[Bis(2-hydroxyethyl)amino]tris(hydroxymethyl)methane (Bis–Tris), an important complexing agent
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801017974/ya6068sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801017974/ya6068Isup2.hkl |
CCDC reference: 176047
The title compound was obtained commercially (Aldrich) and crystallized from a concentrated methanol solution.
All hydroxyl-H atoms were located and refined (O—H 0.78–0.84 Å). All the rest of the H atoms were placed geometrically and included in the refinement in the riding-motion approximation with displacement parameters equal to 1.2Ueq of the corresponding carrier atom.
Data collection: SMART (Bruker, 1997–1998); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: XS in SHELXTL (Sheldrick, 1998); program(s) used to refine structure: XL in SHELXTL; molecular graphics: XP in SHELXTL; software used to prepare material for publication: XCIF in SHELXTL.
C8H19NO5 | Dx = 1.403 Mg m−3 |
Mr = 209.24 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 1001 reflections |
a = 12.1298 (17) Å | θ = 2.4–27.9° |
b = 9.5303 (13) Å | µ = 0.12 mm−1 |
c = 17.144 (2) Å | T = 203 K |
V = 1981.9 (5) Å3 | Needle, colorless |
Z = 8 | 0.32 × 0.20 × 0.11 mm |
F(000) = 912 |
Siemens SMART 1K diffractometer | 1745 independent reflections |
Radiation source: normal-focus sealed tube | 1476 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
Detector resolution: 8.3 pixels mm-1 | θmax = 25.0°, θmin = 2.9° |
ω scans | h = −14→11 |
Absorption correction: empirical (SADABS; Sheldrick, 1999) | k = −11→11 |
Tmin = 0.964, Tmax = 0.987 | l = −20→16 |
14160 measured reflections |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.084 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0399P)2 + 0.7334P] where P = (Fo2 + 2Fc2)/3 |
1745 reflections | (Δ/σ)max < 0.001 |
147 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C8H19NO5 | V = 1981.9 (5) Å3 |
Mr = 209.24 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 12.1298 (17) Å | µ = 0.12 mm−1 |
b = 9.5303 (13) Å | T = 203 K |
c = 17.144 (2) Å | 0.32 × 0.20 × 0.11 mm |
Siemens SMART 1K diffractometer | 1745 independent reflections |
Absorption correction: empirical (SADABS; Sheldrick, 1999) | 1476 reflections with I > 2σ(I) |
Tmin = 0.964, Tmax = 0.987 | Rint = 0.033 |
14160 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.084 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.24 e Å−3 |
1745 reflections | Δρmin = −0.18 e Å−3 |
147 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 | ||
N1 | 0.46638 (9) | 0.21083 (11) | 0.65075 (7) | 0.0200 (3) | |
O1 | 0.58293 (9) | 0.25164 (11) | 0.45071 (6) | 0.0273 (3) | |
O2 | 0.66745 (9) | 0.04041 (11) | 0.59010 (7) | 0.0323 (3) | |
O3 | 0.46313 (10) | 0.48513 (12) | 0.59555 (7) | 0.0355 (3) | |
O4 | 0.26258 (9) | −0.07991 (11) | 0.62309 (7) | 0.0305 (3) | |
O5 | 0.34000 (10) | 0.38224 (12) | 0.76953 (7) | 0.0356 (3) | |
