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Acta Cryst. (2008). E64, o1146-o1147    [ doi:10.1107/S1600536808015110 ]

1,10-Phenanthrolinium 4-chloro-2-hydroxybenzoate-1,10-phenanthroline-4-chloro-2-hydroxybenzoic acid (1/1/1)

H. Shen, J.-J. Nie and D.-J. Xu

Abstract top

The title compound, C12H9N2+·C7H4ClO3-·C12H8N2·C7H5ClO3, contains one phenanthrolinium (Hphen) cation, one phenanthroline (phen) molecule, one 4-chloro-2-hydroxybenzoate anion (hcba) and one 4-chloro-2-hydroxybenzoic acid (Hhcba) molecule in the asymmetric unit. The phen molecule is approximately parallel to Hphen, making a dihedral angle of 1.98 (6)°. The centroid-centroid distance between pyridine rings of adjacent phen and Hphen species is 3.7718 (15) Å, and that between the benzene and pyridine rings of adjacent phen and Hphen species is 3.7922 (16) Å, indicative of [pi]-[pi] stacking interactions. The crystal structure contains an extensive network of classical (O-H...O, N-H...N and O-H...Cl) and weak (C-H...O and C-H...N) hydrogen bonds. Finally, C-H...[pi] interactions are seen between Hphen and hcba and between phen and Hhcba in the crystal structure. The hydroxy group of the anion is disordered over the two sites ortho to the carboxylate group in a 0.75:0.25 ratio.

Comment top

As part of our ongoing investigation on the nature of π-π stacking (Su & Xu, 2004; Pan et al. 2006), the title compound, (I), incorporating 1,10-phenanthroline (phen) has been prepared and its crystal structure is reported here.

The asymmetric unit of (I) contains two neutral molecules, one cation and one anion (Fig. 1), similar to the situation in 1,10-phenanthrolinium 6-carboxypyridine-2-carboxylate 1,10-phenanthroline pyridine-2,6-dicarboxylic acid (Fu et al., 2005). The significant difference in C-O bond distances [1.312 (3) and 1.239 (3)Å] suggests that the C7-carboxyl group is protonated in the crystal. The neutral 4-chloro-2-hydroxybenzoic acid (Hhcba) is hydrogen bonded with the 4-chloro-2-hydroxybenzoate anion (hcba) (Fig. 1 and Table 2). The neutral phenathroline (phen) molecule is approximately parallel to the protonated phenathroline cation (Hphen), with a dihedral angle of 1.98 (6)°. Fig. 2 shows the nearly parallel arrangement of phen and Hphen. The centroid-to-centroid distances between N2-pyridine and N4-pyridine rings is 3.7718 (15) Å; the centroid-to-centroid distance between N1-pyridine and C37i-benzene rings is 3.7922 (16) Å [symmetry code: (i) 1 + x,y,z]. They suggest the existence of π-π stacking between phen and Hphen.

The crystal structure contains C—H···π interactions between Hphen and hcba and between phen and Hhcba (Fig. 1). H25···Cg1 = 2.64 Å, C25—H25···Cg1 = 174° and C25···Cg1 = 3.571 (2) Å (where Cg1 is the centroid of the C8-benzene ring); H40···Cg2 = 2.63 Å, C40—H40···Cg2 = 153° and C40···Cg2 = 3.489 (3) Å (where Cg2 is the centroid of the C1-benzene ring).

Related literature top

For general background, see: Su & Xu (2004); Pan et al. (2006). For a related structure, see: Fu et al. (2005).

Experimental top

4-chloro-2-hydroxybenzoic acid (0.17 g, 1 mmol) and 1,10-phenanthroline (0.20 g, 1 mmol) were dissolved in ethanol-water (10 ml, 7:3 v/v) at room temperature. The solution was filtered and red-brown chunks of (I) were obtained from the filtrate after 3 d.

Refinement top

The O6-hydroxyl group is disordered over two sites; occupancies were initially refined, and fixed as 0.75:0.25 at final cycles of refinement. The H atoms bonded to N1 atom and hydroxyl H atoms were located in a difference Fourier map and refined as riding in their as-found relative position, with Uiso(H) = 1.5Ueq(O,N). Aromatic H atoms were placed in calculated positions with C—H = 0.93 Å, and refined in riding mode with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with 30% probability displacement ellipsoids (arbitrary spheres for H atoms). The minor component of the disordered 4-chloro-2-hydroxybenzoate has been omitted for clarity. Dashed lines indicate hydrogen bonding; dotted lines indicate C—H···π interaction.
[Figure 2] Fig. 2. A packing diagram for (I) showing π-π stacking between phen and Hphen ring systems [symmetry code: (i) 1 + x,y,z]. The H atoms are omitted for clarity.
1,10-Phenanthrolinium 4-chloro-2-hydroxybenzoate–1,10-phenanthroline– 4-chloro-2-hydroxybenzoic acid (1/1/1) top
Crystal data top
C12H9N2+·C7H4ClO3–·C12H8N2·C7H5ClO3F000 = 1456
Mr = 705.53Dx = 1.426 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3820 reflections
a = 8.0627 (6) Åθ = 2.0–25.0º
b = 19.6005 (15) ŵ = 0.25 mm−1
c = 20.7929 (17) ÅT = 295 (2) K
V = 3286.0 (4) Å3Chunk, red brown
Z = 40.43 × 0.37 × 0.32 mm
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer		6394 independent reflections
Radiation source: fine-focus sealed tube4326 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.054
Detector resolution: 10.00 pixels mm-1θmax = 26.0º
T = 295(2) Kθmin = 1.4º
ω scansh = −9→9
Absorption correction: nonek = −24→24
37126 measured reflectionsl = −23→24
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.039  w = 1/[σ2(Fo2) + (0.051P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.098(Δ/σ)max < 0.001
S = 0.98Δρmax = 0.24 e Å−3
6394 reflectionsΔρmin = −0.14 e Å−3
460 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 2739 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: −0.09 (5)
Crystal data top
C12H9N2+·C7H4ClO3–·C12H8N2·C7H5ClO3V = 3286.0 (4) Å3
Mr = 705.53Z = 4
Orthorhombic, P212121Mo Kα
a = 8.0627 (6) ŵ = 0.25 mm−1
b = 19.6005 (15) ÅT = 295 (2) K
c = 20.7929 (17) Å0.43 × 0.37 × 0.32 mm
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer		6394 independent reflections
Absorption correction: none4326 reflections with I > 2σ(I)
37126 measured reflectionsRint = 0.054
Refinement top
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.098Δρmax = 0.24 e Å−3
S = 0.98Δρmin = −0.14 e Å−3
6394 reflectionsAbsolute structure: Flack (1983), 2739 Friedel pairs
460 parametersFlack parameter: −0.09 (5)
Special details top

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cl1−0.36861 (10)0.67865 (4)0.46601 (4)0.0854 (2)
Cl21.02809 (9)0.33001 (4)0.13135 (4)0.0900 (3)
N10.7137 (3)0.28257 (9)0.44997 (10)0.0559 (5)
H1N0.69230.27910.48970.084*
N20.5485 (3)0.38638 (10)0.51279 (11)0.0633 (6)
N30.2373 (3)0.26039 (11)0.41612 (11)0.0681 (6)
N40.0909 (3)0.36501 (10)0.48502 (10)0.0666 (6)
O10.1928 (2)0.60893 (10)0.24138 (10)0.0753 (5)
H1A0.28610.59600.22360.113*
O20.3673 (3)0.63537 (12)0.32124 (11)0.0952 (7)
O30.2480 (2)0.66890 (12)0.43318 (11)0.0951 (6)
H3A0.34180.66280.40620.143*
O40.2843 (2)0.47959 (10)0.15141 (10)0.0746 (5)
O50.4445 (2)0.56412 (9)0.18697 (9)0.0726 (5)
C10.0776 (3)0.64335 (12)0.33999 (13)0.0547 (6)
C20.0958 (3)0.66070 (12)0.40499 (14)0.0611 (7)
C3−0.0418 (3)0.67074 (13)0.44405 (13)0.0626 (7)
H3−0.02910.68100.48740.075*
C4−0.1972 (3)0.66515 (12)0.41731 (13)0.0594 (7)
C5−0.2199 (3)0.64899 (13)0.35319 (14)0.0648 (7)
H5−0.32610.64570.33600.078*
C6−0.0819 (3)0.63782 (13)0.31511 (13)0.0594 (7)
H6−0.09610.62640.27200.071*
C70.2243 (4)0.62942 (13)0.30020 (16)0.0648 (7)
C80.5737 (3)0.46147 (12)0.15467 (10)0.0501 (6)
C90.5603 (3)0.39317 (13)0.13526 (12)0.0595 (6)
H90.45640.37470.12670.071*0.25
C100.7005 (3)0.35299 (13)0.12879 (13)0.0656 (7)
H100.69120.30740.11680.079*
C110.8526 (3)0.38097 (12)0.14023 (13)0.0589 (6)
C120.8724 (3)0.44813 (13)0.15866 (12)0.0569 (6)
H120.97730.46630.16600.068*
C130.7316 (3)0.48752 (13)0.16586 (12)0.0538 (6)
H130.74260.53280.17860.065*0.75
C140.4216 (3)0.50398 (14)0.16457 (12)0.0581 (7)
C210.7978 (4)0.23170 (13)0.42364 (13)0.0662 (7)
H210.82930.19460.44870.079*
C220.8394 (3)0.23341 (14)0.35891 (15)0.0700 (8)
H220.89810.19770.34030.084*
C230.7924 (4)0.28875 (15)0.32288 (13)0.0673 (7)
H230.81820.29010.27930.081*
C240.7056 (3)0.34341 (12)0.35095 (12)0.0560 (6)
C250.6560 (4)0.40270 (15)0.31662 (14)0.0722 (8)
H250.67980.40590.27300.087*
C260.5762 (4)0.45383 (15)0.34530 (15)0.0740 (8)
H260.54590.49200.32140.089*
C270.5366 (3)0.45098 (12)0.41213 (14)0.0618 (7)
C280.4538 (4)0.50332 (13)0.44537 (19)0.0791 (9)
H280.42060.54240.42360.095*
C290.4222 (4)0.49694 (14)0.50952 (18)0.0839 (9)
H290.36880.53170.53180.101*
C300.4707 (4)0.43793 (14)0.54105 (15)0.0779 (8)
H300.44720.43420.58470.093*
C310.5796 (3)0.39333 (11)0.44856 (12)0.0520 (6)
C320.6662 (3)0.33901 (11)0.41681 (11)0.0490 (6)
C330.3118 (4)0.21255 (15)0.38143 (17)0.0835 (10)
H330.33790.17170.40190.100*
C340.3539 (4)0.21872 (16)0.31680 (16)0.0803 (9)
H340.40770.18340.29540.096*
C350.3145 (4)0.27756 (15)0.28567 (15)0.0737 (8)
H350.34090.28310.24240.088*
C360.2336 (3)0.32990 (13)0.31938 (12)0.0565 (6)
C370.1823 (3)0.39218 (13)0.28871 (13)0.0646 (7)
H370.20460.39870.24530.077*
C380.1031 (4)0.44091 (13)0.32165 (12)0.0651 (7)
H380.07160.48070.30060.078*
C390.0659 (3)0.43319 (11)0.38807 (11)0.0537 (6)
C40−0.0182 (3)0.48382 (13)0.42393 (14)0.0649 (7)
H40−0.05840.52270.40360.078*
C41−0.0399 (4)0.47545 (13)0.48783 (15)0.0730 (8)
H41−0.09130.50910.51220.088*
C420.0156 (4)0.41596 (15)0.51631 (14)0.0760 (9)
H42−0.00050.41100.56030.091*
C430.1165 (3)0.37377 (11)0.42085 (11)0.0522 (6)
C440.1987 (3)0.31975 (12)0.38519 (11)0.0532 (6)
O6A0.4152 (3)0.36325 (13)0.12245 (13)0.0825 (8)0.75
H6A0.33250.39580.13170.124*0.75
O6B0.7525 (8)0.5525 (3)0.1865 (4)0.0664 (19)0.25
H6B0.66500.56740.20020.100*0.25
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0676 (4)0.0996 (5)0.0890 (6)−0.0008 (4)0.0144 (4)−0.0178 (4)
Cl20.0706 (5)0.0762 (5)0.1232 (7)0.0177 (4)−0.0119 (4)−0.0287 (5)
N10.0713 (13)0.0502 (11)0.0463 (12)0.0009 (10)0.0083 (11)0.0075 (9)
N20.0744 (16)0.0533 (12)0.0623 (15)−0.0072 (11)0.0111 (12)−0.0037 (11)
N30.0927 (18)0.0526 (12)0.0590 (14)0.0024 (12)−0.0153 (13)0.0074 (11)
N40.0941 (18)0.0588 (12)0.0469 (14)−0.0156 (12)−0.0046 (12)0.0017 (10)
O10.0561 (11)0.0960 (13)0.0736 (14)0.0172 (10)0.0067 (10)0.0066 (11)
O20.0512 (12)0.1293 (18)0.1050 (17)0.0025 (12)0.0000 (12)−0.0156 (14)
O30.0612 (13)0.1030 (15)0.1212 (18)0.0034 (12)−0.0074 (12)−0.0249 (14)
O40.0514 (11)0.0909 (14)0.0816 (14)−0.0026 (10)−0.0025 (10)0.0044 (10)
O50.0605 (12)0.0680 (12)0.0893 (14)0.0038 (10)0.0147 (10)−0.0033 (10)
C10.0466 (14)0.0511 (13)0.0666 (18)0.0076 (11)−0.0001 (13)0.0036 (12)
C20.0502 (16)0.0534 (14)0.0796 (19)−0.0007 (12)−0.0112 (14)−0.0017 (13)
C30.0628 (18)0.0589 (14)0.0660 (17)−0.0047 (13)−0.0036 (14)−0.0064 (13)
C40.0600 (16)0.0477 (13)0.0705 (19)0.0023 (12)0.0074 (14)−0.0026 (13)
C50.0496 (15)0.0712 (17)0.074 (2)0.0037 (13)−0.0044 (14)0.0064 (14)
C60.0514 (16)0.0653 (15)0.0615 (16)0.0066 (12)−0.0045 (13)0.0048 (13)
C70.0534 (18)0.0607 (16)0.080 (2)0.0092 (13)−0.0016 (16)0.0094 (14)
C80.0544 (15)0.0584 (14)0.0376 (13)−0.0047 (12)0.0013 (11)0.0080 (10)
C90.0557 (16)0.0701 (16)0.0525 (16)−0.0088 (14)−0.0026 (13)−0.0023 (13)
C100.0682 (18)0.0590 (15)0.0695 (18)−0.0043 (14)−0.0047 (15)−0.0086 (13)
C110.0594 (16)0.0622 (15)0.0551 (16)0.0072 (13)−0.0017 (13)−0.0042 (12)
C120.0500 (14)0.0604 (15)0.0602 (16)−0.0021 (12)−0.0011 (12)0.0003 (12)
C130.0563 (16)0.0549 (14)0.0502 (16)−0.0038 (12)0.0023 (12)0.0025 (11)
C140.0563 (17)0.0699 (17)0.0481 (16)−0.0007 (14)0.0084 (13)0.0161 (13)
C210.0786 (19)0.0538 (15)0.066 (2)0.0058 (14)0.0056 (16)0.0057 (13)
C220.0707 (19)0.0711 (17)0.068 (2)0.0066 (14)0.0054 (15)−0.0076 (15)
C230.0681 (17)0.087 (2)0.0469 (16)−0.0143 (16)0.0028 (14)−0.0019 (14)
C240.0586 (15)0.0609 (15)0.0486 (16)−0.0076 (12)−0.0043 (12)0.0065 (12)
C250.080 (2)0.084 (2)0.0525 (17)−0.0113 (17)−0.0129 (15)0.0186 (15)
C260.079 (2)0.0660 (17)0.077 (2)−0.0018 (16)−0.0179 (17)0.0259 (16)
C270.0569 (16)0.0526 (14)0.076 (2)−0.0056 (12)−0.0137 (14)0.0085 (14)
C280.073 (2)0.0495 (15)0.114 (3)0.0013 (14)−0.017 (2)0.0003 (16)
C290.084 (2)0.0571 (17)0.111 (3)−0.0002 (16)0.008 (2)−0.0194 (18)
C300.090 (2)0.0618 (17)0.082 (2)−0.0074 (16)0.0166 (17)−0.0185 (16)
C310.0497 (14)0.0463 (12)0.0598 (17)−0.0098 (11)−0.0022 (13)0.0012 (12)
C320.0507 (14)0.0503 (13)0.0461 (15)−0.0090 (11)−0.0019 (11)0.0062 (11)
C330.107 (3)0.0593 (17)0.084 (2)0.0125 (17)−0.023 (2)0.0040 (16)
C340.085 (2)0.0715 (19)0.084 (2)0.0115 (16)−0.0041 (18)−0.0114 (17)
C350.076 (2)0.0766 (19)0.0690 (19)−0.0025 (15)0.0000 (16)−0.0024 (16)
C360.0614 (15)0.0573 (15)0.0508 (16)−0.0067 (13)−0.0046 (12)0.0011 (13)
C370.078 (2)0.0686 (17)0.0472 (16)−0.0104 (15)−0.0025 (14)0.0102 (13)
C380.086 (2)0.0558 (15)0.0536 (17)−0.0028 (14)−0.0090 (15)0.0106 (13)
C390.0597 (16)0.0522 (14)0.0492 (16)−0.0082 (12)−0.0088 (12)0.0023 (12)
C400.0722 (18)0.0515 (14)0.071 (2)−0.0046 (13)−0.0034 (15)−0.0009 (13)
C410.085 (2)0.0613 (16)0.072 (2)−0.0110 (15)0.0050 (16)−0.0137 (15)
C420.107 (2)0.0732 (18)0.0478 (17)−0.0254 (18)0.0091 (16)−0.0070 (15)
C430.0641 (16)0.0487 (13)0.0437 (15)−0.0140 (11)−0.0106 (12)0.0043 (11)
C440.0599 (14)0.0501 (13)0.0495 (15)−0.0065 (12)−0.0114 (12)−0.0003 (12)
O6A0.0541 (15)0.0888 (17)0.105 (2)−0.0090 (14)−0.0027 (15)−0.0180 (16)
O6B0.058 (4)0.048 (4)0.093 (5)−0.006 (3)−0.001 (4)−0.022 (4)
Geometric parameters (Å, °) top
Cl1—C41.734 (3)C21—H210.9300
Cl2—C111.742 (3)C22—C231.372 (4)
N1—C211.324 (3)C22—H220.9300
N1—C321.359 (3)C23—C241.406 (4)
N1—H1N0.8464C23—H230.9300
N2—C301.327 (3)C24—C321.408 (3)
N2—C311.366 (3)C24—C251.421 (4)
N3—C331.327 (4)C25—C261.332 (4)
N3—C441.365 (3)C25—H250.9300
N4—C421.338 (4)C26—C271.427 (4)
N4—C431.361 (3)C26—H260.9300
C7—O11.312 (3)C27—C311.404 (3)
C7—O21.239 (3)C27—C281.405 (4)
O1—H1A0.8758C28—C291.364 (4)
O3—C21.370 (3)C28—H280.9300
O3—H3A0.9483C29—C301.386 (4)
O4—C141.236 (3)C29—H290.9300
O5—C141.281 (3)C30—H300.9300
C1—C61.391 (3)C31—C321.434 (3)
C1—C21.401 (4)C33—C341.391 (4)
C1—C71.469 (4)C33—H330.9300
C2—C31.389 (4)C34—C351.360 (4)
C3—C41.375 (4)C34—H340.9300
C3—H30.9300C35—C361.403 (4)
C4—C51.382 (4)C35—H350.9300
C5—C61.383 (4)C36—C441.411 (3)
C5—H50.9300C36—C371.438 (4)
C6—H60.9300C37—C381.338 (4)
C8—C131.391 (3)C37—H370.9300
C8—C91.402 (3)C38—C391.421 (3)
C8—C141.496 (3)C38—H380.9300
C9—O6A1.336 (3)C39—C431.410 (3)
C9—C101.384 (3)C39—C401.415 (3)
C9—H90.9300C40—C411.350 (4)
C10—C111.364 (3)C40—H400.9300
C10—H100.9300C41—C421.382 (4)
C11—C121.380 (3)C41—H410.9300
C12—C131.381 (3)C42—H420.9300
C12—H120.9300C43—C441.453 (3)
C13—O6B1.354 (6)O6A—H6A0.9422
C13—H130.9300O6B—H6B0.8159
C21—C221.388 (4)
C21—N1—C32123.2 (2)C23—C24—C25123.7 (3)
C21—N1—H1N116.6C32—C24—C25118.3 (2)
C32—N1—H1N120.2C26—C25—C24121.8 (3)
C30—N2—C31116.4 (2)C26—C25—H25119.1
C33—N3—C44116.7 (2)C24—C25—H25119.1
C42—N4—C43116.8 (2)C25—C26—C27121.0 (3)
C7—O1—H1A108.4C25—C26—H26119.5
C2—O3—H3A116.5C27—C26—H26119.5
C6—C1—C2118.3 (2)C31—C27—C28116.1 (3)
C6—C1—C7121.4 (3)C31—C27—C26120.1 (3)
C2—C1—C7120.3 (2)C28—C27—C26123.8 (3)
O3—C2—C3116.7 (2)C29—C28—C27120.2 (3)
O3—C2—C1122.3 (3)C29—C28—H28119.9
C3—C2—C1121.0 (2)C27—C28—H28119.9
C4—C3—C2118.7 (3)C28—C29—C30119.1 (3)
C4—C3—H3120.7C28—C29—H29120.4
C2—C3—H3120.7C30—C29—H29120.4
C3—C4—C5122.0 (3)N2—C30—C29124.0 (3)
C3—C4—Cl1118.6 (2)N2—C30—H30118.0
C5—C4—Cl1119.5 (2)C29—C30—H30118.0
C4—C5—C6118.8 (3)N2—C31—C27124.2 (2)
C4—C5—H5120.6N2—C31—C32117.7 (2)
C6—C5—H5120.6C27—C31—C32118.0 (2)
C5—C6—C1121.3 (3)N1—C32—C24118.7 (2)
C5—C6—H6119.4N1—C32—C31120.5 (2)
C1—C6—H6119.4C24—C32—C31120.8 (2)
O2—C7—O1122.6 (3)N3—C33—C34125.0 (3)
O2—C7—C1122.2 (3)N3—C33—H33117.5
O1—C7—C1115.2 (3)C34—C33—H33117.5
C13—C8—C9118.0 (2)C35—C34—C33118.4 (3)
C13—C8—C14121.5 (2)C35—C34—H34120.8
C9—C8—C14120.5 (2)C33—C34—H34120.8
O6A—C9—C10116.5 (2)C34—C35—C36119.4 (3)
O6A—C9—C8122.9 (3)C34—C35—H35120.3
C10—C9—C8120.5 (2)C36—C35—H35120.3
C10—C9—H9119.7C35—C36—C44118.3 (2)
C8—C9—H9119.7C35—C36—C37122.2 (2)
C11—C10—C9119.2 (2)C44—C36—C37119.5 (2)
C11—C10—H10120.4C38—C37—C36121.1 (2)
C9—C10—H10120.4C38—C37—H37119.5
C10—C11—C12122.4 (2)C36—C37—H37119.5
C10—C11—Cl2118.8 (2)C37—C38—C39121.5 (2)
C12—C11—Cl2118.8 (2)C37—C38—H38119.3
C11—C12—C13117.9 (2)C39—C38—H38119.3
C11—C12—H12121.1C43—C39—C40117.6 (2)
C13—C12—H12121.1C43—C39—C38119.8 (2)
O6B—C13—C12117.2 (4)C40—C39—C38122.6 (2)
O6B—C13—C8120.8 (4)C41—C40—C39119.7 (3)
C12—C13—C8121.9 (2)C41—C40—H40120.1
C12—C13—H13119.0C39—C40—H40120.1
C8—C13—H13119.0C40—C41—C42118.8 (3)
O4—C14—O5124.4 (3)C40—C41—H41120.6
O4—C14—C8119.2 (2)C42—C41—H41120.6
O5—C14—C8116.4 (2)N4—C42—C41124.6 (3)
N1—C21—C22120.4 (2)N4—C42—H42117.7
N1—C21—H21119.8C41—C42—H42117.7
C22—C21—H21119.8N4—C43—C39122.3 (2)
C23—C22—C21118.8 (3)N4—C43—C44118.5 (2)
C23—C22—H22120.6C39—C43—C44119.2 (2)
C21—C22—H22120.6N3—C44—C36122.1 (2)
C22—C23—C24120.9 (3)N3—C44—C43119.0 (2)
C22—C23—H23119.6C36—C44—C43118.9 (2)
C24—C23—H23119.6C9—O6A—H6A106.4
C23—C24—C32118.0 (2)C13—O6B—H6B109.9
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O50.881.612.484 (2)173
N1—H1N···N3i0.852.142.915 (3)153
O3—H3A···Cl1ii0.952.663.1714 (19)114
O3—H3A···O20.951.862.603 (3)133
O6A—H6A···O40.941.742.584 (3)148
O6B—H6B···O50.821.802.494 (7)142
C5—H5···O2iii0.932.503.404 (3)164
C12—H12···O4ii0.932.513.381 (3)157
C21—H21···N2i0.932.513.345 (4)150
C22—H22···O1iv0.932.543.220 (4)130
C37—H37···O40.932.603.430 (3)150
C25—H25···Cg10.932.653.571 (3)174
C40—H40···Cg20.932.633.489 (3)154
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) x+1, y, z; (iii) x−1, y, z; (iv) −x+1, y−1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O50.881.612.484 (2)173
N1—H1N···N3i0.852.142.915 (3)153
O3—H3A···Cl1ii0.952.663.1714 (19)114
O3—H3A···O20.951.862.603 (3)133
O6A—H6A···O40.941.742.584 (3)148
O6B—H6B···O50.821.802.494 (7)142
C5—H5···O2iii0.932.503.404 (3)164
C12—H12···O4ii0.932.513.381 (3)157
C21—H21···N2i0.932.513.345 (4)150
C22—H22···O1iv0.932.543.220 (4)130
C37—H37···O40.932.603.430 (3)150
C25—H25···Cg10.932.653.571 (3)174
C40—H40···Cg20.932.633.489 (3)154
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) x+1, y, z; (iii) x−1, y, z; (iv) −x+1, y−1/2, −z+1/2.
Acknowledgements top

The work was supported by the ZIJIN project of Zhejiang University, China.

references
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