Cd^II-based com­pound as a multi-responsive fluorescent probe for sensing Fe^III cations and Cr^VI oxyanions

A new luminescent Cd^II com­pound, poly[[μ₂-1,4-bis­(1H-imidazol-1-yl)ben­zene]{μ₂-5-[(3-carboxyl­phen­oxy)meth­yl]isophthalato}cadmium(II)], [Cd(C₁₆H₁₀O₇)(C₁₂H₁₀N₄)]_n or [Cd(HL)(1,4-bib)]_n {H₃L is 5-[(3-carb­oxy­phen­oxy)meth­yl]isophthalic acid and 1,4-bib is 1,4-bis­(1H-imidazol-1-yl)benzene}, I, has been synthesized successfully from Cd^II and a semirigid tri­carb­oxy­lic ligand under hydro­thermal conditions. Structure analysis shows that I is a two-dimensional structure with the point symbol {4⁴.6²}. The three-dimensional framework is constructed by O—H...O hydrogen bonds and π–π stacking inter­actions. Furthermore, the obtained Cd^II com­pound displays high solvent stability and excellent thermal stability, as shown by powder X-ray diffraction and thermogravimetry measurements. Studies of the luminescence properties reveal that com­pound I can act as a promising luminescent sensor for detecting Fe^III cations and Cr^VI oxyanions with high selectivity and low detection limits (0.19 µM for Fe³⁺ and 1.13 µM for Cr₂O₇²⁻), and is additionally free from the inter­ference of other ions. The mechanism of selective quenching was studied by measuring the UV–Vis absorption of the host com­pound and the target analytes.

Computing details

For both structures, data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b).

5-[(3-Carboxyphenoxy)methyl]benzene-1,3-dicarboxylic acid (H3L)

Crystal data

C16H12O7	F(000) = 656
Mr = 316.26	Dx = 1.513 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.4465 (4) Å	Cell parameters from 5645 reflections
b = 8.0745 (5) Å	θ = 2.8–33.4°
c = 23.1600 (13) Å	µ = 0.12 mm^−1
β = 94.310 (2)°	T = 298 K
V = 1388.60 (14) Å^3	Needle, colorless
Z = 4	0.30 × 0.10 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer	3308 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.047
Absorption correction: multi-scan (SADABS; Bruker, 2001)	θmax = 33.7°, θmin = 3.1°
Tmin = 0.690, Tmax = 0.747	h = −11→11
18647 measured reflections	k = −12→10
5480 independent reflections	l = −36→31

Refinement

Refinement on F^2	3 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.063	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.147	w = 1/[σ^2(Fo^2) + (0.0425P)^2 + 1.0066P] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max < 0.001
5480 reflections	Δρmax = 0.36 e Å^−3
217 parameters	Δρmin = −0.26 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. Single-crystal diffraction data of H₃L and compound I were collected on a Bruker Smart APEXII CCD diffractometer using graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) at room temperature. All structures were solved via direct methods employed in SHELXT2014 and SHELXL2018, and refined based on F² with full-matrix least-squares techniques (Sheldrick et al., 2015a,b).

