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Journal logoCRYSTALLOGRAPHIC
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ISSN: 2056-9890
Volume 71| Part 10| October 2015| Pages 1222-1225
doi:10.1107/S2056989015017053

Synthesis, characterization and crystal structure of a 2-(di­ethylamino­methyl)indole ligated di­methyl­aluminium complex

CROSSMARK_Color_square_no_text.svg
Logan E. Shepharda and Nicholas B. Kingsleya*

aDepartment of Chemistry and Biochemistry, 556 MSB, 303 E. Kearsley, Flint, MI 48502, USA
*Correspondence e-mail: kingsley@umflint.edu

Edited by M. Zeller, Youngstown State University, USA (Received 25 June 2015; accepted 11 September 2015; online 26 September 2015)

The title compound, [Al(CH3)2(C13H17N2)] (systematic name; {2-[(di­ethyl­amino)­meth­yl]indol-1-yl-κ2N,N′}di­methyl­aluminium), was prepared by methane elimination from the reaction of 2-(di­ethyl­amino­meth­yl)indole and tri­methyl­aluminium. The complex crystallizes readily from a concentrated toluene solution in high yield. The asymmetric unit contains two crystallographically independent mol­ecules. Each mol­ecule has a four-coordinate aluminium atom that has pseudo-tetra­hedral geometry. C—H⋯π inter­actions link the independent mol­ecules into chains extending along the b-axis direction.

CCDC reference: 1423793

1. Chemical context

Organoaluminium chemistry has a long history of active research that has led to numerous applications in industry (Mason, 2005[Mason, M. R. (2005). Encyclopedia of Inorganic Chemistry, Vol. 1, 2nd ed., edited by B. King, pp. 185-210. Hoboken, NJ: Wiley.]). Organoaluminium compounds have garnered much attention in recent years for their use in the formation of polyactides, (Liu et al., 2010[Liu, Z., Gao, W., Zhang, J., Cui, D., Wu, Q. & Mu, Y. (2010). Organometallics, 29, 5783-5790.]; Chisholm et al., 2003[Chisholm, M. H., Lin, C.-C., Gallucci, J. C. & Ko, B. T. (2003). Dalton Trans. pp. 406-412.], 2005[Chisholm, M. H., Patmore, N. J. & Zhou, Z. (2005). Chem. Commun. pp. 127-129.]; Zhang et al., 2014[Zhang, W., Wang, Y., Wang, L., Redshaw, C. & Sun, W.-H. (2014). J. Organomet. Chem. 750, 65-73.]; Chen et al., 2012[Chen, H.-L., Dutta, S., Huang, P.-Y. & Lin, C.-C. (2012). Organo­metallics, 31, 2016-2025.]; Schwarz et al., 2010[Schwarz, A. D., Chu, Z. & Mountford, P. (2010). Organometallics, 29, 1246-1260.]) and hydro­amination (Koller & Bergman, 2010a[Koller, J. & Bergman, R. G. (2010a). Chem. Commun. 46, 4577-4579.],b[Koller, J. & Bergman, R. G. (2010b). Organometallics, 29, 5946-5952.]; Khandelwal & Wehmschulte, 2012[Khandelwal, M. & Wehmschulte, R. J. (2012). J. Organomet. Chem. 696, 4179-4183.]). While many varieties of ancillary ligands on aluminium have been employed in such reactions, a majority of these systems have nitro­gen-donor arms as a component. Our group is inter­ested in particular in the use of 2-(di­alkyl­amino­meth­yl)indoles (Nagarathnam, 1992[Nagarathnam, D. (1992). Synthesis, pp. 743-745.]) as ligands for organoaluminium complexes. Herein we report the synthesis, characterization and crystal structure of the first 2-(di­alkyl­amino­meth­yl)indol­yl–aluminium complex, [Al(CH3)2(C13H17N2)].

[Scheme 1]

2. Structural commentary

The asymmetric unit of the title complex contains two independent mol­ecules (Fig. 1[link]). They are structurally different with regard to the chelate rings that are formed around the aluminium atoms by the indolyl moiety. The most obvious difference between the two crystallographically independent mol­ecules is the displacement of the Al atom from the plane of the chelate ring. Al1 deviates by 0.6831 (5) Å from the plane defined by atoms N1/C10/C1/N2 while Al1A deviates by 0.6150 (5) Å from the plane N1A/C10A/C1A/N2A. Each mol­ecule contains a four-coordinate, pseudo-tetra­hedral, aluminium atom. There are two distinct bond lengths for the Al—N bonds in the mol­ecule. The Al—Nindol­yl bond lengths are 1.8879 (14) Å for Al1—N1 and 1.8779 (15) Å for Al1A—N1A. These lengths are in the range expected for anionically bound indolyl or pyrrolyl moieties (Huang et al., 2001[Huang, J., Chen, H., Chang, C., Zhou, C., Lee, G. & Peng, S. (2001). Organometallics, 20, 2647-2650.]). As expected, these lengths are significantly shorter than those found for the dative Al—Nimine bonds, 2.0355 (15) Å for Al1—N2 and 2.0397 (16) Å for Al1A—N2A [see Huang et al. (2001[Huang, J., Chen, H., Chang, C., Zhou, C., Lee, G. & Peng, S. (2001). Organometallics, 20, 2647-2650.]) for typical values].

