Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041219/bt2487sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041219/bt2487Isup2.hkl |
CCDC reference: 660352
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (C-C) = 0.004 Å
- H-atom completeness 93%
- Disorder in main residue
- R factor = 0.067
- wR factor = 0.220
- Data-to-parameter ratio = 14.1
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) ....... O21
Author Response: The H atoms could not be located in the present study. |
Alert level B PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for N13 PLAT430_ALERT_2_B Short Inter D...A Contact O16 .. O21 .. 2.67 Ang.
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 100 Deg. PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N2 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N11 PLAT301_ALERT_3_C Main Residue Disorder ......................... 5.00 Perc. PLAT320_ALERT_2_C Check Hybridisation of C15 in Main Residue . ? PLAT432_ALERT_2_C Short Inter X...Y Contact C18 .. O18 .. 2.99 Ang.
Alert level G FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C24 H27 N5 O8 Atom count from the _atom_site data: C24 H25 N5 O8 CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected. CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional? From the CIF: _cell_formula_units_Z 2 From the CIF: _chemical_formula_sum C24 H27 N5 O8 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 48.00 48.00 0.00 H 54.00 50.00 4.00 N 10.00 10.00 0.00 O 16.00 16.00 0.00
1 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 10 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 8 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related structures, see: Portalone et al. (2007); Harrison, Ashok et al. (2007); Harrison, Bindya et al. (2007). For background, see: Cohen et al. (1990); Ahmed et al. (2002).
Desipramine hydrochloride (0.8 g, 0.05 mol) and picric acid (0.6 g, 0.05 mol) were dissolved in distilled water (50 ml), mixed and stirred well in a beaker at room temperature. The separated bright yellow salt was washed well with distilled water, filtered and dried in a vacuum desiccator over P2O5. Yellow blocks of (I) were recrystallized from absolute ethanol (m.p.: 387 K). The water of crystallization in (I) was presumably incorporated from the atmosphere.
One of the nitro groups of the anion is disordered over two orientations in a 0.840 (6):0.160 (6) ratio. The N-bound H atoms were located in a differenc map, then relocated to idealized locations (N—H = 0.86 Å) and refined as riding with Uiso(H) = 1.2Ueq(N). The C-bound H atoms were geometrically placed (C—H = 0.93–0.96 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The methyl group was allowed to rotate, but not to tip, to best fit the electron density. The H atoms of the water molecule could not be located in the present study.
Desipramine, 10,11-dihydro-5-[3-(methylamino)propyl]-5H-dibenz[b,f]azepine, C18H22N2, is a tricyclic antidepressant (TCA) and pain reliever that inhibits the reuptake of norepinephrine. Medical applications (Cohen et al., 1990) usually utilize desipramine as its hydrochloride salt, i.e. C18H23N2+·Cl-. A recent proposed new application of desipramine hydrochloride as a reagent for the detection of microamounts of blood in urine (Ahmed et al., 2002).
In continuation of our work on the picrate salts of pharmaceutical compounds (Portalone et al., 2007; Harrison, Ashok et al., 2007; Harrison, Bindya et al., 2007), we now report the structure of the title compound, (I).
The structure of (I) (Fig. 1) shows that proton transfer from picric acid (pa) to desipramine (dp) has occurred, and that the secondary-amine N atom of the side chain has been protonated to yield an –NH2+– grouping. The dihedral angle between the C1–C6 and C9–C14 ring planes in (I) is 53.92 (8)°. The bond-angle sum for N1 is 360.0°, indicating sp2 hybridization. However, the unobserved p orbital appears not to be well aligned to overlap with the π clouds of the adjacent benzene rings, as the C1/C14/C15/N1 grouping makes dihedral angles of 65.28 (10)° and 44.78 (11)° with the C1–C6 and C9–C14 ring planes, respectively. The seven-membered ring in (I) approximates to a boat, with C1/C6/C8/C9 almost co-planar (r.m.s. deviation = 0.002 Å), C7 forming the prow [deviation = 0.721 (3) Å] and N1 and C14 the stern [deviations = 0.787 (4) and 0.351 (4) Å, respectively].
The significant variation of the C—C bond lengths around the picrate aromatic ring in (I) are normal (Harrison, Ashok et al., 2007). The N13 nitro group is disordered over two orientations.
