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Two salts of acyclic Schiff base cationic ligands, namely N,N'-bis(2-nitrobenzyl)propane-1,3-diammonium dichloride monohydrate, C17H22N4O42+·2Cl-·H2O, (I), and 2-hydroxy-N,N'-bis(2-nitrobenzyl)propane-1,3-diammonium dichloride, C17H22N4O52+·2Cl-, (II), were synthesized as precursors in order to obtain new acyclic and macrocyclic multidentate ligands and complexes. The cation conformations in compounds (I) and (II) are different in the solid state, although the cations are closely related chemically. Similarly, the hydrogen-bonding networks involving ammonium cations, hydroxyl groups and chloride anions are also different. In the cation of compound (II), the hydroxyl group is disordered over two sets of sites, with occupancies of 0.785 (8) and 0.215 (8).
Supporting information
CCDC references: 665509; 665510
The title acyclic cationic ligands, (I) and (II), were obtained by a three-step reaction procedure. The condensation between 1,2-diaminoethane, for compound (I), or 1,3-diamino-2-hydroxypropane, for compound (II), with 2-nitrobenzyl chloride produced the corresponding imines. Selective reduction of the imines with sodium borohydride in methanol gave the corresponding amines, which were isolated as oils. They were converted to their chloride salts, using HCl dissolved in ethanol [yields: 70% for compound (I) and 47% for compound (II)]. Suitable colourless crystals of compounds (I) and (II) were obtained by slow evaporation of ethanol solutions at 298 K.
The geometry of the water molecule in compound (I) was regularized using two restraints; O—H = 0.85 (2) Å. Other H atoms were placed in idealized positions and refined using a riding approximation, with C—H bond lengths set to 0.93 (aromatic CH) or 0.97 Å (methylene CH2), and with Uiso(H) = 1.2Ueq(carrier C). For compound (II), the hydroxyl O atom was found to be disordered over two positions and the corresponding site occupation factors were refined, with their sum constrained to 1; the occupancies converged to 0.785 (8) (atom O3A) and 0.215 (8) (atom O3B). In order to obtain a sensible geometry, C—O bond lengths were restrained to 1.45 (1) Å. Site O3A was refined anisotropically, with restrictions on its Uij parameters approximating isotropic behaviour. Site O3B was refined isotropically, due to its limited occupancy. Hydroxyl H atom H3AA bonded to atom O3A was included in a calculated position and refined using a riding model (O—H constrained to 0.85 Å), but allowing free rotation about the C—O axis. The other hydroxyl H atom, H3AB, was included in a calculated position and refined as riding on atom O3B. Other H atoms were placed in idealized positions and all were refined as riding on their carrier atoms, with bond lengths fixed to 0.90 (ammonium NH), 0.93 (aromatic CH), 0.97 (methylene CH2) or 0.98 Å (methine CH). In compound (II), all H atoms were refined with fixed isotropic displacement parameters calculated as Uiso(H) = xUeq(carrier atom), where x = 1.5 for hydroxyl groups and x = 1.2 otherwise. For compound (II), 1557 measured Friedel pairs were used for the refinement of the Flack parameter (Flack, 1983), using this parameter only for crystal chirality determination.
For both compounds, data collection: XSCANS (Siemens, 1999); cell refinement: XSCANS (Siemens, 1999); data reduction: XSCANS (Siemens, 1999); program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 1997); program(s) used to refine structure: SHELXTL-Plus (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL-Plus (Sheldrick, 1997).
(I)
N,
N'-bis(2-nitrobenzyl)propane-1,3-diammonium dichloride monohydrate
top
Crystal data top
C17H22N4O42+·2Cl−·H2O | Z = 2 |
Mr = 435.30 | F(000) = 456 |
Triclinic, P1 | Dx = 1.431 Mg m−3 |
Hall symbol: -P 1 | Melting point: 493 K |
a = 8.630 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.449 (4) Å | Cell parameters from 100 reflections |
c = 11.629 (4) Å | θ = 4.7–12.4° |
α = 116.353 (17)° | µ = 0.36 mm−1 |
β = 92.09 (2)° | T = 297 K |
γ = 98.82 (2)° | Irregular, colourless |
V = 1010.2 (6) Å3 | 0.5 × 0.5 × 0.4 mm |
Data collection top
Siemens P4 diffractometer | 3585 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.072 |
