organic compounds
[1,4-Bis(4-methoxyphenyl)but-3-yn-2-yl](cyano)methylamine
aLife and Health Sciences Department, University of North Texas at Dallas, 7300 University Hills Blvd, Dallas, TX 75241, USA, and bDepartment of Chemistry and Biochemistry, University of Texas at Arlington, 701 S. Nedderman Dr., Arlington, TX 76019, USA
*Correspondence e-mail: myousuf@untdallas.edu
The title compound, C20H20N2O2, crystallizes in the P21/c with one molecule in the It contains an amine with a cyano substituent and hence is classified as a cyanamide. One terminal CH3 group is disordered over two positions with occupancies of 0.874 (9)/0.126 (9).
Keywords: crystal structure; cyanamide.
Structure description
Some of us have been involved in the synthesis of cyanamides from N-methyl propargylamines and using this as a starting point to produce propargyl guanidine derivatives, specifically adapting reports from Looper (Gainer et al., 2011) and van der Eycken (Ermolat'ev et al., 2010). Originally, a very interesting spirocyclization compound was produced while attempting to synthesize the title compound (Singh et al., 2016). It was later discovered that using potassium carbonate as the base afforded the intended cyanamide in good yield.
The title compound crystallizes in the monoclinic P21/c. There is one molecule in the yielding a Z value of 4. The compound contains one cyano bond with an observed C≡N bond distance of 1.143 (2) Å and one C≡C bond with a distance of 1.189 (3) Å. One terminal CH3 group (C12) is disordered over two positions with occupancies of 0.874 (9)/0.126 (9). Intermolecular C—H⋯O interactions are observed in the crystal (Table 1) as well as π–π interactions between C4–C9 phenyl rings [centroid–centroid distance = 3.8766 (14) Å, 1 − x, 1 − y, 2 − z].
Synthesis and crystallization
The title compound was synthesized and crystallized following the procedure reported by our group (Singh et al., 2016).
Refinement
Crystal data, data collection and structure . One terminal CH3 group (C12) is disordered over two positions with occupancies of 0.874 (9)/0.126 (9).
details are summarized in Table 2Structural data
https://doi.org/10.1107/S2414314618003899/bv4015sup1.cif
contains datablocks I, 1R. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618003899/bv4015Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314618003899/bv4015Isup3.cml
Data collection: APEX2 (Bruker, 2016); cell
SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C20H20N2O2 | F(000) = 680 |
Mr = 320.38 | Dx = 1.194 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 15.6203 (19) Å | Cell parameters from 4903 reflections |
b = 8.6349 (11) Å | θ = 2.8–24.2° |
c = 13.9758 (17) Å | µ = 0.08 mm−1 |
β = 108.948 (2)° | T = 299 K |
