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The title compound, Ox3H3 or C9H18N4O3, adopts an open extended structure which does not restrict solvent accessibility or metallation reactivity. An intermolecular O—H...N hydrogen bond is observed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802020135/om6117sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802020135/om6117Isup2.hkl
Contains datablock I

CCDC reference: 202323

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.038
  • wR factor = 0.104
  • Data-to-parameter ratio = 11.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes

REFLT_03 From the CIF: _diffrn_reflns_theta_max 28.22 From the CIF: _reflns_number_total 573 Count of symmetry unique reflns 571 Completeness (_total/calc) 100.35% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 2 Fraction of Friedel pairs measured 0.004 Are heavy atom types Z>Si present no 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.

Comment top

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).

Experimental top

The synthesis of (I) has been reported previously (Mattaiopoulos, 1898; Ogloblin & Potekhin, 1965).

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing 50% probability displacement ellipsoids and the atomic numbering scheme.
tris(1-propan-1-onyl oxime)amine top
Crystal data top
C9H18N4O3Mo Kα radiation, λ = 0.71073 Å
Mr = 230.27Cell parameters from 4620 reflections
Cubic, I43dθ = 2.9–28.2°
a = 17.1677 (9) ŵ = 0.09 mm1
V = 5059.8 (5) Å3T = 150 K
Z = 16Wedge, colorless
F(000) = 19840.38 × 0.20 × 0.18 mm
Dx = 1.209 Mg m3
Data collection top
SMART 1K Platform CCD
diffractometer
573 independent reflections
Radiation source: sealed tube518 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.064
ω scansθmax = 28.2°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 2219
Tmin = 0.966, Tmax = 0.984k = 2216
15298 measured reflectionsl = 2122
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)] = 0.038Hydrogen site location: mixed
wR(F2) = 0.104H-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 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = 0.13 e Å3
Crystal data top
C9H18N4O3Z = 16
Mr = 230.27Mo Kα radiation
Cubic, I43dµ = 0.09 mm1
a = 17.1677 (9) ÅT = 150 K
V = 5059.8 (5) Å30.38 × 0.20 × 0.18 mm
Data collection top
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 = 0.984Rint = 0.064
15298 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.104H-atom parameters constrained
S = 1.07Δρmax = 0.19 e Å3
573 reflectionsΔρmin = 0.13 e Å3
51 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.31224 (10)0.43507 (10)0.89499 (11)0.0398 (5)
H10.31980.39040.91790.060*
N10.10624 (9)0.60624 (9)0.89376 (9)0.0209 (6)
N20.23180 (10)0.44698 (10)0.90191 (11)0.0291 (4)
C10.12282 (12)0.52550 (11)0.87271 (13)0.0253 (5)
H1A0.09980.51400.82110.030*
H1B0.09860.49020.91140.030*
C20.20967 (12)0.51097 (12)0.87001 (12)0.0254 (4)
C30.26180 (13)0.56810 (13)0.83033 (14)0.0318 (5)
H3A0.27010.61310.86440.048*
H3B0.23760.58530.78160.048*
H3C0.31200.54330.81890.048*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0301 (9)0.0370 (9)0.0523 (10)0.0119 (7)0.0082 (8)0.0097 (8)
N10.0209 (6)0.0209 (6)0.0209 (6)0.0013 (6)0.0013 (6)0.0013 (6)
N20.0277 (10)0.0283 (9)0.0312 (9)0.0029 (7)0.0034 (7)0.0007 (7)
C10.0262 (10)0.0211 (10)0.0285 (10)0.0014 (7)0.0011 (7)0.0004 (7)
C20.0294 (10)0.0243 (10)0.0225 (10)0.0027 (8)0.0007 (8)0.0031 (8)
C30.0300 (11)0.0289 (11)0.0364 (11)0.0022 (9)0.0068 (9)0.0032 (9)
Geometric parameters (Å, º) top
O1—N21.401 (2)C1—H1B0.9900
O1—H10.8716C2—C31.492 (3)
N1—C11.460 (2)C3—H3A0.9800
N2—C21.285 (3)C3—H3B0.9800
C1—C21.513 (3)C3—H3C0.9800
C1—H1A0.9900
N2—O1—H1103.7N2—C2—C1114.79 (18)
C2—N2—O1112.33 (18)C3—C2—C1119.80 (17)
N1—C1—C2110.87 (17)C2—C3—H3A109.5
N1—C1—H1A109.5C2—C3—H3B109.5
C2—C1—H1A109.5H3A—C3—H3B109.5
N1—C1—H1B109.5C2—C3—H3C109.5
C2—C1—H1B109.5H3A—C3—H3C109.5
H1A—C1—H1B108.1H3B—C3—H3C109.5
N2—C2—C3125.39 (19)
O1—N2—C2—C30.6 (3)N1—C1—C2—N2136.4 (2)
O1—N2—C2—C1177.62 (18)N1—C1—C2—C345.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N2i0.871.922.782 (3)169
Symmetry code: (i) z+5/4, y+3/4, x+3/4.

Experimental details

Crystal data
Chemical formulaC9H18N4O3
Mr230.27
Crystal system, space groupCubic, I43d
Temperature (K)150
a (Å)17.1677 (9)
V3)5059.8 (5)
Z16
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.38 × 0.20 × 0.18
Data collection
DiffractometerSMART 1K Platform CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.966, 0.984
No. of measured, independent and
observed [I > 2σ(I)] reflections
15298, 573, 518
Rint0.064
(sin θ/λ)max1)0.665
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.104, 1.07
No. of reflections573
No. of parameters51
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.13

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXTL (Bruker, 2000), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N2i0.871.922.782 (3)169
Symmetry code: (i) z+5/4, y+3/4, x+3/4.
 

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