The structure of the title compound, 2-[1-(dimethylammonioethoxy)-1-phenylethyl]pyridinium tetrachlorocuprate(II), (C
17H
24N
2O)[CuCl
4], contains dihydro cations of doxylamine hydrogen bonded to two Cl atoms in two different CuCl
42− anions, with Cl
N distances of 3.101 (9) and 3.253 (10) Å. The ethereal O atom is involved in intramolecular hydrogen bonds, with O
N distances of 2.517 (11) and 2.757 (12) Å. The molecular dimensions in the cation are as expected and the CuCl
42− anion has a flattened tetrahedral geometry.
Supporting information
CCDC reference: 162552
The title compound was synthesized by adding CuCl2·2H20 (1.0 mmol) to
doxylamine succinate (Sigma Inc.) (2.0 mmol) in ethanol (20 ml). HCl was added
until the pH was 2–3. The solution was evaporated slowly at room temperature
and yellow prismatic crystals separated after a few days.
H atoms were located from difference maps and were placed at geometrically
idealized positions (N—H 0.88 and 0.93 Å, C—H 0.95–0.99 Å) utilizing
a riding model, and a torsional parameter was refined for each Me group. The
non-methyl and methyl H atoms were assigned isotropic displacement parameters
1.2 and 1.5 times, respectively, the displacement parameters of the atoms to
which they were attached.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1994); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN; software used to prepare material for publication: SHELXL97.
{2-[1-dimethylammonioethoxy)-1-phenylethyl]pyridinium} tetrachlorocuprate(II)
top
Crystal data top
(C17H24N2O)[CuCl4] | F(000) = 980 |
Mr = 477.72 | Dx = 1.539 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71069 Å |
a = 16.807 (2) Å | Cell parameters from 25 reflections |
b = 9.3006 (16) Å | θ = 10.0–20.0° |
c = 13.7677 (10) Å | µ = 1.59 mm−1 |
β = 106.682 (10)° | T = 170 K |
V = 2061.5 (5) Å3 | Prismatic, yellow |
Z = 4 | 0.45 × 0.23 × 0.18 mm |
Data collection top
Rigaku AFC6S diffractometer | 1140 reflections with I > 2.0σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.00 |
Graphite monochromator | θmax = 25.0°, θmin = 2.5° |
ω/2θ scans | h = 0→20 |
Absorption correction: empirical (using intensity measurements) ψ-scan (3 reflections) (North et al., 1968) | k = 0→11 |
Tmin = 0.54, Tmax = 0.76 | l = −16→15 |
1901 measured reflections | 3 standard reflections every 200 reflections |
1901 independent reflections | intensity decay: 0.6% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.128 | w = 1/[σ2(Fo2) + (0.059P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.01 |
