2,6-Diamino-4-chloro-pyrimidine-benzoic acid (1/1).

The benzoic acid mol-ecule of the title compound, C4H5ClN4·C7H6O2, is approximately planar, with a dihedral angle of 1.28 (9)° between the carb-oxy group and the benzene ring. In the crystal, two acid and two base mol-ecules are linked through N-H⋯O and O-H⋯N hydrogen bonds, forming a centrosymmetric 2 + 2 unit with R2(2)(8) and R4(2)(8) motifs. These units are further linked through a pair of N-H⋯N hydrogen bonds into a tape structure along [1-20]. The crystal structure also features weak π-π [centroid-centroid distance = 3.5984 (11) Å] and C-H⋯π inter-actions.

Related literature

For the biological activity of pyrimidine and amino­pyrimidine derivatives, see: Hunt et al. (1980 ▶); Baker & Santi (1965 ▶). For related structures, see: Schwalbe & Williams (1982 ▶); Hu et al. (2002 ▶); Chinnakali et al. (1999 ▶); Skovsgaard & Bond (2009 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C4H5ClN4·C7H6O2

M = 266.69

Monoclinic,

a = 8.7817 (17) Å

b = 5.7032 (12) Å

c = 24.026 (4) Å

β = 95.493 (4)°

V = 1197.8 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.32 mm−1

T = 100 K

0.36 × 0.30 × 0.16 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.895, T max = 0.951

7539 measured reflections

2097 independent reflections

1891 reflections with I > 2σ(I)

R int = 0.052

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.101

S = 1.09

2097 reflections

183 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.24 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 and PLATON (Spek, 2009 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681204768X/is5218sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681204768X/is5218Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S160053681204768X/is5218Isup3.cml

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

C4H5ClN4·C7H6O2	F(000) = 552
Mr = 266.69	Dx = 1.479 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5646 reflections
a = 8.7817 (17) Å	θ = 3.0–30.0°
b = 5.7032 (12) Å	µ = 0.32 mm−1
c = 24.026 (4) Å	T = 100 K
β = 95.493 (4)°	Block, colourless
V = 1197.8 (4) Å3	0.36 × 0.30 × 0.16 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	2097 independent reflections
Radiation source: fine-focus sealed tube	1891 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
φ and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
Tmin = 0.895, Tmax = 0.951	k = −6→6
7539 measured reflections	l = −28→28

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0471P)2 + 0.4196P] where P = (Fo2 + 2Fc2)/3
2097 reflections	(Δ/σ)max < 0.001
183 parameters	Δρmax = 0.25 e Å−3
1 restraint	Δρmin = −0.24 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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	−0.05557 (4)	0.64565 (9)	0.367228 (16)	0.03348 (18)
O1	0.43197 (13)	0.5175 (2)	0.61239 (5)	0.0312 (3)
O2	0.52962 (16)	0.1720 (2)	0.59015 (5)	0.0372 (3)
N1	0.07033 (15)	0.7543 (3)	0.46563 (5)	0.0274 (4)
N2	0.27154 (14)	0.5362 (3)	0.51588 (5)	0.0266 (4)
N3	0.16941 (19)	0.8669 (3)	0.55310 (6)	0.0313 (4)
N4	0.37676 (16)	0.2112 (3)	0.47835 (7)	0.0325 (4)
C1	0.07703 (17)	0.5991 (3)	0.42471 (7)	0.0272 (4)
C2	0.17389 (17)	0.4136 (4)	0.42399 (7)	0.0287 (4)
H2A	0.1734	0.3108	0.3929	0.034*
C3	0.27541 (17)	0.3846 (3)	0.47284 (7)	0.0272 (4)
C4	0.17144 (17)	0.7163 (3)	0.51057 (6)	0.0265 (4)
C5	0.71603 (19)	0.1587 (3)	0.69200 (7)	0.0264 (4)
H5A	0.7220	0.0302	0.6672	0.032*
C6	0.80722 (19)	0.1626 (3)	0.74236 (7)	0.0276 (4)
H6A	0.8760	0.0372	0.7519	0.033*
C7	0.79790 (17)	0.3497 (3)	0.77877 (7)	0.0251 (4)
H7A	0.8608	0.3526	0.8132	0.030*
C8	0.69723 (17)	0.5321 (3)	0.76507 (7)	0.0258 (4)
H8A	0.6908	0.6594	0.7902	0.031*
C9	0.60544 (17)	0.5293 (3)	0.71455 (7)	0.0241 (4)
H9A	0.5361	0.6542	0.7052	0.029*
C10	0.61545 (17)	0.3430 (3)	0.67768 (6)	0.0214 (4)
C11	0.52134 (18)	0.3366 (3)	0.62273 (7)	0.0249 (4)
H2N3	0.233 (3)	0.851 (4)	0.5785 (10)	0.039 (6)*
H2N4	0.432 (2)	0.196 (4)	0.5105 (10)	0.045 (6)*
H1N4	0.388 (2)	0.113 (4)	0.4508 (9)	0.033 (5)*
H1N3	0.109 (2)	0.983 (4)	0.5499 (9)	0.037 (6)*
H1O1	0.386 (3)	0.508 (7)	0.5789 (7)	0.113 (13)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0286 (3)	0.0508 (4)	0.0183 (2)	−0.00328 (18)	−0.01233 (16)	0.00310 (18)
O1	0.0260 (6)	0.0437 (8)	0.0220 (6)	0.0042 (6)	−0.0080 (5)	0.0035 (6)
O2	0.0521 (8)	0.0321 (8)	0.0240 (6)	−0.0019 (6)	−0.0147 (6)	−0.0010 (6)
N1	0.0230 (6)	0.0382 (9)	0.0190 (7)	−0.0093 (6)	−0.0076 (5)	0.0077 (7)
N2	0.0203 (6)	0.0395 (9)	0.0183 (7)	−0.0085 (6)	−0.0059 (5)	0.0068 (6)
N3	0.0318 (8)	0.0370 (10)	0.0217 (8)	−0.0044 (7)	−0.0144 (6)	0.0040 (7)
N4	0.0262 (7)	0.0503 (11)	0.0195 (7)	−0.0020 (7)	−0.0058 (6)	0.0009 (7)
C1	0.0202 (7)	0.0439 (11)	0.0159 (8)	−0.0113 (7)	−0.0071 (6)	0.0080 (7)
C2	0.0218 (8)	0.0457 (12)	0.0177 (8)	−0.0074 (8)	−0.0032 (6)	0.0029 (8)
C3	0.0178 (7)	0.0447 (12)	0.0181 (8)	−0.0098 (7)	−0.0029 (6)	0.0071 (7)
C4	0.0214 (7)	0.0387 (11)	0.0178 (8)	−0.0124 (7)	−0.0062 (6)	0.0083 (7)
C5	0.0325 (9)	0.0257 (10)	0.0201 (8)	0.0009 (7)	−0.0015 (7)	−0.0003 (7)
C6	0.0283 (8)	0.0292 (10)	0.0244 (8)	0.0070 (7)	−0.0030 (7)	0.0050 (7)
C7	0.0220 (8)	0.0322 (10)	0.0196 (8)	−0.0019 (7)	−0.0053 (6)	0.0024 (7)
C8	0.0249 (8)	0.0268 (10)	0.0244 (8)	−0.0006 (7)	−0.0038 (6)	−0.0034 (7)
C9	0.0199 (7)	0.0248 (10)	0.0267 (8)	0.0005 (7)	−0.0027 (6)	0.0028 (7)
C10	0.0192 (7)	0.0263 (9)	0.0181 (8)	−0.0046 (6)	−0.0014 (6)	0.0039 (6)
C11	0.0243 (8)	0.0291 (10)	0.0205 (8)	−0.0063 (7)	−0.0023 (6)	0.0043 (7)

