Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807030176/lh2440sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807030176/lh2440Isup2.hkl |
CCDC reference: 655043
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.005 Å
- Disorder in main residue
- R factor = 0.047
- wR factor = 0.097
- Data-to-parameter ratio = 13.9
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT430_ALERT_2_A Short Inter D...A Contact O6A .. O7A .. 2.40 Ang.
Author Response: This is an artefact of disorder of the nitro group containing these O atoms. |
Alert level B PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for N4
Alert level C CRYSC01_ALERT_1_C The word below has not been recognised as a standard identifier. very PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for S1 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for N1 PLAT301_ALERT_3_C Main Residue Disorder ......................... 6.00 Perc. PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5 PLAT480_ALERT_4_C Long H...A H-Bond Reported H1 .. O6A .. 2.74 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H1 .. O6B .. 2.77 Ang.
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.58 From the CIF: _reflns_number_total 4124 Count of symmetry unique reflns 2408 Completeness (_total/calc) 171.26% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1716 Fraction of Friedel pairs measured 0.713 Are heavy atom types Z>Si present yes
1 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 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 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For background, see: Bell et al. (1968); McDowell (1976); van de Waal & Feil (1977); Sun et al. (2004); Feinberg & Snyder (1975); Amaral et al. (2001).
For related literature, see: Herbstein & Kaftory (1976); Spek (2003).
Phenothiazine (0.9970 g, 0.05 mol) and picric acid (1.1468 g, 0.05 mol) were dissolved in chloroform separately and the solutions were mixed and stirred in a beaker. After one week, black needle shaped crystals were harvested and washed well with carbon tetrachloride and dried in a vacuum desiccator over P2O5. Dark, very soft, rods of the title compound were recrystallized from CHCl3. When the rods are crushed and smeared on a glass slide, a dark orange colour is apparent. They melt with decomposition at 393 K.
The N4 nitro group is disordered over two orientations with populations 0.54 (2):0.46 (2) (sum constraind to unity).
The O– and N-bound H atoms were located in difference maps and their positions were freely refined with Uiso(H) = 1.2Ueq(carrier).
The C-bound H atoms were geometrically placed (C—H = 0.93 Å) and refined as riding with Uiso(H) = 1.2Ueq(carrier).
Phenothiazine, C12H9NS, has a number of interesting features. It is a potent antibacterial agent (Feinberg & Snyder, 1975; Amaral et al., 2001) and shows remarkable redox properties, easily generating a stable C12H9NS+ radical cation that can be crystallized (Sun et al., 2004). Phenothiazine is polymorphic: as well as a P21 monoclinic form (Bell et al., 1968), a second modification shows unusual twinning, with the true P21/c monoclinic structure (van de Waal & Feil, 1977) masquerading as orthorhombic (McDowell, 1976).
Here we describe the synthesis and structure of the title compound a 1:1 adduct of neutral phenothiazine and picric acid (Fig. 1).
The phenothiazine molecule shows a rather small deviation from planarity [dihedral angle between the C1—C6 and C7—C12 rings = 11.81 (10)°] and the C—S distances [C1—S1 = 1.762 (3) Å, C12—S1 = 1.747 (3) Å] are consistent with the presence of the neutral molecule, rather than the radical cation (Sun et al., 2004), in (I). With respect to the mean plane of the C1—C6 ring, N1 and S1 deviate by 0.034 (5) and 0.122 (4) Å, respectively. For the C7—C12 ring, the equivalent deviations are 0.038 (5) and 0.028 (4) Å.
The significant variation of the C—C bond lengths around the picric acid aromatic ring can be related to the contributions of various resonance forms involving the nitro groups (Herbstein & Kaftory, 1976). The N4/O6/O7 nitro group is disordered over two orientations, with almost equal occupancies of 0.54 (2):0.46 (2). The dihedral angle between the disorder components is 78 (1)°. The other two nitro groups are almost co-planar with the benzene ring.
The two constituents of the title adduct interact by a weak, bifurcated N—H···(O,O) bond from phenothiazine to the disordered nitro group of the picric acid, with both disorder components resulting in similar H bond geometries. A typical (Herbstein & Kaftory, 1976) intramolecular O—H···O hydrogen bond occurs within the picric acid molecule. The disorder of the nitro group appears to be correlated with close intermolecular O···O contacts involving the picric acid molecules in the a unit-cell direction.
