A three-dimensional supra­molecular framework based on the inter­linkage of an inter­penetrating diamondoid coordination network

In the development of coordination-driven crystalline materials, O- and N-atom donors from carboxyl­ate and pyridyl-based ligands are widely used classes of multidentate bridging ligands composed of several terminal coordinating groups linked by either rigid or flexible spacers. The rigidity of the ligands can play a vital role in the determination of the structures formed. A new Cd^II supra­molecular compound, namely poly[μ-adipato-κ²O¹:O⁴-μ-adipato-κ⁴O¹,O^1′:O⁴,O^4′-di­aqua­bis­[μ-1,4-bis­(pyridin-4-yl)-1,3-butadiene-κ²N:N′]dicadmium(II)], [Cd₂(C₆H₈O₄)₂(C₁₄H₁₂N₂)₂(H₂O)₂]_n, (I), has been synthesized by the self-assembly of Cd(NO₃)₂·4H₂O, adipic acid (hexane-1,6-dioic acid; H₂adp) and the dipyridyl ligand 1,4-bis­(pyridin-4-yl)buta-1,3-diene (1,4-bpbd) under hydro­thermal conditions. Single-crystal X-ray diffraction analysis reveals that each Cd^II centre is located in a distorted octa­hedral coordination environment, coordinated by one water O atom, three carboxyl­ate O atoms from two different adp²⁻ ligands and two N atoms from two different 1,4-bpbd ligands. The Cd(H₂O) units are inter­connected by the μ₂,κ²-adp²⁻, μ₂,κ⁴-adp²⁻ and 1,4-bpbd ligands, which lie across centres of inversion, to give a 6⁶-dia network. Large cavities within a single diamondoid network permit the mutual threefold inter­penetration of crystallographically equivalent frameworks. Hydrogen-bonding inter­actions between the coordinated water mol­ecules and adp²⁻ carboxyl­ate O atoms anchor the inter­penetrating networks into a unique three-dimensional supra­molecular structure. Topologically, taking the coordinated water mol­ecules and Cd^II centres as nodes, the whole architecture can be simplified as a binodal (3,7)-connected supra­molecular framework. The identity of (I) was further characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis and powder X-ray diffraction. The solid-state photoluminescence properties of (I) were also investigated.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: publCIF (Westrip, 2010).

Poly[µ-adipato-κ²O¹:O⁴-µ-adipato-κ⁴O¹,O^1':O⁴,O^4'-diaquabis[µ-1,4-bis(pyridin-4-yl)-1,3-butadiene-κ²N:N']dicadmium]

Crystal data

[Cd2(C6H8O4)2(C14H12N2)2(H2O)2]	Z = 2
Mr = 482.81	F(000) = 488
Triclinic, P1	Dx = 1.656 Mg m^−3
a = 8.7119 (17) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.318 (2) Å	Cell parameters from 17848 reflections
c = 10.961 (2) Å	θ = 2.9–27.5°
α = 83.47 (3)°	µ = 1.16 mm^−1
β = 82.91 (3)°	T = 223 K
γ = 84.71 (3)°	Block, light yellow
V = 968.3 (3) Å^3	0.27 × 0.25 × 0.22 mm

Data collection

Bruker D8 goniometer with an APEX CCD detector diffractometer	4226 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
phi and ω scans	θmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −11→11
Tmin = 0.753, Tmax = 0.782	k = −13→13
17848 measured reflections	l = −12→14
4429 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.028	w = 1/[σ^2(Fo^2) + (0.0283P)^2 + 1.5803P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.076	(Δ/σ)max = 0.001
S = 1.16	Δρmax = 1.59 e Å^−3
4429 reflections	Δρmin = −0.53 e Å^−3
262 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.061 (2)

