1,4-Diazo-niabicyclo-[2.2.2]octane bis-(2-chloro-benzoate).

The title compound, C(6)H(14)N(2) (2+)·2C(7)H(4)ClO(2) (-), contains trimeric units linked by N-H⋯O hydrogen bonds. The carboxyl-ate groups of the 2-chloro-benzoate anions form dihedral angles of 66.1 (1) and 76.1 (1)° with the respective chloro-benzene rings to which they are bound. The hydrogen-bonded trimers are arranged in layers in the (200) planes and the chloro-benzoate anions form edge-to-face inter-actions between layers, with dihedral angles of 61.9 (1) and 49.8 (1)° and centroid-centroid distances of 4.85 (1) and 4.65 (1) Å, respectively, for two crystallographically distinct inter-actions.

Related literature

For other co-crystals of 1,4-diazo­niabicyclo­[2.2.2]octane and carboxylic acids, see: Meehan et al. (1997 ▶); Burchell et al. (2000 ▶); Burchell, Glidewell et al. (2001 ▶); Burchell, Ferguson et al. (2001 ▶). For the crystal structure of 2-chloro­benzoic acid, see: Ferguson & Sim (1961 ▶).

Experimental

Crystal data

C6H14N2 2+·2C7H4ClO2 −

M = 425.30

Orthorhombic,

a = 19.7694 (12) Å

b = 11.3986 (6) Å

c = 8.9751 (5) Å

V = 2022.5 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.35 mm−1

T = 298 (2) K

0.30 × 0.20 × 0.10 mm

Data collection

Bruker–Nonius X8 APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.844, T max = 0.966

21779 measured reflections

3538 independent reflections

3251 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.090

S = 1.06

3538 reflections

253 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.26 e Å−3

Δρmin = −0.19 e Å−3

Absolute structure: Flack (1983 ▶), 1629 Friedel pairs

Flack parameter: −0.02 (5)

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808020096/bx2155sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808020096/bx2155Isup2.hkl

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

C6H14N22+·2C7H4ClO2–	F000 = 888
Mr = 425.30	Dx = 1.397 Mg m−3
Orthorhombic, Pca21	Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 9140 reflections
a = 19.7694 (12) Å	θ = 3.1–24.3º
b = 11.3986 (6) Å	µ = 0.35 mm−1
c = 8.9751 (5) Å	T = 298 (2) K
V = 2022.5 (2) Å3	Block, colourless
Z = 4	0.30 × 0.20 × 0.10 mm

Bruker–Nonius X8 APEXII CCD diffractometer	3538 independent reflections
Radiation source: fine-focus sealed tube	3251 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.023
T = 298(2) K	θmax = 25.0º
Thin–slice ω and φ scans	θmin = 3.6º
Absorption correction: multi-scan(SADABS; Sheldrick, 2003)	h = −23→23
Tmin = 0.844, Tmax = 0.966	k = −13→12
21779 measured reflections	l = −10→10

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.033	w = 1/[σ2(Fo2) + (0.0543P)2 + 0.354P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.090	(Δ/σ)max = 0.001
S = 1.07	Δρmax = 0.26 e Å−3
3538 reflections	Δρmin = −0.19 e Å−3
253 parameters	Extinction correction: none
1 restraint	Absolute structure: Flack (1983), 1629 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.02 (5)
Secondary atom site location: difference Fourier map

