N,N,N',N'-Tetra-kis(pyridin-4-yl)methane-diamine monohydrate.

In the title compound, C(21)H(18)N(6)·H(2)O, two 4,4'-dipyridyl-amine groups are linked by a methyl-ene C atom, which sits on a twofold axis. The lattice water mol-ecule is located slightly off a twofold axis, and is therefore disordered over two positions. In the crystal, the organic mol-ecules and the water mol-ecule are linked by O-H⋯N hydrogen bonds. The organic mol-ecules exhibit extensive offset face-to-face π-π inter-actions to symmetry equivalents [centroid-centroid distances = 3.725 (3) and 4.059 (3) Å].

Related literature

For metal-organic frameworks including 4,4′-dipyridyl­amine, see: Braverman & LaDuca (2007 ▶); Shyu et al. (2009 ▶). For the catalysis of multidimensional n class="Chemical">metal-organic frameworks, see: Welbes & Borovik (2005 ▶). For self-assembled metal-organic networks and their luminescent properties, see: Shin et al. (2012 ▶); Zeng et al. (2010 ▶).

Experimental

Crystal data

C21H18n class="Chemical">N6·H2O

M = 372.42

Monoclinic,

a = 13.9048 (11) Å

b = 13.7637 (11) Å

c = 10.0569 (8) Å

β = 109.142 (2)°

V = 1818.3 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 200 K

0.34 × 0.26 × 0.25 mm

Data collection

Siemens SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.973, T max = 0.978

6540 measured reflections

2241 independent reflections

1313 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.163

S = 1.09

2241 reflections

130 parameters

H-atom parameters constrained

Δρmax = 0.23 e Å−3

Δρmin = −0.22 e Å−3

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAIn class="Chemical">NT; 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 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812019010/pk2409sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812019010/pk2409Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812019010/pk2409Isup3.cml

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

C21H18N6·H2O	F(000) = 784
Mr = 372.42	Dx = 1.360 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2155 reflections
a = 13.9048 (11) Å	θ = 2.7–28.2°
b = 13.7637 (11) Å	µ = 0.09 mm−1
c = 10.0569 (8) Å	T = 200 K
β = 109.142 (2)°	Block, colorless
V = 1818.3 (3) Å3	0.34 × 0.26 × 0.25 mm
Z = 4

Siemens SMART CCD diffractometer	2241 independent reflections
Radiation source: fine-focus sealed tube	1313 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
φ and ω scans	θmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→18
Tmin = 0.973, Tmax = 0.978	k = −18→16
6540 measured reflections	l = −13→12

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.163	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0744P)2 + 0.1675P] where P = (Fo2 + 2Fc2)/3
2241 reflections	(Δ/σ)max < 0.001
130 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

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	Occ. (<1)
N1	0.08225 (11)	0.18977 (10)	0.72834 (16)	0.0378 (4)
N2	0.32207 (12)	0.08225 (11)	1.07690 (17)	0.0456 (4)
N3	0.12205 (15)	0.19990 (14)	0.3297 (2)	0.0627 (6)
C1	0.24926 (14)	0.11276 (13)	0.8290 (2)	0.0415 (5)
H1	0.2569	0.1085	0.7387	0.050*
C2	0.32458 (14)	0.07990 (13)	0.9453 (2)	0.0455 (5)
H2	0.3836	0.0532	0.9315	0.055*
C3	0.23734 (15)	0.12101 (13)	1.0907 (2)	0.0444 (5)
H3	0.2327	0.1249	1.1827	0.053*
C4	0.15609 (14)	0.15572 (12)	0.9798 (2)	0.0388 (5)
H4	0.0977	0.1813	0.9966	0.047*
C5	0.16063 (13)	0.15281 (11)	0.84383 (19)	0.0356 (4)
C6	0.09476 (13)	0.19319 (12)	0.5933 (2)	0.0373 (4)
C7	0.09792 (15)	0.28090 (13)	0.5269 (2)	0.0461 (5)
H7	0.0918	0.3406	0.5708	0.055*
C8	0.11000 (16)	0.28004 (16)	0.3965 (2)	0.0569 (6)
H8	0.1097	0.3407	0.3512	0.068*
C9	0.11687 (16)	0.11622 (16)	0.3940 (2)	0.0555 (6)
H9	0.1238	0.0577	0.3480	0.067*
C10	0.10220 (14)	0.10896 (14)	0.5221 (2)	0.0452 (5)
H10	0.0972	0.0471	0.5613	0.054*
C11	0.0000	0.24732 (13)	0.7500	0.0355 (6)
H11A	0.0293	0.2898	0.8329	0.043*	0.50
H11B	−0.0293	0.2898	0.6671	0.043*	0.50
O1	0.4878 (6)	0.01031 (13)	0.7761 (8)	0.0617 (12)	0.50
H1W	0.5532	−0.0300	0.8088	0.130 (11)*

	U11	U22	U33	U12	U13	U23
N1	0.0315 (8)	0.0354 (8)	0.0500 (9)	0.0046 (6)	0.0180 (7)	0.0039 (6)
N2	0.0331 (9)	0.0417 (9)	0.0577 (11)	0.0006 (7)	0.0089 (8)	0.0033 (7)
N3	0.0592 (13)	0.0774 (13)	0.0613 (12)	0.0230 (10)	0.0331 (10)	0.0175 (10)
C1	0.0353 (11)	0.0379 (10)	0.0547 (12)	0.0007 (8)	0.0193 (9)	0.0021 (8)
C2	0.0335 (11)	0.0403 (10)	0.0650 (14)	0.0014 (8)	0.0190 (9)	−0.0005 (9)
C3	0.0454 (12)	0.0394 (10)	0.0498 (12)	−0.0056 (9)	0.0175 (9)	0.0005 (8)
C4	0.0315 (10)	0.0314 (9)	0.0577 (12)	−0.0013 (7)	0.0203 (9)	0.0024 (8)
C5	0.0319 (10)	0.0260 (8)	0.0497 (11)	−0.0037 (7)	0.0146 (8)	0.0022 (7)
C6	0.0262 (9)	0.0382 (10)	0.0498 (11)	0.0035 (7)	0.0158 (8)	0.0066 (8)
C7	0.0407 (12)	0.0382 (10)	0.0663 (14)	0.0027 (8)	0.0270 (10)	0.0090 (9)
C8	0.0490 (14)	0.0604 (14)	0.0709 (15)	0.0124 (10)	0.0326 (11)	0.0269 (11)
C9	0.0514 (14)	0.0595 (13)	0.0595 (14)	0.0176 (10)	0.0235 (11)	0.0006 (10)
C10	0.0433 (12)	0.0387 (10)	0.0572 (12)	0.0078 (8)	0.0214 (10)	0.0033 (8)
C11	0.0285 (13)	0.0291 (12)	0.0509 (15)	0.000	0.0158 (11)	0.000
O1	0.052 (2)	0.0452 (13)	0.072 (2)	0.0162 (17)	−0.0008 (17)	−0.0107 (16)

N1—C5	1.402 (2)	C4—H4	0.9500
N1—C6	1.425 (2)	C6—C10	1.384 (3)
N1—C11	1.4649 (17)	C6—C7	1.387 (2)
N2—C2	1.335 (2)	C7—C8	1.376 (3)
N2—C3	1.341 (2)	C7—H7	0.9500
N3—C8	1.330 (3)	C8—H8	0.9500
N3—C9	1.335 (3)	C9—C10	1.373 (3)
C1—C2	1.366 (3)	C9—H9	0.9500
C1—C5	1.402 (2)	C10—H10	0.9500
C1—H1	0.9500	C11—N1i	1.4649 (17)
C2—H2	0.9500	C11—H11A	0.9900
C3—C4	1.387 (3)	C11—H11B	0.9900
C3—H3	0.9500	O1—O1ii	0.7127
C4—C5	1.390 (2)	O1—H1W	1.0230
C5—N1—C6	119.78 (14)	C10—C6—N1	121.22 (15)
C5—N1—C11	120.38 (13)	C7—C6—N1	121.38 (16)
C6—N1—C11	117.96 (12)	C8—C7—C6	118.99 (18)
C2—N2—C3	114.92 (16)	C8—C7—H7	120.5
C8—N3—C9	115.77 (19)	C6—C7—H7	120.5
C2—C1—C5	119.54 (18)	N3—C8—C7	124.30 (18)
C2—C1—H1	120.2	N3—C8—H8	117.8
C5—C1—H1	120.2	C7—C8—H8	117.8
N2—C2—C1	125.35 (19)	N3—C9—C10	124.49 (19)
N2—C2—H2	117.3	N3—C9—H9	117.8
C1—C2—H2	117.3	C10—C9—H9	117.8
N2—C3—C4	124.43 (18)	C9—C10—C6	118.94 (17)
N2—C3—H3	117.8	C9—C10—H10	120.5
C4—C3—H3	117.8	C6—C10—H10	120.5
C3—C4—C5	119.59 (17)	N1i—C11—N1	114.54 (16)
C3—C4—H4	120.2	N1i—C11—H11A	108.6
C5—C4—H4	120.2	N1—C11—H11A	108.6
C4—C5—C1	116.16 (16)	N1i—C11—H11B	108.6
C4—C5—N1	122.06 (16)	N1—C11—H11B	108.6
C1—C5—N1	121.76 (17)	H11A—C11—H11B	107.6
C10—C6—C7	117.39 (18)	O1ii—O1—H1W	69.5
C3—N2—C2—C1	−0.3 (3)	C11—N1—C6—C10	−129.57 (17)
C5—C1—C2—N2	0.0 (3)	C5—N1—C6—C7	−115.35 (19)
C2—N2—C3—C4	0.8 (3)	C11—N1—C6—C7	49.1 (2)
N2—C3—C4—C5	−1.1 (3)	C10—C6—C7—C8	−1.2 (3)
C3—C4—C5—C1	0.7 (2)	N1—C6—C7—C8	−179.92 (17)
C3—C4—C5—N1	−177.87 (15)	C9—N3—C8—C7	3.2 (3)
C2—C1—C5—C4	−0.2 (2)	C6—C7—C8—N3	−2.1 (3)
C2—C1—C5—N1	178.37 (16)	C8—N3—C9—C10	−1.2 (3)
C6—N1—C5—C4	174.20 (15)	N3—C9—C10—C6	−1.8 (3)
C11—N1—C5—C4	10.1 (2)	C7—C6—C10—C9	2.9 (3)
C6—N1—C5—C1	−4.3 (2)	N1—C6—C10—C9	−178.31 (17)
C11—N1—C5—C1	−168.41 (15)	C5—N1—C11—N1i	−82.93 (13)
C5—N1—C6—C10	65.9 (2)	C6—N1—C11—N1i	112.69 (14)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···N2iii	1.02	1.88	2.869 (2)	161

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1W⋯N2i	1.02	1.88	2.869 (2)	161

Symmetry code: (i) .