Graphite monochromator | θmax = 27.5°, θmin = 2.0° |
2θ/ω scans | h = −11→11 |
Absorption correction: ψ scan (XSCANS; Siemens, 1999) | k = −13→13 |
Tmin = 0.845, Tmax = 0.867 | l = −15→15 |
8783 measured reflections | 3 standard reflections every 97 reflections |
4456 independent reflections | intensity decay: 5.0% |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0317P)2 + 0.255P] where P = (Fo2 + 2Fc2)/3 |
4456 reflections | (Δ/σ)max < 0.001 |
261 parameters | Δρmax = 0.30 e Å−3 |
2 restraints | Δρmin = −0.36 e Å−3 |
Crystal data top
C17H22N4O42+·2Cl−·H2O | γ = 98.82 (2)° |
Mr = 435.30 | V = 1010.2 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.630 (3) Å | Mo Kα radiation |
b = 11.449 (4) Å | µ = 0.36 mm−1 |
c = 11.629 (4) Å | T = 297 K |
α = 116.353 (17)° | 0.5 × 0.5 × 0.4 mm |
β = 92.09 (2)° | |
Data collection top
Siemens P4 diffractometer | 3585 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XSCANS; Siemens, 1999) | Rint = 0.072 |
Tmin = 0.845, Tmax = 0.867 | 3 standard reflections every 97 reflections |
8783 measured reflections | intensity decay: 5.0% |
4456 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.039 | 2 restraints |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.30 e Å−3 |
4456 reflections | Δρmin = −0.36 e Å−3 |
261 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.92967 (5) | 0.19295 (5) | 0.60161 (5) | 0.05788 (15) | |
Cl2 | 0.73437 (7) | 0.56226 (5) | 0.66732 (6) | 0.07018 (17) | |
O1 | 0.75377 (18) | 0.09680 (16) | 0.90725 (16) | 0.0685 (4) | |
O2 | 0.63727 (18) | 0.11416 (12) | 0.75271 (12) | 0.0574 (3) | |
O3 | −0.12907 (17) | −0.08952 (15) | 0.05791 (15) | 0.0744 (5) | |
O4 | −0.37590 (17) | −0.14445 (15) | 0.05984 (15) | 0.0721 (4) | |
N1 | 0.70942 (17) | 0.16290 (15) | 0.85994 (15) | 0.0479 (3) | |
N2 | 0.61736 (14) | 0.29843 (12) | 0.66152 (12) | 0.0355 (3) | |
H2B | 0.6554 | 0.3719 | 0.6537 | 0.043* | |
H2C | 0.6994 | 0.2596 | 0.6648 | 0.043* | |
N3 | 0.12250 (14) | 0.21687 (12) | 0.38934 (12) | 0.0380 (3) | |
H3B | 0.1535 | 0.2959 | 0.3899 | 0.046* | |
H3C | 0.0646 | 0.2295 | 0.4553 | 0.046* | |
N4 | −0.25480 (17) | −0.06289 (16) | 0.09298 (14) | 0.0518 (4) | |
C1 | 0.74305 (18) | 0.30714 (17) | 0.93572 (15) | 0.0437 (4) | |
C2 | 0.8494 (2) | 0.3581 (2) | 1.04487 (18) | 0.0583 (5) | |
H2A | 0.8956 | 0.3017 | 1.0673 | 0.070* | |
C3 | 0.8866 (2) | 0.4923 (2) | 1.12013 (19) | 0.0672 (6) | |
H3A | 0.9578 | 0.5278 | 1.1946 | 0.081* | |
C4 | 0.8191 (2) | 0.5737 (2) | 1.08579 (19) | 0.0645 (6) | |
H4A | 0.8451 | 0.6651 | 1.1369 | 0.077* | |
C5 | 0.7124 (2) | 0.52238 (17) | 0.97581 (17) | 0.0518 (4) | |
H5A | 0.6679 | 0.5797 | 0.9536 | 0.062* | |
C6 | 0.67083 (17) | 0.38687 (16) | 0.89835 (15) | 0.0407 (3) | |
C7 | 0.54753 (17) | 0.33851 (16) | 0.78538 (15) | 0.0409 (3) | |
H7A | 0.4738 | 0.2632 | 0.7811 | 0.049* | |
H7B | 0.4891 | 0.4083 | 0.7976 | 0.049* | |
C8 | 0.50655 (17) | 0.20662 (15) | 0.54548 (15) | 0.0396 (3) | |
H8A | 0.4659 | 0.1267 | 0.5529 | 0.048* | |
H8B | 0.5631 | 0.1815 | 0.4700 | 0.048* | |
C9 | 0.37071 (17) | 0.26646 (15) | 0.52676 (15) | 0.0407 (3) | |
H9A | 0.4096 | 0.3450 | 0.5166 | 0.049* | |
H9B | 0.3134 | 0.2924 | 0.6018 | 0.049* | |
C10 | 0.26260 (17) | 0.16554 (15) | 0.40802 (15) | 0.0398 (3) | |
H10A | 0.3193 | 0.1433 | 0.3328 | 0.048* | |
H10B | 0.2295 | 0.0852 | 0.4166 | 0.048* | |
C11 | 0.02403 (18) | 0.12455 (16) | 0.26619 (16) | 0.0441 (4) | |
H11A | 0.0049 | 0.0359 | 0.2596 | 0.053* | |
H11B | 0.0807 | 0.1219 | 0.1948 | 0.053* | |
C12 | −0.13034 (18) | 0.16457 (16) | 0.25564 (15) | 0.0410 (3) | |
C13 | −0.1514 (2) | 0.29375 (18) | 0.32730 (19) | 0.0528 (4) | |
H13A | −0.0673 | 0.3568 | 0.3840 | 0.063* | |
C14 | −0.2919 (2) | 0.3317 (2) | 0.3175 (2) | 0.0580 (5) | |
H14A | −0.3013 | 0.4197 | 0.3662 | 0.070* | |
C15 | −0.4186 (2) | 0.2412 (2) | 0.23670 (19) | 0.0555 (5) | |
H15A | −0.5137 | 0.2673 | 0.2292 | 0.067* | |
C16 | −0.40387 (19) | 0.1124 (2) | 0.16738 (17) | 0.0502 (4) | |
H16A | −0.4902 | 0.0493 | 0.1141 | 0.060* | |
C17 | −0.26222 (18) | 0.07583 (17) | 0.17609 (15) | 0.0422 (3) | |
O5 | 0.7863 (2) | −0.0754 (2) | 0.34435 (18) | 0.0750 (4) | |
H5B | 0.865 (4) | −0.116 (4) | 0.354 (4) | 0.162 (17)* | |
