Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107037468/fa3097sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107037468/fa3097Isup2.hkl |
CCDC reference: 661818
Compound (I) was prepared by the reaction of AMP with picric acid at room temperature. Aqueous solutions of amitriptyline hydrochloride (0.942 g, 0.03 M) and picric acid (0.689 g, 0.03 M) were mixed and stirred. The mixture yielded a yellow precipitate, which was filtered off, washed thoroughly with water and dried over P2O5 in a vacuum desiccator. Single crystals of (I), suitable for X-ray diffraction, were grown by slow evaporation of a solution in methanol (m.p. 393 K).
The geometric parameters of both disordered components were restrained to be the same by applying soft SADI restraints (SHELXL97; Sheldrick, 1997). In the final stage of refinement, the statistical fractions of the major and minor disordered components were held fixed to the nearest rounded values of 0.6 and 0.4, respectively. All H atoms were placed in geometrically expected positions and refined with riding options, with C(aromatic/sp2)—H = 0.93 Å, C(methyl)—H = 0.96 Å, C(methylene)—H = 0.97 Å and N—H = 0.87 Å, and with Uiso(H) = 1.2Ueq(parent) or 1.5Ueq(C) for methyl groups. In the crystal structure, two (AMP)C(methyl)···O(PCT) short contacts are observed, namely C3···O1- at 2.992 (6) Å and C3'···O7v at 2.932 (6) Å [symmetry code: (v) 1 - x, -y, -z]. However, refinements of the H-atom parameters did not converge well. A search for occurrences of short C(methyl)···O contacts of less than 3.0 Å in the CSD revealed 513 hits. Such short contacts may arise due to the presence of weak intermolecular C(methyl)—H···O interactions, as observed previously in many examples (Schneider et al., 2000; Panda et al., 2001; Domagała et al., 2004; Latip et al., 2005). This appears to be relevant in the present case, as atom C3 is adjacent to the electron-withdrawing group N1+.
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
C20H24N+·C6H2N3O7− | Z = 2 |
Mr = 506.51 | F(000) = 532 |
Triclinic, P1 | Dx = 1.339 Mg m−3 |
Hall symbol: -P 1 | Melting point: 393 K |
a = 10.0649 (11) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.0187 (12) Å | Cell parameters from 8561 reflections |
c = 12.0352 (13) Å | θ = 1.9–27.6° |
α = 73.357 (2)° | µ = 0.10 mm−1 |
β = 79.305 (3)° | T = 301 K |
γ = 85.411 (4)° | Block, yellow |
V = 1256.1 (2) Å3 | 0.48 × 0.31 × 0.26 mm |
Bruker SMART CCD area-detector diffractometer | 4802 independent reflections |
Radiation source: fine-focus sealed tube | 3598 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
ω and ϕ scans | θmax = 26.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.969, Tmax = 0.975 | k = −13→10 |
7632 measured reflections | l = −14→10 |
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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.178 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0969P)2 + 0.2066P] where P = (Fo2 + 2Fc2)/3 |
4802 reflections | (Δ/σ)max < 0.001 |
365 parameters | Δρmax = 0.19 e Å−3 |
15 restraints | Δρmin = −0.30 e Å−3 |
C20H24N+·C6H2N3O7− | γ = 85.411 (4)° |
