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Two different forms of meso-3,3'-[2,2-dimethyl­propane-1,3-diylbis(azanediyl)]dibutan-2-one dioxime, commonly called meso-hexa­methyl propyl­ene amine oxime (HMPAO), C13H28N4O2, designated [alpha] and [beta], were isolated by fractional crystallization and their crystal structures were determined by powder X-ray diffraction using the direct-space method with the parallel tempering algorithm. The [alpha] form was first crystallized from acetonitrile solution, while the [beta] form was obtained by recrystallization of the [alpha] phase from diethyl ether. The [alpha] form crystallizes in the triclinic system (space group P\overline{1}), with one mol­ecule in the asymmetric unit, while the crystal of the [beta] form is monoclinic (space group P21/n), with one mol­ecule in the asymmetric unit. In both phases, the mol­ecules have similar conformations and RS/EE geometric isomerism. The crystal packing of the two phases is dominated by inter­molecular hydrogen-bonding inter­actions between the two O-H oxime groups of an individual mol­ecule and the amine N atoms of two different adjacent mol­ecules, which lead to segregation of extended poly(meso-HMPAO) one-dimensional chains along the c direction. The structures of the two phases are primarily different due to the different orientations of the mol­ecules in the chains.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110032014/sq3256sup1.cif
Contains datablocks global, Ialpha, Ibeta

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108270110032014/sq3256Ialphasup2.rtv
Contains datablock Ialpha

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108270110032014/sq3256Ibetasup3.rtv
Contains datablock Ibeta

CCDC references: 796083; 796084

Comment top

It is well known that both diastereomeric forms of hexamethyl propylene amine oxime, meso-HMPAO, (I), and d,l-HMPAO, (II), have important radiopharmaceutical applications in nuclear medicine after labelling with 99mTc (Neirinckx et al., 1987; Sasaki & Senda, 1997; Roth et al., 1992; Jurisson et al., 1986). For example, 99mTc-d,l-HMPAO has been widely used as a leukocyte labelling agent and for SPECT imaging of regional cerebral blood perfusion (Jurisson et al., 1986).

The most general reported synthetic route to the diastereomeric mixture of HMPAO involves two synthetic procedures (Jurisson et al., 1986; Banerjee et al., 1999), which give a 50:50 diastereomeric mixture of HMPAO, meso-HMPAO, (I), and d,l-HMPAO, (II), that can be separated by fractional crystallization using different solvents (Banerjee et al., 1999). 1H and 13C{1H} NMR spectroscopic techniques may be utilized to assess the relative amounts of meso-HMPAO, (I), and d,l-HMPAO, (II), isomers in the diastereomeric mixture and also to identify the purity of each isomer obtained from such a mixture (Feinstein-Jaffe et al., 1989; Babushkina et al., 2002). Although HMPAO has been used as a polydentate ligand to form metal–HMPAO complexes, some of which have been structurally characterized (Suksai et al., 2008), to the best of our knowledge there are no published reports of the molecular structure of free meso-HMPAO, (I), or d,l-HMPAO, (II). Since we are currently interested in preparing HMPAO for pharmaceutical applications, we generated the HMPAO mixture, isolated meso-HMPAO, and determined the structures of the two crystalline forms that resulted, (Iα) and (Iβ), by powder X-ray diffraction.

Both forms crystallize with one molecule in the asymmetric unit, having almost the same conformations for their corresponding atoms (Fig. 1) and RS/EE geometric isomerism (Table 1). The crystal system of form (Iα) is triclinic, space group P1, with two molecules in the unit cell, while (Iβ) is monoclinic, space group P21/n, with four molecules in the unit cell. In both structures, the molecules are in almost maximally extended forms, with the oxime groups apart. The C—C and N—C bond lengths and bond angles in the {C(HCH3)CNHCH2C(CH3)2CH2NHC(HCH3)C} unit are in their normal ranges (Allen et al., 1987) for single bonds and tetrahedral geometries (Tables 1 and 3). For each individual oxime group in the molecules of (Iα) and (Iβ), the mean distance between the O atom of the CNOH group and the C atom of the attached CH3 group (2.67 Å) lies well within the sum of the van der Waals radii of O and C (3.2 Å; Bondi, 1964), indicating substantial intramolecular C···O interactions. The molecules of (Iα) and (Iβ) display similar bond distances and angles and intermolecular interactions to those in the closely related compound 3,3'-(trimethylenediamino)bis(3-methyl-2-butanone oxime) (C13H28N4O2; Hussain et al., 1984). The geometric data for (Iα) and (Iβ) are also comparable with those reported for the recently structurally characterized complex [Ni(meso-HMPAO)H].ClO4 (Suksai et al., 2008).

In the two phases, a major point of interest is the location of the CH3, C, N and O centres of each CH3C(NOH) unit in almost the same plane, as well as the short C—N bond lengths (average 1.30 Å), which readily indicate a Csp2Nsp2 double bond. The N—O (ca 1.40 Å) bond lengths are also characteristic for an oxime group (Allen et al., 1987).

