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The title compound, C6H13N+·H2PO3, contains monoproton­ated 4-aza-1-azoniabi­cyclo­[2.2.2]­octane (dabconium, C6H13N+) cations and di­hydrogenphosphite (H2PO3) anions. The H2PO3 units are linked into a polymeric chain by P—O—H...O—P hydrogen bonds in the [100] direction. The dabconium cations are pendant to the di­hydrogenphosphite chains by way of N—H...O hydrogen bonds and possible C—H...O interactions. The chains are crosslinked by means of van der Waals forces.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803018130/br6113sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803018130/br6113Isup2.hkl
Contains datablock I

CCDC reference: 222892

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.037
  • wR factor = 0.098
  • Data-to-parameter ratio = 19.4

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT241_ALERT_2_C Check High U(eq) as Compared to Neighbors .... C4 PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors .... N1 PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors .... P1
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.50 From the CIF: _reflns_number_total 2139 Count of symmetry unique reflns 1258 Completeness (_total/calc) 170.03% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 881 Fraction of Friedel pairs measured 0.700 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 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 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The crystal structures of amine (hydrogen) phosphites containing HPO32− or H2PO3 ions are of interest in terms of the interplay between cation–anion and anion–anion hydrogen bonds and for comparison with their phosphate (HPO42− or H2PO4) analogues (Averbuch-Pouchot, 1993a,b). Previous reports of phosphite-containing crystal structures have been recently surveyed by Idrissi et al. (2002).

The structure of (I) (Fig. 1) consists of monoprotonated 4-aza-1-azoniabicyclo[2.2.2]octane (dabconium, C6H13N+) cations and dihydrogenphosphite (H2PO3) anions. The dabconium cation has typical (Bremner & Harrison, 2003) geometrical parameters [dav(N—C) = 1.470 (3) Å, dav(C—C) = 1.528 (3) Å and θav(C—N—C) = 109.1 (2)°]. The (HN1)+—C—C bond angles [θav= 108.2 (2)°] are significantly smaller than the equivalent N2—C—C values [θav= 111.1 (2)°]. The dihydrogenphosphite group shows its usual (Idrissi et al., 2002) pseudo-pyramidal geometry [dav(P—O) = 1.508 (2) Å and θav(O—P—O) = 111.9 (2)°]. The protonated P–O1 vertex shows its expected lengthening relative to the other P—O bonds and the unprotonated O2—P1—O3 bond angle (Table 1) is notably larger than the corresponding O—P—OH angles, as seen previously for the same anion in related compounds (Avebuch-Pouchot, 1993a,b; Harrison 2003b).

Apart from electrostatic forces, the component species in (I) interact by means of O—H···O and N—H···O hydrogen bonds (Table 2), and possibly a C—H···O interaction (see below). The H2PO3 units are linked into a polymeric chain by P—O—H···O—P hydrogen bonds in the [100] direction (Fig. 2), resulting in a P1···P1i [symmetry code: (i) 1/2 + x, 3/2 − y, 1 − z] separation of 4.7846 (8) Å. Similar inter-anion linkages have been seen in a number of amine phosphites, for example, isopropylammonium dihydrogenphosphite, (C3H10N)(H2PO3) (Avebuch-Pouchot, 1993a), guanidinium dihydrogenphosphite, (CH6N3)(H2PO3) (Harrison, 2003a), and triethanolammonium dihydrogenphosphite, (C6H16NO3)(H2PO3) (Harrison, 2003b). In all these cases, a 21 screw axis generates the dihydrogenphosphite chain from a single distinct H2PO3 moiety. The organic species are pendant to the chains by way of the N1—H3···O2 hydrogen bonds. A short C2—H6···O2ii [symmetry code: (ii) 1 − x, y, z] interaction was identified in a PLATON (Spek, 2003) analysis of the structure [d(C—H) = 0.97 Å, d(H···O) = 2.53 Å, d(C···O) = 3.450 (3) Å and θ(C—H···O) = 157.8°]. If it is not merely a packing artefact, it may provide some additional coherence betweeen the phosphite backbone and the pendant dabconium cations (Fig. 2). Inter-chain connectivity normal to [110] (Fig. 3) is mediated by van der Waals forces.

Experimental top

H3PO3 (0.82 g, 1 mmol) and dabco (1,4-dianoniabicyclo[2.2.2]octane, C8H12N2; 1.12 g, 1 mmol) were dissolved in 20 ml deionized water, giving a clear solution. Slab- and block-shaped crystals of (I) grew as the water evaporated from the increasingly viscous liquors over the course of several weeks. These colourless transparent crystals were washed with acetone and dried in air. The same phase, adopting a more platy morphology, can also be crystallized from a 1:1 mixture of H3PO3 and dabco in methanol.

