2-[(2-Hydr-oxy-2,2-diphenyl-ethyl)(meth-yl)amino]-N,N-dimethyl-ethanaminium bromide.

The title compound, C(19)H(27)N(2)O(+)·Br(-), is the hydro-bromide of the trapping product of lithia-ted N,N,N',N'-tetramethylethylenediamine (TMEDA) with benzophenone. Thereby, the N atom of the NMe(2) group is selectively protonated and the respective trapping product represents a potential tridentate ligand with one O and two N donor atoms. The H atoms at N (H2N) and O (H1O) are involved in hydrogen bonds with the Br(-). The mol-ecular structure shows all donor atoms to be arranged on one side of the mol-ecule, thus indicating a potential threefold coordination of a Lewis acid.

Related literature

For related literature on direct deprotonation of tertiary amines, see: Strohmann & Gessner (2007a ▶,b ▶,c ▶, 2008a ▶,b ▶), Gessner & Strohmann (2008 ▶); Bojer et al. (2007 ▶); Karsch (1996 ▶); Strohmann et al. (2008 ▶); Köhler et al. (1987 ▶); Arnold et al. (2002 ▶).

Experimental

Crystal data

C19H27N2O+·Br−

M = 379.34

Orthorhombic,

a = 7.119 (2) Å

b = 15.515 (3) Å

c = 33.585 (7) Å

V = 3710 (1) Å3

Z = 8

Mo Kα radiation

μ = 2.22 mm−1

T = 173 (2) K

0.4 × 0.2 × 0.2 mm

Data collection

Bruker APEX CCD diffractometer

Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 1999 ▶) T min = 0.440, T max = 0.635

78737 measured reflections

3640 independent reflections

3200 reflections with I > 2σ(I)

R int = 0.064

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.099

S = 1.07

3640 reflections

219 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.49 e Å−3

Δρmin = −0.43 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 1999 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS90 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809002414/im2095sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809002414/im2095Isup2.hkl

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

C19H27N2O+·Br−	F(000) = 1584
Mr = 379.34	Dx = 1.358 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	θ = 1.2–26°
a = 7.119 (2) Å	µ = 2.22 mm−1
b = 15.515 (3) Å	T = 173 K
c = 33.585 (7) Å	Needle, colourless
V = 3710 (1) Å3	0.4 × 0.2 × 0.2 mm
Z = 8

Bruker APEX CCD diffractometer	3640 independent reflections
Radiation source: fine-focus sealed tube	3200 reflections with I > 2σ(I)
graphite	Rint = 0.064
ω scans	θmax = 26°, θmin = 1.2°
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 1999)	h = −8→8
Tmin = 0.440, Tmax = 0.635	k = −19→19
78737 measured reflections	l = −41→41

