The structures of two brucinium (2,3-dimethoxy-10-oxostrychnidinium) salts of the α-hydroxy acids L-malic acid and L-tartaric acid, namely brucinium hydrogen (S)-malate pentahydrate, C23H27N2O4+·C4H5O5−·5H2O, (I), and anhydrous brucinium hydrogen (2R,3R)-tartrate, C23H27N2O4+·C4H5O6−,(II), have been determined at 130 K. Compound (I) has two brucinium cations, two hydrogen malate anions and ten water molecules of solvation in the asymmetric unit, and forms an extensively hydrogen-bonded three-dimensional framework structure. In compound (II), the brucinium cations form the common undulating brucine sheet substructures, which accommodate parallel chains of head-to-tail hydrogen-bonded tartrate anion species in the interstitial cavities.
Supporting information
CCDC references: 612475; 612476
Both compounds were synthesized by heating 1 mmol quantities of either D,L-malic acid for (I) or L-tartaric acid for (II) and brucine tetrahydrate in 50 ml of either 50% ethanol–water for (I) or 50% 2-propanol–water for (II) for 10 min under reflux. Compound (I) was obtained as colourless plates (m.p. 493.5–495.8 K), while (II) was obtained as clusters of colourless prisms (m.p. 522.4–523.6 K), after partial room-temperature evaporation of the solvent.
H atoms potentially involved in hydrogen-bonding interactions were generally located by difference methods or, in the case of (I), where the water H atoms could not be located by difference methods, positioned in their probable interactive sites and their positional parameters refined. For (II), both positional and isotropic displacement parameters for the interactive H atoms were refined. However, for (I), because of the low reflection/refined parameter ratio the interactive H atoms were fixed in the final cycle of refinement. Other brucine and hydroxy H atoms in both (I) and (II) were included at calculated positions [C—H(aromatic) = 0.93 Å and C—H(aliphatic) = 0.96–1.00 Å] and treated as riding [Uiso(H) = 1.2Ueq(C)]. In both structures, Friedel pairs were averaged for the data used in the refinements. The absolute configuration determined for the parent strychnine (Peerdeman, 1956) was invoked.
For both compounds, data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) in WinGX (Farrugia, 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) in WinGX; molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.
(I) 2,3-dimethoxy-10-oxostrychnidinium hydrogen (S)-malate pentahydrate
top
Crystal data top
C23H27N2O4+·C4H5O5−·5H2O | Z = 2 |
Mr = 618.63 | F(000) = 660 |
Triclinic, P1 | Dx = 1.438 Mg m−3 |
Hall symbol: P 1 | Melting point = 493.5–495.8 K |
a = 9.2915 (10) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.4337 (9) Å | Cell parameters from 2640 reflections |
c = 16.9287 (17) Å | θ = 2.2–26.5° |
α = 76.401 (2)° | µ = 0.12 mm−1 |
β = 88.716 (2)° | T = 130 K |
γ = 82.104 (2)° | Plate, colourless |
V = 1428.5 (3) Å3 | 0.40 × 0.35 × 0.05 mm |
Data collection top
Bruker CCD area-detector diffractometer | 4397 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.025 |
Graphite monochromator | θmax = 25.0°, θmin = 2.2° |
ϕ and ω scans | h = −11→10 |
7141 measured reflections | k = −9→11 |
5034 independent reflections | l = −20→15 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 0.90 | w = 1/[σ2(Fo2) + (0.0367P)2 + 0.2077P] where P = (Fo2 + 2Fc2)/3 |
5034 reflections | (Δ/σ)max = 0.005 |
772 parameters | Δρmax = 0.17 e Å−3 |
3 restraints | Δρmin = −0.18 e Å−3 |
Crystal data top
C23H27N2O4+·C4H5O5−·5H2O | γ = 82.104 (2)° |
Mr = 618.63 | V = 1428.5 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.2915 (10) Å | Mo Kα radiation |
b = 9.4337 (9) Å | µ = 0.12 mm−1 |
c = 16.9287 (17) Å | T = 130 K |
α = 76.401 (2)° | 0.40 × 0.35 × 0.05 mm |
β = 88.716 (2)° | |
Data collection top
Bruker CCD area-detector diffractometer | 4397 reflections with I > 2σ(I) |
7141 measured reflections | Rint = 0.025 |
5034 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 3 restraints |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 0.90 | Δρmax = 0.17 e Å−3 |
5034 reflections | Δρmin = −0.18 e Å−3 |
772 parameters | |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | |
O2A | 0.8476 (2) | 0.2908 (2) | 0.83173 (14) | 0.0247 (8) | |
O3A | 0.7836 (2) | 0.4006 (2) | 0.95635 (14) | 0.0237 (8) | |
O24A | 0.0801 (3) | 0.9854 (2) | 0.67172 (14) | 0.0272 (8) | |
O25A | 0.3592 (3) | 0.8094 (2) | 0.91036 (14) | 0.0244 (8) | |
N9A | 0.3500 (3) | 0.6944 (3) | 0.80624 (16) | 0.0188 (9) | |
N19A | 0.2973 (3) | 0.5660 (3) | 0.56171 (17) | 0.0232 (10) | |
C1A | 0.6246 (4) | 0.4169 (3) | 0.7601 (2) | 0.0197 (11) | |
C2A | 0.7201 (4) | 0.3836 (3) | 0.8250 (2) | 0.0196 (11) | |
C3A | 0.6863 (4) | 0.4465 (3) | 0.8927 (2) | 0.0193 (11) | |
C4A | 0.5644 (4) | 0.5485 (3) | 0.8917 (2) | 0.0198 (11) | |
C5A | 0.4745 (4) | 0.5851 (3) | 0.8234 (2) | 0.0184 (11) | |
C6A | 0.5004 (4) | 0.5184 (3) | 0.7596 (2) | 0.0199 (11) | |
C7A | 0.3779 (4) | 0.5674 (3) | 0.6980 (2) | 0.0183 (10) | |
C8A | 0.2984 (4) | 0.7069 (3) | 0.7220 (2) | 0.0193 (11) | |
C10A | 0.3147 (4) | 0.8090 (4) | 0.8418 (2) | 0.0206 (11) | |
C11A | 0.2126 (4) | 0.9370 (4) | 0.7934 (2) | 0.0218 (11) | |
C12A | 0.2250 (4) | 0.9741 (4) | 0.6999 (2) | 0.0231 (11) | |
C13A | 0.3310 (3) | 0.8560 (3) | 0.6725 (2) | 0.0194 (11) | |
C14A | 0.3435 (4) | 0.8607 (4) | 0.5808 (2) | 0.0220 (11) | |
C15A | 0.4698 (4) | 0.7433 (4) | 0.5718 (2) | 0.0222 (11) | |
C16A | 0.4271 (4) | 0.5924 (4) | 0.6084 (2) | 0.0211 (11) | |
C17A | 0.2750 (4) | 0.4497 (4) | 0.7040 (2) | 0.0218 (11) | |
C18A | 0.1916 (4) | 0.5000 (4) | 0.6241 (2) | 0.0247 (12) | |
C20A | 0.2272 (4) | 0.7031 (4) | 0.5030 (2) | 0.0269 (12) | |
C21A | 0.2072 (4) | 0.8325 (4) | 0.5431 (2) | 0.0234 (11) | |
C22A | 0.0809 (4) | 0.9130 (4) | 0.5437 (2) | 0.0290 (12) | |
C23A | 0.0581 (5) | 1.0391 (4) | 0.5857 (2) | 0.0340 (12) | |
C25A | 0.8983 (4) | 0.2455 (4) | 0.7602 (2) | 0.0330 (12) | |
C26A | 0.7527 (4) | 0.4659 (4) | 1.0239 (2) | 0.0270 (12) | |
O2B | 1.0912 (2) | 0.5207 (2) | 0.87425 (14) | 0.0261 (8) | |
O3B | 0.9273 (2) | 0.6391 (2) | 0.74872 (14) | 0.0249 (8) | |
O24B | 0.4541 (3) | 1.2088 (2) | 1.03226 (14) | 0.0271 (8) | |
O25B | 0.5337 (2) | 1.0401 (2) | 0.79287 (14) | 0.0245 (8) | |
N9B | 0.6991 (3) | 1.0063 (3) | 0.89500 (16) | 0.0189 (9) | |
N19B | 0.9380 (3) | 0.9591 (3) | 1.13831 (18) | 0.0227 (10) | |
C1B | 0.9988 (4) | 0.7130 (4) | 0.9437 (2) | 0.0207 (11) | |
C2B | 1.0016 (4) | 0.6455 (4) | 0.8793 (2) | 0.0206 (11) | |
C3B | 0.9083 (4) | 0.7072 (4) | 0.8118 (2) | 0.0210 (11) | |
C4B | 0.8063 (4) | 0.8288 (3) | 0.8113 (2) | 0.0205 (11) | |
C5B | 0.8008 (3) | 0.8896 (3) | 0.8793 (2) | 0.0178 (10) | |
C6B | 0.8977 (3) | 0.8368 (4) | 0.94318 (19) | 0.0193 (11) | |
C7B | 0.8759 (4) | 0.9328 (3) | 1.0034 (2) | 0.0199 (11) | |
C8B | 0.7240 (3) | 1.0212 (3) | 0.97923 (19) | 0.0178 (10) | |
C10B | 0.5667 (3) | 1.0559 (3) | 0.8603 (2) | 0.0187 (11) | |
C11B | 0.4602 (4) | 1.1365 (4) | 0.9085 (2) | 0.0213 (11) | |
C12B | 0.4613 (4) | 1.0786 (4) | 1.0016 (2) | 0.0241 (12) | |
C13B | 0.5962 (4) | 0.9658 (4) | 1.0290 (2) | 0.0211 (11) | |
C14B | 0.6319 (4) | 0.9145 (4) | 1.1206 (2) | 0.0218 (11) | |
C15B | 0.7583 (4) | 0.7881 (3) | 1.1311 (2) | 0.0217 (11) | |
C16B | 0.8935 (4) | 0.8491 (3) | 1.0930 (2) | 0.0195 (10) | |
C17B | 0.9939 (4) | 1.0367 (4) | 0.9960 (2) | 0.0218 (11) | |
C18B | 0.9792 (4) | 1.0887 (4) | 1.0747 (2) | 0.0240 (11) | |
C20B | 0.8237 (4) | 1.0041 (4) | 1.1960 (2) | 0.0242 (11) | |
C21B | 0.6753 (4) | 1.0355 (4) | 1.1577 (2) | 0.0235 (11) | |
C22B | 0.5863 (4) | 1.1559 (4) | 1.1592 (2) | 0.0272 (12) | |
C23B | 0.4390 (4) | 1.1862 (4) | 1.1189 (2) | 0.0304 (12) | |
C26B | 0.8296 (4) | 0.6981 (4) | 0.6816 (2) | 0.0275 (12) | |
C25B | 1.1680 (4) | 0.4391 (4) | 0.9463 (2) | 0.0334 (12) | |
O11C | 0.2765 (3) | 0.4093 (2) | 0.44599 (15) | 0.0268 (8) | |
O12C | 0.3335 (3) | 0.1908 (3) | 0.41621 (17) | 0.0348 (9) | |
O21C | 0.5536 (3) | 0.4440 (3) | 0.46374 (16) | 0.0285 (8) | |
O41C | 0.6367 (3) | 0.0732 (3) | 0.64366 (16) | 0.0315 (9) | |
O42C | 0.4428 (3) | 0.2415 (3) | 0.60560 (14) | 0.0300 (8) | |
C1C | 0.3658 (4) | 0.3032 (4) | 0.4352 (2) | 0.0233 (11) | |
C2C | 0.5280 (4) | 0.3114 (4) | 0.4430 (2) | 0.0233 (11) | |
C3C | 0.6071 (4) | 0.1809 (4) | 0.5037 (2) | 0.0226 (11) | |
C4C | 0.5521 (4) | 0.1709 (4) | 0.5886 (2) | 0.0205 (11) | |
O11D | 0.1536 (3) | 0.9111 (2) | 0.25474 (15) | 0.0272 (8) | |
O12D | 0.3891 (3) | 0.8261 (3) | 0.27593 (15) | 0.0299 (9) | |
O21D | 0.0869 (3) | 0.6524 (3) | 0.23655 (14) | 0.0246 (8) | |
O41D | 0.3857 (3) | 0.6330 (3) | 0.05758 (15) | 0.0349 (9) | |
O42D | 0.2462 (3) | 0.8160 (3) | 0.09672 (14) | 0.0285 (9) | |
C1D | 0.2602 (4) | 0.8125 (4) | 0.2623 (2) | 0.0213 (11) | |
C2D | 0.2330 (4) | 0.6566 (4) | 0.2580 (2) | 0.0216 (11) | |
C3D | 0.3311 (4) | 0.5963 (4) | 0.1971 (2) | 0.0230 (11) | |
C4D | 0.3148 (4) | 0.6940 (4) | 0.1130 (2) | 0.0223 (11) | |
O1W | 0.7394 (3) | 0.3885 (3) | 0.24813 (19) | 0.0378 (11) | |
O2W | 0.5077 (3) | 0.9571 (3) | 0.3818 (2) | 0.0419 (11) | |
O3W | 0.8930 (4) | 0.1846 (3) | 0.37631 (19) | 0.0395 (11) | |
O4W | 0.7965 (4) | 0.9032 (3) | 0.41634 (19) | 0.0374 (11) | |
O5W | −0.0085 (3) | 0.4009 (3) | 0.44955 (18) | 0.0336 (10) | |
O6W | 0.0146 (3) | 0.4165 (4) | 0.17855 (19) | 0.0377 (11) | |
O7W | 0.6154 (3) | 0.6176 (3) | 0.32035 (15) | 0.0273 (9) | |
O8W | 0.1499 (3) | 0.1722 (3) | 0.29358 (18) | 0.0354 (10) | |
O9W | 0.8887 (3) | 0.6725 (3) | 0.35537 (17) | 0.0292 (9) | |
O10W | 0.7885 (4) | 0.4385 (4) | 0.56979 (19) | 0.0554 (11) | |
H1A | 0.64290 | 0.37190 | 0.71690 | 0.0240* | |
H4A | 0.54300 | 0.59150 | 0.93540 | 0.0240* | |
H8A | 0.19330 | 0.70440 | 0.72220 | 0.0230* | |
H12A | 0.26000 | 1.06970 | 0.68160 | 0.0280* | |
H13A | 0.42770 | 0.86720 | 0.69020 | 0.0230* | |
H14A | 0.36740 | 0.95750 | 0.55220 | 0.0260* | |
H16A | 0.50960 | 0.51770 | 0.60440 | 0.0250* | |
H19A | 0.3290 | 0.5000 | 0.5250 | 0.0280* | |
H22A | 0.00240 | 0.89190 | 0.51740 | 0.0350* | |
H27A | 0.22670 | 1.02400 | 0.81190 | 0.0260* | |
H28A | 0.11400 | 0.91790 | 0.80690 | 0.0260* | |
H29A | 0.49250 | 0.75230 | 0.51480 | 0.0270* | |
H30A | 0.55540 | 0.75670 | 0.59950 | 0.0270* | |
H31A | 0.32940 | 0.35240 | 0.70920 | 0.0260* | |
H32A | 0.21020 | 0.44820 | 0.74980 | 0.0260* | |
H33 | 0.15680 | 0.41730 | 0.60930 | 0.0300* | |
H34A | 0.10890 | 0.57270 | 0.62820 | 0.0300* | |
H35A | 0.13350 | 0.68670 | 0.48540 | 0.0320* | |
H36A | 0.28770 | 0.72520 | 0.45540 | 0.0320* | |
H37A | 0.12570 | 1.10820 | 0.56440 | 0.0410* | |
H38A | −0.03980 | 1.09050 | 0.57480 | 0.0410* | |
H39A | 0.83250 | 0.18570 | 0.74540 | 0.0500* | |
H40A | 0.99320 | 0.18960 | 0.77040 | 0.0500* | |
H41A | 0.90320 | 0.33070 | 0.71660 | 0.0500* | |
H42A | 0.75210 | 0.57050 | 1.00650 | 0.0400* | |
H43A | 0.82600 | 0.42580 | 1.06530 | 0.0400* | |
H44A | 0.65940 | 0.44540 | 1.04550 | 0.0400* | |
H1B | 1.06390 | 0.67600 | 0.98690 | 0.0250* | |
H4B | 0.74350 | 0.86870 | 0.76730 | 0.0250* | |
H8B | 0.72580 | 1.12500 | 0.97890 | 0.0210* | |
H12B | 0.37400 | 1.03170 | 1.01780 | 0.0290* | |
H13B | 0.57910 | 0.87730 | 1.01180 | 0.0250* | |
H14B | 0.54710 | 0.87720 | 1.14920 | 0.0260* | |
H16B | 0.97280 | 0.76750 | 1.09750 | 0.0230* | |
H19B | 1.0190 | 0.9210 | 1.171 | 0.0270* | |
H22B | 0.61500 | 1.22360 | 1.18560 | 0.0330* | |
H27B | 0.36320 | 1.13590 | 0.88870 | 0.0260* | |
H28B | 0.47780 | 1.23830 | 0.89680 | 0.0260* | |
H29B | 0.77590 | 0.74360 | 1.18840 | 0.0260* | |
H30B | 0.73440 | 0.71310 | 1.10500 | 0.0260* | |
H31B | 1.09000 | 0.98420 | 0.99170 | 0.0260* | |
H32B | 0.97560 | 1.11890 | 0.94910 | 0.0260* | |
H33B | 1.07030 | 1.11600 | 1.08910 | 0.0290* | |
H34B | 0.90440 | 1.17300 | 1.06930 | 0.0290* | |
H35B | 0.82470 | 0.92580 | 1.24490 | 0.0290* | |
H36B | 0.84640 | 1.09130 | 1.21150 | 0.0290* | |
H37B | 0.38580 | 1.10380 | 1.13930 | 0.0370* | |
H38B | 0.38450 | 1.27320 | 1.13170 | 0.0370* | |
H39B | 0.73140 | 0.69650 | 0.70020 | 0.0410* | |
H40B | 0.84730 | 0.63990 | 0.64200 | 0.0410* | |
H41B | 0.84450 | 0.79770 | 0.65740 | 0.0410* | |
H42B | 1.24060 | 0.49370 | 0.95900 | 0.0500* | |
H43B | 1.21390 | 0.34630 | 0.93780 | 0.0500* | |
H44B | 1.10120 | 0.42230 | 0.99050 | 0.0500* | |
H2C | 0.57150 | 0.31140 | 0.38970 | 0.0280* | |
H21C | 0.5740 | 0.5020 | 0.4160 | 0.0340* | |
H31C | 0.59540 | 0.09110 | 0.48760 | 0.0270* | |
H32C | 0.71000 | 0.18930 | 0.50290 | 0.0270* | |
H41C | 0.5910 | 0.0720 | 0.6930 | 0.0380* | |
H2D | 0.25340 | 0.59080 | 0.31180 | 0.0260* | |
H21D | 0.0210 | 0.6590 | 0.2760 | 0.0300* | |
H31D | 0.43140 | 0.58530 | 0.21490 | 0.0280* | |
H32D | 0.30840 | 0.49960 | 0.19570 | 0.0280* | |
H41D | 0.3770 | 0.6930 | 0.0080 | 0.0420* | |
H11W | 0.704 | 0.463 | 0.271 | 0.046* | |
H12W | 0.825 | 0.408 | 0.223 | 0.046* | |
H21W | 0.467 | 0.926 | 0.347 | 0.050* | |
H22W | 0.455 | 1.035 | 0.394 | 0.050* | |
H31W | 0.978 | 0.174 | 0.347 | 0.047* | |
H32W | 0.840 | 0.254 | 0.343 | 0.047* | |
H41W | 0.827 | 0.992 | 0.403 | 0.044* | |
H42W | 0.701 | 0.921 | 0.405 | 0.044* | |
H51W | 0.088 | 0.404 | 0.448 | 0.041* | |
H52W | −0.020 | 0.332 | 0.427 | 0.041* | |
H61W | 0.058 | 0.338 | 0.216 | 0.046* | |
H62W | 0.038 | 0.493 | 0.198 | 0.046* | |
H71W | 0.539 | 0.688 | 0.305 | 0.032* | |
H72W | 0.695 | 0.655 | 0.325 | 0.032* | |
H81W | 0.162 | 0.076 | 0.285 | 0.042* | |
H82W | 0.211 | 0.188 | 0.327 | 0.042* | |
H91W | 0.923 | 0.583 | 0.386 | 0.035* | |
H92W | 0.867 | 0.741 | 0.386 | 0.035* | |
H10W | 0.870 | 0.426 | 0.540 | 0.066* | |
H13W | 0.714 | 0.440 | 0.536 | 0.066* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O2A | 0.0236 (14) | 0.0233 (13) | 0.0244 (14) | 0.0073 (11) | −0.0033 (11) | −0.0059 (11) |
O3A | 0.0252 (14) | 0.0234 (13) | 0.0213 (13) | 0.0037 (10) | −0.0085 (11) | −0.0063 (11) |
O24A | 0.0260 (14) | 0.0300 (14) | 0.0230 (14) | 0.0050 (11) | −0.0067 (11) | −0.0052 (11) |
O25A | 0.0328 (15) | 0.0237 (13) | 0.0168 (13) | 0.0007 (11) | −0.0033 (11) | −0.0071 (11) |
N9A | 0.0214 (16) | 0.0191 (15) | 0.0162 (15) | −0.0011 (12) | −0.0007 (12) | −0.0059 (12) |
N19A | 0.0272 (18) | 0.0243 (16) | 0.0182 (16) | −0.0001 (13) | −0.0027 (13) | −0.0066 (13) |
C1A | 0.0231 (19) | 0.0192 (18) | 0.0176 (18) | 0.0004 (15) | 0.0039 (15) | −0.0081 (15) |
C2A | 0.021 (2) | 0.0163 (18) | 0.0196 (19) | −0.0006 (15) | −0.0016 (15) | −0.0015 (15) |
C3A | 0.0208 (19) | 0.0186 (18) | 0.0181 (19) | −0.0065 (15) | −0.0032 (15) | −0.0008 (15) |
C4A | 0.026 (2) | 0.0185 (18) | 0.0160 (18) | −0.0036 (15) | 0.0009 (15) | −0.0058 (15) |
C5A | 0.0178 (19) | 0.0199 (18) | 0.0174 (19) | −0.0041 (14) | 0.0020 (14) | −0.0034 (15) |
C6A | 0.022 (2) | 0.0206 (18) | 0.0170 (18) | −0.0055 (15) | −0.0017 (15) | −0.0024 (15) |
C7A | 0.0187 (18) | 0.0176 (17) | 0.0189 (18) | −0.0023 (14) | −0.0007 (14) | −0.0048 (14) |
C8A | 0.0174 (18) | 0.0233 (19) | 0.0172 (18) | −0.0030 (14) | −0.0022 (14) | −0.0042 (15) |
C10A | 0.0196 (19) | 0.0233 (19) | 0.020 (2) | −0.0062 (15) | 0.0028 (15) | −0.0059 (16) |
C11A | 0.022 (2) | 0.0193 (19) | 0.024 (2) | 0.0012 (15) | −0.0008 (16) | −0.0071 (16) |
C12A | 0.027 (2) | 0.0177 (18) | 0.024 (2) | −0.0040 (15) | −0.0029 (16) | −0.0031 (15) |
C13A | 0.0149 (18) | 0.0241 (19) | 0.0208 (19) | −0.0047 (14) | −0.0004 (14) | −0.0071 (15) |
C14A | 0.024 (2) | 0.0196 (18) | 0.0215 (19) | −0.0040 (15) | 0.0013 (15) | −0.0023 (15) |
C15A | 0.021 (2) | 0.033 (2) | 0.0136 (18) | −0.0043 (16) | 0.0001 (15) | −0.0074 (16) |
C16A | 0.0183 (18) | 0.0250 (19) | 0.0207 (19) | −0.0003 (15) | −0.0031 (15) | −0.0081 (16) |
C17A | 0.025 (2) | 0.0205 (18) | 0.0208 (19) | −0.0027 (15) | 0.0027 (16) | −0.0070 (15) |
C18A | 0.022 (2) | 0.026 (2) | 0.029 (2) | −0.0056 (15) | −0.0020 (16) | −0.0109 (17) |
C20A | 0.029 (2) | 0.029 (2) | 0.021 (2) | 0.0009 (17) | −0.0109 (16) | −0.0044 (17) |
C21A | 0.026 (2) | 0.026 (2) | 0.0157 (19) | −0.0021 (16) | −0.0006 (15) | −0.0005 (15) |
C22A | 0.033 (2) | 0.031 (2) | 0.021 (2) | −0.0024 (18) | −0.0089 (17) | −0.0023 (17) |
C23A | 0.040 (2) | 0.031 (2) | 0.027 (2) | 0.0063 (18) | −0.0094 (18) | −0.0041 (18) |
C25A | 0.031 (2) | 0.037 (2) | 0.026 (2) | 0.0112 (17) | −0.0010 (18) | −0.0062 (19) |
C26A | 0.030 (2) | 0.028 (2) | 0.023 (2) | −0.0002 (16) | −0.0060 (17) | −0.0076 (16) |
O2B | 0.0231 (14) | 0.0254 (14) | 0.0275 (15) | 0.0067 (11) | −0.0026 (11) | −0.0074 (12) |
O3B | 0.0232 (14) | 0.0297 (14) | 0.0240 (14) | 0.0000 (11) | −0.0017 (11) | −0.0127 (12) |
O24B | 0.0318 (15) | 0.0266 (14) | 0.0228 (14) | 0.0038 (11) | −0.0031 (11) | −0.0100 (11) |
O25B | 0.0227 (14) | 0.0311 (14) | 0.0184 (13) | 0.0001 (11) | −0.0056 (10) | −0.0047 (11) |
N9B | 0.0184 (16) | 0.0198 (15) | 0.0183 (15) | −0.0019 (12) | −0.0005 (12) | −0.0046 (12) |
N19B | 0.0252 (18) | 0.0222 (16) | 0.0194 (16) | −0.0027 (14) | −0.0061 (14) | −0.0018 (13) |
C1B | 0.0192 (19) | 0.0218 (19) | 0.0181 (19) | −0.0015 (15) | −0.0015 (15) | 0.0007 (15) |
C2B | 0.0191 (19) | 0.0207 (19) | 0.0211 (19) | −0.0042 (15) | 0.0046 (15) | −0.0028 (15) |
C3B | 0.0197 (19) | 0.0202 (19) | 0.024 (2) | −0.0061 (15) | 0.0036 (15) | −0.0053 (16) |
C4B | 0.0174 (19) | 0.0259 (19) | 0.0186 (18) | −0.0009 (15) | −0.0037 (15) | −0.0067 (15) |
C5B | 0.0148 (18) | 0.0194 (18) | 0.0187 (18) | −0.0031 (14) | 0.0000 (14) | −0.0031 (15) |
C6B | 0.0201 (19) | 0.0228 (19) | 0.0151 (18) | −0.0051 (15) | 0.0033 (15) | −0.0036 (15) |
C7B | 0.0207 (19) | 0.0204 (18) | 0.0175 (18) | −0.0035 (15) | 0.0011 (15) | −0.0020 (15) |
C8B | 0.0193 (19) | 0.0148 (17) | 0.0195 (18) | −0.0011 (14) | −0.0023 (14) | −0.0050 (15) |
C10B | 0.020 (2) | 0.0173 (18) | 0.0178 (19) | −0.0048 (15) | −0.0032 (15) | −0.0006 (15) |
C11B | 0.0158 (19) | 0.0245 (19) | 0.024 (2) | −0.0007 (15) | −0.0031 (15) | −0.0071 (16) |
C12B | 0.021 (2) | 0.026 (2) | 0.026 (2) | −0.0029 (16) | −0.0008 (16) | −0.0078 (16) |
C13B | 0.025 (2) | 0.0185 (18) | 0.022 (2) | −0.0078 (15) | −0.0005 (16) | −0.0064 (15) |
C14B | 0.0218 (19) | 0.0237 (19) | 0.0198 (19) | −0.0058 (15) | 0.0032 (15) | −0.0036 (16) |
C15B | 0.028 (2) | 0.0182 (18) | 0.0175 (18) | −0.0030 (15) | −0.0027 (15) | −0.0013 (15) |
C16B | 0.0232 (19) | 0.0152 (17) | 0.0201 (18) | 0.0011 (14) | −0.0055 (15) | −0.0057 (14) |
C17B | 0.0192 (19) | 0.0248 (19) | 0.0197 (19) | −0.0022 (15) | −0.0041 (15) | −0.0021 (15) |
C18B | 0.026 (2) | 0.0213 (19) | 0.025 (2) | −0.0080 (15) | −0.0035 (16) | −0.0030 (16) |
C20B | 0.032 (2) | 0.025 (2) | 0.0163 (18) | −0.0016 (16) | −0.0026 (16) | −0.0075 (16) |
C21B | 0.032 (2) | 0.027 (2) | 0.0130 (18) | −0.0084 (17) | 0.0021 (16) | −0.0053 (16) |
C22B | 0.036 (2) | 0.028 (2) | 0.019 (2) | −0.0029 (18) | 0.0023 (17) | −0.0092 (16) |
C23B | 0.033 (2) | 0.033 (2) | 0.028 (2) | 0.0047 (17) | 0.0001 (17) | −0.0177 (18) |
C26B | 0.027 (2) | 0.031 (2) | 0.027 (2) | −0.0012 (16) | 0.0004 (17) | −0.0135 (18) |
C25B | 0.032 (2) | 0.028 (2) | 0.036 (2) | 0.0112 (17) | −0.0026 (19) | −0.0075 (18) |
O11C | 0.0260 (14) | 0.0265 (14) | 0.0288 (15) | 0.0024 (11) | −0.0058 (11) | −0.0110 (12) |
O12C | 0.0325 (16) | 0.0318 (15) | 0.0463 (17) | −0.0033 (12) | −0.0087 (13) | −0.0211 (13) |
O21C | 0.0348 (16) | 0.0292 (14) | 0.0240 (14) | −0.0109 (12) | −0.0017 (12) | −0.0071 (12) |
O41C | 0.0334 (16) | 0.0359 (15) | 0.0192 (14) | 0.0093 (12) | 0.0003 (12) | −0.0024 (12) |
O42C | 0.0320 (16) | 0.0303 (14) | 0.0223 (14) | 0.0097 (12) | 0.0013 (12) | −0.0036 (12) |
C1C | 0.031 (2) | 0.026 (2) | 0.0130 (18) | −0.0054 (17) | −0.0025 (15) | −0.0034 (16) |
C2C | 0.029 (2) | 0.0259 (19) | 0.0162 (19) | −0.0054 (16) | −0.0018 (15) | −0.0061 (15) |
C3C | 0.021 (2) | 0.0233 (19) | 0.024 (2) | 0.0001 (15) | −0.0017 (15) | −0.0079 (16) |
C4C | 0.024 (2) | 0.0176 (18) | 0.0204 (19) | −0.0043 (16) | −0.0002 (16) | −0.0047 (15) |
O11D | 0.0265 (15) | 0.0252 (14) | 0.0316 (15) | 0.0039 (12) | −0.0067 (12) | −0.0136 (12) |
O12D | 0.0250 (15) | 0.0279 (14) | 0.0394 (16) | −0.0005 (11) | −0.0093 (12) | −0.0137 (12) |
O21D | 0.0248 (14) | 0.0291 (14) | 0.0208 (13) | −0.0058 (11) | 0.0020 (11) | −0.0065 (12) |
O41D | 0.0473 (18) | 0.0325 (15) | 0.0209 (14) | 0.0066 (13) | 0.0050 (13) | −0.0056 (12) |
O42D | 0.0326 (16) | 0.0262 (15) | 0.0216 (14) | 0.0067 (12) | 0.0009 (11) | −0.0014 (11) |
C1D | 0.024 (2) | 0.025 (2) | 0.0148 (18) | −0.0008 (16) | −0.0024 (15) | −0.0056 (15) |
C2D | 0.023 (2) | 0.0235 (19) | 0.0167 (19) | −0.0010 (15) | −0.0045 (15) | −0.0026 (15) |
C3D | 0.0229 (19) | 0.0209 (19) | 0.025 (2) | −0.0009 (15) | −0.0045 (15) | −0.0055 (16) |
C4D | 0.0207 (19) | 0.028 (2) | 0.022 (2) | −0.0064 (16) | −0.0023 (16) | −0.0113 (16) |
O1W | 0.0353 (19) | 0.0369 (17) | 0.0449 (19) | −0.0062 (14) | −0.0004 (15) | −0.0163 (15) |
O2W | 0.0397 (19) | 0.0424 (19) | 0.048 (2) | 0.0098 (14) | −0.0162 (15) | −0.0265 (16) |
O3W | 0.0354 (19) | 0.0357 (18) | 0.0457 (19) | −0.0011 (14) | −0.0002 (16) | −0.0081 (15) |
O4W | 0.0357 (19) | 0.0288 (18) | 0.0493 (19) | −0.0016 (15) | −0.0049 (15) | −0.0134 (15) |
O5W | 0.0301 (17) | 0.0332 (17) | 0.0380 (18) | 0.0010 (13) | 0.0005 (13) | −0.0123 (14) |
O6W | 0.0444 (19) | 0.0341 (19) | 0.0378 (18) | −0.0092 (16) | −0.0061 (14) | −0.0120 (16) |
O7W | 0.0277 (16) | 0.0242 (15) | 0.0277 (15) | −0.0016 (13) | −0.0031 (12) | −0.0023 (12) |
O8W | 0.0330 (17) | 0.0284 (16) | 0.0466 (19) | 0.0028 (12) | −0.0128 (14) | −0.0154 (14) |
O9W | 0.0286 (16) | 0.0279 (16) | 0.0278 (16) | −0.0003 (13) | 0.0009 (12) | −0.0022 (14) |
O10W | 0.057 (2) | 0.075 (2) | 0.0394 (18) | −0.0088 (17) | −0.0037 (16) | −0.0234 (17) |
Geometric parameters (Å, º) top
O2A—C2A | 1.363 (4) | C14A—H14A | 0.9800 |
O2A—C25A | 1.426 (4) | C15A—H29A | 0.9700 |
O24A—C12A | 1.420 (5) | C15A—H30A | 0.9700 |
O24A—C23A | 1.434 (4) | C16A—H16A | 0.9800 |
O25A—C10A | 1.242 (4) | C17A—H32A | 0.9700 |
O3A—C3A | 1.372 (4) | C17A—H31A | 0.9700 |
O3A—C26A | 1.427 (4) | C18A—H34A | 0.9700 |
O2B—C25B | 1.427 (4) | C18A—H33 | 0.9700 |
O2B—C2B | 1.364 (4) | C20A—H36A | 0.9700 |
O24B—C12B | 1.435 (4) | C20A—H35A | 0.9700 |
O24B—C23B | 1.438 (4) | C22A—H22A | 0.9300 |
O25B—C10B | 1.236 (4) | C23A—H37A | 0.9700 |
O3B—C3B | 1.367 (4) | C23A—H38A | 0.9700 |
O3B—C26B | 1.427 (4) | C25A—H40A | 0.9600 |
O11C—C1C | 1.255 (4) | C25A—H41A | 0.9600 |
O12C—C1C | 1.253 (5) | C25A—H39A | 0.9600 |
O21C—C2C | 1.427 (5) | C26A—H44A | 0.9600 |
O41C—C4C | 1.329 (5) | C26A—H42A | 0.9600 |
O42C—C4C | 1.204 (5) | C26A—H43A | 0.9600 |
O21C—H21C | 0.90 | C1B—C2B | 1.384 (5) |
O41C—H41C | 0.93 | C1B—C6B | 1.393 (5) |
O11D—C1D | 1.249 (4) | C2B—C3B | 1.410 (5) |
O12D—C1D | 1.254 (5) | C3B—C4B | 1.383 (5) |
O21D—C2D | 1.421 (5) | C4B—C5B | 1.399 (4) |
O41D—C4D | 1.329 (4) | C5B—C6B | 1.377 (4) |
O42D—C4D | 1.210 (5) | C6B—C7B | 1.508 (5) |
O21D—H21D | 0.90 | C7B—C8B | 1.548 (5) |
O41D—H41D | 0.89 | C7B—C16B | 1.537 (5) |
O1W—H12W | 0.91 | C7B—C17B | 1.552 (5) |
O1W—H11W | 0.90 | C8B—C13B | 1.520 (5) |
N9A—C10A | 1.356 (5) | C10B—C11B | 1.507 (5) |
N9A—C5A | 1.426 (4) | C11B—C12B | 1.542 (5) |
N9A—C8A | 1.488 (4) | C12B—C13B | 1.532 (5) |
N19A—C20A | 1.509 (5) | C13B—C14B | 1.541 (5) |
N19A—C18A | 1.510 (5) | C14B—C15B | 1.536 (5) |
N19A—C16A | 1.536 (5) | C14B—C21B | 1.528 (5) |
O2W—H21W | 0.84 | C15B—C16B | 1.521 (5) |
O2W—H22W | 0.89 | C17B—C18B | 1.522 (5) |
N19A—H19A | 0.99 | C20B—C21B | 1.499 (5) |
N9B—C8B | 1.492 (4) | C21B—C22B | 1.315 (5) |
N9B—C10B | 1.350 (4) | C22B—C23B | 1.504 (5) |
N9B—C5B | 1.420 (4) | C1B—H1B | 0.9300 |
N19B—C20B | 1.512 (5) | C4B—H4B | 0.9300 |
N19B—C16B | 1.531 (4) | C8B—H8B | 0.9800 |
N19B—C18B | 1.514 (5) | O8W—H82W | 0.86 |
O3W—H31W | 0.93 | O8W—H81W | 0.94 |
O3W—H32W | 0.86 | C11B—H27B | 0.9700 |
N19B—H19B | 0.92 | C11B—H28B | 0.9700 |
O4W—H42W | 0.90 | C12B—H12B | 0.9800 |
O4W—H41W | 0.90 | C13B—H13B | 0.9800 |
O5W—H52W | 0.85 | C14B—H14B | 0.9800 |
O5W—H51W | 0.90 | C15B—H29B | 0.9700 |
O6W—H62W | 0.91 | C15B—H30B | 0.9700 |
O6W—H61W | 0.91 | C16B—H16B | 0.9800 |
C1A—C2A | 1.378 (5) | C17B—H31B | 0.9700 |
C1A—C6A | 1.393 (5) | C17B—H32B | 0.9700 |
C2A—C3A | 1.420 (4) | C18B—H34B | 0.9700 |
C3A—C4A | 1.379 (5) | C18B—H33B | 0.9700 |
C4A—C5A | 1.389 (5) | C20B—H35B | 0.9700 |
C5A—C6A | 1.374 (4) | C20B—H36B | 0.9700 |
C6A—C7A | 1.510 (5) | C22B—H22B | 0.9300 |
C7A—C8A | 1.554 (4) | C23B—H37B | 0.9700 |
C7A—C17A | 1.547 (5) | C23B—H38B | 0.9700 |
C7A—C16A | 1.548 (5) | C26B—H40B | 0.9600 |
C8A—C13A | 1.524 (4) | C26B—H41B | 0.9600 |
C10A—C11A | 1.511 (5) | C26B—H39B | 0.9600 |
C11A—C12A | 1.544 (5) | C25B—H44B | 0.9600 |
C12A—C13A | 1.532 (5) | C25B—H43B | 0.9600 |
C13A—C14A | 1.545 (5) | C25B—H42B | 0.9600 |
C14A—C21A | 1.514 (5) | C1C—C2C | 1.530 (5) |
C14A—C15A | 1.530 (5) | C2C—C3C | 1.517 (5) |
C15A—C16A | 1.516 (5) | C3C—C4C | 1.501 (5) |
C17A—C18A | 1.516 (5) | C2C—H2C | 0.9800 |
C20A—C21A | 1.519 (5) | C3C—H32C | 0.9700 |
C21A—C22A | 1.309 (5) | C3C—H31C | 0.9700 |
C22A—C23A | 1.512 (5) | O9W—H91W | 0.90 |
C1A—H1A | 0.9300 | O9W—H92W | 0.92 |
C4A—H4A | 0.9300 | C1D—C2D | 1.545 (5) |
O7W—H71W | 0.90 | C2D—C3D | 1.519 (5) |
O7W—H72W | 0.87 | C3D—C4D | 1.501 (5) |
C8A—H8A | 0.9800 | C2D—H2D | 0.9800 |
C11A—H28A | 0.9700 | C3D—H31D | 0.9700 |
C11A—H27A | 0.9700 | C3D—H32D | 0.9700 |
C12A—H12A | 0.9800 | O10W—H10W | 0.91 |
C13A—H13A | 0.9800 | O10W—H13W | 0.90 |
| | | |
C2A—O2A—C25A | 116.8 (3) | C1B—C2B—C3B | 119.9 (3) |
C12A—O24A—C23A | 115.6 (3) | O2B—C2B—C1B | 125.0 (3) |
C3A—O3A—C26A | 115.9 (2) | O3B—C3B—C2B | 115.4 (3) |
C2B—O2B—C25B | 117.3 (3) | C2B—C3B—C4B | 120.9 (3) |
C12B—O24B—C23B | 115.3 (2) | O3B—C3B—C4B | 123.7 (3) |
C3B—O3B—C26B | 115.5 (3) | C3B—C4B—C5B | 117.7 (3) |
C2C—O21C—H21C | 104 | N9B—C5B—C6B | 110.4 (3) |
C4C—O41C—H41C | 106 | N9B—C5B—C4B | 127.6 (3) |
C2D—O21D—H21D | 115 | C4B—C5B—C6B | 122.0 (3) |
C4D—O41D—H41D | 112 | C1B—C6B—C5B | 119.8 (3) |
H11W—O1W—H12W | 109 | C1B—C6B—C7B | 129.9 (3) |
C8A—N9A—C10A | 119.5 (3) | C5B—C6B—C7B | 110.3 (3) |
C5A—N9A—C8A | 109.0 (3) | C6B—C7B—C16B | 114.8 (3) |
C5A—N9A—C10A | 126.9 (3) | C6B—C7B—C8B | 102.6 (3) |
C16A—N19A—C18A | 107.2 (3) | C6B—C7B—C17B | 112.1 (3) |
C18A—N19A—C20A | 112.2 (3) | C8B—C7B—C16B | 115.2 (3) |
C16A—N19A—C20A | 113.2 (3) | C16B—C7B—C17B | 101.4 (3) |
H21W—O2W—H22W | 112 | C8B—C7B—C17B | 111.2 (3) |
C18A—N19A—H19A | 111 | N9B—C8B—C7B | 104.4 (2) |
C20A—N19A—H19A | 102 | N9B—C8B—C13B | 106.2 (2) |
C16A—N19A—H19A | 111 | C7B—C8B—C13B | 116.8 (3) |
C8B—N9B—C10B | 118.8 (3) | O25B—C10B—C11B | 121.2 (3) |
C5B—N9B—C10B | 127.1 (3) | O25B—C10B—N9B | 123.2 (3) |
C5B—N9B—C8B | 108.8 (2) | N9B—C10B—C11B | 115.5 (3) |
