The title compounds, C
15H
16ClN
2O
+·Br
-·1.5H
2O and C
15H
16BrN
2O
+·Br
-·1.5H
2O, are isomorphous. The benzene ring is oriented nearly normal to the pyridine ring in both compounds. The molecular packing is mainly influenced by intermolecular O-H
O and O-H
Br interactions, as well as weak intramolecular C-H
O interactions. The H
2OBr
- units form an extended water-bromide chain, with a bridging water molecule on a twofold axis.
Supporting information
CCDC references: 245874; 245875
To a solution of p-chloro phenacyl bromide (0.85 g, 4 mmol) in dry acetone, DMAP (0.5 g, 41 mmol) was added. The mixture was refluxed for 30 min. After cooling, the resulting solid product was filtered off and washed with dry acetone to give (I) (m.p. 472–474 K), which was dried in a vacuum and recrystallized from ethanol. Compound (II) was prepared in an identical fashion but with p-bromo phenacyl bromide (0.85 g, 4 mmol) in dry acetone as the starting material (m.p. 501–504 K). The resulting solid, (II), was dried in a vaccum and recrystallized from ethanol.
Since the compounds are isostructural, (II) was refined with the coordinates of the dimethylamine pyridinium moiety of (I). The positions of the Br atoms and water molecules were determined from a difference Fourier map. The methyl H atoms were constrained to an ideal geometry (C—H = 0.96 Å), with Uiso(H) values of 1.5 Ueq(C). All remaining H atoms were placed in idealized positions (C—H = 0.93–0.97 Å) and were constrained to ride on their parent non-H atoms, with Uiso(H) values of 1.2 Ueq(C).
For both compounds, data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: WinGX (Farrugia, 1999) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).
(I) 1-[(4-Chlorobenzoyl)methyl]-4-(
N,
N-dimethylamino)pyridinium bromide sesquihydrate
top
Crystal data top
C15H16ClN2O+·Br−·1.5H2O | F(000) = 1560 |
Mr = 382.68 | Dx = 1.475 Mg m−3 |
Monoclinic, C2/c | Melting point: 473 K K |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 20.661 (9) Å | Cell parameters from 873 reflections |
b = 9.795 (4) Å | θ = 2.2–28.9° |
c = 17.249 (7) Å | µ = 2.55 mm−1 |
β = 99.182 (12)° | T = 298 K |
V = 3446 (2) Å3 | Block, colorless |
Z = 8 | 0.30 × 0.30 × 0.20 mm |
Data collection top
Bruker Smart 1K CCD diffractometer | 3632 independent reflections |
Radiation source: fine-focus sealed tube | 2396 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
ω scans | θmax = 27.1°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Siemens, 1996) | h = −25→25 |
Tmin = 0.515, Tmax = 0.630 | k = 0→12 |
13764 measured reflections | l = 0→21 |
Refinement top
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0481P)2 + 2.1711P] where P = (Fo2 + 2Fc2)/3 |
3632 reflections | (Δ/σ)max = 0.001 |
209 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
Crystal data top
C15H16ClN2O+·Br−·1.5H2O | V = 3446 (2) Å3 |
Mr = 382.68 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 20.661 (9) Å | µ = 2.55 mm−1 |
b = 9.795 (4) Å | T = 298 K |
c = 17.249 (7) Å | 0.30 × 0.30 × 0.20 mm |
β = 99.182 (12)° | |
Data collection top
Bruker Smart 1K CCD diffractometer | 3632 independent reflections |
Absorption correction: multi-scan (SADABS; Siemens, 1996) | 2396 reflections with I > 2σ(I) |
Tmin = 0.515, Tmax = 0.630 | Rint = 0.041 |
13764 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.33 e Å−3 |
3632 reflections | Δρmin = −0.39 e Å−3 |
209 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.131559 (17) | 0.98279 (3) | 0.021558 (19) | 0.07272 (16) | |
Cl | 0.31073 (6) | −0.01537 (10) | 0.95388 (7) | 0.0953 (3) | |
O1 | 0.59470 (14) | 0.0002 (2) | 0.8178 (2) | 0.1040 (10) | |
O2W | 0.0000 | 0.0606 (4) | 0.2500 | 0.0810 (10) | |
H20W | 0.001 (2) | 0.009 (3) | 0.213 (2) | 0.090 (14)* | |
O3W | −0.0001 (2) | 0.0729 (4) | 0.89115 (18) | 0.1011 (10) | |
H30W | 0.029 (3) | 0.039 (5) | 0.926 (3) | 0.122 (19)* | |
H31W | −0.031 (2) | 0.069 (5) | 0.906 (2) | 0.095 (18)* | |
N1 | 0.65648 (13) | 0.2379 (2) | 0.82093 (15) | 0.0673 (7) | |
N2 | 0.80471 (13) | 0.2265 (3) | 0.68744 (16) | 0.0703 (7) | |
C1 | 0.60112 (17) | 0.2267 (3) | 0.8635 (2) | 0.0739 (9) | |
H1A | 0.5693 | 0.2972 | 0.8454 | 0.089* | |
H1B | 0.6162 | 0.2410 | 0.9190 | 0.089* | |
C2 | 0.71617 (18) | 0.1839 (3) | 0.84964 (19) | 0.0741 (9) | |
H2 | 0.7229 | 0.1477 | 0.9001 | 0.089* | |
C3 | 0.76544 (17) | 0.1808 (3) | 0.80820 (19) | 0.0704 (9) | |
H3 | 0.8056 | 0.1438 | 0.8305 | 0.084* | |
C4 | 0.75758 (15) | 0.2326 (3) | 0.73126 (17) | 0.0609 (8) | |
C5 | 0.69583 (17) | 0.2918 (3) | 0.70361 (19) | 0.0717 (9) | |
H5 | 0.6883 | 0.3319 | 0.6541 | 0.086* | |
C6 | 0.64808 (18) | 0.2907 (3) | 0.7477 (2) | 0.0763 (9) | |
H6 | 0.6076 | 0.3279 | 0.7271 | 0.092* | |
C7 | 0.86799 (17) | 0.1633 (4) | 0.7141 (2) | 0.0979 (13) | |
H7A | 0.9008 | 0.2330 | 0.7259 | 0.147* | |
H7B | 0.8793 | 0.1050 | 0.6735 | 0.147* | |
H7C | 0.8658 | 0.1103 | 0.7604 | 0.147* | |
C8 | 0.79628 (19) | 0.2818 (4) | 0.6079 (2) | 0.0886 (11) | |
H8A | 0.7763 | 0.2140 | 0.5715 | 0.133* | |
H8B | 0.8383 | 0.3065 | 0.5951 | 0.133* | |
H8C | 0.7687 | 0.3610 | 0.6048 | 0.133* | |
C9 | 0.56883 (16) | 0.0887 (3) | 0.85139 (19) | 0.0682 (8) | |
C10 | 0.50638 (16) | 0.0652 (3) | 0.88073 (17) | 0.0617 (8) | |
C11 | 0.47681 (19) | −0.0616 (4) | 0.8711 (2) | 0.0882 (11) | |
H11 | 0.4977 | −0.1314 | 0.8481 | 0.106* | |
C12 | 0.4181 (2) | −0.0874 (4) | 0.8944 (2) | 0.0903 (11) | |
H12 | 0.3991 | −0.1735 | 0.8876 | 0.108* | |
C13 | 0.38734 (19) | 0.0157 (3) | 0.92811 (18) | 0.0699 (9) | |
C14 | 0.41627 (19) | 0.1403 (3) | 0.9413 (2) | 0.0812 (11) | |
H14 | 0.3958 | 0.2084 | 0.9662 | 0.097* | |
C15 | 0.47567 (18) | 0.1654 (3) | 0.91781 (18) | 0.0727 (9) | |
H15 | 0.4953 | 0.2505 | 0.9270 | 0.087* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0799 (3) | 0.0676 (2) | 0.0650 (2) | −0.00015 (16) | −0.00562 (16) | −0.00631 (15) |
Cl | 0.1196 (8) | 0.0848 (6) | 0.0890 (7) | −0.0048 (5) | 0.0398 (6) | 0.0005 (5) |
O1 | 0.0833 (18) | 0.0803 (17) | 0.148 (3) | 0.0042 (13) | 0.0169 (18) | −0.0512 (16) |
O2W | 0.085 (2) | 0.067 (2) | 0.089 (3) | 0.000 | 0.008 (2) | 0.000 |
O3W | 0.099 (2) | 0.138 (3) | 0.0667 (18) | 0.019 (2) | 0.0135 (18) | 0.0154 (17) |
N1 | 0.0838 (19) | 0.0570 (15) | 0.0606 (16) | 0.0093 (13) | 0.0100 (14) | 0.0001 (12) |
N2 | 0.0754 (18) | 0.0637 (16) | 0.0705 (17) | 0.0051 (13) | 0.0076 (14) | 0.0071 (13) |
C1 | 0.094 (2) | 0.0605 (19) | 0.070 (2) | 0.0048 (17) | 0.0200 (18) | −0.0076 (16) |
C2 | 0.090 (2) | 0.075 (2) | 0.0517 (18) | −0.0017 (19) | −0.0029 (18) | 0.0114 (16) |
C3 | 0.069 (2) | 0.073 (2) | 0.063 (2) | 0.0018 (16) | −0.0071 (16) | 0.0178 (16) |
C4 | 0.072 (2) | 0.0502 (16) | 0.0569 (19) | 0.0040 (15) | 0.0000 (16) | 0.0013 (13) |
C5 | 0.085 (2) | 0.072 (2) | 0.0546 (18) | 0.0184 (18) | 0.0032 (17) | 0.0130 (15) |
C6 | 0.087 (2) | 0.069 (2) | 0.070 (2) | 0.0262 (18) | 0.0018 (19) | 0.0091 (16) |
C7 | 0.074 (2) | 0.095 (3) | 0.127 (4) | 0.016 (2) | 0.023 (2) | 0.025 (3) |
C8 | 0.103 (3) | 0.097 (3) | 0.068 (2) | 0.000 (2) | 0.020 (2) | 0.009 (2) |
C9 | 0.077 (2) | 0.0560 (18) | 0.066 (2) | 0.0125 (16) | −0.0068 (16) | −0.0127 (15) |
C10 | 0.074 (2) | 0.0505 (16) | 0.0558 (17) | 0.0105 (15) | −0.0039 (15) | −0.0053 (13) |
C11 | 0.075 (2) | 0.063 (2) | 0.124 (3) | 0.0049 (18) | 0.009 (2) | −0.033 (2) |
C12 | 0.094 (3) | 0.062 (2) | 0.111 (3) | −0.001 (2) | 0.006 (2) | −0.023 (2) |
C13 | 0.095 (2) | 0.065 (2) | 0.0497 (17) | 0.0084 (17) | 0.0120 (16) | 0.0042 (14) |
C14 | 0.123 (3) | 0.0524 (19) | 0.076 (2) | 0.0090 (19) | 0.041 (2) | −0.0059 (16) |
C15 | 0.106 (3) | 0.0471 (17) | 0.069 (2) | 0.0014 (17) | 0.0256 (19) | −0.0044 (15) |
Geometric parameters (Å, º) top
Cl—C13 | 1.738 (4) | C5—H5 | 0.9300 |
O1—C9 | 1.213 (4) | C6—H6 | 0.9300 |
O2W—H20W | 0.82 (3) | C7—H7A | 0.9600 |
O3W—H30W | 0.84 (6) | C7—H7B | 0.9600 |
O3W—H31W | 0.73 (4) | C7—H7C | 0.9600 |
N1—C6 | 1.350 (4) | C8—H8A | 0.9600 |
N1—C2 | 1.361 (4) | C8—H8B | 0.9600 |
N1—C1 | 1.458 (4) | C8—H8C | 0.9600 |
N2—C4 | 1.326 (4) | C9—C10 | 1.477 (5) |
N2—C7 | 1.453 (4) | C10—C15 | 1.380 (4) |
N2—C8 | 1.459 (4) | C10—C11 | 1.383 (5) |
C1—C9 | 1.508 (4) | C11—C12 | 1.362 (5) |
C1—H1A | 0.9700 | C11—H11 | 0.9300 |
C1—H1B | 0.9700 | C12—C13 | 1.370 (5) |
C2—C3 | 1.334 (4) | C12—H12 | 0.9300 |
C2—H2 | 0.9300 | C13—C14 | 1.362 (5) |
C3—C4 | 1.406 (4) | C14—C15 | 1.375 (5) |
C3—H3 | 0.9300 | C14—H14 | 0.9300 |
C4—C5 | 1.413 (4) | C15—H15 | 0.9300 |
C5—C6 | 1.339 (5) | | |
| | | |
H30W—O3W—H31W | 107 (5) | N2—C7—H7C | 109.5 |
C6—N1—C2 | 117.6 (3) | H7A—C7—H7C | 109.5 |
C6—N1—C1 | 120.4 (3) | H7B—C7—H7C | 109.5 |
C2—N1—C1 | 121.7 (3) | N2—C8—H8A | 109.5 |
C4—N2—C7 | 123.0 (3) | N2—C8—H8B | 109.5 |
C4—N2—C8 | 122.1 (3) | H8A—C8—H8B | 109.5 |
C7—N2—C8 | 114.9 (3) | N2—C8—H8C | 109.5 |
N1—C1—C9 | 111.3 (3) | H8A—C8—H8C | 109.5 |
N1—C1—H1A | 109.4 | H8B—C8—H8C | 109.5 |
C9—C1—H1A | 109.4 | O1—C9—C10 | 121.9 (3) |
N1—C1—H1B | 109.4 | O1—C9—C1 | 119.2 (3) |
C9—C1—H1B | 109.4 | C10—C9—C1 | 118.9 (3) |
H1A—C1—H1B | 108.0 | C15—C10—C11 | 117.9 (3) |
C3—C2—N1 | 122.6 (3) | C15—C10—C9 | 122.7 (3) |
C3—C2—H2 | 118.7 | C11—C10—C9 | 119.5 (3) |
N1—C2—H2 | 118.7 | C12—C11—C10 | 121.9 (3) |
C2—C3—C4 | 121.0 (3) | C12—C11—H11 | 119.1 |
C2—C3—H3 | 119.5 | C10—C11—H11 | 119.1 |
C4—C3—H3 | 119.5 | C11—C12—C13 | 118.9 (3) |
N2—C4—C3 | 122.5 (3) | C11—C12—H12 | 120.5 |
N2—C4—C5 | 122.1 (3) | C13—C12—H12 | 120.5 |
C3—C4—C5 | 115.4 (3) | C14—C13—C12 | 120.7 (4) |
C6—C5—C4 | 120.8 (3) | C14—C13—Cl | 120.5 (3) |
C6—C5—H5 | 119.6 | C12—C13—Cl | 118.8 (3) |
C4—C5—H5 | 119.6 | C13—C14—C15 | 119.9 (3) |
C5—C6—N1 | 122.6 (3) | C13—C14—H14 | 120.0 |
C5—C6—H6 | 118.7 | C15—C14—H14 | 120.0 |
N1—C6—H6 | 118.7 | C14—C15—C10 | 120.5 (3) |
N2—C7—H7A | 109.5 | C14—C15—H15 | 119.7 |
N2—C7—H7B | 109.5 | C10—C15—H15 | 119.7 |
H7A—C7—H7B | 109.5 | | |
| | | |
C6—N1—C1—C9 | 93.1 (3) | N1—C1—C9—O1 | 8.3 (5) |
C2—N1—C1—C9 | −80.2 (4) | N1—C1—C9—C10 | −171.5 (3) |
C6—N1—C2—C3 | −0.5 (5) | O1—C9—C10—C15 | −178.8 (3) |
C1—N1—C2—C3 | 173.0 (3) | C1—C9—C10—C15 | 1.0 (5) |
N1—C2—C3—C4 | −0.8 (5) | O1—C9—C10—C11 | 1.2 (5) |
C7—N2—C4—C3 | 1.4 (5) | C1—C9—C10—C11 | −179.0 (3) |
C8—N2—C4—C3 | −179.4 (3) | C15—C10—C11—C12 | 2.4 (6) |
C7—N2—C4—C5 | −178.6 (3) | C9—C10—C11—C12 | −177.5 (3) |
C8—N2—C4—C5 | 0.6 (5) | C10—C11—C12—C13 | 0.2 (6) |
C2—C3—C4—N2 | −177.4 (3) | C11—C12—C13—C14 | −2.9 (6) |
C2—C3—C4—C5 | 2.5 (5) | C11—C12—C13—Cl | 177.2 (3) |
N2—C4—C5—C6 | 176.8 (3) | C12—C13—C14—C15 | 2.7 (5) |
C3—C4—C5—C6 | −3.2 (5) | Cl—C13—C14—C15 | −177.4 (3) |
C4—C5—C6—N1 | 2.1 (5) | C13—C14—C15—C10 | 0.1 (5) |
C2—N1—C6—C5 | −0.2 (5) | C11—C10—C15—C14 | −2.6 (5) |
C1—N1—C6—C5 | −173.8 (3) | C9—C10—C15—C14 | 177.4 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2W—H20W···O3Wi | 0.82 (3) | 1.96 (4) | 2.764 (4) | 166 (4) |
O3W—H30W···Br1ii | 0.84 (6) | 2.54 (6) | 3.360 (4) | 167 (4) |
O3W—H31W···Br1iii | 0.73 (4) | 2.63 (4) | 3.353 (4) | 168 (5) |
C8—H8A···Cliv | 0.96 | 2.87 | 3.707 (4) | 147 |
C1—H1A···O2Wv | 0.97 | 2.44 | 3.351 (4) | 157 |
C6—H6···O2Wv | 0.93 | 2.56 | 3.394 (4) | 149 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, y−1, z+1; (iii) −x, −y+1, −z+1; (iv) −x+1, y, −z+3/2; (v) x+1/2, −y+1/2, z+1/2. |
(II) 1-[(4-Bromobenzoyl)methyl]-4-(
N,
N-dimethylamino)pyridinium bromide sesquihydrate
top
Crystal data top
C15H16BrN2O+·Br−·1.5H2O | F(000) = 1704 |
Mr = 427.14 | Dx = 1.622 Mg m−3 |
Monoclinic, C2/c | Melting point: 512.5 K K |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 20.403 (6) Å | Cell parameters from 873 reflections |
b = 10.022 (3) Å | θ = 2.3–27.4° |
c = 17.386 (4) Å | µ = 4.64 mm−1 |
β = 100.182 (8)° | T = 298 K |
V = 3499.0 (17) Å3 | Block, colourless |
Z = 8 | 0.40 × 0.30 × 0.30 mm |
Data collection top
Bruker Smart 1K CCD diffractometer | 3587 independent reflections |
Radiation source: fine-focus sealed tube | 2391 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
ω scans | θmax = 26.4°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Siemens, 1996) | h = −25→25 |
Tmin = 0.258, Tmax = 0.337 | k = 0→12 |
20471 measured reflections | l = 0→21 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.111 | w = 1/[σ2(Fo2) + (0.0507P)2 + 3.7037P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
3587 reflections | Δρmax = 0.58 e Å−3 |
210 parameters | Δρmin = −0.79 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00162 (14) |
Crystal data top
C15H16BrN2O+·Br−·1.5H2O | V = 3499.0 (17) Å3 |
Mr = 427.14 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 20.403 (6) Å | µ = 4.64 mm−1 |
b = 10.022 (3) Å | T = 298 K |
c = 17.386 (4) Å | 0.40 × 0.30 × 0.30 mm |
β = 100.182 (8)° | |
Data collection top
Bruker Smart 1K CCD diffractometer | 3587 independent reflections |
Absorption correction: multi-scan (SADABS; Siemens, 1996) | 2391 reflections with I > 2σ(I) |
Tmin = 0.258, Tmax = 0.337 | Rint = 0.045 |
20471 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.111 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.58 e Å−3 |
3587 reflections | Δρmin = −0.79 e Å−3 |
210 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.13308 (2) | 0.98601 (4) | 0.01869 (2) | 0.07221 (18) | |
Br2 | 0.30172 (3) | −0.01585 (5) | 0.94999 (3) | 0.0875 (2) | |
O1 | 0.59599 (16) | 0.0066 (3) | 0.8152 (2) | 0.1054 (12) | |
O2W | 0.0000 | 0.0624 (5) | 0.2500 | 0.0847 (12) | |
H20W | −0.006 (3) | 0.016 (4) | 0.289 (3) | 0.097 (17)* | |
O3W | 0.5039 (2) | 0.4293 (5) | 0.1104 (2) | 0.1077 (13) | |
H30W | 0.478 (3) | 0.450 (5) | 0.078 (3) | 0.095 (18)* | |
H31W | 0.539 (3) | 0.448 (6) | 0.089 (3) | 0.15 (2)* | |
N1 | 0.65949 (16) | 0.2382 (3) | 0.82071 (17) | 0.0689 (8) | |
N2 | 0.80759 (15) | 0.2303 (3) | 0.68656 (18) | 0.0694 (8) | |
C1 | 0.6039 (2) | 0.2262 (4) | 0.8631 (2) | 0.0744 (11) | |
H1A | 0.5716 | 0.2958 | 0.8459 | 0.089* | |
H1B | 0.6202 | 0.2384 | 0.9185 | 0.089* | |
C2 | 0.7200 (2) | 0.1811 (4) | 0.8474 (2) | 0.0709 (10) | |
H2 | 0.7275 | 0.1428 | 0.8969 | 0.085* | |
C3 | 0.76901 (19) | 0.1778 (4) | 0.8054 (2) | 0.0670 (9) | |
H3 | 0.8092 | 0.1371 | 0.8262 | 0.080* | |
C4 | 0.76062 (18) | 0.2349 (3) | 0.7304 (2) | 0.0602 (9) | |
C5 | 0.6984 (2) | 0.2964 (4) | 0.7046 (2) | 0.0719 (10) | |
H5 | 0.6904 | 0.3390 | 0.6563 | 0.086* | |
C6 | 0.6506 (2) | 0.2946 (4) | 0.7486 (2) | 0.0766 (11) | |
H6 | 0.6097 | 0.3335 | 0.7290 | 0.092* | |
C7 | 0.8713 (2) | 0.1639 (5) | 0.7120 (3) | 0.0934 (14) | |
H7A | 0.9044 | 0.2037 | 0.6864 | 0.140* | |
H7B | 0.8670 | 0.0709 | 0.6988 | 0.140* | |
H7C | 0.8843 | 0.1733 | 0.7675 | 0.140* | |
C8 | 0.7986 (2) | 0.2906 (4) | 0.6089 (2) | 0.0864 (12) | |
H8A | 0.7789 | 0.2266 | 0.5706 | 0.130* | |
H8B | 0.8410 | 0.3180 | 0.5978 | 0.130* | |
H8C | 0.7699 | 0.3669 | 0.6072 | 0.130* | |
C9 | 0.57064 (19) | 0.0916 (4) | 0.8496 (2) | 0.0693 (10) | |
C10 | 0.50795 (19) | 0.0681 (4) | 0.8791 (2) | 0.0636 (9) | |
C11 | 0.4776 (2) | −0.0563 (4) | 0.8692 (3) | 0.0913 (14) | |
H11 | 0.4985 | −0.1245 | 0.8465 | 0.110* | |
C12 | 0.4185 (2) | −0.0817 (4) | 0.8914 (3) | 0.0895 (13) | |
H12 | 0.3994 | −0.1661 | 0.8841 | 0.107* | |
C13 | 0.3873 (2) | 0.0173 (4) | 0.9243 (2) | 0.0675 (10) | |
C14 | 0.4164 (2) | 0.1402 (4) | 0.9384 (2) | 0.0807 (12) | |
H14 | 0.3955 | 0.2064 | 0.9627 | 0.097* | |
C15 | 0.4764 (2) | 0.1647 (4) | 0.9163 (2) | 0.0737 (11) | |
H15 | 0.4964 | 0.2478 | 0.9265 | 0.088* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0722 (3) | 0.0767 (3) | 0.0633 (3) | −0.00071 (19) | −0.00033 (18) | −0.00665 (18) |
Br2 | 0.1099 (4) | 0.0803 (3) | 0.0785 (3) | −0.0046 (2) | 0.0336 (3) | −0.0022 (2) |
O1 | 0.082 (2) | 0.084 (2) | 0.151 (3) | 0.0041 (15) | 0.024 (2) | −0.0548 (19) |
O2W | 0.077 (3) | 0.071 (3) | 0.103 (4) | 0.000 | 0.007 (3) | 0.000 |
O3W | 0.093 (3) | 0.165 (4) | 0.065 (2) | 0.017 (3) | 0.015 (2) | 0.022 (2) |
N1 | 0.084 (2) | 0.0597 (19) | 0.0623 (19) | 0.0081 (16) | 0.0118 (16) | −0.0001 (15) |
N2 | 0.074 (2) | 0.066 (2) | 0.0671 (19) | 0.0045 (16) | 0.0073 (16) | 0.0070 (15) |
C1 | 0.092 (3) | 0.066 (2) | 0.067 (2) | 0.007 (2) | 0.021 (2) | −0.0098 (19) |
C2 | 0.084 (3) | 0.067 (2) | 0.055 (2) | 0.004 (2) | −0.007 (2) | 0.0071 (18) |
C3 | 0.066 (2) | 0.071 (2) | 0.061 (2) | 0.0062 (18) | 0.0013 (18) | 0.0110 (18) |
C4 | 0.072 (2) | 0.0498 (19) | 0.055 (2) | 0.0076 (17) | 0.0019 (17) | 0.0016 (15) |
C5 | 0.085 (3) | 0.071 (2) | 0.058 (2) | 0.020 (2) | 0.007 (2) | 0.0156 (18) |
C6 | 0.088 (3) | 0.067 (2) | 0.072 (3) | 0.026 (2) | 0.006 (2) | 0.011 (2) |
C7 | 0.077 (3) | 0.096 (3) | 0.110 (3) | 0.019 (2) | 0.022 (2) | 0.021 (3) |
C8 | 0.104 (3) | 0.087 (3) | 0.069 (3) | −0.001 (2) | 0.017 (2) | 0.013 (2) |
C9 | 0.073 (2) | 0.065 (2) | 0.064 (2) | 0.012 (2) | −0.0055 (18) | −0.0126 (18) |
C10 | 0.075 (2) | 0.054 (2) | 0.057 (2) | 0.0116 (18) | −0.0026 (17) | −0.0045 (16) |
C11 | 0.077 (3) | 0.067 (3) | 0.125 (4) | 0.007 (2) | 0.004 (3) | −0.035 (3) |
C12 | 0.078 (3) | 0.070 (3) | 0.118 (4) | −0.001 (2) | 0.010 (3) | −0.029 (3) |
C13 | 0.088 (3) | 0.065 (2) | 0.0488 (18) | 0.0106 (19) | 0.0101 (17) | 0.0014 (16) |
C14 | 0.118 (4) | 0.060 (2) | 0.073 (3) | 0.001 (2) | 0.043 (2) | −0.0084 (19) |
C15 | 0.105 (3) | 0.050 (2) | 0.069 (2) | −0.002 (2) | 0.026 (2) | −0.0077 (18) |
Geometric parameters (Å, º) top
Br2—C13 | 1.907 (4) | C5—H5 | 0.9300 |
O1—C9 | 1.209 (4) | C6—H6 | 0.9300 |
O2W—H20W | 0.85 (4) | C7—H7A | 0.9600 |
O3W—H30W | 0.74 (5) | C7—H7B | 0.9600 |
O3W—H31W | 0.89 (6) | C7—H7C | 0.9600 |
N1—C6 | 1.357 (5) | C8—H8A | 0.9600 |
N1—C2 | 1.365 (4) | C8—H8B | 0.9600 |
N1—C1 | 1.462 (5) | C8—H8C | 0.9600 |
N2—C4 | 1.327 (4) | C9—C10 | 1.479 (5) |
N2—C7 | 1.457 (5) | C10—C15 | 1.385 (5) |
N2—C8 | 1.461 (5) | C10—C11 | 1.389 (6) |
C1—C9 | 1.510 (5) | C11—C12 | 1.353 (6) |
C1—H1A | 0.9700 | C11—H11 | 0.9300 |
C1—H1B | 0.9700 | C12—C13 | 1.359 (5) |
C2—C3 | 1.339 (5) | C12—H12 | 0.9300 |
C2—H2 | 0.9300 | C13—C14 | 1.370 (5) |
C3—C4 | 1.407 (5) | C14—C15 | 1.369 (5) |
C3—H3 | 0.9300 | C14—H14 | 0.9300 |
C4—C5 | 1.412 (5) | C15—H15 | 0.9300 |
C5—C6 | 1.342 (5) | | |
| | | |
H30W—O3W—H31W | 99 (5) | N2—C7—H7C | 109.5 |
C6—N1—C2 | 117.0 (3) | H7A—C7—H7C | 109.5 |
C6—N1—C1 | 120.7 (3) | H7B—C7—H7C | 109.5 |
C2—N1—C1 | 122.0 (3) | N2—C8—H8A | 109.5 |
C4—N2—C7 | 122.5 (3) | N2—C8—H8B | 109.5 |
C4—N2—C8 | 122.1 (3) | H8A—C8—H8B | 109.5 |
C7—N2—C8 | 115.4 (3) | N2—C8—H8C | 109.5 |
N1—C1—C9 | 111.3 (3) | H8A—C8—H8C | 109.5 |
N1—C1—H1A | 109.4 | H8B—C8—H8C | 109.5 |
C9—C1—H1A | 109.4 | O1—C9—C10 | 122.1 (4) |
N1—C1—H1B | 109.4 | O1—C9—C1 | 119.1 (4) |
C9—C1—H1B | 109.4 | C10—C9—C1 | 118.8 (3) |
H1A—C1—H1B | 108.0 | C15—C10—C11 | 116.9 (4) |
C3—C2—N1 | 122.9 (3) | C15—C10—C9 | 123.5 (4) |
C3—C2—H2 | 118.6 | C11—C10—C9 | 119.6 (3) |
N1—C2—H2 | 118.6 | C12—C11—C10 | 122.3 (4) |
C2—C3—C4 | 121.0 (3) | C12—C11—H11 | 118.9 |
C2—C3—H3 | 119.5 | C10—C11—H11 | 118.9 |
C4—C3—H3 | 119.5 | C11—C12—C13 | 119.3 (4) |
N2—C4—C3 | 122.5 (3) | C11—C12—H12 | 120.3 |
N2—C4—C5 | 122.2 (3) | C13—C12—H12 | 120.3 |
C3—C4—C5 | 115.3 (3) | C12—C13—C14 | 120.8 (4) |
C6—C5—C4 | 121.1 (3) | C12—C13—Br2 | 119.2 (3) |
C6—C5—H5 | 119.5 | C14—C13—Br2 | 120.0 (3) |
C4—C5—H5 | 119.5 | C15—C14—C13 | 119.5 (4) |
C5—C6—N1 | 122.7 (4) | C15—C14—H14 | 120.3 |
C5—C6—H6 | 118.7 | C13—C14—H14 | 120.3 |
N1—C6—H6 | 118.7 | C14—C15—C10 | 121.2 (4) |
N2—C7—H7A | 109.5 | C14—C15—H15 | 119.4 |
N2—C7—H7B | 109.5 | C10—C15—H15 | 119.4 |
H7A—C7—H7B | 109.5 | | |
| | | |
C6—N1—C1—C9 | 94.3 (4) | N1—C1—C9—O1 | 8.3 (5) |
