Bis(guanidinium) 4,5-dichloro-phthalate monohydrate.

In the structure of the title hydrated salt, 2CH(6)N(3) (+)·C(8)H(2)Cl(2)O(4) (2-)·H(2)O, the planes of the carboxyl-ate groups of the dianion are rotated out of the plane of the benzene ring [dihedral angles = 48.42 (10) and 55.64 (9)°]. A duplex-sheet structure is formed through guanidinium-carboxyl-ate N-H⋯O, guanidinium-water N-H⋯O and water-carboxyl-ate O-H⋯O hydrogen-bonding associations.

Related literature

For the structures of 1:1 salts of 4,5-dichloro­phthalate, see: Mallinson et al. (2003 ▶); Bozkurt et al. (2006 ▶); Smith et al. (2008 ▶, 2009 ▶); Smith & Wermuth (2010a ▶,d ▶). For 1:2 salts, see: Büyükgüngör & Odabaşoğlu (2007 ▶); Smith & Wermuth (2010a ▶,c ▶). For guanidinium salts of aromatic dicarb­oxy­lic acids, see: Krumbe & Haussuhl (1986 ▶); Smith & Wermuth (2010b ▶).

Experimental

Crystal data

2CH6N3 +·C8H2Cl2O4 2−·H2O

M = 371.19

Monoclinic,

a = 15.9797 (5) Å

b = 6.9432 (2) Å

c = 15.2266 (5) Å

β = 94.650 (3)°

V = 1683.84 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.42 mm−1

T = 200 K

0.28 × 0.25 × 0.20 mm

Data collection

Oxford Diffraction Gemini-S CCD area-detector diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T min = 0.933, T max = 0.990

11236 measured reflections

3319 independent reflections

2627 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.105

S = 1.16

3319 reflections

264 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.63 e Å−3

Δρmin = −0.83 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); 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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811021192/ng5176sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021192/ng5176Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811021192/ng5176Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

2CH6N3+·C8H2Cl2O42−·H2O	F(000) = 768
Mr = 371.19	Dx = 1.464 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6093 reflections
a = 15.9797 (5) Å	θ = 3.2–28.6°
b = 6.9432 (2) Å	µ = 0.42 mm−1
c = 15.2266 (5) Å	T = 200 K
β = 94.650 (3)°	Block, colourless
V = 1683.84 (9) Å3	0.28 × 0.25 × 0.20 mm
Z = 4

Oxford Diffraction Gemini-S CCD area-detector diffractometer	3319 independent reflections
Radiation source: Enhance (Mo) X-ray source	2627 reflections with I > 2σ(I)
graphite	Rint = 0.022
Detector resolution: 16.077 pixels mm-1	θmax = 26.0°, θmin = 3.2°
ω scans	h = −18→19
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −8→8
Tmin = 0.933, Tmax = 0.990	l = −11→18
11236 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ2(Fo2) + (0.0562P)2 + 0.1489P] where P = (Fo2 + 2Fc2)/3
3319 reflections	(Δ/σ)max = 0.001
264 parameters	Δρmax = 0.63 e Å−3
0 restraints	Δρmin = −0.83 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cl4	1.05872 (4)	0.24406 (13)	0.56212 (5)	0.0786 (3)
Cl5	1.03264 (4)	−0.12369 (11)	0.67711 (5)	0.0676 (3)
O11	0.70520 (8)	0.02886 (19)	0.75803 (8)	0.0304 (4)
O12	0.66435 (8)	0.04844 (17)	0.61463 (8)	0.0260 (4)
O21	0.70448 (9)	0.47401 (19)	0.64857 (9)	0.0325 (4)
O22	0.73076 (9)	0.47465 (18)	0.50680 (9)	0.0313 (4)
C1	0.80565 (11)	0.1185 (2)	0.65803 (11)	0.0207 (5)
C2	0.81671 (11)	0.2830 (2)	0.60675 (11)	0.0221 (5)
C3	0.89502 (12)	0.3185 (3)	0.57737 (13)	0.0338 (6)
C4	0.96178 (12)	0.1945 (4)	0.59905 (14)	0.0397 (7)
C5	0.95069 (13)	0.0335 (3)	0.65047 (14)	0.0361 (7)
C6	0.87267 (12)	−0.0039 (3)	0.68007 (12)	0.0278 (6)
C11	0.71840 (11)	0.0626 (2)	0.67974 (12)	0.0206 (5)
C21	0.74498 (11)	0.4223 (2)	0.58557 (12)	0.0221 (5)
N1A	0.51848 (11)	0.2730 (3)	0.54869 (12)	0.0297 (5)
N2A	0.51734 (11)	0.2568 (3)	0.69927 (12)	0.0318 (5)
N3A	0.40865 (10)	0.4034 (2)	0.61686 (13)	0.0281 (5)
C1A	0.48092 (11)	0.3101 (3)	0.62137 (12)	0.0231 (5)
N1B	0.74241 (11)	0.6136 (3)	0.96559 (11)	0.0288 (5)
N2B	0.73486 (13)	0.3392 (3)	0.88218 (13)	0.0403 (6)
N3B	0.74928 (11)	0.6306 (3)	0.81514 (12)	0.0314 (6)
C1B	0.74182 (11)	0.5289 (3)	0.88781 (12)	0.0246 (6)
O1W	0.56692 (9)	0.7224 (2)	0.63168 (9)	0.0296 (4)
H3	0.90300	0.42630	0.54280	0.0410*
H6	0.86520	−0.11150	0.71490	0.0330*
H11A	0.4941 (13)	0.288 (3)	0.4989 (16)	0.029 (6)*
H12A	0.5663 (15)	0.206 (3)	0.5529 (14)	0.040 (6)*
H21A	0.5643 (18)	0.187 (4)	0.7004 (17)	0.056 (7)*
H22A	0.4931 (16)	0.254 (3)	0.7442 (18)	0.048 (7)*
H31A	0.3862 (16)	0.437 (3)	0.6634 (18)	0.049 (7)*
H32A	0.3855 (14)	0.436 (3)	0.5679 (16)	0.038 (7)*
H11B	0.7413 (13)	0.740 (3)	0.9689 (13)	0.033 (6)*
H12B	0.7272 (14)	0.546 (3)	1.0077 (15)	0.037 (6)*
H21B	0.7375 (16)	0.267 (4)	0.9278 (18)	0.055 (8)*
H22B	0.7359 (15)	0.281 (4)	0.8289 (18)	0.056 (8)*
H31B	0.7401 (14)	0.570 (3)	0.7640 (16)	0.039 (6)*
H32B	0.7451 (13)	0.753 (3)	0.8189 (14)	0.032 (6)*
H11W	0.6032 (18)	0.637 (4)	0.6354 (18)	0.058 (8)*
H12W	0.5946 (16)	0.831 (4)	0.6270 (17)	0.054 (7)*

	U11	U22	U33	U12	U13	U23
Cl4	0.0240 (3)	0.1185 (7)	0.0961 (6)	0.0108 (3)	0.0218 (3)	0.0627 (5)
Cl5	0.0354 (3)	0.0869 (5)	0.0818 (5)	0.0326 (3)	0.0135 (3)	0.0423 (4)
O11	0.0375 (8)	0.0322 (7)	0.0229 (7)	−0.0065 (6)	0.0117 (6)	−0.0002 (6)
O12	0.0220 (7)	0.0265 (7)	0.0292 (7)	−0.0010 (5)	0.0003 (5)	0.0023 (5)
O21	0.0359 (8)	0.0334 (7)	0.0283 (7)	0.0100 (6)	0.0042 (6)	−0.0032 (6)
O22	0.0381 (8)	0.0279 (7)	0.0276 (7)	0.0084 (6)	0.0002 (6)	0.0072 (6)
C1	0.0228 (9)	0.0234 (9)	0.0160 (8)	0.0001 (7)	0.0024 (7)	0.0006 (7)
C2	0.0230 (9)	0.0242 (9)	0.0188 (9)	−0.0003 (7)	0.0007 (7)	0.0030 (7)
C3	0.0274 (10)	0.0399 (11)	0.0345 (11)	−0.0015 (9)	0.0050 (8)	0.0178 (9)
C4	0.0202 (10)	0.0607 (14)	0.0391 (12)	0.0016 (9)	0.0077 (9)	0.0193 (11)
C5	0.0254 (10)	0.0471 (13)	0.0360 (12)	0.0122 (9)	0.0029 (9)	0.0129 (10)
C6	0.0288 (10)	0.0299 (10)	0.0248 (10)	0.0038 (8)	0.0025 (8)	0.0082 (8)
C11	0.0241 (9)	0.0143 (8)	0.0241 (9)	0.0013 (7)	0.0059 (7)	−0.0002 (7)
C21	0.0246 (9)	0.0161 (8)	0.0251 (10)	−0.0023 (7)	−0.0004 (7)	0.0007 (7)
N1A	0.0270 (9)	0.0394 (10)	0.0230 (9)	0.0087 (8)	0.0038 (7)	0.0013 (7)
N2A	0.0275 (9)	0.0451 (10)	0.0232 (9)	0.0083 (8)	0.0051 (7)	0.0033 (8)
N3A	0.0216 (8)	0.0381 (9)	0.0248 (10)	0.0028 (7)	0.0036 (7)	−0.0012 (8)
C1A	0.0211 (9)	0.0228 (9)	0.0258 (10)	−0.0032 (7)	0.0046 (7)	0.0001 (7)
N1B	0.0426 (10)	0.0223 (9)	0.0216 (9)	−0.0005 (7)	0.0027 (7)	−0.0003 (7)
N2B	0.0696 (14)	0.0238 (9)	0.0275 (10)	−0.0036 (9)	0.0042 (9)	−0.0020 (8)
N3B	0.0434 (10)	0.0275 (10)	0.0236 (9)	0.0023 (8)	0.0048 (7)	0.0019 (7)
C1B	0.0251 (9)	0.0247 (10)	0.0237 (10)	−0.0003 (7)	0.0005 (7)	0.0011 (7)
O1W	0.0265 (7)	0.0258 (8)	0.0363 (8)	−0.0026 (6)	0.0021 (6)	0.0010 (6)

