A novel tubular hydrogen-bond pattern in a new di­aza­phosphole oxide: a combination of X-ray crystallography and theoretical study of hydrogen bonds

In the structure of 2-(4-chloro­anilino)-1,3,2λ⁴-di­aza­phosphol-2-one, C₁₂H₁₁ClN₃OP, each mol­ecule is connected with four neighbouring mol­ecules through (N—H)₂...O hydrogen bonds. These hydrogen bonds form a tubular arrangement along the [001] direction built from R³₃(12) and R₄³(14) hydrogen-bond ring motifs, combined with a C(4) chain motif. The hole constructed in the tubular architecture includes a 12-atom arrangement (three P, three N, three O and three H atoms) belonging to three adjacent mol­ecules hydrogen bonded to each other. One of the N—H groups of the di­aza­phosphole ring, not co-operating in classical hydrogen bonding, takes part in an N—H...π inter­action. This inter­action occurs within the tubular array and does not change the dimension of the hydrogen-bond pattern. The energies of the N—H...O and N—H...π hydrogen bonds were studied by NBO (natural bond orbital) analysis, using the experimental hydrogen-bonded cluster of mol­ecules as the input file for the chemical calculations. In the ¹H NMR experiment, the nitro­gen-bound proton of the di­aza­phosphole ring has a high value of 17.2 Hz for the ²J_H–P coupling constant.

Computing details

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: enCIFer (Allen et al., 2004).

(I)

Crystal data

C12H11ClN3OP	Dx = 1.424 Mg m^−3
Mr = 279.67	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3c1	Cell parameters from 15343 reflections
Hall symbol: P 3 -2"c	θ = 3.7–33.8°
a = 15.8635 (2) Å	µ = 0.41 mm^−1
c = 8.9754 (1) Å	T = 293 K
V = 1956.06 (5) Å^3	Prism, light-yellow
Z = 6	0.36 × 0.22 × 0.15 mm
F(000) = 864

Data collection

Agilent Xcalibur Sapphire3 Gemini diffractometer	3965 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3841 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 16.0302 pixels mm^-1	θmax = 30.5°, θmin = 3.4°
ω scans	h = −22→22
Absorption correction: analytical [CrysAlis PRO (Agilent, 2014), based on expressions derived by Clark & Reid (1995)]	k = −22→22
Tmin = 0.894, Tmax = 0.956	l = −12→12
44280 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.041	w = 1/[σ^2(Fo^2) + (0.0687P)^2 + 0.4018P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.108	(Δ/σ)max < 0.001
S = 1.07	Δρmax = 0.68 e Å^−3
3965 reflections	Δρmin = −0.37 e Å^−3
163 parameters	Absolute structure: Flack x determined using 1807 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.004 (16)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
C1	0.42038 (19)	0.43506 (18)	0.1857 (3)	0.0301 (5)
P1	0.48648 (5)	0.34701 (4)	0.02975 (7)	0.02636 (14)
Cl1	0.11062 (8)	−0.11481 (9)	0.2729 (2)	0.0943 (5)
C7	0.37777 (19)	0.15395 (19)	0.1049 (3)	0.0303 (5)
C6	0.36447 (18)	0.40615 (18)	0.0542 (3)	0.0293 (5)
C5	0.2988 (2)	0.4369 (2)	0.0244 (4)	0.0387 (6)
H5	0.2618	0.4179	−0.0624	0.046*
N2	0.46328 (17)	0.23506 (16)	0.0495 (3)	0.0326 (4)
H2A	0.5089	0.2241	0.0227	0.039*
C12	0.3605 (2)	0.0616 (2)	0.0674 (3)	0.0388 (6)
H12	0.4050	0.0552	0.0081	0.047*
C11	0.2780 (3)	−0.0208 (2)	0.1174 (4)	0.0487 (8)
H11	0.2667	−0.0823	0.0912	0.058*
C3	0.3435 (3)	0.5245 (2)	0.2576 (4)	0.0450 (7)
H3	0.3354	0.5642	0.3255	0.054*
N3	0.38993 (18)	0.34958 (18)	−0.0347 (3)	0.0328 (4)
H3A	0.3589	0.3196	−0.1139	0.039*
C8	0.3118 (2)	0.1625 (2)	0.1967 (4)	0.0446 (7)
H8	0.3230	0.2237	0.2242	0.054*
C9	0.2293 (3)	0.0797 (3)	0.2473 (5)	0.0555 (9)
H9	0.1853	0.0855	0.3088	0.067*
C2	0.4098 (2)	0.4938 (2)	0.2884 (3)	0.0383 (6)
H2	0.4460	0.5123	0.3759	0.046*
O1	0.57753 (15)	0.39939 (15)	−0.0583 (2)	0.0358 (4)
C4	0.2892 (3)	0.4970 (2)	0.1274 (4)	0.0459 (7)
H4	0.2458	0.5190	0.1088	0.055*
N1	0.48379 (18)	0.39743 (18)	0.1895 (2)	0.0330 (4)
H1A	0.5175	0.4003	0.2664	0.040*
C10	0.2125 (2)	−0.0110 (3)	0.2063 (5)	0.0500 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0300 (11)	0.0256 (10)	0.0329 (11)	0.0126 (9)	−0.0006 (9)	0.0010 (9)
P1	0.0263 (3)	0.0249 (3)	0.0275 (2)	0.0125 (2)	−0.0024 (2)	0.0010 (2)
Cl1	0.0399 (5)	0.0552 (6)	0.1616 (15)	0.0043 (4)	0.0219 (7)	0.0308 (8)
C7	0.0301 (11)	0.0264 (11)	0.0341 (11)	0.0139 (9)	−0.0004 (9)	0.0025 (9)
C6	0.0277 (11)	0.0263 (10)	0.0332 (11)	0.0130 (9)	−0.0012 (9)	0.0000 (8)
C5	0.0310 (13)	0.0420 (14)	0.0460 (15)	0.0203 (11)	−0.0029 (11)	0.0019 (12)
N2	0.0317 (10)	0.0254 (9)	0.0430 (10)	0.0160 (8)	0.0087 (9)	0.0049 (8)
C12	0.0431 (15)	0.0304 (13)	0.0424 (14)	0.0180 (12)	0.0021 (12)	−0.0022 (11)
C11	0.0457 (17)	0.0279 (13)	0.061 (2)	0.0100 (12)	−0.0077 (15)	−0.0034 (13)
C3	0.0453 (16)	0.0365 (14)	0.0554 (18)	0.0221 (13)	0.0097 (14)	−0.0033 (13)
N3	0.0347 (11)	0.0368 (11)	0.0312 (10)	0.0211 (9)	−0.0096 (8)	−0.0076 (9)
C8	0.0390 (15)	0.0334 (13)	0.0643 (17)	0.0202 (12)	0.0167 (14)	0.0088 (13)
C9	0.0358 (15)	0.0505 (19)	0.085 (3)	0.0249 (15)	0.0211 (16)	0.0199 (18)
C2	0.0436 (15)	0.0321 (12)	0.0379 (13)	0.0180 (12)	−0.0011 (11)	−0.0051 (10)
O1	0.0288 (9)	0.0334 (9)	0.0397 (9)	0.0114 (8)	0.0015 (7)	0.0083 (8)
C4	0.0392 (15)	0.0436 (16)	0.063 (2)	0.0268 (14)	0.0078 (13)	0.0050 (14)
N1	0.0387 (11)	0.0367 (11)	0.0301 (9)	0.0237 (10)	−0.0093 (8)	−0.0060 (8)
C10	0.0271 (13)	0.0376 (15)	0.073 (2)	0.0070 (12)	−0.0021 (13)	0.0122 (15)

