Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111003714/bm3101sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111003714/bm3101Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111003714/bm3101IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111003714/bm3101IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111003714/bm3101IVsup5.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111003714/bm3101Vsup6.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111003714/bm3101VIsup7.hkl |
CCDC references: 819296; 819297; 819298; 819299; 819300; 819301
All chemicals were purchased from commercial sources and used as received. Crystals were grown by slow evaporation, under ambient conditions, of methanol solutions containing a 1:1 ratio of amine and acid for (I)–(III) and (VI), and a ratio of 1:2 for (IV) and (V). Detailed masses and volumes are as follows. For (I): 2-propylamine (0.050 g, 0.85 mmol) and benzoic acid (0.103 g, 0.846 mmol) in methanol (5 ml); for (II): benzylamine (0.050 g, 0.47 mmol) and 2-phenylpropionic acid (0.070 g, 0.47 mmol) in methanol (5 ml); for (III): (RS)-1-phenylethylamine (0.050 g, 0.41 mmol) and 1-naphthalenecarboxylic acid (0.085 g, 0.41 mmol) in methanol (10 ml); for (IV): benzylamine (0.050 g, 0.047 mmol) and benzoic acid (0.114 g, 0.92 mmol) in methanol (10 ml); for (V): cyclopropylamine (0.050 g, 0.088 mmol) and benzoic acid (0.214 g, 0.18 mmol) in methanol (15 ml); and for (VI): cyclopropylamine (0.050 g, 0.088 mmol) and (cis/trans)-1,4-cyclohexanedicarboxylic acid (0.151 g, 0.088 mmol) in methanol (10 ml).
For compound (I), the C-bound H atoms were positioned geometrically, with C—H = 0.99 (methine CH), 0.97 (methylene CH3) or 0.94 Å (Ar—H), and refined as riding, with Uiso(H) = 1.2 or 1.5Ueq(C). The N-bound H atoms were positioned geometrically, with N—H = 0.91 Å, and refined as riding, with Uiso(H) = 1.5Ueq(N). The disorder of the 2-propylammonium cation was resolved by finding alternate positions for atom C9 in the difference Fourier map. These two atoms, C9A and C9B, were then refined anisotropically together with their site occupancy, such that the sum of the occupancies equalled one.
For compounds (II)–(VI), the C-bound H atoms were positioned geometrically, with C—H = 1.00 (methine CH), 0.99 (ethylene CH2), 0.98 (methylene CH3) or 0.95 Å (Ar—H), and refined as riding, with Uiso(H) = 1.2 or 1.5Ueq(C). The N-bound H atoms were positioned geometrically, with N—H = 0.91 Å, and refined as riding, with Uiso(H) = 1.5Ueq(N).
For all compounds, data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004) and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
C3H10N+·C7H5O2− | F(000) = 392 |
Mr = 181.23 | Dx = 1.065 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 1643 reflections |
a = 6.3823 (7) Å | θ = 0.4–27.5° |
b = 9.0629 (5) Å | µ = 0.07 mm−1 |
c = 19.5457 (13) Å | T = 243 K |
V = 1130.57 (16) Å3 | Needle, colourless |
Z = 4 | 0.26 × 0.16 × 0.1 mm |
Bruker APEXII CCD area-detector diffractometer | 869 reflections with I > 2σ(I) |
ω scans | Rint = 0.081 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | θmax = 25.5°, θmin = 3.1° |
Tmin = 0.981, Tmax = 0.993 | h = −7→7 |
9482 measured reflections | k = −10→8 |
1232 independent reflections | l = −23→22 |
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.1081P)2 + 0.123P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.061 | (Δ/σ)max < 0.001 |
wR(F2) = 0.181 | Δρmax = 0.20 e Å−3 |
S = 1.04 | Δρmin = −0.19 e Å−3 |
1232 reflections | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
133 parameters | Extinction coefficient: 0.043 (12) |
23 restraints | Absolute structure: Flack (1983), with 854 Friedel pairs |
C3H10N+·C7H5O2− | V = 1130.57 (16) Å3 |
Mr = 181.23 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.3823 (7) Å | µ = 0.07 mm−1 |
b = 9.0629 (5) Å | T = 243 K |
c = 19.5457 (13) Å | 0.26 × 0.16 × 0.1 mm |
Bruker APEXII CCD area-detector diffractometer | 1232 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 869 reflections with I > 2σ(I) |
Tmin = 0.981, Tmax = 0.993 | Rint = 0.081 |
9482 measured reflections |
R[F2 > 2σ(F2)] = 0.061 | 23 restraints |
wR(F2) = 0.181 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.20 e Å−3 |
1232 reflections | Δρmin = −0.19 e Å−3 |
133 parameters | Absolute structure: Flack (1983), with 854 Friedel pairs |
Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996) |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.8635 (5) | 0.4588 (3) | 0.34254 (15) | 0.0535 (8) | |
C2 | 0.6604 (6) | 0.4581 (6) | 0.3213 (2) | 0.0861 (13) | |
H2 | 0.5614 | 0.5182 | 0.3435 | 0.103* | |
C3 | 0.5987 (8) | 0.3692 (9) | 0.2671 (3) | 0.131 (3) | |
H3 | 0.4584 | 0.3686 | 0.2525 | 0.157* | |
C4 | 0.7434 (12) | 0.2829 (8) | 0.2353 (3) | 0.141 (3) | |
H4 | 0.7021 | 0.2223 | 0.1987 | 0.169* | |
C5 | 0.9443 (11) | 0.2832 (7) | 0.2556 (3) | 0.131 (2) | |
H5 | 1.0435 | 0.2237 | 0.2332 | 0.158* | |
C6 | 1.0036 (6) | 0.3716 (5) | 0.3095 (2) | 0.0854 (12) | |
H6 | 1.1442 | 0.3715 | 0.3238 | 0.103* | |
C7 | 0.9392 (6) | 0.5571 (4) | 0.39933 (17) | 0.0629 (9) | |
O1 | 0.8073 (5) | 0.6296 (4) | 0.43234 (16) | 0.1001 (11) | |
O2 | 1.1284 (4) | 0.5656 (4) | 0.40924 (15) | 0.1023 (11) | |
C8 | 0.4373 (9) | 0.4896 (6) | 0.5529 (2) | 0.1035 (15) | |
H8A | 0.5502 | 0.5104 | 0.5863 | 0.124* | 0.654 (12) |
H8B | 0.4486 | 0.397 | 0.5263 | 0.124* | 0.346 (12) |
C9A | 0.490 (2) | 0.3545 (9) | 0.5162 (5) | 0.160 (5) | 0.654 (12) |
H9A | 0.6235 | 0.3672 | 0.4931 | 0.24* | 0.654 (12) |
H9B | 0.3821 | 0.3333 | 0.4828 | 0.24* | 0.654 (12) |
H9C | 0.5003 | 0.2733 | 0.5484 | 0.24* | 0.654 (12) |
C9B | 0.633 (3) | 0.503 (2) | 0.5926 (10) | 0.145 (7) | 0.346 (12) |
H9D | 0.752 | 0.494 | 0.5621 | 0.218* | 0.346 (12) |
H9E | 0.6384 | 0.4252 | 0.6267 | 0.218* | 0.346 (12) |
H9F | 0.6366 | 0.5982 | 0.6152 | 0.218* | 0.346 (12) |
C10 | 0.2311 (13) | 0.4831 (9) | 0.5910 (3) | 0.146 (2) | |
H10A | 0.2373 | 0.406 | 0.6254 | 0.219* | |
H10B | 0.1188 | 0.4619 | 0.559 | 0.219* | |
H10C | 0.205 | 0.5773 | 0.613 | 0.219* | |
N1 | 0.4289 (4) | 0.6138 (3) | 0.50249 (14) | 0.0686 (9) | |
H1A | 0.5494 | 0.6169 | 0.4786 | 0.103* | |
H1B | 0.4112 | 0.6996 | 0.5249 | 0.103* | |
H1C | 0.321 | 0.5996 | 0.4736 | 0.103* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0547 (18) | 0.0550 (16) | 0.0509 (16) | −0.0060 (13) | 0.0076 (14) | −0.0036 (14) |
C2 | 0.065 (2) | 0.127 (3) | 0.066 (2) | −0.005 (2) | 0.0018 (18) | −0.019 (2) |
C3 | 0.088 (3) | 0.219 (7) | 0.087 (3) | −0.044 (4) | 0.000 (3) | −0.051 (4) |
C4 | 0.139 (5) | 0.180 (6) | 0.105 (4) | −0.071 (5) | 0.027 (4) | −0.077 (4) |
C5 | 0.133 (5) | 0.122 (4) | 0.139 (5) | −0.021 (4) | 0.051 (4) | −0.081 (4) |
C6 | 0.074 (3) | 0.093 (3) | 0.090 (3) | −0.004 (2) | 0.015 (2) | −0.027 (2) |
C7 | 0.064 (2) | 0.0684 (19) | 0.0562 (17) | −0.0085 (18) | 0.0081 (16) | −0.0026 (17) |
O1 | 0.0820 (19) | 0.107 (2) | 0.111 (2) | −0.0111 (16) | 0.0232 (17) | −0.0544 (19) |
O2 | 0.0666 (17) | 0.152 (3) | 0.088 (2) | −0.0107 (17) | −0.0149 (15) | −0.031 (2) |
C8 | 0.118 (3) | 0.106 (3) | 0.086 (3) | 0.020 (3) | 0.005 (3) | 0.019 (2) |
C9A | 0.250 (12) | 0.080 (4) | 0.151 (7) | 0.046 (6) | 0.060 (8) | 0.034 (4) |
C9B | 0.162 (7) | 0.145 (14) | 0.128 (14) | 0.026 (12) | −0.049 (8) | 0.023 (12) |
C10 | 0.161 (5) | 0.159 (5) | 0.118 (4) | 0.002 (5) | 0.044 (4) | 0.028 (4) |
N1 | 0.0621 (16) | 0.0755 (18) | 0.0683 (17) | 0.0024 (14) | −0.0043 (14) | −0.0155 (14) |
C1—C6 | 1.357 (5) | C8—C10 | 1.513 (9) |
C1—C2 | 1.361 (5) | C8—H8A | 0.99 |
C1—C7 | 1.503 (5) | C8—H8B | 0.99 |
C2—C3 | 1.388 (6) | C9A—H8B | 0.5074 |
C2—H2 | 0.94 | C9A—H9A | 0.97 |
C3—C4 | 1.361 (9) | C9A—H9B | 0.97 |
C3—H3 | 0.94 | C9A—H9C | 0.97 |
C4—C5 | 1.342 (10) | C9B—H9D | 0.97 |
C4—H4 | 0.94 | C9B—H9E | 0.97 |
C5—C6 | 1.377 (7) | C9B—H9F | 0.97 |
C5—H5 | 0.94 | C10—H10A | 0.97 |
C6—H6 | 0.94 | C10—H10B | 0.97 |
C7—O2 | 1.226 (4) | C10—H10C | 0.97 |
C7—O1 | 1.247 (4) | N1—H1A | 0.9 |
C8—C9A | 1.458 (10) | N1—H1B | 0.9 |
C8—C9B | 1.474 (18) | N1—H1C | 0.9 |
C8—N1 | 1.497 (5) | ||
C6—C1—C2 | 118.7 (4) | C9B—C8—H8B | 106.6 |
C6—C1—C7 | 119.0 (3) | N1—C8—H8B | 107.1 |
C2—C1—C7 | 122.3 (3) | C10—C8—H8B | 106.8 |
C1—C2—C3 | 120.4 (4) | H8A—C8—H8B | 117.1 |
C1—C2—H2 | 119.8 | C8—C9A—H9A | 109.5 |
C3—C2—H2 | 119.8 | H8B—C9A—H9A | 123.4 |
C4—C3—C2 | 119.3 (5) | C8—C9A—H9B | 109.5 |
C4—C3—H3 | 120.3 | H8B—C9A—H9B | 92.2 |
C2—C3—H3 | 120.3 | C8—C9A—H9C | 109.5 |
C5—C4—C3 | 120.8 (5) | H8B—C9A—H9C | 111 |
C5—C4—H4 | 119.6 | C8—C9B—H9D | 109.5 |
C3—C4—H4 | 119.6 | C8—C9B—H9E | 109.5 |
C4—C5—C6 | 119.3 (5) | H9D—C9B—H9E | 109.5 |
C4—C5—H5 | 120.3 | C8—C9B—H9F | 109.5 |
C6—C5—H5 | 120.3 | H9D—C9B—H9F | 109.5 |
C1—C6—C5 | 121.5 (4) | H9E—C9B—H9F | 109.5 |
C1—C6—H6 | 119.3 | C8—C10—H10A | 109.5 |
C5—C6—H6 | 119.3 | C8—C10—H10B | 109.5 |
O2—C7—O1 | 123.4 (4) | H10A—C10—H10B | 109.5 |
O2—C7—C1 | 118.1 (3) | C8—C10—H10C | 109.5 |
O1—C7—C1 | 118.5 (3) | H10A—C10—H10C | 109.5 |
C9A—C8—N1 | 108.4 (4) | H10B—C10—H10C | 109.5 |
C9B—C8—N1 | 108.4 (10) | C8—N1—H1A | 109.5 |
C9A—C8—C10 | 114.3 (7) | C8—N1—H1B | 109.5 |
C9B—C8—C10 | 118.7 (8) | H1A—N1—H1B | 109.5 |
N1—C8—C10 | 108.8 (4) | C8—N1—H1C | 109.5 |
C9A—C8—H8A | 108.4 | H1A—N1—H1C | 109.5 |
N1—C8—H8A | 108.4 | H1B—N1—H1C | 109.5 |
C10—C8—H8A | 108.4 | ||
C6—C1—C2—C3 | 0.3 (7) | C7—C1—C6—C5 | −177.7 (4) |
C7—C1—C2—C3 | 177.8 (4) | C4—C5—C6—C1 | −0.2 (9) |
C1—C2—C3—C4 | −0.1 (9) | C6—C1—C7—O2 | 7.1 (5) |
C2—C3—C4—C5 | −0.2 (11) | C2—C1—C7—O2 | −170.5 (4) |
C3—C4—C5—C6 | 0.4 (11) | C6—C1—C7—O1 | −175.3 (4) |
C2—C1—C6—C5 | −0.1 (7) | C2—C1—C7—O1 | 7.1 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.9 | 1.88 | 2.781 (4) | 177 |
N1—H1B···O1i | 0.9 | 1.88 | 2.763 (4) | 167 |
N1—H1C···O2ii | 0.9 | 1.79 | 2.681 (4) | 174 |
Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) x−1, y, z. |
C7H10N+·C9H9O2− | F(000) = 552 |
Mr = 257.32 | Dx = 1.217 Mg m−3 Dm = 0 Mg m−3 Dm measured by not measured |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2y | Cell parameters from 4876 reflections |
a = 30.970 (2) Å | θ = 2.7–28.1° |
b = 5.8832 (4) Å | µ = 0.08 mm−1 |
c = 7.8239 (5) Å | T = 173 K |
β = 99.825 (2)° | Plate, colourless |
V = 1404.63 (16) Å3 | 0.63 × 0.26 × 0.09 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 1660 reflections with I > 2σ(I) |
ω scans | Rint = 0.068 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | θmax = 28°, θmin = 1.3° |
Tmin = 0.951, Tmax = 0.993 | h = −40→40 |
16064 measured reflections | k = −7→7 |
1863 independent reflections | l = −10→10 |
Refinement on F2 | 1 restraint |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.035 | w = 1/[σ2(Fo2) + (0.0504P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.086 | (Δ/σ)max < 0.001 |
