Thermally activated delayed fluorescent (TADF) coordination polymer with the generation of singlet oxygen

4,4′-{9,9′-Spirobi[10H-acridine]-10,10′-di­yl}di­benzoic acid (L, C₂₉H₂₆N₂O₄) was designed and synthesized as a new donor–acceptor motif mol­ecule. Due to the large dihedral angle between the planes of the carb­oxy­phenyl group and the spiro­acridine moiety, L possess thermally activated delayed fluorescence (TADF). By applying L as a ligand and using Cd as a metal connector, we synthesized the coordination polymer catena-poly[hemi-μ-aqua-aqua­(μ₃-4,4′-{9,9′-spirobi[10H-acridine]-10,10′-di­yl}dibenzoato)cadmium(II)], [Cd(C₂₉H₂₄N₂O₄)(H₂O)_1.5]_n, (I). X-ray crystallographic analysis revealed that this coordination polymer exhibits one-dimensional chains constructed from mol­ecular twist-ring moieties, with Cd₂O₁₁ clusters as the connection nodes. The stacking pattern of the two-dimensional network was formed by C—H...π inter­actions in the solid state. Similar to L, (I) presents a sky-blue TADF emission, together with a photoluminescence quantum yield (PLQY) of 40%. It is worth noting that the photocatalytic activity toward the generation of singlet oxygen of this coordination polymer is confirmed.

Computing details

For both structures, data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: olex2.solve (Bourhis et al., 2015); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

4,4'-{9,9'-Spirobi[10H-acridine]-10,10'-diyl}dibenzoic acid (L)

Crystal data

C39H26N2O4	Z = 2
Mr = 586.62	F(000) = 612
Triclinic, P1	Dx = 1.009 Mg m^−3
a = 12.6717 (10) Å	Cu Kα radiation, λ = 1.54184 Å
b = 13.0727 (9) Å	Cell parameters from 3153 reflections
c = 13.9254 (11) Å	θ = 7.0–70.6°
α = 65.029 (7)°	µ = 0.53 mm^−1
β = 75.294 (7)°	T = 294 K
γ = 68.420 (7)°	Block, clear light colourless
V = 1931.2 (3) Å^3	0.27 × 0.13 × 0.09 mm

Data collection

Rigaku SuperNova Dual Source diffractometer with an Eos detector	7278 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	4599 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.023
Detector resolution: 16.0793 pixels mm^-1	θmax = 70.9°, θmin = 3.5°
ω scans	h = −15→14
Absorption correction: multi-scan (CrysAlis PRO (Rigaku OD, 2015)	k = −16→8
Tmin = 0.848, Tmax = 1.000	l = −16→14
13193 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.057	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.200	w = 1/[σ^2(Fo^2) + (0.0968P)^2 + 0.174P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max = 0.001
7278 reflections	Δρmax = 0.21 e Å^−3
409 parameters	Δρmin = −0.19 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: iterative	Extinction coefficient: 0.0008 (3)

Special details

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.

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 (Ų)