In the crystal, the cation and anion are linked by a bifurcated N—H···(O,O) hydrogen bond (Table 1), as also seen in related compounds (Harrison, Ashok et al., 2007). The cation also bonds to the O21 water molecule with an N—H···O link. Unfortunately, the water molecule H atoms were not located in this study. One of the H atoms is probably involved in an H bond to O16 [O21···O16 = 2.667 (5) Å], but there is no obvious second H bond and geometrical placement of the H atoms was not attempted.
For related structures, see: Portalone et al. (2007); Harrison, Ashok et al. (2007); Harrison, Bindya et al. (2007). For background, see: Cohen et al. (1990); Ahmed et al. (2002).
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
C18H23N2+·C6H2N3O7−·H2O | Z = 2 |
Mr = 513.51 | F(000) = 540 |
Triclinic, P1 | Dx = 1.374 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.3126 (4) Å | Cell parameters from 5773 reflections |
b = 11.2594 (5) Å | θ = 2.3–27.5° |
c = 11.4304 (5) Å | µ = 0.11 mm−1 |
α = 72.162 (1)° | T = 291 K |
β = 79.288 (1)° | Chunk, yellow |
γ = 87.233 (1)° | 0.60 × 0.50 × 0.45 mm |
V = 1241.35 (9) Å3 |
Bruker SMART1000 CCD diffractometer | 4865 independent reflections |
Radiation source: fine-focus sealed tube | 3688 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
ω scans | θmax = 26.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −11→12 |
Tmin = 0.943, Tmax = 0.954 | k = −13→13 |
11334 measured reflections | l = −14→14 |
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)] = 0.067 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.220 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.1277P)2 + 0.5257P] where P = (Fo2 + 2Fc2)/3 |
4865 reflections | (Δ/σ)max < 0.001 |
344 parameters | Δρmax = 0.47 e Å−3 |
0 restraints | Δρmin = −0.58 e Å−3 |
C18H23N2+·C6H2N3O7−·H2O | γ = 87.233 (1)° |
Mr = 513.51 | V = 1241.35 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.3126 (4) Å | Mo Kα radiation |
b = 11.2594 (5) Å | µ = 0.11 mm−1 |
c = 11.4304 (5) Å | T = 291 K |
α = 72.162 (1)° | 0.60 × 0.50 × 0.45 mm |
β = 79.288 (1)° |
Bruker SMART1000 CCD diffractometer | 4865 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 3688 reflections with I > 2σ(I) |
Tmin = 0.943, Tmax = 0.954 | Rint = 0.015 |
11334 measured reflections |
R[F2 > 2σ(F2)] = 0.067 | 0 restraints |
wR(F2) = 0.220 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.47 e Å−3 |
4865 reflections | Δρmin = −0.58 e Å−3 |
344 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. |
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) | |
C1 | 0.3705 (2) | 0.18454 (19) | 0.4622 (2) | 0.0422 (5) | |
C2 | 0.4803 (3) | 0.1592 (2) | 0.5201 (3) | 0.0557 (6) | |