Mr = 506.51 | V = 1256.1 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.0649 (11) Å | Mo Kα radiation |
b = 11.0187 (12) Å | µ = 0.10 mm−1 |
c = 12.0352 (13) Å | T = 301 K |
α = 73.357 (2)° | 0.48 × 0.31 × 0.26 mm |
β = 79.305 (3)° |
Bruker SMART CCD area-detector diffractometer | 4802 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3598 reflections with I > 2σ(I) |
Tmin = 0.969, Tmax = 0.975 | Rint = 0.040 |
7632 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 15 restraints |
wR(F2) = 0.178 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.19 e Å−3 |
4802 reflections | Δρmin = −0.30 e Å−3 |
365 parameters |
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. Weighted least-squares planes through the starred atoms (Nardelli, Musatti, Domiano & Andreetti Ric·Sci.(1965),15(II—A),807). Equation of the plane: m1*X+m2*Y+m3*Z=d Plane 1 m1 = -0.04409(0.00097) m2 = -0.98689(0.00016) m3 = -0.15524(0.00102) D = -3.63021(0.00213) Atom d s d/s (d/s)**2 C11 * -0.0101 0.0022 - 4.649 21.611 C12 * 0.0069 0.0018 3.733 13.936 C13 * -0.0019 0.0021 - 0.933 0.871 C14 * -0.0062 0.0024 - 2.574 6.628 C15 * 0.0089 0.0031 2.915 8.495 C16 * 0.0058 0.0029 1.964 3.857 C6 0.0391 0.0018 21.286 453.082 C10 - 0.1199 0.0025 - 48.001 2304.069 ============ Sum((d/s)**2) for starred atoms 55.398 Chi-squared at 95% for 3 degrees of freedom: 7.81 The group of atoms deviates significantly from planarity Plane 2 m1 = -0.51021(0.00075) m2 = 0.72828(0.00067) m3 = -0.45749(0.00091) D = 0.65189(0.00664) Atom d s d/s (d/s)**2 C7 * -0.0035 0.0018 - 1.926 3.711 C8 * 0.0043 0.0019 2.270 5.154 C17 * 0.0021 0.0021 0.987 0.974 C18 * 0.0000 0.0024 - 0.004 0.000 C19 * 0.0010 0.0026 0.391 0.153 C20 * -0.0038 0.0022 - 1.720 2.960 C6 - 0.0237 0.0018 - 13.097 171.528 C9 0.0289 0.0023 12.488 155.960 C10 - 0.3661 0.0024 - 155.738 24254.174 ============ Sum((d/s)**2) for starred atoms 12.951 Chi-squared at 95% for 3 degrees of freedom: 7.81 The group of atoms deviates significantly from planarity Plane 3 m1 = -0.55523(0.00030) m2 = 0.64686(0.00031) m3 = -0.52278(0.00042) D = -3.64863(0.00304) Atom d s d/s (d/s)**2 O2 * -0.0991 0.0022 - 44.394 1970.847 O3 * 0.0261 0.0024 10.896 118.721 O4 * 0.0623 0.0026 23.698 561.601 O5 * -0.1096 0.0027 - 40.018 1601.440 C21 * 0.0644 0.0021 31.070 965.318 C22 * 0.0295 0.0020 15.048 226.451 C23 * 0.0077 0.0021 3.632 13.194 C24 * 0.0047 0.0022 2.135 4.557 C25 * -0.0030 0.0021 - 1.389 1.930 C26 * -0.0015 0.0021 - 0.731 0.535 N2 * -0.0052 0.0020 - 2.585 6.682 N3 * -0.0141 0.0026 - 5.450 29.708 O1 0.1911 0.0018 106.835 11413.636 O6 0.5615 0.0023 239.122 57179.109 O7 - 0.7782 0.0028 - 279.892 78339.773 ============ Sum((d/s)**2) for starred atoms 5500.982 Chi-squared at 95% for 9 degrees of freedom: 16.90 The group of atoms deviates significantly from planarity Dihedral angles formed by LSQ-planes Plane - plane angle (s.u.) angle (s.u.) 1 2 51.30 (0.07) 128.70 (0.07) 1 3 57.81 (0.06) 122.19 (0.06) 2 3 6.52 (0.05) 173.48 (0.05) |
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 | Occ. (<1) | |
N1 | 0.21789 (17) | −0.10900 (15) | 0.20423 (15) | 0.0578 (4) | |
H1 | 0.2451 | −0.0554 | 0.2355 | 0.069* | 0.60 |