S = 1.09 | Δρmax = 0.21 e Å−3 |
1863 reflections | Δρmin = −0.15 e Å−3 |
174 parameters | Absolute structure: Flack (1983), with 1534 Friedel pairs |
C7H10N+·C9H9O2− | V = 1404.63 (16) Å3 |
Mr = 257.32 | Z = 4 |
Monoclinic, C2 | Mo Kα radiation |
a = 30.970 (2) Å | µ = 0.08 mm−1 |
b = 5.8832 (4) Å | T = 173 K |
c = 7.8239 (5) Å | 0.63 × 0.26 × 0.09 mm |
β = 99.825 (2)° |
Bruker APEXII CCD area-detector diffractometer | 1863 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1660 reflections with I > 2σ(I) |
Tmin = 0.951, Tmax = 0.993 | Rint = 0.068 |
16064 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 1 restraint |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.21 e Å−3 |
1863 reflections | Δρmin = −0.15 e Å−3 |
174 parameters | Absolute structure: Flack (1983), with 1534 Friedel pairs |
Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996) |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.30330 (5) | 0.6853 (3) | 0.7906 (2) | 0.0261 (3) | |
C2 | 0.31586 (5) | 0.5265 (3) | 0.9455 (2) | 0.0299 (4) | |
H2 | 0.3085 | 0.3672 | 0.9062 | 0.036* | |
C3 | 0.28863 (6) | 0.5874 (4) | 1.0844 (2) | 0.0392 (4) | |
H3A | 0.298 | 0.4938 | 1.1877 | 0.059* | |
H3B | 0.2576 | 0.5591 | 1.0396 | 0.059* | |
H3C | 0.2929 | 0.7484 | 1.1149 | 0.059* | |
C4 | 0.36465 (5) | 0.5402 (3) | 1.01108 (19) | 0.0292 (4) | |
C5 | 0.38331 (6) | 0.7262 (3) | 1.1045 (2) | 0.0366 (4) | |
H5 | 0.3652 | 0.8496 | 1.1264 | 0.044* | |
C6 | 0.42782 (6) | 0.7347 (4) | 1.1664 (2) | 0.0448 (5) | |
H6 | 0.44 | 0.8627 | 1.2312 | 0.054* | |
C7 | 0.45445 (6) | 0.5584 (4) | 1.1342 (2) | 0.0494 (5) | |
H7 | 0.4851 | 0.564 | 1.1766 | 0.059* | |
C8 | 0.43641 (6) | 0.3738 (4) | 1.0402 (2) | 0.0482 (5) | |
H8 | 0.4548 | 0.2525 | 1.0167 | 0.058* | |
C9 | 0.39188 (6) | 0.3632 (3) | 0.9796 (2) | 0.0386 (4) | |
H9 | 0.3798 | 0.2339 | 0.916 | 0.046* | |
O1 | 0.29267 (4) | 0.5987 (2) | 0.64142 (14) | 0.0328 (3) | |
O2 | 0.30422 (4) | 0.8926 (2) | 0.82038 (14) | 0.0339 (3) | |
C10 | 0.12920 (5) | 0.5775 (3) | 0.49970 (19) | 0.0321 (4) | |
C11 | 0.10961 (6) | 0.4026 (4) | 0.3950 (2) | 0.0392 (4) | |
H11 | 0.1263 | 0.273 | 0.3745 | 0.047* | |
C12 | 0.06590 (7) | 0.4164 (4) | 0.3205 (2) | 0.0477 (5) | |
H12 | 0.0527 | 0.2975 | 0.2477 | 0.057* | |
C13 | 0.04147 (6) | 0.6034 (4) | 0.3522 (2) | 0.0491 (5) | |
H13 | 0.0113 | 0.6124 | 0.3019 | 0.059* | |
C14 | 0.06063 (7) | 0.7761 (4) | 0.4559 (3) | 0.0492 (5) | |
H14 | 0.0438 | 0.9046 | 0.4773 | 0.059* | |
C15 | 0.10445 (6) | 0.7636 (4) | 0.5296 (2) | 0.0403 (4) | |
H15 | 0.1176 | 0.8839 | 0.6012 | 0.048* | |
C16 | 0.17665 (6) | 0.5610 (3) | 0.5796 (2) | 0.0351 (4) | |
H16A | 0.1817 | 0.6474 | 0.6898 | 0.042* | |
H16B | 0.1841 | 0.3999 | 0.6071 | 0.042* | |
N1 | 0.20620 (4) | 0.6503 (2) | 0.46383 (17) | 0.0294 (3) | |
H1A | 0.2344 | 0.6447 | 0.52 | 0.044* | |
H1B | 0.1989 | 0.7968 | 0.4348 | 0.044* | |
H1C | 0.2033 | 0.5641 | 0.366 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0210 (7) | 0.0288 (9) | 0.0277 (8) | 0.0001 (6) | 0.0018 (6) | 0.0004 (6) |
C2 | 0.0338 (8) | 0.0256 (8) | 0.0286 (8) | −0.0023 (7) | 0.0009 (6) | 0.0018 (7) |
C3 | 0.0379 (9) | 0.0444 (11) | 0.0361 (9) | −0.0017 (9) | 0.0088 (7) | 0.0086 (8) |
C4 | 0.0343 (9) | 0.0295 (9) | 0.0228 (7) | 0.0022 (7) | 0.0021 (6) | 0.0043 (7) |
C5 | 0.0394 (10) | 0.0338 (10) | 0.0351 (9) | −0.0020 (8) | 0.0023 (7) | 0.0002 (8) |
C6 | 0.0422 (11) | 0.0472 (12) | 0.0418 (10) | −0.0100 (9) | −0.0023 (8) | 0.0024 (9) |
C7 | 0.0311 (9) | 0.0718 (16) | 0.0425 (10) | 0.0001 (10) | −0.0017 (7) | 0.0110 (11) |
C8 | 0.0415 (10) | 0.0611 (14) | 0.0414 (10) | 0.0183 (10) | 0.0050 (8) | 0.0042 (10) |
C9 | 0.0438 (10) | 0.0402 (11) | 0.0294 (8) | 0.0095 (8) | −0.0005 (7) | −0.0016 (8) |
O1 | 0.0366 (6) | 0.0306 (6) | 0.0277 (5) | −0.0007 (5) | −0.0049 (4) | −0.0027 (5) |
O2 | 0.0474 (7) | 0.0244 (6) | 0.0302 (6) | 0.0039 (6) | 0.0072 (5) | 0.0007 (5) |
C10 | 0.0396 (9) | 0.0342 (9) | 0.0229 (7) | −0.0021 (8) | 0.0067 (6) | 0.0022 (7) |
C11 | 0.0437 (10) | 0.0368 (9) | 0.0391 (9) | −0.0053 (9) | 0.0130 (8) | −0.0037 (9) |
C12 | 0.0448 (11) | 0.0553 (13) | 0.0432 (10) | −0.0156 (11) | 0.0083 (8) | −0.0090 (10) |
C13 | 0.0336 (10) | 0.0679 (15) | 0.0455 (10) | −0.0025 (11) | 0.0063 (8) | 0.0066 (11) |
C14 | 0.0473 (12) | 0.0536 (13) | 0.0484 (11) | 0.0098 (10) | 0.0127 (9) | 0.0010 (11) |
C15 | 0.0503 (11) | 0.0368 (11) | 0.0342 (9) | 0.0007 (9) | 0.0087 (8) | −0.0042 (8) |
C16 | 0.0441 (10) | 0.0339 (10) | 0.0257 (7) | −0.0007 (8) | 0.0014 (6) | 0.0023 (7) |
N1 | 0.0317 (7) | 0.0249 (7) | 0.0282 (6) | −0.0003 (6) | −0.0041 (5) | −0.0005 (6) |
C1—O2 | 1.241 (2) | C9—H9 | 0.95 |
C1—O1 | 1.2644 (19) | C10—C15 | 1.379 (3) |
C1—C2 | 1.527 (2) | C10—C11 | 1.389 (3) |
C2—C4 | 1.513 (2) | C10—C16 | 1.499 (2) |
C2—C3 | 1.527 (2) | C11—C12 | 1.382 (3) |
C2—H2 | 1 | C11—H11 | 0.95 |
C3—H3A | 0.98 | C12—C13 | 1.381 (3) |
C3—H3B | 0.98 | C12—H12 | 0.95 |
C3—H3C | 0.98 | C13—C14 | 1.371 (3) |
C4—C5 | 1.386 (2) | C13—H13 | 0.95 |
C4—C9 | 1.388 (3) | C14—C15 | 1.383 (3) |
C5—C6 | 1.381 (3) | C14—H14 | 0.95 |
C5—H5 | 0.95 | C15—H15 | 0.95 |
C6—C7 | 1.375 (3) | C16—N1 | 1.489 (2) |
C6—H6 | 0.95 | C16—H16A | 0.99 |
C7—C8 | 1.376 (3) | C16—H16B | 0.99 |
C7—H7 | 0.95 | N1—H1A | 0.91 |
C8—C9 | 1.381 (3) | N1—H1B | 0.91 |
C8—H8 | 0.95 | N1—H1C | 0.91 |
O2—C1—O1 | 124.28 (15) | C4—C9—H9 | 119.8 |
O2—C1—C2 | 117.23 (14) | C15—C10—C11 | 119.26 (17) |
O1—C1—C2 | 118.49 (15) | C15—C10—C16 | 120.96 (16) |
C4—C2—C3 | 112.77 (13) | C11—C10—C16 | 119.79 (16) |
C4—C2—C1 | 109.92 (13) | C12—C11—C10 | 120.21 (19) |
C3—C2—C1 | 108.91 (14) | C12—C11—H11 | 119.9 |
C4—C2—H2 | 108.4 | C10—C11—H11 | 119.9 |
C3—C2—H2 | 108.4 | C13—C12—C11 | 119.90 (19) |
C1—C2—H2 | 108.4 | C13—C12—H12 | 120.1 |
C2—C3—H3A | 109.5 | C11—C12—H12 | 120.1 |
C2—C3—H3B | 109.5 | C14—C13—C12 | 120.10 (18) |
H3A—C3—H3B | 109.5 | C14—C13—H13 | 119.9 |
C2—C3—H3C | 109.5 | C12—C13—H13 | 119.9 |
H3A—C3—H3C | 109.5 | C13—C14—C15 | 120.2 (2) |
H3B—C3—H3C | 109.5 | C13—C14—H14 | 119.9 |
C5—C4—C9 | 118.33 (16) | C15—C14—H14 | 119.9 |
C5—C4—C2 | 121.57 (15) | C10—C15—C14 | 120.38 (18) |
C9—C4—C2 | 120.09 (15) | C10—C15—H15 | 119.8 |
C6—C5—C4 | 120.97 (18) | C14—C15—H15 | 119.8 |
C6—C5—H5 | 119.5 | N1—C16—C10 | 112.59 (12) |
C4—C5—H5 | 119.5 | N1—C16—H16A | 109.1 |
C7—C6—C5 | 120.16 (19) | C10—C16—H16A | 109.1 |
C7—C6—H6 | 119.9 | N1—C16—H16B | 109.1 |
C5—C6—H6 | 119.9 | C10—C16—H16B | 109.1 |
C6—C7—C8 | 119.47 (17) | H16A—C16—H16B | 107.8 |
C6—C7—H7 | 120.3 | C16—N1—H1A | 109.5 |
C8—C7—H7 | 120.3 | C16—N1—H1B | 109.5 |
C7—C8—C9 | 120.66 (19) | H1A—N1—H1B | 109.5 |
C7—C8—H8 | 119.7 | C16—N1—H1C | 109.5 |
C9—C8—H8 | 119.7 | H1A—N1—H1C | 109.5 |
C8—C9—C4 | 120.41 (18) | H1B—N1—H1C | 109.5 |
C8—C9—H9 | 119.8 | ||
O2—C1—C2—C4 | −71.75 (18) | C7—C8—C9—C4 | 0.7 (3) |
O1—C1—C2—C4 | 108.31 (16) | C5—C4—C9—C8 | −0.1 (3) |
O2—C1—C2—C3 | 52.26 (19) | C2—C4—C9—C8 | −179.50 (16) |
O1—C1—C2—C3 | −127.67 (16) | C15—C10—C11—C12 | 0.6 (3) |
C3—C2—C4—C5 | −47.4 (2) | C16—C10—C11—C12 | −179.88 (16) |
C1—C2—C4—C5 | 74.37 (18) | C10—C11—C12—C13 | −0.9 (3) |
C3—C2—C4—C9 | 132.03 (17) | C11—C12—C13—C14 | 0.6 (3) |
C1—C2—C4—C9 | −106.23 (17) | C12—C13—C14—C15 | −0.1 (3) |
C9—C4—C5—C6 | −0.6 (2) | C11—C10—C15—C14 | −0.1 (3) |
C2—C4—C5—C6 | 178.81 (16) | C16—C10—C15—C14 | −179.60 (16) |
C4—C5—C6—C7 | 0.7 (3) | C13—C14—C15—C10 | −0.2 (3) |
C5—C6—C7—C8 | 0.0 (3) | C15—C10—C16—N1 | −93.06 (18) |
C6—C7—C8—C9 | −0.7 (3) | C11—C10—C16—N1 | 87.43 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.91 | 1.91 | 2.8152 (16) | 174 |
N1—H1B···O1i | 0.91 | 1.91 | 2.7652 (18) | 157 |
N1—H1C···O2ii | 0.91 | 1.76 | 2.6651 (18) | 178 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1; (ii) −x+1/2, y−1/2, −z+1. |
C8H12N+·C11H7O2− | Z = 4 |
Mr = 293.35 | F(000) = 624 |
Triclinic, P1 | Dx = 1.188 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.8979 (9) Å | Cell parameters from 12505 reflections |
b = 12.0013 (8) Å | θ = 0.4–27.1° |
c = 16.0498 (15) Å | µ = 0.08 mm−1 |
α = 100.213 (5)° | T = 173 K |
β = 103.102 (3)° | Needle, colourless |
γ = 90.652 (5)° | 0.51 × 0.35 × 0.12 mm |
V = 1640.5 (3) Å3 |
Bruker APEXII CCD area-detector diffractometer | 3917 reflections with I > 2σ(I) |
ω scans | Rint = 0.075 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | θmax = 27.1°, θmin = 2.4° |
Tmin = 0.962, Tmax = 0.991 | h = −11→11 |
27233 measured reflections | k = −15→14 |
7082 independent reflections | l = −19→20 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.050 | w = 1/[σ2(Fo2) + (0.068P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.135 | (Δ/σ)max < 0.001 |
S = 1.00 | Δρmax = 0.22 e Å−3 |
7082 reflections | Δρmin = −0.25 e Å−3 |
401 parameters |
C8H12N+·C11H7O2− | γ = 90.652 (5)° |
Mr = 293.35 | V = 1640.5 (3) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.8979 (9) Å | Mo Kα radiation |
b = 12.0013 (8) Å | µ = 0.08 mm−1 |
c = 16.0498 (15) Å | T = 173 K |
α = 100.213 (5)° | 0.51 × 0.35 × 0.12 mm |
β = 103.102 (3)° |
Bruker APEXII CCD area-detector diffractometer | 7082 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3917 reflections with I > 2σ(I) |
Tmin = 0.962, Tmax = 0.991 | Rint = 0.075 |
27233 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.22 e Å−3 |
7082 reflections | Δρmin = −0.25 e Å−3 |
401 parameters |
Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996) |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | −0.0372 (2) | 0.66878 (13) | 0.33043 (11) | 0.0291 (4) | |
C2 | 0.0736 (2) | 0.60999 (15) | 0.37703 (12) | 0.0379 (4) | |
H2 | 0.1306 | 0.6457 | 0.4331 | 0.046* | |
C3 | 0.1044 (2) | 0.49875 (16) | 0.34374 (13) | 0.0478 (5) | |
H3 | 0.1799 | 0.4593 | 0.3775 | 0.057* | |
C4 | 0.0254 (2) | 0.44756 (16) | 0.26283 (13) | 0.0465 (5) | |
H4 | 0.0483 | 0.3728 | 0.24 | 0.056* | |
C5 | −0.0896 (2) | 0.50338 (14) | 0.21235 (11) | 0.0368 (4) | |
C6 | −0.1722 (3) | 0.45001 (16) | 0.12847 (13) | 0.0502 (5) | |
H6 | −0.1505 | 0.3747 | 0.1061 | 0.06* | |
C7 | −0.2815 (3) | 0.50399 (17) | 0.07935 (13) | 0.0540 (6) | |
H7 | −0.3358 | 0.4666 | 0.0231 | 0.065* | |
C8 | −0.3144 (3) | 0.61509 (17) | 0.11169 (13) | 0.0481 (5) | |
H8 | −0.3906 | 0.6528 | 0.0768 | 0.058* | |
C9 | −0.2385 (2) | 0.66975 (15) | 0.19248 (11) | 0.0363 (4) | |
H9 | −0.263 | 0.7449 | 0.2131 | 0.044* | |
C10 | −0.1238 (2) | 0.61658 (14) | 0.24634 (11) | 0.0304 (4) | |
C11 | −0.0576 (2) | 0.78893 (14) | 0.37164 (11) | 0.0300 (4) | |
O1 | 0.06319 (14) | 0.84530 (10) | 0.41804 (8) | 0.0357 (3) | |
O2 | −0.18822 (14) | 0.82804 (10) | 0.35959 (8) | 0.0419 (3) | |
C13 | 0.5803 (2) | 0.32449 (14) | 0.37054 (12) | 0.0378 (4) | |
H13 | 0.6408 | 0.3152 | 0.4255 | 0.045* | |