Cl4—C4	1.725 (2)	N2B—C1B	1.324 (3)
Cl5—C5	1.728 (2)	N3B—C1B	1.326 (3)
O11—C11	1.250 (2)	N1B—H12B	0.85 (2)
O12—C11	1.265 (2)	N1B—H11B	0.88 (2)
O21—C21	1.252 (2)	N2B—H21B	0.86 (3)
O22—C21	1.256 (2)	N2B—H22B	0.91 (3)
O1W—H12W	0.88 (3)	N3B—H31B	0.89 (2)
O1W—H11W	0.83 (3)	N3B—H32B	0.86 (2)
N1A—C1A	1.326 (3)	C1—C6	1.387 (3)
N2A—C1A	1.331 (3)	C1—C11	1.510 (2)
N3A—C1A	1.321 (2)	C1—C2	1.403 (2)
N1A—H12A	0.89 (2)	C2—C21	1.514 (2)
N1A—H11A	0.83 (2)	C2—C3	1.385 (3)
N2A—H22A	0.81 (3)	C3—C4	1.390 (3)
N2A—H21A	0.89 (3)	C4—C5	1.384 (3)
N3A—H32A	0.84 (2)	C5—C6	1.384 (3)
N3A—H31A	0.85 (3)	C3—H3	0.9300
N1B—C1B	1.322 (3)	C6—H6	0.9300
H11W—O1W—H12W	105 (3)	C2—C3—C4	120.62 (19)
H11A—N1A—H12A	118 (2)	C3—C4—C5	120.24 (19)
C1A—N1A—H12A	119.0 (14)	Cl4—C4—C3	119.43 (19)
C1A—N1A—H11A	121.8 (15)	Cl4—C4—C5	120.33 (17)
H21A—N2A—H22A	115 (2)	Cl5—C5—C4	120.90 (16)
C1A—N2A—H22A	123.6 (18)	Cl5—C5—C6	119.38 (16)
C1A—N2A—H21A	118.3 (17)	C4—C5—C6	119.71 (19)
C1A—N3A—H32A	120.1 (16)	C1—C6—C5	120.30 (18)
H31A—N3A—H32A	119 (2)	O12—C11—C1	115.63 (15)
C1A—N3A—H31A	121.1 (17)	O11—C11—O12	125.16 (16)
C1B—N1B—H12B	116.8 (15)	O11—C11—C1	119.18 (16)
H11B—N1B—H12B	120 (2)	O22—C21—C2	117.60 (15)
C1B—N1B—H11B	119.8 (13)	O21—C21—C2	116.69 (15)
C1B—N2B—H22B	119.6 (18)	O21—C21—O22	125.71 (16)
C1B—N2B—H21B	122.2 (19)	C2—C3—H3	120.00
H21B—N2B—H22B	118 (3)	C4—C3—H3	120.00
H31B—N3B—H32B	122 (2)	C5—C6—H6	120.00
C1B—N3B—H31B	117.4 (14)	C1—C6—H6	120.00
C1B—N3B—H32B	117.4 (14)	N1A—C1A—N2A	119.67 (18)
C6—C1—C11	119.89 (14)	N1A—C1A—N3A	120.31 (18)
C2—C1—C6	120.26 (16)	N2A—C1A—N3A	120.00 (18)
C2—C1—C11	119.44 (15)	N1B—C1B—N2B	119.68 (19)
C3—C2—C21	120.38 (15)	N1B—C1B—N3B	121.1 (2)
C1—C2—C21	120.74 (15)	N2B—C1B—N3B	119.24 (19)
C1—C2—C3	118.86 (16)
C6—C1—C2—C3	1.2 (2)	C1—C2—C21—O21	47.5 (2)
C6—C1—C2—C21	−177.34 (16)	C1—C2—C21—O22	−131.93 (17)
C11—C1—C2—C3	−171.43 (16)	C3—C2—C21—O21	−131.02 (18)
C11—C1—C2—C21	10.0 (2)	C3—C2—C21—O22	49.6 (2)
C2—C1—C6—C5	−1.1 (3)	C2—C3—C4—Cl4	−179.47 (15)
C11—C1—C6—C5	171.54 (17)	C2—C3—C4—C5	0.0 (3)
