A comparative experimental and theoretical investigation of hydrogen-bond, halogen-bond and π–π inter­actions in the solid-state supra­molecular assembly of 2- and 4-formyl­phenyl aryl­sulfonates

To explore the operational role of noncovalent inter­actions in supra­molecular architectures with designed topologies, a series of solid-state structures of 2- and 4-formyl­phenyl 4-substituted benzene­sulfonates was investigated. The com­pounds are 2-formyl­phenyl 4-methyl­benzene­sulfonate, C₁₄H₁₂O₄S, 3a, 2-formyl­phenyl 4-chloro­benzene­sulfonate, C₁₃H₉ClO₄S, 3b, 2-formyl­phenyl 4-bromo­ben­zene­sulfonate, C₁₃H₉BrO₄S, 3c, 4-formyl­phenyl 4-methyl­benzene­sulfonate, C₁₄H₁₂O₄S, 4a, 4-formyl­phenyl 4-chloro­benzene­sulfonate, 4b, C₁₃H₉ClO₄S, and 4-formyl­phenyl 4-bromo­benzene­sulfonate, C₁₃H₉BrO₄S, 4c. The title com­pounds were synthesized under basic conditions from salicyl­aldehyde/4-hy­droxy­benzaldehydes and various aryl sul­fonyl chlorides. Remarkably, halogen-bonding inter­actions are found to be important to rationalize the solid-state crystal structures. In particular, the formation of O...X (X = Cl and Br) and type I X...X halogen-bonding inter­actions have been analyzed by means of density functional theory (DFT) calculations and characterized using Bader's theory of `atoms in mol­ecules' and mol­ecular electrostatic potential (MEP) surfaces, confirming the relevance and stabilizing nature of these inter­actions. They have been compared to anti­parallel π-stacking inter­actions that are formed between the aryl­sulfonates.

Computing details

Data collection: APEX2 (Bruker, 2011) for (3a), (3b), (4b), (4c); APEX2 (Bruker, 2007) for (3c). Cell refinement: SAINT (Bruker, 2011) for (3a), (3b), (4b), (4c); SAINT (Bruker, 2007) for (3c). Data reduction: SAINT (Bruker, 2011) for (3a), (3b), (4b), (4c); SAINT (Bruker, 2007) for (3c). For all structures, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008). Program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015) for (3a), (3b), (4b), (4c); SHELXL2018 (Sheldrick, 2015) for (3c). For all structures, molecular graphics: Mercury (Macrae et al., 2008). Software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015), enCIFer (Allen et al., 2004), PLATON (Spek, 2009) and WinGX (Farrugia, 2012) for (3a), (3b), (4b), (4c); PLATON (Spek, 2009) and publCIF (Westrip, 2010) for (3c).

2-Formylphenyl 4-methylbenzenesulfonate (3a)

Crystal data

C14H12O4S	F(000) = 1152
Mr = 276.30	Dx = 1.364 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 23.7755 (16) Å	Cell parameters from 2730 reflections
b = 8.3718 (5) Å	θ = 2.1–27.2°
c = 16.3235 (12) Å	µ = 0.25 mm^−1
β = 124.106 (3)°	T = 296 K
V = 2690.3 (3) Å^3	Prism, white
Z = 8	0.40 × 0.30 × 0.26 mm

Data collection

Bruker Kappa APEXII CCD diffractometer	2987 independent reflections
Radiation source: fine-focus sealed tube	2378 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 7.80 pixels mm^-1	θmax = 27.2°, θmin = 2.1°
ω scans	h = −30→30
Absorption correction: multi-scan (SADABS; Bruker, 2011)	k = −7→10
Tmin = 0.593, Tmax = 0.746	l = −20→20
11160 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.039	w = 1/[σ^2(Fo^2) + (0.0517P)^2 + 1.3907P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.112	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.28 e Å^−3
2987 reflections	Δρmin = −0.32 e Å^−3
174 parameters	Extinction correction: SHELXL-2014/7 (Sheldrick 2015b, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0045 (4)

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.

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

	x	y	z	Uiso*/Ueq
S1	0.16506 (2)	0.73107 (5)	0.17846 (3)	0.05234 (17)
O21	0.14649 (8)	1.07324 (16)	0.39949 (13)	0.0815 (5)
O3	0.21404 (5)	0.73434 (13)	0.29703 (9)	0.0478 (3)
O1	0.12514 (8)	0.58997 (15)	0.14871 (10)	0.0688 (4)
O2	0.21042 (8)	0.75780 (18)	0.14989 (12)	0.0773 (5)
C1	0.18769 (7)	0.68614 (18)	0.35162 (11)	0.0413 (4)
C2	0.16864 (7)	0.80182 (18)	0.39226 (11)	0.0416 (4)
C21	0.17411 (9)	0.9749 (2)	0.38059 (13)	0.0522 (4)
H21	0.2001	1.0089	0.3576	0.063*
C3	0.14532 (9)	0.7498 (2)	0.44893 (13)	0.0540 (4)
H3	0.1315	0.8245	0.4764	0.065*
C4	0.14230 (10)	0.5905 (2)	0.46503 (14)	0.0629 (5)
H4	0.1267	0.5579	0.5034	0.075*
C5	0.16222 (10)	0.4790 (2)	0.42479 (14)	0.0621 (5)
H5	0.1604	0.3709	0.4364	0.075*
C6	0.18484 (9)	0.5256 (2)	0.36746 (14)	0.0532 (4)
H6	0.1980	0.4500	0.3397	0.064*
C1'	0.11354 (8)	0.89717 (19)	0.15260 (12)	0.0447 (4)
C2'	0.13768 (9)	1.0468 (2)	0.15141 (13)	0.0519 (4)
H2'	0.1790	1.0573	0.1582	0.062*
C3'	0.10029 (10)	1.1789 (2)	0.14023 (14)	0.0579 (5)
H3'	0.1164	1.2795	0.1389	0.069*
C4'	0.03920 (9)	1.1659 (2)	0.13086 (14)	0.0595 (5)
C5'	0.01555 (9)	1.0150 (3)	0.13122 (15)	0.0629 (5)
H5'	−0.0260	1.0046	0.1240	0.075*
C6'	0.05215 (9)	0.8803 (2)	0.14207 (14)	0.0553 (4)
H13	0.0358	0.7795	0.1423	0.066*
C41'	−0.00108 (13)	1.3124 (3)	0.1199 (2)	0.0946 (8)
H41A	−0.0128	1.3694	0.0613	0.142*
H41B	0.0257	1.3800	0.1767	0.142*
H41C	−0.0418	1.2813	0.1149	0.142*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0687 (3)	0.0473 (3)	0.0549 (3)	0.00435 (19)	0.0431 (2)	−0.00057 (18)
O21	0.0999 (11)	0.0450 (8)	0.1081 (13)	0.0103 (7)	0.0635 (10)	−0.0099 (8)
O3	0.0475 (6)	0.0492 (7)	0.0550 (7)	0.0044 (5)	0.0338 (6)	0.0037 (5)
O1	0.0982 (10)	0.0441 (7)	0.0630 (8)	−0.0067 (7)	0.0444 (8)	−0.0119 (6)
O2	0.0988 (11)	0.0855 (11)	0.0893 (11)	0.0196 (8)	0.0782 (10)	0.0134 (8)
C1	0.0411 (7)	0.0394 (8)	0.0437 (8)	0.0030 (6)	0.0240 (7)	0.0022 (6)
C2	0.0430 (8)	0.0391 (8)	0.0399 (8)	0.0029 (6)	0.0215 (7)	0.0004 (6)
C21	0.0597 (10)	0.0398 (9)	0.0494 (10)	0.0023 (7)	0.0258 (8)	−0.0029 (7)
C3	0.0597 (10)	0.0590 (11)	0.0495 (10)	0.0042 (8)	0.0343 (9)	−0.0017 (8)
C4	0.0736 (12)	0.0641 (12)	0.0611 (12)	−0.0049 (9)	0.0439 (10)	0.0095 (9)
C5	0.0740 (12)	0.0431 (10)	0.0687 (13)	−0.0047 (9)	0.0397 (11)	0.0083 (9)
C6	0.0627 (10)	0.0368 (9)	0.0590 (10)	0.0051 (7)	0.0335 (9)	−0.0005 (7)
C1'	0.0493 (8)	0.0434 (9)	0.0427 (8)	−0.0014 (7)	0.0267 (7)	0.0012 (7)
C2'	0.0512 (9)	0.0517 (10)	0.0574 (10)	−0.0029 (8)	0.0333 (8)	0.0083 (8)
C3'	0.0669 (11)	0.0439 (10)	0.0625 (11)	−0.0005 (8)	0.0361 (9)	0.0089 (8)
C4'	0.0594 (10)	0.0580 (11)	0.0525 (10)	0.0110 (9)	0.0263 (9)	0.0056 (8)
C5'	0.0435 (9)	0.0739 (13)	0.0676 (12)	−0.0014 (8)	0.0289 (9)	−0.0023 (10)
C6'	0.0525 (9)	0.0520 (10)	0.0607 (11)	−0.0121 (8)	0.0313 (9)	−0.0050 (8)
C41'	0.0931 (17)	0.0790 (16)	0.106 (2)	0.0321 (14)	0.0521 (16)	0.0097 (14)

