Bis(N,N',N''-triisopropyl-guanidinium) fumarate-fumaric acid (1/1).

The asymmetric unit of the title compound, C(10)H(24)N(3) (+)·0.5C(4)H(2)O(4) (2-)·0.5C(4)H(4)O(4), comprises a triisopropyl-guanidinium cation, half of a fumarate dianion and half of a fumaric acid mol-ecule; both the fumarate dianion and the fumaric acid mol-ecule are located on inversion centres. In the crystal, inter-molecular O-H⋯O hydrogen bonds between the carboxyl groups of the fumaric acid mol-ecules and the carboxyl-ate groups of the fumarate anions lead to the formation of a hydrogen-bonded supra-molecular twisted chain along the b axis. The triisopropyl-guanidinium cations inter-act with the fumarate-fumaric acid chains via extensive N-H⋯O and C-H⋯O hydrogen bonds, leading to a ladder arrangement, with the cation being the rungs that bridge three curled chains of fumarate-fumaric acid. The crystal packing is stabilized by N-H⋯O and C-H⋯O (cation⋯fumarate/fumaric) and O-H⋯O (fumarate⋯fumaric) hydrogen bonds, consolidating a three-dimensional network.

Related literature

For background information and N,N′,N"-tris­ubstituted guanidinium salts, see: Said et al. (2011 ▶). For related structures, see: Said et al. (2005 ▶); Hemamalini & Fun (2010 ▶); Büyükgüngör et al. (2004 ▶). For the preparation of the triisopropyl guanidine compound, see: Ong et al. (2003 ▶).

Experimental

Crystal data

C10H24N3 +·0.5C4H2O4 2−·0.5C4H4O4

M = 301.39

Monoclinic,

a = 9.714 (3) Å

b = 11.633 (3) Å

c = 16.226 (4) Å

β = 102.291 (4)°

V = 1791.6 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 200 K

0.50 × 0.45 × 0.45 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T min = 0.960, T max = 0.964

11184 measured reflections

2514 independent reflections

2121 reflections with I > 2σ(I)

R int = 0.027

θmax = 23.3°

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.130

S = 1.04

2514 reflections

191 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.18 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; 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: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812023094/pv2540sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812023094/pv2540Isup2.hkl

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

C10H24N3+·0.5C4H2O42−·0.5C4H4O4	F(000) = 656
Mr = 301.39	Dx = 1.117 Mg m−3Dm = n/a Mg m−3Dm measured by not measured
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 309 reflections
a = 9.714 (3) Å	θ = 2.2–23.3°
b = 11.633 (3) Å	µ = 0.08 mm−1
c = 16.226 (4) Å	T = 200 K
β = 102.291 (4)°	Block, colourless
V = 1791.6 (8) Å3	0.50 × 0.45 × 0.45 mm
Z = 4

Bruker APEXII CCD area-detector diffractometer	2514 independent reflections
Radiation source: fine-focus sealed tube	2121 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
phi and ω scans	θmax = 23.3°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −10→10
Tmin = 0.960, Tmax = 0.964	k = −12→12
11184 measured reflections	l = −18→18

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044	H-atom parameters constrained
wR(F2) = 0.130	w = 1/[σ2(Fo2) + (0.0727P)2 + 0.7515P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
2514 reflections	Δρmax = 0.22 e Å−3
191 parameters	Δρmin = −0.18 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.013 (2)

Experimental. Data collection is performed with three batch runs at phi = 0.00 ° (650 frames), at phi = 120.00 ° (650 frames), and at phi = 240.00 ° (650 frames). Frame width = 0.30 ° in omega. Data is merged, corrected for decay (if any), and treated with multi-scan absorption corrections (if required). All symmetry-equivalent reflections are merged for centrosymmetric data. Friedel pairs are not merged for noncentrosymmetric data.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > 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
N1	0.3813 (2)	0.7589 (2)	0.65518 (12)	0.0606 (6)
H1A	0.3496	0.7206	0.6082	0.073*
N2	0.55340 (17)	0.87868 (16)	0.72883 (10)	0.0407 (5)
H2A	0.5134	0.8698	0.7722	0.049*
N3	0.55035 (18)	0.83370 (15)	0.58961 (10)	0.0400 (5)
H3A	0.6221	0.8809	0.5930	0.048*
C1	0.4961 (2)	0.82257 (18)	0.65809 (12)	0.0372 (5)
C2	0.3022 (3)	0.7462 (3)	0.72241 (15)	0.0618 (8)
H2B	0.3531	0.7879	0.7738	0.074*
C3	0.1559 (4)	0.7963 (3)	0.6947 (2)	0.0908 (10)
H3B	0.1630	0.8780	0.6813	0.136*
H3C	0.1047	0.7880	0.7402	0.136*
H3D	0.1053	0.7554	0.6445	0.136*
C4	0.2946 (4)	0.6209 (3)	0.7427 (2)	0.0980 (12)
H4A	0.3902	0.5903	0.7614	0.147*
H4B	0.2463	0.5794	0.6922	0.147*
H4C	0.2424	0.6111	0.7876	0.147*
C5	0.6772 (2)	0.95385 (17)	0.74056 (13)	0.0377 (5)
H5A	0.6841	0.9853	0.6842	0.045*
C6	0.6565 (3)	1.0533 (2)	0.79649 (16)	0.0575 (7)
H6A	0.5696	1.0942	0.7712	0.086*
H6B	0.7367	1.1061	0.8023	0.086*
H6C	0.6500	1.0243	0.8522	0.086*
C7	0.8100 (3)	0.8884 (2)	0.77559 (19)	0.0652 (7)
H7A	0.8199	0.8251	0.7374	0.098*
H7B	0.8056	0.8574	0.8311	0.098*
H7C	0.8911	0.9401	0.7811	0.098*
C8	0.5007 (2)	0.77405 (19)	0.50895 (13)	0.0438 (6)
H8A	0.3956	0.7697	0.4980	0.053*
C9	0.5406 (3)	0.8431 (2)	0.43942 (14)	0.0555 (6)
H9A	0.5003	0.9204	0.4387	0.083*
H9B	0.5041	0.8054	0.3852	0.083*
H9C	0.6434	0.8486	0.4490	0.083*
C10	0.5571 (4)	0.6538 (2)	0.51258 (18)	0.0841 (10)
H10A	0.5288	0.6120	0.5587	0.126*
H10B	0.6602	0.6561	0.5223	0.126*
H10C	0.5193	0.6147	0.4591	0.126*
C11	0.8673 (2)	0.02478 (18)	0.57016 (13)	0.0372 (5)
C12	0.9785 (2)	0.04210 (18)	0.52111 (13)	0.0366 (5)
H12A	1.0196	0.1161	0.5202	0.044*
C13	0.0836 (2)	0.63781 (18)	0.46512 (12)	0.0373 (5)
C14	−0.0139 (2)	0.54111 (18)	0.47181 (12)	0.0388 (5)
H14A	−0.1018	0.5388	0.4327	0.047*
O1	0.81517 (17)	−0.06979 (13)	0.57428 (11)	0.0534 (5)
O2	0.82763 (15)	0.11397 (12)	0.60762 (10)	0.0468 (4)
H2	0.8741	0.1718	0.5986	0.070*
O3	0.19305 (19)	0.64871 (16)	0.51791 (11)	0.0672 (6)
O4	0.04379 (15)	0.70345 (12)	0.40121 (9)	0.0425 (4)

	U11	U22	U33	U12	U13	U23
N1	0.0536 (12)	0.0929 (16)	0.0369 (10)	−0.0418 (11)	0.0131 (9)	−0.0110 (10)
N2	0.0404 (10)	0.0532 (11)	0.0306 (9)	−0.0154 (8)	0.0123 (7)	−0.0032 (8)
N3	0.0414 (10)	0.0462 (10)	0.0337 (9)	−0.0158 (8)	0.0111 (7)	−0.0042 (8)
C1	0.0352 (11)	0.0435 (12)	0.0321 (11)	−0.0100 (9)	0.0058 (9)	0.0015 (9)
C2	0.0527 (14)	0.094 (2)	0.0402 (13)	−0.0384 (14)	0.0138 (11)	−0.0032 (13)
C3	0.093 (2)	0.087 (2)	0.106 (3)	0.0130 (18)	0.051 (2)	0.0107 (19)
C4	0.091 (2)	0.116 (3)	0.098 (2)	0.018 (2)	0.0448 (19)	0.059 (2)
C5	0.0373 (11)	0.0419 (12)	0.0344 (11)	−0.0107 (9)	0.0085 (9)	−0.0029 (9)
C6	0.0753 (17)	0.0488 (15)	0.0524 (14)	−0.0164 (12)	0.0227 (13)	−0.0100 (11)
C7	0.0413 (13)	0.0687 (17)	0.0832 (19)	−0.0008 (12)	0.0076 (13)	0.0107 (14)
C8	0.0505 (13)	0.0483 (13)	0.0303 (11)	−0.0115 (10)	0.0035 (9)	−0.0018 (9)
C9	0.0729 (16)	0.0591 (15)	0.0346 (12)	−0.0105 (12)	0.0115 (11)	−0.0006 (11)
C10	0.143 (3)	0.0518 (17)	0.0493 (16)	0.0038 (17)	0.0019 (17)	−0.0053 (12)
C11	0.0385 (11)	0.0384 (12)	0.0380 (11)	−0.0092 (9)	0.0154 (9)	−0.0038 (9)
C12	0.0381 (11)	0.0344 (11)	0.0404 (11)	−0.0115 (8)	0.0152 (9)	−0.0012 (8)
C13	0.0428 (12)	0.0405 (12)	0.0291 (11)	−0.0111 (9)	0.0089 (9)	−0.0064 (9)
C14	0.0378 (11)	0.0453 (12)	0.0313 (10)	−0.0120 (9)	0.0028 (9)	−0.0033 (8)
O1	0.0598 (10)	0.0442 (9)	0.0669 (11)	−0.0215 (8)	0.0376 (8)	−0.0112 (8)
O2	0.0534 (9)	0.0382 (8)	0.0578 (9)	−0.0073 (7)	0.0316 (8)	−0.0029 (7)
O3	0.0652 (11)	0.0750 (12)	0.0514 (10)	−0.0411 (9)	−0.0100 (9)	0.0121 (9)
O4	0.0539 (9)	0.0377 (8)	0.0366 (8)	−0.0069 (7)	0.0111 (7)	0.0000 (6)

N1—C1	1.331 (3)	C7—H7A	0.9800
N1—C2	1.469 (3)	C7—H7B	0.9800
N1—H1A	0.8800	C7—H7C	0.9800
N2—C1	1.335 (3)	C8—C10	1.499 (4)
N2—C5	1.466 (3)	C8—C9	1.502 (3)
N2—H2A	0.8800	C8—H8A	1.0000
N3—C1	1.334 (3)	C9—H9A	0.9800
N3—C8	1.469 (3)	C9—H9B	0.9800
N3—H3A	0.8800	C9—H9C	0.9800
C2—C4	1.500 (5)	C10—H10A	0.9800
C2—C3	1.513 (4)	C10—H10B	0.9800
C2—H2B	1.0000	C10—H10C	0.9800
C3—H3B	0.9800	C11—O1	1.219 (2)
C3—H3C	0.9800	C11—O2	1.302 (3)
C3—H3D	0.9800	C11—C12	1.485 (3)
C4—H4A	0.9800	C12—C12i	1.314 (4)
C4—H4B	0.9800	C12—H12A	0.9500
C4—H4C	0.9800	C13—O3	1.222 (3)
C5—C7	1.501 (3)	C13—O4	1.279 (3)
C5—C6	1.510 (3)	C13—C14	1.489 (3)
C5—H5A	1.0000	C14—C14ii	1.311 (4)
C6—H6A	0.9800	C14—H14A	0.9500
C6—H6B	0.9800	O2—H2	0.8400
C6—H6C	0.9800
C1—N1—C2	126.59 (19)	H6A—C6—H6C	109.5
C1—N1—H1A	116.7	H6B—C6—H6C	109.5
C2—N1—H1A	116.7	C5—C7—H7A	109.5
C1—N2—C5	125.70 (16)	C5—C7—H7B	109.5
C1—N2—H2A	117.1	H7A—C7—H7B	109.5
C5—N2—H2A	117.1	C5—C7—H7C	109.5
C1—N3—C8	125.69 (17)	H7A—C7—H7C	109.5
C1—N3—H3A	117.2	H7B—C7—H7C	109.5
C8—N3—H3A	117.2	N3—C8—C10	110.97 (19)
N1—C1—N2	119.70 (18)	N3—C8—C9	109.17 (18)
N1—C1—N3	120.07 (18)	C10—C8—C9	112.2 (2)
N2—C1—N3	120.18 (17)	N3—C8—H8A	108.1
N1—C2—C4	108.6 (2)	C10—C8—H8A	108.1
N1—C2—C3	110.3 (2)	C9—C8—H8A	108.1
C4—C2—C3	110.6 (2)	C8—C9—H9A	109.5
N1—C2—H2B	109.1	C8—C9—H9B	109.5
C4—C2—H2B	109.1	H9A—C9—H9B	109.5
C3—C2—H2B	109.1	C8—C9—H9C	109.5
C2—C3—H3B	109.5	H9A—C9—H9C	109.5
C2—C3—H3C	109.5	H9B—C9—H9C	109.5
H3B—C3—H3C	109.5	C8—C10—H10A	109.5
C2—C3—H3D	109.5	C8—C10—H10B	109.5
H3B—C3—H3D	109.5	H10A—C10—H10B	109.5
H3C—C3—H3D	109.5	C8—C10—H10C	109.5
C2—C4—H4A	109.5	H10A—C10—H10C	109.5
C2—C4—H4B	109.5	H10B—C10—H10C	109.5
H4A—C4—H4B	109.5	O1—C11—O2	121.74 (18)
C2—C4—H4C	109.5	O1—C11—C12	120.65 (18)
H4A—C4—H4C	109.5	O2—C11—C12	117.61 (17)
H4B—C4—H4C	109.5	C12i—C12—C11	121.8 (2)
N2—C5—C7	111.20 (19)	C12i—C12—H12A	119.1
N2—C5—C6	108.94 (17)	C11—C12—H12A	119.1
C7—C5—C6	112.0 (2)	O3—C13—O4	125.02 (19)
N2—C5—H5A	108.2	O3—C13—C14	119.94 (19)
C7—C5—H5A	108.2	O4—C13—C14	115.03 (18)
C6—C5—H5A	108.2	C14ii—C14—C13	124.2 (2)
C5—C6—H6A	109.5	C14ii—C14—H14A	117.9
C5—C6—H6B	109.5	C13—C14—H14A	117.9
H6A—C6—H6B	109.5	C11—O2—H2	109.5
C5—C6—H6C	109.5
C2—N1—C1—N2	3.1 (4)	C1—N2—C5—C7	−92.6 (3)
C2—N1—C1—N3	−174.4 (2)	C1—N2—C5—C6	143.5 (2)
C5—N2—C1—N1	−178.4 (2)	C1—N3—C8—C10	−80.4 (3)
C5—N2—C1—N3	−1.0 (3)	C1—N3—C8—C9	155.4 (2)
C8—N3—C1—N1	−4.8 (3)	O1—C11—C12—C12i	1.9 (4)
C8—N3—C1—N2	177.8 (2)	O2—C11—C12—C12i	−177.6 (3)
C1—N1—C2—C4	−123.8 (3)	O3—C13—C14—C14ii	−5.4 (4)
C1—N1—C2—C3	114.8 (3)	O4—C13—C14—C14ii	173.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3	0.88	2.05	2.866 (2)	154
N2—H2A···O4iii	0.88	2.22	2.976 (2)	144
N3—H3A···O1iv	0.88	2.04	2.866 (2)	155
O2—H2···O4v	0.84	1.66	2.484 (2)	168
C8—H8A···O3	1.00	2.49	3.356 (2)	144
C2—H2B···O4iii	1.00	2.46	3.372 (2)	150
C5—H5A···O1iv	1.00	2.48	3.270 (2)	135

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3	0.88	2.05	2.866 (2)	154
N2—H2A⋯O4i	0.88	2.22	2.976 (2)	144
N3—H3A⋯O1ii	0.88	2.04	2.866 (2)	155
O2—H2⋯O4iii	0.84	1.66	2.484 (2)	168
C8—H8A⋯O3	1.00	2.49	3.356 (2)	144
C2—H2B⋯O4i	1.00	2.46	3.372 (2)	150
C5—H5A⋯O1ii	1.00	2.48	3.270 (2)	135

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