensive hydrogen bonding is observed in the crystal structure of (I) (Table 2). The strong O33—H33···O42 and O41—H41···O34i hydrogen bonds [symmetry code (i): 1 − x, 2 − y, 1 − z) link hydrogensquarate moieties to form a cyclic tetramer. Similar motif (α-tetramer)(Gilli et al., 2001) has been reported for guanidinium hydrogen squarate (Kolev et al., 1997).

The tetrahydroisoquinolinium ions are hydrogen-bonded to hydrogensquarate ions through the only donor (N atom) present in the fragment (Fig. 2). In addition, weak C—H···O interactions (H···O = 2.30–2.57 Å and C···O = 3.251 (5)–3.402 (5) Å) stabilize the three-dimensional packing.

Related literature top

For general background, see: Alexandrova et al. (2000); Anderson et al. (1998); Brzezinska (1994); Gargett & Wiley (1997); Loesel et al. (1987); Matsuhashi et al. (2002); Roqué-Rosell et al. (2006); Said et al. (2005). For related literature, see: Gilli et al. (2001); Kolev et al. (1997); Kolev, Spiteller, Sheldrick & Mayer-Figge (2005, 2006); Kolev, Spiteller, Sheldrick, Mayer-Figge & Van Almsick (2005); Kolev, Yancheva et al. (2006).

Experimental top

A mixture of equimolar amounts of squaric acid (2 mmol, 228 mg) and 1,2,3,4-tetrahydroisoquinoline (2 mmol, 266.4 mg) in water (40 ml) was stirred at room temperature for 2 h. The resulting 1,2,3,4-tetrahydroisoquinolinium hydrogensquarate was isolated from the reaction mixture by filtration. Colourless crystals of (I) suitable for X-ray analysis were grown from water.