The molecules in both phases are joined by intermolecular O—H···N hydrogen bonds between the two oxime O—H groups of one molecule and the amine N atoms of two different adjacent molecules (Fig. 2, Tables 2 and 4), leading to one-dimensional chains along the [001] direction. The interactions between the chains for both phases involve short contacts between two methyl groups. In (Iα), this interaction is between the C8 methyl group on one chain and a corresponding C8ii [symmetry code: (ii) -x, -y, -z] methyl group in an adjacent chain (Fig. 3a), while for (Iβ) this interaction is between methyl groups C9 and C3iii [symmetry code: (iii) -x + 1/2, y + 1/2, -z +1/2] in adjacent chains. These C···C distances are 3.579 (4) Å for (Iα) and 3.593 (5) Å for (Iβ). In (Iα), the molecules of an individual chain are arranged in opposite orientations to the corresponding ones in an adjacent chain (as required by the inversion symmetry of the P1 space group), while in (Iβ) the molecules of one chain are rotated by 180° with respect to one another (as required by the two-fold screw axis symmetry along the b axis of the P21/n space group).

As expected, the measured melting points of the two phases are slightly different [424.6 K for (Iα) and 423.1 K for (Iβ)]. Although the difference is small, it may be due to slightly stronger interchain interactions for (Iα) than for (Iβ), which correlates with the marginally shorter interchain contact distances for (Iα).

Related literature top

For related literature, see: Allen et al. (1987); Altomare et al. (1999); Babushkina et al. (2002); Banerjee et al. (1999); Bondi (1964); Boultif & Louër (2004); Favre-Nicolin & Černý (2002); Feinstein-Jaffe, Boazi & Tor (1989); Finger et al. (1994); Hussain et al. (1984); Jurisson et al. (1986); Larson & Von Dreele (2004); Neirinckx et al. (1987); Roisnel & Rodriguez-Carvajal (2001); Roth et al. (1992); Sasaki & Senda (1997); Suksai et al. (2008); Toby (2001); Von Dreele (1997).

Experimental top

All reactions and manipulations were carried out under an inert atmosphere using a two-fold vacuum line and Schlenk techniques. 1H and 13C{1H} NMR spectra were recorded on a Bruker Biospin 400 spectrometer in CDCl3. IR spectra were recorded on a Jasco FTIR 300E instrument. Microanalysis was performed using a EURO EA analyser. X-ray powder diffraction patterns were obtained on a Stoe STADI P diffractometer with monochromatic Cu Kα1 radiation (λ = 1.5406 Å) selected using an incident-beam curved-crystal germanium Ge(111) monochromator, using the Stoe transmission geometry (horizontal set-up) with a linear position-sensitive detector (PSD). Melting points were determined by differential thermal analysis measurements on a Netzsch DTA 404 EP instrument. The diastereomeric mixture of HMPAO was prepared and separated by fractional crystallization according to the published method (Banerjee et al., 1999). Form (Iα) of HMPAO was first crystallized from acetonitrile solution at room temperature, while form (Iβ) was obtained by recrystallization of (Iα) from Et2O at room temperature. The purities of the two meso-HMPAO phases were confirmed by multinuclear NMR and IR spectroscopic techniques and microanalysis. Many attempts were made to grow high-quality crystals of meso-HMPAO suitable for single X-ray diffraction study, but without success.

Refinement top

The powder of (Iα) or (Iβ) was ground, placed between two foils of Mylar, and fixed in the sample holder with a mask of suitable internal diameter (0.7 mm). The pattern of the α form was scanned over the angular range 3–80° (2θ) with a step width of the PSD of 0.1° (2θ) and a counting time of 60 s per step, while the pattern of the β form was scanned over the angular range 5–70° (2θ) with a step width of the PSD of 0.5° (2θ) and a counting time of 420 s per step. Pattern indexing was performed using the DICVOL4.0 program (Boultif & Louër, 2004) with default options. Confidence factors were M(20) = 34.1 and F(20) = 96.4 for the α form, and M(20) = 32.4 and F(20) = 85.4 for the β form. The space groups were obtained using the program CHECK-CELL interfaced by WINPLOTR (Roisnel & Rodriguez-Carvajal, 2001). The unreduced triclinic cell for (Iα) was used to make the c axis the common axis for the molecular chains in the two phases.

Direct methods were initially employed to determine the crystal structures using the program EXPO2004 (Altomare et al., 1999), but they were not successful. Starting models for the two forms were obtained using the direct-space method with the parallel tempering algorithm in the program FOX (Favre-Nicolin & Černý, 2002). One molecule of meso-HMPAO for both phases was introduced randomly with the possibility to translate, to rotate around its centre of mass and to modify its ten torsion angles. The degree of freedom for the molecular replacement for the two forms is 16. In order to accelerate the process during the parallel tempering calculation, the powder patterns were truncated to 36° (Cu Kα1) and the H atoms were not introduced. This method yielded a suitable model with agreement factors of Rp = 0.0776 for (Iα) and Rp = 0.0459 for (Iβ).

The two models thus obtained were used as starting points for Rietveld refinements in the program GSAS (Larson & Von Dreele, 2004), interfaced by EXPGUI (Toby, 2001). The coordinates of the 19 non-H atoms were refined with soft constraints on bond lengths. The profile function used was a pseudo-Voigt function convoluted with an axial divergence asymmetry function (Finger et al., 1994), and with S/L and D/L both fixed at 0.0225.

