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Hydrogen-bonding interactions play an important role in the rational design of crystal systems with desirable architectures. The crystal structures of benzene-1,2-diaminium sulfate sesquihydrate, C
6H
20N
22+·SO
42−·1.5H
2O, (
1), benzene-1,3-diaminium tetrachloridozincate(II), (C
6H
20N
2)[ZnCl
4], (
3), and 3-aminoanilinium perchlorate, C
6H
9N
2+·ClO
4−, (
4), are reported. Hydrated salt (
1) is a polymorph (space group
C2/
c) of a previously reported [Anderson
et al. (2011).
Cryst. Growth Des. 11, 4904–4919] crystalline modification of salt (
2) (space group
P2
1/
c). The contents of the asymmetric unit of (
2) are twice that of (
1). In each, the extended structures exhibit hydrogen bonds, resulting in chains of ions and hydrogen-bonded rings with an
R44(8) motif involving water molecules. Hirshfeld surface analysis shows that a significant difference between the two is the degree of C
C interaction. Salt (
3) exhibits an extended structure having hydrogen-bonded rings and parallel benzene rings, with a centroid-to-centroid separation of 3.860 (2) Å. Salt (
4) displays a three-dimensional superstructure that results from linked planes of ions joined by an extensive hydrogen-bonding network involving N—H
O, N—H
N and C—H
π interactions. The cation–anion and N—H
N interaction energies in (
4), determined using density functional theory (DFT), show significantly stronger aminium–perchlorate than amine–perchlorate interactions.
Supporting information
CCDC references: 1876922; 1876921; 1876920
For all structures, data collection: APEX2 (Bruker, 2015); cell refinement: APEX2 (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
Benzene-1,2-diaminium sulfate sesquihydrate (1)
top
Crystal data top
2C6H10N22+·2SO42−·3H2O | F(000) = 984 |
Mr = 466.49 | Dx = 1.535 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 28.348 (3) Å | Cell parameters from 6495 reflections |
b = 9.6720 (9) Å | θ = 3.4–27.0° |
c = 7.5667 (8) Å | µ = 0.33 mm−1 |
β = 103.308 (4)° | T = 300 K |
V = 2018.9 (4) Å3 | Plate, clear colourless |
Z = 4 | 0.50 × 0.30 × 0.05 mm |
Data collection top
Bruker SMART X2S benchtop diffractometer | 2218 independent reflections |
Radiation source: XOS X-beam microfocus source | 1881 reflections with I > 2σ(I) |
Doubly curved silicon crystal monochromator | Rint = 0.044 |
Detector resolution: 8.3330 pixels mm-1 | θmax = 27.1°, θmin = 2.2° |
ω scans | h = −35→36 |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | k = −12→11 |
Tmin = 0.908, Tmax = 1.000 | l = −9→9 |
15241 measured reflections | |
Refinement top
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)] = 0.043 | Hydrogen site location: mixed |
