The 2-methylbiphenyl-4,4′-dicarboxylate (mbpdc2−) ligand has versatile coordination modes and can be used to construct multinuclear structures. Despite this, reports of the synthesis of coordination complexes involving this ligand are scarce. The title compound, poly[[triaquadi-μ3-hydroxido-hexakis(μ4-2-methylbiphenyl-4,4′-dicarboxylato)calcium(II)hexazinc(II)] monohydrate], {[CaZn6(C15H10O4)6(OH)2(H2O)3]·H2O}n, has been prepared by the hydrothermal assembly of Zn(NO3)2·6H2O, CaCl2 and 2-methylbiphenyl-4,4′-dicarboxylic acid. Two ZnII atoms adopt a four-coordinated distorted tetrahedral geometry by bonding to three O atoms from three different 2-methylbiphenyl-4,4′-dicarboxylate (mbpdc2−) dianionic ligands and one bridging hydroxide O atom. For the remaining ZnII atom, a five-coordinate environment is completed half the time by one carboxylate O atom, and then the same carboxylate O atom and an aqua O atom are present the other half of the time, giving a six-coordinate environment. The CaII atom is coordinated by six O atoms to give an octahedral coordination geometry. The supramolecular secondary building unit (SBU) is a hamburger-like heptanuclear unit (Zn6CaO30) and these units are interconnected through mbpdc2− carboxylate groups to generate a three-dimensional framework with the pcu topology. The single net leaves voids that are filled by mutual interpenetration of an independent equivalent framework in a twofold interpenetrating architecture. The title compound shows thermal stability up to 673 K. The excitation and luminescence data showed the emission of a bright-blue fluorescence.
Supporting information
CCDC reference: 1548247
Data collection: SMART (Bruker, 2008); cell refinement: SMART; data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Olex2 (Dolomanov et al., 2009) and
DIAMOND (Brandenburg, 2005); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).
Poly[triaquadi-µ
3-hydroxido-hexakis(µ
4-2-methylbiphenyl-4,4'-dicarboxylato)calcium(II)hexazinc(II)]
top
Crystal data top
[CaZn6(C15H10O4)6(OH)2(H2O)3] | Dx = 1.482 Mg m−3 |
Mr = 2045.74 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | Cell parameters from 2704 reflections |
a = 33.1506 (12) Å | θ = 2.2–19.1° |
c = 16.6829 (14) Å | µ = 1.68 mm−1 |
V = 18334 (2) Å3 | T = 293 K |
Z = 8 | Block, colourless |
F(000) = 8320 | 0.22 × 0.2 × 0.18 mm |
Data collection top
Bruker SMART CCD area detector diffractometer | Rint = 0.152 |
phi and ω scans | θmax = 25.0°, θmin = 1.2° |
57289 measured reflections | h = −39→38 |
8101 independent reflections | k = −39→38 |
4971 reflections with I > 2σ(I) | l = −19→18 |
Refinement top
Refinement on F2 | 18 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.056 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.159 | w = 1/[σ2(Fo2) + (0.0728P)2 + 32.5817P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
8101 reflections | Δρmax = 0.96 e Å−3 |
607 parameters | Δρmin = −0.51 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Zn1 | 0.24042 (2) | 0.15405 (2) | 0.44302 (4) | 0.0289 (2) | |
Zn2 | 0.15697 (2) | 0.20404 (2) | 0.43840 (4) | 0.0307 (2) | |
Zn3 | 0.16534 (2) | 0.12251 (2) | 0.32299 (5) | 0.0354 (2) | |
Ca1 | 0.2500 | 0.2500 | 0.2500 | 0.0267 (4) | |
O1 | 0.28138 (12) | 0.20906 (12) | 0.3398 (3) | 0.0358 (11) | |
O2 | 0.29626 (12) | 0.15413 (13) | 0.4067 (3) | 0.0404 (11) | |
O3 | 0.60114 (14) | 0.19367 (17) | 0.0908 (3) | 0.0644 (16) | |
O4 | 0.61299 (15) | 0.15123 (19) | 0.1922 (3) | 0.0740 (18) | |
O5 | 0.33454 (14) | 0.31593 (15) | 0.9516 (3) | 0.0479 (12) | |
O6 | 0.26748 (14) | 0.31780 (15) | 0.9546 (3) | 0.0476 (12) | |
O7 | 0.29141 (12) | 0.30432 (13) | 0.2742 (2) | 0.0357 (10) | |
O8 | 0.31138 (13) | 0.36806 (12) | 0.2880 (3) | 0.0401 (11) | |
O9 | 0.20384 (13) | 0.26553 (12) | 0.3473 (3) | 0.0386 (11) | |
O10 | 0.16336 (14) | 0.26140 (13) | 0.4514 (3) | 0.0481 (13) | |
O11 | 0.23654 (14) | 0.59815 (13) | 0.5189 (3) | 0.0522 (14) | |
O12 | 0.2046 (6) | 0.5803 (3) | 0.6265 (8) | 0.033 (5) | 0.50 (4) |
O12A | 0.1808 (10) | 0.5877 (7) | 0.5889 (18) | 0.092 (12) | 0.50 (4) |
O13 | 0.19484 (12) | 0.17008 (11) | 0.3770 (2) | 0.0261 (9) | |
H13 | 0.2003 (17) | 0.1787 (17) | 0.3325 (16) | 0.031* | |
O14 | 0.1374 (2) | 0.07056 (17) | 0.2861 (4) | 0.089 (2) | |
H14A | 0.1563 (13) | 0.0548 (18) | 0.278 (5) | 0.133* | |
H14B | 0.125 (2) | 0.0774 (18) | 0.245 (3) | 0.133* | |
O15 | 0.1356 (3) | 0.1100 (3) | 0.4544 (7) | 0.067 (3) | 0.5 |
H15A | 0.1483 | 0.1206 | 0.4941 | 0.100* | 0.5 |
H15B | 0.1125 | 0.1224 | 0.4652 | 0.100* | 0.5 |
C1 | 0.30610 (17) | 0.18275 (18) | 0.3587 (4) | 0.0294 (14) | |
C2 | 0.34812 (17) | 0.18305 (18) | 0.3266 (4) | 0.0302 (14) | |
C3 | 0.36269 (18) | 0.21716 (19) | 0.2896 (4) | 0.0372 (16) | |
H3 | 0.3466 | 0.2401 | 0.2864 | 0.034 (17)* | |
C4 | 0.40152 (19) | 0.2176 (2) | 0.2567 (4) | 0.0452 (18) | |
H4 | 0.4114 | 0.2408 | 0.2326 | 0.054* | |
C5 | 0.42516 (19) | 0.1832 (2) | 0.2600 (4) | 0.0427 (18) | |
C6 | 0.4098 (2) | 0.1495 (2) | 0.2959 (5) | 0.051 (2) | |
H6 | 0.4254 | 0.1262 | 0.2972 | 0.061* | |
C7 | 0.37145 (19) | 0.14876 (19) | 0.3308 (4) | 0.0404 (17) | |
H7 | 0.3620 | 0.1257 | 0.3562 | 0.048* | |
C8 | 0.4968 (2) | 0.1698 (3) | 0.2791 (5) | 0.085 (3) | |
H8 | 0.4901 | 0.1639 | 0.3320 | 0.102* | |
C9 | 0.4672 (2) | 0.1819 (2) | 0.2282 (5) | 0.055 (2) | |
C10 | 0.4775 (2) | 0.1922 (2) | 0.1498 (5) | 0.059 (2) | |
C11 | 0.4463 (3) | 0.2024 (3) | 0.0848 (7) | 0.104 (4) | |
H11A | 0.4374 | 0.2297 | 0.0914 | 0.157* | |
H11B | 0.4236 | 0.1845 | 0.0896 | 0.157* | |
H11C | 0.4583 | 0.1992 | 0.0329 | 0.157* | |
C12 | 0.5366 (2) | 0.1660 (3) | 0.2547 (6) | 0.094 (4) | |
H12 | 0.5560 | 0.1560 | 0.2898 | 0.112* | |
C13 | 0.5473 (2) | 0.1773 (3) | 0.1775 (5) | 0.061 (2) | |
C14 | 0.5176 (2) | 0.1905 (2) | 0.1254 (5) | 0.062 (2) | |
H14 | 0.5245 | 0.1982 | 0.0736 | 0.074* | |
C15 | 0.5905 (2) | 0.1733 (3) | 0.1513 (5) | 0.058 (2) | |
C16 | 0.3004 (2) | 0.31616 (19) | 0.9178 (4) | 0.0384 (16) | |
C17 | 0.3000 (2) | 0.3161 (2) | 0.8287 (4) | 0.0437 (17) | |
C18 | 0.3349 (2) | 0.3212 (3) | 0.7849 (4) | 0.061 (2) | |
H18 | 0.3595 | 0.3229 | 0.8114 | 0.073* | |
C19 | 0.3340 (2) | 0.3236 (3) | 0.7022 (4) | 0.068 (3) | |
H19 | 0.3577 | 0.3280 | 0.6739 | 0.082* | |
C20 | 0.2980 (2) | 0.3196 (2) | 0.6614 (4) | 0.053 (2) | |
C21 | 0.2628 (2) | 0.3133 (3) | 0.7054 (5) | 0.068 (3) | |
H21 | 0.2383 | 0.3099 | 0.6790 | 0.082* | 0.611 (13) |
C22 | 0.2641 (2) | 0.3123 (3) | 0.7881 (4) | 0.062 (2) | |
H22 | 0.2402 | 0.3089 | 0.8169 | 0.074* | |
C23 | 0.2964 (2) | 0.3226 (2) | 0.5715 (4) | 0.052 (2) | |
C24 | 0.2954 (2) | 0.3608 (2) | 0.5362 (4) | 0.053 (2) | |
H24 | 0.2942 | 0.3837 | 0.5682 | 0.064* | |
C25 | 0.2962 (2) | 0.3644 (2) | 0.4547 (4) | 0.0472 (18) | |
H25 | 0.2962 | 0.3900 | 0.4317 | 0.057* | |
C26 | 0.29703 (18) | 0.3311 (2) | 0.4062 (4) | 0.0342 (15) | |
C27 | 0.2971 (2) | 0.2932 (2) | 0.4413 (4) | 0.0505 (19) | |
