4-Amino-N-(4,6-di-methyl-pyrimidin-2-yl)benzene-sulfonamide-1,4-di-aza-bicyclo-[2.2.2]octane (2/1).

The asymmetric unit of the title co-crystal, C12H14N4O2S·0.5C6H12N2, comprises the sulfonamide mol-ecule and half a mol-ecule of 1,4-di-aza-bicyclo-[2.2.2]octane (DABCO), the latter being disposed about a crystallographic twofold rotation axis. In the sulfonamide mol-ecule, the aromatic rings are almost perpendicular to one another [dihedral angle = 75.01 (8)°]. In the crystal, mol-ecules are connected into a three-mol-ecule aggregate via amide-DABCO N-H⋯N hydrogen bonds, and these are connected into a three-dimensional architecture via amino-DABCO N-H⋯O and amino-pyrimidine N-H⋯N hydrogen bonds.

Related literature

For the structure of the sulfonamide, see: Tiwari et al. (1984 ▶). For related studies of co-crystal formation, see: Ellis et al. (2009 ▶); Arman & Tiekink (2013 ▶). For co-crystals of the sulfonamide with carb­oxy­lic acids, see: Arman et al. (2010 ▶); Ghosh et al. (2011 ▶); Smith & Wermuth (2013 ▶).

Experimental

Crystal data

C12H14N4O2S·0.5C6H12N2

M = 334.42

Orthorhombic,

a = 26.488 (3) Å

b = 9.7886 (11) Å

c = 12.2163 (13) Å

V = 3167.4 (6) Å3

Z = 8

Mo Kα radiation

μ = 0.22 mm−1

T = 98 K

0.35 × 0.31 × 0.21 mm

Data collection

Rigaku AFC12/SATURN724 diffractometer

7965 measured reflections

3616 independent reflections

3264 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.115

S = 0.99

3616 reflections

219 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.41 e Å−3

Δρmin = −0.48 e Å−3

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: Crystal­Clear; 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, 2012 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) general, I. DOI: 10.1107/S1600536813027037/su2652sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813027037/su2652Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813027037/su2652Isup3.cml

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

C12H14N4O2S·0.5C6H12N2	F(000) = 1416
Mr = 334.42	Dx = 1.403 Mg m−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 11130 reflections
a = 26.488 (3) Å	θ = 2.1–40.3°
b = 9.7886 (11) Å	µ = 0.22 mm−1
c = 12.2163 (13) Å	T = 98 K
V = 3167.4 (6) Å3	Block, colourless
Z = 8	0.35 × 0.31 × 0.21 mm

Rigaku AFC12K/SATURN724 diffractometer	3264 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.032
Graphite monochromator	θmax = 27.5°, θmin = 2.2°
ω scans	h = −10→34
7965 measured reflections	k = −8→12
3616 independent reflections	l = −15→10

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ2(Fo2) + (0.0551P)2 + 2.7774P] where P = (Fo2 + 2Fc2)/3
3616 reflections	(Δ/σ)max < 0.001
219 parameters	Δρmax = 0.41 e Å−3
3 restraints	Δρmin = −0.48 e Å−3

