The structures of three isomeric compounds, C
7H
4ClNO
4·C
8H
6N
2, of phthalazine with chloro- and nitro-substituted benzoic acid, namely, 3-chloro-2-nitrobenzoic acid–phthalazine (1/1), (I), 4-chloro-2-nitrobenzoic acid–phthalazine (1/1), (II), and 4-chloro-3-nitrobenzoic acid–phthalazine (1/1), (III), have been determined at 190 K. In the asymmetric unit of each compound, there are two crystallographically independent chloronitrobenzoic acid–phthalazine units, in each of which the two components are held together by a short hydrogen bond between an N atom of the base and a carboxyl O atom. In one hydrogen-bonded unit of (I) and in two units of (II), a weak C—H

O interaction is also observed between the two components. The N

O distances are 2.5715 (15) and 2.5397 (17) Å for (I), 2.5655 (13) and 2.6081 (13) Å for (II), and 2.613 (2) and 2.589 (2) Å for (III). In both hydrogen-bonded units of (I) and (II), the H atoms are each disordered over two positions with (N site):(O site) occupancies of 0.35 (3):0.65 (3) and 0.31 (3):0.69 (3) for (I), and 0.32 (3):0.68 (3) and 0.30 (3):0.70 (3) for (II). The H atoms in the hydrogen-bonded units of (III) are located at the O-atom sites.
Supporting information
CCDC references: 855977; 855978; 855979
Crystals of all three compounds were obtained by slow evaporation from
acetonitrile solutions of phthalazine with the corresponding chloro- and
nitro-substituted benzoic acid in a 1:1 molar ratio at room temperature
[acetonitrile solution (50 ml) of phthalazine (0.200 g) and
3-chloro-2-nitrobenzoic acid (0.310 g) for (I), acetonitrile solution (30 ml)
of phthalazine (0.161 g) and 4-chloro-2-nitrobenzoic acid (0.249 g) for (II),
and acetonitrile solution (90 ml) of phthalazine (0.096 g) and
4-chloro-3-nitrobenzoic acid (0.149 g) for (III)].
For all three compounds, all H atoms were found in difference Fourier maps. H
atoms in(I) and (II) which are involved in N···H···O hydrogen bonds were found
to be disordered over two positions in difference Fourier maps. Since the
site-occupancy factors and isotropic displacement parameters were strongly
correlated, the positional parameters and occupancy factors were refined, with
Uiso(H) = 1.5Ueq(N or O). The positional parameters were
refined with bond restraints of O—H = 0.84 (2) Å and N—H = 0.88 (2) Å.
Atoms H1 and H5A in (III) were refined isotropically. The refined
distances are given in Tables 1–3. The remaining H atoms of all compounds
were positioned geometrically (C—H = 0.95 Å) and treated as riding, with
Uiso(H) = 1.2Ueq(C).
For all compounds, data collection: PROCESS-AUTO (Rigaku/MSC, 2004); cell refinement: PROCESS-AUTO (Rigaku/MSC, 2004); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and WinGX (Farrugia, 1999); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004) and PLATON (Spek, 2009).
(I) 3-chloro-2-nitrobenzoic acid–phthalazine (1/1)
top
Crystal data top
C7H3.67ClNO4·C8H6.33N2 | Z = 4 |
Mr = 331.71 | F(000) = 680.00 |
Triclinic, P1 | Dx = 1.542 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71075 Å |
a = 9.7764 (15) Å | Cell parameters from 18876 reflections |
b = 12.0384 (14) Å | θ = 3.0–30.2° |
c = 12.8889 (15) Å | µ = 0.29 mm−1 |
α = 81.491 (3)° | T = 190 K |
β = 72.328 (5)° | Block, colourless |
γ = 88.390 (5)° | 0.40 × 0.28 × 0.18 mm |
V = 1429.2 (3) Å3 | |
Data collection top
Rigaku R-AXIS RAPID II diffractometer | 6364 reflections with I > 2σ(I) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.035 |
ω scans | θmax = 30.0° |
Absorption correction: numerical (NUMABS; Higashi, 1999) | h = −13→13 |
Tmin = 0.874, Tmax = 0.949 | k = −16→16 |
31515 measured reflections | l = −17→18 |
8271 independent 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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0642P)2 + 0.0877P] where P = (Fo2 + 2Fc2)/3 |
8271 reflections | (Δ/σ)max = 0.001 |
429 parameters | Δρmax = 0.30 e Å−3 |
4 restraints | Δρmin = −0.41 e Å−3 |
Crystal data top
C7H3.67ClNO4·C8H6.33N2 | γ = 88.390 (5)° |
Mr = 331.71 | V = 1429.2 (3) Å3 |
Triclinic, P1 | Z = 4 |
a = 9.7764 (15) Å | Mo Kα radiation |
b = 12.0384 (14) Å | µ = 0.29 mm−1 |
c = 12.8889 (15) Å | T = 190 K |
α = 81.491 (3)° | 0.40 × 0.28 × 0.18 mm |
β = 72.328 (5)° | |
Data collection top
Rigaku R-AXIS RAPID II diffractometer | 8271 independent reflections |
Absorption correction: numerical (NUMABS; Higashi, 1999) | 6364 reflections with I > 2σ(I) |
Tmin = 0.874, Tmax = 0.949 | Rint = 0.035 |
31515 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 4 restraints |
wR(F2) = 0.112 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.30 e Å−3 |
8271 reflections | Δρmin = −0.41 e Å−3 |
429 parameters | |
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 | Occ. (<1) |
Cl1 | 0.54704 (3) | 0.82797 (3) | 0.97698 (2) | 0.04315 (9) | |
Cl2 | 1.06363 (3) | 0.32598 (3) | 0.99901 (2) | 0.04380 (9) | |
O1 | 0.38359 (10) | 0.91589 (7) | 0.60952 (7) | 0.03756 (19) | |
H1 | 0.346 (3) | 0.939 (2) | 0.5577 (18) | 0.056* | 0.65 (3) |
O2 | 0.47212 (11) | 0.77883 (8) | 0.51170 (8) | 0.0479 (2) | |
O3 | 0.27519 (9) | 0.87264 (8) | 0.85370 (7) | 0.0419 (2) | |
O4 | 0.43919 (10) | 1.00169 (7) | 0.80694 (8) | 0.0427 (2) | |
O5 | 0.98421 (13) | 0.31165 (10) | 0.53057 (8) | 0.0608 (3) | |
H5A | 0.928 (3) | 0.337 (3) | 0.495 (3) | 0.091* | 0.69 (3) |
O6 | 0.84798 (11) | 0.40838 (9) | 0.65469 (9) | 0.0554 (3) | |
O7 | 0.77750 (10) | 0.35976 (9) | 0.90326 (9) | 0.0538 (3) | |
O8 | 0.92297 (11) | 0.50129 (7) | 0.83597 (9) | 0.0493 (2) | |
N1 | 0.39857 (10) | 0.90591 (8) | 0.81376 (7) | 0.0307 (2) | |
N2 | 0.25921 (11) | 0.96842 (8) | 0.45998 (8) | 0.0336 (2) | |
H2 | 0.295 (5) | 0.947 (4) | 0.515 (3) | 0.050* | 0.35 (3) |
N3 | 0.17253 (11) | 1.05913 (8) | 0.47405 (8) | 0.0350 (2) | |
N4 | 0.89335 (11) | 0.40241 (8) | 0.85017 (8) | 0.0340 (2) | |
N5 | 0.83498 (12) | 0.38076 (9) | 0.40414 (8) | 0.0380 (2) | |
H5B | 0.886 (5) | 0.363 (5) | 0.450 (4) | 0.057* | 0.31 (3) |
N6 | 0.86168 (12) | 0.32058 (9) | 0.31839 (9) | 0.0408 (2) | |
C1 | 0.53417 (11) | 0.78574 (9) | 0.67521 (9) | 0.0291 (2) | |
C2 | 0.50836 (11) | 0.82266 (9) | 0.77708 (9) | 0.0280 (2) | |
C3 | 0.58214 (12) | 0.77997 (9) | 0.85109 (9) | 0.0312 (2) | |
C4 | 0.68321 (13) | 0.69848 (10) | 0.82410 (11) | 0.0371 (3) | |
H4 | 0.7334 | 0.6681 | 0.8741 | 0.045* | |
C5 | 0.71093 (13) | 0.66125 (10) | 0.72273 (11) | 0.0393 (3) | |
H5 | 0.7812 | 0.6057 | 0.7032 | 0.047* | |
C6 | 0.63705 (12) | 0.70439 (9) | 0.64974 (10) | 0.0352 (2) | |
H6 | 0.6574 | 0.6776 | 0.5810 | 0.042* | |
C7 | 0.45901 (12) | 0.82764 (9) | 0.59034 (9) | 0.0324 (2) | |
C8 | 0.10711 (12) | 1.09080 (9) | 0.39997 (9) | 0.0330 (2) | |
H8 | 0.0460 | 1.1536 | 0.4103 | 0.040* | |
C9 | 0.12024 (11) | 1.03859 (9) | 0.30516 (9) | 0.0289 (2) | |
C10 | 0.04878 (13) | 1.07522 (10) | 0.22679 (10) | 0.0372 (3) | |
H10 | −0.0151 | 1.1364 | 0.2366 | 0.045* | |
C11 | 0.07215 (14) | 1.02161 (11) | 0.13590 (10) | 0.0401 (3) | |
H11 | 0.0243 | 1.0462 | 0.0827 | 0.048* | |
C12 | 0.16524 (14) | 0.93168 (10) | 0.12117 (9) | 0.0384 (3) | |
H12 | 0.1816 | 0.8964 | 0.0574 | 0.046* | |
C13 | 0.23381 (13) | 0.89338 (10) | 0.19804 (9) | 0.0350 (2) | |
H13 | 0.2957 | 0.8310 | 0.1880 | 0.042* | |
C14 | 0.21175 (12) | 0.94705 (9) | 0.29152 (9) | 0.0291 (2) | |
C15 | 0.27834 (13) | 0.91545 (9) | 0.37540 (9) | 0.0337 (2) | |
H15 | 0.3398 | 0.8526 | 0.3695 | 0.040* | |
C16 | 1.03212 (11) | 0.29781 (8) | 0.69955 (9) | 0.0276 (2) | |
C17 | 1.00879 (11) | 0.32664 (8) | 0.80473 (9) | 0.0272 (2) | |
C18 | 1.09072 (12) | 0.28327 (9) | 0.87156 (9) | 0.0300 (2) | |
C19 | 1.19546 (12) | 0.20639 (10) | 0.83629 (10) | 0.0350 (2) | |
H19 | 1.2512 | 0.1752 | 0.8819 | 0.042* | |
C20 | 1.21802 (13) | 0.17540 (10) | 0.73274 (10) | 0.0360 (2) | |
H20 | 1.2893 | 0.1219 | 0.7080 | 0.043* | |
C21 | 1.13844 (12) | 0.22119 (9) | 0.66496 (9) | 0.0318 (2) | |
H21 | 1.1570 | 0.1998 | 0.5940 | 0.038* | |
C22 | 0.94465 (12) | 0.34541 (9) | 0.62580 (9) | 0.0326 (2) | |
C23 | 0.79757 (13) | 0.35112 (10) | 0.24345 (10) | 0.0373 (3) | |
H23 | 0.8176 | 0.3099 | 0.1832 | 0.045* | |
C24 | 0.70101 (12) | 0.44042 (10) | 0.24518 (9) | 0.0317 (2) | |
C25 | 0.63438 (14) | 0.47098 (12) | 0.16209 (11) | 0.0434 (3) | |