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
Cl1	0.58385 (3)	1.34004 (5)	0.57363 (7)	0.05244 (17)
Cl2	0.41713 (4)	0.14065 (6)	0.64801 (8)	0.0658 (2)
O1	0.58704 (9)	1.03874 (14)	0.7359 (2)	0.0556 (5)
O2	0.61776 (12)	1.05458 (17)	0.5009 (2)	0.0716 (6)
O3	0.43357 (9)	0.45727 (15)	0.4822 (2)	0.0542 (4)
O4	0.40470 (10)	0.42055 (18)	0.7161 (2)	0.0653 (5)
N1	0.53241 (8)	0.84726 (14)	0.6495 (2)	0.0351 (4)
H1A	0.5474	0.9192	0.6783	0.042*
N2	0.49115 (9)	0.64905 (14)	0.5697 (2)	0.0383 (4)
H2A	0.4760	0.5771	0.5410	0.046*
C1	0.67102 (10)	1.17744 (18)	0.6779 (2)	0.0357 (4)
C2	0.66021 (10)	1.29512 (17)	0.6508 (2)	0.0353 (4)
C3	0.70790 (11)	1.3795 (2)	0.6867 (3)	0.0459 (5)
H3A	0.6996	1.4582	0.6666	0.055*
C4	0.76781 (12)	1.3457 (2)	0.7524 (3)	0.0574 (7)
H4A	0.8003	1.4019	0.7756	0.069*
C5	0.77993 (13)	1.2290 (3)	0.7838 (3)	0.0590 (7)
H5A	0.8200	1.2061	0.8299	0.071*
C6	0.73135 (12)	1.1464 (2)	0.7456 (3)	0.0503 (6)
H6A	0.7396	1.0677	0.7662	0.060*
C7	0.62150 (12)	1.08377 (18)	0.6306 (3)	0.0402 (5)
C8	0.34750 (10)	0.31988 (18)	0.5241 (2)	0.0349 (4)
C9	0.34941 (10)	0.20060 (18)	0.5500 (2)	0.0389 (5)
C10	0.30020 (12)	0.1256 (2)	0.4960 (3)	0.0506 (6)
H10A	0.3033	0.0453	0.5132	0.061*
C11	0.24651 (13)	0.1707 (2)	0.4167 (3)	0.0581 (7)
H11A	0.2130	0.1209	0.3808	0.070*
C12	0.24255 (13)	0.2890 (3)	0.3909 (3)	0.0582 (6)
H12A	0.2061	0.3197	0.3381	0.070*
C13	0.29285 (12)	0.3629 (2)	0.4434 (3)	0.0480 (6)
H13A	0.2900	0.4429	0.4243	0.058*
C14	0.39949 (10)	0.40479 (18)	0.5813 (3)	0.0390 (5)
C15	0.49080 (17)	0.8594 (2)	0.5144 (3)	0.0643 (7)
H15A	0.5158	0.9018	0.4387	0.077*
H15B	0.4501	0.9033	0.5372	0.077*
C16	0.47206 (16)	0.7375 (2)	0.4566 (3)	0.0635 (8)
H16A	0.4238	0.7335	0.4375	0.076*
H16B	0.4957	0.7219	0.3640	0.076*
C17	0.49289 (16)	0.7947 (2)	0.7703 (3)	0.0612 (7)
H17A	0.4571	0.8479	0.8003	0.073*
H17B	0.5218	0.7807	0.8557	0.073*
C18	0.46232 (14)	0.6791 (2)	0.7171 (3)	0.0584 (7)
H18A	0.4724	0.6173	0.7881	0.070*
H18B	0.4136	0.6865	0.7095	0.070*
C19	0.59035 (12)	0.7722 (2)	0.6143 (4)	0.0605 (7)
H19A	0.6217	0.7717	0.6974	0.073*
H19B	0.6139	0.8028	0.5278	0.073*
C20	0.56618 (12)	0.6470 (2)	0.5826 (4)	0.0594 (7)
H20A	0.5861	0.6185	0.4906	0.071*
H20B	0.5798	0.5951	0.6628	0.071*