[Figure 1]
Figure 1
A view of the asymmetric unit of the title compound, showing the atom labeling. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity.

3. Supra­molecular features

The crystal packing is illustrated in Fig. 2[link]. In the crystal, mol­ecules associate via three different types of C—H⋯π inter­actions, as shown in Figs. 3[link] and 4[link]. There is one inter­action between the methyl proton H5A and the centroid of the (C12A–C17A) aromatic ring of 2.57 Å (Table 1[link]) and another between the methyl­ene proton H4D and the aromatic C14 of 2.88 Å. The third inter­action is between H2B and the centroid of C12Ai–C17Ai [Table 1[link]; symmetry code: (i) 1 − x, −[{1\over 2}] + y, 1 − z]. This inter­action links the two independent mol­ecules in the asymmetric unit into chains that extend along the b-axis direction.

Table 1
C—H⋯π inter­actions (Å, °)

Cg1 is the centroid of the C12A–C17A ring.
D—H⋯A D—H H⋯A D⋯A D—H⋯A
C5—H5A⋯Cg1 0.98 2.57 3.470 (2) 153
C2—H2B⋯Cg1i 0.99 2.55 3.434 (2) 149
Symmetry code: (i) [-x+1, y-{\script{1\over 2}}, -z+1].
[Figure 2]
Figure 2
Crystal packing diagram of the title compound viewed along the a axis.
[Figure 3]
Figure 3
C—H⋯π inter­actions between mol­ecules in the asymmetric unit.
[Figure 4]
Figure 4
All C—H⋯π inter­actions between mol­ecules of the title compound. [Symmetry code: (i) 1 − x, −[{1\over 2}] + y, 1 − z.]

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.36; Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) for indolyl gave 500 hits. A search for indolide generated 18 hits. Neither of these sets of hits included structures involving indolyl moieties bound to aluminium. A substructure search for N-bound indolyl-coordinating aluminium complexes resulted in only five hits (Kingsley et al., 2010[Kingsley, N. B., Kirschbaum, K. & Mason, M. R. (2010). Organomet­allics, 29, 5927-5935.]), all of which contained bridging μ2:η1:η1 coordination modes. The title compound is the first struct­urally characterized complex with a monomeric μ1:η1-coordinating indole moiety to aluminium.

5. Synthesis and crystallization

To a 100 mL side-arm flask was added 2-(di­ethyl­amino­meth­yl)indole (0.402 g, 2.0 mmol) and 25 mL of toluene. A toluene solution of tri­methyl­aluminium (1.0 mL, 2.0 M, 2.0 mmol) was added via syringe. The reaction solution turned bright yellow, which darkened as the solution was stirred for 12 h. The solvent was then removed in vacuo resulting in a yellow solid, which was dissolved in a mixture of 10 mL of hot toluene, followed by cooling to 243 K for 48 h. The resulting yellow crystalline material was isolated by filtration. Yield: 0.462 g, 1.78 mmol, 90%. 1H NMR (CDCl3, 600 MHz): δ 7.55 (d, 3JHH = 7.8 Hz, 1H, H16), 7.36 (d, 3JHH = 7.8 Hz, 1H, H13), 7.07 (t, 3JHH = 7.8 Hz, 1H, H15), 7.00 (t, 3JHH = 7.8 Hz, 1H, H14), 6.31 (s, 1H, H11), 4.00 (s, 2H, indole CH2), 2.88 (q, 3JHH = 7.2 Hz, 4H, amino CH2CH3), 1.13 (t, 3JHH = 7.2 Hz, 6H, amino CH2CH3), −0.59 (s, 6H, AlCH3). 13C{1H} NMR (CDCl3, 150.8 MHz): δ 141.7 (C17), 139.4 (C10), 131.8 (C12), 120.2 (C15), 119.6 (C16), 118.5 (C15), 113.7 (C14), 98.1 (C11), 53.2 (indole CH2), 44.7 (amino CH2CH3), 8.3 (amino CH2CH3), −11.10 (br, AlCH3) (Kingsley et al., 2010[Kingsley, N. B., Kirschbaum, K. & Mason, M. R. (2010). Organomet­allics, 29, 5927-5935.]). Analysis calculated for C15H23N2Al: C, 69.74; H, 8.97; N, 10.84. Found: C, 69.67; H, 8.70; N, 10.63.

[Scheme 2]

X-ray quality crystals were grown from a concentrated solution in hot toluene followed by slow cooling to room temperature followed by storage at 243 K for 72 h.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. All H atoms were positioned geometrically and refined using a riding model with C—H = 0.05–0.99 Å and Uiso(H) = 1.2 or 1.5Ueq(C).