H25 | 0.6576 | 0.4340 | 0.0989 | 0.052* | |
C26 | 0.53647 (16) | 0.55426 (13) | 0.17443 (14) | 0.0556 (4) | |
H26 | 0.4902 | 0.5754 | 0.1196 | 0.067* | |
C27 | 0.50337 (15) | 0.60902 (12) | 0.26717 (15) | 0.0548 (4) | |
H27 | 0.4330 | 0.6658 | 0.2748 | 0.066* | |
C28 | 0.56916 (14) | 0.58351 (10) | 0.34749 (12) | 0.0443 (3) | |
H28 | 0.5470 | 0.6232 | 0.4089 | 0.053* | |
C29 | 0.67014 (12) | 0.49723 (9) | 0.33681 (9) | 0.0313 (2) | |
C30 | 0.74498 (13) | 0.46245 (10) | 0.41426 (9) | 0.0351 (2) | |
H30 | 0.7284 | 0.5007 | 0.4762 | 0.042* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.04729 (18) | 0.05455 (19) | 0.03517 (15) | 0.01104 (13) | −0.02333 (13) | −0.00920 (13) |
Cl2 | 0.04574 (17) | 0.0612 (2) | 0.03053 (14) | 0.00811 (14) | −0.01602 (12) | −0.01759 (13) |
O1 | 0.0486 (5) | 0.0402 (4) | 0.0311 (4) | 0.0143 (4) | −0.0214 (4) | −0.0106 (3) |
O2 | 0.0621 (6) | 0.0534 (5) | 0.0367 (5) | 0.0188 (4) | −0.0224 (4) | −0.0208 (4) |
O3 | 0.0285 (4) | 0.0608 (5) | 0.0376 (4) | 0.0079 (4) | −0.0085 (3) | −0.0155 (4) |
O4 | 0.0473 (5) | 0.0351 (4) | 0.0553 (5) | 0.0133 (4) | −0.0269 (4) | −0.0153 (4) |
O5 | 0.0775 (8) | 0.0806 (7) | 0.0384 (5) | 0.0474 (6) | −0.0345 (5) | −0.0252 (5) |
O6 | 0.0566 (6) | 0.0710 (6) | 0.0566 (6) | 0.0370 (5) | −0.0357 (5) | −0.0332 (5) |
O7 | 0.0332 (5) | 0.0610 (6) | 0.0615 (6) | 0.0090 (4) | −0.0010 (4) | −0.0215 (5) |
O8 | 0.0595 (6) | 0.0325 (4) | 0.0678 (6) | 0.0136 (4) | −0.0317 (5) | −0.0202 (4) |
N1 | 0.0304 (5) | 0.0389 (5) | 0.0274 (4) | 0.0105 (4) | −0.0146 (4) | −0.0092 (4) |
N2 | 0.0390 (5) | 0.0359 (5) | 0.0291 (5) | 0.0032 (4) | −0.0152 (4) | −0.0057 (4) |
N3 | 0.0406 (5) | 0.0352 (5) | 0.0325 (5) | 0.0013 (4) | −0.0131 (4) | −0.0107 (4) |
N4 | 0.0352 (5) | 0.0357 (5) | 0.0365 (5) | 0.0099 (4) | −0.0148 (4) | −0.0158 (4) |
N5 | 0.0424 (6) | 0.0437 (5) | 0.0323 (5) | 0.0071 (4) | −0.0179 (4) | −0.0062 (4) |
N6 | 0.0411 (6) | 0.0417 (5) | 0.0408 (5) | 0.0101 (4) | −0.0126 (4) | −0.0110 (5) |
C1 | 0.0280 (5) | 0.0293 (5) | 0.0293 (5) | 0.0027 (4) | −0.0079 (4) | −0.0036 (4) |
C2 | 0.0246 (5) | 0.0285 (5) | 0.0305 (5) | 0.0048 (4) | −0.0087 (4) | −0.0034 (4) |
C3 | 0.0299 (5) | 0.0330 (5) | 0.0328 (5) | 0.0033 (4) | −0.0137 (4) | −0.0025 (4) |
C4 | 0.0333 (6) | 0.0335 (5) | 0.0464 (7) | 0.0065 (4) | −0.0177 (5) | −0.0006 (5) |
C5 | 0.0323 (6) | 0.0325 (5) | 0.0513 (7) | 0.0092 (4) | −0.0112 (5) | −0.0055 (5) |
C6 | 0.0344 (6) | 0.0319 (5) | 0.0365 (6) | 0.0063 (4) | −0.0054 (5) | −0.0085 (5) |
C7 | 0.0345 (6) | 0.0364 (5) | 0.0262 (5) | 0.0031 (4) | −0.0089 (4) | −0.0054 (4) |
C8 | 0.0354 (6) | 0.0307 (5) | 0.0348 (5) | 0.0029 (4) | −0.0114 (4) | −0.0095 (4) |
C9 | 0.0308 (5) | 0.0282 (5) | 0.0284 (5) | −0.0004 (4) | −0.0098 (4) | −0.0046 (4) |
C10 | 0.0398 (6) | 0.0365 (6) | 0.0397 (6) | 0.0059 (5) | −0.0194 (5) | −0.0049 (5) |
C11 | 0.0478 (7) | 0.0449 (6) | 0.0338 (6) | −0.0001 (5) | −0.0226 (5) | −0.0031 (5) |
C12 | 0.0469 (7) | 0.0434 (6) | 0.0273 (5) | −0.0037 (5) | −0.0126 (5) | −0.0095 (5) |
C13 | 0.0404 (6) | 0.0345 (5) | 0.0313 (5) | 0.0046 (5) | −0.0102 (5) | −0.0104 (5) |
C14 | 0.0324 (5) | 0.0292 (5) | 0.0269 (5) | 0.0005 (4) | −0.0107 (4) | −0.0043 (4) |
C15 | 0.0383 (6) | 0.0339 (5) | 0.0313 (5) | 0.0056 (4) | −0.0143 (5) | −0.0050 (4) |
C16 | 0.0283 (5) | 0.0278 (5) | 0.0296 (5) | 0.0043 (4) | −0.0120 (4) | −0.0067 (4) |
C17 | 0.0261 (5) | 0.0266 (5) | 0.0305 (5) | 0.0035 (4) | −0.0091 (4) | −0.0086 (4) |
C18 | 0.0304 (5) | 0.0353 (5) | 0.0267 (5) | 0.0012 (4) | −0.0107 (4) | −0.0075 (4) |
C19 | 0.0337 (6) | 0.0401 (6) | 0.0352 (6) | 0.0081 (5) | −0.0168 (5) | −0.0056 (5) |
C20 | 0.0346 (6) | 0.0392 (6) | 0.0375 (6) | 0.0133 (5) | −0.0142 (5) | −0.0110 (5) |
C21 | 0.0330 (5) | 0.0352 (5) | 0.0297 (5) | 0.0085 (4) | −0.0113 (4) | −0.0107 (4) |
C22 | 0.0341 (5) | 0.0328 (5) | 0.0351 (5) | 0.0065 (4) | −0.0158 (4) | −0.0083 (4) |
C23 | 0.0381 (6) | 0.0418 (6) | 0.0324 (6) | 0.0021 (5) | −0.0071 (5) | −0.0141 (5) |
C24 | 0.0295 (5) | 0.0379 (6) | 0.0278 (5) | −0.0049 (4) | −0.0090 (4) | −0.0036 (4) |
C25 | 0.0439 (7) | 0.0546 (7) | 0.0351 (6) | −0.0105 (6) | −0.0195 (5) | 0.0011 (5) |
C26 | 0.0477 (8) | 0.0587 (8) | 0.0648 (9) | −0.0097 (6) | −0.0353 (7) | 0.0178 (7) |
C27 | 0.0415 (7) | 0.0413 (7) | 0.0795 (11) | 0.0065 (6) | −0.0228 (7) | 0.0064 (7) |
C28 | 0.0407 (7) | 0.0354 (6) | 0.0544 (8) | 0.0067 (5) | −0.0110 (6) | −0.0077 (6) |
C29 | 0.0300 (5) | 0.0307 (5) | 0.0328 (5) | 0.0008 (4) | −0.0092 (4) | −0.0041 (4) |
C30 | 0.0417 (6) | 0.0373 (6) | 0.0287 (5) | 0.0021 (5) | −0.0121 (5) | −0.0097 (5) |
Geometric parameters (Å, º) top
Cl1—C3 | 1.7357 (12) | C9—C10 | 1.4078 (15) |
Cl2—C18 | 1.7353 (11) | C10—C11 | 1.3763 (17) |
O1—C7 | 1.2870 (14) | C10—H10 | 0.9500 |
O1—H1 | 0.860 (17) | C11—C12 | 1.3917 (18) |
O2—C7 | 1.2175 (14) | C11—H11 | 0.9500 |
O3—N1 | 1.2122 (13) | C12—C13 | 1.3764 (16) |
O4—N1 | 1.2122 (13) | C12—H12 | 0.9500 |
O5—C22 | 1.2930 (15) | C13—C14 | 1.4073 (15) |
O5—H5A | 0.844 (18) | C13—H13 | 0.9500 |
O6—C22 | 1.1985 (14) | C14—C15 | 1.4244 (15) |
O7—N4 | 1.2136 (14) | C15—H15 | 0.9500 |
O8—N4 | 1.2071 (13) | C16—C21 | 1.3843 (14) |
N1—C2 | 1.4669 (13) | C16—C17 | 1.3990 (14) |
N2—C15 | 1.3058 (15) | C16—C22 | 1.5060 (14) |
N2—N3 | 1.3626 (13) | C17—C18 | 1.3850 (14) |
N2—H2 | 0.879 (19) | C18—C19 | 1.3785 (15) |
N3—C8 | 1.3097 (15) | C19—C20 | 1.3904 (16) |
N4—C17 | 1.4655 (13) | C19—H19 | 0.9500 |
N5—C30 | 1.2953 (15) | C20—C21 | 1.3850 (15) |
N5—N6 | 1.3659 (14) | C20—H20 | 0.9500 |
N5—H5B | 0.88 (2) | C21—H21 | 0.9500 |
N6—C23 | 1.3078 (16) | C23—C24 | 1.4088 (17) |
C1—C6 | 1.3849 (14) | C23—H23 | 0.9500 |
C1—C2 | 1.3966 (15) | C24—C29 | 1.4016 (16) |
C1—C7 | 1.5148 (15) | C24—C25 | 1.4143 (16) |
C2—C3 | 1.3950 (14) | C25—C26 | 1.359 (2) |
C3—C4 | 1.3775 (15) | C25—H25 | 0.9500 |
C4—C5 | 1.3903 (18) | C26—C27 | 1.398 (2) |
C4—H4 | 0.9500 | C26—H26 | 0.9500 |
C5—C6 | 1.3869 (17) | C27—C28 | 1.371 (2) |
C5—H5 | 0.9500 | C27—H27 | 0.9500 |
C6—H6 | 0.9500 | C28—C29 | 1.4052 (16) |
C8—C9 | 1.4256 (15) | C28—H28 | 0.9500 |
C8—H8 | 0.9500 | C29—C30 | 1.4176 (16) |
C9—C14 | 1.3972 (15) | C30—H30 | 0.9500 |
| | | |
C7—O1—H1 | 111.4 (18) | C12—C13—H13 | 120.2 |
C22—O5—H5A | 109 (2) | C14—C13—H13 | 120.2 |
O4—N1—O3 | 124.98 (10) | C9—C14—C13 | 119.51 (10) |
O4—N1—C2 | 117.37 (9) | C9—C14—C15 | 116.06 (10) |
O3—N1—C2 | 117.55 (9) | C13—C14—C15 | 124.43 (10) |
C15—N2—N3 | 121.67 (9) | N2—C15—C14 | 123.36 (10) |
C15—N2—H2 | 124 (3) | N2—C15—H15 | 118.3 |
N3—N2—H2 | 114 (3) | C14—C15—H15 | 118.3 |
C8—N3—N2 | 117.45 (9) | C21—C16—C17 | 117.52 (9) |
O8—N4—O7 | 125.41 (10) | C21—C16—C22 | 120.14 (9) |
O8—N4—C17 | 117.40 (10) | C17—C16—C22 | 122.33 (9) |
O7—N4—C17 | 117.10 (9) | C18—C17—C16 | 121.91 (9) |
C30—N5—N6 | 121.72 (10) | C18—C17—N4 | 116.96 (9) |
C30—N5—H5B | 122 (4) | C16—C17—N4 | 121.11 (9) |
N6—N5—H5B | 116 (4) | C19—C18—C17 | 119.85 (10) |
C23—N6—N5 | 117.69 (10) | C19—C18—Cl2 | 119.68 (8) |
C6—C1—C2 | 117.28 (10) | C17—C18—Cl2 | 120.47 (8) |
C6—C1—C7 | 117.42 (10) | C18—C19—C20 | 118.82 (10) |
C2—C1—C7 | 125.30 (9) | C18—C19—H19 | 120.6 |
C3—C2—C1 | 121.99 (9) | C20—C19—H19 | 120.6 |
C3—C2—N1 | 116.23 (9) | C21—C20—C19 | 121.16 (10) |
C1—C2—N1 | 121.75 (9) | C21—C20—H20 | 119.4 |
C4—C3—C2 | 119.59 (10) | C19—C20—H20 | 119.4 |
C4—C3—Cl1 | 119.78 (9) | C16—C21—C20 | 120.70 (10) |
C2—C3—Cl1 | 120.64 (8) | C16—C21—H21 | 119.6 |
C3—C4—C5 | 119.20 (11) | C20—C21—H21 | 119.6 |
C3—C4—H4 | 120.4 | O6—C22—O5 | 124.42 (11) |
C5—C4—H4 | 120.4 | O6—C22—C16 | 121.99 (10) |
C6—C5—C4 | 120.71 (10) | O5—C22—C16 | 113.59 (9) |
C6—C5—H5 | 119.6 | N6—C23—C24 | 125.00 (11) |
C4—C5—H5 | 119.6 | N6—C23—H23 | 117.5 |
C1—C6—C5 | 121.23 (11) | C24—C23—H23 | 117.5 |
C1—C6—H6 | 119.4 | C29—C24—C23 | 116.11 (10) |
C5—C6—H6 | 119.4 | C29—C24—C25 | 120.69 (11) |
O2—C7—O1 | 124.95 (10) | C23—C24—C25 | 123.18 (11) |
O2—C7—C1 | 120.47 (10) | C26—C25—C24 | 118.71 (13) |
O1—C7—C1 | 114.58 (9) | C26—C25—H25 | 120.6 |
N3—C8—C9 | 125.25 (10) | C24—C25—H25 | 120.6 |
N3—C8—H8 | 117.4 | C25—C26—C27 | 120.48 (13) |
C9—C8—H8 | 117.4 | C25—C26—H26 | 119.8 |
C14—C9—C10 | 120.03 (10) | C27—C26—H26 | 119.8 |
C14—C9—C8 | 116.20 (9) | C28—C27—C26 | 122.16 (13) |
C10—C9—C8 | 123.77 (10) | C28—C27—H27 | 118.9 |
