In dibenzylammonium hydrogen maleate [or dibenzylammonium (2
Z)-3-carboxyprop-2-enoate], C
14H
16N
+·C
4H
3O
4-, (I), the anion contains a fairly short and nearly linear O-H
O hydrogen bond, with an O
·O distance of 2.4603 (16) Å, but with the H atom clearly offset from the mid-point of the O
O vector. The counter-ions in (I) are linked by two N-H
O hydrogen bonds to form
C22(6) chains and these chains are weakly linked into sheets by a C-H
O hydrogen bond. Bis(dibenzylamino)methane, C
29H
30N
2, (II), crystallizes with two independent molecules lying across twofold rotation axes in the space group
C2/
c, and the molecules are conformationally chiral; there are no direction-specific intermolecular interactions in the crystal structure of (II).
Supporting information
CCDC references: 957037; 957038
For the synthesis of salt (I), a mixture of dibenzylamine (80 mg) and an excess
of maleic acid (161 mg, 2.5 equivalents) in ethyl acetate (2 ml) was stirred
at ambient temperature of 1 h. The resulting solid product was collected by
filtration, washed with cold ethyl acetate (2 × 1 ml) and dried at
ambient temperature to provide the product (I) as colourless crystals (yield
86%, m.p. 482 K). FT–IR (KBr): 3032, 2828, 2751, 2636, 1705 (C═O), 1629
(C═C), 1384, 1361, 1214, 109=86 [clarify] (C—O) cm-1. Crystals
suitable for single-crystal X-ray diffraction were grown by slow evaporation,
at ambient temperature and in air, from a solution in ethyl acetate. For the
synthesis of compound (II), a mixture of dibenzylamine (201 mg, 2.0 mmol) and
paraformaldehyde (15 mg, 1.0 mmol) in acetonitrile (2 ml) was stirred at
ambient temperature for 3 h. The resulting solid product was collected by
filtration, washed with acetonitrile (1 ml) and dried at ambient temperatur to
provide the aminal (II) (yield 93%, m.p. 372 K). FT-IR (KBr): 3058, 2925,
2877, 1599, 739, 697 cm-1. Colourless crystals suitable for single-crystal
X-ray diffraction were grown by slow evaporation, at ambient temperature and
in air, from a solution in ethanol.
All H atoms were located in difference maps. H atoms bonded to C atoms were
then treated as riding atoms in geometrically idealized positions, with C—H
= 0.95 (aromatic and alkene) or 0.99 Å (CH2) and Uiso(H) =
1.2Ueq(C). H atoms bonded to N or O atoms were permitted to ride at
the positions deduced from difference maps, with Uiso(H) =
1.2Ueq(N) or 1.5Ueq(O), giving the N—H and O—H distances
shown in Table 2.
For both compounds, data collection: COLLECT (Hooft, 1998); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
(I) Dibenzylammonium (2
Z)-3-carboxyprop-2-enoate
top
Crystal data top
C14H16N+·C4H3O4− | F(000) = 664 |
Mr = 313.34 | Dx = 1.313 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3639 reflections |
a = 5.7551 (5) Å | θ = 2.8–27.5° |
b = 16.1579 (19) Å | µ = 0.09 mm−1 |
c = 17.1230 (19) Å | T = 120 K |
β = 95.464 (8)° | Block, colourless |
V = 1585.0 (3) Å3 | 0.32 × 0.30 × 0.26 mm |
Z = 4 | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 3639 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 2621 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.058 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ϕ & ω scans | h = −7→7 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −20→20 |
Tmin = 0.971, Tmax = 0.976 | l = −22→22 |
22681 measured reflections | |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0391P)2 + 0.5921P] where P = (Fo2 + 2Fc2)/3 |
3639 reflections | (Δ/σ)max = 0.001 |
208 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
C14H16N+·C4H3O4− | V = 1585.0 (3) Å3 |
Mr = 313.34 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.7551 (5) Å | µ = 0.09 mm−1 |
b = 16.1579 (19) Å | T = 120 K |
c = 17.1230 (19) Å | 0.32 × 0.30 × 0.26 mm |
β = 95.464 (8)° | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 3639 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2621 reflections with I > 2σ(I) |
Tmin = 0.971, Tmax = 0.976 | Rint = 0.058 |
22681 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.18 e Å−3 |
3639 reflections | Δρmin = −0.25 e Å−3 |
208 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.5366 (2) | 0.29720 (8) | 0.32397 (7) | 0.0191 (3) | |
H1A | 0.3868 | 0.2977 | 0.3365 | 0.023* | |
H1B | 0.6253 | 0.2914 | 0.3695 | 0.023* | |
C17 | 0.5742 (3) | 0.22299 (10) | 0.27401 (9) | 0.0257 (4) | |