	x	y	z	Uiso*/Ueq
C22	0.53570 (17)	0.67838 (18)	0.48653 (15)	0.0406 (4)
N1	0.65184 (15)	0.62169 (18)	0.49259 (14)	0.0519 (5)
C27	0.46400 (17)	0.70674 (17)	0.57183 (15)	0.0383 (4)
C1	0.50747 (17)	0.67556 (17)	0.67685 (15)	0.0387 (4)
N2	0.33683 (17)	0.72755 (17)	0.85048 (15)	0.0564 (5)
C9	0.37209 (19)	0.61385 (19)	0.84749 (16)	0.0465 (5)
O3	0.94039 (18)	0.41989 (18)	0.12965 (16)	0.0796 (6)
H3	0.9798	0.4149	0.0742	0.119*
C15	0.63745 (18)	0.62050 (18)	0.67021 (16)	0.0432 (5)
C20	0.70306 (17)	0.59262 (18)	0.58282 (16)	0.0446 (5)
C7	0.39304 (19)	0.81187 (19)	0.78121 (16)	0.0477 (5)
C23	0.48805 (19)	0.7091 (2)	0.39345 (17)	0.0497 (5)
H23	0.5351	0.6909	0.3360	0.060*
C26	0.34906 (18)	0.76437 (19)	0.56126 (16)	0.0459 (5)
H26	0.3014	0.7838	0.6179	0.055*
C2	0.47551 (18)	0.78941 (18)	0.69887 (15)	0.0413 (4)
O4	0.95665 (18)	0.60151 (19)	0.05478 (16)	0.0843 (6)
C25	0.3024 (2)	0.7942 (2)	0.47000 (18)	0.0535 (6)
H25	0.2249	0.8329	0.4652	0.064*
C14	0.45200 (18)	0.58593 (18)	0.76623 (15)	0.0418 (5)
C13	0.4815 (2)	0.47302 (19)	0.76557 (17)	0.0494 (5)
H13	0.5339	0.4544	0.7107	0.059*
C28	0.72263 (18)	0.5949 (2)	0.40229 (17)	0.0493 (5)
C19	0.8203 (2)	0.5349 (2)	0.5862 (2)	0.0615 (6)
H19	0.8642	0.5150	0.5286	0.074*
C24	0.3736 (2)	0.7652 (2)	0.38586 (18)	0.0527 (5)
H24	0.3438	0.7839	0.3240	0.063*
C3	0.5279 (2)	0.8758 (2)	0.63173 (18)	0.0532 (5)
H3A	0.5817	0.8621	0.5756	0.064*
C31	0.85364 (18)	0.5457 (2)	0.22652 (17)	0.0515 (5)
C10	0.3252 (2)	0.5263 (2)	0.92660 (18)	0.0584 (6)
H10	0.2716	0.5444	0.9811	0.070*
C32	0.7999 (2)	0.4666 (2)	0.30380 (19)	0.0581 (6)
H32	0.8080	0.3961	0.2971	0.070*
C30	0.8421 (2)	0.6502 (2)	0.23725 (18)	0.0549 (6)
H30	0.8778	0.7041	0.1849	0.066*
C11	0.3568 (2)	0.4155 (2)	0.92503 (19)	0.0626 (6)
H11	0.3255	0.3586	0.9785	0.075*
C12	0.4357 (2)	0.3875 (2)	0.84348 (19)	0.0575 (6)
H12	0.4573	0.3122	0.8415	0.069*
C6	0.3661 (2)	0.9199 (2)	0.7938 (2)	0.0638 (7)
H6	0.3100	0.9364	0.8475	0.077*
C29	0.7778 (2)	0.6742 (2)	0.32570 (18)	0.0542 (6)
H29	0.7715	0.7433	0.3338	0.065*
C4	0.5026 (2)	0.9808 (2)	0.6457 (2)	0.0636 (7)
H4	0.5395	1.0368	0.6004	0.076*
C16	0.6916 (2)	0.5923 (2)	0.75704 (18)	0.0572 (6)
H16	0.6483	0.6112	0.8154	0.069*
C34	0.92137 (19)	0.5231 (2)	0.13005 (19)	0.0559 (6)
C37	0.2650 (2)	0.7485 (2)	0.94296 (18)	0.0552 (6)
C40	0.1335 (2)	0.7950 (2)	1.11868 (19)	0.0604 (6)
O1	−0.0419 (2)	0.8608 (3)	1.21770 (19)	0.1048 (8)
O2	0.1199 (2)	0.8055 (3)	1.28629 (18)	0.1035 (8)
H2	0.0760	0.8200	1.3365	0.155*
C38	0.1499 (2)	0.8020 (3)	0.9411 (2)	0.0690 (7)
H38	0.1160	0.8221	0.8811	0.083*
C42	0.3145 (2)	0.7142 (3)	1.0333 (2)	0.0693 (7)
H42	0.3922	0.6750	1.0351	0.083*
C33	0.7338 (2)	0.4919 (2)	0.3915 (2)	0.0604 (6)
H33	0.6970	0.4388	0.4431	0.073*
C5	0.4219 (3)	1.0013 (2)	0.7276 (2)	0.0685 (7)
H5	0.4048	1.0716	0.7383	0.082*
C39	0.0842 (2)	0.8258 (3)	1.0301 (2)	0.0718 (7)
H39	0.0060	0.8630	1.0292	0.086*
C17	0.8071 (2)	0.5374 (3)	0.7595 (2)	0.0723 (8)
H17	0.8417	0.5207	0.8181	0.087*
C41	0.2486 (2)	0.7381 (3)	1.1212 (2)	0.0712 (8)
H41	0.2821	0.7157	1.1820	0.085*
C18	0.8712 (2)	0.5073 (3)	0.6737 (2)	0.0729 (8)
H18	0.9490	0.4682	0.6752	0.087*
C43	0.0611 (3)	0.8235 (3)	1.2125 (2)	0.0708 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C22	0.0393 (11)	0.0459 (11)	0.0368 (10)	−0.0105 (9)	−0.0003 (8)	−0.0197 (9)
N1	0.0432 (10)	0.0695 (12)	0.0438 (10)	−0.0056 (9)	−0.0009 (8)	−0.0333 (9)
C27	0.0435 (11)	0.0391 (10)	0.0333 (9)	−0.0133 (9)	0.0006 (8)	−0.0162 (8)
C1	0.0412 (11)	0.0439 (11)	0.0319 (9)	−0.0131 (9)	0.0021 (8)	−0.0179 (8)
N2	0.0663 (13)	0.0571 (12)	0.0463 (10)	−0.0238 (10)	0.0177 (9)	−0.0284 (9)
C9	0.0507 (12)	0.0519 (13)	0.0370 (10)	−0.0163 (10)	0.0024 (9)	−0.0198 (9)
O3	0.0809 (14)	0.0932 (14)	0.0723 (13)	−0.0251 (11)	0.0247 (10)	−0.0569 (11)
C15	0.0455 (11)	0.0464 (11)	0.0385 (10)	−0.0137 (9)	−0.0023 (8)	−0.0176 (9)
C20	0.0399 (11)	0.0477 (12)	0.0432 (11)	−0.0077 (9)	−0.0031 (9)	−0.0196 (9)
C7	0.0533 (13)	0.0498 (12)	0.0413 (11)	−0.0161 (10)	0.0025 (9)	−0.0217 (9)
C23	0.0541 (13)	0.0592 (14)	0.0391 (11)	−0.0133 (11)	−0.0013 (9)	−0.0263 (10)
C26	0.0430 (11)	0.0512 (12)	0.0421 (11)	−0.0107 (10)	−0.0003 (9)	−0.0213 (9)
C2	0.0471 (11)	0.0443 (11)	0.0359 (10)	−0.0160 (9)	−0.0003 (8)	−0.0185 (8)
O4	0.0943 (15)	0.0992 (15)	0.0657 (12)	−0.0410 (12)	0.0334 (11)	−0.0496 (12)
C25	0.0468 (12)	0.0559 (14)	0.0564 (13)	−0.0082 (10)	−0.0103 (10)	−0.0228 (11)
C14	0.0466 (11)	0.0484 (12)	0.0338 (10)	−0.0191 (9)	−0.0015 (8)	−0.0156 (9)
C13	0.0563 (13)	0.0507 (12)	0.0422 (11)	−0.0153 (10)	−0.0006 (9)	−0.0211 (10)
C28	0.0425 (11)	0.0632 (14)	0.0426 (11)	−0.0089 (10)	0.0042 (9)	−0.0307 (10)
C19	0.0437 (12)	0.0769 (17)	0.0554 (14)	−0.0052 (12)	−0.0025 (10)	−0.0290 (13)
C24	0.0564 (14)	0.0601 (14)	0.0439 (12)	−0.0145 (11)	−0.0132 (10)	−0.0192 (10)
C3	0.0597 (14)	0.0579 (14)	0.0469 (12)	−0.0256 (11)	0.0057 (10)	−0.0234 (10)
C31	0.0403 (11)	0.0700 (15)	0.0475 (12)	−0.0103 (10)	0.0029 (9)	−0.0342 (11)
C10	0.0673 (15)	0.0665 (15)	0.0408 (12)	−0.0301 (13)	0.0118 (10)	−0.0205 (11)
C32	0.0599 (15)	0.0623 (15)	0.0580 (14)	−0.0174 (12)	0.0118 (11)	−0.0386 (12)
C30	0.0527 (13)	0.0643 (15)	0.0487 (12)	−0.0199 (11)	0.0076 (10)	−0.0271 (11)
C11	0.0809 (18)	0.0594 (15)	0.0471 (13)	−0.0351 (13)	−0.0001 (12)	−0.0113 (11)
C12	0.0728 (16)	0.0491 (13)	0.0524 (13)	−0.0222 (12)	−0.0068 (12)	−0.0170 (11)
C6	0.0734 (17)	0.0624 (15)	0.0577 (14)	−0.0188 (13)	0.0101 (12)	−0.0351 (12)
C29	0.0552 (13)	0.0572 (14)	0.0548 (13)	−0.0131 (11)	0.0043 (10)	−0.0340 (11)
C4	0.0776 (18)	0.0572 (15)	0.0621 (15)	−0.0324 (13)	0.0017 (13)	−0.0226 (12)
C16	0.0524 (13)	0.0767 (16)	0.0428 (12)	−0.0199 (12)	−0.0049 (10)	−0.0220 (11)
C34	0.0430 (12)	0.0755 (17)	0.0540 (14)	−0.0114 (12)	0.0037 (10)	−0.0388 (13)
C37	0.0600 (14)	0.0596 (14)	0.0451 (12)	−0.0199 (11)	0.0133 (10)	−0.0273 (11)
C40	0.0633 (16)	0.0671 (16)	0.0524 (14)	−0.0214 (13)	0.0144 (11)	−0.0336 (12)
O1	0.0699 (14)	0.162 (2)	0.1005 (17)	−0.0309 (14)	0.0290 (12)	−0.0896 (17)
O2	0.0859 (15)	0.156 (2)	0.0783 (15)	−0.0162 (15)	0.0114 (12)	−0.0807 (16)
C38	0.0582 (16)	0.092 (2)	0.0551 (15)	−0.0154 (14)	0.0010 (12)	−0.0356 (14)
C42	0.0551 (15)	0.092 (2)	0.0585 (15)	−0.0068 (14)	0.0045 (12)	−0.0447 (15)
C33	0.0639 (15)	0.0640 (15)	0.0558 (14)	−0.0224 (12)	0.0117 (11)	−0.0319 (12)
C5	0.0866 (19)	0.0527 (15)	0.0735 (17)	−0.0216 (14)	−0.0025 (14)	−0.0329 (13)
C39	0.0541 (15)	0.086 (2)	0.0682 (17)	−0.0118 (14)	0.0093 (13)	−0.0385 (15)
C17	0.0613 (16)	0.095 (2)	0.0553 (15)	−0.0190 (15)	−0.0188 (12)	−0.0197 (14)
C41	0.0684 (17)	0.090 (2)	0.0545 (15)	−0.0095 (15)	0.0016 (12)	−0.0429 (14)
C18	0.0443 (14)	0.091 (2)	0.0727 (17)	−0.0075 (13)	−0.0134 (12)	−0.0269 (15)
C43	0.0710 (18)	0.0831 (19)	0.0630 (16)	−0.0261 (15)	0.0185 (13)	−0.0434 (15)

Geometric parameters (Å, º)