Table 2
Experimental details

Crystal data
Chemical formula [Al(CH3)2(C13H17N2)]
Mr 258.33
Crystal system, space group Monoclinic, P21
Temperature (K) 150
a, b, c (Å) 9.7467 (5), 14.1245 (7), 10.9866 (5)
β (°) 94.206 (1)
V (Å3) 1508.42 (13)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.12
Crystal size (mm) 0.20 × 0.20 × 0.15
 
Data collection
Diffractometer Bruker APEXII CCD
Absorption correction Multi-scan (SADABS; Bruker, 2003[Bruker (2003). SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.697, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections 13157, 5440, 5366
Rint 0.025
(sin θ/λ)max (Å−1) 0.624
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.068, 1.05
No. of reflections 5440
No. of parameters 333
No. of restraints 1
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.21, −0.19
Absolute structure Flack x determined using 2203 quotients [(I+)−(I−)]/[(I+)+(I−)] (Parsons et al., 2013[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.])
Absolute structure parameter 0.05 (3)
Computer programs: APEX2 (Bruker, 2005[Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]), SAINT (Bruker, 2003[Bruker (2003). SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), DIAMOND (Brandenburg, 2010[Brandenburg, K. (2010). DIAMOND. Crystal Impact GbR, Bonn, Germany.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.])..

Supporting information

CCDC reference: 1423793

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015017053/zl2630sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015017053/zl2630Isup2.hkl

checkCIF report


Chemical context top

Organoaluminium chemistry has a long history of active research that has led to numerous applications in industry (Mason, 2005). Organoaluminium compounds have garnered much attention in recent years for their use in the formation of polylactides, (Liu et al., 2010; Chisholm et al., 2003, 2005; Zhang et al., 2014; Chen et al., 2012; Schwarz et al., 2010) and hydro­amination. (Koller & Bergman, 2010a,b; Khandelwal & Wehmschulte, 2012) While many varieties of ancillary ligands on aluminium have been employed in such reactions, a majority of these systems have nitro­gen-donor arms as a component. Our group is inter­ested in particular in the use of 2-(di­alkyl­amino­methyl)­indoles (Nagarathnam, 1992) as ligands for organoaluminium complexes. Herein we report the synthesis, characterization and crystal structure of the first 2-(di­alkyl­amino­methyl)­indolyl–aluminium complex.

Structural commentary top

The asymmetric unit of the title compound has two crystallographically independent molecules (Fig. 1) and the molecule crystallizes in the monoclinic space group P21. The two independent molecules are structurally different with regard to the chelate rings that are formed around the aluminium atoms by the indolyl moiety. The most obvious difference between the two crystallographically independent molecules is the displacement of the Al atom from the plane of the chelate ring. Al1 deviates by 0.6831 (5) Å from the plane defined by atoms N1/C10/C1/N2 while Al1A deviates by 0.6150 (5) Å from the plane N1A/C10A/C1A/N2A. Each molecule contains a four-coordinate, pseudo-tetra­hedral, aluminium atom. There are two distinct distances for the Al—N bonds in the molecule. The Al—Nindolyl bond distances are 1.8879 (14) Å for Al1—N1 and 1.8779 (15) Å for Al1A—N1A. These distances are in the range expected for anionically bound indolyl or pyrrolyl moieties (Huang et al., 2001). As expected, these distances are significantly shorter than those found for the dative Al—Nimine bonds, 2.0355 (15) Å for Al1—N2 and 2.0397 (16) Å for Al1A—N2A [see Huang et al. (2001) for typical values].

Supra­molecular features top

The crystal packing is illustrated in Fig. 2. In the crystal, molecules associate via three different types of C—H···π inter­actions, as shown in Figs 3 and 4. There is one inter­action between the methyl proton H5A and the centroid of the (C12A–C17A) aromatic ring of 2.57 Å (Table 1) and another between the methyl­ene proton H4D and the aromatic C14 of 2.88 Å. The third inter­action is between H2B and the centroid of C12Ai–C17Ai [Table 1; symmetry code: (i) 1 - x, -1/2 + y, 1 - z]. This inter­action links the two independent molecules in the asymmetric unit into chains that extend along the b-axis direction.

Database survey top

A search of the Cambridge Structural Database (CSD, Version 5.36; Groom & Allen, 2014) for indolyl gave 500 hits. A search for indolide generated 18 hits. Neither of these sets of hits included structures involving indolyl moieties bound to aluminium. A substructure search for N-bound indolyl-coordinated aluminium complexes resulted in only five hits (Kingsley et al., 2010), all of which contained bridging µ2:η1:η1 coordination modes. The title compound is the first structurally characterized complex with a monomeric µ1:η1-coordinated indole moiety to aluminium.