An isotropic displacement parameter was introduced and refined for each type of atom. Intensities were corrected for absorption effects with an m.d. [Define?] value of 0.1600 for (Iα) and 0.0434 for (Iβ). Before the final refinement, H atoms of the CH, CH2 and CH3 groups were introduced from geometric arguments and refined with constraints to the riding atoms (0.99 Å for CH, 0.98 Å for CH2 and 0.97 Å for CH3). The H atoms of the hydroxyl and amine groups were localized by difference Fourier syntheses and refined with constraints on bond lengths (0.82 Å for OH and 0.87 Å for NH) and angles. The background was refined using a shifted Chebyshev polynomial with 15 coefficients, whereas the preferred orientation was modelled using the generalized spherical-harmonics description (Von Dreele, 1997).

Final agreement factors are provided in the experimental tables. Fig. 4 shows the experimental X-ray patterns, together with the calculated patterns and difference curves from the final Rietveld refinements for both forms.

Computing details top

For both compounds, data collection: WINXPOW (Stoe & Cie, 1999); cell refinement: GSAS (Larson & Von Dreele, 2004); data reduction: WINXPOW (Stoe & Cie, 1999); program(s) used to solve structure: FOX (Favre-Nicolin & Černý, 2002); program(s) used to refine structure: GSAS (Larson & Von Dreele, 2004); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structures of (a) the (Iα) and (b) the (Iβ) forms of meso-HMPAO, with the atom-numbering schemes. Displacement ellipsoids are drawn at the ??% probability level [Please complete] and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. Packing diagrams of (a) the (Iα) and (b) the (Iβ) forms of meso-HMPAO. Oxime–amine O—H···N hydrogen bonds are indicated by dashed lines. H atoms have been omitted for clarity. [Symmetry code: (i) x, y, z + 1.]
[Figure 3] Fig. 3. Portions of adjacent molecular chains, viewed along the c axis, for (a) the (Iα) and (b) the (Iβ) forms of meso-HMPAO. Hydrogen bonds and short contacts between adjacent molecular chains are indicated by dashed lines. H atoms have been omitted for clarity. [Symmetry codes: (i) x, y, z + 1; (ii) -x, -y, -z; (iii) -x + 1/2, y + 1/2, -z + 1/2.]
[Figure 4] Fig. 4. Final observed (points), calculated (line) and difference profiles for Rietveld refinements of (a) the α and (b) the β forms of meso-HMPAO.
(Ialpha) meso-3,3'-[2,2-dimethylpropane-1,3-diylbis(azanediyl)]dibutan-2-one dioxime top
Crystal data top
C13H28N4O2Z = 2
Mr = 272.39F(000) = 300
Triclinic, P1Dx = 1.108 Mg m3
Hall symbol: -p 1Cu Kα1 radiation, λ = 1.5406 Å
a = 15.3159 (3) ŵ = 0.61 mm1
b = 8.74371 (12) ÅT = 298 K
c = 6.21770 (9) ÅParticle morphology: needle (visual estimate)
α = 81.1652 (10)°white
β = 93.4835 (10)°flat sheet, 7 × 7 mm
γ = 96.4282 (8)°Specimen preparation: Prepared at 298 K and 101.3 kPa
V = 816.80 (2) Å3
Data collection top
Stoe STADI P
diffractometer
Data collection mode: transmission
Radiation source: sealed X-ray tube, C-TechScan method: step
Ge 111 monochromator2θmin = 2.992°, 2θmax = 79.982°, 2θstep = 0.01°
Specimen mounting: drifted powder between two Mylar foils
Refinement top
Least-squares matrix: fullProfile function: CW Profile function number 4 with 27 terms Pseudovoigt profile coefficients as parameterized in Thompson et al. (1987). Asymmetry correction of (Finger et al., 1994). Microstrain broadening (Stephens, 1999). #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 10.581 #4(GP) = 0.000 #5(LX) = 3.335 #6(ptec) = 0.00 #7(trns) = 0.00 #8(shft) = 0.0000 #9(sfec) = 0.00 #10(S/L) = 0.0225 #11(H/L) = 0.0225 #12(eta) = 0.5000 Peak tails are ignored where the intensity is below 0.0010 times the peak. Aniso. broadening axis 0.0 0.0 1.0
Stephens, P. W. (1999). J. Appl. Cryst. 32, 281–289.
Thompson, P., Cox, D. E. & Hastings, J. B. (1987). J. Appl. Cryst. 20, 79–83.
Rp = 0.017224 parameters
Rwp = 0.023104 restraints
Rexp = 0.019H-atom parameters constrained
R(F2) = 0.01476(Δ/σ)max = 0.02
χ2 = 1.416Background function: GSAS background function number 1 with 20 terms. Shifted Chebyshev function of 1st kind 1: 2095.63 2: -2093.54 3: 1003.99 4: -224.356 5: -35.0151 6: 46.3120 7: 9.05002 8: -15.5584 9: -4.55608 10: 16.8935 11: -8.33517 12: 3.12503 13: -0.184876 14: -14.2318 15: 26.9383 16: -17.5033 17: 5.55156 18: -2.00997 19: 10.5513 20: -2.64504
7700 data points
Crystal data top
C13H28N4O2γ = 96.4282 (8)°
Mr = 272.39V = 816.80 (2) Å3
Triclinic, P1Z = 2
a = 15.3159 (3) ÅCu Kα1 radiation, λ = 1.5406 Å
b = 8.74371 (12) ŵ = 0.61 mm1
c = 6.21770 (9) ÅT = 298 K
α = 81.1652 (10)°flat sheet, 7 × 7 mm
β = 93.4835 (10)°
Data collection top
Stoe STADI P
diffractometer
Scan method: step
Specimen mounting: drifted powder between two Mylar foils2θmin = 2.992°, 2θmax = 79.982°, 2θstep = 0.01°
Data collection mode: transmission
Refinement top
Rp = 0.0177700 data points
Rwp = 0.023224 parameters
Rexp = 0.019104 restraints
R(F2) = 0.01476H-atom parameters constrained
χ2 = 1.416
Special details top