1901 reflections | Δρmax = 0.53 e Å−3 |
229 parameters | Δρmin = −0.63 e Å−3 |
2 restraints | Absolute structure: (Flack, 1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (4) |
Crystal data top
(C17H24N2O)[CuCl4] | V = 2061.5 (5) Å3 |
Mr = 477.72 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 16.807 (2) Å | µ = 1.59 mm−1 |
b = 9.3006 (16) Å | T = 170 K |
c = 13.7677 (10) Å | 0.45 × 0.23 × 0.18 mm |
β = 106.682 (10)° | |
Data collection top
Rigaku AFC6S diffractometer | 1140 reflections with I > 2.0σ(I) |
Absorption correction: empirical (using intensity measurements) ψ-scan (3 reflections) (North et al., 1968) | Rint = 0.00 |
Tmin = 0.54, Tmax = 0.76 | 3 standard reflections every 200 reflections |
1901 measured reflections | intensity decay: 0.6% |
1901 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.128 | Δρmax = 0.53 e Å−3 |
S = 1.02 | Δρmin = −0.63 e Å−3 |
1901 reflections | Absolute structure: (Flack, 1983) |
229 parameters | Absolute structure parameter: −0.02 (4) |
2 restraints | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.69064 (8) | 0.81817 (16) | 0.34263 (9) | 0.0303 (4) | |
Cl1 | 0.63028 (17) | 0.7246 (3) | 0.4590 (2) | 0.0356 (8) | |
Cl2 | 0.64009 (18) | 1.0062 (3) | 0.2465 (2) | 0.0366 (8) | |
Cl3 | 0.80538 (19) | 0.9111 (4) | 0.4439 (2) | 0.0414 (8) | |
Cl4 | 0.6670 (2) | 0.6371 (3) | 0.2297 (2) | 0.0404 (8) | |
O1 | 0.7734 (5) | 0.4530 (9) | 0.5117 (6) | 0.0304 (19) | |
N1 | 0.7953 (5) | 0.6688 (9) | 0.6267 (6) | 0.026 (2) | |
H1 | 0.7516 | 0.6520 | 0.5747 | 0.032* | |
N2 | 0.6303 (6) | 0.2951 (10) | 0.4891 (7) | 0.033 (2) | |
H2 | 0.6616 | 0.3429 | 0.5468 | 0.039* | |
C1 | 0.7887 (8) | 0.7712 (12) | 0.6905 (9) | 0.032 (3) | |
H1A | 0.7379 | 0.8220 | 0.6801 | 0.039* | |
C2 | 0.8549 (9) | 0.8035 (14) | 0.7710 (9) | 0.043 (3) | |
H2A | 0.8513 | 0.8779 | 0.8168 | 0.052* | |
C3 | 0.9267 (9) | 0.7273 (15) | 0.7850 (11) | 0.050 (4) | |
H3 | 0.9735 | 0.7485 | 0.8408 | 0.060* | |
C4 | 0.9311 (8) | 0.6197 (14) | 0.7182 (9) | 0.042 (3) | |
H4 | 0.9808 | 0.5658 | 0.7286 | 0.051* | |
C5 | 0.8623 (6) | 0.5892 (11) | 0.6346 (8) | 0.024 (2) | |
C6 | 0.8613 (7) | 0.4772 (12) | 0.5554 (9) | 0.029 (3) | |
C7 | 0.9013 (7) | 0.3393 (13) | 0.6063 (9) | 0.031 (3) | |
C8 | 0.8656 (7) | 0.2751 (13) | 0.6746 (9) | 0.034 (3) | |
H8 | 0.8193 | 0.3176 | 0.6901 | 0.041* | |
C9 | 0.8997 (8) | 0.1458 (13) | 0.7198 (10) | 0.039 (3) | |
H9 | 0.8751 | 0.0972 | 0.7646 | 0.047* | |
