Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109024457/sk3332sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109024457/sk33321sup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109024457/sk33322rtsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109024457/sk33322ltsup4.hkl |
CCDC references: 746074; 746075; 746076
To a suspension of 3,3'-[1,4-phenylene-bis-(methylene)]-bis-[6-(hydroxymethyl)-1,4-dimethyl-2,5-piperazinedione] (Polaske et al., 2009) (45 mg, 0.10 mmol) in CH2Cl2 (5 ml), triphenylphosphine (130 mg, 0.50 mmol) and hexachloroacetone (76 µl, 0.50 mmol) were added. After stirring at room temperature for 18 h, the solvent was removed and the residue resuspended in a 1:1 solution of acetonitrile and water (5 ml). The solids were filtered off and the filtrate was purified by semi-preparative HPLC using a 5–95% gradient of 0.05% trifluoroacetic acid in acetonitrile, yielding crystals of form (1) as small colorless rods followed by recrystallization from ethanol to yield crystals of form (2) (26 mg, 54% yield) as colorless prisms. 1H NMR (500 MHz, CDCl3) δ 6.95 (4H, s), 4.28 (2H, br t, J=2.5 Hz), 4.02 (2H, dd, J=12.5 Hz and 1.5 Hz), 3.74 (2H, dd, J=12.5 Hz and 3.5 Hz), 3.43 (2H, dd, J=14 Hz and 2.5 Hz), 3.24 (2H, br s), 3.11 (2H, dd, J=14 Hz and 5 Hz), 3.06 (6H, s), 2.88 (6H, s). 13C NMR (150 MHz, CDCl3) δ 165.6, 163.6, 134.2, 129.8, 69.24, 60.52, 44.19, 37.16, 32.63, 30.68. HRMS (FAB, [M+H]+) found: 483.1570, C22H29Cl2N4O4 requires 483.1566.
Polymorph (1) showed surprisingly weak diffraction, necessitating exposures of 120 s per frame and even this was sufficient only to yield data with an Rσ < 30% cutoff of 2θ = 45°. Owing to this, the value of the Flack absolute structure parameter (Flack, 1983) is indeterminate and Friedel pairs were merged. Polymorph (2rt) has a Flack parameter of -0.03 (8) from 953 Friedel pairs. Polymorph (2lt) has a Flack parameter of 0.07 (7) and a non-merohedral twin scale factor of 0.44487. For all structures, H atoms were either placed geometrically (1) or first located in a difference map (2) and then refined with Uiso(H) = 1.5Ueq(C) for methyl groups and Uiso(H) = 1.2Ueq(C) for all others. Fixed C–H distances of 0.95Å (aryl), 0.98Å (methyl & R3CH) and 0.99Å (methylene) were used.
Data collection: COLLECT (Nonius, 1998) for (1); APEX2 (Bruker, 2007) for 2rt, 2lt. Cell refinement: EVALCCD (Duisenberg et al., 2003) for (1); SAINT (Bruker, 2007) for 2rt; CELL_NOW (Sheldrick, 2004) and SAINT (Bruker, 2007) for 2lt. Data reduction: EVALCCD (Duisenberg et al., 2003) for (1); SAINT (Bruker, 2007) for 2rt, 2lt. For all compounds, program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2009) and local programs.
C22H28Cl2N4O4 | F(000) = 508 |
Mr = 483.38 | Dx = 1.321 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 1266 reflections |
a = 8.4158 (17) Å | θ = 2.5–25.0° |
b = 14.779 (3) Å | µ = 0.30 mm−1 |
c = 10.438 (2) Å | T = 150 K |
β = 110.58 (3)° | Block, colourless |
V = 1215.3 (4) Å3 | 0.32 × 0.13 × 0.07 mm |
Z = 2 |
Nonius KappaCCD diffractometer | 1649 independent reflections |
Radiation source: sealed tube | 1123 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.128 |
ϕ and ω scans | θmax = 22.5°, θmin = 4.1° |
Absorption correction: multi-scan (SADABS 2008/1; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.664, Tmax = 0.917 | k = −15→15 |
8536 measured reflections | l = −10→11 |
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)] = 0.080 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.18 | w = 1/[σ2(Fo2) + 2.8P] where P = (Fo2 + 2Fc2)/3 |
1649 reflections | (Δ/σ)max < 0.001 |
293 parameters | Δρmax = 0.30 e Å−3 |
1 restraint | Δρmin = −0.29 e Å−3 |
C22H28Cl2N4O4 | V = 1215.3 (4) Å3 |
Mr = 483.38 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.4158 (17) Å | µ = 0.30 mm−1 |
b = 14.779 (3) Å | T = 150 K |
c = 10.438 (2) Å | 0.32 × 0.13 × 0.07 mm |
β = 110.58 (3)° |
Nonius KappaCCD diffractometer | 1649 independent reflections |
Absorption correction: multi-scan (SADABS 2008/1; Sheldrick, 1996) | 1123 reflections with I > 2σ(I) |
Tmin = 0.664, Tmax = 0.917 | Rint = 0.128 |
8536 measured reflections | θmax = 22.5° |
R[F2 > 2σ(F2)] = 0.080 | 1 restraint |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.18 | Δρmax = 0.30 e Å−3 |
1649 reflections | Δρmin = −0.29 e Å−3 |
293 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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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 | ||
Cl1 | 0.4483 (4) | 1.0182 (3) | 0.1745 (3) | 0.0475 (10) | |
Cl2 | 1.1416 (4) | 0.9609 (2) | 0.8668 (3) | 0.0504 (11) | |
O1 | 0.6453 (10) | 0.8232 (6) | 0.3582 (8) | 0.039 (2) | |
O2 | 0.7071 (10) | 0.8997 (6) | −0.1244 (8) | 0.045 (3) | |
O3 | 1.2908 (10) | 0.7143 (6) | 0.7559 (8) | 0.036 (2) | |
O4 | 1.0493 (11) | 1.0258 (6) | 0.4970 (8) | 0.040 (2) | |
N1 | 0.6002 (12) | 0.7813 (7) | 0.1396 (10) | 0.033 (3) | |
N2 | 0.7484 (11) | 0.9417 (6) | 0.0952 (9) | 0.025 (3) | |
N3 | 1.0657 (13) | 0.8045 (7) | 0.6558 (9) | 0.025 (2) | |
N4 | 1.2720 (13) | 0.9280 (7) | 0.5822 (9) | 0.031 (3) | |
C1 | 0.6614 (15) | 0.8375 (9) | 0.2453 (12) | 0.029 (4) | |
C2 | 0.6520 (15) | 0.7884 (9) | 0.0204 (11) | 0.031 (3) | |
H2 | 0.5514 | 0.7703 | −0.0606 | 0.038* | |
C3 | 0.7013 (15) | 0.8831 (10) | −0.0093 (12) | 0.034 (4) | |
C4 | 0.7471 (14) | 0.9257 (8) | 0.2306 (11) | 0.023 (3) | |
H4 | 0.8682 | 0.9215 | 0.2930 | 0.028* | |
C5 | 0.6691 (13) | 1.0022 (9) | 0.2806 (11) | 0.032 (3) | |
H5A | 0.7330 | 1.0585 | 0.2806 | 0.038* | |
H5B | 0.6772 | 0.9900 | 0.3760 | 0.038* | |
C6 | 0.5103 (17) | 0.6993 (9) | 0.1539 (13) | 0.044 (4) | |
H6A | 0.5897 | 0.6482 | 0.1780 | 0.067* | |
H6B | 0.4185 | 0.6865 | 0.0672 | 0.067* | |
H6C | 0.4626 | 0.7082 | 0.2262 | 0.067* | |
C7 | 0.8322 (16) | 1.0276 (10) | 0.0761 (12) | 0.049 (4) | |
