Thio­nordazepam: strong inter­molecular N—H...N hydrogen-bonded chains

In the title compound, 7-chloro-1,3-dihydro-5-phenyl-2H-1,4-benzodiazepine-2-thione, C₁₅H₁₁ClN₂S, the central seven-membered diazepinethione ring adopts a boat conformation. The dihedral angle between the planes of the aromatic rings is 63.7 (1)°. The crystal packing is determined by strong N—H...N hydrogen bonds, generating a one-dimensional chain along [001].

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.062
• wR factor = 0.142
• Data-to-parameter ratio = 17.3

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    0.420
           From the CIF: _refine_ls_abs_structure_Flack_su    0.110
PLAT033_ALERT_2_C Flack Parameter Value Deviates from Zero .......       0.42
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          8
PLAT731_ALERT_1_C Bond    Calc     0.88(4), Rep   0.876(10) ......       4.00 su-Rat
              N1   -H1      1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.88(4), Rep   0.880(10) ......       4.00 su-Rat
              N1   -H1      1.555   1.555

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           27.37
           From the CIF: _reflns_number_total               3021
           Count of symmetry unique reflns         1737
           Completeness (_total/calc)            173.92%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1284
           Fraction of Friedel pairs measured     0.739
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   2 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999) and PARST (Nardelli, 1995).

7-Chloro-1,3-dihydro-5-phenyl-2H-1,4-benzodiazepin-2-thione

Crystal data

C15H11ClN2S	Dx = 1.317 Mg m^−3
Mr = 286.77	Melting point: 489 K
Orthorhombic, Pnc2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 -2bc	Cell parameters from 1456 reflections
a = 9.993 (2) Å	θ = 5–35°
b = 14.223 (3) Å	µ = 0.40 mm^−1
c = 10.175 (2) Å	T = 293 K
V = 1446.2 (5) Å^3	Thin-plate, colourless
Z = 4	0.5 × 0.3 × 0.08 mm
F(000) = 592

Data collection

Bruker SMART CCD area-detector diffractometer	3021 independent reflections
Radiation source: fine-focus sealed tube	1505 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
ω scans	θmax = 27.4°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→12
Tmin = 0.865, Tmax = 0.972	k = −18→17
10960 measured reflections	l = −13→13

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)] = 0.062	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.142	w = 1/[σ^2(Fo^2) + (0.0619P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
3021 reflections	Δρmax = 0.25 e Å^−3
175 parameters	Δρmin = −0.15 e Å^−3
2 restraints	Absolute structure: Flack (1983), 1358 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.42 (11)

Special details

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.

Weighted least-squares planes through the starred atoms (Nardelli, Musatti, Domiano & Andreetti Ric·Sci.(1965),15(II—A),807). Equation of the plane: m1*X+m2*Y+m3*Z=d

Plane 1 m1 = 0.13757(0.00154) m2 = -0.98122(0.00042) m3 = -0.13522(0.00196) D = -9.08012(0.00790) Atom d s d/s (d/s)**2 C9 * -0.0215 0.0040 - 5.369 28.824 C10 * 0.0152 0.0037 4.079 16.637 C11 * 0.0148 0.0047 3.143 9.879 C12 * -0.0059 0.0057 - 1.026 1.052 C13 * -0.0214 0.0055 - 3.918 15.354 C14 * -0.0078 0.0049 - 1.580 2.496 C15 * 0.0147 0.0043 3.424 11.723 C5 0.7465 0.0040 186.903 34932.703 N2 - 0.7383 0.0041 - 179.810 32331.744 ============ Sum((d/s)**2) for starred atoms 85.965 Chi-squared at 95% for 4 degrees of freedom: 9.49 The group of atoms deviates significantly from planarity

Plane 2 m1 = 0.78728(0.00048) m2 = 0.59107(0.00043) m3 = -0.17559(0.00138) D = 6.05288(0.00355) Atom d s d/s (d/s)**2 Cl1 * 0.0054 0.0017 3.233 10.454 C1 * -0.0144 0.0046 - 3.146 9.895 C2 * -0.0202 0.0051 - 3.948 15.590 C3 * -0.0127 0.0049 - 2.616 6.842 C4 * -0.0238 0.0042 - 5.672 32.169 C5 * -0.0219 0.0038 - 5.705 32.544 C6 * 0.0001 0.0040 0.031 0.001 N1 * 0.0344 0.0036 9.608 92.312 C9 * 0.0042 0.0044 0.959 0.920 C7 - 0.6012 0.0043 - 138.282 19121.834 C10 0.7792 0.0042 183.675 33736.688 ============ Sum((d/s)**2) for starred atoms 200.726 Chi-squared at 95% for 6 degrees of freedom: 12.60 The group of atoms deviates significantly from planarity

