The salt (ferrocenylmethyl)trimethylammonium iodide, [Fe(C5H5)(C9H15N)]I, is used in an established procedure to attach ferrocenylmethyl frameworks to secondary amines. The title salt, [Fe(C5H5)(C9H15N)]I3, obtained by diffusion of Et2O vapour into a CH2Cl2 solution containing equimolar [Fe(C5H5)(C9H15N)]I and I2, shows the expected cation balanced by an asymmetric but isolated triiodide counteranion [I-I = 3.0006 (4) and 2.8728 (4) Å].
Supporting information
CCDC reference: 231806
Key indicators
- Single-crystal X-ray study
- T = 150 K
- R factor = 0.026
- wR factor = 0.062
- Data-to-parameter ratio = 25.4
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT250_ALERT_2_C Large U3/U1 ratio for average U(i,j) tensor .... 2.80
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
1 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
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT and SHELXTL (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: enCIFer (CCDC, 2003) and PLATON (Spek, 2003).
(Ferrocenylmethyl)trimethylammonium triiodide
top
Crystal data top
[Fe(C5H5)(C9H15N)]I3 | F(000) = 1184 |
Mr = 638.86 | Dx = 2.228 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 7671 reflections |
a = 11.6959 (9) Å | θ = 2.3–27.6° |
b = 10.6136 (9) Å | µ = 5.64 mm−1 |
c = 15.3474 (12) Å | T = 150 K |
β = 91.638 (2)° | Block, red |
V = 1904.4 (3) Å3 | 0.50 × 0.36 × 0.30 mm |
Z = 4 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 4393 independent reflections |
Radiation source: normal-focus sealed tube | 3925 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
ω scans | θmax = 27.6°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −15→14 |
Tmin = 0.064, Tmax = 0.180 | k = −13→12 |
13480 measured reflections | l = −20→19 |
Refinement top
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)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.062 | w = 1/[σ2(Fo2) + (0.029P)2 + 2.356P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
4393 reflections | Δρmax = 1.08 e Å−3 |
173 parameters | Δρmin = −1.18 e Å−3 |
113 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00106 (8) |
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 | |
Fe | 0.57586 (4) | 0.41067 (4) | 0.25079 (2) | 0.01770 (10) | |
C1 | 0.4474 (3) | 0.3846 (3) | 0.16064 (17) | 0.0184 (6) | |
C2 | 0.5574 (3) | 0.3775 (3) | 0.12134 (18) | 0.0235 (6) | |
H2 | 0.5886 | 0.3037 | 0.0892 | 0.028* | |
C3 | 0.6139 (3) | 0.4952 (3) | 0.1362 (2) | 0.0287 (7) | |
H3 | 0.6922 | 0.5178 | 0.1170 | 0.034* | |
C4 | 0.5408 (3) | 0.5734 (3) | 0.1841 (2) | 0.0315 (7) | |
H4 | 0.5592 | 0.6605 | 0.2050 | 0.038* | |
C5 | 0.4381 (3) | 0.5074 (3) | 0.1987 (2) | 0.0243 (6) | |
H5 | 0.3716 | 0.5396 | 0.2317 | 0.029* | |
C6 | 0.5635 (3) | 0.2764 (4) | 0.3459 (2) | 0.0351 (8) | |
H6 | 0.5019 | 0.2116 | 0.3500 | 0.042* | |
C7 | 0.6673 (3) | 0.2630 (4) | 0.3009 (2) | 0.0371 (8) | |
H7 | 0.6908 | 0.1867 | 0.2676 | 0.044* | |
C8 | 0.7307 (3) | 0.3744 (4) | 0.3096 (2) | 0.0387 (9) | |
H8 | 0.8074 | 0.3913 | 0.2848 | 0.046* | |
C9 | 0.6666 (3) | 0.4582 (4) | 0.3613 (2) | 0.0403 (9) | |
H9 | 0.6899 | 0.5454 | 0.3790 | 0.048* | |
C10 | 0.5626 (3) | 0.3968 (4) | 0.3829 (2) | 0.0384 (9) | |
H10 | 0.5003 | 0.4333 | 0.4184 | 0.046* | |
N12 | 0.2867 (2) | 0.2681 (3) | 0.08344 (16) | 0.0237 (6) | |
C11 | 0.3607 (3) | 0.2830 (3) | 0.16649 (18) | 0.0217 (6) | |
H11A | 0.3105 | 0.3013 | 0.2158 | 0.026* | |
H11B | 0.4002 | 0.2023 | 0.1791 | 0.026* | |
C13 | 0.1944 (3) | 0.1737 (3) | 0.1018 (2) | 0.0315 (8) | |
H13A | 0.1455 | 0.1623 | 0.0494 | 0.047* | |
H13B | 0.1481 | 0.2044 | 0.1496 | 0.047* | |
H13C | 0.2294 | 0.0929 | 0.1182 | 0.047* | |
C14 | 0.3576 (3) | 0.2202 (4) | 0.0107 (2) | 0.0369 (8) | |
H14A | 0.3095 | 0.2109 | −0.0422 | 0.055* | |
H14B | 0.3904 | 0.1382 | 0.0269 | 0.055* | |
H14C | 0.4194 | 0.2800 | −0.0001 | 0.055* | |
C15 | 0.2323 (3) | 0.3907 (3) | 0.0578 (2) | 0.0311 (8) | |
H15A | 0.1853 | 0.3790 | 0.0046 | 0.047* | |
H15B | 0.2919 | 0.4533 | 0.0474 | 0.047* | |
H15C | 0.1839 | 0.4200 | 0.1049 | 0.047* | |
I1 | 0.57558 (2) | 0.08364 (2) | −0.202225 (17) | 0.03604 (8) | |
I2 | 0.733082 (18) | 0.20712 (2) | −0.070191 (13) | 0.02773 (7) | |
I3 | 0.88581 (2) | 0.31936 (3) | 0.057543 (16) | 0.03910 (8) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Fe | 0.0160 (2) | 0.0243 (2) | 0.01252 (18) | 0.00239 (16) | −0.00494 (15) | −0.00021 (15) |
C1 | 0.0202 (14) | 0.0222 (14) | 0.0125 (12) | 0.0032 (11) | −0.0050 (10) | 0.0003 (11) |
C2 | 0.0229 (15) | 0.0344 (17) | 0.0131 (12) | 0.0061 (13) | −0.0025 (11) | −0.0013 (12) |
C3 | 0.0256 (16) | 0.0373 (19) | 0.0231 (14) | −0.0037 (14) | −0.0033 (12) | 0.0122 (13) |
C4 | 0.0332 (18) | 0.0236 (16) | 0.0369 (17) | 0.0002 (14) | −0.0115 (15) | 0.0073 (13) |
C5 | 0.0225 (15) | 0.0246 (16) | 0.0254 (14) | 0.0071 (12) | −0.0079 (12) | −0.0042 (12) |
C6 | 0.0342 (18) | 0.046 (2) | 0.0243 (15) | −0.0063 (16) | −0.0121 (14) | 0.0163 (14) |
C7 | 0.039 (2) | 0.043 (2) | 0.0280 (16) | 0.0157 (16) | −0.0131 (15) | 0.0068 (15) |
C8 | 0.0179 (15) | 0.071 (3) | 0.0267 (16) | 0.0015 (16) | −0.0113 (13) | 0.0154 (17) |
C9 | 0.046 (2) | 0.051 (2) | 0.0229 (15) | −0.0084 (18) | −0.0211 (15) | −0.0014 (15) |
C10 | 0.0369 (19) | 0.063 (2) | 0.0146 (13) | 0.0048 (18) | −0.0078 (13) | 0.0006 (15) |
N12 | 0.0231 (13) | 0.0286 (14) | 0.0187 (12) | −0.0020 (11) | −0.0121 (10) | 0.0032 (10) |
C11 | 0.0234 (15) | 0.0271 (16) | 0.0140 (12) | 0.0001 (12) | −0.0095 (11) | 0.0021 (11) |
C13 | 0.0296 (18) | 0.0293 (17) | 0.0346 (17) | −0.0066 (14) | −0.0161 (14) | 0.0049 (14) |
C14 | 0.043 (2) | 0.048 (2) | 0.0186 (15) | −0.0024 (18) | −0.0062 (14) | −0.0087 (14) |
C15 | 0.0320 (18) | 0.0308 (18) | 0.0296 (16) | 0.0018 (14) | −0.0149 (14) | 0.0120 (14) |
I1 | 0.02726 (13) | 0.03188 (13) | 0.04844 (15) | 0.00596 (9) | −0.00824 (10) | 0.00393 (10) |
I2 | 0.02294 (11) | 0.02951 (12) | 0.03092 (12) | 0.00938 (8) | 0.00389 (8) | 0.00381 (8) |
I3 | 0.02922 (13) | 0.04378 (15) | 0.04403 (14) | 0.00875 (10) | −0.00385 (10) | −0.00688 (11) |
Geometric parameters (Å, º) top
Fe—C1 | 2.032 (3) | C8—H8 | 1.0000 |
Fe—C2 | 2.023 (3) | C9—C10 | 1.427 (6) |
Fe—C3 | 2.034 (3) | C9—H9 | 1.0000 |
Fe—C4 | 2.043 (3) | C10—H10 | 1.0000 |
Fe—C5 | 2.053 (3) | C10—C6 | 1.399 (6) |
Fe—C6 | 2.048 (3) | C1—C11 | 1.486 (4) |
Fe—C7 | 2.036 (3) | C11—H11A | 0.9900 |
Fe—C8 | 2.037 (3) | C11—H11B | 0.9900 |
Fe—C9 | 2.038 (3) | C11—N12 | 1.528 (3) |
Fe—C10 | 2.044 (3) | N12—C15 | 1.496 (4) |
C1—C2 | 1.438 (4) | N12—C14 | 1.499 (4) |
C2—C3 | 1.428 (5) | N12—C13 | 1.505 (4) |
C2—H2 | 1.0000 | C13—H13A | 0.9800 |
C3—C4 | 1.412 (5) | C13—H13B | 0.9800 |
C3—H3 | 1.0000 | C13—H13C | 0.9800 |
C4—C5 | 1.415 (5) | C14—H14A | 0.9800 |
C4—H4 | 1.0000 | C14—H14B | 0.9800 |
C5—H5 | 1.0000 | C14—H14C | 0.9800 |
C5—C1 | 1.433 (4) | C15—H15A | 0.9800 |
C6—C7 | 1.421 (5) | C15—H15B | 0.9800 |
C6—H6 | 1.0000 | C15—H15C | 0.9800 |
C7—C8 | 1.400 (6) | I1—I2 | 3.0006 (4) |
C7—H7 | 1.0000 | I2—I3 | 2.8728 (4) |
C8—C9 | 1.420 (6) | | |
| | | |
I3···C15i | 3.791 (3) | I1···H13Civ | 3.19 |
I1···H4i | 3.14 | I1···H15Ciii | 3.25 |
I1···H8ii | 3.15 | I2···H2 | 3.18 |
I1···H11Aiii | 3.29 | I2···H13Civ | 3.30 |
I1···H11Biv | 3.07 | I3···H3 | 3.24 |
I1···H13Biii | 3.33 | I3···H9v | 3.20 |
| | | |
C2—Fe—C1 | 41.56 (12) | Fe—C4—H4 | 125.6 |
C2—Fe—C3 | 41.22 (14) | C4—C5—C1 | 108.1 (3) |
C1—Fe—C3 | 69.33 (12) | C4—C5—Fe | 69.42 (18) |
C2—Fe—C7 | 106.07 (14) | C1—C5—Fe | 68.65 (16) |
C1—Fe—C7 | 121.51 (14) | C4—C5—H5 | 125.9 |
C3—Fe—C7 | 122.72 (15) | C1—C5—H5 | 125.9 |
C2—Fe—C8 | 118.07 (14) | Fe—C5—H5 | 125.9 |
C1—Fe—C8 | 155.05 (15) | C10—C6—C7 | 107.8 (3) |
C3—Fe—C8 | 104.64 (14) | C10—C6—Fe | 69.9 (2) |
C7—Fe—C8 | 40.22 (17) | C7—C6—Fe | 69.2 (2) |
C2—Fe—C9 | 153.98 (15) | C10—C6—H6 | 126.1 |
C1—Fe—C9 | 163.23 (15) | C7—C6—H6 | 126.1 |
C3—Fe—C9 | 119.26 (15) | Fe—C6—H6 | 126.1 |
C7—Fe—C9 | 67.72 (16) | C8—C7—C6 | 109.1 (4) |
C8—Fe—C9 | 40.80 (17) | C8—C7—Fe | 69.9 (2) |
C2—Fe—C4 | 68.96 (14) | C6—C7—Fe | 70.1 (2) |
C1—Fe—C4 | 68.90 (13) | C8—C7—H7 | 125.5 |
C3—Fe—C4 | 40.52 (15) | C6—C7—H7 | 125.5 |
C7—Fe—C4 | 159.33 (16) | Fe—C7—H7 | 125.5 |
C8—Fe—C4 | 123.00 (16) | C7—C8—C9 | 107.2 (3) |
C9—Fe—C4 | 107.45 (16) | C7—C8—Fe | 69.85 (19) |
C2—Fe—C10 | 162.37 (15) | C9—C8—Fe | 69.65 (19) |
C1—Fe—C10 | 126.19 (14) | C7—C8—H8 | 126.4 |
C3—Fe—C10 | 156.07 (16) | C9—C8—H8 | 126.4 |
C7—Fe—C10 | 67.90 (16) | Fe—C8—H8 | 126.4 |
C8—Fe—C10 | 68.80 (15) | C8—C9—C10 | 108.1 (4) |
C9—Fe—C10 | 40.91 (16) | C8—C9—Fe | 69.55 (19) |
C4—Fe—C10 | 122.56 (16) | C10—C9—Fe | 69.76 (19) |
C2—Fe—C6 | 124.81 (15) | C8—C9—H9 | 125.9 |
C1—Fe—C6 | 108.95 (13) | C10—C9—H9 | 125.9 |
C3—Fe—C6 | 160.81 (16) | Fe—C9—H9 | 125.9 |
C7—Fe—C6 | 40.72 (15) | C6—C10—C9 | 107.8 (4) |
C8—Fe—C6 | 68.45 (15) | C6—C10—Fe | 70.16 (19) |
C9—Fe—C6 | 67.96 (16) | C9—C10—Fe | 69.33 (19) |
C4—Fe—C6 | 158.14 (16) | C6—C10—H10 | 126.1 |
C10—Fe—C6 | 39.99 (16) | C9—C10—H10 | 126.1 |
C2—Fe—C5 | 69.17 (12) | Fe—C10—H10 | 126.1 |
C1—Fe—C5 | 41.08 (12) | C15—N12—C14 | 109.9 (3) |
C3—Fe—C5 | 68.38 (13) | C15—N12—C13 | 109.0 (3) |
C7—Fe—C5 | 158.42 (15) | C14—N12—C13 | 109.2 (3) |
C8—Fe—C5 | 160.89 (16) | C15—N12—C11 | 110.8 (2) |
C9—Fe—C5 | 125.76 (15) | C14—N12—C11 | 110.1 (2) |
C4—Fe—C5 | 40.40 (14) | C13—N12—C11 | 107.8 (2) |
C10—Fe—C5 | 109.96 (14) | C1—C11—N12 | 113.3 (2) |
C6—Fe—C5 | 123.70 (14) | C1—C11—H11A | 108.9 |
C5—C1—C2 | 107.4 (3) | N12—C11—H11A | 108.9 |
C5—C1—C11 | 125.1 (3) | C1—C11—H11B | 108.9 |
C2—C1—C11 | 127.4 (3) | N12—C11—H11B | 108.9 |
C5—C1—Fe | 70.28 (16) | H11A—C11—H11B | 107.7 |
C2—C1—Fe | 68.91 (16) | N12—C13—H13A | 109.5 |
C11—C1—Fe | 123.41 (19) | N12—C13—H13B | 109.5 |
C3—C2—C1 | 107.5 (3) | H13A—C13—H13B | 109.5 |
C3—C2—Fe | 69.81 (17) | N12—C13—H13C | 109.5 |
C1—C2—Fe | 69.54 (15) | H13A—C13—H13C | 109.5 |
C3—C2—H2 | 126.2 | H13B—C13—H13C | 109.5 |
C1—C2—H2 | 126.2 | N12—C14—H14A | 109.5 |
Fe—C2—H2 | 126.2 | N12—C14—H14B | 109.5 |
C4—C3—C2 | 108.3 (3) | H14A—C14—H14B | 109.5 |
C4—C3—Fe | 70.08 (19) | N12—C14—H14C | 109.5 |
C2—C3—Fe | 68.97 (17) | H14A—C14—H14C | 109.5 |
C4—C3—H3 | 125.9 | H14B—C14—H14C | 109.5 |
C2—C3—H3 | 125.9 | N12—C15—H15A | 109.5 |
Fe—C3—H3 | 125.9 | N12—C15—H15B | 109.5 |
C3—C4—C5 | 108.7 (3) | H15A—C15—H15B | 109.5 |
C3—C4—Fe | 69.40 (19) | N12—C15—H15C | 109.5 |
C5—C4—Fe | 70.18 (18) | H15A—C15—H15C | 109.5 |
C3—C4—H4 | 125.6 | H15B—C15—H15C | 109.5 |
C5—C4—H4 | 125.6 | I1—I2—I3 | 178.600 (10) |
| | | |
C5—C1—C11—N12 | 102.1 (3) | C14—N12—C11—C1 | 67.6 (3) |
C2—C1—C11—N12 | −81.8 (4) | C13—N12—C11—C1 | −173.4 (3) |
C15—N12—C11—C1 | −54.2 (4) | | |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1/2, −y+1/2, z−1/2; (iii) x+1/2, −y+1/2, z−1/2; (iv) −x+1, −y, −z; (v) −x+3/2, y−1/2, −z+1/2. |