Low-dimensional hydrogen-bonded structures in the 1:1 and 1:2 proton-transfer compounds of 4,5-dichloro­phthalic acid with the aliphatic Lewis bases triethyl­amine, diethyl­amine, n-butyl­amine and piperidine

The structures of the proton-transfer compounds of 4,5-di­chloro­phthalic acid (DCPA) with the aliphatic Lewis bases triethyl­amine, diethyl­amine, n-butyl­amine and piperidine, namely triethyl­aminium 2-carb­oxy-4,5-dichloro­benzoate, C₆H₁₆N⁺·C₈H₃Cl₂O₄⁻, (I), diethyl­aminium 2-carb­oxy-4,5-dichloro­benzoate, C₄H₁₂N⁺·C₈H₃Cl₂O₄⁻, (II), bis­(butan­aminium) 4,5-dichloro­benzene-1,2-dicarboxylate monohydrate, 2C₄H₁₂N⁺·C₈H₂Cl₂O₄²⁻·H₂O, (III), and bis(piperidinium) 4,5-dichloro­benzene-1,2-dicarboxylate monohydrate, 2C₅H₁₂N⁺·C₈H₂Cl₂O₄²⁻·H₂O, (IV), have been determined at 200 K. All compounds have hydrogen-bonding associations, giving discrete cation–anion units in (I) and linear chains in (II), while (III) and (IV) both have two-dimensional structures. In (I), a discrete cation–anion unit is formed through an asymmetric R₁²(4) N⁺—H...O₂ hydrogen-bonding association, whereas in (II), chains are formed through linear N—H...O associations involving both aminium H-atom donors. In compounds (III) and (IV), the primary N—H...O-linked cation–anion units are extended into a two-dimensional sheet structure via amide–carboxyl N—H...O and amide–carbonyl N—H...O inter­actions. In the 1:1 salts (I) and (II), the hydrogen 4,5-dichloro­phthalate anions are essentially planar with short intra­molecular carbox­yl–carboxyl O—H...O hydrogen bonds [O...O = 2.4223 (14) and 2.388 (2) Å, respectively]. This work provides a further example of the uncommon zero-dimensional hydrogen-bonded DCPA–Lewis base salt and the one-dimensional chain structure type, while even with the hydrate structures of the 1:2 salts with the primary and secondary amines, the low dimensionality generally associated with 1:1 DCPA salts is also found.

Computing details

For all compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (I), (II), (IV); SIR92 (Altomare et al., 1994) for (III). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

(I) triethylaminium 2-carboxy-4,5-dichlorobenzoate

Crystal data

C6H16N^+·C8H3Cl2O4^−	F(000) = 704
Mr = 336.20	Dx = 1.411 Mg m^−3
Monoclinic, P21/c	Melting point: 353 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.3206 (7) Å	Cell parameters from 5117 reflections
b = 11.2201 (7) Å	θ = 3.2–28.8°
c = 19.4813 (12) Å	µ = 0.42 mm^−1
β = 98.576 (7)°	T = 200 K
V = 1582.3 (2) Å^3	Block, colourless
Z = 4	0.40 × 0.40 × 0.30 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer	3098 independent reflections
Radiation source: Enhance (Mo) X-ray source	2638 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 16.077 pixels mm^-1	θmax = 26.0°, θmin = 3.3°
ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −13→13
Tmin = 0.96, Tmax = 0.98	l = −20→24
10740 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0454P)^2 + 0.1656P] where P = (Fo^2 + 2Fc^2)/3
3098 reflections	(Δ/σ)max = 0.001
193 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N1A	−0.05058 (17)	0.95062 (10)	0.36011 (6)	0.0229 (3)
C1A	−0.2461 (2)	0.91354 (14)	0.36217 (7)	0.0304 (4)
C1B	−0.0117 (2)	1.07979 (12)	0.37870 (7)	0.0258 (4)
C1C	0.0049 (2)	0.91522 (13)	0.29175 (7)	0.0298 (4)
C2A	−0.3021 (2)	0.92226 (15)	0.43354 (8)	0.0374 (5)
C2B	−0.1025 (2)	1.16623 (13)	0.32431 (8)	0.0380 (5)
C2C	0.2047 (3)	0.94008 (18)	0.28776 (10)	0.0481 (6)
Cl4	0.57140 (5)	0.69357 (4)	0.68165 (2)	0.0346 (1)
Cl5	0.53419 (6)	0.40824 (4)	0.68041 (2)	0.0382 (1)
O11	0.15312 (15)	0.31238 (9)	0.44967 (5)	0.0364 (4)
O12	0.05781 (15)	0.46504 (9)	0.38294 (5)	0.0328 (3)
O21	0.05047 (15)	0.68027 (9)	0.39185 (5)	0.0349 (3)
O22	0.18100 (15)	0.82561 (9)	0.45818 (5)	0.0353 (3)
C1	0.24055 (17)	0.50253 (13)	0.49736 (6)	0.0205 (4)
C2	0.25130 (17)	0.62848 (12)	0.49892 (6)	0.0209 (4)
C3	0.35682 (17)	0.68325 (13)	0.55642 (6)	0.0231 (4)
C4	0.44516 (18)	0.61823 (13)	0.61229 (7)	0.0238 (4)
C5	0.42972 (18)	0.49501 (13)	0.61168 (7)	0.0242 (4)
C6	0.33008 (18)	0.43895 (12)	0.55450 (7)	0.0235 (4)
C11	0.14444 (19)	0.41945 (13)	0.44043 (7)	0.0252 (4)
C21	0.15512 (18)	0.71762 (13)	0.44567 (7)	0.0248 (4)
H1A	0.019 (2)	0.9082 (14)	0.3943 (8)	0.0300*
H12	0.057 (3)	0.553 (2)	0.3840 (11)	0.0590*
H11A	−0.26240	0.83020	0.34570	0.0370*
H11B	0.12350	1.09290	0.38540	0.0310*
H11C	−0.07280	0.95900	0.25400	0.0360*
H12A	−0.32940	0.96440	0.32980	0.0370*
H12B	−0.05570	1.09700	0.42330	0.0310*
H12C	−0.01900	0.82900	0.28420	0.0360*
H21A	−0.42860	0.89250	0.43190	0.0450*
H21B	−0.07430	1.24810	0.33990	0.0460*
H21C	0.23690	0.90650	0.24470	0.0580*
H22A	−0.29630	1.00560	0.44870	0.0450*
H22B	−0.23660	1.15410	0.31740	0.0460*
H22C	0.28200	0.90360	0.32760	0.0580*
H23A	−0.21790	0.87430	0.46630	0.0450*
H23B	−0.05540	1.15240	0.28050	0.0460*
H23C	0.22540	1.02640	0.28840	0.0580*
H3	0.36810	0.76760	0.55710	0.0280*
H6	0.32240	0.35440	0.55410	0.0280*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0293 (6)	0.0191 (6)	0.0185 (6)	0.0008 (5)	−0.0022 (5)	0.0005 (4)
C1A	0.0313 (8)	0.0307 (8)	0.0272 (7)	−0.0049 (7)	−0.0021 (6)	0.0022 (6)
C1B	0.0321 (8)	0.0196 (7)	0.0238 (7)	−0.0011 (6)	−0.0019 (6)	−0.0029 (5)
C1C	0.0405 (8)	0.0257 (8)	0.0226 (7)	0.0003 (7)	0.0025 (6)	−0.0042 (6)
C2A	0.0417 (9)	0.0357 (9)	0.0359 (9)	−0.0040 (7)	0.0094 (7)	0.0008 (7)
C2B	0.0562 (11)	0.0200 (8)	0.0330 (8)	0.0028 (7)	−0.0090 (7)	−0.0008 (6)
C2C	0.0459 (10)	0.0582 (12)	0.0430 (10)	−0.0003 (9)	0.0157 (8)	−0.0085 (8)
Cl4	0.0363 (2)	0.0381 (2)	0.0258 (2)	0.0023 (2)	−0.0076 (2)	−0.0071 (2)
Cl5	0.0447 (2)	0.0362 (2)	0.0302 (2)	0.0083 (2)	−0.0055 (2)	0.0104 (2)
O11	0.0458 (7)	0.0219 (6)	0.0389 (6)	−0.0040 (5)	−0.0018 (5)	−0.0034 (4)
O12	0.0449 (6)	0.0271 (6)	0.0237 (5)	−0.0006 (5)	−0.0036 (5)	−0.0044 (4)
O21	0.0455 (6)	0.0284 (6)	0.0260 (5)	0.0022 (5)	−0.0105 (5)	0.0009 (4)
O22	0.0458 (6)	0.0211 (6)	0.0344 (6)	0.0010 (5)	−0.0091 (5)	0.0030 (4)
C1	0.0183 (6)	0.0232 (7)	0.0208 (7)	0.0015 (6)	0.0052 (5)	−0.0005 (5)
C2	0.0209 (7)	0.0222 (7)	0.0197 (7)	0.0015 (5)	0.0037 (5)	−0.0002 (5)
C3	0.0253 (7)	0.0204 (7)	0.0233 (7)	0.0015 (6)	0.0026 (5)	−0.0013 (5)
C4	0.0212 (7)	0.0286 (8)	0.0208 (7)	0.0026 (6)	0.0009 (5)	−0.0040 (6)
C5	0.0229 (7)	0.0283 (8)	0.0211 (7)	0.0050 (6)	0.0020 (5)	0.0044 (6)
C6	0.0245 (7)	0.0203 (7)	0.0265 (7)	0.0019 (6)	0.0061 (6)	0.0017 (5)
C11	0.0245 (7)	0.0259 (8)	0.0257 (7)	−0.0014 (6)	0.0057 (6)	−0.0022 (6)
C21	0.0266 (7)	0.0239 (8)	0.0234 (7)	0.0034 (6)	0.0026 (6)	0.0018 (6)

