Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010902410X/dn3118sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010902410X/dn3118Isup2.hkl |
CCDC reference: 746070
To a mixture of ytterbium chloride hexahydrate (0.096 mg, 0.247 mmol) and 2,6-diacetylpyridyne [-pyridine?] (61.7 mg, 0.38 mmol) in methanol (15 ml), ytterbium perchlorate hexahydrate (72 mg,0.12 mmol) was added and N,N'-bis(2-aminoethyl)-1,3-propanediamine (60.1 mg,0.38 mmol) was added dropwise with stirring. The reaction mixture was stirred for 24 h at 341 K. Red crystals of (I) were obtained by slow diffusion of toluene into the acetonitrile solution.
The positions of the NH3 h atoms were found geometrically and these atoms were treated as a rigid group with one common N—H distance refined. All other H atoms were found in a difference Fourier map and their positions were freely refined [Please give ranges of refined C—H and N—H distances]. Uiso(H) = 1.2 (1.4 for NH3 groups) times Ueq(parent).
Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C7H24N44+·3ClO4−·Cl− | Z = 2 |
Mr = 498.10 | F(000) = 516 |
Triclinic, P1 | Dx = 1.731 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.9755 (9) Å | Cell parameters from 2192 reflections |
b = 11.2619 (15) Å | θ = 3–24° |
c = 11.4848 (16) Å | µ = 0.69 mm−1 |
α = 77.358 (11)° | T = 100 K |
β = 78.991 (10)° | Block, colourless |
γ = 73.488 (11)° | 0.15 × 0.1 × 0.1 mm |
V = 955.9 (2) Å3 |
Kuma KM-4 CCD area-detector diffractometer | 4148 independent reflections |
Radiation source: fine-focus sealed tube | 2461 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
ω scans | θmax = 28.0°, θmin = 2.7° |
Absorption correction: multi-scan (CrysAlis CCD; Oxford Diffraction, 2009) | h = −10→9 |
Tmin = 0.901, Tmax = 0.936 | k = −14→14 |
9313 measured reflections | l = −14→14 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.061 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.90 | w = 1/[σ2(Fo2) + (0.01P)2] where P = (Fo2 + 2Fc2)/3 |
4148 reflections | (Δ/σ)max < 0.001 |
302 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.45 e Å−3 |
C7H24N44+·3ClO4−·Cl− | γ = 73.488 (11)° |
Mr = 498.10 | V = 955.9 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.9755 (9) Å | Mo Kα radiation |
b = 11.2619 (15) Å | µ = 0.69 mm−1 |
c = 11.4848 (16) Å | T = 100 K |
α = 77.358 (11)° | 0.15 × 0.1 × 0.1 mm |
β = 78.991 (10)° |
