Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802014113/cv6130sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802014113/cv6130Isup2.hkl |
CCDC reference: 197444
1,3-Diaminopropane (32.2 mmol) was added slowly to a solution of Ni(BF4)2 (10.6 mmol) in water. To this solution, Ni(BF4)2 (10.6 mmol) and NaSCN (10.6 mmol) were added. Slow evaporation leads to the formation of purple crystals.
The two tetrafluoroborate anions were found disordered and were refined in sets (set 1: F1, F2, F3 and F4; set 2: F1', F2', F3' and F4'; set 3: F11, F12, F13 and F14; set 4: F11', F12', F13' and F14'). They were refined to partial occupancies of 0.571 (18), 0.429 (18), 0.533 (16) and 0.467 (16), respectively. The B—F bond lengths of each tetrafluoroborate anoion were restrained to the same value, and the F···F distances were restarained to be 1.633 times the corresponding B—F bond lengths.
Data collection: XSCANS (Bruker, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1996); program(s) used to solve structure: XS in SHELXTL; program(s) used to refine structure: XL in SHELXTL; molecular graphics: XP in SHELXTL; software used to prepare material for publication: XCIF in SHELXTL.
[Ni(C9H30N6)](BF4)2 | Dx = 1.516 Mg m−3 |
Mr = 454.72 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 36 reflections |
a = 15.2751 (14) Å | θ = 2.4–16.0° |
b = 15.498 (2) Å | µ = 1.05 mm−1 |
c = 16.835 (2) Å | T = 298 K |
V = 3985.6 (8) Å3 | Chunk, purple |
Z = 8 | 0.4 × 0.3 × 0.2 mm |
F(000) = 1888 |
Siemens P21 upgraded to P4 diffractometer | 1657 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.048 |
Graphite monochromator | θmax = 25.3°, θmin = 2.2° |
ω scans | h = 0→18 |
Absorption correction: ψ scan (XPREP in SHELXTL; Bruker, 1996) | k = 0→18 |
Tmin = 0.654, Tmax = 0.742 | l = 0→20 |
4877 measured reflections | 3 standard reflections every 100 reflections |
3503 independent reflections | intensity decay: no decay was observed |
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0507P)2 + 0.8993P] where P = (Fo2 + 2Fc2)/3 |
3503 reflections | (Δ/σ)max < 0.001 |
311 parameters | Δρmax = 0.31 e Å−3 |
142 restraints | Δρmin = −0.22 e Å−3 |
[Ni(C9H30N6)](BF4)2 | V = 3985.6 (8) Å3 |
Mr = 454.72 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 15.2751 (14) Å | µ = 1.05 mm−1 |
b = 15.498 (2) Å | T = 298 K |
c = 16.835 (2) Å | 0.4 × 0.3 × 0.2 mm |
Siemens P21 upgraded to P4 diffractometer | 1657 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XPREP in SHELXTL; Bruker, 1996) | Rint = 0.048 |