H27 | 0.2974 | 0.2703 | 0.4092 | 0.061* | |
C28 | 0.2968 (3) | 0.2895 (2) | 0.5235 (4) | 0.057 (2) | |
H28 | 0.2973 | 0.2631 | 0.5473 | 0.069* | 0.389 (13) |
C29 | 0.29998 (18) | 0.3347 (2) | 0.3170 (4) | 0.0343 (15) | |
C30 | 0.3059 (5) | 0.2473 (4) | 0.5579 (9) | 0.086 (5) | 0.611 (13) |
H30A | 0.2925 | 0.2442 | 0.6085 | 0.130* | 0.611 (13) |
H30B | 0.3345 | 0.2443 | 0.5653 | 0.130* | 0.611 (13) |
H30C | 0.2964 | 0.2270 | 0.5213 | 0.130* | 0.611 (13) |
C30B | 0.2199 (6) | 0.3095 (10) | 0.6691 (17) | 0.127 (11) | 0.389 (13) |
H30D | 0.2216 | 0.3105 | 0.6117 | 0.190* | 0.389 (13) |
H30E | 0.2082 | 0.2843 | 0.6852 | 0.190* | 0.389 (13) |
H30F | 0.2033 | 0.3313 | 0.6879 | 0.190* | 0.389 (13) |
C31 | 0.18550 (19) | 0.28138 (18) | 0.4030 (4) | 0.0335 (15) | |
C32 | 0.18834 (18) | 0.32579 (18) | 0.4178 (4) | 0.0335 (15) | |
C33 | 0.1810 (2) | 0.3423 (2) | 0.4930 (5) | 0.060 (2) | |
H33 | 0.1731 | 0.3255 | 0.5348 | 0.072* | |
C34 | 0.1850 (2) | 0.3829 (2) | 0.5069 (5) | 0.064 (2) | |
H34 | 0.1800 | 0.3932 | 0.5577 | 0.077* | |
C35 | 0.1966 (2) | 0.4086 (2) | 0.4447 (5) | 0.0470 (18) | |
C36 | 0.20358 (19) | 0.39279 (19) | 0.3701 (4) | 0.0388 (16) | |
C37 | 0.19987 (19) | 0.35183 (19) | 0.3577 (4) | 0.0390 (16) | |
H37 | 0.2053 | 0.3414 | 0.3071 | 0.047* | |
C38 | 0.2008 (2) | 0.4523 (2) | 0.4669 (4) | 0.0459 (18) | |
C39 | 0.1717 (3) | 0.4703 (2) | 0.5125 (6) | 0.073 (3) | |
H39 | 0.1488 | 0.4558 | 0.5264 | 0.088* | |
C40 | 0.2093 (2) | 0.5322 (2) | 0.5186 (5) | 0.056 (2) | |
C41 | 0.1758 (3) | 0.5102 (2) | 0.5389 (6) | 0.078 (3) | |
H41 | 0.1558 | 0.5218 | 0.5702 | 0.094* | |
C42 | 0.2373 (2) | 0.5151 (2) | 0.4696 (5) | 0.059 (2) | |
H42 | 0.2591 | 0.5305 | 0.4520 | 0.071* | |
C43 | 0.2341 (2) | 0.4754 (2) | 0.4456 (5) | 0.056 (2) | |
H43 | 0.2545 | 0.4639 | 0.4148 | 0.067* | |
C44 | 0.2143 (3) | 0.5745 (2) | 0.5511 (5) | 0.061 (2) | |
C45 | 0.2161 (3) | 0.4180 (3) | 0.2977 (7) | 0.103 (4) | |
H45A | 0.2047 | 0.4066 | 0.2499 | 0.154* | |
H45B | 0.2450 | 0.4182 | 0.2934 | 0.154* | |
H45C | 0.2065 | 0.4451 | 0.3042 | 0.154* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.0263 (4) | 0.0334 (4) | 0.0268 (4) | 0.0002 (3) | −0.0021 (3) | 0.0036 (3) |
Zn2 | 0.0316 (4) | 0.0323 (4) | 0.0281 (4) | 0.0036 (3) | −0.0051 (3) | −0.0050 (3) |
Zn3 | 0.0336 (4) | 0.0334 (4) | 0.0392 (5) | −0.0007 (3) | −0.0092 (3) | −0.0057 (3) |
Ca1 | 0.0306 (9) | 0.0248 (9) | 0.0247 (10) | 0.0005 (7) | −0.0007 (8) | 0.0026 (7) |
O1 | 0.029 (2) | 0.037 (3) | 0.041 (3) | 0.010 (2) | 0.002 (2) | 0.008 (2) |
O2 | 0.030 (2) | 0.048 (3) | 0.043 (3) | 0.008 (2) | 0.007 (2) | 0.019 (2) |
O3 | 0.037 (3) | 0.086 (4) | 0.069 (4) | 0.008 (3) | 0.016 (3) | 0.034 (3) |
O4 | 0.038 (3) | 0.116 (5) | 0.068 (4) | 0.025 (3) | 0.009 (3) | 0.045 (4) |
O5 | 0.046 (3) | 0.073 (3) | 0.025 (3) | −0.003 (2) | −0.003 (2) | 0.001 (2) |
O6 | 0.045 (3) | 0.069 (3) | 0.028 (3) | −0.004 (2) | 0.001 (2) | −0.011 (2) |
O7 | 0.046 (3) | 0.037 (3) | 0.024 (2) | −0.010 (2) | −0.003 (2) | −0.005 (2) |
O8 | 0.059 (3) | 0.034 (3) | 0.027 (3) | −0.008 (2) | 0.000 (2) | −0.004 (2) |
O9 | 0.044 (3) | 0.033 (2) | 0.039 (3) | 0.005 (2) | 0.011 (2) | −0.008 (2) |
O10 | 0.062 (3) | 0.033 (3) | 0.050 (3) | −0.005 (2) | 0.023 (3) | −0.002 (2) |
O11 | 0.053 (3) | 0.040 (3) | 0.064 (4) | −0.017 (2) | 0.014 (3) | −0.017 (3) |
O12 | 0.048 (10) | 0.024 (5) | 0.026 (7) | 0.000 (5) | 0.007 (6) | −0.008 (4) |
O12A | 0.10 (2) | 0.078 (11) | 0.094 (17) | −0.049 (13) | 0.041 (17) | −0.045 (12) |