Synthesis and crystallization top

To a 100 mL side-arm flask was added 2-(di­ethyl­amino­methyl)­indole (0.402 g, 2.0 mmol) and 25 mL of toluene. A toluene solution of tri­methyl­aluminium (1.0 mL, 2.0 M, 2.0 mmol) was added via syringe. The reaction solution turned bright yellow, which darkened as the solution was stirred for 12 h. The solvent was then removed in vacuo resulting in a yellow solid, which was dissolved in a mixture of 10 mL of hot toluene, followed by cooling to 243 K for 48 h. The resulting yellow crystalline material was isolated by filtration. Yield: 0.462 g, 1.78 mmol, 90%. 1H NMR (CDCl3, 600 MHz): δ 7.55 (d, 3JHH = 7.8 Hz, 1H, H16), 7.36 (d, 3JHH = 7.8 Hz, 1H, H13), 7.07 (t, 3JHH = 7.8 Hz, 1H, H15), 7.00 (t, 3JHH = 7.8 Hz, 1H, H14), 6.31 (s, 1H, H11), 4.00 (s, 2H, indole CH2), 2.88 (q, 3JHH = 7.2 Hz, 4H, amino CH2CH3), 1.13 (t, 3JHH = 7.2 Hz, 6H, amino CH2CH3), – 0.59 (s, 6H, AlCH3). 13C{1H} NMR (CDCl3, 150.8 MHz): δ 141.7 (C17), 139.4 (C10), 131.8 (C12), 120.2 (C15), 119.6 (C16), 118.5 (C15), 113.7 (C14), 98.1 (C11), 53.2 (indole CH2), 44.7 (amino CH2CH3), 8.3 (amino CH2CH3), –11.10 (br, AlCH3) (Kingsley et al., 2010). Analysis calculated for C15H23N2Al: C, 69.74; H, 8.97; N, 10.84. Found: C, 69.67; H, 8.70; N, 10.63.

X-ray quality crystals were grown from a concentrated solution in hot toluene followed by slow cooling to room temperature followed by storage at 243 K for 72 h.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were positioned geometrically and refined using a riding model with C—H = 0.05–0.99 Å and Uiso(H) = 1.2 or 1.5Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: publCIF (Westrip, 2010)..