H1' | 0.2427 | −0.0633 | 0.2446 | 0.069* | 0.40 |
C1 | 0.1550 (4) | −0.0369 (3) | 0.1062 (3) | 0.0613 (8) | 0.60 |
H1A | 0.1264 | −0.0943 | 0.0679 | 0.074* | 0.60 |
H1B | 0.2205 | 0.0192 | 0.0493 | 0.074* | 0.60 |
C2 | 0.1260 (5) | −0.2010 (3) | 0.2990 (3) | 0.0752 (10) | 0.60 |
H2A | 0.0554 | −0.1549 | 0.3364 | 0.113* | 0.60 |
H2B | 0.1774 | −0.2517 | 0.3564 | 0.113* | 0.60 |
H2C | 0.0869 | −0.2550 | 0.2644 | 0.113* | 0.60 |
C3 | 0.3406 (5) | −0.1852 (5) | 0.1620 (5) | 0.0903 (14) | 0.60 |
H3A | 0.3124 | −0.2424 | 0.1244 | 0.135* | 0.60 |
H3B | 0.3811 | −0.2327 | 0.2282 | 0.135* | 0.60 |
H3C | 0.4053 | −0.1285 | 0.1070 | 0.135* | 0.60 |
C1' | 0.0664 (5) | −0.0886 (4) | 0.2073 (4) | 0.0542 (11) | 0.40 |
H1'B | 0.0353 | −0.1453 | 0.1696 | 0.065* | 0.40 |
H1'A | 0.0210 | −0.1102 | 0.2887 | 0.065* | 0.40 |
C2' | 0.2541 (8) | −0.2364 (5) | 0.2594 (8) | 0.092 (2) | 0.40 |
H2'A | 0.2127 | −0.2585 | 0.3408 | 0.138* | 0.40 |
H2'B | 0.3507 | −0.2450 | 0.2535 | 0.138* | 0.40 |
H2'C | 0.2236 | −0.2917 | 0.2212 | 0.138* | 0.40 |
C3' | 0.2892 (6) | −0.0569 (7) | 0.0789 (5) | 0.0844 (18) | 0.40 |
H3'A | 0.2547 | −0.0954 | 0.0283 | 0.127* | 0.40 |
H3'B | 0.3846 | −0.0753 | 0.0748 | 0.127* | 0.40 |
H3'C | 0.2737 | 0.0332 | 0.0541 | 0.127* | 0.40 |
C4 | 0.0276 (2) | 0.04485 (19) | 0.1474 (2) | 0.0628 (5) | |
H4B | −0.0086 | 0.0956 | 0.0788 | 0.075* | 0.60 |
H4A | −0.0422 | −0.0117 | 0.1971 | 0.075* | 0.60 |
H4'A | 0.0755 | 0.0692 | 0.0669 | 0.075* | 0.40 |
H4'B | −0.0687 | 0.0518 | 0.1457 | 0.075* | 0.40 |
C5 | 0.06332 (18) | 0.13026 (17) | 0.21367 (17) | 0.0520 (4) | |
H5 | 0.0504 | 0.0990 | 0.2952 | 0.062* | |
C6 | 0.11195 (17) | 0.24703 (16) | 0.16755 (16) | 0.0467 (4) | |
C7 | 0.14899 (18) | 0.31612 (16) | 0.24633 (16) | 0.0483 (4) | |
C8 | 0.26852 (18) | 0.38545 (16) | 0.22145 (18) | 0.0530 (4) | |
C9 | 0.3739 (2) | 0.4027 (2) | 0.1112 (2) | 0.0661 (5) | |
H9A | 0.4621 | 0.3968 | 0.1341 | 0.079* | |
H9B | 0.3626 | 0.4881 | 0.0617 | 0.079* | |
C10 | 0.3756 (2) | 0.3124 (2) | 0.0364 (2) | 0.0675 (6) | |
H10A | 0.4588 | 0.3219 | −0.0205 | 0.081* | |
H10B | 0.3738 | 0.2258 | 0.0863 | 0.081* | |
C11 | 0.2569 (2) | 0.33699 (19) | −0.02738 (18) | 0.0613 (5) | |
C12 | 0.12773 (19) | 0.30972 (16) | 0.03873 (16) | 0.0512 (4) | |
C13 | 0.0155 (2) | 0.34122 (18) | −0.01699 (19) | 0.0604 (5) | |
H13 | −0.0708 | 0.3246 | 0.0266 | 0.073* | |
C14 | 0.0316 (3) | 0.3975 (2) | −0.1375 (2) | 0.0767 (7) | |
H14 | −0.0439 | 0.4190 | −0.1743 | 0.092* | |
C15 | 0.1587 (3) | 0.4213 (3) | −0.2024 (2) | 0.0921 (8) | |
H15 | 0.1696 | 0.4576 | −0.2834 | 0.110* | |
C16 | 0.2701 (3) | 0.3914 (3) | −0.1477 (2) | 0.0863 (7) | |
H16 | 0.3559 | 0.4080 | −0.1923 | 0.104* | |
C17 | 0.0608 (2) | 0.31185 (18) | 0.35147 (18) | 0.0580 (5) | |
H17 | −0.0187 | 0.2674 | 0.3685 | 0.070* | |
C18 | 0.0876 (3) | 0.3713 (2) | 0.4308 (2) | 0.0710 (6) | |
H18 | 0.0271 | 0.3663 | 0.5004 | 0.085* | |
C19 | 0.2042 (3) | 0.4382 (2) | 0.4067 (2) | 0.0746 (6) | |
H19 | 0.2230 | 0.4791 | 0.4595 | 0.090* | |
C20 | 0.2921 (2) | 0.44377 (18) | 0.3043 (2) | 0.0652 (5) | |
H20 | 0.3711 | 0.4884 | 0.2892 | 0.078* | |
O1 | 0.38766 (16) | 0.01416 (17) | 0.27372 (15) | 0.0802 (5) | |