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

	x	y	z	Uiso*/Ueq
O1	0.3392 (2)	0.77971 (16)	0.18188 (6)	0.0506 (4)
H1A	0.396 (3)	0.866 (2)	0.1754 (12)	0.076*
O2	0.3189 (2)	0.74442 (15)	0.08608 (5)	0.0408 (3)
O3	0.0650 (2)	0.20701 (18)	0.01144 (6)	0.0522 (4)
H3A	0.043 (4)	0.138 (3)	−0.0144 (9)	0.078*
O4	−0.0070 (2)	0.01071 (16)	0.07338 (6)	0.0484 (4)
O5	0.2174 (2)	0.08550 (14)	0.27862 (5)	0.0396 (3)
O6	0.4711 (2)	−0.45727 (17)	0.33220 (6)	0.0503 (4)
O7	0.5240 (2)	−0.45550 (18)	0.42805 (7)	0.0551 (4)
H7A	0.570 (4)	−0.5481 (19)	0.4248 (12)	0.083*
C1	0.2989 (2)	0.6939 (2)	0.13584 (7)	0.0295 (3)
C2	0.2259 (2)	0.52612 (18)	0.14653 (6)	0.0250 (3)
C3	0.2232 (2)	0.46769 (18)	0.20315 (6)	0.0260 (3)
H3	0.264338	0.535303	0.233857	0.031*
C4	0.1600 (2)	0.31030 (19)	0.21429 (6)	0.0257 (3)
C5	0.1010 (2)	0.20930 (19)	0.16786 (7)	0.0284 (3)
H5	0.058364	0.103441	0.174785	0.034*
C6	0.1056 (2)	0.26583 (19)	0.11120 (6)	0.0269 (3)
C7	0.1665 (2)	0.42518 (19)	0.10029 (7)	0.0273 (3)
H7	0.167423	0.463673	0.062462	0.033*
C8	0.0499 (2)	0.1524 (2)	0.06253 (7)	0.0317 (3)
C9	0.1566 (3)	0.2526 (2)	0.27577 (7)	0.0317 (3)
H9A	0.234607	0.321666	0.301096	0.038*
H9B	0.035264	0.259795	0.288117	0.038*
C10	0.2627 (2)	0.0185 (2)	0.33211 (6)	0.0281 (3)
C11	0.2447 (2)	0.0981 (2)	0.38461 (7)	0.0334 (4)
H11	0.197521	0.204680	0.385384	0.040*
C12	0.2980 (3)	0.0167 (2)	0.43584 (7)	0.0384 (4)
H12	0.286816	0.070232	0.470943	0.046*
C13	0.3671 (2)	−0.1417 (2)	0.43591 (7)	0.0358 (4)
H13	0.401656	−0.195021	0.470574	0.043*
C14	0.3843 (2)	−0.2205 (2)	0.38303 (7)	0.0282 (3)
C15	0.3324 (2)	−0.1406 (2)	0.33141 (7)	0.0284 (3)
H15	0.344426	−0.193821	0.296296	0.034*
C16	0.4633 (2)	−0.3886 (2)	0.38002 (7)	0.0318 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0890 (12)	0.0330 (7)	0.0301 (7)	−0.0272 (7)	0.0069 (7)	−0.0068 (5)
O2	0.0622 (9)	0.0327 (6)	0.0274 (6)	−0.0094 (6)	0.0026 (6)	0.0019 (5)
O3	0.0877 (11)	0.0434 (8)	0.0249 (6)	−0.0253 (8)	0.0004 (7)	−0.0086 (5)
O4	0.0796 (11)	0.0310 (7)	0.0342 (7)	−0.0183 (7)	0.0017 (7)	−0.0084 (5)
O5	0.0700 (9)	0.0262 (6)	0.0220 (5)	0.0089 (6)	−0.0005 (5)	0.0017 (4)
O6	0.0671 (10)	0.0376 (7)	0.0433 (8)	0.0176 (7)	−0.0143 (7)	−0.0099 (6)
O7	0.0785 (11)	0.0410 (8)	0.0435 (8)	0.0169 (8)	−0.0112 (7)	0.0100 (6)
C1	0.0367 (9)	0.0249 (7)	0.0265 (7)	−0.0021 (6)	−0.0003 (6)	−0.0022 (6)
C2	0.0295 (8)	0.0216 (6)	0.0237 (7)	−0.0004 (6)	0.0007 (6)	−0.0019 (5)
C3	0.0320 (8)	0.0230 (7)	0.0226 (7)	0.0009 (6)	−0.0008 (6)	−0.0031 (5)
C4	0.0305 (8)	0.0242 (7)	0.0222 (7)	0.0007 (6)	0.0002 (6)	−0.0009 (5)
C5	0.0357 (8)	0.0227 (7)	0.0266 (7)	−0.0024 (6)	0.0009 (6)	−0.0020 (5)
C6	0.0314 (8)	0.0253 (7)	0.0237 (7)	−0.0025 (6)	−0.0008 (6)	−0.0054 (5)
C7	0.0332 (8)	0.0260 (7)	0.0226 (7)	−0.0007 (6)	0.0008 (6)	−0.0028 (5)
C8	0.0407 (9)	0.0284 (8)	0.0255 (7)	−0.0055 (7)	−0.0007 (6)	−0.0056 (6)
C9	0.0464 (10)	0.0238 (7)	0.0248 (7)	−0.0006 (7)	0.0021 (7)	0.0004 (6)
C10	0.0357 (8)	0.0276 (7)	0.0210 (7)	−0.0010 (6)	0.0016 (6)	0.0015 (5)
C11	0.0429 (10)	0.0309 (8)	0.0269 (8)	0.0048 (7)	0.0053 (7)	−0.0023 (6)
C12	0.0526 (11)	0.0423 (10)	0.0208 (7)	0.0056 (8)	0.0052 (7)	−0.0029 (7)
C13	0.0437 (10)	0.0417 (9)	0.0216 (7)	0.0029 (8)	−0.0002 (7)	0.0041 (6)
C14	0.0296 (8)	0.0282 (7)	0.0264 (7)	−0.0011 (6)	0.0001 (6)	0.0013 (6)
C15	0.0354 (8)	0.0281 (7)	0.0215 (7)	0.0011 (6)	0.0014 (6)	−0.0017 (5)
C16	0.0348 (8)	0.0301 (8)	0.0296 (8)	0.0010 (7)	−0.0039 (6)	0.0031 (6)

Geometric parameters (Å, º)

O1—C1	1.2882 (19)	C5—C6	1.392 (2)
O1—H1A	0.831 (10)	C5—H5	0.9300
O2—C1	1.242 (2)	C6—C7	1.394 (2)
O3—C8	1.276 (2)	C6—C8	1.487 (2)
O3—H3A	0.827 (10)	C7—H7	0.9300
O4—C8	1.252 (2)	C9—H9A	0.9700
O5—C10	1.3704 (18)	C9—H9B	0.9700
O5—C9	1.423 (2)	C10—C11	1.391 (2)
O6—C16	1.244 (2)	C10—C15	1.386 (2)
O7—C16	1.288 (2)	C11—C12	1.388 (2)
O7—H7A	0.827 (10)	C11—H11	0.9300
C1—C2	1.487 (2)	C12—C13	1.379 (3)
C2—C7	1.391 (2)	C12—H12	0.9300
C2—C3	1.395 (2)	C13—C14	1.394 (2)
C3—C4	1.386 (2)	C13—H13	0.9300
C3—H3	0.9300	C14—C15	1.388 (2)
C4—C5	1.394 (2)	C14—C16	1.483 (2)
C4—C9	1.500 (2)	C15—H15	0.9300
C1—O1—H1A	112.9 (19)	O5—C9—C4	108.09 (13)
C8—O3—H3A	114.4 (19)	O5—C9—H9A	110.1
C10—O5—C9	118.16 (12)	C4—C9—H9A	110.1
C16—O7—H7A	115 (2)	O5—C9—H9B	110.1
O2—C1—O1	123.68 (15)	C4—C9—H9B	110.1
O2—C1—C2	121.63 (14)	H9A—C9—H9B	108.4
O1—C1—C2	114.69 (14)	O5—C10—C11	125.06 (15)
C7—C2—C3	119.94 (14)	O5—C10—C15	114.97 (13)
C7—C2—C1	120.30 (14)	C11—C10—C15	119.97 (14)
C3—C2—C1	119.72 (13)	C10—C11—C12	119.22 (16)
C4—C3—C2	120.93 (14)	C10—C11—H11	120.4
C4—C3—H3	119.5	C12—C11—H11	120.4
C2—C3—H3	119.5	C13—C12—C11	121.55 (16)
C3—C4—C5	118.98 (14)	C13—C12—H12	119.2
C3—C4—C9	119.44 (14)	C11—C12—H12	119.2
C5—C4—C9	121.58 (14)	C12—C13—C14	118.77 (15)
C4—C5—C6	120.45 (14)	C12—C13—H13	120.6
C4—C5—H5	119.8	C14—C13—H13	120.6
C6—C5—H5	119.8	C15—C14—C13	120.42 (15)
C7—C6—C5	120.32 (14)	C15—C14—C16	118.09 (14)
C7—C6—C8	120.48 (14)	C13—C14—C16	121.46 (14)
C5—C6—C8	119.17 (14)	C14—C15—C10	120.08 (14)
C2—C7—C6	119.36 (14)	C14—C15—H15	120.0
C2—C7—H7	120.3	C10—C15—H15	120.0
C6—C7—H7	120.3	O6—C16—O7	123.06 (17)
O4—C8—O3	123.84 (15)	O6—C16—C14	119.67 (15)
O4—C8—C6	119.34 (15)	O7—C16—C14	117.26 (15)
O3—C8—C6	116.82 (15)
O2—C1—C2—C7	−4.4 (3)	C10—O5—C9—C4	166.10 (14)
O1—C1—C2—C7	175.92 (16)	C3—C4—C9—O5	−137.88 (15)
O2—C1—C2—C3	173.33 (16)	C5—C4—C9—O5	42.1 (2)
O1—C1—C2—C3	−6.4 (2)	C9—O5—C10—C11	3.8 (3)
C7—C2—C3—C4	−0.7 (2)	C9—O5—C10—C15	−175.74 (15)
C1—C2—C3—C4	−178.43 (15)	O5—C10—C11—C12	−179.18 (17)
C2—C3—C4—C5	0.9 (2)	C15—C10—C11—C12	0.3 (3)
C2—C3—C4—C9	−179.14 (15)	C10—C11—C12—C13	−0.5 (3)
C3—C4—C5—C6	0.0 (2)	C11—C12—C13—C14	0.4 (3)
C9—C4—C5—C6	−179.99 (15)	C12—C13—C14—C15	−0.1 (3)
C4—C5—C6—C7	−1.0 (2)	C12—C13—C14—C16	177.92 (17)
C4—C5—C6—C8	177.14 (15)	C13—C14—C15—C10	−0.1 (3)
C3—C2—C7—C6	−0.3 (2)	C16—C14—C15—C10	−178.17 (15)
C1—C2—C7—C6	177.37 (15)	O5—C10—C15—C14	179.50 (15)
C5—C6—C7—C2	1.2 (2)	C11—C10—C15—C14	0.0 (3)
C8—C6—C7—C2	−176.95 (15)	C15—C14—C16—O6	−4.3 (2)
C7—C6—C8—O4	−178.94 (17)	C13—C14—C16—O6	177.63 (17)
C5—C6—C8—O4	2.9 (3)	C15—C14—C16—O7	174.56 (17)
C7—C6—C8—O3	1.6 (3)	C13—C14—C16—O7	−3.5 (3)
C5—C6—C8—O3	−176.57 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O6^i	0.97	2.57	3.496 (2)	159
O7—H7A···O2^ii	0.83 (1)	1.90 (1)	2.7211 (19)	177 (3)
O3—H3A···O4^iii	0.83 (1)	1.82 (1)	2.6474 (17)	177 (3)
O1—H1A···O6^iv	0.83 (1)	1.76 (1)	2.5848 (19)	175 (3)