C1 | 0.55049 (11) | 0.25295 (14) | 0.59206 (8) | 0.0208 (3) | |
C2 | 0.50554 (12) | 0.21767 (14) | 0.51044 (8) | 0.0226 (3) | |
H2A | 0.4882 | 0.1173 | 0.5079 | 0.027* | |
H2B | 0.4371 | 0.2700 | 0.5016 | 0.027* | |
C3 | 0.66468 (12) | 0.18757 (15) | 0.60385 (9) | 0.0262 (3) | |
H3A | 0.7170 | 0.2335 | 0.5686 | 0.031* | |
H3B | 0.6889 | 0.2058 | 0.6574 | 0.031* | |
C4 | 0.56531 (12) | 0.41289 (14) | 0.59709 (9) | 0.0249 (3) | |
H4A | 0.6043 | 0.4362 | 0.6454 | 0.030* | |
H4B | 0.6108 | 0.4446 | 0.5532 | 0.030* | |
C5 | 0.42278 (12) | 0.06642 (14) | 0.64419 (8) | 0.0213 (3) | |
H5A | 0.4280 | 0.0206 | 0.6952 | 0.026* | |
H5B | 0.4689 | 0.0135 | 0.6077 | 0.026* | |
C6 | 0.30439 (12) | 0.06033 (15) | 0.61667 (9) | 0.0261 (3) | |
H6A | 0.2592 | 0.1238 | 0.6483 | 0.031* | |
H6B | 0.3002 | 0.0913 | 0.5622 | 0.031* | |
C7 | 0.49955 (12) | 0.23876 (16) | 0.73229 (8) | 0.0263 (4) | |
H7A | 0.5452 | 0.3236 | 0.7339 | 0.032* | |
H7B | 0.5442 | 0.1603 | 0.7514 | 0.032* | |
C8 | 0.40143 (13) | 0.25798 (15) | 0.78508 (9) | 0.0288 (4) | |
H8A | 0.3526 | 0.1767 | 0.7795 | 0.035* | |
H8B | 0.4270 | 0.2605 | 0.8393 | 0.035* | |
H5 | 0.3126 (16) | 0.378 (2) | 0.7262 (12) | 0.043 (6)* | |
H4 | 0.3020 (18) | −0.132 (2) | 0.5985 (12) | 0.052 (6)* | |
H1 | 0.5710 (16) | 0.334 (2) | 0.4361 (11) | 0.045 (5)* | |
H2 | 0.6681 (16) | 0.000 (2) | 0.6319 (13) | 0.052 (6)* | |
H3 | 0.4167 (17) | 0.433 (2) | 0.6077 (11) | 0.039 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0210 (6) | 0.0191 (6) | 0.0200 (6) | −0.0019 (5) | 0.0000 (5) | −0.0010 (5) |
O1 | 0.0353 (6) | 0.0212 (5) | 0.0254 (6) | 0.0043 (5) | 0.0094 (5) | 0.0029 (4) |
O2 | 0.0321 (6) | 0.0276 (6) | 0.0371 (7) | 0.0089 (5) | 0.0037 (5) | 0.0041 (5) |
O3 | 0.0314 (7) | 0.0196 (6) | 0.0556 (8) | 0.0025 (5) | 0.0140 (6) | 0.0083 (5) |
O4 | 0.0257 (6) | 0.0201 (5) | 0.0457 (7) | −0.0051 (4) | 0.0103 (5) | −0.0054 (5) |
O5 | 0.0493 (8) | 0.0316 (6) | 0.0259 (7) | 0.0111 (5) | 0.0004 (6) | −0.0042 (5) |
C1 | 0.0205 (7) | 0.0194 (7) | 0.0223 (8) | −0.0014 (6) | 0.0007 (6) | 0.0001 (5) |
C2 | 0.0248 (8) | 0.0199 (7) | 0.0232 (8) | −0.0012 (6) | 0.0018 (6) | 0.0007 (6) |
C3 | 0.0211 (8) | 0.0278 (8) | 0.0297 (8) | 0.0005 (6) | 0.0008 (6) | 0.0015 (6) |
C4 | 0.0253 (8) | 0.0218 (7) | 0.0275 (8) | −0.0020 (6) | 0.0018 (6) | −0.0016 (6) |
C5 | 0.0233 (8) | 0.0177 (7) | 0.0230 (7) | 0.0004 (6) | 0.0015 (6) | 0.0018 (5) |
C6 | 0.0227 (8) | 0.0190 (7) | 0.0368 (9) | −0.0031 (6) | 0.0013 (7) | 0.0012 (6) |
C7 | 0.0292 (8) | 0.0288 (8) | 0.0210 (8) | −0.0021 (6) | −0.0029 (6) | −0.0010 (6) |
C8 | 0.0370 (9) | 0.0274 (8) | 0.0220 (8) | 0.0028 (7) | 0.0010 (7) | −0.0007 (6) |
N1—C5 | 1.4787 (17) | C2—H2A | 0.9800 |
N1—C7 | 1.4788 (18) | C2—H2B | 0.9800 |
N1—C1 | 1.4881 (18) | C3—H3A | 0.9800 |
O1—C2 | 1.4264 (18) | C3—H3B | 0.9800 |
O1—H1 | 0.84 (2) | C4—H4A | 0.9800 |
O2—C3 | 1.4225 (18) | C4—H4B | 0.9800 |
O2—H2 | 0.81 (2) | C5—C6 | 1.513 (2) |
O3—C4 | 1.4179 (19) | C5—H5A | 0.9800 |
O3—H3 | 0.78 (2) | C5—H5B | 0.9800 |
O4—C6 | 1.4338 (17) | C6—H6A | 0.9800 |
O4—H4 | 0.81 (2) | C6—H6B | 0.9800 |
O5—C8 | 1.4243 (18) | C7—C8 | 1.506 (2) |
O5—H5 | 0.82 (2) | C7—H7A | 0.9800 |
C1—C3 | 1.5322 (19) | C7—H7B | 0.9800 |
C1—C4 | 1.5373 (19) | C8—H8A | 0.9800 |
C1—C2 | 1.539 (2) | C8—H8B | 0.9800 |
C5—N1—C7 | 109.67 (11) | C1—C4—H4A | 109.2 |
C5—N1—C1 | 116.41 (11) | O3—C4—H4B | 109.2 |
C7—N1—C1 | 113.84 (11) | C1—C4—H4B | 109.2 |
C2—O1—H1 | 108.3 (13) | H4A—C4—H4B | 107.9 |
C3—O2—H2 | 108.8 (15) | N1—C5—C6 | 113.51 (11) |
C4—O3—H3 | 108.4 (14) | N1—C5—H5A | 108.9 |
C6—O4—H4 | 108.7 (15) | C6—C5—H5A | 108.9 |
C8—O5—H5 | 110.2 (14) | N1—C5—H5B | 108.9 |
N1—C1—C3 | 114.89 (11) | C6—C5—H5B | 108.9 |
N1—C1—C4 | 108.04 (11) | H5A—C5—H5B | 107.7 |
C3—C1—C4 | 106.86 (11) | O4—C6—C5 | 110.34 (12) |
N1—C1—C2 | 108.24 (11) | O4—C6—H6A | 109.6 |
C3—C1—C2 | 110.57 (11) | C5—C6—H6A | 109.6 |
C4—C1—C2 | 108.00 (11) | O4—C6—H6B | 109.6 |
O1—C2—C1 | 111.72 (12) | C5—C6—H6B | 109.6 |
O1—C2—H2A | 109.3 | H6A—C6—H6B | 108.1 |
C1—C2—H2A | 109.3 | N1—C7—C8 | 112.02 (12) |
O1—C2—H2B | 109.3 | N1—C7—H7A | 109.2 |
C1—C2—H2B | 109.3 | C8—C7—H7A | 109.2 |
H2A—C2—H2B | 107.9 | N1—C7—H7B | 109.2 |
O2—C3—C1 | 113.60 (12) | C8—C7—H7B | 109.2 |
O2—C3—H3A | 108.8 | H7A—C7—H7B | 107.9 |
C1—C3—H3A | 108.8 | O5—C8—C7 | 113.71 (13) |
O2—C3—H3B | 108.8 | O5—C8—H8A | 108.8 |
C1—C3—H3B | 108.8 | C7—C8—H8A | 108.8 |
H3A—C3—H3B | 107.7 | O5—C8—H8B | 108.8 |
O3—C4—C1 | 112.22 (12) | C7—C8—H8B | 108.8 |
O3—C4—H4A | 109.2 | H8A—C8—H8B | 107.7 |
C5—N1—C1—C3 | −73.38 (15) | C2—C1—C3—O2 | −54.49 (15) |
C7—N1—C1—C3 | 55.70 (15) | N1—C1—C4—O3 | −49.41 (15) |
C5—N1—C1—C4 | 167.44 (11) | C3—C1—C4—O3 | −173.55 (12) |
C7—N1—C1—C4 | −63.47 (14) | C2—C1—C4—O3 | 67.47 (15) |
C5—N1—C1—C2 | 50.73 (14) | C7—N1—C5—C6 | 119.55 (13) |
C7—N1—C1—C2 | 179.81 (11) | C1—N1—C5—C6 | −109.40 (14) |
N1—C1—C2—O1 | −178.45 (10) | N1—C5—C6—O4 | −171.18 (11) |
C3—C1—C2—O1 | −51.79 (15) | C5—N1—C7—C8 | −73.36 (15) |
C4—C1—C2—O1 | 64.81 (15) | C1—N1—C7—C8 | 154.22 (12) |
N1—C1—C3—O2 | 68.38 (16) | N1—C7—C8—O5 | −67.83 (16) |
C4—C1—C3—O2 | −171.79 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.84 (2) | 1.86 (2) | 2.6897 (16) | 177 (2) |
O2—H2···O5ii | 0.81 (2) | 2.03 (2) | 2.8410 (17) | 174 (2) |
O3—H3···N1 | 0.78 (2) | 2.321 (19) | 2.7804 (16) | 118.6 (17) |
O3—H3···O4iii | 0.78 (2) | 2.19 (2) | 2.8466 (17) | 141.6 (18) |
O4—H4···O1iv | 0.81 (2) | 1.99 (2) | 2.7913 (16) | 171 (2) |
O5—H5···O4iii | 0.82 (2) | 2.03 (2) | 2.8251 (17) | 165.6 (19) |
C4—H4B···O1 | 0.98 | 2.57 | 2.9505 (18) | 103 |
C5—H5B···O2 | 0.98 | 2.44 | 3.1192 (18) | 126 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+1/2, y+1/2, z; (iv) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C8H19NO5 |
Mr | 209.24 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 203 |
