1-Ethyl-4-phenyl-1,5-benzodiazepine-2-thione

In the title compound, C₁₇H₁₆N₂S, the seven-membered ring adopts a boat conformation. The two aromatic rings are inclined at an angle of 34.7 (1)° to one another. The mol­ecules pack in helical chains running along the c-axis direction through C—H...S hydrogen bonds. These are further linked into layers parallel to (100) by weak C—H...π(ring) inter­actions. The structure was refined as a two-component inversion twin.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.045
• wR factor = 0.117
• Data-to-parameter ratio = 19.4

checkCIF/PLATON results

No syntax errors found



Alert level C
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.440
           From the CIF: _refine_ls_abs_structure_Flack_su    0.130
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00438 Ang.

Alert level G
PLAT033_ALERT_4_G Flack x Value Deviates > 3.0 * sigma from Zero .      0.440 Note
PLAT725_ALERT_2_G D-H     Calc     0.93000, Rep     0.97000 Dev...       0.04 Ang.
              C13    -H13           1.555   1.555 ............     #   38 Check
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         17 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          3 Note

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

   0 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
   1 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


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

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Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

1-Ethyl-4-phenyl-1,5-benzodiazepine-2-thione

Crystal data

C17H16N2S	Dx = 1.280 Mg m^−3
Mr = 280.38	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 2911 reflections
a = 8.4001 (8) Å	θ = 2.3–21.0°
b = 9.6239 (9) Å	µ = 0.21 mm^−1
c = 18.0037 (18) Å	T = 296 K
V = 1455.5 (2) Å^3	Plate, colourless
Z = 4	0.32 × 0.14 × 0.05 mm
F(000) = 592

Data collection

Bruker SMART APEX CCD diffractometer	3544 independent reflections
Radiation source: fine-focus sealed tube	2226 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
Detector resolution: 8.3333 pixels mm^-1	θmax = 28.3°, θmin = 2.3°
φ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −12→12
Tmin = 0.83, Tmax = 0.99	l = −23→23
13778 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.117	w = 1/[σ^2(Fo^2) + (0.0489P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
3544 reflections	Δρmax = 0.30 e Å^−3
183 parameters	Δρmin = −0.14 e Å^−3
0 restraints	Absolute structure: Refined as an inversion twin
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.44 (13)

Special details

Experimental. The diffraction data were collected in three sets of 363 frames (0.5° width in ω) at φ = 0, 120 and 240°. A scan time of 40 sec/frame was used.

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.

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 > 2sigma(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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.98 Å). All were included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms. Refined as a 2-component inversion twin.

