Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800018201/na6003sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536800018201/na6003Isup2.hkl |
CCDC reference: 155832
Under an inert nitrogen atmosphere, N,N,N',N'-tetramethylethylenediamine (tmeda) was added slowly to a vigorously stirred solution of zinc dibromide in ethanol, with a 1:1 stoichiometry. After overnight stirring, filtration and washing in ethanol, white crystals with the shape of thin needles were obtained. The melting point was determined to be 452 K (literature 455 K; Noltes, 1964).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997; data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998; software used to prepare material for publication: SHELXTL and the Toledo Cifomatic.
Fig. 1. Plot (Bruker, 1998) of the two molecules of [Zn(tmeda)Br2] in one asymmetric unit. |
[ZnBr2(C6H16N2)] | Dx = 1.979 Mg m−3 |
Mr = 341.40 | Melting point: 179°C K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0995 (5) Å | Cell parameters from 5552 reflections |
b = 11.7771 (4) Å | θ = 3.1–27.3° |
c = 24.3528 (16) Å | µ = 9.07 mm−1 |
β = 99.473 (3)° | T = 100 K |
V = 2291.3 (2) Å3 | Needle, colourless |
Z = 8 | 0.56 × 0.10 × 0.06 mm |
F(000) = 1328 |
Bruker Platform Diffractometer w/1K area-detector | 5889 independent reflections |
Radiation source: Sealed Tube | 4111 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.067 |
Detector resolution: none pixels mm-1 | θmax = 29.7°, θmin = 2.8° |
ω scans | h = −9→10 |
Absorption correction: empirical (using intensity measurements) by multipole expansion (Blessing, 1995) | k = −15→15 |
Tmin = 0.201, Tmax = 0.496 | l = −30→32 |
15672 measured reflections |
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)] = 0.045 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.112 | All H-atom parameters refined |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0608P)2] where P = (Fo2 + 2Fc2)/3 |
5889 reflections | (Δ/σ)max = 0.001 |
327 parameters | Δρmax = 1.38 e Å−3 |
0 restraints | Δρmin = −1.45 e Å−3 |
[ZnBr2(C6H16N2)] | V = 2291.3 (2) Å3 |
Mr = 341.40 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.0995 (5) Å | µ = 9.07 mm−1 |
b = 11.7771 (4) Å | T = 100 K |
c = 24.3528 (16) Å | 0.56 × 0.10 × 0.06 mm |
β = 99.473 (3)° |
Bruker Platform Diffractometer w/1K area-detector | 5889 independent reflections |
Absorption correction: empirical (using intensity measurements) by multipole expansion (Blessing, 1995) | 4111 reflections with I > 2σ(I) |
Tmin = 0.201, Tmax = 0.496 | Rint = 0.067 |
15672 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.112 | All H-atom parameters refined |
S = 0.98 | Δρmax = 1.38 e Å−3 |
5889 reflections | Δρmin = −1.45 e Å−3 |
327 parameters |
Experimental. The decay correction was applied simultaneously with the absorption correction in SADABS (Sheldrick, 1996). No formal measure of the extent of decay is printed out by this program. The final unit cell is obtained from the refinement of the XYZ weighted centroids of reflections above 20 σ(I). |
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 | 1.29245 (7) | −0.32333 (5) | 0.14980 (3) | 0.02323 (14) | |
Br2 | 0.93939 (7) | −0.11222 (5) | 0.07212 (2) | 0.02290 (14) | |
Br3 | 0.76516 (7) | 0.29004 (5) | 0.20956 (2) | 0.02298 (14) | |
Br4 | 0.37663 (6) | 0.36147 (5) | 0.08514 (2) | 0.01979 (13) | |
Zn1 | 1.18605 (7) | −0.13856 (5) | 0.13724 (3) | 0.01467 (14) | |
Zn2 | 0.66413 (7) | 0.37041 (5) | 0.12127 (3) | 0.01462 (14) | |
N1 | 1.3730 (6) | −0.0229 (4) | 0.1244 (2) | 0.0211 (10) | |
N2 | 1.1792 (5) | −0.0587 (4) | 0.21375 (19) | 0.0175 (10) | |
N3 | 0.7645 (5) | 0.5311 (4) | 0.11213 (19) | 0.0174 (9) | |
N4 | 0.8114 (5) | 0.3113 (4) | 0.06241 (19) | 0.0170 (9) | |
C1 | 1.5407 (8) | −0.0724 (8) | 0.1315 (4) | 0.042 (2) | |
C2 | 1.3379 (10) | 0.0345 (7) | 0.0697 (3) | 0.0334 (16) | |
C3 | 1.3553 (10) | 0.0674 (6) | 0.1664 (3) | 0.0364 (16) | |
C4 | 1.3269 (9) | 0.0169 (7) | 0.2201 (3) | 0.0390 (18) | |
C5 | 1.2017 (10) | −0.1394 (7) | 0.2614 (3) | 0.0371 (17) | |
C6 | 1.0213 (8) | 0.0036 (6) | 0.2144 (3) | 0.0278 (14) | |
C7 | 0.6524 (8) | 0.6012 (5) | 0.0719 (3) | 0.0226 (12) | |
C8 | 0.8040 (9) | 0.5949 (6) | 0.1653 (3) | 0.0268 (14) | |
C9 | 0.9205 (7) | 0.5027 (5) | 0.0899 (3) | 0.0225 (12) | |
C10 | 0.8871 (7) | 0.4171 (5) | 0.0436 (3) | 0.0227 (12) | |
C11 | 0.9469 (8) | 0.2348 (6) | 0.0890 (3) | 0.0256 (13) | |
C12 | 0.7122 (8) | 0.2526 (6) | 0.0144 (3) | 0.0286 (14) | |
H1A | 1.607 (8) | −0.011 (6) | 0.134 (3) | 0.026 (18)* | |
H1B | 1.545 (7) | −0.135 (5) | 0.104 (2) | 0.014 (16)* | |
H1C | 1.562 (9) | −0.113 (7) | 0.164 (3) | 0.04 (2)* | |
H2A | 1.406 (9) | 0.090 (7) | 0.066 (3) | 0.033 (19)* | |
H2B | 1.367 (11) | −0.013 (7) | 0.048 (4) | 0.05 (3)* | |
H2C | 1.231 (15) | 0.053 (10) | 0.059 (5) | 0.11 (4)* | |
H3A | 1.468 (10) | 0.113 (7) | 0.170 (3) | 0.05 (2)* | |
H3B | 1.232 (10) | 0.122 (6) | 0.155 (3) | 0.05 (2)* | |
H4A | 1.446 (8) | −0.029 (5) | 0.228 (2) | 0.018 (15)* | |
H4B | 1.318 (7) | 0.073 (5) | 0.250 (2) | 0.014 (14)* | |
H5A | 1.218 (9) | −0.096 (7) | 0.294 (4) | 0.05 (2)* | |
H5B | 1.319 (10) | −0.172 (7) | 0.268 (3) | 0.05 (2)* | |
H5C | 1.092 (12) | −0.202 (9) | 0.260 (4) | 0.08 (3)* | |
H6A | 0.915 (9) | −0.053 (6) | 0.201 (3) | 0.04 (2)* | |
H6B | 0.980 (13) | 0.059 (9) | 0.181 (5) | 0.10 (4)* | |
H6C | 1.030 (9) | 0.042 (7) | 0.246 (3) | 0.05 (2)* | |
H7A | 0.614 (9) | 0.560 (6) | 0.034 (3) | 0.04 (2)* | |
H7B | 0.565 (8) | 0.621 (5) | 0.088 (3) | 0.024 (17)* | |
H7C | 0.707 (7) | 0.676 (5) | 0.070 (3) | 0.021 (16)* | |
H8A | 0.702 (12) | 0.621 (8) | 0.181 (4) | 0.08 (3)* | |