H17A | 0.7414 | 0.2192 | 0.2652 | 0.031* | |
H17B | 0.4832 | 0.2296 | 0.2223 | 0.031* | |
C11 | 0.5009 (3) | 0.14446 (10) | 0.31198 (9) | 0.0228 (3) | |
C12 | 0.6548 (3) | 0.10306 (10) | 0.36598 (10) | 0.0271 (4) | |
H12 | 0.8073 | 0.1246 | 0.3788 | 0.033* | |
C13 | 0.5884 (3) | 0.03080 (11) | 0.40131 (11) | 0.0336 (4) | |
H13 | 0.6947 | 0.0033 | 0.4385 | 0.040* | |
C14 | 0.3674 (3) | −0.00141 (11) | 0.38249 (11) | 0.0344 (4) | |
H14 | 0.3218 | −0.0510 | 0.4066 | 0.041* | |
C15 | 0.2136 (3) | 0.03868 (11) | 0.32862 (11) | 0.0343 (4) | |
H15 | 0.0623 | 0.0164 | 0.3153 | 0.041* | |
C16 | 0.2788 (3) | 0.11154 (11) | 0.29361 (10) | 0.0283 (4) | |
H16 | 0.1712 | 0.1391 | 0.2569 | 0.034* | |
C27 | 0.5999 (3) | 0.37606 (10) | 0.28506 (9) | 0.0225 (3) | |
H27A | 0.5025 | 0.3821 | 0.2345 | 0.027* | |
H27B | 0.7653 | 0.3736 | 0.2738 | 0.027* | |
C21 | 0.5641 (3) | 0.45008 (10) | 0.33596 (9) | 0.0209 (3) | |
C22 | 0.7442 (3) | 0.47900 (10) | 0.38888 (9) | 0.0251 (4) | |
H22 | 0.8900 | 0.4510 | 0.3940 | 0.030* | |
C23 | 0.7124 (3) | 0.54831 (11) | 0.43418 (10) | 0.0318 (4) | |
H23 | 0.8362 | 0.5677 | 0.4702 | 0.038* | |
C24 | 0.5000 (3) | 0.58949 (11) | 0.42711 (11) | 0.0336 (4) | |
H24 | 0.4783 | 0.6370 | 0.4583 | 0.040* | |
C25 | 0.3199 (3) | 0.56126 (11) | 0.37469 (11) | 0.0323 (4) | |
H25 | 0.1746 | 0.5896 | 0.3696 | 0.039* | |
C26 | 0.3511 (3) | 0.49167 (10) | 0.32962 (10) | 0.0267 (4) | |
H26 | 0.2262 | 0.4721 | 0.2941 | 0.032* | |
C31 | 0.0391 (3) | 0.19287 (11) | 0.62431 (10) | 0.0265 (4) | |
C32 | 0.2231 (3) | 0.19375 (10) | 0.56848 (9) | 0.0235 (3) | |
H32 | 0.3669 | 0.1696 | 0.5888 | 0.028* | |
C33 | 0.2229 (3) | 0.22217 (10) | 0.49537 (9) | 0.0224 (3) | |
H33 | 0.3650 | 0.2140 | 0.4724 | 0.027* | |
C34 | 0.0356 (3) | 0.26483 (10) | 0.44335 (9) | 0.0204 (3) | |
O31 | −0.17349 (18) | 0.21716 (8) | 0.60052 (7) | 0.0306 (3) | |
H31 | −0.1673 | 0.2373 | 0.5466 | 0.046* | |
O32 | 0.0899 (2) | 0.16877 (10) | 0.69127 (7) | 0.0472 (4) | |
O33 | 0.08704 (18) | 0.29195 (7) | 0.37947 (6) | 0.0273 (3) | |
O34 | −0.17021 (17) | 0.27045 (7) | 0.46603 (6) | 0.0243 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0174 (6) | 0.0214 (7) | 0.0185 (6) | 0.0016 (5) | 0.0018 (5) | 0.0008 (5) |
C17 | 0.0295 (9) | 0.0243 (9) | 0.0242 (8) | 0.0014 (7) | 0.0076 (7) | −0.0042 (7) |
C11 | 0.0237 (8) | 0.0210 (8) | 0.0243 (8) | 0.0021 (6) | 0.0055 (6) | −0.0056 (6) |
C12 | 0.0249 (8) | 0.0245 (9) | 0.0319 (9) | 0.0000 (7) | 0.0021 (7) | −0.0053 (7) |
C13 | 0.0409 (10) | 0.0260 (10) | 0.0334 (10) | 0.0036 (8) | 0.0011 (8) | −0.0004 (8) |
C14 | 0.0419 (10) | 0.0231 (9) | 0.0404 (10) | −0.0051 (8) | 0.0161 (8) | −0.0040 (8) |
C15 | 0.0255 (9) | 0.0310 (10) | 0.0475 (11) | −0.0050 (7) | 0.0084 (8) | −0.0142 (9) |
C16 | 0.0255 (8) | 0.0273 (9) | 0.0318 (9) | 0.0038 (7) | 0.0012 (7) | −0.0075 (7) |
C27 | 0.0233 (8) | 0.0231 (8) | 0.0213 (8) | −0.0026 (6) | 0.0030 (6) | 0.0021 (6) |
C21 | 0.0213 (8) | 0.0196 (8) | 0.0220 (8) | −0.0013 (6) | 0.0036 (6) | 0.0034 (6) |
C22 | 0.0216 (8) | 0.0251 (9) | 0.0283 (9) | 0.0000 (7) | 0.0008 (7) | 0.0002 (7) |
C23 | 0.0290 (9) | 0.0314 (10) | 0.0346 (9) | −0.0048 (7) | 0.0011 (7) | −0.0053 (8) |
C24 | 0.0376 (10) | 0.0213 (9) | 0.0440 (10) | −0.0028 (7) | 0.0145 (8) | −0.0061 (8) |
C25 | 0.0245 (9) | 0.0249 (9) | 0.0488 (11) | 0.0047 (7) | 0.0105 (8) | 0.0041 (8) |
C26 | 0.0215 (8) | 0.0253 (9) | 0.0330 (9) | −0.0007 (7) | 0.0012 (7) | 0.0043 (7) |
C31 | 0.0213 (8) | 0.0328 (10) | 0.0252 (8) | −0.0006 (7) | 0.0012 (6) | 0.0032 (7) |
C32 | 0.0166 (7) | 0.0270 (9) | 0.0267 (8) | 0.0030 (6) | 0.0003 (6) | 0.0017 (7) |
C33 | 0.0163 (7) | 0.0272 (9) | 0.0242 (8) | 0.0031 (6) | 0.0038 (6) | 0.0000 (7) |
C34 | 0.0177 (7) | 0.0206 (8) | 0.0227 (8) | 0.0004 (6) | 0.0011 (6) | −0.0037 (6) |
O31 | 0.0203 (6) | 0.0458 (8) | 0.0264 (6) | 0.0057 (5) | 0.0057 (5) | 0.0092 (5) |
O32 | 0.0293 (7) | 0.0836 (11) | 0.0290 (7) | 0.0082 (7) | 0.0044 (5) | 0.0217 (7) |
O33 | 0.0230 (6) | 0.0354 (7) | 0.0239 (6) | 0.0043 (5) | 0.0050 (5) | 0.0064 (5) |
O34 | 0.0170 (5) | 0.0314 (7) | 0.0245 (6) | 0.0032 (5) | 0.0025 (4) | 0.0019 (5) |
Geometric parameters (Å, º) top
N1—C27 | 1.4987 (19) | C21—C26 | 1.393 (2) |
N1—C17 | 1.501 (2) | C22—C23 | 1.384 (2) |
N1—H1A | 0.9085 | C22—H22 | 0.9500 |
N1—H1B | 0.8954 | C23—C24 | 1.387 (2) |
C17—C11 | 1.504 (2) | C23—H23 | 0.9500 |