wR(F2) = 0.125 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0539P)2 + 4.0638P] where P = (Fo2 + 2Fc2)/3 |
2218 reflections | (Δ/σ)max = 0.001 |
166 parameters | Δρmax = 0.45 e Å−3 |
2 restraints | Δρmin = −0.38 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refined as a 2-component twin. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.19815 (2) | 0.83419 (6) | 0.25370 (7) | 0.01861 (18) | |
O1 | 0.21519 (8) | 0.7412 (2) | 0.1272 (3) | 0.0371 (5) | |
O2 | 0.18628 (8) | 0.75257 (18) | 0.4004 (3) | 0.0359 (5) | |
O3 | 0.15528 (7) | 0.9103 (2) | 0.1546 (3) | 0.0432 (5) | |
O4 | 0.23676 (6) | 0.93470 (18) | 0.3279 (2) | 0.0276 (4) | |
O5 | 0.0000 | 1.0132 (5) | 0.2500 | 0.0638 (11) | |
H5A | −0.0168 (19) | 0.957 (5) | 0.290 (8) | 0.096* | |
O6 | 0.05449 (9) | 0.8495 (3) | 0.0646 (4) | 0.0635 (7) | |
H6A | 0.0836 (8) | 0.858 (5) | 0.111 (6) | 0.095* | |
H6B | 0.0429 (18) | 0.898 (5) | −0.021 (5) | 0.095* | |
N1 | 0.17746 (9) | 0.1850 (2) | 0.2465 (3) | 0.0284 (5) | |
H1A | 0.1952 (11) | 0.194 (3) | 0.156 (4) | 0.032 (8)* | |
H1B | 0.1670 (11) | 0.102 (4) | 0.226 (4) | 0.034 (8)* | |
H1C | 0.1959 (15) | 0.191 (4) | 0.348 (6) | 0.055 (11)* | |
N2 | 0.19378 (7) | 0.4664 (2) | 0.3650 (3) | 0.0219 (4) | |
H2A | 0.2019 (11) | 0.423 (3) | 0.472 (5) | 0.038 (9)* | |
H2B | 0.1947 (11) | 0.558 (4) | 0.396 (4) | 0.033 (8)* | |
H2C | 0.2147 (11) | 0.458 (3) | 0.291 (4) | 0.033 (8)* | |
C1 | 0.13737 (8) | 0.2826 (2) | 0.2197 (3) | 0.0210 (5) | |
C2 | 0.14542 (8) | 0.4196 (2) | 0.2727 (3) | 0.0208 (5) | |
C3 | 0.10709 (9) | 0.5115 (3) | 0.2437 (4) | 0.0331 (6) | |
H3 | 0.1123 | 0.6034 | 0.2791 | 0.040* | |
C4 | 0.06090 (10) | 0.4666 (3) | 0.1619 (5) | 0.0457 (8) | |
H4 | 0.0351 | 0.5285 | 0.1420 | 0.055* | |
C5 | 0.05289 (10) | 0.3299 (3) | 0.1094 (5) | 0.0463 (8) | |
H5 | 0.0217 | 0.2999 | 0.0552 | 0.056* | |
C6 | 0.09125 (10) | 0.2379 (3) | 0.1375 (4) | 0.0344 (6) | |
H6 | 0.0860 | 0.1462 | 0.1011 | 0.041* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0193 (3) | 0.0137 (3) | 0.0223 (3) | −0.0008 (2) | 0.0037 (2) | −0.0017 (2) |
O1 | 0.0463 (11) | 0.0339 (11) | 0.0340 (10) | −0.0007 (9) | 0.0153 (9) | −0.0141 (8) |
O2 | 0.0537 (13) | 0.0241 (10) | 0.0351 (10) | −0.0082 (9) | 0.0210 (9) | 0.0008 (8) |
O3 | 0.0267 (10) | 0.0255 (10) | 0.0668 (14) | 0.0023 (8) | −0.0112 (9) | 0.0049 (9) |
O4 | 0.0251 (9) | 0.0249 (9) | 0.0308 (9) | −0.0069 (7) | 0.0020 (7) | −0.0034 (7) |
O5 | 0.054 (2) | 0.073 (3) | 0.069 (3) | 0.000 | 0.0233 (18) | 0.000 |
O6 | 0.0384 (13) | 0.071 (2) | 0.0768 (19) | −0.0040 (13) | 0.0054 (13) | −0.0044 (15) |
N1 | 0.0307 (12) | 0.0162 (11) | 0.0355 (13) | 0.0036 (9) | 0.0021 (10) | −0.0031 (9) |
N2 | 0.0229 (10) | 0.0187 (11) | 0.0224 (10) | −0.0017 (8) | 0.0019 (8) | 0.0000 (8) |
