A three-dimensional Zn^II coordination network based on 5,5′-methyl­enebis(2,4,6-tri­methyl­iso­phthalic acid) and 2,7-bis­(1H-imidazol-1-yl)fluorene: synthesis, structure and luminescence properties

In recent years, coordination polymers constructed from multidentate carboxyl­ate ligands and N-containing ligands have attracted much attention since these ligands can adopt a rich variety of coordination modes which can lead to crystal­line products with intriguing structures and inter­esting properties. A new coordination polymer, namely poly[[di­aqua­[μ-2,7-bis­(1H-imidazol-1-yl)fluor­ene-κ²N³:N^3′][μ-5,5′-methyl­enebis(3-carb­oxy-2,4,6-tri­methyl­benzoato)-κ²O¹:O^1′]zinc(II)] hemihydrate], {[Zn(C₂₃H₂₂O₈)(C₁₉H₁₄N₄)(H₂O)₂]·0.5H₂O}_n, 1, was pre­pared by the self-assembly of Zn(NO₃)₂·6H₂O with 5,5′-methyl­enebis(2,4,6-tri­methyl­isophthalic acid) (H₄BTMIPA) and 2,7-bis­(1H-imidazol-1-yl)fluorene (BIF) under solvothermal conditions. The structure of 1 was determined by elemental analysis, single-crystal X-ray crystallography, powder X-ray diffraction, IR spectroscopy and thermogravimetric analysis. Each Zn^II ion is six-coordinated by two O atoms from two H₂BTMIPA²⁻ ligands, by two N atoms from two BIF ligands and by two water mol­ecules, forming a distorted octa­hedral ZnN₂O₄ coordination geometry. Adjacent Zn^II ions are linked by H₂BTMIPA²⁻ ligands and BIF ligands, leading to the formation of a two-dimensional (2D) (4,4)-sql network, and inter­molecular hydrogen-bonding inter­actions connect the 2D layer structure into the three-dimensional (3D) supra­molecular structure. Each 2D layer contains two kinds of helices with the same direction, which are opposite in adjacent layers. The luminescence properties of complex 1 in the solid state have also been investigated.

Computing details

Data collection: SMART (Bruker, 2008); cell refinement: SMART (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: publCIF (Westrip, 2010) and OLEX2 (Dolomanov et al., 2009).

Poly[[diaqua[µ-2,7-bis(1H-imidazol-1-yl)fluorene-κ²N³:N^3'][µ-5,5'-methylenebis(3-carboxy-2,4,6-trimethylbenzoato)-κ²O¹:O^1']zinc(II)] hemihydrate]

Crystal data

[Zn(C23H22O8)(C19H14N4)(H2O)2]·0.5H2O	Dx = 1.455 Mg m^−3
Mr = 833.16	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pcaa	Cell parameters from 3254 reflections
a = 11.099 (9) Å	θ = 2.2–23.1°
b = 12.917 (11) Å	µ = 0.71 mm^−1
c = 26.55 (2) Å	T = 293 K
V = 3806 (6) Å^3	Block, yellow
Z = 4	0.21 × 0.2 × 0.19 mm
F(000) = 1732

Data collection

Bruker SMART CCD area detector diffractometer	2778 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.065
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θmax = 27.1°, θmin = 2.2°
Tmin = 0.871, Tmax = 0.871	h = −14→12
20036 measured reflections	k = −16→16
4122 independent reflections	l = −33→22

Refinement

Refinement on F^2	5 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.139	w = 1/[σ^2(Fo^2) + (0.0725P)^2 + 0.711P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.004
4122 reflections	Δρmax = 0.68 e Å^−3
277 parameters	Δρmin = −0.70 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.27824 (4)	0.500000	0.750000	0.03466 (17)
O1	0.42058 (16)	0.36969 (14)	0.77874 (7)	0.0348 (5)
O1W	0.13711 (17)	0.40313 (16)	0.77388 (9)	0.0411 (5)
H1WA	0.165380	0.343430	0.782687	0.062*
N1	0.31101 (19)	0.43459 (17)	0.68121 (9)	0.0324 (5)
O3	0.6938 (3)	0.1282 (2)	0.95414 (10)	0.0759 (8)
H3	0.683 (6)	0.098 (7)	0.9824 (16)	0.114*	0.5
O2	0.27922 (17)	0.25078 (17)	0.79590 (11)	0.0635 (8)
O4	0.5238 (3)	0.0341 (2)	0.95223 (11)	0.0775 (9)
N2	0.4098 (2)	0.37147 (18)	0.61576 (9)	0.0368 (6)
C9	0.6256 (2)	0.06511 (18)	0.78883 (10)	0.0257 (6)
C1	0.3868 (2)	0.2802 (2)	0.79316 (11)	0.0315 (6)
C3	0.5021 (2)	0.18837 (19)	0.86109 (11)	0.0291 (6)
C19	0.6975 (2)	0.3083 (2)	0.51747 (10)	0.0320 (6)
C7	0.6517 (2)	0.05320 (19)	0.84069 (10)	0.0294 (6)
C2	0.4804 (2)	0.20108 (19)	0.80940 (10)	0.0267 (6)
C5	0.5867 (2)	0.1131 (2)	0.87619 (10)	0.0289 (6)
C11	0.5391 (2)	0.13887 (19)	0.77330 (10)	0.0267 (6)
C13	0.4117 (2)	0.4401 (2)	0.65433 (11)	0.0331 (6)
H13	0.475066	0.485153	0.661072	0.040*
C6	0.6031 (3)	0.0913 (2)	0.93123 (11)	0.0387 (7)
C20	0.6669 (2)	0.4121 (2)	0.52830 (11)	0.0351 (7)
C16	0.5078 (2)	0.3512 (2)	0.58132 (11)	0.0367 (7)
C21	0.5706 (3)	0.4343 (2)	0.56030 (12)	0.0392 (7)
H21	0.548998	0.502291	0.567419	0.047*
C14	0.2426 (3)	0.3588 (3)	0.65844 (13)	0.0500 (9)
H14	0.166575	0.337957	0.669099	0.060*
C10	0.6964 (3)	0.000000	0.750000	0.0301 (8)
H10A	0.748364	0.046786	0.731430	0.036*	0.5
H10B	0.748364	−0.046785	0.768570	0.036*	0.5
C8	0.7483 (3)	−0.0219 (2)	0.85981 (12)	0.0406 (7)
H8A	0.729116	−0.090905	0.849009	0.061*
H8B	0.750973	−0.019681	0.895936	0.061*
H8C	0.825392	−0.002253	0.846472	0.061*
C18	0.6320 (3)	0.2265 (2)	0.53778 (11)	0.0405 (7)
H18	0.651299	0.158430	0.529792	0.049*
C17	0.5373 (3)	0.2484 (2)	0.57016 (12)	0.0429 (7)
H17	0.493391	0.194639	0.584488	0.052*
C12	0.5062 (3)	0.1529 (2)	0.71798 (11)	0.0360 (7)
H12A	0.578422	0.158790	0.698314	0.054*
H12B	0.458841	0.214640	0.714103	0.054*
H12C	0.460494	0.094244	0.706685	0.054*
C15	0.3018 (3)	0.3191 (3)	0.61852 (14)	0.0573 (10)
H15	0.275081	0.266910	0.597138	0.069*
C22	0.750000	0.4852 (3)	0.500000	0.0465 (12)
H22A	0.794961	0.528724	0.523072	0.056*	0.375
H22B	0.705039	0.528724	0.476928	0.056*	0.375
C4	0.4374 (3)	0.2539 (2)	0.90019 (12)	0.0462 (8)
H4A	0.403327	0.313802	0.884212	0.069*
