Benzo[a][1,4]benzothia­zino[3,2-c]phenothia­zine

The title compound, C₂₂H₁₂N₂S₂, crystallizes in space group P2₁/c with four mol­ecules in the asymmetric unit. The heterocyclic mol­ecule is quasi-planar with a dihedral angle between the phenyl rings on the periphery of the mol­ecule of 1.73 (19)°. Short H...S (2.92 Å) and C—H...π [2.836 (3) Å] contacts are observed in the crystal with shorted π–π stacking distances of 3.438 (3) Å along the b axis. Surprisingly, and unlike a closely related material, this mol­ecule readily forms large crystals by sublimation and by slow evaporation from di­chloro­methane. The maximum absorbance in the UV-Vis spectrum is at 533 nm. Emission was measured upon excitation at 533 nm with a fluorescence λ_max of 658 nm and cutoff of 900 nm.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.047
• wR factor = 0.116
• Data-to-parameter ratio = 16.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      3.780 Check

Author Response: ... Acknowledged. VGY

Alert level G
PLAT333_ALERT_2_G Large Aver C6-Ring C-C Dist C1       -C10      .       1.44 Ang.
PLAT883_ALERT_1_G No Info/Value for _atom_sites_solution_primary .     Please Do !
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          2 Note
                1  0  0,   0  0  2,
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         14 Note
PLAT941_ALERT_3_G Average HKL Measurement Multiplicity ...........        3.3 Low
PLAT955_ALERT_1_G Reported (CIF) and Actual (FCF) Lmax Differ by .          1 Units
PLAT969_ALERT_5_G The 'Henn et al.' R-Factor-gap value ...........       2.49 Note
              Predicted wR2: Based on SigI   2  4.68 or SHELX Weight 11.32       
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         16 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   8 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

Benzo[a][1,4]benzothiazino[3,2-c]phenothiazine

Crystal data

C22H12N2S2	F(000) = 760
Mr = 368.46	Dx = 1.544 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.7365 (5) Å	Cell parameters from 2950 reflections
b = 3.8149 (2) Å	θ = 2.3–28.3°
c = 35.7260 (15) Å	µ = 0.34 mm^−1
β = 97.669 (2)°	T = 100 K
V = 1585.27 (13) Å^3	Plate, brown
Z = 4	0.25 × 0.06 × 0.01 mm

Data collection

Bruker PHOTON-III CPAD diffractometer	3341 reflections with I > 2σ(I)
Radiation source: micro-focus	Rint = 0.035
φ and ω scans	θmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −15→15
Tmin = 0.642, Tmax = 0.746	k = −3→5
13015 measured reflections	l = −47→43
3927 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.116	w = 1/[σ^2(Fo^2) + (0.0466P)^2 + 2.0952P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
3927 reflections	Δρmax = 0.52 e Å^−3
235 parameters	Δρmin = −0.56 e Å^−3