For background, see: Bell et al. (1968); McDowell (1976); van de Waal & Feil (1977); Sun et al. (2004); Feinberg & Snyder (1975); Amaral et al. (2001).
For related literature, see: Herbstein & Kaftory (1976); Spek (2003).
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: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
C12H9NS·C6H3N3O7 | Z = 4 |
Mr = 428.38 | F(000) = 880 |
Orthorhombic, P212121 | Dx = 1.582 Mg m−3 |
Hall symbol: P 2ac 2ab | Mo Kα radiation, λ = 0.71073 Å |
a = 7.2723 (7) Å | µ = 0.23 mm−1 |
b = 8.9800 (9) Å | T = 295 K |
c = 27.549 (3) Å | Rod, very dark orange |
V = 1799.1 (3) Å3 | 0.30 × 0.10 × 0.10 mm |
Bruker SMART1000 CCD diffractometer | 2300 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.044 |
Graphite monochromator | θmax = 27.6°, θmin = 4.3° |
ω scans | h = −9→9 |
11121 measured reflections | k = −7→11 |
4124 independent reflections | l = −35→35 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difmap (O-H and N-H) and geom (C-H) |
R[F2 > 2σ(F2)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.0411P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.89 | (Δ/σ)max = 0.001 |
4124 reflections | Δρmax = 0.18 e Å−3 |
296 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1716 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.12 (10) |
C12H9NS·C6H3N3O7 | V = 1799.1 (3) Å3 |
Mr = 428.38 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.2723 (7) Å | µ = 0.23 mm−1 |
b = 8.9800 (9) Å | T = 295 K |
c = 27.549 (3) Å | 0.30 × 0.10 × 0.10 mm |
Bruker SMART1000 CCD diffractometer | 2300 reflections with I > 2σ(I) |
11121 measured reflections | Rint = 0.044 |
4124 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.097 | Δρmax = 0.18 e Å−3 |
S = 0.89 | Δρmin = −0.17 e Å−3 |
4124 reflections | Absolute structure: Flack (1983), 1716 Friedel pairs |
296 parameters | Absolute structure parameter: 0.12 (10) |
0 restraints |
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) | |
C1 | 0.6577 (3) | 0.5800 (3) | 0.33533 (10) | 0.0512 (7) | |
C2 | 0.6216 (4) | 0.6559 (4) | 0.29269 (11) | 0.0675 (9) | |
H2A | 0.6261 | 0.6059 | 0.2632 | 0.081* | |
C3 | 0.5791 (5) | 0.8049 (5) | 0.29381 (15) | 0.0800 (10) | |
H3 | 0.5542 | 0.8554 | 0.2651 | 0.096* | |
C4 | 0.5735 (4) | 0.8792 (4) | 0.33742 (15) | 0.0767 (9) | |
H4 | 0.5426 | 0.9797 | 0.3382 | 0.092* | |
C5 | 0.6135 (4) | 0.8054 (3) | 0.37971 (12) | 0.0664 (9) | |
H5 | 0.6124 | 0.8572 | 0.4089 | 0.080* | |
C6 | 0.6555 (4) | 0.6544 (3) | 0.37959 (10) | 0.0530 (7) | |
C7 | 0.7653 (4) | 0.4400 (3) | 0.42768 (10) | 0.0531 (7) | |
