Download citation
Download citation
link to html
In the crystal structure of the title compound, C16H12Br2N2O2S, mol­ecules are linked by two hydrogen bonds to form a three-dimensional network. The H atom of the NH group has two inter­molecular contacts; one to a sulfonyl O atom (H...O = 2.22 Å) and the other to the Br at the quinoline C-7 position (H...Br = 3.11 Å).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680502773X/su6228sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680502773X/su6228Isup2.hkl
Contains datablock I

CCDC reference: 287729

Key indicators

  • Single-crystal X-ray study
  • T = 299 K
  • Mean [sigma](C-C) = 0.007 Å
  • R factor = 0.041
  • wR factor = 0.109
  • Data-to-parameter ratio = 14.3

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.97 PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.65 mm PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 7 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C16 PLAT480_ALERT_4_C Long H...A H-Bond Reported H1N .. BR1 .. 3.11 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 67.96 From the CIF: _reflns_number_total 2997 Count of symmetry unique reflns 1779 Completeness (_total/calc) 168.47% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1218 Fraction of Friedel pairs measured 0.685 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 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 4 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The investigation of the crystal structure of the title compound, (I), is part of our search for Zinquin Ester analogues (Kimber et al., 2000). This class of the compounds has been shown to be effective in the detection of zinc (II) in a range of mammalian cells (Pearce et al., 2001).

The molecular structure of the title compound (I) is illustrated in Fig. 1. The quinoline ring system is planar and inclined to the phenyl ring of the tosyl moiety [torsion angle C1—N1—S1—C10 being 76.5 (3)°].

The crystal packing of (I) is stabilized through a hydrogen-bonding network, as shown in Fig. 2. Details of the hydrogen bonding are given in Table 1. The H atom of the NH group has an intermolecular contact to atom O1, with an H···O distance of 2.22 Å, and is also connected to the bromine atom, indicating very weak N—H···Br hydrogen bonding, with an H···Br distance of 3.11 Å.

Experimental top

Compound (I) was prepared according to the literature procedure (Xue et al., 2000). Suitable crystals were obtained by recrystallization from methanol-dichloromethane (1:1).

Refinement top

The H atoms were included in idealized positions and refined as riding atoms with Uiso(H) = 1.2Ueq(parent atom), and N—H = 0.86 Å and C—H = 0.93 Å (0.96 Å for methyl groups).

