Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807030802/ci2392sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807030802/ci2392Isup2.hkl |
CCDC reference: 657649
Key indicators
- Single-crystal X-ray study
- T = 290 K
- Mean (C-C) = 0.005 Å
- Disorder in main residue
- R factor = 0.067
- wR factor = 0.234
- Data-to-parameter ratio = 13.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for N22 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.22 PLAT301_ALERT_3_C Main Residue Disorder ......................... 3.00 Perc. PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 12
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 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
checkCIF publication errors
Alert level A PUBL024_ALERT_1_A The number of authors is greater than 5. Please specify the role of each of the co-authors for your paper.
Author Response: All authors have made substantial contributions to the work. |
1 ALERT level A = Data missing that is essential or data in wrong format 0 ALERT level G = General alerts. Data that may be required is missing
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).
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.
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).
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.
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).
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).
C9H12N+·C4HO4− | Z = 4 |
Mr = 247.24 | F(000) = 520 |
Triclinic, P1 | Dx = 1.449 Mg m−3 |
Hall symbol: -P 1 | Melting point: not measured K |
a = 8.1456 (10) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.936 (2) Å | Cell parameters from 22 reflections |
c = 13.6897 (12) Å | θ = 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) Å3 | 0.40 × 0.40 × 0.40 mm |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.042 |
Radiation source: fine-focus sealed tube | θmax = 26.0°, θmin = 1.5° |
Graphite monochromator | h = 0→10 |
non–profiled ω/2θ scans | k = −12→13 |
4773 measured reflections | l = −16→16 |
4444 independent reflections | 3 standard reflections every 120 min |
3226 reflections with I > 2σ(I) | intensity decay: 1% |
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)] = 0.067 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.234 | H-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 parameters | Δρmax = 0.45 e Å−3 |
12 restraints | Δρmin = −0.32 e Å−3 |
C9H12N+·C4HO4− | γ = 74.319 (13)° |
Mr = 247.24 | V = 1133.4 (3) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.1456 (10) Å | Mo Kα radiation |
b = 10.936 (2) Å | µ = 0.11 mm−1 |
c = 13.6897 (12) Å | T = 290 K |
α = 77.81 (2)° | 0.40 × 0.40 × 0.40 mm |