Special details

Experimental. Prof. M. Bader/ Prof. D. Alvacado / A. Bradley

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.54183 (4)	0.21127 (14)	0.30740 (2)	0.01608 (13)
S2	0.33242 (4)	0.20563 (14)	0.34472 (2)	0.01608 (13)
C1	0.55313 (16)	0.3928 (5)	0.35287 (5)	0.0133 (4)
C2	0.66054 (16)	0.5414 (5)	0.37063 (5)	0.0136 (4)
C3	0.66375 (16)	0.6660 (5)	0.40993 (5)	0.0130 (4)
C4	0.76638 (17)	0.7994 (6)	0.42939 (6)	0.0161 (4)
H4	0.833194	0.811698	0.417086	0.019*
C5	0.77115 (17)	0.9132 (6)	0.46631 (6)	0.0173 (4)
H5	0.841216	1.001428	0.479273	0.021*
C6	0.67283 (17)	0.8986 (6)	0.48468 (6)	0.0171 (4)
H6	0.676060	0.977146	0.510033	0.021*
C7	0.57106 (17)	0.7691 (5)	0.46564 (6)	0.0158 (4)
H7	0.504467	0.759988	0.478081	0.019*
C8	0.56486 (16)	0.6513 (5)	0.42822 (5)	0.0139 (4)
C9	0.45459 (16)	0.5176 (5)	0.40854 (5)	0.0136 (4)
C10	0.45630 (16)	0.3844 (5)	0.37040 (5)	0.0131 (4)
N1	0.75471 (14)	0.5822 (5)	0.35518 (5)	0.0152 (3)
C11	0.76197 (17)	0.4805 (5)	0.31800 (6)	0.0149 (4)
C12	0.86667 (17)	0.5499 (6)	0.30445 (6)	0.0174 (4)
H12	0.926848	0.662186	0.320482	0.021*
C13	0.88363 (19)	0.4577 (6)	0.26821 (6)	0.0204 (4)
H13	0.955212	0.505662	0.259611	0.025*
C14	0.79652 (19)	0.2954 (6)	0.24432 (6)	0.0215 (5)
H14	0.808693	0.231235	0.219467	0.026*
C15	0.69185 (19)	0.2267 (6)	0.25667 (6)	0.0186 (4)
H15	0.632088	0.117180	0.240201	0.022*
C16	0.67390 (17)	0.3185 (5)	0.29338 (6)	0.0158 (4)
N2	0.36590 (14)	0.5329 (5)	0.42687 (5)	0.0157 (4)
C17	0.25691 (17)	0.4184 (6)	0.41125 (6)	0.0160 (4)
C18	0.16828 (17)	0.4541 (6)	0.43387 (6)	0.0178 (4)
H18	0.185008	0.553665	0.458358	0.021*
C19	0.05728 (17)	0.3472 (6)	0.42117 (6)	0.0197 (4)
H19	−0.001115	0.371277	0.437018	0.024*
C20	0.03085 (18)	0.2041 (6)	0.38515 (6)	0.0210 (4)
H20	−0.045527	0.132118	0.376360	0.025*
C21	0.11667 (17)	0.1672 (6)	0.36219 (6)	0.0182 (4)
H21	0.098693	0.071365	0.337562	0.022*
C22	0.22938 (17)	0.2703 (5)	0.37509 (6)	0.0155 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0154 (2)	0.0172 (3)	0.0152 (2)	−0.0022 (2)	0.00051 (17)	−0.00166 (19)
S2	0.0136 (2)	0.0180 (3)	0.0160 (2)	−0.0023 (2)	−0.00017 (17)	−0.00226 (19)
C1	0.0148 (9)	0.0119 (9)	0.0125 (9)	0.0016 (8)	−0.0013 (7)	0.0015 (7)
C2	0.0138 (9)	0.0115 (9)	0.0147 (9)	0.0007 (8)	−0.0007 (7)	0.0013 (7)
C3	0.0130 (8)	0.0111 (9)	0.0140 (9)	0.0009 (7)	−0.0012 (7)	0.0011 (7)
C4	0.0131 (8)	0.0160 (10)	0.0187 (10)	0.0001 (8)	0.0001 (7)	−0.0001 (8)
C5	0.0158 (9)	0.0164 (10)	0.0184 (10)	−0.0021 (8)	−0.0028 (7)	−0.0016 (8)
C6	0.0196 (10)	0.0165 (10)	0.0145 (9)	0.0015 (8)	−0.0003 (7)	−0.0014 (8)
C7	0.0154 (9)	0.0156 (10)	0.0161 (9)	−0.0001 (8)	0.0015 (7)	0.0009 (8)
C8	0.0136 (9)	0.0123 (9)	0.0148 (9)	0.0013 (8)	−0.0012 (7)	0.0006 (7)
C9	0.0139 (9)	0.0110 (9)	0.0150 (9)	0.0000 (8)	−0.0011 (7)	0.0017 (7)
C10	0.0116 (8)	0.0104 (9)	0.0160 (9)	−0.0003 (7)	−0.0025 (7)	0.0014 (7)
N1	0.0137 (8)	0.0155 (8)	0.0160 (8)	−0.0002 (7)	0.0001 (6)	−0.0003 (7)
C11	0.0167 (9)	0.0118 (9)	0.0163 (9)	0.0019 (8)	0.0018 (7)	0.0019 (7)
C12	0.0173 (9)	0.0137 (10)	0.0215 (10)	−0.0024 (8)	0.0035 (8)	0.0015 (8)
C13	0.0223 (10)	0.0167 (10)	0.0239 (11)	0.0020 (9)	0.0089 (8)	0.0024 (9)
C14	0.0299 (11)	0.0182 (10)	0.0175 (10)	0.0045 (9)	0.0068 (8)	0.0023 (8)
C15	0.0231 (10)	0.0153 (10)	0.0162 (10)	0.0016 (9)	−0.0013 (8)	−0.0002 (8)
C16	0.0185 (9)	0.0116 (9)	0.0172 (9)	0.0008 (8)	0.0020 (7)	0.0036 (8)
N2	0.0146 (8)	0.0158 (9)	0.0162 (8)	−0.0006 (7)	0.0006 (6)	0.0002 (7)
C17	0.0139 (9)	0.0148 (10)	0.0189 (10)	0.0014 (8)	0.0007 (7)	0.0031 (8)
C18	0.0168 (9)	0.0182 (10)	0.0182 (10)	0.0006 (8)	0.0022 (7)	0.0001 (8)
C19	0.0149 (9)	0.0196 (11)	0.0254 (11)	0.0016 (8)	0.0052 (8)	0.0032 (9)
C20	0.0130 (9)	0.0235 (11)	0.0252 (11)	−0.0022 (9)	−0.0021 (8)	0.0041 (9)
C21	0.0162 (9)	0.0168 (10)	0.0204 (10)	−0.0020 (8)	−0.0022 (7)	0.0001 (8)
C22	0.0139 (8)	0.0132 (10)	0.0187 (9)	0.0017 (8)	0.0002 (7)	0.0028 (8)