Cl1—C1	1.7395 (15)	C2—C3	1.414 (2)
O1—C11	1.306 (2)	C2—H2A	0.9500
O1—H1O1	0.866 (10)	C5—C6	1.386 (2)
O2—C11	1.229 (2)	C5—C10	1.395 (2)
N1—C1	1.328 (2)	C5—H5A	0.9500
N1—C4	1.348 (2)	C6—C7	1.387 (3)
N2—C4	1.350 (2)	C6—H6A	0.9500
N2—C3	1.351 (2)	C7—C8	1.384 (2)
N3—C4	1.336 (2)	C7—H7A	0.9500
N3—H2N3	0.79 (2)	C8—C9	1.392 (2)
N3—H1N3	0.85 (2)	C8—H8A	0.9500
N4—C3	1.328 (3)	C9—C10	1.391 (2)
N4—H2N4	0.88 (2)	C9—H9A	0.9500
N4—H1N4	0.88 (2)	C10—C11	1.490 (2)
C1—C2	1.358 (3)
C11—O1—H1O1	110 (2)	C6—C5—C10	120.18 (16)
C1—N1—C4	114.40 (16)	C6—C5—H5A	119.9
C4—N2—C3	118.60 (14)	C10—C5—H5A	119.9
C4—N3—H2N3	117.1 (16)	C5—C6—C7	119.92 (16)
C4—N3—H1N3	119.2 (15)	C5—C6—H6A	120.0
H2N3—N3—H1N3	123 (2)	C7—C6—H6A	120.0
C3—N4—H2N4	118.1 (15)	C8—C7—C6	120.20 (15)
C3—N4—H1N4	121.4 (13)	C8—C7—H7A	119.9
H2N4—N4—H1N4	121 (2)	C6—C7—H7A	119.9
N1—C1—C2	126.90 (15)	C7—C8—C9	120.15 (16)
N1—C1—Cl1	114.35 (13)	C7—C8—H8A	119.9
C2—C1—Cl1	118.76 (14)	C9—C8—H8A	119.9
C1—C2—C3	115.25 (17)	C10—C9—C8	119.83 (15)
C1—C2—H2A	122.4	C10—C9—H9A	120.1
C3—C2—H2A	122.4	C8—C9—H9A	120.1
N4—C3—N2	117.76 (15)	C9—C10—C5	119.71 (15)
N4—C3—C2	122.23 (17)	C9—C10—C11	121.29 (15)
N2—C3—C2	120.01 (17)	C5—C10—C11	118.99 (15)
N3—C4—N1	116.94 (17)	O2—C11—O1	123.62 (15)
N3—C4—N2	118.24 (15)	O2—C11—C10	121.44 (16)
N1—C4—N2	124.81 (16)	O1—C11—C10	114.94 (15)
C4—N1—C1—C2	−0.5 (2)	C10—C5—C6—C7	0.3 (3)
C4—N1—C1—Cl1	179.02 (11)	C5—C6—C7—C8	0.3 (3)
N1—C1—C2—C3	1.1 (3)	C6—C7—C8—C9	−0.4 (2)
Cl1—C1—C2—C3	−178.45 (11)	C7—C8—C9—C10	−0.2 (2)
C4—N2—C3—N4	178.65 (15)	C8—C9—C10—C5	0.9 (2)
C4—N2—C3—C2	−1.2 (2)	C8—C9—C10—C11	−178.71 (14)
C1—C2—C3—N4	179.98 (15)	C6—C5—C10—C9	−0.9 (2)
C1—C2—C3—N2	−0.1 (2)	C6—C5—C10—C11	178.67 (15)
C1—N1—C4—N3	−179.82 (14)	C9—C10—C11—O2	−179.79 (15)
C1—N1—C4—N2	−1.0 (2)	C5—C10—C11—O2	0.6 (2)
C3—N2—C4—N3	−179.31 (15)	C9—C10—C11—O1	0.5 (2)
C3—N2—C4—N1	1.9 (2)	C5—C10—C11—O1	−179.08 (14)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···N2	0.87 (2)	1.74 (2)	2.5976 (18)	168 (3)
N4—H2N4···O2	0.88 (2)	2.03 (2)	2.894 (2)	171.2 (18)
N4—H1N4···O2i	0.88 (2)	2.07 (2)	2.902 (2)	158.2 (19)
N3—H1N3···N1ii	0.85 (2)	2.18 (2)	3.020 (2)	171 (2)
C9—H9A···Cg1iii	0.95	2.99	3.6557 (19)	128

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C5–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯N2	0.87 (2)	1.74 (2)	2.5976 (18)	168 (3)
N4—H2N4⋯O2	0.88 (2)	2.03 (2)	2.894 (2)	171.2 (18)
N4—H1N4⋯O2i	0.88 (2)	2.07 (2)	2.902 (2)	158.2 (19)
N3—H1N3⋯N1ii	0.85 (2)	2.18 (2)	3.020 (2)	171 (2)
C9—H9A⋯Cg1iii	0.95	2.99	3.6557 (19)	128

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