A new three-dimensional twofold inter­penetrated cadmium(II) metal–organic framework: synthesis, structure and photoluminescence properties

The design and synthesis of metal–organic frameworks (MOFs) have attracted much inter­est due to the aesthetics of their crystalline architectures and their potential applications as new functional materials. A new twofold inter­penetrated three-dimensional (3D) MOF, namely, poly[[tri­aqua­(μ₄-(2R,2′R)-2,2′-{[1,4-phenyl­enebis(carbon­yl)]bis­(aza­nedi­yl)}dipropionato-κ⁷O¹:O¹,O^1′:O⁴:O⁴,O^4′,O^4′′)(μ₃-(2R,2′R)-2,2′-{[1,4-phenyl­enebis(carbon­yl)]bis­(aza­nedi­yl)}dipropionato-κ³O¹:O⁴:O⁴)dicadmium(II)] dihydrate], {[Cd₂(C₁₄H₁₄N₂O₆)₂(H₂O)₃]·2H₂O}_n, (I), has been synthesized by the reaction of Cd(CH₃COO)₂·2H₂O with the syn­thesized ligand (2R,2′R)-2,2′-{[1,4-phenyl­enebis(carbon­yl)]bis­(aza­nedi­yl)}di­pro­pi­onic acid (H₂L). Single-crystal X-ray diffraction analysis reveals that the carboxyl­ate groups from two crystallographically independent L²⁻ dianions link the cadmium cations into a one-dimensional helical secondary building unit (SBU). The resulting SBUs are extended into a 3D metal–organic framework via the terephthalamide moiety of the ligand as a spacer. In the crystal, two independent MOFs inter­penetrate each other, thus producing a twofold inter­penetrated 3D architecture, which shows an unprecedented 2-nodal (7,9)-connected net with the point (Schläfli) symbol (3⁷·4⁶·5⁸)(3⁸·4¹¹·5¹⁶·6). MOF (I) was further characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction and thermogravimetric analysis. The photoluminescence properties and UV–Vis absorption spectrum of (I) have also been investigated. The MOF exhibits enhanced fluorescence emission with a high photoluminescence quantum yield of 31.55% and a longer lifetime com­pared with free H₂L.

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Poly[[triaqua(µ₄-(2R,2'R)-2,2'-{[1,4-phenylenebis(carbonyl)]bis(azanediyl)}dipropionato-κ⁷O¹:O¹,O^1':O⁴:O⁴,O^4',O^4'')(µ₃-(2R,2'R)-2,2'-{[1,4-phenylenebis(carbonyl)]bis(azanediyl)}dipropionato-κ³O¹:O⁴:O⁴)dicadmium(II)] dihydrate]

Crystal data

[Cd2(C14H14N2O6)2(H2O)3]·2H2O	Dx = 1.797 Mg m^−3
Mr = 927.42	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 9942 reflections
a = 13.8013 (8) Å	θ = 2.4–27.6°
b = 14.5077 (8) Å	µ = 1.32 mm^−1
c = 17.1208 (10) Å	T = 298 K
V = 3428.0 (3) Å^3	Block, colorless
