Bis(dimethyl-ammonium) 3,3'-dicarb-oxy-5,5'-(5,7,12,14-tetra-oxo-6,13-diaza-tetra-cyclo-[6.6.2.0(4,16).0(11,15)]hexa-deca-1,3,8,10,15-penta-ene-6,13-di-yl)dibenzoate dihydrate.

The title compound, 2C(2)H(8)N(+)·C(30)H(12)N(2)O(12) (2-)·2H(2)O, comprises dimethyl-ammonium cations, 3,3'-dicarb-oxy-5,5'-(5,7,12,14-tetra-oxo-6,13-diaza-tetra-cyclo-[6.6.2.0(4,16).0(11,15)]hexa-deca-1,3,8,10,15-penta-ene-6,13-di-yl)dibenzoate dianions and water mol-ecules. The dianion is situated on a crystallographic inversion centre. Two very strong symmetry-restricted O⋯H⋯O hydrogen bonds are present which are situated about the crystallographic inversion centres. In one of these hydrogen bonds, the H atom is situated at its centre, while in the other one the H atom is disordered about its centre. Both H atoms are involved in the chain-like C(2) (2)(16) motif, and not in a more common motif R(2) (2)(8) that is composed of a pair of hydrogen carboxyl-ates with the H atoms situated about the centre between the pair of O atoms. In the crystal, inter-action of these hydrogen bonds results in formation of anionic layers of dianions parallel to (-111). The water mol-ecules donate their H atoms to one of two of the carboxyl-ate O atoms, forming strong hydrogen bonds. The dimethyl-ammonium donates a bifurcated hydrogen bond to an oxo group of the dianion, forming weak hydrogen bonds. All the hydrogen bonds form a three-dimensional hydrogen-bonded network.

Related literature

For organic supra­molecular solids, see: Pantos et al. (2007 ▶). For multi-component mol­ecular crystals or organic co-crystals, see: Bond (2007 ▶); MacGillivray (2008 ▶); Yan et al. (2011 ▶). For prediction of organic crystal structures, see: Pigge (2011 ▶). For organic structures based on naphthalaleneteracarb­oxy­lic diimide derivatives, see: Xu et al. (2011 ▶). For hydrogen carboxyl­ates forming chain-like motifs with very strong O—H⋯O hydrogen bonds, see: Foces-Foces et al. (1996 ▶); Hsu et al. (2006 ▶); Aciro et al. (2009 ▶). For in situ hydrolysis of dimethyl­formamide mol­ecules, see: Jain et al. (2008 ▶). For classification of hydrogen bonds, see: Desiraju & Steiner (1999 ▶). For graph-set motifs, see: Etter et al. (1990 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

2C2H8N+·C30H12N2O12 2−·2H2O

M = 720.64

Monoclinic,

a = 10.428 (13) Å

b = 8.651 (10) Å

c = 18.40 (2) Å

β = 91.956 (16)°

V = 1659 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.11 mm−1

T = 293 K

0.20 × 0.20 × 0.20 mm

Data collection

Rigaku Saturn70 diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2008 ▶) T min = 0.788, T max = 1.000

12286 measured reflections

3780 independent reflections

2137 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.081

wR(F 2) = 0.266

S = 1.01

3780 reflections

248 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.36 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2008 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812025470/fb2246sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812025470/fb2246Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812025470/fb2246Isup3.cml

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

2C2H8N+·C30H12N2O122−·2H2O	F(000) = 752
Mr = 720.64	Dx = 1.443 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3435 reflections
a = 10.428 (13) Å	θ = 2.2–27.6°
b = 8.651 (10) Å	µ = 0.11 mm−1
c = 18.40 (2) Å	T = 293 K
β = 91.956 (16)°	Cube-like, colourless
V = 1659 (4) Å3	0.20 × 0.20 × 0.20 mm
Z = 2

Rigaku Saturn70 diffractometer	3780 independent reflections
Radiation source: fine-focus sealed tube	2137 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 28.5714 pixels mm-1	θmax = 27.5°, θmin = 3.2°
CCD_Profile_fitting scans	h = −13→13
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2008)	k = −11→11
Tmin = 0.788, Tmax = 1.000	l = −23→21
12286 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)] = 0.081	Hydrogen site location: difference Fourier map
wR(F2) = 0.266	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.1621P)2] where P = (Fo2 + 2Fc2)/3
3780 reflections	(Δ/σ)max < 0.001
248 parameters	Δρmax = 0.43 e Å−3
3 restraints	Δρmin = −0.36 e Å−3
0 constraints

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. 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 > 2sigma(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	Occ. (<1)
N1	0.6155 (2)	0.9195 (3)	0.17822 (12)	0.0435 (6)
C3	0.7165 (3)	0.7875 (3)	0.39335 (14)	0.0430 (6)
H3A	0.7380	0.7588	0.4409	0.052*
O6	0.7771 (2)	0.7754 (3)	0.13324 (12)	0.0697 (7)
C6	0.7610 (3)	0.9351 (3)	0.28630 (15)	0.0473 (7)
H6A	0.8123	1.0043	0.2617	0.057*
C12	0.5244 (2)	0.9859 (3)	0.03593 (13)	0.0402 (6)
C7	0.6535 (3)	0.8733 (3)	0.25224 (13)	0.0415 (6)
C8	0.5761 (3)	0.7673 (3)	0.28718 (14)	0.0425 (6)
H8A	0.5040	0.7259	0.2633	0.051*
O5	0.4661 (3)	1.0808 (3)	0.22384 (12)	0.0720 (8)
O3	0.9850 (2)	1.0402 (3)	0.36519 (13)	0.0745 (8)
C14	0.5140 (3)	1.0235 (3)	0.17045 (14)	0.0459 (7)
C4	0.7929 (3)	0.8936 (3)	0.35776 (14)	0.0442 (7)
C13	0.4669 (3)	1.0575 (3)	0.09499 (14)	0.0444 (7)
O1	0.5588 (3)	0.5959 (3)	0.46612 (13)	0.0822 (9)
H1	0.5000	0.5000	0.5000	0.17 (4)*
C2	0.6085 (3)	0.7243 (3)	0.35853 (14)	0.0409 (6)
C9	0.6833 (3)	0.8543 (4)	0.12086 (15)	0.0473 (7)
C1	0.5278 (3)	0.6114 (4)	0.39882 (16)	0.0538 (8)
C10	0.6314 (3)	0.8857 (3)	0.04610 (14)	0.0452 (7)
C15	0.3628 (3)	1.1555 (4)	0.08394 (16)	0.0569 (8)
H15A	0.3255	1.2033	0.1232	0.068*
C5	0.9058 (3)	0.9650 (4)	0.39769 (17)	0.0555 (8)
C11	0.6858 (3)	0.8183 (4)	−0.01297 (16)	0.0590 (8)
H11A	0.7565	0.7538	−0.0058	0.071*
N2	0.3624 (5)	0.1938 (5)	0.3549 (2)	0.1119 (15)
H2A	0.4089	0.2749	0.3401	0.134*
H2B	0.3412	0.1375	0.3152	0.134*
C16	0.2451 (4)	0.2531 (6)	0.3843 (3)	0.0923 (13)
H16A	0.1929	0.2981	0.3459	0.138*
H16B	0.2656	0.3303	0.4203	0.138*
H16C	0.1990	0.1701	0.4062	0.138*
C17	0.4449 (5)	0.0987 (6)	0.4027 (3)	0.1022 (15)
H17A	0.5121	0.0541	0.3752	0.153*
H17B	0.3950	0.0178	0.4235	0.153*
H17C	0.4819	0.1619	0.4409	0.153*
O2	0.4408 (3)	0.5385 (3)	0.36690 (14)	0.0844 (10)
O4	0.9083 (2)	0.9425 (3)	0.46707 (12)	0.0759 (8)
H2	0.965 (5)	1.036 (6)	0.500 (3)	0.040 (16)*	0.50
O7	0.6740 (4)	0.5344 (6)	0.7689 (2)	0.1276 (14)
H3	0.620 (6)	0.552 (9)	0.725 (2)	0.191*
H4	0.611 (6)	0.540 (9)	0.808 (3)	0.191*

