metal-organic compounds
Bis(2-aminopyrimidine-κN1)dibromidozinc(II)
aHuazhong Agricultural University, Department of Chemistry, College of Basic Sciences, Wuhan 430070, People's Republic of China, and bSchool of Materials Science and Engineering, Wuhan Institute of Technology, Wuhan, 430073, People's Republic of China
*Correspondence e-mail: doctor-qu@126.com
The title compound, [ZnBr2(C4H5N3)2], is a mononuclear complex in which the ZnII ions have distorted tetrahedral coordination geometry. The ZnII ion binds to two N atoms from two different 2-aminopyrimidine ligands and two bromide ions. N—H⋯N hydrogen bonds link the molecules to form a one-dimensional supramolecular structure. The supramolecular chains are parallel to each other and N—H⋯Br hydrogen bonds link them into a two-dimensional network in the ac plane. Additionally, there are strong π–π interactions [centroid–centroid distance = 3.403 (3) Å].
Related literature
For related literature, see: Bourne et al. (2001); Etter et al. (1990); Lin & Zeng (2007); Pon et al. (1997).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Siemens, 1996); cell SAINT (Siemens, 1996); data reduction: SAINT; 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.
Supporting information
10.1107/S1600536808006466/rn2036sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808006466/rn2036Isup2.hkl
10 ml e thanol solution containing ZnBr2 (0.5 mmol) and 2-aminopyrimidine (1.0 mmol) was stirred at room temperature for 12 h and then filtered. The filtrate was kept at room temperature in the dark for two weeks to give white crystals of (I). The crystals were isolated and washed three times with ethanol and dried in a vacuum desiccator using anhydrous CaCl2. Analysis calculated for C8N6H10 Zn Br2: C 23.13, N 20.23, H 2.43%; found: C 23.19, N 20.46,H 2.61%.
The H atoms bonded to C atoms were placed in calculated positions, and were allowed to ride on their parent C atoms, with a distance of 0.93 Å for aromatic H atoms and Uiso(H) = 1.2 times its parent atom. The H atoms of –NH2 were found from residue peaks in the difference map. The H atoms of the NH2 group were placed in geometrically calculated positions and the N—H distance restrained to 0.86 (2) Å. The isotropic displacement parameters were set equal to 1.5Ueq(parent N atom) for amino H atoms.
Data collection: SMART (Siemens, 1996); cell
SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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 (Sheldrick, 2008).[ZnBr2(C4H5N3)2] | Z = 2 |
Mr = 415.41 | F(000) = 400 |
Triclinic, P1 | Dx = 2.060 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.7912 (11) Å | Cell parameters from 2800 reflections |
b = 7.2197 (12) Å | θ = 2.1–28.7° |
c = 15.512 (3) Å | µ = 7.79 mm−1 |
α = 81.060 (3)° | T = 292 K |
β = 83.823 (3)° | Block, white |
γ = 63.132 (2)° | 0.20 × 0.16 × 0.14 mm |
V = 669.61 (19) Å3 |
Siemens SMART CCD area-detector diffractometer | 2342 independent reflections |
Radiation source: fine-focus sealed tube | 1878 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.074 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→7 |
Tmin = 0.305, Tmax = 0.409 | k = −8→8 |
5351 measured reflections | l = −18→18 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0639P)2] where P = (Fo2 + 2Fc2)/3 |
2342 reflections | (Δ/σ)max < 0.001 |
156 parameters | Δρmax = 0.80 e Å−3 |
0 restraints | Δρmin = −0.69 e Å−3 |
[ZnBr2(C4H5N3)2] | γ = 63.132 (2)° |
Mr = 415.41 | V = 669.61 (19) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.7912 (11) Å | Mo Kα radiation |
b = 7.2197 (12) Å | µ = 7.79 mm−1 |
c = 15.512 (3) Å | T = 292 K |
α = 81.060 (3)° | 0.20 × 0.16 × 0.14 mm |
β = 83.823 (3)° |
Siemens SMART CCD area-detector diffractometer | 2342 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1878 reflections with I > 2σ(I) |
Tmin = 0.305, Tmax = 0.409 | Rint = 0.074 |
5351 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.80 e Å−3 |
2342 reflections | Δρmin = −0.69 e Å−3 |
156 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.19184 (13) | 0.75744 (9) | 0.20800 (4) | 0.0660 (2) | |
Br2 | 0.57558 (9) | 0.19239 (9) | 0.31136 (4) | 0.0528 (2) | |
C1 | 0.2693 (11) | 0.1954 (8) | 0.0989 (3) | 0.0472 (14) | |
C2 | −0.0153 (14) | 0.2437 (10) | 0.0194 (4) | 0.0631 (18) | |
H2 | −0.0664 | 0.2230 | −0.0298 | 0.076* | |
C3 | −0.1718 (12) | 0.3635 (10) | 0.0799 (4) | 0.0613 (17) | |
H3 | −0.3231 | 0.4171 | 0.0737 | 0.074* | |
C4 | −0.0852 (11) | 0.3955 (9) | 0.1486 (4) | 0.0527 (15) | |
H4 | −0.1815 | 0.4767 | 0.1901 | 0.063* | |
C5 | −0.0098 (7) | 0.2696 (8) | 0.4074 (3) | 0.0322 (10) | |
C6 | −0.2637 (9) | 0.4775 (9) | 0.5028 (3) | 0.0470 (14) | |
H6 | −0.3439 | 0.4925 | 0.5559 | 0.056* | |
C7 | −0.2909 (8) | 0.6530 (9) | 0.4488 (4) | 0.0481 (14) | |
H7 | −0.3932 | 0.7848 | 0.4622 | 0.058* | |
C8 | −0.1607 (8) | 0.6272 (8) | 0.3737 (3) | 0.0452 (13) | |
H8 | −0.1738 | 0.7449 | 0.3357 | 0.054* | |
N1 | 0.1338 (8) | 0.3141 (7) | 0.1588 (2) | 0.0412 (10) | |
N2 | 0.1963 (11) | 0.1600 (8) | 0.0279 (3) | 0.0594 (14) | |
N3 | 0.4858 (9) | 0.1121 (9) | 0.1065 (3) | 0.0674 (16) | |
H3A | 0.5101 | 0.1135 | 0.1524 | 0.101* | |
H3B | 0.5506 | 0.1597 | 0.0607 | 0.101* | |
N4 | −0.0134 (6) | 0.4360 (6) | 0.3530 (2) | 0.0356 (9) | |
N5 | −0.1293 (7) | 0.2848 (7) | 0.4844 (3) | 0.0414 (10) | |
N6 | 0.1223 (8) | 0.0761 (7) | 0.3887 (3) | 0.0477 (11) | |
H6A | 0.1646 | 0.0802 | 0.3421 | 0.071* | |
H6B | 0.0449 | 0.0026 | 0.3950 | 0.071* | |
Zn1 | 0.22458 (9) | 0.41974 (8) | 0.25651 (3) | 0.0358 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.1151 (6) | 0.0446 (4) | 0.0495 (4) | −0.0468 (4) | 0.0003 (3) | −0.0032 (3) |
Br2 | 0.0431 (4) | 0.0522 (4) | 0.0541 (4) | −0.0125 (3) | 0.0026 (3) | −0.0125 (3) |
C1 | 0.082 (5) | 0.042 (3) | 0.033 (3) | −0.042 (3) | 0.011 (3) | −0.011 (2) |
C2 | 0.115 (6) | 0.062 (4) | 0.037 (3) | −0.061 (4) | −0.013 (3) | 0.002 (3) |
C3 | 0.086 (5) | 0.067 (4) | 0.051 (4) | −0.051 (4) | −0.017 (3) | 0.005 (3) |
C4 | 0.081 (5) | 0.050 (3) | 0.040 (3) | −0.040 (3) | −0.002 (3) | −0.005 (3) |
C5 | 0.027 (2) | 0.041 (3) | 0.027 (2) | −0.014 (2) | 0.0021 (18) | −0.007 (2) |
C6 | 0.042 (3) | 0.068 (4) | 0.038 (3) | −0.028 (3) | 0.009 (2) | −0.024 (3) |
C7 | 0.032 (3) | 0.050 (3) | 0.058 (3) | −0.010 (3) | 0.009 (2) | −0.024 (3) |
C8 | 0.041 (3) | 0.037 (3) | 0.045 (3) | −0.006 (2) | 0.001 (2) | −0.007 (2) |
N1 | 0.063 (3) | 0.049 (3) | 0.027 (2) | −0.037 (2) | 0.0078 (19) | −0.0118 (19) |
N2 | 0.109 (5) | 0.058 (3) | 0.036 (3) | −0.056 (3) | 0.004 (3) | −0.015 (2) |
N3 | 0.081 (4) | 0.090 (4) | 0.049 (3) | −0.049 (3) | 0.023 (3) | −0.041 (3) |
N4 | 0.036 (2) | 0.038 (2) | 0.030 (2) | −0.0123 (18) | 0.0025 (16) | −0.0095 (18) |
N5 | 0.040 (2) | 0.056 (3) | 0.030 (2) | −0.023 (2) | 0.0061 (18) | −0.011 (2) |
N6 | 0.056 (3) | 0.044 (3) | 0.042 (3) | −0.022 (2) | 0.014 (2) | −0.011 (2) |
Zn1 | 0.0478 (4) | 0.0332 (3) | 0.0277 (3) | −0.0190 (3) | 0.0045 (2) | −0.0081 (2) |
Br1—Zn1 | 2.3528 (9) | C5—N5 | 1.360 (6) |
Br2—Zn1 | 2.3593 (8) | C6—N5 | 1.330 (7) |
C1—N3 | 1.324 (8) | C6—C7 | 1.354 (8) |
C1—N1 | 1.340 (7) | C6—H6 | 0.9300 |
C1—N2 | 1.358 (7) | C7—C8 | 1.368 (8) |
C2—N2 | 1.295 (9) | C7—H7 | 0.9300 |
C2—C3 | 1.401 (10) | C8—N4 | 1.353 (6) |
C2—H2 | 0.9300 | C8—H8 | 0.9300 |
C3—C4 | 1.368 (8) | N1—Zn1 | 2.060 (4) |
C3—H3 | 0.9300 | N3—H3A | 0.7500 |
C4—N1 | 1.347 (8) | N3—H3B | 0.9006 |
C4—H4 | 0.9300 | N4—Zn1 | 2.056 (4) |
C5—N6 | 1.333 (6) | N6—H6A | 0.7500 |
C5—N4 | 1.348 (6) | N6—H6B | 0.8901 |
N3—C1—N1 | 119.5 (5) | N4—C8—H8 | 119.0 |
N3—C1—N2 | 117.2 (5) | C7—C8—H8 | 119.0 |
N1—C1—N2 | 123.2 (6) | C1—N1—C4 | 117.6 (5) |
N2—C2—C3 | 124.1 (6) | C1—N1—Zn1 | 126.4 (4) |
N2—C2—H2 | 118.0 | C4—N1—Zn1 | 115.4 (3) |
C3—C2—H2 | 118.0 | C2—N2—C1 | 117.5 (6) |
C4—C3—C2 | 114.9 (7) | C1—N3—H3A | 109.5 |
C4—C3—H3 | 122.5 | C1—N3—H3B | 111.2 |
C2—C3—H3 | 122.5 | H3A—N3—H3B | 120.6 |
N1—C4—C3 | 122.7 (6) | C5—N4—C8 | 116.8 (4) |
N1—C4—H4 | 118.6 | C5—N4—Zn1 | 124.1 (3) |
C3—C4—H4 | 118.6 | C8—N4—Zn1 | 118.1 (4) |
N6—C5—N4 | 120.2 (4) | C6—N5—C5 | 116.2 (5) |
N6—C5—N5 | 116.0 (5) | C5—N6—H6A | 109.5 |
N4—C5—N5 | 123.8 (4) | C5—N6—H6B | 109.0 |
N5—C6—C7 | 123.9 (5) | H6A—N6—H6B | 108.2 |
N5—C6—H6 | 118.0 | N4—Zn1—N1 | 101.97 (16) |
C7—C6—H6 | 118.0 | N4—Zn1—Br1 | 109.63 (11) |
C6—C7—C8 | 116.9 (5) | N1—Zn1—Br1 | 109.06 (12) |
C6—C7—H7 | 121.6 | N4—Zn1—Br2 | 108.97 (11) |
C8—C7—H7 | 121.6 | N1—Zn1—Br2 | 114.70 (13) |
N4—C8—C7 | 122.1 (5) | Br1—Zn1—Br2 | 112.00 (3) |
N2—C2—C3—C4 | 2.8 (9) | C7—C8—N4—C5 | 3.9 (7) |
C2—C3—C4—N1 | −1.5 (9) | C7—C8—N4—Zn1 | −164.7 (4) |
N5—C6—C7—C8 | −4.1 (8) | C7—C6—N5—C5 | 2.0 (7) |
C6—C7—C8—N4 | 1.0 (8) | N6—C5—N5—C6 | −179.1 (4) |
N3—C1—N1—C4 | −179.8 (5) | N4—C5—N5—C6 | 3.5 (7) |
N2—C1—N1—C4 | 2.2 (8) | C5—N4—Zn1—N1 | 79.9 (4) |
N3—C1—N1—Zn1 | 9.2 (7) | C8—N4—Zn1—N1 | −112.3 (4) |
N2—C1—N1—Zn1 | −168.8 (4) | C5—N4—Zn1—Br1 | −164.6 (3) |
C3—C4—N1—C1 | −0.8 (8) | C8—N4—Zn1—Br1 | 3.2 (4) |
C3—C4—N1—Zn1 | 171.2 (5) | C5—N4—Zn1—Br2 | −41.7 (4) |
C3—C2—N2—C1 | −1.5 (9) | C8—N4—Zn1—Br2 | 126.0 (3) |
N3—C1—N2—C2 | −179.1 (5) | C1—N1—Zn1—N4 | −149.6 (4) |
N1—C1—N2—C2 | −1.1 (8) | C4—N1—Zn1—N4 | 39.2 (4) |
N6—C5—N4—C8 | 176.3 (4) | C1—N1—Zn1—Br1 | 94.5 (4) |
N5—C5—N4—C8 | −6.3 (7) | C4—N1—Zn1—Br1 | −76.7 (4) |
N6—C5—N4—Zn1 | −15.8 (6) | C1—N1—Zn1—Br2 | −32.1 (5) |
N5—C5—N4—Zn1 | 161.6 (3) | C4—N1—Zn1—Br2 | 156.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···Br2i | 0.93 | 2.87 | 3.651 (5) | 142 |
N6—H6B···N5ii | 0.89 | 2.47 | 2.996 (6) | 119 |
N3—H3A···Br2 | 0.75 | 2.74 | 3.480 (5) | 170 |
Symmetry codes: (i) x−1, y+1, z; (ii) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [ZnBr2(C4H5N3)2] |
Mr | 415.41 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 292 |
a, b, c (Å) | 6.7912 (11), 7.2197 (12), 15.512 (3) |
α, β, γ (°) | 81.060 (3), 83.823 (3), 63.132 (2) |
V (Å3) | 669.61 (19) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 7.79 |
Crystal size (mm) | 0.20 × 0.16 × 0.14 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.305, 0.409 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5351, 2342, 1878 |
Rint | 0.074 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.110, 1.02 |
No. of reflections | 2342 |
No. of parameters | 156 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.80, −0.69 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···Br2i | 0.93 | 2.87 | 3.651 (5) | 141.8 |
N6—H6B···N5ii | 0.89 | 2.47 | 2.996 (6) | 118.6 |
N3—H3A···Br2 | 0.75 | 2.74 | 3.480 (5) | 169.9 |
Symmetry codes: (i) x−1, y+1, z; (ii) −x, −y, −z+1. |
Acknowledgements
The authors are grateful for financial support from the Bureau of Science and Technology of Wuhan City, Hubei Province, People's Republic of China (grant No. 20055003059-28).
References
Bourne, S. A., Kilkenny, M. & Nassimbeni, L. R. (2001). Dalton Trans. pp. 1176–1179. CrossRef Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef CAS Web of Science IUCr Journals Google Scholar
Lin, Z.-D. & Zeng, W. (2007). Acta Cryst. E63, m1597. Web of Science CSD CrossRef IUCr Journals Google Scholar
Pon, G., Willett, R. D., Prince, B. A. & Robinson, W. T. (1997). Inorg. Chim. Acta, 255, 325–334. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
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Recently, the design of molecular architecture with pyrimidine and bipyrimidine has aroused interest in the fields of coordination, bioinorganic and magnetochemistry (Pon et al., 1997).
In our laboratory, analogous crystals have been obtained from the interaction of zinc(lI) chloride with 2-aminopyrimidine (Lin & Zeng, 2007). As an extension of this work, we report the crystal structure of the title compound, (I), bis(2-aminopyrimidine)-zinc(II) bromide. Compound I contains discrete L2CuBr2 molecules (L: 2-aminopyrimidine). The ZnII ion is coordinated by two N atoms from two different 2-aminopyrimidine ligands and two Br anions, giving distorted tetrahedral coordination geometry [mean Zn—N = 2.058 (8) Å and mean Zn—Br = 2.356 (4) Å]. The bond lengths and angles of Zn—N and Zn—Br (Table 1) are within the expected ranges (Bourne et al., 2001).
In the crystal structure, N—H···N hydrogen bonds and N—H···Br hydrogen bonds (Table 2) help to establish the crystal packing. The 2-aminopyrimidine molecules form N—H···N hydrogen bonds, resulting in eight membered ring graph-set motif, [R22(8)] (Etter et al., 1990). The N—H···N hydrogen bonds bind the neighboring 2-aminopyrimidine molecules to form a zigzag one-dimensional ribbon structure. The supramolecular ribbons are parallel to each other and N—H···Br hydrogen bonds link them into a two-dimensional network. The close distance, 3.403 (3) Å, between the centroids of two rings (N4,N5,C5,C6,C7,C8 and its symmetry equivalent at -x,1 - y,1 - z) indicates that there are also strong π -π interactions.