Crystal structure of 1H,1'H-[2,2'-biimid-azol]-3-ium hydrogen tartrate hemi-hydrate.

In the crystal of the title hydrated salt, C6H7N4 (+)·C4H5O6 (-)·0.5H2O, the bi-imidazole monocation, 1H,1'H-[2,2'-biimidazol]-3-ium, is hydrogen bonded, via N-H⋯O, O-H⋯O and O-H⋯N hydrogen bonds, to the hydrogen tartrate anion and the water mol-ecule, which is located on a twofold rotation axis, forming sheets parallel to (001). The sheets are linked via C-H⋯O hydrogen bonds, forming a three-dimensional structure. There are also C=O⋯π inter-actions present [O⋯π distances are 3.00 (9) and 3.21 (7) Å], involving the carbonyl O atoms and the imidazolium ring, which may help to consolidate the structure. In the cation, the dihedral angle between the rings is 11.6 (2)°.

Related literature

For background to the use of 2,2′-bi­imidazoles in crystal engineering, see: Shankar et al. (2013 ▶); Gulbransen & Fitchett (2012 ▶); Tadokoro & Nakasuji (2000 ▶). For similar structures, see: Liu & Zhu (2010 ▶); Gao et al. (2009 ▶); Li & Yang (2006 ▶); Mori & Miyoshi (2004 ▶).

Experimental

Crystal data

C4H5O6 −·C6H7N4 +·0.5H2O

M = 293.25

Monoclinic,

a = 19.3211 (13) Å

b = 4.8198 (2) Å

c = 16.1795 (10) Å

β = 122.694 (7)°

V = 1267.99 (13) Å3

Z = 4

Mo Kα radiation

μ = 0.13 mm−1

T = 296 K

0.35 × 0.30 × 0.23 mm

Data collection

Bruker SMART diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T min = 0.956, T max = 0.971

4238 measured reflections

2292 independent reflections

2100 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.099

S = 1.11

2292 reflections

202 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.16 e Å−3

Δρmin = −0.27 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); 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: pubCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S160053681402371X/su5001sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681402371X/su5001Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S160053681402371X/su5001Isup3.cml

Click here for additional data file.

x y z x y z x y z . DOI: 10.1107/S160053681402371X/su5001fig1.tif

Mol­ecular structure and atom labelling of the title compound, with displacement ellipsoids drawn at the 30% probability level. Dashed line indicates hydrogen bonds [see Table 1 for details; symmetry codes: (i) x, y + 1, z; (ii) x + , y + , z + 2; (iii) x + , y + , z + 2].

Click here for additional data file.

x y z x y z x y z x y - z x y z . DOI: 10.1107/S160053681402371X/su5001fig2.tif

Partial crystal packing of the title compound, with the hydrogen bonds (dashed lines) and C=O⋯π inter­actions (dashed solid lines) between neighbouring tapes [symmetry codes: (i) x + , y + , z + 2; (ii) − x, y, − z; (iii) x, y + 1, z; (iv) x + , y - 3/2, z + 2; (v) − x − 1, y, − z].

CCDC reference: 1031345

Additional supporting information: crystallographic information; 3D view; checkCIF report

C4H5O6−·C6H7N4+·0.5H2O	F(000) = 612
Mr = 293.25	Dx = 1.536 Mg m−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 2195 reflections
a = 19.3211 (13) Å	θ = 3.5–25.0°
b = 4.8198 (2) Å	µ = 0.13 mm−1
c = 16.1795 (10) Å	T = 296 K
β = 122.694 (7)°	Plate, colourless
V = 1267.99 (13) Å3	0.35 × 0.30 × 0.23 mm
Z = 4

Bruker SMART diffractometer	2292 independent reflections
Radiation source: fine-focus sealed tube	2100 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
Detector resolution: 16.0733 pixels mm-1	θmax = 25.5°, θmin = 3.6°
phi and ω scans	h = −23→10
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	k = −5→5
Tmin = 0.956, Tmax = 0.971	l = −18→19
4238 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ2(Fo2) + (0.0364P)2 + 0.5619P] where P = (Fo2 + 2Fc2)/3
2292 reflections	(Δ/σ)max < 0.001
202 parameters	Δρmax = 0.16 e Å−3
1 restraint	Δρmin = −0.27 e Å−3

