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Acta Cryst. (2007). E63, o3053    [ doi:10.1107/S1600536807025603 ]

Triethylaminium-trimesate-trimesic acid-water (1/1/1/2)

J.-M. Chen, J.-J. Sun, W.-W. Huang, Y.-N. Lao and S.-P. Yang

Abstract top

The asymmetric unit of the title compound, C6H16N+·C9H5O6-·C9H6O6·2H2O, consists of a protonated triethylamine cation, one singly deprotonated trimesate anion, one trimesic acid molecule, and two water molecules. The trimesic acid molecules form stacks, while pairs of parallel anions also have [pi]-[pi] interactions; the perpendicular distances between adjacent parallel benzene rings are 3.291 (1), 3.347 (1) and 3.390 (1) Å. Intermolecular hydrogen bonds are found, with all O-H and N-H groups as donors, forming a three-dimensional network.

Comment top

On account of its robustness and the presence of three exodentate carboxylic groups, trimesic acid is often used in crystal engineering (Zaworotko, 2001). The compound self-assembles into an infinite interpenetrated framework with a honeycomb motif, through carboxylic acid dimer interactions, with the graph set R22(8) (Duchamp & Marsh, 1969). A non-interpenetrated framework can also be synthesized through the inclusion of neutral guests (Herbstein et al., 1987). Extended frameworks of trimesic acid with neutral guests (Kolotuchin et al., 1999; Liu et al., 2001) or organic cations have also been found, but large voids usually involve interpenetration to stabilize the structure (Zaworotko, 2001).

Recently we have isolated the title compound, (I), and report here its preparation and crystal structure. The asymmetric unit consists of a protonated triethylamine cation, one singly deprotonated trimesic acid anion, one neutral trimesic acid molecele, and two water molecules. Fig. 1 shows the asymmetric unit with the atom numbering. A range of intermolecular hydrogen bonds are found (Table 1 and Fig. 2). The two benzene rings of the asymmetric unit are not parallel with each other. The acid molecules form stacks with π···π interactions (Fig. 2); the perpendicular distances in the stacks are 3.291 (1) and 3.347 (1) Å. Pairs of trimesate anions, parallel by inversion symmetry, also have π···π interactions, with a perpendicular distance of 3.390 (1) (Fig. 3).

Related literature top

For related structures containing trimesic acid, see: Zaworotko (2001); Duchamp & Marsh (1969); Herbstein et al. (1987); Kolotuchin et al. (1999); Liu et al. (2001).

Experimental top

An ethanol solution (10 ml) of trimesic acid (2 mmol, 0.432 g) was mixed with a methanol solution (20 ml) of ZnCl2·6H2O (1 mmol, 0.240 g) and triethylamine (1 mmol, 0.10 g). The mixture was stirred for 1 h at room temperature and then filtered. Single crystals of (I) were obtained from the filtrate after 5 d.

Refinement top

The cation is disordered, with each methylene group having two alternative sites; the occupancy factors refined to 0.548:0.452 (4). C-bound H atoms were positioned geometrically and refined as riding, with C—H = 0.96 or 0.97 Å and Uiso(H) = 1.2 or 1.5 times Ueq(C). Other H atoms were located in a difference map. The N-bound H atom was refined freely, while O-bound H atoms were refined with all O—H distances restrained to be equal; the H···H distances in the two water molecules were also restrained to be equal.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I) with 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. Perspective view of the packing of the title compound, showing stacks of parallel trimesic acid molecules. Hydrogen bonds are shown as dashed lines.
[Figure 3] Fig. 3. Perspective view of the packing of the title compound, showing the stacking of parallel pairs of trimesate anions. Hydrogen bonds are shown as dashed lines.
Triethylaminium–trimesate–trimesic acid–water (1/1/1/2) top
Crystal data top
C6H16N+·C9H5O6–·C9H6O6·2H2OZ = 2
Mr = 557.50F000 = 588
Triclinic, P1Dx = 1.382 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 7.3762 (10) ÅCell parameters from 2512 reflections
b = 9.4733 (12) Åθ = 4.7–27.1º
c = 20.754 (3) ŵ = 0.12 mm−1
α = 87.502 (2)ºT = 298 (2) K
β = 87.584 (2)ºBlock, colorless
γ = 67.711 (2)º0.52 × 0.40 × 0.30 mm
V = 1340.1 (3) Å3
Data collection top
Bruker SMART CCD
diffractometer		5168 independent reflections
Radiation source: fine-focus sealed tube3702 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.062
T = 298(2) Kθmax = 26.0º
φ and ω scansθmin = 2.0º
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		h = −9→9
Tmin = 0.938, Tmax = 0.970k = −11→11
7392 measured reflectionsl = −25→21
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.117  w = 1/[σ2(Fo2) + (0.0561P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.93(Δ/σ)max < 0.001
5168 reflectionsΔρmax = 0.23 e Å−3
445 parametersΔρmin = −0.20 e Å−3
37 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0096 (16)
Crystal data top
C6H16N+·C9H5O6–·C9H6O6·2H2Oγ = 67.711 (2)º
Mr = 557.50V = 1340.1 (3) Å3
Triclinic, P1Z = 2
a = 7.3762 (10) ÅMo Kα
b = 9.4733 (12) ŵ = 0.12 mm−1
c = 20.754 (3) ÅT = 298 (2) K
α = 87.502 (2)º0.52 × 0.40 × 0.30 mm
β = 87.584 (2)º
Data collection top
Bruker SMART CCD
diffractometer		5168 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		3702 reflections with I > 2σ(I)
Tmin = 0.938, Tmax = 0.970Rint = 0.062
7392 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04537 restraints
wR(F2) = 0.117H atoms treated by a mixture of
independent and constrained refinement
S = 0.93Δρmax = 0.23 e Å−3
5168 reflectionsΔρmin = −0.20 e Å−3
445 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(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
xyzUiso*/UeqOcc. (<1)
N10.6420 (3)0.7995 (2)0.24948 (8)0.0526 (4)
H1N0.619 (3)0.738 (2)0.2793 (11)0.065 (7)*
C190.7540 (8)0.7096 (5)0.1922 (2)0.0771 (17)0.548 (4)
H19A0.66830.67420.16920.093*0.548 (4)
H19B0.79330.77630.16300.093*0.548 (4)
C200.9343 (4)0.5737 (3)0.21166 (13)0.0899 (9)
H20A0.99810.51910.17400.135*0.548 (4)
H20B0.89640.50750.24070.135*0.548 (4)
H20C1.02270.60840.23260.135*0.548 (4)
H20X1.07200.54100.20140.135*0.452 (4)
H20Y0.86670.56520.17440.135*0.452 (4)
H20Z0.91350.51070.24640.135*0.452 (4)
C210.4411 (6)0.9081 (5)0.2288 (2)0.0699 (14)0.548 (4)
H21A0.38270.98260.26190.084*0.548 (4)
H21B0.45430.96240.18930.084*0.548 (4)
C220.3090 (4)0.8233 (3)0.21796 (13)0.0830 (8)
H22A0.18300.89450.20490.124*0.548 (4)
H22B0.29420.77090.25720.124*0.548 (4)
H22C0.36580.75060.18480.124*0.548 (4)
H22X0.23390.81780.18220.124*0.452 (4)
H22Y0.25280.92340.23550.124*0.452 (4)
H22Z0.30770.74870.25060.124*0.452 (4)
C230.7499 (8)0.8860 (6)0.2784 (2)0.0730 (15)0.548 (4)
H23A0.88370.81690.28580.088*0.548 (4)
H23B0.75450.96490.24770.088*0.548 (4)
C240.6599 (5)0.9584 (3)0.34048 (16)0.1043 (10)
H24A0.73491.01280.35610.156*0.548 (4)
H24B0.65920.88080.37170.156*0.548 (4)
H24C0.52791.02820.33350.156*0.548 (4)
H24X0.60941.06170.35460.156*0.452 (4)
H24Y0.80020.92220.33640.156*0.452 (4)
H24Z0.62330.89510.37150.156*0.452 (4)
C19X0.8584 (8)0.7341 (7)0.2313 (3)0.0764 (19)0.452 (4)
H19X0.88260.79610.19620.092*0.452 (4)
H19Y0.93150.74170.26790.092*0.452 (4)
C21X0.5205 (9)0.7914 (8)0.1950 (2)0.0740 (19)0.452 (4)
H21X0.57670.69080.17690.089*0.452 (4)
H21Y0.52150.86560.16140.089*0.452 (4)
C23X0.5773 (11)0.9525 (7)0.2768 (3)0.084 (2)0.452 (4)
H23X0.43540.99300.28130.101*0.452 (4)
H23Y0.61271.01890.24630.101*0.452 (4)
C10.5708 (2)0.30422 (18)0.13104 (7)0.0342 (4)
C20.6654 (3)0.17636 (19)0.09499 (8)0.0357 (4)
H20.776 (3)0.095 (2)0.1118 (8)0.037 (5)*
C30.6069 (2)0.16946 (18)0.03272 (8)0.0334 (4)
C40.4541 (2)0.29113 (19)0.00659 (8)0.0342 (4)
H40.415 (2)0.2824 (19)−0.0352 (9)0.041 (5)*
C50.3570 (2)0.41939 (18)0.04285 (7)0.0324 (4)
C60.4151 (3)0.42441 (19)0.10511 (8)0.0344 (4)
H60.354 (3)0.509 (2)0.1298 (9)0.044 (5)*
C70.6419 (3)0.3127 (2)0.19719 (8)0.0400 (4)
C80.7172 (3)0.02888 (19)−0.00336 (8)0.0402 (4)
C90.1953 (2)0.55055 (19)0.01377 (8)0.0361 (4)
O10.80455 (19)0.21718 (15)0.21294 (6)0.0516 (4)
O20.5304 (2)0.41917 (16)0.23152 (6)0.0600 (4)
O30.8326 (2)−0.08334 (16)0.02274 (7)0.0698 (5)
O40.6772 (2)0.03685 (15)−0.06430 (6)0.0553 (4)
H4O0.752 (3)−0.054 (2)−0.0827 (12)0.094 (9)*
O50.14604 (18)0.55484 (14)−0.04160 (6)0.0466 (3)
O60.1127 (2)0.66205 (14)0.05408 (6)0.0522 (4)
H6O0.012 (3)0.742 (2)0.0357 (11)0.076 (7)*
C100.7878 (2)0.25947 (18)0.53374 (8)0.0361 (4)
C110.7343 (3)0.2969 (2)0.46974 (8)0.0366 (4)
H110.714 (2)0.2227 (19)0.4464 (8)0.038 (5)*
C120.7067 (2)0.44105 (18)0.44425 (7)0.0331 (4)
C130.7304 (2)0.5473 (2)0.48242 (8)0.0338 (4)
H130.713 (2)0.649 (2)0.4658 (8)0.037 (5)*
C140.7848 (2)0.51107 (18)0.54653 (8)0.0332 (4)
C150.8140 (2)0.36655 (19)0.57152 (8)0.0350 (4)
H150.845 (3)0.344 (2)0.6155 (9)0.044 (5)*
C160.8095 (3)0.1082 (2)0.56246 (9)0.0439 (4)
C170.6458 (3)0.4833 (2)0.37579 (8)0.0381 (4)
C180.8045 (3)0.6313 (2)0.58549 (8)0.0391 (4)
O70.8630 (2)0.06852 (15)0.61700 (6)0.0634 (4)
O80.7639 (3)0.02296 (16)0.52346 (7)0.0686 (5)
H8O0.771 (3)−0.069 (2)0.5401 (11)0.088 (8)*
O90.6254 (2)0.60924 (16)0.35290 (6)0.0559 (4)
O100.6160 (2)0.37868 (15)0.34633 (6)0.0569 (4)
H10O0.593 (4)0.403 (3)0.3030 (8)0.104 (9)*
O110.7628 (2)0.76037 (15)0.56492 (7)0.0643 (4)
O120.8720 (2)0.58578 (15)0.64318 (6)0.0531 (4)
H12O0.889 (3)0.668 (2)0.6609 (10)0.072 (7)*
O131.1077 (2)0.20607 (16)0.12245 (7)0.0526 (4)
H13A1.013 (3)0.201 (3)0.1503 (10)0.071 (7)*
H13B1.029 (3)0.285 (2)0.0976 (11)0.099 (9)*
O141.0765 (2)0.19261 (16)0.30336 (7)0.0539 (4)
H14A1.076 (4)0.115 (3)0.3294 (12)0.111 (10)*
H14B0.967 (2)0.209 (2)0.2825 (10)0.069 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0631 (12)0.0497 (10)0.0427 (10)−0.0195 (9)−0.0050 (8)0.0116 (8)
C190.103 (4)0.074 (3)0.044 (3)−0.023 (3)0.009 (3)0.003 (2)
C200.0819 (19)0.091 (2)0.0786 (19)−0.0140 (16)0.0173 (15)−0.0045 (16)
C210.066 (3)0.057 (3)0.074 (3)−0.010 (2)−0.020 (2)0.014 (2)
C220.0768 (18)0.0886 (19)0.0835 (18)−0.0305 (15)−0.0244 (15)0.0113 (15)
C230.077 (4)0.065 (3)0.082 (3)−0.033 (3)−0.001 (3)0.000 (2)
C240.117 (3)0.095 (2)0.114 (3)−0.051 (2)−0.013 (2)−0.0345 (19)
C19X0.067 (4)0.088 (4)0.077 (4)−0.035 (3)−0.005 (3)0.014 (3)
C21X0.085 (4)0.090 (5)0.045 (3)−0.031 (4)−0.022 (3)0.017 (3)
C23X0.085 (5)0.063 (4)0.105 (5)−0.027 (4)−0.006 (4)−0.001 (3)
C10.0424 (10)0.0340 (9)0.0245 (8)−0.0120 (8)−0.0072 (7)0.0004 (7)
C20.0410 (10)0.0313 (9)0.0302 (9)−0.0078 (8)−0.0110 (7)0.0027 (7)
C30.0400 (10)0.0288 (9)0.0295 (8)−0.0101 (7)−0.0074 (7)−0.0018 (7)
C40.0409 (10)0.0345 (9)0.0257 (9)−0.0116 (8)−0.0100 (7)0.0003 (7)
C50.0362 (9)0.0307 (9)0.0286 (8)−0.0106 (7)−0.0065 (7)0.0021 (7)
C60.0386 (10)0.0327 (9)0.0284 (9)−0.0090 (8)−0.0033 (7)−0.0032 (7)
C70.0520 (11)0.0408 (10)0.0235 (8)−0.0128 (9)−0.0088 (8)0.0006 (7)
C80.0443 (10)0.0333 (10)0.0363 (10)−0.0055 (8)−0.0107 (8)−0.0053 (8)
C90.0386 (10)0.0345 (9)0.0330 (9)−0.0111 (8)−0.0059 (7)0.0027 (7)
O10.0567 (8)0.0528 (8)0.0326 (7)−0.0043 (7)−0.0203 (6)−0.0019 (6)
O20.0721 (10)0.0593 (9)0.0278 (7)0.0010 (7)−0.0125 (6)−0.0115 (6)
O30.0803 (11)0.0413 (8)0.0567 (9)0.0155 (8)−0.0264 (8)−0.0118 (7)
O40.0695 (9)0.0453 (8)0.0351 (7)−0.0012 (7)−0.0117 (6)−0.0127 (6)
O50.0498 (8)0.0461 (7)0.0347 (7)−0.0073 (6)−0.0150 (6)0.0066 (6)
O60.0570 (9)0.0360 (7)0.0460 (8)0.0037 (7)−0.0132 (7)−0.0027 (6)
C100.0399 (10)0.0330 (9)0.0315 (9)−0.0094 (8)−0.0063 (7)0.0025 (7)
C110.0455 (10)0.0338 (9)0.0294 (9)−0.0131 (8)−0.0049 (7)−0.0041 (7)
C120.0363 (9)0.0365 (9)0.0242 (8)−0.0113 (8)−0.0016 (7)0.0005 (7)
C130.0372 (10)0.0336 (9)0.0295 (9)−0.0126 (8)−0.0039 (7)0.0051 (7)
C140.0362 (9)0.0346 (9)0.0289 (8)−0.0132 (7)−0.0057 (7)0.0007 (7)
C150.0404 (10)0.0365 (9)0.0259 (9)−0.0118 (8)−0.0083 (7)0.0037 (7)
C160.0560 (12)0.0356 (10)0.0391 (10)−0.0158 (9)−0.0110 (9)0.0051 (8)
C170.0408 (10)0.0440 (10)0.0245 (8)−0.0105 (8)−0.0027 (7)−0.0002 (8)
C180.0445 (10)0.0383 (10)0.0372 (10)−0.0179 (8)−0.0100 (8)0.0017 (8)
O70.1019 (12)0.0465 (8)0.0437 (8)−0.0297 (8)−0.0271 (8)0.0170 (6)
O80.1237 (14)0.0427 (9)0.0523 (9)−0.0445 (9)−0.0285 (9)0.0100 (7)
O90.0822 (10)0.0535 (8)0.0320 (7)−0.0261 (8)−0.0127 (7)0.0138 (6)
O100.0888 (11)0.0504 (8)0.0273 (7)−0.0199 (8)−0.0148 (7)−0.0045 (6)
O110.1039 (12)0.0386 (8)0.0593 (9)−0.0352 (8)−0.0273 (8)0.0061 (7)
O120.0762 (10)0.0484 (8)0.0385 (7)−0.0258 (7)−0.0218 (7)−0.0012 (6)
O130.0586 (9)0.0473 (8)0.0397 (8)−0.0056 (7)−0.0004 (7)−0.0076 (6)
O140.0740 (10)0.0496 (9)0.0431 (8)−0.0267 (8)−0.0266 (7)0.0026 (6)
Geometric parameters (Å, °) top
N1—C23X1.474 (6)C1—C61.382 (2)
N1—C21X1.494 (5)C1—C71.506 (2)
N1—C231.498 (5)C2—C31.391 (2)
N1—C19X1.514 (6)C2—H20.952 (17)
N1—C191.514 (5)C3—C41.380 (2)
N1—C211.515 (4)C3—C81.487 (2)
N1—H1N0.88 (2)C4—C51.389 (2)
C19—C201.513 (6)C4—H40.942 (19)
C19—H19A0.970C5—C61.387 (2)
C19—H19B0.970C5—C91.484 (2)
C20—C19X1.475 (7)C6—H60.924 (19)
C20—H20A0.960C7—O11.245 (2)
C20—H20B0.960C7—O21.259 (2)
C20—H20C0.960C8—O31.204 (2)
C20—H20X0.960C8—O41.303 (2)
C20—H20Y0.960C9—O51.2141 (19)
C20—H20Z0.960C9—O61.316 (2)
C21—C221.508 (5)O4—H4O0.917 (15)
C21—H21A0.970O6—H6O0.916 (15)
C21—H21B0.970C10—C151.383 (2)
C22—C21X1.531 (6)C10—C111.394 (2)
C22—H22A0.960C10—C161.482 (2)
C22—H22B0.960C11—C121.386 (2)
C22—H22C0.960C11—H110.933 (18)
C22—H22X0.960C12—C131.373 (2)
C22—H22Y0.960C12—C171.500 (2)
C22—H22Z0.960C13—C141.396 (2)
C23—C241.493 (6)C13—H130.971 (17)
C23—H23A0.970C14—C151.383 (2)
C23—H23B0.970C14—C181.479 (2)