H4B	0.493693	0.275412	0.925571	0.069*
H4C	0.374352	0.213898	0.915474	0.069*
H1WB	0.080 (2)	0.393 (3)	0.7525 (11)	0.069*
H4	0.514 (6)	0.041 (6)	0.9838 (6)	0.069*	0.5
O5	0.750000	0.5749 (9)	0.500000	0.144 (5)	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0280 (3)	0.0426 (3)	0.0334 (3)	0.000	0.000	−0.0101 (2)
O1	0.0325 (10)	0.0279 (10)	0.0440 (13)	0.0018 (8)	0.0036 (9)	−0.0002 (9)
O1W	0.0299 (10)	0.0416 (12)	0.0518 (15)	0.0028 (9)	−0.0015 (9)	0.0031 (11)
N1	0.0283 (11)	0.0359 (13)	0.0329 (13)	−0.0049 (10)	0.0037 (10)	−0.0030 (11)
O3	0.093 (2)	0.100 (2)	0.0354 (15)	−0.0166 (17)	−0.0236 (14)	0.0058 (15)
O2	0.0251 (11)	0.0498 (14)	0.116 (2)	−0.0009 (9)	−0.0071 (12)	0.0277 (14)
O4	0.102 (2)	0.0651 (16)	0.0652 (19)	−0.0088 (16)	0.0404 (17)	0.0168 (16)
N2	0.0347 (12)	0.0431 (14)	0.0326 (13)	−0.0083 (11)	0.0066 (11)	−0.0075 (11)
C9	0.0236 (12)	0.0209 (12)	0.0327 (15)	−0.0036 (10)	−0.0008 (11)	−0.0023 (11)
C1	0.0266 (13)	0.0294 (14)	0.0387 (17)	−0.0001 (11)	0.0019 (12)	−0.0027 (13)
C3	0.0280 (12)	0.0264 (13)	0.0328 (15)	−0.0037 (11)	0.0036 (11)	−0.0026 (12)
C19	0.0320 (14)	0.0384 (15)	0.0256 (14)	−0.0015 (12)	−0.0002 (11)	−0.0014 (12)
C7	0.0326 (13)	0.0250 (13)	0.0307 (15)	−0.0008 (11)	−0.0038 (12)	0.0013 (12)
C2	0.0203 (11)	0.0235 (13)	0.0363 (16)	−0.0027 (10)	0.0003 (11)	0.0002 (11)
C5	0.0293 (13)	0.0278 (13)	0.0296 (15)	−0.0038 (11)	−0.0013 (11)	0.0000 (12)
C11	0.0250 (12)	0.0272 (13)	0.0280 (14)	−0.0050 (11)	−0.0036 (11)	0.0017 (12)
C13	0.0282 (13)	0.0358 (15)	0.0354 (16)	−0.0031 (12)	0.0019 (12)	−0.0029 (13)
C6	0.0491 (17)	0.0334 (15)	0.0337 (16)	0.0021 (13)	0.0015 (14)	0.0004 (13)
C20	0.0352 (15)	0.0371 (16)	0.0330 (16)	−0.0002 (12)	0.0033 (13)	−0.0002 (13)
C16	0.0316 (14)	0.0473 (17)	0.0311 (16)	−0.0048 (13)	0.0070 (12)	−0.0050 (14)
C21	0.0378 (15)	0.0370 (16)	0.0430 (18)	0.0017 (13)	0.0095 (13)	−0.0051 (14)
C14	0.0363 (15)	0.068 (2)	0.046 (2)	−0.0227 (15)	0.0124 (14)	−0.0200 (18)
C10	0.0248 (17)	0.032 (2)	0.033 (2)	0.000	0.000	−0.0044 (17)
C8	0.0443 (16)	0.0410 (17)	0.0364 (17)	0.0118 (13)	−0.0085 (13)	−0.0014 (14)
C18	0.0485 (17)	0.0341 (15)	0.0388 (17)	−0.0019 (14)	0.0108 (14)	−0.0028 (13)
C17	0.0481 (17)	0.0393 (17)	0.0414 (19)	−0.0087 (14)	0.0114 (14)	−0.0005 (14)
C12	0.0365 (15)	0.0357 (15)	0.0360 (17)	0.0040 (12)	−0.0051 (12)	−0.0022 (13)
C15	0.0470 (18)	0.075 (2)	0.050 (2)	−0.0317 (17)	0.0155 (16)	−0.0258 (19)
C22	0.046 (2)	0.033 (2)	0.060 (3)	0.000	0.020 (2)	0.000
C4	0.0479 (17)	0.0487 (19)	0.0420 (19)	0.0065 (15)	0.0102 (15)	−0.0057 (16)
O5	0.170 (11)	0.087 (8)	0.174 (13)	0.000	0.085 (10)	0.000

Geometric parameters (Å, º)

Zn1—N1^i	2.045 (3)	C7—C8	1.532 (4)
Zn1—N1	2.045 (3)	C2—C11	1.410 (4)
Zn1—O1W^i	2.103 (2)	C5—C6	1.499 (4)
Zn1—O1W	2.103 (2)	C11—C12	1.524 (4)
Zn1—O1	2.431 (2)	C13—H13	0.9300
Zn1—O1^i	2.431 (2)	C20—C21	1.395 (4)
O1—C1	1.274 (3)	C20—C22	1.519 (4)
O1W—H1WA	0.8647	C16—C21	1.397 (4)
O1W—H1WB	0.858 (10)	C16—C17	1.399 (4)
N1—C13	1.328 (3)	C21—H21	0.9300
N1—C14	1.379 (4)	C14—C15	1.348 (4)
O3—C6	1.269 (4)	C14—H14	0.9300
O3—H3	0.851 (10)	C10—H10A	0.9700
O2—C1	1.255 (3)	C10—H10B	0.9700
O4—C6	1.277 (4)	C8—H8A	0.9600
O4—H4	0.849 (10)	C8—H8B	0.9600
N2—C13	1.355 (4)	C8—H8C	0.9600
N2—C15	1.378 (4)	C18—C17	1.386 (4)
N2—C16	1.445 (4)	C18—H18	0.9300
C9—C11	1.414 (4)	C17—H17	0.9300
C9—C7	1.415 (4)	C12—H12A	0.9600
C9—C10	1.545 (3)	C12—H12B	0.9600
C1—C2	1.519 (4)	C12—H12C	0.9600
C3—C2	1.403 (4)	C15—H15	0.9300
C3—C5	1.410 (4)	C22—O5	1.159 (11)
C3—C4	1.520 (4)	C22—H22A	0.9700
C19—C18	1.391 (4)	C22—H22B	0.9700
C19—C20	1.413 (4)	C4—H4A	0.9600
C19—C19^ii	1.490 (5)	C4—H4B	0.9600
C7—C5	1.417 (4)	C4—H4C	0.9600
N1^i—Zn1—N1	159.51 (12)	C21—C20—C19	120.2 (3)
N1^i—Zn1—O1W^i	98.97 (9)	C21—C20—C22	129.7 (3)
N1—Zn1—O1W^i	96.26 (10)	C19—C20—C22	110.1 (3)
N1^i—Zn1—O1W	96.26 (10)	C21—C16—C17	121.9 (3)
N1—Zn1—O1W	98.97 (9)	C21—C16—N2	119.3 (3)
O1W^i—Zn1—O1W	83.69 (13)	C17—C16—N2	118.9 (3)
N1^i—Zn1—O1	83.69 (9)	C20—C21—C16	117.9 (3)
N1—Zn1—O1	83.03 (9)	C20—C21—H21	121.1
O1W^i—Zn1—O1	172.17 (7)	C16—C21—H21	121.1
O1W—Zn1—O1	88.71 (9)	C15—C14—N1	110.3 (3)
N1^i—Zn1—O1^i	83.03 (9)	C15—C14—H14	124.9
N1—Zn1—O1^i	83.69 (9)	N1—C14—H14	124.9
O1W^i—Zn1—O1^i	88.70 (9)	C9^iii—C10—C9	118.9 (3)
O1W—Zn1—O1^i	172.17 (7)	C9^iii—C10—H10A	107.6
O1—Zn1—O1^i	98.95 (11)	C9—C10—H10A	107.6
C1—O1—Zn1	122.11 (17)	C9^iii—C10—H10B	107.6
Zn1—O1W—H1WA	110.0	C9—C10—H10B	107.6
Zn1—O1W—H1WB	116 (3)	H10A—C10—H10B	107.0
H1WA—O1W—H1WB	107.6	C7—C8—H8A	109.5
C13—N1—C14	105.4 (2)	C7—C8—H8B	109.5
C13—N1—Zn1	127.41 (19)	H8A—C8—H8B	109.5
C14—N1—Zn1	125.97 (19)	C7—C8—H8C	109.5
C6—O3—H3	98 (5)	H8A—C8—H8C	109.5
C6—O4—H4	117 (4)	H8B—C8—H8C	109.5
C13—N2—C15	107.2 (2)	C17—C18—C19	118.8 (3)
C13—N2—C16	125.8 (2)	C17—C18—H18	120.6
C15—N2—C16	126.8 (3)	C19—C18—H18	120.6
C11—C9—C7	119.7 (2)	C18—C17—C16	120.1 (3)
C11—C9—C10	121.2 (2)	C18—C17—H17	119.9
C7—C9—C10	119.0 (2)	C16—C17—H17	119.9
O2—C1—O1	124.8 (2)	C11—C12—H12A	109.5
O2—C1—C2	115.5 (2)	C11—C12—H12B	109.5
O1—C1—C2	119.6 (2)	H12A—C12—H12B	109.5
C2—C3—C5	118.2 (2)	C11—C12—H12C	109.5
C2—C3—C4	121.5 (2)	H12A—C12—H12C	109.5
C5—C3—C4	120.3 (3)	H12B—C12—H12C	109.5
C18—C19—C20	121.1 (3)	C14—C15—N2	106.2 (3)
C18—C19—C19^ii	130.59 (17)	C14—C15—H15	126.9
C20—C19—C19^ii	108.35 (16)	N2—C15—H15	126.9
C9—C7—C5	118.9 (2)	O5—C22—C20	128.43 (17)
C9—C7—C8	122.3 (2)	O5—C22—C20^ii	128.43 (17)
C5—C7—C8	118.8 (3)	C20—C22—C20^ii	103.1 (3)
C3—C2—C11	121.3 (2)	C20—C22—H22A	111.1
C3—C2—C1	118.3 (2)	C20^ii—C22—H22A	111.1
C11—C2—C1	120.4 (2)	C20—C22—H22B	111.1
C3—C5—C7	121.8 (2)	C20^ii—C22—H22B	111.1
C3—C5—C6	119.2 (2)	H22A—C22—H22B	109.1
C7—C5—C6	118.9 (2)	C3—C4—H4A	109.5
C2—C11—C9	120.0 (2)	C3—C4—H4B	109.5
C2—C11—C12	118.5 (2)	H4A—C4—H4B	109.5
C9—C11—C12	121.6 (2)	C3—C4—H4C	109.5
N1—C13—N2	111.0 (2)	H4A—C4—H4C	109.5
N1—C13—H13	124.5	H4B—C4—H4C	109.5
N2—C13—H13	124.5	C22—O5—H22A^ii	52.9 (5)
O3—C6—O4	123.7 (3)	C22—O5—H22B^ii	52.9 (5)
O3—C6—C5	119.5 (3)	H22A^ii—O5—H22B^ii	105.9
O4—C6—C5	116.8 (3)
Zn1—O1—C1—O2	−2.6 (4)	C16—N2—C13—N1	−175.1 (3)
Zn1—O1—C1—C2	178.39 (18)	C3—C5—C6—O3	−102.5 (3)
C11—C9—C7—C5	2.4 (4)	C7—C5—C6—O3	81.0 (4)
C10—C9—C7—C5	180.0 (2)	C3—C5—C6—O4	78.5 (4)
C11—C9—C7—C8	−177.3 (2)	C7—C5—C6—O4	−98.0 (3)
C10—C9—C7—C8	0.2 (4)	C18—C19—C20—C21	0.8 (4)
C5—C3—C2—C11	1.5 (4)	C19^ii—C19—C20—C21	179.9 (3)
C4—C3—C2—C11	−178.9 (2)	C18—C19—C20—C22	−178.1 (2)
C5—C3—C2—C1	178.4 (2)	C19^ii—C19—C20—C22	0.9 (4)
C4—C3—C2—C1	−2.0 (4)	C13—N2—C16—C21	−45.5 (4)
O2—C1—C2—C3	−80.4 (3)	C15—N2—C16—C21	140.6 (3)
O1—C1—C2—C3	98.7 (3)	C13—N2—C16—C17	134.2 (3)
O2—C1—C2—C11	96.5 (3)	C15—N2—C16—C17	−39.7 (5)
O1—C1—C2—C11	−84.4 (3)	C19—C20—C21—C16	0.8 (4)
C2—C3—C5—C7	1.9 (4)	C22—C20—C21—C16	179.4 (2)
C4—C3—C5—C7	−177.7 (2)	C17—C16—C21—C20	−1.5 (5)
C2—C3—C5—C6	−174.4 (2)	N2—C16—C21—C20	178.3 (3)
C4—C3—C5—C6	6.0 (4)	C13—N1—C14—C15	0.2 (4)
C9—C7—C5—C3	−3.9 (4)	Zn1—N1—C14—C15	−167.9 (3)
C8—C7—C5—C3	175.9 (2)	C11—C9—C10—C9^iii	−55.6 (2)
C9—C7—C5—C6	172.5 (2)	C7—C9—C10—C9^iii	126.9 (2)
C8—C7—C5—C6	−7.8 (4)	C20—C19—C18—C17	−1.7 (4)
C3—C2—C11—C9	−2.9 (4)	C19^ii—C19—C18—C17	179.5 (3)
C1—C2—C11—C9	−179.7 (2)	C19—C18—C17—C16	1.0 (5)
C3—C2—C11—C12	176.7 (2)	C21—C16—C17—C18	0.6 (5)
C1—C2—C11—C12	−0.1 (3)	N2—C16—C17—C18	−179.1 (3)
C7—C9—C11—C2	0.8 (4)	N1—C14—C15—N2	−0.4 (4)
C10—C9—C11—C2	−176.6 (2)	C13—N2—C15—C14	0.4 (4)
C7—C9—C11—C12	−178.8 (2)	C16—N2—C15—C14	175.2 (3)
C10—C9—C11—C12	3.8 (4)	C21—C20—C22—O5	0.9 (4)
C14—N1—C13—N2	0.0 (3)	C19—C20—C22—O5	179.63 (14)
Zn1—N1—C13—N2	167.93 (19)	C21—C20—C22—C20^ii	−179.1 (4)
C15—N2—C13—N1	−0.3 (4)	C19—C20—C22—C20^ii	−0.37 (14)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2	0.86	1.78	2.589 (3)	156
O3—H3···O3^iv	0.85 (1)	2.21 (6)	2.736 (5)	120 (6)
O1W—H1WB···O1^v	0.86 (1)	1.98 (2)	2.813 (3)	163 (4)
O4—H4···O4^vi	0.85 (1)	2.00 (4)	2.737 (6)	145 (7)

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