4-Carbamoylpyridin-1-ium 2,2,2-tri-chloro-acetate-isonicotinamide (1/1).

In the crystal structure of the title 1:1 co-crystal, C(6)H(7)N(2)O(+)·C(2)Cl(3)O(2) (-)·C(6)H(6)N(2)O, the amide groups of the 4-carbamoylpyridin-1-ium ion and the isonicotinamide mol-ecule are twisted out of the plane of the aromatic ring with C-C-C-N torsion angles of 21.5 (4) and -33.5 (4)°, respectively. The 4-carbamoylpyridin-1-ium and isonicotinamide amide groups form R(2) (2)(8) hydrogen-bonded dimers via N-H⋯O=C inter-actions. The two remaining amide H atoms (i) link dimers via the cation to an isonicotinamide and (ii) from the isonicotinamide to a trichloro-acetate anion. The pyridinium H atom also forms an N-H⋯O hydrogen bond with the trichloro-acetate anion. Due to the extended hydrogen bonding, including C-H⋯O and C-H⋯Cl interactions, all components in the structure aggregate into a three-dimensional supra-molecular framework.

Related literature

For applications of co-crystals, see: Karki et al. (2009 ▶); Friščić & Jones (2010 ▶). For related structures, see: Madeley et al. (2011 ▶).

Experimental

Crystal data

C6H7N2O+·C2Cl3O2 −·C6H6N2O

M = 407.63

Orthorhombic,

a = 13.7910 (3) Å

b = 22.6680 (5) Å

c = 5.6340 (1) Å

V = 1761.27 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.55 mm−1

T = 293 K

0.4 × 0.1 × 0.1 mm

Data collection

Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.811, T max = 0.947

16297 measured reflections

4017 independent reflections

3575 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.04

wR(F 2) = 0.091

S = 1.04

4017 reflections

241 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.41 e Å−3

Δρmin = −0.57 e Å−3

Absolute structure: Flack (1983) ▶, 1791 Friedel pairs

Flack parameter: 0.01 (6)

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812037002/gg2095sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812037002/gg2095Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812037002/gg2095Isup3.cml

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

C6H7N2O+·C2Cl3O2−·C6H6N2O	F(000) = 832
Mr = 407.63	Dx = 1.537 Mg m−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 7898 reflections
a = 13.7910 (3) Å	θ = 3.1–30.4°
b = 22.6680 (5) Å	µ = 0.55 mm−1
c = 5.6340 (1) Å	T = 293 K
V = 1761.27 (6) Å3	Prism, colourless
Z = 4	0.4 × 0.1 × 0.1 mm

Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer	4017 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3575 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.031
Detector resolution: 10.4933 pixels mm-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −17→17
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −29→29
Tmin = 0.811, Tmax = 0.947	l = −7→7
16297 measured reflections