C17—H17A | 0.9900 | C24—C25 | 1.382 (3) |
C17—H17B | 0.9900 | C24—H24 | 0.9500 |
C11—C12 | 1.390 (2) | C25—C26 | 1.385 (2) |
C11—C16 | 1.393 (2) | C25—H25 | 0.9500 |
C12—C13 | 1.385 (2) | C26—H26 | 0.9500 |
C12—H12 | 0.9500 | C31—O31 | 1.3120 (19) |
C13—C14 | 1.384 (3) | C31—O32 | 1.220 (2) |
C13—H13 | 0.9500 | C31—C32 | 1.493 (2) |
C14—C15 | 1.378 (3) | C32—C33 | 1.333 (2) |
C14—H14 | 0.9500 | C32—H32 | 0.9500 |
C15—C16 | 1.389 (3) | C33—C34 | 1.499 (2) |
C15—H15 | 0.9500 | C33—H33 | 0.9500 |
C16—H16 | 0.9500 | C34—O33 | 1.2402 (18) |
C27—C21 | 1.506 (2) | C34—O34 | 1.2842 (18) |
C27—H27A | 0.9900 | O31—H31 | 0.9822 |
C27—H27B | 0.9900 | O34—H31 | 1.4792 |
C21—C22 | 1.391 (2) | | |
| | | |
C27—N1—C17 | 111.82 (11) | C21—C27—H27B | 109.3 |
C27—N1—H1A | 112.0 | H27A—C27—H27B | 108.0 |
C17—N1—H1A | 109.5 | C22—C21—C26 | 118.97 (15) |
C27—N1—H1B | 109.5 | C22—C21—C27 | 120.64 (14) |
C17—N1—H1B | 108.1 | C26—C21—C27 | 120.37 (14) |
H1A—N1—H1B | 105.6 | C23—C22—C21 | 120.44 (15) |
N1—C17—C11 | 111.48 (12) | C23—C22—H22 | 119.8 |
N1—C17—H17A | 109.3 | C21—C22—H22 | 119.8 |
C11—C17—H17A | 109.3 | C22—C23—C24 | 120.12 (16) |
N1—C17—H17B | 109.3 | C22—C23—H23 | 119.9 |
C11—C17—H17B | 109.3 | C24—C23—H23 | 119.9 |
H17A—C17—H17B | 108.0 | C25—C24—C23 | 119.90 (17) |
C12—C11—C16 | 118.67 (16) | C25—C24—H24 | 120.0 |
C12—C11—C17 | 120.42 (14) | C23—C24—H24 | 120.0 |
C16—C11—C17 | 120.91 (15) | C24—C25—C26 | 120.04 (16) |
C13—C12—C11 | 120.74 (16) | C24—C25—H25 | 120.0 |
C13—C12—H12 | 119.6 | C26—C25—H25 | 120.0 |
C11—C12—H12 | 119.6 | C25—C26—C21 | 120.52 (16) |
C14—C13—C12 | 120.08 (17) | C25—C26—H26 | 119.7 |
C14—C13—H13 | 120.0 | C21—C26—H26 | 119.7 |
C12—C13—H13 | 120.0 | O32—C31—O31 | 121.36 (15) |
C15—C14—C13 | 119.77 (17) | O32—C31—C32 | 118.92 (15) |
C15—C14—H14 | 120.1 | O31—C31—C32 | 119.71 (14) |
C13—C14—H14 | 120.1 | C33—C32—C31 | 131.85 (15) |
C14—C15—C16 | 120.33 (16) | C33—C32—H32 | 114.1 |
C14—C15—H15 | 119.8 | C31—C32—H32 | 114.1 |
C16—C15—H15 | 119.8 | C32—C33—C34 | 130.74 (14) |
C15—C16—C11 | 120.40 (16) | C32—C33—H33 | 114.6 |
C15—C16—H16 | 119.8 | C34—C33—H33 | 114.6 |
C11—C16—H16 | 119.8 | O33—C34—O34 | 123.11 (14) |
N1—C27—C21 | 111.45 (12) | O33—C34—C33 | 117.90 (13) |
N1—C27—H27A | 109.3 | O34—C34—C33 | 118.98 (14) |
C21—C27—H27A | 109.3 | C31—O31—H31 | 105.9 |
N1—C27—H27B | 109.3 | C34—O34—H31 | 109.1 |
| | | |
C27—N1—C17—C11 | −177.63 (12) | C26—C21—C22—C23 | −0.4 (2) |
N1—C17—C11—C12 | −85.51 (18) | C27—C21—C22—C23 | 178.40 (15) |
N1—C17—C11—C16 | 94.80 (17) | C21—C22—C23—C24 | 0.0 (3) |
C16—C11—C12—C13 | −0.4 (2) | C22—C23—C24—C25 | 0.0 (3) |
C17—C11—C12—C13 | 179.86 (15) | C23—C24—C25—C26 | 0.4 (3) |
C11—C12—C13—C14 | 0.6 (3) | C24—C25—C26—C21 | −0.7 (3) |
C12—C13—C14—C15 | −0.1 (3) | C22—C21—C26—C25 | 0.7 (2) |
C13—C14—C15—C16 | −0.5 (3) | C27—C21—C26—C25 | −178.07 (15) |
C14—C15—C16—C11 | 0.6 (3) | C31—C32—C33—C34 | 0.9 (3) |
C12—C11—C16—C15 | −0.2 (2) | C33—C32—C31—O31 | 6.5 (3) |
C17—C11—C16—C15 | 179.54 (15) | C33—C32—C31—O32 | −174.08 (19) |
C17—N1—C27—C21 | −179.37 (12) | C32—C33—C34—O33 | 173.64 (17) |
N1—C27—C21—C22 | 90.51 (17) | C32—C33—C34—O34 | −7.5 (3) |
N1—C27—C21—C26 | −90.76 (17) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O33 | 0.91 | 1.94 | 2.8412 (16) | 171 |
N1—H1B···O34i | 0.90 | 1.96 | 2.8582 (16) | 175 |
O31—H31···O34 | 0.98 | 1.48 | 2.4603 (16) | 177 |
C27—H27A···O32ii | 0.99 | 2.55 | 3.290 (2) | 131 |
C27—H27B···O32iii | 0.99 | 2.54 | 3.452 (2) | 153 |
Symmetry codes: (i) x+1, y, z; (ii) x, −y+1/2, z−1/2; (iii) x+1, −y+1/2, z−1/2. |
(II) Bis(dibenzylamino)methane
top
Crystal data top
C29H30N2 | F(000) = 1744 |
Mr = 406.55 | Dx = 1.156 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 5366 reflections |
a = 25.548 (6) Å | θ = 2.8–27.5° |
b = 12.9426 (16) Å | µ = 0.07 mm−1 |
c = 18.555 (3) Å | T = 120 K |
β = 130.428 (11)° | Block, colourless |
V = 4670.4 (16) Å3 | 0.42 × 0.24 × 0.23 mm |
Z = 8 | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 5366 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 3223 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ϕ & ω scans | h = −33→33 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −16→16 |
Tmin = 0.972, Tmax = 0.985 | l = −24→24 |
18316 measured reflections | |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0482P)2 + 1.028P] where P = (Fo2 + 2Fc2)/3 |
