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Acta Cryst. (2007). E63, m1480-m1481    [ doi:10.1107/S1600536807019435 ]

[[mu]-Cucurbit[6]uril(2-)]bis[pentaaquacalcium(II)] bis[tetrachloridozincate(II)] heptahydrate

Y. Shao, Y.-Z. Li, J.-P. Shi and G.-Y. Lu

Abstract top

In the title compound, [Ca2(C36H36N24O12)(H2O)10][ZnCl4]2·7H2O, each cucurbit[6]uril molecule is coordinated to two calcium cations as a tetradentate ligand. Each calcium cation is coordinated by two neighboring carbonyl O atoms at a portal of the same cage. Heptacoordination of the calcium cation is completed with five water molecules. The transition-metal salt anion [ZnCl4]2- acts as a counter-ion. The cation is centrosymmetric. The crystal structure involves O-H...O and O-H...Cl hydrogen bonds. One of the water molecules is disordered, with an occupancy of 0.5.

Comment top

The construction of inorganic-organic hybrid supramolecular compounds of cucurbit[6]uril containing large pores or channels has developed significantly in recent years (Freeman et al., 1981; Gerasko et al., 2002). This paper follows a new structural report on cucurbit[6]uril with both coordinated calcium cation and transition-metal salt anion ZnCl42- as contra-ion.

As shown in Fig.1, each cucurbit[6]uril molecule is coordinated to two calcium cations as a tetradentate ligand, which is differs from the works reported by Freeman and Samsonenko in which cucurbit[6]uril molecules serves as bidentate ligands (Freeman et al., 1981; Samsonenko et al., 2001). The inner cavity of the cucurbit[6]uril molecule is filled with a guest water molecule, O7, its occupied probability is 0.5 and disordered over two positions. Each calcium cation is coordinated by two neighboring carbonyl O atoms (O4 and O5) at a portal of the same cage. The bond lengths are 2.383 (3) and 2.479 (3) Å for Ca1—O4 and Ca1—O5, respectively. Hepta-coordination at the Calcium cation is completed with five water molecules O8, O9, O10, O11 and O12. The Ca—O bond lengths vary from 2.366 (3) to 2.389 (3) Å.

Related literature top

For related literature, see: Freeman et al. (1981); Gerasko et al. (2002); Jansen et al. (2001); Samsonenko et al. (2001); Whang et al. (1998); Burrow et al. (1997).

Experimental top

Cucurbit[6]uril was prepared by modified methods (Whang et al., 1998; Jansen et al., 2001), and the other reagents were commercially available and without further purification. The title adduct suitable for X-ray crystallographic analysis was prepared by slow evaporation of the hydrochloric acid (4M) solution of cucurbit[6]uril (50 mg, 0.05 mmol), CaCl2 (35 mg, 0.32 mmol) and ZnCl2 (40 mg, 0.29 mmol).