C1 | 0.0229 (11) | 0.0184 (11) | 0.0209 (10) | 0.0016 (9) | 0.0035 (8) | 0.0025 (9) |
C2 | 0.0203 (11) | 0.0216 (12) | 0.0201 (10) | −0.0001 (9) | 0.0038 (8) | 0.0014 (9) |
C3 | 0.0292 (13) | 0.0240 (13) | 0.0434 (16) | 0.0060 (11) | 0.0031 (11) | −0.0037 (11) |
C4 | 0.0227 (13) | 0.0413 (18) | 0.068 (2) | 0.0096 (12) | −0.0003 (13) | −0.0018 (15) |
C5 | 0.0226 (13) | 0.0439 (18) | 0.065 (2) | −0.0044 (12) | −0.0056 (13) | 0.0000 (15) |
C6 | 0.0304 (13) | 0.0229 (14) | 0.0449 (16) | −0.0064 (11) | −0.0019 (11) | −0.0006 (11) |
Geometric parameters (Å, º) top
S1—O2 | 1.4629 (18) | N2—H2B | 0.92 (3) |
S1—O3 | 1.4699 (19) | N2—H2C | 0.91 (3) |
S1—O1 | 1.4737 (18) | C1—C6 | 1.382 (3) |
S1—O4 | 1.4750 (17) | C1—C2 | 1.388 (3) |
O5—H5A | 0.83 (5) | C2—C3 | 1.382 (3) |
O6—H6A | 0.82 (2) | C3—C4 | 1.383 (4) |
O6—H6B | 0.805 (19) | C3—H3 | 0.9300 |
N1—C1 | 1.455 (3) | C4—C5 | 1.385 (5) |
N1—H1A | 0.94 (3) | C4—H4 | 0.9300 |
N1—H1B | 0.86 (3) | C5—C6 | 1.383 (4) |
N1—H1C | 0.83 (4) | C5—H5 | 0.9300 |
N2—C2 | 1.460 (3) | C6—H6 | 0.9300 |
N2—H2A | 0.89 (3) | | |
| | | |
O2—S1—O3 | 110.46 (13) | C6—C1—C2 | 120.3 (2) |
O2—S1—O1 | 109.30 (12) | C6—C1—N1 | 119.2 (2) |
O3—S1—O1 | 109.29 (13) | C2—C1—N1 | 120.5 (2) |
O2—S1—O4 | 110.30 (11) | C3—C2—C1 | 119.8 (2) |
O3—S1—O4 | 108.56 (11) | C3—C2—N2 | 119.6 (2) |
O1—S1—O4 | 108.90 (11) | C1—C2—N2 | 120.5 (2) |
H6A—O6—H6B | 118 (5) | C2—C3—C4 | 119.8 (3) |
C1—N1—H1A | 111.8 (19) | C2—C3—H3 | 120.1 |
C1—N1—H1B | 111 (2) | C4—C3—H3 | 120.1 |
H1A—N1—H1B | 100 (3) | C3—C4—C5 | 120.3 (3) |
C1—N1—H1C | 113 (3) | C3—C4—H4 | 119.9 |
H1A—N1—H1C | 110 (3) | C5—C4—H4 | 119.9 |
H1B—N1—H1C | 111 (3) | C6—C5—C4 | 119.9 (3) |
C2—N2—H2A | 108 (2) | C6—C5—H5 | 120.0 |
C2—N2—H2B | 113.1 (19) | C4—C5—H5 | 120.0 |
H2A—N2—H2B | 104 (3) | C1—C6—C5 | 119.8 (3) |
C2—N2—H2C | 110.5 (19) | C1—C6—H6 | 120.1 |
H2A—N2—H2C | 117 (3) | C5—C6—H6 | 120.1 |
H2B—N2—H2C | 105 (3) | | |
| | | |
C6—C1—C2—C3 | 0.3 (4) | C2—C3—C4—C5 | 0.2 (5) |
N1—C1—C2—C3 | 179.0 (2) | C3—C4—C5—C6 | −0.5 (5) |
C6—C1—C2—N2 | 178.0 (2) | C2—C1—C6—C5 | −0.6 (4) |
N1—C1—C2—N2 | −3.3 (3) | N1—C1—C6—C5 | −179.3 (3) |
C1—C2—C3—C4 | −0.1 (4) | C4—C5—C6—C1 | 0.7 (5) |
N2—C2—C3—C4 | −177.8 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O6i | 0.83 (5) | 1.99 (5) | 2.803 (4) | 167 (5) |
O6—H6A···O3 | 0.82 (2) | 2.05 (2) | 2.842 (3) | 162 (5) |
O6—H6B···O5ii | 0.81 (2) | 2.06 (2) | 2.851 (4) | 166 (5) |
N1—H1A···O2iii | 0.94 (3) | 1.96 (3) | 2.755 (3) | 140 (3) |
N1—H1B···O3iv | 0.86 (3) | 1.94 (4) | 2.782 (3) | 167 (3) |
N1—H1C···O1v | 0.83 (4) | 2.53 (4) | 3.022 (3) | 119 (3) |
N1—H1C···O1vi | 0.83 (4) | 2.16 (4) | 2.921 (3) | 154 (4) |
N2—H2A···O1vi | 0.89 (3) | 1.96 (3) | 2.789 (3) | 154 (3) |