Refinement top

The nitrogen atom of molecule B is disordered over two positions (N2 and N22) with occupancies of 0.796 (14) and 0.204 (14). The N—C distances involving the disordered atoms were restrained to be equal within 0.03 Å, and the Uij components of the N22 atom were approximated to isotropic behaviour. The H atoms were placed in idealized positions, with O—H = 0.82 Å, C—H = 0.93–0.97 Å and N—H = 0.90 Å. All H atoms were constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C or N) and Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Bruno et al., 2002); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I). Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radii. Both disorder components are shown.
[Figure 2] Fig. 2. A view of the molecular packing in (I). H atoms not involved in hydrogen bonding (dashed lines) have been omitted for clarity. [Symmetry codes: (i) 1 − x, 1 − y, −z; (ii) x, y − 1,z; (iii) 1 − x, 2 − y, 1 − z; (iv) −x, 2 − y, 1 − z].
1,2,3,4-tetrahydroisoquinolinium 2-hydroxy-3,4-dioxocyclobut-1-en-1-olate top
Crystal data top
C9H12N+·C4HO4−Z = 4
Mr = 247.24F(000) = 520
Triclinic, P1Dx = 1.449 Mg m−3
Hall symbol: -P 1Melting point: not measured K
a = 8.1456 (10) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.936 (2) ÅCell parameters from 22 reflections
c = 13.6897 (12) Åθ = 17.9–19.8°
α = 77.81 (2)°µ = 0.11 mm−1
β = 78.170 (17)°T = 290 K
γ = 74.319 (13)°Block, colourless
V = 1133.4 (3) Å30.40 × 0.40 × 0.40 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.042
Radiation source: fine-focus sealed tubeθmax = 26.0°, θmin = 1.5°
graphiteh = 0→10
non–profiled ω/2θ scansk = −12→13
4773 measured reflectionsl = −16→16
4444 independent reflections3 standard reflections every 120 min
3226 reflections with I > 2σ(I) intensity decay: 1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.067Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.234H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.1657P)2 + 0.1541P]
where P = (Fo2 + 2Fc2)/3
4444 reflections(Δ/σ)max = 0.001
335 parametersΔρmax = 0.45 e Å−3
12 restraintsΔρmin = −0.32 e Å−3
Crystal data top
C9H12N+·C4HO4−γ = 74.319 (13)°
Mr = 247.24V = 1133.4 (3) Å3
Triclinic, P1Z = 4
a = 8.1456 (10) ÅMo Kα radiation
b = 10.936 (2) ŵ = 0.11 mm−1
c = 13.6897 (12) ÅT = 290 K
α = 77.81 (2)°0.40 × 0.40 × 0.40 mm
β = 78.170 (17)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.042
4773 measured reflectionsθmax = 26.0°
4444 independent reflections3 standard reflections every 120 min
3226 reflections with I > 2σ(I) intensity decay: 1%
Refinement top
R[F2 > 2σ(F2)] = 0.067H-atom parameters constrained
wR(F2) = 0.234Δρmax = 0.45 e Å−3
S = 1.02Δρmin = −0.32 e Å−3
4444 reflectionsAbsolute structure: ?
335 parametersFlack parameter: ?
12 restraintsRogers parameter: ?
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*/UeqOcc. (<1)
C110.5030 (4)0.7057 (3)0.6246 (2)0.0522 (8)
H11A0.41250.65940.64880.063*
H11B0.52150.73830.68110.063*
