4′,4′,6′,6′-Tetra­chloro-3-(4,6-dimethyl­pyridin-2-yl)-3,4-dihydro­spiro­[1,3,2-benzoxaza­phosphinine-2,2′-(2λ⁵,4λ⁵,6λ⁵-cyclo­triphosphazene)]

The title compound, C₁₄H₁₄Cl₄N₅OP₃, is a phosphazene derivative with a bulky substituent attached through a spiro junction. The C₃NPO ring at the spiro junction has a twist–boat conformation, while the phosphazene ring has a flattened-boat conformation. The P_spiro atom is likely to be stereogenic.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.030
• wR factor = 0.074
• Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.54 Ratio
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C14
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C13

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.05
           From the CIF: _reflns_number_total               4149
           Count of symmetry unique reflns         2538
           Completeness (_total/calc)            163.48%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1611
           Fraction of Friedel pairs measured     0.635
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

4',4',6',6'-Tetrachloro-3-(4,6-dimethylpyridin-2-yl)-3,4-dihydrospiro[1,3,2- benzoxazaphosphinine-2,2'-(2λ⁵,4λ⁵,6λ⁵-cyclotriphosphazene)]

Crystal data

C14H14Cl4N5OP3	F(000) = 1016
Mr = 503.01	Dx = 1.653 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5847 reflections
a = 7.9310 (5) Å	θ = 1.7–27.2°
b = 11.9091 (10) Å	µ = 0.84 mm^−1
c = 21.3948 (15) Å	T = 100 K
V = 2020.8 (3) Å^3	Block, colourless
Z = 4	0.35 × 0.28 × 0.20 mm

Data collection

Stoe IPDS-II diffractometer	4149 independent reflections
Radiation source: fine-focus sealed tube	3874 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
Detector resolution: 6.67 pixels mm^-1	θmax = 27.1°, θmin = 1.9°
φ scans	h = −6→10
Absorption correction: integration (X-RED; Stoe & Cie, 2002)	k = −14→15
Tmin = 0.758, Tmax = 0.850	l = −26→27
9087 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.074	w = 1/[σ^2(Fo^2) + (0.0536P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max = 0.001
4149 reflections	Δρmax = 0.32 e Å^−3
276 parameters	Δρmin = −0.45 e Å^−3
0 restraints	Absolute structure: Flack (1983), with 1667 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.06 (6)

Special details

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.

