In strychninium 4-chlorobenzoate, C
21H
23N
2O
2+·C
7H
4ClO
2−, (I), and strychninium 4-nitrobenzoate, C
21H
23N
2O
2+·C
7H
4NO
4−, (II), the strychninium cations form pillars stabilized by C—H
O and C—H
π hydrogen bonds. Channels between the pillars are occupied by anions linked to one another by C—H
π hydrogen bonds. The cations and anions are linked by ionic N—H
+O
− and C—H
X hydrogen bonds, where
X = O, π and Cl in (I), and O and π in (II).
Supporting information
CCDC references: 621275; 621276
Crystals of (I) and (II) were grown from methanol solutions containing equimolar
amounts of strychnine and 4-chloro- or 4-nitrobenzoic acid, respectively. The
crystallizations were performed at room temperature by slow evaporation of
solvent.
All H atoms were included in idealizing positions and were treated as riding
atoms, with C—H and N—H distances of 0.95–1.00 Å and 0.93 Å,
respectively. Friedel pairs were merged before the final refinement of (II).
The absolute configurations of (I) and (II) were chosen on the basis of the
known absolute configurations of strychnine (Robertson & Beevers, 1951) and
for (I) were confirmed by the value of the Flack (1983) parameter.
For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2001); cell refinement: CrysAlis RED (Oxford Diffraction, 2001); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT (Bruker, 1999); software used to prepare material for publication: SHELXL97.
(I) strychninium 4-chlorobenzoate
top
Crystal data top
C21H23N2O2+·C7H4ClO2− | F(000) = 516 |
Mr = 490.97 | Dx = 1.414 Mg m−3 |
MonoclinicP21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 14059 reflections |
a = 10.557 (4) Å | θ = 3.2–31.0° |
b = 7.682 (2) Å | µ = 0.21 mm−1 |
c = 14.376 (8) Å | T = 100 K |
β = 98.47 (4)° | Needle, colourless |
V = 1153.2 (8) Å3 | 0.35 × 0.20 × 0.20 mm |
Z = 2 | |
Data collection top
Kuma KM-4 CCD diffractometer | 5047 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.053 |
Graphite monochromator | θmax = 31.0°, θmin = 3.2° |
ω scan | h = −15→14 |
15981 measured reflections | k = −11→10 |
6470 independent reflections | l = −20→14 |
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)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.084 | w = 1/[σ2(Fo2) + (0.038P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
6470 reflections | Δρmax = 0.28 e Å−3 |
316 parameters | Δρmin = −0.27 e Å−3 |
1 restraint | Absolute structure: Robertson & Beevers (1951), Flack (1983), 2539 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.01 (5) |
Crystal data top
C21H23N2O2+·C7H4ClO2− | V = 1153.2 (8) Å3 |
Mr = 490.97 | Z = 2 |
MonoclinicP21 | Mo Kα radiation |
a = 10.557 (4) Å | µ = 0.21 mm−1 |
b = 7.682 (2) Å | T = 100 K |
c = 14.376 (8) Å | 0.35 × 0.20 × 0.20 mm |
β = 98.47 (4)° | |
Data collection top
Kuma KM-4 CCD diffractometer | 5047 reflections with I > 2σ(I) |
15981 measured reflections | Rint = 0.053 |
6470 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.084 | Δρmax = 0.28 e Å−3 |
S = 1.01 | Δρmin = −0.27 e Å−3 |
6470 reflections | Absolute structure: Robertson & Beevers (1951), Flack (1983), 2539 Friedel pairs |
316 parameters | Absolute structure parameter: −0.01 (5) |
1 restraint | |
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. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.68498 (10) | 0.31267 (17) | 0.32551 (7) | 0.0223 (2) | |
O2 | 0.99122 (12) | 0.37418 (17) | 0.59727 (7) | 0.0255 (3) | |
N1 | 1.02970 (12) | 0.3169 (2) | 0.44849 (8) | 0.0167 (3) | |
N2 | 1.02147 (12) | 0.3267 (2) | 0.12457 (8) | 0.0201 (3) | |
H22 | 1.0741 | 0.3310 | 0.0782 | 0.024* | |
C1 | 1.24835 (17) | 0.3783 (2) | 0.54250 (11) | 0.0242 (4) | |
H1 | 1.2205 | 0.3743 | 0.6024 | 0.029* | |
C2 | 1.37542 (18) | 0.4104 (3) | 0.53411 (12) | 0.0318 (4) | |
H2 | 1.4356 | 0.4283 | 0.5893 | 0.038* | |
C3 | 1.41684 (18) | 0.4169 (3) | 0.44612 (13) | 0.0341 (5) | |
H3 | 1.5044 | 0.4386 | 0.4420 | 0.041* | |
C4 | 1.33021 (17) | 0.3918 (3) | 0.36499 (12) | 0.0276 (4) | |
H4 | 1.3581 | 0.3954 | 0.3051 | 0.033* | |
C5 | 1.20336 (15) | 0.3616 (2) | 0.37176 (10) | 0.0196 (3) | |
C6 | 1.16263 (15) | 0.3520 (2) | 0.45992 (10) | 0.0192 (3) | |
C7 | 1.09489 (14) | 0.3191 (2) | 0.29421 (9) | 0.0164 (3) | |
C8 | 0.97578 (14) | 0.3202 (2) | 0.34675 (9) | 0.0155 (3) | |
H8 | 0.9238 | 0.2128 | 0.3303 | 0.019* | |
C9 | 0.95010 (16) | 0.3520 (2) | 0.51361 (10) | 0.0206 (3) | |
C10 | 0.80867 (16) | 0.3564 (3) | 0.47628 (11) | 0.0242 (4) | |
H10A | 0.7649 | 0.4216 | 0.5217 | 0.029* | |
H10B | 0.7761 | 0.2354 | 0.4746 | 0.029* | |
C11 | 0.76868 (16) | 0.4379 (2) | 0.37731 (11) | 0.0205 (3) | |
H11 | 0.7200 | 0.5477 | 0.3838 | 0.025* | |
C12 | 0.62062 (17) | 0.3772 (3) | 0.23722 (12) | 0.0264 (4) | |
H12A | 0.6025 | 0.5028 | 0.2434 | 0.032* | |
H12B | 0.5378 | 0.3160 | 0.2211 | 0.032* | |
C13 | 0.69937 (16) | 0.3516 (2) | 0.15921 (11) | 0.0243 (4) | |
H13 | 0.6667 | 0.2779 | 0.1082 | 0.029* | |
C14 | 0.81165 (16) | 0.4267 (2) | 0.15820 (11) | 0.0206 (3) | |
C15 | 0.89152 (17) | 0.3884 (3) | 0.08201 (11) | 0.0243 (4) | |
H15A | 0.8490 | 0.2979 | 0.0393 | 0.029* | |
H15B | 0.8997 | 0.4949 | 0.0446 | 0.029* | |
C16 | 1.02077 (18) | 0.1421 (2) | 0.15928 (11) | 0.0231 (4) | |
H16A | 1.0485 | 0.0609 | 0.1127 | 0.028* | |
H16B | 0.9340 | 0.1084 | 0.1710 | 0.028* | |
C17 | 1.11438 (17) | 0.1399 (2) | 0.24985 (11) | 0.0209 (4) | |
H17A | 1.2035 | 0.1263 | 0.2371 | 0.025* | |
H17B | 1.0945 | 0.0442 | 0.2915 | 0.025* | |
C18 | 0.88877 (16) | 0.4802 (2) | 0.33371 (10) | 0.0172 (3) | |
H18 | 0.9346 | 0.5727 | 0.3745 | 0.021* | |
C19 | 0.87198 (17) | 0.5539 (2) | 0.23314 (11) | 0.0193 (3) | |
H19 | 0.8175 | 0.6608 | 0.2306 | 0.023* | |
C20 | 1.00610 (16) | 0.6052 (2) | 0.21393 (11) | 0.0200 (3) | |
H20A | 0.9999 | 0.6717 | 0.1544 | 0.024* | |
H20B | 1.0487 | 0.6795 | 0.2656 | 0.024* | |
C21 | 1.08281 (16) | 0.4401 (2) | 0.20699 (10) | 0.0179 (3) | |
H21 | 1.1709 | 0.4733 | 0.1957 | 0.021* | |
Cl | 1.65519 (4) | 0.31007 (7) | −0.25034 (3) | 0.03249 (11) | |
O3 | 1.15842 (12) | 0.35716 (19) | −0.00982 (7) | 0.0292 (3) | |
O4 | 1.29935 (15) | 0.2173 (2) | 0.09418 (10) | 0.0473 (4) | |
C22 | 1.26717 (17) | 0.2860 (2) | 0.01686 (11) | 0.0232 (4) | |
C23 | 1.36176 (15) | 0.2903 (2) | −0.05251 (10) | 0.0195 (3) | |
C24 | 1.34149 (16) | 0.3953 (2) | −0.13251 (10) | 0.0190 (3) | |
H24 | 1.2650 | 0.4618 | −0.1455 | 0.023* | |
C25 | 1.43258 (17) | 0.4037 (2) | −0.19379 (11) | 0.0217 (4) | |
H25 | 1.4192 | 0.4757 | −0.2481 | 0.026* | |
C26 | 1.54246 (15) | 0.3049 (3) | −0.17358 (11) | 0.0214 (3) | |
C27 | 1.56350 (18) | 0.1962 (2) | −0.09591 (12) | 0.0250 (4) | |
H27 | 1.6387 | 0.1269 | −0.0843 | 0.030* | |
C28 | 1.47239 (17) | 0.1904 (2) | −0.03523 (12) | 0.0234 (4) | |
H28 | 1.4860 | 0.1174 | 0.0186 | 0.028* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0200 (6) | 0.0184 (6) | 0.0288 (5) | 0.0000 (6) | 0.0047 (4) | 0.0026 (5) |
O2 | 0.0353 (7) | 0.0250 (7) | 0.0177 (5) | 0.0086 (6) | 0.0094 (5) | 0.0019 (5) |
N1 | 0.0200 (6) | 0.0166 (7) | 0.0143 (5) | 0.0019 (6) | 0.0051 (4) | −0.0003 (6) |
N2 | 0.0245 (7) | 0.0223 (8) | 0.0143 (5) | −0.0011 (7) | 0.0052 (5) | −0.0004 (6) |
C1 | 0.0303 (10) | 0.0240 (9) | 0.0179 (7) | 0.0060 (8) | 0.0017 (6) | 0.0030 (7) |
C2 | 0.0269 (10) | 0.0421 (12) | 0.0245 (8) | 0.0036 (9) | −0.0024 (7) | 0.0014 (8) |
C3 | 0.0193 (9) | 0.0491 (13) | 0.0336 (9) | 0.0023 (9) | 0.0033 (7) | 0.0059 (9) |
C4 | 0.0243 (9) | 0.0362 (11) | 0.0233 (8) | 0.0052 (8) | 0.0068 (6) | 0.0038 (8) |
C5 | 0.0222 (8) | 0.0195 (9) | 0.0172 (7) | 0.0060 (7) | 0.0032 (6) | 0.0028 (6) |
C6 | 0.0232 (8) | 0.0169 (9) | 0.0179 (6) | 0.0045 (6) | 0.0048 (6) | 0.0015 (6) |
C7 | 0.0189 (7) | 0.0178 (8) | 0.0137 (6) | 0.0023 (7) | 0.0059 (5) | 0.0014 (7) |
C8 | 0.0190 (7) | 0.0142 (8) | 0.0137 (6) | 0.0001 (7) | 0.0037 (5) | 0.0018 (6) |
C9 | 0.0288 (9) | 0.0153 (9) | 0.0199 (7) | 0.0057 (7) | 0.0112 (6) | 0.0030 (6) |
C10 | 0.0282 (9) | 0.0241 (10) | 0.0229 (7) | 0.0003 (7) | 0.0130 (6) | 0.0016 (7) |
C11 | 0.0197 (8) | 0.0187 (9) | 0.0240 (8) | 0.0015 (7) | 0.0065 (6) | 0.0006 (7) |
C12 | 0.0190 (9) | 0.0267 (10) | 0.0324 (9) | 0.0023 (7) | 0.0000 (7) | 0.0022 (8) |
C13 | 0.0211 (9) | 0.0238 (10) | 0.0262 (8) | 0.0005 (7) | −0.0024 (6) | 0.0024 (7) |
C14 | 0.0216 (9) | 0.0209 (9) | 0.0182 (7) | 0.0035 (7) | −0.0006 (6) | 0.0023 (7) |
C15 | 0.0252 (9) | 0.0282 (10) | 0.0187 (7) | −0.0013 (8) | 0.0006 (6) | 0.0014 (7) |
C16 | 0.0325 (10) | 0.0180 (9) | 0.0206 (8) | −0.0023 (7) | 0.0097 (7) | −0.0025 (7) |
C17 | 0.0279 (9) | 0.0179 (9) | 0.0187 (7) | 0.0028 (7) | 0.0097 (7) | 0.0012 (7) |
C18 | 0.0193 (8) | 0.0154 (8) | 0.0171 (7) | 0.0017 (6) | 0.0034 (6) | 0.0005 (6) |
C19 | 0.0242 (9) | 0.0147 (8) | 0.0186 (7) | 0.0026 (7) | 0.0023 (6) | 0.0028 (6) |
C20 | 0.0252 (9) | 0.0165 (9) | 0.0188 (7) | −0.0005 (7) | 0.0050 (6) | 0.0031 (6) |
C21 | 0.0197 (8) | 0.0185 (8) | 0.0159 (7) | −0.0018 (6) | 0.0045 (6) | 0.0013 (6) |
Cl | 0.0292 (2) | 0.0321 (3) | 0.0399 (2) | −0.0035 (2) | 0.01716 (18) | −0.0045 (2) |
O3 | 0.0272 (7) | 0.0405 (9) | 0.0212 (5) | 0.0067 (6) | 0.0080 (5) | 0.0042 (6) |
O4 | 0.0405 (9) | 0.0733 (12) | 0.0306 (7) | 0.0140 (8) | 0.0132 (6) | 0.0261 (7) |
C22 | 0.0256 (9) | 0.0240 (10) | 0.0209 (7) | −0.0016 (7) | 0.0067 (6) | −0.0005 (7) |
C23 | 0.0204 (8) | 0.0201 (9) | 0.0176 (7) | −0.0042 (7) | 0.0009 (6) | −0.0034 (6) |
C24 | 0.0192 (8) | 0.0176 (9) | 0.0196 (7) | −0.0005 (7) | 0.0006 (6) | −0.0032 (6) |
C25 | 0.0263 (9) | 0.0201 (9) | 0.0190 (7) | −0.0033 (7) | 0.0041 (6) | −0.0023 (7) |
C26 | 0.0205 (8) | 0.0217 (9) | 0.0232 (7) | −0.0042 (8) | 0.0066 (6) | −0.0065 (7) |
C27 | 0.0220 (9) | 0.0207 (10) | 0.0312 (9) | 0.0018 (7) | 0.0007 (7) | −0.0034 (7) |
C28 | 0.0246 (9) | 0.0215 (9) | 0.0228 (8) | −0.0023 (7) | −0.0010 (7) | 0.0009 (7) |
Geometric parameters (Å, º) top
O1—C12 | 1.437 (2) | C12—H12B | 0.9900 |
O1—C11 | 1.438 (2) | C13—C14 | 1.320 (2) |
O2—C9 | 1.229 (2) | C13—H13 | 0.9500 |
N1—C9 | 1.3737 (19) | C14—C15 | 1.507 (2) |
N1—C6 | 1.415 (2) | C14—C19 | 1.523 (2) |
N1—C8 | 1.4895 (19) | C15—H15A | 0.9900 |
N2—C15 | 1.494 (2) | C15—H15B | 0.9900 |
N2—C16 | 1.503 (2) | C16—C17 | 1.514 (2) |
N2—C21 | 1.535 (2) | C16—H16A | 0.9900 |
N2—H22 | 0.9300 | C16—H16B | 0.9900 |
C1—C2 | 1.387 (3) | C17—H17A | 0.9900 |
C1—C6 | 1.397 (2) | C17—H17B | 0.9900 |
C1—H1 | 0.9500 | C18—C19 | 1.538 (2) |
C2—C3 | 1.399 (3) | C18—H18 | 1.0000 |
C2—H2 | 0.9500 | C19—C20 | 1.534 (2) |
C3—C4 | 1.385 (3) | C19—H19 | 1.0000 |
C3—H3 | 0.9500 | C20—C21 | 1.516 (2) |
C4—C5 | 1.377 (2) | C20—H20A | 0.9900 |
C4—H4 | 0.9500 | C20—H20B | 0.9900 |
C5—C6 | 1.399 (2) | C21—H21 | 1.0000 |
C5—C7 | 1.512 (2) | Cl—C26 | 1.7387 (17) |
C7—C17 | 1.544 (2) | O3—C22 | 1.278 (2) |
C7—C21 | 1.551 (2) | O4—C22 | 1.232 (2) |
C7—C8 | 1.559 (2) | C22—C23 | 1.512 (2) |
C8—C18 | 1.529 (2) | C23—C28 | 1.389 (2) |
C8—H8 | 1.0000 | C23—C24 | 1.396 (2) |
C9—C10 | 1.511 (3) | C24—C25 | 1.398 (2) |
C10—C11 | 1.555 (2) | C24—H24 | 0.9500 |
C10—H10A | 0.9900 | C25—C26 | 1.381 (3) |
C10—H10B | 0.9900 | C25—H25 | 0.9500 |
C11—C18 | 1.530 (2) | C26—C27 | 1.386 (3) |
C11—H11 | 1.0000 | C27—C28 | 1.391 (3) |
C12—C13 | 1.504 (3) | C27—H27 | 0.9500 |
C12—H12A | 0.9900 | C28—H28 | 0.9500 |
| | | |
C12—O1—C11 | 113.66 (14) | C13—C14—C19 | 123.71 (15) |
C9—N1—C6 | 125.41 (13) | C15—C14—C19 | 114.78 (15) |
C9—N1—C8 | 118.83 (13) | N2—C15—C14 | 110.03 (13) |
C6—N1—C8 | 109.87 (11) | N2—C15—H15A | 109.7 |
C15—N2—C16 | 112.69 (14) | C14—C15—H15A | 109.7 |
C15—N2—C21 | 113.17 (14) | N2—C15—H15B | 109.7 |
C16—N2—C21 | 107.53 (12) | C14—C15—H15B | 109.7 |
C15—N2—H22 | 107.7 | H15A—C15—H15B | 108.2 |
C16—N2—H22 | 107.7 | N2—C16—C17 | 105.17 (14) |
C21—N2—H22 | 107.7 | N2—C16—H16A | 110.7 |
C2—C1—C6 | 117.74 (15) | C17—C16—H16A | 110.7 |
C2—C1—H1 | 121.1 | N2—C16—H16B | 110.7 |
C6—C1—H1 | 121.1 | C17—C16—H16B | 110.7 |
C1—C2—C3 | 121.36 (17) | H16A—C16—H16B | 108.8 |
C1—C2—H2 | 119.3 | C16—C17—C7 | 103.61 (13) |
C3—C2—H2 | 119.3 | C16—C17—H17A | 111.0 |
C4—C3—C2 | 120.05 (18) | C7—C17—H17A | 111.0 |
C4—C3—H3 | 120.0 | C16—C17—H17B | 111.0 |
C2—C3—H3 | 120.0 | C7—C17—H17B | 111.0 |
C5—C4—C3 | 119.48 (16) | H17A—C17—H17B | 109.0 |
C5—C4—H4 | 120.3 | C8—C18—C11 | 107.35 (13) |
C3—C4—H4 | 120.3 | C8—C18—C19 | 113.27 (13) |
C4—C5—C6 | 120.33 (15) | C11—C18—C19 | 118.40 (14) |
C4—C5—C7 | 128.56 (14) | C8—C18—H18 | 105.6 |
C6—C5—C7 | 110.87 (14) | C11—C18—H18 | 105.6 |
C1—C6—C5 | 121.01 (16) | C19—C18—H18 | 105.6 |
C1—C6—N1 | 129.30 (14) | C14—C19—C20 | 109.79 (14) |
C5—C6—N1 | 109.68 (13) | C14—C19—C18 | 114.01 (15) |
C5—C7—C17 | 111.39 (13) | C20—C19—C18 | 106.40 (13) |
C5—C7—C21 | 115.47 (14) | C14—C19—H19 | 108.8 |
C17—C7—C21 | 101.57 (12) | C20—C19—H19 | 108.8 |
C5—C7—C8 | 102.64 (11) | C18—C19—H19 | 108.8 |
C17—C7—C8 | 111.79 (14) | C21—C20—C19 | 108.23 (14) |
C21—C7—C8 | 114.34 (13) | C21—C20—H20A | 110.1 |
N1—C8—C18 | 105.65 (13) | C19—C20—H20A | 110.1 |
N1—C8—C7 | 104.88 (12) | C21—C20—H20B | 110.1 |
C18—C8—C7 | 117.25 (14) | C19—C20—H20B | 110.1 |
N1—C8—H8 | 109.6 | H20A—C20—H20B | 108.4 |
C18—C8—H8 | 109.6 | C20—C21—N2 | 110.92 (13) |
C7—C8—H8 | 109.6 | C20—C21—C7 | 115.43 (13) |
O2—C9—N1 | 122.06 (16) | N2—C21—C7 | 105.00 (14) |
O2—C9—C10 | 122.18 (14) | C20—C21—H21 | 108.4 |
N1—C9—C10 | 115.73 (13) | N2—C21—H21 | 108.4 |
C9—C10—C11 | 117.05 (14) | C7—C21—H21 | 108.4 |
C9—C10—H10A | 108.0 | O4—C22—O3 | 124.74 (16) |
C11—C10—H10A | 108.0 | O4—C22—C23 | 118.90 (16) |
C9—C10—H10B | 108.0 | O3—C22—C23 | 116.36 (14) |
C11—C10—H10B | 108.0 | C28—C23—C24 | 119.32 (15) |
H10A—C10—H10B | 107.3 | C28—C23—C22 | 119.32 (15) |
O1—C11—C18 | 114.41 (13) | C24—C23—C22 | 121.34 (15) |
O1—C11—C10 | 105.54 (14) | C23—C24—C25 | 120.65 (16) |
C18—C11—C10 | 109.32 (14) | C23—C24—H24 | 119.7 |
O1—C11—H11 | 109.1 | C25—C24—H24 | 119.7 |
C18—C11—H11 | 109.1 | C26—C25—C24 | 118.46 (15) |
C10—C11—H11 | 109.1 | C26—C25—H25 | 120.8 |
O1—C12—C13 | 111.85 (14) | C24—C25—H25 | 120.8 |
O1—C12—H12A | 109.2 | C25—C26—C27 | 122.06 (15) |
C13—C12—H12A | 109.2 | C25—C26—Cl | 119.10 (13) |
O1—C12—H12B | 109.2 | C27—C26—Cl | 118.79 (14) |
C13—C12—H12B | 109.2 | C26—C27—C28 | 118.73 (17) |
H12A—C12—H12B | 107.9 | C26—C27—H27 | 120.6 |
C14—C13—C12 | 123.16 (16) | C28—C27—H27 | 120.6 |
C14—C13—H13 | 118.4 | C23—C28—C27 | 120.74 (16) |
C12—C13—H13 | 118.4 | C23—C28—H28 | 119.6 |
C13—C14—C15 | 121.50 (16) | C27—C28—H28 | 119.6 |
| | | |
C6—C1—C2—C3 | 0.2 (3) | C21—N2—C16—C17 | −16.22 (17) |
C1—C2—C3—C4 | 0.3 (3) | N2—C16—C17—C7 | 36.10 (16) |
C2—C3—C4—C5 | 0.4 (3) | C5—C7—C17—C16 | −164.84 (13) |
C3—C4—C5—C6 | −1.5 (3) | C21—C7—C17—C16 | −41.36 (15) |
C3—C4—C5—C7 | −175.49 (19) | C8—C7—C17—C16 | 80.98 (15) |
C2—C1—C6—C5 | −1.4 (3) | N1—C8—C18—C11 | −73.14 (15) |
C2—C1—C6—N1 | 179.80 (19) | C7—C8—C18—C11 | 170.48 (13) |
C4—C5—C6—C1 | 2.1 (3) | N1—C8—C18—C19 | 154.27 (13) |
C7—C5—C6—C1 | 177.00 (16) | C7—C8—C18—C19 | 37.90 (19) |
C4—C5—C6—N1 | −178.90 (17) | O1—C11—C18—C8 | −70.86 (16) |
C7—C5—C6—N1 | −4.0 (2) | C10—C11—C18—C8 | 47.23 (17) |
C9—N1—C6—C1 | 20.7 (3) | O1—C11—C18—C19 | 58.9 (2) |
C8—N1—C6—C1 | 173.13 (17) | C10—C11—C18—C19 | 176.98 (15) |
C9—N1—C6—C5 | −158.19 (16) | C13—C14—C19—C20 | 175.93 (16) |
C8—N1—C6—C5 | −5.81 (19) | C15—C14—C19—C20 | −2.9 (2) |
C4—C5—C7—C17 | 66.0 (2) | C13—C14—C19—C18 | 56.7 (2) |
C6—C5—C7—C17 | −108.43 (16) | C15—C14—C19—C18 | −122.17 (16) |
C4—C5—C7—C21 | −49.2 (3) | C8—C18—C19—C14 | 60.86 (19) |
C6—C5—C7—C21 | 136.41 (15) | C11—C18—C19—C14 | −66.1 (2) |
C4—C5—C7—C8 | −174.26 (19) | C8—C18—C19—C20 | −60.30 (18) |
C6—C5—C7—C8 | 11.33 (19) | C11—C18—C19—C20 | 172.72 (14) |
C9—N1—C8—C18 | 42.59 (19) | C14—C19—C20—C21 | −54.60 (17) |
C6—N1—C8—C18 | −111.86 (14) | C18—C19—C20—C21 | 69.23 (16) |
C9—N1—C8—C7 | 167.09 (15) | C19—C20—C21—N2 | 62.16 (16) |
C6—N1—C8—C7 | 12.64 (18) | C19—C20—C21—C7 | −57.09 (18) |
C5—C7—C8—N1 | −13.95 (17) | C15—N2—C21—C20 | −9.97 (18) |
C17—C7—C8—N1 | 105.53 (15) | C16—N2—C21—C20 | −135.09 (14) |
C21—C7—C8—N1 | −139.76 (14) | C15—N2—C21—C7 | 115.36 (14) |
C5—C7—C8—C18 | 102.85 (15) | C16—N2—C21—C7 | −9.76 (16) |
C17—C7—C8—C18 | −137.67 (14) | C5—C7—C21—C20 | −85.79 (17) |
C21—C7—C8—C18 | −22.96 (19) | C17—C7—C21—C20 | 153.56 (14) |
C6—N1—C9—O2 | −20.0 (3) | C8—C7—C21—C20 | 33.0 (2) |
C8—N1—C9—O2 | −170.17 (15) | C5—C7—C21—N2 | 151.75 (13) |
C6—N1—C9—C10 | 161.72 (16) | C17—C7—C21—N2 | 31.10 (15) |
C8—N1—C9—C10 | 11.6 (2) | C8—C7—C21—N2 | −89.47 (16) |
O2—C9—C10—C11 | 143.61 (17) | O4—C22—C23—C28 | 11.7 (3) |
N1—C9—C10—C11 | −38.1 (2) | O3—C22—C23—C28 | −168.99 (17) |
C12—O1—C11—C18 | −69.76 (17) | O4—C22—C23—C24 | −166.89 (18) |
C12—O1—C11—C10 | 170.02 (13) | O3—C22—C23—C24 | 12.4 (3) |
C9—C10—C11—O1 | 129.63 (15) | C28—C23—C24—C25 | −1.5 (3) |
C9—C10—C11—C18 | 6.1 (2) | C22—C23—C24—C25 | 177.14 (15) |
C11—O1—C12—C13 | 87.25 (18) | C23—C24—C25—C26 | 0.4 (2) |
O1—C12—C13—C14 | −63.1 (2) | C24—C25—C26—C27 | 1.3 (3) |
C12—C13—C14—C15 | 175.89 (16) | C24—C25—C26—Cl | 178.60 (13) |
C12—C13—C14—C19 | −2.9 (3) | C25—C26—C27—C28 | −1.8 (3) |
C16—N2—C15—C14 | 75.30 (17) | Cl—C26—C27—C28 | −179.14 (14) |
C21—N2—C15—C14 | −46.99 (19) | C24—C23—C28—C27 | 0.9 (3) |
C13—C14—C15—N2 | −124.15 (18) | C22—C23—C28—C27 | −177.70 (16) |
C19—C14—C15—N2 | 54.7 (2) | C26—C27—C28—C23 | 0.7 (3) |
C15—N2—C16—C17 | −141.63 (14) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H22···O3 | 0.93 | 1.66 | 2.589 (2) | 174 |
C17—H17B···O2i | 0.99 | 2.35 | 3.311 (2) | 164 |
C18—H18···O2ii | 1.00 | 2.46 | 3.374 (2) | 152 |
C17—H17A···O4 | 0.99 | 2.52 | 3.235 (3) | 129 |
C17—H17A···Cliii | 0.99 | 2.84 | 3.512 (2) | 126 |
Symmetry codes: (i) −x+2, y−1/2, −z+1; (ii) −x+2, y+1/2, −z+1; (iii) −x+3, y−1/2, −z. |
(II) strychninium 4-nitrobenzoate
top
Crystal data top
C21H23N2O2+·C7H4NO4− | F(000) = 528 |
Mr = 501.53 | Dx = 1.433 Mg m−3 |
MonoclinicP21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 6852 reflections |
a = 10.976 (2) Å | θ = 3.7–28.1° |
b = 7.545 (1) Å | µ = 0.10 mm−1 |
c = 14.187 (2) Å | T = 100 K |
β = 98.29 (3)° | Needle, colourless |
V = 1162.6 (3) Å3 | 0.35 × 0.15 × 0.15 mm |
Z = 2 | |
Data collection top
Kuma KM-4 CCD diffractometer | 2541 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.028 |
Graphite monochromator | θmax = 27.0°, θmin = 3.7° |
ω scan | h = −14→14 |
7610 measured reflections | k = −9→6 |
2666 independent reflections | l = −18→18 |
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)] = 0.031 | H-atom parameters constrained |
wR(F2) = 0.079 | w = 1/[σ2(Fo2) + (0.0517P)2 + 0.1263P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
2666 reflections | Δρmax = 0.19 e Å−3 |
334 parameters | Δρmin = −0.22 e Å−3 |
1 restraint | Absolute structure: Robertson & Beevers (1951) |
Primary atom site location: structure-invariant direct methods | |
Crystal data top
C21H23N2O2+·C7H4NO4− | V = 1162.6 (3) Å3 |
Mr = 501.53 | Z = 2 |
MonoclinicP21 | Mo Kα radiation |
a = 10.976 (2) Å | µ = 0.10 mm−1 |
b = 7.545 (1) Å | T = 100 K |
c = 14.187 (2) Å | 0.35 × 0.15 × 0.15 mm |
β = 98.29 (3)° | |
Data collection top
Kuma KM-4 CCD diffractometer | 2541 reflections with I > 2σ(I) |
7610 measured reflections | Rint = 0.028 |
2666 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.031 | 1 restraint |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.19 e Å−3 |
2666 reflections | Δρmin = −0.22 e Å−3 |
334 parameters | Absolute structure: Robertson & Beevers (1951) |
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. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.70494 (11) | 0.3226 (2) | 0.33473 (9) | 0.0219 (3) | |
O2 | 1.01565 (13) | 0.3919 (2) | 0.60050 (9) | 0.0254 (3) | |
N1 | 1.04468 (14) | 0.3249 (2) | 0.44845 (10) | 0.0181 (3) | |
N2 | 1.01869 (13) | 0.3049 (2) | 0.11982 (10) | 0.0168 (3) | |
H22 | 1.0665 | 0.3039 | 0.0708 | 0.020* | |
C1 | 1.25802 (19) | 0.3983 (3) | 0.53523 (13) | 0.0263 (4) | |
H1 | 1.2350 | 0.3986 | 0.5973 | 0.032* | |
C2 | 1.3782 (2) | 0.4350 (4) | 0.52142 (15) | 0.0332 (5) | |
H2 | 1.4382 | 0.4619 | 0.5750 | 0.040* | |
C3 | 1.41273 (19) | 0.4360 (4) | 0.43050 (16) | 0.0352 (6) | |
H3 | 1.4957 | 0.4623 | 0.4229 | 0.042* | |
C4 | 1.32607 (18) | 0.4014 (3) | 0.35090 (13) | 0.0268 (4) | |