	U11	U22	U33	U12	U13	U23
Cl1	0.0553 (3)	0.0404 (3)	0.0615 (4)	0.0067 (2)	−0.0201 (3)	−0.0033 (3)
Cl2	0.0831 (5)	0.0419 (3)	0.0725 (5)	0.0129 (3)	−0.0271 (4)	−0.0006 (3)
O1	0.0751 (11)	0.0435 (10)	0.0480 (10)	−0.0240 (8)	0.0158 (8)	−0.0078 (8)
O2	0.1056 (15)	0.0635 (12)	0.0456 (10)	−0.0416 (11)	0.0024 (10)	−0.0066 (9)
O3	0.0660 (10)	0.0450 (10)	0.0518 (10)	−0.0245 (8)	0.0108 (8)	−0.0083 (8)
O4	0.0916 (14)	0.0583 (12)	0.0459 (10)	−0.0319 (10)	−0.0071 (10)	−0.0053 (9)
N1	0.0452 (10)	0.0237 (9)	0.0365 (9)	−0.0071 (6)	0.0028 (8)	−0.0031 (8)
N2	0.0507 (10)	0.0275 (9)	0.0367 (9)	−0.0115 (7)	0.0034 (9)	−0.0037 (8)
C1	0.0422 (11)	0.0312 (10)	0.0339 (10)	−0.0038 (8)	0.0013 (8)	0.0011 (9)
C2	0.0407 (11)	0.0314 (11)	0.0339 (10)	−0.0006 (8)	−0.0050 (9)	−0.0029 (9)
C3	0.0535 (13)	0.0293 (11)	0.0548 (14)	−0.0077 (9)	−0.0042 (11)	−0.0029 (10)
C4	0.0486 (14)	0.0515 (16)	0.0722 (18)	−0.0153 (11)	−0.0054 (13)	−0.0106 (13)
C5	0.0471 (13)	0.0652 (18)	0.0646 (16)	0.0005 (12)	−0.0138 (12)	0.0029 (14)
C6	0.0558 (14)	0.0389 (13)	0.0563 (15)	0.0030 (10)	−0.0084 (12)	0.0079 (11)
C7	0.0549 (12)	0.0247 (11)	0.0410 (12)	−0.0012 (9)	−0.0017 (10)	−0.0003 (9)
C8	0.0369 (10)	0.0334 (11)	0.0344 (10)	−0.0019 (8)	0.0037 (8)	0.0010 (9)
C9	0.0423 (11)	0.0347 (11)	0.0397 (12)	−0.0015 (9)	0.0020 (9)	−0.0046 (10)
C10	0.0596 (15)	0.0373 (12)	0.0549 (14)	−0.0141 (11)	0.0100 (12)	−0.0085 (11)
C11	0.0412 (12)	0.0677 (17)	0.0655 (16)	−0.0144 (14)	−0.0008 (12)	−0.0238 (14)
C12	0.0422 (12)	0.0730 (18)	0.0593 (14)	0.0050 (14)	−0.0099 (11)	−0.0093 (15)
C13	0.0540 (13)	0.0431 (14)	0.0468 (13)	0.0025 (11)	−0.0040 (11)	0.0005 (10)
C14	0.0458 (11)	0.0274 (11)	0.0438 (12)	−0.0015 (9)	−0.0034 (11)	−0.0028 (10)
C15	0.101 (2)	0.0358 (14)	0.0562 (15)	0.0020 (14)	−0.0241 (15)	0.0025 (12)
C16	0.091 (2)	0.0486 (16)	0.0506 (13)	−0.0154 (14)	−0.0283 (14)	0.0028 (12)
C17	0.0835 (18)	0.0515 (15)	0.0488 (13)	−0.0258 (14)	0.0192 (13)	−0.0146 (12)
C18	0.0752 (18)	0.0469 (15)	0.0530 (14)	−0.0230 (13)	0.0240 (13)	−0.0150 (12)
C19	0.0451 (13)	0.0421 (14)	0.094 (2)	−0.0066 (10)	0.0046 (12)	−0.0102 (14)
C20	0.0556 (14)	0.0427 (14)	0.0798 (17)	0.0033 (11)	0.0064 (15)	−0.0115 (14)