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

Poly[[µ₂-1,4-bis(1H-imidazol-1-yl)benzene]{µ₂-5-[(3-carboxyphenoxy)methyl]isophthalato}cadmium(II)] (I)

Crystal data

[Cd(C16H10O7)(C12H10N4)]	F(000) = 1280
Mr = 636.88	Dx = 1.680 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.1105 (6) Å	Cell parameters from 9023 reflections
b = 12.0603 (6) Å	θ = 3.0–28.3°
c = 21.2013 (12) Å	µ = 0.93 mm^−1
β = 103.0668 (12)°	T = 298 K
V = 2518.3 (2) Å^3	Block, colourless
Z = 4	0.25 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer	5751 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.021
Absorption correction: multi-scan (SADABS; Bruker, 2001)	θmax = 28.3°, θmin = 3.0°
Tmin = 0.661, Tmax = 0.746	h = −13→13
23463 measured reflections	k = −15→16
6188 independent reflections	l = −28→28

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)] = 0.024	w = 1/[σ^2(Fo^2) + (0.0239P)^2 + 2.0994P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.061	(Δ/σ)max = 0.001
S = 1.08	Δρmax = 0.46 e Å^−3
6188 reflections	Δρmin = −0.37 e Å^−3
363 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0114 (5)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Single-crystal diffraction data of H₃L and compound I were collected on a Bruker Smart APEXII CCD diffractometer using graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) at room temperature. All structures were solved via direct methods employed in SHELXT2014 and SHELXL2018, and refined based on F² with full-matrix least-squares techniques (Sheldrick et al., 2015a,b).