C22—N1	1.389 (3)	C3—C4	1.376 (3)
C22—C27	1.396 (3)	C31—C32	1.378 (3)
C22—C23	1.409 (3)	C31—C30	1.387 (3)
N1—C20	1.405 (3)	C31—C34	1.481 (3)
N1—C28	1.441 (2)	C10—H10	0.9300
C27—C1	1.533 (3)	C10—C11	1.361 (3)
C27—C26	1.385 (3)	C32—H32	0.9300
C1—C15	1.532 (3)	C32—C33	1.385 (3)
C1—C2	1.534 (3)	C30—H30	0.9300
C1—C14	1.532 (3)	C30—C29	1.382 (3)
N2—C9	1.402 (3)	C11—H11	0.9300
N2—C7	1.409 (3)	C11—C12	1.389 (3)
N2—C37	1.443 (3)	C12—H12	0.9300
C9—C14	1.391 (3)	C6—H6	0.9300
C9—C10	1.407 (3)	C6—C5	1.369 (4)
O3—H3	0.8200	C29—H29	0.9300
O3—C34	1.282 (3)	C4—H4	0.9300
C15—C20	1.394 (3)	C4—C5	1.373 (4)
C15—C16	1.388 (3)	C16—H16	0.9300
C20—C19	1.400 (3)	C16—C17	1.376 (4)
C7—C2	1.394 (3)	C37—C38	1.368 (3)
C7—C6	1.402 (3)	C37—C42	1.376 (3)
C23—H23	0.9300	C40—C39	1.363 (4)
C23—C24	1.372 (3)	C40—C41	1.374 (4)
C26—H26	0.9300	C40—C43	1.496 (3)
C26—C25	1.382 (3)	O1—C43	1.208 (4)
C2—C3	1.391 (3)	O2—H2	0.8200
O4—C34	1.242 (3)	O2—C43	1.312 (4)
C25—H25	0.9300	C38—H38	0.9300
C25—C24	1.385 (3)	C38—C39	1.393 (3)
C14—C13	1.386 (3)	C42—H42	0.9300
C13—H13	0.9300	C42—C41	1.380 (3)
C13—C12	1.377 (3)	C33—H33	0.9300
C28—C29	1.386 (3)	C5—H5	0.9300
C28—C33	1.370 (3)	C39—H39	0.9300
C19—H19	0.9300	C17—H17	0.9300
C19—C18	1.374 (4)	C17—C18	1.382 (4)
C24—H24	0.9300	C41—H41	0.9300
C3—H3A	0.9300	C18—H18	0.9300
N1—C22—C27	120.94 (17)	C9—C10—H10	119.3
N1—C22—C23	120.41 (17)	C11—C10—C9	121.3 (2)
C27—C22—C23	118.65 (19)	C11—C10—H10	119.3
C22—N1—C20	122.09 (16)	C31—C32—H32	120.0
C22—N1—C28	118.98 (17)	C31—C32—C33	120.0 (2)
C20—N1—C28	118.90 (17)	C33—C32—H32	120.0
C22—C27—C1	122.51 (18)	C31—C30—H30	120.0
C26—C27—C22	118.63 (17)	C29—C30—C31	120.0 (2)
C26—C27—C1	118.86 (17)	C29—C30—H30	120.0
C27—C1—C2	108.34 (16)	C10—C11—H11	120.0
C15—C1—C27	111.04 (15)	C10—C11—C12	120.0 (2)
C15—C1—C2	109.17 (16)	C12—C11—H11	120.0
C15—C1—C14	108.60 (16)	C13—C12—C11	119.0 (2)
C14—C1—C27	108.74 (15)	C13—C12—H12	120.5
C14—C1—C2	110.95 (15)	C11—C12—H12	120.5
C9—N2—C7	121.08 (17)	C7—C6—H6	119.8
C9—N2—C37	119.08 (18)	C5—C6—C7	120.5 (2)
C7—N2—C37	117.60 (18)	C5—C6—H6	119.8
N2—C9—C10	120.03 (19)	C28—C29—H29	120.1
C14—C9—N2	121.06 (19)	C30—C29—C28	119.8 (2)
C14—C9—C10	118.9 (2)	C30—C29—H29	120.1
C34—O3—H3	109.5	C3—C4—H4	120.6
C20—C15—C1	122.88 (17)	C5—C4—C3	118.8 (2)
C16—C15—C1	118.51 (18)	C5—C4—H4	120.6
C16—C15—C20	118.6 (2)	C15—C16—H16	118.9
C15—C20—N1	120.28 (18)	C17—C16—C15	122.1 (2)
C15—C20—C19	119.3 (2)	C17—C16—H16	118.9
C19—C20—N1	120.45 (19)	O3—C34—C31	116.4 (2)
C2—C7—N2	120.49 (19)	O4—C34—O3	123.2 (2)
C2—C7—C6	119.2 (2)	O4—C34—C31	120.4 (2)
C6—C7—N2	120.4 (2)	C38—C37—N2	120.8 (2)
C22—C23—H23	119.4	C38—C37—C42	120.4 (2)
C24—C23—C22	121.28 (19)	C42—C37—N2	118.8 (2)
C24—C23—H23	119.4	C39—C40—C41	120.0 (2)
C27—C26—H26	118.7	C39—C40—C43	119.4 (2)
C25—C26—C27	122.65 (19)	C41—C40—C43	120.6 (2)
C25—C26—H26	118.7	C43—O2—H2	109.5
C7—C2—C1	122.71 (18)	C37—C38—H38	120.4
C3—C2—C1	118.77 (18)	C37—C38—C39	119.1 (2)
C3—C2—C7	118.47 (19)	C39—C38—H38	120.4
C26—C25—H25	120.7	C37—C42—H42	120.0
C26—C25—C24	118.5 (2)	C37—C42—C41	120.0 (2)
C24—C25—H25	120.7	C41—C42—H42	120.0
C9—C14—C1	122.51 (18)	C28—C33—C32	120.3 (2)
C13—C14—C1	118.85 (18)	C28—C33—H33	119.9
C13—C14—C9	118.64 (19)	C32—C33—H33	119.9
C14—C13—H13	118.9	C6—C5—C4	121.0 (2)
C12—C13—C14	122.2 (2)	C6—C5—H5	119.5
C12—C13—H13	118.9	C4—C5—H5	119.5
C29—C28—N1	120.0 (2)	C40—C39—C38	120.6 (2)
C33—C28—N1	119.9 (2)	C40—C39—H39	119.7
C33—C28—C29	120.1 (2)	C38—C39—H39	119.7
C20—C19—H19	119.6	C16—C17—H17	120.5
C18—C19—C20	120.8 (2)	C16—C17—C18	119.0 (2)