V = 1782.9 (4) Å3 | Plate, colourless |
Z = 4 | 0.25 × 0.15 × 0.05 mm |
Bruker D8 QUEST CCD diffractometer | 2256 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.032 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | θmax = 25.2°, θmin = 2.8° |
Tmin = 0.687, Tmax = 0.745 | h = −18→18 |
15747 measured reflections | k = −10→10 |
3209 independent reflections | l = −16→16 |
Refinement on F2 | 6 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.124 | w = 1/[σ2(Fo2) + (0.0517P)2 + 0.390P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
3209 reflections | Δρmax = 0.11 e Å−3 |
231 parameters | Δρmin = −0.15 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. H atoms were positioned geometrically (C—H = 0.93–0.98 Å) and allowed to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C) for methyl H and 1.2Ueq(C) for other H atoms. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1 | 0.57799 (10) | 0.79026 (19) | 1.22133 (10) | 0.0801 (4) | |
O2 | 0.06643 (10) | 0.24335 (17) | 0.21707 (11) | 0.0851 (5) | |
N1 | 0.15952 (10) | 0.63823 (18) | 0.62029 (11) | 0.0588 (4) | |
N2 | 0.18905 (13) | 0.8975 (2) | 0.56414 (16) | 0.0865 (6) | |
C1 | 0.23575 (13) | 0.5294 (2) | 0.66066 (13) | 0.0610 (5) | |
H1 | 0.209964 | 0.429138 | 0.669741 | 0.073* | |
C2 | 0.29652 (14) | 0.5784 (2) | 0.76050 (15) | 0.0697 (6) | |
C3 | 0.34778 (14) | 0.6166 (2) | 0.84027 (15) | 0.0679 (5) | |
C4 | 0.40886 (13) | 0.6616 (2) | 0.93728 (13) | 0.0587 (5) | |
C5 | 0.48196 (16) | 0.7550 (3) | 0.94619 (15) | 0.0797 (6) | |
H5 | 0.492569 | 0.788760 | 0.887863 | 0.096* | |
C6 | 0.54045 (14) | 0.8005 (3) | 1.03945 (15) | 0.0734 (6) | |
H6 | 0.589565 | 0.864071 | 1.043571 | 0.088* | |
C7 | 0.52533 (13) | 0.7510 (2) | 1.12534 (13) | 0.0578 (5) | |
C8 | 0.45402 (15) | 0.6558 (3) | 1.11778 (15) | 0.0775 (6) | |
H8 | 0.444383 | 0.620286 | 1.176268 | 0.093* | |
C9 | 0.39607 (14) | 0.6114 (3) | 1.02494 (15) | 0.0726 (6) | |
H9 | 0.347567 | 0.546656 | 1.021390 | 0.087* | |
C10 | 0.65565 (16) | 0.8814 (3) | 1.23183 (17) | 0.0907 (7) | |
H10A | 0.695384 | 0.827080 | 1.203500 | 0.136* | |
H10B | 0.686469 | 0.901142 | 1.302242 | 0.136* | |
H10C | 0.637842 | 0.977860 | 1.196884 | 0.136* | |
C11 | 0.17720 (13) | 0.7776 (3) | 0.59205 (14) | 0.0597 (5) | |
C12A | 0.0877 (2) | 0.6328 (4) | 0.6658 (4) | 0.0891 (13) | 0.874 (9) |
H12A | 0.111732 | 0.662393 | 0.735717 | 0.134* | 0.874 (9) |
H12B | 0.063944 | 0.529530 | 0.661001 | 0.134* | 0.874 (9) |
H12C | 0.040208 | 0.702994 | 0.630789 | 0.134* | 0.874 (9) |
C12B | 0.0668 (17) | 0.581 (3) | 0.601 (3) | 0.101 (5) | 0.126 (9) |
H12D | 0.061446 | 0.536197 | 0.661323 | 0.151* | 0.126 (9) |
H12E | 0.053591 | 0.503392 | 0.548461 | 0.151* | 0.126 (9) |
