The title compound, [NiBr2(C4H12N2)2], is a molecular nickel(II) complex. The nickel(II) center is pseudo-octahedral six-coordinate with a trans geometry and is located on an inversion center. The molecules exhibit limited hydrogen bonding between the axial bromide ions and the secondary amine H atoms (each halide interacts with two H atoms) of adjacent molecules.
Supporting information
CCDC reference: 620706
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.005 Å
- R factor = 0.072
- wR factor = 0.147
- Data-to-parameter ratio = 18.0
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT222_ALERT_3_A Large Non-Solvent H Ueq(max)/Ueq(min) ... 6.40 Ratio
| Author Response: see _publ_section_exptl_refinement. One methyl
group is disordered, so one set of hydrogen atoms has
a small Ueq producing a small Ueq(min).
|
Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97
PLAT245_ALERT_2_C U(iso) H10 Smaller than U(eq) C3 by ... 0.04 AngSq
PLAT245_ALERT_2_C U(iso) H11 Smaller than U(eq) C3 by ... 0.04 AngSq
PLAT245_ALERT_2_C U(iso) H12 Smaller than U(eq) C3 by ... 0.04 AngSq
PLAT420_ALERT_2_C D-H Without Acceptor N1 - H2 ... ?
1 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
5 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
4 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: maXus (Mackay et al., 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: TEXSAN for Window (Molecular Structure Corporation, 1999); software used to prepare material for publication: TEXSAN for Windows.
trans-Dibromobis(
N,
N'-dimethylethane-1,2-diamine-
κ2N,
N')nickel(II)
top
Crystal data top
[NiBr2(C4H12N2)2] | F(000) = 396.00 |
Mr = 394.81 | Dx = 1.836 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.5418 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 7.8731 (5) Å | θ = 23.5–46.8° |
b = 8.6501 (4) Å | µ = 8.35 mm−1 |
c = 10.6902 (7) Å | T = 295 K |
β = 101.206 (5)° | Fragment, blue |
V = 714.16 (7) Å3 | 0.22 × 0.15 × 0.10 mm |
Z = 2 | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 1277 reflections with I > 3.00σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.070 |
Graphite monochromator | θmax = 75.1°, θmin = 5.7° |
ω–2θ scans | h = −9→9 |
Absorption correction: ψ scan (North et al, 1968) | k = −10→10 |
Tmin = 0.269, Tmax = 0.434 | l = −13→13 |
4858 measured reflections | 3 standard reflections every 120 min |
1427 independent reflections | intensity decay: 1.5% |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | 5 constraints |
R[F2 > 2σ(F2)] = 0.072 | H-atom parameters constrained |
wR(F2) = 0.147 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.0036|Fo|2] |
S = 1.03 | (Δ/σ)max = 0.001 |
1277 reflections | Δρmax = 0.88 e Å−3 |
71 parameters | Δρmin = −1.02 e Å−3 |
Special details top
Experimental. 1H NMR (300 MHz, D2O): 50, 70, 84, 89, 112, 115. |
Refinement. Refinement of F2. The weighted R-factor wR and goodness
of fit are based on F2, conventional R-factors R are
based on F. R-factors based on F2 are statistically about
twice as large as those based on F. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Br1 | 0.36287 (5) | 0.50734 (4) | 0.70969 (3) | 0.0408 (2) | |
Ni1 | 0.5000 | 0.5000 | 0.5000 | 0.0266 (3) | |
N1 | 0.3228 (3) | 0.3254 (3) | 0.4203 (2) | 0.0324 (5) | |
N2 | 0.3140 (3) | 0.6530 (3) | 0.3946 (2) | 0.0360 (5) | |
C1 | 0.1594 (3) | 0.4077 (4) | 0.3705 (3) | 0.0495 (7) | |
C2 | 0.1953 (4) | 0.5531 (5) | 0.3046 (3) | 0.0535 (9) | |
C3 | 0.2898 (4) | 0.1928 (4) | 0.4967 (3) | 0.0458 (7) | |
C4 | 0.2235 (4) | 0.7613 (4) | 0.4638 (3) | 0.0500 (8) | |
H1 | 0.3747 | 0.7143 | 0.3440 | 0.043* | |
H2 | 0.3630 | 0.2853 | 0.3486 | 0.039* | |
H3 | 0.1639 | 0.8356 | 0.4061 | 0.060* | |
H4 | 0.3050 | 0.8121 | 0.5277 | 0.060* | |
H5 | 0.1428 | 0.7064 | 0.5025 | 0.060* | |
H6 | 0.0899 | 0.6066 | 0.2751 | 0.064* | |
H7 | 0.2475 | 0.5280 | 0.2342 | 0.064* | |
H8 | 0.1039 | 0.4328 | 0.4393 | 0.059* | |
H9 | 0.0858 | 0.3430 | 0.3117 | 0.059* | |
H10 | 0.1931 | 0.2146 | 0.5352 | 0.010* | 0.19 (3) |
H11 | 0.3886 | 0.1735 | 0.5612 | 0.010* | 0.19 |
H12 | 0.2652 | 0.1045 | 0.4436 | 0.010* | 0.19 |
H13 | 0.2626 | 0.2284 | 0.5747 | 0.045* | 0.81 |
H14 | 0.1947 | 0.1352 | 0.4512 | 0.045* | 0.81 |
H15 | 0.3895 | 0.1291 | 0.5141 | 0.045* | 0.81 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0526 (4) | 0.0413 (4) | 0.0344 (4) | −0.00196 (8) | 0.0233 (2) | −0.00341 (8) |
Ni1 | 0.0274 (5) | 0.0264 (6) | 0.0278 (5) | −0.0011 (1) | 0.0102 (3) | −0.0003 (2) |
N1 | 0.0376 (10) | 0.0302 (11) | 0.0311 (10) | −0.0052 (8) | 0.0106 (8) | −0.0036 (9) |
N2 | 0.0363 (10) | 0.0317 (12) | 0.0413 (11) | 0.0013 (8) | 0.0110 (8) | 0.0087 (9) |
C1 | 0.0375 (12) | 0.046 (2) | 0.062 (2) | −0.0069 (10) | 0.0004 (10) | −0.001 (1) |
C2 | 0.049 (1) | 0.052 (2) | 0.053 (2) | 0.002 (2) | −0.0051 (11) | 0.006 (2) |
C3 | 0.058 (2) | 0.032 (1) | 0.050 (1) | −0.0109 (12) | 0.0185 (11) | −0.0031 (13) |
C4 | 0.053 (2) | 0.042 (2) | 0.061 (2) | 0.0128 (11) | 0.0276 (13) | 0.009 (1) |
Geometric parameters (Å, º) top
Ni1—Br1 | 2.6712 (4) | C1—H8 | 0.950 |
Ni1—Br1i | 2.6712 (4) | C1—H9 | 0.950 |
Ni1—N1 | 2.119 (2) | C2—H6 | 0.950 |
Ni1—N1i | 2.119 (2) | C2—H7 | 0.950 |
Ni1—N2 | 2.127 (2) | C3—H10 | 0.952 |
Ni1—N2i | 2.127 (2) | C3—H11 | 0.948 |