H4 | 1.3492 | 0.4036 | 0.2889 | 0.032* | |
C5 | 1.20550 (16) | 0.3666 (3) | 0.36345 (12) | 0.0194 (4) | |
C6 | 1.17255 (17) | 0.3638 (3) | 0.45484 (13) | 0.0195 (4) | |
C7 | 1.09824 (15) | 0.3141 (2) | 0.28971 (11) | 0.0154 (3) | |
C8 | 0.98714 (15) | 0.3199 (3) | 0.34674 (11) | 0.0156 (3) | |
H8 | 0.9367 | 0.2098 | 0.3343 | 0.019* | |
C9 | 0.97196 (18) | 0.3645 (3) | 0.51668 (12) | 0.0207 (4) | |
C10 | 0.83481 (17) | 0.3651 (3) | 0.48228 (12) | 0.0237 (4) | |
H10A | 0.7940 | 0.4308 | 0.5294 | 0.028* | |
H10B | 0.8052 | 0.2411 | 0.4819 | 0.028* | |
C11 | 0.79174 (17) | 0.4460 (3) | 0.38269 (13) | 0.0200 (4) | |
H11 | 0.7486 | 0.5605 | 0.3908 | 0.024* | |
C12 | 0.64050 (16) | 0.3858 (3) | 0.24551 (13) | 0.0233 (4) | |
H12A | 0.6290 | 0.5156 | 0.2493 | 0.028* | |
H12B | 0.5580 | 0.3301 | 0.2336 | 0.028* | |
C13 | 0.70980 (16) | 0.3440 (3) | 0.16375 (13) | 0.0209 (4) | |
H13 | 0.6738 | 0.2654 | 0.1153 | 0.025* | |
C14 | 0.81930 (16) | 0.4135 (3) | 0.15748 (12) | 0.0176 (4) | |
C15 | 0.89118 (16) | 0.3629 (3) | 0.07856 (12) | 0.0204 (4) | |
H15A | 0.8485 | 0.2653 | 0.0405 | 0.025* | |
H15B | 0.8961 | 0.4656 | 0.0359 | 0.025* | |
C16 | 1.02045 (17) | 0.1202 (3) | 0.16118 (13) | 0.0191 (4) | |
H16A | 1.0435 | 0.0319 | 0.1153 | 0.023* | |
H16B | 0.9388 | 0.0885 | 0.1781 | 0.023* | |
C17 | 1.11644 (17) | 0.1278 (3) | 0.24939 (13) | 0.0179 (4) | |
H17A | 1.2005 | 0.1138 | 0.2328 | 0.021* | |
H17B | 1.1019 | 0.0346 | 0.2956 | 0.021* | |
C18 | 0.90384 (17) | 0.4828 (2) | 0.33262 (12) | 0.0163 (4) | |
H18 | 0.9503 | 0.5801 | 0.3698 | 0.020* | |
C19 | 0.88096 (16) | 0.5476 (3) | 0.22863 (12) | 0.0170 (4) | |
H19 | 0.8289 | 0.6568 | 0.2253 | 0.020* | |
C20 | 1.00808 (16) | 0.5972 (3) | 0.20312 (13) | 0.0179 (4) | |
H20A | 0.9987 | 0.6585 | 0.1408 | 0.022* | |
H20B | 1.0512 | 0.6778 | 0.2520 | 0.022* | |
C21 | 1.08164 (15) | 0.4280 (2) | 0.19858 (12) | 0.0158 (4) | |
H21 | 1.1650 | 0.4599 | 0.1832 | 0.019* | |
O3 | 1.15883 (12) | 0.3375 (2) | −0.01537 (9) | 0.0244 (3) | |
O4 | 1.28248 (15) | 0.1596 (3) | 0.08134 (11) | 0.0392 (4) | |
O5 | 1.61925 (13) | 0.4210 (3) | −0.29814 (10) | 0.0340 (4) | |
O6 | 1.74092 (13) | 0.2673 (2) | −0.19560 (12) | 0.0342 (4) | |
N3 | 1.64096 (13) | 0.3356 (2) | −0.22444 (11) | 0.0219 (3) | |
C22 | 1.25924 (17) | 0.2548 (3) | 0.00992 (13) | 0.0200 (4) | |
C23 | 1.35792 (17) | 0.2739 (3) | −0.05452 (12) | 0.0169 (4) | |
C24 | 1.33963 (16) | 0.3825 (3) | −0.13482 (12) | 0.0173 (4) | |
H24 | 1.2635 | 0.4449 | −0.1509 | 0.021* | |
C25 | 1.43203 (16) | 0.4032 (3) | −0.19180 (12) | 0.0173 (4) | |
H25 | 1.4203 | 0.4790 | −0.2466 | 0.021* | |
C26 | 1.54151 (15) | 0.3127 (3) | −0.16594 (12) | 0.0178 (4) | |
C27 | 1.56160 (17) | 0.2005 (3) | −0.08775 (14) | 0.0202 (4) | |
H27 | 1.6371 | 0.1402 | −0.0727 | 0.024* | |
C28 | 1.46802 (16) | 0.1818 (3) | −0.03213 (13) | 0.0196 (4) | |
H28 | 1.4794 | 0.1074 | 0.0217 | 0.024* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0199 (6) | 0.0210 (7) | 0.0257 (6) | −0.0006 (6) | 0.0061 (5) | 0.0030 (6) |
O2 | 0.0397 (8) | 0.0230 (7) | 0.0144 (6) | 0.0089 (6) | 0.0064 (6) | 0.0008 (6) |
N1 | 0.0239 (7) | 0.0172 (7) | 0.0133 (7) | 0.0020 (7) | 0.0032 (6) | −0.0002 (6) |
N2 | 0.0164 (7) | 0.0208 (8) | 0.0136 (6) | −0.0009 (6) | 0.0038 (6) | 0.0001 (6) |
C1 | 0.0323 (10) | 0.0256 (10) | 0.0188 (8) | 0.0069 (9) | −0.0040 (8) | −0.0018 (8) |
C2 | 0.0260 (10) | 0.0434 (14) | 0.0263 (10) | 0.0041 (10) | −0.0092 (9) | −0.0032 (10) |
C3 | 0.0194 (9) | 0.0512 (16) | 0.0329 (11) | −0.0012 (10) | −0.0036 (9) | −0.0004 (11) |
C4 | 0.0200 (9) | 0.0382 (12) | 0.0217 (9) | 0.0021 (9) | 0.0011 (8) | 0.0019 (9) |
C5 | 0.0206 (8) | 0.0182 (10) | 0.0183 (8) | 0.0037 (7) | −0.0005 (7) | 0.0013 (7) |
C6 | 0.0231 (9) | 0.0164 (9) | 0.0181 (8) | 0.0041 (7) | 0.0003 (7) | 0.0006 (7) |
C7 | 0.0159 (8) | 0.0153 (9) | 0.0150 (7) | 0.0016 (7) | 0.0024 (6) | −0.0004 (7) |
C8 | 0.0184 (8) | 0.0164 (8) | 0.0125 (7) | 0.0019 (7) | 0.0040 (6) | 0.0011 (7) |
C9 | 0.0319 (10) | 0.0145 (9) | 0.0169 (8) | 0.0051 (8) | 0.0077 (7) | 0.0012 (7) |
C10 | 0.0291 (10) | 0.0241 (11) | 0.0199 (8) | 0.0002 (9) | 0.0105 (8) | −0.0002 (8) |
C11 | 0.0213 (9) | 0.0168 (9) | 0.0230 (9) | 0.0019 (8) | 0.0071 (8) | −0.0013 (7) |
C12 | 0.0161 (8) | 0.0253 (10) | 0.0286 (9) | 0.0008 (8) | 0.0038 (7) | 0.0037 (9) |
C13 | 0.0173 (8) | 0.0211 (9) | 0.0232 (9) | 0.0013 (8) | −0.0008 (7) | 0.0010 (8) |
C14 | 0.0161 (8) | 0.0186 (9) | 0.0175 (8) | 0.0030 (7) | 0.0002 (7) | 0.0023 (7) |
C15 | 0.0175 (8) | 0.0267 (10) | 0.0162 (8) | −0.0007 (8) | −0.0007 (7) | 0.0002 (8) |
C16 | 0.0224 (9) | 0.0168 (9) | 0.0187 (8) | −0.0012 (7) | 0.0052 (8) | −0.0025 (7) |
C17 | 0.0211 (9) | 0.0169 (9) | 0.0164 (8) | 0.0037 (7) | 0.0054 (7) | 0.0007 (7) |
C18 | 0.0196 (8) | 0.0133 (9) | 0.0165 (8) | 0.0019 (7) | 0.0043 (7) | 0.0001 (7) |
C19 | 0.0165 (8) | 0.0156 (9) | 0.0188 (8) | 0.0016 (7) | 0.0027 (7) | 0.0029 (7) |
C20 | 0.0185 (9) | 0.0163 (9) | 0.0189 (8) | −0.0015 (7) | 0.0025 (7) | 0.0039 (7) |