Geometric parameters (Å, º)

S1—O1	1.4197 (14)	C5—H5	0.9300
S1—O2	1.4122 (14)	C6—H6	0.9300
S1—O3	1.6048 (13)	C1'—C6'	1.378 (2)
S1—C1'	1.7414 (16)	C1'—C2'	1.382 (2)
O21—C21	1.196 (2)	C2'—C3'	1.366 (2)
O3—C1	1.4055 (18)	C2'—H2'	0.9300
C1—C6	1.377 (2)	C3'—C4'	1.377 (3)
C1—C2	1.386 (2)	C3'—H3'	0.9300
C2—C3	1.388 (2)	C4'—C5'	1.384 (3)
C2—C21	1.477 (2)	C4'—C41'	1.504 (3)
C21—H21	0.9300	C5'—C6'	1.374 (3)
C3—C4	1.369 (3)	C5'—H5'	0.9300
C3—H3	0.9300	C6'—H13	0.9300
C4—C5	1.370 (3)	C41'—H41A	0.9600
C4—H4	0.9300	C41'—H41B	0.9600
C5—C6	1.372 (3)	C41'—H41C	0.9600
O2—S1—O1	120.45 (9)	C5—C6—H6	120.5
O2—S1—O3	102.91 (8)	C1—C6—H6	120.5
O1—S1—O3	108.70 (7)	C6'—C1'—C2'	120.68 (16)
O2—S1—C1'	110.92 (8)	C6'—C1'—S1	120.02 (13)
O1—S1—C1'	109.69 (9)	C2'—C1'—S1	119.06 (12)
O3—S1—C1'	102.41 (7)	C3'—C2'—C1'	119.45 (15)
C1—O3—S1	118.67 (10)	C3'—C2'—H2'	120.3
C6—C1—C2	121.89 (16)	C1'—C2'—H2'	120.3
C6—C1—O3	119.05 (14)	C2'—C3'—C4'	121.15 (17)
C2—C1—O3	118.98 (14)	C2'—C3'—H3'	119.4
C1—C2—C3	117.37 (15)	C4'—C3'—H3'	119.4
C1—C2—C21	123.23 (15)	C3'—C4'—C5'	118.54 (17)
C3—C2—C21	119.37 (15)	C3'—C4'—C41'	120.7 (2)
O21—C21—C2	122.76 (18)	C5'—C4'—C41'	120.8 (2)
O21—C21—H21	118.6	C6'—C5'—C4'	121.34 (17)
C2—C21—H21	118.6	C6'—C5'—H5'	119.3
C4—C3—C2	121.11 (17)	C4'—C5'—H5'	119.3
C4—C3—H3	119.4	C5'—C6'—C1'	118.82 (16)
C2—C3—H3	119.4	C5'—C6'—H13	120.6
C3—C4—C5	120.17 (18)	C1'—C6'—H13	120.6
C3—C4—H4	119.9	C4'—C41'—H41A	109.5
C5—C4—H4	119.9	C4'—C41'—H41B	109.5
C4—C5—C6	120.40 (17)	H41A—C41'—H41B	109.5
C4—C5—H5	119.8	C4'—C41'—H41C	109.5
C6—C5—H5	119.8	H41A—C41'—H41C	109.5
C5—C6—C1	119.04 (17)	H41B—C41'—H41C	109.5
O2—S1—O3—C1	−169.91 (11)	O3—C1—C6—C5	176.85 (15)
O1—S1—O3—C1	−41.12 (13)	O2—S1—C1'—C6'	157.65 (15)
C1'—S1—O3—C1	74.90 (12)	O1—S1—C1'—C6'	22.16 (17)
S1—O3—C1—C6	82.36 (16)	O3—S1—C1'—C6'	−93.14 (15)
S1—O3—C1—C2	−100.96 (15)	O2—S1—C1'—C2'	−27.91 (17)
C6—C1—C2—C3	−1.0 (2)	O1—S1—C1'—C2'	−163.40 (13)
O3—C1—C2—C3	−177.55 (14)	O3—S1—C1'—C2'	81.30 (15)
C6—C1—C2—C21	177.05 (16)	C6'—C1'—C2'—C3'	0.4 (3)
O3—C1—C2—C21	0.5 (2)	S1—C1'—C2'—C3'	−174.02 (14)
C1—C2—C21—O21	165.78 (17)	C1'—C2'—C3'—C4'	0.5 (3)
C3—C2—C21—O21	−16.2 (3)	C2'—C3'—C4'—C5'	−1.1 (3)
C1—C2—C3—C4	0.9 (3)	C2'—C3'—C4'—C41'	179.18 (19)
C21—C2—C3—C4	−177.15 (17)	C3'—C4'—C5'—C6'	0.9 (3)
C2—C3—C4—C5	−0.2 (3)	C41'—C4'—C5'—C6'	−179.4 (2)
C3—C4—C5—C6	−0.5 (3)	C4'—C5'—C6'—C1'	−0.1 (3)
C4—C5—C6—C1	0.5 (3)	C2'—C1'—C6'—C5'	−0.6 (3)
C2—C1—C6—C5	0.3 (3)	S1—C1'—C6'—C5'	173.78 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1^i	0.93	2.69	3.579 (2)	159
C5—H5···O21^ii	0.93	2.54	3.417 (2)	157
C6—H6···O2^iii	0.93	2.63	3.479 (2)	151
C2′—H2′···O3^iv	0.93	2.67	3.504 (2)	150
C3′—H3′···O1^v	0.93	2.61	3.481 (2)	157

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

2-Formylphenyl 4-chlorobenzenesulfonate (3b)

Crystal data

C13H9ClO4S	F(000) = 608
Mr = 296.71	Dx = 1.496 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.7066 (8) Å	Cell parameters from 2006 reflections
b = 12.9371 (8) Å	θ = 1.5–27.2°
c = 7.4310 (4) Å	µ = 0.45 mm^−1
β = 91.565 (3)°	T = 296 K
V = 1317.20 (13) Å^3	Prism, white
Z = 4	0.40 × 0.32 × 0.28 mm