N1—C1 | 1.477 (3) | C3—H12 | 0.949 |
N1—C3 | 1.460 (4) | C3—H13 | 0.951 |
N2—C2 | 1.482 (4) | C3—H14 | 0.951 |
N2—C4 | 1.462 (4) | C3—H15 | 0.947 |
C1—C2 | 1.495 (5) | C4—H3 | 0.950 |
N1—H2 | 0.950 | C4—H4 | 0.950 |
N2—H1 | 0.950 | C4—H5 | 0.950 |
| | | |
Br1···N2ii | 3.603 (2) | Br1···C4ii | 3.708 (3) |
Br1···C3iii | 3.665 (3) | C3···C4iv | 3.776 (5) |
Br1···N1iii | 3.705 (2) | | |
| | | |
Br1—Ni1—Br1i | 180.00 | N1—C1—H8 | 109.31 |
Br1—Ni1—N1 | 90.72 (6) | N1—C1—H9 | 109.31 |
Br1—Ni1—N1i | 89.28 (6) | C2—C1—H8 | 109.32 |
Br1—Ni1—N2 | 94.65 (7) | C2—C1—H9 | 109.31 |
Br1—Ni1—N2i | 85.35 (7) | H8—C1—H9 | 109.46 |
Br1i—Ni1—N1 | 89.28 (6) | N2—C2—H6 | 109.41 |
Br1i—Ni1—N1i | 90.72 (6) | N2—C2—H7 | 109.41 |
Br1i—Ni1—N2 | 85.35 (7) | C1—C2—H6 | 109.41 |
Br1i—Ni1—N2i | 94.65 (7) | C1—C2—H7 | 109.42 |
N1—Ni1—N1i | 180.00 | H6—C2—H7 | 109.46 |
N1—Ni1—N2 | 84.2 (1) | N1—C3—H10 | 109.3 |
N1—Ni1—N2i | 95.8 (1) | N1—C3—H11 | 109.6 |
N1i—Ni1—N2 | 95.8 (1) | N1—C3—H12 | 109.6 |
N1i—Ni1—N2i | 84.2 (1) | N1—C3—H13 | 109.3 |
N2—Ni1—N2i | 180.00 | N1—C3—H14 | 109.4 |
Ni1—N1—C1 | 105.1 (2) | N1—C3—H15 | 109.6 |
Ni1—N1—C3 | 120.6 (2) | H10—C3—H11 | 109.4 |
C1—N1—C3 | 110.1 (2) | H10—C3—H12 | 109.3 |
Ni1—N2—C2 | 105.3 (2) | H11—C3—H12 | 109.7 |
Ni1—N2—C4 | 118.9 (2) | H13—C3—H14 | 109.2 |
C2—N2—C4 | 113.2 (2) | H13—C3—H15 | 109.6 |
N1—C1—C2 | 110.1 (2) | H14—C3—H15 | 109.6 |
N2—C2—C1 | 109.7 (3) | N2—C4—H3 | 109.48 |
Ni1—N1—H2 | 106.76 | N2—C4—H4 | 109.47 |
C1—N1—H2 | 106.77 | N2—C4—H5 | 109.47 |
C3—N1—H2 | 106.76 | H3—C4—H4 | 109.47 |
Ni1—N2—H1 | 106.19 | H3—C4—H5 | 109.48 |
C2—N2—H1 | 106.19 | H4—C4—H5 | 109.47 |
C4—N2—H1 | 106.20 | | |
| | | |
Br1—Ni1—N1—C1 | 79.4 (2) | N1—Ni1—N2—C2 | −13.6 (2) |
Br1—Ni1—N1—C3 | −45.6 (2) | N1—Ni1—N2—C4 | 114.5 (2) |
Br1—Ni1—N1i—C1i | 100.6 (2) | N1—Ni1—N2i—C2i | −166.4 (2) |
Br1—Ni1—N1i—C3i | −134.4 (2) | N1—Ni1—N2i—C4i | 65.5 (2) |
Br1—Ni1—N2—C2 | −103.9 (2) | N1—C1—C2—N2 | −58.3 (4) |
Br1—Ni1—N2—C4 | 24.3 (2) | N2—Ni1—N1—C1 | −15.2 (2) |
Br1—Ni1—N2i—C2i | −76.1 (2) | N2—Ni1—N1—C3 | −140.2 (2) |
Br1—Ni1—N2i—C4i | 155.7 (2) | N2—Ni1—N1i—C1i | −164.8 (2) |
Ni1—N1—C1—C2 | 42.4 (3) | N2—Ni1—N1i—C3i | −39.8 (2) |
Ni1—N1i—C1i—C2i | −42.4 (3) | C1—C2—N2—C4 | −90.8 (3) |
Ni1—N2—C2—C1 | 40.7 (3) | C2—C1—N1—C3 | 173.7 (3) |
Ni1—N2i—C2i—C1i | −40.7 (3) | | |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+3/2, z+1/2; (iii) x, −y+1/2, z+1/2; (iv) x, y−1, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1···Br1v | 0.95 | 2.80 | 3.603 (2) | 143 |
N1—H2···Br1vi | 0.95 | 2.93 | 3.705 (2) | 139 |
Symmetry codes: (v) x, −y+3/2, z−1/2; (vi) x, −y+1/2, z−1/2. |