C16B—N19B—C20B | 113.7 (3) | C10B—C11B—C12B | 117.6 (3) |
C16B—N19B—C18B | 107.1 (3) | O24B—C12B—C11B | 104.1 (3) |
C18B—N19B—C20B | 112.8 (3) | C11B—C12B—C13B | 110.3 (3) |
H31W—O3W—H32W | 102 | O24B—C12B—C13B | 114.5 (3) |
C20B—N19B—H19B | 104 | C8B—C13B—C14B | 112.6 (3) |
C16B—N19B—H19B | 112 | C8B—C13B—C12B | 107.9 (3) |
C18B—N19B—H19B | 107 | C12B—C13B—C14B | 118.5 (3) |
H41W—O4W—H42W | 105 | C13B—C14B—C21B | 113.6 (3) |
H51W—O5W—H52W | 105 | C13B—C14B—C15B | 107.1 (3) |
H61W—O6W—H62W | 101 | C15B—C14B—C21B | 109.1 (3) |
C2A—C1A—C6A | 119.6 (3) | C14B—C15B—C16B | 108.9 (3) |
O2A—C2A—C1A | 125.5 (3) | C7B—C16B—C15B | 114.9 (3) |
C1A—C2A—C3A | 119.5 (3) | N19B—C16B—C15B | 110.0 (3) |
O2A—C2A—C3A | 115.0 (3) | N19B—C16B—C7B | 105.7 (2) |
O3A—C3A—C4A | 123.9 (3) | C7B—C17B—C18B | 103.4 (3) |
O3A—C3A—C2A | 115.4 (3) | N19B—C18B—C17B | 105.4 (3) |
C2A—C3A—C4A | 120.7 (3) | N19B—C20B—C21B | 111.3 (3) |
C3A—C4A—C5A | 118.0 (3) | C20B—C21B—C22B | 122.2 (3) |
C4A—C5A—C6A | 122.0 (3) | C14B—C21B—C22B | 122.4 (3) |
N9A—C5A—C6A | 110.1 (3) | C14B—C21B—C20B | 115.3 (3) |
N9A—C5A—C4A | 127.9 (3) | C21B—C22B—C23B | 121.2 (3) |
C1A—C6A—C5A | 119.9 (3) | O24B—C23B—C22B | 110.1 (3) |
C1A—C6A—C7A | 129.3 (3) | C6B—C1B—H1B | 120.00 |
C5A—C6A—C7A | 110.7 (3) | C2B—C1B—H1B | 120.00 |
C6A—C7A—C8A | 102.3 (3) | C3B—C4B—H4B | 121.00 |
C8A—C7A—C16A | 114.6 (3) | C5B—C4B—H4B | 121.00 |
C8A—C7A—C17A | 111.0 (3) | N9B—C8B—H8B | 110.00 |
C16A—C7A—C17A | 102.5 (3) | C13B—C8B—H8B | 110.00 |
C6A—C7A—C16A | 114.5 (3) | C7B—C8B—H8B | 110.00 |
C6A—C7A—C17A | 112.3 (3) | H81W—O8W—H82W | 115 |
N9A—C8A—C7A | 104.5 (3) | C10B—C11B—H28B | 108.00 |
N9A—C8A—C13A | 106.2 (3) | C12B—C11B—H27B | 108.00 |
C7A—C8A—C13A | 117.4 (3) | H27B—C11B—H28B | 107.00 |
O25A—C10A—C11A | 121.3 (3) | C12B—C11B—H28B | 108.00 |
O25A—C10A—N9A | 123.2 (3) | C10B—C11B—H27B | 108.00 |
N9A—C10A—C11A | 115.6 (3) | C13B—C12B—H12B | 109.00 |
C10A—C11A—C12A | 118.1 (3) | C11B—C12B—H12B | 109.00 |
O24A—C12A—C13A | 114.0 (3) | O24B—C12B—H12B | 109.00 |
C11A—C12A—C13A | 110.5 (3) | C12B—C13B—H13B | 106.00 |
O24A—C12A—C11A | 104.3 (3) | C14B—C13B—H13B | 106.00 |
C8A—C13A—C12A | 107.2 (3) | C8B—C13B—H13B | 106.00 |
C12A—C13A—C14A | 118.8 (3) | C21B—C14B—H14B | 109.00 |
C8A—C13A—C14A | 112.2 (3) | C15B—C14B—H14B | 109.00 |
C13A—C14A—C21A | 114.1 (3) | C13B—C14B—H14B | 109.00 |
C13A—C14A—C15A | 106.6 (3) | C14B—C15B—H29B | 110.00 |
C15A—C14A—C21A | 109.7 (3) | C16B—C15B—H29B | 110.00 |
C14A—C15A—C16A | 109.0 (3) | C16B—C15B—H30B | 110.00 |
N19A—C16A—C7A | 104.9 (3) | H29B—C15B—H30B | 108.00 |
N19A—C16A—C15A | 110.4 (3) | C14B—C15B—H30B | 110.00 |
C7A—C16A—C15A | 115.2 (3) | N19B—C16B—H16B | 109.00 |
C7A—C17A—C18A | 102.9 (3) | C7B—C16B—H16B | 109.00 |
N19A—C18A—C17A | 106.1 (3) | C15B—C16B—H16B | 109.00 |
N19A—C20A—C21A | 110.4 (3) | H31B—C17B—H32B | 109.00 |
C14A—C21A—C22A | 123.4 (3) | C7B—C17B—H31B | 111.00 |
C14A—C21A—C20A | 115.0 (3) | C18B—C17B—H31B | 111.00 |
C20A—C21A—C22A | 121.6 (3) | C7B—C17B—H32B | 111.00 |
C21A—C22A—C23A | 122.3 (4) | C18B—C17B—H32B | 111.00 |
O24A—C23A—C22A | 110.4 (3) | C17B—C18B—H33B | 111.00 |
C6A—C1A—H1A | 120.00 | H33B—C18B—H34B | 109.00 |
C2A—C1A—H1A | 120.00 | N19B—C18B—H34B | 111.00 |
C3A—C4A—H4A | 121.00 | N19B—C18B—H33B | 111.00 |
C5A—C4A—H4A | 121.00 | C17B—C18B—H34B | 111.00 |
H71W—O7W—H72W | 112 | N19B—C20B—H36B | 109.00 |
C7A—C8A—H8A | 109.00 | N19B—C20B—H35B | 109.00 |
N9A—C8A—H8A | 109.00 | H35B—C20B—H36B | 108.00 |
C13A—C8A—H8A | 109.00 | C21B—C20B—H36B | 109.00 |
C10A—C11A—H28A | 108.00 | C21B—C20B—H35B | 109.00 |
H27A—C11A—H28A | 107.00 | C23B—C22B—H22B | 119.00 |
C12A—C11A—H27A | 108.00 | C21B—C22B—H22B | 119.00 |
C10A—C11A—H27A | 108.00 | C22B—C23B—H38B | 110.00 |
C12A—C11A—H28A | 108.00 | O24B—C23B—H37B | 110.00 |
C11A—C12A—H12A | 109.00 | H37B—C23B—H38B | 108.00 |
C13A—C12A—H12A | 109.00 | O24B—C23B—H38B | 110.00 |
O24A—C12A—H12A | 109.00 | C22B—C23B—H37B | 110.00 |
C12A—C13A—H13A | 106.00 | O3B—C26B—H40B | 109.00 |
C8A—C13A—H13A | 106.00 | O3B—C26B—H39B | 109.00 |
C14A—C13A—H13A | 106.00 | H39B—C26B—H41B | 109.00 |
C13A—C14A—H14A | 109.00 | O3B—C26B—H41B | 109.00 |
C15A—C14A—H14A | 109.00 | H39B—C26B—H40B | 110.00 |
C21A—C14A—H14A | 109.00 | H40B—C26B—H41B | 109.00 |
C16A—C15A—H30A | 110.00 | O2B—C25B—H43B | 109.00 |
C14A—C15A—H30A | 110.00 | H42B—C25B—H44B | 109.00 |
C14A—C15A—H29A | 110.00 | O2B—C25B—H42B | 109.00 |
H29A—C15A—H30A | 108.00 | H43B—C25B—H44B | 110.00 |
C16A—C15A—H29A | 110.00 | H42B—C25B—H43B | 109.00 |
C7A—C16A—H16A | 109.00 | O2B—C25B—H44B | 109.00 |
C15A—C16A—H16A | 109.00 | O11C—C1C—C2C | 118.4 (3) |
N19A—C16A—H16A | 109.00 | O11C—C1C—O12C | 125.3 (4) |
C18A—C17A—H31A | 111.00 | O12C—C1C—C2C | 116.3 (3) |
H31A—C17A—H32A | 109.00 | O21C—C2C—C3C | 109.0 (3) |
C7A—C17A—H31A | 111.00 | O21C—C2C—C1C | 112.1 (3) |
C18A—C17A—H32A | 111.00 | C1C—C2C—C3C | 113.3 (3) |
C7A—C17A—H32A | 111.00 | C2C—C3C—C4C | 112.4 (3) |
N19A—C18A—H33 | 110.00 | O41C—C4C—C3C | 112.5 (3) |
N19A—C18A—H34A | 111.00 | O42C—C4C—C3C | 124.3 (3) |
C17A—C18A—H33 | 111.00 | O41C—C4C—O42C | 123.2 (3) |
C17A—C18A—H34A | 111.00 | O21C—C2C—H2C | 107.00 |
H33—C18A—H34A | 109.00 | C1C—C2C—H2C | 107.00 |
C21A—C20A—H36A | 110.00 | C3C—C2C—H2C | 107.00 |
N19A—C20A—H35A | 110.00 | C4C—C3C—H32C | 109.00 |
C21A—C20A—H35A | 110.00 | H31C—C3C—H32C | 108.00 |
H35A—C20A—H36A | 108.00 | C2C—C3C—H31C | 109.00 |
N19A—C20A—H36A | 110.00 | C4C—C3C—H31C | 109.00 |
C21A—C22A—H22A | 119.00 | C2C—C3C—H32C | 109.00 |
C23A—C22A—H22A | 119.00 | H91W—O9W—H92W | 112 |
O24A—C23A—H38A | 110.00 | O11D—C1D—C2D | 118.2 (3) |
H37A—C23A—H38A | 108.00 | O12D—C1D—C2D | 115.7 (3) |
C22A—C23A—H38A | 110.00 | O11D—C1D—O12D | 126.1 (4) |
C22A—C23A—H37A | 109.00 | C1D—C2D—C3D | 112.2 (3) |
O24A—C23A—H37A | 110.00 | O21D—C2D—C3D | 107.7 (3) |
O2A—C25A—H41A | 110.00 | O21D—C2D—C1D | 112.3 (3) |
H39A—C25A—H41A | 109.00 | C2D—C3D—C4D | 112.5 (3) |
H40A—C25A—H41A | 109.00 | O41D—C4D—O42D | 123.0 (3) |
H39A—C25A—H40A | 110.00 | O41D—C4D—C3D | 112.8 (3) |
O2A—C25A—H40A | 109.00 | O42D—C4D—C3D | 124.2 (3) |
O2A—C25A—H39A | 109.00 | C3D—C2D—H2D | 108.00 |
O3A—C26A—H44A | 110.00 | C1D—C2D—H2D | 108.00 |
H43A—C26A—H44A | 109.00 | O21D—C2D—H2D | 108.00 |
H42A—C26A—H44A | 109.00 | C2D—C3D—H32D | 109.00 |
O3A—C26A—H42A | 110.00 | C2D—C3D—H31D | 109.00 |
O3A—C26A—H43A | 110.00 | H31D—C3D—H32D | 108.00 |
H42A—C26A—H43A | 109.00 | C4D—C3D—H31D | 109.00 |
C2B—C1B—C6B | 119.4 (3) | C4D—C3D—H32D | 109.00 |
O2B—C2B—C3B | 115.1 (3) | H10W—O10W—H13W | 105 |
| | | |
C25A—O2A—C2A—C1A | 11.8 (5) | O24A—C12A—C13A—C14A | 54.7 (4) |
C25A—O2A—C2A—C3A | −169.4 (3) | C8A—C13A—C14A—C21A | 60.1 (4) |
C23A—O24A—C12A—C11A | 171.9 (3) | C12A—C13A—C14A—C15A | 172.8 (3) |
C23A—O24A—C12A—C13A | −67.5 (4) | C8A—C13A—C14A—C15A | −61.1 (4) |
C12A—O24A—C23A—C22A | 88.8 (4) | C12A—C13A—C14A—C21A | −65.9 (4) |
C26A—O3A—C3A—C2A | 178.5 (3) | C21A—C14A—C15A—C16A | −55.3 (3) |
C26A—O3A—C3A—C4A | −0.4 (4) | C13A—C14A—C21A—C20A | −122.0 (3) |
C25B—O2B—C2B—C1B | 12.2 (5) | C13A—C14A—C15A—C16A | 68.7 (3) |
C25B—O2B—C2B—C3B | −168.8 (3) | C15A—C14A—C21A—C20A | −2.5 (4) |
C23B—O24B—C12B—C11B | 174.1 (3) | C13A—C14A—C21A—C22A | 58.6 (5) |
C23B—O24B—C12B—C13B | −65.4 (4) | C15A—C14A—C21A—C22A | 178.1 (3) |
C12B—O24B—C23B—C22B | 90.2 (4) | C14A—C15A—C16A—C7A | −55.5 (4) |
C26B—O3B—C3B—C2B | 177.9 (3) | C14A—C15A—C16A—N19A | 63.0 (3) |
C26B—O3B—C3B—C4B | −2.5 (5) | C7A—C17A—C18A—N19A | 34.7 (3) |
C5A—N9A—C8A—C13A | −110.4 (3) | N19A—C20A—C21A—C22A | −127.1 (4) |
C10A—N9A—C5A—C4A | 18.1 (6) | N19A—C20A—C21A—C14A | 53.5 (4) |
C5A—N9A—C8A—C7A | 14.4 (3) | C14A—C21A—C22A—C23A | −2.7 (5) |
C10A—N9A—C5A—C6A | −159.9 (3) | C20A—C21A—C22A—C23A | 178.0 (3) |
C8A—N9A—C5A—C4A | 173.4 (3) | C21A—C22A—C23A—O24A | −64.7 (5) |
C8A—N9A—C5A—C6A | −4.7 (4) | C2B—C1B—C6B—C5B | 0.8 (5) |
C10A—N9A—C8A—C13A | 47.0 (4) | C6B—C1B—C2B—O2B | −177.3 (3) |
C8A—N9A—C10A—O25A | −176.6 (3) | C2B—C1B—C6B—C7B | −177.5 (3) |
C10A—N9A—C8A—C7A | 171.8 (3) | C6B—C1B—C2B—C3B | 3.7 (5) |
C5A—N9A—C10A—O25A | −23.6 (6) | C1B—C2B—C3B—O3B | 175.0 (3) |
C5A—N9A—C10A—C11A | 158.1 (3) | O2B—C2B—C3B—O3B | −4.1 (5) |
C8A—N9A—C10A—C11A | 5.2 (5) | O2B—C2B—C3B—C4B | 176.2 (3) |
C18A—N19A—C20A—C21A | 76.1 (4) | C1B—C2B—C3B—C4B | −4.6 (6) |
C16A—N19A—C20A—C21A | −45.3 (4) | C2B—C3B—C4B—C5B | 1.1 (5) |
C20A—N19A—C16A—C15A | −11.0 (4) | O3B—C3B—C4B—C5B | −178.6 (3) |
C20A—N19A—C18A—C17A | −139.9 (3) | C3B—C4B—C5B—C6B | 3.5 (5) |
C20A—N19A—C16A—C7A | 113.7 (3) | C3B—C4B—C5B—N9B | −174.8 (3) |
C18A—N19A—C16A—C15A | −135.2 (3) | N9B—C5B—C6B—C1B | 174.1 (3) |
C16A—N19A—C18A—C17A | −15.1 (4) | C4B—C5B—C6B—C7B | 174.1 (3) |
C18A—N19A—C16A—C7A | −10.5 (3) | C4B—C5B—C6B—C1B | −4.4 (5) |
C10B—N9B—C8B—C7B | 171.5 (3) | N9B—C5B—C6B—C7B | −7.3 (4) |
C10B—N9B—C8B—C13B | 47.5 (4) | C1B—C6B—C7B—C8B | −165.4 (3) |