Computing details top

Data collection: Nonius Diffractometer Control Software (Nonius, 1996); cell refinement: Nonius Diffractometer Control Software; data reduction: REDU4 (Stoe & Cie, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Molecular structure of (I), showing the atom labeling and displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. The packing of (I), with hydrogen bonding shown as dashed lines.
5,7-Dibromo-N-tosylquinolin-8-amine top
Crystal data top
C16H12Br2N2O2SF(000) = 896
Mr = 456.16Dx = 1.825 Mg m3
Orthorhombic, P212121Cu Kα radiation, λ = 1.54180 Å
Hall symbol: P 2ac 2abCell parameters from 25 reflections
a = 4.939 (1) Åθ = 5.3–18.8°
b = 16.595 (3) ŵ = 7.46 mm1
c = 20.254 (4) ÅT = 299 K
V = 1660.1 (6) Å3Long needle, light brown
Z = 40.65 × 0.08 × 0.05 mm
Data collection top
Nonius CAD-4
diffractometer
2758 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.019
Graphite monochromatorθmax = 68.0°, θmin = 3.4°
ω/2θ scansh = 05
Absorption correction: psi-scan
(North et al., 1968)
k = 019
Tmin = 0.486, Tmax = 0.708l = 2424
3465 measured reflections3 standard reflections every 120 min
2997 independent reflections intensity decay: 1.0%
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.041 w = 1/[σ2(Fo2) + (0.076P)2 + 0.4357P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.109(Δ/σ)max < 0.001
S = 1.08Δρmax = 0.69 e Å3
2997 reflectionsΔρmin = 0.92 e Å3
209 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0012 (2)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983)
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.01 (3)
Crystal data top
C16H12Br2N2O2SV = 1660.1 (6) Å3
Mr = 456.16Z = 4
Orthorhombic, P212121Cu Kα radiation
a = 4.939 (1) ŵ = 7.46 mm1
b = 16.595 (3) ÅT = 299 K
c = 20.254 (4) Å0.65 × 0.08 × 0.05 mm
Data collection top
Nonius CAD-4
diffractometer
2758 reflections with I > 2σ(I)
Absorption correction: psi-scan
(North et al., 1968)
Rint = 0.019
Tmin = 0.486, Tmax = 0.7083 standard reflections every 120 min
3465 measured reflections intensity decay: 1.0%
2997 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.109Δρmax = 0.69 e Å3
S = 1.08Δρmin = 0.92 e Å3
2997 reflectionsAbsolute structure: Flack (1983)
209 parametersAbsolute structure parameter: 0.01 (3)
0 restraints
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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 (Å2) top
xyzUiso*/Ueq
Br10.67032 (15)0.06168 (3)0.17545 (3)0.0739 (2)
Br20.72224 (16)0.34697 (5)0.03074 (3)0.0822 (3)
S10.45127 (18)0.15331 (5)0.33555 (5)0.0360 (3)
O10.7323 (5)0.14564 (17)0.31743 (15)0.0460 (8)
O20.3241 (7)0.09229 (18)0.37390 (16)0.0534 (10)
N10.2761 (6)0.15936 (18)0.26682 (15)0.0364 (9)