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0504P)2 + 4.0375P] where P = (Fo2 + 2Fc2)/3
3640 reflections	(Δ/σ)max = 0.003
219 parameters	Δρmax = 0.49 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
Br	0.55743 (4)	0.697337 (19)	0.564819 (9)	0.03232 (11)
C1	0.5689 (4)	0.93459 (17)	0.63574 (8)	0.0250 (6)
C2	0.6972 (4)	0.88169 (17)	0.66284 (8)	0.0250 (6)
C3	0.8583 (4)	0.9173 (2)	0.67970 (9)	0.0320 (7)
H3	0.8892	0.9757	0.6743	0.038*
C4	0.9747 (5)	0.8691 (2)	0.70430 (9)	0.0406 (8)
H4	1.0839	0.8946	0.7155	0.049*
C5	0.9321 (5)	0.7848 (2)	0.71242 (10)	0.0450 (9)
H5	1.0122	0.7516	0.7291	0.054*
C6	0.7726 (5)	0.7483 (2)	0.69634 (10)	0.0429 (8)
H6	0.7427	0.6900	0.7021	0.052*
C7	0.6550 (5)	0.79621 (19)	0.67180 (9)	0.0332 (7)
H7	0.5451	0.7704	0.6611	0.040*
C8	0.4435 (4)	0.99595 (17)	0.65971 (8)	0.0263 (6)
C9	0.4565 (4)	1.0055 (2)	0.70069 (9)	0.0335 (7)
H9	0.5476	0.9736	0.7151	0.040*
C10	0.3373 (5)	1.0615 (2)	0.72079 (9)	0.0380 (7)
H10	0.3473	1.0671	0.7489	0.046*
C11	0.2045 (5)	1.1091 (2)	0.70046 (10)	0.0372 (7)
H11	0.1250	1.1480	0.7143	0.045*
C12	0.1884 (4)	1.09930 (19)	0.65969 (9)	0.0337 (7)
H12	0.0965	1.1312	0.6454	0.040*
C13	0.3059 (4)	1.04315 (18)	0.63960 (9)	0.0290 (6)
H13	0.2928	1.0366	0.6116	0.035*
C14	0.6829 (4)	0.98676 (17)	0.60473 (8)	0.0285 (6)
H14A	0.5987	1.0285	0.5914	0.034*
H14B	0.7824	1.0198	0.6186	0.034*
C15	0.6945 (5)	0.9484 (2)	0.53493 (9)	0.0402 (8)
H15A	0.7315	1.0066	0.5267	0.060*
H15B	0.5572	0.9443	0.5355	0.060*
H15C	0.7445	0.9062	0.5160	0.060*
C16	0.9753 (4)	0.93415 (19)	0.57482 (9)	0.0289 (6)
H16A	1.0205	0.9333	0.6027	0.035*
H16B	1.0168	0.9890	0.5626	0.035*
C17	1.0617 (4)	0.85949 (18)	0.55238 (9)	0.0288 (6)
H17A	1.0360	0.8664	0.5236	0.035*
H17B	1.1995	0.8603	0.5562	0.035*
C18	1.0397 (5)	0.70427 (19)	0.53833 (10)	0.0345 (7)
H18A	1.1761	0.6960	0.5392	0.052*
H18B	1.0018	0.7198	0.5112	0.052*
H18C	0.9767	0.6508	0.5462	0.052*
C19	1.0432 (4)	0.7534 (2)	0.60756 (9)	0.0344 (7)
H19A	0.9805	0.7002	0.6161	0.052*
H19B	1.0071	0.8007	0.6253	0.052*
H19C	1.1796	0.7453	0.6086	0.052*
N1	0.7695 (3)	0.93059 (15)	0.57460 (7)	0.0262 (5)
N2	0.9858 (4)	0.77440 (16)	0.56609 (7)	0.0260 (5)
H2N	0.864 (6)	0.779 (2)	0.5669 (10)	0.044 (10)*
O	0.4411 (3)	0.88041 (14)	0.61458 (7)	0.0298 (5)
H1O	0.494 (5)	0.849 (2)	0.6050 (10)	0.024 (10)*

