The structure of brucinium dihydrogen citrate trihydrate (systematic name: 2,3-dimethoxy-10-oxostrychnidinium dihydrogen citrate trihydrate), C23H27N2O4+·C6H7O7-·3H2O, has been determined at 130 K. The crystallographic asymmetric unit comprises two brucinium cations, two dihydrogen citrate anions and six water molecules of solvation. The two citrate anions, which are conformationally dissimilar, associate through extensive hydrogen-bonding interactions with the common undulating brucinium cation layer substructures and the water molecules, forming a three-dimensional framework polymer.
Supporting information
CCDC reference: 290586
The title compound (I) was synthesized by heating 1 mmol quantities of brucine tetrahydrate and citric acid in 80% ethanol–water (50 ml) for 10 min under reflux. After concentration to ca 30 ml, partial room temperature evaporation of the hot-filtered solution gave large colourless crystal plates (m.p. 489.9–494.1 K).
H atoms potentially involved in hydrogen-bonding interactions were located by difference methods and their positional and isotropic displacement parameters were refined. Other H atoms were included in the refinement at calculated positions (C—H = 0.95–1.00 Å) and treated as riding, with Uiso(H) values of 1.2Ueq(C) or 1.5Ueq(Cmethyl). The atom-numbering scheme employed for the brucinium cation cages in (I) (Fig. 1a) follows the original Robinson convention for strychnine (Holmes, 1952). The absolute configuration determined for the parent strychnidinin-10-one molecule (Peerdeman, 1956) was invoked. Please check changes to text.
Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); 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 (Farrugia, 1999); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.
2,3-dimethoxy-10-oxostrychnidinium dihydrogencitrate trihydrate
top
Crystal data top
C23H27N2O42+·C6H7O72−·3H2O | Z = 2 |
Mr = 640.63 | F(000) = 680 |
Triclinic, P1 | Dx = 1.458 Mg m−3 |
Hall symbol: P 1 | Melting point = 489.9–494.1 K |
a = 9.2355 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.6894 (8) Å | Cell parameters from 2391 reflections |
c = 17.1446 (15) Å | θ = 2.3–25.5° |
α = 75.775 (2)° | µ = 0.12 mm−1 |
β = 80.917 (2)° | T = 130 K |
γ = 81.553 (2)° | Block, colourless |
V = 1459.1 (2) Å3 | 0.45 × 0.40 × 0.30 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 4354 reflections with F2 > 2σ(F2) |
Radiation source: sealed tube | Rint = 0.031 |
Graphite monochromator | θmax = 25.0°, θmin = 2.2° |
ϕ and ω scans | h = −10→9 |
7737 measured reflections | k = −11→11 |
5129 independent reflections | l = −17→20 |
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) = 0.075 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.92 | w = 1/[σ2(Fo2) + (0.0266P)2] where P = (Fo2 + 2Fc2)/3 |
5129 reflections | (Δ/σ)max = 0.027 |
888 parameters | Δρmax = 0.32 e Å−3 |
3 restraints | Δρmin = −0.19 e Å−3 |
Crystal data top
C23H27N2O42+·C6H7O72−·3H2O | γ = 81.553 (2)° |
Mr = 640.63 | V = 1459.1 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.2355 (8) Å | Mo Kα radiation |
b = 9.6894 (8) Å | µ = 0.12 mm−1 |
c = 17.1446 (15) Å | T = 130 K |
α = 75.775 (2)° | 0.45 × 0.40 × 0.30 mm |
β = 80.917 (2)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 4354 reflections with F2 > 2σ(F2) |
7737 measured reflections | Rint = 0.031 |
5129 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 3 restraints |
wR(F2) = 0.075 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.92 | Δρmax = 0.32 e Å−3 |
5129 reflections | Δρmin = −0.19 e Å−3 |
888 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 | 0.9584 (3) | 0.4209 (2) | 0.66281 (17) | 0.0273 (10) | |
O3A | 0.8658 (3) | 0.5248 (2) | 0.78871 (16) | 0.0250 (9) | |
O24A | 0.2218 (3) | 1.1199 (3) | 0.51304 (16) | 0.0266 (10) | |
O25A | 0.4577 (3) | 0.9378 (3) | 0.74584 (16) | 0.0240 (9) | |
N9A | 0.4700 (3) | 0.8285 (3) | 0.64144 (18) | 0.0191 (10) | |
N19A | 0.4633 (3) | 0.7157 (3) | 0.39567 (19) | 0.0245 (11) | |
C1A | 0.7577 (4) | 0.5568 (4) | 0.5906 (2) | 0.0213 (12) | |
C2A | 0.8350 (4) | 0.5182 (4) | 0.6566 (2) | 0.0206 (12) | |
C3A | 0.7875 (4) | 0.5768 (4) | 0.7245 (2) | 0.0220 (12) | |
C4A | 0.6665 (4) | 0.6807 (4) | 0.7254 (2) | 0.0202 (12) | |
C5A | 0.5925 (4) | 0.7220 (4) | 0.6561 (2) | 0.0205 (12) | |
C6A | 0.6344 (4) | 0.6593 (4) | 0.5909 (2) | 0.0193 (12) | |
C7A | 0.5238 (4) | 0.7097 (4) | 0.5306 (2) | 0.0207 (12) | |
C8A | 0.4355 (4) | 0.8432 (4) | 0.5582 (2) | 0.0197 (12) | |
C10A | 0.4251 (4) | 0.9373 (4) | 0.6794 (2) | 0.0206 (12) | |
C11A | 0.3274 (4) | 1.0592 (4) | 0.6335 (2) | 0.0225 (14) | |
C12A | 0.3631 (4) | 1.1025 (4) | 0.5412 (2) | 0.0234 (14) | |
C13A | 0.4752 (4) | 0.9908 (4) | 0.5099 (2) | 0.0214 (12) | |
C14A | 0.5037 (4) | 1.0012 (4) | 0.4181 (2) | 0.0216 (12) | |
C15A | 0.6363 (4) | 0.8888 (4) | 0.4032 (2) | 0.0255 (12) | |
C16A | 0.5874 (4) | 0.7408 (4) | 0.4402 (2) | 0.0231 (14) | |
C17A | 0.4230 (4) | 0.5938 (4) | 0.5355 (2) | 0.0226 (12) | |
C18A | 0.3468 (4) | 0.6482 (4) | 0.4600 (2) | 0.0264 (14) | |
C20A | 0.3997 (4) | 0.8509 (4) | 0.3404 (2) | 0.0293 (14) | |
C21A | 0.3737 (4) | 0.9740 (4) | 0.3815 (2) | 0.0234 (12) | |
C22A | 0.2453 (4) | 1.0570 (4) | 0.3837 (2) | 0.0275 (14) | |
C23A | 0.2214 (4) | 1.1760 (4) | 0.4275 (2) | 0.0270 (16) | |
C25A | 1.0212 (5) | 0.3744 (5) | 0.5911 (3) | 0.0408 (17) | |
C26A | 0.8182 (4) | 0.5829 (4) | 0.8585 (2) | 0.0291 (16) | |
O2B | 1.1856 (3) | −0.3448 (3) | 0.70410 (17) | 0.0297 (10) | |
O3B | 1.0563 (3) | −0.2334 (3) | 0.57864 (17) | 0.0265 (9) | |
O24B | 0.5135 (3) | 0.3586 (3) | 0.84260 (17) | 0.0307 (10) | |
O25B | 0.6567 (3) | 0.1719 (3) | 0.61176 (17) | 0.0266 (10) | |
N9B | 0.7861 (3) | 0.1370 (3) | 0.71849 (19) | 0.0206 (11) | |
N19B | 0.9400 (4) | 0.0768 (3) | 0.9701 (2) | 0.0248 (11) | |
C1B | 1.0653 (4) | −0.1591 (4) | 0.7739 (2) | 0.0216 (12) | |
C2B | 1.0903 (4) | −0.2232 (4) | 0.7092 (2) | 0.0216 (14) | |
C3B | 1.0186 (4) | −0.1638 (4) | 0.6401 (2) | 0.0206 (14) | |
C4B | 0.9176 (4) | −0.0418 (4) | 0.6372 (2) | 0.0202 (12) | |
C5B | 0.8897 (4) | 0.0173 (4) | 0.7050 (2) | 0.0237 (14) | |
C6B | 0.9639 (4) | −0.0377 (4) | 0.7724 (2) | 0.0197 (12) | |
C7B | 0.9254 (4) | 0.0551 (4) | 0.8328 (2) | 0.0209 (12) | |
C8B | 0.7838 (4) | 0.1533 (4) | 0.8017 (2) | 0.0211 (12) | |
C10B | 0.6687 (4) | 0.1908 (4) | 0.6786 (2) | 0.0224 (12) | |
C11B | 0.5503 (4) | 0.2804 (4) | 0.7223 (2) | 0.0219 (12) | |
C12B | 0.5187 (4) | 0.2303 (4) | 0.8146 (2) | 0.0229 (12) | |
C13B | 0.6363 (4) | 0.1109 (4) | 0.8477 (2) | 0.0187 (12) | |
C14B | 0.6370 (4) | 0.0625 (4) | 0.9400 (2) | 0.0219 (12) | |
C15B | 0.7507 (4) | −0.0706 (4) | 0.9546 (2) | 0.0213 (12) | |