Refinement top

H atoms were positioned geometrically and refined using a riding model with C—H = 0.97–0.98 Å, O—H = 0.85–0.97 Å, and with Uiso(H) = 1.2 times Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. View of the title adduct, showing the labeling of the non-H atoms and 30% probability ellipsoids. Labels of H atoms have been omitted for clarity. Symmetry codes: (i) 1/2 - x, 1/2 + y, 3/2 - z.
[µ-Cucurbit[6]uril]bis[pentaaquacalcium(II)] bis[tetrachloridozinc(II)] septhydrate top
Crystal data top
[Ca2(C36H36N24O12)(H2O)10][ZnCl4]2·7H2OF(000) = 1844
Mr = 1797.66Dx = 1.689 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 5973 reflections
a = 14.428 (3) Åθ = 2.1–26.4°
b = 16.397 (4) ŵ = 1.22 mm−1
c = 15.798 (3) ÅT = 291 K
β = 108.987 (3)°Block, colourless
V = 3534.0 (13) Å30.28 × 0.24 × 0.22 mm
Z = 2
Data collection top
Bruker SMART APEX CCD
diffractometer		6860 independent reflections
Radiation source: sealed tube4939 reflections with I > 2σ(I)
graphiteRint = 0.051
φ and ω scansθmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −17→17
Tmin = 0.72, Tmax = 0.76k = −20→13
17975 measured reflectionsl = −19→19
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.061Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.06P)2 + 1.99P]
where P = (Fo2 + 2Fc2)/3
6860 reflections(Δ/σ)max < 0.001
460 parametersΔρmax = 0.37 e Å−3
0 restraintsΔρmin = −0.48 e Å−3
Crystal data top
[Ca2(C36H36N24O12)(H2O)10][ZnCl4]2·7H2OV = 3534.0 (13) Å3
Mr = 1797.66Z = 2
Monoclinic, P21/nMo Kα radiation
a = 14.428 (3) ŵ = 1.22 mm−1
b = 16.397 (4) ÅT = 291 K
c = 15.798 (3) Å0.28 × 0.24 × 0.22 mm
β = 108.987 (3)°
Data collection top
Bruker SMART APEX CCD
diffractometer		6860 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		4939 reflections with I > 2σ(I)
Tmin = 0.72, Tmax = 0.76Rint = 0.051
17975 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.061H-atom parameters constrained
wR(F2) = 0.131Δρmax = 0.37 e Å−3
S = 1.02Δρmin = −0.48 e Å−3
6860 reflectionsAbsolute structure: ?
460 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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)
C1−0.1614 (3)0.2144 (3)0.3505 (3)0.0308 (9)
C2−0.1394 (3)0.0195 (3)0.2032 (3)0.0376 (11)
C3−0.1206 (3)−0.2000 (3)0.3098 (3)0.0308 (9)
C40.1202 (3)0.2273 (3)0.4369 (3)0.0308 (9)
C50.1425 (3)0.0420 (3)0.2987 (3)0.0323 (10)
C60.1614 (3)−0.1851 (3)0.4007 (3)0.0346 (10)
C7−0.1555 (3)0.2874 (3)0.4878 (3)0.0340 (10)
H5A−0.22550.27690.46660.041*
H5B−0.14630.34540.49980.041*
C8−0.1396 (3)0.1682 (3)0.2107 (3)0.0390 (11)
H3B−0.13020.20450.16570.047*