H5C | 0.809 (4) | 0.004 (2) | 0.413 (3) | 0.124 (13)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0485 (2) | 0.0672 (3) | 0.0571 (3) | 0.0205 (2) | 0.01804 (19) | 0.0237 (2) |
Cl2 | 0.0824 (4) | 0.0470 (3) | 0.0901 (4) | 0.0021 (2) | 0.0162 (3) | 0.0419 (3) |
O1 | 0.0725 (9) | 0.0708 (9) | 0.0839 (10) | 0.0217 (7) | 0.0084 (8) | 0.0519 (8) |
O2 | 0.0809 (9) | 0.0431 (7) | 0.0471 (7) | 0.0107 (6) | 0.0071 (6) | 0.0200 (5) |
O3 | 0.0582 (8) | 0.0676 (9) | 0.0658 (9) | 0.0128 (7) | 0.0081 (7) | 0.0021 (7) |
O4 | 0.0558 (8) | 0.0591 (8) | 0.0763 (10) | −0.0081 (6) | −0.0136 (7) | 0.0162 (7) |
N1 | 0.0487 (7) | 0.0507 (8) | 0.0544 (8) | 0.0120 (6) | 0.0153 (6) | 0.0313 (7) |
N2 | 0.0320 (5) | 0.0352 (6) | 0.0417 (6) | 0.0059 (5) | 0.0071 (5) | 0.0197 (5) |
N3 | 0.0357 (6) | 0.0343 (6) | 0.0428 (7) | 0.0021 (5) | 0.0019 (5) | 0.0180 (5) |
N4 | 0.0467 (7) | 0.0550 (9) | 0.0426 (7) | 0.0048 (6) | −0.0042 (6) | 0.0146 (6) |
C1 | 0.0413 (8) | 0.0493 (9) | 0.0412 (8) | 0.0060 (6) | 0.0110 (6) | 0.0217 (7) |
C2 | 0.0529 (10) | 0.0787 (13) | 0.0470 (10) | 0.0066 (9) | 0.0051 (7) | 0.0337 (9) |
C3 | 0.0579 (11) | 0.0843 (15) | 0.0408 (9) | −0.0060 (10) | 0.0010 (8) | 0.0186 (10) |
C4 | 0.0604 (11) | 0.0572 (11) | 0.0472 (10) | −0.0065 (9) | 0.0124 (8) | 0.0034 (9) |
C5 | 0.0524 (9) | 0.0438 (9) | 0.0490 (9) | 0.0075 (7) | 0.0144 (7) | 0.0120 (7) |
C6 | 0.0373 (7) | 0.0433 (8) | 0.0370 (7) | 0.0051 (6) | 0.0109 (6) | 0.0146 (6) |
C7 | 0.0355 (7) | 0.0439 (8) | 0.0424 (8) | 0.0088 (6) | 0.0102 (6) | 0.0179 (6) |
C8 | 0.0388 (7) | 0.0386 (8) | 0.0405 (8) | 0.0069 (6) | 0.0038 (6) | 0.0173 (6) |
C9 | 0.0380 (7) | 0.0365 (8) | 0.0468 (8) | 0.0048 (6) | 0.0016 (6) | 0.0193 (6) |
C10 | 0.0377 (7) | 0.0390 (8) | 0.0444 (8) | 0.0058 (6) | 0.0041 (6) | 0.0208 (6) |
C11 | 0.0386 (7) | 0.0412 (8) | 0.0454 (8) | 0.0031 (6) | 0.0008 (6) | 0.0153 (7) |
C12 | 0.0393 (7) | 0.0453 (8) | 0.0404 (8) | 0.0070 (6) | 0.0051 (6) | 0.0214 (6) |
C13 | 0.0526 (9) | 0.0462 (9) | 0.0560 (10) | 0.0094 (7) | 0.0014 (8) | 0.0204 (8) |
C14 | 0.0641 (11) | 0.0567 (11) | 0.0612 (11) | 0.0237 (9) | 0.0131 (9) | 0.0297 (9) |
C15 | 0.0458 (9) | 0.0784 (13) | 0.0588 (11) | 0.0228 (9) | 0.0128 (8) | 0.0417 (10) |
C16 | 0.0397 (8) | 0.0704 (12) | 0.0468 (9) | 0.0075 (7) | 0.0030 (6) | 0.0333 (8) |
C17 | 0.0418 (8) | 0.0496 (9) | 0.0364 (7) | 0.0055 (6) | 0.0040 (6) | 0.0216 (7) |
O5 | 0.0707 (10) | 0.0792 (12) | 0.0814 (11) | −0.0018 (8) | −0.0074 (8) | 0.0483 (10) |
Geometric parameters (Å, º) top
O1—N1 | 1.210 (2) | C7—H7A | 0.9700 |
O2—N1 | 1.214 (2) | C7—H7B | 0.9700 |
O3—N4 | 1.208 (2) | C8—C9 | 1.500 (2) |
O4—N4 | 1.210 (2) | C8—H8A | 0.9700 |
N1—C1 | 1.459 (2) | C8—H8B | 0.9700 |
N2—C8 | 1.476 (2) | C9—C10 | 1.507 (2) |
N2—C7 | 1.4865 (19) | C9—H9A | 0.9700 |
N2—H2B | 0.9000 | C9—H9B | 0.9700 |
N2—H2C | 0.9000 | C10—H10A | 0.9700 |
N3—C10 | 1.472 (2) | C10—H10B | 0.9700 |
N3—C11 | 1.477 (2) | C11—C12 | 1.492 (2) |
N3—H3B | 0.9000 | C11—H11A | 0.9700 |
N3—H3C | 0.9000 | C11—H11B | 0.9700 |
N4—C17 | 1.461 (2) | C12—C13 | 1.384 (2) |
C1—C2 | 1.373 (3) | C12—C17 | 1.385 (2) |
C1—C6 | 1.385 (3) | C13—C14 | 1.366 (3) |
C2—C3 | 1.365 (3) | C13—H13A | 0.9300 |
C2—H2A | 0.9300 | C14—C15 | 1.365 (3) |
C3—C4 | 1.359 (4) | C14—H14A | 0.9300 |
C3—H3A | 0.9300 | C15—C16 | 1.360 (3) |
C4—C5 | 1.382 (3) | C15—H15A | 0.9300 |
C4—H4A | 0.9300 | C16—C17 | 1.366 (3) |
C5—C6 | 1.383 (2) | C16—H16A | 0.9300 |
C5—H5A | 0.9300 | O5—H5B | 0.91 (4) |
C6—C7 | 1.495 (2) | O5—H5C | 0.89 (3) |
| | | |
O1—N1—O2 | 122.73 (17) | N2—C8—H8A | 109.1 |
O1—N1—C1 | 118.49 (17) | C9—C8—H8A | 109.1 |
O2—N1—C1 | 118.78 (16) | N2—C8—H8B | 109.1 |
C8—N2—C7 | 114.56 (11) | C9—C8—H8B | 109.1 |
C8—N2—H2B | 108.6 | H8A—C8—H8B | 107.8 |
C7—N2—H2B | 108.6 | C8—C9—C10 | 108.96 (13) |
C8—N2—H2C | 108.6 | C8—C9—H9A | 109.9 |
C7—N2—H2C | 108.6 | C10—C9—H9A | 109.9 |
H2B—N2—H2C | 107.6 | C8—C9—H9B | 109.9 |
C10—N3—C11 | 111.58 (12) | C10—C9—H9B | 109.9 |
C10—N3—H3B | 109.3 | H9A—C9—H9B | 108.3 |
C11—N3—H3B | 109.3 | N3—C10—C9 | 111.12 (13) |
C10—N3—H3C | 109.3 | N3—C10—H10A | 109.4 |
C11—N3—H3C | 109.3 | C9—C10—H10A | 109.4 |
H3B—N3—H3C | 108.0 | N3—C10—H10B | 109.4 |
O3—N4—O4 | 123.50 (17) | C9—C10—H10B | 109.4 |