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

	x	y	z	Uiso*/Ueq
S1	0.64858 (14)	0.84588 (9)	0.15748 (5)	0.0727 (3)
N1	0.8093 (3)	0.5444 (3)	0.32883 (13)	0.0490 (6)
N3	0.7707 (3)	0.5908 (2)	0.16493 (13)	0.0463 (6)
C1	0.7918 (3)	0.4569 (3)	0.19853 (16)	0.0458 (7)
C2	0.8075 (4)	0.3419 (3)	0.15237 (17)	0.0557 (8)
H2	0.8015	0.3544	0.1012	0.067*
C3	0.8313 (4)	0.2110 (3)	0.17968 (19)	0.0595 (9)
H3	0.8395	0.1358	0.1474	0.071*
C4	0.8432 (4)	0.1910 (4)	0.2555 (2)	0.0634 (9)
H4	0.8578	0.1024	0.2749	0.076*
C5	0.8330 (4)	0.3037 (3)	0.30166 (18)	0.0583 (9)
H5	0.8445	0.2902	0.3525	0.070*
C6	0.8063 (3)	0.4371 (3)	0.27555 (16)	0.0459 (7)
C7	0.7116 (3)	0.6452 (3)	0.32402 (14)	0.0419 (7)
C8	0.5878 (3)	0.6491 (3)	0.26317 (14)	0.0444 (7)
H8A	0.5381	0.5587	0.2577	0.053*
H8B	0.5060	0.7168	0.2748	0.053*
C9	0.6724 (4)	0.6887 (3)	0.19329 (15)	0.0463 (7)
C10	0.7243 (3)	0.7615 (3)	0.37858 (15)	0.0444 (7)
C11	0.6384 (4)	0.8824 (3)	0.37030 (17)	0.0600 (9)
H11	0.5703	0.8926	0.3299	0.072*
C12	0.6525 (5)	0.9886 (4)	0.4214 (2)	0.0727 (10)
H12	0.5944	1.0700	0.4150	0.087*
C13	0.7510 (5)	0.9753 (4)	0.4813 (2)	0.0733 (11)
H13	0.7582	1.0461	0.5162	0.088*
C14	0.8403 (5)	0.8549 (4)	0.48946 (16)	0.0657 (9)
H14	0.9092	0.8459	0.5296	0.079*
C15	0.8274 (4)	0.7485 (3)	0.43846 (15)	0.0551 (8)
H15	0.8878	0.6682	0.4442	0.066*
C16	0.8645 (4)	0.6230 (3)	0.09777 (15)	0.0586 (9)
H16A	0.9555	0.5611	0.0961	0.070*
H16B	0.9049	0.7171	0.1021	0.070*
C17	0.7743 (5)	0.6106 (4)	0.02465 (17)	0.0767 (12)
H17A	0.8460	0.6265	−0.0160	0.115*
H17B	0.6903	0.6782	0.0233	0.115*
H17C	0.7296	0.5191	0.0205	0.115*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.1136 (8)	0.0476 (5)	0.0567 (5)	0.0110 (5)	0.0115 (5)	0.0089 (4)
N1	0.0552 (15)	0.0485 (14)	0.0431 (13)	0.0009 (13)	−0.0045 (12)	0.0021 (11)
N3	0.0532 (14)	0.0441 (14)	0.0416 (13)	−0.0043 (11)	0.0024 (12)	−0.0025 (11)
C1	0.0447 (17)	0.0413 (15)	0.0515 (17)	−0.0010 (15)	−0.0002 (14)	−0.0027 (14)
C2	0.063 (2)	0.0537 (18)	0.0505 (16)	0.0001 (17)	0.0022 (16)	−0.0089 (16)
C3	0.0574 (19)	0.0484 (18)	0.073 (2)	0.0050 (16)	0.0027 (18)	−0.0126 (16)
C4	0.059 (2)	0.048 (2)	0.083 (2)	0.0093 (18)	0.002 (2)	0.0082 (16)
C5	0.061 (2)	0.057 (2)	0.0566 (19)	0.0122 (18)	−0.0054 (18)	0.0058 (15)
C6	0.0458 (17)	0.0451 (17)	0.0470 (17)	0.0041 (14)	−0.0011 (13)	−0.0007 (13)
C7	0.0493 (17)	0.0406 (15)	0.0357 (14)	−0.0022 (14)	0.0014 (12)	0.0042 (13)
C8	0.0477 (17)	0.0422 (16)	0.0434 (15)	−0.0016 (14)	−0.0009 (13)	−0.0019 (14)
C9	0.0539 (18)	0.0478 (17)	0.0373 (14)	−0.0023 (15)	−0.0051 (14)	−0.0025 (12)
C10	0.0495 (17)	0.0470 (17)	0.0367 (14)	−0.0047 (14)	0.0036 (14)	0.0024 (13)
C11	0.074 (2)	0.055 (2)	0.0511 (17)	0.0073 (18)	−0.0063 (16)	−0.0062 (14)
C12	0.088 (3)	0.059 (2)	0.071 (2)	0.010 (2)	0.000 (2)	−0.0149 (18)
C13	0.100 (3)	0.069 (3)	0.050 (2)	−0.017 (2)	0.008 (2)	−0.0172 (19)
C14	0.084 (2)	0.073 (2)	0.0404 (16)	−0.016 (2)	−0.0088 (17)	0.0011 (17)
C15	0.068 (2)	0.0562 (19)	0.0408 (15)	−0.0064 (18)	−0.0014 (17)	0.0056 (14)
C16	0.073 (2)	0.060 (2)	0.0430 (16)	−0.0084 (18)	0.0098 (15)	−0.0030 (15)
C17	0.116 (3)	0.071 (3)	0.0430 (18)	−0.006 (2)	0.007 (2)	−0.0023 (17)

Geometric parameters (Å, º)