H7A | 0.8434 | 1.0273 | −0.0143 | 0.073* | |
H7B | 0.9450 | 1.0322 | 0.1471 | 0.073* | |
H7C | 0.7631 | 1.0795 | 0.0829 | 0.073* | |
C8 | 0.7960 (15) | 0.7206 (8) | 0.0281 (11) | 0.030 (3) | |
H8A | 0.7553 | 0.6580 | 0.0310 | 0.036* | |
H8B | 0.8261 | 0.7266 | −0.0551 | 0.036* | |
C9 | 0.9541 (16) | 0.7379 (9) | 0.1554 (12) | 0.034 (3) | |
C10 | 0.9755 (15) | 0.6891 (8) | 0.2735 (12) | 0.031 (3) | |
H10 | 0.8937 | 0.6446 | 0.2727 | 0.037* | |
C11 | 1.1141 (17) | 0.7034 (9) | 0.3936 (12) | 0.034 (3) | |
H11 | 1.1241 | 0.6683 | 0.4724 | 0.041* | |
C12 | 1.2383 (15) | 0.7678 (9) | 0.4013 (11) | 0.030 (3) | |
C13 | 1.2131 (15) | 0.8166 (8) | 0.2794 (12) | 0.033 (3) | |
H13 | 1.2943 | 0.8613 | 0.2793 | 0.039* | |
C14 | 1.0751 (16) | 0.8026 (9) | 0.1595 (12) | 0.032 (3) | |
H14 | 1.0638 | 0.8375 | 0.0802 | 0.039* | |
C15 | 1.3881 (14) | 0.7843 (8) | 0.5288 (11) | 0.032 (3) | |
H15A | 1.4766 | 0.8165 | 0.5043 | 0.039* | |
H15B | 1.4358 | 0.7253 | 0.5692 | 0.039* | |
C16 | 1.3446 (15) | 0.8413 (9) | 0.6396 (12) | 0.035 (3) | |
H16 | 1.4526 | 0.8530 | 0.7178 | 0.042* | |
C17 | 1.2291 (16) | 0.7834 (9) | 0.6921 (11) | 0.027 (3) | |
C18 | 1.0015 (14) | 0.8919 (8) | 0.6095 (11) | 0.025 (3) | |
H18 | 0.8931 | 0.8821 | 0.5309 | 0.030* | |
C19 | 1.1092 (15) | 0.9538 (10) | 0.5562 (10) | 0.026 (3) | |
C20 | 0.9540 (17) | 0.7419 (9) | 0.6899 (13) | 0.045 (4) | |
H20A | 0.9557 | 0.6834 | 0.6464 | 0.067* | |
H20B | 0.8382 | 0.7660 | 0.6570 | 0.067* | |
H20C | 0.9927 | 0.7341 | 0.7894 | 0.067* | |
C21 | 1.3839 (16) | 0.9928 (10) | 0.5476 (13) | 0.049 (4) | |
H21A | 1.3742 | 0.9842 | 0.4521 | 0.074* | |
H21B | 1.5017 | 0.9825 | 0.6076 | 0.074* | |
H21C | 1.3503 | 1.0547 | 0.5602 | 0.074* | |
C22 | 0.9545 (15) | 0.9456 (10) | 0.7150 (11) | 0.041 (4) | |
H22A | 0.8661 | 0.9128 | 0.7390 | 0.050* | |
H22B | 0.9081 | 1.0053 | 0.6768 | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.031 (2) | 0.052 (3) | 0.054 (2) | 0.006 (2) | 0.0083 (17) | 0.010 (2) |
Cl2 | 0.067 (3) | 0.052 (3) | 0.0263 (17) | −0.010 (2) | 0.0095 (17) | −0.0053 (19) |
O1 | 0.034 (6) | 0.048 (7) | 0.039 (5) | −0.013 (5) | 0.018 (5) | −0.001 (5) |
O2 | 0.036 (6) | 0.071 (7) | 0.019 (5) | −0.015 (5) | −0.002 (4) | 0.000 (5) |
O3 | 0.024 (5) | 0.030 (6) | 0.045 (5) | 0.009 (4) | 0.001 (4) | 0.010 (5) |
O4 | 0.057 (6) | 0.034 (6) | 0.028 (5) | −0.001 (6) | 0.012 (4) | 0.006 (5) |
N1 | 0.029 (7) | 0.045 (8) | 0.029 (6) | −0.019 (6) | 0.017 (5) | −0.010 (6) |
N2 | 0.029 (6) | 0.028 (8) | 0.024 (6) | 0.001 (5) | 0.016 (5) | 0.002 (5) |
N3 | 0.023 (6) | 0.032 (7) | 0.023 (5) | −0.011 (5) | 0.010 (5) | 0.004 (5) |
N4 | 0.021 (6) | 0.035 (8) | 0.036 (6) | −0.006 (6) | 0.008 (5) | 0.005 (5) |
C1 | 0.031 (9) | 0.047 (10) | 0.011 (7) | 0.019 (7) | 0.008 (6) | 0.007 (7) |
C2 | 0.032 (8) | 0.032 (9) | 0.021 (7) | −0.004 (7) | −0.002 (6) | −0.006 (6) |
C3 | 0.028 (8) | 0.056 (11) | 0.017 (7) | −0.018 (7) | 0.007 (6) | −0.012 (7) |
C4 | 0.019 (7) | 0.027 (9) | 0.023 (7) | −0.009 (6) | 0.007 (6) | −0.006 (6) |
C5 | 0.014 (7) | 0.039 (10) | 0.041 (7) | 0.003 (6) | 0.008 (6) | 0.001 (7) |
C6 | 0.055 (10) | 0.039 (10) | 0.047 (8) | −0.020 (8) | 0.026 (8) | 0.002 (7) |
C7 | 0.049 (9) | 0.051 (11) | 0.049 (8) | −0.008 (9) | 0.023 (7) | 0.007 (9) |
C8 | 0.039 (8) | 0.020 (8) | 0.035 (7) | 0.009 (7) | 0.020 (7) | 0.002 (6) |
C9 | 0.050 (9) | 0.034 (9) | 0.022 (7) | 0.005 (8) | 0.018 (7) | 0.007 (7) |
C10 | 0.026 (8) | 0.018 (8) | 0.047 (8) | −0.009 (6) | 0.010 (7) | −0.012 (7) |
C11 | 0.043 (9) | 0.033 (9) | 0.025 (7) | 0.005 (7) | 0.010 (7) | 0.013 (6) |
C12 | 0.027 (8) | 0.043 (10) | 0.021 (7) | 0.004 (7) | 0.011 (6) | 0.005 (6) |
C13 | 0.027 (8) | 0.039 (10) | 0.041 (8) | −0.002 (7) | 0.023 (7) | −0.007 (7) |
C14 | 0.045 (9) | 0.029 (9) | 0.025 (7) | −0.004 (7) | 0.015 (7) | 0.007 (6) |
C15 | 0.028 (8) | 0.030 (9) | 0.033 (7) | 0.011 (6) | 0.003 (6) | 0.007 (7) |
C16 | 0.024 (8) | 0.044 (10) | 0.030 (7) | 0.006 (7) | 0.001 (6) | 0.005 (7) |
C17 | 0.024 (8) | 0.026 (9) | 0.024 (7) | 0.000 (7) | 0.001 (6) | −0.005 (7) |
C18 | 0.019 (7) | 0.029 (9) | 0.024 (7) | 0.005 (6) | 0.003 (6) | 0.012 (7) |
C19 | 0.032 (9) | 0.039 (10) | 0.006 (6) | −0.004 (8) | 0.006 (6) | 0.001 (7) |
C20 | 0.052 (10) | 0.047 (11) | 0.039 (8) | −0.010 (9) | 0.021 (7) | 0.007 (8) |
C21 | 0.034 (9) | 0.062 (12) | 0.061 (9) | −0.002 (8) | 0.029 (7) | −0.002 (8) |
C22 | 0.032 (8) | 0.059 (11) | 0.032 (7) | −0.012 (8) | 0.011 (6) | −0.008 (8) |
Cl1—C5 | 1.814 (11) | C7—H7C | 0.980 |
Cl2—C22 | 1.813 (12) | C8—H8A | 0.990 |
O1—C1 | 1.251 (12) | C8—H8B | 0.990 |
O2—C3 | 1.244 (13) | C8—C9 | 1.536 (15) |
O3—C17 | 1.231 (13) | C9—C10 | 1.385 (15) |
O4—C19 | 1.244 (14) | C9—C14 | 1.387 (16) |
N1—C1 | 1.332 (14) | C10—H10 | 0.950 |
N1—C2 | 1.460 (14) | C10—C11 | 1.396 (15) |
N1—C6 | 1.465 (15) | C11—H11 | 0.950 |
N2—C3 | 1.339 (14) | C11—C12 | 1.395 (16) |
N2—C4 | 1.437 (13) | C12—C13 | 1.413 (15) |
N2—C7 | 1.499 (15) | C12—C15 | 1.497 (15) |
N3—C17 | 1.329 (14) | C13—H13 | 0.950 |
N3—C18 | 1.419 (14) | C13—C14 | 1.392 (15) |
N3—C20 | 1.449 (14) | C14—H14 | 0.950 |
N4—C16 | 1.456 (15) | C15—H15A | 0.990 |
N4—C19 | 1.354 (14) | C15—H15B | 0.990 |
N4—C21 | 1.474 (15) | C15—C16 | 1.574 (16) |
C1—C4 | 1.523 (16) | C16—H16 | 1.000 |
C2—H2 | 1.000 | C16—C17 | 1.533 (16) |
C2—C3 | 1.523 (17) | C18—H18 | 1.000 |
C2—C8 | 1.553 (15) | C18—C19 | 1.523 (16) |
C4—H4 | 1.000 | C18—C22 | 1.518 (16) |
C4—C5 | 1.491 (15) | C20—H20A | 0.980 |
C5—H5A | 0.990 | C20—H20B | 0.980 |
C5—H5B | 0.990 | C20—H20C | 0.980 |
C6—H6A | 0.980 | C21—H21A | 0.980 |
C6—H6B | 0.980 | C21—H21B | 0.980 |
C6—H6C | 0.980 | C21—H21C | 0.980 |
C7—H7A | 0.980 | C22—H22A | 0.990 |
C7—H7B | 0.980 | C22—H22B | 0.990 |
C1—N1—C2 | 121.1 (10) | C9—C10—H10 | 119.1 |
C1—N1—C6 | 119.7 (10) | C9—C10—C11 | 121.8 (12) |
C2—N1—C6 | 117.8 (10) | H10—C10—C11 | 119.1 |
C3—N2—C4 | 126.3 (10) | C10—C11—H11 | 119.1 |