C16B | 0.9025 (4) | −0.0249 (4) | 0.9220 (2) | 0.0228 (14) | |
C17B | 1.0498 (4) | 0.1468 (4) | 0.8311 (2) | 0.0257 (14) | |
C18B | 1.0110 (5) | 0.1969 (4) | 0.9093 (3) | 0.0296 (16) | |
C20B | 0.8090 (4) | 0.1312 (4) | 1.0233 (2) | 0.0281 (16) | |
C21B | 0.6761 (4) | 0.1742 (4) | 0.9782 (2) | 0.0240 (14) | |
C22B | 0.5983 (5) | 0.3020 (4) | 0.9745 (2) | 0.0287 (16) | |
C23B | 0.4684 (5) | 0.3459 (5) | 0.9266 (3) | 0.0374 (17) | |
C25B | 1.2472 (5) | −0.4203 (4) | 0.7761 (3) | 0.0436 (17) | |
C26B | 0.9793 (4) | −0.1777 (4) | 0.5088 (2) | 0.0287 (14) | |
O3C | 0.7371 (4) | 0.2235 (3) | 0.26169 (18) | 0.0284 (11) | |
O11C | 0.8301 (3) | 0.5679 (3) | 0.05305 (17) | 0.0345 (10) | |
O12C | 0.6366 (3) | 0.4629 (3) | 0.12198 (17) | 0.0302 (10) | |
O31C | 0.5080 (3) | 0.3871 (3) | 0.31579 (16) | 0.0279 (9) | |
O32C | 0.6302 (3) | 0.5792 (3) | 0.29166 (17) | 0.0274 (10) | |
O51C | 0.7242 (3) | 0.3342 (3) | 0.46259 (19) | 0.0368 (11) | |
O52C | 0.8231 (3) | 0.1228 (3) | 0.43870 (18) | 0.0407 (11) | |
C1C | 0.7616 (4) | 0.4900 (4) | 0.1194 (2) | 0.0237 (14) | |
C2C | 0.8508 (4) | 0.4376 (4) | 0.1904 (2) | 0.0224 (12) | |
C3C | 0.7665 (4) | 0.3598 (4) | 0.2690 (2) | 0.0209 (12) | |
C4C | 0.8687 (4) | 0.3352 (4) | 0.3349 (2) | 0.0245 (14) | |
C5C | 0.8040 (4) | 0.2518 (5) | 0.4165 (3) | 0.0284 (16) | |
C31C | 0.6214 (4) | 0.4501 (4) | 0.2940 (2) | 0.0223 (12) | |
O3D | 0.2779 (3) | 0.8571 (3) | 0.12479 (19) | 0.0350 (11) | |
O11D | 0.2416 (3) | 0.5201 (3) | 0.32306 (16) | 0.0297 (10) | |
O12D | 0.0693 (3) | 0.6613 (3) | 0.25768 (18) | 0.0455 (11) | |
O31D | 0.0141 (3) | 0.8276 (3) | 0.08866 (16) | 0.0271 (9) | |
O32D | 0.0889 (3) | 0.6074 (3) | 0.06809 (18) | 0.0356 (11) | |
O51D | 0.4587 (3) | 0.7786 (3) | −0.10473 (18) | 0.0334 (10) | |
O52D | 0.2532 (3) | 0.8990 (3) | −0.05697 (19) | 0.0440 (11) | |
C1D | 0.1937 (5) | 0.6004 (4) | 0.2553 (3) | 0.0276 (16) | |
C2D | 0.3017 (5) | 0.6070 (4) | 0.1797 (2) | 0.0323 (17) | |
C3D | 0.2650 (4) | 0.7248 (4) | 0.1064 (3) | 0.0255 (14) | |
C4D | 0.3786 (4) | 0.7026 (4) | 0.0338 (2) | 0.0279 (14) | |
C5D | 0.3535 (5) | 0.8043 (4) | −0.0459 (3) | 0.0274 (17) | |
C31D | 0.1083 (5) | 0.7217 (5) | 0.0864 (2) | 0.0275 (16) | |
O1W | 0.5257 (4) | 0.9778 (3) | 0.1346 (2) | 0.0406 (11) | |
O2W | 0.7622 (4) | 0.8169 (3) | 0.2036 (2) | 0.0381 (11) | |
O3W | 0.9797 (5) | −0.0069 (4) | 0.2626 (3) | 0.0553 (14) | |
O4W | 0.4606 (4) | 0.2307 (5) | 0.1834 (3) | 0.0604 (17) | |
O5W | 0.2342 (4) | 0.3319 (4) | 0.0866 (3) | 0.0740 (18) | |
O6W | 0.0861 (4) | 0.1063 (3) | 0.1002 (2) | 0.0543 (14) | |
H1A | 0.78790 | 0.51430 | 0.54540 | 0.0260* | |
H4A | 0.63500 | 0.72220 | 0.77090 | 0.0240* | |
H8A | 0.32750 | 0.83910 | 0.55980 | 0.0240* | |
H12A | 0.40420 | 1.19680 | 0.52580 | 0.0280* | |
H13A | 0.57150 | 1.00180 | 0.52600 | 0.0250* | |
H14A | 0.53180 | 1.09880 | 0.39030 | 0.0260* | |
H16A | 0.67380 | 0.66780 | 0.43260 | 0.0280* | |
H19A | 0.503 (4) | 0.650 (4) | 0.364 (3) | 0.040 (11)* | |
H22A | 0.16860 | 1.04070 | 0.35730 | 0.0330* | |
H27A | 0.32910 | 1.14470 | 0.65510 | 0.0270* | |
H28A | 0.22500 | 1.03370 | 0.64610 | 0.0270* | |
H29A | 0.66770 | 0.89970 | 0.34430 | 0.0310* | |
H30A | 0.72060 | 0.90210 | 0.42880 | 0.0310* | |
H31A | 0.48140 | 0.49970 | 0.53520 | 0.0270* | |
H32A | 0.35040 | 0.58460 | 0.58510 | 0.0270* | |
H33A | 0.31190 | 0.56830 | 0.44420 | 0.0320* | |
H34A | 0.26130 | 0.71970 | 0.46900 | 0.0320* | |
H35A | 0.46890 | 0.87450 | 0.29000 | 0.0350* | |
H36A | 0.30540 | 0.83450 | 0.32550 | 0.0350* | |
H37A | 0.30040 | 1.23950 | 0.40670 | 0.0330* | |
H38A | 0.12570 | 1.23370 | 0.41720 | 0.0330* | |
H39A | 1.03670 | 0.45800 | 0.54630 | 0.0610* | |
H40A | 0.95420 | 0.31660 | 0.57760 | 0.0610* | |
H41A | 1.11600 | 0.31650 | 0.60000 | 0.0610* | |
H42A | 0.71650 | 0.56330 | 0.87960 | 0.0440* | |
H43A | 0.82270 | 0.68660 | 0.84360 | 0.0440* | |
H44A | 0.88270 | 0.53850 | 0.90030 | 0.0440* | |
H1B | 1.11710 | −0.19770 | 0.81950 | 0.0260* | |
H4B | 0.86930 | −0.00020 | 0.59050 | 0.0240* | |
H8B | 0.79180 | 0.25550 | 0.80100 | 0.0250* | |
H12B | 0.41970 | 0.19410 | 0.82910 | 0.0280* | |
H13B | 0.61890 | 0.02460 | 0.82980 | 0.0220* | |
H14B | 0.53730 | 0.03490 | 0.96580 | 0.0260* | |
H16B | 0.97600 | −0.11230 | 0.92970 | 0.0270* | |
H19B | 1.005 (4) | 0.036 (4) | 1.009 (3) | 0.033 (12)* | |
H22B | 0.62470 | 0.36650 | 1.00220 | 0.0350* | |
H27B | 0.45730 | 0.28560 | 0.69940 | 0.0260* | |
H28B | 0.57840 | 0.37900 | 0.70980 | 0.0260* | |
H29B | 0.74580 | −0.11490 | 1.01340 | 0.0250* | |
H30B | 0.72950 | −0.14200 | 0.92660 | 0.0250* | |
H31B | 1.14750 | 0.08880 | 0.82950 | 0.0310* | |
H32B | 1.05100 | 0.22910 | 0.78360 | 0.0310* | |
H33B | 0.94160 | 0.28590 | 0.90180 | 0.0360* | |
H34B | 1.10080 | 0.21580 | 0.92790 | 0.0360* | |
H37B | 0.39750 | 0.27380 | 0.94600 | 0.0450* | |
H38B | 0.41750 | 0.43890 | 0.93590 | 0.0450* | |
H39B | 1.16760 | −0.45120 | 0.81920 | 0.0650* | |
H40B | 1.30330 | −0.35710 | 0.79320 | 0.0650* | |
H41B | 1.31290 | −0.50430 | 0.76520 | 0.0650* | |
H42B | 1.00920 | −0.08330 | 0.48060 | 0.0430* | |
H43B | 0.87270 | −0.16870 | 0.52610 | 0.0430* | |
H44B | 1.00350 | −0.24310 | 0.47190 | 0.0430* | |
H71A | 0.78670 | 0.05540 | 1.07260 | 0.0340* | |
H72A | 0.83260 | 0.21480 | 1.04050 | 0.0340* | |
H3C | 0.661 (5) | 0.227 (5) | 0.254 (3) | 0.06 (2)* | |
H11C | 0.913 (3) | 0.581 (3) | 0.062 (3) | 0.065 (10)* | |
H21C | 0.88840 | 0.52100 | 0.20100 | 0.0270* | |
H22C | 0.93730 | 0.37220 | 0.17470 | 0.0270* | |
H41C | 0.96360 | 0.28250 | 0.31730 | 0.0290* | |
H42C | 0.88950 | 0.42920 | 0.34080 | 0.0290* | |
H51C | 0.702 (6) | 0.280 (6) | 0.513 (4) | 0.11 (2)* | |
H3D | 0.200 (7) | 0.900 (6) | 0.113 (4) | 0.081 (12)* | |
H11D | 0.340 (5) | 0.482 (4) | 0.313 (3) | 0.047 (14)* | |
H21D | 0.31130 | 0.51370 | 0.16440 | 0.0380* | |
H22D | 0.39930 | 0.61900 | 0.19260 | 0.0380* | |
H41D | 0.47750 | 0.71160 | 0.04610 | 0.0330* | |
H42D | 0.37950 | 0.60360 | 0.02760 | 0.0330* | |
H51D | 0.438 (6) | 0.844 (5) | −0.155 (4) | 0.085 (19)* | |
H11W | 0.451 (5) | 0.926 (4) | 0.133 (3) | 0.039 (14)* | |
H12W | 0.597 (5) | 0.919 (5) | 0.163 (3) | 0.059 (17)* | |
H21W | 0.840 (5) | 0.814 (5) | 0.176 (3) | 0.044 (17)* | |
H22W | 0.738 (7) | 0.742 (7) | 0.236 (4) | 0.081 (16)* | |
H31W | 0.982 (5) | −0.100 (6) | 0.261 (4) | 0.090 (15)* | |
H32W | 0.905 (4) | 0.065 (4) | 0.262 (2) | 0.074 (12)* | |
H41W | 0.481 (4) | 0.151 (4) | 0.168 (3) | 0.072 (10)* | |
H42W | 0.516 (4) | 0.304 (4) | 0.170 (3) | 0.075 (10)* | |
H51W | 0.307 (3) | 0.299 (3) | 0.1180 (18) | 0.064 (10)* | |
H52W | 0.187 (3) | 0.421 (3) | 0.081 (2) | 0.060 (12)* | |
H61W | 0.136 (3) | 0.182 (3) | 0.0957 (19) | 0.070 (13)* | |