Figures top
[Figure 1] Fig. 1. A view of the asymmetric unit of the title compound, showing the atom labeling. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. Crystal packing diagram of the title compound viewed along the a axis.
[Figure 3] Fig. 3. C—H···π interactions between molecules in the asymmetric unit.
[Figure 4] Fig. 4. All C—H···π interactions between molecules of the title compound. [Symmetry code: (i) 1 - x, -1/2 + y, 1 - z.]
{2-[(Diethylamino)methyl]indol-1-yl-κ2N,N'}dimethylaluminium top
Crystal data top
[Al(CH3)2(C13H17N2)]F(000) = 560
Mr = 258.33Dx = 1.138 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 9.7467 (5) ÅCell parameters from 5904 reflections
b = 14.1245 (7) Åθ = 2.4–26.4°
c = 10.9866 (5) ŵ = 0.12 mm−1
β = 94.206 (1)°T = 150 K
V = 1508.42 (13) Å3Irregular, yellow
Z = 40.20 × 0.20 × 0.15 mm
Data collection top
Bruker APEXII CCD
diffractometer		5366 reflections with I > 2σ(I)
Radiation source: sealed tubeRint = 0.025
φ and ω scansθmax = 26.3°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2003)		h = −12→10
Tmin = 0.697, Tmax = 0.745k = −16→17
13157 measured reflectionsl = −13→12
5440 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.024 w = 1/[σ2(Fo2) + (0.0388P)2 + 0.2513P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.068(Δ/σ)max < 0.001
S = 1.05Δρmax = 0.21 e Å−3
5440 reflectionsΔρmin = −0.19 e Å−3
333 parametersAbsolute structure: Flack x determined using 2203 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraintAbsolute structure parameter: 0.05 (3)
Crystal data top
[Al(CH3)2(C13H17N2)]V = 1508.42 (13) Å3
Mr = 258.33Z = 4
Monoclinic, P21Mo Kα radiation
a = 9.7467 (5) ŵ = 0.12 mm−1
b = 14.1245 (7) ÅT = 150 K
c = 10.9866 (5) Å0.20 × 0.20 × 0.15 mm
β = 94.206 (1)°
Data collection top
Bruker APEXII CCD
diffractometer		5440 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2003)		5366 reflections with I > 2σ(I)
Tmin = 0.697, Tmax = 0.745Rint = 0.025
13157 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.068Δρmax = 0.21 e Å−3
S = 1.05Δρmin = −0.19 e Å−3
5440 reflectionsAbsolute structure: Flack x determined using 2203 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
333 parametersAbsolute structure parameter: 0.05 (3)
1 restraint
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Al10.49235 (5)0.10530 (4)0.05845 (4)0.01712 (12)
Al1A0.00034 (5)0.32156 (4)0.44114 (4)0.01652 (12)
N10.29822 (14)0.10862 (11)0.04241 (13)0.0187 (3)
N1A0.19261 (14)0.30931 (11)0.44801 (12)0.0185 (3)
N20.46863 (14)0.02289 (10)0.20745 (13)0.0166 (3)
N2A0.02362 (15)0.42016 (11)0.30859 (12)0.0185 (3)
C10.33910 (17)−0.03044 (13)0.16893 (16)0.0194 (3)
H1A0.3588−0.08110.11050.023*
H1B0.3005−0.05980.24080.023*
C20.58090 (17)−0.04771 (13)0.23735 (16)0.0210 (4)
H2A0.5922−0.08760.16470.025*
H2B0.5532−0.08960.30350.025*
C30.7178 (2)−0.00237 (15)0.2769 (2)0.0311 (4)
H3A0.7883−0.05160.28930.047*
H3B0.70990.03220.35340.047*
H3C0.74390.04170.21360.047*
C40.44570 (18)0.08681 (13)0.31419 (15)0.0201 (3)
H4A0.36640.12850.29120.024*
H4B0.52760.12780.32910.024*
C50.4190 (2)0.03699 (15)0.43275 (17)0.0319 (4)
H5A0.40530.08430.49600.048*
H5B0.4981−0.00300.45850.048*
H5C0.3365−0.00250.42020.048*
C60.57142 (19)0.23092 (14)0.09103 (18)0.0263 (4)
H6A0.65340.22520.14780.039*
H6B0.50350.27130.12720.039*
H6C0.59690.25920.01440.039*
C70.58197 (19)0.02303 (15)−0.05668 (16)0.0254 (4)
H7A0.67890.0143−0.02840.038*
H7B0.57600.0524−0.13770.038*
H7C0.5357−0.0386−0.06130.038*
C100.23890 (17)0.03923 (13)0.11001 (15)0.0190 (3)
C110.10054 (18)0.05168 (13)0.11525 (16)0.0215 (4)
H110.03910.01260.15590.026*
C120.06711 (17)0.13596 (14)0.04673 (16)0.0204 (4)
C13−0.05440 (18)0.18738 (15)0.01868 (16)0.0256 (4)
H13−0.13970.16510.04420.031*
C14−0.0484 (2)0.27035 (16)−0.04612 (17)0.0283 (4)
H14−0.13040.3053−0.06550.034*
C150.0767 (2)0.30439 (15)−0.08420 (16)0.0281 (4)
H150.07830.3624−0.12770.034*
C160.19806 (19)0.25458 (14)−0.05925 (16)0.0238 (4)
H160.28270.2777−0.08520.029*
C170.19268 (17)0.16992 (13)0.00483 (15)0.0188 (3)
C1A0.14884 (18)0.38445 (14)0.24981 (15)0.0219 (4)
H1D0.12280.33240.19240.026*
H1E0.19000.43610.20370.026*
C2A0.05447 (18)0.51442 (13)0.36912 (15)0.0216 (4)
H2D0.13760.50720.42580.026*
H2E−0.02290.53090.41870.026*