C14 | 0.6114 (2) | 0.41975 (16) | 0.33680 (13) | 0.0475 (5) | |
H14 | 0.6914 | 0.4743 | 0.3687 | 0.057* | |
C15 | 0.5263 (3) | 0.43367 (16) | 0.25806 (13) | 0.0476 (5) | |
H15 | 0.5481 | 0.4981 | 0.2351 | 0.057* | |
C16 | 0.4062 (2) | 0.35450 (15) | 0.20974 (12) | 0.0369 (4) | |
C17 | 0.3170 (3) | 0.36900 (18) | 0.12836 (13) | 0.0531 (6) | |
H17 | 0.338 | 0.4339 | 0.1056 | 0.064* | |
C18 | 0.2017 (3) | 0.29252 (19) | 0.08146 (13) | 0.0569 (6) | |
H18 | 0.143 | 0.3042 | 0.0267 | 0.068* | |
C19 | 0.1693 (2) | 0.19631 (17) | 0.11410 (12) | 0.0473 (5) | |
H19 | 0.0889 | 0.1428 | 0.081 | 0.057* | |
C20 | 0.2525 (2) | 0.17877 (15) | 0.19322 (11) | 0.0360 (4) | |
H20 | 0.2291 | 0.113 | 0.2142 | 0.043* | |
C21 | 0.3727 (2) | 0.25709 (13) | 0.24417 (11) | 0.0296 (4) | |
C22 | 0.4653 (2) | 0.24406 (13) | 0.32678 (11) | 0.0296 (4) | |
C23 | 0.4452 (2) | 0.14361 (14) | 0.36902 (11) | 0.0296 (4) | |
O3 | 0.56591 (14) | 0.11208 (10) | 0.41573 (7) | 0.0365 (3) | |
O4 | 0.31428 (15) | 0.09705 (10) | 0.35766 (8) | 0.0425 (3) | |
C24 | 0.3880 (2) | 0.80597 (15) | 0.26047 (12) | 0.0365 (4) | |
C25 | 0.2674 (3) | 0.72691 (19) | 0.22057 (14) | 0.0538 (6) | |
H25 | 0.2298 | 0.6802 | 0.2542 | 0.065* | |
C26 | 0.2003 (3) | 0.7146 (2) | 0.13242 (15) | 0.0641 (6) | |
H26 | 0.1178 | 0.6597 | 0.1059 | 0.077* | |
C27 | 0.2540 (3) | 0.7824 (2) | 0.08352 (14) | 0.0620 (7) | |
H27 | 0.2076 | 0.7754 | 0.0232 | 0.074* | |
C28 | 0.3747 (3) | 0.8602 (2) | 0.12225 (14) | 0.0617 (6) | |
H28 | 0.4129 | 0.9064 | 0.0885 | 0.074* | |
C29 | 0.4402 (3) | 0.87160 (17) | 0.20931 (13) | 0.0484 (5) | |
H29 | 0.5237 | 0.926 | 0.2351 | 0.058* | |
C30 | 0.4621 (2) | 0.82355 (15) | 0.35694 (12) | 0.0371 (4) | |
H30 | 0.5603 | 0.8706 | 0.3676 | 0.045* | |
C31 | 0.5024 (2) | 0.71338 (16) | 0.39042 (13) | 0.0478 (5) | |
H31A | 0.5507 | 0.731 | 0.4528 | 0.072* | |
H31B | 0.5745 | 0.6733 | 0.3592 | 0.072* | |
H31C | 0.408 | 0.6653 | 0.3807 | 0.072* | |
N1 | 0.35936 (17) | 0.88833 (11) | 0.40702 (9) | 0.0329 (4) | |
H1A | 0.2658 | 0.8501 | 0.3947 | 0.049* | |
H1B | 0.3468 | 0.9579 | 0.392 | 0.049* | |
H1C | 0.4027 | 0.8967 | 0.465 | 0.049* | |
C32 | 0.8890 (2) | 0.06757 (15) | 0.25853 (12) | 0.0379 (4) | |
C33 | 0.7690 (3) | 0.12616 (19) | 0.21794 (14) | 0.0541 (6) | |
H33 | 0.7329 | 0.1895 | 0.251 | 0.065* | |
C34 | 0.7008 (3) | 0.0942 (2) | 0.13029 (14) | 0.0644 (7) | |
H34 | 0.619 | 0.1355 | 0.1035 | 0.077* | |
C35 | 0.7522 (3) | 0.0019 (2) | 0.08197 (14) | 0.0636 (7) | |
H35 | 0.7053 | −0.0212 | 0.0218 | 0.076* | |
C36 | 0.8722 (3) | −0.05630 (19) | 0.12179 (14) | 0.0623 (7) | |
H36 | 0.9087 | −0.1193 | 0.0886 | 0.075* | |
C37 | 0.9394 (3) | −0.02401 (16) | 0.20894 (13) | 0.0479 (5) | |
H37 | 1.0215 | −0.0653 | 0.2354 | 0.057* | |
C38 | 0.9640 (2) | 0.09944 (15) | 0.35446 (12) | 0.0366 (4) | |
H38 | 1.0606 | 0.0573 | 0.3657 | 0.044* | |
C39 | 1.0088 (2) | 0.22533 (16) | 0.38598 (13) | 0.0465 (5) | |
H39A | 0.9168 | 0.2692 | 0.3736 | 0.07* | |
H39B | 1.0849 | 0.2482 | 0.3558 | 0.07* | |
H39C | 1.0536 | 0.2396 | 0.4488 | 0.07* | |
N2 | 0.85974 (17) | 0.06125 (12) | 0.40619 (9) | 0.0321 (3) | |
H2A | 0.7663 | 0.0919 | 0.3923 | 0.048* | |
H2B | 0.9025 | 0.0843 | 0.464 | 0.048* | |
H2C | 0.847 | −0.0157 | 0.3938 | 0.048* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0311 (10) | 0.0265 (9) | 0.0283 (9) | −0.0055 (7) | 0.0058 (8) | 0.0034 (7) |
C2 | 0.0418 (11) | 0.0334 (10) | 0.0344 (11) | −0.0009 (9) | 0.0009 (9) | 0.0054 (8) |
C3 | 0.0545 (13) | 0.0336 (11) | 0.0508 (13) | 0.0079 (10) | −0.0004 (11) | 0.0121 (9) |
C4 | 0.0624 (14) | 0.0280 (10) | 0.0481 (13) | 0.0072 (10) | 0.0126 (11) | 0.0045 (9) |
C5 | 0.0502 (12) | 0.0263 (9) | 0.0326 (10) | −0.0027 (8) | 0.0092 (9) | 0.0028 (8) |
C6 | 0.0738 (16) | 0.0339 (11) | 0.0370 (12) | −0.0036 (10) | 0.0095 (11) | −0.0041 (9) |
C7 | 0.0752 (16) | 0.0483 (13) | 0.0286 (11) | −0.0095 (11) | −0.0005 (11) | −0.0022 (9) |
C8 | 0.0576 (14) | 0.0457 (12) | 0.0358 (11) | −0.0043 (10) | −0.0033 (10) | 0.0126 (9) |
C9 | 0.0400 (11) | 0.0325 (10) | 0.0348 (11) | −0.0022 (8) | 0.0054 (9) | 0.0070 (8) |
C10 | 0.0348 (10) | 0.0274 (9) | 0.0300 (10) | −0.0052 (8) | 0.0089 (8) | 0.0066 (7) |
C11 | 0.0320 (11) | 0.0295 (9) | 0.0280 (10) | −0.0043 (8) | 0.0064 (8) | 0.0050 (7) |
O1 | 0.0326 (7) | 0.0340 (7) | 0.0344 (7) | −0.0077 (6) | 0.0036 (6) | −0.0036 (5) |
O2 | 0.0316 (8) | 0.0329 (7) | 0.0551 (9) | −0.0002 (6) | 0.0065 (6) | −0.0036 (6) |
C13 | 0.0392 (11) | 0.0325 (10) | 0.0375 (11) | −0.0003 (8) | 0.0012 (9) | 0.0053 (8) |
C14 | 0.0525 (13) | 0.0327 (10) | 0.0519 (13) | −0.0092 (9) | 0.0044 (11) | 0.0043 (9) |
C15 | 0.0643 (14) | 0.0305 (10) | 0.0510 (13) | −0.0030 (10) | 0.0157 (11) | 0.0133 (9) |
C16 | 0.0491 (12) | 0.0309 (10) | 0.0334 (10) | 0.0046 (9) | 0.0123 (9) | 0.0091 (8) |
C17 | 0.0782 (17) | 0.0481 (12) | 0.0370 (12) | 0.0041 (12) | 0.0128 (12) | 0.0191 (10) |
C18 | 0.0752 (17) | 0.0649 (15) | 0.0285 (11) | 0.0063 (13) | 0.0020 (11) | 0.0161 (11) |
C19 | 0.0561 (14) | 0.0489 (12) | 0.0303 (11) | 0.0007 (10) | 0.0012 (10) | 0.0011 (9) |
C20 | 0.0411 (11) | 0.0338 (10) | 0.0322 (10) | 0.0034 (9) | 0.0068 (9) | 0.0059 (8) |
C21 | 0.0351 (10) | 0.0263 (9) | 0.0285 (9) | 0.0078 (8) | 0.0096 (8) | 0.0044 (7) |
C22 | 0.0306 (10) | 0.0279 (9) | 0.0315 (10) | 0.0053 (8) | 0.0089 (8) | 0.0062 (7) |
C23 | 0.0304 (11) | 0.0293 (9) | 0.0283 (10) | 0.0056 (8) | 0.0067 (8) | 0.0033 (7) |
O3 | 0.0327 (7) | 0.0436 (7) | 0.0344 (7) | 0.0092 (6) | 0.0035 (6) | 0.0157 (6) |
O4 | 0.0320 (8) | 0.0436 (7) | 0.0555 (9) | 0.0014 (6) | 0.0051 (6) | 0.0250 (6) |
C24 | 0.0367 (11) | 0.0374 (10) | 0.0341 (10) | 0.0067 (9) | 0.0087 (9) | 0.0026 (8) |
C25 | 0.0539 (14) | 0.0634 (14) | 0.0452 (13) | −0.0040 (11) | 0.0127 (11) | 0.0119 (11) |
C26 | 0.0639 (16) | 0.0702 (16) | 0.0459 (14) | −0.0107 (12) | 0.0003 (12) | −0.0046 (12) |
C27 | 0.0839 (19) | 0.0654 (15) | 0.0312 (12) | 0.0110 (14) | 0.0061 (12) | 0.0032 (11) |
C28 | 0.0879 (19) | 0.0596 (14) | 0.0384 (13) | −0.0029 (13) | 0.0130 (13) | 0.0136 (11) |
C29 | 0.0611 (14) | 0.0427 (11) | 0.0399 (12) | −0.0026 (10) | 0.0089 (11) | 0.0075 (9) |
C30 | 0.0331 (10) | 0.0404 (10) | 0.0399 (11) | 0.0073 (8) | 0.0089 (9) | 0.0122 (8) |
C31 | 0.0519 (13) | 0.0446 (12) | 0.0488 (13) | 0.0137 (10) | 0.0106 (10) | 0.0140 (10) |
N1 | 0.0347 (9) | 0.0316 (8) | 0.0316 (8) | −0.0002 (7) | 0.0045 (7) | 0.0077 (6) |
C32 | 0.0429 (11) | 0.0397 (11) | 0.0343 (10) | −0.0025 (9) | 0.0135 (9) | 0.0095 (8) |
C33 | 0.0570 (14) | 0.0657 (14) | 0.0412 (13) | 0.0139 (11) | 0.0157 (11) | 0.0076 (10) |
C34 | 0.0635 (16) | 0.0844 (18) | 0.0469 (15) | 0.0144 (13) | 0.0080 (12) | 0.0213 (13) |
C35 | 0.0820 (18) | 0.0738 (16) | 0.0304 (12) | −0.0061 (14) | 0.0030 (12) | 0.0111 (11) |
C36 | 0.097 (2) | 0.0521 (13) | 0.0370 (13) | 0.0069 (13) | 0.0177 (13) | 0.0042 (10) |
C37 | 0.0673 (15) | 0.0396 (11) | 0.0380 (12) | 0.0044 (10) | 0.0138 (11) | 0.0080 (9) |
C38 | 0.0346 (11) | 0.0358 (10) | 0.0408 (11) | −0.0023 (8) | 0.0119 (9) | 0.0065 (8) |
C39 | 0.0528 (13) | 0.0383 (11) | 0.0480 (13) | −0.0077 (9) | 0.0142 (10) | 0.0041 (9) |
N2 | 0.0341 (8) | 0.0298 (8) | 0.0305 (8) | 0.0014 (6) | 0.0050 (7) | 0.0040 (6) |
C1—C2 | 1.378 (2) | C24—C29 | 1.380 (3) |
C1—C10 | 1.423 (2) | C24—C25 | 1.383 (3) |
C1—C11 | 1.507 (2) | C24—C30 | 1.515 (2) |
C2—C3 | 1.402 (3) | C25—C26 | 1.386 (3) |
C2—H2 | 0.95 | C25—H25 | 0.95 |
C3—C4 | 1.361 (3) | C26—C27 | 1.376 (3) |
C3—H3 | 0.95 | C26—H26 | 0.95 |
C4—C5 | 1.409 (3) | C27—C28 | 1.371 (3) |
C4—H4 | 0.95 | C27—H27 | 0.95 |
C5—C6 | 1.413 (3) | C28—C29 | 1.368 (3) |
C5—C10 | 1.434 (2) | C28—H28 | 0.95 |
C6—C7 | 1.355 (3) | C29—H29 | 0.95 |
C6—H6 | 0.95 | C30—N1 | 1.488 (2) |
C7—C8 | 1.402 (3) | C30—C31 | 1.530 (2) |
C7—H7 | 0.95 | C30—H30 | 1 |
C8—C9 | 1.364 (3) | C31—H31A | 0.98 |
C8—H8 | 0.95 | C31—H31B | 0.98 |
C9—C10 | 1.416 (2) | C31—H31C | 0.98 |
C9—H9 | 0.95 | N1—H1A | 0.91 |
C11—O2 | 1.245 (2) | N1—H1B | 0.91 |
C11—O1 | 1.269 (2) | N1—H1C | 0.91 |
C13—C22 | 1.373 (2) | C32—C37 | 1.380 (3) |
C13—C14 | 1.399 (3) | C32—C33 | 1.387 (3) |
C13—H13 | 0.95 | C32—C38 | 1.510 (3) |
C14—C15 | 1.357 (3) | C33—C34 | 1.382 (3) |
C14—H14 | 0.95 | C33—H33 | 0.95 |
C15—C16 | 1.409 (3) | C34—C35 | 1.379 (3) |
C15—H15 | 0.95 | C34—H34 | 0.95 |
C16—C17 | 1.407 (3) | C35—C36 | 1.380 (3) |
C16—C21 | 1.434 (2) | C35—H35 | 0.95 |
C17—C18 | 1.359 (3) | C36—C37 | 1.374 (3) |
C17—H17 | 0.95 | C36—H36 | 0.95 |
C18—C19 | 1.402 (3) | C37—H37 | 0.95 |
C18—H18 | 0.95 | C38—N2 | 1.494 (2) |
C19—C20 | 1.370 (3) | C38—C39 | 1.524 (3) |
C19—H19 | 0.95 | C38—H38 | 1 |
C20—C21 | 1.416 (2) | C39—H39A | 0.98 |
C20—H20 | 0.95 | C39—H39B | 0.98 |
C21—C22 | 1.429 (2) | C39—H39C | 0.98 |
C22—C23 | 1.511 (2) | N2—H2A | 0.91 |
C23—O4 | 1.247 (2) | N2—H2B | 0.91 |
C23—O3 | 1.2666 (19) | N2—H2C | 0.91 |
C2—C1—C10 | 119.99 (15) | C24—C25—C26 | 121.2 (2) |
C2—C1—C11 | 117.08 (15) | C24—C25—H25 | 119.4 |
C10—C1—C11 | 122.91 (15) | C26—C25—H25 | 119.4 |
C1—C2—C3 | 121.62 (17) | C27—C26—C25 | 119.6 (2) |
C1—C2—H2 | 119.2 | C27—C26—H26 | 120.2 |
C3—C2—H2 | 119.2 | C25—C26—H26 | 120.2 |
C4—C3—C2 | 119.64 (18) | C28—C27—C26 | 119.7 (2) |
C4—C3—H3 | 120.2 | C28—C27—H27 | 120.2 |
C2—C3—H3 | 120.2 | C26—C27—H27 | 120.2 |
C3—C4—C5 | 121.22 (17) | C29—C28—C27 | 120.3 (2) |
C3—C4—H4 | 119.4 | C29—C28—H28 | 119.9 |
C5—C4—H4 | 119.4 | C27—C28—H28 | 119.9 |
C4—C5—C6 | 121.23 (17) | C28—C29—C24 | 121.6 (2) |
C4—C5—C10 | 119.61 (16) | C28—C29—H29 | 119.2 |
C6—C5—C10 | 119.16 (17) | C24—C29—H29 | 119.2 |
C7—C6—C5 | 121.36 (18) | N1—C30—C24 | 109.71 (14) |
C7—C6—H6 | 119.3 | N1—C30—C31 | 110.06 (14) |
C5—C6—H6 | 119.3 | C24—C30—C31 | 113.80 (16) |
C6—C7—C8 | 119.84 (19) | N1—C30—H30 | 107.7 |
C6—C7—H7 | 120.1 | C24—C30—H30 | 107.7 |
C8—C7—H7 | 120.1 | C31—C30—H30 | 107.7 |
C9—C8—C7 | 120.90 (19) | C30—C31—H31A | 109.5 |
C9—C8—H8 | 119.5 | C30—C31—H31B | 109.5 |
C7—C8—H8 | 119.5 | H31A—C31—H31B | 109.5 |
C8—C9—C10 | 121.28 (17) | C30—C31—H31C | 109.5 |
C8—C9—H9 | 119.4 | H31A—C31—H31C | 109.5 |
C10—C9—H9 | 119.4 | H31B—C31—H31C | 109.5 |
C9—C10—C1 | 124.62 (15) | C30—N1—H1A | 109.5 |
C9—C10—C5 | 117.45 (16) | C30—N1—H1B | 109.5 |
C1—C10—C5 | 117.90 (15) | H1A—N1—H1B | 109.5 |
O2—C11—O1 | 123.32 (15) | C30—N1—H1C | 109.5 |
O2—C11—C1 | 120.10 (15) | H1A—N1—H1C | 109.5 |
O1—C11—C1 | 116.58 (15) | H1B—N1—H1C | 109.5 |
C22—C13—C14 | 122.15 (17) | C37—C32—C33 | 118.18 (18) |
C22—C13—H13 | 118.9 | C37—C32—C38 | 119.39 (17) |
C14—C13—H13 | 118.9 | C33—C32—C38 | 122.43 (17) |
C15—C14—C13 | 119.46 (18) | C34—C33—C32 | 121.3 (2) |
C15—C14—H14 | 120.3 | C34—C33—H33 | 119.4 |
C13—C14—H14 | 120.3 | C32—C33—H33 | 119.4 |
C14—C15—C16 | 121.35 (17) | C35—C34—C33 | 119.7 (2) |
C14—C15—H15 | 119.3 | C35—C34—H34 | 120.2 |
C16—C15—H15 | 119.3 | C33—C34—H34 | 120.2 |
C17—C16—C15 | 121.55 (17) | C34—C35—C36 | 119.4 (2) |
C17—C16—C21 | 118.89 (18) | C34—C35—H35 | 120.3 |
C15—C16—C21 | 119.57 (16) | C36—C35—H35 | 120.3 |
C18—C17—C16 | 121.66 (18) | C37—C36—C35 | 120.6 (2) |
C18—C17—H17 | 119.2 | C37—C36—H36 | 119.7 |
C16—C17—H17 | 119.2 | C35—C36—H36 | 119.7 |
C17—C18—C19 | 119.86 (19) | C36—C37—C32 | 120.9 (2) |
C17—C18—H18 | 120.1 | C36—C37—H37 | 119.6 |
C19—C18—H18 | 120.1 | C32—C37—H37 | 119.6 |
C20—C19—C18 | 120.64 (19) | N2—C38—C32 | 109.65 (14) |
C20—C19—H19 | 119.7 | N2—C38—C39 | 109.90 (14) |
C18—C19—H19 | 119.7 | C32—C38—C39 | 114.30 (15) |
C19—C20—C21 | 121.05 (17) | N2—C38—H38 | 107.6 |
C19—C20—H20 | 119.5 | C32—C38—H38 | 107.6 |
C21—C20—H20 | 119.5 | C39—C38—H38 | 107.6 |
C20—C21—C22 | 124.26 (15) | C38—C39—H39A | 109.5 |
C20—C21—C16 | 117.90 (15) | C38—C39—H39B | 109.5 |
C22—C21—C16 | 117.83 (16) | H39A—C39—H39B | 109.5 |
C13—C22—C21 | 119.63 (15) | C38—C39—H39C | 109.5 |
C13—C22—C23 | 117.23 (15) | H39A—C39—H39C | 109.5 |
C21—C22—C23 | 123.13 (15) | H39B—C39—H39C | 109.5 |
O4—C23—O3 | 123.43 (15) | C38—N2—H2A | 109.5 |
O4—C23—C22 | 119.95 (15) | C38—N2—H2B | 109.5 |
O3—C23—C22 | 116.61 (16) | H2A—N2—H2B | 109.5 |
C29—C24—C25 | 117.69 (18) | C38—N2—H2C | 109.5 |
C29—C24—C30 | 119.59 (17) | H2A—N2—H2C | 109.5 |
C25—C24—C30 | 122.72 (17) | H2B—N2—H2C | 109.5 |
C10—C1—C2—C3 | 0.1 (3) | C15—C16—C21—C20 | −179.26 (16) |
C11—C1—C2—C3 | −178.48 (17) | C17—C16—C21—C22 | 179.79 (17) |
C1—C2—C3—C4 | 1.2 (3) | C15—C16—C21—C22 | −0.7 (2) |
C2—C3—C4—C5 | −1.4 (3) | C14—C13—C22—C21 | −0.3 (3) |
C3—C4—C5—C6 | −179.69 (19) | C14—C13—C22—C23 | 178.68 (17) |
C3—C4—C5—C10 | 0.4 (3) | C20—C21—C22—C13 | 179.28 (16) |
C4—C5—C6—C7 | −179.2 (2) | C16—C21—C22—C13 | 0.8 (2) |
C10—C5—C6—C7 | 0.7 (3) | C20—C21—C22—C23 | 0.4 (2) |
C5—C6—C7—C8 | 0.0 (3) | C16—C21—C22—C23 | −178.09 (15) |
C6—C7—C8—C9 | −0.5 (3) | C13—C22—C23—O4 | 148.21 (17) |
C7—C8—C9—C10 | 0.2 (3) | C21—C22—C23—O4 | −32.8 (2) |
C8—C9—C10—C1 | 178.48 (17) | C13—C22—C23—O3 | −31.1 (2) |
C8—C9—C10—C5 | 0.5 (3) | C21—C22—C23—O3 | 147.86 (16) |
C2—C1—C10—C9 | −179.02 (17) | C29—C24—C25—C26 | −0.5 (3) |
C11—C1—C10—C9 | −0.5 (3) | C30—C24—C25—C26 | 178.71 (19) |
C2—C1—C10—C5 | −1.1 (2) | C24—C25—C26—C27 | −0.3 (3) |
C11—C1—C10—C5 | 177.40 (15) | C25—C26—C27—C28 | 1.0 (4) |
C4—C5—C10—C9 | 178.92 (17) | C26—C27—C28—C29 | −0.9 (4) |
C6—C5—C10—C9 | −1.0 (2) | C27—C28—C29—C24 | 0.1 (3) |
C4—C5—C10—C1 | 0.8 (2) | C25—C24—C29—C28 | 0.6 (3) |
C6—C5—C10—C1 | −179.05 (17) | C30—C24—C29—C28 | −178.65 (19) |
C2—C1—C11—O2 | −145.61 (17) | C29—C24—C30—N1 | 103.07 (19) |
C10—C1—C11—O2 | 35.9 (2) | C25—C24—C30—N1 | −76.1 (2) |
C2—C1—C11—O1 | 34.2 (2) | C29—C24—C30—C31 | −133.13 (19) |
C10—C1—C11—O1 | −144.34 (16) | C25—C24—C30—C31 | 47.6 (2) |
C22—C13—C14—C15 | −0.4 (3) | C37—C32—C33—C34 | 0.1 (3) |
C13—C14—C15—C16 | 0.5 (3) | C38—C32—C33—C34 | −179.00 (19) |
C14—C15—C16—C17 | 179.5 (2) | C32—C33—C34—C35 | 0.3 (3) |
C14—C15—C16—C21 | 0.1 (3) | C33—C34—C35—C36 | −0.7 (4) |
C15—C16—C17—C18 | 179.7 (2) | C34—C35—C36—C37 | 0.7 (4) |
C21—C16—C17—C18 | −0.8 (3) | C35—C36—C37—C32 | −0.3 (3) |
C16—C17—C18—C19 | 0.0 (3) | C33—C32—C37—C36 | −0.1 (3) |
C17—C18—C19—C20 | 0.3 (3) | C38—C32—C37—C36 | 179.04 (18) |
C18—C19—C20—C21 | 0.1 (3) | C37—C32—C38—N2 | −103.52 (19) |
C19—C20—C21—C22 | −179.38 (17) | C33—C32—C38—N2 | 75.6 (2) |
C19—C20—C21—C16 | −0.9 (3) | C37—C32—C38—C39 | 132.58 (19) |
C17—C16—C21—C20 | 1.2 (2) | C33—C32—C38—C39 | −48.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.91 | 1.92 | 2.7305 (19) | 147 |
N1—H1B···O4i | 0.91 | 1.86 | 2.7650 (17) | 178 |
N1—H1C···O3ii | 0.91 | 1.89 | 2.7716 (18) | 162 |
N2—H2A···O3 | 0.91 | 1.91 | 2.7232 (18) | 147 |
N2—H2B···O1ii | 0.91 | 1.89 | 2.7695 (19) | 163 |
N2—H2C···O2iii | 0.91 | 1.86 | 2.7678 (18) | 175 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z+1; (iii) x+1, y−1, z. |
C7H10N+·C7H5O2−·C7H6O2 | F(000) = 744 |
Mr = 351.39 | Dx = 1.263 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 24815 reflections |
a = 12.3249 (11) Å | θ = 0.4–27.1° |
b = 6.0804 (6) Å | µ = 0.09 mm−1 |
c = 24.7669 (17) Å | T = 173 K |
β = 95.526 (5)° | Block, colourless |
V = 1847.4 (3) Å3 | 0.5 × 0.08 × 0.06 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 4004 independent reflections |
Radiation source: fine-focus sealed tube | 2214 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.094 |
ω scans | θmax = 27°, θmin = 3.1° |
Absorption correction: integration (XPREP; Bruker, 2004) | h = −15→15 |
Tmin = 0.957, Tmax = 0.995 | k = −7→7 |
22843 measured reflections | l = −31→30 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.045 | w = 1/[σ2(Fo2) + (0.0545P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.114 | (Δ/σ)max = 0.002 |
S = 0.96 | Δρmax = 0.21 e Å−3 |
4004 reflections | Δρmin = −0.22 e Å−3 |
237 parameters |
C7H10N+·C7H5O2−·C7H6O2 | V = 1847.4 (3) Å3 |
Mr = 351.39 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.3249 (11) Å | µ = 0.09 mm−1 |
b = 6.0804 (6) Å | T = 173 K |
c = 24.7669 (17) Å | 0.5 × 0.08 × 0.06 mm |
β = 95.526 (5)° |
Bruker APEXII CCD area-detector diffractometer | 4004 independent reflections |
Absorption correction: integration (XPREP; Bruker, 2004) | 2214 reflections with I > 2σ(I) |
Tmin = 0.957, Tmax = 0.995 | Rint = 0.094 |
22843 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 0.96 | Δρmax = 0.21 e Å−3 |
4004 reflections | Δρmin = −0.22 e Å−3 |
237 parameters |
Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 2004) |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.72097 (13) | 0.1218 (3) | 0.39195 (6) | 0.0243 (4) | |
C2 | 0.77136 (13) | −0.0759 (3) | 0.40748 (7) | 0.0301 (4) | |
H2 | 0.7654 | −0.132 | 0.4429 | 0.036* | |
C3 | 0.83019 (14) | −0.1920 (3) | 0.37203 (7) | 0.0382 (5) | |
H3A | 0.8634 | −0.3278 | 0.383 | 0.046* | |
C4 | 0.84071 (15) | −0.1112 (4) | 0.32093 (8) | 0.0436 (6) | |
H4 | 0.8817 | −0.1902 | 0.2967 | 0.052* | |
C5 | 0.79147 (16) | 0.0850 (4) | 0.30498 (8) | 0.0472 (6) | |
H5 | 0.7983 | 0.1409 | 0.2697 | 0.057* | |
C6 | 0.73197 (14) | 0.2009 (3) | 0.34033 (7) | 0.0365 (5) | |
H6 | 0.6984 | 0.3361 | 0.329 | 0.044* | |
C7 | 0.65643 (13) | 0.2460 (3) | 0.43049 (7) | 0.0236 (4) | |
O1 | 0.63819 (9) | 0.15715 (19) | 0.47483 (4) | 0.0261 (3) | |
O2 | 0.62322 (9) | 0.4378 (2) | 0.41757 (4) | 0.0305 (3) | |
C8 | 0.44262 (14) | 0.9390 (3) | 0.29160 (6) | 0.0282 (4) | |
C9 | 0.45026 (15) | 0.8606 (3) | 0.23976 (7) | 0.0402 (5) | |
H9 | 0.4851 | 0.7239 | 0.2346 | 0.048* | |
C10 | 0.40736 (18) | 0.9804 (4) | 0.19535 (7) | 0.0535 (6) | |
H10 | 0.412 | 0.9248 | 0.1598 | 0.064* | |
C11 | 0.35791 (17) | 1.1800 (4) | 0.20240 (8) | 0.0468 (6) | |
H11 | 0.3293 | 1.2624 | 0.1717 | 0.056* | |
C12 | 0.34980 (16) | 1.2598 (4) | 0.25331 (8) | 0.0456 (6) | |
H12 | 0.3158 | 1.3977 | 0.2581 | 0.055* | |
C13 | 0.39134 (17) | 1.1390 (3) | 0.29801 (7) | 0.0415 (5) | |
H13 | 0.3846 | 1.1937 | 0.3335 | 0.05* | |
C14 | 0.48561 (14) | 0.8134 (3) | 0.34045 (7) | 0.0305 (5) | |
O3 | 0.54779 (11) | 0.6453 (2) | 0.32883 (4) | 0.0401 (4) | |
H3 | 0.573 | 0.5836 | 0.3577 | 0.048* | |
O4 | 0.46587 (10) | 0.8575 (2) | 0.38636 (4) | 0.0421 (4) | |
C15 | 0.25443 (13) | 0.2956 (3) | 0.44232 (6) | 0.0234 (4) | |
C16 | 0.18925 (14) | 0.4720 (3) | 0.45402 (6) | 0.0284 (4) | |
H16 | 0.2217 | 0.6088 | 0.4648 | 0.034* | |
C17 | 0.07698 (15) | 0.4491 (4) | 0.45003 (7) | 0.0346 (5) | |
H17 | 0.0325 | 0.5705 | 0.4579 | 0.042* | |
C18 | 0.02966 (15) | 0.2506 (4) | 0.43475 (7) | 0.0407 (5) | |
H18 | −0.0473 | 0.2346 | 0.4325 | 0.049* | |
C19 | 0.09366 (16) | 0.0757 (3) | 0.42269 (7) | 0.0407 (5) | |
H19 | 0.0608 | −0.0607 | 0.4119 | 0.049* | |
C20 | 0.20618 (15) | 0.0977 (3) | 0.42617 (7) | 0.0321 (5) | |
H20 | 0.2501 | −0.0231 | 0.4174 | 0.039* | |
C21 | 0.37664 (13) | 0.3184 (3) | 0.44681 (6) | 0.0280 (4) | |
H21A | 0.4068 | 0.2182 | 0.4205 | 0.034* | |
H21B | 0.396 | 0.4708 | 0.4375 | 0.034* | |
N1 | 0.42661 (11) | 0.2654 (2) | 0.50288 (5) | 0.0249 (4) | |
H1A | 0.5003 | 0.2555 | 0.5028 | 0.037* | |
H1B | 0.3998 | 0.1349 | 0.5138 | 0.037* | |
H1C | 0.4101 | 0.3736 | 0.5261 | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0201 (9) | 0.0252 (11) | 0.0272 (9) | −0.0020 (8) | 0.0001 (7) | −0.0032 (8) |
C2 | 0.0240 (10) | 0.0296 (12) | 0.0364 (10) | −0.0010 (9) | 0.0020 (8) | −0.0002 (9) |
C3 | 0.0275 (11) | 0.0332 (13) | 0.0536 (13) | 0.0059 (9) | 0.0022 (9) | −0.0062 (11) |
C4 | 0.0324 (11) | 0.0545 (16) | 0.0438 (13) | 0.0082 (11) | 0.0035 (9) | −0.0173 (11) |
C5 | 0.0445 (13) | 0.0664 (17) | 0.0318 (11) | 0.0133 (12) | 0.0094 (9) | −0.0005 (11) |
C6 | 0.0361 (11) | 0.0419 (13) | 0.0317 (10) | 0.0103 (10) | 0.0039 (8) | 0.0027 (10) |
C7 | 0.0208 (9) | 0.0240 (11) | 0.0248 (9) | −0.0034 (8) | −0.0047 (7) | −0.0023 (9) |
O1 | 0.0289 (7) | 0.0262 (7) | 0.0232 (6) | 0.0005 (6) | 0.0024 (5) | 0.0016 (6) |
O2 | 0.0397 (8) | 0.0239 (8) | 0.0280 (7) | 0.0066 (6) | 0.0040 (5) | 0.0019 (6) |
C8 | 0.0299 (10) | 0.0310 (12) | 0.0232 (9) | 0.0003 (9) | 0.0003 (7) | 0.0002 (9) |
C9 | 0.0478 (13) | 0.0445 (13) | 0.0282 (10) | 0.0112 (11) | 0.0039 (9) | −0.0007 (10) |
C10 | 0.0722 (16) | 0.0654 (18) | 0.0230 (11) | 0.0152 (14) | 0.0054 (10) | 0.0040 (11) |
C11 | 0.0496 (13) | 0.0572 (16) | 0.0328 (11) | 0.0062 (12) | −0.0002 (9) | 0.0162 (11) |
C12 | 0.0564 (14) | 0.0371 (13) | 0.0420 (12) | 0.0125 (11) | −0.0023 (10) | 0.0052 (10) |
C13 | 0.0593 (14) | 0.0358 (13) | 0.0281 (10) | 0.0092 (11) | −0.0034 (9) | −0.0033 (10) |
C14 | 0.0309 (11) | 0.0304 (12) | 0.0293 (10) | 0.0012 (9) | −0.0021 (8) | −0.0035 (9) |
O3 | 0.0528 (9) | 0.0408 (9) | 0.0257 (7) | 0.0187 (7) | −0.0005 (6) | 0.0019 (7) |
O4 | 0.0572 (9) | 0.0486 (9) | 0.0202 (7) | 0.0161 (7) | 0.0017 (6) | −0.0010 (6) |
C15 | 0.0263 (10) | 0.0276 (11) | 0.0156 (8) | −0.0027 (9) | −0.0019 (7) | 0.0015 (8) |
C16 | 0.0346 (11) | 0.0279 (11) | 0.0223 (9) | −0.0019 (9) | 0.0011 (8) | −0.0005 (8) |
C17 | 0.0323 (11) | 0.0425 (13) | 0.0299 (10) | 0.0051 (10) | 0.0072 (8) | 0.0028 (10) |
C18 | 0.0249 (11) | 0.0558 (16) | 0.0411 (11) | −0.0071 (11) | 0.0010 (9) | 0.0111 (11) |
C19 | 0.0383 (13) | 0.0335 (13) | 0.0479 (12) | −0.0137 (11) | −0.0073 (10) | 0.0023 (10) |
C20 | 0.0347 (11) | 0.0277 (12) | 0.0323 (10) | −0.0001 (9) | −0.0054 (8) | −0.0010 (9) |
C21 | 0.0294 (10) | 0.0352 (12) | 0.0192 (9) | −0.0027 (9) | 0.0011 (7) | 0.0004 (8) |
N1 | 0.0251 (8) | 0.0251 (9) | 0.0239 (7) | −0.0011 (7) | −0.0001 (6) | 0.0000 (7) |
C1—C6 | 1.385 (2) | C12—H12 | 0.95 |
C1—C2 | 1.390 (2) | C13—H13 | 0.95 |
C1—C7 | 1.504 (2) | C14—O4 | 1.2152 (19) |
C2—C3 | 1.385 (2) | C14—O3 | 1.326 (2) |
C2—H2 | 0.95 | O3—H3 | 0.84 |
C3—C4 | 1.375 (2) | C15—C20 | 1.384 (2) |
C3—H3A | 0.95 | C15—C16 | 1.387 (2) |
C4—C5 | 1.379 (3) | C15—C21 | 1.506 (2) |
C4—H4 | 0.95 | C16—C17 | 1.385 (2) |
C5—C6 | 1.388 (3) | C16—H16 | 0.95 |
C5—H5 | 0.95 | C17—C18 | 1.378 (3) |
C6—H6 | 0.95 | C17—H17 | 0.95 |
C7—O1 | 1.2633 (19) | C18—C19 | 1.374 (3) |
C7—O2 | 1.267 (2) | C18—H18 | 0.95 |
C8—C9 | 1.381 (2) | C19—C20 | 1.388 (3) |
C8—C13 | 1.386 (3) | C19—H19 | 0.95 |
C8—C14 | 1.485 (2) | C20—H20 | 0.95 |
C9—C10 | 1.381 (3) | C21—N1 | 1.4989 (19) |
C9—H9 | 0.95 | C21—H21A | 0.99 |
C10—C11 | 1.377 (3) | C21—H21B | 0.99 |
C10—H10 | 0.95 | N1—H1A | 0.91 |
C11—C12 | 1.364 (3) | N1—H1B | 0.91 |
C11—H11 | 0.95 | N1—H1C | 0.91 |
C12—C13 | 1.385 (3) | ||
C6—C1—C2 | 118.37 (16) | C12—C13—H13 | 119.6 |
C6—C1—C7 | 121.07 (16) | C8—C13—H13 | 119.6 |
C2—C1—C7 | 120.56 (15) | O4—C14—O3 | 123.03 (16) |
C3—C2—C1 | 120.83 (17) | O4—C14—C8 | 124.13 (17) |
C3—C2—H2 | 119.6 | O3—C14—C8 | 112.83 (15) |
C1—C2—H2 | 119.6 | C14—O3—H3 | 109.5 |
C4—C3—C2 | 120.20 (19) | C20—C15—C16 | 119.41 (16) |
C4—C3—H3A | 119.9 | C20—C15—C21 | 120.01 (16) |
C2—C3—H3A | 119.9 | C16—C15—C21 | 120.58 (16) |
C3—C4—C5 | 119.64 (18) | C17—C16—C15 | 120.16 (17) |
C3—C4—H4 | 120.2 | C17—C16—H16 | 119.9 |
C5—C4—H4 | 120.2 | C15—C16—H16 | 119.9 |
C4—C5—C6 | 120.24 (19) | C18—C17—C16 | 120.08 (18) |
C4—C5—H5 | 119.9 | C18—C17—H17 | 120 |
C6—C5—H5 | 119.9 | C16—C17—H17 | 120 |
C1—C6—C5 | 120.70 (19) | C19—C18—C17 | 120.07 (17) |
C1—C6—H6 | 119.6 | C19—C18—H18 | 120 |
C5—C6—H6 | 119.6 | C17—C18—H18 | 120 |
O1—C7—O2 | 122.22 (16) | C18—C19—C20 | 120.21 (18) |
O1—C7—C1 | 119.09 (16) | C18—C19—H19 | 119.9 |
O2—C7—C1 | 118.69 (15) | C20—C19—H19 | 119.9 |
C9—C8—C13 | 118.80 (17) | C15—C20—C19 | 120.05 (18) |
C9—C8—C14 | 121.93 (17) | C15—C20—H20 | 120 |
C13—C8—C14 | 119.26 (15) | C19—C20—H20 | 120 |
C10—C9—C8 | 120.22 (19) | N1—C21—C15 | 111.56 (13) |
C10—C9—H9 | 119.9 | N1—C21—H21A | 109.3 |
C8—C9—H9 | 119.9 | C15—C21—H21A | 109.3 |
C11—C10—C9 | 120.25 (18) | N1—C21—H21B | 109.3 |
C11—C10—H10 | 119.9 | C15—C21—H21B | 109.3 |
C9—C10—H10 | 119.9 | H21A—C21—H21B | 108 |
C12—C11—C10 | 120.24 (18) | C21—N1—H1A | 109.5 |
C12—C11—H11 | 119.9 | C21—N1—H1B | 109.5 |
C10—C11—H11 | 119.9 | H1A—N1—H1B | 109.5 |
C11—C12—C13 | 119.7 (2) | C21—N1—H1C | 109.5 |
C11—C12—H12 | 120.1 | H1A—N1—H1C | 109.5 |
C13—C12—H12 | 120.1 | H1B—N1—H1C | 109.5 |
C12—C13—C8 | 120.74 (17) | ||
C6—C1—C2—C3 | −0.7 (2) | C11—C12—C13—C8 | 1.0 (3) |
C7—C1—C2—C3 | 179.48 (15) | C9—C8—C13—C12 | −0.9 (3) |
C1—C2—C3—C4 | 0.8 (3) | C14—C8—C13—C12 | −179.64 (18) |
C2—C3—C4—C5 | −0.6 (3) | C9—C8—C14—O4 | −167.81 (18) |
C3—C4—C5—C6 | 0.3 (3) | C13—C8—C14—O4 | 10.9 (3) |
C2—C1—C6—C5 | 0.3 (3) | C9—C8—C14—O3 | 11.7 (2) |
C7—C1—C6—C5 | −179.85 (16) | C13—C8—C14—O3 | −169.57 (17) |
C4—C5—C6—C1 | −0.1 (3) | C20—C15—C16—C17 | 0.6 (2) |
C6—C1—C7—O1 | 172.24 (15) | C21—C15—C16—C17 | −179.68 (15) |
C2—C1—C7—O1 | −7.9 (2) | C15—C16—C17—C18 | 0.4 (2) |
C6—C1—C7—O2 | −8.6 (2) | C16—C17—C18—C19 | −0.9 (3) |
C2—C1—C7—O2 | 171.30 (15) | C17—C18—C19—C20 | 0.4 (3) |
C13—C8—C9—C10 | 0.0 (3) | C16—C15—C20—C19 | −1.1 (2) |
C14—C8—C9—C10 | 178.72 (18) | C21—C15—C20—C19 | 179.17 (15) |
C8—C9—C10—C11 | 0.8 (3) | C18—C19—C20—C15 | 0.6 (3) |
C9—C10—C11—C12 | −0.8 (3) | C20—C15—C21—N1 | −91.71 (18) |
C10—C11—C12—C13 | −0.1 (3) | C16—C15—C21—N1 | 88.60 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.84 | 1.79 | 2.6255 (16) | 177 |
N1—H1A···O1 | 0.91 | 1.99 | 2.8399 (18) | 155 |
N1—H1B···O1i | 0.91 | 1.87 | 2.7620 (18) | 168 |
N1—H1C···O2ii | 0.91 | 1.88 | 2.7835 (17) | 171 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1. |
C3H8N+·C7H5O2−·C7H6O2 | F(000) = 640 |
Mr = 301.33 | Dx = 1.248 Mg m−3 Dm = 0 Mg m−3 Dm measured by not measured |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1969 reflections |
a = 15.3307 (10) Å | θ = 2.9–27.6° |
b = 6.3703 (3) Å | µ = 0.09 mm−1 |
c = 17.9989 (11) Å | T = 173 K |
β = 114.199 (2)° | Block, colourless |
V = 1603.33 (16) Å3 | 0.34 × 0.2 × 0.1 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 2461 reflections with I > 2σ(I) |
ω scans | Rint = 0.028 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | θmax = 28.0°, θmin = 1.5° |
Tmin = 0.970, Tmax = 0.991 | h = −14→20 |
9730 measured reflections | k = −7→8 |
3876 independent reflections | l = −23→21 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.044 | w = 1/[σ2(Fo2) + (0.0437P)2 + 0.2204P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.11 | (Δ/σ)max = 0.006 |
S = 1.00 | Δρmax = 0.19 e Å−3 |
3876 reflections | Δρmin = −0.19 e Å−3 |
200 parameters |
C3H8N+·C7H5O2−·C7H6O2 | V = 1603.33 (16) Å3 |
Mr = 301.33 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.3307 (10) Å | µ = 0.09 mm−1 |
b = 6.3703 (3) Å | T = 173 K |
c = 17.9989 (11) Å | 0.34 × 0.2 × 0.1 mm |
β = 114.199 (2)° |
Bruker APEXII CCD area-detector diffractometer | 3876 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2461 reflections with I > 2σ(I) |
Tmin = 0.970, Tmax = 0.991 | Rint = 0.028 |
9730 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.11 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.19 e Å−3 |
3876 reflections | Δρmin = −0.19 e Å−3 |
200 parameters |
Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996) |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.78280 (10) | 0.1676 (2) | 0.57876 (9) | 0.0314 (3) | |
C2 | 0.86076 (12) | 0.2719 (3) | 0.63506 (11) | 0.0472 (4) | |
H2 | 0.8528 | 0.4085 | 0.6525 | 0.057* | |
C3 | 0.95012 (14) | 0.1798 (3) | 0.66630 (12) | 0.0609 (5) | |
H3A | 1.0031 | 0.2535 | 0.705 | 0.073* | |
C4 | 0.96290 (14) | −0.0170 (3) | 0.64184 (12) | 0.0581 (5) | |
H4 | 1.0246 | −0.0795 | 0.6631 | 0.07* | |
C5 | 0.88607 (14) | −0.1231 (3) | 0.58644 (14) | 0.0562 (5) | |
H5 | 0.8943 | −0.2604 | 0.5698 | 0.067* | |
C6 | 0.79663 (12) | −0.0313 (2) | 0.55471 (12) | 0.0448 (4) | |
H6 | 0.7439 | −0.1056 | 0.5159 | 0.054* | |
C7 | 0.68468 (11) | 0.2651 (2) | 0.54413 (9) | 0.0311 (3) | |
O1 | 0.67544 (8) | 0.45045 (15) | 0.56561 (7) | 0.0443 (3) | |
O2 | 0.61583 (7) | 0.16305 (15) | 0.49517 (7) | 0.0365 (3) | |
C8 | 0.76369 (10) | 0.9573 (2) | 0.77606 (9) | 0.0323 (3) | |
C9 | 0.83615 (12) | 0.8712 (3) | 0.84356 (11) | 0.0450 (4) | |
H9 | 0.8564 | 0.7312 | 0.8416 | 0.054* | |
C10 | 0.87921 (14) | 0.9873 (3) | 0.91361 (12) | 0.0588 (5) | |
H10 | 0.9293 | 0.9273 | 0.9597 | 0.071* | |
C11 | 0.85028 (14) | 1.1892 (3) | 0.91732 (12) | 0.0566 (5) | |
H11 | 0.88 | 1.2686 | 0.9659 | 0.068* | |
C12 | 0.77849 (14) | 1.2758 (3) | 0.85077 (12) | 0.0522 (5) | |
H12 | 0.7584 | 1.4156 | 0.8534 | 0.063* | |
C13 | 0.73478 (12) | 1.1614 (2) | 0.77958 (10) | 0.0400 (4) | |
H13 | 0.6852 | 1.2227 | 0.7334 | 0.048* | |
C14 | 0.71382 (11) | 0.8330 (2) | 0.70051 (10) | 0.0334 (3) | |
O3 | 0.75692 (9) | 0.65301 (16) | 0.70143 (7) | 0.0496 (3) | |
H3 | 0.7265 | 0.5879 | 0.6578 | 0.074* | |
O4 | 0.64141 (8) | 0.88983 (16) | 0.64465 (7) | 0.0418 (3) | |
C15 | 0.52382 (12) | 0.7411 (2) | 0.38333 (10) | 0.0389 (4) | |
H15 | 0.4869 | 0.862 | 0.3497 | 0.047* | |
C16 | 0.59417 (14) | 0.6443 (3) | 0.35686 (12) | 0.0518 (5) | |
H16A | 0.6539 | 0.5879 | 0.3995 | 0.062* | |
H16B | 0.6012 | 0.706 | 0.3091 | 0.062* | |
C17 | 0.50236 (13) | 0.5329 (3) | 0.34255 (11) | 0.0509 (5) | |
H17A | 0.4528 | 0.5263 | 0.286 | 0.061* | |
H17B | 0.5056 | 0.4082 | 0.3764 | 0.061* | |
N1 | 0.54718 (9) | 0.75446 (18) | 0.47059 (8) | 0.0335 (3) | |
H1A | 0.5832 | 0.6415 | 0.4965 | 0.05* | |
H1B | 0.4922 | 0.7558 | 0.4785 | 0.05* | |
H1C | 0.5807 | 0.8744 | 0.4911 | 0.05* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0332 (8) | 0.0275 (7) | 0.0386 (8) | 0.0015 (6) | 0.0199 (7) | 0.0018 (6) |
C2 | 0.0374 (10) | 0.0518 (10) | 0.0524 (11) | 0.0007 (8) | 0.0183 (9) | −0.0137 (9) |
C3 | 0.0375 (11) | 0.0867 (15) | 0.0537 (12) | 0.0043 (10) | 0.0138 (9) | −0.0147 (11) |
C4 | 0.0419 (11) | 0.0736 (13) | 0.0646 (13) | 0.0224 (10) | 0.0276 (10) | 0.0162 (11) |
C5 | 0.0542 (12) | 0.0368 (9) | 0.0930 (16) | 0.0112 (8) | 0.0458 (12) | 0.0070 (10) |
C6 | 0.0400 (10) | 0.0290 (8) | 0.0731 (13) | −0.0017 (7) | 0.0309 (9) | −0.0052 (8) |
C7 | 0.0362 (9) | 0.0238 (7) | 0.0372 (8) | 0.0000 (6) | 0.0191 (7) | −0.0016 (6) |
O1 | 0.0470 (7) | 0.0273 (5) | 0.0518 (7) | 0.0073 (5) | 0.0135 (6) | −0.0102 (5) |
O2 | 0.0338 (6) | 0.0269 (5) | 0.0474 (7) | −0.0024 (4) | 0.0153 (5) | −0.0058 (5) |
C8 | 0.0319 (8) | 0.0314 (7) | 0.0367 (8) | −0.0034 (6) | 0.0173 (7) | −0.0025 (6) |
C9 | 0.0403 (10) | 0.0418 (9) | 0.0465 (11) | 0.0012 (7) | 0.0111 (8) | −0.0013 (8) |
C10 | 0.0504 (12) | 0.0685 (13) | 0.0426 (11) | −0.0042 (10) | 0.0039 (9) | −0.0027 (10) |
C11 | 0.0583 (13) | 0.0671 (13) | 0.0436 (11) | −0.0208 (10) | 0.0202 (10) | −0.0218 (10) |
C12 | 0.0608 (13) | 0.0410 (9) | 0.0587 (12) | −0.0085 (9) | 0.0286 (11) | −0.0171 (9) |
C13 | 0.0437 (10) | 0.0332 (8) | 0.0418 (9) | −0.0020 (7) | 0.0161 (8) | −0.0042 (7) |
C14 | 0.0373 (9) | 0.0284 (7) | 0.0375 (9) | 0.0006 (6) | 0.0185 (8) | −0.0003 (7) |
O3 | 0.0580 (8) | 0.0351 (6) | 0.0466 (7) | 0.0120 (5) | 0.0122 (6) | −0.0084 (5) |
O4 | 0.0403 (7) | 0.0395 (6) | 0.0402 (7) | 0.0038 (5) | 0.0111 (6) | −0.0062 (5) |
C15 | 0.0409 (10) | 0.0313 (8) | 0.0432 (9) | 0.0071 (7) | 0.0157 (8) | −0.0023 (7) |
C16 | 0.0576 (12) | 0.0535 (11) | 0.0557 (12) | 0.0132 (9) | 0.0349 (10) | 0.0058 (9) |
C17 | 0.0601 (12) | 0.0408 (9) | 0.0470 (10) | 0.0037 (8) | 0.0171 (9) | −0.0121 (8) |
N1 | 0.0292 (7) | 0.0244 (6) | 0.0470 (8) | −0.0014 (5) | 0.0158 (6) | −0.0084 (6) |
C1—C2 | 1.380 (2) | C11—C12 | 1.367 (3) |
C1—C6 | 1.383 (2) | C11—H11 | 0.95 |
C1—C7 | 1.506 (2) | C12—C13 | 1.385 (2) |
C2—C3 | 1.380 (2) | C12—H12 | 0.95 |
C2—H2 | 0.95 | C13—H13 | 0.95 |
C3—C4 | 1.369 (3) | C14—O4 | 1.2081 (18) |
C3—H3A | 0.95 | C14—O3 | 1.3200 (17) |
C4—C5 | 1.369 (3) | O3—H3 | 0.84 |
C4—H4 | 0.95 | C15—N1 | 1.463 (2) |
C5—C6 | 1.381 (2) | C15—C16 | 1.480 (2) |
C5—H5 | 0.95 | C15—C17 | 1.486 (2) |
C6—H6 | 0.95 | C15—H15 | 1 |
C7—O2 | 1.2454 (17) | C16—C17 | 1.501 (3) |
C7—O1 | 1.2682 (16) | C16—H16A | 0.99 |
C8—C9 | 1.380 (2) | C16—H16B | 0.99 |
C8—C13 | 1.383 (2) | C17—H17A | 0.99 |
C8—C14 | 1.486 (2) | C17—H17B | 0.99 |
C9—C10 | 1.375 (2) | N1—H1A | 0.91 |
C9—H9 | 0.95 | N1—H1B | 0.91 |
C10—C11 | 1.371 (3) | N1—H1C | 0.91 |
C10—H10 | 0.95 | ||
C2—C1—C6 | 118.24 (15) | C11—C12—H12 | 119.7 |
C2—C1—C7 | 121.51 (13) | C13—C12—H12 | 119.7 |
C6—C1—C7 | 120.24 (14) | C12—C13—C8 | 119.62 (17) |
C1—C2—C3 | 120.72 (16) | C12—C13—H13 | 120.2 |
C1—C2—H2 | 119.6 | C8—C13—H13 | 120.2 |
C3—C2—H2 | 119.6 | O4—C14—O3 | 123.73 (14) |
C4—C3—C2 | 120.46 (19) | O4—C14—C8 | 123.66 (13) |
C4—C3—H3A | 119.8 | O3—C14—C8 | 112.61 (14) |
C2—C3—H3A | 119.8 | C14—O3—H3 | 109.5 |
C3—C4—C5 | 119.49 (17) | N1—C15—C16 | 118.66 (14) |
C3—C4—H4 | 120.3 | N1—C15—C17 | 119.31 (14) |
