Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038378/hb2493sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038378/hb2493Isup2.hkl |
CCDC reference: 660257
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.004 Å
- Disorder in main residue
- R factor = 0.037
- wR factor = 0.094
- Data-to-parameter ratio = 14.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.50 Ratio PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.61 Ratio PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N1 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N4 PLAT301_ALERT_3_C Main Residue Disorder ......................... 5.00 Perc. PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 23.10 Deg. O1 -N1 -O1' 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 35.90 Deg. O2' -N1 -O2 1.555 1.555 1.555
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 47
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 11 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
2-Nitro-N-(4-pyridyl)benzenesulfonamide was obtained according to the method of Yu & Li (2007). Colourless blocks of (I) were grown by natural evaporation of an aqueous HCl solution of the amide.
The N-bound H atoms were located in a difference map and refined with the constraint N—H = 0.90 (1) Å and their Uiso values were freely refined. The C-bound H atoms were positioned geometrically (C—H = 0.93 Å) and refined as riding atoms and the O-bound H atoms refined as riding in their as-found relative positions. The constraint Uiso(H) = 1.2Ueq(C or O) was applied. O1 and O2 are disordered over two positions and their occupancy ratio 0.57 (2):0.43 (2).
As part of our ongoing studies of N-sulfonated derivatives of 4-aminopyridine (Yu & Li, 2007), which contain both an acid and a base centre, we had planned to obtain the neutral zwitterionic crystal structure, but failed. Thus, the crystal structure of the semihydrated HCl title salt, (I), is reported herein.
The asymmetric unit of (I) contains two cations, two anions, and a single water molecule (Fig. 1). The short C—N distances [C7—N2 = 1.385 (2), C18—N5 = 1.382 (3) Å] and planar conformations [S1/H2A/N2/C7 0.0012, S2/H5A/N5/C18 0.0039 Å] indicate that N2 and N5 are sp2 hybridized to a large extent which can be related to tautomeric Lewis structures (Fig. 2). The benzene ring makes angles of 81.07 (12) and 74.80 (11)° with the pyridinium ring in the two asymmetric cations.
The crystal structure of (I) is stabilized by a series of intermolecular N—H···Cl, N—H···O and O—H···Cl hydrogen bonds (Table 1) with the water molecules making important contributions.