O2 | 0.1928 (2) | −0.0525 (2) | 0.45912 (19) | 0.1015 (6) | |
O3 | 0.1707 (2) | 0.0474 (2) | 0.5895 (2) | 0.1137 (8) | |
O4 | 0.4912 (3) | 0.3318 (2) | 0.6002 (2) | 0.1207 (8) | |
O5 | 0.6752 (3) | 0.3624 (2) | 0.4709 (2) | 0.1272 (9) | |
O6 | 0.6970 (2) | 0.2155 (2) | 0.12202 (18) | 0.1099 (7) | |
O7 | 0.6535 (3) | 0.0179 (3) | 0.1766 (2) | 0.1277 (9) | |
N2 | 0.23066 (18) | 0.02555 (19) | 0.50083 (17) | 0.0704 (5) | |
N3 | 0.5638 (3) | 0.3145 (2) | 0.5124 (2) | 0.0890 (7) | |
N4 | 0.6396 (2) | 0.1233 (2) | 0.19054 (19) | 0.0804 (6) | |
C21 | 0.42561 (19) | 0.07393 (19) | 0.33499 (18) | 0.0548 (5) | |
C22 | 0.35468 (18) | 0.09219 (18) | 0.44411 (17) | 0.0539 (5) | |
C23 | 0.3981 (2) | 0.16923 (19) | 0.50119 (18) | 0.0596 (5) | |
H23 | 0.3476 | 0.1784 | 0.5715 | 0.072* | |
C24 | 0.5174 (2) | 0.23295 (19) | 0.45338 (19) | 0.0613 (5) | |
C25 | 0.5947 (2) | 0.2185 (2) | 0.35057 (18) | 0.0612 (5) | |
H25 | 0.6750 | 0.2613 | 0.3191 | 0.073* | |
C26 | 0.55176 (19) | 0.1410 (2) | 0.29632 (17) | 0.0575 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0682 (10) | 0.0547 (9) | 0.0600 (10) | −0.0035 (7) | −0.0147 (7) | −0.0282 (8) |
C1 | 0.080 (2) | 0.0573 (19) | 0.0530 (18) | −0.0037 (16) | −0.0167 (16) | −0.0212 (15) |
C2 | 0.106 (3) | 0.054 (2) | 0.067 (2) | −0.016 (2) | −0.020 (2) | −0.0111 (18) |
C3 | 0.086 (3) | 0.101 (3) | 0.105 (4) | 0.026 (3) | −0.028 (3) | −0.064 (3) |
C1' | 0.066 (3) | 0.042 (2) | 0.059 (3) | −0.0167 (19) | −0.010 (2) | −0.018 (2) |
C2' | 0.101 (5) | 0.054 (3) | 0.131 (6) | 0.008 (3) | −0.043 (5) | −0.029 (4) |
C3' | 0.083 (4) | 0.114 (5) | 0.063 (3) | −0.008 (3) | 0.005 (3) | −0.045 (4) |
C4 | 0.0691 (12) | 0.0493 (10) | 0.0752 (14) | −0.0070 (9) | −0.0276 (10) | −0.0143 (10) |
C5 | 0.0555 (10) | 0.0444 (9) | 0.0552 (10) | −0.0057 (7) | −0.0109 (8) | −0.0105 (8) |
C6 | 0.0437 (9) | 0.0404 (9) | 0.0533 (10) | −0.0002 (6) | −0.0057 (7) | −0.0105 (8) |
C7 | 0.0516 (9) | 0.0362 (8) | 0.0545 (10) | −0.0020 (7) | −0.0081 (8) | −0.0088 (7) |
C8 | 0.0558 (10) | 0.0378 (9) | 0.0623 (11) | −0.0049 (7) | −0.0128 (8) | −0.0064 (8) |
C9 | 0.0545 (11) | 0.0635 (12) | 0.0734 (14) | −0.0154 (9) | −0.0060 (9) | −0.0077 (11) |
C10 | 0.0535 (11) | 0.0714 (13) | 0.0674 (13) | −0.0069 (9) | 0.0070 (9) | −0.0126 (11) |
C11 | 0.0689 (12) | 0.0551 (11) | 0.0539 (11) | −0.0047 (9) | −0.0015 (9) | −0.0101 (9) |
C12 | 0.0605 (11) | 0.0383 (9) | 0.0533 (10) | −0.0014 (7) | −0.0091 (8) | −0.0108 (8) |
C13 | 0.0714 (12) | 0.0437 (10) | 0.0686 (13) | −0.0014 (8) | −0.0189 (10) | −0.0152 (9) |
C14 | 0.1095 (19) | 0.0529 (12) | 0.0733 (15) | 0.0003 (12) | −0.0412 (14) | −0.0109 (11) |
C15 | 0.131 (2) | 0.0850 (18) | 0.0545 (13) | −0.0169 (16) | −0.0200 (15) | −0.0033 (12) |
C16 | 0.0964 (18) | 0.0905 (18) | 0.0604 (14) | −0.0188 (14) | 0.0050 (12) | −0.0099 (13) |
C17 | 0.0636 (11) | 0.0471 (10) | 0.0604 (11) | −0.0038 (8) | −0.0030 (9) | −0.0145 (9) |
C18 | 0.0930 (16) | 0.0578 (12) | 0.0619 (13) | −0.0023 (11) | −0.0024 (11) | −0.0230 (11) |
C19 | 0.1038 (18) | 0.0532 (12) | 0.0771 (15) | −0.0019 (11) | −0.0260 (13) | −0.0277 (11) |
C20 | 0.0728 (13) | 0.0432 (10) | 0.0818 (15) | −0.0094 (9) | −0.0226 (11) | −0.0127 (10) |