C10 | 0.9686 (8) | 0.0893 (15) | 0.6995 (9) | 0.042 (3) | |
H10 | 0.9914 | 0.0015 | 0.7305 | 0.050* | |
C11 | 1.0044 (7) | 0.1570 (13) | 0.6358 (10) | 0.036 (3) | |
H11 | 1.0532 | 0.1181 | 0.6243 | 0.044* | |
C12 | 0.9704 (7) | 0.2828 (14) | 0.5872 (10) | 0.037 (3) | |
H12 | 0.9948 | 0.3291 | 0.5412 | 0.045* | |
C13 | 0.8995 (8) | 0.5391 (15) | 0.4777 (10) | 0.047 (4) | |
H13A | 0.8947 | 0.4693 | 0.4230 | 0.071* | |
H13B | 0.9583 | 0.5603 | 0.5100 | 0.071* | |
H13C | 0.8704 | 0.6278 | 0.4498 | 0.071* | |
C14 | 0.7507 (7) | 0.3581 (13) | 0.4281 (8) | 0.031 (3) | |
H14A | 0.7770 | 0.2629 | 0.4463 | 0.037* | |
H14B | 0.7673 | 0.3973 | 0.3699 | 0.037* | |
C15 | 0.6592 (8) | 0.3471 (14) | 0.4035 (9) | 0.040 (3) | |
H15A | 0.6346 | 0.4428 | 0.3824 | 0.049* | |
H15B | 0.6388 | 0.2808 | 0.3454 | 0.049* | |
C16 | 0.5441 (8) | 0.3294 (15) | 0.4777 (11) | 0.052 (4) | |
H16A | 0.5345 | 0.4319 | 0.4620 | 0.077* | |
H16B | 0.5308 | 0.3075 | 0.5409 | 0.077* | |
H16C | 0.5085 | 0.2721 | 0.4224 | 0.077* | |
C17 | 0.6443 (11) | 0.1394 (16) | 0.5088 (11) | 0.065 (5) | |
H17A | 0.6275 | 0.1128 | 0.5689 | 0.097* | |
H17B | 0.7034 | 0.1176 | 0.5205 | 0.097* | |
H17C | 0.6114 | 0.0849 | 0.4501 | 0.097* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0279 (7) | 0.0321 (8) | 0.0291 (8) | −0.0029 (8) | 0.0054 (6) | 0.0028 (8) |
Cl1 | 0.0255 (15) | 0.052 (2) | 0.0303 (16) | 0.0028 (14) | 0.0092 (13) | 0.0096 (14) |
Cl2 | 0.0375 (17) | 0.0335 (18) | 0.0371 (18) | 0.0025 (15) | 0.0079 (14) | 0.0078 (15) |
Cl3 | 0.0318 (16) | 0.043 (2) | 0.0430 (18) | −0.0065 (15) | 0.0009 (14) | 0.0009 (16) |
Cl4 | 0.055 (2) | 0.0369 (19) | 0.0276 (16) | −0.0113 (15) | 0.0098 (15) | 0.0016 (13) |
O1 | 0.024 (4) | 0.038 (5) | 0.028 (4) | 0.000 (4) | 0.007 (3) | −0.008 (4) |
N1 | 0.029 (5) | 0.026 (5) | 0.019 (4) | −0.005 (5) | −0.003 (4) | −0.005 (4) |
N2 | 0.034 (6) | 0.033 (6) | 0.028 (5) | −0.015 (5) | 0.004 (4) | −0.006 (5) |
C1 | 0.037 (7) | 0.012 (6) | 0.048 (8) | 0.004 (5) | 0.013 (6) | 0.000 (5) |
C2 | 0.065 (10) | 0.032 (8) | 0.032 (7) | −0.015 (8) | 0.012 (7) | 0.001 (6) |
C3 | 0.050 (9) | 0.043 (8) | 0.047 (9) | −0.002 (7) | −0.002 (7) | −0.001 (7) |
C4 | 0.034 (7) | 0.043 (8) | 0.048 (8) | 0.001 (6) | 0.009 (6) | 0.003 (7) |
C5 | 0.023 (6) | 0.018 (6) | 0.031 (6) | 0.006 (5) | 0.009 (5) | 0.008 (5) |
C6 | 0.023 (6) | 0.021 (6) | 0.039 (7) | 0.004 (5) | 0.004 (5) | 0.007 (5) |
C7 | 0.018 (6) | 0.037 (7) | 0.034 (6) | 0.009 (6) | 0.003 (5) | 0.002 (6) |
C8 | 0.029 (7) | 0.031 (7) | 0.051 (8) | −0.001 (5) | 0.024 (6) | 0.004 (6) |