C3A0.0777 (2)0.59665 (15)0.28370 (18)0.0299 (4)
H3D0.09660.65430.33170.045*
H3E−0.00470.60610.22840.045*
H3F0.15630.58260.23590.045*
C4A−0.09529 (19)0.42606 (15)0.21401 (16)0.0252 (4)
H4D−0.11060.36290.17640.030*
H4E−0.07140.47040.14900.030*
C5A−0.2272 (2)0.45879 (17)0.26472 (19)0.0327 (5)
H5D−0.30300.45390.20130.049*
H5E−0.21730.52480.29140.049*
H5F−0.24700.41900.33430.049*
C6A−0.0962 (2)0.21207 (14)0.36621 (17)0.0259 (4)
H6D−0.19360.22770.34850.039*
H6E−0.08800.15820.42250.039*
H6F−0.05530.19550.29020.039*
C7A−0.06954 (18)0.37556 (15)0.58896 (16)0.0234 (4)
H7D−0.16980.38200.57750.035*
H7E−0.02810.43800.60480.035*
H7F−0.04560.33370.65850.035*
C10A0.25049 (18)0.34955 (13)0.34895 (15)0.0198 (3)
C11A0.39089 (18)0.34640 (14)0.36008 (16)0.0223 (4)
H11A0.45200.37070.30420.027*
C12A0.42739 (18)0.29896 (12)0.47316 (16)0.0202 (4)
C13A0.55142 (18)0.27146 (14)0.53626 (18)0.0261 (4)
H13A0.63690.28430.50320.031*
C14A0.54780 (19)0.22547 (15)0.64699 (18)0.0284 (4)
H14A0.63160.20670.68990.034*
C15A0.4220 (2)0.20598 (14)0.69735 (17)0.0256 (4)
H15A0.42250.17440.77370.031*
C16A0.29816 (18)0.23198 (13)0.63774 (16)0.0205 (3)
H16A0.21350.21920.67230.025*
C17A0.30091 (17)0.27766 (13)0.52507 (15)0.0179 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Al10.0165 (2)0.0158 (3)0.0194 (2)0.00128 (19)0.00356 (18)0.00057 (19)
Al1A0.0162 (2)0.0184 (3)0.0150 (2)−0.00063 (19)0.00145 (18)−0.00094 (19)
N10.0183 (6)0.0191 (8)0.0189 (7)0.0012 (6)0.0020 (5)0.0021 (6)
N1A0.0193 (7)0.0195 (8)0.0168 (6)0.0008 (6)0.0031 (5)0.0009 (6)
N20.0177 (6)0.0129 (7)0.0192 (6)0.0013 (6)0.0003 (5)−0.0014 (6)
N2A0.0219 (7)0.0181 (7)0.0152 (6)0.0007 (6)0.0000 (5)−0.0016 (5)
C10.0208 (8)0.0148 (8)0.0225 (8)−0.0028 (7)0.0007 (6)0.0005 (6)
C20.0212 (8)0.0159 (9)0.0258 (8)0.0046 (7)−0.0001 (7)0.0011 (7)
C30.0231 (9)0.0283 (11)0.0409 (11)0.0037 (8)−0.0039 (8)0.0035 (9)
C40.0265 (8)0.0148 (9)0.0191 (8)0.0010 (7)0.0022 (6)−0.0021 (6)
C50.0516 (12)0.0236 (10)0.0216 (9)−0.0026 (9)0.0099 (8)−0.0019 (8)
C60.0255 (9)0.0194 (10)0.0348 (10)−0.0016 (7)0.0083 (8)0.0002 (8)
C70.0277 (9)0.0250 (10)0.0241 (9)0.0055 (8)0.0061 (7)0.0005 (7)
C100.0209 (8)0.0165 (8)0.0194 (7)−0.0024 (7)0.0012 (6)−0.0009 (6)
C110.0194 (8)0.0227 (10)0.0225 (8)−0.0037 (7)0.0024 (6)−0.0004 (7)
C120.0194 (8)0.0235 (9)0.0182 (8)0.0007 (7)0.0011 (6)−0.0046 (7)
C130.0211 (8)0.0341 (11)0.0216 (8)0.0050 (8)0.0013 (7)−0.0061 (7)
C140.0283 (9)0.0345 (11)0.0216 (8)0.0148 (8)−0.0018 (7)−0.0042 (8)
C150.0390 (10)0.0253 (10)0.0201 (8)0.0117 (8)0.0026 (7)0.0031 (7)
C160.0275 (9)0.0256 (10)0.0189 (8)0.0042 (7)0.0048 (7)0.0027 (7)
C170.0206 (8)0.0206 (9)0.0152 (7)0.0024 (7)0.0011 (6)−0.0019 (6)
C1A0.0253 (8)0.0244 (9)0.0166 (8)0.0014 (7)0.0053 (6)0.0000 (7)
C2A0.0268 (8)0.0181 (9)0.0197 (8)−0.0009 (7)0.0006 (7)−0.0026 (7)
C3A0.0372 (10)0.0223 (10)0.0301 (9)−0.0035 (8)0.0034 (8)0.0017 (8)
C4A0.0296 (9)0.0271 (10)0.0177 (8)−0.0012 (8)−0.0064 (7)0.0010 (7)
C5A0.0275 (9)0.0354 (12)0.0338 (10)0.0040 (8)−0.0064 (8)0.0004 (9)
C6A0.0291 (9)0.0246 (10)0.0237 (9)−0.0051 (8)−0.0004 (7)−0.0022 (8)
C7A0.0211 (8)0.0295 (10)0.0198 (8)−0.0006 (7)0.0034 (6)−0.0037 (7)
C10A0.0239 (8)0.0183 (8)0.0177 (8)−0.0005 (7)0.0063 (6)−0.0015 (6)
C11A0.0225 (8)0.0211 (9)0.0244 (8)−0.0027 (7)0.0097 (7)−0.0041 (7)
C12A0.0209 (8)0.0158 (9)0.0242 (8)−0.0003 (6)0.0050 (7)−0.0067 (6)
C13A0.0182 (8)0.0244 (10)0.0358 (10)0.0015 (7)0.0040 (7)−0.0085 (8)
C14A0.0227 (9)0.0277 (10)0.0335 (10)0.0079 (7)−0.0063 (7)−0.0081 (8)
C15A0.0307 (9)0.0213 (10)0.0239 (8)0.0056 (8)−0.0031 (7)−0.0024 (7)
C16A0.0226 (8)0.0172 (9)0.0218 (8)0.0021 (7)0.0028 (6)−0.0024 (6)
C17A0.0188 (8)0.0148 (8)0.0203 (8)0.0008 (6)0.0021 (6)−0.0047 (7)
Geometric parameters (Å, º) top
Al1—N11.8879 (14)C12—C171.422 (2)
Al1—C61.957 (2)C13—C141.375 (3)
Al1—C71.9686 (19)C13—H130.9500
Al1—N22.0355 (15)C14—C151.403 (3)
Al1A—N1A1.8779 (15)C14—H140.9500
Al1A—C6A1.960 (2)C15—C161.386 (3)
Al1A—C7A1.9610 (18)C15—H150.9500
Al1A—N2A2.0397 (16)C16—C171.391 (3)
N1—C101.382 (2)C16—H160.9500
N1—C171.384 (2)C1A—C10A1.501 (2)
N1A—C17A1.378 (2)C1A—H1D0.9900
N1A—C10A1.384 (2)C1A—H1E0.9900
N2—C21.499 (2)C2A—C3A1.521 (3)
N2—C11.504 (2)C2A—H2D0.9900
N2—C41.510 (2)C2A—H2E0.9900
N2A—C4A1.501 (2)C3A—H3D0.9800
N2A—C2A1.509 (2)C3A—H3E0.9800
