Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106010407/ga3002sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106010407/ga3002Isup2.hkl |
CCDC reference: 618605
The compound was prepared as reported by Curtis et al. (1993) (see scheme), and a crystal was grown by evaporation of an aqueous solution.
Water H atoms were located in difference syntheses and their positions were refined with restrained O—H distances [O—H = 0.82 (s.u.?) Å] and H—O—H angles [H···H = 1.3 (s.u.) Å???]. The H atoms were placed in calculated positions (C—H = 0.96 and 0.97 Å; N—H = 0.89 and 0.91 Å) and treated as riding on their parent atoms with Uiso(H) values of 1.2Ueq(C,N) for CH2 and NH groups, and 1.5Ueq(C) for CH3 groups. Interchange of the substituent methyl and azonium sites caused an increase of R1 from 0.0164 to 0.0286.
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3.2 (Farrugia, 1997); software used to prepare material for publication: SHELXTL.
Fig. 1. The asymmetric unit of (I), with displacement ellipsoids drawn at 50% confidence levels and with H atoms shown as circles of arbitrary radii. |
[NiCl(C12H32N6)(H2O)]Cl3·3H2O | F(000) = 564 |
Mr = 533.01 | Dx = 1.530 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 3552 reflections |
a = 10.375 (1) Å | θ = 3.1–28.2° |
b = 10.532 (1) Å | µ = 1.33 mm−1 |
c = 10.893 (1) Å | T = 273 K |
β = 103.610 (1)° | Block, blue–violet |
V = 1156.9 (2) Å3 | 0.40 × 0.40 × 0.32 mm |
Z = 2 |
Bruker SMART CCD diffractometer | 3315 independent reflections |
Radiation source: fine-focus sealed tube | 3243 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.010 |
ϕ and ω scans | θmax = 28.2°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −10→12 |
Tmin = 0.535, Tmax = 0.653 | k = −13→11 |
3617 measured reflections | l = −9→14 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.016 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.040 | w = 1/[σ2(Fo2)] |
S = 0.97 | (Δ/σ)max = 0.001 |
4243 reflections | Δρmax = 0.24 e Å−3 |
280 parameters | Δρmin = −0.31 e Å−3 |
13 restraints | Absolute structure: Flack (1983), 313 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.012 (7) |
[NiCl(C12H32N6)(H2O)]Cl3·3H2O | V = 1156.9 (2) Å3 |
Mr = 533.01 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.375 (1) Å | µ = 1.33 mm−1 |
b = 10.532 (1) Å | T = 273 K |
c = 10.893 (1) Å | 0.40 × 0.40 × 0.32 mm |
β = 103.610 (1)° |
Bruker SMART CCD diffractometer | 3315 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 3243 reflections with I > 2σ(I) |
Tmin = 0.535, Tmax = 0.653 | Rint = 0.010 |
3617 measured reflections |
R[F2 > 2σ(F2)] = 0.016 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.040 | Δρmax = 0.24 e Å−3 |
S = 0.97 | Δρmin = −0.31 e Å−3 |
4243 reflections | Absolute structure: Flack (1983), 313 Friedel pairs |
280 parameters | Absolute structure parameter: 0.012 (7) |
13 restraints |
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 | ||
Ni1 | 0.74036 (2) | 0.58166 (2) | 0.75384 (2) | 0.00804 (5) | |
N1 | 0.79466 (13) | 0.49497 (14) | 0.92890 (13) | 0.0093 (3) | |
H1 | 0.7695 | 0.5477 | 0.9852 | 0.011* | |
C2 | 0.94252 (16) | 0.49239 (18) | 0.96154 (17) | 0.0117 (4) | |
H2A | 0.9740 | 0.4241 | 0.9165 | 0.014* | |
H2B | 0.9755 | 0.4782 | 1.0514 | 0.014* | |
C3 | 0.99178 (17) | 0.61824 (17) | 0.92480 (16) | 0.0114 (4) | |
H3A | 0.9635 | 0.6863 | 0.9725 | 0.014* | |
H3B | 1.0879 | 0.6183 | 0.9430 | 0.014* | |
N4 | 0.93598 (14) | 0.63775 (14) | 0.78690 (13) | 0.0096 (3) | |
H4 | 0.9782 | 0.5830 | 0.7449 | 0.012* | |
C5 | 0.95801 (17) | 0.76731 (17) | 0.74468 (16) | 0.0103 (4) | |
H5A | 1.0525 | 0.7846 | 0.7640 | 0.012* | |
H5B | 0.9171 | 0.8279 | 0.7908 | 0.012* | |
C6 | 0.90051 (17) | 0.78506 (17) | 0.60257 (17) | 0.0094 (4) | |
C61 | 0.95810 (17) | 0.69146 (17) | 0.52381 (17) | 0.0112 (4) | |
H61A | 0.9257 | 0.7109 | 0.4358 | 0.017* | |
H61B | 0.9319 | 0.6068 | 0.5399 | 0.017* | |
H61C | 1.0531 | 0.6974 | 0.5459 | 0.017* | |
N6 | 0.94441 (14) | 0.91506 (14) | 0.57217 (14) | 0.0110 (3) | |
H6D | 0.9122 | 0.9314 | 0.4905 | 0.016* | |
H6E | 1.0326 | 0.9180 | 0.5897 | 0.016* | |
H6F | 0.9144 | 0.9728 | 0.6183 | 0.016* | |
C7 | 0.74726 (17) | 0.78866 (17) | 0.56313 (17) | 0.0098 (4) | |
H7A | 0.7149 | 0.8497 | 0.6155 | 0.012* | |
H7B | 0.7195 | 0.8168 | 0.4761 | 0.012* | |
N8 | 0.68776 (13) | 0.66347 (14) | 0.57552 (13) | 0.0091 (3) | |
H8 | 0.7130 | 0.6095 | 0.5203 | 0.011* | |
C9 | 0.54003 (17) | 0.66760 (19) | 0.54396 (18) | 0.0125 (4) | |
H9A | 0.5064 | 0.6820 | 0.4542 | 0.015* | |
H9B | 0.5097 | 0.7362 | 0.5895 | 0.015* | |
C10 | 0.48999 (17) | 0.54071 (17) | 0.58160 (16) | 0.0113 (4) | |
H10A | 0.3939 | 0.5414 | 0.5644 | 0.014* | |
H10B | 0.5168 | 0.4727 | 0.5329 | 0.014* | |
N11 | 0.54663 (14) | 0.51951 (14) | 0.71836 (13) | 0.0091 (3) | |
H11 | 0.5028 | 0.5721 | 0.7610 | 0.011* | |
C12 | 0.52747 (18) | 0.38941 (17) | 0.75920 (16) | 0.0103 (4) | |
H12A | 0.5704 | 0.3306 | 0.7129 | 0.012* | |
H12B | 0.4334 | 0.3701 | 0.7387 | 0.012* | |
C13 | 0.58373 (17) | 0.36976 (17) | 0.90160 (17) | 0.0096 (4) | |
C131 | 0.52423 (17) | 0.46122 (17) | 0.98070 (17) | 0.0122 (4) | |
H13A | 0.4293 | 0.4545 | 0.9575 | 0.018* | |
H13B | 0.5500 | 0.5464 | 0.9661 | 0.018* | |
H13C | 0.5558 | 0.4406 | 1.0685 | 0.018* | |
N13 | 0.54265 (14) | 0.23808 (14) | 0.92972 (14) | 0.0106 (3) | |
H13D | 0.5755 | 0.2206 | 1.0110 | 0.016* | |
H13E | 0.5736 | 0.1823 | 0.8824 | 0.016* | |
H13F | 0.4546 | 0.2335 | 0.9124 | 0.016* | |
C14 | 0.73671 (17) | 0.36936 (17) | 0.94227 (18) | 0.0106 (4) | |
H14A | 0.7641 | 0.3425 | 1.0297 | 0.013* | |
H14B | 0.7709 | 0.3082 | 0.8913 | 0.013* | |
Cl1 | 0.67601 (4) | 0.77095 (4) | 0.85613 (4) | 0.01244 (9) | |
Cl2 | 0.83430 (4) | 0.94679 (4) | 0.27890 (4) | 0.01455 (10) | |
Cl3 | 0.89871 (5) | 0.14288 (5) | 0.74143 (4) | 0.01861 (11) | |
Cl4 | 0.73747 (4) | 0.43082 (4) | 0.36420 (4) | 0.01473 (10) | |
O1 | 0.79164 (13) | 0.41296 (13) | 0.66016 (14) | 0.0144 (3) | |
H1E | 0.777 (2) | 0.410 (2) | 0.5839 (15) | 0.038 (8)* | |
H1F | 0.8293 (19) | 0.3497 (17) | 0.6855 (19) | 0.025 (7)* | |
O2 | 0.62333 (16) | 0.06241 (15) | 0.77669 (14) | 0.0236 (3) | |
H2E | 0.6963 (17) | 0.082 (3) | 0.770 (2) | 0.046 (8)* | |
H2F | 0.630 (2) | −0.0161 (16) | 0.794 (2) | 0.044 (8)* | |
O3 | 0.72995 (14) | 0.66095 (15) | 0.16085 (13) | 0.0191 (3) | |
H3E | 0.740 (2) | 0.611 (2) | 0.219 (2) | 0.042 (8)* | |
H3F | 0.790 (2) | 0.711 (2) | 0.192 (3) | 0.060 (10)* | |
O4 | 0.33849 (14) | 0.68592 (14) | 0.81124 (14) | 0.0171 (3) | |
H4E | 0.319 (3) | 0.746 (2) | 0.759 (2) | 0.075 (11)* | |
H4F | 0.284 (2) | 0.628 (2) | 0.781 (2) | 0.043 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.00835 (10) | 0.00711 (10) | 0.00841 (11) | 0.00007 (9) | 0.00143 (8) | 0.00055 (8) |
N1 | 0.0091 (7) | 0.0092 (8) | 0.0097 (8) | −0.0012 (6) | 0.0022 (6) | −0.0003 (6) |
C2 | 0.0101 (9) | 0.0115 (9) | 0.0120 (10) | −0.0004 (8) | −0.0004 (7) | 0.0032 (7) |
C3 | 0.0105 (8) | 0.0129 (10) | 0.0095 (9) | −0.0021 (7) | −0.0002 (7) | 0.0019 (7) |
N4 | 0.0124 (7) | 0.0075 (7) | 0.0090 (8) | 0.0006 (6) | 0.0027 (6) | 0.0011 (6) |
C5 | 0.0109 (8) | 0.0094 (9) | 0.0105 (9) | −0.0025 (8) | 0.0022 (7) | 0.0002 (7) |
C6 | 0.0107 (8) | 0.0065 (9) | 0.0115 (9) | −0.0019 (7) | 0.0035 (7) | 0.0020 (7) |
C61 | 0.0128 (9) | 0.0100 (9) | 0.0117 (10) | −0.0001 (7) | 0.0044 (7) | −0.0002 (7) |
N6 | 0.0110 (7) | 0.0098 (8) | 0.0123 (8) | −0.0005 (7) | 0.0030 (6) | 0.0011 (6) |
C7 | 0.0098 (8) | 0.0083 (9) | 0.0105 (9) | −0.0002 (7) | 0.0009 (7) | 0.0009 (7) |
N8 | 0.0083 (7) | 0.0073 (8) | 0.0117 (8) | −0.0001 (6) | 0.0025 (6) | −0.0001 (6) |
C9 | 0.0096 (9) | 0.0141 (10) | 0.0126 (10) | 0.0005 (8) | 0.0002 (7) | 0.0037 (7) |
C10 | 0.0105 (8) | 0.0125 (10) | 0.0098 (9) | −0.0026 (7) | 0.0001 (7) | 0.0020 (7) |
N11 | 0.0106 (7) | 0.0074 (7) | 0.0092 (8) | 0.0001 (6) | 0.0021 (6) | 0.0002 (6) |
C12 | 0.0107 (8) | 0.0089 (9) | 0.0109 (10) | −0.0019 (7) | 0.0016 (7) | 0.0003 (7) |
C13 | 0.0105 (9) | 0.0073 (9) | 0.0112 (9) | −0.0009 (7) | 0.0030 (7) | 0.0013 (7) |
C131 | 0.0118 (9) | 0.0109 (10) | 0.0145 (10) | −0.0001 (8) | 0.0044 (7) | 0.0004 (7) |
N13 | 0.0117 (8) | 0.0083 (8) | 0.0118 (8) | −0.0014 (6) | 0.0024 (6) | 0.0011 (6) |
C14 | 0.0113 (9) | 0.0091 (9) | 0.0112 (9) | −0.0004 (7) | 0.0024 (7) | 0.0013 (7) |
Cl1 | 0.0154 (2) | 0.0090 (2) | 0.0140 (2) | 0.00063 (18) | 0.00578 (17) | −0.00082 (16) |
Cl2 | 0.0136 (2) | 0.0150 (2) | 0.0142 (2) | −0.00205 (19) | 0.00154 (16) | 0.00211 (18) |
Cl3 | 0.0281 (3) | 0.0126 (2) | 0.0176 (2) | 0.0044 (2) | 0.0104 (2) | 0.00145 (19) |
Cl4 | 0.0147 (2) | 0.0153 (2) | 0.0135 (2) | 0.00040 (19) | 0.00195 (16) | −0.00169 (18) |
O1 | 0.0200 (7) | 0.0106 (7) | 0.0124 (8) | 0.0042 (6) | 0.0035 (6) | 0.0017 (5) |
O2 | 0.0304 (8) | 0.0126 (8) | 0.0319 (9) | 0.0011 (8) | 0.0154 (7) | −0.0002 (7) |
O3 | 0.0174 (7) | 0.0196 (8) | 0.0177 (8) | −0.0039 (7) | −0.0010 (6) | 0.0025 (6) |
O4 | 0.0185 (7) | 0.0140 (7) | 0.0167 (8) | −0.0009 (6) | 0.0000 (6) | 0.0014 (6) |
Ni1—N1 | 2.069 (2) | N8—C9 | 1.490 (2) |
Ni1—N4 | 2.063 (2) | N8—H8 | 0.9100 |
Ni1—N8 | 2.077 (2) | C9—C10 | 1.524 (2) |
Ni1—N11 | 2.062 (2) | C9—H9A | 0.9700 |
Ni1—O1 | 2.177 (2) | C9—H9B | 0.9700 |
Ni1—Cl1 | 2.4520 (5) | C10—N11 | 1.484 (2) |
N1—C14 | 1.475 (2) | C10—H10A | 0.9700 |
N1—C2 | 1.491 (2) | C10—H10B | 0.9700 |
N1—H1 | 0.9100 | N11—C12 | 1.469 (2) |
C2—C3 | 1.508 (2) | N11—H11 | 0.9100 |
C2—H2A | 0.9700 | C12—C13 | 1.537 (2) |
C2—H2B | 0.9700 | C12—H12A | 0.9700 |
C3—N4 | 1.491 (2) | C12—H12B | 0.9700 |
C3—H3A | 0.9700 | C13—N13 | 1.503 (2) |
C3—H3B | 0.9700 | C13—C131 | 1.517 (2) |
N4—C5 | 1.475 (2) | C13—C14 | 1.544 (2) |
N4—H4 | 0.9100 | C131—H13A | 0.9600 |
C5—C6 | 1.534 (2) | C131—H13B | 0.9600 |
C5—H5A | 0.9700 | C131—H13C | 0.9600 |
C5—H5B | 0.9700 | N13—H13D | 0.8900 |
C6—N6 | 1.504 (2) | N13—H13E | 0.8900 |
C6—C61 | 1.519 (2) | N13—H13F | 0.8900 |
C6—C7 | 1.547 (2) | C14—H14A | 0.9700 |
C61—H61A | 0.9600 | C14—H14B | 0.9700 |
C61—H61B | 0.9600 | O1—H1E | 0.809 (15) |
C61—H61C | 0.9600 | O1—H1F | 0.789 (15) |
N6—H6D | 0.8900 | O2—H2E | 0.804 (15) |
N6—H6E | 0.8900 | O2—H2F | 0.849 (16) |
N6—H6F | 0.8900 | O3—H3E | 0.811 (16) |
C7—N8 | 1.475 (2) | O3—H3F | 0.824 (16) |
C7—H7A | 0.9700 | O4—H4E | 0.840 (17) |
C7—H7B | 0.9700 | O4—H4F | 0.843 (16) |
N1—Ni1—N4 | 85.53 (6) | C6—C7—H7A | 109.2 |
N1—Ni1—N8 | 178.16 (7) | N8—C7—H7B | 109.2 |
N1—Ni1—N11 | 94.28 (6) | C6—C7—H7B | 109.2 |
N4—Ni1—N8 | 94.34 (6) | H7A—C7—H7B | 107.9 |
N4—Ni1—N11 | 177.96 (7) | C7—N8—C9 | 112.49 (14) |
N8—Ni1—N11 | 85.78 (5) | C7—N8—Ni1 | 115.64 (11) |
N1—Ni1—O1 | 91.62 (6) | C9—N8—Ni1 | 104.91 (10) |
N4—Ni1—O1 | 88.66 (6) | C7—N8—H8 | 107.8 |
N8—Ni1—O1 | 86.54 (6) | C9—N8—H8 | 107.8 |
N11—Ni1—O1 | 89.31 (6) | Ni1—N8—H8 | 107.8 |
N1—Ni1—Cl1 | 89.10 (4) | N8—C9—C10 | 108.01 (15) |
N4—Ni1—Cl1 | 92.85 (4) | N8—C9—H9A | 110.1 |
N8—Ni1—Cl1 | 92.75 (4) | C10—C9—H9A | 110.1 |
N11—Ni1—Cl1 | 89.18 (4) | N8—C9—H9B | 110.1 |
O1—Ni1—Cl1 | 178.37 (4) | C10—C9—H9B | 110.1 |
C14—N1—C2 | 112.37 (14) | H9A—C9—H9B | 108.4 |
C14—N1—Ni1 | 117.26 (11) | N11—C10—C9 | 108.81 (14) |
C2—N1—Ni1 | 105.63 (10) | N11—C10—H10A | 109.9 |
C14—N1—H1 | 107.0 | C9—C10—H10A | 109.9 |
C2—N1—H1 | 107.0 | N11—C10—H10B | 109.9 |
Ni1—N1—H1 | 107.0 | C9—C10—H10B | 109.9 |
N1—C2—C3 | 108.33 (15) | H10A—C10—H10B | 108.3 |
N1—C2—H2A | 110.0 | C12—N11—C10 | 113.24 (14) |
C3—C2—H2A | 110.0 | C12—N11—Ni1 | 115.78 (12) |
N1—C2—H2B | 110.0 | C10—N11—Ni1 | 106.18 (10) |
C3—C2—H2B | 110.0 | C12—N11—H11 | 107.1 |
H2A—C2—H2B | 108.4 | C10—N11—H11 | 107.1 |
N4—C3—C2 | 108.23 (14) | Ni1—N11—H11 | 107.1 |
N4—C3—H3A | 110.1 | N11—C12—C13 | 112.64 (14) |
C2—C3—H3A | 110.1 | N11—C12—H12A | 109.1 |
N4—C3—H3B | 110.1 | C13—C12—H12A | 109.1 |
C2—C3—H3B | 110.1 | N11—C12—H12B | 109.1 |
H3A—C3—H3B | 108.4 | C13—C12—H12B | 109.1 |
C5—N4—C3 | 112.93 (14) | H12A—C12—H12B | 107.8 |
C5—N4—Ni1 | 115.39 (11) | N13—C13—C131 | 107.29 (13) |
C3—N4—Ni1 | 105.62 (10) | N13—C13—C12 | 105.74 (14) |
C5—N4—H4 | 107.5 | C131—C13—C12 | 112.27 (15) |
C3—N4—H4 | 107.5 | N13—C13—C14 | 105.10 (14) |
Ni1—N4—H4 | 107.5 | C131—C13—C14 | 111.52 (15) |
N4—C5—C6 | 112.05 (14) | C12—C13—C14 | 114.24 (13) |
N4—C5—H5A | 109.2 | C13—C131—H13A | 109.5 |
C6—C5—H5A | 109.2 | C13—C131—H13B | 109.5 |
N4—C5—H5B | 109.2 | H13A—C131—H13B | 109.5 |
C6—C5—H5B | 109.2 | C13—C131—H13C | 109.5 |
H5A—C5—H5B | 107.9 | H13A—C131—H13C | 109.5 |
N6—C6—C61 | 106.67 (13) | H13B—C131—H13C | 109.5 |
N6—C6—C5 | 105.49 (14) | C13—N13—H13D | 109.5 |
C61—C6—C5 | 112.32 (15) | C13—N13—H13E | 109.5 |
N6—C6—C7 | 105.14 (14) | H13D—N13—H13E | 109.5 |
C61—C6—C7 | 111.99 (15) | C13—N13—H13F | 109.5 |
C5—C6—C7 | 114.42 (14) | H13D—N13—H13F | 109.5 |
C6—C61—H61A | 109.5 | H13E—N13—H13F | 109.5 |
C6—C61—H61B | 109.5 | N1—C14—C13 | 112.62 (15) |
H61A—C61—H61B | 109.5 | N1—C14—H14A | 109.1 |
C6—C61—H61C | 109.5 | C13—C14—H14A | 109.1 |
H61A—C61—H61C | 109.5 | N1—C14—H14B | 109.1 |
H61B—C61—H61C | 109.5 | C13—C14—H14B | 109.1 |
C6—N6—H6D | 109.5 | H14A—C14—H14B | 107.8 |
C6—N6—H6E | 109.5 | Ni1—O1—H1E | 120.3 (17) |
H6D—N6—H6E | 109.5 | Ni1—O1—H1F | 132.9 (16) |
C6—N6—H6F | 109.5 | H1E—O1—H1F | 107 (2) |
H6D—N6—H6F | 109.5 | H2E—O2—H2F | 104 (2) |
H6E—N6—H6F | 109.5 | H3E—O3—H3F | 99 (2) |
N8—C7—C6 | 112.18 (14) | H4E—O4—H4F | 104 (2) |
N8—C7—H7A | 109.2 | ||
N11—Ni1—N1—C14 | 37.57 (12) | N11—Ni1—N8—C7 | 142.02 (12) |
N4—Ni1—N1—C14 | −140.39 (12) | N4—Ni1—N8—C7 | −40.02 (12) |
N8—Ni1—N1—C14 | −54.3 (19) | N1—Ni1—N8—C7 | −126.0 (18) |
O1—Ni1—N1—C14 | −51.86 (12) | O1—Ni1—N8—C7 | −128.41 (11) |
Cl1—Ni1—N1—C14 | 126.68 (11) | Cl1—Ni1—N8—C7 | 53.05 (11) |
N11—Ni1—N1—C2 | 163.64 (11) | N11—Ni1—N8—C9 | 17.48 (11) |
N4—Ni1—N1—C2 | −14.32 (11) | N4—Ni1—N8—C9 | −164.56 (12) |
N8—Ni1—N1—C2 | 71.8 (19) | N1—Ni1—N8—C9 | 109.5 (18) |
O1—Ni1—N1—C2 | 74.21 (11) | O1—Ni1—N8—C9 | 107.05 (11) |
Cl1—Ni1—N1—C2 | −107.25 (11) | Cl1—Ni1—N8—C9 | −71.49 (11) |
C14—N1—C2—C3 | 170.83 (14) | C7—N8—C9—C10 | −170.28 (14) |
Ni1—N1—C2—C3 | 41.81 (16) | Ni1—N8—C9—C10 | −43.77 (16) |
N1—C2—C3—N4 | −58.22 (17) | N8—C9—C10—N11 | 57.90 (17) |
C2—C3—N4—C5 | 169.84 (14) | C9—C10—N11—C12 | −168.14 (14) |
C2—C3—N4—Ni1 | 42.85 (15) | C9—C10—N11—Ni1 | −40.01 (15) |
N11—Ni1—N4—C5 | 134.1 (17) | N4—Ni1—N11—C12 | 45.5 (18) |
N1—Ni1—N4—C5 | −141.05 (12) | N1—Ni1—N11—C12 | −39.14 (12) |
N8—Ni1—N4—C5 | 40.79 (12) | N8—Ni1—N11—C12 | 139.01 (12) |
O1—Ni1—N4—C5 | 127.22 (12) | O1—Ni1—N11—C12 | 52.43 (12) |
Cl1—Ni1—N4—C5 | −52.18 (11) | Cl1—Ni1—N11—C12 | −128.17 (11) |
N11—Ni1—N4—C3 | −100.4 (18) | N4—Ni1—N11—C10 | −81.1 (18) |
N1—Ni1—N4—C3 | −15.57 (11) | N1—Ni1—N11—C10 | −165.75 (11) |
N8—Ni1—N4—C3 | 166.28 (11) | N8—Ni1—N11—C10 | 12.40 (11) |
O1—Ni1—N4—C3 | −107.30 (11) | O1—Ni1—N11—C10 | −74.18 (11) |
Cl1—Ni1—N4—C3 | 73.30 (10) | Cl1—Ni1—N11—C10 | 105.21 (10) |
C3—N4—C5—C6 | 179.70 (13) | C10—N11—C12—C13 | −178.65 (13) |
Ni1—N4—C5—C6 | −58.67 (16) | Ni1—N11—C12—C13 | 58.38 (16) |
N4—C5—C6—N6 | −173.64 (13) | N11—C12—C13—N13 | 173.77 (14) |
N4—C5—C6—C61 | −57.82 (18) | N11—C12—C13—C131 | 57.09 (19) |
N4—C5—C6—C7 | 71.31 (19) | N11—C12—C13—C14 | −71.16 (19) |
N6—C6—C7—N8 | 174.54 (13) | C2—N1—C14—C13 | −176.84 (13) |
C61—C6—C7—N8 | 59.09 (19) | Ni1—N1—C14—C13 | −54.16 (17) |
C5—C6—C7—N8 | −70.20 (19) | N13—C13—C14—N1 | −176.28 (14) |
C6—C7—N8—C9 | 177.08 (14) | C131—C13—C14—N1 | −60.35 (18) |
C6—C7—N8—Ni1 | 56.57 (16) | C12—C13—C14—N1 | 68.28 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3i | 0.91 | 2.37 | 3.270 (2) | 169 |
N4—H4···Cl2ii | 0.91 | 2.48 | 3.323 (2) | 154 |
N6—H6D···Cl2 | 0.89 | 2.26 | 3.147 (2) | 173 |
N6—H6E···Cl4iii | 0.89 | 2.32 | 3.213 (2) | 179 |
N6—H6F···Cl3iv | 0.89 | 2.27 | 3.129 (2) | 163 |
N8—H8···Cl4 | 0.91 | 2.59 | 3.482 (2) | 168 |
N11—H11···O4 | 0.91 | 2.25 | 3.128 (2) | 161 |
N13—H13D···O4v | 0.89 | 1.97 | 2.854 (2) | 176 |
N13—H13E···O2 | 0.89 | 1.86 | 2.750 (2) | 175 |
N13—H13F···O3vi | 0.89 | 2.04 | 2.884 (2) | 158 |
O1—H1E···Cl4 | 0.81 (2) | 2.34 (2) | 3.145 (2) | 172 (2) |
O1—H1F···Cl3 | 0.79 (2) | 2.33 (2) | 3.106 (2) | 168 (2) |
O2—H2E···Cl3 | 0.80 (2) | 2.29 (2) | 3.090 (2) | 177 (2) |
O2—H2F···Cl1vii | 0.85 (2) | 2.36 (2) | 3.201 (2) | 173 (2) |
O3—H3E···Cl4 | 0.81 (2) | 2.47 (2) | 3.272 (2) | 169 (2) |
O3—H3F···Cl2 | 0.82 (2) | 2.66 (2) | 3.352 (2) | 142 (2) |
O4—H4E···Cl4viii | 0.84 (2) | 2.36 (2) | 3.197 (2) | 172 (3) |
O4—H4F···Cl2vi | 0.84 (2) | 2.28 (2) | 3.113 (2) | 169 (2) |
Symmetry codes: (i) x, y, z+1; (ii) −x+2, y−1/2, −z+1; (iii) −x+2, y+1/2, −z+1; (iv) x, y+1, z; (v) −x+1, y−1/2, −z+2; (vi) −x+1, y−1/2, −z+1; (vii) x, y−1, z; (viii) −x+1, y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [NiCl(C12H32N6)(H2O)]Cl3·3H2O |
Mr | 533.01 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 273 |
a, b, c (Å) | 10.375 (1), 10.532 (1), 10.893 (1) |
β (°) | 103.610 (1) |
V (Å3) | 1156.9 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.33 |
Crystal size (mm) | 0.40 × 0.40 × 0.32 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.535, 0.653 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3617, 3315, 3243 |
Rint | 0.010 |
(sin θ/λ)max (Å−1) | 0.665 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.016, 0.040, 0.97 |
No. of reflections | 4243 |
No. of parameters | 280 |
No. of restraints | 13 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.31 |
Absolute structure | Flack (1983), 313 Friedel pairs |
Absolute structure parameter | 0.012 (7) |
Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXTL (Sheldrick, 1997), SHELXTL, ORTEP-3.2 (Farrugia, 1997).