O13 | 0.030 (2) | 0.027 (2) | 0.021 (2) | −0.0037 (17) | −0.0001 (19) | −0.0007 (18) |
O14 | 0.128 (6) | 0.049 (3) | 0.088 (5) | −0.019 (3) | −0.065 (4) | 0.011 (3) |
O15 | 0.076 (8) | 0.064 (7) | 0.062 (8) | 0.003 (6) | 0.015 (6) | −0.001 (6) |
C1 | 0.029 (3) | 0.034 (4) | 0.025 (3) | −0.003 (3) | −0.003 (3) | −0.009 (3) |
C2 | 0.024 (3) | 0.042 (4) | 0.024 (3) | 0.000 (3) | 0.002 (3) | 0.003 (3) |
C3 | 0.030 (4) | 0.035 (4) | 0.046 (4) | 0.000 (3) | 0.003 (3) | 0.004 (3) |
C4 | 0.036 (4) | 0.042 (4) | 0.058 (5) | −0.003 (3) | 0.000 (4) | 0.017 (4) |
C5 | 0.029 (4) | 0.053 (4) | 0.045 (5) | 0.002 (3) | 0.008 (3) | 0.012 (4) |
C6 | 0.038 (4) | 0.047 (4) | 0.068 (6) | 0.023 (3) | 0.019 (4) | 0.021 (4) |
C7 | 0.036 (4) | 0.037 (4) | 0.048 (5) | 0.007 (3) | 0.013 (3) | 0.017 (3) |
C8 | 0.039 (5) | 0.160 (10) | 0.057 (6) | 0.028 (5) | 0.012 (4) | 0.051 (6) |
C9 | 0.028 (4) | 0.076 (6) | 0.062 (5) | 0.008 (4) | 0.014 (4) | 0.026 (4) |
C10 | 0.031 (4) | 0.082 (6) | 0.065 (6) | 0.014 (4) | 0.006 (4) | 0.031 (5) |
C11 | 0.074 (7) | 0.134 (10) | 0.105 (9) | 0.021 (7) | 0.007 (6) | 0.016 (7) |
C12 | 0.037 (5) | 0.161 (10) | 0.083 (7) | 0.023 (5) | 0.021 (5) | 0.069 (7) |
C13 | 0.031 (4) | 0.085 (6) | 0.066 (6) | 0.013 (4) | 0.011 (4) | 0.030 (5) |
C14 | 0.042 (5) | 0.079 (6) | 0.064 (6) | 0.011 (4) | 0.013 (4) | 0.043 (5) |
C15 | 0.031 (4) | 0.084 (6) | 0.060 (6) | 0.003 (4) | 0.008 (4) | 0.018 (5) |
C16 | 0.056 (5) | 0.039 (4) | 0.021 (4) | −0.001 (3) | −0.004 (3) | −0.005 (3) |
C17 | 0.059 (5) | 0.055 (5) | 0.017 (3) | 0.002 (4) | −0.003 (3) | −0.002 (3) |
C18 | 0.055 (5) | 0.102 (7) | 0.025 (4) | 0.011 (5) | −0.008 (4) | −0.007 (4) |
C19 | 0.046 (5) | 0.132 (8) | 0.027 (4) | 0.014 (5) | 0.002 (4) | −0.006 (5) |
C20 | 0.068 (5) | 0.069 (5) | 0.022 (4) | −0.002 (4) | −0.006 (4) | −0.007 (4) |
C21 | 0.060 (5) | 0.115 (8) | 0.030 (5) | −0.029 (5) | −0.007 (4) | 0.002 (4) |
C22 | 0.050 (5) | 0.104 (7) | 0.032 (4) | −0.012 (4) | 0.001 (4) | −0.011 (4) |
C23 | 0.049 (5) | 0.076 (6) | 0.030 (4) | −0.011 (4) | −0.003 (3) | 0.004 (4) |
C24 | 0.078 (6) | 0.055 (5) | 0.025 (4) | 0.005 (4) | −0.006 (4) | −0.014 (4) |
C25 | 0.061 (5) | 0.047 (4) | 0.034 (4) | 0.001 (4) | −0.001 (4) | −0.008 (3) |
C26 | 0.037 (4) | 0.049 (4) | 0.016 (3) | 0.002 (3) | −0.004 (3) | −0.007 (3) |
C27 | 0.077 (5) | 0.046 (4) | 0.029 (4) | −0.008 (4) | −0.010 (4) | −0.001 (3) |
C28 | 0.092 (6) | 0.050 (4) | 0.030 (4) | −0.009 (4) | −0.004 (4) | 0.006 (3) |
C29 | 0.025 (3) | 0.054 (4) | 0.023 (4) | 0.003 (3) | −0.001 (3) | −0.001 (3) |
C30 | 0.143 (15) | 0.061 (7) | 0.054 (10) | −0.021 (7) | −0.003 (9) | 0.014 (6) |
C30B | 0.091 (10) | 0.19 (2) | 0.102 (17) | −0.037 (10) | −0.035 (10) | 0.026 (15) |
C31 | 0.032 (4) | 0.034 (4) | 0.034 (4) | −0.002 (3) | −0.006 (3) | −0.007 (3) |
C32 | 0.037 (4) | 0.027 (3) | 0.036 (4) | 0.000 (3) | 0.009 (3) | −0.009 (3) |
C33 | 0.091 (6) | 0.034 (4) | 0.055 (5) | −0.008 (4) | 0.032 (5) | −0.001 (4) |
C34 | 0.094 (7) | 0.046 (5) | 0.053 (5) | −0.007 (4) | 0.025 (5) | −0.015 (4) |
C35 | 0.056 (5) | 0.032 (4) | 0.053 (5) | −0.001 (3) | 0.010 (4) | −0.007 (4) |
C36 | 0.042 (4) | 0.030 (4) | 0.045 (4) | −0.007 (3) | 0.000 (3) | 0.004 (3) |
C37 | 0.045 (4) | 0.038 (4) | 0.034 (4) | 0.000 (3) | 0.001 (3) | −0.007 (3) |
C38 | 0.054 (5) | 0.034 (4) | 0.049 (5) | −0.001 (3) | 0.004 (4) | −0.013 (3) |
C39 | 0.080 (6) | 0.046 (5) | 0.094 (7) | −0.026 (4) | 0.032 (5) | −0.031 (5) |
