3-Phenyl-N,N,N',N'-tetra-methyl-1-ethyne-1-carboximidamidium bromide.

The reaction of 3,3,3-tris-(dimethyl-amino)-1-phenyl-prop-1-yne with bromine in pentane yields the title compound, C(13)H(17)N(2) (+)·Br(-). The acetyl-enic bond distance [1.197 (2) Å] is consistent with a C C triple bond. The amidinium C=N bonds [1.325 (2) and 1.330 (2) Å] have double-bond character and the positive charge is delocalized between the two dimethyl-amino groups.

Related literature

For the synthesis of alkynyl orthoamides and acetyl­enic amidinium salts, see: Weingärtner et al. (2011 ▶). For the synthesis of vinyl­ogous guanidinium iodides and bromides, see: Kantlehner et al. (2012 ▶). For the crystal structure of N,N,N′,N′,N′′,N′′,N′′′,N′′′-octa­methyl-(but-2-yne)-bis­(amidinium)-bis­(tetra­fluoridoborate), see: Drandarov et al. (2012 ▶).

Experimental

Crystal data

C13H17N2 +·Br−

M = 281.19

Monoclinic,

a = 13.1009 (8) Å

b = 10.6538 (6) Å

c = 9.6611 (6) Å

β = 100.276 (3)°

V = 1326.81 (14) Å3

Z = 4

Mo Kα radiation

μ = 3.08 mm−1

T = 100 K

0.28 × 0.20 × 0.15 mm

Data collection

Bruker Kappa APEXII DUO diffractometer

Absorption correction: multi-scan (Blessing, 1995) ▶ T min = 0.483, T max = 0.630

27687 measured reflections

4075 independent reflections

3466 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.052

S = 1.07

4075 reflections

149 parameters

H-atom parameters constrained

Δρmax = 0.38 e Å−3

Δρmin = −0.43 e Å−3

Data collection: APEX2 (n class="Chemical">Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812021873/kp2415sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812021873/kp2415Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C13H17N2+·Br−	F(000) = 576
Mr = 281.19	Dx = 1.408 Mg m−3
Monoclinic, P21/c	Melting point: 441 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.1009 (8) Å	Cell parameters from 4075 reflections
b = 10.6538 (6) Å	θ = 2.5–30.6°
c = 9.6611 (6) Å	µ = 3.08 mm−1
β = 100.276 (3)°	T = 100 K
V = 1326.81 (14) Å3	Block, yellow
Z = 4	0.28 × 0.20 × 0.15 mm

Bruker Kappa APEXII DUO diffractometer	4075 independent reflections
Radiation source: sealed tube	3466 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
φ scans, and ω scans	θmax = 30.6°, θmin = 2.5°
Absorption correction: multi-scan (Blessing, 1995)	h = −18→18
Tmin = 0.483, Tmax = 0.630	k = −15→15
27687 measured reflections	l = −13→13

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.021	Hydrogen site location: difference Fourier map
wR(F2) = 0.052	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.024P)2 + 0.4023P] where P = (Fo2 + 2Fc2)/3
4075 reflections	(Δ/σ)max < 0.001
149 parameters	Δρmax = 0.38 e Å−3
0 restraints	Δρmin = −0.43 e Å−3

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.