C5B—N9B—C10B—O25B | −24.2 (5) | C5B—C6B—C7B—C17B | −103.0 (3) |
C8B—N9B—C10B—C11B | 6.0 (4) | C1B—C6B—C7B—C17B | 75.3 (4) |
C10B—N9B—C5B—C6B | −159.1 (3) | C5B—C6B—C7B—C16B | 142.0 (3) |
C5B—N9B—C8B—C13B | −108.6 (3) | C5B—C6B—C7B—C8B | 16.3 (3) |
C8B—N9B—C5B—C6B | −5.5 (3) | C1B—C6B—C7B—C16B | −39.7 (5) |
C8B—N9B—C10B—O25B | −175.5 (3) | C8B—C7B—C17B—C18B | 81.5 (3) |
C5B—N9B—C8B—C7B | 15.4 (3) | C6B—C7B—C17B—C18B | −164.4 (3) |
C5B—N9B—C10B—C11B | 157.2 (3) | C17B—C7B—C16B—N19B | 33.2 (3) |
C8B—N9B—C5B—C4B | 172.9 (3) | C17B—C7B—C16B—C15B | 154.6 (3) |
C10B—N9B—C5B—C4B | 19.4 (5) | C16B—C7B—C8B—N9B | −143.9 (3) |
C16B—N19B—C20B—C21B | −44.0 (4) | C16B—C7B—C17B—C18B | −41.5 (3) |
C18B—N19B—C20B—C21B | 78.1 (4) | C6B—C7B—C8B—N9B | −18.5 (3) |
C20B—N19B—C18B—C17B | −139.3 (3) | C6B—C7B—C16B—N19B | 154.2 (3) |
C18B—N19B—C16B—C7B | −12.8 (3) | C6B—C7B—C16B—C15B | −84.3 (3) |
C20B—N19B—C16B—C15B | −12.1 (4) | C8B—C7B—C16B—N19B | −87.0 (3) |
C16B—N19B—C18B—C17B | −13.5 (4) | C6B—C7B—C8B—C13B | 98.4 (3) |
C20B—N19B—C16B—C7B | 112.5 (3) | C8B—C7B—C16B—C15B | 34.5 (4) |
C18B—N19B—C16B—C15B | −137.4 (3) | C16B—C7B—C8B—C13B | −27.0 (4) |
C2A—C1A—C6A—C7A | −177.1 (3) | C17B—C7B—C8B—C13B | −141.6 (3) |
C2A—C1A—C6A—C5A | 0.4 (5) | C17B—C7B—C8B—N9B | 101.5 (3) |
C6A—C1A—C2A—C3A | 3.7 (5) | N9B—C8B—C13B—C14B | 156.7 (3) |
C6A—C1A—C2A—O2A | −177.5 (3) | N9B—C8B—C13B—C12B | −70.7 (3) |
O2A—C2A—C3A—O3A | −2.5 (4) | C7B—C8B—C13B—C14B | 40.8 (4) |
C1A—C2A—C3A—C4A | −4.7 (5) | C7B—C8B—C13B—C12B | 173.4 (3) |
O2A—C2A—C3A—C4A | 176.4 (3) | O25B—C10B—C11B—C12B | 143.4 (3) |
C1A—C2A—C3A—O3A | 176.5 (3) | N9B—C10B—C11B—C12B | −38.0 (4) |
C2A—C3A—C4A—C5A | 1.4 (5) | C10B—C11B—C12B—C13B | 12.0 (4) |
O3A—C3A—C4A—C5A | −179.9 (3) | C10B—C11B—C12B—O24B | 135.3 (3) |
C3A—C4A—C5A—N9A | −174.9 (3) | C11B—C12B—C13B—C14B | 169.6 (3) |
C3A—C4A—C5A—C6A | 2.9 (5) | C11B—C12B—C13B—C8B | 40.3 (4) |
N9A—C5A—C6A—C7A | −7.8 (4) | O24B—C12B—C13B—C14B | 52.6 (4) |
N9A—C5A—C6A—C1A | 174.3 (3) | O24B—C12B—C13B—C8B | −76.7 (3) |
C4A—C5A—C6A—C7A | 174.1 (3) | C8B—C13B—C14B—C15B | −60.5 (4) |
C4A—C5A—C6A—C1A | −3.8 (5) | C8B—C13B—C14B—C21B | 60.1 (4) |
C5A—C6A—C7A—C16A | 140.8 (3) | C12B—C13B—C14B—C15B | 172.5 (3) |
C1A—C6A—C7A—C16A | −41.6 (5) | C12B—C13B—C14B—C21B | −67.0 (4) |
C5A—C6A—C7A—C17A | −102.9 (3) | C13B—C14B—C15B—C16B | 67.2 (3) |
C1A—C6A—C7A—C17A | 74.8 (5) | C15B—C14B—C21B—C20B | −1.2 (4) |
C5A—C6A—C7A—C8A | 16.1 (4) | C15B—C14B—C21B—C22B | −178.3 (3) |
C1A—C6A—C7A—C8A | −166.2 (3) | C13B—C14B—C21B—C22B | 62.3 (5) |
C17A—C7A—C16A—N19A | 31.4 (3) | C13B—C14B—C21B—C20B | −120.7 (3) |
C8A—C7A—C16A—C15A | 32.6 (4) | C21B—C14B—C15B—C16B | −56.2 (3) |
C16A—C7A—C8A—N9A | −142.3 (3) | C14B—C15B—C16B—N19B | 63.7 (3) |
C17A—C7A—C16A—C15A | 153.0 (3) | C14B—C15B—C16B—C7B | −55.3 (3) |
C6A—C7A—C8A—C13A | 99.5 (3) | C7B—C17B—C18B—N19B | 34.3 (3) |
C6A—C7A—C16A—C15A | −85.2 (4) | N19B—C20B—C21B—C14B | 51.8 (4) |
C17A—C7A—C8A—C13A | −140.5 (3) | N19B—C20B—C21B—C22B | −131.2 (4) |
C8A—C7A—C16A—N19A | −88.9 (3) | C14B—C21B—C22B—C23B | −4.3 (5) |
C6A—C7A—C8A—N9A | −17.8 (3) | C20B—C21B—C22B—C23B | 178.8 (3) |
C16A—C7A—C17A—C18A | −40.6 (3) | C21B—C22B—C23B—O24B | −66.2 (4) |
C8A—C7A—C17A—C18A | 82.2 (3) | O11C—C1C—C2C—O21C | 1.1 (4) |
C16A—C7A—C8A—C13A | −25.0 (4) | O11C—C1C—C2C—C3C | 125.0 (3) |
C6A—C7A—C16A—N19A | 153.2 (3) | O12C—C1C—C2C—O21C | 179.3 (3) |
C17A—C7A—C8A—N9A | 102.2 (3) | O12C—C1C—C2C—C3C | −56.8 (4) |
C6A—C7A—C17A—C18A | −163.9 (3) | C1C—C2C—C3C—C4C | −62.9 (4) |
C7A—C8A—C13A—C12A | 172.3 (3) | O21C—C2C—C3C—C4C | 62.7 (4) |
C7A—C8A—C13A—C14A | 40.2 (4) | C2C—C3C—C4C—O41C | −169.1 (3) |
N9A—C8A—C13A—C14A | 156.6 (3) | C2C—C3C—C4C—O42C | 11.8 (5) |
N9A—C8A—C13A—C12A | −71.3 (3) | O11D—C1D—C2D—O21D | 6.6 (4) |
O25A—C10A—C11A—C12A | 147.4 (4) | O12D—C1D—C2D—O21D | −175.7 (3) |
N9A—C10A—C11A—C12A | −34.4 (5) | O12D—C1D—C2D—C3D | −54.2 (4) |
C10A—C11A—C12A—O24A | 130.4 (3) | O11D—C1D—C2D—C3D | 128.1 (3) |
C10A—C11A—C12A—C13A | 7.4 (4) | C1D—C2D—C3D—C4D | −57.5 (4) |
O24A—C12A—C13A—C8A | −73.7 (3) | O21D—C2D—C3D—C4D | 66.7 (4) |
C11A—C12A—C13A—C14A | 171.8 (3) | C2D—C3D—C4D—O42D | 9.0 (5) |
C11A—C12A—C13A—C8A | 43.4 (4) | C2D—C3D—C4D—O41D | −171.8 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N19A—H19A···O11C | 0.99 | 1.86 | 2.742 (4) | 147 |
N19A—H19A···O21C | 0.99 | 2.36 | 3.117 (4) | 133 |
N19A—H19A···O42C | 0.99 | 2.59 | 3.097 (4) | 112 |
N19B—H19B···O11Di | 0.92 | 1.89 | 2.759 (4) | 156 |
N19B—H19B···O21Di | 0.92 | 2.51 | 3.129 (4) | 124 |
O21C—H21C···O7W | 0.90 | 1.79 | 2.689 (4) | 180 |
O21D—H21D···O9Wii | 0.90 | 1.82 | 2.719 (4) | 180 |
O41C—H41C···O25Biii | 0.93 | 1.73 | 2.645 (3) | 168 |
O41D—H41D···O25Aiv | 0.89 | 1.75 | 2.647 (3) | 179 |
O1W—H11W···O7W | 0.90 | 1.93 | 2.826 (4) | 176 |
O1W—H12W···O6Wv | 0.91 | 1.91 | 2.811 (4) | 171 |
O2W—H21W···O12D | 0.84 | 1.90 | 2.731 (4) | 171 |
O2W—H22W···O12Cvi | 0.89 | 1.83 | 2.721 (4) | 175 |
O3W—H31W···O8Wv | 0.93 | 1.82 | 2.743 (5) | 173 |
O3W—H32W···O1W | 0.86 | 1.96 | 2.805 (4) | 167 |
O4W—H41W···O3Wvi | 0.90 | 1.95 | 2.845 (4) | 179 |
O4W—H42W···O2W | 0.90 | 1.82 | 2.712 (5) | 180 |
O5W—H51W···O11C | 0.90 | 1.76 | 2.659 (4) | 179 |
O5W—H52W···O3Wii | 0.85 | 2.06 | 2.880 (4) | 164 |
O6W—H61W···O8W | 0.91 | 1.90 | 2.808 (4) | 179 |
O6W—H62W···O21D | 0.91 | 1.89 | 2.799 (5) | 179 |
O7W—H71W···O12D | 0.90 | 1.76 | 2.664 (4) | 179 |
O7W—H72W···O9W | 0.87 | 1.92 | 2.764 (4) | 161 |
O8W—H81W···O11Diii | 0.94 | 1.76 | 2.690 (4) | 168 |
O8W—H82W···O12C | 0.86 | 1.92 | 2.768 (4) | 169 |
O9W—H91W···O5Wv | 0.90 | 1.84 | 2.738 (4) | 179 |
O9W—H92W···O4W | 0.92 | 1.76 | 2.653 (4) | 162 |
O10W—H10W···O5Wv | 0.91 | 1.92 | 2.795 (5) | 160 |
O10W—H13W···O21C | 0.90 | 1.94 | 2.844 (4) | 180 |
C2D—H2D···O11C | 0.98 | 2.50 | 3.470 (4) | 173 |
C4A—H4A···O25A | 0.93 | 2.45 | 2.974 (4) | 116 |
C4A—H4A···O41Dvii | 0.93 | 2.58 | 3.429 (4) | 152 |
C4B—H4B···O25B | 0.93 | 2.46 | 2.974 (4) | 115 |
C4B—H4B···O41Cvi | 0.93 | 2.60 | 3.461 (4) | 154 |
C12B—H12B···O42Dvii | 0.98 | 2.58 | 3.473 (5) | 152 |
C14B—H14B···O12Dvii | 0.98 | 2.56 | 3.452 (4) | 151 |
C16B—H16B···O21Di | 0.98 | 2.54 | 3.120 (4) | 118 |
C22B—H22B···O1Wviii | 0.93 | 2.49 | 3.408 (5) | 169 |
C17A—H31A···O42C | 0.97 | 2.40 | 3.106 (5) | 129 |
C17B—H31B···O42Di | 0.97 | 2.44 | 3.147 (5) | 130 |
C3D—H31D···O7W | 0.97 | 2.60 | 3.459 (5) | 148 |
C17A—H32A···O2Bii | 0.97 | 2.55 | 3.471 (4) | 159 |
C17B—H32B···O2Avi | 0.97 | 2.46 | 3.386 (4) | 160 |
Symmetry codes: (i) x+1, y, z+1; (ii) x−1, y, z; (iii) x, y−1, z; (iv) x, y, z−1; (v) x+1, y, z; (vi) x, y+1, z; (vii) x, y, z+1; (viii) x, y+1, z+1. |
(II) 2,3-dimethoxy-10-oxostrychnidinium hydrogen 2(
R),3(
R)-tartrate
top
Crystal data top
C23H27N2O4+·C4H5O6− | Dx = 1.516 Mg m−3 |
Mr = 544.55 | Melting point = 522.4–523.6 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P2ac 2ab | Cell parameters from 4092 reflections |
a = 12.2719 (7) Å | θ = 2.7–24.0° |
b = 13.5151 (8) Å | µ = 0.12 mm−1 |
c = 14.3814 (9) Å | T = 130 K |
V = 2385.2 (2) Å3 | Block, colourless |
Z = 4 | 0.45 × 0.25 × 0.20 mm |
F(000) = 1152 | |
Data collection top
Bruker CCD area-detector diffractometer | 2514 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.047 |
Graphite monochromator | θmax = 27.5°, θmin = 2.1° |
ϕ and ω scans | h = −12→15 |
15054 measured reflections | k = −17→17 |
3088 independent reflections | l = −18→15 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.91 | w = 1/[σ2(Fo2) + (0.0258P)2] where P = (Fo2 + 2Fc2)/3 |
3088 reflections | (Δ/σ)max = 0.001 |
368 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
Crystal data top
C23H27N2O4+·C4H5O6− | V = 2385.2 (2) Å3 |
Mr = 544.55 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 12.2719 (7) Å | µ = 0.12 mm−1 |
b = 13.5151 (8) Å | T = 130 K |
c = 14.3814 (9) Å | 0.45 × 0.25 × 0.20 mm |
Data collection top
Bruker CCD area-detector diffractometer | 2514 reflections with I > 2σ(I) |
15054 measured reflections | Rint = 0.047 |
3088 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.91 | Δρmax = 0.24 e Å−3 |
3088 reflections | Δρmin = −0.22 e Å−3 |
368 parameters | |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | |
O11T | 0.20311 (11) | 0.87831 (10) | 0.59809 (9) | 0.0276 (5) | |
O12T | 0.32175 (11) | 0.89712 (11) | 0.71420 (10) | 0.0318 (5) | |
O21T | 0.35075 (12) | 0.79171 (11) | 0.48663 (9) | 0.0289 (5) | |
O31T | 0.41522 (13) | 0.68629 (10) | 0.65222 (11) | 0.0324 (5) | |
O41T | 0.57614 (11) | 0.65356 (10) | 0.53827 (10) | 0.0265 (5) | |
O42T | 0.62478 (11) | 0.81248 (10) | 0.52828 (10) | 0.0308 (5) | |
C1T | 0.29873 (16) | 0.87445 (14) | 0.63389 (13) | 0.0219 (6) | |
C2T | 0.38948 (15) | 0.83956 (14) | 0.56842 (13) | 0.0224 (6) | |
C3T | 0.46886 (16) | 0.77278 (14) | 0.62095 (14) | 0.0227 (6) | |
C4T | 0.56454 (16) | 0.74840 (15) | 0.55777 (14) | 0.0229 (7) | |
O2 | 0.89613 (10) | 0.60666 (9) | −0.04769 (9) | 0.0215 (4) | |
O3 | 0.78668 (10) | 0.63333 (10) | −0.19918 (8) | 0.0216 (4) | |
O24 | 0.18898 (10) | 0.60648 (9) | 0.12600 (9) | 0.0202 (4) | |
O25 | 0.37561 (10) | 0.65377 (10) | −0.15612 (9) | 0.0258 (5) | |
N9 | 0.44948 (12) | 0.65298 (11) | −0.01072 (10) | 0.0162 (5) | |
N19 | 0.52969 (13) | 0.60273 (11) | 0.29886 (11) | 0.0173 (5) | |
C1 | 0.73230 (14) | 0.61302 (13) | 0.04751 (13) | 0.0174 (6) | |
C2 | 0.78570 (14) | 0.61606 (13) | −0.03691 (13) | 0.0167 (6) | |
C3 | 0.72579 (15) | 0.63132 (13) | −0.11936 (13) | 0.0184 (6) | |
C4 | 0.61416 (15) | 0.64446 (13) | −0.11761 (12) | 0.0176 (6) | |
C5 | 0.56242 (14) | 0.64219 (12) | −0.03121 (13) | 0.0160 (6) | |
C6 | 0.62003 (15) | 0.62646 (13) | 0.04969 (12) | 0.0157 (6) | |
C7 | 0.54687 (14) | 0.63432 (13) | 0.13353 (12) | 0.0156 (6) | |
C8 | 0.43118 (14) | 0.63133 (13) | 0.08910 (12) | 0.0153 (5) | |
C10 | 0.36525 (15) | 0.64392 (13) | −0.07155 (13) | 0.0180 (6) | |
C11 | 0.25541 (14) | 0.62223 (13) | −0.02726 (13) | 0.0187 (6) | |
C12 | 0.25361 (15) | 0.55382 (13) | 0.05908 (13) | 0.0181 (6) | |
C13 | 0.36965 (15) | 0.53302 (13) | 0.09238 (13) | 0.0158 (6) | |
C14 | 0.38522 (15) | 0.47764 (13) | 0.18471 (13) | 0.0180 (6) | |
C15 | 0.50837 (15) | 0.45736 (13) | 0.19249 (14) | 0.0179 (6) | |
C16 | 0.56691 (15) | 0.55471 (13) | 0.20753 (12) | 0.0162 (6) | |
C17 | 0.56577 (15) | 0.73029 (13) | 0.18874 (12) | 0.0165 (6) | |
C18 | 0.50801 (16) | 0.71061 (13) | 0.27978 (13) | 0.0201 (6) | |
C20 | 0.43353 (15) | 0.55163 (14) | 0.34309 (13) | 0.0196 (6) | |
C21 | 0.34706 (15) | 0.53348 (13) | 0.27118 (13) | 0.0178 (6) | |
C22 | 0.24538 (16) | 0.56396 (14) | 0.28213 (13) | 0.0209 (6) | |
C23 | 0.16108 (15) | 0.55040 (15) | 0.20745 (14) | 0.0235 (7) | |
C25 | 0.95864 (15) | 0.59697 (15) | 0.03671 (14) | 0.0233 (6) | |
C26 | 0.72647 (16) | 0.64363 (16) | −0.28402 (13) | 0.0253 (7) | |
H2T | 0.430900 | 0.899600 | 0.548200 | 0.0270* | |
H3T | 0.496800 | 0.809600 | 0.676300 | 0.0270* | |
H21T | 0.288 (2) | 0.760 (2) | 0.5054 (19) | 0.077 (10)* | |
H31T | 0.398 (2) | 0.6981 (19) | 0.710 (2) | 0.072 (9)* | |
H41T | 0.6385 (18) | 0.6495 (18) | 0.4954 (17) | 0.063 (8)* | |
H1 | 0.771000 | 0.600700 | 0.102400 | 0.0210* | |
H4 | 0.574800 | 0.654500 | −0.172100 | 0.0210* | |
H8 | 0.385000 | 0.684600 | 0.117000 | 0.0180* | |
H11A | 0.208000 | 0.592200 | −0.075300 | 0.0220* | |
H11B | 0.222000 | 0.686200 | −0.009400 | 0.0220* | |
H12 | 0.216900 | 0.490100 | 0.042900 | 0.0220* | |
H13 | 0.403600 | 0.490300 | 0.043500 | 0.0190* | |
H14 | 0.345800 | 0.413000 | 0.181300 | 0.0220* | |
H15A | 0.522800 | 0.412200 | 0.245300 | 0.0210* | |
H15B | 0.535000 | 0.425500 | 0.134800 | 0.0210* | |
H16 | 0.647000 | 0.541600 | 0.211400 | 0.0190* | |
H17A | 0.644500 | 0.742300 | 0.198700 | 0.0200* | |
H17B | 0.533700 | 0.788000 | 0.156300 | 0.0200* | |
H18A | 0.537900 | 0.752700 | 0.330000 | 0.0240* | |
H18B | 0.428900 | 0.723400 | 0.274000 | 0.0240* | |
H19 | 0.5913 (15) | 0.6029 (13) | 0.3391 (13) | 0.020 (5)* | |
H20A | 0.457100 | 0.487900 | 0.370400 | 0.0240* | |
H20B | 0.403700 | 0.593400 | 0.393600 | 0.0240* | |
H22 | 0.224800 | 0.594600 | 0.337500 | 0.0250* | |
H23A | 0.155700 | 0.479400 | 0.191100 | 0.0280* | |
H23B | 0.089100 | 0.572200 | 0.230900 | 0.0280* | |
H25A | 0.940400 | 0.534200 | 0.067100 | 0.0350* | |
H25B | 0.941400 | 0.652000 | 0.078600 | 0.0350* | |
H25C | 1.036500 | 0.598100 | 0.021800 | 0.0350* | |
H26A | 0.688900 | 0.707600 | −0.284400 | 0.0380* | |
H26B | 0.672800 | 0.590200 | −0.288700 | 0.0380* | |
H26C | 0.776600 | 0.640100 | −0.337000 | 0.0380* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O11T | 0.0199 (8) | 0.0396 (9) | 0.0234 (8) | −0.0014 (6) | 0.0037 (6) | −0.0041 (7) |
O12T | 0.0333 (9) | 0.0412 (9) | 0.0209 (8) | 0.0037 (7) | −0.0007 (6) | −0.0079 (7) |
O21T | 0.0274 (9) | 0.0432 (9) | 0.0160 (8) | 0.0040 (7) | 0.0003 (6) | −0.0029 (7) |
O31T | 0.0491 (10) | 0.0261 (8) | 0.0219 (9) | −0.0014 (7) | 0.0109 (7) | 0.0036 (7) |
O41T | 0.0319 (9) | 0.0220 (8) | 0.0256 (9) | 0.0049 (6) | 0.0043 (7) | −0.0025 (6) |
O42T | 0.0290 (8) | 0.0268 (8) | 0.0367 (9) | −0.0018 (7) | 0.0044 (7) | 0.0019 (7) |
C1T | 0.0259 (12) | 0.0199 (10) | 0.0200 (11) | −0.0029 (9) | 0.0012 (9) | −0.0005 (8) |
C2T | 0.0235 (11) | 0.0254 (11) | 0.0182 (11) | −0.0021 (9) | 0.0006 (8) | 0.0006 (9) |
C3T | 0.0297 (12) | 0.0211 (10) | 0.0174 (11) | −0.0007 (9) | −0.0005 (9) | −0.0010 (9) |
C4T | 0.0267 (12) | 0.0251 (11) | 0.0168 (11) | 0.0027 (9) | −0.0102 (9) | 0.0010 (9) |
O2 | 0.0136 (7) | 0.0325 (8) | 0.0184 (7) | 0.0017 (6) | −0.0017 (5) | −0.0005 (6) |
O3 | 0.0157 (7) | 0.0354 (8) | 0.0136 (7) | 0.0031 (6) | 0.0022 (5) | 0.0003 (6) |
O24 | 0.0194 (7) | 0.0244 (7) | 0.0169 (7) | 0.0032 (6) | 0.0013 (6) | 0.0012 (6) |
O25 | 0.0247 (8) | 0.0367 (8) | 0.0160 (8) | −0.0026 (6) | −0.0017 (6) | 0.0031 (6) |
N9 | 0.0153 (8) | 0.0191 (8) | 0.0141 (8) | −0.0015 (7) | 0.0003 (6) | 0.0020 (7) |
N19 | 0.0174 (9) | 0.0210 (9) | 0.0134 (9) | 0.0006 (7) | 0.0004 (7) | 0.0020 (7) |
C1 | 0.0176 (10) | 0.0167 (10) | 0.0180 (10) | −0.0005 (8) | −0.0037 (8) | 0.0017 (8) |
C2 | 0.0149 (10) | 0.0149 (10) | 0.0202 (11) | 0.0004 (7) | −0.0002 (8) | −0.0008 (8) |
C3 | 0.0229 (11) | 0.0169 (10) | 0.0153 (10) | 0.0001 (8) | 0.0017 (8) | −0.0015 (8) |
C4 | 0.0192 (10) | 0.0205 (10) | 0.0132 (10) | 0.0003 (8) | −0.0011 (8) | 0.0015 (8) |
C5 | 0.0169 (10) | 0.0117 (9) | 0.0194 (10) | 0.0011 (8) | 0.0001 (8) | 0.0009 (8) |
C6 | 0.0187 (10) | 0.0137 (9) | 0.0148 (10) | −0.0019 (8) | 0.0002 (8) | −0.0003 (8) |
C7 | 0.0154 (10) | 0.0158 (9) | 0.0156 (10) | −0.0012 (8) | 0.0022 (7) | −0.0008 (8) |
C8 | 0.0182 (10) | 0.0160 (9) | 0.0116 (9) | 0.0040 (8) | 0.0016 (7) | 0.0012 (8) |
C10 | 0.0219 (11) | 0.0165 (9) | 0.0157 (10) | 0.0020 (8) | −0.0012 (8) | 0.0024 (8) |
C11 | 0.0146 (10) | 0.0208 (10) | 0.0208 (11) | 0.0002 (8) | −0.0039 (8) | −0.0006 (9) |
C12 | 0.0170 (10) | 0.0183 (10) | 0.0189 (11) | −0.0020 (8) | −0.0015 (8) | −0.0017 (8) |
C13 | 0.0161 (10) | 0.0157 (9) | 0.0157 (10) | 0.0009 (8) | 0.0004 (8) | −0.0020 (8) |
C14 | 0.0186 (11) | 0.0145 (9) | 0.0208 (11) | −0.0025 (8) | −0.0006 (8) | 0.0007 (8) |
C15 | 0.0192 (11) | 0.0165 (10) | 0.0180 (11) | 0.0006 (8) | −0.0021 (8) | 0.0018 (8) |
C16 | 0.0165 (10) | 0.0198 (10) | 0.0124 (10) | 0.0033 (8) | 0.0020 (8) | −0.0009 (8) |
C17 | 0.0180 (10) | 0.0171 (10) | 0.0144 (10) | −0.0022 (8) | −0.0016 (8) | 0.0001 (8) |
C18 | 0.0257 (11) | 0.0171 (10) | 0.0176 (11) | 0.0002 (8) | 0.0003 (8) | −0.0022 (8) |
C20 | 0.0208 (11) | 0.0226 (10) | 0.0155 (11) | 0.0006 (8) | 0.0047 (8) | 0.0019 (8) |
C21 | 0.0213 (12) | 0.0163 (10) | 0.0157 (10) | −0.0029 (8) | 0.0022 (8) | 0.0052 (8) |
C22 | 0.0253 (12) | 0.0224 (10) | 0.0149 (11) | −0.0025 (9) | 0.0045 (8) | 0.0033 (8) |
C23 | 0.0169 (11) | 0.0328 (12) | 0.0209 (11) | 0.0003 (9) | 0.0049 (8) | 0.0028 (9) |
C25 | 0.0164 (11) | 0.0314 (11) | 0.0220 (11) | 0.0009 (9) | −0.0042 (8) | −0.0021 (10) |
C26 | 0.0240 (12) | 0.0376 (12) | 0.0143 (10) | 0.0035 (9) | 0.0013 (8) | 0.0026 (10) |
Geometric parameters (Å, º) top
O11T—C1T | 1.282 (2) | C8—C13 | 1.529 (2) |
O12T—C1T | 1.228 (2) | C10—C11 | 1.519 (3) |
O21T—C2T | 1.424 (2) | C11—C12 | 1.548 (3) |
O31T—C3T | 1.415 (2) | C12—C13 | 1.528 (3) |
O41T—C4T | 1.320 (2) | C13—C14 | 1.536 (3) |
O42T—C4T | 1.215 (2) | C14—C21 | 1.528 (3) |
O21T—H21T | 0.92 (3) | C14—C15 | 1.540 (3) |
O31T—H31T | 0.87 (3) | C15—C16 | 1.515 (3) |
O41T—H41T | 0.98 (2) | C17—C18 | 1.512 (3) |
O2—C2 | 1.370 (2) | C20—C21 | 1.502 (3) |
O2—C25 | 1.442 (2) | C21—C22 | 1.323 (3) |
O24—C12 | 1.436 (2) | C22—C23 | 1.502 (3) |
O24—C23 | 1.437 (2) | C1—H1 | 0.9300 |
O25—C10 | 1.230 (2) | C4—H4 | 0.9300 |
O3—C26 | 1.433 (2) | C8—H8 | 1.0002 |
O3—C3 | 1.370 (2) | C11—H11A | 0.9902 |
N9—C5 | 1.424 (2) | C11—H11B | 0.9907 |
N9—C8 | 1.482 (2) | C12—H12 | 0.9994 |
N9—C10 | 1.360 (2) | C13—H13 | 1.0005 |
N19—C20 | 1.508 (2) | C14—H14 | 0.9998 |
N19—C16 | 1.535 (2) | C15—H15A | 0.9903 |
N19—C18 | 1.507 (2) | C15—H15B | 0.9902 |
N19—H19 | 0.952 (19) | C16—H16 | 1.0002 |
C1T—C2T | 1.533 (3) | C17—H17A | 0.9901 |
C2T—C3T | 1.528 (3) | C17—H17B | 0.9904 |
C3T—C4T | 1.521 (3) | C18—H18A | 0.9898 |
C2T—H2T | 1.0007 | C18—H18B | 0.9896 |
C3T—H3T | 0.9994 | C20—H20A | 0.9898 |
C1—C6 | 1.390 (3) | C20—H20B | 0.9901 |
C1—C2 | 1.380 (3) | C22—H22 | 0.9300 |
C2—C3 | 1.410 (3) | C23—H23A | 0.9902 |
C3—C4 | 1.382 (3) | C23—H23B | 0.9904 |
C4—C5 | 1.396 (3) | C25—H25A | 0.9802 |
C5—C6 | 1.378 (3) | C25—H25B | 0.9802 |
C6—C7 | 1.507 (2) | C25—H25C | 0.9794 |
C7—C16 | 1.533 (2) | C26—H26A | 0.9798 |
C7—C17 | 1.538 (2) | C26—H26B | 0.9797 |
C7—C8 | 1.557 (2) | C26—H26C | 0.9804 |
| | | |
C2T—O21T—H21T | 104.4 (17) | C7—C16—C15 | 115.75 (15) |
C3T—O31T—H31T | 105.3 (17) | C7—C17—C18 | 103.17 (14) |