H12F | 0.024869 | 0.665025 | 0.579117 | 0.151* | 0.126 (9) |
C13 | 0.28728 (13) | 0.5050 (2) | 0.58608 (14) | 0.0659 (5) | |
H13A | 0.312140 | 0.603313 | 0.574249 | 0.079* | |
H13B | 0.337506 | 0.435089 | 0.615901 | 0.079* | |
C14 | 0.22912 (12) | 0.4395 (2) | 0.48628 (13) | 0.0555 (5) | |
C15 | 0.20917 (13) | 0.2831 (2) | 0.47567 (14) | 0.0635 (5) | |
H15 | 0.232870 | 0.218169 | 0.531061 | 0.076* | |
C16 | 0.15548 (13) | 0.2209 (2) | 0.38592 (15) | 0.0664 (5) | |
H16 | 0.143494 | 0.115157 | 0.380955 | 0.080* | |
C17 | 0.11941 (12) | 0.3153 (2) | 0.30326 (14) | 0.0584 (5) | |
C18 | 0.13769 (14) | 0.4706 (2) | 0.31150 (14) | 0.0678 (5) | |
H18 | 0.113317 | 0.535283 | 0.256101 | 0.081* | |
C19 | 0.19235 (14) | 0.5311 (2) | 0.40214 (15) | 0.0681 (5) | |
H19 | 0.204728 | 0.636697 | 0.406576 | 0.082* | |
C20 | 0.02856 (19) | 0.3332 (3) | 0.12903 (17) | 0.1032 (9) | |
H20A | −0.008987 | 0.412710 | 0.142382 | 0.155* | |
H20B | −0.007307 | 0.268024 | 0.075259 | 0.155* | |
H20C | 0.076206 | 0.379836 | 0.109588 | 0.155* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0736 (9) | 0.1082 (12) | 0.0514 (8) | −0.0065 (9) | 0.0106 (7) | −0.0141 (8) |
O2 | 0.0909 (11) | 0.0813 (10) | 0.0642 (9) | −0.0046 (8) | −0.0006 (8) | −0.0114 (8) |
N1 | 0.0566 (9) | 0.0574 (10) | 0.0596 (9) | 0.0005 (7) | 0.0148 (7) | −0.0001 (8) |
N2 | 0.0871 (14) | 0.0658 (12) | 0.1086 (15) | 0.0003 (10) | 0.0345 (12) | 0.0091 (11) |
C1 | 0.0661 (12) | 0.0548 (11) | 0.0544 (11) | 0.0019 (9) | 0.0090 (9) | −0.0019 (9) |
C2 | 0.0731 (14) | 0.0681 (13) | 0.0587 (12) | 0.0082 (10) | 0.0088 (11) | −0.0032 (10) |
C3 | 0.0710 (13) | 0.0663 (13) | 0.0584 (12) | 0.0130 (10) | 0.0099 (11) | −0.0042 (10) |
C4 | 0.0577 (11) | 0.0607 (12) | 0.0512 (11) | 0.0116 (9) | 0.0087 (9) | −0.0052 (9) |
C5 | 0.0895 (16) | 0.0968 (17) | 0.0489 (12) | −0.0125 (13) | 0.0173 (11) | 0.0062 (11) |
C6 | 0.0706 (13) | 0.0878 (15) | 0.0578 (12) | −0.0164 (11) | 0.0152 (10) | −0.0005 (11) |
C7 | 0.0553 (11) | 0.0689 (12) | 0.0463 (10) | 0.0082 (9) | 0.0124 (8) | −0.0071 (9) |
C8 | 0.0776 (14) | 0.1084 (18) | 0.0496 (11) | −0.0138 (13) | 0.0250 (11) | −0.0049 (11) |
C9 | 0.0632 (12) | 0.0891 (15) | 0.0663 (13) | −0.0110 (11) | 0.0221 (10) | −0.0096 (11) |
C10 | 0.0737 (15) | 0.1042 (18) | 0.0751 (15) | −0.0065 (13) | −0.0020 (12) | −0.0140 (13) |
C11 | 0.0534 (11) | 0.0636 (13) | 0.0589 (11) | 0.0006 (10) | 0.0140 (9) | −0.0054 (10) |
C12A | 0.089 (2) | 0.076 (2) | 0.120 (3) | −0.0040 (16) | 0.059 (2) | 0.0020 (19) |
C12B | 0.098 (9) | 0.081 (9) | 0.128 (10) | 0.004 (8) | 0.042 (9) | 0.006 (8) |
C13 | 0.0585 (11) | 0.0669 (12) | 0.0658 (12) | 0.0025 (10) | 0.0113 (10) | −0.0093 (10) |
C14 | 0.0556 (10) | 0.0541 (11) | 0.0559 (11) | 0.0045 (8) | 0.0168 (8) | −0.0043 (9) |