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.The line _refine_ls_abs_structure_Flack -1.5 (15) has been removed. According to the comment in an absolute configuration has been assigned, obtained using x by least-squares refinement. There is too high standard uncertainty on x and no information available that the assigned value is confirmed by the diffraction measurements.

	x	y	z	Uiso*/Ueq
C1	0.12363 (19)	0.3256 (7)	0.54798 (19)	0.0501 (8)
H1	0.0811	0.4221	0.4950	0.060*
C2	0.17427 (17)	0.1439 (8)	0.54276 (19)	0.0465 (8)
H2	0.1729	0.0925	0.4865	0.056*
C3	0.20830 (14)	0.1770 (6)	0.69462 (16)	0.0287 (6)
C4	0.25343 (14)	0.1445 (5)	0.80032 (16)	0.0266 (5)
C5	0.33858 (17)	−0.0022 (6)	0.95007 (19)	0.0385 (7)
H5	0.3788	−0.1057	1.0029	0.046*
C6	0.29783 (17)	0.2162 (6)	0.95549 (18)	0.0380 (7)
H6	0.3044	0.2923	1.0121	0.046*
N1	0.14434 (14)	0.3465 (5)	0.64335 (15)	0.0400 (6)
N2	0.22801 (13)	0.0497 (5)	0.63601 (15)	0.0357 (5)
N3	0.24455 (13)	0.3045 (5)	0.86056 (14)	0.0307 (5)
N4	0.31045 (13)	−0.0455 (5)	0.85300 (15)	0.0307 (5)
H2A	0.2689 (17)	−0.079 (6)	0.6544 (19)	0.037*
H3A	0.2032 (17)	0.440 (6)	0.8388 (18)	0.037*
H4A	0.3337 (16)	−0.172 (7)	0.8333 (19)	0.037*
C7	0.38284 (14)	0.5315 (5)	0.74083 (18)	0.0295 (6)
C8	0.44290 (15)	0.3252 (6)	0.74053 (18)	0.0308 (6)
C9	0.51381 (14)	0.4868 (5)	0.74572 (17)	0.0288 (6)
H9	0.4916	0.6076	0.6881	0.035*
C10	0.57380 (15)	0.2829 (6)	0.74598 (17)	0.0299 (6)
O1	0.37823 (11)	0.5416 (4)	0.81509 (13)	0.0379 (5)
O2	0.34295 (11)	0.6789 (4)	0.66602 (12)	0.0436 (5)
O3	0.47460 (11)	0.1317 (4)	0.81901 (13)	0.0382 (5)
H3	0.4744	0.1836	0.8679	0.046*
O4	0.55700 (11)	0.6495 (4)	0.83171 (14)	0.0402 (5)
O5	0.64334 (10)	0.2498 (4)	0.81780 (12)	0.0353 (5)
O6	0.54328 (11)	0.1477 (5)	0.66429 (13)	0.0475 (5)
H6A	0.5803	0.0673	0.6635	0.057*
H4	0.5313 (19)	0.807 (8)	0.832 (2)	0.057*
H8	0.4108 (19)	0.231 (7)	0.676 (2)	0.057*
O7	0.5000	0.3371 (9)	1.0000	0.0714 (10)
H7A	0.4667	0.4934	0.9729	0.086*