C9 | 0.035 (7) | 0.040 (8) | 0.041 (7) | 0.001 (6) | 0.011 (6) | 0.014 (6) |
C10 | 0.048 (9) | 0.035 (8) | 0.036 (8) | 0.012 (6) | 0.003 (6) | 0.003 (6) |
C11 | 0.025 (7) | 0.038 (8) | 0.048 (8) | 0.012 (6) | 0.014 (6) | −0.011 (7) |
C12 | 0.028 (7) | 0.041 (9) | 0.040 (7) | 0.013 (6) | 0.007 (6) | −0.008 (6) |
C13 | 0.040 (7) | 0.051 (9) | 0.059 (9) | 0.018 (7) | 0.029 (7) | 0.003 (7) |
C14 | 0.032 (7) | 0.032 (7) | 0.023 (6) | 0.004 (5) | −0.004 (6) | −0.018 (5) |
C15 | 0.038 (7) | 0.046 (9) | 0.035 (7) | −0.001 (6) | 0.006 (6) | 0.006 (6) |
C16 | 0.041 (8) | 0.061 (9) | 0.054 (8) | −0.012 (8) | 0.015 (6) | −0.013 (8) |
C17 | 0.094 (13) | 0.050 (10) | 0.052 (10) | 0.005 (9) | 0.025 (9) | 0.010 (7) |
Geometric parameters (Å, º) top
Cu1—Cl3 | 2.206 (3) | C7—C8 | 1.386 (17) |
Cu1—Cl2 | 2.210 (3) | C8—C9 | 1.399 (17) |
Cu1—Cl4 | 2.248 (4) | C8—H8 | 0.9500 |
Cu1—Cl1 | 2.299 (3) | C9—C10 | 1.372 (18) |
O1—C14 | 1.413 (12) | C9—H9 | 0.9500 |
O1—C6 | 1.445 (13) | C10—C11 | 1.353 (18) |
N1—C1 | 1.322 (14) | C10—H10 | 0.9500 |
N1—C5 | 1.326 (13) | C11—C12 | 1.387 (17) |
N1—H1 | 0.8800 | C11—H11 | 0.9500 |
N2—C16 | 1.449 (16) | C12—H12 | 0.9500 |
N2—C15 | 1.478 (15) | C13—H13A | 0.9800 |
N2—C17 | 1.479 (17) | C13—H13B | 0.9800 |
N2—H2 | 0.9300 | C13—H13C | 0.9800 |
C1—C2 | 1.360 (17) | C14—C15 | 1.480 (17) |
C1—H1A | 0.9500 | C14—H14A | 0.9900 |
C2—C3 | 1.363 (19) | C14—H14B | 0.9900 |
C2—H2A | 0.9500 | C15—H15A | 0.9900 |
C3—C4 | 1.375 (18) | C15—H15B | 0.9900 |
C3—H3 | 0.9500 | C16—H16A | 0.9800 |
C4—C5 | 1.407 (16) | C16—H16B | 0.9800 |
C4—H4 | 0.9500 | C16—H16C | 0.9800 |
C5—C6 | 1.505 (16) | C17—H17A | 0.9800 |
C6—C13 | 1.510 (17) | C17—H17B | 0.9800 |
C6—C7 | 1.522 (16) | C17—H17C | 0.9800 |
C7—C12 | 1.368 (16) | | |
| | | |
Cl3—Cu1—Cl2 | 100.62 (13) | C10—C9—C8 | 120.0 (12) |
Cl3—Cu1—Cl4 | 132.81 (14) | C10—C9—H9 | 120.0 |
Cl2—Cu1—Cl4 | 102.57 (12) | C8—C9—H9 | 120.0 |
Cl3—Cu1—Cl1 | 100.86 (12) | C11—C10—C9 | 120.8 (12) |
Cl2—Cu1—Cl1 | 123.09 (13) | C11—C10—H10 | 119.6 |
Cl4—Cu1—Cl1 | 99.92 (13) | C9—C10—H10 | 119.6 |
C14—O1—C6 | 116.1 (8) | C10—C11—C12 | 120.5 (11) |
C1—N1—C5 | 125.4 (10) | C10—C11—H11 | 119.8 |
C1—N1—H1 | 117.3 | C12—C11—H11 | 119.8 |
C5—N1—H1 | 117.3 | C7—C12—C11 | 119.1 (13) |
C16—N2—C15 | 112.9 (10) | C7—C12—H12 | 120.5 |
C16—N2—C17 | 109.7 (11) | C11—C12—H12 | 120.5 |
C15—N2—C17 | 113.3 (11) | C6—C13—H13A | 109.5 |
C16—N2—H2 | 106.9 | C6—C13—H13B | 109.5 |
C15—N2—H2 | 106.9 | H13A—C13—H13B | 109.5 |