O1 | 0.0775 (10) | 0.0943 (12) | 0.0866 (11) | −0.0149 (8) | −0.0220 (8) | −0.0446 (10) |
O2 | 0.0939 (13) | 0.1065 (15) | 0.1022 (15) | −0.0477 (11) | −0.0135 (10) | −0.0158 (12) |
O3 | 0.0899 (14) | 0.141 (2) | 0.0946 (15) | −0.0274 (12) | 0.0273 (11) | −0.0291 (14) |
O4 | 0.177 (2) | 0.1136 (17) | 0.0990 (16) | −0.0020 (15) | −0.0406 (15) | −0.0625 (14) |
O5 | 0.156 (2) | 0.1140 (17) | 0.134 (2) | −0.0628 (16) | −0.0425 (16) | −0.0416 (15) |
O6 | 0.0909 (13) | 0.1459 (19) | 0.0836 (13) | −0.0398 (13) | 0.0192 (10) | −0.0291 (13) |
O7 | 0.1340 (19) | 0.1295 (19) | 0.1262 (19) | −0.0096 (15) | 0.0244 (14) | −0.0738 (17) |
N2 | 0.0585 (10) | 0.0744 (12) | 0.0650 (11) | −0.0060 (9) | −0.0091 (9) | 0.0018 (10) |
N3 | 0.127 (2) | 0.0711 (14) | 0.0834 (16) | −0.0101 (13) | −0.0412 (14) | −0.0272 (12) |
N4 | 0.0631 (11) | 0.1083 (17) | 0.0726 (13) | −0.0104 (11) | −0.0034 (9) | −0.0324 (13) |
C21 | 0.0543 (10) | 0.0553 (11) | 0.0580 (11) | −0.0028 (8) | −0.0181 (8) | −0.0154 (9) |
C22 | 0.0491 (10) | 0.0523 (10) | 0.0568 (11) | −0.0031 (8) | −0.0136 (8) | −0.0064 (9) |
C23 | 0.0678 (12) | 0.0590 (11) | 0.0498 (10) | 0.0060 (9) | −0.0141 (9) | −0.0113 (9) |
C24 | 0.0764 (13) | 0.0535 (11) | 0.0607 (12) | −0.0053 (9) | −0.0268 (10) | −0.0157 (9) |
C25 | 0.0582 (11) | 0.0627 (12) | 0.0621 (12) | −0.0116 (9) | −0.0182 (9) | −0.0086 (10) |
C26 | 0.0505 (10) | 0.0684 (12) | 0.0537 (11) | −0.0040 (8) | −0.0104 (8) | −0.0157 (9) |
N1—C2' | 1.420 (6) | C9—H9A | 0.9700 |
N1—C1 | 1.444 (4) | C9—H9B | 0.9700 |
N1—C2 | 1.510 (4) | C10—C11 | 1.503 (3) |
N1—C3' | 1.513 (6) | C10—H10A | 0.9700 |
N1—C1' | 1.519 (5) | C10—H10B | 0.9700 |
N1—C3 | 1.527 (4) | C11—C16 | 1.385 (3) |
N1—H1 | 0.8702 | C11—C12 | 1.398 (3) |
N1—H1' | 0.8705 | C12—C13 | 1.390 (3) |
C1—C4 | 1.592 (4) | C13—C14 | 1.389 (3) |
C1—H1A | 0.9700 | C13—H13 | 0.9300 |
C1—H1B | 0.9700 | C14—C15 | 1.372 (4) |
C2—H2A | 0.9600 | C14—H14 | 0.9300 |
C2—H2B | 0.9600 | C15—C16 | 1.374 (4) |
C2—H2C | 0.9600 | C15—H15 | 0.9300 |
C3—H3A | 0.9600 | C16—H16 | 0.9300 |
C3—H3B | 0.9600 | C17—C18 | 1.376 (3) |
C3—H3C | 0.9600 | C17—H17 | 0.9300 |
C1'—C4 | 1.497 (5) | C18—C19 | 1.377 (3) |
C1'—H1'B | 0.9700 | C18—H18 | 0.9300 |
C1'—H1'A | 0.9700 | C19—C20 | 1.366 (3) |
C2'—H2'A | 0.9600 | C19—H19 | 0.9300 |
C2'—H2'B | 0.9600 | C20—H20 | 0.9300 |
C2'—H2'C | 0.9600 | O1—C21 | 1.243 (2) |
C3'—H3'A | 0.9600 | O2—N2 | 1.228 (3) |
C3'—H3'B | 0.9600 | O3—N2 | 1.202 (3) |
C3'—H3'C | 0.9600 | O4—N3 | 1.222 (3) |
C4—C5 | 1.497 (3) | O5—N3 | 1.233 (3) |
C4—H4B | 0.9700 | O6—N4 | 1.217 (3) |
C4—H4A | 0.9700 | O7—N4 | 1.214 (3) |
C4—H4'A | 0.9700 | N2—C22 | 1.451 (3) |
C4—H4'B | 0.9700 | N3—C24 | 1.444 (3) |
C5—C6 | 1.339 (2) | N4—C26 | 1.462 (3) |
C5—H5 | 0.9300 | C21—C22 | 1.434 (3) |
C6—C7 | 1.486 (2) | C21—C26 | 1.452 (3) |
C6—C12 | 1.489 (3) | C22—C23 | 1.374 (3) |
C7—C17 | 1.396 (3) | C23—C24 | 1.383 (3) |
C7—C8 | 1.415 (2) | C23—H23 | 0.9300 |
C8—C20 | 1.394 (3) | C24—C25 | 1.378 (3) |
C8—C9 | 1.512 (3) | C25—C26 | 1.351 (3) |
C9—C10 | 1.519 (3) | C25—H25 | 0.9300 |
C1—N1—C2 | 114.5 (2) | C7—C8—C9 | 125.39 (17) |
C2'—N1—C3' | 115.0 (5) | C8—C9—C10 | 118.28 (16) |