Ni1—N1 | 2.069 (2) | Ni1—N11 | 2.062 (2) |
Ni1—N4 | 2.063 (2) | Ni1—O1 | 2.177 (2) |
Ni1—N8 | 2.077 (2) | Ni1—Cl1 | 2.4520 (5) |
N1—Ni1—N4 | 85.53 (6) | N1—Ni1—O1 | 91.62 (6) |
N1—Ni1—N8 | 178.16 (7) | N4—Ni1—O1 | 88.66 (6) |
N1—Ni1—N11 | 94.28 (6) | N1—Ni1—Cl1 | 89.10 (4) |
N4—Ni1—N8 | 94.34 (6) | N4—Ni1—Cl1 | 92.85 (4) |
N4—Ni1—N11 | 177.96 (7) | O1—Ni1—Cl1 | 178.37 (4) |
N8—Ni1—N11 | 85.78 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3i | 0.91 | 2.37 | 3.270 (2) | 169.3 |
N4—H4···Cl2ii | 0.91 | 2.48 | 3.323 (2) | 154.3 |
N6—H6D···Cl2 | 0.89 | 2.26 | 3.147 (2) | 172.8 |
N6—H6E···Cl4iii | 0.89 | 2.32 | 3.213 (2) | 178.6 |
N6—H6F···Cl3iv | 0.89 | 2.27 | 3.129 (2) | 163.2 |
N8—H8···Cl4 | 0.91 | 2.59 | 3.482 (2) | 167.6 |
N11—H11···O4 | 0.91 | 2.25 | 3.128 (2) | 160.8 |
N13—H13D···O4v | 0.89 | 1.97 | 2.854 (2) | 175.6 |
N13—H13E···O2 | 0.89 | 1.86 | 2.750 (2) | 175.1 |
N13—H13F···O3vi | 0.89 | 2.04 | 2.884 (2) | 157.7 |
O1—H1E···Cl4 | 0.81 (2) | 2.34 (2) | 3.145 (2) | 172 (2) |
O1—H1F···Cl3 | 0.79 (2) | 2.33 (2) | 3.106 (2) | 168 (2) |
O2—H2E···Cl3 | 0.80 (2) | 2.29 (2) | 3.090 (2) | 177 (2) |
O2—H2F···Cl1vii | 0.85 (2) | 2.36 (2) | 3.201 (2) | 173 (2) |
O3—H3E···Cl4 | 0.81 (2) | 2.47 (2) | 3.272 (2) | 169 (2) |
O3—H3F···Cl2 | 0.82 (2) | 2.66 (2) | 3.352 (2) | 142 (2) |
O4—H4E···Cl4viii | 0.84 (2) | 2.36 (2) | 3.197 (2) | 172 (3) |
O4—H4F···Cl2vi | 0.84 (2) | 2.28 (2) | 3.113 (2) | 169 (2) |
Symmetry codes: (i) x, y, z+1; (ii) −x+2, y−1/2, −z+1; (iii) −x+2, y+1/2, −z+1; (iv) x, y+1, z; (v) −x+1, y−1/2, −z+2; (vi) −x+1, y−1/2, −z+1; (vii) x, y−1, z; (viii) −x+1, y+1/2, −z+1. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
The structures of a variety of compounds of trans-6,13-diamine-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane, diam (Comba et al., 1986), with NiII have been described. Structures have been reported by Curtis et al. (1993) for octahedral, triplet ground state NiII compounds with six-coordinate diam (diam-N6) in the 1RS,4RS,8SR,11SR configuration (labelled as β) for β-[Ni(diam-N6)](ClO4)2·H2O, β-[Ni(diam-N6)]Cl2 and β-[Ni(diam-N6)][ZnCl4]·1.5H2O, and with four-coordinate diam (diam-N4) for trans-β-[Ni(diam-N4)(NCS)2]. The compound α-[Ni(diamH-N5)Cl]ClO4)2·H2O has mono-protonated pentadentate diam in the 1RS,4SR,8RS,11SR (α) configuration, with one coordinated chloride ion, while the compound β-[Ni(diamH2-N4)](ClO4)2, with both amine substituents protonated, has square-planar singlet ground state NiII (Curtis et al., 1993). The structure of the title compound, trans-β-[Ni(diamH2-N4)Cl(H2O)]Cl3·3H2O, (I), formal composition Ni2+.(diam)·2H+·4Cl−·4H2O, which crystallizes from solutions of [Ni(diam)]2+ in HCl, is now reported. It was uncertain if this triplet ground state NiII compound had water or chloride ions completing the octahedral coordination.