Geometric parameters (Å, º)

C1—C2	1.380 (4)	C12—C11	1.383 (5)
C1—N1	1.404 (3)	C12—H12	0.9300
C1—C6	1.408 (3)	C11—C10	1.379 (6)
P1—O1	1.484 (2)	C11—H11	0.9300
P1—N2	1.633 (2)	C3—C4	1.387 (5)
P1—N1	1.653 (2)	C3—C2	1.390 (5)
P1—N3	1.657 (2)	C3—H3	0.9300
Cl1—C10	1.738 (3)	N3—H3A	0.8600
C7—C12	1.390 (4)	C8—C9	1.387 (4)
C7—C8	1.391 (4)	C8—H8	0.9300
C7—N2	1.413 (3)	C9—C10	1.376 (6)
C6—C5	1.380 (4)	C9—H9	0.9300
C6—N3	1.403 (3)	C2—H2	0.9300
C5—C4	1.390 (5)	C4—H4	0.9300
C5—H5	0.9300	N1—H1A	0.8600
N2—H2A	0.8600
C2—C1—N1	128.8 (3)	C12—C11—H11	120.3
C2—C1—C6	120.7 (3)	C4—C3—C2	121.1 (3)
N1—C1—C6	110.5 (2)	C4—C3—H3	119.4
O1—P1—N2	107.09 (12)	C2—C3—H3	119.4
O1—P1—N1	116.40 (13)	C6—N3—P1	112.48 (18)
N2—P1—N1	112.70 (13)	C6—N3—H3A	123.8
O1—P1—N3	116.94 (12)	P1—N3—H3A	123.8
N2—P1—N3	110.86 (13)	C9—C8—C7	120.1 (3)
N1—P1—N3	92.48 (12)	C9—C8—H8	119.9
C12—C7—C8	119.0 (3)	C7—C8—H8	119.9
C12—C7—N2	117.9 (2)	C10—C9—C8	120.0 (3)
C8—C7—N2	123.1 (2)	C10—C9—H9	120.0
C5—C6—N3	128.8 (3)	C8—C9—H9	120.0
C5—C6—C1	120.7 (3)	C1—C2—C3	118.3 (3)
N3—C6—C1	110.4 (2)	C1—C2—H2	120.9
C6—C5—C4	118.3 (3)	C3—C2—H2	120.9
C6—C5—H5	120.8	C3—C4—C5	120.9 (3)
C4—C5—H5	120.8	C3—C4—H4	119.6
C7—N2—P1	128.32 (18)	C5—C4—H4	119.6
C7—N2—H2A	115.8	C1—N1—P1	112.45 (18)
P1—N2—H2A	115.8	C1—N1—H1A	123.8
C11—C12—C7	120.8 (3)	P1—N1—H1A	123.8
C11—C12—H12	119.6	C9—C10—C11	120.6 (3)
C7—C12—H12	119.6	C9—C10—Cl1	120.0 (3)
C10—C11—C12	119.4 (3)	C11—C10—Cl1	119.3 (3)
C10—C11—H11	120.3

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1^i	0.86	2.06	2.909 (3)	171
N1—H1A···O1^ii	0.86	1.97	2.825 (3)	174
N3—H3A···Cg^iii	0.86	2.46	3.303 (3)	169

Symmetry codes: (i) −y+1, x−y, z; (ii) −y+1, −x+1, z+1/2; (iii) x, x−y, z−1/2.