O3—N4—C17 | 118.28 (14) | H10A—C10—H10B | 108.0 |
O4—N4—C17 | 118.18 (15) | N3—C11—C12 | 112.05 (13) |
C2—C1—C6 | 122.48 (17) | N3—C11—H11A | 109.2 |
C2—C1—N1 | 116.31 (18) | C12—C11—H11A | 109.2 |
C6—C1—N1 | 121.21 (15) | N3—C11—H11B | 109.2 |
C3—C2—C1 | 119.4 (2) | C12—C11—H11B | 109.2 |
C3—C2—H2A | 120.3 | H11A—C11—H11B | 107.9 |
C1—C2—H2A | 120.3 | C13—C12—C17 | 115.50 (16) |
C4—C3—C2 | 119.7 (2) | C13—C12—C11 | 121.68 (15) |
C4—C3—H3A | 120.1 | C17—C12—C11 | 122.81 (15) |
C2—C3—H3A | 120.1 | C14—C13—C12 | 122.14 (17) |
C3—C4—C5 | 120.84 (19) | C14—C13—H13A | 118.9 |
C3—C4—H4A | 119.6 | C12—C13—H13A | 118.9 |
C5—C4—H4A | 119.6 | C15—C14—C13 | 120.42 (19) |
C4—C5—C6 | 120.8 (2) | C15—C14—H14A | 119.8 |
C4—C5—H5A | 119.6 | C13—C14—H14A | 119.8 |
C6—C5—H5A | 119.6 | C16—C15—C14 | 119.22 (18) |
C5—C6—C1 | 116.69 (17) | C16—C15—H15A | 120.4 |
C5—C6—C7 | 117.72 (17) | C14—C15—H15A | 120.4 |
C1—C6—C7 | 125.53 (15) | C15—C16—C17 | 119.95 (17) |
N2—C7—C6 | 112.00 (12) | C15—C16—H16A | 120.0 |
N2—C7—H7A | 109.2 | C17—C16—H16A | 120.0 |
C6—C7—H7A | 109.2 | C16—C17—C12 | 122.74 (16) |
N2—C7—H7B | 109.2 | C16—C17—N4 | 116.24 (15) |
C6—C7—H7B | 109.2 | C12—C17—N4 | 120.99 (15) |
H7A—C7—H7B | 107.9 | H5B—O5—H5C | 103 (3) |
N2—C8—C9 | 112.56 (13) | | |
| | | |
C8—N2—C7—C6 | 158.61 (14) | N1—C1—C6—C7 | 3.7 (2) |
C7—N2—C8—C9 | 62.25 (18) | C5—C6—C7—N2 | 102.98 (16) |
N2—C8—C9—C10 | −179.01 (12) | C1—C6—C7—N2 | −79.87 (19) |
C8—C9—C10—N3 | 176.86 (13) | N3—C11—C12—C13 | 22.1 (2) |
C11—N3—C10—C9 | 174.09 (13) | N3—C11—C12—C17 | −156.81 (15) |
C10—N3—C11—C12 | 170.94 (13) | C17—C12—C13—C14 | −1.7 (3) |
O1—N1—C1—C2 | 12.4 (2) | C11—C12—C13—C14 | 179.40 (18) |
O2—N1—C1—C2 | −168.12 (15) | C12—C13—C14—C15 | 1.0 (3) |
O1—N1—C1—C6 | −167.59 (15) | C13—C14—C15—C16 | 0.9 (3) |
O2—N1—C1—C6 | 11.9 (2) | C14—C15—C16—C17 | −2.0 (3) |
C6—C1—C2—C3 | −0.1 (3) | C15—C16—C17—C12 | 1.3 (3) |
N1—C1—C2—C3 | 179.85 (15) | C15—C16—C17—N4 | −176.74 (16) |
C1—C2—C3—C4 | −0.5 (3) | C13—C12—C17—C16 | 0.5 (2) |
C2—C3—C4—C5 | 0.4 (3) | C11—C12—C17—C16 | 179.42 (16) |
C3—C4—C5—C6 | 0.4 (3) | C13—C12—C17—N4 | 178.48 (16) |
C4—C5—C6—C1 | −1.0 (2) | C11—C12—C17—N4 | −2.6 (2) |
C4—C5—C6—C7 | 176.44 (15) | O3—N4—C17—C16 | 151.53 (18) |
C2—C1—C6—C5 | 0.8 (2) | O4—N4—C17—C16 | −26.3 (2) |
N1—C1—C6—C5 | −179.14 (13) | O3—N4—C17—C12 | −26.6 (3) |
C2—C1—C6—C7 | −176.34 (15) | O4—N4—C17—C12 | 155.57 (17) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···Cl2 | 0.90 | 2.11 | 3.0043 (17) | 170 |
N2—H2C···Cl1 | 0.90 | 2.27 | 3.0976 (16) | 153 |
N2—H2C···O2 | 0.90 | 2.32 | 2.773 (2) | 111 |
N3—H3B···Cl2i | 0.90 | 2.13 | 2.9890 (17) | 159 |
N3—H3C···Cl1ii | 0.90 | 2.25 | 3.1142 (17) | 161 |
O5—H5B···Cl1iii | 0.91 (4) | 2.24 (2) | 3.141 (2) | 173 (4) |
O5—H5C···Cl1 | 0.89 (3) | 2.35 (2) | 3.213 (2) | 165 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z; (iii) −x+2, −y, −z+1. |
(II) 2-hydroxy-
N,
N'-bis(2-nitrobenzyl)propane-1,3-diammonium dichloride
top
Crystal data top
C17H22N4O52+·2Cl− | F(000) = 904 |
Mr = 433.29 | Dx = 1.384 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 73 reflections |
a = 7.075 (2) Å | θ = 3.9–11.6° |
b = 15.844 (8) Å | µ = 0.35 mm−1 |
c = 18.554 (6) Å | T = 298 K |
V = 2079.8 (14) Å3 | Irregular, colourless |
Z = 4 | 0.4 × 0.2 × 0.2 mm |
Data collection top
Siemens P4 diffractometer | 2729 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.089 |
Graphite monochromator | θmax = 25.1°, θmin = 2.2° |
2θ/ω scans | h = −8→4 |
Absorption correction: ψ scan (XSCANS; Siemens, 1999) | k = −18→18 |
Tmin = 0.739, Tmax = 0.934 | l = −22→22 |
6209 measured reflections | 3 standard reflections every 97 reflections |
3692 independent reflections | intensity decay: 10.2% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.055 | H-atom parameters constrained |
wR(F2) = 0.145 | w = 1/[σ2(Fo2) + (0.0581P)2 + 0.84P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
3692 reflections | Δρmax = 0.36 e Å−3 |
259 parameters | Δρmin = −0.30 e Å−3 |
8 restraints | Absolute structure: Flack (1983), with 1557 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (11) |
Crystal data top
C17H22N4O52+·2Cl− | V = 2079.8 (14) Å3 |