C11—C10—C9 | 119.46 (11) | C26—C27—H27 | 118.9 |
C11—C10—H10 | 120.3 | C27—C28—C29 | 118.35 (13) |
C9—C10—H10 | 120.3 | C27—C28—H28 | 120.8 |
C10—C11—C12 | 120.59 (11) | C29—C28—H28 | 120.8 |
C10—C11—H11 | 119.7 | C24—C29—C28 | 119.57 (11) |
C12—C11—H11 | 119.7 | C24—C29—C30 | 116.55 (10) |
C13—C12—C11 | 120.71 (11) | C28—C29—C30 | 123.88 (11) |
C13—C12—H12 | 119.6 | N5—C30—C29 | 122.82 (10) |
C11—C12—H12 | 119.6 | N5—C30—H30 | 118.6 |
C12—C13—C14 | 119.68 (11) | C29—C30—H30 | 118.6 |
| | | |
C15—N2—N3—C8 | 0.84 (16) | C13—C14—C15—N2 | 178.10 (11) |
C30—N5—N6—C23 | 2.81 (18) | C21—C16—C17—C18 | 1.75 (16) |
C6—C1—C2—C3 | −0.13 (16) | C22—C16—C17—C18 | −179.36 (10) |
C7—C1—C2—C3 | −179.99 (10) | C21—C16—C17—N4 | −176.69 (10) |
C6—C1—C2—N1 | −178.05 (10) | C22—C16—C17—N4 | 2.21 (16) |
C7—C1—C2—N1 | 2.09 (17) | O8—N4—C17—C18 | 89.08 (13) |
O4—N1—C2—C3 | 79.90 (12) | O7—N4—C17—C18 | −87.66 (13) |
O3—N1—C2—C3 | −96.42 (12) | O8—N4—C17—C16 | −92.41 (13) |
O4—N1—C2—C1 | −102.07 (12) | O7—N4—C17—C16 | 90.85 (14) |
O3—N1—C2—C1 | 81.61 (13) | C16—C17—C18—C19 | −2.29 (17) |
C1—C2—C3—C4 | −0.35 (17) | N4—C17—C18—C19 | 176.21 (10) |
N1—C2—C3—C4 | 177.68 (10) | C16—C17—C18—Cl2 | 177.11 (8) |
C1—C2—C3—Cl1 | −179.99 (8) | N4—C17—C18—Cl2 | −4.40 (14) |
N1—C2—C3—Cl1 | −1.96 (14) | C17—C18—C19—C20 | 1.04 (18) |
C2—C3—C4—C5 | 0.75 (17) | Cl2—C18—C19—C20 | −178.36 (9) |
Cl1—C3—C4—C5 | −179.61 (9) | C18—C19—C20—C21 | 0.67 (19) |
C3—C4—C5—C6 | −0.68 (18) | C17—C16—C21—C20 | −0.01 (17) |
C2—C1—C6—C5 | 0.20 (17) | C22—C16—C21—C20 | −178.93 (11) |
C7—C1—C6—C5 | −179.92 (10) | C19—C20—C21—C16 | −1.19 (19) |
C4—C5—C6—C1 | 0.19 (18) | C21—C16—C22—O6 | 176.94 (12) |
C6—C1—C7—O2 | 11.53 (17) | C17—C16—C22—O6 | −1.93 (18) |
C2—C1—C7—O2 | −168.61 (11) | C21—C16—C22—O5 | −3.00 (16) |
C6—C1—C7—O1 | −168.51 (10) | C17—C16—C22—O5 | 178.14 (11) |
C2—C1—C7—O1 | 11.35 (16) | N5—N6—C23—C24 | −1.07 (19) |
N2—N3—C8—C9 | −0.59 (17) | N6—C23—C24—C29 | −1.96 (18) |
N3—C8—C9—C14 | −0.54 (17) | N6—C23—C24—C25 | 179.73 (12) |
N3—C8—C9—C10 | −179.68 (11) | C29—C24—C25—C26 | −1.99 (18) |
C14—C9—C10—C11 | −1.31 (17) | C23—C24—C25—C26 | 176.25 (12) |
C8—C9—C10—C11 | 177.80 (11) | C24—C25—C26—C27 | 0.5 (2) |
C9—C10—C11—C12 | 0.16 (19) | C25—C26—C27—C28 | 1.4 (2) |
C10—C11—C12—C13 | 1.12 (19) | C26—C27—C28—C29 | −1.8 (2) |
C11—C12—C13—C14 | −1.23 (18) | C23—C24—C29—C28 | −176.72 (11) |
C10—C9—C14—C13 | 1.19 (16) | C25—C24—C29—C28 | 1.64 (17) |
C8—C9—C14—C13 | −177.98 (10) | C23—C24—C29—C30 | 3.20 (15) |
C10—C9—C14—C15 | −179.48 (10) | C25—C24—C29—C30 | −178.44 (10) |
C8—C9—C14—C15 | 1.35 (15) | C27—C28—C29—C24 | 0.23 (18) |
C12—C13—C14—C9 | 0.08 (17) | C27—C28—C29—C30 | −179.69 (12) |
C12—C13—C14—C15 | −179.20 (11) | N6—N5—C30—C29 | −1.41 (19) |
N3—N2—C15—C14 | 0.06 (18) | C24—C29—C30—N5 | −1.72 (17) |
C9—C14—C15—N2 | −1.19 (17) | C28—C29—C30—N5 | 178.20 (12) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N2 | 0.86 (3) | 1.71 (3) | 2.5715 (15) | 173 (3) |
O5—H5A···N5 | 0.84 (3) | 1.71 (3) | 2.5397 (17) | 170 (4) |
N2—H2···O1 | 0.89 (4) | 1.69 (4) | 2.5715 (15) | 172 (4) |
N5—H5B···O5 | 0.88 (5) | 1.66 (5) | 2.5397 (17) | 172 (6) |
C5—H5···O6 | 0.95 | 2.56 | 3.4174 (17) | 150 |
C8—H8···O5i | 0.95 | 2.58 | 3.3560 (17) | 140 |
C12—H12···O3ii | 0.95 | 2.56 | 3.4609 (15) | 158 |
C15—H15···O2 | 0.95 | 2.59 | 3.2204 (17) | 124 |
C20—H20···O4iii | 0.95 | 2.52 | 3.2207 (17) | 131 |
C21—H21···N3iii | 0.95 | 2.43 | 3.2952 (16) | 152 |
C23—H23···Cl2ii | 0.95 | 2.81 | 3.4707 (14) | 128 |
C23—H23···O3iv | 0.95 | 2.56 | 3.3131 (16) | 136 |
C28—H28···O2 | 0.95 | 2.42 | 3.3222 (17) | 158 |
Symmetry codes: (i) x−1, y+1, z; (ii) x, y, z−1; (iii) x+1, y−1, z; (iv) −x+1, −y+1, −z+1. |
(II) 4-chloro-2-nitrobenzoic acid–phthalazine (1/1)
top
Crystal data top
C7H3.69ClNO4·C8H6.31N2 | F(000) = 1360.00 |
Mr = 331.71 | Dx = 1.535 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -P 2ybc | Cell parameters from 42486 reflections |
a = 12.2261 (5) Å | θ = 3.1–29.9° |
b = 16.9779 (7) Å | µ = 0.29 mm−1 |
c = 14.4537 (6) Å | T = 190 K |
β = 106.8955 (13)° | Block, colourless |
V = 2870.7 (2) Å3 | 0.35 × 0.35 × 0.30 mm |
Z = 8 | |
Data collection top
Rigaku R-AXIS RAPID II diffractometer | 6797 reflections with I > 2σ(I) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.030 |
ω scans | θmax = 30.0° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −17→17 |
Tmin = 0.790, Tmax = 0.916 | k = −23→23 |
60079 measured reflections | l = −20→20 |
8318 independent 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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0667P)2 + 0.6974P] where P = (Fo2 + 2Fc2)/3 |
8318 reflections | (Δ/σ)max = 0.002 |
429 parameters | Δρmax = 0.71 e Å−3 |
4 restraints | Δρmin = −0.41 e Å−3 |
Crystal data top
C7H3.69ClNO4·C8H6.31N2 | V = 2870.7 (2) Å3 |
Mr = 331.71 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.2261 (5) Å | µ = 0.29 mm−1 |
b = 16.9779 (7) Å | T = 190 K |
c = 14.4537 (6) Å | 0.35 × 0.35 × 0.30 mm |
β = 106.8955 (13)° | |
Data collection top
Rigaku R-AXIS RAPID II diffractometer | 8318 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 6797 reflections with I > 2σ(I) |
Tmin = 0.790, Tmax = 0.916 | Rint = 0.030 |
60079 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | 4 restraints |
wR(F2) = 0.123 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.71 e Å−3 |
8318 reflections | Δρmin = −0.41 e Å−3 |
429 parameters | |
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 | Occ. (<1) |
Cl1 | 0.55901 (4) | 1.18856 (2) | 0.62196 (4) | 0.05865 (14) | |
Cl2 | 0.05353 (4) | 0.066117 (18) | 0.64095 (3) | 0.04574 (11) | |
O1 | 0.59811 (8) | 0.80083 (5) | 0.69175 (8) | 0.0376 (2) | |
H1 | 0.585 (3) | 0.7517 (11) | 0.686 (2) | 0.056* | 0.68 (3) |
O2 | 0.40830 (9) | 0.80837 (6) | 0.63575 (11) | 0.0538 (3) | |
O3 | 0.26069 (10) | 0.93500 (8) | 0.65252 (10) | 0.0584 (3) | |
O4 | 0.25733 (12) | 0.93652 (10) | 0.50401 (9) | 0.0726 (5) | |
O5 | 0.10102 (8) | 0.45715 (5) | 0.67381 (8) | 0.0373 (2) | |
H5A | 0.086 (3) | 0.5065 (11) | 0.662 (2) | 0.056* | 0.70 (3) |
O6 | −0.08500 (9) | 0.45017 (6) | 0.59582 (11) | 0.0615 (4) | |
O7 | −0.20781 (10) | 0.34531 (9) | 0.68478 (9) | 0.0617 (4) | |
O8 | −0.26342 (8) | 0.30349 (7) | 0.53870 (8) | 0.0462 (3) | |
N1 | 0.30491 (9) | 0.94554 (6) | 0.58779 (9) | 0.0324 (2) | |
N2 | 0.56386 (9) | 0.65231 (6) | 0.66595 (8) | 0.0283 (2) | |
H2 | 0.581 (5) | 0.7017 (15) | 0.681 (4) | 0.042* | 0.32 (3) |
N3 | 0.65839 (9) | 0.60476 (6) | 0.67948 (8) | 0.0297 (2) | |
N4 | −0.19120 (9) | 0.31371 (6) | 0.61492 (8) | 0.0298 (2) | |
N5 | 0.06751 (10) | 0.60825 (6) | 0.64760 (9) | 0.0320 (2) | |
H5B | 0.085 (5) | 0.5573 (14) | 0.653 (5) | 0.048* | 0.30 (3) |
N6 | 0.15748 (9) | 0.65793 (6) | 0.65039 (9) | 0.0341 (2) | |
C1 | 0.51646 (9) | 0.92627 (6) | 0.65260 (8) | 0.0230 (2) | |
C2 | 0.42328 (10) | 0.97588 (7) | 0.61631 (8) | 0.0248 (2) | |
C3 | 0.43361 (11) | 1.05618 (7) | 0.60624 (9) | 0.0307 (3) | |
H3 | 0.3682 | 1.0884 | 0.5810 | 0.037* | |
C4 | 0.54271 (12) | 1.08825 (7) | 0.63415 (10) | 0.0322 (3) | |
C5 | 0.63826 (11) | 1.04195 (7) | 0.67217 (9) | 0.0303 (2) | |
H5 | 0.7123 | 1.0649 | 0.6920 | 0.036* | |
C6 | 0.62447 (10) | 0.96126 (7) | 0.68098 (9) | 0.0258 (2) | |
H6 | 0.6900 | 0.9292 | 0.7069 | 0.031* | |
C7 | 0.50191 (10) | 0.83864 (7) | 0.65949 (9) | 0.0267 (2) | |
C8 | 0.64130 (10) | 0.52950 (7) | 0.66122 (9) | 0.0265 (2) | |
H8 | 0.7065 | 0.4966 | 0.6707 | 0.032* | |
C9 | 0.53156 (9) | 0.49356 (6) | 0.62818 (8) | 0.0218 (2) | |
C10 | 0.51489 (10) | 0.41204 (7) | 0.61081 (9) | 0.0273 (2) | |
H10 | 0.5784 | 0.3774 | 0.6219 | 0.033* | |
C11 | 0.40532 (11) | 0.38357 (7) | 0.57769 (9) | 0.0301 (2) | |
H11 | 0.3934 | 0.3287 | 0.5665 | 0.036* | |
C12 | 0.31042 (11) | 0.43415 (7) | 0.56005 (9) | 0.0299 (2) | |
H12 | 0.2355 | 0.4130 | 0.5361 | 0.036* | |
C13 | 0.32442 (10) | 0.51367 (7) | 0.57697 (9) | 0.0272 (2) | |
H13 | 0.2600 | 0.5476 | 0.5653 | 0.033* | |
C14 | 0.43612 (9) | 0.54386 (6) | 0.61201 (8) | 0.0222 (2) | |
C15 | 0.45979 (10) | 0.62467 (7) | 0.63407 (9) | 0.0262 (2) | |
H15 | 0.3975 | 0.6601 | 0.6253 | 0.031* | |
C16 | 0.01848 (10) | 0.33121 (6) | 0.64156 (8) | 0.0238 (2) | |
C17 | −0.07593 (10) | 0.28156 (7) | 0.62597 (8) | 0.0244 (2) | |