Data collection

Bruker Kappa APEXII CCD diffractometer	2896 independent reflections
Radiation source: fine-focus sealed tube	2006 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 7.80 pixels mm^-1	θmax = 27.2°, θmin = 1.5°
ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Bruker, 2011)	k = −16→16
Tmin = 0.685, Tmax = 0.746	l = −9→9
11311 measured 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)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.116	w = 1/[σ^2(Fo^2) + (0.0485P)^2 + 0.4725P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
2896 reflections	Δρmax = 0.36 e Å^−3
172 parameters	Δρmin = −0.45 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
S1	0.28424 (4)	0.43452 (6)	0.60153 (9)	0.0689 (2)
O1	0.33588 (12)	0.49402 (18)	0.4748 (2)	0.0872 (6)
O2	0.26952 (14)	0.32676 (16)	0.5784 (3)	0.1000 (8)
O3	0.34086 (11)	0.44217 (12)	0.7925 (2)	0.0612 (4)
C1	0.38961 (15)	0.53411 (18)	0.8426 (3)	0.0507 (5)
C2	0.34684 (15)	0.60022 (18)	0.9646 (3)	0.0528 (5)
C21	0.25199 (17)	0.5767 (2)	1.0452 (3)	0.0652 (7)
H21	0.2273	0.5101	1.0311	0.078*
O21	0.20482 (14)	0.63759 (17)	1.1274 (3)	0.0891 (6)
C3	0.39777 (18)	0.6879 (2)	1.0160 (3)	0.0655 (6)
H3	0.3701	0.7345	1.0952	0.079*
C4	0.48940 (19)	0.7073 (2)	0.9510 (3)	0.0720 (7)
H4	0.5233	0.7664	0.9871	0.086*
C5	0.53075 (17)	0.6391 (2)	0.8327 (3)	0.0658 (7)
H5	0.5929	0.6519	0.7908	0.079*
C6	0.48100 (15)	0.5525 (2)	0.7761 (3)	0.0578 (6)
H6	0.5083	0.5070	0.6947	0.069*
C1'	0.17335 (15)	0.49650 (18)	0.6435 (3)	0.0533 (5)
C2'	0.09929 (16)	0.43986 (18)	0.7179 (3)	0.0616 (6)
H2'	0.1073	0.3695	0.7390	0.074*
C3'	0.01372 (16)	0.48809 (18)	0.7607 (3)	0.0604 (6)
H3'	−0.0372	0.4506	0.8090	0.072*
C4'	0.00447 (16)	0.59233 (17)	0.7309 (3)	0.0551 (5)
Cl4'	−0.10263 (5)	0.65318 (5)	0.79106 (11)	0.0829 (3)
C5'	0.07775 (17)	0.64975 (19)	0.6559 (4)	0.0639 (6)
H5'	0.0698	0.7203	0.6364	0.077*
C6'	0.16282 (17)	0.6009 (2)	0.6104 (3)	0.0621 (6)
H6'	0.2127	0.6379	0.5577	0.074*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0439 (3)	0.0876 (5)	0.0755 (4)	0.0071 (3)	0.0080 (3)	−0.0278 (4)
O1	0.0500 (10)	0.151 (2)	0.0610 (10)	0.0036 (11)	0.0117 (8)	−0.0141 (11)
O2	0.0689 (12)	0.0872 (15)	0.1435 (19)	0.0176 (10)	−0.0034 (12)	−0.0616 (14)
O3	0.0480 (9)	0.0634 (10)	0.0723 (10)	0.0054 (7)	0.0048 (7)	−0.0043 (8)
C1	0.0404 (10)	0.0616 (14)	0.0499 (11)	0.0039 (10)	0.0009 (9)	0.0024 (10)
C2	0.0416 (11)	0.0661 (14)	0.0510 (12)	0.0046 (10)	0.0039 (9)	0.0029 (11)
C21	0.0517 (13)	0.0818 (18)	0.0627 (15)	0.0018 (12)	0.0148 (11)	−0.0009 (13)
O21	0.0658 (12)	0.0993 (15)	0.1041 (15)	0.0147 (10)	0.0363 (11)	−0.0075 (12)
C3	0.0613 (14)	0.0751 (17)	0.0604 (14)	0.0028 (13)	0.0059 (11)	−0.0097 (12)
C4	0.0607 (15)	0.0861 (19)	0.0691 (16)	−0.0177 (13)	0.0005 (13)	−0.0042 (14)
C5	0.0424 (12)	0.099 (2)	0.0562 (14)	−0.0083 (12)	0.0047 (10)	0.0072 (13)
C6	0.0405 (11)	0.0832 (17)	0.0499 (12)	0.0077 (11)	0.0054 (9)	0.0009 (12)
C1'	0.0409 (11)	0.0567 (14)	0.0624 (13)	0.0008 (9)	0.0057 (10)	−0.0137 (11)
C2'	0.0546 (13)	0.0427 (12)	0.0884 (17)	0.0002 (10)	0.0143 (12)	−0.0077 (11)
C3'	0.0487 (12)	0.0502 (13)	0.0832 (16)	−0.0034 (10)	0.0185 (11)	−0.0017 (12)
C4'	0.0458 (12)	0.0521 (13)	0.0676 (14)	0.0042 (10)	0.0073 (10)	−0.0024 (11)
Cl4'	0.0593 (4)	0.0659 (4)	0.1248 (6)	0.0184 (3)	0.0245 (4)	0.0072 (4)
C5'	0.0564 (14)	0.0469 (13)	0.0887 (17)	0.0002 (10)	0.0059 (12)	0.0089 (12)
C6'	0.0464 (12)	0.0652 (16)	0.0750 (16)	−0.0103 (11)	0.0090 (11)	0.0034 (12)

Geometric parameters (Å, º)