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
S1	0.132415 (15)	0.06565 (4)	0.45540 (3)	0.01333 (12)
O1	0.11533 (5)	−0.05810 (12)	0.50942 (10)	0.0173 (3)
O2	0.13901 (5)	0.05841 (13)	0.33849 (10)	0.0183 (3)
N1	0.09018 (5)	0.17725 (15)	0.48968 (11)	0.0148 (3)
H1N	0.0745 (7)	0.152 (2)	0.5494 (11)	0.018*
N2	0.12538 (5)	0.36203 (15)	0.39075 (11)	0.0160 (3)
N3	0.07074 (6)	0.39389 (15)	0.54545 (11)	0.0160 (3)
N4	0.32337 (6)	0.25427 (17)	0.65547 (13)	0.0218 (3)
H2N	0.3284 (9)	0.250 (2)	0.7267 (8)	0.026*
H3N	0.3418 (8)	0.308 (2)	0.6139 (16)	0.026*
C1	0.09647 (6)	0.31690 (17)	0.47297 (13)	0.0148 (3)
C2	0.12939 (6)	0.49905 (19)	0.38156 (14)	0.0166 (3)
C3	0.10504 (7)	0.58644 (18)	0.45383 (14)	0.0181 (4)
H3	0.1085	0.6827	0.4474	0.022*
C4	0.07545 (7)	0.52934 (18)	0.53588 (14)	0.0169 (3)
C5	0.16111 (8)	0.55243 (19)	0.28925 (15)	0.0226 (4)
H5A	0.1968	0.5353	0.3050	0.034*
H5B	0.1555	0.6509	0.2812	0.034*
H5C	0.1517	0.5060	0.2212	0.034*
C6	0.04783 (7)	0.61545 (19)	0.61820 (15)	0.0223 (4)
H6A	0.0120	0.5909	0.6180	0.033*
H6B	0.0515	0.7122	0.5990	0.033*
H6C	0.0620	0.5995	0.6912	0.033*
C7	0.18946 (6)	0.11773 (17)	0.51417 (13)	0.0144 (3)
C8	0.19655 (6)	0.10442 (17)	0.62712 (14)	0.0159 (3)
H8	0.1710	0.0640	0.6712	0.019*
C9	0.24078 (6)	0.15020 (18)	0.67437 (14)	0.0173 (3)
H9	0.2456	0.1396	0.7509	0.021*
C10	0.27886 (7)	0.21239 (18)	0.61103 (14)	0.0172 (3)
C11	0.27024 (7)	0.2272 (2)	0.49774 (15)	0.0211 (4)
H11	0.2950	0.2707	0.4535	0.025*
C12	0.22649 (7)	0.17962 (19)	0.45039 (14)	0.0192 (4)
H12	0.2216	0.1890	0.3737	0.023*
N5	0.02978 (6)	0.88272 (15)	0.16824 (11)	0.0165 (3)
C13	0.05365 (6)	0.80970 (18)	0.26139 (13)	0.0168 (3)
H13A	0.0862	0.8535	0.2799	0.020*
H13B	0.0604	0.7137	0.2407	0.020*
C14	0.01889 (8)	1.02566 (18)	0.20149 (15)	0.0234 (4)
H14A	0.0043	1.0765	0.1389	0.028*
H14B	0.0506	1.0716	0.2236	0.028*
C15	−0.01819 (6)	0.81388 (19)	0.13850 (14)	0.0180 (3)
H15A	−0.0111	0.7197	0.1133	0.022*
H15B	−0.0347	0.8639	0.0779	0.022*

	U11	U22	U33	U12	U13	U23
S1	0.0140 (2)	0.0121 (2)	0.0139 (2)	−0.00069 (14)	0.00026 (15)	−0.00111 (14)
O1	0.0176 (6)	0.0125 (6)	0.0219 (6)	−0.0016 (5)	0.0005 (5)	0.0000 (5)
O2	0.0206 (6)	0.0201 (6)	0.0142 (6)	−0.0009 (5)	0.0005 (5)	−0.0043 (5)
N1	0.0135 (6)	0.0136 (7)	0.0174 (6)	−0.0002 (5)	0.0036 (5)	0.0003 (5)
N2	0.0162 (7)	0.0152 (7)	0.0166 (7)	0.0004 (5)	0.0013 (6)	0.0005 (6)
N3	0.0162 (7)	0.0162 (7)	0.0157 (6)	0.0013 (6)	0.0006 (5)	−0.0005 (5)
N4	0.0188 (7)	0.0266 (8)	0.0198 (7)	−0.0053 (6)	−0.0043 (6)	0.0018 (6)
C1	0.0123 (7)	0.0162 (8)	0.0158 (7)	0.0002 (6)	−0.0018 (6)	0.0000 (6)
C2	0.0150 (7)	0.0174 (8)	0.0174 (8)	0.0003 (6)	−0.0006 (6)	0.0022 (7)
C3	0.0188 (8)	0.0132 (7)	0.0225 (9)	0.0012 (6)	−0.0007 (7)	0.0011 (6)
C4	0.0158 (8)	0.0172 (8)	0.0176 (8)	0.0027 (6)	−0.0017 (6)	−0.0012 (6)
C5	0.0255 (9)	0.0181 (8)	0.0243 (9)	−0.0014 (7)	0.0057 (8)	0.0028 (7)
C6	0.0246 (9)	0.0188 (8)	0.0234 (9)	0.0047 (7)	0.0034 (7)	−0.0024 (7)
C7	0.0121 (7)	0.0140 (7)	0.0171 (7)	−0.0002 (6)	−0.0002 (6)	−0.0008 (6)
C8	0.0162 (8)	0.0155 (8)	0.0160 (7)	−0.0004 (6)	0.0034 (6)	0.0001 (6)
C9	0.0181 (8)	0.0181 (8)	0.0157 (7)	0.0007 (7)	−0.0015 (6)	−0.0012 (6)
C10	0.0154 (8)	0.0156 (8)	0.0204 (8)	−0.0002 (6)	−0.0008 (7)	0.0006 (7)
C11	0.0163 (8)	0.0255 (9)	0.0214 (8)	−0.0039 (7)	0.0018 (7)	0.0064 (7)
C12	0.0154 (8)	0.0251 (9)	0.0172 (8)	−0.0008 (7)	−0.0005 (7)	0.0053 (7)
N5	0.0166 (7)	0.0174 (7)	0.0154 (6)	−0.0021 (6)	0.0007 (5)	0.0016 (6)
C13	0.0151 (8)	0.0194 (8)	0.0159 (7)	0.0004 (6)	−0.0001 (6)	−0.0003 (6)
C14	0.0300 (10)	0.0144 (8)	0.0258 (9)	−0.0003 (7)	0.0000 (8)	0.0028 (7)
C15	0.0141 (7)	0.0234 (9)	0.0165 (7)	−0.0010 (7)	−0.0009 (6)	−0.0013 (7)