β = 78.170 (17)° |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.042 |
4773 measured reflections | 3 standard reflections every 120 min |
4444 independent reflections | intensity decay: 1% |
3226 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.067 | 12 restraints |
wR(F2) = 0.234 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.45 e Å−3 |
4444 reflections | Δρmin = −0.32 e Å−3 |
335 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C11 | 0.5030 (4) | 0.7057 (3) | 0.6246 (2) | 0.0522 (8) | |
H11A | 0.4125 | 0.6594 | 0.6488 | 0.063* | |
H11B | 0.5215 | 0.7383 | 0.6811 | 0.063* | |
C12 | 0.6682 (4) | 0.6146 (3) | 0.5848 (2) | 0.0482 (7) | |
H12A | 0.7655 | 0.6479 | 0.5883 | 0.058* | |
H12B | 0.6786 | 0.5318 | 0.6289 | 0.058* | |
C13 | 0.6795 (3) | 0.5948 (2) | 0.4790 (2) | 0.0369 (6) | |
C14 | 0.8152 (4) | 0.5022 (3) | 0.4379 (3) | 0.0488 (8) | |
H14A | 0.8942 | 0.4495 | 0.4784 | 0.059* | |
C15 | 0.8344 (5) | 0.4875 (3) | 0.3385 (3) | 0.0586 (9) | |
H15A | 0.9256 | 0.4252 | 0.3122 | 0.070* | |
C16 | 0.7181 (5) | 0.5654 (4) | 0.2782 (3) | 0.0650 (10) | |
H16A | 0.7321 | 0.5571 | 0.2106 | 0.078* | |
C17 | 0.5813 (5) | 0.6553 (4) | 0.3177 (3) | 0.0565 (8) | |
H17A | 0.5014 | 0.7060 | 0.2769 | 0.068* | |
C18 | 0.5611 (3) | 0.6713 (3) | 0.4173 (2) | 0.0385 (6) | |
C19 | 0.4094 (4) | 0.7697 (3) | 0.4595 (2) | 0.0487 (8) | |
H19A | 0.3802 | 0.8426 | 0.4066 | 0.058* | |
H19B | 0.3103 | 0.7321 | 0.4824 | 0.058* | |
C21 | 0.7842 (5) | 0.1957 (5) | 0.0189 (3) | 0.0763 (13) | |
H21A | 0.8145 | 0.2461 | −0.0465 | 0.092* | 0.796 (14) |
H21B | 0.8907 | 0.1450 | 0.0422 | 0.092* | 0.796 (14) |
H21C | 0.8582 | 0.1265 | 0.0568 | 0.092* | 0.204 (14) |
H21D | 0.8591 | 0.2409 | −0.0300 | 0.092* | 0.204 (14) |
C22 | 0.6897 (4) | 0.2857 (4) | 0.0921 (3) | 0.0645 (10) | |
H22A | 0.7410 | 0.3592 | 0.0785 | 0.077* | |
H22B | 0.7040 | 0.2418 | 0.1603 | 0.077* | |
C23 | 0.4997 (4) | 0.3332 (3) | 0.0863 (2) | 0.0439 (7) | |
C24 | 0.3951 (5) | 0.4308 (3) | 0.1385 (2) | 0.0574 (9) | |
H24A | 0.4456 | 0.4705 | 0.1742 | 0.069* | |
C25 | 0.2221 (5) | 0.4693 (4) | 0.1385 (3) | 0.0667 (10) | |
H25A | 0.1560 | 0.5341 | 0.1743 | 0.080* | |
C26 | 0.1449 (5) | 0.4134 (4) | 0.0864 (3) | 0.0693 (11) | |
H26A | 0.0260 | 0.4387 | 0.0877 | 0.083* | |
C27 | 0.2438 (4) | 0.3191 (3) | 0.0318 (2) | 0.0532 (8) | |
H27A | 0.1918 | 0.2825 | −0.0054 | 0.064* | |
C28 | 0.4209 (4) | 0.2785 (3) | 0.0320 (2) | 0.0402 (6) | |
C29 | 0.5227 (4) | 0.1760 (3) | −0.0282 (3) | 0.0556 (8) | |
H29A | 0.4550 | 0.1139 | −0.0236 | 0.067* | 0.796 (14) |
H29B | 0.5451 | 0.2146 | −0.0988 | 0.067* | 0.796 (14) |
H29C | 0.4949 | 0.2037 | −0.0955 | 0.067* | 0.204 (14) |
H29D | 0.4787 | 0.1008 | −0.0003 | 0.067* | 0.204 (14) |
C31 | 0.0455 (3) | 1.1145 (2) | 0.3028 (2) | 0.0341 (6) | |