H62W | 0.084 (3) | 0.070 (3) | 0.152 (2) | 0.074 (10)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O2A | 0.0278 (17) | 0.0226 (15) | 0.0293 (18) | 0.0092 (13) | −0.0056 (13) | −0.0078 (13) |
O3A | 0.0275 (16) | 0.0217 (14) | 0.0246 (18) | 0.0059 (12) | −0.0082 (13) | −0.0050 (13) |
O24A | 0.0222 (16) | 0.0311 (16) | 0.0250 (18) | 0.0024 (13) | −0.0066 (12) | −0.0044 (13) |
O25A | 0.0316 (17) | 0.0227 (14) | 0.0177 (17) | 0.0016 (12) | −0.0049 (12) | −0.0060 (12) |
N9A | 0.0222 (18) | 0.0172 (16) | 0.0167 (19) | 0.0009 (14) | −0.0052 (14) | −0.0018 (14) |
N19A | 0.027 (2) | 0.0292 (19) | 0.019 (2) | 0.0015 (15) | −0.0063 (15) | −0.0096 (16) |
C1A | 0.025 (2) | 0.017 (2) | 0.020 (2) | −0.0016 (17) | 0.0046 (18) | −0.0056 (18) |
C2A | 0.018 (2) | 0.017 (2) | 0.024 (2) | −0.0009 (17) | 0.0012 (18) | −0.0023 (18) |
C3A | 0.020 (2) | 0.022 (2) | 0.022 (2) | −0.0045 (18) | −0.0058 (18) | 0.0021 (19) |
C4A | 0.020 (2) | 0.018 (2) | 0.021 (2) | −0.0032 (17) | −0.0002 (17) | −0.0021 (18) |
C5A | 0.019 (2) | 0.018 (2) | 0.021 (2) | −0.0015 (17) | 0.0006 (17) | −0.0001 (18) |
C6A | 0.023 (2) | 0.019 (2) | 0.015 (2) | −0.0045 (18) | 0.0012 (17) | −0.0031 (18) |
C7A | 0.018 (2) | 0.021 (2) | 0.022 (2) | 0.0012 (17) | −0.0014 (17) | −0.0058 (18) |
C8A | 0.013 (2) | 0.024 (2) | 0.020 (2) | −0.0011 (17) | 0.0002 (16) | −0.0031 (18) |
C10A | 0.017 (2) | 0.024 (2) | 0.020 (2) | −0.0037 (18) | 0.0022 (17) | −0.0058 (19) |
C11A | 0.019 (2) | 0.021 (2) | 0.025 (3) | 0.0026 (17) | −0.0038 (18) | −0.0030 (18) |
C12A | 0.023 (2) | 0.022 (2) | 0.026 (3) | −0.0041 (18) | −0.0078 (18) | −0.0032 (19) |
C13A | 0.019 (2) | 0.025 (2) | 0.020 (2) | −0.0040 (17) | −0.0021 (17) | −0.0043 (18) |
C14A | 0.024 (2) | 0.020 (2) | 0.017 (2) | −0.0031 (18) | 0.0003 (17) | 0.0014 (17) |
C15A | 0.022 (2) | 0.034 (2) | 0.019 (2) | −0.0030 (19) | −0.0012 (17) | −0.0041 (19) |
C16A | 0.014 (2) | 0.030 (2) | 0.027 (3) | 0.0029 (17) | −0.0067 (17) | −0.0102 (19) |
C17A | 0.023 (2) | 0.023 (2) | 0.023 (2) | −0.0006 (18) | 0.0017 (17) | −0.0117 (18) |
C18A | 0.021 (2) | 0.036 (2) | 0.023 (3) | −0.0032 (19) | 0.0000 (18) | −0.010 (2) |
C20A | 0.030 (3) | 0.036 (2) | 0.020 (2) | 0.001 (2) | −0.0104 (19) | −0.001 (2) |
C21A | 0.025 (2) | 0.025 (2) | 0.018 (2) | −0.0041 (18) | −0.0034 (18) | 0.0005 (18) |
C22A | 0.027 (2) | 0.030 (2) | 0.024 (3) | −0.002 (2) | −0.0110 (19) | 0.001 (2) |
C23A | 0.028 (3) | 0.025 (2) | 0.026 (3) | 0.0039 (19) | −0.0096 (19) | −0.002 (2) |
C25A | 0.038 (3) | 0.041 (3) | 0.033 (3) | 0.018 (2) | −0.001 (2) | −0.004 (2) |
C26A | 0.030 (3) | 0.028 (2) | 0.027 (3) | 0.0021 (19) | −0.010 (2) | −0.001 (2) |
O2B | 0.0252 (16) | 0.0277 (15) | 0.0327 (19) | 0.0092 (13) | −0.0067 (13) | −0.0054 (14) |
O3B | 0.0229 (16) | 0.0280 (15) | 0.0284 (18) | 0.0046 (13) | −0.0051 (13) | −0.0091 (14) |
O24B | 0.0392 (18) | 0.0283 (16) | 0.0243 (18) | 0.0113 (13) | −0.0110 (14) | −0.0097 (14) |
O25B | 0.0268 (17) | 0.0319 (16) | 0.0189 (17) | 0.0031 (13) | −0.0059 (12) | −0.0035 (13) |
N9B | 0.0229 (19) | 0.0157 (16) | 0.022 (2) | 0.0018 (14) | −0.0051 (15) | −0.0031 (15) |
N19B | 0.029 (2) | 0.0218 (18) | 0.024 (2) | −0.0004 (16) | −0.0109 (17) | −0.0028 (16) |
C1B | 0.016 (2) | 0.025 (2) | 0.019 (2) | 0.0028 (17) | −0.0054 (17) | 0.0031 (18) |
C2B | 0.017 (2) | 0.019 (2) | 0.025 (3) | 0.0009 (17) | 0.0008 (18) | −0.0019 (18) |
C3B | 0.015 (2) | 0.020 (2) | 0.025 (3) | −0.0040 (17) | −0.0015 (17) | −0.0013 (19) |
C4B | 0.018 (2) | 0.021 (2) | 0.020 (2) | −0.0048 (17) | −0.0047 (17) | 0.0011 (18) |
C5B | 0.020 (2) | 0.023 (2) | 0.027 (3) | −0.0023 (18) | 0.0013 (18) | −0.0066 (19) |
C6B | 0.020 (2) | 0.019 (2) | 0.017 (2) | −0.0051 (17) | 0.0014 (17) | 0.0010 (17) |
C7B | 0.021 (2) | 0.023 (2) | 0.018 (2) | 0.0001 (17) | −0.0076 (17) | −0.0016 (18) |
C8B | 0.027 (2) | 0.018 (2) | 0.017 (2) | 0.0018 (18) | −0.0046 (18) | −0.0032 (17) |
C10B | 0.020 (2) | 0.026 (2) | 0.018 (2) | −0.0087 (18) | −0.0019 (17) | 0.0044 (19) |
C11B | 0.021 (2) | 0.022 (2) | 0.023 (2) | −0.0001 (18) | −0.0047 (17) | −0.0058 (18) |
C12B | 0.022 (2) | 0.022 (2) | 0.023 (2) | 0.0026 (17) | −0.0047 (18) | −0.0037 (18) |
C13B | 0.020 (2) | 0.017 (2) | 0.019 (2) | −0.0031 (16) | −0.0035 (17) | −0.0028 (17) |
C14B | 0.015 (2) | 0.024 (2) | 0.025 (2) | −0.0014 (17) | −0.0001 (17) | −0.0043 (18) |
C15B | 0.027 (2) | 0.018 (2) | 0.017 (2) | −0.0013 (18) | −0.0035 (17) | −0.0005 (17) |
C16B | 0.026 (2) | 0.017 (2) | 0.025 (3) | 0.0023 (17) | −0.0053 (18) | −0.0054 (18) |
C17B | 0.022 (2) | 0.023 (2) | 0.030 (3) | 0.0031 (18) | −0.0078 (19) | −0.0024 (19) |
C18B | 0.030 (3) | 0.028 (2) | 0.032 (3) | −0.007 (2) | −0.010 (2) | −0.003 (2) |
C20B | 0.037 (3) | 0.028 (2) | 0.022 (3) | −0.003 (2) | −0.006 (2) | −0.0096 (19) |
C21B | 0.031 (3) | 0.025 (2) | 0.014 (2) | −0.004 (2) | −0.0015 (18) | −0.0009 (18) |
C22B | 0.037 (3) | 0.030 (2) | 0.020 (3) | 0.000 (2) | −0.0049 (19) | −0.0091 (19) |
C23B | 0.042 (3) | 0.040 (3) | 0.029 (3) | 0.016 (2) | −0.009 (2) | −0.015 (2) |
C25B | 0.041 (3) | 0.036 (3) | 0.045 (3) | 0.017 (2) | −0.012 (2) | −0.001 (2) |
C26B | 0.025 (2) | 0.037 (2) | 0.024 (3) | 0.000 (2) | −0.0059 (18) | −0.007 (2) |
O3C | 0.0280 (19) | 0.0245 (16) | 0.034 (2) | −0.0005 (14) | −0.0098 (15) | −0.0068 (13) |
O11C | 0.0427 (19) | 0.0377 (17) | 0.0202 (18) | −0.0130 (15) | −0.0061 (14) | 0.0049 (14) |
O12C | 0.0283 (18) | 0.0326 (16) | 0.0294 (18) | −0.0038 (14) | −0.0096 (13) | −0.0028 (14) |
O31C | 0.0216 (16) | 0.0295 (15) | 0.0291 (18) | −0.0049 (13) | −0.0002 (13) | −0.0010 (13) |
O32C | 0.0297 (17) | 0.0206 (15) | 0.0309 (18) | −0.0018 (12) | 0.0007 (13) | −0.0077 (13) |
O51C | 0.052 (2) | 0.0283 (17) | 0.0244 (19) | 0.0043 (15) | 0.0017 (15) | −0.0044 (15) |
O52C | 0.052 (2) | 0.0284 (18) | 0.034 (2) | 0.0011 (16) | −0.0016 (15) | 0.0017 (15) |
C1C | 0.025 (2) | 0.024 (2) | 0.024 (3) | 0.0004 (19) | −0.0040 (19) | −0.0103 (19) |
C2C | 0.021 (2) | 0.025 (2) | 0.020 (2) | −0.0010 (17) | 0.0001 (17) | −0.0054 (18) |
C3C | 0.023 (2) | 0.018 (2) | 0.022 (2) | −0.0023 (17) | −0.0022 (17) | −0.0057 (18) |
C4C | 0.021 (2) | 0.028 (2) | 0.024 (3) | −0.0020 (18) | −0.0053 (18) | −0.0041 (19) |
C5C | 0.023 (2) | 0.034 (3) | 0.031 (3) | −0.003 (2) | −0.011 (2) | −0.008 (2) |
C31C | 0.026 (2) | 0.026 (2) | 0.013 (2) | −0.0006 (19) | −0.0048 (17) | −0.0010 (18) |
O3D | 0.0282 (18) | 0.0328 (17) | 0.047 (2) | −0.0009 (14) | −0.0122 (15) | −0.0114 (15) |
O11D | 0.0237 (18) | 0.0402 (18) | 0.0198 (17) | 0.0058 (14) | −0.0043 (13) | −0.0010 (14) |
O12D | 0.0269 (19) | 0.064 (2) | 0.032 (2) | 0.0132 (16) | −0.0005 (14) | 0.0016 (17) |
O31D | 0.0255 (16) | 0.0257 (15) | 0.0245 (18) | 0.0054 (13) | −0.0067 (13) | 0.0019 (13) |
O32D | 0.0387 (19) | 0.0313 (17) | 0.039 (2) | −0.0118 (14) | 0.0011 (14) | −0.0112 (15) |