Plane 3 m1 = -0.73679(0.00197) m2 = -0.46525(0.00490) m3 = -0.49060(0.00611) D = -5.88482(0.03869) Atom d s d/s (d/s)**2 C4 * 0.0000 0.0044 0.002 0.000 N1 * 0.0000 0.0036 - 0.006 0.000 C7 * 0.0000 0.0044 0.002 0.000 H1 * 0.0010 0.0382 0.025 0.001 S1 - 0.0509 0.0016 - 31.624 1000.085 C3 0.7619 0.0048 157.498 24805.602 ============ Sum((d/s)**2) for starred atoms 0.001 Chi-squared at 95% for 1 degrees of freedom: 3.84 The group of atoms does not deviate significantly from planarity

Plane 4 m1 = -0.40906(0.00619) m2 = 0.69283(0.00489) m3 = 0.59385(0.00241) D = 8.93762(0.04243) Atom d s d/s (d/s)**2 C8 * 0.0000 0.0053 0.000 0.000 N2 * 0.0000 0.0038 0.000 0.000 C7 * 0.0000 0.0049 0.000 0.000 C9 - 1.0832 0.0042 - 255.959 65514.773 N1 - 1.1572 0.0036 - 324.511 105307.344 ============ Sum((d/s)**2) for starred atoms 0.000

Plane 5 m1 = -0.48854(0.00252) m2 = -0.86124(0.00127) m3 = -0.13997(0.00202) D = -9.19395(0.01436) Atom d s d/s (d/s)**2 N1 * 0.0046 0.0036 1.276 1.628 N2 * 0.0073 0.0040 1.833 3.360 C7 * -0.0103 0.0048 - 2.127 4.523 C9 * -0.0065 0.0041 - 1.562 2.441 C8 0.7519 0.0053 143.126 20484.998 C4 0.6376 0.0042 153.217 23475.359 ============ Sum((d/s)**2) for starred atoms 11.952 Chi-squared at 95% for 1 degrees of freedom: 3.84 The group of atoms deviates significantly from planarity

Plane 6 m1 = 0.80468(0.00133) m2 = 0.56282(0.00234) m3 = -0.18901(0.00245) D = 5.78553(0.02423) Atom d s d/s (d/s)**2 C4 * -0.0078 0.0042 - 1.851 3.426 C5 * 0.0063 0.0038 1.648 2.717 N1 * 0.0027 0.0036 0.757 0.573 C9 * -0.0039 0.0044 - 0.885 0.783 C7 - 0.6704 0.0043 - 155.555 24197.275 N2 - 0.6699 0.0038 - 177.590 31538.049 ============ Sum((d/s)**2) for starred atoms 7.499 Chi-squared at 95% for 1 degrees of freedom: 3.84 The group of atoms deviates significantly from planarity

Dihedral angles formed by LSQ-planes Plane - plane angle (s.u.) angle (s.u.) 1 2 63.39 (0.09) 116.61 (0.09) 1 3 65.07 (0.26) 114.93 (0.26) 1 4 35.28 (0.28) 144.72 (0.28) 1 5 37.18 (0.16) 142.82 (0.16) 1 6 65.42 (0.13) 114.58 (0.13) 2 3 39.74 (1/3) 140.26 (1/3) 2 4 89.04 (0.31) 90.96 (0.31) 2 5 29.65 (0.14) 150.35 (0.14) 2 6 2.05 (0.13) 177.95 (0.13) 3 4 71.80 (0.40) 108.20 (0.40) 3 5 33.97 (0.31) 146.03 (0.31) 3 6 40.36 (1/3) 139.64 (1/3) 4 5 61.32 (0.36) 118.68 (0.36) 4 6 87.05 (0.34) 92.95 (0.34) 5 6 31.64 (0.18) 148.36 (0.18)