5366 reflections | (Δ/σ)max = 0.001 |
281 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
Crystal data top
C29H30N2 | V = 4670.4 (16) Å3 |
Mr = 406.55 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 25.548 (6) Å | µ = 0.07 mm−1 |
b = 12.9426 (16) Å | T = 120 K |
c = 18.555 (3) Å | 0.42 × 0.24 × 0.23 mm |
β = 130.428 (11)° | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 5366 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3223 reflections with I > 2σ(I) |
Tmin = 0.972, Tmax = 0.985 | Rint = 0.055 |
18316 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.25 e Å−3 |
5366 reflections | Δρmin = −0.23 e Å−3 |
281 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.5000 | 0.50145 (17) | 0.2500 | 0.0307 (5) | |
H1A | 0.5412 | 0.4566 | 0.2885 | 0.037* | 0.50 |
H1B | 0.4588 | 0.4566 | 0.2115 | 0.037* | 0.50 |
N1 | 0.49758 (6) | 0.56599 (9) | 0.31241 (9) | 0.0276 (3) | |
C117 | 0.56415 (8) | 0.61702 (12) | 0.38317 (11) | 0.0320 (4) | |
H11A | 0.5818 | 0.6415 | 0.3519 | 0.038* | |
H11B | 0.5973 | 0.5658 | 0.4319 | 0.038* | |
C111 | 0.56044 (8) | 0.70735 (12) | 0.43112 (10) | 0.0266 (4) | |
C112 | 0.50511 (8) | 0.77576 (12) | 0.38141 (11) | 0.0298 (4) | |
H112 | 0.4674 | 0.7637 | 0.3163 | 0.036* | |
C113 | 0.50456 (8) | 0.86085 (13) | 0.42574 (11) | 0.0335 (4) | |
H113 | 0.4661 | 0.9061 | 0.3911 | 0.040* | |
C114 | 0.55938 (9) | 0.88093 (13) | 0.51999 (12) | 0.0349 (4) | |
H114 | 0.5590 | 0.9402 | 0.5499 | 0.042* | |
C115 | 0.61455 (9) | 0.81410 (13) | 0.57019 (11) | 0.0362 (4) | |
H115 | 0.6526 | 0.8275 | 0.6349 | 0.043* | |
C116 | 0.61463 (8) | 0.72733 (13) | 0.52643 (11) | 0.0337 (4) | |
H116 | 0.6523 | 0.6807 | 0.5621 | 0.040* | |
C127 | 0.47741 (8) | 0.50487 (13) | 0.35771 (11) | 0.0315 (4) | |
H12A | 0.4843 | 0.5469 | 0.4078 | 0.038* | |
H12B | 0.5076 | 0.4435 | 0.3882 | 0.038* | |
C121 | 0.40329 (8) | 0.46988 (12) | 0.28810 (10) | 0.0276 (4) | |
C122 | 0.35101 (8) | 0.54050 (13) | 0.22746 (11) | 0.0315 (4) | |
H122 | 0.3622 | 0.6111 | 0.2298 | 0.038* | |
C123 | 0.28296 (9) | 0.50947 (14) | 0.16380 (11) | 0.0367 (4) | |
H123 | 0.2479 | 0.5587 | 0.1229 | 0.044* | |
C124 | 0.26594 (9) | 0.40668 (14) | 0.15969 (12) | 0.0373 (4) | |
H124 | 0.2193 | 0.3851 | 0.1160 | 0.045* | |
C125 | 0.31716 (9) | 0.33627 (14) | 0.21932 (12) | 0.0398 (4) | |
H125 | 0.3058 | 0.2657 | 0.2167 | 0.048* | |
C126 | 0.38526 (9) | 0.36730 (12) | 0.28316 (12) | 0.0343 (4) | |
H126 | 0.4201 | 0.3178 | 0.3241 | 0.041* | |
C2 | 0.5000 | 0.97739 (17) | 0.7500 | 0.0296 (5) | |
H2A | 0.4848 | 1.0223 | 0.7765 | 0.035* | 0.50 |
H2B | 0.5152 | 1.0223 | 0.7235 | 0.035* | 0.50 |
N2 | 0.44225 (6) | 0.91302 (10) | 0.67439 (9) | 0.0279 (3) | |
C217 | 0.46209 (8) | 0.85271 (12) | 0.62851 (12) | 0.0325 (4) | |
H21A | 0.5069 | 0.8190 | 0.6780 | 0.039* | |
H21B | 0.4684 | 0.9004 | 0.5929 | 0.039* | |
C211 | 0.41026 (8) | 0.77066 (12) | 0.56140 (11) | 0.0287 (4) | |
C212 | 0.36882 (8) | 0.72257 (12) | 0.57501 (11) | 0.0342 (4) | |
H212 | 0.3710 | 0.7436 | 0.6259 | 0.041* | |
C213 | 0.32439 (9) | 0.64434 (13) | 0.51542 (13) | 0.0443 (5) | |
H213 | 0.2963 | 0.6121 | 0.5257 | 0.053* | |
C214 | 0.32050 (10) | 0.61278 (15) | 0.44124 (13) | 0.0492 (5) | |
H214 | 0.2901 | 0.5586 | 0.4007 | 0.059* | |
C215 | 0.36114 (10) | 0.66048 (15) | 0.42603 (12) | 0.0469 (5) | |
H215 | 0.3587 | 0.6392 | 0.3749 | 0.056* | |
C216 | 0.40538 (9) | 0.73944 (13) | 0.48572 (11) | 0.0366 (4) | |
H216 | 0.4327 | 0.7726 | 0.4746 | 0.044* | |
C227 | 0.38256 (8) | 0.97856 (12) | 0.60460 (11) | 0.0304 (4) | |
H22A | 0.3456 | 0.9347 | 0.5514 | 0.036* | |
H22B | 0.3959 | 1.0292 | 0.5790 | 0.036* | |
C221 | 0.35458 (7) | 1.03623 (12) | 0.64375 (10) | 0.0273 (4) | |
C222 | 0.35201 (8) | 0.99267 (13) | 0.71004 (11) | 0.0311 (4) | |
H222 | 0.3692 | 0.9247 | 0.7326 | 0.037* | |
C223 | 0.32499 (8) | 1.04652 (14) | 0.74361 (11) | 0.0370 (4) | |
H223 | 0.3245 | 1.0160 | 0.7897 | 0.044* | |
C224 | 0.29869 (8) | 1.14460 (14) | 0.71023 (12) | 0.0400 (4) | |
H224 | 0.2800 | 1.1817 | 0.7331 | 0.048* | |
C225 | 0.29975 (8) | 1.18829 (13) | 0.64341 (12) | 0.0397 (4) | |
H225 | 0.2809 | 1.2552 | 0.6194 | 0.048* | |
C226 | 0.32808 (8) | 1.13546 (12) | 0.61092 (11) | 0.0335 (4) | |
H226 | 0.3295 | 1.1671 | 0.5660 | 0.040* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0330 (13) | 0.0289 (12) | 0.0330 (12) | 0.000 | 0.0227 (11) | 0.000 |