C120.6682 (4)0.6146 (3)0.5848 (2)0.0482 (7)
H12A0.76550.64790.58830.058*
H12B0.67860.53180.62890.058*
C130.6795 (3)0.5948 (2)0.4790 (2)0.0369 (6)
C140.8152 (4)0.5022 (3)0.4379 (3)0.0488 (8)
H14A0.89420.44950.47840.059*
C150.8344 (5)0.4875 (3)0.3385 (3)0.0586 (9)
H15A0.92560.42520.31220.070*
C160.7181 (5)0.5654 (4)0.2782 (3)0.0650 (10)
H16A0.73210.55710.21060.078*
C170.5813 (5)0.6553 (4)0.3177 (3)0.0565 (8)
H17A0.50140.70600.27690.068*
C180.5611 (3)0.6713 (3)0.4173 (2)0.0385 (6)
C190.4094 (4)0.7697 (3)0.4595 (2)0.0487 (8)
H19A0.38020.84260.40660.058*
H19B0.31030.73210.48240.058*
C210.7842 (5)0.1957 (5)0.0189 (3)0.0763 (13)
H21A0.81450.2461−0.04650.092*0.796 (14)
H21B0.89070.14500.04220.092*0.796 (14)
H21C0.85820.12650.05680.092*0.204 (14)
H21D0.85910.2409−0.03000.092*0.204 (14)
C220.6897 (4)0.2857 (4)0.0921 (3)0.0645 (10)
H22A0.74100.35920.07850.077*
H22B0.70400.24180.16030.077*
C230.4997 (4)0.3332 (3)0.0863 (2)0.0439 (7)
C240.3951 (5)0.4308 (3)0.1385 (2)0.0574 (9)
H24A0.44560.47050.17420.069*
C250.2221 (5)0.4693 (4)0.1385 (3)0.0667 (10)
H25A0.15600.53410.17430.080*
C260.1449 (5)0.4134 (4)0.0864 (3)0.0693 (11)
H26A0.02600.43870.08770.083*
C270.2438 (4)0.3191 (3)0.0318 (2)0.0532 (8)
H27A0.19180.2825−0.00540.064*
C280.4209 (4)0.2785 (3)0.0320 (2)0.0402 (6)
C290.5227 (4)0.1760 (3)−0.0282 (3)0.0556 (8)
H29A0.45500.1139−0.02360.067*0.796 (14)
H29B0.54510.2146−0.09880.067*0.796 (14)
H29C0.49490.2037−0.09550.067*0.204 (14)
H29D0.47870.1008−0.00030.067*0.204 (14)
C310.0455 (3)1.1145 (2)0.3028 (2)0.0341 (6)
C320.1510 (3)1.0709 (3)0.20780 (19)0.0340 (6)
C330.3049 (3)1.0510 (3)0.25202 (19)0.0340 (6)
C340.2090 (3)1.0895 (2)0.34349 (19)0.0322 (6)
C410.9529 (3)0.8286 (2)0.35799 (18)0.0328 (6)
C420.8025 (3)0.8920 (2)0.31596 (18)0.0313 (6)
C430.8868 (3)0.8533 (3)0.2170 (2)0.0381 (6)
C441.0468 (3)0.7868 (3)0.2646 (2)0.0377 (6)
N10.4485 (3)0.8144 (2)0.54460 (19)0.0476 (6)
H1A0.53310.85680.52180.057*
H1B0.35410.86960.57060.057*
N20.6865 (5)0.1096 (4)0.0066 (4)0.0567 (16)0.796 (14)
H2A0.66560.05830.06610.068*0.796 (14)
H2B0.75040.0590−0.03830.068*0.796 (14)
N220.7023 (16)0.159 (2)−0.0462 (17)0.082 (7)0.204 (14)
H22C0.74900.0748−0.04800.099*0.204 (14)
H22D0.73040.2017−0.10860.099*0.204 (14)
O31−0.1074 (2)1.1535 (2)0.33295 (17)0.0509 (6)
O320.1216 (3)1.0535 (2)0.12745 (15)0.0471 (5)
O330.4673 (2)1.0111 (2)0.21660 (13)0.0478 (6)
H330.52440.99430.26260.072*
O340.2468 (2)1.0950 (2)0.42759 (14)0.0438 (5)
O411.0005 (2)0.8119 (2)0.44593 (14)0.0472 (6)
H410.91830.84260.48630.071*
O420.6533 (2)0.95743 (19)0.34911 (13)0.0389 (5)
O430.8447 (3)0.8715 (3)0.13369 (15)0.0576 (6)
O441.1933 (3)0.7263 (2)0.23680 (17)0.0569 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C110.0468 (18)0.0601 (19)0.0448 (17)−0.0066 (15)−0.0022 (13)−0.0104 (14)
C120.0426 (17)0.0480 (17)0.0509 (17)−0.0027 (13)−0.0111 (13)−0.0082 (13)
C130.0300 (13)0.0327 (13)0.0488 (16)−0.0082 (11)−0.0063 (11)−0.0072 (11)
C140.0351 (16)0.0397 (15)0.071 (2)−0.0025 (12)−0.0089 (14)−0.0149 (14)
