Poly[[(1,10-phenanthroline-κ² N,N′)zinc]-μ-2,5-bis­(all­yloxy)terephthalato-κ² O ¹:O ⁴]

Abstract

The title compound, [Zn(C₁₄H₁₂O₆)(C₁₂H₈N₂)]_n, is a coordination polymer forming one-dimensional infinite zigzag chains along [10] by inter­connection of Zn^II atoms by 2,5-bis­(all­yl­oxy)­terephthalate anions via the carboxyl­ate groups. The Zn^II atom is located on a twofold axis and is in a distorted tetra­hedral coordination formed by the two carboxyl­ate O atoms [Zn—O = 1.9647 (12) Å] and two phenanthroline N atoms [Zn—N = 2.0949 (14) Å].

Related literature

Some other low-dimensional Zn^II complexes based on different organic carb­oxy­lic acids are described by Zhou et al. (2009 ▶). For the preparation of 2,5-bis­(all­yloxy)terephthalic acid, see: Kenichiro et al. (1998 ▶).

Experimental

Crystal data

• [Zn(C₁₄H₁₂O₆)(C₁₂H₈N₂)]

• M _r = 521.81

• Monoclinic,

• a = 21.428 (10) Å

• b = 9.458 (4) Å

• c = 12.897 (6) Å

• β = 118.462 (5)°

• V = 2297.9 (18) ų

• Z = 4

• Mo Kα radiation

• μ = 1.12 mm⁻¹

• T = 293 K

• 0.25 × 0.23 × 0.22 mm

Data collection

• Bruker P4 diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.768, T _max = 0.792

• 8294 measured reflections

• 2546 independent reflections

• 2325 reflections with I > 2σ(I)

• R _int = 0.028

• Standard reflections: 0

Refinement

• R[F ² > 2σ(F ²)] = 0.029

• wR(F ²) = 0.078

• S = 1.04

• 2546 reflections

• 159 parameters

• H-atom parameters constrained

• Δρ_max = 0.32 e Å⁻³

• Δρ_min = −0.34 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Experimental

2,5-Bis(allyloxy)terephthalic acid was prepared according to the literature (Kenichiro et al., 1998). Other chemicals were used as purchased. Zn(NO₃)₂6(H₂O) (8.9 mg, 0.03 mmol), 1,10-phenanthroline (1.98 mg, 0.01 mmol) and 2 ,5-bis(allyloxy)terephthalic acid (2.48 mg, 0.01 mmol) were added to the 15 ml N, N-dimethylacetamide. After stirring at room temperature for 1 h, the solution was kept at 140 °C for 3 days. Crystallization yielded pink crystals suitable for X-ray diffraction analysis (yield 2.25 mg, 39%).

Refinement

The methylene H atoms were placed in calculated positions with a C—H bond distance of 0.97 Å of the carrier atom, and the other C—H distance were placed at 0.93 Å. U_iso(H) was set at 1.2U_eq of the carrier atom. Two reflections have been omitted from the refinement as they were most probably partially affected by the beamstop.

Figures

Fig. 1.

Atom numbering scheme for the title compound with displacement ellipsoids shown at the 30% probability level. [symmetry codes: A, 2 - x, y, 1.5 - z; B, 1.5 - x, 0.5 - y,1 - z; C, 1/2 + x, 0.5 - y, 1/2 + z]

Crystal data

[Zn(C14H12O6)(C12H8N2)]	F(000) = 1072
Mr = 521.81	Dx = 1.508 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 80 reflections
a = 21.428 (10) Å	θ = 2.4–27.2°
b = 9.458 (4) Å	µ = 1.12 mm−1
c = 12.897 (6) Å	T = 293 K
β = 118.462 (5)°	Block, pink
V = 2297.9 (18) Å3	0.25 × 0.23 × 0.22 mm
Z = 4

Data collection

Bruker P4 diffractometer	2546 independent reflections
Radiation source: fine-focus sealed tube	2325 reflections with I > 2σ(I)
graphite	Rint = 0.028
ω scans	θmax = 27.5°, θmin = 3.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −27→27
Tmin = 0.768, Tmax = 0.792	k = −12→7
8294 measured reflections	l = −16→16

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0463P)2 + 0.943P] where P = (Fo2 + 2Fc2)/3
2546 reflections	(Δ/σ)max = 0.001
159 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.34 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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Zn1	1.0000	0.52903 (2)	0.7500	0.02792 (10)
O1	0.89786 (8)	0.40767 (17)	0.77262 (12)	0.0557 (4)
O2	0.91910 (6)	0.43004 (14)	0.62292 (11)	0.0391 (3)
O3	0.80413 (7)	0.19659 (16)	0.73891 (11)	0.0514 (4)
N1	0.97095 (7)	0.69874 (13)	0.82237 (11)	0.0301 (3)
C1	0.88075 (8)	0.38949 (16)	0.66788 (14)	0.0336 (3)
C2	0.81280 (8)	0.31540 (16)	0.58400 (14)	0.0312 (3)
C3	0.77669 (8)	0.22152 (18)	0.62095 (14)	0.0337 (3)
C4	0.78541 (8)	0.34259 (17)	0.46410 (15)	0.0345 (3)
H4	0.8092	0.4055	0.4398	0.041*
C5	0.76293 (11)	0.1225 (3)	0.78059 (18)	0.0574 (5)
H5A	0.7644	0.0218	0.7674	0.069*
H5B	0.7139	0.1533	0.7381	0.069*
C6	0.79184 (12)	0.1506 (3)	0.90851 (19)	0.0650 (6)
H6	0.7738	0.0967	0.9484	0.078*
C7	0.83955 (14)	0.2426 (3)	0.9693 (2)	0.0753 (7)
H7A	0.8592	0.2989	0.9331	0.090*
H7B	0.8545	0.2528	1.0494	0.090*
C8	0.94114 (9)	0.6966 (2)	0.89252 (16)	0.0409 (4)
H8	0.9341	0.6100	0.9195	0.049*
C9	0.92019 (11)	0.8196 (2)	0.92674 (18)	0.0503 (5)
H9	0.8989	0.8143	0.9748	0.060*
C10	0.93107 (11)	0.9478 (2)	0.88954 (18)	0.0482 (5)
H10	0.9163	1.0302	0.9108	0.058*
C11	0.96472 (10)	0.95499 (17)	0.81881 (15)	0.0390 (4)
C12	0.98315 (8)	0.82583 (15)	0.78693 (13)	0.0290 (3)
C13	0.98266 (11)	1.0847 (2)	0.78170 (17)	0.0508 (5)
H13	0.9700	1.1703	0.8020	0.061*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Zn1	0.02088 (14)	0.02229 (15)	0.03263 (15)	0.000	0.00630 (10)	0.000
O1	0.0577 (8)	0.0624 (9)	0.0399 (7)	−0.0299 (7)	0.0174 (6)	−0.0169 (6)
O2	0.0269 (5)	0.0430 (6)	0.0418 (6)	−0.0118 (5)	0.0118 (5)	−0.0097 (5)
O3	0.0367 (7)	0.0751 (10)	0.0331 (6)	−0.0212 (6)	0.0091 (5)	0.0021 (6)
N1	0.0270 (6)	0.0291 (6)	0.0329 (6)	−0.0017 (5)	0.0132 (5)	−0.0011 (5)
C1	0.0248 (7)	0.0271 (8)	0.0398 (8)	−0.0029 (6)	0.0081 (6)	−0.0056 (6)
C2	0.0214 (7)	0.0311 (8)	0.0365 (8)	−0.0030 (5)	0.0101 (6)	−0.0066 (6)
C3	0.0246 (7)	0.0370 (8)	0.0344 (8)	−0.0036 (6)	0.0099 (6)	−0.0026 (6)
C4	0.0252 (7)	0.0353 (8)	0.0393 (8)	−0.0064 (6)	0.0124 (6)	−0.0027 (6)
C5	0.0450 (11)	0.0793 (15)	0.0469 (11)	−0.0162 (10)	0.0210 (9)	0.0023 (10)
C6	0.0535 (12)	0.0975 (19)	0.0473 (11)	−0.0056 (12)	0.0266 (10)	0.0018 (12)
C7	0.0639 (15)	0.103 (2)	0.0546 (13)	−0.0002 (14)	0.0251 (12)	−0.0175 (14)
C8	0.0395 (9)	0.0452 (10)	0.0427 (9)	−0.0084 (7)	0.0235 (8)	−0.0055 (7)
C9	0.0469 (10)	0.0625 (13)	0.0518 (11)	−0.0080 (9)	0.0320 (9)	−0.0180 (9)
C10	0.0451 (10)	0.0499 (11)	0.0482 (10)	0.0069 (8)	0.0211 (9)	−0.0151 (8)
C11	0.0418 (9)	0.0318 (9)	0.0348 (8)	0.0056 (7)	0.0113 (7)	−0.0054 (6)
C12	0.0271 (7)	0.0263 (7)	0.0275 (7)	0.0009 (5)	0.0082 (6)	−0.0016 (5)
C13	0.0718 (14)	0.0241 (8)	0.0441 (10)	0.0068 (8)	0.0175 (9)	−0.0022 (7)

Geometric parameters (Å, °)

Zn1—O2	1.9647 (12)	C5—H5A	0.9700
Zn1—O2i	1.9647 (12)	C5—H5B	0.9700
Zn1—N1	2.0949 (14)	C6—C7	1.285 (4)
Zn1—N1i	2.0950 (14)	C6—H6	0.9300
O1—C1	1.232 (2)	C7—H7A	0.9300
O2—C1	1.270 (2)	C7—H7B	0.9300
O3—C3	1.365 (2)	C8—C9	1.392 (3)
O3—C5	1.418 (2)	C8—H8	0.9300
N1—C8	1.333 (2)	C9—C10	1.365 (3)
N1—C12	1.355 (2)	C9—H9	0.9300
C1—C2	1.510 (2)	C10—C11	1.408 (3)
C2—C4	1.392 (2)	C10—H10	0.9300
C2—C3	1.402 (2)	C11—C12	1.404 (2)
C3—C4ii	1.397 (2)	C11—C13	1.434 (3)
C4—C3ii	1.397 (2)	C12—C12i	1.444 (3)
C4—H4	0.9300	C13—C13i	1.342 (4)
C5—C6	1.484 (3)	C13—H13	0.9300
O2—Zn1—O2i	123.08 (8)	C6—C5—H5B	109.9
O2—Zn1—N1	113.91 (6)	H5A—C5—H5B	108.3
O2i—Zn1—N1	108.96 (6)	C7—C6—C5	126.0 (2)
O2—Zn1—N1i	108.96 (6)	C7—C6—H6	117.0
O2i—Zn1—N1i	113.91 (6)	C5—C6—H6	117.0
N1—Zn1—N1i	79.98 (8)	C6—C7—H7A	120.0
C1—O2—Zn1	105.59 (11)	C6—C7—H7B	120.0
C3—O3—C5	119.50 (14)	H7A—C7—H7B	120.0
C8—N1—C12	118.32 (14)	N1—C8—C9	122.23 (17)
C8—N1—Zn1	129.09 (11)	N1—C8—H8	118.9
C12—N1—Zn1	112.55 (10)	C9—C8—H8	118.9
O1—C1—O2	122.65 (14)	C10—C9—C8	119.77 (16)
O1—C1—C2	122.14 (15)	C10—C9—H9	120.1
O2—C1—C2	115.21 (14)	C8—C9—H9	120.1
C4—C2—C3	119.07 (14)	C9—C10—C11	119.75 (16)
C4—C2—C1	117.55 (14)	C9—C10—H10	120.1
C3—C2—C1	123.39 (15)	C11—C10—H10	120.1
O3—C3—C4ii	122.92 (15)	C12—C11—C10	116.75 (16)
O3—C3—C2	118.29 (14)	C12—C11—C13	119.27 (17)
C4ii—C3—C2	118.79 (15)	C10—C11—C13	123.96 (16)
C2—C4—C3ii	122.14 (15)	N1—C12—C11	123.14 (14)
C2—C4—H4	118.9	N1—C12—C12i	117.39 (8)
C3ii—C4—H4	118.9	C11—C12—C12i	119.47 (10)
O3—C5—C6	109.10 (18)	C13i—C13—C11	121.18 (11)
O3—C5—H5A	109.9	C13i—C13—H13	119.4
C6—C5—H5A	109.9	C11—C13—H13	119.4
O3—C5—H5B	109.9
O2i—Zn1—O2—C1	78.15 (10)	C3—C2—C4—C3ii	−0.5 (3)
N1—Zn1—O2—C1	−57.33 (12)	C1—C2—C4—C3ii	179.32 (15)
N1i—Zn1—O2—C1	−144.52 (10)	C3—O3—C5—C6	−160.82 (19)
O2—Zn1—N1—C8	72.39 (16)	O3—C5—C6—C7	9.4 (4)
O2i—Zn1—N1—C8	−69.20 (15)	C12—N1—C8—C9	2.2 (3)
N1i—Zn1—N1—C8	178.81 (18)	Zn1—N1—C8—C9	−175.24 (14)
O2—Zn1—N1—C12	−105.20 (11)	N1—C8—C9—C10	−1.0 (3)
O2i—Zn1—N1—C12	113.21 (11)	C8—C9—C10—C11	−1.3 (3)
N1i—Zn1—N1—C12	1.21 (7)	C9—C10—C11—C12	2.2 (3)
Zn1—O2—C1—O1	−3.4 (2)	C9—C10—C11—C13	−175.80 (19)
Zn1—O2—C1—C2	177.38 (10)	C8—N1—C12—C11	−1.2 (2)
O1—C1—C2—C4	157.66 (17)	Zn1—N1—C12—C11	176.68 (12)
O2—C1—C2—C4	−23.1 (2)	C8—N1—C12—C12i	178.70 (17)
O1—C1—C2—C3	−22.5 (2)	Zn1—N1—C12—C12i	−3.4 (2)
O2—C1—C2—C3	156.76 (15)	C10—C11—C12—N1	−1.0 (2)
C5—O3—C3—C4ii	−11.2 (3)	C13—C11—C12—N1	177.11 (15)
C5—O3—C3—C2	169.03 (18)	C10—C11—C12—C12i	179.11 (18)
C4—C2—C3—O3	−179.70 (15)	C13—C11—C12—C12i	−2.8 (3)
C1—C2—C3—O3	0.5 (2)	C12—C11—C13—C13i	−0.7 (3)
C4—C2—C3—C4ii	0.5 (3)	C10—C11—C13—C13i	177.2 (2)
C1—C2—C3—C4ii	−179.32 (14)

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