S1—O1	1.420 (2)	C5—C6	1.372 (4)
S1—O2	1.418 (2)	C5—H5	0.9300
S1—O3	1.6015 (18)	C6—H6	0.9300
S1—C1'	1.754 (2)	C1'—C6'	1.379 (3)
O3—C1	1.409 (3)	C1'—C2'	1.380 (3)
C1—C6	1.379 (3)	C2'—C3'	1.373 (3)
C1—C2	1.388 (3)	C2'—H2'	0.9300
C2—C3	1.381 (3)	C3'—C4'	1.372 (3)
C2—C21	1.478 (3)	C3'—H3'	0.9300
C21—O21	1.197 (3)	C4'—C5'	1.379 (3)
C21—H21	0.9300	C4'—Cl4'	1.735 (2)
C3—C4	1.381 (3)	C5'—C6'	1.377 (3)
C3—H3	0.9300	C5'—H5'	0.9300
C4—C5	1.378 (4)	C6'—H6'	0.9300
C4—H4	0.9300
O2—S1—O1	121.63 (13)	C6—C5—H5	119.7
O2—S1—O3	103.40 (12)	C4—C5—H5	119.7
O1—S1—O3	108.40 (10)	C5—C6—C1	118.7 (2)
O2—S1—C1'	110.47 (12)	C5—C6—H6	120.7
O1—S1—C1'	108.67 (12)	C1—C6—H6	120.7
O3—S1—C1'	102.45 (9)	C6'—C1'—C2'	121.1 (2)
C1—O3—S1	120.06 (14)	C6'—C1'—S1	120.18 (17)
C6—C1—C2	122.1 (2)	C2'—C1'—S1	118.62 (18)
C6—C1—O3	118.6 (2)	C3'—C2'—C1'	119.6 (2)
C2—C1—O3	119.14 (19)	C3'—C2'—H2'	120.2
C3—C2—C1	117.9 (2)	C1'—C2'—H2'	120.2
C3—C2—C21	120.1 (2)	C4'—C3'—C2'	119.0 (2)
C1—C2—C21	122.0 (2)	C4'—C3'—H3'	120.5
O21—C21—C2	124.4 (3)	C2'—C3'—H3'	120.5
O21—C21—H21	117.8	C3'—C4'—C5'	122.0 (2)
C2—C21—H21	117.8	C3'—C4'—Cl4'	118.66 (17)
C2—C3—C4	120.6 (2)	C5'—C4'—Cl4'	119.37 (18)
C2—C3—H3	119.7	C6'—C5'—C4'	118.9 (2)
C4—C3—H3	119.7	C6'—C5'—H5'	120.6
C5—C4—C3	120.1 (2)	C4'—C5'—H5'	120.6
C5—C4—H4	120.0	C5'—C6'—C1'	119.4 (2)
C3—C4—H4	120.0	C5'—C6'—H6'	120.3
C6—C5—C4	120.6 (2)	C1'—C6'—H6'	120.3
O2—S1—O3—C1	164.22 (16)	O3—C1—C6—C5	−176.4 (2)
O1—S1—O3—C1	33.87 (18)	O2—S1—C1'—C6'	−158.0 (2)
C1'—S1—O3—C1	−80.89 (17)	O1—S1—C1'—C6'	−22.2 (2)
S1—O3—C1—C6	−80.6 (2)	O3—S1—C1'—C6'	92.4 (2)
S1—O3—C1—C2	103.0 (2)	O2—S1—C1'—C2'	25.1 (2)
C6—C1—C2—C3	1.5 (3)	O1—S1—C1'—C2'	160.89 (18)
O3—C1—C2—C3	177.8 (2)	O3—S1—C1'—C2'	−84.5 (2)
C6—C1—C2—C21	−175.7 (2)	C6'—C1'—C2'—C3'	−0.3 (4)
O3—C1—C2—C21	0.6 (3)	S1—C1'—C2'—C3'	176.59 (19)
C3—C2—C21—O21	15.4 (4)	C1'—C2'—C3'—C4'	−1.1 (4)
C1—C2—C21—O21	−167.4 (2)	C2'—C3'—C4'—C5'	1.4 (4)
C1—C2—C3—C4	−1.6 (4)	C2'—C3'—C4'—Cl4'	−178.25 (19)
C21—C2—C3—C4	175.6 (2)	C3'—C4'—C5'—C6'	−0.3 (4)
C2—C3—C4—C5	0.4 (4)	Cl4'—C4'—C5'—C6'	179.34 (19)
C3—C4—C5—C6	1.0 (4)	C4'—C5'—C6'—C1'	−1.1 (4)
C4—C5—C6—C1	−1.1 (4)	C2'—C1'—C6'—C5'	1.4 (4)
C2—C1—C6—C5	−0.2 (3)	S1—C1'—C6'—C5'	−175.45 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1^i	0.93	2.51	3.224 (3)	134
C2′—H2′···Cl4′^ii	0.93	2.81	3.710 (2)	164
C3′—H3′···O21^iii	0.93	2.62	3.528 (3)	165
C5′—H5′···O21^iv	0.93	2.61	3.266 (3)	128

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

2-Formylphenyl 4-bromobenzenesulfonate (3c)

Crystal data

C13H9BrO4S	Z = 2
Mr = 341.17	F(000) = 340
Triclinic, P1	Dx = 1.718 Mg m^−3
a = 7.8282 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.5963 (6) Å	Cell parameters from 2262 reflections
c = 10.1139 (6) Å	θ = 2.1–27.2°
α = 91.249 (3)°	µ = 3.28 mm^−1
β = 102.818 (2)°	T = 296 K
γ = 95.938 (3)°	Prism, white
V = 659.38 (7) Å^3	0.40 × 0.32 × 0.24 mm

Data collection

Bruker Kappa APEXII CCD diffractometer	2877 independent reflections
Radiation source: fine-focus sealed tube	2262 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 7.80 pixels mm^-1	θmax = 27.2°, θmin = 2.1°
ω scans	h = −10→9
Absorption correction: multi-scan (SADABS; Bruker, 2007)	k = −10→11
Tmin = 0.552, Tmax = 0.746	l = −12→12
10289 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.031	w = 1/[σ^2(Fo^2) + (0.0364P)^2 + 0.2877P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.080	(Δ/σ)max < 0.001
S = 1.02	Δρmax = 0.32 e Å^−3
2877 reflections	Δρmin = −0.45 e Å^−3
173 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.098 (4)

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.

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

	x	y	z	Uiso*/Ueq
Br4'	1.14703 (4)	0.22424 (4)	−0.02018 (3)	0.07010 (16)
S1	0.61998 (8)	0.46297 (6)	0.31643 (6)	0.04895 (17)
O21	0.5722 (4)	−0.0996 (3)	0.1545 (3)	0.0986 (8)
O3	0.5273 (2)	0.30005 (18)	0.35207 (17)	0.0473 (4)
O1	0.7185 (3)	0.5427 (2)	0.4386 (2)	0.0640 (5)
O2	0.4785 (3)	0.5294 (2)	0.2338 (2)	0.0677 (5)
C1	0.6307 (3)	0.1930 (3)	0.4265 (2)	0.0446 (5)
C2	0.6421 (3)	0.0531 (3)	0.3600 (3)	0.0498 (6)
C21	0.5530 (4)	0.0154 (3)	0.2166 (3)	0.0656 (7)
H21	0.478109	0.084334	0.172036	0.079*
C3	0.7364 (4)	−0.0560 (3)	0.4332 (4)	0.0715 (8)
H3	0.744716	−0.151452	0.391402	0.086*
C4	0.8178 (5)	−0.0248 (5)	0.5668 (5)	0.0882 (11)
H4	0.882276	−0.098641	0.614871	0.106*
C5	0.8050 (4)	0.1134 (5)	0.6296 (3)	0.0834 (10)
H5	0.860949	0.132926	0.720484	0.100*
C6	0.7102 (4)	0.2258 (4)	0.5608 (3)	0.0634 (7)
H6	0.700826	0.320089	0.604057	0.076*
C1'	0.7661 (3)	0.4047 (2)	0.2215 (2)	0.0427 (5)
C2'	0.7016 (3)	0.3527 (3)	0.0878 (3)	0.0563 (6)
H2'	0.582801	0.353235	0.047226	0.068*
C3'	0.8152 (4)	0.3000 (3)	0.0155 (3)	0.0615 (7)
H3'	0.773827	0.263712	−0.074387	0.074*
C4'	0.9907 (3)	0.3013 (3)	0.0771 (3)	0.0498 (6)
C5'	1.0561 (3)	0.3565 (3)	0.2092 (3)	0.0541 (6)
H5'	1.175596	0.358904	0.248774	0.065*
C6'	0.9425 (3)	0.4080 (3)	0.2820 (3)	0.0508 (6)
H6'	0.984397	0.444903	0.371650	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br4'	0.0547 (2)	0.0877 (3)	0.0697 (2)	0.01169 (15)	0.01722 (14)	−0.00737 (15)
S1	0.0435 (3)	0.0379 (3)	0.0630 (4)	0.0097 (2)	0.0052 (3)	−0.0061 (3)
O21	0.117 (2)	0.0697 (14)	0.1103 (19)	0.0003 (13)	0.0360 (16)	−0.0360 (13)
O3	0.0339 (8)	0.0457 (9)	0.0610 (10)	0.0070 (7)	0.0072 (7)	−0.0032 (7)
O1	0.0633 (11)	0.0495 (10)	0.0728 (12)	0.0021 (8)	0.0063 (9)	−0.0216 (9)
O2	0.0577 (11)	0.0556 (10)	0.0896 (14)	0.0268 (9)	0.0065 (10)	0.0061 (10)
C1	0.0323 (11)	0.0490 (12)	0.0537 (13)	0.0032 (9)	0.0129 (10)	0.0056 (10)
C2	0.0393 (12)	0.0420 (12)	0.0703 (16)	0.0012 (10)	0.0185 (11)	0.0036 (11)
C21	0.0667 (18)	0.0487 (14)	0.0795 (19)	−0.0021 (13)	0.0173 (15)	−0.0105 (13)
C3	0.0594 (18)	0.0532 (16)	0.108 (3)	0.0129 (14)	0.0259 (18)	0.0229 (16)
C4	0.063 (2)	0.096 (3)	0.114 (3)	0.0243 (19)	0.024 (2)	0.057 (2)
C5	0.0599 (19)	0.127 (3)	0.0607 (18)	0.009 (2)	0.0060 (15)	0.032 (2)
C6	0.0535 (16)	0.0816 (19)	0.0546 (15)	0.0058 (14)	0.0121 (13)	0.0008 (14)
C1'	0.0366 (12)	0.0380 (11)	0.0505 (13)	0.0036 (9)	0.0036 (10)	0.0040 (9)
C2'	0.0372 (13)	0.0709 (16)	0.0532 (14)	0.0100 (12)	−0.0070 (11)	−0.0020 (12)
C3'	0.0481 (15)	0.0824 (19)	0.0481 (14)	0.0102 (13)	−0.0020 (11)	−0.0088 (13)
C4'	0.0417 (13)	0.0538 (14)	0.0530 (14)	0.0042 (11)	0.0090 (11)	0.0044 (11)
C5'	0.0346 (12)	0.0680 (16)	0.0545 (14)	0.0021 (11)	0.0008 (10)	0.0042 (12)
C6'	0.0403 (13)	0.0594 (14)	0.0461 (13)	−0.0021 (11)	−0.0001 (10)	−0.0015 (11)