	U11	U22	U33	U12	U13	U23
C1	0.0480 (17)	0.063 (2)	0.0286 (13)	0.0215 (17)	0.0139 (13)	0.0062 (15)
C2	0.0506 (17)	0.0589 (19)	0.0278 (13)	0.0134 (17)	0.0196 (12)	0.0000 (14)
C3	0.0276 (12)	0.0321 (13)	0.0280 (12)	0.0028 (12)	0.0161 (10)	0.0002 (12)
C4	0.0262 (12)	0.0257 (12)	0.0282 (11)	0.0020 (11)	0.0149 (10)	0.0017 (11)
C5	0.0380 (14)	0.0426 (16)	0.0297 (13)	0.0072 (13)	0.0149 (11)	0.0046 (12)
C6	0.0405 (15)	0.0437 (17)	0.0273 (12)	0.0023 (13)	0.0168 (12)	−0.0015 (12)
N1	0.0373 (12)	0.0501 (14)	0.0286 (11)	0.0179 (12)	0.0152 (10)	0.0038 (11)
N2	0.0348 (12)	0.0400 (13)	0.0305 (11)	0.0110 (11)	0.0165 (10)	−0.0011 (10)
N3	0.0327 (11)	0.0322 (12)	0.0293 (11)	0.0050 (10)	0.0180 (9)	0.0005 (9)
N4	0.0318 (11)	0.0310 (12)	0.0295 (11)	0.0067 (10)	0.0167 (9)	0.0033 (9)
C7	0.0245 (12)	0.0283 (13)	0.0354 (13)	−0.0009 (11)	0.0160 (10)	−0.0059 (11)
C8	0.0300 (13)	0.0297 (14)	0.0312 (12)	0.0041 (11)	0.0155 (11)	−0.0018 (11)
C9	0.0299 (12)	0.0254 (13)	0.0286 (12)	0.0069 (11)	0.0141 (10)	0.0028 (11)
C10	0.0322 (13)	0.0296 (13)	0.0318 (13)	−0.0007 (11)	0.0198 (12)	−0.0003 (11)
O1	0.0442 (11)	0.0357 (10)	0.0423 (10)	0.0090 (9)	0.0290 (9)	0.0043 (8)
O2	0.0412 (11)	0.0545 (13)	0.0332 (9)	0.0233 (11)	0.0190 (8)	0.0074 (10)
O3	0.0501 (11)	0.0284 (10)	0.0445 (10)	0.0103 (9)	0.0311 (9)	0.0066 (9)
O4	0.0355 (10)	0.0283 (9)	0.0462 (10)	0.0036 (9)	0.0151 (8)	−0.0117 (9)
O5	0.0268 (9)	0.0365 (10)	0.0347 (9)	0.0052 (8)	0.0114 (8)	−0.0045 (8)
O6	0.0349 (10)	0.0641 (14)	0.0352 (9)	0.0139 (10)	0.0135 (8)	−0.0140 (10)
O7	0.064 (2)	0.078 (3)	0.061 (2)	0.000	0.0266 (18)	0.000

C1—C2	1.350 (4)	N4—H4A	0.91 (3)
C1—N1	1.373 (3)	C7—O2	1.247 (3)
C1—H1	0.9300	C7—O1	1.253 (3)
C2—N2	1.367 (3)	C7—C8	1.530 (4)
C2—H2	0.9300	C8—O3	1.421 (3)
C3—N1	1.333 (3)	C8—C9	1.538 (4)
C3—N2	1.346 (3)	C8—H8	0.99 (3)
C3—C4	1.449 (3)	C9—O4	1.412 (3)
C4—N3	1.325 (3)	C9—C10	1.518 (3)
C4—N4	1.328 (3)	C9—H9	0.9800
C5—C6	1.346 (4)	C10—O5	1.222 (3)
C5—N4	1.372 (3)	C10—O6	1.295 (3)
C5—H5	0.9300	O3—H3	0.8309
C6—N3	1.375 (3)	O4—H4	0.91 (4)
C6—H6	0.9300	O6—H6A	0.8200
N2—H2A	0.92 (3)	O7—H7A	0.9324
N3—H3A	0.94 (3)
C2—C1—N1	109.7 (2)	C4—N4—C5	107.9 (2)
C2—C1—H1	125.2	C4—N4—H4A	129.2 (17)
N1—C1—H1	125.2	C5—N4—H4A	122.4 (17)
C1—C2—N2	106.9 (2)	O2—C7—O1	125.6 (2)
C1—C2—H2	126.6	O2—C7—C8	116.0 (2)
N2—C2—H2	126.6	O1—C7—C8	118.4 (2)
N1—C3—N2	111.2 (2)	O3—C8—C7	112.7 (2)
N1—C3—C4	124.5 (2)	O3—C8—C9	110.02 (19)
N2—C3—C4	124.3 (2)	C7—C8—C9	109.0 (2)
N3—C4—N4	108.8 (2)	O3—C8—H8	111 (2)
N3—C4—C3	124.8 (2)	C7—C8—H8	105.0 (19)
N4—C4—C3	126.4 (2)	C9—C8—H8	108.7 (18)
C6—C5—N4	108.0 (2)	O4—C9—C10	108.24 (19)
C6—C5—H5	126.0	O4—C9—C8	111.7 (2)
N4—C5—H5	126.0	C10—C9—C8	109.19 (19)
C5—C6—N3	106.3 (2)	O4—C9—H9	109.2
C5—C6—H6	126.8	C10—C9—H9	109.2
N3—C6—H6	126.8	C8—C9—H9	109.2
C3—N1—C1	105.3 (2)	O5—C10—O6	124.4 (2)
C3—N2—C2	106.9 (2)	O5—C10—C9	122.2 (2)
C3—N2—H2A	126.9 (17)	O6—C10—C9	113.4 (2)
C2—N2—H2A	126.1 (17)	C8—O3—H3	115.5
C4—N3—C6	109.0 (2)	C9—O4—H4	116 (2)
C4—N3—H3A	123.3 (16)	C10—O6—H6A	109.5
C6—N3—H3A	127.3 (16)
N1—C1—C2—N2	−0.3 (4)	N3—C4—N4—C5	−0.2 (3)
N1—C3—C4—N3	−9.7 (4)	C3—C4—N4—C5	179.2 (3)
N2—C3—C4—N3	166.9 (3)	C6—C5—N4—C4	0.1 (3)
N1—C3—C4—N4	170.9 (3)	O2—C7—C8—O3	−169.2 (2)
N2—C3—C4—N4	−12.4 (4)	O1—C7—C8—O3	11.6 (3)
N4—C5—C6—N3	0.1 (3)	O2—C7—C8—C9	68.4 (3)
N2—C3—N1—C1	−0.6 (3)	O1—C7—C8—C9	−110.8 (3)
C4—C3—N1—C1	176.5 (3)	O3—C8—C9—O4	−64.0 (2)
C2—C1—N1—C3	0.5 (4)	C7—C8—C9—O4	60.0 (2)
N1—C3—N2—C2	0.4 (3)	O3—C8—C9—C10	55.7 (3)
C4—C3—N2—C2	−176.7 (3)	C7—C8—C9—C10	179.7 (2)
C1—C2—N2—C3	0.0 (4)	O4—C9—C10—O5	9.8 (3)
N4—C4—N3—C6	0.3 (3)	C8—C9—C10—O5	−112.0 (3)
C3—C4—N3—C6	−179.1 (3)	O4—C9—C10—O6	−171.4 (2)
C5—C6—N3—C4	−0.3 (3)	C8—C9—C10—O6	66.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2i	0.92 (3)	1.78 (3)	2.683 (3)	169 (3)
N3—H3A···O5ii	0.94 (3)	1.81 (3)	2.729 (3)	167 (3)
N4—H4A···O1i	0.91 (3)	1.73 (3)	2.630 (3)	167 (3)
O3—H3···O7	0.83	2.05	2.871 (2)	168
O4—H4···O3iii	0.91 (4)	1.86 (4)	2.761 (3)	175 (3)
O6—H6A···N1iv	0.82	1.79	2.598 (3)	168
O7—H7A···O1	0.93	2.19	2.802 (2)	123
C2—H2···O2v	0.93	2.35	3.215 (3)	154
C5—H5···O4vi	0.93	2.55	3.415 (3)	155
C6—H6···O5vii	0.93	2.37	3.205 (3)	149

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N2H2AO2i	0.92(3)	1.78(3)	2.683(3)	169(3)
N3H3AO5ii	0.94(3)	1.81(3)	2.729(3)	167(3)
N4H4AO1i	0.91(3)	1.73(3)	2.630(3)	167(3)
O3H3O7	0.83	2.05	2.871(2)	168
O4H4O3iii	0.91(4)	1.86(4)	2.761(3)	175(3)
O6H6AN1iv	0.82	1.79	2.598(3)	168
O7H7AO1	0.93	2.19	2.802(2)	123
C2H2O2v	0.93	2.35	3.215(3)	154
C5H5O4vi	0.93	2.55	3.415(3)	155
C6H6O5vii	0.93	2.37	3.205(3)	149

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