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Morpholinium 2-chloro-4-nitrobenzoate, C
4H
10NO
+·C
7H
3ClNO
4−, (I), crystallizes in a non-centrosymmetric space group. The cations and anions are connected by N—H
O hydrogen bonds to afford a 2
1 helical chain. Morpholinium 2-chloro-5-nitrobenzoate, C
4H
10NO
+·C
7H
3ClNO
4−, (II), and morpholinium 4-chloro-3-nitrobenzoate, C
4H
10NO
+·C
7H
3ClNO
4−, (III), both crystallize in a centrosymmetric space group. In (II) and (III), two cations and two anions are held together by N—H
O hydrogen bonds to form a centrosymmetric ring with graph-set descriptor
R44(12).
Supporting information
CCDC references: 179282; 179283; 179284
The title compounds were prepared by mixing morpholine with the corresponding
benzoic acid (molar ratio of 1:1) in acetonitrile. Single crystals were grown
by slow evaporation of the solutions at room temperature.
For (I), H atoms were treated as riding atoms with C—H = 0.93 Å (aromatic
H), C—H = 0.97 Å (secondary H) and N—H = 0.89 Å, and Uiso(H)
= 1.2Ueq(C) and Uiso(H) = 1.5Ueq(N). For (II) and
(III), the H atoms were refined isotropically. Refined distances: C—H =
0.86 (3)–0.99 (3) Å and N—H = 0.83 (3)–0.99 (4) Å for (II); C—H =
0.89 (4)–1.05 (4) Å and N—H = 0.93 (3)–1.00 (3) Å for (III).
For all compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1990); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1997-1999). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990) for (I); SIR92 (Altomare et al., 1993) for (II), (III). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: TEXSAN for Windows.
Crystal data top
C4H10NO+·C7H3ClNO4− | F(000) = 600 |
Mr = 288.69 | Dx = 1.478 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 10.304 (2) Å | θ = 11.3–12.4° |
b = 19.557 (6) Å | µ = 0.31 mm−1 |
c = 6.4387 (13) Å | T = 298 K |
V = 1297.5 (5) Å3 | Prismatic, colorless |
Z = 4 | 0.40 × 0.30 × 0.20 mm |
Data collection top
Rigaku AFC-5R diffractometer | 1769 reflections with I > 2σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.058 |
Graphite monochromator | θmax = 29.0°, θmin = 2.1° |
ω–2θ scans | h = −3→14 |
Absorption correction: ψ scan (North et al., 1968) | k = −3→26 |
Tmin = 0.885, Tmax = 0.940 | l = −3→8 |
4209 measured reflections | 3 standard reflections every 97 reflections |
3101 independent reflections | intensity decay: 1.7% |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.053 | w = 1/[σ2(Fo2) + 0.4754P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.075 | (Δ/σ)max = 0.001 |
S = 1.04 | Δρmax = 0.28 e Å−3 |
3101 reflections | Δρmin = −0.23 e Å−3 |
173 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0053 (9) |
0 constraints | Absolute structure: (Flack, 1983), 1102 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.02 (8) |
Secondary atom site location: difference Fourier map | |
Crystal data top
C4H10NO+·C7H3ClNO4− | V = 1297.5 (5) Å3 |
Mr = 288.69 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 10.304 (2) Å | µ = 0.31 mm−1 |
b = 19.557 (6) Å | T = 298 K |
c = 6.4387 (13) Å | 0.40 × 0.30 × 0.20 mm |
Data collection top
Rigaku AFC-5R diffractometer | 1769 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.058 |
Tmin = 0.885, Tmax = 0.940 | 3 standard reflections every 97 reflections |
4209 measured reflections | intensity decay: 1.7% |
3101 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | H-atom parameters constrained |
wR(F2) = 0.075 | Δρmax = 0.28 e Å−3 |
S = 1.04 | Δρmin = −0.23 e Å−3 |
3101 reflections | Absolute structure: (Flack, 1983), 1102 Friedel pairs |
173 parameters | Absolute structure parameter: 0.02 (8) |
0 restraints | |
Special details top
Experimental. The scan width was (1.42 + 0.30tanθ)° with an ω scan speed of 5° per minute
(up to 3 scans to achieve I/σ(I) > 10). Stationary background counts were
recorded at each end of the scan, and the scan time:background time ratio was
2:1. |
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 | |
Cl | 0.92033 (9) | 0.26987 (5) | 1.07561 (13) | 0.0527 (3) | |
O1 | 0.7367 (2) | 0.42775 (11) | 0.8920 (4) | 0.0563 (7) | |
O2 | 0.6418 (2) | 0.35904 (11) | 1.1175 (4) | 0.0533 (7) | |
O3 | 0.8873 (2) | 0.10450 (12) | 0.4440 (4) | 0.0564 (7) | |
O4 | 0.7277 (3) | 0.13867 (12) | 0.2498 (4) | 0.0608 (8) | |
O5 | 1.1351 (2) | 0.45873 (13) | 0.3723 (3) | 0.0529 (7) | |
N1 | 0.7982 (3) | 0.14421 (14) | 0.4035 (5) | 0.0438 (7) | |
N2 | 0.8939 (2) | 0.46701 (12) | 0.5821 (4) | 0.0379 (6) | |
C1 | 0.7295 (3) | 0.30998 (15) | 0.8115 (4) | 0.0312 (8) | |
