Adsorption behaviour of a Cd^II–triazole MOF for butan-2-one in a single-crystal-to-single-crystal (SCSC) fashion: the role of hydrogen bonding and C—H...π inter­actions

The adsorption behaviour of the Cd^II–MOF {[Cd(L)₂(ClO₄)₂]·H₂O (1), where L is 4-amino-3,5-bis­[3-(pyridin-4-yl)phen­yl]-1,2,4-triazole, for butan-2-one was investigated in a single-crystal-to-single-crystal (SCSC) fashion. A new host–guest system that encapsulated butan-2-one mol­ecules, namely poly[[bis­{μ₃-4-amino-3,5-bis­[3-(pyridin-4-yl)phen­yl]-1,2,4-triazole}cadmium(II)] bis­(per­chlo­rate) butanone sesquisolvate], {[Cd(C₂₄H₁₈N₆)₂](ClO₄)₂·1.5C₄H₈O}_n, denoted C₄H₈O@Cd-MOF (2), was obtained via an SCSC transformation. MOF 2 crystallizes in the tetra­gonal space group P4₃2₁2. The specific binding sites for butan-2-one in the host were determined by single-crystal X-ray diffraction studies. N—H...O and C—H...O hydrogen-bonding inter­actions and C—H...π inter­actions between the framework, ClO₄⁻ anions and guest mol­ecules co-operatively bind 1.5 butan-2-one mol­ecules within the channels. The adsorption behaviour was further evidenced by ¹H NMR, IR, TGA and powder X-ray diffraction experiments, which are consistent with the single-crystal X-ray analysis. A ¹H NMR experiment demonstrates that the supra­molecular inter­actions between the framework, ClO₄⁻ anions and guest mol­ecules in MOF 2 lead to a high butan-2-one uptake in the channel.

Computing details

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: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: OLEX2 (Dolomanov et al., 2009); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXL (Sheldrick, 2008).

Poly[[bis{µ₃-4-amino-3,5-bis[3-(pyridin-4-yl)phenyl]-1,2,4-triazole}cadmium(II)] bis(perchlorate) butanone sesquisolvate]

Crystal data

[Cd(C24H18N6)2](ClO4)2·1.5C4H8O	Dx = 1.460 Mg m^−3
Mr = 1200.34	Cu Kα radiation, λ = 1.54184 Å
Tetragonal, P43212	Cell parameters from 4723 reflections
a = 15.9167 (2) Å	θ = 4.4–70.6°
c = 21.5498 (9) Å	µ = 4.68 mm^−1
V = 5459.5 (2) Å^3	T = 100 K
Z = 4	Block, clear light colourless
F(000) = 2456	0.14 × 0.12 × 0.05 mm

Data collection

SuperNova Dual Cu at zero Eos diffractometer	5136 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	4787 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.030