C3—N2—C7 | 117.2 (10) | C10—C11—C12 | 121.9 (11) |
C4—N2—C7 | 115.9 (9) | H11—C11—C12 | 119.1 |
C17—N3—C18 | 122.9 (10) | C11—C12—C13 | 115.1 (11) |
C17—N3—C20 | 118.4 (11) | C11—C12—C15 | 122.8 (11) |
C18—N3—C20 | 117.6 (10) | C13—C12—C15 | 122.0 (12) |
C16—N4—C19 | 125.4 (11) | C12—C13—H13 | 118.4 |
C16—N4—C21 | 117.4 (10) | C12—C13—C14 | 123.2 (12) |
C19—N4—C21 | 117.2 (11) | H13—C13—C14 | 118.4 |
O1—C1—N1 | 122.4 (12) | C9—C14—C13 | 120.1 (12) |
O1—C1—C4 | 116.9 (11) | C9—C14—H14 | 119.9 |
N1—C1—C4 | 120.6 (10) | C13—C14—H14 | 119.9 |
N1—C2—H2 | 106.5 | C12—C15—H15A | 108.9 |
N1—C2—C3 | 115.1 (10) | C12—C15—H15B | 108.9 |
N1—C2—C8 | 111.8 (10) | C12—C15—C16 | 113.6 (10) |
H2—C2—C3 | 106.5 | H15A—C15—H15B | 107.7 |
H2—C2—C8 | 106.5 | H15A—C15—C16 | 108.9 |
C3—C2—C8 | 109.9 (10) | H15B—C15—C16 | 108.9 |
O2—C3—N2 | 124.0 (12) | N4—C16—C15 | 109.9 (10) |
O2—C3—C2 | 118.9 (11) | N4—C16—H16 | 108.2 |
N2—C3—C2 | 116.9 (10) | N4—C16—C17 | 114.2 (10) |
N2—C4—C1 | 114.1 (9) | C15—C16—H16 | 108.2 |
N2—C4—H4 | 107.0 | C15—C16—C17 | 107.7 (10) |
N2—C4—C5 | 112.0 (10) | H16—C16—C17 | 108.2 |
C1—C4—H4 | 107.0 | O3—C17—N3 | 123.1 (12) |
C1—C4—C5 | 109.3 (9) | O3—C17—C16 | 117.2 (11) |
H4—C4—C5 | 107.0 | N3—C17—C16 | 119.3 (11) |
Cl1—C5—C4 | 111.6 (8) | N3—C18—H18 | 106.0 |
Cl1—C5—H5A | 109.3 | N3—C18—C19 | 117.8 (10) |
Cl1—C5—H5B | 109.3 | N3—C18—C22 | 113.2 (10) |
C4—C5—H5A | 109.3 | H18—C18—C19 | 106.0 |
C4—C5—H5B | 109.3 | H18—C18—C22 | 106.0 |
H5A—C5—H5B | 108.0 | C19—C18—C22 | 107.0 (10) |
N1—C6—H6A | 109.5 | O4—C19—N4 | 123.0 (11) |
N1—C6—H6B | 109.5 | O4—C19—C18 | 120.3 (11) |
N1—C6—H6C | 109.5 | N4—C19—C18 | 116.6 (11) |
H6A—C6—H6B | 109.5 | N3—C20—H20A | 109.5 |
H6A—C6—H6C | 109.5 | N3—C20—H20B | 109.5 |
H6B—C6—H6C | 109.5 | N3—C20—H20C | 109.5 |
N2—C7—H7A | 109.5 | H20A—C20—H20B | 109.5 |
N2—C7—H7B | 109.5 | H20A—C20—H20C | 109.5 |
N2—C7—H7C | 109.5 | H20B—C20—H20C | 109.5 |
H7A—C7—H7B | 109.5 | N4—C21—H21A | 109.5 |
H7A—C7—H7C | 109.5 | N4—C21—H21B | 109.5 |
H7B—C7—H7C | 109.5 | N4—C21—H21C | 109.5 |
C2—C8—H8A | 109.4 | H21A—C21—H21B | 109.5 |
C2—C8—H8B | 109.4 | H21A—C21—H21C | 109.5 |
C2—C8—C9 | 111.1 (10) | H21B—C21—H21C | 109.5 |
H8A—C8—H8B | 108.0 | Cl2—C22—C18 | 109.3 (9) |
H8A—C8—C9 | 109.4 | Cl2—C22—H22A | 109.8 |
H8B—C8—C9 | 109.4 | Cl2—C22—H22B | 109.8 |
C8—C9—C10 | 119.0 (12) | C18—C22—H22A | 109.8 |
C8—C9—C14 | 123.0 (11) | C18—C22—H22B | 109.8 |
C10—C9—C14 | 117.9 (12) | H22A—C22—H22B | 108.3 |
C2—N1—C1—O1 | −166.2 (11) | C11—C12—C13—C14 | 0.1 (17) |
C2—N1—C1—C4 | 17.0 (17) | C15—C12—C13—C14 | 180.0 (11) |
C6—N1—C1—O1 | 0.0 (18) | C8—C9—C14—C13 | 178.2 (11) |
C6—N1—C1—C4 | −176.8 (11) | C10—C9—C14—C13 | 0.2 (18) |
C1—N1—C2—C3 | −29.0 (15) | C12—C13—C14—C9 | −0.2 (19) |
C1—N1—C2—C8 | 97.3 (13) | C11—C12—C15—C16 | −77.0 (15) |
C6—N1—C2—C3 | 164.5 (11) | C13—C12—C15—C16 | 103.1 (13) |
C6—N1—C2—C8 | −69.2 (13) | C19—N4—C16—C15 | 111.9 (12) |
C4—N2—C3—O2 | −178.8 (11) | C19—N4—C16—C17 | −9.4 (15) |
C4—N2—C3—C2 | −4.0 (17) | C21—N4—C16—C15 | −67.2 (13) |
C7—N2—C3—O2 | −7.7 (18) | C21—N4—C16—C17 | 171.5 (10) |
C7—N2—C3—C2 | 167.2 (11) | C12—C15—C16—N4 | −57.8 (14) |
N1—C2—C3—O2 | −162.8 (11) | C12—C15—C16—C17 | 67.3 (12) |
N1—C2—C3—N2 | 22.1 (15) | C18—N3—C17—O3 | 165.9 (11) |
C8—C2—C3—O2 | 69.9 (14) | C18—N3—C17—C16 | −21.2 (15) |
C8—C2—C3—N2 | −105.2 (12) | C20—N3—C17—O3 | −1.7 (17) |
C3—N2—C4—C1 | −8.5 (16) | C20—N3—C17—C16 | 171.2 (10) |
C3—N2—C4—C5 | −133.4 (12) | N4—C16—C17—O3 | −171.8 (10) |
C7—N2—C4—C1 | −179.8 (10) | N4—C16—C17—N3 | 14.9 (15) |
C7—N2—C4—C5 | 55.3 (13) | C15—C16—C17—O3 | 65.7 (12) |
O1—C1—C4—N2 | −174.9 (10) | C15—C16—C17—N3 | −107.6 (12) |
O1—C1—C4—C5 | −48.5 (14) | C17—N3—C18—C19 | 20.0 (15) |
N1—C1—C4—N2 | 2.1 (16) | C17—N3—C18—C22 | −105.8 (12) |
N1—C1—C4—C5 | 128.5 (11) | C20—N3—C18—C19 | −172.3 (9) |
N2—C4—C5—Cl1 | 62.4 (11) | C20—N3—C18—C22 | 61.9 (13) |
C1—C4—C5—Cl1 | −65.1 (11) | C16—N4—C19—O4 | −174.1 (11) |
N1—C2—C8—C9 | −60.1 (13) | C16—N4—C19—C18 | 8.8 (15) |
C3—C2—C8—C9 | 69.0 (12) | C21—N4—C19—O4 | 5.0 (16) |
C2—C8—C9—C10 | 94.4 (13) | C21—N4—C19—C18 | −172.2 (10) |
C2—C8—C9—C14 | −83.5 (14) | N3—C18—C19—O4 | 170.0 (10) |
C8—C9—C10—C11 | −178.2 (11) | N3—C18—C19—N4 | −12.8 (14) |
C14—C9—C10—C11 | −0.2 (18) | C22—C18—C19—O4 | −61.3 (13) |
C9—C10—C11—C12 | 0.1 (19) | C22—C18—C19—N4 | 116.0 (11) |
C10—C11—C12—C13 | 0.0 (18) | N3—C18—C22—Cl2 | 60.7 (12) |
C10—C11—C12—C15 | −179.9 (11) | C19—C18—C22—Cl2 | −70.7 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O3i | 1.00 | 2.49 | 3.487 (14) | 173 |
C4—H4···O4 | 1.00 | 2.64 | 3.379 (13) | 131 |
C5—H5A···O3ii | 0.99 | 2.33 | 3.188 (16) | 145 |
C15—H15A···O1iii | 0.99 | 2.42 | 3.301 (15) | 147 |
C16—H16···O2iv | 1.00 | 2.30 | 3.292 (14) | 170 |
C18—H18···O1 | 1.00 | 2.39 | 3.372 (14) | 167 |
C22—H22A···O2v | 0.99 | 2.28 | 3.171 (15) | 149 |
Symmetry codes: (i) x−1, y, z−1; (ii) −x+2, y+1/2, −z+1; (iii) x+1, y, z; (iv) x+1, y, z+1; (v) x, y, z+1. |
C22H28Cl2N4O4 | F(000) = 508 |
Mr = 483.38 | Dx = 1.384 Mg m−3 |
Orthorhombic, P21212 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2 2ab | Cell parameters from 4706 reflections |
a = 9.7566 (5) Å | θ = 2.2–22.6° |
b = 12.7626 (6) Å | µ = 0.32 mm−1 |
c = 9.3138 (4) Å | T = 296 K |
V = 1159.75 (9) Å3 | Prism, colourless |
Z = 2 | 0.20 × 0.15 × 0.09 mm |
Bruker Kappa APEXII DUO CCD diffractometer | 2288 independent reflections |
Radiation source: fine-focus sealed tube with Miracol optics | 1847 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ϕ and ω scans | θmax = 26.0°, θmin = 2.6° |
Absorption correction: numerical (SADABS 2008/1; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.641, Tmax = 0.745 | k = −15→15 |
15349 measured reflections | l = −5→11 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.102 | w = 1/[σ2(Fo2) + (0.0563P)2 + 0.1338P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