The structural study shows triplet ground state NiII in planar coordination by the four intracyclic secondary amine N atoms of the di-protonated diam ligand, with one chloride ion and one water molecule trans-axially coordinated (Fig. 1 and Table 1). The diam ligand is achiral, but the four secondary amine groups become chiral centres when coordinated. The β-[Ni(diam-N4)]2+ cation is generally found to crystallize racemically, e.g. for trans-β-[Ni(diam-N4)(NCS)2], with centrosymmetrically related molecules (Curtis et al., 1993). However the asymmetric coordination environment introduced by the dissimilar additional ligands for the cation of (I) leads to chirality of the cation, and thence to the chiral space group P21 for the crystal. We believe an arbitrary choice was made from a crystal batch containing 50% of each enantiomeric crystal form. The related compounds trans-α-[Ni(diamH-N5)Cl](ClO4)2·H2O and trans-α-[Cu(diam-N5)(OClO3)]ClO4 (Bernhardt et al., 1997) crystallize in centrosymmetric space groups P21/n and P1, respectively, so this condition does not arise.
The four N atoms are coplanar [the {maximum or r.m.s.?} displacements from the N4 plane are ±0.002 (1) Å], with the Ni atom displaced from this plane by 0.035 (1) Å towards the coordinated chloride ion. The cation has the 1R,4R,8S,11S (β) configuration usual for cyclic tetraamines in planar four-coordination, with gauche-conformation five-membered and chair-conformation six-membered chelate rings. The displacements of atoms from the N4 plane (in Å, with an s.u. of 0.002 Å unless specified) are −0.383 for atom C2, 0.356 for C3, 0.840 for C5, 0.450 for C6, 0.827 for C7, 0.405 for C9, −0.336 for C10, −0.865 for C12, −0.487 for C13, −0.828 for C14, −1.004 for C61, 1.279 (1) for N6, 0.957 for C131 and −1.353 (1) for N13.
The 6,13-diazonium substituents are equatorially oriented, as also reported for the amino/azonium substituents of trans-β-[Ni(diam-N4)(NCS)2], trans-β-[Cu(diamH2-N4)(OClO3)2](ClO4)2·6H2O (Comba et al., 1986), trans-β-[Cu(diamH2-N4)(OClO3)2](ClO4)2·2H2O (Bernhardt et al., 1997), trans-β-[Co(diamH2-N4)Cl2][ZnCl4]·0.5H2O·0.5EtOH (Curtis et al., 1992) and trans-β-[Pt(diamH2-N4)Cl2]Cl2(ClO4)2·4H2O (Bernhardt et al., 1991 or 1992?). The amino/azonium substituents are axially oriented for trans-β-[Cu(diam-N4)(OClO3)2] (Lawrance et al., 1986), trans-β-[Cu(diam-N4)(OH2)2](ClO4)2 (Bernhardt et al., 1997) and trans-β-[Pd(diamH2-N4)](ClO4)4 (Bernhardt et al., 1990), as well as for β-diam-N4 compounds of NiII and CuII with amido-substituted (Curtis & Puschmann, 2005; Curtis & Robinson, 2005) and anthracenylmethylamino-substituted diam (Bernhardt et al., 1999, 2002). Disorder precluded making an unambiguous assignment of orientation of the substituents for β-[Ni(diamH2-N4)](ClO4)2 (Gainsford & Rae, 1993).
The mean Ni—N distance of 2.068 (3) Å (Table 1) is comparable to values (Å) reported for other triplet ground state NiII compounds of diam, viz. 2.071 (6) for β-[Ni(diam-N6)](ClO4)2·H2O, 2.07 (1) for β-[Ni(diam-N6)]Cl2, 2.06 (1) for β-[Ni(diam-N6)][ZnCl4]·1.5H2O, 2.058 (6) for trans-β-[Ni(diam-N4)(NCS)2] and 2.058 (8) for trans-α-(diamH-N5)Cl]ClO4)2·H2O (Curtis et al., 1993). This distance is clearly little affected by whether the substituent amine groups are coordinated, free or protonated. The Ni—Cl distance here is somewhat shorter than the 2.553 (1) Å observed for trans-α-(diamH-N5)Cl]ClO4)2·H2O (Curtis et al., 1993) but similar to the 2.442 (2) Å found in a related dinickel(II) complex with perchlorate bound trans to the chloride (Szacilowski et al., 2005).
The secondary amine groups, water molecules, azonium and chloride ions are linked into an extensive network by hydrogen bonding involving all the water and nitrogen-bound H atoms (Table 2).