C17—N2—H2 | 106.9 | C6—C13—H13C | 109.5 |
N1—C1—C2 | 119.7 (12) | H13A—C13—H13C | 109.5 |
N1—C1—H1A | 120.2 | H13B—C13—H13C | 109.5 |
C2—C1—H1A | 120.2 | O1—C14—C15 | 104.4 (9) |
C1—C2—C3 | 119.0 (13) | O1—C14—H14A | 110.9 |
C1—C2—H2A | 120.5 | C15—C14—H14A | 110.9 |
C3—C2—H2A | 120.5 | O1—C14—H14B | 110.9 |
C2—C3—C4 | 119.9 (13) | C15—C14—H14B | 110.9 |
C2—C3—H3 | 120.0 | H14A—C14—H14B | 108.9 |
C4—C3—H3 | 120.0 | N2—C15—C14 | 113.4 (10) |
C3—C4—C5 | 120.3 (12) | N2—C15—H15A | 108.9 |
C3—C4—H4 | 119.8 | C14—C15—H15A | 108.9 |
C5—C4—H4 | 119.8 | N2—C15—H15B | 108.9 |
N1—C5—C4 | 115.7 (10) | C14—C15—H15B | 108.9 |
N1—C5—C6 | 119.7 (9) | H15A—C15—H15B | 107.7 |
C4—C5—C6 | 124.6 (10) | N2—C16—H16A | 109.5 |
O1—C6—C5 | 101.9 (9) | N2—C16—H16B | 109.5 |
O1—C6—C13 | 110.9 (10) | H16A—C16—H16B | 109.5 |
C5—C6—C13 | 109.3 (10) | N2—C16—H16C | 109.5 |
O1—C6—C7 | 108.9 (9) | H16A—C16—H16C | 109.5 |
C5—C6—C7 | 109.8 (9) | H16B—C16—H16C | 109.5 |
C13—C6—C7 | 115.2 (10) | N2—C17—H17A | 109.5 |
C12—C7—C8 | 121.4 (12) | N2—C17—H17B | 109.5 |
C12—C7—C6 | 121.4 (12) | H17A—C17—H17B | 109.5 |
C8—C7—C6 | 117.1 (10) | N2—C17—H17C | 109.5 |
C7—C8—C9 | 118.1 (11) | H17A—C17—H17C | 109.5 |
C7—C8—H8 | 121.0 | H17B—C17—H17C | 109.5 |
C9—C8—H8 | 121.0 | | |
| | | |
C5—N1—C1—C2 | 1.3 (17) | C5—C6—C7—C12 | −119.6 (12) |
N1—C1—C2—C3 | −1.0 (19) | C13—C6—C7—C12 | 4.3 (16) |
C1—C2—C3—C4 | 0 (2) | O1—C6—C7—C8 | −51.6 (14) |
C2—C3—C4—C5 | 1 (2) | C5—C6—C7—C8 | 59.1 (14) |
C1—N1—C5—C4 | −0.4 (16) | C13—C6—C7—C8 | −177.0 (11) |
C1—N1—C5—C6 | −179.3 (10) | C12—C7—C8—C9 | −3.3 (18) |
C3—C4—C5—N1 | −0.7 (17) | C6—C7—C8—C9 | 178.0 (11) |
C3—C4—C5—C6 | 178.1 (11) | C7—C8—C9—C10 | 2.7 (19) |
C14—O1—C6—C5 | 175.7 (9) | C8—C9—C10—C11 | 0 (2) |
C14—O1—C6—C13 | 59.5 (13) | C9—C10—C11—C12 | −2 (2) |
C14—O1—C6—C7 | −68.4 (12) | C8—C7—C12—C11 | 1.3 (18) |
N1—C5—C6—O1 | −21.1 (12) | C6—C7—C12—C11 | 179.9 (12) |
C4—C5—C6—O1 | 160.1 (11) | C10—C11—C12—C7 | 1.5 (18) |
N1—C5—C6—C13 | 96.3 (12) | C6—O1—C14—C15 | 176.7 (10) |
C4—C5—C6—C13 | −82.5 (13) | C16—N2—C15—C14 | 160.5 (11) |
N1—C5—C6—C7 | −136.4 (10) | C17—N2—C15—C14 | −74.1 (14) |
C4—C5—C6—C7 | 44.8 (15) | O1—C14—C15—N2 | −58.0 (13) |
O1—C6—C7—C12 | 129.7 (11) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1 | 0.88 | 2.30 | 3.101 (9) | 152 |
N2—H2···Cl4i | 0.93 | 2.50 | 3.253 (10) | 138 |
N1—H1···O1 | 0.88 | 2.12 | 2.517 (11) | 107 |
N2—H2···O1 | 0.93 | 2.31 | 2.757 (12) | 109 |
Symmetry code: (i) x, −y+1, z+1/2. |
Experimental details
Crystal data |