	U11	U22	U33	U12	U13	U23
Br	0.02792 (17)	0.03281 (18)	0.03624 (18)	−0.00315 (12)	0.00142 (12)	−0.00227 (12)
C1	0.0251 (14)	0.0217 (13)	0.0283 (14)	−0.0032 (11)	−0.0027 (12)	−0.0014 (11)
C2	0.0242 (14)	0.0256 (14)	0.0252 (13)	0.0005 (11)	0.0033 (11)	0.0001 (11)
C3	0.0301 (16)	0.0327 (15)	0.0333 (16)	−0.0008 (13)	−0.0003 (13)	−0.0044 (12)
C4	0.0297 (17)	0.062 (2)	0.0301 (16)	0.0028 (16)	−0.0057 (13)	−0.0061 (15)
C5	0.047 (2)	0.058 (2)	0.0308 (17)	0.0190 (17)	−0.0028 (15)	0.0079 (15)
C6	0.048 (2)	0.0371 (17)	0.0432 (18)	0.0083 (16)	0.0076 (16)	0.0158 (15)
C7	0.0315 (16)	0.0310 (15)	0.0371 (16)	−0.0041 (13)	0.0020 (14)	0.0034 (13)
C8	0.0249 (14)	0.0217 (13)	0.0324 (15)	−0.0050 (11)	−0.0008 (12)	−0.0002 (11)
C9	0.0331 (17)	0.0347 (16)	0.0327 (16)	−0.0002 (14)	−0.0033 (13)	−0.0013 (13)
C10	0.0387 (18)	0.0446 (18)	0.0309 (16)	−0.0019 (15)	0.0036 (14)	−0.0070 (14)
C11	0.0328 (17)	0.0306 (15)	0.0481 (19)	−0.0004 (14)	0.0075 (14)	−0.0079 (14)
C12	0.0261 (15)	0.0286 (15)	0.0464 (18)	−0.0006 (13)	0.0023 (13)	0.0022 (13)
C13	0.0281 (15)	0.0266 (14)	0.0322 (15)	−0.0029 (12)	−0.0012 (12)	0.0007 (12)
C14	0.0335 (16)	0.0203 (13)	0.0316 (15)	0.0005 (12)	−0.0005 (13)	0.0006 (11)
C15	0.0403 (18)	0.0470 (19)	0.0334 (16)	0.0054 (16)	−0.0093 (14)	−0.0049 (14)
C16	0.0276 (15)	0.0301 (15)	0.0289 (14)	−0.0067 (12)	−0.0014 (12)	−0.0005 (12)
C17	0.0252 (15)	0.0317 (15)	0.0295 (14)	−0.0032 (12)	0.0022 (12)	0.0041 (12)
C18	0.0328 (17)	0.0323 (16)	0.0384 (17)	0.0026 (13)	0.0037 (14)	−0.0078 (13)
C19	0.0347 (17)	0.0362 (16)	0.0325 (15)	0.0051 (14)	−0.0004 (13)	0.0063 (13)
N1	0.0266 (12)	0.0263 (12)	0.0255 (11)	−0.0010 (10)	−0.0018 (10)	−0.0005 (9)
N2	0.0198 (12)	0.0276 (12)	0.0306 (13)	0.0001 (10)	0.0033 (10)	0.0010 (10)
O	0.0274 (11)	0.0255 (11)	0.0365 (12)	−0.0004 (9)	−0.0045 (9)	−0.0082 (9)