H8B | 0.875 (9) | 0.667 (6) | 0.162 (3) | 0.04 (2)* | |
H8C | 0.877 (10) | 0.561 (7) | 0.186 (3) | 0.04 (2)* | |
H9A | 0.976 (8) | 0.575 (5) | 0.073 (3) | 0.025 (17)* | |
H9B | 1.010 (8) | 0.467 (5) | 0.122 (3) | 0.025 (17)* | |
H10A | 0.805 (8) | 0.448 (5) | 0.011 (3) | 0.022 (16)* | |
H10B | 1.007 (6) | 0.396 (4) | 0.035 (2) | 0.002 (12)* | |
H11A | 1.020 (6) | 0.273 (4) | 0.122 (2) | 0.003 (12)* | |
H11B | 0.900 (9) | 0.163 (6) | 0.102 (3) | 0.04 (2)* | |
H11C | 1.001 (7) | 0.216 (5) | 0.060 (2) | 0.008 (13)* | |
H12A | 0.781 (8) | 0.229 (6) | −0.009 (3) | 0.026 (17)* | |
H12B | 0.610 (8) | 0.301 (6) | −0.004 (3) | 0.026 (17)* | |
H12C | 0.667 (9) | 0.192 (7) | 0.029 (3) | 0.04 (2)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0235 (3) | 0.0177 (3) | 0.0304 (3) | 0.0024 (2) | 0.0103 (2) | 0.0027 (2) |
Br2 | 0.0162 (3) | 0.0299 (3) | 0.0227 (3) | −0.0003 (2) | 0.0035 (2) | 0.0006 (2) |
Br3 | 0.0228 (3) | 0.0293 (3) | 0.0183 (3) | 0.0018 (2) | 0.0081 (2) | 0.0055 (2) |
Br4 | 0.0120 (2) | 0.0258 (3) | 0.0231 (3) | −0.0024 (2) | 0.0073 (2) | −0.0009 (2) |
Zn1 | 0.0127 (3) | 0.0167 (3) | 0.0164 (3) | −0.0007 (2) | 0.0079 (2) | 0.0000 (2) |
Zn2 | 0.0118 (3) | 0.0173 (3) | 0.0166 (3) | −0.0007 (2) | 0.0079 (2) | 0.0007 (2) |
N1 | 0.020 (2) | 0.022 (3) | 0.025 (3) | −0.0070 (19) | 0.015 (2) | −0.006 (2) |
N2 | 0.015 (2) | 0.023 (3) | 0.016 (2) | 0.0009 (18) | 0.0082 (18) | −0.0008 (18) |
N3 | 0.017 (2) | 0.019 (2) | 0.019 (2) | −0.0026 (18) | 0.0080 (18) | 0.0016 (18) |
N4 | 0.016 (2) | 0.018 (2) | 0.019 (2) | 0.0009 (18) | 0.0103 (18) | 0.0034 (18) |
C1 | 0.014 (3) | 0.046 (5) | 0.068 (6) | −0.002 (3) | 0.009 (3) | 0.021 (4) |
C2 | 0.035 (4) | 0.029 (4) | 0.041 (4) | −0.003 (3) | 0.019 (3) | 0.011 (3) |
C3 | 0.047 (4) | 0.035 (4) | 0.030 (4) | −0.013 (3) | 0.018 (3) | −0.010 (3) |
C4 | 0.037 (4) | 0.049 (5) | 0.035 (4) | −0.019 (3) | 0.018 (3) | −0.023 (3) |
C5 | 0.045 (4) | 0.050 (5) | 0.018 (3) | 0.018 (4) | 0.009 (3) | 0.005 (3) |
C6 | 0.029 (3) | 0.034 (4) | 0.022 (3) | 0.011 (3) | 0.008 (3) | −0.008 (3) |
C7 | 0.029 (3) | 0.017 (3) | 0.024 (3) | 0.003 (2) | 0.010 (3) | 0.003 (2) |
C8 | 0.031 (3) | 0.031 (4) | 0.020 (3) | −0.010 (3) | 0.009 (3) | −0.005 (3) |
C9 | 0.016 (3) | 0.027 (3) | 0.028 (3) | −0.006 (2) | 0.015 (2) | 0.001 (2) |
C10 | 0.020 (3) | 0.024 (3) | 0.029 (3) | −0.001 (2) | 0.017 (3) | 0.004 (3) |
C11 | 0.022 (3) | 0.026 (3) | 0.033 (4) | 0.014 (2) | 0.015 (3) | 0.008 (3) |
C12 | 0.023 (3) | 0.040 (4) | 0.026 (3) | −0.006 (3) | 0.013 (3) | −0.012 (3) |
Br1—Zn1 | 2.3419 (8) | N2—C4 | 1.479 (8) |
Br2—Zn1 | 2.3579 (8) | N2—C5 | 1.488 (8) |
Br3—Zn2 | 2.3685 (8) | N2—C6 | 1.477 (7) |
Br4—Zn2 | 2.3522 (8) | N3—C7 | 1.474 (7) |
Zn1—N1 | 2.099 (5) | N3—C8 | 1.485 (8) |
Zn1—N2 | 2.096 (5) | N3—C9 | 1.492 (7) |