C40 | 0.078 (6) | 0.034 (4) | 0.057 (5) | −0.018 (4) | 0.019 (4) | −0.016 (4) |
C41 | 0.085 (6) | 0.038 (5) | 0.111 (8) | −0.022 (4) | 0.054 (6) | −0.034 (5) |
C42 | 0.068 (5) | 0.037 (4) | 0.072 (6) | −0.013 (4) | 0.030 (5) | −0.015 (4) |
C43 | 0.060 (5) | 0.040 (4) | 0.069 (6) | −0.002 (4) | 0.017 (4) | −0.013 (4) |
C44 | 0.075 (6) | 0.042 (5) | 0.066 (6) | −0.009 (4) | 0.035 (5) | −0.014 (4) |
C45 | 0.101 (8) | 0.078 (7) | 0.130 (11) | 0.007 (6) | −0.012 (7) | −0.013 (7) |
Geometric parameters (Å, º) top
Zn1—O2 | 1.948 (4) | C11—H11A | 0.9600 |
Zn1—O6i | 1.964 (4) | C11—H11B | 0.9600 |
Zn1—O11ii | 1.963 (4) | C11—H11C | 0.9600 |
Zn1—O13 | 1.944 (4) | C12—H12 | 0.9300 |
Zn2—O3iii | 1.945 (5) | C12—C13 | 1.387 (11) |
Zn2—O5i | 1.971 (5) | C13—C14 | 1.384 (10) |
Zn2—O10 | 1.926 (4) | C13—C15 | 1.503 (9) |
Zn2—O13 | 1.973 (4) | C14—H14 | 0.9300 |
Zn3—O4iii | 1.996 (5) | C16—C17 | 1.486 (9) |
Zn3—O8iv | 2.030 (4) | C17—C18 | 1.380 (10) |
Zn3—O12ii | 2.090 (11) | C17—C22 | 1.375 (10) |
Zn3—O12Aii | 1.937 (13) | C18—H18 | 0.9300 |
Zn3—O13 | 2.063 (4) | C18—C19 | 1.382 (10) |
Zn3—O14 | 2.049 (6) | C19—H19 | 0.9300 |
Zn3—O15 | 2.439 (11) | C19—C20 | 1.380 (10) |
Ca1—O1iv | 2.274 (4) | C20—C21 | 1.393 (10) |
Ca1—O1 | 2.274 (4) | C20—C23 | 1.503 (10) |
Ca1—O7iv | 2.300 (4) | C21—H21 | 0.9300 |
Ca1—O7 | 2.300 (4) | C21—C22 | 1.381 (10) |
Ca1—O9 | 2.289 (4) | C21—C30B | 1.552 (15) |
Ca1—O9iv | 2.289 (4) | C22—H22 | 0.9300 |
O1—C1 | 1.238 (7) | C23—C24 | 1.395 (10) |
O2—C1 | 1.284 (7) | C23—C28 | 1.360 (10) |
O3—Zn2v | 1.944 (5) | C24—H24 | 0.9300 |
O3—C15 | 1.263 (9) | C24—C25 | 1.366 (9) |
O4—Zn3v | 1.995 (5) | C25—H25 | 0.9300 |
O4—C15 | 1.249 (9) | C25—C26 | 1.369 (9) |
O5—Zn2i | 1.971 (5) | C26—C27 | 1.385 (9) |
O5—C16 | 1.265 (8) | C26—C29 | 1.498 (8) |
O6—Zn1i | 1.964 (4) | C27—H27 | 0.9300 |
O6—C16 | 1.254 (8) | C27—C28 | 1.378 (10) |
O7—C29 | 1.268 (7) | C28—H28 | 0.9599 |
O8—Zn3iv | 2.030 (4) | C28—C30 | 1.542 (13) |
O8—C29 | 1.263 (7) | C30—H30A | 0.9600 |
O9—C31 | 1.228 (7) | C30—H30B | 0.9600 |
O10—C31 | 1.277 (7) | C30—H30C | 0.9600 |
O11—Zn1vi | 1.963 (4) | C30B—H30D | 0.9600 |
O11—C44 | 1.203 (8) | C30B—H30E | 0.9600 |
O12—Zn3vi | 2.090 (11) | C30B—H30F | 0.9600 |
O12—C44 | 1.312 (14) | C31—C32 | 1.496 (8) |
O12A—Zn3vi | 1.937 (13) | C32—C33 | 1.391 (9) |
O12A—C44 | 1.35 (2) | C32—C37 | 1.377 (9) |
O13—H13 | 0.815 (10) | C33—H33 | 0.9300 |
O14—H14A | 0.825 (10) | C33—C34 | 1.370 (9) |
O14—H14B | 0.825 (10) | C34—H34 | 0.9300 |
O15—H15A | 0.8579 | C34—C35 | 1.396 (10) |
O15—H15B | 0.8875 | C35—C36 | 1.370 (9) |
C1—C2 | 1.492 (8) | C35—C38 | 1.501 (9) |
C2—C3 | 1.376 (8) | C36—C37 | 1.379 (8) |
C2—C7 | 1.377 (8) | C36—C45 | 1.527 (12) |
C3—H3 | 0.9300 | C37—H37 | 0.9300 |
C3—C4 | 1.400 (9) | C38—C39 | 1.366 (10) |
C4—H4 | 0.9300 | C38—C43 | 1.390 (9) |
C4—C5 | 1.383 (9) | C39—H39 | 0.9300 |
C5—C6 | 1.366 (9) | C39—C41 | 1.402 (10) |
C5—C9 | 1.492 (9) | C40—C41 | 1.368 (10) |
C6—H6 | 0.9300 | C40—C42 | 1.361 (10) |
C6—C7 | 1.397 (9) | C40—C44 | 1.512 (9) |
C7—H7 | 0.9300 | C41—H41 | 0.9300 |
C8—H8 | 0.9300 | C42—H42 | 0.9300 |
C8—C9 | 1.357 (10) | C42—C43 | 1.381 (9) |
C8—C12 | 1.388 (10) | C43—H43 | 0.9300 |
C9—C10 | 1.394 (10) | C45—H45A | 0.9600 |
C10—C11 | 1.536 (12) | C45—H45B | 0.9600 |
C10—C14 | 1.391 (9) | C45—H45C | 0.9600 |
| | | |
O2—Zn1—O6i | 113.3 (2) | C10—C14—H14 | 119.7 |
O2—Zn1—O11ii | 99.44 (19) | C13—C14—C10 | 120.6 (7) |
O11ii—Zn1—O6i | 99.1 (2) | C13—C14—H14 | 119.7 |
O13—Zn1—O2 | 124.24 (17) | O3—C15—C13 | 116.9 (7) |
O13—Zn1—O6i | 105.02 (18) | O4—C15—O3 | 125.6 (7) |
O13—Zn1—O11ii | 112.99 (18) | O4—C15—C13 | 117.5 (7) |
O3iii—Zn2—O5i | 108.1 (2) | O5—C16—C17 | 117.1 (6) |
O3iii—Zn2—O13 | 112.01 (19) | O6—C16—O5 | 124.1 (6) |
O5i—Zn2—O13 | 101.57 (18) | O6—C16—C17 | 118.8 (6) |
O10—Zn2—O3iii | 107.9 (2) | C18—C17—C16 | 121.4 (7) |
O10—Zn2—O5i | 102.2 (2) | C22—C17—C16 | 120.1 (7) |
O10—Zn2—O13 | 123.53 (17) | C22—C17—C18 | 118.5 (7) |
O4iii—Zn3—O8iv | 98.1 (2) | C17—C18—H18 | 119.5 |
O4iii—Zn3—O12ii | 155.9 (6) | C17—C18—C19 | 121.1 (7) |
O4iii—Zn3—O13 | 95.91 (19) | C19—C18—H18 | 119.5 |
O4iii—Zn3—O14 | 88.3 (2) | C18—C19—H19 | 119.8 |
O4iii—Zn3—O15 | 81.0 (3) | C20—C19—C18 | 120.4 (8) |
O8iv—Zn3—O12ii | 103.5 (6) | C20—C19—H19 | 119.8 |
O8iv—Zn3—O13 | 95.77 (16) | C19—C20—C21 | 118.5 (7) |
O8iv—Zn3—O14 | 91.6 (2) | C19—C20—C23 | 121.1 (7) |
O8iv—Zn3—O15 | 178.2 (3) | C21—C20—C23 | 120.4 (7) |
O12ii—Zn3—O15 | 77.0 (6) | C20—C21—H21 | 119.8 |
O12Aii—Zn3—O4iii | 127.6 (13) | C20—C21—C30B | 125.0 (13) |
O12Aii—Zn3—O8iv | 133.1 (14) | C22—C21—C20 | 120.4 (7) |
O12Aii—Zn3—O13 | 89.9 (5) | C22—C21—H21 | 119.8 |
O12Aii—Zn3—O14 | 81.2 (5) | C22—C21—C30B | 114.6 (13) |
O12Aii—Zn3—O15 | 47.5 (14) | C17—C22—C21 | 121.0 (7) |
O13—Zn3—O12ii | 92.3 (3) | C17—C22—H22 | 119.5 |
O13—Zn3—O15 | 85.9 (3) | C21—C22—H22 | 119.5 |
O14—Zn3—O12ii | 80.7 (4) | C24—C23—C20 | 118.9 (7) |
O14—Zn3—O13 | 170.9 (2) | C28—C23—C20 | 122.1 (7) |
O14—Zn3—O15 | 86.9 (3) | C28—C23—C24 | 118.9 (7) |
O1iv—Ca1—O1 | 180.00 (16) | C23—C24—H24 | 120.0 |
O1iv—Ca1—O7iv | 94.50 (15) | C25—C24—C23 | 120.0 (7) |
O1—Ca1—O7 | 94.50 (15) | C25—C24—H24 | 120.0 |
O1—Ca1—O7iv | 85.50 (15) | C24—C25—H25 | 119.5 |
O1iv—Ca1—O7 | 85.50 (15) | C24—C25—C26 | 121.1 (7) |
O1—Ca1—O9iv | 91.55 (15) | C26—C25—H25 | 119.5 |
O1—Ca1—O9 | 88.44 (15) | C25—C26—C27 | 118.8 (6) |
O1iv—Ca1—O9 | 91.56 (15) | C25—C26—C29 | 121.6 (6) |
O1iv—Ca1—O9iv | 88.44 (15) | C27—C26—C29 | 119.5 (6) |
O7iv—Ca1—O7 | 180.0 (2) | C26—C27—H27 | 119.9 |
O9—Ca1—O7 | 95.64 (15) | C28—C27—C26 | 120.2 (7) |
O9iv—Ca1—O7 | 84.36 (15) | C28—C27—H27 | 119.9 |
O9—Ca1—O7iv | 84.36 (15) | C23—C28—C27 | 120.9 (7) |
O9iv—Ca1—O7iv | 95.64 (15) | C23—C28—H28 | 119.5 |
O9iv—Ca1—O9 | 180.0 | C23—C28—C30 | 121.1 (8) |
C1—O1—Ca1 | 153.1 (4) | C27—C28—H28 | 119.6 |
C1—O2—Zn1 | 115.9 (4) | C27—C28—C30 | 116.8 (8) |
C15—O3—Zn2v | 124.1 (5) | O7—C29—C26 | 118.8 (6) |
C15—O4—Zn3v | 136.9 (5) | O8—C29—O7 | 123.2 (6) |
C16—O5—Zn2i | 123.1 (4) | O8—C29—C26 | 118.1 (6) |
C16—O6—Zn1i | 124.2 (4) | C28—C30—H30A | 109.5 |
C29—O7—Ca1 | 148.8 (4) | C28—C30—H30B | 109.5 |
C29—O8—Zn3iv | 126.7 (4) | C28—C30—H30C | 109.5 |
C31—O9—Ca1 | 164.4 (4) | H30A—C30—H30B | 109.5 |
C31—O10—Zn2 | 120.2 (4) | H30A—C30—H30C | 109.5 |
C44—O11—Zn1vi | 120.8 (5) | H30B—C30—H30C | 109.5 |
C44—O12—Zn3vi | 129.6 (11) | C21—C30B—H30D | 109.5 |
C44—O12A—Zn3vi | 140 (2) | C21—C30B—H30E | 109.5 |
Zn1—O13—Zn2 | 110.90 (19) | C21—C30B—H30F | 109.5 |
Zn1—O13—Zn3 | 114.02 (18) | H30D—C30B—H30E | 109.5 |
Zn1—O13—H13 | 116 (4) | H30D—C30B—H30F | 109.5 |
Zn2—O13—Zn3 | 111.18 (18) | H30E—C30B—H30F | 109.5 |
Zn2—O13—H13 | 114 (4) | O9—C31—O10 | 122.8 (6) |
Zn3—O13—H13 | 88 (4) | O9—C31—C32 | 121.0 (6) |
Zn3—O14—H14A | 104 (5) | O10—C31—C32 | 116.2 (6) |
Zn3—O14—H14B | 104 (5) | C33—C32—C31 | 121.7 (6) |
H14A—O14—H14B | 114 (2) | C37—C32—C31 | 121.0 (6) |
