Construction and photoluminescence properties of a three-dimensional Zn^II coordination network based on naphthalene-1,4-dicarb­oxy­lic acid and 1,6-bis­(pyridin-3-yl)-1,3,5-hexa­triene

In recent years, coordination polymers constructed from multidentate carboxyl­ate and pyridyl ligands have attracted much attention because these ligands can adopt a rich variety of coordination modes and thus lead to the formation of crystalline products with intriguing structures and inter­esting properties. A new coordination polymer, namely poly[[μ₂-1,6-bis­(pyridin-3-yl)-1,3,5-hexa­triene-κ²N:N′](μ₃-naphthalene-1,4-di­carboxyl­ato-κ⁴O¹,O^1′:O⁴:O^4′)zinc(II)], [Zn(C₁₂H₆O₄)(C₁₆H₁₄N₂)]_n, has been prepared by the self-assembly of Zn(NO₃)₂·6H₂O, naphthalene-1,4-di­carb­oxy­lic acid (1,4-H₂ndc) and 1,6-bis­(pyridin-3-yl)-1,3,5-hexa­triene (3,3′-bphte) 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 Zn^II ion is six-coordinated by four O atoms from three 1,4-ndc²⁻ ligands and by two N atoms from two 3,3′-bphte ligands, forming a distorted octa­hedral ZnO₄N₂ coordination geometry. Pairs of Zn^II ions are linked by 1,4-ndc²⁻ ligands, leading to the formation of a two-dimensional square lattice (sql) layer extending in the ab plane. In the crystal, adjacent layers are further connected by 3,3′-bphte bridges, generating a three-dimensional architecture. From a topological view­point, if each dinuclear zinc unit is considered as a 6-connected node and the 1,4-ndc²⁻ and 3,3′-bphte ligands are regarded as linkers, the structure can be simplified as a unique three-dimensional 6-connected framework with the point symbol 4⁴6¹⁰8. The thermal stability and solid-state photoluminescence properties 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: SHELXT2014 (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[[µ₂-1,6-bis(pyridin-3-yl)-1,3,5-hexatriene-κ²N:N'](µ₃-naphthalene-1,4-dicarboxylato-κ⁴O¹,O^1':O⁴:O^4')zinc(II)]

Crystal data

[Zn(C12H6O4)(C16H14N2)]	F(000) = 1056
Mr = 513.85	Dx = 1.471 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.160 (2) Å	Cell parameters from 29654 reflections
b = 12.917 (3) Å	θ = 2.8–27.6°
c = 18.551 (6) Å	µ = 1.10 mm^−1
β = 119.79 (2)°	T = 223 K
V = 2320.8 (11) Å^3	Block, yellow
Z = 4	0.26 × 0.24 × 0.20 mm

Data collection

Bruker SMART CCD area detector diffractometer	3194 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.095
phi and ω scans	θmax = 27.6°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −14→14
Tmin = 0.853, Tmax = 0.921	k = −16→16
29654 measured reflections	l = −21→24
5295 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)] = 0.058	H-atom parameters constrained
wR(F^2) = 0.119	w = 1/[σ^2(Fo^2) + (0.0319P)^2 + 3.769P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
5295 reflections	Δρmax = 0.57 e Å^−3
316 parameters	Δρmin = −0.50 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
Zn1	0.84302 (4)	0.10700 (3)	0.43534 (3)	0.03160 (14)
N1	0.7505 (3)	0.0199 (2)	0.4940 (2)	0.0362 (8)
N2	−0.0581 (3)	−0.8114 (2)	0.3760 (2)	0.0401 (8)
O1	0.6519 (2)	0.1081 (2)	0.32057 (17)	0.0405 (7)
O2	0.6770 (3)	0.2335 (2)	0.40687 (17)	0.0477 (8)
O3	−0.0166 (3)	0.32691 (19)	0.04400 (16)	0.0407 (7)
O4	0.0964 (3)	0.47216 (19)	0.09999 (17)	0.0417 (7)
C1	0.6735 (4)	−0.0640 (3)	0.4563 (3)	0.0379 (10)
H1	0.6573	−0.0798	0.4027	0.046*
C2	0.6165 (4)	−0.1287 (3)	0.4904 (3)	0.0441 (11)
C3	0.6407 (6)	−0.1038 (4)	0.5689 (3)	0.0699 (16)
H3	0.6053	−0.1455	0.5955	0.084*
C4	0.7179 (6)	−0.0164 (4)	0.6080 (3)	0.0780 (18)
H4	0.7344	0.0023	0.6612	0.094*
C5	0.7697 (5)	0.0425 (4)	0.5685 (3)	0.0529 (12)
H5	0.8215	0.1017	0.5957	0.064*
C6	0.5356 (5)	−0.2181 (3)	0.4423 (3)	0.0535 (12)
H6	0.5302	−0.2298	0.3907	0.064*
C7	0.4691 (5)	−0.2844 (3)	0.4650 (3)	0.0544 (12)
H7	0.4721	−0.2723	0.5158	0.065*
C8	0.3930 (5)	−0.3731 (3)	0.4175 (3)	0.0557 (13)
H8	0.3893	−0.3857	0.3666	0.067*
C9	0.3275 (5)	−0.4382 (3)	0.4415 (3)	0.0520 (12)
H9	0.3363	−0.4270	0.4940	0.062*
C10	0.2441 (5)	−0.5246 (3)	0.3939 (3)	0.0525 (12)
H10	0.2316	−0.5351	0.3405	0.063*
C11	0.1834 (5)	−0.5907 (3)	0.4212 (3)	0.0507 (12)
H11	0.2016	−0.5808	0.4760	0.061*
C12	0.0916 (4)	−0.6768 (3)	0.3754 (3)	0.0448 (11)
C13	0.0521 (6)	−0.7012 (4)	0.2947 (4)	0.0794 (19)
H13	0.0877	−0.6640	0.2660	0.095*
C14	−0.0409 (7)	−0.7813 (5)	0.2558 (4)	0.094 (2)
H14	−0.0687	−0.7991	0.2005	0.113*
C15	−0.0914 (6)	−0.8338 (4)	0.2985 (3)	0.0652 (15)
H15	−0.1530	−0.8888	0.2717	0.078*
C16	0.0327 (4)	−0.7338 (3)	0.4127 (3)	0.0382 (10)
H16	0.0579	−0.7172	0.4678	0.046*
C17	0.4606 (3)	0.2235 (3)	0.2820 (2)	0.0295 (8)
C18	0.4369 (4)	0.3271 (3)	0.2848 (2)	0.0328 (9)
H18	0.5055	0.3682	0.3269	0.039*
C19	0.3123 (4)	0.3727 (3)	0.2263 (2)	0.0295 (8)
H19	0.3008	0.4446	0.2281	0.035*
C20	0.2065 (3)	0.3149 (2)	0.1662 (2)	0.0261 (8)
C21	0.2202 (3)	0.2042 (3)	0.1676 (2)	0.0277 (8)
C22	0.3511 (3)	0.1586 (2)	0.2242 (2)	0.0274 (8)
C23	0.3652 (4)	0.0490 (3)	0.2227 (3)	0.0398 (10)
H23	0.4510	0.0185	0.2587	0.048*
C24	0.2580 (4)	−0.0125 (3)	0.1706 (3)	0.0452 (11)
H24	0.2705	−0.0844	0.1702	0.054*
C25	0.1288 (4)	0.0316 (3)	0.1174 (3)	0.0439 (11)
H25	0.0545	−0.0113	0.0821	0.053*
C26	0.1096 (4)	0.1359 (3)	0.1161 (2)	0.0364 (9)
H26	0.0216	0.1636	0.0806	0.044*
C27	0.6057 (4)	0.1854 (3)	0.3404 (2)	0.0358 (9)
C28	0.0867 (3)	0.3755 (3)	0.0989 (2)	0.0296 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0223 (2)	0.0258 (2)	0.0331 (2)	−0.00409 (18)	0.00353 (17)	0.00225 (19)
N1	0.0314 (17)	0.0347 (17)	0.0376 (19)	−0.0058 (14)	0.0135 (15)	0.0007 (14)
N2	0.0390 (19)	0.0313 (17)	0.047 (2)	−0.0086 (14)	0.0188 (17)	−0.0030 (15)
O1	0.0247 (13)	0.0353 (14)	0.0499 (17)	0.0059 (12)	0.0098 (12)	0.0041 (13)
O2	0.0330 (15)	0.0463 (16)	0.0394 (16)	0.0008 (13)	−0.0006 (13)	0.0024 (13)
O3	0.0300 (14)	0.0326 (13)	0.0362 (15)	0.0083 (11)	−0.0011 (12)	−0.0031 (12)
O4	0.0280 (14)	0.0261 (13)	0.0519 (18)	0.0038 (11)	0.0054 (13)	0.0052 (12)
C1	0.036 (2)	0.038 (2)	0.037 (2)	−0.0059 (17)	0.0162 (19)	−0.0012 (17)
C2	0.046 (2)	0.043 (2)	0.048 (3)	−0.0129 (19)	0.027 (2)	−0.0021 (19)
C3	0.089 (4)	0.081 (4)	0.058 (3)	−0.039 (3)	0.050 (3)	−0.008 (3)
C4	0.102 (4)	0.096 (4)	0.056 (3)	−0.050 (4)	0.054 (3)	−0.030 (3)
C5	0.059 (3)	0.058 (3)	0.048 (3)	−0.022 (2)	0.031 (2)	−0.014 (2)
C6	0.064 (3)	0.049 (3)	0.056 (3)	−0.019 (2)	0.037 (3)	−0.005 (2)
C7	0.055 (3)	0.047 (3)	0.063 (3)	−0.016 (2)	0.032 (3)	0.000 (2)
C8	0.054 (3)	0.049 (3)	0.067 (3)	−0.017 (2)	0.032 (3)	−0.001 (2)
C9	0.054 (3)	0.048 (2)	0.057 (3)	−0.019 (2)	0.029 (2)	−0.003 (2)
C10	0.053 (3)	0.045 (2)	0.065 (3)	−0.014 (2)	0.033 (3)	−0.002 (2)
C11	0.052 (3)	0.045 (2)	0.057 (3)	−0.017 (2)	0.028 (2)	−0.004 (2)
C12	0.047 (2)	0.039 (2)	0.056 (3)	−0.0135 (19)	0.032 (2)	−0.008 (2)
C13	0.110 (5)	0.081 (4)	0.078 (4)	−0.051 (4)	0.070 (4)	−0.024 (3)
C14	0.133 (6)	0.106 (5)	0.070 (4)	−0.073 (4)	0.071 (4)	−0.043 (3)
C15	0.080 (4)	0.066 (3)	0.059 (3)	−0.042 (3)	0.042 (3)	−0.026 (3)
C16	0.040 (2)	0.034 (2)	0.038 (2)	−0.0080 (17)	0.0176 (19)	−0.0007 (17)
C17	0.0223 (17)	0.0310 (18)	0.0290 (19)	0.0021 (14)	0.0081 (16)	0.0019 (15)
C18	0.0271 (19)	0.0301 (18)	0.032 (2)	−0.0026 (15)	0.0076 (17)	−0.0015 (16)
C19	0.0288 (18)	0.0256 (18)	0.0281 (19)	0.0022 (14)	0.0097 (16)	0.0003 (14)
C20	0.0230 (17)	0.0235 (16)	0.0282 (18)	0.0031 (14)	0.0101 (15)	0.0018 (14)
C21	0.0242 (18)	0.0282 (17)	0.0265 (19)	0.0019 (14)	0.0093 (16)	0.0012 (15)
C22	0.0250 (18)	0.0234 (17)	0.0278 (19)	0.0025 (14)	0.0086 (16)	0.0030 (14)
C23	0.031 (2)	0.0267 (19)	0.049 (2)	0.0045 (16)	0.0096 (19)	0.0045 (17)
C24	0.045 (2)	0.0213 (18)	0.057 (3)	−0.0021 (17)	0.017 (2)	−0.0019 (18)
C25	0.038 (2)	0.0307 (19)	0.047 (2)	−0.0079 (17)	0.009 (2)	−0.0047 (18)
C26	0.0281 (19)	0.035 (2)	0.036 (2)	−0.0014 (15)	0.0090 (18)	0.0012 (16)
C27	0.0247 (19)	0.035 (2)	0.039 (2)	−0.0006 (16)	0.0093 (18)	0.0109 (18)
C28	0.0211 (17)	0.037 (2)	0.0269 (19)	0.0053 (15)	0.0089 (15)	−0.0013 (16)

Geometric parameters (Å, º)

Zn1—O3^i	2.027 (3)	C9—C10	1.440 (6)
Zn1—O4^ii	2.088 (3)	C9—H9	0.9400
Zn1—O1	2.138 (3)	C10—C11	1.336 (6)
Zn1—N1	2.153 (3)	C10—H10	0.9400
Zn1—N2^iii	2.178 (3)	C11—C12	1.464 (5)
Zn1—O2	2.325 (3)	C11—H11	0.9400
Zn1—C27	2.551 (4)	C12—C13	1.369 (7)
N1—C5	1.322 (5)	C12—C16	1.381 (6)
N1—C1	1.344 (5)	C13—C14	1.388 (7)
N2—C15	1.326 (6)	C13—H13	0.9400
N2—C16	1.345 (5)	C14—C15	1.360 (7)
N2—Zn1^iv	2.178 (3)	C14—H14	0.9400
O1—C27	1.259 (5)	C15—H15	0.9400
O2—C27	1.251 (5)	C16—H16	0.9400
O3—C28	1.262 (4)	C17—C18	1.370 (5)
O3—Zn1^v	2.027 (2)	C17—C22	1.429 (5)
O4—C28	1.253 (4)	C17—C27	1.515 (5)
O4—Zn1^vi	2.088 (3)	C18—C19	1.400 (5)
C1—C2	1.379 (6)	C18—H18	0.9400
C1—H1	0.9400	C19—C20	1.374 (5)
C2—C3	1.382 (6)	C19—H19	0.9400
C2—C6	1.464 (6)	C20—C21	1.436 (5)
C3—C4	1.386 (7)	C20—C28	1.517 (4)
C3—H3	0.9400	C21—C26	1.429 (5)
C4—C5	1.367 (7)	C21—C22	1.435 (5)
C4—H4	0.9400	C22—C23	1.426 (5)
C5—H5	0.9400	C23—C24	1.359 (5)
C6—C7	1.331 (6)	C23—H23	0.9400
C6—H6	0.9400	C24—C25	1.401 (5)
C7—C8	1.437 (6)	C24—H24	0.9400
C7—H7	0.9400	C25—C26	1.363 (5)
C8—C9	1.328 (6)	C25—H25	0.9400
C8—H8	0.9400	C26—H26	0.9400
O3^i—Zn1—O4^ii	116.90 (10)	C11—C10—H10	118.1
O3^i—Zn1—O1	152.05 (11)	C9—C10—H10	118.1
O4^ii—Zn1—O1	90.66 (10)	C10—C11—C12	127.2 (5)
O3^i—Zn1—N1	92.60 (12)	C10—C11—H11	116.4
O4^ii—Zn1—N1	91.98 (12)	C12—C11—H11	116.4
O1—Zn1—N1	90.87 (11)	C13—C12—C16	116.7 (4)
O3^i—Zn1—N2^iii	87.90 (12)	C13—C12—C11	124.2 (4)
O4^ii—Zn1—N2^iii	85.43 (12)	C16—C12—C11	118.9 (4)
O1—Zn1—N2^iii	89.93 (12)	C12—C13—C14	119.5 (5)
N1—Zn1—N2^iii	177.30 (12)	C12—C13—H13	120.2
O3^i—Zn1—O2	93.73 (10)	C14—C13—H13	120.2
O4^ii—Zn1—O2	149.36 (10)	C15—C14—C13	119.2 (5)
O1—Zn1—O2	58.73 (10)	C15—C14—H14	120.4
N1—Zn1—O2	87.34 (12)	C13—C14—H14	120.4
N2^iii—Zn1—O2	95.27 (12)	N2—C15—C14	123.3 (4)
O3^i—Zn1—C27	122.95 (12)	N2—C15—H15	118.3
O4^ii—Zn1—C27	120.10 (12)	C14—C15—H15	118.3
O1—Zn1—C27	29.51 (11)	N2—C16—C12	124.8 (4)
N1—Zn1—C27	87.85 (12)	N2—C16—H16	117.6
N2^iii—Zn1—C27	94.11 (12)	C12—C16—H16	117.6
O2—Zn1—C27	29.26 (11)	C18—C17—C22	119.5 (3)
C5—N1—C1	116.9 (4)	C18—C17—C27	116.6 (3)
C5—N1—Zn1	123.0 (3)	C22—C17—C27	123.9 (3)
C1—N1—Zn1	120.1 (3)	C17—C18—C19	121.2 (3)
C15—N2—C16	116.5 (4)	C17—C18—H18	119.4
C15—N2—Zn1^iv	120.2 (3)	C19—C18—H18	119.4
C16—N2—Zn1^iv	123.3 (3)	C20—C19—C18	121.5 (3)
C27—O1—Zn1	93.7 (2)	C20—C19—H19	119.3
C27—O2—Zn1	85.4 (2)	C18—C19—H19	119.3
C28—O3—Zn1^v	122.5 (2)	C19—C20—C21	119.1 (3)
C28—O4—Zn1^vi	149.8 (3)	C19—C20—C28	116.0 (3)
N1—C1—C2	124.8 (4)	C21—C20—C28	124.8 (3)
N1—C1—H1	117.6	C26—C21—C22	117.6 (3)
C2—C1—H1	117.6	C26—C21—C20	123.6 (3)
C1—C2—C3	116.7 (4)	C22—C21—C20	118.8 (3)
C1—C2—C6	118.9 (4)	C23—C22—C17	122.4 (3)
C3—C2—C6	124.4 (4)	C23—C22—C21	118.3 (3)
C2—C3—C4	119.1 (4)	C17—C22—C21	119.3 (3)
C2—C3—H3	120.5	C24—C23—C22	121.9 (3)
C4—C3—H3	120.5	C24—C23—H23	119.1
C5—C4—C3	119.4 (5)	C22—C23—H23	119.1
C5—C4—H4	120.3	C23—C24—C25	119.8 (3)
C3—C4—H4	120.3	C23—C24—H24	120.1
N1—C5—C4	123.0 (4)	C25—C24—H24	120.1
N1—C5—H5	118.5	C26—C25—C24	120.8 (4)
C4—C5—H5	118.5	C26—C25—H25	119.6
C7—C6—C2	125.9 (5)	C24—C25—H25	119.6
C7—C6—H6	117.0	C25—C26—C21	121.5 (3)
C2—C6—H6	117.0	C25—C26—H26	119.2
C6—C7—C8	124.9 (5)	C21—C26—H26	119.2
C6—C7—H7	117.6	O2—C27—O1	121.9 (3)
C8—C7—H7	117.6	O2—C27—C17	118.3 (4)
C9—C8—C7	123.8 (5)	O1—C27—C17	119.7 (3)
C9—C8—H8	118.1	O2—C27—Zn1	65.32 (19)
C7—C8—H8	118.1	O1—C27—Zn1	56.74 (18)
C8—C9—C10	125.5 (5)	C17—C27—Zn1	175.5 (3)
C8—C9—H9	117.2	O4—C28—O3	123.1 (3)
C10—C9—H9	117.2	O4—C28—C20	117.9 (3)
C11—C10—C9	123.9 (5)	O3—C28—C20	119.0 (3)

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