Z = 4	0.33 × 0.15 × 0.10 mm
F(000) = 1864

Data collection

Bruker APEX II CCD area detector diffractometer	7587 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.028
phi and ω scans	θmax = 27.6°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −17→17
Tmin = 0.673, Tmax = 0.876	k = −18→18
29962 measured reflections	l = −22→22
7906 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.020	w = 1/[σ^2(Fo^2) + (0.0226P)^2 + 0.6407P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.048	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.34 e Å^−3
7906 reflections	Δρmin = −0.40 e Å^−3
465 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00043 (10)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack x determined using 3249 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.011 (7)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.5901 (2)	0.3792 (2)	0.86129 (18)	0.0228 (6)
C2	0.6153 (2)	0.4766 (2)	0.89150 (18)	0.0224 (6)
H2	0.5743	0.5212	0.8640	0.027*
C3	0.6001 (3)	0.4890 (2)	0.97862 (19)	0.0327 (8)
H3A	0.6403	0.4464	1.0066	0.049*
H3B	0.5333	0.4777	0.9912	0.049*
H3C	0.6169	0.5509	0.9932	0.049*
C4	0.7425 (2)	0.5309 (2)	0.80255 (18)	0.0235 (6)
C5	0.8494 (2)	0.5413 (2)	0.79010 (18)	0.0245 (6)
C6	0.9118 (2)	0.5588 (2)	0.85164 (19)	0.0262 (7)
H6	0.8871	0.5704	0.9012	0.031*
C7	1.0103 (2)	0.5593 (2)	0.8396 (2)	0.0266 (7)
H7	1.0517	0.5721	0.8811	0.032*
C8	1.0487 (2)	0.5409 (2)	0.76630 (18)	0.0285 (6)
C9	0.9863 (3)	0.5280 (3)	0.7038 (2)	0.0358 (9)
H9	1.0111	0.5190	0.6538	0.043*
C10	0.8865 (3)	0.5285 (3)	0.7158 (2)	0.0351 (8)
H10	0.8447	0.5203	0.6738	0.042*
C11	1.1554 (2)	0.5298 (2)	0.7527 (2)	0.0321 (8)
C12	1.3128 (2)	0.4917 (3)	0.8088 (2)	0.0385 (9)
H12	1.3188	0.4352	0.7779	0.046*
C13	1.3545 (3)	0.4735 (4)	0.8899 (3)	0.0630 (15)
H13A	1.3545	0.5297	0.9195	0.095*
H13B	1.4196	0.4511	0.8850	0.095*
H13C	1.3155	0.4282	0.9161	0.095*
C14	1.3714 (2)	0.5669 (2)	0.76906 (19)	0.0269 (7)
C15	0.6211 (2)	0.6098 (2)	0.54791 (17)	0.0217 (6)
C16	0.6437 (3)	0.7105 (2)	0.52828 (18)	0.0265 (7)
H16	0.5948	0.7505	0.5522	0.032*
C17	0.7434 (3)	0.7338 (3)	0.5617 (2)	0.0361 (8)
H17A	0.7921	0.6987	0.5348	0.054*
H17B	0.7449	0.7190	0.6163	0.054*
H17C	0.7560	0.7984	0.5548	0.054*
C18	0.5640 (3)	0.7034 (2)	0.40406 (18)	0.0302 (7)
C19	0.5649 (2)	0.7118 (2)	0.31633 (18)	0.0280 (6)
C20	0.6488 (3)	0.7228 (3)	0.2738 (2)	0.0327 (8)
H20	0.7079	0.7279	0.2994	0.039*
C21	0.6455 (3)	0.7263 (3)	0.1931 (2)	0.0331 (8)
H21	0.7025	0.7332	0.1648	0.040*
C22	0.5581 (3)	0.7194 (2)	0.15437 (18)	0.0283 (7)
C23	0.4736 (3)	0.7083 (3)	0.1968 (2)	0.0394 (9)
H23	0.4144	0.7034	0.1712	0.047*
C24	0.4773 (3)	0.7044 (3)	0.2777 (2)	0.0381 (9)
H24	0.4205	0.6968	0.3061	0.046*
C25	0.5496 (3)	0.7238 (2)	0.06618 (19)	0.0335 (8)
C26	0.6232 (3)	0.7609 (3)	−0.0583 (2)	0.0348 (8)
H26	0.5963	0.7038	−0.0800	0.042*
C27	0.7247 (3)	0.7737 (4)	−0.0913 (2)	0.0611 (14)
H27A	0.7514	0.8306	−0.0724	0.092*
H27B	0.7217	0.7752	−0.1473	0.092*
H27C	0.7651	0.7233	−0.0750	0.092*
C28	0.5583 (3)	0.8409 (2)	−0.08365 (17)	0.0280 (7)
Cd1	0.56639 (2)	0.45816 (2)	0.68095 (2)	0.02414 (6)
Cd2	0.45110 (2)	0.69264 (2)	0.66575 (2)	0.02634 (6)
N1	0.71617 (18)	0.49503 (18)	0.87111 (15)	0.0235 (6)
H1	0.7605	0.4823	0.9047	0.028*
N2	1.21033 (19)	0.5145 (2)	0.81550 (19)	0.0357 (7)
H2A	1.1846	0.5183	0.8611	0.043*
N3	0.6436 (2)	0.7241 (2)	0.44399 (16)	0.0298 (7)
H3	0.6941	0.7451	0.4205	0.036*
N4	0.6272 (2)	0.7514 (2)	0.02618 (16)	0.0351 (7)
H4	0.6801	0.7637	0.0506	0.042*
O1	0.59388 (19)	0.36415 (16)	0.78920 (13)	0.0327 (6)
O2	0.68302 (16)	0.55361 (17)	0.75143 (13)	0.0296 (5)
O3	1.18961 (18)	0.5315 (2)	0.68669 (15)	0.0458 (7)
O4	1.34718 (19)	0.64928 (17)	0.77435 (14)	0.0335 (6)
O5	1.44530 (19)	0.54356 (19)	0.73188 (15)	0.0451 (6)
O6	0.56511 (17)	0.59485 (14)	0.60622 (11)	0.0243 (4)
O7	0.66298 (18)	0.54847 (16)	0.51051 (13)	0.0320 (5)
O8	0.4904 (2)	0.6762 (2)	0.43810 (16)	0.0425 (7)
O9	0.4731 (2)	0.7025 (2)	0.03471 (16)	0.0498 (7)
O10	0.5347 (2)	0.90285 (19)	−0.03889 (16)	0.0473 (7)
O14	0.68973 (19)	0.40905 (17)	0.60721 (15)	0.0362 (6)
H14A	0.6688	0.3707	0.5737	0.043*
H14B	0.7153	0.4547	0.5839	0.043*
O11	0.5321 (2)	0.83824 (18)	−0.15474 (14)	0.0431 (7)
O13	0.31060 (19)	0.64284 (18)	0.60404 (14)	0.0353 (6)
H13D	0.3225	0.5936	0.5788	0.042*
H13E	0.2672	0.6323	0.6381	0.042*
O12	0.5693 (2)	0.31825 (16)	0.90973 (13)	0.0358 (6)
O15	0.58827 (19)	0.73249 (18)	0.72968 (15)	0.0383 (6)
H15A	0.5777	0.7324	0.7786	0.046*
H15B	0.6325	0.6937	0.7191	0.046*
O16	0.6649 (2)	0.22606 (19)	0.57602 (15)	0.0404 (6)
H16A	0.6490	0.2096	0.6191	0.048*
H16B	0.6154	0.2236	0.5409	0.048*
O17	0.63733 (19)	0.04517 (19)	0.02421 (14)	0.0407 (6)
H17D	0.5938	0.0805	0.0371	0.049*
H17E	0.6079	0.0037	0.0063	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0155 (15)	0.0238 (15)	0.0290 (16)	0.0010 (12)	−0.0030 (12)	−0.0017 (12)