O51D | 0.0351 (19) | 0.0360 (17) | 0.0191 (18) | 0.0061 (14) | 0.0003 (14) | 0.0041 (15) |
O52D | 0.0311 (18) | 0.0496 (19) | 0.033 (2) | 0.0134 (16) | −0.0022 (14) | 0.0131 (16) |
C1D | 0.026 (3) | 0.027 (2) | 0.030 (3) | 0.002 (2) | −0.008 (2) | −0.007 (2) |
C2D | 0.031 (3) | 0.039 (3) | 0.021 (3) | 0.008 (2) | −0.0042 (19) | −0.002 (2) |
C3D | 0.022 (2) | 0.025 (2) | 0.025 (3) | 0.0036 (18) | −0.0038 (18) | −0.0006 (19) |
C4D | 0.023 (2) | 0.029 (2) | 0.026 (3) | −0.0009 (19) | −0.0029 (19) | 0.003 (2) |
C5D | 0.026 (3) | 0.034 (3) | 0.020 (3) | −0.009 (2) | −0.001 (2) | 0.000 (2) |
C31D | 0.030 (3) | 0.035 (3) | 0.012 (2) | −0.009 (2) | 0.0003 (18) | 0.0063 (19) |
O1W | 0.035 (2) | 0.0373 (19) | 0.048 (2) | −0.0090 (17) | −0.0103 (17) | −0.0007 (17) |
O2W | 0.034 (2) | 0.0271 (19) | 0.045 (2) | −0.0012 (17) | 0.0061 (17) | −0.0013 (17) |
O3W | 0.051 (2) | 0.053 (2) | 0.065 (3) | −0.0064 (19) | −0.003 (2) | −0.022 (2) |
O4W | 0.064 (3) | 0.062 (3) | 0.064 (3) | −0.022 (2) | 0.007 (2) | −0.032 (2) |
O5W | 0.069 (3) | 0.052 (2) | 0.108 (4) | −0.010 (2) | −0.007 (2) | −0.032 (2) |
O6W | 0.053 (2) | 0.051 (2) | 0.065 (3) | 0.0046 (18) | −0.0221 (19) | −0.0214 (19) |
Geometric parameters (Å, º) top
O2A—C2A | 1.368 (5) | C12A—H12A | 1.0000 |
O2A—C25A | 1.422 (6) | C13A—H13A | 1.0000 |
O3A—C3A | 1.364 (4) | C14A—H14A | 1.0000 |
O3A—C26A | 1.426 (4) | C15A—H29A | 0.9900 |
O24A—C12A | 1.435 (5) | C15A—H30A | 0.9900 |
O24A—C23A | 1.434 (4) | C16A—H16A | 1.0000 |
O25A—C10A | 1.225 (4) | C17A—H31A | 0.9900 |
O2B—C25B | 1.428 (6) | C17A—H32A | 0.9900 |
O2B—C2B | 1.376 (5) | C18A—H34A | 0.9900 |
O3B—C3B | 1.360 (5) | C18A—H33A | 0.9900 |
O3B—C26B | 1.439 (4) | C20A—H36A | 0.9900 |
O24B—C23B | 1.415 (6) | C20A—H35A | 0.9900 |
O24B—C12B | 1.431 (5) | C22A—H22A | 0.9500 |
O25B—C10B | 1.228 (4) | C23A—H37A | 0.9900 |
O3C—C3C | 1.425 (5) | C23A—H38A | 0.9900 |
O11C—C1C | 1.325 (4) | C25A—H39A | 0.9800 |
O12C—C1C | 1.213 (5) | C25A—H41A | 0.9800 |
O31C—C31C | 1.250 (5) | C25A—H40A | 0.9800 |
O32C—C31C | 1.256 (5) | C26A—H43A | 0.9800 |
O51C—C5C | 1.326 (6) | C26A—H44A | 0.9800 |
O52C—C5C | 1.209 (6) | C26A—H42A | 0.9800 |
O3C—H3C | 0.73 (5) | C1B—C2B | 1.373 (5) |
O11C—H11C | 0.84 (3) | C1B—C6B | 1.389 (5) |
O51C—H51C | 0.90 (6) | C2B—C3B | 1.405 (5) |
O3D—C3D | 1.419 (5) | C3B—C4B | 1.390 (5) |
O11D—C1D | 1.330 (6) | C4B—C5B | 1.391 (5) |
O12D—C1D | 1.212 (5) | C5B—C6B | 1.389 (5) |
O31D—C31D | 1.248 (6) | C6B—C7B | 1.502 (5) |
O32D—C31D | 1.267 (6) | C7B—C16B | 1.532 (5) |
O51D—C5D | 1.329 (6) | C7B—C8B | 1.583 (5) |
O52D—C5D | 1.207 (5) | C7B—C17B | 1.545 (5) |
O3D—H3D | 0.81 (6) | C8B—C13B | 1.521 (5) |
O11D—H11D | 0.94 (5) | C10B—C11B | 1.514 (5) |
O51D—H51D | 0.96 (6) | C11B—C12B | 1.531 (5) |
O1W—H11W | 0.92 (4) | C12B—C13B | 1.531 (5) |
O1W—H12W | 0.92 (5) | C13B—C14B | 1.537 (5) |
N9A—C10A | 1.353 (5) | C14B—C21B | 1.506 (5) |
N9A—C5A | 1.424 (5) | C14B—C15B | 1.535 (5) |
N9A—C8A | 1.480 (4) | C15B—C16B | 1.512 (5) |
N19A—C18A | 1.510 (5) | C17B—C18B | 1.510 (6) |
N19A—C16A | 1.551 (5) | C20B—C21B | 1.506 (5) |
N19A—C20A | 1.516 (5) | C21B—C22B | 1.330 (6) |
O2W—H21W | 0.80 (5) | C22B—C23B | 1.511 (6) |
O2W—H22W | 0.83 (7) | C1B—H1B | 0.9500 |
N19A—H19A | 0.93 (4) | C4B—H4B | 0.9500 |
N9B—C10B | 1.345 (5) | C8B—H8B | 1.0000 |
N9B—C5B | 1.432 (5) | C11B—H28B | 0.9900 |
N9B—C8B | 1.470 (5) | C11B—H27B | 0.9900 |
N19B—C18B | 1.511 (6) | C12B—H12B | 1.0000 |
N19B—C16B | 1.537 (5) | C13B—H13B | 1.0000 |
N19B—C20B | 1.508 (5) | C14B—H14B | 1.0000 |
O3W—H31W | 0.91 (6) | C15B—H30B | 0.9900 |
O3W—H32W | 0.91 (4) | C15B—H29B | 0.9900 |
N19B—H19B | 0.94 (4) | C16B—H16B | 1.0000 |
O4W—H42W | 0.90 (4) | C17B—H31B | 0.9900 |
O4W—H41W | 0.86 (4) | C17B—H32B | 0.9900 |
O5W—H51W | 0.90 (3) | C18B—H34B | 0.9900 |
O5W—H52W | 0.90 (3) | C18B—H33B | 0.9900 |
O6W—H61W | 0.90 (3) | C20B—H72A | 0.9900 |
O6W—H62W | 0.87 (3) | C20B—H71A | 0.9900 |
C1A—C2A | 1.378 (5) | C22B—H22B | 0.9500 |
C1A—C6A | 1.397 (5) | C23B—H38B | 0.9900 |
C2A—C3A | 1.400 (5) | C23B—H37B | 0.9900 |
C3A—C4A | 1.391 (5) | C25B—H41B | 0.9800 |
C4A—C5A | 1.408 (5) | C25B—H39B | 0.9800 |
C5A—C6A | 1.377 (5) | C25B—H40B | 0.9800 |
C6A—C7A | 1.513 (5) | C26B—H42B | 0.9800 |
C7A—C16A | 1.540 (5) | C26B—H43B | 0.9800 |
C7A—C8A | 1.559 (5) | C26B—H44B | 0.9800 |
C7A—C17A | 1.540 (5) | C1C—C2C | 1.519 (5) |
C8A—C13A | 1.530 (5) | C2C—C3C | 1.527 (5) |
C10A—C11A | 1.511 (5) | C3C—C31C | 1.550 (5) |
C11A—C12A | 1.529 (5) | C3C—C4C | 1.537 (5) |
C12A—C13A | 1.521 (5) | C4C—C5C | 1.513 (6) |
C13A—C14A | 1.535 (5) | C2C—H21C | 0.9900 |
C14A—C21A | 1.522 (5) | C2C—H22C | 0.9900 |
C14A—C15A | 1.548 (5) | C4C—H42C | 0.9900 |
C15A—C16A | 1.522 (5) | C4C—H41C | 0.9900 |
C17A—C18A | 1.514 (5) | C1D—C2D | 1.500 (6) |
C20A—C21A | 1.501 (5) | C2D—C3D | 1.521 (6) |
C21A—C22A | 1.332 (5) | C3D—C4D | 1.533 (6) |
C22A—C23A | 1.497 (5) | C3D—C31D | 1.545 (6) |
C1A—H1A | 0.9500 | C4D—C5D | 1.504 (6) |
C4A—H4A | 0.9500 | C2D—H21D | 0.9900 |
C8A—H8A | 1.0000 | C2D—H22D | 0.9900 |
C11A—H28A | 0.9900 | C4D—H42D | 0.9900 |
C11A—H27A | 0.9900 | C4D—H41D | 0.9900 |
| | | |
C2A—O2A—C25A | 116.3 (3) | N9B—C5B—C4B | 128.3 (3) |
C3A—O3A—C26A | 116.6 (3) | C4B—C5B—C6B | 122.2 (4) |
C12A—O24A—C23A | 115.3 (3) | C1B—C6B—C7B | 129.3 (3) |
C2B—O2B—C25B | 116.7 (3) | C1B—C6B—C5B | 119.3 (3) |
C3B—O3B—C26B | 116.1 (3) | C5B—C6B—C7B | 111.3 (3) |
C12B—O24B—C23B | 115.3 (3) | C6B—C7B—C17B | 112.2 (3) |
C3C—O3C—H3C | 110 (4) | C8B—C7B—C16B | 114.2 (3) |
C1C—O11C—H11C | 110 (3) | C6B—C7B—C8B | 101.8 (3) |
C5C—O51C—H51C | 109 (4) | C8B—C7B—C17B | 110.7 (3) |
C3D—O3D—H3D | 99 (4) | C6B—C7B—C16B | 115.6 (3) |
C1D—O11D—H11D | 111 (3) | C16B—C7B—C17B | 102.6 (3) |
C5D—O51D—H51D | 109 (3) | N9B—C8B—C7B | 104.8 (3) |
H11W—O1W—H12W | 110 (4) | C7B—C8B—C13B | 115.8 (3) |
C8A—N9A—C10A | 119.7 (3) | N9B—C8B—C13B | 106.5 (3) |
C5A—N9A—C10A | 126.9 (3) | O25B—C10B—C11B | 121.6 (3) |
C5A—N9A—C8A | 109.2 (3) | N9B—C10B—C11B | 114.5 (3) |
C18A—N19A—C20A | 111.9 (3) | O25B—C10B—N9B | 123.9 (4) |
C16A—N19A—C18A | 107.0 (3) | C10B—C11B—C12B | 117.3 (3) |
C16A—N19A—C20A | 113.3 (3) | O24B—C12B—C11B | 103.5 (3) |
H21W—O2W—H22W | 119 (6) | C11B—C12B—C13B | 111.1 (3) |
C16A—N19A—H19A | 108 (2) | O24B—C12B—C13B | 114.2 (3) |
C18A—N19A—H19A | 108 (3) | C8B—C13B—C12B | 106.5 (3) |
C20A—N19A—H19A | 108 (3) | C12B—C13B—C14B | 118.7 (3) |
C5B—N9B—C10B | 125.7 (3) | C8B—C13B—C14B | 113.6 (3) |
C5B—N9B—C8B | 109.6 (3) | C13B—C14B—C15B | 106.4 (3) |
C8B—N9B—C10B | 119.8 (3) | C13B—C14B—C21B | 114.1 (3) |
C18B—N19B—C20B | 112.4 (3) | C15B—C14B—C21B | 109.5 (3) |
C16B—N19B—C18B | 107.0 (3) | C14B—C15B—C16B | 108.4 (3) |
C16B—N19B—C20B | 113.5 (3) | N19B—C16B—C7B | 105.4 (3) |
