Poly[[(μ₃-5-amino­isophthalato-κ³ O ¹:O ³:N)(1H-imidazole-κN ³)zinc] 0.25-hydrate]

Abstract

In the title coordination polymer, {[Zn(C₈H₅NO₄)(C₃H₄N₂)]·0.25H₂O}_n, the Zn²⁺ cation has an N₂O₂ donor set involving two carboxyl­ate O atoms from two 5-amino­isophthalate anions, one N atom from a 5-amino­isophthalate anion, and one imidazole N atom displaying a slightly distorted tetra­hedral geometry with two additional O-atom neighbours, with Zn-to-ligand distances of 2.711 (2) and 2.717 (2) Å, respectively. Each 5-amino­isophthalate anion acts as a μ₃-bridge linking symmetry-related Zn^II ions into a layered polymeric structure parallel to (100). The asymmetric unit also comprises a disordered crystal water molecule located on an inversion centre with 0.25 occupancy. In the crystal, N—H⋯O hydrogen bonds form a three-dimensional network.

Related literature

For related structures, see: Zhang et al. (2007 ▶).

Experimental

Crystal data

• [Zn(C₈H₅NO₄)(C₃H₄N₂)]·0.25H₂O

• M _r = 317.09

• Monoclinic,

• a = 9.6239 (11) Å

• b = 10.1916 (11) Å

• c = 12.1927 (13) Å

• β = 95.146 (2)°

• V = 1191.1 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 2.08 mm⁻¹

• T = 293 K

• 0.20 × 0.20 × 0.18 mm

Data collection

• Bruker SMART APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.681, T _max = 0.706

• 6327 measured reflections

• 2340 independent reflections

• 1542 reflections with I > 2σ(I)

• R _int = 0.038

Refinement

• R[F ² > 2σ(F ²)] = 0.048

• wR(F ²) = 0.098

• S = 1.09

• 2340 reflections

• 178 parameters

• H-atom parameters constrained

• Δρ_max = 0.56 e Å⁻³

• Δρ_min = −0.57 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2000 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811050045/kp2352Isup3.cdx

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

Table 1. Selected bond lengths (Å).

N2—Zn1	1.983 (3)
O2—Zn1	1.989 (2)
Zn1—O4i	1.998 (3)
Zn1—N1ii	2.082 (3)

Symmetry codes: (i) ; (ii) .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O4iii	0.91	2.21	3.018 (4)	147
N1—H1A⋯O2iv	0.88	2.17	2.943 (4)	146
N3—H3⋯O3v	0.95	1.88	2.822 (4)	174

Symmetry codes: (iii) ; (iv) ; (v) .

supplementary crystallographic information

Comment

5-Aminoisophthalic acid is often used as organic ligand to synthesise complexes with variable coordination modes. Herein, we report the crystal structure of title coordination polymer. The asymmetric unit consists of one zinc ion, one 5-aminoisophthalate anion, one imidazole and partly occupied crystal water. Each Zn ion has a N₂O₂ donor set and is coordinated by two carboxylate O atoms from two 5-aminoisophthalate anions, one N atom from the amino group of 5-aminoisophthalate anion, and one N atom from an imidazole, displaying a slightly distorted tetrahedral geometry (Fig. 1 and Table 1) with the two additional neighbours O1 and O3 with Zn-ligad distances of 2.711 (2) and 2.717 (2) Å, respectively. Each 5-aminoisophthalate anion acts as a µ₃-bridge. So in the structure of title complex, every 5-aminoisophthalate anion links three zinc ions and every zinc ion bridges three 5-aminoisophthalate anions. This kind of connection proceeds infinitely to form a layer (Fig. 2). Whithin the crystal structure, there are N—H···O hydrogen bonds (Table 2).

Experimental

Reaction mixture of zinc nitrate hexahydrate (29.7 mg, 0.1 mmol), 5-aminoisophthalic acid (18.1 mg, 0.1 mmol), imidazole (6.81 mg, 0.1 mmol), and potassium hydroxide (11.2 mg, 0.2 mmol) in 8 mL H₂O was sealed in a 16 mL Teflon-lined stainless steel container and heated to(1) 453 K for 3 days. After cooling to the room temperature, colourless block crystals of the title complex were obtained.

Refinement

The hydrogen atoms in all C atoms were located in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). The hydrogen atoms in N or O atoms can be found at reasonable positions in the difference Fourier maps and located there [U_iso(H) = 1.2U_eq(N or O)].

Figures

Fig. 1.

The coordination environment of zinc ion in the title complex with the ellipsoids drawn at the 30% probability level. Symmetry code used: (A) x, 1/2 - y, 1/2 + z; (B) x, -1 + y, z; (C) x, 1 + y, z; (D) x, 1/2 - y, -1/2 + z.

Fig. 2.

The layer built from infinite connection of zinc ions and 5-aminoisophthalate anions.

Crystal data

[Zn(C8H5NO4)(C3H4N2)]·0.25H2O	F(000) = 642
Mr = 317.09	Dx = 1.768 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2609 reflections
a = 9.6239 (11) Å	θ = 2.6–28.0°
b = 10.1916 (11) Å	µ = 2.08 mm−1
c = 12.1927 (13) Å	T = 293 K
β = 95.146 (2)°	Block, colourless
V = 1191.1 (2) Å3	0.20 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker SMART APEXII CCD diffractometer	2340 independent reflections
Radiation source: sealed tube	1542 reflections with I > 2σ(I)
graphite	Rint = 0.038
phi and ω scans	θmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.681, Tmax = 0.706	k = −12→12
6327 measured reflections	l = −14→13

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.04P)2] where P = (Fo2 + 2Fc2)/3
2340 reflections	(Δ/σ)max < 0.001
178 parameters	Δρmax = 0.56 e Å−3
0 restraints	Δρmin = −0.57 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	Occ. (<1)
C1	0.6575 (4)	0.3910 (3)	0.9523 (3)	0.0326 (9)
C2	0.6177 (4)	0.3912 (4)	0.8394 (3)	0.0351 (9)
H2	0.6037	0.3123	0.8016	0.042*
C3	0.5989 (4)	0.5098 (3)	0.7836 (3)	0.0320 (8)
C4	0.6275 (4)	0.6274 (3)	0.8374 (3)	0.0346 (9)
H4	0.6188	0.7060	0.7987	0.042*
C5	0.6696 (4)	0.6277 (3)	0.9507 (3)	0.0330 (9)
C6	0.6827 (4)	0.5094 (4)	1.0076 (3)	0.0361 (9)
H6	0.7084	0.5093	1.0830	0.043*
C7	0.6734 (4)	0.2659 (4)	1.0171 (3)	0.0359 (9)
C8	0.6970 (4)	0.7532 (4)	1.0138 (3)	0.0350 (9)
C9	0.9582 (5)	0.1183 (4)	1.2027 (4)	0.0439 (11)
H9	0.9093	0.1936	1.2188	0.053*
C10	1.0136 (5)	−0.0654 (4)	1.1370 (3)	0.0441 (10)
H10	1.0093	−0.1433	1.0972	0.053*
C11	1.1245 (5)	−0.0237 (4)	1.2012 (4)	0.0449 (10)
H11	1.2095	−0.0667	1.2149	0.054*
N1	0.5567 (3)	0.5092 (3)	0.6679 (2)	0.0355 (7)
H1B	0.4983	0.4405	0.6509	0.043*
H1A	0.5065	0.5794	0.6488	0.043*
N2	0.9069 (3)	0.0238 (3)	1.1382 (3)	0.0353 (7)
N3	1.0886 (4)	0.0935 (3)	1.2423 (3)	0.0438 (9)
H3	1.1418	0.1496	1.2921	0.053*
O1	0.6978 (3)	0.2682 (2)	1.1177 (2)	0.0401 (7)
O2	0.6629 (3)	0.1581 (2)	0.9615 (2)	0.0339 (6)
O3	0.7375 (3)	0.7512 (2)	1.1132 (2)	0.0438 (7)
O4	0.6761 (3)	0.8610 (2)	0.9600 (2)	0.0384 (7)
O1W	0.0000	0.0000	0.5000	0.047 (2)	0.50
H1X	0.0422	0.0359	0.4495	0.056*	0.25
H1Y	0.0453	0.0137	0.5620	0.056*	0.25
Zn1	0.71550 (5)	0.01074 (4)	1.06385 (4)	0.03453 (16)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.034 (2)	0.0284 (18)	0.034 (2)	0.0003 (16)	−0.0028 (18)	−0.0004 (15)
C2	0.035 (2)	0.032 (2)	0.036 (2)	−0.0002 (16)	−0.0064 (17)	−0.0001 (16)
C3	0.0285 (19)	0.035 (2)	0.0310 (19)	0.0022 (16)	−0.0039 (15)	−0.0037 (16)
C4	0.040 (2)	0.029 (2)	0.034 (2)	−0.0010 (16)	−0.0003 (18)	0.0027 (15)
C5	0.034 (2)	0.032 (2)	0.031 (2)	0.0018 (15)	−0.0062 (17)	−0.0021 (15)
C6	0.038 (2)	0.036 (2)	0.032 (2)	0.0021 (16)	−0.0083 (16)	0.0001 (15)
C7	0.035 (2)	0.034 (2)	0.037 (2)	0.0038 (16)	−0.0038 (17)	−0.0024 (17)
C8	0.035 (2)	0.032 (2)	0.037 (2)	−0.0009 (15)	−0.0066 (18)	0.0025 (16)
C9	0.048 (3)	0.0297 (19)	0.051 (3)	0.0036 (18)	−0.014 (2)	−0.0107 (18)
C10	0.049 (3)	0.037 (2)	0.044 (3)	0.0067 (19)	−0.0099 (19)	−0.0063 (18)
C11	0.044 (2)	0.043 (2)	0.046 (3)	0.002 (2)	−0.0061 (19)	0.003 (2)
N1	0.0411 (18)	0.0330 (17)	0.0302 (17)	−0.0026 (14)	−0.0086 (13)	0.0019 (13)
N2	0.0377 (18)	0.0316 (16)	0.0345 (18)	0.0041 (14)	−0.0080 (14)	−0.0050 (14)
N3	0.041 (2)	0.0408 (19)	0.045 (2)	−0.0043 (16)	−0.0191 (17)	−0.0124 (15)
O1	0.0579 (19)	0.0300 (14)	0.0304 (16)	−0.0015 (12)	−0.0078 (13)	0.0032 (11)
O2	0.0494 (17)	0.0292 (13)	0.0213 (12)	0.0004 (12)	−0.0069 (12)	0.0014 (10)
O3	0.0579 (19)	0.0308 (14)	0.0385 (17)	0.0036 (13)	−0.0185 (14)	−0.0028 (12)
O4	0.0510 (18)	0.0314 (15)	0.0303 (14)	0.0001 (12)	−0.0095 (13)	−0.0026 (11)
O1W	0.050 (5)	0.056 (5)	0.034 (4)	0.001 (4)	−0.004 (4)	0.004 (4)
Zn1	0.0402 (3)	0.0300 (3)	0.0312 (3)	0.0001 (2)	−0.00893 (17)	0.0000 (2)

Geometric parameters (Å, °)

C1—C6	1.394 (5)	C9—H9	0.9300
C1—C2	1.396 (5)	C10—C11	1.335 (6)
C1—C7	1.500 (5)	C10—N2	1.372 (5)
C2—C3	1.391 (5)	C10—H10	0.9300
C2—H2	0.9300	C11—N3	1.352 (5)
C3—C4	1.382 (5)	C11—H11	0.9300
C3—N1	1.432 (4)	N1—Zn1i	2.082 (3)
C4—C5	1.405 (5)	N1—H1B	0.9104
C4—H4	0.9300	N1—H1A	0.8832
C5—C6	1.391 (5)	N2—Zn1	1.983 (3)
C5—C8	1.503 (5)	N3—H3	0.9504
C6—H6	0.9300	O2—Zn1	1.989 (2)
C7—O1	1.229 (5)	O4—Zn1ii	1.998 (3)
C7—O2	1.290 (4)	O1W—H1X	0.8500
C8—O3	1.239 (5)	O1W—H1Y	0.8501
C8—O4	1.287 (4)	Zn1—O4iii	1.998 (3)
C9—N2	1.312 (5)	Zn1—N1iv	2.082 (3)
C9—N3	1.327 (5)
C6—C1—C2	119.8 (3)	C11—C10—N2	110.1 (4)
C6—C1—C7	118.4 (3)	C11—C10—H10	125.0
C2—C1—C7	121.8 (3)	N2—C10—H10	125.0
C3—C2—C1	119.7 (3)	C10—C11—N3	106.3 (4)
C3—C2—H2	120.1	C10—C11—H11	126.9
C1—C2—H2	120.1	N3—C11—H11	126.9
C4—C3—C2	120.6 (3)	C3—N1—Zn1i	116.3 (2)
C4—C3—N1	119.9 (3)	C3—N1—H1B	110.0
C2—C3—N1	119.4 (3)	Zn1i—N1—H1B	105.0
C3—C4—C5	119.8 (3)	C3—N1—H1A	110.9
C3—C4—H4	120.1	Zn1i—N1—H1A	109.4
C5—C4—H4	120.1	H1B—N1—H1A	104.5
C6—C5—C4	119.6 (3)	C9—N2—C10	104.5 (3)
C6—C5—C8	118.6 (3)	C9—N2—Zn1	127.4 (3)
C4—C5—C8	121.8 (3)	C10—N2—Zn1	128.0 (3)
C5—C6—C1	120.3 (3)	C9—N3—C11	107.4 (3)
C5—C6—H6	119.8	C9—N3—H3	123.7
C1—C6—H6	119.8	C11—N3—H3	128.8
O1—C7—O2	122.7 (3)	C7—O2—Zn1	108.0 (2)
O1—C7—C1	120.7 (3)	C8—O4—Zn1ii	108.5 (2)
O2—C7—C1	116.6 (3)	H1X—O1W—H1Y	109.5
O3—C8—O4	122.3 (3)	N2—Zn1—O2	114.21 (12)
O3—C8—C5	120.8 (3)	N2—Zn1—O4iii	117.19 (12)
O4—C8—C5	117.0 (3)	O2—Zn1—O4iii	98.96 (10)
N2—C9—N3	111.7 (3)	N2—Zn1—N1iv	115.47 (13)
N2—C9—H9	124.1	O2—Zn1—N1iv	107.26 (12)
N3—C9—H9	124.1	O4iii—Zn1—N1iv	101.77 (12)
C6—C1—C2—C3	−2.2 (6)	C4—C3—N1—Zn1i	92.1 (4)
C7—C1—C2—C3	177.4 (4)	C2—C3—N1—Zn1i	−84.6 (4)
C1—C2—C3—C4	4.0 (6)	N3—C9—N2—C10	−0.6 (5)
C1—C2—C3—N1	−179.4 (4)	N3—C9—N2—Zn1	177.5 (3)
C2—C3—C4—C5	−3.0 (6)	C11—C10—N2—C9	0.9 (5)
N1—C3—C4—C5	−179.6 (4)	C11—C10—N2—Zn1	−177.2 (3)
C3—C4—C5—C6	0.3 (6)	N2—C9—N3—C11	0.1 (5)
C3—C4—C5—C8	−177.8 (4)	C10—C11—N3—C9	0.5 (5)
C4—C5—C6—C1	1.5 (6)	O1—C7—O2—Zn1	−6.9 (5)
C8—C5—C6—C1	179.6 (4)	C1—C7—O2—Zn1	171.8 (3)
C2—C1—C6—C5	−0.6 (6)	O3—C8—O4—Zn1ii	−1.3 (5)
C7—C1—C6—C5	179.8 (4)	C5—C8—O4—Zn1ii	178.6 (3)
C6—C1—C7—O1	5.4 (6)	C9—N2—Zn1—O2	59.6 (4)
C2—C1—C7—O1	−174.2 (4)	C10—N2—Zn1—O2	−122.8 (3)
C6—C1—C7—O2	−173.3 (3)	C9—N2—Zn1—O4iii	174.6 (3)
C2—C1—C7—O2	7.1 (6)	C10—N2—Zn1—O4iii	−7.7 (4)
C6—C5—C8—O3	3.8 (6)	C9—N2—Zn1—N1iv	−65.5 (4)
C4—C5—C8—O3	−178.1 (4)	C10—N2—Zn1—N1iv	112.2 (3)
C6—C5—C8—O4	−176.1 (4)	C7—O2—Zn1—N2	−58.7 (3)
C4—C5—C8—O4	2.0 (6)	C7—O2—Zn1—O4iii	176.0 (3)
N2—C10—C11—N3	−0.8 (5)	C7—O2—Zn1—N1iv	70.6 (3)

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

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O4v	0.91	2.21	3.018 (4)	147.
N1—H1A···O2vi	0.88	2.17	2.943 (4)	146.
N3—H3···O3vii	0.95	1.88	2.822 (4)	174.

Symmetry codes: (v) −x+1, y−1/2, −z+3/2; (vi) −x+1, y+1/2, −z+3/2; (vii) −x+2, y−1/2, −z+5/2.