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

	x	y	z	Uiso*/Ueq
Cl1	0.86957 (8)	0.99117 (5)	0.88126 (3)	0.02084 (13)
Cl2	0.77812 (9)	0.76941 (5)	0.94696 (3)	0.02431 (14)
Cl3	0.26464 (9)	1.00702 (6)	0.80518 (3)	0.02508 (14)
Cl4	0.20380 (8)	0.79022 (5)	0.87994 (3)	0.02556 (14)
P1	0.67277 (8)	0.91546 (5)	0.92224 (3)	0.01599 (13)
P2	0.34745 (8)	0.92823 (5)	0.88202 (3)	0.01711 (13)
P3	0.43946 (8)	1.03700 (5)	0.99012 (3)	0.01546 (13)
O1	0.3668 (2)	1.00203 (13)	1.05646 (7)	0.0193 (4)
N1	0.5360 (3)	0.89155 (17)	0.86995 (9)	0.0201 (4)
N2	0.2998 (3)	0.99908 (17)	0.94158 (9)	0.0180 (4)
N3	0.6204 (3)	0.98061 (17)	0.98269 (9)	0.0176 (4)
N4	0.4525 (3)	1.17528 (16)	0.99733 (9)	0.0181 (4)
N5	0.5270 (3)	1.18751 (17)	0.89303 (9)	0.0190 (4)
C1	0.4524 (3)	1.0409 (2)	1.10965 (10)	0.0198 (5)
C2	0.4860 (4)	0.9669 (2)	1.15773 (12)	0.0248 (6)
C3	0.5686 (4)	1.0064 (3)	1.20972 (12)	0.0299 (6)
C4	0.6180 (4)	1.1168 (3)	1.21357 (13)	0.0318 (7)
C5	0.5837 (4)	1.1911 (3)	1.16475 (12)	0.0275 (6)
C6	0.4974 (3)	1.1528 (2)	1.11187 (11)	0.0207 (5)
C7	0.4513 (4)	1.2308 (2)	1.05925 (11)	0.0202 (5)
C8	0.4779 (3)	1.2430 (2)	0.94425 (11)	0.0184 (5)
C9	0.4534 (3)	1.3584 (2)	0.94720 (12)	0.0200 (5)
C10	0.4846 (3)	1.4211 (2)	0.89364 (12)	0.0217 (5)
C11	0.5380 (4)	1.3649 (2)	0.84073 (12)	0.0232 (5)
C12	0.5561 (3)	1.2492 (2)	0.84108 (11)	0.0220 (5)
C13	0.6144 (4)	1.1877 (2)	0.78389 (12)	0.0298 (6)
C14	0.4592 (4)	1.5466 (2)	0.89427 (14)	0.0310 (6)
H13A	0.6194	1.1087	0.7926	0.045*
H13B	0.7243	1.2141	0.7722	0.045*
H13C	0.5367	1.2010	0.7503	0.045*
H14A	0.4220	1.5697	0.9350	0.046*
H14B	0.3757	1.5667	0.8638	0.046*
H14C	0.5636	1.5833	0.8845	0.046*
H21	0.450 (4)	0.896 (2)	1.1557 (12)	0.013 (7)*
H31	0.595 (4)	0.957 (2)	1.2419 (14)	0.023 (8)*
H41	0.670 (5)	1.144 (3)	1.2455 (16)	0.031 (9)*
H51	0.620 (5)	1.262 (3)	1.1681 (16)	0.032 (9)*
H71	0.345 (5)	1.258 (2)	1.0663 (13)	0.021 (7)*
H72	0.533 (4)	1.292 (2)	1.0605 (13)	0.019 (7)*
H91	0.410 (4)	1.393 (2)	0.9848 (12)	0.014 (7)*
H111	0.552 (6)	1.400 (3)	0.8056 (17)	0.046 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0161 (3)	0.0235 (3)	0.0230 (2)	−0.0003 (2)	0.0035 (2)	−0.0010 (2)
Cl2	0.0230 (3)	0.0185 (3)	0.0314 (3)	0.0051 (2)	0.0005 (2)	0.0006 (2)
Cl3	0.0235 (3)	0.0326 (3)	0.0191 (3)	0.0062 (3)	−0.0037 (2)	−0.0013 (2)
Cl4	0.0190 (3)	0.0208 (3)	0.0370 (3)	−0.0012 (2)	−0.0026 (3)	−0.0074 (2)
P1	0.0138 (3)	0.0166 (3)	0.0175 (3)	0.0019 (2)	0.0004 (2)	−0.0021 (2)
P2	0.0141 (3)	0.0191 (3)	0.0182 (3)	0.0015 (2)	−0.0012 (2)	−0.0040 (2)
P3	0.0155 (3)	0.0163 (3)	0.0145 (2)	0.0006 (2)	0.0020 (2)	−0.0016 (2)
O1	0.0208 (10)	0.0212 (8)	0.0159 (7)	−0.0005 (8)	0.0028 (7)	−0.0024 (6)
N1	0.0149 (11)	0.0251 (10)	0.0202 (10)	0.0026 (9)	−0.0004 (8)	−0.0065 (8)
N2	0.0138 (10)	0.0211 (9)	0.0190 (9)	0.0026 (8)	0.0020 (8)	−0.0055 (8)
N3	0.0151 (10)	0.0219 (10)	0.0158 (9)	0.0013 (8)	−0.0007 (8)	−0.0030 (7)
N4	0.0222 (11)	0.0168 (9)	0.0154 (9)	0.0006 (8)	0.0029 (8)	−0.0032 (7)
N5	0.0176 (11)	0.0203 (9)	0.0191 (10)	0.0016 (8)	0.0019 (8)	0.0003 (8)
C1	0.0160 (12)	0.0287 (12)	0.0146 (10)	0.0033 (10)	0.0038 (9)	−0.0023 (9)
C2	0.0241 (15)	0.0291 (14)	0.0212 (11)	0.0082 (12)	0.0091 (10)	0.0020 (10)
C3	0.0220 (14)	0.0487 (17)	0.0190 (11)	0.0101 (14)	0.0032 (10)	0.0057 (11)
C4	0.0256 (15)	0.0533 (18)	0.0165 (12)	0.0000 (14)	−0.0037 (11)	−0.0022 (12)
C5	0.0250 (15)	0.0380 (15)	0.0194 (11)	−0.0053 (13)	0.0006 (11)	−0.0054 (11)
C6	0.0173 (12)	0.0293 (13)	0.0155 (11)	0.0018 (10)	0.0030 (9)	−0.0035 (10)
C7	0.0236 (14)	0.0192 (11)	0.0177 (11)	0.0004 (11)	0.0016 (10)	−0.0061 (9)
C8	0.0157 (12)	0.0220 (11)	0.0175 (10)	0.0006 (9)	0.0006 (9)	0.0003 (9)
C9	0.0164 (13)	0.0210 (11)	0.0225 (11)	0.0004 (10)	−0.0023 (10)	−0.0028 (9)
C10	0.0163 (13)	0.0208 (11)	0.0280 (13)	−0.0012 (10)	−0.0025 (10)	0.0023 (10)
C11	0.0211 (14)	0.0262 (13)	0.0223 (12)	−0.0016 (11)	0.0011 (11)	0.0072 (10)
C12	0.0166 (13)	0.0315 (14)	0.0178 (11)	0.0008 (11)	0.0023 (10)	0.0009 (9)
C13	0.0342 (17)	0.0337 (14)	0.0216 (11)	0.0047 (13)	0.0075 (11)	0.0014 (11)
C14	0.0349 (17)	0.0220 (13)	0.0360 (15)	0.0019 (12)	−0.0023 (13)	0.0050 (10)

Geometric parameters (Å, º)

P1—Cl1	2.0045 (9)	C5—C4	1.395 (4)
P1—Cl2	2.0008 (9)	C5—H51	0.90 (4)
P1—N1	1.584 (2)	C6—C5	1.399 (4)
P1—N3	1.5643 (19)	C7—C6	1.505 (3)
P2—Cl3	2.0036 (9)	C7—H71	0.91 (4)
P2—Cl4	2.0003 (9)	C7—H72	0.97 (3)
P2—N1	1.579 (2)	C8—N5	1.338 (3)
P2—N2	1.5743 (19)	C8—C9	1.389 (3)
P3—O1	1.5875 (17)	C8—N4	1.408 (3)
P3—N2	1.584 (2)	C9—H91	0.97 (3)
P3—N3	1.592 (2)	C9—C10	1.390 (4)
P3—N4	1.657 (2)	C10—C11	1.382 (4)
O1—C1	1.403 (3)	C10—C14	1.508 (4)
N4—C7	1.481 (3)	C11—C12	1.385 (4)
N5—C12	1.352 (3)	C11—H111	0.87 (4)
C1—C6	1.380 (4)	C13—C12	1.499 (3)
C1—C2	1.380 (4)	C13—H13A	0.9600
C2—H21	0.89 (3)	C13—H13B	0.9600
C3—C2	1.374 (4)	C13—H13C	0.9600
C3—C4	1.375 (5)	C14—H14A	0.9600
C3—H31	0.93 (3)	C14—H14B	0.9600
C4—H41	0.86 (4)	C14—H14C	0.9600
N1—P1—Cl1	107.76 (9)	C4—C5—H51	118 (2)
N1—P1—Cl2	108.44 (8)	C6—C5—H51	122 (2)
N3—P1—N1	119.42 (12)	C1—C6—C5	118.0 (3)
N3—P1—Cl2	108.88 (8)	C1—C6—C7	120.5 (2)
N3—P1—Cl1	110.21 (9)	C5—C6—C7	121.5 (2)
Cl2—P1—Cl1	100.45 (4)	N4—C7—C6	113.1 (2)
N1—P2—Cl3	107.81 (9)	N4—C7—H71	108.1 (19)
N1—P2—Cl4	107.96 (8)	C6—C7—H71	108.6 (18)
N2—P2—N1	120.52 (11)	N4—C7—H72	110.7 (17)
N2—P2—Cl4	108.77 (9)	C6—C7—H72	106.2 (17)
N2—P2—Cl3	109.54 (8)	H71—C7—H72	110 (3)
Cl4—P2—Cl3	100.36 (4)	N5—C8—C9	124.5 (2)
O1—P3—N3	107.80 (10)	N5—C8—N4	114.8 (2)
O1—P3—N4	101.54 (9)	C9—C8—N4	120.7 (2)
N2—P3—O1	104.94 (11)	C8—C9—C10	118.0 (2)
N2—P3—N3	116.38 (11)	C8—C9—H91	120.9 (16)
N2—P3—N4	112.83 (11)	C10—C9—H91	121.0 (16)
N3—P3—N4	111.85 (12)	C11—C10—C9	118.0 (2)
C1—O1—P3	117.58 (16)	C11—C10—C14	121.9 (2)
P2—N1—P1	118.89 (13)	C9—C10—C14	120.1 (2)
P2—N2—P3	121.04 (14)	C10—C11—C12	120.6 (2)
P1—N3—P3	122.09 (13)	C10—C11—H111	121 (3)
C7—N4—P3	121.79 (16)	C12—C11—H111	118 (3)
C8—N4—C7	117.82 (19)	N5—C12—C11	121.8 (2)
C8—N4—P3	120.22 (16)	N5—C12—C13	117.3 (2)
C8—N5—C12	117.0 (2)	C11—C12—C13	120.9 (2)