N1 | 0.0252 (7) | 0.0311 (7) | 0.0289 (7) | −0.0022 (6) | 0.0187 (6) | −0.0009 (6) |
C117 | 0.0220 (8) | 0.0381 (9) | 0.0330 (9) | 0.0009 (7) | 0.0166 (8) | 0.0001 (7) |
C111 | 0.0227 (8) | 0.0317 (9) | 0.0269 (8) | −0.0009 (7) | 0.0167 (7) | 0.0035 (7) |
C112 | 0.0230 (8) | 0.0338 (9) | 0.0250 (8) | −0.0001 (7) | 0.0122 (7) | 0.0026 (7) |
C113 | 0.0281 (9) | 0.0334 (9) | 0.0348 (9) | 0.0033 (7) | 0.0185 (8) | 0.0047 (7) |
C114 | 0.0406 (10) | 0.0341 (9) | 0.0374 (10) | −0.0026 (8) | 0.0285 (9) | −0.0011 (8) |
C115 | 0.0333 (10) | 0.0449 (10) | 0.0226 (8) | −0.0055 (8) | 0.0147 (8) | −0.0006 (8) |
C116 | 0.0256 (9) | 0.0411 (10) | 0.0271 (8) | 0.0046 (8) | 0.0137 (8) | 0.0061 (8) |
C127 | 0.0295 (9) | 0.0349 (9) | 0.0304 (9) | 0.0034 (8) | 0.0196 (8) | 0.0055 (7) |
C121 | 0.0309 (9) | 0.0320 (9) | 0.0283 (8) | −0.0004 (7) | 0.0230 (8) | 0.0006 (7) |
C122 | 0.0319 (9) | 0.0295 (9) | 0.0335 (9) | 0.0004 (8) | 0.0214 (8) | 0.0009 (7) |
C123 | 0.0315 (9) | 0.0455 (11) | 0.0323 (9) | 0.0034 (8) | 0.0203 (8) | 0.0062 (8) |
C124 | 0.0327 (9) | 0.0517 (11) | 0.0314 (9) | −0.0101 (9) | 0.0226 (8) | −0.0017 (8) |
C125 | 0.0459 (11) | 0.0368 (10) | 0.0442 (10) | −0.0102 (9) | 0.0325 (10) | −0.0015 (8) |
C126 | 0.0387 (10) | 0.0325 (9) | 0.0395 (10) | 0.0026 (8) | 0.0289 (9) | 0.0055 (8) |
C2 | 0.0235 (12) | 0.0298 (12) | 0.0308 (12) | 0.000 | 0.0156 (11) | 0.000 |
N2 | 0.0199 (7) | 0.0326 (7) | 0.0279 (7) | 0.0012 (6) | 0.0139 (6) | −0.0042 (6) |
C217 | 0.0291 (9) | 0.0361 (9) | 0.0375 (9) | −0.0005 (8) | 0.0239 (8) | −0.0032 (8) |
C211 | 0.0266 (8) | 0.0290 (9) | 0.0289 (8) | 0.0047 (7) | 0.0172 (7) | 0.0029 (7) |
C212 | 0.0328 (9) | 0.0359 (9) | 0.0357 (9) | −0.0023 (8) | 0.0230 (8) | −0.0011 (8) |
C213 | 0.0384 (11) | 0.0351 (10) | 0.0556 (12) | −0.0058 (9) | 0.0287 (10) | −0.0014 (9) |
C214 | 0.0339 (10) | 0.0385 (11) | 0.0467 (11) | −0.0010 (9) | 0.0135 (9) | −0.0123 (9) |
C215 | 0.0448 (11) | 0.0533 (12) | 0.0318 (10) | 0.0126 (10) | 0.0200 (9) | −0.0065 (9) |
C216 | 0.0383 (10) | 0.0402 (10) | 0.0351 (9) | 0.0067 (8) | 0.0255 (8) | 0.0044 (8) |
C227 | 0.0248 (9) | 0.0371 (9) | 0.0262 (8) | 0.0027 (7) | 0.0151 (7) | 0.0019 (7) |
C221 | 0.0185 (8) | 0.0305 (9) | 0.0259 (8) | −0.0040 (7) | 0.0112 (7) | −0.0049 (7) |
C222 | 0.0244 (8) | 0.0333 (9) | 0.0320 (9) | 0.0026 (7) | 0.0167 (8) | 0.0032 (7) |
C223 | 0.0261 (9) | 0.0512 (11) | 0.0315 (9) | −0.0004 (8) | 0.0178 (8) | −0.0035 (8) |
C224 | 0.0234 (9) | 0.0495 (11) | 0.0363 (10) | 0.0019 (8) | 0.0146 (8) | −0.0115 (9) |
C225 | 0.0287 (9) | 0.0291 (9) | 0.0440 (10) | 0.0036 (8) | 0.0158 (9) | −0.0046 (8) |
C226 | 0.0282 (9) | 0.0298 (9) | 0.0317 (9) | −0.0011 (7) | 0.0146 (8) | 0.0003 (7) |
Geometric parameters (Å, º) top
C1—N1i | 1.4612 (17) | C2—N2 | 1.4678 (17) |
C1—N1 | 1.4612 (17) | C2—N2ii | 1.4678 (17) |
C1—H1A | 0.9900 | C2—H2A | 0.9900 |
C1—H1B | 0.9900 | C2—H2B | 0.9900 |
N1—C117 | 1.4685 (19) | N2—C217 | 1.4663 (19) |
N1—C127 | 1.4694 (19) | N2—C227 | 1.4700 (19) |
C117—C111 | 1.509 (2) | C217—C211 | 1.514 (2) |
C117—H11A | 0.9900 | C217—H21A | 0.9900 |
C117—H11B | 0.9900 | C217—H21B | 0.9900 |
C111—C116 | 1.391 (2) | C211—C212 | 1.385 (2) |
C111—C112 | 1.393 (2) | C211—C216 | 1.387 (2) |
C112—C113 | 1.380 (2) | C212—C213 | 1.381 (2) |
C112—H112 | 0.9500 | C212—H212 | 0.9500 |
C113—C114 | 1.382 (2) | C213—C214 | 1.376 (3) |
C113—H113 | 0.9500 | C213—H213 | 0.9500 |
C114—C115 | 1.378 (2) | C214—C215 | 1.385 (3) |
C114—H114 | 0.9500 | C214—H214 | 0.9500 |
C115—C116 | 1.387 (2) | C215—C216 | 1.387 (2) |
C115—H115 | 0.9500 | C215—H215 | 0.9500 |
C116—H116 | 0.9500 | C216—H216 | 0.9500 |
C127—C121 | 1.512 (2) | C227—C221 | 1.506 (2) |
C127—H12A | 0.9900 | C227—H22A | 0.9900 |
C127—H12B | 0.9900 | C227—H22B | 0.9900 |
C121—C126 | 1.389 (2) | C221—C222 | 1.393 (2) |
C121—C122 | 1.391 (2) | C221—C226 | 1.394 (2) |
C122—C123 | 1.384 (2) | C222—C223 | 1.381 (2) |
C122—H122 | 0.9500 | C222—H222 | 0.9500 |
C123—C124 | 1.386 (2) | C223—C224 | 1.381 (2) |
C123—H123 | 0.9500 | C223—H223 | 0.9500 |
C124—C125 | 1.374 (2) | C224—C225 | 1.379 (2) |
C124—H124 | 0.9500 | C224—H224 | 0.9500 |
C125—C126 | 1.385 (2) | C225—C226 | 1.386 (2) |
C125—H125 | 0.9500 | C225—H225 | 0.9500 |
C126—H126 | 0.9500 | C226—H226 | 0.9500 |
| | | |
N1—C1—N1i | 110.27 (17) | N2—C2—N2ii | 110.83 (17) |
N1i—C1—H1A | 109.6 | N2—C2—H2A | 109.5 |