C32 | 0.1510 (3) | 1.0709 (3) | 0.20780 (19) | 0.0340 (6) | |
C33 | 0.3049 (3) | 1.0510 (3) | 0.25202 (19) | 0.0340 (6) | |
C34 | 0.2090 (3) | 1.0895 (2) | 0.34349 (19) | 0.0322 (6) | |
C41 | 0.9529 (3) | 0.8286 (2) | 0.35799 (18) | 0.0328 (6) | |
C42 | 0.8025 (3) | 0.8920 (2) | 0.31596 (18) | 0.0313 (6) | |
C43 | 0.8868 (3) | 0.8533 (3) | 0.2170 (2) | 0.0381 (6) | |
C44 | 1.0468 (3) | 0.7868 (3) | 0.2646 (2) | 0.0377 (6) | |
N1 | 0.4485 (3) | 0.8144 (2) | 0.54460 (19) | 0.0476 (6) | |
H1A | 0.5331 | 0.8568 | 0.5218 | 0.057* | |
H1B | 0.3541 | 0.8696 | 0.5706 | 0.057* | |
N2 | 0.6865 (5) | 0.1096 (4) | 0.0066 (4) | 0.0567 (16) | 0.796 (14) |
H2A | 0.6656 | 0.0583 | 0.0661 | 0.068* | 0.796 (14) |
H2B | 0.7504 | 0.0590 | −0.0383 | 0.068* | 0.796 (14) |
N22 | 0.7023 (16) | 0.159 (2) | −0.0462 (17) | 0.082 (7) | 0.204 (14) |
H22C | 0.7490 | 0.0748 | −0.0480 | 0.099* | 0.204 (14) |
H22D | 0.7304 | 0.2017 | −0.1086 | 0.099* | 0.204 (14) |
O31 | −0.1074 (2) | 1.1535 (2) | 0.33295 (17) | 0.0509 (6) | |
O32 | 0.1216 (3) | 1.0535 (2) | 0.12745 (15) | 0.0471 (5) | |
O33 | 0.4673 (2) | 1.0111 (2) | 0.21660 (13) | 0.0478 (6) | |
H33 | 0.5244 | 0.9943 | 0.2626 | 0.072* | |
O34 | 0.2468 (2) | 1.0950 (2) | 0.42759 (14) | 0.0438 (5) | |
O41 | 1.0005 (2) | 0.8119 (2) | 0.44593 (14) | 0.0472 (6) | |
H41 | 0.9183 | 0.8426 | 0.4863 | 0.071* | |
O42 | 0.6533 (2) | 0.95743 (19) | 0.34911 (13) | 0.0389 (5) | |
O43 | 0.8447 (3) | 0.8715 (3) | 0.13369 (15) | 0.0576 (6) | |
O44 | 1.1933 (3) | 0.7263 (2) | 0.23680 (17) | 0.0569 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C11 | 0.0468 (18) | 0.0601 (19) | 0.0448 (17) | −0.0066 (15) | −0.0022 (13) | −0.0104 (14) |
C12 | 0.0426 (17) | 0.0480 (17) | 0.0509 (17) | −0.0027 (13) | −0.0111 (13) | −0.0082 (13) |
C13 | 0.0300 (13) | 0.0327 (13) | 0.0488 (16) | −0.0082 (11) | −0.0063 (11) | −0.0072 (11) |
C14 | 0.0351 (16) | 0.0397 (15) | 0.071 (2) | −0.0025 (12) | −0.0089 (14) | −0.0149 (14) |
C15 | 0.0517 (19) | 0.0536 (19) | 0.072 (2) | −0.0102 (15) | 0.0040 (17) | −0.0303 (17) |
C16 | 0.076 (3) | 0.073 (2) | 0.057 (2) | −0.025 (2) | −0.0041 (18) | −0.0291 (18) |
C17 | 0.058 (2) | 0.065 (2) | 0.0494 (18) | −0.0150 (17) | −0.0180 (15) | −0.0064 (16) |
C18 | 0.0308 (14) | 0.0386 (14) | 0.0450 (15) | −0.0086 (11) | −0.0062 (11) | −0.0038 (12) |
C19 | 0.0314 (15) | 0.0486 (17) | 0.0583 (19) | 0.0004 (13) | −0.0103 (13) | −0.0014 (14) |
C21 | 0.0388 (19) | 0.121 (4) | 0.059 (2) | 0.006 (2) | −0.0110 (16) | −0.022 (2) |
C22 | 0.0431 (19) | 0.103 (3) | 0.053 (2) | −0.0139 (18) | −0.0088 (15) | −0.0277 (19) |
C23 | 0.0470 (17) | 0.0510 (17) | 0.0346 (14) | −0.0104 (13) | −0.0054 (12) | −0.0117 (12) |