Geometric parameters (Å, º)

Br4'—C4'	1.892 (2)	C4—C5	1.359 (5)
Br4'—O21^i	3.094 (3)	C4—H4	0.9300
S1—O2	1.4114 (19)	C5—C6	1.384 (5)
S1—O1	1.4219 (18)	C5—H5	0.9300
S1—O3	1.5955 (17)	C6—H6	0.9300
S1—C1'	1.751 (2)	C1'—C6'	1.377 (3)
O21—C21	1.200 (3)	C1'—C2'	1.382 (3)
O3—C1	1.408 (3)	C2'—C3'	1.374 (4)
C1—C6	1.373 (4)	C2'—H2'	0.9300
C1—C2	1.386 (3)	C3'—C4'	1.375 (4)
C2—C3	1.380 (4)	C3'—H3'	0.9300
C2—C21	1.476 (4)	C4'—C5'	1.375 (3)
C21—H21	0.9300	C5'—C6'	1.373 (4)
C3—C4	1.367 (5)	C5'—H5'	0.9300
C3—H3	0.9300	C6'—H6'	0.9300
C4'—Br4'—O21^i	174.78 (9)	C4—C5—H5	119.4
O2—S1—O1	120.49 (11)	C6—C5—H5	119.4
O2—S1—O3	102.58 (11)	C1—C6—C5	117.6 (3)
O1—S1—O3	109.09 (11)	C1—C6—H6	121.2
O2—S1—C1'	111.30 (12)	C5—C6—H6	121.2
O1—S1—C1'	108.95 (11)	C6'—C1'—C2'	121.1 (2)
O3—S1—C1'	102.78 (9)	C6'—C1'—S1	119.66 (18)
C1—O3—S1	119.56 (13)	C2'—C1'—S1	119.27 (18)
C6—C1—C2	122.3 (2)	C3'—C2'—C1'	119.1 (2)
C6—C1—O3	120.4 (2)	C3'—C2'—H2'	120.4
C2—C1—O3	117.2 (2)	C1'—C2'—H2'	120.4
C3—C2—C1	117.9 (3)	C2'—C3'—C4'	119.5 (2)
C3—C2—C21	119.4 (3)	C2'—C3'—H3'	120.3
C1—C2—C21	122.6 (2)	C4'—C3'—H3'	120.3
O21—C21—C2	123.5 (3)	C5'—C4'—C3'	121.5 (2)
O21—C21—H21	118.3	C5'—C4'—Br4'	118.69 (19)
C2—C21—H21	118.3	C3'—C4'—Br4'	119.78 (19)
C4—C3—C2	120.5 (3)	C6'—C5'—C4'	119.0 (2)
C4—C3—H3	119.7	C6'—C5'—H5'	120.5
C2—C3—H3	119.7	C4'—C5'—H5'	120.5
C5—C4—C3	120.3 (3)	C5'—C6'—C1'	119.7 (2)
C5—C4—H4	119.8	C5'—C6'—H6'	120.1
C3—C4—H4	119.8	C1'—C6'—H6'	120.1
C4—C5—C6	121.3 (3)
O2—S1—O3—C1	175.36 (17)	C4—C5—C6—C1	−0.5 (5)
O1—S1—O3—C1	−55.78 (18)	O2—S1—C1'—C6'	149.33 (19)
C1'—S1—O3—C1	59.74 (18)	O1—S1—C1'—C6'	14.1 (2)
S1—O3—C1—C6	69.2 (3)	O3—S1—C1'—C6'	−101.5 (2)
S1—O3—C1—C2	−113.2 (2)	O2—S1—C1'—C2'	−32.2 (2)
C6—C1—C2—C3	0.4 (4)	O1—S1—C1'—C2'	−167.4 (2)
O3—C1—C2—C3	−177.2 (2)	O3—S1—C1'—C2'	77.0 (2)
C6—C1—C2—C21	178.4 (2)	C6'—C1'—C2'—C3'	1.5 (4)
O3—C1—C2—C21	0.8 (3)	S1—C1'—C2'—C3'	−176.9 (2)
C3—C2—C21—O21	−7.9 (4)	C1'—C2'—C3'—C4'	−0.5 (4)
C1—C2—C21—O21	174.1 (3)	C2'—C3'—C4'—C5'	−1.0 (4)
C1—C2—C3—C4	−1.0 (4)	C2'—C3'—C4'—Br4'	178.4 (2)
C21—C2—C3—C4	−179.0 (3)	C3'—C4'—C5'—C6'	1.5 (4)
C2—C3—C4—C5	0.8 (5)	Br4'—C4'—C5'—C6'	−177.93 (19)
C3—C4—C5—C6	−0.1 (5)	C4'—C5'—C6'—C1'	−0.5 (4)
C2—C1—C6—C5	0.3 (4)	C2'—C1'—C6'—C5'	−1.0 (4)
O3—C1—C6—C5	177.8 (2)	S1—C1'—C6'—C5'	177.43 (19)

Symmetry code: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1^ii	0.93	2.68	3.440 (3)	140
C5′—H5′···O2^iii	0.93	2.69	3.436 (3)	138
C6′—H6′···O1^iv	0.93	2.66	3.406 (3)	138

Symmetry codes: (ii) x, y−1, z; (iii) x+1, y, z; (iv) −x+2, −y+1, −z+1.