C8 | 0.8347 (4) | 0.3950 (4) | 0.47242 (11) | 0.0662 (8) | |
H8 | 0.8314 | 0.4601 | 0.4987 | 0.079* | |
C9 | 0.9084 (5) | 0.2543 (5) | 0.47808 (14) | 0.0859 (11) | |
H9 | 0.9551 | 0.2256 | 0.5081 | 0.103* | |
C10 | 0.9133 (5) | 0.1569 (4) | 0.43996 (18) | 0.0901 (12) | |
H10 | 0.9614 | 0.0618 | 0.4440 | 0.108* | |
C11 | 0.8468 (5) | 0.2008 (3) | 0.39565 (13) | 0.0718 (9) | |
H11 | 0.8508 | 0.1347 | 0.3697 | 0.086* | |
C12 | 0.7738 (4) | 0.3412 (3) | 0.38875 (10) | 0.0543 (7) | |
N1 | 0.6881 (5) | 0.5818 (3) | 0.42300 (9) | 0.0762 (9) | |
H1 | 0.697 (5) | 0.631 (4) | 0.4475 (12) | 0.091* | |
S1 | 0.69464 (12) | 0.38660 (9) | 0.33075 (3) | 0.0718 (3) | |
C21 | 0.6419 (4) | 0.7960 (3) | 0.63036 (10) | 0.0486 (7) | |
C22 | 0.6397 (3) | 0.8755 (3) | 0.67412 (9) | 0.0457 (6) | |
C23 | 0.6772 (3) | 1.0262 (3) | 0.67629 (9) | 0.0458 (6) | |
H23 | 0.6704 | 1.0772 | 0.7056 | 0.055* | |
C24 | 0.7245 (3) | 1.0987 (3) | 0.63455 (8) | 0.0427 (6) | |
C25 | 0.7296 (4) | 1.0264 (3) | 0.59049 (9) | 0.0480 (7) | |
H25 | 0.7613 | 1.0774 | 0.5623 | 0.058* | |
C26 | 0.6870 (4) | 0.8776 (3) | 0.58903 (9) | 0.0478 (6) | |
N2 | 0.5977 (4) | 0.8011 (3) | 0.71962 (10) | 0.0636 (7) | |
N3 | 0.7712 (3) | 1.2571 (3) | 0.63615 (9) | 0.0562 (6) | |
N4 | 0.6920 (5) | 0.8059 (3) | 0.54120 (10) | 0.0714 (7) | |
O1 | 0.6062 (3) | 0.6509 (2) | 0.62691 (9) | 0.0744 (7) | |
H2 | 0.572 (5) | 0.623 (4) | 0.6589 (12) | 0.089* | |
O2 | 0.5599 (4) | 0.6672 (3) | 0.71851 (9) | 0.0902 (8) | |
O3 | 0.6021 (4) | 0.8721 (3) | 0.75672 (9) | 0.0945 (8) | |
O4 | 0.7424 (3) | 1.3233 (2) | 0.67420 (8) | 0.0773 (6) | |
O5 | 0.8380 (3) | 1.3140 (2) | 0.59996 (7) | 0.0734 (6) | |
O6A | 0.803 (3) | 0.8473 (16) | 0.5120 (4) | 0.118 (5) | 0.54 (2) |
O7A | 0.576 (2) | 0.7138 (16) | 0.5324 (2) | 0.116 (5) | 0.54 (2) |
O6B | 0.672 (3) | 0.8824 (10) | 0.5057 (3) | 0.109 (5) | 0.46 (2) |
O7B | 0.717 (4) | 0.6743 (8) | 0.5391 (4) | 0.126 (7) | 0.46 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0421 (15) | 0.0557 (17) | 0.0559 (18) | −0.0024 (13) | 0.0034 (14) | −0.0001 (14) |
C2 | 0.066 (2) | 0.083 (3) | 0.0535 (19) | −0.0080 (19) | −0.0008 (16) | 0.0050 (17) |
C3 | 0.080 (2) | 0.079 (3) | 0.081 (3) | −0.004 (2) | −0.008 (2) | 0.026 (2) |
C4 | 0.068 (2) | 0.0543 (19) | 0.108 (3) | 0.0069 (17) | −0.001 (2) | 0.013 (2) |
C5 | 0.070 (2) | 0.055 (2) | 0.074 (2) | 0.0141 (17) | 0.0044 (17) | −0.0071 (16) |
C6 | 0.0517 (18) | 0.0544 (19) | 0.0529 (17) | 0.0086 (14) | −0.0027 (14) | −0.0038 (13) |