S1—O2	1.4406 (12)	C6—H6C	0.9800
S1—O1	1.4518 (12)	C7—C12	1.392 (2)
S1—N1	1.6188 (14)	C7—C8	1.399 (2)
S1—C7	1.7488 (17)	C8—C9	1.381 (2)
N1—C1	1.392 (2)	C8—H8	0.9500
N1—H1N	0.876 (9)	C9—C10	1.409 (2)
N2—C1	1.338 (2)	C9—H9	0.9500
N2—C2	1.350 (2)	C10—C11	1.410 (2)
N3—C4	1.337 (2)	C11—C12	1.377 (2)
N3—C1	1.348 (2)	C11—H11	0.9500
N4—C10	1.361 (2)	C12—H12	0.9500
N4—H2N	0.881 (9)	N5—C15	1.483 (2)
N4—H3N	0.877 (10)	N5—C14	1.485 (2)
C2—C3	1.388 (2)	N5—C13	1.485 (2)
C2—C5	1.500 (2)	C13—C15i	1.542 (2)
C3—C4	1.390 (2)	C13—H13A	0.9900
C3—H3	0.9500	C13—H13B	0.9900
C4—C6	1.502 (2)	C14—C14i	1.551 (4)
C5—H5A	0.9800	C14—H14A	0.9900
C5—H5B	0.9800	C14—H14B	0.9900
C5—H5C	0.9800	C15—C13i	1.542 (2)
C6—H6A	0.9800	C15—H15A	0.9900
C6—H6B	0.9800	C15—H15B	0.9900
O2—S1—O1	116.57 (7)	C12—C7—S1	120.40 (13)
O2—S1—N1	111.93 (8)	C8—C7—S1	119.60 (13)
O1—S1—N1	103.30 (7)	C9—C8—C7	119.74 (16)
O2—S1—C7	108.46 (8)	C9—C8—H8	120.1
O1—S1—C7	109.02 (8)	C7—C8—H8	120.1
N1—S1—C7	107.11 (8)	C8—C9—C10	121.19 (15)
C1—N1—S1	122.82 (12)	C8—C9—H9	119.4
C1—N1—H1N	117.0 (14)	C10—C9—H9	119.4
S1—N1—H1N	110.8 (14)	N4—C10—C11	120.04 (16)
C1—N2—C2	115.81 (15)	N4—C10—C9	122.07 (16)
C4—N3—C1	116.74 (15)	C11—C10—C9	117.86 (16)
C10—N4—H2N	120.7 (15)	C12—C11—C10	120.92 (16)
C10—N4—H3N	115.6 (15)	C12—C11—H11	119.5
H2N—N4—H3N	121 (2)	C10—C11—H11	119.5
N2—C1—N3	126.72 (16)	C11—C12—C7	120.37 (16)
N2—C1—N1	120.18 (15)	C11—C12—H12	119.8
N3—C1—N1	113.09 (15)	C7—C12—H12	119.8
N2—C2—C3	121.51 (16)	C15—N5—C14	109.18 (14)
N2—C2—C5	116.91 (15)	C15—N5—C13	109.49 (13)
C3—C2—C5	121.58 (16)	C14—N5—C13	109.06 (13)
C2—C3—C4	118.22 (16)	N5—C13—C15i	109.61 (13)
C2—C3—H3	120.9	N5—C13—H13A	109.7
C4—C3—H3	120.9	C15i—C13—H13A	109.7
N3—C4—C3	120.97 (16)	N5—C13—H13B	109.7
N3—C4—C6	116.90 (16)	C15i—C13—H13B	109.7
C3—C4—C6	122.13 (16)	H13A—C13—H13B	108.2
C2—C5—H5A	109.5	N5—C14—C14i	109.52 (9)
C2—C5—H5B	109.5	N5—C14—H14A	109.8