For related literature, see: Yu & Li (2007).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
C11H10N3O4S+·Cl−·0.5H2O | F(000) = 1336 |
Mr = 324.74 | Dx = 1.524 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5769 reflections |
a = 8.5250 (9) Å | θ = 2.3–26.3° |
b = 23.686 (3) Å | µ = 0.44 mm−1 |
c = 14.0227 (15) Å | T = 294 K |
β = 90.533 (2)° | Block, colourless |
V = 2831.4 (5) Å3 | 0.18 × 0.16 × 0.16 mm |
Z = 8 |
Bruker SMART 1000 CCD diffractometer | 5788 independent reflections |
Radiation source: fine-focus sealed tube | 4324 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω scans | θmax = 26.4°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −4→10 |
Tmin = 0.925, Tmax = 0.933 | k = −29→29 |
16156 measured reflections | l = −17→17 |
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: difmap and geom |
wR(F2) = 0.094 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0414P)2 + 0.8236P] where P = (Fo2 + 2Fc2)/3 |
5788 reflections | (Δ/σ)max = 0.002 |
405 parameters | Δρmax = 0.21 e Å−3 |
47 restraints | Δρmin = −0.42 e Å−3 |
C11H10N3O4S+·Cl−·0.5H2O | V = 2831.4 (5) Å3 |
Mr = 324.74 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.5250 (9) Å | µ = 0.44 mm−1 |
b = 23.686 (3) Å | T = 294 K |
c = 14.0227 (15) Å | 0.18 × 0.16 × 0.16 mm |
β = 90.533 (2)° |
Bruker SMART 1000 CCD diffractometer | 5788 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4324 reflections with I > 2σ(I) |
Tmin = 0.925, Tmax = 0.933 | Rint = 0.032 |
16156 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 47 restraints |
wR(F2) = 0.094 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.21 e Å−3 |
5788 reflections | Δρmin = −0.42 e Å−3 |
405 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1 | 1.03471 (6) | 0.62128 (2) | 0.81960 (4) | 0.03895 (14) | |
S2 | 0.48816 (6) | 0.39225 (2) | 0.71431 (4) | 0.03662 (14) | |
O1 | 1.1118 (19) | 0.7890 (4) | 0.6842 (10) | 0.121 (3) | 0.57 (2) |
O2 | 1.0429 (14) | 0.7078 (3) | 0.6537 (5) | 0.076 (2) | 0.57 (2) |
O1' | 1.1554 (13) | 0.7854 (5) | 0.7061 (11) | 0.081 (3) | 0.43 (2) |
O2' | 1.117 (2) | 0.7006 (3) | 0.6807 (11) | 0.084 (4) | 0.43 (2) |
O3 | 1.19801 (18) | 0.62714 (8) | 0.80367 (14) | 0.0666 (5) | |
O4 | 0.9807 (2) | 0.58378 (7) | 0.89101 (11) | 0.0608 (5) | |
O5 | 0.3534 (3) | 0.22474 (9) | 0.78593 (15) | 0.0826 (6) | |
O6 | 0.4843 (2) | 0.29184 (8) | 0.85010 (12) | 0.0700 (6) | |
O7 | 0.33755 (17) | 0.38247 (7) | 0.75352 (12) | 0.0521 (4) | |
O8 | 0.5093 (2) | 0.43636 (6) | 0.64641 (11) | 0.0495 (4) | |
N1 | 1.0708 (3) | 0.74400 (11) | 0.71537 (18) | 0.0639 (6) | |
N2 | 0.96220 (19) | 0.60102 (8) | 0.71765 (12) | 0.0375 (4) | |
N3 | 0.5063 (2) | 0.56738 (8) | 0.63932 (14) | 0.0424 (4) | |
N4 | 0.4476 (2) | 0.26339 (8) | 0.78224 (14) | 0.0469 (5) | |
N5 | 0.6065 (2) | 0.40375 (7) | 0.80458 (12) | 0.0359 (4) | |
N6 | 1.0631 (2) | 0.46045 (8) | 0.81160 (13) | 0.0410 (4) | |
C1 | 0.9552 (2) | 0.68867 (9) | 0.85036 (15) | 0.0378 (5) | |
C2 | 0.9868 (3) | 0.74034 (10) | 0.80580 (17) | 0.0464 (6) | |
C3 | 0.9357 (3) | 0.79051 (11) | 0.8440 (2) | 0.0681 (8) | |
H3 | 0.9585 | 0.8245 | 0.8139 | 0.082* | |
C4 | 0.8512 (4) | 0.79018 (14) | 0.9263 (3) | 0.0779 (9) | |
H4 | 0.8177 | 0.8241 | 0.9525 | 0.093* | |
C5 | 0.8156 (3) | 0.74069 (14) | 0.9704 (2) | 0.0696 (8) | |
H5 | 0.7561 | 0.7410 | 1.0256 | 0.084* | |
C6 | 0.8679 (3) | 0.68969 (11) | 0.93307 (16) | 0.0512 (6) | |
H6 | 0.8439 | 0.6561 | 0.9639 | 0.061* | |
C7 | 0.8072 (2) | 0.58892 (8) | 0.69514 (13) | 0.0298 (4) | |
C8 | 0.7726 (2) | 0.57271 (9) | 0.60155 (14) | 0.0368 (5) | |
H8 | 0.8523 | 0.5691 | 0.5571 | 0.044* | |
C9 | 0.6209 (3) | 0.56218 (10) | 0.57608 (16) | 0.0433 (5) | |
H9 | 0.5971 | 0.5513 | 0.5139 | 0.052* | |
C10 | 0.5367 (2) | 0.58106 (9) | 0.72950 (16) | 0.0417 (5) | |
H10 | 0.4544 | 0.5835 | 0.7724 | 0.050* | |
C11 | 0.6855 (2) | 0.59159 (9) | 0.76047 (14) | 0.0369 (5) | |
H11 | 0.7056 | 0.6004 | 0.8241 | 0.044* | |
C12 | 0.5541 (2) | 0.32936 (8) | 0.65867 (14) | 0.0337 (4) | |
C13 | 0.5231 (2) | 0.27450 (9) | 0.69050 (14) | 0.0374 (5) | |
C14 | 0.5657 (3) | 0.22817 (10) | 0.63775 (17) | 0.0490 (6) | |
H14 | 0.5416 | 0.1920 | 0.6590 | 0.059* | |
C15 | 0.6440 (3) | 0.23546 (11) | 0.55351 (18) | 0.0565 (7) | |
H15 | 0.6737 | 0.2041 | 0.5181 | 0.068* | |
C16 | 0.6784 (3) | 0.28830 (12) | 0.52147 (17) | 0.0574 (7) | |
H16 | 0.7331 | 0.2928 | 0.4649 | 0.069* | |
C17 | 0.6319 (3) | 0.33548 (10) | 0.57315 (15) | 0.0449 (5) | |
H17 | 0.6533 | 0.3714 | 0.5500 | 0.054* | |
C18 | 0.7598 (2) | 0.42265 (8) | 0.80218 (13) | 0.0315 (4) | |
C19 | 0.8394 (3) | 0.42707 (9) | 0.88944 (14) | 0.0401 (5) | |
H19 | 0.7899 | 0.4169 | 0.9457 | 0.048* | |
C20 | 0.9895 (3) | 0.44628 (10) | 0.89160 (16) | 0.0442 (5) | |
H20 | 1.0418 | 0.4496 | 0.9498 | 0.053* | |
C21 | 0.9919 (3) | 0.45634 (9) | 0.72684 (15) | 0.0413 (5) | |
H21 | 1.0458 | 0.4663 | 0.6720 | 0.050* | |
C22 | 0.8408 (2) | 0.43766 (9) | 0.71951 (14) | 0.0373 (5) | |
H22 | 0.7920 | 0.4349 | 0.6601 | 0.045* | |