Kuma KM-4 CCD area-detector diffractometer | 4148 independent reflections |
Absorption correction: multi-scan (CrysAlis CCD; Oxford Diffraction, 2009) | 2461 reflections with I > 2σ(I) |
Tmin = 0.901, Tmax = 0.936 | Rint = 0.055 |
9313 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.061 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.90 | Δρmax = 0.39 e Å−3 |
4148 reflections | Δρmin = −0.45 e Å−3 |
302 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 | ||
N1 | 0.4399 (3) | 0.5522 (2) | 0.3040 (2) | 0.0189 (7) | |
H1A | 0.339 | 0.5898 | 0.3552 | 0.026* | |
H1B | 0.5336 | 0.5098 | 0.3503 | 0.026* | |
H1C | 0.411 | 0.4935 | 0.2678 | 0.026* | |
C2 | 0.4961 (4) | 0.6517 (3) | 0.2081 (3) | 0.0185 (8) | |
H2A | 0.587 (4) | 0.606 (2) | 0.155 (3) | 0.022* | |
H2B | 0.554 (3) | 0.696 (3) | 0.252 (3) | 0.022* | |
C3 | 0.3472 (4) | 0.7430 (3) | 0.1482 (3) | 0.0129 (7) | |
H3A | 0.261 (4) | 0.774 (2) | 0.203 (3) | 0.016* | |
H3B | 0.392 (3) | 0.812 (2) | 0.098 (2) | 0.016* | |
N4 | 0.2758 (3) | 0.6895 (2) | 0.0667 (2) | 0.0111 (6) | |
H4A | 0.240 (3) | 0.621 (2) | 0.110 (3) | 0.013* | |
H4B | 0.360 (3) | 0.667 (2) | 0.003 (3) | 0.013* | |
C5 | 0.1211 (4) | 0.7806 (3) | 0.0128 (3) | 0.0130 (8) | |
H5A | 0.164 (3) | 0.853 (2) | −0.028 (2) | 0.016* | |
H5B | 0.035 (3) | 0.800 (2) | 0.078 (3) | 0.016* | |
C6 | 0.0519 (4) | 0.7231 (3) | −0.0699 (3) | 0.0125 (7) | |
H6A | −0.016 (3) | 0.669 (2) | −0.024 (2) | 0.015* | |
H6B | 0.149 (3) | 0.679 (2) | −0.121 (3) | 0.015* | |
C7 | −0.0577 (4) | 0.8288 (3) | −0.1520 (3) | 0.0122 (7) | |
H7A | −0.156 (3) | 0.883 (2) | −0.108 (3) | 0.015* | |
H7B | 0.016 (3) | 0.888 (2) | −0.206 (2) | 0.015* | |
N8 | −0.1284 (3) | 0.7804 (2) | −0.2385 (2) | 0.0108 (6) | |
H8A | −0.214 (3) | 0.737 (2) | −0.194 (2) | 0.013* | |
H8B | −0.041 (3) | 0.720 (2) | −0.271 (3) | 0.013* | |
C9 | −0.1999 (4) | 0.8834 (3) | −0.3370 (3) | 0.0122 (7) | |
H9A | −0.091 (3) | 0.917 (2) | −0.389 (2) | 0.015* | |
H9B | −0.271 (3) | 0.951 (2) | −0.299 (3) | 0.015* | |
C10 | −0.3098 (4) | 0.8439 (3) | −0.4091 (3) | 0.0123 (7) | |
H10A | −0.351 (3) | 0.776 (3) | −0.364 (2) | 0.015* | |
H10B | −0.407 (3) | 0.916 (3) | −0.434 (2) | 0.015* | |
N11 | −0.2077 (3) | 0.7980 (2) | −0.5209 (2) | 0.0152 (7) | |
H11A | −0.182 | 0.8639 | −0.5759 | 0.021* | |
H11B | −0.2733 | 0.7616 | −0.5519 | 0.021* | |
H11C | −0.1060 | 0.7407 | −0.5030 | 0.021* | |