N1—C1—H1A | 109.6 | N2ii—C2—H2A | 109.5 |
N1i—C1—H1B | 109.6 | N2—C2—H2B | 109.5 |
N1—C1—H1B | 109.6 | N2ii—C2—H2B | 109.5 |
H1A—C1—H1B | 108.1 | H2A—C2—H2B | 108.1 |
C1—N1—C117 | 110.24 (11) | C217—N2—C2 | 110.21 (11) |
C1—N1—C127 | 110.87 (12) | C217—N2—C227 | 110.33 (12) |
C117—N1—C127 | 111.29 (12) | C2—N2—C227 | 109.87 (12) |
N1—C117—C111 | 113.35 (13) | N2—C217—C211 | 113.81 (13) |
N1—C117—H11A | 108.9 | N2—C217—H21A | 108.8 |
C111—C117—H11A | 108.9 | C211—C217—H21A | 108.8 |
N1—C117—H11B | 108.9 | N2—C217—H21B | 108.8 |
C111—C117—H11B | 108.9 | C211—C217—H21B | 108.8 |
H11A—C117—H11B | 107.7 | H21A—C217—H21B | 107.7 |
C116—C111—C112 | 118.00 (15) | C212—C211—C216 | 118.43 (15) |
C116—C111—C117 | 120.15 (14) | C212—C211—C217 | 121.96 (15) |
C112—C111—C117 | 121.78 (14) | C216—C211—C217 | 119.57 (15) |
C113—C112—C111 | 120.70 (14) | C213—C212—C211 | 120.79 (17) |
C113—C112—H112 | 119.7 | C213—C212—H212 | 119.6 |
C111—C112—H112 | 119.7 | C211—C212—H212 | 119.6 |
C112—C113—C114 | 120.70 (16) | C214—C213—C212 | 120.46 (18) |
C112—C113—H113 | 119.6 | C214—C213—H213 | 119.8 |
C114—C113—H113 | 119.6 | C212—C213—H213 | 119.8 |
C115—C114—C113 | 119.34 (16) | C213—C214—C215 | 119.60 (17) |
C115—C114—H114 | 120.3 | C213—C214—H214 | 120.2 |
C113—C114—H114 | 120.3 | C215—C214—H214 | 120.2 |
C114—C115—C116 | 120.12 (15) | C214—C215—C216 | 119.72 (17) |
C114—C115—H115 | 119.9 | C214—C215—H215 | 120.1 |
C116—C115—H115 | 119.9 | C216—C215—H215 | 120.1 |
C115—C116—C111 | 121.11 (15) | C211—C216—C215 | 120.98 (17) |
C115—C116—H116 | 119.4 | C211—C216—H216 | 119.5 |
C111—C116—H116 | 119.4 | C215—C216—H216 | 119.5 |
N1—C127—C121 | 112.46 (12) | N2—C227—C221 | 114.00 (12) |
N1—C127—H12A | 109.1 | N2—C227—H22A | 108.8 |
C121—C127—H12A | 109.1 | C221—C227—H22A | 108.8 |
N1—C127—H12B | 109.1 | N2—C227—H22B | 108.8 |
C121—C127—H12B | 109.1 | C221—C227—H22B | 108.8 |
H12A—C127—H12B | 107.8 | H22A—C227—H22B | 107.6 |
C126—C121—C122 | 118.12 (15) | C222—C221—C226 | 118.11 (15) |
C126—C121—C127 | 121.38 (14) | C222—C221—C227 | 122.29 (14) |
C122—C121—C127 | 120.50 (14) | C226—C221—C227 | 119.57 (14) |
C123—C122—C121 | 121.02 (16) | C223—C222—C221 | 121.17 (15) |
C123—C122—H122 | 119.5 | C223—C222—H222 | 119.4 |
C121—C122—H122 | 119.5 | C221—C222—H222 | 119.4 |
C122—C123—C124 | 120.06 (16) | C224—C223—C222 | 120.12 (17) |
C122—C123—H123 | 120.0 | C224—C223—H223 | 119.9 |
C124—C123—H123 | 120.0 | C222—C223—H223 | 119.9 |
C125—C124—C123 | 119.42 (16) | C225—C224—C223 | 119.51 (17) |
C125—C124—H124 | 120.3 | C225—C224—H224 | 120.2 |
C123—C124—H124 | 120.3 | C223—C224—H224 | 120.2 |
C124—C125—C126 | 120.55 (16) | C224—C225—C226 | 120.61 (16) |
C124—C125—H125 | 119.7 | C224—C225—H225 | 119.7 |
C126—C125—H125 | 119.7 | C226—C225—H225 | 119.7 |
C125—C126—C121 | 120.83 (16) | C225—C226—C221 | 120.45 (16) |
C125—C126—H126 | 119.6 | C225—C226—H226 | 119.8 |
C121—C126—H126 | 119.6 | C221—C226—H226 | 119.8 |
| | | |
N1i—C1—N1—C117 | −70.90 (10) | N2ii—C2—N2—C217 | −64.21 (10) |
N1i—C1—N1—C127 | 165.41 (12) | N2ii—C2—N2—C227 | 174.01 (12) |
C1—N1—C117—C111 | 163.10 (13) | C2—N2—C217—C211 | 169.98 (13) |
C127—N1—C117—C111 | −73.45 (16) | C227—N2—C217—C211 | −68.51 (17) |
N1—C117—C111—C116 | 143.96 (15) | N2—C217—C211—C212 | −29.9 (2) |
N1—C117—C111—C112 | −39.3 (2) | N2—C217—C211—C216 | 152.47 (14) |
C116—C111—C112—C113 | 0.2 (2) | C216—C211—C212—C213 | 0.9 (2) |
C117—C111—C112—C113 | −176.60 (15) | C217—C211—C212—C213 | −176.75 (15) |
C111—C112—C113—C114 | 1.1 (2) | C211—C212—C213—C214 | 0.0 (3) |
C112—C113—C114—C115 | −1.0 (2) | C212—C213—C214—C215 | −0.5 (3) |
C113—C114—C115—C116 | −0.4 (2) | C213—C214—C215—C216 | 0.1 (3) |
C114—C115—C116—C111 | 1.7 (3) | C212—C211—C216—C215 | −1.3 (2) |
C112—C111—C116—C115 | −1.6 (2) | C217—C211—C216—C215 | 176.41 (15) |
C117—C111—C116—C115 | 175.26 (15) | C214—C215—C216—C211 | 0.8 (3) |
C1—N1—C127—C121 | −68.89 (15) | C217—N2—C227—C221 | 174.78 (13) |
C117—N1—C127—C121 | 168.02 (13) | C2—N2—C227—C221 | −63.51 (15) |
N1—C127—C121—C126 | 129.53 (15) | N2—C227—C221—C222 | −37.5 (2) |
N1—C127—C121—C122 | −50.98 (19) | N2—C227—C221—C226 | 144.65 (14) |
C126—C121—C122—C123 | −0.2 (2) | C226—C221—C222—C223 | −1.0 (2) |
C127—C121—C122—C123 | −179.67 (14) | C227—C221—C222—C223 | −178.85 (14) |
C121—C122—C123—C124 | 0.0 (2) | C221—C222—C223—C224 | 1.2 (2) |
