Three polymorphs of bis(nitrito-κN)[tris(2-aminoethyl)amine-κ4N,N′,N′′,N′′′]cobalt(III) chloride, [Co(NO2)2(C6H18N4)]Cl, have been structurally characterized in the 100–300 K temperature range. Two orthorhombic polymorphs are related by a solid-state enantiotropic order–disorder k2 phase transition at ca 152 K. The third, monoclinic, polymorph crystallizes as a nonmerohedral twin. In the structure of the high-temperature (300 K) orthorhombic polymorph, the CoIII complex cation resides on a crystallographic mirror plane, whereas the Cl− anion occupies a crystallographic twofold axis. In the unit cell of the monoclinic polymorph, the cationic CoIII complex is in a general position, whose charge is balanced by two halves of two Cl− anions, each residing on a crystallographic twofold axis.
Supporting information
CCDC references: 1050739; 1050740; 1050741
For all compounds, data collection: APEX2 (Bruker, 2014); cell refinement: SAINT-Plus (Bruker, 2014); data reduction: SAINT-Plus (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and PLATON (Spek, 2009).
(pbcm) Bis(nitrito-
κN)[tris(2-aminoethyl)amine-
κ4N,
N',
N'',
N''']cobalt(III) chloride
top
Crystal data top
[Co(NO2)2(C6H18N4)]Cl | Dx = 1.775 Mg m−3 |
Mr = 332.64 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbcm | Cell parameters from 9933 reflections |
a = 8.4892 (1) Å | θ = 2.4–26.4° |
b = 12.1555 (2) Å | µ = 1.61 mm−1 |
c = 12.0631 (2) Å | T = 300 K |
V = 1244.80 (3) Å3 | Block, orange |
Z = 4 | 0.22 × 0.2 × 0.12 mm |
F(000) = 688 | |
Data collection top
Bruker SMART APEXII area-detector diffractometer | 1339 independent reflections |
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs | 1293 reflections with I > 2σ(I) |
Mirror optics monochromator | Rint = 0.022 |
Detector resolution: 7.9 pixels mm-1 | θmax = 26.4°, θmin = 2.4° |
0.5° ω and 0.5° φ scans | h = −10→10 |
Absorption correction: multi-scan (SADABS2014; Krause et al., 2015) | k = −15→15 |
Tmin = 0.341, Tmax = 0.430 | l = −15→15 |
25379 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.019 | H-atom parameters constrained |
wR(F2) = 0.053 | w = 1/[σ2(Fo2) + (0.0277P)2 + 0.5979P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max = 0.001 |
1339 reflections | Δρmax = 0.47 e Å−3 |
96 parameters | Δρmin = −0.22 e Å−3 |
0 restraints | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Co1 | 0.72722 (3) | 0.63251 (2) | 0.7500 | 0.01735 (9) | |
Cl1 | 1.03578 (6) | 0.7500 | 0.5000 | 0.03053 (13) | |
N2 | 0.95694 (19) | 0.64590 (13) | 0.7500 | 0.0223 (3) | |
H2A | 0.9857 | 0.6983 | 0.7026 | 0.027* | 0.5 |
H2B | 0.9896 | 0.6654 | 0.8173 | 0.027* | 0.5 |
N3 | 0.72223 (14) | 0.62018 (10) | 0.58872 (10) | 0.0258 (3) | |
H3A | 0.6327 | 0.6488 | 0.5633 | 0.031* | |
H3B | 0.8017 | 0.6584 | 0.5600 | 0.031* | |
N1 | 0.75791 (18) | 0.47226 (13) | 0.7500 | 0.0222 (3) | |
O1 | 0.70138 (18) | 0.84023 (10) | 0.66206 (10) | 0.0469 (3) | |
N4 | 0.70746 (19) | 0.78937 (13) | 0.7500 | 0.0244 (4) | |
N5 | 0.4950 (2) | 0.63174 (13) | 0.7500 | 0.0286 (4) | |
O2 | 0.42082 (15) | 0.63656 (12) | 0.66216 (11) | 0.0514 (4) | |
C1 | 0.9312 (2) | 0.44485 (17) | 0.7500 | 0.0285 (4) | |
H1A | 0.9613 | 0.4199 | 0.8234 | 0.034* | 0.5 |
H1B | 0.9500 | 0.3850 | 0.6985 | 0.034* | 0.5 |
C3 | 0.68122 (19) | 0.43054 (12) | 0.64690 (13) | 0.0309 (3) | |
H3C | 0.5675 | 0.4333 | 0.6542 | 0.037* | |
H3D | 0.7122 | 0.3549 | 0.6332 | 0.037* | |
C4 | 0.73445 (19) | 0.50344 (13) | 0.55273 (13) | 0.0335 (3) | |
H4A | 0.8425 | 0.4864 | 0.5331 | 0.040* | |
H4B | 0.6687 | 0.4911 | 0.4882 | 0.040* | |
C2 | 1.0323 (3) | 0.5411 (2) | 0.7182 (2) | 0.0301 (7) | 0.5 |
H2C | 1.1338 | 0.5350 | 0.7546 | 0.036* | 0.5 |
H2D | 1.0499 | 0.5402 | 0.6387 | 0.036* | 0.5 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.01923 (14) | 0.01594 (14) | 0.01689 (15) | 0.00010 (9) | 0.000 | 0.000 |
Cl1 | 0.0317 (3) | 0.0340 (3) | 0.0259 (2) | 0.000 | 0.000 | 0.00322 (19) |
N2 | 0.0237 (8) | 0.0216 (8) | 0.0217 (8) | −0.0016 (6) | 0.000 | 0.000 |
N3 | 0.0310 (6) | 0.0267 (6) | 0.0196 (6) | −0.0015 (5) | −0.0018 (5) | 0.0004 (5) |
N1 | 0.0237 (8) | 0.0172 (7) | 0.0257 (9) | −0.0006 (6) | 0.000 | 0.000 |
O1 | 0.0777 (9) | 0.0267 (6) | 0.0364 (7) | 0.0099 (6) | 0.0069 (6) | 0.0104 (5) |
N4 | 0.0228 (8) | 0.0207 (8) | 0.0295 (9) | 0.0023 (6) | 0.000 | 0.000 |
N5 | 0.0242 (8) | 0.0252 (8) | 0.0364 (10) | −0.0012 (7) | 0.000 | 0.000 |
O2 | 0.0297 (6) | 0.0766 (10) | 0.0479 (8) | 0.0036 (6) | −0.0131 (6) | −0.0065 (6) |
C1 | 0.0270 (10) | 0.0225 (9) | 0.0360 (11) | 0.0056 (8) | 0.000 | 0.000 |
C3 | 0.0338 (7) | 0.0229 (7) | 0.0359 (8) | −0.0034 (6) | −0.0057 (7) | −0.0081 (6) |
C4 | 0.0433 (9) | 0.0326 (8) | 0.0245 (8) | 0.0005 (6) | −0.0031 (6) | −0.0097 (6) |
C2 | 0.0238 (12) | 0.0277 (13) | 0.039 (2) | 0.0044 (10) | 0.0068 (10) | 0.0003 (10) |
Geometric parameters (Å, º) top
Co1—N2 | 1.9570 (16) | O1—N4 | 1.2289 (14) |
Co1—N3i | 1.9517 (12) | N4—O1i | 1.2289 (14) |
Co1—N3 | 1.9517 (12) | N5—O2i | 1.2339 (15) |
Co1—N1 | 1.9653 (17) | N5—O2 | 1.2339 (15) |
Co1—N4 | 1.9141 (16) | C1—H1A | 0.9700 |
Co1—N5 | 1.9716 (18) | C1—H1B | 0.9700 |
N2—H2A | 0.8900 | C1—C2 | 1.500 (3) |
N2—H2B | 0.8900 | C3—H3C | 0.9700 |
N2—C2 | 1.477 (3) | C3—H3D | 0.9700 |
N3—H3A | 0.8900 | C3—C4 | 1.510 (2) |
N3—H3B | 0.8900 | C4—H4A | 0.9700 |
N3—C4 | 1.4876 (19) | C4—H4B | 0.9700 |
N1—C1 | 1.508 (2) | C2—H2C | 0.9700 |
N1—C3i | 1.4926 (17) | C2—H2D | 0.9700 |
N1—C3 | 1.4926 (17) | | |
| | | |
N2—Co1—N1 | 87.15 (7) | C3—N1—C3i | 112.87 (16) |
N2—Co1—N5 | 175.50 (7) | O1i—N4—Co1 | 120.32 (9) |
N3i—Co1—N2 | 91.60 (4) | O1—N4—Co1 | 120.32 (9) |
N3—Co1—N2 | 91.60 (4) | O1i—N4—O1 | 119.36 (18) |
N3i—Co1—N3 | 170.84 (7) | O2i—N5—Co1 | 120.66 (9) |
N3—Co1—N1 | 85.80 (4) | O2—N5—Co1 | 120.66 (9) |
N3i—Co1—N1 | 85.80 (4) | O2i—N5—O2 | 118.35 (19) |
N3i—Co1—N5 | 88.74 (4) | N1—C1—H1A | 109.1 |
N3—Co1—N5 | 88.74 (4) | N1—C1—H1B | 109.1 |
N1—Co1—N5 | 97.35 (7) | H1A—C1—H1B | 107.8 |
N4—Co1—N2 | 90.25 (7) | C2—C1—N1 | 112.68 (17) |
N4—Co1—N3 | 94.28 (4) | C2—C1—H1A | 109.1 |
N4—Co1—N3i | 94.28 (4) | C2—C1—H1B | 109.1 |
N4—Co1—N1 | 177.41 (7) | N1—C3—H3C | 110.3 |
N4—Co1—N5 | 85.24 (7) | N1—C3—H3D | 110.3 |
Co1—N2—H2A | 109.4 | N1—C3—C4 | 107.28 (12) |
Co1—N2—H2B | 109.4 | H3C—C3—H3D | 108.5 |
H2A—N2—H2B | 108.0 | C4—C3—H3C | 110.3 |
C2—N2—Co1 | 111.08 (14) | C4—C3—H3D | 110.3 |
C2—N2—H2A | 109.4 | N3—C4—C3 | 108.63 (12) |
C2—N2—H2B | 109.4 | N3—C4—H4A | 110.0 |
Co1—N3—H3A | 109.4 | N3—C4—H4B | 110.0 |
Co1—N3—H3B | 109.4 | C3—C4—H4A | 110.0 |
H3A—N3—H3B | 108.0 | C3—C4—H4B | 110.0 |
C4—N3—Co1 | 111.27 (9) | H4A—C4—H4B | 108.3 |
C4—N3—H3A | 109.4 | N2—C2—C1 | 111.01 (19) |
C4—N3—H3B | 109.4 | N2—C2—H2C | 109.4 |
C1—N1—Co1 | 110.38 (12) | N2—C2—H2D | 109.4 |
C3—N1—Co1 | 106.20 (9) | C1—C2—H2C | 109.4 |
C3i—N1—Co1 | 106.20 (9) | C1—C2—H2D | 109.4 |
C3i—N1—C1 | 110.51 (10) | H2C—C2—H2D | 108.0 |
C3—N1—C1 | 110.51 (10) | | |
| | | |
Co1—N2—C2—C1 | −28.8 (2) | N1—C3—C4—N3 | −45.72 (16) |
Co1—N3—C4—C3 | 22.78 (15) | C1—N1—C3—C4 | −72.68 (16) |
Co1—N1—C1—C2 | −16.11 (12) | C3—N1—C1—C2 | 101.07 (17) |
Co1—N1—C3—C4 | 47.04 (14) | C3i—N1—C1—C2 | −133.28 (15) |
N1—C1—C2—N2 | 29.3 (2) | C3i—N1—C3—C4 | 163.01 (10) |
Symmetry code: (i) x, y, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···Cl1 | 0.89 | 2.56 | 3.3382 (7) | 147 |
N2—H2B···Cl1i | 0.89 | 2.46 | 3.3382 (7) | 168 |
N3—H3A···O2 | 0.89 | 2.16 | 2.7151 (18) | 120 |
N3—H3B···Cl1 | 0.89 | 2.39 | 3.2742 (13) | 173 |
Symmetry code: (i) x, y, −z+3/2. |
(pbca) Bis(nitrito-
κN)[tris(2-aminoethyl)amine-
κ4N,
N',
N'',
N''']cobalt(III) chloride
top
Crystal data top
[Co(NO2)2(C6H18N4)]Cl | Dx = 1.822 Mg m−3 |
Mr = 332.64 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 9947 reflections |
a = 16.7032 (6) Å | θ = 3.0–26.4° |
b = 12.0743 (4) Å | µ = 1.65 mm−1 |
c = 12.0288 (4) Å | T = 100 K |
V = 2425.96 (14) Å3 | Block, orange |
Z = 8 | 0.27 × 0.2 × 0.12 mm |
F(000) = 1376 | |
Data collection top
Bruker SMART APEXII area-detector diffractometer | 2277 reflections with I > 2σ(I) |
Mirror optics monochromator | Rint = 0.021 |
0.5° ω and 0.5° φ scans | θmax = 26.4°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS2014; Krause et al., 2015) | h = −20→20 |
Tmin = 0.322, Tmax = 0.430 | k = −15→15 |
49052 measured reflections | l = −15→15 |
2475 independent reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.018 | H-atom parameters constrained |
wR(F2) = 0.056 | w = 1/[σ2(Fo2) + (0.0335P)2 + 0.7351P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.002 |
2475 reflections | Δρmax = 0.44 e Å−3 |
163 parameters | Δρmin = −0.22 e Å−3 |
0 restraints | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Co1 | 0.63574 (2) | 0.36734 (2) | 0.25510 (2) | 0.00590 (7) | |
O1 | 0.64362 (5) | 0.15880 (7) | 0.16448 (7) | 0.01557 (18) | |
O2 | 0.79136 (5) | 0.36189 (7) | 0.16599 (7) | 0.01750 (19) | |
O3 | 0.65149 (5) | 0.15776 (7) | 0.34258 (7) | 0.01518 (18) | |
O4 | 0.79157 (5) | 0.35893 (7) | 0.34358 (7) | 0.01741 (19) | |
N1 | 0.62188 (6) | 0.52908 (9) | 0.25711 (6) | 0.0082 (2) | |
N2 | 0.51891 (6) | 0.35622 (8) | 0.25260 (6) | 0.0088 (2) | |
H2A | 0.5039 | 0.3012 | 0.2053 | 0.011* | |
H2B | 0.5008 | 0.3387 | 0.3217 | 0.011* | |
N3 | 0.63816 (5) | 0.38214 (8) | 0.09294 (8) | 0.00964 (19) | |
H3A | 0.6834 | 0.3498 | 0.0661 | 0.012* | |
H3B | 0.5954 | 0.3461 | 0.0632 | 0.012* | |
N4 | 0.64472 (6) | 0.20922 (9) | 0.25413 (6) | 0.0091 (2) | |
N5 | 0.75374 (7) | 0.36565 (8) | 0.25509 (6) | 0.0104 (2) | |
N6 | 0.63834 (5) | 0.37710 (7) | 0.41703 (8) | 0.00917 (19) | |
H6A | 0.5976 | 0.3361 | 0.4459 | 0.011* | |
H6B | 0.6853 | 0.3485 | 0.4425 | 0.011* | |
C1 | 0.53413 (7) | 0.55850 (9) | 0.25567 (8) | 0.0101 (2) | |
H1A | 0.5258 | 0.6228 | 0.2060 | 0.012* | |
H1B | 0.5172 | 0.5803 | 0.3315 | 0.012* | |
C2 | 0.48252 (6) | 0.46250 (9) | 0.21619 (9) | 0.0122 (2) | |
H2C | 0.4279 | 0.4695 | 0.2475 | 0.015* | |
H2D | 0.4783 | 0.4640 | 0.1341 | 0.015* | |
C3 | 0.66379 (6) | 0.57144 (9) | 0.15573 (8) | 0.0111 (2) | |
H3C | 0.7225 | 0.5655 | 0.1650 | 0.013* | |
H3D | 0.6500 | 0.6501 | 0.1428 | 0.013* | |
C4 | 0.63614 (6) | 0.50079 (9) | 0.05839 (9) | 0.0123 (2) | |
H4A | 0.5811 | 0.5219 | 0.0366 | 0.015* | |
H4B | 0.6719 | 0.5125 | −0.0062 | 0.015* | |
C5 | 0.65963 (6) | 0.56942 (9) | 0.36251 (9) | 0.0104 (2) | |
H5A | 0.6436 | 0.6469 | 0.3775 | 0.012* | |
H5B | 0.7187 | 0.5663 | 0.3567 | 0.012* | |
C6 | 0.63052 (6) | 0.49387 (9) | 0.45511 (9) | 0.0115 (2) | |
H6C | 0.6630 | 0.5057 | 0.5230 | 0.014* | |
H6D | 0.5739 | 0.5105 | 0.4729 | 0.014* | |
Cl1 | 0.47975 (2) | 0.25197 (2) | −0.00029 (2) | 0.01040 (9) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.00676 (11) | 0.00528 (11) | 0.00567 (11) | 0.00004 (5) | −0.00015 (4) | 0.00014 (4) |
O1 | 0.0236 (4) | 0.0114 (4) | 0.0117 (4) | 0.0018 (3) | −0.0020 (3) | −0.0041 (3) |
O2 | 0.0124 (4) | 0.0241 (5) | 0.0159 (4) | 0.0012 (3) | 0.0053 (3) | 0.0023 (3) |
O3 | 0.0221 (4) | 0.0111 (4) | 0.0123 (4) | 0.0020 (3) | −0.0001 (3) | 0.0037 (3) |
O4 | 0.0116 (4) | 0.0246 (5) | 0.0160 (4) | 0.0005 (3) | −0.0052 (3) | −0.0017 (3) |
N1 | 0.0082 (4) | 0.0077 (5) | 0.0086 (5) | −0.0003 (3) | −0.0001 (3) | −0.0002 (3) |
N2 | 0.0100 (5) | 0.0079 (5) | 0.0086 (5) | −0.0001 (4) | −0.0005 (3) | −0.0001 (3) |
N3 | 0.0114 (5) | 0.0097 (4) | 0.0078 (5) | 0.0001 (3) | 0.0001 (3) | 0.0001 (3) |
N4 | 0.0072 (5) | 0.0094 (5) | 0.0106 (5) | 0.0000 (4) | −0.0001 (3) | 0.0005 (3) |
N5 | 0.0108 (5) | 0.0075 (5) | 0.0129 (5) | −0.0009 (3) | −0.0001 (3) | 0.0003 (3) |
N6 | 0.0105 (5) | 0.0087 (4) | 0.0082 (5) | −0.0006 (3) | −0.0003 (3) | 0.0001 (3) |
C1 | 0.0093 (5) | 0.0079 (5) | 0.0130 (5) | 0.0024 (4) | −0.0004 (3) | −0.0002 (3) |
C2 | 0.0108 (5) | 0.0104 (5) | 0.0154 (5) | 0.0015 (4) | −0.0025 (4) | 0.0004 (4) |
C3 | 0.0127 (5) | 0.0094 (5) | 0.0111 (5) | −0.0024 (4) | 0.0026 (4) | 0.0029 (4) |
C4 | 0.0178 (5) | 0.0103 (5) | 0.0087 (5) | 0.0005 (4) | 0.0011 (4) | 0.0024 (4) |
C5 | 0.0117 (5) | 0.0089 (5) | 0.0106 (5) | −0.0024 (4) | −0.0018 (4) | −0.0016 (4) |
C6 | 0.0158 (5) | 0.0106 (5) | 0.0082 (5) | 0.0003 (4) | −0.0009 (4) | −0.0027 (4) |
Cl1 | 0.01074 (15) | 0.01112 (15) | 0.00934 (15) | 0.00040 (8) | 0.00013 (8) | −0.00088 (9) |
Geometric parameters (Å, º) top
Co1—N1 | 1.9667 (11) | N6—H6A | 0.9100 |
Co1—N2 | 1.9563 (11) | N6—H6B | 0.9100 |
Co1—N3 | 1.9591 (10) | N6—C6 | 1.4881 (14) |
Co1—N4 | 1.9151 (11) | C1—H1A | 0.9900 |
Co1—N5 | 1.9712 (11) | C1—H1B | 0.9900 |
Co1—N6 | 1.9519 (10) | C1—C2 | 1.5207 (15) |
O1—N4 | 1.2386 (12) | C2—H2C | 0.9900 |
O2—N5 | 1.2432 (12) | C2—H2D | 0.9900 |
O3—N4 | 1.2373 (12) | C3—H3C | 0.9900 |
O4—N5 | 1.2405 (12) | C3—H3D | 0.9900 |
N1—C1 | 1.5082 (14) | C3—C4 | 1.5205 (15) |
N1—C3 | 1.4962 (13) | C4—H4A | 0.9900 |
N1—C5 | 1.4974 (13) | C4—H4B | 0.9900 |
N2—H2A | 0.9100 | C5—H5A | 0.9900 |
N2—H2B | 0.9100 | C5—H5B | 0.9900 |
N2—C2 | 1.4860 (14) | C5—C6 | 1.5197 (15) |
N3—H3A | 0.9100 | C6—H6C | 0.9900 |
N3—H3B | 0.9100 | C6—H6D | 0.9900 |
N3—C4 | 1.4921 (14) | | |
| | | |
N1—Co1—N5 | 97.35 (4) | H6A—N6—H6B | 108.0 |
N2—Co1—N1 | 87.19 (4) | C6—N6—Co1 | 111.25 (7) |
N2—Co1—N3 | 90.67 (3) | C6—N6—H6A | 109.4 |
N2—Co1—N5 | 175.39 (4) | C6—N6—H6B | 109.4 |
N3—Co1—N1 | 85.65 (4) | N1—C1—H1A | 109.2 |
N3—Co1—N5 | 88.87 (3) | N1—C1—H1B | 109.2 |
N4—Co1—N1 | 177.71 (4) | N1—C1—C2 | 112.03 (9) |
N4—Co1—N2 | 90.55 (4) | H1A—C1—H1B | 107.9 |
N4—Co1—N3 | 94.78 (4) | C2—C1—H1A | 109.2 |
N4—Co1—N5 | 84.91 (4) | C2—C1—H1B | 109.2 |
N4—Co1—N6 | 93.70 (3) | N2—C2—C1 | 109.53 (8) |
N6—Co1—N1 | 86.01 (3) | N2—C2—H2C | 109.8 |
N6—Co1—N2 | 92.39 (3) | N2—C2—H2D | 109.8 |
N6—Co1—N3 | 170.96 (5) | C1—C2—H2C | 109.8 |
N6—Co1—N5 | 88.76 (3) | C1—C2—H2D | 109.8 |
C1—N1—Co1 | 110.37 (7) | H2C—C2—H2D | 108.2 |
C3—N1—Co1 | 105.92 (7) | N1—C3—H3C | 110.3 |
C3—N1—C1 | 111.39 (8) | N1—C3—H3D | 110.3 |
C3—N1—C5 | 112.45 (9) | N1—C3—C4 | 107.09 (8) |
C5—N1—Co1 | 106.49 (7) | H3C—C3—H3D | 108.6 |
C5—N1—C1 | 110.02 (8) | C4—C3—H3C | 110.3 |
Co1—N2—H2A | 109.5 | C4—C3—H3D | 110.3 |
Co1—N2—H2B | 109.5 | N3—C4—C3 | 108.50 (9) |
H2A—N2—H2B | 108.1 | N3—C4—H4A | 110.0 |
C2—N2—Co1 | 110.69 (7) | N3—C4—H4B | 110.0 |
C2—N2—H2A | 109.5 | C3—C4—H4A | 110.0 |
C2—N2—H2B | 109.5 | C3—C4—H4B | 110.0 |
Co1—N3—H3A | 109.4 | H4A—C4—H4B | 108.4 |
Co1—N3—H3B | 109.4 | N1—C5—H5A | 110.3 |
H3A—N3—H3B | 108.0 | N1—C5—H5B | 110.3 |
C4—N3—Co1 | 111.37 (7) | N1—C5—C6 | 106.89 (8) |
C4—N3—H3A | 109.4 | H5A—C5—H5B | 108.6 |
C4—N3—H3B | 109.4 | C6—C5—H5A | 110.3 |
O1—N4—Co1 | 119.62 (7) | C6—C5—H5B | 110.3 |
O3—N4—Co1 | 120.18 (7) | N6—C6—C5 | 108.36 (9) |
O3—N4—O1 | 120.21 (11) | N6—C6—H6C | 110.0 |
O2—N5—Co1 | 120.38 (7) | N6—C6—H6D | 110.0 |
O4—N5—Co1 | 120.66 (7) | C5—C6—H6C | 110.0 |
O4—N5—O2 | 118.68 (11) | C5—C6—H6D | 110.0 |
Co1—N6—H6A | 109.4 | H6C—C6—H6D | 108.4 |
Co1—N6—H6B | 109.4 | | |
| | | |
Co1—N1—C1—C2 | −18.41 (9) | N1—C5—C6—N6 | 46.66 (11) |
Co1—N1—C3—C4 | 48.30 (9) | C1—N1—C3—C4 | −71.73 (11) |
Co1—N1—C5—C6 | −46.48 (9) | C1—N1—C5—C6 | 73.14 (11) |
Co1—N2—C2—C1 | −32.84 (10) | C3—N1—C1—C2 | 98.96 (10) |
Co1—N3—C4—C3 | 20.92 (10) | C3—N1—C5—C6 | −162.06 (8) |
Co1—N6—C6—C5 | −24.92 (10) | C5—N1—C1—C2 | −135.64 (9) |
N1—C1—C2—N2 | 33.37 (11) | C5—N1—C3—C4 | 164.23 (8) |
N1—C3—C4—N3 | −45.28 (11) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···Cl1 | 0.91 | 2.58 | 3.3564 (8) | 144 |
N2—H2B···Cl1i | 0.91 | 2.43 | 3.3121 (8) | 163 |
N3—H3A···O2 | 0.91 | 2.17 | 2.7165 (12) | 118 |
N3—H3B···Cl1 | 0.91 | 2.37 | 3.2756 (9) | 176 |
N6—H6A···Cl1i | 0.91 | 2.33 | 3.2305 (9) | 170 |
N6—H6B···O4 | 0.91 | 2.14 | 2.7165 (12) | 120 |
Symmetry code: (i) x, −y+1/2, z+1/2. |
(a2) Bis(nitrito-
κN)[tris(2-aminoethyl)amine-
κ4N,
N',
N'',
N''']cobalt(III) chloride
top
Crystal data top
[Co(NO2)2(C6H18N4)]Cl | F(000) = 688 |
Mr = 332.64 | Dx = 1.777 Mg m−3 |
Monoclinic, A2 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.856 (4) Å | Cell parameters from 4064 reflections |
b = 11.950 (5) Å | θ = 3.4–26.2° |
c = 11.750 (4) Å | µ = 1.61 mm−1 |
β = 90.000 (13)° | T = 100 K |
V = 1243.5 (8) Å3 | Block, orange |
Z = 4 | 0.4 × 0.3 × 0.2 mm |
Data collection top
Bruker SMART APEXII area-detector diffractometer | 2533 independent reflections |
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs | 2418 reflections with I > 2σ(I) |
Mirror optics monochromator | Rint = 0.053 |
Detector resolution: 7.9 pixels mm-1 | θmax = 26.3°, θmin = 2.3° |
0.5\ ω and 0.5\ φ scans | h = −10→11 |
Absorption correction: multi-scan (SADABS2014; Krause et al., 2015) | k = −14→14 |
Tmin = 0.671, Tmax = 0.745 | l = −14→14 |
10969 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.070 | w = 1/[σ2(Fo2) + (0.0366P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
2533 reflections | Δρmax = 0.45 e Å−3 |
165 parameters | Δρmin = −0.72 e Å−3 |
1 restraint | Absolute structure: Twinning involves inversion, so Flack parameter cannot be determined |
Special details top
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. Refined as a 2-component inversion twin. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Co1 | 0.28312 (9) | 0.62203 (5) | 0.25609 (10) | 0.00941 (18) | |
O1 | 0.2855 (7) | 0.4024 (5) | 0.1906 (5) | 0.0273 (15) | |
O2 | 0.5810 (8) | 0.6161 (5) | 0.1684 (4) | 0.0203 (14) | |
O3 | 0.3526 (7) | 0.4253 (4) | 0.3640 (5) | 0.0215 (14) | |
O4 | 0.5745 (7) | 0.6384 (5) | 0.3492 (4) | 0.0202 (14) | |
N1 | 0.2418 (6) | 0.7837 (4) | 0.2434 (6) | 0.0120 (10) | |
N2 | 0.0638 (5) | 0.6011 (3) | 0.2563 (7) | 0.0096 (12) | |
H2A | 0.0324 | 0.5812 | 0.1854 | 0.011* | |
H2B | 0.0389 | 0.5450 | 0.3052 | 0.011* | |
N3 | 0.2935 (10) | 0.6210 (6) | 0.0915 (4) | 0.0129 (14) | |
H3A | 0.3874 | 0.5993 | 0.0692 | 0.016* | |
H3B | 0.2259 | 0.5706 | 0.0637 | 0.016* | |
N4 | 0.3107 (6) | 0.4635 (5) | 0.2721 (5) | 0.0125 (14) | |
N5 | 0.5059 (5) | 0.6297 (4) | 0.2587 (7) | 0.0128 (11) | |
N6 | 0.2800 (10) | 0.6479 (5) | 0.4204 (4) | 0.0107 (14) | |
H6A | 0.1989 | 0.6124 | 0.4513 | 0.013* | |
H6B | 0.3649 | 0.6185 | 0.4521 | 0.013* | |
C1 | 0.0740 (6) | 0.8054 (5) | 0.2453 (8) | 0.0137 (12) | |
H1A | 0.0390 | 0.8219 | 0.1671 | 0.016* | |
H1B | 0.0532 | 0.8719 | 0.2930 | 0.016* | |
C2 | −0.0139 (8) | 0.7062 (6) | 0.2916 (6) | 0.0136 (15) | |
H2C | −0.0189 | 0.7104 | 0.3757 | 0.016* | |
H2D | −0.1182 | 0.7072 | 0.2615 | 0.016* | |
C3 | 0.3066 (11) | 0.8199 (6) | 0.1312 (7) | 0.0144 (19) | |
H3C | 0.4180 | 0.8245 | 0.1360 | 0.017* | |
H3D | 0.2669 | 0.8944 | 0.1098 | 0.017* | |
C4 | 0.2602 (11) | 0.7331 (6) | 0.0438 (6) | 0.0156 (19) | |
H4A | 0.1510 | 0.7398 | 0.0269 | 0.019* | |
H4B | 0.3171 | 0.7444 | −0.0278 | 0.019* | |
C5 | 0.3176 (11) | 0.8366 (7) | 0.3423 (6) | 0.017 (2) | |
H5A | 0.2857 | 0.9157 | 0.3497 | 0.020* | |
H5B | 0.4286 | 0.8345 | 0.3325 | 0.020* | |
C6 | 0.2716 (12) | 0.7707 (6) | 0.4475 (5) | 0.0131 (17) | |
H6C | 0.3402 | 0.7886 | 0.5115 | 0.016* | |
H6D | 0.1675 | 0.7910 | 0.4702 | 0.016* | |
Cl1 | 0.0000 | 0.4971 (2) | 0.0000 | 0.0158 (7) | |
Cl2 | 0.0000 | 0.4871 (2) | 0.5000 | 0.0128 (6) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0102 (3) | 0.0061 (3) | 0.0119 (4) | 0.0005 (4) | 0.0004 (6) | 0.0001 (6) |
O1 | 0.041 (4) | 0.012 (2) | 0.029 (3) | 0.007 (3) | −0.010 (3) | −0.004 (3) |
O2 | 0.017 (3) | 0.025 (3) | 0.019 (3) | 0.004 (3) | 0.007 (2) | 0.001 (3) |
O3 | 0.035 (4) | 0.011 (3) | 0.018 (3) | 0.008 (3) | 0.001 (3) | 0.004 (2) |
O4 | 0.015 (3) | 0.026 (3) | 0.019 (3) | −0.004 (3) | −0.005 (2) | −0.001 (2) |
N1 | 0.015 (2) | 0.011 (2) | 0.010 (3) | −0.001 (2) | 0.002 (3) | −0.004 (3) |
N2 | 0.014 (2) | 0.006 (3) | 0.009 (3) | 0.0013 (17) | 0.005 (4) | −0.003 (3) |
N3 | 0.012 (3) | 0.010 (3) | 0.017 (3) | −0.002 (3) | 0.002 (3) | 0.000 (3) |
N4 | 0.012 (3) | 0.010 (3) | 0.016 (4) | −0.001 (2) | 0.003 (3) | −0.002 (3) |
N5 | 0.016 (2) | 0.007 (2) | 0.015 (3) | −0.001 (3) | 0.005 (3) | 0.003 (3) |
N6 | 0.011 (3) | 0.008 (3) | 0.012 (3) | −0.001 (3) | −0.002 (3) | −0.002 (2) |
C1 | 0.016 (3) | 0.012 (3) | 0.013 (3) | 0.005 (2) | 0.002 (5) | 0.000 (4) |
C2 | 0.013 (3) | 0.010 (3) | 0.018 (4) | 0.003 (3) | 0.002 (3) | −0.002 (2) |
C3 | 0.013 (5) | 0.011 (3) | 0.019 (4) | −0.002 (3) | 0.003 (4) | 0.005 (3) |
C4 | 0.020 (5) | 0.013 (4) | 0.014 (4) | 0.004 (4) | 0.002 (3) | −0.002 (3) |
C5 | 0.024 (6) | 0.014 (4) | 0.011 (4) | −0.003 (4) | 0.004 (4) | −0.005 (3) |
C6 | 0.019 (4) | 0.006 (3) | 0.015 (4) | 0.000 (3) | −0.004 (3) | −0.004 (3) |
Cl1 | 0.0193 (18) | 0.0139 (13) | 0.0143 (13) | 0.000 | −0.0017 (14) | 0.000 |
Cl2 | 0.0144 (17) | 0.0118 (13) | 0.0121 (12) | 0.000 | 0.0018 (13) | 0.000 |
Geometric parameters (Å, º) top
Co1—N1 | 1.972 (5) | N6—H6A | 0.9100 |
Co1—N2 | 1.959 (5) | N6—H6B | 0.9100 |
Co1—N3 | 1.936 (5) | N6—C6 | 1.503 (8) |
Co1—N4 | 1.919 (6) | C1—H1A | 0.9900 |
Co1—N5 | 1.975 (5) | C1—H1B | 0.9900 |
Co1—N6 | 1.956 (5) | C1—C2 | 1.518 (9) |
O1—N4 | 1.225 (8) | C2—H2C | 0.9900 |
O2—N5 | 1.263 (9) | C2—H2D | 0.9900 |
O3—N4 | 1.230 (8) | C3—H3C | 0.9900 |
O4—N5 | 1.229 (9) | C3—H3D | 0.9900 |
N1—C1 | 1.509 (7) | C3—C4 | 1.517 (10) |
N1—C3 | 1.502 (10) | C4—H4A | 0.9900 |
N1—C5 | 1.484 (10) | C4—H4B | 0.9900 |
N2—H2A | 0.9100 | C5—H5A | 0.9900 |
N2—H2B | 0.9100 | C5—H5B | 0.9900 |
N2—C2 | 1.490 (8) | C5—C6 | 1.521 (10) |
N3—H3A | 0.9100 | C6—H6C | 0.9900 |
N3—H3B | 0.9100 | C6—H6D | 0.9900 |
N3—C4 | 1.481 (10) | | |
| | | |
N1—Co1—N5 | 98.1 (2) | H6A—N6—H6B | 108.0 |
N2—Co1—N1 | 86.60 (19) | C6—N6—Co1 | 111.4 (4) |
N2—Co1—N5 | 175.2 (2) | C6—N6—H6A | 109.4 |
N3—Co1—N1 | 86.5 (3) | C6—N6—H6B | 109.4 |
N3—Co1—N2 | 92.7 (4) | N1—C1—H1A | 109.2 |
N3—Co1—N5 | 88.2 (4) | N1—C1—H1B | 109.2 |
N3—Co1—N6 | 171.1 (3) | N1—C1—C2 | 112.1 (5) |
N4—Co1—N1 | 176.4 (3) | H1A—C1—H1B | 107.9 |
N4—Co1—N2 | 90.0 (2) | C2—C1—H1A | 109.2 |
N4—Co1—N3 | 94.9 (3) | C2—C1—H1B | 109.2 |
N4—Co1—N5 | 85.2 (2) | N2—C2—C1 | 108.7 (5) |
N4—Co1—N6 | 93.5 (3) | N2—C2—H2C | 109.9 |
N6—Co1—N1 | 85.2 (3) | N2—C2—H2D | 109.9 |
N6—Co1—N2 | 90.3 (4) | C1—C2—H2C | 109.9 |
N6—Co1—N5 | 89.5 (4) | C1—C2—H2D | 109.9 |
C1—N1—Co1 | 110.5 (4) | H2C—C2—H2D | 108.3 |
C3—N1—Co1 | 106.1 (4) | N1—C3—H3C | 110.3 |
C3—N1—C1 | 109.9 (7) | N1—C3—H3D | 110.3 |
C5—N1—Co1 | 105.9 (5) | N1—C3—C4 | 107.1 (6) |
C5—N1—C1 | 111.2 (7) | H3C—C3—H3D | 108.6 |
C5—N1—C3 | 113.1 (6) | C4—C3—H3C | 110.3 |
Co1—N2—H2A | 109.5 | C4—C3—H3D | 110.3 |
Co1—N2—H2B | 109.5 | N3—C4—C3 | 107.9 (6) |
H2A—N2—H2B | 108.1 | N3—C4—H4A | 110.1 |
C2—N2—Co1 | 110.5 (4) | N3—C4—H4B | 110.1 |
C2—N2—H2A | 109.5 | C3—C4—H4A | 110.1 |
C2—N2—H2B | 109.5 | C3—C4—H4B | 110.1 |
Co1—N3—H3A | 109.4 | H4A—C4—H4B | 108.4 |
Co1—N3—H3B | 109.4 | N1—C5—H5A | 110.3 |
H3A—N3—H3B | 108.0 | N1—C5—H5B | 110.3 |
C4—N3—Co1 | 111.3 (5) | N1—C5—C6 | 107.1 (7) |
C4—N3—H3A | 109.4 | H5A—C5—H5B | 108.5 |
C4—N3—H3B | 109.4 | C6—C5—H5A | 110.3 |
O1—N4—Co1 | 119.2 (5) | C6—C5—H5B | 110.3 |
O1—N4—O3 | 121.3 (6) | N6—C6—C5 | 108.7 (6) |
O3—N4—Co1 | 119.5 (5) | N6—C6—H6C | 110.0 |
O2—N5—Co1 | 120.5 (5) | N6—C6—H6D | 110.0 |
O4—N5—Co1 | 120.8 (6) | C5—C6—H6C | 110.0 |
O4—N5—O2 | 118.5 (5) | C5—C6—H6D | 110.0 |
Co1—N6—H6A | 109.4 | H6C—C6—H6D | 108.3 |
Co1—N6—H6B | 109.4 | | |
| | | |
Co1—N1—C1—C2 | 17.5 (9) | N1—C5—C6—N6 | 43.7 (10) |
Co1—N1—C3—C4 | 44.9 (7) | C1—N1—C3—C4 | −74.6 (7) |
Co1—N1—C5—C6 | −49.3 (7) | C1—N1—C5—C6 | 70.8 (8) |
Co1—N2—C2—C1 | 35.6 (8) | C3—N1—C1—C2 | 134.2 (7) |
Co1—N3—C4—C3 | 28.4 (9) | C3—N1—C5—C6 | −165.1 (7) |
Co1—N6—C6—C5 | −17.7 (10) | C5—N1—C1—C2 | −99.9 (7) |
N1—C1—C2—N2 | −34.4 (9) | C5—N1—C3—C4 | 160.6 (7) |
N1—C3—C4—N3 | −48.1 (9) | | |
Selected metric parameters (Å, °) of the
[Co(NO2)2(tren)]+ cation in Forms I–III and in the
DFT-optimized geometry of [Co(NO2)2(tren)]Cl top | Form I (Pcmb) (Chin et al., 1990) | Form I (Pbcm) | Form II (Pbca) | Form III (A2) | DFT of [Co(NO2)2(tren)]+ |
Co1—N1 | 1.963 (3) | 1.9653 (17) | 1.9667 (11) | 1.972 (5) | 2.013 |
Co1—N2 | 1.943 (4) | 1.9570 (16) | 1.9563 (11) | 1.959 (5) | 1.993 |
Co1—N3 | 1.950 (2) | 1.9517 (12) | 1.9591 (10) | 1.936 (5) | 1.988 |
Co1—N4 | 1.909 (3) | 1.9141 (16) | 1.9151 (11) | 1.919 (6) | 1.929 |
Co1—N5 | 1.955 (4) | 1.9716 (18) | 1.9712 (11) | 1.975 (5) | 2.014 |
Co1—N6 | | | 1.9519 (10) | 1.956 (5) | 1.987 |
| | | | | |
Dihedral angles | | | | | |
O1/O3/N4—NCoN | 90 | 90 | 93.51 (3) | 107.4 (3) | 126.6 |
O2/O4/N5—NCoN | 90 | 90 | 90.60 (4) | 91.6 (3) | 96.2 |
Metric parameters (Å, °) of the hydrogen-bonding
interactions observed in Forms I–III of
[Co(NO2)2(tren)]Cl topD—H···A | D—H | H···A | D···A | D—H···A |
Form I (space group Pbcm) | | | | |
N2—H2A···Cl1 | 0.89 | 2.56 | 3.3382 (8) | 147 |
N2—H2B···Cl1i | 0.89 | 2.46 | 3.3382 (7) | 168 |
N3—H3A···O2 | 0.89 | 2.16 | 2.7151 (18) | 120 |
N3—H3B···Cl1 | 0.89 | 2.39 | 3.2742 (13) | 173 |
| | | | |
Form II (space group Pbca) | | | | |
N2—H2A···Cl1 | 0.91 | 2.58 | 3.3564 (8) | 144 |
N2—H2B···Cl1ii | 0.91 | 2.43 | 3.3121 (8) | 163 |
N3—H3A···O2 | 0.91 | 2.17 | 2.7165 (12) | 118 |
N3—H3B···Cl1 | 0.91 | 2.37 | 3.2756 (9) | 176 |
N6—H6A···Cl1ii | 0.91 | 2.33 | 3.2305 (9) | 170 |
N6—H6B···O4 | 0.91 | 2.14 | 2.7165 (12) | 120 |
| | | | |
Form III (space group A2) | | | | |
N2—H2A···Cl1 | 0.91 | 2.42 | 3.307 (8) | 166 |
N2—H2B···Cl2 | 0.91 | 2.42 | 3.220 (8) | 148 |
N3—H3A···O2 | 0.91 | 2.08 | 2.703 (10) | 124 |
N3—H3B···Cl1 | 0.91 | 2.31 | 3.178 (8) | 160 |
N6—H6A···Cl2 | 0.91 | 2.38 | 3.274 (8) | 167 |
N6—H6B···O4iii | 0.91 | 2.41 | 3.001 (8) | 123 |
Symmetry codes: (i) x, y, -z+3/2;
(ii) x, -y+1/2, z+1/2;
(iii) -x+1, y, -z+1. |