For the new organic salt 1H-imidazol-3-ium 1,4-dioxo-1,4-dihydronaphthalen-2-olate, C3H5N2+·C10H5O3-, ab initio calculations of the gas-phase structures of the lawsonate and imidazolium ions were performed to help in the interpretation of the structural features observed. Three different types of hydrogen bond are responsible for the three-dimensional packing of the salt.
Supporting information
CCDC reference: 934613
Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
1
H-Imidazol-3-ium 1,4-dioxo-1,4-dihydronaphthalen-2-olate
top
Crystal data top
C3H5N2+·C10H5O3− | F(000) = 504 |
Mr = 242.23 | Dx = 1.364 Mg m−3 |
Orthorhombic, P212121 | Cu Kα radiation, λ = 1.5418 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 5844 reflections |
a = 4.7783 (1) Å | θ = 3.9–66.5° |
b = 10.7727 (2) Å | µ = 0.83 mm−1 |
c = 22.9128 (5) Å | T = 298 K |
V = 1179.44 (4) Å3 | Needle, orange |
Z = 4 | 0.28 × 0.21 × 0.12 mm |
Data collection top
Oxford Xcalibur Gemini Ultra diffractometer with Atlas detector | 2091 independent reflections |
Radiation source: Enhance Ultra (Cu) X-ray Source | 1966 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.062 |
Detector resolution: 10.4186 pixels mm-1 | θmax = 66.6°, θmin = 3.9° |
w scans | h = −5→5 |
Absorption correction: analytical (CrysAlisPro; Agilent, 2012) | k = −12→12 |
Tmin = 0.861, Tmax = 0.924 | l = −27→27 |
10612 measured reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.035 | w = 1/[σ2(Fo2) + (0.0499P)2 + 0.0821P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.088 | (Δ/σ)max < 0.001 |
S = 1.05 | Δρmax = 0.16 e Å−3 |
2091 reflections | Δρmin = −0.12 e Å−3 |
170 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0032 (6) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), with how many Friedel pairs? |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.1 (2) |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R-factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O4 | −0.0065 (3) | 0.23173 (10) | 0.36739 (6) | 0.0582 (4) | |
O2 | 0.6384 (3) | 0.53669 (11) | 0.31088 (5) | 0.0545 (3) | |
O1 | 0.4704 (3) | 0.67443 (11) | 0.40191 (5) | 0.0574 (4) | |
C9 | 0.0664 (4) | 0.59711 (15) | 0.48453 (7) | 0.0435 (4) | |
H9 | 0.1469 | 0.6746 | 0.4907 | 0.052* | |
C5 | 0.0249 (3) | 0.40963 (14) | 0.42746 (6) | 0.0376 (3) | |
C2 | 0.4506 (3) | 0.49163 (14) | 0.34490 (7) | 0.0406 (3) | |
C3 | 0.3269 (4) | 0.37835 (15) | 0.33886 (7) | 0.0454 (4) | |
H3 | 0.387 | 0.3277 | 0.3085 | 0.054* | |
C10 | 0.1470 (3) | 0.52621 (13) | 0.43676 (6) | 0.0369 (3) | |
C6 | −0.1761 (4) | 0.36641 (16) | 0.46604 (7) | 0.0451 (4) | |
H6 | −0.26 | 0.2897 | 0.4598 | 0.054* | |
C7 | −0.2525 (4) | 0.43715 (17) | 0.51387 (7) | 0.0499 (4) | |
H7 | −0.3844 | 0.407 | 0.5401 | 0.06* | |
C8 | −0.1327 (4) | 0.55279 (16) | 0.52275 (7) | 0.0492 (4) | |
H8 | −0.1869 | 0.6006 | 0.5546 | 0.059* | |
C1 | 0.3623 (4) | 0.57319 (13) | 0.39573 (6) | 0.0395 (3) | |
C4 | 0.1112 (4) | 0.33248 (13) | 0.37613 (7) | 0.0421 (4) | |
N1 | 0.1010 (3) | 0.25871 (13) | 0.18337 (6) | 0.0481 (4) | |
N2 | −0.1444 (3) | 0.40035 (13) | 0.22501 (6) | 0.0483 (3) | |
C12 | −0.0294 (5) | 0.45191 (17) | 0.17647 (8) | 0.0583 (5) | |
H12 | −0.0527 | 0.5331 | 0.1636 | 0.07* | |
C13 | 0.1243 (5) | 0.36318 (18) | 0.15059 (8) | 0.0596 (5) | |
H13 | 0.2277 | 0.3718 | 0.1165 | 0.072* | |
C11 | −0.0612 (4) | 0.28451 (16) | 0.22807 (7) | 0.0500 (4) | |
H11 | −0.1097 | 0.229 | 0.2575 | 0.06* | |
H1 | 0.194 (6) | 0.190 (2) | 0.1794 (11) | 0.075* | |
H2 | −0.243 (5) | 0.445 (2) | 0.2525 (12) | 0.075* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O4 | 0.0750 (8) | 0.0399 (6) | 0.0598 (7) | −0.0138 (6) | 0.0085 (7) | −0.0117 (5) |
O2 | 0.0630 (8) | 0.0473 (6) | 0.0531 (6) | −0.0096 (6) | 0.0226 (6) | −0.0121 (5) |
O1 | 0.0714 (8) | 0.0433 (7) | 0.0576 (7) | −0.0156 (6) | 0.0208 (6) | −0.0118 (5) |
C9 | 0.0501 (9) | 0.0410 (8) | 0.0394 (8) | −0.0031 (7) | 0.0022 (7) | −0.0066 (6) |
C5 | 0.0419 (8) | 0.0351 (7) | 0.0359 (7) | 0.0010 (6) | −0.0039 (6) | 0.0016 (6) |
C2 | 0.0435 (8) | 0.0411 (8) | 0.0372 (7) | 0.0013 (7) | 0.0040 (6) | −0.0030 (6) |
C3 | 0.0502 (9) | 0.0432 (8) | 0.0428 (8) | 0.0006 (7) | 0.0056 (7) | −0.0138 (6) |
C10 | 0.0395 (7) | 0.0363 (8) | 0.0348 (7) | 0.0017 (6) | −0.0010 (6) | −0.0005 (5) |
C6 | 0.0484 (9) | 0.0394 (8) | 0.0476 (8) | −0.0042 (7) | 0.0010 (7) | 0.0039 (6) |
C7 | 0.0507 (10) | 0.0571 (10) | 0.0417 (8) | −0.0036 (8) | 0.0078 (7) | 0.0052 (7) |
C8 | 0.0568 (10) | 0.0526 (9) | 0.0381 (8) | 0.0026 (8) | 0.0065 (8) | −0.0058 (7) |
C1 | 0.0437 (8) | 0.0346 (8) | 0.0402 (8) | −0.0001 (6) | 0.0023 (6) | −0.0027 (6) |
C4 | 0.0495 (9) | 0.0332 (7) | 0.0436 (8) | −0.0009 (7) | −0.0016 (7) | −0.0028 (6) |
N1 | 0.0548 (9) | 0.0459 (7) | 0.0435 (7) | 0.0095 (7) | 0.0004 (7) | −0.0042 (6) |
N2 | 0.0590 (8) | 0.0446 (7) | 0.0414 (7) | 0.0064 (7) | 0.0068 (7) | −0.0051 (6) |
C12 | 0.0792 (13) | 0.0460 (9) | 0.0496 (9) | 0.0089 (9) | 0.0068 (9) | 0.0064 (7) |
C13 | 0.0739 (12) | 0.0606 (10) | 0.0444 (9) | 0.0089 (10) | 0.0185 (9) | 0.0046 (8) |
C11 | 0.0615 (10) | 0.0465 (9) | 0.0421 (8) | 0.0023 (8) | 0.0037 (8) | 0.0024 (7) |
Geometric parameters (Å, º) top
O4—C4 | 1.2387 (19) | C6—H6 | 0.93 |
O2—C2 | 1.284 (2) | C7—C8 | 1.386 (3) |
O1—C1 | 1.2151 (19) | C7—H7 | 0.93 |
C9—C8 | 1.378 (2) | C8—H8 | 0.93 |
C9—C10 | 1.389 (2) | N1—C11 | 1.314 (2) |
C9—H9 | 0.93 | N1—C13 | 1.358 (2) |
C5—C6 | 1.386 (2) | N1—H1 | 0.87 (3) |
C5—C10 | 1.401 (2) | N2—C11 | 1.312 (2) |
C5—C4 | 1.498 (2) | N2—C12 | 1.359 (2) |