C18—C19—H19	119.6	C18—C17—H17	120.5
C23—C24—C25	120.23 (19)	C40—C41—C42	119.9 (2)
C23—C24—H24	119.9	C40—C41—H41	120.1
C25—C24—H24	119.9	C42—C41—H41	120.1
C2—C3—H3A	118.9	C19—C18—C17	120.2 (2)
C4—C3—C2	122.1 (2)	C19—C18—H18	119.9
C4—C3—H3A	118.9	C17—C18—H18	119.9
C32—C31—C30	119.8 (2)	O1—C43—C40	122.1 (3)
C32—C31—C34	121.2 (2)	O1—C43—O2	124.1 (2)
C30—C31—C34	119.0 (2)	O2—C43—C40	113.8 (3)
C22—N1—C20—C15	0.0 (3)	C7—C6—C5—C4	2.0 (4)
C22—N1—C20—C19	179.7 (2)	C23—C22—N1—C20	178.2 (2)
C22—N1—C28—C29	92.4 (3)	C23—C22—N1—C28	0.0 (3)
C22—N1—C28—C33	−86.6 (3)	C23—C22—C27—C1	179.15 (18)
C22—C27—C1—C15	4.6 (3)	C23—C22—C27—C26	−0.3 (3)
C22—C27—C1—C2	124.5 (2)	C26—C27—C1—C15	−175.95 (17)
C22—C27—C1—C14	−114.8 (2)	C26—C27—C1—C2	−56.1 (2)
C22—C27—C26—C25	0.4 (3)	C26—C27—C1—C14	64.6 (2)
C22—C23—C24—C25	0.7 (4)	C26—C25—C24—C23	−0.6 (3)
N1—C22—C27—C1	−1.2 (3)	C2—C1—C15—C20	−125.5 (2)
N1—C22—C27—C26	179.33 (19)	C2—C1—C15—C16	57.5 (2)
N1—C22—C23—C24	−179.9 (2)	C2—C1—C14—C9	7.7 (3)
N1—C20—C19—C18	179.3 (2)	C2—C1—C14—C13	−173.01 (18)
N1—C28—C29—C30	−177.6 (2)	C2—C7—C6—C5	−1.5 (4)
N1—C28—C33—C32	178.7 (2)	C2—C3—C4—C5	−1.0 (4)
C27—C22—N1—C20	−1.4 (3)	C14—C1—C15—C20	113.4 (2)
C27—C22—N1—C28	−179.57 (19)	C14—C1—C15—C16	−63.6 (2)
C27—C22—C23—C24	−0.3 (3)	C14—C1—C2—C7	−9.0 (3)
C27—C1—C15—C20	−6.1 (3)	C14—C1—C2—C3	173.32 (19)
C27—C1—C15—C16	176.87 (19)	C14—C9—C10—C11	0.2 (4)
C27—C1—C2—C7	110.3 (2)	C14—C13—C12—C11	0.5 (4)
C27—C1—C2—C3	−67.4 (2)	C28—N1—C20—C15	178.1 (2)
C27—C1—C14—C9	−111.3 (2)	C28—N1—C20—C19	−2.2 (3)
C27—C1—C14—C13	67.9 (2)	C3—C4—C5—C6	−0.8 (4)
C27—C26—C25—C24	0.0 (3)	C31—C32—C33—C28	−0.7 (4)
C1—C27—C26—C25	−179.0 (2)	C31—C30—C29—C28	−1.5 (4)
C1—C15—C20—N1	4.1 (3)	C10—C9—C14—C1	180.0 (2)
C1—C15—C20—C19	−175.6 (2)	C10—C9—C14—C13	0.7 (3)
C1—C15—C16—C17	176.8 (2)	C10—C11—C12—C13	0.5 (4)
C1—C2—C3—C4	179.2 (2)	C32—C31—C30—C29	0.6 (4)
C1—C14—C13—C12	179.6 (2)	C32—C31—C34—O3	−9.5 (3)
N2—C9—C14—C1	1.0 (3)	C32—C31—C34—O4	170.5 (2)
N2—C9—C14—C13	−178.3 (2)	C30—C31—C32—C33	0.5 (4)
N2—C9—C10—C11	179.2 (2)	C30—C31—C34—O3	172.2 (2)
N2—C7—C2—C1	1.7 (3)	C30—C31—C34—O4	−7.8 (3)
N2—C7—C2—C3	179.3 (2)	C6—C7—C2—C1	−177.9 (2)
N2—C7—C6—C5	179.0 (2)	C6—C7—C2—C3	−0.2 (3)
N2—C37—C38—C39	−177.0 (2)	C29—C28—C33—C32	−0.2 (4)
N2—C37—C42—C41	177.1 (2)	C16—C15—C20—N1	−178.8 (2)
C9—N2—C7—C2	8.3 (3)	C16—C15—C20—C19	1.5 (3)
C9—N2—C7—C6	−172.2 (2)	C16—C17—C18—C19	1.7 (5)
C9—N2—C37—C38	−101.3 (3)	C34—C31—C32—C33	−177.8 (2)
C9—N2—C37—C42	78.9 (3)	C34—C31—C30—C29	178.9 (2)
C9—C14—C13—C12	−1.1 (3)	C37—N2—C9—C14	−172.3 (2)
C9—C10—C11—C12	−0.8 (4)	C37—N2—C9—C10	8.8 (3)
C15—C1—C2—C7	−128.7 (2)	C37—N2—C7—C2	171.1 (2)
C15—C1—C2—C3	53.7 (2)	C37—N2—C7—C6	−9.3 (3)
C15—C1—C14—C9	127.7 (2)	C37—C38—C39—C40	−0.8 (4)
C15—C1—C14—C13	−53.0 (2)	C37—C42—C41—C40	0.7 (5)
C15—C20—C19—C18	−1.0 (4)	C38—C37—C42—C41	−2.7 (4)
C15—C16—C17—C18	−1.2 (4)	C42—C37—C38—C39	2.8 (4)
C20—N1—C28—C29	−85.8 (3)	C33—C28—C29—C30	1.3 (4)
C20—N1—C28—C33	95.2 (3)	C39—C40—C41—C42	1.2 (4)
C20—C15—C16—C17	−0.4 (4)	C39—C40—C43—O1	8.7 (4)
C20—C19—C18—C17	−0.7 (5)	C39—C40—C43—O2	−170.6 (3)
C7—N2—C9—C14	−9.7 (3)	C41—C40—C39—C38	−1.2 (4)
C7—N2—C9—C10	171.3 (2)	C41—C40—C43—O1	−171.2 (3)
C7—N2—C37—C38	95.5 (3)	C41—C40—C43—O2	9.5 (4)
C7—N2—C37—C42	−84.3 (3)	C43—C40—C39—C38	179.0 (3)
C7—C2—C3—C4	1.5 (3)	C43—C40—C41—C42	−178.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4^i	0.82	1.84	2.648 (2)	168
C4—H4···Cg1^ii	0.93	2.90	3.7568 (3)	154
C33—H33···Cg1^iii	0.93	2.85	3.7156 (3)	156

Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y, −z+1; (iii) −x+1, −y+1, −z+1.

catena-Poly[hemi-µ-aqua-aqua(µ₃-4,4'-{9,9'-spirobi[10H-\ acridine]-10,10'-diyl}dibenzoato)cadmium(II)] (I)

Crystal data

[Cd(C39H24N2O4)(H2O)1.5]	F(000) = 2936
Mr = 724.03	Dx = 1.006 Mg m^−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
a = 27.4361 (19) Å	Cell parameters from 4113 reflections
b = 9.0861 (9) Å	θ = 7.0–70.7°
c = 40.473 (2) Å	µ = 3.94 mm^−1
β = 108.581 (7)°	T = 293 K
V = 9563.5 (13) Å^3	Block, colourless
Z = 8	0.29 × 0.23 × 0.14 mm

Data collection

Rigaku OD SuperNova Dual source diffractometer with an Eos detector	8499 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	5609 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.057
Detector resolution: 16.0793 pixels mm^-1	θmax = 71.3°, θmin = 3.4°
ω scans	h = −30→33
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −8→10
Tmin = 0.660, Tmax = 1.000	l = −48→49
16822 measured reflections

Refinement

Refinement on F^2	Primary atom site location: iterative
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.227	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ^2(Fo^2) + (0.1147P)^2 + 0.6298P] where P = (Fo^2 + 2Fc^2)/3
8499 reflections	(Δ/σ)max = 0.001
429 parameters	Δρmax = 0.62 e Å^−3
0 restraints	Δρmin = −1.22 e Å^−3

Special details

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.