Experimental. The sample was ground lightly in a mortar, loaded between two Mylar foils and fixed in the sample holder with a mask of 7.0 mm internal diameter.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.8535 (3)0.2572 (5)0.5458 (7)0.0384 (14)*
C20.8898 (2)0.4043 (4)0.6396 (5)0.0384 (14)*
C30.9297 (2)0.1916 (4)0.4536 (6)0.0384 (14)*
C40.7864 (2)0.2921 (4)0.3527 (6)0.0384 (14)*
C50.8146 (2)0.1333 (4)0.7298 (6)0.0384 (14)*
N10.7022 (3)0.3372 (5)0.4180 (8)0.040 (2)*
N20.7779 (3)0.0133 (5)0.6474 (7)0.040 (2)*
C60.6527 (3)0.4088 (5)0.2256 (7)0.0384 (14)*
C70.7319 (3)0.1032 (5)0.8360 (7)0.0384 (14)*
C80.5772 (2)0.4852 (4)0.3012 (5)0.0384 (14)*
C90.6775 (2)0.2449 (4)0.7572 (5)0.0384 (14)*
C100.6267 (6)0.2786 (7)0.0933 (10)0.0384 (14)*
C110.7902 (4)0.1690 (9)1.0215 (10)0.0384 (14)*
C120.5702 (2)0.1332 (4)0.2004 (6)0.0384 (14)*
C130.8665 (2)0.2550 (4)0.9718 (5)0.0384 (14)*
N30.6410 (5)0.3115 (9)0.1105 (10)0.040 (2)*
N40.7815 (5)0.1252 (9)1.2052 (10)0.040 (2)*
O10.6002 (5)0.1967 (6)0.2299 (8)0.048 (2)*
O20.8376 (5)0.1993 (7)1.3625 (8)0.048 (2)*
H2A0.888140.493960.526840.05*
H2B0.854250.417180.757940.05*
H2C0.949880.394840.693830.05*
H3A0.953550.265870.333460.05*
H3B0.97550.173450.567390.05*
H3C0.908590.094280.401680.05*
H4A0.773750.199270.281320.05*
H4B0.813310.377190.248230.05*
H5A0.861070.109590.841650.05*
H5B0.767750.175920.795190.05*
H6A0.692580.490150.141250.05*
H7A0.692020.037530.890320.05*
H8A0.541350.408870.398010.05*
H8B0.601020.570220.378160.05*
H8C0.541360.524990.175440.05*
H9A0.716590.317220.724250.05*
H9B0.639010.296230.870540.05*
H9C0.642480.210370.627310.05*
H12A0.603180.043320.212780.05*
H12B0.555050.148760.344220.05*
H12C0.516670.115460.111780.05*
H13A0.909520.182160.890970.05*
H13B0.844520.335760.885760.05*
H13C0.893930.301611.107520.05*
H2O0.847910.147631.462070.05*
H2N0.739810.007690.540430.05*
H1O0.599150.231720.360180.05*
H1N0.712770.402710.510530.05*
Geometric parameters (Å, º) top
C1—C21.528 (4)C6—H6A0.991
C1—C31.535 (5)C7—C91.541 (4)
C1—C41.548 (4)C7—C111.498 (5)
C1—C51.548 (5)C7—H7A0.9910
C2—C11.528 (4)C8—H8A0.9715
C2—H2A0.9696C8—H8B0.9708
C2—H2B0.9683C8—H8C0.9697
C2—H2C0.9687C9—H9A0.9696
C3—H3A0.9717C9—H9B0.9696
C3—H3B0.9732C9—H9C0.9695
C3—H3C0.9711C10—C121.540 (5)
C4—N11.487 (5)C10—N31.282 (5)
C4—H4A0.979C11—C131.529 (5)
C4—H4B0.980C11—N41.278 (5)
C5—H5A0.981C12—H12A0.9720
C5—H5B0.979C12—H12B0.9701
N1—C41.487 (5)C12—H12C0.9705
N1—C61.471 (5)C13—H13A0.9699
N1—H1N0.869C13—H13B0.9689
N2—C51.492 (4)C13—H13C0.9714
N2—C71.477 (5)N3—O11.407 (5)
N2—H2N0.869N4—O21.394 (5)
C6—C81.530 (4)O1—H1O0.820
C6—C101.510 (5)O2—H2O0.819
C2—C1—C3108.4 (3)C10—C6—H6A109.2
C2—C1—C4111.9 (3)N2—C7—C9107.6 (3)
C2—C1—C5109.6 (3)N2—C7—C11115.5 (5)
C3—C1—C4106.3 (3)N2—C7—H7A109.4
C3—C1—C5108.0 (3)C9—C7—C11105.5 (4)
C4—C1—C5112.5 (3)C9—C7—H7A109.40
C1—C2—H2A109.54C11—C7—H7A109.10
C1—C2—H2B109.42C6—C8—H8A109.58
C1—C2—H2C109.32C6—C8—H8B109.42
H2A—C2—H2B109.40C6—C8—H8C109.35
H2A—C2—H2C109.68H8A—C8—H8B109.39
H2B—C2—H2C109.47H8A—C8—H8C109.55
C1—C3—H3A109.36H8B—C8—H8C109.54
C1—C3—H3B109.41C7—C9—H9A109.67
C1—C3—H3C109.63C7—C9—H9B109.43
H3A—C3—H3B109.48C7—C9—H9C109.46
H3A—C3—H3C109.39H9A—C9—H9B109.39
H3B—C3—H3C109.56H9A—C9—H9C109.44
C1—C4—N1113.7 (4)H9B—C9—H9C109.44
C1—C4—H4A108.61C6—C10—C12118.1 (4)
C1—C4—H4B108.30C6—C10—N3115.5 (5)
N1—C4—H4A108.68C12—C10—N3125.2 (6)
N1—C4—H4B108.7C7—C11—C13118.7 (4)
H4A—C4—H4B108.7C7—C11—N4116.2 (5)
C1—C5—N2112.0 (4)C13—C11—N4123.9 (6)
C1—C5—H5A108.91C10—C12—H12A109.40
C1—C5—H5B108.83C10—C12—H12B109.51
N2—C5—H5A108.95C10—C12—H12C109.70
N2—C5—H5B109.18H12A—C12—H12B109.58
H5A—C5—H5B108.9H12A—C12—H12C109.34
C4—N1—C6110.1 (4)H12B—C12—H12C109.35
C4—N1—H1N109.7C11—C13—H13A109.40