2288 reflections | Δρmax = 0.22 e Å−3 |
148 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (8) |
C22H28Cl2N4O4 | V = 1159.75 (9) Å3 |
Mr = 483.38 | Z = 2 |
Orthorhombic, P21212 | Mo Kα radiation |
a = 9.7566 (5) Å | µ = 0.32 mm−1 |
b = 12.7626 (6) Å | T = 296 K |
c = 9.3138 (4) Å | 0.20 × 0.15 × 0.09 mm |
Bruker Kappa APEXII DUO CCD diffractometer | 2288 independent reflections |
Absorption correction: numerical (SADABS 2008/1; Sheldrick, 1996) | 1847 reflections with I > 2σ(I) |
Tmin = 0.641, Tmax = 0.745 | Rint = 0.025 |
15349 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.102 | Δρmax = 0.22 e Å−3 |
S = 1.03 | Δρmin = −0.18 e Å−3 |
2288 reflections | Absolute structure: Flack (1983) |
148 parameters | Absolute structure parameter: −0.03 (8) |
0 restraints |
Experimental. Flack parameter from 953 Friedel pairs. |
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 | ||
Cl1 | 0.84190 (9) | 0.45208 (6) | 0.16838 (9) | 0.0910 (3) | |
O1 | 0.5898 (2) | 0.35297 (15) | 0.4250 (2) | 0.0780 (5) | |
O2 | 0.89126 (19) | 0.12669 (14) | 0.0653 (2) | 0.0763 (5) | |
N1 | 0.7504 (2) | 0.22967 (14) | 0.3946 (2) | 0.0541 (5) | |
N2 | 0.7185 (2) | 0.23960 (15) | 0.0965 (2) | 0.0559 (5) | |
C1 | 0.6584 (2) | 0.29701 (16) | 0.3456 (3) | 0.0545 (5) | |
C2 | 0.8289 (2) | 0.15828 (16) | 0.3047 (2) | 0.0547 (6) | |
H2 | 0.9257 | 0.1682 | 0.3294 | 0.066* | |
C3 | 0.8163 (2) | 0.17551 (17) | 0.1456 (3) | 0.0532 (5) | |
C4 | 0.6391 (2) | 0.30947 (16) | 0.1851 (3) | 0.0557 (6) | |
H4 | 0.5423 | 0.2954 | 0.1646 | 0.067* | |
C5 | 0.6650 (3) | 0.4227 (2) | 0.1484 (3) | 0.0762 (8) | |
H5A | 0.6114 | 0.4674 | 0.2113 | 0.091* | |
H5B | 0.6368 | 0.4362 | 0.0503 | 0.091* | |
C6 | 0.7736 (3) | 0.2262 (2) | 0.5494 (3) | 0.0815 (9) | |
H6A | 0.6907 | 0.2052 | 0.5969 | 0.122* | |
H6B | 0.8004 | 0.2944 | 0.5826 | 0.122* | |
H6C | 0.8449 | 0.1767 | 0.5703 | 0.122* | |
C7 | 0.7009 (4) | 0.2486 (2) | −0.0583 (3) | 0.0839 (9) | |
H7A | 0.7198 | 0.1822 | −0.1026 | 0.126* | |
H7B | 0.7629 | 0.3005 | −0.0951 | 0.126* | |
H7C | 0.6083 | 0.2690 | −0.0792 | 0.126* | |
C8 | 0.7935 (3) | 0.04213 (18) | 0.3380 (3) | 0.0670 (6) | |
H8A | 0.8394 | −0.0024 | 0.2687 | 0.080* | |
H8B | 0.8287 | 0.0245 | 0.4324 | 0.080* | |
C9 | 0.6422 (2) | 0.01950 (15) | 0.3342 (3) | 0.0543 (5) | |
C10 | 0.5694 (3) | 0.0095 (3) | 0.4588 (3) | 0.0836 (9) | |
H10 | 0.6150 | 0.0158 | 0.5460 | 0.100* | |
C11 | 0.5695 (3) | 0.0099 (2) | 0.2090 (2) | 0.0650 (7) | |
H11 | 0.6150 | 0.0169 | 0.1218 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.1184 (7) | 0.0881 (5) | 0.0666 (4) | −0.0479 (4) | −0.0136 (4) | 0.0130 (4) |
O1 | 0.0778 (13) | 0.0795 (11) | 0.0767 (12) | 0.0048 (10) | 0.0193 (10) | −0.0216 (9) |
O2 | 0.0737 (12) | 0.0759 (10) | 0.0793 (12) | 0.0106 (10) | 0.0172 (9) | −0.0187 (10) |
N1 | 0.0583 (11) | 0.0546 (11) | 0.0493 (10) | −0.0055 (9) | 0.0019 (8) | −0.0016 (9) |
N2 | 0.0597 (12) | 0.0572 (11) | 0.0506 (11) | −0.0003 (9) | −0.0018 (9) | −0.0062 (9) |
C1 | 0.0470 (12) | 0.0538 (12) | 0.0627 (13) | −0.0084 (10) | 0.0060 (12) | −0.0089 (11) |
C2 | 0.0440 (11) | 0.0564 (13) | 0.0636 (15) | −0.0017 (10) | −0.0030 (10) | −0.0008 (10) |
C3 | 0.0484 (12) | 0.0491 (11) | 0.0621 (14) | −0.0048 (10) | 0.0056 (11) | −0.0073 (10) |
C4 | 0.0452 (12) | 0.0564 (12) | 0.0656 (14) | 0.0008 (10) | −0.0061 (10) | −0.0091 (11) |
C5 | 0.096 (2) | 0.0602 (14) | 0.0723 (17) | 0.0128 (13) | −0.0166 (16) | 0.0024 (12) |
C6 | 0.092 (2) | 0.096 (2) | 0.0571 (17) | −0.0088 (17) | −0.0059 (14) | 0.0022 (14) |
C7 | 0.103 (2) | 0.094 (2) | 0.0551 (16) | 0.0049 (18) | −0.0098 (15) | −0.0099 (15) |
C8 | 0.0616 (15) | 0.0546 (13) | 0.0847 (17) | 0.0043 (11) | −0.0121 (14) | 0.0095 (13) |
C9 | 0.0673 (14) | 0.0383 (10) | 0.0573 (12) | −0.0011 (9) | −0.0044 (12) | 0.0064 (10) |
C10 | 0.101 (2) | 0.108 (2) | 0.0423 (14) | −0.0420 (19) | −0.0146 (13) | 0.0140 (14) |
C11 | 0.0803 (16) | 0.0696 (14) | 0.0451 (13) | −0.0220 (13) | 0.0084 (11) | −0.0067 (11) |
Cl1—C5 | 1.776 (3) | C5—H5B | 0.970 |
O1—C1 | 1.227 (3) | C6—H6A | 0.960 |
O2—C3 | 1.218 (3) | C6—H6B | 0.960 |
N1—C1 | 1.324 (3) | C6—H6C | 0.960 |
N1—C2 | 1.455 (3) | C7—H7A | 0.960 |
N1—C6 | 1.459 (3) | C7—H7B | 0.960 |
N2—C3 | 1.338 (3) | C7—H7C | 0.960 |
N2—C4 | 1.441 (3) | C8—H8A | 0.970 |
N2—C7 | 1.456 (3) | C8—H8B | 0.970 |
C1—C4 | 1.515 (3) | C8—C9 | 1.505 (3) |
C2—H2 | 0.980 | C9—C10 | 1.366 (3) |
C2—C3 | 1.503 (3) | C9—C11 | 1.370 (3) |
C2—C8 | 1.553 (3) | C10—C10i | 1.375 (6) |
C4—H4 | 0.980 | C10—H10 | 0.930 |
C4—C5 | 1.507 (3) | C11—C11i | 1.379 (5) |
C5—H5A | 0.970 | C11—H11 | 0.930 |
C1—N1—C2 | 124.4 (2) | H5A—C5—H5B | 108.2 |
C1—N1—C6 | 117.8 (2) | N1—C6—H6A | 109.5 |
C2—N1—C6 | 117.9 (2) | N1—C6—H6B | 109.5 |
C3—N2—C4 | 124.5 (2) | N1—C6—H6C | 109.5 |
C3—N2—C7 | 118.1 (2) | H6A—C6—H6B | 109.5 |
C4—N2—C7 | 117.0 (2) | H6A—C6—H6C | 109.5 |
O1—C1—N1 | 122.6 (2) | H6B—C6—H6C | 109.5 |
O1—C1—C4 | 117.8 (2) | N2—C7—H7A | 109.5 |
N1—C1—C4 | 119.55 (19) | N2—C7—H7B | 109.5 |
N1—C2—H2 | 106.9 | N2—C7—H7C | 109.5 |
N1—C2—C3 | 115.65 (18) | H7A—C7—H7B | 109.5 |
N1—C2—C8 | 111.45 (19) | H7A—C7—H7C | 109.5 |
H2—C2—C3 | 106.9 | H7B—C7—H7C | 109.5 |
H2—C2—C8 | 106.9 | C2—C8—H8A | 108.9 |
C3—C2—C8 | 108.57 (19) | C2—C8—H8B | 108.9 |
O2—C3—N2 | 122.1 (2) | C2—C8—C9 | 113.35 (18) |
O2—C3—C2 | 118.8 (2) | H8A—C8—H8B | 107.7 |
N2—C3—C2 | 119.0 (2) | H8A—C8—C9 | 108.9 |
N2—C4—C1 | 115.66 (19) | H8B—C8—C9 | 108.9 |
N2—C4—H4 | 107.0 | C8—C9—C10 | 120.5 (2) |
N2—C4—C5 | 111.9 (2) | C8—C9—C11 | 123.0 (2) |
C1—C4—H4 | 107.0 | C10—C9—C11 | 116.5 (2) |
C1—C4—C5 | 107.67 (19) | C9—C10—C10i | 121.87 (15) |
H4—C4—C5 | 107.0 | C9—C10—H10 | 119.1 |
Cl1—C5—C4 | 109.98 (18) | C10i—C10—H10 | 119.1 |
Cl1—C5—H5A | 109.7 | C9—C11—C11i | 121.68 (14) |
Cl1—C5—H5B | 109.7 | C9—C11—H11 | 119.2 |
C4—C5—H5A | 109.7 | C11i—C11—H11 | 119.2 |
C4—C5—H5B | 109.7 | ||