C15 | 0.0710 (13) | 0.0553 (12) | 0.0576 (11) | 0.0058 (9) | 0.0120 (10) | 0.0066 (9) |
C16 | 0.0756 (13) | 0.0489 (11) | 0.0681 (13) | −0.0048 (10) | 0.0143 (11) | −0.0019 (10) |
C17 | 0.0573 (11) | 0.0607 (12) | 0.0541 (11) | 0.0010 (9) | 0.0137 (9) | −0.0057 (9) |
C18 | 0.0860 (14) | 0.0591 (12) | 0.0524 (11) | 0.0105 (10) | 0.0144 (10) | 0.0057 (9) |
C19 | 0.0891 (14) | 0.0472 (11) | 0.0660 (13) | −0.0001 (10) | 0.0225 (11) | −0.0002 (10) |
C20 | 0.1074 (19) | 0.119 (2) | 0.0610 (14) | 0.0096 (17) | −0.0036 (13) | −0.0046 (14) |
O1—C7 | 1.369 (2) | C10—H10B | 0.9600 |
O1—C10 | 1.413 (3) | C10—H10C | 0.9600 |
O2—C17 | 1.369 (2) | C12A—H12A | 0.9600 |
O2—C20 | 1.412 (3) | C12A—H12B | 0.9600 |
N1—C11 | 1.323 (3) | C12A—H12C | 0.9600 |
N1—C12A | 1.459 (3) | C12B—H12D | 0.9600 |
N1—C12B | 1.47 (3) | C12B—H12E | 0.9600 |
N1—C1 | 1.478 (2) | C12B—H12F | 0.9600 |
N2—C11 | 1.143 (2) | C13—C14 | 1.506 (2) |
C1—C2 | 1.472 (3) | C13—H13A | 0.9700 |
C1—C13 | 1.524 (3) | C13—H13B | 0.9700 |
C1—H1 | 0.9800 | C14—C19 | 1.378 (3) |
C2—C3 | 1.189 (3) | C14—C15 | 1.383 (3) |
C3—C4 | 1.435 (3) | C15—C16 | 1.372 (2) |
C4—C5 | 1.370 (3) | C15—H15 | 0.9300 |
C4—C9 | 1.374 (3) | C16—C17 | 1.376 (3) |
C5—C6 | 1.384 (3) | C16—H16 | 0.9300 |
C5—H5 | 0.9300 | C17—C18 | 1.368 (3) |
C6—C7 | 1.365 (3) | C18—C19 | 1.380 (3) |
C6—H6 | 0.9300 | C18—H18 | 0.9300 |
C7—C8 | 1.361 (3) | C19—H19 | 0.9300 |
C8—C9 | 1.374 (3) | C20—H20A | 0.9600 |
C8—H8 | 0.9300 | C20—H20B | 0.9600 |
C9—H9 | 0.9300 | C20—H20C | 0.9600 |
C10—H10A | 0.9600 | ||
C7—O1—C10 | 117.52 (16) | N1—C12A—H12B | 109.5 |
C17—O2—C20 | 118.68 (17) | H12A—C12A—H12B | 109.5 |
C11—N1—C12A | 115.07 (19) | N1—C12A—H12C | 109.5 |
C11—N1—C12B | 122.7 (10) | H12A—C12A—H12C | 109.5 |
C11—N1—C1 | 118.17 (16) | H12B—C12A—H12C | 109.5 |
C12A—N1—C1 | 116.83 (19) | N1—C12B—H12D | 109.5 |
C12B—N1—C1 | 118.6 (10) | N1—C12B—H12E | 109.5 |
C2—C1—N1 | 111.74 (15) | H12D—C12B—H12E | 109.5 |
C2—C1—C13 | 111.52 (16) | N1—C12B—H12F | 109.5 |
N1—C1—C13 | 111.45 (15) | H12D—C12B—H12F | 109.5 |
C2—C1—H1 | 107.3 | H12E—C12B—H12F | 109.5 |
N1—C1—H1 | 107.3 | C14—C13—C1 | 113.05 (15) |
C13—C1—H1 | 107.3 | C14—C13—H13A | 109.0 |
C3—C2—C1 | 178.0 (2) | C1—C13—H13A | 109.0 |
C2—C3—C4 | 179.2 (2) | C14—C13—H13B | 109.0 |
C5—C4—C9 | 117.56 (18) | C1—C13—H13B | 109.0 |
C5—C4—C3 | 121.59 (19) | H13A—C13—H13B | 107.8 |
C9—C4—C3 | 120.85 (19) | C19—C14—C15 | 116.85 (17) |
C4—C5—C6 | 121.91 (19) | C19—C14—C13 | 122.28 (18) |
C4—C5—H5 | 119.0 | C15—C14—C13 | 120.86 (17) |
C6—C5—H5 | 119.0 | C16—C15—C14 | 122.01 (18) |
C7—C6—C5 | 119.3 (2) | C16—C15—H15 | 119.0 |
C7—C6—H6 | 120.3 | C14—C15—H15 | 119.0 |
C5—C6—H6 | 120.3 | C15—C16—C17 | 119.82 (18) |
C8—C7—C6 | 119.46 (18) | C15—C16—H16 | 120.1 |
