Benzoic acid–3,4-bis­[(pyridin-3-ylmeth­yl)amino]­cyclo­but-3-ene-1,2-dione (1/2)

Abstract

In the title co-crystal, C₁₆H₁₄N₄O₂·2C₇H₆O₂, the 3,4-bis­[(pyridin-3-ylmeth­yl)amino]­cyclo­but-3-ene-1,2-dione squareamide mol­ecules assemble into chains along the b axis via N—H⋯O hydrogen bonds. The benzoic acid mol­ecules then hydrogen bond to the pyridine rings via O—H⋯N hydrogen bonds, supported by weaker C—H⋯O hydrogen bonds, forming extended ribbons. The asymmetric unit consists of a half squareamide mol­ecule, sitting on a special position around a twofold axis, and one benzoic acid mol­ecule on a general position.

Related literature

For the synthesis of related squareamides and co-crystals, see: Liu et al. (2002 ▶).

Experimental

Crystal data

• C₁₆H₁₄N₄O₂·2C₇H₆O₂

• M _r = 538.55

• Monoclinic,

• a = 24.617 (5) Å

• b = 6.0285 (12) Å

• c = 17.806 (4) Å

• β = 93.08 (3)°

• V = 2638.6 (9) ų

• Z = 4

• Mo Kα radiation

• μ = 0.10 mm⁻¹

• T = 173 K

• 0.49 × 0.16 × 0.14 mm

Data collection

• Nonius KappaCCD area-detector diffractometer

• Absorption correction: integration (XPREP; Bruker, 2004 ▶) T _min = 0.944, T _max = 0.989

• 15016 measured reflections

• 3166 independent reflections

• 2110 reflections with I > 2σ(I)

• R _int = 0.076

Refinement

• R[F ² > 2σ(F ²)] = 0.044

• wR(F ²) = 0.116

• S = 0.99

• 3166 reflections

• 190 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.23 e Å⁻³

• Δρ_min = −0.24 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN; 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 PLATON (Spek, 2009 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812000220/fy2039Isup3.mol

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.915 (16)	1.889 (17)	2.7697 (15)	161.0 (13)
O2—H2⋯N2	1.07 (2)	1.57 (2)	2.6380 (15)	178.0 (17)
C2—H2A⋯O3	0.95	2.68	3.3341 (18)	127

Symmetry code: (i) .

supplementary crystallographic information

Comment

The title compound is a further example of co-crystals formed by squareamide molecules, in this case 3,4-bis[(pyridin-3-ylmethyl)amino]cyclobut-3-ene-1,2-dione, with carboxylic acid containing co-former molecules. Related co-crystals where the squaureamide molecule has the pyridine N atom in the 4 position are reported by Liu et al. (2002). The asymmetric unit consists of one half squareamide molecule, sitting around a twofold axis, and one complete benzoic acid molecule, on a general position (Fig. 1). The squareamide self-assembles into chains using the two N—H···O hydrogen bonds formed from the two amine N—-H groups to the diketones. The pyridine rings then act as hydrogen bond acceptors to the carboxylic acid functional group of the two benzoic acid molecules (Fig. 2).

Experimental

The title squareamide compound was synthesized according to literature procedures (Liu et al., 2002) by double condensation of diethyl squarate with 1-(pyridin-3-yl)methanamine in ethanol by stirring for 12 h. The resulting solid was filtered and dried. The squareamide was then dissolved in a 1:2 stoichiometric ratio with benzoic acid in a 1/1 v/v mixture of methanol and water. Plate-like, colourless crystals were harvested after a few days by slow evaporation at ambient conditions.

Refinement

The C-bound H atoms were geometrically placed with C—H bond lengths of 0.95 Å (aromatic CH) and 0.99 Å (methylene CH₂) and were refined as riding with U_iso(H) = 1.2U_eq(C). The N-bound and O-bound H atoms were located in the difference map and their coordinates and isotropic displacement parameters were refined freely.

Figures

Fig. 1.

The asymmetric unit of (I) showing the atom numbering scheme. Displacement ellipsoids are shown at the 50% probability level. Atoms with superscript i are generated by the symmetry operation (-x, y, -z + 1/2).