N2—H2B···O2 | 0.92 (3) | 1.90 (3) | 2.794 (3) | 166 (3) |
N2—H2C···O4v | 0.91 (3) | 1.82 (3) | 2.725 (3) | 172 (3) |
Symmetry codes: (i) −x, y, −z+1/2; (ii) −x, −y+2, −z; (iii) x, −y+1, z−1/2; (iv) x, y−1, z; (v) −x+1/2, y−1/2, −z+1/2; (vi) x, −y+1, z+1/2. |
3-Aminoanilinium perchlorate (4)
top
Crystal data top
C6H9N2+·ClO4− | Dx = 1.571 Mg m−3 |
Mr = 208.60 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 6504 reflections |
a = 5.7979 (19) Å | θ = 2.5–27.4° |
b = 9.866 (4) Å | µ = 0.42 mm−1 |
c = 15.421 (6) Å | T = 200 K |
V = 882.1 (6) Å3 | Plate, clear colourless |
Z = 4 | 0.60 × 0.48 × 0.20 mm |
F(000) = 432 | |
Data collection top
Bruker SMART X2S benchtop diffractometer | 1898 independent reflections |
Radiation source: XOS X-beam microfocus source | 1783 reflections with I > 2σ(I) |
Doubly curved silicon crystal monochromator | Rint = 0.030 |
Detector resolution: 8.3330 pixels mm-1 | θmax = 27.1°, θmin = 2.5° |
ω scans | h = −7→5 |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | k = −12→12 |
Tmin = 0.75, Tmax = 0.92 | l = −19→19 |
5983 measured reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.029 | w = 1/[σ2(Fo2) + (0.0445P)2 + 0.1509P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.077 | (Δ/σ)max < 0.001 |
S = 1.02 | Δρmax = 0.23 e Å−3 |
1898 reflections | Δρmin = −0.27 e Å−3 |
139 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015) |
0 restraints | Extinction coefficient: 0.061 (5) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack x determined using 678 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.03 (3) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F2, conventional R-factors R are based
on F, with F set to zero for negative F2. The threshold expression of
F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F2 are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.08993 (10) | 0.32402 (6) | 0.37637 (3) | 0.03545 (19) | |
O1 | 0.2989 (4) | 0.3778 (3) | 0.41188 (17) | 0.0652 (7) | |
O2 | 0.0379 (5) | 0.3889 (2) | 0.29567 (13) | 0.0597 (6) | |
O3 | 0.1136 (4) | 0.17999 (19) | 0.36341 (16) | 0.0586 (6) | |
O4 | −0.0963 (4) | 0.3466 (2) | 0.43551 (14) | 0.0633 (6) | |
N1 | 0.2940 (4) | 0.6659 (2) | 0.28748 (14) | 0.0396 (5) | |
H1A | 0.268 (6) | 0.589 (4) | 0.312 (2) | 0.064 (11)* | |
H1B | 0.168 (8) | 0.708 (4) | 0.294 (2) | 0.075 (13)* | |
N2 | 0.6047 (5) | 1.0979 (2) | 0.38845 (15) | 0.0358 (5) | |
H2A | 0.630 (7) | 1.131 (3) | 0.337 (2) | 0.065 (11)* | |
H2B | 0.701 (6) | 1.133 (3) | 0.423 (2) | 0.053 (10)* | |
H2C | 0.457 (8) | 1.124 (4) | 0.405 (2) | 0.073 (12)* | |
C1 | 0.4605 (4) | 0.7387 (2) | 0.33616 (13) | 0.0298 (5) | |
C2 | 0.4484 (4) | 0.8800 (2) | 0.34173 (14) | 0.0277 (5) | |
H2 | 0.3249 | 0.9278 | 0.3152 | 0.033* | |
C3 | 0.6179 (4) | 0.9490 (2) | 0.38614 (13) | 0.0277 (5) | |
C4 | 0.8014 (5) | 0.8841 (3) | 0.42598 (16) | 0.0358 (5) | |
H4 | 0.9168 | 0.9338 | 0.456 | 0.043* | |
C5 | 0.8108 (5) | 0.7433 (3) | 0.42049 (16) | 0.0399 (6) | |
H5 | 0.9335 | 0.6961 | 0.4479 | 0.048* | |
C6 | 0.6437 (4) | 0.6708 (2) | 0.37561 (15) | 0.0360 (5) | |
H6 | 0.6541 | 0.5749 | 0.3718 | 0.043* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0362 (3) | 0.0308 (3) | 0.0394 (3) | −0.0059 (2) | −0.0053 (3) | 0.0020 (2) |
O1 | 0.0536 (13) | 0.0594 (14) | 0.0828 (16) | −0.0218 (12) | −0.0247 (13) | −0.0001 (12) |
O2 | 0.0785 (16) | 0.0548 (12) | 0.0459 (10) | −0.0150 (12) | −0.0114 (11) | 0.0145 (9) |
O3 | 0.0493 (12) | 0.0308 (9) | 0.0958 (16) | −0.0012 (9) | −0.0123 (12) | −0.0022 (10) |
O4 | 0.0627 (14) | 0.0737 (16) | 0.0536 (11) | −0.0018 (14) | 0.0136 (11) | −0.0073 (10) |
N1 | 0.0455 (13) | 0.0297 (10) | 0.0436 (11) | −0.0084 (10) | 0.0000 (10) | −0.0041 (9) |
N2 | 0.0393 (12) | 0.0273 (10) | 0.0407 (11) | −0.0047 (9) | 0.0032 (11) | −0.0032 (8) |
C1 | 0.0354 (13) | 0.0280 (11) | 0.0261 (9) | −0.0036 (9) | 0.0053 (9) | −0.0003 (8) |
C2 | 0.0281 (12) | 0.0269 (10) | 0.0281 (9) | 0.0014 (9) | 0.0002 (9) | 0.0016 (8) |
C3 | 0.0316 (11) | 0.0268 (10) | 0.0247 (9) | −0.0021 (9) | 0.0040 (10) | 0.0008 (7) |
C4 | 0.0311 (12) | 0.0459 (14) | 0.0304 (11) | −0.0006 (11) | −0.0011 (10) | 0.0009 (9) |
C5 | 0.0375 (13) | 0.0467 (15) | 0.0355 (12) | 0.0120 (12) | −0.0018 (11) | 0.0079 (10) |
C6 | 0.0449 (14) | 0.0264 (10) | 0.0366 (11) | 0.0080 (10) | 0.0065 (10) | 0.0049 (10) |
Geometric parameters (Å, º) top
Cl1—O4 | 1.431 (2) | C1—C6 | 1.396 (3) |
Cl1—O2 | 1.431 (2) | C1—C2 | 1.398 (3) |
Cl1—O1 | 1.432 (2) | C2—C3 | 1.378 (3) |
Cl1—O3 | 1.442 (2) | C2—H2 | 0.95 |
N1—C1 | 1.418 (3) | C3—C4 | 1.385 (4) |
N1—H1A | 0.86 (4) | C4—C5 | 1.392 (4) |
N1—H1B | 0.85 (4) | C4—H4 | 0.95 |
N2—C3 | 1.471 (3) | C5—C6 | 1.389 (4) |
N2—H2A | 0.87 (4) | C5—H5 | 0.95 |
N2—H2B | 0.85 (4) | C6—H6 | 0.95 |
N2—H2C | 0.93 (5) | | |
| | | |
O4—Cl1—O2 | 109.01 (15) | C2—C1—N1 | 120.2 (2) |
O4—Cl1—O1 | 109.70 (15) | C3—C2—C1 | 119.2 (2) |
O2—Cl1—O1 | 110.19 (15) | C3—C2—H2 | 120.4 |
O4—Cl1—O3 | 108.28 (14) | C1—C2—H2 | 120.4 |
O2—Cl1—O3 | 109.88 (14) | C2—C3—C4 | 122.7 (2) |
O1—Cl1—O3 | 109.75 (14) | C2—C3—N2 | 117.9 (2) |
C1—N1—H1A | 109 (2) | C4—C3—N2 | 119.4 (2) |
C1—N1—H1B | 106 (3) | C3—C4—C5 | 117.6 (2) |
H1A—N1—H1B | 103 (3) | C3—C4—H4 | 121.2 |
C3—N2—H2A | 110 (2) | C5—C4—H4 | 121.2 |
C3—N2—H2B | 113 (2) | C6—C5—C4 | 121.1 (3) |
H2A—N2—H2B | 108 (3) | C6—C5—H5 | 119.4 |
C3—N2—H2C | 109 (2) | C4—C5—H5 | 119.4 |
H2A—N2—H2C | 107 (4) | C5—C6—C1 | 120.1 (2) |
H2B—N2—H2C | 109 (3) | C5—C6—H6 | 120.0 |
C6—C1—C2 | 119.3 (2) | C1—C6—H6 | 120.0 |