Geometric parameters (Å, º)

S1—C16	1.740 (2)	C11—C12	1.405 (3)
S1—C1	1.755 (2)	C11—C16	1.407 (3)
S2—C22	1.747 (2)	C12—C13	1.382 (3)
S2—C10	1.751 (2)	C12—H12	0.9500
C1—C10	1.369 (3)	C13—C14	1.387 (3)
C1—C2	1.449 (3)	C13—H13	0.9500
C2—N1	1.309 (2)	C14—C15	1.385 (3)
C2—C3	1.478 (3)	C14—H14	0.9500
C3—C4	1.404 (3)	C15—C16	1.400 (3)
C3—C8	1.407 (3)	C15—H15	0.9500
C4—C5	1.382 (3)	N2—C17	1.396 (3)
C4—H4	0.9500	C17—C18	1.406 (3)
C5—C6	1.403 (3)	C17—C22	1.407 (3)
C5—H5	0.9500	C18—C19	1.383 (3)
C6—C7	1.384 (3)	C18—H18	0.9500
C6—H6	0.9500	C19—C20	1.394 (3)
C7—C8	1.403 (3)	C19—H19	0.9500
C7—H7	0.9500	C20—C21	1.389 (3)
C8—C9	1.479 (3)	C20—H20	0.9500
C9—N2	1.303 (2)	C21—C22	1.398 (3)
C9—C10	1.457 (3)	C21—H21	0.9500
N1—C11	1.398 (3)
C16—S1—C1	102.32 (10)	C12—C11—C16	118.08 (18)
C22—S2—C10	102.41 (10)	C13—C12—C11	121.1 (2)
C10—C1—C2	122.38 (18)	C13—C12—H12	119.4
C10—C1—S1	116.71 (15)	C11—C12—H12	119.4
C2—C1—S1	120.91 (14)	C12—C13—C14	120.25 (19)
N1—C2—C1	126.58 (18)	C12—C13—H13	119.9
N1—C2—C3	116.52 (17)	C14—C13—H13	119.9
C1—C2—C3	116.89 (16)	C15—C14—C13	120.1 (2)
C4—C3—C8	119.40 (18)	C15—C14—H14	120.0
C4—C3—C2	119.92 (17)	C13—C14—H14	120.0
C8—C3—C2	120.68 (17)	C14—C15—C16	120.1 (2)
C5—C4—C3	120.62 (18)	C14—C15—H15	119.9
C5—C4—H4	119.7	C16—C15—H15	119.9
C3—C4—H4	119.7	C15—C16—C11	120.35 (19)
C4—C5—C6	120.19 (19)	C15—C16—S1	117.50 (16)
C4—C5—H5	119.9	C11—C16—S1	122.11 (15)
C6—C5—H5	119.9	C9—N2—C17	122.41 (17)
C7—C6—C5	119.59 (19)	N2—C17—C18	116.65 (18)
C7—C6—H6	120.2	N2—C17—C22	125.35 (18)
C5—C6—H6	120.2	C18—C17—C22	118.00 (18)
C6—C7—C8	120.95 (18)	C19—C18—C17	121.3 (2)
C6—C7—H7	119.5	C19—C18—H18	119.3
C8—C7—H7	119.5	C17—C18—H18	119.3
C7—C8—C3	119.24 (18)	C18—C19—C20	120.15 (19)
C7—C8—C9	119.63 (17)	C18—C19—H19	119.9
C3—C8—C9	121.12 (17)	C20—C19—H19	119.9
N2—C9—C10	126.69 (18)	C21—C20—C19	119.70 (19)
N2—C9—C8	116.92 (17)	C21—C20—H20	120.1
C10—C9—C8	116.40 (16)	C19—C20—H20	120.1