H3C−0.20940.15840.19550.047*
C9−0.1092 (3)−0.1247 (3)0.1791 (3)0.0435 (12)
H10A−0.0902−0.14650.13010.052*
H10B−0.1801−0.12690.16150.052*
C100.1016 (3)0.2972 (3)0.5671 (3)0.0355 (10)
H2B0.08630.35480.56800.043*
H2C0.17240.29200.58690.043*
C110.1138 (3)0.1896 (3)0.2852 (3)0.0390 (11)
H6A0.18470.19190.31040.047*
H6B0.09440.22300.23160.047*
C120.1465 (3)−0.1053 (3)0.2653 (3)0.0359 (10)
H8A0.2161−0.09730.29540.043*
H8B0.1384−0.12830.20680.043*
C13−0.0255 (3)0.2994 (3)0.4111 (3)0.0325 (10)
H9A−0.02630.35910.40970.039*
C14−0.0222 (3)0.2635 (3)0.3232 (3)0.0313 (9)
H14A−0.02760.30610.27840.038*
C15−0.0014 (3)0.0829 (3)0.1866 (3)0.0387 (11)
H4A−0.00420.11070.13090.046*
C160.0098 (3)−0.0092 (3)0.1801 (3)0.0404 (11)
H7A0.0155−0.02520.12230.048*
C170.0256 (3)−0.2159 (3)0.2784 (3)0.0351 (10)
H11A0.0315−0.24730.22760.042*
C180.0280 (3)−0.2717 (3)0.3574 (3)0.0340 (10)
H17A0.0340−0.32930.34340.041*
Ca10.34045 (6)0.11550 (5)0.48616 (6)0.0311 (2)
Cl10.60289 (9)0.00034 (7)0.96932 (8)0.0412 (3)
Cl20.85289 (9)0.06280 (9)0.97036 (8)0.0503 (3)
Cl30.73290 (9)−0.11430 (7)0.84019 (8)0.0426 (3)
Cl40.62931 (9)0.09276 (8)0.77144 (8)0.0430 (3)
N1−0.1162 (3)0.2666 (2)0.4182 (3)0.0362 (9)
N2−0.1056 (2)0.2085 (2)0.2959 (2)0.0339 (8)
N3−0.0919 (3)0.0918 (2)0.2066 (3)0.0377 (9)
N4−0.0793 (3)−0.0415 (2)0.1923 (2)0.0349 (8)
N5−0.0687 (3)−0.1766 (2)0.2567 (2)0.0346 (8)
N6−0.0648 (3)−0.2551 (2)0.3708 (3)0.0336 (8)
N70.0629 (2)0.2681 (2)0.4773 (2)0.0312 (8)
N80.0725 (3)0.2238 (2)0.3483 (3)0.0350 (8)
N90.0849 (3)0.1063 (2)0.2604 (2)0.0346 (8)
N100.0985 (3)−0.0272 (2)0.2537 (3)0.0371 (9)
N110.1100 (3)−0.1633 (2)0.3164 (2)0.0349 (8)
N120.1124 (2)−0.2437 (2)0.4295 (2)0.0310 (8)
O1−0.2394 (2)0.1809 (2)0.3391 (2)0.0415 (8)
O2−0.2196 (2)0.0094 (2)0.2103 (3)0.0495 (9)
O3−0.2035 (2)−0.1792 (2)0.3023 (2)0.0415 (8)
O40.2022 (2)0.19935 (19)0.4755 (2)0.0365 (7)
O50.2185 (2)0.0438 (2)0.3605 (2)0.0406 (8)
O60.2422 (2)−0.15661 (19)0.4453 (2)0.0378 (7)
O70.9032 (4)1.0047 (4)0.4553 (4)0.0431 (16)0.50
H7C0.90871.02170.40630.052*0.50
H7D0.89670.95340.44740.052*0.50
O80.4028 (2)0.2508 (2)0.4978 (2)0.0456 (8)
H8C0.45400.21970.54080.055*
H8D0.38090.30030.51910.055*
O90.5117 (2)0.0987 (2)0.5633 (2)0.0451 (8)
H9B0.55310.12300.54420.054*
H9C0.53150.05740.59680.054*
O100.4048 (2)0.1092 (2)0.3657 (2)0.0427 (8)
H10C0.44290.06940.36650.051*
H10D0.42290.15390.34870.051*
O110.3528 (2)−0.02801 (19)0.5115 (2)0.0388 (7)
H11B0.3621−0.07940.54350.047*
H11C0.37090.02160.54640.047*
O120.3432 (2)0.1156 (2)0.6367 (2)0.0431 (8)
H12D0.37780.07260.67670.052*
H12C0.33060.16620.66280.052*
O1W0.5848 (2)0.1119 (2)0.3298 (2)0.0420 (8)