Tmin = 0.654, Tmax = 0.742 | 3 standard reflections every 100 reflections |
4877 measured reflections | intensity decay: no decay was observed |
3503 independent reflections |
R[F2 > 2σ(F2)] = 0.059 | 142 restraints |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.31 e Å−3 |
3503 reflections | Δρmin = −0.22 e Å−3 |
311 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 | Occ. (<1) | |
F11 | 0.2036 (6) | 0.4730 (11) | 0.2484 (12) | 0.169 (9) | 0.533 (16) |
F12 | 0.0839 (10) | 0.5213 (11) | 0.3073 (8) | 0.193 (8) | 0.533 (16) |
F13 | 0.0978 (10) | 0.5372 (9) | 0.1828 (8) | 0.161 (7) | 0.533 (16) |
F14 | 0.0818 (9) | 0.4081 (7) | 0.2290 (11) | 0.149 (6) | 0.533 (16) |
F11' | 0.1335 (11) | 0.5735 (6) | 0.2424 (11) | 0.153 (7) | 0.467 (16) |
F12' | 0.1925 (10) | 0.4531 (11) | 0.1993 (11) | 0.153 (7) | 0.467 (16) |
F13' | 0.1432 (12) | 0.4609 (8) | 0.3177 (7) | 0.140 (7) | 0.467 (16) |
F14' | 0.0526 (9) | 0.4591 (16) | 0.2164 (13) | 0.212 (12) | 0.467 (16) |
F1 | 0.0880 (10) | 0.7549 (6) | 0.3658 (9) | 0.136 (7) | 0.571 (18) |
F2 | 0.1863 (8) | 0.8101 (9) | 0.4403 (11) | 0.162 (9) | 0.571 (18) |
F3 | 0.0613 (7) | 0.8672 (11) | 0.4430 (10) | 0.145 (6) | 0.571 (18) |
F4 | 0.1386 (16) | 0.8824 (12) | 0.3410 (7) | 0.214 (10) | 0.571 (18) |
F1' | 0.0771 (10) | 0.9009 (7) | 0.3815 (17) | 0.143 (9) | 0.429 (18) |
F2' | 0.139 (2) | 0.8212 (13) | 0.4708 (9) | 0.187 (12) | 0.429 (18) |
F3' | 0.1779 (14) | 0.8135 (15) | 0.3497 (16) | 0.214 (10) | 0.429 (18) |
F4' | 0.0532 (15) | 0.7649 (12) | 0.3870 (15) | 0.204 (14) | 0.429 (18) |
B1 | 0.1149 (5) | 0.8266 (6) | 0.3959 (5) | 0.082 (2) | |
B2 | 0.1243 (7) | 0.4857 (6) | 0.2428 (6) | 0.106 (3) | |
Ni | 0.37602 (4) | 0.67037 (4) | 0.33755 (4) | 0.0517 (2) | |
N1 | 0.4308 (3) | 0.5881 (3) | 0.4260 (3) | 0.0691 (14) | |
H1A | 0.4356 | 0.5351 | 0.4045 | 0.083* | |
H1B | 0.4856 | 0.6068 | 0.4355 | 0.083* | |
N5 | 0.2521 (3) | 0.6288 (3) | 0.3788 (3) | 0.0700 (14) | |
H5A | 0.2139 | 0.6708 | 0.3661 | 0.084* | |
H5B | 0.2375 | 0.5826 | 0.3492 | 0.084* | |
N6 | 0.3814 (3) | 0.5629 (3) | 0.2542 (3) | 0.0770 (14) | |
H6A | 0.4289 | 0.5315 | 0.2667 | 0.092* | |
H6B | 0.3344 | 0.5294 | 0.2639 | 0.092* | |
N10 | 0.3092 (4) | 0.7449 (4) | 0.2480 (3) | 0.0937 (18) | |
H10A | 0.2515 | 0.7380 | 0.2566 | 0.112* | |
H10B | 0.3214 | 0.8006 | 0.2579 | 0.112* | |
N11 | 0.4990 (3) | 0.7140 (3) | 0.2968 (3) | 0.0792 (15) | |
H11A | 0.5265 | 0.6683 | 0.2752 | 0.095* | |
H11B | 0.4889 | 0.7516 | 0.2571 | 0.095* | |
N15 | 0.3738 (3) | 0.7833 (3) | 0.4120 (3) | 0.0791 (14) | |
H15A | 0.3523 | 0.8268 | 0.3823 | 0.095* | |
H15B | 0.3344 | 0.7733 | 0.4507 | 0.095* | |
C2 | 0.3878 (5) | 0.5779 (5) | 0.5031 (4) | 0.102 (2) | |
H2A | 0.3862 | 0.6334 | 0.5298 | 0.122* | |
H2B | 0.4219 | 0.5387 | 0.5357 | 0.122* | |
C3 | 0.2967 (5) | 0.5440 (5) | 0.4960 (5) | 0.115 (3) | |
H3A | 0.2977 | 0.4922 | 0.4636 | 0.138* | |
H3B | 0.2760 | 0.5278 | 0.5484 | 0.138* | |
C4 | 0.2344 (4) | 0.6056 (5) | 0.4610 (4) | 0.101 (2) | |
H4A | 0.1760 | 0.5811 | 0.4640 | 0.121* | |
H4B | 0.2346 | 0.6578 | 0.4928 | 0.121* | |
C7 | 0.3841 (5) | 0.5779 (5) | 0.1676 (4) | 0.105 (2) | |
H7A | 0.4416 | 0.5996 | 0.1535 | 0.126* | |
H7B | 0.3761 | 0.5231 | 0.1406 | 0.126* | |
C8 | 0.3176 (6) | 0.6390 (6) | 0.1389 (4) | 0.118 (3) | |
H8A | 0.2608 | 0.6176 | 0.1558 | 0.141* | |
H8B | 0.3182 | 0.6371 | 0.0813 | 0.141* | |
C9 | 0.3234 (5) | 0.7315 (6) | 0.1632 (5) | 0.108 (3) | |
H9A | 0.3808 | 0.7535 | 0.1491 | 0.129* | |
H9B | 0.2802 | 0.7644 | 0.1338 | 0.129* | |
C12 | 0.5592 (4) | 0.7540 (6) | 0.3501 (4) | 0.105 (3) | |
H12A | 0.6098 | 0.7727 | 0.3199 | 0.126* | |
H12B | 0.5792 | 0.7108 | 0.3877 | 0.126* | |
C13 | 0.5249 (4) | 0.8301 (5) | 0.3963 (5) | 0.095 (2) | |
H13A | 0.5729 | 0.8535 | 0.4274 | 0.114* | |
H13B | 0.5077 | 0.8742 | 0.3585 | 0.114* | |
C14 | 0.4514 (5) | 0.8150 (5) | 0.4497 (4) | 0.109 (3) | |
H14A | 0.4694 | 0.7739 | 0.4899 | 0.131* | |
H14B | 0.4375 | 0.8687 | 0.4765 | 0.131* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F11 | 0.058 (7) | 0.176 (13) | 0.27 (3) | 0.003 (7) | −0.056 (10) | −0.028 (15) |
F12 | 0.171 (13) | 0.230 (19) | 0.177 (13) | −0.018 (12) | 0.038 (11) | −0.055 (14) |
F13 | 0.188 (14) | 0.143 (12) | 0.150 (12) | 0.057 (10) | −0.030 (9) | 0.050 (10) |
F14 | 0.143 (13) | 0.111 (8) | 0.193 (11) | −0.050 (8) | −0.015 (10) | 0.000 (8) |
F11' | 0.176 (13) | 0.110 (9) | 0.172 (16) | 0.001 (9) | −0.048 (11) | 0.017 (9) |
F12' | 0.136 (15) | 0.150 (13) | 0.172 (15) | 0.012 (11) | 0.001 (11) | −0.006 (11) |
F13' | 0.194 (18) | 0.120 (10) | 0.106 (9) | −0.027 (10) | −0.036 (10) | 0.026 (8) |
F14' | 0.092 (10) | 0.30 (3) | 0.25 (2) | −0.029 (16) | −0.041 (11) | −0.05 (3) |
F1 | 0.148 (12) | 0.105 (9) | 0.155 (12) | 0.027 (8) | −0.078 (11) | −0.053 (8) |
F2 | 0.082 (7) | 0.136 (9) | 0.27 (2) | 0.049 (6) | −0.046 (9) | −0.078 (12) |
F3 | 0.114 (8) | 0.170 (12) | 0.153 (12) | 0.030 (8) | 0.067 (8) | −0.002 (9) |
F4 | 0.30 (2) | 0.200 (18) | 0.144 (10) | −0.042 (17) | 0.068 (12) | 0.084 (11) |
F1' | 0.109 (11) | 0.081 (9) | 0.24 (3) | 0.054 (9) | −0.005 (13) | −0.006 (13) |
F2' | 0.32 (3) | 0.148 (16) | 0.090 (9) | −0.04 (2) | −0.060 (17) | 0.038 (10) |
F3' | 0.179 (15) | 0.22 (2) | 0.25 (2) | 0.099 (15) | 0.147 (15) | 0.080 (17) |
F4' | 0.19 (2) | 0.19 (2) | 0.23 (2) | −0.114 (18) | 0.039 (16) | 0.028 (18) |
B1 | 0.057 (5) | 0.082 (6) | 0.106 (7) | 0.008 (6) | 0.013 (6) | 0.004 (7) |
B2 | 0.087 (8) | 0.127 (10) | 0.103 (9) | −0.049 (10) | 0.024 (8) | −0.015 (9) |
Ni | 0.0461 (4) | 0.0546 (4) | 0.0544 (4) | 0.0046 (4) | 0.0040 (4) | 0.0020 (4) |
N1 | 0.053 (3) | 0.082 (3) | 0.072 (3) | 0.009 (3) | −0.005 (3) | 0.009 (3) |
N5 | 0.052 (3) | 0.076 (3) | 0.082 (3) | 0.003 (3) | 0.000 (3) | −0.006 (3) |
N6 | 0.074 (3) | 0.079 (3) | 0.079 (4) | 0.005 (3) | 0.010 (3) | −0.013 (3) |
N10 | 0.094 (4) | 0.104 (4) | 0.082 (4) | 0.018 (4) | −0.001 (3) | 0.023 (3) |
N11 | 0.062 (3) | 0.090 (4) | 0.086 (4) | −0.006 (3) | 0.018 (3) | −0.001 (3) |
N15 | 0.067 (3) | 0.075 (3) | 0.095 (4) | 0.003 (3) | 0.006 (3) | −0.017 (3) |
C2 | 0.103 (6) | 0.130 (6) | 0.073 (5) | 0.022 (5) | −0.002 (5) | 0.031 (5) |
C3 | 0.098 (6) | 0.116 (6) | 0.131 (7) | 0.011 (5) | 0.049 (6) | 0.053 (6) |
C4 | 0.075 (5) | 0.121 (6) | 0.106 (6) | 0.000 (5) | 0.036 (4) | 0.011 (5) |
C7 | 0.115 (6) | 0.139 (6) | 0.060 (4) | 0.004 (6) | 0.020 (5) | −0.023 (5) |
C8 | 0.140 (8) | 0.145 (8) | 0.069 (5) | −0.016 (7) | −0.011 (5) | 0.011 (5) |
C9 | 0.114 (6) | 0.133 (7) | 0.075 (5) | 0.010 (6) | 0.000 (5) | 0.033 (6) |
C12 | 0.052 (4) | 0.163 (8) | 0.102 (6) | −0.012 (5) | 0.009 (4) | −0.005 (6) |
C13 | 0.065 (4) | 0.098 (5) | 0.121 (6) | −0.021 (4) | −0.018 (5) | 0.000 (6) |
C14 | 0.098 (6) | 0.136 (7) | 0.093 (5) | −0.014 (5) | −0.010 (5) | −0.042 (5) |
F11—B2 | 1.231 (12) | N10—H10A | 0.9000 |
F12—B2 | 1.366 (12) | N10—H10B | 0.9000 |
F13—B2 | 1.351 (12) | N11—C12 | 1.427 (8) |
F14—B2 | 1.386 (12) | N11—H11A | 0.9000 |
F11'—B2 | 1.369 (12) | N11—H11B | 0.9000 |
F12'—B2 | 1.370 (14) | N15—C14 | 1.432 (8) |
F13'—B2 | 1.349 (12) | N15—H15A | 0.9000 |
F14'—B2 | 1.252 (13) | N15—H15B | 0.9000 |
F1—B1 | 1.290 (11) | C2—C3 | 1.492 (9) |
F2—B1 | 1.347 (11) | C2—H2A | 0.9700 |
F3—B1 | 1.301 (11) | C2—H2B | 0.9700 |
F4—B1 | 1.316 (11) | C3—C4 | 1.472 (9) |
F1'—B1 | 1.310 (12) | C3—H3A | 0.9700 |
F2'—B1 | 1.315 (12) | C3—H3B | 0.9700 |
F3'—B1 | 1.255 (12) | C4—H4A | 0.9700 |
F4'—B1 | 1.352 (14) | C4—H4B | 0.9700 |
Ni—N11 | 2.111 (5) | C7—C8 | 1.471 (10) |
Ni—N5 | 2.116 (5) | C7—H7A | 0.9700 |
Ni—N1 | 2.132 (4) | C7—H7B | 0.9700 |
Ni—N15 | 2.153 (4) | C8—C9 | 1.494 (10) |
Ni—N10 | 2.156 (5) | C8—H8A | 0.9700 |