H2 | 0.5632 | 0.1876 | 0.4743 | 0.067* | |
C3 | 0.4669 (3) | 0.0915 (3) | 0.6462 (3) | 0.0676 (8) | |
H3 | 0.5407 | 0.0748 | 0.6844 | 0.081* | |
C4 | 0.3441 (4) | 0.0493 (3) | 0.7141 (3) | 0.0735 (9) | |
H4 | 0.3349 | 0.0041 | 0.7982 | 0.088* | |
C5 | 0.2351 (3) | 0.0740 (3) | 0.6576 (2) | 0.0614 (7) | |
H5 | 0.1525 | 0.0456 | 0.7043 | 0.074* | |
C6 | 0.2464 (2) | 0.1412 (2) | 0.5309 (2) | 0.0447 (5) | |
C7 | 0.1308 (2) | 0.1630 (2) | 0.4653 (2) | 0.0499 (6) | |
H7A | 0.1287 | 0.2503 | 0.4171 | 0.060* | |
H7B | 0.0499 | 0.1436 | 0.5266 | 0.060* | |
C8 | 0.1382 (2) | 0.0830 (2) | 0.3790 (2) | 0.0515 (6) | |
H8A | 0.1503 | −0.0027 | 0.4274 | 0.062* | |
H8B | 0.0533 | 0.0870 | 0.3531 | 0.062* | |
C9 | 0.2437 (2) | 0.11361 (19) | 0.2627 (2) | 0.0461 (5) | |
C10 | 0.2280 (3) | 0.0574 (2) | 0.1725 (3) | 0.0613 (7) | |
H10 | 0.1550 | 0.0060 | 0.1876 | 0.074* | |
C11 | 0.3157 (4) | 0.0751 (3) | 0.0634 (3) | 0.0779 (9) | |
H11 | 0.3026 | 0.0356 | 0.0059 | 0.093* | |
C12 | 0.4236 (4) | 0.1518 (3) | 0.0391 (3) | 0.0789 (10) | |
H12 | 0.4837 | 0.1651 | −0.0354 | 0.095* | |
C13 | 0.4424 (3) | 0.2094 (2) | 0.1266 (2) | 0.0606 (7) | |
H13 | 0.5158 | 0.2608 | 0.1098 | 0.073* | |
C14 | 0.3542 (2) | 0.19202 (19) | 0.2385 (2) | 0.0436 (5) | |
C15 | 0.4229 (2) | 0.3765 (2) | 0.2848 (2) | 0.0475 (5) | |
H15A | 0.3560 | 0.4218 | 0.2395 | 0.057* | |
H15B | 0.5017 | 0.3791 | 0.2226 | 0.057* | |
C16 | 0.4542 (3) | 0.4549 (2) | 0.3614 (3) | 0.0588 (7) | |
H16A | 0.5492 | 0.4615 | 0.3522 | 0.071* | |
H16B | 0.4193 | 0.4139 | 0.4488 | 0.071* | |
C17 | 0.3969 (3) | 0.5852 (2) | 0.3232 (3) | 0.0618 (7) | |
H17A | 0.4266 | 0.6343 | 0.3698 | 0.074* | |
H17B | 0.4294 | 0.6253 | 0.2351 | 0.074* | |
C18 | 0.1933 (4) | 0.7103 (3) | 0.3209 (4) | 0.0896 (11) | |
H18A | 0.0988 | 0.7040 | 0.3386 | 0.134* | |
H18B | 0.2221 | 0.7567 | 0.2348 | 0.134* | |
H18C | 0.2221 | 0.7523 | 0.3732 | 0.134* | |
N1 | 0.3828 (2) | 0.2574 (2) | 0.3275 (2) | 0.0554 (5) | |
N2 | 0.2508 (2) | 0.5830 (2) | 0.3460 (2) | 0.0559 (5) | |
H1N | 0.2230 | 0.5440 | 0.3014 | 0.067* | |
H2N | 0.2161 | 0.5385 | 0.4198 | 0.067* | |
C21 | 0.0489 (2) | 0.4204 (2) | 0.1836 (2) | 0.0428 (5) | |
C22 | 0.1382 (2) | 0.4268 (2) | 0.0688 (2) | 0.0442 (5) | |
C23 | 0.1227 (3) | 0.3566 (2) | −0.0082 (2) | 0.0529 (6) | |
H23 | 0.1833 | 0.3644 | −0.0815 | 0.063* | |
C24 | 0.0174 (3) | 0.2750 (2) | 0.0241 (2) | 0.0551 (6) | |
C25 | −0.0728 (3) | 0.2612 (2) | 0.1328 (2) | 0.0541 (6) | |
H25 | −0.1427 | 0.2048 | 0.1550 | 0.065* | |
C26 | −0.0576 (2) | 0.3315 (2) | 0.2070 (2) | 0.0462 (5) | |
N11 | 0.2504 (2) | 0.5128 (2) | 0.0260 (2) | 0.0598 (6) | |
N12 | −0.0004 (3) | 0.2036 (3) | −0.0585 (3) | 0.0804 (8) | |
N13 | −0.1562 (2) | 0.3130 (2) | 0.3202 (2) | 0.0631 (6) | |