Mr = 433.29 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.075 (2) Å | µ = 0.35 mm−1 |
b = 15.844 (8) Å | T = 298 K |
c = 18.554 (6) Å | 0.4 × 0.2 × 0.2 mm |
Data collection top
Siemens P4 diffractometer | 2729 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XSCANS; Siemens, 1999) | Rint = 0.089 |
Tmin = 0.739, Tmax = 0.934 | 3 standard reflections every 97 reflections |
6209 measured reflections | intensity decay: 10.2% |
3692 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | H-atom parameters constrained |
wR(F2) = 0.145 | Δρmax = 0.36 e Å−3 |
S = 1.04 | Δρmin = −0.30 e Å−3 |
3692 reflections | Absolute structure: Flack (1983), with 1557 Friedel pairs |
259 parameters | Absolute structure parameter: −0.03 (11) |
8 restraints | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cl1 | −0.00591 (15) | 0.56475 (9) | 0.50575 (6) | 0.0737 (4) | |
Cl2 | −0.01826 (16) | 0.85474 (9) | 0.62691 (7) | 0.0797 (4) | |
O1 | 0.2619 (9) | 0.3278 (2) | 0.6517 (2) | 0.1179 (19) | |
O2 | 0.3090 (6) | 0.4599 (2) | 0.63676 (18) | 0.0773 (10) | |
O4 | 0.2676 (6) | 0.8259 (2) | 0.77899 (18) | 0.0822 (11) | |
O5 | 0.1602 (8) | 0.8900 (3) | 0.8701 (2) | 0.1102 (15) | |
N1 | 0.2874 (7) | 0.3883 (3) | 0.6130 (2) | 0.0708 (11) | |
N2 | 0.4296 (4) | 0.5762 (2) | 0.52583 (19) | 0.0505 (8) | |
H2D | 0.4209 | 0.6013 | 0.4824 | 0.061* | |
H2E | 0.3114 | 0.5660 | 0.5415 | 0.061* | |
N3 | 0.4213 (4) | 0.85546 (19) | 0.64045 (16) | 0.0450 (7) | |
H3C | 0.2995 | 0.8473 | 0.6526 | 0.054* | |
H3D | 0.4233 | 0.8802 | 0.5968 | 0.054* | |
N4 | 0.2207 (6) | 0.8900 (3) | 0.80974 (19) | 0.0606 (10) | |
C1 | 0.2910 (6) | 0.3757 (3) | 0.5361 (2) | 0.0540 (11) | |
C2 | 0.1787 (7) | 0.3110 (3) | 0.5091 (3) | 0.0668 (13) | |
H2B | 0.1033 | 0.2790 | 0.5397 | 0.080* | |
C3 | 0.1813 (8) | 0.2956 (3) | 0.4367 (3) | 0.0723 (14) | |
H3B | 0.1071 | 0.2524 | 0.4178 | 0.087* | |
C4 | 0.2917 (8) | 0.3428 (3) | 0.3914 (3) | 0.0735 (14) | |
H4A | 0.2928 | 0.3318 | 0.3422 | 0.088* | |
C5 | 0.4009 (7) | 0.4068 (3) | 0.4193 (3) | 0.0661 (13) | |
H5A | 0.4758 | 0.4384 | 0.3882 | 0.079* | |
C6 | 0.4028 (5) | 0.4257 (2) | 0.4919 (2) | 0.0515 (10) | |
C7 | 0.5309 (6) | 0.4946 (2) | 0.5176 (3) | 0.0609 (12) | |
H7A | 0.5854 | 0.4786 | 0.5636 | 0.073* | |
H7B | 0.6335 | 0.5017 | 0.4834 | 0.073* | |
C8 | 0.5237 (6) | 0.6345 (2) | 0.5766 (2) | 0.0522 (10) | |
H8A | 0.6489 | 0.6481 | 0.5588 | 0.063* | |
H8B | 0.5377 | 0.6071 | 0.6231 | 0.063* | |
C9 | 0.4120 (6) | 0.7145 (3) | 0.5858 (2) | 0.0526 (10) | |
H9AA | 0.3824 | 0.7413 | 0.5395 | 0.063* | 0.785 (8) |
H9AB | 0.2766 | 0.7076 | 0.5951 | 0.063* | 0.215 (8) |
C10 | 0.5164 (6) | 0.7728 (2) | 0.6356 (2) | 0.0498 (9) | |
H10A | 0.5233 | 0.7476 | 0.6832 | 0.060* | |
H10B | 0.6445 | 0.7806 | 0.6182 | 0.060* | |
C11 | 0.5092 (7) | 0.9132 (3) | 0.6936 (2) | 0.0538 (10) | |
H11A | 0.6193 | 0.9396 | 0.6721 | 0.065* | |
H11B | 0.5511 | 0.8809 | 0.7350 | 0.065* | |
C12 | 0.3735 (6) | 0.9805 (2) | 0.7180 (2) | 0.0483 (10) | |
C13 | 0.3818 (7) | 1.0591 (3) | 0.6873 (2) | 0.0634 (12) | |
H13A | 0.4664 | 1.0684 | 0.6498 | 0.076* | |
C14 | 0.2692 (9) | 1.1245 (3) | 0.7103 (3) | 0.0761 (15) | |
H14A | 0.2798 | 1.1773 | 0.6887 | 0.091* | |
C15 | 0.1420 (8) | 1.1123 (3) | 0.7645 (3) | 0.0743 (15) | |
H15A | 0.0633 | 1.1562 | 0.7789 | 0.089* | |
C16 | 0.1304 (7) | 1.0359 (3) | 0.7974 (3) | 0.0642 (12) | |
H16A | 0.0477 | 1.0277 | 0.8357 | 0.077* | |
C17 | 0.2421 (6) | 0.9712 (2) | 0.7734 (2) | 0.0488 (10) | |
O3A | 0.2431 (5) | 0.6877 (2) | 0.6240 (2) | 0.0612 (13) | 0.785 (8) |
H3AA | 0.1492 | 0.6886 | 0.5954 | 0.092* | 0.785 (8) |
O3B | 0.468 (3) | 0.7513 (14) | 0.5147 (8) | 0.120 (8)* | 0.215 (8) |
H3BA | 0.4160 | 0.7993 | 0.5095 | 0.180* | 0.215 (8) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0372 (5) | 0.1164 (10) | 0.0676 (6) | −0.0028 (7) | −0.0023 (6) | 0.0293 (7) |
Cl2 | 0.0397 (5) | 0.1011 (9) | 0.0982 (9) | −0.0019 (6) | 0.0001 (6) | 0.0194 (8) |
O1 | 0.202 (6) | 0.067 (2) | 0.085 (3) | −0.014 (3) | −0.021 (3) | 0.025 (2) |
O2 | 0.102 (3) | 0.060 (2) | 0.070 (2) | −0.001 (2) | −0.010 (2) | −0.0083 (17) |
O4 | 0.130 (3) | 0.0524 (18) | 0.0646 (19) | 0.000 (2) | 0.016 (2) | 0.0101 (17) |
O5 | 0.162 (4) | 0.098 (3) | 0.070 (2) | 0.006 (3) | 0.043 (3) | 0.011 (2) |