Cl1—C2	1.738 (2)	C8—C13	1.390 (3)
Cl2—C9	1.742 (2)	C8—C14	1.502 (3)
O1—C7	1.273 (3)	C9—C10	1.383 (3)
O2—C7	1.213 (3)	C10—C11	1.378 (4)
O3—C14	1.266 (3)	C10—H10A	0.930
O4—C14	1.228 (3)	C11—C12	1.370 (4)
N1—C17	1.464 (3)	C11—H11A	0.930
N1—C19	1.465 (3)	C12—C13	1.386 (4)
N1—C15	1.472 (3)	C12—H12A	0.930
N1—H1A	0.910	C13—H13A	0.930
N2—C16	1.480 (3)	C15—C16	1.529 (4)
N2—C18	1.480 (3)	C15—H15A	0.970
N2—C20	1.488 (3)	C15—H15B	0.970
N2—H2A	0.910	C16—H16A	0.970
C1—C2	1.380 (3)	C16—H16B	0.970
C1—C6	1.385 (3)	C17—C18	1.526 (3)
C1—C7	1.509 (3)	C17—H17A	0.970
C2—C3	1.385 (3)	C17—H17B	0.970
C3—C4	1.378 (4)	C18—H18A	0.970
C3—H3A	0.930	C18—H18B	0.970
C4—C5	1.381 (4)	C19—C20	1.531 (3)
C4—H4A	0.930	C19—H19A	0.970
C5—C6	1.388 (4)	C19—H19B	0.970
C5—H5A	0.930	C20—H20A	0.970
C6—H6A	0.930	C20—H20B	0.970
C8—C9	1.380 (3)
C17—N1—C19	109.7 (2)	C11—C12—C13	119.9 (2)
C17—N1—C15	110.5 (2)	C11—C12—H12A	120.0
C19—N1—C15	108.3 (2)	C13—C12—H12A	120.0
C17—N1—H1A	109.4	C12—C13—C8	121.4 (2)
C19—N1—H1A	109.4	C12—C13—H13A	119.3
C15—N1—H1A	109.4	C8—C13—H13A	119.3
C16—N2—C18	110.9 (2)	O4—C14—O3	125.4 (2)
C16—N2—C20	108.5 (2)	O4—C14—C8	119.2 (2)
C18—N2—C20	108.6 (2)	O3—C14—C8	115.4 (2)
C16—N2—H2A	109.6	N1—C15—C16	109.28 (19)
C18—N2—H2A	109.6	N1—C15—H15A	109.8
C20—N2—H2A	109.6	C16—C15—H15A	109.8
C2—C1—C6	117.32 (19)	N1—C15—H15B	109.8
C2—C1—C7	122.53 (19)	C16—C15—H15B	109.8
C6—C1—C7	120.10 (19)	H15A—C15—H15B	108.3
C1—C2—C3	121.9 (2)	N2—C16—C15	108.9 (2)
C1—C2—Cl1	119.41 (15)	N2—C16—H16A	109.9
C3—C2—Cl1	118.65 (16)	C15—C16—H16A	109.9
C4—C3—C2	119.4 (2)	N2—C16—H16B	109.9
C4—C3—H3A	120.3	C15—C16—H16B	109.9
C2—C3—H3A	120.3	H16A—C16—H16B	108.3
C3—C4—C5	120.4 (2)	N1—C17—C18	109.5 (2)
C3—C4—H4A	119.8	N1—C17—H17A	109.8
C5—C4—H4A	119.8	C18—C17—H17A	109.8
C4—C5—C6	118.9 (2)	N1—C17—H17B	109.8
C4—C5—H5A	120.6	C18—C17—H17B	109.8
C6—C5—H5A	120.6	H17A—C17—H17B	108.2
C1—C6—C5	122.1 (2)	N2—C18—C17	109.06 (19)
C1—C6—H6A	119.0	N2—C18—H18A	109.9