C6—N1—H1N109.5C11—C13—H13B109.50
C5—N2—C7103.2 (4)C11—C13—H13C109.48
C5—N2—H2N109.7H13A—C13—H13B109.46
C7—N2—H2N109.3H13A—C13—H13C109.45
N1—C6—C8108.9 (3)H13B—C13—H13C109.54
N1—C6—C10104.8 (5)C10—N3—O1112.3 (7)
N1—C6—H6A108.7C11—N4—O2109.7 (6)
C8—C6—C10116.1 (5)N3—O1—H1O109.3
C8—C6—H6A108.8N4—O2—H2O109.5
C6—N1—C4—C1164.5 (3)C2—C1—C5—N2179.9 (3)
C4—N1—C6—C8167.9 (3)C5—C1—C4—N154.4 (4)
C4—N1—C6—C1067.2 (5)C3—C1—C4—N1172.3 (3)
C5—N2—C7—C1172.3 (5)C2—C1—C4—N169.5 (4)
C7—N2—C5—C1170.9 (3)N1—C6—C10—C1259.1 (7)
C5—N2—C7—C9170.2 (3)C8—C6—C10—C1261.1 (7)
O1—N3—C10—C121.2 (11)C8—C6—C10—N3107.1 (8)
O1—N3—C10—C6168.5 (6)N1—C6—C10—N3132.6 (7)
O2—N4—C11—C1314.5 (10)N2—C7—C11—C1347.4 (7)
O2—N4—C11—C7178.1 (6)C9—C7—C11—N4120.6 (7)
C3—C1—C5—N262.1 (4)C9—C7—C11—C1371.3 (6)
C4—C1—C5—N254.8 (4)N2—C7—C11—N4120.7 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···N1i0.822.192.811 (8)133
O2—H2O···N2ii0.822.172.834 (7)138
Symmetry codes: (i) x, y, z1; (ii) x, y, z+1.
(Ibeta) meso-3,3'-[2,2-dimethylpropane-1,3-diylbis(azanediyl)]dibutan-2-one dioxime top
Crystal data top
C13H28N4O2F(000) = 600
Mr = 272.39Dx = 1.116 Mg m3
Monoclinic, P21/nCu Kα1 radiation, λ = 1.5406 Å
Hall symbol: -p 2ynµ = 0.61 mm1
a = 16.4453 (4) ÅT = 298 K
b = 15.9587 (3) ÅParticle morphology: fine powder (visual estimate)
c = 6.20073 (11) Åwhite
β = 94.7097 (13)°flat sheet, 7 × 7 mm
V = 1621.86 (7) Å3Specimen preparation: Prepared at 298 K and 101.3 kPa
Z = 4
Data collection top
Stoe STADI P
diffractometer
Data collection mode: transmission
Radiation source: sealed X-ray tube, C-TechScan method: step
Ge 111 monochromator2θmin = 5.970°, 2θmax = 69.960°, 2θstep = 0.01°
Specimen mounting: drifted powder between two Mylar foils
Refinement top
Least-squares matrix: fullProfile function: CW Profile function number 4 with 21 terms Pseudovoigt profile coefficients as parameterized in Thompson et al. (1987). Asymmetry correction of (Finger et al., 1994) Microstrain broadening by (Stephens, 1999). #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 10.448 #4(GP) = 0.000 #5(LX) = 2.798 #6(ptec) = 0.00 #7(trns) = 0.00 #8(shft) = 0.0000 #9(sfec) = 0.00 #10(S/L) = 0.0225 #11(H/L) = 0.0225 #12(eta) = 0.6000 #13(S400 ) = 7.2E-03 #14(S040 ) = 1.2E-02 #15(S004 ) = 1.9E-01 #16(S220 ) = -1.1E-03 #17(S202 ) = 3.5E-02 #18(S022 ) = 4.8E-02 #19(S301 ) = -1.7E-02 #20(S103 ) = -1.3E-02 #21(S121 ) = 1.0E-02
Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0
Stephens, P. W. (1999). J. Appl. Cryst. 32, 281–289.
Thompson, P., Cox, D. E. & Hastings, J. B. (1987). J. Appl. Cryst. 20, 79–83.
Rp = 0.020160 parameters
Rwp = 0.027104 restraints
Rexp = 0.024H-atom parameters constrained
R(F2) = 0.03684(Δ/σ)max = 0.02
χ2 = 1.346Background function: GSAS background function number 1 with 20 terms. Shifted Chebyshev function of 1st kind 1: 1694.08 2: -1888.90 3: 780.704 4: -143.263 5: -45.4949 6: 51.0746 7: 7.48171 8: -51.4972 9: 12.7024 10: 17.5629 11: -17.3374 12: 2.64363 13: 3.91414 14: -2.81271 15: 4.80400 16: 5.62048 17: -5.95626 18: 1.07944 19: 1.90253 20: -5.42175
? data points
Crystal data top
C13H28N4O2V = 1621.86 (7) Å3
Mr = 272.39Z = 4
Monoclinic, P21/nCu Kα1 radiation, λ = 1.5406 Å
a = 16.4453 (4) ŵ = 0.61 mm1
b = 15.9587 (3) ÅT = 298 K
c = 6.20073 (11) Åflat sheet, 7 × 7 mm
β = 94.7097 (13)°
Data collection top
Stoe STADI P
diffractometer
Scan method: step
Specimen mounting: drifted powder between two Mylar foils2θmin = 5.970°, 2θmax = 69.960°, 2θstep = 0.01°
Data collection mode: transmission
Refinement top
Rp = 0.020? data points
Rwp = 0.027160 parameters
Rexp = 0.024104 restraints
R(F2) = 0.03684H-atom parameters constrained
χ2 = 1.346
Special details top