C122—C123—C124—C125 | 0.1 (3) | C222—C223—C224—C225 | −0.1 (2) |
C123—C124—C125—C126 | 0.1 (3) | C223—C224—C225—C226 | −1.2 (2) |
C124—C125—C126—C121 | −0.2 (3) | C224—C225—C226—C221 | 1.5 (2) |
C122—C121—C126—C125 | 0.3 (2) | C222—C221—C226—C225 | −0.4 (2) |
C127—C121—C126—C125 | 179.78 (15) | C227—C221—C226—C225 | 177.57 (14) |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1, y, −z+3/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C14H16N+·C4H3O4− | C29H30N2 |
Mr | 313.34 | 406.55 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, C2/c |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 5.7551 (5), 16.1579 (19), 17.1230 (19) | 25.548 (6), 12.9426 (16), 18.555 (3) |
β (°) | 95.464 (8) | 130.428 (11) |
V (Å3) | 1585.0 (3) | 4670.4 (16) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.07 |
Crystal size (mm) | 0.32 × 0.30 × 0.26 | 0.42 × 0.24 × 0.23 |
|
Data collection |
Diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.971, 0.976 | 0.972, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22681, 3639, 2621 | 18316, 5366, 3223 |
Rint | 0.058 | 0.055 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.110, 1.08 | 0.050, 0.115, 1.01 |
No. of reflections | 3639 | 5366 |
No. of parameters | 208 | 281 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.25 | 0.25, −0.23 |
Selected geometric parameters (Å, º) for (I) topC31—O31 | 1.3120 (19) | C34—O33 | 1.2402 (18) |
C31—O32 | 1.220 (2) | C34—O34 | 1.2842 (18) |
| | | |
C27—N1—C17—C11 | −177.63 (12) | C33—C32—C31—O31 | 6.5 (3) |
N1—C17—C11—C12 | −85.51 (18) | C33—C32—C31—O32 | −174.08 (19) |
C17—N1—C27—C21 | −179.37 (12) | C32—C33—C34—O33 | 173.64 (17) |
N1—C27—C21—C22 | 90.51 (17) | C32—C33—C34—O34 | −7.5 (3) |
C31—C32—C33—C34 | 0.9 (3) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O33 | 0.91 | 1.94 | 2.8412 (16) | 171 |
N1—H1B···O34i | 0.90 | 1.96 | 2.8582 (16) | 175 |
O31—H31···O34 | 0.98 | 1.48 | 2.4603 (16) | 177 |
C27—H27A···O32ii | 0.99 | 2.55 | 3.290 (2) | 131 |
C27—H27B···O32iii | 0.99 | 2.54 | 3.452 (2) | 153 |
Symmetry codes: (i) x+1, y, z; (ii) x, −y+1/2, z−1/2; (iii) x+1, −y+1/2, z−1/2. |
Selected geometric parameters (Å, º) for (II) topC1—N1 | 1.4612 (17) | C2—N2 | 1.4678 (17) |
| | | |
N1—C1—N1i | 110.27 (17) | N2—C2—N2ii | 110.83 (17) |
| | | |
N1i—C1—N1—C117 | −70.90 (10) | N2ii—C2—N2—C217 | −64.21 (10) |
N1i—C1—N1—C127 | 165.41 (12) | N2ii—C2—N2—C227 | 174.01 (12) |
C1—N1—C117—C111 | 163.10 (13) | C2—N2—C217—C211 | 169.98 (13) |
N1—C117—C111—C112 | −39.3 (2) | N2—C217—C211—C212 | −29.9 (2) |
C1—N1—C127—C121 | −68.89 (15) | C2—N2—C227—C221 | −63.51 (15) |
N1—C127—C121—C122 | −50.98 (19) | N2—C227—C221—C222 | −37.5 (2) |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1, y, −z+3/2. |
We report here the molecular and supramolecular structure of dibenzylammonium hydrogen maleate, (I) (Fig. 1), and a redetermination of bis(dibenzylamino)methane, (II) (Fig. 2). Aminoethers are valuable building blocks in organic synthesis as they are important precursors in the synthesis of a wide range of pharmaceutical products (Pinder & Wieringa, 1993; Franchini et al., 2003; Cavalluzzi et al., 2007; Huang et al., 2009). In recent years, a series of selective serotonin (5-HT)-reuptake inhibitor antidepressants (e.g. Fluexetine and Paroxetine) and selective norepinephrine-reuptake inhibitor antidepressants (e.g. Tomoxetine and Viloxazine) have been developed (Pinder & Wieringa, 1993), and several of these compounds contain γ-aminoether functionality, which could be related to their biologivcal activity. Continuing with our current studies on the synthetic utility of benzylamines (Castillo et al., 2009; Abonía et al., 2010), the aminal (II) was isolated as a possible intermediate in a synthetic route to novel γ-aminoether derivatives starting from secondary benzylamines and using a four-component strategy mediated by a Mannich-type reaction (Abonía et al., 2013). In order to confirm the role of (II) in this route, it has been prepared from the reaction of dibenzylamine with paraformaldehyde in acetonitrile and then used to obtain the γ-aminoethers, thus confirming its intermediacy. As a model for the crystallization and characterization of new secondary benzylamine derivatives needed in this synthetic route we have prepared and crystallized the dibenzylammonium hydrogen maleate salt, (I).