Detector resolution: 16.0793 pixels mm^-1	θmax = 70.7°, θmin = 5.0°
ω scans	h = −19→19
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −12→18
Tmin = 0.845, Tmax = 1.000	l = −12→25
11211 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.053	w = 1/[σ^2(Fo^2) + (0.0913P)^2 + 8.7372P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.152	(Δ/σ)max = 0.002
S = 1.07	Δρmax = 0.90 e Å^−3
5136 reflections	Δρmin = −1.18 e Å^−3
395 parameters	Extinction correction: SHELXL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
66 restraints	Extinction coefficient: 0.00027 (8)
Primary atom site location: iterative	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.016 (11)

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	0.5859 (3)	−0.3606 (3)	0.1402 (3)	0.0303 (11)
H1	0.5373	−0.3895	0.1510	0.036*
C2	0.6153 (4)	−0.2975 (3)	0.1807 (3)	0.0299 (11)
H2	0.5866	−0.2859	0.2173	0.036*
C3	0.6876 (4)	−0.2527 (3)	0.1653 (3)	0.0313 (12)
C4	0.7301 (4)	−0.2794 (4)	0.1132 (3)	0.0346 (12)
H4	0.7814	−0.2551	0.1031	0.041*
C5	0.6971 (4)	−0.3426 (4)	0.0754 (3)	0.0350 (13)
H5	0.7269	−0.3589	0.0403	0.042*
C6	0.7195 (3)	−0.1809 (3)	0.2025 (3)	0.0292 (11)
C7	0.6921 (3)	−0.1671 (4)	0.2636 (3)	0.0339 (13)
H7	0.6533	−0.2034	0.2816	0.041*
C8	0.7227 (4)	−0.1001 (5)	0.2970 (3)	0.0477 (17)
H8	0.7039	−0.0911	0.3373	0.057*
C9	0.7820 (4)	−0.0450 (4)	0.2708 (3)	0.0392 (14)
H9	0.8025	0.0000	0.2938	0.047*
C10	0.8100 (3)	−0.0586 (3)	0.2101 (2)	0.0253 (10)
C11	0.7787 (4)	−0.1262 (3)	0.1773 (3)	0.0294 (11)
H11	0.7978	−0.1356	0.1371	0.035*
C12	0.8726 (3)	−0.0036 (3)	0.1803 (2)	0.0252 (10)
C13	0.9235 (3)	0.0924 (3)	0.1182 (2)	0.0249 (10)
C14	0.9322 (3)	0.1616 (3)	0.0747 (2)	0.0279 (10)
C15	1.0030 (4)	0.1632 (4)	0.0372 (3)	0.0406 (14)
H15	1.0430	0.1208	0.0403	0.049*
C16	1.0141 (4)	0.2282 (4)	−0.0049 (4)	0.0473 (16)
H16	1.0620	0.2296	−0.0296	0.057*
C17	0.9541 (4)	0.2912 (4)	−0.0105 (3)	0.0416 (14)
H17	0.9612	0.3335	−0.0398	0.050*
C18	0.8838 (3)	0.2914 (4)	0.0274 (3)	0.0308 (12)
C19	0.8718 (3)	0.2261 (3)	0.0692 (3)	0.0284 (11)
H19	0.8238	0.2248	0.0937	0.034*
C20	0.8174 (3)	0.3577 (4)	0.0222 (3)	0.0315 (12)
C21	0.8059 (4)	0.4015 (4)	−0.0323 (3)	0.0375 (14)
H21	0.8422	0.3926	−0.0655	0.045*