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

	x	y	z	Uiso*/Ueq
Cd1	0.22022 (2)	0.38276 (2)	0.23617 (2)	0.02121 (6)
N1	0.24027 (15)	0.44834 (13)	0.33613 (7)	0.0261 (3)
N2	0.31339 (16)	0.55128 (13)	0.42279 (7)	0.0271 (3)
N3	0.6367 (2)	0.86303 (16)	0.58522 (9)	0.0407 (4)
N4	0.71218 (19)	0.98365 (16)	0.66246 (9)	0.0396 (4)
O1	0.47355 (15)	0.37864 (13)	0.25505 (9)	0.0439 (4)
O2	0.34446 (15)	0.25102 (14)	0.19874 (10)	0.0514 (5)
O3	0.05765 (13)	0.25058 (12)	0.21928 (8)	0.0348 (3)
O4	−0.04586 (13)	0.41081 (11)	0.21878 (7)	0.0312 (3)
O5	0.62576 (14)	−0.05304 (10)	0.08521 (6)	0.0277 (3)
O6	0.7315 (3)	−0.54307 (14)	0.07708 (9)	0.0672 (6)
O7	0.78970 (17)	−0.43324 (12)	0.16245 (7)	0.0402 (4)
H7	0.832251	−0.488287	0.178216	0.060*
C1	0.45852 (17)	0.29353 (15)	0.22111 (9)	0.0253 (4)
C2	0.58088 (16)	0.23891 (14)	0.20496 (8)	0.0207 (3)
C3	0.57477 (17)	0.12970 (14)	0.18392 (8)	0.0231 (3)
H3	0.493198	0.091071	0.177501	0.028*
C4	0.68993 (17)	0.07742 (14)	0.17232 (8)	0.0216 (3)
C5	0.81139 (17)	0.13589 (15)	0.18281 (9)	0.0246 (3)
H5	0.889475	0.100569	0.176930	0.030*
C6	0.81796 (16)	0.24649 (15)	0.20199 (8)	0.0219 (3)
C7	0.70149 (16)	0.29803 (14)	0.21243 (8)	0.0209 (3)
H7A	0.704414	0.372305	0.224447	0.025*
C8	−0.04921 (17)	0.30707 (15)	0.21368 (8)	0.0227 (3)
C9	0.68673 (18)	−0.04234 (14)	0.15311 (8)	0.0241 (3)
H9A	0.778391	−0.071717	0.162082	0.029*
H9B	0.634812	−0.084499	0.178121	0.029*
C10	0.61151 (18)	−0.15980 (15)	0.06217 (9)	0.0237 (3)
C11	0.66990 (18)	−0.25148 (15)	0.09716 (9)	0.0250 (3)
H11	0.716571	−0.243958	0.140087	0.030*
C12	0.6578 (2)	−0.35499 (16)	0.06723 (9)	0.0296 (4)
C13	0.5846 (3)	−0.36701 (18)	0.00406 (11)	0.0449 (6)
H13	0.577335	−0.436160	−0.015842	0.054*
C14	0.5224 (3)	−0.27539 (19)	−0.02934 (10)	0.0462 (6)
H14	0.470604	−0.283855	−0.071289	0.055*
C15	0.5362 (2)	−0.17182 (17)	−0.00117 (9)	0.0328 (4)
H15	0.495691	−0.110440	−0.024249	0.039*
C16	0.7283 (2)	−0.45376 (16)	0.10194 (10)	0.0338 (4)
C17	0.31535 (19)	0.53468 (16)	0.35980 (9)	0.0271 (4)
H17	0.363176	0.578285	0.336400	0.033*
C18	0.18628 (19)	0.40822 (17)	0.38586 (10)	0.0297 (4)
H18	0.128264	0.347660	0.382955	0.036*
C19	0.2308 (2)	0.47055 (17)	0.43944 (10)	0.0323 (4)
H19	0.209816	0.460923	0.479606	0.039*
C20	0.3902 (2)	0.63287 (16)	0.46446 (9)	0.0302 (4)
C21	0.4144 (2)	0.62113 (16)	0.53108 (9)	0.0294 (4)
H21	0.377766	0.561282	0.548953	0.035*
C22	0.4932 (2)	0.69857 (18)	0.57113 (9)	0.0314 (4)
H22	0.508012	0.691674	0.615872	0.038*
C23	0.4437 (4)	0.7223 (2)	0.43794 (12)	0.0609 (8)
H23	0.425369	0.731428	0.393250	0.073*
C24	0.5246 (4)	0.7981 (2)	0.47793 (13)	0.0657 (9)
H24	0.562256	0.857517	0.460181	0.079*
C25	0.5493 (2)	0.78549 (19)	0.54446 (10)	0.0374 (5)
C26	0.7625 (4)	0.8966 (3)	0.57827 (17)	0.0776 (12)
H26	0.807336	0.873294	0.546852	0.093*
C27	0.8079 (3)	0.9703 (3)	0.62623 (16)	0.0737 (11)
H27	0.891196	1.006468	0.633625	0.088*
C28	0.6128 (2)	0.91638 (19)	0.63701 (11)	0.0381 (5)
H28	0.535083	0.906755	0.652919	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.01754 (7)	0.02276 (8)	0.02298 (8)	0.00044 (4)	0.00386 (5)	−0.00162 (4)
N1	0.0214 (7)	0.0300 (8)	0.0264 (7)	−0.0007 (6)	0.0045 (6)	−0.0033 (6)
N2	0.0281 (8)	0.0289 (8)	0.0243 (7)	−0.0028 (6)	0.0063 (6)	−0.0041 (6)
N3	0.0446 (10)	0.0420 (11)	0.0384 (10)	−0.0147 (8)	0.0154 (8)	−0.0167 (8)
N4	0.0364 (9)	0.0446 (11)	0.0415 (10)	−0.0116 (8)	0.0164 (8)	−0.0173 (8)
O1	0.0272 (7)	0.0489 (10)	0.0557 (10)	0.0069 (6)	0.0093 (7)	−0.0232 (8)
O2	0.0199 (7)	0.0449 (9)	0.0920 (14)	−0.0031 (6)	0.0182 (8)	−0.0236 (9)
O3	0.0178 (6)	0.0311 (7)	0.0562 (9)	−0.0002 (5)	0.0102 (6)	−0.0068 (6)
O4	0.0227 (6)	0.0250 (6)	0.0432 (8)	−0.0031 (5)	0.0016 (6)	−0.0012 (6)
O5	0.0372 (7)	0.0190 (6)	0.0246 (6)	0.0041 (5)	0.0022 (5)	0.0010 (5)
O6	0.1114 (18)	0.0282 (8)	0.0496 (11)	0.0203 (10)	−0.0081 (11)	−0.0085 (8)
O7	0.0523 (9)	0.0260 (7)	0.0359 (8)	0.0115 (7)	−0.0036 (7)	0.0004 (6)
C1	0.0192 (8)	0.0284 (9)	0.0303 (9)	0.0055 (6)	0.0095 (7)	0.0033 (7)
C2	0.0161 (7)	0.0249 (8)	0.0211 (7)	0.0030 (6)	0.0041 (6)	0.0014 (6)
C3	0.0179 (7)	0.0242 (8)	0.0265 (8)	−0.0019 (6)	0.0036 (6)	0.0010 (6)
C4	0.0205 (8)	0.0196 (8)	0.0244 (8)	0.0000 (6)	0.0041 (6)	−0.0008 (6)
C5	0.0185 (7)	0.0245 (9)	0.0313 (9)	0.0016 (6)	0.0068 (6)	−0.0034 (7)
C6	0.0159 (7)	0.0252 (8)	0.0249 (8)	−0.0014 (6)	0.0047 (6)	−0.0021 (6)
C7	0.0186 (7)	0.0215 (8)	0.0218 (8)	0.0009 (6)	0.0030 (6)	−0.0027 (6)
C8	0.0173 (7)	0.0284 (9)	0.0225 (8)	−0.0025 (6)	0.0047 (6)	−0.0034 (6)
C9	0.0260 (8)	0.0201 (8)	0.0246 (8)	0.0017 (6)	0.0025 (6)	−0.0003 (6)
C10	0.0256 (8)	0.0200 (8)	0.0262 (8)	0.0009 (6)	0.0073 (7)	−0.0010 (6)
C11	0.0273 (8)	0.0225 (8)	0.0238 (8)	0.0016 (7)	0.0032 (7)	−0.0006 (7)
C12	0.0369 (10)	0.0217 (8)	0.0291 (9)	0.0020 (7)	0.0053 (8)	−0.0001 (7)
C13	0.0712 (16)	0.0265 (10)	0.0313 (11)	0.0017 (10)	−0.0003 (10)	−0.0071 (8)
C14	0.0701 (16)	0.0362 (12)	0.0240 (10)	0.0006 (11)	−0.0068 (10)	−0.0022 (8)
C15	0.0421 (11)	0.0281 (10)	0.0252 (9)	0.0038 (8)	0.0009 (8)	0.0044 (7)
C16	0.0411 (11)	0.0230 (9)	0.0359 (10)	0.0031 (8)	0.0056 (8)	0.0001 (8)
C17	0.0256 (8)	0.0317 (9)	0.0242 (8)	−0.0028 (7)	0.0062 (7)	−0.0025 (7)
C18	0.0257 (9)	0.0317 (10)	0.0331 (10)	−0.0041 (7)	0.0095 (7)	−0.0031 (8)
C19	0.0328 (10)	0.0364 (10)	0.0307 (10)	−0.0056 (8)	0.0133 (8)	−0.0030 (8)
C20	0.0348 (10)	0.0288 (10)	0.0264 (9)	−0.0034 (8)	0.0054 (7)	−0.0058 (7)
C21	0.0282 (9)	0.0343 (10)	0.0267 (9)	−0.0039 (7)	0.0082 (7)	−0.0023 (7)
C22	0.0291 (9)	0.0397 (11)	0.0258 (9)	−0.0013 (8)	0.0068 (7)	−0.0071 (8)
C23	0.106 (2)	0.0486 (15)	0.0250 (11)	−0.0341 (15)	0.0089 (12)	−0.0025 (10)
C24	0.112 (3)	0.0466 (15)	0.0383 (13)	−0.0427 (16)	0.0152 (14)	−0.0042 (11)
C25	0.0429 (12)	0.0355 (11)	0.0340 (11)	−0.0092 (9)	0.0094 (9)	−0.0120 (8)
C26	0.077 (2)	0.095 (2)	0.078 (2)	−0.0506 (18)	0.0556 (18)	−0.0562 (19)
C27	0.0673 (18)	0.091 (2)	0.079 (2)	−0.0479 (17)	0.0489 (17)	−0.0527 (18)
C28	0.0328 (10)	0.0425 (12)	0.0402 (11)	−0.0061 (9)	0.0111 (9)	−0.0151 (9)