C150.0517 (19)0.0536 (19)0.072 (2)−0.0102 (15)0.0040 (17)−0.0303 (17)
C160.076 (3)0.073 (2)0.057 (2)−0.025 (2)−0.0041 (18)−0.0291 (18)
C170.058 (2)0.065 (2)0.0494 (18)−0.0150 (17)−0.0180 (15)−0.0064 (16)
C180.0308 (14)0.0386 (14)0.0450 (15)−0.0086 (11)−0.0062 (11)−0.0038 (12)
C190.0314 (15)0.0486 (17)0.0583 (19)0.0004 (13)−0.0103 (13)−0.0014 (14)
C210.0388 (19)0.121 (4)0.059 (2)0.006 (2)−0.0110 (16)−0.022 (2)
C220.0431 (19)0.103 (3)0.053 (2)−0.0139 (18)−0.0088 (15)−0.0277 (19)
C230.0470 (17)0.0510 (17)0.0346 (14)−0.0104 (13)−0.0054 (12)−0.0117 (12)
C240.072 (2)0.0558 (19)0.0489 (18)−0.0170 (17)−0.0027 (16)−0.0224 (15)
C250.061 (2)0.059 (2)0.064 (2)0.0084 (17)0.0049 (18)−0.0197 (17)
C260.047 (2)0.077 (3)0.069 (2)0.0066 (18)−0.0076 (18)−0.012 (2)
C270.0472 (18)0.066 (2)0.0489 (18)−0.0156 (16)−0.0131 (14)−0.0066 (15)
C280.0435 (16)0.0431 (15)0.0325 (13)−0.0065 (12)−0.0037 (11)−0.0101 (11)
C290.055 (2)0.059 (2)0.0529 (18)0.0006 (16)−0.0100 (15)−0.0272 (16)
C310.0298 (13)0.0357 (13)0.0375 (13)−0.0048 (10)−0.0051 (10)−0.0114 (11)
C320.0324 (13)0.0386 (14)0.0314 (13)−0.0024 (11)−0.0092 (10)−0.0106 (10)
C330.0289 (13)0.0416 (14)0.0286 (12)0.0001 (10)−0.0068 (10)−0.0084 (10)
C340.0283 (13)0.0349 (13)0.0331 (13)−0.0031 (10)−0.0051 (10)−0.0105 (10)
C410.0258 (12)0.0395 (14)0.0314 (13)−0.0026 (10)−0.0045 (10)−0.0093 (10)
C420.0243 (12)0.0372 (13)0.0323 (13)−0.0041 (10)−0.0037 (10)−0.0104 (10)
C430.0330 (14)0.0494 (16)0.0335 (14)−0.0077 (12)−0.0061 (11)−0.0122 (11)
C440.0328 (14)0.0456 (15)0.0342 (13)−0.0041 (11)−0.0040 (11)−0.0133 (11)
N10.0331 (13)0.0422 (13)0.0601 (16)−0.0029 (10)0.0069 (11)−0.0141 (12)
N20.067 (3)0.056 (2)0.036 (2)0.0162 (18)−0.0130 (17)−0.0197 (19)
N220.092 (10)0.077 (9)0.057 (10)−0.005 (7)0.001 (7)0.003 (7)
O310.0249 (10)0.0641 (14)0.0639 (14)−0.0019 (9)−0.0023 (9)−0.0271 (11)
O320.0438 (12)0.0605 (13)0.0403 (11)0.0000 (10)−0.0177 (9)−0.0202 (9)
O330.0278 (10)0.0801 (15)0.0286 (10)0.0042 (9)−0.0047 (8)−0.0158 (10)
O340.0343 (11)0.0662 (13)0.0325 (10)−0.0051 (9)−0.0060 (8)−0.0199 (9)
O410.0311 (10)0.0732 (14)0.0309 (10)0.0081 (9)−0.0092 (8)−0.0169 (9)
O420.0251 (9)0.0548 (12)0.0361 (10)−0.0007 (8)−0.0064 (7)−0.0159 (8)
O430.0468 (13)0.0953 (18)0.0313 (11)−0.0076 (12)−0.0088 (9)−0.0212 (11)
O440.0351 (12)0.0780 (16)0.0488 (12)0.0093 (11)−0.0010 (9)−0.0263 (11)
Geometric parameters (Å, °) top
C11—N11.475 (4)C25—H25A0.93
C11—C121.518 (4)C26—C271.379 (5)
C11—H11A0.97C26—H26A0.93
C11—H11B0.97C27—C281.391 (4)
C12—C131.491 (4)C27—H27A0.93
C12—H12A0.97C28—C291.494 (4)
C12—H12B0.97C29—N221.400 (12)
C13—C141.394 (4)C29—N21.457 (5)
C13—C181.395 (4)C29—H29A0.97
C14—C151.376 (5)C29—H29B0.97
C14—H14A0.93C29—H29C0.96
C15—C161.375 (5)C29—H29D0.96
C15—H15A0.93C31—O311.216 (3)
C16—C171.373 (5)C31—C341.484 (3)
C16—H16A0.93C31—C321.497 (3)
C17—C181.382 (4)C32—O321.235 (3)
C17—H17A0.93C32—C331.447 (3)
C18—C191.506 (4)C33—O331.299 (3)
C19—N11.475 (4)C33—C341.414 (3)
C19—H19A0.97C34—O341.268 (3)
C19—H19B0.97C41—O411.301 (3)