H1WA0.58280.07770.28880.063*
H1WB0.60830.15670.31900.063*
O2W0.5973 (2)0.2777 (2)0.5188 (2)0.0434 (8)
H2WA0.63520.24110.54970.065*
H2WC0.59390.31710.55270.065*
O3W0.5930 (3)−0.0055 (2)0.2081 (2)0.0460 (8)
H3WA0.56560.02910.15710.069*
H3WB0.6620−0.01200.21880.069*
Zn10.70585 (4)0.01177 (3)0.88953 (3)0.03279 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.022 (2)0.031 (2)0.032 (2)0.0042 (17)−0.0022 (17)0.0092 (18)
C20.028 (2)0.050 (3)0.028 (2)−0.002 (2)−0.0007 (18)−0.001 (2)
C30.028 (2)0.032 (2)0.028 (2)−0.0056 (18)0.0042 (17)−0.0099 (18)
C40.029 (2)0.028 (2)0.032 (2)−0.0014 (17)0.0068 (18)0.0094 (18)
C50.030 (2)0.045 (3)0.022 (2)−0.0009 (19)0.0083 (18)0.0044 (18)
C60.023 (2)0.040 (3)0.038 (3)0.0015 (19)0.0056 (19)−0.0092 (19)
C70.029 (2)0.026 (2)0.045 (3)0.0086 (17)0.0082 (19)0.0002 (19)
C80.031 (2)0.056 (3)0.025 (2)0.002 (2)0.0026 (18)0.013 (2)
C90.029 (2)0.056 (3)0.036 (3)−0.008 (2)−0.0019 (19)−0.013 (2)
C100.029 (2)0.030 (2)0.042 (3)−0.0089 (18)0.0044 (19)−0.002 (2)
C110.035 (2)0.047 (3)0.032 (2)−0.002 (2)0.007 (2)0.009 (2)
C120.035 (2)0.044 (3)0.031 (2)0.003 (2)0.0126 (19)−0.005 (2)
C130.030 (2)0.025 (2)0.040 (3)0.0052 (18)0.0083 (19)0.0108 (18)
C140.029 (2)0.028 (2)0.033 (2)0.0027 (17)0.0052 (18)0.0137 (18)
C150.027 (2)0.049 (3)0.033 (3)−0.005 (2)−0.0002 (18)0.005 (2)
C160.031 (2)0.049 (3)0.036 (3)−0.002 (2)0.003 (2)0.000 (2)
C170.036 (2)0.037 (3)0.030 (2)0.0040 (19)0.0077 (19)−0.0145 (19)
C180.031 (2)0.034 (2)0.034 (2)−0.0014 (18)0.0058 (18)−0.0099 (19)
Ca10.0262 (4)0.0315 (5)0.0298 (4)0.0022 (3)0.0013 (3)−0.0012 (4)
Cl10.0536 (7)0.0444 (7)0.0435 (6)0.0105 (5)0.0403 (6)0.0066 (5)
Cl20.0398 (6)0.0648 (8)0.0355 (7)−0.0135 (6)−0.0027 (5)−0.0041 (6)
Cl30.0498 (7)0.0398 (6)0.0434 (7)0.0038 (5)0.0223 (5)−0.0032 (5)
Cl40.0395 (6)0.0496 (7)0.0385 (6)0.0177 (5)0.0106 (5)0.0175 (5)
N10.037 (2)0.0281 (19)0.040 (2)−0.0044 (16)0.0069 (17)−0.0003 (16)
N20.0246 (18)0.040 (2)0.033 (2)−0.0034 (16)0.0050 (15)0.0055 (16)
N30.0265 (19)0.046 (2)0.036 (2)0.0023 (17)0.0043 (16)−0.0043 (17)
N40.032 (2)0.040 (2)0.030 (2)−0.0081 (17)0.0059 (16)0.0008 (16)
N50.0269 (18)0.045 (2)0.028 (2)−0.0005 (16)0.0038 (15)−0.0053 (16)
N60.0276 (19)0.039 (2)0.033 (2)0.0031 (16)0.0090 (15)−0.0057 (16)
N70.0263 (18)0.0329 (19)0.030 (2)0.0020 (15)0.0028 (15)−0.0014 (15)
N80.0313 (19)0.041 (2)0.031 (2)0.0040 (16)0.0079 (16)0.0139 (16)
N90.0280 (19)0.039 (2)0.031 (2)−0.0042 (16)0.0006 (15)0.0021 (16)
N100.034 (2)0.039 (2)0.034 (2)−0.0012 (17)0.0055 (16)0.0014 (17)
N110.0234 (18)0.044 (2)0.032 (2)−0.0035 (16)0.0011 (15)−0.0023 (17)
N120.0258 (18)0.0274 (19)0.035 (2)−0.0035 (15)0.0033 (15)−0.0003 (15)
O10.0319 (17)0.049 (2)0.041 (2)−0.0062 (15)0.0093 (15)0.0006 (15)
O20.0330 (18)0.058 (2)0.057 (2)−0.0008 (16)0.0135 (16)−0.0056 (18)
O30.0305 (17)0.051 (2)0.0401 (19)−0.0005 (15)0.0078 (14)−0.0087 (15)
O40.0277 (16)0.0439 (18)0.0342 (17)0.0034 (14)0.0051 (13)0.0023 (14)
O50.0260 (16)0.049 (2)0.0353 (18)−0.0048 (14)−0.0056 (13)0.0007 (15)
O60.0287 (16)0.0379 (18)0.0395 (18)−0.0066 (14)0.0010 (13)0.0032 (14)
O70.032 (3)0.051 (4)0.040 (4)0.011 (3)0.002 (3)0.008 (3)
O80.0425 (19)0.0368 (18)0.057 (2)0.0019 (15)0.0160 (17)−0.0069 (16)
O90.0315 (17)0.051 (2)0.0425 (19)0.0078 (15)−0.0020 (14)−0.0039 (16)
O100.0338 (17)0.054 (2)0.0378 (18)−0.0160 (15)0.0079 (14)−0.0038 (16)
O110.0356 (17)0.0289 (16)0.0409 (18)−0.0001 (13)−0.0026 (14)−0.0028 (13)
O120.0485 (19)0.0417 (19)0.0385 (19)0.0203 (15)0.0130 (15)−0.0049 (15)
O1W0.0357 (17)0.0478 (19)0.0422 (19)−0.0104 (15)0.0125 (14)0.0183 (15)
O2W0.0388 (18)0.0439 (19)0.047 (2)−0.0014 (15)0.0131 (15)−0.0033 (16)
O3W0.0438 (19)0.048 (2)0.0361 (18)−0.0156 (16)−0.0008 (15)−0.0049 (15)
Zn10.0340 (3)0.0351 (3)0.0277 (3)−0.0006 (2)0.0079 (2)−0.0002 (2)
Geometric parameters (Å, °) top
C1—O11.212 (5)C14—N21.453 (5)
C1—N11.359 (6)C14—H14A0.9800
C1—N21.361 (6)C15—N31.447 (6)
C2—O21.209 (5)C15—N91.453 (5)
C2—N31.362 (6)C15—C161.526 (7)
C2—N41.370 (6)C15—H4A0.9800
C3—O31.212 (5)C16—N101.452 (6)
C3—N51.350 (6)C16—N41.460 (6)
C3—N61.373 (6)C16—H7A0.9800
C4—O41.230 (5)C17—N51.442 (6)
C4—N81.345 (6)C17—N111.453 (6)
C4—N71.372 (5)C17—C181.540 (6)
C5—O51.208 (5)C17—H11A0.9800
C5—N91.357 (6)C18—N121.445 (5)
C5—N101.380 (6)C18—N61.447 (5)
C6—O61.241 (5)C18—H17A0.9800
C6—N111.345 (6)Ca1—O122.366 (3)
C6—N121.357 (6)Ca1—O102.376 (3)
C7—N11.432 (6)Ca1—O82.379 (3)
C7—N12i1.441 (6)Ca1—O42.384 (3)
C7—H5A0.9700Ca1—O112.384 (3)
C7—H5B0.9700Ca1—O92.389 (3)
C8—N21.436 (6)Ca1—O52.479 (3)
C8—N31.441 (6)Cl1—Zn12.2471 (11)
C8—H3B0.9700Cl2—Zn12.2512 (13)
C8—H3C0.9700Cl3—Zn12.2871 (13)
C9—N41.426 (6)Cl4—Zn12.2634 (12)
C9—N51.450 (6)N6—C10i1.436 (6)
C9—H10A0.9700N12—C7i1.441 (6)
C9—H10B0.9700O7—H7C0.8502
C10—N71.427 (6)O7—H7D0.8501
C10—N6i1.436 (6)O8—H8C0.9701
C10—H2B0.9700O8—H8D0.9699
C10—H2C0.9700O9—H9B0.8502
C11—N81.432 (6)O9—H9C0.8498
C11—N91.444 (6)O10—H10C0.8500
C11—H6A0.9700O10—H10D0.8499
C11—H6B0.9700O11—H11B0.9700
C12—N101.438 (6)O11—H11C0.9702
C12—N111.452 (6)O12—H12D0.9697
C12—H8A0.9700O12—H12C0.9698
C12—H8B0.9700O1W—H1WA0.8501
C13—N11.453 (5)O1W—H1WB0.8497
C13—N71.454 (5)O2W—H2WA0.8498
C13—C141.523 (6)O2W—H2WC0.8498
C13—H9A0.9800O3W—H3WA0.9596