Zn2—N3 | 2.086 (5) | N4—C10 | 1.493 (7) |
Zn2—N4 | 2.127 (4) | N4—C11 | 1.484 (7) |
N1—C1 | 1.462 (8) | N4—C12 | 1.477 (8) |
N1—C2 | 1.477 (9) | C3—C4 | 1.489 (10) |
N1—C3 | 1.499 (8) | C9—C10 | 1.503 (9) |
Br1—Zn1—Br2 | 117.57 (3) | Zn1—N2—C6 | 112.5 (4) |
Br1—Zn1—N1 | 111.33 (14) | C4—N2—C5 | 108.0 (6) |
Br1—Zn1—N2 | 111.33 (13) | C4—N2—C6 | 112.7 (5) |
Br2—Zn1—N1 | 111.49 (14) | C5—N2—C6 | 107.7 (5) |
Br2—Zn1—N2 | 113.30 (12) | Zn2—N3—C7 | 111.8 (4) |
N1—Zn1—N2 | 88.10 (18) | Zn2—N3—C8 | 113.4 (4) |
Br3—Zn2—Br4 | 119.63 (3) | Zn2—N3—C9 | 101.8 (3) |
Br3—Zn2—N3 | 112.14 (13) | C7—N3—C8 | 108.4 (5) |
Br3—Zn2—N4 | 109.43 (12) | C7—N3—C9 | 110.5 (5) |
Br4—Zn2—N3 | 112.34 (13) | C8—N3—C9 | 110.8 (5) |
Br4—Zn2—N4 | 111.33 (13) | Zn2—N4—C10 | 103.7 (3) |
N3—Zn2—N4 | 87.31 (18) | Zn2—N4—C11 | 111.2 (4) |
Zn1—N1—C1 | 113.7 (4) | Zn2—N4—C12 | 113.2 (3) |
Zn1—N1—C2 | 113.2 (4) | C10—N4—C11 | 109.2 (4) |
Zn1—N1—C3 | 101.9 (4) | C10—N4—C12 | 110.2 (5) |
C2—N1—C1 | 109.1 (5) | C11—N4—C12 | 109.1 (5) |
C2—N1—C3 | 105.4 (5) | N1—C3—C4 | 111.3 (6) |
C3—N1—C1 | 113.1 (6) | N2—C4—C3 | 112.8 (6) |
Zn1—N2—C4 | 103.0 (3) | N3—C9—C10 | 111.3 (4) |
Zn1—N2—C5 | 112.9 (4) | N4—C10—C9 | 111.3 (5) |
Experimental details
Crystal data | |
Chemical formula | [ZnBr2(C6H16N2)] |
Mr | 341.40 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 8.0995 (5), 11.7771 (4), 24.3528 (16) |
β (°) | 99.473 (3) |
V (Å3) | 2291.3 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 9.07 |
Crystal size (mm) | 0.56 × 0.10 × 0.06 |
Data collection | |
Diffractometer | Bruker Platform Diffractometer w/1K area-detector |
Absorption correction | Empirical (using intensity measurements) by multipole expansion (Blessing, 1995) |
Tmin, Tmax | 0.201, 0.496 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15672, 5889, 4111 |
Rint | 0.067 |
(sin θ/λ)max (Å−1) | 0.696 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.112, 0.98 |
No. of reflections | 5889 |
No. of parameters | 327 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 1.38, −1.45 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997, SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998, SHELXTL and the Toledo Cifomatic.
Br1—Zn1 | 2.3419 (8) | Zn1—N1 | 2.099 (5) |
Br2—Zn1 | 2.3579 (8) | Zn1—N2 | 2.096 (5) |
Br3—Zn2 | 2.3685 (8) | Zn2—N3 | 2.086 (5) |
Br4—Zn2 | 2.3522 (8) | Zn2—N4 | 2.127 (4) |
Br1—Zn1—Br2 | 117.57 (3) | Br3—Zn2—Br4 | 119.63 (3) |
N1—Zn1—N2 | 88.10 (18) | N3—Zn2—N4 | 87.31 (18) |
It is interesting to note that in the title compound, (I), there are weak interactions between Br atomsand their neighboring H atoms, as evidenced by short Br···H distances, e.g. Br1···H4Bi = 3.00 (5), Br1···H7Bii = 2.94 (7) Å [symmetry codes: (i) 3/2 - x, -1/2 + y, 1/2 - z; (ii) x + 1, y - 1, z; sum of Pauling's (1960) van der Waals radii is 3.15 Å].