Benzene-1,2-diaminium bis­(4-methyl­benzene-1-sulfonate)

The structure of the title salt, C₆H₁₀N₂²⁺·2C₇H₇O₃S⁻, consists of a unique benzene-1,2-diaminium dication charge balanced by a pair of crystallographically independent 4-methyl­benzene-1-sulfonate anions. The cations and anions are inter­linked by several N—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.040
• wR factor = 0.126
• Data-to-parameter ratio = 23.8

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT220_ALERT_2_C NonSolvent Resd 2  C   Ueq(max) / Ueq(min) Range        3.2 Ratio
PLAT242_ALERT_2_C Low    MainMol Ueq as Compared to Neighbors of        C22 Check
PLAT761_ALERT_1_C CIF Contains no X-H Bonds ......................     Please Check
PLAT762_ALERT_1_C CIF Contains no X-Y-H or H-Y-H Angles ..........     Please Check
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1 Note
              C7 H7 O3 S
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -2.922 Report
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          3 Report

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          6 Report
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT128_ALERT_4_G Alternate Setting for Input Space Group     C2/c       I2/a Note
PLAT802_ALERT_4_G CIF Input Record(s) with more than 80 Characters          3 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          3 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          3 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         11 Info

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

   3 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
   4 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

Data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2018); data reduction: SAINT (Bruker, 2018); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: shelXle (Hübschle et al., 2011).

Benzene-1,2-diaminium bis(4-methylbenzene-1-sulfonate)

Crystal data

C6H10N2^2+·2C7H7O3S^−	F(000) = 1904
Mr = 452.53	Dx = 1.396 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 29.1537 (9) Å	Cell parameters from 9968 reflections
b = 8.8739 (3) Å	θ = 2.9–29.9°
c = 19.9919 (6) Å	µ = 0.29 mm^−1
β = 123.621 (1)°	T = 293 K
V = 4306.9 (2) Å^3	Block, colourless
Z = 8	0.56 × 0.14 × 0.12 mm

Data collection

Bruker D8 Quest ECO diffractometer	4705 reflections with I > 2σ(I)
Radiation source: Sealed Tube	Rint = 0.046
φ and ω scans	θmax = 30.5°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2018)	h = −41→41
Tmin = 0.696, Tmax = 0.746	k = −12→12
59056 measured reflections	l = −28→28
6568 independent 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)] = 0.040	w = 1/[σ^2(Fo^2) + (0.0525P)^2 + 2.9966P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.126	(Δ/σ)max = 0.001
S = 1.07	Δρmax = 0.34 e Å^−3
6568 reflections	Δρmin = −0.39 e Å^−3
276 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0026 (3)

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.

Refinement. All hydrogen atoms were located in appropriate positions and were included in calculated positions and refined with a riding model for both C—H and N—H protons. C–H distances ranged from = 0.93 and 0.96 Å for aromatic and methyl H atoms, respectively, and 0.89 for NH₃⁺ H atoms with U_iso(H) = 1.2 U_eq(C-aromatic) and U_iso(H) = 1.5 U_eq(C-methyl, NH₃⁺).