C22	0.7401 (4)	0.4593 (4)	−0.0382 (3)	0.0379 (14)
H22	0.7342	0.4880	−0.0755	0.045*
C23	0.6979 (4)	0.4336 (4)	0.0612 (3)	0.0379 (13)
H23	0.6613	0.4439	0.0940	0.045*
C24	0.7625 (4)	0.3764 (4)	0.0699 (3)	0.0367 (14)
H24	0.7690	0.3503	0.1082	0.044*
C25	0.6123 (12)	0.9435 (15)	−0.006 (2)	0.248 (9)	0.75
H25A	0.6609	0.9788	−0.0100	0.371*	0.75
H25B	0.6032	0.9134	−0.0439	0.371*	0.75
H25C	0.6211	0.9042	0.0273	0.371*	0.75
C26	0.5344 (13)	0.9984 (17)	0.009 (2)	0.247 (9)	0.75
H26A	0.5314	1.0425	−0.0223	0.296*	0.75
H26B	0.4848	0.9637	0.0036	0.296*	0.75
C27	0.5298 (15)	1.0383 (17)	0.070 (2)	0.246 (9)	0.75
C28	0.4534 (13)	1.0838 (15)	0.100 (2)	0.244 (9)	0.75
H28A	0.4200	1.0441	0.1222	0.366*	0.75
H28B	0.4201	1.1089	0.0674	0.366*	0.75
H28C	0.4730	1.1268	0.1274	0.366*	0.75
Cd1	0.557972 (19)	0.557972 (19)	0.0000	0.02464 (16)
Cl2	0.88222 (13)	0.88222 (13)	1.0000	0.0724 (8)
N1	0.6238 (3)	−0.3805 (3)	0.0881 (2)	0.0300 (9)
N2	0.9547 (3)	−0.0071 (3)	0.1836 (2)	0.0282 (9)
N3	0.9871 (3)	0.0538 (3)	0.1443 (2)	0.0294 (9)
N4	0.8499 (3)	0.0580 (3)	0.1401 (2)	0.0281 (9)
N5	0.7679 (3)	0.0797 (4)	0.1208 (3)	0.0463 (14)
H5A	0.7504	0.0435	0.0920	0.069*
H5B	0.7336	0.0775	0.1534	0.069*
N6	0.6858 (3)	0.4751 (3)	0.0071 (2)	0.0306 (10)
O1	0.9009 (10)	0.8341 (11)	1.0555 (6)	0.080 (4)	0.50
O2	0.9277 (12)	0.9563 (10)	1.0212 (9)	0.133 (7)	0.50
O3	0.9467 (10)	0.8468 (11)	0.9609 (7)	0.106 (5)	0.50
O4	0.2131 (12)	0.3541 (8)	−0.0018 (11)	0.131 (6)	0.50
O5	0.3256 (6)	0.3256 (6)	0.0000	0.131 (4)
O6	0.2268 (5)	0.2358 (5)	0.0532 (3)	0.085 (2)
O7	0.5932 (10)	1.0264 (11)	0.1180 (16)	0.250 (9)	0.75
O8	0.871 (2)	0.8066 (12)	1.0250 (17)	0.23 (2)	0.50
Cl1	0.2548 (3)	0.2783 (3)	0.0020 (6)	0.0564 (17)	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.024 (2)	0.025 (3)	0.043 (3)	−0.005 (2)	−0.004 (2)	0.006 (2)
C2	0.032 (3)	0.022 (2)	0.035 (3)	−0.003 (2)	−0.002 (2)	0.001 (2)
C3	0.032 (3)	0.020 (2)	0.042 (3)	0.000 (2)	−0.002 (2)	0.000 (2)
C4	0.032 (3)	0.027 (3)	0.045 (3)	−0.011 (2)	0.004 (3)	−0.004 (2)
C5	0.029 (3)	0.029 (3)	0.047 (3)	−0.007 (2)	0.000 (2)	−0.003 (2)
C6	0.026 (3)	0.023 (3)	0.038 (3)	−0.002 (2)	−0.002 (2)	0.002 (2)
C7	0.023 (3)	0.040 (3)	0.039 (3)	−0.006 (2)	0.000 (2)	0.002 (2)
C8	0.040 (4)	0.064 (4)	0.039 (3)	−0.020 (3)	0.009 (3)	−0.012 (3)
