Di­bromo(N,N,N′,N′-tetra­methyl­ethane-1,2-di­amine)­zinc(II)

Citeau, H.; Conrad, O.; Giolando, D.M.

doi:10.1107/S1600536800018201

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Dibromo(N,N,N′,N′-tetramethylethane-1,2-diamine)zinc(II)

H. Citeau, O. Conrad and D. M. Giolando

The structure of the title compound, [ZnBr₂(C₆H₁₆N₂)], which is interesting from the metal coordination point of view, was determined by direct methods on 15672 observed reflections with Mo Kα radiation. The asymmetric unit contains two molecules on general positions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800018201/na6003sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536800018201/na6003Isup2.hkl Contains datablock I

CCDC reference: 155832

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.009 Å
R factor = 0.045
wR factor = 0.112
Data-to-parameter ratio = 18.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           29.66
         From the CIF: _reflns_number_total               5889
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         6473
         Completeness (_total/calc)             90.98%
          Alert C: < 95% complete

General Notes



ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      1.170
          Tmax scaled      0.580 Tmin scaled      0.235


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

Comment top

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].

Experimental top

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).

Computing details top

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.

Figures top

Fig. 1. Plot (Bruker, 1998) of the two molecules of [Zn(tmeda)Br₂] in one asymmetric unit.

Dibromo(N,N,N',N'-tetramethylethane-1,2-diamine)zinc(II) top

Crystal data top

[ZnBr₂(C₆H₁₆N₂)]	D_x = 1.979 Mg m⁻³
M_r = 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

Data collection top

Bruker Platform Diffractometer w/1K area-detector	5889 independent reflections
Radiation source: Sealed Tube	4111 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.067
Detector resolution: none pixels mm^-1	θ_max = 29.7°, θ_min = 2.8°
ω scans	h = −9→10
Absorption correction: empirical (using intensity measurements) by multipole expansion (Blessing, 1995)	k = −15→15
T_min = 0.201, T_max = 0.496	l = −30→32
15672 measured reflections

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)] = 0.045	Hydrogen site location: difference Fourier map
wR(F²) = 0.112	All H-atom parameters refined
S = 0.98	w = 1/[σ²(F_o²) + (0.0608P)²] where P = (F_o² + 2F_c²)/3
5889 reflections	(Δ/σ)_max = 0.001
327 parameters	Δρ_max = 1.38 e Å⁻³
0 restraints	Δρ_min = −1.45 e Å⁻³

Crystal data top

[ZnBr₂(C₆H₁₆N₂)]	V = 2291.3 (2) Å³
M_r = 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)°

Data collection top

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)
T_min = 0.201, T_max = 0.496	R_int = 0.067
15672 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.112	All H-atom parameters refined
S = 0.98	Δρ_max = 1.38 e Å⁻³
5889 reflections	Δρ_min = −1.45 e Å⁻³
327 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)]
M_r	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)
T_min, T_max	0.201, 0.496
No. of measured, independent and observed [I > 2σ(I)] reflections	15672, 5889, 4111
R_int	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
Δρ_max, Δρ_min (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.

Selected geometric parameters (Å, º) top

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)

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