Experimental. The sample was ground lightly in a mortar, loaded between two Mylar foils and fixed in the sample holder with a mask of 7.0 mm intrnal diameter.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2621 (3)0.2472 (3)0.0673 (7)0.034 (2)*
C20.3255 (2)0.2898 (2)0.2283 (5)0.034 (2)*
C30.2973 (2)0.1715 (2)0.0442 (6)0.034 (2)*
C40.2023 (2)0.2112 (2)0.2237 (6)0.034 (2)*
C50.2295 (2)0.3101 (2)0.1064 (6)0.034 (2)*
N10.1251 (3)0.1791 (3)0.1229 (8)0.026 (2)*
N20.1826 (3)0.3768 (3)0.0125 (8)0.026 (2)*
C60.0647 (3)0.1662 (3)0.2803 (7)0.034 (2)*
C70.1689 (3)0.4465 (3)0.1642 (7)0.034 (2)*
C80.0163 (2)0.1410 (2)0.1551 (5)0.034 (2)*
C90.1334 (2)0.5255 (2)0.0695 (6)0.034 (2)*
C100.0887 (5)0.0963 (3)0.4438 (11)0.034 (2)*
C110.1093 (4)0.4093 (6)0.3413 (11)0.034 (2)*
C120.1049 (2)0.0075 (2)0.3684 (6)0.034 (2)*
C130.0217 (2)0.3839 (2)0.3036 (6)0.034 (2)*
N30.0934 (6)0.1332 (5)0.6256 (10)0.026 (2)*
N40.1271 (5)0.4075 (6)0.5395 (11)0.026 (2)*
O10.1129 (5)0.0690 (3)0.7776 (8)0.041 (3)*
O20.0659 (3)0.3877 (5)0.7017 (9)0.041 (3)*
H2A0.305620.344560.267360.05*
H2B0.334260.255650.357660.05*
H2C0.376430.296070.162020.05*
H3A0.25330.140060.120660.05*
H3B0.325840.135690.063360.05*
H3C0.334880.190490.146390.05*
H4A0.190050.255530.325220.05*
H4B0.230060.165540.306080.05*
H5A0.275670.334830.174130.05*
H5B0.194270.280580.216640.05*
H6A0.057030.219160.359310.05*
H7A0.220820.460730.225940.05*
H8A0.006440.126630.007220.05*
H8B0.054440.187480.154340.05*
H8C0.039120.092920.224740.05*
H9A0.082140.512070.01040.05*
H9B0.124150.567220.182630.05*
H9C0.171520.547390.044320.05*
H12A0.163040.000280.360570.05*
H12B0.076770.001560.226850.05*
H12C0.085090.032150.47030.05*
H13A0.016370.420110.387270.05*
H13B0.013540.389470.151180.05*
H13C0.012670.326140.348440.05*
H1N0.105790.213740.023420.05*
H2N0.20880.394760.106310.05*
H1O0.125930.089850.896530.05*
H2O0.086860.371660.809670.05*
Geometric parameters (Å, º) top
C1—C21.541 (5)C7—C111.530 (5)
C1—C31.529 (5)C7—H7A0.991
C1—C41.547 (5)C8—C61.538 (4)
C1—C51.536 (5)C8—H8A0.9717
C2—H2A0.9705C8—H8B0.9714
C2—H2B0.9704C8—H8C0.9713
C2—H2C0.9683C9—H9A0.9707
C3—H3A0.9708C9—H9B0.9704
C3—H3B0.9694C9—H9C0.9698
C3—H3C0.9697C10—C121.522 (5)
C4—N11.462 (4)C10—N31.269 (5)
C4—H4A0.979C11—C131.531 (5)
C4—H4B0.981C11—N41.287 (5)
C5—N21.464 (4)C12—H12A0.9696