Fig. 2.

Hydrogen bonding diagram of the ribbons of (I). Intermolecular N—H···O and O—H···N hydrogen bonds are shown as dashed red lines.

Crystal data

C16H14N4O2·2C7H6O2	F(000) = 1128
Mr = 538.55	Dx = 1.356 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 16004 reflections
a = 24.617 (5) Å	θ = 0.2–28.3°
b = 6.0285 (12) Å	µ = 0.10 mm−1
c = 17.806 (4) Å	T = 173 K
β = 93.08 (3)°	Plate, colourless
V = 2638.6 (9) Å3	0.49 × 0.16 × 0.14 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	2110 reflections with I > 2σ(I)
2.0° ω scans	Rint = 0.076
Absorption correction: integration (XPREP; Bruker, 2004)	θmax = 28.0°, θmin = 2.3°
Tmin = 0.944, Tmax = 0.989	h = −32→26
15016 measured reflections	k = −7→7
3166 independent reflections	l = −23→21

Refinement

Refinement on F2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0659P)2 + ] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.044	(Δ/σ)max < 0.001
wR(F2) = 0.116	Δρmax = 0.23 e Å−3
S = 0.99	Δρmin = −0.24 e Å−3
3166 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
190 parameters	Extinction coefficient: 0.0097 (11)
0 restraints

Special details

Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 2004).

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.

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

	x	y	z	Uiso*/Ueq
C1	0.09548 (5)	0.7538 (2)	0.57965 (7)	0.0286 (3)
C2	0.10973 (5)	0.5561 (2)	0.54679 (7)	0.0333 (3)
H2A	0.0814	0.4569	0.5308	0.04*
C3	0.20066 (6)	0.6353 (3)	0.55968 (8)	0.0417 (4)
H3	0.2373	0.5946	0.5526	0.05*
C4	0.19060 (6)	0.8346 (3)	0.59354 (8)	0.0430 (4)
H4	0.2198	0.929	0.61	0.052*
C5	0.13726 (6)	0.8956 (2)	0.60321 (7)	0.0366 (3)
H5	0.1293	1.0337	0.6259	0.044*
C6	0.03667 (5)	0.8124 (2)	0.58837 (7)	0.0307 (3)
H6A	0.0312	0.9723	0.5777	0.037*
H6B	0.0136	0.7275	0.5513	0.037*
C7	0.00897 (5)	0.91990 (19)	0.71280 (7)	0.0261 (3)
C8	0.01001 (5)	1.16213 (19)	0.71131 (7)	0.0293 (3)
N1	0.02002 (4)	0.76350 (17)	0.66414 (6)	0.0298 (3)
H1	0.0195 (6)	0.616 (3)	0.6757 (8)	0.041 (4)*
N2	0.16108 (5)	0.49629 (19)	0.53623 (6)	0.0384 (3)
O1	0.02247 (4)	1.30418 (13)	0.66529 (5)	0.0373 (3)
C9	0.14385 (5)	−0.1060 (2)	0.36020 (7)	0.0350 (3)
C10	0.18500 (6)	−0.0836 (2)	0.31016 (8)	0.0423 (4)
H10	0.208	0.0431	0.3128	0.051*
C11	0.19255 (7)	−0.2448 (3)	0.25655 (9)	0.0513 (4)
H11	0.2201	−0.2273	0.2217	0.062*
C12	0.16006 (8)	−0.4312 (3)	0.25359 (9)	0.0573 (5)
H12	0.1657	−0.543	0.2172	0.069*
C13	0.11934 (8)	−0.4557 (3)	0.30324 (10)	0.0559 (5)
H13	0.0972	−0.5848	0.3013	0.067*
C14	0.11075 (6)	−0.2923 (3)	0.35590 (8)	0.0452 (4)
H14	0.0821	−0.3078	0.3892	0.054*
C15	0.13450 (6)	0.0665 (2)	0.41783 (8)	0.0374 (4)
O2	0.17883 (4)	0.18069 (17)	0.43789 (6)	0.0443 (3)
H2	0.1708 (7)	0.309 (3)	0.4774 (11)	0.080 (6)*
O3	0.09068 (4)	0.09691 (18)	0.44435 (6)	0.0484 (3)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0315 (7)	0.0303 (7)	0.0247 (6)	0.0022 (5)	0.0069 (5)	0.0042 (5)
C2	0.0308 (7)	0.0342 (7)	0.0355 (7)	0.0025 (6)	0.0083 (6)	−0.0004 (5)
C3	0.0282 (8)	0.0576 (9)	0.0400 (8)	0.0050 (7)	0.0092 (6)	0.0049 (7)
C4	0.0339 (8)	0.0501 (9)	0.0452 (8)	−0.0078 (7)	0.0033 (6)	0.0024 (7)
C5	0.0401 (8)	0.0324 (7)	0.0376 (8)	−0.0007 (6)	0.0065 (6)	0.0003 (6)
C6	0.0320 (7)	0.0289 (7)	0.0319 (7)	0.0048 (5)	0.0081 (5)	0.0008 (5)
C7	0.0227 (6)	0.0211 (6)	0.0353 (7)	0.0006 (5)	0.0073 (5)	0.0000 (5)
C8	0.0282 (7)	0.0219 (6)	0.0384 (7)	0.0012 (5)	0.0084 (5)	0.0004 (5)
N1	0.0355 (6)	0.0203 (6)	0.0348 (6)	0.0017 (5)	0.0130 (5)	0.0013 (4)
N2	0.0335 (7)	0.0443 (7)	0.0384 (7)	0.0092 (5)	0.0103 (5)	−0.0012 (5)
O1	0.0468 (6)	0.0225 (5)	0.0440 (5)	−0.0014 (4)	0.0159 (4)	0.0046 (4)
C9	0.0308 (7)	0.0419 (8)	0.0324 (7)	0.0077 (6)	0.0018 (6)	0.0064 (6)
C10	0.0372 (8)	0.0459 (8)	0.0445 (9)	0.0044 (6)	0.0093 (7)	0.0008 (6)
C11	0.0507 (10)	0.0624 (11)	0.0417 (9)	0.0148 (8)	0.0099 (7)	−0.0028 (8)
C12	0.0702 (12)	0.0560 (11)	0.0441 (9)	0.0146 (9)	−0.0110 (9)	−0.0100 (7)
C13	0.0640 (12)	0.0507 (10)	0.0510 (10)	−0.0084 (8)	−0.0155 (9)	−0.0003 (8)
C14	0.0393 (9)	0.0593 (10)	0.0367 (8)	−0.0032 (7)	−0.0025 (6)	0.0077 (7)
C15	0.0310 (8)	0.0460 (9)	0.0356 (8)	0.0100 (6)	0.0066 (6)	0.0074 (6)
O2	0.0331 (6)	0.0490 (6)	0.0518 (6)	0.0063 (5)	0.0112 (5)	−0.0115 (5)
O3	0.0322 (6)	0.0669 (7)	0.0472 (6)	0.0120 (5)	0.0133 (5)	0.0027 (5)

Geometric parameters (Å, °)

