Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807042390/bi2235sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807042390/bi2235Isup2.hkl |
CCDC reference: 1296690
Ethylenediamine (0.120 g, 0.002 mol) and Zn(NO3)2 (0.189 g, 0.001 mol) were added to 25 ml me thanol. The mixture was heated for 5 h under reflux with stirring and the resulting solution was filtered. Single crystals suitable for X-ray diffraction were formed after a week by slow evaporation of the filtrate.
H atoms were placed at calculated positions and refined as riding on their parent C or N atoms, with C—H = 0.97 Å or N—H = 0.90 Å, and with Uiso(H) = 1.2Ueq(C/N).
The title compound (Fig. 1) is a mononuclear ZnII complex. The ZnII atom lies on a centre of inversion and is coordinated to four N atoms belonging to two ethylenediamine molecules and two O atoms belonging to two nitrate anions arranged in a trans manner. In the crystal, adjacent molecules are connected by N—H···O hydrogen bonds involving the H atoms of the amino groups and the non-bonded O atoms of the nitrate ions (Fig. 2).
For the structure of the analogous CuII compound, see: Komiyama & Lingafelter (1964); Fronczek et al. (1995); Manriquez et al. (1996).
Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
[Zn(NO3)2(C2H8N2)2] | F(000) = 320 |
Mr = 309.62 | Dx = 1.689 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2202 reflections |
a = 8.2127 (7) Å | θ = 2.7–27.8° |
b = 9.9673 (8) Å | µ = 2.05 mm−1 |
c = 7.9733 (7) Å | T = 293 K |
β = 111.171 (1)° | Block, colourless |
V = 608.63 (9) Å3 | 0.24 × 0.17 × 0.09 mm |
Z = 2 |
Bruker APEXII CCD diffractometer | 1116 independent reflections |
Radiation source: fine-focus sealed tube | 811 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
φ and ω scans | θmax = 25.5°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −9→9 |
Tmin = 0.668, Tmax = 0.823 | k = −12→11 |
3715 measured reflections | l = −9→9 |
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) = 0.148 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0901P)2 + 0.4042P] where P = (Fo2 + 2Fc2)/3 |
1116 reflections | (Δ/σ)max < 0.001 |
79 parameters | Δρmax = 0.71 e Å−3 |
0 restraints | Δρmin = −0.84 e Å−3 |
[Zn(NO3)2(C2H8N2)2] | V = 608.63 (9) Å3 |
Mr = 309.62 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.2127 (7) Å | µ = 2.05 mm−1 |
b = 9.9673 (8) Å | T = 293 K |
c = 7.9733 (7) Å | 0.24 × 0.17 × 0.09 mm |
β = 111.171 (1)° |
Bruker APEXII CCD diffractometer | 1116 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 811 reflections with I > 2σ(I) |
Tmin = 0.668, Tmax = 0.823 | Rint = 0.026 |
3715 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.71 e Å−3 |
1116 reflections | Δρmin = −0.84 e Å−3 |
79 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 | ||
Zn1 | 1.0000 | 0.5000 | 0.5000 | 0.0411 (3) | |
N3 | 0.8252 (6) | 0.5573 (4) | 0.8297 (6) | 0.0547 (11) | |
O1 | 0.7756 (5) | 0.6261 (4) | 0.9285 (5) | 0.0637 (10) | |
O2 | 0.9006 (5) | 0.6110 (3) | 0.7375 (5) | 0.0600 (10) | |
O3 | 0.7984 (5) | 0.4342 (4) | 0.8202 (6) | 0.0675 (11) | |
C2 | 0.6379 (8) | 0.5160 (5) | 0.3000 (9) | 0.0620 (15) | |
H2A | 0.5473 | 0.5332 | 0.1840 | 0.074* | |
H2B | 0.5968 | 0.5474 | 0.3929 | 0.074* | |
N1 | 0.8360 (5) | 0.3461 (4) | 0.4743 (6) | 0.0544 (11) | |
H3B | 0.8856 | 0.2696 | 0.4563 | 0.065* | |
H3A | 0.8125 | 0.3370 | 0.5755 | 0.065* | |
N2 | 0.7978 (5) | 0.5876 (4) | 0.3128 (6) | 0.0515 (11) | |
H4A | 0.7904 | 0.6739 | 0.3423 | 0.062* | |
H4B | 0.8120 | 0.5853 | 0.2061 | 0.062* | |
C1 | 0.6745 (7) | 0.3712 (5) | 0.3217 (8) | 0.0649 (15) | |
H1A | 0.5784 | 0.3256 | 0.3408 | 0.078* | |
H1B | 0.6851 | 0.3356 | 0.2128 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.090 (3) | 0.044 (2) | 0.062 (2) | −0.0035 (18) | 0.045 (2) | −0.0026 (16) |
O3 | 0.095 (3) | 0.039 (2) | 0.075 (3) | −0.0047 (19) | 0.039 (2) | 0.0023 (19) |
Zn1 | 0.0495 (5) | 0.0314 (5) | 0.0439 (5) | 0.0007 (3) | 0.0187 (3) | 0.0030 (3) |
N3 | 0.082 (3) | 0.037 (2) | 0.056 (3) | −0.001 (2) | 0.039 (2) | 0.000 (2) |
O1 | 0.093 (3) | 0.052 (2) | 0.060 (2) | 0.0047 (19) | 0.044 (2) | −0.0022 (17) |
C2 | 0.058 (3) | 0.052 (3) | 0.069 (4) | −0.001 (2) | 0.014 (3) | 0.002 (2) |
N1 | 0.057 (2) | 0.037 (2) | 0.069 (3) | −0.0039 (18) | 0.021 (2) | −0.0027 (19) |
N2 | 0.054 (2) | 0.044 (2) | 0.054 (3) | 0.0043 (18) | 0.0172 (19) | 0.0036 (18) |
C1 | 0.061 (3) | 0.049 (3) | 0.076 (4) | −0.004 (2) | 0.014 (3) | −0.003 (3) |
O2—N3 | 1.241 (5) | C2—H2A | 0.970 |
O2—Zn1 | 2.568 (3) | C2—H2B | 0.970 |
O3—N3 | 1.243 (6) | N1—C1 | 1.462 (6) |
Zn1—N2i | 1.989 (4) | N1—H3B | 0.900 |
Zn1—N2 | 1.989 (4) | N1—H3A | 0.900 |
Zn1—N1 | 2.002 (4) | N2—H4A | 0.900 |
Zn1—N1i | 2.002 (4) | N2—H4B | 0.900 |
N3—O1 | 1.221 (5) | C1—H1A | 0.970 |
C2—N2 | 1.466 (7) | C1—H1B | 0.970 |
C2—C1 | 1.472 (7) | ||
N3—O2—Zn1 | 127.6 (3) | H2A—C2—H2B | 108.3 |
N2i—Zn1—N2 | 180.0 | C1—N1—Zn1 | 109.2 (3) |
N2i—Zn1—N1 | 95.11 (16) | C1—N1—H3B | 109.8 |
N2—Zn1—N1 | 84.89 (16) | Zn1—N1—H3B | 109.8 |
N2i—Zn1—N1i | 84.89 (16) | C1—N1—H3A | 109.8 |
N2—Zn1—N1i | 95.11 (16) | Zn1—N1—H3A | 109.8 |
N1—Zn1—N1i | 180.00 (14) | H3B—N1—H3A | 108.3 |
N2i—Zn1—O2 | 92.14 (15) | C2—N2—Zn1 | 108.9 (3) |
N2—Zn1—O2 | 87.86 (15) | C2—N2—H4A | 109.9 |
N1—Zn1—O2 | 91.40 (15) | Zn1—N2—H4A | 109.9 |
N1i—Zn1—O2 | 88.60 (15) | C2—N2—H4B | 109.9 |
O1—N3—O2 | 119.6 (4) | Zn1—N2—H4B | 109.9 |
O1—N3—O3 | 120.0 (4) | H4A—N2—H4B | 108.3 |
O2—N3—O3 | 120.3 (4) | N1—C1—C2 | 110.6 (4) |
N2—C2—C1 | 109.2 (5) | N1—C1—H1A | 109.5 |
N2—C2—H2A | 109.8 | C2—C1—H1A | 109.5 |
C1—C2—H2A | 109.8 | N1—C1—H1B | 109.5 |
N2—C2—H2B | 109.8 | C2—C1—H1B | 109.5 |
C1—C2—H2B | 109.8 | H1A—C1—H1B | 108.1 |
Symmetry code: (i) −x+2, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H3B···O3ii | 0.90 | 2.29 | 3.023 (6) | 138 |
N1—H3A···O3 | 0.90 | 2.22 | 3.015 (6) | 147 |
N2—H4A···O1iii | 0.90 | 2.13 | 3.025 (5) | 176 |
N2—H4A···O2iii | 0.90 | 2.58 | 3.235 (5) | 130 |
N2—H4B···O1iv | 0.90 | 2.16 | 3.027 (6) | 161 |
Symmetry codes: (ii) x, −y+1/2, z−1/2; (iii) x, −y+3/2, z−1/2; (iv) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | [Zn(NO3)2(C2H8N2)2] |
Mr | 309.62 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 8.2127 (7), 9.9673 (8), 7.9733 (7) |
β (°) | 111.171 (1) |
V (Å3) | 608.63 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.05 |
Crystal size (mm) | 0.24 × 0.17 × 0.09 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.668, 0.823 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3715, 1116, 811 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.148, 1.07 |
No. of reflections | 1116 |
No. of parameters | 79 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.71, −0.84 |
Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).
O2—Zn1 | 2.568 (3) | Zn1—N1 | 2.002 (4) |
Zn1—N2 | 1.989 (4) | ||
N2i—Zn1—N2 | 180.0 | N2i—Zn1—O2 | 92.14 (15) |
N2i—Zn1—N1 | 95.11 (16) | N2—Zn1—O2 | 87.86 (15) |
N2—Zn1—N1 | 84.89 (16) | N1—Zn1—O2 | 91.40 (15) |
N1—Zn1—N1i | 180.00 (14) | N1i—Zn1—O2 | 88.60 (15) |
Symmetry code: (i) −x+2, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H3B···O3ii | 0.90 | 2.29 | 3.023 (6) | 138.1 |
N1—H3A···O3 | 0.90 | 2.22 | 3.015 (6) | 147.3 |
N2—H4A···O1iii | 0.90 | 2.13 | 3.025 (5) | 176.4 |
N2—H4A···O2iii | 0.90 | 2.58 | 3.235 (5) | 130.2 |
N2—H4B···O1iv | 0.90 | 2.16 | 3.027 (6) | 161.1 |
Symmetry codes: (ii) x, −y+1/2, z−1/2; (iii) x, −y+3/2, z−1/2; (iv) x, y, z−1. |
The title compound (Fig. 1) is a mononuclear ZnII complex. The ZnII atom lies on a centre of inversion and is coordinated to four N atoms belonging to two ethylenediamine molecules and two O atoms belonging to two nitrate anions arranged in a trans manner. In the crystal, adjacent molecules are connected by N—H···O hydrogen bonds involving the H atoms of the amino groups and the non-bonded O atoms of the nitrate ions (Fig. 2).