C1—O	1.428 (3)	C13—H13	0.9500
C1—C2	1.528 (4)	C14—N1	1.471 (4)
C1—C8	1.534 (4)	C14—H14A	0.9900
C1—C14	1.549 (4)	C14—H14B	0.9900
C2—C7	1.393 (4)	C15—N1	1.462 (4)
C2—C3	1.393 (4)	C15—H15A	0.9800
C3—C4	1.388 (4)	C15—H15B	0.9800
C3—H3	0.9500	C15—H15C	0.9800
C4—C5	1.370 (5)	C16—N1	1.466 (4)
C4—H4	0.9500	C16—C17	1.513 (4)
C5—C6	1.379 (5)	C16—H16A	0.9900
C5—H5	0.9500	C16—H16B	0.9900
C6—C7	1.390 (5)	C17—N2	1.499 (4)
C6—H6	0.9500	C17—H17A	0.9900
C7—H7	0.9500	C17—H17B	0.9900
C8—C9	1.387 (4)	C18—N2	1.483 (4)
C8—C13	1.397 (4)	C18—H18A	0.9800
C9—C10	1.389 (4)	C18—H18B	0.9800
C9—H9	0.9500	C18—H18C	0.9800
C10—C11	1.380 (5)	C19—N2	1.487 (4)
C10—H10	0.9500	C19—H19A	0.9800
C11—C12	1.382 (4)	C19—H19B	0.9800
C11—H11	0.9500	C19—H19C	0.9800
C12—C13	1.383 (4)	N2—H2N	0.87 (4)
C12—H12	0.9500	O—H1O	0.69 (3)
O—C1—C2	111.2 (2)	C1—C14—H14A	109.2
O—C1—C8	104.8 (2)	N1—C14—H14B	109.2
C2—C1—C8	111.6 (2)	C1—C14—H14B	109.2
O—C1—C14	107.9 (2)	H14A—C14—H14B	107.9
C2—C1—C14	111.6 (2)	N1—C15—H15A	109.5
C8—C1—C14	109.5 (2)	N1—C15—H15B	109.5
C7—C2—C3	117.8 (3)	H15A—C15—H15B	109.5
C7—C2—C1	120.7 (3)	N1—C15—H15C	109.5
C3—C2—C1	121.4 (2)	H15A—C15—H15C	109.5
C4—C3—C2	121.3 (3)	H15B—C15—H15C	109.5
C4—C3—H3	119.3	N1—C16—C17	112.0 (2)
C2—C3—H3	119.3	N1—C16—H16A	109.2
C5—C4—C3	120.0 (3)	C17—C16—H16A	109.2
C5—C4—H4	120.0	N1—C16—H16B	109.2
C3—C4—H4	120.0	C17—C16—H16B	109.2
C4—C5—C6	119.7 (3)	H16A—C16—H16B	107.9
C4—C5—H5	120.2	N2—C17—C16	112.0 (2)
C6—C5—H5	120.2	N2—C17—H17A	109.2
C5—C6—C7	120.6 (3)	C16—C17—H17A	109.2
C5—C6—H6	119.7	N2—C17—H17B	109.2
C7—C6—H6	119.7	C16—C17—H17B	109.2
C2—C7—C6	120.5 (3)	H17A—C17—H17B	107.9
C2—C7—H7	119.8	N2—C18—H18A	109.5
C6—C7—H7	119.8	N2—C18—H18B	109.5
C9—C8—C13	118.0 (3)	H18A—C18—H18B	109.5
C9—C8—C1	123.3 (3)	N2—C18—H18C	109.5
C13—C8—C1	118.7 (2)	H18A—C18—H18C	109.5
C8—C9—C10	120.6 (3)	H18B—C18—H18C	109.5
C8—C9—H9	119.7	N2—C19—H19A	109.5
C10—C9—H9	119.7	N2—C19—H19B	109.5
C11—C10—C9	120.8 (3)	H19A—C19—H19B	109.5
C11—C10—H10	119.6	N2—C19—H19C	109.5
C9—C10—H10	119.6	H19A—C19—H19C	109.5
C12—C11—C10	119.2 (3)	H19B—C19—H19C	109.5
C12—C11—H11	120.4	C15—N1—C16	111.3 (2)
C10—C11—H11	120.4	C15—N1—C14	111.2 (2)
C11—C12—C13	120.1 (3)	C16—N1—C14	113.2 (2)
C11—C12—H12	119.9	C18—N2—C19	110.9 (2)
C13—C12—H12	119.9	C18—N2—C17	111.1 (2)
C12—C13—C8	121.2 (3)	C19—N2—C17	112.5 (2)
C12—C13—H13	119.4	C18—N2—H2N	110 (2)
C8—C13—H13	119.4	C19—N2—H2N	105 (2)
N1—C14—C1	111.9 (2)	C17—N2—H2N	107 (2)
N1—C14—H14A	109.2	C1—O—H1O	107 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···Br	0.87 (4)	2.52 (4)	3.276 (3)	145 (4)
O—H1O···Br	0.69 (3)	2.76 (3)	3.398 (2)	156 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯Br	0.87 (4)	2.52 (4)	3.276 (3)	145 (4)
O—H1O⋯Br	0.69 (3)	2.76 (3)	3.398 (2)	156 (3)