Geometric parameters (Å, º)

Cd1—N1	2.2280 (15)	C6—C7	1.393 (2)
Cd1—N4^i	2.2332 (17)	C6—C8^ii	1.500 (2)
Cd1—O3	2.2595 (14)	C7—H7A	0.9300
Cd1—O2	2.2765 (15)	C9—H9A	0.9700
Cd1—O1	2.5019 (15)	C9—H9B	0.9700
Cd1—O4	2.6532 (13)	C10—C11	1.387 (2)
N1—C17	1.319 (2)	C10—C15	1.393 (3)
N1—C18	1.380 (2)	C11—C12	1.393 (3)
N2—C17	1.355 (2)	C11—H11	0.9300
N2—C19	1.380 (2)	C12—C13	1.384 (3)
N2—C20	1.429 (2)	C12—C16	1.494 (3)
N3—C28	1.341 (3)	C13—C14	1.384 (3)
N3—C26	1.374 (3)	C13—H13	0.9300
N3—C25	1.434 (3)	C14—C15	1.378 (3)
N4—C28	1.309 (3)	C14—H14	0.9300
N4—C27	1.374 (3)	C15—H15	0.9300
O1—C1	1.243 (2)	C17—H17	0.9300
O2—C1	1.253 (2)	C18—C19	1.352 (3)
O3—C8	1.260 (2)	C18—H18	0.9300
O4—C8	1.256 (2)	C19—H19	0.9300
O5—C10	1.373 (2)	C20—C23	1.382 (3)
O5—C9	1.438 (2)	C20—C21	1.385 (3)
O6—C16	1.203 (3)	C21—C22	1.386 (3)
O7—C16	1.316 (3)	C21—H21	0.9300
O7—H7	0.8200	C22—C25	1.373 (3)
C1—C2	1.508 (2)	C22—H22	0.9300
C2—C3	1.388 (2)	C23—C24	1.382 (3)
C2—C7	1.390 (2)	C23—H23	0.9300
C3—C4	1.394 (2)	C24—C25	1.384 (3)
C3—H3	0.9300	C24—H24	0.9300
C4—C5	1.390 (2)	C26—C27	1.350 (4)
C4—C9	1.499 (2)	C26—H26	0.9300
C5—C6	1.392 (2)	C27—H27	0.9300
C5—H5	0.9300	C28—H28	0.9300
N1—Cd1—N4^i	112.99 (7)	O5—C9—H9B	109.7
N1—Cd1—O3	107.92 (6)	C4—C9—H9B	109.7
N4^i—Cd1—O3	119.21 (7)	H9A—C9—H9B	108.2
N1—Cd1—O2	129.84 (7)	O5—C10—C11	124.03 (16)
N4^i—Cd1—O2	101.26 (7)	O5—C10—C15	115.53 (16)
O3—Cd1—O2	83.76 (5)	C11—C10—C15	120.41 (17)
N1—Cd1—O1	89.15 (5)	C12—C11—C10	119.20 (17)
N4^i—Cd1—O1	90.02 (6)	C12—C11—H11	120.4
O3—Cd1—O1	133.88 (5)	C10—C11—H11	120.4
O2—Cd1—O1	54.29 (5)	C13—C12—C11	120.50 (18)
N1—Cd1—O4	87.61 (5)	C13—C12—C16	118.98 (18)
N4^i—Cd1—O4	86.30 (6)	C11—C12—C16	120.47 (17)
O3—Cd1—O4	52.37 (4)	C12—C13—C14	119.55 (19)
O2—Cd1—O4	131.50 (5)	C12—C13—H13	120.2
O1—Cd1—O4	173.71 (5)	C14—C13—H13	120.2
C17—N1—C18	106.21 (16)	C15—C14—C13	120.78 (19)
C17—N1—Cd1	124.25 (13)	C15—C14—H14	119.6
C18—N1—Cd1	129.47 (13)	C13—C14—H14	119.6
C17—N2—C19	107.02 (16)	C14—C15—C10	119.47 (18)
C17—N2—C20	125.75 (16)	C14—C15—H15	120.3
C19—N2—C20	127.11 (16)	C10—C15—H15	120.3
C28—N3—C26	106.79 (19)	O6—C16—O7	122.8 (2)
C28—N3—C25	127.28 (19)	O6—C16—C12	123.7 (2)
C26—N3—C25	125.93 (19)	O7—C16—C12	113.43 (17)
C28—N4—C27	105.59 (19)	N1—C17—N2	110.86 (16)
C28—N4—Cd1^iii	129.70 (15)	N1—C17—H17	124.6
C27—N4—Cd1^iii	123.84 (16)	N2—C17—H17	124.6
C1—O1—Cd1	86.39 (11)	C19—C18—N1	109.47 (17)
C1—O2—Cd1	96.64 (12)	C19—C18—H18	125.3
C8—O3—Cd1	102.18 (11)	N1—C18—H18	125.3
C8—O4—Cd1	83.78 (10)	C18—C19—N2	106.44 (17)
C10—O5—C9	115.28 (13)	C18—C19—H19	126.8
C16—O7—H7	109.5	N2—C19—H19	126.8
O1—C1—O2	122.59 (17)	C23—C20—C21	119.96 (19)
O1—C1—C2	119.54 (16)	C23—C20—N2	119.60 (18)
O2—C1—C2	117.86 (17)	C21—C20—N2	120.41 (18)
C3—C2—C7	119.84 (15)	C22—C21—C20	120.01 (18)
C3—C2—C1	120.57 (15)	C22—C21—H21	120.0
C7—C2—C1	119.58 (15)	C20—C21—H21	120.0
C2—C3—C4	120.52 (15)	C25—C22—C21	119.72 (18)
C2—C3—H3	119.7	C25—C22—H22	120.1
C4—C3—H3	119.7	C21—C22—H22	120.1
C5—C4—C3	119.04 (16)	C20—C23—C24	119.9 (2)
C5—C4—C9	119.76 (15)	C20—C23—H23	120.0
C3—C4—C9	121.07 (15)	C24—C23—H23	120.0
C6—C5—C4	121.01 (16)	C23—C24—C25	119.9 (2)
C6—C5—H5	119.5	C23—C24—H24	120.1
C4—C5—H5	119.5	C25—C24—H24	120.1
C5—C6—C7	119.21 (15)	C22—C25—C24	120.5 (2)
C5—C6—C8^ii	119.81 (15)	C22—C25—N3	120.35 (19)
C7—C6—C8^ii	120.94 (15)	C24—C25—N3	119.1 (2)
C2—C7—C6	120.29 (16)	C27—C26—N3	106.2 (2)
C2—C7—H7A	119.9	C27—C26—H26	126.9
C6—C7—H7A	119.9	N3—C26—H26	126.9
O4—C8—O3	121.66 (16)	C26—C27—N4	109.6 (2)
O4—C8—C6^iv	120.36 (15)	C26—C27—H27	125.2
O3—C8—C6^iv	117.96 (16)	N4—C27—H27	125.2
O5—C9—C4	109.66 (14)	N4—C28—N3	111.80 (19)
O5—C9—H9A	109.7	N4—C28—H28	124.1
C4—C9—H9A	109.7	N3—C28—H28	124.1
Cd1—O1—C1—O2	−3.0 (2)	C11—C12—C16—O6	−173.5 (2)
Cd1—O1—C1—C2	176.13 (15)	C13—C12—C16—O7	−177.3 (2)
Cd1—O2—C1—O1	3.3 (2)	C11—C12—C16—O7	5.2 (3)
Cd1—O2—C1—C2	−175.83 (13)	C18—N1—C17—N2	0.7 (2)
O1—C1—C2—C3	161.41 (18)	Cd1—N1—C17—N2	−176.69 (12)
O2—C1—C2—C3	−19.4 (3)	C19—N2—C17—N1	−0.5 (2)
O1—C1—C2—C7	−17.4 (3)	C20—N2—C17—N1	175.78 (17)
O2—C1—C2—C7	161.84 (18)	C17—N1—C18—C19	−0.6 (2)
C7—C2—C3—C4	2.2 (3)	Cd1—N1—C18—C19	176.58 (14)
C1—C2—C3—C4	−176.54 (16)	N1—C18—C19—N2	0.3 (2)
C2—C3—C4—C5	0.7 (3)	C17—N2—C19—C18	0.1 (2)
C2—C3—C4—C9	176.60 (16)	C20—N2—C19—C18	−176.10 (18)
C3—C4—C5—C6	−2.7 (3)	C17—N2—C20—C23	18.6 (3)
C9—C4—C5—C6	−178.65 (16)	C19—N2—C20—C23	−165.8 (2)
C4—C5—C6—C7	1.7 (3)	C17—N2—C20—C21	−159.50 (19)
C4—C5—C6—C8^ii	179.31 (16)	C19—N2—C20—C21	16.1 (3)
C3—C2—C7—C6	−3.2 (3)	C23—C20—C21—C22	−0.5 (3)
C1—C2—C7—C6	175.58 (16)	N2—C20—C21—C22	177.61 (18)
C5—C6—C7—C2	1.2 (3)	C20—C21—C22—C25	−1.3 (3)
C8^ii—C6—C7—C2	−176.32 (15)	C21—C20—C23—C24	1.8 (5)
Cd1—O4—C8—O3	0.83 (17)	N2—C20—C23—C24	−176.3 (3)
Cd1—O4—C8—C6^iv	179.54 (15)	C20—C23—C24—C25	−1.3 (5)
Cd1—O3—C8—O4	−1.0 (2)	C21—C22—C25—C24	1.9 (4)
Cd1—O3—C8—C6^iv	−179.73 (12)	C21—C22—C25—N3	−176.79 (19)
C10—O5—C9—C4	−177.29 (14)	C23—C24—C25—C22	−0.5 (5)
C5—C4—C9—O5	−104.31 (19)	C23—C24—C25—N3	178.1 (3)
C3—C4—C9—O5	79.8 (2)	C28—N3—C25—C22	−49.6 (4)
C9—O5—C10—C11	−10.4 (2)	C26—N3—C25—C22	130.2 (3)
C9—O5—C10—C15	171.63 (16)	C28—N3—C25—C24	131.7 (3)
O5—C10—C11—C12	−174.93 (17)	C26—N3—C25—C24	−48.4 (4)
C15—C10—C11—C12	3.0 (3)	C28—N3—C26—C27	−0.7 (4)
C10—C11—C12—C13	−2.1 (3)	C25—N3—C26—C27	179.4 (3)
C10—C11—C12—C16	175.35 (18)	N3—C26—C27—N4	−0.5 (5)
C11—C12—C13—C14	−0.4 (4)	C28—N4—C27—C26	1.5 (4)
C16—C12—C13—C14	−178.0 (2)	Cd1^iii—N4—C27—C26	−168.7 (3)
C12—C13—C14—C15	2.2 (4)	C27—N4—C28—N3	−2.0 (3)
C13—C14—C15—C10	−1.4 (4)	Cd1^iii—N4—C28—N3	167.41 (17)
O5—C10—C15—C14	176.8 (2)	C26—N3—C28—N4	1.8 (3)
C11—C10—C15—C14	−1.3 (3)	C25—N3—C28—N4	−178.4 (2)
C13—C12—C16—O6	4.0 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7···O4^v	0.82	1.81	2.613 (2)	168
C9—H9B···O4^vi	0.97	2.55	3.387 (2)	145
C15—H15···O5^vii	0.93	2.52	3.449 (2)	177
C17—H17···O3^viii	0.93	2.60	3.495 (2)	161
C23—H23···O3^viii	0.93	2.44	3.348 (3)	165
C28—H28···O7^ix	0.93	2.55	3.435 (3)	158

Symmetry codes: (v) x+1, y−1, z; (vi) −x+1/2, y−1/2, −z+1/2; (vii) −x+1, −y, −z; (viii) −x+1/2, y+1/2, −z+1/2; (ix) x−1/2, −y+1/2, z+1/2.