C5—H5A0.980C12—H12B0.9688
C5—H5B0.980C12—H12C0.9691
N1—C61.463 (5)C13—H13A0.9704
N1—H1N0.869C13—H13B0.9697
N2—C71.462 (5)C13—H13C0.9714
N2—H2N0.871N3—O11.411 (5)
C6—C81.538 (4)N4—O21.400 (5)
C6—C101.537 (5)O1—H1O0.821
C6—H6A0.990O2—H2O0.819
C7—C91.527 (4)
C2—C1—C3112.4 (3)C10—C6—H6A109.30
C2—C1—C4100.9 (3)N2—C7—C9115.1 (4)
C2—C1—C5110.2 (3)N2—C7—C11102.9 (5)
C3—C1—C4105.9 (3)N2—C7—H7A109.30
C3—C1—C5108.8 (3)C9—C7—C11110.7 (5)
C4—C1—C5118.6 (4)C9—C7—H7A109.10
C1—C2—H2A109.60C11—C7—H7A109.50
C1—C2—H2B109.55C6—C8—H8A109.53
C1—C2—H2C109.45C6—C8—H8B109.59
H2A—C2—H2B109.26C6—C8—H8C109.41
H2A—C2—H2C109.48H8A—C8—H8B109.45
H2B—C2—H2C109.49H8A—C8—H8C109.47
C1—C3—H3A109.53H8B—C8—H8C109.37
C1—C3—H3B109.51C7—C9—H9A109.54
C1—C3—H3C109.43C7—C9—H9B109.36
H3A—C3—H3B109.37C7—C9—H9C109.50
H3A—C3—H3C109.39H9A—C9—H9B109.53
H3B—C3—H3C109.59H9A—C9—H9C109.51
C1—C4—N1115.9 (4)H9B—C9—H9C109.39
C1—C4—H4A108.09C6—C10—C12121.0 (4)
C1—C4—H4B108.07C6—C10—N3104.0 (5)
N1—C4—H4A108.10C12—C10—N3134.9 (6)
N1—C4—H4B108.20C7—C11—C13123.2 (4)
H4A—C4—H4B108.30C7—C11—N4120.7 (6)
C1—C5—N2111.2 (4)C13—C11—N4115.5 (6)
C1—C5—H5A109.00C10—C12—H12A109.40
C1—C5—H5B109.12C10—C12—H12B109.50
N2—C5—H5A109.30C10—C12—H12C109.40
N2—C5—H5B109.02H12A—C12—H12B109.56
H5A—C5—H5B109.30H12A—C12—H12C109.55
C4—N1—C6112.2 (4)H12B—C12—H12C109.41
C4—N1—H1N109.50C11—C13—H13A109.60
C6—N1—H1N109.60C11—C13—H13B109.41
C5—N2—C7110.8 (4)C11—C13—H13C109.30
C5—N2—H2N109.60H13A—C13—H13B109.36
C7—N2—H2N109.50H13A—C13—H13C109.56
N1—C6—C8107.9 (3)H13B—C13—H13C109.57
N1—C6—C10112.9 (5)C10—N3—O1104.5 (7)
N1—C6—H6A109.30C11—N4—O2119.0 (7)
C8—C6—C10108.0 (4)N3—O1—H1O109.50
C8—C6—H6A109.50N4—O2—H2O109.30
C6—N1—C4—C1165.5 (4)C2—C1—C5—N266.3 (4)
C4—N1—C6—C8174.5 (3)C5—C1—C4—N148.7 (5)
C4—N1—C6—C1066.3 (5)C3—C1—C4—N173.8 (4)
C5—N2—C7—C1169.5 (5)C2—C1—C4—N1169.0 (3)
C7—N2—C5—C1166.1 (4)N1—C6—C10—C1257.8 (7)
C5—N2—C7—C9170.0 (4)C8—C6—C10—C1261.4 (7)
O1—N3—C10—C125.3 (14)C8—C6—C10—N3121.5 (7)
O1—N3—C10—C6178.2 (6)N1—C6—C10—N3119.3 (7)
O2—N4—C11—C133.4 (13)N2—C7—C11—C1366.6 (8)
O2—N4—C11—C7168.2 (7)C9—C7—C11—N4114.2 (8)
C3—C1—C5—N2170.2 (3)C9—C7—C11—C1356.9 (8)
C4—C1—C5—N249.2 (5)N2—C7—C11—N4122.4 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···N1i0.822.002.764 (7)154
O2—H2O···N2ii0.822.102.835 (7)150
Symmetry codes: (i) x, y, z+1; (ii) x, y, z1.