C6—C1—C2	122.7 (3)	C12—C13—H13A	109.5
C6—C1—O1	118.1 (2)	C12—C13—H13B	109.5
C2—C1—O1	119.1 (2)	H13A—C13—H13B	109.5
C3—C2—C1	118.5 (3)	C12—C13—H13C	109.5
C3—C2—H21	121.0 (18)	H13A—C13—H13C	109.5
C1—C2—H21	120.5 (18)	H13B—C13—H13C	109.5
C2—C3—C4	120.8 (3)	C10—C14—H14A	109.5
C2—C3—H31	119.2 (19)	C10—C14—H14B	109.5
C4—C3—H31	120.0 (19)	H14A—C14—H14B	109.5
C3—C4—C5	120.4 (3)	C10—C14—H14C	109.5
C3—C4—H41	123 (2)	H14A—C14—H14C	109.5
C5—C4—H41	117 (2)	H14B—C14—H14C	109.5
C4—C5—C6	119.6 (3)
N3—P1—N1—P2	−3.4 (2)	P3—N4—C7—C6	19.9 (3)
Cl2—P1—N1—P2	121.98 (12)	C8—N5—C12—C11	0.7 (4)
Cl1—P1—N1—P2	−130.10 (12)	C8—N5—C12—C13	178.9 (3)
N1—P1—N3—P3	−7.6 (2)	C2—C1—C6—C5	1.4 (4)
Cl2—P1—N3—P3	−132.81 (12)	O1—C1—C6—C5	−179.6 (2)
Cl1—P1—N3—P3	117.91 (13)	C2—C1—C6—C7	−177.4 (2)
N2—P2—N1—P1	6.7 (2)	O1—C1—C6—C7	1.6 (4)
Cl4—P2—N1—P1	−119.05 (13)	C6—C1—C2—C3	−0.5 (4)
Cl3—P2—N1—P1	133.33 (12)	O1—C1—C2—C3	−179.5 (2)
N1—P2—N2—P3	1.0 (2)	C2—C3—C4—C5	0.5 (5)
Cl4—P2—N2—P3	126.38 (13)	C6—C5—C4—C3	0.5 (5)
Cl3—P2—N2—P3	−124.83 (12)	C1—C6—C5—C4	−1.4 (4)
O1—P3—N2—P2	−130.47 (14)	C7—C6—C5—C4	177.4 (3)
N3—P3—N2—P2	−11.4 (2)	N4—C7—C6—C1	−33.7 (4)
N4—P3—N2—P2	119.84 (15)	N4—C7—C6—C5	147.5 (3)
N2—P3—O1—C1	−170.39 (17)	N5—C8—C9—C10	−1.2 (4)
N3—P3—O1—C1	64.95 (18)	N4—C8—C9—C10	178.4 (2)
N4—P3—O1—C1	−52.72 (19)	N5—C8—N4—C7	161.2 (2)
N2—P3—N4—C8	−54.7 (2)	C9—C8—N4—C7	−18.5 (4)
O1—P3—N4—C8	−166.5 (2)	N5—C8—N4—P3	−14.3 (3)
N3—P3—N4—C8	78.8 (2)	C9—C8—N4—P3	166.1 (2)
N2—P3—N4—C7	130.1 (2)	C9—C8—N5—C12	0.8 (4)
O1—P3—N4—C7	18.3 (2)	N4—C8—N5—C12	−178.8 (2)
N3—P3—N4—C7	−96.4 (2)	C4—C3—C2—C1	−0.5 (4)
N2—P3—N3—P1	14.8 (2)	C9—C10—C11—C12	1.3 (4)
O1—P3—N3—P1	132.32 (14)	C14—C10—C11—C12	−178.3 (3)
N4—P3—N3—P1	−116.88 (15)	C11—C10—C9—C8	0.1 (4)
P3—O1—C1—C6	46.9 (3)	C14—C10—C9—C8	179.7 (3)
P3—O1—C1—C2	−134.1 (2)	C10—C11—C12—N5	−1.8 (4)
C8—N4—C7—C6	−155.4 (2)	C10—C11—C12—C13	−179.9 (3)