C7 | 0.0487 (17) | 0.0538 (18) | 0.0568 (18) | 0.0030 (14) | 0.0045 (14) | 0.0016 (14) |
C8 | 0.0632 (19) | 0.076 (2) | 0.0595 (18) | 0.0041 (18) | 0.0086 (16) | 0.0085 (16) |
C9 | 0.076 (2) | 0.097 (3) | 0.085 (3) | 0.020 (2) | 0.018 (2) | 0.044 (3) |
C10 | 0.091 (3) | 0.063 (2) | 0.116 (3) | 0.021 (2) | 0.029 (3) | 0.031 (2) |
C11 | 0.073 (2) | 0.050 (2) | 0.092 (3) | −0.0019 (17) | 0.0130 (19) | 0.0046 (17) |
C12 | 0.0458 (16) | 0.0477 (17) | 0.0694 (19) | −0.0047 (14) | 0.0077 (14) | −0.0011 (14) |
N1 | 0.117 (2) | 0.0646 (19) | 0.0475 (16) | 0.0315 (19) | −0.0094 (16) | −0.0129 (12) |
S1 | 0.0836 (5) | 0.0639 (5) | 0.0680 (5) | 0.0109 (5) | −0.0123 (5) | −0.0211 (4) |
C21 | 0.0466 (17) | 0.0352 (16) | 0.0639 (19) | −0.0031 (13) | −0.0079 (13) | 0.0002 (13) |
C22 | 0.0460 (15) | 0.0444 (15) | 0.0465 (15) | 0.0011 (12) | −0.0011 (12) | 0.0046 (14) |
C23 | 0.0501 (15) | 0.0424 (15) | 0.0450 (15) | 0.0047 (13) | −0.0031 (13) | 0.0005 (12) |
C24 | 0.0480 (15) | 0.0330 (14) | 0.0469 (15) | 0.0007 (13) | −0.0051 (12) | −0.0012 (12) |
C25 | 0.0550 (17) | 0.0450 (16) | 0.0440 (15) | 0.0011 (14) | 0.0012 (13) | 0.0027 (12) |
C26 | 0.0520 (15) | 0.0441 (15) | 0.0473 (15) | 0.0047 (15) | −0.0048 (13) | −0.0096 (12) |
N2 | 0.0690 (16) | 0.0524 (18) | 0.0694 (18) | 0.0041 (14) | 0.0053 (14) | 0.0146 (14) |
N3 | 0.0658 (17) | 0.0432 (14) | 0.0597 (16) | −0.0010 (13) | −0.0043 (13) | −0.0022 (13) |
N4 | 0.095 (2) | 0.0576 (19) | 0.0618 (18) | 0.003 (2) | −0.004 (2) | −0.0163 (15) |
O1 | 0.0936 (16) | 0.0415 (13) | 0.0881 (15) | −0.0134 (12) | −0.0104 (13) | −0.0010 (11) |
O2 | 0.118 (2) | 0.0613 (16) | 0.0916 (17) | −0.0266 (14) | −0.0041 (15) | 0.0236 (13) |
O3 | 0.153 (2) | 0.0712 (15) | 0.0594 (14) | 0.0167 (17) | 0.0229 (15) | 0.0142 (13) |
O4 | 0.1124 (18) | 0.0496 (11) | 0.0700 (14) | −0.0081 (12) | 0.0071 (13) | −0.0163 (10) |
O5 | 0.1043 (18) | 0.0492 (12) | 0.0668 (13) | −0.0180 (12) | 0.0052 (13) | 0.0078 (10) |
O6A | 0.161 (11) | 0.120 (7) | 0.072 (4) | −0.036 (7) | 0.029 (6) | −0.025 (4) |
O7A | 0.160 (10) | 0.086 (7) | 0.100 (4) | −0.034 (7) | −0.029 (4) | −0.035 (4) |
O6B | 0.176 (13) | 0.101 (5) | 0.049 (4) | 0.027 (6) | −0.005 (5) | −0.011 (4) |
O7B | 0.235 (19) | 0.054 (4) | 0.088 (5) | 0.030 (5) | 0.002 (7) | −0.034 (3) |
C1—C2 | 1.383 (4) | C12—S1 | 1.747 (3) |
C1—C6 | 1.390 (3) | N1—H1 | 0.81 (3) |
C1—S1 | 1.762 (3) | C21—O1 | 1.332 (3) |
C2—C3 | 1.373 (5) | C21—C26 | 1.393 (4) |
C2—H2A | 0.9300 | C21—C22 | 1.401 (3) |
C3—C4 | 1.375 (5) | C22—C23 | 1.381 (3) |
C3—H3 | 0.9300 | C22—N2 | 1.453 (3) |
C4—C5 | 1.372 (4) | C23—C24 | 1.365 (3) |