C2	0.0170 (15)	0.0227 (16)	0.0277 (15)	−0.0002 (12)	−0.0013 (12)	−0.0004 (12)
C3	0.0319 (19)	0.0374 (19)	0.0288 (17)	−0.0012 (15)	0.0017 (14)	−0.0064 (14)
C4	0.0185 (14)	0.0240 (15)	0.0279 (15)	−0.0020 (12)	−0.0026 (12)	−0.0017 (13)
C5	0.0183 (15)	0.0262 (15)	0.0290 (15)	−0.0025 (13)	0.0002 (12)	0.0024 (14)
C6	0.0191 (15)	0.0324 (17)	0.0272 (15)	−0.0018 (13)	−0.0008 (12)	−0.0013 (13)
C7	0.0208 (15)	0.0280 (16)	0.0309 (17)	−0.0037 (12)	−0.0054 (13)	0.0008 (13)
C8	0.0196 (15)	0.0317 (16)	0.0343 (16)	−0.0045 (15)	0.0029 (14)	0.0036 (14)
C9	0.0288 (18)	0.053 (2)	0.0257 (16)	−0.0074 (17)	0.0046 (14)	0.0012 (16)
C10	0.0276 (18)	0.051 (2)	0.0268 (17)	−0.0072 (16)	−0.0049 (14)	0.0027 (16)
C11	0.0222 (17)	0.0341 (19)	0.0399 (19)	−0.0059 (14)	0.0056 (14)	−0.0010 (16)
C12	0.0198 (16)	0.0338 (17)	0.062 (3)	0.0014 (14)	0.0105 (17)	0.0043 (17)
C13	0.024 (2)	0.077 (3)	0.088 (3)	0.003 (2)	0.001 (2)	0.054 (3)
C14	0.0175 (16)	0.0380 (19)	0.0252 (16)	0.0003 (13)	0.0007 (13)	0.0016 (13)
C15	0.0231 (16)	0.0248 (15)	0.0172 (13)	−0.0011 (12)	−0.0006 (12)	0.0009 (12)
C16	0.0321 (18)	0.0249 (16)	0.0226 (15)	−0.0005 (13)	0.0068 (13)	0.0012 (12)
C17	0.039 (2)	0.039 (2)	0.0298 (18)	−0.0123 (17)	0.0015 (16)	−0.0011 (15)
C18	0.0330 (18)	0.0285 (16)	0.0291 (15)	0.0024 (16)	0.0054 (15)	0.0063 (12)
C19	0.0287 (16)	0.0280 (15)	0.0273 (15)	0.0007 (13)	−0.0008 (15)	0.0054 (12)
C20	0.0260 (18)	0.045 (2)	0.0266 (17)	−0.0005 (15)	−0.0027 (15)	0.0019 (15)
C21	0.0289 (18)	0.044 (2)	0.0261 (17)	0.0007 (15)	0.0020 (14)	0.0022 (15)
C22	0.0322 (18)	0.0268 (15)	0.0259 (14)	0.0032 (13)	0.0002 (15)	0.0011 (12)
C23	0.0251 (18)	0.055 (2)	0.038 (2)	−0.0019 (16)	−0.0069 (15)	0.0076 (17)
C24	0.0281 (19)	0.051 (2)	0.0350 (19)	−0.0039 (17)	0.0052 (15)	0.0076 (17)
C25	0.035 (2)	0.0375 (18)	0.0277 (16)	0.0087 (16)	−0.0067 (17)	0.0021 (13)
C26	0.037 (2)	0.042 (2)	0.0249 (17)	0.0140 (17)	−0.0041 (15)	−0.0013 (15)
C27	0.037 (2)	0.113 (4)	0.034 (2)	0.023 (3)	0.0020 (18)	0.004 (2)
C28	0.0265 (17)	0.0314 (16)	0.0261 (14)	0.0012 (14)	−0.0021 (15)	−0.0011 (12)
Cd1	0.02322 (11)	0.02370 (10)	0.02549 (11)	−0.00043 (9)	0.00154 (9)	0.00060 (8)
Cd2	0.02356 (12)	0.02722 (11)	0.02824 (11)	0.00393 (9)	0.00023 (9)	0.00367 (9)
N1	0.0159 (13)	0.0270 (13)	0.0276 (14)	−0.0033 (11)	−0.0040 (10)	0.0030 (11)
N2	0.0160 (13)	0.0474 (17)	0.0438 (18)	0.0012 (11)	0.0057 (13)	0.0086 (15)
N3	0.0293 (16)	0.0366 (16)	0.0236 (14)	−0.0038 (13)	0.0047 (12)	0.0095 (12)
N4	0.0328 (17)	0.0494 (19)	0.0231 (14)	0.0072 (14)	−0.0071 (12)	0.0039 (13)
O1	0.0426 (16)	0.0285 (12)	0.0270 (12)	−0.0039 (11)	−0.0032 (10)	−0.0041 (9)
O2	0.0211 (11)	0.0342 (12)	0.0336 (12)	−0.0026 (10)	−0.0064 (10)	0.0054 (10)
O3	0.0301 (13)	0.0655 (18)	0.0419 (15)	−0.0099 (13)	0.0131 (12)	−0.0043 (14)
O4	0.0353 (14)	0.0301 (12)	0.0349 (13)	0.0005 (11)	0.0078 (11)	0.0013 (10)
O5	0.0312 (14)	0.0502 (15)	0.0540 (15)	0.0098 (14)	0.0221 (13)	0.0097 (13)
O6	0.0271 (12)	0.0251 (10)	0.0206 (9)	0.0007 (10)	0.0056 (10)	0.0001 (8)
O7	0.0399 (14)	0.0266 (11)	0.0296 (11)	0.0037 (11)	0.0137 (10)	−0.0007 (10)
O8	0.0318 (14)	0.0573 (18)	0.0385 (14)	−0.0081 (13)	0.0095 (11)	0.0058 (13)
O9	0.0383 (16)	0.074 (2)	0.0372 (14)	−0.0037 (15)	−0.0142 (12)	0.0030 (14)
O10	0.0557 (19)	0.0402 (14)	0.0461 (15)	0.0131 (13)	−0.0082 (14)	−0.0153 (12)
O14	0.0340 (14)	0.0347 (13)	0.0399 (14)	0.0037 (11)	0.0062 (12)	0.0005 (11)
O11	0.0538 (17)	0.0484 (15)	0.0270 (12)	0.0216 (13)	−0.0102 (12)	−0.0010 (11)
O13	0.0313 (14)	0.0444 (15)	0.0302 (12)	−0.0018 (12)	0.0024 (11)	0.0010 (11)
O12	0.0486 (15)	0.0255 (12)	0.0334 (12)	−0.0100 (12)	0.0000 (12)	0.0025 (9)
O15	0.0380 (15)	0.0421 (14)	0.0349 (13)	0.0102 (12)	−0.0068 (11)	−0.0102 (11)
O16	0.0390 (15)	0.0512 (16)	0.0309 (13)	−0.0086 (13)	−0.0023 (12)	0.0038 (12)
O17	0.0367 (14)	0.0425 (14)	0.0428 (14)	0.0033 (13)	0.0005 (11)	−0.0019 (13)

Geometric parameters (Å, º)

C1—O12	1.246 (4)	C21—C22	1.381 (5)
C1—O1	1.255 (4)	C21—H21	0.9300
C1—C2	1.543 (4)	C22—C23	1.384 (5)
C2—N1	1.460 (4)	C22—C25	1.516 (4)
C2—C3	1.517 (4)	C23—C24	1.386 (5)
C2—H2	0.9800	C23—H23	0.9300
C3—H3A	0.9600	C24—H24	0.9300
C3—H3B	0.9600	C25—O9	1.225 (5)
C3—H3C	0.9600	C25—N4	1.333 (5)
C4—O2	1.244 (4)	C26—N4	1.454 (4)
C4—N1	1.334 (4)	C26—C27	1.522 (6)
C4—C5	1.499 (4)	C26—C28	1.530 (5)
C5—C10	1.384 (5)	C26—H26	0.9800
C5—C6	1.385 (4)	C27—H27A	0.9600
C6—C7	1.374 (4)	C27—H27B	0.9600
C6—H6	0.9300	C27—H27C	0.9600
C7—C8	1.389 (5)	C28—O10	1.225 (4)
C7—H7	0.9300	C28—O11	1.270 (4)
C8—C9	1.387 (5)	Cd1—O14	2.236 (2)
C8—C11	1.499 (5)	Cd1—O11^i	2.253 (2)
C9—C10	1.392 (5)	Cd1—O5^ii	2.256 (2)
C9—H9	0.9300	Cd1—O1	2.332 (2)
C10—H10	0.9300	Cd1—O6	2.360 (2)
C11—O3	1.225 (4)	Cd1—O2	2.442 (2)
C11—N2	1.334 (5)	Cd2—O12^iii	2.252 (2)
C12—N2	1.457 (4)	Cd2—O15	2.262 (3)
C12—C14	1.519 (5)	Cd2—O13	2.323 (3)
C12—C13	1.525 (6)	Cd2—O6	2.351 (2)
C12—H12	0.9800	Cd2—O4^ii	2.431 (2)
C13—H13A	0.9600	Cd2—O5^ii	2.442 (3)
C13—H13B	0.9600	Cd1—O3^iii	2.678 (2)
C13—H13C	0.9600	N1—H1	0.8600
C14—O4	1.244 (4)	N2—H2A	0.8600
C14—O5	1.249 (4)	N3—H3	0.8600
C15—O7	1.239 (4)	N4—H4	0.8600
C15—O6	1.281 (4)	O4—Cd2^iv	2.431 (2)
C15—C16	1.530 (4)	O5—Cd1^iv	2.256 (2)
C16—N3	1.457 (4)	O5—Cd2^iv	2.443 (3)
C16—C17	1.529 (5)	O14—H14A	0.8499
C16—H16	0.9800	O14—H14B	0.8501
C17—H17A	0.9600	O11—Cd1^v	2.253 (2)
C17—H17B	0.9600	O13—H13D	0.8500
C17—H17C	0.9600	O13—H13E	0.8500
C18—O8	1.236 (4)	O12—Cd2^vi	2.252 (2)
C18—N3	1.328 (5)	O15—H15A	0.8500
C18—C19	1.507 (4)	O15—H15B	0.8500
C19—C20	1.378 (5)	O16—H16A	0.8064
C19—C24	1.382 (5)	O16—H16B	0.9115
C20—C21	1.382 (5)	O17—H17D	0.8209
C20—H20	0.9300	O17—H17E	0.7878
O12—C1—O1	122.7 (3)	C24—C23—H23	120.1
O12—C1—C2	118.6 (3)	C19—C24—C23	120.5 (3)
O1—C1—C2	118.7 (3)	C19—C24—H24	119.7
N1—C2—C3	110.2 (3)	C23—C24—H24	119.7
N1—C2—C1	107.6 (2)	O9—C25—N4	122.8 (3)
C3—C2—C1	114.0 (3)	O9—C25—C22	119.6 (3)
N1—C2—H2	108.3	N4—C25—C22	117.5 (3)
C3—C2—H2	108.3	N4—C26—C27	110.2 (3)
C1—C2—H2	108.3	N4—C26—C28	112.1 (3)
C2—C3—H3A	109.5	C27—C26—C28	109.9 (3)
C2—C3—H3B	109.5	N4—C26—H26	108.1
H3A—C3—H3B	109.5	C27—C26—H26	108.1
C2—C3—H3C	109.5	C28—C26—H26	108.1
H3A—C3—H3C	109.5	C26—C27—H27A	109.5
H3B—C3—H3C	109.5	C26—C27—H27B	109.5
O2—C4—N1	122.9 (3)	H27A—C27—H27B	109.5
O2—C4—C5	121.5 (3)	C26—C27—H27C	109.5
N1—C4—C5	115.6 (3)	H27A—C27—H27C	109.5
C10—C5—C6	119.6 (3)	H27B—C27—H27C	109.5
C10—C5—C4	118.8 (3)	O10—C28—O11	123.1 (3)
C6—C5—C4	121.5 (3)	O10—C28—C26	122.3 (3)
C7—C6—C5	120.1 (3)	O11—C28—C26	114.5 (3)
C7—C6—H6	119.9	O14—Cd1—O11^i	95.79 (10)
C5—C6—H6	119.9	O14—Cd1—O5^ii	163.20 (9)
C6—C7—C8	120.8 (3)	O11^i—Cd1—O5^ii	93.10 (11)
C6—C7—H7	119.6	O14—Cd1—O1	97.96 (9)
C8—C7—H7	119.6	O11^i—Cd1—O1	78.75 (9)
C9—C8—C7	119.1 (3)	O5^ii—Cd1—O1	97.73 (9)
C9—C8—C11	118.4 (3)	O14—Cd1—O6	88.13 (8)
C7—C8—C11	122.4 (3)	O11^i—Cd1—O6	122.44 (8)
C8—C9—C10	120.0 (3)	O5^ii—Cd1—O6	75.07 (8)
C8—C9—H9	120.0	O1—Cd1—O6	157.43 (8)
C10—C9—H9	120.0	O14—Cd1—O2	87.59 (9)
C5—C10—C9	120.2 (3)	O11^i—Cd1—O2	159.06 (8)
C5—C10—H10	119.9	O5^ii—Cd1—O2	89.19 (10)
C9—C10—H10	119.9	O1—Cd1—O2	80.31 (8)
O3—C11—N2	121.8 (3)	O6—Cd1—O2	78.25 (8)
O3—C11—C8	121.3 (3)	O12^iii—Cd2—O15	100.10 (10)
N2—C11—C8	116.8 (3)	O12^iii—Cd2—O13	83.49 (10)
N2—C12—C14	112.9 (3)	O15—Cd2—O13	176.41 (9)
N2—C12—C13	109.5 (3)	O12^iii—Cd2—O6	108.85 (8)
C14—C12—C13	109.4 (3)	O15—Cd2—O6	78.69 (8)
N2—C12—H12	108.3	O13—Cd2—O6	100.01 (9)
C14—C12—H12	108.3	O12^iii—Cd2—O4^ii	125.08 (9)
C13—C12—H12	108.3	O15—Cd2—O4^ii	100.94 (9)
C12—C13—H13A	109.5	O13—Cd2—O4^ii	77.00 (9)
C12—C13—H13B	109.5	O6—Cd2—O4^ii	124.77 (8)
H13A—C13—H13B	109.5	O12^iii—Cd2—O5^ii	168.13 (10)
C12—C13—H13C	109.5	O15—Cd2—O5^ii	91.69 (10)
H13A—C13—H13C	109.5	O13—Cd2—O5^ii	84.72 (10)
H13B—C13—H13C	109.5	O6—Cd2—O5^ii	71.85 (7)
O4—C14—O5	121.1 (3)	O4^ii—Cd2—O5^ii	52.91 (8)
O4—C14—C12	120.9 (3)	C4—N1—C2	122.8 (3)
O5—C14—C12	117.9 (3)	C4—N1—H1	118.6
O7—C15—O6	124.2 (3)	C2—N1—H1	118.6
O7—C15—C16	118.5 (3)	C11—N2—C12	121.8 (3)
O6—C15—C16	117.1 (3)	C11—N2—H2A	119.1
N3—C16—C17	110.0 (3)	C12—N2—H2A	119.1
N3—C16—C15	110.3 (3)	C18—N3—C16	118.7 (3)
C17—C16—C15	108.2 (3)	C18—N3—H3	120.7
N3—C16—H16	109.4	C16—N3—H3	120.7
C17—C16—H16	109.4	C25—N4—C26	120.6 (3)
C15—C16—H16	109.4	C25—N4—H4	119.7
C16—C17—H17A	109.5	C26—N4—H4	119.7
C16—C17—H17B	109.5	C1—O1—Cd1	132.3 (2)
H17A—C17—H17B	109.5	C4—O2—Cd1	129.2 (2)
C16—C17—H17C	109.5	C14—O4—Cd2^iv	92.0 (2)
H17A—C17—H17C	109.5	C14—O5—Cd1^iv	162.0 (2)
H17B—C17—H17C	109.5	C14—O5—Cd2^iv	91.3 (2)
O8—C18—N3	120.6 (3)	Cd1^iv—O5—Cd2^iv	106.43 (9)
O8—C18—C19	120.1 (3)	C15—O6—Cd2	129.75 (19)
N3—C18—C19	119.2 (3)	C15—O6—Cd1	124.07 (19)
C20—C19—C24	119.4 (3)	Cd2—O6—Cd1	106.09 (8)
C20—C19—C18	122.9 (3)	Cd1—O14—H14A	109.3
C24—C19—C18	117.7 (3)	Cd1—O14—H14B	109.4
C19—C20—C21	120.3 (3)	H14A—O14—H14B	109.5
C19—C20—H20	119.8	C28—O11—Cd1^v	109.8 (2)
C21—C20—H20	119.8	Cd2—O13—H13D	109.3
C22—C21—C20	120.4 (3)	Cd2—O13—H13E	109.4
C22—C21—H21	119.8	H13D—O13—H13E	109.5
C20—C21—H21	119.8	C1—O12—Cd2^vi	102.79 (19)
C21—C22—C23	119.5 (3)	Cd2—O15—H15A	109.4
C21—C22—C25	122.9 (3)	Cd2—O15—H15B	109.2
C23—C22—C25	117.6 (3)	H15A—O15—H15B	109.5
C22—C23—C24	119.9 (4)	H16A—O16—H16B	112.8
C22—C23—H23	120.1	H17D—O17—H17E	101.8
O12—C1—C2—N1	115.8 (3)	C22—C23—C24—C19	0.1 (6)
O1—C1—C2—N1	−62.3 (4)	C21—C22—C25—O9	168.1 (3)
O12—C1—C2—C3	−6.7 (4)	C23—C22—C25—O9	−12.1 (5)
O1—C1—C2—C3	175.1 (3)	C21—C22—C25—N4	−12.0 (5)
O2—C4—C5—C10	−34.0 (5)	C23—C22—C25—N4	167.9 (3)
N1—C4—C5—C10	145.2 (3)	N4—C26—C28—O10	18.0 (5)
O2—C4—C5—C6	149.1 (3)	C27—C26—C28—O10	−104.9 (4)
N1—C4—C5—C6	−31.7 (4)	N4—C26—C28—O11	−162.7 (3)
C10—C5—C6—C7	−3.1 (5)	C27—C26—C28—O11	74.3 (4)
C4—C5—C6—C7	173.8 (3)	O2—C4—N1—C2	1.9 (5)
C5—C6—C7—C8	−1.0 (5)	C5—C4—N1—C2	−177.3 (3)
C6—C7—C8—C9	4.3 (5)	C3—C2—N1—C4	−148.0 (3)
C6—C7—C8—C11	−172.7 (3)	C1—C2—N1—C4	87.1 (3)
C7—C8—C9—C10	−3.6 (6)	O3—C11—N2—C12	−5.0 (6)
C11—C8—C9—C10	173.5 (3)	C8—C11—N2—C12	172.5 (3)
C6—C5—C10—C9	3.8 (6)	C14—C12—N2—C11	60.8 (5)
C4—C5—C10—C9	−173.2 (3)	C13—C12—N2—C11	−177.1 (4)
C8—C9—C10—C5	−0.4 (6)	O8—C18—N3—C16	2.5 (5)
C9—C8—C11—O3	17.4 (6)	C19—C18—N3—C16	−176.4 (3)
C7—C8—C11—O3	−165.7 (3)	C17—C16—N3—C18	177.2 (3)
C9—C8—C11—N2	−160.1 (3)	C15—C16—N3—C18	57.9 (4)
C7—C8—C11—N2	16.8 (5)	O9—C25—N4—C26	2.4 (6)
N2—C12—C14—O4	30.0 (5)	C22—C25—N4—C26	−177.5 (3)
C13—C12—C14—O4	−92.2 (4)	C27—C26—N4—C25	−168.4 (4)
N2—C12—C14—O5	−151.0 (3)	C28—C26—N4—C25	68.8 (5)
C13—C12—C14—O5	86.8 (4)	O12—C1—O1—Cd1	150.7 (3)
O7—C15—C16—N3	45.3 (4)	C2—C1—O1—Cd1	−31.2 (5)
O6—C15—C16—N3	−139.7 (3)	N1—C4—O2—Cd1	−61.7 (4)
O7—C15—C16—C17	−75.0 (4)	C5—C4—O2—Cd1	117.5 (3)
O6—C15—C16—C17	100.0 (3)	O5—C14—O4—Cd2^iv	16.8 (4)
O8—C18—C19—C20	−166.1 (3)	C12—C14—O4—Cd2^iv	−164.3 (3)
N3—C18—C19—C20	12.8 (5)	O4—C14—O5—Cd1^iv	173.4 (6)
O8—C18—C19—C24	11.4 (5)	C12—C14—O5—Cd1^iv	−5.6 (10)
N3—C18—C19—C24	−169.7 (3)	O4—C14—O5—Cd2^iv	−16.7 (3)
C24—C19—C20—C21	−0.1 (5)	C12—C14—O5—Cd2^iv	164.3 (3)
C18—C19—C20—C21	177.3 (3)	O7—C15—O6—Cd2	−163.5 (2)
C19—C20—C21—C22	0.5 (6)	C16—C15—O6—Cd2	21.8 (4)
C20—C21—C22—C23	−0.5 (5)	O7—C15—O6—Cd1	20.5 (4)
C20—C21—C22—C25	179.3 (3)	C16—C15—O6—Cd1	−154.2 (2)
C21—C22—C23—C24	0.3 (6)	O10—C28—O11—Cd1^v	−2.5 (5)
C25—C22—C23—C24	−179.6 (4)	C26—C28—O11—Cd1^v	178.2 (2)
C20—C19—C24—C23	−0.2 (6)	O1—C1—O12—Cd2^vi	1.4 (4)
C18—C19—C24—C23	−177.7 (4)	C2—C1—O12—Cd2^vi	−176.7 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21···O16^vii	0.93	2.45	3.368 (5)	169
O17—H17E···O10^viii	0.79	1.94	2.727 (4)	179
O17—H17D···O8^i	0.82	1.86	2.672 (4)	170
O16—H16B···O9^i	0.91	1.81	2.710 (4)	171
O16—H16A···O4^ix	0.81	2.02	2.798 (4)	161
O15—H15B···O2	0.85	2.22	2.930 (3)	141
O15—H15A···O11^x	0.85	2.01	2.621 (3)	128
O13—H13E···O3^ii	0.85	1.99	2.720 (4)	143
O13—H13D···O17^v	0.85	1.98	2.710 (4)	144
O14—H14B···O7	0.85	1.99	2.640 (3)	133
O14—H14A···O16	0.85	2.10	2.729 (4)	131
N4—H4···O16^vii	0.86	2.19	3.011 (4)	160
N3—H3···O13^xi	0.86	2.33	3.117 (4)	153
N2—H2A···O17^xii	0.86	2.26	3.049 (4)	152
N1—H1···O7^xiii	0.86	2.14	2.979 (3)	164

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x−1, y, z; (v) −x+1, y+1/2, −z+1/2; (vii) −x+3/2, −y+1, z−1/2; (viii) x, y−1, z; (ix) −x+2, y−1/2, −z+3/2; (x) x, y, z+1; (xi) x+1/2, −y+3/2, −z+1; (xii) x+1/2, −y+1/2, −z+1; (xiii) −x+3/2, −y+1, z+1/2.