a, b, c (Å) | 12.1298 (17), 9.5303 (13), 17.144 (2) |
V (Å3) | 1981.9 (5) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.32 × 0.20 × 0.11 |
Data collection | |
Diffractometer | Siemens SMART 1K diffractometer |
Absorption correction | Empirical (SADABS; Sheldrick, 1999) |
Tmin, Tmax | 0.964, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14160, 1745, 1476 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.084, 1.03 |
No. of reflections | 1745 |
No. of parameters | 147 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.18 |
Computer programs: SMART (Bruker, 1997–1998), SMART, SAINT-Plus (Bruker, 1999), XS in SHELXTL (Sheldrick, 1998), XL in SHELXTL, XP in SHELXTL, XCIF in SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.84 (2) | 1.86 (2) | 2.6897 (16) | 177 (2) |
O2—H2···O5ii | 0.81 (2) | 2.03 (2) | 2.8410 (17) | 174 (2) |
O3—H3···N1 | 0.78 (2) | 2.321 (19) | 2.7804 (16) | 118.6 (17) |
O3—H3···O4iii | 0.78 (2) | 2.19 (2) | 2.8466 (17) | 141.6 (18) |
O4—H4···O1iv | 0.81 (2) | 1.99 (2) | 2.7913 (16) | 171 (2) |
O5—H5···O4iii | 0.82 (2) | 2.03 (2) | 2.8251 (17) | 165.6 (19) |
C4—H4B···O1 | 0.98 | 2.57 | 2.9505 (18) | 103.3 |
C5—H5B···O2 | 0.98 | 2.44 | 3.1192 (18) | 126.1 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+1/2, y+1/2, z; (iv) −x+1, −y, −z+1. |
The title compound, (I), commonly called Bis-Tris, is an important polyalcohol used in the complexation of metal ions (Hong et al., 1995; Sigel et al., 1982; Scheller et al., 1980; Wesolowski & Palmer, 1989; Wesolowski et al., 1990). It has received special attention as a chelation agent for some lanthanide ions (Oh et al., 1998; Chen et al., 1997; Pfefferle & Bunzli, 1989). The structure of (I) was determined in the course of an ongoing investigation into the complexation properties of Bis-Tris with various lanthanide halides (Wood et al., 2000).
All five hydroxyl-H atoms in (I) (Fig. 1) are involved in intermolecular hydrogen bonds (Table 1), which link the molecules in the crystal of (I) into a three-dimensional infinite network. Fig. 2 shows the three-dimensional network down [010]. It can be seen from this direction that the hydrogen bonding is localized in regular supramolecular synthons (Desiraju & Steiner, 2001). One of these synthons is shown in Fig. 3 and Fig. 4.
The O3—H3 hydroxyl group also serves as a donor for an intramolecular O3—H3···N1 bond (see Table 1), thus giving rise to a bifurcated hydrogen bond and closing the five-membered N1—C1—C4—O3—H3 pseudo-cycle. There are two other possibilities for intramolecular hydrogen bonding in (I). However, the C4—H4B···O1 and C5—H5B···O2 interactions should in fact be classified as extremely weak, if existing at all. As these are not bifurcated, it appears that this bonding is geometrically unlikely in the former, and extremely weak in the latter case. The corresponding distances and angles, are, nevertheless, included in Table 1 for comparison.