C2—N1—C1—O1 | 176.8 (2) | C3—N2—C4—C5 | 115.8 (3) |
C2—N1—C1—C4 | −5.5 (3) | C7—N2—C4—C1 | 179.2 (2) |
C6—N1—C1—O1 | −2.6 (3) | C7—N2—C4—C5 | −57.0 (3) |
C6—N1—C1—C4 | 175.2 (2) | O1—C1—C4—N2 | −177.97 (19) |
C1—N1—C2—C3 | 9.1 (3) | O1—C1—C4—C5 | 56.0 (3) |
C1—N1—C2—C8 | −115.5 (2) | N1—C1—C4—N2 | 4.2 (3) |
C6—N1—C2—C3 | −171.6 (2) | N1—C1—C4—C5 | −121.9 (2) |
C6—N1—C2—C8 | 63.8 (3) | N2—C4—C5—Cl1 | −58.2 (2) |
C4—N2—C3—O2 | −171.5 (2) | C1—C4—C5—Cl1 | 70.0 (2) |
C4—N2—C3—C2 | 12.2 (3) | N1—C2—C8—C9 | 51.9 (3) |
C7—N2—C3—O2 | 1.2 (3) | C3—C2—C8—C9 | −76.6 (3) |
C7—N2—C3—C2 | −175.1 (2) | C2—C8—C9—C10 | −102.6 (3) |
N1—C2—C3—O2 | 171.6 (2) | C2—C8—C9—C11 | 76.0 (3) |
N1—C2—C3—N2 | −12.0 (3) | C8—C9—C10—C10i | 179.0 (4) |
C8—C2—C3—O2 | −62.3 (3) | C11—C9—C10—C10i | 0.2 (5) |
C8—C2—C3—N2 | 114.1 (2) | C8—C9—C11—C11i | −179.4 (3) |
C3—N2—C4—C1 | −8.0 (3) | C10—C9—C11—C11i | −0.7 (4) |
Symmetry code: (i) −x+1, −y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6C···O1ii | 0.96 | 2.42 | 3.255 (4) | 145 |
C8—H8B···O1iii | 0.97 | 2.68 | 3.463 (3) | 138 |
C5—H5B···O2iv | 0.97 | 2.67 | 3.323 (3) | 125 |
C7—H7C···O2v | 0.96 | 2.50 | 3.415 (4) | 158 |
Symmetry codes: (ii) x+1/2, −y+1/2, −z+1; (iii) −x+3/2, y−1/2, −z+1; (iv) −x+3/2, y+1/2, −z; (v) x−1/2, −y+1/2, −z. |
C22H28Cl2N4O4 | F(000) = 508 |
Mr = 483.38 | Dx = 1.421 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 1653 reflections |
a = 9.2208 (13) Å | θ = 2.7–27.6° |
b = 12.6517 (19) Å | µ = 0.33 mm−1 |
c = 9.6894 (15) Å | T = 100 K |
β = 92.123 (2)° | Prism, colourless |
V = 1129.6 (3) Å3 | 0.19 × 0.16 × 0.10 mm |
Z = 2 |
Bruker Kappa APEXII DUO CCD diffractometer | 2919 independent reflections |
Radiation source: fine-focus sealed tube with Miracol optics | 2603 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ϕ and ω scans | θmax = 28.3°, θmin = 2.1° |
Absorption correction: multi-scan (TWINABS 2008/2; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.632, Tmax = 0.746 | k = 0→16 |
2919 measured reflections | l = 0→12 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.085 | w = 1/[σ2(Fo2) + (0.0515P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
2919 reflections | Δρmax = 0.32 e Å−3 |
294 parameters | Δρmin = −0.23 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.07 (7) |
C22H28Cl2N4O4 | V = 1129.6 (3) Å3 |
Mr = 483.38 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.2208 (13) Å | µ = 0.33 mm−1 |
b = 12.6517 (19) Å | T = 100 K |
c = 9.6894 (15) Å | 0.19 × 0.16 × 0.10 mm |
β = 92.123 (2)° |
Bruker Kappa APEXII DUO CCD diffractometer | 2919 independent reflections |
Absorption correction: multi-scan (TWINABS 2008/2; Sheldrick, 1996) | 2603 reflections with I > 2σ(I) |
Tmin = 0.632, Tmax = 0.746 | Rint = 0.034 |
2919 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.085 | Δρmax = 0.32 e Å−3 |
S = 1.02 | Δρmin = −0.23 e Å−3 |
2919 reflections | Absolute structure: Flack (1983) |
294 parameters | Absolute structure parameter: 0.07 (7) |
1 restraint |
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 | ||
Cl1 | 0.33843 (8) | 1.19205 (6) | 0.39512 (8) | 0.0325 (2) | |
Cl2 | 0.32739 (9) | 0.28478 (6) | 1.08306 (8) | 0.0325 (2) | |
O1 | 0.0896 (2) | 1.09490 (19) | 0.6629 (2) | 0.0275 (5) | |
O2 | 0.4453 (2) | 0.87240 (17) | 0.3538 (2) | 0.0241 (5) | |
O3 | 0.0580 (2) | 0.38588 (18) | 0.8309 (2) | 0.0250 (5) | |
O4 | 0.4258 (2) | 0.61604 (19) | 1.1450 (2) | 0.0276 (5) | |
N1 | 0.1162 (3) | 0.9680 (2) | 0.5037 (2) | 0.0198 (5) | |
N2 | 0.4185 (3) | 0.9841 (2) | 0.5311 (2) | 0.0199 (5) | |
N3 | 0.0919 (3) | 0.5056 (2) | 1.0011 (2) | 0.0188 (5) | |
N4 | 0.3925 (3) | 0.5039 (2) | 0.9675 (2) | 0.0197 (5) | |
C1 | 0.1676 (3) | 1.0390 (2) | 0.5937 (3) | 0.0191 (6) | |
C2 | 0.2036 (3) | 0.8988 (2) | 0.4195 (3) | 0.0188 (6) | |
H2 | 0.1725 | 0.9113 | 0.3209 | 0.023* | |
C3 | 0.3657 (3) | 0.9197 (2) | 0.4317 (3) | 0.0178 (6) | |
C4 | 0.3309 (3) | 1.0556 (3) | 0.6100 (3) | 0.0200 (6) | |
H4 | 0.3584 | 1.0445 | 0.7097 | 0.024* | |
C5 | 0.3640 (4) | 1.1698 (3) | 0.5767 (3) | 0.0272 (7) | |
H5A | 0.4654 | 1.1864 | 0.6060 | 0.033* | |
H5B | 0.2990 | 1.2169 | 0.6277 | 0.033* | |
C6 | −0.0419 (3) | 0.9581 (3) | 0.4875 (3) | 0.0262 (7) | |
H6A | −0.0791 | 0.9201 | 0.5669 | 0.039* | |
H6B | −0.0667 | 0.9190 | 0.4026 | 0.039* | |
H6C | −0.0856 | 1.0287 | 0.4822 | 0.039* | |
C7 | 0.5758 (3) | 0.9973 (3) | 0.5448 (3) | 0.0284 (7) | |
H7A | 0.6232 | 0.9287 | 0.5340 | 0.043* | |
H7B | 0.6017 | 1.0263 | 0.6362 | 0.043* | |
H7C | 0.6079 | 1.0460 | 0.4734 | 0.043* | |
C8 | 0.1763 (3) | 0.7805 (3) | 0.4501 (3) | 0.0222 (6) | |
H8A | 0.0826 | 0.7592 | 0.4052 | 0.027* | |
H8B | 0.2537 | 0.7378 | 0.4091 | 0.027* | |
C9 | 0.1727 (3) | 0.7565 (2) | 0.6016 (3) | 0.0198 (6) | |
C10 | 0.2953 (3) | 0.7609 (3) | 0.6903 (3) | 0.0246 (7) | |
H10 | 0.3869 | 0.7774 | 0.6541 | 0.029* | |
C11 | 0.2856 (3) | 0.7416 (3) | 0.8301 (3) | 0.0235 (6) | |
H11 | 0.3709 | 0.7449 | 0.8881 | 0.028* | |
C12 | 0.1541 (3) | 0.7173 (3) | 0.8877 (3) | 0.0211 (6) | |
C13 | 0.0336 (3) | 0.7095 (3) | 0.7989 (3) | 0.0273 (7) | |
H13 | −0.0571 | 0.6900 | 0.8348 | 0.033* | |
C14 | 0.0423 (3) | 0.7293 (3) | 0.6597 (3) | 0.0263 (7) | |
H14 | −0.0429 | 0.7243 | 0.6020 | 0.032* | |
C15 | 0.1433 (3) | 0.6963 (3) | 1.0400 (3) | 0.0239 (6) | |
H15A | 0.0432 | 0.7118 | 1.0677 | 0.029* | |
H15B | 0.2098 | 0.7446 | 1.0919 | 0.029* | |
C16 | 0.1817 (3) | 0.5804 (2) | 1.0797 (3) | 0.0188 (6) | |
H16 | 0.1599 | 0.5710 | 1.1794 | 0.023* | |
C17 | 0.3448 (3) | 0.5661 (3) | 1.0669 (3) | 0.0198 (6) | |
C18 | 0.3016 (3) | 0.4335 (2) | 0.8824 (3) | 0.0180 (6) | |
H18 | 0.3188 | 0.4509 | 0.7837 | 0.022* | |
C19 | 0.1388 (3) | 0.4421 (2) | 0.9026 (3) | 0.0181 (6) | |
C20 | −0.0648 (3) | 0.5046 (3) | 1.0253 (3) | 0.0276 (7) | |
H20A | −0.1182 | 0.5298 | 0.9423 | 0.041* | |
H20B | −0.0850 | 0.5511 | 1.1032 | 0.041* | |
H20C | −0.0955 | 0.4324 | 1.0464 | 0.041* | |
C21 | 0.5485 (3) | 0.4965 (3) | 0.9517 (3) | 0.0274 (7) | |
H21A | 0.5916 | 0.5672 | 0.9591 | 0.041* | |
H21B | 0.5680 | 0.4664 | 0.8611 | 0.041* | |
H21C | 0.5911 | 0.4510 | 1.0243 | 0.041* | |
C22 | 0.3438 (3) | 0.3181 (3) | 0.9050 (3) | 0.0267 (7) | |
H22A | 0.4451 | 0.3068 | 0.8777 | 0.032* | |
H22B | 0.2797 | 0.2721 | 0.8471 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0230 (4) | 0.0374 (5) | 0.0372 (4) | −0.0015 (4) | 0.0008 (3) | 0.0181 (4) |
Cl2 | 0.0277 (4) | 0.0327 (5) | 0.0378 (4) | 0.0086 (3) | 0.0098 (3) | 0.0175 (4) |
O1 | 0.0271 (11) | 0.0284 (12) | 0.0275 (12) | 0.0099 (10) | 0.0072 (9) | −0.0003 (9) |
O2 | 0.0240 (11) | 0.0250 (12) | 0.0238 (11) | 0.0058 (10) | 0.0067 (8) | −0.0018 (9) |
O3 | 0.0241 (11) | 0.0249 (11) | 0.0258 (11) | −0.0070 (10) | −0.0019 (9) | −0.0004 (9) |
O4 | 0.0286 (11) | 0.0284 (12) | 0.0255 (12) | −0.0070 (10) | −0.0050 (9) | −0.0015 (9) |
N1 | 0.0150 (11) | 0.0232 (13) | 0.0215 (12) | 0.0032 (10) | 0.0023 (9) | 0.0027 (10) |
N2 | 0.0180 (12) | 0.0214 (13) | 0.0204 (12) | 0.0003 (10) | 0.0014 (9) | 0.0002 (10) |
N3 | 0.0172 (11) | 0.0194 (13) | 0.0198 (12) | 0.0009 (10) | 0.0009 (9) | 0.0018 (10) |
N4 | 0.0127 (11) | 0.0244 (13) | 0.0220 (12) | −0.0014 (10) | 0.0011 (9) | 0.0000 (10) |
C1 | 0.0213 (14) | 0.0183 (16) | 0.0178 (14) | 0.0030 (11) | 0.0011 (11) | 0.0047 (11) |
C2 | 0.0183 (13) | 0.0234 (16) | 0.0146 (13) | 0.0016 (12) | 0.0013 (10) | −0.0011 (11) |
C3 | 0.0192 (13) | 0.0176 (15) | 0.0167 (13) | 0.0003 (12) | 0.0015 (10) | 0.0040 (11) |
C4 | 0.0215 (14) | 0.0234 (15) | 0.0152 (13) | 0.0018 (12) | 0.0005 (11) | −0.0007 (11) |
C5 | 0.0307 (16) | 0.0237 (18) | 0.0271 (16) | −0.0032 (14) | −0.0025 (13) | −0.0013 (13) |
C6 | 0.0144 (14) | 0.0319 (18) | 0.0324 (17) | −0.0012 (13) | 0.0021 (12) | 0.0042 (14) |
C7 | 0.0178 (14) | 0.0336 (19) | 0.0336 (17) | 0.0007 (14) | −0.0008 (12) | −0.0044 (14) |
C8 | 0.0230 (13) | 0.0212 (15) | 0.0222 (14) | −0.0009 (13) | −0.0003 (11) | −0.0008 (13) |
C9 | 0.0210 (14) | 0.0151 (14) | 0.0234 (15) | −0.0001 (11) | 0.0025 (11) | 0.0003 (11) |
C10 | 0.0173 (13) | 0.0238 (18) | 0.0327 (16) | −0.0020 (12) | 0.0021 (11) | 0.0083 (13) |
C11 | 0.0183 (13) | 0.0240 (15) | 0.0279 (16) | −0.0042 (12) | −0.0041 (11) | 0.0037 (13) |
C12 | 0.0246 (14) | 0.0132 (14) | 0.0258 (15) | 0.0043 (11) | 0.0043 (12) | 0.0003 (11) |
C13 | 0.0172 (13) | 0.0315 (18) | 0.0335 (17) | 0.0030 (13) | 0.0042 (12) | 0.0076 (14) |
C14 | 0.0177 (14) | 0.0282 (17) | 0.0323 (17) | −0.0073 (13) | −0.0067 (12) | 0.0043 (13) |
C15 | 0.0300 (15) | 0.0181 (15) | 0.0238 (15) | 0.0031 (14) | 0.0032 (11) | −0.0031 (13) |
C16 | 0.0215 (14) | 0.0183 (15) | 0.0166 (14) | 0.0006 (12) | 0.0021 (11) | 0.0000 (11) |
C17 | 0.0240 (14) | 0.0173 (15) | 0.0179 (14) | −0.0023 (12) | −0.0011 (11) | 0.0012 (11) |
C18 | 0.0199 (13) | 0.0178 (14) | 0.0163 (13) | −0.0036 (12) | 0.0020 (10) | 0.0007 (11) |
C19 | 0.0198 (13) | 0.0171 (15) | 0.0175 (14) | −0.0030 (11) | 0.0002 (10) | 0.0041 (11) |
C20 | 0.0173 (14) | 0.0330 (18) | 0.0326 (17) | 0.0031 (14) | 0.0047 (12) | 0.0015 (14) |
C21 | 0.0176 (14) | 0.0311 (18) | 0.0336 (17) | −0.0002 (14) | 0.0042 (12) | −0.0023 (14) |
C22 | 0.0260 (15) | 0.0264 (17) | 0.0282 (16) | 0.0003 (13) | 0.0087 (13) | −0.0018 (13) |
Cl1—C5 | 1.788 (3) | C7—H7C | 0.980 |
Cl2—C22 | 1.788 (3) | C8—H8A | 0.990 |
O1—C1 | 1.226 (4) | C8—H8B | 0.990 |
O2—C3 | 1.228 (3) | C8—C9 | 1.500 (4) |
O3—C19 | 1.227 (4) | C9—C10 | 1.396 (4) |
O4—C17 | 1.219 (4) | C9—C14 | 1.390 (4) |
N1—C1 | 1.328 (4) | C10—H10 | 0.950 |
N1—C2 | 1.460 (4) | C10—C11 | 1.383 (4) |
N1—C6 | 1.465 (4) | C11—H11 | 0.950 |
N2—C3 | 1.339 (4) | C11—C12 | 1.388 (4) |
N2—C4 | 1.450 (4) | C12—C13 | 1.383 (4) |
N2—C7 | 1.461 (4) | C12—C15 | 1.507 (4) |
N3—C16 | 1.454 (4) | C13—H13 | 0.950 |
N3—C19 | 1.332 (4) | C13—C14 | 1.378 (4) |
N3—C20 | 1.472 (4) | C14—H14 | 0.950 |
N4—C17 | 1.331 (4) | C15—H15A | 0.990 |
N4—C18 | 1.456 (4) | C15—H15B | 0.990 |
N4—C21 | 1.455 (4) | C15—C16 | 1.554 (4) |
C1—C4 | 1.523 (4) | C16—H16 | 1.000 |
C2—H2 | 1.000 | C16—C17 | 1.525 (4) |
C2—C3 | 1.518 (4) | C18—H18 | 1.000 |
C2—C8 | 1.548 (5) | C18—C19 | 1.525 (4) |
C4—H4 | 1.000 | C18—C22 | 1.525 (5) |
C4—C5 | 1.514 (5) | C20—H20A | 0.980 |
C5—H5A | 0.990 | C20—H20B | 0.980 |
C5—H5B | 0.990 | C20—H20C | 0.980 |
C6—H6A | 0.980 | C21—H21A | 0.980 |
C6—H6B | 0.980 | C21—H21B | 0.980 |
C6—H6C | 0.980 | C21—H21C | 0.980 |
C7—H7A | 0.980 | C22—H22A | 0.990 |
C7—H7B | 0.980 | C22—H22B | 0.990 |
C1—N1—C2 | 125.6 (2) | C9—C10—H10 | 119.5 |
C1—N1—C6 | 117.2 (3) | C9—C10—C11 | 121.1 (3) |
C2—N1—C6 | 117.2 (3) | H10—C10—C11 | 119.5 |
C3—N2—C4 | 124.3 (2) | C10—C11—H11 | 119.3 |
C3—N2—C7 | 117.9 (3) | C10—C11—C12 | 121.5 (3) |
C4—N2—C7 | 116.8 (3) | H11—C11—C12 | 119.3 |
C16—N3—C19 | 125.0 (2) | C11—C12—C13 | 117.4 (3) |
C16—N3—C20 | 117.7 (2) | C11—C12—C15 | 121.6 (3) |
C19—N3—C20 | 117.1 (3) | C13—C12—C15 | 121.0 (3) |
C17—N4—C18 | 124.9 (2) | C12—C13—H13 | 119.3 |
C17—N4—C21 | 117.9 (3) | C12—C13—C14 | 121.4 (3) |
C18—N4—C21 | 116.9 (2) | H13—C13—C14 | 119.3 |
O1—C1—N1 | 123.2 (3) | C9—C14—C13 | 121.6 (3) |
O1—C1—C4 | 117.5 (3) | C9—C14—H14 | 119.2 |
N1—C1—C4 | 119.3 (3) | C13—C14—H14 | 119.2 |
N1—C2—H2 | 107.1 | C12—C15—H15A | 109.0 |
N1—C2—C3 | 114.5 (3) | C12—C15—H15B | 109.0 |
N1—C2—C8 | 112.1 (2) | C12—C15—C16 | 112.8 (2) |
H2—C2—C3 | 107.1 | H15A—C15—H15B | 107.8 |
H2—C2—C8 | 107.1 | H15A—C15—C16 | 109.0 |
C3—C2—C8 | 108.7 (2) | H15B—C15—C16 | 109.0 |
O2—C3—N2 | 121.9 (3) | N3—C16—C15 | 111.4 (2) |
O2—C3—C2 | 118.4 (3) | N3—C16—H16 | 107.4 |
N2—C3—C2 | 119.5 (3) | N3—C16—C17 | 115.1 (2) |
N2—C4—C1 | 115.3 (2) | C15—C16—H16 | 107.4 |
N2—C4—H4 | 107.1 | C15—C16—C17 | 107.9 (3) |
N2—C4—C5 | 111.3 (2) | H16—C16—C17 | 107.4 |
C1—C4—H4 | 107.2 | O4—C17—N4 | 123.0 (3) |
C1—C4—C5 | 108.4 (3) | O4—C17—C16 | 118.1 (3) |
H4—C4—C5 | 107.1 | N4—C17—C16 | 118.8 (3) |
Cl1—C5—C4 | 109.8 (2) | N4—C18—H18 | 107.4 |
Cl1—C5—H5A | 109.7 | N4—C18—C19 | 115.6 (2) |
Cl1—C5—H5B | 109.7 | N4—C18—C22 | 111.4 (2) |
C4—C5—H5A | 109.7 | H18—C18—C19 | 107.4 |
C4—C5—H5B | 109.7 | H18—C18—C22 | 107.4 |
H5A—C5—H5B | 108.2 | C19—C18—C22 | 107.3 (3) |
N1—C6—H6A | 109.5 | O3—C19—N3 | 123.3 (3) |
N1—C6—H6B | 109.5 | O3—C19—C18 | 117.8 (3) |
N1—C6—H6C | 109.5 | N3—C19—C18 | 118.8 (3) |
H6A—C6—H6B | 109.5 | N3—C20—H20A | 109.5 |
H6A—C6—H6C | 109.5 | N3—C20—H20B | 109.5 |
H6B—C6—H6C | 109.5 | N3—C20—H20C | 109.5 |
N2—C7—H7A | 109.5 | H20A—C20—H20B | 109.5 |
N2—C7—H7B | 109.5 | H20A—C20—H20C | 109.5 |
N2—C7—H7C | 109.5 | H20B—C20—H20C | 109.5 |
H7A—C7—H7B | 109.5 | N4—C21—H21A | 109.5 |
H7A—C7—H7C | 109.5 | N4—C21—H21B | 109.5 |
H7B—C7—H7C | 109.5 | N4—C21—H21C | 109.5 |
C2—C8—H8A | 109.0 | H21A—C21—H21B | 109.5 |
C2—C8—H8B | 109.0 | H21A—C21—H21C | 109.5 |
C2—C8—C9 | 113.1 (3) | H21B—C21—H21C | 109.5 |
H8A—C8—H8B | 107.8 | Cl2—C22—C18 | 109.5 (2) |
H8A—C8—C9 | 109.0 | Cl2—C22—H22A | 109.8 |
H8B—C8—C9 | 109.0 | Cl2—C22—H22B | 109.8 |
C8—C9—C10 | 123.2 (3) | C18—C22—H22A | 109.8 |
C8—C9—C14 | 119.8 (3) | C18—C22—H22B | 109.8 |
C10—C9—C14 | 117.0 (3) | H22A—C22—H22B | 108.2 |
C2—N1—C1—O1 | −179.5 (3) | C11—C12—C13—C14 | −2.7 (5) |
C2—N1—C1—C4 | 2.6 (4) | C15—C12—C13—C14 | 179.5 (3) |
C6—N1—C1—O1 | 0.5 (4) | C12—C13—C14—C9 | 1.0 (6) |
C6—N1—C1—C4 | −177.4 (3) | C8—C9—C14—C13 | −178.2 (3) |
C1—N1—C2—C3 | −5.3 (4) | C10—C9—C14—C13 | 1.1 (5) |
C1—N1—C2—C8 | 119.1 (3) | C11—C12—C15—C16 | −83.5 (4) |
C6—N1—C2—C3 | 174.8 (3) | C13—C12—C15—C16 | 94.1 (4) |
C6—N1—C2—C8 | −60.8 (3) | C19—N3—C16—C15 | 109.9 (3) |
C4—N2—C3—O2 | 168.8 (3) | C19—N3—C16—C17 | −13.4 (4) |
C4—N2—C3—C2 | −15.1 (4) | C20—N3—C16—C15 | −65.8 (3) |
C7—N2—C3—O2 | 0.3 (4) | C20—N3—C16—C17 | 171.0 (3) |
C7—N2—C3—C2 | 176.4 (3) | C12—C15—C16—N3 | −55.9 (4) |
N1—C2—C3—O2 | −172.6 (3) | C12—C15—C16—C17 | 71.4 (3) |
N1—C2—C3—N2 | 11.1 (4) | C18—N4—C17—O4 | 172.5 (3) |
C8—C2—C3—O2 | 61.2 (3) | C18—N4—C17—C16 | −10.7 (4) |
C8—C2—C3—N2 | −115.1 (3) | C21—N4—C17—O4 | −0.5 (5) |
C3—N2—C4—C1 | 11.7 (4) | C21—N4—C17—C16 | 176.3 (3) |
C3—N2—C4—C5 | −112.3 (3) | N3—C16—C17—O4 | −169.7 (3) |
C7—N2—C4—C1 | −179.7 (3) | N3—C16—C17—N4 | 13.4 (4) |
C7—N2—C4—C5 | 56.3 (3) | C15—C16—C17—O4 | 65.2 (3) |
O1—C1—C4—N2 | 177.0 (3) | C15—C16—C17—N4 | −111.7 (3) |
O1—C1—C4—C5 | −57.4 (3) | C17—N4—C18—C19 | 6.2 (4) |
N1—C1—C4—N2 | −4.9 (4) | C17—N4—C18—C22 | −116.6 (3) |
N1—C1—C4—C5 | 120.6 (3) | C21—N4—C18—C19 | 179.3 (3) |
N2—C4—C5—Cl1 | 56.2 (3) | C21—N4—C18—C22 | 56.4 (3) |
C1—C4—C5—Cl1 | −71.7 (3) | C16—N3—C19—O3 | −174.1 (3) |
N1—C2—C8—C9 | −44.8 (3) | C16—N3—C19—C18 | 9.5 (4) |
C3—C2—C8—C9 | 82.8 (3) | C20—N3—C19—O3 | 1.6 (4) |
C2—C8—C9—C10 | −69.5 (4) | C20—N3—C19—C18 | −174.8 (3) |
C2—C8—C9—C14 | 109.9 (3) | N4—C18—C19—O3 | 178.5 (3) |
C8—C9—C10—C11 | 177.8 (3) | N4—C18—C19—N3 | −4.9 (4) |
C14—C9—C10—C11 | −1.6 (5) | C22—C18—C19—O3 | −56.5 (3) |
C9—C10—C11—C12 | −0.2 (5) | C22—C18—C19—N3 | 120.1 (3) |
C10—C11—C12—C13 | 2.3 (5) | N4—C18—C22—Cl2 | 58.7 (3) |
C10—C11—C12—C15 | −180.0 (3) | C19—C18—C22—Cl2 | −68.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O3i | 1.00 | 2.56 | 3.362 (4) | 137 |
C4—H4···O4ii | 1.00 | 2.56 | 3.296 (4) | 130 |
C5—H5A···O2iii | 0.99 | 2.52 | 3.167 (4) | 123 |
C6—H6B···O3i | 0.98 | 2.30 | 3.215 (4) | 154 |
C7—H7B···O4ii | 0.98 | 2.43 | 3.361 (4) | 159 |
C8—H8A···O1iv | 0.99 | 2.68 | 3.539 (4) | 145 |
C15—H15A···O3v | 0.99 | 2.60 | 3.307 (4) | 129 |
C20—H20B···O1vi | 0.98 | 2.33 | 3.246 (4) | 154 |
C21—H21B···O2vii | 0.98 | 2.40 | 3.353 (4) | 165 |
C22—H22A···O2vii | 0.99 | 2.63 | 3.302 (4) | 125 |
C22—H22A···O4viii | 0.99 | 2.70 | 3.371 (4) | 125 |
Symmetry codes: (i) −x, y+1/2, −z+1; (ii) −x+1, y+1/2, −z+2; (iii) −x+1, y+1/2, −z+1; (iv) −x, y−1/2, −z+1; (v) −x, y+1/2, −z+2; (vi) −x, y−1/2, −z+2; (vii) −x+1, y−1/2, −z+1; (viii) −x+1, y−1/2, −z+2. |
Experimental details
(1) | (2rt) | (2lt) | |
Crystal data | |||
Chemical formula | C22H28Cl2N4O4 | C22H28Cl2N4O4 | C22H28Cl2N4O4 |
Mr | 483.38 | 483.38 | 483.38 |
Crystal system, space group | Monoclinic, P21 | Orthorhombic, P21212 | Monoclinic, P21 |
Temperature (K) | 150 | 296 | 100 |
a, b, c (Å) | 8.4158 (17), 14.779 (3), 10.438 (2) | 9.7566 (5), 12.7626 (6), 9.3138 (4) | 9.2208 (13), 12.6517 (19), 9.6894 (15) |
α, β, γ (°) | 90, 110.58 (3), 90 | 90, 90, 90 | 90, 92.123 (2), 90 |
V (Å3) | 1215.3 (4) | 1159.75 (9) | 1129.6 (3) |
Z | 2 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.30 | 0.32 | 0.33 |
Crystal size (mm) | 0.32 × 0.13 × 0.07 | 0.20 × 0.15 × 0.09 | 0.19 × 0.16 × 0.10 |
Data collection | |||
Diffractometer | Nonius KappaCCD diffractometer | Bruker Kappa APEXII DUO CCD diffractometer | Bruker Kappa APEXII DUO CCD diffractometer |
Absorption correction | Multi-scan (SADABS 2008/1; Sheldrick, 1996) | Numerical (SADABS 2008/1; Sheldrick, 1996) | Multi-scan (TWINABS 2008/2; Sheldrick, 1996) |
Tmin, Tmax | 0.664, 0.917 | 0.641, 0.745 | 0.632, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8536, 1649, 1123 | 15349, 2288, 1847 | 2919, 2919, 2603 |
Rint | 0.128 | 0.025 | 0.034 |
θmax (°) | 22.5 | 26.0 | 28.3 |
(sin θ/λ)max (Å−1) | 0.538 | 0.618 | 0.668 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.080, 0.134, 1.18 | 0.037, 0.102, 1.03 | 0.035, 0.085, 1.02 |
No. of reflections | 1649 | 2288 | 2919 |
No. of parameters | 293 | 148 | 294 |
No. of restraints | 1 | 0 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.29 | 0.22, −0.18 | 0.32, −0.23 |
Absolute structure | ? | Flack (1983) | Flack (1983) |
Absolute structure parameter | ? | −0.03 (8) | 0.07 (7) |
Computer programs: COLLECT (Nonius, 1998), APEX2 (Bruker, 2007), EVALCCD (Duisenberg et al., 2003), CELL_NOW (Sheldrick, 2004) and SAINT (Bruker, 2007), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2009) and local programs.