Cl1 | 0.17769 (6) | 0.55281 (3) | 0.55557 (4) | 0.04462 (15) | |
Cl2 | 0.47855 (7) | 0.40063 (2) | 1.01277 (4) | 0.04624 (15) | |
H2A | 1.033 (2) | 0.5975 (9) | 0.6730 (12) | 0.046 (6)* | |
H3A | 0.4067 (15) | 0.5622 (11) | 0.6200 (18) | 0.067 (8)* | |
H5A | 0.566 (3) | 0.3957 (10) | 0.8619 (10) | 0.051 (7)* | |
H6A | 1.1596 (16) | 0.4746 (10) | 0.8193 (16) | 0.054 (7)* | |
O9 | 0.3370 (2) | 0.49762 (7) | 0.88677 (14) | 0.0659 (5) | |
H9A | 0.3647 | 0.5306 | 0.9052 | 0.079* | |
H9B | 0.3606 | 0.4712 | 0.9262 | 0.079* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0333 (3) | 0.0443 (3) | 0.0391 (3) | 0.0065 (2) | −0.0087 (2) | −0.0084 (2) |
S2 | 0.0367 (3) | 0.0363 (3) | 0.0368 (3) | 0.0019 (2) | −0.0038 (2) | −0.0046 (2) |
O1 | 0.151 (7) | 0.092 (4) | 0.120 (6) | −0.017 (4) | 0.020 (5) | 0.040 (4) |
O2 | 0.085 (5) | 0.082 (3) | 0.061 (3) | −0.002 (3) | 0.022 (3) | 0.007 (2) |
O1' | 0.059 (4) | 0.081 (4) | 0.102 (6) | −0.036 (3) | −0.004 (3) | 0.041 (3) |
O2' | 0.103 (7) | 0.073 (4) | 0.075 (5) | −0.007 (4) | 0.049 (5) | 0.002 (3) |
O3 | 0.0276 (8) | 0.0855 (13) | 0.0866 (13) | 0.0101 (9) | −0.0136 (8) | −0.0393 (11) |
O4 | 0.0938 (14) | 0.0483 (10) | 0.0400 (9) | 0.0097 (10) | −0.0093 (9) | 0.0078 (8) |
O5 | 0.0980 (16) | 0.0706 (13) | 0.0795 (14) | −0.0444 (12) | 0.0195 (12) | −0.0031 (11) |
O6 | 0.0959 (15) | 0.0742 (13) | 0.0398 (9) | −0.0324 (11) | 0.0064 (9) | −0.0037 (9) |
O7 | 0.0333 (8) | 0.0607 (10) | 0.0623 (10) | 0.0006 (8) | 0.0023 (7) | −0.0177 (8) |
O8 | 0.0672 (11) | 0.0386 (8) | 0.0426 (9) | 0.0057 (8) | −0.0135 (8) | 0.0036 (7) |
N1 | 0.0532 (14) | 0.0618 (15) | 0.0769 (17) | −0.0045 (13) | 0.0097 (12) | 0.0191 (14) |
N2 | 0.0243 (9) | 0.0565 (11) | 0.0318 (9) | −0.0019 (8) | 0.0041 (7) | −0.0112 (8) |
N3 | 0.0274 (9) | 0.0438 (11) | 0.0559 (12) | −0.0043 (8) | −0.0067 (9) | 0.0009 (9) |
N4 | 0.0528 (12) | 0.0417 (11) | 0.0463 (11) | −0.0074 (10) | 0.0006 (9) | 0.0040 (9) |
N5 | 0.0367 (10) | 0.0442 (10) | 0.0268 (9) | −0.0064 (8) | 0.0039 (7) | −0.0023 (8) |
N6 | 0.0338 (10) | 0.0394 (10) | 0.0498 (11) | −0.0044 (8) | 0.0013 (9) | 0.0022 (8) |
C1 | 0.0299 (11) | 0.0431 (12) | 0.0403 (11) | 0.0027 (9) | −0.0032 (9) | −0.0075 (10) |
C2 | 0.0359 (12) | 0.0466 (13) | 0.0568 (14) | −0.0003 (10) | −0.0005 (11) | −0.0015 (11) |
C3 | 0.0618 (17) | 0.0426 (15) | 0.100 (2) | 0.0033 (13) | −0.0060 (17) | −0.0067 (15) |
C4 | 0.072 (2) | 0.062 (2) | 0.099 (2) | 0.0185 (17) | −0.0040 (18) | −0.0375 (18) |
C5 | 0.0628 (18) | 0.085 (2) | 0.0612 (17) | 0.0119 (16) | 0.0072 (14) | −0.0286 (16) |
C6 | 0.0494 (14) | 0.0611 (16) | 0.0431 (13) | 0.0021 (12) | 0.0029 (11) | −0.0110 (12) |
C7 | 0.0256 (10) | 0.0310 (10) | 0.0327 (10) | 0.0015 (8) | −0.0002 (8) | −0.0005 (8) |
C8 | 0.0330 (11) | 0.0477 (12) | 0.0297 (10) | 0.0017 (10) | 0.0022 (8) | −0.0018 (9) |
C9 | 0.0418 (12) | 0.0504 (13) | 0.0375 (12) | −0.0028 (11) | −0.0080 (10) | −0.0012 (10) |
C10 | 0.0302 (11) | 0.0442 (12) | 0.0510 (13) | 0.0005 (10) | 0.0104 (10) | −0.0021 (10) |
C11 | 0.0327 (11) | 0.0458 (12) | 0.0324 (10) | 0.0001 (9) | 0.0054 (9) | −0.0075 (9) |
C12 | 0.0323 (10) | 0.0376 (11) | 0.0310 (10) | −0.0003 (9) | −0.0044 (8) | −0.0041 (8) |
C13 | 0.0374 (11) | 0.0390 (12) | 0.0358 (11) | −0.0026 (9) | −0.0053 (9) | −0.0015 (9) |
C14 | 0.0535 (14) | 0.0382 (12) | 0.0551 (15) | 0.0002 (11) | −0.0077 (12) | −0.0071 (11) |
C15 | 0.0609 (16) | 0.0526 (15) | 0.0560 (15) | 0.0090 (13) | −0.0011 (13) | −0.0214 (12) |
C16 | 0.0622 (16) | 0.0704 (18) | 0.0397 (13) | 0.0004 (14) | 0.0113 (12) | −0.0127 (12) |
C17 | 0.0533 (14) | 0.0478 (13) | 0.0337 (11) | −0.0057 (11) | 0.0024 (10) | −0.0022 (10) |
C18 | 0.0379 (11) | 0.0255 (10) | 0.0311 (10) | 0.0006 (8) | 0.0030 (8) | −0.0008 (8) |
C19 | 0.0441 (12) | 0.0486 (13) | 0.0278 (10) | −0.0071 (11) | 0.0031 (9) | 0.0021 (9) |
C20 | 0.0468 (13) | 0.0482 (13) | 0.0374 (12) | −0.0068 (11) | −0.0066 (10) | 0.0000 (10) |
C21 | 0.0430 (12) | 0.0410 (12) | 0.0400 (12) | −0.0004 (10) | 0.0097 (10) | 0.0038 (10) |
C22 | 0.0436 (12) | 0.0390 (12) | 0.0294 (10) | −0.0016 (10) | 0.0017 (9) | 0.0014 (9) |
Cl1 | 0.0289 (3) | 0.0648 (4) | 0.0403 (3) | −0.0078 (2) | 0.0057 (2) | −0.0085 (3) |
Cl2 | 0.0581 (4) | 0.0463 (3) | 0.0345 (3) | −0.0068 (3) | 0.0103 (2) | −0.0017 (2) |
O9 | 0.0635 (11) | 0.0456 (10) | 0.0881 (14) | −0.0060 (9) | −0.0275 (10) | −0.0018 (9) |
S1—O4 | 1.4186 (18) | C4—H4 | 0.9300 |
S1—O3 | 1.4187 (17) | C5—C6 | 1.391 (4) |
S1—N2 | 1.6248 (17) | C5—H5 | 0.9300 |
S1—C1 | 1.788 (2) | C6—H6 | 0.9300 |
S2—O7 | 1.4205 (16) | C7—C11 | 1.392 (3) |
S2—O8 | 1.4262 (16) | C7—C8 | 1.396 (3) |
S2—N5 | 1.6343 (17) | C8—C9 | 1.362 (3) |
S2—C12 | 1.775 (2) | C8—H8 | 0.9300 |
O1—N1 | 1.204 (7) | C9—H9 | 0.9300 |
O2—N1 | 1.240 (6) | C10—C11 | 1.360 (3) |
O1'—N1 | 1.225 (7) | C10—H10 | 0.9300 |
O2'—N1 | 1.206 (7) | C11—H11 | 0.9300 |
O5—N4 | 1.219 (2) | C12—C17 | 1.383 (3) |
O6—N4 | 1.205 (2) | C12—C13 | 1.400 (3) |
N1—C2 | 1.465 (3) | C13—C14 | 1.374 (3) |
N2—C7 | 1.385 (2) | C14—C15 | 1.373 (3) |
N2—H2A | 0.878 (10) | C14—H14 | 0.9300 |