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.39074 (18)	0.37536 (10)	0.09580 (18)	0.1276 (7)
S1	−0.11734 (13)	0.83597 (14)	0.25400 (18)	0.1197 (7)
N1	0.0504 (4)	0.7113 (3)	0.1617 (4)	0.0696 (10)
H1	0.060 (4)	0.750 (3)	0.095 (3)	0.084*
N2	0.0777 (4)	0.6675 (3)	0.4431 (4)	0.0742 (11)
C1	0.2895 (5)	0.4731 (3)	0.1211 (6)	0.0819 (14)
C2	0.2234 (5)	0.5114 (4)	0.0133 (6)	0.0906 (15)
H2	0.2322	0.4844	−0.0695	0.109*
C3	0.1448 (5)	0.5896 (4)	0.0311 (5)	0.0805 (14)
H3	0.1016	0.6163	−0.0407	0.097*
C4	0.1292 (4)	0.6291 (3)	0.1544 (5)	0.0627 (12)
C5	0.1954 (4)	0.5905 (3)	0.2631 (5)	0.0609 (11)
C6	0.2774 (4)	0.5118 (3)	0.2418 (5)	0.0704 (12)
H6	0.3242	0.4859	0.3120	0.085*
C7	−0.0352 (4)	0.7357 (4)	0.2555 (5)	0.0792 (13)
C8	−0.0448 (4)	0.6646 (4)	0.3649 (5)	0.0907 (15)
H8A	−0.1213	0.6788	0.4202	0.109*
H8B	−0.0570	0.6022	0.3284	0.109*
C9	0.1850 (5)	0.6314 (3)	0.3953 (4)	0.0592 (11)
C10	0.3036 (5)	0.6316 (3)	0.4850 (5)	0.0613 (11)
C11	0.2872 (5)	0.6170 (3)	0.6174 (5)	0.0831 (14)
H11	0.2026	0.6044	0.6510	0.100*
C12	0.3960 (7)	0.6210 (4)	0.7009 (6)	0.1040 (19)
H12	0.3840	0.6112	0.7904	0.125*
C13	0.5212 (7)	0.6391 (4)	0.6531 (7)	0.1033 (19)
H13	0.5939	0.6421	0.7101	0.124*
C14	0.5389 (5)	0.6528 (3)	0.5224 (7)	0.0898 (17)
H14	0.6242	0.6648	0.4897	0.108*
C15	0.4302 (4)	0.6489 (3)	0.4364 (5)	0.0744 (14)
H15	0.4430	0.6580	0.3467	0.089*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.1550 (15)	0.0789 (8)	0.1490 (15)	0.0358 (8)	−0.0427 (12)	−0.0419 (10)
S1	0.0824 (9)	0.1687 (15)	0.1078 (12)	0.0567 (9)	−0.0141 (10)	−0.0419 (12)
N1	0.059 (2)	0.085 (3)	0.065 (2)	0.007 (2)	−0.004 (2)	−0.0088 (19)
N2	0.051 (2)	0.111 (3)	0.061 (2)	−0.017 (2)	0.003 (2)	0.000 (2)
C1	0.081 (3)	0.062 (3)	0.103 (4)	−0.002 (2)	−0.021 (3)	−0.019 (3)
C2	0.101 (4)	0.081 (3)	0.089 (4)	0.008 (3)	−0.010 (3)	−0.037 (3)
C3	0.086 (4)	0.081 (3)	0.075 (4)	0.011 (3)	−0.013 (3)	−0.020 (3)
C4	0.058 (3)	0.060 (3)	0.070 (3)	−0.004 (2)	−0.002 (2)	−0.012 (2)
C5	0.055 (3)	0.058 (3)	0.070 (3)	−0.019 (2)	−0.007 (3)	0.001 (2)
C6	0.075 (3)	0.054 (3)	0.082 (3)	−0.010 (2)	−0.018 (3)	−0.008 (3)
C7	0.043 (2)	0.132 (4)	0.064 (3)	0.002 (3)	−0.011 (3)	−0.023 (3)
C8	0.043 (3)	0.151 (4)	0.078 (4)	−0.022 (3)	0.001 (3)	−0.013 (4)
C9	0.051 (3)	0.070 (3)	0.057 (3)	−0.020 (2)	0.001 (3)	0.003 (2)
C10	0.056 (3)	0.057 (2)	0.072 (3)	−0.0102 (19)	−0.007 (3)	−0.002 (2)
C11	0.074 (3)	0.100 (3)	0.075 (4)	−0.006 (3)	−0.008 (3)	0.012 (3)
C12	0.103 (5)	0.127 (5)	0.083 (4)	0.003 (4)	−0.033 (4)	0.006 (4)
C13	0.088 (5)	0.100 (4)	0.123 (6)	0.009 (3)	−0.039 (5)	−0.021 (4)
C14	0.060 (3)	0.080 (3)	0.129 (6)	−0.005 (3)	−0.010 (4)	−0.026 (4)
C15	0.055 (3)	0.076 (3)	0.092 (4)	−0.007 (2)	0.002 (3)	−0.020 (3)

Geometric parameters (Å, º)