C9	0.033 (3)	0.049 (4)	0.036 (3)	−0.017 (3)	−0.001 (2)	−0.010 (3)
C10	0.021 (2)	0.024 (2)	0.031 (2)	0.000 (2)	−0.0049 (19)	−0.001 (2)
C11	0.033 (3)	0.024 (3)	0.031 (3)	−0.003 (2)	0.001 (2)	0.000 (2)
C12	0.021 (3)	0.024 (2)	0.031 (2)	−0.0001 (19)	−0.005 (2)	−0.003 (2)
C13	0.022 (3)	0.017 (2)	0.035 (2)	−0.0023 (18)	0.0009 (19)	−0.005 (2)
C14	0.022 (2)	0.025 (2)	0.037 (3)	−0.001 (2)	0.001 (2)	−0.003 (2)
C15	0.031 (3)	0.034 (3)	0.057 (4)	0.013 (2)	0.006 (3)	0.007 (3)
C16	0.034 (3)	0.046 (3)	0.062 (4)	0.016 (3)	0.013 (3)	0.020 (3)
C17	0.034 (3)	0.038 (3)	0.053 (4)	0.009 (2)	0.011 (3)	0.017 (3)
C18	0.020 (2)	0.026 (3)	0.046 (3)	0.000 (2)	0.001 (2)	0.005 (2)
C19	0.024 (3)	0.022 (2)	0.040 (3)	−0.001 (2)	0.002 (2)	0.004 (2)
C20	0.020 (3)	0.029 (3)	0.045 (3)	0.002 (2)	−0.001 (2)	0.002 (2)
C21	0.029 (3)	0.033 (3)	0.051 (3)	0.016 (2)	0.004 (3)	0.006 (3)
C22	0.036 (3)	0.034 (3)	0.044 (3)	0.012 (3)	−0.003 (3)	0.006 (3)
C23	0.032 (3)	0.031 (3)	0.051 (3)	0.010 (2)	0.011 (3)	0.014 (3)
C24	0.026 (3)	0.035 (3)	0.049 (3)	0.009 (2)	0.006 (3)	0.013 (3)
C25	0.077 (7)	0.145 (11)	0.52 (3)	0.000 (8)	0.047 (13)	0.039 (15)
C26	0.077 (6)	0.145 (11)	0.52 (3)	−0.003 (7)	0.044 (12)	0.039 (14)
C27	0.078 (6)	0.142 (10)	0.52 (3)	0.002 (7)	0.038 (12)	0.043 (14)
C28	0.078 (7)	0.138 (11)	0.51 (3)	0.001 (8)	0.042 (12)	0.043 (14)
Cd1	0.01629 (17)	0.01629 (17)	0.0413 (3)	−0.00149 (17)	−0.00097 (15)	0.00097 (15)
Cl2	0.0803 (12)	0.0803 (12)	0.0566 (14)	−0.0261 (16)	0.0070 (13)	−0.0070 (13)
N1	0.023 (2)	0.023 (2)	0.045 (2)	−0.0032 (16)	−0.008 (2)	−0.002 (2)
N2	0.025 (2)	0.0184 (19)	0.041 (2)	−0.0003 (16)	0.0012 (19)	0.0013 (18)
N3	0.019 (2)	0.022 (2)	0.047 (2)	0.0032 (18)	−0.0007 (18)	0.002 (2)
N4	0.021 (2)	0.023 (2)	0.040 (2)	−0.0022 (19)	−0.0069 (17)	0.008 (2)
N5	0.025 (2)	0.054 (3)	0.060 (3)	−0.006 (2)	−0.013 (2)	0.024 (3)
N6	0.019 (2)	0.023 (2)	0.050 (3)	−0.0006 (16)	−0.001 (2)	0.004 (2)
O1	0.060 (6)	0.115 (10)	0.065 (6)	−0.031 (7)	0.002 (5)	0.014 (7)
O2	0.141 (8)	0.126 (8)	0.133 (8)	0.004 (5)	−0.015 (5)	−0.015 (5)
O3	0.103 (6)	0.120 (6)	0.094 (6)	0.001 (5)	0.014 (5)	−0.010 (5)
O4	0.140 (8)	0.119 (7)	0.133 (7)	0.001 (5)	−0.005 (5)	0.002 (5)
O5	0.133 (4)	0.133 (4)	0.128 (6)	−0.024 (5)	0.012 (3)	−0.012 (3)
O6	0.096 (5)	0.105 (6)	0.054 (3)	−0.030 (4)	−0.002 (3)	0.022 (4)
O7	0.083 (6)	0.147 (10)	0.52 (3)	0.002 (7)	0.030 (12)	0.046 (14)
O8	0.31 (4)	0.054 (10)	0.33 (5)	0.018 (17)	0.22 (4)	0.037 (18)
Cl1	0.063 (3)	0.060 (3)	0.0467 (17)	−0.024 (3)	−0.002 (3)	0.003 (3)

Geometric parameters (Å, º)

C1—H1	0.9300	C24—H24	0.9300
C1—C2	1.409 (8)	C25—H25A	0.9600
C1—N1	1.315 (8)	C25—H25B	0.9600
C2—H2	0.9300	C25—H25C	0.9600
C2—C3	1.395 (8)	C25—C26	1.550 (10)
C3—C4	1.377 (8)	C26—H26A	0.9700
C3—C6	1.485 (7)	C26—H26B	0.9700
C4—H4	0.9300	C26—C27	1.47 (6)
C4—C5	1.397 (8)	C27—C28	1.549 (10)
C5—H5	0.9300	C27—O7	1.45 (5)
C5—N1	1.341 (7)	C28—H28A	0.9600
C6—C7	1.405 (8)	C28—H28B	0.9600
C6—C11	1.393 (7)	C28—H28C	0.9600
C7—H7	0.9300	Cd1—N1^i	2.379 (4)
C7—C8	1.375 (9)	Cd1—N1^ii	2.379 (4)
C8—H8	0.9300	Cd1—N2^iii	2.325 (5)
C8—C9	1.406 (9)	Cd1—N2^iv	2.325 (5)
C9—H9	0.9300	Cd1—N6	2.430 (4)
C9—C10	1.400 (8)	Cd1—N6^v	2.430 (4)
C10—C11	1.381 (7)	Cl2—O1^vi	1.452 (11)
C10—C12	1.473 (7)	Cl2—O1	1.451 (11)
C11—H11	0.9300	Cl2—O2	1.457 (11)
C12—N2	1.309 (7)	Cl2—O2^vi	1.457 (11)
C12—N4	1.357 (7)	Cl2—O3	1.442 (11)
C13—C14	1.453 (7)	Cl2—O3^vi	1.442 (11)
C13—N3	1.311 (6)	Cl2—O8^vi	1.33 (2)
C13—N4	1.378 (6)	Cl2—O8	1.33 (2)
C14—C15	1.386 (8)	N1—Cd1^vii	2.379 (4)
C14—C19	1.411 (7)	N2—Cd1^viii	2.325 (5)
C15—H15	0.9300	N2—N3	1.386 (6)
C15—C16	1.388 (9)	N4—N5	1.414 (6)
C16—H16	0.9300	N5—H5A	0.8901
C16—C17	1.390 (8)	N5—H5B	0.8901
C17—H17	0.9300	O2—O2^vi	1.12 (4)
C17—C18	1.385 (8)	O2—O3^vi	1.35 (2)
C18—C19	1.390 (8)	O3—O2^vi	1.35 (2)
C18—C20	1.497 (8)	O4—Cl1^v	1.890 (14)
C19—H19	0.9300	O4—Cl1	1.379 (9)
C20—C21	1.378 (8)	O5—Cl1	1.354 (14)
C20—C24	1.382 (9)	O5—Cl1^v	1.354 (14)
C21—H21	0.9300	O6—Cl1^v	1.475 (12)
C21—C22	1.399 (7)	O6—Cl1	1.369 (12)
C22—H22	0.9300	O8—O8^vi	1.81 (7)
C22—N6	1.328 (8)	Cl1—O4^v	1.890 (14)
C23—H23	0.9300	Cl1—O6^v	1.475 (12)
C23—C24	1.386 (8)	Cl1—Cl1^v	0.536 (12)
C23—N6	1.353 (8)
C2—C1—H1	118.4	C27—C28—H28B	109.5
N1—C1—H1	118.4	C27—C28—H28C	109.5
N1—C1—C2	123.2 (5)	H28A—C28—H28B	109.5
C1—C2—H2	120.3	H28A—C28—H28C	109.5
C3—C2—C1	119.5 (5)	H28B—C28—H28C	109.5
C3—C2—H2	120.3	N1^ii—Cd1—N1^i	105.9 (2)
C2—C3—C6	123.2 (5)	N1^ii—Cd1—N6	78.71 (17)
C4—C3—C2	116.1 (5)	N1^i—Cd1—N6	86.84 (17)
C4—C3—C6	120.7 (5)	N1^i—Cd1—N6^v	78.72 (17)
C3—C4—H4	119.5	N1^ii—Cd1—N6^v	86.84 (17)
C3—C4—C5	120.9 (5)	N2^iv—Cd1—N1^ii	87.95 (15)
C5—C4—H4	119.5	N2^iii—Cd1—N1^ii	159.30 (16)
C4—C5—H5	118.9	N2^iii—Cd1—N1^i	87.95 (15)
N1—C5—C4	122.2 (6)	N2^iv—Cd1—N1^i	159.30 (16)
N1—C5—H5	118.9	N2^iii—Cd1—N2^iv	83.4 (2)
C7—C6—C3	121.3 (5)	N2^iv—Cd1—N6	111.35 (15)
C11—C6—C3	120.1 (5)	N2^iii—Cd1—N6^v	111.35 (15)
C11—C6—C7	118.6 (5)	N2^iv—Cd1—N6^v	86.93 (15)
C6—C7—H7	119.9	N2^iii—Cd1—N6	86.93 (15)
C8—C7—C6	120.1 (5)	N6^v—Cd1—N6	156.0 (2)
C8—C7—H7	119.9	O1—Cl2—O1^vi	153.6 (12)
C7—C8—H8	119.6	O1—Cl2—O2	93.9 (11)
C7—C8—C9	120.7 (6)	O1^vi—Cl2—O2	110.8 (11)
C9—C8—H8	119.6	O1—Cl2—O2^vi	110.8 (11)
C8—C9—H9	120.2	O1^vi—Cl2—O2^vi	93.9 (11)
C10—C9—C8	119.5 (6)	O2—Cl2—O2^vi	45.1 (15)
C10—C9—H9	120.2	O3—Cl2—O1	97.4 (10)
C9—C10—C12	122.1 (5)	O3^vi—Cl2—O1	88.5 (10)
C11—C10—C9	118.9 (5)	O3^vi—Cl2—O1^vi	97.4 (10)
C11—C10—C12	119.0 (5)	O3—Cl2—O1^vi	88.5 (10)
C6—C11—H11	118.9	O3^vi—Cl2—O2^vi	98.4 (13)
C10—C11—C6	122.1 (5)	O3—Cl2—O2	98.4 (13)
C10—C11—H11	118.9	O3^vi—Cl2—O2	55.7 (9)
N2—C12—C10	128.8 (5)	O3—Cl2—O2^vi	55.7 (9)
N2—C12—N4	109.3 (5)	O3—Cl2—O3^vi	153.9 (16)
N4—C12—C10	121.8 (4)	O8^vi—Cl2—O1	117 (2)
N3—C13—C14	124.0 (4)	O8—Cl2—O1	38.3 (18)
N3—C13—N4	108.8 (4)	O8—Cl2—O1^vi	117 (2)
N4—C13—C14	127.2 (4)	O8^vi—Cl2—O1^vi	38.3 (18)
C15—C14—C13	117.9 (5)	O8^vi—Cl2—O2^vi	132 (2)
C15—C14—C19	119.4 (5)	O8—Cl2—O2^vi	133.0 (18)
C19—C14—C13	122.7 (5)	O8—Cl2—O2	132 (2)
C14—C15—H15	120.1	O8^vi—Cl2—O2	133.0 (18)
C14—C15—C16	119.9 (5)	O8—Cl2—O3	88.6 (14)
C16—C15—H15	120.1	O8^vi—Cl2—O3	110.9 (14)
C15—C16—H16	119.8	O8—Cl2—O3^vi	110.9 (14)
C15—C16—C17	120.5 (6)	O8^vi—Cl2—O3^vi	88.6 (14)
C17—C16—H16	119.8	O8^vi—Cl2—O8	86 (4)
C16—C17—H17	119.8	C1—N1—C5	117.7 (5)
C18—C17—C16	120.4 (6)	C1—N1—Cd1^vii	125.4 (4)
C18—C17—H17	119.8	C5—N1—Cd1^vii	114.0 (4)
C17—C18—C19	119.4 (5)	C12—N2—Cd1^viii	138.9 (4)
C17—C18—C20	121.9 (5)	C12—N2—N3	108.0 (4)
C19—C18—C20	118.7 (5)	N3—N2—Cd1^viii	110.8 (3)
C14—C19—H19	119.8	C13—N3—N2	107.6 (4)
C18—C19—C14	120.4 (5)	C12—N4—C13	106.2 (4)
C18—C19—H19	119.8	C12—N4—N5	127.7 (4)
C21—C20—C18	120.9 (5)	C13—N4—N5	126.0 (4)
C21—C20—C24	116.2 (5)	N4—N5—H5A	109.5
C24—C20—C18	122.8 (5)	N4—N5—H5B	108.8
C20—C21—H21	119.7	H5A—N5—H5B	109.5
C20—C21—C22	120.5 (6)	C22—N6—C23	116.6 (5)
C22—C21—H21	119.7	C22—N6—Cd1	127.0 (4)
C21—C22—H22	118.5	C23—N6—Cd1	116.0 (4)
N6—C22—C21	123.1 (6)	O2^vi—O2—Cl2	67.5 (8)
N6—C22—H22	118.5	O2^vi—O2—O3^vi	125.1 (14)
C24—C23—H23	118.6	O3^vi—O2—Cl2	61.6 (6)
N6—C23—H23	118.6	O2^vi—O3—Cl2	62.7 (6)
N6—C23—C24	122.8 (5)	Cl1—O4—Cl1^v	5.7 (6)
C20—C24—C23	120.6 (6)	Cl1^v—O5—Cl1	22.8 (5)
C20—C24—H24	119.7	Cl1—O6—Cl1^v	21.3 (5)
C23—C24—H24	119.7	Cl2—O8—O8^vi	47.0 (18)
H25A—C25—H25B	109.5	O4—Cl1—O4^v	152.0 (15)
H25A—C25—H25C	109.5	O4—Cl1—O6^v	109.8 (12)
H25B—C25—H25C	109.5	O5—Cl1—O4^v	67.1 (7)
C26—C25—H25A	109.5	O5—Cl1—O4	85.0 (9)
C26—C25—H25B	109.5	O5—Cl1—O6^v	117.0 (8)
C26—C25—H25C	109.5	O5—Cl1—O6	124.8 (9)
C25—C26—H26A	107.9	O6^v—Cl1—O4^v	82.2 (8)
C25—C26—H26B	107.9	O6—Cl1—O4^v	90.1 (9)
H26A—C26—H26B	107.2	O6—Cl1—O4	108.8 (12)
C27—C26—C25	118 (3)	O6—Cl1—O6^v	107.9 (6)
C27—C26—H26A	107.9	Cl1^v—Cl1—O4	160 (2)
C27—C26—H26B	107.9	Cl1^v—Cl1—O4^v	14.7 (15)
C26—C27—C28	127 (3)	Cl1^v—Cl1—O5	78.6 (3)
O7—C27—C26	123 (2)	Cl1^v—Cl1—O6^v	68 (2)
O7—C27—C28	109 (3)	Cl1^v—Cl1—O6	91 (2)
C27—C28—H28A	109.5
C1—C2—C3—C4	−5.8 (8)	Cd1^viii—N2—N3—C13	−166.4 (3)
C1—C2—C3—C6	175.1 (5)	N1—C1—C2—C3	0.6 (9)
C2—C1—N1—C5	4.8 (8)	N1^i—Cd1—N6—C22	−22.3 (5)
C2—C1—N1—Cd1^vii	−154.5 (4)	N1^ii—Cd1—N6—C22	−129.2 (5)
C2—C3—C4—C5	5.9 (9)	N1^ii—Cd1—N6—C23	58.3 (4)
C2—C3—C6—C7	17.0 (8)	N1^i—Cd1—N6—C23	165.2 (4)
C2—C3—C6—C11	−164.1 (6)	N2—C12—N4—C13	0.3 (6)
C3—C4—C5—N1	−0.7 (10)	N2—C12—N4—N5	176.5 (6)
C3—C6—C7—C8	180.0 (6)	N2^iii—Cd1—N6—C22	65.8 (5)
C3—C6—C11—C10	179.9 (5)	N2^iv—Cd1—N6—C22	147.5 (5)
C4—C3—C6—C7	−162.1 (6)	N2^iii—Cd1—N6—C23	−106.7 (4)
C4—C3—C6—C11	16.8 (8)	N2^iv—Cd1—N6—C23	−25.0 (5)
C4—C5—N1—C1	−4.7 (9)	N3—C13—C14—C15	30.8 (8)
C4—C5—N1—Cd1^vii	156.9 (5)	N3—C13—C14—C19	−149.4 (5)
C6—C3—C4—C5	−175.0 (5)	N3—C13—N4—C12	−0.4 (6)
C6—C7—C8—C9	−0.6 (11)	N3—C13—N4—N5	−176.7 (5)
C7—C6—C11—C10	−1.1 (8)	N4—C12—N2—Cd1^viii	160.1 (4)
C7—C8—C9—C10	0.2 (11)	N4—C12—N2—N3	−0.1 (6)
C8—C9—C10—C11	−0.3 (9)	N4—C13—C14—C15	−151.0 (6)
C8—C9—C10—C12	−179.4 (6)	N4—C13—C14—C19	28.8 (8)
C9—C10—C11—C6	0.7 (8)	N4—C13—N3—N2	0.4 (6)
C9—C10—C12—N2	84.9 (8)	N6—C23—C24—C20	−1.3 (10)
C9—C10—C12—N4	−99.8 (6)	N6^v—Cd1—N6—C22	−75.1 (5)
C10—C12—N2—Cd1^viii	−24.1 (9)	N6^v—Cd1—N6—C23	112.4 (4)
C10—C12—N2—N3	175.7 (5)	O1—Cl2—O2—O2^vi	116 (2)
C10—C12—N4—C13	−175.8 (5)	O1^vi—Cl2—O2—O2^vi	−74 (2)