O11 | 0.05959 (19) | 0.47933 (17) | 0.25813 (17) | 0.0595 (5) | |
O12 | 0.2615 (2) | 0.5890 (2) | 0.0801 (2) | 0.0795 (6) | |
O13 | 0.3289 (3) | 0.5073 (3) | −0.0639 (3) | 0.1196 (11) | |
O14 | 0.0784 (4) | 0.2197 (3) | −0.1557 (3) | 0.1102 (10) | |
O15 | −0.0951 (4) | 0.1312 (3) | −0.0257 (3) | 0.1176 (11) | |
O16 | −0.2029 (3) | 0.4031 (3) | 0.3489 (3) | 0.1007 (13) | 0.840 (6) |
O17 | −0.1854 (3) | 0.2071 (3) | 0.3862 (3) | 0.0971 (13) | 0.840 (6) |
O18 | −0.1390 (18) | 0.2968 (17) | 0.4109 (18) | 0.092 (6)* | 0.160 (6) |
O19 | −0.278 (3) | 0.301 (2) | 0.301 (2) | 0.144 (10)* | 0.160 (6) |
O21 | 0.1305 (4) | 0.4099 (3) | 0.5790 (3) | 0.1427 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0435 (12) | 0.0359 (10) | 0.0494 (12) | 0.0018 (8) | −0.0119 (9) | −0.0144 (9) |
C2 | 0.0515 (14) | 0.0504 (13) | 0.0714 (16) | 0.0057 (10) | −0.0231 (12) | −0.0210 (12) |
C3 | 0.087 (2) | 0.0567 (15) | 0.0725 (18) | 0.0144 (14) | −0.0477 (17) | −0.0217 (13) |
C4 | 0.111 (3) | 0.0626 (17) | 0.0477 (14) | 0.0047 (17) | −0.0259 (16) | −0.0120 (12) |
C5 | 0.0774 (18) | 0.0564 (15) | 0.0467 (13) | −0.0057 (13) | −0.0035 (12) | −0.0138 (11) |
C6 | 0.0486 (12) | 0.0391 (11) | 0.0457 (11) | −0.0002 (9) | −0.0054 (9) | −0.0136 (9) |
C7 | 0.0376 (11) | 0.0487 (12) | 0.0564 (13) | −0.0044 (9) | −0.0003 (10) | −0.0099 (10) |
C8 | 0.0492 (13) | 0.0418 (12) | 0.0627 (14) | −0.0085 (10) | −0.0182 (11) | −0.0086 (10) |
C9 | 0.0554 (13) | 0.0331 (10) | 0.0525 (12) | 0.0067 (9) | −0.0223 (10) | −0.0105 (9) |
C10 | 0.0791 (19) | 0.0462 (13) | 0.0680 (16) | 0.0080 (12) | −0.0317 (14) | −0.0214 (12) |
C11 | 0.115 (3) | 0.0649 (18) | 0.0684 (18) | 0.0157 (18) | −0.0309 (18) | −0.0348 (15) |
C12 | 0.106 (3) | 0.077 (2) | 0.0487 (15) | 0.0230 (19) | −0.0022 (15) | −0.0218 (14) |
C13 | 0.0653 (17) | 0.0540 (14) | 0.0549 (14) | 0.0046 (12) | 0.0005 (12) | −0.0129 (11) |
C14 | 0.0473 (12) | 0.0356 (10) | 0.0456 (11) | 0.0053 (9) | −0.0098 (9) | −0.0089 (9) |
C15 | 0.0358 (11) | 0.0431 (12) | 0.0589 (13) | −0.0047 (9) | −0.0044 (9) | −0.0105 (10) |
C16 | 0.0502 (14) | 0.0498 (13) | 0.0802 (17) | −0.0091 (11) | −0.0226 (12) | −0.0174 (12) |
C17 | 0.0684 (17) | 0.0453 (13) | 0.0765 (17) | −0.0121 (12) | −0.0238 (14) | −0.0172 (12) |
C18 | 0.111 (3) | 0.071 (2) | 0.111 (3) | 0.0295 (19) | −0.051 (2) | −0.050 (2) |
N1 | 0.0438 (11) | 0.0580 (12) | 0.0614 (12) | 0.0002 (9) | −0.0078 (9) | −0.0148 (10) |
N2 | 0.0644 (13) | 0.0542 (12) | 0.0569 (12) | 0.0019 (10) | −0.0198 (10) | −0.0230 (9) |
C21 | 0.0434 (12) | 0.0413 (11) | 0.0434 (11) | 0.0041 (9) | −0.0129 (9) | −0.0100 (9) |
C22 | 0.0386 (11) | 0.0465 (12) | 0.0439 (11) | 0.0008 (9) | −0.0108 (9) | −0.0065 (9) |