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

	x	y	z	Uiso*/Ueq
N1	0.52597 (6)	0.42385 (15)	0.43447 (8)	0.0399 (3)
H1A	0.516000	0.511465	0.408451	0.060*
H1B	0.552390	0.439398	0.485886	0.060*
H1C	0.497014	0.381592	0.430938	0.060*
N2	0.54019 (6)	0.10069 (15)	0.46813 (8)	0.0374 (3)
H2A	0.505767	0.066255	0.439229	0.056*
H2B	0.543473	0.168126	0.503495	0.056*
H2C	0.563230	0.024462	0.494094	0.056*
C1	0.54643 (6)	0.32416 (17)	0.39869 (9)	0.0349 (3)
C2	0.55343 (6)	0.17140 (17)	0.41510 (9)	0.0344 (3)
C3	0.57224 (8)	0.0796 (2)	0.37927 (12)	0.0505 (4)
H3	0.576521	−0.023317	0.389900	0.061*
C4	0.58462 (11)	0.1411 (3)	0.32770 (14)	0.0661 (6)
H4	0.597256	0.079592	0.303508	0.079*
C5	0.57830 (11)	0.2935 (3)	0.31201 (15)	0.0664 (6)
H5	0.586983	0.334936	0.277609	0.080*
C6	0.55909 (9)	0.3848 (2)	0.34726 (12)	0.0529 (4)
H6	0.554660	0.487571	0.336310	0.064*
S11	0.60971 (2)	−0.26457 (4)	0.57918 (2)	0.03904 (11)
O11	0.61408 (5)	−0.40103 (15)	0.54362 (8)	0.0562 (3)
O12	0.61358 (6)	−0.12891 (15)	0.54200 (8)	0.0563 (3)
O13	0.56134 (5)	−0.26132 (16)	0.58310 (9)	0.0573 (4)
C11	0.81185 (11)	−0.2503 (3)	0.92035 (15)	0.0827 (8)
H11A	0.833550	−0.338591	0.929269	0.124*
H11B	0.801302	−0.248348	0.958103	0.124*
H11C	0.833111	−0.161970	0.927333	0.124*
C12	0.76068 (8)	−0.2532 (2)	0.83564 (12)	0.0540 (5)
C13	0.71405 (8)	−0.1716 (2)	0.81418 (11)	0.0541 (5)
H13	0.713844	−0.113580	0.852757	0.065*
C14	0.66758 (7)	−0.1744 (2)	0.73639 (11)	0.0460 (4)
H14	0.636634	−0.118206	0.722766	0.055*
C15	0.66778 (6)	−0.26174 (17)	0.67934 (10)	0.0363 (3)
C16	0.71387 (7)	−0.3444 (2)	0.69966 (12)	0.0523 (4)
H16	0.713945	−0.403424	0.661270	0.063*
C17	0.76014 (8)	−0.3390 (3)	0.77780 (13)	0.0616 (5)
H17	0.791258	−0.394165	0.791294	0.074*
S21	0.45059 (2)	0.76496 (4)	0.35286 (2)	0.03714 (11)
O21	0.49995 (5)	0.70837 (16)	0.36096 (8)	0.0547 (3)
O22	0.44084 (6)	0.69248 (16)	0.40921 (7)	0.0559 (3)
O23	0.44971 (6)	0.92776 (14)	0.35764 (8)	0.0565 (4)
C21	0.26881 (15)	0.5602 (4)	0.01997 (17)	0.1233 (14)
H21A	0.233080	0.582893	0.009049	0.185*
H21B	0.272805	0.452969	0.018852	0.185*
H21C	0.272661	0.606499	−0.020056	0.185*
C22	0.31300 (11)	0.6205 (3)	0.10249 (13)	0.0742 (7)
C23	0.30782 (11)	0.6004 (3)	0.16652 (16)	0.0813 (7)
H23	0.275944	0.556751	0.157815	0.098*
C24	0.34940 (9)	0.6443 (3)	0.24375 (13)	0.0609 (5)
H24	0.345911	0.627550	0.286660	0.073*
C25	0.39576 (7)	0.71265 (18)	0.25587 (9)	0.0387 (3)