	U11	U22	U33	U12	U13	U23
N1	0.0534 (13)	0.0541 (13)	0.0224 (11)	−0.0007 (10)	−0.0079 (9)	0.0064 (9)
C3	0.0529 (15)	0.0514 (15)	0.0242 (13)	−0.0022 (12)	−0.0059 (11)	0.0043 (11)
O6	0.0693 (14)	0.1023 (18)	0.0368 (13)	0.0242 (13)	−0.0068 (10)	0.0118 (12)
C6	0.0531 (15)	0.0600 (17)	0.0282 (14)	−0.0161 (13)	−0.0071 (11)	0.0086 (12)
C12	0.0476 (14)	0.0478 (14)	0.0249 (14)	−0.0043 (12)	−0.0036 (11)	0.0055 (10)
C7	0.0525 (14)	0.0500 (15)	0.0214 (13)	−0.0042 (12)	−0.0082 (11)	0.0021 (10)
C8	0.0495 (14)	0.0488 (15)	0.0285 (14)	−0.0065 (12)	−0.0082 (11)	0.0037 (11)
O5	0.0876 (17)	0.1009 (19)	0.0271 (12)	0.0284 (14)	−0.0023 (11)	−0.0034 (11)
O3	0.0663 (14)	0.111 (2)	0.0455 (14)	−0.0401 (14)	−0.0119 (11)	0.0173 (13)
C14	0.0555 (16)	0.0581 (16)	0.0238 (14)	−0.0009 (13)	−0.0035 (11)	0.0045 (11)
C4	0.0467 (14)	0.0576 (16)	0.0277 (14)	−0.0103 (12)	−0.0087 (11)	0.0040 (11)
C13	0.0514 (15)	0.0588 (16)	0.0226 (13)	−0.0014 (13)	−0.0049 (11)	0.0043 (11)
O1	0.1009 (19)	0.107 (2)	0.0378 (13)	−0.0553 (16)	−0.0163 (13)	0.0252 (13)
C2	0.0485 (14)	0.0443 (14)	0.0294 (14)	−0.0070 (11)	−0.0032 (11)	0.0035 (11)
C9	0.0530 (15)	0.0601 (17)	0.0286 (14)	0.0031 (14)	−0.0032 (12)	0.0076 (12)
C1	0.0645 (18)	0.0637 (18)	0.0327 (16)	−0.0190 (15)	−0.0064 (13)	0.0127 (13)
C10	0.0502 (15)	0.0582 (16)	0.0269 (14)	−0.0009 (13)	−0.0047 (11)	0.0084 (11)
C15	0.0705 (19)	0.074 (2)	0.0262 (14)	0.0165 (16)	−0.0010 (13)	−0.0003 (13)
C5	0.0581 (18)	0.075 (2)	0.0327 (16)	−0.0185 (16)	−0.0135 (13)	0.0072 (14)
C11	0.0644 (18)	0.079 (2)	0.0332 (16)	0.0206 (16)	−0.0042 (13)	0.0068 (14)
N2	0.180 (4)	0.084 (2)	0.075 (3)	0.040 (3)	0.051 (3)	0.013 (2)
C16	0.083 (3)	0.096 (3)	0.098 (4)	−0.009 (3)	0.002 (2)	0.004 (2)
C17	0.099 (3)	0.109 (3)	0.098 (4)	0.019 (3)	−0.007 (3)	−0.019 (3)
O2	0.0893 (18)	0.106 (2)	0.0561 (16)	−0.0564 (16)	−0.0266 (13)	0.0311 (14)
O4	0.0778 (16)	0.115 (2)	0.0328 (12)	−0.0436 (15)	−0.0197 (11)	0.0107 (12)
O7	0.128 (3)	0.165 (4)	0.090 (3)	−0.030 (3)	0.017 (2)	−0.026 (3)

N1—C14	1.393 (4)	C2—C1	1.501 (4)
N1—C9	1.408 (4)	C9—C10	1.486 (4)
N1—C7	1.461 (3)	C1—O2	1.237 (4)
C3—C2	1.389 (4)	C10—C11	1.373 (4)
C3—C4	1.394 (4)	C15—C11i	1.403 (4)
C3—H3A	0.9300	C15—H15A	0.9300
O6—C9	1.208 (4)	C5—O4	1.291 (4)
C6—C7	1.374 (4)	C11—C15i	1.403 (4)
C6—C4	1.393 (4)	C11—H11A	0.9300
C6—H6A	0.9300	N2—C16	1.448 (6)
C12—C13	1.403 (4)	N2—C17	1.463 (6)
C12—C10	1.421 (4)	N2—H2A	0.9000
C12—C12i	1.421 (5)	N2—H2B	0.9000
C7—C8	1.393 (4)	C16—H16A	0.9600
C8—C2	1.395 (4)	C16—H16B	0.9600
C8—H8A	0.9300	C16—H16C	0.9600
O5—C14	1.222 (4)	C17—H17A	0.9600
O3—C5	1.224 (4)	C17—H17B	0.9600
C14—C13	1.486 (4)	C17—H17C	0.9600
C4—C5	1.499 (4)	O4—H2	1.15 (6)
C13—C15	1.387 (4)	O7—H3	0.98 (2)
O1—C1	1.276 (4)	O7—H4	0.98 (2)
O1—H1	1.216 (2)
C14—N1—C9	125.5 (2)	O2—C1—C2	120.8 (3)
C14—N1—C7	117.0 (2)	O1—C1—C2	114.8 (2)
C9—N1—C7	117.5 (2)	C11—C10—C12	119.9 (2)
C2—C3—C4	120.7 (2)	C11—C10—C9	120.5 (3)
C2—C3—H3A	119.7	C12—C10—C9	119.5 (3)
C4—C3—H3A	119.7	C13—C15—C11i	119.4 (3)
C7—C6—C4	119.7 (3)	C13—C15—H15A	120.3
C7—C6—H6A	120.2	C11i—C15—H15A	120.3
C4—C6—H6A	120.2	O3—C5—O4	124.9 (3)
C13—C12—C10	121.5 (2)	O3—C5—C4	120.8 (3)
C13—C12—C12i	119.8 (3)	O4—C5—C4	114.3 (3)
C10—C12—C12i	118.8 (3)	C10—C11—C15i	121.5 (3)
C6—C7—C8	121.5 (2)	C10—C11—H11A	119.3
C6—C7—N1	120.6 (2)	C15i—C11—H11A	119.3
C8—C7—N1	117.9 (2)	C16—N2—C17	117.5 (4)
C7—C8—C2	119.0 (2)	C16—N2—H2A	107.9
C7—C8—H8A	120.5	C17—N2—H2A	107.9
C2—C8—H8A	120.5	C16—N2—H2B	107.9
O5—C14—N1	120.6 (3)	C17—N2—H2B	107.9
O5—C14—C13	122.7 (3)	H2A—N2—H2B	107.2
N1—C14—C13	116.7 (2)	N2—C16—H16A	109.5
C6—C4—C3	119.4 (2)	N2—C16—H16B	109.5
C6—C4—C5	121.0 (3)	H16A—C16—H16B	109.5
C3—C4—C5	119.6 (2)	N2—C16—H16C	109.5
C15—C13—C12	120.6 (3)	H16A—C16—H16C	109.5
C15—C13—C14	119.3 (3)	H16B—C16—H16C	109.5
C12—C13—C14	120.0 (3)	N2—C17—H17A	109.5
C1—O1—H1	117.0 (2)	N2—C17—H17B	109.5
C3—C2—C8	119.7 (2)	H17A—C17—H17B	109.5
C3—C2—C1	119.2 (2)	N2—C17—H17C	109.5
C8—C2—C1	121.1 (2)	H17A—C17—H17C	109.5
O6—C9—N1	120.6 (3)	H17B—C17—H17C	109.5
O6—C9—C10	123.0 (3)	C5—O4—H2	114 (3)
N1—C9—C10	116.4 (2)	H3—O7—H4	102 (4)
O2—C1—O1	124.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ii	1.22 (1)	1.22 (1)	2.432 (5)	180 (1)
O4—H2···O4iii	1.15 (6)	1.45 (5)	2.441 (5)	139 (4)
N2—H2B···O5iv	0.90	2.22	2.850 (5)	127
O7—H3···O2ii	0.98 (2)	1.95 (5)	2.805 (6)	144 (6)
O7—H4···O3v	0.98 (2)	1.85 (4)	2.771 (6)	154 (7)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O1i	1.22 (1)	1.22 (1)	2.432 (5)	180 (1)
O4—H2⋯O4ii	1.15 (6)	1.45 (5)	2.441 (5)	139 (4)
N2—H2B⋯O5iii	0.90	2.22	2.850 (5)	127
O7—H3⋯O2i	0.98 (2)	1.95 (5)	2.805 (6)	144 (6)
O7—H4⋯O3iv	0.98 (2)	1.85 (4)	2.771 (6)	154 (7)

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