Poly[(μ3-camphorato-κ3O:O′:O′′)(2-methyl-1H-imidazole-κN3)zinc(II)]

Shi, H.; Li, C.; Gao, F.; Chen, J.; Han, F.

doi:10.1107/S1600536810007105

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page m352

doi:10.1107/S1600536810007105

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Poly[(μ₃-camphorato-κ³O:O′:O′′)(2-methyl-1H-imidazole-κN³)zinc(II)]

Haochen Shi,^a ^* Chunjie Li,^a Feng Gao,^a Jingyan Chen ^a and Fei Han ^a

^aDepartment of Physics Education, Changchun Normal University, 667 Changji Highway (North), Erdao District, Jilin Province 130032, People's Republic of China
^*Correspondence e-mail: haochenshi@yahoo.cn

(Received 11 February 2010; accepted 24 February 2010; online 3 March 2010)

In the title compound, [Zn(C₁₀H₁₄O₄)(C₄H₆N₂)]_n, each Zn^II ion is coordinated by one N atom from one 2-methyl-1H-imidazole ligand and three O atoms from two camphorate (cap) ligands in a distorted tetrahedral geometry. In one of the cap ligands, one methyl group is disordered between positions 1 and 3 in a 0.518 (12):0.482 (12) ratio. Each cap ligand bridges three Zn^II ions, forming two-dimensional layers, which interact further via N—H⋯O hydrogen bonds.

Related literature

For general background to coordination polymers based on camphoric acid, see: Zhang et al. (2007 ).

Experimental

Crystal data

[Zn(C₁₀H₁₄O₄)(C₄H₆N₂)]
M_r = 345.69
Monoclinic, P 2₁ /n
a = 12.098 (2) Å
b = 10.438 (5) Å
c = 12.873 (2) Å
β = 111.700 (5)°
V = 1510.4 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.64 mm⁻¹
T = 293 K
0.31 × 0.25 × 0.21 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.57, T_max = 0.72
9848 measured reflections
3004 independent reflections
2433 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.121
S = 1.08
3004 reflections
200 parameters
H-atom parameters constrained
Δρ_max = 1.13 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O3ⁱ	0.86	1.86	2.722 (5)	176
Symmetry code: (i) -x-1, -y, -z.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810007105/cv2697sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810007105/cv2697Isup2.hkl

checkCIF report

Comment top

Coordination polymers based on camphoric acid (cap) have received intense interests because of their potential applications as functional solid materials, as well as their fascinating framework structures (Zhang et al., 2007). We report here the synthesis and structure of the title compound (I).

In (I) (Fig. 1), each Zn^II atom is four-coordinated by one nitrogen atom from one 2-methyl-1H-imidazole (mid) ligand and three oxygen atoms from two different camphorate anions (cap) in a distorted tetrahedral geometry. Each cap ligand bridges three Zn^II atoms to form a two-dimensional layer structure. Further, the N—H···O H-bonding interactions (Table 1) stabilize the structure of (I).

Related literature top

For general background to coordination polymers based on camphoric acid, see: Zhang et al. (2007).

Experimental top

A mixture of ZnCl^.2H₂O (1 mmol), NaOH (1 mmol), D-camphoric acid (1 mmol) and 2-methyl-1H-imidazole (1 mmol) in water (12 ml) was heated to 140 °C for three days in a 25 ml Teflon-lined stainless steel vessel under autogenous pressure. Subsequently, it was cooled to room temperature. Then, single crystals of (I) were obtained.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A portion of the crystal structure of (I), showing the atomic numbering and 30% probability displacement ellipsoids [symmetry codes: (i) -x, -y, -z; (ii) x+1/2, -1/2-y, z+1/2]. Only major parts of disordered atoms are shown.

Poly[(µ₃-camphorato-κ³O:O':O'')(2- methyl-1H-imidazole-κN³)zinc(II)] top

Crystal data top

[Zn(C₁₀H₁₄O₄)(C₄H₆N₂)]	F(000) = 720
M_r = 345.69	D_x = 1.520 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yn	Cell parameters from 3004 reflections
a = 12.098 (2) Å	θ = 2.0–26.2°
b = 10.438 (5) Å	µ = 1.64 mm⁻¹
c = 12.873 (2) Å	T = 293 K
β = 111.700 (5)°	Block, colourless
V = 1510.4 (8) Å³	0.31 × 0.25 × 0.21 mm
Z = 4

Data collection top

Bruker APEX CCD area-detector diffractometer	3004 independent reflections
Radiation source: fine-focus sealed tube	2433 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ϕ and ω scans	θ_max = 26.2°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.57, T_max = 0.72	k = −12→9
9848 measured reflections	l = −15→15

Refinement top

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0392P)² + 5.0738P] where P = (F_o² + 2F_c²)/3
3004 reflections	(Δ/σ)_max < 0.001
200 parameters	Δρ_max = 1.13 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

[Zn(C₁₀H₁₄O₄)(C₄H₆N₂)]	V = 1510.4 (8) Å³
M_r = 345.69	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.098 (2) Å	µ = 1.64 mm⁻¹
b = 10.438 (5) Å	T = 293 K
c = 12.873 (2) Å	0.31 × 0.25 × 0.21 mm
β = 111.700 (5)°

Data collection top

Bruker APEX CCD area-detector diffractometer	3004 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2433 reflections with I > 2σ(I)
T_min = 0.57, T_max = 0.72	R_int = 0.041
9848 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.121	H-atom parameters constrained
S = 1.08	Δρ_max = 1.13 e Å⁻³
3004 reflections	Δρ_min = −0.41 e Å⁻³
200 parameters

Special details top

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.

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	−0.1477 (5)	0.3115 (6)	0.2334 (4)	0.0469 (14)
H1A	−0.1842	0.3736	0.2655	0.070*
H1B	−0.1009	0.3547	0.1980	0.070*
H1C	−0.0974	0.2562	0.2911	0.070*
C2	−0.2432 (4)	0.2327 (4)	0.1474 (4)	0.0295 (10)
C3	−0.3337 (4)	0.0952 (5)	0.0210 (5)	0.0423 (13)
H3	−0.3476	0.0292	−0.0308	0.051*
C4	−0.4157 (5)	0.1593 (6)	0.0419 (5)	0.0483 (14)
H4	−0.4975	0.1475	0.0082	0.058*
C5	−0.0941 (4)	−0.1910 (4)	−0.0050 (3)	0.0238 (9)
C6	−0.4416 (4)	−0.4768 (4)	−0.2027 (3)	0.0216 (9)
C7	−0.1627 (4)	−0.3138 (4)	−0.0087 (3)	0.0248 (9)
H7	−0.1055	−0.3841	0.0182	0.030*	0.518 (12)
C14'	−0.0756 (10)	−0.4218 (9)	0.0453 (10)	0.042 (3)	0.482 (12)
H14A	−0.0215	−0.4318	0.0070	0.063*	0.482 (12)
H14B	−0.1187	−0.5002	0.0406	0.063*	0.482 (12)
H14C	−0.0317	−0.4015	0.1224	0.063*	0.482 (12)
C8	−0.2402 (5)	−0.3118 (5)	0.0598 (4)	0.0426 (13)
H8A	−0.2719	−0.2265	0.0603	0.051*
H8B	−0.1948	−0.3371	0.1363	0.051*
C9	−0.3432 (4)	−0.4089 (5)	0.0035 (4)	0.0325 (11)
H9A	−0.3379	−0.4809	0.0527	0.039*
H9B	−0.4199	−0.3678	−0.0140	0.039*
C10	−0.3275 (4)	−0.4530 (4)	−0.1027 (4)	0.0241 (9)
H10	−0.2816	−0.5328	−0.0860	0.029*	0.482 (12)
C14	−0.2562 (8)	−0.5802 (9)	−0.0776 (8)	0.034 (3)	0.518 (12)
H14D	−0.1835	−0.5686	−0.0144	0.051*	0.518 (12)
H14E	−0.2383	−0.6046	−0.1416	0.051*	0.518 (12)
H14F	−0.3027	−0.6461	−0.0614	0.051*	0.518 (12)
C11	−0.2500 (4)	−0.3472 (5)	−0.1293 (4)	0.0289 (10)
C12	−0.3273 (5)	−0.2323 (5)	−0.1839 (4)	0.0477 (15)
H12A	−0.3682	−0.2029	−0.1371	0.072*
H12B	−0.3844	−0.2569	−0.2555	0.072*
H12C	−0.2781	−0.1647	−0.1935	0.072*
C13	−0.1875 (5)	−0.3910 (6)	−0.2067 (5)	0.0504 (15)
H13A	−0.1376	−0.4632	−0.1741	0.076*
H13B	−0.1397	−0.3223	−0.2169	0.076*
H13C	−0.2458	−0.4151	−0.2778	0.076*
N1	−0.2211 (4)	0.1414 (4)	0.0891 (3)	0.0356 (9)
N2	−0.3575 (4)	0.2492 (4)	0.1247 (4)	0.0424 (11)
H2	−0.3898	0.3040	0.1545	0.051*
O1	−0.1397 (3)	−0.0873 (3)	0.0066 (3)	0.0305 (7)
O2	0.0054 (3)	−0.2004 (3)	−0.0152 (3)	0.0268 (7)
O3	−0.5387 (3)	−0.4312 (3)	−0.2099 (3)	0.0360 (8)
O4	−0.4297 (3)	−0.5450 (3)	−0.2795 (2)	0.0276 (7)
Zn1	−0.06957 (4)	0.06945 (4)	0.08772 (4)	0.02053 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.050 (3)	0.050 (3)	0.034 (3)	−0.018 (3)	0.007 (2)	−0.005 (2)
C2	0.031 (3)	0.028 (2)	0.034 (3)	0.006 (2)	0.018 (2)	0.006 (2)
C3	0.027 (3)	0.044 (3)	0.049 (3)	−0.002 (2)	0.006 (2)	−0.014 (3)
C4	0.034 (3)	0.049 (3)	0.058 (4)	−0.003 (3)	0.012 (3)	−0.015 (3)
C5	0.025 (2)	0.025 (2)	0.017 (2)	−0.0031 (18)	0.0029 (17)	0.0006 (17)
C6	0.022 (2)	0.017 (2)	0.026 (2)	−0.0033 (17)	0.0086 (18)	0.0000 (17)
C7	0.024 (2)	0.024 (2)	0.021 (2)	−0.0043 (18)	0.0019 (18)	0.0012 (17)
C14'	0.044 (6)	0.016 (5)	0.066 (8)	−0.002 (5)	0.021 (6)	0.008 (5)
C8	0.049 (3)	0.048 (3)	0.036 (3)	−0.016 (3)	0.022 (3)	−0.010 (2)
C9	0.033 (3)	0.035 (3)	0.028 (2)	0.000 (2)	0.010 (2)	−0.001 (2)
C10	0.024 (2)	0.021 (2)	0.026 (2)	−0.0017 (17)	0.0079 (18)	0.0007 (18)
C14	0.029 (5)	0.038 (6)	0.034 (5)	0.016 (4)	0.010 (4)	0.013 (4)
C11	0.028 (2)	0.031 (3)	0.025 (2)	−0.0091 (19)	0.0054 (19)	0.0008 (19)
C12	0.044 (3)	0.038 (3)	0.040 (3)	−0.016 (3)	−0.009 (2)	0.016 (2)
C13	0.047 (3)	0.065 (4)	0.047 (3)	−0.023 (3)	0.027 (3)	−0.020 (3)
N1	0.033 (2)	0.035 (2)	0.042 (2)	0.0060 (18)	0.0166 (19)	0.0021 (19)
N2	0.039 (2)	0.045 (3)	0.049 (3)	0.014 (2)	0.022 (2)	0.000 (2)
O1	0.0250 (16)	0.0240 (17)	0.0390 (18)	−0.0056 (13)	0.0076 (14)	−0.0079 (14)
O2	0.0243 (16)	0.0238 (17)	0.0314 (17)	−0.0002 (13)	0.0091 (13)	0.0064 (13)
O3	0.0220 (16)	0.042 (2)	0.0415 (19)	0.0034 (15)	0.0094 (14)	−0.0164 (16)
O4	0.0251 (16)	0.0278 (17)	0.0286 (16)	0.0008 (13)	0.0083 (13)	−0.0088 (13)
Zn1	0.0181 (2)	0.0174 (3)	0.0269 (3)	0.0014 (2)	0.00920 (19)	−0.0012 (2)

Geometric parameters (Å, º) top

C1—C2	1.513 (7)	C8—H8B	0.9700
C1—H1A	0.9600	C9—C10	1.519 (6)
C1—H1B	0.9600	C9—H9A	0.9700
C1—H1C	0.9600	C9—H9B	0.9700
C2—N1	1.300 (6)	C10—C14	1.550 (9)
C2—N2	1.315 (6)	C10—C11	1.567 (6)
C3—C4	1.304 (7)	C10—H10	0.9800
C3—N1	1.405 (6)	C14—H14D	0.9600
C3—H3	0.9300	C14—H14E	0.9600
C4—N2	1.399 (7)	C14—H14F	0.9600
C4—H4	0.9300	C11—C12	1.523 (7)
C5—O1	1.249 (5)	C11—C13	1.527 (7)
C5—O2	1.262 (5)	C12—H12A	0.9600
C5—C7	1.519 (6)	C12—H12B	0.9600
C6—O3	1.238 (5)	C12—H12C	0.9600
C6—O4	1.269 (5)	C13—H13A	0.9600
C6—C10	1.521 (6)	C13—H13B	0.9600
C7—C8	1.506 (6)	C13—H13C	0.9600
C7—C14'	1.524 (11)	N1—Zn1	1.988 (4)
C7—C11	1.560 (6)	N2—H2	0.8600
C7—H7	0.9800	O1—Zn1	1.957 (3)
C14'—H14A	0.9600	O2—Zn1ⁱ	1.968 (3)
C14'—H14B	0.9600	O4—Zn1ⁱⁱ	1.926 (3)
C14'—H14C	0.9600	Zn1—O4ⁱⁱⁱ	1.926 (3)
C8—C9	1.561 (7)	Zn1—O2ⁱ	1.968 (3)
C8—H8A	0.9700

C2—C1—H1A	109.5	C9—C10—C6	115.8 (4)
C2—C1—H1B	109.5	C9—C10—C14	108.5 (5)
H1A—C1—H1B	109.5	C6—C10—C14	107.3 (5)
C2—C1—H1C	109.5	C9—C10—C11	105.5 (4)
H1A—C1—H1C	109.5	C6—C10—C11	111.1 (3)
H1B—C1—H1C	109.5	C14—C10—C11	108.5 (5)
N1—C2—N2	113.0 (5)	C9—C10—H10	108.1
N1—C2—C1	123.8 (4)	C6—C10—H10	108.1
N2—C2—C1	123.2 (4)	C14—C10—H10	0.8
C4—C3—N1	109.4 (5)	C11—C10—H10	108.1
C4—C3—H3	125.3	C10—C14—H14D	109.5
N1—C3—H3	125.3	C10—C14—H14E	109.5
C3—C4—N2	107.1 (5)	H14D—C14—H14E	109.5
C3—C4—H4	126.5	C10—C14—H14F	109.5
N2—C4—H4	126.5	H14D—C14—H14F	109.5
O1—C5—O2	124.1 (4)	H14E—C14—H14F	109.5
O1—C5—C7	118.3 (4)	C12—C11—C13	107.6 (4)
O2—C5—C7	117.6 (4)	C12—C11—C7	110.9 (4)
O3—C6—O4	122.3 (4)	C13—C11—C7	113.6 (4)
O3—C6—C10	122.7 (4)	C12—C11—C10	109.9 (4)
O4—C6—C10	115.0 (4)	C13—C11—C10	114.4 (4)
C8—C7—C5	114.9 (4)	C7—C11—C10	100.3 (3)
C8—C7—C14'	102.6 (5)	C11—C12—H12A	109.5
C5—C7—C14'	109.4 (5)	C11—C12—H12B	109.5
C8—C7—C11	104.3 (4)	H12A—C12—H12B	109.5
C5—C7—C11	112.4 (3)	C11—C12—H12C	109.5
C14'—C7—C11	112.8 (6)	H12A—C12—H12C	109.5
C8—C7—H7	108.3	H12B—C12—H12C	109.5
C5—C7—H7	108.3	C11—C13—H13A	109.5
C14'—C7—H7	6.3	C11—C13—H13B	109.5
C11—C7—H7	108.3	H13A—C13—H13B	109.5
C7—C14'—H14A	109.5	C11—C13—H13C	109.5
C7—C14'—H14B	109.5	H13A—C13—H13C	109.5
H14A—C14'—H14B	109.5	H13B—C13—H13C	109.5
C7—C14'—H14C	109.5	C2—N1—C3	104.7 (4)
H14A—C14'—H14C	109.5	C2—N1—Zn1	132.0 (4)
H14B—C14'—H14C	109.5	C3—N1—Zn1	123.4 (3)
C7—C8—C9	106.4 (4)	C2—N2—C4	105.9 (4)
C7—C8—H8A	110.5	C2—N2—H2	127.0
C9—C8—H8A	110.5	C4—N2—H2	127.0
C7—C8—H8B	110.5	C5—O1—Zn1	131.7 (3)
C9—C8—H8B	110.5	C5—O2—Zn1ⁱ	123.6 (3)
H8A—C8—H8B	108.6	C6—O4—Zn1ⁱⁱ	116.8 (3)
C10—C9—C8	105.7 (4)	O4ⁱⁱⁱ—Zn1—O1	115.33 (13)
C10—C9—H9A	110.6	O4ⁱⁱⁱ—Zn1—O2ⁱ	98.14 (12)
C8—C9—H9A	110.6	O1—Zn1—O2ⁱ	119.76 (13)
C10—C9—H9B	110.6	O4ⁱⁱⁱ—Zn1—N1	123.56 (15)
C8—C9—H9B	110.6	O1—Zn1—N1	95.81 (15)
H9A—C9—H9B	108.7	O2ⁱ—Zn1—N1	105.57 (15)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3^iv	0.86	1.86	2.722 (5)	176

Symmetry code: (iv) −x−1, −y, −z.

Experimental details

Crystal data
Chemical formula	[Zn(C₁₀H₁₄O₄)(C₄H₆N₂)]
M_r	345.69
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	12.098 (2), 10.438 (5), 12.873 (2)
β (°)	111.700 (5)
V (Å³)	1510.4 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.64
Crystal size (mm)	0.31 × 0.25 × 0.21

Data collection
Diffractometer	Bruker APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.57, 0.72
No. of measured, independent and observed [I > 2σ(I)] reflections	9848, 3004, 2433
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.620

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.121, 1.08
No. of reflections	3004
No. of parameters	200
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.13, −0.41

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3ⁱ	0.86	1.86	2.722 (5)	175.6

Symmetry code: (i) −x−1, −y, −z.

Acknowledgements

We gratefully acknowledge the support of this work by funding from the Department of Education of Jilin Province, People's Republic of China.

References

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Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
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