C2—C3 | 1.363 (2) | N2—H2 | 0.92 (3) |
C2—C1 | 1.519 (2) | C12—C13 | 1.343 (3) |
C3—C4 | 1.427 (2) | C12—H12 | 0.93 |
C3—H3 | 0.93 | C13—H13 | 0.93 |
C10—C1 | 1.483 (2) | C11—H11 | 0.93 |
C6—C7 | 1.384 (3) | | |
| | | |
C8—C9—C10 | 120.10 (15) | C7—C8—H8 | 119.9 |
C8—C9—H9 | 119.9 | O1—C1—C10 | 121.83 (14) |
C10—C9—H9 | 120 | O1—C1—C2 | 119.37 (14) |
C6—C5—C10 | 119.51 (14) | C10—C1—C2 | 118.79 (13) |
C6—C5—C4 | 120.34 (14) | O4—C4—C3 | 122.33 (14) |
C10—C5—C4 | 120.15 (14) | O4—C4—C5 | 119.21 (15) |
O2—C2—C3 | 125.45 (14) | C3—C4—C5 | 118.46 (13) |
O2—C2—C1 | 116.17 (13) | C11—N1—C13 | 107.71 (15) |
C3—C2—C1 | 118.37 (14) | C11—N1—H1 | 124.3 (17) |
C2—C3—C4 | 124.24 (14) | C13—N1—H1 | 127.4 (17) |
C2—C3—H3 | 117.9 | C11—N2—C12 | 108.06 (15) |
C4—C3—H3 | 117.9 | C11—N2—H2 | 128.2 (16) |
C9—C10—C5 | 119.82 (15) | C12—N2—H2 | 123.3 (16) |
C9—C10—C1 | 120.29 (14) | C13—C12—N2 | 106.94 (16) |
C5—C10—C1 | 119.89 (13) | C13—C12—H12 | 126.5 |
C7—C6—C5 | 120.18 (16) | N2—C12—H12 | 126.5 |
C7—C6—H6 | 119.9 | C12—C13—N1 | 107.51 (16) |
C5—C6—H6 | 119.9 | C12—C13—H13 | 126.2 |
C6—C7—C8 | 120.17 (16) | N1—C13—H13 | 126.2 |
C6—C7—H7 | 119.9 | N1—C11—N2 | 109.78 (15) |
C8—C7—H7 | 119.9 | N1—C11—H11 | 125.1 |
C9—C8—C7 | 120.20 (15) | N2—C11—H11 | 125.1 |
C9—C8—H8 | 119.9 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.87 (3) | 2.46 (3) | 2.9726 (19) | 118 (2) |
N1—H1···O2i | 0.87 (3) | 1.85 (3) | 2.6999 (19) | 166 (3) |
N2—H2···O2ii | 0.92 (3) | 1.76 (3) | 2.6658 (17) | 168 (2) |
C12—H12···O4iii | 0.93 | 2.27 | 3.182 (2) | 166 |
C11—H11···O4 | 0.93 | 2.57 | 3.253 (2) | 131 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x−1, y, z; (iii) −x, y+1/2, −z+1/2. |
Selected bond lengths (Å) for lawsonate taken from X-ray diffraction
refinements, for the lawsonate and lawsone forms obtained after ab
initio optimization and from the literature top | C1—O1 | C2—O2 | C4—O4 | C3—C4 |
This work | 1.220 (2) | 1.287 (3) | 1.239 (2) | 1.423 (3) |
Lawsonate, theoreticala | 1.251 | 1.274 | 1.282 | 1.4117 |
Lawsone, theoreticala | 1.224 | 1.351 | 1.223 | 1.465 |
Lawsone, experimentalb | 1.207 (2) | 1.333 (2) | 1.228 (2) | 1.450 (3) |
Notes: (a) ab initio calculations; (b) Dekkers et
al.
(1996). |
Selected bond lengths (Å) for 1H-imidazolium taken from X-ray
diffraction refinements, for 1H-imidazolium obtained after
ab initio optimization and from the literature top | N1—C11 | N2—C11 | N2—C12 | C12—C13 | N1—C13 |
This work | 1.314 (2) | 1.312 (2) | 1.359 (2) | 1.343 (3) | 1.358 (2) |
1H-Imidazolium, theoreticala | 1.334 | 1.334 | 1.383 | 1.360 | 1.383 |
1H-Imidazole, experimentalb | 1.349 (18) | 1.313 (11) | 1.376 (11) | 1.360 (14) | 1.370 (10) |
Notes: (a) ab initio calculations; (b) Allen
(2002). |