C24 | 0.072 (2) | 0.0558 (19) | 0.0489 (18) | −0.0170 (17) | −0.0027 (16) | −0.0224 (15) |
C25 | 0.061 (2) | 0.059 (2) | 0.064 (2) | 0.0084 (17) | 0.0049 (18) | −0.0197 (17) |
C26 | 0.047 (2) | 0.077 (3) | 0.069 (2) | 0.0066 (18) | −0.0076 (18) | −0.012 (2) |
C27 | 0.0472 (18) | 0.066 (2) | 0.0489 (18) | −0.0156 (16) | −0.0131 (14) | −0.0066 (15) |
C28 | 0.0435 (16) | 0.0431 (15) | 0.0325 (13) | −0.0065 (12) | −0.0037 (11) | −0.0101 (11) |
C29 | 0.055 (2) | 0.059 (2) | 0.0529 (18) | 0.0006 (16) | −0.0100 (15) | −0.0272 (16) |
C31 | 0.0298 (13) | 0.0357 (13) | 0.0375 (13) | −0.0048 (10) | −0.0051 (10) | −0.0114 (11) |
C32 | 0.0324 (13) | 0.0386 (14) | 0.0314 (13) | −0.0024 (11) | −0.0092 (10) | −0.0106 (10) |
C33 | 0.0289 (13) | 0.0416 (14) | 0.0286 (12) | 0.0001 (10) | −0.0068 (10) | −0.0084 (10) |
C34 | 0.0283 (13) | 0.0349 (13) | 0.0331 (13) | −0.0031 (10) | −0.0051 (10) | −0.0105 (10) |
C41 | 0.0258 (12) | 0.0395 (14) | 0.0314 (13) | −0.0026 (10) | −0.0045 (10) | −0.0093 (10) |
C42 | 0.0243 (12) | 0.0372 (13) | 0.0323 (13) | −0.0041 (10) | −0.0037 (10) | −0.0104 (10) |
C43 | 0.0330 (14) | 0.0494 (16) | 0.0335 (14) | −0.0077 (12) | −0.0061 (11) | −0.0122 (11) |
C44 | 0.0328 (14) | 0.0456 (15) | 0.0342 (13) | −0.0041 (11) | −0.0040 (11) | −0.0133 (11) |
N1 | 0.0331 (13) | 0.0422 (13) | 0.0601 (16) | −0.0029 (10) | 0.0069 (11) | −0.0141 (12) |
N2 | 0.067 (3) | 0.056 (2) | 0.036 (2) | 0.0162 (18) | −0.0130 (17) | −0.0197 (19) |
N22 | 0.092 (10) | 0.077 (9) | 0.057 (10) | −0.005 (7) | 0.001 (7) | 0.003 (7) |
O31 | 0.0249 (10) | 0.0641 (14) | 0.0639 (14) | −0.0019 (9) | −0.0023 (9) | −0.0271 (11) |
O32 | 0.0438 (12) | 0.0605 (13) | 0.0403 (11) | 0.0000 (10) | −0.0177 (9) | −0.0202 (9) |
O33 | 0.0278 (10) | 0.0801 (15) | 0.0286 (10) | 0.0042 (9) | −0.0047 (8) | −0.0158 (10) |
O34 | 0.0343 (11) | 0.0662 (13) | 0.0325 (10) | −0.0051 (9) | −0.0060 (8) | −0.0199 (9) |
O41 | 0.0311 (10) | 0.0732 (14) | 0.0309 (10) | 0.0081 (9) | −0.0092 (8) | −0.0169 (9) |
O42 | 0.0251 (9) | 0.0548 (12) | 0.0361 (10) | −0.0007 (8) | −0.0064 (7) | −0.0159 (8) |
O43 | 0.0468 (13) | 0.0953 (18) | 0.0313 (11) | −0.0076 (12) | −0.0088 (9) | −0.0212 (11) |
O44 | 0.0351 (12) | 0.0780 (16) | 0.0488 (12) | 0.0093 (11) | −0.0010 (9) | −0.0263 (11) |
C11—N1 | 1.475 (4) | C25—H25A | 0.93 |
C11—C12 | 1.518 (4) | C26—C27 | 1.379 (5) |
C11—H11A | 0.97 | C26—H26A | 0.93 |
C11—H11B | 0.97 | C27—C28 | 1.391 (4) |
C12—C13 | 1.491 (4) | C27—H27A | 0.93 |
C12—H12A | 0.97 | C28—C29 | 1.494 (4) |
C12—H12B | 0.97 | C29—N22 | 1.400 (12) |
C13—C14 | 1.394 (4) | C29—N2 | 1.457 (5) |
C13—C18 | 1.395 (4) | C29—H29A | 0.97 |
C14—C15 | 1.376 (5) | C29—H29B | 0.97 |
C14—H14A | 0.93 | C29—H29C | 0.96 |
C15—C16 | 1.375 (5) | C29—H29D | 0.96 |
C15—H15A | 0.93 | C31—O31 | 1.216 (3) |
