Propane-1,3-diaminium bis-(perchlorate)-18-crown-6 (1/2).

In the title compound, C(3)H(12)N(2) (2+)·2ClO(4) (-)·2C(12)H(24)O(6), the central C atom of the propane-1,3-diammonium cation is located on a twofold rotation axis and the two terminal -NH(3) groups insert into the crown rings through N-H⋯O hydrogen bonding, resulting in the formation of a 1:2 supra-molecular [(C(3)H(12)N(2))·(C(12)H(24)O(6))(2)](+) complex. The perchlorate anion links with the supra-molecular complex via weak C-H⋯O hydrogen bonding.

Related literature

For the properties and structures of related compounds, see: Fu et al. (2007 ▶, 2008 ▶, 2009 ▶); Fu & Xiong (2008 ▶). For the ferroelectric properties of related amino derivatives, see: Fu et al. (2011a ▶,b ▶,c ▶).

Experimental

Crystal data

C3H12N2 2+·2ClO4 −·2C12H24O6

M = 803.67

Monoclinic,

a = 22.984 (5) Å

b = 9.0055 (18) Å

c = 21.620 (4) Å

β = 113.59 (3)°

V = 4101.0 (17) Å3

Z = 4

Mo Kα radiation

μ = 0.23 mm−1

T = 298 K

0.10 × 0.03 × 0.03 mm

Data collection

Rigaku Mercury2 diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.910, T max = 1.000

16855 measured reflections

3606 independent reflections

2059 reflections with I > 2σ(I)

R int = 0.086

Refinement

R[F 2 > 2σ(F 2)] = 0.085

wR(F 2) = 0.248

S = 1.07

3606 reflections

232 parameters

H-atom parameters constrained

Δρmax = 0.65 e Å−3

Δρmin = −0.42 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811056248/xu5433sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811056248/xu5433Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C3H12N22+·2ClO4−·2C12H24O6	F(000) = 1720
Mr = 803.67	Dx = 1.302 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3606 reflections
a = 22.984 (5) Å	θ = 3.3–27.5°
b = 9.0055 (18) Å	µ = 0.23 mm−1
c = 21.620 (4) Å	T = 298 K
β = 113.59 (3)°	Block, colorless
V = 4101.0 (17) Å3	0.10 × 0.03 × 0.03 mm
Z = 4

Rigaku Mercury2 diffractometer	3606 independent reflections
Radiation source: fine-focus sealed tube	2059 reflections with I > 2σ(I)
graphite	Rint = 0.086
Detector resolution: 13.6612 pixels mm-1	θmax = 25.0°, θmin = 3.3°
CCD profile fitting scans	h = −27→27
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
Tmin = 0.910, Tmax = 1.000	l = −25→25
16855 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.085	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.248	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.1136P)2 + 6.3277P] where P = (Fo2 + 2Fc2)/3
3606 reflections	(Δ/σ)max < 0.001
232 parameters	Δρmax = 0.65 e Å−3
0 restraints	Δρmin = −0.42 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cl1	0.07984 (6)	0.10040 (17)	0.43221 (7)	0.0626 (5)
N1	0.10533 (15)	0.4168 (4)	0.23756 (18)	0.0394 (9)
H1C	0.1367	0.3550	0.2409	0.059*
H1D	0.1195	0.4836	0.2706	0.059*
H1E	0.0915	0.4628	0.1978	0.059*
C14	0.0000	0.4263 (7)	0.2500	0.0401 (15)
H14A	−0.0183	0.4888	0.2110	0.048*
C13	0.0522 (2)	0.3310 (5)	0.2433 (3)	0.0489 (12)
H13A	0.0693	0.2672	0.2820	0.059*
H13B	0.0334	0.2691	0.2041	0.059*
O1	0.19599 (14)	0.1670 (4)	0.26636 (16)	0.0522 (9)
O2	0.14880 (16)	0.2723 (4)	0.13018 (17)	0.0610 (10)
O6	0.22044 (16)	0.3852 (4)	0.37058 (16)	0.0600 (10)
O5	0.15115 (18)	0.6523 (4)	0.3449 (2)	0.0699 (11)
O3	0.07323 (17)	0.5386 (5)	0.10111 (19)	0.0694 (11)
O4	0.10201 (18)	0.7507 (4)	0.2076 (2)	0.0748 (12)
C11	0.2347 (2)	0.2291 (6)	0.3837 (3)	0.0613 (15)
H11A	0.1988	0.1794	0.3863	0.074*
H11B	0.2701	0.2174	0.4263	0.074*
C12	0.2501 (2)	0.1626 (6)	0.3288 (3)	0.0593 (14)
H12A	0.2846	0.2154	0.3246	0.071*
H12B	0.2629	0.0612	0.3398	0.071*
C2	0.1526 (3)	0.1189 (6)	0.1466 (3)	0.0683 (16)
H2A	0.1580	0.0620	0.1117	0.082*
H2B	0.1142	0.0871	0.1503	0.082*
C1	0.2077 (3)	0.0951 (6)	0.2127 (3)	0.0634 (15)
H1A	0.2155	−0.0089	0.2223	0.076*
H1B	0.2449	0.1381	0.2102	0.076*
C9	0.2026 (3)	0.6201 (8)	0.4103 (3)	0.0796 (19)
H9A	0.1956	0.6718	0.4455	0.096*
H9B	0.2419	0.6542	0.4096	0.096*
C4	0.0927 (3)	0.4672 (8)	0.0535 (3)	0.080 (2)
H4A	0.1335	0.5054	0.0591	0.096*
H4B	0.0631	0.4888	0.0084	0.096*
C3	0.0976 (3)	0.3036 (7)	0.0654 (3)	0.0751 (18)
H3A	0.0581	0.2673	0.0648	0.090*
H3B	0.1056	0.2548	0.0300	0.090*
C6	0.0487 (3)	0.7661 (7)	0.1465 (4)	0.086 (2)
H6A	0.0386	0.8695	0.1376	0.104*
H6B	0.0127	0.7165	0.1488	0.104*
C5	0.0641 (3)	0.6996 (7)	0.0914 (3)	0.085 (2)
H5A	0.0303	0.7185	0.0482	0.102*
H5B	0.1022	0.7436	0.0917	0.102*
C8	0.1502 (4)	0.8053 (7)	0.3269 (4)	0.087 (2)
H8A	0.1882	0.8290	0.3206	0.104*
H8B	0.1483	0.8674	0.3622	0.104*
C10	0.2064 (3)	0.4562 (7)	0.4218 (3)	0.0716 (17)
H10A	0.2388	0.4350	0.4655	0.086*
H10B	0.1665	0.4209	0.4205	0.086*
C7	0.0943 (3)	0.8322 (6)	0.2623 (4)	0.083 (2)
H7A	0.0571	0.7967	0.2673	0.099*
H7B	0.0889	0.9362	0.2518	0.099*
O9	0.0609 (3)	0.0673 (6)	0.3637 (2)	0.1150 (18)
O8	0.0368 (2)	0.0512 (6)	0.4595 (3)	0.1106 (18)
O10	0.0830 (5)	0.2559 (8)	0.4361 (5)	0.231 (5)
O7	0.1380 (3)	0.0480 (16)	0.4675 (4)	0.257 (6)

	U11	U22	U33	U12	U13	U23
Cl1	0.0603 (8)	0.0785 (10)	0.0606 (8)	−0.0265 (7)	0.0363 (7)	−0.0224 (7)
N1	0.037 (2)	0.037 (2)	0.048 (2)	0.0041 (16)	0.0206 (17)	0.0043 (17)
C14	0.038 (3)	0.038 (4)	0.049 (4)	0.000	0.021 (3)	0.000
C13	0.040 (3)	0.040 (3)	0.071 (3)	−0.002 (2)	0.027 (2)	0.001 (2)
O1	0.0417 (18)	0.054 (2)	0.060 (2)	0.0123 (15)	0.0193 (17)	0.0100 (17)
O2	0.058 (2)	0.062 (2)	0.056 (2)	−0.0107 (17)	0.0150 (18)	−0.0049 (18)
O6	0.067 (2)	0.070 (2)	0.045 (2)	−0.0079 (18)	0.0247 (18)	0.0007 (18)
O5	0.076 (3)	0.052 (2)	0.091 (3)	−0.0118 (19)	0.044 (2)	−0.015 (2)
O3	0.068 (2)	0.074 (3)	0.055 (2)	−0.0096 (19)	0.0132 (19)	0.020 (2)
O4	0.057 (2)	0.059 (2)	0.104 (3)	0.0210 (19)	0.026 (2)	0.017 (2)
C11	0.052 (3)	0.065 (4)	0.058 (3)	−0.003 (3)	0.014 (3)	0.025 (3)
C12	0.043 (3)	0.055 (3)	0.070 (4)	0.003 (2)	0.013 (3)	0.020 (3)
C2	0.074 (4)	0.063 (4)	0.079 (4)	−0.008 (3)	0.042 (3)	−0.014 (3)
C1	0.071 (4)	0.046 (3)	0.089 (4)	0.012 (3)	0.049 (3)	−0.002 (3)
C9	0.087 (4)	0.101 (6)	0.056 (4)	−0.018 (4)	0.034 (4)	−0.025 (3)
C4	0.064 (4)	0.103 (5)	0.049 (3)	−0.027 (4)	−0.003 (3)	0.016 (3)
C3	0.072 (4)	0.095 (5)	0.044 (3)	−0.020 (3)	0.009 (3)	−0.013 (3)
C6	0.062 (4)	0.066 (4)	0.125 (6)	0.008 (3)	0.030 (4)	0.041 (4)
C5	0.059 (4)	0.076 (4)	0.084 (5)	−0.011 (3)	−0.009 (3)	0.053 (4)
C8	0.110 (5)	0.052 (4)	0.122 (6)	−0.004 (4)	0.071 (5)	−0.033 (4)
C10	0.070 (4)	0.093 (5)	0.054 (3)	−0.014 (3)	0.027 (3)	−0.005 (3)
C7	0.085 (4)	0.043 (3)	0.149 (7)	0.018 (3)	0.078 (5)	0.002 (4)
O9	0.159 (5)	0.123 (4)	0.065 (3)	0.033 (3)	0.045 (3)	0.005 (3)
O8	0.118 (4)	0.112 (4)	0.146 (4)	−0.048 (3)	0.100 (4)	−0.035 (3)
O10	0.412 (14)	0.111 (5)	0.310 (10)	−0.140 (7)	0.292 (11)	−0.112 (6)
O7	0.076 (4)	0.533 (19)	0.133 (6)	0.024 (7)	0.012 (4)	0.140 (9)

Cl1—O7	1.332 (7)	C12—H12A	0.9599
Cl1—O9	1.399 (5)	C12—H12B	0.9600
Cl1—O10	1.403 (7)	C2—C1	1.500 (8)
Cl1—O8	1.410 (4)	C2—H2A	0.9600
N1—C13	1.492 (5)	C2—H2B	0.9601
N1—H1C	0.8900	C1—H1A	0.9599
N1—H1D	0.8900	C1—H1B	0.9600
N1—H1E	0.8900	C9—C10	1.493 (8)
C14—C13	1.528 (5)	C9—H9A	0.9600
C14—C13i	1.528 (5)	C9—H9B	0.9601
C14—H14A	0.9600	C4—C3	1.492 (8)
C13—H13A	0.9600	C4—H4A	0.9599
C13—H13B	0.9600	C4—H4B	0.9600
O1—C12	1.423 (6)	C3—H3A	0.9600
O1—C1	1.444 (6)	C3—H3B	0.9600
O2—C2	1.420 (6)	C6—C5	1.496 (9)
O2—C3	1.452 (6)	C6—H6A	0.9601
O6—C10	1.422 (6)	C6—H6B	0.9600
O6—C11	1.445 (6)	C5—H5A	0.9600
O5—C8	1.430 (7)	C5—H5B	0.9600
O5—C9	1.462 (7)	C8—C7	1.492 (9)
O3—C4	1.429 (8)	C8—H8A	0.9602
O3—C5	1.468 (7)	C8—H8B	0.9600
O4—C6	1.403 (7)	C10—H10A	0.9602
O4—C7	1.462 (7)	C10—H10B	0.9600
C11—C12	1.494 (7)	C7—H7A	0.9601
C11—H11A	0.9600	C7—H7B	0.9599
C11—H11B	0.9600
O7—Cl1—O9	110.3 (5)	H1A—C1—H1B	108.3
O7—Cl1—O10	107.6 (7)	O5—C9—C10	109.1 (5)
O9—Cl1—O10	105.2 (5)	O5—C9—H9A	110.1
O7—Cl1—O8	111.1 (4)	C10—C9—H9A	111.4
O9—Cl1—O8	113.7 (3)	O5—C9—H9B	108.9
O10—Cl1—O8	108.5 (4)	C10—C9—H9B	109.0
C13—N1—H1C	109.5	H9A—C9—H9B	108.3
C13—N1—H1D	109.5	O3—C4—C3	110.2 (5)
H1C—N1—H1D	109.5	O3—C4—H4A	108.6
C13—N1—H1E	109.5	C3—C4—H4A	109.2
H1C—N1—H1E	109.5	O3—C4—H4B	110.0
H1D—N1—H1E	109.5	C3—C4—H4B	110.5
C13—C14—C13i	111.6 (5)	H4A—C4—H4B	108.3
C13—C14—H14A	109.3	O2—C3—C4	109.5 (4)
C13i—C14—H14A	109.2	O2—C3—H3A	110.1
N1—C13—C14	114.6 (4)	C4—C3—H3A	109.1
N1—C13—H13A	108.5	O2—C3—H3B	109.9
C14—C13—H13A	108.5	C4—C3—H3B	110.0
N1—C13—H13B	108.7	H3A—C3—H3B	108.3
C14—C13—H13B	108.5	O4—C6—C5	108.3 (5)
H13A—C13—H13B	107.8	O4—C6—H6A	109.6
C12—O1—C1	112.1 (4)	C5—C6—H6A	110.2
C2—O2—C3	112.0 (4)	O4—C6—H6B	110.6
C10—O6—C11	112.8 (4)	C5—C6—H6B	109.8
C8—O5—C9	111.8 (5)	H6A—C6—H6B	108.4
C4—O3—C5	114.2 (5)	O3—C5—C6	110.3 (5)
C6—O4—C7	111.7 (5)	O3—C5—H5A	109.2
O6—C11—C12	109.9 (4)	C6—C5—H5A	110.2
O6—C11—H11A	109.4	O3—C5—H5B	109.2
C12—C11—H11A	110.0	C6—C5—H5B	109.5
O6—C11—H11B	109.5	H5A—C5—H5B	108.3
C12—C11—H11B	109.8	O5—C8—C7	108.9 (5)
H11A—C11—H11B	108.2	O5—C8—H8A	109.8
O1—C12—C11	110.4 (4)	C7—C8—H8A	108.7
O1—C12—H12A	109.8	O5—C8—H8B	110.2
C11—C12—H12A	110.1	C7—C8—H8B	110.6
O1—C12—H12B	109.0	H8A—C8—H8B	108.6
C11—C12—H12B	109.2	O6—C10—C9	109.4 (5)
H12A—C12—H12B	108.2	O6—C10—H10A	110.4
O2—C2—C1	108.7 (4)	C9—C10—H10A	109.4
O2—C2—H2A	109.7	O6—C10—H10B	109.9
C1—C2—H2A	110.3	C9—C10—H10B	109.3
O2—C2—H2B	110.1	H10A—C10—H10B	108.5
C1—C2—H2B	109.4	O4—C7—C8	109.8 (4)
H2A—C2—H2B	108.6	O4—C7—H7A	109.0
O1—C1—C2	110.1 (4)	C8—C7—H7A	108.1
O1—C1—H1A	110.0	O4—C7—H7B	110.3
C2—C1—H1A	111.0	C8—C7—H7B	111.2
O1—C1—H1B	108.8	H7A—C7—H7B	108.3
C2—C1—H1B	108.6
C13i—C14—C13—N1	−179.1 (5)	O3—C4—C3—O2	−66.2 (6)
C10—O6—C11—C12	−178.9 (4)	C7—O4—C6—C5	171.5 (5)
C1—O1—C12—C11	−176.3 (4)	C4—O3—C5—C6	−175.6 (5)
O6—C11—C12—O1	−64.8 (5)	O4—C6—C5—O3	65.9 (6)
C3—O2—C2—C1	178.0 (4)	C9—O5—C8—C7	−176.3 (5)
C12—O1—C1—C2	−173.0 (4)	C11—O6—C10—C9	171.0 (4)
O2—C2—C1—O1	66.2 (6)	O5—C9—C10—O6	61.6 (6)
C8—O5—C9—C10	−172.4 (5)	C6—O4—C7—C8	176.6 (5)
C5—O3—C4—C3	−177.2 (4)	O5—C8—C7—O4	−65.6 (6)
C2—O2—C3—C4	175.4 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O1	0.89	2.10	2.958 (4)	161.
N1—H1E···O3	0.89	2.08	2.951 (5)	167.
N1—H1D···O5	0.89	2.12	3.007 (5)	177.
C10—H10B···O10	0.96	2.55	3.478 (13)	161
C13—H13A···O9	0.96	2.58	3.470 (7)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O1	0.89	2.10	2.958 (4)	161
N1—H1E⋯O3	0.89	2.08	2.951 (5)	167
N1—H1D⋯O5	0.89	2.12	3.007 (5)	177
C10—H10B⋯O10	0.96	2.55	3.478 (13)	161
C13—H13A⋯O9	0.96	2.58	3.470 (7)	154