N1 | 0.083 (3) | 0.060 (3) | 0.070 (3) | 0.001 (2) | −0.012 (2) | 0.012 (2) |
N2 | 0.0364 (16) | 0.0436 (18) | 0.072 (2) | −0.0009 (15) | −0.0023 (15) | −0.0049 (17) |
N3 | 0.0407 (16) | 0.0467 (18) | 0.0476 (17) | 0.0005 (15) | −0.0001 (14) | −0.0010 (15) |
N4 | 0.073 (3) | 0.061 (2) | 0.049 (2) | −0.004 (2) | 0.0086 (19) | 0.0022 (19) |
C1 | 0.050 (2) | 0.045 (2) | 0.067 (3) | 0.002 (2) | −0.009 (2) | −0.005 (2) |
C2 | 0.067 (3) | 0.044 (2) | 0.089 (4) | −0.008 (2) | −0.006 (3) | 0.003 (3) |
C3 | 0.070 (3) | 0.048 (3) | 0.099 (4) | −0.010 (2) | −0.010 (3) | −0.021 (3) |
C4 | 0.078 (3) | 0.060 (3) | 0.083 (3) | 0.000 (3) | −0.005 (3) | −0.020 (3) |
C5 | 0.055 (3) | 0.058 (3) | 0.085 (3) | 0.003 (2) | 0.014 (2) | −0.016 (3) |
C6 | 0.0384 (19) | 0.044 (2) | 0.072 (3) | 0.0025 (18) | 0.000 (2) | −0.009 (2) |
C7 | 0.040 (2) | 0.046 (2) | 0.097 (3) | 0.0024 (19) | 0.003 (2) | −0.011 (2) |
C8 | 0.043 (2) | 0.047 (2) | 0.067 (2) | 0.002 (2) | −0.008 (2) | −0.0042 (19) |
C9 | 0.044 (2) | 0.048 (2) | 0.066 (3) | 0.0015 (19) | −0.004 (2) | −0.010 (2) |
C10 | 0.042 (2) | 0.048 (2) | 0.059 (2) | −0.0005 (19) | −0.009 (2) | −0.0043 (18) |
C11 | 0.048 (2) | 0.059 (2) | 0.055 (2) | −0.002 (2) | −0.002 (2) | −0.0094 (19) |
C12 | 0.053 (2) | 0.046 (2) | 0.045 (2) | −0.0064 (19) | −0.0034 (19) | −0.0060 (19) |
C13 | 0.074 (3) | 0.051 (3) | 0.065 (3) | −0.010 (3) | −0.001 (2) | 0.004 (2) |
C14 | 0.104 (4) | 0.039 (2) | 0.086 (4) | −0.003 (3) | −0.017 (4) | 0.000 (2) |
C15 | 0.084 (4) | 0.063 (3) | 0.077 (3) | 0.017 (3) | −0.020 (3) | −0.025 (3) |
C16 | 0.062 (3) | 0.067 (3) | 0.064 (3) | 0.010 (2) | −0.003 (2) | −0.016 (3) |
C17 | 0.056 (2) | 0.047 (2) | 0.043 (2) | −0.001 (2) | 0.000 (2) | −0.0034 (18) |
O3A | 0.042 (2) | 0.057 (2) | 0.084 (3) | −0.0094 (18) | 0.016 (2) | −0.009 (2) |
Geometric parameters (Å, º) top
O1—N1 | 1.212 (5) | C8—C9 | 1.503 (6) |
O2—N1 | 1.226 (5) | C8—H8A | 0.9700 |
O4—N4 | 1.211 (5) | C8—H8B | 0.9700 |
O5—N4 | 1.198 (5) | C9—O3A | 1.453 (5) |
N1—C1 | 1.440 (6) | C9—O3B | 1.495 (10) |
N2—C8 | 1.478 (5) | C9—C10 | 1.501 (6) |
N2—C7 | 1.486 (5) | C9—H9AA | 0.9800 |
N2—H2D | 0.9000 | C9—H9AB | 0.9800 |
N2—H2E | 0.9000 | C10—H10A | 0.9700 |
N3—C10 | 1.476 (5) | C10—H10B | 0.9700 |
N3—C11 | 1.482 (5) | C11—C12 | 1.504 (6) |
N3—H3C | 0.9000 | C11—H11A | 0.9700 |
N3—H3D | 0.9000 | C11—H11B | 0.9700 |
N4—C17 | 1.460 (6) | C12—C13 | 1.370 (6) |
C1—C6 | 1.388 (6) | C12—C17 | 1.394 (6) |
C1—C2 | 1.390 (6) | C13—C14 | 1.375 (7) |
C2—C3 | 1.366 (7) | C13—H13A | 0.9300 |
C2—H2B | 0.9300 | C14—C15 | 1.364 (8) |
C3—C4 | 1.370 (7) | C14—H14A | 0.9300 |
C3—H3B | 0.9300 | C15—C16 | 1.357 (7) |
C4—C5 | 1.375 (7) | C15—H15A | 0.9300 |
C4—H4A | 0.9300 | C16—C17 | 1.369 (6) |
C5—C6 | 1.381 (6) | C16—H16A | 0.9300 |
C5—H5A | 0.9300 | O3A—H9AB | 0.6655 |
C6—C7 | 1.497 (6) | O3A—H3AA | 0.8501 |
C7—H7A | 0.9700 | O3B—H3BA | 0.8501 |
C7—H7B | 0.9700 | | |
| | | |
O1—N1—O2 | 122.5 (4) | H8A—C8—H8B | 108.0 |
O1—N1—C1 | 118.6 (4) | O3A—C9—O3B | 139.7 (10) |
O2—N1—C1 | 118.8 (4) | O3A—C9—C10 | 106.5 (4) |
C8—N2—C7 | 113.1 (3) | O3B—C9—C10 | 100.0 (9) |
C8—N2—H2D | 109.0 | O3A—C9—C8 | 103.9 (3) |
C7—N2—H2D | 109.0 | O3B—C9—C8 | 95.1 (10) |
C8—N2—H2E | 109.0 | C10—C9—C8 | 109.2 (3) |
C7—N2—H2E | 109.0 | O3A—C9—H9AA | 112.2 |
H2D—N2—H2E | 107.8 | C10—C9—H9AA | 112.2 |
C10—N3—C11 | 113.4 (3) | C8—C9—H9AA | 112.2 |
C10—N3—H3C | 108.9 | O3B—C9—H9AB | 117.3 |
C11—N3—H3C | 108.9 | C10—C9—H9AB | 116.2 |
C10—N3—H3D | 108.9 | C8—C9—H9AB | 116.0 |
C11—N3—H3D | 108.9 | H9AA—C9—H9AB | 89.7 |
H3C—N3—H3D | 107.7 | N3—C10—C9 | 111.0 (3) |
O5—N4—O4 | 122.6 (4) | N3—C10—H10A | 109.4 |
O5—N4—C17 | 117.9 (4) | C9—C10—H10A | 109.4 |
O4—N4—C17 | 119.5 (3) | N3—C10—H10B | 109.4 |
C6—C1—C2 | 122.2 (4) | C9—C10—H10B | 109.4 |
C6—C1—N1 | 121.1 (4) | H10A—C10—H10B | 108.0 |
C2—C1—N1 | 116.7 (4) | N3—C11—C12 | 111.7 (4) |
C3—C2—C1 | 118.7 (5) | N3—C11—H11A | 109.3 |
C3—C2—H2B | 120.7 | C12—C11—H11A | 109.3 |
C1—C2—H2B | 120.7 | N3—C11—H11B | 109.3 |
C2—C3—C4 | 120.8 (5) | C12—C11—H11B | 109.3 |
C2—C3—H3B | 119.6 | H11A—C11—H11B | 107.9 |
C4—C3—H3B | 119.6 | C13—C12—C17 | 115.5 (4) |
C3—C4—C5 | 119.5 (5) | C13—C12—C11 | 119.5 (4) |
C3—C4—H4A | 120.2 | C17—C12—C11 | 124.9 (4) |
C5—C4—H4A | 120.2 | C12—C13—C14 | 122.1 (5) |
C4—C5—C6 | 122.1 (5) | C12—C13—H13A | 118.9 |
C4—C5—H5A | 118.9 | C14—C13—H13A | 118.9 |
C6—C5—H5A | 118.9 | C15—C14—C13 | 120.2 (5) |
C5—C6—C1 | 116.6 (4) | C15—C14—H14A | 119.9 |
C5—C6—C7 | 118.3 (4) | C13—C14—H14A | 119.9 |
C1—C6—C7 | 125.0 (4) | C16—C15—C14 | 119.9 (5) |
N2—C7—C6 | 112.1 (3) | C16—C15—H15A | 120.1 |
N2—C7—H7A | 109.2 | C14—C15—H15A | 120.1 |
C6—C7—H7A | 109.2 | C15—C16—C17 | 119.1 (5) |
N2—C7—H7B | 109.2 | C15—C16—H16A | 120.4 |
C6—C7—H7B | 109.2 | C17—C16—H16A | 120.4 |
H7A—C7—H7B | 107.9 | C16—C17—C12 | 123.1 (4) |
N2—C8—C9 | 111.2 (3) | C16—C17—N4 | 116.8 (4) |
N2—C8—H8A | 109.4 | C12—C17—N4 | 120.2 (4) |
C9—C8—H8A | 109.4 | C9—O3A—H3AA | 109.5 |
N2—C8—H8B | 109.4 | H9AB—O3A—H3AA | 76.6 |
C9—C8—H8B | 109.4 | C9—O3B—H3BA | 109.5 |
| | | |
C8—N2—C7—C6 | 156.9 (4) | C1—C6—C7—N2 | −85.8 (5) |
C7—N2—C8—C9 | −177.5 (3) | N2—C8—C9—O3A | 68.7 (4) |
N2—C8—C9—C10 | −178.0 (3) | N2—C8—C9—O3B | −75.5 (10) |
C8—C9—C10—N3 | 174.4 (3) | O3A—C9—C10—N3 | −74.0 (4) |
C11—N3—C10—C9 | 175.2 (3) | O3B—C9—C10—N3 | 75.3 (10) |
C10—N3—C11—C12 | −158.2 (3) | N3—C11—C12—C13 | −98.6 (5) |
O1—N1—C1—C6 | −148.2 (5) | N3—C11—C12—C17 | 85.0 (5) |
O2—N1—C1—C6 | 32.2 (7) | C17—C12—C13—C14 | 0.6 (7) |
O1—N1—C1—C2 | 31.3 (7) | C11—C12—C13—C14 | −176.1 (4) |
O2—N1—C1—C2 | −148.3 (5) | C12—C13—C14—C15 | −0.9 (8) |
C6—C1—C2—C3 | 1.0 (7) | C13—C14—C15—C16 | 1.9 (8) |
N1—C1—C2—C3 | −178.5 (4) | C14—C15—C16—C17 | −2.6 (7) |
C1—C2—C3—C4 | −0.2 (7) | C15—C16—C17—C12 | 2.4 (7) |
C2—C3—C4—C5 | −0.2 (8) | C15—C16—C17—N4 | −178.7 (4) |
C3—C4—C5—C6 | −0.3 (7) | C13—C12—C17—C16 | −1.3 (6) |
C4—C5—C6—C1 | 1.1 (7) | C11—C12—C17—C16 | 175.2 (4) |
C4—C5—C6—C7 | 178.1 (4) | C13—C12—C17—N4 | 179.8 (4) |
C2—C1—C6—C5 | −1.4 (6) | C11—C12—C17—N4 | −3.7 (6) |
N1—C1—C6—C5 | 178.1 (4) | O5—N4—C17—C16 | −24.0 (6) |
C2—C1—C6—C7 | −178.2 (4) | O4—N4—C17—C16 | 157.4 (5) |
N1—C1—C6—C7 | 1.3 (6) | O5—N4—C17—C12 | 154.9 (5) |
C5—C6—C7—N2 | 97.4 (5) | O4—N4—C17—C12 | −23.6 (6) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2D···Cl2i | 0.90 | 2.19 | 3.060 (4) | 163 |
N2—H2E···Cl1 | 0.90 | 2.34 | 3.109 (3) | 143 |
N3—H3C···Cl2 | 0.90 | 2.30 | 3.120 (3) | 151 |
N3—H3D···Cl1i | 0.90 | 2.15 | 3.037 (3) | 167 |
O3A—H3AA···Cl1 | 0.85 | 2.80 | 3.422 (4) | 132 |
O3B—H3BA···Cl1i | 0.85 | 2.24 | 2.95 (2) | 140 |
Symmetry code: (i) x+1/2, −y+3/2, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C17H22N4O42+·2Cl−·H2O | C17H22N4O52+·2Cl− |
Mr | 435.30 | 433.29 |
Crystal system, space group | Triclinic, P1 | Orthorhombic, P212121 |
Temperature (K) | 297 | 298 |
a, b, c (Å) | 8.630 (3), 11.449 (4), 11.629 (4) | 7.075 (2), 15.844 (8), 18.554 (6) |
α, β, γ (°) | 116.353 (17), 92.09 (2), 98.82 (2) | 90, 90, 90 |
V (Å3) | 1010.2 (6) | 2079.8 (14) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.36 | 0.35 |
Crystal size (mm) | 0.5 × 0.5 × 0.4 | 0.4 × 0.2 × 0.2 |
|
Data collection |
Diffractometer | Siemens P4 diffractometer | Siemens P4 diffractometer |
Absorption correction | ψ scan (XSCANS; Siemens, 1999) | ψ scan (XSCANS; Siemens, 1999) |
Tmin, Tmax | 0.845, 0.867 | 0.739, 0.934 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8783, 4456, 3585 | 6209, 3692, 2729 |
Rint | 0.072 | 0.089 |
(sin θ/λ)max (Å−1) | 0.650 | 0.596 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.113, 1.05 | 0.055, 0.145, 1.04 |
No. of reflections | 4456 | 3692 |
No. of parameters | 261 | 259 |
No. of restraints | 2 | 8 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.36 | 0.36, −0.30 |
Absolute structure | ? | Flack (1983), with 1557 Friedel pairs |
Absolute structure parameter | ? | −0.03 (11) |
Selected torsion angles (º) for (I) topC8—N2—C7—C6 | 158.61 (14) | C8—C9—C10—N3 | 176.86 (13) |
C7—N2—C8—C9 | 62.25 (18) | C11—N3—C10—C9 | 174.09 (13) |
N2—C8—C9—C10 | −179.01 (12) | C10—N3—C11—C12 | 170.94 (13) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···Cl2 | 0.90 | 2.11 | 3.0043 (17) | 170.2 |
N2—H2C···Cl1 | 0.90 | 2.27 | 3.0976 (16) | 153.1 |
N3—H3B···Cl2i | 0.90 | 2.13 | 2.9890 (17) | 159.0 |
N3—H3C···Cl1ii | 0.90 | 2.25 | 3.1142 (17) | 161.3 |
O5—H5B···Cl1iii | 0.91 (4) | 2.24 (2) | 3.141 (2) | 173 (4) |