C21 | 0.0155 (8) | 0.0175 (9) | 0.0144 (7) | −0.0022 (7) | 0.0019 (7) | 0.0013 (7) |
O3 | 0.0189 (6) | 0.0354 (8) | 0.0197 (6) | 0.0036 (6) | 0.0054 (5) | 0.0021 (6) |
O4 | 0.0369 (9) | 0.0536 (11) | 0.0306 (8) | 0.0157 (9) | 0.0171 (7) | 0.0221 (8) |
O5 | 0.0231 (7) | 0.0581 (11) | 0.0212 (7) | −0.0097 (8) | 0.0042 (6) | 0.0060 (7) |
O6 | 0.0213 (7) | 0.0286 (8) | 0.0561 (10) | 0.0050 (6) | 0.0165 (7) | 0.0054 (8) |
N3 | 0.0190 (7) | 0.0216 (8) | 0.0259 (8) | −0.0050 (7) | 0.0058 (6) | −0.0050 (7) |
C22 | 0.0204 (9) | 0.0225 (10) | 0.0179 (8) | −0.0014 (8) | 0.0057 (7) | −0.0012 (8) |
C23 | 0.0173 (8) | 0.0182 (9) | 0.0153 (8) | −0.0032 (7) | 0.0022 (7) | −0.0040 (7) |
C24 | 0.0153 (8) | 0.0171 (9) | 0.0193 (8) | 0.0003 (7) | 0.0013 (7) | −0.0016 (7) |
C25 | 0.0196 (8) | 0.0160 (9) | 0.0161 (7) | −0.0020 (8) | 0.0017 (7) | −0.0008 (7) |
C26 | 0.0154 (8) | 0.0187 (9) | 0.0198 (8) | −0.0036 (7) | 0.0044 (7) | −0.0039 (7) |
C27 | 0.0156 (8) | 0.0206 (9) | 0.0235 (9) | 0.0016 (7) | 0.0001 (7) | −0.0005 (8) |
C28 | 0.0183 (9) | 0.0199 (10) | 0.0199 (9) | 0.0000 (8) | 0.0003 (7) | 0.0020 (7) |
Geometric parameters (Å, º) top
O1—C11 | 1.432 (2) | C13—C14 | 1.326 (3) |
O1—C12 | 1.439 (2) | C13—H13 | 0.9500 |
O2—C9 | 1.234 (2) | C14—C15 | 1.509 (2) |
N1—C9 | 1.373 (2) | C14—C19 | 1.518 (3) |
N1—C6 | 1.424 (2) | C15—H15A | 0.9900 |
N1—C8 | 1.490 (2) | C15—H15B | 0.9900 |
N2—C15 | 1.502 (2) | C16—C17 | 1.516 (3) |
N2—C16 | 1.511 (2) | C16—H16A | 0.9900 |
N2—C21 | 1.538 (2) | C16—H16B | 0.9900 |
N2—H22 | 0.9300 | C17—H17A | 0.9900 |
C1—C2 | 1.389 (3) | C17—H17B | 0.9900 |
C1—C6 | 1.393 (3) | C18—C19 | 1.540 (2) |
C1—H1 | 0.9502 | C18—H18 | 1.0000 |
C2—C3 | 1.396 (3) | C19—C20 | 1.537 (2) |
C2—H2 | 0.9533 | C19—H19 | 1.0000 |
C3—C4 | 1.392 (3) | C20—C21 | 1.517 (3) |
C3—H3 | 0.9531 | C20—H20A | 0.9900 |
C4—C5 | 1.386 (3) | C20—H20B | 0.9900 |
C4—H4 | 0.9499 | C21—H21 | 1.0000 |
C5—C6 | 1.396 (3) | O3—C22 | 1.272 (2) |
C5—C7 | 1.511 (2) | O4—C22 | 1.238 (2) |
C7—C21 | 1.541 (2) | O5—N3 | 1.222 (2) |
C7—C17 | 1.541 (3) | O6—N3 | 1.228 (2) |
C7—C8 | 1.558 (2) | N3—C26 | 1.474 (2) |
C8—C18 | 1.527 (2) | C22—C23 | 1.522 (2) |
C8—H8 | 1.0000 | C23—C28 | 1.390 (3) |
C9—C10 | 1.514 (3) | C23—C24 | 1.394 (3) |
C10—C11 | 1.549 (3) | C24—C25 | 1.394 (2) |
C10—H10A | 0.9900 | C24—H24 | 0.9572 |
C10—H10B | 0.9900 | C25—C26 | 1.385 (3) |
C11—C18 | 1.532 (2) | C25—H25 | 0.9586 |
C11—H11 | 1.0000 | C26—C27 | 1.387 (3) |
C12—C13 | 1.509 (3) | C27—C28 | 1.390 (3) |
C12—H12A | 0.9900 | C27—H27 | 0.9429 |
C12—H12B | 0.9900 | C28—H28 | 0.9414 |
| | | |
C11—O1—C12 | 114.30 (15) | N2—C15—C14 | 109.99 (14) |
C9—N1—C6 | 125.32 (15) | N2—C15—H15A | 109.7 |
C9—N1—C8 | 118.68 (15) | C14—C15—H15A | 109.7 |
C6—N1—C8 | 110.07 (13) | N2—C15—H15B | 109.7 |
C15—N2—C16 | 112.27 (14) | C14—C15—H15B | 109.7 |
C15—N2—C21 | 113.77 (14) | H15A—C15—H15B | 108.2 |
C16—N2—C21 | 107.18 (13) | N2—C16—C17 | 104.72 (14) |
C15—N2—H22 | 107.8 | N2—C16—H16A | 110.8 |
C16—N2—H22 | 107.8 | C17—C16—H16A | 110.8 |
C21—N2—H22 | 107.8 | N2—C16—H16B | 110.8 |
C2—C1—C6 | 117.57 (18) | C17—C16—H16B | 110.8 |
C2—C1—H1 | 121.0 | H16A—C16—H16B | 108.9 |
C6—C1—H1 | 121.4 | C16—C17—C7 | 103.23 (14) |
C1—C2—C3 | 121.44 (19) | C16—C17—H17A | 111.1 |
C1—C2—H2 | 119.4 | C7—C17—H17A | 111.1 |
C3—C2—H2 | 119.2 | C16—C17—H17B | 111.1 |
C4—C3—C2 | 120.23 (19) | C7—C17—H17B | 111.1 |
C4—C3—H3 | 119.9 | H17A—C17—H17B | 109.1 |
C2—C3—H3 | 119.8 | C8—C18—C11 | 107.40 (14) |
C5—C4—C3 | 118.99 (18) | C8—C18—C19 | 113.15 (15) |
C5—C4—H4 | 120.7 | C11—C18—C19 | 118.08 (15) |
C3—C4—H4 | 120.3 | C8—C18—H18 | 105.8 |
C4—C5—C6 | 120.17 (17) | C11—C18—H18 | 105.8 |
C4—C5—C7 | 128.61 (16) | C19—C18—H18 | 105.8 |
C6—C5—C7 | 111.03 (16) | C14—C19—C20 | 109.78 (15) |
C1—C6—C5 | 121.59 (18) | C14—C19—C18 | 114.88 (16) |
C1—C6—N1 | 129.19 (17) | C20—C19—C18 | 105.94 (14) |
C5—C6—N1 | 109.21 (15) | C14—C19—H19 | 108.7 |
C5—C7—C21 | 114.87 (15) | C20—C19—H19 | 108.7 |
C5—C7—C17 | 111.51 (15) | C18—C19—H19 | 108.7 |
C21—C7—C17 | 101.73 (13) | C21—C20—C19 | 108.19 (15) |
C5—C7—C8 | 102.88 (13) | C21—C20—H20A | 110.1 |
C21—C7—C8 | 114.39 (14) | C19—C20—H20A | 110.1 |
C17—C7—C8 | 111.81 (15) | C21—C20—H20B | 110.1 |
N1—C8—C18 | 105.60 (14) | C19—C20—H20B | 110.1 |
N1—C8—C7 | 104.44 (13) | H20A—C20—H20B | 108.4 |
C18—C8—C7 | 116.95 (15) | C20—C21—N2 | 110.66 (14) |
N1—C8—H8 | 109.8 | C20—C21—C7 | 115.65 (14) |
C18—C8—H8 | 109.8 | N2—C21—C7 | 105.02 (14) |
C7—C8—H8 | 109.8 | C20—C21—H21 | 108.4 |
O2—C9—N1 | 122.09 (17) | N2—C21—H21 | 108.4 |
O2—C9—C10 | 122.70 (16) | C7—C21—H21 | 108.4 |
N1—C9—C10 | 115.17 (15) | O5—N3—O6 | 124.14 (16) |
C9—C10—C11 | 116.97 (15) | O5—N3—C26 | 118.34 (15) |
C9—C10—H10A | 108.1 | O6—N3—C26 | 117.52 (16) |
C11—C10—H10A | 108.1 | O4—C22—O3 | 125.68 (18) |
C9—C10—H10B | 108.1 | O4—C22—C23 | 117.79 (18) |
C11—C10—H10B | 108.1 | O3—C22—C23 | 116.53 (16) |
H10A—C10—H10B | 107.3 | C28—C23—C24 | 119.89 (16) |
O1—C11—C18 | 114.92 (15) | C28—C23—C22 | 119.06 (17) |
O1—C11—C10 | 105.78 (15) | C24—C23—C22 | 121.04 (17) |
C18—C11—C10 | 109.54 (15) | C25—C24—C23 | 120.57 (16) |