C18 | −0.06837 (11) | 0.20045 (7) | 0.62387 (9) | 0.0285 (2) | |
H18 | −0.1346 | 0.1683 | 0.6118 | 0.034* | |
C19 | 0.03963 (11) | 0.16757 (7) | 0.64005 (9) | 0.0295 (2) | |
C20 | 0.13647 (11) | 0.21412 (7) | 0.65704 (9) | 0.0297 (2) | |
H20 | 0.2097 | 0.1906 | 0.6683 | 0.036* | |
C21 | 0.12533 (10) | 0.29557 (7) | 0.65749 (9) | 0.0272 (2) | |
H21 | 0.1916 | 0.3276 | 0.6688 | 0.033* | |
C22 | 0.00558 (10) | 0.41941 (7) | 0.63517 (9) | 0.0293 (2) | |
C23 | 0.13553 (10) | 0.73295 (7) | 0.63441 (10) | 0.0301 (2) | |
H23 | 0.1976 | 0.7669 | 0.6355 | 0.036* | |
C24 | 0.02458 (9) | 0.76726 (6) | 0.61544 (8) | 0.0235 (2) | |
C25 | 0.00269 (11) | 0.84859 (7) | 0.60091 (10) | 0.0293 (2) | |
H25 | 0.0632 | 0.8841 | 0.6021 | 0.035* | |
C26 | −0.10699 (11) | 0.87592 (7) | 0.58500 (10) | 0.0318 (3) | |
H26 | −0.1220 | 0.9307 | 0.5754 | 0.038* | |
C27 | −0.19758 (11) | 0.82383 (8) | 0.58274 (9) | 0.0304 (2) | |
H27 | −0.2729 | 0.8439 | 0.5713 | 0.036* | |
C28 | −0.17816 (10) | 0.74457 (7) | 0.59685 (9) | 0.0281 (2) | |
H28 | −0.2394 | 0.7097 | 0.5956 | 0.034* | |
C29 | −0.06596 (9) | 0.71544 (7) | 0.61326 (8) | 0.0235 (2) | |
C30 | −0.03699 (11) | 0.63489 (7) | 0.63011 (9) | 0.0284 (2) | |
H30 | −0.0963 | 0.5984 | 0.6287 | 0.034* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0642 (3) | 0.02301 (17) | 0.0863 (3) | −0.00631 (16) | 0.0179 (2) | 0.01464 (17) |
Cl2 | 0.0610 (2) | 0.01785 (14) | 0.0515 (2) | 0.00608 (13) | 0.00546 (17) | −0.00207 (12) |
O1 | 0.0260 (4) | 0.0196 (4) | 0.0629 (7) | 0.0009 (3) | 0.0062 (4) | −0.0011 (4) |
O2 | 0.0274 (5) | 0.0239 (5) | 0.1024 (10) | −0.0036 (4) | 0.0066 (6) | 0.0012 (5) |
O3 | 0.0417 (6) | 0.0732 (8) | 0.0690 (8) | −0.0217 (6) | 0.0300 (6) | −0.0239 (7) |
O4 | 0.0535 (7) | 0.1081 (12) | 0.0420 (7) | −0.0334 (8) | −0.0085 (6) | 0.0052 (7) |
O5 | 0.0254 (4) | 0.0196 (4) | 0.0618 (6) | −0.0004 (3) | 0.0044 (4) | 0.0018 (4) |
O6 | 0.0372 (6) | 0.0224 (5) | 0.0987 (10) | 0.0037 (4) | −0.0216 (6) | 0.0015 (5) |
O7 | 0.0464 (6) | 0.0907 (10) | 0.0448 (6) | 0.0345 (7) | 0.0084 (5) | −0.0099 (6) |
O8 | 0.0271 (5) | 0.0572 (7) | 0.0449 (6) | 0.0003 (4) | −0.0043 (4) | −0.0013 (5) |
N1 | 0.0240 (5) | 0.0273 (5) | 0.0420 (6) | 0.0002 (4) | 0.0034 (4) | 0.0000 (4) |
N2 | 0.0311 (5) | 0.0180 (4) | 0.0336 (5) | 0.0001 (4) | 0.0058 (4) | −0.0001 (4) |
N3 | 0.0250 (5) | 0.0236 (5) | 0.0383 (6) | −0.0017 (4) | 0.0058 (4) | 0.0014 (4) |
N4 | 0.0243 (5) | 0.0293 (5) | 0.0339 (5) | 0.0024 (4) | 0.0053 (4) | 0.0043 (4) |
N5 | 0.0337 (5) | 0.0198 (5) | 0.0405 (6) | 0.0013 (4) | 0.0076 (5) | 0.0003 (4) |
N6 | 0.0282 (5) | 0.0251 (5) | 0.0480 (7) | 0.0025 (4) | 0.0095 (5) | −0.0005 (4) |
C1 | 0.0239 (5) | 0.0201 (5) | 0.0251 (5) | −0.0005 (4) | 0.0073 (4) | −0.0016 (4) |
C2 | 0.0232 (5) | 0.0239 (5) | 0.0266 (5) | −0.0007 (4) | 0.0063 (4) | −0.0004 (4) |
C3 | 0.0332 (6) | 0.0238 (5) | 0.0335 (6) | 0.0041 (5) | 0.0073 (5) | 0.0053 (4) |
C4 | 0.0406 (7) | 0.0210 (5) | 0.0359 (6) | −0.0042 (5) | 0.0123 (5) | 0.0036 (5) |
C5 | 0.0302 (6) | 0.0256 (6) | 0.0352 (6) | −0.0080 (5) | 0.0098 (5) | −0.0009 (5) |
C6 | 0.0237 (5) | 0.0231 (5) | 0.0301 (5) | −0.0012 (4) | 0.0071 (4) | −0.0019 (4) |
C7 | 0.0249 (5) | 0.0207 (5) | 0.0340 (6) | −0.0006 (4) | 0.0076 (4) | −0.0031 (4) |
C8 | 0.0218 (5) | 0.0232 (5) | 0.0334 (6) | 0.0011 (4) | 0.0060 (4) | 0.0025 (4) |
C9 | 0.0224 (5) | 0.0185 (5) | 0.0242 (5) | 0.0008 (4) | 0.0064 (4) | 0.0010 (4) |
C10 | 0.0280 (6) | 0.0187 (5) | 0.0349 (6) | 0.0035 (4) | 0.0084 (5) | 0.0001 (4) |
C11 | 0.0336 (6) | 0.0204 (5) | 0.0349 (6) | −0.0034 (4) | 0.0077 (5) | −0.0030 (4) |
C12 | 0.0254 (5) | 0.0302 (6) | 0.0319 (6) | −0.0051 (5) | 0.0047 (5) | −0.0024 (5) |
C13 | 0.0221 (5) | 0.0279 (5) | 0.0298 (6) | 0.0027 (4) | 0.0047 (4) | −0.0012 (4) |
C14 | 0.0235 (5) | 0.0199 (5) | 0.0227 (5) | 0.0028 (4) | 0.0057 (4) | 0.0004 (4) |
C15 | 0.0281 (5) | 0.0192 (5) | 0.0297 (5) | 0.0034 (4) | 0.0059 (4) | 0.0002 (4) |
C16 | 0.0241 (5) | 0.0187 (5) | 0.0259 (5) | 0.0015 (4) | 0.0031 (4) | −0.0002 (4) |
C17 | 0.0229 (5) | 0.0232 (5) | 0.0247 (5) | 0.0026 (4) | 0.0031 (4) | 0.0000 (4) |
C18 | 0.0310 (6) | 0.0216 (5) | 0.0293 (6) | −0.0037 (4) | 0.0029 (5) | −0.0009 (4) |
C19 | 0.0398 (6) | 0.0181 (5) | 0.0277 (6) | 0.0042 (5) | 0.0050 (5) | −0.0008 (4) |
C20 | 0.0293 (6) | 0.0253 (5) | 0.0322 (6) | 0.0085 (5) | 0.0051 (5) | 0.0000 (4) |
C21 | 0.0238 (5) | 0.0233 (5) | 0.0323 (6) | 0.0022 (4) | 0.0047 (4) | 0.0006 (4) |
C22 | 0.0268 (6) | 0.0198 (5) | 0.0369 (6) | 0.0019 (4) | 0.0022 (5) | −0.0005 (4) |
C23 | 0.0239 (5) | 0.0255 (6) | 0.0411 (7) | −0.0005 (4) | 0.0095 (5) | −0.0004 (5) |
C24 | 0.0229 (5) | 0.0201 (5) | 0.0264 (5) | −0.0010 (4) | 0.0057 (4) | −0.0005 (4) |
C25 | 0.0294 (6) | 0.0195 (5) | 0.0380 (6) | −0.0023 (4) | 0.0082 (5) | 0.0012 (4) |
C26 | 0.0353 (6) | 0.0219 (5) | 0.0372 (6) | 0.0046 (5) | 0.0088 (5) | 0.0020 (5) |
C27 | 0.0262 (5) | 0.0319 (6) | 0.0330 (6) | 0.0067 (5) | 0.0086 (5) | 0.0024 (5) |
C28 | 0.0240 (5) | 0.0295 (6) | 0.0309 (6) | −0.0023 (4) | 0.0080 (4) | 0.0003 (4) |
C29 | 0.0242 (5) | 0.0214 (5) | 0.0242 (5) | −0.0019 (4) | 0.0060 (4) | −0.0006 (4) |
C30 | 0.0313 (6) | 0.0198 (5) | 0.0326 (6) | −0.0036 (4) | 0.0070 (5) | 0.0000 (4) |
Geometric parameters (Å, º) top
Cl1—C4 | 1.7296 (13) | C9—C10 | 1.4108 (15) |
Cl2—C19 | 1.7304 (12) | C10—C11 | 1.3728 (17) |
O1—C7 | 1.3015 (15) | C10—H10 | 0.9500 |
O1—H1 | 0.849 (18) | C11—C12 | 1.4060 (18) |
O2—C7 | 1.2097 (15) | C11—H11 | 0.9500 |
O3—N1 | 1.2222 (17) | C12—C13 | 1.3737 (17) |
O4—N1 | 1.1911 (16) | C12—H12 | 0.9500 |
O5—C22 | 1.3059 (15) | C13—C14 | 1.4079 (16) |
O5—H5A | 0.865 (18) | C13—H13 | 0.9500 |
O6—C22 | 1.2068 (15) | C14—C15 | 1.4191 (15) |
O7—N4 | 1.2115 (16) | C15—H15 | 0.9500 |
O8—N4 | 1.2074 (14) | C16—C17 | 1.3937 (16) |
N1—C2 | 1.4774 (15) | C16—C21 | 1.3967 (15) |
N2—C15 | 1.3079 (16) | C16—C22 | 1.5057 (15) |
N2—N3 | 1.3763 (14) | C17—C18 | 1.3812 (16) |
N2—H2 | 0.87 (2) | C18—C19 | 1.3894 (18) |
N3—C8 | 1.3092 (15) | C18—H18 | 0.9500 |
N4—C17 | 1.4761 (15) | C19—C20 | 1.3848 (18) |
N5—C30 | 1.3089 (16) | C20—C21 | 1.3897 (16) |
N5—N6 | 1.3773 (15) | C20—H20 | 0.9500 |
N5—H5B | 0.89 (2) | C21—H21 | 0.9500 |
N6—C23 | 1.3084 (16) | C23—C24 | 1.4276 (16) |
C1—C2 | 1.3911 (16) | C23—H23 | 0.9500 |
C1—C6 | 1.3965 (15) | C24—C29 | 1.4072 (15) |
C1—C7 | 1.5051 (15) | C24—C25 | 1.4105 (16) |
C2—C3 | 1.3808 (16) | C25—C26 | 1.3738 (18) |
C3—C4 | 1.3877 (18) | C25—H25 | 0.9500 |
C3—H3 | 0.9500 | C26—C27 | 1.4103 (18) |
C4—C5 | 1.3826 (19) | C26—H26 | 0.9500 |
C5—C6 | 1.3905 (16) | C27—C28 | 1.3714 (17) |
C5—H5 | 0.9500 | C27—H27 | 0.9500 |
C6—H6 | 0.9500 | C28—C29 | 1.4119 (16) |
C8—C9 | 1.4242 (15) | C28—H28 | 0.9500 |
C8—H8 | 0.9500 | C29—C30 | 1.4159 (15) |
C9—C14 | 1.4096 (15) | C30—H30 | 0.9500 |
| | | |
C7—O1—H1 | 109 (2) | C12—C13—H13 | 120.7 |
C22—O5—H5A | 106 (2) | C14—C13—H13 | 120.7 |
O4—N1—O3 | 124.43 (13) | C13—C14—C9 | 120.57 (10) |
O4—N1—C2 | 118.55 (12) | C13—C14—C15 | 123.09 (10) |
O3—N1—C2 | 116.92 (11) | C9—C14—C15 | 116.33 (10) |
C15—N2—N3 | 122.03 (10) | N2—C15—C14 | 122.68 (10) |
C15—N2—H2 | 124 (4) | N2—C15—H15 | 118.7 |
N3—N2—H2 | 114 (4) | C14—C15—H15 | 118.7 |
C8—N3—N2 | 117.75 (10) | C17—C16—C21 | 117.11 (10) |
O8—N4—O7 | 124.67 (12) | C17—C16—C22 | 121.63 (10) |
O8—N4—C17 | 117.88 (11) | C21—C16—C22 | 121.15 (10) |
O7—N4—C17 | 117.36 (11) | C18—C17—C16 | 123.30 (11) |
C30—N5—N6 | 121.37 (10) | C18—C17—N4 | 115.73 (10) |
C30—N5—H5B | 123 (4) | C16—C17—N4 | 120.91 (10) |
N6—N5—H5B | 115 (4) | C17—C18—C19 | 117.60 (11) |
C23—N6—N5 | 118.02 (10) | C17—C18—H18 | 121.2 |
C2—C1—C6 | 117.01 (10) | C19—C18—H18 | 121.2 |
C2—C1—C7 | 121.59 (10) | C20—C19—C18 | 121.48 (11) |
C6—C1—C7 | 121.39 (10) | C20—C19—Cl2 | 119.33 (10) |
C3—C2—C1 | 123.20 (11) | C18—C19—Cl2 | 119.19 (10) |
C3—C2—N1 | 115.28 (10) | C19—C20—C21 | 119.27 (11) |
C1—C2—N1 | 121.51 (10) | C19—C20—H20 | 120.4 |
C2—C3—C4 | 117.81 (11) | C21—C20—H20 | 120.4 |
C2—C3—H3 | 121.1 | C20—C21—C16 | 121.23 (11) |
C4—C3—H3 | 121.1 | C20—C21—H21 | 119.4 |
C5—C4—C3 | 121.48 (11) | C16—C21—H21 | 119.4 |
C5—C4—Cl1 | 119.43 (10) | O6—C22—O5 | 124.94 (11) |
C3—C4—Cl1 | 119.09 (10) | O6—C22—C16 | 121.65 (11) |
C4—C5—C6 | 119.06 (11) | O5—C22—C16 | 113.39 (10) |