N20.0963 (8)0.3138 (2)0.24236 (19)0.0459 (11)
C10.3804 (8)0.2041 (2)0.21271 (19)0.0368 (10)
C20.5625 (10)0.1704 (3)0.1682 (2)0.0470 (12)
C30.6661 (11)0.2144 (3)0.1149 (2)0.0543 (16)
C40.5827 (10)0.2916 (3)0.1050 (2)0.0510 (16)
C50.3953 (9)0.3298 (2)0.1475 (2)0.0443 (12)
C60.3020 (13)0.4095 (3)0.1402 (2)0.0600 (14)
C70.1102 (12)0.4385 (3)0.1829 (3)0.0650 (16)
C80.0162 (12)0.3887 (3)0.2315 (3)0.0603 (17)
C90.2905 (8)0.2838 (2)0.20064 (19)0.0397 (11)
C100.4153 (8)0.2452 (2)0.37766 (18)0.0369 (10)
C110.5991 (9)0.3069 (3)0.3663 (2)0.0470 (12)
C120.5790 (11)0.3769 (3)0.4025 (2)0.0537 (16)
C130.3806 (11)0.3870 (3)0.4501 (2)0.0553 (16)
C140.1963 (11)0.3243 (3)0.4598 (2)0.0581 (15)
C150.2108 (9)0.2538 (3)0.4241 (2)0.0483 (12)
C160.3710 (16)0.4613 (4)0.4915 (3)0.080 (2)
H1N0.121900.135600.263600.0440*
H30.791300.191100.086500.0650*
H60.370000.442100.106800.0720*
H70.045300.490900.178900.0780*
H80.116000.409300.259500.0720*
H110.734200.301000.334700.0560*
H120.701500.418400.394700.0650*
H140.060400.330200.491200.0700*
H150.085700.212800.430900.0580*
H16A0.349500.507600.463600.0960*
H16B0.536300.466100.516100.0960*
H16C0.220900.458000.521500.0960*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.1012 (5)0.0548 (3)0.0657 (3)0.0222 (3)0.0097 (3)0.0118 (2)
Br20.0905 (5)0.1038 (5)0.0522 (3)0.0254 (4)0.0097 (3)0.0225 (3)
S10.0288 (4)0.0363 (4)0.0428 (5)0.0004 (3)0.0020 (3)0.0059 (4)
O10.0222 (12)0.0534 (15)0.0623 (16)0.0042 (11)0.0014 (12)0.0051 (13)
O20.0516 (18)0.0503 (15)0.0582 (17)0.0002 (14)0.0007 (15)0.0177 (14)
N10.0285 (15)0.0374 (15)0.0434 (15)0.0033 (13)0.0042 (13)0.0023 (13)
N20.0404 (19)0.0442 (18)0.053 (2)0.0040 (15)0.0017 (16)0.0005 (15)
C10.0359 (19)0.0389 (18)0.0355 (17)0.0026 (15)0.0017 (15)0.0044 (14)
C20.052 (2)0.045 (2)0.044 (2)0.0047 (18)0.003 (2)0.0028 (18)
C30.058 (3)0.064 (3)0.041 (2)0.000 (2)0.010 (2)0.0023 (19)
C40.053 (3)0.065 (3)0.035 (2)0.012 (2)0.0020 (18)0.0078 (19)
C50.047 (2)0.042 (2)0.044 (2)0.0095 (16)0.0116 (17)0.0056 (16)
C60.074 (3)0.051 (2)0.055 (2)0.012 (2)0.011 (3)0.017 (2)
C70.075 (3)0.043 (2)0.077 (3)0.004 (2)0.019 (3)0.009 (2)
C80.063 (3)0.049 (3)0.069 (3)0.007 (2)0.003 (3)0.000 (2)
C90.0370 (19)0.0425 (19)0.0397 (18)0.0062 (17)0.0089 (16)0.0006 (15)
C100.0319 (18)0.0452 (19)0.0336 (17)0.0004 (15)0.0018 (14)0.0053 (15)
C110.041 (2)0.048 (2)0.052 (2)0.0017 (18)0.0074 (18)0.0003 (18)
C120.052 (3)0.050 (2)0.059 (3)0.002 (2)0.006 (2)0.004 (2)
C130.068 (3)0.056 (3)0.042 (2)0.019 (2)0.013 (2)0.0046 (19)
C140.056 (3)0.081 (3)0.0374 (19)0.010 (3)0.007 (2)0.002 (2)
C150.037 (2)0.062 (2)0.046 (2)0.0037 (19)0.0098 (18)0.0038 (19)
C160.107 (5)0.071 (3)0.061 (3)0.024 (3)0.015 (3)0.019 (3)
Geometric parameters (Å, º) top
Br1—C21.887 (5)C10—C151.388 (6)
