[1,4-Bis(4-meth­oxy­phen­yl)but-3-yn-2-yl](cyano)­methyl­amine

Yousufuddin, M.; Morales, R.; Cassis, W.; Brown, G.W.; Singh, R.P.; Lovely, C.J.

doi:10.1107/S2414314618003899

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 3| March 2018| x180389

https://doi.org/10.1107/S2414314618003899

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[1,4-Bis(4-methoxyphenyl)but-3-yn-2-yl](cyano)methylamine

Muhammed Yousufuddin,^a ^* Ruth Morales,^a Waleed Cassis,^a Gary W. Brown,^a Ravi P. Singh ^b and Carl J. Lovely ^b

^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

Edited by R. J. Butcher, Howard University, USA (Received 26 February 2018; accepted 6 March 2018; online 23 March 2018)

The title compound, C₂₀H₂₀N₂O₂, crystallizes in the P2₁/c space group with one molecule in the asymmetric unit. 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 crystal system, P2₁/c. There is one molecule in the asymmetric unit 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, symmetry operation 1 − x, 1 − y, 2 − z].

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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 refinement details are summarized in Table 2. One terminal CH₃ group (C12) is disordered over two positions with occupancies of 0.874 (9)/0.126 (9).

Table 2
Experimental details

Crystal data
Chemical formula	C₂₀H₂₀N₂O₂
M_r	320.38
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	299
a, b, c (Å)	15.6203 (19), 8.6349 (11), 13.9758 (17)
β (°)	108.948 (2)
V (Å³)	1782.9 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.25 × 0.15 × 0.05

Data collection
Diffractometer	Bruker D8 QUEST CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.687, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	15747, 3209, 2256
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.124, 1.04
No. of reflections	3209
No. of parameters	231
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.15
Computer programs: APEX2 and SAINT (Bruker, 2016), SHELXT2014 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ) and SHELXTL (Sheldrick, 2008 ).

Structural data

Crystal structure: contains datablocks I, 1R. DOI: https://doi.org/10.1107/S2414314618003899/bv4015sup1.cif

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

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2016); cell refinement: 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).

[1,4-Bis(4-methoxyphenyl)but-3-yn-2-yl](cyano)methylamine top

Crystal data top

C₂₀H₂₀N₂O₂	F(000) = 680
M_r = 320.38	D_x = 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

Data collection top

Bruker D8 QUEST CCD diffractometer	2256 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.032
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 25.2°, θ_min = 2.8°
T_min = 0.687, T_max = 0.745	h = −18→18
15747 measured reflections	k = −10→10
3209 independent reflections	l = −16→16

Refinement top

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(F_o²) + (0.0517P)² + 0.390P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3209 reflections	Δρ_max = 0.11 e Å⁻³
231 parameters	Δρ_min = −0.15 e Å⁻³

Special details top

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 U_iso(H) = 1.5U_eq(C) for methyl H and 1.2U_eq(C) for other H atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

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