S1—C9	1.657 (3)	C8—H8A	0.9700
N1—C7	1.274 (3)	C8—H8B	0.9700
N1—C6	1.409 (4)	C10—C11	1.377 (4)
N3—C9	1.353 (4)	C10—C15	1.389 (4)
N3—C1	1.434 (4)	C11—C12	1.380 (4)
N3—C16	1.476 (4)	C11—H11	0.9300
C1—C2	1.391 (4)	C12—C13	1.364 (5)
C1—C6	1.405 (4)	C12—H12	0.9300
C2—C3	1.367 (4)	C13—C14	1.388 (5)
C2—H2	0.9300	C13—H13	0.9300
C3—C4	1.383 (5)	C14—C15	1.380 (4)
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.368 (5)	C15—H15	0.9300
C4—H4	0.9300	C16—C17	1.524 (4)
C5—C6	1.386 (4)	C16—H16A	0.9700
C5—H5	0.9300	C16—H16B	0.9700
C7—C10	1.493 (4)	C17—H17A	0.9600
C7—C8	1.511 (4)	C17—H17B	0.9600
C8—C9	1.494 (4)	C17—H17C	0.9600
C7—N1—C6	120.0 (2)	N3—C9—S1	124.2 (2)
C9—N3—C1	122.8 (2)	C8—C9—S1	120.2 (2)
C9—N3—C16	119.3 (2)	C11—C10—C15	119.1 (3)
C1—N3—C16	117.9 (2)	C11—C10—C7	121.7 (3)
C2—C1—C6	118.3 (3)	C15—C10—C7	119.2 (3)
C2—C1—N3	118.4 (3)	C10—C11—C12	120.6 (3)
C6—C1—N3	123.3 (2)	C10—C11—H11	119.7
C3—C2—C1	122.2 (3)	C12—C11—H11	119.7
C3—C2—H2	118.9	C13—C12—C11	120.6 (3)
C1—C2—H2	118.9	C13—C12—H12	119.7
C2—C3—C4	119.6 (3)	C11—C12—H12	119.7
C2—C3—H3	120.2	C12—C13—C14	119.4 (3)
C4—C3—H3	120.2	C12—C13—H13	120.3
C5—C4—C3	119.0 (3)	C14—C13—H13	120.3
C5—C4—H4	120.5	C15—C14—C13	120.4 (3)
C3—C4—H4	120.5	C15—C14—H14	119.8
C4—C5—C6	122.6 (3)	C13—C14—H14	119.8
C4—C5—H5	118.7	C14—C15—C10	119.9 (3)
C6—C5—H5	118.7	C14—C15—H15	120.0
C5—C6—C1	118.3 (3)	C10—C15—H15	120.0
C5—C6—N1	116.4 (3)	N3—C16—C17	115.2 (3)
C1—C6—N1	125.0 (2)	N3—C16—H16A	108.5
N1—C7—C10	118.7 (2)	C17—C16—H16A	108.5
N1—C7—C8	120.8 (2)	N3—C16—H16B	108.5
C10—C7—C8	120.5 (2)	C17—C16—H16B	108.5
C9—C8—C7	106.8 (2)	H16A—C16—H16B	107.5
C9—C8—H8A	110.4	C16—C17—H17A	109.5
C7—C8—H8A	110.4	C16—C17—H17B	109.5
C9—C8—H8B	110.4	H17A—C17—H17B	109.5
C7—C8—H8B	110.4	C16—C17—H17C	109.5
H8A—C8—H8B	108.6	H17A—C17—H17C	109.5
N3—C9—C8	115.5 (2)	H17B—C17—H17C	109.5
C9—N3—C1—C2	141.7 (3)	C1—N3—C9—C8	0.8 (4)
C16—N3—C1—C2	−40.1 (4)	C16—N3—C9—C8	−177.4 (3)
C9—N3—C1—C6	−41.9 (4)	C1—N3—C9—S1	178.2 (2)
C16—N3—C1—C6	136.3 (3)	C16—N3—C9—S1	0.0 (4)
C6—C1—C2—C3	2.0 (5)	C7—C8—C9—N3	70.5 (3)
N3—C1—C2—C3	178.6 (3)	C7—C8—C9—S1	−107.0 (3)
C1—C2—C3—C4	−1.1 (5)	N1—C7—C10—C11	170.5 (3)
C2—C3—C4—C5	−1.0 (5)	C8—C7—C10—C11	−7.9 (4)
C3—C4—C5—C6	2.1 (6)	N1—C7—C10—C15	−8.3 (4)
C4—C5—C6—C1	−1.1 (5)	C8—C7—C10—C15	173.2 (3)
C4—C5—C6—N1	−175.8 (3)	C15—C10—C11—C12	−1.0 (5)
C2—C1—C6—C5	−0.9 (4)	C7—C10—C11—C12	−179.8 (3)
N3—C1—C6—C5	−177.3 (3)	C10—C11—C12—C13	−0.4 (6)
C2—C1—C6—N1	173.3 (3)	C11—C12—C13—C14	1.6 (6)
N3—C1—C6—N1	−3.1 (5)	C12—C13—C14—C15	−1.3 (6)
C7—N1—C6—C5	−142.0 (3)	C13—C14—C15—C10	−0.2 (5)
C7—N1—C6—C1	43.7 (4)	C11—C10—C15—C14	1.3 (5)
C6—N1—C7—C10	−176.3 (2)	C7—C10—C15—C14	−179.8 (3)
C6—N1—C7—C8	2.1 (4)	C9—N3—C16—C17	−80.5 (3)
N1—C7—C8—C9	−75.7 (3)	C1—N3—C16—C17	101.3 (3)
C10—C7—C8—C9	102.7 (3)

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···Cg1^i	0.97	2.92	3.810 (3)	154
C13—H13···S1^ii	0.97	2.86	3.706 (4)	152

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+3/2, −y+2, z+1/2.