Triethyl­ammonium hydrogen fumarate

In crystals of the title compound, the hydrogen fumarate anions form one-dimensional chains through an O-H...O hydrogen bonding along the c and (a+b)/2 directions. There are three sites of the hydrogen fumarate, two of which have an inversion centre.

S1. Comment

The crystal structures of the ammonium and isopropylammonium salts of the fumaric acid dianion were reported by Hosomi et al. (1998). In the title crystals, (I), trans–cis photoisomerization was observed, but no photodimerization occurred. There is a strong O5—H5···O7 hydrogen bond; the O5—H5 and O7—H5 distances are 1.19 (3) and 1.26 (3) Å, respectively.

S2. Experimental

The crystals of (I) were grown from a diethyl ether/2-propanol solution.

S3. Refinement

All H atoms were located from difference syntheses and were refined isotropically. The C—H bond distances are in the range 0.89 (2)–1.05 (4) Å, the N—H distances are 0.87 (2) and 0.90 (2) Å, and the O—H distance is 1.08 (3) Å, except for those involving the H5 atom.

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: TEXSAN.

(I)

Crystal data

C6H16N^+·C4H3O4^−	Z = 4
Mr = 217.26	Dx = 1.166 Mg m^−3
Triclinic, P1	Mo Kα radiation, λ = 0.71073 Å
a = 13.409 (3) Å	Cell parameters from 25 reflections
b = 13.656 (3) Å	θ = 14.4–15.0°
c = 7.432 (2) Å	µ = 0.09 mm^−1
α = 95.03 (3)°	T = 295 K
β = 90.11 (2)°	Prism, colourless
γ = 113.99 (1)°	0.6 × 0.6 × 0.4 mm
V = 1237.5 (5) Å^3

Data collection

Rigaku AFC5 diffractometer	θmax = 26.0°, θmin = 2.0°
θ–2θ scans	h = 0→17
5071 measured reflections	k = −17→17
4850 independent reflections	l = −9→9
3040 reflections with I > 2σ(I)	3 standard reflections every 100 reflections
Rint = 0.016	intensity decay: 4.4%

Refinement

Refinement on F^2	w = 1/[σ^2(Fo^2) + (0.051P)^2 + 0.1858P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.045	(Δ/σ)max = 0.001
wR(F^2) = 0.117	Δρmax = 0.21 e Å^−3
S = 1.02	Δρmin = −0.12 e Å^−3
4850 reflections	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
424 parameters	Extinction coefficient: 0.026 (2)
All H-atom parameters refined

Special details

Refinement. Refinement was based on F² against all reflections. The weighted R-factor (wR) and goodness of fit (S) were based on F², and conventional R-factor (R) was calculated on F, with F set to zero for negative F². The threshold expression of I > 2σ(I) was used only for calculating R-factor(gt).