Cl1—C1	1.738 (5)	C6—H6	0.93
S1—C7	1.645 (5)	C7—C8	1.507 (7)
N1—C7	1.328 (5)	C8—H8A	0.97
N1—C4	1.413 (5)	C8—H8B	0.97
N1—H1	0.876 (10)	C9—C10	1.496 (6)
N2—C9	1.284 (5)	C10—C11	1.373 (6)
N2—C8	1.460 (5)	C10—C15	1.380 (6)
C1—C6	1.352 (6)	C11—C12	1.380 (7)
C1—C2	1.391 (6)	C11—H11	0.93
C2—C3	1.373 (7)	C12—C13	1.366 (7)
C2—H2	0.93	C12—H12	0.93
C3—C4	1.383 (6)	C13—C14	1.356 (8)
C3—H3	0.93	C13—H13	0.93
C4—C5	1.401 (6)	C14—C15	1.396 (7)
C5—C6	1.403 (6)	C14—H14	0.93
C5—C9	1.469 (6)	C15—H15	0.93
C7—N1—C4	127.8 (4)	N2—C8—H8A	109.8
C7—N1—H1	117 (3)	C7—C8—H8A	109.8
C4—N1—H1	115 (3)	N2—C8—H8B	109.8
C9—N2—C8	118.8 (4)	C7—C8—H8B	109.8
C6—C1—C2	121.0 (4)	H8A—C8—H8B	108.3
C6—C1—Cl1	120.8 (4)	N2—C9—C5	124.4 (4)
C2—C1—Cl1	118.2 (4)	N2—C9—C10	115.4 (4)
C3—C2—C1	119.0 (5)	C5—C9—C10	120.2 (4)
C3—C2—H2	120.5	C11—C10—C15	119.2 (4)
C1—C2—H2	120.5	C11—C10—C9	120.3 (4)
C2—C3—C4	120.9 (5)	C15—C10—C9	120.5 (4)
C2—C3—H3	119.6	C10—C11—C12	120.2 (5)
C4—C3—H3	119.6	C10—C11—H11	119.9
C3—C4—C5	120.2 (4)	C12—C11—H11	119.9
C3—C4—N1	116.5 (4)	C13—C12—C11	120.7 (6)
C5—C4—N1	123.1 (4)	C13—C12—H12	119.7
C4—C5—C6	117.8 (4)	C11—C12—H12	119.7
C4—C5—C9	122.3 (4)	C14—C13—C12	119.7 (6)
C6—C5—C9	119.9 (4)	C14—C13—H13	120.2
C1—C6—C5	121.2 (4)	C12—C13—H13	120.2
C1—C6—H6	119.4	C13—C14—C15	120.5 (6)
C5—C6—H6	119.4	C13—C14—H14	119.8
N1—C7—C8	113.4 (4)	C15—C14—H14	119.8
N1—C7—S1	122.8 (4)	C10—C15—C14	119.7 (5)
C8—C7—S1	123.8 (4)	C10—C15—H15	120.2
N2—C8—C7	109.3 (3)	C14—C15—H15	120.2
C6—C1—C2—C3	−0.1 (7)	S1—C7—C8—N2	−105.9 (4)
Cl1—C1—C2—C3	−178.9 (4)	C8—N2—C9—C5	2.9 (6)
C1—C2—C3—C4	−1.2 (7)	C8—N2—C9—C10	−176.1 (4)
C2—C3—C4—C5	1.0 (7)	C4—C5—C9—N2	37.6 (6)
C2—C3—C4—N1	177.8 (4)	C6—C5—C9—N2	−144.5 (4)
C7—N1—C4—C3	142.0 (4)	C4—C5—C9—C10	−143.4 (4)
C7—N1—C4—C5	−41.3 (6)	C6—C5—C9—C10	34.4 (5)
C3—C4—C5—C6	0.4 (6)	N2—C9—C10—C11	36.5 (6)
N1—C4—C5—C6	−176.1 (3)	C5—C9—C10—C11	−142.6 (4)
C3—C4—C5—C9	178.3 (4)	N2—C9—C10—C15	−141.8 (4)
N1—C4—C5—C9	1.7 (6)	C5—C9—C10—C15	39.1 (6)
C2—C1—C6—C5	1.5 (7)	C15—C10—C11—C12	0.9 (7)
Cl1—C1—C6—C5	−179.7 (3)	C9—C10—C11—C12	−177.4 (4)
C4—C5—C6—C1	−1.6 (6)	C10—C11—C12—C13	−0.2 (8)
C9—C5—C6—C1	−179.6 (4)	C11—C12—C13—C14	−0.4 (9)
C4—N1—C7—C8	0.2 (6)	C12—C13—C14—C15	0.4 (8)
C4—N1—C7—S1	177.9 (3)	C11—C10—C15—C14	−1.0 (7)
C9—N2—C8—C7	−74.3 (5)	C9—C10—C15—C14	177.3 (4)
N1—C7—C8—N2	71.7 (5)	C13—C14—C15—C10	0.4 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2^i	0.88 (1)	1.95 (3)	2.827 (5)	177 (3)

Symmetry code: (i) x, −y+3/2, z−1/2.