C2'—N1—C1' | 112.5 (4) | C8—C9—H9A | 107.7 |
C3'—N1—C1' | 108.8 (3) | C10—C9—H9A | 107.7 |
C1—N1—C3 | 110.5 (3) | C8—C9—H9B | 107.7 |
C2—N1—C3 | 107.3 (3) | C10—C9—H9B | 107.7 |
C1—N1—H1 | 107.5 | H9A—C9—H9B | 107.1 |
C2—N1—H1 | 108.3 | C11—C10—C9 | 111.64 (18) |
C3—N1—H1 | 108.7 | C11—C10—H10A | 109.3 |
C2'—N1—H1' | 106.1 | C9—C10—H10A | 109.3 |
C3'—N1—H1' | 106.2 | C11—C10—H10B | 109.3 |
C1'—N1—H1' | 107.9 | C9—C10—H10B | 109.3 |
N1—C1—C4 | 111.6 (2) | H10A—C10—H10B | 108.0 |
N1—C1—H1A | 109.3 | C16—C11—C12 | 119.0 (2) |
C4—C1—H1A | 109.3 | C16—C11—C10 | 122.5 (2) |
N1—C1—H1B | 109.3 | C12—C11—C10 | 118.36 (18) |
C4—C1—H1B | 109.3 | C13—C12—C11 | 119.38 (19) |
H1A—C1—H1B | 108.0 | C13—C12—C6 | 120.82 (17) |
N1—C2—H2A | 109.5 | C11—C12—C6 | 119.80 (17) |
N1—C2—H2B | 109.5 | C14—C13—C12 | 120.3 (2) |
N1—C2—H2C | 109.5 | C14—C13—H13 | 119.8 |
H2A—C2—H2B | 109.5 | C12—C13—H13 | 119.8 |
H2A—C2—H2C | 109.5 | C15—C14—C13 | 120.1 (2) |
H2B—C2—H2C | 109.5 | C15—C14—H14 | 120.0 |
N1—C3—H3A | 109.5 | C13—C14—H14 | 120.0 |
N1—C3—H3B | 109.5 | C14—C15—C16 | 119.9 (2) |
N1—C3—H3C | 109.5 | C14—C15—H15 | 120.0 |
H3A—C3—H3B | 109.5 | C16—C15—H15 | 120.0 |
H3A—C3—H3C | 109.5 | C15—C16—C11 | 121.3 (2) |
H3B—C3—H3C | 109.5 | C15—C16—H16 | 119.4 |
C4—C1'—N1 | 112.8 (3) | C11—C16—H16 | 119.4 |
C4—C1'—H1'B | 109.0 | C18—C17—C7 | 122.08 (19) |
N1—C1'—H1'B | 109.0 | C18—C17—H17 | 119.0 |
C4—C1'—H1'A | 109.0 | C7—C17—H17 | 119.0 |
N1—C1'—H1'A | 109.0 | C17—C18—C19 | 119.8 (2) |
H1'B—C1'—H1'A | 107.8 | C17—C18—H18 | 120.1 |
N1—C2'—H2'A | 109.5 | C19—C18—H18 | 120.1 |
N1—C2'—H2'B | 109.5 | C20—C19—C18 | 119.2 (2) |
H2'A—C2'—H2'B | 109.5 | C20—C19—H19 | 120.4 |
N1—C2'—H2'C | 109.5 | C18—C19—H19 | 120.4 |
H2'A—C2'—H2'C | 109.5 | C19—C20—C8 | 122.9 (2) |
H2'B—C2'—H2'C | 109.5 | C19—C20—H20 | 118.6 |
N1—C3'—H3'A | 109.5 | C8—C20—H20 | 118.6 |
N1—C3'—H3'B | 109.5 | O3—N2—O2 | 122.6 (2) |
H3'A—C3'—H3'B | 109.5 | O3—N2—C22 | 117.8 (2) |
N1—C3'—H3'C | 109.5 | O2—N2—C22 | 119.5 (2) |
H3'A—C3'—H3'C | 109.5 | O4—N3—O5 | 123.9 (2) |
H3'B—C3'—H3'C | 109.5 | O4—N3—C24 | 118.4 (3) |
C5—C4—C1' | 108.6 (2) | O5—N3—C24 | 117.7 (2) |
C5—C4—C1 | 112.01 (18) | O7—N4—O6 | 123.5 (2) |
C5—C4—H4B | 109.2 | O7—N4—C26 | 118.6 (2) |
C1—C4—H4B | 109.2 | O6—N4—C26 | 117.8 (2) |
C5—C4—H4A | 109.2 | O1—C21—C22 | 127.38 (18) |
C1—C4—H4A | 109.2 | O1—C21—C26 | 120.88 (19) |
H4B—C4—H4A | 107.9 | C22—C21—C26 | 111.67 (17) |
C5—C4—H4'A | 110.0 | C23—C22—C21 | 123.73 (18) |
C1'—C4—H4'A | 110.0 | C23—C22—N2 | 116.59 (19) |
C5—C4—H4'B | 110.0 | C21—C22—N2 | 119.68 (18) |
C1'—C4—H4'B | 110.0 | C22—C23—C24 | 119.52 (19) |
H4'A—C4—H4'B | 108.3 | C22—C23—H23 | 120.2 |
C6—C5—C4 | 126.66 (18) | C24—C23—H23 | 120.2 |
C6—C5—H5 | 116.7 | C25—C24—C23 | 120.99 (18) |
C4—C5—H5 | 116.7 | C25—C24—N3 | 119.0 (2) |
C5—C6—C7 | 119.50 (17) | C23—C24—N3 | 120.0 (2) |
C5—C6—C12 | 121.16 (17) | C26—C25—C24 | 118.85 (19) |
C7—C6—C12 | 119.34 (14) | C26—C25—H25 | 120.6 |
C17—C7—C8 | 118.07 (17) | C24—C25—H25 | 120.6 |
C17—C7—C6 | 117.95 (16) | C25—C26—C21 | 125.12 (18) |
C8—C7—C6 | 123.98 (16) | C25—C26—N4 | 117.25 (18) |
C20—C8—C7 | 118.03 (18) | C21—C26—N4 | 117.63 (18) |
C20—C8—C9 | 116.58 (17) | ||
C2—N1—C1—C4 | 59.4 (3) | C10—C11—C16—C15 | −175.2 (2) |
C3—N1—C1—C4 | −179.4 (3) | C8—C7—C17—C18 | −0.7 (3) |
C2'—N1—C1'—C4 | −178.9 (4) | C6—C7—C17—C18 | 178.99 (18) |
C3'—N1—C1'—C4 | −50.3 (4) | C7—C17—C18—C19 | 0.4 (3) |
N1—C1—C4—C5 | 55.6 (3) | C17—C18—C19—C20 | −0.4 (4) |
N1—C1'—C4—C5 | −64.4 (3) | C18—C19—C20—C8 | 0.7 (3) |
C1—C4—C5—C6 | 86.3 (3) | C7—C8—C20—C19 | −1.0 (3) |
C1'—C4—C5—C6 | 142.7 (3) | C9—C8—C20—C19 | 178.7 (2) |
C4—C5—C6—C7 | −176.72 (17) | O1—C21—C22—C23 | −173.9 (2) |
C4—C5—C6—C12 | 4.2 (3) | C26—C21—C22—C23 | 3.2 (3) |
C5—C6—C7—C17 | −43.5 (2) | O1—C21—C22—N2 | 7.1 (3) |
C12—C6—C7—C17 | 135.60 (18) | C26—C21—C22—N2 | −175.86 (16) |
C5—C6—C7—C8 | 136.18 (19) | O3—N2—C22—C23 | 4.1 (3) |
C11—C12—C6—C7 | 66.2 (2) | O2—N2—C22—C23 | −174.0 (2) |
C12—C6—C7—C8 | −44.7 (2) | O3—N2—C22—C21 | −176.8 (2) |
C17—C7—C8—C20 | 1.0 (3) | O2—N2—C22—C21 | 5.1 (3) |
C6—C7—C8—C20 | −178.73 (16) | C21—C22—C23—C24 | −0.7 (3) |
C17—C7—C8—C9 | −178.65 (18) | N2—C22—C23—C24 | 178.38 (17) |
C6—C7—C8—C9 | 1.6 (3) | C22—C23—C24—C25 | −1.3 (3) |
C20—C8—C9—C10 | 162.38 (19) | C22—C23—C24—N3 | 179.81 (18) |
C7—C8—C9—C10 | −18.0 (3) | O4—N3—C24—C25 | 176.3 (2) |
C8—C9—C10—C11 | 71.5 (2) | O5—N3—C24—C25 | −3.9 (3) |
C9—C10—C11—C16 | 108.2 (2) | O4—N3—C24—C23 | −4.8 (3) |
C9—C10—C11—C12 | −68.4 (2) | O5—N3—C24—C23 | 175.1 (2) |
C16—C11—C12—C13 | −1.9 (3) | C23—C24—C25—C26 | 0.3 (3) |
C10—C11—C12—C13 | 174.80 (18) | N3—C24—C25—C26 | 179.22 (19) |
C16—C11—C12—C6 | 177.83 (19) | C24—C25—C26—C21 | 2.7 (3) |
C10—C11—C12—C6 | −5.4 (3) | C24—C25—C26—N4 | −177.2 (2) |
C5—C6—C12—C13 | 65.1 (2) | O1—C21—C26—C25 | 173.0 (2) |
C7—C6—C12—C13 | −114.05 (19) | C22—C21—C26—C25 | −4.3 (3) |
C5—C6—C12—C11 | −114.7 (2) | O1—C21—C26—N4 | −7.1 (3) |
C11—C12—C13—C14 | 1.0 (3) | C22—C21—C26—N4 | 175.63 (18) |
C6—C12—C13—C14 | −178.76 (17) | O7—N4—C26—C25 | 139.1 (3) |
C12—C13—C14—C15 | 0.5 (3) | O6—N4—C26—C25 | −39.6 (3) |
C13—C14—C15—C16 | −1.1 (4) | O7—N4—C26—C21 | −40.9 (3) |
C14—C15—C16—C11 | 0.1 (4) | O6—N4—C26—C21 | 140.5 (2) |
C12—C11—C16—C15 | 1.4 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1+—H1···O1- | 0.87 | 1.87 | 2.648 (2) | 149 |
N1+—H1′···O1- | 0.87 | 1.88 | 2.648 (3) | 146 |
C4—H4A···O3i | 0.97 | 2.59 | 3.343 (3) | 135 |
C19—H19···O5ii | 0.93 | 2.50 | 3.379 (4) | 158 |
C14—H14···Cg1iii | 0.93 | 2.87 | 3.667 (3) | 144 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C20H24N+·C6H2N3O7− |
Mr | 506.51 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 301 |
a, b, c (Å) | 10.0649 (11), 11.0187 (12), 12.0352 (13) |
α, β, γ (°) | 73.357 (2), 79.305 (3), 85.411 (4) |
V (Å3) | 1256.1 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.48 × 0.31 × 0.26 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.969, 0.975 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7632, 4802, 3598 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.178, 1.06 |
No. of reflections | 4802 |
No. of parameters | 365 |
No. of restraints | 15 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.30 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003), SHELXL97.