Geometric parameters (Å, º)

Cl4—C4	1.7383 (14)	C2A—H21A	0.9800
Cl5—C5	1.7378 (14)	C2A—H22A	0.9800
O11—C11	1.2150 (18)	C2A—H23A	0.9800
O12—C11	1.3063 (17)	C2B—H21B	0.9800
O21—C21	1.2737 (17)	C2B—H22B	0.9800
O22—C21	1.2448 (18)	C2B—H23B	0.9800
O12—H12	0.99 (2)	C2C—H21C	0.9800
N1A—C1A	1.4968 (19)	C2C—H22C	0.9800
N1A—C1B	1.5106 (18)	C2C—H23C	0.9800
N1A—C1C	1.5025 (18)	C1—C2	1.415 (2)
N1A—H1A	0.910 (15)	C1—C11	1.5366 (19)
C1A—C2A	1.510 (2)	C1—C6	1.4000 (18)
C1B—C2B	1.515 (2)	C2—C3	1.4040 (17)
C1C—C2C	1.502 (3)	C2—C21	1.5344 (19)
C1A—H12A	0.9900	C3—C4	1.3875 (19)
C1A—H11A	0.9900	C4—C5	1.387 (2)
C1B—H11B	0.9900	C5—C6	1.3879 (19)
C1B—H12B	0.9900	C3—H3	0.9500
C1C—H12C	0.9900	C6—H6	0.9500
C1C—H11C	0.9900
C11—O12—H12	112.2 (12)	H21B—C2B—H23B	109.00
C1A—N1A—C1C	109.65 (11)	H22B—C2B—H23B	110.00
C1B—N1A—C1C	113.58 (11)	C1B—C2B—H22B	109.00
C1A—N1A—C1B	114.02 (11)	C1C—C2C—H21C	109.00
C1B—N1A—H1A	105.2 (10)	C1C—C2C—H23C	109.00
C1C—N1A—H1A	108.3 (10)	H21C—C2C—H22C	109.00
C1A—N1A—H1A	105.6 (9)	C1C—C2C—H22C	109.00
N1A—C1A—C2A	113.49 (12)	H22C—C2C—H23C	109.00
N1A—C1B—C2B	113.53 (11)	H21C—C2C—H23C	110.00
N1A—C1C—C2C	113.00 (13)	C2—C1—C6	118.28 (11)
N1A—C1A—H12A	109.00	C2—C1—C11	129.73 (11)
C2A—C1A—H11A	109.00	C6—C1—C11	111.99 (12)
C2A—C1A—H12A	109.00	C1—C2—C3	118.45 (11)
H11A—C1A—H12A	108.00	C1—C2—C21	128.16 (11)
N1A—C1A—H11A	109.00	C3—C2—C21	113.36 (12)
N1A—C1B—H11B	109.00	C2—C3—C4	122.17 (13)
N1A—C1B—H12B	109.00	Cl4—C4—C5	121.64 (11)
C2B—C1B—H12B	109.00	C3—C4—C5	119.31 (13)
H11B—C1B—H12B	108.00	Cl4—C4—C3	119.05 (11)
C2B—C1B—H11B	109.00	Cl5—C5—C6	118.86 (11)
N1A—C1C—H11C	109.00	C4—C5—C6	119.41 (13)
N1A—C1C—H12C	109.00	Cl5—C5—C4	121.73 (11)
C2C—C1C—H12C	109.00	C1—C6—C5	122.34 (13)
H11C—C1C—H12C	108.00	O11—C11—C1	118.99 (12)
C2C—C1C—H11C	109.00	O12—C11—C1	119.52 (12)
C1A—C2A—H22A	110.00	O11—C11—O12	121.48 (13)
C1A—C2A—H23A	109.00	O21—C21—C2	120.07 (12)
H21A—C2A—H22A	109.00	O22—C21—C2	117.45 (12)
H21A—C2A—H23A	109.00	O21—C21—O22	122.46 (13)
H22A—C2A—H23A	109.00	C2—C3—H3	119.00
C1A—C2A—H21A	109.00	C4—C3—H3	119.00
C1B—C2B—H21B	109.00	C1—C6—H6	119.00
C1B—C2B—H23B	109.00	C5—C6—H6	119.00
H21B—C2B—H22B	109.00
C1B—N1A—C1A—C2A	−63.19 (16)	C6—C1—C11—O12	−178.56 (12)
C1C—N1A—C1A—C2A	168.20 (12)	C1—C2—C3—C4	−2.12 (19)
C1A—N1A—C1B—C2B	−69.93 (15)	C21—C2—C3—C4	175.95 (12)
C1C—N1A—C1B—C2B	56.65 (16)	C1—C2—C21—O21	−0.1 (2)
C1A—N1A—C1C—C2C	−175.17 (13)	C1—C2—C21—O22	178.46 (13)
C1B—N1A—C1C—C2C	55.98 (16)	C3—C2—C21—O21	−177.98 (12)
C6—C1—C2—C3	2.37 (18)	C3—C2—C21—O22	0.62 (17)
C6—C1—C2—C21	−175.38 (12)	C2—C3—C4—Cl4	−179.47 (10)
C11—C1—C2—C3	−176.80 (12)	C2—C3—C4—C5	0.12 (19)
C11—C1—C2—C21	5.5 (2)	Cl4—C4—C5—Cl5	0.45 (17)
C2—C1—C6—C5	−0.73 (19)	Cl4—C4—C5—C6	−178.84 (10)
C11—C1—C6—C5	178.57 (12)	C3—C4—C5—Cl5	−179.14 (10)
C2—C1—C11—O11	179.64 (13)	C3—C4—C5—C6	1.6 (2)
C2—C1—C11—O12	0.7 (2)	Cl5—C5—C6—C1	179.42 (10)
C6—C1—C11—O11	0.44 (18)	C4—C5—C6—C1	−1.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O21	0.910 (15)	2.569 (16)	3.1614 (15)	123.3 (12)
N1A—H1A···O22	0.910 (15)	1.837 (15)	2.7433 (16)	173.7 (14)
O12—H12···O21	0.99 (2)	1.44 (2)	2.4223 (14)	175 (2)
C3—H3···O22	0.95	2.29	2.6714 (16)	103
C6—H6···O11	0.95	2.27	2.6602 (17)	104

(II) diethylaminium 2-carboxy-4,5-dichlorobenzoate

Crystal data

C4H12N^+·C8H3Cl2O4^−	F(000) = 640
Mr = 308.14	Dx = 1.392 Mg m^−3
Monoclinic, P21/c	Melting point: 443 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.9588 (13) Å	Cell parameters from 2315 reflections
b = 9.9042 (11) Å	θ = 2.9–32.4°
c = 17.062 (3) Å	µ = 0.45 mm^−1
β = 104.580 (14)°	T = 200 K
V = 1465.2 (3) Å^3	Plate, colourless
Z = 4	0.35 × 0.35 × 0.15 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer	2802 independent reflections
Radiation source: Enhance (Mo) X-ray source	2159 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ω scans	θmax = 26.0°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→10
Tmin = 0.926, Tmax = 0.980	k = −12→7
5638 measured reflections	l = −18→21

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0641P)^2 + 0.1213P] where P = (Fo^2 + 2Fc^2)/3
2802 reflections	(Δ/σ)max = 0.002
184 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl4	0.43514 (6)	−0.20944 (6)	0.30016 (3)	0.0438 (2)
Cl5	0.45031 (7)	−0.32604 (6)	0.47681 (4)	0.0495 (2)
O11	0.82585 (18)	−0.02229 (15)	0.66675 (8)	0.0437 (5)
O12	0.9418 (2)	0.12902 (18)	0.60850 (10)	0.0531 (6)
O21	0.92748 (19)	0.21909 (18)	0.47700 (9)	0.0508 (6)
O22	0.7828 (2)	0.20048 (17)	0.35291 (9)	0.0552 (6)
C1	0.7437 (2)	−0.01323 (18)	0.52381 (11)	0.0274 (5)
C2	0.7347 (2)	0.04067 (19)	0.44596 (11)	0.0280 (6)
C3	0.6346 (2)	−0.0214 (2)	0.37922 (11)	0.0313 (6)
C4	0.5489 (2)	−0.1348 (2)	0.38645 (11)	0.0308 (6)
C5	0.5570 (2)	−0.18594 (19)	0.46316 (12)	0.0310 (6)
C6	0.6516 (2)	−0.12484 (19)	0.52986 (11)	0.0290 (6)
C11	0.8434 (2)	0.0344 (2)	0.60563 (11)	0.0330 (6)
C21	0.8196 (2)	0.1619 (2)	0.42353 (12)	0.0362 (7)
N1A	0.9508 (2)	0.41802 (18)	0.32003 (10)	0.0332 (5)
C1A	1.1027 (3)	0.3524 (3)	0.32661 (17)	0.0586 (9)
C1B	0.9510 (3)	0.5322 (2)	0.37563 (14)	0.0499 (8)
C2A	1.2148 (3)	0.4385 (4)	0.30110 (18)	0.0765 (13)
C2B	0.7912 (4)	0.5749 (4)	0.3736 (2)	0.0921 (14)
H3	0.62520	0.01590	0.32690	0.0380*
H6	0.65440	−0.15980	0.58210	0.0350*
H12	0.936 (4)	0.167 (3)	0.554 (2)	0.086*
H1A	0.914 (2)	0.442 (2)	0.2684 (14)	0.038 (6)*
H2A	0.888 (3)	0.349 (3)	0.3314 (16)	0.060 (8)*
H11A	1.14620	0.32490	0.38360	0.0700*
H11B	1.00780	0.60910	0.35990	0.0600*
H12A	1.08660	0.26960	0.29310	0.0700*
H12B	1.00490	0.50510	0.43140	0.0600*
H21A	1.23180	0.52080	0.33400	0.0920*
H21B	0.71830	0.50620	0.34570	0.1110*
H22A	1.17520	0.46240	0.24390	0.0920*
H22B	0.76880	0.66100	0.34480	0.1110*
H23A	1.31250	0.38970	0.30840	0.0920*
H23B	0.78090	0.58570	0.42910	0.1110*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl4	0.0422 (3)	0.0457 (3)	0.0369 (3)	0.0000 (2)	−0.0024 (2)	−0.0119 (2)
Cl5	0.0572 (4)	0.0336 (3)	0.0569 (4)	−0.0110 (2)	0.0127 (3)	0.0009 (2)
O11	0.0622 (10)	0.0417 (9)	0.0237 (7)	−0.0002 (7)	0.0043 (6)	0.0001 (6)
O12	0.0602 (11)	0.0574 (10)	0.0333 (8)	−0.0215 (9)	−0.0041 (7)	0.0010 (8)
O21	0.0511 (10)	0.0562 (10)	0.0402 (9)	−0.0220 (8)	0.0023 (7)	0.0072 (8)
O22	0.0672 (11)	0.0540 (10)	0.0379 (9)	−0.0187 (9)	0.0010 (8)	0.0165 (8)
C1	0.0282 (10)	0.0272 (9)	0.0255 (9)	0.0089 (8)	0.0046 (7)	−0.0012 (8)
C2	0.0271 (10)	0.0297 (10)	0.0273 (9)	0.0063 (8)	0.0068 (8)	0.0024 (8)
C3	0.0327 (11)	0.0362 (11)	0.0242 (9)	0.0060 (8)	0.0057 (8)	0.0011 (8)
C4	0.0287 (10)	0.0307 (10)	0.0306 (10)	0.0044 (8)	0.0028 (8)	−0.0057 (8)
C5	0.0298 (10)	0.0244 (10)	0.0390 (11)	0.0050 (8)	0.0093 (8)	−0.0014 (8)
C6	0.0337 (11)	0.0269 (10)	0.0267 (10)	0.0075 (8)	0.0080 (8)	0.0033 (8)
C11	0.0381 (11)	0.0310 (10)	0.0267 (10)	0.0080 (9)	0.0023 (8)	−0.0018 (8)
C21	0.0354 (12)	0.0384 (11)	0.0341 (11)	−0.0002 (9)	0.0076 (9)	0.0033 (9)
N1A	0.0431 (10)	0.0321 (9)	0.0248 (9)	0.0045 (8)	0.0093 (7)	0.0043 (7)
C1A	0.0611 (17)	0.0593 (16)	0.0605 (16)	0.0212 (13)	0.0251 (13)	0.0154 (13)
C1B	0.0694 (17)	0.0424 (13)	0.0364 (12)	0.0043 (12)	0.0105 (11)	−0.0094 (10)
C2A	0.0464 (16)	0.119 (3)	0.0653 (18)	0.0012 (17)	0.0161 (13)	0.0123 (18)
C2B	0.091 (2)	0.093 (3)	0.097 (2)	0.037 (2)	0.0325 (19)	−0.021 (2)

Geometric parameters (Å, º)

Cl4—C4	1.731 (2)	C4—C5	1.388 (3)
Cl5—C5	1.734 (2)	C5—C6	1.376 (3)
O11—C11	1.229 (2)	C3—H3	0.9500
O12—C11	1.279 (3)	C6—H6	0.9500
O21—C21	1.282 (3)	C1A—C2A	1.465 (4)
O22—C21	1.227 (2)	C1B—C2B	1.485 (5)
O12—H12	0.99 (3)	C1A—H11A	0.9900
N1A—C1B	1.476 (3)	C1A—H12A	0.9900
N1A—C1A	1.487 (3)	C1B—H11B	0.9900
N1A—H2A	0.94 (3)	C1B—H12B	0.9900
N1A—H1A	0.89 (2)	C2A—H21A	0.9800
C1—C6	1.399 (3)	C2A—H22A	0.9800
C1—C2	1.415 (3)	C2A—H23A	0.9800
C1—C11	1.530 (3)	C2B—H21B	0.9800
C2—C21	1.521 (3)	C2B—H22B	0.9800
C2—C3	1.402 (3)	C2B—H23B	0.9800
C3—C4	1.383 (3)
C11—O12—H12	111.7 (19)	C4—C3—H3	119.00
C1A—N1A—C1B	115.69 (19)	C1—C6—H6	119.00
C1B—N1A—H1A	111.8 (13)	C5—C6—H6	119.00
C1B—N1A—H2A	109.3 (17)	N1A—C1A—C2A	114.0 (2)
H1A—N1A—H2A	108 (2)	N1A—C1B—C2B	111.0 (2)
C1A—N1A—H1A	107.2 (13)	N1A—C1A—H11A	109.00
C1A—N1A—H2A	104.6 (18)	N1A—C1A—H12A	109.00
C6—C1—C11	113.33 (16)	C2A—C1A—H11A	109.00
C2—C1—C6	118.18 (17)	C2A—C1A—H12A	109.00
C2—C1—C11	128.49 (16)	H11A—C1A—H12A	108.00
C1—C2—C21	128.33 (17)	N1A—C1B—H11B	109.00
C1—C2—C3	118.09 (17)	N1A—C1B—H12B	109.00
C3—C2—C21	113.58 (16)	C2B—C1B—H11B	109.00
C2—C3—C4	122.65 (17)	C2B—C1B—H12B	110.00
Cl4—C4—C5	121.73 (15)	H11B—C1B—H12B	108.00
C3—C4—C5	118.81 (17)	C1A—C2A—H21A	109.00
Cl4—C4—C3	119.47 (14)	C1A—C2A—H22A	109.00
Cl5—C5—C4	121.26 (15)	C1A—C2A—H23A	109.00
Cl5—C5—C6	119.11 (15)	H21A—C2A—H22A	110.00
C4—C5—C6	119.63 (17)	H21A—C2A—H23A	109.00
C1—C6—C5	122.58 (17)	H22A—C2A—H23A	109.00
O11—C11—O12	122.44 (18)	C1B—C2B—H21B	110.00
O11—C11—C1	117.61 (17)	C1B—C2B—H22B	110.00
O12—C11—C1	119.95 (17)	C1B—C2B—H23B	109.00
O21—C21—O22	121.95 (19)	H21B—C2B—H22B	109.00
O22—C21—C2	117.71 (18)	H21B—C2B—H23B	109.00
O21—C21—C2	120.33 (17)	H22B—C2B—H23B	109.00
C2—C3—H3	119.00
C1A—N1A—C1B—C2B	−170.6 (2)	C1—C2—C21—O22	−172.41 (19)
C1B—N1A—C1A—C2A	−67.1 (3)	C21—C2—C3—C4	178.72 (17)
C6—C1—C2—C21	178.71 (18)	C3—C2—C21—O22	6.7 (3)
C6—C1—C2—C3	−0.4 (3)	C3—C2—C21—O21	−172.07 (18)
C2—C1—C6—C5	2.0 (3)	C1—C2—C3—C4	−2.1 (3)
C11—C1—C6—C5	−177.95 (17)	C2—C3—C4—Cl4	−176.95 (15)
C2—C1—C11—O11	175.50 (19)	C2—C3—C4—C5	2.9 (3)
C2—C1—C11—O12	−5.3 (3)	Cl4—C4—C5—C6	178.62 (15)
C6—C1—C11—O11	−4.6 (3)	C3—C4—C5—Cl5	178.93 (15)
C11—C1—C2—C3	179.57 (18)	Cl4—C4—C5—Cl5	−1.2 (2)
C11—C1—C2—C21	−1.3 (3)	C3—C4—C5—C6	−1.2 (3)
C6—C1—C11—O12	174.69 (18)	C4—C5—C6—C1	−1.2 (3)
C1—C2—C21—O21	8.8 (3)	Cl5—C5—C6—C1	178.64 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O11^i	0.89 (2)	1.89 (2)	2.772 (2)	169.6 (19)
N1A—H2A···O22	0.94 (3)	1.83 (3)	2.765 (3)	173 (3)
O12—H12···O21	0.99 (3)	1.40 (3)	2.388 (2)	179 (4)
C3—H3···O22	0.95	2.28	2.663 (3)	103
C6—H6···O11	0.95	2.28	2.662 (2)	103

Symmetry code: (i) x, −y+1/2, z−1/2.