C5—C4—H4 | 120.3 | C16—C15—C17 | 60.80 (11) |
C4—C5—C6 | 120.27 (17) | N1—C15—H15 | 115.7 |
C4—C5—H5 | 119.9 | C16—C15—H15 | 115.7 |
C6—C5—H5 | 119.9 | C17—C15—H15 | 115.7 |
C5—C6—C1 | 120.81 (17) | C15—C16—C17 | 59.78 (11) |
C5—C6—H6 | 119.6 | C15—C16—H16A | 117.8 |
C1—C6—H6 | 119.6 | C17—C16—H16A | 117.8 |
O2—C7—O1 | 122.25 (14) | C15—C16—H16B | 117.8 |
O2—C7—C1 | 119.36 (12) | C17—C16—H16B | 117.8 |
O1—C7—C1 | 118.39 (13) | H16A—C16—H16B | 114.9 |
C9—C8—C13 | 119.39 (15) | C15—C17—C16 | 59.42 (11) |
C9—C8—C14 | 121.35 (14) | C15—C17—H17A | 117.8 |
C13—C8—C14 | 119.24 (14) | C16—C17—H17A | 117.8 |
C10—C9—C8 | 120.29 (16) | C15—C17—H17B | 117.8 |
C10—C9—H9 | 119.9 | C16—C17—H17B | 117.8 |
C8—C9—H9 | 119.9 | H17A—C17—H17B | 115 |
C11—C10—C9 | 120.39 (18) | C15—N1—H1A | 109.5 |
C11—C10—H10 | 119.8 | C15—N1—H1B | 109.5 |
C9—C10—H10 | 119.8 | H1A—N1—H1B | 109.5 |
C12—C11—C10 | 119.75 (17) | C15—N1—H1C | 109.5 |
C12—C11—H11 | 120.1 | H1A—N1—H1C | 109.5 |
C10—C11—H11 | 120.1 | H1B—N1—H1C | 109.5 |
C11—C12—C13 | 120.57 (17) | ||
C6—C1—C2—C3 | 0.1 (3) | C14—C8—C9—C10 | −177.98 (16) |
C7—C1—C2—C3 | 179.85 (16) | C8—C9—C10—C11 | 0.4 (3) |
C1—C2—C3—C4 | 0.0 (3) | C9—C10—C11—C12 | −0.3 (3) |
C2—C3—C4—C5 | −0.5 (3) | C10—C11—C12—C13 | −0.1 (3) |
C3—C4—C5—C6 | 0.8 (3) | C11—C12—C13—C8 | 0.4 (3) |
C4—C5—C6—C1 | −0.7 (3) | C9—C8—C13—C12 | −0.3 (2) |
C2—C1—C6—C5 | 0.2 (2) | C14—C8—C13—C12 | 177.63 (15) |
C7—C1—C6—C5 | −179.53 (15) | C9—C8—C14—O4 | 168.67 (15) |
C2—C1—C7—O2 | −178.00 (15) | C13—C8—C14—O4 | −9.3 (2) |
C6—C1—C7—O2 | 1.7 (2) | C9—C8—C14—O3 | −10.8 (2) |
C2—C1—C7—O1 | 2.6 (2) | C13—C8—C14—O3 | 171.22 (14) |
C6—C1—C7—O1 | −177.69 (14) | N1—C15—C16—C17 | 109.49 (16) |
C13—C8—C9—C10 | 0.0 (2) | N1—C15—C17—C16 | −108.45 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O1 | 0.84 | 1.75 | 2.5881 (16) | 173 |
N1—H1A···O1 | 0.91 | 1.89 | 2.7901 (16) | 168 |
N1—H1B···O2i | 0.91 | 1.97 | 2.8573 (16) | 165 |
N1—H1C···O2ii | 0.91 | 1.91 | 2.7743 (15) | 158 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z. |
2C3H8N+·C8H10O42−·C8H12O4 | F(000) = 992 |
Mr = 458.54 | Dx = 1.297 Mg m−3 Dm = 0 Mg m−3 Dm measured by not measured |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 8893 reflections |
a = 10.2478 (4) Å | θ = 2.3–28.1° |
b = 9.6134 (4) Å | µ = 0.10 mm−1 |
c = 23.8354 (9) Å | T = 173 K |
V = 2348.17 (16) Å3 | Triangle, colourless |
Z = 4 | 0.56 × 0.4 × 0.07 mm |
Bruker APEXII CCD area-detector diffractometer | 2735 reflections with I > 2σ(I) |
ω scans | Rint = 0.037 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | θmax = 28.0°, θmin = 1.7° |
Tmin = 0.947, Tmax = 0.993 | h = −13→13 |
27099 measured reflections | k = −12→11 |
2909 independent reflections | l = −26→31 |
Refinement on F2 | 1 restraint |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.035 | w = 1/[σ2(Fo2) + (0.0621P)2 + 0.3462P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.094 | (Δ/σ)max = 0.001 |
S = 1.04 | Δρmax = 0.33 e Å−3 |
2909 reflections | Δρmin = −0.18 e Å−3 |
293 parameters | Absolute structure: Flack (1983), with 2122 Friedel pairs |
2C3H8N+·C8H10O42−·C8H12O4 | V = 2348.17 (16) Å3 |
Mr = 458.54 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 10.2478 (4) Å | µ = 0.10 mm−1 |
b = 9.6134 (4) Å | T = 173 K |
c = 23.8354 (9) Å | 0.56 × 0.4 × 0.07 mm |
Bruker APEXII CCD area-detector diffractometer | 2909 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2735 reflections with I > 2σ(I) |
Tmin = 0.947, Tmax = 0.993 | Rint = 0.037 |
27099 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 1 restraint |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.33 e Å−3 |
2909 reflections | Δρmin = −0.18 e Å−3 |
293 parameters | Absolute structure: Flack (1983), with 2122 Friedel pairs |
Experimental. Absorption corrections were made using the program SADABS (Sheldrick, 1996) |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.53031 (18) | 0.8886 (2) | 0.61593 (8) | 0.0159 (4) | |
H1 | 0.459 | 0.9243 | 0.6407 | 0.019* | |
C2 | 0.47606 (19) | 0.76215 (19) | 0.58481 (8) | 0.0170 (4) | |
H2D | 0.4449 | 0.6928 | 0.6124 | 0.02* | |
H2E | 0.5467 | 0.7186 | 0.5625 | 0.02* | |
C3 | 0.36322 (19) | 0.8022 (2) | 0.54561 (8) | 0.0184 (4) | |
H3A | 0.3341 | 0.7189 | 0.5247 | 0.022* | |
H3B | 0.2887 | 0.836 | 0.5683 | 0.022* | |
C4 | 0.40401 (18) | 0.9149 (2) | 0.50418 (8) | 0.0172 (4) | |
H4 | 0.3245 | 0.9434 | 0.4827 | 0.021* | |
C5 | 0.4519 (2) | 1.0418 (2) | 0.53664 (9) | 0.0226 (4) | |
H5A | 0.3792 | 1.08 | 0.5593 | 0.027* | |
H5B | 0.4799 | 1.1146 | 0.5098 | 0.027* | |
C6 | 0.5656 (2) | 1.0056 (2) | 0.57531 (8) | 0.0212 (4) | |
H6A | 0.591 | 1.0893 | 0.5969 | 0.025* | |
H6B | 0.6415 | 0.9769 | 0.5524 | 0.025* | |
C7 | 0.64613 (18) | 0.8536 (2) | 0.65394 (8) | 0.0161 (4) | |
C8 | 0.50671 (18) | 0.8663 (2) | 0.46154 (8) | 0.0170 (4) | |
O1 | 0.65311 (14) | 0.72828 (15) | 0.67225 (6) | 0.0213 (3) | |
O2 | 0.72535 (16) | 0.94572 (16) | 0.66630 (7) | 0.0276 (3) | |
O3 | 0.50529 (14) | 0.73805 (15) | 0.44698 (6) | 0.0217 (3) | |
O4 | 0.58416 (15) | 0.95240 (16) | 0.44247 (6) | 0.0261 (3) | |
C9 | 0.78798 (18) | 0.5424 (2) | 0.31075 (8) | 0.0171 (4) | |
H9 | 0.7624 | 0.5184 | 0.2714 | 0.021* | |
C10 | 0.83307 (18) | 0.4084 (2) | 0.34001 (9) | 0.0195 (4) | |
H10A | 0.8568 | 0.4292 | 0.3794 | 0.023* | |
H10B | 0.7609 | 0.34 | 0.3403 | 0.023* | |
C11 | 0.95106 (19) | 0.3465 (2) | 0.30950 (9) | 0.0193 (4) | |
H11A | 0.9813 | 0.2625 | 0.3297 | 0.023* | |
H11B | 0.9253 | 0.3185 | 0.2711 | 0.023* | |
C12 | 1.06206 (18) | 0.4521 (2) | 0.30630 (8) | 0.0161 (4) | |
H12 | 1.0886 | 0.4761 | 0.3455 | 0.019* | |
C13 | 1.01603 (19) | 0.5862 (2) | 0.27744 (9) | 0.0197 (4) | |
H13A | 1.0882 | 0.6547 | 0.2769 | 0.024* | |
H13B | 0.9916 | 0.5657 | 0.2381 | 0.024* | |
C14 | 0.89913 (19) | 0.6479 (2) | 0.30821 (9) | 0.0193 (4) | |
H14A | 0.8692 | 0.7328 | 0.2885 | 0.023* | |
H14B | 0.9251 | 0.6745 | 0.3467 | 0.023* | |
C15 | 1.18106 (18) | 0.4006 (2) | 0.27562 (8) | 0.0168 (4) | |
C16 | 0.66857 (18) | 0.5964 (2) | 0.34083 (8) | 0.0173 (4) | |
O5 | 0.69379 (14) | 0.67242 (17) | 0.38507 (7) | 0.0270 (3) | |
H5 | 0.6239 | 0.6901 | 0.4021 | 0.04* | |
O6 | 0.55794 (14) | 0.56647 (16) | 0.32570 (6) | 0.0227 (3) | |
O7 | 1.15657 (15) | 0.31369 (17) | 0.23494 (7) | 0.0261 (3) | |
H7 | 1.2259 | 0.2964 | 0.2174 | 0.039* | |
O8 | 1.29028 (14) | 0.44374 (16) | 0.28676 (6) | 0.0227 (3) | |
C17 | 0.5095 (2) | 0.3923 (2) | 0.67976 (11) | 0.0304 (5) | |
H17 | 0.4443 | 0.3155 | 0.6835 | 0.036* | |
C18 | 0.5772 (4) | 0.4002 (3) | 0.62473 (11) | 0.0460 (8) | |
H18A | 0.6013 | 0.4934 | 0.6104 | 0.055* | |
H18B | 0.5523 | 0.3319 | 0.5955 | 0.055* | |
C19 | 0.6470 (3) | 0.3474 (3) | 0.67527 (12) | 0.0398 (6) | |
H19A | 0.6656 | 0.2465 | 0.6773 | 0.048* | |
H19B | 0.7145 | 0.4079 | 0.6922 | 0.048* | |
N1 | 0.47602 (17) | 0.52266 (19) | 0.70892 (8) | 0.0223 (4) | |
H1B | 0.479 | 0.5087 | 0.7467 | 0.033* | |
H1C | 0.3942 | 0.5497 | 0.6989 | 0.033* | |
H1A | 0.5342 | 0.59 | 0.6993 | 0.033* | |
C20 | 0.3644 (2) | 0.4084 (2) | 0.43062 (10) | 0.0277 (5) | |
H20 | 0.3104 | 0.3268 | 0.419 | 0.033* | |
C21 | 0.4022 (3) | 0.4101 (3) | 0.48986 (12) | 0.0447 (7) | |
H21A | 0.3705 | 0.3335 | 0.514 | 0.054* | |
H21B | 0.4095 | 0.5016 | 0.5087 | 0.054* | |
C22 | 0.4998 (3) | 0.3756 (3) | 0.44567 (14) | 0.0451 (7) | |
H22A | 0.5677 | 0.4458 | 0.437 | 0.054* | |
H22B | 0.5286 | 0.2777 | 0.4424 | 0.054* | |
N2 | 0.33162 (17) | 0.54013 (18) | 0.40263 (7) | 0.0216 (4) | |
H2A | 0.3863 | 0.6082 | 0.4149 | 0.032* | |
H2B | 0.2478 | 0.5637 | 0.4108 | 0.032* | |
H2C | 0.3405 | 0.5299 | 0.3649 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0178 (8) | 0.0186 (9) | 0.0112 (8) | 0.0024 (7) | −0.0012 (7) | 0.0022 (7) |
C2 | 0.0209 (8) | 0.0167 (8) | 0.0136 (8) | 0.0001 (7) | −0.0020 (7) | 0.0041 (7) |
C3 | 0.0165 (8) | 0.0264 (9) | 0.0124 (8) | −0.0005 (7) | 0.0014 (7) | 0.0015 (7) |
C4 | 0.0172 (8) | 0.0234 (9) | 0.0109 (8) | 0.0058 (7) | 0.0001 (7) | 0.0021 (7) |
C5 | 0.0344 (11) | 0.0177 (9) | 0.0157 (9) | 0.0088 (8) | 0.0005 (9) | 0.0036 (8) |
C6 | 0.0316 (10) | 0.0151 (8) | 0.0171 (9) | −0.0031 (8) | −0.0037 (8) | −0.0011 (7) |
C7 | 0.0170 (8) | 0.0215 (9) | 0.0099 (8) | 0.0019 (7) | −0.0008 (7) | −0.0011 (7) |
C8 | 0.0164 (8) | 0.0261 (9) | 0.0084 (8) | 0.0036 (7) | −0.0015 (6) | −0.0008 (7) |
O1 | 0.0204 (7) | 0.0243 (7) | 0.0191 (7) | 0.0006 (5) | −0.0048 (6) | 0.0071 (6) |
O2 | 0.0270 (8) | 0.0271 (8) | 0.0287 (8) | −0.0032 (6) | −0.0097 (7) | 0.0009 (7) |
O3 | 0.0216 (7) | 0.0254 (7) | 0.0181 (7) | −0.0008 (6) | 0.0038 (6) | −0.0058 (6) |
O4 | 0.0266 (8) | 0.0290 (8) | 0.0227 (7) | −0.0031 (6) | 0.0082 (6) | 0.0024 (6) |
C9 | 0.0154 (8) | 0.0228 (9) | 0.0132 (8) | 0.0014 (7) | 0.0008 (7) | −0.0041 (7) |
C10 | 0.0183 (9) | 0.0179 (9) | 0.0223 (10) | −0.0015 (7) | 0.0065 (8) | −0.0011 (8) |
C11 | 0.0190 (9) | 0.0159 (9) | 0.0229 (9) | 0.0004 (7) | 0.0057 (8) | −0.0017 (7) |
C12 | 0.0149 (8) | 0.0208 (9) | 0.0127 (8) | 0.0007 (7) | 0.0011 (7) | −0.0036 (7) |
C13 | 0.0191 (9) | 0.0185 (9) | 0.0214 (10) | 0.0007 (7) | 0.0053 (8) | −0.0001 (8) |
C14 | 0.0205 (9) | 0.0164 (9) | 0.0210 (9) | 0.0016 (7) | 0.0045 (8) | 0.0000 (7) |
C15 | 0.0169 (8) | 0.0204 (9) | 0.0132 (8) | 0.0018 (7) | 0.0017 (7) | 0.0001 (7) |
C16 | 0.0176 (9) | 0.0188 (9) | 0.0157 (9) | 0.0017 (7) | 0.0017 (7) | −0.0019 (7) |
O5 | 0.0182 (7) | 0.0388 (9) | 0.0239 (8) | 0.0000 (6) | 0.0036 (6) | −0.0160 (7) |
O6 | 0.0162 (6) | 0.0304 (8) | 0.0214 (7) | 0.0012 (6) | 0.0004 (6) | −0.0065 (6) |
O7 | 0.0188 (7) | 0.0370 (8) | 0.0225 (7) | 0.0000 (6) | 0.0044 (6) | −0.0125 (7) |
O8 | 0.0172 (7) | 0.0297 (8) | 0.0212 (7) | −0.0006 (6) | 0.0013 (6) | −0.0065 (6) |
C17 | 0.0320 (11) | 0.0210 (10) | 0.0381 (13) | −0.0020 (9) | −0.0056 (10) | 0.0058 (10) |
C18 | 0.083 (2) | 0.0281 (12) | 0.0274 (13) | 0.0166 (13) | −0.0013 (14) | −0.0006 (10) |
C19 | 0.0429 (14) | 0.0381 (13) | 0.0385 (15) | 0.0114 (11) | −0.0079 (12) | −0.0103 (12) |
N1 | 0.0186 (8) | 0.0280 (9) | 0.0203 (8) | 0.0000 (7) | −0.0017 (7) | 0.0063 (7) |
C20 | 0.0342 (11) | 0.0180 (9) | 0.0310 (11) | 0.0006 (8) | 0.0078 (9) | −0.0012 (9) |
C21 | 0.073 (2) | 0.0315 (12) | 0.0298 (13) | 0.0163 (13) | 0.0050 (13) | 0.0104 (11) |
C22 | 0.0383 (13) | 0.0430 (15) | 0.0540 (18) | 0.0129 (12) | 0.0069 (13) | 0.0234 (14) |
N2 | 0.0208 (8) | 0.0242 (8) | 0.0198 (8) | 0.0003 (7) | 0.0024 (7) | 0.0000 (7) |
C1—C6 | 1.528 (3) | C13—C14 | 1.525 (3) |
C1—C2 | 1.528 (3) | C13—H13A | 0.99 |
C1—C7 | 1.530 (3) | C13—H13B | 0.99 |
C1—H1 | 1 | C14—H14A | 0.99 |
C2—C3 | 1.536 (3) | C14—H14B | 0.99 |
C2—H2D | 0.99 | C15—O8 | 1.223 (2) |
C2—H2E | 0.99 | C15—O7 | 1.305 (2) |
C3—C4 | 1.525 (3) | C16—O6 | 1.224 (2) |
C3—H3A | 0.99 | C16—O5 | 1.309 (2) |
C3—H3B | 0.99 | O5—H5 | 0.84 |
C4—C5 | 1.526 (3) | O7—H7 | 0.84 |
C4—C8 | 1.536 (3) | C17—N1 | 1.474 (3) |
C4—H4 | 1 | C17—C19 | 1.477 (4) |
C5—C6 | 1.526 (3) | C17—C18 | 1.485 (4) |
C5—H5A | 0.99 | C17—H17 | 1 |
C5—H5B | 0.99 | C18—C19 | 1.490 (4) |
C6—H6A | 0.99 | C18—H18A | 0.99 |
C6—H6B | 0.99 | C18—H18B | 0.99 |
C7—O2 | 1.237 (3) | C19—H19A | 0.99 |
C7—O1 | 1.283 (2) | C19—H19B | 0.99 |
C8—O4 | 1.234 (3) | N1—H1B | 0.91 |
C8—O3 | 1.281 (2) | N1—H1C | 0.91 |
C9—C16 | 1.510 (3) | N1—H1A | 0.91 |
C9—C14 | 1.527 (3) | C20—C21 | 1.464 (4) |
C9—C10 | 1.535 (3) | C20—C22 | 1.468 (4) |
C9—H9 | 1 | C20—N2 | 1.470 (3) |
C10—C11 | 1.531 (3) | C20—H20 | 1 |
C10—H10A | 0.99 | C21—C22 | 1.490 (4) |
C10—H10B | 0.99 | C21—H21A | 0.99 |
C11—C12 | 1.527 (3) | C21—H21B | 0.99 |
C11—H11A | 0.99 | C22—H22A | 0.99 |
C11—H11B | 0.99 | C22—H22B | 0.99 |
C12—C15 | 1.506 (2) | N2—H2A | 0.91 |
C12—C13 | 1.535 (3) | N2—H2B | 0.91 |
C12—H12 | 1 | N2—H2C | 0.91 |
C6—C1—C2 | 111.36 (15) | C14—C13—H13A | 109.5 |
C6—C1—C7 | 110.68 (16) | C12—C13—H13A | 109.5 |
C2—C1—C7 | 113.25 (15) | C14—C13—H13B | 109.5 |
C6—C1—H1 | 107.1 | C12—C13—H13B | 109.5 |
C2—C1—H1 | 107.1 | H13A—C13—H13B | 108.1 |
C7—C1—H1 | 107.1 | C13—C14—C9 | 110.28 (16) |
C1—C2—C3 | 111.71 (15) | C13—C14—H14A | 109.6 |
C1—C2—H2D | 109.3 | C9—C14—H14A | 109.6 |
C3—C2—H2D | 109.3 | C13—C14—H14B | 109.6 |
C1—C2—H2E | 109.3 | C9—C14—H14B | 109.6 |
C3—C2—H2E | 109.3 | H14A—C14—H14B | 108.1 |
H2D—C2—H2E | 107.9 | O8—C15—O7 | 123.68 (18) |
C4—C3—C2 | 111.46 (15) | O8—C15—C12 | 121.63 (18) |
C4—C3—H3A | 109.3 | O7—C15—C12 | 114.58 (16) |
C2—C3—H3A | 109.3 | O6—C16—O5 | 123.47 (18) |
C4—C3—H3B | 109.3 | O6—C16—C9 | 121.99 (18) |
C2—C3—H3B | 109.3 | O5—C16—C9 | 114.49 (16) |
H3A—C3—H3B | 108 | C16—O5—H5 | 109.5 |
C3—C4—C5 | 109.15 (16) | C15—O7—H7 | 109.5 |
C3—C4—C8 | 113.59 (16) | N1—C17—C19 | 120.3 (2) |
C5—C4—C8 | 111.00 (17) | N1—C17—C18 | 118.8 (2) |
C3—C4—H4 | 107.6 | C19—C17—C18 | 60.4 (2) |
C5—C4—H4 | 107.6 | N1—C17—H17 | 115.4 |
C8—C4—H4 | 107.6 | C19—C17—H17 | 115.4 |
C4—C5—C6 | 111.69 (15) | C18—C17—H17 | 115.4 |
C4—C5—H5A | 109.3 | C17—C18—C19 | 59.53 (18) |
C6—C5—H5A | 109.3 | C17—C18—H18A | 117.8 |
C4—C5—H5B | 109.3 | C19—C18—H18A | 117.8 |
C6—C5—H5B | 109.3 | C17—C18—H18B | 117.8 |
H5A—C5—H5B | 107.9 | C19—C18—H18B | 117.8 |
C5—C6—C1 | 111.70 (16) | H18A—C18—H18B | 115 |
C5—C6—H6A | 109.3 | C17—C19—C18 | 60.08 (19) |
C1—C6—H6A | 109.3 | C17—C19—H19A | 117.8 |
C5—C6—H6B | 109.3 | C18—C19—H19A | 117.8 |
C1—C6—H6B | 109.3 | C17—C19—H19B | 117.8 |
H6A—C6—H6B | 107.9 | C18—C19—H19B | 117.8 |
O2—C7—O1 | 123.67 (18) | H19A—C19—H19B | 114.9 |
O2—C7—C1 | 119.52 (18) | C17—N1—H1B | 109.5 |
O1—C7—C1 | 116.79 (17) | C17—N1—H1C | 109.5 |
O4—C8—O3 | 123.59 (18) | H1B—N1—H1C | 109.5 |
O4—C8—C4 | 118.72 (18) | C17—N1—H1A | 109.5 |
O3—C8—C4 | 117.68 (17) | H1B—N1—H1A | 109.5 |
C16—C9—C14 | 113.25 (16) | H1C—N1—H1A | 109.5 |
C16—C9—C10 | 108.45 (16) | C21—C20—C22 | 61.1 (2) |
C14—C9—C10 | 110.54 (16) | C21—C20—N2 | 119.2 (2) |
C16—C9—H9 | 108.2 | C22—C20—N2 | 120.8 (2) |
C14—C9—H9 | 108.2 | C21—C20—H20 | 115 |
C10—C9—H9 | 108.2 | C22—C20—H20 | 115 |
C11—C10—C9 | 110.36 (16) | N2—C20—H20 | 115 |
C11—C10—H10A | 109.6 | C20—C21—C22 | 59.57 (18) |
C9—C10—H10A | 109.6 | C20—C21—H21A | 117.8 |
C11—C10—H10B | 109.6 | C22—C21—H21A | 117.8 |
C9—C10—H10B | 109.6 | C20—C21—H21B | 117.8 |
H10A—C10—H10B | 108.1 | C22—C21—H21B | 117.8 |
C12—C11—C10 | 110.70 (16) | H21A—C21—H21B | 115 |
C12—C11—H11A | 109.5 | C20—C22—C21 | 59.33 (18) |
C10—C11—H11A | 109.5 | C20—C22—H22A | 117.8 |
C12—C11—H11B | 109.5 | C21—C22—H22A | 117.8 |
C10—C11—H11B | 109.5 | C20—C22—H22B | 117.8 |
H11A—C11—H11B | 108.1 | C21—C22—H22B | 117.8 |
C15—C12—C11 | 114.14 (16) | H22A—C22—H22B | 115 |
C15—C12—C13 | 107.90 (16) | C20—N2—H2A | 109.5 |
C11—C12—C13 | 110.60 (16) | C20—N2—H2B | 109.5 |
C15—C12—H12 | 108 | H2A—N2—H2B | 109.5 |
C11—C12—H12 | 108 | C20—N2—H2C | 109.5 |
C13—C12—H12 | 108 | H2A—N2—H2C | 109.5 |
C14—C13—C12 | 110.64 (16) | H2B—N2—H2C | 109.5 |
C6—C1—C2—C3 | −52.5 (2) | C9—C10—C11—C12 | 56.9 (2) |
C7—C1—C2—C3 | −178.03 (15) | C10—C11—C12—C15 | −178.60 (17) |
C1—C2—C3—C4 | 55.8 (2) | C10—C11—C12—C13 | −56.7 (2) |
C2—C3—C4—C5 | −57.7 (2) | C15—C12—C13—C14 | −177.33 (16) |
C2—C3—C4—C8 | 66.8 (2) | C11—C12—C13—C14 | 57.2 (2) |
C3—C4—C5—C6 | 58.0 (2) | C12—C13—C14—C9 | −57.7 (2) |
C8—C4—C5—C6 | −68.0 (2) | C16—C9—C14—C13 | 179.89 (17) |
C4—C5—C6—C1 | −56.2 (2) | C10—C9—C14—C13 | 58.0 (2) |
C2—C1—C6—C5 | 52.7 (2) | C11—C12—C15—O8 | −151.41 (19) |
C7—C1—C6—C5 | 179.63 (16) | C13—C12—C15—O8 | 85.2 (2) |
C6—C1—C7—O2 | 29.9 (2) | C11—C12—C15—O7 | 32.2 (2) |
C2—C1—C7—O2 | 155.77 (18) | C13—C12—C15—O7 | −91.2 (2) |
C6—C1—C7—O1 | −151.58 (17) | C14—C9—C16—O6 | 143.5 (2) |
C2—C1—C7—O1 | −25.7 (2) | C10—C9—C16—O6 | −93.4 (2) |
C3—C4—C8—O4 | −150.54 (18) | C14—C9—C16—O5 | −38.9 (2) |
C5—C4—C8—O4 | −27.1 (2) | C10—C9—C16—O5 | 84.1 (2) |
C3—C4—C8—O3 | 30.7 (2) | N1—C17—C18—C19 | 110.5 (2) |
C5—C4—C8—O3 | 154.18 (17) | N1—C17—C19—C18 | −108.0 (3) |
C16—C9—C10—C11 | 177.79 (16) | N2—C20—C21—C22 | −111.2 (3) |
C14—C9—C10—C11 | −57.5 (2) | N2—C20—C22—C21 | 108.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···O3 | 0.84 | 1.68 | 2.511 (2) | 168 |
O7—H7···O1i | 0.84 | 1.66 | 2.490 (2) | 169 |
N1—H1A···O1 | 0.91 | 1.91 | 2.822 (2) | 175 |
N1—H1B···O6ii | 0.91 | 2.05 | 2.933 (2) | 162 |
N1—H1C···O2iii | 0.91 | 1.9 | 2.779 (2) | 163 |
N2—H2A···O3 | 0.91 | 1.91 | 2.812 (2) | 174 |
N2—H2B···O4iii | 0.91 | 1.85 | 2.709 (2) | 158 |
N2—H2C···O8iv | 0.91 | 2.1 | 2.944 (2) | 153 |
Symmetry codes: (i) −x+2, −y+1, z−1/2; (ii) −x+1, −y+1, z+1/2; (iii) x−1/2, −y+3/2, z; (iv) x−1, y, z. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C3H10N+·C7H5O2− | C7H10N+·C9H9O2− | C8H12N+·C11H7O2− | C7H10N+·C7H5O2−·C7H6O2 |
Mr | 181.23 | 257.32 | 293.35 | 351.39 |
Crystal system, space group | Orthorhombic, P212121 | Monoclinic, C2 | Triclinic, P1 | Monoclinic, P21/n |
Temperature (K) | 243 | 173 | 173 | 173 |
a, b, c (Å) | 6.3823 (7), 9.0629 (5), 19.5457 (13) | 30.970 (2), 5.8832 (4), 7.8239 (5) | 8.8979 (9), 12.0013 (8), 16.0498 (15) | 12.3249 (11), 6.0804 (6), 24.7669 (17) |
α, β, γ (°) | 90, 90, 90 | 90, 99.825 (2), 90 | 100.213 (5), 103.102 (3), 90.652 (5) | 90, 95.526 (5), 90 |
V (Å3) | 1130.57 (16) | 1404.63 (16) | 1640.5 (3) | 1847.4 (3) |
Z | 4 | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.07 | 0.08 | 0.08 | 0.09 |
Crystal size (mm) | 0.26 × 0.16 × 0.1 | 0.63 × 0.26 × 0.09 | 0.51 × 0.35 × 0.12 | 0.5 × 0.08 × 0.06 |
Data collection | ||||
Diffractometer | Bruker APEXII CCD area-detector diffractometer | Bruker APEXII CCD area-detector diffractometer | Bruker APEXII CCD area-detector diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) | Integration (XPREP; Bruker, 2004) |
Tmin, Tmax | 0.981, 0.993 | 0.951, 0.993 | 0.962, 0.991 | 0.957, 0.995 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9482, 1232, 869 | 16064, 1863, 1660 | 27233, 7082, 3917 | 22843, 4004, 2214 |
Rint | 0.081 | 0.068 | 0.075 | 0.094 |
(sin θ/λ)max (Å−1) | 0.606 | 0.661 | 0.640 | 0.639 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.061, 0.181, 1.04 | 0.035, 0.086, 1.09 | 0.050, 0.135, 1.00 | 0.045, 0.114, 0.96 |
No. of reflections | 1232 | 1863 | 7082 | 4004 |
No. of parameters | 133 | 174 | 401 | 237 |
No. of restraints | 23 | 1 | 0 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.19 | 0.21, −0.15 | 0.22, −0.25 | 0.21, −0.22 |
Absolute structure | Flack (1983), with 854 Friedel pairs | Flack (1983), with 1534 Friedel pairs | ? | ? |
(V) | (VI) | |
Crystal data | ||
Chemical formula | C3H8N+·C7H5O2−·C7H6O2 | 2C3H8N+·C8H10O42−·C8H12O4 |
Mr | 301.33 | 458.54 |
Crystal system, space group | Monoclinic, P21/c | Orthorhombic, Pna21 |
Temperature (K) | 173 | 173 |
a, b, c (Å) | 15.3307 (10), 6.3703 (3), 17.9989 (11) | 10.2478 (4), 9.6134 (4), 23.8354 (9) |
α, β, γ (°) | 90, 114.199 (2), 90 | 90, 90, 90 |
V (Å3) | 1603.33 (16) | 2348.17 (16) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.10 |
Crystal size (mm) | 0.34 × 0.2 × 0.1 | 0.56 × 0.4 × 0.07 |
Data collection | ||
Diffractometer | Bruker APEXII CCD area-detector diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.970, 0.991 | 0.947, 0.993 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9730, 3876, 2461 | 27099, 2909, 2735 |
Rint | 0.028 | 0.037 |
(sin θ/λ)max (Å−1) | 0.660 | 0.660 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.11, 1.00 | 0.035, 0.094, 1.04 |
No. of reflections | 3876 | 2909 |
No. of parameters | 200 | 293 |
No. of restraints | 0 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.19 | 0.33, −0.18 |
Absolute structure | ? | Flack (1983), with 2122 Friedel pairs |
Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004) and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.9 | 1.88 | 2.781 (4) | 177 |
N1—H1B···O1i | 0.9 | 1.88 | 2.763 (4) | 167 |
N1—H1C···O2ii | 0.9 | 1.79 | 2.681 (4) | 174 |
Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.91 | 1.91 | 2.8152 (16) | 174 |
N1—H1B···O1i | 0.91 | 1.91 | 2.7652 (18) | 157 |
N1—H1C···O2ii | 0.91 | 1.76 | 2.6651 (18) | 178 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1; (ii) −x+1/2, y−1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.91 | 1.92 | 2.7305 (19) | 147 |
N1—H1B···O4i | 0.91 | 1.86 | 2.7650 (17) | 178 |
N1—H1C···O3ii | 0.91 | 1.89 | 2.7716 (18) | 162 |
N2—H2A···O3 | 0.91 | 1.91 | 2.7232 (18) | 147 |
N2—H2B···O1ii | 0.91 | 1.89 | 2.7695 (19) | 163 |
N2—H2C···O2iii | 0.91 | 1.86 | 2.7678 (18) | 175 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z+1; (iii) x+1, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.84 | 1.79 | 2.6255 (16) | 177 |
N1—H1A···O1 | 0.91 | 1.99 | 2.8399 (18) | 155 |
N1—H1B···O1i | 0.91 | 1.87 | 2.7620 (18) | 168 |
N1—H1C···O2ii | 0.91 | 1.88 | 2.7835 (17) | 171 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O1 | 0.84 | 1.75 | 2.5881 (16) | 173 |
N1—H1A···O1 | 0.91 | 1.89 | 2.7901 (16) | 168 |
N1—H1B···O2i | 0.91 | 1.97 | 2.8573 (16) | 165 |
N1—H1C···O2ii | 0.91 | 1.91 | 2.7743 (15) | 158 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···O3 | 0.84 | 1.68 | 2.511 (2) | 168 |
O7—H7···O1i | 0.84 | 1.66 | 2.490 (2) | 169 |
N1—H1A···O1 | 0.91 | 1.91 | 2.822 (2) | 175 |
N1—H1B···O6ii | 0.91 | 2.05 | 2.933 (2) | 162 |
N1—H1C···O2iii | 0.91 | 1.9 | 2.779 (2) | 163 |
N2—H2A···O3 | 0.91 | 1.91 | 2.812 (2) | 174 |
N2—H2B···O4iii | 0.91 | 1.85 | 2.709 (2) | 158 |
N2—H2C···O8iv | 0.91 | 2.1 | 2.944 (2) | 153 |
Symmetry codes: (i) −x+2, −y+1, z−1/2; (ii) −x+1, −y+1, z+1/2; (iii) x−1/2, −y+3/2, z; (iv) x−1, y, z. |
Ammonium carboxylate salts of the general formula (R-NH3+).(R'-COO-) are known to form hydrogen-bonded one-dimensional ladders in the solid state, among other motifs (Lemmerer et al., 2008a, 2010). The ladders are formed by hydrogen-bonded rings formed from four N—H···O hydrogen bonds and consist of two cation–anion pairs (Odendal et al., 2010). The ladders are predominantly of two types, as classified by Nagahama et al. (2003): type II consists of repeating hydrogen-bonded rings, described using graph-set notation (Bernstein et al., 1995) as R43(10), and type III consists of the repetition of two differently sized rings, described as R42(8) and R44(12) (Fig. 1). Together with the ladder concept used to describe the hydrogen-bonded pattern of ammonium carboxylate salts, the four hydrogen bonds forming the rings can be divided into legs and rungs (Fig. 1). These two ladders have also been described as robust heterosynthons (Lemmerer et al., 2008b), as they form even in the presence of other hydrogen-bonding functional groups. The type of ladder observed is also dependent on the presence of a chiral ion. If either of the ions is present as the optically active enantiomer only (either R or S), then a type II ladder is formed almost exclusively, while if the ion is present as the racemate (RS), type III ladders form (with a minority of type II) (Lemmerer et al., 2008a).
When combining an amine and an acid, the difference in pKa can be indicative of whether a salt or a neutral complex is formed. Generally, a difference of 3 units should result in a salt (Bhogala et al., 2005). However, it has been observed that salts formed with succinic and fumaric acids often include un-ionized acid molecules, even with large differences in pKa (Haynes & Pietersen, 2008). We have observed the inclusion of un-ionized acid molecules together with ionized acid and amine molecules in the salt (4-pyridylmethyl)ammonium.m-iodobenzoate.m-iodobenzoic acid (Lemmerer et al., 2008c). In this salt, the peripheral un-ionized m-iodobenzoic acid molecule forms hydrogen bonds to the pyridine N atom of the (4-pyridylmethyl)ammonium cation, thus forming a type II salt. This 1:1:1 salt was synthesized from a 1:1 ratio of amine to acid (with a large difference in pKa), and the 1:1 salt (containing no un-ionized acid) was not obtained. The 1:1:1 salt was successfully synthesized using a ratio of amine to acid of 1:2, by having an excess of acid available which is then unable to undergo proton transfer to the amine. This had led us to believe that we might selectively prepare these three-component salts by controlling the molecular ratio in the crystallization synthesis. In this study, we wished to include un-ionized acid molecules into the salt structure, in order to observe if the ladders are still formed and how the un-ionized acid molecule becomes incorporated. In addition, three related 1:1 salts have been synthesized that illustrate the different types of ladders and how their formation is controlled. The six salts synthesized and reported here are 2-propylammonium benzoate, (I), benzylammonium (R)-2-phenylpropyl-1-carboxylate, (II), (RS)-1-phenylethylammonium naphthalene-1-carboxylate, (III), benzylammonium benzoate–benzoic acid (1/1), (IV), cyclopropylammonium benzoate–benzoic acid (1/1), (V), and bis(cyclopropylammonium) ea-cis-cyclohexane-1,4-dicarboxylate–ee-trans-cyclohexane-1,4-dicarboxylic acid (1/1), (VI).
The molecular structure and atomic numbering scheme of the asymmetric unit of the 1:1 salt (I) are shown in Fig. 2. The asymmetric unit consists of one disordered 2-propylammonium cation and one benzoate anion, both on general positions. The ammonium group forms three charge-assisted hydrogen bonds to form a ring, graph-set notation R43(10), consisting of two ammonium cations and two carboxylate anions, one involving both atoms O1 and O2 and the second involving only atom O1 (see Fig. 3). This hydrogen-bonded pattern has translational symmetry via a twofold screw axis along the crystallographic a axis inherent in the space group P212121. All three ammonium H atoms are used to form the ring and atom O1 acts as a bifurcated hydrogen-bond acceptor. Salt (I) thus forms a type II hydrogen-bonded ladder.
The molecular structure and atomic numbering scheme of the asymmetric unit of the 1:1 salt (II) are shown in Fig. 4. The asymmetric unit consists of one benzylammonium cation and one (R)-2-phenyl-propane-1-carboxylate anion, both on general positions. The salt crystallizes in the chiral space group C2 and features a type II ladder, extending along the twofold rotation axis in the direction of the b axis (Fig. 5).
The molecular structure and atomic numbering scheme of the asymmetric unit of the 1:1 salt (III) are shown in Fig. 6. The asymmetric unit consists of one (S)-1-phenylethylammonium cation (labelled N1), one (R)-1-phenylethylammonium cation (N2) and two naphthalene-1-carboxylate anions, labelled O1/O2 and O3/O4, all on general positions. Both N1 and N2 cations form two charge-assisted hydrogen bonds to form a ring, graph-set notation R42(8), consisting of the two ammonium cations and the two carboxylate anions, involving atoms O1 and O3 (see Fig. 7). A second type of ring is formed by two N1 cations and two O3/O4 anions, again using four N+—H···O- hydrogen bonds, to generate an R44(12) ring. Another similar R44(12) ring is present, this time involving two N2 cations and two O1/O2 anions. The sequence of these three unique rings generates a type III hydrogen-bonded ladder along the a axis.
The molecular structure and atomic numbering scheme of the asymmetric unit of the 1:1:1 salt (IV) are shown in Fig. 8. The asymmetric unit consists of one (un-ionized) benzoic acid molecule, one benzylammonium cation and one benzoate anion, all on general positions. The cation and anion form a type III ladder via N+—H···O- hydrogen bonds along the b axis. The benzoic acid molecule forms O—H···O- hydrogen bonds to one of the carboxylate O atoms of the ladder (Fig. 9).
The molecular structure and atomic numbering scheme of the asymmetric unit of the 1:1:1 salt (V) are shown in Fig. 10. The asymmetric unit consists of one neutral benzoic acid molecule, one cyclopropylammonium cation and one benzoate anion, all on general positions. The cation and anion form a type III ladder via N+—H···O- hydrogen bonds along the b axis. The benzoic acid molecule forms O—H···O- hydrogen bonds to one of the carboxylate O atoms of the ladder (Fig. 11).
The molecular structure and atomic numbering scheme of the asymmetric unit of the 1:2:1 salt (VI) are shown in Fig. 12. The asymmetric unit consists of one neutral ee-trans-1,4-cyclohexanedicarboxylic acid molecule, two cyclopropylammonium cations and one ea-cis-1,4-cyclohexanedicarboxylate anion, all on general positions. The hydrogen-bonding pattern does not correspond to any of the three rings described above. Each of the two cyclopentylammonium cations forms hydrogen bonds to two separate cations (to one of their O atoms). The third hydrogen bond from the cations is to the carbonyl O atom of the neutral dicarboxylic acid molecule. In addition, the neutral dicarboxylic acid molecule forms hydrogen bonds to the carboxylate anion via an O—H···O- hydrogen bond. A number of larger hydrogen-bonded rings are formed through this combination of un-ionized and ionized species (Fig. 13). The two rings R46(16) and R55(21) are formed using all three species, whereas the R44(22) ring is formed using only the ionized species.
The 1:1 salts (I)–(III) form type II and III ladders in accordance with previous studies (Lemmerer, 2008). The type II ladder was found to be the most common motif observed in general ammonium carboxylate salts deposited in the Cambridge Structural Database (CSD; Version ?; Allen, 2002). According to a detailed CSD analysis of 317 primary ammonium carboxylate salts performed by Yuge et al. (2008), 185 of the salts have a type II ladder (58%). Type II ladders are helical in nature and frequently crystallize in space groups with twofold screw axes. This is also observed for (I). If any of the ions are chiral in nature, and only the optically active enantiomer is present, then the chance of forming a type II ladder increases considerably (Lemmerer et al., 2010, and references therein), and hence a type II ladder is again observed in salt (II), which has the R enantiomer of the 2-phenylpropyl-1-carboxylate cation. In salt (III), which contains the racemate of the 1-phenthylammonium cation, a type III ladder forms, and the hydrogen-bonded rings are all centrosymmetric. It was observed previously that the racemate of the 1-phenylethylammonium cation often produces a type III ladder (Lemmerer et al., 2008a).
The 1:1:1 salts (IV)–(VI) were prepared by including un-ionized acid molecules in the crystallization solution. This does not necessarily guarantee that they will be incorporated into the crystallized salts, but nonetheless they were incorporated in all three. A reason for this is the increased acceptor potential of the O atoms on the carboxylate anions. As they are now negatively charged, the electrostatic interaction is stronger between the un-ionized acid molecules and the ionized anions hydrogen-bonding to each other. In salts (IV) and (V), the ladder motif is still observed, in this case a type III ladder. The benzoic acid molecules form hydrogen bonds to the O atoms of the carboxylate anions, as they are the only acceptor atoms available, and they are arranged as pendant molecules to the ladders. In the 1:2:1 salt (VI), the un-ionized and ionized acid molecules have different conformations. The 1,4-cyclohexanedicarboxylic acid used consisted of a cis/trans mixture. In (VI), while the cis conformer underwent proton transfer to the two cyclopropylamine molecules, the trans conformer remained un-ionized. It is not clear at this stage why the cis conformer underwent proton transfer and the trans isomer did not. In contrast with the 1:1:1 salts of (IV) and (V), no ladder motif is formed in (VI) and the un-ionized acid molecules are incorporated into the rings formed by the ionized species. Previous work has shown that ammonium carboxylate salts that have two carboxylate functional groups on one ion form two-dimensional networks by joining two ladders together (Lemmerer et al., 2008a; Lemmerer, 2011). It was hoped that the two-dimensional network would be retained and that the un-ionized diacid species would connect the two-dimensional networks into three-dimensional networks.
In conclusion, we have shown that is it possible to create three-component salt structures with a ladder motif by reducing the ratio of amine to acid in the synthesis.