C2 | 0.8235 (3) | 0.26118 (16) | 0.8542 (4) | 0.0334 (8) | |
C3 | 0.8469 (3) | 0.20654 (15) | 0.7258 (5) | 0.0354 (8) | |
C4 | 0.7744 (3) | 0.20165 (15) | 0.5466 (5) | 0.0347 (8) | |
C5 | 0.6818 (3) | 0.24974 (19) | 0.4936 (5) | 0.0402 (8) | |
C6 | 0.6616 (3) | 0.30375 (16) | 0.6263 (5) | 0.0389 (8) | |
C7 | 0.7010 (3) | 0.36942 (16) | 0.9559 (5) | 0.0343 (8) | |
C8 | 0.9174 (3) | 0.41577 (16) | 0.4179 (5) | 0.0456 (8) | |
C9 | 1.0180 (4) | 0.4435 (2) | 0.2674 (5) | 0.0544 (11) | |
C10 | 1.1129 (3) | 0.51107 (19) | 0.5230 (5) | 0.0527 (10) | |
C11 | 1.0167 (3) | 0.48916 (19) | 0.6842 (4) | 0.0452 (10) | |
H1 | 0.9094 | 0.1740 | 0.7585 | 0.042* | |
H2 | 0.6345 | 0.2457 | 0.3712 | 0.048* | |
H3 | 0.6008 | 0.3370 | 0.5912 | 0.047* | |
H4 | 0.8410 | 0.4493 | 0.6773 | 0.057* | |
H5 | 0.8548 | 0.5033 | 0.5269 | 0.057* | |
H6 | 0.8372 | 0.4062 | 0.3446 | 0.055* | |
H7 | 0.9483 | 0.3735 | 0.4794 | 0.055* | |
H8 | 1.0346 | 0.4099 | 0.1598 | 0.065* | |
H9 | 0.9849 | 0.4845 | 0.2016 | 0.065* | |
H10 | 1.0811 | 0.5518 | 0.4536 | 0.063* | |
H11 | 1.1944 | 0.5225 | 0.5901 | 0.063* | |
H12 | 1.0522 | 0.4517 | 0.7649 | 0.054* | |
H13 | 0.9991 | 0.5269 | 0.7779 | 0.054* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl | 0.0537 (5) | 0.0565 (6) | 0.0478 (5) | 0.0121 (5) | −0.0151 (5) | −0.0085 (5) |
O1 | 0.0744 (17) | 0.0293 (13) | 0.0652 (16) | −0.0018 (13) | 0.0380 (15) | −0.0009 (13) |
O2 | 0.0655 (17) | 0.0484 (15) | 0.0460 (15) | −0.0015 (13) | 0.0206 (14) | 0.0016 (12) |
O3 | 0.0496 (16) | 0.0448 (15) | 0.0748 (17) | 0.0084 (13) | 0.0070 (15) | −0.0168 (14) |
O4 | 0.0779 (19) | 0.0534 (17) | 0.0512 (15) | −0.0068 (15) | −0.0110 (17) | −0.0165 (13) |
O5 | 0.0399 (14) | 0.0707 (19) | 0.0482 (15) | −0.0027 (13) | 0.0086 (12) | 0.0011 (14) |
N1 | 0.0463 (18) | 0.0379 (18) | 0.0473 (18) | −0.0112 (15) | 0.0133 (18) | −0.0075 (16) |
N2 | 0.0385 (15) | 0.0374 (15) | 0.0377 (14) | 0.0023 (12) | 0.0026 (14) | 0.0060 (14) |
C1 | 0.0290 (17) | 0.0276 (18) | 0.0368 (18) | 0.0002 (15) | 0.0049 (15) | 0.0029 (14) |
C2 | 0.0335 (17) | 0.0354 (19) | 0.0312 (16) | −0.0033 (16) | 0.0021 (14) | 0.0026 (15) |
C3 | 0.0347 (18) | 0.0318 (19) | 0.0396 (18) | 0.0034 (15) | 0.0024 (17) | 0.0005 (15) |
C4 | 0.0368 (17) | 0.0309 (18) | 0.0364 (18) | −0.0022 (15) | 0.0074 (17) | −0.0028 (15) |
C5 | 0.0394 (19) | 0.045 (2) | 0.0358 (17) | −0.0006 (16) | −0.0063 (14) | 0.0000 (14) |
C6 | 0.0365 (18) | 0.037 (2) | 0.043 (2) | 0.0073 (16) | −0.0022 (18) | 0.0048 (16) |
C7 | 0.0333 (17) | 0.0306 (18) | 0.039 (2) | 0.0036 (15) | 0.0011 (17) | 0.0012 (16) |
C8 | 0.048 (2) | 0.0439 (19) | 0.0448 (19) | −0.0063 (18) | 0.006 (2) | −0.0027 (19) |
C9 | 0.066 (3) | 0.062 (3) | 0.036 (2) | −0.002 (2) | 0.013 (2) | −0.005 (2) |
C10 | 0.041 (2) | 0.059 (3) | 0.058 (2) | −0.0123 (19) | −0.0015 (18) | −0.0005 (19) |
C11 | 0.054 (2) | 0.049 (2) | 0.0324 (19) | 0.0052 (18) | −0.0076 (18) | −0.0005 (17) |
Geometric parameters (Å, º) top
Cl—C2 | 1.748 (3) | O5—C9 | 1.414 (4) |
O1—C7 | 1.267 (3) | O5—C10 | 1.429 (4) |
O2—C7 | 1.223 (4) | N2—C8 | 1.477 (4) |
O3—N1 | 1.230 (3) | N2—C11 | 1.490 (4) |
O4—N1 | 1.232 (3) | N2—H4 | 0.89 |
N1—C4 | 1.474 (4) | N2—H5 | 0.89 |
C1—C2 | 1.387 (4) | C8—C9 | 1.519 (4) |
C1—C6 | 1.388 (4) | C8—H6 | 0.97 |
C1—C7 | 1.517 (4) | C8—H7 | 0.97 |
C2—C3 | 1.372 (4) | C9—H8 | 0.97 |
C3—C4 | 1.378 (4) | C9—H9 | 0.97 |
C3—H1 | 0.93 | C10—C11 | 1.499 (4) |
C4—C5 | 1.382 (4) | C10—H10 | 0.97 |
C5—C6 | 1.375 (4) | C10—H11 | 0.97 |
C5—H2 | 0.93 | C11—H12 | 0.97 |
C6—H3 | 0.93 | C11—H13 | 0.97 |
| | | |
O1···N2 | 2.682 (3) | O5···N1ii | 2.994 (4) |
O1···N2i | 2.747 (3) | | |
| | | |
O3—N1—O4 | 123.7 (3) | O5—C9—H9 | 109.5 |
O3—N1—C4 | 118.2 (3) | C8—C9—H9 | 109.5 |
O4—N1—C4 | 118.1 (3) | H8—C9—H9 | 108.1 |
C2—C1—C6 | 117.5 (3) | O5—C10—C11 | 111.8 (3) |
C2—C1—C7 | 122.8 (3) | O5—C10—H10 | 109.3 |
C6—C1—C7 | 119.7 (3) | C11—C10—H10 | 109.3 |
C3—C2—C1 | 122.6 (3) | O5—C10—H11 | 109.3 |
C3—C2—Cl | 117.9 (2) | C11—C10—H11 | 109.3 |
C1—C2—Cl | 119.6 (2) | H10—C10—H11 | 107.9 |
C2—C3—C4 | 117.6 (3) | N2—C8—C9 | 109.1 (2) |
C2—C3—H1 | 121.2 | N2—C8—H6 | 109.9 |
C4—C3—H1 | 121.2 | C9—C8—H6 | 109.9 |
C3—C4—C5 | 122.3 (3) | N2—C8—H7 | 109.9 |
C3—C4—N1 | 119.1 (3) | C9—C8—H7 | 109.9 |
C5—C4—N1 | 118.6 (3) | N2—C11—C10 | 109.8 (2) |
C6—C5—C4 | 118.3 (3) | N2—C11—H12 | 109.7 |
C6—C5—H2 | 120.9 | C10—C11—H12 | 109.7 |
C4—C5—H2 | 120.9 | N2—C11—H13 | 109.7 |
C5—C6—C1 | 121.7 (3) | C10—C11—H13 | 109.7 |
C5—C6—H3 | 119.2 | H12—C11—H13 | 108.2 |
C1—C6—H3 | 119.2 | C8—N2—C11 | 112.0 (2) |
O2—C7—O1 | 124.8 (3) | C8—N2—H4 | 109.2 |
O2—C7—C1 | 119.4 (3) | C11—N2—H4 | 109.2 |
O1—C7—C1 | 115.7 (3) | C8—N2—H5 | 109.2 |
H6—C8—H7 | 108.3 | C11—N2—H5 | 109.2 |
O5—C9—C8 | 110.6 (3) | H4—N2—H5 | 107.9 |
O5—C9—H8 | 109.5 | C9—O5—C10 | 109.8 (3) |
C8—C9—H8 | 109.5 | | |
| | | |
C6—C1—C2—C3 | −2.8 (4) | C4—C5—C6—C1 | −1.3 (5) |
C7—C1—C2—C3 | 178.3 (3) | C2—C1—C6—C5 | 2.9 (4) |
C6—C1—C2—Cl | 175.3 (2) | C7—C1—C6—C5 | −178.2 (3) |
C7—C1—C2—Cl | −3.5 (4) | C2—C1—C7—O2 | −74.1 (4) |
C1—C2—C3—C4 | 1.1 (4) | C6—C1—C7—O2 | 107.1 (4) |
Cl—C2—C3—C4 | −177.1 (2) | C2—C1—C7—O1 | 108.9 (3) |
C2—C3—C4—C5 | 0.6 (4) | C6—C1—C7—O1 | −69.9 (4) |
C2—C3—C4—N1 | 179.1 (3) | C11—N2—C8—C9 | −53.3 (3) |
O3—N1—C4—C3 | −3.9 (4) | C10—O5—C9—C8 | −62.5 (4) |
O4—N1—C4—C3 | 176.2 (3) | N2—C8—C9—O5 | 58.6 (4) |
O3—N1—C4—C5 | 174.6 (3) | C9—O5—C10—C11 | 61.3 (4) |
O4—N1—C4—C5 | −5.3 (4) | C8—N2—C11—C10 | 52.0 (4) |
C3—C4—C5—C6 | −0.6 (5) | O5—C10—C11—N2 | −55.2 (4) |
N1—C4—C5—C6 | −179.0 (3) | | |
Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) x+1/2, −y+1/2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H4···O1 | 0.89 | 1.80 | 2.682 (3) | 170 |
N2—H5···O1iii | 0.89 | 1.86 | 2.747 (3) | 174 |
C6—H3···O3iv | 0.93 | 2.49 | 3.378 (4) | 160 |
C10—H11···O5v | 0.97 | 2.55 | 3.486 (4) | 161 |
C11—H12···O4ii | 0.97 | 2.53 | 3.340 (4) | 141 |
Symmetry codes: (ii) x+1/2, −y+1/2, −z+1; (iii) −x+3/2, −y+1, z−1/2; (iv) x−1/2, −y+1/2, −z+1; (v) −x+5/2, −y+1, z+1/2. |
Crystal data top
C4H10NO+·C7H3ClNO4− | F(000) = 1200 |
Mr = 288.69 | Dx = 1.492 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 25 reflections |
a = 18.680 (6) Å | θ = 11.2–12.5° |
b = 10.498 (3) Å | µ = 0.32 mm−1 |
c = 13.125 (3) Å | T = 298 K |
β = 93.35 (2)° | Prismatic, colorless |
V = 2569.5 (13) Å3 | 0.40 × 0.30 × 0.20 mm |
Z = 8 | |
Data collection top
Rigaku AFC-5R diffractometer | 1741 reflections with I > 2σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.025 |
Graphite monochromator | θmax = 27.5°, θmin = 2.2° |
ω–2θ scans | h = −1→24 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→13 |
Tmin = 0.884, Tmax = 0.940 | l = −17→17 |
3215 measured reflections | 3 standard reflections every 97 reflections |
2945 independent reflections | intensity decay: 1.5% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.046 | All H-atom parameters refined |
wR(F2) = 0.121 | w = 1/[σ2(Fo2) + (0.0219P)2 + 1.024P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.001 |
2945 reflections | Δρmax = 0.26 e Å−3 |
225 parameters | Δρmin = −0.24 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0240 (11) |
Crystal data top
C4H10NO+·C7H3ClNO4− | V = 2569.5 (13) Å3 |
Mr = 288.69 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 18.680 (6) Å | µ = 0.32 mm−1 |
b = 10.498 (3) Å | T = 298 K |
c = 13.125 (3) Å | 0.40 × 0.30 × 0.20 mm |
β = 93.35 (2)° | |
Data collection top
Rigaku AFC-5R diffractometer | 1741 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.025 |
Tmin = 0.884, Tmax = 0.940 | 3 standard reflections every 97 reflections |
3215 measured reflections | intensity decay: 1.5% |
2945 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.121 | All H-atom parameters refined |
S = 1.00 | Δρmax = 0.26 e Å−3 |
2945 reflections | Δρmin = −0.24 e Å−3 |
225 parameters | |
Special details top
Experimental. The scan width was (1.37 + 0.30tanθ)° with an ω scan speed of 4° per minute
(up to 4 scans to achieve I/σ(I) > 10). Stationary background counts were
recorded at each end of the scan, and the scan time:background time ratio was
2:1. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl | 0.58105 (4) | 0.37294 (7) | 0.32979 (6) | 0.0559 (3) | |
O1 | 0.61609 (11) | 0.00193 (18) | 0.36764 (15) | 0.0556 (5) | |
O2 | 0.58973 (9) | 0.14191 (18) | 0.48707 (14) | 0.0506 (5) | |
O3 | 0.92286 (11) | 0.2335 (3) | 0.30218 (17) | 0.0784 (8) | |
O4 | 0.89280 (11) | 0.0791 (2) | 0.3986 (2) | 0.0720 (7) | |
O5 | 0.31960 (10) | 0.29981 (19) | 0.43692 (15) | 0.0550 (5) | |
N1 | 0.87919 (12) | 0.1750 (3) | 0.34898 (18) | 0.0527 (6) | |
N2 | 0.44683 (12) | 0.1719 (2) | 0.50853 (18) | 0.0432 (6) | |
C1 | 0.68165 (12) | 0.1917 (2) | 0.37796 (17) | 0.0335 (5) | |
C2 | 0.66822 (13) | 0.3131 (2) | 0.33920 (18) | 0.0377 (6) | |
C3 | 0.72200 (16) | 0.3875 (3) | 0.3022 (2) | 0.0472 (7) | |
C4 | 0.79118 (16) | 0.3433 (3) | 0.3050 (2) | 0.0477 (7) | |
C5 | 0.80519 (13) | 0.2243 (2) | 0.34609 (18) | 0.0392 (6) | |
C6 | 0.75198 (13) | 0.1480 (2) | 0.38116 (18) | 0.0371 (6) | |
C7 | 0.62345 (12) | 0.1057 (2) | 0.41338 (18) | 0.0373 (6) | |
C8 | 0.41171 (17) | 0.1445 (3) | 0.4057 (2) | 0.0527 (7) | |
C9 | 0.33271 (16) | 0.1724 (3) | 0.4082 (2) | 0.0523 (7) | |
C10 | 0.35140 (16) | 0.3231 (3) | 0.5362 (2) | 0.0524 (7) | |
C11 | 0.43096 (15) | 0.3038 (3) | 0.5412 (2) | 0.0475 (7) | |
H1 | 0.7123 (15) | 0.460 (3) | 0.275 (2) | 0.057 (9)* | |
H2 | 0.8270 (15) | 0.390 (2) | 0.283 (2) | 0.048 (8)* | |
H3 | 0.7624 (12) | 0.062 (3) | 0.4072 (18) | 0.040 (7)* | |
H4 | 0.4906 (16) | 0.161 (3) | 0.503 (2) | 0.049 (8)* | |
H5 | 0.4300 (17) | 0.108 (3) | 0.558 (3) | 0.080 (10)* | |
H6 | 0.4323 (18) | 0.197 (3) | 0.361 (3) | 0.073 (10)* | |
H7 | 0.4214 (15) | 0.055 (3) | 0.387 (2) | 0.064 (9)* | |
H8 | 0.3075 (16) | 0.159 (3) | 0.336 (2) | 0.062 (9)* | |
H9 | 0.3098 (14) | 0.117 (3) | 0.454 (2) | 0.051 (8)* | |
H10 | 0.3438 (15) | 0.411 (3) | 0.550 (2) | 0.060 (9)* | |
H11 | 0.3310 (16) | 0.268 (3) | 0.584 (2) | 0.061 (9)* | |
H12 | 0.4530 (14) | 0.359 (2) | 0.495 (2) | 0.045 (8)* | |
H13 | 0.4546 (16) | 0.311 (3) | 0.610 (2) | 0.064 (9)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl | 0.0463 (4) | 0.0548 (4) | 0.0658 (5) | 0.0102 (3) | −0.0024 (3) | 0.0033 (4) |
O1 | 0.0674 (13) | 0.0458 (11) | 0.0557 (12) | −0.0179 (10) | 0.0207 (10) | −0.0075 (9) |
O2 | 0.0397 (10) | 0.0620 (12) | 0.0520 (11) | −0.0028 (9) | 0.0180 (9) | −0.0051 (9) |
O3 | 0.0406 (11) | 0.132 (2) | 0.0645 (13) | −0.0101 (13) | 0.0187 (10) | 0.0137 (14) |
O4 | 0.0443 (12) | 0.0661 (15) | 0.1056 (19) | 0.0073 (11) | 0.0033 (12) | 0.0037 (14) |
O5 | 0.0477 (11) | 0.0564 (12) | 0.0596 (12) | 0.0025 (10) | −0.0091 (9) | 0.0078 (10) |
N1 | 0.0351 (12) | 0.0757 (18) | 0.0477 (14) | −0.0077 (12) | 0.0049 (11) | −0.0124 (13) |
N2 | 0.0307 (12) | 0.0499 (14) | 0.0497 (13) | −0.0009 (10) | 0.0084 (10) | 0.0079 (11) |
C1 | 0.0343 (12) | 0.0373 (13) | 0.0293 (11) | −0.0034 (10) | 0.0042 (10) | −0.0035 (10) |
C2 | 0.0350 (12) | 0.0415 (14) | 0.0365 (13) | 0.0023 (11) | 0.0006 (10) | −0.0030 (11) |
C3 | 0.0600 (18) | 0.0366 (15) | 0.0451 (15) | −0.0056 (14) | 0.0029 (13) | 0.0048 (13) |
C4 | 0.0477 (16) | 0.0530 (17) | 0.0433 (15) | −0.0184 (14) | 0.0092 (13) | −0.0019 (13) |
C5 | 0.0341 (13) | 0.0498 (15) | 0.0338 (13) | −0.0044 (12) | 0.0026 (10) | −0.0076 (12) |
C6 | 0.0368 (13) | 0.0413 (15) | 0.0335 (12) | −0.0042 (11) | 0.0043 (10) | −0.0028 (11) |
C7 | 0.0331 (12) | 0.0429 (14) | 0.0360 (13) | −0.0009 (11) | 0.0032 (10) | 0.0008 (11) |
C8 | 0.0596 (19) | 0.054 (2) | 0.0457 (16) | −0.0022 (15) | 0.0125 (14) | 0.0003 (14) |
C9 | 0.0526 (17) | 0.0575 (19) | 0.0457 (16) | −0.0119 (15) | −0.0055 (14) | 0.0068 (14) |
C10 | 0.0476 (17) | 0.0522 (18) | 0.0571 (19) | 0.0045 (14) | 0.0013 (15) | −0.0034 (16) |
C11 | 0.0407 (15) | 0.0492 (17) | 0.0522 (17) | −0.0043 (13) | −0.0017 (13) | 0.0008 (14) |
Geometric parameters (Å, º) top
Cl—C2 | 1.743 (3) | O5—C10 | 1.421 (3) |
O1—C7 | 1.247 (3) | N1—C5 | 1.474 (3) |
O2—C7 | 1.244 (3) | N2—C11 | 1.484 (4) |
O3—N1 | 1.216 (3) | N2—C8 | 1.494 (4) |
O4—N1 | 1.218 (3) | N2—H4 | 0.83 (3) |
C1—C2 | 1.389 (3) | N2—H5 | 0.99 (4) |
C1—C6 | 1.390 (3) | C8—C9 | 1.507 (4) |
C1—C7 | 1.508 (3) | C8—H6 | 0.91 (3) |
C2—C3 | 1.383 (4) | C8—H7 | 0.99 (3) |
C3—C4 | 1.372 (4) | C9—H8 | 1.04 (3) |
C3—H1 | 0.86 (3) | C9—H9 | 0.96 (3) |
C4—C5 | 1.379 (4) | C10—C11 | 1.497 (4) |
C4—H2 | 0.89 (3) | C10—H10 | 0.95 (3) |
C5—C6 | 1.376 (3) | C10—H11 | 0.95 (3) |
C6—H3 | 0.98 (3) | C11—H12 | 0.95 (3) |
O5—C9 | 1.415 (4) | C11—H13 | 0.99 (3) |
| | | |
O1···N2i | 2.753 (3) | O2···O3ii | 3.081 (3) |
O2···N2 | 2.719 (3) | O2···C5ii | 3.181 (3) |
O2···N1ii | 2.918 (3) | | |
| | | |
O3—N1—O4 | 124.2 (3) | O1—C7—C1 | 115.9 (2) |
O3—N1—C5 | 117.7 (3) | N2—C8—H6 | 107 (2) |
O4—N1—C5 | 118.0 (2) | C9—C8—H6 | 110 (2) |
C11—N2—H4 | 111.3 (19) | N2—C8—H7 | 109.2 (17) |
C8—N2—H4 | 107 (2) | C9—C8—H7 | 112.5 (17) |
C11—N2—H5 | 111.1 (19) | H6—C8—H7 | 109 (3) |
C8—N2—H5 | 108.7 (19) | O5—C9—C8 | 112.0 (2) |
H4—N2—H5 | 108 (3) | O5—C9—H8 | 107.0 (16) |
C2—C1—C6 | 117.6 (2) | C8—C9—H8 | 110.3 (17) |
C2—C1—C7 | 123.0 (2) | O5—C9—H9 | 108.6 (16) |
C6—C1—C7 | 119.4 (2) | C8—C9—H9 | 111.6 (16) |
C3—C2—C1 | 121.8 (2) | H8—C9—H9 | 107 (2) |
C3—C2—Cl | 117.8 (2) | O5—C10—C11 | 112.2 (3) |
C1—C2—Cl | 120.29 (19) | O5—C10—H10 | 106.2 (17) |
C4—C3—C2 | 120.2 (3) | C11—C10—H10 | 106.3 (17) |
C4—C3—H1 | 119 (2) | O5—C10—H11 | 109.8 (17) |
C2—C3—H1 | 121 (2) | C11—C10—H11 | 108.9 (18) |
C3—C4—C5 | 118.3 (3) | H10—C10—H11 | 113 (3) |
C3—C4—H2 | 122.0 (17) | N2—C8—C9 | 108.8 (2) |
C5—C4—H2 | 119.7 (17) | N2—C11—C10 | 109.2 (2) |
C6—C5—C4 | 122.2 (2) | N2—C11—H12 | 106.3 (15) |
C6—C5—N1 | 118.8 (2) | C10—C11—H12 | 110.8 (16) |
C4—C5—N1 | 118.9 (2) | N2—C11—H13 | 104.4 (17) |
C5—C6—C1 | 119.8 (2) | C10—C11—H13 | 114.7 (18) |
C5—C6—H3 | 121.4 (14) | H12—C11—H13 | 111 (2) |
C1—C6—H3 | 118.8 (14) | C8—N2—C11 | 110.8 (2) |
O2—C7—O1 | 126.5 (2) | C9—O5—C10 | 109.7 (2) |
O2—C7—C1 | 117.6 (2) | | |
| | | |
C6—C1—C2—C3 | 1.8 (4) | N1—C5—C6—C1 | −179.1 (2) |
C7—C1—C2—C3 | −176.5 (2) | C2—C1—C6—C5 | −0.3 (3) |
C6—C1—C2—Cl | 178.40 (18) | C7—C1—C6—C5 | 178.0 (2) |
C7—C1—C2—Cl | 0.1 (3) | C2—C1—C7—O2 | −63.1 (3) |
C1—C2—C3—C4 | −1.4 (4) | C6—C1—C7—O2 | 118.7 (3) |
Cl—C2—C3—C4 | −178.1 (2) | C2—C1—C7—O1 | 119.8 (3) |
C2—C3—C4—C5 | −0.5 (4) | C6—C1—C7—O1 | −58.5 (3) |
C3—C4—C5—C6 | 1.9 (4) | C11—N2—C8—C9 | −54.4 (3) |
C3—C4—C5—N1 | 179.6 (2) | C10—O5—C9—C8 | −60.5 (3) |
O3—N1—C5—C6 | 167.6 (2) | N2—C8—C9—O5 | 57.7 (3) |
O4—N1—C5—C6 | −13.0 (4) | C9—O5—C10—C11 | 60.4 (3) |
O3—N1—C5—C4 | −10.1 (4) | C8—N2—C11—C10 | 54.5 (3) |
O4—N1—C5—C4 | 169.3 (2) | O5—C10—C11—N2 | −57.6 (3) |
C4—C5—C6—C1 | −1.5 (4) | | |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+3/2, −y+1/2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H4···O2 | 0.83 (3) | 1.89 (3) | 2.719 (3) | 178 (2) |
N2—H5···O1i | 1.00 (4) | 1.77 (3) | 2.753 (3) | 169 (3) |
C4—H2···O1iii | 0.89 (3) | 2.58 (3) | 3.371 (4) | 148 (2) |
C11—H13···O3ii | 0.98 (3) | 2.55 (3) | 3.344 (4) | 138 (2) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+3/2, −y+1/2, −z+1; (iii) −x+3/2, y+1/2, −z+1/2. |
Crystal data top
C4H10NO+·C7H3ClNO4− | F(000) = 1200.0 |
Mr = 288.69 | Dx = 1.493 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 25 reflections |
a = 19.76 (2) Å | θ = 11.1–12.4° |
b = 10.085 (7) Å | µ = 0.32 mm−1 |
c = 13.639 (5) Å | T = 296 K |
β = 109.09 (4)° | Prismatic, colorless |
V = 2569 (3) Å3 | 0.40 × 0.30 × 0.25 mm |
Z = 8 | |
Data collection top
Rigaku AFC-5R diffractometer | 1850 reflections with I > 2σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.025 |
Graphite monochromator | θmax = 27.5°, θmin = 2.2° |
ω–2θ scans | h = −1→25 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→13 |
Tmin = 0.884, Tmax = 0.925 | l = −17→16 |
3198 measured reflections | 3 standard reflections every 97 reflections |
2945 independent reflections | intensity decay: none |
Refinement top
Refinement on F2 | 0 constraints |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.047 | w = 1/[σ2(Fo2) + 2.0068P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.116 | (Δ/σ)max = 0.001 |
S = 1.03 | Δρmax = 0.25 e Å−3 |
2945 reflections | Δρmin = −0.20 e Å−3 |
225 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0053 (4) |
Crystal data top
C4H10NO+·C7H3ClNO4− | V = 2569 (3) Å3 |
Mr = 288.69 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 19.76 (2) Å | µ = 0.32 mm−1 |
b = 10.085 (7) Å | T = 296 K |
c = 13.639 (5) Å | 0.40 × 0.30 × 0.25 mm |
β = 109.09 (4)° | |
Data collection top
Rigaku AFC-5R diffractometer | 1850 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.025 |
Tmin = 0.884, Tmax = 0.925 | 3 standard reflections every 97 reflections |
3198 measured reflections | intensity decay: none |
2945 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.116 | All H-atom parameters refined |
S = 1.03 | Δρmax = 0.25 e Å−3 |
2945 reflections | Δρmin = −0.20 e Å−3 |
225 parameters | |
Special details top
Experimental. The scan width was (1.78 + 0.30tanθ)° with an ω scan speed of 6° per minute
(up to 3 scans to achieve I/σ(I) > 10). Stationary background counts were
recorded at each end of the scan, and the scan time:background time ratio was
2:1. |
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 | |
Cl | 1.17692 (3) | 0.32746 (7) | 0.71584 (6) | 0.0542 (2) | |
O1 | 0.83337 (9) | 0.49794 (19) | 0.51908 (17) | 0.0551 (6) | |
O2 | 0.87669 (10) | 0.69523 (19) | 0.57879 (17) | 0.0600 (6) | |
O3 | 1.13261 (12) | 0.7507 (2) | 0.66169 (19) | 0.0721 (7) | |
O4 | 1.20375 (10) | 0.6031 (2) | 0.74928 (19) | 0.0742 (7) | |
O5 | 0.93652 (10) | 1.0593 (2) | 0.6065 (2) | 0.0685 (7) | |
N1 | 1.14522 (10) | 0.6378 (2) | 0.69468 (17) | 0.0425 (5) | |
N2 | 0.80195 (10) | 0.9304 (2) | 0.53913 (18) | 0.0415 (5) | |
C1 | 0.95747 (11) | 0.5167 (2) | 0.60193 (17) | 0.0292 (5) | |
C2 | 1.01702 (12) | 0.5977 (2) | 0.63248 (18) | 0.0308 (5) | |
C3 | 1.08556 (11) | 0.5438 (2) | 0.66716 (17) | 0.0299 (5) | |
C4 | 1.09512 (11) | 0.4071 (2) | 0.67291 (17) | 0.0327 (5) | |
C5 | 1.03493 (12) | 0.3269 (3) | 0.64108 (19) | 0.0368 (6) | |
C6 | 0.96719 (12) | 0.3806 (2) | 0.60579 (18) | 0.0318 (5) | |
C7 | 0.88264 (11) | 0.5755 (3) | 0.56369 (18) | 0.0344 (5) | |
C8 | 0.83071 (15) | 0.9979 (4) | 0.4643 (3) | 0.0567 (8) | |
C9 | 0.91125 (16) | 0.9987 (4) | 0.5074 (3) | 0.0637 (9) | |
C10 | 0.91069 (17) | 0.9912 (4) | 0.6780 (3) | 0.0596 (9) | |
C11 | 0.83031 (16) | 0.9912 (4) | 0.6432 (3) | 0.0554 (8) | |
H1 | 1.0113 (13) | 0.691 (3) | 0.6308 (18) | 0.041 (7)* | |
H2 | 1.0399 (13) | 0.228 (3) | 0.6427 (18) | 0.042 (7)* | |
H3 | 0.9274 (13) | 0.322 (2) | 0.5834 (18) | 0.037 (7)* | |
H4 | 0.8170 (15) | 0.842 (3) | 0.545 (2) | 0.050 (8)* | |
H5 | 0.7490 (18) | 0.941 (3) | 0.516 (2) | 0.068 (9)* | |
H6 | 0.8137 (19) | 0.949 (3) | 0.397 (3) | 0.084 (12)* | |
H7 | 0.8124 (16) | 1.093 (3) | 0.463 (2) | 0.068 (10)* | |
H8 | 0.9282 (16) | 0.910 (3) | 0.516 (2) | 0.063 (10)* | |
H9 | 0.9276 (17) | 1.051 (3) | 0.464 (2) | 0.074 (11)* | |
H10 | 0.9286 (17) | 0.893 (4) | 0.684 (2) | 0.078 (11)* | |
H11 | 0.927 (2) | 1.037 (4) | 0.737 (3) | 0.108 (15)* | |
H12 | 0.8142 (19) | 0.951 (3) | 0.696 (3) | 0.086 (12)* | |
H13 | 0.8107 (17) | 1.078 (3) | 0.634 (2) | 0.072 (10)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl | 0.0297 (3) | 0.0566 (5) | 0.0721 (5) | 0.0162 (3) | 0.0107 (3) | 0.0181 (4) |
O1 | 0.0234 (8) | 0.0544 (13) | 0.0792 (15) | 0.0038 (8) | 0.0055 (9) | −0.0024 (10) |
O2 | 0.0403 (10) | 0.0404 (11) | 0.0920 (16) | 0.0157 (9) | 0.0115 (10) | −0.0041 (10) |
O3 | 0.0583 (13) | 0.0485 (13) | 0.0971 (18) | −0.0207 (11) | 0.0083 (12) | 0.0153 (12) |
O4 | 0.0281 (10) | 0.0741 (16) | 0.1012 (18) | −0.0086 (10) | −0.0053 (11) | −0.0002 (13) |
O5 | 0.0377 (11) | 0.0541 (13) | 0.0997 (19) | −0.0195 (10) | 0.0034 (11) | 0.0003 (13) |
N1 | 0.0317 (11) | 0.0463 (13) | 0.0469 (13) | −0.0085 (10) | 0.0091 (10) | −0.0020 (10) |
N2 | 0.0192 (9) | 0.0354 (12) | 0.0632 (15) | 0.0000 (9) | 0.0043 (9) | −0.0034 (11) |
C1 | 0.0251 (10) | 0.0332 (12) | 0.0293 (12) | 0.0042 (9) | 0.0089 (9) | 0.0015 (10) |
C2 | 0.0306 (11) | 0.0274 (12) | 0.0343 (13) | 0.0004 (9) | 0.0106 (10) | −0.0004 (10) |
C3 | 0.0234 (10) | 0.0346 (13) | 0.0309 (12) | −0.0028 (9) | 0.0076 (9) | 0.0013 (10) |
C4 | 0.0251 (10) | 0.0404 (13) | 0.0321 (13) | 0.0077 (10) | 0.0087 (9) | 0.0073 (10) |
C5 | 0.0332 (12) | 0.0307 (13) | 0.0464 (15) | 0.0050 (10) | 0.0130 (11) | 0.0064 (11) |
C6 | 0.0263 (11) | 0.0319 (12) | 0.0369 (13) | −0.0015 (9) | 0.0099 (10) | 0.0022 (10) |
C7 | 0.0241 (11) | 0.0401 (14) | 0.0385 (14) | 0.0060 (10) | 0.0093 (10) | 0.0030 (11) |
C8 | 0.0348 (14) | 0.070 (2) | 0.060 (2) | 0.0003 (14) | 0.0078 (14) | 0.0103 (17) |
C9 | 0.0360 (15) | 0.076 (2) | 0.079 (3) | 0.0007 (16) | 0.0187 (16) | 0.025 (2) |
C10 | 0.0420 (15) | 0.066 (2) | 0.059 (2) | −0.0076 (15) | −0.0001 (15) | −0.0185 (17) |
C11 | 0.0423 (15) | 0.061 (2) | 0.062 (2) | 0.0041 (14) | 0.0162 (15) | −0.0108 (17) |
Geometric parameters (Å, º) top
Cl—C4 | 1.727 (3) | O5—C9 | 1.416 (4) |
O1—C7 | 1.242 (3) | O5—C10 | 1.418 (4) |
O2—C7 | 1.237 (3) | N2—C11 | 1.479 (4) |
O3—N1 | 1.220 (3) | N2—C8 | 1.486 (4) |
O4—N1 | 1.204 (3) | N2—H4 | 0.93 (3) |
N1—C3 | 1.463 (3) | N2—H5 | 1.00 (3) |
C1—C2 | 1.380 (3) | C8—C9 | 1.505 (4) |
C1—C6 | 1.384 (3) | C8—H6 | 1.00 (3) |
C1—C7 | 1.518 (3) | C8—H7 | 1.02 (3) |
C2—C3 | 1.391 (3) | C9—H8 | 0.95 (3) |
C2—H1 | 0.95 (3) | C9—H9 | 0.93 (3) |
C3—C4 | 1.390 (3) | C10—C11 | 1.501 (4) |
C4—C5 | 1.386 (3) | C10—H10 | 1.05 (4) |
C5—C6 | 1.377 (3) | C10—H11 | 0.89 (4) |
C5—H2 | 1.00 (3) | C11—H12 | 0.96 (4) |
C6—H3 | 0.95 (2) | C11—H13 | 0.95 (3) |
| | | |
O1···N2i | 2.629 (4) | C2···C6ii | 3.372 (4) |
O2···N2 | 2.752 (3) | C4···C7ii | 3.400 (4) |
| | | |
O4—N1—O3 | 122.5 (2) | O1—C7—C1 | 116.2 (2) |
O4—N1—C3 | 120.0 (2) | N2—C8—H6 | 109 (2) |
O3—N1—C3 | 117.4 (2) | C9—C8—H6 | 111 (2) |
C11—N2—H4 | 107.7 (16) | N2—C8—H7 | 103.2 (18) |
C8—N2—H4 | 108.1 (17) | C9—C8—H7 | 109.0 (18) |
C11—N2—H5 | 106.8 (18) | H6—C8—H7 | 116 (3) |
C8—N2—H5 | 109.1 (18) | O5—C9—C8 | 111.9 (3) |
H4—N2—H5 | 114 (2) | O5—C9—H8 | 107.0 (18) |
C2—C1—C6 | 118.8 (2) | C8—C9—H8 | 109.1 (19) |
C2—C1—C7 | 120.7 (2) | O5—C9—H9 | 106 (2) |
C6—C1—C7 | 120.5 (2) | C8—C9—H9 | 107 (2) |
C1—C2—C3 | 120.7 (2) | H8—C9—H9 | 116 (3) |
C1—C2—H1 | 119.8 (15) | O5—C10—C11 | 111.4 (3) |
C3—C2—H1 | 119.5 (15) | O5—C10—H10 | 108.7 (18) |
C4—C3—C2 | 120.4 (2) | C11—C10—H10 | 108.6 (18) |
C4—C3—N1 | 123.0 (2) | O5—C10—H11 | 105 (3) |