C4—H4 | 0.9300 | C23—H23 | 0.9300 |
C5—C6 | 1.390 (4) | C24—C25 | 1.377 (3) |
C5—H5 | 0.9300 | C24—N3 | 1.463 (3) |
C6—N1 | 1.382 (3) | C25—C26 | 1.373 (4) |
C7—C8 | 1.392 (4) | C25—H25 | 0.9300 |
C7—C12 | 1.393 (4) | C26—N4 | 1.467 (3) |
C7—N1 | 1.398 (4) | N2—O3 | 1.205 (3) |
C8—C9 | 1.382 (5) | N2—O2 | 1.234 (3) |
C8—H8 | 0.9300 | N3—O5 | 1.221 (3) |
C9—C10 | 1.367 (5) | N3—O4 | 1.223 (3) |
C9—H9 | 0.9300 | N4—O7B | 1.197 (8) |
C10—C11 | 1.371 (5) | N4—O6B | 1.205 (9) |
C10—H10 | 0.9300 | N4—O6A | 1.197 (9) |
C11—C12 | 1.381 (4) | N4—O7A | 1.207 (7) |
C11—H11 | 0.9300 | O1—H2 | 0.95 (3) |
C2—C1—C6 | 120.4 (3) | C7—N1—H1 | 113 (2) |
C2—C1—S1 | 117.0 (2) | C12—S1—C1 | 102.40 (14) |
C6—C1—S1 | 122.6 (2) | O1—C21—C26 | 120.1 (3) |
C3—C2—C1 | 120.3 (3) | O1—C21—C22 | 123.9 (3) |
C3—C2—H2A | 119.9 | C26—C21—C22 | 116.0 (2) |
C1—C2—H2A | 119.9 | C23—C22—C21 | 122.3 (2) |
C2—C3—C4 | 120.0 (3) | C23—C22—N2 | 117.1 (2) |
C2—C3—H3 | 120.0 | C21—C22—N2 | 120.7 (2) |
C4—C3—H3 | 120.0 | C24—C23—C22 | 118.7 (2) |
C5—C4—C3 | 120.1 (3) | C24—C23—H23 | 120.6 |
C5—C4—H4 | 120.0 | C22—C23—H23 | 120.6 |
C3—C4—H4 | 120.0 | C23—C24—C25 | 121.6 (2) |
C4—C5—C6 | 121.1 (3) | C23—C24—N3 | 119.8 (2) |
C4—C5—H5 | 119.5 | C25—C24—N3 | 118.6 (2) |
C6—C5—H5 | 119.5 | C26—C25—C24 | 118.6 (2) |
N1—C6—C5 | 119.7 (3) | C26—C25—H25 | 120.7 |
N1—C6—C1 | 122.0 (3) | C24—C25—H25 | 120.7 |
C5—C6—C1 | 118.2 (3) | C25—C26—C21 | 122.8 (2) |
C8—C7—C12 | 118.7 (3) | C25—C26—N4 | 116.6 (3) |
C8—C7—N1 | 119.5 (3) | C21—C26—N4 | 120.6 (3) |
C12—C7—N1 | 121.8 (3) | O3—N2—O2 | 122.9 (3) |
C9—C8—C7 | 120.4 (3) | O3—N2—C22 | 118.8 (3) |
C9—C8—H8 | 119.8 | O2—N2—C22 | 118.3 (3) |
C7—C8—H8 | 119.8 | O5—N3—O4 | 124.4 (2) |
C10—C9—C8 | 120.6 (3) | O5—N3—C24 | 118.3 (2) |
C10—C9—H9 | 119.7 | O4—N3—C24 | 117.3 (2) |
C8—C9—H9 | 119.7 | O7B—N4—O6B | 122.8 (7) |
C9—C10—C11 | 119.4 (3) | O7B—N4—O6A | 99.9 (7) |
C9—C10—H10 | 120.3 | O6B—N4—O6A | 50.1 (4) |
C11—C10—H10 | 120.3 | O7B—N4—O7A | 54.6 (6) |
C10—C11—C12 | 121.4 (3) | O6B—N4—O7A | 98.1 (7) |
C10—C11—H11 | 119.3 | O6A—N4—O7A | 123.2 (7) |
C12—C11—H11 | 119.3 | O7B—N4—C26 | 118.7 (6) |
C11—C12—C7 | 119.5 (3) | O6B—N4—C26 | 118.5 (5) |
C11—C12—S1 | 117.8 (2) | O6A—N4—C26 | 119.0 (5) |
C7—C12—S1 | 122.8 (2) | O7A—N4—C26 | 117.7 (6) |
C6—N1—C7 | 125.3 (2) | C21—O1—H2 | 104 (2) |
C6—N1—H1 | 119 (2) | ||
C6—C1—C2—C3 | −1.5 (5) | C26—C21—C22—C23 | 0.9 (4) |
S1—C1—C2—C3 | 175.6 (3) | O1—C21—C22—N2 | 0.3 (4) |
C1—C2—C3—C4 | 0.4 (5) | C26—C21—C22—N2 | −178.9 (2) |
C2—C3—C4—C5 | 1.2 (5) | C21—C22—C23—C24 | −2.4 (4) |
