Propane-1,3-diaminium tetra­chloridozincate(II) 18-crown-6 clathrate

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)], (C₃H₁₂N₂)[ZnCl₄]·C₁₂H₂₄O₆, 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. [C₃H₁₂N₂(18-crown-6)]²⁺, in which one of the -NH₃⁺ substituents nests in the crown and inter­acts through N-H...O hydrogen bonding. The other -NH₃⁺ group inter­acts with the [ZnCl₄]^2- anion via N-H...Cl hydrogen bonding, forming cation-crown-anion ribbons parallel to [010].

Computing details

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)

Crystal data

(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) Å^3	Block, colourless
Z = 4	0.40 × 0.30 × 0.20 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	H-atom parameters constrained
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0471P)^2] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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···Cl4^i	0.89	2.35	3.233 (3)	174
N1—H1A···Cl4^ii	0.89	2.79	3.315 (3)	120
N1—H1A···Cl1^i	0.89	2.95	3.370 (3)	111
N1—H1B···Cl1^ii	0.89	2.36	3.215 (3)	162

Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1/2, −z+1/2.