Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802020135/om6117sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802020135/om6117Isup2.hkl |
CCDC reference: 202323
The synthesis of (I) has been reported previously (Mattaiopoulos, 1898; Ogloblin & Potekhin, 1965).
The hydroxyl H atom was located directly from the difference map and held fixed at that location (N—H = 0.87 Å). The remaining H atoms were either located directly or calculated based on geometric criteria and treated with a riding model (C—H = 0.98 and 0.99 Å for CH3 and CH2, respectively). H atom isotropic displacement parameters were defined as aUeq of the adjacent atom, where a = 1.2 for CH2 and 1.5 for all others. Since this is a light-atom structure collected with Mo Kα radiation, the data was merged. The Flack parameter refinement, 0(10), is meaningless.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. The structure of (I), showing 50% probability displacement ellipsoids and the atomic numbering scheme. |
C9H18N4O3 | Mo Kα radiation, λ = 0.71073 Å |
Mr = 230.27 | Cell parameters from 4620 reflections |
Cubic, I43d | θ = 2.9–28.2° |
a = 17.1677 (9) Å | µ = 0.09 mm−1 |
V = 5059.8 (5) Å3 | T = 150 K |
Z = 16 | Wedge, colorless |
F(000) = 1984 | 0.38 × 0.20 × 0.18 mm |
Dx = 1.209 Mg m−3 |
SMART 1K Platform CCD diffractometer | 573 independent reflections |
Radiation source: sealed tube | 518 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
ω scans | θmax = 28.2°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −22→19 |
Tmin = 0.966, Tmax = 0.984 | k = −22→16 |
15298 measured reflections | l = −21→22 |
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)] = 0.038 | Hydrogen site location: mixed |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0657P)2 + 1.25P] where P = (Fo2 + 2Fc2)/3 |
573 reflections | (Δ/σ)max < 0.001 |
51 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.13 e Å−3 |
C9H18N4O3 | Z = 16 |
Mr = 230.27 | Mo Kα radiation |
Cubic, I43d | µ = 0.09 mm−1 |
a = 17.1677 (9) Å | T = 150 K |
V = 5059.8 (5) Å3 | 0.38 × 0.20 × 0.18 mm |
SMART 1K Platform CCD diffractometer | 573 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 518 reflections with I > 2σ(I) |
Tmin = 0.966, Tmax = 0.984 | Rint = 0.064 |
15298 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.19 e Å−3 |
573 reflections | Δρmin = −0.13 e Å−3 |
51 parameters |
Experimental. A series of 20 − s data frames measured at 0.3° increments of ω were collected to calculate a unit cell (5 cm crystal-to-detector distance). Data frames were measured for a duration of 30 − s at 0.3° increments of ω, which combined measured nearly a hemisphere of intensity data. The first 50 frames of data were recollected for a decay correction. The decay correction was applied simultaneously with the absorption correction in SADABS. No formal measure of the extent of decay is printed out by this program. The final unit cell is obtained from the refinement of the XYZ weighted centroids of reflections above 20 σ(I). Note that the absorption correction parameters Tmin and Tmax also reflect beam corrections, etc. As a result, the numerical values for Tmin and Tmax may differ from expected values based solely absorption effects and crystal size. Output from SADABS gives the following in terms of corrections applied: Maximum and minimum effective transmission: 0.942 0.721 |
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 | ||
O1 | 0.31224 (10) | 0.43507 (10) | 0.89499 (11) | 0.0398 (5) | |
H1 | 0.3198 | 0.3904 | 0.9179 | 0.060* | |
N1 | 0.10624 (9) | 0.60624 (9) | 0.89376 (9) | 0.0209 (6) | |
N2 | 0.23180 (10) | 0.44698 (10) | 0.90191 (11) | 0.0291 (4) | |
C1 | 0.12282 (12) | 0.52550 (11) | 0.87271 (13) | 0.0253 (5) | |
H1A | 0.0998 | 0.5140 | 0.8211 | 0.030* | |
H1B | 0.0986 | 0.4902 | 0.9114 | 0.030* | |
C2 | 0.20967 (12) | 0.51097 (12) | 0.87001 (12) | 0.0254 (4) | |
C3 | 0.26180 (13) | 0.56810 (13) | 0.83033 (14) | 0.0318 (5) | |
H3A | 0.2701 | 0.6131 | 0.8644 | 0.048* | |