H31W—O3W—H32W | 132 (4) | C7B—C16B—C15B | 116.6 (3) |
C16B—N19B—H19B | 116 (2) | N19B—C16B—C15B | 110.0 (3) |
C18B—N19B—H19B | 108 (3) | C7B—C17B—C18B | 103.6 (3) |
C20B—N19B—H19B | 100 (3) | N19B—C18B—C17B | 105.9 (3) |
H41W—O4W—H42W | 126 (4) | N19B—C20B—C21B | 110.5 (3) |
H51W—O5W—H52W | 123 (3) | C14B—C21B—C22B | 123.2 (3) |
H61W—O6W—H62W | 100 (3) | C14B—C21B—C20B | 115.6 (3) |
C2A—C1A—C6A | 119.2 (3) | C20B—C21B—C22B | 121.2 (4) |
O2A—C2A—C3A | 115.0 (3) | C21B—C22B—C23B | 120.7 (4) |
C1A—C2A—C3A | 120.5 (4) | O24B—C23B—C22B | 111.5 (4) |
O2A—C2A—C1A | 124.5 (3) | C2B—C1B—H1B | 120.00 |
C2A—C3A—C4A | 121.1 (3) | C6B—C1B—H1B | 120.00 |
O3A—C3A—C2A | 116.0 (3) | C5B—C4B—H4B | 121.00 |
O3A—C3A—C4A | 122.9 (3) | C3B—C4B—H4B | 121.00 |
C3A—C4A—C5A | 117.3 (3) | C7B—C8B—H8B | 110.00 |
N9A—C5A—C4A | 127.8 (3) | N9B—C8B—H8B | 110.00 |
N9A—C5A—C6A | 110.5 (3) | C13B—C8B—H8B | 110.00 |
C4A—C5A—C6A | 121.7 (4) | C10B—C11B—H28B | 108.00 |
C5A—C6A—C7A | 110.2 (3) | C12B—C11B—H27B | 108.00 |
C1A—C6A—C7A | 129.5 (3) | C10B—C11B—H27B | 108.00 |
C1A—C6A—C5A | 120.1 (3) | H27B—C11B—H28B | 107.00 |
C6A—C7A—C16A | 116.4 (3) | C12B—C11B—H28B | 108.00 |
C6A—C7A—C8A | 102.4 (3) | O24B—C12B—H12B | 109.00 |
C16A—C7A—C17A | 101.8 (3) | C13B—C12B—H12B | 109.00 |
C8A—C7A—C16A | 113.6 (3) | C11B—C12B—H12B | 109.00 |
C8A—C7A—C17A | 111.5 (3) | C8B—C13B—H13B | 106.00 |
C6A—C7A—C17A | 111.4 (3) | C14B—C13B—H13B | 106.00 |
C7A—C8A—C13A | 117.3 (3) | C12B—C13B—H13B | 106.00 |
N9A—C8A—C7A | 104.7 (3) | C13B—C14B—H14B | 109.00 |
N9A—C8A—C13A | 106.4 (3) | C15B—C14B—H14B | 109.00 |
O25A—C10A—N9A | 123.7 (3) | C21B—C14B—H14B | 109.00 |
N9A—C10A—C11A | 114.2 (3) | C16B—C15B—H29B | 110.00 |
O25A—C10A—C11A | 122.0 (3) | C16B—C15B—H30B | 110.00 |
C10A—C11A—C12A | 118.1 (3) | H29B—C15B—H30B | 108.00 |
O24A—C12A—C11A | 103.7 (3) | C14B—C15B—H30B | 110.00 |
O24A—C12A—C13A | 114.5 (3) | C14B—C15B—H29B | 110.00 |
C11A—C12A—C13A | 110.8 (3) | C7B—C16B—H16B | 108.00 |
C8A—C13A—C14A | 112.7 (3) | C15B—C16B—H16B | 108.00 |
C12A—C13A—C14A | 118.3 (3) | N19B—C16B—H16B | 108.00 |
C8A—C13A—C12A | 107.5 (3) | C7B—C17B—H31B | 111.00 |
C13A—C14A—C21A | 114.7 (3) | C7B—C17B—H32B | 111.00 |
C15A—C14A—C21A | 109.0 (3) | C18B—C17B—H32B | 111.00 |
C13A—C14A—C15A | 106.9 (3) | H31B—C17B—H32B | 109.00 |
C14A—C15A—C16A | 107.9 (3) | C18B—C17B—H31B | 111.00 |
C7A—C16A—C15A | 116.9 (3) | C17B—C18B—H34B | 111.00 |
N19A—C16A—C7A | 104.8 (3) | C17B—C18B—H33B | 111.00 |
N19A—C16A—C15A | 110.1 (3) | H33B—C18B—H34B | 109.00 |
C7A—C17A—C18A | 103.6 (3) | N19B—C18B—H33B | 111.00 |
N19A—C18A—C17A | 104.8 (3) | N19B—C18B—H34B | 111.00 |
N19A—C20A—C21A | 110.8 (3) | N19B—C20B—H72A | 110.00 |
C20A—C21A—C22A | 121.7 (3) | N19B—C20B—H71A | 110.00 |
C14A—C21A—C22A | 122.1 (3) | C21B—C20B—H72A | 110.00 |
C14A—C21A—C20A | 116.2 (3) | H71A—C20B—H72A | 108.00 |
C21A—C22A—C23A | 120.4 (3) | C21B—C20B—H71A | 110.00 |
O24A—C23A—C22A | 110.6 (3) | C23B—C22B—H22B | 120.00 |
C6A—C1A—H1A | 120.00 | C21B—C22B—H22B | 120.00 |
C2A—C1A—H1A | 120.00 | O24B—C23B—H37B | 109.00 |
C5A—C4A—H4A | 121.00 | C22B—C23B—H38B | 109.00 |
C3A—C4A—H4A | 121.00 | C22B—C23B—H37B | 109.00 |
C7A—C8A—H8A | 109.00 | O24B—C23B—H38B | 109.00 |
C13A—C8A—H8A | 109.00 | H37B—C23B—H38B | 108.00 |
N9A—C8A—H8A | 109.00 | H39B—C25B—H40B | 110.00 |
H27A—C11A—H28A | 107.00 | O2B—C25B—H41B | 109.00 |
C12A—C11A—H28A | 108.00 | H39B—C25B—H41B | 110.00 |
C10A—C11A—H28A | 108.00 | H40B—C25B—H41B | 109.00 |
C12A—C11A—H27A | 108.00 | O2B—C25B—H39B | 109.00 |
C10A—C11A—H27A | 108.00 | O2B—C25B—H40B | 109.00 |
O24A—C12A—H12A | 109.00 | O3B—C26B—H42B | 110.00 |
C11A—C12A—H12A | 109.00 | O3B—C26B—H43B | 110.00 |
C13A—C12A—H12A | 109.00 | H42B—C26B—H43B | 109.00 |
C8A—C13A—H13A | 106.00 | O3B—C26B—H44B | 110.00 |
C12A—C13A—H13A | 106.00 | H42B—C26B—H44B | 109.00 |
C14A—C13A—H13A | 106.00 | H43B—C26B—H44B | 109.00 |
C21A—C14A—H14A | 109.00 | O11C—C1C—C2C | 115.3 (3) |
C15A—C14A—H14A | 109.00 | O12C—C1C—C2C | 123.2 (3) |
C13A—C14A—H14A | 109.00 | O11C—C1C—O12C | 121.4 (3) |
H29A—C15A—H30A | 108.00 | C1C—C2C—C3C | 115.0 (3) |
C14A—C15A—H29A | 110.00 | C4C—C3C—C31C | 109.1 (3) |
C14A—C15A—H30A | 110.00 | C2C—C3C—C4C | 106.4 (3) |
C16A—C15A—H29A | 110.00 | C2C—C3C—C31C | 111.9 (3) |
C16A—C15A—H30A | 110.00 | O3C—C3C—C4C | 108.2 (3) |
N19A—C16A—H16A | 108.00 | O3C—C3C—C31C | 110.6 (3) |
C7A—C16A—H16A | 108.00 | O3C—C3C—C2C | 110.5 (3) |
C15A—C16A—H16A | 108.00 | C3C—C4C—C5C | 113.1 (3) |
C7A—C17A—H31A | 111.00 | O51C—C5C—O52C | 122.5 (4) |
C18A—C17A—H32A | 111.00 | O51C—C5C—C4C | 113.5 (4) |
H31A—C17A—H32A | 109.00 | O52C—C5C—C4C | 124.0 (4) |
C18A—C17A—H31A | 111.00 | O31C—C31C—O32C | 126.4 (4) |
C7A—C17A—H32A | 111.00 | O31C—C31C—C3C | 117.1 (3) |
C17A—C18A—H34A | 111.00 | O32C—C31C—C3C | 116.5 (3) |
N19A—C18A—H33A | 111.00 | C1C—C2C—H22C | 109.00 |
N19A—C18A—H34A | 111.00 | C3C—C2C—H21C | 109.00 |
C17A—C18A—H33A | 111.00 | H21C—C2C—H22C | 107.00 |
H33A—C18A—H34A | 109.00 | C3C—C2C—H22C | 109.00 |
C21A—C20A—H36A | 110.00 | C1C—C2C—H21C | 109.00 |
C21A—C20A—H35A | 109.00 | C3C—C4C—H41C | 109.00 |
N19A—C20A—H36A | 109.00 | C5C—C4C—H42C | 109.00 |
N19A—C20A—H35A | 109.00 | C3C—C4C—H42C | 109.00 |
H35A—C20A—H36A | 108.00 | H41C—C4C—H42C | 108.00 |
C21A—C22A—H22A | 120.00 | C5C—C4C—H41C | 109.00 |
C23A—C22A—H22A | 120.00 | O11D—C1D—O12D | 119.7 (4) |
O24A—C23A—H37A | 110.00 | O12D—C1D—C2D | 124.6 (4) |
H37A—C23A—H38A | 108.00 | O11D—C1D—C2D | 115.7 (4) |
C22A—C23A—H38A | 109.00 | C1D—C2D—C3D | 116.5 (4) |
O24A—C23A—H38A | 110.00 | C2D—C3D—C4D | 108.1 (3) |
C22A—C23A—H37A | 110.00 | O3D—C3D—C31D | 110.9 (3) |
O2A—C25A—H39A | 109.00 | O3D—C3D—C2D | 107.1 (4) |
O2A—C25A—H40A | 109.00 | C4D—C3D—C31D | 109.5 (3) |
H39A—C25A—H40A | 109.00 | C2D—C3D—C31D | 111.6 (3) |
O2A—C25A—H41A | 109.00 | O3D—C3D—C4D | 109.6 (3) |
H40A—C25A—H41A | 109.00 | C3D—C4D—C5D | 115.6 (3) |
H39A—C25A—H41A | 109.00 | O51D—C5D—C4D | 111.2 (4) |
O3A—C26A—H42A | 109.00 | O52D—C5D—C4D | 126.0 (4) |
H42A—C26A—H43A | 110.00 | O51D—C5D—O52D | 122.8 (4) |
H42A—C26A—H44A | 109.00 | O31D—C31D—O32D | 125.9 (4) |
O3A—C26A—H44A | 109.00 | O32D—C31D—C3D | 114.6 (4) |
H43A—C26A—H44A | 110.00 | O31D—C31D—C3D | 119.6 (4) |
O3A—C26A—H43A | 109.00 | C3D—C2D—H21D | 108.00 |
C2B—C1B—C6B | 119.8 (3) | C1D—C2D—H22D | 108.00 |
O2B—C2B—C3B | 114.2 (3) | C1D—C2D—H21D | 108.00 |
O2B—C2B—C1B | 125.2 (3) | C3D—C2D—H22D | 108.00 |
C1B—C2B—C3B | 120.6 (4) | H21D—C2D—H22D | 107.00 |
O3B—C3B—C4B | 124.2 (3) | H41D—C4D—H42D | 107.00 |
O3B—C3B—C2B | 115.3 (3) | C3D—C4D—H41D | 108.00 |
C2B—C3B—C4B | 120.5 (3) | C3D—C4D—H42D | 108.00 |
C3B—C4B—C5B | 117.7 (3) | C5D—C4D—H41D | 108.00 |
N9B—C5B—C6B | 109.6 (3) | C5D—C4D—H42D | 108.00 |
| | | |