Ni—N6 | 2.179 (4) | C8—H8B | 0.9700 |
N1—C2 | 1.464 (7) | C9—H9A | 0.9700 |
N1—H1A | 0.9000 | C9—H9B | 0.9700 |
N1—H1B | 0.9000 | C12—C13 | 1.507 (9) |
N5—C4 | 1.455 (7) | C12—H12A | 0.9700 |
N5—H5A | 0.9000 | C12—H12B | 0.9700 |
N5—H5B | 0.9000 | C13—C14 | 1.458 (9) |
N6—C7 | 1.477 (7) | C13—H13A | 0.9700 |
N6—H6A | 0.9000 | C13—H13B | 0.9700 |
N6—H6B | 0.9000 | C14—H14A | 0.9700 |
N10—C9 | 1.459 (8) | C14—H14B | 0.9700 |
F3'—B1—F1 | 82.0 (15) | Ni—N5—H5B | 106.4 |
F3'—B1—F3 | 159.8 (14) | H5A—N5—H5B | 106.5 |
F1—B1—F3 | 117.2 (10) | C7—N6—Ni | 121.1 (4) |
F3'—B1—F1' | 111.4 (12) | C7—N6—H6A | 107.0 |
F1—B1—F1' | 123.0 (11) | Ni—N6—H6A | 107.0 |
F3—B1—F1' | 53.9 (9) | C7—N6—H6B | 107.0 |
F3'—B1—F2' | 111.9 (13) | Ni—N6—H6B | 107.0 |
F1—B1—F2' | 114.2 (12) | H6A—N6—H6B | 106.8 |
F3—B1—F2' | 67.7 (12) | C9—N10—Ni | 122.6 (5) |
F1'—B1—F2' | 110.8 (12) | C9—N10—H10A | 106.7 |
F3'—B1—F4 | 57.3 (9) | Ni—N10—H10A | 106.7 |
F1—B1—F4 | 112.2 (10) | C9—N10—H10B | 106.7 |
F3—B1—F4 | 106.5 (10) | Ni—N10—H10B | 106.7 |
F1'—B1—F4 | 54.2 (9) | H10A—N10—H10B | 106.6 |
F2'—B1—F4 | 129.8 (13) | C12—N11—Ni | 120.5 (4) |
F3'—B1—F2 | 72.0 (11) | C12—N11—H11A | 107.2 |
F1—B1—F2 | 108.1 (10) | Ni—N11—H11A | 107.2 |
F3—B1—F2 | 105.3 (9) | C12—N11—H11B | 107.2 |
F1'—B1—F2 | 128.8 (11) | Ni—N11—H11B | 107.2 |
F2'—B1—F2 | 39.9 (12) | H11A—N11—H11B | 106.8 |
F4—B1—F2 | 107.0 (10) | C14—N15—Ni | 121.6 (4) |
F3'—B1—F4' | 110.5 (13) | C14—N15—H15A | 106.9 |
F1—B1—F4' | 28.7 (13) | Ni—N15—H15A | 106.9 |
F3—B1—F4' | 88.4 (13) | C14—N15—H15B | 106.9 |
F1'—B1—F4' | 107.1 (12) | Ni—N15—H15B | 106.9 |
F2'—B1—F4' | 104.7 (12) | H15A—N15—H15B | 106.7 |
F4—B1—F4' | 125.3 (14) | N1—C2—C3 | 112.7 (6) |
F2—B1—F4' | 119.4 (14) | N1—C2—H2A | 109.1 |
F11—B2—F14' | 146.7 (14) | C3—C2—H2A | 109.1 |
F11—B2—F13' | 70.9 (11) | N1—C2—H2B | 109.1 |
F14'—B2—F13' | 115.2 (14) | C3—C2—H2B | 109.1 |
F11—B2—F13 | 116.5 (13) | H2A—C2—H2B | 107.8 |
F14'—B2—F13 | 70.5 (12) | C4—C3—C2 | 114.0 (6) |
F13'—B2—F13 | 158.8 (11) | C4—C3—H3A | 108.8 |
F11—B2—F12 | 116.7 (12) | C2—C3—H3A | 108.8 |
F14'—B2—F12 | 91.2 (13) | C4—C3—H3B | 108.8 |
F13'—B2—F12 | 57.9 (8) | C2—C3—H3B | 108.8 |
F13—B2—F12 | 102.7 (11) | H3A—C3—H3B | 107.7 |
F11—B2—F11' | 93.4 (12) | N5—C4—C3 | 114.9 (6) |
F14'—B2—F11' | 114.5 (13) | N5—C4—H4A | 108.5 |
F13'—B2—F11' | 105.4 (10) | C3—C4—H4A | 108.5 |
F13—B2—F11' | 55.9 (8) | N5—C4—H4B | 108.5 |
F12—B2—F11' | 69.4 (9) | C3—C4—H4B | 108.5 |
F11—B2—F12' | 39.9 (8) | H4A—C4—H4B | 107.5 |
F14'—B2—F12' | 110.8 (12) | C8—C7—N6 | 113.9 (6) |
F13'—B2—F12' | 103.4 (11) | C8—C7—H7A | 108.8 |
F13—B2—F12' | 92.6 (11) | N6—C7—H7A | 108.8 |
F12—B2—F12' | 156.6 (12) | C8—C7—H7B | 108.8 |
F11'—B2—F12' | 106.6 (11) | N6—C7—H7B | 108.8 |
F11—B2—F14 | 109.6 (11) | H7A—C7—H7B | 107.7 |
F14'—B2—F14 | 41.0 (10) | C7—C8—C9 | 119.1 (7) |
F13'—B2—F14 | 90.6 (11) | C7—C8—H8A | 107.5 |
F13—B2—F14 | 104.3 (11) | C9—C8—H8A | 107.5 |
F12—B2—F14 | 105.8 (11) | C7—C8—H8B | 107.5 |
F11'—B2—F14 | 155.5 (12) | C9—C8—H8B | 107.5 |
F12'—B2—F14 | 87.0 (12) | H8A—C8—H8B | 107.0 |
N11—Ni—N5 | 179.0 (2) | N10—C9—C8 | 113.2 (7) |
N11—Ni—N1 | 93.95 (19) | N10—C9—H9A | 108.9 |
N5—Ni—N1 | 86.57 (18) | C8—C9—H9A | 108.9 |
N11—Ni—N15 | 86.74 (19) | N10—C9—H9B | 108.9 |
N5—Ni—N15 | 92.43 (19) | C8—C9—H9B | 108.9 |
N1—Ni—N15 | 94.94 (19) | H9A—C9—H9B | 107.7 |
N11—Ni—N10 | 91.3 (2) | N11—C12—C13 | 116.2 (6) |
N5—Ni—N10 | 88.2 (2) | N11—C12—H12A | 108.2 |
N1—Ni—N10 | 174.2 (2) | C13—C12—H12A | 108.2 |
N15—Ni—N10 | 87.9 (2) | N11—C12—H12B | 108.2 |
N11—Ni—N6 | 90.11 (19) | C13—C12—H12B | 108.2 |
N5—Ni—N6 | 90.70 (19) | H12A—C12—H12B | 107.4 |
N1—Ni—N6 | 88.75 (18) | C14—C13—C12 | 117.4 (6) |
N15—Ni—N6 | 175.30 (19) | C14—C13—H13A | 108.0 |
N10—Ni—N6 | 88.6 (2) | C12—C13—H13A | 108.0 |
C2—N1—Ni | 120.5 (4) | C14—C13—H13B | 108.0 |
C2—N1—H1A | 107.2 | C12—C13—H13B | 108.0 |
Ni—N1—H1A | 107.2 | H13A—C13—H13B | 107.2 |
C2—N1—H1B | 107.2 | N15—C14—C13 | 114.8 (6) |
Ni—N1—H1B | 107.2 | N15—C14—H14A | 108.6 |
H1A—N1—H1B | 106.8 | C13—C14—H14A | 108.6 |
C4—N5—Ni | 123.6 (4) | N15—C14—H14B | 108.6 |
C4—N5—H5A | 106.4 | C13—C14—H14B | 108.6 |
Ni—N5—H5A | 106.4 | H14A—C14—H14B | 107.5 |
C4—N5—H5B | 106.4 | ||
N11—Ni—N1—C2 | 143.1 (5) | N10—Ni—N11—C12 | 125.6 (6) |
N5—Ni—N1—C2 | −36.1 (5) | N6—Ni—N11—C12 | −145.8 (5) |
N15—Ni—N1—C2 | 56.1 (5) | N11—Ni—N15—C14 | −37.7 (5) |
N6—Ni—N1—C2 | −126.9 (5) | N5—Ni—N15—C14 | 142.8 (5) |
N1—Ni—N5—C4 | 31.9 (5) | N1—Ni—N15—C14 | 56.0 (5) |
N15—Ni—N5—C4 | −62.9 (5) | N10—Ni—N15—C14 | −129.1 (5) |
N10—Ni—N5—C4 | −150.8 (6) | Ni—N1—C2—C3 | 59.2 (8) |
N6—Ni—N5—C4 | 120.6 (5) | N1—C2—C3—C4 | −69.8 (9) |
N11—Ni—N6—C7 | −62.3 (5) | Ni—N5—C4—C3 | −50.3 (9) |
N5—Ni—N6—C7 | 117.1 (5) | C2—C3—C4—N5 | 64.6 (9) |
N1—Ni—N6—C7 | −156.3 (5) | Ni—N6—C7—C8 | −48.7 (8) |
N10—Ni—N6—C7 | 28.9 (5) | N6—C7—C8—C9 | 66.8 (10) |
N11—Ni—N10—C9 | 60.3 (6) | Ni—N10—C9—C8 | 49.1 (9) |
N5—Ni—N10—C9 | −120.5 (6) | C7—C8—C9—N10 | −66.6 (10) |
N15—Ni—N10—C9 | 147.0 (6) | Ni—N11—C12—C13 | −54.4 (8) |
N6—Ni—N10—C9 | −29.7 (6) | N11—C12—C13—C14 | 61.4 (9) |