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.5584 (3)	0.7956 (8)	0.29867 (12)	0.106 (2)
C2	0.5682 (2)	0.6943 (6)	0.32910 (13)	0.0791 (14)
C3	0.5327 (2)	0.6755 (6)	0.34653 (12)	0.0755 (13)
H3	0.5011	0.7231	0.3388	0.091*
C4	0.5444 (2)	0.5851 (6)	0.37567 (12)	0.0694 (12)
H4	0.5204	0.5716	0.3872	0.083*
C5	0.5911 (2)	0.5156 (5)	0.38766 (12)	0.0625 (11)
C6	0.6267 (2)	0.5341 (7)	0.37075 (16)	0.0885 (17)
H6	0.6580	0.4851	0.3787	0.106*
C7	0.6162 (2)	0.6263 (7)	0.34158 (13)	0.0885 (17)
H7	0.6409	0.6419	0.3307	0.106*
C8	0.62467 (15)	0.4923 (4)	0.45093 (11)	0.0497 (9)
C9	0.64304 (16)	0.6383 (5)	0.45344 (12)	0.0586 (10)
H9	0.6404	0.6909	0.4332	0.070*
C10	0.66477 (16)	0.7036 (5)	0.48533 (12)	0.0608 (10)
H10	0.6765	0.8001	0.4865	0.073*
C11	0.66945 (15)	0.6279 (5)	0.51564 (13)	0.0607 (11)
H11	0.6846	0.6718	0.5372	0.073*
C12	0.65121 (16)	0.4854 (4)	0.51333 (12)	0.0525 (9)
H12	0.6537	0.4349	0.5338	0.063*
C13	0.62916 (13)	0.4142 (4)	0.48160 (10)	0.0439 (8)
C14	0.60750 (13)	0.2580 (4)	0.48100 (10)	0.0458 (8)
C15	0.59464 (13)	0.1907 (4)	0.44474 (10)	0.0486 (8)
C16	0.59139 (16)	0.2758 (5)	0.41552 (10)	0.0558 (9)
C17	0.5745 (2)	0.2097 (6)	0.38240 (12)	0.0726 (13)
H17	0.5712	0.2664	0.3627	0.087*
C18	0.5627 (2)	0.0610 (6)	0.37884 (14)	0.0752 (14)
H18	0.5518	0.0181	0.3568	0.090*
C19	0.5674 (2)	−0.0239 (5)	0.40832 (14)	0.0717 (13)
H19	0.5598	−0.1239	0.4062	0.086*
C20	0.58333 (18)	0.0416 (5)	0.44068 (13)	0.0612 (11)
H20	0.5866	−0.0155	0.4603	0.073*
C21	0.64751 (13)	0.1647 (4)	0.50724 (10)	0.0459 (8)
C22	0.69388 (14)	0.1350 (4)	0.50128 (12)	0.0538 (9)
H22	0.6992	0.1715	0.4812	0.065*
C23	0.73240 (16)	0.0523 (5)	0.52445 (14)	0.0623 (11)
H23	0.7633	0.0353	0.5202	0.075*
C24	0.72417 (18)	−0.0034 (5)	0.55340 (15)	0.0652 (12)
H24	0.7495	−0.0608	0.5687	0.078*
C25	0.6791 (2)	0.0231 (6)	0.56065 (14)	0.0674 (12)
H25	0.6746	−0.0150	0.5808	0.081*
C26	0.63992 (15)	0.1085 (5)	0.53733 (11)	0.0543 (9)
C27	0.55297 (16)	0.2083 (5)	0.52074 (12)	0.0587 (10)
C28	0.50587 (18)	0.2225 (6)	0.52781 (14)	0.0727 (13)
H28	0.5027	0.1855	0.5485	0.087*
C29	0.46532 (16)	0.2903 (6)	0.50434 (15)	0.0762 (14)
H29	0.4341	0.2956	0.5087	0.091*
C30	0.46954 (17)	0.3506 (6)	0.47460 (14)	0.0712 (13)
H30	0.4420	0.4008	0.4593	0.085*
C31	0.51546 (15)	0.3359 (5)	0.46752 (12)	0.0598 (10)
H31	0.5179	0.3736	0.4467	0.072*
C32	0.55763 (13)	0.2673 (4)	0.49024 (10)	0.0498 (9)
C33	0.59179 (17)	0.1076 (6)	0.57899 (12)	0.0630 (11)
C34	0.5714 (2)	−0.0190 (6)	0.58660 (14)	0.0733 (14)
H34	0.5596	−0.0905	0.5695	0.088*
C35	0.5681 (2)	−0.0430 (6)	0.61983 (15)	0.0792 (14)
H35	0.5540	−0.1301	0.6248	0.095*
C36	0.5853 (2)	0.0607 (6)	0.64484 (13)	0.0730 (13)
C37	0.6055 (3)	0.1877 (8)	0.63714 (16)	0.108 (2)
H37	0.6173	0.2590	0.6543	0.130*
C38	0.6088 (3)	0.2130 (7)	0.60375 (16)	0.103 (2)
H38	0.6225	0.3006	0.5987	0.123*
C39	0.5798 (3)	0.0383 (8)	0.68039 (15)	0.0851 (16)
Cd1	0.559298 (17)	0.02398 (6)	0.741018 (9)	0.0866 (2)
N1	0.60290 (16)	0.4276 (4)	0.41861 (9)	0.0632 (9)
N2	0.59425 (14)	0.1350 (5)	0.54462 (10)	0.0691 (10)
O1	0.56019 (18)	−0.0740 (5)	0.68698 (10)	0.0923 (11)
O2	0.5947 (2)	0.1424 (7)	0.70227 (12)	0.1301 (19)
O3	0.5889 (2)	0.8127 (7)	0.28346 (12)	0.142 (2)
O4	0.5179 (3)	0.8665 (8)	0.29007 (13)	0.154 (3)
O5	0.5000	−0.1318 (9)	0.7500	0.208 (6)
H5A	0.4849	−0.1937	0.7298	0.250*	0.50
H5B	0.5151	−0.1937	0.7702	0.250*	0.50
O6	0.6240 (4)	−0.1355 (13)	0.76825 (19)	0.303 (7)
H6A	0.6368	−0.1803	0.7512	0.454*
H6B	0.6512	−0.0817	0.7847	0.454*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.156 (6)	0.118 (5)	0.029 (2)	0.017 (5)	0.010 (3)	0.011 (3)
C2	0.101 (4)	0.077 (3)	0.055 (3)	0.015 (3)	0.019 (3)	0.010 (2)
C3	0.089 (3)	0.076 (3)	0.057 (3)	0.020 (3)	0.016 (2)	−0.002 (2)
C4	0.083 (3)	0.069 (3)	0.057 (3)	0.005 (3)	0.022 (2)	0.007 (2)
C5	0.080 (3)	0.061 (2)	0.048 (2)	0.003 (2)	0.022 (2)	0.0097 (19)
C6	0.089 (4)	0.106 (4)	0.074 (4)	0.020 (3)	0.031 (3)	0.035 (3)
C7	0.084 (3)	0.127 (5)	0.061 (3)	0.009 (3)	0.031 (3)	0.028 (3)
C8	0.049 (2)	0.051 (2)	0.052 (2)	0.0016 (16)	0.0190 (17)	−0.0002 (17)
C9	0.063 (2)	0.051 (2)	0.067 (3)	0.0035 (19)	0.028 (2)	0.007 (2)
C10	0.058 (2)	0.052 (2)	0.074 (3)	−0.0039 (19)	0.024 (2)	−0.003 (2)
C11	0.051 (2)	0.056 (2)	0.070 (3)	−0.0012 (19)	0.0121 (19)	−0.016 (2)
C12	0.052 (2)	0.054 (2)	0.053 (2)	0.0049 (17)	0.0183 (18)	−0.0005 (17)
C13	0.0413 (17)	0.0458 (19)	0.048 (2)	0.0083 (15)	0.0182 (15)	0.0018 (16)
C14	0.0426 (18)	0.049 (2)	0.0471 (19)	0.0039 (16)	0.0162 (15)	0.0051 (16)
C15	0.0447 (18)	0.051 (2)	0.051 (2)	0.0044 (17)	0.0167 (16)	−0.0011 (17)
C16	0.061 (2)	0.057 (2)	0.049 (2)	0.0056 (19)	0.0172 (18)	−0.0061 (18)
C17	0.090 (3)	0.075 (3)	0.050 (2)	0.006 (3)	0.018 (2)	−0.006 (2)
C18	0.084 (3)	0.073 (3)	0.063 (3)	0.002 (3)	0.015 (2)	−0.020 (3)
C19	0.090 (3)	0.058 (3)	0.064 (3)	−0.004 (2)	0.019 (3)	−0.017 (2)
C20	0.065 (2)	0.051 (2)	0.069 (3)	−0.002 (2)	0.023 (2)	−0.005 (2)
C21	0.0434 (18)	0.0446 (19)	0.053 (2)	0.0035 (16)	0.0192 (15)	0.0040 (16)
C22	0.048 (2)	0.052 (2)	0.065 (2)	0.0042 (18)	0.0235 (18)	0.0027 (19)
C23	0.045 (2)	0.065 (3)	0.082 (3)	0.011 (2)	0.026 (2)	0.001 (2)
C24	0.059 (2)	0.060 (3)	0.074 (3)	0.007 (2)	0.018 (2)	0.003 (2)
C25	0.070 (3)	0.080 (3)	0.055 (3)	0.006 (2)	0.023 (2)	0.016 (2)
C26	0.051 (2)	0.064 (2)	0.052 (2)	0.0036 (19)	0.0216 (17)	0.0052 (19)
C27	0.050 (2)	0.066 (3)	0.068 (3)	0.003 (2)	0.0304 (19)	0.001 (2)
C28	0.066 (3)	0.080 (3)	0.086 (3)	0.015 (2)	0.044 (3)	0.014 (3)
C29	0.042 (2)	0.089 (3)	0.107 (4)	0.008 (2)	0.037 (2)	−0.002 (3)
C30	0.050 (2)	0.077 (3)	0.087 (3)	0.014 (2)	0.023 (2)	0.002 (3)
C31	0.051 (2)	0.063 (2)	0.067 (3)	0.012 (2)	0.0212 (19)	0.004 (2)
C32	0.0418 (18)	0.050 (2)	0.061 (2)	0.0042 (16)	0.0221 (17)	−0.0007 (18)
C33	0.061 (2)	0.082 (3)	0.055 (2)	0.000 (2)	0.029 (2)	−0.002 (2)
C34	0.091 (4)	0.086 (3)	0.051 (3)	−0.008 (3)	0.034 (3)	−0.002 (2)
C35	0.095 (4)	0.085 (3)	0.072 (3)	−0.009 (3)	0.047 (3)	0.000 (3)
C36	0.083 (3)	0.091 (3)	0.050 (3)	−0.010 (3)	0.030 (2)	−0.012 (2)
C37	0.152 (6)	0.114 (5)	0.074 (4)	−0.039 (5)	0.059 (4)	−0.030 (4)
C38	0.140 (6)	0.093 (4)	0.095 (4)	−0.030 (4)	0.066 (4)	−0.012 (4)
C39	0.095 (4)	0.111 (5)	0.055 (3)	−0.001 (3)	0.032 (3)	−0.010 (3)
Cd1	0.1117 (4)	0.1101 (4)	0.0434 (3)	0.0093 (2)	0.0321 (2)	−0.00852 (17)
N1	0.090 (3)	0.0519 (19)	0.0467 (19)	0.0004 (19)	0.0209 (18)	0.0005 (16)
N2	0.063 (2)	0.094 (3)	0.061 (2)	0.018 (2)	0.0351 (18)	0.017 (2)
O1	0.122 (3)	0.110 (3)	0.057 (2)	−0.004 (3)	0.045 (2)	−0.001 (2)
O2	0.175 (5)	0.158 (5)	0.077 (3)	−0.048 (4)	0.068 (3)	−0.040 (3)
O3	0.175 (5)	0.179 (5)	0.068 (3)	0.011 (4)	0.033 (3)	0.067 (3)
O4	0.190 (6)	0.185 (6)	0.071 (3)	0.079 (5)	0.020 (3)	0.048 (4)
O5	0.330 (14)	0.099 (5)	0.302 (14)	0.000	0.250 (13)	0.000
O6	0.367 (13)	0.334 (13)	0.121 (6)	0.229 (12)	−0.044 (7)	−0.045 (7)

Geometric parameters (Å, º)

C1—C2	1.491 (7)	C23—C24	1.360 (7)
C1—O3	1.198 (9)	C24—H24	0.9300
C1—O4	1.233 (9)	C24—C25	1.379 (7)
C2—C3	1.385 (7)	C25—H25	0.9300
C2—C7	1.394 (8)	C25—C26	1.416 (6)
C3—H3	0.9300	C26—N2	1.397 (5)
C3—C4	1.388 (7)	C27—C28	1.416 (5)
C4—H4	0.9300	C27—C32	1.388 (6)
C4—C5	1.371 (7)	C27—N2	1.401 (6)
C5—C6	1.369 (8)	C28—H28	0.9300
C5—N1	1.434 (6)	C28—C29	1.359 (7)
C6—H6	0.9300	C29—H29	0.9300
C6—C7	1.400 (7)	C29—C30	1.360 (7)
C7—H7	0.9300	C30—H30	0.9300
C8—C9	1.411 (6)	C30—C31	1.385 (6)
C8—C13	1.401 (6)	C31—H31	0.9300
C8—N1	1.384 (6)	C31—C32	1.377 (5)
C9—H9	0.9300	C33—C34	1.356 (7)
C9—C10	1.372 (6)	C33—C38	1.357 (7)
C10—H10	0.9300	C33—N2	1.436 (5)
C10—C11	1.376 (6)	C34—H34	0.9300
C11—H11	0.9300	C34—C35	1.394 (7)
C11—C12	1.380 (6)	C35—H35	0.9300
C12—H12	0.9300	C35—C36	1.353 (7)
C12—C13	1.392 (6)	C36—C37	1.358 (8)
C13—C14	1.536 (5)	C36—C39	1.508 (7)
C14—C15	1.524 (5)	C37—H37	0.9300
C14—C21	1.519 (5)	C37—C38	1.403 (8)
C14—C32	1.531 (5)	C38—H38	0.9300
C15—C16	1.392 (6)	C39—Cd1	2.689 (6)
C15—C20	1.387 (6)	C39—O1	1.222 (7)
C16—C17	1.406 (6)	C39—O2	1.271 (7)
C16—N1	1.411 (6)	Cd1—O1	2.369 (4)
C17—H17	0.9300	Cd1—O2	2.352 (5)
C17—C18	1.386 (7)	Cd1—O3^i	2.219 (4)
C18—H18	0.9300	Cd1—O4^ii	2.316 (6)
C18—C19	1.392 (8)	Cd1—O5	2.272 (5)
C19—H19	0.9300	Cd1—O6	2.284 (7)
C19—C20	1.377 (7)	O3—Cd1^iii	2.219 (4)
C20—H20	0.9300	O4—Cd1^ii	2.316 (6)
C21—C22	1.395 (5)	O5—Cd1^iv	2.272 (5)
C21—C26	1.396 (5)	O5—H5A	0.9700
C22—H22	0.9300	O5—H5B	0.9700
C22—C23	1.389 (6)	O6—H6A	0.9600
C23—H23	0.9300	O6—H6B	0.9600
O3—C1—C2	122.1 (7)	C32—C27—N2	120.9 (3)
O3—C1—O4	120.1 (6)	N2—C27—C28	119.5 (4)
O4—C1—C2	117.8 (7)	C27—C28—H28	120.1
C3—C2—C1	121.7 (6)	C29—C28—C27	119.8 (4)
C3—C2—C7	119.8 (5)	C29—C28—H28	120.1
C7—C2—C1	118.4 (6)	C28—C29—H29	119.4
C2—C3—H3	120.1	C28—C29—C30	121.3 (4)
C2—C3—C4	119.7 (5)	C30—C29—H29	119.4
C4—C3—H3	120.1	C29—C30—H30	120.5
C3—C4—H4	119.6	C29—C30—C31	118.9 (4)
C5—C4—C3	120.7 (5)	C31—C30—H30	120.5
C5—C4—H4	119.6	C30—C31—H31	118.9
C4—C5—N1	119.4 (4)	C32—C31—C30	122.1 (4)
C6—C5—C4	120.1 (4)	C32—C31—H31	118.9
C6—C5—N1	120.5 (4)	C27—C32—C14	122.6 (3)
C5—C6—H6	119.8	C31—C32—C14	119.2 (4)
C5—C6—C7	120.4 (5)	C31—C32—C27	118.2 (3)
C7—C6—H6	119.8	C34—C33—C38	120.0 (5)
C2—C7—C6	119.2 (5)	C34—C33—N2	121.1 (5)
C2—C7—H7	120.4	C38—C33—N2	118.8 (5)
C6—C7—H7	120.4	C33—C34—H34	119.6
C13—C8—C9	118.9 (4)	C33—C34—C35	120.7 (5)
N1—C8—C9	120.3 (4)	C35—C34—H34	119.6
N1—C8—C13	120.8 (4)	C34—C35—H35	120.1
C8—C9—H9	119.6	C36—C35—C34	119.8 (5)
C10—C9—C8	120.8 (4)	C36—C35—H35	120.1
C10—C9—H9	119.6	C35—C36—C37	119.4 (5)
C9—C10—H10	119.6	C35—C36—C39	120.1 (5)
C9—C10—C11	120.8 (4)	C37—C36—C39	120.4 (5)
C11—C10—H10	119.6	C36—C37—H37	119.4
C10—C11—H11	120.7	C36—C37—C38	121.2 (6)
C10—C11—C12	118.7 (4)	C38—C37—H37	119.4
C12—C11—H11	120.7	C33—C38—C37	118.9 (6)
C11—C12—H12	118.7	C33—C38—H38	120.6
C11—C12—C13	122.7 (4)	C37—C38—H38	120.6
C13—C12—H12	118.7	C36—C39—Cd1	172.2 (5)
C8—C13—C14	122.0 (3)	O1—C39—C36	120.4 (5)
C12—C13—C8	118.1 (4)	O1—C39—Cd1	61.7 (3)
C12—C13—C14	119.8 (3)	O1—C39—O2	122.4 (5)
C15—C14—C13	110.9 (3)	O2—C39—C36	117.1 (6)
C15—C14—C32	107.8 (3)	O2—C39—Cd1	61.0 (3)
C21—C14—C13	108.3 (3)	O1—Cd1—C39	27.01 (16)
C21—C14—C15	110.1 (3)	O2—Cd1—C39	28.21 (17)
C21—C14—C32	111.3 (3)	O2—Cd1—O1	55.14 (16)
C32—C14—C13	108.5 (3)	O3^i—Cd1—C39	122.9 (2)
C16—C15—C14	121.8 (3)	O3^i—Cd1—O1	149.0 (2)
C20—C15—C14	118.7 (4)	O3^i—Cd1—O2	94.8 (2)
C20—C15—C16	119.4 (4)	O3^i—Cd1—O4^ii	100.3 (2)
C15—C16—C17	119.0 (4)	O3^i—Cd1—O5	113.4 (2)
C15—C16—N1	121.1 (4)	O3^i—Cd1—O6	90.8 (3)
C17—C16—N1	119.9 (4)	O4^ii—Cd1—C39	84.5 (2)
C16—C17—H17	119.6	O4^ii—Cd1—O1	86.37 (19)
C18—C17—C16	120.7 (5)	O4^ii—Cd1—O2	86.7 (2)
C18—C17—H17	119.6	O5—Cd1—C39	123.00 (17)
C17—C18—H18	120.1	O5—Cd1—O1	97.59 (15)
C17—C18—C19	119.8 (5)	O5—Cd1—O2	149.42 (13)
C19—C18—H18	120.1	O5—Cd1—O4^ii	77.1 (2)
C18—C19—H19	120.3	O5—Cd1—O6	90.8 (4)
C20—C19—C18	119.4 (4)	O6—Cd1—C39	96.6 (3)
C20—C19—H19	120.3	O6—Cd1—O1	88.4 (2)
C15—C20—H20	119.1	O6—Cd1—O2	100.9 (4)
C19—C20—C15	121.7 (5)	O6—Cd1—O4^ii	166.0 (4)
C19—C20—H20	119.1	C8—N1—C5	119.9 (4)
C22—C21—C14	118.9 (3)	C8—N1—C16	121.0 (4)
C22—C21—C26	118.5 (4)	C16—N1—C5	119.1 (4)
C26—C21—C14	122.6 (3)	C26—N2—C27	121.2 (3)
C21—C22—H22	119.1	C26—N2—C33	119.8 (4)
C23—C22—C21	121.8 (4)	C27—N2—C33	118.3 (3)
C23—C22—H22	119.1	C39—O1—Cd1	91.3 (3)
C22—C23—H23	120.5	C39—O2—Cd1	90.8 (4)
C24—C23—C22	118.9 (4)	C1—O3—Cd1^iii	109.9 (5)
C24—C23—H23	120.5	C1—O4—Cd1^ii	164.3 (5)
C23—C24—H24	119.2	Cd1^iv—O5—Cd1	102.9 (3)
C23—C24—C25	121.6 (4)	Cd1—O5—H5A	111.2
C25—C24—H24	119.2	Cd1^iv—O5—H5A	111.2
