supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

xu2375 scheme

Acta Cryst. (2007). E63, m3113    [ doi:10.1107/S1600536807059296 ]

Bis(4-formylbenzoato-[kappa]O)bis(1H-imidazole-[kappa]N3)zinc(II)

Z.-P. Deng, S. Gao and S. W. Ng

Abstract top

The zinc centre in the title complex, [Zn(C8H5O3)2(C3H4N2)2], shows tetrahedral coordination. Adjacent molecules are linked by N-H...O hydrogen bonds into a layer structure.

Comment top

As a part of our ongoing investigation on 4-formylbenzoate complexes (Deng et al., 2006a, 2006b, 2007), the title ZnII complex has been prepared and its structure is reported here. The molecular structure is shown in Fig. 1. The ZnII ion displays a tetrahedral coordination geometry (Table 1). Adjacent molecules are linked by N—H···O hydrogen bonds into a layer structure (Table 2 and Fig. 2).

Related literature top

For the diaqua complex, see Deng et al. (2006a), and for the aqua phenanthroline adduct, see Deng et al. (2006b). The monohydrated bis(benzimidazole) adduct is hydrogen bonded into a chain structure (see Deng et al., 2007).

Experimental top

Zinc sulfate heptahydrate (1.44 g, 5 mmol) was added to an aqueous solution (25 ml) of 4-formylbenzoic acid (1.5 g, 10 mmol) and imidazole (0.68 g, 10 mmol). The pH value of the mixture was about 6. The solution was allowed to evaporate at room temperature; colorless prismatic crystals separated from the filtered solution after several days. CH&N elemental analysis. Calc. for C22H18N4O6Zn: C 52.87, H 3.63, N 11.21%. Found: C 52.88, H 3.68, N 11.18%.

Refinement top

The carbon- and nitrogen bound H atoms were generated geometrically (C–H 0.93, N–H 0.86 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2Ueq(C,N).

The final difference Fourier map had a large peak /deep hole near Zn1.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001) and OLEX (Dolomanov et al., 2003); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot of the molecular structure. Displacement ellipsoids are drawn at the 50% probability level, and H atoms are drawn as spheres of arbitrary radii.
[Figure 2] Fig. 2. OLEX (Dolomanov et al., 2003) representation of the hydrogen-bonded layer structure.
Bis(4-formylbenzoato-κO)bis(1H-imidazole-κN3)zinc(II) top
Crystal data top
[Zn(C8H5O3)2(C3H4N2)2]F000 = 512
Mr = 499.77Dx = 1.477 Mg m−3
Monoclinic, P21Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 8013 reflections
a = 11.9413 (9) Åθ = 3.1–27.5º
b = 7.0455 (5) ŵ = 1.14 mm−1
c = 14.2092 (9) ÅT = 295 (2) K
β = 109.904 (2)ºPrism, colorless
V = 1124.1 (1) Å30.36 × 0.25 × 0.21 mm
Z = 2
Data collection top
Rigaku RAXIS-RAPID IP
diffractometer		4493 independent reflections
Radiation source: fine-focus sealed tube2901 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.042
T = 295(2) Kθmax = 27.5º
ω scanθmin = 3.1º
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −15→15
Tmin = 0.662, Tmax = 0.796k = −9→8
11106 measured reflectionsl = −18→18
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.040  w = 1/[σ2(Fo2) + (0.0471P)2 + 1.7346P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.150(Δ/σ)max = 0.001
S = 1.13Δρmax = 1.17 e Å−3
4493 reflectionsΔρmin = −1.11 e Å−3
299 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983) parameter from 1716 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.01 (2)
Secondary atom site location: difference Fourier map
Crystal data top
[Zn(C8H5O3)2(C3H4N2)2]V = 1124.1 (1) Å3
Mr = 499.77Z = 2
Monoclinic, P21Mo Kα
a = 11.9413 (9) ŵ = 1.14 mm−1
b = 7.0455 (5) ÅT = 295 (2) K
c = 14.2092 (9) Å0.36 × 0.25 × 0.21 mm
β = 109.904 (2)º
Data collection top
Rigaku RAXIS-RAPID IP
diffractometer		4493 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2901 reflections with I > 2σ(I)
Tmin = 0.662, Tmax = 0.796Rint = 0.042
11106 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.150Δρmax = 1.17 e Å−3
S = 1.13Δρmin = −1.11 e Å−3
4493 reflectionsAbsolute structure: Flack (1983) parameter from 1716 Friedel pairs
299 parametersFlack parameter: 0.01 (2)
1 restraint
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.77235 (5)0.49998 (13)0.20968 (4)0.0464 (2)
O10.8971 (4)0.3416 (7)0.1932 (4)0.0585 (13)
O20.7697 (4)0.1549 (8)0.0823 (4)0.0684 (15)
O31.3608 (7)−0.2711 (12)0.1953 (5)0.111 (3)
O40.6612 (4)0.3861 (8)0.2687 (3)0.0608 (13)
O50.7938 (4)0.3692 (9)0.4217 (4)0.0719 (15)
O60.1902 (7)0.3427 (14)0.4523 (6)0.126 (3)
N10.6505 (4)0.5887 (8)0.0812 (4)0.0461 (12)
N20.4747 (5)0.6479 (9)−0.0238 (5)0.0631 (17)
H2n0.39980.6732−0.04690.076*
N30.8663 (4)0.7125 (8)0.2943 (4)0.0473 (13)
N41.0097 (5)0.8557 (10)0.4062 (4)0.0622 (16)
H4n1.07740.87590.45210.075*
C10.6901 (5)0.3684 (10)0.3637 (5)0.0498 (16)
C20.5873 (6)0.3511 (9)0.4011 (4)0.0462 (15)
C30.6076 (7)0.3316 (11)0.5034 (5)0.0585 (18)
H30.68470.32350.54890.070*
C40.5090 (8)0.3245 (11)0.5363 (5)0.064 (2)
H40.52150.31250.60430.077*
C50.3954 (7)0.3348 (11)0.4702 (6)0.0616 (19)
C60.3780 (7)0.3571 (12)0.3701 (6)0.064 (2)
H60.30080.36800.32490.077*
C70.4699 (6)0.3635 (11)0.3360 (5)0.0535 (17)
H70.45500.37650.26770.064*
C80.2937 (10)0.3301 (16)0.5073 (8)0.091 (3)
H80.30940.31680.57570.109*
C90.8711 (5)0.1953 (10)0.1381 (5)0.0450 (14)
C100.9721 (6)0.0645 (9)0.1431 (5)0.0459 (16)
C110.9491 (7)−0.1102 (12)0.0963 (6)0.064 (2)
H110.8710−0.14690.06180.077*
C121.0425 (8)−0.2306 (12)0.1007 (6)0.074 (2)
H121.0270−0.34780.06880.089*
C131.1581 (7)−0.1771 (12)0.1522 (6)0.062 (2)
C141.1811 (6)−0.0046 (18)0.1993 (5)0.073 (2)
H141.25930.03170.23360.087*
C151.0887 (5)0.1152 (11)0.1958 (6)0.062 (2)
H151.10470.23100.22920.075*
C161.2565 (9)−0.3093 (15)0.1549 (7)0.082 (3)
H161.2368−0.42700.12410.098*
C170.6563 (6)0.5897 (11)−0.0136 (5)0.0551 (17)
H170.72420.5678−0.03000.066*
C180.5469 (7)0.6276 (12)−0.0788 (5)0.064 (2)
H180.52520.6379−0.14800.077*
C190.5387 (5)0.6224 (10)0.0710 (5)0.0496 (16)
H190.50890.62740.12350.060*
C200.8343 (6)0.8961 (11)0.3001 (5)0.0549 (17)
H200.76220.95050.26190.066*
C210.9231 (6)0.9861 (16)0.3696 (5)0.0631 (17)
H210.92481.11260.38870.076*
C220.9740 (6)0.6922 (12)0.3605 (5)0.0578 (18)
H221.01800.58030.37310.069*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0356 (3)0.0558 (4)0.0432 (3)0.0037 (4)0.0074 (2)−0.0028 (5)
O10.041 (2)0.057 (3)0.070 (3)0.004 (2)0.009 (2)−0.011 (3)
O20.035 (2)0.080 (4)0.074 (3)0.004 (2)−0.002 (2)−0.016 (3)
O30.096 (5)0.148 (7)0.102 (5)0.067 (5)0.051 (4)0.033 (5)
O40.054 (3)0.076 (4)0.044 (2)−0.005 (2)0.006 (2)0.003 (2)
O50.049 (3)0.101 (4)0.055 (3)0.007 (3)0.005 (2)0.016 (3)
O60.090 (5)0.172 (8)0.134 (6)0.009 (6)0.061 (5)0.006 (6)
N10.032 (2)0.061 (3)0.043 (3)0.005 (2)0.010 (2)−0.004 (2)
N20.034 (3)0.072 (4)0.072 (4)0.007 (3)0.003 (3)0.008 (3)
N30.037 (3)0.056 (4)0.044 (3)0.004 (2)0.007 (2)0.001 (3)
N40.058 (4)0.071 (4)0.048 (3)−0.015 (3)0.006 (3)−0.015 (3)
C10.040 (3)0.052 (4)0.051 (4)0.007 (3)0.007 (3)0.002 (3)
C20.055 (4)0.042 (4)0.042 (3)0.005 (3)0.018 (3)−0.001 (3)
C30.062 (4)0.061 (5)0.053 (4)0.010 (3)0.019 (3)0.003 (4)
C40.096 (6)0.054 (5)0.048 (4)0.006 (4)0.032 (4)0.009 (3)
C50.061 (5)0.057 (5)0.074 (5)0.007 (4)0.031 (4)0.004 (4)
C60.050 (4)0.075 (5)0.070 (5)−0.006 (4)0.025 (4)−0.004 (4)
C70.049 (4)0.062 (5)0.047 (3)0.003 (3)0.013 (3)−0.006 (3)
C80.099 (8)0.095 (8)0.099 (7)0.014 (6)0.060 (6)0.003 (6)
C90.040 (3)0.048 (4)0.046 (3)0.005 (3)0.012 (3)0.001 (3)
C100.040 (3)0.046 (4)0.054 (4)0.008 (2)0.019 (3)0.003 (3)
C110.059 (5)0.060 (5)0.073 (5)−0.003 (4)0.023 (4)−0.013 (4)
C120.096 (7)0.055 (5)0.077 (5)0.016 (4)0.037 (5)−0.010 (4)
C130.067 (5)0.069 (5)0.058 (4)0.019 (4)0.032 (4)0.008 (4)
C140.046 (3)0.090 (6)0.079 (4)0.027 (6)0.017 (3)−0.012 (7)
C150.033 (3)0.067 (5)0.083 (5)0.003 (3)0.013 (3)−0.021 (4)
C160.093 (7)0.091 (7)0.073 (5)0.042 (6)0.042 (5)0.018 (5)
C170.053 (4)0.066 (5)0.043 (3)0.002 (3)0.012 (3)0.003 (3)
C180.058 (4)0.076 (6)0.046 (4)0.001 (4)0.003 (3)0.008 (4)
C190.031 (3)0.062 (4)0.049 (3)0.004 (3)0.005 (3)−0.003 (3)
C200.049 (4)0.065 (5)0.051 (4)0.011 (3)0.017 (3)0.003 (3)
C210.077 (4)0.054 (4)0.061 (4)−0.004 (5)0.027 (3)−0.010 (5)
C220.045 (4)0.064 (5)0.052 (4)−0.003 (3)0.000 (3)−0.010 (4)
Geometric parameters (Å, °) top
Zn1—O11.938 (5)C5—C61.375 (10)
Zn1—O41.966 (5)C5—C81.480 (12)
Zn1—N12.007 (5)C6—C71.342 (9)
Zn1—N32.007 (6)C6—H60.9300
O1—C91.267 (8)C7—H70.9300
O2—C91.235 (7)C8—H80.9300
O3—C161.212 (11)C9—C101.500 (9)
O4—C11.281 (7)C10—C111.382 (10)
O5—C11.232 (7)C10—C151.384 (9)
O6—C81.220 (11)C11—C121.385 (11)
N1—C191.315 (7)C11—H110.9300
N1—C171.373 (8)C12—C131.377 (12)
N2—C191.315 (8)C12—H120.9300
N2—C181.354 (10)C13—C141.369 (14)
N2—H2n0.8600C13—C161.489 (11)
N3—C221.318 (8)C14—C151.377 (10)
N3—C201.360 (9)C14—H140.9300
N4—C221.320 (10)C15—H150.9300
N4—C211.348 (11)C16—H160.9300
N4—H4n0.8600C17—C181.346 (10)
C1—C21.499 (9)C17—H170.9300
C2—C71.395 (9)C18—H180.9300
C2—C31.397 (9)C19—H190.9300
C3—C41.408 (11)C20—C211.337 (10)
C3—H30.9300C20—H200.9300
C4—C51.364 (11)C21—H210.9300
C4—H40.9300C22—H220.9300
O1—Zn1—O4118.3 (2)C5—C8—H8118.5
O1—Zn1—N1114.7 (2)O2—C9—O1124.4 (6)
O1—Zn1—N3101.9 (2)O2—C9—C10119.1 (6)
O4—Zn1—N197.4 (2)O1—C9—C10116.5 (5)
O4—Zn1—N3111.7 (2)C11—C10—C15119.3 (6)
N1—Zn1—N3113.4 (2)C11—C10—C9120.0 (7)
C9—O1—Zn1120.4 (4)C15—C10—C9120.7 (6)
C1—O4—Zn1120.7 (4)C10—C11—C12119.9 (8)
C19—N1—C17106.2 (5)C10—C11—H11120.1
C19—N1—Zn1123.5 (4)C12—C11—H11120.1
C17—N1—Zn1129.1 (4)C13—C12—C11120.2 (8)
C19—N2—C18108.4 (5)C13—C12—H12119.9
C19—N2—H2n125.8C11—C12—H12119.9
C18—N2—H2n125.8C14—C13—C12120.1 (7)
C22—N3—C20106.6 (6)C14—C13—C16121.1 (8)
C22—N3—Zn1123.9 (5)C12—C13—C16118.8 (9)
C20—N3—Zn1129.5 (4)C13—C14—C15120.1 (7)
C22—N4—C21109.2 (6)C13—C14—H14120.0
C22—N4—H4n125.4C15—C14—H14120.0
C21—N4—H4n125.4C14—C15—C10120.5 (8)
O5—C1—O4123.6 (6)C14—C15—H15119.8
O5—C1—C2121.4 (6)C10—C15—H15119.8
O4—C1—C2115.0 (5)O3—C16—C13123.3 (10)
C7—C2—C3118.4 (6)O3—C16—H16118.4
C7—C2—C1121.3 (6)C13—C16—H16118.4
C3—C2—C1120.3 (6)C18—C17—N1108.4 (7)
C2—C3—C4118.7 (7)C18—C17—H17125.8
C2—C3—H3120.6N1—C17—H17125.8
C4—C3—H3120.6C17—C18—N2106.4 (6)
C5—C4—C3121.1 (7)C17—C18—H18126.8
C5—C4—H4119.4N2—C18—H18126.8
C3—C4—H4119.4N1—C19—N2110.6 (6)
C4—C5—C6118.9 (7)N1—C19—H19124.7
C4—C5—C8119.8 (8)N2—C19—H19124.7
C6—C5—C8121.2 (8)C21—C20—N3109.1 (7)
C7—C6—C5121.5 (7)C21—C20—H20125.4
C7—C6—H6119.2N3—C20—H20125.4
C5—C6—H6119.2C20—C21—N4105.9 (8)
C6—C7—C2121.3 (7)C20—C21—H21127.1
C6—C7—H7119.4N4—C21—H21127.1
C2—C7—H7119.4N3—C22—N4109.2 (7)
O6—C8—C5123.0 (10)N3—C22—H22125.4
O6—C8—H8118.5N4—C22—H22125.4
O4—Zn1—O1—C961.0 (5)C4—C5—C8—O6178.4 (10)
N3—Zn1—O1—C9−176.1 (5)C6—C5—C8—O61.1 (15)
N1—Zn1—O1—C9−53.2 (6)Zn1—O1—C9—O29.4 (9)
O1—Zn1—O4—C181.4 (6)Zn1—O1—C9—C10−170.2 (4)
N3—Zn1—O4—C1−36.4 (6)O2—C9—C10—C11−8.5 (10)
N1—Zn1—O4—C1−155.2 (5)O1—C9—C10—C11171.1 (6)
O1—Zn1—N1—C19149.5 (5)O2—C9—C10—C15172.6 (7)
O4—Zn1—N1—C1923.6 (6)O1—C9—C10—C15−7.7 (10)
N3—Zn1—N1—C19−94.0 (5)C15—C10—C11—C12−1.4 (11)
O1—Zn1—N1—C17−16.0 (7)C9—C10—C11—C12179.8 (7)
O4—Zn1—N1—C17−141.9 (6)C10—C11—C12—C130.4 (13)
N3—Zn1—N1—C17100.5 (6)C11—C12—C13—C140.1 (13)
O1—Zn1—N3—C22−31.2 (6)C11—C12—C13—C16−179.6 (8)
O4—Zn1—N3—C2296.1 (6)C12—C13—C14—C150.4 (13)
N1—Zn1—N3—C22−155.0 (5)C16—C13—C14—C15−179.9 (8)
O1—Zn1—N3—C20152.0 (6)C13—C14—C15—C10−1.4 (13)
O4—Zn1—N3—C20−80.7 (6)C11—C10—C15—C141.9 (12)
N1—Zn1—N3—C2028.2 (6)C9—C10—C15—C14−179.3 (7)
Zn1—O4—C1—O5−20.8 (10)C14—C13—C16—O3−2.4 (14)
Zn1—O4—C1—C2157.8 (5)C12—C13—C16—O3177.2 (8)
O5—C1—C2—C7175.5 (7)C19—N1—C17—C181.1 (8)
O4—C1—C2—C7−3.1 (10)Zn1—N1—C17—C18168.6 (5)
O5—C1—C2—C3−1.3 (11)N1—C17—C18—N2−0.6 (9)
O4—C1—C2—C3−179.8 (6)C19—N2—C18—C17−0.2 (9)
C7—C2—C3—C40.3 (11)C17—N1—C19—N2−1.2 (8)
C1—C2—C3—C4177.1 (7)Zn1—N1—C19—N2−169.6 (5)
C2—C3—C4—C50.5 (11)C18—N2—C19—N10.9 (9)
C3—C4—C5—C6−1.6 (12)C22—N3—C20—C210.3 (8)
C3—C4—C5—C8−179.0 (8)Zn1—N3—C20—C21177.4 (5)
C4—C5—C6—C71.9 (13)N3—C20—C21—N40.0 (8)
C8—C5—C6—C7179.3 (9)C22—N4—C21—C20−0.2 (8)
C5—C6—C7—C2−1.1 (13)C20—N3—C22—N4−0.4 (8)
C3—C2—C7—C60.0 (11)Zn1—N3—C22—N4−177.7 (5)
C1—C2—C7—C6−176.8 (7)C21—N4—C22—N30.4 (8)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2n···O2i0.861.922.749 (7)163
N4—H4n···O5ii0.861.932.754 (7)162
Symmetry codes: (i) −x+1, y+1/2, −z; (ii) −x+2, y+1/2, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Zn1—O11.938 (5)Zn1—N12.007 (5)
Zn1—O41.966 (5)Zn1—N32.007 (6)
O1—Zn1—O4118.3 (2)O4—Zn1—N197.4 (2)
O1—Zn1—N1114.7 (2)O4—Zn1—N3111.7 (2)
O1—Zn1—N3101.9 (2)N1—Zn1—N3113.4 (2)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2n···O2i0.861.922.749 (7)163
N4—H4n···O5ii0.861.932.754 (7)162
Symmetry codes: (i) −x+1, y+1/2, −z; (ii) −x+2, y+1/2, −z+1.
Acknowledgements top

The authors thank the Heilongjiang Province Natural Science Foundation (grant No. B200501), the Scientific Fund for Remarkable Teachers of Heilongjiang Province (grant No. 1054 G036) and the University of Malaya for supporting this study.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Deng, Z.-P., Gao, S., Huo, L.-H. & Zhao, H. (2006a). Acta Cryst. E62, m3524–m3526.

Deng, Z.-P., Gao, S., Huo, L.-H. & Zhao, H. (2006b). Acta Cryst. E62, m3527–m3529.

Deng, Z.-P., Gao, S. & Ng, S. W. (2007). Acta Cryst. E63, m1712–?.

Dolomanov, O. V., Blake, A. J., Champness, N. R. & Schröder, M. (2003). J. Appl. Cryst. 36, 1283–1284.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Westrip, S. P. (2007). publCIF. In preparation.