N3—C10 | 1.328 (3) | C15—C16 | 1.363 (4) |
N3—C9 | 1.331 (3) | C15—H15 | 0.9300 |
N3—H3A | 0.897 (10) | C16—C17 | 1.392 (3) |
N4—C13 | 1.468 (3) | C16—H16 | 0.9300 |
N5—C18 | 1.382 (3) | C17—H17 | 0.9300 |
N5—H5A | 0.897 (10) | C18—C19 | 1.398 (3) |
N6—C21 | 1.333 (3) | C18—C22 | 1.401 (3) |
N6—C20 | 1.333 (3) | C19—C20 | 1.358 (3) |
N6—H6A | 0.894 (10) | C19—H19 | 0.9300 |
C1—C6 | 1.384 (3) | C20—H20 | 0.9300 |
C1—C2 | 1.401 (3) | C21—C22 | 1.365 (3) |
C2—C3 | 1.376 (3) | C21—H21 | 0.9300 |
C3—C4 | 1.366 (4) | C22—H22 | 0.9300 |
C3—H3 | 0.9300 | O9—H9A | 0.8562 |
C4—C5 | 1.361 (4) | O9—H9B | 0.8575 |
O4—S1—O3 | 119.87 (12) | C1—C6—C5 | 120.5 (3) |
O4—S1—N2 | 108.22 (10) | C1—C6—H6 | 119.8 |
O3—S1—N2 | 104.84 (10) | C5—C6—H6 | 119.8 |
O4—S1—C1 | 105.20 (10) | N2—C7—C11 | 123.75 (18) |
O3—S1—C1 | 108.99 (11) | N2—C7—C8 | 117.63 (18) |
N2—S1—C1 | 109.51 (10) | C11—C7—C8 | 118.62 (18) |
O7—S2—O8 | 119.89 (11) | C9—C8—C7 | 119.3 (2) |
O7—S2—N5 | 106.33 (9) | C9—C8—H8 | 120.4 |
O8—S2—N5 | 108.30 (9) | C7—C8—H8 | 120.4 |
O7—S2—C12 | 108.93 (10) | N3—C9—C8 | 120.6 (2) |
O8—S2—C12 | 106.19 (10) | N3—C9—H9 | 119.7 |
N5—S2—C12 | 106.53 (9) | C8—C9—H9 | 119.7 |
O1—N1—O2' | 120.7 (8) | N3—C10—C11 | 121.4 (2) |
O1—N1—O1' | 23.1 (9) | N3—C10—H10 | 119.3 |
O2'—N1—O1' | 116.4 (10) | C11—C10—H10 | 119.3 |
O1—N1—O2 | 114.4 (9) | C10—C11—C7 | 118.70 (19) |
O2'—N1—O2 | 35.9 (6) | C10—C11—H11 | 120.6 |
O1'—N1—O2 | 126.1 (8) | C7—C11—H11 | 120.6 |
O1—N1—C2 | 120.9 (7) | C17—C12—C13 | 117.85 (19) |
O2'—N1—C2 | 117.6 (5) | C17—C12—S2 | 116.70 (16) |
O1'—N1—C2 | 115.6 (8) | C13—C12—S2 | 125.25 (16) |
O2—N1—C2 | 118.1 (4) | C14—C13—C12 | 121.2 (2) |
C7—N2—S1 | 128.01 (14) | C14—C13—N4 | 116.7 (2) |
C7—N2—H2A | 118.6 (15) | C12—C13—N4 | 122.11 (18) |
S1—N2—H2A | 113.4 (15) | C15—C14—C13 | 119.7 (2) |
C10—N3—C9 | 121.26 (19) | C15—C14—H14 | 120.1 |
C10—N3—H3A | 119.8 (17) | C13—C14—H14 | 120.1 |
C9—N3—H3A | 118.9 (17) | C16—C15—C14 | 120.5 (2) |
O6—N4—O5 | 123.6 (2) | C16—C15—H15 | 119.8 |
O6—N4—C13 | 118.63 (19) | C14—C15—H15 | 119.8 |
O5—N4—C13 | 117.80 (19) | C15—C16—C17 | 120.2 (2) |
C18—N5—S2 | 127.75 (14) | C15—C16—H16 | 119.9 |
C18—N5—H5A | 117.5 (15) | C17—C16—H16 | 119.9 |
S2—N5—H5A | 114.8 (15) | C12—C17—C16 | 120.6 (2) |
C21—N6—C20 | 121.20 (19) | C12—C17—H17 | 119.7 |
C21—N6—H6A | 123.1 (15) | C16—C17—H17 | 119.7 |
C20—N6—H6A | 115.6 (15) | N5—C18—C19 | 117.04 (17) |
C6—C1—C2 | 117.7 (2) | N5—C18—C22 | 125.15 (18) |
C6—C1—S1 | 115.20 (18) | C19—C18—C22 | 117.82 (19) |
C2—C1—S1 | 126.65 (17) | C20—C19—C18 | 119.63 (19) |
C3—C2—C1 | 121.2 (2) | C20—C19—H19 | 120.2 |
C3—C2—N1 | 116.4 (2) | C18—C19—H19 | 120.2 |
C1—C2—N1 | 122.4 (2) | N6—C20—C19 | 121.1 (2) |
C4—C3—C2 | 119.7 (3) | N6—C20—H20 | 119.5 |
C4—C3—H3 | 120.2 | C19—C20—H20 | 119.5 |
C2—C3—H3 | 120.2 | N6—C21—C22 | 120.8 (2) |
C5—C4—C3 | 120.7 (3) | N6—C21—H21 | 119.6 |
C5—C4—H4 | 119.7 | C22—C21—H21 | 119.6 |
C3—C4—H4 | 119.7 | C21—C22—C18 | 119.47 (19) |
C4—C5—C6 | 120.2 (3) | C21—C22—H22 | 120.3 |
C4—C5—H5 | 119.9 | C18—C22—H22 | 120.3 |
C6—C5—H5 | 119.9 | H9A—O9—H9B | 114.1 |
O4—S1—N2—C7 | 50.4 (2) | C7—C8—C9—N3 | 0.2 (3) |
O3—S1—N2—C7 | 179.47 (19) | C9—N3—C10—C11 | 1.6 (3) |
C1—S1—N2—C7 | −63.7 (2) | N3—C10—C11—C7 | 1.3 (3) |
O7—S2—N5—C18 | −170.52 (18) | N2—C7—C11—C10 | 177.3 (2) |
O8—S2—N5—C18 | −40.4 (2) | C8—C7—C11—C10 | −3.2 (3) |
C12—S2—N5—C18 | 73.41 (19) | O7—S2—C12—C17 | 140.21 (16) |
O4—S1—C1—C6 | 1.64 (19) | O8—S2—C12—C17 | 9.81 (19) |
O3—S1—C1—C6 | −128.10 (18) | N5—S2—C12—C17 | −105.48 (17) |
N2—S1—C1—C6 | 117.74 (17) | O7—S2—C12—C13 | −34.6 (2) |
O4—S1—C1—C2 | 174.05 (19) | O8—S2—C12—C13 | −164.97 (17) |
O3—S1—C1—C2 | 44.3 (2) | N5—S2—C12—C13 | 79.74 (19) |
N2—S1—C1—C2 | −69.9 (2) | C17—C12—C13—C14 | −1.2 (3) |
C6—C1—C2—C3 | 1.4 (3) | S2—C12—C13—C14 | 173.48 (17) |
S1—C1—C2—C3 | −170.88 (19) | C17—C12—C13—N4 | 177.22 (19) |
C6—C1—C2—N1 | −176.7 (2) | S2—C12—C13—N4 | −8.1 (3) |
S1—C1—C2—N1 | 11.1 (3) | O6—N4—C13—C14 | 138.6 (2) |
O1—N1—C2—C3 | 10.3 (10) | O5—N4—C13—C14 | −39.6 (3) |
O2'—N1—C2—C3 | 179.7 (13) | O6—N4—C13—C12 | −39.9 (3) |
O1'—N1—C2—C3 | 35.9 (7) | O5—N4—C13—C12 | 141.8 (2) |
O2—N1—C2—C3 | −139.5 (7) | C12—C13—C14—C15 | 1.8 (3) |
O1—N1—C2—C1 | −171.6 (10) | N4—C13—C14—C15 | −176.7 (2) |
O2'—N1—C2—C1 | −2.2 (13) | C13—C14—C15—C16 | −0.6 (4) |
O1'—N1—C2—C1 | −145.9 (7) | C14—C15—C16—C17 | −1.2 (4) |
O2—N1—C2—C1 | 38.6 (8) | C13—C12—C17—C16 | −0.5 (3) |
C1—C2—C3—C4 | −0.7 (4) | S2—C12—C17—C16 | −175.69 (18) |
N1—C2—C3—C4 | 177.5 (3) | C15—C16—C17—C12 | 1.7 (4) |
C2—C3—C4—C5 | −0.7 (5) | S2—N5—C18—C19 | −177.51 (16) |
C3—C4—C5—C6 | 1.4 (5) | S2—N5—C18—C22 | 2.6 (3) |
C2—C1—C6—C5 | −0.7 (3) | N5—C18—C19—C20 | −178.9 (2) |
S1—C1—C6—C5 | 172.4 (2) | C22—C18—C19—C20 | 1.0 (3) |
C4—C5—C6—C1 | −0.6 (4) | C21—N6—C20—C19 | 0.1 (3) |
S1—N2—C7—C11 | −1.2 (3) | C18—C19—C20—N6 | −0.8 (3) |
S1—N2—C7—C8 | 179.33 (16) | C20—N6—C21—C22 | 0.3 (3) |
N2—C7—C8—C9 | −178.0 (2) | N6—C21—C22—C18 | 0.0 (3) |
C11—C7—C8—C9 | 2.5 (3) | N5—C18—C22—C21 | 179.3 (2) |