C24—C25—H25	120.1	Cd1—O5—H5B	111.2
C24—C25—C26	119.7 (4)	Cd1^iv—O5—H5B	111.2
C26—C25—H25	120.1	H5A—O5—H5B	109.1
C21—C26—C25	119.3 (4)	Cd1—O6—H6A	109.1
C21—C26—N2	120.9 (4)	Cd1—O6—H6B	108.9
N2—C26—C25	119.8 (4)	H6A—O6—H6B	109.4
C32—C27—C28	119.6 (4)
C1—C2—C3—C4	−177.1 (5)	C28—C29—C30—C31	3.1 (8)
C1—C2—C7—C6	178.2 (6)	C29—C30—C31—C32	−2.6 (7)
C2—C1—O3—Cd1^iii	−178.7 (5)	C30—C31—C32—C14	−178.7 (4)
C2—C1—O4—Cd1^ii	−132 (2)	C30—C31—C32—C27	1.6 (7)
C2—C3—C4—C5	0.8 (8)	C32—C14—C15—C16	104.0 (4)
C3—C2—C7—C6	3.0 (9)	C32—C14—C15—C20	−72.7 (4)
C3—C4—C5—C6	−0.4 (8)	C32—C14—C21—C22	175.0 (3)
C3—C4—C5—N1	177.6 (4)	C32—C14—C21—C26	−5.6 (5)
C4—C5—C6—C7	1.3 (9)	C32—C27—C28—C29	1.6 (8)
C4—C5—N1—C8	−87.5 (6)	C32—C27—N2—C26	−5.2 (7)
C4—C5—N1—C16	91.7 (6)	C32—C27—N2—C33	165.3 (4)
C5—C6—C7—C2	−2.6 (10)	C33—C34—C35—C36	0.0 (9)
C6—C5—N1—C8	90.5 (6)	C34—C33—C38—C37	0.7 (10)
C6—C5—N1—C16	−90.3 (6)	C34—C33—N2—C26	−98.3 (6)
C7—C2—C3—C4	−2.1 (8)	C34—C33—N2—C27	91.1 (6)
C8—C9—C10—C11	0.4 (6)	C34—C35—C36—C37	0.3 (9)
C8—C13—C14—C15	14.7 (5)	C34—C35—C36—C39	177.5 (6)
C8—C13—C14—C21	135.6 (3)	C35—C36—C37—C38	0.0 (11)
C8—C13—C14—C32	−103.5 (4)	C35—C36—C39—Cd1	−103 (3)
C9—C8—C13—C12	0.7 (5)	C35—C36—C39—O1	0.6 (9)
C9—C8—C13—C14	176.7 (3)	C35—C36—C39—O2	−177.1 (6)
C9—C8—N1—C5	−10.4 (6)	C36—C37—C38—C33	−0.5 (11)
C9—C8—N1—C16	170.4 (4)	C36—C39—Cd1—O1	108 (4)
C9—C10—C11—C12	−0.9 (6)	C36—C39—Cd1—O2	−78 (3)
C10—C11—C12—C13	1.3 (6)	C36—C39—Cd1—O3^i	−84 (3)
C11—C12—C13—C8	−1.2 (6)	C36—C39—Cd1—O4^ii	15 (3)
C11—C12—C13—C14	−177.3 (3)	C36—C39—Cd1—O5	86 (3)
C12—C13—C14—C15	−169.3 (3)	C36—C39—Cd1—O6	−179 (100)
C12—C13—C14—C21	−48.5 (4)	C36—C39—O1—Cd1	−171.4 (5)
C12—C13—C14—C32	72.4 (4)	C36—C39—O2—Cd1	171.4 (5)
C13—C8—C9—C10	−0.3 (6)	C37—C36—C39—Cd1	74 (4)
C13—C8—N1—C5	170.0 (4)	C37—C36—C39—O1	177.8 (6)
C13—C8—N1—C16	−9.2 (6)	C37—C36—C39—O2	0.1 (10)
C13—C14—C15—C16	−14.6 (5)	C38—C33—C34—C35	−0.4 (9)
C13—C14—C15—C20	168.7 (3)	C38—C33—N2—C26	83.7 (7)
C13—C14—C21—C22	−65.9 (4)	C38—C33—N2—C27	−86.9 (6)
C13—C14—C21—C26	113.6 (4)	C39—C36—C37—C38	−177.2 (6)
C13—C14—C32—C27	−113.3 (4)	C39—Cd1—O5—Cd1^iv	−116.36 (19)
C13—C14—C32—C31	67.0 (5)	N1—C5—C6—C7	−176.6 (5)
C14—C15—C16—C17	−173.9 (4)	N1—C8—C9—C10	−179.9 (4)
C14—C15—C16—N1	3.8 (6)	N1—C8—C13—C12	−179.7 (4)
C14—C15—C20—C19	174.7 (4)	N1—C8—C13—C14	−3.7 (6)
C14—C21—C22—C23	179.1 (4)	N1—C16—C17—C18	−179.6 (5)
C14—C21—C26—C25	−179.7 (4)	N2—C27—C28—C29	−178.4 (5)
C14—C21—C26—N2	0.5 (6)	N2—C27—C32—C14	−0.8 (7)
C15—C14—C21—C22	55.5 (5)	N2—C27—C32—C31	178.9 (4)
C15—C14—C21—C26	−125.1 (4)	N2—C33—C34—C35	−178.4 (5)
C15—C14—C32—C27	126.6 (4)	N2—C33—C38—C37	178.7 (6)
C15—C14—C32—C31	−53.1 (5)	O1—C39—Cd1—O2	174.1 (7)
C15—C16—C17—C18	−2.0 (7)	O1—C39—Cd1—O3^i	168.5 (4)
C15—C16—N1—C5	−170.0 (4)	O1—C39—Cd1—O4^ii	−92.8 (4)
C15—C16—N1—C8	9.3 (6)	O1—C39—Cd1—O5	−22.0 (5)
C16—C15—C20—C19	−2.0 (7)	O1—C39—Cd1—O6	73.2 (5)
C16—C17—C18—C19	0.3 (8)	O1—C39—O2—Cd1	−6.2 (7)
C17—C16—N1—C5	7.6 (7)	O1—Cd1—O2—C39	3.3 (4)
C17—C16—N1—C8	−173.1 (4)	O1—Cd1—O5—Cd1^iv	−126.24 (11)
C17—C18—C19—C20	0.5 (8)	O2—C39—Cd1—O1	−174.1 (7)
C18—C19—C20—C15	0.4 (8)	O2—C39—Cd1—O3^i	−5.6 (5)
C20—C15—C16—C17	2.8 (6)	O2—C39—Cd1—O4^ii	93.2 (5)
C20—C15—C16—N1	−179.6 (4)	O2—C39—Cd1—O5	163.9 (4)
C21—C14—C15—C16	−134.5 (4)	O2—C39—Cd1—O6	−100.8 (6)
C21—C14—C15—C20	48.9 (5)	O2—C39—O1—Cd1	6.1 (7)
C21—C14—C32—C27	5.7 (5)	O2—Cd1—O1—C39	−3.4 (4)
C21—C14—C32—C31	−174.0 (4)	O2—Cd1—O5—Cd1^iv	−101.5 (4)
C21—C22—C23—C24	1.3 (7)	O3—C1—C2—C3	180.0 (7)
C21—C26—N2—C27	5.3 (7)	O3—C1—C2—C7	4.8 (10)
C21—C26—N2—C33	−165.0 (4)	O3—C1—O4—Cd1^ii	50 (3)
C22—C21—C26—C25	−0.2 (6)	O3^i—Cd1—O1—C39	−19.0 (6)
C22—C21—C26—N2	179.9 (4)	O3^i—Cd1—O2—C39	175.3 (4)
C22—C23—C24—C25	−1.5 (7)	O3^i—Cd1—O5—Cd1^iv	54.05 (19)
C23—C24—C25—C26	0.9 (8)	O4—C1—C2—C3	2.3 (10)
C24—C25—C26—C21	0.0 (7)	O4—C1—C2—C7	−172.8 (7)
C24—C25—C26—N2	179.8 (5)	O4—C1—O3—Cd1^iii	−1.1 (9)
C25—C26—N2—C27	−174.5 (5)	O4^ii—Cd1—O1—C39	85.1 (4)
C25—C26—N2—C33	15.1 (7)	O4^ii—Cd1—O2—C39	−84.6 (5)
C26—C21—C22—C23	−0.4 (6)	O4^ii—Cd1—O5—Cd1^iv	−41.74 (16)
C27—C28—C29—C30	−2.7 (8)	O5—Cd1—O1—C39	161.5 (4)
C28—C27—C32—C14	179.2 (4)	O5—Cd1—O2—C39	−27.1 (7)
C28—C27—C32—C31	−1.1 (7)	O6—Cd1—O1—C39	−107.9 (5)
C28—C27—N2—C26	174.8 (5)	O6—Cd1—O2—C39	83.5 (5)
C28—C27—N2—C33	−14.6 (7)	O6—Cd1—O5—Cd1^iv	145.28 (19)

Symmetry codes: (i) x, −y+1, z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1, z−1/2; (iv) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C23—H23···Cg1^iv	0.93	2.66	3.5712 (4)	168
C29—H29···Cg1^v	0.93	2.69	3.5457 (4)	154

Symmetry codes: (iv) −x+1, y, −z+3/2; (v) x+3/2, y+3/2, z+1.