C23 | 0.0573 (14) | 0.0571 (14) | 0.0418 (11) | 0.0160 (11) | −0.0119 (10) | −0.0118 (10) |
C24 | 0.0691 (16) | 0.0481 (13) | 0.0561 (14) | 0.0089 (11) | −0.0261 (12) | −0.0201 (11) |
C25 | 0.0542 (14) | 0.0453 (13) | 0.0645 (15) | −0.0034 (10) | −0.0236 (12) | −0.0108 (11) |
C26 | 0.0408 (12) | 0.0470 (12) | 0.0470 (12) | 0.0020 (9) | −0.0094 (9) | −0.0082 (9) |
N11 | 0.0488 (12) | 0.0693 (14) | 0.0516 (12) | −0.0075 (10) | −0.0080 (10) | −0.0036 (10) |
N12 | 0.109 (2) | 0.0686 (16) | 0.0815 (18) | 0.0172 (16) | −0.0413 (17) | −0.0378 (14) |
N13 | 0.0460 (12) | 0.0755 (17) | 0.0641 (14) | −0.0049 (11) | −0.0061 (10) | −0.0173 (12) |
O11 | 0.0621 (11) | 0.0657 (11) | 0.0569 (10) | −0.0069 (9) | −0.0078 (8) | −0.0283 (9) |
O12 | 0.0817 (15) | 0.0814 (14) | 0.0741 (13) | −0.0331 (11) | −0.0150 (11) | −0.0161 (11) |
O13 | 0.0870 (18) | 0.154 (3) | 0.106 (2) | −0.0507 (18) | 0.0476 (16) | −0.0526 (19) |
O14 | 0.153 (3) | 0.118 (2) | 0.0835 (17) | 0.0271 (19) | −0.0289 (18) | −0.0645 (16) |
O15 | 0.154 (3) | 0.096 (2) | 0.134 (2) | −0.0217 (19) | −0.050 (2) | −0.0633 (18) |
O16 | 0.087 (2) | 0.103 (2) | 0.111 (2) | −0.0076 (17) | 0.0254 (18) | −0.055 (2) |
O17 | 0.081 (2) | 0.089 (2) | 0.087 (2) | −0.0174 (15) | 0.0176 (15) | 0.0065 (16) |
O21 | 0.215 (4) | 0.099 (2) | 0.0909 (19) | −0.009 (2) | 0.043 (2) | −0.0353 (16) |
C1—C2 | 1.390 (3) | C16—C17 | 1.521 (4) |
C1—C6 | 1.394 (3) | C16—H16A | 0.9700 |
C1—N1 | 1.491 (3) | C16—H16B | 0.9700 |
C2—C3 | 1.393 (4) | C17—N2 | 1.481 (4) |
C2—H2 | 0.9300 | C17—H17A | 0.9700 |
C3—C4 | 1.378 (5) | C17—H17B | 0.9700 |
C3—H3 | 0.9300 | C18—N2 | 1.489 (4) |
C4—C5 | 1.373 (4) | C18—H18A | 0.9600 |
C4—H4 | 0.9300 | C18—H18B | 0.9600 |
C5—C6 | 1.399 (3) | C18—H18C | 0.9600 |
C5—H5 | 0.9300 | N2—H1N | 0.8596 |
C6—C7 | 1.495 (3) | N2—H2N | 0.8577 |
C7—C8 | 1.516 (4) | C21—O11 | 1.252 (3) |
C7—H7A | 0.9700 | C21—C22 | 1.440 (3) |
C7—H7B | 0.9700 | C21—C26 | 1.453 (3) |
C8—C9 | 1.513 (4) | C22—C23 | 1.385 (3) |
C8—H8A | 0.9700 | C22—N11 | 1.457 (3) |
C8—H8B | 0.9700 | C23—C24 | 1.379 (4) |
C9—C10 | 1.401 (3) | C23—H23 | 0.9300 |
C9—C14 | 1.409 (3) | C24—C25 | 1.379 (4) |
C10—C11 | 1.363 (5) | C24—N12 | 1.453 (3) |
C10—H10 | 0.9300 | C25—C26 | 1.357 (3) |
C11—C12 | 1.376 (5) | C25—H25 | 0.9300 |
C11—H11 | 0.9300 | C26—N13 | 1.456 (3) |
C12—C13 | 1.394 (4) | N11—O13 | 1.200 (3) |
C12—H12 | 0.9300 | N11—O12 | 1.222 (3) |
C13—C14 | 1.389 (3) | N12—O14 | 1.218 (4) |
C13—H13 | 0.9300 | N12—O15 | 1.229 (4) |
C14—N1 | 1.502 (3) | N13—O18 | 1.044 (19) |
C15—N1 | 1.336 (3) | N13—O16 | 1.211 (4) |
C15—C16 | 1.502 (3) | N13—O17 | 1.217 (4) |
C15—H15A | 0.9700 | N13—O19 | 1.33 (3) |
C15—H15B | 0.9700 | ||
