Synthesis, structure and photoluminescence properties of a three-dimensional cadmium(II) (4,5)-connected coordination network

The assembly of coordination polymers from metal ions and organic moieties is currently attracting considerable attention in crystal engineering due to their intriguing architectures and potential applications as functional materials. A new coordination polymer, namely poly[[μ₂-trans-1,2-bis­(pyridin-3-yl)ethyl­ene-κ²N:N′]bis­(μ₄-4,4′-oxydibenzoato-κ⁶O:O,O′:O′′:O′′,O′′′)dicadmium(II)], [Cd₂(C₁₄H₈O₅)₂(C₁₂H₁₀N₂)]_n or [Cd₂(4,4′-OBB)₂(3,3′-BPE)]_n, has been synthesized by the the self-assembly of Cd(NO₃)₂·4H₂O, 4,4′-oxydi­benzoic acid (4,4′-H₂OBB) and trans-1,2-bis­(pyridin-3-yl)ethene (3,3′-BPE) under hydro­thermal conditions. The title compound was structurally characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction analysis. Each Cd^II centre is coordinated by six carboxyl­ate O atoms from four different 4,4′-OBB²⁻ ligands and by one pyridyl N atom form a 3,3′-BPE ligand. Adjacent crystallographically equivalent Cd^II ions are bridged by 4,4′-OBB²⁻ ligands, affording a two-dimensional [Cd(4,4′-OBB)]_n net extending in the ac plane. Neighbouring [Cd(4,4′-OBB)]_n nets are inter­linked by 3,3′-BPE along the b axis to form a three-dimensional (3D) [Cd₂(4,4′-OBB)₂(3,3′-BPE)]_n coordination network. In the network, each Cd^II centre is linked by four different 4,4′-OBB²⁻ ligands and one 3,3′-BPE ligand. Meanwhile, each 4,4′-OBB²⁻ ligand connects four separate Cd^II ions. Therefore, if the 4,4′-OBB²⁻ ligands and Cd^II ions are considered as 4- and 5-connecting nodes, the structure of the title compound can be simplified as a 3D (4,5)-connected binodal framework with the rare (4⁴6²)(4⁴6⁶) TCS topology (Pearson, 1985; Blake et al., 2011). The thermal stability and photoluminescence properties of the title compound have also 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).

Poly[[µ₂-trans-1,2-bis(pyridin-3-yl)ethylene-κ²N:N']bis(µ₄-4,4'-oxydibenzoato-κ⁶O:O,O':O'':O'',O''')dicadmium(II)]

Crystal data

[Cd2(C14H8O5)2(C12H10N2)]	Z = 1
Mr = 919.44	F(000) = 456
Triclinic, P1	Dx = 1.620 Mg m^−3
a = 7.6924 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.128 (2) Å	Cell parameters from 17558 reflections
c = 12.240 (2) Å	θ = 3.1–27.5°
α = 84.85 (3)°	µ = 1.19 mm^−1
β = 85.98 (3)°	T = 223 K
γ = 83.70 (3)°	Block, colorless
V = 942.3 (3) Å^3	0.28 × 0.25 × 0.16 mm