C4—C5—H5 | 120.5 | N6—C23—C24 | 124.46 (11) |
C6—C5—H5 | 120.5 | N6—C23—H23 | 117.8 |
C5—C6—C1 | 121.44 (11) | C24—C23—H23 | 117.8 |
C5—C6—H6 | 119.3 | C29—C24—C25 | 119.65 (10) |
C1—C6—H6 | 119.3 | C29—C24—C23 | 116.52 (10) |
O2—C7—O1 | 125.03 (11) | C25—C24—C23 | 123.82 (11) |
O2—C7—C1 | 121.43 (11) | C26—C25—C24 | 119.30 (11) |
O1—C7—C1 | 113.54 (10) | C26—C25—H25 | 120.4 |
N3—C8—C9 | 124.43 (11) | C24—C25—H25 | 120.4 |
N3—C8—H8 | 117.8 | C25—C26—C27 | 120.92 (11) |
C9—C8—H8 | 117.8 | C25—C26—H26 | 119.5 |
C14—C9—C10 | 119.68 (10) | C27—C26—H26 | 119.5 |
C14—C9—C8 | 116.73 (10) | C28—C27—C26 | 120.73 (11) |
C10—C9—C8 | 123.60 (10) | C28—C27—H27 | 119.6 |
C11—C10—C9 | 118.90 (11) | C26—C27—H27 | 119.6 |
C11—C10—H10 | 120.5 | C27—C28—C29 | 119.11 (11) |
C9—C10—H10 | 120.5 | C27—C28—H28 | 120.4 |
C10—C11—C12 | 121.22 (11) | C29—C28—H28 | 120.4 |
C10—C11—H11 | 119.4 | C24—C29—C28 | 120.28 (10) |
C12—C11—H11 | 119.4 | C24—C29—C30 | 116.37 (10) |
C13—C12—C11 | 120.96 (11) | C28—C29—C30 | 123.33 (11) |
C13—C12—H12 | 119.5 | N5—C30—C29 | 123.25 (11) |
C11—C12—H12 | 119.5 | N5—C30—H30 | 118.4 |
C12—C13—C14 | 118.66 (11) | C29—C30—H30 | 118.4 |
| | | |
C15—N2—N3—C8 | −1.41 (18) | C9—C14—C15—N2 | 1.27 (17) |
C30—N5—N6—C23 | −0.41 (19) | C21—C16—C17—C18 | −1.25 (18) |
C6—C1—C2—C3 | 0.98 (17) | C22—C16—C17—C18 | 174.87 (11) |
C7—C1—C2—C3 | −178.01 (12) | C21—C16—C17—N4 | 175.93 (10) |
C6—C1—C2—N1 | −177.55 (11) | C22—C16—C17—N4 | −7.94 (17) |
C7—C1—C2—N1 | 3.45 (17) | O8—N4—C17—C18 | −65.48 (15) |
O4—N1—C2—C3 | 79.00 (17) | O7—N4—C17—C18 | 111.16 (14) |
O3—N1—C2—C3 | −97.57 (15) | O8—N4—C17—C16 | 117.13 (13) |
O4—N1—C2—C1 | −102.36 (16) | O7—N4—C17—C16 | −66.22 (17) |
O3—N1—C2—C1 | 81.07 (16) | C16—C17—C18—C19 | 1.25 (18) |
C1—C2—C3—C4 | −0.15 (19) | N4—C17—C18—C19 | −176.07 (10) |
N1—C2—C3—C4 | 178.47 (11) | C17—C18—C19—C20 | −0.43 (18) |
C2—C3—C4—C5 | −0.93 (19) | C17—C18—C19—Cl2 | 178.47 (9) |
C2—C3—C4—Cl1 | 179.65 (10) | C18—C19—C20—C21 | −0.31 (19) |
C3—C4—C5—C6 | 1.1 (2) | Cl2—C19—C20—C21 | −179.21 (10) |
Cl1—C4—C5—C6 | −179.47 (10) | C19—C20—C21—C16 | 0.29 (19) |
C4—C5—C6—C1 | −0.22 (19) | C17—C16—C21—C20 | 0.45 (18) |
C2—C1—C6—C5 | −0.79 (17) | C22—C16—C21—C20 | −175.70 (11) |
C7—C1—C6—C5 | 178.21 (11) | C17—C16—C22—O6 | −17.0 (2) |
C2—C1—C7—O2 | −1.73 (19) | C21—C16—C22—O6 | 158.95 (15) |
C6—C1—C7—O2 | 179.31 (13) | C17—C16—C22—O5 | 164.43 (12) |
C2—C1—C7—O1 | 177.63 (11) | C21—C16—C22—O5 | −19.60 (17) |
C6—C1—C7—O1 | −1.32 (17) | N5—N6—C23—C24 | 0.9 (2) |
N2—N3—C8—C9 | 0.11 (18) | N6—C23—C24—C29 | −0.65 (19) |
N3—C8—C9—C14 | 1.81 (18) | N6—C23—C24—C25 | 178.23 (13) |
N3—C8—C9—C10 | −178.63 (12) | C29—C24—C25—C26 | 0.12 (18) |
C14—C9—C10—C11 | 0.46 (17) | C23—C24—C25—C26 | −178.72 (12) |
C8—C9—C10—C11 | −179.09 (11) | C24—C25—C26—C27 | −0.2 (2) |
C9—C10—C11—C12 | 0.66 (19) | C25—C26—C27—C28 | 0.3 (2) |
C10—C11—C12—C13 | −1.1 (2) | C26—C27—C28—C29 | −0.34 (19) |
C11—C12—C13—C14 | 0.32 (19) | C25—C24—C29—C28 | −0.15 (17) |
C12—C13—C14—C9 | 0.80 (17) | C23—C24—C29—C28 | 178.77 (11) |
C12—C13—C14—C15 | −178.39 (12) | C25—C24—C29—C30 | −178.94 (11) |
C10—C9—C14—C13 | −1.20 (17) | C23—C24—C29—C30 | −0.02 (16) |
C8—C9—C14—C13 | 178.38 (11) | C27—C28—C29—C24 | 0.26 (17) |
C10—C9—C14—C15 | 178.04 (11) | C27—C28—C29—C30 | 178.96 (12) |
C8—C9—C14—C15 | −2.38 (15) | N6—N5—C30—C29 | −0.2 (2) |
N3—N2—C15—C14 | 0.70 (18) | C24—C29—C30—N5 | 0.44 (18) |
C13—C14—C15—N2 | −179.50 (11) | C28—C29—C30—N5 | −178.31 (12) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N2 | 0.85 (2) | 1.72 (2) | 2.5655 (13) | 175 (3) |
O5—H5A···N5 | 0.86 (2) | 1.75 (2) | 2.6081 (13) | 174 (2) |
N2—H2···O1 | 0.88 (3) | 1.70 (3) | 2.5655 (13) | 171 (6) |
N5—H5B···O5 | 0.89 (3) | 1.73 (3) | 2.6081 (13) | 170 (6) |
C10—H10···O7i | 0.95 | 2.56 | 3.4371 (18) | 153 |
C15—H15···O2 | 0.95 | 2.52 | 3.1832 (16) | 127 |
C15—H15···O8ii | 0.95 | 2.54 | 3.1627 (17) | 124 |
C25—H25···O3 | 0.95 | 2.47 | 3.3602 (19) | 157 |
C30—H30···O6 | 0.95 | 2.57 | 3.2026 (16) | 124 |
Symmetry codes: (i) x+1, y, z; (ii) −x, −y+1, −z+1. |
(III) 4-chloro-3-nitrobenzoic acid–phthalazine (1/1)
top
Crystal data top
C7H4ClNO4·C8H6N2 | Z = 4 |
Mr = 331.71 | F(000) = 680.00 |
Triclinic, P1 | Dx = 1.571 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71075 Å |
a = 6.9197 (5) Å | Cell parameters from 15895 reflections |
b = 14.4263 (12) Å | θ = 3.0–30.1° |
c = 14.4750 (9) Å | µ = 0.30 mm−1 |
α = 81.704 (2)° | T = 190 K |
β = 79.0781 (18)° | Needle, colourless |
γ = 85.647 (2)° | 0.40 × 0.18 × 0.06 mm |
V = 1402.20 (17) Å3 | |
Data collection top
Rigaku R-AXIS RAPID II diffractometer | 4765 reflections with I > 2σ(I) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.056 |
ω scans | θmax = 30.0° |
Absorption correction: numerical (NUMABS; Higashi, 1999) | h = −9→9 |
Tmin = 0.929, Tmax = 0.982 | k = −20→20 |
22476 measured reflections | l = −20→20 |
7849 independent 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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.154 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | w = 1/[σ2(Fo2) + (0.081P)2] where P = (Fo2 + 2Fc2)/3 |
7849 reflections | (Δ/σ)max < 0.001 |
423 parameters | Δρmax = 0.53 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
Crystal data top
C7H4ClNO4·C8H6N2 | γ = 85.647 (2)° |
Mr = 331.71 | V = 1402.20 (17) Å3 |
Triclinic, P1 | Z = 4 |
a = 6.9197 (5) Å | Mo Kα radiation |
b = 14.4263 (12) Å | µ = 0.30 mm−1 |
c = 14.4750 (9) Å | T = 190 K |
α = 81.704 (2)° | 0.40 × 0.18 × 0.06 mm |
β = 79.0781 (18)° | |
Data collection top
Rigaku R-AXIS RAPID II diffractometer | 7849 independent reflections |
Absorption correction: numerical (NUMABS; Higashi, 1999) | 4765 reflections with I > 2σ(I) |
Tmin = 0.929, Tmax = 0.982 | Rint = 0.056 |
22476 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.154 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.53 e Å−3 |
7849 reflections | Δρmin = −0.48 e Å−3 |
423 parameters | |
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 | |
Cl1 | 0.90846 (8) | 0.11798 (4) | −0.29615 (4) | 0.03773 (15) | |
Cl2 | 0.44568 (8) | 0.11350 (4) | 0.20068 (4) | 0.04165 (16) | |
O1 | 0.7875 (2) | 0.49754 (10) | −0.07530 (10) | 0.0390 (4) | |
O2 | 0.7307 (2) | 0.39169 (11) | 0.05393 (10) | 0.0394 (4) | |
O3 | 0.6714 (3) | 0.06281 (12) | −0.00799 (13) | 0.0578 (5) | |
O4 | 0.9263 (3) | 0.01878 (12) | −0.10527 (13) | 0.0575 (5) | |
O5 | 0.2416 (3) | 0.41899 (11) | 0.51448 (11) | 0.0415 (4) | |
O6 | 0.2946 (2) | 0.52181 (10) | 0.38222 (11) | 0.0400 (4) | |
O7 | 0.3389 (3) | 0.09591 (11) | 0.50899 (11) | 0.0538 (5) | |
O8 | 0.2970 (3) | 0.03085 (11) | 0.39038 (12) | 0.0477 (4) | |
N1 | 0.8053 (3) | 0.07913 (12) | −0.07481 (13) | 0.0348 (4) | |
N2 | 0.7277 (3) | 0.62891 (12) | 0.03523 (12) | 0.0327 (4) | |
N3 | 0.7535 (3) | 0.71534 (13) | −0.01737 (12) | 0.0343 (4) | |
N4 | 0.3245 (2) | 0.09936 (12) | 0.42563 (12) | 0.0314 (4) | |
N5 | 0.1963 (2) | 0.56614 (12) | 0.60132 (12) | 0.0315 (4) | |
N6 | 0.1509 (3) | 0.54527 (12) | 0.69854 (12) | 0.0338 (4) | |
C1 | 0.8083 (3) | 0.33866 (14) | −0.09750 (13) | 0.0259 (4) | |
C2 | 0.7880 (3) | 0.24528 (14) | −0.05996 (14) | 0.0268 (4) | |
H2 | 0.7496 | 0.2284 | 0.0066 | 0.032* | |
C3 | 0.8238 (3) | 0.17658 (14) | −0.11969 (14) | 0.0274 (4) | |
C4 | 0.8761 (3) | 0.20009 (14) | −0.21815 (14) | 0.0276 (4) | |
C5 | 0.8941 (3) | 0.29344 (14) | −0.25478 (14) | 0.0290 (4) | |
H5 | 0.9285 | 0.3106 | −0.3215 | 0.035* | |
C6 | 0.8623 (3) | 0.36230 (14) | −0.19538 (13) | 0.0275 (4) | |
H6 | 0.8775 | 0.4262 | −0.2215 | 0.033* | |
C7 | 0.7714 (3) | 0.41187 (14) | −0.03132 (14) | 0.0286 (4) | |
C8 | 0.7271 (3) | 0.78899 (15) | 0.02742 (14) | 0.0313 (4) | |
H8 | 0.7443 | 0.8487 | −0.0098 | 0.038* | |
C9 | 0.6748 (3) | 0.78670 (14) | 0.12736 (13) | 0.0258 (4) | |
C10 | 0.6488 (3) | 0.86741 (15) | 0.17393 (15) | 0.0318 (4) | |
H10 | 0.6648 | 0.9280 | 0.1385 | 0.038* | |
C11 | 0.6000 (3) | 0.85712 (16) | 0.27094 (15) | 0.0352 (5) | |
H11 | 0.5821 | 0.9111 | 0.3028 | 0.042* | |
C12 | 0.5762 (3) | 0.76823 (17) | 0.32376 (15) | 0.0350 (5) | |
H12 | 0.5429 | 0.7629 | 0.3910 | 0.042* | |
C13 | 0.6002 (3) | 0.68848 (15) | 0.28024 (14) | 0.0321 (4) | |
H13 | 0.5834 | 0.6285 | 0.3168 | 0.039* | |
C14 | 0.6501 (3) | 0.69723 (14) | 0.18042 (14) | 0.0262 (4) | |