Zn3—O15—H15A | 115.3 | C37—C32—C33 | 117.3 (6) |
Zn3—O15—H15B | 117.0 | C32—C33—H33 | 119.3 |
H15A—O15—H15B | 94.5 | C34—C33—C32 | 121.4 (7) |
O1—C1—O2 | 120.8 (5) | C34—C33—H33 | 119.3 |
O1—C1—C2 | 121.4 (6) | C33—C34—H34 | 120.0 |
O2—C1—C2 | 117.8 (5) | C33—C34—C35 | 120.0 (7) |
C3—C2—C1 | 119.6 (5) | C35—C34—H34 | 120.0 |
C3—C2—C7 | 120.3 (6) | C34—C35—C38 | 115.6 (7) |
C7—C2—C1 | 120.0 (6) | C36—C35—C34 | 119.2 (6) |
C2—C3—H3 | 119.8 | C36—C35—C38 | 125.2 (7) |
C2—C3—C4 | 120.4 (6) | C35—C36—C37 | 119.8 (6) |
C4—C3—H3 | 119.8 | C35—C36—C45 | 123.8 (7) |
C3—C4—H4 | 120.1 | C37—C36—C45 | 116.4 (7) |
C5—C4—C3 | 119.8 (6) | C32—C37—C36 | 122.2 (6) |
C5—C4—H4 | 120.1 | C32—C37—H37 | 118.9 |
C4—C5—C9 | 122.6 (6) | C36—C37—H37 | 118.9 |
C6—C5—C4 | 118.6 (6) | C39—C38—C35 | 119.6 (7) |
C6—C5—C9 | 118.7 (6) | C39—C38—C43 | 117.5 (6) |
C5—C6—H6 | 118.8 | C43—C38—C35 | 122.9 (6) |
C5—C6—C7 | 122.5 (6) | C38—C39—H39 | 119.3 |
C7—C6—H6 | 118.8 | C38—C39—C41 | 121.3 (7) |
C2—C7—C6 | 118.3 (6) | C41—C39—H39 | 119.3 |
C2—C7—H7 | 120.8 | C41—C40—C44 | 119.6 (7) |
C6—C7—H7 | 120.8 | C42—C40—C41 | 118.7 (7) |
C9—C8—H8 | 119.0 | C42—C40—C44 | 121.6 (7) |
C9—C8—C12 | 122.1 (8) | C39—C41—H41 | 119.9 |
C12—C8—H8 | 119.0 | C40—C41—C39 | 120.3 (7) |
C8—C9—C5 | 117.4 (7) | C40—C41—H41 | 119.9 |
C8—C9—C10 | 118.8 (7) | C40—C42—H42 | 119.4 |
C10—C9—C5 | 123.8 (7) | C40—C42—C43 | 121.2 (7) |
C9—C10—C11 | 123.4 (7) | C43—C42—H42 | 119.4 |
C14—C10—C9 | 119.9 (7) | C38—C43—H43 | 119.6 |
C14—C10—C11 | 116.5 (8) | C42—C43—C38 | 120.9 (7) |
C10—C11—H11A | 109.5 | C42—C43—H43 | 119.6 |
C10—C11—H11B | 109.5 | O11—C44—O12 | 118.8 (9) |
C10—C11—H11C | 109.5 | O11—C44—O12A | 119.9 (11) |
H11A—C11—H11B | 109.5 | O11—C44—C40 | 120.9 (7) |
H11A—C11—H11C | 109.5 | O12—C44—C40 | 116.9 (8) |
H11B—C11—H11C | 109.5 | O12A—C44—C40 | 112.2 (8) |
C8—C12—H12 | 120.3 | C36—C45—H45A | 109.5 |
C13—C12—C8 | 119.4 (8) | C36—C45—H45B | 109.5 |
C13—C12—H12 | 120.3 | C36—C45—H45C | 109.5 |
C12—C13—C15 | 119.3 (7) | H45A—C45—H45B | 109.5 |
C14—C13—C12 | 119.1 (7) | H45A—C45—H45C | 109.5 |
C14—C13—C15 | 121.5 (7) | H45B—C45—H45C | 109.5 |
| | | |
Zn1—O2—C1—O1 | 2.4 (8) | C15—C13—C14—C10 | 177.1 (8) |
Zn1—O2—C1—C2 | −177.5 (4) | C16—C17—C18—C19 | −175.9 (8) |
Zn1i—O6—C16—O5 | 31.8 (9) | C16—C17—C22—C21 | 178.1 (8) |
Zn1i—O6—C16—C17 | −145.6 (5) | C17—C18—C19—C20 | −2.4 (14) |
Zn1vi—O11—C44—O12 | −25.5 (14) | C18—C17—C22—C21 | 0.1 (13) |
Zn1vi—O11—C44—O12A | 28 (2) | C18—C19—C20—C21 | 0.6 (14) |
Zn1vi—O11—C44—C40 | 176.0 (6) | C18—C19—C20—C23 | 179.3 (8) |
Zn2v—O3—C15—O4 | −13.6 (13) | C19—C20—C21—C22 | 1.5 (14) |
Zn2v—O3—C15—C13 | 164.2 (6) | C19—C20—C21—C30B | 178.1 (17) |
Zn2i—O5—C16—O6 | 26.2 (9) | C19—C20—C23—C24 | −81.6 (10) |
Zn2i—O5—C16—C17 | −156.4 (5) | C19—C20—C23—C28 | 96.7 (10) |
Zn2—O10—C31—O9 | −0.8 (9) | C20—C21—C22—C17 | −1.9 (14) |
Zn2—O10—C31—C32 | 179.6 (4) | C20—C23—C24—C25 | 176.4 (7) |
Zn3v—O4—C15—O3 | −22.0 (15) | C20—C23—C28—C27 | −177.1 (7) |
Zn3v—O4—C15—C13 | 160.2 (6) | C20—C23—C28—C30 | −9.9 (14) |
Zn3iv—O8—C29—O7 | −19.6 (9) | C21—C20—C23—C24 | 97.1 (10) |
Zn3iv—O8—C29—C26 | 159.6 (4) | C21—C20—C23—C28 | −84.6 (11) |
Zn3vi—O12—C44—O11 | 74.2 (19) | C22—C17—C18—C19 | 2.0 (13) |
Zn3vi—O12—C44—C40 | −126.4 (11) | C23—C20—C21—C22 | −177.2 (8) |
Zn3vi—O12A—C44—O11 | −61 (4) | C23—C20—C21—C30B | −1 (2) |
Zn3vi—O12A—C44—C40 | 148 (3) | C23—C24—C25—C26 | 1.5 (12) |
Ca1—O1—C1—O2 | −136.0 (7) | C24—C23—C28—C27 | 1.2 (12) |
Ca1—O1—C1—C2 | 43.8 (12) | C24—C23—C28—C30 | 168.4 (10) |
Ca1—O7—C29—O8 | −139.1 (6) | C24—C25—C26—C27 | −0.1 (11) |
Ca1—O7—C29—C26 | 41.7 (11) | C24—C25—C26—C29 | −176.9 (7) |
Ca1—O9—C31—O10 | −149.6 (13) | C25—C26—C27—C28 | −0.7 (11) |
Ca1—O9—C31—C32 | 30 (2) | C25—C26—C29—O7 | −163.9 (6) |
O1—C1—C2—C3 | 14.2 (9) | C25—C26—C29—O8 | 16.8 (9) |
O1—C1—C2—C7 | −162.8 (6) | C26—C27—C28—C23 | 0.1 (12) |
O2—C1—C2—C3 | −166.0 (6) | C26—C27—C28—C30 | −167.6 (9) |
O2—C1—C2—C7 | 17.0 (9) | C27—C26—C29—O7 | 19.3 (9) |
O5—C16—C17—C18 | −8.6 (10) | C27—C26—C29—O8 | −160.0 (6) |
O5—C16—C17—C22 | 173.5 (7) | C28—C23—C24—C25 | −2.0 (12) |
O6—C16—C17—C18 | 169.0 (7) | C29—C26—C27—C28 | 176.2 (7) |
O6—C16—C17—C22 | −8.9 (11) | C30B—C21—C22—C17 | −178.8 (15) |
O9—C31—C32—C33 | −156.2 (7) | C31—C32—C33—C34 | 177.7 (7) |
O9—C31—C32—C37 | 21.4 (10) | C31—C32—C37—C36 | −178.6 (6) |
O10—C31—C32—C33 | 23.4 (10) | C32—C33—C34—C35 | 0.3 (13) |
O10—C31—C32—C37 | −159.0 (6) | C33—C32—C37—C36 | −0.9 (10) |
C1—C2—C3—C4 | −177.8 (6) | C33—C34—C35—C36 | 0.3 (12) |
C1—C2—C7—C6 | 176.3 (6) | C33—C34—C35—C38 | −179.0 (7) |
C2—C3—C4—C5 | 1.2 (11) | C34—C35—C36—C37 | −1.2 (11) |
C3—C2—C7—C6 | −0.7 (10) | C34—C35—C36—C45 | 179.6 (8) |
C3—C4—C5—C6 | −0.1 (11) | C34—C35—C38—C39 | −45.1 (11) |
C3—C4—C5—C9 | −178.3 (7) | C34—C35—C38—C43 | 132.3 (8) |
C4—C5—C6—C7 | −1.4 (12) | C35—C36—C37—C32 | 1.5 (10) |
C4—C5—C9—C8 | 125.0 (9) | C35—C38—C39—C41 | 175.8 (9) |
C4—C5—C9—C10 | −55.0 (12) | C35—C38—C43—C42 | −177.8 (8) |
C5—C6—C7—C2 | 1.8 (12) | C36—C35—C38—C39 | 135.7 (9) |
C5—C9—C10—C11 | −6.0 (14) | C36—C35—C38—C43 | −46.9 (12) |
C5—C9—C10—C14 | 179.3 (8) | C37—C32—C33—C34 | 0.0 (12) |
C6—C5—C9—C8 | −53.2 (12) | C38—C35—C36—C37 | 178.0 (7) |
C6—C5—C9—C10 | 126.8 (9) | C38—C35—C36—C45 | −1.2 (12) |
C7—C2—C3—C4 | −0.8 (10) | C38—C39—C41—C40 | 0.5 (16) |
C8—C9—C10—C11 | 174.0 (9) | C39—C38—C43—C42 | −0.3 (13) |
C8—C9—C10—C14 | −0.7 (14) | C40—C42—C43—C38 | 3.8 (14) |
C8—C12—C13—C14 | −2.8 (16) | C41—C40—C42—C43 | −5.1 (14) |
C8—C12—C13—C15 | 179.7 (9) | C41—C40—C44—O11 | −159.7 (9) |
C9—C5—C6—C7 | 176.8 (7) | C41—C40—C44—O12 | 41.4 (16) |
C9—C8—C12—C13 | 4.3 (18) | C41—C40—C44—O12A | −9 (2) |
C9—C10—C14—C13 | 2.1 (14) | C42—C40—C41—C39 | 2.9 (15) |
C11—C10—C14—C13 | −172.9 (8) | C42—C40—C44—O11 | 20.7 (14) |
C12—C8—C9—C5 | 177.4 (9) | C42—C40—C44—O12 | −138.2 (13) |
C12—C8—C9—C10 | −2.6 (16) | C42—C40—C44—O12A | 171 (2) |
C12—C13—C14—C10 | −0.3 (14) | C43—C38—C39—C41 | −1.8 (14) |
C12—C13—C15—O3 | −160.9 (9) | C44—C40—C41—C39 | −176.7 (9) |
C12—C13—C15—O4 | 17.1 (14) | C44—C40—C42—C43 | 174.6 (8) |
C14—C13—C15—O3 | 21.7 (13) | C45—C36—C37—C32 | −179.2 (7) |
C14—C13—C15—O4 | −160.4 (9) | | |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+3/2; (ii) x, y−1/2, −z+1; (iii) x−1/2, y, −z+1/2; (iv) −x+1/2, −y+1/2, −z+1/2; (v) x+1/2, y, −z+1/2; (vi) x, y+1/2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O13—H13···O7iv | 0.82 (1) | 1.89 (1) | 2.701 (6) | 175 (6) |
O13—H13···O8iv | 0.82 (1) | 2.57 (5) | 3.036 (6) | 118 (5) |
O14—H14A···O11vii | 0.83 (1) | 2.40 (5) | 2.971 (7) | 127 (6) |
O14—H14B···O2viii | 0.83 (1) | 2.05 (5) | 2.685 (7) | 134 (6) |
O15—H15A···O5i | 0.86 | 2.36 | 3.075 (12) | 141 |
O15—H15B···O3iii | 0.89 | 2.57 | 3.092 (12) | 118 |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+3/2; (iii) x−1/2, y, −z+1/2; (iv) −x+1/2, −y+1/2, −z+1/2; (vii) −y+3/4, x−1/4, −z+3/4; (viii) −y+1/4, x−1/4, z−1/4. |