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

	x	y	z	Uiso*/Ueq
O1	0.7149 (1)	0.2734 (1)	0.8165 (2)	0.0790 (5)
O2	0.5465 (1)	0.1503 (1)	0.7510 (2)	0.0644 (4)
O3	0.6783 (1)	0.2505 (1)	0.1407 (2)	0.0724 (5)
O4	0.8513 (1)	0.3609 (1)	0.2025 (2)	0.0660 (4)
O5	0.8233 (1)	−0.1624 (1)	0.4545 (2)	0.0537 (4)
O6	0.8579 (1)	−0.1450 (1)	0.7516 (2)	0.0636 (4)
O7	0.6549 (1)	−0.3208 (1)	0.4898 (2)	0.0684 (5)
O8	0.7092 (1)	−0.4316 (1)	0.3233 (2)	0.0714 (5)
N9	0.6003 (1)	−0.1378 (1)	0.9926 (2)	0.0488 (4)
N10	0.8992 (1)	−0.3563 (1)	0.1308 (2)	0.0498 (4)
C11	0.6366 (2)	0.2156 (2)	0.7091 (2)	0.0509 (5)
C12	0.6544 (2)	0.2258 (2)	0.5117 (3)	0.0550 (5)
C13	0.7388 (2)	0.2973 (2)	0.4453 (2)	0.0519 (5)
C14	0.7610 (2)	0.3063 (2)	0.2501 (2)	0.0478 (5)
C15	0.8812 (1)	−0.1167 (1)	0.6008 (3)	0.0430 (4)
C16	0.9843 (2)	−0.0206 (1)	0.5768 (3)	0.0435 (4)
C17	0.6443 (1)	−0.4130 (2)	0.4212 (3)	0.0476 (5)
C18	0.5417 (2)	−0.5048 (2)	0.4629 (3)	0.0479 (5)
C19	0.5884 (2)	−0.0611 (2)	0.8697 (3)	0.0562 (5)
C20	0.6635 (3)	−0.0396 (3)	0.7138 (4)	0.0822 (9)
C21	0.7063 (2)	−0.0938 (2)	1.1004 (3)	0.0659 (6)
C22	0.7241 (3)	0.0054 (3)	1.2208 (4)	0.0799 (8)
C23	0.5769 (3)	−0.2453 (2)	0.8914 (3)	0.0673 (6)
C24	0.5422 (4)	−0.3348 (3)	1.0123 (5)	0.098 (1)
C25	0.9282 (2)	−0.2414 (2)	0.0972 (4)	0.0572 (6)
C26	1.0368 (3)	−0.1878 (3)	0.0141 (5)	0.0865 (9)
C27	0.8772 (2)	−0.4305 (2)	−0.0402 (3)	0.0646 (6)
C28	0.7815 (3)	−0.4362 (3)	−0.1515 (5)	0.0878 (9)
C29	0.9795 (2)	−0.3709 (2)	0.2549 (4)	0.0685 (7)
C30	0.9897 (3)	−0.3115 (4)	0.4387 (5)	0.101 (1)
H3	0.699 (3)	0.260 (2)	0.001 (4)	0.1281 (1)*
H5	0.744 (3)	−0.242 (2)	0.473 (4)	0.1210 (1)*
H9	0.546 (2)	−0.149 (2)	1.071 (3)	0.05829 (8)*
H10	0.838 (2)	−0.376 (2)	0.186 (3)	0.05359 (7)*
H12	0.599 (2)	0.175 (2)	0.435 (3)	0.07964 (10)*
H13	0.794 (2)	0.349 (2)	0.528 (3)	0.06794 (8)*
H16	1.027 (2)	0.012 (2)	0.687 (3)	0.05385 (7)*
H18	0.540 (2)	−0.570 (2)	0.432 (3)	0.04613 (7)*
H19A	0.602 (2)	0.006 (2)	0.945 (3)	0.06567 (8)*
H19B	0.510 (2)	−0.094 (2)	0.824 (3)	0.07506 (9)*
H20A	0.651 (2)	−0.107 (2)	0.644 (4)	0.0917 (1)*
H20B	0.646 (2)	0.010 (3)	0.642 (4)	0.1146 (1)*
H20C	0.744 (3)	−0.009 (3)	0.769 (5)	0.1402 (2)*
H21A	0.763 (2)	−0.081 (2)	1.011 (4)	0.0883 (1)*
H21B	0.701 (2)	−0.152 (2)	1.171 (3)	0.07443 (9)*
H22A	0.665 (2)	−0.001 (2)	1.295 (4)	0.0863 (1)*
H22B	0.789 (3)	0.023 (2)	1.302 (4)	0.1108 (1)*
H22C	0.734 (2)	0.066 (2)	1.152 (4)	0.1043 (1)*
H23A	0.646 (2)	−0.237 (2)	0.825 (3)	0.08292 (10)*
H23B	0.516 (2)	−0.257 (2)	0.799 (4)	0.0882 (1)*
H24A	0.529 (2)	−0.399 (3)	0.943 (4)	0.1083 (1)*
H24B	0.608 (3)	−0.317 (3)	1.098 (5)	0.1450 (2)*
H24C	0.485 (3)	−0.338 (3)	1.079 (5)	0.1221 (2)*
H25A	0.926 (2)	−0.207 (2)	0.206 (3)	0.07549 (9)*
H25B	0.873 (2)	−0.244 (2)	0.017 (3)	0.06133 (8)*
H26A	1.037 (3)	−0.228 (3)	−0.104 (5)	0.1308 (2)*
H26B	1.098 (3)	−0.184 (2)	0.097 (4)	0.1148 (1)*
H26C	1.049 (2)	−0.117 (3)	0.005 (4)	0.1065 (1)*
H27A	0.947 (2)	−0.406 (2)	−0.096 (3)	0.06638 (8)*
H27B	0.867 (2)	−0.500 (3)	0.000 (4)	0.1053 (1)*
H28A	0.768 (3)	−0.493 (3)	−0.243 (5)	0.1163 (1)*
H28B	0.720 (3)	−0.452 (3)	−0.083 (5)	0.1206 (2)*
H28C	0.801 (3)	−0.363 (3)	−0.195 (5)	0.1533 (2)*
H29A	1.047 (2)	−0.348 (2)	0.193 (3)	0.07096 (8)*
H29B	0.951 (2)	−0.450 (3)	0.267 (4)	0.1068 (1)*
H30A	0.915 (3)	−0.335 (3)	0.483 (5)	0.1386 (2)*
H30B	1.033 (4)	−0.233 (4)	0.422 (6)	0.1818 (3)*
H30C	1.029 (3)	−0.342 (3)	0.523 (5)	0.1442 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.071 (1)	0.110 (1)	0.0270 (7)	0.0062 (9)	0.0055 (7)	0.0147 (8)
O2	0.0617 (9)	0.078 (1)	0.0426 (8)	0.0162 (8)	0.0213 (7)	0.0122 (7)
O3	0.0564 (9)	0.108 (1)	0.0281 (7)	0.0059 (9)	0.0053 (7)	0.0162 (8)
O4	0.0544 (9)	0.086 (1)	0.0457 (8)	0.0133 (8)	0.0144 (7)	0.0195 (7)
O5	0.0418 (7)	0.0451 (8)	0.0524 (8)	−0.0044 (6)	0.0092 (6)	0.0034 (6)
O6	0.0549 (9)	0.0671 (9)	0.0556 (9)	0.0083 (7)	0.0135 (7)	0.0221 (7)
O7	0.0457 (8)	0.0460 (9)	0.085 (1)	−0.0078 (7)	0.0254 (7)	−0.0082 (8)
O8	0.0483 (8)	0.0648 (9)	0.085 (1)	0.0071 (7)	0.0347 (8)	0.0044 (8)
N9	0.0532 (10)	0.057 (1)	0.0396 (9)	0.0253 (8)	0.0145 (8)	0.0080 (7)
N10	0.0397 (9)	0.057 (1)	0.0530 (10)	0.0174 (8)	0.0161 (8)	0.0159 (8)
C11	0.059 (1)	0.063 (1)	0.0292 (9)	0.022 (1)	0.0105 (9)	0.0098 (9)
C12	0.052 (1)	0.074 (1)	0.0286 (10)	0.014 (1)	0.0036 (9)	0.0077 (10)
C13	0.049 (1)	0.069 (1)	0.0297 (9)	0.016 (1)	0.0037 (9)	0.0062 (9)
C14	0.051 (1)	0.060 (1)	0.0322 (9)	0.0205 (10)	0.0087 (9)	0.0111 (9)
C15	0.0367 (10)	0.0372 (10)	0.051 (1)	0.0097 (8)	0.0133 (9)	0.0086 (9)
C16	0.0369 (10)	0.0368 (10)	0.048 (1)	0.0061 (8)	0.0066 (8)	0.0019 (8)
C17	0.0330 (10)	0.050 (1)	0.044 (1)	0.0016 (8)	0.0087 (8)	0.0040 (9)
C18	0.038 (1)	0.039 (1)	0.050 (1)	0.0004 (9)	0.0098 (8)	−0.0029 (9)
C19	0.063 (1)	0.069 (1)	0.046 (1)	0.034 (1)	0.010 (1)	0.011 (1)
C20	0.112 (3)	0.097 (2)	0.064 (2)	0.065 (2)	0.041 (2)	0.036 (2)
C21	0.060 (1)	0.091 (2)	0.052 (1)	0.036 (1)	0.003 (1)	0.010 (1)
C22	0.065 (2)	0.097 (2)	0.061 (2)	0.019 (2)	0.001 (1)	−0.007 (2)
C23	0.087 (2)	0.063 (1)	0.058 (1)	0.037 (1)	0.013 (1)	0.006 (1)
C24	0.138 (3)	0.067 (2)	0.093 (2)	0.045 (2)	0.025 (3)	0.017 (2)
C25	0.062 (1)	0.053 (1)	0.056 (1)	0.023 (1)	0.016 (1)	0.010 (1)
C26	0.069 (2)	0.066 (2)	0.107 (3)	0.007 (1)	0.028 (2)	0.028 (2)
C27	0.069 (2)	0.059 (1)	0.065 (1)	0.025 (1)	0.019 (1)	0.006 (1)
C28	0.090 (2)	0.092 (2)	0.072 (2)	0.029 (2)	−0.007 (2)	−0.008 (2)
C29	0.053 (1)	0.082 (2)	0.078 (2)	0.033 (1)	0.009 (1)	0.020 (1)
C30	0.092 (2)	0.155 (4)	0.074 (2)	0.070 (3)	−0.009 (2)	0.003 (2)

Geometric parameters (Å, º)

O1—C11	1.255 (2)	C20—H20A	0.97 (3)
O2—C11	1.235 (2)	C20—H20B	0.99 (4)
O3—C14	1.293 (2)	C20—H20C	1.05 (4)
O3—H3	1.08 (3)	C21—C22	1.488 (4)
O4—C14	1.208 (2)	C21—H21A	0.98 (3)
O5—C15	1.288 (2)	C21—H21B	0.97 (3)
O5—H5	1.19 (3)	C22—H22A	0.95 (3)
O6—C15	1.217 (2)	C22—H22B	0.99 (3)
O7—C17	1.268 (3)	C22—H22C	0.97 (3)
O7—H5	1.26 (3)	C23—C24	1.500 (5)
O8—C17	1.226 (3)	C23—H23A	1.02 (3)
N9—C19	1.503 (4)	C23—H23B	1.02 (3)
N9—C21	1.497 (3)	C24—H24A	0.93 (3)
N9—C23	1.500 (3)	C24—H24B	1.01 (4)
N9—H9	0.90 (2)	C24—H24C	0.90 (4)
N10—C25	1.500 (3)	C25—C26	1.502 (4)
N10—C27	1.503 (3)	C25—H25A	0.91 (3)
N10—C29	1.501 (4)	C25—H25B	0.94 (3)
N10—H10	0.87 (2)	C26—H26A	0.99 (4)
C11—C12	1.497 (3)	C26—H26B	1.01 (4)
C12—C13	1.290 (3)	C26—H26C	0.92 (4)
C12—H12	0.93 (2)	C27—C28	1.496 (5)
C13—C14	1.487 (3)	C27—H27A	0.97 (2)
C13—H13	0.96 (2)	C27—H27B	0.98 (4)
C15—C16	1.493 (2)	C28—H28A	0.95 (3)
C16—C16^i	1.312 (4)	C28—H28B	0.93 (4)
C16—H16	0.97 (2)	C28—H28C	1.01 (5)
C17—C18	1.493 (2)	C29—C30	1.502 (5)
C18—C18^ii	1.296 (4)	C29—H29A	0.96 (2)
C18—H18	0.89 (2)	C29—H29B	1.01 (3)
C19—C20	1.506 (4)	C30—H30A	0.99 (4)
C19—H19A	0.97 (2)	C30—H30B	1.00 (5)
C19—H19B	1.00 (3)	C30—H30C	1.03 (5)
C14—O3—H3	111 (1)	H21A—C21—H21B	111 (2)
C15—O5—H5	114 (1)	C21—C22—H22A	113 (1)
C17—O7—H5	118 (1)	C21—C22—H22B	109 (2)
C19—N9—C21	114.1 (2)	C21—C22—H22C	111 (1)
C19—N9—C23	111.1 (2)	H22A—C22—H22B	107 (2)
C19—N9—H9	104 (1)	H22A—C22—H22C	104 (2)
C21—N9—C23	112.5 (2)	H22B—C22—H22C	109 (2)
C21—N9—H9	107 (1)	N9—C23—C24	112.7 (2)
C23—N9—H9	105 (1)	N9—C23—H23A	106 (1)
C25—N10—C27	113.1 (2)	N9—C23—H23B	105 (1)
C25—N10—C29	113.9 (2)	C24—C23—H23A	112 (1)
C25—N10—H10	105 (1)	C24—C23—H23B	110 (1)
C27—N10—C29	110.9 (2)	H23A—C23—H23B	108 (2)
C27—N10—H10	106 (1)	C23—C24—H24A	108 (2)
C29—N10—H10	106 (1)	C23—C24—H24B	104 (2)
O1—C11—O2	126.1 (2)	C23—C24—H24C	112 (2)
O1—C11—C12	117.0 (2)	H24A—C24—H24B	109 (3)
O2—C11—C12	116.9 (2)	H24A—C24—H24C	112 (2)
C11—C12—C13	124.9 (2)	H24B—C24—H24C	108 (3)
C11—C12—H12	114 (1)	N10—C25—C26	114.3 (3)
C13—C12—H12	120 (1)	N10—C25—H25A	105 (1)
C12—C13—C14	126.1 (2)	N10—C25—H25B	104 (1)
C12—C13—H13	118 (1)	C26—C25—H25A	111 (1)
C14—C13—H13	115 (1)	C26—C25—H25B	109 (1)
O3—C14—O4	124.3 (2)	H25A—C25—H25B	111 (2)
O3—C14—C13	115.0 (2)	C25—C26—H26A	109 (1)
O4—C14—C13	120.7 (2)	C25—C26—H26B	110 (1)
O5—C15—O6	125.6 (1)	C25—C26—H26C	107 (2)
O5—C15—C16	115.1 (2)	H26A—C26—H26B	110 (3)
O6—C15—C16	119.4 (2)	H26A—C26—H26C	113 (2)
C15—C16—C16^i	125.1 (2)	H26B—C26—H26C	104 (2)
C15—C16—H16	113 (1)	N10—C27—C28	113.2 (3)
C16^i—C16—H16	120 (1)	N10—C27—H27A	103 (1)
O7—C17—O8	125.7 (2)	N10—C27—H27B	104 (1)
O7—C17—C18	115.6 (2)	C28—C27—H27A	117 (1)
O8—C17—C18	118.7 (2)	C28—C27—H27B	112 (1)
C17—C18—C18^ii	124.9 (3)	H27A—C27—H27B	103 (2)
C17—C18—H18	114 (1)	C27—C28—H28A	105 (2)
C18^ii—C18—H18	120 (1)	C27—C28—H28B	110 (2)
N9—C19—C20	114.2 (3)	C27—C28—H28C	107 (2)
N9—C19—H19A	106 (1)	H28A—C28—H28B	108 (2)
N9—C19—H19B	106 (1)	H28A—C28—H28C	115 (3)
C20—C19—H19A	110 (1)	H28B—C28—H28C	108 (3)
C20—C19—H19B	110 (1)	N10—C29—C30	112.4 (3)
H19A—C19—H19B	108 (2)	N10—C29—H29A	105 (1)
C19—C20—H20A	109 (1)	N10—C29—H29B	106 (1)
C19—C20—H20B	106 (1)	C30—C29—H29A	113 (1)
C19—C20—H20C	107 (2)	C30—C29—H29B	109 (1)
H20A—C20—H20B	112 (2)	H29A—C29—H29B	110 (2)
H20A—C20—H20C	106 (2)	C29—C30—H30A	106 (1)
H20B—C20—H20C	115 (2)	C29—C30—H30B	105 (2)
N9—C21—C22	113.4 (3)	C29—C30—H30C	106 (2)
N9—C21—H21A	105 (1)	H30A—C30—H30B	119 (4)
N9—C21—H21B	103 (1)	H30A—C30—H30C	104 (3)
C22—C21—H21A	111 (1)	H30B—C30—H30C	113 (3)
C22—C21—H21B	110 (1)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1^iii	1.08 (3)	1.40 (3)	2.481 (2)	174 (3)
O5—H5···O7	1.19 (3)	1.26 (3)	2.445 (2)	175 (4)
N9—H9···O2^iv	0.90 (2)	1.81 (2)	2.708 (2)	170 (2)
N10—H10···O8	0.87 (2)	1.92 (2)	2.781 (2)	173 (2)

Symmetry codes: (iii) x, y, z−1; (iv) −x+1, −y, −z+2.