C25A—O2A—C2A—C1A | 9.7 (5) | C15A—C14A—C21A—C20A | −0.3 (4) |
C25A—O2A—C2A—C3A | −171.6 (3) | C13A—C14A—C15A—C16A | 67.2 (4) |
C26A—O3A—C3A—C2A | −179.7 (3) | C13A—C14A—C21A—C22A | 61.8 (5) |
C26A—O3A—C3A—C4A | −0.3 (5) | C14A—C15A—C16A—C7A | −55.3 (4) |
C23A—O24A—C12A—C11A | 173.6 (3) | C14A—C15A—C16A—N19A | 64.1 (3) |
C23A—O24A—C12A—C13A | −65.6 (4) | C7A—C17A—C18A—N19A | 37.2 (4) |
C12A—O24A—C23A—C22A | 90.9 (4) | N19A—C20A—C21A—C22A | −130.3 (3) |
C25B—O2B—C2B—C1B | 9.1 (5) | N19A—C20A—C21A—C14A | 51.5 (4) |
C25B—O2B—C2B—C3B | −172.2 (3) | C20A—C21A—C22A—C23A | 178.0 (3) |
C26B—O3B—C3B—C2B | 177.4 (3) | C14A—C21A—C22A—C23A | −3.9 (5) |
C26B—O3B—C3B—C4B | −3.0 (5) | C21A—C22A—C23A—O24A | −66.3 (4) |
C23B—O24B—C12B—C11B | 172.9 (3) | C6B—C1B—C2B—C3B | 2.6 (6) |
C23B—O24B—C12B—C13B | −66.2 (4) | C6B—C1B—C2B—O2B | −178.8 (3) |
C12B—O24B—C23B—C22B | 89.3 (4) | C2B—C1B—C6B—C7B | −175.8 (4) |
C10A—N9A—C5A—C6A | −160.3 (3) | C2B—C1B—C6B—C5B | −0.3 (5) |
C5A—N9A—C8A—C7A | 13.5 (4) | O2B—C2B—C3B—O3B | −1.3 (5) |
C10A—N9A—C5A—C4A | 19.6 (6) | C1B—C2B—C3B—C4B | −2.1 (6) |
C8A—N9A—C5A—C6A | −4.0 (4) | O2B—C2B—C3B—C4B | 179.1 (3) |
C8A—N9A—C10A—C11A | 6.4 (5) | C1B—C2B—C3B—O3B | 177.6 (3) |
C5A—N9A—C8A—C13A | −111.4 (3) | O3B—C3B—C4B—C5B | 179.7 (3) |
C8A—N9A—C5A—C4A | 175.8 (4) | C2B—C3B—C4B—C5B | −0.7 (6) |
C10A—N9A—C8A—C13A | 46.8 (4) | C3B—C4B—C5B—N9B | −176.5 (4) |
C8A—N9A—C10A—O25A | −174.8 (3) | C3B—C4B—C5B—C6B | 3.0 (6) |
C10A—N9A—C8A—C7A | 171.7 (3) | C4B—C5B—C6B—C1B | −2.6 (6) |
C5A—N9A—C10A—O25A | −20.8 (6) | C4B—C5B—C6B—C7B | 173.7 (3) |
C5A—N9A—C10A—C11A | 160.4 (3) | N9B—C5B—C6B—C1B | 177.0 (3) |
C20A—N19A—C18A—C17A | −141.8 (3) | N9B—C5B—C6B—C7B | −6.7 (4) |
C18A—N19A—C16A—C15A | −136.1 (3) | C1B—C6B—C7B—C16B | −45.4 (5) |
C20A—N19A—C16A—C7A | 114.4 (3) | C5B—C6B—C7B—C16B | 138.8 (3) |
C20A—N19A—C16A—C15A | −12.2 (4) | C5B—C6B—C7B—C17B | −104.0 (4) |
C16A—N19A—C20A—C21A | −44.1 (4) | C1B—C6B—C7B—C8B | −169.8 (4) |
C18A—N19A—C20A—C21A | 77.1 (4) | C5B—C6B—C7B—C8B | 14.4 (4) |
C16A—N19A—C18A—C17A | −17.0 (4) | C1B—C6B—C7B—C17B | 71.8 (5) |
C18A—N19A—C16A—C7A | −9.5 (4) | C8B—C7B—C17B—C18B | 82.7 (3) |
C8B—N9B—C5B—C6B | −5.0 (4) | C6B—C7B—C17B—C18B | −164.3 (3) |
C5B—N9B—C10B—C11B | 159.8 (3) | C6B—C7B—C16B—C15B | −84.6 (4) |
C10B—N9B—C5B—C6B | −160.1 (3) | C8B—C7B—C16B—N19B | −89.1 (4) |
C5B—N9B—C8B—C13B | −109.6 (3) | C6B—C7B—C8B—C13B | 100.7 (3) |
C10B—N9B—C8B—C7B | 170.5 (3) | C16B—C7B—C8B—N9B | −141.8 (3) |
C10B—N9B—C8B—C13B | 47.2 (4) | C16B—C7B—C8B—C13B | −24.7 (5) |
C8B—N9B—C5B—C4B | 174.6 (4) | C17B—C7B—C8B—N9B | 103.0 (3) |
C8B—N9B—C10B—C11B | 7.0 (5) | C17B—C7B—C8B—C13B | −139.9 (3) |
C5B—N9B—C8B—C7B | 13.7 (4) | C6B—C7B—C16B—N19B | 153.2 (3) |
C8B—N9B—C10B—O25B | −173.9 (3) | C17B—C7B—C16B—N19B | 30.8 (4) |
C10B—N9B—C5B—C4B | 19.5 (6) | C6B—C7B—C8B—N9B | −16.4 (4) |
C5B—N9B—C10B—O25B | −21.1 (6) | C8B—C7B—C16B—C15B | 33.1 (5) |
C20B—N19B—C18B—C17B | −139.3 (3) | C16B—C7B—C17B—C18B | −39.6 (4) |
C16B—N19B—C20B—C21B | −43.8 (4) | C17B—C7B—C16B—C15B | 153.0 (3) |
C20B—N19B—C16B—C7B | 113.7 (3) | C7B—C8B—C13B—C14B | 40.4 (4) |
C16B—N19B—C18B—C17B | −14.1 (4) | N9B—C8B—C13B—C12B | −71.0 (4) |
C18B—N19B—C20B—C21B | 77.9 (4) | C7B—C8B—C13B—C12B | 172.9 (3) |
C18B—N19B—C16B—C7B | −10.9 (4) | N9B—C8B—C13B—C14B | 156.6 (3) |
C20B—N19B—C16B—C15B | −12.7 (4) | O25B—C10B—C11B—C12B | 142.8 (4) |
C18B—N19B—C16B—C15B | −137.3 (3) | N9B—C10B—C11B—C12B | −38.0 (5) |
C2A—C1A—C6A—C5A | 0.9 (6) | C10B—C11B—C12B—O24B | 133.8 (3) |
C2A—C1A—C6A—C7A | −173.7 (4) | C10B—C11B—C12B—C13B | 10.9 (5) |
C6A—C1A—C2A—O2A | −179.0 (3) | C11B—C12B—C13B—C14B | 170.8 (3) |
C6A—C1A—C2A—C3A | 2.4 (6) | O24B—C12B—C13B—C14B | 54.2 (4) |
O2A—C2A—C3A—C4A | 177.8 (3) | O24B—C12B—C13B—C8B | −75.4 (4) |
O2A—C2A—C3A—O3A | −2.9 (5) | C11B—C12B—C13B—C8B | 41.3 (4) |
C1A—C2A—C3A—C4A | −3.5 (6) | C12B—C13B—C14B—C21B | −67.1 (4) |
C1A—C2A—C3A—O3A | 175.9 (3) | C8B—C13B—C14B—C15B | −61.8 (4) |
C2A—C3A—C4A—C5A | 1.3 (6) | C12B—C13B—C14B—C15B | 172.0 (3) |
O3A—C3A—C4A—C5A | −178.1 (3) | C8B—C13B—C14B—C21B | 59.1 (4) |
C3A—C4A—C5A—N9A | −177.7 (4) | C15B—C14B—C21B—C20B | −2.2 (4) |
C3A—C4A—C5A—C6A | 2.1 (6) | C13B—C14B—C21B—C20B | −121.3 (3) |
C4A—C5A—C6A—C1A | −3.2 (6) | C13B—C14B—C21B—C22B | 60.0 (5) |
N9A—C5A—C6A—C7A | −7.8 (4) | C13B—C14B—C15B—C16B | 67.8 (4) |
C4A—C5A—C6A—C7A | 172.4 (3) | C21B—C14B—C15B—C16B | −55.9 (3) |
N9A—C5A—C6A—C1A | 176.7 (3) | C15B—C14B—C21B—C22B | 179.1 (3) |
C1A—C6A—C7A—C8A | −169.6 (4) | C14B—C15B—C16B—C7B | −55.7 (4) |
C1A—C6A—C7A—C16A | −45.0 (6) | C14B—C15B—C16B—N19B | 64.1 (3) |
C1A—C6A—C7A—C17A | 71.1 (5) | C7B—C17B—C18B—N19B | 33.3 (4) |
C5A—C6A—C7A—C17A | −103.9 (4) | N19B—C20B—C21B—C14B | 52.6 (4) |
C5A—C6A—C7A—C16A | 140.0 (3) | N19B—C20B—C21B—C22B | −128.6 (4) |
C5A—C6A—C7A—C8A | 15.4 (4) | C14B—C21B—C22B—C23B | −3.5 (6) |
C17A—C7A—C8A—C13A | −140.0 (3) | C20B—C21B—C22B—C23B | 177.8 (3) |
C8A—C7A—C17A—C18A | 78.8 (3) | C21B—C22B—C23B—O24B | −65.4 (5) |
C16A—C7A—C8A—C13A | −25.7 (4) | O11C—C1C—C2C—C3C | 174.6 (3) |
C17A—C7A—C8A—N9A | 102.4 (3) | O12C—C1C—C2C—C3C | −5.8 (5) |
C6A—C7A—C17A—C18A | −167.4 (3) | C1C—C2C—C3C—C31C | −53.3 (4) |
C6A—C7A—C16A—N19A | 152.9 (3) | C1C—C2C—C3C—C4C | −172.3 (3) |
C17A—C7A—C16A—C15A | 153.8 (3) | C1C—C2C—C3C—O3C | 70.5 (4) |
C16A—C7A—C17A—C18A | −42.6 (4) | O3C—C3C—C31C—O31C | 10.6 (4) |
C16A—C7A—C8A—N9A | −143.3 (3) | O3C—C3C—C31C—O32C | −170.6 (3) |
C17A—C7A—C16A—N19A | 31.6 (4) | C2C—C3C—C4C—C5C | −177.1 (3) |
C6A—C7A—C8A—C13A | 100.7 (3) | C31C—C3C—C4C—C5C | 62.0 (4) |
C6A—C7A—C8A—N9A | −16.9 (3) | C4C—C3C—C31C—O31C | −108.2 (4) |
C6A—C7A—C16A—C15A | −84.9 (4) | C2C—C3C—C31C—O31C | 134.3 (3) |
C8A—C7A—C16A—N19A | −88.4 (4) | C2C—C3C—C31C—O32C | −46.9 (4) |
C8A—C7A—C16A—C15A | 33.8 (4) | O3C—C3C—C4C—C5C | −58.3 (4) |
N9A—C8A—C13A—C14A | 157.7 (3) | C4C—C3C—C31C—O32C | 70.6 (4) |
C7A—C8A—C13A—C14A | 41.0 (4) | C3C—C4C—C5C—O52C | 91.0 (5) |
C7A—C8A—C13A—C12A | 173.1 (3) | C3C—C4C—C5C—O51C | −89.6 (4) |
N9A—C8A—C13A—C12A | −70.2 (3) | O11D—C1D—C2D—C3D | −165.4 (3) |
O25A—C10A—C11A—C12A | 142.8 (4) | O12D—C1D—C2D—C3D | 15.2 (6) |
N9A—C10A—C11A—C12A | −38.4 (5) | C1D—C2D—C3D—C4D | −173.8 (3) |
C10A—C11A—C12A—O24A | 135.5 (3) | C1D—C2D—C3D—O3D | 68.2 (4) |
C10A—C11A—C12A—C13A | 12.2 (5) | C1D—C2D—C3D—C31D | −53.3 (5) |
O24A—C12A—C13A—C8A | −76.7 (4) | O3D—C3D—C31D—O31D | −0.5 (5) |
C11A—C12A—C13A—C14A | 169.0 (3) | C4D—C3D—C31D—O32D | 58.0 (4) |
C11A—C12A—C13A—C8A | 40.0 (4) | C2D—C3D—C4D—C5D | 176.1 (3) |
O24A—C12A—C13A—C14A | 52.3 (4) | C31D—C3D—C4D—C5D | 54.4 (5) |
C12A—C13A—C14A—C15A | 172.2 (3) | O3D—C3D—C31D—O32D | 179.0 (3) |
C8A—C13A—C14A—C15A | −61.2 (4) | C2D—C3D—C31D—O31D | 118.8 (4) |
C12A—C13A—C14A—C21A | −66.8 (4) | C2D—C3D—C31D—O32D | −61.7 (4) |