C16—C17 | 1.373 (5) | C31—C34 | 1.484 (3) |
C16—H16A | 0.93 | C31—C32 | 1.497 (3) |
C17—C18 | 1.382 (4) | C32—O32 | 1.235 (3) |
C17—H17A | 0.93 | C32—C33 | 1.447 (3) |
C18—C19 | 1.506 (4) | C33—O33 | 1.299 (3) |
C19—N1 | 1.475 (4) | C33—C34 | 1.414 (3) |
C19—H19A | 0.97 | C34—O34 | 1.268 (3) |
C19—H19B | 0.97 | C41—O41 | 1.301 (3) |
C21—N22 | 1.392 (13) | C41—C42 | 1.405 (3) |
C21—N2 | 1.441 (6) | C41—C44 | 1.444 (3) |
C21—C22 | 1.503 (5) | C42—O42 | 1.279 (3) |
C21—H21A | 0.97 | C42—C43 | 1.479 (3) |
C21—H21B | 0.97 | C43—O43 | 1.220 (3) |
C21—H21C | 0.96 | C43—C44 | 1.513 (4) |
C21—H21D | 0.96 | C44—O44 | 1.224 (3) |
C22—C23 | 1.507 (4) | N1—H1A | 0.90 |
C22—H22A | 0.97 | N1—H1B | 0.90 |
C22—H22B | 0.97 | N2—H2A | 0.90 |
C23—C28 | 1.382 (4) | N2—H2B | 0.90 |
C23—C24 | 1.400 (4) | N22—H22C | 0.90 |
C24—C25 | 1.358 (5) | N22—H22D | 0.90 |
C24—H24A | 0.93 | O33—H33 | 0.82 |
C25—C26 | 1.361 (6) | O41—H41 | 0.82 |
N1—C11—C12 | 110.7 (2) | C25—C26—H26A | 120.1 |
N1—C11—H11A | 109.5 | C27—C26—H26A | 120.1 |
C12—C11—H11A | 109.5 | C26—C27—C28 | 120.3 (3) |
N1—C11—H11B | 109.5 | C26—C27—H27A | 119.9 |
C12—C11—H11B | 109.5 | C28—C27—H27A | 119.9 |
H11A—C11—H11B | 108.1 | C23—C28—C27 | 120.3 (3) |
C13—C12—C11 | 114.7 (2) | C23—C28—C29 | 121.3 (3) |
C13—C12—H12A | 108.6 | C27—C28—C29 | 118.4 (3) |
C11—C12—H12A | 108.6 | N22—C29—C28 | 116.8 (7) |
C13—C12—H12B | 108.6 | N2—C29—C28 | 112.4 (3) |
C11—C12—H12B | 108.6 | N22—C29—H29A | 129.1 |
H12A—C12—H12B | 107.6 | N2—C29—H29A | 109.1 |
C14—C13—C18 | 118.4 (3) | C28—C29—H29A | 109.1 |
C14—C13—C12 | 120.1 (3) | N22—C29—H29B | 77.2 |
C18—C13—C12 | 121.4 (2) | N2—C29—H29B | 109.1 |
C15—C14—C13 | 121.2 (3) | C28—C29—H29B | 109.1 |
C15—C14—H14A | 119.4 | H29A—C29—H29B | 107.8 |
C13—C14—H14A | 119.4 | N22—C29—H29C | 101.8 |
C16—C15—C14 | 119.6 (3) | N2—C29—H29C | 130.5 |
C16—C15—H15A | 120.2 | C28—C29—H29C | 106.9 |
C14—C15—H15A | 120.2 | H29A—C29—H29C | 84.1 |
C17—C16—C15 | 120.2 (3) | N22—C29—H29D | 117.1 |
C17—C16—H16A | 119.9 | N2—C29—H29D | 89.9 |
C15—C16—H16A | 119.9 | C28—C29—H29D | 106.7 |
C16—C17—C18 | 120.7 (3) | H29B—C29—H29D | 128.1 |
C16—C17—H17A | 119.7 | H29C—C29—H29D | 106.6 |
C18—C17—H17A | 119.7 | O31—C31—C34 | 136.3 (2) |
C17—C18—C13 | 119.9 (3) | O31—C31—C32 | 135.8 (3) |
C17—C18—C19 | 119.9 (3) | C34—C31—C32 | 87.98 (19) |
C13—C18—C19 | 120.1 (3) | O32—C32—C33 | 134.9 (2) |
N1—C19—C18 | 111.1 (2) | O32—C32—C31 | 136.3 (2) |
N1—C19—H19A | 109.4 | C33—C32—C31 | 88.76 (19) |
C18—C19—H19A | 109.4 | O33—C33—C34 | 136.0 (2) |
N1—C19—H19B | 109.4 | O33—C33—C32 | 131.2 (2) |
C18—C19—H19B | 109.4 | C34—C33—C32 | 92.7 (2) |
H19A—C19—H19B | 108.0 | O34—C34—C33 | 134.7 (2) |
N22—C21—C22 | 122.9 (7) | O34—C34—C31 | 134.7 (2) |