C2—C1—C6 | 119.7 (2) | C17—C16—H16B | 109.1 |
C2—C1—N1 | 121.2 (2) | H16A—C16—H16B | 107.8 |
C6—C1—N1 | 119.15 (19) | N2—C17—C16 | 112.1 (2) |
C1—C2—C3 | 120.4 (3) | N2—C17—H17A | 109.2 |
C1—C2—H2 | 119.8 | C16—C17—H17A | 109.2 |
C3—C2—H2 | 119.8 | N2—C17—H17B | 109.2 |
C4—C3—C2 | 119.8 (3) | C16—C17—H17B | 109.2 |
C4—C3—H3 | 120.1 | H17A—C17—H17B | 107.9 |
C2—C3—H3 | 120.1 | N2—C18—H18A | 109.5 |
C5—C4—C3 | 120.1 (3) | N2—C18—H18B | 109.5 |
C5—C4—H4 | 119.9 | H18A—C18—H18B | 109.5 |
C3—C4—H4 | 119.9 | N2—C18—H18C | 109.5 |
C4—C5—C6 | 121.0 (3) | H18A—C18—H18C | 109.5 |
C4—C5—H5 | 119.5 | H18B—C18—H18C | 109.5 |
C6—C5—H5 | 119.5 | C15—N1—C1 | 121.6 (2) |
C1—C6—C5 | 119.0 (2) | C15—N1—C14 | 120.1 (2) |
C1—C6—C7 | 118.9 (2) | C1—N1—C14 | 118.30 (18) |
C5—C6—C7 | 122.1 (2) | C17—N2—C18 | 112.6 (2) |
C6—C7—C8 | 111.2 (2) | C17—N2—H1N | 110.2 |
C6—C7—H7A | 109.4 | C18—N2—H1N | 109.9 |
C8—C7—H7A | 109.4 | C17—N2—H2N | 113.6 |
C6—C7—H7B | 109.4 | C18—N2—H2N | 109.1 |
C8—C7—H7B | 109.4 | H1N—N2—H2N | 100.9 |
H7A—C7—H7B | 108.0 | O11—C21—C22 | 126.3 (2) |
C9—C8—C7 | 118.18 (18) | O11—C21—C26 | 122.4 (2) |
C9—C8—H8A | 107.8 | C22—C21—C26 | 111.3 (2) |
C7—C8—H8A | 107.8 | C23—C22—C21 | 123.6 (2) |
C9—C8—H8B | 107.8 | C23—C22—N11 | 116.1 (2) |
C7—C8—H8B | 107.8 | C21—C22—N11 | 120.3 (2) |
H8A—C8—H8B | 107.1 | C24—C23—C22 | 119.8 (2) |
C10—C9—C14 | 118.3 (2) | C24—C23—H23 | 120.1 |
C10—C9—C8 | 115.8 (2) | C22—C23—H23 | 120.1 |
C14—C9—C8 | 125.9 (2) | C23—C24—C25 | 121.0 (2) |
C11—C10—C9 | 122.6 (3) | C23—C24—N12 | 119.7 (3) |
C11—C10—H10 | 118.7 | C25—C24—N12 | 119.3 (3) |
C9—C10—H10 | 118.7 | C26—C25—C24 | 118.7 (2) |
C10—C11—C12 | 119.4 (3) | C26—C25—H25 | 120.7 |
C10—C11—H11 | 120.3 | C24—C25—H25 | 120.7 |
C12—C11—H11 | 120.3 | C25—C26—C21 | 125.6 (2) |
C11—C12—C13 | 119.6 (3) | C25—C26—N13 | 116.1 (2) |
C11—C12—H12 | 120.2 | C21—C26—N13 | 118.3 (2) |
C13—C12—H12 | 120.2 | O13—N11—O12 | 121.8 (3) |
C14—C13—C12 | 121.7 (3) | O13—N11—C22 | 118.2 (3) |
C14—C13—H13 | 119.2 | O12—N11—C22 | 120.0 (2) |
C12—C13—H13 | 119.2 | O14—N12—O15 | 124.2 (3) |
C13—C14—C9 | 118.4 (2) | O14—N12—C24 | 118.2 (3) |
C13—C14—N1 | 118.0 (2) | O15—N12—C24 | 117.6 (3) |
C9—C14—N1 | 123.6 (2) | O18—N13—O16 | 76.0 (10) |
N1—C15—C16 | 126.5 (2) | O18—N13—O17 | 67.5 (10) |
N1—C15—H15A | 105.7 | O16—N13—O17 | 121.7 (3) |
C16—C15—H15A | 105.7 | O18—N13—O19 | 119.9 (15) |
N1—C15—H15B | 105.7 | O16—N13—O19 | 82.9 (11) |
C16—C15—H15B | 105.7 | O17—N13—O19 | 78.2 (11) |
H15A—C15—H15B | 106.1 | O18—N13—C26 | 127.0 (10) |
C15—C16—C17 | 112.5 (2) | O16—N13—C26 | 119.3 (3) |
C15—C16—H16A | 109.1 | O17—N13—C26 | 118.9 (3) |
C17—C16—H16A | 109.1 | O19—N13—C26 | 112.5 (11) |
C15—C16—H16B | 109.1 | ||
