Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807030802/ci2392sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807030802/ci2392Isup2.hkl
Contains datablock I

CCDC reference: 657649

Key indicators

  • Single-crystal X-ray study
  • T = 290 K
  • Mean [sigma](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

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 CO 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).

Structure description 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 CO 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).

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+·C4HO4Z = 4
Mr = 247.24F(000) = 520
Triclinic, P1Dx = 1.449 Mg m3
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 mm1
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°
Graphite monochromatorh = 010
non–profiled ω/2θ scansk = 1213
4773 measured reflectionsl = 1616
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 Å3
12 restraintsΔρmin = 0.32 e Å3
Crystal data top
C9H12N+·C4HO4γ = 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 mm1
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 reflections3 standard reflections every 120 min
4444 independent reflections intensity decay: 1%
3226 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.06712 restraints
wR(F2) = 0.234H-atom parameters constrained
S = 1.02Δρmax = 0.45 e Å3
4444 reflectionsΔρmin = 0.32 e Å3
335 parameters
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)
H21A0.81450.24610.04650.092*0.796 (14)
H21B0.89070.14500.04220.092*0.796 (14)
H21C0.85820.12650.05680.092*0.204 (14)
H21D0.85910.24090.03000.092*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)
H27A0.19180.28250.00540.064*
C280.4209 (4)0.2785 (3)0.0320 (2)0.0402 (6)
C290.5227 (4)0.1760 (3)0.0282 (3)0.0556 (8)
H29A0.45500.11390.02360.067*0.796 (14)
H29B0.54510.21460.09880.067*0.796 (14)
H29C0.49490.20370.09550.067*0.204 (14)
H29D0.47870.10080.00030.067*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)
H2B0.75040.05900.03830.068*0.796 (14)
N220.7023 (16)0.159 (2)0.0462 (17)0.082 (7)0.204 (14)
H22C0.74900.07480.04800.099*0.204 (14)
H22D0.73040.20170.10860.099*0.204 (14)
O310.1074 (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, º) 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—C1338.3 (4)C34—C31—C32—C330.9 (2)
C11—C12—C13—C14172.6 (3)O32—C32—C33—O333.1 (6)
C11—C12—C13—C1810.6 (4)C31—C32—C33—O33179.6 (3)
C18—C13—C14—C151.0 (4)O32—C32—C33—C34176.4 (3)
C12—C13—C14—C15176.0 (3)C31—C32—C33—C341.0 (2)
C13—C14—C15—C160.1 (5)O33—C33—C34—O343.1 (6)
C14—C15—C16—C171.5 (6)C32—C33—C34—O34176.3 (3)
C15—C16—C17—C181.8 (6)O33—C33—C34—C31179.7 (3)
C16—C17—C18—C130.6 (5)C32—C33—C34—C311.0 (2)
C16—C17—C18—C19179.5 (3)O31—C31—C34—O343.8 (6)
C14—C13—C18—C170.7 (4)C32—C31—C34—O34176.3 (3)
C12—C13—C18—C17176.2 (3)O31—C31—C34—C33178.9 (3)
C14—C13—C18—C19178.1 (3)C32—C31—C34—C330.9 (2)
C12—C13—C18—C195.0 (4)O41—C41—C42—O420.5 (6)
C17—C18—C19—N1154.1 (3)C44—C41—C42—O42179.3 (3)
C13—C18—C19—N127.1 (4)O41—C41—C42—C43179.1 (3)
N22—C21—C22—C231.0 (15)C44—C41—C42—C430.3 (2)
N2—C21—C22—C2337.7 (5)O42—C42—C43—O431.1 (6)
C21—C22—C23—C2811.2 (5)C41—C42—C43—O43178.5 (4)
C21—C22—C23—C24171.2 (3)O42—C42—C43—C44179.3 (3)
C28—C23—C24—C251.5 (5)C41—C42—C43—C440.3 (2)
C22—C23—C24—C25176.2 (4)O41—C41—C44—O440.6 (6)
C23—C24—C25—C260.4 (6)C42—C41—C44—O44178.3 (4)
C24—C25—C26—C271.3 (6)O41—C41—C44—C43179.2 (3)
C25—C26—C27—C281.8 (6)C42—C41—C44—C430.3 (2)
C24—C23—C28—C271.0 (5)O43—C43—C44—O440.1 (7)
C22—C23—C28—C27176.7 (3)C42—C43—C44—O44178.2 (4)
C24—C23—C28—C29178.4 (3)O43—C43—C44—C41178.4 (4)
C22—C23—C28—C293.9 (5)C42—C43—C44—C410.3 (2)
C26—C27—C28—C230.6 (5)C12—C11—N1—C1962.4 (3)
C26—C27—C28—C29179.9 (3)C18—C19—N1—C1155.9 (3)
C23—C28—C29—N2214.2 (13)N22—C21—N2—C2955.8 (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—N2158.6 (4)C28—C29—N2—C2148.9 (5)
O31—C31—C32—O323.8 (6)N2—C21—N22—C2966.4 (17)
C34—C31—C32—O32176.3 (3)N2—C29—N22—C2166.0 (18)
O31—C31—C32—C33178.9 (3)
Hydrogen-bond geometry (Å, º) 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, y1, z; (iii) x+1, y+1, z; (iv) x+2, y+1, z; (v) x, y+2, z+1.

Experimental details

Crystal data
Chemical formulaC9H12N+·C4HO4
Mr247.24
Crystal system, space groupTriclinic, 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)
V3)1133.4 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.40 × 0.40 × 0.40
Data collection
DiffractometerEnraf–Nonius CAD-4
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4773, 4444, 3226
Rint0.042
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.067, 0.234, 1.02
No. of reflections4444
No. of parameters335
No. of restraints12
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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).

Hydrogen-bond geometry (Å, º) 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, y1, z; (iii) x+1, y+1, z; (iv) x+2, y+1, z; (v) x, y+2, z+1.
 

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds