5-Methyl-1,3-phenyl­ene bis­[5-(di­methyl­amino)­naphthalene-1-sulfonate]: crystal structure and DFT calculations

The title compound possesses crystallographically imposed twofold symmetry with the two C atoms of the central benzene ring and the C atom of its methyl substituent lying on the twofold rotation axis. The two dansyl groups are twisted away from the plane of methyl­phenyl bridging unit in opposite directions. The crystal packing features weak C—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.037
• wR factor = 0.106
• Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1B      ..O3       .       2.70 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H16C     ..O2       .       2.63 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Theta(Min).          5 Note
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         41 Report

Alert level G
PLAT005_ALERT_5_G No Embedded Refinement Details Found  in the CIF     Please Do !
PLAT300_ALERT_4_G Atom Site Occupancy of H1A        Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H1B        Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H1C        Constrained at        0.5 Check
PLAT367_ALERT_2_G Long?  C(sp?)-C(sp?) Bond  C1       - C2       .       1.51 Ang.
PLAT395_ALERT_2_G Deviating  X-O-Y    Angle From 120 for O1             119.1 Degree
PLAT789_ALERT_4_G Atoms with Negative _atom_site_disorder_group  #          3 Check
PLAT898_ALERT_4_G Second Reported H-M Symbol in CIF Ignored ......          ! Check
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         14 Note
PLAT960_ALERT_3_G Number of Intensities with I  <   - 2*sig(I) ...          2 Check
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          9 Info

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   8 ALERT type 4 Improvement, methodology, query or suggestion
   1 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

---

Computing details

Data collection: APEX CCD (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

5-Methyl-1,3-phenylene bis[5-(dimethylamino)naphthalene-1-sulfonate]

Crystal data

C31H30N2O6S2	F(000) = 1240
Mr = 590.69	Dx = 1.385 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.5072 (6) Å	Cell parameters from 8490 reflections
b = 12.3504 (5) Å	θ = 3.0–26.4°
c = 16.3017 (5) Å	µ = 0.24 mm^−1
β = 114.868 (1)°	T = 296 K
V = 2832.62 (18) Å^3	Block, light green
Z = 4	0.44 × 0.44 × 0.4 mm

Data collection

Bruker D8 QUEST CMOS diffractometer	2857 independent reflections
Radiation source: sealed tube	2437 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
φ and ω scans	θmax = 26.4°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −19→19
Tmin = 0.710, Tmax = 0.745	k = −15→15
18169 measured reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.106	w = 1/[σ^2(Fo^2) + (0.0573P)^2 + 1.5124P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
2857 reflections	Δρmax = 0.23 e Å^−3
190 parameters	Δρmin = −0.33 e Å^−3
0 restraints

Special details

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	Occ. (<1)
S1	0.24891 (3)	0.59066 (4)	0.67336 (3)	0.04868 (15)
O1	0.35036 (8)	0.59425 (9)	0.75828 (7)	0.0458 (3)
O2	0.21860 (9)	0.69851 (11)	0.64561 (10)	0.0632 (4)
O3	0.19426 (9)	0.52398 (12)	0.70474 (10)	0.0675 (4)
N1	0.43181 (10)	0.25203 (12)	0.48853 (10)	0.0535 (4)
C6	0.27383 (10)	0.52632 (13)	0.58976 (11)	0.0424 (4)
C7	0.25296 (12)	0.58335 (13)	0.51133 (12)	0.0483 (4)
H7	0.2260	0.6519	0.5041	0.058*
C8	0.27244 (12)	0.53779 (15)	0.44241 (12)	0.0526 (4)
H8	0.2545	0.5739	0.3876	0.063*
C9	0.31748 (12)	0.44083 (14)	0.45540 (11)	0.0473 (4)
H9	0.3316	0.4125	0.4096	0.057*
C10	0.34350 (10)	0.38180 (12)	0.53666 (10)	0.0400 (3)
C11	0.39393 (11)	0.28115 (13)	0.55059 (11)	0.0458 (4)
C12	0.40220 (13)	0.21854 (14)	0.62272 (14)	0.0586 (5)
H12	0.4305	0.1507	0.6302	0.070*
C13	0.36883 (15)	0.25495 (16)	0.68541 (14)	0.0644 (5)
H13	0.3740	0.2096	0.7328	0.077*
C14	0.32938 (13)	0.35391 (15)	0.67920 (12)	0.0532 (4)
H14	0.3114	0.3778	0.7238	0.064*
C15	0.31559 (10)	0.42115 (12)	0.60409 (10)	0.0405 (3)
C16	0.51087 (14)	0.32132 (16)	0.49436 (14)	0.0616 (5)
H16A	0.4915	0.3958	0.4888	0.092*
H16B	0.5289	0.3032	0.4465	0.092*
H16C	0.5640	0.3103	0.5516	0.092*
C17	0.45713 (16)	0.13831 (16)	0.48903 (16)	0.0728 (6)
H17A	0.5091	0.1212	0.5457	0.109*
H17B	0.4755	0.1250	0.4406	0.109*
H17C	0.4034	0.0939	0.4812	0.109*
C4	0.42508 (10)	0.65401 (13)	0.75150 (10)	0.0400 (3)
C3	0.42371 (11)	0.76504 (14)	0.75244 (11)	0.0459 (4)
H3	0.3723	0.8016	0.7547	0.055*
C2	0.5000	0.82262 (19)	0.7500	0.0490 (5)
C5	0.5000	0.59523 (18)	0.7500	0.0398 (5)
H5	0.5000	0.5199	0.7500	0.048*
C1	0.5000	0.9447 (2)	0.7500	0.0765 (9)
H1A	0.4591	0.9706	0.6908	0.115*	0.5
H1B	0.5635	0.9706	0.7663	0.115*	0.5
H1C	0.4774	0.9706	0.7929	0.115*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0324 (2)	0.0582 (3)	0.0573 (3)	−0.00268 (16)	0.02067 (19)	−0.00729 (18)
O1	0.0378 (6)	0.0558 (7)	0.0467 (6)	−0.0065 (5)	0.0208 (5)	−0.0008 (5)
O2	0.0455 (6)	0.0600 (8)	0.0765 (9)	0.0133 (6)	0.0182 (6)	−0.0078 (6)
O3	0.0482 (7)	0.0864 (10)	0.0816 (9)	−0.0191 (7)	0.0407 (7)	−0.0157 (7)
N1	0.0461 (8)	0.0486 (8)	0.0618 (9)	0.0003 (6)	0.0189 (7)	−0.0103 (7)
C6	0.0325 (7)	0.0458 (9)	0.0473 (9)	−0.0036 (6)	0.0153 (6)	−0.0010 (7)
C7	0.0429 (8)	0.0426 (9)	0.0548 (10)	0.0020 (7)	0.0158 (8)	0.0066 (7)
C8	0.0509 (9)	0.0554 (10)	0.0452 (9)	0.0027 (8)	0.0142 (8)	0.0142 (7)
C9	0.0451 (9)	0.0538 (10)	0.0411 (8)	−0.0015 (7)	0.0163 (7)	0.0013 (7)
C10	0.0336 (7)	0.0395 (8)	0.0423 (8)	−0.0059 (6)	0.0114 (6)	0.0000 (6)
C11	0.0375 (8)	0.0397 (8)	0.0531 (9)	−0.0052 (6)	0.0121 (7)	−0.0032 (7)
C12	0.0564 (10)	0.0414 (9)	0.0743 (13)	0.0032 (8)	0.0241 (10)	0.0119 (8)
C13	0.0662 (12)	0.0583 (11)	0.0700 (12)	−0.0002 (9)	0.0300 (10)	0.0265 (10)
C14	0.0517 (10)	0.0575 (11)	0.0545 (10)	−0.0016 (8)	0.0264 (8)	0.0113 (8)
C15	0.0336 (7)	0.0425 (8)	0.0433 (8)	−0.0062 (6)	0.0141 (6)	0.0029 (6)
C16	0.0507 (10)	0.0686 (12)	0.0671 (12)	0.0000 (9)	0.0263 (9)	−0.0005 (9)
C17	0.0682 (13)	0.0544 (11)	0.0892 (15)	0.0032 (10)	0.0266 (12)	−0.0176 (10)
C4	0.0332 (7)	0.0499 (9)	0.0360 (8)	−0.0049 (6)	0.0136 (6)	−0.0008 (6)
C3	0.0373 (8)	0.0487 (9)	0.0518 (9)	0.0027 (6)	0.0186 (7)	−0.0020 (7)
C2	0.0446 (12)	0.0440 (12)	0.0577 (14)	0.000	0.0208 (11)	0.000
C5	0.0372 (10)	0.0432 (12)	0.0363 (11)	0.000	0.0129 (9)	0.000
C1	0.0671 (18)	0.0455 (15)	0.124 (3)	0.000	0.0475 (19)	0.000

Geometric parameters (Å, º)

S1—O1	1.6006 (12)	C13—H13	0.9300
S1—O2	1.4215 (14)	C13—C14	1.352 (3)
S1—O3	1.4223 (13)	C14—H14	0.9300
S1—C6	1.7552 (16)	C14—C15	1.419 (2)
O1—C4	1.4166 (17)	C16—H16A	0.9600
N1—C11	1.413 (2)	C16—H16B	0.9600
N1—C16	1.465 (2)	C16—H16C	0.9600
N1—C17	1.458 (2)	C17—H17A	0.9600
C6—C7	1.374 (2)	C17—H17B	0.9600
C6—C15	1.426 (2)	C17—H17C	0.9600
C7—H7	0.9300	C4—C3	1.372 (2)
C7—C8	1.399 (3)	C4—C5	1.3789 (19)
C8—H8	0.9300	C3—H3	0.9300
C8—C9	1.357 (2)	C3—C2	1.395 (2)
C9—H9	0.9300	C2—C3^i	1.395 (2)
C9—C10	1.414 (2)	C2—C1	1.507 (3)
C10—C11	1.435 (2)	C5—C4^i	1.3789 (19)
C10—C15	1.426 (2)	C5—H5	0.9300
C11—C12	1.367 (3)	C1—H1A	0.9600
C12—H12	0.9300	C1—H1B	0.9600
C12—C13	1.400 (3)	C1—H1C	0.9600
O1—S1—C6	103.11 (7)	C13—C14—C15	119.53 (17)
O2—S1—O1	108.81 (7)	C15—C14—H14	120.2
O2—S1—O3	119.32 (9)	C10—C15—C6	116.65 (14)
O2—S1—C6	109.18 (8)	C14—C15—C6	124.57 (15)
O3—S1—O1	102.86 (8)	C14—C15—C10	118.77 (15)
O3—S1—C6	112.10 (8)	N1—C16—H16A	109.5
C4—O1—S1	119.05 (9)	N1—C16—H16B	109.5
C11—N1—C16	113.17 (14)	N1—C16—H16C	109.5
C11—N1—C17	115.68 (16)	H16A—C16—H16B	109.5
C17—N1—C16	110.26 (16)	H16A—C16—H16C	109.5
C7—C6—S1	116.60 (13)	H16B—C16—H16C	109.5
C7—C6—C15	122.16 (15)	N1—C17—H17A	109.5
C15—C6—S1	121.22 (12)	N1—C17—H17B	109.5
C6—C7—H7	120.1	N1—C17—H17C	109.5
C6—C7—C8	119.70 (15)	H17A—C17—H17B	109.5
C8—C7—H7	120.1	H17A—C17—H17C	109.5
C7—C8—H8	120.0	H17B—C17—H17C	109.5
C9—C8—C7	120.03 (15)	C3—C4—O1	120.20 (13)
C9—C8—H8	120.0	C3—C4—C5	122.93 (15)
C8—C9—H9	119.1	C5—C4—O1	116.74 (14)
C8—C9—C10	121.77 (16)	C4—C3—H3	120.3
C10—C9—H9	119.1	C4—C3—C2	119.48 (16)
C9—C10—C11	121.12 (15)	C2—C3—H3	120.3
C9—C10—C15	119.14 (14)	C3—C2—C3^i	118.7 (2)
C15—C10—C11	119.69 (14)	C3^i—C2—C1	120.64 (11)
N1—C11—C10	118.03 (15)	C3—C2—C1	120.65 (11)
C12—C11—N1	123.69 (16)	C4—C5—C4^i	116.5 (2)
C12—C11—C10	118.28 (16)	C4—C5—H5	121.8
C11—C12—H12	119.5	C4^i—C5—H5	121.8
C11—C12—C13	121.09 (17)	C2—C1—H1A	109.5
C13—C12—H12	119.5	C2—C1—H1B	109.5
C12—C13—H13	119.0	C2—C1—H1C	109.5
C14—C13—C12	122.05 (17)	H1A—C1—H1B	109.5
C14—C13—H13	119.0	H1A—C1—H1C	109.5
C13—C14—H14	120.2	H1B—C1—H1C	109.5
S1—O1—C4—C3	72.98 (16)	C9—C10—C11—N1	11.1 (2)
S1—O1—C4—C5	−111.07 (11)	C9—C10—C11—C12	−168.50 (16)
S1—C6—C7—C8	178.93 (13)	C9—C10—C15—C6	−8.3 (2)
S1—C6—C15—C10	−172.59 (11)	C9—C10—C15—C14	170.72 (15)
S1—C6—C15—C14	8.4 (2)	C10—C11—C12—C13	−4.8 (3)
O1—S1—C6—C7	−121.15 (13)	C11—C10—C15—C6	174.23 (13)
O1—S1—C6—C15	57.51 (13)	C11—C10—C15—C14	−6.7 (2)
O1—C4—C3—C2	176.99 (11)	C11—C12—C13—C14	−1.7 (3)
O1—C4—C5—C4^i	−176.50 (14)	C12—C13—C14—C15	4.0 (3)
O2—S1—O1—C4	−53.02 (13)	C13—C14—C15—C6	179.28 (16)
O2—S1—C6—C7	−5.58 (15)	C13—C14—C15—C10	0.3 (2)
O2—S1—C6—C15	173.07 (12)	C15—C6—C7—C8	0.3 (2)
O3—S1—O1—C4	179.51 (11)	C15—C10—C11—N1	−171.45 (13)
O3—S1—C6—C7	128.91 (14)	C15—C10—C11—C12	8.9 (2)
O3—S1—C6—C15	−52.44 (15)	C16—N1—C11—C10	68.68 (19)
N1—C11—C12—C13	175.62 (17)	C16—N1—C11—C12	−111.71 (19)
C6—S1—O1—C4	62.80 (12)	C17—N1—C11—C10	−162.74 (15)
C6—C7—C8—C9	−4.3 (3)	C17—N1—C11—C12	16.9 (2)
C7—C6—C15—C10	6.0 (2)	C4—C3—C2—C3^i	−0.62 (10)
C7—C6—C15—C14	−172.98 (16)	C4—C3—C2—C1	179.38 (10)
C7—C8—C9—C10	1.8 (3)	C3—C4—C5—C4^i	−0.66 (11)
C8—C9—C10—C11	−177.88 (15)	C5—C4—C3—C2	1.3 (2)
C8—C9—C10—C15	4.7 (2)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O3	0.93	2.49	3.116 (2)	125
C1—H1B···O3^ii	0.96	2.70	3.528 (2)	145
C9—H9···O1^iii	0.93	2.60	3.486 (2)	158
C16—H16C···O2^iv	0.96	2.63	3.475 (2)	147

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