O1—C11—H11 | 108.8 | C25—C24—H24 | 119.4 |
C18—C11—H11 | 108.8 | C23—C24—H24 | 120.1 |
C10—C11—H11 | 108.8 | C26—C25—C24 | 117.87 (16) |
O1—C12—C13 | 111.62 (15) | C26—C25—H25 | 121.3 |
O1—C12—H12A | 109.3 | C24—C25—H25 | 120.8 |
C13—C12—H12A | 109.3 | C25—C26—C27 | 122.98 (16) |
O1—C12—H12B | 109.3 | C25—C26—N3 | 118.56 (16) |
C13—C12—H12B | 109.3 | C27—C26—N3 | 118.46 (16) |
H12A—C12—H12B | 108.0 | C26—C27—C28 | 118.07 (17) |
C14—C13—C12 | 122.06 (18) | C26—C27—H27 | 120.6 |
C14—C13—H13 | 119.0 | C28—C27—H27 | 121.4 |
C12—C13—H13 | 119.0 | C27—C28—C23 | 120.58 (17) |
C13—C14—C15 | 121.70 (17) | C27—C28—H28 | 119.9 |
C13—C14—C19 | 122.73 (17) | C23—C28—H28 | 119.5 |
C15—C14—C19 | 115.56 (15) | | |
| | | |
C6—C1—C2—C3 | −0.5 (4) | C5—C7—C17—C16 | −165.50 (15) |
C1—C2—C3—C4 | 0.6 (4) | C21—C7—C17—C16 | −42.58 (16) |
C2—C3—C4—C5 | 0.2 (4) | C8—C7—C17—C16 | 79.92 (16) |
C3—C4—C5—C6 | −1.0 (3) | N1—C8—C18—C11 | −73.03 (17) |
C3—C4—C5—C7 | −175.6 (2) | C7—C8—C18—C11 | 171.34 (14) |
C2—C1—C6—C5 | −0.3 (3) | N1—C8—C18—C19 | 154.87 (14) |
C2—C1—C6—N1 | −179.2 (2) | C7—C8—C18—C19 | 39.2 (2) |
C4—C5—C6—C1 | 1.1 (3) | O1—C11—C18—C8 | −73.78 (18) |
C7—C5—C6—C1 | 176.53 (18) | C10—C11—C18—C8 | 45.10 (19) |
C4—C5—C6—N1 | −179.84 (19) | O1—C11—C18—C19 | 55.6 (2) |
C7—C5—C6—N1 | −4.4 (2) | C10—C11—C18—C19 | 174.45 (16) |
C9—N1—C6—C1 | 20.6 (3) | C13—C14—C19—C20 | 178.22 (17) |
C8—N1—C6—C1 | 172.9 (2) | C15—C14—C19—C20 | −1.5 (2) |
C9—N1—C6—C5 | −158.34 (18) | C13—C14—C19—C18 | 59.0 (2) |
C8—N1—C6—C5 | −6.1 (2) | C15—C14—C19—C18 | −120.75 (17) |
C4—C5—C7—C21 | −47.8 (3) | C8—C18—C19—C14 | 60.3 (2) |
C6—C5—C7—C21 | 137.25 (16) | C11—C18—C19—C14 | −66.3 (2) |
C4—C5—C7—C17 | 67.3 (3) | C8—C18—C19—C20 | −61.05 (19) |
C6—C5—C7—C17 | −107.70 (17) | C11—C18—C19—C20 | 172.32 (16) |
C4—C5—C7—C8 | −172.8 (2) | C14—C19—C20—C21 | −55.54 (19) |
C6—C5—C7—C8 | 12.3 (2) | C18—C19—C20—C21 | 69.05 (18) |
C9—N1—C8—C18 | 43.9 (2) | C19—C20—C21—N2 | 62.25 (18) |
C6—N1—C8—C18 | −110.47 (16) | C19—C20—C21—C7 | −57.0 (2) |
C9—N1—C8—C7 | 167.78 (16) | C15—N2—C21—C20 | −10.31 (19) |
C6—N1—C8—C7 | 13.4 (2) | C16—N2—C21—C20 | −135.03 (15) |
C5—C7—C8—N1 | −14.94 (18) | C15—N2—C21—C7 | 115.15 (15) |
C21—C7—C8—N1 | −140.21 (15) | C16—N2—C21—C7 | −9.57 (17) |
C17—C7—C8—N1 | 104.84 (16) | C5—C7—C21—C20 | −85.37 (19) |
C5—C7—C8—C18 | 101.33 (17) | C17—C7—C21—C20 | 154.04 (15) |
C21—C7—C8—C18 | −23.9 (2) | C8—C7—C21—C20 | 33.3 (2) |
C17—C7—C8—C18 | −138.89 (15) | C5—C7—C21—N2 | 152.35 (14) |
C6—N1—C9—O2 | −21.0 (3) | C17—C7—C21—N2 | 31.75 (16) |
C8—N1—C9—O2 | −171.09 (18) | C8—C7—C21—N2 | −88.97 (17) |
C6—N1—C9—C10 | 161.22 (18) | O4—C22—C23—C28 | 1.4 (3) |
C8—N1—C9—C10 | 11.1 (3) | O3—C22—C23—C28 | −177.89 (18) |
O2—C9—C10—C11 | 142.26 (19) | O4—C22—C23—C24 | −178.32 (19) |
N1—C9—C10—C11 | −40.0 (3) | O3—C22—C23—C24 | 2.4 (3) |
C12—O1—C11—C18 | −67.6 (2) | C28—C23—C24—C25 | −1.6 (3) |
C12—O1—C11—C10 | 171.48 (14) | C22—C23—C24—C25 | 178.11 (17) |
C9—C10—C11—O1 | 133.52 (17) | C23—C24—C25—C26 | 0.0 (3) |
C9—C10—C11—C18 | 9.1 (2) | C24—C25—C26—C27 | 1.5 (3) |
C11—O1—C12—C13 | 88.3 (2) | C24—C25—C26—N3 | −178.93 (16) |
O1—C12—C13—C14 | −64.4 (3) | O5—N3—C26—C25 | −6.3 (3) |
C12—C13—C14—C15 | 176.42 (17) | O6—N3—C26—C25 | 173.57 (18) |
C12—C13—C14—C19 | −3.3 (3) | O5—N3—C26—C27 | 173.26 (18) |
C16—N2—C15—C14 | 76.33 (19) | O6—N3—C26—C27 | −6.8 (3) |
C21—N2—C15—C14 | −45.6 (2) | C25—C26—C27—C28 | −1.4 (3) |
C13—C14—C15—N2 | −127.02 (19) | N3—C26—C27—C28 | 179.03 (17) |
C19—C14—C15—N2 | 52.7 (2) | C26—C27—C28—C23 | −0.2 (3) |
C15—N2—C16—C17 | −142.68 (14) | C24—C23—C28—C27 | 1.7 (3) |
C21—N2—C16—C17 | −17.06 (17) | C22—C23—C28—C27 | −178.00 (17) |
N2—C16—C17—C7 | 37.18 (17) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H22···O3 | 0.93 | 1.72 | 2.6373 (19) | 171 |
C17—H17B···O2i | 0.99 | 2.35 | 3.270 (2) | 154 |
C18—H18···O2ii | 1.00 | 2.41 | 3.312 (2) | 150 |
C17—H17A···O4 | 0.99 | 2.47 | 3.212 (2) | 131 |
C17—H17A···O5iii | 0.99 | 2.52 | 3.279 (2) | 133 |
C2—H2···O5iv | 0.95 | 2.50 | 3.408 (3) | 159 |
C21—H21···O6v | 1.00 | 2.53 | 3.220 (2) | 126 |
Symmetry codes: (i) −x+2, y−1/2, −z+1; (ii) −x+2, y+1/2, −z+1; (iii) −x+3, y−1/2, −z; (iv) x, y, z+1; (v) −x+3, y+1/2, −z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C21H23N2O2+·C7H4ClO2− | C21H23N2O2+·C7H4NO4− |
Mr | 490.97 | 501.53 |
Crystal system, space group | MonoclinicP21 | MonoclinicP21 |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 10.557 (4), 7.682 (2), 14.376 (8) | 10.976 (2), 7.545 (1), 14.187 (2) |
β (°) | 98.47 (4) | 98.29 (3) |
V (Å3) | 1153.2 (8) | 1162.6 (3) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.21 | 0.10 |
Crystal size (mm) | 0.35 × 0.20 × 0.20 | 0.35 × 0.15 × 0.15 |
|
Data collection |
Diffractometer | Kuma KM-4 CCD diffractometer | Kuma KM-4 CCD diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15981, 6470, 5047 | 7610, 2666, 2541 |
Rint | 0.053 | 0.028 |
(sin θ/λ)max (Å−1) | 0.725 | 0.639 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.084, 1.01 | 0.031, 0.079, 1.06 |