Experimental details

(Ialpha)(Ibeta)
Crystal data
Chemical formulaC13H28N4O2C13H28N4O2
Mr272.39272.39
Crystal system, space groupTriclinic, P1Monoclinic, P21/n
Temperature (K)298298
a, b, c (Å)15.3159 (3), 8.74371 (12), 6.21770 (9)16.4453 (4), 15.9587 (3), 6.20073 (11)
α, β, γ (°)81.1652 (10), 93.4835 (10), 96.4282 (8)90, 94.7097 (13), 90
V3)816.80 (2)1621.86 (7)
Z24
Radiation typeCu Kα1, λ = 1.5406 ÅCu Kα1, λ = 1.5406 Å
µ (mm1)0.610.61
Specimen shape, size (mm)Flat sheet, 7 × 7Flat sheet, 7 × 7
Data collection
DiffractometerStoe STADI P
diffractometer
Stoe STADI P
diffractometer
Specimen mountingDrifted powder between two Mylar foilsDrifted powder between two Mylar foils
Data collection modeTransmissionTransmission
Scan methodStepStep
Absorption correction?
GSAS absorption/surface roughness correction (Larson & Von Dreele, 2004): function number 4. Flat plate in transmission mode, absorption correction Term (= MU.r/wave) = 0.16000 Correction is not refined.
Tmin, Tmax0.660, 0.669
2θ values (°)2θmin = 2.992 2θmax = 79.982 2θstep = 0.012θmin = 5.970 2θmax = 69.960 2θstep = 0.01
Refinement
R factors and goodness of fitRp = 0.017, Rwp = 0.023, Rexp = 0.019, R(F2) = 0.01476, χ2 = 1.416Rp = 0.020, Rwp = 0.027, Rexp = 0.024, R(F2) = 0.03684, χ2 = 1.346
No. of data points7700?
No. of parameters224160
No. of restraints104104
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained

Computer programs: WINXPOW (Stoe & Cie, 1999), GSAS (Larson & Von Dreele, 2004), FOX (Favre-Nicolin & Černý, 2002), ORTEP-3 (Farrugia, 1997), publCIF (Westrip, 2010).

Selected geometric parameters (Å, º) for (Ialpha) top
C4—N11.487 (5)C7—C111.498 (5)
N1—C61.471 (5)C10—N31.282 (5)
N2—C51.492 (4)C11—N41.278 (5)
N2—C71.477 (5)N3—O11.407 (5)
C6—C101.510 (5)N4—O21.394 (5)
N1—C6—C10104.8 (5)C7—C11—C13118.7 (4)
N2—C7—C11115.5 (5)C7—C11—N4116.2 (5)
C6—C10—C12118.1 (4)C13—C11—N4123.9 (6)
C6—C10—N3115.5 (5)C10—N3—O1112.3 (7)
C12—C10—N3125.2 (6)C11—N4—O2109.7 (6)
C6—N1—C4—C1164.5 (3)O2—N4—C11—C1314.5 (10)
C4—N1—C6—C8167.9 (3)C8—C6—C10—C1261.1 (7)
C7—N2—C5—C1170.9 (3)N1—C6—C10—N3132.6 (7)
C5—N2—C7—C9170.2 (3)C9—C7—C11—C1371.3 (6)
O1—N3—C10—C121.2 (11)N2—C7—C11—N4120.7 (6)
Hydrogen-bond geometry (Å, º) for (Ialpha) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···N1i0.822.192.811 (8)133
O2—H2O···N2ii0.822.172.834 (7)138
Symmetry codes: (i) x, y, z1; (ii) x, y, z+1.
Selected geometric parameters (Å, º) for (Ibeta) top
C4—N11.462 (4)C7—C111.530 (5)
C5—N21.464 (4)C10—N31.269 (5)
N1—C61.463 (5)C11—N41.287 (5)
N2—C71.462 (5)N3—O11.411 (5)
C6—C101.537 (5)N4—O21.400 (5)
N1—C6—C10112.9 (5)C7—C11—C13123.2 (4)
N2—C7—C11102.9 (5)C7—C11—N4120.7 (6)
C6—C10—C12121.0 (4)C13—C11—N4115.5 (6)
C6—C10—N3104.0 (5)C10—N3—O1104.5 (7)
C12—C10—N3134.9 (6)C11—N4—O2119.0 (7)
C6—N1—C4—C1165.5 (4)O2—N4—C11—C133.4 (13)
C4—N1—C6—C8174.5 (3)C8—C6—C10—C1261.4 (7)
C7—N2—C5—C1166.1 (4)N1—C6—C10—N3119.3 (7)
C5—N2—C7—C9170.0 (4)C9—C7—C11—C1356.9 (8)
O1—N3—C10—C125.3 (14)N2—C7—C11—N4122.4 (9)
Hydrogen-bond geometry (Å, º) for (Ibeta) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···N1i0.822.002.764 (7)154
O2—H2O···N2ii0.822.102.835 (7)150
Symmetry codes: (i) x, y, z+1; (ii) x, y, z1.
 

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