C1—C2	1.3816 (18)	C8—C8i	1.488 (3)
C1—C5	1.3849 (19)	N1—H1	0.915 (16)
C1—C6	1.5061 (18)	C9—C14	1.387 (2)
C2—N2	1.3374 (17)	C9—C10	1.391 (2)
C2—H2A	0.95	C9—C15	1.487 (2)
C3—N2	1.3351 (19)	C10—C11	1.382 (2)
C3—C4	1.373 (2)	C10—H10	0.95
C3—H3	0.95	C11—C12	1.378 (2)
C4—C5	1.383 (2)	C11—H11	0.95
C4—H4	0.95	C12—C13	1.380 (3)
C5—H5	0.95	C12—H12	0.95
C6—N1	1.4612 (16)	C13—C14	1.384 (2)
C6—H6A	0.99	C13—H13	0.95
C6—H6B	0.99	C14—H14	0.95
C7—N1	1.3187 (16)	C15—O3	1.2146 (16)
C7—C7i	1.419 (2)	C15—O2	1.3231 (17)
C7—C8	1.4607 (17)	O2—H2	1.07 (2)
C8—O1	1.2354 (15)
C2—C1—C5	117.35 (12)	C7—N1—C6	122.71 (11)
C2—C1—C6	120.89 (12)	C7—N1—H1	122.9 (9)
C5—C1—C6	121.76 (12)	C6—N1—H1	114.3 (9)
N2—C2—C1	123.74 (13)	C3—N2—C2	117.80 (12)
N2—C2—H2A	118.1	C14—C9—C10	119.28 (14)
C1—C2—H2A	118.1	C14—C9—C15	119.46 (13)
N2—C3—C4	122.74 (13)	C10—C9—C15	121.26 (13)
N2—C3—H3	118.6	C11—C10—C9	120.24 (15)
C4—C3—H3	118.6	C11—C10—H10	119.9
C3—C4—C5	118.83 (14)	C9—C10—H10	119.9
C3—C4—H4	120.6	C12—C11—C10	120.03 (16)
C5—C4—H4	120.6	C12—C11—H11	120
C4—C5—C1	119.53 (13)	C10—C11—H11	120
C4—C5—H5	120.2	C11—C12—C13	120.19 (15)
C1—C5—H5	120.2	C11—C12—H12	119.9
N1—C6—C1	111.52 (10)	C13—C12—H12	119.9
N1—C6—H6A	109.3	C12—C13—C14	120.03 (16)
C1—C6—H6A	109.3	C12—C13—H13	120
N1—C6—H6B	109.3	C14—C13—H13	120
C1—C6—H6B	109.3	C13—C14—C9	120.20 (16)
H6A—C6—H6B	108	C13—C14—H14	119.9
N1—C7—C7i	134.35 (7)	C9—C14—H14	119.9
N1—C7—C8	134.30 (12)	O3—C15—O2	123.58 (13)
C7i—C7—C8	91.35 (7)	O3—C15—C9	123.19 (14)
O1—C8—C7	135.25 (12)	O2—C15—C9	113.22 (12)
O1—C8—C8i	136.11 (7)	C15—O2—H2	111.9 (10)
C7—C8—C8i	88.64 (7)
C5—C1—C2—N2	−0.52 (19)	C4—C3—N2—C2	−0.2 (2)
C6—C1—C2—N2	178.76 (11)	C1—C2—N2—C3	0.8 (2)
N2—C3—C4—C5	−0.7 (2)	C14—C9—C10—C11	0.3 (2)
C3—C4—C5—C1	0.9 (2)	C15—C9—C10—C11	−179.30 (13)
C2—C1—C5—C4	−0.35 (19)	C9—C10—C11—C12	−1.5 (2)
C6—C1—C5—C4	−179.62 (12)	C10—C11—C12—C13	1.1 (2)
C2—C1—C6—N1	98.57 (14)	C11—C12—C13—C14	0.5 (2)
C5—C1—C6—N1	−82.19 (14)	C12—C13—C14—C9	−1.6 (2)
N1—C7—C8—O1	−1.8 (3)	C10—C9—C14—C13	1.2 (2)
C7i—C7—C8—O1	178.55 (15)	C15—C9—C14—C13	−179.17 (13)
N1—C7—C8—C8i	178.45 (15)	C14—C9—C15—O3	−25.7 (2)
C7i—C7—C8—C8i	−1.20 (14)	C10—C9—C15—O3	153.96 (14)
C7i—C7—N1—C6	178.04 (17)	C14—C9—C15—O2	153.46 (12)
C8—C7—N1—C6	−1.5 (2)	C10—C9—C15—O2	−26.92 (18)
C1—C6—N1—C7	110.22 (13)

Symmetry codes: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ii	0.915 (16)	1.889 (17)	2.7697 (15)	161.0 (13)
O2—H2···N2	1.07 (2)	1.57 (2)	2.6380 (15)	178.0 (17)
C2—H2A···O3	0.95	2.68	3.3341 (18)	127

Symmetry codes: (ii) x, y−1, z.