N2A—C1A1.509 (2)C3A—H3F0.9800
C1—C101.500 (2)C4A—C5A1.511 (3)
C1—H1A0.9900C4A—H4D0.9900
C1—H1B0.9900C4A—H4E0.9900
C2—C31.515 (3)C5A—H5D0.9800
C2—H2A0.9900C5A—H5E0.9800
C2—H2B0.9900C5A—H5F0.9800
C3—H3A0.9800C6A—H6D0.9800
C3—H3B0.9800C6A—H6E0.9800
C3—H3C0.9800C6A—H6F0.9800
C4—C51.520 (2)C7A—H7D0.9800
C4—H4A0.9900C7A—H7E0.9800
C4—H4B0.9900C7A—H7F0.9800
C5—H5A0.9800C10A—C11A1.366 (2)
C5—H5B0.9800C11A—C12A1.433 (3)
C5—H5C0.9800C11A—H11A0.9500
C6—H6A0.9800C12A—C13A1.404 (2)
C6—H6B0.9800C12A—C17A1.428 (2)
C6—H6C0.9800C13A—C14A1.382 (3)
C7—H7A0.9800C13A—H13A0.9500
C7—H7B0.9800C14A—C15A1.409 (3)
C7—H7C0.9800C14A—H14A0.9500
C10—C111.365 (2)C15A—C16A1.380 (2)
C11—C121.433 (3)C15A—H15A0.9500
C11—H110.9500C16A—C17A1.398 (2)
C12—C131.404 (2)C16A—H16A0.9500
N1—Al1—C6111.91 (8)C14—C13—C12119.17 (18)
N1—Al1—C7116.33 (8)C14—C13—H13120.4
C6—Al1—C7117.73 (8)C12—C13—H13120.4
N1—Al1—N285.25 (6)C13—C14—C15121.16 (17)
C6—Al1—N2115.96 (7)C13—C14—H14119.4
C7—Al1—N2105.14 (7)C15—C14—H14119.4
N1A—Al1A—C6A113.03 (8)C16—C15—C14120.99 (19)
N1A—Al1A—C7A114.12 (7)C16—C15—H15119.5
C6A—Al1A—C7A118.00 (8)C14—C15—H15119.5
N1A—Al1A—N2A85.91 (6)C15—C16—C17118.25 (17)
C6A—Al1A—N2A108.30 (7)C15—C16—H16120.9
C7A—Al1A—N2A112.91 (8)C17—C16—H16120.9
C10—N1—C17105.83 (13)N1—C17—C16129.35 (16)
C10—N1—Al1112.84 (11)N1—C17—C12109.32 (16)
C17—N1—Al1139.57 (13)C16—C17—C12121.28 (16)
C17A—N1A—C10A106.15 (14)C10A—C1A—N2A108.11 (13)
C17A—N1A—Al1A140.50 (12)C10A—C1A—H1D110.1
C10A—N1A—Al1A113.18 (11)N2A—C1A—H1D110.1
C2—N2—C1108.22 (13)C10A—C1A—H1E110.1
C2—N2—C4112.02 (12)N2A—C1A—H1E110.1
C1—N2—C4110.43 (13)H1D—C1A—H1E108.4
C2—N2—Al1115.63 (10)N2A—C2A—C3A115.85 (14)
C1—N2—Al1101.69 (10)N2A—C2A—H2D108.3
C4—N2—Al1108.35 (10)C3A—C2A—H2D108.3
C4A—N2A—C2A112.02 (14)N2A—C2A—H2E108.3
C4A—N2A—C1A109.27 (13)C3A—C2A—H2E108.3
C2A—N2A—C1A110.02 (13)H2D—C2A—H2E107.4
C4A—N2A—Al1A114.30 (11)C2A—C3A—H3D109.5
C2A—N2A—Al1A108.47 (10)C2A—C3A—H3E109.5
C1A—N2A—Al1A102.31 (11)H3D—C3A—H3E109.5
C10—C1—N2107.43 (14)C2A—C3A—H3F109.5
C10—C1—H1A110.2H3D—C3A—H3F109.5
N2—C1—H1A110.2H3E—C3A—H3F109.5
C10—C1—H1B110.2N2A—C4A—C5A113.37 (15)
N2—C1—H1B110.2N2A—C4A—H4D108.9
H1A—C1—H1B108.5C5A—C4A—H4D108.9
N2—C2—C3113.28 (15)N2A—C4A—H4E108.9
N2—C2—H2A108.9C5A—C4A—H4E108.9
C3—C2—H2A108.9H4D—C4A—H4E107.7
N2—C2—H2B108.9C4A—C5A—H5D109.5
C3—C2—H2B108.9C4A—C5A—H5E109.5
H2A—C2—H2B107.7H5D—C5A—H5E109.5
C2—C3—H3A109.5C4A—C5A—H5F109.5
C2—C3—H3B109.5H5D—C5A—H5F109.5
H3A—C3—H3B109.5H5E—C5A—H5F109.5
C2—C3—H3C109.5Al1A—C6A—H6D109.5
H3A—C3—H3C109.5Al1A—C6A—H6E109.5
H3B—C3—H3C109.5H6D—C6A—H6E109.5
N2—C4—C5115.68 (15)Al1A—C6A—H6F109.5
N2—C4—H4A108.4H6D—C6A—H6F109.5
C5—C4—H4A108.4H6E—C6A—H6F109.5
N2—C4—H4B108.4Al1A—C7A—H7D109.5
C5—C4—H4B108.4Al1A—C7A—H7E109.5
H4A—C4—H4B107.4H7D—C7A—H7E109.5
C4—C5—H5A109.5Al1A—C7A—H7F109.5
C4—C5—H5B109.5H7D—C7A—H7F109.5
H5A—C5—H5B109.5H7E—C7A—H7F109.5
C4—C5—H5C109.5C11A—C10A—N1A112.32 (15)
H5A—C5—H5C109.5C11A—C10A—C1A132.80 (16)
H5B—C5—H5C109.5N1A—C10A—C1A114.84 (14)
Al1—C6—H6A109.5C10A—C11A—C12A106.03 (15)
Al1—C6—H6B109.5C10A—C11A—H11A127.0
H6A—C6—H6B109.5C12A—C11A—H11A127.0
Al1—C6—H6C109.5C13A—C12A—C17A118.82 (17)
H6A—C6—H6C109.5C13A—C12A—C11A135.04 (17)
H6B—C6—H6C109.5C17A—C12A—C11A106.14 (15)
Al1—C7—H7A109.5C14A—C13A—C12A119.22 (17)
Al1—C7—H7B109.5C14A—C13A—H13A120.4
H7A—C7—H7B109.5C12A—C13A—H13A120.4
Al1—C7—H7C109.5C13A—C14A—C15A121.12 (17)
H7A—C7—H7C109.5C13A—C14A—H14A119.4
H7B—C7—H7C109.5C15A—C14A—H14A119.4
C11—C10—N1112.64 (15)C16A—C15A—C14A121.18 (18)
C11—C10—C1132.87 (16)C16A—C15A—H15A119.4
N1—C10—C1114.36 (14)C14A—C15A—H15A119.4
C10—C11—C12105.78 (15)C15A—C16A—C17A118.04 (17)
C10—C11—H11127.1C15A—C16A—H16A121.0
C12—C11—H11127.1C17A—C16A—H16A121.0
C13—C12—C17119.11 (18)N1A—C17A—C16A129.05 (16)
C13—C12—C11134.47 (17)N1A—C17A—C12A109.34 (15)
C17—C12—C11106.40 (15)C16A—C17A—C12A121.61 (16)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C12A–C17A ring.
D—H···AD—HH···AD···AD—H···A
C5—H5A···Cg10.982.573.470 (2)153
C2—H2B···Cg1i0.992.553.434 (2)149
Symmetry code: (i) −x+1, y−1/2, −z+1.
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C12A–C17A ring.
D—H···AD—HH···AD···AD—H···A
C5—H5A···Cg10.982.573.470 (2)153
C2—H2B···Cg1i0.992.553.434 (2)149
Symmetry code: (i) −x+1, y−1/2, −z+1.