C15 | 0.6794 (3) | 0.62040 (14) | 0.12769 (14) | 0.0298 (4) | |
H15 | 0.6632 | 0.5591 | 0.1615 | 0.036* | |
C16 | 0.3195 (3) | 0.35862 (14) | 0.36924 (14) | 0.0266 (4) | |
C17 | 0.3045 (3) | 0.26855 (14) | 0.41692 (14) | 0.0263 (4) | |
H17 | 0.2688 | 0.2593 | 0.4842 | 0.032* | |
C18 | 0.3409 (3) | 0.19156 (13) | 0.36776 (13) | 0.0256 (4) | |
C19 | 0.3927 (3) | 0.20401 (14) | 0.26844 (14) | 0.0280 (4) | |
C20 | 0.4088 (3) | 0.29465 (15) | 0.22163 (14) | 0.0308 (4) | |
H20 | 0.4459 | 0.3043 | 0.1545 | 0.037* | |
C21 | 0.3719 (3) | 0.37094 (14) | 0.27075 (14) | 0.0297 (4) | |
H21 | 0.3824 | 0.4325 | 0.2371 | 0.036* | |
C22 | 0.2831 (3) | 0.44220 (14) | 0.42219 (14) | 0.0293 (4) | |
C23 | 0.1152 (3) | 0.61542 (14) | 0.74862 (14) | 0.0303 (4) | |
H23 | 0.0807 | 0.6009 | 0.8156 | 0.036* | |
C24 | 0.1242 (3) | 0.71131 (14) | 0.71005 (14) | 0.0262 (4) | |
C25 | 0.0860 (3) | 0.78511 (15) | 0.76636 (15) | 0.0332 (5) | |
H25 | 0.0511 | 0.7720 | 0.8335 | 0.040* | |
C26 | 0.0999 (3) | 0.87563 (15) | 0.72323 (17) | 0.0375 (5) | |
H26 | 0.0741 | 0.9256 | 0.7607 | 0.045* | |
C27 | 0.1519 (3) | 0.89573 (15) | 0.62415 (17) | 0.0380 (5) | |
H27 | 0.1619 | 0.9592 | 0.5956 | 0.046* | |
C28 | 0.1886 (3) | 0.82524 (15) | 0.56790 (15) | 0.0335 (5) | |
H28 | 0.2229 | 0.8396 | 0.5009 | 0.040* | |
C29 | 0.1746 (3) | 0.73151 (13) | 0.61081 (14) | 0.0258 (4) | |
C30 | 0.2083 (3) | 0.65275 (15) | 0.56057 (14) | 0.0308 (4) | |
H30 | 0.2415 | 0.6637 | 0.4933 | 0.037* | |
H1 | 0.755 (5) | 0.544 (3) | −0.028 (3) | 0.108 (12)* | |
H5A | 0.216 (5) | 0.479 (3) | 0.545 (3) | 0.125 (14)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0435 (3) | 0.0352 (3) | 0.0387 (3) | 0.0052 (2) | −0.0098 (2) | −0.0196 (2) |
Cl2 | 0.0505 (3) | 0.0405 (3) | 0.0370 (3) | 0.0057 (2) | −0.0070 (3) | −0.0206 (2) |
O1 | 0.0614 (10) | 0.0236 (8) | 0.0303 (8) | −0.0008 (7) | −0.0011 (7) | −0.0088 (6) |
O2 | 0.0559 (10) | 0.0366 (9) | 0.0247 (7) | −0.0062 (7) | 0.0003 (7) | −0.0087 (6) |
O3 | 0.0684 (12) | 0.0377 (10) | 0.0560 (11) | −0.0067 (9) | 0.0107 (10) | 0.0043 (8) |
O4 | 0.0800 (13) | 0.0303 (9) | 0.0560 (11) | 0.0088 (9) | 0.0001 (10) | −0.0080 (8) |
O5 | 0.0687 (11) | 0.0239 (8) | 0.0320 (8) | 0.0000 (7) | −0.0068 (8) | −0.0089 (6) |
O6 | 0.0574 (10) | 0.0220 (8) | 0.0408 (9) | −0.0028 (7) | −0.0092 (8) | −0.0038 (6) |
O7 | 0.0978 (14) | 0.0318 (9) | 0.0320 (8) | −0.0124 (9) | −0.0116 (9) | −0.0003 (7) |
O8 | 0.0722 (11) | 0.0238 (8) | 0.0512 (10) | −0.0038 (8) | −0.0163 (9) | −0.0109 (7) |
N1 | 0.0418 (10) | 0.0266 (9) | 0.0352 (9) | −0.0017 (8) | −0.0050 (9) | −0.0046 (7) |
N2 | 0.0372 (9) | 0.0279 (9) | 0.0344 (9) | 0.0011 (7) | −0.0065 (8) | −0.0105 (7) |
N3 | 0.0433 (10) | 0.0331 (10) | 0.0278 (9) | 0.0006 (8) | −0.0079 (8) | −0.0075 (7) |
N4 | 0.0357 (9) | 0.0267 (9) | 0.0318 (9) | −0.0006 (7) | −0.0040 (8) | −0.0071 (7) |
N5 | 0.0376 (9) | 0.0277 (9) | 0.0309 (9) | −0.0001 (7) | −0.0064 (8) | −0.0096 (7) |
N6 | 0.0419 (10) | 0.0265 (9) | 0.0333 (9) | −0.0016 (7) | −0.0070 (8) | −0.0041 (7) |
C1 | 0.0242 (9) | 0.0270 (10) | 0.0271 (9) | −0.0009 (7) | −0.0030 (8) | −0.0082 (8) |
C2 | 0.0269 (9) | 0.0292 (10) | 0.0242 (9) | −0.0007 (8) | −0.0033 (8) | −0.0054 (8) |
C3 | 0.0258 (9) | 0.0248 (10) | 0.0321 (10) | −0.0013 (7) | −0.0050 (8) | −0.0060 (8) |
C4 | 0.0251 (9) | 0.0305 (11) | 0.0293 (10) | 0.0033 (8) | −0.0055 (8) | −0.0124 (8) |
C5 | 0.0292 (10) | 0.0334 (11) | 0.0252 (9) | 0.0020 (8) | −0.0049 (8) | −0.0086 (8) |
C6 | 0.0282 (10) | 0.0267 (10) | 0.0270 (9) | −0.0005 (8) | −0.0033 (8) | −0.0045 (8) |
C7 | 0.0269 (10) | 0.0311 (11) | 0.0286 (10) | −0.0013 (8) | −0.0034 (8) | −0.0091 (8) |
C8 | 0.0378 (11) | 0.0279 (11) | 0.0283 (10) | 0.0001 (8) | −0.0067 (9) | −0.0041 (8) |
C9 | 0.0253 (9) | 0.0266 (10) | 0.0273 (9) | 0.0010 (7) | −0.0072 (8) | −0.0072 (8) |
C10 | 0.0321 (10) | 0.0278 (11) | 0.0367 (11) | 0.0006 (8) | −0.0059 (9) | −0.0095 (9) |
C11 | 0.0327 (11) | 0.0371 (12) | 0.0393 (12) | 0.0038 (9) | −0.0070 (10) | −0.0185 (10) |
C12 | 0.0290 (10) | 0.0509 (14) | 0.0265 (10) | 0.0023 (9) | −0.0044 (9) | −0.0123 (9) |
C13 | 0.0294 (10) | 0.0358 (12) | 0.0296 (10) | −0.0003 (8) | −0.0038 (9) | −0.0021 (9) |
C14 | 0.0225 (9) | 0.0285 (10) | 0.0288 (10) | 0.0010 (7) | −0.0059 (8) | −0.0070 (8) |
C15 | 0.0321 (10) | 0.0246 (10) | 0.0339 (10) | 0.0007 (8) | −0.0078 (9) | −0.0062 (8) |
C16 | 0.0248 (9) | 0.0259 (10) | 0.0305 (10) | −0.0003 (7) | −0.0066 (8) | −0.0068 (8) |
C17 | 0.0273 (9) | 0.0270 (10) | 0.0260 (9) | −0.0016 (7) | −0.0048 (8) | −0.0075 (8) |
C18 | 0.0271 (9) | 0.0235 (10) | 0.0270 (9) | 0.0005 (7) | −0.0071 (8) | −0.0044 (7) |
C19 | 0.0272 (9) | 0.0309 (11) | 0.0283 (10) | 0.0017 (8) | −0.0075 (8) | −0.0107 (8) |
C20 | 0.0294 (10) | 0.0389 (12) | 0.0239 (9) | −0.0004 (8) | −0.0037 (8) | −0.0059 (8) |
C21 | 0.0313 (10) | 0.0269 (10) | 0.0298 (10) | −0.0017 (8) | −0.0047 (9) | −0.0016 (8) |
C22 | 0.0299 (10) | 0.0264 (11) | 0.0329 (10) | −0.0014 (8) | −0.0063 (9) | −0.0072 (8) |
C23 | 0.0338 (10) | 0.0304 (11) | 0.0268 (10) | −0.0017 (8) | −0.0053 (9) | −0.0042 (8) |
C24 | 0.0222 (9) | 0.0278 (10) | 0.0287 (10) | −0.0005 (7) | −0.0036 (8) | −0.0052 (8) |
C25 | 0.0341 (11) | 0.0340 (12) | 0.0324 (11) | 0.0018 (9) | −0.0041 (9) | −0.0120 (9) |
C26 | 0.0341 (11) | 0.0282 (11) | 0.0506 (13) | 0.0013 (8) | −0.0031 (10) | −0.0148 (10) |
C27 | 0.0343 (11) | 0.0237 (11) | 0.0517 (13) | 0.0006 (8) | −0.0005 (10) | −0.0012 (9) |
C28 | 0.0345 (11) | 0.0294 (11) | 0.0328 (11) | −0.0002 (8) | −0.0002 (9) | 0.0000 (9) |
C29 | 0.0221 (9) | 0.0249 (10) | 0.0292 (10) | −0.0001 (7) | −0.0010 (8) | −0.0050 (8) |
C30 | 0.0319 (10) | 0.0323 (11) | 0.0277 (10) | −0.0013 (8) | −0.0018 (9) | −0.0071 (8) |
Geometric parameters (Å, º) top
Cl1—C4 | 1.7257 (18) | C10—C11 | 1.370 (3) |
Cl2—C19 | 1.7210 (19) | C10—H10 | 0.9500 |
O1—C7 | 1.309 (3) | C11—C12 | 1.399 (3) |
O1—H1 | 1.01 (4) | C11—H11 | 0.9500 |
O2—C7 | 1.210 (2) | C12—C13 | 1.374 (3) |
O3—N1 | 1.215 (2) | C12—H12 | 0.9500 |
O4—N1 | 1.230 (2) | C13—C14 | 1.410 (3) |
O5—C22 | 1.311 (2) | C13—H13 | 0.9500 |
O5—H5A | 1.02 (4) | C14—C15 | 1.415 (3) |
O6—C22 | 1.210 (2) | C15—H15 | 0.9500 |
O7—N4 | 1.223 (2) | C16—C17 | 1.382 (3) |
O8—N4 | 1.218 (2) | C16—C21 | 1.391 (3) |
N1—C3 | 1.465 (3) | C16—C22 | 1.501 (3) |
N2—C15 | 1.307 (3) | C17—C18 | 1.386 (2) |
N2—N3 | 1.369 (3) | C17—H17 | 0.9500 |
N3—C8 | 1.307 (2) | C18—C19 | 1.403 (3) |
N4—C18 | 1.466 (3) | C19—C20 | 1.385 (3) |
N5—C30 | 1.304 (3) | C20—C21 | 1.377 (3) |
N5—N6 | 1.376 (2) | C20—H20 | 0.9500 |
N6—C23 | 1.310 (2) | C21—H21 | 0.9500 |
C1—C2 | 1.385 (3) | C23—C24 | 1.416 (3) |
C1—C6 | 1.394 (3) | C23—H23 | 0.9500 |
C1—C7 | 1.502 (2) | C24—C29 | 1.405 (3) |
C2—C3 | 1.386 (2) | C24—C25 | 1.412 (3) |
C2—H2 | 0.9500 | C25—C26 | 1.366 (3) |
C3—C4 | 1.400 (3) | C25—H25 | 0.9500 |
C4—C5 | 1.380 (3) | C26—C27 | 1.404 (3) |
C5—C6 | 1.384 (2) | C26—H26 | 0.9500 |
C5—H5 | 0.9500 | C27—C28 | 1.372 (3) |
C6—H6 | 0.9500 | C27—H27 | 0.9500 |
C8—C9 | 1.419 (3) | C28—C29 | 1.407 (3) |
C8—H8 | 0.9500 | C28—H28 | 0.9500 |
C9—C14 | 1.408 (3) | C29—C30 | 1.417 (3) |
C9—C10 | 1.411 (3) | C30—H30 | 0.9500 |
| | | |
C7—O1—H1 | 110 (2) | C9—C14—C13 | 119.81 (18) |
C22—O5—H5A | 108 (2) | C9—C14—C15 | 116.13 (18) |
O3—N1—O4 | 123.56 (19) | C13—C14—C15 | 124.06 (19) |
O3—N1—C3 | 117.54 (17) | N2—C15—C14 | 123.76 (19) |
O4—N1—C3 | 118.89 (18) | N2—C15—H15 | 118.1 |
C15—N2—N3 | 120.85 (16) | C14—C15—H15 | 118.1 |
C8—N3—N2 | 118.15 (17) | C17—C16—C21 | 118.89 (17) |
O8—N4—O7 | 123.10 (19) | C17—C16—C22 | 120.99 (18) |
O8—N4—C18 | 120.11 (17) | C21—C16—C22 | 120.11 (18) |
O7—N4—C18 | 116.79 (16) | C16—C17—C18 | 120.75 (18) |
C30—N5—N6 | 121.11 (16) | C16—C17—H17 | 119.6 |
C23—N6—N5 | 117.75 (17) | C18—C17—H17 | 119.6 |
C2—C1—C6 | 119.32 (17) | C17—C18—C19 | 120.35 (18) |
C2—C1—C7 | 118.94 (17) | C17—C18—N4 | 116.12 (17) |
C6—C1—C7 | 121.74 (18) | C19—C18—N4 | 123.53 (17) |
C1—C2—C3 | 119.83 (18) | C20—C19—C18 | 118.28 (17) |
C1—C2—H2 | 120.1 | C20—C19—Cl2 | 117.52 (15) |
C3—C2—H2 | 120.1 | C18—C19—Cl2 | 124.16 (16) |
C2—C3—C4 | 121.03 (18) | C21—C20—C19 | 121.16 (18) |
C2—C3—N1 | 116.85 (17) | C21—C20—H20 | 119.4 |
C4—C3—N1 | 122.12 (17) | C19—C20—H20 | 119.4 |