C3—C4—C5—C6 | −1.7 (5) | N2—C22—C23—C24 | 177.4 (2) |
C4—C5—C6—N1 | −177.5 (3) | C22—C23—C24—C25 | 2.2 (4) |
C4—C5—C6—C1 | 0.6 (5) | C22—C23—C24—N3 | −177.8 (2) |
C2—C1—C6—N1 | 179.0 (3) | C23—C24—C25—C26 | −0.4 (4) |
S1—C1—C6—N1 | 2.1 (4) | N3—C24—C25—C26 | 179.6 (2) |
C2—C1—C6—C5 | 1.0 (4) | C24—C25—C26—C21 | −1.1 (4) |
S1—C1—C6—C5 | −175.9 (2) | C24—C25—C26—N4 | 179.2 (3) |
C12—C7—C8—C9 | −0.8 (4) | O1—C21—C26—C25 | −178.3 (3) |
N1—C7—C8—C9 | 178.8 (3) | C22—C21—C26—C25 | 0.9 (4) |
C7—C8—C9—C10 | −0.4 (5) | O1—C21—C26—N4 | 1.3 (4) |
C8—C9—C10—C11 | 1.0 (6) | C22—C21—C26—N4 | −179.5 (3) |
C9—C10—C11—C12 | −0.4 (6) | C23—C22—N2—O3 | −1.9 (4) |
C10—C11—C12—C7 | −0.8 (5) | C21—C22—N2—O3 | 177.9 (3) |
C10—C11—C12—S1 | 179.4 (3) | C23—C22—N2—O2 | 178.5 (3) |
C8—C7—C12—C11 | 1.4 (4) | C21—C22—N2—O2 | −1.7 (4) |
N1—C7—C12—C11 | −178.2 (3) | C23—C24—N3—O5 | 169.7 (2) |
C8—C7—C12—S1 | −178.9 (2) | C25—C24—N3—O5 | −10.3 (4) |
N1—C7—C12—S1 | 1.5 (4) | C23—C24—N3—O4 | −9.4 (4) |
C5—C6—N1—C7 | −167.0 (3) | C25—C24—N3—O4 | 170.6 (2) |
C1—C6—N1—C7 | 15.1 (5) | C25—C26—N4—O7B | 155.5 (15) |
C8—C7—N1—C6 | 163.4 (3) | C21—C26—N4—O7B | −24.2 (16) |
C12—C7—N1—C6 | −17.0 (5) | C25—C26—N4—O6B | −24.1 (14) |
C11—C12—S1—C1 | −169.1 (2) | C21—C26—N4—O6B | 156.2 (14) |
C7—C12—S1—C1 | 11.2 (3) | C25—C26—N4—O6A | 33.6 (14) |
C2—C1—S1—C12 | 169.9 (2) | C21—C26—N4—O6A | −146.0 (13) |
C6—C1—S1—C12 | −13.0 (3) | C25—C26—N4—O7A | −141.9 (11) |
O1—C21—C22—C23 | −179.9 (3) | C21—C26—N4—O7A | 38.5 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O6A | 0.81 (3) | 2.74 (4) | 3.520 (7) | 162 (3) |
N1—H1···O6B | 0.81 (3) | 2.77 (3) | 3.533 (8) | 157 (3) |
N1—H1···O7A | 0.81 (3) | 2.60 (3) | 3.339 (10) | 151 (3) |
N1—H1···O7B | 0.81 (3) | 2.56 (3) | 3.311 (11) | 156 (3) |
O1—H2···O2 | 0.95 (3) | 1.69 (3) | 2.550 (3) | 148 (3) |
Experimental details
Crystal data | |
Chemical formula | C12H9NS·C6H3N3O7 |
Mr | 428.38 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 295 |
a, b, c (Å) | 7.2723 (7), 8.9800 (9), 27.549 (3) |
V (Å3) | 1799.1 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.23 |
Crystal size (mm) | 0.30 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART1000 CCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11121, 4124, 2300 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.097, 0.89 |
No. of reflections | 4124 |
No. of parameters | 296 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.18, −0.17 |
Absolute structure | Flack (1983), 1716 Friedel pairs |