C21—N221.392 (13)C41—C421.405 (3)
C21—N21.441 (6)C41—C441.444 (3)
C21—C221.503 (5)C42—O421.279 (3)
C21—H21A0.97C42—C431.479 (3)
C21—H21B0.97C43—O431.220 (3)
C21—H21C0.96C43—C441.513 (4)
C21—H21D0.96C44—O441.224 (3)
C22—C231.507 (4)N1—H1A0.90
C22—H22A0.97N1—H1B0.90
C22—H22B0.97N2—H2A0.90
C23—C281.382 (4)N2—H2B0.90
C23—C241.400 (4)N22—H22C0.90
C24—C251.358 (5)N22—H22D0.90
C24—H24A0.93O33—H330.82
C25—C261.361 (6)O41—H410.82
N1—C11—C12110.7 (2)C25—C26—H26A120.1
N1—C11—H11A109.5C27—C26—H26A120.1
C12—C11—H11A109.5C26—C27—C28120.3 (3)
N1—C11—H11B109.5C26—C27—H27A119.9
C12—C11—H11B109.5C28—C27—H27A119.9
H11A—C11—H11B108.1C23—C28—C27120.3 (3)
C13—C12—C11114.7 (2)C23—C28—C29121.3 (3)
C13—C12—H12A108.6C27—C28—C29118.4 (3)
C11—C12—H12A108.6N22—C29—C28116.8 (7)
C13—C12—H12B108.6N2—C29—C28112.4 (3)
C11—C12—H12B108.6N22—C29—H29A129.1
H12A—C12—H12B107.6N2—C29—H29A109.1
C14—C13—C18118.4 (3)C28—C29—H29A109.1
C14—C13—C12120.1 (3)N22—C29—H29B77.2
C18—C13—C12121.4 (2)N2—C29—H29B109.1
C15—C14—C13121.2 (3)C28—C29—H29B109.1
C15—C14—H14A119.4H29A—C29—H29B107.8
C13—C14—H14A119.4N22—C29—H29C101.8
C16—C15—C14119.6 (3)N2—C29—H29C130.5
C16—C15—H15A120.2C28—C29—H29C106.9
C14—C15—H15A120.2H29A—C29—H29C84.1
C17—C16—C15120.2 (3)N22—C29—H29D117.1
C17—C16—H16A119.9N2—C29—H29D89.9
C15—C16—H16A119.9C28—C29—H29D106.7
C16—C17—C18120.7 (3)H29B—C29—H29D128.1
C16—C17—H17A119.7H29C—C29—H29D106.6
C18—C17—H17A119.7O31—C31—C34136.3 (2)
C17—C18—C13119.9 (3)O31—C31—C32135.8 (3)
C17—C18—C19119.9 (3)C34—C31—C3287.98 (19)
C13—C18—C19120.1 (3)O32—C32—C33134.9 (2)
N1—C19—C18111.1 (2)O32—C32—C31136.3 (2)
N1—C19—H19A109.4C33—C32—C3188.76 (19)
C18—C19—H19A109.4O33—C33—C34136.0 (2)
N1—C19—H19B109.4O33—C33—C32131.2 (2)
C18—C19—H19B109.4C34—C33—C3292.7 (2)
H19A—C19—H19B108.0O34—C34—C33134.7 (2)
N22—C21—C22122.9 (7)O34—C34—C31134.7 (2)
N2—C21—C22113.7 (3)C33—C34—C3190.5 (2)
N22—C21—H21A75.7O41—C41—C42135.8 (2)
N2—C21—H21A108.8O41—C41—C44130.6 (2)
C22—C21—H21A108.8C42—C41—C4493.5 (2)
N22—C21—H21B124.3O42—C42—C41134.9 (2)
N2—C21—H21B108.8O42—C42—C43134.4 (2)
C22—C21—H21B108.8C41—C42—C4390.7 (2)
H21A—C21—H21B107.7O43—C43—C42135.3 (3)
N22—C21—H21C115.4O43—C43—C44136.8 (3)
N2—C21—H21C91.2C42—C43—C4487.85 (19)
C22—C21—H21C105.3O44—C44—C41135.5 (3)
H21A—C21—H21C128.1O44—C44—C43136.6 (3)
N22—C21—H21D99.5C41—C44—C4387.9 (2)
N2—C21—H21D130.4C11—N1—C19111.3 (2)
C22—C21—H21D106.0C11—N1—H1A109.4
H21B—C21—H21D83.9C19—N1—H1A109.4
H21C—C21—H21D106.1C11—N1—H1B109.4
C21—C22—C23113.1 (3)C19—N1—H1B109.4
C21—C22—H22A109.0H1A—N1—H1B108.0
C23—C22—H22A109.0C21—N2—C29113.4 (4)
C21—C22—H22B109.0C21—N2—H2A108.9
C23—C22—H22B109.0C29—N2—H2A108.9
H22A—C22—H22B107.8C21—N2—H2B108.9
C28—C23—C24117.5 (3)C29—N2—H2B108.9
C28—C23—C22121.2 (3)H2A—N2—H2B107.7
C24—C23—C22121.3 (3)C21—N22—C29120.3 (12)
C25—C24—C23121.8 (3)C21—N22—H22C107.2
C25—C24—H24A119.1C29—N22—H22C107.2
C23—C24—H24A119.1C21—N22—H22D107.2
C24—C25—C26120.3 (3)C29—N22—H22D107.2
C24—C25—H25A119.8H22C—N22—H22D106.9
C26—C25—H25A119.8C33—O33—H33109.5