Chemical formula | (C17H24N2O)[CuCl4] |
Mr | 477.72 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 170 |
a, b, c (Å) | 16.807 (2), 9.3006 (16), 13.7677 (10) |
β (°) | 106.682 (10) |
V (Å3) | 2061.5 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.59 |
Crystal size (mm) | 0.45 × 0.23 × 0.18 |
|
Data collection |
Diffractometer | Rigaku AFC6S diffractometer |
Absorption correction | Empirical (using intensity measurements) ψ-scan (3 reflections) (North et al., 1968) |
Tmin, Tmax | 0.54, 0.76 |
No. of measured, independent and observed [I > 2.0σ(I)] reflections | 1901, 1901, 1140 |
Rint | 0.00 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.128, 1.02 |
No. of reflections | 1901 |
No. of parameters | 229 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.53, −0.63 |
Absolute structure | (Flack, 1983) |
Absolute structure parameter | −0.02 (4) |
Selected geometric parameters (Å, º) topCu1—Cl3 | 2.206 (3) | N1—C1 | 1.322 (14) |
Cu1—Cl2 | 2.210 (3) | N1—C5 | 1.326 (13) |
Cu1—Cl4 | 2.248 (4) | N2—C16 | 1.449 (16) |
Cu1—Cl1 | 2.299 (3) | N2—C15 | 1.478 (15) |
O1—C14 | 1.413 (12) | N2—C17 | 1.479 (17) |
O1—C6 | 1.445 (13) | | |
| | | |
Cl3—Cu1—Cl2 | 100.62 (13) | C14—O1—C6 | 116.1 (8) |
Cl3—Cu1—Cl4 | 132.81 (14) | C1—N1—C5 | 125.4 (10) |
Cl2—Cu1—Cl4 | 102.57 (12) | C16—N2—C15 | 112.9 (10) |
Cl3—Cu1—Cl1 | 100.86 (12) | C16—N2—C17 | 109.7 (11) |
Cl2—Cu1—Cl1 | 123.09 (13) | C15—N2—C17 | 113.3 (11) |
Cl4—Cu1—Cl1 | 99.92 (13) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1 | 0.88 | 2.30 | 3.101 (9) | 152 |
N2—H2···Cl4i | 0.93 | 2.50 | 3.253 (10) | 138 |
N1—H1···O1 | 0.88 | 2.12 | 2.517 (11) | 107 |
N2—H2···O1 | 0.93 | 2.31 | 2.757 (12) | 109 |
Symmetry code: (i) x, −y+1, z+1/2. |
Doxylamine, C17H22N2O, is a chiral tertiary aminoalkyl ether effective on H1 receptor site (Casy, 1991). Unlike the crystal structures of tetrachlorozincate and tetrachlorocobaltate salts of doxylamine which have been reported from our laboratory in centrosymmetric space group (Parvez & Sabir, 1998), this antihistamine has now been crystallized as a dihydrocation with CuCl42- anion in a non-centrosymmetric space group. In this paper, we report the structure of doxylamine tetrachlorocuprate(II), (I). \sch