C2—N1—C1—C9 | −78.4 (4) | N1—C1—C9—C10 | −171.9 (3) |
C6—N1—C2—C3 | −0.8 (6) | O1—C9—C10—C15 | −177.7 (4) |
C1—N1—C2—C3 | 172.2 (4) | C1—C9—C10—C15 | 2.5 (5) |
N1—C2—C3—C4 | 0.4 (6) | O1—C9—C10—C11 | 1.6 (6) |
C7—N2—C4—C3 | 1.0 (6) | C1—C9—C10—C11 | −178.2 (4) |
C8—N2—C4—C3 | −179.6 (4) | C15—C10—C11—C12 | 2.8 (6) |
C7—N2—C4—C5 | −178.3 (4) | C9—C10—C11—C12 | −176.5 (4) |
C8—N2—C4—C5 | 1.0 (6) | C10—C11—C12—C13 | 0.2 (7) |
C2—C3—C4—N2 | −178.2 (4) | C11—C12—C13—C14 | −2.9 (7) |
C2—C3—C4—C5 | 1.1 (5) | C11—C12—C13—Br2 | 176.4 (4) |
N2—C4—C5—C6 | 177.0 (4) | C12—C13—C14—C15 | 2.4 (6) |
C3—C4—C5—C6 | −2.4 (6) | Br2—C13—C14—C15 | −176.9 (3) |
C4—C5—C6—N1 | 2.2 (7) | C13—C14—C15—C10 | 0.8 (6) |
C2—N1—C6—C5 | −0.5 (6) | C11—C10—C15—C14 | −3.3 (6) |
C1—N1—C6—C5 | −173.6 (4) | C9—C10—C15—C14 | 176.0 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2W—H20W···O3Wi | 0.85 (4) | 1.95 (4) | 2.784 (5) | 167 (5) |
O3W—H30W···Br1ii | 0.74 (5) | 2.65 (5) | 3.369 (4) | 168 (5) |
O3W—H31W···Br1iii | 0.89 (6) | 2.48 (6) | 3.360 (4) | 174 (5) |
C8—H8A···Br2iv | 0.96 | 2.92 | 3.732 (5) | 143 |
C1—H1A···O2Wv | 0.97 | 2.46 | 3.373 (5) | 156 |
C6—H6···O2Wv | 0.93 | 2.55 | 3.394 (5) | 151 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, −y+3/2, −z; (iii) x+1/2, y−1/2, z; (iv) −x+1, y, −z+3/2; (v) x+1/2, −y+1/2, z+1/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C15H16ClN2O+·Br−·1.5H2O | C15H16BrN2O+·Br−·1.5H2O |
Mr | 382.68 | 427.14 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, C2/c |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 20.661 (9), 9.795 (4), 17.249 (7) | 20.403 (6), 10.022 (3), 17.386 (4) |
β (°) | 99.182 (12) | 100.182 (8) |
V (Å3) | 3446 (2) | 3499.0 (17) |
Z | 8 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 2.55 | 4.64 |
Crystal size (mm) | 0.30 × 0.30 × 0.20 | 0.40 × 0.30 × 0.30 |
|
Data collection |
Diffractometer | Bruker Smart 1K CCD diffractometer | Bruker Smart 1K CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Siemens, 1996) | Multi-scan (SADABS; Siemens, 1996) |
Tmin, Tmax | 0.515, 0.630 | 0.258, 0.337 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13764, 3632, 2396 | 20471, 3587, 2391 |
Rint | 0.041 | 0.045 |
(sin θ/λ)max (Å−1) | 0.640 | 0.626 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.107, 1.01 | 0.038, 0.111, 1.02 |
No. of reflections | 3632 | 3587 |
No. of parameters | 209 | 210 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.33, −0.39 | 0.58, −0.79 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2W—H20W···O3Wi | 0.82 (3) | 1.96 (4) | 2.764 (4) | 166 (4) |
O3W—H30W···Br1ii | 0.84 (6) | 2.54 (6) | 3.360 (4) | 167 (4) |
O3W—H31W···Br1iii | 0.73 (4) | 2.63 (4) | 3.353 (4) | 168 (5) |
C8—H8A···Cliv | 0.96 | 2.87 | 3.707 (4) | 147 |
C1—H1A···O2Wv | 0.97 | 2.44 | 3.351 (4) | 157 |
C6—H6···O2Wv | 0.93 | 2.56 | 3.394 (4) | 149 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, y−1, z+1; (iii) −x, −y+1, −z+1; (iv) −x+1, y, −z+3/2; (v) x+1/2, −y+1/2, z+1/2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2W—H20W···O3Wi | 0.85 (4) | 1.95 (4) | 2.784 (5) | 167 (5) |
O3W—H30W···Br1ii | 0.74 (5) | 2.65 (5) | 3.369 (4) | 168 (5) |
O3W—H31W···Br1iii | 0.89 (6) | 2.48 (6) | 3.360 (4) | 174 (5) |