	x	y	z	Uiso*/Ueq
Br1	0.313905 (9)	0.523031 (12)	0.155779 (13)	0.01703 (4)
C1	0.29358 (9)	0.46256 (11)	0.66879 (12)	0.0128 (2)
N1	0.35589 (8)	0.56042 (10)	0.66379 (10)	0.01344 (19)
N2	0.30756 (8)	0.37987 (10)	0.77285 (11)	0.0147 (2)
C2	0.41450 (10)	0.62002 (12)	0.79005 (13)	0.0164 (2)
H2A	0.3882	0.5904	0.8731	0.025*
H2B	0.4065	0.7113	0.7823	0.025*
H2C	0.4881	0.5982	0.7992	0.025*
C3	0.35920 (11)	0.62655 (13)	0.53213 (13)	0.0205 (3)
H3A	0.3140	0.5838	0.4546	0.031*
H3B	0.4305	0.6271	0.5143	0.031*
H3C	0.3353	0.7131	0.5392	0.031*
C4	0.22431 (11)	0.29642 (12)	0.79900 (15)	0.0207 (3)
H4A	0.1580	0.3255	0.7451	0.031*
H4B	0.2210	0.2970	0.8995	0.031*
H4C	0.2382	0.2109	0.7699	0.031*
C5	0.40815 (10)	0.35338 (13)	0.86079 (14)	0.0203 (3)
H5A	0.4635	0.3900	0.8175	0.031*
H5B	0.4181	0.2624	0.8695	0.031*
H5C	0.4103	0.3900	0.9543	0.031*
C6	0.20698 (10)	0.44506 (11)	0.55744 (13)	0.0153 (2)
C7	0.13169 (9)	0.42701 (11)	0.46956 (13)	0.0148 (2)
C8	0.04099 (9)	0.40275 (11)	0.36723 (12)	0.0133 (2)
C9	−0.02930 (10)	0.31159 (11)	0.39520 (14)	0.0170 (2)
H9A	−0.0156	0.2651	0.4804	0.020*
C10	−0.11893 (10)	0.28928 (12)	0.29838 (15)	0.0204 (3)
H10A	−0.1669	0.2274	0.3171	0.024*
C11	−0.13845 (10)	0.35719 (13)	0.17439 (14)	0.0203 (3)
H11A	−0.2002	0.3420	0.1084	0.024*
C12	−0.06867 (10)	0.44725 (13)	0.14572 (14)	0.0195 (3)
H12A	−0.0828	0.4935	0.0603	0.023*
C13	0.02160 (10)	0.46995 (12)	0.24136 (13)	0.0167 (2)
H13A	0.0699	0.5308	0.2213	0.020*

	U11	U22	U33	U12	U13	U23
Br1	0.01516 (6)	0.01901 (6)	0.01757 (7)	0.00196 (5)	0.00471 (4)	−0.00012 (5)
C1	0.0109 (5)	0.0140 (5)	0.0139 (5)	0.0021 (4)	0.0035 (4)	−0.0027 (4)
N1	0.0132 (5)	0.0152 (4)	0.0115 (4)	−0.0012 (4)	0.0012 (4)	−0.0005 (4)
N2	0.0138 (5)	0.0147 (5)	0.0158 (5)	0.0012 (4)	0.0034 (4)	0.0016 (4)
C2	0.0149 (6)	0.0184 (6)	0.0150 (6)	−0.0022 (4)	0.0001 (4)	−0.0030 (4)
C3	0.0242 (7)	0.0219 (6)	0.0151 (6)	−0.0052 (5)	0.0028 (5)	0.0034 (5)
C4	0.0224 (7)	0.0158 (6)	0.0258 (7)	−0.0025 (5)	0.0091 (5)	0.0024 (5)
C5	0.0184 (6)	0.0224 (6)	0.0194 (6)	0.0077 (5)	0.0010 (5)	0.0047 (5)
C6	0.0148 (6)	0.0131 (5)	0.0182 (6)	0.0011 (4)	0.0034 (4)	−0.0018 (4)
C7	0.0140 (5)	0.0130 (5)	0.0179 (6)	0.0008 (4)	0.0045 (4)	−0.0020 (4)
C8	0.0105 (5)	0.0125 (5)	0.0167 (6)	0.0008 (4)	0.0023 (4)	−0.0039 (4)
C9	0.0162 (6)	0.0141 (5)	0.0216 (6)	−0.0001 (4)	0.0056 (5)	−0.0007 (4)
C10	0.0131 (6)	0.0171 (6)	0.0323 (7)	−0.0037 (5)	0.0076 (5)	−0.0081 (5)
C11	0.0105 (6)	0.0252 (6)	0.0246 (6)	0.0019 (5)	0.0010 (5)	−0.0124 (5)
C12	0.0171 (6)	0.0254 (6)	0.0153 (6)	0.0034 (5)	0.0009 (5)	−0.0022 (5)
C13	0.0140 (6)	0.0169 (6)	0.0191 (6)	−0.0015 (4)	0.0032 (5)	−0.0005 (5)