The structure of compound (II) has been reported previously using diffraction data collected at 298 K [Cambridge Structural Database (CSD; Allen, 2002) refcode MIKQON (Lu et al., 2007)], but the refinement converged to a rather high R1 value of 0.0794, while the value of wR2 was also quoted as 0.0794, suggesting that unweighted data were used in the final refinements. Alongside the high R index is the rather low precision, with s.u. values for the bonded C—C distances ranging from 0.006 to 0.014 Å, with a mean s.u. of 0.009 Å. Accordingly, we have now taken the opportunity to reinvestigate compound (II) using diffraction data collected at 120 K, resulting in a lower R value and significantly better precision, with s.u. values for the bonded C—C distances typically equal to 0.002 Å.
In the cation of salt (I), the central backbone between atoms C11 and C21 (Fig. 1) is almost planar, as indicated by the relevant torsion angles (Table 1), while the two independent phenyl rings are almost orthogonal to this central plane. The anion of (I) contains a rather short and almost linear O—H···O hydrogen bond, forming an S(7) motif (Bernstein et al., 1995) (Fig. 1 and Table 2); however, despite the short O···O distance, the hydroxy H atom is clearly offset from the mid-point of the O···O vector. The C—O distances in the anion (Table 1) are fully consistent with the location of the hydroxy H atom as deduced from a difference map. Similarly short and nearly linear O—H···O hydrogen bonds are found in the hydrogen maelate salts formed with both 1,2-bis(pyridin-4-yl)ethane and 4,4'-bipyridyl, where the O···O distances are 2.4528 (18) and 2.463 (2) Å, respectively, with O—H···O angles of 178 and 176°, respectively (Bowes et al., 2003); in both of these salts, the H atom in the O—H···O hydrogen bond is clearly offset from the mid-point of the O···O vector, just as in salt (I).
The C—C—C—O torsion angles in the anion of (I) (Table 1) show that both of the carboxyl fragments are rotated slightly away from the plane defined by atoms C31–C34, such that atoms O31 and O34 (those involved in the intra-anion hydrogen bond) are both displaced to one side of the plane of C31–C34, by 0.143 (2) and 0.134 (2) Å, respectively, while atoms O32 and O33 are displaced to the other side of this plane, by 0.117 (2) and 0.115 (2) Å, respectively, corresponding to a disrotatory motion of the carboxyl groups around the C31—C32 and C33—C34 bonds. By contrast, the anions in the salts formed with 1,2-bis(pyridin-4-yl)ethane and 4,4'-bipyridyl are both effectively planar, with maximum deviations from the mean plane of the eight non-H atoms of the anions of 0.041 (2) Å in the former salt and only 0.013 (2) Å in the latter (Bowes et al., 2003).
In the asymmetric unit selected for salt (I) (Fig. 1), the two ions are linked by an N—H···O hydrogen bond (Table 2), while a second N—H···O hydrogen bond links such ion pairs which are related by translation to form a C22(6) (Bernstein et al., 1995) chain running parallel to the [100] direction (Fig. 3). There are also two short intermolecular C—H···O contacts present in the structure of (I) (Table 2). One of these interactions, having a C—H···O angle of 153°, weakly links the chains along [100] into a sheet parallel to (010) and built from S(7) and R76(25) rings (Fig. 4). In the other such interaction, which lies within the (010) sheet, the C—H···O angle is only 131°, so that this contact is probably not structurally significant (Wood et al., 2009). It is notable that the strong and nearly linear O—H···O and N—H···O hydrogen bonds in the structure of (I) all involve the negatively charged O atoms of the carboxylate group, whereas the C—H···O contacts involve the formally neutral O32 atom in the carboxylic acid unit.
Compound (II) crystallizes in the space group C2/c with two independent molecules both lying across twofold rotation axes. Comparison of the unit-cell dimensions at 298 K (Lu et al., 2007) and at 120 K indicates that no phase change has occurred between these two temperatures. The molecules of (II) exhibit no internal symmetry other that the twofold rotation axis and hence they are conformationally chiral, although the space group accommodates equal numbers of the two conformational enantiomers. There is thus considerable flexibility available in the choice of the asymmetric unit, but that selected here contains two independent molecules of the same enantiomeric form, as indicated by the general similarity of corresponding torsion angles (Table 3). On this basis, the type 1 molecule containing atom C1 lies across the rotation axis along (1/2, y, 1/4), while the type 2 molecule containing atom C2 lies across the axis along (1/2, y, 3/4).
In each molecule of (II), the arrangement of the benzyl groups is probably dominated by a combination of steric factors and the mutual repulsion of the lone pairs on the two N atoms, which adopt an anticlinal conformation relative to the N···N direction (Fig. 5). The projections along the N···N vectors, together with the detailed comparison of the relevant torsion angles (Table 3) confirm that there are sufficient conformational differences between the two independent molecules to preclude the possibility of any additional crystallographic symmetry.
Despite the bulk of the dibenzylamino group, the interbond angles (Table 3) at the central atoms C1 and C2 are unexceptional, and the C—N bond lengths involving atoms C1 and C2 are typical of their type [mean value (Allen et al., 1987) 1.469 Å]. Both of the N atom in compound (II) are markedly pyramidal, with sums of interbond angles of 332.4 (2)° at N1 and 330.4 (2)° at N2. Despite this, there are no C—H···N hydrogen bonds within the crystal structure of (II); indeed, there are no direction-specific interactions of any type, as both C—H···π(arene) hydrogen bonds and aromatic π–π stacking interactions are also absent.