C8—C7—O1 | 116.22 (17) | C17—C16—H16 | 120.1 |
C6—C7—O1 | 124.32 (19) | C18—C17—O2 | 124.68 (17) |
C7—C8—C9 | 120.91 (19) | C18—C17—C16 | 119.52 (17) |
C7—C8—H8 | 119.5 | O2—C17—C16 | 115.80 (17) |
C9—C8—H8 | 119.5 | C17—C18—C19 | 119.89 (18) |
C8—C9—C4 | 120.8 (2) | C17—C18—H18 | 120.1 |
C8—C9—H9 | 119.6 | C19—C18—H18 | 120.1 |
C4—C9—H9 | 119.6 | C14—C19—C18 | 121.89 (18) |
O1—C10—H10A | 109.5 | C14—C19—H19 | 119.1 |
O1—C10—H10B | 109.5 | C18—C19—H19 | 119.1 |
H10A—C10—H10B | 109.5 | O2—C20—H20A | 109.5 |
O1—C10—H10C | 109.5 | O2—C20—H20B | 109.5 |
H10A—C10—H10C | 109.5 | H20A—C20—H20B | 109.5 |
H10B—C10—H10C | 109.5 | O2—C20—H20C | 109.5 |
N2—C11—N1 | 177.0 (2) | H20A—C20—H20C | 109.5 |
N1—C12A—H12A | 109.5 | H20B—C20—H20C | 109.5 |
C11—N1—C1—C2 | 69.5 (2) | C3—C4—C9—C8 | −179.32 (19) |
C12A—N1—C1—C2 | −74.5 (3) | C2—C1—C13—C14 | 174.28 (17) |
C12B—N1—C1—C2 | −118.6 (19) | N1—C1—C13—C14 | −60.1 (2) |
C11—N1—C1—C13 | −56.0 (2) | C1—C13—C14—C19 | 99.5 (2) |
C12A—N1—C1—C13 | 160.0 (3) | C1—C13—C14—C15 | −79.6 (2) |
C12B—N1—C1—C13 | 115.9 (19) | C19—C14—C15—C16 | 0.1 (3) |
C9—C4—C5—C6 | −1.1 (3) | C13—C14—C15—C16 | 179.21 (18) |
C3—C4—C5—C6 | 179.1 (2) | C14—C15—C16—C17 | −0.3 (3) |
C4—C5—C6—C7 | 0.1 (3) | C20—O2—C17—C18 | 1.2 (3) |
C5—C6—C7—C8 | 1.1 (3) | C20—O2—C17—C16 | −179.0 (2) |
C5—C6—C7—O1 | −179.14 (19) | C15—C16—C17—C18 | 0.1 (3) |
C10—O1—C7—C8 | 176.30 (19) | C15—C16—C17—O2 | −179.76 (17) |
C10—O1—C7—C6 | −3.4 (3) | O2—C17—C18—C19 | −179.79 (18) |
C6—C7—C8—C9 | −1.3 (3) | C16—C17—C18—C19 | 0.3 (3) |
O1—C7—C8—C9 | 178.92 (19) | C15—C14—C19—C18 | 0.4 (3) |
C7—C8—C9—C4 | 0.3 (3) | C13—C14—C19—C18 | −178.73 (18) |
C5—C4—C9—C8 | 1.0 (3) | C17—C18—C19—C14 | −0.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12A—H12B···O2i | 0.96 | 2.48 | 3.366 (4) | 154 |
C12B—H12D···O2i | 0.96 | 2.53 | 3.24 (2) | 131 |
Symmetry code: (i) x, −y+1/2, z+1/2. |
Acknowledgements
The authors thank the Center for Nanostructured Materials at the University of Texas at Arlington for the use of their diffractometer and the Robert A. Welch Foundation (4-1362) for supporting our research program.
References
Bruker (2016). APEX2, SAINT, and SADABS. Bruker AXS Inc., Madison, WI, USA Google Scholar
Ermolat'ev, D. S., Bariwal, J. B., Steenackers, H. P. L., De Keersmaecker, S. C. J. & Van der Eycken, E. V. (2010). Angew. Chem. Int. Ed. 49, 9465–9468. CAS Google Scholar
Gainer, M. J., Bennett, N. R., Takahashi, Y. & Looper, R. E. (2011). Angew. Chem. Int. Ed. 50, 684–687. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Singh, R. P., Spears, J. A., Dalipe, A., Yousufuddin, M. & Lovely, C. J. (2016). Tetrahedron Lett. 57, 3096–3099. CSD CrossRef CAS Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.