C5—C6—H6A	119.0	C17—C18—H18A	109.9
O2—C7—O1	124.7 (2)	N2—C18—H18B	109.9
O2—C7—C1	120.2 (2)	C17—C18—H18B	109.9
O1—C7—C1	115.07 (19)	H18A—C18—H18B	108.3
C9—C8—C13	117.1 (2)	N1—C19—C20	109.92 (18)
C9—C8—C14	123.97 (19)	N1—C19—H19A	109.7
C13—C8—C14	118.9 (2)	C20—C19—H19A	109.7
C8—C9—C10	122.1 (2)	N1—C19—H19B	109.7
C8—C9—Cl2	119.51 (16)	C20—C19—H19B	109.7
C10—C9—Cl2	118.36 (18)	H19A—C19—H19B	108.2
C11—C10—C9	119.5 (2)	N2—C20—C19	108.11 (18)
C11—C10—H10A	120.3	N2—C20—H20A	110.1
C9—C10—H10A	120.3	C19—C20—H20A	110.1
C12—C11—C10	119.9 (2)	N2—C20—H20B	110.1
C12—C11—H11A	120.0	C19—C20—H20B	110.1
C10—C11—H11A	120.0	H20A—C20—H20B	108.4
C6—C1—C2—C3	1.3 (3)	C11—C12—C13—C8	−0.7 (4)
C7—C1—C2—C3	−176.0 (2)	C9—C8—C13—C12	−0.2 (3)
C6—C1—C2—Cl1	−177.17 (17)	C14—C8—C13—C12	−178.5 (2)
C7—C1—C2—Cl1	5.6 (3)	C9—C8—C14—O4	−65.8 (3)
C1—C2—C3—C4	−0.5 (3)	C13—C8—C14—O4	112.4 (3)
Cl1—C2—C3—C4	177.9 (2)	C9—C8—C14—O3	116.1 (2)
C2—C3—C4—C5	−0.8 (4)	C13—C8—C14—O3	−65.7 (3)
C3—C4—C5—C6	1.2 (4)	C17—N1—C15—C16	−65.6 (3)
C2—C1—C6—C5	−0.8 (4)	C19—N1—C15—C16	54.6 (3)
C7—C1—C6—C5	176.6 (2)	C18—N2—C16—C15	52.6 (3)
C4—C5—C6—C1	−0.4 (4)	C20—N2—C16—C15	−66.6 (3)
C2—C1—C7—O2	75.5 (3)	N1—C15—C16—N2	10.2 (3)
C6—C1—C7—O2	−101.7 (3)	C19—N1—C17—C18	−65.0 (3)
C2—C1—C7—O1	−106.1 (2)	C15—N1—C17—C18	54.4 (3)
C6—C1—C7—O1	76.7 (3)	C16—N2—C18—C17	−63.8 (3)
C13—C8—C9—C10	1.3 (3)	C20—N2—C18—C17	55.4 (3)
C14—C8—C9—C10	179.6 (2)	N1—C17—C18—N2	8.7 (3)
C13—C8—C9—Cl2	179.07 (17)	C17—N1—C19—C20	53.6 (3)
C14—C8—C9—Cl2	−2.7 (3)	C15—N1—C19—C20	−67.1 (3)
C8—C9—C10—C11	−1.5 (4)	C16—N2—C20—C19	54.3 (3)
Cl2—C9—C10—C11	−179.29 (19)	C18—N2—C20—C19	−66.4 (3)
C9—C10—C11—C12	0.5 (4)	N1—C19—C20—N2	10.7 (3)
C10—C11—C12—C13	0.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.91	1.65	2.556 (2)	170
N2—H2A···O3	0.91	1.69	2.587 (2)	169

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.91	1.65	2.556 (2)	170
N2—H2A⋯O3	0.91	1.69	2.587 (2)	169