C6—C1—N1 | 120.4 (2) | | |
| | | |
C6—C1—C2—C3 | 0.0 (3) | N2—C3—C4—C5 | −178.4 (2) |
N1—C1—C2—C3 | −177.1 (2) | C3—C4—C5—C6 | 0.9 (4) |
C1—C2—C3—C4 | −0.1 (3) | C4—C5—C6—C1 | −1.0 (4) |
C1—C2—C3—N2 | 178.0 (2) | C2—C1—C6—C5 | 0.5 (3) |
C2—C3—C4—C5 | −0.4 (4) | N1—C1—C6—C5 | 177.6 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.86 (4) | 2.60 (4) | 3.429 (4) | 163 (3) |
N1—H1A···O2 | 0.86 (4) | 2.40 (4) | 3.113 (3) | 141 (3) |
N1—H1B···O2i | 0.85 (4) | 2.55 (4) | 3.191 (3) | 134 (3) |
N2—H2A···N1ii | 0.87 (4) | 2.00 (4) | 2.856 (3) | 168 (3) |
N2—H2B···O1iii | 0.85 (4) | 2.61 (3) | 3.287 (4) | 138 (3) |
N2—H2B···O3iv | 0.85 (4) | 2.61 (4) | 3.084 (4) | 117 (3) |
N2—H2B···O4iv | 0.85 (4) | 2.42 (4) | 3.091 (4) | 137 (3) |
N2—H2C···O3v | 0.93 (5) | 2.16 (4) | 2.985 (4) | 147 (3) |
N2—H2C···O4iii | 0.93 (5) | 2.50 (4) | 3.004 (3) | 114 (3) |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x+1/2, −y+3/2, −z+1; (iv) x+1, y+1, z; (v) x, y+1, z. |
benzene-1,3-diaminium tetrachloridozincate(II) (3)
top
Crystal data top
(C6H10N2)[ZnCl4] | Dx = 1.793 Mg m−3 |
Mr = 317.35 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pna21 | Cell parameters from 7163 reflections |
a = 14.0070 (11) Å | θ = 2.3–26.2° |
b = 11.6085 (9) Å | µ = 2.96 mm−1 |
c = 7.2286 (5) Å | T = 300 K |
V = 1175.37 (15) Å3 | Plate, clear brown |
Z = 4 | 0.60 × 0.40 × 0.15 mm |
F(000) = 632 | |
Data collection top
Bruker SMART X2S benchtop diffractometer | 2373 independent reflections |
Radiation source: XOS X-beam microfocus source | 2242 reflections with I > 2σ(I) |
Doubly curved silicon crystal monochromator | Rint = 0.047 |
Detector resolution: 8.3330 pixels mm-1 | θmax = 26.4°, θmin = 2.9° |
ω scans | h = −17→12 |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | k = −14→14 |
Tmin = 0.39, Tmax = 0.73 | l = −8→8 |
13300 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.024 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.057 | w = 1/[σ2(Fo2) + (0.0302P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
2373 reflections | Δρmax = 0.23 e Å−3 |
137 parameters | Δρmin = −0.43 e Å−3 |
7 restraints | Absolute structure: Refined as an inversion twin. |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.217 (16) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refined as a 2-component inversion twin. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Zn1 | 0.62942 (2) | 0.59599 (3) | 0.11294 (8) | 0.03168 (13) | |
Cl1 | 0.70069 (7) | 0.71712 (8) | −0.09310 (14) | 0.0427 (2) | |
Cl2 | 0.69054 (6) | 0.41969 (7) | 0.05242 (16) | 0.0444 (3) | |
Cl3 | 0.67671 (7) | 0.66110 (9) | 0.39359 (15) | 0.0481 (3) | |
Cl4 | 0.47047 (7) | 0.60647 (10) | 0.0747 (2) | 0.0586 (3) | |
N1 | 0.7761 (2) | 0.4550 (3) | 0.6358 (6) | 0.0440 (8) | |
H1A | 0.771 (4) | 0.390 (3) | 0.565 (6) | 0.066* | |
H1B | 0.737 (3) | 0.500 (4) | 0.570 (7) | 0.066* | |
H1C | 0.749 (4) | 0.448 (4) | 0.743 (5) | 0.066* | |
N2 | 0.9972 (2) | 0.7825 (3) | 0.6528 (6) | 0.0435 (9) | |
H2B | 0.948 (3) | 0.827 (4) | 0.607 (7) | 0.065* | |
H2C | 1.046 (3) | 0.804 (4) | 0.577 (6) | 0.065* | |
H2A | 1.003 (4) | 0.820 (4) | 0.758 (5) | 0.065* | |
C1 | 0.8746 (2) | 0.4998 (3) | 0.6432 (6) | 0.0338 (8) | |
C2 | 0.8882 (2) | 0.6177 (3) | 0.6437 (6) | 0.0337 (9) | |
H2 | 0.8367 | 0.6684 | 0.6414 | 0.04* | |
C3 | 0.9809 (2) | 0.6573 (3) | 0.6477 (5) | 0.0332 (8) | |
C4 | 1.0589 (3) | 0.5835 (3) | 0.6496 (6) | 0.0393 (10) | |
H4 | 1.1208 | 0.6124 | 0.651 | 0.047* | |
C5 | 1.0425 (3) | 0.4662 (4) | 0.6495 (6) | 0.0433 (10) | |
H5 | 1.0939 | 0.4154 | 0.6507 | 0.052* | |
C6 | 0.9499 (3) | 0.4235 (3) | 0.6476 (6) | 0.0402 (10) | |
H6 | 0.9389 | 0.3445 | 0.6494 | 0.048* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.0333 (2) | 0.0277 (2) | 0.0340 (2) | 0.00183 (13) | −0.00168 (19) | −0.0002 (2) |
Cl1 | 0.0495 (5) | 0.0401 (5) | 0.0386 (5) | 0.0033 (4) | 0.0126 (4) | 0.0072 (4) |
Cl2 | 0.0390 (4) | 0.0277 (4) | 0.0664 (7) | 0.0060 (3) | 0.0081 (4) | 0.0031 (4) |
Cl3 | 0.0561 (6) | 0.0528 (6) | 0.0354 (5) | −0.0058 (5) | −0.0074 (5) | −0.0064 (5) |
Cl4 | 0.0299 (4) | 0.0692 (7) | 0.0768 (10) | 0.0000 (4) | −0.0001 (5) | 0.0125 (6) |
N1 | 0.0363 (15) | 0.0399 (17) | 0.056 (2) | −0.0068 (13) | 0.0070 (17) | −0.0011 (19) |
N2 | 0.0355 (16) | 0.0373 (19) | 0.058 (3) | −0.0016 (13) | −0.0073 (15) | −0.0106 (17) |
C1 | 0.0301 (15) | 0.0373 (19) | 0.034 (2) | −0.0008 (13) | 0.0029 (14) | −0.0022 (17) |
C2 | 0.0269 (15) | 0.0366 (18) | 0.037 (3) | 0.0043 (13) | 0.0015 (15) | −0.0037 (17) |
C3 | 0.0311 (16) | 0.0338 (19) | 0.035 (2) | −0.0003 (13) | −0.0021 (14) | −0.0070 (16) |
C4 | 0.0299 (16) | 0.045 (2) | 0.043 (3) | 0.0045 (14) | −0.0031 (16) | −0.0096 (17) |
C5 | 0.0383 (18) | 0.046 (2) | 0.046 (3) | 0.0155 (15) | −0.0048 (17) | −0.0086 (18) |
C6 | 0.048 (2) | 0.0332 (19) | 0.040 (3) | 0.0031 (15) | −0.0017 (18) | −0.0021 (17) |
Geometric parameters (Å, º) top
Zn1—Cl4 | 2.2469 (10) | N2—H2A | 0.88 (3) |
Zn1—Cl2 | 2.2611 (9) | C1—C6 | 1.378 (5) |
Zn1—Cl3 | 2.2640 (12) | C1—C2 | 1.383 (5) |
Zn1—Cl1 | 2.2785 (10) | C2—C3 | 1.378 (5) |
N1—C1 | 1.474 (4) | C2—H2 | 0.93 |
N1—H1A | 0.92 (3) | C3—C4 | 1.389 (5) |
N1—H1B | 0.90 (3) | C4—C5 | 1.381 (6) |
N1—H1C | 0.87 (3) | C4—H4 | 0.93 |
N2—C3 | 1.473 (5) | C5—C6 | 1.389 (5) |
N2—H2B | 0.92 (2) | C5—H5 | 0.93 |
N2—H2C | 0.92 (3) | C6—H6 | 0.93 |
| | | |
Cl4—Zn1—Cl2 | 113.60 (4) | C6—C1—C2 | 122.0 (3) |
Cl4—Zn1—Cl3 | 112.46 (5) | C6—C1—N1 | 119.4 (3) |
Cl2—Zn1—Cl3 | 111.39 (4) | C2—C1—N1 | 118.6 (3) |
Cl4—Zn1—Cl1 | 108.68 (4) | C3—C2—C1 | 117.4 (3) |
Cl2—Zn1—Cl1 | 105.44 (4) | C3—C2—H2 | 121.3 |
Cl3—Zn1—Cl1 | 104.57 (4) | C1—C2—H2 | 121.3 |
C1—N1—H1A | 112 (3) | C2—C3—C4 | 122.5 (3) |
C1—N1—H1B | 113 (3) | C2—C3—N2 | 118.4 (3) |
H1A—N1—H1B | 98 (5) | C4—C3—N2 | 119.1 (3) |
C1—N1—H1C | 114 (4) | C5—C4—C3 | 118.5 (3) |
H1A—N1—H1C | 113 (5) | C5—C4—H4 | 120.7 |
H1B—N1—H1C | 105 (5) | C3—C4—H4 | 120.7 |
C3—N2—H2B | 115 (3) | C4—C5—C6 | 120.5 (3) |
C3—N2—H2C | 112 (3) | C4—C5—H5 | 119.8 |
H2B—N2—H2C | 102 (4) | C6—C5—H5 | 119.8 |
C3—N2—H2A | 121 (4) | C1—C6—C5 | 119.1 (4) |
H2B—N2—H2A | 96 (5) | C1—C6—H6 | 120.4 |
H2C—N2—H2A | 108 (5) | C5—C6—H6 | 120.4 |
Hydrogen-bond geometry (Å, º) topThe N–H bond distances were restrained to 0.89 Å. See section 2.2 for
details. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl1i | 0.92 (3) | 2.34 (3) | 3.236 (4) | 166 (4) |
N1—H1B···Cl3 | 0.90 (3) | 2.41 (3) | 3.276 (4) | 162 (4) |
N1—H1C···Cl2ii | 0.87 (3) | 2.40 (3) | 3.267 (4) | 174 (5) |
N2—H2B···Cl2iii | 0.92 (2) | 2.25 (3) | 3.158 (3) | 167 (5) |
N2—H2C···Cl3iv | 0.92 (3) | 2.29 (3) | 3.203 (4) | 174 (4) |
N2—H2A···Cl1v | 0.88 (3) | 3.00 (5) | 3.391 (4) | 109 (4) |
N2—H2A···Cl4v | 0.88 (3) | 2.49 (3) | 3.332 (4) | 161 (5) |
C2—H2···Cl1ii | 0.93 | 2.76 | 3.442 (4) | 131 |
C2—H2···Cl3 | 0.93 | 2.87 | 3.506 (4) | 127 |
C4—H4···Cl1v | 0.93 | 2.93 | 3.572 (4) | 127 |
C4—H4···Cl2vi | 0.93 | 2.76 | 3.580 (4) | 147 |
Symmetry codes: (i) −x+3/2, y−1/2, z+1/2; (ii) x, y, z+1; (iii) −x+3/2, y+1/2, z+1/2; (iv) x+1/2, −y+3/2, z; (v) x+1/2, −y+3/2, z+1; (vi) −x+2, −y+1, z+1/2. |
Hirshfeld surface coverage for diamminium ions in (1) and (2) topValues reported are percentages from fingerprint plots. |
Interaction | (1) | (2a) | (2b) |
H···H | 37.0 | 36.2 | 35.5 |
H···O | 42.0 | 41.2 | 42.6 |
H···C | 15.4 | 16.8 | 16.2 |
C···C | 4.0 | 3.5 | 3.9 |
C···O | 1.7 | 2.2 | 1.7 |
Calculated interaction energies for (6) topEnergies are expressed in kJ mol-1.
Values in parentheses include correction for BSSE. |
Primary Interactiona | B3LYP/6-31G(d,p) | M06-2X/6-31G(d,p) | ωB97X-D/6-31G(d,p) |
N1—H1A···O2 | -480.96 (-483.45) | -549.04 (-543.54) | -523.46 (-518.25) |
N1—H1B···O2i | -523.71 (-521.07) | -587.45 (-582.57) | -560.56 (-555.59) |
N2—H2C···O3v | -616.52 (-595.67) | -689.80 (-668.96) | -667.09 (-664.03) |
N2—H2B···O3iv | -608.87 (-587.89) | -684.87 (-663.76) | -661.40 (-647.04) |
N2—H2C···O4iii | -613.96 (-591.90) | -684.14 (-665.93) | -664.66 (-647.76) |
N2—H2C···N1iib | -87.21 (-81.34) | -105.42 (-94.88) | -108.75 (-95.48) |
Notes: (a) symmetry identifiers are the same as those in Table 5;
(b) two perchlorate counter-ions were included in these calculations. |
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