Refinement top

The O—H hydrogen atom was found in a difference map and refined by riding in its as-found position. The N—H hydrogen atom was found in a difference map and refined by riding in an idealized position [d(N—H) = 0.91 Å]. H atoms bonded to C and P atoms were placed in calculated positions [d(C—H) = 0.97 Å and d(P—H) = 1.32 Å] and refined by riding. For all H atoms, the constraint Uiso(H) = 1.2Ueq(parent atom) was applied.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97; molecular graphics: ORTEP-3 (Farrugia, 1997) and ATOMS (Shape Software, 1999); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. View of (I) (30% displacement ellipsoids). H atoms are drawn as small spheres of arbitrary radius and hydrogen bonds are indicated by dashed lines. All C—H H atoms have been omitted for clarity.
[Figure 2] Fig. 2. Detail of a [100] dihydrogen phosphite chain and pendant dabconium cations in (I). Colour key: [H2PO3] tetrahedra yellow, O atoms red, C atoms blue, N atoms green, H atoms grey (all radii arbitrary). The H···O portions of the N—H···O hydrogen bonds and C—H···O interactions are highlighted in yellow and light blue, respectively. All C—H H atoms except H5 have been omitted for clarity.
[Figure 3] Fig. 3. [010] projection of (I). Colour key as in Fig. 2. A l l C—H H atoms except H5 have been omitted for clarity.
4-Aza-1-azoniabicyclo[2.2.2]octane dihydrogenphosphite top
Crystal data top
C6H13N2+·H2O3PF(000) = 416
Mr = 194.17Dx = 1.389 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3200 reflections
a = 6.6418 (4) Åθ = 2.5–27.3°
b = 9.9428 (6) ŵ = 0.27 mm1
c = 14.0575 (8) ÅT = 293 K
V = 928.33 (10) Å3Slab, colourless
Z = 40.45 × 0.15 × 0.07 mm
Data collection top
Bruker SMART1000 CCD
diffractometer
2139 independent reflections
Radiation source: fine-focus sealed tube1861 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
ω scansθmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
h = 78
Tmin = 0.886, Tmax = 0.990k = 1012
6962 measured reflectionsl = 1817
Refinement top
Refinement on F2Hydrogen site location: difmap (O-H, N-H) and geom (C-H, P-H)
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.037 w = 1/[σ2(Fo2) + (0.0606P)2 + 0.0257P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.098(Δ/σ)max = 0.001
S = 1.04Δρmax = 0.23 e Å3
2139 reflectionsΔρmin = 0.26 e Å3
110 parametersAbsolute structure: Flack (1983), 881 Friedel pairs
0 restraintsAbsolute structure parameter: 0.15 (12)
Primary atom site location: structure-invariant direct methods
Crystal data top
C6H13N2+·H2O3PV = 928.33 (10) Å3
Mr = 194.17Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.6418 (4) ŵ = 0.27 mm1
b = 9.9428 (6) ÅT = 293 K
c = 14.0575 (8) Å0.45 × 0.15 × 0.07 mm
Data collection top
Bruker SMART1000 CCD
diffractometer
2139 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
1861 reflections with I > 2σ(I)
Tmin = 0.886, Tmax = 0.990Rint = 0.028
6962 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.098Δρmax = 0.23 e Å3
S = 1.04Δρmin = 0.26 e Å3
2139 reflectionsAbsolute structure: Flack (1983), 881 Friedel pairs
110 parametersAbsolute structure parameter: 0.15 (12)
0 restraints
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*/Ueq
P10.72109 (8)0.62955 (5)0.58804 (4)0.04115 (15)
H10.66940.54010.52310.049*
O10.9539 (2)0.64524 (19)0.58243 (12)0.0655 (5)
H21.00900.68530.52410.079*
O20.6770 (3)0.5684 (2)0.68263 (12)0.0697 (6)
O30.6123 (3)0.75504 (19)0.56514 (13)0.0698 (5)
N10.3717 (3)0.61178 (18)0.79192 (12)0.0432 (4)
H30.47840.60260.75180.052*
N20.0775 (3)0.63634 (19)0.90403 (15)0.0540 (4)
C10.2246 (4)0.5024 (2)0.77401 (16)0.0515 (5)
H40.29000.41560.78000.062*
H50.17080.51010.71010.062*
C20.0544 (4)0.5145 (2)0.84689 (19)0.0597 (6)
H60.07400.51680.81410.072*
H70.05550.43640.88820.072*
C30.4417 (4)0.6009 (3)0.89150 (17)0.0682 (8)
H80.54710.66630.90350.082*
H90.49590.51180.90310.082*
C40.2638 (5)0.6269 (4)0.95691 (18)0.0770 (8)
H100.25370.55441.00290.092*
H110.28580.71000.99150.092*
C50.2721 (5)0.7432 (2)0.7746 (2)0.0652 (7)
H120.23410.75100.70820.078*
H130.36340.81620.78990.078*
C60.0845 (4)0.7503 (2)0.8380 (2)0.0652 (7)
H140.08600.83370.87380.078*
H150.03520.74980.79850.078*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0450 (3)0.0391 (2)0.0394 (2)0.0019 (2)0.0010 (2)0.0008 (2)
O10.0491 (9)0.0900 (13)0.0575 (9)0.0011 (9)0.0012 (8)0.0288 (11)
O20.0639 (12)0.0796 (12)0.0657 (11)0.0160 (10)0.0243 (9)0.0282 (10)
O30.0758 (13)0.0634 (10)0.0702 (12)0.0191 (9)0.0149 (9)0.0115 (9)
N10.0410 (8)0.0435 (9)0.0450 (8)0.0003 (7)0.0036 (7)0.0014 (8)
N20.0542 (10)0.0473 (10)0.0607 (10)0.0074 (9)0.0144 (9)0.0016 (11)
C10.0593 (14)0.0393 (10)0.0558 (12)0.0046 (10)0.0007 (11)0.0043 (9)
C20.0515 (14)0.0450 (12)0.0825 (17)0.0061 (10)0.0080 (13)0.0028 (12)
C30.0520 (14)0.097 (2)0.0553 (13)0.0019 (13)0.0110 (10)0.0049 (14)
C40.0820 (19)0.103 (2)0.0457 (12)0.0073 (19)0.0005 (13)0.0099 (15)
C50.0828 (19)0.0349 (10)0.0778 (16)0.0053 (12)0.0222 (15)0.0121 (11)
C60.0681 (16)0.0369 (12)0.0908 (19)0.0101 (11)0.0117 (15)0.0019 (13)
Geometric parameters (Å, º) top
P1—O31.4774 (19)C1—H50.9700
P1—O21.4910 (16)C2—H60.9700
P1—O11.5561 (18)C2—H70.9700
P1—H11.3200C3—C41.519 (4)
O1—H20.9825C3—H80.9700
N1—C31.479 (3)C3—H90.9700
N1—C11.483 (3)C4—H100.9700
N1—C51.485 (3)C4—H110.9700
N1—H30.9100C5—C61.534 (4)
N2—C41.447 (4)C5—H120.9700
N2—C21.462 (3)C5—H130.9700
N2—C61.465 (3)C6—H140.9700
C1—C21.530 (3)C6—H150.9700
C1—H40.9700
O3—P1—O2116.25 (11)C1—C2—H7109.5
O3—P1—O1112.98 (12)H6—C2—H7108.1
O2—P1—O1106.34 (10)N1—C3—C4108.4 (2)
O3—P1—H1106.9N1—C3—H8110.0
O2—P1—H1106.9C4—C3—H8110.0
O1—P1—H1106.9N1—C3—H9110.0
P1—O1—H2117.0C4—C3—H9110.0
C3—N1—C1108.32 (19)H8—C3—H9108.4
C3—N1—C5111.1 (2)N2—C4—C3111.43 (19)
C1—N1—C5108.90 (19)N2—C4—H10109.3
C3—N1—H3109.5C3—C4—H10109.3
C1—N1—H3109.5N2—C4—H11109.3
C5—N1—H3109.5C3—C4—H11109.3
C4—N2—C2108.5 (2)H10—C4—H11108.0
C4—N2—C6110.4 (2)N1—C5—C6107.86 (18)
C2—N2—C6107.24 (19)N1—C5—H12110.1
N1—C1—C2108.39 (17)C6—C5—H12110.1
N1—C1—H4110.0N1—C5—H13110.1
C2—C1—H4110.0C6—C5—H13110.1
N1—C1—H5110.0H12—C5—H13108.4
C2—C1—H5110.0N2—C6—C5111.02 (19)
H4—C1—H5108.4N2—C6—H14109.4
N2—C2—C1110.81 (19)C5—C6—H14109.4
N2—C2—H6109.5N2—C6—H15109.4
C1—C2—H6109.5C5—C6—H15109.4
N2—C2—H7109.5H14—C6—H15108.0
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H2···O3i0.981.552.528 (2)176
N1—H3···O20.911.672.580 (2)174
Symmetry code: (i) x+1/2, y+3/2, z+1.

Experimental details

Crystal data
Chemical formulaC6H13N2+·H2O3P
Mr194.17
Crystal system, space groupOrthorhombic, P212121
Temperature (K)293
a, b, c (Å)6.6418 (4), 9.9428 (6), 14.0575 (8)
V3)928.33 (10)
Z4
Radiation typeMo Kα
µ (mm1)0.27
Crystal size (mm)0.45 × 0.15 × 0.07
Data collection
DiffractometerBruker SMART1000 CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.886, 0.990
No. of measured, independent and
observed [I > 2σ(I)] reflections
6962, 2139, 1861
Rint0.028
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.098, 1.04
No. of reflections2139
No. of parameters110
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.23, 0.26
Absolute structureFlack (1983), 881 Friedel pairs
Absolute structure parameter0.15 (12)

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97, ORTEP-3 (Farrugia, 1997) and ATOMS (Shape Software, 1999).

Selected geometric parameters (Å, º) top
P1—O31.4774 (19)P1—O11.5561 (18)
P1—O21.4910 (16)
O3—P1—O2116.25 (11)O2—P1—O1106.34 (10)
O3—P1—O1112.98 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H2···O3i0.981.552.528 (2)176
N1—H3···O20.911.672.580 (2)174
Symmetry code: (i) x+1/2, y+3/2, z+1.
 

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