Experimental details

Crystal data
Chemical formula[Al(CH3)2(C13H17N2)]
Mr258.33
Crystal system, space groupMonoclinic, P21
Temperature (K)150
a, b, c (Å)9.7467 (5), 14.1245 (7), 10.9866 (5)
β (°) 94.206 (1)
V (Å3)1508.42 (13)
Z4
Radiation typeMo Kα
µ (mm−1)0.12
Crystal size (mm)0.20 × 0.20 × 0.15
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2003)
Tmin, Tmax0.697, 0.745
No. of measured, independent and
observed [I > 2σ(I)] reflections		13157, 5440, 5366
Rint0.025
(sin θ/λ)max (Å−1)0.624
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.068, 1.05
No. of reflections5440
No. of parameters333
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.21, −0.19
Absolute structureFlack x determined using 2203 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Absolute structure parameter0.05 (3)

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), DIAMOND (Brandenburg, 2010), publCIF (Westrip, 2010)..

 

Acknowledgements

The authors would like to thank the University of Michigan-Flint Office of Research and Sponsored Programs for their support of this project. Special acknowledgement is given to Dr Chris Gianopoulos for assistance in data collection and structure refinement and to the University of Toledo Instrumentation Center for the use of their Bruker APEXII diffractometer.

References

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Journal logoCRYSTALLOGRAPHIC
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ISSN: 2056-9890
Volume 71| Part 10| October 2015| Pages 1222-1225
doi:10.1107/S2056989015017053
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