Cl4 | 0.39415 (9) | 0.39015 (7) | 0.12660 (7) | 0.0167 (2) | |
Cl2 | 0.29209 (9) | 0.76166 (7) | −0.46282 (7) | 0.01362 (19) | |
O21 | 0.1861 (2) | 0.7561 (2) | −0.55049 (19) | 0.0229 (6) | |
O22 | 0.2812 (2) | 0.89031 (18) | −0.4603 (2) | 0.0217 (6) | |
O23 | 0.2285 (2) | 0.70112 (19) | −0.34518 (18) | 0.0194 (5) | |
O24 | 0.4732 (2) | 0.69349 (18) | −0.49555 (19) | 0.0175 (5) | |
Cl1 | −0.33868 (10) | 0.95303 (8) | −0.80726 (7) | 0.0196 (2) | |
O11 | −0.4324 (3) | 1.0810 (2) | −0.8461 (2) | 0.0430 (8) | |
O12 | −0.3068 (3) | 0.8828 (2) | −0.9031 (2) | 0.0345 (7) | |
O13 | −0.1720 (3) | 0.94997 (19) | −0.77252 (19) | 0.0222 (6) | |
O14 | −0.4433 (2) | 0.89698 (18) | −0.70434 (18) | 0.0181 (5) | |
Cl3 | 0.95147 (10) | 0.53687 (7) | 0.31430 (7) | 0.01299 (18) | |
O31 | 0.7812 (2) | 0.56698 (19) | 0.38721 (19) | 0.0189 (5) | |
O32 | 1.0338 (3) | 0.63899 (18) | 0.29900 (19) | 0.0215 (6) | |
O33 | 0.9303 (3) | 0.51784 (19) | 0.19863 (19) | 0.0203 (5) | |
O34 | 1.0636 (2) | 0.42402 (18) | 0.37423 (18) | 0.0163 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0215 (16) | 0.0177 (15) | 0.0187 (17) | 0.0009 (12) | −0.0132 (13) | −0.0044 (13) |
C2 | 0.015 (2) | 0.023 (2) | 0.019 (2) | −0.0050 (16) | −0.0056 (16) | −0.0036 (16) |
C3 | 0.0139 (19) | 0.0149 (19) | 0.012 (2) | −0.0037 (15) | −0.0044 (15) | −0.0034 (15) |
N4 | 0.0088 (14) | 0.0138 (15) | 0.0108 (17) | −0.0021 (12) | 0.0006 (12) | −0.0053 (12) |
C5 | 0.0126 (18) | 0.0108 (17) | 0.015 (2) | 0.0003 (15) | −0.0068 (15) | −0.0015 (15) |
C6 | 0.0141 (18) | 0.0125 (18) | 0.0101 (19) | −0.0033 (14) | −0.0030 (15) | 0.0008 (14) |
C7 | 0.0134 (18) | 0.0182 (18) | 0.0075 (18) | −0.0057 (15) | −0.0014 (14) | −0.0051 (14) |
N8 | 0.0112 (15) | 0.0134 (15) | 0.0088 (16) | −0.0036 (12) | −0.0009 (12) | −0.0042 (12) |
C9 | 0.0124 (18) | 0.0105 (18) | 0.013 (2) | 0.0007 (14) | −0.0067 (15) | −0.0005 (14) |
C10 | 0.0124 (18) | 0.0126 (18) | 0.012 (2) | −0.0020 (14) | −0.0044 (15) | −0.0025 (15) |
N11 | 0.0146 (15) | 0.0209 (15) | 0.0128 (16) | −0.0062 (12) | −0.0062 (12) | −0.0027 (13) |
Cl4 | 0.0172 (4) | 0.0142 (4) | 0.0190 (5) | −0.0063 (3) | 0.0027 (4) | −0.0045 (4) |
Cl2 | 0.0098 (4) | 0.0195 (4) | 0.0129 (5) | −0.0054 (3) | −0.0020 (3) | −0.0031 (4) |
O21 | 0.0128 (12) | 0.0440 (15) | 0.0169 (14) | −0.0088 (11) | −0.0072 (10) | −0.0088 (12) |
O22 | 0.0211 (13) | 0.0136 (12) | 0.0297 (15) | −0.0006 (10) | −0.0059 (11) | −0.0051 (11) |