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
Cd1	0.74987 (2)	0.13373 (2)	0.37448 (2)	0.02405 (10)
N1	0.8738 (3)	−0.0343 (2)	0.2647 (2)	0.0289 (5)
N2	0.6341 (3)	0.2425 (2)	0.5447 (2)	0.0286 (5)
O1	0.5161 (3)	0.1143 (3)	0.3132 (2)	0.0418 (5)
O2	0.6578 (3)	0.1785 (2)	0.1403 (2)	0.0427 (5)
O3	0.8479 (3)	0.3472 (2)	0.3058 (2)	0.0436 (5)
O4	0.9929 (3)	0.1970 (2)	0.4055 (3)	0.0440 (6)
O5	0.7440 (3)	−0.0435 (3)	0.5344 (2)	0.0447 (6)
H1W	0.671 (5)	−0.060 (4)	0.581 (4)	0.050 (12)*
H2W	0.814 (6)	−0.091 (5)	0.555 (4)	0.056 (13)*
C1	0.7978 (4)	−0.1420 (3)	0.2698 (3)	0.0390 (7)
H1	0.7094	−0.1513	0.3277	0.047*
C2	0.8429 (4)	−0.2399 (3)	0.1941 (3)	0.0378 (7)
H2	0.7851	−0.3134	0.2004	0.045*
C3	0.9740 (3)	−0.2296 (3)	0.1084 (2)	0.0259 (5)
C4	1.0532 (3)	−0.1179 (3)	0.1040 (3)	0.0296 (6)
H4	1.1425	−0.1062	0.0477	0.036*
C5	0.9995 (3)	−0.0242 (3)	0.1831 (3)	0.0306 (6)
H5	1.0547	0.0505	0.1790	0.037*
C6	1.0256 (3)	−0.3310 (3)	0.0256 (3)	0.0308 (6)
H6	1.0998	−0.3109	−0.0422	0.037*
C7	0.9738 (4)	−0.4503 (3)	0.0406 (3)	0.0323 (6)
H7	0.8989	−0.4705	0.1078	0.039*
C8	0.7131 (4)	0.2372 (3)	0.6429 (3)	0.0356 (7)
H8	0.8032	0.1799	0.6460	0.043*
C9	0.6684 (4)	0.3118 (3)	0.7393 (3)	0.0340 (6)
H9	0.7277	0.3048	0.8062	0.041*
C10	0.5353 (3)	0.3978 (3)	0.7382 (2)	0.0256 (5)
C11	0.4542 (3)	0.4028 (3)	0.6360 (3)	0.0282 (5)
H11	0.3639	0.4595	0.6302	0.034*
C12	0.5066 (3)	0.3241 (3)	0.5430 (3)	0.0289 (6)
H12	0.4494	0.3285	0.4751	0.035*
C13	0.4815 (4)	0.4793 (3)	0.8385 (3)	0.0317 (6)
H13	0.4091	0.5507	0.8224	0.038*
C14	0.5280 (4)	0.4593 (3)	0.9513 (3)	0.0331 (6)
H14	0.6010	0.3886	0.9681	0.040*
C15	0.5377 (3)	0.1377 (3)	0.1951 (3)	0.0307 (6)
C16	0.4053 (4)	0.1118 (4)	0.1254 (3)	0.0463 (8)
H16A	0.3369	0.1923	0.1157	0.056*
H16B	0.3446	0.0452	0.1752	0.056*
C17	0.4561 (4)	0.0663 (4)	−0.0015 (3)	0.0451 (8)
H17A	0.3639	0.0640	−0.0440	0.054*
H17B	0.5216	0.1304	−0.0499	0.054*
C18	0.9685 (3)	0.3119 (3)	0.3545 (3)	0.0319 (6)
C19	1.0891 (4)	0.4085 (4)	0.3573 (3)	0.0446 (8)
H19A	1.0752	0.4814	0.2931	0.053*
H19B	1.1931	0.3651	0.3394	0.053*
C20	1.0757 (4)	0.4612 (4)	0.4827 (4)	0.0477 (8)
H20A	1.0887	0.3873	0.5462	0.057*
H20B	1.1608	0.5169	0.4829	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02315 (12)	0.02481 (12)	0.02578 (13)	−0.00254 (7)	−0.00112 (7)	−0.01075 (7)
N1	0.0311 (12)	0.0271 (11)	0.0292 (12)	−0.0027 (9)	0.0003 (9)	−0.0095 (9)
N2	0.0331 (12)	0.0301 (12)	0.0231 (11)	−0.0004 (9)	−0.0022 (9)	−0.0085 (9)
O1	0.0303 (11)	0.0687 (16)	0.0285 (11)	−0.0076 (10)	−0.0038 (9)	−0.0107 (10)
O2	0.0360 (12)	0.0499 (14)	0.0441 (13)	−0.0160 (10)	−0.0029 (10)	−0.0049 (11)
O3	0.0430 (13)	0.0470 (13)	0.0445 (13)	−0.0149 (10)	−0.0157 (10)	0.0006 (10)
O4	0.0321 (11)	0.0340 (12)	0.0674 (16)	−0.0043 (9)	−0.0086 (11)	−0.0065 (11)
O5	0.0370 (13)	0.0448 (14)	0.0426 (13)	0.0085 (11)	0.0101 (11)	0.0110 (11)
C1	0.0392 (16)	0.0337 (15)	0.0435 (17)	−0.0105 (13)	0.0151 (13)	−0.0167 (13)
C2	0.0377 (16)	0.0311 (15)	0.0454 (17)	−0.0116 (12)	0.0101 (13)	−0.0168 (13)
C3	0.0286 (13)	0.0253 (12)	0.0239 (12)	0.0023 (10)	−0.0033 (10)	−0.0061 (10)
C4	0.0269 (13)	0.0293 (13)	0.0308 (14)	−0.0009 (10)	0.0038 (11)	−0.0041 (11)
C5	0.0306 (14)	0.0255 (13)	0.0359 (15)	−0.0035 (11)	−0.0006 (11)	−0.0059 (11)
C6	0.0336 (14)	0.0298 (14)	0.0278 (13)	0.0024 (11)	0.0024 (11)	−0.0089 (11)
C7	0.0378 (15)	0.0299 (14)	0.0286 (14)	0.0008 (12)	0.0013 (12)	−0.0098 (12)
C8	0.0349 (15)	0.0411 (16)	0.0308 (15)	0.0117 (12)	−0.0070 (12)	−0.0124 (12)
C9	0.0346 (15)	0.0432 (16)	0.0258 (13)	0.0061 (12)	−0.0096 (11)	−0.0119 (12)
C10	0.0300 (13)	0.0259 (12)	0.0207 (12)	−0.0018 (10)	0.0010 (10)	−0.0058 (10)
C11	0.0278 (13)	0.0313 (13)	0.0248 (13)	0.0026 (10)	−0.0022 (10)	−0.0048 (10)
C12	0.0313 (14)	0.0333 (14)	0.0232 (12)	−0.0020 (11)	−0.0056 (11)	−0.0062 (11)
C13	0.0356 (15)	0.0316 (14)	0.0272 (14)	0.0041 (11)	0.0001 (11)	−0.0094 (11)
C14	0.0388 (16)	0.0335 (15)	0.0270 (14)	0.0040 (12)	−0.0017 (12)	−0.0112 (12)
C15	0.0286 (14)	0.0346 (14)	0.0313 (14)	−0.0036 (11)	−0.0056 (11)	−0.0108 (11)
C16	0.0342 (16)	0.070 (2)	0.0407 (18)	−0.0089 (16)	−0.0119 (14)	−0.0179 (17)
C17	0.054 (2)	0.055 (2)	0.0317 (16)	−0.0115 (16)	−0.0181 (15)	−0.0083 (15)
C18	0.0315 (14)	0.0360 (15)	0.0310 (14)	−0.0104 (12)	−0.0006 (11)	−0.0131 (12)
C19	0.0424 (18)	0.0475 (19)	0.0488 (19)	−0.0230 (15)	−0.0060 (15)	−0.0098 (15)
C20	0.052 (2)	0.0438 (19)	0.055 (2)	−0.0165 (16)	−0.0215 (17)	−0.0114 (16)

Geometric parameters (Å, º)

Cd1—O1	2.254 (2)	C7—C7^i	1.439 (5)
Cd1—N1	2.330 (2)	C7—H7	0.9400
Cd1—O4	2.347 (2)	C8—C9	1.374 (4)
Cd1—N2	2.358 (2)	C8—H8	0.9400
Cd1—O5	2.384 (3)	C9—C10	1.394 (4)
Cd1—O3	2.441 (2)	C9—H9	0.9400
Cd1—C18	2.740 (3)	C10—C11	1.390 (4)
Cd1—O2	2.760 (3)	C10—C13	1.466 (4)
Cd1—C15	2.855 (3)	C11—C12	1.383 (4)
N1—C5	1.329 (4)	C11—H11	0.9400
N1—C1	1.338 (4)	C12—H12	0.9400
N2—C12	1.331 (4)	C13—C14	1.336 (4)
N2—C8	1.341 (4)	C13—H13	0.9400
O1—C15	1.284 (4)	C14—C14^ii	1.443 (5)
O2—C15	1.226 (4)	C14—H14	0.9400
O3—C18	1.243 (4)	C15—C16	1.519 (4)
O4—C18	1.263 (4)	C16—C17	1.519 (5)
O5—H1W	0.79 (5)	C16—H16A	0.9800
O5—H2W	0.79 (5)	C16—H16B	0.9800
C1—C2	1.378 (4)	C17—C17^iii	1.504 (8)
C1—H1	0.9400	C17—H17A	0.9800
C2—C3	1.391 (4)	C17—H17B	0.9800
C2—H2	0.9400	C18—C19	1.519 (4)
C3—C4	1.390 (4)	C19—C20	1.522 (5)
C3—C6	1.466 (4)	C19—H19A	0.9800
C4—C5	1.384 (4)	C19—H19B	0.9800
C4—H4	0.9400	C20—C20^iv	1.509 (8)
C5—H5	0.9400	C20—H20A	0.9800
C6—C7	1.336 (4)	C20—H20B	0.9800
C6—H6	0.9400
O1—Cd1—N1	94.00 (9)	C7—C6—C3	124.1 (3)
O1—Cd1—O4	166.83 (9)	C7—C6—H6	118.0
N1—Cd1—O4	89.50 (9)	C3—C6—H6	118.0
O1—Cd1—N2	91.39 (9)	C6—C7—C7^i	123.6 (4)
N1—Cd1—N2	159.02 (9)	C6—C7—H7	118.2
O4—Cd1—N2	89.82 (9)	C7^i—C7—H7	118.2
O1—Cd1—O5	97.47 (10)	N2—C8—C9	123.0 (3)
N1—Cd1—O5	79.87 (9)	N2—C8—H8	118.5
O4—Cd1—O5	95.64 (10)	C9—C8—H8	118.5
N2—Cd1—O5	79.34 (9)	C8—C9—C10	120.1 (3)
O1—Cd1—O3	112.85 (9)	C8—C9—H9	119.9
N1—Cd1—O3	113.71 (9)	C10—C9—H9	119.9
O4—Cd1—O3	54.34 (8)	C11—C10—C9	116.5 (2)
N2—Cd1—O3	82.51 (9)	C11—C10—C13	120.9 (3)
O5—Cd1—O3	144.87 (9)	C9—C10—C13	122.6 (3)
O1—Cd1—C18	139.81 (10)	C12—C11—C10	119.8 (3)
N1—Cd1—C18	103.66 (9)	C12—C11—H11	120.1
O4—Cd1—C18	27.39 (9)	C10—C11—H11	120.1
N2—Cd1—C18	84.79 (9)	N2—C12—C11	123.3 (3)
O5—Cd1—C18	120.83 (10)	N2—C12—H12	118.4
O3—Cd1—C18	26.97 (9)	C11—C12—H12	118.4
O1—Cd1—O2	50.86 (8)	C14—C13—C10	124.6 (3)
N1—Cd1—O2	73.59 (9)	C14—C13—H13	117.7
O4—Cd1—O2	118.65 (9)	C10—C13—H13	117.7
N2—Cd1—O2	124.47 (8)	C13—C14—C14^ii	123.4 (4)
O5—Cd1—O2	135.60 (9)	C13—C14—H14	118.3
O3—Cd1—O2	79.22 (8)	C14^ii—C14—H14	118.3
C18—Cd1—O2	99.90 (8)	O2—C15—O1	122.5 (3)
O1—Cd1—C15	25.84 (8)	O2—C15—C16	121.2 (3)
N1—Cd1—C15	81.41 (9)	O1—C15—C16	116.3 (3)
O4—Cd1—C15	143.64 (9)	O2—C15—Cd1	73.07 (17)
N2—Cd1—C15	110.68 (9)	O1—C15—Cd1	49.93 (14)
O5—Cd1—C15	116.96 (10)	C16—C15—Cd1	164.4 (2)
O3—Cd1—C15	97.52 (9)	C15—C16—C17	114.5 (3)
C18—Cd1—C15	122.00 (9)	C15—C16—H16A	108.6
O2—Cd1—C15	25.14 (8)	C17—C16—H16A	108.6
C5—N1—C1	117.3 (2)	C15—C16—H16B	108.6
C5—N1—Cd1	125.39 (19)	C17—C16—H16B	108.6
C1—N1—Cd1	116.40 (19)	H16A—C16—H16B	107.6
C12—N2—C8	117.3 (2)	C17^iii—C17—C16	114.1 (4)
C12—N2—Cd1	124.09 (18)	C17^iii—C17—H17A	108.7
C8—N2—Cd1	117.91 (19)	C16—C17—H17A	108.7
C15—O1—Cd1	104.22 (18)	C17^iii—C17—H17B	108.7
C15—O2—Cd1	81.79 (18)	C16—C17—H17B	108.7
C18—O3—Cd1	90.03 (19)	H17A—C17—H17B	107.6
C18—O4—Cd1	93.88 (18)	O3—C18—O4	121.6 (3)
Cd1—O5—H1W	125 (3)	O3—C18—C19	120.3 (3)
Cd1—O5—H2W	128 (3)	O4—C18—C19	118.1 (3)
H1W—O5—H2W	107 (5)	O3—C18—Cd1	63.00 (16)
N1—C1—C2	123.1 (3)	O4—C18—Cd1	58.73 (15)
N1—C1—H1	118.5	C19—C18—Cd1	174.3 (2)
C2—C1—H1	118.5	C18—C19—C20	111.3 (3)
C1—C2—C3	119.9 (3)	C18—C19—H19A	109.4
C1—C2—H2	120.1	C20—C19—H19A	109.4
C3—C2—H2	120.1	C18—C19—H19B	109.4
C4—C3—C2	116.8 (2)	C20—C19—H19B	109.4
C4—C3—C6	121.5 (3)	H19A—C19—H19B	108.0
C2—C3—C6	121.7 (3)	C20^iv—C20—C19	114.6 (4)
C5—C4—C3	119.5 (3)	C20^iv—C20—H20A	108.6
C5—C4—H4	120.3	C19—C20—H20A	108.6
C3—C4—H4	120.3	C20^iv—C20—H20B	108.6
N1—C5—C4	123.4 (3)	C19—C20—H20B	108.6
N1—C5—H5	118.3	H20A—C20—H20B	107.6
C4—C5—H5	118.3

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1W···O1^v	0.79 (5)	1.96 (5)	2.748 (4)	175 (5)
O5—H2W···O4^vi	0.79 (5)	1.98 (5)	2.768 (4)	173 (5)

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