C2—C3—N1 | 116.6 (2) | C11—C10—H11 | 109 (3) |
C5—C4—C3 | 118.3 (2) | H10—C10—H11 | 114 (3) |
C5—C4—Cl | 116.5 (2) | N2—C8—C9 | 109.1 (3) |
C3—C4—Cl | 125.14 (18) | N2—C11—C10 | 109.4 (3) |
C6—C5—C4 | 121.1 (2) | N2—C11—H12 | 115 (2) |
C6—C5—H2 | 118.5 (15) | C10—C11—H12 | 110 (2) |
C4—C5—H2 | 120.4 (14) | N2—C11—H13 | 104.1 (19) |
C5—C6—C1 | 120.7 (2) | C10—C11—H13 | 113 (2) |
C5—C6—H3 | 118.3 (15) | H12—C11—H13 | 106 (3) |
C1—C6—H3 | 121.0 (15) | C8—N2—C11 | 111.1 (2) |
O2—C7—O1 | 126.5 (2) | C9—O5—C10 | 110.7 (2) |
O2—C7—C1 | 117.3 (2) | | |
| | | |
C6—C1—C2—C3 | −0.4 (4) | C4—C5—C6—C1 | −0.5 (4) |
C7—C1—C2—C3 | −179.8 (2) | C2—C1—C6—C5 | 1.1 (4) |
C1—C2—C3—C4 | −0.9 (4) | C7—C1—C6—C5 | −179.6 (2) |
C1—C2—C3—N1 | 178.1 (2) | C2—C1—C7—O2 | −12.9 (4) |
O4—N1—C3—C4 | −20.3 (4) | C6—C1—C7—O2 | 167.7 (2) |
O3—N1—C3—C4 | 160.9 (3) | C2—C1—C7—O1 | 166.3 (2) |
O4—N1—C3—C2 | 160.8 (2) | C6—C1—C7—O1 | −13.0 (3) |
O3—N1—C3—C2 | −18.1 (3) | C11—N2—C8—C9 | 54.2 (4) |
C2—C3—C4—C5 | 1.5 (4) | C10—O5—C9—C8 | 59.7 (4) |
N1—C3—C4—C5 | −177.5 (2) | N2—C8—C9—O5 | −56.4 (4) |
C2—C3—C4—Cl | −179.21 (18) | C9—O5—C10—C11 | −59.9 (4) |
N1—C3—C4—Cl | 1.9 (4) | C8—N2—C11—C10 | −55.0 (4) |
C3—C4—C5—C6 | −0.8 (4) | O5—C10—C11—N2 | 57.5 (4) |
Cl—C4—C5—C6 | 179.8 (2) | | |
Symmetry codes: (i) −x+3/2, −y+3/2, −z+1; (ii) −x+2, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H4···O2 | 0.93 (3) | 1.85 (3) | 2.752 (4) | 160 (3) |
N2—H5···O1i | 0.99 (4) | 1.66 (4) | 2.629 (4) | 164 (3) |
C5—H2···O5iii | 1.00 (3) | 2.58 (3) | 3.269 (5) | 125.9 (19) |
C8—H6···O4iv | 1.00 (4) | 2.49 (4) | 3.335 (6) | 142 (3) |
C10—H10···O2 | 1.05 (4) | 2.48 (4) | 3.255 (6) | 131 (2) |
Symmetry codes: (i) −x+3/2, −y+3/2, −z+1; (iii) x, y−1, z; (iv) x−1/2, −y+3/2, z−1/2. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C4H10NO+·C7H3ClNO4− | C4H10NO+·C7H3ClNO4− | C4H10NO+·C7H3ClNO4− |
Mr | 288.69 | 288.69 | 288.69 |
Crystal system, space group | Orthorhombic, P212121 | Monoclinic, C2/c | Monoclinic, C2/c |
Temperature (K) | 298 | 298 | 296 |
a, b, c (Å) | 10.304 (2), 19.557 (6), 6.4387 (13) | 18.680 (6), 10.498 (3), 13.125 (3) | 19.76 (2), 10.085 (7), 13.639 (5) |
α, β, γ (°) | 90, 90, 90 | 90, 93.35 (2), 90 | 90, 109.09 (4), 90 |
V (Å3) | 1297.5 (5) | 2569.5 (13) | 2569 (3) |
Z | 4 | 8 | 8 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.31 | 0.32 | 0.32 |
Crystal size (mm) | 0.40 × 0.30 × 0.20 | 0.40 × 0.30 × 0.20 | 0.40 × 0.30 × 0.25 |
|
Data collection |
Diffractometer | Rigaku AFC-5R diffractometer | Rigaku AFC-5R diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | ψ scan (North et al., 1968) | ψ scan (North et al., 1968) | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.885, 0.940 | 0.884, 0.940 | 0.884, 0.925 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4209, 3101, 1769 | 3215, 2945, 1741 | 3198, 2945, 1850 |
Rint | 0.058 | 0.025 | 0.025 |
(sin θ/λ)max (Å−1) | 0.682 | 0.650 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.075, 1.04 | 0.046, 0.121, 1.00 | 0.047, 0.116, 1.03 |
No. of reflections | 3101 | 2945 | 2945 |
No. of parameters | 173 | 225 | 225 |
H-atom treatment | H-atom parameters constrained | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.28, −0.23 | 0.26, −0.24 | 0.25, −0.20 |
Absolute structure | (Flack, 1983), 1102 Friedel pairs | ? | ? |
Absolute structure parameter | 0.02 (8) | ? | ? |
Selected geometric parameters (Å, º) for (I) topCl—C2 | 1.748 (3) | O3—N1 | 1.230 (3) |
O1—C7 | 1.267 (3) | O4—N1 | 1.232 (3) |
O2—C7 | 1.223 (4) | | |
| | | |
O3—N1—C4—C3 | −3.9 (4) | C2—C1—C7—O2 | −74.1 (4) |
O4—N1—C4—C3 | 176.2 (3) | C2—C1—C7—O1 | 108.9 (3) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H4···O1 | 0.89 | 1.80 | 2.682 (3) | 170 |
N2—H5···O1i | 0.89 | 1.86 | 2.747 (3) | 174 |
C6—H3···O3ii | 0.93 | 2.49 | 3.378 (4) | 160 |
C10—H11···O5iii | 0.97 | 2.55 | 3.486 (4) | 161 |
C11—H12···O4iv | 0.97 | 2.53 | 3.340 (4) | 141 |
Symmetry codes: (i) −x+3/2, −y+1, z−1/2; (ii) x−1/2, −y+1/2, −z+1; (iii) −x+5/2, −y+1, z+1/2; (iv) x+1/2, −y+1/2, −z+1. |
Selected geometric parameters (Å, º) for (II) topCl—C2 | 1.743 (3) | O3—N1 | 1.216 (3) |
O1—C7 | 1.247 (3) | O4—N1 | 1.218 (3) |
O2—C7 | 1.244 (3) | | |
| | | |
O3—N1—C5—C6 | 167.6 (2) | C2—C1—C7—O2 | −63.1 (3) |
O4—N1—C5—C6 | −13.0 (4) | C2—C1—C7—O1 | 119.8 (3) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H4···O2 | 0.83 (3) | 1.89 (3) | 2.719 (3) | 178 (2) |
N2—H5···O1i | 1.00 (4) | 1.77 (3) | 2.753 (3) | 169 (3) |
C4—H2···O1ii | 0.89 (3) | 2.58 (3) | 3.371 (4) | 148 (2) |
C11—H13···O3iii | 0.98 (3) | 2.55 (3) | 3.344 (4) | 138 (2) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+3/2, y+1/2, −z+1/2; (iii) −x+3/2, −y+1/2, −z+1. |
Selected geometric parameters (Å, º) for (III) topCl—C4 | 1.727 (3) | O3—N1 | 1.220 (3) |
O1—C7 | 1.242 (3) | O4—N1 | 1.204 (3) |
O2—C7 | 1.237 (3) | | |
| | | |
O4—N1—C3—C4 | −20.3 (4) | C2—C1—C7—O2 | −12.9 (4) |
O3—N1—C3—C4 | 160.9 (3) | C2—C1—C7—O1 | 166.3 (2) |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H4···O2 | 0.93 (3) | 1.85 (3) | 2.752 (4) | 160 (3) |
N2—H5···O1i | 0.99 (4) | 1.66 (4) | 2.629 (4) | 164 (3) |
C5—H2···O5ii | 1.00 (3) | 2.58 (3) | 3.269 (5) | 125.9 (19) |
C8—H6···O4iii | 1.00 (4) | 2.49 (4) | 3.335 (6) | 142 (3) |
C10—H10···O2 | 1.05 (4) | 2.48 (4) | 3.255 (6) | 131 (2) |
Symmetry codes: (i) −x+3/2, −y+3/2, −z+1; (ii) x, y−1, z; (iii) x−1/2, −y+3/2, z−1/2. |
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Chiral crystals composed of two achiral molecules have attracted much interest because of their potential use for absolute asymmetric synthesis (Green et al., 1979; Koshima, Ding et al., 1996; Tanaka & Toda, 2000) and non-linear optics (Koshima, Wang et al., 1996). In the course of our study on D—H···A hydrogen bonding (D: N, O or C; A: N, O or Cl) in chloro- and nitro-substituted benzoic acid–amine systems (Ishida et al., 2001a,b,cd), we found that imidazolium 2-chloro-4-nitrobezoate crystallizes in the non-centrosymmetric space group P21. In the crystal, the cations and anions are connected by N—H···O hydrogen bonds to afford a 21 helical chain (Ishida et al., 2001 d). This is the first example of a chloro- and nitro-substituted benzoic acid–amine system that shows spontaneous resolution of a chiral rotational isomer of the benzoate ion. Thus, we have prepared crystals composed of chloro- and nitro-substituted benzoic acid and amine, with the expectation that such a chiral rotational isomer exists widely in these systems; we have chosen morpholine as the counter-cation and prepared salts with 2-chloro-4-nitro-, (I), 2-chloro-5-nitro-, (II), and 4-chloro-3-nitrobenzoic acid, (III), and determined their crystal structures. Of these salts, (I) crystallizes in the non-centrosymmetric space group P212121.
The asymmetric units of (I), (II) and (III) are composed of C4H10NO+·C7H3ClNO4-. In these crystals, an acid–base interaction involving a proton transfer is observed as expected from the high basicity of the present amine. In (I), the cations and anions are held together by short N—H···O hydrogen bonds (Table 2), forming a 21 helical chain along the c axis (Figs. 1 and 2). One of the O atoms of the carboxylate group, O1, forms two hydrogen bonds with the cations, while the other O atom, O2, forms no hydrogen bond. The C—O bond involved in the hydrogen bond is rather long [C7—O1 1.267 (3) Å] compared with the other C—O bond length [C7—O2 1.223 (4) Å] and the C—O bond lengths in (II) and (III) [1.237 (3)–1.247 (3) Å], where both O atoms of the carboxylate groups are involved in N—H···O hydrogen bonds (see below). The helical chains are linked by three leading C—H···O interactions (Table 2) involving both O atoms of the nitro group and the O atom of the cation (Fig. 2). The carboxylate group is considerably twisted out of the plane of the benzene ring [dihedral angle 72.1 (2)°] compared with the calculated value (41.1°) for the isolated anion in the gas phase using the GAUSSIAN98/HF program (Frisch et al., 1998) with the 6–31G** basis set. On the other hand, the nitro group makes a small angle of 1.8 (2)° with the benzene ring, which is comparable to the calculated angle of 0.5°.
In (II) and (III), two cations and two anions are held together by short N—H···O hydrogen bonds (Tables 4 and 6). Both O atoms of the carboxylate groups are involved in the hydrogen bonds, forming centrosymmetric hydrogen-bonded rings (Figs. 3 and 4) with graph-set descriptor R44(12) (Bernstein et al., 1995), in a similar manner to those observed in morpholinium 4-chloro-2-nitrobenzoate and 5-cholro-2-nitrobenzoate (Ishida et al., 2001b,c). In (II), the dihedral angle between the carboxylate group and the benzene ring is 61.0 (2)° and that between the nitro group and the benzene ring is 11.7 (2)°. In (III), these dihedral angles are 13.2 (2) and 19.3 (2)°, in the same order. There are two and three important C—H···O interactions in (II) and (III), respectively, which connect the macro-rings (Tables 4 and 6).