O5—H5C···Cl1 | 0.89 (3) | 2.35 (2) | 3.213 (2) | 165 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z; (iii) −x+2, −y, −z+1. |
Selected torsion angles (º) for (II) topC8—N2—C7—C6 | 156.9 (4) | C8—C9—C10—N3 | 174.4 (3) |
C7—N2—C8—C9 | −177.5 (3) | C11—N3—C10—C9 | 175.2 (3) |
N2—C8—C9—C10 | −178.0 (3) | C10—N3—C11—C12 | −158.2 (3) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2D···Cl2i | 0.90 | 2.19 | 3.060 (4) | 163.1 |
N2—H2E···Cl1 | 0.90 | 2.34 | 3.109 (3) | 143.2 |
N3—H3C···Cl2 | 0.90 | 2.30 | 3.120 (3) | 151.1 |
N3—H3D···Cl1i | 0.90 | 2.15 | 3.037 (3) | 167.4 |
O3A—H3AA···Cl1 | 0.85 | 2.80 | 3.422 (4) | 131.8 |
O3B—H3BA···Cl1i | 0.85 | 2.24 | 2.95 (2) | 140.1 |
Symmetry code: (i) x+1/2, −y+3/2, −z+1. |
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The Schiff base acyclic cations in the title salts, (I) and (II), are chemical precursors for a variety of acyclic and macrocyclic multidentate ligands and their metal complexes. The cations in compounds (I) and (II) are closely related, compound (II) formally resulting from (I) after substitution of an H atom by an OH functionality. The hydroxyl group is known to be an efficient donor and acceptor group for hydrogen bonding, and the introduction of this functional group is thus expected to induce significant changes in the crystal structure. However, an unexpected conformational modification was also observed for the cations. Moreover, compound (I) crystallizes as a hydrate, while compound (II) is unsolvated.
The cation in compound (II) approximates to Cs point group symmetry (Fig. 2), while in compound (I) the cation is clearly asymmetric (Fig. 1). The aryl rings make significantly different dihedral angles in each cation, 35.2 (1)° for compound (I) and 63.8 (2)° for compound (II). The nitro groups are twisted out of the planes of the adjacent aryl rings, with dihedral angles NO2/arene of 12.0 (2) and 27.3 (2)° for the nitro groups containing atoms N1 and N4 in compound (I), and 31.7 (3) and 24.2 (5)° for the corresponding groups in compound (II). This twisted arrangement for nitro groups is a common feature in molecules including a nitrobenzene fragment [e.g. 40.5° (Peseke et al., 1999), 34.4° (Qiu et al., 2006), and 23.3 and 17.6° (Obregón-Solís et al., 2001)].
The conformation of the central chain linking the nitrophenyl groups for both ligands is described by the C—C—N—C and N—C—C—C torsion angles (Tables 1 and 2). As can be seen, the conformation stabilized for compound (II) is the expected all-trans chain commonly found in aliphatic systems, while compound (I) presents a synclinal conformation for the C7/N2/C8/C9 section, defining a trans–gauche–trans–trans–trans conformation for the complete C6–C12 chain. These observations suggest that compounds (I) and (II) are highly flexible cations, with quite a free rotation about all σ bonds, assuming that no hindrance occurs with peripheral nitrobenzene groups. This flexible behaviour, probably retained or even increased in solution, makes compounds (I) and (II) good candidates for coordinating transition metals.
In both compounds, the cations and anions are engaged in hydrogen-bond networks, two-dimensional in compound (I) and one-dimensional in compound (II), involving NH2+ or O—H functionalities as donor groups and Cl− or nitro groups as acceptor. In the case of compound (II), the O—H group is disordered over two sites with occupancies of 0.785 (8) and 0.215 (8) for atoms O3A and O3B, respectively (see Experimental). The major component of the disordered hydroxyl group forms a hydrogen bond with a Cl− anion in the asymmetric unit, and two Cl− anions are also connected to NH2+ groups, one within the asymmetric unit and the other a symmetry-related one. The minor component of the disordered hydroxyl group forms a weaker bond with a symmetry-related Cl− anion. Finally, two strong intermolecular N—H···Cl bonds form a two-dimensional network stabilizing the crystal structure (Table 4 and Fig. 4). For compound (I), as the hydroxyl donor group is no longer present in the cation, a water molecule is inserted in the lattice, which participates in efficient O—H···Cl contacts (Table 3 and Fig. 3).