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)] = 0.04	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.091	w = 1/[σ2(Fo2) + (0.0359P)2 + 0.8943P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
4017 reflections	Δρmax = 0.41 e Å−3
241 parameters	Δρmin = −0.57 e Å−3
1 restraint	Absolute structure: Flack (1983), 1791 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.01 (6)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.49348 (5)	0.58322 (3)	0.45563 (14)	0.04547 (17)
Cl2	0.44990 (9)	0.67585 (4)	0.11741 (18)	0.0850 (4)
Cl3	0.32105 (7)	0.65069 (5)	0.50880 (15)	0.0770 (3)
N1	−0.29717 (16)	0.50785 (9)	1.1681 (4)	0.0377 (5)
H15	−0.330 (2)	0.4892 (15)	1.285 (6)	0.057*
N2	−0.16743 (16)	0.62843 (10)	0.4929 (5)	0.0396 (5)
H16A	−0.217 (2)	0.6478 (14)	0.551 (7)	0.059*
H16B	−0.135 (3)	0.6394 (15)	0.362 (6)	0.059*
N3	0.19060 (17)	0.78523 (10)	−0.3220 (5)	0.0425 (5)
N4	0.06680 (19)	0.61873 (11)	0.1998 (5)	0.0495 (7)
H17A	0.030 (3)	0.5952 (17)	0.294 (8)	0.074*
H17B	0.131 (3)	0.6133 (15)	0.197 (7)	0.074*
O1	0.25905 (13)	0.57929 (9)	0.1146 (4)	0.0524 (5)
O2	0.40234 (13)	0.54301 (8)	0.0115 (4)	0.0426 (4)
O3	−0.06660 (12)	0.66646 (9)	0.0707 (4)	0.0473 (5)
O4	−0.05512 (13)	0.55797 (8)	0.5595 (4)	0.0488 (5)
C1	−0.20142 (19)	0.49801 (11)	1.1584 (5)	0.0384 (6)
H1	−0.1721	0.4742	1.2722	0.046*
C2	−0.14636 (17)	0.52287 (10)	0.9812 (5)	0.0356 (5)
H2	−0.0801	0.5155	0.9729	0.043*
C3	−0.19079 (17)	0.55906 (10)	0.8150 (4)	0.0293 (5)
C4	−0.29018 (18)	0.56864 (11)	0.8322 (5)	0.0335 (5)
H4	−0.3214	0.5929	0.7233	0.04*
C5	−0.34193 (18)	0.54211 (11)	1.0107 (5)	0.0387 (6)
H5	−0.4085	0.5481	1.0217	0.046*
C6	−0.13130 (17)	0.58311 (10)	0.6111 (5)	0.0320 (5)
C7	0.2246 (2)	0.76108 (12)	−0.1226 (6)	0.0454 (7)
H7	0.2848	0.7735	−0.0675	0.055*
C8	0.17586 (17)	0.71890 (11)	0.0064 (5)	0.0396 (6)
H8	0.2034	0.7027	0.1424	0.048*
C9	0.08482 (16)	0.70091 (10)	−0.0701 (5)	0.0305 (5)
C10	0.0493 (2)	0.72548 (12)	−0.2753 (5)	0.0384 (6)
H10	−0.0114	0.7145	−0.3326	0.046*
C11	0.1043 (2)	0.76648 (11)	−0.3955 (5)	0.0433 (6)
H11	0.0797	0.7819	−0.5361	0.052*
