Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803016982/cv6217sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803016982/cv6217Isup2.hkl |
CCDC reference: 222850
H3PO3 (0.81 g, 1 mmol) and triethanolamine (1.49 g, 1 mmol) were dissolved in 20 ml deionized water in a Petri dish to result in a clear solution. Rod-shaped crystals of (I) grew as the water evaporated over the course of a few days. These colourless transparent crystals were rinsed with acetone and dried in air.
The site occupancies of the two conformations (C1, C3, C5 and their attached H atoms/C11, C13, C15 and their attached H atoms) of the partially disordered organic species were constrained to sum to unity. The O—H and N—H hydrogen atoms were found in difference maps and were refined by riding in their as-found positions. The H atoms bonded to carbon and phosphorus 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.
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.
C6H16NO3+·H2PO3− | F(000) = 248 |
Mr = 231.18 | Dx = 1.419 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.9280 (7) Å | Cell parameters from 1408 reflections |
b = 5.5192 (5) Å | θ = 2.7–23.3° |
c = 12.7940 (11) Å | µ = 0.26 mm−1 |
β = 104.803 (2)° | T = 293 K |
V = 541.24 (8) Å3 | Rod, colourless |
Z = 2 | 0.52 × 0.08 × 0.07 mm |
Bruker SMART1000 CCD diffractometer | 2362 independent reflections |
Radiation source: fine-focus sealed tube | 1743 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ω scans | θmax = 27.6°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −10→10 |
Tmin = 0.876, Tmax = 0.977 | k = −7→7 |
3955 measured reflections | l = −11→16 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difmap (N-H and O-H) and geom (C-H, P-H) |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.087 | w = 1/[σ2(Fo2) + (0.0414P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.94 | (Δ/σ)max < 0.001 |
2362 reflections | Δρmax = 0.18 e Å−3 |
140 parameters | Δρmin = −0.24 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 1128 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.11 (12) |
C6H16NO3+·H2PO3− | V = 541.24 (8) Å3 |
Mr = 231.18 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.9280 (7) Å | µ = 0.26 mm−1 |
b = 5.5192 (5) Å | T = 293 K |
c = 12.7940 (11) Å | 0.52 × 0.08 × 0.07 mm |
β = 104.803 (2)° |
Bruker SMART1000 CCD diffractometer | 2362 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 1743 reflections with I > 2σ(I) |
Tmin = 0.876, Tmax = 0.977 | Rint = 0.028 |
3955 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.087 | Δρmax = 0.18 e Å−3 |
S = 0.94 | Δρmin = −0.24 e Å−3 |
2362 reflections | Absolute structure: Flack (1983), 1128 Friedel pairs |
140 parameters | Absolute structure parameter: 0.11 (12) |
1 restraint |
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) | |
P1 | −0.01075 (9) | 0.62827 (12) | 0.13758 (5) | 0.04477 (18) | |
H1 | −0.1527 | 0.5016 | 0.0944 | 0.054* | |
O1 | 0.1222 (2) | 0.5583 (4) | 0.07939 (13) | 0.0577 (5) | |
O2 | 0.0316 (2) | 0.5861 (4) | 0.25649 (13) | 0.0604 (5) | |
O3 | −0.0608 (3) | 0.9015 (4) | 0.11817 (15) | 0.0701 (7) | |
H2 | −0.0925 | 0.9635 | 0.0384 | 0.084* | |
N1 | 0.5510 (2) | 0.1123 (4) | 0.29094 (14) | 0.0407 (4) | |
H3 | 0.5417 | 0.2756 | 0.2976 | 0.049* | |
C1 | 0.4568 (5) | −0.0011 (6) | 0.3667 (3) | 0.0571 (10) | 0.866 (5) |
H4 | 0.4319 | −0.1692 | 0.3464 | 0.069* | 0.866 (5) |
H5 | 0.5322 | 0.0017 | 0.4395 | 0.069* | 0.866 (5) |
C11 | 0.376 (3) | 0.017 (4) | 0.2955 (19) | 0.047 (5)* | 0.134 (5) |
H11A | 0.2998 | 0.0272 | 0.2232 | 0.056* | 0.134 (5) |
H11B | 0.3903 | −0.1539 | 0.3138 | 0.056* | 0.134 (5) |
C2 | 0.2917 (4) | 0.1247 (6) | 0.3658 (2) | 0.0617 (7) | |
H6 | 0.2052 | 0.0899 | 0.2988 | 0.074* | |
H7 | 0.2473 | 0.0670 | 0.4253 | 0.074* | |
O4 | 0.3212 (2) | 0.3773 (4) | 0.37577 (13) | 0.0568 (5) | |
H8 | 0.2245 | 0.4521 | 0.3332 | 0.068* | |
C3 | 0.7434 (5) | 0.0539 (6) | 0.3234 (3) | 0.0575 (10) | 0.866 (5) |
H9 | 0.7590 | −0.1125 | 0.3484 | 0.069* | 0.866 (5) |
H10 | 0.7902 | 0.0684 | 0.2607 | 0.069* | 0.866 (5) |
C13 | 0.695 (3) | 0.055 (4) | 0.3870 (18) | 0.047 (5)* | 0.134 (5) |
H13A | 0.6479 | 0.0524 | 0.4499 | 0.056* | 0.134 (5) |
H13B | 0.7366 | −0.1071 | 0.3781 | 0.056* | 0.134 (5) |
C4 | 0.8410 (4) | 0.2145 (6) | 0.4091 (2) | 0.0621 (9) | |
H11 | 0.8060 | 0.1831 | 0.4751 | 0.074* | |
H12 | 0.9646 | 0.1791 | 0.4228 | 0.074* | |
O5 | 0.8128 (2) | 0.4609 (4) | 0.38149 (14) | 0.0569 (5) | |
H13 | 0.8980 | 0.5182 | 0.3349 | 0.068* | |
C5 | 0.4654 (6) | 0.0520 (6) | 0.1755 (3) | 0.0561 (10) | 0.866 (5) |
H14 | 0.5093 | −0.1022 | 0.1572 | 0.067* | 0.866 (5) |
H15 | 0.3405 | 0.0364 | 0.1661 | 0.067* | 0.866 (5) |
C15 | 0.599 (3) | 0.073 (3) | 0.1850 (13) | 0.037 (5)* | 0.134 (5) |
H15A | 0.7231 | 0.0987 | 0.1951 | 0.044* | 0.134 (5) |
H15B | 0.5726 | −0.0931 | 0.1610 | 0.044* | 0.134 (5) |
C6 | 0.4999 (5) | 0.2416 (6) | 0.1023 (2) | 0.0600 (8) | |
H16 | 0.6203 | 0.2300 | 0.0984 | 0.072* | |
H17 | 0.4256 | 0.2151 | 0.0302 | 0.072* | |
O6 | 0.4694 (3) | 0.4742 (3) | 0.13740 (14) | 0.0546 (5) | |
H18 | 0.3386 | 0.4991 | 0.1132 | 0.066* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0462 (3) | 0.0469 (4) | 0.0403 (3) | 0.0004 (4) | 0.0094 (2) | 0.0037 (3) |
O1 | 0.0603 (11) | 0.0684 (13) | 0.0446 (10) | 0.0085 (9) | 0.0134 (8) | −0.0144 (9) |
O2 | 0.0685 (12) | 0.0703 (14) | 0.0452 (10) | 0.0152 (11) | 0.0195 (8) | 0.0224 (10) |
O3 | 0.1132 (17) | 0.0614 (14) | 0.0419 (11) | 0.0325 (12) | 0.0310 (11) | 0.0124 (10) |
N1 | 0.0509 (11) | 0.0315 (10) | 0.0433 (10) | 0.0003 (11) | 0.0188 (8) | −0.0001 (10) |
C1 | 0.066 (2) | 0.050 (2) | 0.063 (2) | 0.0034 (15) | 0.0295 (19) | 0.0187 (16) |
C2 | 0.0620 (17) | 0.0655 (19) | 0.0651 (18) | 0.001 (2) | 0.0297 (14) | 0.0109 (19) |
O4 | 0.0551 (11) | 0.0637 (13) | 0.0489 (12) | 0.0083 (10) | 0.0082 (9) | −0.0073 (9) |
C3 | 0.067 (2) | 0.0458 (19) | 0.069 (2) | 0.0192 (15) | 0.034 (2) | 0.0099 (16) |
C4 | 0.0487 (17) | 0.078 (2) | 0.0560 (18) | 0.0065 (14) | 0.0071 (15) | 0.0189 (15) |
O5 | 0.0573 (12) | 0.0593 (12) | 0.0546 (12) | −0.0040 (10) | 0.0150 (10) | −0.0004 (9) |
C5 | 0.081 (3) | 0.0437 (18) | 0.0459 (19) | −0.0153 (16) | 0.0209 (17) | −0.0146 (14) |
C6 | 0.071 (2) | 0.0663 (19) | 0.0463 (16) | −0.0012 (15) | 0.0221 (15) | −0.0100 (15) |
O6 | 0.0626 (13) | 0.0486 (12) | 0.0522 (12) | −0.0039 (9) | 0.0137 (10) | 0.0028 (9) |
P1—O1 | 1.4883 (19) | O4—H8 | 0.9173 |
P1—O2 | 1.4901 (16) | C3—C4 | 1.467 (5) |
P1—O3 | 1.563 (2) | C3—H9 | 0.9700 |
P1—H1 | 1.3200 | C3—H10 | 0.9700 |
O3—H2 | 1.0445 | C13—C4 | 1.42 (2) |
N1—C13 | 1.483 (19) | C13—H13A | 0.9700 |
N1—C11 | 1.50 (2) | C13—H13B | 0.9700 |
N1—C5 | 1.497 (4) | C4—O5 | 1.408 (3) |
N1—C1 | 1.503 (3) | C4—H11 | 0.9700 |
N1—C3 | 1.509 (4) | C4—H12 | 0.9700 |
N1—C15 | 1.514 (16) | O5—H13 | 1.0569 |
N1—H3 | 0.9100 | C5—C6 | 1.476 (4) |
C1—C2 | 1.480 (4) | C5—H14 | 0.9700 |
C1—H4 | 0.9700 | C5—H15 | 0.9700 |
C1—H5 | 0.9700 | C15—C6 | 1.477 (16) |
C11—C2 | 1.39 (2) | C15—H15A | 0.9700 |
C11—H11A | 0.9700 | C15—H15B | 0.9700 |
C11—H11B | 0.9700 | C6—O6 | 1.401 (3) |
C2—O4 | 1.414 (4) | C6—H16 | 0.9700 |
C2—H6 | 0.9700 | C6—H17 | 0.9700 |
C2—H7 | 0.9700 | O6—H18 | 1.0131 |
O1—P1—O2 | 117.83 (11) | C4—C3—H9 | 109.1 |
O1—P1—O3 | 110.75 (12) | N1—C3—H9 | 109.1 |
O2—P1—O3 | 107.14 (11) | C4—C3—H10 | 109.1 |
O1—P1—H1 | 106.9 | N1—C3—H10 | 109.1 |
O2—P1—H1 | 106.9 | H9—C3—H10 | 107.9 |
O3—P1—H1 | 106.9 | C4—C13—N1 | 116.6 (14) |
P1—O3—H2 | 117.3 | C4—C13—H13A | 108.1 |
C13—N1—C11 | 114.7 (12) | N1—C13—H13A | 108.1 |
C5—N1—C1 | 111.7 (2) | C4—C13—H13B | 108.1 |
C5—N1—C3 | 113.3 (2) | N1—C13—H13B | 108.1 |
C1—N1—C3 | 111.5 (2) | H13A—C13—H13B | 107.3 |
C13—N1—C15 | 113.3 (11) | O5—C4—C13 | 118.6 (8) |
C11—N1—C15 | 115.4 (11) | O5—C4—C3 | 112.1 (2) |
C13—N1—H3 | 101.3 | O5—C4—H11 | 109.2 |
C11—N1—H3 | 104.3 | C3—C4—H11 | 109.2 |
C5—N1—H3 | 106.6 | O5—C4—H12 | 109.2 |
C1—N1—H3 | 106.6 | C3—C4—H12 | 109.2 |
C3—N1—H3 | 106.6 | H11—C4—H12 | 107.9 |
C15—N1—H3 | 105.8 | C4—O5—H13 | 110.3 |
C2—C1—N1 | 112.6 (2) | C6—C5—N1 | 110.9 (2) |
C2—C1—H4 | 109.1 | C6—C5—H14 | 109.5 |
N1—C1—H4 | 109.1 | N1—C5—H14 | 109.5 |
C2—C1—H5 | 109.1 | C6—C5—H15 | 109.5 |
N1—C1—H5 | 109.1 | N1—C5—H15 | 109.5 |
H4—C1—H5 | 107.8 | H14—C5—H15 | 108.0 |
C2—C11—N1 | 118.7 (14) | C6—C15—N1 | 109.9 (11) |
C2—C11—H11A | 107.6 | C6—C15—H15A | 109.7 |
N1—C11—H11A | 107.6 | N1—C15—H15A | 109.7 |
C2—C11—H11B | 107.6 | C6—C15—H15B | 109.7 |
N1—C11—H11B | 107.6 | N1—C15—H15B | 109.7 |
H11A—C11—H11B | 107.1 | H15A—C15—H15B | 108.2 |
C11—C2—O4 | 112.6 (8) | O6—C6—C5 | 111.8 (2) |
O4—C2—C1 | 109.6 (2) | O6—C6—C15 | 116.9 (7) |
O4—C2—H6 | 109.7 | O6—C6—H16 | 109.3 |
C1—C2—H6 | 109.7 | C5—C6—H16 | 109.3 |
O4—C2—H7 | 109.7 | O6—C6—H17 | 109.3 |
C1—C2—H7 | 109.7 | C5—C6—H17 | 109.3 |
H6—C2—H7 | 108.2 | H16—C6—H17 | 107.9 |
C2—O4—H8 | 107.2 | C6—O6—H18 | 105.9 |
C4—C3—N1 | 112.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H2···O1i | 1.04 | 1.56 | 2.597 (3) | 175 |
N1—H3···O6 | 0.91 | 2.27 | 2.760 (3) | 114 |
N1—H3···O4 | 0.91 | 2.29 | 2.765 (3) | 112 |
N1—H3···O5 | 0.91 | 2.37 | 2.850 (3) | 113 |
O4—H8···O2 | 0.92 | 1.76 | 2.672 (2) | 176 |
O6—H18···O1 | 1.01 | 1.69 | 2.702 (3) | 176 |
O5—H13···O2ii | 1.06 | 1.68 | 2.731 (2) | 175 |
C1—H5···O4iii | 0.97 | 2.45 | 3.382 (4) | 161 |
C3—H9···O5iv | 0.97 | 2.41 | 3.370 (4) | 170 |
C3—H10···O3v | 0.97 | 2.58 | 3.478 (4) | 154 |
C5—H14···O6iv | 0.97 | 2.36 | 3.227 (4) | 148 |
Symmetry codes: (i) −x, y+1/2, −z; (ii) x+1, y, z; (iii) −x+1, y−1/2, −z+1; (iv) x, y−1, z; (v) x+1, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C6H16NO3+·H2PO3− |
Mr | 231.18 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 7.9280 (7), 5.5192 (5), 12.7940 (11) |
β (°) | 104.803 (2) |
V (Å3) | 541.24 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.26 |
Crystal size (mm) | 0.52 × 0.08 × 0.07 |
Data collection | |
Diffractometer | Bruker SMART1000 CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.876, 0.977 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3955, 2362, 1743 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.653 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.087, 0.94 |
No. of reflections | 2362 |
No. of parameters | 140 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.24 |
Absolute structure | Flack (1983), 1128 Friedel pairs |
Absolute structure parameter | 0.11 (12) |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97, ORTEP-3 (Farrugia, 1997) and ATOMS (Shape Software, 1999).
P1—O1 | 1.4883 (19) | N1—C5 | 1.497 (4) |
P1—O2 | 1.4901 (16) | N1—C1 | 1.503 (3) |
P1—O3 | 1.563 (2) | N1—C3 | 1.509 (4) |
O1—P1—O2 | 117.83 (11) | O2—P1—O3 | 107.14 (11) |
O1—P1—O3 | 110.75 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H2···O1i | 1.04 | 1.56 | 2.597 (3) | 175 |
N1—H3···O6 | 0.91 | 2.27 | 2.760 (3) | 114 |
N1—H3···O4 | 0.91 | 2.29 | 2.765 (3) | 112 |
N1—H3···O5 | 0.91 | 2.37 | 2.850 (3) | 113 |
O4—H8···O2 | 0.92 | 1.76 | 2.672 (2) | 176 |
O6—H18···O1 | 1.01 | 1.69 | 2.702 (3) | 176 |
O5—H13···O2ii | 1.06 | 1.68 | 2.731 (2) | 175 |
C1—H5···O4iii | 0.97 | 2.45 | 3.382 (4) | 161 |
C3—H9···O5iv | 0.97 | 2.41 | 3.370 (4) | 170 |
C3—H10···O3v | 0.97 | 2.58 | 3.478 (4) | 154 |
C5—H14···O6iv | 0.97 | 2.36 | 3.227 (4) | 148 |
Symmetry codes: (i) −x, y+1/2, −z; (ii) x+1, y, z; (iii) −x+1, y−1/2, −z+1; (iv) x, y−1, z; (v) x+1, y−1, z. |
Triethanolammonium dihydrogenphosphite, [HN(C2H4OH)3](H2PO3), (I), is isostructural with the recently reported triethanolammonium h ydrogenselenite, [HN(C2H4OH)3](HSeO3), which shows cytotoxic activity (Lukevics et al., 2002).
The structure of (I) consists of triethanolammonium cations and dihydrogenphosphate anions (Fig. 1). The triethanolammonium cation is partially disordered over two positions [major component: atoms C1, C3, and C5 with an occupancy of 0.866 (5) and dav(N—C) = 1.503 (4) Å; minor component: atoms C11, C13, and C15 with an occupancy of 0.134 (5) and dav(N—C) = 1.50 (2) Å]. Otherwise, it exibits a typical (Yilmaz et al. 1996; Demir et al., 2003) tripodal conformation [for the major component; dav(C—C) = 1.474 (4) Å and dav(C—O) = 1.408 (4) Å] in which the ammonium H atom forms an intramolecular trifurcated hydrogen bond with the O atoms of the three ethanol groups [dav(H···O) = 2.31 Å and θav(N—H···O) = 112.7°]. The dihydrogenphosphite group shows its usual (Gordon & Harrison, 2003) pseudo-pyramidal geometry [dav(P—O) = 1.514 (2) Å and θav(O—P—O) = 111.9 (2)°], with the protonated P—O3 vertex showing its expected lengthening relative to the other two P—O bonds.
The component species in (I) interact by means of an extensive network of O—H···O hydrogen bonds and C—H···O intermolecular contacts (Table 2). The H2PO3 units are linked into a polymeric chain by P—O—H···O—P hydrogen bonds in the polar [010] direction (Fig. 2). A similar dihydrogenphosphite chain was seen in (CN3H6)(H2PO3) (Harrison, 2003). The organic species crosslink the chains in the a direction by way of OE—H···OP (E = ethanol and P = phosphite) hydrogen bonds, such that each cation makes two hydrogen bonds to one adjacent phosphite moiety (Fig. 1). This results in (001) slabs (Fig. 3). The possible C—H···O interactions [dav(H···O) = 2.45 Å, θav(C—H···O) = 158° and dav(C···O) = 3.364 (4) Å] were identified in a PLATON (Spek, 2003) analysis of the structure. Those involving H5, H9 and H14 provide additional coherence between adjacent organic molecules, in the c direction for H5 and in the b direction for H9 and H14. The bond involving H10 links a [HN(C2H4OH)3]+ grouping with a (H2PO3)− anion in the a direction.
Triethanolammonium dihydrogenphosphate, [HN(C2H4OH)3](H2PO4) (Demir et al., 2003) crystallizes in the same space group and has a rather similar structure to (I) in which chains of [H2PO4]− anions are crosslinked into sheets by the triethanolammonium cations. However, the (H2PO4)− moieties in [HN(C2H4OH)3](H2PO4) are linked together by a distinctly different hydrogen bonding motif involving alternating single and double P—O—H···O—P links.