C4T—O41T—H41T | 105.7 (14) | N19—C18—C17 | 104.18 (14) |
C2—O2—C25 | 116.07 (14) | N19—C20—C21 | 109.71 (15) |
C12—O24—C23 | 114.62 (13) | C14—C21—C22 | 122.65 (17) |
C3—O3—C26 | 115.73 (14) | C14—C21—C20 | 115.12 (15) |
C5—N9—C8 | 109.12 (14) | C20—C21—C22 | 122.23 (17) |
C5—N9—C10 | 126.68 (15) | C21—C22—C23 | 121.75 (17) |
C8—N9—C10 | 119.35 (15) | O24—C23—C22 | 110.76 (15) |
C18—N19—C20 | 112.44 (14) | C2—C1—H1 | 120.48 |
C16—N19—C20 | 113.59 (14) | C6—C1—H1 | 120.40 |
C16—N19—C18 | 107.81 (14) | C3—C4—H4 | 121.16 |
C20—N19—H19 | 111.5 (11) | C5—C4—H4 | 121.16 |
C18—N19—H19 | 104.4 (11) | N9—C8—H8 | 109.41 |
C16—N19—H19 | 106.6 (11) | C7—C8—H8 | 109.47 |
O12T—C1T—C2T | 119.17 (17) | C13—C8—H8 | 109.47 |
O11T—C1T—C2T | 115.51 (16) | C10—C11—H11A | 107.93 |
O11T—C1T—O12T | 125.31 (18) | C10—C11—H11B | 107.91 |
O21T—C2T—C3T | 110.67 (15) | C12—C11—H11A | 107.84 |
C1T—C2T—C3T | 109.95 (15) | C12—C11—H11B | 107.90 |
O21T—C2T—C1T | 113.87 (15) | H11A—C11—H11B | 107.18 |
O31T—C3T—C2T | 110.40 (16) | O24—C12—H12 | 109.52 |
C2T—C3T—C4T | 108.96 (16) | C11—C12—H12 | 109.53 |
O31T—C3T—C4T | 111.72 (16) | C13—C12—H12 | 109.54 |
O41T—C4T—C3T | 114.88 (17) | C8—C13—H13 | 105.91 |
O41T—C4T—O42T | 123.53 (18) | C12—C13—H13 | 105.90 |
O42T—C4T—C3T | 121.59 (18) | C14—C13—H13 | 105.92 |
C3T—C2T—H2T | 107.39 | C13—C14—H14 | 108.85 |
C1T—C2T—H2T | 107.34 | C15—C14—H14 | 108.84 |
O21T—C2T—H2T | 107.32 | C21—C14—H14 | 108.85 |
C4T—C3T—H3T | 108.59 | C14—C15—H15A | 109.93 |
C2T—C3T—H3T | 108.57 | C14—C15—H15B | 109.90 |
O31T—C3T—H3T | 108.53 | C16—C15—H15A | 109.94 |
C2—C1—C6 | 119.11 (17) | C16—C15—H15B | 109.93 |
O2—C2—C1 | 124.50 (16) | H15A—C15—H15B | 108.39 |
C1—C2—C3 | 119.76 (16) | N19—C16—H16 | 108.65 |
O2—C2—C3 | 115.73 (16) | C7—C16—H16 | 108.70 |
C2—C3—C4 | 121.36 (17) | C15—C16—H16 | 108.67 |
O3—C3—C4 | 123.61 (16) | C7—C17—H17A | 111.10 |
O3—C3—C2 | 115.03 (16) | C7—C17—H17B | 111.16 |
C3—C4—C5 | 117.68 (16) | C18—C17—H17A | 111.16 |
N9—C5—C4 | 128.65 (16) | C18—C17—H17B | 111.10 |
N9—C5—C6 | 109.90 (16) | H17A—C17—H17B | 109.08 |
C4—C5—C6 | 121.44 (16) | N19—C18—H18A | 110.96 |
C5—C6—C7 | 111.04 (16) | N19—C18—H18B | 110.94 |
C1—C6—C5 | 120.64 (17) | C17—C18—H18A | 110.91 |
C1—C6—C7 | 128.15 (16) | C17—C18—H18B | 110.88 |
C6—C7—C8 | 102.30 (14) | H18A—C18—H18B | 108.93 |
C6—C7—C16 | 114.22 (15) | N19—C20—H20A | 109.71 |
C6—C7—C17 | 112.49 (14) | N19—C20—H20B | 109.73 |
C16—C7—C17 | 102.08 (14) | C21—C20—H20A | 109.73 |
C8—C7—C17 | 111.78 (14) | C21—C20—H20B | 109.70 |
C8—C7—C16 | 114.38 (14) | H20A—C20—H20B | 108.24 |
C7—C8—C13 | 117.39 (15) | C21—C22—H22 | 119.11 |
N9—C8—C13 | 106.04 (14) | C23—C22—H22 | 119.15 |
N9—C8—C7 | 104.72 (13) | O24—C23—H23A | 109.48 |
O25—C10—N9 | 123.22 (17) | O24—C23—H23B | 109.47 |
O25—C10—C11 | 121.81 (16) | C22—C23—H23A | 109.50 |
N9—C10—C11 | 114.97 (16) | C22—C23—H23B | 109.54 |
C10—C11—C12 | 117.65 (15) | H23A—C23—H23B | 108.04 |
C11—C12—C13 | 110.35 (15) | O2—C25—H25A | 109.42 |
O24—C12—C11 | 104.44 (14) | O2—C25—H25B | 109.49 |
O24—C12—C13 | 113.31 (15) | O2—C25—H25C | 109.47 |
C8—C13—C12 | 106.90 (14) | H25A—C25—H25B | 109.47 |
C8—C13—C14 | 112.87 (15) | H25A—C25—H25C | 109.51 |
C12—C13—C14 | 118.45 (15) | H25B—C25—H25C | 109.47 |
C15—C14—C21 | 109.24 (15) | O3—C26—H26A | 109.45 |
C13—C14—C15 | 105.76 (15) | O3—C26—H26B | 109.48 |
C13—C14—C21 | 115.13 (15) | O3—C26—H26C | 109.47 |
C14—C15—C16 | 108.74 (14) | H26A—C26—H26B | 109.49 |
N19—C16—C7 | 104.45 (14) | H26A—C26—H26C | 109.50 |
N19—C16—C15 | 110.39 (14) | H26B—C26—H26C | 109.43 |
| | | |
C25—O2—C2—C3 | 176.42 (15) | N9—C5—C6—C7 | −4.8 (2) |
C25—O2—C2—C1 | −2.5 (2) | C4—C5—C6—C1 | 0.5 (3) |
C12—O24—C23—C22 | 90.78 (18) | C5—C6—C7—C17 | −106.56 (17) |
C23—O24—C12—C13 | −69.28 (18) | C1—C6—C7—C8 | −171.21 (18) |
C23—O24—C12—C11 | 170.58 (14) | C5—C6—C7—C16 | 137.68 (16) |
C26—O3—C3—C4 | −4.0 (2) | C5—C6—C7—C8 | 13.53 (19) |
C26—O3—C3—C2 | 176.89 (16) | C1—C6—C7—C17 | 68.7 (2) |
C5—N9—C10—C11 | 158.84 (16) | C1—C6—C7—C16 | −47.1 (2) |
C10—N9—C5—C6 | −161.74 (17) | C17—C7—C16—N19 | 31.70 (17) |
C8—N9—C5—C6 | −6.89 (19) | C6—C7—C8—C13 | 100.60 (17) |
C8—N9—C10—O25 | −174.74 (16) | C6—C7—C16—C15 | −85.03 (19) |
C5—N9—C8—C13 | −109.79 (15) | C16—C7—C8—C13 | −23.4 (2) |
C5—N9—C10—O25 | −22.2 (3) | C17—C7—C8—C13 | −138.81 (16) |
C10—N9—C5—C4 | 17.3 (3) | C16—C7—C17—C18 | −42.96 (17) |
C8—N9—C5—C4 | 172.12 (17) | C6—C7—C8—N9 | −16.64 (17) |
C8—N9—C10—C11 | 6.3 (2) | C8—C7—C16—C15 | 32.4 (2) |
C10—N9—C8—C13 | 47.2 (2) | C8—C7—C16—N19 | −89.21 (17) |
C5—N9—C8—C7 | 14.99 (17) | C8—C7—C17—C18 | 79.73 (17) |
C10—N9—C8—C7 | 171.97 (15) | C6—C7—C17—C18 | −165.83 (15) |
C18—N19—C20—C21 | 75.30 (18) | C17—C7—C8—N9 | 103.94 (16) |
C20—N19—C16—C7 | 115.98 (15) | C6—C7—C16—N19 | 153.38 (14) |
C16—N19—C20—C21 | −47.48 (19) | C16—C7—C8—N9 | −140.69 (14) |
C20—N19—C16—C15 | −9.1 (2) | C17—C7—C16—C15 | 153.28 (15) |
C18—N19—C16—C15 | −134.37 (15) | N9—C8—C13—C12 | −72.35 (17) |
C16—N19—C18—C17 | −17.37 (18) | C7—C8—C13—C14 | 39.2 (2) |
C20—N19—C18—C17 | −143.35 (15) | C7—C8—C13—C12 | 171.12 (15) |
C18—N19—C16—C7 | −9.31 (18) | N9—C8—C13—C14 | 155.71 (14) |
O11T—C1T—C2T—O21T | −16.1 (2) | N9—C10—C11—C12 | −36.3 (2) |
O12T—C1T—C2T—C3T | 39.8 (2) | O25—C10—C11—C12 | 144.71 (17) |
O12T—C1T—C2T—O21T | 164.62 (17) | C10—C11—C12—O24 | 130.72 (16) |
O11T—C1T—C2T—C3T | −140.97 (17) | C10—C11—C12—C13 | 8.6 (2) |
C1T—C2T—C3T—C4T | −173.82 (15) | O24—C12—C13—C14 | 55.5 (2) |
O21T—C2T—C3T—O31T | −63.5 (2) | C11—C12—C13—C14 | 172.19 (15) |
O21T—C2T—C3T—C4T | 59.5 (2) | C11—C12—C13—C8 | 43.40 (19) |
C1T—C2T—C3T—O31T | 63.1 (2) | O24—C12—C13—C8 | −73.32 (18) |
O31T—C3T—C4T—O41T | 4.4 (2) | C8—C13—C14—C15 | −60.75 (18) |
O31T—C3T—C4T—O42T | −175.57 (18) | C8—C13—C14—C21 | 59.9 (2) |
C2T—C3T—C4T—O41T | −117.85 (18) | C12—C13—C14—C21 | −66.0 (2) |
C2T—C3T—C4T—O42T | 62.2 (2) | C12—C13—C14—C15 | 173.29 (15) |
C6—C1—C2—C3 | −0.9 (3) | C13—C14—C21—C22 | 58.8 (2) |
C2—C1—C6—C7 | −174.57 (17) | C13—C14—C21—C20 | −121.08 (17) |
C6—C1—C2—O2 | 178.08 (16) | C21—C14—C15—C16 | −55.56 (19) |
C2—C1—C6—C5 | 0.3 (3) | C15—C14—C21—C22 | 177.55 (17) |
C1—C2—C3—O3 | 179.83 (19) | C15—C14—C21—C20 | −2.3 (2) |
O2—C2—C3—O3 | 0.8 (2) | C13—C14—C15—C16 | 68.90 (18) |
C1—C2—C3—C4 | 0.7 (3) | C14—C15—C16—N19 | 61.97 (19) |
O2—C2—C3—C4 | −178.32 (16) | C14—C15—C16—C7 | −56.4 (2) |
C2—C3—C4—C5 | 0.0 (3) | C7—C17—C18—N19 | 37.31 (17) |
O3—C3—C4—C5 | −179.01 (16) | N19—C20—C21—C22 | −125.78 (19) |
C3—C4—C5—C6 | −0.6 (3) | N19—C20—C21—C14 | 54.1 (2) |
C3—C4—C5—N9 | −179.53 (16) | C20—C21—C22—C23 | 176.52 (17) |
C4—C5—C6—C7 | 176.13 (16) | C14—C21—C22—C23 | −3.3 (3) |
N9—C5—C6—C1 | 179.57 (15) | C21—C22—C23—O24 | −64.4 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N19—H19···O11Ti | 0.952 (19) | 1.662 (19) | 2.606 (2) | 170.4 (17) |
O21T—H21T···O11T | 0.92 (3) | 2.33 (3) | 2.687 (2) | 102.8 (19) |
O21T—H21T···O42Tii | 0.92 (3) | 2.28 (3) | 3.118 (2) | 151 (2) |
O31T—H31T···O25iii | 0.87 (3) | 2.04 (3) | 2.833 (2) | 152 (2) |
O41T—H41T···O11Ti | 0.98 (2) | 1.61 (2) | 2.5415 (19) | 157 (2) |
C4—H4···O25 | 0.93 | 2.46 | 2.982 (2) | 116 |
C15—H15A···O3iv | 0.99 | 2.55 | 3.202 (2) | 124 |
C16—H16···O12Ti | 1.00 | 2.54 | 3.387 (2) | 143 |
C20—H20A···O2iv | 0.99 | 2.50 | 3.378 (2) | 147 |
C23—H23A···O31Tv | 0.99 | 2.47 | 3.426 (2) | 163 |
C25—H25A···O41Tvi | 0.98 | 2.58 | 3.413 (2) | 143 |
C25—H25C···O24vii | 0.98 | 2.40 | 3.107 (2) | 129 |
C26—H26C···O21Tviii | 0.98 | 2.51 | 3.403 (2) | 151 |
Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) x−1/2, −y+3/2, −z+1; (iii) x, y, z+1; (iv) −x+3/2, −y+1, z+1/2; (v) −x+1/2, −y+1, z−1/2; (vi) −x+3/2, −y+1, z−1/2; (vii) x+1, y, z; (viii) x+1/2, −y+3/2, −z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C23H27N2O4+·C4H5O5−·5H2O | C23H27N2O4+·C4H5O6− |
Mr | 618.63 | 544.55 |
Crystal system, space group | Triclinic, P1 | Orthorhombic, P212121 |
Temperature (K) | 130 | 130 |
a, b, c (Å) | 9.2915 (10), 9.4337 (9), 16.9287 (17) | 12.2719 (7), 13.5151 (8), 14.3814 (9) |
α, β, γ (°) | 76.401 (2), 88.716 (2), 82.104 (2) | 90, 90, 90 |
V (Å3) | 1428.5 (3) | 2385.2 (2) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.12 | 0.12 |
Crystal size (mm) | 0.40 × 0.35 × 0.05 | 0.45 × 0.25 × 0.20 |
|
Data collection |
Diffractometer | Bruker CCD area-detector diffractometer | Bruker CCD area-detector diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7141, 5034, 4397 | 15054, 3088, 2514 |
Rint | 0.025 | 0.047 |
(sin θ/λ)max (Å−1) | 0.595 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.072, 0.90 | 0.040, 0.071, 0.91 |
No. of reflections | 5034 | 3088 |
No. of parameters | 772 | 368 |
No. of restraints | 3 | 0 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.17, −0.18 | 0.24, −0.22 |
Selected torsion angles (º) for (I) topO11C—C1C—C2C—O21C | 1.1 (4) | O11D—C1D—C2D—O21D | 6.6 (4) |
O11C—C1C—C2C—C3C | 125.0 (3) | O12D—C1D—C2D—O21D | −175.7 (3) |
O12C—C1C—C2C—O21C | 179.3 (3) | O12D—C1D—C2D—C3D | −54.2 (4) |
O12C—C1C—C2C—C3C | −56.8 (4) | O11D—C1D—C2D—C3D | 128.1 (3) |
C1C—C2C—C3C—C4C | −62.9 (4) | C1D—C2D—C3D—C4D | −57.5 (4) |
O21C—C2C—C3C—C4C | 62.7 (4) | O21D—C2D—C3D—C4D | 66.7 (4) |
C2C—C3C—C4C—O41C | −169.1 (3) | C2D—C3D—C4D—O42D | 9.0 (5) |
C2C—C3C—C4C—O42C | 11.8 (5) | C2D—C3D—C4D—O41D | −171.8 (3) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N19A—H19A···O11C | 0.99 | 1.86 | 2.742 (4) | 147 |
N19A—H19A···O21C | 0.99 | 2.36 | 3.117 (4) | 133 |
N19A—H19A···O42C | 0.99 | 2.59 | 3.097 (4) | 112 |
N19B—H19B···O11Di | 0.92 | 1.89 | 2.759 (4) | 156 |
N19B—H19B···O21Di | 0.92 | 2.51 | 3.129 (4) | 124 |
O21C—H21C···O7W | 0.90 | 1.79 | 2.689 (4) | 180 |
O21D—H21D···O9Wii | 0.90 | 1.82 | 2.719 (4) | 180 |
O41C—H41C···O25Biii | 0.93 | 1.73 | 2.645 (3) | 168 |
O41D—H41D···O25Aiv | 0.89 | 1.75 | 2.647 (3) | 179 |
O1W—H11W···O7W | 0.90 | 1.93 | 2.826 (4) | 176 |
O1W—H12W···O6Wv | 0.91 | 1.91 | 2.811 (4) | 171 |
O2W—H21W···O12D | 0.84 | 1.90 | 2.731 (4) | 171 |
O2W—H22W···O12Cvi | 0.89 | 1.83 | 2.721 (4) | 175 |
O3W—H31W···O8Wv | 0.93 | 1.82 | 2.743 (5) | 173 |
O3W—H32W···O1W | 0.86 | 1.96 | 2.805 (4) | 167 |
O4W—H41W···O3Wvi | 0.90 | 1.95 | 2.845 (4) | 179 |
O4W—H42W···O2W | 0.90 | 1.82 | 2.712 (5) | 180 |
O5W—H51W···O11C | 0.90 | 1.76 | 2.659 (4) | 179 |
O5W—H52W···O3Wii | 0.85 | 2.06 | 2.880 (4) | 164 |
O6W—H61W···O8W | 0.91 | 1.90 | 2.808 (4) | 179 |
O6W—H62W···O21D | 0.91 | 1.89 | 2.799 (5) | 179 |
O7W—H71W···O12D | 0.90 | 1.76 | 2.664 (4) | 179 |
O7W—H72W···O9W | 0.87 | 1.92 | 2.764 (4) | 161 |
O8W—H81W···O11Diii | 0.94 | 1.76 | 2.690 (4) | 168 |
O8W—H82W···O12C | 0.86 | 1.92 | 2.768 (4) | 169 |
O9W—H91W···O5Wv | 0.90 | 1.84 | 2.738 (4) | 179 |
O9W—H92W···O4W | 0.92 | 1.76 | 2.653 (4) | 162 |
O10W—H10W···O5Wv | 0.91 | 1.92 | 2.795 (5) | 160 |
O10W—H13W···O21C | 0.90 | 1.94 | 2.844 (4) | 180 |
C3D—H31D···O7W | 0.97 | 2.60 | 3.459 (5) | 148 |
Symmetry codes: (i) x+1, y, z+1; (ii) x−1, y, z; (iii) x, y−1, z; (iv) x, y, z−1; (v) x+1, y, z; (vi) x, y+1, z. |
Selected torsion angles (º) for (II) topO11T—C1T—C2T—O21T | −16.1 (2) | O21T—C2T—C3T—C4T | 59.5 (2) |
O12T—C1T—C2T—C3T | 39.8 (2) | C1T—C2T—C3T—O31T | 63.1 (2) |
O12T—C1T—C2T—O21T | 164.62 (17) | O31T—C3T—C4T—O41T | 4.4 (2) |
O11T—C1T—C2T—C3T | −140.97 (17) | O31T—C3T—C4T—O42T | −175.57 (18) |
C1T—C2T—C3T—C4T | −173.82 (15) | C2T—C3T—C4T—O41T | −117.85 (18) |
O21T—C2T—C3T—O31T | −63.5 (2) | C2T—C3T—C4T—O42T | 62.2 (2) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N19—H19···O11Ti | 0.952 (19) | 1.662 (19) | 2.606 (2) | 170.4 (17) |
O21T—H21T···O11T | 0.92 (3) | 2.33 (3) | 2.687 (2) | 102.8 (19) |
O21T—H21T···O42Tii | 0.92 (3) | 2.28 (3) | 3.118 (2) | 151 (2) |
O31T—H31T···O25iii | 0.87 (3) | 2.04 (3) | 2.833 (2) | 152 (2) |
O41T—H41T···O11Ti | 0.98 (2) | 1.61 (2) | 2.5415 (19) | 157 (2) |
Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) x−1/2, −y+3/2, −z+1; (iii) x, y, z+1. |
Although the crystal structures of the strychnine salts of both D-tartaric acid [strychninium hydrogen 2(S),3(S)-tartrate trihydrate] and L-tartaric acid [bis(strychninium) 2(R),3(R)-tartrate hexahydrate] have been reported by Gould et al. (1987), surprisingly no brucinium tartrate salts are known. Although brucine is well known as an agent for the resolution of chiral species from enantiomeric mixtures of many organic molecule types including α-hydroxy acids (Wilen, 1972), it is not considered the usual one for the simple series analogues, which include glyceric, malic and tartaric acids. However, the reported resolution of L-glyceric acid from a racemic mixture of the acid and the structure determination of its brucinium salt by Bialońska et al. (2005) prompted us to attempt similar resolutions with malic and tartaric acids. We subsequently obtained crystals of brucinium hydrogen L-malate pentahydrate, (I), by simple refluxing of brucine with D,L-malic acid in 50% ethanol–water. The resolution of D,L-tartaric acid was not as successful under these conditions, so the reaction with L-tartaric acid was completed in 50% 2-propanol–water. The use of 2-propanol rather than ethanol was also to test the observation of Sada et al. (1998) that this solvent promoted the crystallization of brucinium carboxylates, often with incorporation of 2-propanol molecules of solvation. However, with our preparation the well formed clusters of crystals obtained were found to have no molecules of solvation, giving brucinium hydrogen L-tartrate, (II). The structures of both (I) and (II) are reported here.
The structure determination of (I) confirmed the presence of two independent brucinium cations (A and B) (Fig. 1), two hydrogen L-malate anions (C and D) and ten water molecules of solvation (Fig. 2) in the crystallographic asymmetric unit. In (I) as well as in (II) (Fig. 3), the atom-numbering scheme for the brucine cage follows the original Robinson convention employed for strychnine (Holmes, 1952). In both (I) and (II), this gives the overall Cahn–Ingold–Prelog absolute configuration for the protonated brucinium species as C7(S), C8(S), C12(S), C13(R), C14(R), C16(S), N19(S). In the hydrogen malate anions in (I), the carboxylic acid adjacent to the α-hydroxyl group is preferentially deprotonated on the basis of its decreased pKa compared with the C4 carboxylic acid group (Tapscott, 1982). This is consistent with observations for other hydrogen malates, e.g. ammonium hydrogen (S)-malate (Versichel et al., 1978).
In (I), the isolation of the enantiomeric L-malate salt of (I) represents a facile resolution from D,L-malic acid using brucine, which has not previously been considered among recognized resolving agents for this acid. More commonly, 1-phenylethylamine or cinchonine have been the agents of choice for the resolution of both D– and L-malic acid, while both of these as well as quinine have been used for D-malic acid resolution (McKenzie et al., 1923; Newman, 1981). The structures of three configurational isomers of 1-phenylethylaminium D–, L– and DL-malate have been reported (Turkington et al., 2004). In (I), the crystallographic asymmetric unit comprises two independent brucine cations, together with two hydrogen L-malate anions (having the expected S configuration and being conformationally similar; Table 1) and ten water molecules of hydration, which form an extensively hydrogen-bonded three-dimensional framework structure (Fig. 4 and Table 2). This structure is in many respects [viz. space group (P1), unit-cell dimensions and contents] similar to the structures of both brucinium L-glycerate 4.75 hydrate (Bialońska et al., 2005) and brucinium citrate pentahydrate (Smith et al., 2005). With brucine compounds generally, the brucine species commonly form regular undulating parallel or antiparallel host sheet substructures built from partially overlapping head-to-tail molecular associations (Gould & Walkinshaw, 1984; Dijksma, Gould, Parsons, Taylor & Walkinshaw, 1998; Bialońska & Ciunik, 2004). However, in (I) there is no such directional substructuring, although, as with the L-glycerate and citrate compounds, there is the presence of significant structuring within the guest cavity, including numerous cyclic and extended-chain water–water and water–anion hydrogen-bonding interactions. In addition, in (I), there are brucine N+—H ···O(malate) interactions (four-centred in A and three-centred in B) and malate O—H···O (brucine) host–guest interactions.
The brucine molecules in (II) form the previously described parallel-mode substructures, which in (II) extend along the a direction in the unit cell, with a dimeric repeat of ca 12.27 Å and a chain offset angle α (Smith et al., 2006) of ca 118° (Fig. 5). These values compare with 12.66 Å and 123°, respectively, in the similar parallel-mode brucinium D-glucuronate structure (Dijksma, Gould, Parsons & Walkinshaw, 1998). The inter-sheet cavities accommodate the hydrogen tartrate anion species, which form parallel chain structures through head-to-tail cyclic R22(9) hydrogen-bonding interactions (Table 4). These associations incorporate an intramolecular tartrate O21T(hydroxy)—H···O11T(carboxyl) hydrogen bond (Table 4). The chains are linked peripherally to the brucinium cation substructure through O(hydroxy)—H···O(carbonyl) and N+(brucine)—H···O(carboxyl) interactions, giving a three-dimensional cage structure. The tartrate chains in (II) are similar to the succinate chain substructure found in strychnidinium hydrogen succinate (Maurin et al., 2006). In this analysis, the accepted 2(R),3(R) absolute configuration is confirmed for the L-tartrate residue, which also adopts an extended conformation (Table 3).