C6—C1—C2—C3 | −0.4 (4) | C9—C14—N1—C15 | −136.8 (2) |
N1—C1—C2—C3 | 179.7 (2) | C13—C14—N1—C1 | −133.9 (2) |
C1—C2—C3—C4 | 0.0 (4) | C9—C14—N1—C1 | 45.6 (3) |
C2—C3—C4—C5 | 0.0 (4) | C16—C17—N2—C18 | 174.3 (3) |
C3—C4—C5—C6 | 0.4 (4) | O11—C21—C22—C23 | 178.2 (2) |
C2—C1—C6—C5 | 0.8 (3) | C26—C21—C22—C23 | 0.1 (3) |
N1—C1—C6—C5 | −179.3 (2) | O11—C21—C22—N11 | −3.4 (3) |
C2—C1—C6—C7 | −176.5 (2) | C26—C21—C22—N11 | 178.48 (19) |
N1—C1—C6—C7 | 3.4 (3) | C21—C22—C23—C24 | −0.1 (3) |
C4—C5—C6—C1 | −0.8 (4) | N11—C22—C23—C24 | −178.6 (2) |
C4—C5—C6—C7 | 176.4 (2) | C22—C23—C24—C25 | −0.6 (4) |
C1—C6—C7—C8 | 70.7 (3) | C22—C23—C24—N12 | 178.5 (2) |
C5—C6—C7—C8 | −106.4 (3) | C23—C24—C25—C26 | 1.3 (4) |
C6—C7—C8—C9 | −69.7 (3) | N12—C24—C25—C26 | −177.8 (2) |
C7—C8—C9—C10 | −165.8 (2) | C24—C25—C26—C21 | −1.4 (4) |
C7—C8—C9—C14 | 14.5 (3) | C24—C25—C26—N13 | 179.8 (2) |
C14—C9—C10—C11 | 0.4 (4) | O11—C21—C26—C25 | −177.5 (2) |
C8—C9—C10—C11 | −179.3 (2) | C22—C21—C26—C25 | 0.7 (3) |
C9—C10—C11—C12 | −0.6 (5) | O11—C21—C26—N13 | 1.3 (3) |
C10—C11—C12—C13 | 0.5 (5) | C22—C21—C26—N13 | 179.5 (2) |
C11—C12—C13—C14 | −0.3 (4) | C23—C22—N11—O13 | −8.1 (4) |
C12—C13—C14—C9 | 0.1 (4) | C21—C22—N11—O13 | 173.4 (3) |
C12—C13—C14—N1 | 179.7 (2) | C23—C22—N11—O12 | 170.7 (2) |
C10—C9—C14—C13 | −0.2 (3) | C21—C22—N11—O12 | −7.8 (3) |
C8—C9—C14—C13 | 179.6 (2) | C23—C24—N12—O14 | −1.0 (4) |
C10—C9—C14—N1 | −179.7 (2) | C25—C24—N12—O14 | 178.1 (3) |
C8—C9—C14—N1 | 0.0 (3) | C23—C24—N12—O15 | 179.5 (3) |
N1—C15—C16—C17 | −136.0 (3) | C25—C24—N12—O15 | −1.5 (4) |
C15—C16—C17—N2 | 64.2 (3) | C25—C26—N13—O18 | 130.1 (13) |
C16—C15—N1—C1 | −3.1 (4) | C21—C26—N13—O18 | −48.8 (14) |
C16—C15—N1—C14 | 179.5 (2) | C25—C26—N13—O16 | −135.5 (3) |
C2—C1—N1—C15 | −63.9 (3) | C21—C26—N13—O16 | 45.6 (4) |
C6—C1—N1—C15 | 116.2 (2) | C25—C26—N13—O17 | 47.6 (4) |
C2—C1—N1—C14 | 113.6 (2) | C21—C26—N13—O17 | −131.3 (3) |
C6—C1—N1—C14 | −66.3 (3) | C25—C26—N13—O19 | −40.9 (12) |
C13—C14—N1—C15 | 43.6 (3) | C21—C26—N13—O19 | 140.1 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N···O11 | 0.86 | 2.06 | 2.817 (3) | 146 |
N2—H1N···O12 | 0.86 | 2.38 | 3.001 (3) | 129 |
N2—H2N···O21 | 0.86 | 2.03 | 2.873 (4) | 170 |
Experimental details
Crystal data | |
Chemical formula | C18H23N2+·C6H2N3O7−·H2O |
Mr | 513.51 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 291 |
a, b, c (Å) | 10.3126 (4), 11.2594 (5), 11.4304 (5) |
α, β, γ (°) | 72.162 (1), 79.288 (1), 87.233 (1) |
V (Å3) | 1241.35 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.60 × 0.50 × 0.45 |
Data collection | |
Diffractometer | Bruker SMART1000 CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.943, 0.954 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11334, 4865, 3688 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.220, 1.04 |
No. of reflections | 4865 |
No. of parameters | 344 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.47, −0.58 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N···O11 | 0.86 | 2.06 | 2.817 (3) | 146 |
N2—H1N···O12 | 0.86 | 2.38 | 3.001 (3) | 129 |
N2—H2N···O21 | 0.86 | 2.03 | 2.873 (4) | 170 |
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Desipramine, 10,11-dihydro-5-[3-(methylamino)propyl]-5H-dibenz[b,f]azepine, C18H22N2, is a tricyclic antidepressant (TCA) and pain reliever that inhibits the reuptake of norepinephrine. Medical applications (Cohen et al., 1990) usually utilize desipramine as its hydrochloride salt, i.e. C18H23N2+·Cl-. A recent proposed new application of desipramine hydrochloride as a reagent for the detection of microamounts of blood in urine (Ahmed et al., 2002).
In continuation of our work on the picrate salts of pharmaceutical compounds (Portalone et al., 2007; Harrison, Ashok et al., 2007; Harrison, Bindya et al., 2007), we now report the structure of the title compound, (I).
The structure of (I) (Fig. 1) shows that proton transfer from picric acid (pa) to desipramine (dp) has occurred, and that the secondary-amine N atom of the side chain has been protonated to yield an –NH2+– grouping. The dihedral angle between the C1–C6 and C9–C14 ring planes in (I) is 53.92 (8)°. The bond-angle sum for N1 is 360.0°, indicating sp2 hybridization. However, the unobserved p orbital appears not to be well aligned to overlap with the π clouds of the adjacent benzene rings, as the C1/C14/C15/N1 grouping makes dihedral angles of 65.28 (10)° and 44.78 (11)° with the C1–C6 and C9–C14 ring planes, respectively. The seven-membered ring in (I) approximates to a boat, with C1/C6/C8/C9 almost co-planar (r.m.s. deviation = 0.002 Å), C7 forming the prow [deviation = 0.721 (3) Å] and N1 and C14 the stern [deviations = 0.787 (4) and 0.351 (4) Å, respectively].
The significant variation of the C—C bond lengths around the picrate aromatic ring in (I) are normal (Harrison, Ashok et al., 2007). The N13 nitro group is disordered over two orientations.
In the crystal, the cation and anion are linked by a bifurcated N—H···(O,O) hydrogen bond (Table 1), as also seen in related compounds (Harrison, Ashok et al., 2007). The cation also bonds to the O21 water molecule with an N—H···O link. Unfortunately, the water molecule H atoms were not located in this study. One of the H atoms is probably involved in an H bond to O16 [O21···O16 = 2.667 (5) Å], but there is no obvious second H bond and geometrical placement of the H atoms was not attempted.