C14—N81.447 (5)O3W—H3WB0.9600
O1—C1—N1125.9 (4)O10—Ca1—O4120.34 (12)
O1—C1—N2125.8 (4)O8—Ca1—O475.77 (11)
N1—C1—N2108.2 (4)O12—Ca1—O1181.71 (12)
O2—C2—N3126.8 (5)O10—Ca1—O1193.68 (12)
O2—C2—N4125.2 (5)O8—Ca1—O11154.45 (12)
N3—C2—N4108.0 (4)O4—Ca1—O11126.60 (11)
O3—C3—N5126.1 (4)O12—Ca1—O979.11 (12)
O3—C3—N6126.0 (4)O10—Ca1—O978.14 (12)
N5—C3—N6107.8 (4)O8—Ca1—O976.46 (12)
O4—C4—N8125.7 (4)O4—Ca1—O9143.67 (12)
O4—C4—N7125.4 (4)O11—Ca1—O978.01 (11)
N8—C4—N7108.9 (4)O12—Ca1—O5125.49 (12)
O5—C5—N9127.3 (4)O10—Ca1—O572.47 (11)
O5—C5—N10125.5 (4)O8—Ca1—O5131.00 (12)
N9—C5—N10107.2 (4)O4—Ca1—O581.80 (11)
O6—C6—N11125.2 (4)O11—Ca1—O570.18 (11)
O6—C6—N12124.9 (4)O9—Ca1—O5134.48 (11)
N11—C6—N12109.9 (4)O12—Ca1—H8C81.2
N1—C7—N12i114.5 (3)O10—Ca1—H8C85.3
N1—C7—H5A108.6O8—Ca1—H8C23.7
N12i—C7—H5A108.6O4—Ca1—H8C94.3
N1—C7—H5B108.6O11—Ca1—H8C131.1
N12i—C7—H5B108.6O9—Ca1—H8C53.8
H5A—C7—H5B107.6O5—Ca1—H8C151.0
N2—C8—N3114.8 (4)O12—Ca1—H11C62.9
N2—C8—H3B108.6O10—Ca1—H11C107.2
N3—C8—H3B108.6O8—Ca1—H11C137.8
N2—C8—H3C108.6O4—Ca1—H11C126.1
N3—C8—H3C108.6O11—Ca1—H11C21.4
H3B—C8—H3C107.6O9—Ca1—H11C66.1
N4—C9—N5114.8 (4)O5—Ca1—H11C90.3
N4—C9—H10A108.6H8C—Ca1—H11C114.4
N5—C9—H10A108.6C1—N1—C7123.1 (4)
N4—C9—H10B108.6C1—N1—C13112.7 (4)
N5—C9—H10B108.6C7—N1—C13124.2 (4)
H10A—C9—H10B107.6C1—N2—C8122.3 (4)
N7—C10—N6i113.9 (4)C1—N2—C14111.8 (4)
N7—C10—H2B108.8C8—N2—C14124.2 (4)
N6i—C10—H2B108.8C2—N3—C8121.1 (4)
N7—C10—H2C108.8C2—N3—C15112.5 (4)
N6i—C10—H2C108.8C8—N3—C15125.1 (4)
H2B—C10—H2C107.7C2—N4—C9122.9 (4)
N8—C11—N9114.2 (4)C2—N4—C16111.9 (4)
N8—C11—H6A108.7C9—N4—C16124.4 (4)
N9—C11—H6A108.7C3—N5—C17113.3 (4)
N8—C11—H6B108.7C3—N5—C9122.7 (4)
N9—C11—H6B108.7C17—N5—C9123.6 (4)
H6A—C11—H6B107.6C3—N6—C10i122.2 (3)
N10—C12—N11114.1 (4)C3—N6—C18112.4 (4)
N10—C12—H8A108.7C10i—N6—C18125.0 (4)
N11—C12—H8A108.7C4—N7—C10121.7 (4)
N10—C12—H8B108.7C4—N7—C13110.9 (3)
N11—C12—H8B108.7C10—N7—C13124.4 (4)
H8A—C12—H8B107.6C4—N8—C11123.6 (4)
N1—C13—N7114.5 (3)C4—N8—C14112.5 (4)
N1—C13—C14103.0 (4)C11—N8—C14123.7 (4)
N7—C13—C14103.8 (3)C5—N9—C11122.1 (4)
N1—C13—H9A111.6C5—N9—C15113.2 (4)
N7—C13—H9A111.6C11—N9—C15124.3 (4)
C14—C13—H9A111.6C5—N10—C12123.0 (4)
N8—C14—N2114.7 (3)C5—N10—C16112.5 (4)
N8—C14—C13103.4 (3)C12—N10—C16123.1 (4)
N2—C14—C13104.0 (3)C6—N11—C12122.8 (4)
N8—C14—H14A111.4C6—N11—C17111.7 (4)
N2—C14—H14A111.4C12—N11—C17124.5 (4)
C13—C14—H14A111.4C6—N12—C7i122.5 (4)
N3—C15—N9113.4 (4)C6—N12—C18111.0 (4)
N3—C15—C16103.7 (4)C7i—N12—C18124.1 (4)
N9—C15—C16103.5 (4)C4—O4—Ca1153.9 (3)
N3—C15—H4A111.9C5—O5—Ca1151.6 (3)
N9—C15—H4A111.9H7C—O7—H7D103.2