C5—C4—C3 | 118.60 (17) | C20—C21—C16 | 120.56 (19) |
C5—C4—Cl1 | 118.46 (15) | C20—C21—H21 | 119.7 |
C3—C4—Cl1 | 122.88 (16) | C16—C21—H21 | 119.7 |
C4—C5—C6 | 120.69 (18) | O6—C22—O5 | 124.83 (18) |
C4—C5—H5 | 119.7 | O6—C22—C16 | 122.36 (18) |
C6—C5—H5 | 119.7 | O5—C22—C16 | 112.80 (18) |
C5—C6—C1 | 120.52 (19) | N6—C23—C24 | 124.70 (19) |
C5—C6—H6 | 119.7 | N6—C23—H23 | 117.7 |
C1—C6—H6 | 119.7 | C24—C23—H23 | 117.7 |
O2—C7—O1 | 124.59 (18) | C29—C24—C25 | 119.96 (19) |
O2—C7—C1 | 122.13 (19) | C29—C24—C23 | 116.91 (17) |
O1—C7—C1 | 113.28 (17) | C25—C24—C23 | 123.13 (19) |
N3—C8—C9 | 125.0 (2) | C26—C25—C24 | 119.2 (2) |
N3—C8—H8 | 117.5 | C26—C25—H25 | 120.4 |
C9—C8—H8 | 117.5 | C24—C25—H25 | 120.4 |
C14—C9—C10 | 120.10 (18) | C25—C26—C27 | 120.79 (19) |
C14—C9—C8 | 116.09 (17) | C25—C26—H26 | 119.6 |
C10—C9—C8 | 123.81 (19) | C27—C26—H26 | 119.6 |
C11—C10—C9 | 119.0 (2) | C28—C27—C26 | 121.1 (2) |
C11—C10—H10 | 120.5 | C28—C27—H27 | 119.5 |
C9—C10—H10 | 120.5 | C26—C27—H27 | 119.5 |
C10—C11—C12 | 120.94 (19) | C27—C28—C29 | 119.1 (2) |
C10—C11—H11 | 119.5 | C27—C28—H28 | 120.4 |
C12—C11—H11 | 119.5 | C29—C28—H28 | 120.4 |
C13—C12—C11 | 121.27 (19) | C24—C29—C28 | 119.86 (17) |
C13—C12—H12 | 119.4 | C24—C29—C30 | 115.69 (18) |
C11—C12—H12 | 119.4 | C28—C29—C30 | 124.45 (19) |
C12—C13—C14 | 118.9 (2) | N5—C30—C29 | 123.81 (19) |
C12—C13—H13 | 120.6 | N5—C30—H30 | 118.1 |
C14—C13—H13 | 120.6 | C29—C30—H30 | 118.1 |
| | | |
C15—N2—N3—C8 | −0.5 (3) | C13—C14—C15—N2 | −179.26 (18) |
C30—N5—N6—C23 | 1.7 (3) | C21—C16—C17—C18 | 0.0 (3) |
C6—C1—C2—C3 | 0.8 (3) | C22—C16—C17—C18 | −179.10 (17) |
C7—C1—C2—C3 | −179.15 (17) | C16—C17—C18—C19 | −0.3 (3) |
C1—C2—C3—C4 | −1.5 (3) | C16—C17—C18—N4 | 178.84 (16) |
C1—C2—C3—N1 | 178.21 (16) | O8—N4—C18—C17 | 158.68 (18) |
O3—N1—C3—C2 | 39.3 (3) | O7—N4—C18—C17 | −21.1 (3) |
O4—N1—C3—C2 | −139.6 (2) | O8—N4—C18—C19 | −22.2 (3) |
O3—N1—C3—C4 | −141.0 (2) | O7—N4—C18—C19 | 158.08 (19) |
O4—N1—C3—C4 | 40.1 (3) | C17—C18—C19—C20 | 0.9 (3) |
C2—C3—C4—C5 | 0.9 (3) | N4—C18—C19—C20 | −178.24 (17) |
N1—C3—C4—C5 | −178.81 (17) | C17—C18—C19—Cl2 | 178.65 (15) |
C2—C3—C4—Cl1 | −176.15 (15) | N4—C18—C19—Cl2 | −0.5 (3) |
N1—C3—C4—Cl1 | 4.2 (3) | C18—C19—C20—C21 | −1.1 (3) |
C3—C4—C5—C6 | 0.4 (3) | Cl2—C19—C20—C21 | −178.99 (15) |
Cl1—C4—C5—C6 | 177.59 (15) | C19—C20—C21—C16 | 0.7 (3) |
C4—C5—C6—C1 | −1.1 (3) | C17—C16—C21—C20 | −0.1 (3) |
C2—C1—C6—C5 | 0.5 (3) | C22—C16—C21—C20 | 178.93 (17) |
C7—C1—C6—C5 | −179.56 (17) | C17—C16—C22—O6 | −179.76 (19) |
C2—C1—C7—O2 | 2.4 (3) | C21—C16—C22—O6 | 1.2 (3) |
C6—C1—C7—O2 | −177.53 (18) | C17—C16—C22—O5 | 1.2 (3) |
C2—C1—C7—O1 | −177.47 (17) | C21—C16—C22—O5 | −177.84 (17) |
C6—C1—C7—O1 | 2.6 (3) | N5—N6—C23—C24 | −1.5 (3) |
N2—N3—C8—C9 | 0.5 (3) | N6—C23—C24—C29 | 0.2 (3) |
N3—C8—C9—C14 | −0.1 (3) | N6—C23—C24—C25 | −179.51 (19) |
N3—C8—C9—C10 | 179.46 (19) | C29—C24—C25—C26 | −0.4 (3) |
C14—C9—C10—C11 | 0.2 (3) | C23—C24—C25—C26 | 179.38 (18) |
C8—C9—C10—C11 | −179.36 (18) | C24—C25—C26—C27 | −0.2 (3) |
C9—C10—C11—C12 | 0.1 (3) | C25—C26—C27—C28 | 0.6 (3) |
C10—C11—C12—C13 | −0.2 (3) | C26—C27—C28—C29 | −0.4 (3) |
C11—C12—C13—C14 | 0.1 (3) | C25—C24—C29—C28 | 0.5 (3) |
C10—C9—C14—C13 | −0.3 (3) | C23—C24—C29—C28 | −179.22 (17) |
C8—C9—C14—C13 | 179.29 (16) | C25—C24—C29—C30 | −179.44 (17) |
C10—C9—C14—C15 | −179.90 (17) | C23—C24—C29—C30 | 0.8 (3) |
C8—C9—C14—C15 | −0.3 (3) | C27—C28—C29—C24 | −0.2 (3) |
C12—C13—C14—C9 | 0.1 (3) | C27—C28—C29—C30 | 179.82 (19) |
C12—C13—C14—C15 | 179.70 (18) | N6—N5—C30—C29 | −0.7 (3) |
N3—N2—C15—C14 | 0.1 (3) | C24—C29—C30—N5 | −0.6 (3) |
C9—C14—C15—N2 | 0.3 (3) | C28—C29—C30—N5 | 179.45 (18) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N2 | 1.01 (4) | 1.61 (4) | 2.613 (2) | 171 (4) |
O5—H5A···N5 | 1.02 (4) | 1.58 (4) | 2.589 (2) | 172 (3) |
C13—H13···O6 | 0.95 | 2.57 | 3.316 (3) | 136 |
C20—H20···O2 | 0.95 | 2.52 | 3.203 (3) | 129 |
C23—H23···O2i | 0.95 | 2.51 | 3.220 (2) | 132 |
C26—H26···O4ii | 0.95 | 2.53 | 3.441 (3) | 160 |
C27—H27···O7iii | 0.95 | 2.46 | 3.340 (3) | 155 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y+1, z+1; (iii) x, y+1, z. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C7H3.67ClNO4·C8H6.33N2 | C7H3.69ClNO4·C8H6.31N2 | C7H4ClNO4·C8H6N2 |
Mr | 331.71 | 331.71 | 331.71 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 190 | 190 | 190 |
a, b, c (Å) | 9.7764 (15), 12.0384 (14), 12.8889 (15) | 12.2261 (5), 16.9779 (7), 14.4537 (6) | 6.9197 (5), 14.4263 (12), 14.4750 (9) |
α, β, γ (°) | 81.491 (3), 72.328 (5), 88.390 (5) | 90, 106.8955 (13), 90 | 81.704 (2), 79.0781 (18), 85.647 (2) |
V (Å3) | 1429.2 (3) | 2870.7 (2) | 1402.20 (17) |
Z | 4 | 8 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.29 | 0.29 | 0.30 |
Crystal size (mm) | 0.40 × 0.28 × 0.18 | 0.35 × 0.35 × 0.30 | 0.40 × 0.18 × 0.06 |
|
Data collection |
Diffractometer | Rigaku R-AXIS RAPID II diffractometer | Rigaku R-AXIS RAPID II diffractometer | Rigaku R-AXIS RAPID II diffractometer |
Absorption correction | Numerical (NUMABS; Higashi, 1999) | Multi-scan (ABSCOR; Higashi, 1995) | Numerical (NUMABS; Higashi, 1999) |
Tmin, Tmax | 0.874, 0.949 | 0.790, 0.916 | 0.929, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 31515, 8271, 6364 | 60079, 8318, 6797 | 22476, 7849, 4765 |
Rint | 0.035 | 0.030 | 0.056 |
(sin θ/λ)max (Å−1) | 0.703 | 0.703 | 0.704 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.112, 1.10 | 0.042, 0.123, 1.07 | 0.057, 0.154, 0.99 |
No. of reflections | 8271 | 8318 | 7849 |
No. of parameters | 429 | 429 | 423 |
No. of restraints | 4 | 4 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.41 | 0.71, −0.41 | 0.53, −0.48 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N2 | 0.86 (3) | 1.71 (3) | 2.5715 (15) | 173 (3) |
O5—H5A···N5 | 0.84 (3) | 1.71 (3) | 2.5397 (17) | 170 (4) |
N2—H2···O1 | 0.89 (4) | 1.69 (4) | 2.5715 (15) | 172 (4) |
N5—H5B···O5 | 0.88 (5) | 1.66 (5) | 2.5397 (17) | 172 (6) |
C5—H5···O6 | 0.95 | 2.56 | 3.4174 (17) | 150 |
C8—H8···O5i | 0.95 | 2.58 | 3.3560 (17) | 140 |
C12—H12···O3ii | 0.95 | 2.56 | 3.4609 (15) | 158 |
C15—H15···O2 | 0.95 | 2.59 | 3.2204 (17) | 124 |
C20—H20···O4iii | 0.95 | 2.52 | 3.2207 (17) | 131 |
C21—H21···N3iii | 0.95 | 2.43 | 3.2952 (16) | 152 |
C23—H23···Cl2ii | 0.95 | 2.81 | 3.4707 (14) | 128 |
C23—H23···O3iv | 0.95 | 2.56 | 3.3131 (16) | 136 |
C28—H28···O2 | 0.95 | 2.42 | 3.3222 (17) | 158 |
Symmetry codes: (i) x−1, y+1, z; (ii) x, y, z−1; (iii) x+1, y−1, z; (iv) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N2 | 0.849 (19) | 1.719 (19) | 2.5655 (13) | 175 (3) |
O5—H5A···N5 | 0.864 (19) | 1.747 (19) | 2.6081 (13) | 174 (2) |
N2—H2···O1 | 0.88 (3) | 1.70 (3) | 2.5655 (13) | 171 (6) |
N5—H5B···O5 | 0.89 (3) | 1.73 (3) | 2.6081 (13) | 170 (6) |
C10—H10···O7i | 0.95 | 2.56 | 3.4371 (18) | 153 |
C15—H15···O2 | 0.95 | 2.52 | 3.1832 (16) | 127 |
C15—H15···O8ii | 0.95 | 2.54 | 3.1627 (17) | 124 |
C25—H25···O3 | 0.95 | 2.47 | 3.3602 (19) | 157 |
C30—H30···O6 | 0.95 | 2.57 | 3.2026 (16) | 124 |
Symmetry codes: (i) x+1, y, z; (ii) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N2 | 1.01 (4) | 1.61 (4) | 2.613 (2) | 171 (4) |
O5—H5A···N5 | 1.02 (4) | 1.58 (4) | 2.589 (2) | 172 (3) |
C13—H13···O6 | 0.95 | 2.57 | 3.316 (3) | 136 |
C20—H20···O2 | 0.95 | 2.52 | 3.203 (3) | 129 |
C23—H23···O2i | 0.95 | 2.51 | 3.220 (2) | 132 |
C26—H26···O4ii | 0.95 | 2.53 | 3.441 (3) | 160 |
C27—H27···O7iii | 0.95 | 2.46 | 3.340 (3) | 155 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y+1, z+1; (iii) x, y+1, z. |
Geometries of π–π stacking interactions for compounds (I)–(III) topCgI···CgJ, α, CgI-Perp and CgJ-Perp are,
respectively, the centroid-to-centroid distance between rings I and J (Å),
the inter-ring dihedral angle (°), the perpendicular distance of CgI
from ring J (Å) and the perpendicular distance of CgJ from ring I
(Å). Cg1, Cg2, Cg3, Cg4, Cg5 and
Cg6 are the centroids of the C1–C6, C16–C21, N2/N3/C8/C9/C14/C15,
C9–C14, N5/N6/C23/C24/C29/C30 and C24–C29 rings, respectively. |
| CgI···CgJ | α | CgI-Perp | CgJ-Perp |
(I) | | | | |
Cg1···Cg3i | 3.5926 (9) | 9.40 (6) | 3.3707 (5) | 3.4833 (5) |
Cg2···Cg6ii | 3.8215 (9) | 7.77 (6) | 3.4644 (5) | 3.5953 (6) |
(II) | | | | |