C12	0.02224 (18)	0.65981 (11)	0.0724 (5)	0.0358 (6)
C13	0.34726 (17)	0.57605 (10)	0.1255 (4)	0.0306 (5)
C14	0.40010 (19)	0.61971 (11)	0.2972 (5)	0.0368 (6)

	U11	U22	U33	U12	U13	U23
Cl1	0.0384 (3)	0.0586 (4)	0.0395 (3)	0.0069 (3)	−0.0118 (3)	0.0020 (3)
Cl2	0.1224 (9)	0.0644 (5)	0.0681 (6)	−0.0526 (6)	−0.0447 (6)	0.0302 (5)
Cl3	0.0848 (6)	0.0950 (6)	0.0510 (5)	0.0508 (5)	−0.0198 (4)	−0.0362 (5)
N1	0.0414 (12)	0.0353 (11)	0.0365 (13)	−0.0078 (9)	0.0084 (10)	0.0028 (9)
N2	0.0375 (12)	0.0379 (11)	0.0435 (13)	0.0082 (9)	0.0147 (11)	0.0077 (11)
N3	0.0423 (13)	0.0351 (11)	0.0503 (14)	−0.0051 (9)	0.0080 (11)	0.0057 (10)
N4	0.0317 (12)	0.0490 (14)	0.0678 (17)	0.0069 (10)	0.0141 (12)	0.0256 (13)
O1	0.0277 (9)	0.0589 (12)	0.0706 (14)	0.0023 (8)	−0.0027 (10)	−0.0192 (12)
O2	0.0346 (9)	0.0506 (10)	0.0426 (10)	0.0042 (8)	−0.0017 (8)	−0.0179 (9)
O3	0.0278 (9)	0.0557 (11)	0.0585 (13)	0.0039 (8)	0.0068 (9)	0.0201 (10)
O4	0.0367 (10)	0.0514 (11)	0.0585 (14)	0.0153 (8)	0.0200 (9)	0.0148 (10)
C1	0.0444 (15)	0.0377 (13)	0.0332 (15)	0.0002 (11)	−0.0051 (11)	0.0055 (11)
C2	0.0307 (11)	0.0348 (12)	0.0413 (14)	0.0014 (9)	0.0001 (12)	0.0002 (12)
C3	0.0297 (12)	0.0279 (11)	0.0304 (12)	−0.0023 (9)	0.0021 (10)	−0.0034 (9)
C4	0.0300 (13)	0.0340 (13)	0.0364 (13)	0.0012 (10)	0.0031 (11)	0.0044 (10)
C5	0.0347 (13)	0.0381 (13)	0.0435 (14)	−0.0010 (10)	0.0099 (12)	0.0013 (12)
C6	0.0295 (12)	0.0343 (12)	0.0321 (12)	−0.0013 (9)	0.0071 (10)	−0.0003 (11)
C7	0.0327 (14)	0.0460 (16)	0.0577 (18)	−0.0081 (12)	−0.0007 (12)	0.0027 (14)
C8	0.0317 (12)	0.0450 (14)	0.0422 (15)	0.0006 (10)	−0.0029 (11)	0.0061 (13)
C9	0.0288 (11)	0.0289 (11)	0.0337 (12)	0.0018 (9)	0.0050 (10)	0.0020 (10)
C10	0.0337 (13)	0.0412 (14)	0.0404 (14)	−0.0027 (11)	−0.0053 (11)	0.0025 (12)
C11	0.0490 (15)	0.0441 (14)	0.0369 (14)	0.0005 (12)	−0.0016 (13)	0.0113 (13)
C12	0.0313 (13)	0.0343 (12)	0.0418 (15)	0.0018 (10)	0.0064 (11)	0.0060 (11)
C13	0.0323 (12)	0.0325 (11)	0.0269 (11)	−0.0016 (9)	−0.0010 (10)	−0.0008 (10)
C14	0.0435 (15)	0.0342 (14)	0.0327 (12)	0.0039 (11)	−0.0083 (11)	−0.0023 (11)

