The reaction of propane-1,3-diamine hydrochloride, 18-crown-6 and zinc(II) chloride in methanol solution yields the title complex salt [systematic name: propane-1,3-diaminium tetrachloridozincate(II)-1,4,7,10,13,16-hexaoxacyclooctadecane (1/1)], (C
3H
12N
2)[ZnCl
4]·C
12H
24O
6, with an unusual supramolecular structure. The diprotonated propane-1,3-diaminium cation forms an unexpected 1:1 supramolecular rotator-stator complex with the crown ether,
viz. [C
3H
12N
2(18-crown-6)]
2+, in which one of the -NH
3+ substituents nests in the crown and interacts through N-H
O hydrogen bonding. The other -NH
3+ group interacts with the [ZnCl
4]
2- anion
via N-H
Cl hydrogen bonding, forming cation-crown-anion ribbons parallel to [010].
Supporting information
CCDC reference: 786802
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999).
propane-1,3-diaminium tetrachloridozincate(II)–
1,4,7,10,13,16-hexaoxacyclooctadecane (1/1)
top
Crystal data top
(C3H12N2)[ZnCl4]·C12H24O6 | F(000) = 1144 |
Mr = 547.65 | Dx = 1.452 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 6712 reflections |
a = 9.134 (3) Å | θ = 2.2–27.5° |
b = 9.862 (3) Å | µ = 1.44 mm−1 |
c = 27.810 (8) Å | T = 93 K |
V = 2505.1 (13) Å3 | Block, colourless |
Z = 4 | 0.40 × 0.30 × 0.20 mm |
Data collection top
Rigaku SCXmini diffractometer | 5729 independent reflections |
Radiation source: fine-focus sealed tube | 5432 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 2.2° |
CCD_Profile_fitting scans | h = −11→11 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −12→12 |
Tmin = 0.602, Tmax = 0.750 | l = −36→36 |
24776 measured reflections | |
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)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.095 | w = 1/[σ2(Fo2) + (0.0471P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max = 0.001 |
5729 reflections | Δρmax = 0.47 e Å−3 |
253 parameters | Δρmin = −0.52 e Å−3 |
0 restraints | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.003 (11) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 > 2sigma(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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Zn1 | 0.46558 (4) | 0.65561 (4) | 0.161731 (12) | 0.01562 (9) | |
Cl4 | 0.67684 (8) | 0.69672 (8) | 0.20614 (3) | 0.01763 (16) | |
Cl3 | 0.46586 (9) | 0.78186 (8) | 0.09510 (2) | 0.02090 (16) | |
Cl2 | 0.43509 (8) | 0.42960 (8) | 0.15330 (3) | 0.02101 (17) | |
Cl1 | 0.29348 (9) | 0.71748 (9) | 0.21838 (3) | 0.02212 (17) | |
O1 | 0.9391 (2) | 0.3326 (2) | 0.15619 (7) | 0.0194 (5) | |
N2 | 0.7991 (3) | 0.1513 (3) | 0.08904 (8) | 0.0155 (5) | |
H2A | 0.7944 | 0.1900 | 0.0602 | 0.023* | |
H2B | 0.8438 | 0.0715 | 0.0866 | 0.023* | |
H2C | 0.8492 | 0.2046 | 0.1089 | 0.023* | |
C11 | 0.7052 (4) | 0.4743 (3) | 0.03805 (12) | 0.0206 (7) | |
H11A | 0.6951 | 0.5712 | 0.0331 | 0.025* | |
H11B | 0.6173 | 0.4415 | 0.0538 | 0.025* | |
O6 | 0.8302 (2) | 0.4474 (2) | 0.06755 (7) | 0.0195 (5) | |
C13 | 0.6479 (3) | 0.1311 (3) | 0.10813 (10) | 0.0158 (6) | |
H13A | 0.5926 | 0.0739 | 0.0863 | 0.019* | |
H13B | 0.5984 | 0.2179 | 0.1104 | 0.019* | |
O2 | 1.0464 (3) | 0.0700 (2) | 0.15335 (8) | 0.0245 (5) | |
O4 | 0.8237 (2) | −0.0038 (2) | −0.00096 (8) | 0.0208 (5) | |
O5 | 0.7145 (3) | 0.2623 (2) | −0.00182 (8) | 0.0189 (5) | |
O3 | 0.9304 (2) | −0.1156 (2) | 0.08594 (8) | 0.0223 (5) | |
C7 | 1.0446 (4) | 0.1449 (4) | 0.19705 (12) | 0.0263 (7) | |
H7A | 1.1246 | 0.1160 | 0.2176 | 0.032* | |
H7B | 0.9534 | 0.1291 | 0.2140 | 0.032* | |
C9 | 0.9456 (3) | 0.4735 (3) | 0.14473 (11) | 0.0210 (7) | |
H9A | 1.0353 | 0.4933 | 0.1275 | 0.025* | |
H9B | 0.9443 | 0.5270 | 0.1740 | 0.025* | |
C3 | 0.8051 (4) | −0.1430 (3) | 0.01154 (12) | 0.0230 (7) | |
H3A | 0.7987 | −0.1978 | −0.0173 | 0.028* | |
H3B | 0.7154 | −0.1546 | 0.0298 | 0.028* | |
C2 | 0.7165 (4) | 0.0405 (4) | −0.03512 (12) | 0.0258 (8) | |
H2D | 0.6190 | 0.0264 | −0.0223 | 0.031* | |
H2E | 0.7258 | −0.0113 | −0.0646 | 0.031* | |
C14 | 0.6544 (3) | 0.0652 (3) | 0.15737 (10) | 0.0176 (6) | |
H14A | 0.7183 | 0.1179 | 0.1780 | 0.021* | |
H14B | 0.6961 | −0.0249 | 0.1543 | 0.021* | |
C6 | 1.0379 (4) | −0.0717 (4) | 0.16237 (13) | 0.0311 (8) | |
H6A | 0.9442 | −0.0937 | 0.1769 | 0.037* | |
H6B | 1.1148 | −0.0987 | 0.1844 | 0.037* | |
C12 | 0.7243 (4) | 0.4040 (3) | −0.00941 (12) | 0.0235 (7) | |
H12A | 0.6489 | 0.4332 | −0.0317 | 0.028* | |
H12B | 0.8190 | 0.4267 | −0.0231 | 0.028* | |
C4 | 0.9342 (4) | −0.1867 (3) | 0.04120 (12) | 0.0240 (7) | |
H4A | 0.9301 | −0.2836 | 0.0469 | 0.029* | |
H4B | 1.0244 | −0.1663 | 0.0243 | 0.029* | |
C5 | 1.0544 (4) | −0.1450 (4) | 0.11593 (14) | 0.0294 (8) | |
H5A | 1.1437 | −0.1165 | 0.1000 | 0.035* | |
H5B | 1.0604 | −0.2419 | 0.1217 | 0.035* | |
N1 | 0.5215 (3) | −0.0153 (3) | 0.22817 (9) | 0.0190 (5) | |
H1A | 0.4344 | −0.0225 | 0.2423 | 0.028* | |
H1B | 0.5813 | 0.0328 | 0.2468 | 0.028* | |
H1C | 0.5589 | −0.0976 | 0.2236 | 0.028* | |
C15 | 0.5043 (3) | 0.0545 (3) | 0.18061 (11) | 0.0179 (6) | |
H15A | 0.4631 | 0.1442 | 0.1852 | 0.022* | |
H15B | 0.4388 | 0.0030 | 0.1601 | 0.022* | |
C10 | 0.8150 (4) | 0.5083 (3) | 0.11400 (11) | 0.0199 (7) | |
H10A | 0.7263 | 0.4756 | 0.1293 | 0.024* | |
H10B | 0.8075 | 0.6059 | 0.1107 | 0.024* | |
C8 | 1.0600 (4) | 0.2922 (4) | 0.18556 (12) | 0.0255 (7) | |
H8A | 1.0612 | 0.3450 | 0.2150 | 0.031* | |
H8C | 1.1513 | 0.3081 | 0.1686 | 0.031* | |
C1 | 0.7401 (4) | 0.1886 (4) | −0.04528 (11) | 0.0261 (8) | |
H1D | 0.8394 | 0.2038 | −0.0563 | 0.031* | |
H1E | 0.6732 | 0.2189 | −0.0701 | 0.031* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.01578 (18) | 0.01615 (17) | 0.01495 (16) | 0.00069 (15) | −0.00042 (14) | 0.00005 (13) |
Cl4 | 0.0167 (4) | 0.0181 (4) | 0.0181 (3) | 0.0013 (3) | −0.0024 (3) | −0.0014 (3) |
Cl3 | 0.0250 (4) | 0.0222 (4) | 0.0154 (3) | −0.0027 (4) | −0.0021 (3) | 0.0025 (3) |
Cl2 | 0.0214 (4) | 0.0171 (4) | 0.0245 (4) | −0.0039 (3) | 0.0019 (3) | −0.0022 (3) |
Cl1 | 0.0197 (4) | 0.0244 (4) | 0.0222 (4) | 0.0086 (3) | 0.0045 (3) | 0.0043 (3) |
O1 | 0.0166 (11) | 0.0208 (11) | 0.0209 (11) | −0.0011 (9) | −0.0048 (9) | 0.0009 (9) |
N2 | 0.0169 (13) | 0.0143 (12) | 0.0152 (12) | 0.0011 (12) | 0.0006 (10) | 0.0014 (10) |
C11 | 0.0224 (17) | 0.0135 (15) | 0.0258 (16) | 0.0036 (14) | −0.0040 (13) | 0.0002 (13) |
O6 | 0.0214 (12) | 0.0197 (11) | 0.0175 (10) | 0.0028 (10) | 0.0004 (9) | −0.0017 (9) |
C13 | 0.0127 (14) | 0.0172 (15) | 0.0176 (14) | −0.0006 (12) | −0.0002 (11) | 0.0011 (12) |
O2 | 0.0236 (12) | 0.0214 (12) | 0.0286 (12) | 0.0015 (11) | −0.0060 (10) | 0.0049 (10) |
O4 | 0.0230 (12) | 0.0173 (11) | 0.0222 (11) | −0.0011 (10) | 0.0001 (9) | −0.0019 (9) |
O5 | 0.0282 (12) | 0.0143 (11) | 0.0143 (10) | 0.0034 (10) | −0.0002 (9) | −0.0005 (8) |
O3 | 0.0182 (12) | 0.0195 (12) | 0.0291 (12) | 0.0045 (10) | 0.0011 (9) | 0.0014 (9) |
C7 | 0.0212 (17) | 0.0358 (19) | 0.0219 (16) | −0.0007 (17) | −0.0075 (13) | 0.0039 (14) |
C9 | 0.0191 (17) | 0.0200 (16) | 0.0238 (15) | −0.0017 (14) | 0.0016 (13) | −0.0054 (12) |
C3 | 0.0246 (17) | 0.0166 (16) | 0.0278 (16) | −0.0025 (15) | 0.0065 (14) | −0.0047 (14) |
C2 | 0.0296 (19) | 0.0275 (19) | 0.0204 (16) | 0.0020 (16) | −0.0047 (14) | −0.0067 (14) |
C14 | 0.0179 (15) | 0.0192 (15) | 0.0159 (14) | 0.0010 (13) | −0.0013 (12) | 0.0017 (12) |
C6 | 0.0269 (18) | 0.0284 (19) | 0.0380 (19) | 0.0040 (17) | −0.0113 (18) | 0.0114 (16) |
C12 | 0.0321 (19) | 0.0182 (16) | 0.0203 (15) | 0.0016 (15) | −0.0036 (14) | 0.0050 (13) |
C4 | 0.0239 (18) | 0.0131 (15) | 0.0351 (18) | 0.0008 (14) | 0.0109 (14) | −0.0005 (13) |
C5 | 0.0211 (18) | 0.0177 (16) | 0.049 (2) | 0.0066 (15) | −0.0075 (16) | 0.0069 (16) |
N1 | 0.0207 (13) | 0.0169 (13) | 0.0193 (13) | −0.0023 (12) | 0.0037 (11) | −0.0016 (10) |
C15 | 0.0181 (16) | 0.0190 (15) | 0.0168 (14) | −0.0004 (13) | 0.0027 (11) | 0.0009 (12) |
C10 | 0.0193 (16) | 0.0169 (15) | 0.0233 (16) | 0.0004 (14) | 0.0047 (13) | −0.0038 (13) |
C8 | 0.0183 (17) | 0.0351 (19) | 0.0230 (16) | −0.0020 (16) | −0.0097 (13) | −0.0031 (14) |
C1 | 0.035 (2) | 0.0270 (19) | 0.0160 (15) | 0.0061 (16) | −0.0024 (14) | −0.0030 (13) |
Geometric parameters (Å, º) top
Zn1—Cl3 | 2.2323 (9) | C9—H9B | 0.9700 |
Zn1—Cl2 | 2.2585 (10) | C3—C4 | 1.502 (5) |
Zn1—Cl1 | 2.3076 (9) | C3—H3A | 0.9700 |
Zn1—Cl4 | 2.3267 (9) | C3—H3B | 0.9700 |
O1—C9 | 1.427 (4) | C2—C1 | 1.503 (5) |
O1—C8 | 1.430 (4) | C2—H2D | 0.9700 |
N2—C13 | 1.493 (4) | C2—H2E | 0.9700 |
N2—H2A | 0.8900 | C14—C15 | 1.519 (4) |
N2—H2B | 0.8900 | C14—H14A | 0.9700 |
N2—H2C | 0.8900 | C14—H14B | 0.9700 |
C11—O6 | 1.431 (4) | C6—C5 | 1.488 (5) |
C11—C12 | 1.501 (4) | C6—H6A | 0.9700 |
C11—H11A | 0.9700 | C6—H6B | 0.9700 |
C11—H11B | 0.9700 | C12—H12A | 0.9700 |
O6—C10 | 1.431 (4) | C12—H12B | 0.9700 |
C13—C14 | 1.517 (4) | C4—H4A | 0.9700 |
C13—H13A | 0.9700 | C4—H4B | 0.9700 |
C13—H13B | 0.9700 | C5—H5A | 0.9700 |
O2—C6 | 1.422 (4) | C5—H5B | 0.9700 |
O2—C7 | 1.422 (4) | N1—C15 | 1.499 (4) |
O4—C3 | 1.426 (4) | N1—H1A | 0.8900 |
O4—C2 | 1.433 (4) | N1—H1B | 0.8900 |
O5—C12 | 1.417 (4) | N1—H1C | 0.8900 |
O5—C1 | 1.429 (4) | C15—H15A | 0.9700 |
O3—C4 | 1.428 (4) | C15—H15B | 0.9700 |
O3—C5 | 1.436 (4) | C10—H10A | 0.9700 |
C7—C8 | 1.494 (5) | C10—H10B | 0.9700 |
C7—H7A | 0.9700 | C8—H8A | 0.9700 |
C7—H7B | 0.9700 | C8—H8C | 0.9700 |
C9—C10 | 1.507 (4) | C1—H1D | 0.9700 |
C9—H9A | 0.9700 | C1—H1E | 0.9700 |
| | | |
Cl3—Zn1—Cl2 | 117.67 (3) | C13—C14—H14B | 109.2 |
Cl3—Zn1—Cl1 | 114.84 (4) | C15—C14—H14B | 109.2 |
Cl2—Zn1—Cl1 | 104.35 (3) | H14A—C14—H14B | 107.9 |
Cl3—Zn1—Cl4 | 110.03 (3) | O2—C6—C5 | 108.6 (3) |
Cl2—Zn1—Cl4 | 109.23 (3) | O2—C6—H6A | 110.0 |
Cl1—Zn1—Cl4 | 99.00 (4) | C5—C6—H6A | 110.0 |
C9—O1—C8 | 111.5 (2) | O2—C6—H6B | 110.0 |
C13—N2—H2A | 109.5 | C5—C6—H6B | 110.0 |
C13—N2—H2B | 109.5 | H6A—C6—H6B | 108.3 |
H2A—N2—H2B | 109.5 | O5—C12—C11 | 108.5 (3) |
C13—N2—H2C | 109.5 | O5—C12—H12A | 110.0 |
H2A—N2—H2C | 109.5 | C11—C12—H12A | 110.0 |
H2B—N2—H2C | 109.5 | O5—C12—H12B | 110.0 |
O6—C11—C12 | 109.0 (3) | C11—C12—H12B | 110.0 |
O6—C11—H11A | 109.9 | H12A—C12—H12B | 108.4 |
C12—C11—H11A | 109.9 | O3—C4—C3 | 108.6 (3) |
O6—C11—H11B | 109.9 | O3—C4—H4A | 110.0 |
C12—C11—H11B | 109.9 | C3—C4—H4A | 110.0 |
H11A—C11—H11B | 108.3 | O3—C4—H4B | 110.0 |
C11—O6—C10 | 111.3 (2) | C3—C4—H4B | 110.0 |
N2—C13—C14 | 110.0 (2) | H4A—C4—H4B | 108.4 |
N2—C13—H13A | 109.7 | O3—C5—C6 | 109.0 (3) |
C14—C13—H13A | 109.7 | O3—C5—H5A | 109.9 |
N2—C13—H13B | 109.7 | C6—C5—H5A | 109.9 |
C14—C13—H13B | 109.7 | O3—C5—H5B | 109.9 |
H13A—C13—H13B | 108.2 | C6—C5—H5B | 109.9 |
C6—O2—C7 | 111.0 (3) | H5A—C5—H5B | 108.3 |
C3—O4—C2 | 112.0 (3) | C15—N1—H1A | 109.5 |
C12—O5—C1 | 111.4 (3) | C15—N1—H1B | 109.5 |
C4—O3—C5 | 112.8 (3) | H1A—N1—H1B | 109.5 |
O2—C7—C8 | 108.7 (3) | C15—N1—H1C | 109.5 |
O2—C7—H7A | 109.9 | H1A—N1—H1C | 109.5 |
C8—C7—H7A | 109.9 | H1B—N1—H1C | 109.5 |
O2—C7—H7B | 109.9 | N1—C15—C14 | 108.2 (2) |
C8—C7—H7B | 109.9 | N1—C15—H15A | 110.1 |
H7A—C7—H7B | 108.3 | C14—C15—H15A | 110.1 |
O1—C9—C10 | 108.4 (3) | N1—C15—H15B | 110.1 |
O1—C9—H9A | 110.0 | C14—C15—H15B | 110.1 |
C10—C9—H9A | 110.0 | H15A—C15—H15B | 108.4 |
O1—C9—H9B | 110.0 | O6—C10—C9 | 109.9 (3) |
C10—C9—H9B | 110.0 | O6—C10—H10A | 109.7 |
H9A—C9—H9B | 108.4 | C9—C10—H10A | 109.7 |
O4—C3—C4 | 108.4 (3) | O6—C10—H10B | 109.7 |
O4—C3—H3A | 110.0 | C9—C10—H10B | 109.7 |
C4—C3—H3A | 110.0 | H10A—C10—H10B | 108.2 |
O4—C3—H3B | 110.0 | O1—C8—C7 | 108.7 (3) |
C4—C3—H3B | 110.0 | O1—C8—H8A | 110.0 |
H3A—C3—H3B | 108.4 | C7—C8—H8A | 110.0 |
O4—C2—C1 | 108.9 (3) | O1—C8—H8C | 110.0 |
O4—C2—H2D | 109.9 | C7—C8—H8C | 110.0 |
C1—C2—H2D | 109.9 | H8A—C8—H8C | 108.3 |
O4—C2—H2E | 109.9 | O5—C1—C2 | 108.2 (3) |
C1—C2—H2E | 109.9 | O5—C1—H1D | 110.1 |
H2D—C2—H2E | 108.3 | C2—C1—H1D | 110.1 |
C13—C14—C15 | 112.2 (2) | O5—C1—H1E | 110.1 |
C13—C14—H14A | 109.2 | C2—C1—H1E | 110.1 |
C15—C14—H14A | 109.2 | H1D—C1—H1E | 108.4 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2C···O1 | 0.89 | 2.00 | 2.884 (3) | 173 |
N2—H2C···O2 | 0.89 | 2.56 | 2.991 (3) | 111 |
N2—H2B···O3 | 0.89 | 2.01 | 2.894 (4) | 174 |
N2—H2B···O4 | 0.89 | 2.55 | 2.942 (3) | 107 |
N2—H2A···O5 | 0.89 | 2.00 | 2.860 (3) | 161 |
N2—H2A···O6 | 0.89 | 2.57 | 2.994 (4) | 110 |
N1—H1C···Cl4i | 0.89 | 2.35 | 3.233 (3) | 174 |
N1—H1A···Cl4ii | 0.89 | 2.79 | 3.315 (3) | 120 |
N1—H1A···Cl1i | 0.89 | 2.95 | 3.370 (3) | 111 |
N1—H1B···Cl1ii | 0.89 | 2.36 | 3.215 (3) | 162 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1/2, −z+1/2. |