4-Formylphenyl 4-chlorobenzenesulfonate (4b)

Crystal data

C13H9ClO4S	F(000) = 608
Mr = 296.71	Dx = 1.493 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.4670 (5) Å	Cell parameters from 1977 reflections
b = 11.9547 (5) Å	θ = 2.0–27.0°
c = 10.6575 (4) Å	µ = 0.45 mm^−1
β = 98.045 (1)°	T = 296 K
V = 1320.45 (10) Å^3	Plate, colorless
Z = 4	0.38 × 0.34 × 0.32 mm

Data collection

Bruker Kappa APEXII CCD diffractometer	2854 independent reflections
Radiation source: fine-focus sealed tube	2188 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Detector resolution: 7.80 pixels mm^-1	θmax = 27.0°, θmin = 2.0°
ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Bruker, 2011)	k = −15→14
Tmin = 0.617, Tmax = 0.746	l = −13→10
10509 measured 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)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.107	w = 1/[σ^2(Fo^2) + (0.0473P)^2 + 0.4702P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
2854 reflections	Δρmax = 0.47 e Å^−3
172 parameters	Δρmin = −0.32 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
S1	0.23967 (5)	−0.12072 (4)	0.43688 (5)	0.04835 (17)
O1	0.15829 (15)	−0.18133 (13)	0.34357 (16)	0.0634 (4)
O2	0.28054 (16)	−0.16797 (13)	0.55797 (15)	0.0644 (4)
O3	0.37398 (13)	−0.09681 (11)	0.38571 (13)	0.0506 (4)
C1	0.37465 (17)	−0.03426 (16)	0.27268 (18)	0.0430 (4)
C2	0.3159 (2)	−0.07404 (18)	0.1574 (2)	0.0531 (5)
H2	0.2726	−0.1422	0.1516	0.064*
C3	0.3231 (2)	−0.0101 (2)	0.0515 (2)	0.0558 (6)
H3	0.2829	−0.0347	−0.0270	0.067*
C4	0.3891 (2)	0.09025 (19)	0.0601 (2)	0.0519 (5)
C41	0.3978 (3)	0.1597 (2)	−0.0542 (3)	0.0684 (7)
H41	0.4464	0.2250	−0.0434	0.082*
O41	0.3479 (2)	0.13841 (19)	−0.15732 (19)	0.0921 (6)
C5	0.4491 (2)	0.12623 (18)	0.1761 (2)	0.0580 (6)
H5	0.4954	0.1929	0.1819	0.070*
C6	0.4412 (2)	0.06442 (17)	0.2839 (2)	0.0519 (5)
H6	0.4804	0.0893	0.3626	0.062*
C1'	0.17525 (17)	0.01302 (16)	0.45191 (18)	0.0416 (4)
C2'	0.2136 (2)	0.07337 (17)	0.56100 (19)	0.0479 (5)
H2'	0.2713	0.0428	0.6263	0.057*
C3'	0.1653 (2)	0.17974 (18)	0.5720 (2)	0.0517 (5)
H3'	0.1895	0.2216	0.6451	0.062*
C4'	0.08076 (19)	0.22314 (16)	0.4737 (2)	0.0480 (5)
Cl4'	0.02169 (6)	0.35742 (5)	0.48752 (7)	0.0738 (2)
C5'	0.0414 (2)	0.16315 (18)	0.3655 (2)	0.0523 (5)
H5'	−0.0165	0.1940	0.3006	0.063*
C6'	0.08882 (19)	0.05639 (18)	0.35388 (19)	0.0489 (5)
H6'	0.0630	0.0143	0.2814	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0516 (3)	0.0346 (3)	0.0577 (3)	−0.0020 (2)	0.0035 (2)	0.0046 (2)
O1	0.0636 (9)	0.0503 (9)	0.0748 (10)	−0.0145 (8)	0.0047 (8)	−0.0088 (8)
O2	0.0781 (11)	0.0456 (9)	0.0673 (10)	0.0033 (8)	0.0023 (8)	0.0200 (8)
O3	0.0467 (8)	0.0441 (8)	0.0599 (9)	0.0071 (6)	0.0039 (6)	0.0044 (7)
C1	0.0397 (9)	0.0387 (10)	0.0506 (12)	0.0061 (8)	0.0064 (8)	−0.0053 (9)
C2	0.0509 (12)	0.0443 (11)	0.0647 (14)	−0.0064 (9)	0.0099 (10)	−0.0145 (11)
C3	0.0516 (12)	0.0661 (15)	0.0487 (13)	−0.0004 (11)	0.0034 (9)	−0.0152 (11)
C4	0.0487 (11)	0.0523 (12)	0.0559 (13)	0.0046 (10)	0.0111 (9)	−0.0019 (10)
C41	0.0713 (16)	0.0707 (16)	0.0656 (17)	0.0011 (13)	0.0176 (13)	0.0061 (14)
O41	0.0966 (15)	0.1180 (18)	0.0602 (12)	0.0079 (12)	0.0053 (10)	0.0137 (12)
C5	0.0660 (14)	0.0449 (12)	0.0634 (14)	−0.0109 (10)	0.0099 (11)	−0.0059 (11)
C6	0.0557 (12)	0.0469 (12)	0.0514 (12)	−0.0068 (10)	0.0014 (9)	−0.0115 (10)
C1'	0.0419 (10)	0.0367 (10)	0.0464 (11)	0.0002 (8)	0.0067 (8)	0.0063 (8)
C2'	0.0506 (11)	0.0465 (11)	0.0442 (11)	0.0048 (9)	−0.0016 (8)	0.0029 (9)
C3'	0.0539 (12)	0.0489 (12)	0.0506 (12)	0.0006 (10)	0.0013 (9)	−0.0044 (10)
C4'	0.0431 (10)	0.0370 (10)	0.0651 (13)	0.0011 (8)	0.0116 (9)	0.0051 (10)
Cl4'	0.0710 (4)	0.0433 (3)	0.1061 (5)	0.0115 (3)	0.0091 (3)	0.0009 (3)
C5'	0.0500 (11)	0.0521 (12)	0.0524 (12)	0.0088 (10)	−0.0018 (9)	0.0121 (10)
C6'	0.0500 (11)	0.0503 (12)	0.0445 (11)	0.0028 (9)	−0.0003 (9)	−0.0010 (9)

Geometric parameters (Å, º)