C26	0.40091 (9)	0.7360 (2)	0.19192 (11)	0.0496 (4)
H26	0.432285	0.782254	0.200184	0.060*
C27	0.35939 (11)	0.6905 (3)	0.11584 (12)	0.0665 (6)
H27	0.362871	0.707427	0.072940	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0434 (7)	0.0323 (6)	0.0424 (7)	0.0035 (5)	0.0229 (6)	−0.0005 (5)
N2	0.0435 (7)	0.0346 (6)	0.0376 (7)	0.0003 (5)	0.0246 (6)	0.0022 (5)
C1	0.0357 (7)	0.0340 (7)	0.0356 (7)	−0.0015 (6)	0.0202 (6)	−0.0014 (6)
C2	0.0390 (8)	0.0329 (7)	0.0352 (7)	−0.0019 (6)	0.0230 (6)	−0.0009 (6)
C3	0.0707 (12)	0.0390 (9)	0.0597 (11)	0.0038 (8)	0.0473 (10)	−0.0019 (8)
C4	0.0979 (17)	0.0598 (12)	0.0792 (15)	0.0033 (11)	0.0732 (14)	−0.0036 (11)
C5	0.0924 (16)	0.0672 (13)	0.0737 (14)	−0.0001 (12)	0.0673 (14)	0.0091 (11)
C6	0.0669 (12)	0.0435 (9)	0.0623 (11)	−0.0018 (8)	0.0444 (10)	0.0082 (8)
S11	0.03285 (19)	0.0358 (2)	0.0398 (2)	0.00174 (14)	0.01463 (16)	−0.00139 (15)
O11	0.0498 (7)	0.0493 (7)	0.0513 (7)	0.0054 (6)	0.0165 (6)	−0.0134 (6)
O12	0.0558 (8)	0.0497 (7)	0.0522 (7)	0.0056 (6)	0.0227 (6)	0.0147 (6)
O13	0.0324 (6)	0.0628 (9)	0.0694 (9)	−0.0034 (5)	0.0237 (6)	−0.0094 (7)
C11	0.0602 (14)	0.095 (2)	0.0504 (12)	0.0003 (12)	0.0039 (11)	−0.0007 (12)
C12	0.0433 (9)	0.0557 (11)	0.0440 (10)	−0.0025 (8)	0.0122 (8)	0.0027 (8)
C13	0.0534 (11)	0.0615 (12)	0.0427 (9)	−0.0035 (9)	0.0236 (8)	−0.0089 (8)
C14	0.0403 (8)	0.0516 (10)	0.0449 (9)	0.0032 (7)	0.0229 (7)	−0.0038 (7)
C15	0.0320 (7)	0.0356 (7)	0.0390 (8)	−0.0009 (6)	0.0182 (6)	0.0017 (6)
C16	0.0413 (9)	0.0563 (11)	0.0504 (10)	0.0096 (8)	0.0199 (8)	−0.0063 (8)
C17	0.0403 (10)	0.0659 (13)	0.0586 (12)	0.0134 (9)	0.0149 (9)	−0.0009 (10)
S21	0.0452 (2)	0.03159 (19)	0.03394 (19)	0.00202 (14)	0.02151 (17)	0.00074 (13)
O21	0.0502 (7)	0.0599 (8)	0.0523 (7)	0.0147 (6)	0.0274 (6)	0.0096 (6)
O22	0.0741 (9)	0.0606 (8)	0.0383 (6)	−0.0077 (7)	0.0345 (7)	−0.0003 (6)
O23	0.0581 (8)	0.0318 (6)	0.0582 (8)	0.0003 (5)	0.0188 (7)	−0.0062 (5)
C21	0.131 (3)	0.089 (2)	0.0642 (16)	−0.005 (2)	0.0007 (17)	−0.0314 (16)
C22	0.0841 (16)	0.0541 (12)	0.0475 (11)	0.0005 (11)	0.0132 (11)	−0.0131 (9)
C23	0.0700 (15)	0.0772 (17)	0.0764 (16)	−0.0281 (13)	0.0279 (13)	−0.0191 (13)
C24	0.0641 (12)	0.0657 (13)	0.0564 (11)	−0.0176 (10)	0.0355 (10)	−0.0091 (10)
C25	0.0486 (9)	0.0326 (7)	0.0356 (7)	0.0005 (6)	0.0237 (7)	−0.0019 (6)
C26	0.0659 (12)	0.0465 (10)	0.0406 (9)	0.0041 (8)	0.0320 (9)	0.0042 (7)
C27	0.0919 (17)	0.0610 (12)	0.0383 (9)	0.0128 (12)	0.0309 (11)	0.0004 (9)

Geometric parameters (Å, º)

N1—C1	1.4570 (19)	C13—C14	1.386 (3)
N2—C2	1.4561 (18)	C14—C15	1.382 (2)
C1—C6	1.380 (2)	C15—C16	1.380 (2)
C1—C2	1.383 (2)	C16—C17	1.389 (3)
C2—C3	1.383 (2)	S21—O21	1.4462 (14)
C3—C4	1.380 (3)	S21—O23	1.4490 (13)
C4—C5	1.378 (3)	S21—O22	1.4554 (13)
C5—C6	1.380 (3)	S21—C25	1.7602 (17)
S11—O11	1.4451 (13)	C21—C22	1.521 (3)
S11—O12	1.4517 (14)	C22—C27	1.373 (4)
S11—O13	1.4553 (14)	C22—C23	1.381 (4)
S11—C15	1.7671 (16)	C23—C24	1.390 (3)
C11—C12	1.515 (3)	C24—C25	1.375 (3)
C12—C17	1.377 (3)	C25—C26	1.383 (2)
C12—C13	1.382 (3)	C26—C27	1.379 (3)
C6—C1—C2	119.60 (15)	C16—C15—C14	120.25 (16)
C6—C1—N1	118.71 (15)	C16—C15—S11	119.46 (13)
C2—C1—N1	121.69 (13)	C14—C15—S11	120.27 (12)
C3—C2—C1	120.23 (14)	C15—C16—C17	119.57 (18)
C3—C2—N2	117.66 (14)	C12—C17—C16	121.09 (18)
C1—C2—N2	122.10 (13)	O21—S21—O23	113.06 (9)
C4—C3—C2	119.78 (17)	O21—S21—O22	111.63 (9)
C5—C4—C3	120.09 (18)	O23—S21—O22	111.81 (9)
C4—C5—C6	120.07 (18)	O21—S21—C25	105.80 (8)
C5—C6—C1	120.23 (18)	O23—S21—C25	107.28 (8)
O11—S11—O12	112.95 (9)	O22—S21—C25	106.77 (8)
O11—S11—O13	113.27 (8)	C27—C22—C23	118.7 (2)
O12—S11—O13	111.32 (8)	C27—C22—C21	121.4 (3)
O11—S11—C15	106.21 (7)	C23—C22—C21	119.9 (3)
O12—S11—C15	105.73 (8)	C22—C23—C24	121.2 (2)
O13—S11—C15	106.72 (8)	C25—C24—C23	119.1 (2)
C17—C12—C13	118.48 (17)	C24—C25—C26	120.16 (17)
C17—C12—C11	119.6 (2)	C24—C25—S21	121.00 (14)
C13—C12—C11	121.9 (2)	C26—C25—S21	118.79 (14)
C12—C13—C14	121.40 (18)	C27—C26—C25	119.8 (2)
C15—C14—C13	119.22 (17)	C22—C27—C26	121.0 (2)
C6—C1—C2—C3	−0.9 (2)	C14—C15—C16—C17	−0.2 (3)
N1—C1—C2—C3	179.13 (16)	S11—C15—C16—C17	178.16 (16)
C6—C1—C2—N2	−179.29 (16)	C13—C12—C17—C16	−0.2 (3)
N1—C1—C2—N2	0.8 (2)	C11—C12—C17—C16	179.8 (2)
C1—C2—C3—C4	0.7 (3)	C15—C16—C17—C12	0.5 (3)
N2—C2—C3—C4	179.15 (19)	C27—C22—C23—C24	−2.5 (4)
C2—C3—C4—C5	0.0 (4)	C21—C22—C23—C24	175.2 (3)
C3—C4—C5—C6	−0.6 (4)	C22—C23—C24—C25	1.8 (4)
C4—C5—C6—C1	0.4 (4)	C23—C24—C25—C26	−0.6 (3)
C2—C1—C6—C5	0.4 (3)	C23—C24—C25—S21	−177.95 (19)
N1—C1—C6—C5	−179.68 (19)	O21—S21—C25—C24	131.47 (17)
C17—C12—C13—C14	−0.3 (3)	O23—S21—C25—C24	−107.57 (17)
C11—C12—C13—C14	179.6 (2)	O22—S21—C25—C24	12.44 (18)
C12—C13—C14—C15	0.6 (3)	O21—S21—C25—C26	−45.95 (16)
C13—C14—C15—C16	−0.3 (3)	O23—S21—C25—C26	75.00 (16)
C13—C14—C15—S11	−178.67 (15)	O22—S21—C25—C26	−164.99 (14)
O11—S11—C15—C16	22.07 (17)	C24—C25—C26—C27	0.0 (3)
O12—S11—C15—C16	−98.17 (16)	S21—C25—C26—C27	177.46 (15)
O13—S11—C15—C16	143.20 (15)	C23—C22—C27—C26	1.9 (4)
O11—S11—C15—C14	−159.58 (14)	C21—C22—C27—C26	−175.7 (2)
O12—S11—C15—C14	80.18 (15)	C25—C26—C27—C22	−0.7 (3)
O13—S11—C15—C14	−38.45 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O21	0.89	1.92	2.8062 (19)	175
N1—H1B···O11^i	0.89	2.07	2.7509 (19)	133
N1—H1B···O22^ii	0.89	2.31	2.9017 (18)	124
N1—H1C···O13^iii	0.89	1.89	2.7733 (19)	170
N2—H2A···O13^iii	0.89	2.46	2.9128 (19)	112
N2—H2A···O23^iv	0.89	1.97	2.7820 (18)	151
N2—H2B···O22^ii	0.89	1.98	2.8611 (19)	173
N2—H2C···O12	0.89	1.84	2.7224 (19)	175

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