N2—C21—C22 | 113.7 (3) | C33—C34—C31 | 90.5 (2) |
N22—C21—H21A | 75.7 | O41—C41—C42 | 135.8 (2) |
N2—C21—H21A | 108.8 | O41—C41—C44 | 130.6 (2) |
C22—C21—H21A | 108.8 | C42—C41—C44 | 93.5 (2) |
N22—C21—H21B | 124.3 | O42—C42—C41 | 134.9 (2) |
N2—C21—H21B | 108.8 | O42—C42—C43 | 134.4 (2) |
C22—C21—H21B | 108.8 | C41—C42—C43 | 90.7 (2) |
H21A—C21—H21B | 107.7 | O43—C43—C42 | 135.3 (3) |
N22—C21—H21C | 115.4 | O43—C43—C44 | 136.8 (3) |
N2—C21—H21C | 91.2 | C42—C43—C44 | 87.85 (19) |
C22—C21—H21C | 105.3 | O44—C44—C41 | 135.5 (3) |
H21A—C21—H21C | 128.1 | O44—C44—C43 | 136.6 (3) |
N22—C21—H21D | 99.5 | C41—C44—C43 | 87.9 (2) |
N2—C21—H21D | 130.4 | C11—N1—C19 | 111.3 (2) |
C22—C21—H21D | 106.0 | C11—N1—H1A | 109.4 |
H21B—C21—H21D | 83.9 | C19—N1—H1A | 109.4 |
H21C—C21—H21D | 106.1 | C11—N1—H1B | 109.4 |
C21—C22—C23 | 113.1 (3) | C19—N1—H1B | 109.4 |
C21—C22—H22A | 109.0 | H1A—N1—H1B | 108.0 |
C23—C22—H22A | 109.0 | C21—N2—C29 | 113.4 (4) |
C21—C22—H22B | 109.0 | C21—N2—H2A | 108.9 |
C23—C22—H22B | 109.0 | C29—N2—H2A | 108.9 |
H22A—C22—H22B | 107.8 | C21—N2—H2B | 108.9 |
C28—C23—C24 | 117.5 (3) | C29—N2—H2B | 108.9 |
C28—C23—C22 | 121.2 (3) | H2A—N2—H2B | 107.7 |
C24—C23—C22 | 121.3 (3) | C21—N22—C29 | 120.3 (12) |
C25—C24—C23 | 121.8 (3) | C21—N22—H22C | 107.2 |
C25—C24—H24A | 119.1 | C29—N22—H22C | 107.2 |
C23—C24—H24A | 119.1 | C21—N22—H22D | 107.2 |
C24—C25—C26 | 120.3 (3) | C29—N22—H22D | 107.2 |
C24—C25—H25A | 119.8 | H22C—N22—H22D | 106.9 |
C26—C25—H25A | 119.8 | C33—O33—H33 | 109.5 |
C25—C26—C27 | 119.7 (3) | C41—O41—H41 | 109.5 |
N1—C11—C12—C13 | −38.3 (4) | C34—C31—C32—C33 | −0.9 (2) |
C11—C12—C13—C14 | −172.6 (3) | O32—C32—C33—O33 | 3.1 (6) |
C11—C12—C13—C18 | 10.6 (4) | C31—C32—C33—O33 | −179.6 (3) |
C18—C13—C14—C15 | 1.0 (4) | O32—C32—C33—C34 | −176.4 (3) |
C12—C13—C14—C15 | −176.0 (3) | C31—C32—C33—C34 | 1.0 (2) |
C13—C14—C15—C16 | 0.1 (5) | O33—C33—C34—O34 | −3.1 (6) |
C14—C15—C16—C17 | −1.5 (6) | C32—C33—C34—O34 | 176.3 (3) |
C15—C16—C17—C18 | 1.8 (6) | O33—C33—C34—C31 | 179.7 (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—O34 | 3.8 (6) |
C14—C13—C18—C17 | −0.7 (4) | C32—C31—C34—O34 | −176.3 (3) |
C12—C13—C18—C17 | 176.2 (3) | O31—C31—C34—C33 | −178.9 (3) |
C14—C13—C18—C19 | 178.1 (3) | C32—C31—C34—C33 | 0.9 (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—N1 | 27.1 (4) | O41—C41—C42—C43 | 179.1 (3) |
N22—C21—C22—C23 | −1.0 (15) | C44—C41—C42—C43 | 0.3 (2) |
N2—C21—C22—C23 | −37.7 (5) | O42—C42—C43—O43 | 1.1 (6) |
C21—C22—C23—C28 | 11.2 (5) | C41—C42—C43—O43 | −178.5 (4) |
C21—C22—C23—C24 | −171.2 (3) | O42—C42—C43—C44 | 179.3 (3) |
C28—C23—C24—C25 | 1.5 (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—O44 | 178.3 (4) |
C24—C25—C26—C27 | −1.3 (6) | O41—C41—C44—C43 | −179.2 (3) |