C24—C23X1.491 (7)C15—H150.945 (19)
C24—H24A0.960C16—O71.211 (2)
C24—H24B0.960C16—O81.306 (2)
C24—H24C0.960C17—O91.221 (2)
C24—H24X0.960C17—O101.279 (2)
C24—H24Y0.960C18—O111.205 (2)
C24—H24Z0.960C18—O121.308 (2)
C19X—H19X0.970O8—H8O0.907 (15)
C19X—H19Y0.970O10—H10O0.924 (16)
C21X—H21X0.970O12—H12O0.925 (15)
C21X—H21Y0.970O13—H13A0.901 (14)
C23X—H23X0.970O13—H13B0.908 (15)
C23X—H23Y0.970O14—H14A0.894 (15)
C1—C21.381 (2)O14—H14B0.889 (14)
C23X—N1—C21X113.4 (4)C23—C24—H24C109.5
C23X—N1—C2347.1 (3)H24A—C24—H24C109.5
C21X—N1—C23146.2 (3)H24B—C24—H24C109.5
C23X—N1—C19X113.2 (4)C23X—C24—H24X109.5
C21X—N1—C19X111.3 (4)C23—C24—H24X133.5
C23—N1—C19X68.2 (3)H24A—C24—H24X53.5
C23X—N1—C19141.5 (3)H24B—C24—H24X116.9
C21X—N1—C1964.2 (3)H24C—C24—H24X56.8
C23—N1—C19111.7 (3)C23X—C24—H24Y109.5
C19X—N1—C1947.9 (3)C23—C24—H24Y63.5
C23X—N1—C2165.5 (3)H24A—C24—H24Y56.9
C21X—N1—C2149.7 (3)H24B—C24—H24Y94.7
C23—N1—C21110.2 (3)H24C—C24—H24Y155.6
C19X—N1—C21145.0 (3)H24X—C24—H24Y109.5
C19—N1—C21109.6 (3)C23X—C24—H24Z109.5
C23X—N1—H1N107.4 (15)C23—C24—H24Z116.1
C21X—N1—H1N102.7 (14)H24A—C24—H24Z116.4
C23—N1—H1N109.5 (14)H24C—C24—H24Z94.7
C19X—N1—H1N108.1 (15)H24X—C24—H24Z109.5
C19—N1—H1N110.5 (15)H24Y—C24—H24Z109.5
C21—N1—H1N105.1 (15)C20—C19X—N1114.8 (4)
C20—C19—N1112.6 (3)C20—C19X—H19X108.6
C20—C19—H19A109.1N1—C19X—H19X108.6
N1—C19—H19A109.1C20—C19X—H19Y108.6
C20—C19—H19B109.1N1—C19X—H19Y108.6
N1—C19—H19B109.1H19X—C19X—H19Y107.5
H19A—C19—H19B107.8N1—C21X—C22111.0 (4)
C19X—C20—C1948.5 (3)N1—C21X—H21X109.4
C19X—C20—H20A136.2C22—C21X—H21X109.4
C19—C20—H20A109.5N1—C21X—H21Y109.4
C19X—C20—H20B113.7C22—C21X—H21Y109.4
C19—C20—H20B109.5H21X—C21X—H21Y108.0
H20A—C20—H20B109.5N1—C23X—C24115.2 (5)
C19X—C20—H20C62.5N1—C23X—H23X108.5
C19—C20—H20C109.5C24—C23X—H23X108.5
H20A—C20—H20C109.5N1—C23X—H23Y108.5
H20B—C20—H20C109.5C24—C23X—H23Y108.5
C19X—C20—H20X109.5H23X—C23X—H23Y107.5
C19—C20—H20X134.8C2—C1—C6119.40 (15)
H20A—C20—H20X55.1C2—C1—C7119.65 (15)
H20B—C20—H20X115.7C6—C1—C7120.93 (15)
H20C—C20—H20X55.5C1—C2—C3120.39 (15)
C19X—C20—H20Y109.5C1—C2—H2119.8 (10)
C19—C20—H20Y62.2C3—C2—H2119.7 (10)
H20A—C20—H20Y55.9C4—C3—C2119.95 (15)
H20B—C20—H20Y98.4C4—C3—C8122.76 (15)
H20C—C20—H20Y152.0C2—C3—C8117.28 (15)
H20X—C20—H20Y109.5C3—C4—C5119.93 (15)
C19X—C20—H20Z109.5C3—C4—H4118.2 (11)
C19—C20—H20Z115.1C5—C4—H4121.8 (11)
H20A—C20—H20Z114.3C6—C5—C4119.63 (15)
H20C—C20—H20Z98.3C6—C5—C9120.97 (15)
H20X—C20—H20Z109.5C4—C5—C9119.39 (14)
H20Y—C20—H20Z109.5C1—C6—C5120.68 (16)
C22—C21—N1111.1 (3)C1—C6—H6118.4 (11)
C22—C21—H21A109.4C5—C6—H6120.9 (11)
N1—C21—H21A109.4O1—C7—O2125.67 (16)
C22—C21—H21B109.4O1—C7—C1118.21 (15)
N1—C21—H21B109.4O2—C7—C1116.11 (15)
H21A—C21—H21B108.0O3—C8—O4123.44 (16)
C21—C22—C21X49.2 (3)O3—C8—C3121.67 (16)
C21—C22—H22A109.5O4—C8—C3114.89 (15)
C21X—C22—H22A134.5O5—C9—O6123.69 (16)
C21—C22—H22B109.5O5—C9—C5123.40 (15)
C21X—C22—H22B115.6O6—C9—C5112.91 (14)
H22A—C22—H22B109.5C8—O4—H4O109.0 (17)
C21—C22—H22C109.5C9—O6—H6O112.0 (15)
C21X—C22—H22C61.4C15—C10—C11119.67 (16)
H22A—C22—H22C109.5C15—C10—C16119.61 (15)
H22B—C22—H22C109.5C11—C10—C16120.68 (16)
C21—C22—H22X133.7C12—C11—C10120.09 (16)
C21X—C22—H22X109.5C12—C11—H11122.9 (10)
H22A—C22—H22X51.6C10—C11—H11116.9 (10)
H22B—C22—H22X116.7C13—C12—C11119.80 (15)
H22C—C22—H22X58.7C13—C12—C17119.67 (15)
C21—C22—H22Y61.2C11—C12—C17120.50 (15)
C21X—C22—H22Y109.5C12—C13—C14120.67 (15)
H22A—C22—H22Y58.9C12—C13—H13121.6 (10)
H22B—C22—H22Y95.0C14—C13—H13117.7 (10)
H22C—C22—H22Y155.5C15—C14—C13119.27 (15)
H22X—C22—H22Y109.5C15—C14—C18122.61 (15)
C21—C22—H22Z116.4C13—C14—C18118.11 (15)
C21X—C22—H22Z109.5C10—C15—C14120.49 (15)
H22A—C22—H22Z115.9C10—C15—H15120.6 (11)
H22C—C22—H22Z95.0C14—C15—H15118.9 (11)
H22X—C22—H22Z109.5O7—C16—O8123.58 (17)
H22Y—C22—H22Z109.5O7—C16—C10122.95 (17)
C24—C23—N1113.7 (3)O8—C16—C10113.46 (15)
C24—C23—H23A108.8O9—C17—O10125.42 (16)
N1—C23—H23A108.8O9—C17—C12120.53 (16)
C24—C23—H23B108.8O10—C17—C12114.04 (15)
N1—C23—H23B108.8O11—C18—O12123.21 (16)
H23A—C23—H23B107.7O11—C18—C14122.05 (16)
C23X—C24—C2346.9 (3)O12—C18—C14114.74 (15)
C23X—C24—H24A134.0C16—O8—H8O115.7 (16)
C23—C24—H24A109.5C17—O10—H10O112.2 (17)
C23X—C24—H24B115.6C18—O12—H12O106.3 (14)
C23—C24—H24B109.5H13A—O13—H13B96.5 (18)
H24A—C24—H24B109.5H14A—O14—H14B98.8 (19)
C23X—C24—H24C63.6
C23X—N1—C19—C20118.9 (6)C3—C4—C5—C60.3 (2)
C21X—N1—C19—C20−145.4 (5)C3—C4—C5—C9178.90 (15)
C23—N1—C19—C2071.4 (4)C2—C1—C6—C5−1.8 (2)
C19X—N1—C19—C2045.4 (4)C7—C1—C6—C5176.52 (15)
C21—N1—C19—C20−166.2 (3)C4—C5—C6—C11.1 (2)
N1—C19—C20—C19X−46.3 (4)C9—C5—C6—C1−177.51 (15)
C23X—N1—C21—C22−148.1 (5)C2—C1—C7—O112.8 (2)
C21X—N1—C21—C2248.5 (4)C6—C1—C7—O1−165.46 (16)
C23—N1—C21—C22−163.4 (3)C2—C1—C7—O2−168.32 (16)
C19X—N1—C21—C22116.1 (6)C6—C1—C7—O213.4 (2)
C19—N1—C21—C2273.3 (4)C4—C3—C8—O3−170.31 (18)
N1—C21—C22—C21X−47.4 (3)C2—C3—C8—O310.7 (3)
C23X—N1—C23—C2447.1 (4)C4—C3—C8—O48.9 (3)
C21X—N1—C23—C24112.6 (6)C2—C3—C8—O4−170.15 (16)
C19X—N1—C23—C24−151.2 (5)C6—C5—C9—O5176.00 (16)
C19—N1—C23—C24−171.7 (4)C4—C5—C9—O5−2.6 (3)
C21—N1—C23—C2466.2 (4)C6—C5—C9—O6−3.3 (2)
N1—C23—C24—C23X−46.6 (4)C4—C5—C9—O6178.04 (15)
C19—C20—C19X—N147.4 (4)C15—C10—C11—C12−0.3 (3)
C23X—N1—C19X—C20172.6 (4)C16—C10—C11—C12177.35 (16)
C21X—N1—C19X—C20−58.4 (5)C10—C11—C12—C13−0.7 (3)
C23—N1—C19X—C20158.0 (6)C10—C11—C12—C17−178.95 (15)
C19—N1—C19X—C20−47.9 (4)C11—C12—C13—C140.9 (3)
C21—N1—C19X—C20−107.6 (6)C17—C12—C13—C14179.25 (15)
C23X—N1—C21X—C22−63.8 (5)C12—C13—C14—C15−0.3 (3)
C23—N1—C21X—C22−110.5 (6)C12—C13—C14—C18−178.94 (16)
C19X—N1—C21X—C22167.2 (4)C11—C10—C15—C140.9 (3)
C19—N1—C21X—C22158.6 (5)C16—C10—C15—C14−176.72 (16)
C21—N1—C21X—C22−47.5 (4)C13—C14—C15—C10−0.7 (3)
C21—C22—C21X—N148.3 (4)C18—C14—C15—C10177.94 (16)
C21X—N1—C23X—C24165.6 (4)C15—C10—C16—O7−5.3 (3)
C23—N1—C23X—C24−47.9 (4)C11—C10—C16—O7177.07 (19)
C19X—N1—C23X—C24−66.4 (6)C15—C10—C16—O8174.17 (17)
C19—N1—C23X—C24−117.1 (6)C11—C10—C16—O8−3.4 (3)
C21—N1—C23X—C24151.9 (6)C13—C12—C17—O93.2 (3)
C23—C24—C23X—N148.3 (4)C11—C12—C17—O9−178.48 (17)
C6—C1—C2—C31.1 (3)C13—C12—C17—O10−175.64 (16)
C7—C1—C2—C3−177.21 (15)C11—C12—C17—O102.7 (2)
C1—C2—C3—C40.2 (3)C15—C14—C18—O11−173.63 (18)
C1—C2—C3—C8179.31 (15)C13—C14—C18—O115.0 (3)
C2—C3—C4—C5−0.9 (3)C15—C14—C18—O127.0 (3)
C8—C3—C4—C5−179.94 (15)C13—C14—C18—O12−174.39 (16)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O90.88 (2)1.90 (2)2.771 (2)166 (2)
O4—H4O···O13i0.917 (15)1.651 (16)2.5653 (18)174 (2)
O6—H6O···O3ii0.916 (15)1.703 (16)2.5895 (18)162 (2)
O8—H8O···O11iii0.907 (15)1.697 (15)2.5993 (19)173 (2)
O10—H10O···O20.924 (16)1.557 (17)2.4671 (17)167 (3)
O12—H12O···O14iv0.925 (15)1.651 (15)2.5740 (18)176 (2)
O13—H13A···O10.901 (14)1.936 (15)2.832 (2)173 (2)
O13—H13B···O5v0.908 (15)1.951 (15)2.8577 (18)176 (3)
O14—H14A···O7vi0.894 (15)1.935 (16)2.8141 (19)167 (3)
O14—H14B···O10.889 (14)1.896 (16)2.7433 (18)159 (2)
Symmetry codes: (i) −x+2, −y, −z; (ii) x−1, y+1, z; (iii) x, y−1, z; (iv) −x+2, −y+1, −z+1; (v) −x+1, −y+1, −z; (vi) −x+2, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O90.88 (2)1.90 (2)2.771 (2)166 (2)
O4—H4O···O13i0.917 (15)1.651 (16)2.5653 (18)174 (2)
O6—H6O···O3ii0.916 (15)1.703 (16)2.5895 (18)162 (2)
O8—H8O···O11iii0.907 (15)1.697 (15)2.5993 (19)173 (2)
O10—H10O···O20.924 (16)1.557 (17)2.4671 (17)167 (3)
O12—H12O···O14iv0.925 (15)1.651 (15)2.5740 (18)176 (2)
O13—H13A···O10.901 (14)1.936 (15)2.832 (2)173 (2)
O13—H13B···O5v0.908 (15)1.951 (15)2.8577 (18)176 (3)
O14—H14A···O7vi0.894 (15)1.935 (16)2.8141 (19)167 (3)
O14—H14B···O10.889 (14)1.896 (16)2.7433 (18)159 (2)
Symmetry codes: (i) −x+2, −y, −z; (ii) x−1, y+1, z; (iii) x, y−1, z; (iv) −x+2, −y+1, −z+1; (v) −x+1, −y+1, −z; (vi) −x+2, −y, −z+1.
Acknowledgements top

We acknowledge financial support from the Science and Technology Foundation of Shanghai (No. 065212050).

references
References top

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