C8—H8A···Br2iv | 0.96 | 2.92 | 3.732 (5) | 143.0 |
C1—H1A···O2Wv | 0.97 | 2.46 | 3.373 (5) | 156 |
C6—H6···O2Wv | 0.93 | 2.55 | 3.394 (5) | 151 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, −y+3/2, −z; (iii) x+1/2, y−1/2, z; (iv) −x+1, y, −z+3/2; (v) x+1/2, −y+1/2, z+1/2. |
Aminopyridines are key intermediates for the synthesis of important pharmaceuticals and agrochemicals. 4-Dimethylaminopyridine (DMAP) is an excellent catalyst for a variety of synthetic transformations under mild conditions, such as alkylations, acylations, silylations, esterifications, polymerizations and rearrangements (Prabakaran et al., 2001, and references therein). As part of our interest in the identification of bioactive compounds, we report here the structure determination of two of the derivatives of DMAP, the title compounds, (I) and (II). Compound (II) is isostructural with (I).
Perspective views of DMAP moieties of molecules of (I) and (II), with the atomic numbering schemes, are shown in Figs. 1 and 2, respectively. The corresponding bond lengths and angles in (I) and (II) are essentially equivalent and are comparable to those in a related structure (Prabakaran et al., 2001). The dimethylamine N atom is almost coplanar with the plane of pyridine ring in both (I) and (II) [2.9 (3)° in (I) and 2.6 (4)° in (II)]. The angles between the least-squares planes of the pyridine and phenyl rings are 81.01 (11)° in (I) and 78.64 (13)° in (II).
An interesting feature of the pyridinium systems is that they have a substantial degree of quinoidal character, since the C2—C3 and C5—C6 bond lengths in (I) and (II) [1.334 (4) and 1.339 (5) Å, and 1.339 (5) and 1.342 (5) Å] are significantly shorter than those observed for C3—C4 and C4—C5 [1.406 (4) and 1.413 (4) Å, and 1.407 (5) and 1.412 (5) Å]. The C4—N2 bond lengths in (I) and (II) are the same within experimental error [1.326 (4) and 1.327 (4) Å] and are intermediate between the C—N single- and double-bond distances [1.458 (4) and 1.326 (4) Å in (I), and 1.462 (5) and 1.327 (4) Å in (II)], indicating a significant conjugation. The sum of the bond angles at atoms N1 and N2 [359.7 (3) and 360.0 (3)°, and 359.7 (3) and 359.9 (3)°] for (I) and (II) are almost 360°, and hence there is little evidence for the presence of an sp3 lone pair.
Even after the substitution of halide atoms at the para position, the general conformation of the molecule has not been affected in (I) and (II). In both compounds, the asymmetric units contain two water molecules each, with the O atom of one of the water molecules lying on a special position (O2W, 0.0, 0.06, 1/4) on the twofold axis. In addition to the hydrogen-bonded clusters in the form of quadrilaterals as reported in the structure (Prabakaran et al., 2001), we observe additional hydrogen bonds connecting two quadrilaterals through the water molecule in the special position, running along the c axis as an infinite continuous chain. The (H2O,Br)2 clusters in (I) and (II) are sandwiched between organic molecules by C—H···Br− hydrogen bonds and are illustrated in Figs. 3 and 4, respectively. The hydrogen-bonding geometry is given in Tables 1 and 2 for (I) and (II), respectively.