Figure 1 shows an ORTEPII (Johnson, 1976) drawing of (I). The molecular dimensions in the doxylamine dication are normal. The important mean bond distances are: Csp3-Csp3 1.497 (17), Csp3-Csp2 1.514 (9), C—Caromatic 1.378 (15), C—Cpyridyl 1.376 (19), N—Csp3 1.469 (14), N—Csp2 1.324 (2), and O—Csp3 1.429 (16) Å. The pyridyl and phenyl rings are essentially planar with maximum deviations of atoms from the least-squares planes being 0.007 (8) and 0.019 (9) Å, respectively. The dihedral angle between these planes in (I) is 82.9 (3)°; the corresponding angles in the structures of tetrachlorozincate and tetrachlorocobaltate salts of doxylamine are 87.68 (14) and 88.1 (2)°, respectively (Parvez & Sabir, 1998).
The atoms C6, O1, C14 and C15 of the side chain in (I) are coplanar and are fully extended, with N2 lying in a non-extended conformation. This is in contrast to the conformation adopted by the corresponding atoms C6, O1, C14, C15, N2 in the structures of tetrachlorozincate and tetrachlorocobaltate salts of doxylamine were essentially planar with deviations of 0.042 (2) and 0.058 (4) Å, respectively (Parvez & Sabir, 1998).
It is interesting to note that in (I), O1 is hydrogen bonded to two hydrogen atoms, one H from the pyridyl ring [O1···N1 2.517 (11) Å] and one H from the ammonium N [O1···N2 2.757 (12) Å]. A similar pattern of hydrogen bonding has been observed in the structures of tetrachlorozincate and tetrachlorocobaltate salts of doxylamine (Parvez & Sabir, 1998). The N—H groups are also hydrogen bonded to the Cl atoms of two CuCl42- anions with N···Cl distances of 3.101 (9) Å for the pyridinyl N and 3.253 (10) Å for the ammonium N. Similar bifurcated hydrogen bonding has been found in the structure of chloropyramine tetrachlorocuprate (II) (Parvez & Sabir, 1997). The structure of (I) is stabilized by the extensive hydrogen bonding involving the ethereal O and both N atoms of the cations and two Cl atoms of the anions; details of the hydrogen-bonding geometry are presented in Table 2.
The CuCl42- anion shows a flattened tetrahedral geometry. The Cu—Cl bond lengths for Cl-atoms not involved in hydrogen bonding are identical [2.206 (3) and 2.210 (3) Å] while those involved in hydrogen bonds are significantly longer with values 2.248 (4) and 2.299 (3) Å. The bond angles Cl—Cu—Cl lie in two ranges, four being in the range 99.92 (13)–102.57 (12)° and the remaining two angles are 123.09 (13) and 132.81 (14)°.
The crystal structures of a number of closely related compounds have been determined, e.g. diphenhydramine (Glaser & Maartmann-Moe, 1990), diphenhydramine thiourea complex (Wiedenfield & Knoch, 1987), carbinoxamine maleate (Bertolasi et al., 1980), and clemastine hydrogen fumerate (Parvez & Wendling, 1991).