Cg1···Cg3iii | 3.6109 (7) | 4.35 (6) | 3.4477 (5) | 3.4910 (5) |
Cg1···Cg4iii | 3.7346 (7) | 3.20 (6) | 3.4567 (5) | 3.4135 (5) |
Cg2···Cg5iv | 3.8139 (7) | 7.07 (6) | 3.4937 (5) | 3.4622 (5) |
Cg2···Cg6iv | 3.7051 (7) | 6.55 (6) | 3.4873 (5) | 3.5827 (5) |
Cg3···Cg4v | 3.6714 (7) | 1.58 (6) | 3.4791 (5) | 3.4485 (5) |
(III) | | | | |
Cg1···Cg3vi | 3.7248 (12) | 0.78 (10) | 3.5065 (4) | 3.5066 (4) |
Cg1···Cg3vii | 3.5985 (12) | 0.78 (10) | 3.44488 (4) | 3.4722 (4) |
Cg1···Cg4vi | 3.6921 (13) | 1.29 (10) | 3.4319 (4) | 3.4669 (4) |
Cg1···Cg4vii | 3.6698 (13) | 1.29 (10) | 3.4485 (4) | 3.4336 (4) |
Cg2···Cg6viii | 3.6536 (12) | 0.89 (10) | 3.3383 (4) | 3.3225 (5) |
Cg2···Cg6v | 3.7211 (12) | 0.89 (10) | 3.4475 (5) | 3.4475 (5) |
Cg2···Cg7viii | 3.6812 (13) | 0.60 (10) | 3.4475 (5) | 3.4475 (5) |
Cg2···Cg7v | 3.6555 (13) | 0.60 (10) | 3.4475 (5) | 3.4475 (5) |
Symmetry codes: (i) -x + 1, -y + 2, -z + 1;
(ii) -x + 2, -y + 1, -z + 1;
(iii) -x + 1, y + 1/2, -z + 3/2;
(iv) -x, y - 1/2, -z + 3/2;
(v) -x + 1, -y + 1, -z + 1;
(vi) -x + 1, -y + 1, -z + 1;
(vii) -x + 2, -y + 1, -z;
(viii) -x, -y + 1, -z + 1. |
The hydrogen bonds formed between organic acids and organic bases vary from an O—H···N to an O···H—N type with increasing pKa or proton affinities (PA) of the bases, and at an appropriate ΔpKa [pKa(base) - pKa(acid)] the critical (inversion) point at 50% proton transfer occurs, in the region of which a short strong hydrogen bond with a broad single minimum potential-energy curve for the H atom or a double-minimum potential is expected (Jerzykiewicz et al., 1998; Kalenik et al., 1989; Steiner et al., 2001; Schmidtmann & Wilson, 2008; Gilli & Gilli, 2009). For the pyridine derivative–chloro- and nitro-substituted benzoic acid systems, we have shown that the three isomeric compounds, namely, quinoline–3-chloro-2-nitrobenzoic acid (1/1), (IV), quinoline–4-chloro-2-nitrobenzoic acid (1/1), (V), and quinoline–5-chloro-2-nitrobenzoic acid (1/1), (VI), are in a critical region and have a short double-well N···H···O hydrogen bond between the pyridine N atom and the carboxyl group (Gotoh & Ishida, 2009). The (N site):(O site) occupancies of the H atom are 0.39 (3):0.61 (3), 0.47 (3):0.53 (3) and 0.65 (3):0.35 (3) for (IV), (V) and (VI), respectively. The ΔpKa values are 3.08, 2.93 and 3.04, respectively, for (IV), (V) and (VI).
In this communication, we report the three isomeric compounds, phthalazine–3-chloro-2-nitrobenzoic acid (1/1), (I), phthalazine–4-chloro-2-nitrobenzoic acid (1/1), (II), and phthalazine–4-chloro-3-nitrobenzoic acid (1/1), (III), in order to extend our studies of the critical region and hydrogen bonding in the pyridine derivative–chloro- and nitro-substituted benzoic acid systems (Gotoh & Ishida, 2007, 2009). Phthalazine is a weaker base (pKa 3.47) than quinoline (pKa 4.90), and the ΔpKa values are 1.65, 1.50 and 0.12, respectively, for (I), (II) and (III).
The molecular structures of the three compounds, (I), (II) and (III), are shown in Figs. 1, 2 and 3, respectively. The asymmetric unit of each compound consists of two crystallographically independent chloronitrobenzoic acid–phthalazine units, where the two components are held together by a short hydrogen bond between one N atom of the base and the carboxyl group of the acid (Tables 1–3). The N···O distances are 2.5715 (15) and 2.5397 (17) Å for (I), 2.5655 (13) and 2.6081 (13) Å for (II), and 2.613 (2) and 2.589 (2) Å for (III). In the hydrogen bonds of (I) and (II), the H atoms were found to be disordered from difference Fourier maps (see supplementary figure), each of which shows two distinct peaks. The site occupancies refined to 0.35 (3):0.65 (3) (N2 site:O1 site) and 0.31 (3):0.69 (3) (N5 site:O5 site) for (I), and 0.32 (3):0.68 (3) (N2 site:O1 site) and 0.30 (3):0.70 (3) (N5 site:O5 site) for (II). On the other hand, in (III) no disordered H atom was observed, although one of the O···N distances [2.589 (2) Å] is shorter than the O5···N5 distance [2.6081 (3) Å] in (I); the H atoms in the hydrogen bonds are located at an O site (Table 3). In addition, a weak C—H···O interaction is observed in one hydrogen-bonded unit of (I) (C15—H15···O2; Table 2) and in each unit of (II) (C15—H15···O2 and C30—H30···O6; Table 3).
In the hydrogen-bonded units of (I) and (II), the benzene (C1–C6 or C16–C21) ring, the carboxyl (O1/C7/O2 or O5/C22/O6) plane and the phthalazine (N2/N3/C8–C15 or N5/N6/C23–C30) ring system are slightly twisted relative to each other. The dihedral angles between the C1–C6 and O1/C7/O2 planes, the C16–C21 and O5/C22/O6 planes, the O1/C7/O2 and N2/N3/C8–C15 planes, the O5/C22/O6 and N5/N6/C23–C30 planes, the C1–C6 and N2/N3/C8–C15 planes, and the C16–C21 and N5/N6/C23–C30 planes are 11.41 (14), 2.93 (15), 2.99 (14), 11.93 (15), 8.59 (5) and 9.02 (5)°, respectively, in (I), and 2.75 (17), 18.76 (17), 14.24 (16), 22.03 (16), 16.84 (5) and 9.56 (5)°, respectively, in (II). By contrast, in (III) these three planes are approximately coplanar with each other; the corresponding dihedral angles are 2.2 (2), 2.1 (3), 1.3 (2), 1.5 (3), 1.03 (8) and 0.66 (8)°. The planarity in both units of (III) may lead to a packing scheme accompanied by π–π stacking interactions in the crystal structure, as mentioned below.
The packing diagrams of the three compounds are given in Figs. 4–9. In (I), the two crystallographically independent hydrogen-bonded units are alternately arranged via C—H···O and C—H···N hydrogen bonds (C5—H5···O6, C8—H8···O5i, C20—H20···O4iii, C21—H21···N3iii and C28—H28···O2; details and symmetry codes in Table 1), forming a tape structure along the [110] direction (Fig. 4). These tapes are further linked via C—H···O and C—H···Cl hydrogen bonds (C12—H12···O3ii and C23—H23···Cl2ii; details and symmetry code in Table 1) into a sheet expanding parallel to the (110) plane (Fig. 5). Between these sheets, which are related to each other by an inversion centre, a C—H···O interaction (C23—H23···O3iv; see Table 1 for symmetry code) and π–π stacking interactions between the C1–C6 and N2/N3/C8/C9/C14/C15 rings, and the C16–C21 and C24–C29 rings, are observed. The centroid-to-centroid distances are in the range 3.5926 (9)–3.8215 (10) Å and the detailed geometries are given in Table 4.
In (II), there are fewer observable intermolecular hydrogen bonds than in (I), which may reflect the less dense crystal than (I). The two independent hydrogen-bonded units are alternately linked in a head-to-tail manner via C—H···O hydrogen bonds (C10—H10···O7i and C25—H25···O3; details and symmetry codes in Table 2), forming a tape structure along the a axis (Fig. 6). These tapes, related to each other by an inversion centre, are further linked by a weak C—H···O interaction (C15—H15···O8ii; details and symmetry code in Table 2) and a π–π stacking interaction between the N2/N3/C8/C9/C14/C15 and C9–C14 rings (Table 5), forming a double-tape structure (Fig. 7). Between the double-tapes other π–π stacking interactions are also observed (Table 4). The centroid-to-centroid distances are in the range 3.6109 (7)–3.8139 (7) Å.
In (III), the two hydrogen-bonded units are linked by C—H···O hydrogen bonds (C13—H13···O6, C20—H20···O2, C26—H26···O4ii and C27—H27···O7iii; details and symmetry codes in Table 3), forming a molecular sheet parallel to the (101) plane (Fig. 8). The arrangement of the two components in the sheet is similar to that in (I), but there are fewer hydrogen bonds than (I). On the other hand, between the sheets, related to each other by an inversion centre, relatively short π–π interactions between the acid rings and the phthalazine ring systems are observed, with centroid-to-centroid distances of 3.5985 (12)–3.7248 (12) Å (Table 4), and each hydrogen-bonded unit is stacked in a column in an antiparallel manner along the a axis (Fig. 9), resulting in the most dense crystal of the three compounds.
We have thus shown the existence of short double-well N···H···O hydrogen bonds in the structures of (I) and (II). Therefore, the critical region of chloronitrobenzoic acid–phthalazine systems may be expected around ΔpKa = 1.6, which is much smaller than ΔpKa = 2.93–3.08 found in quinoline–chloronitrobenzoic acid systems.