C1—N2	1.3246 (15)	C5—H5A	0.9800
C1—N1	1.3304 (16)	C5—H5B	0.9800
C1—C6	1.4296 (17)	C5—H5C	0.9800
N1—C3	1.4615 (15)	C6—C7	1.1966 (17)
N1—C2	1.4651 (15)	C7—C8	1.4273 (17)
N2—C5	1.4625 (16)	C8—C13	1.3949 (17)
N2—C4	1.4636 (16)	C8—C9	1.3974 (17)
C2—H2A	0.9800	C9—C10	1.3851 (18)
C2—H2B	0.9800	C9—H9A	0.9500
C2—H2C	0.9800	C10—C11	1.384 (2)
C3—H3A	0.9800	C10—H10A	0.9500
C3—H3B	0.9800	C11—C12	1.3870 (19)
C3—H3C	0.9800	C11—H11A	0.9500
C4—H4A	0.9800	C12—C13	1.3860 (18)
C4—H4B	0.9800	C12—H12A	0.9500
C4—H4C	0.9800	C13—H13A	0.9500
N2—C1—N1	123.10 (11)	N2—C5—H5A	109.5
N2—C1—C6	117.91 (11)	N2—C5—H5B	109.5
N1—C1—C6	118.99 (11)	H5A—C5—H5B	109.5
C1—N1—C3	121.53 (10)	N2—C5—H5C	109.5
C1—N1—C2	122.91 (10)	H5A—C5—H5C	109.5
C3—N1—C2	115.04 (10)	H5B—C5—H5C	109.5
C1—N2—C5	123.89 (11)	C7—C6—C1	176.30 (13)
C1—N2—C4	121.91 (11)	C6—C7—C8	178.36 (13)
C5—N2—C4	113.86 (10)	C13—C8—C9	120.10 (11)
N1—C2—H2A	109.5	C13—C8—C7	120.69 (11)
N1—C2—H2B	109.5	C9—C8—C7	119.20 (11)
H2A—C2—H2B	109.5	C10—C9—C8	119.81 (12)
N1—C2—H2C	109.5	C10—C9—H9A	120.1
H2A—C2—H2C	109.5	C8—C9—H9A	120.1
H2B—C2—H2C	109.5	C11—C10—C9	119.90 (12)
N1—C3—H3A	109.5	C11—C10—H10A	120.0
N1—C3—H3B	109.5	C9—C10—H10A	120.0
H3A—C3—H3B	109.5	C10—C11—C12	120.53 (12)
N1—C3—H3C	109.5	C10—C11—H11A	119.7
H3A—C3—H3C	109.5	C12—C11—H11A	119.7
H3B—C3—H3C	109.5	C13—C12—C11	120.13 (12)
N2—C4—H4A	109.5	C13—C12—H12A	119.9
N2—C4—H4B	109.5	C11—C12—H12A	119.9
H4A—C4—H4B	109.5	C12—C13—C8	119.51 (11)
N2—C4—H4C	109.5	C12—C13—H13A	120.2
H4A—C4—H4C	109.5	C8—C13—H13A	120.2
H4B—C4—H4C	109.5
N2—C1—N1—C3	160.73 (11)	C13—C8—C9—C10	−0.83 (18)
C6—C1—N1—C3	−19.49 (17)	C7—C8—C9—C10	178.38 (11)
N2—C1—N1—C2	−27.94 (18)	C8—C9—C10—C11	0.07 (18)
C6—C1—N1—C2	151.84 (11)	C9—C10—C11—C12	0.32 (19)
N1—C1—N2—C5	−25.57 (18)	C10—C11—C12—C13	0.06 (19)
C6—C1—N2—C5	154.65 (11)	C11—C12—C13—C8	−0.82 (19)
N1—C1—N2—C4	161.57 (12)	C9—C8—C13—C12	1.20 (18)
C6—C1—N2—C4	−18.20 (17)	C7—C8—C13—C12	−178.00 (11)