Absolute structure parameter | 0.12 (10) |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O6A | 0.81 (3) | 2.74 (4) | 3.520 (7) | 162 (3) |
N1—H1···O6B | 0.81 (3) | 2.77 (3) | 3.533 (8) | 157 (3) |
N1—H1···O7A | 0.81 (3) | 2.60 (3) | 3.339 (10) | 151 (3) |
N1—H1···O7B | 0.81 (3) | 2.56 (3) | 3.311 (11) | 156 (3) |
O1—H2···O2 | 0.95 (3) | 1.69 (3) | 2.550 (3) | 148 (3) |
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Phenothiazine, C12H9NS, has a number of interesting features. It is a potent antibacterial agent (Feinberg & Snyder, 1975; Amaral et al., 2001) and shows remarkable redox properties, easily generating a stable C12H9NS+ radical cation that can be crystallized (Sun et al., 2004). Phenothiazine is polymorphic: as well as a P21 monoclinic form (Bell et al., 1968), a second modification shows unusual twinning, with the true P21/c monoclinic structure (van de Waal & Feil, 1977) masquerading as orthorhombic (McDowell, 1976).
Here we describe the synthesis and structure of the title compound a 1:1 adduct of neutral phenothiazine and picric acid (Fig. 1).
The phenothiazine molecule shows a rather small deviation from planarity [dihedral angle between the C1—C6 and C7—C12 rings = 11.81 (10)°] and the C—S distances [C1—S1 = 1.762 (3) Å, C12—S1 = 1.747 (3) Å] are consistent with the presence of the neutral molecule, rather than the radical cation (Sun et al., 2004), in (I). With respect to the mean plane of the C1—C6 ring, N1 and S1 deviate by 0.034 (5) and 0.122 (4) Å, respectively. For the C7—C12 ring, the equivalent deviations are 0.038 (5) and 0.028 (4) Å.
The significant variation of the C—C bond lengths around the picric acid aromatic ring can be related to the contributions of various resonance forms involving the nitro groups (Herbstein & Kaftory, 1976). The N4/O6/O7 nitro group is disordered over two orientations, with almost equal occupancies of 0.54 (2):0.46 (2). The dihedral angle between the disorder components is 78 (1)°. The other two nitro groups are almost co-planar with the benzene ring.
The two constituents of the title adduct interact by a weak, bifurcated N—H···(O,O) bond from phenothiazine to the disordered nitro group of the picric acid, with both disorder components resulting in similar H bond geometries. A typical (Herbstein & Kaftory, 1976) intramolecular O—H···O hydrogen bond occurs within the picric acid molecule. The disorder of the nitro group appears to be correlated with close intermolecular O···O contacts involving the picric acid molecules in the a unit-cell direction.