Br2—C41.893 (4)C10—C111.388 (6)
S1—O11.441 (3)C11—C121.377 (7)
S1—O21.422 (3)C12—C131.385 (7)
S1—N11.642 (3)C13—C161.492 (8)
S1—C101.756 (4)C13—C141.396 (7)
N1—C11.421 (5)C14—C151.377 (7)
N2—C81.323 (6)C3—H30.9300
N2—C91.372 (5)C6—H60.9300
N1—H1N0.8600C7—H70.9300
C1—C21.391 (6)C8—H80.9300
C1—C91.416 (5)C11—H110.9300
C2—C31.400 (6)C12—H120.9300
C3—C41.361 (7)C14—H140.9300
C4—C51.414 (6)C15—H150.9300
C5—C61.408 (6)C16—H16A0.9600
C5—C91.417 (5)C16—H16B0.9600
C6—C71.370 (8)C16—H16C0.9600
C7—C81.367 (8)
Br1···S13.7413 (14)C15···C14vii3.600 (7)
Br1···O13.210 (3)C8···H11v2.9000
Br1···N13.137 (3)C10···H14vii3.0200
Br1···C7i3.686 (6)C11···H8ii3.0900
Br1···C12i3.662 (5)C12···H14ii3.0800
Br1···H1Nii3.1100C13···H15vii3.0900
Br1···H16Ai2.9600C14···H15vii3.0000
Br2···H62.8100C15···H11v3.0700
S1···Br13.7413 (14)C15···H14vii2.8000
O1···Br13.210 (3)C16···H6viii3.0700
O1···N1ii2.884 (4)H1N···Br1v3.1100
O1···C23.164 (5)H1N···O1v2.2200
O1···H1Nii2.2200H6···Br22.8100
O1···H112.6000H6···C16ix3.0700
O1···H7i2.7900H6···H16Cix2.4400
O2···H152.5900H7···O1vi2.7900
O2···H16Biii2.8100H7···O2x2.7000
O2···H7iv2.7000H8···C11v3.0900
N1···Br13.137 (3)H8···H11v2.4700
N1···O1v2.884 (4)H11···O12.6000
N1···N22.757 (5)H11···N2ii2.6000
N2···N12.757 (5)H11···C8ii2.9000
N2···C103.360 (5)H11···C15ii3.0700
N2···H11v2.6000H11···H8ii2.4700
C2···O13.164 (5)H14···C12v3.0800
C7···Br1vi3.686 (6)H14···H16C2.3500
C10···N23.360 (5)H14···C10iii3.0200
C11···C14ii3.517 (7)H14···C15iii2.8000
C11···C15ii3.358 (6)H15···O22.5900
C12···Br1vi3.662 (5)H15···C13iii3.0900
C12···C14ii3.377 (7)H15···C14iii3.0000
C14···C15iii3.600 (7)H16A···Br1vi2.9600
C14···C11v3.517 (7)H16B···O2vii2.8100
C14···C12v3.377 (7)H16C···H142.3500
C15···C11v3.358 (6)H16C···H6viii2.4400
O1—S1—O2120.09 (19)S1—C10—C15119.5 (3)
O1—S1—N1107.27 (17)C10—C11—C12119.1 (4)
O1—S1—C10107.32 (18)C11—C12—C13121.6 (5)
O2—S1—N1105.89 (18)C12—C13—C16120.9 (5)
O2—S1—C10107.96 (18)C12—C13—C14118.0 (4)
N1—S1—C10107.78 (17)C14—C13—C16121.1 (5)
S1—N1—C1119.7 (3)C13—C14—C15121.7 (4)
C8—N2—C9116.6 (4)C10—C15—C14118.8 (4)
C1—N1—H1N120.00C2—C3—H3120.00
S1—N1—H1N120.00C4—C3—H3120.00
C2—C1—C9117.8 (4)C5—C6—H6120.00
N1—C1—C9120.5 (3)C7—C6—H6120.00
N1—C1—C2121.6 (3)C6—C7—H7121.00
Br1—C2—C1121.1 (3)C8—C7—H7121.00
Br1—C2—C3117.1 (3)N2—C8—H8117.00
C1—C2—C3121.8 (4)C7—C8—H8117.00
C2—C3—C4119.6 (4)C10—C11—H11120.00
C3—C4—C5122.0 (4)C12—C11—H11120.00
Br2—C4—C3117.7 (3)C11—C12—H12119.00
Br2—C4—C5120.3 (3)C13—C12—H12119.00
C4—C5—C6124.8 (4)C13—C14—H14119.00
C4—C5—C9117.4 (3)C15—C14—H14119.00
C6—C5—C9117.8 (4)C10—C15—H15121.00
C5—C6—C7119.3 (4)C14—C15—H15121.00
C6—C7—C8118.5 (5)C13—C16—H16A110.00
N2—C8—C7125.9 (5)C13—C16—H16B109.00
N2—C9—C5121.8 (3)C13—C16—H16C109.00