O23 | 0.0179 (12) | 0.0292 (13) | 0.0109 (13) | −0.0108 (10) | 0.0029 (10) | −0.0011 (11) |
O24 | 0.0059 (11) | 0.0246 (13) | 0.0198 (14) | 0.0005 (10) | 0.0003 (9) | −0.0068 (11) |
Cl1 | 0.0182 (5) | 0.0210 (5) | 0.0152 (5) | −0.0022 (4) | 0.0007 (4) | −0.0005 (4) |
O11 | 0.0332 (15) | 0.0245 (14) | 0.0463 (19) | 0.0067 (12) | 0.0037 (13) | 0.0195 (13) |
O12 | 0.0235 (14) | 0.0669 (18) | 0.0179 (15) | −0.0116 (13) | 0.0031 (11) | −0.0224 (14) |
O13 | 0.0222 (13) | 0.0238 (13) | 0.0243 (15) | −0.0125 (10) | −0.0024 (11) | −0.0036 (11) |
O14 | 0.0159 (12) | 0.0193 (12) | 0.0150 (13) | −0.0047 (10) | 0.0034 (10) | 0.0010 (10) |
Cl3 | 0.0117 (4) | 0.0136 (4) | 0.0143 (5) | −0.0019 (3) | −0.0033 (3) | −0.0039 (3) |
O31 | 0.0080 (11) | 0.0280 (13) | 0.0212 (14) | −0.0008 (10) | 0.0033 (10) | −0.0145 (11) |
O32 | 0.0238 (13) | 0.0140 (12) | 0.0283 (15) | −0.0085 (10) | −0.0029 (11) | −0.0026 (11) |
O33 | 0.0221 (13) | 0.0282 (13) | 0.0119 (13) | −0.0018 (10) | −0.0065 (10) | −0.0084 (11) |
O34 | 0.0145 (12) | 0.0150 (12) | 0.0164 (13) | 0.0019 (10) | −0.0066 (10) | 0.0001 (10) |
N1—C2 | 1.492 (4) | N8—H8A | 0.96 (3) |
N1—H1A | 0.9523 | N8—H8B | 0.91 (3) |
N1—H1B | 0.9523 | C9—C10 | 1.521 (4) |
N1—H1C | 0.9523 | C9—H9A | 1.07 (3) |
C2—C3 | 1.500 (4) | C9—H9B | 0.95 (3) |
C2—H2A | 0.96 (3) | C10—N11 | 1.494 (4) |
C2—H2B | 1.02 (3) | C10—H10A | 0.93 (3) |
C3—N4 | 1.486 (4) | C10—H10B | 0.98 (2) |
C3—H3A | 0.89 (3) | N11—H11A | 0.9083 |
C3—H3B | 0.98 (3) | N11—H11B | 0.9083 |
N4—C5 | 1.501 (4) | N11—H11C | 0.9083 |
N4—H4A | 0.91 (3) | Cl2—O22 | 1.433 (2) |
N4—H4B | 0.92 (3) | Cl2—O23 | 1.442 (2) |
C5—C6 | 1.515 (4) | Cl2—O24 | 1.4509 (19) |
C5—H5A | 0.97 (3) | Cl2—O21 | 1.454 (2) |
C5—H5B | 0.93 (3) | Cl1—O12 | 1.435 (2) |
C6—C7 | 1.517 (4) | Cl1—O11 | 1.438 (2) |
C6—H6A | 0.94 (3) | Cl1—O14 | 1.445 (2) |
C6—H6B | 0.96 (3) | Cl1—O13 | 1.449 (2) |
C7—N8 | 1.493 (4) | Cl3—O33 | 1.439 (2) |
C7—H7A | 0.97 (3) | Cl3—O32 | 1.443 (2) |
C7—H7B | 1.04 (3) | Cl3—O31 | 1.445 (2) |
N8—C9 | 1.499 (4) | Cl3—O34 | 1.4474 (18) |
C2—N1—H1A | 109.5 | C7—N8—C9 | 111.7 (2) |
C2—N1—H1B | 109.5 | C7—N8—H8A | 108.3 (17) |
H1A—N1—H1B | 109.5 | C9—N8—H8A | 112.8 (16) |
C2—N1—H1C | 109.5 | C7—N8—H8B | 109.2 (18) |
H1A—N1—H1C | 109.5 | C9—N8—H8B | 109.9 (18) |
H1B—N1—H1C | 109.5 | H8A—N8—H8B | 105 (2) |
N1—C2—C3 | 113.9 (3) | N8—C9—C10 | 112.8 (3) |
N1—C2—H2A | 104.4 (17) | N8—C9—H9A | 107.3 (14) |
C3—C2—H2A | 114.6 (17) | C10—C9—H9A | 114.9 (15) |
N1—C2—H2B | 104.3 (16) | N8—C9—H9B | 106.1 (17) |
C3—C2—H2B | 110.8 (15) | C10—C9—H9B | 109.6 (17) |
H2A—C2—H2B | 108 (2) | H9A—C9—H9B | 106 (2) |
N4—C3—C2 | 114.0 (3) | N11—C10—C9 | 113.6 (3) |
N4—C3—H3A | 109.9 (19) | N11—C10—H10A | 104.9 (17) |
C2—C3—H3A | 110.4 (18) | C9—C10—H10A | 109.6 (18) |
N4—C3—H3B | 106.0 (17) | N11—C10—H10B | 107.3 (16) |
C2—C3—H3B | 108.0 (15) | C9—C10—H10B | 109.3 (16) |
H3A—C3—H3B | 108 (2) | H10A—C10—H10B | 112 (2) |
C3—N4—C5 | 112.9 (2) | C10—N11—H11A | 109.5 |
C3—N4—H4A | 108.7 (18) | C10—N11—H11B | 109.5 |
C5—N4—H4A | 108.0 (17) | H11A—N11—H11B | 109.5 |
C3—N4—H4B | 110.8 (17) | C10—N11—H11C | 109.5 |
C5—N4—H4B | 106.2 (17) | H11A—N11—H11C | 109.5 |
H4A—N4—H4B | 110 (2) | H11B—N11—H11C | 109.5 |
N4—C5—C6 | 111.5 (2) | O22—Cl2—O23 | 109.73 (13) |
N4—C5—H5A | 104.9 (15) | O22—Cl2—O24 | 111.00 (12) |
C6—C5—H5A | 113.3 (17) | O23—Cl2—O24 | 108.04 (12) |
N4—C5—H5B | 105.6 (17) | O22—Cl2—O21 | 109.65 (13) |
C6—C5—H5B | 109.9 (18) | O23—Cl2—O21 | 109.66 (13) |
H5A—C5—H5B | 111 (2) | O24—Cl2—O21 | 108.73 (13) |
C5—C6—C7 | 108.4 (2) | O12—Cl1—O11 | 109.87 (15) |
C5—C6—H6A | 109.7 (18) | O12—Cl1—O14 | 109.47 (14) |
C7—C6—H6A | 111.1 (16) | O11—Cl1—O14 | 109.22 (13) |
C5—C6—H6B | 109.8 (17) | O12—Cl1—O13 | 109.56 (13) |
C7—C6—H6B | 106.8 (17) | O11—Cl1—O13 | 109.93 (14) |
H6A—C6—H6B | 111 (2) | O14—Cl1—O13 | 108.78 (13) |
N8—C7—C6 | 112.0 (2) | O33—Cl3—O32 | 109.89 (13) |
N8—C7—H7A | 108.9 (17) | O33—Cl3—O31 | 109.95 (13) |
C6—C7—H7A | 113.0 (17) | O32—Cl3—O31 | 109.06 (12) |
N8—C7—H7B | 104.8 (16) | O33—Cl3—O34 | 109.60 (12) |
C6—C7—H7B | 112.1 (14) | O32—Cl3—O34 | 108.47 (12) |
H7A—C7—H7B | 106 (2) | O31—Cl3—O34 | 109.83 (12) |
N1—C2—C3—N4 | −72.2 (4) | C5—C6—C7—N8 | 178.8 (3) |
C2—C3—N4—C5 | 177.1 (3) | C6—C7—N8—C9 | −166.8 (2) |
C3—N4—C5—C6 | 179.9 (3) | C7—N8—C9—C10 | −166.7 (3) |
N4—C5—C6—C7 | −161.0 (2) | N8—C9—C10—N11 | −94.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O21i | 0.95 | 2.29 | 3.147 (3) | 149 |
N1—H1A···O32ii | 0.95 | 2.52 | 3.114 (3) | 121 |
N1—H1B···O31 | 0.95 | 2.38 | 3.110 (3) | 133 |
N1—H1B···O23iii | 0.95 | 2.59 | 3.110 (3) | 133 |
N1—H1B···O24iii | 0.95 | 2.53 | 3.131 (3) | 121 |
N1—H1C···Cl4 | 0.95 | 2.24 | 3.147 (3) | 160 |
C2—H2B···O14iv | 1.02 (3) | 2.43 (3) | 3.321 (4) | 146 (2) |
N4—H4A···O32ii | 0.91 (3) | 2.47 (3) | 3.026 (3) | 120 (2) |
N4—H4A···Cl4 | 0.91 (3) | 2.52 (3) | 3.187 (3) | 130 (2) |
N4—H4B···Cl4iii | 0.92 (3) | 2.25 (3) | 3.156 (3) | 168 (2) |
C5—H5A···O11v | 0.97 (3) | 2.54 (3) | 3.367 (4) | 143 (2) |
C6—H6B···O23 | 0.96 (3) | 2.51 (3) | 3.238 (4) | 133 (2) |
C7—H7A···O12i | 0.97 (3) | 2.43 (3) | 3.224 (4) | 138 (2) |
C7—H7B···O13v | 1.04 (3) | 2.43 (3) | 3.370 (4) | 150 (2) |
N8—H8A···Cl4vi | 0.96 (3) | 2.23 (3) | 3.167 (3) | 166 (2) |
N8—H8B···O23 | 0.91 (3) | 2.12 (3) | 2.846 (3) | 135 (2) |
N8—H8B···O33iii | 0.91 (3) | 2.57 (3) | 3.252 (3) | 132 (2) |
N8—H8B···O34iii | 0.91 (3) | 2.27 (3) | 2.930 (3) | 129 (2) |
N11—H11A···O13 | 0.91 | 2.25 | 3.026 (3) | 143 |
N11—H11B···O31vii | 0.91 | 2.34 | 3.043 (3) | 134 |
N11—H11B···O24ii | 0.91 | 2.29 | 3.037 (3) | 139 |
N11—H11B···O14 | 0.91 | 2.41 | 2.916 (3) | 116 |
N11—H11B···O31vii | 0.91 | 2.34 | 3.043 (3) | 134 |
N11—H11C···O34iii | 0.91 | 2.09 | 2.770 (3) | 131 |
N11—H11C···O21 | 0.91 | 2.34 | 3.004 (3) | 130 |
Symmetry codes: (i) x, y, z+1; (ii) x−1, y, z; (iii) −x+1, −y+1, −z; (iv) x+1, y, z+1; (v) −x, −y+2, −z−1; (vi) −x, −y+1, −z; (vii) x−1, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C7H24N44+·3ClO4−·Cl− |
Mr | 498.10 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 7.9755 (9), 11.2619 (15), 11.4848 (16) |
α, β, γ (°) | 77.358 (11), 78.991 (10), 73.488 (11) |
V (Å3) | 955.9 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.69 |
Crystal size (mm) | 0.15 × 0.1 × 0.1 |
Data collection | |
Diffractometer | Kuma KM-4 CCD area-detector diffractometer |
Absorption correction | Multi-scan (CrysAlis CCD; Oxford Diffraction, 2009) |
Tmin, Tmax | 0.901, 0.936 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9313, 4148, 2461 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.660 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.061, 0.90 |
No. of reflections | 4148 |
No. of parameters | 302 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.39, −0.45 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Stereochemical Workstation Operation Manual (Siemens, 1989) and Mercury (Macrae et al., 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O21i | 0.95 | 2.29 | 3.147 (3) | 149 |
N1—H1A···O32ii | 0.95 | 2.52 | 3.114 (3) | 121 |
N1—H1B···O31 | 0.95 | 2.38 | 3.110 (3) | 133 |
N1—H1B···O23iii | 0.95 | 2.59 | 3.110 (3) | 133 |
N1—H1B···O24iii | 0.95 | 2.53 | 3.131 (3) | 121 |
N1—H1C···Cl4 | 0.95 | 2.24 | 3.147 (3) | 160 |
C2—H2B···O14iv | 1.02 (3) | 2.43 (3) | 3.321 (4) | 146 (2) |
N4—H4A···O32ii | 0.91 (3) | 2.47 (3) | 3.026 (3) | 120 (2) |
N4—H4A···Cl4 | 0.91 (3) | 2.52 (3) | 3.187 (3) | 130 (2) |
N4—H4B···Cl4iii | 0.92 (3) | 2.25 (3) | 3.156 (3) | 168 (2) |
C5—H5A···O11v | 0.97 (3) | 2.54 (3) | 3.367 (4) | 143 (2) |
C6—H6B···O23 | 0.96 (3) | 2.51 (3) | 3.238 (4) | 133 (2) |
C7—H7A···O12i | 0.97 (3) | 2.43 (3) | 3.224 (4) | 138 (2) |
C7—H7B···O13v | 1.04 (3) | 2.43 (3) | 3.370 (4) | 150 (2) |
N8—H8A···Cl4vi | 0.96 (3) | 2.23 (3) | 3.167 (3) | 166 (2) |
N8—H8B···O23 | 0.91 (3) | 2.12 (3) | 2.846 (3) | 135 (2) |
N8—H8B···O33iii | 0.91 (3) | 2.57 (3) | 3.252 (3) | 132 (2) |
N8—H8B···O34iii | 0.91 (3) | 2.27 (3) | 2.930 (3) | 129 (2) |
N11—H11A···O13 | 0.91 | 2.25 | 3.026 (3) | 143 |
N11—H11B···O31vii | 0.91 | 2.34 | 3.043 (3) | 134 |
N11—H11B···O24ii | 0.91 | 2.29 | 3.037 (3) | 139 |
N11—H11B···O14 | 0.91 | 2.41 | 2.916 (3) | 116 |
N11—H11B···O31vii | 0.91 | 2.34 | 3.043 (3) | 134 |
N11—H11C···O34iii | 0.91 | 2.09 | 2.770 (3) | 131 |
N11—H11C···O21 | 0.91 | 2.34 | 3.004 (3) | 130 |
Symmetry codes: (i) x, y, z+1; (ii) x−1, y, z; (iii) −x+1, −y+1, −z; (iv) x+1, y, z+1; (v) −x, −y+2, −z−1; (vi) −x, −y+1, −z; (vii) x−1, y, z−1. |
Condensation reactions of carbonyl compounds and primary amines lead to the formation of the azomethine bond (see, for example, Ibrahim & Sharif, 2007), which is a characteristic structural feature of Schiff bases and therefore may be applied in analytical determination. The importance of these compounds is mainly due to their resemblance to natural biological substances (de Hoog et al., 2004; Mukherjee et al., 2005), and their relatively simple preparation procedures and synthetic flexibility, which make the introduction of suitable structural properties relatively easy. Unfortunately, the serious drawback of the majority of Schiff bases is their chemical instability, which concerns equilibrium lability, i.e. hydrolysis, tautomeric interconversions or ionized species formation (Galic et al., 1997). In the course of our studies of the synthesis of a macrocyclic Schiff base with the ytterbium ion that has already been reported (Patroniak et al., 2004), we obtained, quite unexpectedly, the title salt, (I), of the quadruply protonated N,N'-bis(2-aminoethyl)propane-1,3-diamine with one chloride and three perchlorate anions.