C25—C26—C27119.7 (3)C41—O41—H41109.5
N1—C11—C12—C13−38.3 (4)C34—C31—C32—C33−0.9 (2)
C11—C12—C13—C14−172.6 (3)O32—C32—C33—O333.1 (6)
C11—C12—C13—C1810.6 (4)C31—C32—C33—O33−179.6 (3)
C18—C13—C14—C151.0 (4)O32—C32—C33—C34−176.4 (3)
C12—C13—C14—C15−176.0 (3)C31—C32—C33—C341.0 (2)
C13—C14—C15—C160.1 (5)O33—C33—C34—O34−3.1 (6)
C14—C15—C16—C17−1.5 (6)C32—C33—C34—O34176.3 (3)
C15—C16—C17—C181.8 (6)O33—C33—C34—C31179.7 (3)
C16—C17—C18—C13−0.6 (5)C32—C33—C34—C31−1.0 (2)
C16—C17—C18—C19−179.5 (3)O31—C31—C34—O343.8 (6)
C14—C13—C18—C17−0.7 (4)C32—C31—C34—O34−176.3 (3)
C12—C13—C18—C17176.2 (3)O31—C31—C34—C33−178.9 (3)
C14—C13—C18—C19178.1 (3)C32—C31—C34—C330.9 (2)
C12—C13—C18—C19−5.0 (4)O41—C41—C42—O42−0.5 (6)
C17—C18—C19—N1−154.1 (3)C44—C41—C42—O42−179.3 (3)
C13—C18—C19—N127.1 (4)O41—C41—C42—C43179.1 (3)
N22—C21—C22—C23−1.0 (15)C44—C41—C42—C430.3 (2)
N2—C21—C22—C23−37.7 (5)O42—C42—C43—O431.1 (6)
C21—C22—C23—C2811.2 (5)C41—C42—C43—O43−178.5 (4)
C21—C22—C23—C24−171.2 (3)O42—C42—C43—C44179.3 (3)
C28—C23—C24—C251.5 (5)C41—C42—C43—C44−0.3 (2)
C22—C23—C24—C25−176.2 (4)O41—C41—C44—O44−0.6 (6)
C23—C24—C25—C26−0.4 (6)C42—C41—C44—O44178.3 (4)
C24—C25—C26—C27−1.3 (6)O41—C41—C44—C43−179.2 (3)
C25—C26—C27—C281.8 (6)C42—C41—C44—C43−0.3 (2)
C24—C23—C28—C27−1.0 (5)O43—C43—C44—O44−0.1 (7)
C22—C23—C28—C27176.7 (3)C42—C43—C44—O44−178.2 (4)
C24—C23—C28—C29178.4 (3)O43—C43—C44—C41178.4 (4)
C22—C23—C28—C29−3.9 (5)C42—C43—C44—C410.3 (2)
C26—C27—C28—C23−0.6 (5)C12—C11—N1—C1962.4 (3)
C26—C27—C28—C29179.9 (3)C18—C19—N1—C11−55.9 (3)
C23—C28—C29—N22−14.2 (13)N22—C21—N2—C29−55.8 (12)
C27—C28—C29—N22165.2 (13)C22—C21—N2—C2958.4 (5)
C23—C28—C29—N222.0 (5)N22—C29—N2—C2156.1 (12)
C27—C28—C29—N2−158.6 (4)C28—C29—N2—C21−48.9 (5)
O31—C31—C32—O32−3.8 (6)N2—C21—N22—C2966.4 (17)
C34—C31—C32—O32176.3 (3)N2—C29—N22—C21−66.0 (18)
O31—C31—C32—C33178.9 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O33—H33···O420.821.662.476 (2)176
O41—H41···O34i0.821.692.509 (3)178
N1—H1A···O420.902.513.195 (3)133
N2—H2A···O43ii0.902.302.943 (5)128
N2—H2A···O33ii0.902.403.201 (6)148
N2—H2B···O32iii0.901.872.773 (4)177
N22—H22C···O32iii0.901.912.708 (2)147
N22—H22D···O44iv0.901.822.72 (3)174
N1—H1B···O31v0.902.212.910 (3)134
N1—H1B···O42i0.902.362.992 (3)127
N1—H1A···O34i0.902.273.027 (3)142
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x, y−1, z; (iii) −x+1, −y+1, −z; (iv) −x+2, −y+1, −z; (v) −x, −y+2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O33—H33···O420.821.662.476 (2)176
O41—H41···O34i0.821.692.509 (3)178
N1—H1A···O420.902.513.195 (3)133
N2—H2A···O43ii0.902.302.943 (5)128
N2—H2A···O33ii0.902.403.201 (6)148
N2—H2B···O32iii0.901.872.773 (4)177
N22—H22C···O32iii0.901.912.708 (2)147
N22—H22D···O44iv0.901.822.72 (3)174
N1—H1B···O31v0.902.212.910 (3)134
N1—H1B···O42i0.902.362.992 (3)127
N1—H1A···O34i0.902.273.027 (3)142
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x, y−1, z; (iii) −x+1, −y+1, −z; (iv) −x+2, −y+1, −z; (v) −x, −y+2, −z+1.
Acknowledgements top