C10—N3—C9—C8 | −2.3 (3) | C19—C18—C22—C21 | −0.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···Cl1i | 0.88 (1) | 2.32 (1) | 3.1500 (17) | 157 (2) |
N3—H3A···Cl1 | 0.90 (1) | 2.16 (1) | 3.0472 (18) | 173 (2) |
N5—H5A···Cl2 | 0.90 (1) | 2.25 (1) | 3.1270 (17) | 164 (2) |
N6—H6A···O9i | 0.89 (1) | 1.86 (1) | 2.700 (2) | 156 (2) |
O9—H9A···Cl2ii | 0.86 | 2.39 | 3.1979 (18) | 157 |
O9—H9B···Cl2 | 0.86 | 2.29 | 3.1332 (19) | 167 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C11H10N3O4S+·Cl−·0.5H2O |
Mr | 324.74 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 8.5250 (9), 23.686 (3), 14.0227 (15) |
β (°) | 90.533 (2) |
V (Å3) | 2831.4 (5) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.44 |
Crystal size (mm) | 0.18 × 0.16 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.925, 0.933 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16156, 5788, 4324 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.094, 1.04 |
No. of reflections | 5788 |
No. of parameters | 405 |
No. of restraints | 47 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.21, −0.42 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···Cl1i | 0.878 (10) | 2.321 (13) | 3.1500 (17) | 157 (2) |
N3—H3A···Cl1 | 0.897 (10) | 2.155 (11) | 3.0472 (18) | 173 (2) |
N5—H5A···Cl2 | 0.897 (10) | 2.253 (11) | 3.1270 (17) | 164 (2) |
N6—H6A···O9i | 0.894 (10) | 1.858 (13) | 2.700 (2) | 156 (2) |
O9—H9A···Cl2ii | 0.86 | 2.39 | 3.1979 (18) | 157 |
O9—H9B···Cl2 | 0.86 | 2.29 | 3.1332 (19) | 167 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+2. |
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As part of our ongoing studies of N-sulfonated derivatives of 4-aminopyridine (Yu & Li, 2007), which contain both an acid and a base centre, we had planned to obtain the neutral zwitterionic crystal structure, but failed. Thus, the crystal structure of the semihydrated HCl title salt, (I), is reported herein.
The asymmetric unit of (I) contains two cations, two anions, and a single water molecule (Fig. 1). The short C—N distances [C7—N2 = 1.385 (2), C18—N5 = 1.382 (3) Å] and planar conformations [S1/H2A/N2/C7 0.0012, S2/H5A/N5/C18 0.0039 Å] indicate that N2 and N5 are sp2 hybridized to a large extent which can be related to tautomeric Lewis structures (Fig. 2). The benzene ring makes angles of 81.07 (12) and 74.80 (11)° with the pyridinium ring in the two asymmetric cations.
The crystal structure of (I) is stabilized by a series of intermolecular N—H···Cl, N—H···O and O—H···Cl hydrogen bonds (Table 1) with the water molecules making important contributions.