H3B | 0.2376 | 0.5853 | 0.7816 | 0.048* | |
H3C | 0.3120 | 0.5433 | 0.8189 | 0.048* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0301 (9) | 0.0370 (9) | 0.0523 (10) | 0.0119 (7) | 0.0082 (8) | 0.0097 (8) |
N1 | 0.0209 (6) | 0.0209 (6) | 0.0209 (6) | 0.0013 (6) | −0.0013 (6) | −0.0013 (6) |
N2 | 0.0277 (10) | 0.0283 (9) | 0.0312 (9) | 0.0029 (7) | 0.0034 (7) | 0.0007 (7) |
C1 | 0.0262 (10) | 0.0211 (10) | 0.0285 (10) | 0.0014 (7) | −0.0011 (7) | 0.0004 (7) |
C2 | 0.0294 (10) | 0.0243 (10) | 0.0225 (10) | 0.0027 (8) | 0.0007 (8) | −0.0031 (8) |
C3 | 0.0300 (11) | 0.0289 (11) | 0.0364 (11) | 0.0022 (9) | 0.0068 (9) | 0.0032 (9) |
O1—N2 | 1.401 (2) | C1—H1B | 0.9900 |
O1—H1 | 0.8716 | C2—C3 | 1.492 (3) |
N1—C1 | 1.460 (2) | C3—H3A | 0.9800 |
N2—C2 | 1.285 (3) | C3—H3B | 0.9800 |
C1—C2 | 1.513 (3) | C3—H3C | 0.9800 |
C1—H1A | 0.9900 | ||
N2—O1—H1 | 103.7 | N2—C2—C1 | 114.79 (18) |
C2—N2—O1 | 112.33 (18) | C3—C2—C1 | 119.80 (17) |
N1—C1—C2 | 110.87 (17) | C2—C3—H3A | 109.5 |
N1—C1—H1A | 109.5 | C2—C3—H3B | 109.5 |
C2—C1—H1A | 109.5 | H3A—C3—H3B | 109.5 |
N1—C1—H1B | 109.5 | C2—C3—H3C | 109.5 |
C2—C1—H1B | 109.5 | H3A—C3—H3C | 109.5 |
H1A—C1—H1B | 108.1 | H3B—C3—H3C | 109.5 |
N2—C2—C3 | 125.39 (19) | ||
O1—N2—C2—C3 | −0.6 (3) | N1—C1—C2—N2 | 136.4 (2) |
O1—N2—C2—C1 | 177.62 (18) | N1—C1—C2—C3 | −45.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N2i | 0.87 | 1.92 | 2.782 (3) | 169 |
Symmetry code: (i) −z+5/4, −y+3/4, x+3/4. |
Experimental details
Crystal data | |
Chemical formula | C9H18N4O3 |
Mr | 230.27 |
Crystal system, space group | Cubic, I43d |
Temperature (K) | 150 |
a (Å) | 17.1677 (9) |
V (Å3) | 5059.8 (5) |
Z | 16 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.38 × 0.20 × 0.18 |
Data collection | |
Diffractometer | SMART 1K Platform CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.966, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15298, 573, 518 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.665 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.104, 1.07 |
No. of reflections | 573 |
No. of parameters | 51 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.13 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXTL (Bruker, 2000), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N2i | 0.87 | 1.92 | 2.782 (3) | 169 |
Symmetry code: (i) −z+5/4, −y+3/4, x+3/4. |
Compounds with multiple varied functional groups are of interest as chelating ligands for transition metals. For the past couple of years, our research effort has focused on the reactivity of Ni, Cu and Zn complexes (Goldcamp, Robison, Krause Bauer & Baldwin, 2002; Goldcamp, Robison, Squires et al., 2002) of ligands sporting the tripodal geometry and incorporating oximate and mixed oxime/amide functionality (Goldcamp, Krause Bauer & Baldwin, 2000; Goldcamp, Rosa et al., 2000). Tris(1-propan-2-onyl oxime)amine, (I), otherwise known as tris(2-hydroxyiminopropyl)amine, Ox3H3, is such a ligand.
The molecular structure of (I) is similar to that observed for [N-(1-propan-2-onyl oxime)]bis[N-2-(N',N''-trimethylacetyl)aminoethyl]amine (Goldcamp, Rosa et al., 2000) in that both have an open extended geometry rather than a folded geometry, as exhibited by tris[2-benzoylamino)ethyl]amine (Goldcamp, Krause Bauer & Baldwin, 2000). Viewing (I) from N1 down to the methyl groups, one observes a rather shallow symmetrical cavity with a depth of 1.8 Å (distance from N1 to the centroid of the methyl C atoms) and a width of 4.1 Å (distance between methyl C atoms). The opposite side of the molecule is open, making it accessible for reactivity with metals. Upon metallation, the three donor arms clamp down on the metal, forming a tripod motif, as observed in Ni(Ox3H3)Cl2 (Goldcamp, Robison, Squires et al., 2002) and [Ni(Ox3H3)(NO3)(H2O)]NO3·H2O (Goldcamp, Robison, Krause Bauer & Baldwin, 2002). An intermolecular O—H.·N hydrogen bond is observed (O1—H1···N2i = 2.782 (3) Å and 169°; see Table 1 for symmetry code).