C1—C10—C9	122.38 (17)	C20—C21—C22	120.4 (2)
C1—C10—S2	116.83 (15)	C20—C21—H21	119.8
C9—C10—S2	120.79 (14)	C22—C21—H21	119.8
C2—N1—C11	122.00 (17)	C21—C22—C17	120.46 (18)
N1—C11—C12	116.25 (18)	C21—C22—S2	117.29 (16)
N1—C11—C16	125.67 (18)	C17—C22—S2	122.25 (15)
C16—S1—C1—C10	173.32 (16)	C1—C2—N1—C11	−0.2 (3)
C16—S1—C1—C2	−7.01 (19)	C3—C2—N1—C11	−178.92 (17)
C10—C1—C2—N1	−175.1 (2)	C2—N1—C11—C12	177.87 (19)
S1—C1—C2—N1	5.3 (3)	C2—N1—C11—C16	−1.7 (3)
C10—C1—C2—C3	3.7 (3)	N1—C11—C12—C13	179.44 (19)
S1—C1—C2—C3	−175.95 (14)	C16—C11—C12—C13	−0.9 (3)
N1—C2—C3—C4	−3.8 (3)	C11—C12—C13—C14	0.4 (3)
C1—C2—C3—C4	177.34 (18)	C12—C13—C14—C15	0.4 (3)
N1—C2—C3—C8	176.48 (19)	C13—C14—C15—C16	−0.5 (3)
C1—C2—C3—C8	−2.4 (3)	C14—C15—C16—C11	−0.1 (3)
C8—C3—C4—C5	0.5 (3)	C14—C15—C16—S1	−177.97 (17)
C2—C3—C4—C5	−179.23 (19)	N1—C11—C16—C15	−179.62 (19)
C3—C4—C5—C6	−0.5 (3)	C12—C11—C16—C15	0.8 (3)
C4—C5—C6—C7	0.1 (3)	N1—C11—C16—S1	−1.9 (3)
C5—C6—C7—C8	0.2 (3)	C12—C11—C16—S1	178.56 (16)
C6—C7—C8—C3	−0.1 (3)	C1—S1—C16—C15	−176.64 (16)
C6—C7—C8—C9	−179.42 (19)	C1—S1—C16—C11	5.5 (2)
C4—C3—C8—C7	−0.2 (3)	C10—C9—N2—C17	−0.2 (3)
C2—C3—C8—C7	179.50 (18)	C8—C9—N2—C17	179.35 (18)
C4—C3—C8—C9	179.07 (19)	C9—N2—C17—C18	−179.1 (2)
C2—C3—C8—C9	−1.2 (3)	C9—N2—C17—C22	1.2 (3)
C7—C8—C9—N2	3.3 (3)	N2—C17—C18—C19	−179.7 (2)
C3—C8—C9—N2	−176.02 (19)	C22—C17—C18—C19	0.1 (3)
C7—C8—C9—C10	−177.15 (18)	C17—C18—C19—C20	−0.7 (3)
C3—C8—C9—C10	3.5 (3)	C18—C19—C20—C21	0.4 (3)
C2—C1—C10—C9	−1.3 (3)	C19—C20—C21—C22	0.5 (3)
S1—C1—C10—C9	178.35 (15)	C20—C21—C22—C17	−1.1 (3)
C2—C1—C10—S2	178.49 (15)	C20—C21—C22—S2	178.64 (17)
S1—C1—C10—S2	−1.8 (2)	N2—C17—C22—C21	−179.5 (2)
N2—C9—C10—C1	177.2 (2)	C18—C17—C22—C21	0.8 (3)
C8—C9—C10—C1	−2.3 (3)	N2—C17—C22—S2	0.8 (3)
N2—C9—C10—S2	−2.6 (3)	C18—C17—C22—S2	−178.90 (16)
C8—C9—C10—S2	177.87 (14)	C10—S2—C22—C21	177.42 (17)
C22—S2—C10—C1	−176.21 (16)	C10—S2—C22—C17	−2.8 (2)
C22—S2—C10—C9	3.60 (18)