C2—N1—C1—C4 | 59.4 (3) | C11—C12—C6—C7 | 66.2 (2) |
C3—N1—C1—C4 | −179.4 (3) | C12—C6—C7—C8 | −44.7 (2) |
C2'—N1—C1'—C4 | −178.9 (4) | C6—C7—C8—C9 | 1.6 (3) |
C3'—N1—C1'—C4 | −50.3 (4) | C7—C8—C9—C10 | −18.0 (3) |
N1—C1—C4—C5 | 55.6 (3) | C8—C9—C10—C11 | 71.5 (2) |
N1—C1'—C4—C5 | −64.4 (3) | C9—C10—C11—C12 | −68.4 (2) |
C1—C4—C5—C6 | 86.3 (3) | C10—C11—C12—C6 | −5.4 (3) |
C1'—C4—C5—C6 | 142.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1+—H1···O1- | 0.87 | 1.87 | 2.648 (2) | 149 |
N1+—H1'···O1- | 0.87 | 1.88 | 2.648 (3) | 146 |
C4—H4A···O3i | 0.97 | 2.59 | 3.343 (3) | 135 |
C19—H19···O5ii | 0.93 | 2.50 | 3.379 (4) | 158 |
C14—H14···Cg1iii | 0.93 | 2.87 | 3.667 (3) | 144 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z. |
Amitriptyline (Elavil) is a well known tricyclic antidepressant with anticholinergic and sedative properties. It is believed to prevent the reuptake of norepinephrine and serotonin at neurotransmitters (Garattini et al., 1998; DrugBank ID APRD00227; https://redpoll.pharmacy.ualberta.ca/drugbank/; Wishart et al., 2006). The structure of the title salt, amitriptyline picrate, (I), is presented here.
The dimethylaminopropyl subunit (DMAP; atoms N1/C1–C5) of (I) exhibits a classical static conformational disorder. There are two conformational states of DMAP, where the state corresponding to the minor disordered component is interconvertible from the major one by approximate rotations of 60, -120 and 120° about the C4—C5, C1—C4 and C1—N1 bonds, respectively. The torsion angles in (I) are provided in Table 1. A text search for conformational disorder in the Cambridge Structural Database (CSD, Version 5.28; Allen, 2002) revealed that such compounds represent hardly 0.001% of all reported structures. A great majority of them are populated by conformational disorders of terminal hydrocarbon chains and multiple puckering states of alicyclic rings. The multi-conformational states of a molecule or part thereof, separated by low-energy barriers, are also represented in conformational polymorphs. Even if all of the 0.5% of polymorph cases present in the CSD (van de Streek & Motherwell, 2005) are included, this under-representation is in sharp contrast to the otherwise plentiful conformational states of a molecule that are populated in solution. This anomalous observation could be partially rationalized by the fact that, among several conformers in solution, only those that exhibit similar steric bulk and are relatively disposed in a similar manner occur in the crystal structure, so that there is a minimal violation of crystal translational symmetry.
The central seven-membered cycloheptadiene ring of (I) (C6–C12) adopts a bent conformation (Table 1), giving rise to an overall butterfly shape of the tricyclic ring (Fig. 1). The fused benzene rings (C11–C16 and C7/C8/C17–C20) on either side subtend an angle of 51.3 (1)°. The bent transition state is an intermediate conformation state of a cycloheptane, between boat and chair, and is characterized in the ideal case by the following contiguous torsion angles as calculated by Bocian et al. (1975) and Bocian & Strauss (1977): 75.1, -60.3, -1.8, 1.7, 60.3, -75.1 and 0.0°. Similar conformations of the tricyclic ring were also observed in nortriptyline and amitriptyline hydrochloride (Klein et al., 1991, 1994) and related compounds (Vijay et al., 2005; Portalone et al., 2007).
The crystal packing of (I) is predominantly stabilized by cooperative interactions, as shown in Fig. 2. Amitriptyline (AMP) and picrate (PCT) molecules play a complementary role. The intermolecular salt bridges and hydrogen bonds are formed between the donors of the AMP and the acceptors of the PCT (Table 2). The N1+—H1 (or H1')···O1- salt bridges and C19—H19···O5ii [symmetry code: (ii) 1 - x, 1 - y, 1 - z] hydrogen bonds cluster them into a hetero-tetramer. This assembly is characterized by an R44(36) pattern (Bernstein et al., 1995). Orthogonal to this assemblage, AMP molecules are clustered into homodimers, which are mediated by C14—H14···Cg1iii interactions [symmetry code: (iii) -x, 1 - y, -z].
Significant π–π interactions are also observed in the packing of (I). Cg3 (the centroid of the PCT C21–C26 ring) makes a stacking interaction with Cg1 (the centroid of the AMP C7/C8/C17–C20 ring) of the same asymmetric unit, with a centroid-to-centroid distance of 3.774 (1) Å and a perpendicular distance of 3.475 Å. On its other face, PCT is associated by a parallel stacking interaction, with Cg3···Cg3iv = 3.406 Å and a slippage of 1.348 Å, and a centroid-to-centroid distance of 3.663 (1) Å [symmetry code: (iv) 1 - x, -y, 1 - z].
These interactions between AMP and PCT pairs, in combination with C—H···π interactions with another two AMP molecules, form a one-dimensional chain along the [111] direction (Fig 2). The cooperative association of intermolecular interactions into characteristic patterns has been unambiguously characterized using graph theory based notations (Bernstein et al., 1995). Unfortunately, such notations are of limited applicability, as they cannot be used to characterize interactions involving π-acceptors or those which do not come under the category of donor–acceptor types, such as aromatic π–π interactions. It would be of particular interest to formulate a similar scheme which can be specifically applied in those cases.
Apart from cooperative interactions, the major component of DMAP is involved in C4—H4A···O3i hydrogen bonding [symmetry code: (i) -x, -y, 1 - z]. A short contact associated with the methyl atom, C3—H3B···O4v [H···A = 2.56 Å, C—H···A = 172°; symmetry code: (v) 1 - x, -y, 1 - z], is also observed. However, short contacts like this involving methyl atoms are unlikely to have any structural significance, due to the very low acidity of the C—H bond and the rapid rotation of the methyl group about N1—C3 bond.