Crystal structure of N,N'-bis-(diiso-propyl-phosphan-yl)-4-methyl-pyridine-2,6-di-amine.

In the mol-ecule of the title compound, C18H35N3P2, the methyl-pyridine-2,6-di-amine moiety is almost planar, with a maximum deviation of 0.0129 (9) Å for one of the amine N atoms. Whereas one of the P atoms is co-planar with this mean plane [deviation = 0.0158 (10) Å], the other P atom is considerably displaced out of the mean plane by 0.5882 (10) Å. In the crystal, no directional intermolecular interactions beyond van der Waals contacts could be identified.

Related literature

The title compound belongs to the family of PNP pincer ligands that are capable of forming complexes with various transition metals, leading to inter­esting properties and applications, see: Benito-Garagorri & Kirchner (2008 ▶); Langer et al. (2011 ▶); Bichler et al. (2013 ▶). For general aspects of pincer ligands and derived complexes, see: Morales-Morales & Jensen (2007 ▶).

Experimental

Crystal data

C18H35N3P2

M = 355.4

Orthorhombic,

a = 14.3394 (12) Å

b = 10.0089 (16) Å

c = 29.562 (3) Å

V = 4242.9 (9) Å3

Z = 8

Mo Kα radiation

μ = 0.21 mm−1

T = 100 K

0.70 × 0.28 × 0.04 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2013 ▶) T min = 0.93, T max = 0.99

149837 measured reflections

6241 independent reflections

4614 reflections with I > 3σ(I)

R int = 0.066

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.046

S = 1.39

6241 reflections

216 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.29 e Å−3

Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2013 ▶); cell refinement: SAINT-Plus (Bruker, 2013 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: JANA2006 (Petříček, et al., 2014 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814010976/su0004sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814010976/su0004Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814010976/su0004Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814010976/su0004fig1.tif

The mol­ecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 80% probability level.

CCDC reference: 1004282

Additional supporting information: crystallographic information; 3D view; checkCIF report

C18H35N3P2	F(000) = 1552
Mr = 355.4	Dx = 1.113 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9974 reflections
a = 14.3394 (12) Å	θ = 2.5–30°
b = 10.0089 (16) Å	µ = 0.21 mm−1
c = 29.562 (3) Å	T = 100 K
V = 4242.9 (9) Å3	Plate, translucent colourless
Z = 8	0.70 × 0.28 × 0.04 mm

Bruker APEXII CCD diffractometer	6241 independent reflections
Radiation source: X-ray tube	4614 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.066
ω and φ scans	θmax = 30.1°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2013)	h = −20→20
Tmin = 0.93, Tmax = 0.99	k = −14→14
149837 measured reflections	l = −41→41

Refinement on F	Primary atom site location: iterative
R[F2 > 2σ(F2)] = 0.031	Secondary atom site location: none
wR(F2) = 0.046	Hydrogen site location: geom,difmap
S = 1.39	H atoms treated by a mixture of independent and constrained refinement
6241 reflections	Weighting scheme based on measured s.u.'s w = 1/(σ2(F) + 0.0004F2)
216 parameters	(Δ/σ)max = 0.014
2 restraints	Δρmax = 0.29 e Å−3
132 constraints	Δρmin = −0.21 e Å−3

Experimental. Spectroscopic data for the title compound:1H-NMR (400 MHz, CDCl3) 6.34 (s, 2H), 4.88 (bs, 2H), 2.18 (s, 3H), 1.87–1.60 (m, 4H), 1.15–0.92 (m, 24H). 31P NMR (162 MHz, CDCl3) 55.65. 13C-NMR (63 MHz, CDCl3) 156.59 (d, J = 21.9 Hz), 153.94 (s), 99.14 (d, J = 19.7 Hz), 26.27 (d, J = 11.4 Hz), 21.80 (d, J = 15.3 Hz), 18.46 (d, J = 19.7 Hz), 17.18 (d, J = 7.9 Hz).

	x	y	z	Uiso*/Ueq
P1	0.781952 (19)	0.61761 (3)	0.277629 (10)	0.01628 (8)
P2	0.62798 (2)	0.33177 (3)	0.045775 (10)	0.01837 (8)
N1	0.70180 (6)	0.42925 (9)	0.16952 (3)	0.0149 (2)
N2	0.73728 (7)	0.50053 (10)	0.24153 (3)	0.0176 (3)
N3	0.66959 (7)	0.33964 (10)	0.10001 (3)	0.0200 (3)
C1	0.69814 (7)	0.52954 (11)	0.19953 (4)	0.0146 (3)
C2	0.65663 (7)	0.65213 (11)	0.19012 (4)	0.0166 (3)
C3	0.61705 (7)	0.67148 (11)	0.14781 (4)	0.0164 (3)
C4	0.62017 (8)	0.56884 (11)	0.11637 (4)	0.0180 (3)
C5	0.66312 (7)	0.44882 (11)	0.12890 (4)	0.0158 (3)
C6	0.57228 (8)	0.80360 (11)	0.13652 (4)	0.0220 (3)
C7	0.76791 (8)	0.52642 (12)	0.33135 (4)	0.0211 (3)
C8	0.66449 (9)	0.50783 (15)	0.34168 (5)	0.0326 (4)
C9	0.81669 (11)	0.60387 (14)	0.36929 (4)	0.0321 (4)
C10	0.90932 (8)	0.60456 (12)	0.26658 (4)	0.0207 (3)
C11	0.92671 (9)	0.64908 (13)	0.21773 (4)	0.0280 (4)
C12	0.95354 (8)	0.46787 (12)	0.27535 (4)	0.0251 (3)
C13	0.71074 (8)	0.20717 (12)	0.02331 (4)	0.0196 (3)
C14	0.80702 (9)	0.27110 (14)	0.01819 (4)	0.0304 (4)
C15	0.67652 (9)	0.15302 (14)	−0.02210 (4)	0.0288 (4)
C16	0.51998 (8)	0.23173 (12)	0.05297 (4)	0.0218 (3)
C17	0.44882 (9)	0.31763 (15)	0.07830 (5)	0.0322 (4)
C18	0.53214 (9)	0.09667 (13)	0.07581 (4)	0.0285 (4)
H1c2	0.655417	0.721798	0.212436	0.0199*
H1c4	0.593587	0.579767	0.086795	0.0216*
H1c6	0.531526	0.829737	0.160715	0.0264*
H2c6	0.619791	0.870155	0.132575	0.0264*
H3c6	0.536997	0.795035	0.109071	0.0264*
H1c7	0.795933	0.439591	0.328992	0.0253*
H1c8	0.634885	0.463114	0.316796	0.0392*
H2c8	0.657585	0.4551	0.368598	0.0392*
H3c8	0.635919	0.593558	0.346145	0.0392*
H1c9	0.88155	0.614221	0.362035	0.0386*
H2c9	0.788416	0.690318	0.372402	0.0386*
H3c9	0.810676	0.555582	0.397193	0.0386*
H1c10	0.939505	0.661523	0.288221	0.0248*
H1c11	0.897622	0.734181	0.212703	0.0336*
H2c11	0.992597	0.656607	0.212556	0.0336*
H3c11	0.900823	0.584359	0.197319	0.0336*
H1c12	0.950231	0.447657	0.307053	0.0302*
H2c12	0.920525	0.400794	0.258548	0.0302*
H3c12	1.017612	0.469408	0.265948	0.0302*
H1c13	0.714996	0.133665	0.044067	0.0235*
H1c14	0.823637	0.315444	0.045839	0.0365*
H2c14	0.852243	0.203124	0.011583	0.0365*
H3c14	0.805635	0.334884	−0.006051	0.0365*
H1c15	0.620148	0.103025	−0.0176	0.0345*
H2c15	0.664577	0.226133	−0.042306	0.0345*
H3c15	0.723356	0.095883	−0.034922	0.0345*
H1c16	0.498808	0.208867	0.023147	0.0262*
H1c17	0.440136	0.400466	0.062477	0.0386*
H2c17	0.390461	0.270903	0.080008	0.0386*
H3c17	0.471218	0.335423	0.108302	0.0386*
H1c18	0.569613	0.039846	0.056995	0.0343*
H2c18	0.562348	0.108617	0.104509	0.0343*
H3c18	0.472136	0.056297	0.080352	0.0343*
H1n3	0.6939 (10)	0.2689 (9)	0.1124 (5)	0.042 (4)*
H1n2	0.7548 (9)	0.4176 (4)	0.2438 (5)	0.027 (4)*

	U11	U22	U33	U12	U13	U23
P1	0.01745 (13)	0.01506 (14)	0.01634 (13)	0.00115 (10)	−0.00312 (10)	−0.00393 (11)
P2	0.02390 (15)	0.01747 (15)	0.01375 (13)	0.00096 (11)	−0.00236 (10)	−0.00068 (11)
N1	0.0140 (4)	0.0141 (4)	0.0165 (4)	−0.0004 (3)	−0.0013 (3)	−0.0016 (3)
N2	0.0208 (5)	0.0137 (4)	0.0182 (4)	0.0012 (4)	−0.0056 (4)	−0.0025 (4)
N3	0.0287 (5)	0.0153 (5)	0.0160 (4)	0.0045 (4)	−0.0058 (4)	−0.0028 (4)
C1	0.0112 (4)	0.0159 (5)	0.0167 (5)	−0.0022 (4)	−0.0006 (4)	−0.0010 (4)
C2	0.0156 (5)	0.0141 (5)	0.0199 (5)	0.0001 (4)	−0.0007 (4)	−0.0034 (4)
C3	0.0139 (5)	0.0135 (5)	0.0217 (5)	−0.0003 (4)	0.0000 (4)	0.0010 (4)
C4	0.0207 (5)	0.0163 (5)	0.0170 (5)	0.0016 (4)	−0.0031 (4)	0.0002 (4)
C5	0.0156 (5)	0.0155 (5)	0.0162 (5)	−0.0014 (4)	0.0003 (4)	−0.0020 (4)
C6	0.0239 (6)	0.0168 (5)	0.0253 (6)	0.0045 (4)	−0.0025 (4)	0.0002 (5)
C7	0.0249 (6)	0.0211 (6)	0.0171 (5)	0.0032 (4)	−0.0013 (4)	−0.0022 (4)
C8	0.0296 (6)	0.0423 (8)	0.0260 (6)	0.0022 (6)	0.0067 (5)	0.0028 (6)
C9	0.0461 (8)	0.0318 (7)	0.0185 (6)	0.0040 (6)	−0.0077 (5)	−0.0039 (5)
C10	0.0177 (5)	0.0183 (6)	0.0260 (6)	−0.0018 (4)	−0.0031 (4)	−0.0044 (5)
C11	0.0260 (6)	0.0249 (6)	0.0332 (7)	−0.0011 (5)	0.0065 (5)	0.0012 (5)
C12	0.0182 (5)	0.0240 (6)	0.0332 (7)	0.0018 (4)	−0.0041 (5)	−0.0020 (5)
C13	0.0227 (5)	0.0198 (5)	0.0161 (5)	−0.0014 (4)	0.0030 (4)	−0.0015 (4)
C14	0.0269 (6)	0.0341 (8)	0.0301 (7)	−0.0059 (5)	0.0072 (5)	−0.0027 (6)
C15	0.0374 (7)	0.0300 (7)	0.0189 (6)	−0.0014 (6)	0.0031 (5)	−0.0060 (5)
C16	0.0192 (5)	0.0272 (6)	0.0191 (5)	0.0018 (5)	−0.0018 (4)	−0.0049 (5)
C17	0.0242 (6)	0.0400 (8)	0.0323 (7)	0.0051 (6)	0.0006 (5)	−0.0097 (6)
C18	0.0271 (6)	0.0282 (7)	0.0303 (7)	−0.0062 (5)	0.0044 (5)	−0.0002 (5)

P1—N2	1.7094 (10)	C9—H2c9	0.96
P1—C7	1.8426 (12)	C9—H3c9	0.96
P1—C10	1.8599 (12)	C10—C11	1.5319 (18)
P2—N3	1.7125 (11)	C10—C12	1.5300 (17)
P2—C13	1.8452 (12)	C10—H1c10	0.96
P2—C16	1.8564 (12)	C11—H1c11	0.96
N1—C1	1.3408 (14)	C11—H2c11	0.96
N1—C5	1.3372 (14)	C11—H3c11	0.96
N2—C1	1.3932 (14)	C12—H1c12	0.96
N2—H1n2	0.870 (6)	C12—H2c12	0.96
N3—C5	1.3901 (15)	C12—H3c12	0.96
N3—H1n3	0.870 (11)	C13—C14	1.5292 (18)
C1—C2	1.3918 (16)	C13—C15	1.5286 (17)
C2—C3	1.3872 (16)	C13—H1c13	0.96
C2—H1c2	0.96	C14—H1c14	0.96
C3—C4	1.3861 (16)	C14—H2c14	0.96
C3—C6	1.5074 (16)	C14—H3c14	0.96
C4—C5	1.3998 (16)	C15—H1c15	0.96
C4—H1c4	0.96	C15—H2c15	0.96
C6—H1c6	0.96	C15—H3c15	0.96
C6—H2c6	0.96	C16—C17	1.5301 (18)
C6—H3c6	0.96	C16—C18	1.5212 (18)
C7—C8	1.5256 (17)	C16—H1c16	0.96
C7—C9	1.5324 (18)	C17—H1c17	0.96
C7—H1c7	0.96	C17—H2c17	0.96
C8—H1c8	0.96	C17—H3c17	0.96
C8—H2c8	0.96	C18—H1c18	0.96
C8—H3c8	0.96	C18—H2c18	0.96
C9—H1c9	0.96	C18—H3c18	0.96
N2—P1—C7	99.06 (5)	P1—C10—C12	116.11 (8)
N2—P1—C10	102.14 (5)	P1—C10—H1c10	106.5
C7—P1—C10	102.93 (5)	C11—C10—C12	110.63 (10)
N3—P2—C13	98.28 (5)	C11—C10—H1c10	112.45
N3—P2—C16	102.02 (5)	C12—C10—H1c10	103.38
C13—P2—C16	102.31 (5)	C10—C11—H1c11	109.47
C1—N1—C5	117.93 (9)	C10—C11—H2c11	109.47
P1—N2—C1	124.36 (8)	C10—C11—H3c11	109.47
P1—N2—H1n2	119.8 (9)	H1c11—C11—H2c11	109.47
C1—N2—H1n2	112.7 (9)	H1c11—C11—H3c11	109.47
P2—N3—C5	126.02 (8)	H2c11—C11—H3c11	109.47
P2—N3—H1n3	119.7 (9)	C10—C12—H1c12	109.47
C5—N3—H1n3	114.1 (9)	C10—C12—H2c12	109.47
N1—C1—N2	114.71 (9)	C10—C12—H3c12	109.47
N1—C1—C2	122.99 (10)	H1c12—C12—H2c12	109.47
N2—C1—C2	122.29 (10)	H1c12—C12—H3c12	109.47
C1—C2—C3	118.57 (10)	H2c12—C12—H3c12	109.47
C1—C2—H1c2	120.71	P2—C13—C14	109.48 (9)
C3—C2—H1c2	120.71	P2—C13—C15	110.44 (8)
C2—C3—C4	119.21 (10)	P2—C13—H1c13	109.19
C2—C3—C6	119.76 (10)	C14—C13—C15	110.57 (10)
C4—C3—C6	121.02 (10)	C14—C13—H1c13	109.06
C3—C4—C5	118.21 (10)	C15—C13—H1c13	108.06
C3—C4—H1c4	120.89	C13—C14—H1c14	109.47
C5—C4—H1c4	120.89	C13—C14—H2c14	109.47
N1—C5—N3	114.13 (9)	C13—C14—H3c14	109.47
N1—C5—C4	123.08 (10)	H1c14—C14—H2c14	109.47
N3—C5—C4	122.78 (10)	H1c14—C14—H3c14	109.47
C3—C6—H1c6	109.47	H2c14—C14—H3c14	109.47
C3—C6—H2c6	109.47	C13—C15—H1c15	109.47
C3—C6—H3c6	109.47	C13—C15—H2c15	109.47
H1c6—C6—H2c6	109.47	C13—C15—H3c15	109.47
H1c6—C6—H3c6	109.47	H1c15—C15—H2c15	109.47
H2c6—C6—H3c6	109.47	H1c15—C15—H3c15	109.47
P1—C7—C8	109.83 (8)	H2c15—C15—H3c15	109.47
P1—C7—C9	109.29 (8)	P2—C16—C17	108.02 (9)
P1—C7—H1c7	109.89	P2—C16—C18	115.76 (8)
C8—C7—C9	111.03 (10)	P2—C16—H1c16	106.69
C8—C7—H1c7	108.11	C17—C16—C18	111.01 (10)
C9—C7—H1c7	108.66	C17—C16—H1c16	111.87
C7—C8—H1c8	109.47	C18—C16—H1c16	103.42
C7—C8—H2c8	109.47	C16—C17—H1c17	109.47
C7—C8—H3c8	109.47	C16—C17—H2c17	109.47
H1c8—C8—H2c8	109.47	C16—C17—H3c17	109.47
H1c8—C8—H3c8	109.47	H1c17—C17—H2c17	109.47
H2c8—C8—H3c8	109.47	H1c17—C17—H3c17	109.47
C7—C9—H1c9	109.47	H2c17—C17—H3c17	109.47
C7—C9—H2c9	109.47	C16—C18—H1c18	109.47
C7—C9—H3c9	109.47	C16—C18—H2c18	109.47
H1c9—C9—H2c9	109.47	C16—C18—H3c18	109.47
H1c9—C9—H3c9	109.47	H1c18—C18—H2c18	109.47
H2c9—C9—H3c9	109.47	H1c18—C18—H3c18	109.47
P1—C10—C11	107.76 (8)	H2c18—C18—H3c18	109.47