C10—C12—N4—N5	0.4 (9)	O1—Cl2—O2—O3^vi	−85.6 (13)
C11—C6—C7—C8	1.1 (9)	O1^vi—Cl2—O2—O3^vi	84.7 (14)
C11—C10—C12—N2	−94.2 (7)	O1—Cl2—O3—O2^vi	−110.1 (14)
C11—C10—C12—N4	81.1 (7)	O1^vi—Cl2—O3—O2^vi	95.7 (14)
C12—C10—C11—C6	179.9 (5)	O1^vi—Cl2—O8—O8^vi	−23 (2)
C12—N2—N3—C13	−0.2 (6)	O1—Cl2—O8—O8^vi	145 (3)
C13—C14—C15—C16	−179.8 (6)	O2^vi—Cl2—O2—O3^vi	159 (3)
C13—C14—C19—C18	179.2 (5)	O2—Cl2—O3—O2^vi	−15 (2)
C14—C13—N3—N2	178.8 (5)	O2—Cl2—O8—O8^vi	148.9 (15)
C14—C13—N4—C12	−178.8 (5)	O2^vi—Cl2—O8—O8^vi	−148.4 (14)
C14—C13—N4—N5	4.9 (9)	O3—Cl2—O2—O2^vi	18 (2)
C14—C15—C16—C17	−0.9 (11)	O3^vi—Cl2—O2—O2^vi	−159 (3)
C15—C14—C19—C18	−1.1 (8)	O3—Cl2—O2—O3^vi	176.3 (6)
C15—C16—C17—C18	2.1 (11)	O3^vi—Cl2—O3—O2^vi	−8.2 (12)
C16—C17—C18—C19	−2.7 (10)	O3—Cl2—O8—O8^vi	−111.0 (15)
C16—C17—C18—C20	−179.3 (6)	O3^vi—Cl2—O8—O8^vi	86.9 (19)
C17—C18—C19—C14	2.2 (9)	O8—Cl2—O2—O2^vi	113 (3)
C17—C18—C20—C21	24.2 (9)	O8^vi—Cl2—O2—O2^vi	−111 (3)
C17—C18—C20—C24	−158.4 (6)	O8^vi—Cl2—O2—O3^vi	47 (3)
C18—C20—C21—C22	175.7 (6)	O8—Cl2—O2—O3^vi	−88 (2)
C18—C20—C24—C23	−174.9 (6)	O8^vi—Cl2—O3—O2^vi	127 (2)
C19—C14—C15—C16	0.4 (9)	O8—Cl2—O3—O2^vi	−147 (2)
C19—C18—C20—C21	−152.4 (6)	Cl1^v—O4—Cl1—O4^v	31 (6)
C19—C18—C20—C24	25.0 (9)	Cl1^v—O4—Cl1—O5	37 (7)
C20—C18—C19—C14	178.9 (5)	Cl1^v—O4—Cl1—O6	162 (8)
C20—C21—C22—N6	−0.2 (10)	Cl1^v—O4—Cl1—O6^v	−80 (8)
C21—C20—C24—C23	2.6 (9)	Cl1^v—O5—Cl1—O4^v	10 (3)
C21—C22—N6—C23	1.6 (9)	Cl1^v—O5—Cl1—O4	−168 (3)
C21—C22—N6—Cd1	−170.9 (5)	Cl1^v—O5—Cl1—O6^v	−58 (2)
C24—C20—C21—C22	−1.9 (9)	Cl1^v—O5—Cl1—O6	83 (3)
C24—C23—N6—C22	−0.9 (9)	Cl1^v—O6—Cl1—O4^v	−14.7 (15)
C24—C23—N6—Cd1	172.4 (5)	Cl1^v—O6—Cl1—O4	−174 (2)
C25—C26—C27—C28	−170 (2)	Cl1^v—O6—Cl1—O5	−76.5 (15)
C25—C26—C27—O7	−2 (5)	Cl1^v—O6—Cl1—O6^v	67.1 (15)

Symmetry codes: (i) y+1, x, −z; (ii) x, y+1, z; (iii) −y+1/2, x−1/2, z−1/4; (iv) x−1/2, −y+1/2, −z+1/4; (v) y, x, −z; (vi) y, x, −z+2; (vii) x, y−1, z; (viii) y+1/2, −x+1/2, z+1/4.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C28—H28B···O4^ix	0.96	2.42	3.34 (4)	161
N5—H5A···O3^x	0.89	2.46	3.027 (12)	122
N5—H5B···O4^xi	0.89	2.41	3.14 (2)	140
N5—H5B···O7^vii	0.89	2.50	2.908 (17)	109

Symmetry codes: (vii) x, y−1, z; (ix) y, x+1, −z; (x) y, x−1, −z+1; (xi) x+1/2, −y+1/2, −z+1/4.