C1—C9—C5121.3 (3)H16A—C16—H16B109.00
N2—C9—C1116.9 (3)H16A—C16—H16C109.00
C11—C10—C15120.9 (4)H16B—C16—H16C109.00
S1—C10—C11119.6 (3)
O1—S1—N1—C138.8 (3)C2—C3—C4—Br2178.3 (4)
O2—S1—N1—C1168.2 (3)C2—C3—C4—C50.7 (7)
C10—S1—N1—C176.5 (3)Br2—C4—C5—C9177.5 (3)
N1—S1—C10—C1190.6 (3)C3—C4—C5—C91.5 (7)
O1—S1—C10—C15152.4 (3)Br2—C4—C5—C61.3 (7)
O2—S1—C10—C1521.6 (4)C3—C4—C5—C6179.7 (5)
N1—S1—C10—C1592.4 (3)C6—C5—C9—N22.7 (6)
O1—S1—C10—C1124.7 (4)C6—C5—C9—C1177.9 (4)
O2—S1—C10—C11155.5 (3)C4—C5—C6—C7176.9 (5)
S1—N1—C1—C284.2 (4)C9—C5—C6—C71.9 (7)
S1—N1—C1—C999.0 (4)C4—C5—C9—C13.2 (6)
C8—N2—C9—C1179.0 (4)C4—C5—C9—N2176.2 (4)
C8—N2—C9—C51.6 (6)C5—C6—C7—C80.2 (8)
C9—N2—C8—C70.3 (8)C6—C7—C8—N21.0 (9)
N1—C1—C9—N21.5 (5)S1—C10—C15—C14175.8 (3)
N1—C1—C9—C5179.0 (4)C15—C10—C11—C120.9 (6)
C9—C1—C2—C33.2 (6)S1—C10—C11—C12176.1 (3)
C2—C1—C9—C54.0 (6)C11—C10—C15—C141.2 (6)
N1—C1—C2—Br12.5 (6)C10—C11—C12—C130.3 (7)
C2—C1—C9—N2175.4 (4)C11—C12—C13—C141.1 (7)
N1—C1—C2—C3179.9 (4)C11—C12—C13—C16176.5 (5)
C9—C1—C2—Br1174.4 (3)C16—C13—C14—C15176.9 (5)
Br1—C2—C3—C4176.1 (4)C12—C13—C14—C150.8 (7)
C1—C2—C3—C41.6 (7)C13—C14—C15—C100.4 (7)
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x+1, y, z; (iii) x1/2, y+1/2, z+1; (iv) x, y1/2, z+1/2; (v) x1, y, z; (vi) x+1, y+1/2, z+1/2; (vii) x+1/2, y+1/2, z+1; (viii) x+1/2, y+1, z+1/2; (ix) x+1/2, y+1, z1/2; (x) x, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O1v0.862.222.884 (4)134
N1—H1N···Br1v0.863.113.873 (3)149
C6—H6···Br20.932.813.209 (5)107
C11—H11···N2ii0.932.603.514 (6)169
C15—H15···O20.932.592.921 (6)101
Symmetry codes: (ii) x+1, y, z; (v) x1, y, z.

Experimental details

Crystal data
Chemical formulaC16H12Br2N2O2S
Mr456.16
Crystal system, space groupOrthorhombic, P212121
Temperature (K)299
a, b, c (Å)4.939 (1), 16.595 (3), 20.254 (4)
V3)1660.1 (6)
Z4
Radiation typeCu Kα
µ (mm1)7.46
Crystal size (mm)0.65 × 0.08 × 0.05
Data collection
DiffractometerNonius CAD-4
diffractometer
Absorption correctionPsi-scan
(North et al., 1968)
Tmin, Tmax0.486, 0.708
No. of measured, independent and
observed [I > 2σ(I)] reflections
3465, 2997, 2758
Rint0.019
(sin θ/λ)max1)0.601
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.109, 1.08
No. of reflections2997
No. of parameters209
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.69, 0.92
Absolute structureFlack (1983)
Absolute structure parameter0.01 (3)

Computer programs: Nonius Diffractometer Control Software (Nonius, 1996), Nonius Diffractometer Control Software, REDU4 (Stoe & Cie, 1987), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O1i0.862.222.884 (4)134
N1—H1N···Br1i0.863.113.873 (3)149
Symmetry code: (i) x1, y, z.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds