Construction of a three-dimensional supra­molecular framework based on an anionic cadmium(II) coordination network and protonated dipyridine organic cations

As a class of multifunctional materials, crystalline supra­molecular complexes have attracted much attention because of their unique architectures, intriguing topologies and potential applications. In this article, a new supra­molecular compound, namely catena-poly[4,4′-(buta-1,3-diene-1,4-di­yl)dipyridin-1-ium [(μ₄-benzene-1,2,4,5-tetra­carboxyl­ato-κ⁶O¹,O^1′:O²:O⁴,O^4′:O⁵)cadmium(II)]], {(C₁₄H₁₄N₂)[Cd(C₁₀H₂O₈)]}_n or {(1,4-H₂bpbd)[Cd(1,2,4,5-btc)]}_n, has been pre­pared by the self-assembly of Cd(NO₃)₂·4H₂O, benzene-1,2,4,5-tetra­car­boxy­lic acid (1,2,4,5-H₄btc) and 1,4-bis­(pyridin-4-yl)buta-1,3-diene (1,4-bpbd) under hydro­thermal conditions. The title compound has been structurally characterized by IR spectroscopy, elemental analysis, powder X-ray diffraction and single-crystal X-ray diffraction analysis. Each Cd^II centre is coordinated by six O atoms from four different (1,2,4,5-btc)⁴⁻ tetra­anions. Each Cd^II cation, located on a site of twofold symmetry, binds to four carboxyl­ate groups belonging to four separate (1,2,4,5-btc)⁴⁻ ligands. Each (1,2,4,5-btc)⁴⁻ anion, situated on a position of symmetry, binds to four crystallographically equivalent Cd^II centres. Neighbouring Cd^II cations inter­connect bridging (1,2,4,5-btc)⁴⁻ anions to form a three-dimensional {[Cd(1,2,4,5-btc)]²⁻}_n anionic coordination network with infinite tubular channels. The channels are visible in both the [10] and the [001] direction. Such a coordination network can be simplified as a (4,4)-connected framework with the point symbol (4²8⁴)(4²8⁴). To balance the negative charge of the metal–carboxyl­ate coordination network, the cavities of the network are occupied by protonated (1,4-H₂bpbd)²⁺ cations that are located on sites of twofold symmetry. In the crystal, there are strong hydrogen-bonding inter­actions between the anionic coordination network and the (1,4-H₂bpbd)²⁺ cations. Considering the hydrogen-bonding inter­actions, the structure can be further regarded as a three-dimensional (4,6)-connected supra­molecular architecture with the point symbol (4²6⁴)(4²6⁸7·8⁴). The thermal stability and photoluminescence properties of the title compound have been 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).

catena-Poly[4,4'-(buta-1,3-diene-1,4-diyl)dipyridin-1-ium [(µ₄-benzene-1,2,4,5-tetracarboxylato-κ⁶O¹,O^1':O²:O⁴,O^4':O⁵)cadmium(II)]]

Crystal data

(C14H14N2)[Cd(C10H2O8)]	F(000) = 1144
Mr = 572.80	Dx = 1.874 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.392 (2) Å	Cell parameters from 18574 reflections
b = 12.459 (3) Å	θ = 2.9–27.5°
c = 15.726 (3) Å	µ = 1.14 mm^−1
β = 94.25 (3)°	T = 223 K
V = 2030.5 (7) Å^3	Block, yellow
Z = 4	0.12 × 0.08 × 0.07 mm

Data collection

Bruker SMART CCD area detector diffractometer	2240 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
phi and ω scans	θmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −13→13
Tmin = 0.853, Tmax = 0.921	k = −14→16
18574 measured reflections	l = −20→20
2337 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.018	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.052	w = 1/[σ^2(Fo^2) + (0.0306P)^2 + 2.7443P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
2337 reflections	Δρmax = 0.38 e Å^−3
163 parameters	Δρmin = −0.62 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.

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

	x	y	z	Uiso*/Ueq
Cd1	0.5000	0.49448 (2)	0.7500	0.01338 (6)
N1	0.69212 (15)	0.86219 (12)	0.60852 (9)	0.0228 (3)
H1	0.706 (3)	0.852 (2)	0.6605 (18)	0.046 (7)*
O1	0.90691 (13)	0.87312 (12)	0.82656 (8)	0.0330 (3)
O2	0.71262 (15)	0.81903 (13)	0.77233 (8)	0.0393 (4)
O3	0.69232 (12)	0.57138 (11)	0.81480 (8)	0.0265 (3)
O4	0.50545 (13)	0.62278 (14)	0.85667 (9)	0.0409 (4)
C1	0.66919 (14)	0.66518 (12)	1.01167 (9)	0.0154 (3)
H1A	0.6134	0.6072	1.0194	0.018*
C2	0.69112 (14)	0.69659 (12)	0.92904 (9)	0.0142 (3)
C3	0.77305 (14)	0.78339 (12)	0.91679 (9)	0.0140 (3)
C4	0.79915 (16)	0.82832 (12)	0.83020 (10)	0.0184 (3)
C5	0.62575 (15)	0.62775 (12)	0.86007 (9)	0.0168 (3)
C6	0.56910 (17)	0.86382 (14)	0.57607 (10)	0.0229 (3)
H6	0.5020	0.8562	0.6125	0.028*
C7	0.54034 (16)	0.87658 (14)	0.48974 (10)	0.0212 (3)
H7	0.4538	0.8779	0.4675	0.025*
C8	0.64010 (16)	0.88766 (13)	0.43484 (10)	0.0187 (3)
C9	0.76708 (16)	0.88676 (14)	0.47214 (10)	0.0214 (3)
H9	0.8367	0.8950	0.4378	0.026*
C10	0.79015 (16)	0.87386 (14)	0.55896 (11)	0.0230 (3)
H10	0.8754	0.8733	0.5835	0.028*
C11	0.62006 (17)	0.89565 (15)	0.34199 (10)	0.0238 (3)
H11	0.6942	0.8995	0.3113	0.029*
C12	0.50556 (17)	0.89795 (15)	0.29653 (10)	0.0237 (3)
H12	0.4298	0.8996	0.3257	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.01605 (9)	0.01498 (9)	0.00897 (9)	0.000	0.00000 (6)	0.000
N1	0.0322 (8)	0.0236 (7)	0.0118 (6)	−0.0047 (6)	−0.0039 (5)	0.0009 (5)
O1	0.0304 (7)	0.0427 (8)	0.0266 (7)	−0.0092 (6)	0.0073 (5)	0.0164 (6)
O2	0.0506 (9)	0.0525 (9)	0.0130 (6)	−0.0181 (7)	−0.0092 (6)	0.0115 (6)
O3	0.0248 (6)	0.0305 (7)	0.0236 (6)	0.0027 (5)	−0.0017 (5)	−0.0119 (5)
O4	0.0200 (6)	0.0710 (11)	0.0320 (7)	−0.0136 (6)	0.0048 (5)	−0.0311 (7)
C1	0.0175 (7)	0.0151 (7)	0.0137 (7)	−0.0041 (5)	0.0014 (5)	0.0009 (5)
C2	0.0155 (6)	0.0158 (7)	0.0110 (6)	−0.0010 (5)	−0.0008 (5)	−0.0007 (5)
C3	0.0163 (7)	0.0161 (6)	0.0098 (6)	−0.0013 (5)	0.0011 (5)	0.0016 (5)
C4	0.0281 (8)	0.0160 (7)	0.0113 (7)	−0.0006 (6)	0.0039 (6)	0.0024 (5)
C5	0.0213 (7)	0.0183 (7)	0.0106 (6)	−0.0045 (6)	0.0007 (5)	−0.0002 (5)
C6	0.0279 (8)	0.0258 (8)	0.0154 (7)	−0.0060 (7)	0.0035 (6)	−0.0001 (6)
C7	0.0203 (7)	0.0267 (8)	0.0163 (7)	−0.0031 (6)	−0.0008 (6)	0.0009 (6)
C8	0.0235 (8)	0.0197 (7)	0.0125 (7)	−0.0023 (6)	−0.0007 (6)	0.0005 (6)
C9	0.0211 (8)	0.0253 (8)	0.0178 (8)	−0.0029 (6)	0.0015 (6)	−0.0009 (6)
C10	0.0241 (8)	0.0249 (8)	0.0189 (8)	−0.0022 (6)	−0.0058 (6)	−0.0019 (6)
C11	0.0275 (8)	0.0316 (9)	0.0125 (7)	−0.0012 (7)	0.0023 (6)	0.0009 (6)
C12	0.0280 (8)	0.0300 (9)	0.0129 (8)	−0.0005 (7)	0.0003 (6)	0.0000 (6)

Geometric parameters (Å, º)

Cd1—O1^i	2.2010 (13)	C1—H1A	0.9400
Cd1—O1^ii	2.2010 (13)	C2—C3	1.399 (2)
Cd1—O4	2.3147 (14)	C2—C5	1.505 (2)
Cd1—O3	2.3767 (13)	C3—C1^v	1.392 (2)
Cd1—O3^iii	2.3767 (13)	C3—C4	1.515 (2)
Cd1—O4^iii	2.3148 (14)	C6—C7	1.378 (2)
Cd1—C5^iii	2.6694 (16)	C6—H6	0.9400
Cd1—C5	2.6694 (16)	C7—C8	1.404 (2)
N1—C10	1.336 (2)	C7—H7	0.9400
N1—C6	1.341 (2)	C8—C9	1.404 (2)
N1—H1	0.83 (3)	C8—C11	1.463 (2)
O1—C4	1.256 (2)	C9—C10	1.378 (2)
O1—Cd1^iv	2.2009 (13)	C9—H9	0.9400
O2—C4	1.236 (2)	C10—H10	0.9400
O3—C5	1.246 (2)	C11—C12	1.342 (2)
O4—C5	1.249 (2)	C11—H11	0.9400
C1—C3^v	1.392 (2)	C12—C12^vi	1.459 (3)
C1—C2	1.392 (2)	C12—H12	0.9400
O1^ii—Cd1—O1^i	93.21 (8)	C1—C2—C3	119.30 (13)
O1^ii—Cd1—O4	151.97 (5)	C1—C2—C5	114.60 (13)
O1^i—Cd1—O4	93.79 (6)	C3—C2—C5	126.04 (13)
O1^ii—Cd1—O4^iii	93.79 (6)	C1^v—C3—C2	118.37 (13)
O1^i—Cd1—O4^iii	151.97 (5)	C1^v—C3—C4	117.47 (13)
O4—Cd1—O4^iii	92.65 (9)	C2—C3—C4	124.11 (13)
O1^ii—Cd1—O3^iii	115.60 (5)	O2—C4—O1	127.60 (15)
O1^i—Cd1—O3^iii	96.99 (5)	O2—C4—C3	117.25 (15)
O4—Cd1—O3^iii	90.40 (6)	O1—C4—C3	115.13 (14)
O4^iii—Cd1—O3^iii	55.69 (5)	O3—C5—O4	122.97 (15)
O1^ii—Cd1—O3	96.99 (5)	O3—C5—C2	119.55 (14)
O1^i—Cd1—O3	115.60 (5)	O4—C5—C2	117.14 (14)
O4—Cd1—O3	55.69 (5)	O3—C5—Cd1	62.91 (8)
O4^iii—Cd1—O3	90.40 (6)	O4—C5—Cd1	60.07 (9)
O3^iii—Cd1—O3	132.46 (7)	C2—C5—Cd1	174.33 (10)
O1^ii—Cd1—C5^iii	106.65 (5)	N1—C6—C7	120.51 (16)
O1^i—Cd1—C5^iii	124.62 (5)	N1—C6—H6	119.7
O4—Cd1—C5^iii	91.43 (6)	C7—C6—H6	119.7
O4^iii—Cd1—C5^iii	27.88 (5)	C6—C7—C8	120.08 (15)
O3^iii—Cd1—C5^iii	27.81 (5)	C6—C7—H7	120.0
O3—Cd1—C5^iii	112.52 (5)	C8—C7—H7	120.0
O1^ii—Cd1—C5	124.62 (5)	C9—C8—C7	117.15 (14)
O1^i—Cd1—C5	106.65 (5)	C9—C8—C11	118.51 (15)
O4—Cd1—C5	27.88 (5)	C7—C8—C11	124.29 (15)
O4^iii—Cd1—C5	91.43 (6)	C10—C9—C8	120.26 (15)
O3^iii—Cd1—C5	112.52 (5)	C10—C9—H9	119.9
O3—Cd1—C5	27.81 (5)	C8—C9—H9	119.9
C5^iii—Cd1—C5	103.07 (7)	N1—C10—C9	120.44 (15)
C10—N1—C6	121.54 (15)	N1—C10—H10	119.8
C10—N1—H1	120.2 (19)	C9—C10—H10	119.8
C6—N1—H1	118.3 (19)	C12—C11—C8	126.02 (16)
C4—O1—Cd1^iv	139.43 (12)	C12—C11—H11	117.0
C5—O3—Cd1	89.28 (10)	C8—C11—H11	117.0
C5—O4—Cd1	92.06 (10)	C11—C12—C12^vi	122.4 (2)
C3^v—C1—C2	122.32 (14)	C11—C12—H12	118.8
C3^v—C1—H1A	118.8	C12^vi—C12—H12	118.8
C2—C1—H1A	118.8

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.83 (3)	1.80 (3)	2.6249 (19)	171 (3)