S1—O1	1.4150 (16)	C5—C6	1.377 (3)
S1—O2	1.4189 (15)	C5—H5	0.9300
S1—O3	1.6031 (15)	C6—H6	0.9300
S1—C1'	1.7512 (19)	C1'—C2'	1.379 (3)
O3—C1	1.419 (2)	C1'—C6'	1.384 (3)
C1—C6	1.367 (3)	C2'—C3'	1.380 (3)
C1—C2	1.379 (3)	C2'—H2'	0.9300
C2—C3	1.374 (3)	C3'—C4'	1.375 (3)
C2—H2	0.9300	C3'—H3'	0.9300
C3—C4	1.381 (3)	C4'—C5'	1.372 (3)
C3—H3	0.9300	C4'—Cl4'	1.734 (2)
C4—C5	1.375 (3)	Cl4'—Cl4'^i	3.4542 (12)
C4—C41	1.488 (3)	C5'—C6'	1.381 (3)
C41—O41	1.177 (3)	C5'—H5'	0.9300
C41—H41	0.9300	C6'—H6'	0.9300
O1—S1—O2	120.70 (10)	C6—C5—H5	119.7
O1—S1—O3	108.81 (9)	C1—C6—C5	118.66 (19)
O2—S1—O3	102.31 (9)	C1—C6—H6	120.7
O1—S1—C1'	109.28 (10)	C5—C6—H6	120.7
O2—S1—C1'	110.56 (10)	C2'—C1'—C6'	121.53 (18)
O3—S1—C1'	103.63 (8)	C2'—C1'—S1	118.96 (14)
C1—O3—S1	119.44 (11)	C6'—C1'—S1	119.51 (15)
C6—C1—C2	122.3 (2)	C1'—C2'—C3'	119.14 (18)
C6—C1—O3	116.35 (17)	C1'—C2'—H2'	120.4
C2—C1—O3	121.33 (18)	C3'—C2'—H2'	120.4
C3—C2—C1	118.12 (19)	C4'—C3'—C2'	119.17 (19)
C3—C2—H2	120.9	C4'—C3'—H3'	120.4
C1—C2—H2	120.9	C2'—C3'—H3'	120.4
C2—C3—C4	120.8 (2)	C5'—C4'—C3'	121.93 (19)
C2—C3—H3	119.6	C5'—C4'—Cl4'	119.13 (16)
C4—C3—H3	119.6	C3'—C4'—Cl4'	118.93 (17)
C5—C4—C3	119.5 (2)	C4'—Cl4'—Cl4'^i	166.54 (8)
C5—C4—C41	119.3 (2)	C4'—C5'—C6'	119.28 (19)
C3—C4—C41	121.2 (2)	C4'—C5'—H5'	120.4
O41—C41—C4	125.0 (3)	C6'—C5'—H5'	120.4
O41—C41—H41	117.5	C5'—C6'—C1'	118.94 (19)
C4—C41—H41	117.5	C5'—C6'—H6'	120.5
C4—C5—C6	120.6 (2)	C1'—C6'—H6'	120.5
C4—C5—H5	119.7
O1—S1—O3—C1	60.07 (16)	O2—S1—C1'—C2'	24.81 (19)
O2—S1—O3—C1	−171.15 (14)	O3—S1—C1'—C2'	−84.18 (17)
C1'—S1—O3—C1	−56.13 (15)	O1—S1—C1'—C6'	−20.97 (19)
S1—O3—C1—C6	118.03 (17)	O2—S1—C1'—C6'	−156.12 (16)
S1—O3—C1—C2	−64.8 (2)	O3—S1—C1'—C6'	94.90 (16)
C6—C1—C2—C3	−1.4 (3)	C6'—C1'—C2'—C3'	−0.5 (3)
O3—C1—C2—C3	−178.47 (17)	S1—C1'—C2'—C3'	178.58 (16)
C1—C2—C3—C4	1.0 (3)	C1'—C2'—C3'—C4'	−0.4 (3)
C2—C3—C4—C5	0.4 (3)	C2'—C3'—C4'—C5'	1.0 (3)
C2—C3—C4—C41	179.7 (2)	C2'—C3'—C4'—Cl4'	−179.33 (16)
C5—C4—C41—O41	−178.1 (3)	C5'—C4'—Cl4'—Cl4'^i	−113.2 (4)
C3—C4—C41—O41	2.5 (4)	C3'—C4'—Cl4'—Cl4'^i	67.1 (4)
C3—C4—C5—C6	−1.6 (3)	C3'—C4'—C5'—C6'	−0.7 (3)
C41—C4—C5—C6	179.1 (2)	Cl4'—C4'—C5'—C6'	179.66 (16)
C2—C1—C6—C5	0.3 (3)	C4'—C5'—C6'—C1'	−0.2 (3)
O3—C1—C6—C5	177.51 (18)	C2'—C1'—C6'—C5'	0.8 (3)
C4—C5—C6—C1	1.2 (3)	S1—C1'—C6'—C5'	−178.24 (16)
O1—S1—C1'—C2'	159.95 (16)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2^ii	0.93	2.49	3.266 (3)	142
C6—H6···O2^iii	0.93	2.70	3.388 (3)	132
C2′—H2′···O41^iv	0.93	2.60	3.227 (3)	125
C3′—H3′···O41^iv	0.93	2.68	3.267 (3)	122
C5′—H5′···O1^v	0.93	2.48	3.389 (2)	166

Symmetry codes: (ii) x, −y−1/2, z−1/2; (iii) −x+1, −y, −z+1; (iv) x, y, z+1; (v) −x, y+1/2, −z+1/2.

4-Formylphenyl 4-bromobenzenesulfonate (4c)

Crystal data

C13H9BrO4S	Z = 2
Mr = 341.17	F(000) = 340
Triclinic, P1	Dx = 1.686 Mg m^−3
a = 6.8248 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.2849 (4) Å	Cell parameters from 1977 reflections
c = 15.1587 (9) Å	θ = 3.2–27.9°
α = 79.746 (3)°	µ = 3.22 mm^−1
β = 83.570 (2)°	T = 296 K
γ = 65.091 (2)°	Needle, white
V = 672.06 (6) Å^3	0.38 × 0.24 × 0.22 mm

Data collection

Bruker Kappa APEXII CCD diffractometer	3167 independent reflections
Radiation source: fine-focus sealed tube	1978 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 7.60 pixels mm^-1	θmax = 27.9°, θmin = 3.2°
ω scans	h = −5→8
Absorption correction: multi-scan (SADABS; Bruker, 2011)	k = −9→9
Tmin = 0.635, Tmax = 0.746	l = −19→19
11049 measured 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)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + (0.042P)^2 + 0.0141P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
3167 reflections	Δρmax = 0.26 e Å^−3
172 parameters	Δρmin = −0.29 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
S1	0.33633 (8)	0.55505 (8)	0.27314 (3)	0.05267 (16)
O1	0.3154 (3)	0.4404 (2)	0.21135 (10)	0.0659 (4)
O2	0.1717 (2)	0.6312 (2)	0.33930 (10)	0.0690 (4)
O3	0.3521 (2)	0.7588 (2)	0.21914 (9)	0.0548 (3)
C1	0.5027 (3)	0.7454 (3)	0.14598 (13)	0.0454 (4)
C2	0.4574 (3)	0.7204 (3)	0.06445 (13)	0.0497 (5)
H2	0.3338	0.7013	0.0575	0.060*
C3	0.5998 (3)	0.7242 (3)	−0.00724 (13)	0.0500 (5)
H3	0.5725	0.7064	−0.0632	0.060*
C4	0.7823 (3)	0.7540 (3)	0.00292 (13)	0.0458 (4)
C41	0.9258 (3)	0.7648 (3)	−0.07551 (14)	0.0563 (5)
H41	0.8913	0.7446	−0.1296	0.068*
O41	1.0837 (3)	0.7976 (3)	−0.07564 (10)	0.0728 (4)
C5	0.8226 (3)	0.7788 (3)	0.08671 (13)	0.0540 (5)
H5	0.9450	0.7995	0.0940	0.065*
C6	0.6847 (3)	0.7732 (3)	0.15871 (13)	0.0548 (5)
H6	0.7130	0.7878	0.2151	0.066*
C1'	0.5890 (3)	0.4246 (3)	0.32114 (12)	0.0459 (5)
C2'	0.6329 (3)	0.4946 (3)	0.39171 (14)	0.0591 (5)
H2'	0.5277	0.6079	0.4147	0.071*
C3'	0.8321 (4)	0.3966 (4)	0.42789 (16)	0.0671 (6)
H3'	0.8631	0.4424	0.4758	0.081*
C4'	0.9841 (4)	0.2321 (4)	0.39340 (16)	0.0594 (6)
Br4'	1.25989 (4)	0.09733 (5)	0.44290 (2)	0.10291 (17)
C5'	0.9427 (4)	0.1613 (4)	0.32313 (17)	0.0715 (6)
H5'	1.0488	0.0482	0.3004	0.086*
C6'	0.7430 (4)	0.2586 (3)	0.28651 (15)	0.0610 (6)
H6'	0.7126	0.2122	0.2386	0.073*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0480 (3)	0.0592 (3)	0.0510 (3)	−0.0234 (2)	0.0003 (2)	−0.0064 (3)
O1	0.0746 (10)	0.0763 (10)	0.0612 (9)	−0.0427 (8)	−0.0122 (7)	−0.0097 (8)
O2	0.0512 (8)	0.0827 (11)	0.0670 (10)	−0.0250 (8)	0.0116 (8)	−0.0111 (8)
O3	0.0495 (7)	0.0505 (8)	0.0568 (8)	−0.0147 (6)	0.0047 (6)	−0.0080 (7)
C1	0.0435 (10)	0.0391 (10)	0.0479 (11)	−0.0126 (8)	−0.0035 (9)	−0.0019 (9)
C2	0.0454 (11)	0.0514 (12)	0.0541 (13)	−0.0215 (9)	−0.0109 (9)	−0.0025 (10)
C3	0.0542 (11)	0.0511 (12)	0.0472 (11)	−0.0234 (10)	−0.0111 (9)	−0.0033 (9)
C4	0.0485 (10)	0.0385 (10)	0.0492 (11)	−0.0177 (8)	−0.0045 (9)	−0.0020 (9)
C41	0.0623 (13)	0.0521 (13)	0.0557 (13)	−0.0258 (11)	−0.0042 (10)	−0.0038 (10)
O41	0.0685 (10)	0.0955 (12)	0.0683 (10)	−0.0492 (9)	0.0060 (8)	−0.0120 (9)
C5	0.0538 (11)	0.0626 (13)	0.0550 (13)	−0.0331 (10)	−0.0110 (10)	−0.0029 (10)
C6	0.0609 (13)	0.0638 (14)	0.0468 (12)	−0.0314 (11)	−0.0096 (10)	−0.0060 (10)
C1'	0.0481 (10)	0.0487 (12)	0.0405 (11)	−0.0207 (9)	0.0034 (8)	−0.0066 (9)
C2'	0.0551 (12)	0.0656 (14)	0.0576 (13)	−0.0213 (11)	0.0034 (10)	−0.0239 (11)
C3'	0.0668 (15)	0.0798 (17)	0.0615 (14)	−0.0333 (13)	−0.0060 (12)	−0.0170 (13)
C4'	0.0540 (12)	0.0606 (14)	0.0590 (13)	−0.0246 (11)	−0.0068 (10)	0.0084 (11)
Br4'	0.0686 (2)	0.0937 (3)	0.1298 (3)	−0.02494 (17)	−0.03928 (17)	0.02523 (19)
C5'	0.0672 (15)	0.0551 (14)	0.0719 (16)	−0.0071 (12)	0.0045 (12)	−0.0099 (12)
C6'	0.0684 (14)	0.0541 (13)	0.0535 (13)	−0.0150 (12)	−0.0039 (11)	−0.0151 (11)