Data collection

Bruker SMART CCD area detector diffractometer	4065 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.016
phi and ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −9→9
Tmin = 0.743, Tmax = 0.821	k = −13→13
17558 measured reflections	l = −14→15
4296 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.019	H-atom parameters constrained
wR(F^2) = 0.049	w = 1/[σ^2(Fo^2) + (0.0229P)^2 + 0.3899P] where P = (Fo^2 + 2Fc^2)/3
S = 1.13	(Δ/σ)max = 0.001
4296 reflections	Δρmax = 0.32 e Å^−3
244 parameters	Δρmin = −0.59 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	0.25340 (2)	0.48919 (2)	0.47730 (2)	0.02732 (5)
N1	0.20476 (18)	0.71564 (13)	0.44404 (12)	0.0305 (3)
O1	0.30676 (17)	0.31702 (14)	0.61377 (11)	0.0404 (3)
O2	0.45967 (16)	0.48771 (13)	0.61720 (10)	0.0357 (3)
O3	1.00031 (18)	0.45799 (13)	1.38430 (10)	0.0386 (3)
O4	1.24677 (19)	0.33918 (15)	1.34201 (13)	0.0509 (4)
O5	0.7588 (3)	0.11391 (14)	1.02079 (13)	0.0644 (5)
C1	0.0762 (2)	0.76843 (18)	0.38000 (17)	0.0387 (4)
H1	0.0035	0.7116	0.3530	0.046*
C2	0.0477 (3)	0.9037 (2)	0.3527 (2)	0.0522 (5)
H2	−0.0452	0.9389	0.3093	0.063*
C3	0.1572 (3)	0.98658 (19)	0.3899 (2)	0.0501 (5)
H3	0.1386	1.0791	0.3723	0.060*
C4	0.2946 (2)	0.93398 (16)	0.45301 (16)	0.0342 (4)
C5	0.3098 (2)	0.79683 (16)	0.48036 (14)	0.0306 (3)
H5	0.3981	0.7596	0.5266	0.037*
C6	0.4198 (3)	1.02021 (17)	0.48638 (17)	0.0404 (4)
H6	0.3820	1.1115	0.4884	0.048*
C7	0.4986 (2)	0.31090 (18)	0.75858 (14)	0.0332 (3)
C8	0.6013 (3)	0.38123 (19)	0.81647 (16)	0.0421 (4)
H8	0.6123	0.4715	0.7948	0.050*
C9	0.6877 (3)	0.3195 (2)	0.90602 (17)	0.0482 (5)
H9	0.7563	0.3675	0.9456	0.058*
C10	0.6717 (3)	0.18627 (19)	0.93639 (15)	0.0428 (4)
C11	0.5696 (3)	0.11523 (19)	0.87970 (15)	0.0435 (4)
H11	0.5596	0.0248	0.9011	0.052*
C12	0.4824 (3)	0.17765 (19)	0.79145 (15)	0.0389 (4)
H12	0.4116	0.1298	0.7533	0.047*
C13	0.8390 (3)	0.18334 (19)	1.09348 (16)	0.0480 (5)
C14	0.7381 (3)	0.2539 (2)	1.16951 (19)	0.0533 (5)
H14	0.6152	0.2591	1.1710	0.064*
C15	0.8198 (3)	0.3177 (2)	1.24429 (16)	0.0442 (4)
H15	0.7514	0.3682	1.2955	0.053*
C16	1.0004 (2)	0.30787 (16)	1.24446 (13)	0.0332 (4)
C17	1.0994 (3)	0.2344 (2)	1.16737 (18)	0.0506 (5)
H17	1.2224	0.2263	1.1669	0.061*
C18	1.0185 (3)	0.1727 (2)	1.09095 (19)	0.0579 (6)
H18	1.0859	0.1242	1.0381	0.070*
C19	0.4152 (2)	0.37528 (18)	0.65794 (14)	0.0326 (3)
C20	1.0878 (2)	0.37190 (16)	1.32863 (13)	0.0320 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.02974 (7)	0.02179 (6)	0.03276 (7)	−0.00512 (4)	−0.01441 (5)	−0.00227 (4)
N1	0.0287 (7)	0.0235 (6)	0.0401 (8)	−0.0051 (5)	−0.0052 (6)	−0.0018 (6)
O1	0.0367 (6)	0.0461 (7)	0.0403 (7)	−0.0061 (5)	−0.0197 (5)	0.0008 (6)
O2	0.0340 (6)	0.0403 (7)	0.0326 (6)	−0.0029 (5)	−0.0086 (5)	0.0026 (5)
O3	0.0492 (7)	0.0389 (7)	0.0320 (6)	−0.0126 (6)	−0.0067 (5)	−0.0141 (5)
O4	0.0503 (8)	0.0469 (8)	0.0607 (9)	−0.0024 (6)	−0.0254 (7)	−0.0190 (7)
O5	0.1140 (14)	0.0343 (7)	0.0518 (9)	0.0009 (8)	−0.0583 (9)	−0.0102 (6)
C1	0.0324 (8)	0.0324 (9)	0.0532 (11)	−0.0071 (7)	−0.0129 (8)	−0.0006 (8)
C2	0.0479 (11)	0.0357 (10)	0.0737 (15)	−0.0009 (8)	−0.0288 (11)	0.0072 (10)
C3	0.0543 (12)	0.0242 (8)	0.0718 (14)	−0.0017 (8)	−0.0199 (10)	0.0055 (9)
C4	0.0373 (9)	0.0229 (7)	0.0434 (9)	−0.0049 (6)	−0.0046 (7)	−0.0039 (7)
C5	0.0312 (8)	0.0237 (7)	0.0380 (9)	−0.0046 (6)	−0.0059 (7)	−0.0037 (6)
C6	0.0477 (10)	0.0205 (7)	0.0551 (11)	−0.0072 (7)	−0.0074 (9)	−0.0064 (7)
C7	0.0330 (8)	0.0421 (9)	0.0260 (8)	−0.0058 (7)	−0.0086 (6)	−0.0023 (7)
C8	0.0557 (11)	0.0366 (9)	0.0370 (9)	−0.0106 (8)	−0.0186 (8)	−0.0009 (8)
C9	0.0680 (13)	0.0409 (10)	0.0416 (10)	−0.0114 (9)	−0.0310 (10)	−0.0076 (8)
C10	0.0626 (12)	0.0380 (9)	0.0305 (9)	−0.0009 (8)	−0.0238 (8)	−0.0072 (7)
C11	0.0669 (13)	0.0342 (9)	0.0329 (9)	−0.0116 (8)	−0.0194 (9)	−0.0015 (7)
C12	0.0462 (10)	0.0434 (10)	0.0311 (8)	−0.0144 (8)	−0.0152 (7)	−0.0035 (7)
C13	0.0798 (15)	0.0314 (9)	0.0368 (10)	0.0023 (9)	−0.0364 (10)	−0.0083 (8)
C14	0.0533 (12)	0.0559 (13)	0.0556 (13)	−0.0015 (10)	−0.0275 (10)	−0.0178 (10)
C15	0.0504 (11)	0.0468 (11)	0.0389 (10)	−0.0016 (8)	−0.0148 (8)	−0.0181 (8)
C16	0.0487 (10)	0.0254 (7)	0.0273 (8)	−0.0017 (7)	−0.0159 (7)	−0.0042 (6)
C17	0.0521 (12)	0.0529 (12)	0.0492 (11)	0.0059 (9)	−0.0149 (9)	−0.0228 (10)
C18	0.0770 (16)	0.0545 (13)	0.0448 (11)	0.0112 (11)	−0.0200 (11)	−0.0275 (10)
C19	0.0282 (8)	0.0428 (9)	0.0269 (8)	−0.0003 (7)	−0.0057 (6)	−0.0039 (7)
C20	0.0471 (10)	0.0239 (7)	0.0272 (8)	−0.0095 (7)	−0.0119 (7)	0.0008 (6)

Geometric parameters (Å, º)

Cd1—O1	2.3271 (15)	C4—C6	1.470 (2)
Cd1—O2	2.4128 (14)	C5—H5	0.9400
Cd1—O2^i	2.4436 (14)	C6—C6^v	1.313 (4)
Cd1—O3^ii	2.3867 (14)	C6—H6	0.9400
Cd1—O3^iii	2.5366 (15)	C7—C8	1.388 (2)
Cd1—O4^ii	2.3524 (15)	C7—C12	1.390 (3)
Cd1—N1	2.2872 (14)	C7—C19	1.493 (2)
Cd1—C19	2.7170 (18)	C8—C9	1.386 (3)
Cd1—C20^ii	2.7187 (18)	C8—H8	0.9400
N1—C5	1.337 (2)	C9—C10	1.383 (3)
N1—C1	1.340 (2)	C9—H9	0.9400
O1—C19	1.251 (2)	C10—C11	1.381 (3)
O2—C19	1.273 (2)	C11—C12	1.379 (3)
O2—Cd1^i	2.4436 (14)	C11—H11	0.9400
O3—C20	1.261 (2)	C12—H12	0.9400
O3—Cd1^iv	2.3867 (14)	C13—C14	1.370 (3)
O3—Cd1^iii	2.5366 (15)	C13—C18	1.372 (4)
O4—C20	1.250 (2)	C14—C15	1.388 (3)
O4—Cd1^iv	2.3524 (15)	C14—H14	0.9400
O5—C10	1.381 (2)	C15—C16	1.382 (3)
O5—C13	1.397 (2)	C15—H15	0.9400
C1—C2	1.378 (3)	C16—C17	1.388 (3)
C1—H1	0.9400	C16—C20	1.499 (2)
C2—C3	1.378 (3)	C17—C18	1.387 (3)
C2—H2	0.9400	C17—H17	0.9400
C3—C4	1.384 (3)	C18—H18	0.9400
C3—H3	0.9400	C20—Cd1^iv	2.7187 (18)
C4—C5	1.393 (2)
N1—Cd1—O1	144.00 (5)	C3—C4—C5	116.90 (16)
N1—Cd1—O4^ii	123.66 (6)	C3—C4—C6	120.64 (16)
O1—Cd1—O4^ii	92.29 (5)	C5—C4—C6	122.45 (17)
N1—Cd1—O3^ii	91.54 (6)	N1—C5—C4	123.20 (16)
O1—Cd1—O3^ii	110.24 (5)	N1—C5—H5	118.4
O4^ii—Cd1—O3^ii	54.97 (5)	C4—C5—H5	118.4
N1—Cd1—O2	96.89 (6)	C6^v—C6—C4	125.1 (2)
O1—Cd1—O2	55.28 (5)	C6^v—C6—H6	117.4
O4^ii—Cd1—O2	129.11 (5)	C4—C6—H6	117.4
O3^ii—Cd1—O2	162.53 (5)	C8—C7—C12	119.35 (16)
N1—Cd1—O2^i	85.40 (6)	C8—C7—C19	120.32 (17)
O1—Cd1—O2^i	104.30 (5)	C12—C7—C19	120.22 (16)
O4^ii—Cd1—O2^i	80.49 (6)	C9—C8—C7	120.57 (18)
O3^ii—Cd1—O2^i	123.16 (4)	C9—C8—H8	119.7
O2—Cd1—O2^i	72.95 (5)	C7—C8—H8	119.7
N1—Cd1—O3^iii	79.12 (6)	C10—C9—C8	119.12 (17)
O1—Cd1—O3^iii	78.98 (5)	C10—C9—H9	120.4
O4^ii—Cd1—O3^iii	123.42 (5)	C8—C9—H9	120.4
O3^ii—Cd1—O3^iii	75.88 (5)	C11—C10—O5	115.34 (17)
O2—Cd1—O3^iii	90.69 (4)	C11—C10—C9	120.91 (17)
O2^i—Cd1—O3^iii	155.99 (4)	O5—C10—C9	123.70 (17)
N1—Cd1—C19	121.50 (6)	C12—C11—C10	119.67 (18)
O1—Cd1—C19	27.35 (5)	C12—C11—H11	120.2
O4^ii—Cd1—C19	112.60 (6)	C10—C11—H11	120.2
O3^ii—Cd1—C19	136.69 (5)	C11—C12—C7	120.37 (17)
O2—Cd1—C19	27.95 (5)	C11—C12—H12	119.8
O2^i—Cd1—C19	89.30 (5)	C7—C12—H12	119.8
O3^iii—Cd1—C19	83.38 (5)	C14—C13—C18	121.42 (18)
N1—Cd1—C20^ii	109.01 (6)	C14—C13—O5	119.7 (2)
O1—Cd1—C20^ii	102.75 (5)	C18—C13—O5	118.7 (2)
O4^ii—Cd1—C20^ii	27.33 (5)	C13—C14—C15	119.1 (2)
O3^ii—Cd1—C20^ii	27.64 (5)	C13—C14—H14	120.5
O2—Cd1—C20^ii	153.30 (5)	C15—C14—H14	120.5
O2^i—Cd1—C20^ii	102.15 (5)	C16—C15—C14	120.85 (19)
O3^iii—Cd1—C20^ii	100.21 (5)	C16—C15—H15	119.6
C19—Cd1—C20^ii	128.95 (5)	C14—C15—H15	119.6
C5—N1—C1	118.72 (15)	C15—C16—C17	118.86 (17)
C5—N1—Cd1	121.52 (11)	C15—C16—C20	120.60 (16)
C1—N1—Cd1	119.57 (12)	C17—C16—C20	120.51 (17)
C19—O1—Cd1	93.95 (11)	C18—C17—C16	120.5 (2)
C19—O2—Cd1	89.43 (10)	C18—C17—H17	119.7
C19—O2—Cd1^i	121.99 (11)	C16—C17—H17	119.7
Cd1—O2—Cd1^i	107.05 (5)	C13—C18—C17	119.2 (2)
C20—O3—Cd1^iv	90.99 (11)	C13—C18—H18	120.4
C20—O3—Cd1^iii	147.54 (12)	C17—C18—H18	120.4
Cd1^iv—O3—Cd1^iii	104.12 (5)	O1—C19—O2	121.25 (16)
C20—O4—Cd1^iv	92.88 (11)	O1—C19—C7	119.80 (16)
C10—O5—C13	118.23 (15)	O2—C19—C7	118.93 (15)
N1—C1—C2	121.80 (17)	O1—C19—Cd1	58.70 (9)
N1—C1—H1	119.1	O2—C19—Cd1	62.62 (9)
C2—C1—H1	119.1	C7—C19—Cd1	178.09 (12)
C1—C2—C3	119.11 (18)	O4—C20—O3	121.15 (16)
C1—C2—H2	120.4	O4—C20—C16	119.20 (16)
C3—C2—H2	120.4	O3—C20—C16	119.65 (16)
C2—C3—C4	120.17 (17)	O4—C20—Cd1^iv	59.79 (9)
C2—C3—H3	119.9	O3—C20—Cd1^iv	61.37 (9)
C4—C3—H3	119.9	C16—C20—Cd1^iv	178.49 (13)

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