(III) bis(butanaminium) 4,5-dichlorobenzene-1,2-dicarboxylate monohydrate

Crystal data

2C4H12N^+·C8H2Cl2O4^2^−·H2O	Z = 2
Mr = 399.30	F(000) = 424
Triclinic, P1	Dx = 1.253 Mg m^−3
Hall symbol: -P 1	Melting point: 457 K
a = 8.1362 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.3043 (11) Å	Cell parameters from 6406 reflections
c = 15.406 (1) Å	θ = 3.0–32.5°
α = 78.678 (7)°	µ = 0.33 mm^−1
β = 85.846 (6)°	T = 200 K
γ = 67.777 (9)°	Prism, colourless
V = 1058.62 (18) Å^3	0.55 × 0.30 × 0.20 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer	4851 independent reflections
Radiation source: Enhance (Mo) X-ray source	3858 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
Detector resolution: 16.077 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −12→12
Tmin = 0.865, Tmax = 0.940	l = −19→19
15869 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	w = 1/[σ^2(Fo^2) + (0.0837P)^2 + 0.0287P] where P = (Fo^2 + 2Fc^2)/3
4851 reflections	(Δ/σ)max = 0.001
260 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N1A	0.83030 (18)	0.40803 (16)	0.43961 (9)	0.0301 (4)
C2A	0.8506 (2)	0.53396 (18)	0.36814 (11)	0.0363 (5)
C3A	0.8949 (3)	0.4766 (2)	0.28024 (13)	0.0498 (6)
C4A	0.8915 (3)	0.6078 (3)	0.20387 (16)	0.0660 (8)
C5A	0.7110 (4)	0.7306 (3)	0.18164 (17)	0.0741 (9)
N1B	0.32948 (19)	−0.11939 (16)	0.40526 (10)	0.0331 (4)
C2B	0.1554 (2)	−0.0456 (2)	0.35886 (13)	0.0438 (6)
C3B	0.1793 (2)	−0.0228 (2)	0.25901 (13)	0.0482 (6)
C4B	0.0032 (3)	0.0372 (3)	0.21012 (16)	0.0626 (8)
C5B	0.0245 (5)	0.0527 (5)	0.1113 (2)	0.1087 (13)
Cl4	0.46735 (10)	0.17647 (7)	0.03754 (3)	0.0717 (2)
Cl5	0.26463 (8)	0.54775 (7)	0.02437 (3)	0.0627 (2)
O11	0.45042 (17)	0.59391 (14)	0.35104 (9)	0.0444 (4)
O12	0.31110 (18)	0.43995 (16)	0.41980 (9)	0.0493 (5)
O21	0.68790 (15)	0.18640 (13)	0.41153 (7)	0.0364 (4)
O22	0.61194 (15)	−0.00555 (12)	0.38236 (8)	0.0351 (3)
C1	0.42808 (18)	0.40301 (16)	0.27681 (10)	0.0254 (4)
C2	0.51625 (18)	0.23900 (16)	0.28276 (10)	0.0257 (4)
C3	0.5259 (2)	0.17325 (18)	0.20775 (11)	0.0340 (5)
C4	0.4510 (2)	0.2661 (2)	0.12824 (11)	0.0405 (5)
C5	0.3648 (2)	0.4280 (2)	0.12225 (11)	0.0392 (5)
C6	0.3565 (2)	0.49536 (18)	0.19618 (11)	0.0330 (5)
C11	0.39599 (18)	0.48459 (16)	0.35637 (10)	0.0270 (4)
C21	0.61058 (18)	0.13221 (16)	0.36576 (10)	0.0256 (4)
O1W	0.18354 (16)	0.20557 (14)	0.47498 (9)	0.0410 (4)
H11A	0.781 (3)	0.447 (2)	0.4846 (15)	0.048 (6)*
H12A	0.936 (3)	0.329 (2)	0.4554 (12)	0.035 (5)*
H13A	0.763 (3)	0.357 (2)	0.4210 (13)	0.041 (5)*
H21A	0.94650	0.56500	0.38430	0.0430*
H22A	0.73900	0.62810	0.36210	0.0430*
H31A	1.01440	0.39180	0.28420	0.0600*
H32A	0.80840	0.43120	0.26860	0.0600*
H41A	0.96950	0.65950	0.21850	0.0790*
H42A	0.94130	0.56080	0.15090	0.0790*
H51A	0.71990	0.81250	0.13290	0.0890*
H52A	0.66030	0.77810	0.23360	0.0890*
H53A	0.63420	0.68170	0.16390	0.0890*
H11B	0.398 (3)	−0.064 (2)	0.3886 (14)	0.046 (5)*
H12B	0.315 (3)	−0.126 (2)	0.4632 (17)	0.049 (6)*
H13B	0.380 (3)	−0.216 (3)	0.3920 (13)	0.043 (5)*
H21B	0.08830	0.05800	0.37610	0.0530*
H22B	0.08560	−0.11360	0.37710	0.0530*
H31B	0.25720	−0.12460	0.24260	0.0580*
H32B	0.23870	0.05360	0.24040	0.0580*
H41B	−0.05890	−0.03630	0.23140	0.0750*
H42B	−0.07200	0.14150	0.22440	0.0750*
H51B	−0.09080	0.07900	0.08400	0.1300*
H52B	0.10830	−0.04750	0.09690	0.1300*
H53B	0.06990	0.13660	0.08860	0.1300*
H3	0.58500	0.06250	0.21130	0.0410*
H6	0.30080	0.60660	0.19140	0.0400*
H11W	0.233 (3)	0.276 (3)	0.4557 (14)	0.051 (6)*
H12W	0.242 (4)	0.153 (3)	0.5268 (19)	0.078 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0276 (7)	0.0331 (7)	0.0318 (7)	−0.0118 (6)	−0.0005 (5)	−0.0098 (5)
C2A	0.0328 (8)	0.0327 (8)	0.0402 (9)	−0.0102 (6)	0.0000 (7)	−0.0037 (6)
C3A	0.0480 (11)	0.0480 (10)	0.0435 (11)	−0.0085 (8)	0.0091 (8)	−0.0083 (8)
C4A	0.0640 (14)	0.0732 (15)	0.0523 (14)	−0.0219 (12)	0.0087 (11)	−0.0025 (11)
C5A	0.0809 (17)	0.0767 (16)	0.0498 (14)	−0.0204 (13)	−0.0099 (12)	0.0075 (11)
N1B	0.0381 (7)	0.0303 (7)	0.0348 (8)	−0.0149 (6)	−0.0019 (6)	−0.0100 (6)
C2B	0.0365 (9)	0.0495 (10)	0.0476 (11)	−0.0122 (8)	−0.0053 (8)	−0.0199 (8)
C3B	0.0392 (10)	0.0500 (10)	0.0496 (12)	−0.0116 (8)	−0.0055 (8)	−0.0039 (8)
C4B	0.0576 (13)	0.0642 (13)	0.0617 (14)	−0.0125 (11)	−0.0184 (10)	−0.0160 (10)
C5B	0.091 (2)	0.148 (3)	0.0578 (18)	−0.014 (2)	−0.0309 (16)	−0.0031 (18)
Cl4	0.1103 (5)	0.0770 (4)	0.0354 (3)	−0.0340 (4)	−0.0094 (3)	−0.0258 (2)
Cl5	0.0678 (4)	0.0743 (4)	0.0323 (3)	−0.0172 (3)	−0.0134 (2)	0.0077 (2)
O11	0.0576 (8)	0.0330 (6)	0.0521 (8)	−0.0238 (6)	0.0047 (6)	−0.0168 (5)
O12	0.0630 (8)	0.0618 (8)	0.0433 (8)	−0.0404 (7)	0.0230 (6)	−0.0288 (6)
O21	0.0452 (7)	0.0362 (6)	0.0348 (6)	−0.0223 (5)	−0.0114 (5)	−0.0037 (4)
O22	0.0389 (6)	0.0251 (5)	0.0421 (7)	−0.0125 (5)	−0.0086 (5)	−0.0037 (4)
C1	0.0215 (6)	0.0275 (7)	0.0290 (8)	−0.0106 (5)	0.0006 (5)	−0.0067 (5)
C2	0.0248 (7)	0.0274 (7)	0.0287 (8)	−0.0126 (6)	0.0006 (5)	−0.0080 (5)
C3	0.0403 (9)	0.0336 (8)	0.0327 (9)	−0.0158 (7)	0.0007 (7)	−0.0128 (6)
C4	0.0491 (10)	0.0510 (10)	0.0273 (8)	−0.0221 (8)	−0.0011 (7)	−0.0130 (7)
C5	0.0398 (9)	0.0482 (10)	0.0282 (9)	−0.0171 (7)	−0.0040 (7)	−0.0007 (7)
C6	0.0305 (8)	0.0321 (8)	0.0347 (9)	−0.0118 (6)	0.0009 (6)	−0.0024 (6)
C11	0.0218 (6)	0.0241 (7)	0.0335 (8)	−0.0051 (5)	−0.0022 (6)	−0.0080 (5)
C21	0.0229 (7)	0.0258 (7)	0.0292 (8)	−0.0085 (5)	0.0017 (5)	−0.0096 (5)
O1W	0.0353 (6)	0.0332 (6)	0.0526 (8)	−0.0114 (5)	−0.0122 (6)	−0.0019 (5)

Geometric parameters (Å, º)

Cl4—C4	1.7356 (18)	C5A—H51A	0.9800
Cl5—C5	1.7352 (18)	C5A—H52A	0.9800
O11—C11	1.241 (2)	C5A—H53A	0.9800
O12—C11	1.251 (2)	C2B—C3B	1.520 (3)
O21—C21	1.2613 (19)	C3B—C4B	1.523 (3)
O22—C21	1.2528 (18)	C4B—C5B	1.504 (4)
O1W—H11W	0.89 (3)	C2B—H22B	0.9900
O1W—H12W	0.91 (3)	C2B—H21B	0.9900
N1A—C2A	1.492 (2)	C3B—H32B	0.9900
N1A—H13A	0.94 (2)	C3B—H31B	0.9900
N1A—H12A	0.91 (2)	C4B—H42B	0.9900
N1A—H11A	0.85 (2)	C4B—H41B	0.9900
N1B—C2B	1.486 (2)	C5B—H53B	0.9800
N1B—H12B	0.89 (3)	C5B—H52B	0.9800
N1B—H13B	0.89 (3)	C5B—H51B	0.9800
N1B—H11B	0.89 (2)	C1—C11	1.522 (2)
C2A—C3A	1.522 (3)	C1—C2	1.407 (2)
C3A—C4A	1.513 (3)	C1—C6	1.388 (2)
C4A—C5A	1.493 (4)	C2—C21	1.509 (2)
C2A—H21A	0.9900	C2—C3	1.394 (2)
C2A—H22A	0.9900	C3—C4	1.383 (2)
C3A—H32A	0.9900	C4—C5	1.388 (2)
C3A—H31A	0.9900	C5—C6	1.390 (2)
C4A—H42A	0.9900	C3—H3	0.9500
C4A—H41A	0.9900	C6—H6	0.9500
H11W—O1W—H12W	103 (2)	H21B—C2B—H22B	108.00
H12A—N1A—H13A	103.8 (18)	N1B—C2B—H21B	109.00
C2A—N1A—H13A	112.1 (12)	C2B—C3B—H31B	109.00
H11A—N1A—H13A	109 (2)	C2B—C3B—H32B	109.00
C2A—N1A—H12A	111.8 (13)	C4B—C3B—H32B	109.00
C2A—N1A—H11A	110.2 (13)	H31B—C3B—H32B	108.00
H11A—N1A—H12A	109.8 (19)	C4B—C3B—H31B	109.00
C2B—N1B—H11B	112.0 (14)	C3B—C4B—H41B	109.00
H11B—N1B—H13B	111 (2)	C5B—C4B—H41B	109.00
H12B—N1B—H13B	110.1 (17)	C5B—C4B—H42B	109.00
C2B—N1B—H13B	106.0 (16)	C3B—C4B—H42B	109.00
C2B—N1B—H12B	110.8 (16)	H41B—C4B—H42B	108.00
H11B—N1B—H12B	107 (2)	C4B—C5B—H52B	109.00
N1A—C2A—C3A	110.92 (13)	C4B—C5B—H53B	109.00
C2A—C3A—C4A	112.32 (16)	H51B—C5B—H52B	109.00
C3A—C4A—C5A	114.3 (2)	H51B—C5B—H53B	109.00
N1A—C2A—H22A	109.00	H52B—C5B—H53B	109.00
H21A—C2A—H22A	108.00	C4B—C5B—H51B	109.00
C3A—C2A—H21A	109.00	C2—C1—C6	119.26 (14)
N1A—C2A—H21A	109.00	C2—C1—C11	123.08 (13)
C3A—C2A—H22A	109.00	C6—C1—C11	117.54 (13)
C4A—C3A—H32A	109.00	C1—C2—C21	122.55 (13)
C2A—C3A—H31A	109.00	C3—C2—C21	118.43 (13)
C4A—C3A—H31A	109.00	C1—C2—C3	118.92 (14)
H31A—C3A—H32A	108.00	C2—C3—C4	121.28 (15)
C2A—C3A—H32A	109.00	Cl4—C4—C3	118.88 (13)
H41A—C4A—H42A	108.00	Cl4—C4—C5	121.31 (13)
C5A—C4A—H41A	109.00	C3—C4—C5	119.81 (15)
C3A—C4A—H41A	109.00	Cl5—C5—C6	119.35 (13)
C3A—C4A—H42A	109.00	C4—C5—C6	119.50 (15)
C5A—C4A—H42A	109.00	Cl5—C5—C4	121.14 (13)
C4A—C5A—H51A	109.00	C1—C6—C5	121.20 (15)
C4A—C5A—H52A	109.00	O11—C11—C1	116.95 (14)
C4A—C5A—H53A	109.00	O12—C11—C1	117.25 (14)
H51A—C5A—H52A	109.00	O11—C11—O12	125.74 (15)
H51A—C5A—H53A	110.00	O21—C21—C2	117.53 (13)
H52A—C5A—H53A	109.00	O22—C21—C2	117.62 (14)
N1B—C2B—C3B	111.23 (15)	O21—C21—O22	124.80 (14)
C2B—C3B—C4B	112.19 (16)	C2—C3—H3	119.00
C3B—C4B—C5B	113.1 (2)	C4—C3—H3	119.00
N1B—C2B—H22B	109.00	C1—C6—H6	119.00
C3B—C2B—H21B	109.00	C5—C6—H6	119.00
C3B—C2B—H22B	109.00
N1A—C2A—C3A—C4A	172.11 (18)	C1—C2—C3—C4	0.1 (3)
C2A—C3A—C4A—C5A	−68.3 (3)	C21—C2—C3—C4	−176.29 (15)
N1B—C2B—C3B—C4B	174.22 (16)	C1—C2—C21—O21	−35.3 (2)
C2B—C3B—C4B—C5B	−177.1 (2)	C1—C2—C21—O22	147.30 (15)
C6—C1—C2—C3	−1.4 (2)	C3—C2—C21—O21	140.96 (16)
C6—C1—C2—C21	174.86 (15)	C3—C2—C21—O22	−36.4 (2)
C11—C1—C2—C3	174.49 (15)	C2—C3—C4—Cl4	−179.82 (14)
C11—C1—C2—C21	−9.3 (2)	C2—C3—C4—C5	0.2 (3)
C2—C1—C6—C5	2.4 (3)	Cl4—C4—C5—Cl5	1.6 (2)
C11—C1—C6—C5	−173.73 (15)	Cl4—C4—C5—C6	−179.23 (14)
C2—C1—C11—O11	125.03 (17)	C3—C4—C5—Cl5	−178.45 (14)
C2—C1—C11—O12	−57.7 (2)	C3—C4—C5—C6	0.7 (3)
C6—C1—C11—O11	−59.0 (2)	Cl5—C5—C6—C1	177.15 (13)
C6—C1—C11—O12	118.20 (17)	C4—C5—C6—C1	−2.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O12^i	0.85 (2)	1.92 (2)	2.762 (2)	170 (2)
N1A—H12A···O1W^ii	0.91 (2)	1.92 (2)	2.799 (2)	164 (2)
N1A—H13A···O21	0.94 (2)	1.94 (2)	2.831 (2)	158.4 (17)
N1B—H11B···O22	0.89 (2)	2.00 (3)	2.847 (2)	158.9 (19)
N1B—H12B···O21^iii	0.89 (3)	1.90 (3)	2.7737 (19)	167.9 (17)
N1B—H13B···O11^iv	0.89 (3)	1.86 (3)	2.7481 (19)	170 (2)
O1W—H11W···O12	0.89 (3)	1.84 (3)	2.723 (2)	173 (2)
O1W—H12W···O22^iii	0.91 (3)	1.87 (3)	2.7648 (18)	166 (3)
C2B—H21B···O1W	0.99	2.57	3.289 (2)	130
C2A—H22A···O11	0.99	2.51	3.110 (2)	119

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

(IV) bis(piperidinium) 4,5-dichlorobenzene-1,2-dicarboxylate monohydrate

Crystal data

2C5H12N^+·C8H2Cl2O4^2^−·H2O	F(000) = 896
Mr = 423.32	Dx = 1.332 Mg m^−3
Monoclinic, P21/c	Melting point: 405 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.8481 (10) Å	Cell parameters from 6842 reflections
b = 10.5937 (8) Å	θ = 3.4–28.8°
c = 14.6129 (10) Å	µ = 0.34 mm^−1
β = 99.903 (7)°	T = 200 K
V = 2111.8 (3) Å^3	Plate, colourless
Z = 4	0.35 × 0.20 × 0.18 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer	4805 independent reflections
Radiation source: Enhance (Mo) X-ray source	3570 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
Detector resolution: 16.077 pixels mm^-1	θmax = 27.5°, θmin = 3.4°
ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −13→13
Tmin = 0.701, Tmax = 0.980	l = −18→18
26626 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0644P)^2] where P = (Fo^2 + 2Fc^2)/3
4805 reflections	(Δ/σ)max < 0.001
268 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N1A	0.06019 (10)	0.62705 (12)	0.30611 (8)	0.0248 (4)
C2A	0.08561 (12)	0.59975 (16)	0.40785 (10)	0.0342 (5)
C3A	0.19204 (12)	0.55895 (17)	0.43278 (11)	0.0389 (5)
C4A	0.21235 (12)	0.44461 (15)	0.37525 (11)	0.0360 (5)
C5A	0.18615 (12)	0.47509 (15)	0.27239 (11)	0.0345 (5)
C6A	0.07982 (12)	0.51771 (15)	0.24770 (11)	0.0336 (5)
N1B	−0.18744 (9)	0.53788 (12)	0.07825 (9)	0.0259 (4)
C2B	−0.17157 (12)	0.47472 (15)	−0.00943 (11)	0.0331 (5)
C3B	−0.25761 (14)	0.39003 (16)	−0.04612 (12)	0.0422 (6)
C4B	−0.35296 (14)	0.46454 (18)	−0.06222 (13)	0.0497 (6)
C5B	−0.36718 (13)	0.53043 (18)	0.02755 (13)	0.0450 (6)
C6B	−0.27991 (11)	0.61271 (14)	0.06581 (11)	0.0307 (5)
Cl4	0.54291 (3)	1.11882 (5)	0.10952 (4)	0.0515 (2)
Cl5	0.54725 (3)	0.83387 (4)	0.18411 (4)	0.0524 (2)
O11	0.18070 (8)	0.83778 (9)	0.29506 (7)	0.0299 (3)
O12	0.11586 (8)	0.85918 (11)	0.14445 (8)	0.0389 (4)
O21	0.13624 (7)	1.13683 (10)	0.22891 (7)	0.0297 (3)
O22	0.15811 (8)	1.22425 (10)	0.09345 (7)	0.0358 (3)
C1	0.27323 (10)	0.94353 (13)	0.19485 (9)	0.0210 (4)
C2	0.27163 (10)	1.06951 (13)	0.16393 (9)	0.0210 (4)
C3	0.35526 (11)	1.12116 (14)	0.13754 (10)	0.0268 (4)
C4	0.44021 (11)	1.05035 (15)	0.14302 (11)	0.0305 (4)
C5	0.44221 (11)	0.92640 (15)	0.17569 (11)	0.0301 (4)
C6	0.35922 (11)	0.87368 (14)	0.20170 (10)	0.0269 (4)
C11	0.18131 (10)	0.87618 (13)	0.21301 (10)	0.0232 (4)
C21	0.18026 (10)	1.15032 (12)	0.16064 (10)	0.0231 (4)
O1W	−0.03247 (9)	0.70087 (11)	0.06512 (9)	0.0373 (4)
H11A	−0.0042 (15)	0.6453 (17)	0.2911 (12)	0.044 (5)*
H12A	0.0983 (13)	0.6934 (18)	0.2940 (12)	0.047 (5)*
H21A	0.04250	0.53200	0.42450	0.0410*
H22A	0.07470	0.67630	0.44360	0.0410*
H31A	0.20710	0.53740	0.49960	0.0470*
H32A	0.23520	0.62960	0.42130	0.0470*
H41A	0.28250	0.42150	0.39070	0.0430*
H42A	0.17310	0.37180	0.39020	0.0430*
H51A	0.19630	0.39930	0.23550	0.0410*
H52A	0.22980	0.54270	0.25650	0.0410*
H61A	0.06540	0.54200	0.18130	0.0400*
H62A	0.03600	0.44680	0.25720	0.0400*
H11B	−0.1854 (13)	0.4805 (16)	0.1236 (12)	0.039 (5)*
H12B	−0.1311 (14)	0.5936 (17)	0.0945 (12)	0.044 (5)*
H21B	−0.11070	0.42400	0.00270	0.0400*
H22B	−0.16390	0.53940	−0.05660	0.0400*
H31B	−0.26200	0.32150	−0.00100	0.0510*
H32B	−0.24730	0.35100	−0.10520	0.0510*
H41B	−0.40870	0.40680	−0.08300	0.0600*
H42B	−0.35120	0.52820	−0.11150	0.0600*
H51B	−0.42700	0.58320	0.01540	0.0540*
H52B	−0.37650	0.46610	0.07440	0.0540*
H61B	−0.27540	0.68360	0.02260	0.0370*
H62B	−0.28900	0.64860	0.12630	0.0370*
H3	0.35400	1.20570	0.11560	0.0320*
H6	0.36120	0.78950	0.22430	0.0320*
H11W	0.0098 (15)	0.749 (2)	0.0907 (14)	0.058 (6)*
H12W	−0.0602 (15)	0.733 (2)	0.0152 (15)	0.062 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1A	0.0213 (6)	0.0236 (6)	0.0299 (7)	−0.0011 (5)	0.0052 (5)	0.0039 (5)
C2A	0.0371 (9)	0.0404 (9)	0.0275 (8)	0.0061 (7)	0.0125 (7)	0.0033 (7)
C3A	0.0399 (10)	0.0512 (10)	0.0245 (8)	0.0100 (8)	0.0024 (7)	0.0046 (7)
C4A	0.0330 (9)	0.0295 (8)	0.0462 (10)	0.0073 (7)	0.0091 (8)	0.0095 (7)
C5A	0.0378 (9)	0.0297 (8)	0.0379 (9)	0.0027 (7)	0.0117 (7)	−0.0075 (7)
C6A	0.0375 (9)	0.0314 (8)	0.0307 (8)	−0.0028 (7)	0.0025 (7)	−0.0055 (7)
N1B	0.0287 (7)	0.0250 (6)	0.0233 (6)	−0.0024 (5)	0.0022 (5)	0.0025 (5)
C2B	0.0396 (9)	0.0299 (8)	0.0311 (8)	0.0024 (7)	0.0102 (7)	−0.0005 (7)
C3B	0.0607 (12)	0.0288 (9)	0.0369 (9)	−0.0078 (8)	0.0078 (8)	−0.0084 (7)
C4B	0.0457 (11)	0.0503 (11)	0.0469 (11)	−0.0139 (9)	−0.0094 (9)	−0.0086 (9)
C5B	0.0278 (9)	0.0525 (11)	0.0531 (11)	−0.0037 (8)	0.0021 (8)	−0.0069 (9)
C6B	0.0323 (8)	0.0286 (8)	0.0302 (8)	0.0032 (6)	0.0026 (7)	−0.0034 (6)
Cl4	0.0308 (2)	0.0537 (3)	0.0743 (3)	−0.0102 (2)	0.0215 (2)	0.0062 (2)
Cl5	0.0289 (2)	0.0503 (3)	0.0797 (4)	0.0127 (2)	0.0138 (2)	0.0071 (2)
O11	0.0381 (6)	0.0253 (5)	0.0275 (6)	−0.0063 (5)	0.0090 (5)	0.0026 (4)
O12	0.0322 (6)	0.0507 (7)	0.0315 (6)	−0.0181 (5)	−0.0007 (5)	−0.0057 (5)
O21	0.0250 (5)	0.0354 (6)	0.0286 (6)	0.0035 (4)	0.0047 (4)	0.0006 (5)
O22	0.0364 (6)	0.0337 (6)	0.0352 (6)	0.0048 (5)	0.0001 (5)	0.0126 (5)
C1	0.0239 (7)	0.0227 (7)	0.0157 (6)	−0.0034 (5)	0.0017 (5)	−0.0030 (5)
C2	0.0216 (7)	0.0237 (7)	0.0164 (6)	−0.0028 (5)	−0.0001 (5)	−0.0020 (5)
C3	0.0261 (8)	0.0264 (7)	0.0270 (8)	−0.0045 (6)	0.0024 (6)	0.0027 (6)
C4	0.0228 (7)	0.0349 (8)	0.0347 (8)	−0.0079 (6)	0.0074 (6)	−0.0007 (7)
C5	0.0220 (7)	0.0327 (8)	0.0352 (8)	0.0031 (6)	0.0040 (6)	−0.0019 (7)
C6	0.0281 (8)	0.0232 (7)	0.0283 (8)	−0.0003 (6)	0.0014 (6)	0.0004 (6)
C11	0.0263 (7)	0.0180 (7)	0.0263 (7)	−0.0016 (5)	0.0075 (6)	−0.0040 (6)
C21	0.0222 (7)	0.0209 (7)	0.0240 (7)	−0.0040 (5)	−0.0019 (6)	−0.0029 (6)
O1W	0.0325 (6)	0.0351 (7)	0.0400 (7)	−0.0093 (5)	−0.0061 (6)	0.0099 (5)

Geometric parameters (Å, º)

Cl4—C4	1.7401 (16)	C5A—H52A	0.9900
Cl5—C5	1.7408 (16)	C6A—H62A	0.9900
O11—C11	1.2675 (18)	C6A—H61A	0.9900
O12—C11	1.2431 (18)	C2B—C3B	1.514 (2)
O21—C21	1.2635 (17)	C3B—C4B	1.522 (3)
O22—C21	1.2522 (17)	C4B—C5B	1.528 (3)
O1W—H11W	0.82 (2)	C5B—C6B	1.517 (2)
O1W—H12W	0.84 (2)	C2B—H21B	0.9900
N1A—C6A	1.491 (2)	C2B—H22B	0.9900
N1A—C2A	1.4960 (19)	C3B—H31B	0.9900
N1A—H11A	0.90 (2)	C3B—H32B	0.9900
N1A—H12A	0.914 (19)	C4B—H41B	0.9900
N1B—C6B	1.490 (2)	C4B—H42B	0.9900
N1B—C2B	1.495 (2)	C5B—H52B	0.9900
N1B—H12B	0.975 (19)	C5B—H51B	0.9900
N1B—H11B	0.896 (17)	C6B—H62B	0.9900
C2A—C3A	1.519 (2)	C6B—H61B	0.9900
C3A—C4A	1.528 (2)	C1—C11	1.522 (2)
C4A—C5A	1.519 (2)	C1—C2	1.4080 (19)
C5A—C6A	1.523 (2)	C1—C6	1.391 (2)
C2A—H22A	0.9900	C2—C21	1.522 (2)
C2A—H21A	0.9900	C2—C3	1.394 (2)
C3A—H31A	0.9900	C3—C4	1.386 (2)
C3A—H32A	0.9900	C4—C5	1.396 (2)
C4A—H41A	0.9900	C5—C6	1.388 (2)
C4A—H42A	0.9900	C3—H3	0.9500
C5A—H51A	0.9900	C6—H6	0.9500
H11W—O1W—H12W	109 (2)	C3B—C2B—H21B	110.00
C2A—N1A—C6A	112.57 (12)	N1B—C2B—H21B	110.00
C6A—N1A—H11A	107.3 (11)	H21B—C2B—H22B	108.00
H11A—N1A—H12A	111.6 (16)	C3B—C2B—H22B	110.00
C2A—N1A—H12A	107.2 (11)	C2B—C3B—H32B	109.00
C2A—N1A—H11A	109.7 (11)	C4B—C3B—H31B	109.00
C6A—N1A—H12A	108.6 (11)	C2B—C3B—H31B	109.00
C2B—N1B—C6B	112.55 (12)	H31B—C3B—H32B	108.00
C2B—N1B—H11B	109.9 (11)	C4B—C3B—H32B	109.00
H11B—N1B—H12B	108.0 (15)	C3B—C4B—H41B	110.00
C6B—N1B—H11B	111.6 (12)	C5B—C4B—H41B	110.00
C6B—N1B—H12B	110.0 (11)	C5B—C4B—H42B	110.00
C2B—N1B—H12B	104.5 (11)	H41B—C4B—H42B	108.00
N1A—C2A—C3A	110.25 (13)	C3B—C4B—H42B	110.00
C2A—C3A—C4A	110.88 (13)	C4B—C5B—H52B	109.00
C3A—C4A—C5A	109.92 (13)	C6B—C5B—H51B	109.00
C4A—C5A—C6A	110.74 (13)	C4B—C5B—H51B	109.00
N1A—C6A—C5A	111.02 (13)	H51B—C5B—H52B	108.00
H21A—C2A—H22A	108.00	C6B—C5B—H52B	109.00
N1A—C2A—H21A	110.00	N1B—C6B—H62B	110.00
C3A—C2A—H21A	110.00	C5B—C6B—H61B	110.00
C3A—C2A—H22A	110.00	C5B—C6B—H62B	110.00
N1A—C2A—H22A	110.00	H61B—C6B—H62B	108.00
C2A—C3A—H32A	109.00	N1B—C6B—H61B	110.00
C2A—C3A—H31A	109.00	C2—C1—C6	119.57 (13)
C4A—C3A—H32A	109.00	C2—C1—C11	122.20 (12)
C4A—C3A—H31A	109.00	C6—C1—C11	118.00 (12)
H31A—C3A—H32A	108.00	C1—C2—C21	120.70 (12)
H41A—C4A—H42A	108.00	C3—C2—C21	119.76 (12)
C3A—C4A—H42A	110.00	C1—C2—C3	119.53 (13)
C5A—C4A—H41A	110.00	C2—C3—C4	120.59 (14)
C5A—C4A—H42A	110.00	Cl4—C4—C3	119.00 (12)
C3A—C4A—H41A	110.00	Cl4—C4—C5	121.28 (12)
C4A—C5A—H52A	110.00	C3—C4—C5	119.71 (14)
C6A—C5A—H52A	110.00	Cl5—C5—C6	118.37 (12)
H51A—C5A—H52A	108.00	C4—C5—C6	120.23 (14)
C4A—C5A—H51A	110.00	Cl5—C5—C4	121.41 (12)
C6A—C5A—H51A	109.00	C1—C6—C5	120.34 (14)
N1A—C6A—H62A	109.00	O11—C11—C1	117.21 (12)
N1A—C6A—H61A	109.00	O12—C11—C1	116.31 (12)
C5A—C6A—H62A	109.00	O11—C11—O12	126.39 (14)
C5A—C6A—H61A	109.00	O21—C21—C2	115.02 (12)
H61A—C6A—H62A	108.00	O22—C21—C2	117.83 (12)
N1B—C2B—C3B	110.24 (13)	O21—C21—O22	127.12 (13)
C2B—C3B—C4B	110.89 (14)	C2—C3—H3	120.00
C3B—C4B—C5B	109.92 (15)	C4—C3—H3	120.00
C4B—C5B—C6B	111.52 (15)	C1—C6—H6	120.00
N1B—C6B—C5B	110.65 (13)	C5—C6—H6	120.00
N1B—C2B—H22B	110.00
C6A—N1A—C2A—C3A	56.24 (17)	C2—C1—C11—O11	−118.74 (15)
C2A—N1A—C6A—C5A	−55.92 (17)	C2—C1—C11—O12	64.50 (18)
C6B—N1B—C2B—C3B	−57.31 (16)	C6—C1—C11—O11	66.86 (17)
C2B—N1B—C6B—C5B	56.01 (17)	C6—C1—C11—O12	−109.90 (15)
N1A—C2A—C3A—C4A	−56.58 (17)	C1—C2—C3—C4	−1.1 (2)
C2A—C3A—C4A—C5A	57.19 (18)	C21—C2—C3—C4	177.83 (13)
C3A—C4A—C5A—C6A	−56.35 (17)	C1—C2—C21—O21	40.40 (18)
C4A—C5A—C6A—N1A	55.68 (17)	C1—C2—C21—O22	−141.41 (13)
N1B—C2B—C3B—C4B	57.22 (18)	C3—C2—C21—O21	−138.54 (13)
C2B—C3B—C4B—C5B	−56.38 (19)	C3—C2—C21—O22	39.65 (19)
C3B—C4B—C5B—C6B	55.2 (2)	C2—C3—C4—Cl4	−179.89 (11)
C4B—C5B—C6B—N1B	−54.75 (18)	C2—C3—C4—C5	−0.3 (2)
C6—C1—C2—C3	2.2 (2)	Cl4—C4—C5—Cl5	−0.3 (2)
C6—C1—C2—C21	−176.73 (13)	Cl4—C4—C5—C6	−179.77 (12)
C11—C1—C2—C3	−172.11 (13)	C3—C4—C5—Cl5	−179.84 (12)
C11—C1—C2—C21	8.95 (19)	C3—C4—C5—C6	0.7 (2)
C2—C1—C6—C5	−1.9 (2)	Cl5—C5—C6—C1	−179.07 (11)
C11—C1—C6—C5	172.68 (13)	C4—C5—C6—C1	0.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O21^i	0.90 (2)	1.80 (2)	2.6820 (17)	164.0 (17)
N1A—H12A···O11	0.914 (19)	1.907 (19)	2.8085 (17)	168.4 (16)
N1B—H11B···O11^i	0.896 (17)	1.917 (17)	2.8054 (16)	170.7 (16)
N1B—H12B···O1W	0.975 (19)	1.882 (19)	2.7866 (18)	153.1 (15)
O1W—H11W···O12	0.82 (2)	1.93 (2)	2.7490 (17)	176 (2)
O1W—H12W···O22^ii	0.84 (2)	1.96 (2)	2.7639 (17)	162 (2)

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