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O3i | 1.00 | 2.49 | 3.487 (14) | 173 |
C4—H4···O4 | 1.00 | 2.64 | 3.379 (13) | 131 |
C18—H18···O1 | 1.00 | 2.39 | 3.372 (14) | 167 |
Symmetry code: (i) x−1, y, z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6C···O1i | 0.96 | 2.42 | 3.255 (4) | 145 |
C8—H8B···O1ii | 0.97 | 2.68 | 3.463 (3) | 138 |
C5—H5B···O2iii | 0.97 | 2.67 | 3.323 (3) | 125 |
C7—H7C···O2iv | 0.96 | 2.50 | 3.415 (4) | 158 |
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) −x+3/2, y−1/2, −z+1; (iii) −x+3/2, y+1/2, −z; (iv) x−1/2, −y+1/2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O3i | 1.00 | 2.56 | 3.362 (4) | 137 |
C4—H4···O4ii | 1.00 | 2.56 | 3.296 (4) | 130 |
C5—H5A···O2iii | 0.99 | 2.52 | 3.167 (4) | 123 |
C6—H6B···O3i | 0.98 | 2.30 | 3.215 (4) | 154 |
C7—H7B···O4ii | 0.98 | 2.43 | 3.361 (4) | 159 |
C8—H8A···O1iv | 0.99 | 2.68 | 3.539 (4) | 145 |
C15—H15A···O3v | 0.99 | 2.60 | 3.307 (4) | 129 |
C20—H20B···O1vi | 0.98 | 2.33 | 3.246 (4) | 154 |
C21—H21B···O2vii | 0.98 | 2.40 | 3.353 (4) | 165 |
C22—H22A···O2vii | 0.99 | 2.63 | 3.302 (4) | 125 |
C22—H22A···O4viii | 0.99 | 2.70 | 3.371 (4) | 125 |
Symmetry codes: (i) −x, y+1/2, −z+1; (ii) −x+1, y+1/2, −z+2; (iii) −x+1, y+1/2, −z+1; (iv) −x, y−1/2, −z+1; (v) −x, y+1/2, −z+2; (vi) −x, y−1/2, −z+2; (vii) −x+1, y−1/2, −z+1; (viii) −x+1, y−1/2, −z+2. |
Sporidesmins are a diverse class of natural products containing molecules with one or two epidithiodioxopiperazine (ETP) rings that display a wide variety of biological activities (Waksman & Bugie, 1944; Saito et al., 1988; Fujimoto et al., 2004; Gardiner et al., 2005; Li et al., 2006). While toxic to mammalian cells, studies have suggested that certain sporidesmins, namely bis-ETPs chetomin (Waksman & Bugie, 1944) and chaetocin (Hauser et al.,1970), may possess anticancer activity due to their ability to suppress neovascularization (Waksman & Bugie, 1944; Hauser et al., 1970; McInnes et al., 1976; Brewer et al., 1978; Kung, et al., 2004). In order to understand better the chemistry and biology of the bridged bis-ETPs, diketopiperazines (1,4-piperazine-2,5-diones, DKPs) (Martins & Carvalho, 2007) and bridged bis-DKP structures lacking a disulfide bridge must also be studied. Even in the absence of the disulfide bridge many compounds of this class exhibit a broad spectrum of interesting biological activity. Natural products, such as ditryptophenaline (Springer et al., 1977), WIN-64821,WIN-64745, (Barrow et al., 1993; Popp et al., 1994) and Leptosin S (Yamada et al., 2004) incorporate a 3a,3a'-bispyrrolidinoindoline core with contiguous stereogenic quaternary carbons and display cytotoxicity in various cell lines. Perhaps the most interesting is a C2-symmetrical piperazine-2,5-dione WIN-64821, which is a competitive substance- P antagonist against the human NK1 receptor at submicromolar concentrations (Barrow et al., 1993; Popp et al., 1994; Oleynek et al., 1994; Sedlock, et al. 1994) and also serves as an antagonist of the cholecystokinin type-B receptor (Hiramoto et al., 1994). The title compound was synthesized as part of a wider project to develop new synthetic methods for the preparation of bridged bis-DKPs (Polaske et al., 2009). Unlike other model compounds, which we observed to crystallize consistently in one form only, this compound crystallizes as at least two polymorphic forms, obtained by different methods of crystallization. The molecular structures of the polymorphs are very different: one adopts a `C' shape (1) while the other adopts an `S' shape (2). The `S'-shaped polymorph also undergoes a reversible orthorhombic-to-monoclinic phase transition upon cooling (the `C'-shaped structure is insensitive to temperature).
The molecular structure of polymorph (1) is shown in Fig. 1. The `C' shape is supported by weak, distorted intra- and intermolecular C–H···O interactions and by Cl···Cl interactions (Fig. 2). The refined Cl1···Cl2i [(i) = x-1, y, z-1] distance is 3.445 (4) Å and the pertinent angles are C5-Cl1···Cl2i,143.9 (4)° and C22i-Cl2i···Cl1, 168.9 (5)°. This is slightly longer than a mean Cl···Cl distance of 3.38 Å obtained by a search of the Cambridge Structural Database (CSD, version 5.30 plus three updates; Allen, 2002) for Cl···Cl contact distances between two Cl atoms (not including those reported structures with Cl···Cl interactions between dichloromethane and chloroform), yielding 774 hits. Two R22(8) rings, one intermolecular, one intramolecular, are formed by C–H···O interactions. In all cases the C–H···O interactions are weak, with poorly activated H atoms, long H···O distances and the motif is rather distorted. Nevertheless, these motifs represent the favorable arrangement of mildy electropositive and electronegative sites such as to maximize electrostatic interaction; they are not a direct cause of the `C' shape, nor are they merely an effect of the shape.
The molecular structure of the polymorph determined at room temperature, (2rt), is shown in Fig. 3. The `S'-shaped molecule has crystallographic twofold rotational symmetry and as with (1) the crystal packing is dominated by an extensive network of weak intermolecular C–H···O interactions with all O atoms acting as bifurcated 'acceptors' although as in the case of (1) the geometry of the interactions and the poorly acidic nature of each donor H atom are indicative of very weak hydrogen bonding. There are no intramolecular interactions in this structure but here the Cl1···Cl1i [(i) = 2-x, 1-y, z] distance, at 3.319 (1) Å, is shorter than that observed in (1). The arrangement of C–H···O interactions is not trivial; contacts from the discrete crystallographically unique molecule touch eight adjacent molecules but do not form small cyclic motifs as in (1) and this is most easily seen by considering a perspective c-axis plot (Fig. 4). In Fig. 4 the discrete unique molecule is colored red and hydrogen- bonding contacts have been expanded to show all eight acceptor molecules.
The structural behavior of (2) was first noted by comparison of experimental X-ray powder diffraction patterns, which were measured at room temperature, with calculated X-ray powder diffraction patterns based on a low-temperature (100 K) single-crystal structure. The two did not match and it was then that a room-temperature single-crystal analysis was carried out. Although we have not carried out a systematic variable-temperature study of this compound, flash cooling to 100 K produces a single-crystal structure, (2lt), with some striking differences when compared with (2rt). The compound undergoes an orthorhombic-to-monoclinic phase transition; the obvious effect of this reduction in symmetry is loss of the twofold axis and consequently loss of crystallographically imposed symmetry on the discrete molecule (Fig. 5). Although the molecule retains an `S' shape, the two piperazinedione rings are able to twist further away from the central benzene ring. In (2lt) the torsion angles about the methylene linker are 109.9 (3)° (C2–C8–C9–C14) and 94.2 (4)° (C13–C12–C15–C16) whereas in (2rt) the equivalent torsion angle is 76.0 (3)°. This reduction in symmetry also causes the onset of non-merohedral twinning in the monoclinic structure; this is typical behavior in such situations. The crystal packing of (2lt) is not significantly different from that of (2rt) except that the twisting of the piperazinedione rings causes a change in the weak hydrogen-bonding geometry, bringing the oxygen acceptor sites into closer proximity with potential weak hydrogen donor sites. For example in (2rt) the approximate distance between H2 and O1i [(i) = 1/2+x, 1/2-y, 1-z] is approximately 2.81 Å; in (2lt) the equivalent distance, H2···O3vi [(vi) = -x, 1/2 + y, 1 - z] is approximately 2.56 Å. The Cl1···Cl2ii [(ii) = x, 1/2+y, z-1] distance in (2lt) is the shortest of all three structures, 3.2414 (11) Å. This behaviour of polymorph (2) was found to be reversible and the crystal suffered no physical defects (e.g. cracking) as a result of the phase change.
In summary, two polymorphs of the title compound have been identified. Both polymorphs differ entirely in their molecular structure and consequently in the crystal packing. `C'-shaped monoclinic polymorph (1) is insensitive to temperature change; `S'-shaped polymorph (2) is orthorhombic at room temperature but forms a monoclinic non-merohedrally twinned structure when flash cooled to 100 K. The weak inter- and intramolecular interactions in (1) are more conducive to retaining the `C' shape as is and probably prevent such temperature-induced behavior.