Geometric parameters (Å, º)

S1—O1	1.4156 (15)	C5—C6	1.365 (3)
S1—O2	1.4130 (15)	C5—H5	0.9300
S1—O3	1.6024 (14)	C6—H6	0.9300
S1—C1'	1.749 (2)	C1'—C6'	1.369 (3)
O3—C1	1.412 (2)	C1'—C2'	1.374 (3)
C1—C2	1.367 (3)	C2'—C3'	1.367 (3)
C1—C6	1.378 (3)	C2'—H2'	0.9300
C2—C3	1.379 (3)	C3'—C4'	1.356 (3)
C2—H2	0.9300	C3'—H3'	0.9300
C3—C4	1.380 (2)	C4'—C5'	1.367 (3)
C3—H3	0.9300	C4'—Br4'	1.888 (2)
C4—C5	1.387 (3)	Br4'—Br4'^i	3.4974 (5)
C4—C41	1.466 (3)	C5'—C6'	1.372 (3)
C41—O41	1.198 (2)	C5'—H5'	0.9300
C41—H41	0.9300	C6'—H6'	0.9300
O1—S1—O2	120.66 (9)	C4—C5—H5	119.6
O1—S1—O3	109.03 (8)	C5—C6—C1	118.51 (18)
O2—S1—O3	102.66 (8)	C5—C6—H6	120.7
O1—S1—C1'	109.48 (10)	C1—C6—H6	120.7
O2—S1—C1'	110.81 (9)	C6'—C1'—C2'	120.7 (2)
O3—S1—C1'	102.44 (8)	C6'—C1'—S1	119.99 (16)
C1—O3—S1	119.82 (11)	C2'—C1'—S1	119.30 (15)
C2—C1—C6	122.43 (18)	C3'—C2'—C1'	119.6 (2)
C2—C1—O3	119.73 (16)	C3'—C2'—H2'	120.2
C6—C1—O3	117.67 (17)	C1'—C2'—H2'	120.2
C1—C2—C3	118.22 (17)	C4'—C3'—C2'	119.6 (2)
C1—C2—H2	120.9	C4'—C3'—H3'	120.2
C3—C2—H2	120.9	C2'—C3'—H3'	120.2
C4—C3—C2	120.86 (17)	C3'—C4'—C5'	121.4 (2)
C4—C3—H3	119.6	C3'—C4'—Br4'	119.64 (19)
C2—C3—H3	119.6	C5'—C4'—Br4'	118.91 (18)
C3—C4—C5	119.18 (17)	C4'—Br4'—Br4'^i	171.27 (8)
C3—C4—C41	119.36 (18)	C4'—C5'—C6'	119.3 (2)
C5—C4—C41	121.43 (17)	C4'—C5'—H5'	120.3
O41—C41—C4	125.4 (2)	C6'—C5'—H5'	120.3
O41—C41—H41	117.3	C1'—C6'—C5'	119.4 (2)
C4—C41—H41	117.3	C1'—C6'—H6'	120.3
C6—C5—C4	120.79 (17)	C5'—C6'—H6'	120.3
C6—C5—H5	119.6
O1—S1—O3—C1	−50.95 (15)	O1—S1—C1'—C6'	10.64 (19)
O2—S1—O3—C1	179.97 (13)	O2—S1—C1'—C6'	146.14 (16)
C1'—S1—O3—C1	64.98 (15)	O3—S1—C1'—C6'	−104.96 (17)
S1—O3—C1—C2	78.78 (19)	O1—S1—C1'—C2'	−171.44 (15)
S1—O3—C1—C6	−105.78 (18)	O2—S1—C1'—C2'	−35.95 (18)
C6—C1—C2—C3	−0.3 (3)	O3—S1—C1'—C2'	72.95 (17)
O3—C1—C2—C3	174.94 (17)	C6'—C1'—C2'—C3'	−0.3 (3)
C1—C2—C3—C4	−0.5 (3)	S1—C1'—C2'—C3'	−178.23 (17)
C2—C3—C4—C5	0.5 (3)	C1'—C2'—C3'—C4'	0.3 (3)
C2—C3—C4—C41	−177.70 (18)	C2'—C3'—C4'—C5'	−0.2 (4)
C3—C4—C41—O41	177.1 (2)	C2'—C3'—C4'—Br4'	179.70 (16)
C5—C4—C41—O41	−1.1 (3)	C3'—C4'—C5'—C6'	0.1 (4)
C3—C4—C5—C6	0.3 (3)	Br4'—C4'—C5'—C6'	−179.79 (17)
C41—C4—C5—C6	178.41 (19)	C2'—C1'—C6'—C5'	0.2 (3)
C4—C5—C6—C1	−1.0 (3)	S1—C1'—C6'—C5'	178.13 (17)
C2—C1—C6—C5	1.0 (3)	C4'—C5'—C6'—C1'	−0.1 (3)
O3—C1—C6—C5	−174.31 (17)

Symmetry code: (i) −x+3, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O41^ii	0.93	2.60	3.303 (2)	133
C5′—H5′···O3^iii	0.93	2.63	3.556 (3)	173
C3—H3···O1^iv	0.93	2.56	3.418 (2)	153
C6′—H6′···O41^v	0.93	2.69	3.316 (3)	125

Symmetry codes: (ii) x−1, y, z; (iii) x+1, y−1, z; (iv) −x+1, −y+1, −z; (v) −x+2, −y+1, −z.