Cl1—C14	1.772 (3)	C1—H1	0.93
Cl2—C14	1.765 (3)	C2—C3	1.387 (4)
Cl3—C14	1.762 (3)	C2—H2	0.93
N1—C5	1.331 (4)	C3—C4	1.391 (3)
N1—C1	1.340 (3)	C3—C6	1.513 (3)
N1—H15	0.90 (3)	C4—C5	1.372 (4)
N2—C6	1.322 (3)	C4—H4	0.93
N2—H16A	0.87 (3)	C5—H5	0.93
N2—H16B	0.90 (4)	C7—C8	1.376 (4)
N3—C11	1.330 (4)	C7—H7	0.93
N3—C7	1.335 (4)	C8—C9	1.389 (3)
N4—C12	1.326 (3)	C8—H8	0.93
N4—H17A	0.91 (4)	C9—C10	1.374 (4)
N4—H17B	0.89 (4)	C9—C12	1.503 (3)
O1—C13	1.220 (3)	C10—C11	1.378 (4)
O2—C13	1.245 (3)	C10—H10	0.93
O3—C12	1.234 (3)	C11—H11	0.93
O4—C6	1.230 (3)	C13—C14	1.564 (3)
C1—C2	1.375 (4)
C5—N1—C1	121.8 (2)	N3—C7—C8	123.9 (3)
C5—N1—H15	122 (2)	N3—C7—H7	118
C1—N1—H15	116 (2)	C8—C7—H7	118
C6—N2—H16A	120 (2)	C7—C8—C9	118.8 (3)
C6—N2—H16B	116 (2)	C7—C8—H8	120.6
H16A—N2—H16B	124 (3)	C9—C8—H8	120.6
C11—N3—C7	116.4 (2)	C10—C9—C8	117.7 (2)
C12—N4—H17A	118 (2)	C10—C9—C12	119.7 (2)
C12—N4—H17B	123 (2)	C8—C9—C12	122.4 (2)
H17A—N4—H17B	119 (3)	C9—C10—C11	119.4 (2)
N1—C1—C2	120.3 (2)	C9—C10—H10	120.3
N1—C1—H1	119.8	C11—C10—H10	120.3
C2—C1—H1	119.8	N3—C11—C10	123.7 (3)
C1—C2—C3	119.2 (2)	N3—C11—H11	118.1
C1—C2—H2	120.4	C10—C11—H11	118.1
C3—C2—H2	120.4	O3—C12—N4	123.4 (2)
C2—C3—C4	118.7 (2)	O3—C12—C9	119.3 (2)
C2—C3—C6	119.1 (2)	N4—C12—C9	117.3 (2)
C4—C3—C6	122.1 (2)	O1—C13—O2	128.2 (2)
C5—C4—C3	119.7 (2)	O1—C13—C14	117.2 (2)
C5—C4—H4	120.2	O2—C13—C14	114.6 (2)
C3—C4—H4	120.2	C13—C14—Cl3	112.49 (18)
N1—C5—C4	120.2 (2)	C13—C14—Cl2	106.43 (18)
N1—C5—H5	119.9	Cl3—C14—Cl2	109.97 (15)
C4—C5—H5	119.9	C13—C14—Cl1	110.78 (17)
O4—C6—N2	124.3 (2)	Cl3—C14—Cl1	107.15 (15)
O4—C6—C3	118.4 (2)	Cl2—C14—Cl1	110.04 (15)
N2—C6—C3	117.3 (2)
C5—N1—C1—C2	−0.8 (4)	C7—C8—C9—C12	−173.6 (2)
N1—C1—C2—C3	1.1 (4)	C8—C9—C10—C11	−0.1 (4)
C1—C2—C3—C4	−0.5 (4)	C12—C9—C10—C11	175.2 (2)
C1—C2—C3—C6	−176.0 (2)	C7—N3—C11—C10	1.5 (4)
C2—C3—C4—C5	−0.4 (4)	C9—C10—C11—N3	−1.5 (4)
C6—C3—C4—C5	175.0 (2)	C10—C9—C12—O3	−30.3 (4)
C1—N1—C5—C4	−0.1 (4)	C8—C9—C12—O3	144.8 (3)
C3—C4—C5—N1	0.7 (4)	C10—C9—C12—N4	151.4 (3)
C2—C3—C6—O4	20.0 (4)	C8—C9—C12—N4	−33.5 (4)
C4—C3—C6—O4	−155.4 (3)	O1—C13—C14—Cl3	17.9 (3)
C2—C3—C6—N2	−163.1 (2)	O2—C13—C14—Cl3	−163.93 (19)
C4—C3—C6—N2	21.5 (4)	O1—C13—C14—Cl2	−102.6 (3)
C11—N3—C7—C8	0.1 (4)	O2—C13—C14—Cl2	75.6 (2)
N3—C7—C8—C9	−1.6 (4)	O1—C13—C14—Cl1	137.8 (2)
C7—C8—C9—C10	1.5 (4)	O2—C13—C14—Cl1	−44.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H15···O2i	0.90 (3)	1.78 (3)	2.679 (3)	175 (3)
N2—H16A···N3ii	0.87 (3)	2.11 (3)	2.958 (3)	164 (3)
N2—H16B···O3	0.90 (4)	1.99 (4)	2.887 (3)	178 (3)
N4—H17A···O4	0.91 (4)	2.08 (4)	2.972 (3)	167 (4)
N4—H17B···O1	0.89 (4)	1.98 (4)	2.839 (3)	160 (3)
C1—H1···O1i	0.93	2.58	3.211 (3)	126
C2—H2···O4iii	0.93	2.55	3.358 (3)	146
C7—H7···O3iv	0.93	2.58	3.489 (3)	166
C11—H11···Cl2v	0.93	2.82	3.711 (3)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H15⋯O2i	0.90 (3)	1.78 (3)	2.679 (3)	175 (3)
N2—H16A⋯N3ii	0.87 (3)	2.11 (3)	2.958 (3)	164 (3)
N2—H16B⋯O3	0.90 (4)	1.99 (4)	2.887 (3)	178 (3)
N4—H17A⋯O4	0.91 (4)	2.08 (4)	2.972 (3)	167 (4)
N4—H17B⋯O1	0.89 (4)	1.98 (4)	2.839 (3)	160 (3)
C1—H1⋯O1i	0.93	2.58	3.211 (3)	126
C2—H2⋯O4iii	0.93	2.55	3.358 (3)	146
C7—H7⋯O3iv	0.93	2.58	3.489 (3)	166
C11—H11⋯Cl2v	0.93	2.82	3.711 (3)	162

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