C16—C15—H4A111.9Ca1—O8—H8C75.3
N10—C16—N4113.9 (4)Ca1—O8—H8D130.5
N10—C16—C15103.4 (4)H8C—O8—H8D117.1
N4—C16—C15103.5 (4)Ca1—O9—H9B119.6
N10—C16—H7A111.8Ca1—O9—H9C119.5
N4—C16—H7A111.8H9B—O9—H9C117.4
C15—C16—H7A111.8Ca1—O10—H10C116.1
N5—C17—N11115.6 (4)Ca1—O10—H10D117.1
N5—C17—C18103.2 (3)H10C—O10—H10D113.8
N11—C17—C18102.9 (3)Ca1—O11—H11B159.4
N5—C17—H11A111.5H11B—O11—H11C117.8
N11—C17—H11A111.5Ca1—O12—H12D119.5
C18—C17—H11A111.5Ca1—O12—H12C118.9
N12—C18—N6114.0 (4)H12D—O12—H12C118.2
N12—C18—C17103.9 (3)H1WA—O1W—H1WB109.5
N6—C18—C17103.2 (4)H2WA—O2W—H2WC109.5
N12—C18—H17A111.7H3WA—O3W—H3WB109.5
N6—C18—H17A111.7Cl1—Zn1—Cl2112.69 (5)
C17—C18—H17A111.7Cl1—Zn1—Cl4106.08 (5)
O12—Ca1—O10157.25 (11)Cl2—Zn1—Cl4111.50 (6)
O12—Ca1—O892.29 (12)Cl1—Zn1—Cl3109.46 (5)
O10—Ca1—O882.28 (12)Cl2—Zn1—Cl3107.18 (5)
O12—Ca1—O479.07 (11)Cl4—Zn1—Cl3109.93 (5)
Symmetry codes: (i) −x, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O8—H8C···O90.972.142.950 (5)141
O8—H8D···Cl2ii0.972.363.137 (4)136
O9—H9B···O11iii0.852.412.840 (5)112
O11—H11B···O1Wiii0.971.972.742 (4)135
O12—H12D···O3Wiii0.972.052.940 (5)152
O2W—H2WA···O6iii0.852.232.961 (5)145
O3W—H3WA···Cl1iii0.962.643.271 (4)124
O9—H9C···Cl40.852.723.173 (4)115
O10—H10C···O1W0.852.412.833 (4)112
O11—H11C···O120.972.223.107 (4)151
O11—H11C···O90.972.333.004 (5)126
O1W—H1WA···O3W0.851.912.750 (5)173
O12—H12C···O3i0.972.092.710 (4)120
O1W—H1WB···O1iv0.852.152.737 (4)126
O3W—H3WB···O2iv0.961.792.704 (5)158
O2W—H2WC···Cl3v0.852.763.248 (4)118
Symmetry codes: (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+1, −y, −z+1; (i) −x, −y, −z+1; (iv) x+1, y, z; (v) −x+3/2, y+1/2, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O8—H8C···O90.972.142.950 (5)141
O8—H8D···Cl2i0.972.363.137 (4)136
O9—H9B···O11ii0.852.412.840 (5)112
O11—H11B···O1Wii0.971.972.742 (4)135
O12—H12D···O3Wii0.972.052.940 (5)152
O2W—H2WA···O6ii0.852.232.961 (5)145
O3W—H3WA···Cl1ii0.962.643.271 (4)124
O9—H9C···Cl40.852.723.173 (4)115
O10—H10C···O1W0.852.412.833 (4)112
O11—H11C···O120.972.223.107 (4)151
O11—H11C···O90.972.333.004 (5)126
O1W—H1WA···O3W0.851.912.750 (5)173
O12—H12C···O3iii0.972.092.710 (4)120
O1W—H1WB···O1iv0.852.152.737 (4)126
O3W—H3WB···O2iv0.961.792.704 (5)158
O2W—H2WC···Cl3v0.852.763.248 (4)118
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+1, −y, −z+1; (iii) −x, −y, −z+1; (iv) x+1, y, z; (v) −x+3/2, y+1/2, −z+3/2.
Acknowledgements top

This work was supported by the National Natural Science Foundation of China (research grant No. 20372032).

references
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