C25—C26—C27—C28 | 1.8 (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—C27 | 176.7 (3) | C42—C43—C44—O44 | −178.2 (4) |
C24—C23—C28—C29 | 178.4 (3) | O43—C43—C44—C41 | 178.4 (4) |
C22—C23—C28—C29 | −3.9 (5) | C42—C43—C44—C41 | 0.3 (2) |
C26—C27—C28—C23 | −0.6 (5) | C12—C11—N1—C19 | 62.4 (3) |
C26—C27—C28—C29 | 179.9 (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—N22 | 165.2 (13) | C22—C21—N2—C29 | 58.4 (5) |
C23—C28—C29—N2 | 22.0 (5) | N22—C29—N2—C21 | 56.1 (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—C29 | 66.4 (17) |
C34—C31—C32—O32 | 176.3 (3) | N2—C29—N22—C21 | −66.0 (18) |
O31—C31—C32—C33 | 178.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O33—H33···O42 | 0.82 | 1.66 | 2.476 (2) | 176 |
O41—H41···O34i | 0.82 | 1.69 | 2.509 (3) | 178 |
N1—H1A···O42 | 0.90 | 2.51 | 3.195 (3) | 133 |
N2—H2A···O43ii | 0.90 | 2.30 | 2.943 (5) | 128 |
N2—H2A···O33ii | 0.90 | 2.40 | 3.201 (6) | 148 |
N2—H2B···O32iii | 0.90 | 1.87 | 2.773 (4) | 177 |
N22—H22C···O32iii | 0.90 | 1.91 | 2.708 (2) | 147 |
N22—H22D···O44iv | 0.90 | 1.82 | 2.72 (3) | 174 |
N1—H1B···O31v | 0.90 | 2.21 | 2.910 (3) | 134 |
N1—H1B···O42i | 0.90 | 2.36 | 2.992 (3) | 127 |
N1—H1A···O34i | 0.90 | 2.27 | 3.027 (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. |
Experimental details
Crystal data | |
Chemical formula | C9H12N+·C4HO4− |
Mr | 247.24 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 290 |
a, b, c (Å) | 8.1456 (10), 10.936 (2), 13.6897 (12) |
α, β, γ (°) | 77.81 (2), 78.170 (17), 74.319 (13) |
V (Å3) | 1133.4 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.40 × 0.40 × 0.40 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4773, 4444, 3226 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.234, 1.02 |
No. of reflections | 4444 |
No. of parameters | 335 |
No. of restraints | 12 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.32 |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Bruno et al., 2002), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O33—H33···O42 | 0.82 | 1.66 | 2.476 (2) | 176 |
O41—H41···O34i | 0.82 | 1.69 | 2.509 (3) | 178 |
N1—H1A···O42 | 0.90 | 2.51 | 3.195 (3) | 133 |
N2—H2A···O43ii | 0.90 | 2.30 | 2.943 (5) | 128 |
N2—H2A···O33ii | 0.90 | 2.40 | 3.201 (6) | 148 |
N2—H2B···O32iii | 0.90 | 1.87 | 2.773 (4) | 177 |
N22—H22C···O32iii | 0.90 | 1.91 | 2.708 (2) | 147 |
N22—H22D···O44iv | 0.90 | 1.82 | 2.72 (3) | 174 |
N1—H1B···O31v | 0.90 | 2.21 | 2.910 (3) | 134 |
N1—H1B···O42i | 0.90 | 2.36 | 2.992 (3) | 127 |
N1—H1A···O34i | 0.90 | 2.27 | 3.027 (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. |
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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.