N1—Ni—N11—C12 | −57.0 (6) | Ni—N15—C14—C13 | 53.5 (9) |
N15—Ni—N11—C12 | 37.7 (5) | C12—C13—C14—N15 | −60.0 (9) |
Experimental details
Crystal data | |
Chemical formula | [Ni(C9H30N6)](BF4)2 |
Mr | 454.72 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 298 |
a, b, c (Å) | 15.2751 (14), 15.498 (2), 16.835 (2) |
V (Å3) | 3985.6 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.05 |
Crystal size (mm) | 0.4 × 0.3 × 0.2 |
Data collection | |
Diffractometer | Siemens P21 upgraded to P4 diffractometer |
Absorption correction | ψ scan (XPREP in SHELXTL; Bruker, 1996) |
Tmin, Tmax | 0.654, 0.742 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4877, 3503, 1657 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.139, 1.00 |
No. of reflections | 3503 |
No. of parameters | 311 |
No. of restraints | 142 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.22 |
Computer programs: XSCANS (Bruker, 1996), XSCANS, SHELXTL (Bruker, 1996), XS in SHELXTL, XL in SHELXTL, XP in SHELXTL, XCIF in SHELXTL.
The title compound, (I), was obtained in attempt to prepare the analogous compounds [Ni(en)2ClO4](ClO4) and [Ni(en)2ClO4](PF6) (en is ethylenediamine) (Landee et al., 1997). These compounds contain chains of nitrito-bridged nickel(II). These chains of S = 1 ions exhibit antiferromagnetic exchange coupling (Meyer et al., 1982). Accordingly, they are ideal candidates for investigating the conjecture by Haldane that integer spin antiferromagnetic chains exhibit an energy gap between the nonmagnetic singlet ground state and the lowest lying excited state (Haldane, 1983).
In the title compound, the average Ni—N bond distance is 2.140 (24) Å, with N—Ni—N chelate bite angles ranging from 86.57 (18) to 88.6 (2)°. Furthermore, the trans angles are different from the typical octahedral angle 174.2 (2)–179.0 (2)°. The structure is different from the corresponding nitrate structure (Vezzosi et al., 1985). The three six-membered rings are similar to each other, with chair conformations, as shown in Fig. 1. The Ni—N—C and N—C—C angles are close in value, with ranges of 120.5 (4)–123.6 (4) and 112.7 (6)–116.2 (6)°, respectively. The analogous nitrate structure shows a pronounced flattening in one of the six-membered rings, as indicated by wider ranges of the above angles of 114 (1)–128 (1) and 113 (1)–127 (2)°, respectively. N—H···F hydrogen bonds stabilize the packing of the formula units in the crystal. The two tetrafluoroborate anions are disordered, as reflected by the large displacement ellipsoids of the F atoms.