TK shows appreciation to the DAAD and the Alexander von Humboldt Foundation. RP thanks the Japan Society for the Promotion of Science (JSPS) financial support. This work was supported by the Bulgarian National Fund of Scientific Research (contract No. X-1510/F1212).

references
References top

Alexandrova, R., Varadinova, T., Velcheva, M., Genova, P. & Sainova, I. (2000). Exp. Pathol. Parasitol. 4, 8–14.

Anderson, W. K., Heider, A. R., Raju, N. & Yutch, J. A. (1998). J. Med. Chem. 31, 2097–2102.

Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389–397.

Brzezinska, E. (1994). Acta Pol. Pharm. (Drug. Res.), 51, 137–141.

Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Gargett, C. & Wiley, J. (1997). Br. J. Pharmacol. 120, 1483–1490.

Gilli, G., Bertolasi, V., Gilli, P. & Ferretti, V. (2001). Acta Cryst. B57, 859–865.

Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.

Kolev, T., Preut, H., Bleckmann, P. & Radomirska, V. (1997). Acta Cryst. C53, 805–807.

Kolev, T., Spiteller, M., Sheldrick, W. S. & Mayer-Figge, H. (2005). Acta Cryst. E61, o4292–o4294.

Kolev, T., Spiteller, M., Sheldrick, W. S. & Mayer-Figge, H. (2006). Acta Cryst. C62, o299–o300.

Kolev, T., Spiteller, M., Sheldrick, W. S., Mayer-Figge, H. & Van Almsick, T. (2005). Acta Cryst. E61, o3819–o3821.

Kolev, T., Yancheva, D., Spiteller, M., Sheldrick, W. S. & Mayer-Figge, H. (2006). Acta Cryst. E62, o463–o465.

Loesel, W., Roos, O. & Schnorrenberger, G. (1987). US Patent No. 4 694 085.

Matsuhashi, R., Satou, T., Koike, K., Yokosuka, A., Mimaki, Y., Sashida, Y. & Nikaido, T. (2002). Planta Med. 68, 169–171.

Roqué-Rosell, N., Cironi, P., Solans, X., Albericio, F. & Álvarez, M. (2006). Acta Cryst. E62, o2285–o2287.

Said, I. M., Hamid, N. A. A., Latif, J., Din, L. B. & Yamin, B. M. (2005). Acta Cryst. E61, o797–o798.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.