No. of reflections | 6470 | 2666 |
No. of parameters | 316 | 334 |
No. of restraints | 1 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.27 | 0.19, −0.22 |
Absolute structure | Robertson & Beevers (1951), Flack (1983), 2539 Friedel pairs | Robertson & Beevers (1951) |
Absolute structure parameter | −0.01 (5) | ? |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H22···O3 | 0.93 | 1.66 | 2.589 (2) | 174 |
C17—H17B···O2i | 0.99 | 2.35 | 3.311 (2) | 164 |
C18—H18···O2ii | 1.00 | 2.46 | 3.374 (2) | 152 |
C17—H17A···O4 | 0.99 | 2.52 | 3.235 (3) | 129 |
C17—H17A···Cliii | 0.99 | 2.84 | 3.512 (2) | 126 |
Symmetry codes: (i) −x+2, y−1/2, −z+1; (ii) −x+2, y+1/2, −z+1; (iii) −x+3, y−1/2, −z. |
C—H···π hydrogen bonds (Å, °) in (I). Cg1 and CG2 represent the
centroids of the C1–C6 and C23–C28 rings. topD—H···A | D—H | H···A | D···A | D—H···A | Offset |
C10—H10B···Cg1i | 0.99 | 3.00 | 3.939 (2) | 158.5 | 1.20 |
C12—H12A···Cg2iv | 0.99 | 2.93 | 3.705 (2) | 135.8 | 0.86 |
C28—H28···Cg2iii | 0.95 | 2.85 | 3.724 (2) | 154.1 | 0.74 |
Symmetry codes: (i) 2-x, -0.5+y, 1-z, (iv) 2-x, 0.5+y, -z,
(iii) 3-x, -0.5+y, -z |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H22···O3 | 0.93 | 1.72 | 2.6373 (19) | 171 |
C17—H17B···O2i | 0.99 | 2.35 | 3.270 (2) | 154 |
C18—H18···O2ii | 1.00 | 2.41 | 3.312 (2) | 150 |
C17—H17A···O4 | 0.99 | 2.47 | 3.212 (2) | 131 |
C17—H17A···O5iii | 0.99 | 2.52 | 3.279 (2) | 133 |
C2—H2···O5iv | 0.95 | 2.50 | 3.408 (3) | 159 |
C21—H21···O6v | 1.00 | 2.53 | 3.220 (2) | 126 |
Symmetry codes: (i) −x+2, y−1/2, −z+1; (ii) −x+2, y+1/2, −z+1; (iii) −x+3, y−1/2, −z; (iv) x, y, z+1; (v) −x+3, y+1/2, −z. |
C—H···π hydrogen bonds (Å, °) in (II). Cg1 and Cg2 represent the centroids
of the C1–C6 and C23–C28 rings. topD—H···A | D—H | H···A | D···A | D—H···A | offset |
C10—H10B···Cg1i | 0.99 | 3.03 | 3.963 (2) | 158.3 | 1.41 |
C12—H12A···Cg2vi | 0.99 | 2.92 | 3.685 (2) | 134.8 | 0.48 |
C28—H28···Cg2iii | 0.94 | 2.74 | 3.600 (2) | 152.3 | 0.33 |
Symmetry codes: (i) 2-x, -0.5+y, 1-z, (iv) 2-x, 0.5+y, -z,
(iii) 3-x, -0.5+y, -z |
Strychnine is one of the resolving agents used for the separation of racemic acids by fractional crystallization of strychninium diastereomeric salts (Jacques et al., 1991). During racemic resolution of N-4-nitrobenzoyl-DL-amino acids, strychninium diastereomeric salts have crystallized (Bialonska & Ciunik, 2006b). In the crystal structures of the strychninium salts, strychninium cations are assembled in corrugated layers. Holes at the surfaces of these layers have been recognized by the 4-nitrobenzoyl group of the amino acid derivative. Since the 4-nitrobenzoyl group plays a significant role in the racemic resolution of N-4-nitrobenzoyl-DL-amino acids, we decided to investigate the importance of the 4-nitrobenzoyl group for strychninium self-assembly. Thus, we have crystallized the strychninium salts, (I) and (II), respectively, of 4-nitro- and 4-chlorobenzoic acid.
Strychninium cations have seven stereogenic centers. Taking into account the numbering scheme employed in this paper these are N2(S), C7(S), C8(S), C11(S), C18(R), C19(R) and C21(S). The geometry of the strychninium cation in the crystal structures of (I) and (II) (Figs. 1 and 2) is comparable to that found in other related compounds (Gould et al., 1985, 1987; Mostad, 1985; Białońska & Ciunik, 2005, 2004, 2006a,b; Bottcher & Buchkremer-Hermanns, 1987; Ghosh et al., 1989; Sato & Yano, 1989; Costante et al., 1996; Robertson & Beevers, 1951; Bokhoven et al., 1951; Yano et al., 1994; Yuan et al., 1994).
In both (I) and (II), the cations form pillars (Fig. 2) extending in the [010] direction. The pillars are stabilized by C—H···O(amide) and C—H···π(arene) hydrogen bonds (see Tables 2 and 4). Similar pillars are present in the previously described crystals of (-)-strychninium (+)-neopentyl phthalate chloroform solvate, (-)-strychninium (+)-neopentyl-1-deutero-phthalate chloroform solvate (Yuan et al., 1994) and strychninium N-phthaloyl-β-alaninate N-phthaloyl-β-alanine (Białońska & Ciunik, 2006a).
Channels are formed between four neighboring strychninium pillars (see Fig. 3). The channels are occupied by 4-chloro- or 4-nitrobenzoate anions in the crystals of (I) and (II), respectively. The anions are linked to one another by C—H···π hydrogen bonds. The strychninium cations and the 4-chloro- or 4-nitrobenzoate anions are linked by ionic N—H+···O- hydrogen bonds (Tables 1 and 3), in which the protonated amine atom N2 of the strychninium cation and atom O5 of the deprotonated carboxyl group of the 4-chloro- or 4-nitrobenzoate anion act as a donor and an acceptor, respectively. Moreover, the cations and the anions are linked by weak hydrogen bonds. In the crystal structure of (I), the 4-chlorobenzoate anions are acceptors of C—H···O, C—H···Cl and C—H···π hydrogen bonds (see Tables 1 and 2). In the crystal structure of (II), the 4-nitrobenzoate anions are acceptors of C—H···O and C—H···π hydrogen bonds (Tables 3 and 4).