H5A—C5—H5B	109.5	C14i—C14—H14A	109.8
C2—C5—H5C	109.5	N5—C14—H14B	109.8
H5A—C5—H5C	109.5	C14i—C14—H14B	109.8
H5B—C5—H5C	109.5	H14A—C14—H14B	108.2
C4—C6—H6A	109.5	N5—C15—C13i	109.84 (13)
C4—C6—H6B	109.5	N5—C15—H15A	109.7
H6A—C6—H6B	109.5	C13i—C15—H15A	109.7
C4—C6—H6C	109.5	N5—C15—H15B	109.7
H6A—C6—H6C	109.5	C13i—C15—H15B	109.7
H6B—C6—H6C	109.5	H15A—C15—H15B	108.2
C12—C7—C8	119.89 (15)
O2—S1—N1—C1	−66.25 (15)	O2—S1—C7—C8	−166.16 (13)
O1—S1—N1—C1	167.54 (13)	O1—S1—C7—C8	−38.28 (16)
C7—S1—N1—C1	52.51 (15)	N1—S1—C7—C8	72.86 (15)
C2—N2—C1—N3	1.0 (3)	C12—C7—C8—C9	−1.4 (3)
C2—N2—C1—N1	−179.64 (15)	S1—C7—C8—C9	−177.55 (13)
C4—N3—C1—N2	−1.6 (3)	C7—C8—C9—C10	1.0 (3)
C4—N3—C1—N1	179.01 (15)	C8—C9—C10—N4	−177.89 (17)
S1—N1—C1—N2	28.3 (2)	C8—C9—C10—C11	0.4 (3)
S1—N1—C1—N3	−152.26 (12)	N4—C10—C11—C12	176.87 (18)
C1—N2—C2—C3	0.3 (2)	C9—C10—C11—C12	−1.5 (3)
C1—N2—C2—C5	−179.32 (15)	C10—C11—C12—C7	1.1 (3)
N2—C2—C3—C4	−1.0 (3)	C8—C7—C12—C11	0.3 (3)
C5—C2—C3—C4	178.66 (16)	S1—C7—C12—C11	176.48 (15)
C1—N3—C4—C3	0.8 (2)	C15—N5—C13—C15i	−61.24 (15)
C1—N3—C4—C6	−178.58 (15)	C14—N5—C13—C15i	58.17 (18)
C2—C3—C4—N3	0.4 (3)	C15—N5—C14—C14i	57.7 (2)
C2—C3—C4—C6	179.74 (16)	C13—N5—C14—C14i	−61.9 (2)
O2—S1—C7—C12	17.69 (17)	C14—N5—C15—C13i	−61.68 (17)
O1—S1—C7—C12	145.57 (14)	C13—N5—C15—C13i	57.66 (16)
N1—S1—C7—C12	−103.29 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N5ii	0.88 (2)	1.90 (2)	2.768 (2)	169 (2)
N4—H2N···O2iii	0.88 (1)	2.48 (2)	3.058 (2)	124 (2)
N4—H2N···N2iii	0.88 (1)	2.59 (2)	3.376 (2)	149 (2)
N4—H3N···O1iv	0.88 (2)	2.15 (2)	3.032 (2)	178 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯N5i	0.88 (2)	1.90 (2)	2.768 (2)	169 (2)
N4—H2N⋯O2ii	0.88 (1)	2.48 (2)	3.058 (2)	124 (2)
N4—H2N⋯N2ii	0.88 (1)	2.59 (2)	3.376 (2)	149 (2)
N4—H3N⋯O1iii	0.88 (2)	2.15 (2)	3.032 (2)	178 (2)

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