Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100012129/qa0379sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100012129/qa0379Isup2.hkl |
CCDC reference: 152654
Colourless transparent needles of (I) were found as an impurity amongst the main yellow product 4-(dimethylamino)pyridinium tetrachlorocuprate(II) (Haddad & Willett, 2000). The source of tin was apparently a corroding spatula. The reaction medium contained 5 mmol CuCl2·2H2O and 5 mmol of 4-(dimethylamino)pyridine in 20 ml 3 M HCl. The medium was heated at 348 K for 5 min. Yellow crystals of the copper(II) compound developed in two days together with few colourless crystals of the title compound of tin(IV).
All H atoms were located from a difference Fourier and were refined isotropically.
Data collection: SMART (Bruker, 1996); cell refinement: SAINT (Bruker, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.
(C7H11N2)2[SnCl6] | F(000) = 572 |
Mr = 577.74 | Dx = 1.758 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.3328 (17) Å | Cell parameters from 4787 reflections |
b = 11.680 (2) Å | θ = 2.0–28.2° |
c = 11.724 (2) Å | µ = 1.91 mm−1 |
β = 106.92 (3)° | T = 293 K |
V = 1091.7 (4) Å3 | Parallelepiped, colourless |
Z = 2 | 0.4 × 0.2 × 0.15 mm |
Siemens SMART 1000 diffractometer | 1854 independent reflections |
Radiation source: normal-focus sealed tube | 1629 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ω scans | θmax = 24.7°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 1996) | h = −5→9 |
Tmin = 0.528, Tmax = 0.751 | k = −13→12 |
5296 measured reflections | l = −13→13 |
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)] = 0.025 | All H-atom parameters refined |
wR(F2) = 0.065 | w = 1/[σ2(Fo2) + (0.0309P)2 + 0.2141P] where P = (Fo2 + 2Fc2)/3 |
S = 1.19 | (Δ/σ)max = 0.001 |
1854 reflections | Δρmax = 0.32 e Å−3 |
162 parameters | Δρmin = −0.34 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0036 (6) |
(C7H11N2)2[SnCl6] | V = 1091.7 (4) Å3 |
Mr = 577.74 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.3328 (17) Å | µ = 1.91 mm−1 |
b = 11.680 (2) Å | T = 293 K |
c = 11.724 (2) Å | 0.4 × 0.2 × 0.15 mm |
β = 106.92 (3)° |
Siemens SMART 1000 diffractometer | 1854 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1996) | 1629 reflections with I > 2σ(I) |
Tmin = 0.528, Tmax = 0.751 | Rint = 0.035 |
5296 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.065 | All H-atom parameters refined |
S = 1.19 | Δρmax = 0.32 e Å−3 |
1854 reflections | Δρmin = −0.34 e Å−3 |
162 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) | |
Sn | 0.5000 | 0.5000 | 0.0000 | 0.03134 (14) | 0.989 (2) |
Cl1 | 0.50471 (12) | 0.63254 (7) | 0.16141 (7) | 0.0573 (3) | |
Cl2 | 0.58090 (12) | 0.34573 (7) | 0.14365 (7) | 0.0564 (3) | |
Cl3 | 0.79094 (11) | 0.54174 (10) | 0.02168 (9) | 0.0663 (3) | |
N1 | 0.9065 (3) | 0.3422 (2) | 0.5524 (2) | 0.0489 (7) | |
C1 | 0.8195 (4) | 0.4351 (3) | 0.5633 (2) | 0.0391 (7) | |
N2 | 0.6484 (4) | 0.6321 (3) | 0.5846 (4) | 0.0643 (9) | |
C2 | 0.8081 (5) | 0.4737 (3) | 0.6747 (3) | 0.0528 (9) | |
C4 | 0.6528 (5) | 0.5979 (3) | 0.4765 (4) | 0.0578 (9) | |
C5 | 0.7331 (4) | 0.5015 (3) | 0.4624 (3) | 0.0461 (8) | |
C3 | 0.7220 (5) | 0.5714 (4) | 0.6811 (4) | 0.0623 (11) | |
C6 | 0.9064 (6) | 0.2969 (4) | 0.4362 (4) | 0.0626 (11) | |
C7 | 1.0031 (7) | 0.2747 (5) | 0.6545 (5) | 0.0742 (13) | |
H6A | 0.945 (7) | 0.351 (5) | 0.397 (5) | 0.13 (2)* | |
H4 | 0.593 (4) | 0.645 (3) | 0.417 (3) | 0.056 (10)* | |
H2 | 0.870 (5) | 0.432 (3) | 0.737 (3) | 0.066 (12)* | |
H7B | 1.045 (6) | 0.331 (5) | 0.712 (4) | 0.11 (2)* | |
H7A | 0.924 (6) | 0.244 (4) | 0.686 (4) | 0.094 (16)* | |
H5 | 0.731 (4) | 0.483 (3) | 0.388 (4) | 0.050 (10)* | |
H6C | 0.803 (6) | 0.272 (4) | 0.387 (4) | 0.081 (13)* | |
H3 | 0.709 (5) | 0.590 (4) | 0.756 (4) | 0.088 (13)* | |
H2' | 0.594 (5) | 0.691 (3) | 0.589 (3) | 0.068 (12)* | |
H6B | 0.974 (7) | 0.242 (5) | 0.453 (5) | 0.12 (2)* | |
H7C | 1.098 (7) | 0.249 (5) | 0.634 (5) | 0.13 (2)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn | 0.0338 (2) | 0.03110 (19) | 0.02929 (18) | −0.00423 (11) | 0.00937 (12) | 0.00026 (10) |
Cl1 | 0.0886 (7) | 0.0444 (5) | 0.0451 (5) | −0.0089 (4) | 0.0290 (4) | −0.0106 (4) |
Cl2 | 0.0752 (6) | 0.0434 (5) | 0.0438 (5) | −0.0007 (4) | 0.0063 (4) | 0.0124 (4) |
Cl3 | 0.0401 (5) | 0.0851 (7) | 0.0745 (6) | −0.0151 (5) | 0.0178 (4) | 0.0008 (5) |
N1 | 0.0483 (16) | 0.0497 (17) | 0.0455 (15) | 0.0081 (13) | 0.0084 (12) | 0.0054 (12) |
C1 | 0.0375 (16) | 0.0409 (18) | 0.0381 (16) | −0.0046 (13) | 0.0098 (13) | 0.0011 (13) |
N2 | 0.055 (2) | 0.0481 (19) | 0.094 (3) | −0.0010 (15) | 0.0294 (18) | −0.0173 (19) |
C2 | 0.054 (2) | 0.061 (2) | 0.045 (2) | −0.0087 (18) | 0.0160 (17) | −0.0010 (17) |
C4 | 0.051 (2) | 0.050 (2) | 0.067 (2) | 0.0057 (17) | 0.0093 (18) | 0.0063 (19) |
C5 | 0.048 (2) | 0.049 (2) | 0.0391 (18) | 0.0004 (15) | 0.0090 (14) | 0.0025 (15) |
C3 | 0.061 (2) | 0.074 (3) | 0.059 (2) | −0.021 (2) | 0.028 (2) | −0.025 (2) |
C6 | 0.063 (3) | 0.060 (3) | 0.062 (2) | 0.007 (2) | 0.013 (2) | −0.013 (2) |
C7 | 0.072 (3) | 0.074 (3) | 0.071 (3) | 0.018 (2) | 0.013 (3) | 0.027 (3) |
Sn—Cl3i | 2.4127 (10) | N1—C7 | 1.464 (5) |
Sn—Cl3 | 2.4127 (10) | C1—C2 | 1.411 (4) |
Sn—Cl2 | 2.4242 (9) | C1—C5 | 1.423 (4) |
Sn—Cl2i | 2.4242 (9) | N2—C3 | 1.325 (5) |
Sn—Cl1i | 2.4364 (8) | N2—C4 | 1.340 (5) |
Sn—Cl1 | 2.4364 (8) | C2—C3 | 1.362 (6) |
N1—C1 | 1.331 (4) | C4—C5 | 1.344 (5) |
N1—C6 | 1.461 (5) | ||
Cl3i—Sn—Cl3 | 180.00 (5) | Cl2i—Sn—Cl1 | 90.33 (3) |
Cl3i—Sn—Cl2 | 89.47 (4) | Cl1i—Sn—Cl1 | 180.00 (2) |
Cl3—Sn—Cl2 | 90.53 (4) | C1—N1—C6 | 122.2 (3) |
Cl3i—Sn—Cl2i | 90.53 (4) | C1—N1—C7 | 123.1 (3) |
Cl3—Sn—Cl2i | 89.47 (4) | C6—N1—C7 | 114.7 (4) |
Cl2—Sn—Cl2i | 180.00 (3) | N1—C1—C2 | 122.3 (3) |
Cl3i—Sn—Cl1i | 90.07 (4) | N1—C1—C5 | 121.5 (3) |
Cl3—Sn—Cl1i | 89.93 (4) | C2—C1—C5 | 116.2 (3) |
Cl2—Sn—Cl1i | 90.33 (3) | C3—N2—C4 | 121.0 (4) |
Cl2i—Sn—Cl1i | 89.67 (3) | C3—C2—C1 | 119.8 (4) |
Cl3i—Sn—Cl1 | 89.93 (4) | N2—C4—C5 | 121.2 (4) |
Cl3—Sn—Cl1 | 90.07 (4) | C4—C5—C1 | 120.3 (3) |
Cl2—Sn—Cl1 | 89.67 (3) | N2—C3—C2 | 121.4 (4) |
C6—N1—C1—C2 | 174.7 (4) | C3—N2—C4—C5 | −0.6 (6) |
C7—N1—C1—C2 | −2.5 (5) | N2—C4—C5—C1 | −1.8 (5) |
C6—N1—C1—C5 | −5.6 (5) | N1—C1—C5—C4 | −176.8 (3) |
C7—N1—C1—C5 | 177.2 (4) | C2—C1—C5—C4 | 2.9 (5) |
N1—C1—C2—C3 | 177.9 (3) | C4—N2—C3—C2 | 1.6 (6) |
C5—C1—C2—C3 | −1.8 (5) | C1—C2—C3—N2 | −0.3 (6) |
Symmetry code: (i) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | (C7H11N2)2[SnCl6] |
Mr | 577.74 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 8.3328 (17), 11.680 (2), 11.724 (2) |
β (°) | 106.92 (3) |
V (Å3) | 1091.7 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.91 |
Crystal size (mm) | 0.4 × 0.2 × 0.15 |
Data collection | |
Diffractometer | Siemens SMART 1000 diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1996) |
Tmin, Tmax | 0.528, 0.751 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5296, 1854, 1629 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.588 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.065, 1.19 |
No. of reflections | 1854 |
No. of parameters | 162 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.32, −0.34 |
Computer programs: SMART (Bruker, 1996), SAINT (Bruker, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.
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
Synthesis of extended metal halide systems could be achieved by the use of organic counter-cations as templating agents based on their shape and hydrogen-bonding capabilities. 4-(Dimethylamino)pyridine has two different N atoms susceptible to protonation, the pyridine and the amine. The pyridine N atom is the first choice for protonation in metal(II) halides (Halverson et al., 1990). The structural determination of the title compound, (I), was undertaken to examine catination of 4-(dimethylamino)pyridine in the presence of metal(IV). The structure consists of [SnCl6]2− bridging two (C7H11N2)+ via hydrogen bonding through two pyridinium N atoms. Protonation occurs only on the pyridine N atom. Atom N1 is π bonded to the pyridine ring with a short N1—C1 bond of 1.335 (4) Å, comparable to the ring's nitrogen contacts [N2—C4 1.335 (5) Å and N2—C3 1.322 (6) Å]. The dimethylamine moiety is basically planar with the pyridine ring with only 4.4 (2)° twist from the plane of the ring. The pyridine N2 atom is hydrogen bonded to Cl1 [N2···Cl1 3.231 (5) Å]. The pyridinium cations are oriented so as to lie in the bc plane and form stacks parallel to the a axis.