C8A—C13A—C14A—C21A | 59.7 (4) | C4D—C3D—C31D—O31D | −121.5 (4) |
C13A—C14A—C21A—C20A | −120.0 (3) | O3D—C3D—C4D—C5D | −67.4 (4) |
C21A—C14A—C15A—C16A | −57.2 (3) | C3D—C4D—C5D—O51D | 178.8 (3) |
C15A—C14A—C21A—C22A | −178.4 (3) | C3D—C4D—C5D—O52D | −0.4 (6) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N19A—H19A···O32C | 0.93 (4) | 1.76 (4) | 2.645 (4) | 156 (4) |
N19B—H19B···O31Di | 0.94 (4) | 2.14 (4) | 2.824 (4) | 128 (3) |
N19B—H19B···O6Wii | 0.94 (4) | 2.12 (4) | 2.873 (5) | 135 (3) |
O3C—H3C···O4W | 0.73 (5) | 2.36 (5) | 3.051 (5) | 159 (5) |
O3C—H3C···O31C | 0.73 (5) | 2.28 (5) | 2.640 (4) | 111 (4) |
O3D—H3D···O6Wiii | 0.81 (6) | 2.10 (6) | 2.761 (4) | 140 (6) |
O3D—H3D···O31D | 0.81 (6) | 2.08 (7) | 2.678 (4) | 131 (5) |
O11C—H11C···O32Div | 0.84 (3) | 1.70 (3) | 2.537 (4) | 173 (5) |
O11D—H11D···O31C | 0.94 (5) | 1.69 (5) | 2.604 (4) | 167 (4) |
O51C—H51C···O25B | 0.90 (6) | 1.78 (7) | 2.685 (4) | 179 (8) |
O51D—H51D···O25Av | 0.96 (6) | 1.72 (6) | 2.647 (4) | 162 (5) |
O1W—H11W···O3D | 0.92 (4) | 1.86 (5) | 2.764 (5) | 169 (4) |
O1W—H12W···O2W | 0.92 (5) | 1.83 (5) | 2.740 (5) | 170 (4) |
O2W—H21W···O31Div | 0.80 (5) | 2.01 (5) | 2.798 (4) | 169 (5) |
O2W—H22W···O32C | 0.83 (7) | 1.95 (7) | 2.758 (4) | 162 (7) |
O3W—H31W···O12Dvi | 0.91 (6) | 2.35 (6) | 3.218 (5) | 161 (4) |
O3W—H32W···O3C | 0.91 (4) | 2.02 (4) | 2.920 (5) | 179 (5) |
O4W—H41W···O1Wvii | 0.86 (4) | 1.87 (4) | 2.735 (6) | 180 (6) |
O4W—H42W···O12C | 0.90 (4) | 1.97 (4) | 2.861 (5) | 171 (5) |
O5W—H51W···O4W | 0.90 (3) | 1.89 (3) | 2.790 (6) | 180 (4) |
O5W—H52W···O32D | 0.90 (3) | 1.88 (3) | 2.774 (5) | 179 (4) |
O6W—H61W···O5W | 0.90 (3) | 1.79 (3) | 2.689 (5) | 180 (4) |
O6W—H62W···O3Wviii | 0.87 (3) | 2.01 (3) | 2.806 (6) | 153 (3) |
C4A—H4A···O25A | 0.95 | 2.45 | 2.975 (5) | 115 |
C4A—H4A···O51Dix | 0.95 | 2.59 | 3.482 (5) | 156 |
C4B—H4B···O25B | 0.95 | 2.42 | 2.951 (5) | 115 |
C13B—H13B···O25Avii | 1.00 | 2.58 | 3.427 (5) | 143 |
C22B—H22B···O12Cix | 0.95 | 2.48 | 3.366 (5) | 155 |
C15A—H30A···O52Ciii | 0.99 | 2.51 | 3.263 (5) | 132 |
C17B—H31B···O52Di | 0.99 | 2.54 | 3.244 (5) | 128 |
C17A—H32A···O2Bx | 0.99 | 2.52 | 3.461 (5) | 159 |
C17B—H32B···O2A | 0.99 | 2.58 | 3.526 (4) | 159 |
C18A—H33A···O11D | 0.99 | 2.44 | 3.241 (5) | 138 |
C18A—H34A···O3Bx | 0.99 | 2.52 | 3.342 (5) | 140 |
C25B—H41B···O24Bvi | 0.98 | 2.48 | 3.174 (5) | 128 |
C26B—H42B···O52C | 0.98 | 2.48 | 3.098 (5) | 121 |
Symmetry codes: (i) x+1, y−1, z+1; (ii) x+1, y, z+1; (iii) x, y+1, z; (iv) x+1, y, z; (v) x, y, z−1; (vi) x+1, y−1, z; (vii) x, y−1, z; (viii) x−1, y, z; (ix) x, y, z+1; (x) x−1, y+1, z. |
Experimental details
Crystal data |
Chemical formula | C23H27N2O42+·C6H7O72−·3H2O |
Mr | 640.63 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 130 |
a, b, c (Å) | 9.2355 (8), 9.6894 (8), 17.1446 (15) |
α, β, γ (°) | 75.775 (2), 80.917 (2), 81.553 (2) |
V (Å3) | 1459.1 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.45 × 0.40 × 0.30 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 7737, 5129, 4354 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.075, 0.92 |
No. of reflections | 5129 |
No. of parameters | 888 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.19 |
Selected torsion angles (º) topO11C—C1C—C2C—C3C | 174.6 (3) | O11D—C1D—C2D—C3D | −165.4 (3) |
O12C—C1C—C2C—C3C | −5.8 (5) | O12D—C1D—C2D—C3D | 15.2 (6) |
C1C—C2C—C3C—O3C | 70.5 (4) | C1D—C2D—C3D—O3D | 68.2 (4) |
O3C—C3C—C31C—O31C | 10.6 (4) | O3D—C3D—C31D—O31D | −0.5 (5) |
O3C—C3C—C31C—O32C | −170.6 (3) | C4D—C3D—C31D—O32D | 58.0 (4) |
C4C—C3C—C31C—O31C | −108.2 (4) | O3D—C3D—C31D—O32D | 179.0 (3) |
C2C—C3C—C31C—O31C | 134.3 (3) | C2D—C3D—C31D—O31D | 118.8 (4) |
C2C—C3C—C31C—O32C | −46.9 (4) | C2D—C3D—C31D—O32D | −61.7 (4) |
O3C—C3C—C4C—C5C | −58.3 (4) | C4D—C3D—C31D—O31D | −121.5 (4) |
C4C—C3C—C31C—O32C | 70.6 (4) | O3D—C3D—C4D—C5D | −67.4 (4) |
C3C—C4C—C5C—O52C | 91.0 (5) | C3D—C4D—C5D—O51D | 178.8 (3) |
C3C—C4C—C5C—O51C | −89.6 (4) | C3D—C4D—C5D—O52D | −0.4 (6) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N19A—H19A···O32C | 0.93 (4) | 1.76 (4) | 2.645 (4) | 156 (4) |
N19B—H19B···O31Di | 0.94 (4) | 2.14 (4) | 2.824 (4) | 128 (3) |
N19B—H19B···O6Wii | 0.94 (4) | 2.12 (4) | 2.873 (5) | 135 (3) |
O3C—H3C···O4W | 0.73 (5) | 2.36 (5) | 3.051 (5) | 159 (5) |
O3C—H3C···O31C | 0.73 (5) | 2.28 (5) | 2.640 (4) | 111 (4) |
O3D—H3D···O6Wiii | 0.81 (6) | 2.10 (6) | 2.761 (4) | 140 (6) |
O3D—H3D···O31D | 0.81 (6) | 2.08 (7) | 2.678 (4) | 131 (5) |
O11C—H11C···O32Div | 0.84 (3) | 1.70 (3) | 2.537 (4) | 173 (5) |
O11D—H11D···O31C | 0.94 (5) | 1.69 (5) | 2.604 (4) | 167 (4) |
O51C—H51C···O25B | 0.90 (6) | 1.78 (7) | 2.685 (4) | 179 (8) |
O51D—H51D···O25Av | 0.96 (6) | 1.72 (6) | 2.647 (4) | 162 (5) |
O1W—H11W···O3D | 0.92 (4) | 1.86 (5) | 2.764 (5) | 169 (4) |
O1W—H12W···O2W | 0.92 (5) | 1.83 (5) | 2.740 (5) | 170 (4) |
O2W—H21W···O31Div | 0.80 (5) | 2.01 (5) | 2.798 (4) | 169 (5) |
O2W—H22W···O32C | 0.83 (7) | 1.95 (7) | 2.758 (4) | 162 (7) |
O3W—H31W···O12Dvi | 0.91 (6) | 2.35 (6) | 3.218 (5) | 161 (4) |
O3W—H32W···O3C | 0.91 (4) | 2.02 (4) | 2.920 (5) | 179 (5) |
O4W—H41W···O1Wvii | 0.86 (4) | 1.87 (4) | 2.735 (6) | 180 (6) |
O4W—H42W···O12C | 0.90 (4) | 1.97 (4) | 2.861 (5) | 171 (5) |
O5W—H51W···O4W | 0.90 (3) | 1.89 (3) | 2.790 (6) | 180 (4) |
O5W—H52W···O32D | 0.90 (3) | 1.88 (3) | 2.774 (5) | 179 (4) |
O6W—H61W···O5W | 0.90 (3) | 1.79 (3) | 2.689 (5) | 180 (4) |
O6W—H62W···O3Wviii | 0.87 (3) | 2.01 (3) | 2.806 (6) | 153 (3) |
Symmetry codes: (i) x+1, y−1, z+1; (ii) x+1, y, z+1; (iii) x, y+1, z; (iv) x+1, y, z; (v) x, y, z−1; (vi) x+1, y−1, z; (vii) x, y−1, z; (viii) x−1, y, z. |
Citric acid has been commonly employed to form water-soluble salts with organic compounds having little aqueous solubility. This has direct application in the preparation of pharmaceutical products where water solubility and biological compatibility are desirable. Because the ionization constants for the three carboxylic acid groups of citric acid are similar (pKa1–3 = 3.1, 4.8, 6.4), stoichiometric reaction with strong bases readily results in possible formation of the full range of salts viz. dihydrogencitrates, hydrogencitrates and normal citrates. However the 1:1 interaction with compounds having nitrogen Lewis base functional groups, such as those commonly incorporated in drug molecules, will, depending on the number and base strength of the N-acceptor group, usually give dihydrogencitrate salts. This is the case with the antiestrogenic drug tamoxifen citrate (O'Neil, 2001) and sildenafil citrate monohydrate (Viagra), while with the opiate fentanyl citrate (O'Neil, 2001) (two N-acceptors), the citrate is dianionic. This behaviour has been confirmed in the crystal structure determinations of tamoxifen citrate (Goldberg & Becker, 1987), fenantyl citrate [Peeters et al., 1960; Duchamp et al., 1977 (123 K)] and sildenafil citrate monohydrate (Yathirajan et al., 2005). The Strychnos alkaloids strychnine and brucine have two N-acceptors (pKa1 = 6.0 and pKa2 = 11.7), the widely separated values meaning that only with strong acids is the rare dication species formed. Crystallographically characterized examples include strychninium sulfate pentahydrate (Bokhoven et al., 1951) and brucinium binaphtholphosphate dihydrate ethanol solvate (Bao et al., 1996). Although the structures of a large number of the proton-transfer compounds of both alkaloids are known, those with the α-hydroxy acids are rare, although both strychnine and brucine have been used for the resolution of a number of such acids (Wilen, 1972). The known crystal structures comprise two strychnine salts with resolved enantiomorphic tartrates, strychninium hydrogen-(2S,3S)-tartrate trihydrate and bis(strychninium) (2R,3R)- tartrate hexahydrate (Gould et al., 1987) and brucinium L-glycerate 4.5 hydrate (Bialońska et al., 2005). No examples of compounds with achiral α-hydroxy acids have been reported. Therefore, the formation of large well formed crystals from the 1:1 stoichiometric interaction of brucine with citric acid in 80% ethanol–water were of interest, and this compound, brucinium dihydrogencitrate trihydrate (I), C23H27N2O4+. C5H7O7-. 3H2O, reported here, represents the first example of its type. Because of the lability of the interstitial water molecules in many hydrated compounds of brucine (Gould et al., 2002; Bialońska et al., 2005; Smith et al., 2005), data collection using a CCD-detector diffractometer operating at low temperature [130 (2) K] was employed.
The structure of (I) shows the presence of two independent brucinium cations (molecules A and B) (Fig. 1), two dihydrogencitrate anions (molecules C and D) and six water molecules of solvation (Fig. 2) in the triclinic (P1) asymmetric unit. Protonation occurs as expected at atom N19 of the brucine cage in each molecule, the invoked Peerdeman (1956) absolute configuration giving the overall Cahn–Ingold–Prelog stereochemistry of the cation molecules (Eliel, 1962) as C7(S), C8(S), C12(S), C13(R), C14(R), C16(S), N19(S). The central carboxylic acid group of citric acid [associated with the first dissociation constant (pKa1 = 3.1)] is deprotonated in both residues, this being consistent with what is found in the structures of tamoxifen citrate (Goldberg & Becker, 1987), sildenafil citrate (Yathirajan et al., 2005) and the alkali metal dihydrogencitrates, e.g. the Na salt (Glusker et al., 1965). O atoms of the same central carboxylate groups in both the C and D anions act as acceptors in intramolecular hydrogen bonds with the O3 hydroxyl groups, resulting in near-coplanarity of the carboxylate group and the C3—O3 bond vector [O3···O31 = 2.640 (4) (C) and 2.678 (4) Å (D); O3—C3—C31—O31 = 10.6 (4) (C) and −0.5 (5)° (D)]. The structure also features extensive intermolecular hydrogen bonding (Table 1) involving all molecular species.
The brucinium cations in (I) form into the previously described undulating sheet host substructures, which are the reason for the molecular recognition peculiar to brucine (Gould & Walkinshaw, 1984; Gould et al., 1985; Dijksma et al., 1998; Oshikawa et al., 2002; Bialońska & Ciunik, 2004a,b). In (I), these structures extend through the crystal along the b cell direction (Fig. 3), with the dihydrogencitrate anions and the water molecules occupying the interstitial spaces. The protonated N19 centres of cation A give a single hydrogen bonding interaction with an O-atom acceptor of the central carboxylate group of a C-citrate residue [N19A···O31C = 2.645 (4) Å], while cation B forms a three-centred interaction with a D-citrate O-atom [N19B···O31Di = 2.824 (4) Å] and a water molecule [N19B···O6Wii = 2.873 (5) Å; symmetry codes: (i) 1 + x, y − 1, 1 + z; (ii) 1 + x, y, 1 + z]. However, the molecules within the brucinium host structures do not give either the 2121 propagation in the orthorhombic (P212121) examples or the 21 propagation in the monoclinic (P21) examples which constitute the large majority of structural types in this series. Instead, there is a pseudo-21 structural framework, similar to that in the low-temperature brucinium L-glycerate 4.75 hydrate structure (Bialońska et al., 2005). The similarity extends also to space group (P1, Z = 2), its cell parameters (a = 9.31 Å, b = 9.58 Å, c = 16.13 Å, α = 77.21°, β = 87.36°, γ = 81.57°) and the general pseudo-21 propagation of the basic undulating brucinium cation substructural framework.
The terminal carboxylic acid residues of C and D also extend the structure in the c cell direction through interactions with brucinium carbonyl O-atom acceptors [O51C—H51C···O25B = 2.685 (4) Å; O51D—H51D···O25Av = 2.647 (4) Å; symmetry code: (v) x, y, z − 1]. The six water molecules of solvation complete an extensive secondary hydrogen-bonding framework through both water–water and water–anion interactions (Table 1) which associates with the brucinium-cation host structure, resulting in a three-dimensional polymer.
Although both C and D dihydrogen citrate residues adopt similar extended conformations, the two are conformationally dissimilar (Table 2), particularly with respect to the terminal carboxylic acid groups, as indicated by the comparative torsion angles C3—C2—C1—O12 [−5.8 (5)° (C) cf. 15.2 (6)° (D)] and C3—C4—C5—O52 [91.0 (5)° (C) cf. −0.4 (6)° (D)]. The previously mentioned intramolecularly hydrogen-bonded central carboxylate groups show a smaller variation. It is also of interest to note the presence of anti-related protons on the O11C and O11D carboxylic acid O atoms. These provide both strong A···D intra-unit anion associations [O11D···O31C = 2.694 (4) Å] and catemeric A···D inter-unit associations [O11D ···O31Civ = 2.573 (4) Å; symmetry code: (iv) 1 + x, y, z], which extend down the a cell direction. This overall molecular flexibility is a characteristic feature of citrates, and in the case of (I) not only results in the conformational variation within anions C and D but subsequently contributes largely to the degeneration of the crystal space symmetry to P1. Also contributing to this is probably the presence of the six water molecules of solvatio, which act in a semi-random manner in both a proton-donor/acceptor and a space-filling capacity. These aspects of the structure of (I) also resemble those of the brucinium L-glycerate structure (Bialońska et al., 2005).