In the Cambridge Structural Database (CSD, Version 5.30 of November 2008; Allen, 2002) there are only two structures of uncomplexed N,N'-bis(2-aminoethyl)propane-1,3-diamine, one a tetracation (benzene-1,2,4,5-tetracarboxylate; Su et al., 2002) and one an uncommon trication (tris-trifluoromethanesulfonate; Patroniak et al., 2008). Their conformations differ substantially: while the tetracation is gttttttg (g denotes gauche and t trans), in the trication the intramolecular N—H···N hydrogen bond enforces a more complicated gttggggt conformation. The conformation of (I) is similar to that found earlier in the tetracation (Su et al., 2002); the torsion angles along the chain are -71.9 (3), 176.8 (2), 179.7 (2), -160.9 (2), 178.8 (2), -167.1 (2), -167.1 (2) and -94.5 (3)°. The mean length of the Csp3—Csp3 bond is 1.519 (8) Å and that of the Nsp3—Csp3 bond is 1.491 (5) Å. The perchlorate anions are close to a tetrahedral geometry, with a mean Cl—O distance of 1.445 (8) Å.
The crystal packing of (I) is determined by the electrostatic interactions between the charged species and by an extensive network of hydrogen bonds. Probably due to the great number of hydrogen-bond donors and acceptors, the resulting interactions are relatively weak (see Table 1). In the crystal structure these hydrogen bonds create a complicated network of rings and chains.
The presence of both perchlorate and chloride anions in the structure is not particularly rare. There are 160 examples in the CSD (most of which, 149, are organometallics) including one similar structure, of diethylenetriammonium chloride diperchlorate (Mazus et al., 1987). Such a situation might be regarded as an example of undecided competition between the anions (see, for example, Warden et al., 2004). In every case one should find the packing advantages of such a composition of the `supramolecule'. In the case of (I) it might be noted that the terminal hydrogen-bond donor groups (atoms N1 and N11) interact mainly with the perchlorate anions, while the `internal' ones (atoms N4 and N8) interact mainly with the chlorides. This can be connected with the tendency to form centrosymmetric `face-to-face' dimers by means of N—H···Cl···H—N hydrogen-bond networks, and the small Cl- anions, accessible from all directions, are well suited for this. Indeed, such dimers can be seen in the crystal structure of (I). Pairs of cations at (x, y, z) and (1 - x, 1 - y, -z) are connected into a hydrogen-bonded dimer involving both N4—H groups as acceptors, and two Cl4 anions (Fig. 2, top). The graph set (Etter et al., 1990; Bernstein et al., 1995) connected with this dimer is R42(8). Additional N1—H1C···Cl4 hydrogen bonds [R21(7) ring motif] add to the formation of this dimer. Another dimer is created by a pair of cations at (x, y, z) and (-x, 1 - y, -z). While the first dimer displays a kind of shift between the constituent long molecules, this one is almost exactly in a head-to-tail disposition (Fig. 2, bottom), with the ends closed by hydrogen bonds between terminal amine groups and perchlorate anions. The hydrogen-bond motifs in this dimer can be described by graph symbols R42(16) (the `inner' ring) and R44(32) (the `outer' ring). Together, these two dimeric structures form a ribbon of cations extending approximately along the [110] direction (Fig. 2c [There is no part (c) - please clarify]). N—H···O hydrogen bonds with perchlorate anions connect these ribbons into infinite tapes one unit-cell parameter wide, extending along the [001] direction (Fig. 3). Only weak interactions are observed between these tapes. Some relatively short and directional C—H···O contacts are also present in the structure, but they are probably `secondary' interactions, a consequence of the geometry of the molecules.
The Cl- anion accepts four hydrogen bonds, with the donor N atoms forming a distorted tetrahedron. Such an arrangement is less common than a three-coordinated one, with the Cl atom on top of a more or less flattened tripodal coordination pyramid (Warden et al., 2004). There are 492 organic structures (N···Cl distances shorter than 3.25 Å) with three N—H donor groups in the CSD, while only 65 have four such groups.