C2—C1—C11—O11	−129.41 (16)	Cl4—C4—C5—Cl5	−1.3 (3)
C2—C1—C11—O12	52.6 (2)	Cl4—C4—C5—C6	179.63 (16)
C6—C1—C11—O11	57.9 (2)	C3—C4—C5—Cl5	179.30 (17)
C6—C1—C11—O12	−120.04 (17)	C3—C4—C5—C6	0.2 (3)
C1—C2—C3—C4	−0.7 (3)	Cl5—C5—C6—C1	−178.78 (15)
C21—C2—C3—C4	177.87 (18)	C4—C5—C6—C1	0.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H11A···O1Wi	0.83 (2)	2.14 (2)	2.966 (2)	171 (2)
N1A—H12A···O12	0.89 (2)	2.07 (2)	2.914 (2)	156.8 (19)
N1B—H11B···O22ii	0.88 (2)	2.07 (2)	2.936 (2)	166.3 (19)
N1B—H12B···O12iii	0.85 (2)	2.09 (2)	2.904 (2)	162 (2)
N2A—H21A···O11	0.89 (3)	2.59 (3)	3.447 (2)	160 (2)
N2A—H21A···O12	0.89 (3)	2.35 (3)	3.125 (2)	145 (2)
N2A—H22A···O1Wiv	0.81 (3)	2.20 (3)	3.010 (2)	175 (2)
N2B—H21B···O22iii	0.86 (3)	2.07 (3)	2.894 (2)	161 (3)
N2B—H22B···O11	0.91 (3)	2.09 (3)	2.880 (2)	144 (2)
N3A—H31A···O11v	0.85 (3)	2.06 (3)	2.874 (2)	159 (2)
N3A—H32A···O22i	0.84 (2)	2.19 (2)	2.923 (2)	147 (2)
N3B—H31B···O21	0.89 (2)	1.92 (2)	2.799 (2)	169 (2)
N3B—H32B···O11vi	0.86 (2)	2.20 (2)	2.966 (2)	149.2 (19)
O1W—H11W···O21	0.83 (3)	1.97 (3)	2.789 (2)	169 (3)
O1W—H12W···O12vi	0.88 (3)	1.90 (3)	2.7716 (19)	174 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H11A⋯O1Wi	0.83 (2)	2.14 (2)	2.966 (2)	171 (2)
N1A—H12A⋯O12	0.89 (2)	2.07 (2)	2.914 (2)	156.8 (19)
N1B—H11B⋯O22ii	0.88 (2)	2.07 (2)	2.936 (2)	166.3 (19)
N1B—H12B⋯O12iii	0.85 (2)	2.09 (2)	2.904 (2)	162 (2)
N2A—H21A⋯O11	0.89 (3)	2.59 (3)	3.447 (2)	160 (2)
N2A—H21A⋯O12	0.89 (3)	2.35 (3)	3.125 (2)	145 (2)
N2A—H22A⋯O1Wiv	0.81 (3)	2.20 (3)	3.010 (2)	175 (2)
N2B—H21B⋯O22iii	0.86 (3)	2.07 (3)	2.894 (2)	161 (3)
N2B—H22B⋯O11	0.91 (3)	2.09 (3)	2.880 (2)	144 (2)
N3A—H31A⋯O11v	0.85 (3)	2.06 (3)	2.874 (2)	159 (2)
N3A—H32A⋯O22i	0.84 (2)	2.19 (2)	2.923 (2)	147 (2)
N3B—H31B⋯O21	0.89 (2)	1.92 (2)	2.799 (2)	169 (2)
N3B—H32B⋯O11vi	0.86 (2)	2.20 (2)	2.966 (2)	149.2 (19)
O1W—H11W⋯O21	0.83 (3)	1.97 (3)	2.789 (2)	169 (3)
O1W—H12W⋯O12vi	0.88 (3)	1.90 (3)	2.7716 (19)	174 (3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .